You are on page 1of 17

§ 50.15 40 CFR Ch.

I (7–1–10 Edition)
NOTE: EPA notes that the table of revised part, is less than or equal to 0.15
deadlines only applies to data EPA will use micrograms per cubic meter.
to establish the final initial designations for
new or revised NAAQS. The general schedule [73 FR 67052, Nov. 12, 2008]
applies for all other purposes, most notably,
for data used by EPA for redesignations to § 50.17 National primary ambient air
attainment. quality standards for sulfur oxides
(sulfur dioxide).
(a) The level of the national primary
* * * * *
1-hour annual ambient air quality
§ 50.15 National primary and sec- standard for oxides of sulfur is 75 parts
ondary ambient air quality stand- per billion (ppb, which is 1 part in
ards for ozone. 1,000,000,000), measured in the ambient
air as sulfur dioxide (SO2).
(a) The level of the national 8-hour (b) The 1-hour primary standard is
primary and secondary ambient air met at an ambient air quality moni-
quality standards for ozone (O3) is 0.075 toring site when the three-year average
parts per million (ppm), daily max- of the annual (99th percentile) of the
imum 8-hour average, measured by a daily maximum 1-hour average con-
reference method based on appendix D centrations is less than or equal to 75
to this part and designated in accord- ppb, as determined in accordance with
ance with part 53 of this chapter or an appendix T of this part.
equivalent method designated in ac- (c) The level of the standard shall be
cordance with part 53 of this chapter. measured by a reference method based
(b) The 8-hour primary and secondary on appendix A or A–1 of this part, or by
O3 ambient air quality standards are a Federal Equivalent Method (FEM)
met at an ambient air quality moni- designated in accordance with part 53
toring site when the 3-year average of of this chapter.
the annual fourth-highest daily max- [75 FR 35592, June 22, 2010]
imum 8-hour average O3 concentration EFFECTIVE DATE NOTE: At 75 FR 35592, June
is less than or equal to 0.075 ppm, as de- 22, 2010, § 50.17 was added, effective Aug. 23,
termined in accordance with appendix 2010.
P to this part.
APPENDIX A TO PART 50—REFERENCE
[73 FR 16511, Mar. 27, 2008] METHOD FOR THE DETERMINATION OF
SULFUR DIOXIDE IN THE ATMOS-
§ 50.16 National primary and sec- PHERE (PARAROSANILINE METHOD)
ondary ambient air quality stand-
ards for lead. 1.0 Applicability.
1.1 This method provides a measurement of
(a) The national primary and sec- the concentration of sulfur dioxide (SO2) in
ondary ambient air quality standards ambient air for determining compliance with
for lead (Pb) and its compounds are 0.15 the primary and secondary national ambient
micrograms per cubic meter, arith- air quality standards for sulfur oxides (sulfur
metic mean concentration over a 3- dioxide) as specified in § 50.4 and § 50.5 of this
chapter. The method is applicable to the
month period, measured in the ambient
measurement of ambient SO2 concentrations
air as Pb either by: using sampling periods ranging from 30 min-
(1) A reference method based on Ap- utes to 24 hours. Additional quality assur-
pendix G of this part and designated in ance procedures and guidance are provided in
accordance with part 53 of this chapter part 58, appendixes A and B, of this chapter
or; and in references 1 and 2.
2.0 Principle.
(2) An equivalent method designated 2.1 A measured volume of air is bubbled
in accordance with part 53 of this chap- through a solution of 0.04 M potassium
ter. tetrachloromercurate (TCM). The SO2
(b) The national primary and sec- present in the air stream reacts with the
ondary ambient air quality standards TCM solution to form a stable
monochlorosulfonatomercurate(3) complex.
for Pb are met when the maximum
wwoods2 on DSKDVH8Z91PROD with CFR

Once formed, this complex resists air oxida-


arithmetic 3-month mean concentra- tion(4, 5) and is stable in the presence of
tion for a 3-year period, as determined strong oxidants such as ozone and oxides of
in accordance with Appendix R of this nitrogen. During subsequent analysis, the

14

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00024 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Environmental Protection Agency Pt. 50, App. A
complex is reacted with acid-bleached • The day-to-day variability within an indi-
pararosaniline dye and formaldehyde to form vidual laboratory (repeatability) varies
an intensely colored pararosaniline methyl linearly with concentration from ±18.1 μg/
sulfonic acid.(6) The optical density of this m3 at levels of 100 μg/m3 to ±50.9 μg/m3 at
species is determined levels of 400 μg/m3.
spectrophotometrically at 548 nm and is di- • The day-to-day variability between two or
rectly related to the amount of SO2 col- more laboratories (reproducibility) varies
lected. The total volume of air sampled, cor- linearly with concentration from ±36.9 μg/
rected to EPA reference conditions (25 °C, 760 m3 at levels of 100 μg/m3 to ±103.5 μ g/m3 at
mm Hg [101 kPa]), is determined from the levels of 400 μg/m3.
measured flow rate and the sampling time. • The method has a concentration-dependent
The concentration of SO2 in the ambient air bias, which becomes significant at the 95
is computed and expressed in micrograms per percent confidence level at the high con-
standard cubic meter (μg/std m3). centration level. Observed values tend to
3.0 Range. be lower than the expected SO2 concentra-
3.1 The lower limit of detection of SO2 in 10 tion level.
mL of TCM is 0.75 μg (based on collaborative 6.0 Stability.
test results).(7) This represents a concentra- 6.1 By sampling in a controlled tempera-
tion of 25 μg SO2/m3 (0.01 ppm) in an air sam- ture environment of 15°±10 °C, greater than
ple of 30 standard liters (short-term sam- 98.9 percent of the SO2–TCM complex is re-
pling) and a concentration of 13 μg SO2/m3 tained at the completion of sampling. (15) If
(0.005 ppm) in an air sample of 288 standard kept at 5 °C following the completion of sam-
liters (long-term sampling). Concentrations pling, the collected sample has been found to
less than 25 μg SO2/m3 can be measured by be stable for up to 30 days.(10) The presence
sampling larger volumes of ambient air; of EDTA enhances the stability of SO2 in the
however, the collection efficiency falls off TCM solution and the rate of decay is inde-
rapidly at low concentrations.(8, 9) Beer’s pendent of the concentration of SO2.(16)
law is adhered to up to 34 μg of SO2 in 25 mL 7.0 Apparatus.
of final solution. This upper limit of the 7.1 Sampling.
analysis range represents a concentration of 7.1.1 Sample probe: A sample probe meeting
1,130 μg SO2/m3 (0.43 ppm) in an air sample of the requirements of section 7 of 40 CFR part
30 standard liters and a concentration of 590 58, appendix E (Teflon ® or glass with resi-
μg SO2/m3 (0.23 ppm) in an air sample of 288 dence time less than 20 sec.) is used to trans-
standard liters. Higher concentrations can be port ambient air to the sampling train loca-
measured by collecting a smaller volume of tion. The end of the probe should be designed
air, by increasing the volume of absorbing or oriented to preclude the sampling of pre-
solution, or by diluting a suitable portion of cipitation, large particles, etc. A suitable
the collected sample with absorbing solution probe can be constructed from Teflon ® tub-
prior to analysis. ing connected to an inverted funnel.
4.0 Interferences. 7.1.2 Absorber—short-term sampling: An all
4.1 The effects of the principal potential glass midget impinger having a solution ca-
interferences have been minimized or elimi- pacity of 30 mL and a stem clearance of 4 ±1
nated in the following manner: Nitrogen ox- mm from the bottom of the vessel is used for
ides by the addition of sulfamic acid,(10, 11) sampling periods of 30 minutes and 1 hour (or
heavy metals by the addition of ethylene- any period considerably less than 24 hours).
diamine tetracetic acid disodium salt Such an impinger is shown in Figure 1. These
(EDTA) and phosphoric acid,(10, 12) and impingers are commercially available from
ozone by time delay.(10) Up to 60 μg Fe (III), distributors such as Ace Glass, Incorporated.
22 μg V (V), 10 μg Cu (II), 10 μg Mn (II), and 7.1.3 Absorber—24-hour sampling: A poly-
10 μg Cr (III) in 10 mL absorbing reagent can propylene tube 32 mm in diameter and 164
be tolerated in the procedure.(10) No signifi- mm long (available from Bel Art Products,
cant interference has been encountered with Pequammock, NJ) is used as the absorber.
2.3 μg NH3.(13) The cap of the absorber must be a poly-
5.0 Precision and Accuracy. propylene cap with two ports (rubber stop-
5.1 The precision of the analysis is 4.6 per- pers are unacceptable because the absorbing
cent (at the 95 percent confidence level) reagent can react with the stopper to yield
based on the analysis of standard sulfite erroneously high SO2 concentrations). A
samples.(10) glass impinger stem, 6 mm in diameter and
5.2 Collaborative test results (14) based on 158 mm long, is inserted into one port of the
the analysis of synthetic test atmospheres absorber cap. The tip of the stem is tapered
(SO2 in scrubbed air) using the 24-hour sam- to a small diameter orifice (0.4 ±0.1 mm) such
pling procedure and the sulfite-TCM calibra- that a No. 79 jeweler’s drill bit will pass
tion procedure show that: through the opening but a No. 78 drill bit
• The replication error varies linearly with
wwoods2 on DSKDVH8Z91PROD with CFR

will not. Clearance from the bottom of the


concentration from ±2.5 μg/m3 at con- absorber to the tip of the stem must be 6 ±2
centrations of 100 μg/m3 to ±7 μg/m3 at con- mm. Glass stems can be fabricated by any
centrations of 400 μg/m3. reputable glass blower or can be obtained

15

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00025 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Pt. 50, App. A 40 CFR Ch. I (7–1–10 Edition)
from a scientific supply firm. Upon receipt, as shown in Figure 2. Glass wool may be sub-
the orifice test should be performed to verify stituted for silica gel when collecting short-
the orifice size. The 50 mL volume level term samples (1 hour or less) as shown in
should be permanently marked on the ab- Figure 1, or for long term (24 hour) samples
sorber. The assembled absorber is shown in if flow changes are not routinely encoun-
Figure 2. tered.
7.1.4 Moisture trap: A moisture trap con- 7.1.5 Cap seals: The absorber and moisture
structed of a glass trap as shown in Figure 1
trap caps must seal securely to prevent leaks
or a polypropylene tube as shown in Figure
during use. Heat-shrink material as shown in
2 is placed between the absorber tube and
Figure 2 can be used to retain the cap seals
flow control device to prevent entrained liq-
uid from reaching the flow control device. if there is any chance of the caps coming
The tube is packed with indicating silica gel loose during sampling, shipment, or storage.
wwoods2 on DSKDVH8Z91PROD with CFR

16

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00026 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Environmental Protection Agency Pt. 50, App. A
wwoods2 on DSKDVH8Z91PROD with CFR

17
50-702.eps</GPH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00027 Fmt 8010 Sfmt 8006 Y:\SGML\220144.XXX 220144
Pt. 50, App. A 40 CFR Ch. I (7–1–10 Edition)
wwoods2 on DSKDVH8Z91PROD with CFR

18
50-703.eps</GPH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00028 Fmt 8010 Sfmt 8006 Y:\SGML\220144.XXX 220144
Environmental Protection Agency Pt. 50, App. A
7.1.6 Flow control device: A calibrated ro- meter is also recommended to determine the
tameter and needle valve combination capa- duration of the sampling period.
ble of maintaining and measuring air flow to 7.2 Shipping.
within ±2 percent is suitable for short-term 7.2.1 Shipping container: A shipping con-
sampling but may not be used for long-term tainer that can maintain a temperature of 5°
sampling. A critical orifice can be used for ±5 °C is used for transporting the sample
regulating flow rate for both long-term and from the collection site to the analytical
short-term sampling. A 22-gauge hypodermic laboratory. Ice coolers or refrigerated ship-
needle 25 mm long may be used as a critical ping containers have been found to be satis-
orifice to yield a flow rate of approximately factory. The use of eutectic cold packs in-
1 L/min for a 30-minute sampling period. stead of ice will give a more stable tempera-
When sampling for 1 hour, a 23-gauge hypo- ture control. Such equipment is available
dermic needle 16 mm in length will provide a from Cole-Parmer Company, 7425 North Oak
flow rate of approximately 0.5 L/min. Flow Park Avenue, Chicago, IL 60648.
control for a 24-hour sample may be provided
7.3 Analysis.
by a 27-gauge hypodermic needle critical ori-
fice that is 9.5 mm in length. The flow rate 7.3.1 Spectrophotometer: A spectrophotom-
should be in the range of 0.18 to 0.22 L/min. eter suitable for measurement of
7.1.7 Flow measurement device: Device cali- absorbances at 548 nm with an effective spec-
brated as specified in 9.4.1 and used to meas- tral bandwidth of less than 15 nm is required
ure sample flow rate at the monitoring site. for analysis. If the spectrophotometer reads
7.1.8 Membrane particle filter: A membrane out in transmittance, convert to absorbance
filter of 0.8 to 2 μm porosity is used to pro- as follows:
tect the flow controller from particles dur-
ing long-term sampling. This item is op- A = log10 (1/T ) (1)
tional for short-term sampling. where:
7.1.9 Vacuum pump: A vacuum pump
equipped with a vacuum gauge and capable A = absorbance, and
of maintaining at least 70 kPa (0.7 atm) vac- T = transmittance (0<≥T<1).
uum differential across the flow control de- A standard wavelength filter traceable to
vice at the specified flow rate is required for the National Bureau of Standards is used to
sampling. verify the wavelength calibration according
7.1.10 Temperature control device: The tem- to the procedure enclosed with the filter.
perature of the absorbing solution during The wavelength calibration must be verified
sampling must be maintained at 15° ±10 °C. upon initial receipt of the instrument and
As soon as possible following sampling and after each 160 hours of normal use or every 6
until analysis, the temperature of the col- months, whichever occurs first.
lected sample must be maintained at 5° ±5 °C.
7.3.2 Spectrophotometer cells: A set of 1-cm
Where an extended period of time may elapse
path length cells suitable for use in the visi-
before the collected sample can be moved to
ble region is used during analysis. If the cells
the lower storage temperature, a collection
are unmatched, a matching correction factor
temperature near the lower limit of the 15
must be determined according to Section
±10 °C range should be used to minimize
10.1.
losses during this period. Thermoelectric
coolers specifically designed for this tem- 7.3.3 Temperature control device: The color
perature control are available commercially development step during analysis must be
and normally operate in the range of 5° to 15 conducted in an environment that is in the
°C. Small refrigerators can be modified to range of 20° to 30 °C and controlled to ±1 °C.
provide the required temperature control; Both calibration and sample analysis must
however, inlet lines must be insulated from be performed under identical conditions
the lower temperatures to prevent condensa- (within 1 °C). Adequate temperature control
tion when sampling under humid conditions. may be obtained by means of constant tem-
A small heating pad may be necessary when perature baths, water baths with manual
sampling at low temperatures (<7 °C) to pre- temperature control, or temperature con-
vent the absorbing solution from freez- trolled rooms.
ing.(17) 7.3.4 Glassware: Class A volumetric glass-
7.1.11 Sampling train container: The absorb- ware of various capacities is required for pre-
ing solution must be shielded from light dur- paring and standardizing reagents and stand-
ing and after sampling. Most commercially ards and for dispensing solutions during
available sampler trains are enclosed in a analysis. These included pipets, volumetric
light-proof box. flasks, and burets.
7.1.12 Timer: A timer is recommended to 7.3.5 TCM waste receptacle: A glass waste re-
initiate and to stop sampling for the 24-hour ceptacle is required for the storage of spent
TCM solution. This vessel should be
wwoods2 on DSKDVH8Z91PROD with CFR

period. The timer is not a required piece of


equipment; however, without the timer a stoppered and stored in a hood at all times.
technician would be required to start and 8.0 Reagents.
stop the sampling manually. An elapsed time 8.1 Sampling.

19
EC08NO91.000</MATH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00029 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Pt. 50, App. A 40 CFR Ch. I (7–1–10 Edition)
8.1.1 Distilled water: Purity of distilled 8.2.7 Potassium iodate solution: Accurately
water must be verified by the following pro- weigh to the nearest 0.1 mg, 1.5 g (record
cedure:(18) weight) of primary standard grade potassium
• Place 0.20 mL of potassium permanganate iodate that has been previously dried at 180
solution (0.316 g/L), 500 mL of distilled °C for at least 3 hours and cooled in a
water, and 1mL of concentrated sulfuric dessicator. Dissolve, then dilute to volume in
acid in a chemically resistant glass bottle, a 500-mL volumetric flask with distilled
stopper the bottle, and allow to stand. water.
• If the permanganate color (pink) does not 8.2.8 Stock sodium thiosulfate solution (0.1 N):
disappear completely after a period of 1 Prepare a stock solution by dissolving 25 g
hour at room temperature, the water is sodium thiosulfate (Na2 S2 O3÷5H2 O) in 1,000
suitable for use. mL freshly boiled, cooled, distilled water and
• If the permanganate color does disappear, adding 0.1 g sodium carbonate to the solu-
the water can be purified by redistilling tion. Allow the solution to stand at least 1
with one crystal each of barium hydroxide day before standardizing. To standardize, ac-
and potassium permanganate in an all curately pipet 50 mL of potassium iodate so-
glass still. lution (Section 8.2.7) into a 500-mL iodine
8.1.2 Absorbing reagent (0.04 M potassium flask and add 2.0 g of potassium iodide and 10
tetrachloromercurate [TCM]): Dissolve 10.86 mL of 1 N HCl. Stopper the flask and allow
g mercuric chloride, 0.066 g EDTA, and 6.0 g to stand for 5 minutes. Titrate the solution
potassium chloride in distilled water and di- with stock sodium thiosulfate solution (Sec-
lute to volume with distilled water in a 1,000- tion 8.2.8) to a pale yellow color. Add 5 mL of
mL volumetric flask. (Caution: Mercuric starch solution (Section 8.2.5) and titrate
chloride is highly poisonous. If spilled on until the blue color just disappears. Cal-
skin, flush with water immediately.) The pH culate the normality (Ns) of the stock so-
of this reagent should be between 3.0 and 5.0 dium thiosulfate solution as follows:
(10) Check the pH of the absorbing solution
W
by using pH indicating paper or a pH meter.
If the pH of the solution is not between 3.0
NS = × 2.80 (2)
and 5.0, dispose of the solution according to M
one of the disposal techniques described in where:
Section 13.0. The absorbing reagent is nor- M = volume of thiosulfate required in mL,
mally stable for 6 months. If a precipitate and
forms, dispose of the reagent according to W = weight of potassium iodate in g (re-
one of the procedures described in Section corded weight in Section 8.2.7).
13.0.
8.2 Analysis. 10 3 (conversion of g to mg) × 0.1(fraction iodate used )
2.80 =
8.2.1 Sulfamic acid (0.6%): Dissolve 0.6 g sul- 35.67 (equivalent weight of potassium iodate)
famic acid in 100 mL distilled water. Perpare 8.2.9 Working sodium thiosulfate titrant (0.01
fresh daily. N): Accurately pipet 100 mL of stock sodium
8.2.2 Formaldehyde (0.2%): Dilute 5 mL thiosulfate solution (Section 8.2.8) into a
formaldehyde solution (36 to 38 percent) to 1,000-mL volumetric flask and dilute to vol-
1,000 mL with distilled water. Prepare fresh ume with freshly boiled, cooled, distilled
daily. water. Calculate the normality of the work-
8.2.3 Stock iodine solution (0.1 N): Place 12.7 ing sodium thiosulfate titrant (NT) as fol-
g resublimed iodine in a 250-mL beaker and lows:
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
N T = N S × 0.100 (3)
distilled water. 8.2.10 Standardized sulfite solution for the
8.2.4 Iodine solution (0.01 N): Prepare ap- preparation of working sulfite-TCM solution:
proximately 0.01 N iodine solution by dilut- Dissolve 0.30 g sodium metabisulfite (Na2 S2
ing 50 mL of stock iodine solution (Section O5) or 0.40 g sodium sulfite (Na2 SO3) in 500
8.2.3) to 500 mL with distilled water. mL of recently boiled, cooled, distilled
8.2.5 Starch indicator solution: Triturate 0.4 water. (Sulfite solution is unstable; it is
g soluble starch and 0.002 g mercuric iodide therefore important to use water of the high-
(preservative) with enough distilled water to est purity to minimize this instability.) This
EC08NO91.003</MATH>

form a paste. Add the paste slowly to 200 mL solution contains the equivalent of 320 to 400
of boiling distilled water and continue boil- μg SO2/mL. The actual concentration of the
ing until clear. Cool and transfer the solu- solution is determined by adding excess io-
tion to a glass stopperd bottle. dine and back-titrating with standard so-
8.2.6 1 N hydrochloric acid: Slowly and while dium thiosulfate solution. To back-titrate,
wwoods2 on DSKDVH8Z91PROD with CFR

stirring, add 86 mL of concentrated hydro- pipet 50 mL of the 0.01 N iodine solution


EC08NO91.002</MATH>

chloric acid to 500 mL of distilled water. (Section 8.2.4) into each of two 500-mL iodine
Allow to cool and dilute to 1,000 mL with dis- flasks (A and B). To flask A (blank) add 25
tilled water. mL distilled water, and to flask B (sample)

20
EC08NO91.001</MATH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00030 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Environmental Protection Agency Pt. 50, App. A
pipet 25 mL sulfite solution. Stopper the tinue the titration until the blue color just
flasks and allow to stand for 5 minutes. Pre- disappears.
pare the working sulfite-TCM solution (Sec- 8.2.11 Working sulfite-TCM solution: Accu-
tion 8.2.11) immediately prior to adding the rately pipet 5 mL of the standard sulfite so-
iodine solution to the flasks. Using a buret lution (Section 8.2.10) into a 250-mL volu-
containing standardized 0.01 N thiosulfate metric flask and dilute to volume with 0.04
titrant (Section 8.2.9), titrate the solution in M TCM. Calculate the concentration of sul-
each flask to a pale yellow color. Then add 5 fur dioxide in the working solution as fol-
mL starch solution (Section 8.2.5) and con- lows:

( A − B)( N T )(32,000)
C TCM / SO 2 (μg SO 2 /mL ) = × 0.02 ( 4)
25

where: percent potassium iodide (KI) solution in a


A = volume of thiosulfate titrant required 50-mL separatory funnel and shake thor-
for the blank, mL; oughly. If a yellow color appears in the alco-
B = volume of thiosulfate titrant required hol phase, redistill the 1-butanol from silver
for the sample, mL; oxide and collect the middle fraction or pur-
NT = normality of the thiosulfate titrant, chase a new supply of 1-butanol.
from equation (3); 2. Weigh 100 mg of pararosaniline hydro-
32,000 = milliequivalent weight of SO2, μg; chloride dye (PRA) in a small beaker. Add 50
25 = volume of standard sulfite solution, mL; mL of the equilibrated acid (drain in acid
and from the bottom of the separatory funnel in
0.02 = dilution factor. 1.) to the beaker and let stand for several
This solution is stable for 30 days if kept at minutes. Discard the remaining acid phase in
5 °C. (16) If not kept at 5 °C, prepare fresh the separatory funnel.
daily. 3. To a 125-mL separatory funnel, add 50
8.2.12 Purified pararosaniline (PRA) stock so- mL of the equilibrated 1-butanol (draw the 1-
lution (0.2% nominal): butanol from the top of the separatory fun-
8.2.12.1 Dye specifications— nel in 1.). Transfer the acid solution (from 2.)
• The dye must have a maximum absorbance containing the dye to the funnel and shake
at a wavelength of 540 nm when assayed in carefully to extract. The violet impurity will
a buffered solution of 0.1 M sodium ace- transfer to the organic phase.
tate-acetic acid; 4. Transfer the lower aqueous phase into
• The absorbance of the reagent blank, another separatory funnel, add 20 mL of
which is temperature sensitive (0.015 ab- equilibrated 1-butanol, and extract again.
sorbance unit/ °C), must not exceed 0.170 at 5. Repeat the extraction procedure with
22 °C with a 1-cm optical path length when three more 10-mL portions of equilibrated 1-
the blank is prepared according to the butanol.
specified procedure; 6. After the final extraction, filter the acid
• The calibration curve (Section 10.0) must phase through a cotton plug into a 50-mL
have a slope equal to 0.030 ±0.002 absorb- volumetric flask and bring to volume with 1
ance unit/μg SO2 with a 1-cm optical path N HCl. This stock reagent will be a yellowish
length when the dye is pure and the sulfite red.
solution is properly standardized. 7. To check the purity of the PRA, perform
8.2.12.2 Preparation of stock PRA solution—A the assay and adjustment of concentration
specially purified (99 to 100 percent pure) so- (Section 8.2.12.4) and prepare a reagent blank
lution of pararosaniline, which meets the (Section 11.2); the absorbance of this reagent
above specifications, is commercially avail- blank at 540 nm should be less than 0.170 at
able in the required 0.20 percent concentra- 22 °C. If the absorbance is greater than 0.170
tion (Harleco Co.). Alternatively, the dye under these conditions, further extractions
may be purified, a stock solution prepared, should be performed.
and then assayed according to the procedure 8.2.12.4 PRA assay procedure—The con-
as described below.(10) centration of pararosaniline hydrochloride
8.2.12.3 Purification procedure for PRA— (PRA) need be assayed only once after purifi-
1. Place 100 mL each of 1-butanol and 1 N cation. It is also recommended that commer-
HCl in a large separatory funnel (250-mL) cial solutions of pararosaniline be assayed
wwoods2 on DSKDVH8Z91PROD with CFR

and allow to equilibrate. Note: Certain when first purchased. The assay procedure is
batches of 1-butanol contain oxidants that as follows:(10)
create an SO2 demand. Before using, check 1. Prepare 1 M acetate-acetic acid buffer
by placing 20 mL of 1-butanol and 5 mL of 20 stock solution with a pH of 4.79 by dissolving

21
EC08NO91.004</MATH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00031 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Pt. 50, App. A 40 CFR Ch. I (7–1–10 Edition)
13.61 g of sodium acetate trihydrate in dis- cally described, the conditions must be ad-
tilled water in a 100-mL volumetric flask. justed so that linearity is maintained be-
Add 5.70 mL of glacial acetic acid and dilute tween absorbance and concentration over the
to volume with distilled water. dynamic range. Absorbing reagent volumes
2. Pipet 1 mL of the stock PRA solution ob- less than 10 mL are not recommended. The
tained from the purification process or from collection efficiency is above 98 percent for
a commercial source into a 100-mL volu- the conditions described; however, the effi-
metric flask and dilute to volume with dis- ciency may be substantially lower when
tilled water. sampling concentrations below 25 μgSO2/
3. Transfer a 5–mL aliquot of the diluted m3.(8,9)
PRA solution from 2. into a 50–mL volu- 9.2 30-Minute and 1-Hour Sampling. Place 10
metric flask. Add 5mL of 1 M acetate-acetic mL of TCM absorbing reagent in a midget
acid buffer solution from 1. and dilute the impinger and seal the impinger with a thin
mixture to volume with distilled water. Let film of silicon stopcock grease (around the
the mixture stand for 1 hour. ground glass joint). Insert the sealed im-
4. Measure the absorbance of the above so- pinger into the sampling train as shown in
lution at 540 nm with a spectrophotometer Figure 1, making sure that all connections
against a distilled water reference. Compute between the various components are leak
the percentage of nominal concentration of tight. Greaseless ball joint fittings, heat
PRA by shrinkable Teflon ® tubing, or Teflon ® tube
fittings may be used to attain leakfree con-
A×K ditions for portions of the sampling train
%PRA = ( 5) that come into contact with air containing
W SO2. Shield the absorbing reagent from di-
where: rect sunlight by covering the impinger with
aluminum foil or by enclosing the sampling
A = measured absorbance of the final mix- train in a light-proof box. Determine the
ture (absorbance units); flow rate according to Section 9.4.2. Collect
W = weight in grams of the PRA dye used in the sample at 1 ±0.10 L/min for 30-minute
the assay to prepare 50 mL of stock solu- sampling or 0.500 ±0.05 L/min for 1-hour sam-
tion (for example, 0.100 g of dye was used to pling. Record the exact sampling time in
prepare 50 mL of solution in the purifi- minutes, as the sample volume will later be
cation procedure; when obtained from com- determined using the sampling flow rate and
mercial sources, use the stated concentra- the sampling time. Record the atmospheric
tion to compute W; for 98% PRA, W=.098 pressure and temperature.
g.); and 9.3 24-Hour Sampling. Place 50 mL of TCM
K = 21.3 for spectrophotometers having a absorbing solution in a large absorber, close
spectral bandwidth of less than 15 nm and the cap, and, if needed, apply the heat shrink
a path length of 1 cm. material as shown in Figure 3. Verify that
8.2.13 Pararosaniline reagent: To a 250–mL the reagent level is at the 50 mL mark on the
volumetric flask, add 20 mL of stock PRA so- absorber. Insert the sealed absorber into the
lution. Add an additional 0.2 mL of stock so- sampling train as shown in Figure 2. At this
lution for each percentage that the stock as- time verify that the absorber temperature is
says below 100 percent. Then add 25 mL of 3 controlled to 15 ±10 °C. During sampling, the
M phosphoric acid and dilute to volume with absorber temperature must be controlled to
distilled water. The reagent is stable for at prevent decomposition of the collected com-
least 9 months. Store away from heat and plex. From the onset of sampling until anal-
light. ysis, the absorbing solution must be pro-
9.0 Sampling Procedure. tected from direct sunlight. Determine the
9.1 General Considerations. Procedures are flow rate according to Section 9.4.2. Collect
described for short-term sampling (30-minute the sample for 24 hours from midnight to
and 1-hour) and for long-term sampling (24- midnight at a flow rate of 0.200 ±0.020 L/min.
hour). Different combinations of absorbing A start/stop timer is helpful for initiating
reagent volume, sampling rate, and sampling and stopping sampling and an elapsed time
time can be selected to meet special needs. meter will be useful for determining the
For combinations other than those specifi- sampling time.
wwoods2 on DSKDVH8Z91PROD with CFR

22
EC08NO91.005</MATH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00032 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Environmental Protection Agency Pt. 50, App. A

9.4 Flow Measurement. For 24-hour samples, the standard flow rate
9.4.1 Calibration: Flow measuring devices is determined at the time the absorber is
used for the on-site flow measurements re- placed in the sampling train and again when
quired in 9.4.2 must be calibrated against a the absorber is removed from the train for
reliable flow or volume standard such as an shipment to the analytical laboratory with a
NBS traceable bubble flowmeter or cali- calibrated flow measuring device connected
brated wet test meter. Rotameters or crit- to the inlet of the sampling train. The flow
ical orifices used in the sampling train may rate determination must be made with all
be calibrated, if desired, as a quality control components of the sampling system in oper-
check, but such calibration shall not replace ation (e.g., the absorber temperature con-
the on-site flow measurements required by troller and any sample box heaters must also
9.4.2. In-line rotameters, if they are to be be operating). Equation 6 may be used to de-
calibrated, should be calibrated in situ, with termine the standard flow rate when a cali-
the appropriate volume of solution in the ab- brated positive displacement meter is used
sorber. as the flow measuring device. Other types of
9.4.2 Determination of flow rate at sampling calibrated flow measuring devices may also
site: For short-term samples, the standard be used to determine the flow rate at the
wwoods2 on DSKDVH8Z91PROD with CFR

flow rate is determined at the sampling site sampling site provided that the user applies
at the initiation and completion of sample any appropriate corrections to devices for
collection with a calibrated flow measuring which output is dependent on temperature or
device connected to the inlet of the absorber. pressure.

23
50-708.eps</GPH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00033 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Pt. 50, App. A 40 CFR Ch. I (7–1–10 Edition)

Pb − (1 − RH)PH 2 O 298.16.
Q std = Q act × × (6)
Pstd (Tmeter + 27316
. ).

where: volume standards only, i.e., bubble flow-


Qstd = flow rate at standard conditions, std L/ meter or wet test meter; for dry standards,
min (25 °C and 760 mm Hg); i.e., dry test meter, PH2O=0);
Qact = flow rate at monitoring site conditions, Pstd = standard barometric pressure, in the
L/min; same units as Pb (760 mm Hg or 101 kPa);
Pb = barometric pressure at monitoring site and
conditions, mm Hg or kPa; Tmeter = temperature of the air in the flow or
RH = fractional relative humidity of the air volume standard, °C (e.g., bubble flow-
being measured; meter).
PH2O = vapor pressure of water at the tem- If a barometer is not available, the fol-
perature of the air in the flow or volume lowing equation may be used to determine
standard, in the same units as Pb, (for wet the barometric pressure:

Pb = 760 −.076(H) mm Hg, or Pb = 101−.01(H)kPa (7)

where: ture is above 10 °C. Store the sample at 5° ±5


H = sampling site elevation above sea level °C until it is analyzed.
in meters. 10.0 Analytical Calibration.
10.1 Spectrophotometer Cell Matching. If un-
If the initial flow rate (Qi) differs from the matched spectrophotometer cells are used,
flow rate of the critical orifice or the flow an absorbance correction factor must be de-
rate indicated by the flowmeter in the sam- termined as follows:
pling train (Qc) by more than 5 percent as de- 1. Fill all cells with distilled water and des-
termined by equation (8), check for leaks and ignate the one that has the lowest absorb-
redetermine Qi. ance at 548 nm as the reference. (This ref-
erence cell should be marked as such and
Qi − Qc continually used for this purpose throughout
% Diff = ×100 ( 8) all future analyses.)
Qc 2. Zero the spectrophotometer with the ref-
Invalidate the sample if the difference be- erence cell.
tween the initial (Qi) and final (Qf) flow rates 3. Determine the absorbance of the remain-
is more than 5 percent as determined by ing cells (Ac) in relation to the reference cell
equation (9): and record these values for future use. Mark
all cells in a manner that adequately identi-

EC08NO91.010</MATH>
Qi − Qf fies the correction.
% Diff = ×100 ( 9) The corrected absorbance during future
analyses using each cell is determining as
Qf follows:
9.5 Sample Storage and Shipment. Remove
the impinger or absorber from the sampling A = A obs − A c (10 )
train and stopper immediately. Verify that EC08NO91.009</MATH>
where:
the temperature of the absorber is not above
25 °C. Mark the level of the solution with a A = corrected absorbance,
temporary (e.g., grease pencil) mark. If the Aobs = uncorrected absorbance, and
sample will not be analyzed within 12 hours Ac = cell correction.
of sampling, it must be stored at 5° ±5 °C 10.2 Static Calibration Procedure (Option 1).
EC08NO91.008</MATH>

until analysis. Analysis must occur within 30 Prepare a dilute working sulfite-TCM solu-
days. If the sample is transported or shipped tion by diluting 10 mL of the working sul-
for a period exceeding 12 hours, it is rec- fite-TCM solution (Section 8.2.11) to 100 mL
ommended that thermal coolers using with TCM absorbing reagent. Following the
eutectic ice packs, refrigerated shipping con- table below, accurately pipet the indicated
wwoods2 on DSKDVH8Z91PROD with CFR

tainers, etc., be used for periods up to 48 volumes of the sulfite-TCM solutions into a
EC08NO91.007</MATH>

hours. (17) Measure the temperature of the series of 25-mL volumetric flasks. Add TCM
absorber solution when the shipment is re- absorbing reagent as indicated to bring the
ceived. Invalidate the sample if the tempera- volume in each flask to 10 mL.

24
EC08NO91.006</MATH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00034 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Environmental Protection Agency Pt. 50, App. A

Volume timer that has been set for 30 minutes. Bring


Volume Total μg
of sulfite- all flasks to volume with recently boiled and
Sulfite-TCM solution of TCM, SO2
TCM so- cooled distilled water and mix thoroughly.
mL (approx.*
lution
The color must be developed (during the 30-
Working ......................... 4.0 6.0 28.8 minute period) in a temperature environ-
Working ......................... 3.0 7.0 21.6 ment in the range of 20° to 30 °C, which is
Working ......................... 2.0 8.0 14.4 controlled to ±1 °C. For increased precision,
Dilute working ................ 10.0 0.0 7.2 a constant temperature bath is rec-
Dilute working ................ 5.0 5.0 3.6 ommended during the color development
0.0 10.0 0.0
step. After 30 minutes, determine the cor-
*Based on working sulfite-TCM solution concentration of 7.2 rected absorbance of each standard at 548 nm
μg SO2/mL; the actual total μg SO2 must be calculated using against a distilled water reference (Section
equation 11 below.
10.1). Denote this absorbance as (A). Distilled
To each volumetric flask, add 1 mL 0.6% water is used in the reference cell rather
sulfamic acid (Section 8.2.1), accurately than the reagant blank because of the tem-
pipet 2 mL 0.2% formaldehyde solution (Sec- perature sensitivity of the reagent blank.
tion 8.2.2), then add 5 mL pararosaniline so- Calculate the total micrograms SO2 in each
lution (Section 8.2.13). Start a laboratory solution:

μg SO 2 = VTCM / SO 2 × C TCM / SO 2 × D (11)

where: a low flow of dry carrier gas to a mixing


VTCM/SO2 = volume of sulfite-TCM solution chamber where it is diluted with SO2-free air
used, mL; to the desired concentration and supplied to
CTCM/SO2 = concentration of sulfur dioxide in a vented manifold. A typical system is shown
the working sulfite-TCM, μg SO2/mL (from schematically in Figure 4 and this system
equation 4); and and other similar systems have been de-
D = dilution factor (D = 1 for the working scribed in detail by O’Keeffe and Ortman; (19)
sulfite-TCM solution; D = 0.1 for the di- Scaringelli, Frey, and Saltzman, (20) and
luted working sulfite-TCM solution). Scaringelli, O’Keeffe, Rosenberg, and Bell.
A calibration equation is determined using (21) Permeation devices may be prepared or
the method of linear least squares (Section purchased and in both cases must be trace-
12.1). The total micrograms SO2 contained in able either to a National Bureau of Stand-
each solution is the x variable, and the cor- ards (NBS) Standard Reference Material
rected absorbance (eq. 10) associated with (SRM 1625, SRM 1626, SRM 1627) or to an
each solution is the y variable. For the cali- NBS/EPA-approved commercially available
bration to be valid, the slope must be in the Certified Reference Material (CRM). CRM’s
range of 0.030 ±0.002 absorbance unit/μg SO2, are described in Reference 22, and a list of
the intercept as determined by the least CRM sources is available from the address
squares method must be equal to or less than shown for Reference 22. A recommended pro-
0.170 absorbance unit when the color is devel- tocol for certifying a permeation device to
oped at 22 °C (add 0.015 to this 0.170 specifica- an NBS SRM or CRM is given in Section 2.0.7
tion for each °C above 22 °C) and the correla- of Reference 2. Device permeation rates of 0.2
tion coefficient must be greater than 0.998. If
to 0.4 μg/min, inert gas flows of about 50 mL/
these criteria are not met, it may be the re-
min, and dilution air flow rates from 1.1 to 15
sult of an impure dye and/or an improperly
L/min conveniently yield standard
standardized sulfite-TCM solution. A calibra-
atmospheres in the range of 25 to 600 μg SO2/
tion factor (Bs) is determined by calculating
the reciprocal of the slope and is subse- m3 (0.010 to 0.230 ppm).
quently used for calculating the sample con- 10.3.1 Calibration Option 2A (30-minute and
centration (Section 12.3). 1-hour samples): Generate a series of six
10.3 Dynamic Calibration Procedures (Option standard atmospheres of SO2 (e.g., 0, 50, 100,
2). Atmospheres containing accurately 200, 350, 500, 750 μg/m3) by adjusting the dilu-
known concentrations of sulfur dioxide are tion flow rates appropriately. The concentra-
prepared using permeation devices. In the tion of SO2 in each atmosphere is calculated
systems for generating these atmospheres, as follows:
the permeation device emits gaseous SO2 at
3
a known, low, constant rate, provided the Pr × 10
Ca =
wwoods2 on DSKDVH8Z91PROD with CFR

temperature of the device is held constant (12 )


ER31AU93.014</MATH>

(±0.1 °C) and the device has been accurately Qd + Qp


calibrated at the temperature of use. The
SO2 permeating from the device is carried by where:

25
EC08NO91.011</MATH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00035 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Pt. 50, App. A 40 CFR Ch. I (7–1–10 Edition)
Ca = concentration of SO2 at standard condi- Qd = flow rate of dilution air, std L/min; and
tions, μg/m3; Qp = flow rate of carrier gas across perme-
Pr = permeation rate, μg/min; ation device, std L/min.
wwoods2 on DSKDVH8Z91PROD with CFR

26
50-712.eps</GPH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00036 Fmt 8010 Sfmt 8006 Y:\SGML\220144.XXX 220144
Environmental Protection Agency Pt. 50, App. A
Be sure that the total flow rate of the
standard exceeds the flow demand of the Vb × C s
t= (14 )
sample train, with the excess flow vented at −3
atmospheric pressure. Sample each atmos- C a × Q s × 10
phere using similar apparatus as shown in where:
Figure 1 and under the same conditions as t = sampling time, min;
field sampling (i.e., use same absorbing rea- Vb = volume of absorbing solution used for
gent volume and sample same volume of air sampling (50 mL);
at an equivalent flow rate). Due to the Cs = desired concentration of SO2 in the ab-
length of the sampling periods required, this sorbing solution, μg/mL;
method is not recommended for 24-hour sam- Ca = concentration of the standard atmos-
pling. At the completion of sampling, quan- phere calculated according to equation 12,
titatively transfer the contents of each im- μg/m3; and
pinger to one of a series of 25-mL volumetric Qs = sampling flow rate, std L/min.
flasks (if 10 mL of absorbing solution was At the completion of sampling, bring the
used) using small amounts of distilled water absorber solutions to original volume with
for rinse (<5mL). If >10 mL of absorbing solu- distilled water. Pipet a 10-mL portion from
tion was used, bring the absorber solution in each absorber into one of a series of 25-mL
each impinger to orginal volume with dis- volumetric flasks. If the color development
tilled H2 O and pipet 10-mL portions from steps are not to be started within 12 hours of
each impinger into a series of 25-mL volu- sampling, store the solutions at 5° ±5 °C. Add
metric flasks. If the color development steps the remaining reagents for color develop-
are not to be started within 12 hours of sam- ment in the same manner as in Section 10.2
pling, store the solutions at 5° ±5 °C. Cal- for static solutions. Calculate the total μg
culate the total micrograms SO2 in each so- SO2 in each standard as follows:
lution as follows: −3
C a × Q s × t × Va × 10
C a × Q s × t × Va × 10
−3 μgSO 2 = (15)
μgSO 2 = (13) Vb
Vb
where:
where: Va = volume of absorbing solution used for
Ca = concentration of SO2 in the standard at- color development (10 mL).
mosphere, μg/m3; All other parameters are defined in equation
Os = sampling flow rate, std L/min; 14.
t=sampling time, min; Calculate a calibration equation and a
Va = volume of absorbing solution used for calibration factor (Bt) according to Section
color development (10 mL); and 10.2 adhering to all the specified criteria.
Vb = volume of absorbing solution used for 11.0 Sample Preparation and Analysis.
sampling, mL. 11.1 Sample Preparation. Remove the sam-
ples from the shipping container. If the ship-
Add the remaining reagents for color de- ment period exceeded 12 hours from the com-
velopment in the same manner as in Section pletion of sampling, verify that the tempera-
10.2 for static solutions. Calculate a calibra- ture is below 10 °C. Also, compare the solu-
tion equation and a calibration factor (Bg) tion level to the temporary level mark on
according to Section 10.2, adhering to all the the absorber. If either the temperature is
specified criteria. above 10 °C or there was significant loss
10.3.2 Calibration Option 2B (24-hour sam- (more than 10 mL) of the sample during ship-
ples): Generate a standard atmosphere con- ping, make an appropriate notation in the
taining approximately 1,050 μg SO2/m3 and record and invalidate the sample. Prepare
calculate the exact concentration according the samples for analysis as follows:
to equation 12. Set up a series of six absorb- 1. For 30-minute or 1-hour samples: Quan-
ers according to Figure 2 and connect to a titatively transfer the entire 10 mL amount
common manifold for sampling the standard of absorbing solution to a 25-mL volumetric
atmosphere. Be sure that the total flow rate flask and rinse with a small amount (<5 mL)
of distilled water.
ER31AU93.017</MATH>

of the standard exceeds the flow demand at


the sample manifold, with the excess flow 2. For 24-hour samples: If the volume of the
sample is less than the original 50-mL vol-
vented at atmospheric pressure. The absorb-
ume (permanent mark on the absorber), ad-
ers are then allowed to sample the atmos-
just the volume back to the original volume
phere for varying time periods to yield solu-
with distilled water to compensate for water
tions containing 0, 0.2, 0.6, 1.0, 1.4, 1.8, and 2.2
wwoods2 on DSKDVH8Z91PROD with CFR

lost to evaporation during sampling. If the


ER31AU93.016</MATH>

μg SO2/mL solution. The sampling times re- final volume is greater than the original vol-
quired to attain these solution concentra- ume, the volume must be measured using a
tions are calculated as follows: graduated cylinder. To analyze, pipet 10 mL

27
ER31AU93.015</MATH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00037 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Pt. 50, App. A 40 CFR Ch. I (7–1–10 Edition)
of the solution into a 25-mL volumetric is used to calculate a calibration equation in
flask. the form of:
11.2 Sample Analysis. For each set of deter-
minations, prepare a reagent blank by add- y = mx + b (16 )
ing 10 mL TCM absorbing solution to a 25-
mL volumetric flask, and two control stand- where:
ards containing approximately 5 and 15 μg y = corrected absorbance,
SO2, respectively. The control standards are m = slope, absorbance unit/μg SO2,
prepared according to Section 10.2 or 10.3. x = micrograms of SO2,
The analysis is carried out as follows: b = y intercept (absorbance units).
1. Allow the sample to stand 20 minutes The slope (m), intercept (b), and correla-
after the completion of sampling to allow tion coefficient (r) are calculated as follows:
any ozone to decompose (if applicable).
2. To each 25-mL volumetric flask con- n ∑ xy − ( ∑ x)( ∑ y)
taining reagent blank, sample, or control m= (17)
standard, add 1 mL of 0.6% sulfamic acid n ∑ x 2 − ( ∑ x )2
(Section 8.2.1) and allow to react for 10 min.
3. Accurately pipet 2 mL of 0.2% formalde- ∑y − m∑x
b= (18 )
hyde solution (Section 8.2.2) and then 5 mL n
of pararosaniline solution (Section 8.2.13)
into each flask. Start a laboratory timer set
m ( ∑ xy − ∑ x ∑ y / n )
at 30 minutes. r= (19 )
4. Bring each flask to volume with recently 2 2
∑ y − (∑ y) / n
boiled and cooled distilled water and mix
thoroughly. where n is the number of calibration points.
5. During the 30 minutes, the solutions A data form (Figure 5) is supplied for eas-
must be in a temperature controlled environ- ily organizing calibration data when the
ment in the range of 20° to 30 °C maintained slope, intercept, and correlation coefficient
to ±1 °C. This temperature must also be with- are calculated by hand.
in 1 °C of that used during calibration. 12.2 Total Sample Volume. Determine the
6. After 30 minutes and before 60 minutes, sampling volume at standard conditions as
determine the corrected absorbances (equa- follows:
tion 10) of each solution at 548 nm using 1-cm
optical path length cells against a distilled Qi + Qf
Vstd = ×t ( 20 )
water reference (Section 10.1). (Distilled water
is used as a reference instead of the reagent 2
blank because of the sensitivity of the reagent where:
blank to temperature.) Vstd = sampling volume in std L,
7. Do not allow the colored solution to Qi = standard flow rate determined at the

ER31AU93.022</MATH>
stand in the cells because a film may be de- initiation of sampling in std L/min,
posited. Clean the cells with isopropyl alco- Qf = standard flow rate determined at the
hol after use. completion of sampling is std L/min, and
8. The reagent blank must be within 0.03 t = total sampling time, min.
absorbance units of the intercept of the cali-
bration equation determined in Section 10. 12.3 Sulfur Dioxide Concentration. Calculate
and report the concentration of each sample

ER31AU93.021</MATH>
11.3 Absorbance range. If the absorbance of
the sample solution ranges between 1.0 and as follows:
2.0, the sample can be diluted 1:1 with a por- 3
tion of the reagent blank and the absorbance 3 ( A − A o )( B x )(10 ) Vb
redetermined within 5 minutes. Solutions μg SO 2 /m = × ( 21)
with higher absorbances can be diluted up to Vstd Va
sixfold with the reagent blank in order to ob-
ER31AU93.020</MATH>
tain scale readings of less than 1.0 absorb- where:
ance unit. However, it is recommended that A = corrected absorbance of the sample solu-
a smaller portion (<10 mL) of the original tion, from equation (10);
sample be reanalyzed (if possible) if the sam- Ao = corrected absorbance of the reagent
ple requires a dilution greater than 1:1. blank, using equation (10);
11.4 Reagent disposal. All reagents con- BX = calibration factor equal to Bs, Bg, or Bt
ER31AU93.019</MATH>

taining mercury compounds must be stored depending on the calibration procedure


and disposed of using one of the procedures used, the reciprocal of the slope of the cali-
contained in Section 13. Until disposal, the bration equation;
discarded solutions can be stored in closed Va = volume of absorber solution analyzed,
glass containers and should be left in a fume mL;
wwoods2 on DSKDVH8Z91PROD with CFR

hood. Vb = total volume of solution in absorber (see


ER31AU93.018</MATH>

12.0 Calculations. 11.1–2), mL; and


12.1 Calibration Slope, Intercept, and Correla- Vstd = standard air volume sampled, std L
tion Coefficient. The method of least squares (from Section 12.2).

28
EC08NO91.012</MATH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00038 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Environmental Protection Agency Pt. 50, App. A

DATA FORM 5. After 24 hours, allow the solution to


[For hand calculations] stand without stirring to allow the mercury
amalgam (solid black material) to settle to
Calibra- the bottom of the waste receptacle.
Micro- Absor-
tion point grams So 6. Upon settling, decant and discard the su-
2 bance units
no.
pernatant liquid.
(x) (y) x2 xy y2 7. Quantitatively transfer the solid mate-
1 ........... .................. ................... .......... .......... ........ rial to a container and allow to dry.
2 ........... .................. ................... .......... .......... ........ 8. The solid material can be sent to a mer-
3 ........... .................. ................... .......... .......... ........ cury reclaiming plant. It must not be dis-
4 ........... .................. ................... .......... .......... ........ carded.
5 ........... .................. ................... .......... .......... ........ 13.3 Method Using Aluminum Foil Strips.
6 ........... .................. ................... .......... .......... ........ 1. Place the waste solution in an uncapped
vessel in a hood.
S x=lll S y=lll S x =lll Sxylll 2 2. For each liter of waste solution, add ap-
Sy2lll proximately 10 g of aluminum foil strips. If
n=lll (number of pairs of coordinates.) all the aluminum is consumed and no gas is
llllllllllllllllllllllll evolved, add an additional 10 g of foil. Repeat
until the foil is no longer consumed and
FIGURE 5. Data form for hand calculations.
allow the gas to evolve for 24 hours.
12.4 Control Standards. Calculate the ana- 3. Decant the supernatant liquid and dis-
lyzed micrograms of SO2 in each control card.
standard as follows: 4. Transfer the elemental mercury that has
settled to the bottom of the vessel to a stor-
(
C q = A − A o × Bx ) (22) age container.
5. The mercury can be sent to a mercury
where: reclaiming plant. It must not be discarded.
Cq = analyzed μg SO2 in each control stand- 14.0 References for SO2 Method.
ard, 1. Quality Assurance Handbook for Air Pol-
A = corrected absorbance of the control lution Measurement Systems, Volume I,
standard, and Principles. EPA–600/9–76–005, U.S. Environ-
Ao = corrected absorbance of the reagent mental Protection Agency, Research Tri-
blank. angle Park, NC 27711, 1976.
2. Quality Assurance Handbook for Air Pol-
The difference between the true and ana-
lution Measurement Systems, Volume II,
lyzed values of the control standards must
Ambient Air Specific Methods. EPA–600/4–77–
not be greater than 1 μg. If the difference is
027a, U.S. Environmental Protection Agency,
greater than 1 μg, the source of the discrep-
Research Triangle Park, NC 27711, 1977.
ancy must be identified and corrected.
3. Dasqupta, P. K., and K. B. DeCesare. Sta-
12.5 Conversion of μg/m3 to ppm (v/v). If de-
bility of Sulfur Dioxide in Formaldehyde and
sired, the concentration of sulfur dioxide at
Its Anomalous Behavior in
reference conditions can be converted to ppm
Tetrachloromercurate (II). Submitted for
SO2 (v/v) as follows:
publication in Atmospheric Environment, 1982.
μg SO 2 4. West, P. W., and G. C. Gaeke. Fixation of
−4
ppm SO 2 = × 3.82 × 10 ( 23) Sulfur Dioxide as Disulfitomercurate (II) and
3 Subsequent Colorimetric Estimation. Anal.
m
Chem., 28:1816, 1956.
13.0 The TCM absorbing solution and any 5. Ephraim, F. Inorganic Chemistry. P. C.
reagents containing mercury compounds L. Thorne and E. R. Roberts, Eds., 5th Edi-
must be treated and disposed of by one of the tion, Interscience, 1948, p. 562.
methods discussed below. Both methods re- 6. Lyles, G. R., F. B. Dowling, and V. J.
move greater than 99.99 percent of the mer- Blanchard. Quantitative Determination of
cury. Formaldehyde in the Parts Per Hundred Mil-
13.1 Disposal of Mercury-Containing Solu- lion Concentration Level. J. Air. Poll. Cont.
tions. Assoc., Vol. 15(106), 1965.
13.2 Method for Forming an Amalgam. 7. McKee, H. C., R. E. Childers, and O.
1. Place the waste solution in an uncapped Saenz, Jr. Collaborative Study of Reference
vessel in a hood. Method for Determination of Sulfur Dioxide
2. For each liter of waste solution, add ap- in the Atmosphere (Pararosaniline Method).
proximately 10 g of sodium carbonate until EPA-APTD-0903, U.S. Environmental Protec-
neutralization has occurred (NaOH may have tion Agency, Research Triangle Park, NC
to be used). 27711, September 1971.
3. Following neutralization, add 10 g of 8. Urone, P., J. B. Evans, and C. M. Noyes.
wwoods2 on DSKDVH8Z91PROD with CFR

granular zinc or magnesium. Tracer Techniques in Sulfur—Air Pollution


ER31AU93.023</MATH>

4. Stir the solution in a hood for 24 hours. Studies Apparatus and Studies of Sulfur Di-
Caution must be exercised as hydrogen gas is oxide Colorimetric and Conductometric
evolved by this treatment process. Methods. Anal. Chem., 37: 1104, 1965.

29
EC08NO91.070</MATH>

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00039 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144
Pt. 50, App. A–1 40 CFR Ch. I (7–1–10 Edition)
9. Bostrom, C. E. The Absorption of Sulfur (MD–77), Research Triangle Park, NC 27711,
Dioxide at Low Concentrations (pphm) Stud- January 1981.
ied by an Isotopic Tracer Method. Intern. J.
[47 FR 54899, Dec. 6, 1982; 48 FR 17355, Apr. 22,
Air Water Poll., 9:333, 1965.
1983]
10. Scaringelli, F. P., B. E. Saltzman, and
S. A. Frey. Spectrophotometric Determina- EFFECTIVE DATE NOTE: At 75 FR 35595, June
tion of Atmospheric Sulfur Dioxide. Anal. 22, 2010, appendix A to part 50 was redesig-
Chem., 39: 1709, 1967. nated as appendix A–2 to part 50, effective
11. Pate, J. B., B. E. Ammons, G. A. Swan- Aug. 23, 2010.
son, and J. P. Lodge, Jr. Nitrite Interference
in Spectrophotometric Determination of At- APPENDIX A–1 TO PART 50—REFERENCE
mospheric Sulfur Dioxide. Anal. Chem., MEASUREMENT PRINCIPLE AND CALI-
37:942, 1965. BRATION PROCEDURE FOR THE MEAS-
12. Zurlo, N., and A. M. Griffini. Measure- UREMENT OF SULFUR DIOXIDE IN THE
ment of the Sulfur Dioxide Content of the ATMOSPHERE (ULTRAVIOLET FLUO-
Air in the Presence of Oxides of Nitrogen and RESCENCE METHOD)
Heavy Metals. Medicina Lavoro, 53:330, 1962.
13. Rehme, K. A., and F. P. Scaringelli. Ef- 1.0 APPLICABILITY
fect of Ammonia on the Spectrophotometric
Determination of Atmospheric Concentra- 1.1 This ultraviolet fluorescence (UVF)
tions of Sulfur Dioxide. Anal. Chem., 47:2474, method provides a measurement of the con-
1975. centration of sulfur dioxide (SO2) in ambient
air for determining compliance with the na-
14. McCoy, R. A., D. E. Camann, and H. C.
tional primary and secondary ambient air
McKee. Collaborative Study of Reference
quality standards for sulfur oxides (sulfur di-
Method for Determination of Sulfur Dioxide
oxide) as specified in § 50.4, § 50.5, and § 50.17
in the Atmosphere (Pararosaniline Method)
of this chapter. The method is applicable to
(24-Hour Sampling). EPA–650/4–74–027, U.S.
the measurement of ambient SO2 concentra-
Environmental Protection Agency, Research
tions using continuous (real-time) sampling.
Triangle Park, NC 27711, December 1973.
Additional quality assurance procedures and
15. Fuerst, R. G. Improved Temperature guidance are provided in part 58, Appendix A,
Stability of Sulfur Dioxide Samples Col- of this chapter and in Reference 3.
lected by the Federal Reference Method.
EPA–600/4–78–018, U.S. Environmental Pro- 2.0 PRINCIPLE
tection Agency, Research Triangle Park, NC
27711, April 1978. 2.1 This reference method is based on
16. Scaringelli, F. P., L. Elfers, D. Norris, automated measurement of the intensity of
and S. Hochheiser. Enhanced Stability of the characteristic fluorescence released by
Sulfur Dioxide in Solution. Anal. Chem., SO2 in an ambient air sample contained in a
42:1818, 1970. measurement cell of an analyzer when the
air sample is irradiated by ultraviolet (UV)
17. Martin, B. E. Sulfur Dioxide Bubbler
light passed through the cell. The fluores-
Temperature Study. EPA–600/4–77–040, U.S.
cent light released by the SO2 is also in the
Environmental Protection Agency, Research
ultraviolet region, but at longer wavelengths
Triangle Park, NC 27711, August 1977.
than the excitation light. Typically, opti-
18. American Society for Testing and Mate- mum instrumental measurement of SO2 con-
rials. ASTM Standards, Water; Atmospheric centrations is obtained with an excitation
Analysis. Part 23. Philadelphia, PA, October wavelength in a band between approximately
1968, p. 226. 190 to 230 nm, and measurement of the SO2
19. O’Keeffe, A. E., and G. C. Ortman. Pri- fluorescence in a broad band around 320 nm,
mary Standards for Trace Gas Analysis. but these wavelengths are not necessarily
Anal. Chem., 38:760, 1966. constraints of this reference method. Gen-
20. Scaringelli, F. P., S. A. Frey, and B. E. erally, the measurement system (analyzer)
Saltzman. Evaluation of Teflon Permeation also requires means to reduce the effects of
Tubes for Use with Sulfur Dioxide. Amer. aromatic hydrocarbon species, and possibly
Ind. Hygiene Assoc. J., 28:260, 1967. other compounds, in the air sample to con-
21. Scaringelli, F. P., A. E. O’Keeffe, E. trol measurement interferences from these
Rosenberg, and J. P. Bell, Preparation of compounds, which may be present in the am-
Known Concentrations of Gases and Vapors bient air. References 1 and 2 describe UVF
With Permeation Devices Calibrated Gravi- method.
metrically. Anal. Chem., 42:871, 1970. 2.2 The measurement system is calibrated
22. A Procedure for Establishing by referencing the instrumental fluorescence
Traceability of Gas Mixtures to Certain Na- measurements to SO2 standard concentra-
wwoods2 on DSKDVH8Z91PROD with CFR

tional Bureau of Standards Standard Ref- tions traceable to a National Institute of


erence Materials. EPA–600/7–81–010, U.S. En- Standards and Technology (NIST) primary
vironmental Protection Agency, Environ- standard for SO2 (see Calibration Procedure
mental Monitoring Systems Laboratory below).

30

VerDate Mar<15>2010 10:40 Aug 04, 2010 Jkt 220144 PO 00000 Frm 00040 Fmt 8010 Sfmt 8002 Y:\SGML\220144.XXX 220144

You might also like