Designation: D 858 – 07

Standard Test Methods for

Manganese in Water1
This standard is issued under the fixed designation D 858; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense.

1. Scope Steam in Closed Conduits3

1.1 These test methods cover the atomic absorption deter- D 1193 Specification for Reagent Water
mination of dissolved and total recoverable manganese in D 1687 Test Methods for Chromium in Water
water and certain wastewaters. Three test methods are given as D 1688 Test Methods for Copper in Water
follows: D 1691 Test Methods for Zinc in Water
Test Method Concentration Range Sections
D 1886 Test Methods for Nickel in Water
A—Atomic Absorption, Direct 0.1 to 5 mg/L 7 to 15 D 2777 Practice for Determination of Precision and Bias of
B—Atomic Absorption, 10 to 500 µg/L 16 to 24 Applicable Test Methods of Committee D19 on Water
Chelation-Extraction
C—Atomic Absorption, Graphite 5 to 50 µg/L 25 to 33
D 3370 Practices for Sampling Water from Closed Conduits
Furnace D 3557 Test Methods for Cadmium in Water
1.2 Test Methods A, B, and C were used successfully on D 3558 Test Methods for Cobalt in Water
reagent grade and natural waters. Other matrices used in the D 3559 Test Methods for Lead in Water
study were brine (Test Method B), effluent from a wood D 3919 Practice for Measuring Trace Elements in Water by
treatment plant, and condensate from a medium BTU coal Graphite Furnace Atomic Absorption Spectrophotometry
gasification process (Test Method C). It is the user’s responsi- D 4841 Practice for Estimation of Holding Time for Water
bility to ensure the validity of a test method for waters of Samples Containing Organic and Inorganic Constituents
untested matrices. D 5810 Guide for Spiking into Aqueous Samples
1.3 This standard does not purport to address all of the D 5847 Practice for Writing Quality Control Specifications
safety concerns, if any, associated with its use. It is the for Standard Test Methods for Water Analysis
responsibility of the user of this standard to establish appro- 3. Terminology
priate safety and health practices and determine the applica-
3.1 Definitions of Terms Specific to This Standard:
bility of regulatory limitations prior to use. For specific hazard
3.1.1 total recoverable manganese—an arbitrary analytical
statements, see 11.7, 20.2, 20.9, and 22.10.
term relating to the recoverable forms of manganese that are
1.4 Former Test Method A (Colorimetric) was discontinued.
determinable by the digestion method which is included in the
For historical information, see Appendix X1.
procedure.
2. Referenced Documents 3.2 Definitions:
2.1 ASTM Standards: 2 3.2.1 For definitions of terms used in these test methods,
D 1066 Practice for Sampling Steam refer to Terminology D 1129.
D 1068 Test Methods for Iron in Water 4. Significance and Use
D 1129 Terminology Relating to Water
4.1 Elemental constituents in potable water, receiving water,
D 1192 Guide for Equipment for Sampling Water and
and wastewater need to be identified for support of effective
pollution control programs. Test Methods A, B, and C provide
the techniques necessary to make such measurements.
1
These test methods are under the jurisdiction of ASTM Committee D19 on 4.2 Although inhaled manganese dusts have been reported
Water and are the direct responsibility of Subcommittee D19.05 on Inorganic to be toxic to humans, manganese normally is ingested as a
Constituents in Water.
Current edition approved Aug. 1, 2007. Published August 2007. Originally trace nutrient in both food and water. Because it is considered
approved in 1945. Last previous edition approved in 2002 as D 858 – 02. to be relatively nontoxic to man, as well as aquatic life, a limit
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
3
the ASTM website. Withdrawn.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 D 858 – 07
of 50 µg/L has been established in the EPA National Secondary 8. Summary of Test Method
Drinking Water Regulations. This limit is based primarily on 8.1 Manganese is determined by atomic absorption spectro-
its ability to stain laundry and produce objectionable tastes in photometry. Dissolved manganese is determined by atomizing
beverages. a filtered sample directly with no pretreatment. Total recover-
4.3 Manganese does not occur naturally as a metal but is able manganese in the sample is determined in a portion of the
found in various salts and minerals, frequently in association filtrate obtained after a hydrochloric-nitric acid digestion of the
with iron compounds. Manganese is not mined in the United sample. The same digestion procedure is used to determine
States except when manganese is contained in iron ores that are total recoverable cadmium (Test Methods D 3557), chromium
deliberately used to form ferro-manganese alloys. Manganese (Test Methods D 1687), cobalt (Test Methods D 3558), copper
salts are used as fertilizer additives and are commonly found in (Test Methods D 1688), iron (Test Methods D 1068), lead (Test
surface and ground waters. Methods D 3559), nickel (Test Methods D 1886), and zinc
(Test Methods D 1691).
5. Purity of Reagents
9. Interferences
5.1 Reagent grade chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all reagents shall 9.1 Magnesium in concentrations greater than 100 mg/L
conform to the specifications of the Committee on Analytical may interfere.
Reagents of the American Chemical Society, where such 9.2 No interference from SiO2 in concentrations up to 100
specifications are available. 4 Other grades may be used, mg/L has been observed.
provided it is first ascertained that the reagent is of sufficiently 9.3 Background correction or chelation-extraction (see Test
high purity to permit its use without lessening the accuracy of Method B) to remove interferences may be necessary to
the determination. determine low levels of manganese in some waters.
5.2 Purity of Water—Unless otherwise indicated, references NOTE 1—Instrument manufacturers’ instructions for use of the specific
to water shall be understood to mean reagent water conforming correction technique should be followed.
to Specification D 1193, Type I. Other reagent water types may
10. Apparatus
be used, provided it is first ascertained that the water is of
sufficiently high purity to permit its use without lessening the 10.1 Atomic Absorption Spectrophotometer, for use at 279.5
bias and precision of the determination. Type II water was nm.
specified at the time of round-robin testing of this test method. NOTE 2—The manufacturer’s instructions should be followed for all
instrumental parameters. A wavelength other than 279.5 nm may be used
6. Sampling if it has been determined to be equally suitable.
6.1 Collect the sample in accordance with Practice D 1066, 10.1.1 Manganese Light Source—Multielement lamps,
Specification D 1192, or Practices D 3370 as applicable. electrodeless discharge lamps, or hollow-cathode lamps have
6.2 Samples shall be preserved with HNO3(sp gr 1.42), been found satisfactory.
normally about 2 mL/L, to a pH of 2 or less immediately at the 10.2 Pressure-Reducing Valves—The supplies of fuel and
time of collection. If only dissolved manganese is to be oxidant shall be maintained at pressures somewhat higher than
determined, the sample shall be filtered through a 0.45-µm (No. the controlled operating pressure of the instrument by suitable
325) membrane filter before acidification. The holding time for valves.
samples may be calculated in accordance with Practice D 4841. 11. Reagents and Materials
TEST METHOD A—ATOMIC ABSORPTION, DIRECT 11.1 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
chloric acid (HCl).
7. Scope NOTE 3—If a high reagent blank is obtained, distill the HCl or use
spectrograde acid. (Warning—When HCl is distilled, an azeotropic
7.1 This test method covers the determination of dissolved mixture is obtained (approximately 6 NHCl). Therefore, whenever con-
and total recoverable manganese and has been used success- centrated HCl is specified in the preparation of a reagent or in the
fully with reagent and natural water. It is the analyst’s procedure, use double the amount specified if distilled acid is used.)
responsibility to ensure the validity of the method in a 11.2 Manganese Solution, Stock (1.0 mL = 1.0 mg Mn)—
particular matrix. Dissolve 3.076 g of manganous sulfate monohydrate
7.2 This test method is applicable in the range from 0.1 to 5 (MnSO4·H2O) in a mixture of 10 mL of HNO3(sp gr 1.42) and
mg/L of manganese. The range may be extended to concentra- 100 mL of water. Dilute to 1 L with water. A purchased stock
tions greater than 5 mg/L by dilution of the sample. solution of appropriate purity is also acceptable.
11.3 Manganese Solution, Standard (1.0 mL = 0.1 mg
Mn)—Dilute 100.0 mL of manganese stock solution to 1 L
4
Reagent Chemicals, American Chemical Society Specifications, American
with water.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not 11.4 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
listed by the American Chemical Society, see Analar Standards for Laboratory (HNO3).
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, NOTE 4—If a high reagent blank is obtained, distill the HNO3 or use
MD. spectrograde acid.

2
 D 858 – 07
11.5 Nitric Acid (1 + 499)—Add 1 volume of HNO3(sp gr TABLE 1 Precision and Concentration, Direct Aspiration
1.42) to 499 volumes of water. Reagent water:
Concentration (X̄), mg/L 0.424 2.034 4.053
11.6 Oxidant: ST 0.045 0.177 0.317
11.6.1 Air, which has been passed through a suitable filter to SO 0.021 0.070 0.151
remove oil, water, and other foreign substances, is the usual Natural water:
Concentration (X̄), mg/L 0.417 2.033 4.076
oxidant. ST 0.045 0.179 0.305
11.7 Fuel: SO 0.037 0.074 0.149
Acetylene—standard, commercially available acetylene is
the usual fuel. Acetone, always present in acetylene cylinders,
can affect analytical results. The cylinder should be replaced at 14. Calculation
50 psig (345 kPa).Warning—“Purified” grade acetylene con- 14.1 Determine the concentration of manganese in each
taining a special proprietary solvent other than acetone should sample, in milligrams per L, using an analytical curve or,
not be used with poly(vinyl chloride) tubing as weakening of alternatively, read directly in concentration (see 12.4).
the tubing walls can cause a potentially hazardous situation.
15. Precision and Bias 5
12. Standardization 15.1 The supporting data on this collaborative study in-
12.1 Prepare 100 mL each of a blank and at least four cludes reagent and natural water matrices. It is the responsi-
standard solutions to bracket the expected manganese concen- bility of the analyst to ensure the validity of the test method in
tration range of the samples to be analyzed by diluting the a particular matrix.
manganese standard solution with HNO3(1 + 499). Prepare the 15.2 The precision of this test method was tested by eleven
standards each time the test is to be performed, and select so as laboratories. Five laboratories reported data for two operators.
to give zero, middle, and maximum points for an analytical The precision of this test method is shown in Table 1; the bias
curve. is shown in Table 2.
15.3 Precision and bias for this test method conform to
NOTE 5—It is recommended that the blank (zero standard) be compared
Practice D 2777-77, which was in place at the time of
with reagent grade water to avoid the possibility of using a high blank.
collaborative testing. Under the allowances made in 1.4 of
12.2 When determining total recoverable manganese add Practice D 2777-06, these precision and bias data do meet
0.5 mL of HNO3(sp gr 1.42) and proceed as directed in 13.2. existing requirements for interlaboratory studies of Committee
When determining dissolved manganese proceed with 13.5. D19 test methods.
12.3 Aspirate the blank and standards and record the instru-
ment readings. Aspirate HNO3(1 + 499) between each stan- TEST METHOD B—ATOMIC ABSORPTION,
dard. CHELATION-EXTRACTION
12.4 Prepare an analytical curve by plotting the absorbance 16. Scope
of each standard versus its concentration on linear graph paper.
Alternatively read directly in concentration from the instru- 16.1 This test method covers the determination of dissolved
ment. and total recoverable manganese and has been used success-
fully with reagent water, tap water, river water, artificial
13. Procedure seawater and a synthetic (NaCl) brine. It is the user’s respon-
sibility to ensure the validity of this test method for waters of
13.1 Measure 100.0 mL of a well-mixed acidified sample other matrices.
into a 125-mL beaker or flask. 16.2 This test method is applicable in the range from 10 to
NOTE 6—If only dissolved manganese is to be determined, start with 500 µg/L of manganese. The range may be extended to
13.5. concentrations greater than 500 µg/L by dilution of the sample.
13.2 Add 5 mL of HCl (sp gr 1.19) to each sample. 17. Summary of Test Method
13.3 Heat the samples on a steam bath or hot plate in a 17.1 Manganese is determined by atomic absorption spec-
well-ventilated hood until the volume has been reduced to 15 trophotometry. The element, either dissolved or total recover-
or 20 mL, making certain that the samples do not boil. able, is chelated with pyrrolidine dithiocarbamic acid and
NOTE 7—For brines and samples with high levels of suspended matter, extracted with chloroform. The extract is evaporated to dry-
the amount of reduction in volume is left to the discretion of the analyst. ness, treated with hot HNO3 to destroy organic matter, dis-
solved in HCl, and diluted to a specified volume with water. A
13.4 Cool and filter the samples through a suitable filter
portion of the resulting solution is then atomized into the
paper, such as fine-textured, acid-washed, ashless paper into
air-acetylene flame of the spectrophotometer. The digestion
100-mL volumetric flasks. Wash the filter paper two or three
procedure summarized in 8.1 is used to determine total
times with water and adjust to volume.
recoverable manganese.
13.5 Set the instrument to zero using reagent blank (zero
standard). Aspirate each filtered acidified sample and standard;
record its absorbance or concentration. Aspirate 5
Supporting data for Test Methods A and B are available from ASTM
HNO3(1 + 499) between each sample and standard. International Headquarters. Request RR: D19-1034.

3
 D 858 – 07
TABLE 2 Determination of Bias, Direct Aspiration 21.2 To determine total recoverable manganese use 125-mL
Statistically beakers or flasks, add 0.5 mL of HNO3(sp gr 1.42) and proceed
Amount Amount Significant as directed in 22.2. To determine dissolved manganese use
Added, Found, Bias, mg/L % Bias (95%
mg/L mg/L Confidence 250-mL separatory funnels and proceed as directed in 22.5.
Level) 21.3 Construct an analytical curve by plotting the absor-
Reagent water: bances of standards versus micrograms of manganese. Alter-
0.4 0.424 + 0.024 +6 yes natively read directly in concentration from the instrument.
2.0 2.034 + 0.034 + 1.7 no
4.0 4.053 + 0.053 + 1.3 no 22. Procedure
Natural water:
0.4 0.417 + 0.017 + 4.2 yes 22.1 Measure a volume of a well-mixed acidified sample
2.0 2.033 + 0.033 + 1.7 no containing less than 50.0 µg of manganese (100-mL maximum)
4.0 4.076 + 0.076 + 1.9 yes
into a 125-mL beaker or flask and adjust the volume to 100 mL
with water.
18. Interferences NOTE 8—If only dissolved manganese is to be determined, measure a
18.1 See Section 9. volume of sample filtered through a 0.45-µm (No. 325) membrane filter
and acidified (6.2) containing less than 50.0 µg of manganese (100-mL
19. Apparatus maximum) into a 250-mL separatory funnel, and start with 22.5.
19.1 All items of apparatus described in Section 10 are 22.2 Add 5 mL of HCl (sp gr 1.19) to each sample.
required. 22.3 Heat the samples on a steam bath or hot plate until the
volume has been reduced to 15 to 20 mL, making certain that
20. Reagents and Materials the samples do not boil.
20.1 Bromcresol Green Indicator Solution (1 g/L)— NOTE 9—For brines and samples with high levels of suspended matter,
Dissolve 0.1 g of bromcresol green in 100 mL of 20 % ethanol. the amount of reduction in volume is left to the discretion of the analyst.
20.2 Chloroform (CHCl 3 ) (Warning—Use in well-
22.4 Cool and filter the samples through a suitable filter
ventilated hood.)
such as fine-textured, acid-washed, ashless paper into 250-mL
20.3 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
separatory funnels. Wash the filter paper two or three times
chloric acid (HCl) (see Note 3).
with water and adjust the volume to approximately 100 mL.
20.4 Hydrochloric Acid (1 + 2)—Add 1 volume of HCl (sp
22.5 Add 2 drops of bromcresol green indicator solution and
gr 1.19) to 2 volumes of water (see Note 3).
mix.
20.5 Hydrochloric Acid (1 + 49)—Add 1 volume of HCl (sp
22.6 Adjust the pH by addition of NaOH solution (100 g/L)
gr 1.19) to 49 volumes of water.
until a blue color persists. Add HCl (1 + 49) by drops until a
20.6 Manganese Solution, Stock (1.0 mL = 100 µg Mn)—
light olive-green color is obtained. The pH at this point should
Dissolve 0.3076 g of manganous sulfate monohydrate
be 4.0.
(MnSO4·H2O) in water containing 1 mL of HNO3(sp gr 1.42)
and dilute to 1 L with water. NOTE 10—The pH adjustment in 22.6 may be made with a pH meter
20.7 Manganese Solution, Standard (1.0 mL = 1.0 µg instead of using an indicator.
Mn)—Dilute 10.0 mL of manganese stock solution and 1 mL 22.7 Add 10 mL of pyrrolidine dithiocarbamic acid-
of HNO3(sp gr 1.42) to 1 L with water. This standard is used to chloroform reagent and shake vigorously for 2 min.
prepare working standards at the time of analysis. 22.8 Plug the tip of the separatory funnel with cotton, allow
20.8 Nitric Acid (sp gr 1.42)—Concentrated nitric acid the phases to separate, and drain the chloroform phase into a
(HNO3) (see Note 4). 100-mL beaker.
20.9 Pyrrolidine Dithiocarbamic Acid-Chloroform 22.9 Repeat the extraction with 10 mL of chloroform and
Reagent—Add 36 mL of pyrrolidine to 1 L of CHCl3. Cool the drain the chloroform layer into the same beakers.
solution and add 30 mL of CS2 in small portions, swirling NOTE 11—If color still remains in the chloroform extract, reextract the
between additions. Dilute to 2 L with CHCl3. The reagent can aqueous phase until the chloroform layer is colorless.
be used for several months if stored in a cool, dark place. 22.10 Place the beaker on a hotplate set at low heat or on a
(Warning—All components of this reagent are highly toxic. steam bath and evaporate to near dryness. Remove beaker from
Prepare and use in a well-ventilated hood. Avoid inhalation and heat and allow residual solvent to evaporate without further
direct contact.) heating. (Warning—Perform in a well-ventilated hood.)
20.10 Sodium Hydroxide Solution (100 g/L)—Dissolve 100 22.11 Hold the beaker at a 45° angle, and slowly dropwise
g of sodium hydroxide (NaOH) in water and dilute to 1 L. add 2 mL of HNO3(sp gr 1.42), rotating the beaker to effect
20.11 Oxidant—See 11.6. thorough contact of the acid with the residue.
20.12 Fuel—See 11.7.
NOTE 12—If acid is added to the beaker in a vertical position, a violent
21. Standardization reaction will occur accompanied by high heat and spattering.
21.1 Prepare a blank and sufficient standards containing 22.12 Place the beaker on a hotplate set at low heat or on a
from 0.0 to 50.0 µg of manganese by diluting 0 to 50.0-mL steam bath and evaporate to near dryness. Remove beaker from
portions of manganese standard solution (20.7) to 100 mL with heat and allow residual solvent to evaporate without further
water. heating.

4
 D 858 – 07
TABLE 3 Precision and Concentration, Chelation–Extraction TABLE 4 Determination of Bias, Chelation–Extraction
Reagent water: Statistically
Concentration (X̄), µg/L 21.47 121.47 292.83 Amount Amount Significant
ST 2.4 10.50 27.36 Added, Found, Bias, µg/L % Bias (95 %
SO 2.2 7.37 9.10 µg/L µg/L Confidence
Natural water: Level)
Concentration (X̄), µg/L 22.17 120.87 268.02
Reagent water:
ST 3.50 9.00 14.99
20 21.47 + 1.47 + 7.4 yes
SO 3.74 7.21 12.08
120 121.47 + 1.47 + 1.2 no
300 292.83 −7.13 −2.4 no
Natural water:
20 22.17 + 2.17 + 10.9 yes
120 120.87 + 0.87 + 0.7 no
22.13 Add 2 mL of HCl (1 + 2) to the beaker, and heat, 300 268.02 −31.98 −10.6 yes
while swirling, for 1 min.
NOTE 13—If a precipitate appears when the hydrochloric acid (1 + 2) is
added to the dried residue, obtain a fresh supply of pyrrolidine that has a 25.2 This test method is applicable in the range from
different lot number or redistill the pyrrolidine just before preparing the approximately 5 to 50 µg/L of manganese using a 20-µL
pyrrolidine dithiocarbamic acid-chloroform reagent.
injection. The range can be increased or decreased by varying
22.14 Cool and quantitatively transfer the solution to a the volume of sample injected or the instrumental settings.
10-mL volumetric flask and adjust to volume with water. Samples containing high concentrations may be diluted but
22.15 Aspirate each sample and record the scale reading or preferably should be analyzed by direct aspiration atomic
concentration. absorption spectrophotometry (Test Method A).
25.3 The analyst is encouraged to consult Practice D 3919
23. Calculation for a general discussion of interferences and sample analysis
23.1 Determine the weight of manganese in each sample by procedures for graphite furnace atomic absorption spectropho-
referring to 21.3. Calculate the concentration of manganese in tometry.
micrograms per L using Eq 1:
26. Summary of Test Method
1000 3 B
Manganese, µg/L 5 A (1) 26.1 Manganese is determined by an atomic absorption
spectrophotometer used in conjunction with a graphite furnace.
where: A sample is placed in a graphite tube, evaporated to dryness,
A = volume of sample, mL, and charred (pyrolyzed or ashed), and atomized. The absorption
B = weight of manganese in sample, µg. signal generated during atomization is recorded and compared
to standards. A general guide for the application of the graphite
24. Precision and Bias 5 furnace is given in Practice D 3919.
24.1 The precision of this test method was tested by six 26.2 Dissolved manganese is determined on a filtered
laboratories in reagent water, natural waters, and in synthetic sample with no pretreatment.
brines. One laboratory reported data from two operators. The 26.3 Total recoverable manganese is determined following
precision of this test method for reagent and natural water acid digestion and filtration. Because chlorides interfere with
matrices is shown in Table 3; the bias is shown in Table 4. furnace procedures for some metals, the use of hydrochloric
24.2 It is the user’s responsibility to ensure the validity of acid in any digestion or solubilization step is to be avoided. If
this test method for waters of untested matrices. suspended material is not present, this digestion and filtration
24.3 Precision and bias for this test method conform to may be omitted.
Practice D 2777-77, which was in place at the time of
collaborative testing. Under the allowances made in 1.4 of 27. Interferences
Practice D 2777-06, these precision and bias data do meet 27.1 For a complete discussion on general interferences
existing requirements for interlaboratory studies of Committee with furnace procedures, the analyst is referred to Practice
D19 test methods. D 3919.

TEST METHOD C—ATOMIC ABSORPTION, 28. Apparatus

GRAPHITE FURNACE 28.1 Atomic Absorption Spectrophotometer, for use at 279.5
nm with background correction (see Note 14 and Note 15).
25. Scope NOTE 14—A wavelength other than 279.5 nm may be used if it has been
25.1 This test method covers the determination of dissolved determined to be suitable.
and total recoverable manganese and has been used success- NOTE 15—The manufacturer’s instructions should be followed for all
fully with reagent water, river water, well and filtered tap instrumental parameters.
water, an effluent from a wood treatment plant, and a conden- 28.2 Manganese Hollow-Cathode Lamp—A single-element
sate from a medium BTU coal gasification process. It is the lamp is preferred, but multielement lamps may be used.
user’s responsibility to ensure the validity of the test method to 28.3 Graphite Furnace, capable of reaching temperatures
waters of other matrices. sufficient to atomize the element of interest.

5
 D 858 – 07
28.4 Graphite Tubes, compatible with furnace device. Py- TABLE 5 Determination of Bias and Overall Precision in Reagent
rolytically coated tubes are preferred. Water, Atomic Absorption Graphite Furnace
28.5 Pipettes, microlitre with disposable tips. Sizes may Amount Amount
Statistically
Added, Found, ST Bias, µg/L % Bias
range from 5 µL to 100 µL, as required. µg/L µg/L
Significant
28.6 Data Storage and Reduction Devices, Computer- and
7.5 7.37 0.74 −0.13 −1.7 no
Microprocessor-Controlled Devices, or Strip Chart Recorder- 15 14.9 1.78 −0.1 −0.7 no
s shall be utilized for collection, storage, reduction, and 44 42.9 7.44 −1.1 −2.5 no
problem recognition (such as drift, incomplete atomization,
changes in sensitivity, etc.).
28.7 Automatic sampling is recommended.
33. Precision and Bias 6
29. Reagents and Materials 33.1 The precision of this test method was tested by 13
29.1 Manganese Solution, Stock (1.0 mL = 100 µg Mn)— laboratories in reagent water, river water, well water, filtered
See 20.6. tap water, an effluent from a wood treatment plant, and
29.2 Manganese Solution, Standard (1.0 mL = 1.0 µg condensate from a medium BTU coal gas process. Two
Mn)—See 20.7. laboratories reported data from two operators. Although mul-
29.3 Nitric Acid (sp gr 1.42)—Concentrated nitric acid tiple injections may have been made, the report sheets provided
(HNO3) (Note 4). allowed only for reporting single values. Thus, no single-
29.4 Argon, standard, welders grade, commercially avail- operator precision data can be calculated. Bias data and overall
able. Nitrogen may also be used if recommended by the precision data are given in Table 5 and Table 6.
instrument manufacturer. 33.2 These data may not apply to waters of other matrices,
therefore, it is the responsibility of the analyst to ensure the
30. Standardization validity of this test method in a particular matrix.
33.3 3 Precision and bias for this test method conform to
30.1 Initially, set the instrument in accordance with the
Practice D 2777-77, which was in place at the time of
manufacturer’s specifications. Follow the general instructions
collaborative testing. Under the allowances made in 1.4 of
as provided in Practice D 3919.
Practice D 2777-06, these precision and bias data do meet
existing requirements for interlaboratory studies of Committee
31. Procedure
D19 test methods.
31.1 Clean all glassware to be used for preparation of
standard solutions or in the solubilization step, or both, by 34. Quality Control
rinsing first with HNO3(1 + 1) and then with water.
34.1 In order to be certain that analytical values obtained
31.2 Measure 100.0 mL of each standard and well-mixed
using these test methods are valid and accurate within the
sample into 125-mL beakers or flasks. For total recoverable
confidence limits of the test, the following QC procedures must
manganese add HNO3(sp gr 1.42) to each standard and sample
be followed when analyzing manganese.
at a rate of 5 mL/L and proceed as directed in 31.4-31.6.
34.2 Calibration and Calibration Verification:
31.3 If only dissolved manganese is to be determined, filter
34.2.1 Analyze at least three working standards containing
the sample through a 0.45-µm membrane filter prior to acidi-
concentrations of manganese that bracket the expected sample
fication, and proceed to 31.6.
concentration prior to analysis of samples to calibrate the
31.4 Heat the samples at 95°C on a steam bath or hotplate
instrument.
in a well-ventilated fume hood until the volume has been
34.2.2 Verify instrument calibration after standardization by
reduced to 15 to 20 mL, making certain that the samples do not
analyzing a standard at the concentration of one of the
boil (Note 8).
calibration standards. The absorbance shall fall within 4 % of
31.5 Cool and filter the sample through a suitable filter
the absorbance from the calibration. Alternately, the concen-
(such as fine-textured, acid-washed, ashless paper) into a
tration of a mid-range standard should fall within 6 10 % of
100-mL volumetric flask. Wash the filter paper two or three
the known concentration.
times with water, and bring to volume (Note 16). The acid
34.2.3 If calibration cannot be verified, recalibrate the
concentration at this point should be 0.5 % HNO3.
instrument.
NOTE 16—If suspended material is not present, this filtration may be 34.3 Initial Demonstration of Laboratory Capability:
omitted but the sample must still be diluted to 100 mL. 34.3.1 If a laboratory has not performed the test before, or if
31.6 Inject a measured aliquot of sample into the furnace there has been a major change in the measurement system, for
device following the directions as provided by the particular example, new analyst, new instrument, etc., a precision and
instrument manufacturer. Refer to Practice D 3919. bias study must be performed to demonstrate laboratory
capability.
32. Calculation
32.1 Determine the concentration of manganese in each
sample in accordance with the Samples Analysis Procedure in 6
Supporting data are available from ASTM International Headquarters. Request
Practice D 3919. RR: D19-1106.

6
 D 858 – 07
TABLE 6 Determination of Bias and Overall Precision in Water of standard. The spike must produce a concentration in the spiked
Choice, Atomic Absorption Graphite Furnace sample that is 2 to 5 times the analyte concentration in the
Amount Amount unspiked sample, or 10 to 50 times the detection limit of the
Statistically
Added, Found, ST Bias, µg/L % Bias
µg/L µg/L
Significant test method, whichever is greater.
7.5 7.66 1.13 + 0.16 + 2.1 no
34.6.3 Calculate the percent recovery of the spike (P) using
15 15.8 2.86 + 0.8 + 5.3 no the following formula:
44 42.6 8.13 −1.4 −3.2 no
P 5 100 [A~Vs 1 V! 2 B Vs#
CV (2)

34.3.2 Analyze seven replicates of a standard solution where:

prepared from an Independent Reference Material containing a A = Analyte Concentration (µg/L) in Spiked Sample;
mid-range concentration of manganese. The matrix and chem- B = Analyte Concentration (µg/L) in Unspiked Sample;
istry of the solution should be equivalent to the solution used C = Concentration (µg/L) of Analyte in Spiking Solution;
in the collaborative study. Each replicate must be taken through Vs = Volume (mL) of Sample Used; and
the complete analytical test method including any sample V = Volume (mL) added with Spike.
preservation and pretreatment steps. The replicates may be 34.6.4 The percent recovery of the spike shall fall within the
interspersed with samples. limits based on the analyte concentration, listed in Guide
34.3.3 Calculate the mean and standard deviation of the D 5810, Table 1. If the percent recovery is not within these
seven values and compare to the acceptable ranges of bias in limits, a matrix interference may be present in the sample
Table 1. This study should be repeated until the recoveries are selected for spiking. Under these circumstances, one of the
within the limits given in Table 1. If a concentration other than following remedies must be employed: the matrix interference
the recommended concentration is used, refer to Test Method must be removed, all samples in the batch must be analyzed by
D 5847 for information on applying the F test and t test in a test method not affected by the matrix interference, or the
evaluating the acceptability of the mean and standard devia- results must be qualified with an indication that they do not fall
tion. within the performance criteria of the test method. Note:
34.4 Laboratory Control Sample (LCS) : acceptable spike recoveries are dependent on the concentration
34.4.1 To ensure that the test method is in control, analyze of the component of interest. See Guide 5810 for additional
a LCS containing a mid-range concentration of manganese information.
with each batch every 10 samples if large numbers of samples 34.7 Duplicate:
are analyzed in the batch. The LCS must be taken through all 34.7.1 To check the precision of sample analyses, analyze a
of the steps of the analytical method including sample preser- sample in duplicate with each batch. If the concentration of the
vation and pretreatment. The result obtained for the LCS shall analyte in the sample (and duplicate) is less than five times the
fall within 6 15 % of the known concentration. detection limit for the analyte, a matrix spike duplicate (MSD)
34.4.2 If the result is not within these limits, analysis of should be used.
samples is halted until the problem is corrected, and either all 34.7.2 Calculate the standard deviation of the duplicate
the samples in the batch must be reanalyzed, or the results must values and compare to the precision in the collaborative study
be qualified with an indication that they do not fall within the using an F test. Refer to 6.4.4 of Test Method D 5847 for
performance criteria of the test method. information on applying the F test.
34.5 Method Blank: 34.7.3 If the result exceeds the precision limit, the batch
34.5.1 Analyze a reagent water test blank with each batch. must be reanalyzed or the results must be qualified with an
The concentration of manganese found in the blank should be indication that they do not fall within the performance criteria
less than 0.5 times the lowest calibration standard. If the of the test method.
concentration of manganese is found above this level, analysis
34.8 Independent Reference Material (IRM):
of samples is halted until the contamination is eliminated and
a blank shows no contamination at or above this level, or the 34.8.1 In order to verify the quantitative value produced by
results must be qualified with an indication that they do not fall the test method, analyze an IRM submitted as a regular sample
within the performance criteria of the test method. (if practical) to the laboratory at least once per quarter. The
34.6 Matrix Spike (MS): concentration of the reference material should be in the
34.6.1 To check for interferences in the specific matrix concentration mid-range for the method chosen. The value
being tested, perform a MS on at least one sample from each obtained must fall within the control limits established by the
batch by spiking an aliquot of the sample with a known laboratory.
concentration of manganese and taking it through the analytical
method. 35. Keywords
34.6.2 The spike concentration plus the sample concentra- 35.1 atomic absorption; chelation; flame; graphite furnace;
tion of manganese must not exceed the high calibration manganese; water

7
 D 858 – 07
APPENDIX

(Nonmandatory Information)

X1. RATIONALE FOR DISCONTINUATION OF TEST METHODS

X1.1 Test Method A, Colorimetric (for concentrations of X1.1.3 Particulate manganese is solubilized by acid diges-
manganese ranging from 0.025 to 15 mg/L): tion and the dissolved manganese is oxidized to permanganate
X1.1.1 This test method was discontinued in 1988. It was with ammonium persulfate in the presence of silver nitrate. The
published in its entirety in the 1988 Annual Book of ASTM color is compared with standards either visually or instrumen-
Standards, Vol 11.01. tally.
X1.1.2 This test method covers the determination of man- X1.1.4 This test method was discontinued because there
ganese in water and includes both dissolved and particulate were insufficient laboratories interested in participating in a
material. It is applicable for manganese present as Mn in the collaborative study to obtain the necessary precision and bias
range from 0.025 to 15 mg/L. as required by Practice D 2777.

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website
(www.astm.org).