Appendix A-2 To Part 50 - Title 40 (Up To Date As of 8-01-2023)

Appendix A-2 to Part 50, Title 40 (up to date as of 8/01/2023)
Appendix A-2 to Part 50, Title 40 (Aug. 1, 2023)

Reference Method for the Determination of Sulfur Dioxide in the...
This content is from the eCFR and is authoritative but unofficial.
Title 40 —Protection of Environment

Chapter I —Environmental Protection Agency
Subchapter C —Air Programs
Part 50 —National Primary and Secondary Ambient Air Quality Standards
Authority: 42 U.S.C. 7401, et seq.
Source: 36 FR 22384, Nov. 25, 1971, unless otherwise noted.
Appendix A–2 to Part 50—Reference Method for the Determination of Sulfur Dioxide in the
Atmosphere (Pararosaniline Method)
1.0 Applicability.
1.1 This method provides a measurement of the concentration of sulfur dioxide (SO2) in ambient air for
determining compliance with the primary and secondary national ambient air quality standards for
sulfur oxides (sulfur dioxide) as specified in § 50.4 and § 50.5 of this chapter. The method is
applicable to the measurement of ambient SO2 concentrations using sampling periods ranging from
30 minutes to 24 hours. Additional quality assurance procedures and guidance are provided in part
58, appendixes A and B, of this chapter and in references 1 and 2.
2.0 Principle.
2.1 A measured volume of air is bubbled through a solution of 0.04 M potassium tetrachloromercurate
(TCM). The SO2 present in the air stream reacts with the TCM solution to form a stable
monochlorosulfonatomercurate(3) complex. Once formed, this complex resists air oxidation(4, 5)
and is stable in the presence of strong oxidants such as ozone and oxides of nitrogen. During
subsequent analysis, the complex is reacted with acid-bleached pararosaniline dye and
formaldehyde to form an intensely colored pararosaniline methyl sulfonic acid.
(6) The optical density of this species is determined spectrophotometrically at 548 nm and is directly
related to the amount of SO2 collected. The total volume of air sampled, corrected to EPA reference
conditions (25 °C, 760 mm Hg [101 kPa]), is determined from the measured flow rate and the
sampling time. The concentration of SO2 in the ambient air is computed and expressed in
micrograms per standard cubic meter (µg/std m3).
3.0 Range.
3.1 The lower limit of detection of SO2 in 10 mL of TCM is 0.75 µg (based on collaborative test
results).(7) This represents a concentration of 25 µg SO2/m3 (0.01 ppm) in an air sample of 30
standard liters (short-term sampling) and a concentration of 13 µg SO2/m3 (0.005 ppm) in an air
sample of 288 standard liters (long-term sampling). Concentrations less than 25 µg SO2/m3 can be
measured by sampling larger volumes of ambient air; however, the collection efficiency falls off
rapidly at low concentrations.(8, 9) Beer's law is adhered to up to 34 µg of SO2 in 25 mL of final
solution. This upper limit of the analysis range represents a concentration of 1,130 µg SO2/m3 (0.43
ppm) in an air sample of 30 standard liters and a concentration of 590 µg SO2/m3 (0.23 ppm) in an
air sample of 288 standard liters. Higher concentrations can be measured by collecting a smaller
volume of air, by increasing the volume of absorbing solution, or by diluting a suitable portion of the
collected sample with absorbing solution prior to analysis.
Appendix A-2 to Part 50, Title 40 (Aug. 1, 2023) (enhanced display) page 1 of 26
4.0 Interferences.
4.1 The effects of the principal potential interferences have been minimized or eliminated in the
following manner: Nitrogen oxides by the addition of sulfamic acid,(10, 11) heavy metals by the
addition of ethylenediamine tetracetic acid disodium salt (EDTA) and phosphoric acid,(10, 12) and
ozone by time delay.(10) Up to 60 µg Fe (III), 22 µg V (V), 10 µg Cu (II), 10 µg Mn (II), and 10 µg Cr (III)
in 10 mL absorbing reagent can be tolerated in the procedure.(10) No significant interference has
been encountered with 2.3 µg NH3.(13)
5.0 Precision and Accuracy.
5.1 The precision of the analysis is 4.6 percent (at the 95 percent confidence level) based on the analysis
of standard sulfite samples.(10)
5.2 Collaborative test results (14) based on the analysis of synthetic test atmospheres (SO2 in scrubbed
air) using the 24-hour sampling procedure and the sulfite-TCM calibration procedure show that:
• The replication error varies linearly with concentration from ±2.5 µg/m3 at concentrations of 100
µg/m3 to ±7 µg/m3 at concentrations of 400 µg/m3.
• The day-to-day variability within an individual laboratory (repeatability) varies linearly with
concentration from ±18.1 µg/m3 at levels of 100 µg/m3 to ±50.9 µg/m3 at levels of 400 µg/m3.
• The day-to-day variability between two or more laboratories (reproducibility) varies linearly with
concentration from ±36.9 µg/m3 at levels of 100 µg/m3 to ±103.5 µ g/m3 at levels of 400 µg/m3.
• The method has a concentration-dependent bias, which becomes significant at the 95 percent
confidence level at the high concentration level. Observed values tend to be lower than the expected
SO2 concentration level.
6.0 Stability.
6.1 By sampling in a controlled temperature environment of 15° ±10 °C, greater than 98.9 percent of the
SO2–TCM complex is retained at the completion of sampling. (15) If kept at 5 °C following the
completion of sampling, the collected sample has been found to be stable for up to 30 days. (10)
The presence of EDTA enhances the stability of SO2 in the TCM solution and the rate of decay is
independent of the concentration of SO2. (16)
7.0 Apparatus.
7.1 Sampling.
7.1.1 Sample probe: A sample probe meeting the requirements of section 7 of 40 CFR part 58,
appendix E (Teflon ® or glass with residence time less than 20 sec.) is used to transport
ambient air to the sampling train location. The end of the probe should be designed or oriented
to preclude the sampling of precipitation, large particles, etc. A suitable probe can be
constructed from Teflon ® tubing connected to an inverted funnel.
7.1.2 Absorber—short-term sampling: An all glass midget impinger having a solution capacity of 30
mL and a stem clearance of 4 ±1 mm from the bottom of the vessel is used for sampling
periods of 30 minutes and 1 hour (or any period considerably less than 24 hours). Such an
impinger is shown in Figure 1. These impingers are commercially available from distributors
such as Ace Glass, Incorporated.
7.1.3 Absorber—24-hour sampling: A polypropylene tube 32 mm in diameter and 164 mm long

(available from Bel Art Products, Pequammock, NJ) is used as the absorber. The cap of the
absorber must be a polypropylene cap with two ports (rubber stoppers are unacceptable
because the absorbing reagent can react with the stopper to yield erroneously high SO2
concentrations). A glass impinger stem, 6 mm in diameter and 158 mm long, is inserted into
one port of the absorber cap. The tip of the stem is tapered to a small diameter orifice (0.4 ±0.1
mm) such that a No. 79 jeweler's drill bit will pass through the opening but a No. 78 drill bit will
not. Clearance from the bottom of the absorber to the tip of the stem must be 6 ±2 mm. Glass
stems can be fabricated by any reputable glass blower or can be obtained from a scientific
supply firm. Upon receipt, the orifice test should be performed to verify the orifice size. The 50
mL volume level should be permanently marked on the absorber. The assembled absorber is
shown in Figure 2.
7.1.4 Moisture trap: A moisture trap constructed of a glass trap as shown in Figure 1 or a
polypropylene tube as shown in Figure 2 is placed between the absorber tube and flow control
device to prevent entrained liquid from reaching the flow control device. The tube is packed
with indicating silica gel as shown in Figure 2. Glass wool may be substituted for silica gel
when collecting short-term samples (1 hour or less) as shown in Figure 1, or for long term (24
hour) samples if flow changes are not routinely encountered.
7.1.5 Cap seals: The absorber and moisture trap caps must seal securely to prevent leaks during use.
Heat-shrink material as shown in Figure 2 can be used to retain the cap seals if there is any
chance of the caps coming loose during sampling, shipment, or storage.
7.1.6 Flow control device: A calibrated rotameter and needle valve combination capable of
maintaining and measuring air flow to within ±2 percent is suitable for short-term sampling but
may not be used for long-term sampling. A critical orifice can be used for regulating flow rate
for both long-term and short-term sampling. A 22-gauge hypodermic needle 25 mm long may
be used as a critical orifice to yield a flow rate of approximately 1 L/min for a 30-minute
sampling period. When sampling for 1 hour, a 23-gauge hypodermic needle 16 mm in length will
provide a flow rate of approximately 0.5 L/min. Flow control for a 24-hour sample may be
provided by a 27-gauge hypodermic needle critical orifice that is 9.5 mm in length. The flow rate
should be in the range of 0.18 to 0.22 L/min.
7.1.7 Flow measurement device: Device calibrated as specified in 9.4.1 and used to measure sample
flow rate at the monitoring site.
7.1.8 Membrane particle filter: A membrane filter of 0.8 to 2 µm porosity is used to protect the flow
controller from particles during long-term sampling. This item is optional for short-term
sampling.
7.1.9 Vacuum pump: A vacuum pump equipped with a vacuum gauge and capable of maintaining at
least 70 kPa (0.7 atm) vacuum differential across the flow control device at the specified flow
rate is required for sampling.
7.1.10 Temperature control device: The temperature of the absorbing solution during sampling must
be maintained at 15° ±10 °C. As soon as possible following sampling and until analysis, the
temperature of the collected sample must be maintained at 5° ±5 °C. Where an extended period
of time may elapse before the collected sample can be moved to the lower storage
temperature, a collection temperature near the lower limit of the 15 ±10 °C range should be
used to minimize losses during this period. Thermoelectric coolers specifically designed for
this temperature control are available commercially and normally operate in the range of 5° to
15 °C. Small refrigerators can be modified to provide the required temperature control; however,
inlet lines must be insulated from the lower temperatures to prevent condensation when
sampling under humid conditions. A small heating pad may be necessary when sampling at low
temperatures (<7 °C) to prevent the absorbing solution from freezing.(17)
7.1.11 Sampling train container: The absorbing solution must be shielded from light during and after
sampling. Most commercially available sampler trains are enclosed in a light-proof box.
7.1.12 Timer: A timer is recommended to initiate and to stop sampling for the 24-hour period. The
timer is not a required piece of equipment; however, without the timer a technician would be
required to start and stop the sampling manually. An elapsed time meter is also recommended
to determine the duration of the sampling period.
7.2 Shipping.
7.2.1 Shipping container: A shipping container that can maintain a temperature of 5° ±5 °C is used for
transporting the sample from the collection site to the analytical laboratory. Ice coolers or
refrigerated shipping containers have been found to be satisfactory. The use of eutectic cold
packs instead of ice will give a more stable temperature control. Such equipment is available
from Cole-Parmer Company, 7425 North Oak Park Avenue, Chicago, IL 60648.
7.3 Analysis.
7.3.1 Spectrophotometer: A spectrophotometer suitable for measurement of absorbances at 548 nm

with an effective spectral bandwidth of less than 15 nm is required for analysis. If the
spectrophotometer reads out in transmittance, convert to absorbance as follows:
where:
A = absorbance, and
T = transmittance (0<≥T<1).
A standard wavelength filter traceable to the National Bureau of Standards is used to verify the
wavelength calibration according to the procedure enclosed with the filter. The wavelength
calibration must be verified upon initial receipt of the instrument and after each 160 hours of
normal use or every 6 months, whichever occurs first.
7.3.2 Spectrophotometer cells: A set of 1-cm path length cells suitable for use in the visible region is
used during analysis. If the cells are unmatched, a matching correction factor must be
determined according to Section 10.1.
7.3.3 Temperature control device: The color development step during analysis must be conducted in
an environment that is in the range of 20° to 30 °C and controlled to ±1 °C. Both calibration and
sample analysis must be performed under identical conditions (within 1 °C). Adequate
temperature control may be obtained by means of constant temperature baths, water baths
with manual temperature control, or temperature controlled rooms.
7.3.4 Glassware: Class A volumetric glassware of various capacities is required for preparing and
standardizing reagents and standards and for dispensing solutions during analysis. These
included pipets, volumetric flasks, and burets.
7.3.5 TCM waste receptacle: A glass waste receptacle is required for the storage of spent TCM
solution. This vessel should be stoppered and stored in a hood at all times.
8.0 Reagents.
8.1 Sampling.
8.1.1 Distilled water: Purity of distilled water must be verified by the following procedure:(18)
• Place 0.20 mL of potassium permanganate solution (0.316 g/L), 500 mL of distilled water, and
1mL of concentrated sulfuric acid in a chemically resistant glass bottle, stopper the bottle, and
allow to stand.
• If the permanganate color (pink) does not disappear completely after a period of 1 hour at
room temperature, the water is suitable for use.
• If the permanganate color does disappear, the water can be purified by redistilling with one
crystal each of barium hydroxide and potassium permanganate in an all glass still.
8.1.2 Absorbing reagent (0.04 M potassium tetrachloromercurate [TCM]): Dissolve 10.86 g mercuric
chloride, 0.066 g EDTA, and 6.0 g potassium chloride in distilled water and dilute to volume with
distilled water in a 1,000-mL volumetric flask. (Caution: Mercuric chloride is highly poisonous. If
spilled on skin, flush with water immediately.) The pH of this reagent should be between 3.0
and 5.0 (10) Check the pH of the absorbing solution by using pH indicating paper or a pH meter.
If the pH of the solution is not between 3.0 and 5.0, dispose of the solution according to one of
the disposal techniques described in Section 13.0. The absorbing reagent is normally stable for
6 months. If a precipitate forms, dispose of the reagent according to one of the procedures
described in Section 13.0.
8.2 Analysis.
8.2.1 Sulfamic acid (0.6%): Dissolve 0.6 g sulfamic acid in 100 mL distilled water. Perpare fresh daily.
8.2.2 Formaldehyde (0.2%): Dilute 5 mL formaldehyde solution (36 to 38 percent) to 1,000 mL with
distilled water. Prepare fresh daily.
8.2.3 Stock iodine solution (0.1 N): Place 12.7 g resublimed iodine in a 250-mL beaker and add 40 g
potassium iodide and 25 mL water. Stir until dissolved, transfer to a 1,000 mL volumetric flask
and dilute to volume with distilled water.
8.2.4 Iodine solution (0.01 N): Prepare approximately 0.01 N iodine solution by diluting 50 mL of
stock iodine solution (Section 8.2.3) to 500 mL with distilled water.
8.2.5 Starch indicator solution: Triturate 0.4 g soluble starch and 0.002 g mercuric iodide
(preservative) with enough distilled water to form a paste. Add the paste slowly to 200 mL of
boiling distilled water and continue boiling until clear. Cool and transfer the solution to a glass
stopperd bottle.
8.2.6 1 N hydrochloric acid: Slowly and while stirring, add 86 mL of concentrated hydrochloric acid to
500 mL of distilled water. Allow to cool and dilute to 1,000 mL with distilled water.
8.2.7 Potassium iodate solution: Accurately weigh to the nearest 0.1 mg, 1.5 g (record weight) of
primary standard grade potassium iodate that has been previously dried at 180 °C for at least 3
hours and cooled in a dessicator. Dissolve, then dilute to volume in a 500-mL volumetric flask
with distilled water.
8.2.8 Stock sodium thiosulfate solution (0.1 N): Prepare a stock solution by dissolving 25 g sodium
thiosulfate (Na2 S2 O3 ÷ 5H2 O) in 1,000 mL freshly boiled, cooled, distilled water and adding 0.1
g sodium carbonate to the solution. Allow the solution to stand at least 1 day before
standardizing. To standardize, accurately pipet 50 mL of potassium iodate solution (Section
8.2.7) into a 500-mL iodine flask and add 2.0 g of potassium iodide and 10 mL of 1 N HCl.
Stopper the flask and allow to stand for 5 minutes. Titrate the solution with stock sodium
thiosulfate solution (Section 8.2.8) to a pale yellow color. Add 5 mL of starch solution (Section
8.2.5) and titrate until the blue color just disappears. Calculate the normality (Ns) of the stock
sodium thiosulfate solution as follows:
where:
M = volume of thiosulfate required in mL, and
W = weight of potassium iodate in g (recorded weight in Section 8.2.7).
8.2.9 Working sodium thiosulfate titrant (0.01 N): Accurately pipet 100 mL of stock sodium
thiosulfate solution (Section 8.2.8) into a 1,000-mL volumetric flask and dilute to volume with
freshly boiled, cooled, distilled water. Calculate the normality of the working sodium thiosulfate
titrant (NT) as follows:
8.2.10 Standardized sulfite solution for the preparation of working sulfite-TCM solution: Dissolve 0.30
g sodium metabisulfite (Na2 S2 O5) or 0.40 g sodium sulfite (Na2 SO3) in 500 mL of recently
boiled, cooled, distilled water. (Sulfite solution is unstable; it is therefore important to use water
of the highest purity to minimize this instability.) This solution contains the equivalent of 320 to
400 µg SO2/mL. The actual concentration of the solution is determined by adding excess iodine
and back-titrating with standard sodium thiosulfate solution. To back-titrate, pipet 50 mL of the
0.01 N iodine solution (Section 8.2.4) into each of two 500-mL iodine flasks (A and B). To flask
A (blank) add 25 mL distilled water, and to flask B (sample) pipet 25 mL sulfite solution.
Stopper the flasks and allow to stand for 5 minutes. Prepare the working sulfite-TCM solution
(Section 8.2.11) immediately prior to adding the iodine solution to the flasks. Using a buret
containing standardized 0.01 N thiosulfate titrant (Section 8.2.9), titrate the solution in each
flask to a pale yellow color. Then add 5 mL starch solution (Section 8.2.5) and continue the
titration until the blue color just disappears.
8.2.11 Working sulfite-TCM solution: Accurately pipet 5 mL of the standard sulfite solution (Section
8.2.10) into a 250-mL volumetric flask and dilute to volume with 0.04 M TCM. Calculate the
concentration of sulfur dioxide in the working solution as follows:
where:
A = volume of thiosulfate titrant required for the blank, mL;
B = volume of thiosulfate titrant required for the sample, mL;
NT = normality of the thiosulfate titrant, from equation (3);
32,000 = milliequivalent weight of SO2, µg;
25 = volume of standard sulfite solution, mL; and
0.02 = dilution factor.
This solution is stable for 30 days if kept at 5 °C. (16) If not kept at 5 °C, prepare fresh daily.
8.2.12 Purified pararosaniline (PRA) stock solution (0.2% nominal):
8.2.12.1 Dye specifications —

• The dye must have a maximum absorbance at a wavelength of 540 nm when assayed in
a buffered solution of 0.1 M sodium acetate-acetic acid;
• The absorbance of the reagent blank, which is temperature sensitive (0.015 absorbance
unit/ °C), must not exceed 0.170 at 22 °C with a 1-cm optical path length when the blank is
prepared according to the specified procedure;
• The calibration curve (Section 10.0) must have a slope equal to 0.030 ±0.002 absorbance
unit/µg SO2 with a 1-cm optical path length when the dye is pure and the sulfite solution is
properly standardized.
8.2.12.2 Preparation of stock PRA solution —A specially purified (99 to 100 percent pure)
solution of pararosaniline, which meets the above specifications, is commercially available
in the required 0.20 percent concentration (Harleco Co.). Alternatively, the dye may be
purified, a stock solution prepared, and then assayed according to the procedure as
described below.(10)
8.2.12.3 Purification procedure for PRA —
1. Place 100 mL each of 1-butanol and 1 N HCl in a large separatory funnel (250-mL) and
allow to equilibrate. Note: Certain batches of 1-butanol contain oxidants that create an
SO2 demand. Before using, check by placing 20 mL of 1-butanol and 5 mL of 20 percent
potassium iodide (KI) solution in a 50-mL separatory funnel and shake thoroughly. If a
yellow color appears in the alcohol phase, redistill the 1-butanol from silver oxide and
collect the middle fraction or purchase a new supply of 1-butanol.
2. Weigh 100 mg of pararosaniline hydrochloride dye (PRA) in a small beaker. Add 50 mL of

the equilibrated acid (drain in acid from the bottom of the separatory funnel in 1.) to the
beaker and let stand for several minutes. Discard the remaining acid phase in the
separatory funnel.
3. To a 125-mL separatory funnel, add 50 mL of the equilibrated 1-butanol (draw the

1-butanol from the top of the separatory funnel in 1.). Transfer the acid solution (from 2.)
containing the dye to the funnel and shake carefully to extract. The violet impurity will
transfer to the organic phase.
4. Transfer the lower aqueous phase into another separatory funnel, add 20 mL of
equilibrated 1-butanol, and extract again.
5. Repeat the extraction procedure with three more 10-mL portions of equilibrated 1-butanol.
6. After the final extraction, filter the acid phase through a cotton plug into a 50-mL
volumetric flask and bring to volume with 1 N HCl. This stock reagent will be a yellowish
red.
7. To check the purity of the PRA, perform the assay and adjustment of concentration
(Section 8.2.12.4) and prepare a reagent blank (Section 11.2); the absorbance of this
reagent blank at 540 nm should be less than 0.170 at 22 °C. If the absorbance is greater
than 0.170 under these conditions, further extractions should be performed.
8.2.12.4 PRA assay procedure—The concentration of pararosaniline hydrochloride (PRA) need be assayed only once
after purification. It is also recommended that commercial solutions of pararosaniline be assayed when first
purchased. The assay procedure is as follows:(10)
1. Prepare 1 M acetate-acetic acid buffer stock solution with a pH of 4.79 by dissolving 13.61
g of sodium acetate trihydrate in distilled water in a 100-mL volumetric flask. Add 5.70 mL
of glacial acetic acid and dilute to volume with distilled water.
2. Pipet 1 mL of the stock PRA solution obtained from the purification process or from a
commercial source into a 100-mL volumetric flask and dilute to volume with distilled
water.
3. Transfer a 5–mL aliquot of the diluted PRA solution from 2. into a 50–mL volumetric flask.
Add 5mL of 1 M acetate-acetic acid buffer solution from 1. and dilute the mixture to
volume with distilled water. Let the mixture stand for 1 hour.
4. Measure the absorbance of the above solution at 540 nm with a spectrophotometer

against a distilled water reference. Compute the percentage of nominal concentration of
PRA by
where:
A = measured absorbance of the final mixture (absorbance units);
W = weight in grams of the PRA dye used in the assay to prepare 50 mL of stock solution (for example, 0.100 g of
dye was used to prepare 50 mL of solution in the purification procedure; when obtained from commercial sources,
use the stated concentration to compute W; for 98% PRA, W = .098 g.); and
K = 21.3 for spectrophotometers having a spectral bandwidth of less than 15 nm and a path length of 1 cm.
8.2.13 Pararosaniline reagent: To a 250–mL volumetric flask, add 20 mL of stock PRA solution. Add
an additional 0.2 mL of stock solution for each percentage that the stock assays below 100
percent. Then add 25 mL of 3 M phosphoric acid and dilute to volume with distilled water. The
reagent is stable for at least 9 months. Store away from heat and light.
9.0 Sampling Procedure.
9.1 General Considerations. Procedures are described for short-term sampling (30-minute and 1-hour)
and for long-term sampling (24-hour). Different combinations of absorbing reagent volume, sampling
rate, and sampling time can be selected to meet special needs. For combinations other than those
specifically described, the conditions must be adjusted so that linearity is maintained between
absorbance and concentration over the dynamic range. Absorbing reagent volumes less than 10 mL
are not recommended. The collection efficiency is above 98 percent for the conditions described;
however, the efficiency may be substantially lower when sampling concentrations below 25
µγSO2/m3.(8,9)
9.2 30-Minute and 1-Hour Sampling. Place 10 mL of TCM absorbing reagent in a midget impinger and
seal the impinger with a thin film of silicon stopcock grease (around the ground glass joint). Insert
the sealed impinger into the sampling train as shown in Figure 1, making sure that all connections
between the various components are leak tight. Greaseless ball joint fittings, heat shrinkable Teflon
® tubing, or Teflon ® tube fittings may be used to attain leakfree conditions for portions of the
sampling train that come into contact with air containing SO2. Shield the absorbing reagent from
direct sunlight by covering the impinger with aluminum foil or by enclosing the sampling train in a
light-proof box. Determine the flow rate according to Section 9.4.2. Collect the sample at 1 ±0.10 L/
min for 30-minute sampling or 0.500 ±0.05 L/min for 1-hour sampling. Record the exact sampling
time in minutes, as the sample volume will later be determined using the sampling flow rate and the
sampling time. Record the atmospheric pressure and temperature.
9.3 24-Hour Sampling. Place 50 mL of TCM absorbing solution in a large absorber, close the cap, and, if
needed, apply the heat shrink material as shown in Figure 3. Verify that the reagent level is at the 50
mL mark on the absorber. Insert the sealed absorber into the sampling train as shown in Figure 2. At
this time verify that the absorber temperature is controlled to 15 ±10 °C. During sampling, the
absorber temperature must be controlled to prevent decomposition of the collected complex. From
the onset of sampling until analysis, the absorbing solution must be protected from direct sunlight.
Determine the flow rate according to Section 9.4.2. Collect the sample for 24 hours from midnight to
midnight at a flow rate of 0.200 ±0.020 L/min. A start/stop timer is helpful for initiating and stopping
sampling and an elapsed time meter will be useful for determining the sampling time.
9.4 Flow Measurement.
9.4.1 Calibration: Flow measuring devices used for the on-site flow measurements required in 9.4.2
must be calibrated against a reliable flow or volume standard such as an NBS traceable bubble
flowmeter or calibrated wet test meter. Rotameters or critical orifices used in the sampling train
may be calibrated, if desired, as a quality control check, but such calibration shall not replace
the on-site flow measurements required by 9.4.2. In-line rotameters, if they are to be calibrated,
should be calibrated in situ, with the appropriate volume of solution in the absorber.
9.4.2 Determination of flow rate at sampling site: For short-term samples, the standard flow rate is
determined at the sampling site at the initiation and completion of sample collection with a
calibrated flow measuring device connected to the inlet of the absorber. For 24-hour samples,
the standard flow rate is determined at the time the absorber is placed in the sampling train and
again when the absorber is removed from the train for shipment to the analytical laboratory
with a calibrated flow measuring device connected to the inlet of the sampling train. The flow
rate determination must be made with all components of the sampling system in operation
(e.g., the absorber temperature controller and any sample box heaters must also be operating).
Equation 6 may be used to determine the standard flow rate when a calibrated positive
displacement meter is used as the flow measuring device. Other types of calibrated flow
measuring devices may also be used to determine the flow rate at the sampling site provided
that the user applies any appropriate corrections to devices for which output is dependent on
temperature or pressure.
where:
Qstd = flow rate at standard conditions, std L/min (25 °C and 760 mm Hg);
Qact = flow rate at monitoring site conditions, L/min;
Pb = barometric pressure at monitoring site conditions, mm Hg or kPa;
RH = fractional relative humidity of the air being measured;
PH2O = vapor pressure of water at the temperature of the air in the flow or volume standard, in the same units as Pb,
(for wet volume standards only, i.e., bubble flowmeter or wet test meter; for dry standards, i.e., dry test meter, PH2O =
0);
Pstd = standard barometric pressure, in the same units as Pb (760 mm Hg or 101 kPa); and
Tmeter = temperature of the air in the flow or volume standard, °C (e.g., bubble flowmeter).
If a barometer is not available, the following equation may be used to determine the barometric pressure:
where:
H = sampling site elevation above sea level in meters.
If the initial flow rate (Qi) differs from the flow rate of the critical orifice or the flow rate indicated by the flowmeter in
the sampling train (Qc) by more than 5 percent as determined by equation (8), check for leaks and redetermine Qi.
Invalidate the sample if the difference between the initial (Qi) and final (Qf) flow rates is more than 5 percent as
determined by equation (9):
9.5 Sample Storage and Shipment. Remove the impinger or absorber from the sampling train and stopper
immediately. Verify that the temperature of the absorber is not above 25 °C. Mark the level of the
solution with a temporary (e.g., grease pencil) mark. If the sample will not be analyzed within 12
hours of sampling, it must be stored at 5° ±5 °C until analysis. Analysis must occur within 30 days. If
the sample is transported or shipped for a period exceeding 12 hours, it is recommended that
thermal coolers using eutectic ice packs, refrigerated shipping containers, etc., be used for periods
up to 48 hours. (17) Measure the temperature of the absorber solution when the shipment is
received. Invalidate the sample if the temperature is above 10 °C. Store the sample at 5° ±5 °C until it
is analyzed.
10.0 Analytical Calibration.
10.1 Spectrophotometer Cell Matching. If unmatched spectrophotometer cells are used, an absorbance
correction factor must be determined as follows:
1. Fill all cells with distilled water and designate the one that has the lowest absorbance at 548 nm as
the reference. (This reference cell should be marked as such and continually used for this purpose
throughout all future analyses.)
2. Zero the spectrophotometer with the reference cell.
3. Determine the absorbance of the remaining cells (Ac) in relation to the reference cell and record these values for
future use. Mark all cells in a manner that adequately identifies the correction.
The corrected absorbance during future analyses using each cell is determining as follows:
where:
A = corrected absorbance,
Aobs = uncorrected absorbance, and
Ac = cell correction.
10.2 Static Calibration Procedure (Option 1). Prepare a dilute working sulfite-TCM solution by diluting 10 mL of the
working sulfite-TCM solution (Section 8.2.11) to 100 mL with TCM absorbing reagent. Following the table below,
accurately pipet the indicated volumes of the sulfite-TCM solutions into a series of 25-mL volumetric flasks. Add
TCM absorbing reagent as indicated to bring the volume in each flask to 10 mL.
Sulfite-TCM solution Volume of sulfite-TCM solution Volume of TCM, mL Total µg SO2 (approx.*
Working 4.0 6.0 28.8
Working 3.0 7.0 21.6
Working 2.0 8.0 14.4
Dilute working 10.0 0.0 7.2
Dilute working 5.0 5.0 3.6
0.0 10.0 0.0
*Based on working sulfite-TCM solution concentration of 7.2 µg SO2/mL; the actual total µg SO2
must be calculated using equation 11 below.
To each volumetric flask, add 1 mL 0.6% sulfamic acid (Section 8.2.1), accurately pipet 2 mL 0.2% formaldehyde
solution (Section 8.2.2), then add 5 mL pararosaniline solution (Section 8.2.13). Start a laboratory timer that has
been set for 30 minutes. Bring all flasks to volume with recently boiled and cooled distilled water and mix
thoroughly. The color must be developed (during the 30-minute period) in a temperature environment in the range of
20° to 30 °C, which is controlled to ±1 °C. For increased precision, a constant temperature bath is recommended
during the color development step. After 30 minutes, determine the corrected absorbance of each standard at 548
nm against a distilled water reference (Section 10.1). Denote this absorbance as (A). Distilled water is used in the
reference cell rather than the reagant blank because of the temperature sensitivity of the reagent blank. Calculate
the total micrograms SO2 in each solution:
where:
VTCM/SO2 = volume of sulfite-TCM solution used, mL;
CTCM/SO2 = concentration of sulfur dioxide in the working sulfite-TCM, µg SO2/mL (from equation 4); and
D = dilution factor (D = 1 for the working sulfite-TCM solution; D = 0.1 for the diluted working sulfite-TCM solution).
A calibration equation is determined using the method of linear least squares (Section 12.1). The total micrograms
SO2 contained in each solution is the x variable, and the corrected absorbance (eq. 10) associated with each
solution is the y variable. For the calibration to be valid, the slope must be in the range of 0.030 ±0.002 absorbance
unit/µg SO2, the intercept as determined by the least squares method must be equal to or less than 0.170
absorbance unit when the color is developed at 22 °C (add 0.015 to this 0.170 specification for each °C above 22
°C) and the correlation coefficient must be greater than 0.998. If these criteria are not met, it may be the result of an
impure dye and/or an improperly standardized sulfite-TCM solution. A calibration factor (Bs) is determined by
calculating the reciprocal of the slope and is subsequently used for calculating the sample concentration (Section
12.3).
10.3 Dynamic Calibration Procedures (Option 2). Atmospheres containing accurately known
concentrations of sulfur dioxide are prepared using permeation devices. In the systems for
generating these atmospheres, the permeation device emits gaseous SO2 at a known, low, constant
rate, provided the temperature of the device is held constant (±0.1 °C) and the device has been
accurately calibrated at the temperature of use. The SO2 permeating from the device is carried by a
low flow of dry carrier gas to a mixing chamber where it is diluted with SO2-free air to the desired
concentration and supplied to a vented manifold. A typical system is shown schematically in Figure
4 and this system and other similar systems have been described in detail by O'Keeffe and Ortman;
(19) Scaringelli, Frey, and Saltzman, (20) and Scaringelli, O'Keeffe, Rosenberg, and Bell. (21)
Permeation devices may be prepared or purchased and in both cases must be traceable either to a
National Bureau of Standards (NBS) Standard Reference Material (SRM 1625, SRM 1626, SRM 1627)
or to an NBS/EPA-approved commercially available Certified Reference Material (CRM). CRM's are
described in Reference 22, and a list of CRM sources is available from the address shown for
Reference 22. A recommended protocol for certifying a permeation device to an NBS SRM or CRM is
given in Section 2.0.7 of Reference 2. Device permeation rates of 0.2 to 0.4 µg/min, inert gas flows
of about 50 mL/min, and dilution air flow rates from 1.1 to 15 L/min conveniently yield standard
atmospheres in the range of 25 to 600 µg SO2/m3 (0.010 to 0.230 ppm).
10.3.1 Calibration Option 2A (30-minute and 1-hour samples): Generate a series of six standard
atmospheres of SO2 (e.g., 0, 50, 100, 200, 350, 500, 750 µg/m3) by adjusting the dilution flow
rates appropriately. The concentration of SO2 in each atmosphere is calculated as follows:
where:
Ca = concentration of SO2 at standard conditions, µg/m3;
Pr = permeation rate, µg/min;
Qd = flow rate of dilution air, std L/min; and
Qp = flow rate of carrier gas across permeation device, std L/min.
Be sure that the total flow rate of the standard exceeds the flow demand of the sample train, with the excess flow
vented at atmospheric pressure. Sample each atmosphere using similar apparatus as shown in Figure 1 and under
the same conditions as field sampling (i.e., use same absorbing reagent volume and sample same volume of air at
an equivalent flow rate). Due to the length of the sampling periods required, this method is not recommended for
24-hour sampling. At the completion of sampling, quantitatively transfer the contents of each impinger to one of a
series of 25-mL volumetric flasks (if 10 mL of absorbing solution was used) using small amounts of distilled water
for rinse (<5mL). If >10 mL of absorbing solution was used, bring the absorber solution in each impinger to orginal
volume with distilled H2 O and pipet 10-mL portions from each impinger into a series of 25-mL volumetric flasks. If
the color development steps are not to be started within 12 hours of sampling, store the solutions at 5° ±5 °C.
Calculate the total micrograms SO2 in each solution as follows:
where:
Ca = concentration of SO2 in the standard atmosphere, µg/m3;
Os = sampling flow rate, std L/min;
t = sampling time, min;
Va = volume of absorbing solution used for color development (10 mL); and
Vb = volume of absorbing solution used for sampling, mL.
Add the remaining reagents for color development in the same manner as in Section 10.2 for static solutions.
Calculate a calibration equation and a calibration factor (Bg) according to Section 10.2, adhering to all the specified
criteria.
10.3.2 Calibration Option 2B (24-hour samples): Generate a standard atmosphere containing

approximately 1,050 µg SO2/m3 and calculate the exact concentration according to equation
12. Set up a series of six absorbers according to Figure 2 and connect to a common manifold
for sampling the standard atmosphere. Be sure that the total flow rate of the standard exceeds
the flow demand at the sample manifold, with the excess flow vented at atmospheric pressure.
The absorbers are then allowed to sample the atmosphere for varying time periods to yield
solutions containing 0, 0.2, 0.6, 1.0, 1.4, 1.8, and 2.2 µg SO2/mL solution. The sampling times
required to attain these solution concentrations are calculated as follows:
where:
t = sampling time, min;
Vb = volume of absorbing solution used for sampling (50 mL);

Cs = desired concentration of SO2 in the absorbing solution, µg/mL;
Ca = concentration of the standard atmosphere calculated according to equation 12, µg/m3; and
Qs = sampling flow rate, std L/min.
At the completion of sampling, bring the absorber solutions to original volume with distilled water. Pipet a 10-mL
portion from each absorber into one of a series of 25-mL volumetric flasks. If the color development steps are not
to be started within 12 hours of sampling, store the solutions at 5° ±5 °C. Add the remaining reagents for color
development in the same manner as in Section 10.2 for static solutions. Calculate the total µg SO2 in each standard
as follows:
where:
Va = volume of absorbing solution used for color development (10 mL).
All other parameters are defined in equation 14.
Calculate a calibration equation and a calibration factor (Bt) according to Section 10.2 adhering to all the specified
criteria.
11.0 Sample Preparation and Analysis.
11.1 Sample Preparation. Remove the samples from the shipping container. If the shipment period
exceeded 12 hours from the completion of sampling, verify that the temperature is below 10 °C.
Also, compare the solution level to the temporary level mark on the absorber. If either the
temperature is above 10 °C or there was significant loss (more than 10 mL) of the sample during
shipping, make an appropriate notation in the record and invalidate the sample. Prepare the samples
for analysis as follows:
1. For 30-minute or 1-hour samples: Quantitatively transfer the entire 10 mL amount of absorbing
solution to a 25-mL volumetric flask and rinse with a small amount (<5 mL) of distilled water.
2. For 24-hour samples: If the volume of the sample is less than the original 50-mL volume (permanent
mark on the absorber), adjust the volume back to the original volume with distilled water to
compensate for water lost to evaporation during sampling. If the final volume is greater than the
original volume, the volume must be measured using a graduated cylinder. To analyze, pipet 10 mL
of the solution into a 25-mL volumetric flask.
11.2 Sample Analysis. For each set of determinations, prepare a reagent blank by adding 10 mL TCM absorbing
solution to a 25-mL volumetric flask, and two control standards containing approximately 5 and 15 µg SO2,
respectively. The control standards are prepared according to Section 10.2 or 10.3. The analysis is carried out as
follows:
1. Allow the sample to stand 20 minutes after the completion of sampling to allow any ozone to
decompose (if applicable).
2. To each 25-mL volumetric flask containing reagent blank, sample, or control standard, add 1 mL of
0.6% sulfamic acid (Section 8.2.1) and allow to react for 10 min.
3. Accurately pipet 2 mL of 0.2% formaldehyde solution (Section 8.2.2) and then 5 mL of pararosaniline
solution (Section 8.2.13) into each flask. Start a laboratory timer set at 30 minutes.
4. Bring each flask to volume with recently boiled and cooled distilled water and mix thoroughly.
5. During the 30 minutes, the solutions must be in a temperature controlled environment in the range of
20° to 30 °C maintained to ±1 °C. This temperature must also be within 1 °C of that used during
calibration.
6. After 30 minutes and before 60 minutes, determine the corrected absorbances (equation 10) of each
solution at 548 nm using 1-cm optical path length cells against a distilled water reference (Section
10.1). (Distilled water is used as a reference instead of the reagent blank because of the sensitivity of
the reagent blank to temperature.)
7. Do not allow the colored solution to stand in the cells because a film may be deposited. Clean the
cells with isopropyl alcohol after use.
8. The reagent blank must be within 0.03 absorbance units of the intercept of the calibration equation
determined in Section 10.
11.3 Absorbance range. If the absorbance of the sample solution ranges between 1.0 and 2.0, the sample can be
diluted 1:1 with a portion of the reagent blank and the absorbance redetermined within 5 minutes. Solutions with
higher absorbances can be diluted up to sixfold with the reagent blank in order to obtain scale readings of less than
1.0 absorbance unit. However, it is recommended that a smaller portion (<10 mL) of the original sample be
reanalyzed (if possible) if the sample requires a dilution greater than 1:1.
11.4 Reagent disposal. All reagents containing mercury compounds must be stored and disposed of using one of
the procedures contained in Section 13. Until disposal, the discarded solutions can be stored in closed glass
containers and should be left in a fume hood.
12.0 Calculations.
12.1 Calibration Slope, Intercept, and Correlation Coefficient. The method of least squares is used to
calculate a calibration equation in the form of:
where:
y = corrected absorbance,
m = slope, absorbance unit/µg SO2,
x = micrograms of SO2,
b = y intercept (absorbance units).
The slope (m), intercept (b), and correlation coefficient (r) are calculated as follows:
where n is the number of calibration points.
A data form (Figure 5) is supplied for easily organizing calibration data when the slope, intercept, and correlation
coefficient are calculated by hand.
12.2 Total Sample Volume. Determine the sampling volume at standard conditions as follows:
where:
Vstd = sampling volume in std L,
Qi = standard flow rate determined at the initiation of sampling in std L/min,
Qf = standard flow rate determined at the completion of sampling is std L/min, and
t = total sampling time, min.
12.3 Sulfur Dioxide Concentration. Calculate and report the concentration of each sample as follows:
where:
A = corrected absorbance of the sample solution, from equation (10);
Ao = corrected absorbance of the reagent blank, using equation (10);
BX = calibration factor equal to Bs, Bg, or Bt depending on the calibration procedure used, the reciprocal of the slope
of the calibration equation;
Va = volume of absorber solution analyzed, mL;
Vb = total volume of solution in absorber (see 11.1–2), mL; and
Vstd = standard air volume sampled, std L (from Section 12.2).
Data Form
[For hand calculations]
Calibration point no. Micro- grams So2 Absor- bance units

(x) (y) x2 xy y2
1
2
3
4
5
6
Σ x=______ Σ y=______ Σ x2=______ Σxy______ Σy2______
n=______ (number of pairs of coordinates.)
FIGURE 5. Data form for hand calculations.
12.4 Control Standards. Calculate the analyzed micrograms of SO2 in each control standard as follows:
where:
Cq = analyzed µg SO2 in each control standard,
A = corrected absorbance of the control standard, and
Ao = corrected absorbance of the reagent blank.
The difference between the true and analyzed values of the control standards must not be greater than 1 µg. If the
difference is greater than 1 µg, the source of the discrepancy must be identified and corrected.
12.5 Conversion of µg/m3 to ppm (v/v). If desired, the concentration of sulfur dioxide at reference
conditions can be converted to ppm SO2 (v/v) as follows:
13.0 The TCM absorbing solution and any reagents containing mercury compounds must be treated and
disposed of by one of the methods discussed below. Both methods remove greater than 99.99 percent of
the mercury.
13.1 Disposal of Mercury-Containing Solutions.
13.2 Method for Forming an Amalgam.
1. Place the waste solution in an uncapped vessel in a hood.
2. For each liter of waste solution, add approximately 10 g of sodium carbonate until neutralization has
occurred (NaOH may have to be used).
3. Following neutralization, add 10 g of granular zinc or magnesium.
4. Stir the solution in a hood for 24 hours. Caution must be exercised as hydrogen gas is evolved by this
treatment process.
5. After 24 hours, allow the solution to stand without stirring to allow the mercury amalgam (solid black
material) to settle to the bottom of the waste receptacle.
6. Upon settling, decant and discard the supernatant liquid.
7. Quantitatively transfer the solid material to a container and allow to dry.
8. The solid material can be sent to a mercury reclaiming plant. It must not be discarded.
13.3 Method Using Aluminum Foil Strips.
1. Place the waste solution in an uncapped vessel in a hood.
2. For each liter of waste solution, add approximately 10 g of aluminum foil strips. If all the aluminum is
consumed and no gas is evolved, add an additional 10 g of foil. Repeat until the foil is no longer
consumed and allow the gas to evolve for 24 hours.
3. Decant the supernatant liquid and discard.
4. Transfer the elemental mercury that has settled to the bottom of the vessel to a storage container.
5. The mercury can be sent to a mercury reclaiming plant. It must not be discarded.
14.0 References for SO2 Method.
1. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume I, Principles. EPA–600/
9–76–005, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, 1976.
2. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II, Ambient Air Specific
Methods. EPA–600/4–77–027a, U.S. Environmental Protection Agency, Research Triangle Park, NC
27711, 1977.
3. Dasqupta, P. K., and K. B. DeCesare. Stability of Sulfur Dioxide in Formaldehyde and Its Anomalous
Behavior in Tetrachloromercurate (II). Submitted for publication in Atmospheric Environment, 1982.
4. West, P. W., and G. C. Gaeke. Fixation of Sulfur Dioxide as Disulfitomercurate (II) and Subsequent
Colorimetric Estimation. Anal. Chem., 28:1816, 1956.
5. Ephraim, F. Inorganic Chemistry. P. C. L. Thorne and E. R. Roberts, Eds., 5th Edition, Interscience, 1948, p.
562.
6. Lyles, G. R., F. B. Dowling, and V. J. Blanchard. Quantitative Determination of Formaldehyde in the Parts Per
Hundred Million Concentration Level. J. Air. Poll. Cont. Assoc., Vol. 15(106), 1965.
7. McKee, H. C., R. E. Childers, and O. Saenz, Jr. Collaborative Study of Reference Method for Determination
of Sulfur Dioxide in the Atmosphere (Pararosaniline Method). EPA-APTD-0903, U.S. Environmental
Protection Agency, Research Triangle Park, NC 27711, September 1971.
8. Urone, P., J. B. Evans, and C. M. Noyes. Tracer Techniques in Sulfur—Air Pollution Studies Apparatus and
Studies of Sulfur Dioxide Colorimetric and Conductometric Methods. Anal. Chem., 37: 1104, 1965.
9. Bostrom, C. E. The Absorption of Sulfur Dioxide at Low Concentrations (pphm) Studied by an Isotopic
Tracer Method. Intern. J. Air Water Poll., 9:333, 1965.
10. Scaringelli, F. P., B. E. Saltzman, and S. A. Frey. Spectrophotometric Determination of Atmospheric Sulfur
Dioxide. Anal. Chem., 39: 1709, 1967.
11. Pate, J. B., B. E. Ammons, G. A. Swanson, and J. P. Lodge, Jr. Nitrite Interference in Spectrophotometric
Determination of Atmospheric Sulfur Dioxide. Anal. Chem., 37:942, 1965.
12. Zurlo, N., and A. M. Griffini. Measurement of the Sulfur Dioxide Content of the Air in the Presence of
Oxides of Nitrogen and Heavy Metals. Medicina Lavoro, 53:330, 1962.
13. Rehme, K. A., and F. P. Scaringelli. Effect of Ammonia on the Spectrophotometric Determination of
Atmospheric Concentrations of Sulfur Dioxide. Anal. Chem., 47:2474, 1975.
14. McCoy, R. A., D. E. Camann, and H. C. McKee. Collaborative Study of Reference Method for Determination
of Sulfur Dioxide in the Atmosphere (Pararosaniline Method) (24-Hour Sampling). EPA–650/4–74–027,
U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, December 1973.
15. Fuerst, R. G. Improved Temperature Stability of Sulfur Dioxide Samples Collected by the Federal Reference
Method. EPA–600/4–78–018, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711,
April 1978.
16. Scaringelli, F. P., L. Elfers, D. Norris, and S. Hochheiser. Enhanced Stability of Sulfur Dioxide in Solution.
Anal. Chem., 42:1818, 1970.
17. Martin, B. E. Sulfur Dioxide Bubbler Temperature Study. EPA–600/4–77–040, U.S. Environmental
Protection Agency, Research Triangle Park, NC 27711, August 1977.
18. American Society for Testing and Materials. ASTM Standards, Water; Atmospheric Analysis. Part 23.
Philadelphia, PA, October 1968, p. 226.
19. O'Keeffe, A. E., and G. C. Ortman. Primary Standards for Trace Gas Analysis. Anal. Chem., 38:760, 1966.
20. Scaringelli, F. P., S. A. Frey, and B. E. Saltzman. Evaluation of Teflon Permeation Tubes for Use with Sulfur
Dioxide. Amer. Ind. Hygiene Assoc. J., 28:260, 1967.
21. Scaringelli, F. P., A. E. O'Keeffe, E. Rosenberg, and J. P. Bell, Preparation of Known Concentrations of Gases
and Vapors With Permeation Devices Calibrated Gravimetrically. Anal. Chem., 42:871, 1970.
22. A Procedure for Establishing Traceability of Gas Mixtures to Certain National Bureau of Standards
Standard Reference Materials. EPA–600/7–81–010, U.S. Environmental Protection Agency, Environmental
Monitoring Systems Laboratory (MD–77), Research Triangle Park, NC 27711, January 1981.
[47 FR 54899, Dec. 6, 1982; 48 FR 17355, Apr. 22, 1983. Redesignated at 75 FR 35595, June 22, 2010]

Appendix A-2 To Part 50 - Title 40 (Up To Date As of 8-01-2023)

Uploaded by

Copyright:

Available Formats

Appendix A-2 To Part 50 - Title 40 (Up To Date As of 8-01-2023)

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Appendix A-2 To Part 50 - Title 40 (Up To Date As of 8-01-2023)

Uploaded by

Copyright:

Available Formats

Appendix A-2 to Part 50, Title 40 (up to date as of 8/01/2023)

Appendix A-2 to Part 50, Title 40 (Aug. 1, 2023)

This content is from the eCFR and is authoritative but unofficial.

Title 40 —Protection of Environment

5.0 Precision and Accuracy.

7.1.3 Absorber—24-hour sampling: A polypropylene tube 32 mm in diameter and 164 mm long

7.3.1 Spectrophotometer: A spectrophotometer suitable for measurement of absorbances at 548 nm

M = volume of thiosulfate required in mL, and

W = weight of potassium iodate in g (recorded weight in Section 8.2.7).

A = volume of thiosulfate titrant required for the blank, mL;

B = volume of thiosulfate titrant required for the sample, mL;

NT = normality of the thiosulfate titrant, from equation (3);

32,000 = milliequivalent weight of SO2, µg;

25 = volume of standard sulfite solution, mL; and

0.02 = dilution factor.

8.2.12 Purified pararosaniline (PRA) stock solution (0.2% nominal):

8.2.12.1 Dye specifications —

8.2.12.3 Purification procedure for PRA —

2. Weigh 100 mg of pararosaniline hydrochloride dye (PRA) in a small beaker. Add 50 mL of

3. To a 125-mL separatory funnel, add 50 mL of the equilibrated 1-butanol (draw the

4. Measure the absorbance of the above solution at 540 nm with a spectrophotometer

A = measured absorbance of the final mixture (absorbance units);

9.0 Sampling Procedure.

9.4 Flow Measurement.

Qact = flow rate at monitoring site conditions, L/min;

Pb = barometric pressure at monitoring site conditions, mm Hg or kPa;

RH = fractional relative humidity of the air being measured;

H = sampling site elevation above sea level in meters.

10.0 Analytical Calibration.

2. Zero the spectrophotometer with the reference cell.

Aobs = uncorrected absorbance, and

VTCM/SO2 = volume of sulfite-TCM solution used, mL;

Ca = concentration of SO2 at standard conditions, µg/m3;

Pr = permeation rate, µg/min;

Qd = flow rate of dilution air, std L/min; and

Qp = flow rate of carrier gas across permeation device, std L/min.

Ca = concentration of SO2 in the standard atmosphere, µg/m3;

Os = sampling flow rate, std L/min;

t = sampling time, min;

Vb = volume of absorbing solution used for sampling, mL.

10.3.2 Calibration Option 2B (24-hour samples): Generate a standard atmosphere containing

t = sampling time, min;

Vb = volume of absorbing solution used for sampling (50 mL);

Cs = desired concentration of SO2 in the absorbing solution, µg/mL;

Qs = sampling flow rate, std L/min.

Va = volume of absorbing solution used for color development (10 mL).

All other parameters are defined in equation 14.

11.0 Sample Preparation and Analysis.

m = slope, absorbance unit/µg SO2,

b = y intercept (absorbance units).

where n is the number of calibration points.

Vstd = sampling volume in std L,

Qi = standard flow rate determined at the initiation of sampling in std L/min,

t = total sampling time, min.

A = corrected absorbance of the sample solution, from equation (10);

Ao = corrected absorbance of the reagent blank, using equation (10);

Va = volume of absorber solution analyzed, mL;

Vb = total volume of solution in absorber (see 11.1–2), mL; and

Vstd = standard air volume sampled, std L (from Section 12.2).

Σ x= Σ y= Σ x2= Σxy Σy2__