Compilation of EPA's Sampling and Analysis Methods

Keith, Lawrence H.
"E, F, H, 1, K, L"
Compilation of EPA's Sampling and Analysis Methods
Edited by Lawrence H. Keith
Boca Raton: CRC Press LLC,1996
E
n-Eicosane EPA Method 1625 PRECISION & ACCURACY The detection limits of the
CAS #112-95-8 method are usually dependent on the level of interferences
rather than instrumental limitations. The limits typify the min-
TITLE Semivolatile Organic Compounds by Isotope Dilu- imum quantities that can be detected with no interferences
tion GC/MS present.
MATRIX The compounds may be determined in waters, The minimum level (in g/mL) was 10. This is defined as a
soils, and municipal sludges by this method. minimum level at which the analytical system shall give recog-
nizable mass spectra (background corrected) and acceptable
METHOD SUMMARY This method is used to determine
calibration points.
176 semivolatile toxic organic pollutants associated with the
CWA (as amended 1987); the RCRA (as amended 1986); the The MDL (in g/kg) in low solids was 83 and in high solids
CERCLA (as amended 1986); and other compounds amenable was 229; these were determined in digested sludge (low solids)
to extraction and analysis by capillary column gas chromatog- and in filter cake or compost (high solids).
raphy-mass spectrometry (GC/MS).
Note: Background levels of this compound were present in the
Stable isotopically-labeled analogs of the compounds of interest sludge tested, resulting in higher than expected MDLs. The
are added to the sample. If the solids content is less than 1%, MDL for this compound is expected to be approximately
a 1-L sample is extracted at pH 12–13, then at pH <2 with 50 g/kg with no interferences present.
methylene chloride using continuous extraction techniques.
The labeled and native compound initial precision as standard
If the solids content is 30% or less, the sample is diluted to 1% deviation (in g/L) was 59.
solids with reagent water, homogenized ultrasonically, and The labeled and native compound initial accuracy as average
extracted at pH 12–13, then at pH <2 with methylene chloride recovery (in g/L) was 53–263.
using continuous extraction techniques. If the solids content is
SAMPLE COLLECTION, PRESERVATION & HANDLING
greater than 30%, the sample is extracted using ultrasonic
Collect samples in glass containers. Aqueous samples which
techniques.
flow freely are collected in refrigerated bottles using automatic
Each extract is dried over sodium sulfate, concentrated to a sampling equipment. Solid samples are collected as grab sam-
volume of 5 mL, cleaned up using GPC, if necessary, and con- ples using widemouth jars. Maintain samples at 0 to 4C from
centrated. Extracts are concentrated to 1 mL if GPC is not the time of collection until extraction. If residual chlorine is
performed, and to 0.5 mL if GPC is performed. present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
An internal standard is added to the extract, and a 1-mL aliquot
and analyze all extracts within 40 days of extraction.
of the extract is injected into the GC. The compounds are
separated by GC and detected by a MS. The labeled compounds SAMPLE PREPARATION Samples containing 1% solids or
serve to correct the variability of the analytical technique. less are extracted directly using continuous liquid-liquid
extraction techniques. Samples containing 1 to 30% solids are
INTERFERENCES Solvents, reagents, glassware, and other
diluted to the 1% level with reagent water and extracted using
sample processing hardware may yield artifacts and/or elevated
continuous liquid-liquid extraction techniques. Samples con-
baselines causing misinterpretation of chromatograms and
taining greater than 30% solids are extracted using ultrasonic
spectra. Materials used in the analysis must be demonstrated
techniques.
to be free from interferences under the conditions of analysis
by running method blanks initially and with each sample lot Base/neutral extraction — Adjust the pH of the waters in the
(sample started through the extraction process on a given 8-h extractors to 12–13 with 6 N NaOH. Extract with methylene
shift, to a maximum of 20). Specific selection of reagents and chloride for 24–48 h.
purification of solvents by distillation in all glass systems may Acid extraction — Adjust the pH of the waters in the extractors
be required. Glassware and, where possible, reagents are to 2 or less using 6 N sulfuric acid. Extract with methylene
cleaned by solvent rinse and baking at 450C for 1-h minimum. chloride for 24–48 h.
Interferences coextracted from samples will vary considerably Ultrasonic extraction of high solids samples — Add anhy-
from source to source, depending on the diversity of the site drous sodium sulfate to the sample and QC aliquot(s).
being sampled. Add acetone:methylene chloride (1:1) to the sample and
mix thoroughly
INSTRUMENTATION Major instrumentation includes a GC
with a splitless or on-column injection port for capillary col- Concentrate extracts using a K-D apparatus.
umn, a MS with 70 eV electron impact ionization, and a data
QUALITY CONTROL The analyst is permitted to modify
system to collect and record MS data, and process it. A K-D
this method to improve separations or lower the costs of mea-
apparatus is used to concentrate extracts.
surements, provided all performance specifications are met.
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1% Analyses of blanks are required to demonstrate freedom from
vinyl silicone bonded phased fused silica capillary column. contamination. When results of spikes indicate atypical
©1996 CRC Press LLC

method performance for samples, the samples are diluted to taminants that are coextracted from the sample. The base-
bring method performance within acceptable limits. neutral extraction may cause significantly reduced recovery of
phenols. The packed gas chromatographic columns recom-
For low solids (aqueous samples), extract, concentrate, and
mended for the basic fraction may not exhibit sufficient reso-
analyze two sets of four 1-L aliquots (8 aliquots total) of the
lution for some analytes.
precision and recovery standard. For high solids samples, two
sets of four 30-g aliquots of the high solids reference matrix INSTRUMENTATION A GC/MS system with an injection
are used. port designed for on-column injection when using packed col-
umns and for splitless injection when using capillary columns.
Spike all samples with labeled compounds to assess method
performance. Compute percent recovery of the labeled com- Column for base/neutrals: 1.8 m long  2 mm I.D. glass,
pounds using the internal standard method. Compare the packed with 3% SP-2550 on Supelcoport (100/120 mesh)
labeled compound recovery for each compound with the cor- or equivalent.
responding labeled compound recovery. Column for acids: 1.8 m long 2 mm I.D. glass, packed with
1% SP-1240DA on Supelcoport (100/120 mesh) or equivalent.
Reagent water and high solids reference matrix blanks are ana-
lyzed to demonstrate freedom from contamination. Extract PRECISION & ACCURACY The MDL concentrations were
and concentrate a 1-L reagent water blank or a high solids obtained using reagent water. The MDL actually achieved in a
reference matrix blank with each sample’s lot (samples started given analysis will vary depending on instrument sensitivity
through the extraction process on the same 8-h shift, to a and matrix effects. This method was tested by 15 laboratories
maximum of 20 samples). using reagent water, drinking water, surface water, and indus-
trial wastewaters spiked at six concentrations over the range 5
Field replicates may be collected to determine the precision of
to 100 g/L. Single operator precision, overall precision, and
the sampling technique, and spiked samples may be required
method accuracy were found to be directly related to the con-
to determine the accuracy of the analysis when the internal
centration of the parameter matrix.
standard method is used.
The MDL (in g/L) in reagent water was not detected.
REFERENCE Semivolatile Organic Compounds by Isotope
The standard deviation (in g/L based on 4 recovery measure-
Dilution GC/MS. Office of Water Regulation and Standards,
ments) was not reported.
U.S. EPA Industrial Technology Division, Washington, DC,
The range (in g/L) for average recovery for 4 measurements
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
was not reported.
U.S. EPA, Office of Water Regulations and Standards, 401 M
The range (in %) for percent recovery was not reported.
St., SW, Washington, DC, 20460. Phone: 202-382-7131).
Accuracy (in g/L) as expected recovery for one or more mea-
surements of a sample containing a true concentration of
C was not reported.
Endosulfan I EPA Method 625 Precision (in g/L) as expected single analyst standard devia-
CAS #959-98-8 tion of measurements at an average concentration found at
X was not reported.
TITLE Base/Neutrals and Acids, U.S. EPA Method 625 Overall precision (in g/L) as expected interlaboratory stan-
dard deviation of measurements in an average concentra-
MATRIX This methods covers municipal and industrial
tion found at X was not reported.
wastewaters.
C = True value of the concentration in g/L.
METHOD SUMMARY Approximately 1 L of sample is seri-
X = Average recovery found for measurements of samples con-
ally extracted with methylene chloride at a pH greater than 11
taining a concentration at C in g/L.
and again at a pH less than 2 using a separatory funnel or a
continuous extractor. The methylene chloride extract is dried, SAMPLE PREPARATION Adjust the pH to >11 with sodium
concentrated to a volume of 1 mL, and analyzed by GC/MS. hydroxide and serially extract in a separatory funnel with meth-
Qualitative identification of the parameters in the extract is ylene chloride or else in a continuous extractor. Next, adjust
performed using the retention time and the relative abundance the pH to <2 with sulfuric acid and serially extract in a sepa-
of three characteristic masses (m/z). Qualitative analysis is per- ratory funnel with methylene chloride or else in a continuous
formed using either external or internal standard techniques extractor. Dry the extracts separately through a column of
with a single characteristic m/z. anhydrous sodium sulfate and then concentrate each of the
extracts to 1.0 mL using a K-D apparatus.
INTERFERENCES Method interferences may be caused by
contaminants in solvents, reagents, glassware, and other sample SAMPLE COLLECTION, PRESERVATION & HANDLING
processing hardware. Glassware must be scrupulously cleaned. Grab samples must be collected in glass containers. All samples
Glassware should be heated in a muffle furnace at 400C for 5 must be refrigerated at 4C from the time of collection until
to 30 min. Some thermally stable materials, such as PCBs, may extraction. If residual chlorine is present, add 80 mg of sodium
not be eliminated by this treatment. Solvent rinses with acetone thiosulfate/L of sample and mix well. All samples must be
and pesticide quality hexane may be substituted for the muffle extracted within 7 days of collection and completely analyzed
furnace heating. Matrix interferences may be caused by con- within 40 days of extraction.

QUALITY CONTROL Make an initial, one-time, demonstra- Column 2: Supelcoport (100/120 mesh) coated with 3% OV-1
tion of the ability to generate acceptable accuracy and precision in a 1.8 m 4 mm I.D. glass column.
with this method. Before processing any samples, the analyst
PRECISION & ACCURACY The method was tested by 20
must analyze a reagent water blank to demonstrate that inter-
laboratories using organic-free reagent water, drinking water,
ferences from the analytical system and glassware are under
surface water, and three industrial wastewaters spiked at six
control. Each time a set of samples is extracted or reagents are
changed, a reagent water blank must be processed. Spike and concentrations. Concentrations used in the study ranged from
0.5 to 30 g/L for single-component pesticides and from 8.5 to
analyze a minimum of 5% of all samples to monitor and eval-
uate lab data quality. A QC check sample concentrate that 400 g/L for multicomponent parameters. Overall precision
contains each parameter of interest at a concentration of and method accuracy were found to be directly related to the
concentration of the analyte and essentially independent of the
100 g/mL in acetone is required. PCBs and multicomponent
pesticides may be omitted from this test. sample matrix. The sensitivity of this method usually depends
on the concentration of interferences rather than on instru-
After analysis of five spiked wastewater samples, calculate the mental limitations.
average percent recovery and the standard deviation of the
MDL in g/L was 0.014.
percent recovery. Spike all samples with the surrogate standard
Concentration range in g/L was 0.5–30.
spiking solution and calculate the percent recovery of each
Accuracy as recovery (x*) in g/L was 0.97C + 0.04 .
surrogate compound.
Overall precision (S*) in g/L was 0.18x + 0.08.
REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct.
x* = Expected recovery for one or more measurements of a sample
26, 1984.
containing concentration C, in g/L.
S* = Expected interlaboratory standard deviation of measure-
ments at an average concentration found of the analyte
Endosulfan I EPA Method 8080 in g/L.
CAS #959-98-8 C = True value for the concentration, in g/L.
TITLE Organochlorine Pesticides and Polychlorinated taining a concentration of C, in g/L.
Biphenyls By Gas Chromatography
SAMPLING METHOD
MATRIX This method is used to determine the concentra- Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
tion of various organochlorine pesticides and polychlorinated a screw-top Teflon®-lined cover. Pre-wash the bottle with deter-
biphenyls in extracts prepared from water, groundwater, soils, gent, rinse with distilled water and methanol (or isopropanol).
and sediments.
Soil, sediments, and sludges — Use an 8-oz. widemouth glass
METHOD SUMMARY This method covers 26 pesticides and with a screw-top Teflon®-lined cover. Pre-wash the bottle with
Aroclor (PCB) mixtures and it is suitable for monitoring-type detergent, rinse with distilled water and methanol (or isopro-
analyses. After extraction, concentration and solvent exchange panol).
to hexane, a 2- to 5-L sample aliquot is injected into a GC
SAMPLE PRESERVATION Cool water, soil, sediment, or
using the solvent flush technique, and the analytes are detected
sludge samples immediately to 4C.
by an electron capture detector (ECD) or an electrolytic con-
ductivity detector in the halogen mode (HECD). Both neat and Water samples — If residual chlorine is present, add 3 mL of
diluted organic liquids may be analyzed by direct injection. 10% sodium thiosulfate per gallon and cool to 4C. All extracts
and samples should be stored under refrigeration.
INTERFERENCES Interferences coextracted from the sam-
ples will vary considerably from source to source. Interferences MHT Liquid samples must be extracted within 7 days and
by phthalate esters can pose a major problem in pesticide deter- the extracts must be analyzed within 40 days. Soils, sediments,
minations when using the ECD. Cross-contamination of clean and sludges may be stored for a maximum of 14 days prior to
glassware routinely occurs when plastics are handled during extraction.
extraction steps, especially when solvent-wetted surfaces are
handled. The contamination from phthalate esters can be com- SAMPLE PREPARATION
pletely eliminated with a microcoulometric or electrolytic con- Liquid samples — Extract 1 L samples in a continuous extrac-
ductivity detector. Solvents, reagent, glassware, and other tor at pH 5–9 with methylene chloride after adding 1.0 mL of
sample processing hardware may yield artifacts and/or inter- surrogate spiking solution to each sample. Pass the extract
ferences to sample analysis. through a column of anhydrous sodium sulfate to dry and
concentrate it in a K-D apparatus to 1 mL volume.
INSTRUMENTATION A gas chromatograph capable of on-
column injections is needed. It must be equipped with an ECD Soils, sediments and sludges — Rapidly weigh approximately
or a HECD and one of the following GC columns: 30 g of sample into a 400-mL beaker to avoid loss of the more
volatile extractables. Nonporous or wet samples (gummy or
Column 1: Supelcoport (100/120 mesh) coated with 1.5% SP- clay type) that do not have a free-flowing sandy texture must
2250/1.95% SP-2401 packed in a 1.8 m 4 mm I.D. glass be mixed with anhydrous sodium sulfate until the sample is
column. free flowing. Add 1 mL of surrogate standards to all samples,

spikes, standards, and blanks. Add 100 mL of 1:1 methylene and 200 ng of acid surrogates (for a 1-L injection). Analysis
chloride:acetone and extract ultrasonically. Decant and filter is performed by GC/MS using a capillary GC column.
extracts, dry the extract by passing it through a drying column
INTERFERENCES Raw GC/MS data from all blanks, sam-
containing anhydrous sodium sulfate and concentrate to 1 mL
ples, and spikes must be evaluated for interferences. Contam-
in a K-D apparatus.
ination by carryover can occur whenever high-concentration
Hexane solvent exchange — Add 50 mL of hexane, a new boil- and low-concentration samples are sequentially analyzed. To
ing chip, and concentrate until the apparent volume of liquid reduce carryover, the sample syringe must be rinsed out
reaches 1 mL. Adjust the extract volume to 10.0 mL. Stopper between samples with solvent. Whenever an unusually concen-
the concentration tube and store refrigerated at 4C if further trated sample is encountered, it should be followed by the
processing will not be performed immediately. If the extract analysis of blank solvent to check for cross-contamination.
will be stored longer than two days, transfer it to a vial with
Teflon®-lined screw-cap or crimp top. INSTRUMENTATION A GC/MS and a data system are
required. The GC column used is a 30 m 0.25 mm I.D. (or
QUALITY CONTROL Demonstrate through the analysis of 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
a reagent water blank, that all glassware and reagents are inter- capillary column. A continuous liquid-liquid extractor
ference free. Each time a set of samples is processed, a method equipped with Teflon® or glass connection joints and stopcocks
blank should be processed as a safeguard against chronic lab requiring no lubrication, a K-D concentrating apparatus, water
contamination. A reagent blank, a matrix spike, and a duplicate bath, and an ultrasonic disrupter with a minimum power of
or matrix spike duplicate must be performed for each analytical 300 W and with pulsing capability are also required.
batch (up to a maximum of 20 samples) analyzed.
PRECISION & ACCURACY The estimated quantitation
Analytical system performance must be verified by analyzing limit (EQL) of Method 8270B for determining an individual
QC check samples. The QC check sample concentration should compound is approximately 1 mg/kg (wet weight) for soil or
contain each single-component analyte at the following con- sediment samples, 1–200 mg/kg for wastes (dependent on
centrations in acetone: 4,4-DDD, 10 g/mL; 4,4-DDT, matrix and method of preparation), and 10 g/L for ground-
10 g/mL; endosulfan II, 10 g/mL; endosulfan sulfate, water samples. EQLs will be proportionately higher for sample
10 g/mL; and any other single-component pesticide at extracts that require dilution to avoid saturation of the detector.
2 g/mL. If the method is only to be used to analyze PCBs,
Chlordane, or Toxaphene, the QC check sample concentrate The EQL(b) for groundwater in g/L is not listed.
should contain the most representative multicomponent The EQL (a, b) for low concentrations in soil and sediment
parameter at a concentration of 50 g/mL in acetone. in g/kg is not listed.
Accuracy as g/L is not listed.
REFERENCE Test Methods for Evaluating Solid Waste (SW- Overall precision in g/L is not listed.
846). U.S. EPA. 1983. Method 8080B, Rev. 2, Nov. 1990. Office
of Solid Wastes, Washington, DC. (a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample.
This calculation is based on a 30-g sample and gel perme-
Endosulfan I EPA Method 8270 ation chromatography cleanup.
CAS #959-98-8 (b) Sample EQLs are highly matrix-dependent. The EQLs are
provided for guidance and may not always be achievable.
TITLE Semivolatile Organic Compounds by GC/MS C = True value for concentration, in g/L.
MATRIX This method is used to determine the concentra- X = Average recovery found for measurements of samples con-
tion of semivolatile organic compounds in extracts prepared taining a concentration of C, in g/L.
from all types of solid waste matrices, soils, and groundwater. ESTIMATED QUANTITATION LIMIT
Although surface waters are not specifically mentioned, this Other Matrices Factor (a)
method should be applicable to water samples from rivers,
lakes, etc. High-concentration soil and sludges by sonicator 7.5
Non-water miscible waste 75
METHOD SUMMARY This method covers 259 semivolatile
organic compounds. In very limited applications direct injec- (a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
tion of the sample into the GC/MS system may be appropriate, This estimated EQL is similar to an EPA “Practical Quantitation
but this results in very high detection limits (approximately Limit.”
10,000 g/L). Typically, a 1-L liquid sample, containing surro-
SAMPLING METHOD
gate, and matrix spiking standards, is extracted in a continuous
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
extractor first under acid conditions and then under basic con-
a screw-top Teflon®-lined cover that has been prewashed with
ditions. Typically 30 g of a solid sample, containing surrogate,
detergent and rinsed with distilled water and methanol (or
and matrix spiking standards, is extracted ultrasonically. After
isopropanol).
concentrating the extract to 1 mL it is spiked with 10 L of an
internal standard solution just prior to analysis by GC/MS. The Soils, sediments, or sludges — Use an 8-oz. widemouth glass
volume injected should contain about 100 ng of base/neutral with a screw-top Teflon®-lined cover that has been prewashed

with detergent and rinsed with distilled water and methanol inertness and GC column performance. A calibration standard
(or isopropanol). at mid-concentration, containing each compound of interest,
including all required surrogates, must be performed every 12 h
SAMPLE PRESERVATION
during analysis. After the system performance check is met,
Liquid samples — If residual chlorine is present, add 3 mL of
calibration check compounds (CCCs) are used to check the
10% sodium thiosulfate per gallon, cool to 4C and store in a
validity of the initial calibration.
solvent-free refrigerator until analysis; if chlorine is not present,
then eliminate the sodium thiosulfate addition. The internal standard responses and retention times in the
calibration check standard must be evaluated immediately after
Soils, sediments, or sludges — Cool samples to 4C and store
or during data acquisition. If the retention time for any internal
in a solvent-free refrigerator.
standard changes by more than 30 seconds from the last check
MHT Liquid samples must be extracted within 7 days and calibration (12 h), the chromatographic system must be
the extracts analyzed within 40 days. Soils, sediments, or slud- inspected for malfunctions and corrections must be made, as
ges may be stored for a maximum of 14 days and the extracts required. If the electron ionization current plot (EICP) area for
analyzed within 40 days. any of the internal standards changes by a factor of two from
the last daily calibration standard check, the mass spectrometer
SAMPLE PREPARATION must be inspected for malfunctions and corrections must be
Liquid samples — Transfer 1 L quantitatively to a continuous made, as appropriate.
extractor. If high concentrations are anticipated, a smaller vol-
ume may be used and then diluted with organic-free reagent Demonstrate, through the analysis of a reagent water blank,
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) that interferences from the analytical system, glassware, and
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking reagents are under control. The blank samples should be car-
solution into each sample. For the sample in each analytical ried through all stages of the sample preparation and measure-
batch selected for spiking, add 1.0 mL of a matrix spiking stan- ment steps. For each analytical batch (up to 20 samples), a
dard. For base/neutral acid analysis, the amount of the surro- reagent blank, matrix spike, and matrix spike duplicate/dupli-
gates and matrix spiking compounds added to the sample cate must be analyzed (the frequency of the spikes may be
should result in a final concentration of 100 ng/L of each different for different monitoring programs). The blank and
analyte in the extract to be analyzed (assuming a 1- L injec- spiked samples must be carried through all stages of the sample
tion). Extract with methylene chloride for 18–24 h. Next, adjust preparation and measurement steps. A QC reference sample
the pH of the aqueous phase to pH >11 using 10 N sodium concentrate containing each analyte at a concentration of
hydroxide and extract it with methylene chloride again for 100 mg/L in methanol is required.
18–24 h. Dry the extract through a column containing anhy-
REFERENCE Test Methods for Evaluating Solid Waste (SW-
drous sodium sulfate and concentrate it to 1 mL using a K-D
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
concentrator.
of Solid Waste, Washington, DC.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous
or wet samples (gummy or clay type) that do not have a free-
flowing sandy texture must be mixed with anhydrous sodium
Endosulfan II EPA Method 625
sulfate until the sample is free flowing. Add 1 mL of surrogate
standards to all samples, spikes, standards, and blanks. For the CAS #33213-65-9
sample in each analytical batch selected for spiking, add 1.0 mL
of a matrix spiking standard. For base/neutral acid analysis, the TITLE Base/Neutrals and Acids, U.S. EPA Method 625
amount added of the surrogates and matrix spiking com- MATRIX This methods covers municipal and industrial
pounds should result in a final concentration of 100 ng/ L of wastewaters.
each base/neutral analyte and 200 ng/L of each acid analyte
in the extract to be analyzed (assuming a 1- L injection).
Immediately add a 100-mL mixture of 1:1 methylene chlo-
ride:acetone and extract the sample ultrasonically for 3 min
continuous extractor. The methylene chloride extract is dried,
and then decant or filter the extracts. Repeat the extraction two
concentrated to a volume of 1 mL, and analyzed by GC/MS.
or more times. Dry the extract using a column with anhydrous
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. Qualitative identification of the parameters in the extract is
performed using the retention time and the relative abundance
Note: Under the alkaline conditions of the extraction step of three characteristic masses (m/z). Qualitative analysis is per-
endosulfan I is subject to decomposition so neutral extraction formed using either external or internal standard techniques
should be performed if this compound is expected. with a single characteristic m/z.
QUALITY CONTROL A methylene chloride solution con- INTERFERENCES Method interferences may be caused by
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is contaminants in solvents, reagents, glassware, and other sample
used for tuning the GC/MS system each 12-h shift. A system processing hardware. Glassware must be scrupulously cleaned.
performance check also must be made during every 12-h shift. Glassware should be heated in a muffle furnace at 400C for 5
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- to 30 min. Some thermally stable materials, such as PCBs, may
rophenol, and benzidine is required to verify injection port not be eliminated by this treatment. Solvent rinses with acetone

taminants that are coextracted from the sample. The base-
QUALITY CONTROL Make an initial, one-time, demonstra-
neutral extraction may cause significantly reduced recovery of
tion of the ability to generate acceptable accuracy and precision
INSTRUMENTATION A GC/MS system with an injection control. Each time a set of samples is extracted or reagents are
port designed for on-column injection when using packed col- changed, a reagent water blank must be processed. Spike and
umns and for splitless injection when using capillary columns. analyze a minimum of 5% of all samples to monitor and eval-
uate lab data quality. A QC check sample concentrate that
Column for base/neutrals: 1.8 m long  2 mm I.D. glass,
contains each parameter of interest at a concentration of
packed with 3% SP-2550 on Supelcoport (100/120 mesh)
or equivalent. 100 g/mL in acetone is required. PCBs and multicomponent
Column for acids: 1.8 m long 2 mm I.D. glass, packed with pesticides may be omitted from this test.
1% SP-1240DA on Supelcoport (100/120 mesh) or equivalent. After analysis of five spiked wastewater samples, calculate the
PRECISION & ACCURACY The MDL concentrations were average percent recovery and the standard deviation of the
obtained using reagent water. The MDL actually achieved in a percent recovery. Spike all samples with the surrogate standard
given analysis will vary depending on instrument sensitivity spiking solution and calculate the percent recovery of each
and matrix effects. This method was tested by 15 laboratories surrogate compound.
using reagent water, drinking water, surface water, and indus- REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct.
trial wastewaters spiked at six concentrations over the range 5 26, 1984.
Endosulfan II EPA Method 8080
The MDL (in g/L) in reagent water was not reported. CAS #33213-65-9
ments) was not reported. TITLE Organochlorine Pesticides and Polychlorinated
The range (in g/L) for average recovery for 4 measurements Biphenyls By Gas Chromatography
was not reported.
The range (in %) for percent recovery was not reported. MATRIX This method is used to determine the concentra-
Accuracy (in g/L) as expected recovery for one or more mea- tion of various organochlorine pesticides and polychlorinated
surements of a sample containing a true concentration of biphenyls in extracts prepared from water, groundwater, soils,
C was not reported. and sediments.
Precision (in g/L) as expected single analyst standard devia- METHOD SUMMARY This method covers 26 pesticides and
tion of measurements at an average concentration found at Aroclor (PCB) mixtures and it is suitable for monitoring-type
X was not reported. analyses. After extraction, concentration and solvent exchange
Overall precision (in g/L) as expected interlaboratory stan- to hexane, a 2- to 5-L sample aliquot is injected into a GC
dard deviation of measurements in an average concentra- using the solvent flush technique, and the analytes are detected
tion found at X was not reported. by an electron capture detector (ECD) or an electrolytic con-
C = True value of the concentration in g/L. ductivity detector in the halogen mode (HECD). Both neat and
X = Average recovery found for measurements of samples con- diluted organic liquids may be analyzed by direct injection.
taining a concentration at C in g/L. INTERFERENCES Interferences coextracted from the sam-
SAMPLE PREPARATION Adjust the pH to >11 with sodium ples will vary considerably from source to source. Interferences
hydroxide and serially extract in a separatory funnel with meth- by phthalate esters can pose a major problem in pesticide deter-
ylene chloride or else in a continuous extractor. Next, adjust minations when using the ECD. Cross-contamination of clean
the pH to <2 with sulfuric acid and serially extract in a sepa- glassware routinely occurs when plastics are handled during
ratory funnel with methylene chloride or else in a continuous extraction steps, especially when solvent-wetted surfaces are
extractor. Dry the extracts separately through a column of handled. The contamination from phthalate esters can be com-
anhydrous sodium sulfate and then concentrate each of the pletely eliminated with a microcoulometric or electrolytic con-
extracts to 1.0 mL using a K-D apparatus. ductivity detector. Solvents, reagent, glassware, and other
sample processing hardware may yield artifacts and/or inter-
ferences to sample analysis.
Grab samples must be collected in glass containers. All samples
must be refrigerated at 4C from the time of collection until INSTRUMENTATION A gas chromatograph capable of on-
extraction. If residual chlorine is present, add 80 mg of sodium column injections is needed. It must be equipped with an ECD
thiosulfate/L of sample and mix well. All samples must be or a HECD and one of the following GC columns:

Column 1: Supelcoport (100/120 mesh) coated with 1.5% SP- clay type) that do not have a free-flowing sandy texture must
2250/1.95% SP-2401 packed in a 1.8 m 4 mm I.D. glass be mixed with anhydrous sodium sulfate until the sample is
column. free flowing. Add 1 mL of surrogate standards to all samples,
Column 2: Supelcoport (100/120 mesh) coated with 3% OV-1 spikes, standards, and blanks. Add 100 mL of 1:1 methylene
in a 1.8 m 4 mm I.D. glass column. chloride:acetone and extract ultrasonically. Decant and filter
laboratories using organic-free reagent water, drinking water, in a K-D apparatus.
concentrations. Concentrations used in the study ranged from Hexane solvent exchange — Add 50 mL of hexane, a new boil-
0.5 to 30 g/L for single-component pesticides and from 8.5 to ing chip, and concentrate until the apparent volume of liquid
400 g/L for multicomponent parameters. Overall precision reaches 1 mL. Adjust the extract volume to 10.0 mL. Stopper
and method accuracy were found to be directly related to the the concentration tube and store refrigerated at 4C if further
concentration of the analyte and essentially independent of the processing will not be performed immediately. If the extract
sample matrix. The sensitivity of this method usually depends will be stored longer than two days, transfer it to a vial with
on the concentration of interferences rather than on instru- Teflon®-lined screw-cap or crimp top.
mental limitations. QUALITY CONTROL Demonstrate through the analysis of
MDL in g/L was 0.004. a reagent water blank, that all glassware and reagents are inter-
Concentration range in g/L was 0.5–30. ference free. Each time a set of samples is processed, a method
Accuracy as recovery (x*) in g/L was 0.93C + 0.34 . blank should be processed as a safeguard against chronic lab
Overall precision (S*) in g/L was 0.47x–0.20. contamination. A reagent blank, a matrix spike, and a duplicate
or matrix spike duplicate must be performed for each analytical
x* = Expected recovery for one or more measurements of a sample batch (up to a maximum of 20 samples) analyzed.
S* = Expected interlaboratory standard deviation of measure- Analytical system performance must be verified by analyzing
ments at an average concentration found of the analyte QC check samples. The QC check sample concentration should
in g/L. contain each single-component analyte at the following con-
C = True value for the concentration, in g/L. centrations in acetone: 4,4-DDD, 10 g/mL; 4,4-DDT,
X = Average recovery found for measurements of samples con- 10 g/mL; endosulfan II, 10 g/mL; endosulfan sulfate,
taining a concentration of C, in g/L. 10 g/mL; and any other single-component pesticide at
2 g/mL. If the method is only to be used to analyze PCBs,
SAMPLING METHOD Chlordane, or Toxaphene, the QC check sample concentrate
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with should contain the most representative multicomponent
a screw-top Teflon®-lined cover. Pre-wash the bottle with deter- parameter at a concentration of 50 g/mL in acetone.
gent, rinse with distilled water and methanol (or isopropanol).
Soil, sediments, and sludges — Use an 8-oz. widemouth glass 846). U.S. EPA. 1983. Method 8080B, Rev. 2, Nov. 1990. Office
with a screw-top Teflon®-lined cover. Pre-wash the bottle with of Solid Wastes, Washington, DC.
detergent, rinse with distilled water and methanol (or isopro-
panol).
SAMPLE PRESERVATION Cool water, soil, sediment, or Endosulfan II EPA Method 8270
sludge samples immediately to 4C. CAS #33213-65-9
Water samples — If residual chlorine is present, add 3 mL of
10% sodium thiosulfate per gallon and cool to 4C. All extracts TITLE Semivolatile Organic Compounds by GC/MS
and samples should be stored under refrigeration. MATRIX This method is used to determine the concentra-
MHT Liquid samples must be extracted within 7 days and tion of semivolatile organic compounds in extracts prepared
the extracts must be analyzed within 40 days. Soils, sediments, from all types of solid waste matrices, soils, and groundwater.
and sludges may be stored for a maximum of 14 days prior to Although surface waters are not specifically mentioned, this
extraction. method should be applicable to water samples from rivers,
lakes, etc.
SAMPLE PREPARATION
Liquid samples — Extract 1 L samples in a continuous extrac- METHOD SUMMARY This method covers 259 semivolatile
tor at pH 5–9 with methylene chloride after adding 1.0 mL of organic compounds. In very limited applications direct injec-
surrogate spiking solution to each sample. Pass the extract tion of the sample into the GC/MS system may be appropriate,
through a column of anhydrous sodium sulfate to dry and but this results in very high detection limits (approximately
concentrate it in a K-D apparatus to 1 mL volume. 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
Soils, sediments and sludges — Rapidly weigh approximately extractor first under acid conditions and then under basic con-
30 g of sample into a 400-mL beaker to avoid loss of the more ditions. Typically 30 g of a solid sample, containing surrogate,
volatile extractables. Nonporous or wet samples (gummy or and matrix spiking standards, is extracted ultrasonically. After

concentrating the extract to 1 mL it is spiked with 10 L of an Soils, sediments, or sludges — Use an 8-oz. widemouth glass
internal standard solution just prior to analysis by GC/MS. The with a screw-top Teflon®-lined cover that has been prewashed
volume injected should contain about 100 ng of base/neutral with detergent and rinsed with distilled water and methanol
and 200 ng of acid surrogates (for a 1-L injection). Analysis (or isopropanol).
is performed by GC/MS using a capillary GC column.
SAMPLE PRESERVATION
INTERFERENCES Raw GC/MS data from all blanks, sam- Liquid samples — If residual chlorine is present, add 3 mL of
ples, and spikes must be evaluated for interferences. Contam- 10% sodium thiosulfate per gallon, cool to 4C and store in a
ination by carryover can occur whenever high-concentration solvent-free refrigerator until analysis; if chlorine is not present,
and low-concentration samples are sequentially analyzed. To then eliminate the sodium thiosulfate addition.
reduce carryover, the sample syringe must be rinsed out
between samples with solvent. Whenever an unusually concen- Soils, sediments, or sludges — Cool samples to 4C and store
trated sample is encountered, it should be followed by the in a solvent-free refrigerator.
analysis of blank solvent to check for cross-contamination. MHT Liquid samples must be extracted within 7 days and
INSTRUMENTATION A GC/MS and a data system are the extracts analyzed within 40 days. Soils, sediments, or slud-
required. The GC column used is a 30 m 0.25 mm I.D. (or ges may be stored for a maximum of 14 days and the extracts
0.32 mm I.D.) 1um film thickness silicone-coated fused silica analyzed within 40 days.
capillary column. A continuous liquid-liquid extractor SAMPLE PREPARATION
equipped with Teflon® or glass connection joints and stopcocks Liquid samples — Transfer 1 L quantitatively to a continuous
requiring no lubrication, a K-D concentrating apparatus, water extractor. If high concentrations are anticipated, a smaller vol-
bath, and an ultrasonic disrupter with a minimum power of ume may be used and then diluted with organic-free reagent
300 W and with pulsing capability are also required. water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
PRECISION & ACCURACY The estimated quantitation sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
limit (EQL) of Method 8270B for determining an individual solution into each sample. For the sample in each analytical
compound is approximately 1 mg/kg (wet weight) for soil or batch selected for spiking, add 1.0 mL of a matrix spiking stan-
sediment samples, 1–200 mg/kg for wastes (dependent on dard. For base/neutral acid analysis, the amount of the surro-
matrix and method of preparation), and 10 g/L for ground- gates and matrix spiking compounds added to the sample
water samples. EQLs will be proportionately higher for sample should result in a final concentration of 100 ng/L of each
extracts that require dilution to avoid saturation of the detector. analyte in the extract to be analyzed (assuming a 1- L injec-
tion). Extract with methylene chloride for 18–24 h. Next, adjust
The EQL(b) for groundwater in g/L is not listed. the pH of the aqueous phase to pH >11 using 10 N sodium
The EQL (a, b) for low concentrations in soil and sediment hydroxide and extract it with methylene chloride again for
in g/kg is not listed. 18–24 h. Dry the extract through a column containing anhy-
Accuracy as g/L is not listed. drous sodium sulfate and concentrate it to 1 mL using a K-D
Overall precision in g/L is not listed. concentrator.
(a) EQLs listed for soil/sediment are based on wet weight. Nor- Soils, sediments, or sludges — Use 30 g of sample. Nonporous
mally data is reported in a dry-weight basis; therefore, EQLs or wet samples (gummy or clay type) that do not have a free-
will be higher based on the % dry weight of each sample. flowing sandy texture must be mixed with anhydrous sodium
This calculation is based on a 30-g sample and gel perme- sulfate until the sample is free flowing. Add 1 mL of surrogate
ation chromatography cleanup. standards to all samples, spikes, standards, and blanks. For the
(b) Sample EQLs are highly matrix-dependent. The EQLs are sample in each analytical batch selected for spiking, add 1.0 mL
provided for guidance and may not always be achievable. of a matrix spiking standard. For base/neutral acid analysis, the
C = True value for concentration, in g/L. amount added of the surrogates and matrix spiking com-
X = Average recovery found for measurements of samples con- pounds should result in a final concentration of 100 ng/ L of
taining a concentration of C, in g/L. each base/neutral analyte and 200 ng/L of each acid analyte
ESTIMATED QUANTITATION LIMIT in the extract to be analyzed (assuming a 1- L injection).
Other Matrices Factor (a)
High-concentration soil and sludges by sonicator 7.5 and then decant or filter the extracts. Repeat the extraction two
Non-water miscible waste 75 or more times. Dry the extract using a column with anhydrous
sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
This estimated EQL is similar to an EPA “Practical Quantitation Note: Under the alkaline conditions of the extraction step
Limit.” endosulfan II is subject to decomposition so neutral extraction
should be performed if this compound is expected.
SAMPLING METHOD
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with QUALITY CONTROL A methylene chloride solution con-
a screw-top Teflon®-lined cover that has been prewashed with taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
detergent and rinsed with distilled water and methanol (or used for tuning the GC/MS system each 12-h shift. A system
isopropanol). performance check also must be made during every 12-h shift.

A standard containing 50 ng/L each of 4,4-DDT, pentachlo- to 30 min. Some thermally stable materials, such as PCBs, may
rophenol, and benzidine is required to verify injection port not be eliminated by this treatment. Solvent rinses with acetone
inertness and GC column performance. A calibration standard and pesticide quality hexane may be substituted for the muffle
at mid-concentration, containing each compound of interest, furnace heating. Matrix interferences may be caused by con-
including all required surrogates, must be performed every 12 h taminants that are coextracted from the sample. The base-
during analysis. After the system performance check is met, neutral extraction may cause significantly reduced recovery of
calibration check compounds (CCCs) are used to check the phenols. The packed gas chromatographic columns recom-
validity of the initial calibration. mended for the basic fraction may not exhibit sufficient reso-
The internal standard responses and retention times in the
calibration check standard must be evaluated immediately after INSTRUMENTATION A GC/MS system with an injection
or during data acquisition. If the retention time for any internal port designed for on-column injection when using packed col-
standard changes by more than 30 seconds from the last check umns and for splitless injection when using capillary columns.
calibration (12 h), the chromatographic system must be
inspected for malfunctions and corrections must be made, as
required. If the electron ionization current plot (EICP) area for
or equivalent.
any of the internal standards changes by a factor of two from
Column for acids: 1.8 m long 2 mm I.D. glass, packed with
1% SP-1240DA on Supelcoport (100/120 mesh) or equivalent.
must be inspected for malfunctions and corrections must be
made, as appropriate. PRECISION & ACCURACY The MDL concentrations were
obtained using reagent water. The MDL actually achieved in a
Demonstrate, through the analysis of a reagent water blank,
given analysis will vary depending on instrument sensitivity
that interferences from the analytical system, glassware, and
and matrix effects. This method was tested by 15 laboratories
reagents are under control. The blank samples should be car-
using reagent water, drinking water, surface water, and indus-
ried through all stages of the sample preparation and measure-
ment steps. For each analytical batch (up to 20 samples), a
reagent blank, matrix spike, and matrix spike duplicate/dupli-
cate must be analyzed (the frequency of the spikes may be
different for different monitoring programs). The blank and
spiked samples must be carried through all stages of the sample The MDL (in g/L) in reagent water was 5.6.
preparation and measurement steps. A QC reference sample The standard deviation (in g/L based on 4 recovery measure-
concentrate containing each analyte at a concentration of ments) was 16.7.
100 mg/L in methanol is required. The range (in g/L) for average recovery for 4 measurements
was D-103.5.
The range (in %) for percent recovery was D-107.
of Solid Waste, Washington, DC. Accuracy (in g/L) as expected recovery for one or more mea-
C was 0.39C + 0.41.
Precision (in g/L) as expected single analyst standard devia-
Endosulfan sulfate EPA Method 625 tion of measurements at an average concentration found at
CAS #1031-07-8 X was 0.12X + 2.47.
Overall precision (in g/L) as expected interlaboratory stan-
TITLE Base/Neutrals and Acids, U.S. EPA Method 625 dard deviation of measurements in an average concentra-
tion found at X was 0.63X–1.03.
wastewaters. C = True value of the concentration in g/L.
and again at a pH less than 2 using a separatory funnel or a SAMPLE PREPARATION Adjust the pH to >11 with sodium
continuous extractor. The methylene chloride extract is dried, hydroxide and serially extract in a separatory funnel with meth-
concentrated to a volume of 1 mL, and analyzed by GC/MS. ylene chloride or else in a continuous extractor. Next, adjust
Qualitative identification of the parameters in the extract is the pH to <2 with sulfuric acid and serially extract in a sepa-
performed using the retention time and the relative abundance ratory funnel with methylene chloride or else in a continuous
of three characteristic masses (m/z). Qualitative analysis is per- extractor. Dry the extracts separately through a column of
formed using either external or internal standard techniques anhydrous sodium sulfate and then concentrate each of the
with a single characteristic m/z. extracts to 1.0 mL using a K-D apparatus.
INTERFERENCES Method interferences may be caused by SAMPLE COLLECTION, PRESERVATION & HANDLING
contaminants in solvents, reagents, glassware, and other sample Grab samples must be collected in glass containers. All samples
processing hardware. Glassware must be scrupulously cleaned. must be refrigerated at 4C from the time of collection until
Glassware should be heated in a muffle furnace at 400C for 5 extraction. If residual chlorine is present, add 80 mg of sodium

thiosulfate/L of sample and mix well. All samples must be Column 1: Supelcoport (100/120 mesh) coated with 1.5% SP-
extracted within 7 days of collection and completely analyzed 2250/1.95% SP-2401 packed in a 1.8 m 4 mm I.D. glass
within 40 days of extraction. column.
Column 2: Supelcoport (100/120 mesh) coated with 3% OV-1
in a 1.8 m 4 mm I.D. glass column.
with this method. Before processing any samples, the analyst PRECISION & ACCURACY The method was tested by 20
must analyze a reagent water blank to demonstrate that inter- laboratories using organic-free reagent water, drinking water,
ferences from the analytical system and glassware are under surface water, and three industrial wastewaters spiked at six
control. Each time a set of samples is extracted or reagents are concentrations. Concentrations used in the study ranged from
changed, a reagent water blank must be processed. Spike and 0.5 to 30 g/L for single-component pesticides and from 8.5 to
analyze a minimum of 5% of all samples to monitor and eval- 400 g/L for multicomponent parameters. Overall precision
uate lab data quality. A QC check sample concentrate that and method accuracy were found to be directly related to the
contains each parameter of interest at a concentration of concentration of the analyte and essentially independent of the
100 g/mL in acetone is required. PCBs and multicomponent sample matrix. The sensitivity of this method usually depends
pesticides may be omitted from this test. on the concentration of interferences rather than on instru-
mental limitations.
After analysis of five spiked wastewater samples, calculate the
average percent recovery and the standard deviation of the MDL in g/L was 0.066.
percent recovery. Spike all samples with the surrogate standard Concentration range in g/L was 0.5–30.
spiking solution and calculate the percent recovery of each Accuracy as recovery (x*) in g/L was 0.89C-0.37 .
surrogate compound. Overall precision (S*) in g/L was 0.24x + 0.35.
REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct. x* = Expected recovery for one or more measurements of a sample
26, 1984. containing concentration C, in g/L.
ments at an average concentration found of the analyte
in g/L.
Endosulfan Sulfate EPA Method 8080
C = True value for the concentration, in g/L.
CAS #1031-07-8
taining a concentration of C, in g/L.
TITLE Organochlorine Pesticides and Polychlorinated
Biphenyls By Gas Chromatography SAMPLING METHOD
MATRIX This method is used to determine the concentra-
a screw-top Teflon®-lined cover. Pre-wash the bottle with deter-
tion of various organochlorine pesticides and polychlorinated
gent, rinse with distilled water and methanol (or isopropanol).
biphenyls in extracts prepared from water, groundwater, soils,
and sediments. Soil, sediments, and sludges — Use an 8-oz. widemouth glass
with a screw-top Teflon®-lined cover. Pre-wash the bottle with
METHOD SUMMARY This method covers 26 pesticides and
Aroclor (PCB) mixtures and it is suitable for monitoring-type
panol).
analyses. After extraction, concentration and solvent exchange
to hexane, a 2- to 5-L sample aliquot is injected into a GC SAMPLE PRESERVATION Cool water, soil, sediment, or
using the solvent flush technique, and the analytes are detected sludge samples immediately to 4C.
by an electron capture detector (ECD) or an electrolytic con-
ductivity detector in the halogen mode (HECD). Both neat and
10% sodium thiosulfate per gallon and cool to 4C. All extracts
diluted organic liquids may be analyzed by direct injection.
INTERFERENCES Interferences coextracted from the sam-
MHT Liquid samples must be extracted within 7 days and
ples will vary considerably from source to source. Interferences
the extracts must be analyzed within 40 days. Soils, sediments,
by phthalate esters can pose a major problem in pesticide deter-
and sludges may be stored for a maximum of 14 days prior to
minations when using the ECD. Cross-contamination of clean
extraction.
glassware routinely occurs when plastics are handled during
extraction steps, especially when solvent-wetted surfaces are SAMPLE PREPARATION
handled. The contamination from phthalate esters can be com- Liquid samples — Extract 1 L samples in a continuous extrac-
pletely eliminated with a microcoulometric or electrolytic con- tor at pH 5–9 with methylene chloride after adding 1.0 mL of
ductivity detector. Solvents, reagent, glassware, and other surrogate spiking solution to each sample. Pass the extract
sample processing hardware may yield artifacts and/or inter- through a column of anhydrous sodium sulfate to dry and
ferences to sample analysis. concentrate it in a K-D apparatus to 1 mL volume.
INSTRUMENTATION A gas chromatograph capable of on- Soils, sediments and sludges — Rapidly weigh approximately
column injections is needed. It must be equipped with an ECD 30 g of sample into a 400-mL beaker to avoid loss of the more
or a HECD and one of the following GC columns: volatile extractables. Nonporous or wet samples (gummy or

clay type) that do not have a free-flowing sandy texture must concentrating the extract to 1 mL it is spiked with 10 L of an
be mixed with anhydrous sodium sulfate until the sample is internal standard solution just prior to analysis by GC/MS. The
free flowing. Add 1 mL of surrogate standards to all samples, volume injected should contain about 100 ng of base/neutral
spikes, standards, and blanks. Add 100 mL of 1:1 methylene and 200 ng of acid surrogates (for a 1-L injection). Analysis
in a K-D apparatus.
INSTRUMENTATION A GC/MS and a data system are
Teflon®-lined screw-cap or crimp top.
batch (up to a maximum of 20 samples) analyzed. PRECISION & ACCURACY The estimated quantitation
2 g/mL. If the method is only to be used to analyze PCBs, The EQL(b) for groundwater in g/L is not listed.
Chlordane, or Toxaphene, the QC check sample concentrate The EQL (a, b) for low concentrations in soil and sediment
should contain the most representative multicomponent in g/kg is not listed.
parameter at a concentration of 50 g/mL in acetone. Accuracy as g/L is 0.39C + 0.41.
REFERENCE Test Methods for Evaluating Solid Waste (SW- Overall precision in g/L is 0.63X–1.03.
846). U.S. EPA. 1983. Method 8080B, Rev. 2, Nov. 1990. Office (a) EQLs listed for soil/sediment are based on wet weight. Nor-
of Solid Wastes, Washington, DC. mally data is reported in a dry-weight basis; therefore, EQLs
Endosulfan sulfate EPA Method 8270 ation chromatography cleanup.
MATRIX This method is used to determine the concentra- taining a concentration of C, in g/L.
tion of semivolatile organic compounds in extracts prepared
method should be applicable to water samples from rivers, High-concentration soil and sludges by sonicator 7.5
lakes, etc. Non-water miscible waste 75
METHOD SUMMARY This method covers 259 semivolatile (a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
organic compounds. In very limited applications direct injec- This estimated EQL is similar to an EPA “Practical Quantitation
tion of the sample into the GC/MS system may be appropriate, Limit.”
but this results in very high detection limits (approximately
10,000 g/L). Typically, a 1-L liquid sample, containing surro- SAMPLING METHOD
gate, and matrix spiking standards, is extracted in a continuous Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
extractor first under acid conditions and then under basic con- a screw-top Teflon®-lined cover that has been prewashed with
ditions. Typically 30 g of a solid sample, containing surrogate, detergent and rinsed with distilled water and methanol (or
and matrix spiking standards, is extracted ultrasonically. After isopropanol).

Soils, sediments, or sludges — Use an 8-oz. widemouth glass at mid-concentration, containing each compound of interest,
with a screw-top Teflon®-lined cover that has been prewashed including all required surrogates, must be performed every 12 h
with detergent and rinsed with distilled water and methanol during analysis. After the system performance check is met,
(or isopropanol). calibration check compounds (CCCs) are used to check the
SAMPLE PRESERVATION
Liquid samples — If residual chlorine is present, add 3 mL of The internal standard responses and retention times in the
10% sodium thiosulfate per gallon, cool to 4C and store in a calibration check standard must be evaluated immediately after
solvent-free refrigerator until analysis; if chlorine is not present, or during data acquisition. If the retention time for any internal
then eliminate the sodium thiosulfate addition. standard changes by more than 30 seconds from the last check
MHT Liquid samples must be extracted within 7 days and any of the internal standards changes by a factor of two from
the extracts analyzed within 40 days. Soils, sediments, or slud- the last daily calibration standard check, the mass spectrometer
ges may be stored for a maximum of 14 days and the extracts must be inspected for malfunctions and corrections must be
analyzed within 40 days. made, as appropriate.
SAMPLE PREPARATION Demonstrate, through the analysis of a reagent water blank,
Liquid samples — Transfer 1 L quantitatively to a continuous that interferences from the analytical system, glassware, and
extractor. If high concentrations are anticipated, a smaller vol- reagents are under control. The blank samples should be car-
ume may be used and then diluted with organic-free reagent ried through all stages of the sample preparation and measure-
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) ment steps. For each analytical batch (up to 20 samples), a
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking reagent blank, matrix spike, and matrix spike duplicate/dupli-
solution into each sample. For the sample in each analytical cate must be analyzed (the frequency of the spikes may be
batch selected for spiking, add 1.0 mL of a matrix spiking stan- different for different monitoring programs). The blank and
dard. For base/neutral acid analysis, the amount of the surro- spiked samples must be carried through all stages of the sample
gates and matrix spiking compounds added to the sample preparation and measurement steps. A QC reference sample
should result in a final concentration of 100 ng/L of each concentrate containing each analyte at a concentration of
analyte in the extract to be analyzed (assuming a 1- L injec- 100 mg/L in methanol is required.
tion). Extract with methylene chloride for 18–24 h. Next, adjust REFERENCE Test Methods for Evaluating Solid Waste (SW-
the pH of the aqueous phase to pH >11 using 10 N sodium
hydroxide and extract it with methylene chloride again for
concentrator.
Endrin EPA Method 505
CAS #72-20-8
TITLE Analysis of Organohalide Pesticides and Commercial
Polychlorinated Biphenyl (PCB) Products in Water by Microex-
standards to all samples, spikes, standards, and blanks. For the
traction and Gas Chromatography. U.S. EPA Method 505, Rev.
2.0, 1989.
of a matrix spiking standard. For base/neutral acid analysis, the
amount added of the surrogates and matrix spiking com- MATRIX This method is applicable to drinking water and
pounds should result in a final concentration of 100 ng/ L of raw source water. The latter should include most surface water
each base/neutral analyte and 200 ng/L of each acid analyte and groundwater sources.
in the extract to be analyzed (assuming a 1- L injection). METHOD SUMMARY Method 505 covers 25 pesticides and
Immediately add a 100-mL mixture of 1:1 methylene chlo- commercial PCB products. This is a very sensitive method that
ride:acetone and extract the sample ultrasonically for 3 min is more useful for monitoring than for exploratory analyses.
and then decant or filter the extracts. Repeat the extraction two 5-mL of water are saturated with sodium chloride and then
or more times. Dry the extract using a column with anhydrous extracted by shaking with 2 mL of hexane. The sample extracts
are transferred to an autosampler setup to inject 1–2 L por-
QUALITY CONTROL A methylene chloride solution con- tions into a gas chromatograph (GC) for analysis. Alternatively,
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is 1–2 L portions of samples, blanks, and standards may be
used for tuning the GC/MS system each 12-h shift. A system manually injected. Each extract is analyzed by capillary
performance check also must be made during every 12-h shift. GC/ECD with confirmation using either a second capillary
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- column or GC/MS. The electron capture detector is easy to use,
rophenol, and benzidine is required to verify injection port but it is a nonselective detector. The microextraction technique
inertness and GC column performance. A calibration standard also eliminates the expensive sample preparation costs of other

methods, but it has the disadvantage of being less sensitive than SAMPLING METHOD Collect samples using a 40-mL
most because the extracts are not concentrated. screw-cap vial (prewashed with detergent, rinsed with distilled
water and oven dried at 400C for one h) with a Teflon®-faced
silicone septum . Collect bubble-free samples and place the sep-
contaminants in solvents, reagents, glassware, and other sample
tum with the Teflon® side down on the water.
processing apparatus that lead to discrete artifacts or elevated
baselines. Interfering contamination may occur when a sample SAMPLE PRESERVATION If residual chlorine is present in
containing low concentrations of analytes is analyzed immedi- the water add about 3 mg of sodium thiosulfate to each vial
ately following a sample containing relatively high concentra- before samples are collected to remove the chlorine. Alterna-
tions of the analytes. Matrix interferences also may be caused tively, add 75 L of 0.04 g/mL solution of sodium thiosulfate
by contaminants that are coextracted from the sample; cleanup to each vial just prior to sampling. Immediately cool samples
of sample extracts may be necessary in these cases. Some pes- to 4C, and store them in a solvent-free refrigerator at 4C until
ticides and commercial PCB products from aqueous solutions analysis.
adhere to glass surfaces, so sample transfers and contact with MHT The maximum holding time is 14 days from the time
glass surfaces should be minimized. Some pesticides are rapidly the sample was collected until it must be analyzed.
oxidized by chlorine so dechlorination with sodium thiosulfate
at the time of sample collection is important. Also, splitless SAMPLE PREPARATION Remove the sample from storage
injectors may cause degradation of some pesticides. and allow it to come to room temperature. Remove a 5-mL
volume from each container and weigh the container to the
INSTRUMENTATION A gas chromatograph/electron cap- nearest 0.1 g. Add 6 g of sodium chloride and 2.0 mL of hexane
ture detector/data system, with temperature programming and to each sample bottle. Recap the sample and shake it vigorously
split/splitless injector suitable for use with capillary columns is for one min. Allow the water and hexane phases to separate,
needed. remove the cap, and transfer 0.5 mL of hexane into an autosam-
Column 1: 0.32 mm I.D.  30 m fused silica capillary with pler vial using a disposable glass pipette. Transfer the remaining
chemically bond methyl polysiloxane phase (DB-1, 1.0 m hexane phase into a second autosampler vial and store at 4C
film, or equivalent). for reanalysis, if necessary. Discard the remaining sample/hex-
Column 2: 0.32 mm I.D. 30 m fused silica capillary with 1:1 ane mixture and reweigh the empty container to determine net
mixed phase of dimethyl silicone and polyethylene glycol weight of sample.
(Durawax-DX3, 0.25 m film, or equivalent). QUALITY CONTROL Minimum quality control require-
Column 3: 0.32 mm I.D.  25 m fused silica capillary with ments are initial demonstration of lab capability, analysis of lab
chemically bonded 50:50 methyl-phenyl silicone (OV-17, reagent blanks, fortified blanks, fortified sample matrix, and
1.5 m film, or equivalent). quality control samples. The lab must analyze at least one for-
Column 1 should be used as the primary analytical column. tified blank per sample set, or at least one for every 20 samples.
Columns 2 and 3 are recommended for use as confirmatory The fortifying concentration of each analyte should be 10 times
columns when GC/MS confirmation is not available. the method detection limit or the maximum calibration limit
(MCL), whichever is less. Calculate accuracy as percent recov-
PRECISION & ACCURACY Method detection limits are
ery and develop control limits from the mean percent recovery
dependent upon the characteristics of the gas chromatographic
and standard deviation.
system used. Analytes that are not separated chromatographi-
cally cannot be individually identified and used in the same The lab must add a known concentration of the analytes to a
calibration mixture or water samples unless an alternative tech- minimum of 10% of the routine samples, or one lab fortified
nique for identification and quantification, such as mass spec- sample matrix per sample set. Calculate the percent recovery
trometry, is used. for each analyte and compare to the control limits established
from the analyses of the fortified blanks.
The concentration(s) (in g/L) used for these QC measure-
ments was 0.10 and 3.6. EPA CONTACT & HOTLINE For technical questions contact
The MDL (in g/L) was 0.063. Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
The accuracy (% recovery) for reagent water at the above con- Drinking Water (WH-550D), 401 M St. SW, Washington, DC
centration(s) was 119 and 99 and the precision (%) was 29.8 20460. Tel. (202) 260-3040. For further information the EPA
and 6.5. Safe Drinking Water Hotline may be called at: (800) 426-4791.
The accuracy (% recovery) for groundwater at the above con-
REFERENCE Methods for the Determination of Organic
centration(s) was 94 and 100 and the precision (%) was 20.2
Compounds in Drinking Water, EPA/600/4-88/039 (revised
and 11.3.
July 1991). U.S. EPA Environmental Monitoring Systems Lab-
The accuracy (% recovery) for tap water at the above concen-
oratory, Cincinnati, OH, 45268, U.S.A. Available from the
tration(s) was 106 and 85 and the precision (5) was 14.7
National Technical Information Service (NTIS), 5285 Port
and 12.4.
Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS
Note: No range of concentrations is provided with this method. Order Number is PB91-231480.

Endrin EPA Method 625 Precision (in g/L) as expected single analyst standard devia-
CAS #72-20-8 tion of measurements at an average concentration found at
X was not reported.
TITLE Base/Neutrals and Acids, U.S. EPA Method 625 Overall precision (in g/L) as expected interlaboratory stan-
dard deviation of measurements in an average concentra-
MATRIX This methods covers municipal and industrial tion found at X was not reported.
wastewaters.
METHOD SUMMARY Approximately 1 L of sample is seri- X = Average recovery found for measurements of samples con-
ally extracted with methylene chloride at a pH greater than 11 taining a concentration at C in g/L.
continuous extractor. The methylene chloride extract is dried, SAMPLE PREPARATION Adjust the pH to >11 with sodium
concentrated to a volume of 1 mL, and analyzed by GC/MS. hydroxide and serially extract in a separatory funnel with meth-
Qualitative identification of the parameters in the extract is ylene chloride or else in a continuous extractor. Next, adjust
performed using the retention time and the relative abundance the pH to <2 with sulfuric acid and serially extract in a sepa-
of three characteristic masses (m/z). Qualitative analysis is per- ratory funnel with methylene chloride or else in a continuous
formed using either external or internal standard techniques extractor. Dry the extracts separately through a column of
packed with 3% SP-2550 on Supelcoport (100/120 mesh) contains each parameter of interest at a concentration of
or equivalent. 100 g/mL in acetone is required. PCBs and multicomponent
Column for acids: 1.8 m long 2 mm I.D. glass, packed with pesticides may be omitted from this test.
PRECISION & ACCURACY The MDL concentrations were average percent recovery and the standard deviation of the
obtained using reagent water. The MDL actually achieved in a percent recovery. Spike all samples with the surrogate standard
given analysis will vary depending on instrument sensitivity spiking solution and calculate the percent recovery of each
and matrix effects. This method was tested by 15 laboratories surrogate compound.
Endrin EPA Method 8080
ments) was not reported. TITLE Organochlorine Pesticides and Polychlorinated
The range (in g/L) for average recovery for 4 measurements Biphenyls By Gas Chromatography
was not reported.
The range (in %) for percent recovery was not reported. MATRIX This method is used to determine the concentra-
Accuracy (in g/L) as expected recovery for one or more mea- tion of various organochlorine pesticides and polychlorinated
surements of a sample containing a true concentration of biphenyls in extracts prepared from water, groundwater, soils,
C was not reported. and sediments.

METHOD SUMMARY This method covers 26 pesticides and Soil, sediments, and sludges — Use an 8-oz. widemouth glass
Aroclor (PCB) mixtures and it is suitable for monitoring-type with a screw-top Teflon®-lined cover. Pre-wash the bottle with
analyses. After extraction, concentration and solvent exchange detergent, rinse with distilled water and methanol (or isopro-
to hexane, a 2- to 5-L sample aliquot is injected into a GC panol).
using the solvent flush technique, and the analytes are detected
by an electron capture detector (ECD) or an electrolytic con- sludge samples immediately to 4C.
ductivity detector in the halogen mode (HECD). Both neat and
diluted organic liquids may be analyzed by direct injection. Water samples — If residual chlorine is present, add 3 mL of
10% sodium thiosulfate per gallon and cool to 4C. All extracts
INTERFERENCES Interferences coextracted from the sam- and samples should be stored under refrigeration.
ples will vary considerably from source to source. Interferences
by phthalate esters can pose a major problem in pesticide deter- MHT Liquid samples must be extracted within 7 days and
minations when using the ECD. Cross-contamination of clean the extracts must be analyzed within 40 days. Soils, sediments,
glassware routinely occurs when plastics are handled during and sludges may be stored for a maximum of 14 days prior to
extraction steps, especially when solvent-wetted surfaces are extraction.
handled. The contamination from phthalate esters can be com- SAMPLE PREPARATION
pletely eliminated with a microcoulometric or electrolytic con- Liquid samples — Extract 1 L samples in a continuous extrac-
ductivity detector. Solvents, reagent, glassware, and other tor at pH 5–9 with methylene chloride after adding 1.0 mL of
sample processing hardware may yield artifacts and/or inter- surrogate spiking solution to each sample. Pass the extract
ferences to sample analysis. through a column of anhydrous sodium sulfate to dry and
INSTRUMENTATION A gas chromatograph capable of on- concentrate it in a K-D apparatus to 1 mL volume.
column injections is needed. It must be equipped with an ECD Soils, sediments and sludges — Rapidly weigh approximately
or a HECD and one of the following GC columns: 30 g of sample into a 400-mL beaker to avoid loss of the more
Column 1: Supelcoport (100/120 mesh) coated with 1.5% SP-
clay type) that do not have a free-flowing sandy texture must
2250/1.95% SP-2401 packed in a 1.8 m 4 mm I.D. glass
be mixed with anhydrous sodium sulfate until the sample is
column.
free flowing. Add 1 mL of surrogate standards to all samples,
spikes, standards, and blanks. Add 100 mL of 1:1 methylene
in a 1.8 m 4 mm I.D. glass column.
chloride:acetone and extract ultrasonically. Decant and filter
PRECISION & ACCURACY The method was tested by 20 extracts, dry the extract by passing it through a drying column
laboratories using organic-free reagent water, drinking water, containing anhydrous sodium sulfate and concentrate to 1 mL
surface water, and three industrial wastewaters spiked at six in a K-D apparatus.
concentrations. Concentrations used in the study ranged from
Hexane solvent exchange — Add 50 mL of hexane, a new boil-
ing chip, and concentrate until the apparent volume of liquid
400 g/L for multicomponent parameters. Overall precision reaches 1 mL. Adjust the extract volume to 10.0 mL. Stopper
and method accuracy were found to be directly related to the
the concentration tube and store refrigerated at 4C if further
concentration of the analyte and essentially independent of the processing will not be performed immediately. If the extract
sample matrix. The sensitivity of this method usually depends will be stored longer than two days, transfer it to a vial with
on the concentration of interferences rather than on instru- Teflon®-lined screw-cap or crimp top.
mental limitations.
QUALITY CONTROL Demonstrate through the analysis of
MDL in g/L was 0.006. a reagent water blank, that all glassware and reagents are inter-
Concentration range in g/L was 0.5–30. ference free. Each time a set of samples is processed, a method
Accuracy as recovery (x*) in g/L was 0.89C-0.04 . blank should be processed as a safeguard against chronic lab
Overall precision (S*) in g/L was 0.24x + 0.25. contamination. A reagent blank, a matrix spike, and a duplicate
x* = Expected recovery for one or more measurements of a sample or matrix spike duplicate must be performed for each analytical
containing concentration C, in g/L. batch (up to a maximum of 20 samples) analyzed.
Analytical system performance must be verified by analyzing
ments at an average concentration found of the analyte QC check samples. The QC check sample concentration should
in g/L. contain each single-component analyte at the following con-
C = True value for the concentration, in g/L. centrations in acetone: 4,4-DDD, 10 g/mL; 4,4-DDT,
10 g/mL; endosulfan II, 10 g/mL; endosulfan sulfate,
10 g/mL; and any other single-component pesticide at
SAMPLING METHOD 2 g/mL. If the method is only to be used to analyze PCBs,
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with Chlordane, or Toxaphene, the QC check sample concentrate
a screw-top Teflon®-lined cover. Pre-wash the bottle with deter- should contain the most representative multicomponent
gent, rinse with distilled water and methanol (or isopropanol). parameter at a concentration of 50 g/mL in acetone.

REFERENCE Test Methods for Evaluating Solid Waste (SW- Overall precision in g/L is not listed.
(a) EQLs listed for soil/sediment are based on wet weight. Nor-
of Solid Wastes, Washington, DC.
Endrin EPA Method 8270 ation chromatography cleanup.
and 200 ng of acid surrogates (for a 1-L injection). Analysis with detergent and rinsed with distilled water and methanol
is performed by GC/MS using a capillary GC column. (or isopropanol).
INTERFERENCES Raw GC/MS data from all blanks, sam- SAMPLE PRESERVATION
ples, and spikes must be evaluated for interferences. Contam- Liquid samples — If residual chlorine is present, add 3 mL of
ination by carryover can occur whenever high-concentration 10% sodium thiosulfate per gallon, cool to 4C and store in a
and low-concentration samples are sequentially analyzed. To solvent-free refrigerator until analysis; if chlorine is not present,
reduce carryover, the sample syringe must be rinsed out then eliminate the sodium thiosulfate addition.
analysis of blank solvent to check for cross-contamination.
capillary column. A continuous liquid-liquid extractor
equipped with Teflon® or glass connection joints and stopcocks SAMPLE PREPARATION
requiring no lubrication, a K-D concentrating apparatus, water Liquid samples — Transfer 1 L quantitatively to a continuous
bath, and an ultrasonic disrupter with a minimum power of extractor. If high concentrations are anticipated, a smaller vol-
300 W and with pulsing capability are also required. ume may be used and then diluted with organic-free reagent
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
extracts that require dilution to avoid saturation of the detector.
analyte in the extract to be analyzed (assuming a 1- L injec-
The EQL(b) for groundwater in g/L is not listed. tion). Extract with methylene chloride for 18–24 h. Next, adjust
The EQL (a, b) for low concentrations in soil and sediment the pH of the aqueous phase to pH >11 using 10 N sodium
in g/kg is not listed. hydroxide and extract it with methylene chloride again for
Accuracy as g/L is not listed. 18–24 h. Dry the extract through a column containing anhydrous

sodium sulfate and concentrate it to 1 mL using a K-D con-
Endrin aldehyde EPA Method 625
centrator. CAS #7421-93-4
or wet samples (gummy or clay type) that do not have a free- TITLE Base/Neutrals and Acids, U.S. EPA Method 625
flowing sandy texture must be mixed with anhydrous sodium MATRIX This methods covers municipal and industrial
sulfate until the sample is free flowing. Add 1 mL of surrogate wastewaters.
sample in each analytical batch selected for spiking, add 1.0 mL METHOD SUMMARY Approximately 1 L of sample is seri-
of a matrix spiking standard. For base/neutral acid analysis, the ally extracted with methylene chloride at a pH greater than 11
amount added of the surrogates and matrix spiking com- and again at a pH less than 2 using a separatory funnel or a
pounds should result in a final concentration of 100 ng/ L of continuous extractor. The methylene chloride extract is dried,
each base/neutral analyte and 200 ng/L of each acid analyte concentrated to a volume of 1 mL, and analyzed by GC/MS.
in the extract to be analyzed (assuming a 1- L injection). Qualitative identification of the parameters in the extract is
Immediately add a 100-mL mixture of 1:1 methylene chlo- performed using the retention time and the relative abundance
ride:acetone and extract the sample ultrasonically for 3 min of three characteristic masses (m/z). Qualitative analysis is per-
and then decant or filter the extracts. Repeat the extraction two formed using either external or internal standard techniques
or more times. Dry the extract using a column with anhydrous with a single characteristic m/z.
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. INTERFERENCES Method interferences may be caused by
QUALITY CONTROL A methylene chloride solution con- contaminants in solvents, reagents, glassware, and other sample
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is processing hardware. Glassware must be scrupulously cleaned.
used for tuning the GC/MS system each 12-h shift. A system Glassware should be heated in a muffle furnace at 400C for 5
performance check also must be made during every 12-h shift. to 30 min. Some thermally stable materials, such as PCBs, may
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- not be eliminated by this treatment. Solvent rinses with acetone
rophenol, and benzidine is required to verify injection port and pesticide quality hexane may be substituted for the muffle
inertness and GC column performance. A calibration standard furnace heating. Matrix interferences may be caused by con-
at mid-concentration, containing each compound of interest, taminants that are coextracted from the sample. The base-
including all required surrogates, must be performed every 12 h neutral extraction may cause significantly reduced recovery of
during analysis. After the system performance check is met, phenols. The packed gas chromatographic columns recom-
calibration check compounds (CCCs) are used to check the mended for the basic fraction may not exhibit sufficient reso-
validity of the initial calibration. lution for some analytes.
The internal standard responses and retention times in the INSTRUMENTATION A GC/MS system with an injection
calibration check standard must be evaluated immediately after port designed for on-column injection when using packed col-
or during data acquisition. If the retention time for any internal umns and for splitless injection when using capillary columns.
standard changes by more than 30 seconds from the last check Column for base/neutrals: 1.8 m long  2 mm I.D. glass,
calibration (12 h), the chromatographic system must be packed with 3% SP-2550 on Supelcoport (100/120 mesh)
inspected for malfunctions and corrections must be made, as or equivalent.
required. If the electron ionization current plot (EICP) area for Column for acids: 1.8 m long 2 mm I.D. glass, packed with
any of the internal standards changes by a factor of two from 1% SP-1240DA on Supelcoport (100/120 mesh) or equivalent.
must be inspected for malfunctions and corrections must be PRECISION & ACCURACY The MDL concentrations were
made, as appropriate. obtained using reagent water. The MDL actually achieved in a
Demonstrate, through the analysis of a reagent water blank, and matrix effects. This method was tested by 15 laboratories
that interferences from the analytical system, glassware, and using reagent water, drinking water, surface water, and indus-
reagents are under control. The blank samples should be car- trial wastewaters spiked at six concentrations over the range 5
ried through all stages of the sample preparation and measure- to 100 g/L. Single operator precision, overall precision, and
ment steps. For each analytical batch (up to 20 samples), a method accuracy were found to be directly related to the con-
reagent blank, matrix spike, and matrix spike duplicate/dupli- centration of the parameter matrix.
different for different monitoring programs). The blank and The MDL (in g/L) in reagent water was not detected.
spiked samples must be carried through all stages of the sample The standard deviation (in g/L based on 4 recovery measure-
preparation and measurement steps. A QC reference sample ments) was 32.5.
concentrate containing each analyte at a concentration of The range (in g/L) for average recovery for 4 measurements
100 mg/L in methanol is required. was D-188.8.
The range (in %) for percent recovery was D-209.
REFERENCE Test Methods for Evaluating Solid Waste (SW- Accuracy (in g/L) as expected recovery for one or more mea-
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office surements of a sample containing a true concentration of
of Solid Waste, Washington, DC. C was 0.76C-3.86.

X was 0.18X + 3.91. analyses. After extraction, concentration and solvent exchange
tion found at X was 0.73X–0.62. by an electron capture detector (ECD) or an electrolytic con-
SAMPLE COLLECTION, PRESERVATION & HANDLING ferences to sample analysis.
extracted within 7 days of collection and completely analyzed Column 1: Supelcoport (100/120 mesh) coated with 1.5% SP-
within 40 days of extraction. 2250/1.95% SP-2401 packed in a 1.8 m 4 mm I.D. glass
QUALITY CONTROL Make an initial, one-time, demonstra- column.
tion of the ability to generate acceptable accuracy and precision Column 2: Supelcoport (100/120 mesh) coated with 3% OV-1
with this method. Before processing any samples, the analyst in a 1.8 m 4 mm I.D. glass column.
changed, a reagent water blank must be processed. Spike and
400 g/L for multicomponent parameters. Overall precision
pesticides may be omitted from this test.
sample matrix. The sensitivity of this method usually depends
After analysis of five spiked wastewater samples, calculate the on the concentration of interferences rather than on instru-
average percent recovery and the standard deviation of the mental limitations.
surrogate compound.
Accuracy as recovery (x*) in g/L was not listed .
REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct. Overall precision (S*) in g/L was not listed.
26, 1984.
Endrin aldehyde EPA Method 8080 ments at an average concentration found of the analyte
CAS #7421-93-4 in g/L.
TITLE Organochlorine Pesticides and Polychlorinated X = Average recovery found for measurements of samples con-
Biphenyls By Gas Chromatography taining a concentration of C, in g/L.
MATRIX This method is used to determine the concentra- SAMPLING METHOD
tion of various organochlorine pesticides and polychlorinated Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
biphenyls in extracts prepared from water, groundwater, soils, a screw-top Teflon®-lined cover. Pre-wash the bottle with deter-
and sediments. gent, rinse with distilled water and methanol (or isopropanol).

Soil, sediments, and sludges — Use an 8-oz. widemouth glass REFERENCE Test Methods for Evaluating Solid Waste (SW-
with a screw-top Teflon®-lined cover. Pre-wash the bottle with 846). U.S. EPA. 1983. Method 8080B, Rev. 2, Nov. 1990. Office
detergent, rinse with distilled water and methanol (or isopro- of Solid Wastes, Washington, DC.
panol).
sludge samples immediately to 4C. Endrin aldehyde EPA Method 8270
CAS #7421-93-4
SAMPLE PREPARATION lakes, etc.
Soils, sediments and sludges — Rapidly weigh approximately gate, and matrix spiking standards, is extracted in a continuous
30 g of sample into a 400-mL beaker to avoid loss of the more extractor first under acid conditions and then under basic con-
internal standard solution just prior to analysis by GC/MS. The
volume injected should contain about 100 ng of base/neutral
and 200 ng of acid surrogates (for a 1-L injection). Analysis
containing anhydrous sodium sulfate and concentrate to 1 mL INTERFERENCES Raw GC/MS data from all blanks, sam-
in a K-D apparatus. ples, and spikes must be evaluated for interferences. Contam-
parameter at a concentration of 50 g/mL in acetone. Accuracy as g/L is 0.76C–3.86.

Overall precision in g/L is 0.73X–0.62. drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator.
mally data is reported in a dry-weight basis; therefore, EQLs Soils, sediments, or sludges — Use 30 g of sample. Nonporous
will be higher based on the % dry weight of each sample. or wet samples (gummy or clay type) that do not have a free-
This calculation is based on a 30-g sample and gel perme- flowing sandy texture must be mixed with anhydrous sodium
ation chromatography cleanup. sulfate until the sample is free flowing. Add 1 mL of surrogate
(b) Sample EQLs are highly matrix-dependent. The EQLs are standards to all samples, spikes, standards, and blanks. For the
provided for guidance and may not always be achievable. sample in each analytical batch selected for spiking, add 1.0 mL
C = True value for concentration, in g/L. of a matrix spiking standard. For base/neutral acid analysis, the
X = Average recovery found for measurements of samples con- amount added of the surrogates and matrix spiking com-
taining a concentration of C, in g/L. pounds should result in a final concentration of 100 ng/ L of
ESTIMATED QUANTITATION LIMIT each base/neutral analyte and 200 ng/L of each acid analyte
High-concentration soil and sludges by sonicator 7.5 ride:acetone and extract the sample ultrasonically for 3 min
Non-water miscible waste 75 and then decant or filter the extracts. Repeat the extraction two
This estimated EQL is similar to an EPA “Practical Quantitation
Limit.” QUALITY CONTROL A methylene chloride solution con-
SAMPLING METHOD taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
used for tuning the GC/MS system each 12-h shift. A system
performance check also must be made during every 12-h shift.
detergent and rinsed with distilled water and methanol (or A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
isopropanol). rophenol, and benzidine is required to verify injection port
inertness and GC column performance. A calibration standard
SAMPLE PRESERVATION validity of the initial calibration.
Soils, sediments, or sludges — Cool samples to 4C and store calibration (12 h), the chromatographic system must be
in a solvent-free refrigerator. inspected for malfunctions and corrections must be made, as
gates and matrix spiking compounds added to the sample
preparation and measurement steps. A QC reference sample
the pH of the aqueous phase to pH >11 using 10 N sodium REFERENCE Test Methods for Evaluating Solid Waste (SW-
hydroxide and extract it with methylene chloride again for 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
18–24 h. Dry the extract through a column containing anhy- of Solid Waste, Washington, DC.

Endrin ketone EPA Method 8270
ation chromatography cleanup.
CAS #53494-70-5
(b) Sample EQLs are highly matrix-dependent. The EQLs are
TITLE Semivolatile Organic Compounds by GC/MS provided for guidance and may not always be achievable.
C = True value for concentration, in g/L.
from all types of solid waste matrices, soils, and groundwater.
Although surface waters are not specifically mentioned, this ESTIMATED QUANTITATION LIMIT
method should be applicable to water samples from rivers, Other Matrices Factor (a)
METHOD SUMMARY This method covers 259 semivolatile Non-water miscible waste 75
organic compounds. In very limited applications direct injec- (a) EQL forother matrices =[EQL forlow soil/sediment] [Factor].
gate, and matrix spiking standards, is extracted in a continuous SAMPLING METHOD
extractor first under acid conditions and then under basic con- Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
ditions. Typically 30 g of a solid sample, containing surrogate, a screw-top Teflon®-lined cover that has been prewashed with
and matrix spiking standards, is extracted ultrasonically. After detergent and rinsed with distilled water and methanol (or
concentrating the extract to 1 mL it is spiked with 10 L of an isopropanol).
between samples with solvent. Whenever an unusually concen-
trated sample is encountered, it should be followed by the Soils, sediments, or sludges — Cool samples to 4C and store
analysis of blank solvent to check for cross-contamination. in a solvent-free refrigerator.
INSTRUMENTATION A GC/MS and a data system are MHT Liquid samples must be extracted within 7 days and
required. The GC column used is a 30 m 0.25 mm I.D. (or the extracts analyzed within 40 days. Soils, sediments, or slud-
0.32 mm I.D.) 1um film thickness silicone-coated fused silica ges may be stored for a maximum of 14 days and the extracts
capillary column. A continuous liquid-liquid extractor analyzed within 40 days.
PRECISION & ACCURACY The estimated quantitation water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
limit (EQL) of Method 8270B for determining an individual sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
compound is approximately 1 mg/kg (wet weight) for soil or solution into each sample. For the sample in each analytical
sediment samples, 1–200 mg/kg for wastes (dependent on batch selected for spiking, add 1.0 mL of a matrix spiking stan-
dard. For base/neutral acid analysis, the amount of the surro-
matrix and method of preparation), and 10 g/L for ground-
water samples. EQLs will be proportionately higher for sample
extracts that require dilution to avoid saturation of the detector. should result in a final concentration of 100 ng/L of each
The EQL(b) for groundwater in g/L is not listed. tion). Extract with methylene chloride for 18–24 h. Next, adjust
in g/kg is not listed. hydroxide and extract it with methylene chloride again for
Accuracy as g/L is not listed. 18–24 h. Dry the extract through a column containing anhy-
Overall precision in g/L is not listed. drous sodium sulfate and concentrate it to 1 mL using a K-D
(a) EQLs listed for soil/sediment are based on wet weight. Nor- concentrator.
mally data is reported in a dry-weight basis; therefore, EQLs Soils, sediments, or sludges — Use 30 g of sample. Nonporous or
will be higher based on the % dry weight of each sample. wet samples (gummy or clay type) that do not have a free-flowing

sandy texture must be mixed with anhydrous sodium sulfate
Epichlorohydrin EPA Method 8240
until the sample is free flowing. Add 1 mL of surrogate stan- CAS #106-89-8
dards to all samples, spikes, standards, and blanks. For the
sample in each analytical batch selected for spiking, add 1.0 mL TITLE Volatile Organics By GC/MS: Packed Column Technique
amount added of the surrogates and matrix spiking com- MATRIX Nearly all types of sample matarices, regardless of
water content, can be analyzed using this method. This includes
pounds should result in a final concentration of 100 ng/ L of
groundwater, aqueous sludges, caustic liquors, acid liquors,
each base/neutral analyte and 200 ng/L of each acid analyte waste solvents, oily wastes, mousses, tars, fibrous wastes, poly-
in the extract to be analyzed (assuming a 1- L injection). metric emulsions, filter cakes, spent carbons, spent catalysts,
Immediately add a 100-mL mixture of 1:1 methylene chlo- soils, and sediments.
METHOD SUMMARY Method 8240B covers 80 volatile
organic compounds that are introduced into a gas chromato-
graph by the purge-and-trap method or by direct injection (in
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. limited applications). For the purge-and-trap method an inert
QUALITY CONTROL A methylene chloride solution con- gas (zero grade nitrogen or helium) is bubbled through a 5-mL
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is solution at ambient temperature. Purged sample components
used for tuning the GC/MS system each 12-h shift. A system are trapped in a tube of sorbent materials. When purging is
complete, the sorbent tube is heated and backflushed with inert
gas to desorb the trapped components onto a GC column.
A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
rophenol, and benzidine is required to verify injection port INTERFERENCES Impurities in the purge gas and from
inertness and GC column performance. A calibration standard organic compounds outgassing from the plumbing ahead of
at mid-concentration, containing each compound of interest, the trap account for many contamination problems. Interfer-
including all required surrogates, must be performed every 12 h ences purged or coextracted from the samples will vary con-
siderably from source to source. Cross-contamination can
occur whenever high-level and low-level samples are analyzed
sequentially. Whenever an unusually concentrated sample is
validity of the initial calibration. analyzed, it should be followed by the analysis of organic-free
The internal standard responses and retention times in the reagent water to check for cross-contamination. Samples also
calibration check standard must be evaluated immediately after can be contaminated by diffusion of volatile organics (partic-
or during data acquisition. If the retention time for any internal ularly methylene chloride and fluorocarbons) through the sep-
tum seal into the sample during shipment and storage. A trip
blank can serve as a check on such contamination. The lab
calibration (12 h), the chromatographic system must be where volatile analysis is performed and also the refrigerated
inspected for malfunctions and corrections must be made, as storage area should be completely free of solvents.
any of the internal standards changes by a factor of two from INSTRUMENTATION A gas chromatograph/mass spec-
the last daily calibration standard check, the mass spectrometer trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
I.D. glass column packed with 1% SP-1000 on Carbopack-B
(60/80 mesh) is required.Also needed is a 5-mL purging device,
made, as appropriate.
a sorbent trap, and a thermal desorption apparatus.
PRECISION & ACCURACY This method is reported to have
that interferences from the analytical system, glassware, and been tested by 15 laboratories using organic-free reagent water,
reagents are under control. The blank samples should be car- drinking water, surface water, and industrial wastewaters (not
ried through all stages of the sample preparation and measure- specified) fortified at six concentrations over the range 5–
ment steps. For each analytical batch (up to 20 samples), a 600 g/L.
Sample estimated quantitation limits (EQLs) are highly
matrix-dependent. The EQLs listed may not always be achiev-
different for different monitoring programs). The blank and able. EQLs listed for soils or sediments are based on wet weight.
spiked samples must be carried through all stages of the sample Normally, data is reported on a dry-weight basis; therefore,
preparation and measurement steps. A QC reference sample EQLs will be higher, based on the percent dry weight of each
concentrate containing each analyte at a concentration of sample. Note that EQLs are even more variable than MDLs and
100 mg/L in methanol is required. that they are highly variable depending on the matrix being
analyzed.
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office EQL in groundwater in g/L was not listed.
of Solid Waste, Washington, DC. EQL in low soil or sediment in g/kg was not listed.

Accuracy (a) in g/L was not listed. (EPA Method 3810) or the hexadecane extraction and screen-
Precision (b) in g/L was not listed. ing method (EPA Method 3820). Use the screening data to
determine whether to use the low-concentration method
(a) Average recovery found for measurements of samples con- (0.005–1 mg/kg) or the high-concentration method (>1 mg/kg).
(b) Overall precision found for measurements of samples with Low-concentration method — The low-concentration method
average recovery X for samples containing a concentration is based on purging a heated sediment or soil sample mixed
of C in g/L. with organic-free reagent water containing the surrogate and
X = Average recovery found for measurement of samples con- internal standards. Analyze all reagent blanks and standards
taining a concentration of C in g/L. under the same conditions as the samples.
MULTIPLICATION FACTORS FOR OTHER MATRICES Use a 5-g sample if the expected concentration is <0.1 mg/kg
Other Matrices Factor (a) or a 1-g sample for expected concentrations between 0.1 and
1 mg/kg. Mix the contents of the sample container with a nar-
Waste miscible liquid waste 50 row metal spatula. Weigh the amount of the sample into a tared
High-concentration soil and sludge 125 purge device. Add the spiked water to the purge device, which
Non-water miscible waste 500 contains the weighed amount of sample, and connect the
(a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous device to the purge-and-trap system.
samples, the factor is on a wet-weight basis. High-concentration method — This method is based on
extracting the sediment or soil with methanol. A waste sample
SAMPLING METHOD
Liquid samples — Use a 40-mL glass screw-cap VOA vial with is either extracted or diluted, depending on its solubility in
methanol. Wastes that are insoluble in methanol are diluted
a Teflon®-faced silicone septum that has been prewashed,
with reagent tetraglyme or possibly polyethylene glycol (PEG).
rinsed with distilled deionized water, and oven dried. However,
An aliquot of the extract is added to organic-free reagent water
if residual chlorine is present, collect sample in a 40-oz. soil
containing surrogate and internal standards. This is purged at
VOA container which has been pre-preserved with 4 drops of ambient temperature. All samples with an expected concentra-
10% sodium thiosulfate, mix gently, and then transfer the sam- tion of >1.0 mg/kg should be analyzed by this method.
ple to a 40-mL VOA vial. Collect bubble-free samples in dupli-
cate and seal them in separate plastic bags. Mix the contents of the sample container with a narrow metal
spatula. For sediments or soils and solid wastes that are insol-
Soils or sediments, and sludges — Use an 8-oz. widemouth uble in methanol, weigh 4 g (wet weight) of sample into a tared
glass bottle with a Teflon®-faced silicone septum that has been 20-mL vial. For waste that is soluble in methanol, tetraglyme,
prewashed with detergent, rinsed with distilled deionized or PEG, weigh 1 g (wet weight) into a tared scintillation vial
water, and oven dried. Tap slightly to eliminate free air space. or culture tube or a 10-mL volumetric flask. Quickly add
Collect samples in duplicate and seal them in separate plastic bags. 9.0 mL of appropriate solvent then add 1.0 mL of a surrogate
SAMPLE PRESERVATION spiking solution to the vial, cap it, and shake it for 2 min.
Liquid samples — Add 4 drops of concentrated HCL and METHANOL EXTRACT REQUIRED FOR ANALYSIS
immediately cool samples to 4C and store in a solvent-free OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
refrigerator. Approximate Volume of
Soils or sediments, and sludges — Cool samples to 4C and Concentration Range Methanol Extract (a)
store in a solvent-free refrigerator. 500–10,000 g/kg 100 L
MHT Maximum holding time is 14 days from the date of 1,000–20,000 g/kg 50 L
sample collection. 5,000–100,000 g/kg 10 L
25,000–500,000 g/kg 100 L of 1/50 dilution (b)
SAMPLE PREPARATION
Liquid samples — Remove the plunger from a 5-mL syringe Calculate appropriate dilution factor for concentrations
and carefully pour the sample into the syringe barrel to just exceeding this table.
short of overflowing. Replace the syringe plunger and compress (a) The volume of methanol added to 5 mL of water being purged
the sample. Open the syringe valve and vent any residual air should be kept constant. Therefore, add to the 5-mLsyringe whatever
while adjusting the sample volume to 5.0 mL. If there is only volume of methanol is necessary to maintain a volume of 100 L
one volatile organic analysis (VOA) vial, a second syringe added to the syringe.
should be filled at this time to protect against possible loss of (b) Dilute an aliquot of the methanol extract and then take 100 L
sample integrity. Add 10 L of surrogate spiking solution and for analysis.
10 L of internal standard spiking solution through the valve
bore of the 5-mL syringe, then close the valve. The surrogate QUALITY CONTROL Demonstrate, through the analysis of
a reagent water blank, that interferences from the analytical
and internal standards may be mixed and added as a single
system, glassware, and reagents are under control. Blank sam-
spiking solution.
ples should be carried through all stages of the sample prepa-
Sediments, soils, and waste samples — All samples of this type ration and measurement steps. For each analytical batch (up
should be screened by GC analysis using a headspace method to 20 samples), a reagent blank, matrix spike, and matrix spike

duplicate must be analyzed (the frequency of the spikes may pounds by flame photometric gas chromatography. Sulfur
be different for different monitoring programs). The blank and cleanup using EPA Method 3660 may alleviate this interference.
spiked samples must be carried through all stages of the sample A nitrogen phosphorus detector (NPD) is also recommended.
preparation and measurement steps. QC samples mentioned
A few analytes coelute on certain columns. Therefore, select a
in the section on Interferences will also be needed as appropri-
second column for confirmation where coelution of the ana-
ate to those situations.
lytes of interest does not occur.
Method interferences may be caused by contaminants in sol-
vents, reagents, glassware, and other sample processing hard-
ware that lead to discrete artifacts or elevated baselines in gas
chromatograms. All these materials must be routinely demon-
strated to be free from interferences under the conditions of
EPN EPA Method 8141 the analysis by analyzing reagent blanks.
CAS #2104-64-5
INSTRUMENTATION A GC with a NPD or a FPD will be
needed. A data system or integrator is recommended for mea-
TITLE Organophosphorus Compounds by Gas Chromatog-
suring peak areas and/or peak heights. A Kuderna-Danish
raphy: Capillary Column Technique
(K-D) apparatus will be needed for extract concentration.
MATRIX This method covers aqueous and solid matrices.
Column 1: 15 m  0.53 mm megabore capillary column,
This includes a wide variety such as drinking water, ground-
1.0 m film thickness, DB-210.
water, industrial wastewaters, surface waters, soils, solids, and
sediments.
1.5 m film thickness, SPB-608.
METHOD SUMMARY This is a GC method used to deter- Column 3: 15 m  0.53 mm megabore capillary column,
mine the concentration of 28 organophosphorus pesticides. 1.0 m film thickness, DB-5.
The use of Gel Permeation Cleanup (EPA Method 3640) for Three megabore capillary columns are included for analysis of
sample cleanup has been demonstrated to yield recoveries of organophosphates by this method. Column 1 (DB-210 or
less than 85% for many method analytes and is therefore not equivalent) and Column 2 (SPB-608 or equivalent) are recom-
recommended for use with this method. mended if a large number of organophosphorus analytes are
to be determined. If the superior resolution offered by Column
This method provides GC conditions for the detection of ppb
1 and Column 2 is not required, Column 3 (DB-5 or equiva-
concentrations of organophosphorus compounds. Prior to the
lent) may be used. For megabore capillary columns, automatic
use of this method, appropriate sample preparation techniques
injections of 1 L are recommended.
must be used. Water samples are extracted at a neutral pH with
methylene chloride as a solvent by using a separatory funnel PRECISION & ACCURACY The MDL actually achieved in
(EPA Method 3510) or a continuous liquid-liquid extractor a given analysis will vary, as it is dependent on instrument
(EPA Method 3520). Soxhlet extraction (EPA Method 3540) or sensitivity and matrix effects. Single operator accuracy and
ultrasonic extraction (EPA Method 3550) using methylene precision studies have been conducted with spiked water and
chloride/acetone (1:1) are used for solid samples. Both neat soil samples.
and diluted organic liquids (EPA Method 3580) may be ana-
MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
lyzed by direct injection. Spiked samples are used to verify the
applicability of the chosen extraction technique to each new Matrix Factor (b)
sample type. A GC with a flame photometric (FPD) or nitro- Groundwater 10
gen-phosphorus detector (NPD) is used for this multiresidue (EPA Method 3510 or EPA Method 3520)
procedure. Low-concentration soil by Soxhlet and no cleanup 10 (c)
INTERFERENCES The use of Florisil cleanup materials (EPA Low-concentration soil by ultrasonic extraction 6.7 (c)
Method 3620) for some of the compounds in this method has with GPC cleanup
been demonstrated to yield recoveries less than 85% and is High-concentration soil and sludges 500 (c)
therefore not recommended for all compounds. Use of phos- by ultrasonic extraction
Non-water miscible waste (EPA Method 3580) 1000 (c)
phorus or halogen specific detectors, however, often obviates
the necessity for cleanup for relatively clean sample matrices. (a) SampleEQLs are highly matrix-dependent. TheEQLslisted here
If particular circumstances demand the use of an alternative are provided for guidance and may not always be achievable.
cleanup procedure, the analyst must determine the elution pro- (b) EQL = [Method detection limit] [Factor]. For non-aqueous
file and demonstrate that the recovery of each analyte is no less samples the factor is on a wet-weight basis.
than 85%. (c) Multiply this factory times the soil MDL.
Use of a flame photometric detector (FPD) in the phosphorus The MDL (in g/L) when reagent water was extracted using a
mode will minimize interferences from materials that do not separatory funnel was 0.04.
contain phosphorus. Elemental sulfur, however, may interfere The MDL (in g/kg) when soil was extracted using Soxhlet
with the determination of certain organophosphorus com- extraction (EPA Method 3540) was 2.0.

Accuracy (as % recovery) with separatory funnel extraction made with this method. Follow the GC/MS operating require-
ranged from 113 (with low spikes) to 97 (with high spikes). ments specified in EPA Method 8270.
Accuracy (as % recovery) with continuous liquid-liquid extrac-
When available, chemical ionization mass spectra may be
tion ranged from not recovered (with low spikes) to 119
employed to aid in the qualitative identification process. To
(with high spikes).
confirm an identification of a compound, the background-
Accuracy (as % recovery) with Soxhlet extraction of soils
corrected mass spectrum of the compound must be obtained
ranged from 114 (with low spikes to 82 (with high spikes).
from the sample extract and must be compared with a mass
Accuracy (as % recovery) with ultrasonic extraction of soils
spectrum from a stock or calibration standard analyzed under
ranged from 14 (with low spikes) to 105 (with high spikes).
the same chromatographic conditions. The molecular ion and
SAMPLE COLLECTION, PRESERVATION & HANDLING all other ions present above 20% relative abundance in the mass
Containers used to collect samples for the determination of spectrum of the standard must be present in the mass spectrum
semivolatile organic compounds should be soap and water of the sample with agreement to 20%. The retention time of
washed followed by methanol (or isopropanol) rinsing. The the compound in the sample must be within six seconds of the
sample containers should be of glass or Teflon® and have screw- retention time for the same compound in the standard solution.
top covers with Teflon® liners.
Should the MS procedure fail to provide satisfactory results,
No preservation is used with concentrated waste samples. With additional steps may be taken before reanalysis. These steps
liquid samples containing no residual chlorine and with soil, may include the use of alternate packed or capillary GC col-
sediment, and sludge samples, immediately cooling to 4C is umns or additional sample cleanup.
the only preservation used. When residual chlorine is present
then 3 mL of 10% aqueous sodium sulfate is added for each REFERENCE Test Methods for Evaluating Solid Waste, Phys-
gallon of sample collected, followed by cooling to 4C. ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
of Solid Waste, Washington, DC, EPA Method 8141 July 1992.
Liquid samples must be extracted within 7 days and their
extracts analyzed within 40 days. Concentrated waste, soil, sed-
iment, and sludge samples must be extracted within 14 days
and their extracts analyzed within 40 days. EPN EPA Method 8270
CAS #2104-64-5
SAMPLE PREPARATION In general, water samples are
extracted at a neutral pH with methylene chloride, using either TITLE Semivolatile Organic Compounds by GC/MS
EPA Method 3510 or EPA Method 3520. Solid samples are
extracted using either EPA Method 3540 or EPA Method 3550
with methylene chloride/acetone (1:1) as the extraction solvent.
Prior to GC analysis, the extraction solvent may be exchanged Although surface waters are not specifically mentioned, this
to hexane. Single lab data indicates that samples should not be method should be applicable to water samples from rivers,
transferred with 100% hexane during sample workup as the lakes, etc.
more water soluble organophosphorus compounds may be lost.
If cleanup is performed on the samples, the analyst should organic compounds. In very limited applications direct injec-
analyze the samples by GC. This will confirm elution patterns tion of the sample into the GC/MS system may be appropriate,
and the absence of interferences from the reagents. If peak but this results in very high detection limits (approximately
detection and identification is prevented by the presence of 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
interferences, further cleanup is required. gate, and matrix spiking standards, is extracted in a continuous
QUALITY CONTROL The analyst should monitor the per-
formance of the extraction, cleanup (when used), and analyt-
ical system and the effectiveness of the method in dealing with
each sample matrix by spiking each sample, standard, and concentrating the extract to 1 mL it is spiked with 10 L of an
blank with one or two surrogates (e.g., organophosphorus
compounds not expected to be present in the sample). Deu-
terated analogs of analytes should not be used as surrogates for and 200 ng of acid surrogates (for a 1-L injection). Analysis
gas chromatographic analysis due to coelution problems. is performed by GC/MS using a capillary GC column.
A minimum of five concentrations for each analyte of interest INTERFERENCES Raw GC/MS data from all blanks, sam-
should be prepared through dilution of the stock standards ples, and spikes must be evaluated for interferences. Contam-
with isooctane. One of the concentrations should be at a con- ination by carryover can occur whenever high-concentration
centration near, but above, the MDL. and low-concentration samples are sequentially analyzed. To
Include a mid-level check standard after each group of 10 sam- between samples with solvent. Whenever an unusually concen-
ples in the analysis sequence. GC/MS techniques should be trated sample is encountered, it should be followed by the
judiciously employed to support qualitative identifications analysis of blank solvent to check for cross-contamination.

equipped with Teflon® or glass connection joints and stopcocks
SAMPLE PREPARATION
PRECISION & ACCURACY The estimated quantitation water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
limit (EQL) of Method 8270B for determining an individual sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
compound is approximately 1 mg/kg (wet weight) for soil or solution into each sample. For the sample in each analytical
matrix and method of preparation), and 10 g/L for ground- dard. For base/neutral acid analysis, the amount of the surro-
water samples. EQLs will be proportionately higher for sample gates and matrix spiking compounds added to the sample
The EQL(b) for groundwater in g/L is 10. tion). Extract with methylene chloride for 18–24 h. Next, adjust
in g/kg is not determined. hydroxide and extract it with methylene chloride again for
ESTIMATED QUANTITATION LIMIT
Other Matrices Factor (a) Immediately add a 100-mL mixture of 1:1 methylene chlo-
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor]. sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
SAMPLING METHOD used for tuning the GC/MS system each 12-h shift. A system
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with performance check also must be made during every 12-h shift.
a screw-top Teflon®-lined cover that has been prewashed with A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
detergent and rinsed with distilled water and methanol (or rophenol, and benzidine is required to verify injection port
isopropanol). inertness and GC column performance. A calibration standard
SAMPLE PRESERVATION
then eliminate the sodium thiosulfate addition.
Soils, sediments, or sludges — Cool samples to 4C and store inspected for malfunctions and corrections must be made, as
in a solvent-free refrigerator. required. If the electron ionization current plot (EICP) area for

any of the internal standards changes by a factor of two from Column 2: 30 m 0.25 mm I.D. DB-1701 bonded fused silica
the last daily calibration standard check, the mass spectrometer column, 0.25 m film thickness, or equivalent.
PRECISION & ACCURACY This method has been validated
in a single lab and estimated detection limits (EDLs) have been
Demonstrate, through the analysis of a reagent water blank, determined for each analyte. Observed detection limits may
that interferences from the analytical system, glassware, and vary among waters, depending upon the nature of the inter-
reagents are under control. The blank samples should be car- ferences in the sample matrix and the specific instrumentation
ried through all stages of the sample preparation and measure- used. Analytes that are not separated chromatographically can-
ment steps. For each analytical batch (up to 20 samples), a not be individually identified and measured unless an alterna-
reagent blank, matrix spike, and matrix spike duplicate/dupli- tive technique for identification and quantification exist.
cate must be analyzed (the frequency of the spikes may be The estimated detection limit (in g/L) was 0.25. The EDL is
different for different monitoring programs). The blank and defined as either method detection limit or a level of compound
spiked samples must be carried through all stages of the sample in a sample yielding a peak in the final extract with signal-to-
preparation and measurement steps. A QC reference sample noise ratio of approximately 5, whichever value is higher.
concentrate containing each analyte at a concentration of
100 mg/L in methanol is required. The concentration used for these measurements (in g/L) was
2.5.
REFERENCE Test Methods for Evaluating Solid Waste (SW- The accuracy (as % recovery) was 85.
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office The precision (% RSD) was 9.
SAMPLING METHOD Grab samples are collected in 1-L
glass sample bottles (prewashed with detergent and hot tap
water, rinsed with reagent water, and dried in an oven at 400C
EPTC EPA Method 507 for 1 h) with screw caps lined with PTFE-fluorocarbon.
CAS #759-94-4
SAMPLE PRESERVATION Add mercuric chloride to the
TITLE Determination of Nitrogen and Phosphorus-Con- sample bottle in amounts to produce a concentration of
10 mg/L. If residual chlorine is present, add 80 mg of sodium
taining Pesticides in Water by GC/NPD
thiosulfate/L of sample to the sample bottle prior to collection.
MATRIX This method is applicable to the determination of After collection, seal bottle and shake vigorously for 1 min, then
certain nitrogen and phosphorus-containing pesticides in fin- cool the sample to 4C immediately and store it at 4C in the
ished drinking water and groundwater. dark until extraction.
METHOD SUMMARY Method 507 covers 46 nitrogen- and MHT Maximum holding time of the samples, and in some
phosphorus-containing pesticides. A 1-L sample is fortified cases the extracts, is 14 days.
with a surrogate standard, salted, buffered, extracted with
Note: Samples with this compound exhibited recoveries of less
methylene chloride, and concentrated; then the solvent is
than 60% after 14 days.
exchanged with methyl tert-butyl ether (MTBE) and concen-
trated again, and a 2-L aliquot of a sample extract is injected SAMPLE PREPARATION Fortify the sample with 50 L of
into a GC system equipped with a selective nitrogen-phospho- the surrogate standard solution, adjust to pH 7 with phosphate
rus detector and a capillary column for analysis. buffer, add 100 g NaCl to the sample, and seal and shake to
dissolve the salt; then extract with methylene chloride in a
INTERFERENCES Method interferences may be caused by separatory funnel or in a mechanical tumbler bottle. Dry the
contaminants in solvents, reagents, glassware, and other sample extract by pouring it through a solvent-rinsed drying column
processing apparatus. Interfering contamination may occur containing about 10 cm of anhydrous sodium sulfate. Collect
when a sample containing low concentrations of analytes is the extract in a Kuderna-Danish (K-D) concentrator and rinse
analyzed immediately following a sample containing relatively the column with 20–30 mL methylene chloride. Concentrate
high concentrations. One or more injections of MTBE should the extract to about 2 mL and rinse the flask and its lower joint
be made following the analysis of a sample with high concen- into the concentrator tube with 1 to 2 mL of methyl t-butyl
trations of analytes to check for analyte carryover. Matrix inter- ether (MTBE). Add 5–10 mL of MTBE and concentrate the
ferences may be caused by contaminants that are coextracted extract twice (adding more MTBE) to a final volume of 5.0 mL
from the sample. The extent of matrix interferences will vary and store it at 4C until analysis.
considerably from source to source, depending upon the water
sampled. Note: If methylene chloride is not completely removed from
the final extract, it may cause detector problems.
INSTRUMENTATION A gas chromatograph system (GC)
equipped with a nitrogen-phosphorus detector (NPD) is QUALITY CONTROL Minimum quality control require-
ments are initial demonstration of lab capability, determina-
needed.
tion of surrogate compound recoveries in each sample and
Column 1: 30 m 0.25 mm I.D. DB-5 bonded fused silica col- blank, monitoring internal standard peak area or height in each
umn, 0.25 m film thickness, or equivalent. sample and blank, analysis of lab reagent blanks, lab fortified

samples, lab fortified blanks, and other QC samples. A lab occur whenever high-level and low-level samples are analyzed
reagent blank is analyzed to demonstrate that all glassware and sequentially. Whenever an unusually concentrated sample is
reagent interferences are under control. analyzed, it should be followed by the analysis of organic-free
reagent water to check for cross-contamination. Samples also
Initial demonstration of capability is fulfilled by analyzing four can be contaminated by diffusion of volatile organics (partic-
fortified reagent water samples with the recovery value for each ularly methylene chloride and fluorocarbons) through the sep-
analyte falling within the acceptable range ( 30% average tum seal into the sample during shipment and storage. A trip
recovery). Surrogate recoveries from samples or method blanks blank can serve as a check on such contamination. The lab
must be 70–130%. The internal standard response for any sam- where volatile analysis is performed and also the refrigerated
ple chromatogram should not deviate from the daily calibra- storage area should be completely free of solvents.
tion check standard’s internal standard response by more than
30% or lab fortified blanks and sample matrices are used to INSTRUMENTATION A gas chromatograph/mass spec-
assess lab performance and analyte recovery, respectively. trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
If the response for the target analyte peak exceeds the working (60/80 mesh) is required.Also needed is a 5-mL purging device,
range of the system, dilute the extract and reanalyze.Alternative a sorbent trap, and a thermal desorption apparatus.
techniques such as an alternate detector or second chromatog-
raphy column should be used to confirm peak identification PRECISION & ACCURACY This method is reported to have
when sample components are not resolved adequately. been tested by 15 laboratories using organic-free reagent water,
drinking water, surface water, and industrial wastewaters (not
EPA CONTACT & HOTLINE For technical questions contact specified) fortified at six concentrations over the range 5–
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and 600 g/L.
Drinking Water (WH-550D), 401 M St. SW, Washington, DC
20460. Tel. (202) 260-3040. For further information the EPA Sample estimated quantitation limits (EQLs) are highly
Safe Drinking Water Hotline may be called at: (800) 426-4791. matrix-dependent. The EQLs listed may not always be achiev-
able. EQLs listed for soils or sediments are based on wet weight.
REFERENCE Methods for the Determination of Organic Normally, data is reported on a dry-weight basis; therefore,
Compounds in Drinking Water, EPA/600/4-88/039 (revised EQLs will be higher, based on the percent dry weight of each
July 1991). U.S. EPA Environmental Monitoring Systems Lab- sample. Note that EQLs are even more variable than MDLs and
oratory, Cincinnati, OH, 45268, U.S.A. Available from the that they are highly variable depending on the matrix being
National Technical Information Service (NTIS), 5285 Port analyzed.
EQL in groundwater in g/L was not listed.
Order Number is PB91-231480.
EQL in low soil or sediment in g/kg was not listed.
Accuracy (a) in g/L was not listed.
Precision (b) in g/L was not listed.
Ethanol EPA Method 8240
(a) Average recovery found for measurements of samples con-
CAS #64-17-5
(b) Overall precision found for measurements of samples with
TITLE Volatile Organics By GC/MS: Packed Column Technique
average recovery X for samples containing a concentration
MATRIX Nearly all types of sample matarices, regardless of of C in g/L.
water content, can be analyzed using this method. This includes X = Average recovery found for measurement of samples con-
groundwater, aqueous sludges, caustic liquors, acid liquors, taining a concentration of C in g/L.
waste solvents, oily wastes, mousses, tars, fibrous wastes, poly-
MULTIPLICATION FACTORS FOR OTHER MATRICES
metric emulsions, filter cakes, spent carbons, spent catalysts,
soils, and sediments. Other Matrices Factor (a)
METHOD SUMMARY Method 8240B covers 80 volatile Waste miscible liquid waste 50
organic compounds that are introduced into a gas chromato- High-concentration soil and sludge 125
graph by the purge-and-trap method or by direct injection (in Non-water miscible waste 500
limited applications). For the purge-and-trap method an inert (a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous
gas (zero grade nitrogen or helium) is bubbled through a 5-mL samples, the factor is on a wet-weight basis.
solution at ambient temperature. Purged sample components
are trapped in a tube of sorbent materials. When purging is SAMPLING METHOD
complete, the sorbent tube is heated and backflushed with inert Liquid samples — Use a 40-mL glass screw-cap VOA vial with
gas to desorb the trapped components onto a GC column. a Teflon®-faced silicone septum that has been prewashed,
INTERFERENCES Impurities in the purge gas and from if residual chlorine is present, collect sample in a 40-oz. soil
organic compounds outgassing from the plumbing ahead of VOA container which has been pre-preserved with 4 drops of
the trap account for many contamination problems. Interfer- 10% sodium thiosulfate, mix gently, and then transfer the sam-
ences purged or coextracted from the samples will vary con- ple to a 40-mL VOA vial. Collect bubble-free samples in dupli-
siderably from source to source. Cross-contamination can cate and seal them in separate plastic bags.

spiking solution to the vial, cap it, and shake it for 2 min.
SAMPLE PRESERVATION
SAMPLE PREPARATION
and internal standards may be mixed and added as a single a reagent water blank, that interferences from the analytical
spiking solution. system, glassware, and reagents are under control. Blank sam-
(EPA Method 3810) or the hexadecane extraction and screen- duplicate must be analyzed (the frequency of the spikes may
ing method (EPA Method 3820). Use the screening data to be different for different monitoring programs). The blank and
determine whether to use the low-concentration method spiked samples must be carried through all stages of the sample
(0.005–1 mg/kg) or the high-concentration method (>1 mg/kg). preparation and measurement steps. QC samples mentioned
Low-concentration method — The low-concentration method in the section on Interferences will also be needed as appropri-
is based on purging a heated sediment or soil sample mixed ate to those situations.
with organic-free reagent water containing the surrogate and REFERENCE Test Methods for Evaluating Solid Waste (SW-
internal standards. Analyze all reagent blanks and standards 846). U.S. EPA. 1983. Method 8240B, Rev. 2, Nov. 1990. Office
under the same conditions as the samples. of Solid Wastes, Washington, DC.
Use a 5-g sample if the expected concentration is <0.1 mg/kg
or a 1-g sample for expected concentrations between 0.1 and
1 mg/kg. Mix the contents of the sample container with a nar- Ethanol EPA Method 8015
row metal spatula. Weigh the amount of the sample into a tared CAS #64-17-5
purge device. Add the spiked water to the purge device, which
contains the weighed amount of sample, and connect the TITLE Nonhalogenated Volatile Organics
device to the purge-and-trap system.
MATRIX Groundwater, soils, sludges, water miscible liquid
High-concentration method — This method is based on wastes, and non-water miscible wastes.
is either extracted or diluted, depending on its solubility in APPLICATION This method is used for the analysis of 6
methanol. Wastes that are insoluble in methanol are diluted nonhalogenated VOCs. Samples are analyzed using direct injec-
with reagent tetraglyme or possibly polyethylene glycol (PEG). tion or purge-and-trap methods. Groundwater must be ana-
An aliquot of the extract is added to organic-free reagent water lyzed by the purge-and-trap method. The method provides an
containing surrogate and internal standards. This is purged at optional GC column that may help resolve analytes from inter-
ambient temperature. All samples with an expected concentra- ferences and which is also used for analyte confirmation.
tion of >1.0 mg/kg should be analyzed by this method.
INTERFERENCES There can be carryover contamination
Mix the contents of the sample container with a narrow metal with high- and low-level samples. Impurities may come from
spatula. For sediments or soils and solid wastes that are insol- the purge-and-trap apparatus, organic compounds outgassing

from the plumbing ahead of trap, diffusion of VOCs through and 200 ng of acid surrogates (for a 1-L injection). Analysis
the sample bottle septum during shipping or storage, or from is performed by GC/MS using a capillary GC column.
solvent vapors in the lab.
INSTRUMENTATION GC capable of on-column injections ples, and spikes must be evaluated for interferences. Contam-
or purge-and-trap sample introduction and a flame ionization ination by carryover can occur whenever high-concentration
detector (FID). Column 1: an 8 ft by 0.1 in 1% SP-1000 on and low-concentration samples are sequentially analyzed. To
Carbopack-B column. Column 2: a 6 ft by 0.1 in bonded n- reduce carryover, the sample syringe must be rinsed out
octane on Porasil-C. between samples with solvent. Whenever an unusually concen-
trated sample is encountered, it should be followed by the
RANGE Not available. analysis of blank solvent to check for cross-contamination.
MDL Not available.
PRECISION Not available. required. The GC column used is a 30 m 0.25 mm I.D. (or
0.32 mm I.D.) 1um film thickness silicone-coated fused silica
ACCURACY Not available. capillary column. A continuous liquid-liquid extractor
SAMPLING METHOD For water and liquid samples; use equipped with Teflon® or glass connection joints and stopcocks
glass 40-mL vials with Teflon®-lined septum caps and collect requiring no lubrication, a K-D concentrating apparatus, water
two vials per sample location with no headspace. For solids bath, and an ultrasonic disrupter with a minimum power of
and concentrated waste samples; use widemouth glass bottles 300 W and with pulsing capability are also required.
with Teflon® liners. Cool all samples to 4C PRECISION & ACCURACY The estimated quantitation
STABILITY For concentrated wastes, soils, sediments, or limit (EQL) of Method 8270B for determining an individual
sludges: cool to 4C. For liquids: add 4 drops of concentrated compound is approximately 1 mg/kg (wet weight) for soil or
hydrochloric acid, cool to 4C. sediment samples, 1–200 mg/kg for wastes (dependent on
MHT 14 days. water samples. EQLs will be proportionately higher for sample
QUALITY CONTROL Analyze a reagent blank, matrix spike, extracts that require dilution to avoid saturation of the detector.
and matrix spike duplicate/duplicate for each analytical batch The EQL(b) for groundwater in g/L is 10.
(up to 20 samples). Demonstrate the purity of glassware and The EQL (a, b) for low concentrations in soil and sediment
reagents by analyzing a reagent water method blank. Internal, in g/kg is not determined.
surrogate, and five concentration level calibration standards are Accuracy as g/L is not listed.
used. Overall precision in g/L is not listed.
REFERENCE Method 8015, SW-846, 3rd ed., Nov.1986. (a) EQLs listed for soil/sediment are based on wet weight. Nor-
Ethion EPA Method 8270
CAS #563-12-2
TITLE Semivolatile Organic Compounds by GC/MS
Although surface waters are not specifically mentioned, this
isopropanol).

SAMPLE PRESERVATION
the pH of the aqueous phase to pH >11 using 10 N sodium 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
hydroxide and extract it with methylene chloride again for of Solid Waste, Washington, DC.
concentrator.
Ethoprop EPA Method 507
Soils, sediments, or sludges — Use 30 g of sample. Nonporous CAS #13194-48-4
flowing sandy texture must be mixed with anhydrous sodium TITLE Determination of Nitrogen and Phosphorus-Con-
sulfate until the sample is free flowing. Add 1 mL of surrogate taining Pesticides in Water by GC/NPD
sample in each analytical batch selected for spiking, add 1.0 mL MATRIX This method is applicable to the determination of
of a matrix spiking standard. For base/neutral acid analysis, the certain nitrogen and phosphorus-containing pesticides in fin-
amount added of the surrogates and matrix spiking com- ished drinking water and groundwater.
pounds should result in a final concentration of 100 ng/ L of METHOD SUMMARY Method 507 covers 46 nitrogen- and
each base/neutral analyte and 200 ng/L of each acid analyte phosphorus-containing pesticides. A 1-L sample is fortified
in the extract to be analyzed (assuming a 1- L injection). with a surrogate standard, salted, buffered, extracted with
Immediately add a 100-mL mixture of 1:1 methylene chlo- methylene chloride, and concentrated; then the solvent is
ride:acetone and extract the sample ultrasonically for 3 min exchanged with methyl tert-butyl ether (MTBE) and concen-
and then decant or filter the extracts. Repeat the extraction two trated again, and a 2-L aliquot of a sample extract is injected
or more times. Dry the extract using a column with anhydrous into a GC system equipped with a selective nitrogen-phospho-
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. rus detector and a capillary column for analysis.
QUALITY CONTROL A methylene chloride solution con- INTERFERENCES Method interferences may be caused by
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is contaminants in solvents, reagents, glassware, and other sample
used for tuning the GC/MS system each 12-h shift. A system processing apparatus. Interfering contamination may occur
performance check also must be made during every 12-h shift. when a sample containing low concentrations of analytes is
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- analyzed immediately following a sample containing relatively
rophenol, and benzidine is required to verify injection port high concentrations. One or more injections of MTBE should
inertness and GC column performance. A calibration standard be made following the analysis of a sample with high concen-
at mid-concentration, containing each compound of interest, trations of analytes to check for analyte carryover. Matrix inter-
including all required surrogates, must be performed every 12 h ferences may be caused by contaminants that are coextracted

from the sample. The extent of matrix interferences will vary Note: If methylene chloride is not completely removed from
considerably from source to source, depending upon the water the final extract, it may cause detector problems.
sampled.
QUALITY CONTROL Minimum quality control require-
INSTRUMENTATION A gas chromatograph system (GC) ments are initial demonstration of lab capability, determina-
equipped with a nitrogen-phosphorus detector (NPD) is tion of surrogate compound recoveries in each sample and
needed. blank, monitoring internal standard peak area or height in each
sample and blank, analysis of lab reagent blanks, lab fortified
Column 1: 30 m 0.25 mm I.D. DB-5 bonded fused silica col-
samples, lab fortified blanks, and other QC samples. A lab
umn, 0.25 m film thickness, or equivalent.
reagent blank is analyzed to demonstrate that all glassware and
Column 2: 30 m 0.25 mm I.D. DB-1701 bonded fused silica
reagent interferences are under control.
column, 0.25 m film thickness, or equivalent.
Initial demonstration of capability is fulfilled by analyzing four
fortified reagent water samples with the recovery value for each
in a single lab and estimated detection limits (EDLs) have been
determined for each analyte. Observed detection limits may analyte falling within the acceptable range ( 30% average
vary among waters, depending upon the nature of the inter- recovery). Surrogate recoveries from samples or method blanks
ferences in the sample matrix and the specific instrumentation must be 70–130%. The internal standard response for any sam-
used. Analytes that are not separated chromatographically can- ple chromatogram should not deviate from the daily calibra-
not be individually identified and measured unless an alterna-
30% or lab fortified blanks and sample matrices are used to
tive technique for identification and quantification exist.
assess lab performance and analyte recovery, respectively.
The estimated detection limit (in g/L) was 0.19. The EDL is
If the response for the target analyte peak exceeds the working
defined as either method detection limit or a level of compound
range of the system, dilute the extract and reanalyze.Alternative
in a sample yielding a peak in the final extract with signal-to-
noise ratio of approximately 5, whichever value is higher.
raphy column should be used to confirm peak identification
The concentration used for these measurements (in g/L) was when sample components are not resolved adequately.
1.9.
EPA CONTACT & HOTLINE For technical questions contact
The accuracy (as % recovery) was 103.
The precision (% RSD) was 5. Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
SAMPLING METHOD Grab samples are collected in 1-L 20460. Tel. (202) 260-3040. For further information the EPA
glass sample bottles (prewashed with detergent and hot tap Safe Drinking Water Hotline may be called at: (800) 426-4791.
for 1 h) with screw caps lined with PTFE-fluorocarbon. REFERENCE Methods for the Determination of Organic
SAMPLE PRESERVATION Add mercuric chloride to the July 1991). U.S. EPA Environmental Monitoring Systems Lab-
sample bottle in amounts to produce a concentration of oratory, Cincinnati, OH, 45268, U.S.A. Available from the
10 mg/L. If residual chlorine is present, add 80 mg of sodium National Technical Information Service (NTIS), 5285 Port
thiosulfate/L of sample to the sample bottle prior to collection. Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS
After collection, seal bottle and shake vigorously for 1 min, then Order Number is PB91-231480.
cool the sample to 4C immediately and store it at 4C in the
dark until extraction.
MHT Maximum holding time of the samples, and in some Ethoprop EPA Method 8141
cases the extracts, is 14 days. CAS #13194-48-4
SAMPLE PREPARATION Fortify the sample with 50 L of
the surrogate standard solution, adjust to pH 7 with phosphate
raphy: Capillary Column Technique
buffer, add 100 g NaCl to the sample, and seal and shake to
dissolve the salt; then extract with methylene chloride in a MATRIX This method covers aqueous and solid matrices.
separatory funnel or in a mechanical tumbler bottle. Dry the This includes a wide variety such as drinking water, ground-
extract by pouring it through a solvent-rinsed drying column water, industrial wastewaters, surface waters, soils, solids, and
containing about 10 cm of anhydrous sodium sulfate. Collect sediments.
the extract in a Kuderna-Danish (K-D) concentrator and rinse
METHOD SUMMARY This is a GC method used to deter-
the column with 20–30 mL methylene chloride. Concentrate
mine the concentration of 28 organophosphorus pesticides.
the extract to about 2 mL and rinse the flask and its lower joint
into the concentrator tube with 1 to 2 mL of methyl t-butyl The use of Gel Permeation Cleanup (EPA Method 3640) for
ether (MTBE). Add 5–10 mL of MTBE and concentrate the sample cleanup has been demonstrated to yield recoveries of
extract twice (adding more MTBE) to a final volume of 5.0 mL less than 85% for many method analytes and is therefore not
and store it at 4C until analysis. recommended for use with this method.

This method provides GC conditions for the detection of ppb 1 and Column 2 is not required, Column 3 (DB-5 or equiva-
concentrations of organophosphorus compounds. Prior to the lent) may be used. For megabore capillary columns, automatic
use of this method, appropriate sample preparation techniques injections of 1 L are recommended.
PRECISION & ACCURACY The MDL actually achieved in
methylene chloride as a solvent by using a separatory funnel
a given analysis will vary, as it is dependent on instrument
(EPA Method 3510) or a continuous liquid-liquid extractor
sensitivity and matrix effects. Single operator accuracy and
(EPA Method 3520). Soxhlet extraction (EPA Method 3540) or
precision studies have been conducted with spiked water and
ultrasonic extraction (EPA Method 3550) using methylene
soil samples.
chloride/acetone (1:1) are used for solid samples. Both neat
and diluted organic liquids (EPA Method 3580) may be ana- MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
lyzed by direct injection. Spiked samples are used to verify the Matrix Factor (b)
applicability of the chosen extraction technique to each new
sample type. A GC with a flame photometric (FPD) or nitro- Groundwater 10
gen-phosphorus detector (NPD) is used for this multiresidue (EPA Method 3510 or EPA Method 3520)
procedure. Low-concentration soil by Soxhlet and no cleanup 10 (c)
Low-concentration soil by ultrasonic extraction 6.7 (c)
INTERFERENCES The use of Florisil cleanup materials (EPA with GPC cleanup
Method 3620) for some of the compounds in this method has High-concentration soil and sludges 500 (c)
been demonstrated to yield recoveries less than 85% and is by ultrasonic extraction
therefore not recommended for all compounds. Use of phos- Non-water miscible waste (EPA Method 3580) 1000 (c)
the necessity for cleanup for relatively clean sample matrices. (a) SampleEQLs are highly matrix-dependent. TheEQLslisted here
If particular circumstances demand the use of an alternative are provided for guidance and may not always be achievable.
cleanup procedure, the analyst must determine the elution pro- (b) EQL = [Method detection limit] [Factor]. For non-aqueous
file and demonstrate that the recovery of each analyte is no less samples the factor is on a wet-weight basis.
than 85%. (c) Multiply this factory times the soil MDL.
pounds by flame photometric gas chromatography. Sulfur Accuracy (as % recovery) with separatory funnel extraction
cleanup using EPA Method 3660 may alleviate this interference. ranged from 82 (with low spikes) to 80 (with high spikes).
A nitrogen phosphorus detector (NPD) is also recommended. Accuracy (as % recovery) with continuous liquid-liquid extrac-
tion ranged from 39 (with low spikes) to 83 (with high
A few analytes coelute on certain columns. Therefore, select a spikes).
second column for confirmation where coelution of the ana- Accuracy (as % recovery) with Soxhlet extraction of soils
lytes of interest does not occur. ranged from 65 (with low spikes to 75 (with high spikes).
Accuracy (as % recovery) with ultrasonic extraction of soils
Method interferences may be caused by contaminants in sol-
ranged from 19 (with low spikes) to 35 (with high spikes).
vents, reagents, glassware, and other sample processing hard-
ware that lead to discrete artifacts or elevated baselines in gas SAMPLE COLLECTION, PRESERVATION & HANDLING
chromatograms. All these materials must be routinely demon- Containers used to collect samples for the determination of
strated to be free from interferences under the conditions of semivolatile organic compounds should be soap and water
the analysis by analyzing reagent blanks. washed followed by methanol (or isopropanol) rinsing. The
sample containers should be of glass or Teflon® and have screw-
INSTRUMENTATION A GC with a NPD or a FPD will be top covers with Teflon® liners.
needed. A data system or integrator is recommended for mea-
suring peak areas and/or peak heights. A Kuderna-Danish No preservation is used with concentrated waste samples. With
(K-D) apparatus will be needed for extract concentration. liquid samples containing no residual chlorine and with soil,
sediment, and sludge samples, immediately cooling to 4C is
the only preservation used. When residual chlorine is present
1.0 m film thickness, DB-210. then 3 mL of 10% aqueous sodium sulfate is added for each
Column 2: 15 m  0.53 mm megabore capillary column, gallon of sample collected, followed by cooling to 4C.
Column 3: 15 m  0.53 mm megabore capillary column, Liquid samples must be extracted within 7 days and their
1.0 m film thickness, DB-5. extracts analyzed within 40 days. Concentrated waste, soil, sed-
iment, and sludge samples must be extracted within 14 days
Three megabore capillary columns are included for analysis of and their extracts analyzed within 40 days.
organophosphates by this method. Column 1 (DB-210 or
equivalent) and Column 2 (SPB-608 or equivalent) are recom- SAMPLE PREPARATION In general, water samples are
mended if a large number of organophosphorus analytes are extracted at a neutral pH with methylene chloride, using either
to be determined. If the superior resolution offered by Column EPA Method 3510 or EPA Method 3520. Solid samples are

extracted using either EPA Method 3540 or EPA Method 3550 MATRIX Groundwater, soils, sludges, water miscible liquid
with methylene chloride/acetone (1:1) as the extraction solvent. wastes, and non-water miscible wastes.
Prior to GC analysis, the extraction solvent may be exchanged APPLICATION This method is used for the analysis of 21
to hexane. Single lab data indicates that samples should not be organophosphorus pesticides. Samples are extracted, concen-
transferred with 100% hexane during sample workup as the trated, and analyzed using direct injection of both neat and
more water soluble organophosphorus compounds may be lost. diluted organic liquid into a gas chromatograph (GC).
If cleanup is performed on the samples, the analyst should INTERFERENCES Solvents, reagents, and glassware may
analyze the samples by GC. This will confirm elution patterns introduce artifacts. Other interferences may come from coex-
and the absence of interferences from the reagents. If peak tracted compounds from samples. The use of Florisil cleanup
detection and identification is prevented by the presence of materials may produce low recoveries. Elemental sulfur may
interferences, further cleanup is required. interfere with some compounds when using a flame photomet-
QUALITY CONTROL The analyst should monitor the per- ric detector. Sulfur cleanup (Method 3660) may alleviate sulfur
formance of the extraction, cleanup (when used), and analyt- interference.
ical system and the effectiveness of the method in dealing with INSTRUMENTATION GC capable of on-column injections
each sample matrix by spiking each sample, standard, and
and a flame photometric detector (FPD) or a thermionic detec-
tor. Column 1: 1.8 m by 2 mm with 5% SP-2401 on Supelco-
port. Column 2: 1.8 m by 2 mm with 3% SP-2401 on
terated analogs of analytes should not be used as surrogates for
gas chromatographic analysis due to coelution problems. Supelcoport. Column 3: 50 cm by in eflon® with 15% SE-
54 on Gas Chrom Q. The preferred column is Column Number 2.
A minimum of five concentrations for each analyte of interest
should be prepared through dilution of the stock standards RANGE 1.0–51.5 g/L.
with isooctane. One of the concentrations should be at a con- MDL 0.25 g/L (in reagent water).
centration near, but above, the MDL.
PQL FACTORS FOR MULTIPLYING  FID MDL VALUE
Include a mid-level check standard after each group of 10 sam- Matrix Multiplication Factor
ples in the analysis sequence. GC/MS techniques should be
judiciously employed to support qualitative identifications Groundwater 10
made with this method. Follow the GC/MS operating require- Low-level soil by sonication with GPC cleanup 670
ments specified in EPA Method 8270. High-level soil and sludge by sonication 10,000
Non-water miscible waste 100,000
employed to aid in the qualitative identification process. To PRECISION 4.1% (single operator standard deviation)
confirm an identification of a compound, the background- ACCURACY 100.5% (single operator average recovery)
from the sample extract and must be compared with a mass SAMPLING METHOD Use 8-oz. widemouth glass bottles
spectrum from a stock or calibration standard analyzed under with Teflon®-lined caps for concentrated waste samples, soils,
the same chromatographic conditions. The molecular ion and sediments, and sludges. Use 1 or 2½ gallon amber glass bottles
all other ions present above 20% relative abundance in the mass with Teflon®-lined caps for liquid (water) samples.
spectrum of the standard must be present in the mass spectrum
of the sample with agreement to 20%. The retention time of STABILITY Cool soil, sediment, sludge, and liquid samples
the compound in the sample must be within six seconds of the to 4C. If residual chlorine is present in liquid samples add
retention time for the same compound in the standard solution. 3 mL of 10% sodium thiosulfate per gallon of sample and cool
to 4C.
additional steps may be taken before reanalysis. These steps MHT 14 days for concentrated waste, soil, sediment, or
may include the use of alternate packed or capillary GC col- sludge; 7 days for liquid samples; all extracts must be analyzed
umns or additional sample cleanup. within 40 days.
REFERENCE Test Methods for Evaluating Solid Waste, Phys- QUALITY CONTROL A quality control check sample con-
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office centrate containing this compound in acetone at a concentra-
of Solid Waste, Washington, DC, EPA Method 8141 July 1992. tion 1,000 times more concentrated than the selected spike
concentration is required. The QC check sample concentrate
may be prepared from pure standard materials or purchased
as certified solutions. Use appropriate trip, matrix, control site,
Ethoprop EPA Method 8140
method, reagent, and solvent blanks. Internal, surrogate, and
CAS #13194-48-4
five concentration level calibration standards are used.
TITLE Organophosphorus Pesticides REFERENCE Method 8140, SW-846, 3rd ed., Sept. 1986.

Ethyl carbamate EPA Method 8270
CAS #51-79-6 This calculation is based on a 30-g sample and gel perme-
TITLE Semivolatile Organic Compounds by GC/MS (b) Sample EQLs are highly matrix-dependent. The EQLs are
MATRIX This method is used to determine the concentra- C = True value for concentration, in g/L.
tion of semivolatile organic compounds in extracts prepared X = Average recovery found for measurements of samples con-
from all types of solid waste matrices, soils, and groundwater. taining a concentration of C, in g/L.
method should be applicable to water samples from rivers, ESTIMATED QUANTITATION LIMIT
lakes, etc. Other Matrices Factor (a)
METHOD SUMMARY This method covers 259 semivolatile High-concentration soil and sludges by sonicator 7.5
organic compounds. In very limited applications direct injec- Non-water miscible waste 75
tion of the sample into the GC/MS system may be appropriate, (a) EQL forother matrices =[EQL forlow soil/sediment] [Factor].
but this results in very high detection limits (approximately This estimated EQL is similar to an EPA “Practical Quantitation
10,000 g/L). Typically, a 1-L liquid sample, containing surro- Limit.”
extractor first under acid conditions and then under basic con- SAMPLING METHOD
ditions. Typically 30 g of a solid sample, containing surrogate, Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
and matrix spiking standards, is extracted ultrasonically. After a screw-top Teflon®-lined cover that has been prewashed with
concentrating the extract to 1 mL it is spiked with 10 L of an detergent and rinsed with distilled water and methanol (or
internal standard solution just prior to analysis by GC/MS. The isopropanol).
volume injected should contain about 100 ng of base/neutral Soils, sediments, or sludges — Use an 8-oz. widemouth glass
and 200 ng of acid surrogates (for a 1-L injection). Analysis with a screw-top Teflon®-lined cover that has been prewashed
is performed by GC/MS using a capillary GC column. with detergent and rinsed with distilled water and methanol
INTERFERENCES Raw GC/MS data from all blanks, sam- (or isopropanol).
ples, and spikes must be evaluated for interferences. Contam- SAMPLE PRESERVATION
ination by carryover can occur whenever high-concentration Liquid samples — If residual chlorine is present, add 3 mL of
and low-concentration samples are sequentially analyzed. To 10% sodium thiosulfate per gallon, cool to 4C and store in a
reduce carryover, the sample syringe must be rinsed out solvent-free refrigerator until analysis; if chlorine is not present,
between samples with solvent. Whenever an unusually concen- then eliminate the sodium thiosulfate addition.
analysis of blank solvent to check for cross-contamination. Soils, sediments, or sludges — Cool samples to 4C and store
required. The GC column used is a 30 m 0.25 mm I.D. (or MHT Liquid samples must be extracted within 7 days and
0.32 mm I.D.) 1um film thickness silicone-coated fused silica the extracts analyzed within 40 days. Soils, sediments, or slud-
capillary column. A continuous liquid-liquid extractor ges may be stored for a maximum of 14 days and the extracts
equipped with Teflon® or glass connection joints and stopcocks analyzed within 40 days.
requiring no lubrication, a K-D concentrating apparatus, water
SAMPLE PREPARATION
bath, and an ultrasonic disrupter with a minimum power of Liquid samples — Transfer 1 L quantitatively to a continuous
300 W and with pulsing capability are also required. extractor. If high concentrations are anticipated, a smaller vol-
PRECISION & ACCURACY The estimated quantitation ume may be used and then diluted with organic-free reagent
limit (EQL) of Method 8270B for determining an individual water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
compound is approximately 1 mg/kg (wet weight) for soil or sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
sediment samples, 1–200 mg/kg for wastes (dependent on solution into each sample. For the sample in each analytical
matrix and method of preparation), and 10 g/L for ground- batch selected for spiking, add 1.0 mL of a matrix spiking stan-
water samples. EQLs will be proportionately higher for sample dard. For base/neutral acid analysis, the amount of the surro-
extracts that require dilution to avoid saturation of the detector. gates and matrix spiking compounds added to the sample
should result in a final concentration of 100 ng/L of each
The EQL(b) for groundwater in g/L is 50.
The EQL (a, b) for low concentrations in soil and sediment
in g/kg is not determined.
Overall precision in g/L is not listed.
(a) EQLs listed for soil/sediment are based on wet weight. Nor- drous sodium sulfate and concentrate it to 1 mL using a K-D
mally data is reported in a dry-weight basis; therefore, EQLs concentrator.

Soils, sediments, or sludges — Use 30 g of sample. Nonporous or
Ethyl cyanide EPA Method 1624
wet samples (gummy or clay type) that do not have a free-flowing CAS #107-12-0
sandy texture must be mixed with anhydrous sodium sulfate
until the sample is free flowing. Add 1 mL of surrogate stan- TITLE Volatile Organic Compounds by Isotope Dilution
dards to all samples, spikes, standards, and blanks. For the GC/MS
of a matrix spiking standard. For base/neutral acid analysis, the MATRIX Compounds may be determined in waters, soils,
amount added of the surrogates and matrix spiking com- and municipal sludges by this method.
pounds should result in a final concentration of 100 ng/ L of METHOD SUMMARY This method is used to determine 58
each base/neutral analyte and 200 ng/L of each acid analyte volatile toxic organic pollutants associated with the CWA (as
in the extract to be analyzed (assuming a 1- L injection). amended 1987); the RCRA (as amended 1986); the CERCLA
Immediately add a 100-mL mixture of 1:1 methylene chlo- (as amended 1986); and other compounds amenable to purge-
ride:acetone and extract the sample ultrasonically for 3 min and-trap gas chromatography-mass spectrometry (GC/MS).
and then decant or filter the extracts. Repeat the extraction two If the solids content is less than 1%, stable isotopically-labeled
or more times. Dry the extract using a column with anhydrous analogs of the compounds of interest are added to a 5-mL
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. sample and the sample is purged with an inert gas at 20–25 C
QUALITY CONTROL A methylene chloride solution con- in a chamber designed for soil or water samples. If the solids
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is content is greater than 1%, 5 mL of reagent water and the
used for tuning the GC/MS system each 12-h shift. A system labeled compounds are added to a 5-g aliquot of sample and
performance check also must be made during every 12-h shift. the mixture is purged at 40C. Compounds that will not purge
at 20–25C or at 40C are purged at 78–85C. In the purging
process, the volatile compounds are transferred from the aque-
rophenol, and benzidine is required to verify injection port
ous phase into the gaseous phase where they are passed into a
sorbent column, and trapped. After purging is completed, the
at mid-concentration, containing each compound of interest, trap is backflushed and heated rapidly to desorb the com-
including all required surrogates, must be performed every 12 h pounds into a GC. The compounds are separated by the GC
during analysis. After the system performance check is met, and detected by a MS. The labeled compounds serve to correct
calibration check compounds (CCCs) are used to check the the variability of the analytical technique.
INTERFERENCES Impurities in the purge gas, organic com-
The internal standard responses and retention times in the pounds outgassing from the plumbing upstream of the trap,
calibration check standard must be evaluated immediately after and solvent vapors in the lab account for most problems. Sam-
or during data acquisition. If the retention time for any internal ples can be contaminated by diffusion of volatile organic com-
standard changes by more than 30 seconds from the last check pounds (particularly methylene chloride) through the bottle
calibration (12 h), the chromatographic system must be seal during shipment and storage. Contamination by carryover
inspected for malfunctions and corrections must be made, as can occur when high-level and low-level samples are analyzed
required. If the electron ionization current plot (EICP) area for sequentially. When an unusually concentrated sample is
any of the internal standards changes by a factor of two from encountered, follow it by analysis of a reagent water blank to
the last daily calibration standard check, the mass spectrometer check for carryover.
must be inspected for malfunctions and corrections must be INSTRUMENTATION Major equipment includes a GC with
made, as appropriate. linear temperature programming and a glass jet separator as
Demonstrate, through the analysis of a reagent water blank, the MS interface, a MS with 70 eV electron impact ionization,
that interferences from the analytical system, glassware, and and a data system to collect and record response factors.
reagents are under control. The blank samples should be car- Column: 2.8 m 2 mm I.D. glass, packed with 1% SP-1000 on
ried through all stages of the sample preparation and measure- Carbopak B, 60/80 mesh, or equivalent.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
rather than instrumental limitations. The method detection
limits were determined in digested sludge (low solids) and in
spiked samples must be carried through all stages of the sample filter cake or compost (high solids).
concentrate containing each analyte at a concentration of The MDL (in g/kg) for low solids is not listed and for high
100 mg/L in methanol is required. solids is not listed.
Labeled and native compound precision (in g/L) as standard
REFERENCE Test Methods for Evaluating Solid Waste (SW- deviation was not listed.
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office Labeled and native compound accuracy (in g/L) as average
of Solid Waste, Washington, DC. recovery was not listed.

Acceptance criteria are at 20 g/L for this compound. METHOD SUMMARY This method is used to determine 58
volatile toxic organic pollutants associated with the CWA (as
amended 1987); the RCRA (as amended 1986); the CERCLA
Grab samples are collected in glass containers having a total
(as amended 1986); and other compounds amenable to purge-
volume greater than 20 mL. Fill and seal each bottle so that no
and-trap gas chromatography-mass spectrometry (GC/MS).
air bubbles are entrapped. Samples are maintained at 0 to 4 C
from the time of collection until analysis. If an aqueous sample If the solids content is less than 1%, stable isotopically-labeled
contains residual chlorine, add sodium thiosulfate preservative analogs of the compounds of interest are added to a 5-mL
(10 mg/40 mL) to the empty sample bottles just prior to ship- sample and the sample is purged with an inert gas at 20–25 C
ment to the sample site. All samples must be analyzed within in a chamber designed for soil or water samples. If the solids
14 days of collection. content is greater than 1%, 5 mL of reagent water and the
SAMPLE PREPARATION Samples containing less than 1% labeled compounds are added to a 5-g aliquot of sample and
solids are analyzed directly as aqueous samples. Samples con- the mixture is purged at 40C. Compounds that will not purge
taining 1% solids or greater are analyzed as solid samples uti- at 20–25C or at 40C are purged at 78–85C. In the purging
lizing one of two methods, depending on the levels of process, the volatile compounds are transferred from the aque-
pollutants, in the sample. Samples containing 1% solids or ous phase into the gaseous phase where they are passed into a
greater, and low to moderate levels of pollutants are analyzed sorbent column, and trapped. After purging is completed, the
by purging a known weight of sample added to 5 mL of reagent trap is backflushed and heated rapidly to desorb the com-
water. Samples containing 1% solids or greater, and high levels pounds into a GC. The compounds are separated by the GC
of pollutants, are extracted with methanol, and an aliquot of and detected by a MS. The labeled compounds serve to correct
the methanol extract is added to reagent water and purged. the variability of the analytical technique.
QUALITY CONTROL A field blank prepared from reagent INTERFERENCES Impurities in the purge gas, organic com-
water and carried through the sampling and handling protocol pounds outgassing from the plumbing upstream of the trap,
may serve as a check on contamination from shipment and and solvent vapors in the lab account for most problems. Sam-
storage. ples can be contaminated by diffusion of volatile organic com-
pounds (particularly methylene chloride) through the bottle
The analyst is permitted to modify this method to improve
seal during shipment and storage. Contamination by carryover
separations or lower the costs of measurements, provided all
can occur when high-level and low-level samples are analyzed
performance specifications are met. Analyses of blanks are
sequentially. When an unusually concentrated sample is
required. When results of spikes indicate atypical method per-
encountered, follow it by analysis of a reagent water blank to
formance for samples, the samples are diluted to bring method
check for carryover.
performance within acceptable limits. Analyze two sets of four
5-mL aliquots (8 aliquots total) of the aqueous performance INSTRUMENTATION Major equipment includes a GC with
standard. Spike all samples with labeled compounds to assess linear temperature programming and a glass jet separator as
method performance on the sample matrix. Compute the per- the MS interface, a MS with 70 eV electron impact ionization,
cent recovery of the labeled compounds using the internal stan- and a data system to collect and record response factors.
dard method. Compare the percent recovery for each
compound with the corresponding labeled compound recov- Column: 2.8 m 2 mm I.D. glass, packed with 1% SP-1000 on
ery. Reagent water blanks are analyzed to demonstrate freedom Carbopak B, 60/80 mesh, or equivalent.
from carryover contamination. Field replicates may be col- PRECISION & ACCURACY The detection limits of the
lected to determine the precision of the sampling technique, method are usually dependent on the level of interferences
and spiked samples may be required to determine the accuracy rather than instrumental limitations. The method detection
of the analysis when the internal method is used. limits were determined in digested sludge (low solids) and in
REFERENCE Volatile Organic Compounds by Isotope Dilu- filter cake or compost (high solids).
tion GC/MS. Office of Water Regulation and Standards, U.S. The MDL (in g/kg) for low solids is not listed and for high
EPA Industrial Technology Division, Washington, DC, EPA solids is not listed.
Method 1624, Rev. C, June 1989 (contact W.A. Telliard, U.S. Labeled and native compound precision (in g/L) as standard
EPA, Office of Water Regulations and Standards, 401 M St., deviation was not listed.
SW, Washington, DC, 20460. Phone: 202-382-7131). Labeled and native compound accuracy (in g/L) as average
recovery was not listed.
Acceptance criteria are at 20 g/L for this compound.
Ethyl methacrylate EPA Method 1624 SAMPLE COLLECTION, PRESERVATION & HANDLING
CAS #97-63-2 Grab samples are collected in glass containers having a total
TITLE Volatile Organic Compounds by Isotope Dilution
air bubbles are entrapped. Samples are maintained at 0 to 4 C
GC/MS
from the time of collection until analysis. If an aqueous sample
MATRIX Compounds may be determined in waters, soils, contains residual chlorine, add sodium thiosulfate preservative
and municipal sludges by this method. (10 mg/40 mL) to theempty sample bottles just prior to shipment

to the sample site. All samples must be analyzed within 14 days solution at ambient temperature. Purged sample components
of collection. are trapped in a tube of sorbent materials. When purging is
SAMPLE PREPARATION Samples containing less than 1%
solids are analyzed directly as aqueous samples. Samples con-
taining 1% solids or greater are analyzed as solid samples uti- INTERFERENCES Impurities in the purge gas and from
lizing one of two methods, depending on the levels of organic compounds outgassing from the plumbing ahead of
pollutants, in the sample. Samples containing 1% solids or the trap account for many contamination problems. Interfer-
greater, and low to moderate levels of pollutants are analyzed ences purged or coextracted from the samples will vary con-
by purging a known weight of sample added to 5 mL of reagent siderably from source to source. Cross-contamination can
water. Samples containing 1% solids or greater, and high levels occur whenever high-level and low-level samples are analyzed
of pollutants, are extracted with methanol, and an aliquot of sequentially. Whenever an unusually concentrated sample is
the methanol extract is added to reagent water and purged. analyzed, it should be followed by the analysis of organic-free
QUALITY CONTROL A field blank prepared from reagent can be contaminated by diffusion of volatile organics (partic-
water and carried through the sampling and handling protocol ularly methylene chloride and fluorocarbons) through the sep-
may serve as a check on contamination from shipment and tum seal into the sample during shipment and storage. A trip
storage. blank can serve as a check on such contamination. The lab
The analyst is permitted to modify this method to improve where volatile analysis is performed and also the refrigerated
separations or lower the costs of measurements, provided all storage area should be completely free of solvents.
performance specifications are met. Analyses of blanks are INSTRUMENTATION A gas chromatograph/mass spec-
required. When results of spikes indicate atypical method per- trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
formance for samples, the samples are diluted to bring method I.D. glass column packed with 1% SP-1000 on Carbopack-B
performance within acceptable limits. Analyze two sets of four (60/80 mesh) is required.Also needed is a 5-mL purging device,
5-mL aliquots (8 aliquots total) of the aqueous performance a sorbent trap, and a thermal desorption apparatus.
standard. Spike all samples with labeled compounds to assess
method performance on the sample matrix. Compute the per- PRECISION & ACCURACY This method is reported to have
cent recovery of the labeled compounds using the internal stan- been tested by 15 laboratories using organic-free reagent water,
dard method. Compare the percent recovery for each drinking water, surface water, and industrial wastewaters (not
compound with the corresponding labeled compound recov- specified) fortified at six concentrations over the range 5–
ery. Reagent water blanks are analyzed to demonstrate freedom 600 g/L.
from carryover contamination. Field replicates may be col- Sample estimated quantitation limits (EQLs) are highly
lected to determine the precision of the sampling technique, matrix-dependent. The EQLs listed may not always be achiev-
and spiked samples may be required to determine the accuracy able. EQLs listed for soils or sediments are based on wet weight.
of the analysis when the internal method is used. Normally, data is reported on a dry-weight basis; therefore,
REFERENCE Volatile Organic Compounds by Isotope Dilu- EQLs will be higher, based on the percent dry weight of each
tion GC/MS. Office of Water Regulation and Standards, U.S. sample. Note that EQLs are even more variable than MDLs and
EPA Industrial Technology Division, Washington, DC, EPA that they are highly variable depending on the matrix being
Method 1624, Rev. C, June 1989 (contact W.A. Telliard, U.S. analyzed.
EPA, Office of Water Regulations and Standards, 401 M St., EQL in groundwater in g/L was 5.
SW, Washington, DC, 20460. Phone: 202-382-7131). EQL in low soil or sediment in g/kg was 5.
Precision (b) in g/L was not listed.
Ethyl methacrylate EPA Method 8240 (a) Average recovery found for measurements of samples con-
CAS #97-63-2 taining a concentration of C, in g/L.
TITLE Volatile Organics By GC/MS: Packed Column Technique average recovery X for samples containing a concentration
of C in g/L.
MATRIX Nearly all types of sample matarices, regardless of
water content, can be analyzed using this method. This includes X = Average recovery found for measurement of samples con-
groundwater, aqueous sludges, caustic liquors, acid liquors, taining a concentration of C in g/L.
waste solvents, oily wastes, mousses, tars, fibrous wastes, poly- MULTIPLICATION FACTORS FOR OTHER MATRICES
metric emulsions, filter cakes, spent carbons, spent catalysts, Other Matrices Factor (a)
soils, and sediments.
Waste miscible liquid waste 50
METHOD SUMMARY Method 8240B covers 80 volatile High-concentration soil and sludge 125
organic compounds that are introduced into a gas chromato- Non-water miscible waste 500
limited applications). For the purge-and-trap method an inert (a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous
gas (zero grade nitrogen or helium) is bubbled through a 5-mL samples, the factor is on a wet-weight basis.

SAMPLING METHOD High-concentration method — This method is based on
Liquid samples — Use a 40-mL glass screw-cap VOA vial with extracting the sediment or soil with methanol. A waste sample
a Teflon®-faced silicone septum that has been prewashed, is either extracted or diluted, depending on its solubility in
rinsed with distilled deionized water, and oven dried. However, methanol. Wastes that are insoluble in methanol are diluted
if residual chlorine is present, collect sample in a 40-oz. soil with reagent tetraglyme or possibly polyethylene glycol (PEG).
VOA container which has been pre-preserved with 4 drops of An aliquot of the extract is added to organic-free reagent water
10% sodium thiosulfate, mix gently, and then transfer the sam- containing surrogate and internal standards. This is purged at
ple to a 40-mL VOA vial. Collect bubble-free samples in dupli- ambient temperature. All samples with an expected concentra-
cate and seal them in separate plastic bags. tion of >1.0 mg/kg should be analyzed by this method.
Soils or sediments, and sludges — Use an 8-oz. widemouth Mix the contents of the sample container with a narrow metal
glass bottle with a Teflon®-faced silicone septum that has been spatula. For sediments or soils and solid wastes that are insol-
uble in methanol, weigh 4 g (wet weight) of sample into a tared
prewashed with detergent, rinsed with distilled deionized
20-mL vial. For waste that is soluble in methanol, tetraglyme,
water, and oven dried. Tap slightly to eliminate free air space.
or PEG, weigh 1 g (wet weight) into a tared scintillation vial
Collect samples in duplicate and seal them in separate plastic bags.
or culture tube or a 10-mL volumetric flask. Quickly add
SAMPLE PRESERVATION 9.0 mL of appropriate solvent then add 1.0 mL of a surrogate
Liquid samples — Add 4 drops of concentrated HCL and spiking solution to the vial, cap it, and shake it for 2 min.
immediately cool samples to 4C and store in a solvent-free METHANOL EXTRACT REQUIRED FOR ANALYSIS
refrigerator. OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
Soils or sediments, and sludges — Cool samples to 4C and Approximate Volume of
store in a solvent-free refrigerator. Concentration Range Methanol Extract (a)
MHT Maximum holding time is 14 days from the date of 500–10,000 g/kg 100 L
5,000–100,000 g/kg 10 L
SAMPLE PREPARATION 25,000–500,000 g/kg 100 L of 1/50 dilution (b)
Liquid samples — Remove the plunger from a 5-mL syringe
and carefully pour the sample into the syringe barrel to just Calculate appropriate dilution factor for concentrations
short of overflowing. Replace the syringe plunger and compress exceeding this table.
the sample. Open the syringe valve and vent any residual air (a) The volume of methanol added to 5 mL of water being purged
while adjusting the sample volume to 5.0 mL. If there is only should be kept constant. Therefore, add to the 5-mLsyringe whatever
one volatile organic analysis (VOA) vial, a second syringe volume of methanol is necessary to maintain a volume of 100 L
should be filled at this time to protect against possible loss of added to the syringe.
sample integrity. Add 10 L of surrogate spiking solution and (b) Dilute an aliquot of the methanol extract and then take 100 L
10 L of internal standard spiking solution through the valve for analysis.
Sediments, soils, and waste samples — All samples of this type ples should be carried through all stages of the sample prepa-
should be screened by GC analysis using a headspace method ration and measurement steps. For each analytical batch (up
(EPA Method 3810) or the hexadecane extraction and screen- to 20 samples), a reagent blank, matrix spike, and matrix spike
ing method (EPA Method 3820). Use the screening data to duplicate must be analyzed (the frequency of the spikes may
determine whether to use the low-concentration method be different for different monitoring programs). The blank and
spiked samples must be carried through all stages of the sample
(0.005–1 mg/kg) or the high-concentration method (>1 mg/kg).
with organic-free reagent water containing the surrogate and
1 mg/kg. Mix the contents of the sample container with a nar- Ethyl methanesulfonate EPA Method 1625
contains the weighed amount of sample, and connect the TITLE Semivolatile Organic Compounds by Isotope Dilu-
device to the purge-and-trap system. tion GC/MS

MATRIX The compounds may be determined in waters, recognizable mass spectra (background corrected) and accept-
soils, and municipal sludges by this method. able calibration points.
METHOD SUMMARY This method is used to determine The MDL (in g/kg) in low solids was not listed and in high
176 semivolatile toxic organic pollutants associated with the solids was not listed; these were determined in digested sludge
CWA (as amended 1987); the RCRA (as amended 1986); the (low solids) and in filter cake or compost (high solids).
CERCLA (as amended 1986); and other compounds amenable
to extraction and analysis by capillary column gas chromatog- The labeled and native compound initial precision as standard
raphy-mass spectrometry (GC/MS). deviation (in g/L) was not listed.
The labeled and native compound initial accuracy as average
Stable isotopically-labeled analogs of the compounds of interest recovery (in g/L) was not listed.
are added to the sample. If the solids content is less than 1%,
a 1-L sample is extracted at pH 12–13, then at pH <2 with SAMPLE COLLECTION, PRESERVATION & HANDLING
methylene chloride using continuous extraction techniques. Collect samples in glass containers. Aqueous samples which
If the solids content is 30% or less, the sample is diluted to 1% sampling equipment. Solid samples are collected as grab sam-
solids with reagent water, homogenized ultrasonically, and ples using widemouth jars. Maintain samples at 0 to 4C from
extracted at pH 12–13, then at pH <2 with methylene chloride the time of collection until extraction. If residual chlorine is
present in aqueous samples, add 80 mg sodium thiosulfate/L
techniques.
Each extract is dried over sodium sulfate, concentrated to a
SAMPLE PREPARATION Samples containing 1% solids or
volume of 5 mL, cleaned up using GPC, if necessary, and con-
less are extracted directly using continuous liquid-liquid
centrated. Extracts are concentrated to 1 mL if GPC is not
performed, and to 0.5 mL if GPC is performed. extraction techniques. Samples containing 1 to 30% solids are
An internal standard is added to the extract, and a 1-mL aliquot continuous liquid-liquid extraction techniques. Samples con-
of the extract is injected into the GC. The compounds are taining greater than 30% solids are extracted using ultrasonic
separated by GC and detected by a MS. The labeled compounds techniques.
serve to correct the variability of the analytical technique.
Base/neutral extraction — Adjust the pH of the waters in the
INTERFERENCES Solvents, reagents, glassware, and other extractors to 12–13 with 6 N NaOH. Extract with methylene
sample processing hardware may yield artifacts and/or elevated chloride for 24–48 h.
baselines causing misinterpretation of chromatograms and Acid extraction — Adjust the pH of the waters in the extractors
spectra. Materials used in the analysis must be demonstrated to 2 or less using 6 N sulfuric acid. Extract with methylene
chloride for 24–48 h.
by running method blanks initially and with each sample lot
Ultrasonic extraction of high solids samples — Add anhy-
(sample started through the extraction process on a given 8-h
drous sodium sulfate to the sample and QC aliquot(s).
shift, to a maximum of 20). Specific selection of reagents and
purification of solvents by distillation in all glass systems may Add acetone:methylene chloride (1:1) to the sample and
be required. Glassware and, where possible, reagents are mix thoroughly
cleaned by solvent rinse and baking at 450C for 1-h minimum. Concentrate extracts using a K-D apparatus.
Interferences coextracted from samples will vary considerably
from source to source, depending on the diversity of the site QUALITY CONTROL The analyst is permitted to modify
being sampled. this method to improve separations or lower the costs of mea-
INSTRUMENTATION Major instrumentation includes a GC Analyses of blanks are required to demonstrate freedom from
with a splitless or on-column injection port for capillary col- contamination. When results of spikes indicate atypical
umn, a MS with 70 eV electron impact ionization, and a data method performance for samples, the samples are diluted to
system to collect and record MS data, and process it. A K-D bring method performance within acceptable limits.
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1% analyze two sets of four 1-L aliquots (8 aliquots total) of the
vinyl silicone bonded phased fused silica capillary column.
PRECISION & ACCURACY The detection limits of the sets of four 30-g aliquots of the high solids reference matrix
method are usually dependent on the level of interferences are used.
imum quantities that can be detected with no interferences
present. performance. Compute percent recovery of the labeled com-
pounds using the internal standard method. Compare the
The minimum level (in g/mL) was not listed. This is defined labeled compound recovery for each compound with the cor-
as a minimum level at which the analytical system shall give responding labeled compound recovery.

Reagent water and high solids reference matrix blanks are ana- requiring no lubrication, a K-D concentrating apparatus, water
lyzed to demonstrate freedom from contamination. Extract bath, and an ultrasonic disrupter with a minimum power of
and concentrate a 1-L reagent water blank or a high solids 300 W and with pulsing capability are also required.
reference matrix blank with each sample’s lot (samples started
through the extraction process on the same 8-h shift, to a PRECISION & ACCURACY The estimated quantitation
maximum of 20 samples). limit (EQL) of Method 8270B for determining an individual
compound is approximately 1 mg/kg (wet weight) for soil or
Field replicates may be collected to determine the precision of sediment samples, 1–200 mg/kg for wastes (dependent on
the sampling technique, and spiked samples may be required matrix and method of preparation), and 10 g/L for ground-
to determine the accuracy of the analysis when the internal water samples. EQLs will be proportionately higher for sample
standard method is used. extracts that require dilution to avoid saturation of the detector.
REFERENCE Semivolatile Organic Compounds by Isotope The EQL(b) for groundwater in g/L is 20.
Dilution GC/MS. Office of Water Regulation and Standards, The EQL (a, b) for low concentrations in soil and sediment
U.S. EPA Industrial Technology Division, Washington, DC, in g/kg is not determined.
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, Accuracy as g/L is not listed.
U.S. EPA, Office of Water Regulations and Standards, 401 M Overall precision in g/L is not listed.
Ethyl methanesulfonate EPA Method 8270 This calculation is based on a 30-g sample and gel perme-
CAS #62-50-0 ation chromatography cleanup.
High-concentration soil and sludges by sonicator 7.5
organic compounds. In very limited applications direct injec-
required. The GC column used is a 30 m 0.25 mm I.D. (or MHT Liquid samples must be extracted within 7 days and
0.32 mm I.D.) 1um film thickness silicone-coated fused silica the extracts analyzed within 40 days. Soils, sediments, or slud-

100 mg/L in methanol is required.
concentrator.
Ethyl parathion EPA Method 8141
flowing sandy texture must be mixed with anhydrous sodium TITLE Organophosphorus Compounds by Gas Chromatog-
sulfate until the sample is free flowing. Add 1 mL of surrogate raphy: Capillary Column Technique
standards to all samples, spikes, standards, and blanks. For the MATRIX This method covers aqueous and solid matrices.
sample in each analytical batch selected for spiking, add 1.0 mL This includes a wide variety such as drinking water, ground-
of a matrix spiking standard. For base/neutral acid analysis, the water, industrial wastewaters, surface waters, soils, solids, and
amount added of the surrogates and matrix spiking com- sediments.
each base/neutral analyte and 200 ng/L of each acid analyte METHOD SUMMARY This is a GC method used to deter-
mine the concentration of 28 organophosphorus pesticides.
Immediately add a 100-mL mixture of 1:1 methylene chlo- The use of Gel Permeation Cleanup (EPA Method 3640) for
ride:acetone and extract the sample ultrasonically for 3 min sample cleanup has been demonstrated to yield recoveries of
and then decant or filter the extracts. Repeat the extraction two less than 85% for many method analytes and is therefore not
or more times. Dry the extract using a column with anhydrous recommended for use with this method.
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. This method provides GC conditions for the detection of ppb
QUALITY CONTROL A methylene chloride solution con- concentrations of organophosphorus compounds. Prior to the
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is use of this method, appropriate sample preparation techniques
used for tuning the GC/MS system each 12-h shift. A system must be used. Water samples are extracted at a neutral pH with
performance check also must be made during every 12-h shift. methylene chloride as a solvent by using a separatory funnel
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- (EPA Method 3510) or a continuous liquid-liquid extractor
rophenol, and benzidine is required to verify injection port (EPA Method 3520). Soxhlet extraction (EPA Method 3540) or
inertness and GC column performance. A calibration standard ultrasonic extraction (EPA Method 3550) using methylene
chloride/acetone (1:1) are used for solid samples. Both neat
at mid-concentration, containing each compound of interest,
lyzed by direct injection. Spiked samples are used to verify the
applicability of the chosen extraction technique to each new
sample type. A GC with a flame photometric (FPD) or nitro-
gen-phosphorus detector (NPD) is used for this multiresidue
The internal standard responses and retention times in the procedure.
calibration check standard must be evaluated immediately after INTERFERENCES The use of Florisil cleanup materials (EPA
or during data acquisition. If the retention time for any internal Method 3620) for some of the compounds in this method has
standard changes by more than 30 seconds from the last check been demonstrated to yield recoveries less than 85% and is
calibration (12 h), the chromatographic system must be therefore not recommended for all compounds. Use of phos-
inspected for malfunctions and corrections must be made, as phorus or halogen specific detectors, however, often obviates
required. If the electron ionization current plot (EICP) area for the necessity for cleanup for relatively clean sample matrices.
any of the internal standards changes by a factor of two from If particular circumstances demand the use of an alternative
the last daily calibration standard check, the mass spectrometer cleanup procedure, the analyst must determine the elution profile
must be inspected for malfunctions and corrections must be and demonstrate that the recovery of each analyte is no less
made, as appropriate. than 85%.
pounds by flame photometric gas chromatography. Sulfur Accuracy (as % recovery) with separatory funnel extraction
cleanup using EPA Method 3660 may alleviate this interference. ranged from 101 (with low spikes) to 86 (with high spikes).
A nitrogen phosphorus detector (NPD) is also recommended. Accuracy (as % recovery) with continuous liquid-liquid extrac-
spikes).
Accuracy (as % recovery) with Soxhlet extraction of soils
lytes of interest does not occur.
ranged from 75 (with low spikes to 80 (with high spikes).
Method interferences may be caused by contaminants in sol- Accuracy (as % recovery) with ultrasonic extraction of soils
vents, reagents, glassware, and other sample processing hard- ranged from not recovered (with low spikes) to 75 (with
ware that lead to discrete artifacts or elevated baselines in gas high spikes).
Containers used to collect samples for the determination of
the analysis by analyzing reagent blanks.
semivolatile organic compounds should be soap and water
INSTRUMENTATION A GC with a NPD or a FPD will be washed followed by methanol (or isopropanol) rinsing. The
needed. A data system or integrator is recommended for mea- sample containers should be of glass or Teflon® and have screw-
suring peak areas and/or peak heights. A Kuderna-Danish top covers with Teflon® liners.
No preservation is used with concentrated waste samples. With
Column 1: 15 m  0.53 mm megabore capillary column, liquid samples containing no residual chlorine and with soil,
1.0 m film thickness, DB-210. sediment, and sludge samples, immediately cooling to 4C is
Column 2: 15 m  0.53 mm megabore capillary column, the only preservation used. When residual chlorine is present
1.5 m film thickness, SPB-608. then 3 mL of 10% aqueous sodium sulfate is added for each
Column 3: 15 m  0.53 mm megabore capillary column, gallon of sample collected, followed by cooling to 4C.
1.0 m film thickness, DB-5.
Three megabore capillary columns are included for analysis of extracts analyzed within 40 days. Concentrated waste, soil, sed-
organophosphates by this method. Column 1 (DB-210 or iment, and sludge samples must be extracted within 14 days
equivalent) and Column 2 (SPB-608 or equivalent) are recom- and their extracts analyzed within 40 days.
mended if a large number of organophosphorus analytes are
to be determined. If the superior resolution offered by Column SAMPLE PREPARATION In general, water samples are
1 and Column 2 is not required, Column 3 (DB-5 or equiva- extracted at a neutral pH with methylene chloride, using either
lent) may be used. For megabore capillary columns, automatic EPA Method 3510 or EPA Method 3520. Solid samples are
injections of 1 L are recommended. extracted using either EPA Method 3540 or EPA Method 3550
with methylene chloride/acetone (1:1) as the extraction solvent.
PRECISION & ACCURACY The MDL actually achieved in
a given analysis will vary, as it is dependent on instrument Prior to GC analysis, the extraction solvent may be exchanged
sensitivity and matrix effects. Single operator accuracy and to hexane. Single lab data indicates that samples should not be
precision studies have been conducted with spiked water and transferred with 100% hexane during sample workup as the
soil samples. more water soluble organophosphorus compounds may be lost.
MULTIPLICATION FACTORS FOR OTHER MATRICES (a) If cleanup is performed on the samples, the analyst should
Matrix Factor (b) analyze the samples by GC. This will confirm elution patterns
and the absence of interferences from the reagents. If peak
Groundwater 10 detection and identification is prevented by the presence of
(EPA Method 3510 or EPA Method 3520) interferences, further cleanup is required.
Low-concentration soil by Soxhlet and no cleanup 10 (c)
Low-concentration soil by ultrasonic extraction 6.7 (c) QUALITY CONTROL The analyst should monitor the per-
with GPC cleanup formance of the extraction, cleanup (when used), and analyt-
High-concentration soil and sludges 500 (c) ical system and the effectiveness of the method in dealing with
by ultrasonic extraction each sample matrix by spiking each sample, standard, and
Non-water miscible waste (EPA Method 3580) 1000 (c) blank with one or two surrogates (e.g., organophosphorus
(a) SampleEQLs are highly matrix-dependent. TheEQLslisted here
terated analogs of analytes should not be used as surrogates for
are provided for guidance and may not always be achievable.
gas chromatographic analysis due to coelution problems.
(b) EQL = [Method detection limit] [Factor]. For non-aqueous
samples the factor is on a wet-weight basis. A minimum of five concentrations for each analyte of interest
(c) Multiply this factory times the soil MDL. should be prepared through dilution of the stock standards

with isooctane. One of the concentrations should be at a con- and low-concentration samples are sequentially analyzed. To
centration near, but above, the MDL. reduce carryover, the sample syringe must be rinsed out
Include a mid-level check standard after each group of 10 sam-
judiciously employed to support qualitative identifications
made with this method. Follow the GC/MS operating require- INSTRUMENTATION A GC/MS and a data system are
ments specified in EPA Method 8270. required. The GC column used is a 30 m 0.25 mm I.D. (or
employed to aid in the qualitative identification process. To
confirm an identification of a compound, the background-
bath, and an ultrasonic disrupter with a minimum power of
from the sample extract and must be compared with a mass
300 W and with pulsing capability are also required.
spectrum from a stock or calibration standard analyzed under
the same chromatographic conditions. The molecular ion and PRECISION & ACCURACY The estimated quantitation
all other ions present above 20% relative abundance in the mass limit (EQL) of Method 8270B for determining an individual
spectrum of the standard must be present in the mass spectrum compound is approximately 1 mg/kg (wet weight) for soil or
of the sample with agreement to 20%. The retention time of sediment samples, 1–200 mg/kg for wastes (dependent on
the compound in the sample must be within six seconds of the matrix and method of preparation), and 10 g/L for ground-
retention time for the same compound in the standard solution. water samples. EQLs will be proportionately higher for sample
additional steps may be taken before reanalysis. These steps The EQL(b) for groundwater in g/L is not listed.
may include the use of alternate packed or capillary GC col- The EQL (a, b) for low concentrations in soil and sediment
umns or additional sample cleanup. in g/kg is not listed.
REFERENCE Test Methods for Evaluating Solid Waste, Phys-
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
of Solid Waste, Washington, DC, EPA Method 8141 July 1992. (a) EQLs listed for soil/sediment are based on wet weight. Nor-
Ethyl parathion EPA Method 8270 ation chromatography cleanup.

concentrator.
Ethylbenzene EPA Method 1624
flowing sandy texture must be mixed with anhydrous sodium TITLE Volatile Organic Compounds by Isotope Dilution
sulfate until the sample is free flowing. Add 1 mL of surrogate GC/MS
sample in each analytical batch selected for spiking, add 1.0 mL MATRIX Compounds may be determined in waters, soils,
of a matrix spiking standard. For base/neutral acid analysis, the and municipal sludges by this method.
amount added of the surrogates and matrix spiking com- METHOD SUMMARY This method is used to determine 58
pounds should result in a final concentration of 100 ng/ L of volatile toxic organic pollutants associated with the CWA (as
each base/neutral analyte and 200 ng/L of each acid analyte amended 1987); the RCRA (as amended 1986); the CERCLA
in the extract to be analyzed (assuming a 1- L injection). (as amended 1986); and other compounds amenable to purge-
Immediately add a 100-mL mixture of 1:1 methylene chlo- and-trap gas chromatography-mass spectrometry (GC/MS).
and then decant or filter the extracts. Repeat the extraction two If the solids content is less than 1%, stable isotopically-labeled
or more times. Dry the extract using a column with anhydrous analogs of the compounds of interest are added to a 5-mL
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. sample and the sample is purged with an inert gas at 20–25 C
in a chamber designed for soil or water samples. If the solids
QUALITY CONTROL A methylene chloride solution con- content is greater than 1%, 5 mL of reagent water and the
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is labeled compounds are added to a 5-g aliquot of sample and
used for tuning the GC/MS system each 12-h shift. A system the mixture is purged at 40C. Compounds that will not purge
performance check also must be made during every 12-h shift. at 20–25C or at 40C are purged at 78–85C. In the purging
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- process, the volatile compounds are transferred from the aque-
rophenol, and benzidine is required to verify injection port ous phase into the gaseous phase where they are passed into a
inertness and GC column performance. A calibration standard sorbent column, and trapped. After purging is completed, the
at mid-concentration, containing each compound of interest, trap is backflushed and heated rapidly to desorb the com-
including all required surrogates, must be performed every 12 h pounds into a GC. The compounds are separated by the GC
during analysis. After the system performance check is met, and detected by a MS. The labeled compounds serve to correct
calibration check compounds (CCCs) are used to check the the variability of the analytical technique.
INTERFERENCES Impurities in the purge gas, organic com-
The internal standard responses and retention times in the pounds outgassing from the plumbing upstream of the trap, and
calibration check standard must be evaluated immediately after solvent vapors in the lab account for most problems.Sam ples can

be contaminated by diffusion of volatile organic compounds method performance on the sample matrix. Compute the per-
(particularly methylene chloride) through the bottle seal dur- cent recovery of the labeled compounds using the internal stan-
ing shipment and storage. Contamination by carryover can dard method. Compare the percent recovery for each
occur when high-level and low-level samples are analyzed compound with the corresponding labeled compound recov-
sequentially. When an unusually concentrated sample is ery. Reagent water blanks are analyzed to demonstrate freedom
encountered, follow it by analysis of a reagent water blank to from carryover contamination. Field replicates may be col-
check for carryover. lected to determine the precision of the sampling technique,
and spiked samples may be required to determine the accuracy
INSTRUMENTATION Major equipment includes a GC with
of the analysis when the internal method is used.
linear temperature programming and a glass jet separator as
the MS interface, a MS with 70 eV electron impact ionization, REFERENCE Volatile Organic Compounds by Isotope Dilu-
and a data system to collect and record response factors. tion GC/MS. Office of Water Regulation and Standards, U.S.
EPA Industrial Technology Division, Washington, DC, EPA
Column: 2.8 m 2 mm I.D. glass, packed with 1% SP-1000 on
Method 1624, Rev. C, June 1989 (contact W.A. Telliard, U.S.
Carbopak B, 60/80 mesh, or equivalent.
EPA, Office of Water Regulations and Standards, 401 M St.,
PRECISION & ACCURACY The detection limits of the SW, Washington, DC, 20460. Phone: 202-382-7131).
filter cake or compost (high solids).
CAS #100-41-4
The MDL (in g/kg) for low solids is 28 and for high solids is 4.
Labeled and native compound precision (in g/L) as standard TITLE Volatile Organic Compounds in Water By Purge and
deviation was 9.6. Trap Capillary Column Gas Chromatography with Photoion-
Labeled and native compound accuracy (in g/L) as average ization and Electrolytic Conductivity Detectors in Series. U.S.
recovery was 16–29. EPA Method 502.2, Rev. 2.0, 1989.
Acceptance criteria are at 20 g/L for this compound.
MATRIX Drinking water and raw source water. The latter
SAMPLE COLLECTION, PRESERVATION & HANDLING should include most surface water and groundwater sources.
METHOD SUMMARY This method covers 60 volatile
organic compounds that contain halogen atoms and/or that
air bubbles are entrapped. Samples are maintained at 0 to 4 C are aromatic. An inert gas (zero grade nitrogen or helium) is
from the time of collection until analysis. If an aqueous sample
bubbled through a 25-mL or a 5-mL water sample (depending
contains residual chlorine, add sodium thiosulfate preservative
on the expected concentration of the analytes). Purged sample
(10 mg/40 mL) to the empty sample bottles just prior to ship-
components are trapped in a tube of sorbent materials. When
ment to the sample site. All samples must be analyzed within
purging is complete, the sorbent tube is heated and backflushed
14 days of collection.
with helium to desorb the trapped sample onto a capillary GC
SAMPLE PREPARATION Samples containing less than 1% column. The column is temperature programmed to separate
solids are analyzed directly as aqueous samples. Samples con- the method analytes which are then detected with a photoion-
taining 1% solids or greater are analyzed as solid samples uti- ization detector (PID) and a Hall electrolytic conductivity
lizing one of two methods, depending on the levels of (HECD) placed in series. The PID is selective for aromatic
pollutants, in the sample. Samples containing 1% solids or compounds and the HECD is selective for halogenated com-
greater, and low to moderate levels of pollutants are analyzed pounds.
by purging a known weight of sample added to 5 mL of reagent
INTERFERENCES Impurities in the purge gas and from
water. Samples containing 1% solids or greater, and high levels
organic compounds outgassing from the plumbing ahead of
of pollutants, are extracted with methanol, and an aliquot of
the trap account for many contamination problems. Interfer-
the methanol extract is added to reagent water and purged.
ences purged or coextracted from the samples will vary con-
QUALITY CONTROL A field blank prepared from reagent siderably from source to source, depending upon the particular
water and carried through the sampling and handling protocol sample or extract being tested. Cross-contamination can occur
may serve as a check on contamination from shipment and whenever high-level and low-level samples are analyzed
storage. sequentially. Samples also can be contaminated by diffusion of
volatile organics (particularly methylene chloride and fluoro-
The analyst is permitted to modify this method to improve carbons) through the septum seal into the sample during ship-
separations or lower the costs of measurements, provided all
ment and storage. The lab where volatile analysis is performed
performance specifications are met. Analyses of blanks are
and also the refrigerated storage area should be completely free
of solvents.
performance within acceptable limits. Analyze two sets of four INSTRUMENTATION A GC containing a series configura-
5-mL aliquots (8 aliquots total) of the aqueous performance tion of a high temperature photoionization detector (PID)
standard. Spike all samples with labeled compounds to assess equipped with 10.0 eV (nominal) lamp and Hall electrolytic

conductivity detector (HECD) is required. Also required is an SAMPLE PREPARATION Remove the plungers from two
all-glass 5-mL purging device, a sorbent trap, and a thermal 5-mL syringes and attach a closed syringe valve to each. Warm
desorption apparatus which is connected to the GC system. the sample to room temperature, open the sample bottle, and
carefully pour the sample into one of the syringe barrels to just
Column 1: VOCOL glass wide-bore capillary column.
short of overflowing. Replace the syringe plunger, invert the
Column 2: RTX–502.2 mega-bore capillary column.
syringe, and compress the sample. Open the syringe valve and
Column 3: DB-62 mega-bore capillary column.
vent any residual air while adjusting the sample volume to
PRECISION & ACCURACY Method detection limits are 5.0 mL. Add 10 L of the internal calibration standard to the
dependent upon the characteristics of the gas chromatographic sample through the syringe valve. Close the valve. Fill the sec-
system used. Analytes that are not separated chromatographi- ond syringe in an identical manner from the same sample
cally cannot be individually identified and used in the same bottle. Reserve this second syringe for a reanalysis if necessary.
calibration mixture or water samples unless an alternative tech- QUALITY CONTROL As an initial demonstration of lab
nique for identification and quantification, such as mass spec- accuracy and precision, analyze 4 to 7 replicates of a lab fortified
trometry, is used. blank containing analyte at 0.1–5 g/L. Collect all samples in
Electrolytic conductivity detetor (c) range in g/L (a) was duplicate. Surrogate analytes (similar to those of the analytes
0.02–200. of interest), whose concentration is known in every sample, are
Electrolytic conductivity detetor (c) MDL in g/L (b) was not measured using the same internal standard calibration proce-
listed. dure. Duplicate field reagent water blanks (trip blanks) must
Electrolytic conductivity detetor (c) accuracy as % recoverywas be analyzed with each set of samples, lab reagent blanks
not listed. (method blanks) must be analyzed with each batch of samples
Electrolytic conductivity detetor (c) precision as % RSD was processed as a group within a work shift. Also, a single lab-
not listed. fortified blank that contains each of the analytes of interest
Photoionization detector (d) range in g/L (a) was 0.02–200. should be analyzed with each batch of samples processed as a
Photoionization detector (d) MDL in g/L (b) was 0.01. group within a work shift. A 3- to 5-point calibration curve is
Photoionization detector (d) accuracy as % recovery was 101. needed depending on the calibration range factor required.
Photoionization detector (d) precision as % RSD was 1.4. EPA CONTACT & HOTLINE For technical questions contact
(a) The applicable concentration range of this method is com- Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
pound, instrument, and matrix-dependent. It is listed as Drinking Water (WH-550D), 401 M St. SW, Washington, DC
being approximately 0.02 to 200 g/L but no specific infor- 20460. Tel. (202) 260-3040. For further information the EPA
mation is provided so caution should be observed. Safe Drinking Water Hotline may be called at: (800) 426-4791.
(b) The method detection limits reports with this method are REFERENCE Methods for the Determination of Organic
compound, instrument, and matrix-dependent. The values Compounds in Drinking Water, EPA/600/4-88/039 (revised
reported were calculated using reagent water fortifi d with July 1991; Final Rule for determination of compliance with the
the corresponding compounds at 10 g/L and a MCL for Total Trihalomethanes under 141.30, in 40 CFR Part
GC-equipped with a 60 m 0.75 mm VOLCOL wide bore 141, Vol. 58, No. 147, Fed. Reg., Tuesday Aug. 3, 1993). U.S.
capillary column with 1.5 m fi m thickness and using EPA Environmental Monitoring Systems Laboratory, Cincin-
helium carrier gas. nati, OH, 45268, U.S.A. Available from the National Technical
(c) Recoveries and relative standard deviations were deter- Information Service (NTIS), 5285 Port Royal Road, Spring-
mined from seven samples of reagent water fortifi d with field, VA 22161; Tel. 800-553-6847. NTIS Order Number is
10 g/L of each compound. 2-Bromo-1-chloropropane was PB91-231480.
used as the internalstandard forcalculatingaverage recoveries.
(d) Recoveries and relative standard deviations were deter-
mined from seven samples of reagent water fortifi d with
10 g/L of each compound. Fluorobenzene was used as the Ethylbenzene EPA Method 524
internal standard for calculating average recoveries. CAS #100-41-4
SAMPLING METHOD Collect samples using a 40- to TITLE Measurement of Purgeable Organic Compounds in
120-mL screw-cap vial (prewashed with detergent, rinsed with Water by Capillary Column GC/MS.
distilled water and oven dried at 105C) with a Teflon®-faced
MATRIX Drinking water and raw source water; the latter
should include most surface water and groundwater sources.
METHOD SUMMARY Method 524.2 covers 60 volatile
SAMPLE PRESERVATION If residual chlorine is present in
organic compounds. An inert gas (zero grade nitrogen or
the water add about 25 mg of ascorbic acid to each vial before
helium) is bubbled through a 25-mL or a 5-mL water sample
samples are collected to remove the chlorine. Add hydrochloric
(depending on the expected concentration of the analytes).
acid to reduce pH to <2, immediately cool samples to 4 C, and
Purged sample components are trapped in a tube of sorbent
store them in a solvent-free refrigerator at 4C until analysis. materials. When purging is complete, the sorbent tube is heated
MHT The maximum holding time for samples is 14 days and backflushed with helium to desorb the trapped sample
from the time they were collected. onto a capillary GC column.
INTERFERENCES Impurities in the purge gas and from samples are collected to remove the chlorine. Add hydrochloric
organic compounds outgassing from the plumbing ahead of acid to reduce pH to <2, and immediately cool samples to 4 C,
the trap account for many contamination problems. Interfer- and store them in a solvent-free refrigerator at 4C until analysis.
MHT The maximum holding time for samples is 14 days
siderably from source to source, depending upon the particular
sample or extract being tested. Cross-contamination can occur from the time they were collected.
whenever high-level and low-level samples are analyzed SAMPLE PREPARATION Remove the plungers from two
sequentially. Samples also can be contaminated by diffusion of 25-mL (or 5-mL depending on sample size) syringes and attach
volatile organics (particularly methylene chloride and fluoro- a closed syringe valve to each. Warm the sample to room tem-
carbons) through the septum seal into the sample during ship- perature, open the sample bottle, and carefully pour the sample
ment and storage. into one of the syringe barrels to just short of overflowing.
INSTRUMENTATION A GC/MS with a data system Replace the syringe plunger, invert the syringe, and compress
equipped with one of the following capillary GC columns: the sample. Open the syringe valve and vent any residual air
while adjusting the sample volume to 25.0 mL (or 5 mL). For
Column 1: VOCOL glass wide bore capillary column. samples and blanks, add 5 L of the fortification solution con-
Column 2: DB-624 fused silica capillary column. taining the internal standard and the surrogates to the sample
Column 3: DB-5 fused silica capillary column. through the syringe valve. For calibration standards and lab
Also required is an all-glass 25 mL or 5-mL purging device, a fortified blanks, add 5 L of the fortification solution contain-
sorbent trap, and a thermal desorption apparatus which is ing the internal standard only. Close the valve. Fill the second
connected to the GC/MS system. syringe in an identical manner from the same sample bottle.
Reserve this second syringe for a reanalysis if necessary.
compound- and instrument-dependent, and may vary from QUALITY CONTROL As an initial demonstration of lab
approximately 0.02–0.35 g/L. Note in the table below that the accuracy and precision, analyze 4 to 7 replicates of a lab fortified
“true” concentration range used for accuracy and precision blank containing analyte at 0.2–5 g/L. Collect all samples in
measurements was quite narrow. However, the applicable con- duplicate. Surrogate analytes (similar to those of the analytes
centration range of this method is primarily column dependent of interest), whose concentration is known in every sample, are
and is approximately 0.02 to 200 g/L for the wide-bore thick- measured using the same internal standard calibration proce-
film columns. Narrow-bore thin-film columns may have a dure. Duplicate field reagent water blanks (trip blanks) must
capacity which limits the range to about 0.02 to 20 g/L. Ana- be analyzed with each set of samples, lab reagent blanks
lytes that are inefficiently purged from water will not be (method blanks) must be analyzed with each batch of samples
detected when present at low concentrations, but they can be processed as a group within a work shift. Also, a single lab-
measured with acceptable accuracy and precision when present fortified blank that contains each of the analytes of interest
in sufficient amounts. should be analyzed with each batch of samples processed as a
group within a work shift. A 3- to 5-point calibration curve is
Analytes that are not separated chromatographically, but which needed depending on the calibration range factor required.
have different mass spectra and non-interfering quantification
ions, can be identified and measured in the same calibration EPA CONTACT & HOTLINE For technical questions contact
mixture or water sample.Analytes which have very similar mass Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
spectra cannot be individually identified and measured in the Drinking Water (WH-550D), 401 M St. SW, Washington, DC
same calibration mixture or water samples unless they have 20460. Tel. (202) 260-3040. For further information the EPA
different retention times. Co-eluting compounds with very Safe Drinking Water Hotline may be called at: (800) 426-4791.
similar mass spectra, typically many structural isomers, must
be reported as an isomeric group or pair.
The range (in g/L) was 0.1–10. July 1991; Final Rule for determination of compliance with the
The Method Detection Limig (in g/L) was 0.06. MCL for Total Trihalomethanes under 141.30, in 40 CFR Part
The accuracy (as % recovery) was 99. 141, Vol. 58, No. 147, Fed. Reg., Tuesday Aug. 3, 1993). U.S.
The precision (in %) was 8.6. EPA Environmental Monitoring Systems Laboratory, Cincin-
nati, OH, 45268, U.S.A. Available from the National Technical
Note: Data were obtained from 16–31 determinations using a
Information Service (NTIS), 5285 Port Royal Road, Spring-
wide-bore capillary column and a jet separator interfaced to a
field, VA 22161; Tel. 800-553-6847. NTIS Order Number is
quadrupole mass spectrometer. All analytes were in a reagent
PB91-231480.
water matrix.
SAMPLING METHOD Collect samples using a 40- to
120-mL screw-cap vial (prewashed with detergent, rinsed with
CAS #100-41-4
TITLE Halogenated Volatile by Gas Chromatography Using
SAMPLE PRESERVATION If residual chlorine is present in Photoionization and Electrolytic Conductivity Detectors in
the water add about 25 mg of ascorbic acid to each vial before Series: Capillary Column Technique
MATRIX This method is applicable to nearly all types of Recoveries and standard deviations were determined from
samples, regardless of water content, including groundwater, seven samples and spiked at 10 g/L of each analyte. Recoveries
aqueous sludges, caustic liquors, acid liquors, waste solvents, were determined by the internal standard method. Internal
oily wastes, mousses, tars, fibrous wastes, polymeric emulsions, standards were: Fluorobenzene for PID and 2-Bromo-1-chlo-
filter cakes, spent carbons, spent catalysts, soils, and sediments. ropropane for HECD.
METHOD SUMMARY This method is used to determine 60 The average recovery (in percent) for the PID was 101.
volatile organic compounds in a variety of solid waste matrices. The standard deviation of the recovery for the PID was 1.4.
It provides GC conditions for the detection of halogenated and The MDL (in g/mL) for the PID was 0.005.
aromatic volatile organic compounds. Samples can be analyzed The average recovery (in percent) for the HECD was none (no
using direct injection or purge-and-trap (EPA Method 5030). response for this detector).
Groundwater samples must be analyzed using EPA Method The standard deviation of the recovery for the HECD was none
5030 (where applicable). A temperature program is used with (no response for this detector)-.
the GC. Detection is achieved by a photoionization detector The MDL (in g/mL) for the HECD was none (no response
(PID) and a Hall electrolytic conductivity detector (HECD) in for this detector).
series. SAMPLE COLLECTION, PRESERVATION & HANDLING
INTERFERENCES Samples can be contaminated by diffu- Volatile Organics — Standard 40-mL glass screw-cap VOA vials
with Teflon®-faced silicone septum may be used for both liquid
sion of volatile organics (particularly chlorofluorocarbons and
and solid matrices. When collecting samples, liquids and solids
methylene chloride) through the sample container septum dur-
should be introduced into the vials gently to reduce agitation
ing shipment and storage.
which might drive off volatile compounds. If there are any air
INSTRUMENTATION A GC-equipped with variable-con- bubbles present the sample must be retaken. Tap slightly as
stant differential flow controllers, subambient oven controller, they are filled to try and eliminate as much free air space as
PID and HECD detectors connected with a short piece of possible. The two vials from each sampling locations should
uncoated capillary tubing and a data system. be sealed in separate plastic bags to prevent cross-contamina-
tion between samples particularly if the sampled waste is sus-
Column: 60 m 0.75 mm I.D.VOCOLwide-bore capillary col- pected of containing high levels of volatile organics.
umn with 1.5 m film thickness.
Semivolatile organics — Containers used to collect samples for
PRECISION & ACCURACY MDLs are compound-depen- the determination of semivolatile organic compounds should
dent and vary with purging efficiency and concentration. The be soap and water washed followed by methanol (or isopro-
applicable concentration range of this method is compound- panol) rinsing. The sample containers should be of glass or
and instrument-dependent but is approximately 0.1 to Teflon® and have screw-top covers with Teflon® liners.
200 g/L. Analytes that are inefficiently purged from water will
not be detected when present at low concentrations, but they Preservation for volatile organics — No preservation is used
can be measured with acceptable accuracy and precision when with concentrated waste samples. With liquid samples contain-
present in sufficient amounts. The estimated quantitation limit ing no residual chlorine, 4 drops of concentrated hydrochloric
(EQL) for an individual compound is approximately 1 g/kg acid are added and the samples are immediately cooled to 4 C.
When liquid samples contain residual chlorine, they are treated
(wet weight) for soil/sediment samples, 100 g/kg (wet weight)
as above and, in addition, 4 drops of 4% aqueous sodium
for wastes, and 1 g/L for groundwater. EQLs will be propor-
thiosulfate are added. Soil, sediment, and sludge samples are
tionately higher for sample extracts and samples that require
only cooled to 4C.
dilution or reduced sample size to avoid saturation of the detector.
Preservation for semivolatile organics — No preservation is
MULTIPLICATION FACTORS FOR OTHER MATRICES (a) used with concentrated waste samples. With liquid samples
Matrix Factor (b) containing no residual chlorine and with soil, sediment, and
Groundwater 10 sludge samples, immediately cooling to 4C is the only preser-
Low-concentration soil 10 vation used. When residual chlorine is present then 3 mL of
Water miscible liquid waste 500 10% aqueous sodium sulfate is added for each gallon of sample
High-concentration soil and sludge 1250 collected, followed by cooling to 4C.
Non-water miscible waste 1250 MHT The holding time for all volatile organics samples is
(a) Sample EQLs are highly matrix-dependent. The EQLs listed 14 days. Liquid samples must be extracted within 7 days and
herein are provided for guidance and may not always be achievable. their extracts analyzed within 40 days. Concentrated waste, soil,
(b) EQL = [Method detection limit] [Factor]. For non-aqueous sediment, and sludge samples must be extracted within 14 days
samples, the factor is on a wet-weight basis. and their extracts analyzed within 40 days.
SINGLE LABORATORY ACCURACY & PRECISION DATA SAMPLE PREPARATION Volatile compounds are intro-
FOR VOCs IN WATER duced into the gas chromatograph either by direct injector or
purge-and-trap (EPA Method 5030). EPA Method 5030 may
This method was tested in a single lab using water spiked at be used directly on groundwater samples or low-concentration
10 g/L and the following data was reported: contaminated soils and sediments. For medium-concentration

soils or sediments, methanolic extraction, as described in EPA I.D. glass column packed with 1% SP-1000 on Carbopack-B
Method 5030, may be necessary prior to purge-and-trap analysis. (60/80 mesh) is required.Also needed is a 5-mL purging device,
QUALITY CONTROL Calculate surrogate standard recovery a sorbent trap, and a thermal desorption apparatus.
on all samples, blanks, and spikes.A trip blank is recommended PRECISION & ACCURACY This method is reported to have
to check on sampling, storage, and handling contamination. been tested by 15 laboratories using organic-free reagent water,
Calibration standards, at a minimum of five concentration lev- drinking water, surface water, and industrial wastewaters (not
els, are prepared in organic-free reagent water. One of the con- specified) fortified at six concentrations over the range 5–
centration levels should be at a concentration near, but above, 600 g/L.
the method detection limit.
Sample estimated quantitation limits (EQLs) are highly
A combination of bromochloromethane, 2-bromo-1-chloro-
matrix-dependent. The EQLs listed may not always be achiev-
propane, 1,4-dichlorobutane, and bromochlorobenzene are
able. EQLs listed for soils or sediments are based on wet weight.
recommended as surrogate standards to encompass the range
of the temperature program used in this method. Normally, data is reported on a dry-weight basis; therefore,
EQLs will be higher, based on the percent dry weight of each
REFERENCE Test Methods for Evaluating Solid Waste, Phys- sample. Note that EQLs are even more variable than MDLs and
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office that they are highly variable depending on the matrix being
of Solid Waste, Washington, DC, EPA Method 8021A, Rev. 1, analyzed.
Nov. 1992.
EQL in groundwater in g/L was 5.
EQL in low soil or sediment in g/kg was 5.
Accuracy (a) in g/L was 0.98C + 2.48.
Ethylbenzene EPA Method 8240 Precision (b) in g/L was 0.26x–1.72.
CAS #100-41-4
TITLE Volatile Organics By GC/MS: Packed Column Technique taining a concentration of C, in g/L.
MATRIX Nearly all types of sample matarices, regardless of average recovery X for samples containing a concentration
water content, can be analyzed using this method. This includes
of C in g/L.
groundwater, aqueous sludges, caustic liquors, acid liquors,
X = Average recovery found for measurement of samples con-
taining a concentration of C in g/L.
soils, and sediments. MULTIPLICATION FACTORS FOR OTHER MATRICES
METHOD SUMMARY Method 8240B covers 80 volatile Other Matrices Factor (a)
organic compounds that are introduced into a gas chromato- Waste miscible liquid waste 50
graph by the purge-and-trap method or by direct injection (in High-concentration soil and sludge 125
limited applications). For the purge-and-trap method an inert Non-water miscible waste 500
gas (zero grade nitrogen or helium) is bubbled through a 5-mL
solution at ambient temperature. Purged sample components (a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous
are trapped in a tube of sorbent materials. When purging is samples, the factor is on a wet-weight basis.
complete, the sorbent tube is heated and backflushed with inert SAMPLING METHOD
gas to desorb the trapped components onto a GC column. Liquid samples — Use a 40-mL glass screw-cap VOA vial with
INTERFERENCES Impurities in the purge gas and from a Teflon®-faced silicone septum that has been prewashed,
organic compounds outgassing from the plumbing ahead of rinsed with distilled deionized water, and oven dried. However,
the trap account for many contamination problems. Interfer- if residual chlorine is present, collect sample in a 40-oz. soil
ences purged or coextracted from the samples will vary con- VOA container which has been pre-preserved with 4 drops of
siderably from source to source. Cross-contamination can 10% sodium thiosulfate, mix gently, and then transfer the sam-
occur whenever high-level and low-level samples are analyzed ple to a 40-mL VOA vial. Collect bubble-free samples in dupli-
sequentially. Whenever an unusually concentrated sample is cate and seal them in separate plastic bags.
analyzed, it should be followed by the analysis of organic-free
reagent water to check for cross-contamination. Samples also Soils or sediments, and sludges — Use an 8-oz. widemouth
can be contaminated by diffusion of volatile organics (partic- glass bottle with a Teflon®-faced silicone septum that has been
ularly methylene chloride and fluorocarbons) through the sep- prewashed with detergent, rinsed with distilled deionized
tum seal into the sample during shipment and storage. A trip water, and oven dried. Tap slightly to eliminate free air space.
blank can serve as a check on such contamination. The lab Collect samples in duplicate and seal them in separate plastic bags.
where volatile analysis is performed and also the refrigerated
storage area should be completely free of solvents. SAMPLE PRESERVATION
Liquid samples — Add 4 drops of concentrated HCL and
INSTRUMENTATION A gas chromatograph/mass spec- immediately cool samples to 4C and store in a solvent-free
trometry/data system (GC/MS) equipped with a 6 ft 0.1 in refrigerator.

Soils or sediments, and sludges — Cool samples to 4C and METHANOL EXTRACT REQUIRED FOR ANALYSIS
store in a solvent-free refrigerator. OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
MHT Maximum holding time is 14 days from the date of Approximate Volume of
sample collection. Concentration Range Methanol Extract (a)
500–10,000 g/kg 100 L
SAMPLE PREPARATION
1,000–20,000 g/kg 50 L
5,000–100,000 g/kg 10 L
and carefully pour the sample into the syringe barrel to just
short of overflowing. Replace the syringe plunger and compress
the sample. Open the syringe valve and vent any residual air Calculate appropriate dilution factor for concentrations
while adjusting the sample volume to 5.0 mL. If there is only exceeding this table.
one volatile organic analysis (VOA) vial, a second syringe (a) The volume of methanol added to 5 mL of water being purged
should be filled at this time to protect against possible loss of should be kept constant. Therefore, add to the 5-mLsyringe whatever
sample integrity. Add 10 L of surrogate spiking solution and volume of methanol is necessary to maintain a volume of 100 L
10 L of internal standard spiking solution through the valve added to the syringe.
bore of the 5-mL syringe, then close the valve. The surrogate (b) Dilute an aliquot of the methanol extract and then take 100 L
and internal standards may be mixed and added as a single for analysis.
spiking solution. QUALITY CONTROL Demonstrate, through the analysis of
Sediments, soils, and waste samples — All samples of this type a reagent water blank, that interferences from the analytical
should be screened by GC analysis using a headspace method system, glassware, and reagents are under control. Blank sam-
(EPA Method 3810) or the hexadecane extraction and screen-
ration and measurement steps. For each analytical batch (up
ing method (EPA Method 3820). Use the screening data to
to 20 samples), a reagent blank, matrix spike, and matrix spike
determine whether to use the low-concentration method duplicate must be analyzed (the frequency of the spikes may
(0.005–1 mg/kg) or the high-concentration method (>1 mg/kg). be different for different monitoring programs). The blank and
Low-concentration method — The low-concentration method spiked samples must be carried through all stages of the sample
is based on purging a heated sediment or soil sample mixed preparation and measurement steps. QC samples mentioned
with organic-free reagent water containing the surrogate and in the section on Interferences will also be needed as appropri-
ate to those situations.
internal standards. Analyze all reagent blanks and standards
under the same conditions as the samples. REFERENCE Test Methods for Evaluating Solid Waste (SW-
row metal spatula. Weigh the amount of the sample into a tared
purge device. Add the spiked water to the purge device, which Ethylbenzene EPA Method 8260
contains the weighed amount of sample, and connect the CAS #100-41-4
TITLE Volatile Organic Compounds by GC/MS: Capillary
High-concentration method — This method is based on Column Technique
MATRIX This method is applicable to nearly all types of
is either extracted or diluted, depending on its solubility in
samples, regardless of water content, including groundwater,
methanol. Wastes that are insoluble in methanol are diluted soils, and sediments.
An aliquot of the extract is added to organic-free reagent water METHOD SUMMARY Method 8260A covers 58 volatile
containing surrogate and internal standards. This is purged at organic compounds that are introduced into a gas chromato-
ambient temperature. All samples with an expected concentra- graph by the purge-and-trap method or by direct injection (in
limited applications). Zero-grade helium is bubbled through a
5-mL solution at ambient temperature. Purged sample com-
Mix the contents of the sample container with a narrow metal ponents are trapped in a tube containing suitable sorbent mate-
spatula. For sediments or soils and solid wastes that are insol- rials. When purging is complete, the sorbent tube is heated and
uble in methanol, weigh 4 g (wet weight) of sample into a tared backflushed with helium to desorb trapped sample compo-
20-mL vial. For waste that is soluble in methanol, tetraglyme, nents. The analytes are desorbed directly to a large bore capil-
or PEG, weigh 1 g (wet weight) into a tared scintillation vial lary or cryofocussed on a capillary precolumn before being
or culture tube or a 10-mL volumetric flask. Quickly add flash evaporated to a narrow bore capillary for analysis.
9.0 mL of appropriate solvent then add 1.0 mL of a surrogate INTERFERENCES Major contaminant sources are volatile
spiking solution to the vial, cap it, and shake it for 2 min. materials in the lab and impurities in the inert purging gas and

in the sorbent trap. Interfering contamination may occur when Soils, sediments and sludges — Use an 8-oz widemouth glass
a sample containing low concentrations of volatile organic bottle with Teflon®-faced silicone septum that has been pre-
compounds is analyzed immediately after a sample containing washed, rinsed with distilled deionized water, and oven dried.
high concentrations of volatile organic compounds. After anal- Do not heat the septum for more than 1 h. Tap slightly to
ysis of a sample containing high concentrations of volatile eliminate any free air space. Collect samples in duplicate and
organic compounds, one or more calibration blanks should be seal each one in a separate plastic bag.
analyzed to check for cross-contamination. Screening of the
SAMPLE PRESERVATION
samples prior to purge-and-trap GC/MS analysis is highly rec-
Liquid samples — Add 4 drops of concentrated HCL, cool to
ommended to prevent contamination of the system. This is
4C and store in a solvent-free refrigerator.
especially true for soil and waste samples.
Soils, sediments and sludges — Cool samples to 4C and store
Special precautions must be taken to analyze for methylene in a solvent-free refrigerator.
chloride. The analytical and sample storage area should be
isolated from all atmospheric sources of methylene chloride. MHT The maximum holding time of any sample (liquids,
All gas chromatography carrier gas lines and purge gas plumb- soils, sediments, and sludges) is 14 days.
ing should be constructed from stainless steel or copper tubing.
SAMPLE PREPARATION
Laboratory clothing previously exposed to methylene chloride Liquid samples — Remove the plunger from a 5-mL syringe
fumes during liquid-liquid extraction procedures can contrib- and carefully pour the sample into the syringe barrel to just
ute to sample contamination. short of overflowing. Replace the syringe plunger and compress
Samples can also be contaminated by diffusion of volatile the sample. Open the syringe valve and vent any residual air
organics (particularly methylene chloride and fluorocarbons) while adjusting the sample volume to 5.0 mL. If there is only
through the septum seal during shipment and storage. A trip one volatile organic analysis (VOA) vial, a second syringe
blank can serve as a check on such contamination. should be filled at this time to protect against possible loss of
sample integrity. Add 10 L of surrogate spiking solution and
INSTRUMENTATION GC/MS with a temperature-pro- 10 L of internal standard spiking solution through the valve
grammable chromatograph suitable for splitless injection bore of the 5-mL syringe, then close the valve. The surrogate
equipped with variable constant differential flow controllers, a and internal standards may be mixed and added as a single
subambient oven controller, a purging device, sorbent trap, a spiking solution.
thermal desorption apparatus and a capillary precolumn inter-
face when using cryogenic cooling will be needed. The follow- Sediments, soils, and waste samples — All samples of this type
ing GC columns may be used: should be screened by GC analysis using a headspace method
Column 1: 60 m 0.75 mm I.D. capillary column coated with ing method (EPA Method 3820). Use the screening data to
VOCOL, 1.5 m film thickness. determine whether to use the low-concentration method
Column 2: 30 m 0.53 mm capillary column coated with DB- (0.005–1 mg/kg) or the high-concentration method (>1 mg/kg).
624 or VOCOL, 3 m film thickness.
Column 3: 30 m 0.32 mm I.D. capillary column coated with Low-concentration method — The low-concentration method
DB-5 or SE-54, 1-m film thickness. is based on purging a heated sediment or soil sample mixed
PRECISION & ACCURACY This method has been tested in internal standards. Analyze all reagent blanks and standards
a single lab using spiked water. Using a wide-bore capillary under the same conditions as the samples.
column, water was spiked at concentrations between 0.5 and
10 g/L. Single lab accuracy and precision data are presented. Use a 5-g sample if the expected concentration is <0.1 mg/kg
The MDL actually achieved in a given analysis will vary or a 1-g sample for expected concentrations between 0.1 and
depending on instrument sensitivity and matrix effects. 1 mg/kg. Mix the contents of the sample container with a nar-
row metal spatula. Weigh the amount of the sample into a tared
The MDL (a) in g/L was 0.06. purge device. Add the spiked water to the purge device, which
The concentration range in g/L was 0.1–10. contains the weighed amount of sample, and connect the
The mean accuracy (% of true value) was 99. device to the purge-and-trap system.
The precision as relative standard deviation was 8.6.
High-concentration method — This method is based on
Note: The MDL is based on a 25-mL sample volume instead extracting the sediment or soil with methanol. A waste sample
of a 5-mL sample volume. is either extracted or diluted, depending on its solubility in
SAMPLING METHOD
Liquid samples — Use a 40-mL glass screw-cap VOA vial with
rinsed with distilled deionized water, and oven dried. If residual
ambient temperature. All samples with an expected concentra-
chlorine is present, collect the sample in a 4-oz soil VOA con-
tainer which has been pre-preserved with 4 drops of 10%
sodium thiosulfate. Mix gently and transfer the sample to a Mix the contents of the sample container with a narrow metal
40-mL VOA vial. Collect bubble-free samples in duplicate and spatula. For sediments or soils and solid wastes that are insol-
seal each sample in a separate plastic bag. uble in methanol, weigh 4 g (wet weight) of sample into a tared
20-mL vial. For waste that is soluble in methanol, tetraglyme, MATRIX Drinking water (finished or in Water any treatment
or PEG, weigh 1 g (wet weight) into a tared scintillation vial stage) and raw source water.
APPLICATION Method covers 28 aromatic and unsaturated
9.0 mL of appropriate solvent then add 1.0 mL of a surrogate VOCs. An inert gas is bubbled through a 5-mL water sample.
spiking solution to the vial, cap it, and shake it for 2 min. Purged sample components are trapped in tube of sorbent
METHANOL EXTRACT REQUIRED FOR ANALYSIS materials.When purging is complete, sorbent tube is heated
OF HIGH-CONCENTRATION SOILS OR SEDIMENTS and backflushed with inert gas to desorb trapped sample onto
a packed GC column.
Approximate Volume of
Concentration Range Methanol Extract (a) INTERFERENCES During analysis, major contaminant
500–10,000 g/kg 100 L sources are volatile materials in the lab and impurities in purg-
1,000–20,000 g/kg 50 L ing gas and sorbent trap. With high and low level samples, there
5,000–100,000 g/kg 10 L can be carryover contamination. Excess water causes a negative
25,000–500,000 g/kg 100 L of 1/50 dilution (b) baseline deflection.
Calculate appropriate dilution factor for concentrations INSTRUMENTATION Purge and Trap GC w/photoioniza-
exceeding this table. tion detector. ( Two GC columns are recommended);
Column 1: 5% SP-1200 and 1.75% Bentone 34 on Supelcoport;
(a) The volume of methanol added to 5 mL of water being purged Column 2: 1,2,3-tris(2-cyanoethoxy)propane on Chromosorb W.
should be kept constant. Therefore, add to the 5-mLsyringe whatever
RANGE 2.2–600 g/L. (Drinking water).
volume of methanol is necessary to maintain a volume of 100 L
added to the syringe. MDL 0.002 g/L in water
(b) Dilute an aliquot of the methanol extract and then take 100 L
PRECISION RSD = 8.5% at 0.40 g/L conc.; 7 samples
for analysis.
ACCURACY Average recovery = 93% at 0.40 g/L conc.;
QUALITY CONTROL Demonstrate, through the analysis of
7 samples
system, glassware, and reagents are under control. Blank sam- SAMPLING METHOD Use a 40–120-mL screw-cap vial
ples should be carried through all stages of the sample prepa- (prewashed with detergent, rinsed with distilled water and oven
ration and measurement steps. For each analytical batch (up dried at 105C) with a PTFE-faced silicone septum . If residual
to 20 samples), a reagent blank, matrix spike, and matrix spike chlorine is in the water add about 25 mg of ascorbic acid to
duplicate must be analyzed (the frequency of the spikes may each vial before sample collection. Collect bubble-free samples.
be different for different monitoring programs). The blank and STABILITY Cool to 4C; HCl to pH <2.
preparation and measurement steps. QC samples mentioned MHT 14 days.
in the section on Interferences will also be needed as appropri- QUALITY CONTROL As initial demonstration of lab accu-
ate to those situations. racy and precision, analyze 4 to 7 replicates of a lab fortified
Matrix spiking standards should be prepared from volatile blank containing the analyte at 0.1–5 g/L. Collect all samples
organic compounds which will be representative of the com- in duplicate.
pounds being investigated. The recommended internal standards REFERENCE Method 503.1, Volatile Aromatic & Unsatur-
are chlorobenzene-d5, 1,4-difluorobenzene, 1,4-dichloro- ated Organic Compounds in H2O by Purge and Trap GC, EPA
benzene-d4, and pentafluorobenzene. Using stock standard 600/4-88/039.
solutions, prepare secondary dilution standards containing the
compounds of interest, either singly or mixed together in meth-
anol. Store them in a vial with no headspace for no more than
one week. Surrogates recommended are toluene-d8, 4-bromof- Ethylbenzene EPA Method 602
luorobenzene, and dibromofluoromethane. Each sample CAS #100-41-4
undergoing GC/MS analysis must be spiked with 10 L of the
TITLE Purgeable Aromatics
surrogate spiking solution prior to analysis.
MATRIX Wastewater
846). U.S. EPA 1983, Method 8260A, Rev. 1, Nov. 1990. Office APPLICATION Method covers 7 purgeable aromatics.
of Solid Waste, Washington, DC. (Method 624 provides GC/MS conditions appropriate for the
qualitative and quantitative confirmation of results). EPA
Method describes conditions for a 2nd GC column to confirm
measurements made with primary column.
Ethylbenzene EPA Method 503.1
CAS #100-41-4 INTERFERENCES Impurities in the purge gas and organic
compounds outgassing from the plumbing ahead of the trap.
TITLE Aromatic & Unsaturated VOCs With high- and low-level samples, there can be carryover

contamination. Diffusion of volatile organics through the sep- REFERENCE Method 624, Federal Register Part VIII 40 CFR
tum seal into the sample. Part 136, Oct 26, 1984.
INSTRUMENTATION GC-equipped with photoionization
detector. (With purge-and-trap unit)
RANGE 2.1–550 g/L. CAS #100-41-4
MDL 0.2 g/L.
TITLE Aromatic Volatile Organics
PRECISION 0.26X + 0.23 g/L (overall precision).
ACCURACY 0.94C + 0.31 g/L (as recovery). wastes, and non-water miscible wastes.
SAMPLING METHOD 25-mL glass vial. Teflon®-lined septum. APPLICATION This method is used to analyze for 8 aro-
STABILITY Cool, 4C, 0.008% Na2S2O3. HCl to pH 2. matic VOCs. Samples are analyzed using direct injection or
purge-and-trap methods. Groundwater must be analyzed by
MHT 14 days. the purge-and-trap method. The method provides an optional
QUALITY CONTROL The lab must on an ongoing basis, GC column that is used for analyte confirmation and may also
spike at least 10% of the samples from each sample site being help resolve analytes from interferences.
monitored to assess accuracy. INTERFERENCES There can be carryover contamination
REFERENCE Method 602, Federal Register Part VIII 40 CFR with high- and low-level samples. Impurities may come from
the purge-and-trap apparatus, organic compounds outgassing
Part 136, Oct 26, 1984.
from the plumbing ahead of trap, diffusion of VOCs through
the sample bottle septum during shipping or storage, or from
solvent vapors in the lab.
INSTRUMENTATION GC capable of on-column injections
CAS #100-41-4 or purge-and-trap sample introduction and a photoionization
detector (PID). Column 1: 6 ft by 0.082 in with 5% SP-1200
TITLE Purgeables and 1.75% Bentone-34 on Supelcoport. Column 2: 8 ft by 0.1 in
MATRIX Wastewater with 5% 1,2,3-tris(2-cyanoethoxy)propane on Chromosorb
W-AW.
APPLICATION Method covers 31 purgeable organics. An
inert gas is bubbled through a 5-mL water sample in a specially RANGE 2.1–500 g/L
designed purging chamber. Here, purgeables are transferred MDL 0.2 g/L (reagent water).
from aqueous to gaseous phase, passed onto a sorbent column,
and trapped. Trap is heated and backflushed with inert gas to PQL FACTORS FOR MULTIPLYING  MDL VALUE
desorb purgeables onto a GC column, where purgeables are Matrix Multiplication Factor
separated.
Groundwater 10
INTERFERENCES Impurities in the purge gas, organic com- Low-level soil 10
pounds outgassing from the plumbing ahead of the trap, and Water miscible liquid waste 500
solvent vapors in the lab. With high- and low-level samples, High-level soil and sludge 1250
there can be carryover contamination. Non-water miscible waste 1250
INSTRUMENTATION GC/MS with purge-and-trap unit. PRECISION 0.26X + 0.23 g/L (overall precision).
RANGE 5–600 g/L ACCURACY 0.94C + 0.31 g/L (as recovery).
MDL 7.2 g/L SAMPLING METHOD For water and liquid samples use
glass 40-mL vials with Teflon®-lined septum caps and collect
PRECISION 0.26X–1.72 g/L (overall precision). two vials per sample location with no headspace. For solids
ACCURACY 0.98C + 2.48 g/L (as recovery). and concentrated waste samples use widemouth glass bottles
with Teflon® liners. Cool all samples to 4C
SAMPLING METHOD 25-mL glass vial. Teflon®-lined septum.
STABILITY For concentrated wastes, soils, sediments, or
STABILITY Cool, 4C, 0.008% Na2S2O3. HCl to pH 2. sludges cool to 4C. For liquids, add 4 drops of concentrated
MHT 14 days. hydrochloric acid and cool to 4C.
QUALITY CONTROL The lab must on an ongoing basis, MHT 14 days.

spike at least 5% of the samples from each sample site being QUALITY CONTROL Analyze a reagent blank, matrix spike,
monitored to assess accuracy. and matrix spike duplicate/duplicate for each analytical batch

(up to 20 samples). Demonstrate the purity of glassware and Sample estimated quantitation limits (EQLs) are highly
reagents by analyzing a reagent water method blank. Internal, matrix-dependent. The EQLs listed may not always be achiev-
surrogate, and five concentration level calibration standards are able. EQLs listed for soils or sediments are based on wet weight.
used. The QC check sample concentrate should contain this Normally, data is reported on a dry-weight basis; therefore,
compound at 10 g/mL in methanol. EQLs will be higher, based on the percent dry weight of each
sample. Note that EQLs are even more variable than MDLs and
REFERENCE Test Methods for Evaluating Solid Waste that they are highly variable depending on the matrix being
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC, analyzed.
Method 8020A, Rev. 1, Nov. 1992.
EQL in groundwater in g/L was not listed.
EQL in low soil or sediment in g/kg was not listed.
Ethylene oxide EPA Method 8240 Precision (b) in g/L was not listed.
CAS #75-21-8
TITLE Volatile Organics By GC/MS: Packed Column Technique taining a concentration of C, in g/L.
MATRIX Nearly all types of sample matarices, regardless of average recovery X for samples containing a concentration
water content, can be analyzed using this method. This includes of C in g/L.
groundwater, aqueous sludges, caustic liquors, acid liquors, X = Average recovery found for measurement of samples con-
waste solvents, oily wastes, mousses, tars, fibrous wastes, poly- taining a concentration of C in g/L.
soils, and sediments. MULTIPLICATION FACTORS FOR OTHER MATRICES
organic compounds that are introduced into a gas chromato- Waste miscible liquid waste 50
graph by the purge-and-trap method or by direct injection (in High-concentration soil and sludge 125
limited applications). For the purge-and-trap method an inert Non-water miscible waste 500
gas (zero grade nitrogen or helium) is bubbled through a 5-mL (a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous
solution at ambient temperature. Purged sample components samples, the factor is on a wet-weight basis.
are trapped in a tube of sorbent materials. When purging is
complete, the sorbent tube is heated and backflushed with inert SAMPLING METHOD
INTERFERENCES Impurities in the purge gas and from rinsed with distilled deionized water, and oven dried. However,
organic compounds outgassing from the plumbing ahead of if residual chlorine is present, collect sample in a 40-oz. soil
the trap account for many contamination problems. Interfer- VOA container which has been pre-preserved with 4 drops of
ences purged or coextracted from the samples will vary con- 10% sodium thiosulfate, mix gently, and then transfer the sam-
siderably from source to source. Cross-contamination can ple to a 40-mL VOA vial. Collect bubble-free samples in dupli-
occur whenever high-level and low-level samples are analyzed cate and seal them in separate plastic bags.
Soils or sediments, and sludges — Use an 8-oz. widemouth
analyzed, it should be followed by the analysis of organic-free glass bottle with a Teflon®-faced silicone septum that has been
reagent water to check for cross-contamination. Samples also prewashed with detergent, rinsed with distilled deionized
can be contaminated by diffusion of volatile organics (partic- water, and oven dried. Tap slightly to eliminate free air space.
ularly methylene chloride and fluorocarbons) through the sep- Collect samples in duplicate and seal them in separate plastic bags.
blank can serve as a check on such contamination. The lab SAMPLE PRESERVATION
where volatile analysis is performed and also the refrigerated Liquid samples — Add 4 drops of concentrated HCL and
storage area should be completely free of solvents. immediately cool samples to 4C and store in a solvent-free
refrigerator.
INSTRUMENTATION A gas chromatograph/mass spec-
trometry/data system (GC/MS) equipped with a 6 ft 0.1 in Soils or sediments, and sludges — Cool samples to 4C and
I.D. glass column packed with 1% SP-1000 on Carbopack-B store in a solvent-free refrigerator.
(60/80 mesh) is required.Also needed is a 5-mL purging device, MHT Maximum holding time is 14 days from the date of
a sorbent trap, and a thermal desorption apparatus. sample collection.
PRECISION & ACCURACY This method is reported to have SAMPLE PREPARATION
been tested by 15 laboratories using organic-free reagent water, Liquid samples — Remove the plunger from a 5-mL syringe
drinking water, surface water, and industrial wastewaters (not and carefully pour the sample into the syringe barrel to just
specified) fortified at six concentrations over the range 5– short of overflowing. Replace the syringe plunger and compress
600 g/L. the sample. Open the syringe valve and vent any residual air

bore of the 5-mL syringe, then close the valve. The surrogate
with organic-free reagent water containing the surrogate and REFERENCE Test Methods for Evaluating Solid Waste (SW-
1 mg/kg. Mix the contents of the sample container with a nar- Ethylenethiourea EPA Method 1625
contains the weighed amount of sample, and connect the TITLE Semivolatile Organic Compounds by Isotope Dilu-
device to the purge-and-trap system. tion GC/MS
High-concentration method — This method is based on MATRIX The compounds may be determined in waters,
extracting the sediment or soil with methanol. A waste sample soils, and municipal sludges by this method.
methanol. Wastes that are insoluble in methanol are diluted METHOD SUMMARY This method is used to determine
with reagent tetraglyme or possibly polyethylene glycol (PEG). 176 semivolatile toxic organic pollutants associated with the
An aliquot of the extract is added to organic-free reagent water CWA (as amended 1987); the RCRA (as amended 1986); the
containing surrogate and internal standards. This is purged at CERCLA (as amended 1986); and other compounds amenable
ambient temperature. All samples with an expected concentra- to extraction and analysis by capillary column gas chromatog-
tion of >1.0 mg/kg should be analyzed by this method. raphy-mass spectrometry (GC/MS).
Mix the contents of the sample container with a narrow metal Stable isotopically-labeled analogs of the compounds of interest
spatula. For sediments or soils and solid wastes that are insol- are added to the sample. If the solids content is less than 1%,
uble in methanol, weigh 4 g (wet weight) of sample into a tared a 1-L sample is extracted at pH 12–13, then at pH <2 with
20-mL vial. For waste that is soluble in methanol, tetraglyme, methylene chloride using continuous extraction techniques.
or culture tube or a 10-mL volumetric flask. Quickly add If the solids content is 30% or less, the sample is diluted to 1%
9.0 mL of appropriate solvent then add 1.0 mL of a surrogate solids with reagent water, homogenized ultrasonically, and
spiking solution to the vial, cap it, and shake it for 2 min. extracted at pH 12–13, then at pH <2 with methylene chloride
METHANOL EXTRACT REQUIRED FOR ANALYSIS greater than 30%, the sample is extracted using ultrasonic
OF HIGH-CONCENTRATION SOILS OR SEDIMENTS techniques.
Concentration Range Methanol Extract (a)
500–10,000 g/kg 100 L centrated. Extracts are concentrated to 1 mL if GPC is not
1,000–20,000 g/kg 50 L performed, and to 0.5 mL if GPC is performed.
5,000–100,000 g/kg 10 L
25,000–500,000 g/kg 100 L of 1/50 dilution (b) An internal standard is added to the extract, and a 1-mL aliquot
Calculate appropriate dilution factor for concentrations separated by GC and detected by a MS. The labeled compounds
exceeding this table. serve to correct the variability of the analytical technique.
(a) The volume of methanol added to 5 mL of water being purged INTERFERENCES Solvents, reagents, glassware, and other
should be kept constant. Therefore, add to the 5-mLsyringe whatever sample processing hardware may yield artifacts and/or elevated

to be free from interferences under the conditions of analysis chloride for 24–48 h.
by running method blanks initially and with each sample lot Ultrasonic extraction of high solids samples — Add anhy-
(sample started through the extraction process on a given 8-h drous sodium sulfate to the sample and QC aliquot(s).
shift, to a maximum of 20). Specific selection of reagents and Add acetone:methylene chloride (1:1) to the sample and
purification of solvents by distillation in all glass systems may mix thoroughly
be required. Glassware and, where possible, reagents are
Interferences coextracted from samples will vary considerably QUALITY CONTROL The analyst is permitted to modify
from source to source, depending on the diversity of the site this method to improve separations or lower the costs of mea-
being sampled. surements, provided all performance specifications are met.
apparatus is used to concentrate extracts. For low solids (aqueous samples), extract, concentrate, and
vinyl silicone bonded phased fused silica capillary column. precision and recovery standard. For high solids samples, two
sets of four 30-g aliquots of the high solids reference matrix
PRECISION & ACCURACY The detection limits of the are used.
rather than instrumental limitations. The limits typify the min- Spike all samples with labeled compounds to assess method
imum quantities that can be detected with no interferences performance. Compute percent recovery of the labeled com-
present. pounds using the internal standard method. Compare the
labeled compound recovery for each compound with the cor-
The minimum level (in g/mL) was not listed. This is defined responding labeled compound recovery.
as a minimum level at which the analytical system shall give
recognizable mass spectra (background corrected) and accept- Reagent water and high solids reference matrix blanks are ana-
able calibration points. lyzed to demonstrate freedom from contamination. Extract
and concentrate a 1-L reagent water blank or a high solids
The MDL (in g/kg) in low solids was not listed and in high reference matrix blank with each sample’s lot (samples started
solids was not listed; these were determined in digested sludge through the extraction process on the same 8-h shift, to a
(low solids) and in filter cake or compost (high solids). maximum of 20 samples).
The labeled and native compound initial precision as standard Field replicates may be collected to determine the precision of
deviation (in g/L) was not listed. the sampling technique, and spiked samples may be required
The labeled and native compound initial accuracy as average to determine the accuracy of the analysis when the internal
recovery (in g/L) was not listed. standard method is used.
SAMPLE COLLECTION, PRESERVATION & HANDLING REFERENCE Semivolatile Organic Compounds by Isotope
Collect samples in glass containers. Aqueous samples which Dilution GC/MS. Office of Water Regulation and Standards,
flow freely are collected in refrigerated bottles using automatic U.S. EPA Industrial Technology Division, Washington, DC,
sampling equipment. Solid samples are collected as grab sam- EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
ples using widemouth jars. Maintain samples at 0 to 4C from
the time of collection until extraction. If residual chlorine is
Ethynylestradiol-3 methyl ether EPA Method 1625
SAMPLE PREPARATION Samples containing 1% solids or CAS #72-33-3
extraction techniques. Samples containing 1 to 30% solids are TITLE Semivolatile Organic Compounds by Isotope Dilu-
diluted to the 1% level with reagent water and extracted using tion GC/MS
taining greater than 30% solids are extracted using ultrasonic MATRIX The compounds may be determined in waters,
techniques. soils, and municipal sludges by this method.
Base/neutral extraction — Adjust the pH of the waters in the METHOD SUMMARY This method is used to determine
extractors to 12–13 with 6 N NaOH. Extract with methylene 176 semivolatile toxic organic pollutants associated with the
chloride for 24–48 h. CWA (as amended 1987); the RCRA (as amended 1986); the

CERCLA (as amended 1986); and other compounds amenable The MDL (in g/kg) in low solids was not listed and in high
to extraction and analysis by capillary column gas chromatog- solids was not listed; these were determined in digested sludge
raphy-mass spectrometry (GC/MS). (low solids) and in filter cake or compost (high solids).
Stable isotopically-labeled analogs of the compounds of interest The labeled and native compound initial precision as standard
are added to the sample. If the solids content is less than 1%, deviation (in g/L) was not listed.
a 1-L sample is extracted at pH 12–13, then at pH <2 with The labeled and native compound initial accuracy as average
methylene chloride using continuous extraction techniques. recovery (in g/L) was not listed.
If the solids content is 30% or less, the sample is diluted to 1% SAMPLE COLLECTION, PRESERVATION & HANDLING
solids with reagent water, homogenized ultrasonically, and Collect samples in glass containers. Aqueous samples which
extracted at pH 12–13, then at pH <2 with methylene chloride flow freely are collected in refrigerated bottles using automatic
sampling equipment. Solid samples are collected as grab sam-
techniques.
Each extract is dried over sodium sulfate, concentrated to a of water. Begin sample extraction within 7 days of collection,
volume of 5 mL, cleaned up using GPC, if necessary, and con- and analyze all extracts within 40 days of extraction.
centrated. Extracts are concentrated to 1 mL if GPC is not SAMPLEPREPARATION Samples containing 1% solids or less
performed, and to 0.5 mL if GPC is performed. are extracted directly using continuous liquid-liquid extraction
An internal standard is added to the extract, and a 1-mL aliquot techniques. Samples containing 1 to 30% solids are diluted to the
of the extract is injected into the GC. The compounds are 1% level with reagent water and extracted using continuous
separated by GC and detected by a MS. The labeled compounds liquid-liquid extraction techniques. Samples containing greater
serve to correct the variability of the analytical technique. than 30% solids are extracted using ultrasonic techniques.
INTERFERENCES Solvents, reagents, glassware, and other Base/neutral extraction — Adjust the pH of the waters in the
sample processing hardware may yield artifacts and/or elevated extractors to 12–13 with 6 N NaOH. Extract with methylene
baselines causing misinterpretation of chromatograms and chloride for 24–48 h.
Acid extraction — Adjust the pH of the waters in the extractors
to 2 or less using 6 N sulfuric acid. Extract with methylene
contamination. When results of spikes indicate atypical
with a splitless or on-column injection port for capillary col-
method performance for samples, the samples are diluted to
bring method performance within acceptable limits.
apparatus is used to concentrate extracts. For low solids (aqueous samples), extract, concentrate, and ana-
lyze two sets of four 1-L aliquots (8 aliquots total) of the precision
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1% and recovery standard. For high solids samples, two sets of four
vinyl silicone bonded phased fused silica capillary column. 30-g aliquots of the high solids reference matrix are used.
PRECISION & ACCURACY The detection limits of the Spike all samples with labeled compounds to assess method
method are usually dependent on the level of interferences performance. Compute percent recovery of the labeled com-
rather than instrumental limitations. The limits typify the min- pounds using the internal standard method. Compare the
imum quantities that can be detected with no interferences labeled compound recovery for each compound with the cor-
present. responding labeled compound recovery.
The minimum level (in g/mL) was not listed. This is defined Reagent water and high solids reference matrix blanks are ana-
as a minimum level at which the analytical system shall give lyzed to demonstrate freedom from contamination. Extract
recognizable mass spectra (background corrected) and accept- and concentrate a 1-L reagent water blank or a high solids
able calibration points. reference matrix blank with each sample’s lot (samples started

through the extraction process on the same 8-h shift, to a REFERENCE Semivolatile Organic Compounds by Isotope
maximum of 20 samples). Dilution GC/MS. Office of Water Regulation and Standards,
Field replicates may be collected to determine the precision of EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
the sampling technique, and spiked samples may be required U.S. EPA, Office of Water Regulations and Standards, 401 M
to determine the accuracy of the analysis when the internal St., SW, Washington, DC, 20460. Phone: 202-382-7131).

F
Famphur EPA Method 8270 (a) EQLs listed for soil/sediment are based on wet weight. Nor-
CAS #52-85-7 mally data is reported in a dry-weight basis; therefore, EQLs
TITLE Semivolatile Organic Compounds by GC/MS This calculation is based on a 30-g sample and gel perme-
tion of semivolatile organic compounds in extracts prepared provided for guidance and may not always be achievable.
from all types of solid waste matrices, soils, and groundwater. C = True value for concentration, in g/L.
Although surface waters are not specifically mentioned, this X = Average recovery found for measurements of samples con-
method should be applicable to water samples from rivers, taining a concentration of C, in g/L.
lakes, etc.
METHOD SUMMARY This method covers 259 semivolatile Other Matrices Factor (a)
tion of the sample into the GC/MS system may be appropriate, High-concentration soil and sludges by sonicator 7.5
but this results in very high detection limits (approximately Non-water miscible waste 75
10,000 g/L). Typically, a 1-L liquid sample, containing surro- (a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
gate, and matrix spiking standards, is extracted in a continuous This estimated EQL is similar to an EPA “Practical Quantitation
extractor first under acid conditions and then under basic con- Limit.”
and matrix spiking standards, is extracted ultrasonically. After SAMPLING METHOD
isopropanol).
is performed by GC/MS using a capillary GC column. Soils, sediments, or sludges — Use an 8-oz. widemouth glass
with a screw-top Teflon®-lined cover that has been prewashed
INTERFERENCES Raw GC/MS data from all blanks, sam- with detergent and rinsed with distilled water and methanol
ples, and spikes must be evaluated for interferences. Contam- (or isopropanol).
and low-concentration samples are sequentially analyzed. To SAMPLE PRESERVATION
reduce carryover, the sample syringe must be rinsed out Liquid samples — If residual chlorine is present, add 3 mL of
between samples with solvent. Whenever an unusually concen- 10% sodium thiosulfate per gallon, cool to 4C and store in a
trated sample is encountered, it should be followed by the solvent-free refrigerator until analysis; if chlorine is not present,
analysis of blank solvent to check for cross-contamination. then eliminate the sodium thiosulfate addition.
INSTRUMENTATION A GC/MS and a data system are Soils, sediments, or sludges — Cool samples to 4C and store
0.32 mm I.D.) 1um film thickness silicone-coated fused silica MHT Liquid samples must be extracted within 7 days and
capillary column. A continuous liquid-liquid extractor the extracts analyzed within 40 days. Soils, sediments, or slud-
equipped with Teflon® or glass connection joints and stopcocks ges may be stored for a maximum of 14 days and the extracts
requiring no lubrication, a K-D concentrating apparatus, water analyzed within 40 days.
bath, and an ultrasonic disrupter with a minimum power of SAMPLE PREPARATION
300 W and with pulsing capability are also required. Liquid samples — Transfer 1 L quantitatively to a continuous
PRECISION & ACCURACY The estimated quantitation extractor. If high concentrations are anticipated, a smaller vol-
limit (EQL) of Method 8270B for determining an individual ume may be used and then diluted with organic-free reagent
compound is approximately 1 mg/kg (wet weight) for soil or water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
sediment samples, 1–200 mg/kg for wastes (dependent on sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
solution into each sample. For the sample in each analytical
batch selected for spiking, add 1.0 mL of a matrix spiking stan-
The EQL(b) for groundwater in g/L is 20. should result in a final concentration of 100 ng/L of each
The EQL (a, b) for low concentrations in soil and sediment analyte in the extract to be analyzed (assuming a 1- L injec-
in g/kg is not determined. tion). Extract with methylene chloride for 18–24 h. Next, adjust
Accuracy as g/L is not listed. the pH of the aqueous phase to pH >11 using 10 N sodium
Overall precision in g/L is not listed. hydroxide and extract it with methylene chloride again for

Fenamiphos EPA Method 507
CAS #22224-92-6
concentrator.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous TITLE Determination of Nitrogen and Phosphorus-Con-
or wet samples (gummy or clay type) that do not have a free- taining Pesticides in Water by GC/NPD
MATRIX This method is applicable to the determination of
certain nitrogen and phosphorus-containing pesticides in fin-
ished drinking water and groundwater.
of a matrix spiking standard. For base/neutral acid analysis, the METHOD SUMMARY Method 507 covers 46 nitrogen- and
amount added of the surrogates and matrix spiking com- phosphorus-containing pesticides. A 1-L sample is fortified
pounds should result in a final concentration of 100 ng/ L of with a surrogate standard, salted, buffered, extracted with
each base/neutral analyte and 200 ng/L of each acid analyte methylene chloride, and concentrated; then the solvent is
in the extract to be analyzed (assuming a 1- L injection). exchanged with methyl tert-butyl ether (MTBE) and concen-
Immediately add a 100-mL mixture of 1:1 methylene chlo- trated again, and a 2-L aliquot of a sample extract is injected
ride:acetone and extract the sample ultrasonically for 3 min into a GC system equipped with a selective nitrogen-phospho-
and then decant or filter the extracts. Repeat the extraction two rus detector and a capillary column for analysis.
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. INTERFERENCES Method interferences may be caused by
QUALITY CONTROL A methylene chloride solution con- processing apparatus. Interfering contamination may occur
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is when a sample containing low concentrations of analytes is
used for tuning the GC/MS system each 12-h shift. A system analyzed immediately following a sample containing relatively
performance check also must be made during every 12-h shift. high concentrations. One or more injections of MTBE should
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- be made following the analysis of a sample with high concen-
rophenol, and benzidine is required to verify injection port trations of analytes to check for analyte carryover. Matrix inter-
inertness and GC column performance. A calibration standard ferences may be caused by contaminants that are coextracted
at mid-concentration, containing each compound of interest, from the sample. The extent of matrix interferences will vary
including all required surrogates, must be performed every 12 h considerably from source to source, depending upon the water
during analysis. After the system performance check is met, sampled.
validity of the initial calibration. INSTRUMENTATION A gas chromatograph system (GC)
equipped with a nitrogen-phosphorus detector (NPD) is
The internal standard responses and retention times in the needed.
or during data acquisition. If the retention time for any internal Column 1: 30 m 0.25 mm I.D. DB-5 bonded fused silica col-
standard changes by more than 30 seconds from the last check umn, 0.25 m film thickness, or equivalent.
calibration (12 h), the chromatographic system must be Column 2: 30 m 0.25 mm I.D. DB-1701 bonded fused silica
inspected for malfunctions and corrections must be made, as column, 0.25 m film thickness, or equivalent.
required. If the electron ionization current plot (EICP) area for PRECISION & ACCURACY This method has been validated
any of the internal standards changes by a factor of two from in a single lab and estimated detection limits (EDLs) have been
the last daily calibration standard check, the mass spectrometer determined for each analyte. Observed detection limits may
must be inspected for malfunctions and corrections must be vary among waters, depending upon the nature of the inter-
made, as appropriate. ferences in the sample matrix and the specific instrumentation
Demonstrate, through the analysis of a reagent water blank, used. Analytes that are not separated chromatographically can-
that interferences from the analytical system, glassware, and not be individually identified and measured unless an alterna-
reagents are under control. The blank samples should be car- tive technique for identification and quantification exist.
The estimated detection limit (in g/L) was 1. The EDL is
defined as either method detection limit or a level of compound
in a sample yielding a peak in the final extract with signal-to-
spiked samples must be carried through all stages of the sample The concentration used for these measurements (in g/L) was 10.
preparation and measurement steps. A QC reference sample The accuracy (as % recovery) was 90.
concentrate containing each analyte at a concentration of The precision (% RSD) was 8.
REFERENCE Test Methods for Evaluating Solid Waste (SW- glass sample bottles (prewashed with detergent and hot tap
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office water, rinsed with reagent water, and dried in an oven at 400C
of Solid Waste, Washington, DC. for 1 h) with screw caps lined with PTFE-fluorocarbon.

SAMPLE PRESERVATION Add mercuric chloride to the oratory, Cincinnati, OH, 45268, U.S.A. Available from the
sample bottle in amounts to produce a concentration of National Technical Information Service (NTIS), 5285 Port
10 mg/L. If residual chlorine is present, add 80 mg of sodium Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS
thiosulfate/L of sample to the sample bottle prior to collection. Order Number is PB91-231480.
After collection, seal bottle and shake vigorously for 1 min, then
Fenarimol EPA Method 507
MHT Maximum holding time of the samples, and in some CAS #60168-88-9
cases the extracts, is 14 days.
TITLE Determination of Nitrogen and Phosphorus-Con-
SAMPLE PREPARATION Fortify the sample with 50 L of taining Pesticides in Water by GC/NPD
buffer, add 100 g NaCl to the sample, and seal and shake to MATRIX This method is applicable to the determination of
dissolve the salt; then extract with methylene chloride in a certain nitrogen and phosphorus-containing pesticides in fin-
separatory funnel or in a mechanical tumbler bottle. Dry the ished drinking water and groundwater.
extract by pouring it through a solvent-rinsed drying column
METHOD SUMMARY Method 507 covers 46 nitrogen- and
containing about 10 cm of anhydrous sodium sulfate. Collect
phosphorus-containing pesticides. A 1-L sample is fortified
the extract in a Kuderna-Danish (K-D) concentrator and rinse with a surrogate standard, salted, buffered, extracted with
the column with 20–30 mL methylene chloride. Concentrate methylene chloride, and concentrated; then the solvent is
the extract to about 2 mL and rinse the flask and its lower joint exchanged with methyl tert-butyl ether (MTBE) and concen-
into the concentrator tube with 1 to 2 mL of methyl t-butyl
trated again, and a 2-L aliquot of a sample extract is injected
ether (MTBE). Add 5–10 mL of MTBE and concentrate the into a GC system equipped with a selective nitrogen-phospho-
extract twice (adding more MTBE) to a final volume of 5.0 mL rus detector and a capillary column for analysis.
and store it at 4C until analysis.
Note: If methylene chloride is not completely removed from contaminants in solvents, reagents, glassware, and other sample
the final extract, it may cause detector problems. processing apparatus. Interfering contamination may occur
QUALITY CONTROL Minimum quality control require- when a sample containing low concentrations of analytes is
ments are initial demonstration of lab capability, determina- analyzed immediately following a sample containing relatively
tion of surrogate compound recoveries in each sample and high concentrations. One or more injections of MTBE should
blank, monitoring internal standard peak area or height in each be made following the analysis of a sample with high concen-
sample and blank, analysis of lab reagent blanks, lab fortified trations of analytes to check for analyte carryover. Matrix inter-
samples, lab fortified blanks, and other QC samples. A lab ferences may be caused by contaminants that are coextracted
reagent blank is analyzed to demonstrate that all glassware and from the sample. The extent of matrix interferences will vary
reagent interferences are under control. considerably from source to source, depending upon the water
sampled.
Initial demonstration of capability is fulfilled by analyzing four
fortified reagent water samples with the recovery value for each INSTRUMENTATION A gas chromatograph system (GC)
analyte falling within the acceptable range ( 30% average equipped with a nitrogen-phosphorus detector (NPD) is
recovery). Surrogate recoveries from samples or method blanks needed.
must be 70–130%. The internal standard response for any sam- Column 1: 30 m 0.25 mm I.D. DB-5 bonded fused silica col-
ple chromatogram should not deviate from the daily calibra- umn, 0.25 m film thickness, or equivalent.
tion check standard’s internal standard response by more than Column 2: 30 m 0.25 mm I.D. DB-1701 bonded fused silica
30% or lab fortified blanks and sample matrices are used to column, 0.25 m film thickness, or equivalent.
If the response for the target analyte peak exceeds the working in a single lab and estimated detection limits (EDLs) have been
range of the system, dilute the extract and reanalyze.Alternative determined for each analyte. Observed detection limits may
techniques such as an alternate detector or second chromatog- vary among waters, depending upon the nature of the inter-
raphy column should be used to confirm peak identification ferences in the sample matrix and the specific instrumentation
when sample components are not resolved adequately. used. Analytes that are not separated chromatographically can-
not be individually identified and measured unless an alterna-
tive technique for identification and quantification exist.
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
Drinking Water (WH-550D), 401 M St. SW, Washington, DC The estimated detection limit (in g/L) was 0.38. The EDL is
20460. Tel. (202) 260-3040. For further information the EPA defined as either method detection limit or a level of compound
Safe Drinking Water Hotline may be called at: (800) 426-4791. in a sample yielding a peak in the final extract with signal-to-
Compounds in Drinking Water, EPA/600/4-88/039 (revised The concentration used for these measurements (in g/L) was
July 1991). U.S. EPA Environmental Monitoring Systems Lab- 3.8.

The accuracy (as % recovery) was 99. Drinking Water (WH-550D), 401 M St. SW, Washington, DC
The precision (% RSD) was 5. 20460. Tel. (202) 260-3040. For further information the EPA
Safe Drinking Water Hotline may be called at: (800) 426-4791.
glass sample bottles (prewashed with detergent and hot tap REFERENCE Methods for the Determination of Organic
water, rinsed with reagent water, and dried in an oven at 400C Compounds in Drinking Water, EPA/600/4-88/039 (revised
for 1 h) with screw caps lined with PTFE-fluorocarbon. July 1991). U.S. EPA Environmental Monitoring Systems Lab-
sample bottle in amounts to produce a concentration of
10 mg/L. If residual chlorine is present, add 80 mg of sodium
dark until extraction. Fensulfothion EPA Method 8141
SAMPLE PREPARATION Fortify the sample with 50 L of raphy: Capillary Column Technique
buffer, add 100 g NaCl to the sample, and seal and shake to MATRIX This method covers aqueous and solid matrices.
dissolve the salt; then extract with methylene chloride in a This includes a wide variety such as drinking water, ground-
separatory funnel or in a mechanical tumbler bottle. Dry the water, industrial wastewaters, surface waters, soils, solids, and
extract by pouring it through a solvent-rinsed drying column sediments.
containing about 10 cm of anhydrous sodium sulfate. Collect METHOD SUMMARY This is a GC method used to deter-
the extract in a Kuderna-Danish (K-D) concentrator and rinse mine the concentration of 28 organophosphorus pesticides.
the extract to about 2 mL and rinse the flask and its lower joint The use of Gel Permeation Cleanup (EPA Method 3640) for
into the concentrator tube with 1 to 2 mL of methyl t-butyl sample cleanup has been demonstrated to yield recoveries of
ether (MTBE). Add 5–10 mL of MTBE and concentrate the less than 85% for many method analytes and is therefore not
extract twice (adding more MTBE) to a final volume of 5.0 mL recommended for use with this method.
and store it at 4C until analysis. This method provides GC conditions for the detection of ppb
Note: If methylene chloride is not completely removed from concentrations of organophosphorus compounds. Prior to the
the final extract, it may cause detector problems. use of this method, appropriate sample preparation techniques
QUALITY CONTROL Minimum quality control require- methylene chloride as a solvent by using a separatory funnel
ments are initial demonstration of lab capability, determina- (EPA Method 3510) or a continuous liquid-liquid extractor
tion of surrogate compound recoveries in each sample and (EPA Method 3520). Soxhlet extraction (EPA Method 3540) or
blank, monitoring internal standard peak area or height in each ultrasonic extraction (EPA Method 3550) using methylene
sample and blank, analysis of lab reagent blanks, lab fortified chloride/acetone (1:1) are used for solid samples. Both neat
samples, lab fortified blanks, and other QC samples. A lab and diluted organic liquids (EPA Method 3580) may be ana-
reagent blank is analyzed to demonstrate that all glassware and lyzed by direct injection. Spiked samples are used to verify the
reagent interferences are under control. applicability of the chosen extraction technique to each new
Initial demonstration of capability is fulfilled by analyzing four sample type. A GC with a flame photometric (FPD) or nitro-
fortified reagent water samples with the recovery value for each gen-phosphorus detector (NPD) is used for this multiresidue
analyte falling within the acceptable range ( 30% average procedure.
recovery). Surrogate recoveries from samples or method blanks INTERFERENCES The use of Florisil cleanup materials (EPA
must be 70–130%. The internal standard response for any sam- Method 3620) for some of the compounds in this method has
ple chromatogram should not deviate from the daily calibra- been demonstrated to yield recoveries less than 85% and is
tion check standard’s internal standard response by more than therefore not recommended for all compounds. Use of phos-
30% or lab fortified blanks and sample matrices are used to
the necessity for cleanup for relatively clean sample matrices.
If the response for the target analyte peak exceeds the working If particular circumstances demand the use of an alternative
range of the system, dilute the extract and reanalyze.Alternative cleanup procedure, the analyst must determine the elution pro-
techniques such as an alternate detector or second chromatog- file and demonstrate that the recovery of each analyte is no less
raphy column should be used to confirm peak identification than 85%.
when sample components are not resolved adequately.
Use of a flame photometric detector (FPD) in the phosphorus
EPA CONTACT & HOTLINE For technical questions contact mode will minimize interferences from materials that do not
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and contain phosphorus. Elemental sulfur, however, may interfere

with the determination of certain organophosphorus com- The MDL (in g/kg) when soil was extracted using Soxhlet
pounds by flame photometric gas chromatography. Sulfur extraction (EPA Method 3540) was 4.0.
cleanup using EPA Method 3660 may alleviate this interference. Accuracy (as % recovery) with separatory funnel extraction
A nitrogen phosphorus detector (NPD) is also recommended. ranged from 84 (with low spikes) to 96 (with high spikes).
spikes).
lytes of interest does not occur. Accuracy (as % recovery) with Soxhlet extraction of soils
Method interferences may be caused by contaminants in sol- ranged from 72 (with low spikes to 111 (with high spikes).
vents, reagents, glassware, and other sample processing hard- Accuracy (as % recovery) with ultrasonic extraction of soils
ware that lead to discrete artifacts or elevated baselines in gas ranged from not recovered (with low spikes) to 2 (with high
chromatograms. All these materials must be routinely demon- spikes).
strated to be free from interferences under the conditions of SAMPLE COLLECTION, PRESERVATION & HANDLING
the analysis by analyzing reagent blanks. Containers used to collect samples for the determination of
INSTRUMENTATION A GC with a NPD or a FPD will be semivolatile organic compounds should be soap and water
needed. A data system or integrator is recommended for mea- washed followed by methanol (or isopropanol) rinsing. The
suring peak areas and/or peak heights. A Kuderna-Danish sample containers should be of glass or Teflon® and have screw-
(K-D) apparatus will be needed for extract concentration. top covers with Teflon® liners.
Column 1: 15 m  0.53 mm megabore capillary column, No preservation is used with concentrated waste samples. With
1.0 m film thickness, DB-210. liquid samples containing no residual chlorine and with soil,
Column 2: 15 m  0.53 mm megabore capillary column, sediment, and sludge samples, immediately cooling to 4C is
1.5 m film thickness, SPB-608. the only preservation used. When residual chlorine is present
Column 3: 15 m  0.53 mm megabore capillary column, then 3 mL of 10% aqueous sodium sulfate is added for each
1.0 m film thickness, DB-5. gallon of sample collected, followed by cooling to 4C.
Three megabore capillary columns are included for analysis of Liquid samples must be extracted within 7 days and their
organophosphates by this method. Column 1 (DB-210 or extracts analyzed within 40 days. Concentrated waste, soil, sed-
equivalent) and Column 2 (SPB-608 or equivalent) are recom- iment, and sludge samples must be extracted within 14 days
mended if a large number of organophosphorus analytes are and their extracts analyzed within 40 days.
to be determined. If the superior resolution offered by Column SAMPLE PREPARATION In general, water samples are
1 and Column 2 is not required, Column 3 (DB-5 or equiva- extracted at a neutral pH with methylene chloride, using either
lent) may be used. For megabore capillary columns, automatic EPA Method 3510 or EPA Method 3520. Solid samples are
injections of 1 L are recommended. extracted using either EPA Method 3540 or EPA Method 3550
PRECISION & ACCURACY The MDL actually achieved in with methylene chloride/acetone (1:1) as the extraction solvent.
a given analysis will vary, as it is dependent on instrument Prior to GC analysis, the extraction solvent may be exchanged
sensitivity and matrix effects. Single operator accuracy and to hexane. Single lab data indicates that samples should not be
precision studies have been conducted with spiked water and transferred with 100% hexane during sample workup as the
soil samples. more water soluble organophosphorus compounds may be lost.
MULTIPLICATION FACTORS FOR OTHER MATRICES (a) If cleanup is performed on the samples, the analyst should
Matrix Factor (b) analyze the samples by GC. This will confirm elution patterns
Groundwater 10 and the absence of interferences from the reagents. If peak
(EPA Method 3510 or EPA Method 3520) detection and identification is prevented by the presence of
Low-concentration soil by Soxhlet and no cleanup 10 (c) interferences, further cleanup is required.
Low-concentration soil by ultrasonic extraction 6.7 (c) QUALITY CONTROL The analyst should monitor the per-
with GPC cleanup formance of the extraction, cleanup (when used), and analyt-
High-concentration soil and sludges 500 (c) ical system and the effectiveness of the method in dealing with
by ultrasonic extraction
Non-water miscible waste (EPA Method 3580) 1000 (c)
(a) SampleEQLs are highly matrix-dependent. TheEQLslisted here compounds not expected to be present in the sample). Deu-
are provided for guidance and may not always be achievable. terated analogs of analytes should not be used as surrogates for
(b) EQL = [Method detection limit] [Factor]. For non-aqueous gas chromatographic analysis due to coelution problems.
samples the factor is on a wet-weight basis.
(c) Multiply this factory times the soil MDL.
should be prepared through dilution of the stock standards
The MDL (in g/L) when reagent water was extracted using a with isooctane. One of the concentrations should be at a con-
separatory funnel was 0.08. centration near, but above, the MDL.

Include a mid-level check standard after each group of 10 sam- between samples with solvent. Whenever an unusually concen-
ples in the analysis sequence. GC/MS techniques should be trated sample is encountered, it should be followed by the
judiciously employed to support qualitative identifications analysis of blank solvent to check for cross-contamination.
made with this method. Follow the GC/MS operating require-
ments specified in EPA Method 8270. INSTRUMENTATION A GC/MS and a data system are
When available, chemical ionization mass spectra may be 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
employed to aid in the qualitative identification process. To capillary column. A continuous liquid-liquid extractor
confirm an identification of a compound, the background- equipped with Teflon® or glass connection joints and stopcocks
corrected mass spectrum of the compound must be obtained requiring no lubrication, a K-D concentrating apparatus, water
from the sample extract and must be compared with a mass bath, and an ultrasonic disrupter with a minimum power of
spectrum from a stock or calibration standard analyzed under 300 W and with pulsing capability are also required.
the same chromatographic conditions. The molecular ion and
all other ions present above 20% relative abundance in the mass PRECISION & ACCURACY The estimated quantitation
spectrum of the standard must be present in the mass spectrum limit (EQL) of Method 8270B for determining an individual
of the sample with agreement to 20%. The retention time of compound is approximately 1 mg/kg (wet weight) for soil or
the compound in the sample must be within six seconds of the sediment samples, 1–200 mg/kg for wastes (dependent on
retention time for the same compound in the standard solution. matrix and method of preparation), and 10 g/L for ground-
Should the MS procedure fail to provide satisfactory results, water samples. EQLs will be proportionately higher for sample
additional steps may be taken before reanalysis. These steps extracts that require dilution to avoid saturation of the detector.
may include the use of alternate packed or capillary GC col- The EQL(b) for groundwater in g/L is 40.
umns or additional sample cleanup. The EQL (a, b) for low concentrations in soil and sediment
REFERENCE Test Methods for Evaluating Solid Waste, Phys- in g/kg is not determined.
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office Accuracy as g/L is not listed.
of Solid Waste, Washington, DC, EPA Method 8141 July 1992. Overall precision in g/L is not listed.
Fensulfothion EPA Method 8270 will be higher based on the % dry weight of each sample.
CAS #115-90-2 This calculation is based on a 30-g sample and gel perme-
TITLE Semivolatile Organic Compounds by GC/MS (b) Sample EQLs are highly matrix-dependent. The EQLs are
tion of the sample into the GC/MS system may be appropriate,
10,000 g/L). Typically, a 1-L liquid sample, containing surro- This estimated EQL is similar to an EPA “Practical Quantitation
gate, and matrix spiking standards, is extracted in a continuous Limit.”
and 200 ng of acid surrogates (for a 1-L injection). Analysis Soils, sediments, or sludges — Use an 8-oz. widemouth glass
is performed by GC/MS using a capillary GC column. with a screw-top Teflon®-lined cover that has been prewashed
with detergent and rinsed with distilled water and methanol
(or isopropanol).
ination by carryover can occur whenever high-concentration SAMPLE PRESERVATION
and low-concentration samples are sequentially analyzed. To Liquid samples — If residual chlorine is present, add 3 mL of
reduce carryover, the sample syringe must be rinsed out 10% sodium thiosulfate per gallon, cool to 4C and store in a

solvent-free refrigerator until analysis; if chlorine is not present, The internal standard responses and retention times in the
then eliminate the sodium thiosulfate addition. calibration check standard must be evaluated immediately after
MHT Liquid samples must be extracted within 7 days and inspected for malfunctions and corrections must be made, as
the extracts analyzed within 40 days. Soils, sediments, or slud- required. If the electron ionization current plot (EICP) area for
ges may be stored for a maximum of 14 days and the extracts any of the internal standards changes by a factor of two from
analyzed within 40 days. the last daily calibration standard check, the mass spectrometer
SAMPLE PREPARATION made, as appropriate.
Liquid samples — Transfer 1 L quantitatively to a continuous
extractor. If high concentrations are anticipated, a smaller vol- Demonstrate, through the analysis of a reagent water blank,
ume may be used and then diluted with organic-free reagent that interferences from the analytical system, glassware, and
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) reagents are under control. The blank samples should be car-
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking ried through all stages of the sample preparation and measure-
solution into each sample. For the sample in each analytical ment steps. For each analytical batch (up to 20 samples), a
batch selected for spiking, add 1.0 mL of a matrix spiking stan- reagent blank, matrix spike, and matrix spike duplicate/dupli-
dard. For base/neutral acid analysis, the amount of the surro- cate must be analyzed (the frequency of the spikes may be
gates and matrix spiking compounds added to the sample different for different monitoring programs). The blank and
should result in a final concentration of 100 ng/L of each spiked samples must be carried through all stages of the sample
analyte in the extract to be analyzed (assuming a 1- L injec- preparation and measurement steps. A QC reference sample
tion). Extract with methylene chloride for 18–24 h. Next, adjust concentrate containing each analyte at a concentration of
the pH of the aqueous phase to pH >11 using 10 N sodium 100 mg/L in methanol is required.
hydroxide and extract it with methylene chloride again for REFERENCE Test Methods for Evaluating Solid Waste (SW-
18–24 h. Dry the extract through a column containing anhy- 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
drous sodium sulfate and concentrate it to 1 mL using a K-D of Solid Waste, Washington, DC.
concentrator.
or wet samples (gummy or clay type) that do not have a free- Fensulfothion EPA Method 8140
flowing sandy texture must be mixed with anhydrous sodium CAS #115-90-2
standards to all samples, spikes, standards, and blanks. For the TITLE Organophosphorus Pesticides
wastes, and non-water miscible wastes.
amount added of the surrogates and matrix spiking com-
pounds should result in a final concentration of 100 ng/ L of APPLICATION This method is used for the analysis of 21
each base/neutral analyte and 200 ng/L of each acid analyte organophosphorus pesticides. Samples are extracted, concen-
in the extract to be analyzed (assuming a 1- L injection). trated, and analyzed using direct injection of both neat and
Immediately add a 100-mL mixture of 1:1 methylene chlo- diluted organic liquid into a gas chromatograph (GC).
ride:acetone and extract the sample ultrasonically for 3 min INTERFERENCES Solvents, reagents, and glassware may
and then decant or filter the extracts. Repeat the extraction two introduce artifacts. Other interferences may come from coex-
or more times. Dry the extract using a column with anhydrous tracted compounds from samples. The use of Florisil cleanup
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. materials may produce low recoveries. Elemental sulfur may
QUALITY CONTROL A methylene chloride solution con- interfere with some compounds when using a flame photomet-
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is ric detector. Sulfur cleanup (Method 3660) may alleviate sulfur
used for tuning the GC/MS system each 12-h shift. A system interference.
performance check also must be made during every 12-h shift. INSTRUMENTATION GC capable of on-column injections
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- and a flame photometric detector (FPD) or a thermionic detec-
rophenol, and benzidine is required to verify injection port tor. Column 1: 1.8 m by 2 mm with 5% SP-2401 on Supelco-
inertness and GC column performance. A calibration standard port. Column 2: 1.8 m by 2 mm with 3% SP-2401 on
at mid-concentration, containing each compound of interest, Supelcoport. Column 3: 50 cm by in eflon® with 15% SE-
including all required surrogates, must be performed every 12 h 54 on Gas Chrom Q. The preferred column is Column Number 1.
RANGE 23.9–110 g/L
validity of the initial calibration. MDL 1.5 g/L (in reagent water).

PQL FACTORS FOR MULTIPLYING  FID MDL VALUE ultrasonic extraction (EPA Method 3550) using methylene
Matrix Multiplication Factor chloride/acetone (1:1) are used for solid samples. Both neat
Groundwater 10 lyzed by direct injection. Spiked samples are used to verify the
Low-level soil by sonication with GPC cleanup 670 applicability of the chosen extraction technique to each new
High-level soil and sludge by sonication 10,000 sample type. A GC with a flame photometric (FPD) or nitro-
Non-water miscible waste 100,000 gen-phosphorus detector (NPD) is used for this multiresidue
PRECISION 17.1% (single operator standard deviation) procedure.
ACCURACY 94.1% (single operator average recovery) INTERFERENCES The use of Florisil cleanup materials (EPA
Method 3620) for some of the compounds in this method has
SAMPLING METHOD Use 8-oz. widemouth glass bottles been demonstrated to yield recoveries less than 85% and is
with Teflon®-lined caps for concentrated waste samples, soils, therefore not recommended for all compounds. Use of phos-
sediments, and sludges. Use 1 or 2½ gallon amber glass bottles phorus or halogen specific detectors, however, often obviates
with Teflon®-lined caps for liquid (water) samples. the necessity for cleanup for relatively clean sample matrices.
STABILITY Cool soil, sediment, sludge, and liquid samples If particular circumstances demand the use of an alternative
to 4C. If residual chlorine is present in liquid samples add cleanup procedure, the analyst must determine the elution pro-
3 mL of 10% sodium thiosulfate per gallon of sample and cool file and demonstrate that the recovery of each analyte is no less
to 4C. than 85%.
MHT 14 days for concentrated waste, soil, sediment, or Use of a flame photometric detector (FPD) in the phosphorus
sludge; 7 days for liquid samples; all extracts must be analyzed mode will minimize interferences from materials that do not
within 40 days. contain phosphorus. Elemental sulfur, however, may interfere
with the determination of certain organophosphorus com-
QUALITY CONTROL A quality control check sample con- pounds by flame photometric gas chromatography. Sulfur
centrate containing this compound in acetone at a concentra- cleanup using EPA Method 3660 may alleviate this interference.
tion 1,000 times more concentrated than the selected spike A nitrogen phosphorus detector (NPD) is also recommended.
concentration is required. The QC check sample concentrate
may be prepared from pure standard materials or purchased A few analytes coelute on certain columns. Therefore, select a
as certified solutions. Use appropriate trip, matrix, control site, second column for confirmation where coelution of the ana-
method, reagent, and solvent blanks. Internal, surrogate, and lytes of interest does not occur.
five concentration level calibration standards are used. Method interferences may be caused by contaminants in sol-
REFERENCE Method 8140, SW-846, 3rd ed., Sept. 1986. vents, reagents, glassware, and other sample processing hard-
ware that lead to discrete artifacts or elevated baselines in gas
Fenthion EPA Method 8141 the analysis by analyzing reagent blanks.
CAS #55-38-9
INSTRUMENTATION A GC with a NPD or a FPD will be
TITLE Organophosphorus Compounds by Gas Chromatog- needed. A data system or integrator is recommended for mea-
raphy: Capillary Column Technique suring peak areas and/or peak heights. A Kuderna-Danish
MATRIX This method covers aqueous and solid matrices.
This includes a wide variety such as drinking water, ground- Column 1: 15 m  0.53 mm megabore capillary column,
water, industrial wastewaters, surface waters, soils, solids, and 1.0 m film thickness, DB-210.
sediments. Column 2: 15 m  0.53 mm megabore capillary column,
METHOD SUMMARY This is a GC method used to deter- Column 3: 15 m  0.53 mm megabore capillary column,
mine the concentration of 28 organophosphorus pesticides. 1.0 m film thickness, DB-5.
The use of Gel Permeation Cleanup (EPA Method 3640) for Three megabore capillary columns are included for analysis of
sample cleanup has been demonstrated to yield recoveries of organophosphates by this method. Column 1 (DB-210 or
less than 85% for many method analytes and is therefore not equivalent) and Column 2 (SPB-608 or equivalent) are recom-
recommended for use with this method. mended if a large number of organophosphorus analytes are
to be determined. If the superior resolution offered by Column
This method provides GC conditions for the detection of ppb
1 and Column 2 is not required, Column 3 (DB-5 or equiva-
concentrations of organophosphorus compounds. Prior to the
lent) may be used. For megabore capillary columns, automatic
use of this method, appropriate sample preparation techniques
injections of 1 L are recommended.
methylene chloride as a solvent by using a separatory funnel PRECISION & ACCURACY The MDL actually achieved in
(EPA Method 3510) or a continuous liquid-liquid extractor a given analysis will vary, as it is dependent on instrument
(EPA Method 3520). Soxhlet extraction (EPA Method 3540) or sensitivity and matrix effects. Single operator accuracy and

precision studies have been conducted with spiked water and Prior to GC analysis, the extraction solvent may be exchanged
soil samples. to hexane. Single lab data indicates that samples should not be
transferred with 100% hexane during sample workup as the
MULTIPLICATION FACTORS FOR OTHER MATRICES (a) more water soluble organophosphorus compounds may be lost.
Matrix Factor (b)
If cleanup is performed on the samples, the analyst should
Groundwater 10 analyze the samples by GC. This will confirm elution patterns
(EPA Method 3510 or EPA Method 3520) and the absence of interferences from the reagents. If peak
Low-concentration soil by Soxhlet and no cleanup 10 (c) detection and identification is prevented by the presence of
Low-concentration soil by ultrasonic extraction 6.7 (c) interferences, further cleanup is required.
with GPC cleanup
High-concentration soil and sludges 500 (c) QUALITY CONTROL The analyst should monitor the per-
by ultrasonic extraction formance of the extraction, cleanup (when used), and analyt-
Non-water miscible waste (EPA Method 3580) 1000 (c) ical system and the effectiveness of the method in dealing with
(a) SampleEQLs are highly matrix-dependent. TheEQLslisted here blank with one or two surrogates (e.g., organophosphorus
are provided for guidance and may not always be achievable. compounds not expected to be present in the sample). Deu-
(b) EQL = [Method detection limit] [Factor]. For non-aqueous terated analogs of analytes should not be used as surrogates for
samples the factor is on a wet-weight basis. gas chromatographic analysis due to coelution problems.
(c) Multiply this factory times the soil MDL.
The MDL (in g/L) when reagent water was extracted using a should be prepared through dilution of the stock standards
separatory funnel was 0.08. with isooctane. One of the concentrations should be at a con-
The MDL (in g/kg) when soil was extracted using Soxhlet centration near, but above, the MDL.
extraction (EPA Method 3540) was 5.0.
Accuracy (as % recovery) with separatory funnel extraction Include a mid-level check standard after each group of 10 sam-
ranged from not recovered (with low spikes) to 89 (with
judiciously employed to support qualitative identifications
high spikes).
made with this method. Follow the GC/MS operating require-
ments specified in EPA Method 8270.
spikes). When available, chemical ionization mass spectra may be
Accuracy (as % recovery) with Soxhlet extraction of soils employed to aid in the qualitative identification process. To
ranged from not recovered (with low spikes to 89 (with high confirm an identification of a compound, the background-
spikes). corrected mass spectrum of the compound must be obtained
Accuracy (as % recovery) with ultrasonic extraction of soils from the sample extract and must be compared with a mass
ranged from not recovered (with low spikes) to 84 (with spectrum from a stock or calibration standard analyzed under
high spikes). the same chromatographic conditions. The molecular ion and
all other ions present above 20% relative abundance in the mass
SAMPLE COLLECTION, PRESERVATION & HANDLING spectrum of the standard must be present in the mass spectrum
Containers used to collect samples for the determination of of the sample with agreement to 20%. The retention time of
semivolatile organic compounds should be soap and water the compound in the sample must be within six seconds of the
washed followed by methanol (or isopropanol) rinsing. The retention time for the same compound in the standard solution.
sample containers should be of glass or Teflon® and have screw- Should the MS procedure fail to provide satisfactory results,
top covers with Teflon® liners. additional steps may be taken before reanalysis. These steps
No preservation is used with concentrated waste samples. With may include the use of alternate packed or capillary GC col-
liquid samples containing no residual chlorine and with soil, umns or additional sample cleanup.
sediment, and sludge samples, immediately cooling to 4C is REFERENCE Test Methods for Evaluating Solid Waste, Phys-
the only preservation used. When residual chlorine is present ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
then 3 mL of 10% aqueous sodium sulfate is added for each of Solid Waste, Washington, DC, EPA Method 8141 July 1992.
gallon of sample collected, followed by cooling to 4C.
extracts analyzed within 40 days. Concentrated waste, soil, sed- Fenthion EPA Method 8270
iment, and sludge samples must be extracted within 14 days CAS #55-38-9
and their extracts analyzed within 40 days.
extracted at a neutral pH with methylene chloride, using either MATRIX This method is used to determine the concentra-
EPA Method 3510 or EPA Method 3520. Solid samples are tion of semivolatile organic compounds in extracts prepared
extracted using either EPA Method 3540 or EPA Method 3550 from all types of solid waste matrices, soils, and groundwater.
with methylene chloride/acetone (1:1) as the extraction solvent. Although surface waters are not specifically mentioned, this

(a) EQL forother matrices =[EQL forlow soil/sediment] [Factor].
isopropanol).
(or isopropanol).
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
in g/kg is not 18–24 h. Dry the extract through a column containing anhy-
determined. Accuracy as g/L drous sodium sulfate and concentrate it to 1 mL using a K-D
is not listed. concentrator.
Overall precision in g/L is not listed.
C = True value for concentration, in g/L. amount added of the surrogates and matrix spiking com-
X = Average recovery found for measurements of samples con- pounds should result in a final concentration of 100 ng/L of
taining a concentration of C, in g/L. each base/neutral analyte and 200 ng/L of each acid analyte

in the extract to be analyzed (assuming a 1- L injection). INTERFERENCES Solvents, reagents, and glassware may
Immediately add a 100-mL mixture of 1:1 methylene chlo- introduce artifacts. Other interferences may come from coex-
ride:acetone and extract the sample ultrasonically for 3 min tracted compounds from samples. The use of Florisil cleanup
and then decant or filter the extracts. Repeat the extraction two materials may produce low recoveries. Elemental sulfur may
or more times. Dry the extract using a column with anhydrous interfere with some compounds when using a flame photomet-
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. ric detector. Sulfur cleanup (Method 3660) may alleviate sulfur
interference.
QUALITY CONTROL A methylene chloride solution con-
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is INSTRUMENTATION GC capable of on-column injections
used for tuning the GC/MS system each 12-h shift. A system and a flame photometric detector (FPD) or a thermionic detec-
performance check also must be made during every 12-h shift. tor. Column 1: 1.8 m by 2 mm with 5% SP-2401 on Supelco-
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- port. Column 2: 1.8 m by 2 mm with 3% SP-2401 on
rophenol, and benzidine is required to verify injection port Supelcoport. Column 3: 50 cm by in eflon® with 15% SE-
inertness and GC column performance. A calibration standard 54 on Gas Chrom Q. The preferred column is Column Number 1.
RANGE 5.3–64 g/L
during analysis. After the system performance check is met, MDL 0.10 g/L (in reagent water).
validity of the initial calibration. PQL FACTORS FOR MULTIPLYING  FID MDL VALUE
Matrix Multiplication Factor
calibration check standard must be evaluated immediately after Groundwater 10
or during data acquisition. If the retention time for any internal Low-level soil by sonication with GPC cleanup 670
standard changes by more than 30 seconds from the last check High-level soil and sludge by sonication 10,000
calibration (12 h), the chromatographic system must be Non-water miscible waste 100,000
inspected for malfunctions and corrections must be made, as PRECISION 19.9% (single operator standard deviation)
any of the internal standards changes by a factor of two from ACCURACY 68.7% (single operator average recovery)
SAMPLING METHOD Use 8-oz. widemouth glass bottles
with Teflon®-lined caps for concentrated waste samples, soils,
sediments, and sludges. Use 1 or 2½ gallon amber glass bottles
Demonstrate, through the analysis of a reagent water blank, with Teflon®-lined caps for liquid (water) samples.
STABILITY Cool soil, sediment, sludge, and liquid samples
to 4C. If residual chlorine is present in liquid samples add
3 mL of 10% sodium thiosulfate per gallon of sample and cool
to 4C.
cate must be analyzed (the frequency of the spikes may be MHT 14 days for concentrated waste, soil, sediment, or
different for different monitoring programs). The blank and sludge; 7 days for liquid samples; all extracts must be analyzed
spiked samples must be carried through all stages of the sample within 40 days.
QUALITY CONTROL A quality control check sample con-
centrate containing this compound in acetone at a concentra-
tion 1,000 times more concentrated than the selected spike
REFERENCE Test Methods for Evaluating Solid Waste (SW- concentration is required. The QC check sample concentrate
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office may be prepared from pure standard materials or purchased
of Solid Waste, Washington, DC. as certified solutions. Use appropriate trip, matrix, control site,
method, reagent, and solvent blanks. Internal, surrogate, and
five concentration level calibration standards are used.
Fenthion EPA Method 8140 REFERENCE Method 8140, SW-846, 3rd ed., Sept. 1986.
CAS #55-38-9
TITLE Organophosphorus Pesticides

Fluchloralin EPA Method 8270
MATRIX Groundwater, soils, sludges, water miscible liquid CAS #33245-39-5
APPLICATION This method is used for the analysis of 21
organophosphorus pesticides. Samples are extracted, concen- MATRIX This method is used to determine the concentra-
trated, and analyzed using direct injection of both neat and tion of semivolatile organic compounds in extracts prepared
diluted organic liquid into a gas chromatograph (GC). from all types of solid waste matrices, soils, and groundwater.

lakes, etc.
Limit.”
The EQL(b) for groundwater in g/L is 20. the pH of the aqueous phase to pH >11 using 10 N sodium
in g/kg is not 18–24 h. Dry the extract through a column containing anhy-
determined. Accuracy as g/L drous sodium sulfate and concentrate it to 1 mL using a K-D
is not listed. concentrator.
Overall precision in g/L is not listed.
C = True value for concentration, in g/L. amount added of the surrogates and matrix spiking com-
X = Average recovery found for measurements of samples con- pounds should result in a final concentration of 100 ng/L of
taining a concentration of C, in g/L. each base/neutral analyte and 200 ng/L of each acid analyte

in the extract to be analyzed (assuming a 1- L injection). CERCLA (as amended 1986); and other compounds amenable
Immediately add a 100-mL mixture of 1:1 methylene chlo- to extraction and analysis by capillary column gas chromatog-
ride:acetone and extract the sample ultrasonically for 3 min raphy-mass spectrometry (GC/MS).
or more times. Dry the extract using a column with anhydrous Stable isotopically-labeled analogs of the compounds of interest
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. are added to the sample. If the solids content is less than 1%,
a 1-L sample is extracted at pH 12–13, then at pH <2 with
QUALITY CONTROL A methylene chloride solution con- methylene chloride using continuous extraction techniques.
If the solids content is 30% or less, the sample is diluted to 1%
solids with reagent water, homogenized ultrasonically, and
extracted at pH 12–13, then at pH <2 with methylene chloride
rophenol, and benzidine is required to verify injection port
at mid-concentration, containing each compound of interest, techniques.
including all required surrogates, must be performed every 12 h Each extract is dried over sodium sulfate, concentrated to a
during analysis. After the system performance check is met, volume of 5 mL, cleaned up using GPC, if necessary, and con-
calibration check compounds (CCCs) are used to check the centrated. Extracts are concentrated to 1 mL if GPC is not
validity of the initial calibration. performed, and to 0.5 mL if GPC is performed.
The internal standard responses and retention times in the An internal standard is added to the extract, and a 1-mL aliquot
calibration check standard must be evaluated immediately after of the extract is injected into the GC. The compounds are
or during data acquisition. If the retention time for any internal separated by GC and detected by a MS. The labeled compounds
standard changes by more than 30 seconds from the last check serve to correct the variability of the analytical technique.
inspected for malfunctions and corrections must be made, as INTERFERENCES Solvents, reagents, glassware, and other
required. If the electron ionization current plot (EICP) area for sample processing hardware may yield artifacts and/or elevated
any of the internal standards changes by a factor of two from baselines causing misinterpretation of chromatograms and
the last daily calibration standard check, the mass spectrometer spectra. Materials used in the analysis must be demonstrated
must be inspected for malfunctions and corrections must be to be free from interferences under the conditions of analysis
made, as appropriate. by running method blanks initially and with each sample lot
Demonstrate, through the analysis of a reagent water blank, shift, to a maximum of 20). Specific selection of reagents and
that interferences from the analytical system, glassware, and purification of solvents by distillation in all glass systems may
reagents are under control. The blank samples should be car- be required. Glassware and, where possible, reagents are
ried through all stages of the sample preparation and measure- cleaned by solvent rinse and baking at 450C for 1-h minimum.
ment steps. For each analytical batch (up to 20 samples), a Interferences coextracted from samples will vary considerably
reagent blank, matrix spike, and matrix spike duplicate/dupli- from source to source, depending on the diversity of the site
cate must be analyzed (the frequency of the spikes may be being sampled.
spiked samples must be carried through all stages of the sample INSTRUMENTATION Major instrumentation includes a GC
preparation and measurement steps. A QC reference sample with a splitless or on-column injection port for capillary col-
concentrate containing each analyte at a concentration of umn, a MS with 70 eV electron impact ionization, and a data
100 mg/L in methanol is required. system to collect and record MS data, and process it. A K-D
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
of Solid Waste, Washington, DC. vinyl silicone bonded phased fused silica capillary column.
Fluoranthene EPA Method 1625 rather than instrumental limitations. The limits typify the min-
CAS #206-44-0 imum quantities that can be detected with no interferences
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu-
The minimum level (in g/mL) was 10. This is defined as a
tion GC/MS
minimum level at which the analytical system shall give recog-
MATRIX The compounds may be determined in waters, nizable mass spectra (background corrected) and acceptable
soils, and municipal sludges by this method. calibration points.
METHOD SUMMARY This method is used to determine The MDL (in g/kg) in low solids was 54 and in high solids
176 semivolatile toxic organic pollutants associated with the was 22; these were determined in digested sludge (low solids)
CWA (as amended 1987); the RCRA (as amended 1986); the and in filter cake or compost (high solids).

deviation (in g/L) was 33. the sampling technique, and spiked samples may be required
The labeled and native compound initial accuracy as average to determine the accuracy of the analysis when the internal
recovery (in g/L) was 71–177. standard method is used.
SAMPLE COLLECTION, PRESERVATION & HANDLING REFERENCE Semivolatile Organic Compounds by Isotope
Collect samples in glass containers. Aqueous samples which Dilution GC/MS. Office of Water Regulation and Standards,
flow freely are collected in refrigerated bottles using automatic U.S. EPA Industrial Technology Division, Washington, DC,
sampling equipment. Solid samples are collected as grab sam- EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
ples using widemouth jars. Maintain samples at 0 to 4C from U.S. EPA, Office of Water Regulations and Standards, 401 M
the time of collection until extraction. If residual chlorine is St., SW, Washington, DC, 20460. Phone: 202-382-7131).
and analyze all extracts within 40 days of extraction. Fluoranthene EPA Method 625
SAMPLE PREPARATION Samples containing 1% solids or CAS #206-44-0
extraction techniques. Samples containing 1 to 30% solids are TITLE Base/Neutrals and Acids, U.S. EPA Method 625
diluted to the 1% level with reagent water and extracted using MATRIX This methods covers municipal and industrial
continuous liquid-liquid extraction techniques. Samples con- wastewaters.
techniques. METHOD SUMMARY Approximately 1 L of sample is seri-
Base/neutral extraction — Adjust the pH of the waters in the and again at a pH less than 2 using a separatory funnel or a
extractors to 12–13 with 6 N NaOH. Extract with methylene continuous extractor. The methylene chloride extract is dried,
chloride for 24–48 h. concentrated to a volume of 1 mL, and analyzed by GC/MS.
Acid extraction — Adjust the pH of the waters in the extractors Qualitative identification of the parameters in the extract is
to 2 or less using 6 N sulfuric acid. Extract with methylene performed using the retention time and the relative abundance
chloride for 24–48 h. of three characteristic masses (m/z). Qualitative analysis is per-
Ultrasonic extraction of high solids samples — Add anhy- formed using either external or internal standard techniques
drous sodium sulfate to the sample and QC aliquot(s). with a single characteristic m/z.
Add acetone:methylene chloride (1:1) to the sample and
mix thoroughly contaminants in solvents, reagents, glassware, and other sample
Concentrate extracts using a K-D apparatus. processing hardware. Glassware must be scrupulously cleaned.
Glassware should be heated in a muffle furnace at 400C for 5
QUALITY CONTROL The analyst is permitted to modify to 30 min. Some thermally stable materials, such as PCBs, may
this method to improve separations or lower the costs of mea- not be eliminated by this treatment. Solvent rinses with acetone
surements, provided all performance specifications are met. and pesticide quality hexane may be substituted for the muffle
Analyses of blanks are required to demonstrate freedom from furnace heating. Matrix interferences may be caused by con-
contamination. When results of spikes indicate atypical taminants that are coextracted from the sample. The base-
method performance for samples, the samples are diluted to neutral extraction may cause significantly reduced recovery of
bring method performance within acceptable limits. phenols. The packed gas chromatographic columns recom-
For low solids (aqueous samples), extract, concentrate, and mended for the basic fraction may not exhibit sufficient reso-
analyze two sets of four 1-L aliquots (8 aliquots total) of the lution for some analytes.
precision and recovery standard. For high solids samples, two INSTRUMENTATION A GC/MS system with an injection
sets of four 30-g aliquots of the high solids reference matrix port designed for on-column injection when using packed col-
are used. umns and for splitless injection when using capillary columns.
Spike all samples with labeled compounds to assess method Column for base/neutrals: 1.8 m long  2 mm I.D. glass,
performance. Compute percent recovery of the labeled com- packed with 3% SP-2550 on Supelcoport (100/120 mesh)
pounds using the internal standard method. Compare the or equivalent.
labeled compound recovery for each compound with the cor- Column for acids: 1.8 m long 2 mm I.D. glass, packed with
responding labeled compound recovery. 1% SP-1240DA on Supelcoport (100/120 mesh) or equivalent.
Reagent water and high solids reference matrix blanks are ana- PRECISION & ACCURACY The MDL concentrations were
lyzed to demonstrate freedom from contamination. Extract obtained using reagent water. The MDL actually achieved in a
and concentrate a 1-L reagent water blank or a high solids given analysis will vary depending on instrument sensitivity
reference matrix blank with each sample’s lot (samples started and matrix effects. This method was tested by 15 laboratories
through the extraction process on the same 8-h shift, to a using reagent water, drinking water, surface water, and indus-
maximum of 20 samples). trial wastewaters spiked at six concentrations over the range 5

Fluoranthene EPA Method 8270
method accuracy were found to be directly related to the con- CAS #206-44-0
The MDL (in g/L) in reagent water was 2.2. TITLE Semivolatile Organic Compounds by GC/MS
The standard deviation (in g/L based on 4 recovery measure- MATRIX This method is used to determine the concentra-
ments) was 32.8. tion of semivolatile organic compounds in extracts prepared
The range (in g/L) for average recovery for 4 measurements from all types of solid waste matrices, soils, and groundwater.
was 42.9–121.3. Although surface waters are not specifically mentioned, this
The range (in %) for percent recovery was 26–137. method should be applicable to water samples from rivers,
Accuracy (in g/L) as expected recovery for one or more mea- lakes, etc.
C was 0.81C + 1.10. METHOD SUMMARY This method covers 259 semivolatile
Precision (in g/L) as expected single analyst standard devia- organic compounds. In very limited applications direct injec-
tion of measurements at an average concentration found at tion of the sample into the GC/MS system may be appropriate,
X was 0.22X–0.73. but this results in very high detection limits (approximately
Overall precision (in g/L) as expected interlaboratory stan- 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
dard deviation of measurements in an average concentra- gate, and matrix spiking standards, is extracted in a continuous
tion found at X was 0.28X–0.60. extractor first under acid conditions and then under basic con-
C = True value of the concentration in g/L. and matrix spiking standards, is extracted ultrasonically. After
X = Average recovery found for measurements of samples con- concentrating the extract to 1 mL it is spiked with 10 L of an
taining a concentration at C in g/L. internal standard solution just prior to analysis by GC/MS. The
SAMPLE PREPARATION Adjust the pH to >11 with sodium volume injected should contain about 100 ng of base/neutral
hydroxide and serially extract in a separatory funnel with meth- and 200 ng of acid surrogates (for a 1-L injection). Analysis
ylene chloride or else in a continuous extractor. Next, adjust is performed by GC/MS using a capillary GC column.
the pH to <2 with sulfuric acid and serially extract in a sepa- INTERFERENCES Raw GC/MS data from all blanks, sam-
ratory funnel with methylene chloride or else in a continuous ples, and spikes must be evaluated for interferences. Contam-
extractor. Dry the extracts separately through a column of ination by carryover can occur whenever high-concentration
anhydrous sodium sulfate and then concentrate each of the and low-concentration samples are sequentially analyzed. To
extracts to 1.0 mL using a K-D apparatus. reduce carryover, the sample syringe must be rinsed out
SAMPLE COLLECTION, PRESERVATION & HANDLING between samples with solvent. Whenever an unusually concen-
Grab samples must be collected in glass containers. All samples trated sample is encountered, it should be followed by the
must be refrigerated at 4C from the time of collection until analysis of blank solvent to check for cross-contamination.
extraction. If residual chlorine is present, add 80 mg of sodium INSTRUMENTATION A GC/MS and a data system are
thiosulfate/L of sample and mix well. All samples must be required. The GC column used is a 30 m 0.25 mm I.D. (or
extracted within 7 days of collection and completely analyzed 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
within 40 days of extraction. capillary column. A continuous liquid-liquid extractor
QUALITY CONTROL Make an initial, one-time, demonstra- equipped with Teflon® or glass connection joints and stopcocks
tion of the ability to generate acceptable accuracy and precision requiring no lubrication, a K-D concentrating apparatus, water
with this method. Before processing any samples, the analyst bath, and an ultrasonic disrupter with a minimum power of
must analyze a reagent water blank to demonstrate that inter- 300 W and with pulsing capability are also required.
ferences from the analytical system and glassware are under PRECISION & ACCURACY The estimated quantitation
control. Each time a set of samples is extracted or reagents are limit (EQL) of Method 8270B for determining an individual
changed, a reagent water blank must be processed. Spike and compound is approximately 1 mg/kg (wet weight) for soil or
analyze a minimum of 5% of all samples to monitor and eval- sediment samples, 1–200 mg/kg for wastes (dependent on
uate lab data quality. A QC check sample concentrate that matrix and method of preparation), and 10 g/L for ground-
contains each parameter of interest at a concentration of water samples. EQLs will be proportionately higher for sample
100 g/mL in acetone is required. PCBs and multicomponent extracts that require dilution to avoid saturation of the detector.
After analysis of five spiked wastewater samples, calculate the The EQL (a, b) for low concentrations in soil and sediment
average percent recovery and the standard deviation of the in g/kg is 660.
percent recovery. Spike all samples with the surrogate standard Accuracy as g/L is 0.81C + 1.10.
spiking solution and calculate the percent recovery of each Overall precision in g/L is 0.28X–0.60.
surrogate compound.
REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct. mally data is reported in a dry-weight basis; therefore, EQLs
26, 1984. will be higher based on the % dry weight of each sample.

This estimated EQL is similar to an EPA “Practical Quantitation QUALITY CONTROL A methylene chloride solution con-
Limit.” taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
SAMPLING METHOD
Soils, sediments, or sludges — Use an 8-oz. widemouth glass including all required surrogates, must be performed every 12 h
with a screw-top Teflon®-lined cover that has been prewashed during analysis. After the system performance check is met,
with detergent and rinsed with distilled water and methanol calibration check compounds (CCCs) are used to check the
(or isopropanol). validity of the initial calibration.
SAMPLE PRESERVATION The internal standard responses and retention times in the
Liquid samples — If residual chlorine is present, add 3 mL of calibration check standard must be evaluated immediately after
10% sodium thiosulfate per gallon, cool to 4C and store in a or during data acquisition. If the retention time for any internal
solvent-free refrigerator until analysis; if chlorine is not present, standard changes by more than 30 seconds from the last check
then eliminate the sodium thiosulfate addition. calibration (12 h), the chromatographic system must be
MHT Liquid samples must be extracted within 7 days and the last daily calibration standard check, the mass spectrometer
the extracts analyzed within 40 days. Soils, sediments, or slud- must be inspected for malfunctions and corrections must be
ges may be stored for a maximum of 14 days and the extracts made, as appropriate.
analyzed within 40 days.
SAMPLE PREPARATION that interferences from the analytical system, glassware, and
Liquid samples — Transfer 1 L quantitatively to a continuous reagents are under control. The blank samples should be car-
extractor. If high concentrations are anticipated, a smaller vol- ried through all stages of the sample preparation and measure-
ume may be used and then diluted with organic-free reagent ment steps. For each analytical batch (up to 20 samples), a
concentrator.
flowing sandy texture must be mixed with anhydrous sodium TITLE Polynuclear Aromatic Hydrocarbons
MATRIX Groundwater, soils, sludges, water miscible liquid APPLICATION This method is used for the analysis of 16
wastes, and non-water miscible wastes. polynuclear aromatic hydrocarbons (PAHs). Samples are
APPLICATION This method is used for the analysis of var- extracted, concentrated, and analyzed using HPLC with detec-
ious PAHs. Samples are extracted, concentrated, and analyzed tion by UV and fluorescence detectors.
using direct injection of both neat and diluted organic liquids. INTERFERENCES Solvents, reagents, and glassware may
The method provides two optional GC columns that are better introduce artifacts. Other interferences may come from coex-
than Column 1 and that may help resolve analytes from inter- tracted compounds from samples.
ferences.
INSTRUMENTATION HPLC with a gradient pumping sys-
INTERFERENCES Solvents, reagents, and glassware may tem and a 250 mm by 2.6 mm reverse phase HC-ODS Sil-X
introduce artifacts. Other interferences may come from coex- 5-micron particle-size column. The fluorescence detector uses
tracted compounds from samples. an excitation wavelength of 280 nm and emission greater than
INSTRUMENTATION GC capable of on-column injections 389 nm cutoff with dispersive optics.
and a flame with detector (FID). Column 1: a 1.8 m by 2 mm
RANGE 0.1–425 g/L
3% OV-17 on Chromosorb W-AW-DCMS column. Column 2:
a 30 m by 0.25 mm SE-54 fused silica capillary colunm. Col- MDL 0.21 g/L (fluorescence; reagent water).
umn 3: a 30 m by 0.32 mm SE-54 fused silica capillary column.
RANGE 0.1–425 g/L Matrix Multiplication Factor
MDL Not reported. Groundwater 10
Low-level soil by sonication with GPC cleanup 670
PQL FACTORS FOR MULTIPLYING FID MDL
High-level soil and sludge by sonication 10,000
VALUE Not available.
ACCURACY 0.68C + 0.07 g/L (as recovery).
with Teflon®-lined caps for liquid (water) samples. sediments, and sludges. Use 1 or 2½ gallon amber glass bottles
with Teflon®-lined caps for liquid (water) samples.
STABILITY Cool soil, sediment, sludge, and liquid samples
to 4C. If residual chlorine is present in liquid samples add STABILITY Cool soil, sediment, sludge, and liquid samples
3 mL of 10% sodium thiosulfate per gallon of sample and cool to 4C. If residual chlorine is present in liquid samples add
to 4C. 3 mL of 10% sodium thiosulfate per gallon of sample and cool
to 4C.
MHT 14 days for concentrated waste, soil, sediment, or
sludge; 7 days for liquid samples; all extracts must be analyzed MHT 14 days for concentrated waste, soil, sediment, or
within 40 days. sludge; 7 days for liquid samples; all extracts must be analyzed
within 40 days.
centrate containing each analyte of interest is required. The QC QUALITY CONTROL Internal, surrogate, and five concen-
check sample concentrate may be prepared from pure standard tration level calibration standards are used. The calibration
materials or purchased as certified solutions Use appropriate standards must be used with the analytical method blank. A
trip, matrix, control site, method, reagent, and solvent blanks. quality control check sample concentrate containing fluoran-
Internal, surrogate, and five concentration level calibration thene at 10 g/mL is required. The QC check sample concen-
standards are used. The quality control check sample concentrate may be prepared from pure standard materials or
trate should contain fluoranthene at 10 g/mL in acetonitrile. purchased as certified solutions. Use appropriate trip, matrix,
REFERENCE Test Methods for Evaluating Solid Waste control site, method, reagent, and solvent blanks.
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC, REFERENCE Test Methods for Evaluating Solid Waste
Method 8100, Nov. 1986. (SW-846), U.S. EPA Office of Solid Waste, Washington, DC,
Method 8310, Rev. 0, Nov. 1986.

CAS #206-44-0 Fluorene EPA Method 1625
CAS #86-73-7
TITLE Polynuclear Aromatic Hydrocarbons
MATRIX Groundwater, soils, sludges, water miscible liquid TITLE Semivolatile Organic Compounds by Isotope Dilu-
wastes, and non-water miscible wastes. tion GC/MS
to extraction and analysis by capillary column gas chromatog- The labeled and native compound initial precision as standard
raphy-mass spectrometry (GC/MS). deviation (in g/L) was 29.
Stable isotopically-labeled analogs of the compounds of interest recovery (in g/L) was 81–132.
techniques.
performed, and to 0.5 mL if GPC is performed. extraction techniques. Samples containing 1 to 30% solids are
imum quantities that can be detected with no interferences
present. performance. Compute percent recovery of the labeled com-
pounds using the internal standard method. Compare the
The minimum level (in g/mL) was 10. This is defined as a labeled compound recovery for each compound with the cor-
minimum level at which the analytical system shall give recog- responding labeled compound recovery.

Reagent water and high solids reference matrix blanks are ana- PRECISION & ACCURACY The MDL concentrations were
lyzed to demonstrate freedom from contamination. Extract obtained using reagent water. The MDL actually achieved in a
and concentrate a 1-L reagent water blank or a high solids given analysis will vary depending on instrument sensitivity
reference matrix blank with each sample’s lot (samples started and matrix effects. This method was tested by 15 laboratories
through the extraction process on the same 8-h shift, to a using reagent water, drinking water, surface water, and indus-
maximum of 20 samples). trial wastewaters spiked at six concentrations over the range 5
standard method is used. The MDL (in g/L) in reagent water was 1.9.
ments) was 20.7.
was 71.6–108.4.
The range (in %) for percent recovery was 59–121.
C was 0.90C-0.00.
Fluorene EPA Method 625 tion of measurements at an average concentration found at
CAS #86-73-7 X was 0.12X + 0.26.
tion found at X was 0.13X + 0.61.
METHOD SUMMARY Approximately 1 L of sample is seri- taining a concentration at C in g/L.
concentrated to a volume of 1 mL, and analyzed by GC/MS. ylene chloride or else in a continuous extractor. Next, adjust
Qualitative identification of the parameters in the extract is the pH to <2 with sulfuric acid and serially extract in a sepa-
performed using the retention time and the relative abundance ratory funnel with methylene chloride or else in a continuous
of three characteristic masses (m/z). Qualitative analysis is per- extractor. Dry the extracts separately through a column of
formed using either external or internal standard techniques anhydrous sodium sulfate and then concentrate each of the
with a single characteristic m/z. extracts to 1.0 mL using a K-D apparatus.
to 30 min. Some thermally stable materials, such as PCBs, may thiosulfate/L of sample and mix well. All samples must be
not be eliminated by this treatment. Solvent rinses with acetone extracted within 7 days of collection and completely analyzed
and pesticide quality hexane may be substituted for the muffle within 40 days of extraction.
furnace heating. Matrix interferences may be caused by con-
INSTRUMENTATION A GC/MS system with an injection changed, a reagent water blank must be processed. Spike and
port designed for on-column injection when using packed col- analyze a minimum of 5% of all samples to monitor and eval-
umns and for splitless injection when using capillary columns. uate lab data quality. A QC check sample concentrate that
or equivalent.
Column for acids: 1.8 m long 2 mm I.D. glass, packed with After analysis of five spiked wastewater samples, calculate the
1% SP-1240DA on Supelcoport (100/120 mesh) or equivalent. average percent recovery and the standard deviation of the

percent recovery. Spike all samples with the surrogate standard The EQL (a, b) for low concentrations in soil and sediment
spiking solution and calculate the percent recovery of each in g/kg is 660.
surrogate compound. Accuracy as g/L is 0.90C–0.00.
Overall precision in g/L is 0.13X + 0.61.
26, 1984. (a) EQLs listed for soil/sediment are based on wet weight. Nor-
Fluorene EPA Method 8270 ation chromatography cleanup.
limit (EQL) of Method 8270B for determining an individual
sediment samples, 1–200 mg/kg for wastes (dependent on

concentrator.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous Fluorene EPA Method 8100
or wet samples (gummy or clay type) that do not have a free- CAS #86-73-7
sulfate until the sample is free flowing. Add 1 mL of surrogate TITLE Polynuclear Aromatic Hydrocarbons
sample in each analytical batch selected for spiking, add 1.0 mL MATRIX Groundwater, soils, sludges, water miscible liquid
of a matrix spiking standard. For base/neutral acid analysis, the wastes, and non-water miscible wastes.
amount added of the surrogates and matrix spiking com- APPLICATION This method is used for the analysis of var-
pounds should result in a final concentration of 100 ng/ L of ious PAHs. Samples are extracted, concentrated, and analyzed
each base/neutral analyte and 200 ng/L of each acid analyte using direct injection of both neat and diluted organic liquids.
in the extract to be analyzed (assuming a 1- L injection). The method provides two optional GC columns that are better
Immediately add a 100-mL mixture of 1:1 methylene chlo- than Column 1 and that may help resolve analytes from inter-
ride:acetone and extract the sample ultrasonically for 3 min ferences.
or more times. Dry the extract using a column with anhydrous INTERFERENCES Solvents, reagents, and glassware may
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. introduce artifacts. Other interferences may come from coex-
tracted compounds from samples.
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is INSTRUMENTATION GC capable of on-column injections
used for tuning the GC/MS system each 12-h shift. A system and a flame with detector (FID). Column 1: a 1.8 m by 2 mm
performance check also must be made during every 12-h shift. 3% OV-17 on Chromosorb W-AW-DCMS column. Column 2:
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- a 30 m by 0.25 mm SE-54 fused silica capillary colunm. Col-
rophenol, and benzidine is required to verify injection port umn 3: a 30 m by 0.32 mm SE-54 fused silica capillary column.
RANGE 0.1–425 g/L
including all required surrogates, must be performed every 12 h MDL Not reported.
PQL FACTORS FOR MULTIPLYING FID MDL
PRECISION 0.63X–0.65 g/L (overall precision).
calibration check standard must be evaluated immediately after ACCURACY 0.56C–0.52 g/L (as recovery).
with Teflon®-lined caps for liquid (water) samples.
any of the internal standards changes by a factor of two from STABILITY Cool soil, sediment, sludge, and liquid samples
the last daily calibration standard check, the mass spectrometer to 4C. If residual chlorine is present in liquid samples add
must be inspected for malfunctions and corrections must be 3 mL of 10% sodium thiosulfate per gallon of sample and cool
made, as appropriate. to 4C.
Demonstrate, through the analysis of a reagent water blank, MHT 14 days for concentrated waste, soil, sediment, or
that interferences from the analytical system, glassware, and sludge; 7 days for liquid samples; all extracts must be analyzed
reagents are under control. The blank samples should be car- within 40 days.
ment steps. For each analytical batch (up to 20 samples), a QUALITY CONTROL A quality control check sample con-
reagent blank, matrix spike, and matrix spike duplicate/dupli- centrate containing each analyte of interest is required. The QC
cate must be analyzed (the frequency of the spikes may be check sample concentrate may be prepared from pure standard
different for different monitoring programs). The blank and materials or purchased as certified solutions Use appropriate
spiked samples must be carried through all stages of the sample trip, matrix, control site, method, reagent, and solvent blanks.
preparation and measurement steps. A QC reference sample Internal, surrogate, and five concentration level calibration
concentrate containing each analyte at a concentration of standards are used. The quality control check sample concen-
100 mg/L in methanol is required. trate should contain fluorene at 100 g/mL in acetonitrile.

REFERENCE Test Methods for Evaluating Solid Waste may be prepared from pure standard materials or purchased
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC, as certified solutions. Use appropriate trip, matrix, control site,
Method 8100, Nov. 1986. method, reagent, and solvent blanks.
REFERENCE Test Methods for Evaluating Solid Waste
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC,
Fluorene EPA Method 8310 Method 8310, Rev. 0, Nov. 1986.
CAS #86-73-7
TITLE Polynuclear Aromatic Hydrocarbons

Fluoride EPA Method 340
wastes, and non-water miscible wastes. TITLE Fluoride (Potentiometric, Ion Selective Electrode)
APPLICATION This method is used for the analysis of 16 MATRIX This method is applicable to the measurement of
polynuclear aromatic hydrocarbons (PAHs). Samples are total and dissolved fluoride in drinking, surface and saline
extracted, concentrated, and analyzed using HPLC with detec- waters, domestic and industrial wastes.
tion by UV and fluorescence detectors.
METHOD SUMMARY Fluoride is determined potentiomet-
INTERFERENCES Solvents, reagents, and glassware may rically using a fluoride electrode in conjunction with a standard
introduce artifacts. Other interferences may come from coex- single junction sleeve-type reference electrode and a pH meter
tracted compounds from samples. with an expanded millivolt scale or a selective ion m with a
INSTRUMENTATION HPLC with a gradient pumping sys- direct concentration scale for fluoride. Check the pH first and
tem and a 250 mm by 2.6 mm reverse phase HC-ODS Sil-X if it is highly basic (>9), add 1N hydrochloric acid to adjust the
5-micron particle-size column. The UV detector uses an exci- pH to 8.3. Immerse the electrodes in a buffered solution and
tation wavelength of 254 nm coupled to the fluorescence detec- observe the m reading while mixing. The electrodes must
tor. The fluorescence detector uses an excitation wavelength of remain in the solution for at least three min or until the reading
280 nm and emission greater than 389 nm cutoff with disper- has stabilized.At concentrations under 0.5 mg/L, it may require
sive optics. as long as five min to reach a stable m reading; high concen-
trations stabilize more quickly. If a pH meter is used, record
RANGE 0.1–425 g/L
the potential measurements for each unknown sample and
MDL 0.21 g/L (UV detector; reagent water). convert the potential reading to the fluoride ion concentration
of the unknown using a standard’s concentration curve. If a
PQL FACTORS FOR MULTIPLYING FID MDL VALUE
selective ion m is used, read the fluoride level in the unknown
Matrix Multiplication Factor sample directly in mg/L on the fluoride scale.
Groundwater 10 INTERFERENCES Extremes of pH interfere so the sample
pH should be between 5 and 9. Polyvalent cations of silicon
Non-water miscible waste 100,000 (Si+4), iron (Fe+3), and aluminum (Al+3) interfere by forming
complexes with fluoride. The degree of interference depends
PRECISION 0.63X–0.65 g/L (overall precision). upon the concentration of the complexing cations, the concen-
ACCURACY 0.56C–0.52 g/L (as recovery). tration of fluoride and the pH of the sample. The addition of
a pH 5.0 buffer containing a strong chelating agent preferen-
SAMPLING METHOD Use 8-oz. widemouth glass bottles tially complexes aluminum (the most common interference),
with Teflon®-lined caps for concentrated waste samples, soils, silicon, and iron and eliminates the pH problem.
with Teflon®-lined caps for liquid (water) samples. INSTRUMENTATION Electrometer (pH meter) with an
expanded mv scale or a selective ion meter; fluoride ion activity
STABILITY Cool soil, sediment, sludge, and liquid samples electrode; and a single junction, sleeve-type reference electrode.
to 4C. If residual chlorine is present in liquid samples add
3 mL of 10% sodium thiosulfate per gallon of sample and cool RANGE 0.1–1000 mg/L
to 4C. MDL Not listed.
MHT 14 days for concentrated waste, soil, sediment, or PRECISION When a synthetic sample containing 0.85 mg/L
sludge; 7 days for liquid samples; all extracts must be analyzed fluoride and no interferences was analyzed by 111 analysts, a
within 40 days. mean of 0.84 mg/L with a standard deviation of  0.03 was
QUALITY CONTROL Internal, surrogate, and five concen- obtained. On the same study, a synthetic sample containing
tration level calibration standards are used. The calibration 0.75 mg/L fluoride, 2.5 mg/L polyphosphate and 300 mg/L
standards must be used with the analytical method blank. A alkalinity, was analyzed by the same 111 analysts and a mean
quality control check sample concentrate containing fluorene of 0.75 mg/L fluoride with a standard deviation of 0.036 was
at 100 g/mL is required. The QC check sample concentrate obtained.

ACCURACY 99% of true value at a concentration of
Fluoride EPA Method 340.3
0.75 mg/L or higher.
SAMPLING METHOD No special requirements; 50 to TITLE Inorganics, Non-Metallics
300 mL of sample is needed; collect samples in a high density MATRIX Drinking, surface, and saline waters. Wastewater.
polyethylene (HDPE) bottle.
APPLICATION Date issued 1971. (Colorimetric, automated
STABILITY No special requirements; no preservatives are complexone).
needed.
Fluoride (F) ion reacts with the red cerous chelate of alizarin
MHT 28 days complexone. There is a positive color developed in contrast to
QUALITY CONTROL A calibration standard curve as well a bleaching action in other fluoride Methods. For total or total
as instrument calibration are required. dissolved fluoride, the bellack distillation must be performed
prior to complexone analysis.
REFERENCE Methods for Chemical Analysis of Water and
INTERFERENCES Aluminum forms an extremely stable flu-
Wastes, EPA-600/4-79-020, Method 340.2, Fluoride (Potentio-
oro compound, which is overcome by treatment with 8-hydrox-
metric, Ion Selective Electrode), March 1983; EPA Environ-
yquinoline (complexes the aluminum) and extraction with
mental Monitor ing Systems Labor atory, Cincinnati, chloroform. At aluminum levels <0.2 mg/L, extraction proce-
OH,45268. dure is not required.
INSTRUMENTATION Technicon auto analyzer, 650 nm fil-
ters, 15 mm tubular flow cell.
Fluoride EPA Method 340.2
RANGE 0.05–1.5 mg F/L.
TITLE Inorganics, Non-Metallics MDL Not listed.
MATRIX Drinking, surface, and saline waters. Wastewater. PRECISION SD = 0.018 at Concentrations of 0.06, 0.15 and
APPLICATION Date issued 1971. Editorial Rev. 1974. 1.08 mg F/L.
(Potentiometric, ion selective electrode). Fluoride(F) is deter- ACCURACY Recoveries = 89 and 102% at concentrations of
mined potentiometrically using a fluoride electrode in con- 0.14 and 1.25 mg F/L.
junction with a standard single junction sleeve type reference
electrode and a pH meter. SAMPLING METHOD Plastic.
INTERFERENCES pH extremes interfere; sample pH should STABILITY No preservation required.

be between 5 and 9. Polyvalent cations of silicon, iron and MHT 28 Days.
aluminum interfere (form complexes with fluoride). Degree of
QUALITY CONTROL Arrange fluoride standards in sampler
interference depends on complexing cations, concentration of
in order of decreasing concentration.
fluoride and pH of sample.
REFERENCE Methods for the Chemical Analysis of Water
INSTRUMENTATION Selective ion m with direct concen-
and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979.
tration scale for (F) or pH meter with expanded mv scale
RANGE 0.1–1000 mg/L F.
MDL Not listed. Fluoride EPA Method 340
PRECISION SD = 0.03 at 0.85 mg/L F. TITLE Fluoride (Potentiometric, Ion Selective Electrode)
ACCURACY Mean = 0.84 mg/L at 0.85 mg/L F. MATRIX This method is applicable to the measurement of
SAMPLING METHOD Plastic. total and dissolved fluoride in drinking, surface and saline
waters, domestic and industrial wastes.
STABILITY No preservation required.
METHOD SUMMARY Fluoride is determined potentiomet-
MHT 28 days. rically using a fluoride electrode in conjunction with a standard
QUALITY CONTROL For industrial waste samples, regular single junction sleeve-type reference electrode and a pH meter
amount buffer may not be adequate. Analyst should check pH with an expanded millivolt scale or a selective ion m with a
first. If highly basic (pH >9), add 1N HCl and adjust pH to direct concentration scale for fluoride. Check the pH first and
8.3. [Electrodes must remain in the solution at least 3 min or if it is highly basic (pH >9), add 1N hydrochloric acid to adjust
until reading has stabilized. (Up to 5 min)] the pH to 8.3. Immerse the electrodes in a buffered solution
and observe the m reading while mixing. The electrodes must
REFERENCE Methods for the Chemical Analysis of Water remain in the solution for at least three min or until the reading
and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979. has stabilized.At concentrations under 0.5 mg/L, it may require

as long as five min to reach a stable m reading; high concen- MATRIX Drinking, surface, and saline waters. Wastewater.
trations stabilize more quickly. If a pH meter is used, record
APPLICATION Date issued 1971. Editorial Rev. 1978. (Col-
the potential measurements for each unknown sample and
orimetric, spadns with bellack distillation). After distillation to
convert the potential reading to the fluoride ion concentration
remove interferences, sample is treated with spadns reagent.
of the unknown using a standard’s concentration curve. If a
Loss of color resulting from fluoride reaction with z-s dye is
selective ion m is used, read the fluoride level in the unknown
function of fluoride concentration.
sample directly in mg/L on the fluoride scale.
INTERFERENCES A small error in reagent addition is most
INTERFERENCES Extremes of pH interfere so the sample
prominent source of error in this test. Care must be taken to
pH should be between 5 and 9. Polyvalent cations of silicon
avoid overheating flask above level of solution. (Maintain an
(Si+4), iron (Fe+3), and aluminum (Al+3) interfere by forming
even flame entirely under boiling flask). Extend range using
complexes with fluoride. The degree of interference depends
fluoride ion selective method.
upon the concentration of the complexing cations, the concen-
tration of fluoride and the pH of the sample. The addition of INSTRUMENTATION Distillation equipment. Spectropho-
a pH 5.0 buffer containing a strong chelating agent preferen- tometer at 570 nm or filterphotometer at 550–580 nm.
tially complexes aluminum (the most common interference),
RANGE 0.1–2.5 mg/L F. (Can be extended).
silicon, and iron and eliminates the pH problem.
MDL Not listed.
INSTRUMENTATION Electrometer (pH meter) with an
expanded mv scale or a selective ion meter; fluoride ion activity PRECISION SD = 0.089 mg/L F at 0.83 mg/L F.
electrode; and a single junction, sleeve-type reference electrode.
ACCURACY Mean = 0.81 mg/L F at 0.83 m/L F
PRECISION & ACCURACY
SAMPLING METHOD Plastic.
RANGE 0.1–1000 mg/L
STABILITY No preservation required.
MDL Not listed.
MHT 28 Days.
PRECISION When a synthetic sample containing 0.85 mg/L
QUALITY CONTROL Plot absorbance vs. concentration.
fluoride and no interferences was analyzed by 111 analysts, a
Prepare a new standard curve whenever fresh reagent is made.
mean of 0.84 mg/L with a standard deviation of  0.03 was
(Fluoride concentration is measured as the diffeence of absor-
obtained. On the same study, a synthetic sample containing
bance in the blank and the sample).
0.75 mg/L fluoride, 2.5 mg/L polyphosphate and 300 mg/L
alkalinity, was analyzed by the same 111 analysts and a mean REFERENCE EPA Methods for the Chemical Analysis of
of 0.75 mg/L fluoride with a standard deviation of 0.036 was Water and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979.
obtained.
ACCURACY 99% of true value at a concentration of
0.75 mg/L or higher. Fluridone EPA Method 507
SAMPLE COLLECTION, PRESERVATION & HANDLING No CAS #59756-60-4
information was provided.
TITLE Determination of Nitrogen and Phosphorus-Con-
SAMPLING METHOD No special requirements; 50 to taining Pesticides in Water by GC/NPD
300 mL of sample is needed; collect samples in a high density
polyethylene (HDPE) bottle. MATRIX This method is applicable to the determination of
STABILITY No special requirements; no preservatives are ished drinking water and groundwater.
needed.
METHOD SUMMARY Method 507 covers 46 nitrogen- and
MHT 28 days phosphorus-containing pesticides. A 1-L sample is fortified
with a surrogate standard, salted, buffered, extracted with
QUALITY CONTROL A calibration standard curve as well
methylene chloride, and concentrated; then the solvent is
as instrument calibration are required.
exchanged with methyl tert-butyl ether (MTBE) and concen-
REFERENCE Methods for Chemical Analysis of Water and trated again, and a 2-L aliquot of a sample extract is injected
Wastes, EPA-600/4-79-020, Method 340.2, Fluoride (Potentio- into a GC system equipped with a selective nitrogen-phospho-
metric, Ion Selective Electrode), March 1983; EPA Environ- rus detector and a capillary column for analysis.
mental Monitor ing Systems Labor atory, Cincinnati,
OH,45268.
processing apparatus. Interfering contamination may occur
when a sample containing low concentrations of analytes is
Fluoride, Total EPA Method 340.1 analyzed immediately following a sample containing relatively
high concentrations. One or more injections of MTBE should be
TITLE Inorganics, Non-Metallics made following the analysis of a sample with high concentrations

of analytes to check for analyte carryover. Matrix interferences separatory funnel or in a mechanical tumbler bottle. Dry the
may be caused by contaminants that are coextracted from the extract by pouring it through a solvent-rinsed drying column
sample. The extent of matrix interferences will vary consider- containing about 10 cm of anhydrous sodium sulfate. Collect
ably from source to source, depending upon the water sampled. the extract in a Kuderna-Danish (K-D) concentrator and rinse
INSTRUMENTATION A gas chromatograph system (GC)
equipped with a nitrogen-phosphorus detector (NPD) is the extract to about 2 mL and rinse the flask and its lower joint
needed. into the concentrator tube with 1 to 2 mL of methyl t-butyl
ether (MTBE). Add 5–10 mL of MTBE and concentrate the
Column 1: 30 m 0.25 mm I.D. DB-5 bonded fused silica col- extract twice (adding more MTBE) to a final volume of 5.0 mL
umn, 0.25 m film thickness, or equivalent. and store it at 4C until analysis.
column, 0.25 m film thickness, or equivalent. Note: If methylene chloride is not completely removed from
in a single lab and estimated detection limits (EDLs) have been QUALITY CONTROL Minimum quality control require-
determined for each analyte. Observed detection limits may ments are initial demonstration of lab capability, determina-
vary among waters, depending upon the nature of the inter- tion of surrogate compound recoveries in each sample and
ferences in the sample matrix and the specific instrumentation blank, monitoring internal standard peak area or height in each
used. Analytes that are not separated chromatographically can- sample and blank, analysis of lab reagent blanks, lab fortified
not be individually identified and measured unless an alterna- samples, lab fortified blanks, and other QC samples. A lab
tive technique for identification and quantification exist. reagent blank is analyzed to demonstrate that all glassware and
reagent interferences are under control.
The estimated detection limit (in g/L) was 3.8. The EDL is
defined as either method detection limit or a level of compound Initial demonstration of capability is fulfilled by analyzing four
in a sample yielding a peak in the final extract with signal-to- fortified reagent water samples with the recovery value for each
noise ratio of approximately 5, whichever value is higher. analyte falling within the acceptable range ( 30% average
The concentration used for these measurements (in g/L) was 38. recovery). Surrogate recoveries from samples or method blanks
The accuracy (as % recovery) was 87. must be 70–130%. The internal standard response for any sam-
The precision (% RSD) was 9. ple chromatogram should not deviate from the daily calibra-
SAMPLING METHOD Grab samples are collected in 1-L 30% or lab fortified blanks and sample matrices are used to
glass sample bottles (prewashed with detergent and hot tap assess lab performance and analyte recovery, respectively.
for 1 h) with screw caps lined with PTFE-fluorocarbon. If the response for the target analyte peak exceeds the working
SAMPLE PRESERVATION Add mercuric chloride to the techniques such as an alternate detector or second chromatog-
sample bottle in amounts to produce a concentration of raphy column should be used to confirm peak identification
10 mg/L. If residual chlorine is present, add 80 mg of sodium when sample components are not resolved adequately.
After collection, seal bottle and shake vigorously for 1 min, then EPA CONTACT & HOTLINE For technical questions contact
cool the sample to 4C immediately and store it at 4C in the Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
dark until extraction. Drinking Water (WH-550D), 401 M St. SW, Washington, DC
20460. Tel. (202) 260-3040. For further information the EPA
MHT Maximum holding time of the samples, and in some Safe Drinking Water Hotline may be called at: (800) 426-4791.
Note: Samples with this compound exhibited recoveries of less Compounds in Drinking Water, EPA/600/4-88/039 (revised
than 60% after 14 days. July 1991). U.S. EPA Environmental Monitoring Systems Lab-
SAMPLE PREPARATION Fortify the sample with 50 L of oratory, Cincinnati, OH, 45268, U.S.A. Available from the
the surrogate standard solution, adjust to pH 7 with phosphate National Technical Information Service (NTIS), 5285 Port
buffer, add 100 g NaCl to the sample, and seal and shake to Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS
dissolve the salt; then extract with methylene chloride in a Order Number is PB91-231480.

H
Hardness, Total (mg/L as CaCO3) EPA Method 130.1 RANGE All concentration ranges of hardness.
TITLE Physical Properties MDL Not listed.
MATRIX Drinking, surface, and saline waters. PRECISION SD = 2.98 mg/L, CaCO3 at 194 mg/L, CaCO3.
ACCURACY As bias, –2.0 mg/L, CaCO3 at 194 mg/L, CaCO3.
APPLICATION Date issued 1971. (Colorimetric, automated
EDTA). The magnesium edta exchanges magnesium on an SAMPLING METHOD Plastic or glass (100 mL).
equiv basis for any calcium and/or other cations to form a more
STABILITY HNO3 to pH <2. H2SO4 to pH <2.
stable EDTA chelate than magnesium. The free Mg reacts with
calmagite at pH 10. MHT 6 months.
INTERFERENCES No significant interferences. (The free QUALITY CONTROL Use a sample aliquot containing not
magnesium (Mg) plus calgamite reaction gives a red-violet more than 25 mg calcium carbonate(CaCO3). Use inhibitors
complex, and by measuring only magnesium concentration in to reduce metal ion interference during titration. Automated
the final reaction stream, total hardness can be measured accu- titration may be used.
rately).
INSTRUMENTATION Technicon auto analyzer, 520 nm fil- and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979.
ters, 15 mm tubular flow cell.
RANGE 10–400 mg/L as CaCO3.
MDL Not listed. Heptachlor EPA Method 505
CAS #76-44-8
PRECISION SD = 1.5 at 19 and 120 mg/L as CaCO3.
ACCURACY At concentrations, 39 and 296 mg/L as CaCO3,
Polychlorinated Biphenyl (PCB) Products in Water by Microex-
recoveries, 89 and 93%.
traction and Gas Chromatography. U.S. EPA Method 505, Rev.
SAMPLING METHOD Plastic or glass (100 mL). 2.0, 1989.
STABILITY HNO3 to pH <2. H2SO4 to pH <2. MATRIX This method is applicable to drinking water and
MHT 6 months. raw source water. The latter should include most surface water
and groundwater sources.
QUALITY CONTROL For most wastewaters and highly pol-
luted waters, the sample must be digested as in atomic absorp- METHOD SUMMARY Method 505 covers 25 pesticides and
tion method. Arrange working standards in sampler in order commercial PCB products. This is a very sensitive method that
of decreasing concentrations. is more useful for monitoring than for exploratory analyses.
5-mL of water are saturated with sodium chloride and then
REFERENCE EPA Methods for the Chemical Analysis of extracted by shaking with 2 mL of hexane. The sample extracts
Water and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979. are transferred to an autosampler setup to inject 1–2 L por-
tions into a gas chromatograph (GC) for analysis. Alternatively,
1–2 L portions of samples, blanks, and standards may be
Hardness, Total (mg/L as CaCO3) EPA Method 130.2 manually injected. Each extract is analyzed by capillary
GC/ECD with confirmation using either a second capillary
TITLE Physical Properties column or GC/MS. The electron capture detector is easy to use,
but it is a nonselective detector. The microextraction technique
MATRIX Drinking, surface, and saline waters. Wastewater. also eliminates the expensive sample preparation costs of other
APPLICATION Date issued 1971. Editorial Rev. 1978. (Tit- methods, but it has the disadvantage of being less sensitive than
rimetric, EDTA). Calcium (Ca) and magnesium (Mg) ions are most because the extracts are not concentrated.
sequestered upon addition of disodium-EDTA. Reaction end INTERFERENCES Method interferences may be caused by
point, using indicator, has red color in presence of Ca and Mg, contaminants in solvents, reagents, glassware, and other sample
a blue color when they’re sequestered. processing apparatus that lead to discrete artifacts or elevated
INTERFERENCES Excessive amounts of heavy metals can baselines. Interfering contamination may occur when a sample
interfere. This is usually overcome by complexing the metals containing low concentrations of analytes is analyzed immedi-
with cyanide. Routine addition of sodium cyanide solution ately following a sample containing relatively high concentra-
(caution:deadly poisin) to prevent potential metallic interfer- tions of the analytes. Matrix interferences also may be caused
ence is recommended. by contaminants that are coextracted from the sample; cleanup
of sample extracts may be necessary in these cases. Some pes-
INSTRUMENTATION Standard lab titrimetric equipment. ticides and commercial PCB products from aqueous solutions

adhere to glass surfaces, so sample transfers and contact with SAMPLE PREPARATION Remove the sample from storage
glass surfaces should be minimized. Some pesticides are rapidly and allow it to come to room temperature. Remove a 5-mL
oxidized by chlorine so dechlorination with sodium thiosulfate volume from each container and weigh the container to the
at the time of sample collection is important. Also, splitless nearest 0.1 g. Add 6 g of sodium chloride and 2.0 mL of hexane
injectors may cause degradation of some pesticides. to each sample bottle. Recap the sample and shake it vigorously
for one min. Allow the water and hexane phases to separate,
INSTRUMENTATION A gas chromatograph/electron cap-
remove the cap, and transfer 0.5 mL of hexane into an autosam-
ture detector/data system, with temperature programming and
pler vial using a disposable glass pipette. Transfer the remaining
split/splitless injector suitable for use with capillary columns is
needed. hexane phase into a second autosampler vial and store at 4C
for reanalysis, if necessary. Discard the remaining sample/hex-
Column 1: 0.32 mm I.D.  30 m fused silica capillary with ane mixture and reweigh the empty container to determine net
chemically bond methyl polysiloxane phase (DB-1, 1.0 m weight of sample.
film, or equivalent).
Column 2: 0.32 mm I.D. 30 m fused silica capillary with 1:1 QUALITY CONTROL Minimum quality control require-
mixed phase of dimethyl silicone and polyethylene glycol ments are initial demonstration of lab capability, analysis of lab
(Durawax-DX3, 0.25 m film, or equivalent). reagent blanks, fortified blanks, fortified sample matrix, and
Column 3: 0.32 mm I.D.  25 m fused silica capillary with quality control samples. The lab must analyze at least one for-
chemically bonded 50:50 methyl-phenyl silicone (OV-17, tified blank per sample set, or at least one for every 20 samples.
1.5 m film, or equivalent). The fortifying concentration of each analyte should be 10 times
the method detection limit or the maximum calibration limit
Column 1 should be used as the primary analytical column. (MCL), whichever is less. Calculate accuracy as percent recov-
Columns 2 and 3 are recommended for use as confirmatory ery and develop control limits from the mean percent recovery
columns when GC/MS confirmation is not available. and standard deviation.
PRECISION & ACCURACY Method detection limits are The lab must add a known concentration of the analytes to a
dependent upon the characteristics of the gas chromatographic minimum of 10% of the routine samples, or one lab fortified
system used. Analytes that are not separated chromatographi- sample matrix per sample set. Calculate the percent recovery
cally cannot be individually identified and used in the same
for each analyte and compare to the control limits established
calibration mixture or water samples unless an alternative tech-
from the analyses of the fortified blanks.
nique for identification and quantification, such as mass spec-
trometry, is used. EPA CONTACT & HOTLINE For technical questions contact
The concentration(s) (in g/L) used for these QC measure-
ments was 0.032 and 1.2.
The MDL (in g/L) was 0.003.
The accuracy (% recovery) for reagent water at the above con-
centration(s) was 77 and 80 and the precision (%) was 10.2 REFERENCE Methods for the Determination of Organic
and 7.4. Compounds in Drinking Water, EPA/600/4-88/039 (revised
The accuracy (% recovery) for groundwater at the above con- July 1991). U.S. EPA Environmental Monitoring Systems Lab-
centration(s) was 37 and 71 and the precision (%) was 6.8 oratory, Cincinnati, OH, 45268, U.S.A. Available from the
and 9.8. National Technical Information Service (NTIS), 5285 Port
The accuracy (% recovery) for tap water at the above concen- Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS
tration(s) was 200 and 106 and the precision (5) was 22.6 Order Number is PB91-231480.
and 16.8.
Note: No range of concentrations is provided with this method.
SAMPLING METHOD Collect samples using a 40-mL Heptachlor EPA Method 625
screw-cap vial (prewashed with detergent, rinsed with distilled CAS #76-44-8
water and oven dried at 400C for one h) with a Teflon®-faced
silicone septum . Collect bubble-free samples and place the sep- TITLE Base/Neutrals and Acids, U.S. EPA Method 625
tum with the Teflon® side down on the water. MATRIX This methods covers municipal and industrial
SAMPLE PRESERVATION If residual chlorine is present in wastewaters.
the water add about 3 mg of sodium thiosulfate to each vial METHOD SUMMARY Approximately 1 L of sample is seri-
before samples are collected to remove the chlorine. Alterna- ally extracted with methylene chloride at a pH greater than 11
tively, add 75 L of 0.04 g/mL solution of sodium thiosulfate and again at a pH less than 2 using a separatory funnel or a
to each vial just prior to sampling. Immediately cool samples continuous extractor. The methylene chloride extract is dried,
to 4C, and store them in a solvent-free refrigerator at 4C until concentrated to a volume of 1 mL, and analyzed by GC/MS. Qual-
analysis. itative identification of the parameters in the extract is performed
MHT The maximum holding time is 14 days from the time using the retention time and the relative abundance of three char-
the sample was collected until it must be analyzed. acteristic masses (m/z). Qualitative analysis is performed using

either external or internal standard techniques with a single anhydrous sodium sulfate and then concentrate each of the
characteristic m/z. extracts to 1.0 mL using a K-D apparatus.
neutral extraction may cause significantly reduced recovery of tion of the ability to generate acceptable accuracy and precision
phenols. The packed gas chromatographic columns recom- with this method. Before processing any samples, the analyst
mended for the basic fraction may not exhibit sufficient reso- must analyze a reagent water blank to demonstrate that inter-
lution for some analytes. ferences from the analytical system and glassware are under
packed with 3% SP-2550 on Supelcoport (100/120 mesh) 100 g/mL in acetone is required. PCBs and multicomponent
or equivalent. pesticides may be omitted from this test.
PRECISION & ACCURACY The MDL concentrations were percent recovery. Spike all samples with the surrogate standard
obtained using reagent water. The MDL actually achieved in a spiking solution and calculate the percent recovery of each
given analysis will vary depending on instrument sensitivity surrogate compound.
and matrix effects. This method was tested by 15 laboratories REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct.
using reagent water, drinking water, surface water, and indus- 26, 1984.
centration of the parameter matrix. Heptachlor EPA Method 8080
CAS #76-44-8
The MDL (in g/L) in reagent water was 1.9.
The standard deviation (in g/L based on 4 recovery measure- TITLE Organochlorine Pesticides and Polychlorinated
ments) was 37.2. Biphenyls By Gas Chromatography
was D-172.2. MATRIX This method is used to determine the concentra-
The range (in %) for percent recovery was D-192. tion of various organochlorine pesticides and polychlorinated
Accuracy (in g/L) as expected recovery for one or more mea- biphenyls in extracts prepared from water, groundwater, soils,
surements of a sample containing a true concentration of and sediments.
C was 0.87C-2.97. METHOD SUMMARY This method covers 26 pesticides and
Precision (in g/L) as expected single analyst standard devia- Aroclor (PCB) mixtures and it is suitable for monitoring-type
tion of measurements at an average concentration found at analyses. After extraction, concentration and solvent exchange
X was 0.24X–0.56. to hexane, a 2- to 5-L sample aliquot is injected into a GC
Overall precision (in g/L) as expected interlaboratory stan- using the solvent flush technique, and the analytes are detected
dard deviation of measurements in an average concentra- by an electron capture detector (ECD) or an electrolytic con-
tion found at X was 0.50X–0.23. ductivity detector in the halogen mode (HECD). Both neat and
C = True value of the concentration in g/L. diluted organic liquids may be analyzed by direct injection.
X = Average recovery found for measurements of samples con- INTERFERENCES Interferences coextracted from the sam-
taining a concentration at C in g/L. ples will vary considerably from source to source. Interferences
SAMPLE PREPARATION Adjust the pH to >11 with sodium by phthalate esters can pose a major problem in pesticide deter-
hydroxide and serially extract in a separatory funnel with meth- minations when using the ECD. Cross-contamination of clean
ylene chloride or else in a continuous extractor. Next, adjust glassware routinely occurs when plastics are handled during
the pH to <2 with sulfuric acid and serially extract in a sepa- extraction steps, especially when solvent-wetted surfaces are han-
ratory funnel with methylene chloride or else in a continuous dled. The contamination from phthalate esters can be completely
extractor. Dry the extracts separately through a column of eliminated with a microcoulometric or electrolytic conductivity

detector. Solvents, reagent, glassware, and other sample pro- through a column of anhydrous sodium sulfate to dry and
cessing hardware may yield artifacts and/or interferences to concentrate it in a K-D apparatus to 1 mL volume.
sample analysis.
Soils, sediments and sludges — Rapidly weigh approximately
INSTRUMENTATION A gas chromatograph capable of on- 30 g of sample into a 400-mL beaker to avoid loss of the more
column injections is needed. It must be equipped with an ECD volatile extractables. Nonporous or wet samples (gummy or
or a HECD and one of the following GC columns: clay type) that do not have a free-flowing sandy texture must
Column 1: Supelcoport (100/120 mesh) coated with 1.5% SP-
2250/1.95% SP-2401 packed in a 1.8 m 4 mm I.D. glass
column.
chloride:acetone and extract ultrasonically. Decant and filter
in a 1.8 m 4 mm I.D. glass column. extracts, dry the extract by passing it through a drying column
PRECISION & ACCURACY The method was tested by 20 in a K-D apparatus.
surface water, and three industrial wastewaters spiked at six Hexane solvent exchange — Add 50 mL of hexane, a new boil-
concentrations. Concentrations used in the study ranged from ing chip, and concentrate until the apparent volume of liquid
0.5 to 30 g/L for single-component pesticides and from 8.5 to reaches 1 mL. Adjust the extract volume to 10.0 mL. Stopper
400 g/L for multicomponent parameters. Overall precision the concentration tube and store refrigerated at 4C if further
and method accuracy were found to be directly related to the processing will not be performed immediately. If the extract
concentration of the analyte and essentially independent of the will be stored longer than two days, transfer it to a vial with
sample matrix. The sensitivity of this method usually depends Teflon®-lined screw-cap or crimp top.
on the concentration of interferences rather than on instru- QUALITY CONTROL Demonstrate through the analysis of
mental limitations. a reagent water blank, that all glassware and reagents are inter-
MDL in g/L was 0.003. ference free. Each time a set of samples is processed, a method
Concentration range in g/L was 0.5–30. blank should be processed as a safeguard against chronic lab
Accuracy as recovery (x*) in g/L was 0.69C + 0.04 . contamination. A reagent blank, a matrix spike, and a duplicate
Overall precision (S*) in g/L was 0.16x + 0.08. or matrix spike duplicate must be performed for each analytical
containing concentration C, in g/L. Analytical system performance must be verified by analyzing
S* = Expected interlaboratory standard deviation of measure- QC check samples. The QC check sample concentration should
ments at an average concentration found of the analyte contain each single-component analyte at the following con-
in g/L. centrations in acetone: 4,4-DDD, 10 g/mL; 4,4-DDT,
C = True value for the concentration, in g/L. 10 g/mL; endosulfan II, 10 g/mL; endosulfan sulfate,
X = Average recovery found for measurements of samples con- 10 g/mL; and any other single-component pesticide at
taining a concentration of C, in g/L. 2 g/mL. If the method is only to be used to analyze PCBs,
Chlordane, or Toxaphene, the QC check sample concentrate
SAMPLING METHOD should contain the most representative multicomponent
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with parameter at a concentration of 50 g/mL in acetone.
a screw-top Teflon®-lined cover. Pre-wash the bottle with deter-
gent, rinse with distilled water and methanol (or isopropanol). REFERENCE Test Methods for Evaluating Solid Waste (SW-
Soil, sediments, and sludges — Use an 8-oz. widemouth glass of Solid Wastes, Washington, DC.
with a screw-top Teflon®-lined cover. Pre-wash the bottle with
panol).
Heptachlor EPA Method 8270
SAMPLE PRESERVATION Cool water, soil, sediment, or CAS #76-44-8
sludge samples immediately to 4C.
Water samples — If residual chlorine is present, add 3 mL of TITLE Semivolatile Organic Compounds by GC/MS
10% sodium thiosulfate per gallon and cool to 4C. All extracts MATRIX This method is used to determine the concentra-
and samples should be stored under refrigeration. tion of semivolatile organic compounds in extracts prepared
MHT Liquid samples must be extracted within 7 days and from all types of solid waste matrices, soils, and groundwater.
the extracts must be analyzed within 40 days. Soils, sediments, Although surface waters are not specifically mentioned, this
and sludges may be stored for a maximum of 14 days prior to method should be applicable to water samples from rivers,
extraction. lakes, etc.
SAMPLE PREPARATION METHOD SUMMARY This method covers 259 semivolatile
Liquid samples — Extract 1 L samples in a continuous extrac- organic compounds. In very limited applications direct injection
tor at pH 5–9 with methylene chloride after adding 1.0 mL of of the sample into the GC/MS system may be appropriate, but
surrogate spiking solution to each sample. Pass the extract this results in very high detection limits (approximately
Soils, sediments, or sludges — Use an 8-oz. widemouth glass
(or isopropanol).
SAMPLE PRESERVATION
and low-concentration samples are sequentially analyzed. To
SAMPLE PREPARATION
bath, and an ultrasonic disrupter with a minimum power of ume may be used and then diluted with organic-free reagent
300 W and with pulsing capability are also required. water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
The EQL(b) for groundwater in g/L is not listed. the pH of the aqueous phase to pH >11 using 10 N sodium
in g/kg is not listed. 18–24 h. Dry the extract through a column containing anhy-
Accuracy as g/L is 0.87C–2.97. drous sodium sulfate and concentrate it to 1 mL using a K-D
Overall precision in g/L is 0.50X–0.23. concentrator.
(a) EQLs listed for soil/sediment are based on wet weight. Nor- Soils, sediments, or sludges — Use 30 g of sample. Nonporous

used for tuning the GC/MS system each 12-h shift. A system manually injected. Each extract is analyzed by capillary
performance check also must be made during every 12-h shift. GC/ECD with confirmation using either a second capillary
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- column or GC/MS. The electron capture detector is easy to use,
rophenol, and benzidine is required to verify injection port but it is a nonselective detector. The microextraction technique
inertness and GC column performance. A calibration standard also eliminates the expensive sample preparation costs of other
at mid-concentration, containing each compound of interest, methods, but it has the disadvantage of being less sensitive than
including all required surrogates, must be performed every 12 h most because the extracts are not concentrated.
processing apparatus that lead to discrete artifacts or elevated
The internal standard responses and retention times in the baselines. Interfering contamination may occur when a sample
calibration check standard must be evaluated immediately after containing low concentrations of analytes is analyzed immedi-
or during data acquisition. If the retention time for any internal ately following a sample containing relatively high concentra-
standard changes by more than 30 seconds from the last check tions of the analytes. Matrix interferences also may be caused
calibration (12 h), the chromatographic system must be by contaminants that are coextracted from the sample; cleanup
inspected for malfunctions and corrections must be made, as of sample extracts may be necessary in these cases. Some pes-
required. If the electron ionization current plot (EICP) area for ticides and commercial PCB products from aqueous solutions
any of the internal standards changes by a factor of two from adhere to glass surfaces, so sample transfers and contact with
the last daily calibration standard check, the mass spectrometer glass surfaces should be minimized. Some pesticides are rapidly
must be inspected for malfunctions and corrections must be oxidized by chlorine so dechlorination with sodium thiosulfate
made, as appropriate. at the time of sample collection is important. Also, splitless
injectors may cause degradation of some pesticides.
that interferences from the analytical system, glassware, and INSTRUMENTATION A gas chromatograph/electron cap-
reagents are under control. The blank samples should be car- ture detector/data system, with temperature programming and
ried through all stages of the sample preparation and measure- split/splitless injector suitable for use with capillary columns is
ment steps. For each analytical batch (up to 20 samples), a needed.
cate must be analyzed (the frequency of the spikes may be Column 1: 0.32 mm I.D.  30 m fused silica capillary with
different for different monitoring programs). The blank and chemically bond methyl polysiloxane phase (DB-1, 1.0 m
spiked samples must be carried through all stages of the sample film, or equivalent).
preparation and measurement steps. A QC reference sample Column 2: 0.32 mm I.D. 30 m fused silica capillary with 1:1
concentrate containing each analyte at a concentration of mixed phase of dimethyl silicone and polyethylene glycol
100 mg/L in methanol is required. (Durawax-DX3, 0.25 m film, or equivalent).
Column 3: 0.32 mm I.D.  25 m fused silica capillary with
REFERENCE Test Methods for Evaluating Solid Waste (SW- chemically bonded 50:50 methyl-phenyl silicone (OV-17,
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office 1.5 m film, or equivalent).
Column 1 should be used as the primary analytical column.
Columns 2 and 3 are recommended for use as confirmatory
columns when GC/MS confirmation is not available.
Heptachlor epoxide EPA Method 505
CAS #1024-57-3
Polychlorinated Biphenyl (PCB) Products in Water by Microex- cally cannot be individually identified and used in the same
traction and Gas Chromatography. U.S. EPA Method 505, Rev. calibration mixture or water samples unless an alternative tech-
2.0, 1989. nique for identification and quantification, such as mass spec-
trometry, is used.
MATRIX This method is applicable to drinking water and
raw source water. The latter should include most surface water The concentration(s) (in g/L) used for these QC measure-
and groundwater sources. ments was 0.04 and 1.4.
The MDL (in g/L) was 0.004.
METHOD SUMMARY Method 505 covers 25 pesticides and The accuracy (% recovery) for reagent water at the above con-
commercial PCB products. This is a very sensitive method that centration(s) was 100 and 115 and the precision (%) was
is more useful for monitoring than for exploratory analyses. 15.6 and 6.6.
5-mL of water are saturated with sodium chloride and then The accuracy (% recovery) for groundwater at the above con-
extracted by shaking with 2 mL of hexane. The sample extracts centration(s) was 90 and 103 and the precision (%) was 14.2
are transferred to an autosampler setup to inject 1–2 L por- and 6.9.
tions into a gas chromatograph (GC) for analysis. Alternatively, The accuracy (% recovery) for tap water at the above concen-
1–2 L portions of samples, blanks, and standards may be tration(s) was 112 and 81 and the precision (5) was 7.5 and 5.9.

Note: No range of concentrations is provided with this method.
Heptachlor epoxide EPA Method 625
SAMPLING METHOD Collect samples using a 40-mL CAS #1024-57-3
screw-cap vial (prewashed with detergent, rinsed with distilled
water and oven dried at 400C for one h) with a Teflon®-faced TITLE Base/Neutrals and Acids, U.S. EPA Method 625
silicone septum . Collect bubble-free samples and place the sep- MATRIX This methods covers municipal and industrial
tum with the Teflon® side down on the water. wastewaters.
SAMPLE PRESERVATION If residual chlorine is present in METHOD SUMMARY Approximately 1 L of sample is seri-
the water add about 3 mg of sodium thiosulfate to each vial ally extracted with methylene chloride at a pH greater than 11
before samples are collected to remove the chlorine. Alterna- and again at a pH less than 2 using a separatory funnel or a
tively, add 75 L of 0.04 g/mL solution of sodium thiosulfate continuous extractor. The methylene chloride extract is dried,
to each vial just prior to sampling. Immediately cool samples concentrated to a volume of 1 mL, and analyzed by GC/MS.
to 4C, and store them in a solvent-free refrigerator at 4C until Qualitative identification of the parameters in the extract is
analysis. performed using the retention time and the relative abundance
MHT The maximum holding time is 14 days from the time of three characteristic masses (m/z). Qualitative analysis is per-
the sample was collected until it must be analyzed. formed using either external or internal standard techniques
with a single characteristic m/z.
SAMPLE PREPARATION Remove the sample from storage
and allow it to come to room temperature. Remove a 5-mL INTERFERENCES Method interferences may be caused by
volume from each container and weigh the container to the contaminants in solvents, reagents, glassware, and other sample
nearest 0.1 g. Add 6 g of sodium chloride and 2.0 mL of hexane processing hardware. Glassware must be scrupulously cleaned.
to each sample bottle. Recap the sample and shake it vigorously Glassware should be heated in a muffle furnace at 400C for 5
for one min. Allow the water and hexane phases to separate, to 30 min. Some thermally stable materials, such as PCBs, may
remove the cap, and transfer 0.5 mL of hexane into an autosam- not be eliminated by this treatment. Solvent rinses with acetone
pler vial using a disposable glass pipette. Transfer the remaining and pesticide quality hexane may be substituted for the muffle
hexane phase into a second autosampler vial and store at 4C
for reanalysis, if necessary. Discard the remaining sample/hex-
ane mixture and reweigh the empty container to determine net
weight of sample.
QUALITY CONTROL Minimum quality control require- lution for some analytes.
ments are initial demonstration of lab capability, analysis of lab
INSTRUMENTATION A GC/MS system with an injection
reagent blanks, fortified blanks, fortified sample matrix, and
port designed for on-column injection when using packed col-
quality control samples. The lab must analyze at least one for-
tified blank per sample set, or at least one for every 20 samples.
The fortifying concentration of each analyte should be 10 times Column for base/neutrals: 1.8 m long  2 mm I.D. glass,
the method detection limit or the maximum calibration limit packed with 3% SP-2550 on Supelcoport (100/120 mesh)
(MCL), whichever is less. Calculate accuracy as percent recov- or equivalent.
ery and develop control limits from the mean percent recovery Column for acids: 1.8 m long 2 mm I.D. glass, packed with
and standard deviation. 1% SP-1240DA on Supelcoport (100/120 mesh) or equivalent.
The lab must add a known concentration of the analytes to a PRECISION & ACCURACY The MDL concentrations were
minimum of 10% of the routine samples, or one lab fortified obtained using reagent water. The MDL actually achieved in a
sample matrix per sample set. Calculate the percent recovery given analysis will vary depending on instrument sensitivity
for each analyte and compare to the control limits established and matrix effects. This method was tested by 15 laboratories
from the analyses of the fortified blanks. using reagent water, drinking water, surface water, and indus-
EPA CONTACT & HOTLINE For technical questions contact to 100 g/L. Single operator precision, overall precision, and
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and method accuracy were found to be directly related to the con-
Drinking Water (WH-550D), 401 M St. SW, Washington, DC centration of the parameter matrix.
Safe Drinking Water Hotline may be called at: (800) 426-4791. The MDL (in g/L) in reagent water was 2.2.
REFERENCE Methods for the Determination of Organic ments) was 54.7.
Compounds in Drinking Water, EPA/600/4-88/039 (revised The range (in g/L) for average recovery for 4 measurements
July 1991). U.S. EPA Environmental Monitoring Systems Lab- was 70.9–109.4.
oratory, Cincinnati, OH, 45268, U.S.A. Available from the The range (in %) for percent recovery was 26–155.
National Technical Information Service (NTIS), 5285 Port Accuracy (in g/L) as expected recovery for one or more mea-
Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS surements of a sample containing a true concentration of
Order Number is PB91-231480. C was 0.92C-1.87.

X was 0.33X–0.46. analyses. After extraction, concentration and solvent exchange
tion found at X was 0.28X + 0.64. by an electron capture detector (ECD) or an electrolytic con-
SAMPLE COLLECTION, PRESERVATION & HANDLING ferences to sample analysis.
extracted within 7 days of collection and completely analyzed Column 1: Supelcoport (100/120 mesh) coated with 1.5% SP-
within 40 days of extraction. 2250/1.95% SP-2401 packed in a 1.8 m 4 mm I.D. glass
QUALITY CONTROL Make an initial, one-time, demonstra- column.
tion of the ability to generate acceptable accuracy and precision Column 2: Supelcoport (100/120 mesh) coated with 3% OV-1
with this method. Before processing any samples, the analyst in a 1.8 m 4 mm I.D. glass column.
changed, a reagent water blank must be processed. Spike and
400 g/L for multicomponent parameters. Overall precision
sample matrix. The sensitivity of this method usually depends
After analysis of five spiked wastewater samples, calculate the on the concentration of interferences rather than on instru-
average percent recovery and the standard deviation of the mental limitations.
surrogate compound.
Accuracy as recovery (x*) in g/L was 0.89C + 0.10 .
REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct. Overall precision (S*) in g/L was 0.25x–0.08.
26, 1984.
Heptachlor epoxide EPA Method 8080 ments at an average concentration found of the analyte
CAS #1024-57-3 in g/L.
TITLE Organochlorine Pesticides and Polychlorinated X = Average recovery found for measurements of samples con-
Biphenyls By Gas Chromatography taining a concentration of C, in g/L.
MATRIX This method is used to determine the concentra- SAMPLING METHOD
tion of various organochlorine pesticides and polychlorinated Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
biphenyls in extracts prepared from water, groundwater, soils, a screw-top Teflon®-lined cover. Pre-wash the bottle with deter-
and sediments. gent, rinse with distilled water and methanol (or isopropanol).

Soil, sediments, and sludges — Use an 8-oz. widemouth glass REFERENCE Test Methods for Evaluating Solid Waste (SW-
with a screw-top Teflon®-lined cover. Pre-wash the bottle with 846). U.S. EPA. 1983. Method 8080B, Rev. 2, Nov. 1990. Office
detergent, rinse with distilled water and methanol (or isopro- of Solid Wastes, Washington, DC.
panol).
sludge samples immediately to 4C. Heptachlor epoxide EPA Method 8270
CAS #1024-57-3
SAMPLE PREPARATION lakes, etc.
Soils, sediments and sludges — Rapidly weigh approximately gate, and matrix spiking standards, is extracted in a continuous
30 g of sample into a 400-mL beaker to avoid loss of the more extractor first under acid conditions and then under basic con-
containing anhydrous sodium sulfate and concentrate to 1 mL INTERFERENCES Raw GC/MS data from all blanks, sam-
in a K-D apparatus. ples, and spikes must be evaluated for interferences. Contam-
parameter at a concentration of 50 g/mL in acetone. Accuracy as g/L is 0.92C–1.87.

Overall precision in g/L is 0.28X + 0.64. drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator.

Hexachlorobenzene EPA Method 1625
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu- The minimum level (in g/mL) was 10. This is defined as a
tion GC/MS minimum level at which the analytical system shall give recog-
to extraction and analysis by capillary column gas chromatog-
deviation (in g/L) was 16.
using continuous extraction techniques. If the solids content is present in aqueous samples, add 80 mg sodium thiosulfate/L
greater than 30%, the sample is extracted using ultrasonic of water. Begin sample extraction within 7 days of collection,
techniques. and analyze all extracts within 40 days of extraction.
Each extract is dried over sodium sulfate, concentrated to a SAMPLE PREPARATION Samples containing 1% solids or
performed, and to 0.5 mL if GPC is performed.
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%

Spike all samples with labeled compounds to assess method of sample extracts may be necessary in these cases. Some pes-
performance. Compute percent recovery of the labeled com- ticides and commercial PCB products from aqueous solutions
pounds using the internal standard method. Compare the adhere to glass surfaces, so sample transfers and contact with
labeled compound recovery for each compound with the cor- glass surfaces should be minimized. Some pesticides are rapidly
responding labeled compound recovery. oxidized by chlorine so dechlorination with sodium thiosulfate
at the time of sample collection is important. Also, splitless
lyzed to demonstrate freedom from contamination. Extract
and concentrate a 1-L reagent water blank or a high solids INSTRUMENTATION A gas chromatograph/electron cap-
reference matrix blank with each sample’s lot (samples started ture detector/data system, with temperature programming and
through the extraction process on the same 8-h shift, to a split/splitless injector suitable for use with capillary columns is
maximum of 20 samples). needed.
Field replicates may be collected to determine the precision of Column 1: 0.32 mm I.D.  30 m fused silica capillary with
the sampling technique, and spiked samples may be required chemically bond methyl polysiloxane phase (DB-1, 1.0 m
to determine the accuracy of the analysis when the internal film, or equivalent).
standard method is used. Column 2: 0.32 mm I.D. 30 m fused silica capillary with 1:1
REFERENCE Semivolatile Organic Compounds by Isotope mixed phase of dimethyl silicone and polyethylene glycol
Dilution GC/MS. Office of Water Regulation and Standards, (Durawax-DX3, 0.25 m film, or equivalent).
U.S. EPA Industrial Technology Division, Washington, DC, Column 3: 0.32 mm I.D.  25 m fused silica capillary with
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, chemically bonded 50:50 methyl-phenyl silicone (OV-17,
U.S. EPA, Office of Water Regulations and Standards, 401 M 1.5 m film, or equivalent).
St., SW, Washington, DC, 20460. Phone: 202-382-7131). Column 1 should be used as the primary analytical column.
Hexachlorobenzene EPA Method 505 PRECISION & ACCURACY Method detection limits are
CAS #118-74-1 dependent upon the characteristics of the gas chromatographic
TITLE Analysis of Organohalide Pesticides and Commercial cally cannot be individually identified and used in the same
Polychlorinated Biphenyl (PCB) Products in Water by Microex- calibration mixture or water samples unless an alternative tech-
traction and Gas Chromatography. U.S. EPA Method 505, Rev. nique for identification and quantification, such as mass spec-
2.0, 1989. trometry, is used.
MATRIX This method is applicable to drinking water and The concentration(s) (in g/L) used for these QC measure-
raw source water. The latter should include most surface water ments was 0.003 and 0.09.
and groundwater sources. The MDL (in g/L) was 0.002.
commercial PCB products. This is a very sensitive method that centration(s) was 104 and 103 and the precision (%) was
is more useful for monitoring than for exploratory analyses. 13.5 and 6.6.
extracted by shaking with 2 mL of hexane. The sample extracts centration(s) was 91 and 1.1 and the precision (%) was 10.9
1–2 L portions of samples, blanks, and standards may be tration(s) was 100 and 88 and the precision (5) was 15.6
manually injected. Each extract is analyzed by capillary and 13.4.
GC/ECD with confirmation using either a second capillary Note: No range of concentrations is provided with this method.
column or GC/MS. The electron capture detector is easy to use,
but it is a nonselective detector. The microextraction technique SAMPLING METHOD Collect samples using a 40-mL
also eliminates the expensive sample preparation costs of other screw-cap vial (prewashed with detergent, rinsed with distilled
methods, but it has the disadvantage of being less sensitive than water and oven dried at 400C for one h) with a Teflon®-faced
most because the extracts are not concentrated. silicone septum . Collect bubble-free samples and place the sep-
contaminants in solvents, reagents, glassware, and other sample SAMPLE PRESERVATION If residual chlorine is present in
processing apparatus that lead to discrete artifacts or elevated the water add about 3 mg of sodium thiosulfate to each vial
baselines. Interfering contamination may occur when a sample before samples are collected to remove the chlorine. Alterna-
containing low concentrations of analytes is analyzed immedi- tively, add 75 L of 0.04 g/mL solution of sodium thiosulfate
ately following a sample containing relatively high concentra- to each vial just prior to sampling. Immediately cool samples
tions of the analytes. Matrix interferences also may be caused to 4C, and store them in a solvent-free refrigerator at 4C until
by contaminants that are coextracted from the sample; cleanup analysis.

MHT The maximum holding time is 14 days from the time performed using the retention time and the relative abundance
the sample was collected until it must be analyzed. of three characteristic masses (m/z). Qualitative analysis is per-
formed using either external or internal standard techniques
with a single characteristic m/z.
and allow it to come to room temperature. Remove a 5-mL
volume from each container and weigh the container to the INTERFERENCES Method interferences may be caused by
nearest 0.1 g. Add 6 g of sodium chloride and 2.0 mL of hexane contaminants in solvents, reagents, glassware, and other sample
to each sample bottle. Recap the sample and shake it vigorously processing hardware. Glassware must be scrupulously cleaned.
for one min. Allow the water and hexane phases to separate, Glassware should be heated in a muffle furnace at 400C for 5
remove the cap, and transfer 0.5 mL of hexane into an autosam- to 30 min. Some thermally stable materials, such as PCBs, may
pler vial using a disposable glass pipette. Transfer the remaining not be eliminated by this treatment. Solvent rinses with acetone
hexane phase into a second autosampler vial and store at 4C and pesticide quality hexane may be substituted for the muffle
for reanalysis, if necessary. Discard the remaining sample/hex- furnace heating. Matrix interferences may be caused by con-
ane mixture and reweigh the empty container to determine net taminants that are coextracted from the sample. The base-
weight of sample. neutral extraction may cause significantly reduced recovery of
QUALITY CONTROL Minimum quality control require- mended for the basic fraction may not exhibit sufficient reso-
ments are initial demonstration of lab capability, analysis of lab lution for some analytes.
reagent blanks, fortified blanks, fortified sample matrix, and
quality control samples. The lab must analyze at least one for- INSTRUMENTATION A GC/MS system with an injection
tified blank per sample set, or at least one for every 20 samples. port designed for on-column injection when using packed col-
The fortifying concentration of each analyte should be 10 times umns and for splitless injection when using capillary columns.
the method detection limit or the maximum calibration limit Column for base/neutrals: 1.8 m long  2 mm I.D. glass,
(MCL), whichever is less. Calculate accuracy as percent recov- packed with 3% SP-2550 on Supelcoport (100/120 mesh)
ery and develop control limits from the mean percent recovery or equivalent.
and standard deviation. Column for acids: 1.8 m long 2 mm I.D. glass, packed with
The lab must add a known concentration of the analytes to a 1% SP-1240DA on Supelcoport (100/120 mesh) or equivalent.
minimum of 10% of the routine samples, or one lab fortified PRECISION & ACCURACY The MDL concentrations were
sample matrix per sample set. Calculate the percent recovery obtained using reagent water. The MDL actually achieved in a
for each analyte and compare to the control limits established given analysis will vary depending on instrument sensitivity
from the analyses of the fortified blanks. and matrix effects. This method was tested by 15 laboratories
EPA CONTACT & HOTLINE For technical questions contact using reagent water, drinking water, surface water, and indus-
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and trial wastewaters spiked at six concentrations over the range 5
Drinking Water (WH-550D), 401 M St. SW, Washington, DC to 100 g/L. Single operator precision, overall precision, and
20460. Tel. (202) 260-3040. For further information the EPA method accuracy were found to be directly related to the con-
Safe Drinking Water Hotline may be called at: (800) 426-4791. centration of the parameter matrix.
REFERENCE Methods for the Determination of Organic The MDL (in g/L) in reagent water was 1.9.
Compounds in Drinking Water, EPA/600/4-88/039 (revised The standard deviation (in g/L based on 4 recovery measure-
July 1991). U.S. EPA Environmental Monitoring Systems Lab- ments) was 24.9.
oratory, Cincinnati, OH, 45268, U.S.A. Available from the The range (in g/L) for average recovery for 4 measurements
National Technical Information Service (NTIS), 5285 Port was 7.8–141.5.
Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS The range (in %) for percent recovery was D-152.
Order Number is PB91-231480. Accuracy (in g/L) as expected recovery for one or more mea-
C was 0.74C + 0.66.
Hexachlorobenzene EPA Method 625 tion of measurements at an average concentration found at
CAS #118-74-1 X was 0.18X–0.10.
tion found at X was 0.43X–0.52.
concentrated to a volume of 1 mL, and analyzed by GC/MS. ylene chloride or else in a continuous extractor. Next, adjust the
Qualitative identification of the parameters in the extract is pH to <2 with sulfuric acid and serially extract in a separatory

funnel with methylene chloride or else in a continuous extrac- siderably from source to source, depending upon the waste
tor. Dry the extracts separately through a column of anhydrous being sampled.
sodium sulfate and then concentrate each of the extracts to
INSTRUMENTATION An analytical system complete with
1.0 mL using a K-D apparatus.
GC suitable for on-column injections and accessories, includ-
SAMPLE COLLECTION, PRESERVATION & HANDLING ing detectors, column supplies, recorder, gases and syringes is
Grab samples must be collected in glass containers. All samples required. A data system for measuring peak areas and/or peak
must be refrigerated at 4C from the time of collection until heights is recommended. The GC is equipped with an electron
extraction. If residual chlorine is present, add 80 mg of sodium capture detector (ECD). A K-D apparatus is needed for sample
thiosulfate/L of sample and mix well. All samples must be preparation.
extracted within 7 days of collection and completely analyzed
within 40 days of extraction. Column 1: 1.8 m 2 mm I.D. glass column packed with 1%
SP-1000 on Supelcoport (100/120 mesh) or equivalent.
QUALITY CONTROL Make an initial, one-time, demonstra- Column 2: 1.8 m 2 mm I.D. glass column packed with 1.5%
tion of the ability to generate acceptable accuracy and precision OV-1/2.4% OV-225 on Supelcoport (80/100 mesh) or
with this method. Before processing any samples, the analyst equivalent.
ferences from the analytical system and glassware are under PRECISION & ACCURACY The method was tested by 20
control. Each time a set of samples is extracted or reagents are laboratories using organic-free reagent water, drinking water,
changed, a reagent water blank must be processed. Spike and surface water, and three industrial wastewaters spiked at six
analyze a minimum of 5% of all samples to monitor and eval- concentrations over the range 1.0 to 356 g/L. Single operator
uate lab data quality. A QC check sample concentrate that precision, overall precision, and method accuracy were found
contains each parameter of interest at a concentration of to be directly related to the concentration of the parameter and
100 g/mL in acetone is required. PCBs and multicomponent essentially independent of the sample matrix.
pesticides may be omitted from this test. MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
After analysis of five spiked wastewater samples, calculate the Matrix Factor (b)
average percent recovery and the standard deviation of the Groundwater 10
percent recovery. Spike all samples with the surrogate standard Low-concentration soil by ultrasonic cleanup 670
spiking solution and calculate the percent recovery of each extraction with GPC
surrogate compound. High-concentration soil and sludges 10,000
REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct. by ultrasonic extraction
26, 1984. Non-water miscible waste 100,000
(a) Sample EQLs are highly matrix-dependent. The EQLs listed are
Hexachlorobenzene EPA Method 8120 (b) EQL = [Method detection limit] [Factor]. For non-aqueous
CAS #118-74-1 samples, the factor is on a wet-weight basis.
PRECISION & ACCURACY The estimates below are based
TITLE Chlorinated Hydrocarbons by Gas Chromatography upon the performance in a single lab.
MATRIX This method covers aqueous and solid matrices. The accuracy (in g/L) as expected recovery for one or more
measurements of a sample containing a concentration of C
water, industrial wastewaters, surface waters, soils, solids, and
was 0.87C-0.02.
sediments.
The precision (in g/L) as expected single analyst standard
METHOD SUMMARY This method is used to determine the deviation of measurements at an average concentration of
concentration of 14 chlorinated hydrocarbons. It provides gas x” was 0.14 x”-0.07.
chromatographic conditions for the detection of ppb concen- The precision (in g/L) as expected interlaboratory standard
trations of certain chlorinated hydrocarbons. Prior to use of deviation measurements at an average concentration found
this method, appropriate sample extraction techniques must of x” was 0.36x” -0.19.
be used. Both neat and diluted organic liquids (EPA Method
3580, Waste Dilution) may be analyzed by direct injection. A
x”= Average recovery found for measurements of samples con-
2 to 5 g/mL aliquot of the extract is injected into a gas chro- taining a concentration of C, in g/L.
matograph (GC) using the solvent flush technique, and com-
pounds in the GC effluent are detected by an electron capture SAMPLE COLLECTION, PRESERVATION & HANDLING
detector (ECD). Extracts must be stored under refrigeration at 4C and analyzed
within 40 days of extraction.
sample processing hardware may yield discrete artifacts and/or SAMPLE PREPARATION In general, water samples are
elevated baselines causing misinterpretation of gas chromato- extracted at a neutral, or as is, pH with methylene chloride
grams. Interferences coextracted from samples will vary con- using either EPA Method 3510 or EPA Method 3520. Solid

samples are extracted using either EPA Method 3540 or EPA must be scrupulously clean. Phthalate esters, if present in a
Method 3550. Prior to gas chromatographic analysis, the sample, will interfere only with the BHC isomers. The presence
extraction solvent must be exchanged to hexane. of elemental sulfur will result in large peaks, and can often
mask the region of compounds eluting after 1,2,4,5-tetrachloro-
QUALITY CONTROL The quality control check concentrate
benzene. The tetrabutylammonium (TBA)-sulfite procedure
(EPA Method 8000) should contain each parameter of interest
(EPA Method 3660) works well for the removal of elemental
in acetone at the following concentrations: hexachloro-substi-
sulfur. Waxes and lipids can be removed by gel permeation
tuted hydrocarbon, 10 g/mL; and any other chlorinated
chromatography (EPA Method 3640).
hydrocarbon, 100 g/mL. Calculate surrogate standard recov-
ery on all samples, blanks, and spikes. INSTRUMENTATION A GC suitable for on-column injec-
tions and all required accessories, including and electron cap-
Prepare stock standard solutions in isooctane or hexane. Cali-
ture detector (ECD), analytical columns, recorder, gases, and
bration standards at a minimum of five concentrations should
syringes are needed. A data system for measuring peak heights
be prepared through dilution of the stock standards with isooc-
and/or peak areas is recommended. A Kuderna-Danish (K-D)
tane or hexane. Internal standards and surrogate standards are
apparatus will also be needed to concentrate extracts.
also needed.
Column 1: 30 m 0.53 mm I.D. fused-silica capillary column
chemically bonded with trifluoropropyl methyl silicone
(DB-210 or equivalent).
of Solid Waste, Washington, DC, 1990. EPA Method 8120 A
Rev. 1, Nov. 1990.
chemically bonded with polyethylene glycol (DB-WAX or
equivalent).
PRECISION & ACCURACY This method has been tested in
Hexachlorobenzene EPA Method 8121 a single lab by using organic-free reagent water, sandy loam
CAS #118-74-1 samples, and extracts which were spiked with the test com-
pounds at one concentration. Single-operator precision and
TITLE Chlorinated Hydrocarbons by GC: Capillary Column
method accuracy were found to be related to the concentration
Technique
of compound and the type of matrix. The accuracy and preci-
MATRIX This method covers aqueous and solid matrices. sion technique will be determined by the sample matrix, sam-
This includes a wide variety such as drinking water, ground- ple preparation technique, optional cleanup techniques, and
water, industrial wastewaters, surface waters, soils, solids, and calibration procedures used.
sediments.
METHOD SUMMARY This method provides procedures for Matrix Factor (b)
the determination of 22 chlorinated hydrocarbons in water,
soil/sediment, and waste matrices. A measured volume or Groundwater 10
weight of sample is extracted by using one of the appropriate Low-concentration soil by ultrasonic cleanup 670
sample extraction techniques specified in EPA Method 3510, extraction with GPC
EPA Method 3520, EPA Method 3540, or EPA Method 3550, High-concentration soil and sludges 10,000
or diluted using EPA Method 3580. Aqueous samples are by ultrasonic extraction
extracted at neutral pH with methylene chloride by using either Non-water miscible waste 100,000
a separatory funnel (EPA Method 3510) or a continuous liquid- (a) Sample EQLs are highly matrix-dependent. The EQLs listed are
liquid extractor (EPA Method 3520). Solid samples are provided for guidance and may not always be achievable.
extracted with hexane/acetone (1:1) by using a Soxhlet extrac- (b) EQL = [Method detection limit] [Factor]. For non-aqueous
tor (EPA Method 3540) or with methylene chloride/acetone samples, the factor is on a wet-weight basis.
(1:1) by using an ultrasonic extractor (EPA Method 3550).After
cleanup, the extract or diluted sample is analyzed by gas chro- PRECISION & ACCURACY MDL is the method detection
matography with electron capture detection (GC/ECD). limit for organic-free reagent water. MDLwas determined from
the analysis of eight replicate aliquots processed through the
The sensitivity level of this method usually depends on the level entire analytical method (extraction, Florisil cartridge cleanup,
of interferences rather than on instrumental limitations. This and GC/ECD analysis).
method may be used in conjunction with EPA Method 3620,
Florisil Column Cleanup, EPA Method 3660, Sulfur Cleanup, The MDL (in ng/L) was 5.6.
and EPA Method 3640, Gel Permeation Chromatography, to The accuracy (as average % recovery using 5 determinations
aid in the elimination of interferences. and no Florisil cleanup) from a spike concentration of 1.0 g/L
INTERFERENCES Solvents, reagents, glassware, and other and separatory funnel extraction was 92% with a final volume
hardware used in sample processing may introduce artifacts of 10 mL.
which may result in elevated baselines, causing misinterpreta- The precision (as RSD% using 5 determinations and no Florisil
tion of gas chromatograms. Interferants coextracted from the cleanup) from a spike concentration of 1.0 g/L and separatory
samples will vary considerably from waste to waste. Glassware funnel extraction was 7.1% with a final volume of 10 mL.

The accuracy (as average % recovery using 5 determinations 3520). Solid samples are extracted with hexane/acetone (1:1
and no Florisil cleanup), from a spike concentration of 330 g/L v:v) using a Soxhlet extractor (EPA Method 3540) or with
and ultrasonic extraction of solid samples using 1:1 methylene methylene chloride/acetone (1:1 v:v) using an ultrasonic
chloride and acetone, was 81% with a final volume of 10 mL. extractor (EPA Method 3550). Non-aqueous waste samples
may be diluted using EPA Method 3580. Prior to Florisil
The precision (as RSD% using 5 determinations and no Florisil
cleanup or gas chromatographic analysis, the extraction solvent
cleanup), from a spike concentration of 330 g/L and ultra-
must be exchanged to hexane. Sample extracts that will be
sonic extraction of solid samples using 1:1 methylene chloride
subjected to gel permeation chromatography do not need sol-
and acetone, was 3.2% with a final volume of 10 mL.
vent exchange.
Cleanup procedures may not be necessary for a relatively clean
Volatile Organics — Standard 40-mL glass screw-cap VOA vials
matrix. If removal of interferences such as chlorinated phenols,
phthalate esters, etc., is required, proceed with the procedure
outlined in EPA Method 3620.
which might drive off volatile compounds. If there are any air QUALITY CONTROL Analyze a quality control check stan-
bubbles present the sample must be retaken. The vials with dard to demonstrate that the operation of the GC is in control.
solids should be tapped slightly as they are filled to try and The frequency of the check standard analysis is equivalent to
eliminate as much free air space as possible. Two vials from 10% of the samples analyzed. If the recovery of any compound
each sampling location should be sealed in separate plastic bags found in the check standard is less than 80% of the certified
to prevent cross-contamination between samples. value, the problem must be corrected and a new set of calibra-
tion standards must be prepared and analyzed. Calculate sur-
rogate standard recoveries for all samples, blanks, and spikes.
the determination of semivolatile organic compounds should
An internal standard peak area check must be performed on
be soap and water washed followed by methanol (or isopro-
all samples. The internal standard must be evaluated for accep-
panol) rinsing. The sample containers should be of glass or
tance by determining whether the measured area for the inter-
Teflon® and have screw-top covers with Teflon® liners.
nal standard deviates by more than 30% from the average area
Preservation for volatile organics — No preservation is used for the internal standard in the calibration standards. When
with concentrated waste samples. With liquid samples contain- the internal standard peak area is outside that limit, all samples
ing no residual chlorine, 4 drops of concentrated hydrochloric that fall outside the QC criteria must be reanalyzed. Any com-
acid are added and the samples are immediately cooled to 4 C. pound confirmed by two columns may also be confirmed by
When liquid samples contain residual chlorine, they are treated GC/MS (EPA Method 8270). The GC/MS would normally
as above and, in addition, 4 drops of 4% aqueous sodium require a minimum concentration of 1 ng/L in the final
thiosulfate are added to remove the residual chlorine. Soil, extract for each compound. Include a mid-concentration cal-
sediment, and sludge samples are only cooled to 4C. ibration standard after each group of 20 samples in the analysis
sequence. The response factors for the mid-concentration cal-
ibration must be within 15% of the average values for the
used with concentrated waste samples. With liquid samples
multiconcentration calibration.
containing no residual chlorine and with soil, sediment, and
sludge samples, immediately cooling to 4C is the only preser- REFERENCE Test Methods for Evaluating Solid Waste, Phys-
vation used. When residual chlorine is present then 3 mL of ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
10% aqueous sodium sulfate is added for each gallon of sample of Solid Waste, Washington, DC, 1990. EPA Method 8121, Rev.
collected, followed by cooling to 4C. 0, Nov. 1990.
Holding times — The holding time for all volatile organics
samples is 14 days. Liquid samples must be extracted within
7 days and their extracts analyzed within 40 days. Concentrated Hexachlorobenzene EPA Method 8270
waste, soil, sediment, and sludge samples must be extracted CAS #118-74-1
within 14 days and their extracts analyzed within 40 days.
SAMPLE PREPARATION Prepare stock standard solutions
in hexane. Calibration standards at a minimum of five con- MATRIX This method is used to determine the concentra-
centrations should be prepared through dilution of the stock tion of semivolatile organic compounds in extracts prepared
standards with hexane. The suggested internal standards are: from all types of solid waste matrices, soils, and groundwater.
2,5-dibromotoluene, 1,3,5-t r ibromobenzene, and , Although surface waters are not specifically mentioned, this
dibromo-m-xylene. The analyst can use any of the three com- method should be applicable to water samples from rivers,
pounds provided that theyare resolved from matrix interferences. lakes, etc.
Recommended surrogate compounds are -2,6-trichlorotoluene,
1,4-dichloronaphthalene, and 2,3,4,5,6-pentachlorotoluene.
In general, water samples are extracted at a neutral pH with tion of the sample into the GC/MS system may be appropriate,
methylene chloride using a separatory funnel (EPA Method but this results in very high detection limits (approximately
3510) or a continuous liquid-liquid extractor (EPA Method 10,000 g/L). Typically, a 1-L liquid sample,containing surrogate,
and matrix spiking standards, is extracted in a continuous SAMPLING METHOD
the extracts analyzed within 40 days. Soils, sediments, or slud-
ges may be stored for a maximum of 14 days and the extracts
in g/kg is 660.
Accuracy as g/L is 0.74C + 0.66.
Overall precision in g/L is 0.43X–0.52.
concentrator.

used for tuning the GC/MS system each 12-h shift. A system If the solids content is 30% or less, the sample is diluted to 1%
performance check also must be made during every 12-h shift. solids with reagent water, homogenized ultrasonically, and
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- extracted at pH 12–13, then at pH <2 with methylene chloride
rophenol, and benzidine is required to verify injection port using continuous extraction techniques. If the solids content is
inertness and GC column performance. A calibration standard greater than 30%, the sample is extracted using ultrasonic
validity of the initial calibration. performed, and to 0.5 mL if GPC is performed.
The internal standard responses and retention times in the An internal standard is added to the extract, and a 1-mL aliquot
calibration check standard must be evaluated immediately after of the extract is injected into the GC. The compounds are
or during data acquisition. If the retention time for any internal separated by GC and detected by a MS. The labeled compounds
Demonstrate, through the analysis of a reagent water blank, shift, to a maximum of 20). Specific selection of reagents and
ried through all stages of the sample preparation and measure- cleaned by solvent rinse and baking at 450C for 1-h minimum.
ment steps. For each analytical batch (up to 20 samples), a Interferences coextracted from samples will vary considerably
Hexachlorobutadiene EPA Method 1625 rather than instrumental limitations. The limits typify the min-
present.
CERCLA (as amended 1986); and other compounds amenable The labeled and native compound initial precision as standard
to extraction and analysis by capillary column gas chromatog- deviation (in g/L) was 56.
raphy-mass spectrometry (GC/MS). The labeled and native compound initial accuracy as average
recovery (in g/L) was 51–251.
Stable isotopically-labeled analogs of the compounds of interest
are added to the sample. If the solids content is less than 1%, SAMPLE COLLECTION, PRESERVATION & HANDLING
a 1-L sample is extracted at pH 12–13, then at pH <2 with Collect samples in glass containers. Aqueous samples which
methylene chloride using continuous extraction techniques. flow freely are collected in refrigerated bottles using automatic

sampling equipment. Solid samples are collected as grab sam- U.S. EPA, Office of Water Regulations and Standards, 401 M
ples using widemouth jars. Maintain samples at 0 to 4C from St., SW, Washington, DC, 20460. Phone: 202-382-7131).
Hexachlorobutadiene EPA Method 502
CAS #87-68-3
less are extracted directly using continuous liquid-liquid TITLE Volatile Organic Compounds in Water By Purge and
extraction techniques. Samples containing 1 to 30% solids are Trap Capillary Column Gas Chromatography with Photoion-
diluted to the 1% level with reagent water and extracted using ization and Electrolytic Conductivity Detectors in Series. U.S.
continuous liquid-liquid extraction techniques. Samples con- EPA Method 502.2, Rev. 2.0, 1989.
techniques. MATRIX Drinking water and raw source water. The latter
extractors to 12–13 with 6 N NaOH. Extract with methylene METHOD SUMMARY This method covers 60 volatile
chloride for 24–48 h. organic compounds that contain halogen atoms and/or that
Acid extraction — Adjust the pH of the waters in the extractors are aromatic. An inert gas (zero grade nitrogen or helium) is
to 2 or less using 6 N sulfuric acid. Extract with methylene bubbled through a 25-mL or a 5-mL water sample (depending
chloride for 24–48 h. on the expected concentration of the analytes). Purged sample
Ultrasonic extraction of high solids samples — Add anhy- components are trapped in a tube of sorbent materials. When
drous sodium sulfate to the sample and QC aliquot(s). purging is complete, the sorbent tube is heated and backflushed
Add acetone:methylene chloride (1:1) to the sample and with helium to desorb the trapped sample onto a capillary GC
mix thoroughly column. The column is temperature programmed to separate
the method analytes which are then detected with a photoion-
Concentrate extracts using a K-D apparatus. ization detector (PID) and a Hall electrolytic conductivity
(HECD) placed in series. The PID is selective for aromatic
compounds and the HECD is selective for halogenated com-
pounds.
Analyses of blanks are required to demonstrate freedom from INTERFERENCES Impurities in the purge gas and from
contamination. When results of spikes indicate atypical organic compounds outgassing from the plumbing ahead of
method performance for samples, the samples are diluted to the trap account for many contamination problems. Interfer-
bring method performance within acceptable limits. ences purged or coextracted from the samples will vary con-
analyze two sets of four 1-L aliquots (8 aliquots total) of the sample or extract being tested. Cross-contamination can occur
precision and recovery standard. For high solids samples, two whenever high-level and low-level samples are analyzed
sets of four 30-g aliquots of the high solids reference matrix sequentially. Samples also can be contaminated by diffusion of
are used. volatile organics (particularly methylene chloride and fluoro-
carbons) through the septum seal into the sample during ship-
Spike all samples with labeled compounds to assess method ment and storage. The lab where volatile analysis is performed
performance. Compute percent recovery of the labeled com- and also the refrigerated storage area should be completely free
pounds using the internal standard method. Compare the of solvents.
responding labeled compound recovery. INSTRUMENTATION A GC containing a series configura-
tion of a high temperature photoionization detector (PID)
Reagent water and high solids reference matrix blanks are ana- equipped with 10.0 eV (nominal) lamp and Hall electrolytic
lyzed to demonstrate freedom from contamination. Extract conductivity detector (HECD) is required. Also required is an
and concentrate a 1-L reagent water blank or a high solids all-glass 5-mL purging device, a sorbent trap, and a thermal
reference matrix blank with each sample’s lot (samples started desorption apparatus which is connected to the GC system.
through the extraction process on the same 8-h shift, to a
maximum of 20 samples). Column 1: VOCOL glass wide-bore capillary column.
Column 2: RTX–502.2 mega-bore capillary column.
Field replicates may be collected to determine the precision of Column 3: DB-62 mega-bore capillary column.
to determine the accuracy of the analysis when the internal PRECISION & ACCURACY Method detection limits are
standard method is used. dependent upon the characteristics of the gas chromatographic
REFERENCE Semivolatile Organic Compounds by Isotope cally cannot be individually identified and used in the same
Dilution GC/MS. Office of Water Regulation and Standards, calibration mixture or water samples unless an alternative tech-
U.S. EPA Industrial Technology Division, Washington, DC, nique for identification and quantification, such as mass spec-
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, trometry, is used.

Electrolytic conductivity detetor (c) range in g/L (a) was of interest), whose concentration is known in every sample, are
0.02–200. measured using the same internal standard calibration proce-
Electrolytic conductivity detetor (c) MDL in g/L (b) was 0.02. dure. Duplicate field reagent water blanks (trip blanks) must
Electrolytic conductivity detetor (c) accuracy as % recoverywas be analyzed with each set of samples, lab reagent blanks
98. (method blanks) must be analyzed with each batch of samples
Electrolytic conductivity detetor (c) precision as % RSD was 8.3. processed as a group within a work shift. Also, a single lab-
Photoionization detector (d) range in g/L (a) was 0.02–200. fortified blank that contains each of the analytes of interest
Photoionization detector (d) MDL in g/L (b) was 0.06. should be analyzed with each batch of samples processed as a
Photoionization detector (d) accuracy as % recovery was 99. group within a work shift. A 3- to 5-point calibration curve is
Photoionization detector (d) precision as % RSD was 9.5. needed depending on the calibration range factor required.
(a) The applicable concentration range of this method is com- EPA CONTACT & HOTLINE For technical questions contact
pound, instrument, and matrix-dependent. It is listed as Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
being approximately 0.02 to 200 g/L but no specific infor- Drinking Water (WH-550D), 401 M St. SW, Washington, DC
mation is provided so caution should be observed. 20460. Tel. (202) 260-3040. For further information the EPA
(b) The method detection limits reports with this method are Safe Drinking Water Hotline may be called at: (800) 426-4791.
compound, instrument, and matrix-dependent. The values
reported were calculated using reagent water fortifi d with REFERENCE Methods for the Determination of Organic
the corresponding compounds at 10 g/L and a Compounds in Drinking Water, EPA/600/4-88/039 (revised
GC-equipped with a 60 m 0.75 mm VOLCOL wide bore July 1991; Final Rule for determination of compliance with the
capillary column with 1.5 m fi m thickness and using MCL for Total Trihalomethanes under 141.30, in 40 CFR Part
helium carrier gas. 141, Vol. 58, No. 147, Fed. Reg., Tuesday Aug. 3, 1993). U.S.
(c) Recoveries and relative standard deviations were deter- EPA Environmental Monitoring Systems Laboratory, Cincin-
mined from seven samples of reagent water fortifi d with nati, OH, 45268, U.S.A. Available from the National Technical
10 g/L of each compound. 2-Bromo-1-chloropropane was Information Service (NTIS), 5285 Port Royal Road, Spring-
used as the internalstandard forcalculatingaverage recoveries. field, VA 22161; Tel. 800-553-6847. NTIS Order Number is
(d) Recoveries and relative standard deviations were deter- PB91-231480.
10 g/L of each compound. Fluorobenzene was used as the
internal standard for calculating average recoveries.
SAMPLING METHOD Collect samples using a 40- to CAS #87-68-3
distilled water and oven dried at 105C) with a Teflon®-faced TITLE Measurement of Purgeable Organic Compounds in
silicone septum . Collect bubble-free samples and place the sep- Water by Capillary Column GC/MS.
tum with the Teflon® side down on the water. MATRIX Drinking water and raw source water; the latter
SAMPLE PRESERVATION If residual chlorine is present in should include most surface water and groundwater sources.
the water add about 25 mg of ascorbic acid to each vial before METHOD SUMMARY Method 524.2 covers 60 volatile
samples are collected to remove the chlorine. Add hydrochloric organic compounds. An inert gas (zero grade nitrogen or
acid to reduce pH to <2, immediately cool samples to 4 C, and helium) is bubbled through a 25-mL or a 5-mL water sample
store them in a solvent-free refrigerator at 4C until analysis. (depending on the expected concentration of the analytes).
MHT The maximum holding time for samples is 14 days Purged sample components are trapped in a tube of sorbent
from the time they were collected. materials. When purging is complete, the sorbent tube is heated
and backflushed with helium to desorb the trapped sample
SAMPLE PREPARATION Remove the plungers from two onto a capillary GC column.
5-mL syringes and attach a closed syringe valve to each. Warm
the sample to room temperature, open the sample bottle, and INTERFERENCES Impurities in the purge gas and from
carefully pour the sample into one of the syringe barrels to just organic compounds outgassing from the plumbing ahead of
short of overflowing. Replace the syringe plunger, invert the the trap account for many contamination problems. Interfer-
syringe, and compress the sample. Open the syringe valve and ences purged or coextracted from the samples will vary con-
vent any residual air while adjusting the sample volume to siderably from source to source, depending upon the particular
5.0 mL. Add 10 L of the internal calibration standard to the sample or extract being tested. Cross-contamination can occur
sample through the syringe valve. Close the valve. Fill the sec- whenever high-level and low-level samples are analyzed
ond syringe in an identical manner from the same sample sequentially. Samples also can be contaminated by diffusion of
bottle. Reserve this second syringe for a reanalysis if necessary. volatile organics (particularly methylene chloride and fluoro-
QUALITY CONTROL As an initial demonstration of lab
ment and storage.
accuracy and precision, analyze 4 to 7 replicates of a lab fortified
blank containing analyte at 0.1–5 g/L. Collect all samples in INSTRUMENTATION A GC/MS with a data system
duplicate. Surrogate analytes (similar to those of the analytes equipped with one of the following capillary GC columns:

Column 1: VOCOL glass wide bore capillary column. while adjusting the sample volume to 25.0 mL (or 5 mL). For
Column 2: DB-624 fused silica capillary column. samples and blanks, add 5 L of the fortification solution con-
Also required is an all-glass 25 mL or 5-mL purging device, a through the syringe valve. For calibration standards and lab
sorbent trap, and a thermal desorption apparatus which is fortified blanks, add 5 L of the fortification solution contain-
connected to the GC/MS system. ing the internal standard only. Close the valve. Fill the second
syringe in an identical manner from the same sample bottle.
PRECISION & ACCURACY Method detection limits are Reserve this second syringe for a reanalysis if necessary.
compound- and instrument-dependent, and may vary from
approximately 0.02–0.35 g/L. Note in the table below that the QUALITY CONTROL As an initial demonstration of lab
“true” concentration range used for accuracy and precision accuracy and precision, analyze 4 to 7 replicates of a lab fortified
measurements was quite narrow. However, the applicable con- blank containing analyte at 0.2–5 g/L. Collect all samples in
centration range of this method is primarily column dependent duplicate. Surrogate analytes (similar to those of the analytes
and is approximately 0.02 to 200 g/L for the wide-bore thick- of interest), whose concentration is known in every sample, are
film columns. Narrow-bore thin-film columns may have a measured using the same internal standard calibration proce-
capacity which limits the range to about 0.02 to 20 g/L. Ana- dure. Duplicate field reagent water blanks (trip blanks) must
lytes that are inefficiently purged from water will not be be analyzed with each set of samples, lab reagent blanks
detected when present at low concentrations, but they can be (method blanks) must be analyzed with each batch of samples
measured with acceptable accuracy and precision when present processed as a group within a work shift. Also, a single lab-
in sufficient amounts. fortified blank that contains each of the analytes of interest
should be analyzed with each batch of samples processed as a
Analytes that are not separated chromatographically, but which
needed depending on the calibration range factor required.
ions, can be identified and measured in the same calibration
mixture or water sample.Analytes which have very similar mass EPA CONTACT & HOTLINE For technical questions contact
spectra cannot be individually identified and measured in the Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
same calibration mixture or water samples unless they have Drinking Water (WH-550D), 401 M St. SW, Washington, DC
different retention times. Co-eluting compounds with very 20460. Tel. (202) 260-3040. For further information the EPA
similar mass spectra, typically many structural isomers, must Safe Drinking Water Hotline may be called at: (800) 426-4791.
be reported as an isomeric group or pair.
The range (in g/L) was 0.5–10. Compounds in Drinking Water, EPA/600/4-88/039 (revised
The Method Detection Limig (in g/L) was 0.11. July 1991; Final Rule for determination of compliance with the
The accuracy (as % recovery) was 100. MCL for Total Trihalomethanes under 141.30, in 40 CFR Part
The precision (in %) was 6.8. 141, Vol. 58, No. 147, Fed. Reg., Tuesday Aug. 3, 1993). U.S.
Note: Data were obtained from 16–31 determinations using a EPA Environmental Monitoring Systems Laboratory, Cincin-
wide-bore capillary column and a jet separator interfaced to a nati, OH, 45268, U.S.A. Available from the National Technical
quadrupole mass spectrometer. All analytes were in a reagent Information Service (NTIS), 5285 Port Royal Road, Spring-
water matrix. field, VA 22161; Tel. 800-553-6847. NTIS Order Number is
PB91-231480.
silicone septum . Collect bubble-free samples and place the sep- Hexachlorobutadiene EPA Method 625
tum with the Teflon® side down on the water. CAS #87-88-3
the water add about 25 mg of ascorbic acid to each vial before TITLE Base/Neutrals and Acids, U.S. EPA Method 625
samples are collected to remove the chlorine. Add hydrochloric MATRIX This methods covers municipal and industrial
acid to reduce pH to <2, and immediately cool samples to 4 C, wastewaters.
and store them in a solvent-free refrigerator at 4C until analysis.
MHT The maximum holding time for samples is 14 days ally extracted with methylene chloride at a pH greater than 11
from the time they were collected. and again at a pH less than 2 using a separatory funnel or a
SAMPLE PREPARATION Remove the plungers from two continuous extractor. The methylene chloride extract is dried,
25-mL (or 5-mL depending on sample size) syringes and attach concentrated to a volume of 1 mL, and analyzed by GC/MS.
a closed syringe valve to each. Warm the sample to room tem- Qualitative identification of the parameters in the extract is
perature, open the sample bottle, and carefully pour the sample performed using the retention time and the relative abundance
into one of the syringe barrels to just short of overflowing. of three characteristic masses (m/z). Qualitative analysis is per-
Replace the syringe plunger, invert the syringe, and compress formed using either external or internal standard techniques
the sample. Open the syringe valve and vent any residual air with a single characteristic m/z.

Column for base/neutrals: 1.8 m long  2 mm I.D. glass, 100 g/mL in acetone is required. PCBs and multicomponent
packed with 3% SP-2550 on Supelcoport (100/120 mesh) pesticides may be omitted from this test.
or equivalent.
PRECISION & ACCURACY The MDL concentrations were
surrogate compound.
and matrix effects. This method was tested by 15 laboratories REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct.
using reagent water, drinking water, surface water, and indus- 26, 1984.
CAS #87-68-3
The MDL (in g/L) in reagent water was not reported.
The standard deviation (in g/L based on 4 recovery measure- TITLE Halogenated Volatile by Gas Chromatography Using
ments) was 26.3. Photoionization and Electrolytic Conductivity Detectors in
The range (in g/L) for average recovery for 4 measurements Series: Capillary Column Technique
was 37.8–102.2.
MATRIX This method is applicable to nearly all types of
Accuracy (in g/L) as expected recovery for one or more mea- aqueous sludges, caustic liquors, acid liquors, waste solvents,
surements of a sample containing a true concentration of oily wastes, mousses, tars, fibrous wastes, polymeric emulsions,
C was 0.71C-1.01. filter cakes, spent carbons, spent catalysts, soils, and sediments.
tion of measurements at an average concentration found at METHOD SUMMARY This method is used to determine 60
X was 0.19X + 0.92. volatile organic compounds in a variety of solid waste matrices.
Overall precision (in g/L) as expected interlaboratory stan- It provides GC conditions for the detection of halogenated and
dard deviation of measurements in an average concentra- aromatic volatile organic compounds. Samples can be analyzed
tion found at X was 0.26X + 0.49. using direct injection or purge-and-trap (EPA Method 5030).
Groundwater samples must be analyzed using EPA Method
C = True value of the concentration in g/L. 5030 (where applicable). A temperature program is used with
the GC. Detection is achieved by a photoionization detector
(PID) and a Hall electrolytic conductivity detector (HECD) in
SAMPLE PREPARATION Adjust the pH to >11 with sodium series.
hydroxide and serially extract in a separatory funnel with meth-
INTERFERENCES Samples can be contaminated by diffu-
ylene chloride or else in a continuous extractor. Next, adjust sion of volatile organics (particularly chlorofluorocarbons and
the pH to <2 with sulfuric acid and serially extract in a sepa- methylene chloride) through the sample container septum dur-
ratory funnel with methylene chloride or else in a continuous ing shipment and storage.
extractor. Dry the extracts separately through a column of
anhydrous sodium sulfate and then concentrate each of the INSTRUMENTATION A GC-equipped with variable-con-
extracts to 1.0 mL using a K-D apparatus. stant differential flow controllers, subambient oven controller,

PID and HECD detectors connected with a short piece of Semivolatile organics — Containers used to collect samples for
uncoated capillary tubing and a data system. the determination of semivolatile organic compounds should
be soap and water washed followed by methanol (or isopro-
Column: 60 m 0.75 mm I.D.VOCOLwide-bore capillary col-
panol) rinsing. The sample containers should be of glass or
Teflon® and have screw-top covers with Teflon® liners.
PRECISION & ACCURACY MDLs are compound-depen-
Preservation for volatile organics — No preservation is used
dent and vary with purging efficiency and concentration. The
with concentrated waste samples. With liquid samples contain-
applicable concentration range of this method is compound-
and instrument-dependent but is approximately 0.1 to ing no residual chlorine, 4 drops of concentrated hydrochloric
200 g/L. Analytes that are inefficiently purged from water will acid are added and the samples are immediately cooled to 4 C.
not be detected when present at low concentrations, but they When liquid samples contain residual chlorine, they are treated
can be measured with acceptable accuracy and precision when as above and, in addition, 4 drops of 4% aqueous sodium
present in sufficient amounts. The estimated quantitation limit thiosulfate are added. Soil, sediment, and sludge samples are
(EQL) for an individual compound is approximately 1 g/kg only cooled to 4C.
(wet weight) for soil/sediment samples, 100 g/kg (wet weight) Preservation for semivolatile organics — No preservation is
for wastes, and 1 g/L for groundwater. EQLs will be propor- used with concentrated waste samples. With liquid samples
tionately higher for sample extracts and samples that require containing no residual chlorine and with soil, sediment, and
dilution or reduced sample size to avoid saturation of the detector. sludge samples, immediately cooling to 4C is the only preser-
MULTIPLICATION FACTORS FOR OTHER MATRICES (a) vation used. When residual chlorine is present then 3 mL of
10% aqueous sodium sulfate is added for each gallon of sample
Matrix Factor (b)
collected, followed by cooling to 4C.
Groundwater 10
MHT The holding time for all volatile organics samples is
Low-concentration soil 10
14 days. Liquid samples must be extracted within 7 days and
Water miscible liquid waste 500
High-concentration soil and sludge 1250 their extracts analyzed within 40 days. Concentrated waste, soil,
Non-water miscible waste 1250 sediment, and sludge samples must be extracted within 14 days
(a) Sample EQLs are highly matrix-dependent. The EQLs listed
herein are provided for guidance and may not always be achievable. SAMPLE PREPARATION Volatile compounds are intro-
(b) EQL = [Method detection limit] [Factor]. For non-aqueous duced into the gas chromatograph either by direct injector or
samples, the factor is on a wet-weight basis. purge-and-trap (EPA Method 5030). EPA Method 5030 may
be used directly on groundwater samples or low-concentration
SINGLE LABORATORY ACCURACY & PRECISION DATA contaminated soils and sediments. For medium-concentration
FOR VOCs IN WATER soils or sediments, methanolic extraction, as described in EPA
This method was tested in a single lab using water spiked at Method 5030, may be necessary prior to purge-and-trap analysis.
10 g/L and the following data was reported: QUALITY CONTROL Calculate surrogate standard recovery
Recoveries and standard deviations were determined from on all samples, blanks, and spikes.A trip blank is recommended
seven samples and spiked at 10 g/L of each analyte. Recoveries to check on sampling, storage, and handling contamination.
were determined by the internal standard method. Internal Calibration standards, at a minimum of five concentration lev-
standards were: Fluorobenzene for PID and 2-Bromo-1-chlo- els, are prepared in organic-free reagent water. One of the con-
ropropane for HECD. centration levels should be at a concentration near, but above,
The average recovery (in percent) for the PID was 99.
The standard deviation of the recovery for the PID was 9.5. A combination of bromochloromethane, 2-bromo-1-chloro-
The MDL (in g/mL) for the PID was 0.06. propane, 1,4-dichlorobutane, and bromochlorobenzene are
The average recovery (in percent) for the HECD was 98. recommended as surrogate standards to encompass the range
The standard deviation of the recovery for the HECD was 8.3. of the temperature program used in this method.
The MDL (in g/mL) for the HECD was 0.02.
SAMPLE COLLECTION, PRESERVATION & HANDLING ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
Volatile Organics — Standard 40-mL glass screw-cap VOA vials of Solid Waste, Washington, DC, EPA Method 8021A, Rev. 1,
with Teflon®-faced silicone septum may be used for both liquid Nov. 1992.
bubbles present the sample must be retaken. Tap slightly as Hexachlorobutadiene EPA Method 8120
they are filled to try and eliminate as much free air space as CAS #87-68-3
possible. The two vials from each sampling locations should
be sealed in separate plastic bags to prevent cross-contamina- TITLE Chlorinated Hydrocarbons by Gas Chromatography
tion between samples particularly if the sampled waste is sus- MATRIX This method covers aqueous and solid matrices. This
pected of containing high levels of volatile organics. includes a wide variety such as drinking water, groundwater,
industrial wastewaters, surface waters, soils, solids, and sedi- The precision (in g/L) as expected single analyst standard
ments. deviation of measurements at an average concentration of
x” was 0.18 x”-0.08.
METHOD SUMMARY This method is used to determine the
The precision (in g/L) as expected interlaboratory standard
concentration of 14 chlorinated hydrocarbons. It provides gas
deviation measurements at an average concentration found
chromatographic conditions for the detection of ppb concen-
of x” was 0.53x” -0.12.
trations of certain chlorinated hydrocarbons. Prior to use of
this method, appropriate sample extraction techniques must C = True value for the concentration, in g/L.
be used. Both neat and diluted organic liquids (EPA Method x”= Average recovery found for measurements of samples con-
3580, Waste Dilution) may be analyzed by direct injection. A taining a concentration of C, in g/L.
2 to 5 g/mL aliquot of the extract is injected into a gas chro-
Extracts must be stored under refrigeration at 4C and analyzed
pounds in the GC effluent are detected by an electron capture
detector (ECD).
extracted at a neutral, or as is, pH with methylene chloride
sample processing hardware may yield discrete artifacts and/or
using either EPA Method 3510 or EPA Method 3520. Solid
elevated baselines causing misinterpretation of gas chromato-
samples are extracted using either EPA Method 3540 or EPA
grams. Interferences coextracted from samples will vary con-
Method 3550. Prior to gas chromatographic analysis, the
siderably from source to source, depending upon the waste
extraction solvent must be exchanged to hexane.
being sampled.
QUALITY CONTROL The quality control check concentrate
INSTRUMENTATION An analytical system complete with
(EPA Method 8000) should contain each parameter of interest
GC suitable for on-column injections and accessories, includ-
in acetone at the following concentrations: hexachloro-substi-
ing detectors, column supplies, recorder, gases and syringes is
required. A data system for measuring peak areas and/or peak
heights is recommended. The GC is equipped with an electron
ery on all samples, blanks, and spikes.
capture detector (ECD). A K-D apparatus is needed for sample
preparation. Prepare stock standard solutions in isooctane or hexane. Cali-
bration standards at a minimum of five concentrations should
Column 1: 1.8 m 2 mm I.D. glass column packed with 1% be prepared through dilution of the stock standards with isooc-
SP-1000 on Supelcoport (100/120 mesh) or equivalent. tane or hexane. Internal standards and surrogate standards are
Column 2: 1.8 m 2 mm I.D. glass column packed with 1.5% also needed.
OV-1/2.4% OV-225 on Supelcoport (80/100 mesh) or
equivalent. REFERENCE Test Methods for Evaluating Solid Waste, Phys-
PRECISION & ACCURACY The method was tested by 20 of Solid Waste, Washington, DC, 1990. EPA Method 8120 A
laboratories using organic-free reagent water, drinking water, Rev. 1, Nov. 1990.
concentrations over the range 1.0 to 356 g/L. Single operator
precision, overall precision, and method accuracy were found
to be directly related to the concentration of the parameter and Hexachlorobutadiene EPA Method 8121
essentially independent of the sample matrix. CAS #87-68-3
MULTIPLICATION FACTORS FOR OTHER MATRICES (a) TITLE Chlorinated Hydrocarbons by GC: Capillary Column
Matrix Factor (b) Technique
Groundwater 10 MATRIX This method covers aqueous and solid matrices.
Low-concentration soil by ultrasonic cleanup 670 This includes a wide variety such as drinking water, ground-
extraction with GPC water, industrial wastewaters, surface waters, soils, solids, and
High-concentration soil and sludges 10,000 sediments.
Non-water miscible waste 100,000 METHOD SUMMARY This method provides procedures for
the determination of 22 chlorinated hydrocarbons in water,
(a) Sample EQLs are highly matrix-dependent. The EQLs listed are soil/sediment, and waste matrices. A measured volume or
provided for guidance and may not always be achievable. weight of sample is extracted by using one of the appropriate
(b) EQL = [Method detection limit] [Factor]. For non-aqueous sample extraction techniques specified in EPA Method 3510,
samples, the factor is on a wet-weight basis. EPA Method 3520, EPA Method 3540, or EPA Method 3550,
or diluted using EPA Method 3580. Aqueous samples are
extracted at neutral pH with methylene chloride by using either
upon the performance in a single lab.
a separatory funnel (EPA Method 3510) or a continuous liquid-
The accuracy (in g/L) as expected recovery for one or more liquid extractor (EPA Method 3520). Solid samples are
measurements of a sample containing a concentration of C extracted with hexane/acetone (1:1) by using a Soxhlet extrac-
was 0.61C + 0.03. tor (EPA Method 3540) or with methylene chloride/acetone
(1:1) by using an ultrasonic extractor (EPA Method 3550).After PRECISION & ACCURACY MDL is the method detection
cleanup, the extract or diluted sample is analyzed by gas chro- limit for organic-free reagent water. MDLwas determined from
matography with electron capture detection (GC/ECD). the analysis of eight replicate aliquots processed through the
entire analytical method (extraction, Florisil cartridge cleanup,
The sensitivity level of this method usually depends on the level and GC/ECD analysis).
of interferences rather than on instrumental limitations. This
method may be used in conjunction with EPA Method 3620, The MDL (in ng/L) was 1.4.
Florisil Column Cleanup, EPA Method 3660, Sulfur Cleanup, The accuracy (as average % recovery using 5 determinations
and EPA Method 3640, Gel Permeation Chromatography, to and no Florisil cleanup) from a spike concentration of 1.0 g/L
aid in the elimination of interferences. and separatory funnel extraction was 95% with a final volume
INTERFERENCES Solvents, reagents, glassware, and other of 10 mL.
hardware used in sample processing may introduce artifacts The precision (as RSD% using 5 determinations and no Florisil
which may result in elevated baselines, causing misinterpreta- cleanup) from a spike concentration of 1.0 g/L and separatory
tion of gas chromatograms. Interferants coextracted from the funnel extraction was 3.6% with a final volume of 10 mL.
samples will vary considerably from waste to waste. Glassware
must be scrupulously clean. Phthalate esters, if present in a The accuracy (as average % recovery using 5 determinations
sample, will interfere only with the BHC isomers. The presence and no Florisil cleanup), from a spike concentration of 330 g/L
of elemental sulfur will result in large peaks, and can often and ultrasonic extraction of solid samples using 1:1 methylene
mask the region of compounds eluting after 1,2,4,5-tetrachloro- chloride and acetone, was 83% with a final volume of 10 mL.
benzene. The tetrabutylammonium (TBA)-sulfite procedure The precision (as RSD% using 5 determinations and no Florisil
(EPA Method 3660) works well for the removal of elemental cleanup), from a spike concentration of 330 g/L and ultra-
sulfur. Waxes and lipids can be removed by gel permeation sonic extraction of solid samples using 1:1 methylene chloride
chromatography (EPA Method 3640). and acetone, was 4.7% with a final volume of 10 mL.
INSTRUMENTATION A GC suitable for on-column injec- SAMPLE COLLECTION, PRESERVATION & HANDLING
tions and all required accessories, including and electron cap- Volatile Organics — Standard 40-mL glass screw-cap VOA vials
ture detector (ECD), analytical columns, recorder, gases, and with Teflon®-faced silicone septum may be used for both liquid
syringes are needed. A data system for measuring peak heights and solid matrices. When collecting samples, liquids and solids
and/or peak areas is recommended. A Kuderna-Danish (K-D) should be introduced into the vials gently to reduce agitation
apparatus will also be needed to concentrate extracts. which might drive off volatile compounds. If there are any air
bubbles present the sample must be retaken. The vials with
solids should be tapped slightly as they are filled to try and
eliminate as much free air space as possible. Two vials from
(DB-210 or equivalent). each sampling location should be sealed in separate plastic bags
Column 2: 30 m 0.53 mm I.D. fused-silica capillary column to prevent cross-contamination between samples.
chemically bonded with polyethylene glycol (DB-WAX or
equivalent). Semivolatile organics — Containers used to collect samples for
the determination of semivolatile organic compounds should
PRECISION & ACCURACY This method has been tested in be soap and water washed followed by methanol (or isopro-
a single lab by using organic-free reagent water, sandy loam panol) rinsing. The sample containers should be of glass or
samples, and extracts which were spiked with the test com- Teflon® and have screw-top covers with Teflon® liners.
method accuracy were found to be related to the concentration Preservation for volatile organics — No preservation is used
of compound and the type of matrix. The accuracy and preci- with concentrated waste samples. With liquid samples contain-
sion technique will be determined by the sample matrix, sam- ing no residual chlorine, 4 drops of concentrated hydrochloric
ple preparation technique, optional cleanup techniques, and acid are added and the samples are immediately cooled to 4 C.
calibration procedures used. When liquid samples contain residual chlorine, they are treated
MULTIPLICATION FACTORS FOR OTHER MATRICES (a) thiosulfate are added to remove the residual chlorine. Soil,
Matrix Factor (b) sediment, and sludge samples are only cooled to 4C.
Groundwater 10 Preservation for semivolatile organics — No preservation is
Low-concentration soil by ultrasonic cleanup 670 used with concentrated waste samples. With liquid samples
extraction with GPC containing no residual chlorine and with soil, sediment, and
High-concentration soil and sludges 10,000 sludge samples, immediately cooling to 4C is the only preser-
by ultrasonic extraction vation used. When residual chlorine is present then 3 mL of
Non-water miscible waste 100,000 10% aqueous sodium sulfate is added for each gallon of sample
provided for guidance and may not always be achievable. Holding times — The holding time for all volatile organics
(b) EQL = [Method detection limit] [Factor]. For non-aqueous samples is 14 days. Liquid samples must be extracted within
samples, the factor is on a wet-weight basis. 7 days and their extracts analyzed within 40 days. Concentrated
waste, soil, sediment, and sludge samples must be extracted Hexachlorobutadiene EPA Method 8260
within 14 days and their extracts analyzed within 40 days. CAS #87-68-3
in hexane. Calibration standards at a minimum of five concen- TITLE Volatile Organic Compounds by GC/MS: Capillary
trations should be prepared through dilution of the stock stan- Column Technique
dards with hexane. The suggested internal standards are: MATRIX This method is applicable to nearly all types of
2,5-dibromotoluene, 1,3,5-t r ibromobenzene, and , samples, regardless of water content, including groundwater,
dibromo-m-xylene. The analyst can use any of the three com- soils, and sediments.
pounds provided that theyare resolved from matrix interferences.
METHOD SUMMARY Method 8260A covers 58 volatile
1,4-dichloronaphthalene, and 2,3,4,5,6-pentachlorotoluene.
In general, water samples are extracted at a neutral pH with limited applications). Zero-grade helium is bubbled through a
methylene chloride using a separatory funnel (EPA Method 5-mL solution at ambient temperature. Purged sample com-
3510) or a continuous liquid-liquid extractor (EPA Method ponents are trapped in a tube containing suitable sorbent mate-
3520). Solid samples are extracted with hexane/acetone (1:1 rials. When purging is complete, the sorbent tube is heated and
v:v) using a Soxhlet extractor (EPA Method 3540) or with backflushed with helium to desorb trapped sample compo-
methylene chloride/acetone (1:1 v:v) using an ultrasonic nents. The analytes are desorbed directly to a large bore capil-
extractor (EPA Method 3550). Non-aqueous waste samples lary or cryofocussed on a capillary precolumn before being
may be diluted using EPA Method 3580. Prior to Florisil flash evaporated to a narrow bore capillary for analysis.
cleanup or gas chromatographic analysis, the extraction solvent INTERFERENCES Major contaminant sources are volatile
must be exchanged to hexane. Sample extracts that will be materials in the lab and impurities in the inert purging gas and
subjected to gel permeation chromatography do not need sol- in the sorbent trap. Interfering contamination may occur when
vent exchange. a sample containing low concentrations of volatile organic
Cleanup procedures may not be necessary for a relatively clean compounds is analyzed immediately after a sample containing
matrix. If removal of interferences such as chlorinated phenols, high concentrations of volatile organic compounds. After anal-
phthalate esters, etc., is required, proceed with the procedure ysis of a sample containing high concentrations of volatile
outlined in EPA Method 3620. organic compounds, one or more calibration blanks should be
QUALITY CONTROL Analyze a quality control check stan- samples prior to purge-and-trap GC/MS analysis is highly rec-
dard to demonstrate that the operation of the GC is in control. ommended to prevent contamination of the system. This is
The frequency of the check standard analysis is equivalent to especially true for soil and waste samples.
10% of the samples analyzed. If the recovery of any compound
found in the check standard is less than 80% of the certified Special precautions must be taken to analyze for methylene
value, the problem must be corrected and a new set of calibra- chloride. The analytical and sample storage area should be
tion standards must be prepared and analyzed. Calculate sur- isolated from all atmospheric sources of methylene chloride.
rogate standard recoveries for all samples, blanks, and spikes. All gas chromatography carrier gas lines and purge gas plumb-
An internal standard peak area check must be performed on
Laboratory clothing previously exposed to methylene chloride
all samples. The internal standard must be evaluated for accep-
fumes during liquid-liquid extraction procedures can contrib-
ute to sample contamination.
nal standard deviates by more than 30% from the average area
for the internal standard in the calibration standards. When Samples can also be contaminated by diffusion of volatile
the internal standard peak area is outside that limit, all samples organics (particularly methylene chloride and fluorocarbons)
that fall outside the QC criteria must be reanalyzed. Any com- through the septum seal during shipment and storage. A trip
pound confirmed by two columns may also be confirmed by blank can serve as a check on such contamination.
GC/MS (EPA Method 8270). The GC/MS would normally INSTRUMENTATION GC/MS with a temperature-pro-
require a minimum concentration of 1 ng/L in the final grammable chromatograph suitable for splitless injection
extract for each compound. Include a mid-concentration cal- equipped with variable constant differential flow controllers, a
ibration standard after each group of 20 samples in the analysis subambient oven controller, a purging device, sorbent trap, a
sequence. The response factors for the mid-concentration cal- thermal desorption apparatus and a capillary precolumn inter-
ibration must be within 15% of the average values for the face when using cryogenic cooling will be needed. The follow-
multiconcentration calibration. ing GC columns may be used:
REFERENCE Test Methods for Evaluating Solid Waste, Phys- Column 1: 60 m 0.75 mm I.D. capillary column coated with
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office VOCOL, 1.5 m film thickness.
of Solid Waste, Washington, DC, 1990. EPA Method 8121, Rev. Column 2: 30 m 0.53 mm capillary column coated with DB-
0, Nov. 1990. 624 or VOCOL, 3 m film thickness.

Column 3: 30 m 0.32 mm I.D. capillary column coated with determine whether to use the low-concentration method
DB-5 or SE-54, 1-m film thickness. (0.005–1 mg/kg) or the high-concentration method (>1 mg/kg).
PRECISION & ACCURACY This method has been tested in Low-concentration method — The low-concentration method
a single lab using spiked water. Using a wide-bore capillary is based on purging a heated sediment or soil sample mixed
column, water was spiked at concentrations between 0.5 and with organic-free reagent water containing the surrogate and
10 g/L. Single lab accuracy and precision data are presented. internal standards. Analyze all reagent blanks and standards
The MDL actually achieved in a given analysis will vary under the same conditions as the samples.
depending on instrument sensitivity and matrix effects. Use a 5-g sample if the expected concentration is <0.1 mg/kg
The MDL (a) in g/L was 0.11. or a 1-g sample for expected concentrations between 0.1 and
The concentration range in g/L was 0.5–10. 1 mg/kg. Mix the contents of the sample container with a nar-
The mean accuracy (% of true value) was 100. row metal spatula. Weigh the amount of the sample into a tared
The precision as relative standard deviation was 6.8. purge device. Add the spiked water to the purge device, which
contains the weighed amount of sample, and connect the
Note: The MDL is based on a 25-mL sample volume instead device to the purge-and-trap system.
of a 5-mL sample volume.
SAMPLING METHOD extracting the sediment or soil with methanol. A waste sample
Liquid samples — Use a 40-mL glass screw-cap VOA vial with is either extracted or diluted, depending on its solubility in
a Teflon®-faced silicone septum that has been prewashed, methanol. Wastes that are insoluble in methanol are diluted
rinsed with distilled deionized water, and oven dried. If residual with reagent tetraglyme or possibly polyethylene glycol (PEG).
chlorine is present, collect the sample in a 4-oz soil VOA con- An aliquot of the extract is added to organic-free reagent water
tainer which has been pre-preserved with 4 drops of 10% containing surrogate and internal standards. This is purged at
sodium thiosulfate. Mix gently and transfer the sample to a ambient temperature. All samples with an expected concentra-
40-mL VOA vial. Collect bubble-free samples in duplicate and tion of >1.0 mg/kg should be analyzed by this method.
seal each sample in a separate plastic bag. Mix the contents of the sample container with a narrow metal
Soils, sediments and sludges — Use an 8-oz widemouth glass spatula. For sediments or soils and solid wastes that are insol-
bottle with Teflon®-faced silicone septum that has been pre- uble in methanol, weigh 4 g (wet weight) of sample into a tared
washed, rinsed with distilled deionized water, and oven dried. 20-mL vial. For waste that is soluble in methanol, tetraglyme,
Do not heat the septum for more than 1 h. Tap slightly to
eliminate any free air space. Collect samples in duplicate and
9.0 mL of appropriate solvent then add 1.0 mL of a surrogate
seal each one in a separate plastic bag.
SAMPLE PRESERVATION
METHANOL EXTRACT REQUIRED FOR ANALYSIS
Liquid samples — Add 4 drops of concentrated HCL, cool to
OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
Soils, sediments and sludges — Cool samples to 4C and store Concentration Range Methanol Extract (a)
500–10,000 g/kg 100 L
MHT The maximum holding time of any sample (liquids, 1,000–20,000 g/kg 50 L
soils, sediments, and sludges) is 14 days. 5,000–100,000 g/kg 10 L
SAMPLE PREPARATION
short of overflowing. Replace the syringe plunger and compress
(a) The volume of methanol added to 5 mL of water being purged
system, glassware, and reagents are under control. Blank sam-
spiking solution.

spiked samples must be carried through all stages of the sample capillary column. A continuous liquid-liquid extractor
preparation and measurement steps. QC samples mentioned equipped with Teflon® or glass connection joints and stopcocks
in the section on Interferences will also be needed as appropri- requiring no lubrication, a K-D concentrating apparatus, water
ate to those situations. bath, and an ultrasonic disrupter with a minimum power of
Matrix spiking standards should be prepared from volatile 300 W and with pulsing capability are also required.
organic compounds which will be representative of the com- PRECISION & ACCURACY The estimated quantitation
pounds being investigated. The recommended internal stan- limit (EQL) of Method 8270B for determining an individual
dards are chlorobenzene-d 5, 1,4 -difluorobenzene, compound is approximately 1 mg/kg (wet weight) for soil or
1,4-dichlorobenzene-d4, and pentafluorobenzene. Using stock sediment samples, 1–200 mg/kg for wastes (dependent on
standard solutions, prepare secondary dilution standards con-
taining the compounds of interest, either singly or mixed
together in methanol. Store them in a vial with no headspace water samples. EQLs will be proportionately higher for sample
for no more than one week. Surrogates recommended are tol- extracts that require dilution to avoid saturation of the detector.
uene-d8, 4-bromofluorobenzene, and dibromofluoromethane. The EQL(b) for groundwater in g/L is 10.
Each sample undergoing GC/MS analysis must be spiked with The EQL (a, b) for low concentrations in soil and sediment
10 L of the surrogate spiking solution prior to analysis. in g/kg is 660.
REFERENCE Test Methods for Evaluating Solid Waste (SW- Accuracy as g/L is 0.71C–1.01.
846). U.S. EPA 1983, Method 8260A, Rev. 1, Nov. 1990. Office Overall precision in g/L is 0.26X + 0.49.
of Solid Waste, Washington, DC. (a) EQLs listed for soil/sediment are based on wet weight. Nor-
Hexachlorobutadiene EPA Method 8270 This calculation is based on a 30-g sample and gel perme-
lakes, etc.
required. The GC column used is a 30 m 0.25 mm I.D. (or MHT Liquid samples must be extracted within 7 days and the
0.32 mm I.D.) 1um film thickness silicone-coated fused silica extracts analyzed within 40 days. Soils, sediments, or sludges may

be stored for a maximum of 14 days and the extracts analyzed must be inspected for malfunctions and corrections must be
within 40 days. made, as appropriate.
concentrator.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous Hexachlorobutadiene EPA Method 503.1
sulfate until the sample is free flowing. Add 1 mL of surrogate TITLE Aromatic & Unsaturated VOCs
MATRIX Drinking water (finished or in Water any treatment
stage) and raw source water.
amount added of the surrogates and matrix spiking com- APPLICATION Method covers 28 aromatic and unsaturated
pounds should result in a final concentration of 100 ng/ L of VOCs. An inert gas is bubbled through a 5-mL water sample.
each base/neutral analyte and 200 ng/L of each acid analyte Purged sample components are trapped in tube of sorbent
in the extract to be analyzed (assuming a 1- L injection). materials. When purging is complete, sorbent tube is heated
Immediately add a 100-mL mixture of 1:1 methylene chlo- and backflushed with inert gas to desorb trapped sample onto
ride:acetone and extract the sample ultrasonically for 3 min a packed GC column.
INTERFERENCES During analysis, major contaminant
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. sources are volatile materials in the lab and impurities in purg-
ing gas and sorbent trap. With high and low level samples, there
QUALITY CONTROL A methylene chloride solution con- can be carryover contamination. Excess water causes a negative
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is baseline deflection.
performance check also must be made during every 12-h shift. INSTRUMENTATION Purge and Trap GC w/photoioniza-
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- tion detector. ( Two GC columns are recommended);
rophenol, and benzidine is required to verify injection port Column 1: 5% SP-1200 and 1.75% Bentone 34 on Supelcoport;
inertness and GC column performance. A calibration standard 5% 1,2,3-tris(2-cyanoethoxy)propane on Chromosorb W.
at mid-concentration, containing each compound of interest, RANGE 2.2–600 g/L (Drinking water)
during analysis. After the system performance check is met, MDL 0.02 g/L in water
calibration check compounds (CCCs) are used to check the PRECISION RSD = 16.8% at 0.50 g/L; 10 samples
ACCURACY Average recovery = 74% at 0.50 g/L; 10 samples
calibration check standard must be evaluated immediately after SAMPLING METHOD Use a 40–120-mL screw-cap vial
or during data acquisition. If the retention time for any internal (prewashed with detergent, rinsed with distilled water and oven
standard changes by more than 30 seconds from the last check dried at 105C) with a PTFE-faced silicone septum . If residual
calibration (12 h), the chromatographic system must be chlorine is in the water add about 25 mg of ascorbic acid to
inspected for malfunctions and corrections must be made, as each vial before sample collection. Collect bubble-free samples.
STABILITY Cool to 4C; HCl to pH <2.
the last daily calibration standard check, the mass spectrometer MHT 14 days.

QUALITY CONTROL As an initial demonstration of lab MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
accuracy and precision, analyze 4 to 7 replicates of a lab fortified Matrix Factor (b)
blank containing analyte at 0.1–5 g/L. Collect all samples in
duplicate. Groundwater 10
Low-concentration soil by ultrasonic cleanup 670
REFERENCE Method 503.1, Volatile Aromatic & Unsatur- extraction with GPC
ated Organic Compounds in H2O by Purge and Trap GC, EPA High-concentration soil and sludges 10,000
600/4-88/039. by ultrasonic extraction
Hexachlorocyclohexane EPA Method 8120 provided for guidance and may not always be achievable.
CAS #608-73-1 (b) EQL = [Method detection limit] [Factor]. For non-aqueous
samples, the factor is on a wet-weight basis.
TITLE Chlorinated Hydrocarbons by Gas Chromatography
MATRIX This method covers aqueous and solid matrices. upon the performance in a single lab.
water, industrial wastewaters, surface waters, soils, solids, and The accuracy (in g/L) as expected recovery for one or more
sediments. measurements of a sample containing a concentration of C
was No Data.
METHOD SUMMARY This method is used to determine the
concentration of 14 chlorinated hydrocarbons. It provides gas The precision (in g/L) as expected single analyst standard
chromatographic conditions for the detection of ppb concen- deviation of measurements at an average concentration of
trations of certain chlorinated hydrocarbons. Prior to use of x” was No Data.
this method, appropriate sample extraction techniques must The precision (in g/L) as expected interlaboratory standard
be used. Both neat and diluted organic liquids (EPA Method deviation measurements at an average concentration found
3580, Waste Dilution) may be analyzed by direct injection. A of x” was No Data.
2 to 5 g/mL aliquot of the extract is injected into a gas chro- C = True value for the concentration, in g/L.
matograph (GC) using the solvent flush technique, and com- x”= Average recovery found for measurements of samples con-
pounds in the GC effluent are detected by an electron capture taining a concentration of C, in g/L.
detector (ECD).
Extracts must be stored under refrigeration at 4C and analyzed
sample processing hardware may yield discrete artifacts and/or
elevated baselines causing misinterpretation of gas chromato-
grams. Interferences coextracted from samples will vary con- SAMPLE PREPARATION In general, water samples are
siderably from source to source, depending upon the waste extracted at a neutral, or as is, pH with methylene chloride
being sampled. using either EPA Method 3510 or EPA Method 3520. Solid
INSTRUMENTATION An analytical system complete with samples are extracted using either EPA Method 3540 or EPA
GC suitable for on-column injections and accessories, includ- Method 3550. Prior to gas chromatographic analysis, the
ing detectors, column supplies, recorder, gases and syringes is extraction solvent must be exchanged to hexane.
required. A data system for measuring peak areas and/or peak QUALITY CONTROL The quality control check concentrate
heights is recommended. The GC is equipped with an electron (EPA Method 8000) should contain each parameter of interest
capture detector (ECD). A K-D apparatus is needed for sample in acetone at the following concentrations: hexachloro-substi-
preparation.
Column 1: 1.8 m 2 mm I.D. glass column packed with 1% hydrocarbon, 100 g/mL. Calculate surrogate standard recov-
SP-1000 on Supelcoport (100/120 mesh) or equivalent. ery on all samples, blanks, and spikes.
Column 2: 1.8 m 2 mm I.D. glass column packed with 1.5%
OV-1/2.4% OV-225 on Supelcoport (80/100 mesh) or Prepare stock standard solutions in isooctane or hexane. Cali-
equivalent. bration standards at a minimum of five concentrations should
be prepared through dilution of the stock standards with isooc-
PRECISION & ACCURACY The method was tested by 20 tane or hexane. Internal standards and surrogate standards are
laboratories using organic-free reagent water, drinking water, also needed.
concentrations over the range 1.0 to 356 g/L. Single operator REFERENCE Test Methods for Evaluating Solid Waste, Phys-
precision, overall precision, and method accuracy were found ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
to be directly related to the concentration of the parameter and of Solid Waste, Washington, DC, 1990. EPA Method 8120 A
essentially independent of the sample matrix. Rev. 1, Nov. 1990.

Hexachlorocyclopentadiene EPA Method 1625
present.
METHOD SUMMARY This method is used to determine The MDL (in g/kg) in low solids was not detected and in high
176 semivolatile toxic organic pollutants associated with the solids was not detected; these were determined in digested
CWA (as amended 1987); the RCRA (as amended 1986); the sludge (low solids) and in filter cake or compost (high solids).

Spike all samples with labeled compounds to assess method of sample extracts may be necessary in these cases. Some pes-
performance. Compute percent recovery of the labeled com- ticides and commercial PCB products from aqueous solutions
pounds using the internal standard method. Compare the adhere to glass surfaces, so sample transfers and contact with
labeled compound recovery for each compound with the cor- glass surfaces should be minimized. Some pesticides are rapidly
responding labeled compound recovery. oxidized by chlorine so dechlorination with sodium thiosulfate
at the time of sample collection is important. Also, splitless
and concentrate a 1-L reagent water blank or a high solids INSTRUMENTATION A gas chromatograph/electron cap-
reference matrix blank with each sample’s lot (samples started ture detector/data system, with temperature programming and
through the extraction process on the same 8-h shift, to a split/splitless injector suitable for use with capillary columns is
maximum of 20 samples). needed.
Field replicates may be collected to determine the precision of Column 1: 0.32 mm I.D.  30 m fused silica capillary with
the sampling technique, and spiked samples may be required chemically bond methyl polysiloxane phase (DB-1, 1.0 m
to determine the accuracy of the analysis when the internal film, or equivalent).
standard method is used. Column 2: 0.32 mm I.D. 30 m fused silica capillary with 1:1
REFERENCE Semivolatile Organic Compounds by Isotope mixed phase of dimethyl silicone and polyethylene glycol
Dilution GC/MS. Office of Water Regulation and Standards, (Durawax-DX3, 0.25 m film, or equivalent).
U.S. EPA Industrial Technology Division, Washington, DC, Column 3: 0.32 mm I.D.  25 m fused silica capillary with
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, chemically bonded 50:50 methyl-phenyl silicone (OV-17,
U.S. EPA, Office of Water Regulations and Standards, 401 M 1.5 m film, or equivalent).
St., SW, Washington, DC, 20460. Phone: 202-382-7131). Column 1 should be used as the primary analytical column.
Hexachlorocyclopentadiene EPA Method 505 PRECISION & ACCURACY Method detection limits are
CAS #77-47-4 dependent upon the characteristics of the gas chromatographic
TITLE Analysis of Organohalide Pesticides and Commercial cally cannot be individually identified and used in the same
Polychlorinated Biphenyl (PCB) Products in Water by Microex- calibration mixture or water samples unless an alternative tech-
traction and Gas Chromatography. U.S. EPA Method 505, Rev. nique for identification and quantification, such as mass spec-
2.0, 1989. trometry, is used.
MATRIX This method is applicable to drinking water and The concentration(s) (in g/L) used for these QC measure-
raw source water. The latter should include most surface water ments was 0.15 and 0.35.
and groundwater sources. The MDL (in g/L) was 0.13.
commercial PCB products. This is a very sensitive method that centration(s) was 73 and 73 and the precision (%) was 5.1
is more useful for monitoring than for exploratory analyses. and 11.7.
extracted by shaking with 2 mL of hexane. The sample extracts centration(s) was 87 and 69 and the precision (%) was 5.1
1–2 L portions of samples, blanks, and standards may be tration(s) was 191 and 109 and the precision (5) was 18.5
manually injected. Each extract is analyzed by capillary and 14.3.
GC/ECD with confirmation using either a second capillary Note: No range of concentrations is provided with this method.
column or GC/MS. The electron capture detector is easy to use,
but it is a nonselective detector. The microextraction technique SAMPLING METHOD Collect samples using a 40-mL
also eliminates the expensive sample preparation costs of other screw-cap vial (prewashed with detergent, rinsed with distilled
methods, but it has the disadvantage of being less sensitive than water and oven dried at 400C for one h) with a Teflon®-faced
most because the extracts are not concentrated. silicone septum . Collect bubble-free samples and place the sep-
contaminants in solvents, reagents, glassware, and other sample SAMPLE PRESERVATION If residual chlorine is present in
processing apparatus that lead to discrete artifacts or elevated the water add about 3 mg of sodium thiosulfate to each vial
baselines. Interfering contamination may occur when a sample before samples are collected to remove the chlorine. Alterna-
containing low concentrations of analytes is analyzed immedi- tively, add 75 L of 0.04 g/mL solution of sodium thiosulfate
ately following a sample containing relatively high concentra- to each vial just prior to sampling. Immediately cool samples
tions of the analytes. Matrix interferences also may be caused to 4C, and store them in a solvent-free refrigerator at 4C until
by contaminants that are coextracted from the sample; cleanup analysis.

MHT The maximum holding time is 14 days from the time this method, appropriate sample extraction techniques must
the sample was collected until it must be analyzed. be used. Both neat and diluted organic liquids (EPA Method
3580, Waste Dilution) may be analyzed by direct injection. A
2 to 5 g/mL aliquot of the extract is injected into a gas chro-
and allow it to come to room temperature. Remove a 5-mL
volume from each container and weigh the container to the
nearest 0.1 g. Add 6 g of sodium chloride and 2.0 mL of hexane
detector (ECD).
to each sample bottle. Recap the sample and shake it vigorously
for one min. Allow the water and hexane phases to separate, INTERFERENCES Solvents, reagents, glassware, and other
remove the cap, and transfer 0.5 mL of hexane into an autosam- sample processing hardware may yield discrete artifacts and/or
pler vial using a disposable glass pipette. Transfer the remaining elevated baselines causing misinterpretation of gas chromato-
hexane phase into a second autosampler vial and store at 4C grams. Interferences coextracted from samples will vary con-
for reanalysis, if necessary. Discard the remaining sample/hex- siderably from source to source, depending upon the waste
ane mixture and reweigh the empty container to determine net being sampled.
weight of sample. INSTRUMENTATION An analytical system complete with
QUALITY CONTROL Minimum quality control require- GC suitable for on-column injections and accessories, includ-
ments are initial demonstration of lab capability, analysis of lab ing detectors, column supplies, recorder, gases and syringes is
reagent blanks, fortified blanks, fortified sample matrix, and required. A data system for measuring peak areas and/or peak
quality control samples. The lab must analyze at least one for- heights is recommended. The GC is equipped with an electron
tified blank per sample set, or at least one for every 20 samples. capture detector (ECD). A K-D apparatus is needed for sample
The fortifying concentration of each analyte should be 10 times preparation.
the method detection limit or the maximum calibration limit Column 1: 1.8 m 2 mm I.D. glass column packed with 1%
(MCL), whichever is less. Calculate accuracy as percent recov- SP-1000 on Supelcoport (100/120 mesh) or equivalent.
ery and develop control limits from the mean percent recovery Column 2: 1.8 m 2 mm I.D. glass column packed with 1.5%
and standard deviation. OV-1/2.4% OV-225 on Supelcoport (80/100 mesh) or
The lab must add a known concentration of the analytes to a equivalent.
minimum of 10% of the routine samples, or one lab fortified PRECISION & ACCURACY The method was tested by 20
sample matrix per sample set. Calculate the percent recovery laboratories using organic-free reagent water, drinking water,
for each analyte and compare to the control limits established surface water, and three industrial wastewaters spiked at six
from the analyses of the fortified blanks. concentrations over the range 1.0 to 356 g/L. Single operator
EPA CONTACT & HOTLINE For technical questions contact precision, overall precision, and method accuracy were found
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and to be directly related to the concentration of the parameter and
essentially independent of the sample matrix.
20460. Tel. (202) 260-3040. For further information the EPA MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
Safe Drinking Water Hotline may be called at: (800) 426-4791. Matrix Factor (b)
REFERENCE Methods for the Determination of Organic Groundwater 10
Compounds in Drinking Water, EPA/600/4-88/039 (revised Low-concentration soil by ultrasonic cleanup 670
July 1991). U.S. EPA Environmental Monitoring Systems Lab- extraction with GPC
oratory, Cincinnati, OH, 45268, U.S.A. Available from the High-concentration soil and sludges 10,000
National Technical Information Service (NTIS), 5285 Port by ultrasonic extraction
Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS Non-water miscible waste 100,000
Hexachlorocyclopentadiene EPA Method 8120 samples, the factor is on a wet-weight basis.
CAS #77-47-4
TITLE Chlorinated Hydrocarbons by Gas Chromatography upon the performance in a single lab.
MATRIX This method covers aqueous and solid matrices. The accuracy (in g/L) as expected recovery for one or more
This includes a wide variety such as drinking water, ground- measurements of a sample containing a concentration of C
water, industrial wastewaters, surface waters, soils, solids, and was 0.47C.
sediments. The precision (in g/L) as expected single analyst standard
deviation of measurements at an average concentration of
METHOD SUMMARY This method is used to determine the x” was 0.24x”.
concentration of 14 chlorinated hydrocarbons. It provides gas The precision (in g/L) as expected interlaboratory standard
chromatographic conditions for the detection of ppb concen- deviation measurements at an average concentration found
trations of certain chlorinated hydrocarbons. Prior to use of of x” was 0.50x”.

C = True value for the concentration, in g/L. method may be used in conjunction with EPA Method 3620,
x”= Average recovery found for measurements of samples con- Florisil Column Cleanup, EPA Method 3660, Sulfur Cleanup,
taining a concentration of C, in g/L. and EPA Method 3640, Gel Permeation Chromatography, to
aid in the elimination of interferences.
Extracts must be stored under refrigeration at 4C and analyzed INTERFERENCES Solvents, reagents, glassware, and other
within 40 days of extraction. hardware used in sample processing may introduce artifacts
which may result in elevated baselines, causing misinterpreta-
tion of gas chromatograms. Interferants coextracted from the
extracted at a neutral, or as is, pH with methylene chloride
samples will vary considerably from waste to waste. Glassware
using either EPA Method 3510 or EPA Method 3520. Solid
must be scrupulously clean. Phthalate esters, if present in a
samples are extracted using either EPA Method 3540 or EPA
sample, will interfere only with the BHC isomers. The presence
Method 3550. Prior to gas chromatographic analysis, the
of elemental sulfur will result in large peaks, and can often
extraction solvent must be exchanged to hexane.
mask the region of compounds eluting after 1,2,4,5-tetrachloro-
QUALITY CONTROL The quality control check concentrate benzene. The tetrabutylammonium (TBA)-sulfite procedure
(EPA Method 8000) should contain each parameter of interest (EPA Method 3660) works well for the removal of elemental
in acetone at the following concentrations: hexachloro-substi- sulfur. Waxes and lipids can be removed by gel permeation
tuted hydrocarbon, 10 g/mL; and any other chlorinated chromatography (EPA Method 3640).
ery on all samples, blanks, and spikes. INSTRUMENTATION A GC suitable for on-column injec-
tions and all required accessories, including and electron cap-
Prepare stock standard solutions in isooctane or hexane. Cali- ture detector (ECD), analytical columns, recorder, gases, and
bration standards at a minimum of five concentrations should syringes are needed. A data system for measuring peak heights
be prepared through dilution of the stock standards with isooc- and/or peak areas is recommended. A Kuderna-Danish (K-D)
tane or hexane. Internal standards and surrogate standards are apparatus will also be needed to concentrate extracts.
also needed.
REFERENCE Test Methods for Evaluating Solid Waste, Phys- chemically bonded with trifluoropropyl methyl silicone
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office (DB-210 or equivalent).
of Solid Waste, Washington, DC, 1990. EPA Method 8120 A Column 2: 30 m 0.53 mm I.D. fused-silica capillary column
Rev. 1, Nov. 1990. chemically bonded with polyethylene glycol (DB-WAX or
equivalent).
PRECISION & ACCURACY This method has been tested in
Hexachlorocyclopentadiene EPA Method 8121 a single lab by using organic-free reagent water, sandy loam
CAS #77-47-4 samples, and extracts which were spiked with the test com-
TITLE Chlorinated Hydrocarbons by GC: Capillary Column method accuracy were found to be related to the concentration
Technique of compound and the type of matrix. The accuracy and preci-
MATRIX This method covers aqueous and solid matrices. sion technique will be determined by the sample matrix, sam-
This includes a wide variety such as drinking water, ground- ple preparation technique, optional cleanup techniques, and
water, industrial wastewaters, surface waters, soils, solids, and calibration procedures used.
sediments. MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
METHOD SUMMARY This method provides procedures for Matrix Factor (b)
the determination of 22 chlorinated hydrocarbons in water, Groundwater 10
soil/sediment, and waste matrices. A measured volume or Low-concentration soil by ultrasonic cleanup 670
weight of sample is extracted by using one of the appropriate extraction with GPC
sample extraction techniques specified in EPA Method 3510, High-concentration soil and sludges 10,000
EPA Method 3520, EPA Method 3540, or EPA Method 3550, by ultrasonic extraction
or diluted using EPA Method 3580. Aqueous samples are
extracted at neutral pH with methylene chloride by using either
a separatory funnel (EPA Method 3510) or a continuous liquid- (a) Sample EQLs are highly matrix-dependent. The EQLs listed are
liquid extractor (EPA Method 3520). Solid samples are provided for guidance and may not always be achievable.
extracted with hexane/acetone (1:1) by using a Soxhlet extrac- (b) EQL = [Method detection limit] [Factor]. For non-aqueous
tor (EPA Method 3540) or with methylene chloride/acetone samples, the factor is on a wet-weight basis.
PRECISION & ACCURACY MDL is the method detection
cleanup, the extract or diluted sample is analyzed by gas chro-
limit for organic-free reagent water. MDLwas determined from
matography with electron capture detection (GC/ECD).
the analysis of eight replicate aliquots processed through the
The sensitivity level of this method usually depends on the level entire analytical method (extraction, Florisil cartridge cleanup,
of interferences rather than on instrumental limitations. This and GC/ECD analysis).

The MDL (in ng/L) was 240. trations should be prepared through dilution of the stock stan-
dards with hexane. The suggested internal standards are:
The accuracy (as average % recovery using 5 determinations
2,5-dibromotoluene, 1,3,5-t r ibromobenzene, and ,
and no Florisil cleanup) from a spike concentration of 10 g/L
dibromo-m-xylene. The analyst can use any of the three com-
and separatory funnel extraction was 97% with a final volume
pounds provided that theyare resolved from matrix interferences.
of 10 mL.
The precision (as RSD% using 5 determinations and no Florisil 1,4-dichloronaphthalene, and 2,3,4,5,6-pentachlorotoluene.
cleanup) from a spike concentration of 10 g/L and separatory
In general, water samples are extracted at a neutral pH with
funnel extraction was 5.1% with a final volume of 10 mL.
methylene chloride using a separatory funnel (EPA Method
The accuracy (as average % recovery using 5 determinations 3510) or a continuous liquid-liquid extractor (EPA Method
and no Florisil cleanup), from a spike concentration of 330 g/L 3520). Solid samples are extracted with hexane/acetone (1:1
and ultrasonic extraction of solid samples using 1:1 methylene v:v) using a Soxhlet extractor (EPA Method 3540) or with
chloride and acetone, was 44% with a final volume of 10 mL. methylene chloride/acetone (1:1 v:v) using an ultrasonic
The precision (as RSD% using 5 determinations and no Florisil extractor (EPA Method 3550). Non-aqueous waste samples
may be diluted using EPA Method 3580. Prior to Florisil
cleanup), from a spike concentration of 330 g/L and ultra-
sonic extraction of solid samples using 1:1 methylene chloride cleanup or gas chromatographic analysis, the extraction solvent
and acetone, was 25.9% with a final volume of 10 mL. must be exchanged to hexane. Sample extracts that will be
subjected to gel permeation chromatography do not need sol-
SAMPLE COLLECTION, PRESERVATION & HANDLING vent exchange.
Volatile Organics — Standard 40-mL glass screw-cap VOA vials
with Teflon®-faced silicone septum may be used for both liquid Cleanup procedures may not be necessary for a relatively clean
and solid matrices. When collecting samples, liquids and solids matrix. If removal of interferences such as chlorinated phenols,
should be introduced into the vials gently to reduce agitation phthalate esters, etc., is required, proceed with the procedure
which might drive off volatile compounds. If there are any air outlined in EPA Method 3620.
bubbles present the sample must be retaken. The vials with QUALITY CONTROL Analyze a quality control check stan-
solids should be tapped slightly as they are filled to try and dard to demonstrate that the operation of the GC is in control.
eliminate as much free air space as possible. Two vials from The frequency of the check standard analysis is equivalent to
each sampling location should be sealed in separate plastic bags 10% of the samples analyzed. If the recovery of any compound
to prevent cross-contamination between samples. found in the check standard is less than 80% of the certified
Semivolatile organics — Containers used to collect samples for value, the problem must be corrected and a new set of calibra-
the determination of semivolatile organic compounds should tion standards must be prepared and analyzed. Calculate sur-
be soap and water washed followed by methanol (or isopro- rogate standard recoveries for all samples, blanks, and spikes.
panol) rinsing. The sample containers should be of glass or An internal standard peak area check must be performed on
Teflon® and have screw-top covers with Teflon® liners. all samples. The internal standard must be evaluated for accep-
Preservation for volatile organics — No preservation is used nal standard deviates by more than 30% from the average area
with concentrated waste samples. With liquid samples contain- for the internal standard in the calibration standards. When
ing no residual chlorine, 4 drops of concentrated hydrochloric the internal standard peak area is outside that limit, all samples
acid are added and the samples are immediately cooled to 4 C. that fall outside the QC criteria must be reanalyzed. Any com-
When liquid samples contain residual chlorine, they are treated pound confirmed by two columns may also be confirmed by
as above and, in addition, 4 drops of 4% aqueous sodium GC/MS (EPA Method 8270). The GC/MS would normally
thiosulfate are added to remove the residual chlorine. Soil, require a minimum concentration of 1 ng/L in the final
sediment, and sludge samples are only cooled to 4C. extract for each compound. Include a mid-concentration cal-
Preservation for semivolatile organics — No preservation is ibration standard after each group of 20 samples in the analysis
used with concentrated waste samples. With liquid samples sequence. The response factors for the mid-concentration cal-
containing no residual chlorine and with soil, sediment, and ibration must be within 15% of the average values for the
sludge samples, immediately cooling to 4C is the only preser- multiconcentration calibration.
vation used. When residual chlorine is present then 3 mL of
10% aqueous sodium sulfate is added for each gallon of sample
of Solid Waste, Washington, DC, 1990. EPA Method 8121, Rev.
Holding times — The holding time for all volatile organics 0, Nov. 1990.
7 days and their extracts analyzed within 40 days. Concentrated
waste, soil, sediment, and sludge samples must be extracted
Hexachlorocyclopentadiene EPA Method 8270
within 14 days and their extracts analyzed within 40 days.
CAS #77-47-4
in hexane. Calibration standards at a minimum of five concen- TITLE Semivolatile Organic Compounds by GC/MS

the extracts analyzed within 40 days. Soils, sediments, or slud-
ges may be stored for a maximum of 14 days and the extracts
in g/kg is 660. hydroxide and extract it with methylene chloride again for
concentrator.

amount added of the surrogates and matrix spiking com- MATRIX The compounds may be determined in waters, soils,
pounds should result in a final concentration of 100 ng/ L of and municipal sludges by this method.
METHOD SUMMARY This method is used to determine 176
semivolatile toxic organic pollutants associated with the CWA (as
amended 1987); the RCRA (as amended 1986); the CERCLA (as
amended 1986); and other compounds amenable to extraction
or more times. Dry the extract using a column with anhydrous and analysis by capillary column gas chromatography-mass spec-
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. trometry (GC/MS).
Note: Hexachlorocyclopentadiene is subject to thermal and Stable isotopically-labeled analogs of the compounds of interest
photochemical decomposition so samples must be proteccted are added to the sample. If the solids content is less than 1%, a
from light and heat. 1-L sample is extracted at pH 12–13, then at pH <2 with meth-
ylene chloride using continuous extraction techniques.
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is If the solids content is 30% or less, the sample is diluted to 1%
used for tuning the GC/MS system each 12-h shift. A system solids with reagent water, homogenized ultrasonically, and
performance check also must be made during every 12-h shift. extracted at pH 12–13, then at pH <2 with methylene chloride
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- using continuous extraction techniques. If the solids content is
rophenol, and benzidine is required to verify injection port greater than 30%, the sample is extracted using ultrasonic tech-
inertness and GC column performance. A calibration standard niques.
at mid-concentration, containing each compound of interest, Each extract is dried over sodium sulfate, concentrated to a vol-
including all required surrogates, must be performed every 12 h ume of 5 mL, cleaned up using GPC, if necessary, and concen-
during analysis. After the system performance check is met, trated.Extracts are concentrated to 1 mLif GPC is not performed,
calibration check compounds (CCCs) are used to check the and to 0.5 mL if GPC is performed.
The internal standard responses and retention times in the of the extract is injected into the GC. The compounds are sepa-
rated by GC and detected by a MS. The labeled compounds serve
to correct the variability of the analytical technique.
calibration (12 h), the chromatographic system must be INTERFERENCES Solvents, reagents, glassware, and other
inspected for malfunctions and corrections must be made, as sample processing hardware may yield artifacts and/or elevated
required. If the electron ionization current plot (EICP) area for baselines causing misinterpretation of chromatograms and spec-
any of the internal standards changes by a factor of two from tra. Materials used in the analysis must be demonstrated to be
the last daily calibration standard check, the mass spectrometer free from interferences under the conditions of analysis by run-
must be inspected for malfunctions and corrections must be ning method blanks initially and with each sample lot (sample
made, as appropriate. started through the extraction process on a given 8-h shift, to a
maximum of 20). Specific selection of reagents and purification
of solvents by distillation in all glass systems may be required.
reagents are under control. The blank samples should be car- Glassware and, where possible, reagents are cleaned by solvent
ried through all stages of the sample preparation and measure- rinse and baking at 450C for 1-h minimum. Interferences coex-
ment steps. For each analytical batch (up to 20 samples), a tracted from samples will vary considerably from source to
reagent blank, matrix spike, and matrix spike duplicate/dupli- source, depending on the diversity of the site being sampled.
cate must be analyzed (the frequency of the spikes may be INSTRUMENTATION Major instrumentation includes a GC
different for different monitoring programs). The blank and with a splitless or on-column injection port for capillary column,
spiked samples must be carried through all stages of the sample a MS with 70 eV electron impact ionization, and a data system
preparation and measurement steps. A QC reference sample to collect and record MS data, and process it. A K-D apparatus
concentrate containing each analyte at a concentration of is used to concentrate extracts.
REFERENCE Test Methods for Evaluating Solid Waste (SW- vinyl silicone bonded phased fused silica capillary column.
of Solid Waste, Washington, DC. PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences rather
than instrumental limitations. The limits typify the minimum
quantities that can be detected with no interferences present.
Hexachloroethane EPA Method 1625
CAS #67-72-1 The minimum level (in g/mL) was 10. This is defined as a min-
imum level at which the analytical system shall give recognizable
TITLE Semivolatile Organic Compounds by Isotope Dilution mass spectra (background corrected) and acceptable calibra-
GC/MS tion points.
The MDL (in g/kg) in low solids was 58 and in high solids Reagent water and high solids reference matrix blanks are ana-
was 55; these were determined in digested sludge (low solids) lyzed to demonstrate freedom from contamination. Extract
and in filter cake or compost (high solids). and concentrate a 1-L reagent water blank or a high solids
through the extraction process on the same 8-h shift, to a
maximum of 20 samples).
recovery (in g/L) was 21-ns. Field replicates may be collected to determine the precision of
ns = no specification; the limit was outside the range that could the sampling technique, and spiked samples may be required
be reliably measured. to determine the accuracy of the analysis when the internal
Collect samples in glass containers. Aqueous samples which REFERENCE Semivolatile Organic Compounds by Isotope
flow freely are collected in refrigerated bottles using automatic Dilution GC/MS. Office of Water Regulation and Standards,
sampling equipment. Solid samples are collected as grab sam- U.S. EPA Industrial Technology Division, Washington, DC,
ples using widemouth jars. Maintain samples at 0 to 4C from EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
the time of collection until extraction. If residual chlorine is U.S. EPA, Office of Water Regulations and Standards, 401 M
present in aqueous samples, add 80 mg sodium thiosulfate/L St., SW, Washington, DC, 20460. Phone: 202-382-7131).
SAMPLE PREPARATION Samples containing 1% solids or Hexachloroethane EPA Method 625
less are extracted directly using continuous liquid-liquid CAS #67-72-1
diluted to the 1% level with reagent water and extracted using TITLE Base/Neutrals and Acids, U.S. EPA Method 625
continuous liquid-liquid extraction techniques. Samples con- MATRIX This methods covers municipal and industrial
taining greater than 30% solids are extracted using ultrasonic wastewaters.
techniques.
Base/neutral extraction — Adjust the pH of the waters in the ally extracted with methylene chloride at a pH greater than 11
extractors to 12–13 with 6 N NaOH. Extract with methylene and again at a pH less than 2 using a separatory funnel or a
chloride for 24–48 h. continuous extractor. The methylene chloride extract is dried,
Acid extraction — Adjust the pH of the waters in the extractors concentrated to a volume of 1 mL, and analyzed by GC/MS.
to 2 or less using 6 N sulfuric acid. Extract with methylene Qualitative identification of the parameters in the extract is
chloride for 24–48 h. performed using the retention time and the relative abundance
Ultrasonic extraction of high solids samples — Add anhy- of three characteristic masses (m/z). Qualitative analysis is per-
drous sodium sulfate to the sample and QC aliquot(s). formed using either external or internal standard techniques
Add acetone:methylene chloride (1:1) to the sample and with a single characteristic m/z.
mix thoroughly
Concentrate extracts using a K-D apparatus. contaminants in solvents, reagents, glassware, and other sample
QUALITY CONTROL The analyst is permitted to modify processing hardware. Glassware must be scrupulously cleaned.
this method to improve separations or lower the costs of mea- Glassware should be heated in a muffle furnace at 400C for 5
surements, provided all performance specifications are met. to 30 min. Some thermally stable materials, such as PCBs, may
Analyses of blanks are required to demonstrate freedom from not be eliminated by this treatment. Solvent rinses with acetone
contamination. When results of spikes indicate atypical and pesticide quality hexane may be substituted for the muffle
method performance for samples, the samples are diluted to furnace heating. Matrix interferences may be caused by con-
bring method performance within acceptable limits. taminants that are coextracted from the sample. The base-
For low solids (aqueous samples), extract, concentrate, and phenols. The packed gas chromatographic columns recom-
analyze two sets of four 1-L aliquots (8 aliquots total) of the mended for the basic fraction may not exhibit sufficient reso-
precision and recovery standard. For high solids samples, two lution for some analytes.
are used. INSTRUMENTATION A GC/MS system with an injection
port designed for on-column injection when using packed col-
performance. Compute percent recovery of the labeled com-
pounds using the internal standard method. Compare the Column for base/neutrals: 1.8 m long  2 mm I.D. glass,
labeled compound recovery for each compound with the cor- packed with 3% SP-2550 on Supelcoport (100/120 mesh)
responding labeled compound recovery. or equivalent.

Column for acids: 1.8 m long 2 mm I.D. glass, packed with 100 g/mL in acetone is required. PCBs and multicomponent
1% SP-1240DA on Supelcoport (100/120 mesh) or equivalent. pesticides may be omitted from this test.
PRECISION & ACCURACY The MDL concentrations were After analysis of five spiked wastewater samples, calculate the
obtained using reagent water. The MDL actually achieved in a average percent recovery and the standard deviation of the
given analysis will vary depending on instrument sensitivity percent recovery. Spike all samples with the surrogate standard
and matrix effects. This method was tested by 15 laboratories spiking solution and calculate the percent recovery of each
using reagent water, drinking water, surface water, and indus- surrogate compound.
to 100 g/L. Single operator precision, overall precision, and 26, 1984.
The MDL (in g/L) in reagent water was not reported. Hexachloroethane EPA Method 8120
The standard deviation (in g/L based on 4 recovery measure- CAS #67-72-1
ments) was 24.5.
The range (in g/L) for average recovery for 4 measurements TITLE Chlorinated Hydrocarbons by Gas Chromatography
was 55.2–100.0.
The range (in %) for percent recovery was 40–113. MATRIX This method covers aqueous and solid matrices.
Accuracy (in g/L) as expected recovery for one or more mea- This includes a wide variety such as drinking water, ground-
surements of a sample containing a true concentration of water, industrial wastewaters, surface waters, soils, solids, and
C was 0.73C-0.83. sediments.
Precision (in g/L) as expected single analyst standard devia- METHOD SUMMARY This method is used to determine the
tion of measurements at an average concentration found at concentration of 14 chlorinated hydrocarbons. It provides gas
X was 0.17X + 0.67. chromatographic conditions for the detection of ppb concen-
Overall precision (in g/L) as expected interlaboratory stan- trations of certain chlorinated hydrocarbons. Prior to use of
dard deviation of measurements in an average concentra- this method, appropriate sample extraction techniques must
tion found at X was 0.17X + 0.80. be used. Both neat and diluted organic liquids (EPA Method
C = True value of the concentration in g/L. 3580, Waste Dilution) may be analyzed by direct injection. A
X = Average recovery found for measurements of samples con- 2 to 5 g/mL aliquot of the extract is injected into a gas chro-
taining a concentration at C in g/L. matograph (GC) using the solvent flush technique, and com-
SAMPLE PREPARATION Adjust the pH to >11 with sodium detector (ECD).
hydroxide and serially extract in a separatory funnel with meth-
ylene chloride or else in a continuous extractor. Next, adjust INTERFERENCES Solvents, reagents, glassware, and other
the pH to <2 with sulfuric acid and serially extract in a sepa- sample processing hardware may yield discrete artifacts and/or
ratory funnel with methylene chloride or else in a continuous elevated baselines causing misinterpretation of gas chromato-
extractor. Dry the extracts separately through a column of grams. Interferences coextracted from samples will vary con-
anhydrous sodium sulfate and then concentrate each of the siderably from source to source, depending upon the waste
extracts to 1.0 mL using a K-D apparatus. being sampled.
SAMPLE COLLECTION, PRESERVATION & HANDLING INSTRUMENTATION An analytical system complete with
Grab samples must be collected in glass containers. All samples GC suitable for on-column injections and accessories, includ-
must be refrigerated at 4C from the time of collection until ing detectors, column supplies, recorder, gases and syringes is
extraction. If residual chlorine is present, add 80 mg of sodium required. A data system for measuring peak areas and/or peak
thiosulfate/L of sample and mix well. All samples must be heights is recommended. The GC is equipped with an electron
capture detector (ECD). A K-D apparatus is needed for sample
preparation.
QUALITY CONTROL Make an initial, one-time, demonstra- Column 1: 1.8 m 2 mm I.D. glass column packed with 1%
SP-1000 on Supelcoport (100/120 mesh) or equivalent.
Column 2: 1.8 m 2 mm I.D. glass column packed with 1.5%
OV-1/2.4% OV-225 on Supelcoport (80/100 mesh) or
equivalent.
control. Each time a set of samples is extracted or reagents are PRECISION & ACCURACY The method was tested by 20
changed, a reagent water blank must be processed. Spike and laboratories using organic-free reagent water, drinking water,
analyze a minimum of 5% of all samples to monitor and eval- surface water, and three industrial wastewaters spiked at six
uate lab data quality. A QC check sample concentrate that concentrations over the range 1.0 to 356 g/L. Single operator
contains each parameter of interest at a concentration of precision, overall precision, and method accuracy were found

to be directly related to the concentration of the parameter and
Hexachloroethane EPA Method 8121
essentially independent of the sample matrix. CAS #67-72-1
Matrix Factor (b) TITLE Chlorinated Hydrocarbons by GC: Capillary Column
Technique
Groundwater 10
Low-concentration soil by ultrasonic cleanup 670 MATRIX This method covers aqueous and solid matrices.
extraction with GPC This includes a wide variety such as drinking water, ground-
High-concentration soil and sludges 10,000 water, industrial wastewaters, surface waters, soils, solids, and
by ultrasonic extraction sediments.
Non-water miscible waste 100,000 METHOD SUMMARY This method provides procedures for
(a) Sample EQLs are highly matrix-dependent. The EQLs listed are the determination of 22 chlorinated hydrocarbons in water,
provided for guidance and may not always be achievable. soil/sediment, and waste matrices. A measured volume or
(b) EQL = [Method detection limit] [Factor]. For non-aqueous weight of sample is extracted by using one of the appropriate
samples, the factor is on a wet-weight basis. sample extraction techniques specified in EPA Method 3510,
EPA Method 3520, EPA Method 3540, or EPA Method 3550,
PRECISION & ACCURACY The estimates below are based or diluted using EPA Method 3580. Aqueous samples are
upon the performance in a single lab. extracted at neutral pH with methylene chloride by using either
a separatory funnel (EPA Method 3510) or a continuous liquid-
The accuracy (in g/L) as expected recovery for one or more
liquid extractor (EPA Method 3520). Solid samples are
measurements of a sample containing a concentration of C
extracted with hexane/acetone (1:1) by using a Soxhlet extrac-
was 0.74C-0.02.
tor (EPA Method 3540) or with methylene chloride/acetone
The precision (in g/L) as expected single analyst standard
deviation of measurements at an average concentration of
cleanup, the extract or diluted sample is analyzed by gas chro-
x” was 0.23 x”-0.07.
matography with electron capture detection (GC/ECD).
The precision (in g/L) as expected interlaboratory standard
deviation measurements at an average concentration found The sensitivity level of this method usually depends on the level
of x” was 0.36 x”-0.00. of interferences rather than on instrumental limitations. This
method may be used in conjunction with EPA Method 3620,
C = True value for the concentration, in g/L. Florisil Column Cleanup, EPA Method 3660, Sulfur Cleanup,
x”= Average recovery found for measurements of samples con-
and EPA Method 3640, Gel Permeation Chromatography, to
taining a concentration of C, in g/L. aid in the elimination of interferences.
SAMPLE COLLECTION, PRESERVATION & HANDLING INTERFERENCES Solvents, reagents, glassware, and other
Extracts must be stored under refrigeration at 4C and analyzed hardware used in sample processing may introduce artifacts
within 40 days of extraction. which may result in elevated baselines, causing misinterpreta-
SAMPLE PREPARATION In general, water samples are tion of gas chromatograms. Interferants coextracted from the
extracted at a neutral, or as is, pH with methylene chloride samples will vary considerably from waste to waste. Glassware
using either EPA Method 3510 or EPA Method 3520. Solid must be scrupulously clean. Phthalate esters, if present in a
samples are extracted using either EPA Method 3540 or EPA sample, will interfere only with the BHC isomers. The presence
Method 3550. Prior to gas chromatographic analysis, the of elemental sulfur will result in large peaks, and can often
extraction solvent must be exchanged to hexane. mask the region of compounds eluting after 1,2,4,5-tetrachloro-
benzene. The tetrabutylammonium (TBA)-sulfite procedure
QUALITY CONTROL The quality control check concentrate (EPA Method 3660) works well for the removal of elemental
(EPA Method 8000) should contain each parameter of interest sulfur. Waxes and lipids can be removed by gel permeation
in acetone at the following concentrations: hexachloro-substi- chromatography (EPA Method 3640).
hydrocarbon, 100 g/mL. Calculate surrogate standard recov- INSTRUMENTATION A GC suitable for on-column injec-
ery on all samples, blanks, and spikes. tions and all required accessories, including and electron cap-
ture detector (ECD), analytical columns, recorder, gases, and
Prepare stock standard solutions in isooctane or hexane. Cali- syringes are needed. A data system for measuring peak heights
bration standards at a minimum of five concentrations should and/or peak areas is recommended. A Kuderna-Danish (K-D)
be prepared through dilution of the stock standards with isooc- apparatus will also be needed to concentrate extracts.
tane or hexane. Internal standards and surrogate standards are
also needed.
REFERENCE Test Methods for Evaluating Solid Waste, Phys- (DB-210 or equivalent).
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office Column 2: 30 m 0.53 mm I.D. fused-silica capillary column
of Solid Waste, Washington, DC, 1990. EPA Method 8120 A chemically bonded with polyethylene glycol (DB-WAX or
Rev. 1, Nov. 1990. equivalent).

PRECISION & ACCURACY This method has been tested in Semivolatile organics — Containers used to collect samples for
a single lab by using organic-free reagent water, sandy loam the determination of semivolatile organic compounds should
samples, and extracts which were spiked with the test com- be soap and water washed followed by methanol (or isopro-
pounds at one concentration. Single-operator precision and panol) rinsing. The sample containers should be of glass or
method accuracy were found to be related to the concentration Teflon® and have screw-top covers with Teflon® liners.
of compound and the type of matrix. The accuracy and preci- Preservation for volatile organics — No preservation is used
sion technique will be determined by the sample matrix, sam- with concentrated waste samples. With liquid samples contain-
ple preparation technique, optional cleanup techniques, and ing no residual chlorine, 4 drops of concentrated hydrochloric
calibration procedures used. acid are added and the samples are immediately cooled to 4 C.
MULTIPLICATION FACTORS FOR OTHER MATRICES (a) When liquid samples contain residual chlorine, they are treated
Matrix Factor (b) as above and, in addition, 4 drops of 4% aqueous sodium
thiosulfate are added to remove the residual chlorine. Soil,
Groundwater 10 sediment, and sludge samples are only cooled to 4C.
Low-concentration soil by ultrasonic cleanup 670
extraction with GPC
used with concentrated waste samples. With liquid samples
High-concentration soil and sludges 10,000
containing no residual chlorine and with soil, sediment, and
sludge samples, immediately cooling to 4C is the only preser-
vation used. When residual chlorine is present then 3 mL of
(a) Sample EQLs are highly matrix-dependent. The EQLs listed are 10% aqueous sodium sulfate is added for each gallon of sample
provided for guidance and may not always be achievable. collected, followed by cooling to 4C.
Holding times — The holding time for all volatile organics
PRECISION & ACCURACY MDL is the method detection 7 days and their extracts analyzed within 40 days. Concentrated
limit for organic-free reagent water. MDLwas determined from waste, soil, sediment, and sludge samples must be extracted
the analysis of eight replicate aliquots processed through the within 14 days and their extracts analyzed within 40 days.
entire analytical method (extraction, Florisil cartridge cleanup, SAMPLE PREPARATION Prepare stock standard solutions
and GC/ECD analysis). in hexane. Calibration standards at a minimum of five concen-
The MDL (in ng/L) was 1.6. trations should be prepared through dilution of the stock stan-
dards with hexane. The suggested internal standards are:
The accuracy (as average % recovery using 5 determinations 2,5-dibromotoluene, 1,3,5-t r ibromobenzene, and ,
and no Florisil cleanup) from a spike concentration of 1.0 g/L dibromo-m-xylene. The analyst can use any of the three com-
and separatory funnel extraction was 96% with a final volume pounds provided that theyare resolved from matrix interferences.
of 10 mL. Recommended surrogate compounds are -2,6-trichlorotoluene,
The precision (as RSD% using 5 determinations and no Florisil 1,4-dichloronaphthalene, and 2,3,4,5,6-pentachlorotoluene.
cleanup) from a spike concentration of 1.0 g/L and separatory In general, water samples are extracted at a neutral pH with
funnel extraction was 4.0% with a final volume of 10 mL. methylene chloride using a separatory funnel (EPA Method
The accuracy (as average % recovery using 5 determinations 3510) or a continuous liquid-liquid extractor (EPA Method
3520). Solid samples are extracted with hexane/acetone (1:1
and no Florisil cleanup), from a spike concentration of 330 g/L
v:v) using a Soxhlet extractor (EPA Method 3540) or with
and ultrasonic extraction of solid samples using 1:1 methylene
methylene chloride/acetone (1:1 v:v) using an ultrasonic
chloride and acetone, was 83% with a final volume of 10 mL.
extractor (EPA Method 3550). Non-aqueous waste samples
The precision (as RSD% using 5 determinations and no Florisil may be diluted using EPA Method 3580. Prior to Florisil
cleanup), from a spike concentration of 330 g/L and ultra- cleanup or gas chromatographic analysis, the extraction solvent
sonic extraction of solid samples using 1:1 methylene chloride must be exchanged to hexane. Sample extracts that will be
and acetone, was 4.6% with a final volume of 10 mL. subjected to gel permeation chromatography do not need sol-
vent exchange.
Volatile Organics — Standard 40-mL glass screw-cap VOA vials Cleanup procedures may not be necessary for a relatively clean
with Teflon®-faced silicone septum may be used for both liquid matrix. If removal of interferences such as chlorinated phenols,
and solid matrices. When collecting samples, liquids and solids phthalate esters, etc., is required, proceed with the procedure
should be introduced into the vials gently to reduce agitation outlined in EPA Method 3620.
which might drive off volatile compounds. If there are any air QUALITY CONTROL Analyze a quality control check stan-
bubbles present the sample must be retaken. The vials with dard to demonstrate that the operation of the GC is in control.
solids should be tapped slightly as they are filled to try and The frequency of the check standard analysis is equivalent to
eliminate as much free air space as possible. Two vials from 10% of the samples analyzed. If the recovery of any compound
each sampling location should be sealed in separate plastic bags found in the check standard is less than 80% of the certified value,
to prevent cross-contamination between samples. the problem must be corrected and a new set of calibration

standards must be prepared and analyzed. Calculate surrogate INSTRUMENTATION A GC/MS and a data system are
standard recoveries for all samples, blanks, and spikes.An inter- required. The GC column used is a 30 m 0.25 mm I.D. (or
nal standard peak area check must be performed on all samples. 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
The internal standard must be evaluated for acceptance by capillary column. A continuous liquid-liquid extractor
determining whether the measured area for the internal stan- equipped with Teflon® or glass connection joints and stopcocks
dard deviates by more than 30% from the average area for the requiring no lubrication, a K-D concentrating apparatus, water
internal standard in the calibration standards. When the inter- bath, and an ultrasonic disrupter with a minimum power of
nal standard peak area is outside that limit, all samples that fall 300 W and with pulsing capability are also required.
outside the QC criteria must be reanalyzed. Any compound
confirmed by two columns may also be confirmed by GC/MS
(EPA Method 8270). The GC/MS would normally require a
minimum concentration of 1 ng/L in the final extract for each sediment samples, 1–200 mg/kg for wastes (dependent on
compound. Include a mid-concentration calibration standard
after each group of 20 samples in the analysis sequence. The water samples. EQLs will be proportionately higher for sample
response factors for the mid-concentration calibration must be extracts that require dilution to avoid saturation of the detector.
within 15% of the average values for the multiconcentration
calibration. The EQL(b) for groundwater in g/L is 10.
REFERENCE Test Methods for Evaluating Solid Waste, Phys- in g/kg is 660.
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office Accuracy as g/L is 0.73C–0.83.
of Solid Waste, Washington, DC, 1990. EPA Method 8121, Rev. Overall precision in g/L is 0.17X + 0.80.
0, Nov. 1990.
Hexachloroethane EPA Method 8270 This calculation is based on a 30-g sample and gel perme-
lakes, etc.
tion of the sample into the GC/MS system may be appropriate, (a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
(or isopropanol).

concentrator.
Hexachlorophene EPA Method 8270
flowing sandy texture must be mixed with anhydrous sodium TITLE Semivolatile Organic Compounds by GC/MS
standards to all samples, spikes, standards, and blanks. For the MATRIX This method is used to determine the concentra-
sample in each analytical batch selected for spiking, add 1.0 mL tion of semivolatile organic compounds in extracts prepared
of a matrix spiking standard. For base/neutral acid analysis, the from all types of solid waste matrices, soils, and groundwater.
amount added of the surrogates and matrix spiking com- Although surface waters are not specifically mentioned, this
pounds should result in a final concentration of 100 ng/ L of method should be applicable to water samples from rivers,
each base/neutral analyte and 200 ng/L of each acid analyte lakes, etc.
in the extract to be analyzed (assuming a 1- L injection). METHOD SUMMARY This method covers 259 semivolatile
Immediately add a 100-mL mixture of 1:1 methylene chlo- organic compounds. In very limited applications direct injec-
ride:acetone and extract the sample ultrasonically for 3 min tion of the sample into the GC/MS system may be appropriate,
and then decant or filter the extracts. Repeat the extraction two but this results in very high detection limits (approximately
or more times. Dry the extract using a column with anhydrous 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. gate, and matrix spiking standards, is extracted in a continuous
QUALITY CONTROL A methylene chloride solution con- extractor first under acid conditions and then under basic con-
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is ditions. Typically 30 g of a solid sample, containing surrogate,
used for tuning the GC/MS system each 12-h shift. A system and matrix spiking standards, is extracted ultrasonically. After
performance check also must be made during every 12-h shift. concentrating the extract to 1 mL it is spiked with 10 L of an
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- internal standard solution just prior to analysis by GC/MS. The
rophenol, and benzidine is required to verify injection port volume injected should contain about 100 ng of base/neutral
inertness and GC column performance. A calibration standard and 200 ng of acid surrogates (for a 1-L injection). Analysis
at mid-concentration, containing each compound of interest, is performed by GC/MS using a capillary GC column.
including all required surrogates, must be performed every 12 h INTERFERENCES Raw GC/MS data from all blanks, sam-
during analysis. After the system performance check is met, ples, and spikes must be evaluated for interferences. Contam-
calibration check compounds (CCCs) are used to check the ination by carryover can occur whenever high-concentration
validity of the initial calibration. and low-concentration samples are sequentially analyzed. To
The internal standard responses and retention times in the reduce carryover, the sample syringe must be rinsed out
calibration check standard must be evaluated immediately after between samples with solvent. Whenever an unusually concen-
or during data acquisition. If the retention time for any internal trated sample is encountered, it should be followed by the
calibration (12 h), the chromatographic system must be INSTRUMENTATION A GC/MS and a data system are
inspected for malfunctions and corrections must be made, as required. The GC column used is a 30 m 0.25 mm I.D. (or
required. If the electron ionization current plot (EICP) area for 0.32 mm I.D.) 1um film thickness silicone-coated fused silica

SAMPLE PREPARATION
bath, and an ultrasonic disrupter with a minimum power of Liquid samples — Transfer 1 L quantitatively to a continuous
300 W and with pulsing capability are also required. extractor. If high concentrations are anticipated, a smaller vol-
PRECISION & ACCURACY The estimated quantitation ume may be used and then diluted with organic-free reagent
limit (EQL) of Method 8270B for determining an individual water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
compound is approximately 1 mg/kg (wet weight) for soil or sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
sediment samples, 1–200 mg/kg for wastes (dependent on solution into each sample. For the sample in each analytical
The EQL(b) for groundwater in g/L is 50. analyte in the extract to be analyzed (assuming a 1- L injec-
The EQL (a, b) for low concentrations in soil and sediment tion). Extract with methylene chloride for 18–24 h. Next, adjust
in g/kg is not determined. the pH of the aqueous phase to pH >11 using 10 N sodium
Accuracy as g/L is not listed. hydroxide and extract it with methylene chloride again for
Overall precision in g/L is not listed. 18–24 h. Dry the extract through a column containing anhy-
concentrator.
will be higher based on the % dry weight of each sample. Soils, sediments, or sludges — Use 30 g of sample. Nonporous
This calculation is based on a 30-g sample and gel perme- or wet samples (gummy or clay type) that do not have a free-
ation chromatography cleanup. flowing sandy texture must be mixed with anhydrous sodium
(b) Sample EQLs are highly matrix-dependent. The EQLs are sulfate until the sample is free flowing. Add 1 mL of surrogate
provided for guidance and may not always be achievable. standards to all samples, spikes, standards, and blanks. For the
C = True value for concentration, in g/L. sample in each analytical batch selected for spiking, add 1.0 mL
X = Average recovery found for measurements of samples con- of a matrix spiking standard. For base/neutral acid analysis, the
taining a concentration of C, in g/L. amount added of the surrogates and matrix spiking com-
Other Matrices Factor (a) in the extract to be analyzed (assuming a 1- L injection).
High-concentration soil and sludges by sonicator 7.5 Immediately add a 100-mL mixture of 1:1 methylene chlo-
Non-water miscible waste 75 ride:acetone and extract the sample ultrasonically for 3 min
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor]. or more times. Dry the extract using a column with anhydrous
This estimated EQL is similar to an EPA “Practical Quantitation sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
Limit.”
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with used for tuning the GC/MS system each 12-h shift. A system
a screw-top Teflon®-lined cover that has been prewashed with performance check also must be made during every 12-h shift.

cleaned by solvent rinse and baking at 450C for 1-h minimum.
Hexachloropropene EPA Method 1625 rather than instrumental limitations. The limits typify the min-
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu- The minimum level (in g/mL) was not listed. This is defined
tion GC/MS as a minimum level at which the analytical system shall give
CERCLA (as amended 1986); and other compounds amenable The labeled and native compound initial precision as standard
to extraction and analysis by capillary column gas chromatog- deviation (in g/L) was not listed.
raphy-mass spectrometry (GC/MS). The labeled and native compound initial accuracy as average
are added to the sample. If the solids content is less than 1%, SAMPLE COLLECTION, PRESERVATION & HANDLING
a 1-L sample is extracted at pH 12–13, then at pH <2 with Collect samples in glass containers. Aqueous samples which
methylene chloride using continuous extraction techniques. flow freely are collected in refrigerated bottles using automatic
volume of 5 mL, cleaned up using GPC, if necessary, and con- less are extracted directly using continuous liquid-liquid
centrated. Extracts are concentrated to 1 mL if GPC is not extraction techniques. Samples containing 1 to 30% solids are
performed, and to 0.5 mL if GPC is performed. diluted to the 1% level with reagent water and extracted using
An internal standard is added to the extract, and a 1-mL aliquot taining greater than 30% solids are extracted using ultrasonic
of the extract is injected into the GC. The compounds are techniques.
separated by GC and detected by a MS. The labeled compounds
extractors to 12–13 with 6 N NaOH. Extract with methylene
INTERFERENCES Solvents, reagents, glassware, and other chloride for 24–48 h.
sample processing hardware may yield artifacts and/or elevated Acid extraction — Adjust the pH of the waters in the extractors
baselines causing misinterpretation of chromatograms and to 2 or less using 6 N sulfuric acid. Extract with methylene
spectra. Materials used in the analysis must be demonstrated chloride for 24–48 h.

Ultrasonic extraction of high solids samples — Add anhy- 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
drous sodium sulfate to the sample and QC aliquot(s). gate, and matrix spiking standards, is extracted in a continuous
Add acetone:methylene chloride (1:1) to the sample and extractor first under acid conditions and then under basic con-
mix thoroughly ditions. Typically 30 g of a solid sample, containing surrogate,
Concentrate extracts using a K-D apparatus.
QUALITY CONTROL The analyst is permitted to modify internal standard solution just prior to analysis by GC/MS. The
this method to improve separations or lower the costs of mea- volume injected should contain about 100 ng of base/neutral
surements, provided all performance specifications are met. and 200 ng of acid surrogates (for a 1-L injection). Analysis
Analyses of blanks are required to demonstrate freedom from is performed by GC/MS using a capillary GC column.
For low solids (aqueous samples), extract, concentrate, and and low-concentration samples are sequentially analyzed. To
analyze two sets of four 1-L aliquots (8 aliquots total) of the reduce carryover, the sample syringe must be rinsed out
precision and recovery standard. For high solids samples, two between samples with solvent. Whenever an unusually concen-
sets of four 30-g aliquots of the high solids reference matrix trated sample is encountered, it should be followed by the
are used. analysis of blank solvent to check for cross-contamination.
Spike all samples with labeled compounds to assess method INSTRUMENTATION A GC/MS and a data system are
performance. Compute percent recovery of the labeled com- required. The GC column used is a 30 m 0.25 mm I.D. (or
pounds using the internal standard method. Compare the 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
labeled compound recovery for each compound with the cor- capillary column. A continuous liquid-liquid extractor
responding labeled compound recovery. equipped with Teflon® or glass connection joints and stopcocks
reference matrix blank with each sample’s lot (samples started PRECISION & ACCURACY The estimated quantitation
through the extraction process on the same 8-h shift, to a limit (EQL) of Method 8270B for determining an individual
maximum of 20 samples). compound is approximately 1 mg/kg (wet weight) for soil or
REFERENCE Semivolatile Organic Compounds by Isotope The EQL (a, b) for low concentrations in soil and sediment
Dilution GC/MS. Office of Water Regulation and Standards, in g/kg is not determined.
U.S. EPA Industrial Technology Division, Washington, DC, Accuracy as g/L is not listed.
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, Overall precision in g/L is not listed.
St., SW, Washington, DC, 20460. Phone: 202-382-7131). (a) EQLs listed for soil/sediment are based on wet weight. Nor-
Hexachloropropene EPA Method 8270 ation chromatography cleanup.

SAMPLE PRESERVATION

concentrator.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous n-Hexacosane EPA Method 1625
sulfate until the sample is free flowing. Add 1 mL of surrogate TITLE Semivolatile Organic Compounds by Isotope Dilu-
standards to all samples, spikes, standards, and blanks. For the tion GC/MS
sample in each analytical batch selected for spiking, add 1.0 mL MATRIX The compounds may be determined in waters,
of a matrix spiking standard. For base/neutral acid analysis, the soils, and municipal sludges by this method.
pounds should result in a final concentration of 100 ng/ L of METHOD SUMMARY This method is used to determine
each base/neutral analyte and 200 ng/L of each acid analyte 176 semivolatile toxic organic pollutants associated with the
in the extract to be analyzed (assuming a 1- L injection). CWA (as amended 1987); the RCRA (as amended 1986); the
Immediately add a 100-mL mixture of 1:1 methylene chlo- CERCLA (as amended 1986); and other compounds amenable
ride:acetone and extract the sample ultrasonically for 3 min to extraction and analysis by capillary column gas chromatog-
and then decant or filter the extracts. Repeat the extraction two raphy-mass spectrometry (GC/MS).
QUALITY CONTROL A methylene chloride solution con- a 1-L sample is extracted at pH 12–13, then at pH <2 with
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is methylene chloride using continuous extraction techniques.

If the solids content is 30% or less, the sample is diluted to 1% The labeled and native compound initial accuracy as average
solids with reagent water, homogenized ultrasonically, and recovery (in g/L) was 35–193.
techniques.
Each extract is dried over sodium sulfate, concentrated to a ples using widemouth jars. Maintain samples at 0 to 4C from
volume of 5 mL, cleaned up using GPC, if necessary, and con- the time of collection until extraction. If residual chlorine is
centrated. Extracts are concentrated to 1 mL if GPC is not present in aqueous samples, add 80 mg sodium thiosulfate/L
performed, and to 0.5 mL if GPC is performed. of water. Begin sample extraction within 7 days of collection,
of the extract is injected into the GC. The compounds are SAMPLE PREPARATION Samples containing 1% solids or
separated by GC and detected by a MS. The labeled compounds less are extracted directly using continuous liquid-liquid
serve to correct the variability of the analytical technique. extraction techniques. Samples containing 1 to 30% solids are
INTERFERENCES Solvents, reagents, glassware, and other continuous liquid-liquid extraction techniques. Samples con-
sample processing hardware may yield artifacts and/or elevated taining greater than 30% solids are extracted using ultrasonic
baselines causing misinterpretation of chromatograms and techniques.
to be free from interferences under the conditions of analysis Base/neutral extraction — Adjust the pH of the waters in the
by running method blanks initially and with each sample lot extractors to 12–13 with 6 N NaOH. Extract with methylene
(sample started through the extraction process on a given 8-h chloride for 24–48 h.
shift, to a maximum of 20). Specific selection of reagents and Acid extraction — Adjust the pH of the waters in the extractors
purification of solvents by distillation in all glass systems may to 2 or less using 6 N sulfuric acid. Extract with methylene
be required. Glassware and, where possible, reagents are chloride for 24–48 h.
cleaned by solvent rinse and baking at 450C for 1-h minimum. Ultrasonic extraction of high solids samples — Add anhy-
Interferences coextracted from samples will vary considerably drous sodium sulfate to the sample and QC aliquot(s).
from source to source, depending on the diversity of the site Add acetone:methylene chloride (1:1) to the sample and
being sampled. mix thoroughly
INSTRUMENTATION Major instrumentation includes a GC Concentrate extracts using a K-D apparatus.

with a splitless or on-column injection port for capillary col- QUALITY CONTROL The analyst is permitted to modify
umn, a MS with 70 eV electron impact ionization, and a data this method to improve separations or lower the costs of mea-
system to collect and record MS data, and process it. A K-D surements, provided all performance specifications are met.
apparatus is used to concentrate extracts. Analyses of blanks are required to demonstrate freedom from
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1% contamination. When results of spikes indicate atypical
vinyl silicone bonded phased fused silica capillary column. method performance for samples, the samples are diluted to
method are usually dependent on the level of interferences For low solids (aqueous samples), extract, concentrate, and
rather than instrumental limitations. The limits typify the min- analyze two sets of four 1-L aliquots (8 aliquots total) of the
imum quantities that can be detected with no interferences precision and recovery standard. For high solids samples, two
present. sets of four 30-g aliquots of the high solids reference matrix
are used.
minimum level at which the analytical system shall give recog- Spike all samples with labeled compounds to assess method
nizable mass spectra (background corrected) and acceptable performance. Compute percent recovery of the labeled com-
calibration points. pounds using the internal standard method. Compare the
The MDL (in g/kg) in low solids was 609 and in high solids responding labeled compound recovery.
was 886; these were determined in digested sludge (low solids)
and in filter cake or compost (high solids).
Note: Background levels of this compound were present in the and concentrate a 1-L reagent water blank or a high solids
sludge tested, resulting in higher than expected MDLs. The reference matrix blank with each sample’s lot (samples started
MDL for this compound is expected to be approximately through the extraction process on the same 8-h shift, to a
50 g/kg with no interferences present. maximum of 20 samples).
deviation (in g/L) was 35. the sampling technique, and spiked samples may be required

to determine the accuracy of the analysis when the internal INSTRUMENTATION Major instrumentation includes a GC
standard method is used. with a splitless or on-column injection port for capillary col-
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
U.S. EPA, Office of Water Regulations and Standards, 401 M vinyl silicone bonded phased fused silica capillary column.
n-Hexadecane EPA Method 1625 imum quantities that can be detected with no interferences
CAS #544-76-3 present.
nizable mass spectra (background corrected) and acceptable
MATRIX The compounds may be determined in waters, calibration points.
soils, and municipal sludges by this method.
The MDL (in g/kg) in low solids was 116 and in high solids
METHOD SUMMARY This method is used to determine was 644; these were determined in digested sludge (low solids)
176 semivolatile toxic organic pollutants associated with the and in filter cake or compost (high solids).
CWA (as amended 1987); the RCRA (as amended 1986); the
CERCLA (as amended 1986); and other compounds amenable Note: Background levels of this compound were present in the
to extraction and analysis by capillary column gas chromatog- sludge tested, resulting in higher than expected MDLs. The
raphy-mass spectrometry (GC/MS). MDL for this compound is expected to be approximately
50 g/kg with no interferences present.
are added to the sample. If the solids content is less than 1%, The labeled and native compound initial precision as standard
a 1-L sample is extracted at pH 12–13, then at pH <2 with deviation (in g/L) was 33.
methylene chloride using continuous extraction techniques. The labeled and native compound initial accuracy as average
If the solids content is 30% or less, the sample is diluted to 1%
solids with reagent water, homogenized ultrasonically, and SAMPLE COLLECTION, PRESERVATION & HANDLING
extracted at pH 12–13, then at pH <2 with methylene chloride Collect samples in glass containers. Aqueous samples which
using continuous extraction techniques. If the solids content is flow freely are collected in refrigerated bottles using automatic
greater than 30%, the sample is extracted using ultrasonic sampling equipment. Solid samples are collected as grab sam-
techniques. ples using widemouth jars. Maintain samples at 0 to 4C from
Each extract is dried over sodium sulfate, concentrated to a present in aqueous samples, add 80 mg sodium thiosulfate/L
volume of 5 mL, cleaned up using GPC, if necessary, and con- of water. Begin sample extraction within 7 days of collection,
centrated. Extracts are concentrated to 1 mL if GPC is not and analyze all extracts within 40 days of extraction.
An internal standard is added to the extract, and a 1-mL aliquot less are extracted directly using continuous liquid-liquid
of the extract is injected into the GC. The compounds are extraction techniques. Samples containing 1 to 30% solids are
separated by GC and detected by a MS. The labeled compounds diluted to the 1% level with reagent water and extracted using
serve to correct the variability of the analytical technique. continuous liquid-liquid extraction techniques. Samples con-
INTERFERENCES Solvents, reagents, glassware, and other taining greater than 30% solids are extracted using ultrasonic
sample processing hardware may yield artifacts and/or elevated techniques.
baselines causing misinterpretation of chromatograms and Base/neutral extraction — Adjust the pH of the waters in the
spectra. Materials used in the analysis must be demonstrated extractors to 12–13 with 6 N NaOH. Extract with methylene
by running method blanks initially and with each sample lot Acid extraction — Adjust the pH of the waters in the extractors
(sample started through the extraction process on a given 8-h to 2 or less using 6 N sulfuric acid. Extract with methylene
purification of solvents by distillation in all glass systems may
cleaned by solvent rinse and baking at 450C for 1-h minimum. Add acetone:methylene chloride (1:1) to the sample and
mix thoroughly
from source to source, depending on the diversity of the site
being sampled. Concentrate extracts using a K-D apparatus.

bring method performance within acceptable limits. ples, and spikes must be evaluated for interferences. Contam-
Reagent water and high solids reference matrix blanks are ana- requiring no lubrication, a K-D concentrating apparatus, water
lyzed to demonstrate freedom from contamination. Extract bath, and an ultrasonic disrupter with a minimum power of
and concentrate a 1-L reagent water blank or a high solids 300 W and with pulsing capability are also required.
U.S. EPA Industrial Technology Division, Washington, DC, in g/kg is not determined.
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, Accuracy as g/L is not listed.
U.S. EPA, Office of Water Regulations and Standards, 401 M Overall precision in g/L is not listed.
Hexamethyl phosphoramide EPA Method 8270 This calculation is based on a 30-g sample and gel perme-
lakes, etc.
Limit.”

SAMPLE PRESERVATION
concentrator.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous Hexanoic acid EPA Method 1625
sulfate until the sample is free flowing. Add 1 mL of surrogate TITLE Semivolatile Organic Compounds by Isotope Dilu-
standards to all samples, spikes, standards, and blanks. For the tion GC/MS
of a matrix spiking standard. For base/neutral acid analysis, the MATRIX The compounds may be determined in waters,
amount added of the surrogates and matrix spiking com- soils, and municipal sludges by this method.
pounds should result in a final concentration of 100 ng/ L of METHOD SUMMARY This method is used to determine
each base/neutral analyte and 200 ng/L of each acid analyte 176 semivolatile toxic organic pollutants associated with the
in the extract to be analyzed (assuming a 1- L injection). CWA (as amended 1987); the RCRA (as amended 1986); the
Immediately add a 100-mL mixture of 1:1 methylene chlo- CERCLA (as amended 1986); and other compounds amenable
ride:acetone and extract the sample ultrasonically for 3 min to extraction and analysis by capillary column gas chromatog-
and then decant or filter the extracts. Repeat the extraction two raphy-mass spectrometry (GC/MS).
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. Stable isotopically-labeled analogs of the compounds of interest
QUALITY CONTROL A methylene chloride solution con- a 1-L sample is extracted at pH 12–13, then at pH <2 with
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is methylene chloride using continuous extraction techniques.
performance check also must be made during every 12-h shift. If the solids content is 30% or less, the sample is diluted to 1%
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- solids with reagent water, homogenized ultrasonically, and
rophenol, and benzidine is required to verify injection port extracted at pH 12–13, then at pH <2 with methylene chloride
inertness and GC column performance. A calibration standard using continuous extraction techniques. If the solids content is

volume of 5 mL, cleaned up using GPC, if necessary, and con- less are extracted directly using continuous liquid-liquid
centrated. Extracts are concentrated to 1 mL if GPC is not extraction techniques. Samples containing 1 to 30% solids are
performed, and to 0.5 mL if GPC is performed. diluted to the 1% level with reagent water and extracted using
serve to correct the variability of the analytical technique. Base/neutral extraction — Adjust the pH of the waters in the
by running method blanks initially and with each sample lot Ultrasonic extraction of high solids samples — Add anhy-
(sample started through the extraction process on a given 8-h drous sodium sulfate to the sample and QC aliquot(s).
apparatus is used to concentrate extracts. For low solids (aqueous samples), extract, concentrate, and
vinyl silicone bonded phased fused silica capillary column. precision and recovery standard. For high solids samples, two
are used.
rather than instrumental limitations. The limits typify the min- Spike all samples with labeled compounds to assess method
imum quantities that can be detected with no interferences performance. Compute percent recovery of the labeled com-
present. pounds using the internal standard method. Compare the
The minimum level (in g/mL) was not listed. This is defined
as a minimum level at which the analytical system shall give responding labeled compound recovery.
recognizable mass spectra (background corrected) and accept- Reagent water and high solids reference matrix blanks are ana-
able calibration points. lyzed to demonstrate freedom from contamination. Extract
The MDL (in g/kg) in low solids was not listed and in high and concentrate a 1-L reagent water blank or a high solids
solids was not listed; these were determined in digested sludge reference matrix blank with each sample’s lot (samples started
(low solids) and in filter cake or compost (high solids). through the extraction process on the same 8-h shift, to a
maximum of 20 samples).
deviation (in g/L) was not listed. Field replicates may be collected to determine the precision of
The labeled and native compound initial accuracy as average the sampling technique, and spiked samples may be required
recovery (in g/L) was not listed. to determine the accuracy of the analysis when the internal
Collect samples in glass containers. Aqueous samples which REFERENCE Semivolatile Organic Compounds by Isotope
flow freely are collected in refrigerated bottles using automatic Dilution GC/MS. Office of Water Regulation and Standards,
sampling equipment. Solid samples are collected as grab sam- U.S. EPA Industrial Technology Division, Washington, DC,
ples using widemouth jars. Maintain samples at 0 to 4C from EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
the time of collection until extraction. If residual chlorine is U.S. EPA, Office of Water Regulations and Standards, 401 M
present in aqueous samples, add 80 mg sodium thiosulfate/L St., SW, Washington, DC, 20460. Phone: 202-382-7131).

2-Hexanone EPA Method 1624 SAMPLE COLLECTION, PRESERVATION & HANDLING
TITLE Volatile Organic Compounds by Isotope Dilution air bubbles are entrapped. Samples are maintained at 0 to 4 C
GC/MS from the time of collection until analysis. If an aqueous sample
MATRIX Compounds may be determined in waters, soils, (10 mg/40 mL) to the empty sample bottles just prior to ship-
and municipal sludges by this method. ment to the sample site. All samples must be analyzed within
METHOD SUMMARY This method is used to determine 58 14 days of collection.
volatile toxic organic pollutants associated with the CWA (as SAMPLE PREPARATION Samples containing less than 1%
amended 1987); the RCRA (as amended 1986); the CERCLA solids are analyzed directly as aqueous samples. Samples con-
(as amended 1986); and other compounds amenable to purge- taining 1% solids or greater are analyzed as solid samples uti-
and-trap gas chromatography-mass spectrometry (GC/MS). lizing one of two methods, depending on the levels of
If the solids content is less than 1%, stable isotopically-labeled pollutants, in the sample. Samples containing 1% solids or
analogs of the compounds of interest are added to a 5-mL greater, and low to moderate levels of pollutants are analyzed
sample and the sample is purged with an inert gas at 20–25 C by purging a known weight of sample added to 5 mL of reagent
in a chamber designed for soil or water samples. If the solids water. Samples containing 1% solids or greater, and high levels
content is greater than 1%, 5 mL of reagent water and the of pollutants, are extracted with methanol, and an aliquot of
labeled compounds are added to a 5-g aliquot of sample and the methanol extract is added to reagent water and purged.
the mixture is purged at 40C. Compounds that will not purge QUALITY CONTROL A field blank prepared from reagent
at 20–25C or at 40C are purged at 78–85C. In the purging water and carried through the sampling and handling protocol
process, the volatile compounds are transferred from the aque- may serve as a check on contamination from shipment and
ous phase into the gaseous phase where they are passed into a storage.
trap is backflushed and heated rapidly to desorb the com- The analyst is permitted to modify this method to improve
pounds into a GC. The compounds are separated by the GC separations or lower the costs of measurements, provided all
and detected by a MS. The labeled compounds serve to correct performance specifications are met. Analyses of blanks are
the variability of the analytical technique. required. When results of spikes indicate atypical method per-
INTERFERENCES Impurities in the purge gas, organic com- performance within acceptable limits. Analyze two sets of four
pounds outgassing from the plumbing upstream of the trap, 5-mL aliquots (8 aliquots total) of the aqueous performance
and solvent vapors in the lab account for most problems. Sam- standard. Spike all samples with labeled compounds to assess
ples can be contaminated by diffusion of volatile organic com- method performance on the sample matrix. Compute the per-
pounds (particularly methylene chloride) through the bottle cent recovery of the labeled compounds using the internal stan-
seal during shipment and storage. Contamination by carryover dard method. Compare the percent recovery for each
can occur when high-level and low-level samples are analyzed compound with the corresponding labeled compound recov-
INSTRUMENTATION Major equipment includes a GC with and spiked samples may be required to determine the accuracy
linear temperature programming and a glass jet separator as of the analysis when the internal method is used.
Column: 2.8 m 2 mm I.D. glass, packed with 1% SP-1000 on EPA Industrial Technology Division, Washington, DC, EPA
Carbopak B, 60/80 mesh, or equivalent. Method 1624, Rev. C, June 1989 (contact W.A. Telliard, U.S.
filter cake or compost (high solids). 2-Hexanone EPA Method 8240
CAS #591-78-6
The MDL (in g/kg) for low solids is not listed and for high
solids is not listed.
deviation was not listed. MATRIX Nearly all types of sample matarices, regardless of
Labeled and native compound accuracy (in g/L) as average water content, can be analyzed using this method. This includes
recovery was not listed. groundwater, aqueous sludges, caustic liquors, acid liquors, waste
Acceptance criteria are at 20 g/L for this compound. solvents, oily wastes, mousses, tars, fibrous wastes, polymetric

emulsions, filter cakes, spent carbons, spent catalysts, soils, and MULTIPLICATION FACTORS FOR OTHER MATRICES
sediments. Other Matrices Factor (a)
limited applications). For the purge-and-trap method an inert
gas (zero grade nitrogen or helium) is bubbled through a 5-mL (a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous
solution at ambient temperature. Purged sample components samples, the factor is on a wet-weight basis.
if residual chlorine is present, collect sample in a 40-oz. soil
sequentially. Whenever an unusually concentrated sample is Soils or sediments, and sludges — Use an 8-oz. widemouth
refrigerator.
Sample estimated quantitation limits (EQLs) are highly while adjusting the sample volume to 5.0 mL. If there is only
matrix-dependent. The EQLs listed may not always be achiev- one volatile organic analysis (VOA) vial, a second syringe
able. EQLs listed for soils or sediments are based on wet weight. should be filled at this time to protect against possible loss of
Normally, data is reported on a dry-weight basis; therefore, sample integrity. Add 10 L of surrogate spiking solution and
EQLs will be higher, based on the percent dry weight of each 10 L of internal standard spiking solution through the valve
sample. Note that EQLs are even more variable than MDLs and bore of the 5-mL syringe, then close the valve. The surrogate
that they are highly variable depending on the matrix being and internal standards may be mixed and added as a single
analyzed. spiking solution.
EQL in groundwater in g/L was 50. Sediments, soils, and waste samples — All samples of this type
EQL in low soil or sediment in g/kg was 50. should be screened by GC analysis using a headspace method

Hexazinone EPA Method 507
CAS #51235-04-2
row metal spatula. Weigh the amount of the sample into a tared TITLE Determination of Nitrogen and Phosphorus-Con-
taining Pesticides in Water by GC/NPD
device to the purge-and-trap system. MATRIX This method is applicable to the determination of
ished drinking water and groundwater.
is either extracted or diluted, depending on its solubility in METHOD SUMMARY Method 507 covers 46 nitrogen- and
methanol. Wastes that are insoluble in methanol are diluted phosphorus-containing pesticides. A 1-L sample is fortified
with reagent tetraglyme or possibly polyethylene glycol (PEG). with a surrogate standard, salted, buffered, extracted with
An aliquot of the extract is added to organic-free reagent water methylene chloride, and concentrated; then the solvent is
containing surrogate and internal standards. This is purged at exchanged with methyl tert-butyl ether (MTBE) and concen-
ambient temperature. All samples with an expected concentra- trated again, and a 2-L aliquot of a sample extract is injected
tion of >1.0 mg/kg should be analyzed by this method. into a GC system equipped with a selective nitrogen-phospho-
Mix the contents of the sample container with a narrow metal rus detector and a capillary column for analysis.
spatula. For sediments or soils and solid wastes that are insol- INTERFERENCES Method interferences may be caused by
uble in methanol, weigh 4 g (wet weight) of sample into a tared contaminants in solvents, reagents, glassware, and other sample
20-mL vial. For waste that is soluble in methanol, tetraglyme, processing apparatus. Interfering contamination may occur
or PEG, weigh 1 g (wet weight) into a tared scintillation vial when a sample containing low concentrations of analytes is
or culture tube or a 10-mL volumetric flask. Quickly add analyzed immediately following a sample containing relatively
9.0 mL of appropriate solvent then add 1.0 mL of a surrogate high concentrations. One or more injections of MTBE should
be made following the analysis of a sample with high concen-
METHANOL EXTRACT REQUIRED FOR ANALYSIS trations of analytes to check for analyte carryover. Matrix inter-
OF HIGH-CONCENTRATION SOILS OR SEDIMENTS ferences may be caused by contaminants that are coextracted
Approximate Volume of from the sample. The extent of matrix interferences will vary
Concentration Range Methanol Extract (a) considerably from source to source, depending upon the water
sampled.
500–10,000 g/kg 100 L
1,000–20,000 g/kg 50 L INSTRUMENTATION A gas chromatograph system (GC)
5,000–100,000 g/kg 10 L equipped with a nitrogen-phosphorus detector (NPD) is
25,000–500,000 g/kg 100 L of 1/50 dilution (b) needed.
Calculate appropriate dilution factor for concentrations Column 1: 30 m 0.25 mm I.D. DB-5 bonded fused silica col-
exceeding this table. umn, 0.25 m film thickness, or equivalent.
(a) The volume of methanol added to 5 mL of water being purged
column, 0.25 m film thickness, or equivalent.
volume of methanol is necessary to maintain a volume of 100 L PRECISION & ACCURACY This method has been validated
added to the syringe. in a single lab and estimated detection limits (EDLs) have been
(b) Dilute an aliquot of the methanol extract and then take 100 L determined for each analyte. Observed detection limits may
for analysis. vary among waters, depending upon the nature of the inter-
QUALITY CONTROL Demonstrate, through the analysis of ferences in the sample matrix and the specific instrumentation
a reagent water blank, that interferences from the analytical used. Analytes that are not separated chromatographically can-
system, glassware, and reagents are under control. Blank sam- not be individually identified and measured unless an alterna-
ples should be carried through all stages of the sample prepa- tive technique for identification and quantification exist.
ration and measurement steps. For each analytical batch (up The estimated detection limit (in g/L) was 0.76. The EDL is
to 20 samples), a reagent blank, matrix spike, and matrix spike defined as either method detection limit or a level of compound
duplicate must be analyzed (the frequency of the spikes may in a sample yielding a peak in the final extract with signal-to-
be different for different monitoring programs). The blank and noise ratio of approximately 5, whichever value is higher.
preparation and measurement steps. QC samples mentioned The concentration used for these measurements (in g/L) was
in the section on Interferences will also be needed as appropri- 7.6.
ate to those situations. The accuracy (as % recovery) was 90.
The precision (% RSD) was 7.
846). U.S. EPA. 1983. Method 8240B, Rev. 2, Nov. 1990. Office SAMPLING METHOD Grab samples are collected in 1-L
of Solid Wastes, Washington, DC. glass sample bottles (prewashed with detergent and hot tap

water, rinsed with reagent water, and dried in an oven at 400C REFERENCE Methods for the Determination of Organic
for 1 h) with screw caps lined with PTFE-fluorocarbon. Compounds in Drinking Water, EPA/600/4-88/039 (revised
July 1991). U.S. EPA Environmental Monitoring Systems Lab-
sample bottle in amounts to produce a concentration of
10 mg/L. If residual chlorine is present, add 80 mg of sodium Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS
thiosulfate/L of sample to the sample bottle prior to collection. Order Number is PB91-231480.
Hexyl 2-ethylhexyl phthalate EPA Method 8061
SAMPLE PREPARATION Fortify the sample with 50 L of TITLE Phthalate Esters by Capillary Gas Chromatography
the surrogate standard solution, adjust to pH 7 with phosphate With Electron Capture Detection (GC/ECD)
buffer, add 100 g NaCl to the sample, and seal and shake to MATRIX This method covers aqueous and solid matrices.
dissolve the salt; then extract with methylene chloride in a This includes a wide variety such as drinking water, ground-
separatory funnel or in a mechanical tumbler bottle. Dry the water, industrial wastewaters, surface waters, soils, solids, and
extract by pouring it through a solvent-rinsed drying column sediments.
containing about 10 cm of anhydrous sodium sulfate. Collect
the extract in a Kuderna-Danish (K-D) concentrator and rinse METHOD SUMMARY This method is used to determine the
the column with 20–30 mL methylene chloride. Concentrate identities and concentrations of phthalate esters in liquid, solid
the extract to about 2 mL and rinse the flask and its lower joint and sludge matrices. When used to analyze for any or all of the
into the concentrator tube with 1 to 2 mL of methyl t-butyl target analytes, compound identification should be supported
ether (MTBE). Add 5–10 mL of MTBE and concentrate the by at least one additional qualitative technique. This method
extract twice (adding more MTBE) to a final volume of 5.0 mL describes conditions for parallel column, dual electron capture
detector analysis, which fulfills the above requirement. Alter-
and store it at 4C until analysis.
natively, GC/MS could be used for compound confirmation.
Note: If methylene chloride is not completely removed from
A measured volume or weight of sample (approximately 1 L
for liquids, 10 to 30 g for solids and sludges) is extracted by
QUALITY CONTROL Minimum quality control require- using the appropriate sample extraction technique specified in
ments are initial demonstration of lab capability, determina- EPA Method 3510, EPA Method 3540, and EPA Method 3550.
tion of surrogate compound recoveries in each sample and After cleanup, the extract is analyzed by GC/ECD.
blank, monitoring internal standard peak area or height in each
INTERFERENCES The sensitivity of this method usually
sample and blank, analysis of lab reagent blanks, lab fortified depends on the level of interferences rather than on instrumen-
samples, lab fortified blanks, and other QC samples. A lab tal limitations. If interferences prevent detection of the analytes,
reagent blank is analyzed to demonstrate that all glassware and cleanup of the sample extracts is necessary. Either EPA Method
reagent interferences are under control. 3610 or EPA Method 3620 alone or followed by EPA Method
Initial demonstration of capability is fulfilled by analyzing four 3660, Sulfur Cleanup, may be used to eliminate interferences
fortified reagent water samples with the recovery value for each in the analysis. EPA Method 3640, Gel Permeation Cleanup, is
analyte falling within the acceptable range ( 30% average applicable for samples that contain high amounts of lipids and
recovery). Surrogate recoveries from samples or method blanks waxes.
must be 70–130%. The internal standard response for any sam- Interferences coextracted from the samples will vary consider-
ple chromatogram should not deviate from the daily calibra- ably from waste to waste. Glassware must be scrupulously
tion check standard’s internal standard response by more than clean. All glassware require treatment in a muffle furnace at
30% or lab fortified blanks and sample matrices are used to 400C for 2 to 4 h, or thorough rinsing with pesticide-grade
assess lab performance and analyte recovery, respectively. solvent, prior to use.Volumetric glassware should not be heated
If the response for the target analyte peak exceeds the working in a muffle furnace. Storage of glassware in the lab introduces
contamination, even if the glassware is wrapped in aluminum
foil.Sodium sulfate, Florisil, and alumina may be contaminated
with phthalate esters and, therefore, use of these materials in
raphy column should be used to confirm peak identification
sample cleanup should be employed cautiously. If these mate-
when sample components are not resolved adequately.
rials are used, they must be obtained packaged in glass. Heating
EPA CONTACT & HOTLINE For technical questions contact at 400C for sodium sulfate, 320C for Florisil, and 210C for
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and alumina is recommended. Glass wool used in any step of sam-
Drinking Water (WH-550D), 401 M St. SW, Washington, DC ple preparation should be a specially treated pyrex wool, pes-
20460. Tel. (202) 260-3040. For further information the EPA ticide grade, and must be baked at 400C for 4 h immediately
Safe Drinking Water Hotline may be called at: (800) 426-4791. prior to use.

Paper thimbles and filter paper must be exhaustively washed The average recovery (in %) with %RSD (in parenthesis) from
with the solvent that will be used in the sample extraction. 3 determinations and a spike concentration of 20 g/L in
Soxhlet extraction of paper thimbles and filter paper for 12 h leachate was 91.1 (27.5) using 3M Empore Disks and EPA
with fresh solvent should be repeated for a minimum of three Method 8061.
times. Method blanks should be obtained before any of the The average recovery (in %) with %RSD (in parenthesis) from
precleaned thimbles or filter papers are used. 3 determinations and a spike concentration of 20 g/L in
INSTRUMENTATION Gas chromatograph suitable for on- estuarine groundwater was 81.4 (17.6) using 3M Empore
Disks and EPA Method 8061.
column and split/splitless injections.
The average recovery (in %) with %RSD (in parenthesis) from
Column 1: 30 m 0.53 mm ID, 5% phenyl/95% methyl sili- 3 determinations and a spike concentration of 1 mg/kg in
cone fused-silica open tubular column, DB-5, 1.5 g film estuarine sediment was not determined (matrix interferant)
thickness. after sulfur cleanup with EPA Method 3660.
Column 2: 30 m 0.53 mm ID, 14% cyanopropyl phenyl sili- The average recovery (in %) with %RSD (in parenthesis) from
cone fused-silica open tubular column, DB-1701, 1.0 g 3 determinations and a spike concentration of 1 mg/kg in
film thickness. municipal sludge was 114 (10.5).
A dual electron capture detector (ECD) is used. A Kuderna- The average recovery (in %) with %RSD (in parenthesis) from
Danish (K-D) apparatus is required along with a vacuum man- 3 determinations and a spike concentration of 1 mg/kg in
ifold consisting of individually adjustable, easily accessible sandy loam soil was 57.7 (2.8).
flow-control valves for up to 24 cartridges, sample rack, chem- SAMPLE COLLECTION, PRESERVATION & HANDLING
ically resistant cover and seals, heavy-duty glass basin, remov- Containers used to collect samples for the determination of
able stainless steel solvent guides, built-in vacuum gauge and semivolatile organic compounds should be soap and water
valve. Also, 6-mL, 1-g solid-phase extraction cartridges, LC- washed followed by methanol (or isopropanol) rinsing. The
Florisil or equivalent, prepackaged, ready to use will be needed. sample containers should be of glass or Teflon® and have screw-
PRECISION & ACCURACY The MDL actually achieved in top covers with Teflon® liners. Sample containers should be
a given analysis will vary, as it is dependent on instrument filled with care to prevent any portion of the collected sample
sensitivity and matrix effects. This method has been tested in coming in contact with the sampler’s gloves.
a single lab. Single-operator precision, overall precision, and No preservation is used with concentrated waste samples. With
method accuracy were found to be related to the concentration liquid samples containing no residual chlorine and with soil,
of the compounds and the type of matrix. sediment, and sludge samples, immediately cooling to 4C is
MULTIPLICATION FACTORS FOR OTHER MATRICES (a) the only preservation used. When residual chlorine is present
then 3 mL of 10% aqueous sodium sulfate is added for each
Matrix Factor (b)
gallon of sample collected, followed by cooling to 4C.
Groundwater 10
Low-concentration soil by ultrasonic cleanup 670 MHT Liquid samples must be extracted within 7 days and
extraction with GPC their extracts analyzed within 40 days. Concentrated waste, soil,
High-concentration soil and sludges 10,000 sediment, and sludge samples must be extracted within 14 days
by ultrasonic extraction and their extracts analyzed within 40 days.
Non-water miscible waste 100,000 SAMPLE PREPARATION In general, water samples are
(a) Sample EQLs are highly matrix-dependent. The EQLs listed are extracted at a pH of 5 to 7 with methylene chloride in a sepa-
provided for guidance and may not always be achievable. ratory funnel (EPA Method 3510). EPA Method 3520 is not
(b) EQL = [Method detection limit] [Factor]. For non-aqueous recommended for the extraction of aqueous samples because
samples, the factor is on a wet-weight basis. the longer chain esters tend to adsorb to the glassware and
consequently, their extraction recoveries may be poor. Solid
The MDL using 7 replicate determinations and a spike concen- samples are extracted with hexane/acetone (1:) or methylene
tration of 100 g/L was 130 ng/L. chloride/acetone (1:1) in a Soxhlet extractor (EPA Method
The average recovery from HPLC-grade water using 4 deter-
3540) or with an ultrasonic extractor (EPA Method 3550).
minatons and a spike concentration of 100 g/L was 93.9%.
Immediately prior to extraction, spike 500 L of the surrogate
The precision (as RSD) from HPLC-grade water using 4 deter-
standard spiking solution into 1-Laqueoussample or 30-g solid
minatons and a spike concentration of 100 g/L was 22.4%.
sample. Extraction of particulate-free aqueous samples using
The average recovery from groundwater using 4 determinatons
C-18 extraction disks is an optional method that can be used.
and a spike concentration of 100 g/L was 83.4%.
The precision (as RSD) from groundwater using 4 determina- Prior to Florisil cleanup or GC analysis, the methylene chloride
tons and a spike concentration of 100 g/L was 8.8%. and methylene chloride/acetone extracts must be exchanged to
The average recovery (in %) with %RSD (in parenthesis) from hexane. Exchange is not required for the acetonitrile extracts.
3 determinations and a spike concentration of 20 g/L in Cleanup may not be necessary for extracts from a relatively
water was 84.7 (5.3) using 3M Empore Disks and EPA clean sample matrix. Florisil Cartridge Cleanup may be used
Method 8061. for extract cleanup.

If PCBs and organochlorine pesticides are known to be present REFERENCE Test Methods for Evaluating Solid Waste, Phys-
in the sample, and if Florisil Cartridge Cleanup is considered, ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
then two fractions are collected: Fraction 1 is eluted with 5 mL of Solid Waste, Washington, DC, EPA Method 8061, Nov. 1990.
of 20% methylene chloride in hexane and Fraction 2 is eluted
with 5 mL of 10% acetone in hexane. Fraction 1 contains the
organochlorine pesticides and PCBs, and can be discarded. 1,2,3,4,6,7,8-HpCDD EPA Method 8280
Fraction 2 contains the phthalate esters and is analyzed by CAS #35822-46-9
GC/ECD.
QUALITY CONTROL Identify compounds in the sample by TITLE The Analysis of Polychlorinated Dibenzo-P-Dioxins
and Polychlorinated Dibenzofurans.
comparing the retention times of the peaks in the sample chro-
matogram with those of the peaks in standard chromatograms. MATRIX This method is appropriate for the determination
The retention time window used to make identification is based of tetra-, penta-, hexa-, hepta-, and octachlorinated dibenzo-
upon measurements of actual retention time variations over p-dioxins (PCDDs) and dibenzofurans (PCDFs) in chemical
the course of 10 consecutive injections. wastes including still bottoms, fuel oils, sludges, fl ash, reactor
residues, soil and water.
Calibration standards are prepared at a minimum of five con-
centrations for each parameter of interest through dilution of METHOD SUMMARY This method covers 22 PCDD and
the stock standard solutions with hexane. One of the concen- PCDF compounds and it uses a high resolution capillary GC
trations should be at a concentration near, but above, the column with low resolution mass spectrometry. Samples are
method detection limit. Prepare stock standard solutions in extracted and concentrated by several methods that vary
depending on the matrix involved. The organic extracts are
hexane. Stock standards should be checked frequently for signs
cleaned-up by washing with aqueous basic and acid solutions
of degradation or evaporation, especially just prior to prepar-
and then separated into fractions using a column of neutral
ing calibration standards from them. Stock standard solutions alumina. The fraction containing the PCDDs and PCDFs is
must be replaced after one year, or sooner if comparison with then further cleaned-up using a column of activated carbon.
check standards indicates a problem. The suggested internal The final extract is concentrated and Carbon-13 labeled inter-
standards are: 2,5-dibromotoluene, 1,3,5-tribromobenzene, nal standards are added prior to analysis by GC/MS using a
and , -dibromo-m-xylene. The analyst can use any of the capillary GC column and selected ion monitoring using five
three compounds provided that they are resolved from matrix sets of ions that are detailed in the method. Certain 2,3,7,8-
interferences. Recommended surrogate compounds are substituted congeners are used to provide calibration and
-2,6-trichlorotoluene, 1,4-dichloronaphth alene, and method recovery information. Proper column selection and
2,3,4,5,6-pentachlorotoluene. access to reference isomer standards, may in certain cases, pro-
vide isomer specific data.
Spike each sample, standard, and blank with surrogate com-
pounds. Three surrogates are suggested for this method: diphe- INTERFERENCES Solvents, reagents, glassware, and other
nyl phthalate, diphenyl isophthalate, and dibenzyl phthalate. sample processing hardware may yield discrete artifacts and/or
elevated baselines which may cause misinterpretation of chro-
The quality control check sample concentrate should contain matographic data. Use high purity reagents and solvents to
the test compounds at 5 to 10 ng/ LAn internal standard peak minimize interference problems. Interferents coextracted from
area check must be performed on all samples. The internal the sample will vary considerably from source to source.
standard must be evaluated for acceptance by determining PCDDs and PCDFs are often associated with other interfering
whether the measured area for the internal standard deviates chlorinated compounds such as PCBs and polychlorinated
by more than 30% from the average are for the internal stan- diphenyl ethers which may be found at concentrations several
dard in the calibration standards. When the internal standard orders of magnitude higher than that of the analytes of interest.
peak area is outside that limit, all samples that fall outside the INSTRUMENTATION A low resolution GC/MS utilizing 70
QC criteria must be reanalyzed. Benzyl benzoate has been ev must be capable of selected ion monitoring (SIM) for at
tested and found appropriate as an internal standard for this least 11 ions simultaneously, with a cycle time of 1 second or
method. less. Minimum integration time for SIM is 50 ms per m/z. Also
Any compounds confirmed by two columns may also be con- required is a GC-to-MS interface constructed of all glass or
glass-lined materials. One of the following GC columns is
firmed by GC/MS. The sample extract and associated blank
required:
should be analyzed by GC/MS. A reference standard of the
compound must also be analyzed by GC/MS. Include a mid- Column 1: 50 m CP-Sil-88 fused silica capillary column.
concentration calibration standard after each group of Column 2: DB-5 (30 m  0.25 mm I.D., 0.25-um film thick-
20 samples. The response factors for the mid-concentration ness) fused silica capillary column.
calibration must be within 15% of the average values for the Column 3: 30 m SP-2250 fused silica capillary column.
multiconcentration calibration. Demonstrate through the When toluene is employed as the final solvent, use of a bonded
analyses of standards that the Florisil fractionation scheme is phase column is recommended. Solvent exchange into tride-
reproducible. cane is required for other liquid phases or nonbonded columns

such as CP-Sil-88. Chromatographic conditions must be column with 15 mL of 60 percent (v/v) methylene chloride in
adjusted to account for solvent boiling points. hexane and collect this second fraction in a conical shaped
concentrator tube.
PRECISION & ACCURACY Accuracy, precision, MDLs and
concentration ranges for the compounds covered by this Carbon column clean-up — Using a carefully regulated stream
method have not been determined or published by EPA yet. of nitrogen, concentrate the first 8 percent fraction (methylene
The sensitivity of this method is dependent upon the level of chloride in hexane) from the alumina column to about 1 mL.
interferents within a given matrix. Proposed quantification lev- Save this 8 percent concentrate for GC/MS analysis to check
els for target analytes were 2 ppb in soil samples, up to 10 ppb for breakthrough of PCDDs and PCDFs. Concentrate the sec-
in other solid wastes and 10 ppt in water. Actual values have ond 60 percent fraction (methylene chloride in hexane) to
been shown to vary by homologous series and, to a lesser about 2 to 3 mL. Prepare a carbon column and rinse the carbon
degree, by individual isomer. with 5 mL cyclohexane/methylene chloride (50:50 v/v) in the
forward direction of flow and then in the reverse direction of
SAMPLING METHOD Grab and composite samples must
flow. While still in the reverse direction of flow, transfer the
be collected in 1 L or 1-quart amber glass bottles with Teflon®-
sample concentrate to the column and elute with 10 mL of
lined screw-caps that have been acid-washed and solvent rinsed
methylene chloride/methanol/benzene (75:20:5, v/v). Save all
before use. If compositing equipment is used, the system must
above eluates and combine them (this fraction may be used as
incorporate glass sample containers for the collection of a min-
a check on column efficiency). Next, turn the column over and,
imum of 250 mL. samples.
in the direction of forward flow, elute the PCDD/PCDF frac-
SAMPLE PRESERVATION Samples must be cooled and tion with 20 mL toluene. Evaporate the toluene fraction to
stored at 4C. about 1 mL on a rotary evaporator and transfer this concen-
trate to a 2.0-mL Reacti-vial. Concentrate the sample using a
MHT Samples must be extracted within 30 days and analyzed
stream of nitrogen gas. The final volume will depend on the
within 45 days of collection.
relative concentration of target analytes but it is typically
SAMPLE PREPARATION 100 L for soil samples and 500 L for sludge, still bottom, and
Soil samples — Extract 20 g of a 1:1 soil and anhydrous sodium fl ash samples. Extracts which are determined to be outside
sulfate mixture with 1:4 methanol-petroleum ether for 2 h in the calibration range for individual analytes must be diluted or
a wrist-action shaker. Concentrate the extract in a K-D and a smaller portion of the sample must be re-extracted.
then exchange the solvent with hexane in the K-D. The final
An alternate carbon column clean-up also may be used with a
volume is 15 mL of hexane.
1 mL HPLC injector loop. The injector loop is connected to
Aqueous samples — Extract a 1 L sample with methylene chlo- the optional HPLC column.
ride, dry it with anhydrous sodium sulfate and concentrate it
QUALITY CONTROL Demonstrate, using a method blank,
in a K-D followed by exchange with hexane in the K-D. A
that all glassware and reagents are interferent-free at the MDL
continuous liquid-liquid extractor may be used in place of a
of the matrix of interest. A “method blank” must be run with
separatory funnel to avoid emulsions. The final volume is
each 20 or fewer samples. The method blank is also dosed with
15 mL of hexane.
the internal standards. For water samples, 1 L of deionized
Alumina column clean-up — The clean-up procedure and/or distilled water should be used as the method blank.
described below consists of two phases. The first phase involves Mineral oil may be used as the method blank for other matrices.
a sequential basic and acid washing of the extract that contains
Calculate response factors for standards relative to the internal
the analytes.
standards. Add a recovery standard to the samples prior to
Wash the 15 mL hexane extract with 20% potassium hydroxide injection. The concentration of the recovery standard in the
in a separatory funnel. Repeat the washing until no color is sample extract must be the same as that in the calibration
visible in the bottom layer but no more than four times because standards used to measure the response factors.
strong base is known to degrade certain PCDDs/PCDFs, so
Field duplicates (individual samples taken from the same loca-
contact time must be minimized. Next, partition the 15 mL
tion at the same time) should be analyzed periodically to deter-
hexane against 40 mL of 5% sodium chloride. Next, partition
mine the total precision (field and lab). Where appropriate,
the 15 mL hexane against 40 mL of concentrated sulfuric acid.
field blanks should be provided to monitor for possible cross-
Repeat the acid washings until no color is visible in the acid
contamination of samples in the field. GC column performance
layer (but no more than four times). Finally, partition the
must be demonstrated initially and verified prior to analyzing
15 mL hexane against 40 mL of 5% sodium chloride. Dry the
any sample in a 12-hr period. The GC column performance
organic layer with anhydrous sodium sulfate and concentrate
check solution must be analyzed under the same chromato-
it to near dryness with a rotary evaporator. Dissolve the hexane
graphic and mass spectrometric conditions used for other sam-
residue from the first phase of the clean-up in 2 mL of hexane
ples and standards.
and apply it carefully to the top of a pre-eluted Woelm super
1 neutral alumina column. Elute the column with 10 mL of 8 Retention times of target analytes must be verified using refer-
percent (v/v) methylene chloride in hexane. Check by GC/MS ence standards. These values must correspond to the retention
analysis that no PCDDs of PCDFs are elute in this fraction time windows established. While certain cleanup techniques
before discarding it. Elute the PCDDs and PCDFs from the are provided as part of this method, unique samples may

require additional cleanup techniques to achieve the method Column 2: 30 m DB-225 fused silica capillary column, or
detection limit. equivalent.
REFERENCE Test Methods for Evaluating Solid Waste (SW- PRECISION & ACCURACY Precision, bias and concentra-
846). U.S.E.P.A., 1986. Method 8280, Rev. 0, Sept. 1986. Office tion ranges for the compounds covered by this method have
of Solid Wastes, Washington, DC. not been determined yet. The sensitivity of Method 8290 is
dependent upon the level of interferences within a given
matrix. Samples containing concentrations of specific conge-
neric analytes of PCDDs and PCDFs that are greater than ten
1,2,3,4,6,7,8-HpCDD EPA Method 8290
times the upper method calibration limits must be analyzed by
CAS #35822-46-9
a protocol designed for such concentration levels, e.g., EPA
TITLE Polychlorinated Dibenzodioxins (PCDDs) and Poly- Method 8280.
chlorinated Dibenzofurans (PCDFs) by High-Resolution Gas SAMPLE PREPARATION
Chromatography/High-Resolution Mass Spectrometry Sludge/wet fuel oil — Extract aqueous sludge or wet fuel oil
(HRGC/HRMS). samples by refluxing a sample with toluene using a Dean-Stark
MATRIX This method is applicable with a variety of envi- water separator until all the water is removed. Filter the toluene
ronmental matrices including: water, soil, sediment, paper extract through a glass fiber filter, or equivalent, and concen-
pulp, fl ash, fish tissue, human adipose tissue, sludges, fuel oil, trate it to near dryness either on a rotary evaporator using an
chemical reactor residue, and still bottoms. inert gas. Transfer the concentrate to a separatory funnel using
hexane and wash it with 5% sodium chloride solution. Proceed
METHOD SUMMARY This method provides procedures for to clean up.
the detection and quantitative measurement of polychlorinated
dibenzo-p-dioxins (tetra- through octachlorinated homo- Soil/sediment — If the sample is wet, add anhydrous powdered
logues; PCDDs), and polychlorinated dibenzofurans (tetra- sodium sulfate to it until a free flowing mixture is obtained.
through octachlorinated homologues; PCDFs) in a variety of Place the soil/sodium sulfate mixture in the Soxhlet apparatus,
environmental matrices and at part-per-trillion (ppt) to part- add toluene, and reflux for 16 h. The solvent must cycle com-
per-quadrillion (ppq) concentrations. High-resolution gas pletely through the system five times per h. Cool and filter the
chromatography and high-resolution mass spectrometry extract through a glass fiber filter and concentrate to near dry-
(HRGC/HRMS) on purified sample extracts provides highly ness on a rotary evaporator. Transfer the residue to a separatory
specific identification of each analyte. Quantification is pro- funnel, using hexane. Proceed to clean up.
vided using calibration standards. Aqueous samples — Use a 1-L sample; the method may require
INTERFERENCES Solvents, reagents, glassware, and other acetone to be added to it. When the sample is judged to contain
sample processing hardware may yield discrete artifacts that 1% or more solids, it must be filtered through a glass fiber filter
may cause misinterpretation of the chromatographic data. that has been rinsed with toluene. If the suspended solids con-
Analysts should avoid using PVC gloves. Interferants coex- tent is too great to filter, centrifuge the sample, decant, and
tracted from the sample will vary considerably from matrix to then filter the aqueous phase. Combine the solids from the
matrix. PCDDs and PCDFs are often associated with other centrifuge bottle(s) with the particulates on the filter and with
interfering chlorinated substances such as polychlorinated the filter itself and proceed with Soxhlet extraction for soil/sed-
biphenyls (PCBs), polychlorinated diphenyl ethers (PCDEs), iment. Extract the aqueous filtrate with methylene chloride in
polychlorinated naphthalenes, and polychlorinated alkyldiben- a separatory funnel, filter the extract through anhydrous
zofurans that may be found at concentrations several orders of sodium sulfate, and concentrate it using a K-D apparatus or a
magnitude higher than the PCDDs or PCDFs. rotary evaporator. Exchange the solvent with hexane and pro-
ceed to clean up.
A high-resolution capillary column is used in this method.
However, no single column is known to resolve all isomers. The Clean up — The sample extract is cleaned up utilizing a num-
60 m DB-5 GC column is capable of 2,3,7,8-TCDD isomer ber of different techniques. Partition cleanup is where the sam-
specificity. In order to determine the concentration of the ple extract is partitioned with concentrated sulfuric acid, 5%
2,3,7,8-TCDD (if detected on the DB-5 column), the sample aqueous sodium chloride, and 20% aqueous potassium
extract must be reanalyzed on a column capable of hydroxide. Silica/alumina column cleanup involves packing
2,3,7,8-TCDF isomer specificity (e.g., DB-225, SP-2330, SP- gravity columns with silica gel and alumina and sequentially
2331, or equivalent). eluting the residue from the partition cleanup. Carbon column
cleanup involves packing a column with a mixture of AX–21
INSTRUMENTATION High-Resolution Gas Chromato-
and Celite 545 and sequentially eluting the sample concentrate
graph/High-Resolution Mass Spectrometer/Data System
from the silica/alumina cleanup with hexane, cyclohex-
(HRGC/HRMS/DS) equipped with a GC injection port
ane/methylene chloride (50:50), and methylene chloride/meth-
designed so that the separation of 2,3,7,8-TCDD from the other
anol/toluene (75:20:5). Then the column is turned upside
TCDD isomers achieved in the gas chromatographic column
down and the PCDD/PCDF fraction is eluted with toluene.
is not appreciably degraded.
The toluene fraction is concentrated and stored in the dark at
Column 1: 60 m DB-5 fused silica capillary column. room temperature until analysis.

1,2,3,4,6,7,8-HpCDF EPA Method 8280
a reagent water blank, that interferences from the analytical CAS #67562-39-4
system, glassware, and reagents are under control. For each
analytical batch (up to 20 samples), a reagent blank, matrix TITLE The Analysis of Polychlorinated Dibenzo-P-Dioxins
spike, and matrix spike duplicate/duplicate must be analyzed and Polychlorinated Dibenzofurans.
(the frequency of the spikes may be different for different mon-
itoring programs). The blank and spiked samples must be car- MATRIX This method is appropriate for the determination
ried through all stages of the sample preparation and of tetra-, penta-, hexa-, hepta-, and octachlorinated dibenzo-
measurement steps. p-dioxins (PCDDs) and dibenzofurans (PCDFs) in chemical
wastes including still bottoms, fuel oils, sludges, fl ash, reactor
A GC column performance check is required at the beginning residues, soil and water.
of each 12-h period during which samples are analyzed. An
HRGC/HRMS method blank run is required between a cali- METHOD SUMMARY This method covers 22 PCDD and
bration run and the first sample run. The same method blank PCDF compounds and it uses a high resolution capillary GC
extract may thus be analyzed more than once if the number of column with low resolution mass spectrometry. Samples are
samples within a batch requires more than 12 h of analyses. extracted and concentrated by several methods that vary
depending on the matrix involved. The organic extracts are
At the beginning of each 12-h period during which samples cleaned-up by washing with aqueous basic and acid solutions
are to be analyzed, an aliquot of the 1) GC column performance and then separated into fractions using a column of neutral
check solution and 2) a high-resolution concentration calibra- alumina. The fraction containing the PCDDs and PCDFs is
tion must be analyzed to demonstrate adequate GC resolution then further cleaned-up using a column of activated carbon.
and sensitivity, response factor reproducibility, and mass range The final extract is concentrated and Carbon-13 labeled inter-
calibration, and to establish the PCDD/PCDF retention time nal standards are added prior to analysis by GC/MS using a
windows. A mass resolution check must also be performed to capillary GC column and selected ion monitoring using five
demonstrate adequate mass resolution using an appropriate sets of ions that are detailed in the method. Certain 2,3,7,8-
reference compound (perfluorokerosene (PFK) is recom- substituted congeners are used to provide calibration and
mended). If the required criteria are not met, remedial action method recovery information. Proper column selection and
must be taken before any samples are analyzed. access to reference isomer standards, may in certain cases, pro-
Routine or continuing calibration (using a high resolution cal-
ibration solution) and the mass resolution check must also be INTERFERENCES Solvents, reagents, glassware, and other
performed at the end of each 12 h period. Furthermore, a sample processing hardware may yield discrete artifacts and/or
HRGC/HRMS method blank analysis must be recorded follow- elevated baselines which may cause misinterpretation of chro-
ing a calibration analysis and the first sample analysis. matographic data. Use high purity reagents and solvents to
minimize interference problems. Interferents coextracted from
To evaluate the performance of the analytical method, the QC the sample will vary considerably from source to source.
check samples must be handled in exactly the same manner as PCDDs and PCDFs are often associated with other interfering
actual samples. Therefore, 1.0 mL of the QC check sample chlorinated compounds such as PCBs and polychlorinated
concentrate is spiked into each of four 1 L aliquots of reagent diphenyl ethers which may be found at concentrations several
water (which becomes the QC check sample), extracted, and orders of magnitude higher than that of the analytes of interest.
then analyzed by GC. The variety of semivolatile analytes which
may be analyzed by GC is such that the concentration of the INSTRUMENTATION A low resolution GC/MS utilizing 70
QC check sample concentrate is different for the different ana- ev must be capable of selected ion monitoring (SIM) for at
lytical techniques presented in the full method. least 11 ions simultaneously, with a cycle time of 1 second or
less. Minimum integration time for SIM is 50 ms per m/z. Also
The analyst must demonstrate also that the compounds of required is a GC-to-MS interface constructed of all glass or
interest are being quantitatively recovered by the cleanup tech- glass-lined materials. One of the following GC columns is
nique before the cleanup is applied to actual samples. For sam- required:
ple extracts that are cleaned up, the associated quality control
samples (e.g., spikes, blanks, and duplicates) must also be pro- Column 1: 50 m CP-Sil-88 fused silica capillary column.
Column 2: DB-5 (30 m  0.25 mm I.D., 0.25-um film thick-
cessed through the same cleanup procedure. The analysis using
ness) fused silica capillary column.
each determinative method (GC, GC/MS, HPLC) specifies
Column 3: 30 m SP-2250 fused silica capillary column.
instrument calibration procedures using stock standards. It is
recommended that cleanup also be performed on a series of When toluene is employed as the final solvent, use of a bonded
the same type of standards to validate chromatographic elution phase column is recommended. Solvent exchange into tride-
patterns for the compounds of interest and to verify the absence cane is required for other liquid phases or nonbonded columns
of interferences from reagents. such as CP-Sil-88. Chromatographic conditions must be
adjusted to account for solvent boiling points.
846). U.S. EPA. 1983. Method 8290, Rev. 0, Nov. 1990. Office PRECISION & ACCURACY Accuracy, precision, MDLs and
of Solid Wastes, Washington, DC. concentration ranges for the compounds covered by this

method have not been determined or published by EPA yet. Carbon column clean-up — Using a carefully regulated stream
The sensitivity of this method is dependent upon the level of of nitrogen, concentrate the first 8 percent fraction (methylene
interferents within a given matrix. Proposed quantification lev- chloride in hexane) from the alumina column to about 1 mL.
els for target analytes were 2 ppb in soil samples, up to 10 ppb Save this 8 percent concentrate for GC/MS analysis to check
in other solid wastes and 10 ppt in water. Actual values have for breakthrough of PCDDs and PCDFs. Concentrate the sec-
been shown to vary by homologous series and, to a lesser ond 60 percent fraction (methylene chloride in hexane) to
degree, by individual isomer. about 2 to 3 mL. Prepare a carbon column and rinse the carbon
with 5 mL cyclohexane/methylene chloride (50:50 v/v) in the
SAMPLE PRESERVATION Samples must be cooled and in the direction of forward flow, elute the PCDD/PCDF frac-
stored at 4C. tion with 20 mL toluene. Evaporate the toluene fraction to
about 1 mL on a rotary evaporator and transfer this concen-
SAMPLE PREPARATION relative concentration of target analytes but it is typically
Soil samples — Extract 20 g of a 1:1 soil and anhydrous sodium 100 L for soil samples and 500 L for sludge, still bottom, and
sulfate mixture with 1:4 methanol-petroleum ether for 2 h in fl ash samples. Extracts which are determined to be outside
a wrist-action shaker. Concentrate the extract in a K-D and the calibration range for individual analytes must be diluted or
then exchange the solvent with hexane in the K-D. The final a smaller portion of the sample must be re-extracted.
Aqueous samples — Extract a 1 L sample with methylene chlo- 1 mL HPLC injector loop. The injector loop is connected to
ride, dry it with anhydrous sodium sulfate and concentrate it the optional HPLC column.
15 mL of hexane.
Alumina column clean-up — The clean-up procedure the internal standards. For water samples, 1 L of deionized
described below consists of two phases. The first phase involves and/or distilled water should be used as the method blank.
a sequential basic and acid washing of the extract that contains Mineral oil may be used as the method blank for other matrices.
the analytes.
Wash the 15 mL hexane extract with 20% potassium hydroxide standards. Add a recovery standard to the samples prior to
in a separatory funnel. Repeat the washing until no color is injection. The concentration of the recovery standard in the
visible in the bottom layer but no more than four times because sample extract must be the same as that in the calibration
strong base is known to degrade certain PCDDs/PCDFs, so standards used to measure the response factors.
ples and standards.
1 neutral alumina column. Elute the column with 10 mL of 8
percent (v/v) methylene chloride in hexane. Check by GC/MS Retention times of target analytes must be verified using refer-
analysis that no PCDDs of PCDFs are elute in this fraction ence standards. These values must correspond to the retention
before discarding it. Elute the PCDDs and PCDFs from the time windows established. While certain cleanup techniques
column with 15 mL of 60 percent (v/v) methylene chloride in are provided as part of this method, unique samples may
hexane and collect this second fraction in a conical shaped require additional cleanup techniques to achieve the method
concentrator tube. detection limit.

1,2,3,4,6,7,8-HpCDF EPA Method 8290 times the upper method calibration limits must be analyzed by
CAS #67562-39-4 a protocol designed for such concentration levels, e.g., EPA
Method 8280.
TITLE Polychlorinated Dibenzodioxins (PCDDs) and Poly-
water separator until all the water is removed. Filter the toluene
MATRIX This method is applicable with a variety of envi- extract through a glass fiber filter, or equivalent, and concen-
ronmental matrices including: water, soil, sediment, paper trate it to near dryness either on a rotary evaporator using an
pulp, fl ash, fish tissue, human adipose tissue, sludges, fuel oil, inert gas. Transfer the concentrate to a separatory funnel using
chemical reactor residue, and still bottoms. hexane and wash it with 5% sodium chloride solution. Proceed
the detection and quantitative measurement of polychlorinated Soil/sediment — If the sample is wet, add anhydrous powdered
dibenzo-p-dioxins (tetra- through octachlorinated homo- sodium sulfate to it until a free flowing mixture is obtained.
logues; PCDDs), and polychlorinated dibenzofurans (tetra- Place the soil/sodium sulfate mixture in the Soxhlet apparatus,
through octachlorinated homologues; PCDFs) in a variety of add toluene, and reflux for 16 h. The solvent must cycle com-
environmental matrices and at part-per-trillion (ppt) to part- pletely through the system five times per h. Cool and filter the
per-quadrillion (ppq) concentrations. High-resolution gas extract through a glass fiber filter and concentrate to near dry-
chromatography and high-resolution mass spectrometry ness on a rotary evaporator. Transfer the residue to a separatory
(HRGC/HRMS) on purified sample extracts provides highly funnel, using hexane. Proceed to clean up.
specific identification of each analyte. Quantification is pro-
Aqueous samples — Use a 1-L sample; the method may require
vided using calibration standards.
acetone to be added to it. When the sample is judged to contain
INTERFERENCES Solvents, reagents, glassware, and other 1% or more solids, it must be filtered through a glass fiber filter
sample processing hardware may yield discrete artifacts that that has been rinsed with toluene. If the suspended solids con-
may cause misinterpretation of the chromatographic data. tent is too great to filter, centrifuge the sample, decant, and
Analysts should avoid using PVC gloves. Interferants coex- then filter the aqueous phase. Combine the solids from the
tracted from the sample will vary considerably from matrix to centrifuge bottle(s) with the particulates on the filter and with
matrix. PCDDs and PCDFs are often associated with other the filter itself and proceed with Soxhlet extraction for soil/sed-
interfering chlorinated substances such as polychlorinated iment. Extract the aqueous filtrate with methylene chloride in
biphenyls (PCBs), polychlorinated diphenyl ethers (PCDEs), a separatory funnel, filter the extract through anhydrous
polychlorinated naphthalenes, and polychlorinated alkyldiben- sodium sulfate, and concentrate it using a K-D apparatus or a
zofurans that may be found at concentrations several orders of rotary evaporator. Exchange the solvent with hexane and pro-
magnitude higher than the PCDDs or PCDFs. ceed to clean up.
A high-resolution capillary column is used in this method. Clean up — The sample extract is cleaned up utilizing a num-
However, no single column is known to resolve all isomers. The ber of different techniques. Partition cleanup is where the sam-
60 m DB-5 GC column is capable of 2,3,7,8-TCDD isomer ple extract is partitioned with concentrated sulfuric acid, 5%
specificity. In order to determine the concentration of the aqueous sodium chloride, and 20% aqueous potassium
2,3,7,8-TCDD (if detected on the DB-5 column), the sample hydroxide. Silica/alumina column cleanup involves packing
extract must be reanalyzed on a column capable of gravity columns with silica gel and alumina and sequentially
2,3,7,8-TCDF isomer specificity (e.g., DB-225, SP-2330, SP- eluting the residue from the partition cleanup. Carbon column
2331, or equivalent). cleanup involves packing a column with a mixture of AX–21
INSTRUMENTATION High-Resolution Gas Chromato- from the silica/alumina cleanup with hexane, cyclohex-
graph/High-Resolution Mass Spectrometer/Data System ane/methylene chloride (50:50), and methylene chloride/meth-
(HRGC/HRMS/DS) equipped with a GC injection port anol/toluene (75:20:5). Then the column is turned upside
designed so that the separation of 2,3,7,8-TCDD from the other down and the PCDD/PCDF fraction is eluted with toluene.
TCDD isomers achieved in the gas chromatographic column The toluene fraction is concentrated and stored in the dark at
is not appreciably degraded. room temperature until analysis.
Column 1: 60 m DB-5 fused silica capillary column. QUALITY CONTROL Demonstrate, through the analysis of
Column 2: 30 m DB-225 fused silica capillary column, or a reagent water blank, that interferences from the analytical
equivalent. system, glassware, and reagents are under control. For each

analytical batch (up to 20 samples), a reagent blank, matrix
1,2,3,4,7,8,9-HpCDF EPA Method 8290
spike, and matrix spike duplicate/duplicate must be analyzed CAS #55673-89-7
itoring programs). The blank and spiked samples must be car- TITLE Polychlorinated Dibenzodioxins (PCDDs) and Poly-
ried through all stages of the sample preparation and chlorinated Dibenzofurans (PCDFs) by High-Resolution Gas
measurement steps. Chromatography/High-Resolution Mass Spectrometry
(HRGC/HRMS).
A GC column performance check is required at the beginning
of each 12-h period during which samples are analyzed. An MATRIX This method is applicable with a variety of envi-
HRGC/HRMS method blank run is required between a cali- ronmental matrices including: water, soil, sediment, paper
bration run and the first sample run. The same method blank pulp, fl ash, fish tissue, human adipose tissue, sludges, fuel oil,
extract may thus be analyzed more than once if the number of chemical reactor residue, and still bottoms.
samples within a batch requires more than 12 h of analyses. METHOD SUMMARY This method provides procedures for
At the beginning of each 12-h period during which samples
dibenzo-p-dioxins (tetra- through octachlorinated homo-
are to be analyzed, an aliquot of the 1) GC column performance logues; PCDDs), and polychlorinated dibenzofurans (tetra-
check solution and 2) a high-resolution concentration calibra- through octachlorinated homologues; PCDFs) in a variety of
tion must be analyzed to demonstrate adequate GC resolution environmental matrices and at part-per-trillion (ppt) to part-
and sensitivity, response factor reproducibility, and mass range per-quadrillion (ppq) concentrations. High-resolution gas
calibration, and to establish the PCDD/PCDF retention time chromatography and high-resolution mass spectrometry
windows. A mass resolution check must also be performed to (HRGC/HRMS) on purified sample extracts provides highly
demonstrate adequate mass resolution using an appropriate specific identification of each analyte. Quantification is pro-
reference compound (perfluorokerosene (PFK) is recom- vided using calibration standards.
mended). If the required criteria are not met, remedial action INTERFERENCES Solvents, reagents, glassware, and other
must be taken before any samples are analyzed. sample processing hardware may yield discrete artifacts that
may cause misinterpretation of the chromatographic data.
Analysts should avoid using PVC gloves. Interferants coex-
ibration solution) and the mass resolution check must also be tracted from the sample will vary considerably from matrix to
performed at the end of each 12 h period. Furthermore, a matrix. PCDDs and PCDFs are often associated with other
HRGC/HRMS method blank analysis must be recorded follow- interfering chlorinated substances such as polychlorinated
ing a calibration analysis and the first sample analysis. biphenyls (PCBs), polychlorinated diphenyl ethers (PCDEs),
To evaluate the performance of the analytical method, the QC polychlorinated naphthalenes, and polychlorinated alkyldiben-
zofurans that may be found at concentrations several orders of
check samples must be handled in exactly the same manner as
magnitude higher than the PCDDs or PCDFs.
actual samples. Therefore, 1.0 mL of the QC check sample
concentrate is spiked into each of four 1 L aliquots of reagent A high-resolution capillary column is used in this method.
water (which becomes the QC check sample), extracted, and However, no single column is known to resolve all isomers. The
then analyzed by GC. The variety of semivolatile analytes which 60 m DB-5 GC column is capable of 2,3,7,8-TCDD isomer
may be analyzed by GC is such that the concentration of the specificity. In order to determine the concentration of the
2,3,7,8-TCDD (if detected on the DB-5 column), the sample
QC check sample concentrate is different for the different ana-
extract must be reanalyzed on a column capable of
lytical techniques presented in the full method. 2,3,7,8-TCDF isomer specificity (e.g., DB-225, SP-2330, SP-
The analyst must demonstrate also that the compounds of 2331, or equivalent).
interest are being quantitatively recovered by the cleanup tech- INSTRUMENTATION High-Resolution Gas Chromato-
nique before the cleanup is applied to actual samples. For sam- graph/High-Resolution Mass Spectrometer/Data System
ple extracts that are cleaned up, the associated quality control (HRGC/HRMS/DS) equipped with a GC injection port
samples (e.g., spikes, blanks, and duplicates) must also be pro- designed so that the separation of 2,3,7,8-TCDD from the other
cessed through the same cleanup procedure. The analysis using TCDD isomers achieved in the gas chromatographic column
each determinative method (GC, GC/MS, HPLC) specifies is not appreciably degraded.
instrument calibration procedures using stock standards. It is Column 1: 60 m DB-5 fused silica capillary column.
recommended that cleanup also be performed on a series of Column 2: 30 m DB-225 fused silica capillary column, or
the same type of standards to validate chromatographic elution equivalent.
patterns for the compounds of interest and to verify the absence
PRECISION & ACCURACY Precision, bias and concentra-
of interferences from reagents. tion ranges for the compounds covered by this method have
REFERENCE Test Methods for Evaluating Solid Waste (SW- not been determined yet. The sensitivity of Method 8290 is
846). U.S. EPA. 1983. Method 8290, Rev. 0, Nov. 1990. Office dependent upon the level of interferences within a given matrix.
of Solid Wastes, Washington, DC. Samples containing concentrations of specific congeneric

analytes of PCDDs and PCDFs that are greater than ten times ried through all stages of the sample preparation and
the upper method calibration limits must be analyzed by a measurement steps.
protocol designed for such concentration levels, e.g., EPA
Method 8280.
SAMPLE PREPARATION HRGC/HRMS method blank run is required between a cali-
Sludge/wet fuel oil — Extract aqueous sludge or wet fuel oil bration run and the first sample run. The same method blank
samples by refluxing a sample with toluene using a Dean-Stark extract may thus be analyzed more than once if the number of
water separator until all the water is removed. Filter the toluene samples within a batch requires more than 12 h of analyses.
extract through a glass fiber filter, or equivalent, and concen-
trate it to near dryness either on a rotary evaporator using an
are to be analyzed, an aliquot of the 1) GC column performance
inert gas. Transfer the concentrate to a separatory funnel using
check solution and 2) a high-resolution concentration calibra-
tion must be analyzed to demonstrate adequate GC resolution
to clean up.
and sensitivity, response factor reproducibility, and mass range
Soil/sediment — If the sample is wet, add anhydrous powdered calibration, and to establish the PCDD/PCDF retention time
sodium sulfate to it until a free flowing mixture is obtained. windows. A mass resolution check must also be performed to
Place the soil/sodium sulfate mixture in the Soxhlet apparatus, demonstrate adequate mass resolution using an appropriate
add toluene, and reflux for 16 h. The solvent must cycle com- reference compound (perfluorokerosene (PFK) is recom-
pletely through the system five times per h. Cool and filter the mended). If the required criteria are not met, remedial action
extract through a glass fiber filter and concentrate to near dry- must be taken before any samples are analyzed.
ness on a rotary evaporator. Transfer the residue to a separatory
funnel, using hexane. Proceed to clean up.
ibration solution) and the mass resolution check must also be
Aqueous samples — Use a 1-L sample; the method may require performed at the end of each 12 h period. Furthermore, a
acetone to be added to it. When the sample is judged to contain HRGC/HRMS method blank analysis must be recorded follow-
1% or more solids, it must be filtered through a glass fiber filter ing a calibration analysis and the first sample analysis.
that has been rinsed with toluene. If the suspended solids con-
To evaluate the performance of the analytical method, the QC
tent is too great to filter, centrifuge the sample, decant, and
then filter the aqueous phase. Combine the solids from the
centrifuge bottle(s) with the particulates on the filter and with
concentrate is spiked into each of four 1 L aliquots of reagent
the filter itself and proceed with Soxhlet extraction for soil/sed-
water (which becomes the QC check sample), extracted, and
iment. Extract the aqueous filtrate with methylene chloride in
a separatory funnel, filter the extract through anhydrous
may be analyzed by GC is such that the concentration of the
sodium sulfate, and concentrate it using a K-D apparatus or a
rotary evaporator. Exchange the solvent with hexane and pro-
lytical techniques presented in the full method.
ceed to clean up.
The analyst must demonstrate also that the compounds of
Clean up — The sample extract is cleaned up utilizing a num-
interest are being quantitatively recovered by the cleanup tech-
ber of different techniques. Partition cleanup is where the sam-
nique before the cleanup is applied to actual samples. For sam-
ple extract is partitioned with concentrated sulfuric acid, 5%
aqueous sodium chloride, and 20% aqueous potassium
samples (e.g., spikes, blanks, and duplicates) must also be pro-
hydroxide. Silica/alumina column cleanup involves packing
gravity columns with silica gel and alumina and sequentially
eluting the residue from the partition cleanup. Carbon column
recommended that cleanup also be performed on a series of
the same type of standards to validate chromatographic elution
of interferences from reagents.
down and the PCDD/PCDF fraction is eluted with toluene. REFERENCE Test Methods for Evaluating Solid Waste (SW-
The toluene fraction is concentrated and stored in the dark at 846). U.S. EPA. 1983. Method 8290, Rev. 0, Nov. 1990. Office
room temperature until analysis. of Solid Wastes, Washington, DC.
system, glassware, and reagents are under control. For each 1,2,3,4,7,8-HxCDD EPA Method 8280
analytical batch (up to 20 samples), a reagent blank, matrix CAS #57653-85-7
spike, and matrix spike duplicate/duplicate must be analyzed
(the frequency of the spikes may be different for different mon- TITLE The Analysis of Polychlorinated Dibenzo-P-Dioxins
itoring programs). The blank and spiked samples must be car- and Polychlorinated Dibenzofurans.

MATRIX This method is appropriate for the determination been shown to vary by homologous series and, to a lesser
of tetra-, penta-, hexa-, hepta-, and octachlorinated dibenzo- degree, by individual isomer.
p-dioxins (PCDDs) and dibenzofurans (PCDFs) in chemical
wastes including still bottoms, fuel oils, sludges, fl ash, reactor
residues, soil and water. lined screw-caps that have been acid-washed and solvent rinsed
METHOD SUMMARY This method covers 22 PCDD and before use. If compositing equipment is used, the system must
PCDF compounds and it uses a high resolution capillary GC incorporate glass sample containers for the collection of a min-
column with low resolution mass spectrometry. Samples are imum of 250 mL. samples.
extracted and concentrated by several methods that vary SAMPLE PRESERVATION Samples must be cooled and
depending on the matrix involved. The organic extracts are stored at 4C.
and then separated into fractions using a column of neutral MHT Samples must be extracted within 30 days and analyzed
alumina. The fraction containing the PCDDs and PCDFs is within 45 days of collection.
then further cleaned-up using a column of activated carbon. SAMPLE PREPARATION
The final extract is concentrated and Carbon-13 labeled inter- Soil samples — Extract 20 g of a 1:1 soil and anhydrous sodium
nal standards are added prior to analysis by GC/MS using a sulfate mixture with 1:4 methanol-petroleum ether for 2 h in
capillary GC column and selected ion monitoring using five a wrist-action shaker. Concentrate the extract in a K-D and
sets of ions that are detailed in the method. Certain 2,3,7,8- then exchange the solvent with hexane in the K-D. The final
substituted congeners are used to provide calibration and volume is 15 mL of hexane.
method recovery information. Proper column selection and
access to reference isomer standards, may in certain cases, pro- Aqueous samples — Extract a 1 L sample with methylene chlo-
ride, dry it with anhydrous sodium sulfate and concentrate it
INTERFERENCES Solvents, reagents, glassware, and other continuous liquid-liquid extractor may be used in place of a
sample processing hardware may yield discrete artifacts and/or separatory funnel to avoid emulsions. The final volume is
elevated baselines which may cause misinterpretation of chro- 15 mL of hexane.
matographic data. Use high purity reagents and solvents to
Alumina column clean-up — The clean-up procedure
minimize interference problems. Interferents coextracted from
described below consists of two phases. The first phase involves
the sample will vary considerably from source to source.
a sequential basic and acid washing of the extract that contains
PCDDs and PCDFs are often associated with other interfering the analytes.
chlorinated compounds such as PCBs and polychlorinated
diphenyl ethers which may be found at concentrations several Wash the 15 mL hexane extract with 20% potassium hydroxide
orders of magnitude higher than that of the analytes of interest. in a separatory funnel. Repeat the washing until no color is
visible in the bottom layer but no more than four times because
INSTRUMENTATION A low resolution GC/MS utilizing 70 strong base is known to degrade certain PCDDs/PCDFs, so
ev must be capable of selected ion monitoring (SIM) for at contact time must be minimized. Next, partition the 15 mL
least 11 ions simultaneously, with a cycle time of 1 second or hexane against 40 mL of 5% sodium chloride. Next, partition
less. Minimum integration time for SIM is 50 ms per m/z. Also the 15 mL hexane against 40 mL of concentrated sulfuric acid.
required is a GC-to-MS interface constructed of all glass or Repeat the acid washings until no color is visible in the acid
glass-lined materials. One of the following GC columns is layer (but no more than four times). Finally, partition the
required: 15 mL hexane against 40 mL of 5% sodium chloride. Dry the
Column 1: 50 m CP-Sil-88 fused silica capillary column. organic layer with anhydrous sodium sulfate and concentrate
Column 2: DB-5 (30 m  0.25 mm I.D., 0.25-um film thick- it to near dryness with a rotary evaporator. Dissolve the hexane
ness) fused silica capillary column. residue from the first phase of the clean-up in 2 mL of hexane
Column 3: 30 m SP-2250 fused silica capillary column. and apply it carefully to the top of a pre-eluted Woelm super
When toluene is employed as the final solvent, use of a bonded percent (v/v) methylene chloride in hexane. Check by GC/MS
phase column is recommended. Solvent exchange into tride- analysis that no PCDDs of PCDFs are elute in this fraction
cane is required for other liquid phases or nonbonded columns before discarding it. Elute the PCDDs and PCDFs from the
concentrator tube.

about 2 to 3 mL. Prepare a carbon column and rinse the carbon
1,2,3,6,7,8-HxCDD EPA Method 8280
with 5 mL cyclohexane/methylene chloride (50:50 v/v) in the CAS #34465-46-8
flow. While still in the reverse direction of flow, transfer the TITLE The Analysis of Polychlorinated Dibenzo-P-Dioxins
sample concentrate to the column and elute with 10 mL of and Polychlorinated Dibenzofurans.
MATRIX This method is appropriate for the determination
of tetra-, penta-, hexa-, hepta-, and octachlorinated dibenzo-
a check on column efficiency). Next, turn the column over and, p-dioxins (PCDDs) and dibenzofurans (PCDFs) in chemical
in the direction of forward flow, elute the PCDD/PCDF frac- wastes including still bottoms, fuel oils, sludges, fl ash, reactor
tion with 20 mL toluene. Evaporate the toluene fraction to residues, soil and water.
METHOD SUMMARY This method covers 22 PCDD and
PCDF compounds and it uses a high resolution capillary GC
column with low resolution mass spectrometry. Samples are
relative concentration of target analytes but it is typically extracted and concentrated by several methods that vary
100 L for soil samples and 500 L for sludge, still bottom, and depending on the matrix involved. The organic extracts are
fl ash samples. Extracts which are determined to be outside cleaned-up by washing with aqueous basic and acid solutions
the calibration range for individual analytes must be diluted or and then separated into fractions using a column of neutral
a smaller portion of the sample must be re-extracted. alumina. The fraction containing the PCDDs and PCDFs is
then further cleaned-up using a column of activated carbon.
An alternate carbon column clean-up also may be used with a The final extract is concentrated and Carbon-13 labeled inter-
1 mL HPLC injector loop. The injector loop is connected to nal standards are added prior to analysis by GC/MS using a
the optional HPLC column. capillary GC column and selected ion monitoring using five
QUALITY CONTROL Demonstrate, using a method blank, sets of ions that are detailed in the method. Certain 2,3,7,8-
substituted congeners are used to provide calibration and
method recovery information. Proper column selection and
access to reference isomer standards, may in certain cases, pro-
each 20 or fewer samples. The method blank is also dosed with vide isomer specific data.
the internal standards. For water samples, 1 L of deionized
and/or distilled water should be used as the method blank. INTERFERENCES Solvents, reagents, glassware, and other
Mineral oil may be used as the method blank for other matrices. sample processing hardware may yield discrete artifacts and/or
elevated baselines which may cause misinterpretation of chro-
Calculate response factors for standards relative to the internal matographic data. Use high purity reagents and solvents to
standards. Add a recovery standard to the samples prior to minimize interference problems. Interferents coextracted from
injection. The concentration of the recovery standard in the the sample will vary considerably from source to source.
sample extract must be the same as that in the calibration PCDDs and PCDFs are often associated with other interfering
standards used to measure the response factors. chlorinated compounds such as PCBs and polychlorinated
diphenyl ethers which may be found at concentrations several
Field duplicates (individual samples taken from the same loca- orders of magnitude higher than that of the analytes of interest.
INSTRUMENTATION A low resolution GC/MS utilizing 70
ev must be capable of selected ion monitoring (SIM) for at
field blanks should be provided to monitor for possible cross- least 11 ions simultaneously, with a cycle time of 1 second or
contamination of samples in the field. GC column performance less. Minimum integration time for SIM is 50 ms per m/z. Also
must be demonstrated initially and verified prior to analyzing required is a GC-to-MS interface constructed of all glass or
any sample in a 12-hr period. The GC column performance glass-lined materials. One of the following GC columns is
check solution must be analyzed under the same chromato- required:
Column 1: 50 m CP-Sil-88 fused silica capillary column.
ples and standards. Column 2: DB-5 (30 m  0.25 mm I.D., 0.25-um film thick-
Retention times of target analytes must be verified using refer- ness) fused silica capillary column.
ence standards. These values must correspond to the retention Column 3: 30 m SP-2250 fused silica capillary column.
time windows established. While certain cleanup techniques When toluene is employed as the final solvent, use of a bonded
are provided as part of this method, unique samples may phase column is recommended. Solvent exchange into tride-
require additional cleanup techniques to achieve the method cane is required for other liquid phases or nonbonded columns
detection limit. such as CP-Sil-88. Chromatographic conditions must be
adjusted to account for solvent boiling points.
846). U.S.E.P.A., 1986. Method 8280, Rev. 0, Sept. 1986. Office PRECISION & ACCURACY Accuracy, precision, MDLs and
of Solid Wastes, Washington, DC. concentration ranges for the compounds covered by this

method have not been determined or published by EPA yet. Carbon column clean-up — Using a carefully regulated stream
The sensitivity of this method is dependent upon the level of of nitrogen, concentrate the first 8 percent fraction (methylene
interferents within a given matrix. Proposed quantification lev- chloride in hexane) from the alumina column to about 1 mL.
els for target analytes were 2 ppb in soil samples, up to 10 ppb Save this 8 percent concentrate for GC/MS analysis to check
in other solid wastes and 10 ppt in water. Actual values have for breakthrough of PCDDs and PCDFs. Concentrate the sec-
been shown to vary by homologous series and, to a lesser ond 60 percent fraction (methylene chloride in hexane) to
degree, by individual isomer. about 2 to 3 mL. Prepare a carbon column and rinse the carbon
with 5 mL cyclohexane/methylene chloride (50:50 v/v) in the
SAMPLE PRESERVATION Samples must be cooled and in the direction of forward flow, elute the PCDD/PCDF frac-
stored at 4C. tion with 20 mL toluene. Evaporate the toluene fraction to
SAMPLE PREPARATION relative concentration of target analytes but it is typically
Soil samples — Extract 20 g of a 1:1 soil and anhydrous sodium 100 L for soil samples and 500 L for sludge, still bottom, and
sulfate mixture with 1:4 methanol-petroleum ether for 2 h in fl ash samples. Extracts which are determined to be outside
a wrist-action shaker. Concentrate the extract in a K-D and the calibration range for individual analytes must be diluted or
then exchange the solvent with hexane in the K-D. The final a smaller portion of the sample must be re-extracted.
Aqueous samples — Extract a 1 L sample with methylene chlo- 1 mL HPLC injector loop. The injector loop is connected to
ride, dry it with anhydrous sodium sulfate and concentrate it the optional HPLC column.
15 mL of hexane.
Alumina column clean-up — The clean-up procedure the internal standards. For water samples, 1 L of deionized
described below consists of two phases. The first phase involves and/or distilled water should be used as the method blank.
a sequential basic and acid washing of the extract that contains Mineral oil may be used as the method blank for other matrices.
the analytes.
Wash the 15 mL hexane extract with 20% potassium hydroxide standards. Add a recovery standard to the samples prior to
in a separatory funnel. Repeat the washing until no color is injection. The concentration of the recovery standard in the
visible in the bottom layer but no more than four times because sample extract must be the same as that in the calibration
strong base is known to degrade certain PCDDs/PCDFs, so standards used to measure the response factors.
ples and standards.
percent (v/v) methylene chloride in hexane. Check by GC/MS Retention times of target analytes must be verified using refer-
analysis that no PCDDs of PCDFs are elute in this fraction ence standards. These values must correspond to the retention
before discarding it. Elute the PCDDs and PCDFs from the time windows established. While certain cleanup techniques
column with 15 mL of 60 percent (v/v) methylene chloride in are provided as part of this method, unique samples may
hexane and collect this second fraction in a conical shaped require additional cleanup techniques to achieve the method
concentrator tube. detection limit.

1,2,3,4,7,8-HxCDD EPA Method 8290 times the upper method calibration limits must be analyzed by
Method 8280.

1,2,3,6,7,8-HxCDD EPA Method 8290
(HRGC/HRMS).

Method 8280.
trate it to near dryness either on a rotary evaporator using an
are to be analyzed, an aliquot of the 1) GC column performance
to clean up.
funnel, using hexane. Proceed to clean up.
To evaluate the performance of the analytical method, the QC
tent is too great to filter, centrifuge the sample, decant, and
then filter the aqueous phase. Combine the solids from the
centrifuge bottle(s) with the particulates on the filter and with
concentrate is spiked into each of four 1 L aliquots of reagent
the filter itself and proceed with Soxhlet extraction for soil/sed-
water (which becomes the QC check sample), extracted, and
iment. Extract the aqueous filtrate with methylene chloride in
a separatory funnel, filter the extract through anhydrous
may be analyzed by GC is such that the concentration of the
sodium sulfate, and concentrate it using a K-D apparatus or a
rotary evaporator. Exchange the solvent with hexane and pro-
lytical techniques presented in the full method.
ceed to clean up.
The analyst must demonstrate also that the compounds of
Clean up — The sample extract is cleaned up utilizing a num-
interest are being quantitatively recovered by the cleanup tech-
ber of different techniques. Partition cleanup is where the sam-
nique before the cleanup is applied to actual samples. For sam-
ple extract is partitioned with concentrated sulfuric acid, 5%
aqueous sodium chloride, and 20% aqueous potassium
samples (e.g., spikes, blanks, and duplicates) must also be pro-
hydroxide. Silica/alumina column cleanup involves packing
gravity columns with silica gel and alumina and sequentially
eluting the residue from the partition cleanup. Carbon column
recommended that cleanup also be performed on a series of
the same type of standards to validate chromatographic elution
down and the PCDD/PCDF fraction is eluted with toluene. REFERENCE Test Methods for Evaluating Solid Waste (SW-
The toluene fraction is concentrated and stored in the dark at 846). U.S. EPA. 1983. Method 8290, Rev. 0, Nov. 1990. Office
room temperature until analysis. of Solid Wastes, Washington, DC.
system, glassware, and reagents are under control. For each 1,2,3,7,8,9-HxCDD EPA Method 8290
analytical batch (up to 20 samples), a reagent blank, matrix CAS #19408-74-3
(the frequency of the spikes may be different for different mon- TITLE Polychlorinated Dibenzodioxins (PCDDs) and Poly-
itoring programs). The blank and spiked samples must be car- chlorinated Dibenzofurans (PCDFs) by High-Resolution Gas

Chromatography/High-Resolution Mass Spectrometry SAMPLE PREPARATION
(HRGC/HRMS). Sludge/wet fuel oil — Extract aqueous sludge or wet fuel oil
samples by refluxing a sample with toluene using a Dean-Stark
MATRIX This method is applicable with a variety of envi-
ronmental matrices including: water, soil, sediment, paper extract through a glass fiber filter, or equivalent, and concen-
pulp, fl ash, fish tissue, human adipose tissue, sludges, fuel oil, trate it to near dryness either on a rotary evaporator using an
chemical reactor residue, and still bottoms. inert gas. Transfer the concentrate to a separatory funnel using
METHOD SUMMARY This method provides procedures for hexane and wash it with 5% sodium chloride solution. Proceed
the detection and quantitative measurement of polychlorinated to clean up.
dibenzo-p-dioxins (tetra- through octachlorinated homo- Soil/sediment — If the sample is wet, add anhydrous powdered
logues; PCDDs), and polychlorinated dibenzofurans (tetra- sodium sulfate to it until a free flowing mixture is obtained.
through octachlorinated homologues; PCDFs) in a variety of Place the soil/sodium sulfate mixture in the Soxhlet apparatus,
environmental matrices and at part-per-trillion (ppt) to part- add toluene, and reflux for 16 h. The solvent must cycle com-
per-quadrillion (ppq) concentrations. High-resolution gas pletely through the system five times per h. Cool and filter the
chromatography and high-resolution mass spectrometry extract through a glass fiber filter and concentrate to near dry-
(HRGC/HRMS) on purified sample extracts provides highly ness on a rotary evaporator. Transfer the residue to a separatory
specific identification of each analyte. Quantification is pro- funnel, using hexane. Proceed to clean up.
INTERFERENCES Solvents, reagents, glassware, and other acetone to be added to it. When the sample is judged to contain
sample processing hardware may yield discrete artifacts that 1% or more solids, it must be filtered through a glass fiber filter
may cause misinterpretation of the chromatographic data. that has been rinsed with toluene. If the suspended solids con-
Analysts should avoid using PVC gloves. Interferants coex- tent is too great to filter, centrifuge the sample, decant, and
tracted from the sample will vary considerably from matrix to then filter the aqueous phase. Combine the solids from the
matrix. PCDDs and PCDFs are often associated with other centrifuge bottle(s) with the particulates on the filter and with
interfering chlorinated substances such as polychlorinated the filter itself and proceed with Soxhlet extraction for soil/sed-
biphenyls (PCBs), polychlorinated diphenyl ethers (PCDEs), iment. Extract the aqueous filtrate with methylene chloride in
polychlorinated naphthalenes, and polychlorinated alkyldiben- a separatory funnel, filter the extract through anhydrous
zofurans that may be found at concentrations several orders of sodium sulfate, and concentrate it using a K-D apparatus or a
magnitude higher than the PCDDs or PCDFs. rotary evaporator. Exchange the solvent with hexane and pro-
ceed to clean up.
A high-resolution capillary column is used in this method.
However, no single column is known to resolve all isomers. The Clean up — The sample extract is cleaned up utilizing a num-
60 m DB-5 GC column is capable of 2,3,7,8-TCDD isomer ber of different techniques. Partition cleanup is where the sam-
specificity. In order to determine the concentration of the ple extract is partitioned with concentrated sulfuric acid, 5%
2,3,7,8-TCDD (if detected on the DB-5 column), the sample aqueous sodium chloride, and 20% aqueous potassium
extract must be reanalyzed on a column capable of hydroxide. Silica/alumina column cleanup involves packing
2,3,7,8-TCDF isomer specificity (e.g., DB-225, SP-2330, SP- gravity columns with silica gel and alumina and sequentially
2331, or equivalent). eluting the residue from the partition cleanup. Carbon column
INSTRUMENTATION High-Resolution Gas Chromato- and Celite 545 and sequentially eluting the sample concentrate
graph/High-Resolution Mass Spectrometer/Data System from the silica/alumina cleanup with hexane, cyclohex-
(HRGC/HRMS/DS) equipped with a GC injection port ane/methylene chloride (50:50), and methylene chloride/meth-
designed so that the separation of 2,3,7,8-TCDD from the other anol/toluene (75:20:5). Then the column is turned upside
TCDD isomers achieved in the gas chromatographic column down and the PCDD/PCDF fraction is eluted with toluene.
is not appreciably degraded. The toluene fraction is concentrated and stored in the dark at
Column 1: 60 m DB-5 fused silica capillary column. room temperature until analysis.
Column 2: 30 m DB-225 fused silica capillary column, or QUALITY CONTROL Demonstrate, through the analysis of
equivalent. a reagent water blank, that interferences from the analytical
PRECISION & ACCURACY Precision, bias and concentra- system, glassware, and reagents are under control. For each
tion ranges for the compounds covered by this method have analytical batch (up to 20 samples), a reagent blank, matrix
not been determined yet. The sensitivity of Method 8290 is spike, and matrix spike duplicate/duplicate must be analyzed
itoring programs). The blank and spiked samples must be car-
ried through all stages of the sample preparation and
measurement steps.
times the upper method calibration limits must be analyzed by
a protocol designed for such concentration levels, e.g., EPA A GC column performance check is required at the beginning
Method 8280. of each 12-h period during which samples are analyzed. An

HRGC/HRMS method blank run is required between a cali- method is dependent on the level of interferents within the
bration run and the first sample run. The same method blank matrix. Only experienced analysts should be used. Special
extract may thus be analyzed more than once if the number of safety precautions must be observed and an EPA-approved
samples within a batch requires more than 12 h of analyses. sample disposal plan must be used.
At the beginning of each 12-h period during which samples INTERFERENCES Solvents, reagents, and glassware may
are to be analyzed, an aliquot of the 1) GC column performance introduce artifacts. Other interferences may come from coex-
check solution and 2) a high-resolution concentration calibra- tracted compounds from samples; PCBs and polychlorinated
tion must be analyzed to demonstrate adequate GC resolution diphenyl ethers are common interferents.
INSTRUMENTATION GC/MS with a fused silica capillary
calibration, and to establish the PCDD/PCDF retention time
column. Also, solvent extraction and concentration glassware
windows. A mass resolution check must also be performed to
and either a gravity flow activated carbon AX–21/silica gel Type
demonstrate adequate mass resolution using an appropriate
60 EM reagent column or a HPLC with a 10 mm by 7 cm
reference compound (perfluorokerosene (PFK) is recom-
silanized glass column with active carbon AX–21 and Spher-
mended). If the required criteria are not met, remedial action
isorb S10W silica for sample cleanup. One of three fused silica
must be taken before any samples are analyzed.
capillary GC columns may be used: column 1: 50 m CP-Sil-88;
Routine or continuing calibration (using a high resolution cal- Column 2: 30 m by 0.25 mm DB-5; colunm 3: 30 m SP-2250.
RANGE 50–6,000 picograms.
performed at the end of each 12 h period. Furthermore, a
HRGC/HRMS method blank analysis must be recorded follow- MDL Not determined.
ing a calibration analysis and the first sample analysis.
PRECISION as (RSD) 38% with 5 ng/g in clay; 8.8% with
To evaluate the performance of the analytical method, the QC 25 ng/g soil; 3.4% with 125 ng/g in sludge.
actual samples. Therefore, 1.0 mL of the QC check sample ACCURACY (as Mean % Recovery): 46.8% with 5 ng/g in
concentrate is spiked into each of four 1 L aliquots of reagent clay; 65.0% with 25 ng/g in soil; 81.9% with 125 ng/g in sludge;
water (which becomes the QC check sample), extracted, and 125.4% with 46 ng/g in fl ash; 89.1% with 2500 ng/g in still
then analyzed by GC. The variety of semivolatile analytes which bottom.
may be analyzed by GC is such that the concentration of the SAMPLING METHOD Use 1 L (or quart) amber glass bot-
QC check sample concentrate is different for the different ana- tles with Teflon®-lined or solvent washed foil screw caps. Tape
lytical techniques presented in the full method. caps to bottle after sampling.
The analyst must demonstrate also that the compounds of Compositing equipment must use glass containers and contain
interest are being quantitatively recovered by the cleanup tech- no Tygon or rubber tubing. Sample bottles must not be pre-
nique before the cleanup is applied to actual samples. For sam- washed with the sample before its collection. Aqueous samples
ple extracts that are cleaned up, the associated quality control cannot be aliquoted from sample containers — the entire sam-
samples (e.g., spikes, blanks, and duplicates) must also be pro- ple must be used and the container is washed out with the
cessed through the same cleanup procedure. The analysis using extracting solvent.
instrument calibration procedures using stock standards. It is STABILITY Cool to 4C and store at this temperature. When
recommended that cleanup also be performed on a series of toluene is employed as the final solvent use a bonded phase GC
the same type of standards to validate chromatographic elution column for separation. Otherwise, solvent exchange into tride-
patterns for the compounds of interest and to verify the absence cane is required for other liquid phases or the CP-Sil-88 GC
of interferences from reagents. column.
REFERENCE Test Methods for Evaluating Solid Waste (SW- MHT 30 days; samples must be completely analyzed within
846). U.S. EPA. 1983. Method 8290, Rev. 0, Nov. 1990. Office 45 days of collection.
of Solid Wastes, Washington, DC. QUALITY CONTROL A method blank must be analyzed
each time a set of samples is extracted or there is a change in
reagents. A lab method blank must be run with each analytical
1,2,3,4,7,8-HxCDD EPA Method 8280 batch of 20 or fewer samples. Field duplicates and field blanks
CAS #39227-28-6 should be analyzed periodically. GC column performance must
be demonstrated initially and verified prior to analyzing any
TITLE Analysis of PCDDs and PCDFs sample in a 12 h period. A series of calibration standards must
be processed through the procedure to validate elution patterns
MATRIX chemical wastes, fuel oils, still bottoms, sludges, and absence of interferents from reagents. Both the alumina
water, soil, fl ash, reactor residues. column and carbon column performance must be routinely
APPLICATION This method is used for the analysis of tetra-, checked for presence of the analyte.
penta-, hexa-, hepta-, and octachlorinated dibenzo-p-dioxins Performance evaluation samples and split samples with other
(PCDDs) and dibenzofurans (PCDFs). The sensitivity of the laboratories are also expected to be periodically analyzed.

REFERENCE Method 8280, SW-846, 3rd ed., Nov.1986. QUALITY CONTROL A method blank must be analyzed
each time a set of samples is extracted or there is a change in
reagents. A lab method blank must be run with each analytical
batch of 20 or fewer samples. Field duplicates and field blanks
1,2,3,6,7,8-HxCDD EPA Method 8280 should be analyzed periodically. GC column performance must
CAS #57653-85-7 be demonstrated initially and verified prior to analyzing any
sample in a 12 h period. A series of calibration standards must
TITLE Analysis of PCDDs and PCDFs be processed through the procedure to validate elution patterns
MATRIX chemical wastes, fuel oils, still bottoms, sludges, and absence of interferents from reagents. Both the alumina
water, soil, fl ash, reactor residues. column and carbon column performance must be routinely
checked for presence of the analyte.
APPLICATION This method is used for the analysis of tetra-,
penta-, hexa-, hepta-, and octachlorinated dibenzo-p-dioxins Performance evaluation samples and split samples with other
(PCDDs) and dibenzofurans (PCDFs). The sensitivity of the laboratories are also expected to be periodically analyzed.
method is dependent on the level of interferents within the REFERENCE Method 8280, SW-846, 3rd ed., Nov.1986.
matrix. Only experienced analysts should be used. Special
safety precautions must be observed and an EPA-approved
sample disposal plan must be used.
1,2,3,4,7,8-HxCDF EPA Method 8280
INTERFERENCES Solvents, reagents, and glassware may
CAS #70648-26-9
introduce artifacts. Other interferences may come from coex-
TITLE The Analysis of Polychlorinated Dibenzo-P-Dioxins
PCBs and polychlorinated diphenyl ethers are common inter- and Polychlorinated Dibenzofurans.
ferents. MATRIX This method is appropriate for the determination
INSTRUMENTATION GC/MS with a fused silica capillary of tetra-, penta-, hexa-, hepta-, and octachlorinated dibenzo-
column. Also, solvent extraction and concentration glassware p-dioxins (PCDDs) and dibenzofurans (PCDFs) in chemical
and either a gravity flow activated carbon AX–21/silica gel Type wastes including still bottoms, fuel oils, sludges, fl ash, reactor
60 EM reagent column or a HPLC with a 10 mm by 7 cm residues, soil and water.
silanized glass column with active carbon AX–21 and Spher- METHOD SUMMARY This method covers 22 PCDD and
isorb S10W silica for sample cleanup. One of three fused silica PCDF compounds and it uses a high resolution capillary GC
capillary GC columns may be used: column 1: 50 m CP-Sil-88; column with low resolution mass spectrometry. Samples are
Column 2: 30 m by 0.25 mm DB-5; colunm 3: 30 m SP-2250. extracted and concentrated by several methods that vary
RANGE 50–6,000 picograms. depending on the matrix involved. The organic extracts are
MDL 2.21 ng/L (in reagent water); 1.25 g/kg (in Missouri and then separated into fractions using a column of neutral
soil); 0.55 g/kg (in fl ash); 2.30 g/kg (in industrial sludge); alumina. The fraction containing the PCDDs and PCDFs is
6.21 g/kg (in still bottom); 5.02 g/kg (in fuel oil) MDLs are then further cleaned-up using a column of activated carbon.
for carbon-13 labeled analyte. The final extract is concentrated and Carbon-13 labeled inter-
PRECISION (as RSD) Not determined. nal standards are added prior to analysis by GC/MS using a
capillary GC column and selected ion monitoring using five
ACCURACY (as Mean % Recovery) Not determined. sets of ions that are detailed in the method. Certain 2,3,7,8-
SAMPLING METHOD Use 1 L (or quart) amber glass bot- substituted congeners are used to provide calibration and
tles with Teflon®-lined or solvent washed foil screw caps. Tape method recovery information. Proper column selection and
caps to bottle after sampling. access to reference isomer standards, may in certain cases, pro-
Compositing equipment must use glass containers and contain
no Tygon or rubber tubing. Sample bottles must not be pre- INTERFERENCES Solvents, reagents, glassware, and other
washed with the sample before its collection. Aqueous samples sample processing hardware may yield discrete artifacts and/or
cannot be aliquoted from sample containers — the entire sam- elevated baselines which may cause misinterpretation of chro-
ple must be used and the container is washed out with the matographic data. Use high purity reagents and solvents to
extracting solvent. minimize interference problems. Interferents coextracted from
the sample will vary considerably from source to source.
STABILITY Cool to 4C and store at this temperature. When PCDDs and PCDFs are often associated with other interfering
toluene is employed as the final solvent use a bonded phase GC chlorinated compounds such as PCBs and polychlorinated
column for separation. Otherwise, solvent exchange into tride- diphenyl ethers which may be found at concentrations several
cane is required for other liquid phases or the CP-Sil-88 GC orders of magnitude higher than that of the analytes of interest.
column.
INSTRUMENTATION A low resolution GC/MS utilizing 70
MHT 30 days; samples must be completely analyzed within ev must be capable of selected ion monitoring (SIM) for at
45 days of collection. least 11 ions simultaneously, with a cycle time of 1 second or

less. Minimum integration time for SIM is 50 ms per m/z. Also the 15 mL hexane against 40 mL of concentrated sulfuric acid.
required is a GC-to-MS interface constructed of all glass or Repeat the acid washings until no color is visible in the acid
glass-lined materials. One of the following GC columns is layer (but no more than four times). Finally, partition the
required: 15 mL hexane against 40 mL of 5% sodium chloride. Dry the
Column 1: 50 m CP-Sil-88 fused silica capillary column.
Column 2: DB-5 (30 m  0.25 mm I.D., 0.25-um film thick-
ness) fused silica capillary column.
Column 3: 30 m SP-2250 fused silica capillary column.
When toluene is employed as the final solvent, use of a bonded percent (v/v) methylene chloride in hexane. Check by GC/MS
phase column is recommended. Solvent exchange into tride- analysis that no PCDDs of PCDFs are elute in this fraction
cane is required for other liquid phases or nonbonded columns before discarding it. Elute the PCDDs and PCDFs from the
concentrator tube.
been shown to vary by homologous series and, to a lesser about 2 to 3 mL. Prepare a carbon column and rinse the carbon
degree, by individual isomer. with 5 mL cyclohexane/methylene chloride (50:50 v/v) in the
SAMPLING METHOD Grab and composite samples must flow. While still in the reverse direction of flow, transfer the
be collected in 1 L or 1-quart amber glass bottles with Teflon®- sample concentrate to the column and elute with 10 mL of
lined screw-caps that have been acid-washed and solvent rinsed methylene chloride/methanol/benzene (75:20:5, v/v). Save all
before use. If compositing equipment is used, the system must above eluates and combine them (this fraction may be used as
incorporate glass sample containers for the collection of a min- a check on column efficiency). Next, turn the column over and,
imum of 250 mL. samples. in the direction of forward flow, elute the PCDD/PCDF frac-
SAMPLE PRESERVATION Samples must be cooled and tion with 20 mL toluene. Evaporate the toluene fraction to
stored at 4C. about 1 mL on a rotary evaporator and transfer this concen-
MHT Samples must be extracted within 30 days and analyzed stream of nitrogen gas. The final volume will depend on the
within 45 days of collection. relative concentration of target analytes but it is typically
100 L for soil samples and 500 L for sludge, still bottom, and
SAMPLE PREPARATION
Soil samples — Extract 20 g of a 1:1 soil and anhydrous sodium fl ash samples. Extracts which are determined to be outside
sulfate mixture with 1:4 methanol-petroleum ether for 2 h in the calibration range for individual analytes must be diluted or
a wrist-action shaker. Concentrate the extract in a K-D and a smaller portion of the sample must be re-extracted.
then exchange the solvent with hexane in the K-D. The final An alternate carbon column clean-up also may be used with a
volume is 15 mL of hexane. 1 mL HPLC injector loop. The injector loop is connected to
the optional HPLC column.
Aqueous samples — Extract a 1 L sample with methylene chlo-
ride, dry it with anhydrous sodium sulfate and concentrate it QUALITY CONTROL Demonstrate, using a method blank,
in a K-D followed by exchange with hexane in the K-D. A that all glassware and reagents are interferent-free at the MDL
continuous liquid-liquid extractor may be used in place of a of the matrix of interest. A “method blank” must be run with
separatory funnel to avoid emulsions. The final volume is each 20 or fewer samples. The method blank is also dosed with
15 mL of hexane. the internal standards. For water samples, 1 L of deionized
and/or distilled water should be used as the method blank.
Alumina column clean-up — The clean-up procedure
Mineral oil may be used as the method blank for other matrices.
described below consists of two phases. The first phase involves
a sequential basic and acid washing of the extract that contains Calculate response factors for standards relative to the internal
the analytes. standards. Add a recovery standard to the samples prior to
injection. The concentration of the recovery standard in the
Wash the 15 mL hexane extract with 20% potassium hydroxide
sample extract must be the same as that in the calibration
in a separatory funnel. Repeat the washing until no color is
standards used to measure the response factors.
visible in the bottom layer but no more than four times because
strong base is known to degrade certain PCDDs/PCDFs, so Field duplicates (individual samples taken from the same loca-
contact time must be minimized. Next, partition the 15 mL tion at the same time) should be analyzed periodically to deter-
hexane against 40 mL of 5% sodium chloride. Next, partition mine the total precision (field and lab). Where appropriate,

field blanks should be provided to monitor for possible cross- extract must be reanalyzed on a column capable of
contamination of samples in the field. GC column performance 2,3,7,8-TCDF isomer specificity (e.g., DB-225, SP-2330, SP-
must be demonstrated initially and verified prior to analyzing 2331, or equivalent).
INSTRUMENTATION High-Resolution Gas Chromato-
graph/High-Resolution Mass Spectrometer/Data System
(HRGC/HRMS/DS) equipped with a GC injection port
ples and standards.
designed so that the separation of 2,3,7,8-TCDD from the other
Retention times of target analytes must be verified using refer- TCDD isomers achieved in the gas chromatographic column
ence standards. These values must correspond to the retention is not appreciably degraded.
time windows established. While certain cleanup techniques
Column 1: 60 m DB-5 fused silica capillary column.
are provided as part of this method, unique samples may
Column 2: 30 m DB-225 fused silica capillary column, or
require additional cleanup techniques to achieve the method
equivalent.
detection limit.
tion ranges for the compounds covered by this method have
846). U.S.E.P.A., 1986. Method 8280, Rev. 0, Sept. 1986. Office
not been determined yet. The sensitivity of Method 8290 is
1,2,3,4,7,8-HxCDF EPA Method 8290 times the upper method calibration limits must be analyzed by
Method 8280.
SAMPLE PREPARATION
chlorinated Dibenzofurans (PCDFs) by High-Resolution Gas
Sludge/wet fuel oil — Extract aqueous sludge or wet fuel oil
Chromatography/High-Resolution Mass Spectrometry
samples by refluxing a sample with toluene using a Dean-Stark
(HRGC/HRMS).
to clean up.
METHOD SUMMARY This method provides procedures for

gravity columns with silica gel and alumina and sequentially each determinative method (GC, GC/MS, HPLC) specifies
eluting the residue from the partition cleanup. Carbon column instrument calibration procedures using stock standards. It is
cleanup involves packing a column with a mixture of AX–21 recommended that cleanup also be performed on a series of
and Celite 545 and sequentially eluting the sample concentrate the same type of standards to validate chromatographic elution
from the silica/alumina cleanup with hexane, cyclohex- patterns for the compounds of interest and to verify the absence
ane/methylene chloride (50:50), and methylene chloride/meth- of interferences from reagents.
846). U.S. EPA. 1983. Method 8290, Rev. 0, Nov. 1990. Office
The toluene fraction is concentrated and stored in the dark at
room temperature until analysis.
CAS #57117-44-9
chlorinated Dibenzofurans (PCDFs) by High-Resolution Gas
itoring programs). The blank and spiked samples must be car-
Chromatography/High-Resolution Mass Spectrometry
ried through all stages of the sample preparation and
(HRGC/HRMS).
measurement steps.
MATRIX This method is applicable with a variety of envi-
ronmental matrices including: water, soil, sediment, paper
pulp, fl ash, fish tissue, human adipose tissue, sludges, fuel oil,
HRGC/HRMS method blank run is required between a cali-
chemical reactor residue, and still bottoms.
bration run and the first sample run. The same method blank
extract may thus be analyzed more than once if the number of METHOD SUMMARY This method provides procedures for
samples within a batch requires more than 12 h of analyses. the detection and quantitative measurement of polychlorinated
At the beginning of each 12-h period during which samples logues; PCDDs), and polychlorinated dibenzofurans (tetra-
are to be analyzed, an aliquot of the 1) GC column performance through octachlorinated homologues; PCDFs) in a variety of
check solution and 2) a high-resolution concentration calibra- environmental matrices and at part-per-trillion (ppt) to part-
tion must be analyzed to demonstrate adequate GC resolution per-quadrillion (ppq) concentrations. High-resolution gas
and sensitivity, response factor reproducibility, and mass range chromatography and high-resolution mass spectrometry
calibration, and to establish the PCDD/PCDF retention time (HRGC/HRMS) on purified sample extracts provides highly
windows. A mass resolution check must also be performed to specific identification of each analyte. Quantification is pro-
demonstrate adequate mass resolution using an appropriate vided using calibration standards.
reference compound (perfluorokerosene (PFK) is recom-
Routine or continuing calibration (using a high resolution cal- Analysts should avoid using PVC gloves. Interferants coex-
check samples must be handled in exactly the same manner as zofurans that may be found at concentrations several orders of
actual samples. Therefore, 1.0 mL of the QC check sample magnitude higher than the PCDDs or PCDFs.
QC check sample concentrate is different for the different ana- 2,3,7,8-TCDD (if detected on the DB-5 column), the sample
lytical techniques presented in the full method. extract must be reanalyzed on a column capable of
The analyst must demonstrate also that the compounds of 2,3,7,8-TCDF isomer specificity (e.g., DB-225, SP-2330, SP-
interest are being quantitatively recovered by the cleanup tech- 2331, or equivalent).
nique before the cleanup is applied to actual samples. For sam- INSTRUMENTATION High-Resolution Gas Chromato-
ple extracts that are cleaned up, the associated quality control graph/High-Resolution Mass Spectrometer/Data System
samples (e.g., spikes, blanks, and duplicates) must also be pro- (HRGC/HRMS/DS) equipped with a GC injection port
cessed through the same cleanup procedure. The analysis using designed so that the separation of 2,3,7,8-TCDD from the other

TCDD isomers achieved in the gas chromatographic column down and the PCDD/PCDF fraction is eluted with toluene.
is not appreciably degraded. The toluene fraction is concentrated and stored in the dark at
room temperature until analysis.
Column 1: 60 m DB-5 fused silica capillary column.
Column 2: 30 m DB-225 fused silica capillary column, or QUALITY CONTROL Demonstrate, through the analysis of
equivalent. a reagent water blank, that interferences from the analytical
PRECISION & ACCURACY Precision, bias and concentra- system, glassware, and reagents are under control. For each
tion ranges for the compounds covered by this method have analytical batch (up to 20 samples), a reagent blank, matrix
not been determined yet. The sensitivity of Method 8290 is spike, and matrix spike duplicate/duplicate must be analyzed
dependent upon the level of interferences within a given (the frequency of the spikes may be different for different mon-
matrix. Samples containing concentrations of specific conge- itoring programs). The blank and spiked samples must be car-
neric analytes of PCDDs and PCDFs that are greater than ten ried through all stages of the sample preparation and
times the upper method calibration limits must be analyzed by measurement steps.
a protocol designed for such concentration levels, e.g., EPA A GC column performance check is required at the beginning
Method 8280. of each 12-h period during which samples are analyzed. An
extract through a glass fiber filter, or equivalent, and concen- At the beginning of each 12-h period during which samples
trate it to near dryness either on a rotary evaporator using an are to be analyzed, an aliquot of the 1) GC column performance
to clean up.
funnel, using hexane. Proceed to clean up. Routine or continuing calibration (using a high resolution cal-
tent is too great to filter, centrifuge the sample, decant, and To evaluate the performance of the analytical method, the QC
then filter the aqueous phase. Combine the solids from the check samples must be handled in exactly the same manner as
centrifuge bottle(s) with the particulates on the filter and with actual samples. Therefore, 1.0 mL of the QC check sample
the filter itself and proceed with Soxhlet extraction for soil/sed- concentrate is spiked into each of four 1 L aliquots of reagent
iment. Extract the aqueous filtrate with methylene chloride in water (which becomes the QC check sample), extracted, and
a separatory funnel, filter the extract through anhydrous then analyzed by GC. The variety of semivolatile analytes which
sodium sulfate, and concentrate it using a K-D apparatus or a may be analyzed by GC is such that the concentration of the
rotary evaporator. Exchange the solvent with hexane and pro- QC check sample concentrate is different for the different ana-
ceed to clean up. lytical techniques presented in the full method.
Clean up — The sample extract is cleaned up utilizing a num- The analyst must demonstrate also that the compounds of
ber of different techniques. Partition cleanup is where the sam- interest are being quantitatively recovered by the cleanup tech-
ple extract is partitioned with concentrated sulfuric acid, 5% nique before the cleanup is applied to actual samples. For sam-
aqueous sodium chloride, and 20% aqueous potassium ple extracts that are cleaned up, the associated quality control
hydroxide. Silica/alumina column cleanup involves packing samples (e.g., spikes, blanks, and duplicates) must also be pro-
gravity columns with silica gel and alumina and sequentially cessed through the same cleanup procedure. The analysis using
eluting the residue from the partition cleanup. Carbon column each determinative method (GC, GC/MS, HPLC) specifies
cleanup involves packing a column with a mixture of AX–21 instrument calibration procedures using stock standards. It is
and Celite 545 and sequentially eluting the sample concentrate recommended that cleanup also be performed on a series of
from the silica/alumina cleanup with hexane, cyclohex- the same type of standards to validate chromatographic elution
ane/methylene chloride (50:50), and methylene chloride/meth- patterns for the compounds of interest and to verify the absence
anol/toluene (75:20:5). Then the column is turned upside of interferences from reagents.

846). U.S. EPA. 1983. Method 8290, Rev. 0, Nov. 1990. Office tion ranges for the compounds covered by this method have
1,2,3,7,8,9-HxCDF EPA Method 8290 times the upper method calibration limits must be analyzed by
Method 8280.

(HRGC/HRMS).

Method 8280.
trate it to near dryness either on a rotary evaporator using an At the beginning of each 12-h period during which samples
inert gas. Transfer the concentrate to a separatory funnel using are to be analyzed, an aliquot of the 1) GC column performance
hexane and wash it with 5% sodium chloride solution. Proceed check solution and 2) a high-resolution concentration calibra-
to clean up. tion must be analyzed to demonstrate adequate GC resolution
funnel, using hexane. Proceed to clean up. Routine or continuing calibration (using a high resolution cal-
performed at the end of each 12 h period. Furthermore, a
HRGC/HRMS method blank analysis must be recorded follow-
1% or more solids, it must be filtered through a glass fiber filter
ing a calibration analysis and the first sample analysis.
tent is too great to filter, centrifuge the sample, decant, and To evaluate the performance of the analytical method, the QC
then filter the aqueous phase. Combine the solids from the check samples must be handled in exactly the same manner as
centrifuge bottle(s) with the particulates on the filter and with actual samples. Therefore, 1.0 mL of the QC check sample
the filter itself and proceed with Soxhlet extraction for soil/sed- concentrate is spiked into each of four 1 L aliquots of reagent
iment. Extract the aqueous filtrate with methylene chloride in water (which becomes the QC check sample), extracted, and
a separatory funnel, filter the extract through anhydrous then analyzed by GC. The variety of semivolatile analytes which
sodium sulfate, and concentrate it using a K-D apparatus or a may be analyzed by GC is such that the concentration of the
rotary evaporator. Exchange the solvent with hexane and pro- QC check sample concentrate is different for the different ana-
ceed to clean up. lytical techniques presented in the full method.
Clean up — The sample extract is cleaned up utilizing a num- The analyst must demonstrate also that the compounds of
ber of different techniques. Partition cleanup is where the sam- interest are being quantitatively recovered by the cleanup tech-
ple extract is partitioned with concentrated sulfuric acid, 5% nique before the cleanup is applied to actual samples. For sam-
aqueous sodium chloride, and 20% aqueous potassium ple extracts that are cleaned up, the associated quality control
hydroxide. Silica/alumina column cleanup involves packing samples (e.g., spikes, blanks, and duplicates) must also be pro-
gravity columns with silica gel and alumina and sequentially cessed through the same cleanup procedure. The analysis using
eluting the residue from the partition cleanup. Carbon column each determinative method (GC, GC/MS, HPLC) specifies
cleanup involves packing a column with a mixture of AX–21 instrument calibration procedures using stock standards. It is
and Celite 545 and sequentially eluting the sample concentrate recommended that cleanup also be performed on a series of
from the silica/alumina cleanup with hexane, cyclohex- the same type of standards to validate chromatographic elution
The toluene fraction is concentrated and stored in the dark at REFERENCE Test Methods for Evaluating Solid Waste (SW-
room temperature until analysis. 846). U.S. EPA. 1983. Method 8290, Rev. 0, Nov. 1990. Office
analytical batch (up to 20 samples), a reagent blank, matrix 1,2,3,4,7,8-HxCDF EPA Method 8280
itoring programs). The blank and spiked samples must be car- TITLE Analysis of PCDDs and PCDFs

MATRIX chemical wastes, fuel oils, still bottoms, sludges, should be analyzed periodically. GC column performance must
water, soil, fl ash, reactor residues. be demonstrated initially and verified prior to analyzing any
sample in a 12 h period. A series of calibration standards must
APPLICATION This method is used for the analysis of tetra-,
be processed through the procedure to validate elution patterns
penta-, hexa-, hepta-, and octachlorinated dibenzo-p-dioxins
and absence of interferents from reagents. Both the alumina
(PCDDs) and dibenzofurans (PCDFs). The sensitivity of the
column and carbon column performance must be routinely
method is dependent on the level of interferents within the
checked for presence of the analyte.
matrix. Only experienced analysts should be used. Special
safety precautions must be observed and an EPA-approved Performance evaluation samples and split samples with other
sample disposal plan must be used. laboratories are also expected to be periodically analyzed.
INTERFERENCES Solvents, reagents, and glassware may REFERENCE Method 8280, SW-846, 3rd ed., Nov.1986.
tracted compounds from samples; PCBs and polychlorinated
diphenyl ethers are common interferents.
Hydroquinone EPA Method 8270
INSTRUMENTATION GC/MS with a fused silica capillary CAS #123-31-9
column. Also, solvent extraction and concentration glassware
and either a gravity flow activated carbon AX–21/silica gel Type TITLE Semivolatile Organic Compounds by GC/MS
60 EM reagent column or a HPLC with a 10 mm by 7 cm
silanized glass column with active carbon AX–21 and Spher-
isorb S10W silica for sample cleanup. One of three fused silica
capillary GC columns may be used: column 1: 50 m CP-Sil-88;
Column 2: 30 m by 0.25 mm DB-5; colunm 3: 30 m SP-2250.
RANGE 50–6,000 picograms. lakes, etc.
MDL 2.53 ng/L (in reagent water); 0.83 g/kg (in Missouri METHOD SUMMARY This method covers 259 semivolatile
soil); 0.30 g/kg (in fl ash); 2.17 g/kg (in industrial sludge); organic compounds. In very limited applications direct injec-
2.27 g/kg (in still bottom); 2.09 g/kg (in fuel oil); MDLs are tion of the sample into the GC/MS system may be appropriate,
for carbon-13 labeled analyte. but this results in very high detection limits (approximately
PRECISION as (RSD) 26% with 5 ng/g in clay; 6.8% with
25 ng/g soil. 5.6% with 139 ng/g in sludge; 13.5% with
24.2 ng/g in fl ash. ditions. Typically 30 g of a solid sample, containing surrogate,
ACCURACY (as Mean % Recovery) 54.2% with 5 ng/g in and matrix spiking standards, is extracted ultrasonically. After
clay; 68.5% with 25 ng/g in soil; 82.2% with 125 ng/g in sludge; concentrating the extract to 1 mL it is spiked with 10 L of an
91.0% with 46 ng/g in fl ash; 92.9% with 2500 ng/g in still internal standard solution just prior to analysis by GC/MS. The
bottom. volume injected should contain about 100 ng of base/neutral
SAMPLING METHOD Use 1 L (or quart) amber glass bot-
tles with Teflon®-lined or solvent washed foil screw caps. Tape
caps to bottle after sampling. INTERFERENCES Raw GC/MS data from all blanks, sam-
Compositing equipment must use glass containers and contain
no Tygon or rubber tubing. Sample bottles must not be pre-
washed with the sample before its collection. Aqueous samples
cannot be aliquoted from sample containers — the entire sam-
ple must be used and the container is washed out with the
extracting solvent.
STABILITY Cool to 4C and store at this temperature. When
toluene is employed as the final solvent use a bonded phase GC
column for separation. Otherwise, solvent exchange into tride-
cane is required for other liquid phases or the CP-Sil-88 GC
column.
MHT 30 days; samples must be completely analyzed within requiring no lubrication, a K-D concentrating apparatus, water
45 days of collection. bath, and an ultrasonic disrupter with a minimum power of
QUALITY CONTROL A method blank must be analyzed
each time a set of samples is extracted or there is a change in PRECISION & ACCURACY The estimated quantitation
reagents. A lab method blank must be run with each analytical limit (EQL) of Method 8270B for determining an individual
batch of 20 or fewer samples. Field duplicates and field blanks compound is approximately 1 mg/kg (wet weight) for soil or

matrix and method of preparation), and 10 g/L for ground- dard. For base/neutral acid analysis, the amount of the surro-
water samples. EQLs will be proportionately higher for sample gates and matrix spiking compounds added to the sample
The EQL(b) for groundwater in g/L is not determined.
Other Matrices Factor (a) in the extract to be analyzed (assuming a 1- L injection).
(a) EQL forother matrices =[EQL forlow soil/sediment] [Factor]. or more times. Dry the extract using a column with anhydrous
This estimated EQL is similar to an EPA “Practical Quantitation sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with used for tuning the GC/MS system each 12-h shift. A system
a screw-top Teflon®-lined cover that has been prewashed with performance check also must be made during every 12-h shift.

different for different monitoring programs). The blank and generator, a centrifuge and an ultrasonic disrupter will be
spiked samples must be carried through all stages of the sample required.
Narrow Bore Columns:
Primary Column 1: 30 m 0.25 mm, 5% phenyl/95% methyl
silicone (DB-5), 0.25 m film thickness.
REFERENCE Test Methods for Evaluating Solid Waste (SW- Primary Column 1a (GC/MS): 30 m  0.32 mm, 5% phe-
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office nyl/95% methyl silicone (DB-5), 1-m film thickness.
of Solid Waste, Washington, DC. Column 2: 30 m 0.25 mm DB-608 with a 25 m film thickness.
Confirmation Column: 30 m  0.25 mm, 14% cyanopropyl
phenyl silicone (DB-1701), 0.25 m film thickness.
5-Hydroxydicamba EPA Method 8151 Megabore Columns:
CAS #7600-50-2 Primary Column: 30 m 0.53 mm DB-608 with 0.83 m film
thickness.
TITLE Chlorinated Herbicides by GC Using Methylation or Confirmation Column: 30 m  0.53 mm, 14% cyanopropyl
Pentafluorobenzylation Derivatization: Capillary Column phenyl silicone (DB-1701), 1.0 m film thickness.
Technique.
PRECISION & ACCURACY Method detection limits
MATRIX This method covers aqueous and solid matrices. (MDLs) are compound-dependent and vary with derivitization
This includes a wide variety such as drinking water, ground- efficiency, derivative recovery, the matrix sampled, and herbi-
water, industrial wastewaters, surface waters, soils, solids, and cide concentration.
sediments.
The estimated MDL (in g/L) was 0.04 for aqueous samples
METHOD SUMMARY This is a GC method for determining using GC/ECD.
19 chlorinated acid herbicides in aqueous, soil, and waste
matrices. Because these compounds are produced and used in The estimated MDL (in g/kg) was No Data for soil samples
various forms (i.e., acid, salt, ester, etc.) a hydrolysis step is using GC/ECD when corrected back to 50 g samples extracted
included to convert the herbicide to the acid form prior to and concentrated to 10 mL with 5-L injections.
analysis. This method provides hydrolysis, extraction, deriva- The estimated GC/MS identification limit (in ng) was No Data
tization and GC conditions for the analysis of chlorinated acid for soil samples using GC/MS.
herbicides in water, soil, and waste samples. Water samples are
hydrolyzed in situ, extracted with diethyl ether, and then ester- Mean percent recovery, calculated from 7–8 determinations of
ified with either diazomethane or pentafluorobenzyl bromide. spiked reagent water, after diazomethane derivatization, from
The derivatives are determined by gas chromatography with an a spike concentration (in g/L) of 0.2 was 103 with a standard
electron capture detector (GC/ECD). The results are reported deviation of the percent recovery of 16.5.
as acid equivalents. The sensitivity of this method depends on Mean percent recovery, calculated from 10 determinations of
the level of interferences in addition to instrumental limitations. spiked clay and clay/still bottom samples over the linear con-
INTERFERENCES Method interferences may be caused by centration range (in ng/g) of no data was none reported with
contaminants in solvents, reagents, glassware, and other sample a percent relative standard deviation of none. The RSD % was
processing hardware. Immediately prior to use, glassware calculated on 10 samples high in the linear concentration range
should be rinsed with the next solvent to be used. Matrix inter- and 10 low in the range. The linear concentration range was
ferences may be caused by contaminants that are coextracted determined using standard solutions and corrected to 50 g soil
from the sample. Organic acids, especially chlorinated acids, samples.
cause the most direct interference with the determination by
methylation. Phenols, including chlorophenols, may also inter-
Containers used to collect samples for the determination of
fere with this procedure. The determination using pentafluo-
semivolatile organic compounds should be soap and water
robenzylation is more sensitive, and more prone to
washed followed by methanol (or isopropanol) rinsing. The
interferences from the presence of organic acids of phenols than
sample containers should be of glass or Teflon® and have screw-
by methylation. Alkaline hydrolysis and subsequent extraction
top covers with Teflon® liners.
of the basic solution removes many chlorinated hydrocarbons
and phthalate esters that might otherwise interfere with the No preservation is used with concentrated waste samples. With
ECD analysis. The herbicides, being strong organic acids, react liquid samples containing no residual chlorine and with soil,
readily with alkaline substances and may be lost during analy- sediment, and sludge samples, immediately cooling to 4C is
sis. Therefore, glassware must be acid-rinsed and then rinsed the only preservation used. When residual chlorine is present
to constant pH with organic-free reagent water. then 3 mL of 10% aqueous sodium sulfate is added for each
INSTRUMENTATION A GC suitable for Grob-type injec- gallon of sample collected, followed by cooling to 4C.
tion using capillary columns. A data system for measuring peak The holding time for all volatile organics samples is 14 days.
heights and/or peak areas is recommended.An electron capture Liquid samples must be extracted within 7 days and their
detector (ECD) is used. Also a K-D apparatus, a diazomethane extracts analyzed within 40 days. Concentrated waste, soil,

sediment, and sludge samples must be extracted within 14 days spectra may be employed to aid the qualitative identification
and their extracts analyzed within 40 days. process.
SAMPLE PREPARATION REFERENCE Test Methods for Evaluating Solid Waste, Phys-
Preparation of soil, sediment, and other solid samples — Acid- ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
ify 30 g (dry weight) solids with 0.1 M phosphate buffer (pH = of Solid Waste, Washington, DC, EPA Method 8151, Nov. 1990.
2.5) and thoroughly mix the contents. Spike the sample with
surrogate compound(s). The ultrasonic extraction of solids
must be optimized for each type of sample. In order for the
2-Hydroxypropionitrile EPA Method 8240
ultrasonic extractor to efficiently extract solid samples, the
CAS #78-97-7
sample must be free flowing when the solvent is added. Acid-
ified anhydrous sodium sulfate should be added to clay-type
soils, or any other solid that is not a free-flowing sandy texture,
until a free flowing mixture is obtained. Add methylene chlo- MATRIX Nearly all types of sample matarices, regardless of
ride and perform ultrasonic extraction. Combine organic water content, can be analyzed using this method. This includes
extracts from the repetitive extractings of the sample and cen- groundwater, aqueous sludges, caustic liquors, acid liquors,
trifuge. Add aqueous potassium hydroxide, water, and metha- waste solvents, oily wastes, mousses, tars, fibrous wastes, poly-
nol to the extract and reflux the mixture on a water bath. metric emulsions, filter cakes, spent carbons, spent catalysts,
Extract the solution three times with methylene chloride and soils, and sediments.
discard the methylene chloride phase. The basic solution con-
tains the herbicide salts. Adjust the pH of the solution to <2
with cold sulfuric acid and extract three times with methylene
chloride. Combine the extracts and pour them through a pre-
rinsed drying column containing acidified anhydrous sodium
sulfate. Collect the dried extracts in a K-D flask and concentrate
them.
Preparation of aqueous samples — Measure 1 L of sample into complete, the sorbent tube is heated and backflushed with inert
a 2 L separatory funnel and spike it with surrogate com- gas to desorb the trapped components onto a GC column.
pound( s). Add NaCl to the sample, then add 6 N NaOH to the
sample to a pH of 12 or more and let the sample sit at room
temperature for 1 h to hydrolyze esters. Extract the sample
the trap account for many contamination problems. Interfer-
three times with methylene chloride and discard the extracts.
Then add cold 12 N sulfuric acid to a pH less than or equal to
siderably from source to source. Cross-contamination can
2, and extract the sample three times with ethyl ether. Collect
occur whenever high-level and low-level samples are analyzed
the ether phase in a flask containing acidified anhydrous
sodium sulfate and allow it to remain in contact with the
sodium sulfate for a minimum of 2 h. The drying step is very
critical to ensuring complete esterification; any moisture
can be contaminated by diffusion of volatile organics (partic-
remaining in the ether will result in low herbicide recoveries. ularly methylene chloride and fluorocarbons) through the sep-
Extract concentration and derivatization — The combined tum seal into the sample during shipment and storage. A trip
ether extract is concentrated to about 1 mL using a K-D appa- blank can serve as a check on such contamination. The lab
ratus followed by using a micro Snyder column or nitrogen gas where volatile analysis is performed and also the refrigerated
blowdown. If methyl esters are to be produced, then dilute the storage area should be completely free of solvents.
concentrated ether extract with 1 mL of isooctane and 0.5 mL
of methanol, dilute to a final volume of 4 mL, and esterify with
trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
diazomethane. If pentafluorobenzene esters are to be produced, I.D. glass column packed with 1% SP-1000 on Carbopack-B
then dilute concentrated ether extract with acetone to a final (60/80 mesh) is required.Also needed is a 5-mL purging device,
volume of 4 mL and esterify with pentafluorobenzyl bromide. a sorbent trap, and a thermal desorption apparatus.
QUALITY CONTROL Select a representative spike concen- PRECISION & ACCURACY This method is reported to have
tration for each compound (acid or ester) to be measured. been tested by 15 laboratories using organic-free reagent water,
Using stock standard, prepare a quality control check sample drinking water, surface water, and industrial wastewaters (not
concentrate, in acetone, that is 1000 times more concentrated specified) fortified at six concentrations over the range 5–
than the selected concentrations. Use this quality control check 600 g/L.
sample concentrate to prepare quality control check samples.
Calculate surrogate standard recovery on all standards, sam- Sample estimated quantitation limits (EQLs) are highly
ples, blanks, and spikes. GC/MS techniques should be judi- matrix-dependent. The EQLs listed may not always be achiev-
ciously employed to support qualitative identifications made able. EQLs listed for soils or sediments are based on wet weight.
with this method. When available, chemical ionization mass Normally, data is reported on a dry-weight basis; therefore,

EQL in groundwater in g/L was not listed. Sediments, soils, and waste samples — All samples of this type
EQL in low soil or sediment in g/kg was not listed. should be screened by GC analysis using a headspace method
Other Matrices Factor (a) or a 1-g sample for expected concentrations between 0.1 and
(a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous
SAMPLING METHOD
a Teflon®-faced silicone septum that has been prewashed, with reagent tetraglyme or possibly polyethylene glycol (PEG).
rinsed with distilled deionized water, and oven dried. However, An aliquot of the extract is added to organic-free reagent water
if residual chlorine is present, collect sample in a 40-oz. soil containing surrogate and internal standards. This is purged at
cate and seal them in separate plastic bags. Mix the contents of the sample container with a narrow metal
SAMPLE PRESERVATION
1,000–20,000 g/kg 50 L
MHT Maximum holding time is 14 days from the date of
5,000–100,000 g/kg 10 L
sample collection.
SAMPLE PREPARATION
Calculate appropriate dilution factor for concentrations
exceeding this table.

QUALITY CONTROL Demonstrate, through the analysis of spiked samples must be carried through all stages of the sample
a reagent water blank, that interferences from the analytical preparation and measurement steps. QC samples mentioned
system, glassware, and reagents are under control. Blank sam- in the section on Interferences will also be needed as appropri-
ples should be carried through all stages of the sample prepa- ate to those situations.
duplicate must be analyzed (the frequency of the spikes may
be different for different monitoring programs). The blank and

I
Indeno(1,2,3-cd)pyrene EPA Method 625 Accuracy (in g/L) as expected recovery for one or more mea-
CAS #193-39-5 surements of a sample containing a true concentration of
C was 0.78C-3.10.
TITLE Base/Neutrals and Acids, U.S. EPA Method 625 Precision (in g/L) as expected single analyst standard devia-
tion of measurements at an average concentration found at
X was 0.29X + 1.46.
wastewaters.
METHOD SUMMARY Approximately 1 L of sample is seri- dard deviation of measurements in an average concentra-
ally extracted with methylene chloride at a pH greater than 11 tion found at X was 0.50X + 0.44.
and again at a pH less than 2 using a separatory funnel or a C = True value of the concentration in g/L.
continuous extractor. The methylene chloride extract is dried, X = Average recovery found for measurements of samples con-
concentrated to a volume of 1 mL, and analyzed by GC/MS. taining a concentration at C in g/L.
Qualitative identification of the parameters in the extract is
performed using the retention time and the relative abundance SAMPLE PREPARATION Adjust the pH to >11 with sodium
of three characteristic masses (m/z). Qualitative analysis is per- hydroxide and serially extract in a separatory funnel with meth-
formed using either external or internal standard techniques ylene chloride or else in a continuous extractor. Next, adjust
with a single characteristic m/z. the pH to <2 with sulfuric acid and serially extract in a sepa-
ratory funnel with methylene chloride or else in a continuous
INTERFERENCES Method interferences may be caused by extractor. Dry the extracts separately through a column of
contaminants in solvents, reagents, glassware, and other sample anhydrous sodium sulfate and then concentrate each of the
processing hardware. Glassware must be scrupulously cleaned. extracts to 1.0 mL using a K-D apparatus.
Glassware should be heated in a muffle furnace at 400C for 5
to 30 min. Some thermally stable materials, such as PCBs, may SAMPLE COLLECTION, PRESERVATION & HANDLING
not be eliminated by this treatment. Solvent rinses with acetone
and pesticide quality hexane may be substituted for the muffle must be refrigerated at 4C from the time of collection until
extraction. If residual chlorine is present, add 80 mg of sodium
thiosulfate/L of sample and mix well. All samples must be
mended for the basic fraction may not exhibit sufficient reso- QUALITY CONTROL Make an initial, one-time, demonstra-
lution for some analytes. tion of the ability to generate acceptable accuracy and precision
INSTRUMENTATION A GC/MS system with an injection must analyze a reagent water blank to demonstrate that inter-
port designed for on-column injection when using packed col- ferences from the analytical system and glassware are under
umns and for splitless injection when using capillary columns. control. Each time a set of samples is extracted or reagents are
Column for base/neutrals: 1.8 m long  2 mm I.D. glass, changed, a reagent water blank must be processed. Spike and
packed with 3% SP-2550 on Supelcoport (100/120 mesh) analyze a minimum of 5% of all samples to monitor and eval-
or equivalent. uate lab data quality. A QC check sample concentrate that
Column for acids: 1.8 m long 2 mm I.D. glass, packed with contains each parameter of interest at a concentration of
1% SP-1240DA on Supelcoport (100/120 mesh) or equivalent. 100 g/mL in acetone is required. PCBs and multicomponent
obtained using reagent water. The MDL actually achieved in a After analysis of five spiked wastewater samples, calculate the
given analysis will vary depending on instrument sensitivity average percent recovery and the standard deviation of the
and matrix effects. This method was tested by 15 laboratories percent recovery. Spike all samples with the surrogate standard
using reagent water, drinking water, surface water, and indus- spiking solution and calculate the percent recovery of each
trial wastewaters spiked at six concentrations over the range 5 surrogate compound.
to 100 g/L. Single operator precision, overall precision, and REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct.
method accuracy were found to be directly related to the con- 26, 1984.
The MDL (in g/L) in reagent water was 3.7.
The standard deviation (in g/L based on 4 recovery measure- Indeno(1,2,3-cd)pyrene EPA Method 1625
ments) was 44.6. CAS #193-39-5
was D-150.9. TITLE Semivolatile Organic Compounds by Isotope Dilu-
The range (in %) for percent recovery was D-171. tion GC/MS

Note: Background levels of this compound were present in the
sludge tested, resulting in higher than expected MDLs. The
MDL for this compound is expected to be approximately
Stable isotopically-labeled analogs of the compounds of interest 50 g/kg with no interferences present.
If the solids content is 30% or less, the sample is diluted to 1% recovery (in g/L) was 23–299.
solids with reagent water, homogenized ultrasonically, and
techniques.
Each extract is dried over sodium sulfate, concentrated to a the time of collection until extraction. If residual chlorine is
volume of 5 mL, cleaned up using GPC, if necessary, and con- present in aqueous samples, add 80 mg sodium thiosulfate/L
centrated. Extracts are concentrated to 1 mL if GPC is not of water. Begin sample extraction within 7 days of collection,
performed, and to 0.5 mL if GPC is performed. and analyze all extracts within 40 days of extraction.
An internal standard is added to the extract, and a 1-mL aliquot SAMPLE PREPARATION Samples containing 1% solids or
of the extract is injected into the GC. The compounds are less are extracted directly using continuous liquid-liquid
separated by GC and detected by a MS. The labeled compounds extraction techniques. Samples containing 1 to 30% solids are
serve to correct the variability of the analytical technique. diluted to the 1% level with reagent water and extracted using
techniques.
spectra. Materials used in the analysis must be demonstrated Base/neutral extraction — Adjust the pH of the waters in the
to be free from interferences under the conditions of analysis extractors to 12–13 with 6 N NaOH. Extract with methylene
by running method blanks initially and with each sample lot chloride for 24–48 h.
(sample started through the extraction process on a given 8-h Acid extraction — Adjust the pH of the waters in the extractors
shift, to a maximum of 20). Specific selection of reagents and to 2 or less using 6 N sulfuric acid. Extract with methylene
purification of solvents by distillation in all glass systems may chloride for 24–48 h.
be required. Glassware and, where possible, reagents are Ultrasonic extraction of high solids samples — Add anhy-
cleaned by solvent rinse and baking at 450C for 1-h minimum. drous sodium sulfate to the sample and QC aliquot(s).
Interferences coextracted from samples will vary considerably Add acetone:methylene chloride (1:1) to the sample and
from source to source, depending on the diversity of the site mix thoroughly
being sampled.
INSTRUMENTATION Major instrumentation includes a GC
with a splitless or on-column injection port for capillary col-
Analyses of blanks are required to demonstrate freedom from
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1% method performance for samples, the samples are diluted to
vinyl silicone bonded phased fused silica capillary column. bring method performance within acceptable limits.
PRECISION & ACCURACY The detection limits of the For low solids (aqueous samples), extract, concentrate, and
method are usually dependent on the level of interferences analyze two sets of four 1-L aliquots (8 aliquots total) of the
rather than instrumental limitations. The limits typify the min- precision and recovery standard. For high solids samples, two
imum quantities that can be detected with no interferences sets of four 30-g aliquots of the high solids reference matrix
present. are used.
The minimum level (in g/mL) was 20. This is defined as a Spike all samples with labeled compounds to assess method per-
minimum level at which the analytical system shall give recog- formance. Compute percent recovery of the labeled compounds

using the internal standard method. Compare the labeled com- 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
pound recovery for each compound with the corresponding capillary column. A continuous liquid-liquid extractor
labeled compound recovery. equipped with Teflon® or glass connection joints and stopcocks
U.S. EPA Industrial Technology Division, Washington, DC, in g/kg is 660.
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, Accuracy as g/L is 0.78C–3.10.
U.S. EPA, Office of Water Regulations and Standards, 401 M Overall precision in g/L is 0.50X–0.44.
Indeno(1,2,3-cd)pyrene EPA Method 8270 This calculation is based on a 30-g sample and gel perme-
Limit.”
(or isopropanol).
SAMPLE PRESERVATION
INSTRUMENTATION A GC/MS and a data system are MHT Liquid samples must be extracted within 7 days and the
required. The GC column used is a 30 m 0.25 mm I.D. (or extracts analyzed within 40 days. Soils, sediments, or sludges may

be stored for a maximum of 14 days and the extracts analyzed the last daily calibration standard check, the mass spectrometer
within 40 days. must be inspected for malfunctions and corrections must be
SAMPLE PREPARATION
Liquid samples — Transfer 1 L quantitatively to a continuous Demonstrate, through the analysis of a reagent water blank,
extractor. If high concentrations are anticipated, a smaller vol- that interferences from the analytical system, glassware, and
ume may be used and then diluted with organic-free reagent reagents are under control. The blank samples should be car-
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) ried through all stages of the sample preparation and measure-
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking ment steps. For each analytical batch (up to 20 samples), a
solution into each sample. For the sample in each analytical reagent blank, matrix spike, and matrix spike duplicate/dupli-
hydroxide and extract it with methylene chloride again for REFERENCE Test Methods for Evaluating Solid Waste (SW-
18–24 h. Dry the extract through a column containing anhy- 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
drous sodium sulfate and concentrate it to 1 mL using a K-D of Solid Waste, Washington, DC.
concentrator.
or wet samples (gummy or clay type) that do not have a free- Indeno(1,2,3-cd)pyrene EPA Method 8100
flowing sandy texture must be mixed with anhydrous sodium CAS #193-39-5
standards to all samples, spikes, standards, and blanks. For the TITLE Polynuclear Aromatic Hydrocarbons
of a matrix spiking standard. For base/neutral acid analysis, the MATRIX Groundwater, soils, sludges, water miscible liquid
amount added of the surrogates and matrix spiking com- wastes, and non-water miscible wastes.
pounds should result in a final concentration of 100 ng/ L of APPLICATION This method is used for the analysis of var-
each base/neutral analyte and 200 ng/L of each acid analyte ious PAHs. Samples are extracted, concentrated, and analyzed
in the extract to be analyzed (assuming a 1- L injection). using direct injection of both neat and diluted organic liquids.
The method provides two optional GC columns that are better
than Column 1 and that may help resolve analytes from inter-
or more times. Dry the extract using a column with anhydrous ferences.
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. INTERFERENCES Solvents, reagents, and glassware may
QUALITY CONTROL A methylene chloride solution con- introduce artifacts. Other interferences may come from coex-
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is tracted compounds from samples.
used for tuning the GC/MS system each 12-h shift. A system INSTRUMENTATION GC capable of on-column injections
performance check also must be made during every 12-h shift. and a flame with detector (FID). Column 1: a 1.8 m by 2 mm
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- 3% OV-17 on Chromosorb W-AW-DCMS column. Column 2:
rophenol, and benzidine is required to verify injection port a 30 m by 0.25 mm SE-54 fused silica capillary colunm. Col-
inertness and GC column performance. A calibration standard umn 3: a 30 m by 0.32 mm SE-54 fused silica capillary column.
including all required surrogates, must be performed every 12 h RANGE 0.1–425 g/L
during analysis. After the system performance check is met, MDL Not reported.
validity of the initial calibration. PQL FACTORS FOR MULTIPLYING FID MDL
calibration check standard must be evaluated immediately after PRECISION 0.42X + 0.01 g/L (overall precision).
calibration (12 h), the chromatographic system must be SAMPLING METHOD Use 8-oz. widemouth glass bottles
inspected for malfunctions and corrections must be made, as with Teflon®-lined caps for concentrated waste samples, soils,
required. If the electron ionization current plot (EICP) area for sediments, and sludges. Use 1 or 2½ gallon amber glass bottles
any of the internal standards changes by a factor of two from with Teflon®-lined caps for liquid (water) samples.

STABILITY Cool soil, sediment, sludge, and liquid samples SAMPLING METHOD Use 8-oz. widemouth glass bottles
to 4C. If residual chlorine is present in liquid samples add with Teflon®-lined caps for concentrated waste samples, soils,
3 mL of 10% sodium thiosulfate per gallon of sample and cool sediments, and sludges. Use 1 or 2½ gallon amber glass bottles
to 4C. with Teflon®-lined caps for liquid (water) samples.
MHT 14 days for concentrated waste, soil, sediment, or STABILITY Cool soil, sediment, sludge, and liquid samples
sludge; 7 days for liquid samples; all extracts must be analyzed to 4C. If residual chlorine is present in liquid samples add
within 40 days. 3 mL of 10% sodium thiosulfate per gallon of sample and cool
to 4C.
centrate containing each analyte of interest is required. The QC MHT 14 days for concentrated waste, soil, sediment, or
check sample concentrate may be prepared from pure standard sludge; 7 days for liquid samples; all extracts must be analyzed
materials or purchased as certified solutions Use appropriate within 40 days.
trip, matrix, control site, method, reagent, and solvent blanks. QUALITY CONTROL Internal, surrogate, and five concen-
Internal, surrogate, and five concentration level calibration tration level calibration standards are used. The calibration
standards are used. The quality control check sample concen- standards must be used with the analytical method blank. A
trate should contain indeno(1,2,3-cd)pyrene at 10 g/mL in quality control check sample concentrate containing
acetonitrile. indeno(1,2,3-cd)pyrene at 10 g/mL is required. The QC check
sample concentrate may be prepared from pure standard mate-
REFERENCE Test Methods for Evaluating Solid Waste rials or purchased as certified solutions. Use appropriate trip,
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC, matrix, control site, method, reagent, and solvent blanks.
Method 8100, Nov. 1986.
REFERENCE Test Methods for Evaluating Solid Waste
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC,
Method 8310, Rev. 0, Nov. 1986.
Indeno(1,2,3-cd)pyrene EPA Method 8310
CAS #193-39-5
TITLE Polynuclear Aromatic Hydrocarbons Iodide (Titrimetric) EPA Method 345.1
MATRIX Groundwater, soils, sludges, water miscible liquid TITLE Inorganics, Non-Metallics
MATRIX Drinking, surface, and saline waters. Wastewater.
APPLICATION This method is used for the analysis of 16
APPLICATION Date issued 1974. After pretreatment to
polynuclear aromatic hydrocarbons (PAHs). Samples are
remove interferences, the sample is analyzed for iodide by con-
extracted, concentrated, and analyzed using HPLC with detec-
verting the iodide to iodate with bromine water and titrating
tion by UV and fluorescence detectors. with phenylarsine oxide (PAO) or sodium thiosulfate.
INTERFERENCES Solvents, reagents, and glassware may INTERFERENCES Iron, manganese and organic matter can
introduce artifacts. Other interferences may come from coex- interfere. (Calcium oxide pretreatment nullifies this interfer-
tracted compounds from samples. ence). Color interferes with observation of indicator and bro-
INSTRUMENTATION HPLC with a gradient pumping sys- mine-water color changes. (Overcome by using a pH meter and
tem and a 250 mm by 2.6 mm reverse phase HC-ODS Sil-X standardized amounts of reagents).
5-micron particle-size column. The fluorescence detector uses INSTRUMENTATION Laboratory iodometric titration
an excitation wavelength of 280 nm and emission greater than equipment and glassware.
389 nm cutoff with dispersive optics.
RANGE 2–20 mg/L of iodide.
RANGE 0.1–425 g/L.
MDL Not listed.
MDL 0.043 g/L (fluorescence; reagent water).
PRECISION SD = 0.06 mg/L at 11.6 mg/L of iodide.
ACCURACY Recovery = 97% at 11.6 mg/L of iodide.
Matrix Multiplication Factor
SAMPLING METHOD Plastic or glass (100 mL).
Groundwater 10
Low-level soil by sonication with GPC cleanup 670 STABILITY No Federal Register rules apply.
QUALITY CONTROL A distilled water blank must be run
with each set of samples because of iodide in reagents.
ACCURACY 0.54C + 0.06 g/L (as recovery). and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979.

Iodomethane EPA Method 1624 SAMPLE COLLECTION, PRESERVATION & HANDLING
TITLE Volatile Organic Compounds by Isotope Dilution air bubbles are entrapped. Samples are maintained at 0 to 4 C
GC/MS from the time of collection until analysis. If an aqueous sample
MATRIX Compounds may be determined in waters, soils, (10 mg/40 mL) to the empty sample bottles just prior to ship-
and municipal sludges by this method. ment to the sample site. All samples must be analyzed within
METHOD SUMMARY This method is used to determine 58 14 days of collection.
volatile toxic organic pollutants associated with the CWA (as SAMPLE PREPARATION Samples containing less than 1%
amended 1987); the RCRA (as amended 1986); the CERCLA solids are analyzed directly as aqueous samples. Samples con-
(as amended 1986); and other compounds amenable to purge- taining 1% solids or greater are analyzed as solid samples uti-
and-trap gas chromatography-mass spectrometry (GC/MS). lizing one of two methods, depending on the levels of
If the solids content is less than 1%, stable isotopically-labeled pollutants, in the sample. Samples containing 1% solids or
analogs of the compounds of interest are added to a 5-mL greater, and low to moderate levels of pollutants are analyzed
sample and the sample is purged with an inert gas at 20–25 C by purging a known weight of sample added to 5 mL of reagent
in a chamber designed for soil or water samples. If the solids water. Samples containing 1% solids or greater, and high levels
content is greater than 1%, 5 mL of reagent water and the of pollutants, are extracted with methanol, and an aliquot of
labeled compounds are added to a 5-g aliquot of sample and the methanol extract is added to reagent water and purged.
the mixture is purged at 40C. Compounds that will not purge QUALITY CONTROL A field blank prepared from reagent
at 20–25C or at 40C are purged at 78–85C. In the purging water and carried through the sampling and handling protocol
process, the volatile compounds are transferred from the aque- may serve as a check on contamination from shipment and
ous phase into the gaseous phase where they are passed into a storage.
trap is backflushed and heated rapidly to desorb the com- The analyst is permitted to modify this method to improve
pounds into a GC. The compounds are separated by the GC separations or lower the costs of measurements, provided all
and detected by a MS. The labeled compounds serve to correct performance specifications are met. Analyses of blanks are
the variability of the analytical technique. required. When results of spikes indicate atypical method per-
INTERFERENCES Impurities in the purge gas, organic com- performance within acceptable limits. Analyze two sets of four
pounds outgassing from the plumbing upstream of the trap, 5-mL aliquots (8 aliquots total) of the aqueous performance
and solvent vapors in the lab account for most problems. Sam- standard. Spike all samples with labeled compounds to assess
ples can be contaminated by diffusion of volatile organic com- method performance on the sample matrix. Compute the per-
pounds (particularly methylene chloride) through the bottle cent recovery of the labeled compounds using the internal stan-
seal during shipment and storage. Contamination by carryover dard method. Compare the percent recovery for each
can occur when high-level and low-level samples are analyzed compound with the corresponding labeled compound recov-
INSTRUMENTATION Major equipment includes a GC with and spiked samples may be required to determine the accuracy
linear temperature programming and a glass jet separator as of the analysis when the internal method is used.
Column: 2.8 m 2 mm I.D. glass, packed with 1% SP-1000 on EPA Industrial Technology Division, Washington, DC, EPA
Carbopak B, 60/80 mesh, or equivalent. Method 1624, Rev. C, June 1989 (contact W.A. Telliard, U.S.
filter cake or compost (high solids). Iodomethane EPA Method 8240
CAS #74-88-4
deviation was not listed. MATRIX Nearly all types of sample matarices, regardless of
Labeled and native compound accuracy (in g/L) as average water content, can be analyzed using this method. This includes
recovery was not listed. groundwater, aqueous sludges, caustic liquors, acid liquors, waste
Acceptance criteria are at 20 g/L for this compound. solvents, oily wastes, mousses, tars, fibrous wastes, polymetric

emulsions, filter cakes, spent carbons, spent catalysts, soils, and MULTIPLICATION FACTORS FOR OTHER MATRICES
sediments. Other Matrices Factor (a)
organic compounds outgassing from the plumbing ahead of if residual chlorine is present, collect sample in a 40-oz. soil
sequentially. Whenever an unusually concentrated sample is Soils or sediments, and sludges — Use an 8-oz. widemouth
refrigerator.
EQL in groundwater in g/L was not listed. Sediments, soils, and waste samples — All samples of this type
EQL in low soil or sediment in g/kg was not listed. should be screened by GC analysis using a headspace method

Iron EPA Method 6010
CAS #7439-89-6
row metal spatula. Weigh the amount of the sample into a tared TITLE Inductively Coupled Plasma-Atomic Emission Spec-
purge device. Add the spiked water to the purge device, which troscopy
device to the purge-and-trap system. MATRIX This method is applicable to the determination of
trace elements, including metals, in groundwater, soils, sludges,
High-concentration method — This method is based on sediments, and other solid wastes. All matrices require diges-
tion prior to analysis. The method of standard addition must
be used for the analysis of all sample digests unless either serial
dilution or matrix spike addition demonstrates it is not
required.
containing surrogate and internal standards. This is purged at METHOD SUMMARY Method 6010 covers 25 elements
ambient temperature. All samples with an expected concentra- using ICP analysis. It measures element-emitted light by optical
tion of >1.0 mg/kg should be analyzed by this method. spectrometry. Samples, following an appropriate acid diges-
tion, are nebulized and the resulting aerosol is transported to
Mix the contents of the sample container with a narrow metal
the plasma torch. Element-specific atomic line emission spectra
are produced by a radio-frequency inductively coupled plasma.
20-mL vial. For waste that is soluble in methanol, tetraglyme, INTERFERENCES Interferences may be categorized as spec-
or PEG, weigh 1 g (wet weight) into a tared scintillation vial tral or non-spectral. Spectral interferences are caused by over-
or culture tube or a 10-mL volumetric flask. Quickly add lap of a spectral line from another element, unresolved overlap
9.0 mL of appropriate solvent then add 1.0 mL of a surrogate of molecular band spectra, background contribution from con-
spiking solution to the vial, cap it, and shake it for 2 min. tinuous or recombination phenomenon, and stray light from
the line emission of high concentration elements. Non-spectral
METHANOL EXTRACT REQUIRED FOR ANALYSIS
interferences include physical and chemical interferences. Phys-
OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
ical interferences are effects associated with the sample nebu-
Approximate Volume of lization and transport processes. Changes in viscosity and
Concentration Range Methanol Extract (a) surface tension can cause significant inaccuracies. Chemical
500–10,000 g/kg 100 L interferences include molecular compound formation, ioniza-
1,000–20,000 g/kg 50 L tion effects, and solute vaporization effects. Normally these
5,000–100,000 g/kg 10 L effects are not significant and can be minimized by careful
25,000–500,000 g/kg 100 L of 1/50 dilution (b) selection of operating conditions. Chemical interferences are
highly dependent on matrix type and the specific analyte element.
Calculate appropriate dilution factor for concentrations
exceeding this table. INSTRUMENTATION An inductively coupled argon plasma
emission spectrometer (ICP) capable of background correction
(a) The volume of methanol added to 5 mL of water being purged is required.
volume of methanol is necessary to maintain a volume of 100 L PRECISION & ACCURACY Detection limits, sensitivity, and
added to the syringe. optimum ranges of the metals will vary with the matrices and
(b) Dilute an aliquot of the methanol extract and then take 100 L model of the spectrometer. In a single lab evaluation, seven
for analysis. wastes were analyzed for 22 elements. The mean percent rela-
tive standard deviation from triplicate analyses for all elements
QUALITY CONTROL Demonstrate, through the analysis of and wastes was 9 2%. The mean percent recovery of spiked
a reagent water blank, that interferences from the analytical elements for all wastes was 93 6%. Spike levels ranged from
system, glassware, and reagents are under control. Blank sam- 100 g/L to 100 mg/L. The wastes included sludges and indus-
ples should be carried through all stages of the sample prepa- trial wastewaters.
to 20 samples), a reagent blank, matrix spike, and matrix spike Estimated instrument detection limit in g/L is 7.
duplicate must be analyzed (the frequency of the spikes may Spiked concentration in g/L is 20.
be different for different monitoring programs). The blank and Mean reported value in g/L is 19.
spiked samples must be carried through all stages of the sample Precision as RSD % is 15.
preparation and measurement steps. QC samples mentioned SAMPLING METHOD Samples should be collected in boro-
in the section on Interferences will also be needed as appropri- silicate glass, linear polyethylene, polypropylene, or Teflon®
ate to those situations. bottles that have been prewashed with detergent and tap water,
REFERENCE Test Methods for Evaluating Solid Waste (SW- and rinsed with 1:1 nitric acid and tap water or 1:1 hydrochloric
846). U.S. EPA. 1983. Method 8240B, Rev. 2, Nov. 1990. Office acid and tap water. Collect at least 2 g of solids and 200 mL of
of Solid Wastes, Washington, DC. aqueous samples.

SAMPLE PRESERVATION Add nitric acid to make the sam- on method performance must be demonstrated: when appro-
ples pH <2. priate, there should be at least one matrix spike and either one
matrix duplicate or one matrix spike duplicate per analytical
MHT The maximum holding time for properly preserved
batch. The bias and precision of the method, as well as the
samples is 6 months.
method detection limit for each specific matrix type, must be
SAMPLE PREPARATION Preliminary treatment of most measured.
matrices is necessary because of the complexity and variability
of sample matrices. Water samples that have been prefiltered Dilute and reanalyze samples that are more concentrated than
and acidified will not need acid digestion. Methods for acid the linear calibration limit. Employ a minimum of one reagent
digestion of waters for total recoverable or dissolved metals, blank per sample batch to determine if contamination or any
acid digestions of aqueous samples and extracts for total metals, memory effects are occurring. Whenever a new or unusual
and acid digestion of sediments, sludges, and soils are summa- sample matrix is encountered, perform either a serial dilution
rized below. test or a matrix spike addition test to ensure that neither pos-
itive or negative interferences are operating on any of the ana-
Total recoverable or dissolved metals in water — To prepare lyte elements. Check the instrument standardization by
surface and groundwater samples for determination of total verifying calibration every 10 samples using a calibration blank
recoverable and dissolved metals, a 100-mL aliquot of well- and a check standard.
mixed sample is acidified with concentrated nitric acid and
concentrated hydrochloric acid, then heated until the volume REFERENCE Test Methods for Evaluating Solid Waste (SW-
is reduced to 15–20 mL.Adjust the final volume to 100 mLwith 846). U.S. EPA. 1983. Method 6010, Rev. 0, Sept. 1986. Office
reagent water. of Solid Wastes, Washington, DC.
Total metals in aqueous samples, soil and sediment extracts —
To prepare aqueous samples, soil and sediment extracts, and
wastes that contain suspended solids, a 100-mL aliquot is made Iron EPA Method 200.7
acidic with concentrated nitric acid and the solution is evapo- CAS #7439-89-6
rated to about 5 mL on a hot plate. Continue heating and
adding additional acid until sample digestion is complete, TITLE Inductively Coupled Plasma (ICP)
which is usually indicated when the digestate is light in color
MATRIX Dissolved, suspended, or total element in drinking
or does not change in appearance. Evaporate the solution to
and surface waters and in domestic and industrial wastewaters.
about 3 mL and cool it and add a small quantity of 1:1 hydro-
chloric acid (10 mL/100 mL of final solution). Cover the beaker APPLICATION The method covers the determination of 25
and reflux for 15 min. Wash down the beaker walls and filters metals. Dissolved elements are determined in filtered and acid-
or centrifuge the sample to remove silicates and other insoluble ified samples after appropriate digestion (which increases dis-
material. Filter the sample and adjust the final volume to solved solids). Its primary advantage is that ICP instruments
100 mL with reagent water and the final acid concentration to allow simultaneous or rapid sequential determination of many
10%. elements in a short time. Samples are first nebulized and the
Sediments, sludges, and soils — To prepare sediments, sludges aerosol is transported to a plasma torch in which element spe-
and soil samples, transfer 1–2 g to a conical beaker and add cific atomic line emission spectra are produced by a radio fre-
10 mL of 1:1 nitric acid, mix the slurry, and cover it with a quency inductively coupled plasma. Background correction is
watch glass. Heat the sample and reflux for 10–15 min without required for trace element detection except in the case of line
boiling. Allow it to cool, then add 5 mL of concentrated nitric broadning.
acid and reflux for 30 min. Repeat last step and then allow the INTERFERENCES There are spectral, physical, and chemical
solution to evaporate to 5 mL without boiling. Cool and add interferences. The primary disadvantage of ICP instruments is
2 mL of water and 3 mL of 30% hydrogen peroxide. Cover and background radiation from other elements and the plasma
place the beaker on the hot plate. Heat and add 30% hydrogen gases (spectral interferences). Changes in sample viscosity and
peroxide in 1-mL aliquots with warming until the effervescence surface tension with samples containing high dissolved solids
is minimal but do not add more than a total of 10 mL of 30% (especially those exceeding 1500 mg/L) or high acid concentra-
hydrogen peroxide. If the sample is being prepared for the
tions can cause physical interferences. Ionization effects, solute
analysis of Ag, Al, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg,
vaporization and molecular compound formation can cause
Mn, Mo, Na, Ni, Os, Pb, Se, Tl, V, and Zn, then add 5 mL of
chemical interferences. Manganese can cause interference at the
concentrated hydrochloric acid and 10 mL of water and return
100 mg/L level.
the covered beaker to a hot plate for 15 min of additional
refluxing without boiling. Dilute the sample to a 100 mL vol- INSTRUMENTATION Inductively coupled argon plasma
ume with water after cooling and filter or centrifuge to remove emission spectroscopy. 259.940 nm wavelength
particulates.
RANGE Not listed.
QUALITY CONTROL Laboratory control samples must be
analyzed for each analytical method. A method blank should MDL 7 g/L.
be analyzed with each batch of samples. The effect of the matrix PRECISION SD = 3.0% Mean at true value 600 g/L.

ACCURACY Mean recovery = 93% 6% of spiked elements tube. Lack of reproducibility or significant change in the signal
for all wastes. for the standard indicates tube should be replaced.
SAMPLING METHOD Wash sample container with deter- REFERENCE EPA Methods for the Chemical Analysis of
gent and tap water, rinse with 1 + 1 nitric acid and tap water, Water and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979.
then rinse with 1 + 1 hydrochloric acid and tap water, then
rinse with deionized, distilled water in that order. Perform any
filtration or acid preservation steps when the sample is col-
lected or as soon as possible thereafter. Iron EPA Method 315 B
CAS #7439-89-6
STABILITY Cool samples to 4C.
MHT 24 h. TITLE Phenanthroline Method
QUALITY CONTROL Mixed calibration standards, an MATRIX Natural or treated waters total dissolved ferrous
instrument check standard, and an interference check solution APPLICATION Iron is brought into solution, reduced to fer-
are used in addition to a quality control sample. The quality rous state by boiling with acid and hydroxylamine and treated
control sample should be prepared in the same acid matrix as with 1,10-phenanthroline at pH 3.2 to 3.3. Three molecules of
the calibration standards at 10 times the instrumental detection phenanthroline chelate each atom of ferrous iron to form an
limits and in accordance with the instructions provided by the orange-red complex.
supplier. Furthermore, two types of blanks are required: a cal-
ibration blank and a reagent blank. INTERFERENCES Strong oxidizing agents, cyanide, nitrite,
and phosphates (particularly polyphosphates), chromium,
REFERENCE Method 200.7, U.S. EPA, EMSL-Cincinnati, zinc, cobalt, copper, and nickel interfere. Bismuth, cadmium,
OH, Nov. 1980
mercury, molybdate and silver precipitate phenanthroline.
INSTRUMENTATION Spectro (or filter) photometer with
green filter. 510 nm. Light path > 1 cm.
Iron EPA Method 236.2
CAS #7439-89-6 RANGE Not listed.
MDL 10 g/L.
TITLE Metals (Total, Dissolved, Suspended) AA Furnace
Technique PRECISION SD = 25.5% at 300 g Fe/L (aqueous mixture
of 8 metals)
MATRIX Drinking, surface and saline, waters. Wastewater
ACCURACY Relative error = 13.3% at 300 g Fe/L (aqueous
APPLICATION Date issued 1978. A representative sample
aliquot is placed in a graphite tube in furnace, evaporated to mix of 8 metals)
dryness,charred and atomized. Radiation from excited element SAMPLING METHOD Plastic or glass. Clean with acid.
is passed through vapor and radiation intensity decreases pro- Rinse with distilled water.
portional to amount of Fe in vapor.
STABILITY HNO3 to pH <2.
INTERFERENCES Furnace technique subject to chemical
and matrix interferences. Furnace gases may have molecular MHT 6 months.
absorption bands enclosing analytical wavelength. Smoke-pro- QUALITY CONTROL Use reagents low in iron. Use iron-free
ducing sample matrix can interfere. If Fe isn’t volitalized and distilled water in preparing standards and reagent solutions.
removed from furnace, memory effects occur. Store reagents in glass stoppered bottles. Calculate ferric iron
INSTRUMENTATION AAS. Iron (Fe) hollow cathode lamp by subtracting ferrous iron from total iron. Don’t expose
or EDL. Graphite furnace. Pipets. phenanthroline solutions to sunlight.
RANGE 5–100 g/L. REFERENCE Standard Methods for the Examination of
Water and Waste Water, 16th ed., Page 215, 1985.
MDL 1 g/L.
PRECISION Not listed.
ACCURACY Not listed. Iron EPA Method 7380
CAS #7439-89-6
SAMPLING METHOD Prewashed plastic or glass containers.
STABILITY HNO3 to pH <2. TITLE Atomic Absorption (AA) Direct Aspiration
MHT 6 months. MATRIX Drinking, surface, and saline waters, wastewater
QUALITY CONTROL A check standard should be run APPLICATION Sample is aspirated and atomized in a flame.
approximately after every 10 sample injections. Standards are A light beam from an Fe hollow cathode lamp is directed
run in part to monitor the life and performance of the graphite through the flame into a monochromator and onto a detector.

Since wavelength of light beam is specific for Fe, light energy PRECISION Not listed.
absorbed by detector is measure of iron.
ACCURACY Not listed.
INTERFERENCES The most troublesomee type is chemical,
SAMPLING METHOD Use glass or plastic containers. Col-
caused by lack of absorption of atoms bound in molecular
lect 200 g of solids and 600 mL of liquid samples.
combination in the flame. High dissolved solids in sample may
result in nonatomic absorbance interference. Iron is a universal STABILITY Cool solid samples to 4C and analyze as soon
contaminant; avoid contamination. as possible.Add nitric acid to liquid samples to pH <2.
INSTRUMENTATION Atomic absorption spectrometer. MHT 6 months.
Iron hollow cathode lamp. [248.3 nm wavelength(primary)]
QUALITY CONTROL At least one duplicate and one spike
RANGE 0.3–5 mg/L. sample should be run every 20 samples, or with each matrix
type to verify method precision. If 20 or more samples are run
MDL 0.03 mg/L
a day, run a standard (at or near mid-range) every 10 samples.
PRECISION Standard deviation = 173 g/L at 840 g/L
REFERENCE Method 7381, SW-846, 3rd ed., (Included as
(true value) 82 labs
Rev. 0, Dec. 1987)
ACCURACY As bias = +1.8% at 840 g/L (true value) 82 labs
lect 200 g of solids and 600 mL of liquid samples. Isobutyl alcohol EPA Method 1624
CAS #78-83-1
STABILITY Cool solid samples to 4C and analyze as soon
as possible. Add nitric acid to liquid samples to pH <2.
TITLE Volatile Organic Compounds by Isotope Dilution
MHT 6 months. GC/MS
QUALITY CONTROL At least one duplicate and one spike MATRIX Compounds may be determined in waters, soils,
sample should be run every 20 samples or with each matrix and municipal sludges by this method.
type to verify precision of the method. For 20 or more samples
METHOD SUMMARY This method is used to determine 58
per day, verify working standard curve. Run an additional stan-
volatile toxic organic pollutants associated with the CWA (as
dard at or near mid-range every 10 samples.
amended 1987); the RCRA (as amended 1986); the CERCLA
REFERENCE Method 7380, SW-846, 3rd ed., Nov.1986. (as amended 1986); and other compounds amenable to purge-
and-trap gas chromatography-mass spectrometry (GC/MS).
If the solids content is less than 1%, stable isotopically-labeled
Iron EPA Method 7381 analogs of the compounds of interest are added to a 5-mL
CAS #7439-89-6 sample and the sample is purged with an inert gas at 20–25 C
in a chamber designed for soil or water samples. If the solids
TITLE Atomic Absorption (AA) Furnace Technique content is greater than 1%, 5 mL of reagent water and the
MATRIX Wastes, mobility procedure extracts, soils and labeled compounds are added to a 5-g aliquot of sample and
groundwater the mixture is purged at 40C. Compounds that will not purge
at 20–25C or at 40C are purged at 78–85C. In the purging
APPLICATION Aqueous samples, EP extracts, industrial process, the volatile compounds are transferred from the aque-
wastes, soils, sludges, sediments, and solid wastes require diges- ous phase into the gaseous phase where they are passed into a
tion before analysis.An aliquot of sample is placed in the graph- sorbent column, and trapped. After purging is completed, the
ite tube in the furnace and slowly evaporated, charred and trap is backflushed and heated rapidly to desorb the com-
atomized. Absorption of lamp radiation during atomization is pounds into a GC. The compounds are separated by the GC
proportional to iron concentration. and detected by a MS. The labeled compounds serve to correct
INTERFERENCES The furnace technique is subject to chem- the variability of the analytical technique.
ical interferences. Composition of sample matrix can have INTERFERENCES Impurities in the purge gas, organic com-
major effect on analysis. Modify matrix to remove interfer- pounds outgassing from the plumbing upstream of the trap,
ences. Iron is a universal contaminant. Use great care to avoid and solvent vapors in the lab account for most problems. Sam-
contamination. ples can be contaminated by diffusion of volatile organic com-
INSTRUMENTATION Atomic absorption spectrometer. pounds (particularly methylene chloride) through the bottle
Iron hollow cathode lamp or electrodeless discharge lamp. seal during shipment and storage. Contamination by carryover
Graphite furnace. Strip-chart recorder can occur when high-level and low-level samples are analyzed
sequentially. When an unusually concentrated sample is
RANGE 5–100 g/L.
encountered, follow it by analysis of a reagent water blank to
MDL 1 g/L (248.3 nm wavelength) check for carryover.

INSTRUMENTATION Major equipment includes a GC with lected to determine the precision of the sampling technique,
linear temperature programming and a glass jet separator as and spiked samples may be required to determine the accuracy
the MS interface, a MS with 70 eV electron impact ionization, of the analysis when the internal method is used.
and a data system to collect and record response factors.
REFERENCE Volatile Organic Compounds by Isotope Dilu-
Column: 2.8 m 2 mm I.D. glass, packed with 1% SP-1000 on tion GC/MS. Office of Water Regulation and Standards, U.S.
Carbopak B, 60/80 mesh, or equivalent. EPA Industrial Technology Division, Washington, DC, EPA
Method 1624, Rev. C, June 1989 (contact W.A. Telliard, U.S.
SW, Washington, DC, 20460. Phone: 202-382-7131).
Isobutyl alcohol EPA Method 8240
CAS #78-83-1
deviation was not listed.
Labeled and native compound accuracy (in g/L) as average MATRIX Nearly all types of sample matarices, regardless of
recovery was not listed. water content, can be analyzed using this method. This includes
Acceptance criteria are at 20 g/L for this compound. groundwater, aqueous sludges, caustic liquors, acid liquors,
soils, and sediments.
air bubbles are entrapped. Samples are maintained at 0 to 4 C METHOD SUMMARY Method 8240B covers 80 volatile
from the time of collection until analysis. If an aqueous sample organic compounds that are introduced into a gas chromato-
contains residual chlorine, add sodium thiosulfate preservative graph by the purge-and-trap method or by direct injection (in
(10 mg/40 mL) to the empty sample bottles just prior to ship- limited applications). For the purge-and-trap method an inert
ment to the sample site. All samples must be analyzed within gas (zero grade nitrogen or helium) is bubbled through a 5-mL
14 days of collection. solution at ambient temperature. Purged sample components
SAMPLE PREPARATION Samples containing less than 1%
solids are analyzed directly as aqueous samples. Samples con-
taining 1% solids or greater are analyzed as solid samples uti-
lizing one of two methods, depending on the levels of INTERFERENCES Impurities in the purge gas and from
pollutants, in the sample. Samples containing 1% solids or organic compounds outgassing from the plumbing ahead of
greater, and low to moderate levels of pollutants are analyzed the trap account for many contamination problems. Interfer-
by purging a known weight of sample added to 5 mL of reagent ences purged or coextracted from the samples will vary con-
water. Samples containing 1% solids or greater, and high levels siderably from source to source. Cross-contamination can
of pollutants, are extracted with methanol, and an aliquot of occur whenever high-level and low-level samples are analyzed
the methanol extract is added to reagent water and purged. sequentially. Whenever an unusually concentrated sample is
QUALITY CONTROL A field blank prepared from reagent
water and carried through the sampling and handling protocol
can be contaminated by diffusion of volatile organics (partic-
may serve as a check on contamination from shipment and
ularly methylene chloride and fluorocarbons) through the sep-
storage.
The analyst is permitted to modify this method to improve blank can serve as a check on such contamination. The lab
separations or lower the costs of measurements, provided all where volatile analysis is performed and also the refrigerated
performance specifications are met. Analyses of blanks are storage area should be completely free of solvents.
trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
performance within acceptable limits. Analyze two sets of four
5-mL aliquots (8 aliquots total) of the aqueous performance
(60/80 mesh) is required.Also needed is a 5-mL purging device,
standard. Spike all samples with labeled compounds to assess
a sorbent trap, and a thermal desorption apparatus.
method performance on the sample matrix. Compute the per-
cent recovery of the labeled compounds using the internal stan- PRECISION & ACCURACY This method is reported to have
dard method. Compare the percent recovery for each been tested by 15 laboratories using organic-free reagent water,
compound with the corresponding labeled compound recov- drinking water, surface water, and industrial wastewaters (not
ery. Reagent water blanks are analyzed to demonstrate freedom specified) fortified at six concentrations over the range 5–
from carryover contamination. Field replicates may be col- 600 g/L.

EQL in groundwater in g/L was 100. Sediments, soils, and waste samples — All samples of this type
EQL in low soil or sediment in g/kg was 100. should be screened by GC analysis using a headspace method
Other Matrices Factor (a) 1 mg/kg. Mix the contents of the sample container with a nar-
SAMPLING METHOD is either extracted or diluted, depending on its solubility in
Liquid samples — Use a 40-mL glass screw-cap VOA vial with methanol. Wastes that are insoluble in methanol are diluted
a Teflon®-faced silicone septum that has been prewashed, with reagent tetraglyme or possibly polyethylene glycol (PEG).
rinsed with distilled deionized water, and oven dried. However, An aliquot of the extract is added to organic-free reagent water
if residual chlorine is present, collect sample in a 40-oz. soil containing surrogate and internal standards. This is purged at
cate and seal them in separate plastic bags.
SAMPLE PRESERVATION
Concentration Range Methanol Extract (a)
Soils or sediments, and sludges — Cool samples to 4C and
1,000–20,000 g/kg 50 L
sample collection. 25,000–500,000 g/kg 100 L of 1/50 dilution (b)
SAMPLE PREPARATION Calculate appropriate dilution factor for concentrations
Liquid samples — Remove the plunger from a 5-mL syringe exceeding this table.

volume of methanol is necessary to maintain a volume of 100 L capillary column. A continuous liquid-liquid extractor
added to the syringe. equipped with Teflon® or glass connection joints and stopcocks
(b) Dilute an aliquot of the methanol extract and then take 100 L requiring no lubrication, a K-D concentrating apparatus, water
for analysis. bath, and an ultrasonic disrupter with a minimum power of
QUALITY CONTROL Demonstrate, through the analysis of 300 W and with pulsing capability are also required.
a reagent water blank, that interferences from the analytical PRECISION & ACCURACY The estimated quantitation
system, glassware, and reagents are under control. Blank sam- limit (EQL) of Method 8270B for determining an individual
ples should be carried through all stages of the sample prepa- compound is approximately 1 mg/kg (wet weight) for soil or
ration and measurement steps. For each analytical batch (up sediment samples, 1–200 mg/kg for wastes (dependent on
spiked samples must be carried through all stages of the sample extracts that require dilution to avoid saturation of the detector.
preparation and measurement steps. QC samples mentioned The EQL(b) for groundwater in g/L is 20.
in the section on Interferences will also be needed as appropri- The EQL (a, b) for low concentrations in soil and sediment
ate to those situations. in g/kg is not determined.
REFERENCE Test Methods for Evaluating Solid Waste (SW- Accuracy as g/L is not listed.
846). U.S. EPA. 1983. Method 8240B, Rev. 2, Nov. 1990. Office Overall precision in g/L is not listed.
of Solid Wastes, Washington, DC. (a) EQLs listed for soil/sediment are based on wet weight. Nor-
Isodrin EPA Method 8270 This calculation is based on a 30-g sample and gel perme-
lakes, etc.
tion of the sample into the GC/MS system may be appropriate, (a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
(or isopropanol).
required. The GC column used is a 30 m 0.25 mm I.D. (or MHT Liquid samples must be extracted within 7 days and the
0.32 mm I.D.) 1um film thickness silicone-coated fused silica extracts analyzed within 40 days. Soils, sediments, or sludges may

be stored for a maximum of 14 days and the extracts analyzed must be inspected for malfunctions and corrections must be
within 40 days. made, as appropriate.
concentrator.
Isophorone EPA Method 1625
CAS #78-59-1
tion GC/MS
sample in each analytical batch selected for spiking, add 1.0 mL MATRIX The compounds may be determined in waters,
of a matrix spiking standard. For base/neutral acid analysis, the soils, and municipal sludges by this method.
in the extract to be analyzed (assuming a 1- L injection). CERCLA (as amended 1986); and other compounds amenable
Immediately add a 100-mL mixture of 1:1 methylene chlo- to extraction and analysis by capillary column gas chromatog-
ride:acetone and extract the sample ultrasonically for 3 min raphy-mass spectrometry (GC/MS).
used for tuning the GC/MS system each 12-h shift. A system If the solids content is 30% or less, the sample is diluted to 1%
performance check also must be made during every 12-h shift. solids with reagent water, homogenized ultrasonically, and
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- extracted at pH 12–13, then at pH <2 with methylene chloride
rophenol, and benzidine is required to verify injection port using continuous extraction techniques. If the solids content is
inertness and GC column performance. A calibration standard greater than 30%, the sample is extracted using ultrasonic

to be free from interferences under the conditions of analysis Ultrasonic extraction of high solids samples — Add anhy-
by running method blanks initially and with each sample lot drous sodium sulfate to the sample and QC aliquot(s).
(sample started through the extraction process on a given 8-h Add acetone:methylene chloride (1:1) to the sample and
shift, to a maximum of 20). Specific selection of reagents and mix thoroughly
purification of solvents by distillation in all glass systems may
be required. Glassware and, where possible, reagents are Concentrate extracts using a K-D apparatus.
cleaned by solvent rinse and baking at 450C for 1-h minimum. QUALITY CONTROL The analyst is permitted to modify
Interferences coextracted from samples will vary considerably this method to improve separations or lower the costs of mea-
from source to source, depending on the diversity of the site surements, provided all performance specifications are met.
being sampled. Analyses of blanks are required to demonstrate freedom from
INSTRUMENTATION Major instrumentation includes a GC contamination. When results of spikes indicate atypical
with a splitless or on-column injection port for capillary col- method performance for samples, the samples are diluted to
umn, a MS with 70 eV electron impact ionization, and a data bring method performance within acceptable limits.
system to collect and record MS data, and process it. A K-D For low solids (aqueous samples), extract, concentrate, and
apparatus is used to concentrate extracts. analyze two sets of four 1-L aliquots (8 aliquots total) of the
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1% precision and recovery standard. For high solids samples, two
vinyl silicone bonded phased fused silica capillary column. sets of four 30-g aliquots of the high solids reference matrix
are used.
method are usually dependent on the level of interferences Spike all samples with labeled compounds to assess method
rather than instrumental limitations. The limits typify the min- performance. Compute percent recovery of the labeled com-
imum quantities that can be detected with no interferences pounds using the internal standard method. Compare the
present. labeled compound recovery for each compound with the cor-
responding labeled compound recovery.
minimum level at which the analytical system shall give recog- Reagent water and high solids reference matrix blanks are ana-
nizable mass spectra (background corrected) and acceptable lyzed to demonstrate freedom from contamination. Extract
calibration points. and concentrate a 1-L reagent water blank or a high solids
The MDL (in g/kg) in low solids was 8 and in high solids was through the extraction process on the same 8-h shift, to a
5; these were determined in digested sludge (low solids) and in maximum of 20 samples).
The labeled and native compound initial precision as standard the sampling technique, and spiked samples may be required
deviation (in g/L) was 25. to determine the accuracy of the analysis when the internal
The labeled and native compound initial accuracy as average standard method is used.
SAMPLE COLLECTION, PRESERVATION & HANDLING Dilution GC/MS. Office of Water Regulation and Standards,
Collect samples in glass containers. Aqueous samples which U.S. EPA Industrial Technology Division, Washington, DC,
flow freely are collected in refrigerated bottles using automatic EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
and analyze all extracts within 40 days of extraction. Isophorone EPA Method 625
CAS #78-59-1
less are extracted directly using continuous liquid-liquid TITLE Base/Neutrals and Acids, U.S. EPA Method 625
diluted to the 1% level with reagent water and extracted using MATRIX This methods covers municipal and industrial
continuous liquid-liquid extraction techniques. Samples con- wastewaters.
techniques.
Base/neutral extraction — Adjust the pH of the waters in the and again at a pH less than 2 using a separatory funnel or a
extractors to 12–13 with 6 N NaOH. Extract with methylene continuous extractor. The methylene chloride extract is dried,
chloride for 24–48 h. concentrated to a volume of 1 mL, and analyzed by GC/MS.
Acid extraction — Adjust the pH of the waters in the extractors Qualitative identification of the parameters in the extract is per-
to 2 or less using 6 N sulfuric acid. Extract with methylene formed using the retention time and the relative abundance of
chloride for 24–48 h. three characteristic masses (m/z). Qualitative analysis is

performed using either external or internal standard techniques extractor. Dry the extracts separately through a column of
phenols. The packed gas chromatographic columns recom- with this method. Before processing any samples, the analyst
mended for the basic fraction may not exhibit sufficient reso- must analyze a reagent water blank to demonstrate that inter-
lution for some analytes. ferences from the analytical system and glassware are under
Column for base/neutrals: 1.8 m long  2 mm I.D. glass, contains each parameter of interest at a concentration of
or equivalent.
Column for acids: 1.8 m long 2 mm I.D. glass, packed with
average percent recovery and the standard deviation of the
surrogate compound.
and matrix effects. This method was tested by 15 laboratories
Isophorone EPA Method 8270
ments) was 63.3. TITLE Semivolatile Organic Compounds by GC/MS
The range (in g/L) for average recovery for 4 measurements MATRIX This method is used to determine the concentra-
was 46.6–180.2. tion of semivolatile organic compounds in extracts prepared
C was 1.12C + 1.41. lakes, etc.
tion of measurements at an average concentration found at METHOD SUMMARY This method covers 259 semivolatile
X was 0.27X + 0.77. organic compounds. In very limited applications direct injec-
Overall precision (in g/L) as expected interlaboratory stan- tion of the sample into the GC/MS system may be appropriate,
dard deviation of measurements in an average concentra- but this results in very high detection limits (approximately
tion found at X was 0.33X + 0.26. 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
SAMPLE PREPARATION Adjust the pH to >11 with sodium concentrating the extract to 1 mL it is spiked with 10 L of an
hydroxide and serially extract in a separatory funnel with meth- internal standard solution just prior to analysis by GC/MS. The
ylene chloride or else in a continuous extractor. Next, adjust volume injected should contain about 100 ng of base/neutral
the pH to <2 with sulfuric acid and serially extract in a sepa- and 200 ng of acid surrogates (for a 1-L injection). Analysis
ratory funnel with methylene chloride or else in a continuous is performed by GC/MS using a capillary GC column.

in g/kg is 660. hydroxide and extract it with methylene chloride again for
Accuracy as g/L is 1.12C + 1.14.
Overall precision in g/L is 0.33X + 0.26.
concentrator.
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor]. sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
Soils, sediments, or sludges — Use an 8-oz. widemouth glass including all required surrogates, must be performed every 12 h
with a screw-top Teflon®-lined cover that has been prewashed during analysis. After the system performance check is met,
with detergent and rinsed with distilled water and methanol calibration check compounds (CCCs) are used to check the
(or isopropanol). validity of the initial calibration.

The internal standard responses and retention times in the PQL FACTORS FOR MULTIPLYING  FID MDL VALUE
calibration check standard must be evaluated immediately after Matrix Multiplication Factor
standard changes by more than 30 seconds from the last check Groundwater 10
any of the internal standards changes by a factor of two from PRECISION 0.46X + 0.31 g/L (overall precision).
made, as appropriate. SAMPLING METHOD Use 8-oz. widemouth glass bottles
Demonstrate, through the analysis of a reagent water blank, sediments, and sludges. Use 1 or 2½ gallon amber glass bottles
that interferences from the analytical system, glassware, and with Teflon®-lined caps for liquid (water) samples.
ried through all stages of the sample preparation and measure- STABILITY Cool soil, sediment, sludge, and liquid samples
ment steps. For each analytical batch (up to 20 samples), a to 4C. If residual chlorine is present in liquid samples add
reagent blank, matrix spike, and matrix spike duplicate/dupli- 3 mL of 10% sodium thiosulfate per gallon of sample and cool
cate must be analyzed (the frequency of the spikes may be to 4C.
different for different monitoring programs). The blank and MHT 14 days for concentrated waste, soil, sediment, or
spiked samples must be carried through all stages of the sample sludge; 7 days for liquid samples; all extracts must be analyzed
preparation and measurement steps. A QC reference sample within 40 days.
100 mg/L in methanol is required. QUALITY CONTROL A quality control check sample con-
centrate containing each analyte of interest is required. The QC
REFERENCE Test Methods for Evaluating Solid Waste (SW- check sample concentrate may be prepared from pure standard
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office materials or purchased as certified solutions Use appropriate
of Solid Waste, Washington, DC. trip, matrix, control site, method, reagent, and solvent blanks.
Internal, surrogate, and five concentration level calibration
standards are used. The QC check sample concentrate should
Isophorone EPA Method 8090 contain this compound at 100 g/mL in acetone.
CAS #78-59-1 REFERENCE Method 8090, SW-846, 3rd ed., Nov.1986.
TITLE Nitroaromatics & Cyclic Ketones

MATRIX Groundwater, soils, sludges, water miscible liquid Isopropylbenzene EPA Method 502
wastes, and non-water miscible wastes. CAS #98-82-8
APPLICATION This method is used for the analysis of var-
ious nitroaromatic and cyclic ketone compounds. Samples are TITLE Volatile Organic Compounds in Water By Purge and
extracted, concentrated, and analyzed using direct injection of Trap Capillary Column Gas Chromatography with Photoion-
both neat and diluted organic liquids. ization and Electrolytic Conductivity Detectors in Series. U.S.
EPA Method 502.2, Rev. 2.0, 1989.
Dinitrotoluenes are determined using ECD and the other com-
pounds amenable to this method are determined using FID. MATRIX Drinking water and raw source water. The latter
The method provides an optional GC column which is used
for analyte confirmation and that may help resolve analytes METHOD SUMMARY This method covers 60 volatile
from interferences. organic compounds that contain halogen atoms and/or that
are aromatic. An inert gas (zero grade nitrogen or helium) is
INTERFERENCES Solvents, reagents, and glassware may
bubbled through a 25-mL or a 5-mL water sample (depending
on the expected concentration of the analytes). Purged sample
components are trapped in a tube of sorbent materials. When
INSTRUMENTATION GC capable of on-column injections purging is complete, the sorbent tube is heated and backflushed
and a flame with detector (FID) or electron capture detector with helium to desorb the trapped sample onto a capillary GC
(ECD). Column 1: a 1.2 m by 2 mm or 4 mm with 1.95% QF- column. The column is temperature programmed to separate
1/1.5% OV-17 on Gas-Chrom Q. Column 2: a 3 meter by 2 mm the method analytes which are then detected with a photoion-
or 4 mm with 3% OV-101 on Gas-Chrom Q. ization detector (PID) and a Hall electrolytic conductivity
(HECD) placed in series. The PID is selective for aromatic
RANGE 1–515 g/L. compounds and the HECD is selective for halogenated com-
MDL 5.7 g/L (FID) and 15.7 g/L (ECD) pounds.

INTERFERENCES Impurities in the purge gas and from (d) Recoveries and relative standard deviations were deter-
organic compounds outgassing from the plumbing ahead of mined from seven samples of reagent water fortifi d with
the trap account for many contamination problems. Interfer- 10 g/L of each compound. Fluorobenzene was used as the
ences purged or coextracted from the samples will vary con- internal standard for calculating average recoveries.
sample or extract being tested. Cross-contamination can occur
whenever high-level and low-level samples are analyzed distilled water and oven dried at 105C) with a Teflon®-faced
sequentially. Samples also can be contaminated by diffusion of silicone septum . Collect bubble-free samples and place the sep-
volatile organics (particularly methylene chloride and fluoro- tum with the Teflon® side down on the water.
ment and storage. The lab where volatile analysis is performed SAMPLE PRESERVATION If residual chlorine is present in
and also the refrigerated storage area should be completely free the water add about 25 mg of ascorbic acid to each vial before
of solvents. samples are collected to remove the chlorine. Add hydrochloric
INSTRUMENTATION A GC containing a series configura- store them in a solvent-free refrigerator at 4C until analysis.
equipped with 10.0 eV (nominal) lamp and Hall electrolytic MHT The maximum holding time for samples is 14 days
conductivity detector (HECD) is required. Also required is an from the time they were collected.
all-glass 5-mL purging device, a sorbent trap, and a thermal SAMPLE PREPARATION Remove the plungers from two
desorption apparatus which is connected to the GC system. 5-mL syringes and attach a closed syringe valve to each. Warm
Column 1: VOCOL glass wide-bore capillary column. the sample to room temperature, open the sample bottle, and
Column 2: RTX–502.2 mega-bore capillary column. carefully pour the sample into one of the syringe barrels to just
Column 3: DB-62 mega-bore capillary column. short of overflowing. Replace the syringe plunger, invert the
syringe, and compress the sample. Open the syringe valve and
PRECISION & ACCURACY Method detection limits are vent any residual air while adjusting the sample volume to
dependent upon the characteristics of the gas chromatographic 5.0 mL. Add 10 L of the internal calibration standard to the
system used. Analytes that are not separated chromatographi- sample through the syringe valve. Close the valve. Fill the sec-
cally cannot be individually identified and used in the same ond syringe in an identical manner from the same sample
calibration mixture or water samples unless an alternative tech- bottle. Reserve this second syringe for a reanalysis if necessary.
nique for identification and quantification, such as mass spec-
QUALITY CONTROL As an initial demonstration of lab
trometry, is used.
accuracy and precision, analyze 4 to 7 replicates of a lab fortified
Electrolytic conductivity detetor (c) range in g/L (a) was blank containing analyte at 0.1–5 g/L. Collect all samples in
0.02–200. duplicate. Surrogate analytes (similar to those of the analytes
Electrolytic conductivity detetor (c) MDL in g/L (b) was not of interest), whose concentration is known in every sample, are
listed. measured using the same internal standard calibration proce-
Electrolytic conductivity detetor (c) accuracy as % recoverywas dure. Duplicate field reagent water blanks (trip blanks) must
not listed. be analyzed with each set of samples, lab reagent blanks
Electrolytic conductivity detetor (c) precision as % RSD was (method blanks) must be analyzed with each batch of samples
not listed. processed as a group within a work shift. Also, a single lab-
Photoionization detector (d) range in g/L (a) was 0.02–200. fortified blank that contains each of the analytes of interest
Photoionization detector (d) MDL in g/L (b) was 0.05. should be analyzed with each batch of samples processed as a
Photoionization detector (d) accuracy as % recovery was 98. group within a work shift. A 3- to 5-point calibration curve is
Photoionization detector (d) precision as % RSD was 0.9. needed depending on the calibration range factor required.
(a) The applicable concentration range of this method is com- EPA CONTACT & HOTLINE For technical questions contact
pound, instrument, and matrix-dependent. It is listed as Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
being approximately 0.02 to 200 g/L but no specific infor- Drinking Water (WH-550D), 401 M St. SW, Washington, DC
mation is provided so caution should be observed. 20460. Tel. (202) 260-3040. For further information the EPA
(b) The method detection limits reports with this method are Safe Drinking Water Hotline may be called at: (800) 426-4791.
compound, instrument, and matrix-dependent. The values REFERENCE Methods for the Determination of Organic
reported were calculated using reagent water fortifi d with Compounds in Drinking Water, EPA/600/4-88/039 (revised
the corresponding compounds at 10 g/L and a July 1991; Final Rule for determination of compliance with the
GC-equipped with a 60 m 0.75 mm VOLCOL wide bore MCL for Total Trihalomethanes under 141.30, in 40 CFR Part
capillary column with 1.5 m fi m thickness and using 141, Vol. 58, No. 147, Fed. Reg., Tuesday Aug. 3, 1993). U.S.
helium carrier gas. EPA Environmental Monitoring Systems Laboratory, Cincin-
(c) Recoveries and relative standard deviations were deter- nati, OH, 45268, U.S.A. Available from the National Technical
mined from seven samples of reagent water fortifi d with Information Service (NTIS), 5285 Port Royal Road, Spring-
10 g/L of each compound. 2-Bromo-1-chloropropane was field, VA 22161; Tel. 800-553-6847. NTIS Order Number is
used as the internalstandard forcalculatingaverage recoveries. PB91-231480.

similar mass spectra, typically many structural isomers, must
Isopropylbenzene EPA Method 524
CAS #98-82-8 be reported as an isomeric group or pair.
The range (in g/L) was 0.5–10.
TITLE Measurement of Purgeable Organic Compounds in The Method Detection Limig (in g/L) was 0.15.
Water by Capillary Column GC/MS. The accuracy (as % recovery) was 101.
MATRIX Drinking water and raw source water; the latter The precision (in %) was 7.6.
should include most surface water and groundwater sources. Note: Data were obtained from 16–31 determinations using a
METHOD SUMMARY Method 524.2 covers 60 volatile wide-bore capillary column and a jet separator interfaced to a
organic compounds. An inert gas (zero grade nitrogen or quadrupole mass spectrometer. All analytes were in a reagent
helium) is bubbled through a 25-mL or a 5-mL water sample water matrix.
(depending on the expected concentration of the analytes). SAMPLING METHOD Collect samples using a 40- to
Purged sample components are trapped in a tube of sorbent 120-mL screw-cap vial (prewashed with detergent, rinsed with
materials. When purging is complete, the sorbent tube is heated distilled water and oven dried at 105C) with a Teflon®-faced
and backflushed with helium to desorb the trapped sample silicone septum . Collect bubble-free samples and place the sep-
onto a capillary GC column. tum with the Teflon® side down on the water.
INTERFERENCES Impurities in the purge gas and from SAMPLE PRESERVATION If residual chlorine is present in
organic compounds outgassing from the plumbing ahead of the water add about 25 mg of ascorbic acid to each vial before
the trap account for many contamination problems. Interfer- samples are collected to remove the chlorine. Add hydrochloric
ences purged or coextracted from the samples will vary con- acid to reduce pH to <2, and immediately cool samples to 4 C,
siderably from source to source, depending upon the particular and store them in a solvent-free refrigerator at 4C until analysis.
whenever high-level and low-level samples are analyzed MHT The maximum holding time for samples is 14 days
sequentially. Samples also can be contaminated by diffusion of from the time they were collected.
volatile organics (particularly methylene chloride and fluoro- SAMPLE PREPARATION Remove the plungers from two
carbons) through the septum seal into the sample during ship- 25-mL (or 5-mL depending on sample size) syringes and attach
ment and storage. a closed syringe valve to each. Warm the sample to room tem-
INSTRUMENTATION A GC/MS with a data system perature, open the sample bottle, and carefully pour the sample
equipped with one of the following capillary GC columns: into one of the syringe barrels to just short of overflowing.
Replace the syringe plunger, invert the syringe, and compress
Column 1: VOCOL glass wide bore capillary column. the sample. Open the syringe valve and vent any residual air
Column 2: DB-624 fused silica capillary column. while adjusting the sample volume to 25.0 mL (or 5 mL). For
Also required is an all-glass 25 mL or 5-mL purging device, a taining the internal standard and the surrogates to the sample
sorbent trap, and a thermal desorption apparatus which is through the syringe valve. For calibration standards and lab
connected to the GC/MS system. fortified blanks, add 5 L of the fortification solution contain-
ing the internal standard only. Close the valve. Fill the second
PRECISION & ACCURACY Method detection limits are syringe in an identical manner from the same sample bottle.
compound- and instrument-dependent, and may vary from Reserve this second syringe for a reanalysis if necessary.
approximately 0.02–0.35 g/L. Note in the table below that the
“true” concentration range used for accuracy and precision QUALITY CONTROL As an initial demonstration of lab
measurements was quite narrow. However, the applicable con- accuracy and precision, analyze 4 to 7 replicates of a lab fortified
centration range of this method is primarily column dependent blank containing analyte at 0.2–5 g/L. Collect all samples in
and is approximately 0.02 to 200 g/L for the wide-bore thick- duplicate. Surrogate analytes (similar to those of the analytes
film columns. Narrow-bore thin-film columns may have a of interest), whose concentration is known in every sample, are
capacity which limits the range to about 0.02 to 20 g/L. Ana- measured using the same internal standard calibration proce-
lytes that are inefficiently purged from water will not be dure. Duplicate field reagent water blanks (trip blanks) must
detected when present at low concentrations, but they can be be analyzed with each set of samples, lab reagent blanks
measured with acceptable accuracy and precision when present (method blanks) must be analyzed with each batch of samples
in sufficient amounts. processed as a group within a work shift. Also, a single lab-
fortified blank that contains each of the analytes of interest
Analytes that are not separated chromatographically, but which
mixture or water sample.Analytes which have very similar mass
spectra cannot be individually identified and measured in the EPA CONTACT & HOTLINE For technical questions contact
same calibration mixture or water samples unless they have Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
different retention times. Co-eluting compounds with very Drinking Water (WH-550D), 401 M St. SW, Washington, DC

20460. Tel. (202) 260-3040. For further information the EPA for wastes, and 1 g/L for groundwater. EQLs will be propor-
Safe Drinking Water Hotline may be called at: (800) 426-4791. tionately higher for sample extracts and samples that require
Compounds in Drinking Water, EPA/600/4-88/039 (revised MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
July 1991; Final Rule for determination of compliance with the Matrix Factor (b)
MCL for Total Trihalomethanes under 141.30, in 40 CFR Part
141, Vol. 58, No. 147, Fed. Reg., Tuesday Aug. 3, 1993). U.S. Groundwater 10
EPA Environmental Monitoring Systems Laboratory, Cincin- Low-concentration soil 10
nati, OH, 45268, U.S.A. Available from the National Technical Water miscible liquid waste 500
Information Service (NTIS), 5285 Port Royal Road, Spring- High-concentration soil and sludge 1250
field, VA 22161; Tel. 800-553-6847. NTIS Order Number is Non-water miscible waste 1250
PB91-231480. (a) Sample EQLs are highly matrix-dependent. The EQLs listed
herein are provided for guidance and may not always be achievable.
Isopropylbenzene EPA Method 8021 samples, the factor is on a wet-weight basis.
CAS #98-82-8 SINGLE LABORATORY ACCURACY & PRECISION DATA
FOR VOCs IN WATER
TITLE Halogenated Volatile by Gas Chromatography Using
Photoionization and Electrolytic Conductivity Detectors in This method was tested in a single lab using water spiked at
Series: Capillary Column Technique 10 g/L and the following data was reported:
5030 (where applicable). A temperature program is used with (no response for this detector)-.
sion of volatile organics (particularly chlorofluorocarbons and with Teflon®-faced silicone septum may be used for both liquid
methylene chloride) through the sample container septum dur- and solid matrices. When collecting samples, liquids and solids
ing shipment and storage. should be introduced into the vials gently to reduce agitation
Column: 60 m 0.75 mm I.D.VOCOLwide-bore capillary col- tion between samples particularly if the sampled waste is sus-
umn with 1.5 m film thickness. pected of containing high levels of volatile organics.
PRECISION & ACCURACY MDLs are compound-depen- Semivolatile organics — Containers used to collect samples for
dent and vary with purging efficiency and concentration. The the determination of semivolatile organic compounds should
applicable concentration range of this method is compound- be soap and water washed followed by methanol (or isopro-
and instrument-dependent but is approximately 0.1 to panol) rinsing. The sample containers should be of glass or
200 g/L. Analytes that are inefficiently purged from water will Teflon® and have screw-top covers with Teflon® liners.
(wet weight) for soil/sediment samples, 100 g/kg (wet weight) When liquid samples contain residual chlorine, they are treated

as above and, in addition, 4 drops of 4% aqueous sodium nents. The analytes are desorbed directly to a large bore capil-
thiosulfate are added. Soil, sediment, and sludge samples are lary or cryofocussed on a capillary precolumn before being
only cooled to 4C. flash evaporated to a narrow bore capillary for analysis.
Preservation for semivolatile organics — No preservation is INTERFERENCES Major contaminant sources are volatile
used with concentrated waste samples. With liquid samples materials in the lab and impurities in the inert purging gas and
containing no residual chlorine and with soil, sediment, and in the sorbent trap. Interfering contamination may occur when
sludge samples, immediately cooling to 4C is the only preser- a sample containing low concentrations of volatile organic
vation used. When residual chlorine is present then 3 mL of compounds is analyzed immediately after a sample containing
10% aqueous sodium sulfate is added for each gallon of sample high concentrations of volatile organic compounds. After anal-
collected, followed by cooling to 4C. ysis of a sample containing high concentrations of volatile
organic compounds, one or more calibration blanks should be
MHT The holding time for all volatile organics samples is
14 days. Liquid samples must be extracted within 7 days and
their extracts analyzed within 40 days. Concentrated waste, soil,
ommended to prevent contamination of the system. This is
sediment, and sludge samples must be extracted within 14 days
especially true for soil and waste samples.
Special precautions must be taken to analyze for methylene
SAMPLE PREPARATION Volatile compounds are intro-
chloride. The analytical and sample storage area should be
duced into the gas chromatograph either by direct injector or
isolated from all atmospheric sources of methylene chloride.
All gas chromatography carrier gas lines and purge gas plumb-
be used directly on groundwater samples or low-concentration
contaminated soils and sediments. For medium-concentration
Laboratory clothing previously exposed to methylene chloride
soils or sediments, methanolic extraction, as described in EPA
fumes during liquid-liquid extraction procedures can contrib-
Method 5030, may be necessary prior to purge-and-trap analysis.
QUALITY CONTROL Calculate surrogate standard recovery
Samples can also be contaminated by diffusion of volatile
on all samples, blanks, and spikes.A trip blank is recommended
organics (particularly methylene chloride and fluorocarbons)
to check on sampling, storage, and handling contamination.
Calibration standards, at a minimum of five concentration lev- through the septum seal during shipment and storage. A trip
els, are prepared in organic-free reagent water. One of the con- blank can serve as a check on such contamination.
centration levels should be at a concentration near, but above, INSTRUMENTATION GC/MS with a temperature-pro-
the method detection limit. grammable chromatograph suitable for splitless injection
A combination of bromochloromethane, 2-bromo-1-chloro- equipped with variable constant differential flow controllers, a
propane, 1,4-dichlorobutane, and bromochlorobenzene are subambient oven controller, a purging device, sorbent trap, a
recommended as surrogate standards to encompass the range thermal desorption apparatus and a capillary precolumn inter-
of the temperature program used in this method. face when using cryogenic cooling will be needed. The follow-
ing GC columns may be used:
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office Column 1: 60 m 0.75 mm I.D. capillary column coated with
of Solid Waste, Washington, DC, EPA Method 8021A, Rev. 1, VOCOL, 1.5 m film thickness.
Nov. 1992. Column 2: 30 m 0.53 mm capillary column coated with DB-
Column 3: 30 m 0.32 mm I.D. capillary column coated with
DB-5 or SE-54, 1-m film thickness.
Isopropylbenzene EPA Method 8260
CAS #98-82-8 PRECISION & ACCURACY This method has been tested in
a single lab using spiked water. Using a wide-bore capillary
TITLE Volatile Organic Compounds by GC/MS: Capillary column, water was spiked at concentrations between 0.5 and
Column Technique 10 g/L. Single lab accuracy and precision data are presented.
The MDL actually achieved in a given analysis will vary
MATRIX This method is applicable to nearly all types of depending on instrument sensitivity and matrix effects.
soils, and sediments. The MDL (a) in g/L was 0.15.
The concentration range in g/L was 0.5–10.
METHOD SUMMARY Method 8260A covers 58 volatile The mean accuracy (% of true value) was 101.
organic compounds that are introduced into a gas chromato- The precision as relative standard deviation was 7.6.
limited applications). Zero-grade helium is bubbled through a Note: The MDL is based on a 25-mL sample volume instead
5-mL solution at ambient temperature. Purged sample com- of a 5-mL sample volume.
ponents are trapped in a tube containing suitable sorbent mate- SAMPLING METHOD
rials. When purging is complete, the sorbent tube is heated and Liquid samples — Use a 40-mL glass screw-cap VOA vial with
backflushed with helium to desorb trapped sample compo- a Teflon®-faced silicone septum that has been prewashed,

rinsed with distilled deionized water, and oven dried. If residual An aliquot of the extract is added to organic-free reagent water
chlorine is present, collect the sample in a 4-oz soil VOA con- containing surrogate and internal standards. This is purged at
tainer which has been pre-preserved with 4 drops of 10% ambient temperature. All samples with an expected concentra-
sodium thiosulfate. Mix gently and transfer the sample to a tion of >1.0 mg/kg should be analyzed by this method.
40-mL VOA vial. Collect bubble-free samples in duplicate and
seal each sample in a separate plastic bag. Mix the contents of the sample container with a narrow metal
Soils, sediments and sludges — Use an 8-oz widemouth glass uble in methanol, weigh 4 g (wet weight) of sample into a tared
bottle with Teflon®-faced silicone septum that has been pre- 20-mL vial. For waste that is soluble in methanol, tetraglyme,
washed, rinsed with distilled deionized water, and oven dried. or PEG, weigh 1 g (wet weight) into a tared scintillation vial
Do not heat the septum for more than 1 h. Tap slightly to or culture tube or a 10-mL volumetric flask. Quickly add
eliminate any free air space. Collect samples in duplicate and 9.0 mL of appropriate solvent then add 1.0 mL of a surrogate
seal each one in a separate plastic bag. spiking solution to the vial, cap it, and shake it for 2 min.
SAMPLE PRESERVATION METHANOL EXTRACT REQUIRED FOR ANALYSIS
Liquid samples — Add 4 drops of concentrated HCL, cool to OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
4C and store in a solvent-free refrigerator. Approximate Volume of
Soils, sediments and sludges — Cool samples to 4C and store Concentration Range Methanol Extract (a)
in a solvent-free refrigerator. 500–10,000 g/kg 100 L
MHT The maximum holding time of any sample (liquids, 1,000–20,000 g/kg 50 L
soils, sediments, and sludges) is 14 days. 5,000–100,000 g/kg 10 L
SAMPLE PREPARATION
while adjusting the sample volume to 5.0 mL. If there is only
volume of methanol is necessary to maintain a volume of 100 L
one volatile organic analysis (VOA) vial, a second syringe
added to the syringe.
should be filled at this time to protect against possible loss of
(b) Dilute an aliquot of the methanol extract and then take 100 L
ing method (EPA Method 3820). Use the screening data to
(0.005–1 mg/kg) or the high-concentration method (>1 mg/kg).
Matrix spiking standards should be prepared from volatile
internal standards. Analyze all reagent blanks and standards
organic compounds which will be representative of the com-
under the same conditions as the samples.
pounds being investigated. The recommended internal standards
Use a 5-g sample if the expected concentration is <0.1 mg/kg are chlorobenzene-d5, 1,4-difluorobenzene, 1,4-dichloro-
or a 1-g sample for expected concentrations between 0.1 and benzene-d4, and pentafluorobenzene. Using stock standard
1 mg/kg. Mix the contents of the sample container with a nar- solutions, prepare secondary dilution standards containing the
row metal spatula. Weigh the amount of the sample into a tared compounds of interest, either singly or mixed together in meth-
purge device. Add the spiked water to the purge device, which anol. Store them in a vial with no headspace for no more than
contains the weighed amount of sample, and connect the one week. Surrogates recommended are toluene-d8, 4-bromof-
device to the purge-and-trap system. luorobenzene, and dibromofluoromethane. Each sample
undergoing GC/MS analysis must be spiked with 10 L of the
surrogate spiking solution prior to analysis.
is either extracted or diluted, depending on its solubility in REFERENCE Test Methods for Evaluating Solid Waste (SW-
methanol. Wastes that are insoluble in methanol are diluted 846). U.S. EPA 1983, Method 8260A, Rev. 1, Nov. 1990. Office
with reagent tetraglyme or possibly polyethylene glycol (PEG). of Solid Waste, Washington, DC.

Isopropylbenzene EPA Method 503.1
CAS #98-82-8
TITLE Aromatic & Unsaturated VOCs in Water
MATRIX Drinking water (finished or any treatment stage) raphy-mass spectrometry (GC/MS).
and raw source water.
APPLICATION Method covers 28 aromatic and unsaturated are added to the sample. If the solids content is less than 1%,
VOCs. An inert gas is bubbled through a 5-mL water sample. a 1-L sample is extracted at pH 12–13, then at pH <2 with
Purged sample components are trapped in tube of sorbent methylene chloride using continuous extraction techniques.
materials. When purging is complete, sorbent tube is heated If the solids content is 30% or less, the sample is diluted to 1%
and backflushed with inert gas to desorb trapped sample onto solids with reagent water, homogenized ultrasonically, and
a packed GC column. extracted at pH 12–13, then at pH <2 with methylene chloride
INTERFERENCES During analysis, major contaminant using continuous extraction techniques. If the solids content is
sources are volatile materials in the lab and impurities in purg- greater than 30%, the sample is extracted using ultrasonic
techniques.
ing gas and sorbent trap. With high and low level samples, there
can be carryover contamination. Excess water causes a negative Each extract is dried over sodium sulfate, concentrated to a
baseline deflection. volume of 5 mL, cleaned up using GPC, if necessary, and con-
INSTRUMENTATION Purge and Trap GC w/photoioniza- performed, and to 0.5 mL if GPC is performed.
tion detector. ( Two GC columns are recommended);
Column 1: 5% SP-1200 and 1.75% Bentone 34 on Supelcoport; An internal standard is added to the extract, and a 1-mL aliquot
Column 2: 1,2,3-tris(2-cyanoethoxy)propane on Chromosorb W. of the extract is injected into the GC. The compounds are
RANGE 2.2–600 g/L. (Drinking water) serve to correct the variability of the analytical technique.
MDL 0.005 g/L in water INTERFERENCES Solvents, reagents, glassware, and other
PRECISION RSD = 8.7% at 0.40 g/L conc.; 7 samples sample processing hardware may yield artifacts and/or elevated
ACCURACY Average recovery = 88% at 0.40 g/L conc.; 7 spectra. Materials used in the analysis must be demonstrated
samples to be free from interferences under the conditions of analysis
SAMPLING METHOD Use a 40–120-mL screw-cap vial
(prewashed with detergent, rinsed with distilled water and oven
dried at 105C) with a PTFE-faced silicone septum . If residual purification of solvents by distillation in all glass systems may
chlorine is in the water add about 25 mg of ascorbic acid to be required. Glassware and, where possible, reagents are
each vial before sample collection. Collect bubble-free samples. cleaned by solvent rinse and baking at 450C for 1-h minimum.
STABILITY Cool to 4C; HCl to pH <2. Interferences coextracted from samples will vary considerably
MHT 14 days. being sampled.
QUALITY CONTROL As initial demonstration of lab accu- INSTRUMENTATION Major instrumentation includes a GC
racy and precision, analyze 4 to 7 replicates of a lab fortified with a splitless or on-column injection port for capillary col-
blank containing the analyte at 0.1–5 g/L. Collect all samples umn, a MS with 70 eV electron impact ionization, and a data
in duplicate. system to collect and record MS data, and process it. A K-D
REFERENCE Method 503.1, Volatile Aromatic & Unsatur-
ated Organic Compounds in H2O by Purge and Trap GC, EPA GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
600/4-88/039. vinyl silicone bonded phased fused silica capillary column.
2-Isopropylnaphthalene EPA Method 1625 rather than instrumental limitations. The limits typify the min-
present.
tion GC/MS The minimum level (in g/mL) was not listed. This is defined

The MDL (in g/kg) in low solids was not listed and in high through the extraction process on the same 8-h shift, to a
solids was not listed; these were determined in digested sludge maximum of 20 samples).
(low solids) and in filter cake or compost (high solids).
The labeled and native compound initial precision as standard the sampling technique, and spiked samples may be required
deviation (in g/L) was not listed. to determine the accuracy of the analysis when the internal
The labeled and native compound initial accuracy as average standard method is used.
recovery (in g/L) was not listed.
SAMPLE COLLECTION, PRESERVATION & HANDLING Dilution GC/MS. Office of Water Regulation and Standards,
Collect samples in glass containers. Aqueous samples which U.S. EPA Industrial Technology Division, Washington, DC,
flow freely are collected in refrigerated bottles using automatic EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
and analyze all extracts within 40 days of extraction. 4-Isopropyltoluene EPA Method 502
CAS #99-87-6
less are extracted directly using continuous liquid-liquid TITLE Volatile Organic Compounds in Water By Purge and
extraction techniques. Samples containing 1 to 30% solids are Trap Capillary Column Gas Chromatography with Photoion-
diluted to the 1% level with reagent water and extracted using ization and Electrolytic Conductivity Detectors in Series. U.S.
continuous liquid-liquid extraction techniques. Samples con- EPA Method 502.2, Rev. 2.0, 1989.
techniques. MATRIX Drinking water and raw source water. The latter
extractors to 12–13 with 6 N NaOH. Extract with methylene METHOD SUMMARY This method covers 60 volatile
chloride for 24–48 h. organic compounds that contain halogen atoms and/or that
Acid extraction — Adjust the pH of the waters in the extractors are aromatic. An inert gas (zero grade nitrogen or helium) is
to 2 or less using 6 N sulfuric acid. Extract with methylene bubbled through a 25-mL or a 5-mL water sample (depending
chloride for 24–48 h. on the expected concentration of the analytes). Purged sample
Ultrasonic extraction of high solids samples — Add anhy- components are trapped in a tube of sorbent materials. When
drous sodium sulfate to the sample and QC aliquot(s). purging is complete, the sorbent tube is heated and backflushed
Add acetone:methylene chloride (1:1) to the sample and with helium to desorb the trapped sample onto a capillary GC
mix thoroughly column. The column is temperature programmed to separate
the method analytes which are then detected with a photoion-
Concentrate extracts using a K-D apparatus. ization detector (PID) and a Hall electrolytic conductivity
QUALITY CONTROL The analyst is permitted to modify (HECD) placed in series. The PID is selective for aromatic
this method to improve separations or lower the costs of mea- compounds and the HECD is selective for halogenated com-
surements, provided all performance specifications are met. pounds.
Analyses of blanks are required to demonstrate freedom from INTERFERENCES Impurities in the purge gas and from
contamination. When results of spikes indicate atypical organic compounds outgassing from the plumbing ahead of
method performance for samples, the samples are diluted to the trap account for many contamination problems. Interfer-
bring method performance within acceptable limits. ences purged or coextracted from the samples will vary con-
For low solids (aqueous samples), extract, concentrate, and siderably from source to source, depending upon the particular
analyze two sets of four 1-L aliquots (8 aliquots total) of the sample or extract being tested. Cross-contamination can occur
precision and recovery standard. For high solids samples, two whenever high-level and low-level samples are analyzed
sets of four 30-g aliquots of the high solids reference matrix sequentially. Samples also can be contaminated by diffusion of
are used. volatile organics (particularly methylene chloride and fluoro-
Spike all samples with labeled compounds to assess method ment and storage. The lab where volatile analysis is performed
performance. Compute percent recovery of the labeled com- and also the refrigerated storage area should be completely free
pounds using the internal standard method. Compare the of solvents.
responding labeled compound recovery. INSTRUMENTATION A GC containing a series configura-
Reagent water and high solids reference matrix blanks are ana- equipped with 10.0 eV (nominal) lamp and Hall electrolytic
lyzed to demonstrate freedom from contamination. Extract conductivity detector (HECD) is required. Also required is an
and concentrate a 1-L reagent water blank or a high solids all-glass 5-mL purging device, a sorbent trap, and a thermal
reference matrix blank with each sample’s lot (samples started desorption apparatus which is connected to the GC system.

Column 1: VOCOL glass wide-bore capillary column. carefully pour the sample into one of the syringe barrels to just
Column 2: RTX–502.2 mega-bore capillary column. short of overflowing. Replace the syringe plunger, invert the
Column 3: DB-62 mega-bore capillary column. syringe, and compress the sample. Open the syringe valve and
vent any residual air while adjusting the sample volume to
5.0 mL. Add 10 L of the internal calibration standard to the
sample through the syringe valve. Close the valve. Fill the sec-
ond syringe in an identical manner from the same sample
cally cannot be individually identified and used in the same
bottle. Reserve this second syringe for a reanalysis if necessary.
calibration mixture or water samples unless an alternative tech-
nique for identification and quantification, such as mass spec- QUALITY CONTROL As an initial demonstration of lab
trometry, is used. accuracy and precision, analyze 4 to 7 replicates of a lab fortified
blank containing analyte at 0.1–5 g/L. Collect all samples in
Electrolytic conductivity detetor (c) range in g/L (a) was
duplicate. Surrogate analytes (similar to those of the analytes
0.02–200.
of interest), whose concentration is known in every sample, are
Electrolytic conductivity detetor (c) MDL in g/L (b) was not
measured using the same internal standard calibration proce-
listed.
dure. Duplicate field reagent water blanks (trip blanks) must
Electrolytic conductivity detetor (c) accuracy as % recoverywas
be analyzed with each set of samples, lab reagent blanks
not listed.
(method blanks) must be analyzed with each batch of samples
Electrolytic conductivity detetor (c) precision as % RSD was
processed as a group within a work shift. Also, a single lab-
not listed.
fortified blank that contains each of the analytes of interest
Photoionization detector (d) range in g/L (a) was 0.02–200.
Photoionization detector (d) MDL in g/L (b) was 0.01.
Photoionization detector (d) accuracy as % recovery was 98.
Photoionization detector (d) precision as % RSD was 2.4.
(a) The applicable concentration range of this method is com-
pound, instrument, and matrix-dependent. It is listed as
being approximately 0.02 to 200 g/L but no specific infor-
mation is provided so caution should be observed.
(b) The method detection limits reports with this method are
compound, instrument, and matrix-dependent. The values REFERENCE Methods for the Determination of Organic
reported were calculated using reagent water fortifi d with Compounds in Drinking Water, EPA/600/4-88/039 (revised
the corresponding compounds at 10 g/L and a July 1991; Final Rule for determination of compliance with the
GC-equipped with a 60 m 0.75 mm VOLCOL wide bore MCL for Total Trihalomethanes under 141.30, in 40 CFR Part
capillary column with 1.5 m fi m thickness and using 141, Vol. 58, No. 147, Fed. Reg., Tuesday Aug. 3, 1993). U.S.
helium carrier gas. EPA Environmental Monitoring Systems Laboratory, Cincin-
(c) Recoveries and relative standard deviations were deter- nati, OH, 45268, U.S.A. Available from the National Technical
mined from seven samples of reagent water fortifi d with Information Service (NTIS), 5285 Port Royal Road, Spring-
10 g/L of each compound. 2-Bromo-1-chloropropane was field, VA 22161; Tel. 800-553-6847. NTIS Order Number is
used as the internalstandard forcalculatingaverage recoveries. PB91-231480.
(d) Recoveries and relative standard deviations were deter-
10 g/L of each compound. Fluorobenzene was used as the
internal standard for calculating average recoveries. 4-Isopropyltoluene EPA Method 524
CAS #99-87-6
120-mL screw-cap vial (prewashed with detergent, rinsed with TITLE Measurement of Purgeable Organic Compounds in
distilled water and oven dried at 105C) with a Teflon®-faced Water by Capillary Column GC/MS.
MATRIX Drinking water and raw source water; the latter
METHOD SUMMARY Method 524.2 covers 60 volatile
the water add about 25 mg of ascorbic acid to each vial before
organic compounds. An inert gas (zero grade nitrogen or
samples are collected to remove the chlorine. Add hydrochloric
helium) is bubbled through a 25-mL or a 5-mL water sample
(depending on the expected concentration of the analytes).
store them in a solvent-free refrigerator at 4C until analysis.
Purged sample components are trapped in a tube of sorbent
MHT The maximum holding time for samples is 14 days materials. When purging is complete, the sorbent tube is heated
from the time they were collected. and backflushed with helium to desorb the trapped sample
onto a capillary GC column.
SAMPLE PREPARATION Remove the plungers from two
5-mL syringes and attach a closed syringe valve to each. Warm INTERFERENCES Impurities in the purge gas and from
the sample to room temperature, open the sample bottle, and organic compounds outgassing from the plumbing ahead of

the trap account for many contamination problems. Interfer- acid to reduce pH to <2, and immediately cool samples to 4 C,
ences purged or coextracted from the samples will vary con- and store them in a solvent-free refrigerator at 4C until analysis.
MHT The maximum holding time for samples is 14 days
from the time they were collected.
whenever high-level and low-level samples are analyzed
sequentially. Samples also can be contaminated by diffusion of SAMPLE PREPARATION Remove the plungers from two
volatile organics (particularly methylene chloride and fluoro- 25-mL (or 5-mL depending on sample size) syringes and attach
carbons) through the septum seal into the sample during ship- a closed syringe valve to each. Warm the sample to room tem-
ment and storage. perature, open the sample bottle, and carefully pour the sample
into one of the syringe barrels to just short of overflowing.
INSTRUMENTATION A GC/MS with a data system
Replace the syringe plunger, invert the syringe, and compress
equipped with one of the following capillary GC columns:
the sample. Open the syringe valve and vent any residual air
Column 1: VOCOL glass wide bore capillary column. while adjusting the sample volume to 25.0 mL (or 5 mL). For
Also required is an all-glass 25 mL or 5-mL purging device, a through the syringe valve. For calibration standards and lab
sorbent trap, and a thermal desorption apparatus which is fortified blanks, add 5 L of the fortification solution contain-
connected to the GC/MS system. ing the internal standard only. Close the valve. Fill the second
syringe in an identical manner from the same sample bottle.
PRECISION & ACCURACY Method detection limits are Reserve this second syringe for a reanalysis if necessary.
compound- and instrument-dependent, and may vary from
approximately 0.02–0.35 g/L. Note in the table below that the QUALITY CONTROL As an initial demonstration of lab
“true” concentration range used for accuracy and precision accuracy and precision, analyze 4 to 7 replicates of a lab fortified
measurements was quite narrow. However, the applicable con- blank containing analyte at 0.2–5 g/L. Collect all samples in
centration range of this method is primarily column dependent duplicate. Surrogate analytes (similar to those of the analytes
and is approximately 0.02 to 200 g/L for the wide-bore thick- of interest), whose concentration is known in every sample, are
film columns. Narrow-bore thin-film columns may have a measured using the same internal standard calibration proce-
capacity which limits the range to about 0.02 to 20 g/L. Ana- dure. Duplicate field reagent water blanks (trip blanks) must
lytes that are inefficiently purged from water will not be be analyzed with each set of samples, lab reagent blanks
detected when present at low concentrations, but they can be (method blanks) must be analyzed with each batch of samples
measured with acceptable accuracy and precision when present processed as a group within a work shift. Also, a single lab-
in sufficient amounts. fortified blank that contains each of the analytes of interest
Analytes that are not separated chromatographically, but which group within a work shift. A 3- to 5-point calibration curve is
have different mass spectra and non-interfering quantification needed depending on the calibration range factor required.
mixture or water sample.Analytes which have very similar mass EPA CONTACT & HOTLINE For technical questions contact
spectra cannot be individually identified and measured in the Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
same calibration mixture or water samples unless they have Drinking Water (WH-550D), 401 M St. SW, Washington, DC
different retention times. Co-eluting compounds with very 20460. Tel. (202) 260-3040. For further information the EPA
similar mass spectra, typically many structural isomers, must Safe Drinking Water Hotline may be called at: (800) 426-4791.
be reported as an isomeric group or pair. REFERENCE Methods for the Determination of Organic
The range (in g/L) was 0.1–10. Compounds in Drinking Water, EPA/600/4-88/039 (revised
The Method Detection Limig (in g/L) was 0.12. July 1991; Final Rule for determination of compliance with the
The accuracy (as % recovery) was 99. MCL for Total Trihalomethanes under 141.30, in 40 CFR Part
The precision (in %) was 6.7. 141, Vol. 58, No. 147, Fed. Reg., Tuesday Aug. 3, 1993). U.S.
EPA Environmental Monitoring Systems Laboratory, Cincin-
Note: Data were obtained from 16–31 determinations using a nati, OH, 45268, U.S.A. Available from the National Technical
wide-bore capillary column and a jet separator interfaced to a Information Service (NTIS), 5285 Port Royal Road, Spring-
quadrupole mass spectrometer. All analytes were in a reagent field, VA 22161; Tel. 800-553-6847. NTIS Order Number is
water matrix. PB91-231480.
distilled water and oven dried at 105C) with a Teflon®-faced 4-Isopropyltoluene EPA Method 8021
silicone septum . Collect bubble-free samples and place the sep- CAS #99-87-6
SAMPLE PRESERVATION If residual chlorine is present in TITLE Halogenated Volatile by Gas Chromatography Using
the water add about 25 mg of ascorbic acid to each vial before Photoionization and Electrolytic Conductivity Detectors in
samples are collected to remove the chlorine. Add hydrochloric Series: Capillary Column Technique

5030 (where applicable). A temperature program is used with (no response for this detector).
sion of volatile organics (particularly chlorofluorocarbons and
methylene chloride) through the sample container septum dur-
ing shipment and storage.
tion between samples particularly if the sampled waste is sus-
Column: 60 m 0.75 mm I.D.VOCOLwide-bore capillary col- pected of containing high levels of volatile organics.
PRECISION & ACCURACY MDLs are compound-depen- the determination of semivolatile organic compounds should
dent and vary with purging efficiency and concentration. The be soap and water washed followed by methanol (or isopro-
applicable concentration range of this method is compound- panol) rinsing. The sample containers should be of glass or
and instrument-dependent but is approximately 0.1 to Teflon® and have screw-top covers with Teflon® liners.
200 g/L. Analytes that are inefficiently purged from water will
When liquid samples contain residual chlorine, they are treated
(wet weight) for soil/sediment samples, 100 g/kg (wet weight)
for wastes, and 1 g/L for groundwater. EQLs will be propor-
thiosulfate are added. Soil, sediment, and sludge samples are
tionately higher for sample extracts and samples that require
only cooled to 4C.
MULTIPLICATION FACTORS FOR OTHER MATRICES (a) used with concentrated waste samples. With liquid samples
Matrix Factor (b) containing no residual chlorine and with soil, sediment, and
Groundwater 10 sludge samples, immediately cooling to 4C is the only preser-
Low-concentration soil 10 vation used. When residual chlorine is present then 3 mL of
Water miscible liquid waste 500 10% aqueous sodium sulfate is added for each gallon of sample
High-concentration soil and sludge 1250 collected, followed by cooling to 4C.
Non-water miscible waste 1250 MHT The holding time for all volatile organics samples is
(a) Sample EQLs are highly matrix-dependent. The EQLs listed 14 days. Liquid samples must be extracted within 7 days and
herein are provided for guidance and may not always be achievable. their extracts analyzed within 40 days. Concentrated waste, soil,
(b) EQL = [Method detection limit] [Factor]. For non-aqueous sediment, and sludge samples must be extracted within 14 days
samples, the factor is on a wet-weight basis. and their extracts analyzed within 40 days.
SINGLE LABORATORY ACCURACY & PRECISION DATA SAMPLE PREPARATION Volatile compounds are intro-
FOR VOCs IN WATER duced into the gas chromatograph either by direct injector or
This method was tested in a single lab using water spiked at be used directly on groundwater samples or low-concentration
10 g/L and the following data was reported: contaminated soils and sediments. For medium-concentration

soils or sediments, methanolic extraction, as described in EPA Laboratory clothing previously exposed to methylene chloride
Method 5030, may be necessary prior to purge-and-trap analysis. fumes during liquid-liquid extraction procedures can contrib-
QUALITY CONTROL Calculate surrogate standard recovery
on all samples, blanks, and spikes.A trip blank is recommended Samples can also be contaminated by diffusion of volatile
to check on sampling, storage, and handling contamination. organics (particularly methylene chloride and fluorocarbons)
Calibration standards, at a minimum of five concentration lev- through the septum seal during shipment and storage. A trip
els, are prepared in organic-free reagent water. One of the con- blank can serve as a check on such contamination.
centration levels should be at a concentration near, but above,
INSTRUMENTATION GC/MS with a temperature-pro-
grammable chromatograph suitable for splitless injection
A combination of bromochloromethane, 2-bromo-1-chloro- equipped with variable constant differential flow controllers, a
propane, 1,4-dichlorobutane, and bromochlorobenzene are subambient oven controller, a purging device, sorbent trap, a
recommended as surrogate standards to encompass the range thermal desorption apparatus and a capillary precolumn inter-
of the temperature program used in this method. face when using cryogenic cooling will be needed. The follow-
ing GC columns may be used:
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office Column 1: 60 m 0.75 mm I.D. capillary column coated with
of Solid Waste, Washington, DC, EPA Method 8021A, Rev. 1, VOCOL, 1.5 m film thickness.
Nov. 1992. Column 2: 30 m 0.53 mm capillary column coated with DB-
Column 3: 30 m 0.32 mm I.D. capillary column coated with
DB-5 or SE-54, 1-m film thickness.
p-Isopropyltoluene EPA Method 8260
CAS #99-87-6 PRECISION & ACCURACY This method has been tested in
a single lab using spiked water. Using a wide-bore capillary
TITLE Volatile Organic Compounds by GC/MS: Capillary column, water was spiked at concentrations between 0.5 and
Column Technique 10 g/L. Single lab accuracy and precision data are presented.
The MDL actually achieved in a given analysis will vary
MATRIX This method is applicable to nearly all types of depending on instrument sensitivity and matrix effects.
soils, and sediments. The MDL (a) in g/L was 0.12.
The concentration range in g/L was 0.1–10.
METHOD SUMMARY Method 8260A covers 58 volatile The mean accuracy (% of true value) was 99.
organic compounds that are introduced into a gas chromato- The precision as relative standard deviation was 6.7.
limited applications). Zero-grade helium is bubbled through a Note: The MDL is based on a 25-mL sample volume instead
5-mL solution at ambient temperature. Purged sample com- of a 5-mL sample volume.
ponents are trapped in a tube containing suitable sorbent mate- SAMPLING METHOD
rials. When purging is complete, the sorbent tube is heated and Liquid samples — Use a 40-mL glass screw-cap VOA vial with
backflushed with helium to desorb trapped sample compo- a Teflon®-faced silicone septum that has been prewashed,
nents. The analytes are desorbed directly to a large bore capil- rinsed with distilled deionized water, and oven dried. If residual
lary or cryofocussed on a capillary precolumn before being chlorine is present, collect the sample in a 4-oz soil VOA con-
flash evaporated to a narrow bore capillary for analysis. tainer which has been pre-preserved with 4 drops of 10%
INTERFERENCES Major contaminant sources are volatile sodium thiosulfate. Mix gently and transfer the sample to a
materials in the lab and impurities in the inert purging gas and 40-mL VOA vial. Collect bubble-free samples in duplicate and
in the sorbent trap. Interfering contamination may occur when seal each sample in a separate plastic bag.
a sample containing low concentrations of volatile organic Soils, sediments and sludges — Use an 8-oz widemouth glass
compounds is analyzed immediately after a sample containing bottle with Teflon®-faced silicone septum that has been pre-
high concentrations of volatile organic compounds. After anal- washed, rinsed with distilled deionized water, and oven dried.
ysis of a sample containing high concentrations of volatile Do not heat the septum for more than 1 h. Tap slightly to
organic compounds, one or more calibration blanks should be eliminate any free air space. Collect samples in duplicate and
analyzed to check for cross-contamination. Screening of the seal each one in a separate plastic bag.
ommended to prevent contamination of the system. This is SAMPLE PRESERVATION
especially true for soil and waste samples. Liquid samples — Add 4 drops of concentrated HCL, cool to
Special precautions must be taken to analyze for methylene
chloride. The analytical and sample storage area should be Soils, sediments and sludges — Cool samples to 4C and store
isolated from all atmospheric sources of methylene chloride.
All gas chromatography carrier gas lines and purge gas plumb- MHT The maximum holding time of any sample (liquids,
ing should be constructed from stainless steel or copper tubing. soils, sediments, and sludges) is 14 days.

SAMPLE PREPARATION Calculate appropriate dilution factor for concentrations
Liquid samples — Remove the plunger from a 5-mL syringe exceeding this table.
10 L of internal standard spiking solution through the valve QUALITY CONTROL Demonstrate, through the analysis of
bore of the 5-mL syringe, then close the valve. The surrogate a reagent water blank, that interferences from the analytical
and internal standards may be mixed and added as a single system, glassware, and reagents are under control. Blank sam-
spiking solution. ples should be carried through all stages of the sample prepa-
with organic-free reagent water containing the surrogate and Matrix spiking standards should be prepared from volatile
internal standards. Analyze all reagent blanks and standards organic compounds which will be representative of the com-
under the same conditions as the samples. pounds being investigated. The recommended internal stan-
Use a 5-g sample if the expected concentration is <0.1 mg/kg dards are chlorobenzene-d 5, 1,4 -difluorobenzene,
or a 1-g sample for expected concentrations between 0.1 and 1,4-dichlorobenzene-d4, and pentafluorobenzene. Using stock
1 mg/kg. Mix the contents of the sample container with a nar- standard solutions, prepare secondary dilution standards con-
row metal spatula. Weigh the amount of the sample into a tared taining the compounds of interest, either singly or mixed
purge device. Add the spiked water to the purge device, which together in methanol. Store them in a vial with no headspace
contains the weighed amount of sample, and connect the for no more than one week. Surrogates recommended are tol-
device to the purge-and-trap system. uene-d8, 4-bromofluorobenzene, and dibromofluoromethane.
Each sample undergoing GC/MS analysis must be spiked with
extracting the sediment or soil with methanol. A waste sample 10 L of the surrogate spiking solution prior to analysis.
is either extracted or diluted, depending on its solubility in REFERENCE Test Methods for Evaluating Solid Waste (SW-
methanol. Wastes that are insoluble in methanol are diluted 846). U.S. EPA 1983, Method 8260A, Rev. 1, Nov. 1990. Office
with reagent tetraglyme or possibly polyethylene glycol (PEG). of Solid Waste, Washington, DC.
ambient temperature. All samples with an expected concentra-
tion of >1.0 mg/kg should be analyzed by this method. 4-Isopropyltoluene EPA Method 503.1
CAS #99-87-6
spatula. For sediments or soils and solid wastes that are insol- TITLE Aromatic & Unsaturated VOCs in Water
20-mL vial. For waste that is soluble in methanol, tetraglyme, MATRIX Drinking water (finished or any treatment stage)
or PEG, weigh 1 g (wet weight) into a tared scintillation vial and raw source water.
or culture tube or a 10-mL volumetric flask. Quickly add APPLICATION Method covers 28 aromatic and unsaturated
9.0 mL of appropriate solvent then add 1.0 mL of a surrogate
VOCs. An inert gas is bubbled through a 5-mL water sample.
Purged sample components are trapped in tube of sorbent
METHANOL EXTRACT REQUIRED FOR ANALYSIS materials. When purging is complete, sorbent tube is heated
OF HIGH-CONCENTRATION SOILS OR SEDIMENTS and backflushed with inert gas to desorb trapped sample onto
Approximate Volume of a packed GC column.
Concentration Range Methanol Extract (a) INTERFERENCES During analysis, major contaminant
500–10,000 g/kg 100 L sources are volatile materials in the lab and impurities in purg-
1,000–20,000 g/kg 50 L ing gas and sorbent trap. With high and low level samples, there
5,000–100,000 g/kg 10 L can be carryover contamination. Excess water causes a negative
25,000–500,000 g/kg 100 L of 1/50 dilution (b) baseline deflection.

INSTRUMENTATION Purge and Trap GC w/photoioniza- An internal standard is added to the extract, and a 1-mL aliquot
tion detector. ( Two GC columns are recommended); of the extract is injected into the GC. The compounds are
Column 1: 5% SP-1200 and 1.75% Bentone 34 on Supelcoport; separated by GC and detected by a MS. The labeled compounds
Column 2: 1,2,3-tris(2-cyanoethoxy)propane on Chromosorb W. serve to correct the variability of the analytical technique.
RANGE 2.2–600 g/L. (Drinking water). INTERFERENCES Solvents, reagents, glassware, and other
MDL 0.009 g/L in water
PRECISION Not listed. spectra. Materials used in the analysis must be demonstrated
ACCURACY Not listed.
SAMPLING METHOD Use a 40–120-mL screw-cap vial (sample started through the extraction process on a given 8-h
(prewashed with detergent, rinsed with distilled water and oven shift, to a maximum of 20). Specific selection of reagents and
dried at 105C) with a PTFE-faced silicone septum . If residual purification of solvents by distillation in all glass systems may
chlorine is in the water add about 25 mg of ascorbic acid to be required. Glassware and, where possible, reagents are
each vial before sample collection. Collect bubble-free samples. cleaned by solvent rinse and baking at 450C for 1-h minimum.
STABILITY Cool to 4C; HCl to pH <2.
MHT 14 days. being sampled.
QUALITY CONTROL As initial demonstration of lab accu- INSTRUMENTATION Major instrumentation includes a GC
racy and precision, analyze 4 to 7 replicates of a lab fortified with a splitless or on-column injection port for capillary col-
blank containing the analyte at 0.1–5 g/L. Collect all samples umn, a MS with 70 eV electron impact ionization, and a data
in duplicate. system to collect and record MS data, and process it. A K-D
REFERENCE Method 503.1, Volatile Aromatic & Unsatur-
ated Organic Compounds in H2O by Purge and Trap GC, EPA GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
600/4-88/039. vinyl silicone bonded phased fused silica capillary column.
Isosafrole EPA Method 1625 rather than instrumental limitations. The limits typify the min-
present.
The minimum level (in g/mL) was not listed. This is defined
tion GC/MS
deviation (in g/L) was not listed.
volume of 5 mL, cleaned up using GPC, if necessary, and con- less are extracted directly using continuous liquid-liquid extrac-
centrated. Extracts are concentrated to 1 mL if GPC is not tion techniques. Samples containing 1 to 30% solids are diluted
performed, and to 0.5 mL if GPC is performed. to the 1% level with reagent water and extracted using continuous

liquid-liquid extraction techniques. Samples containing greater from all types of solid waste matrices, soils, and groundwater.
than 30% solids are extracted using ultrasonic techniques. Although surface waters are not specifically mentioned, this
lakes, etc.
extractors to 12–13 with 6 N NaOH. Extract with methylene
chloride for 24–48 h. METHOD SUMMARY This method covers 259 semivolatile
Acid extraction — Adjust the pH of the waters in the extractors organic compounds. In very limited applications direct injec-
to 2 or less using 6 N sulfuric acid. Extract with methylene tion of the sample into the GC/MS system may be appropriate,
chloride for 24–48 h. but this results in very high detection limits (approximately
Ultrasonic extraction of high solids samples — Add anhy- 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
drous sodium sulfate to the sample and QC aliquot(s). gate, and matrix spiking standards, is extracted in a continuous
Add acetone:methylene chloride (1:1) to the sample and extractor first under acid conditions and then under basic con-
mix thoroughly ditions. Typically 30 g of a solid sample, containing surrogate,
Isosafrole EPA Method 8270
CAS #120-58-1

ESTIMATED QUANTITATION LIMIT sulfate until the sample is free flowing. Add 1 mL of surrogate
Other Matrices Factor (a) standards to all samples, spikes, standards, and blanks. For the
High-concentration soil and sludges by sonicator 7.5 of a matrix spiking standard. For base/neutral acid analysis, the
Non-water miscible waste 75 amount added of the surrogates and matrix spiking com-
(a) EQL forother matrices =[EQL forlow soil/sediment] [Factor]. pounds should result in a final concentration of 100 ng/ L of
This estimated EQL is similar to an EPA “Practical Quantitation each base/neutral analyte and 200 ng/L of each acid analyte
Limit.” in the extract to be analyzed (assuming a 1- L injection).
SAMPLING METHOD ride:acetone and extract the sample ultrasonically for 3 min
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with and then decant or filter the extracts. Repeat the extraction two
a screw-top Teflon®-lined cover that has been prewashed with or more times. Dry the extract using a column with anhydrous
detergent and rinsed with distilled water and methanol (or sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
isopropanol).
Soils, sediments, or sludges — Use an 8-oz. widemouth glass taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
with a screw-top Teflon®-lined cover that has been prewashed used for tuning the GC/MS system each 12-h shift. A system
with detergent and rinsed with distilled water and methanol performance check also must be made during every 12-h shift.
(or isopropanol). A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
SAMPLE PRESERVATION rophenol, and benzidine is required to verify injection port
Liquid samples — If residual chlorine is present, add 3 mL of inertness and GC column performance. A calibration standard
10% sodium thiosulfate per gallon, cool to 4C and store in a at mid-concentration, containing each compound of interest,
solvent-free refrigerator until analysis; if chlorine is not present, including all required surrogates, must be performed every 12 h
then eliminate the sodium thiosulfate addition. during analysis. After the system performance check is met,
Soils, sediments, or sludges — Cool samples to 4C and store validity of the initial calibration.
MHT Liquid samples must be extracted within 7 days and calibration check standard must be evaluated immediately after
the extracts analyzed within 40 days. Soils, sediments, or slud- or during data acquisition. If the retention time for any internal
ges may be stored for a maximum of 14 days and the extracts standard changes by more than 30 seconds from the last check
analyzed within 40 days. calibration (12 h), the chromatographic system must be
SAMPLE PREPARATION
ume may be used and then diluted with organic-free reagent
solution into each sample. For the sample in each analytical Demonstrate, through the analysis of a reagent water blank,
batch selected for spiking, add 1.0 mL of a matrix spiking stan- that interferences from the analytical system, glassware, and
dard. For base/neutral acid analysis, the amount of the surro- reagents are under control. The blank samples should be car-
gates and matrix spiking compounds added to the sample ried through all stages of the sample preparation and measure-
should result in a final concentration of 100 ng/L of each ment steps. For each analytical batch (up to 20 samples), a
analyte in the extract to be analyzed (assuming a 1- L injec- reagent blank, matrix spike, and matrix spike duplicate/dupli-
tion). Extract with methylene chloride for 18–24 h. Next, adjust cate must be analyzed (the frequency of the spikes may be
the pH of the aqueous phase to pH >11 using 10 N sodium different for different monitoring programs). The blank and
hydroxide and extract it with methylene chloride again for spiked samples must be carried through all stages of the sample
18–24 h. Dry the extract through a column containing anhy- preparation and measurement steps. A QC reference sample
drous sodium sulfate and concentrate it to 1 mL using a K-D concentrate containing each analyte at a concentration of
concentrator. 100 mg/L in methanol is required.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous REFERENCE Test Methods for Evaluating Solid Waste (SW-
or wet samples (gummy or clay type) that do not have a free- 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
flowing sandy texture must be mixed with anhydrous sodium of Solid Waste, Washington, DC.

K
Kepone EPA Method 8270 (a) EQLs listed for soil/sediment are based on wet weight. Nor-
CAS #143-50-0 mally data is reported in a dry-weight basis; therefore, EQLs
TITLE Semivolatile Organic Compounds by GC/MS This calculation is based on a 30-g sample and gel perme-
tion of semivolatile organic compounds in extracts prepared provided for guidance and may not always be achievable.
from all types of solid waste matrices, soils, and groundwater. C = True value for concentration, in g/L.
Although surface waters are not specifically mentioned, this X = Average recovery found for measurements of samples con-
method should be applicable to water samples from rivers, taining a concentration of C, in g/L.
lakes, etc.
METHOD SUMMARY This method covers 259 semivolatile Other Matrices Factor (a)
tion of the sample into the GC/MS system may be appropriate, High-concentration soil and sludges by sonicator 7.5
but this results in very high detection limits (approximately Non-water miscible waste 75
10,000 g/L). Typically, a 1-L liquid sample, containing surro- (a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
gate, and matrix spiking standards, is extracted in a continuous This estimated EQL is similar to an EPA “Practical Quantitation
extractor first under acid conditions and then under basic con- Limit.”
and matrix spiking standards, is extracted ultrasonically. After SAMPLING METHOD
isopropanol).
is performed by GC/MS using a capillary GC column. Soils, sediments, or sludges — Use an 8-oz. widemouth glass
INTERFERENCES Raw GC/MS data from all blanks, sam- with detergent and rinsed with distilled water and methanol
ples, and spikes must be evaluated for interferences. Contam- (or isopropanol).
and low-concentration samples are sequentially analyzed. To SAMPLE PRESERVATION
reduce carryover, the sample syringe must be rinsed out Liquid samples — If residual chlorine is present, add 3 mL of
between samples with solvent. Whenever an unusually concen- 10% sodium thiosulfate per gallon, cool to 4C and store in a
trated sample is encountered, it should be followed by the solvent-free refrigerator until analysis; if chlorine is not present,
analysis of blank solvent to check for cross-contamination. then eliminate the sodium thiosulfate addition.
INSTRUMENTATION A GC/MS and a data system are Soils, sediments, or sludges — Cool samples to 4C and store
0.32 mm I.D.) 1um film thickness silicone-coated fused silica MHT Liquid samples must be extracted within 7 days and
capillary column. A continuous liquid-liquid extractor the extracts analyzed within 40 days. Soils, sediments, or slud-
equipped with Teflon® or glass connection joints and stopcocks ges may be stored for a maximum of 14 days and the extracts
requiring no lubrication, a K-D concentrating apparatus, water analyzed within 40 days.
bath, and an ultrasonic disrupter with a minimum power of SAMPLE PREPARATION
300 W and with pulsing capability are also required. Liquid samples — Transfer 1 L quantitatively to a continuous
PRECISION & ACCURACY The estimated quantitation extractor. If high concentrations are anticipated, a smaller vol-
limit (EQL) of Method 8270B for determining an individual ume may be used and then diluted with organic-free reagent
compound is approximately 1 mg/kg (wet weight) for soil or water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
sediment samples, 1–200 mg/kg for wastes (dependent on sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
The EQL(b) for groundwater in g/L is 20. should result in a final concentration of 100 ng/L of each
The EQL (a, b) for low concentrations in soil and sediment analyte in the extract to be analyzed (assuming a 1- L injec-
in g/kg is not determined. tion). Extract with methylene chloride for 18–24 h. Next, adjust
Accuracy as g/L is not listed. the pH of the aqueous phase to pH >11 using 10 N sodium
Overall precision in g/L is not listed. hydroxide and extract it with methylene chloride again for

18–24 h. Dry the extract through a column containing anhy- calibration check compounds (CCCs) are used to check the
drous sodium sulfate and concentrate it to 1 mL using a K-D validity of the initial calibration.
concentrator.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous calibration check standard must be evaluated immediately after
or wet samples (gummy or clay type) that do not have a free- or during data acquisition. If the retention time for any internal
flowing sandy texture must be mixed with anhydrous sodium standard changes by more than 30 seconds from the last check
sulfate until the sample is free flowing. Add 1 mL of surrogate calibration (12 h), the chromatographic system must be
standards to all samples, spikes, standards, and blanks. For the inspected for malfunctions and corrections must be made, as
sample in each analytical batch selected for spiking, add 1.0 mL required. If the electron ionization current plot (EICP) area for
of a matrix spiking standard. For base/neutral acid analysis, the any of the internal standards changes by a factor of two from
amount added of the surrogates and matrix spiking com- the last daily calibration standard check, the mass spectrometer
pounds should result in a final concentration of 100 ng/ L of must be inspected for malfunctions and corrections must be
each base/neutral analyte and 200 ng/L of each acid analyte made, as appropriate.
Immediately add a 100-mL mixture of 1:1 methylene chlo- Demonstrate, through the analysis of a reagent water blank,
ride:acetone and extract the sample ultrasonically for 3 min that interferences from the analytical system, glassware, and
and then decant or filter the extracts. Repeat the extraction two reagents are under control. The blank samples should be car-
or more times. Dry the extract using a column with anhydrous ried through all stages of the sample preparation and measure-
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. ment steps. For each analytical batch (up to 20 samples), a
QUALITY CONTROL A methylene chloride solution con- cate must be analyzed (the frequency of the spikes may be
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is different for different monitoring programs). The blank and
used for tuning the GC/MS system each 12-h shift. A system spiked samples must be carried through all stages of the sample
performance check also must be made during every 12-h shift. preparation and measurement steps. A QC reference sample
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- concentrate containing each analyte at a concentration of
rophenol, and benzidine is required to verify injection port 100 mg/L in methanol is required.
at mid-concentration, containing each compound of interest, REFERENCE Test Methods for Evaluating Solid Waste (SW-
including all required surrogates, must be performed every 12 h 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
during analysis. After the system performance check is met, of Solid Waste, Washington, DC.

L
Lead EPA Method 6010 acid and tap water. Collect at least 2 g of solids and 200 mL of
CAS #7439-92-1 aqueous samples.
SAMPLE PRESERVATION Add nitric acid to make the sam-
TITLE Inductively Coupled Plasma-Atomic Emission Spec-
ples pH <2.
troscopy
MHT The maximum holding time for properly preserved
MATRIX This method is applicable to the determination of
samples is 6 months.
trace elements, including metals, in groundwater, soils, sludges,
sediments, and other solid wastes. All matrices require diges- SAMPLE PREPARATION Preliminary treatment of most
tion prior to analysis. The method of standard addition must matrices is necessary because of the complexity and variability
be used for the analysis of all sample digests unless either serial of sample matrices. Water samples that have been prefiltered
dilution or matrix spike addition demonstrates it is not and acidified will not need acid digestion. Methods for acid
required. digestion of waters for total recoverable or dissolved metals,
METHOD SUMMARY Method 6010 covers 25 elements acid digestions of aqueous samples and extracts for total metals,
using ICP analysis. It measures element-emitted light by optical and acid digestion of sediments, sludges, and soils are summa-
spectrometry. Samples, following an appropriate acid diges- rized below.
tion, are nebulized and the resulting aerosol is transported to Total recoverable or dissolved metals in water — To prepare
the plasma torch. Element-specific atomic line emission spectra surface and groundwater samples for determination of total
are produced by a radio-frequency inductively coupled plasma. recoverable and dissolved metals, a 100-mL aliquot of well-
INTERFERENCES Interferences may be categorized as spec- mixed sample is acidified with concentrated nitric acid and
tral or non-spectral. Spectral interferences are caused by over- concentrated hydrochloric acid, then heated until the volume
lap of a spectral line from another element, unresolved overlap is reduced to 15–20 mL.Adjust the final volume to 100 mLwith
of molecular band spectra, background contribution from con- reagent water.
tinuous or recombination phenomenon, and stray light from Total metals in aqueous samples, soil and sediment extracts —
the line emission of high concentration elements. Non-spectral To prepare aqueous samples, soil and sediment extracts, and
interferences include physical and chemical interferences. Phys- wastes that contain suspended solids, a 100-mL aliquot is made
ical interferences are effects associated with the sample nebu- acidic with concentrated nitric acid and the solution is evapo-
lization and transport processes. Changes in viscosity and rated to about 5 mL on a hot plate. Continue heating and
surface tension can cause significant inaccuracies. Chemical adding additional acid until sample digestion is complete,
interferences include molecular compound formation, ioniza- which is usually indicated when the digestate is light in color
tion effects, and solute vaporization effects. Normally these or does not change in appearance. Evaporate the solution to
effects are not significant and can be minimized by careful about 3 mL and cool it and add a small quantity of 1:1 hydro-
selection of operating conditions. Chemical interferences are chloric acid (10 mL/100 mL of final solution). Cover the beaker
highly dependent on matrix type and the specific analyte element. and reflux for 15 min. Wash down the beaker walls and filters
INSTRUMENTATION An inductively coupled argon plasma or centrifuge the sample to remove silicates and other insoluble
emission spectrometer (ICP) capable of background correction material. Filter the sample and adjust the final volume to
is required. 100 mL with reagent water and the final acid concentration to
10%.
PRECISION & ACCURACY Detection limits, sensitivity, and
optimum ranges of the metals will vary with the matrices and Sediments, sludges, and soils — To prepare sediments, sludges
model of the spectrometer. In a single lab evaluation, seven and soil samples, transfer 1–2 g to a conical beaker and add
wastes were analyzed for 22 elements. The mean percent rela- 10 mL of 1:1 nitric acid, mix the slurry, and cover it with a
tive standard deviation from triplicate analyses for all elements watch glass. Heat the sample and reflux for 10–15 min without
and wastes was 9 2%. The mean percent recovery of spiked boiling. Allow it to cool, then add 5 mL of concentrated nitric
elements for all wastes was 93 6%. Spike levels ranged from acid and reflux for 30 min. Repeat last step and then allow the
100 g/L to 100 mg/L. The wastes included sludges and indus- solution to evaporate to 5 mL without boiling. Cool and add
trial wastewaters. 2 mL of water and 3 mL of 30% hydrogen peroxide. Cover and
place the beaker on the hot plate. Heat and add 30% hydrogen
Estimated instrument detection limit in g/L is 42. peroxide in 1-mL aliquots with warming until the effervescence
Spiked concentration in g/L is 24. is minimal but do not add more than a total of 10 mL of 30%
Mean reported value in g/L is 30. hydrogen peroxide. If the sample is being prepared for the
Precision as RSD % is 32. analysis of Ag, Al, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg,
SAMPLING METHOD Samples should be collected in boro- Mn, Mo, Na, Ni, Os, Pb, Se, Tl, V, and Zn, then add 5 mL of
silicate glass, linear polyethylene, polypropylene, or Teflon® concentrated hydrochloric acid and 10 mL of water and return
bottles that have been prewashed with detergent and tap water, the covered beaker to a hot plate for 15 min of additional refluxing
and rinsed with 1:1 nitric acid and tap water or 1:1 hydrochloric without boiling. Dilute the sample to a 100 mL volume with

water after cooling and filter or centrifuge to remove particu- INSTRUMENTATION Inductively coupled argon plasma
lates. emission spectroscopy. 220.353 nm wavelength
QUALITY CONTROL Laboratory control samples must be RANGE Not listed.
analyzed for each analytical method. A method blank should
MDL 42 g/L.
be analyzed with each batch of samples. The effect of the matrix
on method performance must be demonstrated: when appro- PRECISION SD = 16% Mean at true value 250 g/L.
priate, there should be at least one matrix spike and either one ACCURACY Mean recovery = 93% 6% of spiked elements
matrix duplicate or one matrix spike duplicate per analytical for all wastes.
batch. The bias and precision of the method, as well as the
method detection limit for each specific matrix type, must be SAMPLING METHOD Wash sample container with deter-
measured. gent and tap water, rinse with 1 + 1 nitric acid and tap water,
then rinse with 1 + 1 hydrochloric acid and tap water, then
Dilute and reanalyze samples that are more concentrated than rinse with deionized, distilled water in that order. Perform any
the linear calibration limit. Employ a minimum of one reagent filtration or acid preservation steps when the sample is col-
blank per sample batch to determine if contamination or any lected or as soon as possible thereafter.
memory effects are occurring. Whenever a new or unusual
sample matrix is encountered, perform either a serial dilution STABILITY Cool samples to 4C.
test or a matrix spike addition test to ensure that neither pos- MHT 24 h.
itive or negative interferences are operating on any of the ana-
lyte elements. Check the instrument standardization by QUALITY CONTROL Mixed calibration standards, an
verifying calibration every 10 samples using a calibration blank instrument check standard, and an interference check solution
and a check standard. are used in addition to a quality control sample. The quality
control sample should be prepared in the same acid matrix as
REFERENCE Test Methods for Evaluating Solid Waste (SW- the calibration standards at 10 times the instrumental detection
846). U.S. EPA. 1983. Method 6010, Rev. 0, Sept. 1986. Office limits and in accordance with the instructions provided by the
of Solid Wastes, Washington, DC. supplier. Furthermore, two types of blanks are required: a cal-
ibration blank and a reagent blank.
REFERENCE Method 200.7, U.S. EPA, EMSL-Cincinnati,
Lead EPA Method 200.7 OH, Nov. 1980
CAS #7439-92-1
TITLE Inductively Coupled Plasma

Lead EPA Method 7420
MATRIX Dissolved, suspended or (ICP) total element in
CAS #7439-92-1
drinking and surface waters and in domestic and industrial
wastewaters. TITLE Atomic Absorption (AA) Direct Aspiration
APPLICATION The method covers the determination of 25 MATRIX Drinking, surface, and saline waters. Wastewater
metals. Dissolved elements are determined in filtered and acid-
ified samples after appropriate digestion (which increases dis- APPLICATION Sample is aspirated and atomized in a flame.
solved solids). Its primary advantage is that ICP instruments A light beam from a Pb hollow cathode lamp is directed
allow simultaneous or rapid sequential determination of many through the flame into a monochromator and onto a detector.
elements in a short time. Samples are first nebulized and the Since wavelength of light beam is specific for Pb, light energy
aerosol is transported to a plasma torch in which element spe- absorbed by detector is measure of lead.
cific atomic line emission spectra are produced by a radio fre- INTERFERENCES The most troublesomee type is chemical,
quency inductively coupled plasma. Background correction is caused by lack of absorption of atoms bound in molecular
required for trace element detection except in the case of line combination in the flame. High dissolved solids in sample may
broadning. result in nonatomic absorbance interference. Background cor-
INTERFERENCES There are spectral, physical, and chemical rection is required.
interferences. The primary disadvantage of ICP instruments is INSTRUMENTATION Atomic absorption spectrometer.
background radiation from other elements and the plasma Lead hollow cathode lamp. [283.3 nm wavelength(primary)]
gases (spectral interferences). Changes in sample viscosity and
surface tension with samples containing high dissolved solids RANGE 1–20 mg/L.
(especially those exceeding 1500 mg/L) or high acid concentra- MDL 0.1 mg/L
tions can cause physical interferences. Ionization effects, solute
vaporization and molecular compound formation can cause PRECISION Standard deviation = 128 g/L at 367 g/L
chemical interferences.Aluminum can cause interference at the (true value) 74 labs
100 mg/L level. ACCURACY As bias = +2.9% at 367 g/L (true value) 74 labs

Leptophos EPA Method 8270
lect 200 g of solids and 600 mL of liquid samples. CAS #21609-90-5
STABILITY Cool solid samples to 4C and analyze as soon
as possible. Add nitric acid to liquid samples to pH <2. TITLE Semivolatile Organic Compounds by GC/MS
MHT 6 months. MATRIX This method is used to determine the concentra-

QUALITY CONTROL At least one duplicate and one spike from all types of solid waste matrices, soils, and groundwater.
sample should be run every 20 samples or with each matrix Although surface waters are not specifically mentioned, this
type to verify precision of the method. For 20 or more samples method should be applicable to water samples from rivers,
per day, verify working standard curve. Run an additional stan- lakes, etc.
dard at or near mid-range every 10 samples.
REFERENCE Method 7420, SW-846, 3rd ed., Nov.1986. organic compounds. In very limited applications direct injec-
Lead EPA Method 7421 gate, and matrix spiking standards, is extracted in a continuous
CAS #7439-92-1 extractor first under acid conditions and then under basic con-
TITLE Atomic Absorption (AA) and matrix spiking standards, is extracted ultrasonically. After
MATRIX Drinking, surface, and furnace technique saline concentrating the extract to 1 mL it is spiked with 10 L of an
waters. Wastewater. internal standard solution just prior to analysis by GC/MS. The
APPLICATION Pb in solution is readily determined by and 200 ng of acid surrogates (for a 1-L injection). Analysis
atomic absorption spectrometer, but detection limits, sensitiv- is performed by GC/MS using a capillary GC column.
ity and optimum range vary with the matrices and models of
AA spectrophotometers. While drinking water may be analyzed
directly, ground water, other aqueous samples, EP extracts,
industrial wastes, soils, sludges, and sediments require digestion. and low-concentration samples are sequentially analyzed. To
INTERFERENCES “Chemical” interference is caused by lack reduce carryover, the sample syringe must be rinsed out
of absorption of atoms bound in molecular combination in the between samples with solvent. Whenever an unusually concen-
flame. High dissolved solids in sample may cause interference trated sample is encountered, it should be followed by the
from non atomic absorbance. Ionization and spectral interfer- analysis of blank solvent to check for cross-contamination.
ences can occur. INSTRUMENTATION A GC/MS and a data system are
INSTRUMENTATION Atomic absorption spectrometer. required. The GC column used is a 30 m 0.25 mm I.D. (or
Lead (Pb) hollow cathode lamp. Graphite furnace. 283 nm
wavelength.
RANGE 5–100 g/L. requiring no lubrication, a K-D concentrating apparatus, water
MDL 1 g/L
PRECISION Standard deviation = 3.7 at 100 g Pb/L.
ACCURACY Recovery = 95% at 100 g Pb/L. limit (EQL) of Method 8270B for determining an individual
SAMPLING METHOD Use glass or plastic containers. Col- sediment samples, 1–200 mg/kg for wastes (dependent on
lect 200 g of solids and 600 mL of liquid samples. matrix and method of preparation), and 10 g/L for ground-
STABILITY Cool solid samples to 4C and analyze as soon water samples. EQLs will be proportionately higher for sample
as possible. Add nitric acid to liquid samples to pH <2. extracts that require dilution to avoid saturation of the detector.
MHT 6 months. The EQL(b) for groundwater in g/L is 10.

QUALITY CONTROL At least one duplicate and one spike in g/kg is not determined.
sample should be run every 20 samples, or with each matrix Accuracy as g/L is not listed.
type to verify method precision. If 20 or more samples are run, Overall precision in g/L is not listed.
run a standard (at or near mid-range) every 10 samples.
REFERENCE Method 7421, SW-846, 3rd ed., Nov.1986. mally data is reported in a dry-weight basis; therefore, EQLs

will be higher based on the % dry weight of each sample. Soils, sediments, or sludges — Use 30 g of sample. Nonporous
This calculation is based on a 30-g sample and gel perme- or wet samples (gummy or clay type) that do not have a free-
ation chromatography cleanup. flowing sandy texture must be mixed with anhydrous sodium
(b) Sample EQLs are highly matrix-dependent. The EQLs are sulfate until the sample is free flowing. Add 1 mL of surrogate
provided for guidance and may not always be achievable. standards to all samples, spikes, standards, and blanks. For the
C = True value for concentration, in g/L. sample in each analytical batch selected for spiking, add 1.0 mL
X = Average recovery found for measurements of samples con- of a matrix spiking standard. For base/neutral acid analysis, the
taining a concentration of C, in g/L. amount added of the surrogates and matrix spiking com-
ESTIMATED QUANTITATION LIMIT pounds should result in a final concentration of 100 ng/ L of
Other Matrices Factor (a) each base/neutral analyte and 200 ng/L of each acid analyte
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor]. and then decant or filter the extracts. Repeat the extraction two
This estimated EQL is similar to an EPA “Practical Quantitation or more times. Dry the extract using a column with anhydrous
Limit.” sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
SAMPLING METHOD QUALITY CONTROL A methylene chloride solution con-
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
a screw-top Teflon®-lined cover that has been prewashed with used for tuning the GC/MS system each 12-h shift. A system
detergent and rinsed with distilled water and methanol (or performance check also must be made during every 12-h shift.
isopropanol). A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
Soils, sediments, or sludges — Use an 8-oz. widemouth glass rophenol, and benzidine is required to verify injection port
with a screw-top Teflon®-lined cover that has been prewashed inertness and GC column performance. A calibration standard
with detergent and rinsed with distilled water and methanol at mid-concentration, containing each compound of interest,
(or isopropanol). including all required surrogates, must be performed every 12 h
SAMPLE PRESERVATION
solvent-free refrigerator until analysis; if chlorine is not present, The internal standard responses and retention times in the
then eliminate the sodium thiosulfate addition. calibration check standard must be evaluated immediately after
MHT Liquid samples must be extracted within 7 days and inspected for malfunctions and corrections must be made, as
the extracts analyzed within 40 days. Soils, sediments, or slud- required. If the electron ionization current plot (EICP) area for
ges may be stored for a maximum of 14 days and the extracts any of the internal standards changes by a factor of two from
analyzed within 40 days. the last daily calibration standard check, the mass spectrometer
SAMPLE PREPARATION must be inspected for malfunctions and corrections must be
Liquid samples — Transfer 1 L quantitatively to a continuous made, as appropriate.
extractor. If high concentrations are anticipated, a smaller vol- Demonstrate, through the analysis of a reagent water blank,
ume may be used and then diluted with organic-free reagent that interferences from the analytical system, glassware, and
18–24 h. Dry the extract through a column containing anhy- REFERENCE Test Methods for Evaluating Solid Waste (SW-
drous sodium sulfate and concentrate it to 1 mL using a K-D 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
concentrator. of Solid Waste, Washington, DC.

Longifolene EPA Method 1625
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu- The minimum level (in g/mL) was not listed. This is defined
tion GC/MS as a minimum level at which the analytical system shall give
deviation (in g/L) was not listed.

Spike all samples with labeled compounds to assess method Field replicates may be collected to determine the precision of
performance. Compute percent recovery of the labeled com- the sampling technique, and spiked samples may be required
pounds using the internal standard method. Compare the to determine the accuracy of the analysis when the internal
labeled compound recovery for each compound with the cor- standard method is used.
responding labeled compound recovery.
Reagent water and high solids reference matrix blanks are ana- Dilution GC/MS. Office of Water Regulation and Standards,
lyzed to demonstrate freedom from contamination. Extract and U.S. EPA Industrial Technology Division, Washington, DC,
concentrate a 1-L reagent water blank or a high solids reference EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
matrix blank with each sample’s lot (samples started through the U.S. EPA, Office of Water Regulations and Standards, 401 M
extraction process on the same 8-h shift, to a maximum of St., SW, Washington, DC, 20460. Phone: 202-382-7131).
20 samples).

Compilation of EPA's Sampling and Analysis Methods

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Keith, Lawrence H.

©1996 CRC Press LLC

©1996 CRC Press LLC

©1996 CRC Press LLC

©1996 CRC Press LLC

©1996 CRC Press LLC

©1996 CRC Press LLC

©1996 CRC Press LLC

©1996 CRC Press LLC

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©1996 CRC Press LLC

©1996 CRC Press LLC

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©1996 CRC Press LLC

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RANGE 5–600 g/L ACCURACY 0.94C + 0.31 g/L (as recovery).

QUALITY CONTROL The lab must on an ongoing basis, MHT 14 days.

©1996 CRC Press LLC

©1996 CRC Press LLC

©1996 CRC Press LLC

©1996 CRC Press LLC

©1996 CRC Press LLC

©1996 CRC Press LLC

©1996 CRC Press LLC