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Federal Register / Vol. 65, No.

201 / Tuesday, October 17, 2000 / Rules and Regulations 61893

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61894 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 61895

BILLING CODE 6560–50–P

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61896 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

Method 6A—Determination of Sulfur supplies) and procedures (e.g., sampling and of at least the following additional test
Dioxide, Moisture, and Carbon Dioxide analytical) essential to its performance. Some methods: Method 1, Method 2, Method 3,
From Fossil Fuel Combustion Sources material is incorporated by reference from Method 5, Method 6, and Method 19.
other methods in this part. Therefore, to
Note: This method does not include all of obtain reliable results, persons using this
1.0 Scope and Application
the specifications (e.g., equipment and method should have a thorough knowledge 1.1 Analytes.

Analyte CAS No. Sensitivity

SO2 ................................................................................................................. 7449–09–05 3.4 mg SO2/m3
(2.12 × 10¥7 lb/ft3)
CO2 ................................................................................................................. 124–38–9 N/A
H2O ................................................................................................................. 7732–18–5 N/A

1.2 Applicability. This method is 6.1.1.1 Impingers and Bubblers. Two 7.1.1 Drierite. Anhydrous calcium
applicable for the determination of 30=ml midget impingers with a 1=mm sulfate (CaSO4) desiccant, 8 mesh,
sulfur dioxide (SO2) emissions from restricted tip and two 30=ml midget indicating type is recommended.
fossil fuel combustion sources in terms bubblers with unrestricted tips. Other Note: Do not use silica gel or similar
of concentration (mg/dscm or lb/dscf) types of impingers and bubblers (e.g., desiccant in this application.
and in terms of emission rate (ng/J or lb/ Mae West for SO2 collection and rigid
106 Btu) and for the determination of cylinders containing Drierite for 7.1.2 CO2 Absorbing Material.
carbon dioxide (CO2) concentration moisture absorbers), may be used with Ascarite II. Sodium hydroxide-coated
(percent). Moisture content (percent), if proper attention to reagent volumes and silica, 8- to 20-mesh.
desired, may also be determined by this levels, subject to the approval of the 7.2 Sample Recovery and Analysis.
method. Administrator. Same as Method 6, Sections 7.2 and 7.3,
1.3 Data Quality Objectives. 6.1.1.2 CO2 Absorber. A sealable respectively.
Adherence to the requirements of this rigid cylinder or bottle with an inside 8.0 Sample Collection, Preservation,
method will enhance the quality of the diameter between 30 and 90 mm , a Transport, and Storage
data obtained from air pollutant length between 125 and 250 mm, and
sampling methods. appropriate connections at both ends. 8.1 Preparation of Sampling Train.
The filter may be a separate heated unit 8.1.1 Measure 15 ml of 80 percent
2.0 Summary of Method isopropanol into the first midget bubbler
or may be within the heated portion of
2.1 A gas sample is extracted from a the probe. If the filter is within the and 15 ml of 3 percent hydrogen
sampling point in the stack. The SO2 sampling probe, the filter should not be peroxide into each of the two midget
and the sulfur trioxide, including those within 15 cm of the probe inlet or any impingers (the second and third vessels
fractions in any sulfur acid mist, are unheated section of the probe, such as in the train) as described in Method 6,
separated. The SO2 fraction is measured the connection to the first bubbler. The Section 8.1. Insert the glass wool into
by the barium-thorin titration method. probe and filter should be heated to at the top of the isopropanol bubbler as
Moisture and CO2 fractions are collected least 20 °C (68 °F) above the source shown in Figure 6A–1. Place about 25
in the same sampling train, and are temperature, but not greater than 120 °C g of Drierite into the second midget
determined gravimetrically. (248 °F). The filter temperature (i.e., the bubbler (the fourth vessel in the train).
sample gas temperature) should be Clean the outside of the bubblers and
3.0 Definitions. [Reserved] impingers and allow the vessels to reach
monitored to assure the desired
4.0 Interferences temperature is maintained. A heated room temperature. Weigh the four
Teflon connector may be used to vessels simultaneously to the nearest 0.1
Same as Method 6, Section 4.0. g, and record this initial weight (mwi).
connect the filter holder or probe to the
5.0 Safety first impinger. 8.1.2 With one end of the CO2
absorber sealed, place glass wool into
5.1 Disclaimer. This method may Note: For applications downstream of wet the cylinder to a depth of about 1 cm
involve hazardous materials, operations, scrubbers, a heated out-of-stack filter (either
borosilicate glass wool or glass fiber mat) is
(0.5 in.). Place about 150 g of CO2
and equipment. This test method may absorbing material in the cylinder on
necessary.
not address all of the safety problems top of the glass wool, and fill the
associated with its use. It is the 6.2 Sample Recovery. Same as remaining space in the cylinder with
responsibility of the user to establish Method 6, Section 6.2. glass wool. Assemble the cylinder as
appropriate safety and health practices 6.3 Sample Analysis. Same as shown in Figure 6A–2. With the
and determine the applicability of Method 6, Section 6.3, with the addition cylinder in a horizontal position, rotate
regulatory limitations prior to of a balance to measure within 0.05 g. it around the horizontal axis. The CO2
performing this test method. absorbing material should remain in
7.0 Reagents and Standards
5.2 Corrosive reagents. Same as position during the rotation, and no
Method 6, Section 5.2. Note: Unless otherwise indicated, all open spaces or channels should be
reagents must conform to the specifications formed. If necessary, pack more glass
6.0 Equipment and Supplies established by the Committee on Analytical wool into the cylinder to make the CO2
6.1 Sample Collection. Same as Reagents of the American Chemical Society. absorbing material stable. Clean the
Method 6, Section 6.1, with the Where such specifications are not available, outside of the cylinder of loose dirt and
exception of the following: use the best available grade.
moisture and allow the cylinder to reach
6.1.1 Sampling Train. A schematic 7.1 Sample Collection. Same as room temperature. Weigh the cylinder
of the sampling train used in this Method 6, Section 7.1, with the addition to the nearest 0.1 g, and record this
method is shown in Figure 6A–1. of the following: initial weight (mai).

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 61897

8.1.3 Assemble the train as shown in midget impingers and connecting tubes ESO2 = Emission rate of SO2, ng/J (lb/106
Figure 6A–1. Adjust the probe heater to with water, and add the washing to the Btu).
a temperature sufficient to prevent same storage container. FC = Carbon F-factor from Method 19 for
condensation (see Note in Section 6.1). 8.3.3 CO2 Absorber. Allow the CO2 the fuel burned, dscm/J (dscf/106
Place crushed ice and water around the absorber to warm to room temperature Btu).
impingers and bubblers. Mount the CO2 (about 10 minutes), clean the outside of mwi = Initial weight of impingers,
absorber outside the water bath in a loose dirt and moisture, and weigh to bubblers, and moisture absorber, g.
vertical flow position with the sample the nearest 0.1 g in the same manner as
in Section 8.1. Record this final weight mwf = Final weight of impingers,
gas inlet at the bottom. Flexible tubing
(maf). Discard used Ascarite II material. bubblers, and moisture absorber, g.
(e.g., Tygon) may be used to connect the
last SO2 absorbing impinger to the mai = Initial weight of CO2 absorber, g.
9.0 Quality Control maf = Final weight of CO2 absorber, g.
moisture absorber and to connect the
moisture absorber to the CO2 absorber. Same as Method 6, Section 9.0. mSO2 = Mass of SO2 collected, mg.
A second, smaller CO2 absorber 10.0 Calibration and Standardization VCO2(std) = Equivalent volume of CO2
containing Ascarite II may be added in- collected at standard conditions,
line downstream of the primary CO2 Same as Method 6, Section 10.0.
dscm (dscf).
absorber as a breakthrough indicator. 11.0 Analytical Procedure Vw(std) = Equivalent volume of moisture
Ascarite II turns white when CO2 is collected at standard conditions,
11.1 Sample Analysis. The sample
absorbed. scm (scf).
analysis procedure for SO2 is the same
8.2 Sampling Train Leak-Check as that specified in Method 6, Section 12.2 CO2 Volume Collected,
Procedure and Sample Collection. Same 11.0. Corrected to Standard Conditions.
as Method 6, Sections 8.2 and 8.3, 11.2 Quality Assurance (QA) Audit
respectively. Samples. Analysis of QA audit samples VCO ( std ) = K 3 ( m af − m ai ) Eq. 6 A-1
8.3 Sample Recovery. is required only when this method is 2

8.3.1 Moisture Measurement. used for compliance determinations. Where:
Disconnect the isopropanol bubbler, the Obtain an audit sample set as directed K3 = Equivalent volume of gaseous CO2
SO2 impingers, and the moisture in Section 7.3.6 of Method 6. Analyze at standard conditions, 5.467 ×
absorber from the sample train. Allow the audit samples, and report the results 10¥4 dscm/g (1.930 × 10¥2 dscf/g).
about 10 minutes for them to reach as directed in Section 11.3 of Method 6.
room temperature, clean the outside of Acceptance criteria for the audit results 12.3 Moisture Volume Collected,
loose dirt and moisture, and weigh them are the same as those in Method 6. Corrected to Standard Conditions.
simultaneously in the same manner as
in Section 8.1. Record this final weight 12.0 Data Analysis and Calculations Vw(std ) = K 4 ( m wf − m wi ) Eq. 6 A-2
(mwf). Same as Method 6, Section 12.0, with Where:
8.3.2 Peroxide Solution. Discard the the addition of the following:
contents of the isopropanol bubbler and 12.1 Nomenclature. K4 = Equivalent volume of water vapor
pour the contents of the midget Cw = Concentration of moisture, percent. at standard conditions, 1.336 ×
impingers into a leak-free polyethylene CCO2 = Concentration of CO2, dry basis, 10¥3 scm/g (4.717 × 10¥2 scf/g).
bottle for shipping. Rinse the two percent. 12.4 SO2 Concentration.

K 2 N (Vt − Vtb )(Vso ln / Va )
Cso2 = Eq. 6A-3
Vm (std ) + Vco2 (std )
Where:
K2 = 32.03 mg SO2/meq. SO2 (7.061 × 10¥5 lb SO2/meq. SO2)
12.5 CO2 Concentration.

Vco2 (std )
C co2 = Eq. 6A- 4
Vm (std ) + Vco2 (std )
12.6 Moisture Concentration.

Vw (std )
Cw = Eq. 6A-5
Vm (std ) + Vw (std ) + Vco2 (std )

13.0 Method Performance liter sample, this method has a precision 14.0 Pollution Prevention [Reserved]
of ±0.5 percent CO2 for concentrations 15.0 Waste Management. [Reserved]
13.1 Range and Precision. The
between 2.5 and 25 percent CO2 and
minimum detectable limit and the
±1.0 percent moisture for moisture 16.0 Alternative Methods
upper limit for the measurement of SO2
concentrations greater than 5 percent. If the only emission measurement
are the same as for Method 6. For a 20-
desired is in terms of emission rate of
SO2 (ng/J or lb/106 Btu), an abbreviated

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61898 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

procedure may be used. The differences Section 8.1, except do not weigh the 16.4 Sample Recovery. Follow the
between the above procedure and the isopropanol bubbler, the SO2 absorbing procedure in Section 8.3, except do not
abbreviated procedure are described impingers, or the moisture absorber. weigh the isopropanol bubbler, the SO2
below. absorbing impingers, or the moisture
16.3 Sampling Train Leak-Check
16.1 Sampling Train. The sampling absorber.
Procedure and Sample Collection. Leak-
train is the same as that shown in Figure 16.5 Sample Analysis. Analysis of
check and operate the sampling train as
6A–1 and as described in Section 6.1, the peroxide solution and QA audit
described in Section 8.2, except that dry
except that the dry gas meter is not samples is the same as that described in
gas meter readings, barometric pressure,
needed. Sections 11.1 and 11.2, respectively.
and dry gas meter temperatures need
16.2 Preparation of the Sampling 16.6 Calculations.
not be recorded during sampling.
Train. Follow the same procedure as in 16.6.1 SO2 Collected.

m SO2 = K 2 N (Vt − Vtb )(Vsoln / Va ) Eq. 6A-6
Where:
K2 = 32.03 mg SO2/meq. SO2
K2 = 7.061 × 10¥5 lb SO2/meq. SO2
16.6.2 Sulfur Dioxide Emission Rate.

E SO2 = K 5 Fc m so2 / ( m af − m ai ) Eq. 6A-7

Where: 1. Stanley, Jon and P.R. Westlin. An Standard and Engineering Division, Emission
Alternate Method for Stack Gas Moisture Measurement Branch. Research Triangle
K5 = 1.829 × 109 mg/dscm
Determination. Source Evaluation Society Park, NC. December 1979. 14 pp.
K2 = 0.1142 lb/dscf Newsletter. 3(4). November 1978. BILLING CODE 6560–50–P
17.0 References 2. Whittle, Richard N. and P.R. Westlin.
Air Pollution Test Report: Development and
Same as Method 6, Section 17.0, Evaluation of an Intermittent Integrated SO2/
References 1 through 8, with the CO2 Emission Sampling Procedure.
addition of the following: Environmental Protection Agency, Emission

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 61899

18.0 Tables, Diagrams, Flowcharts, and Validation Data

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61900 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

BILLING CODE 6560–50–C

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 61901

Method 6B—Determination of Sulfur supplies) and procedures (e.g., sampling and methods: Method 1, Method 2, Method 3,
Dioxide and Carbon Dioxide Daily analytical) essential to its performance. Some Method 5, Method 6, and Method 6A.
Average Emissions From Fossil Fuel material is incorporated by reference from
Combustion Sources other methods in this part. Therefore, to 1.0 Scope and Application
obtain reliable results, persons using this
Note: This method does not include all of method should have a thorough knowledge 1.1 Analytes.
the specifications (e.g., equipment and of at least the following additional test

Analyte CAS No. Sensitivity

Sulfur dioxide (SO2) .................................................................... 7449–09–05 3.4 mg SO2/m3
(2.12 × 10¥7 lb/ft3)
Carbon dioxide (CO2) ................................................................. 124–38–9 N/A

1.2 Applicability. This method is designed to operate in the ‘‘on’’ position 8.0 Sample Collection, Preservation,
applicable for the determination of SO2 at least 2 minutes continuously and Transport, and Storage
emissions from combustion sources in ‘‘off’’ the remaining period over a 8.1 Preparation of Sampling Train.
terms of concentration (ng/dscm or lb/ repeating cycle. The cycle of operation Same as Method 6A, Section 8.1, with
dscf) and emission rate (ng/J or lb/106 is designated in the applicable the addition of the following:
Btu), and for the determination of CO2 regulation. At a minimum, the sampling 8.1.1 The sampling train is
concentration (percent) on a daily (24 operation should include at least 12, assembled as shown in Figure 6A–1 of
hours) basis. equal, evenly-spaced periods per 24 Method 6A, except that the isopropanol
1.3 Data Quality Objectives. hours. bubbler is not included.
Adherence to the requirements of this 6.3 Stainless steel sampling probes, 8.1.2 Adjust the timer-switch to
method will enhance the quality of the type 316, are not recommended for use operate in the ‘‘on’’ position from 2 to
data obtained from air pollutant with Method 6B because of potential 4 minutes on a 2-hour repeating cycle or
sampling methods. sample contamination due to corrosion. other cycle specified in the applicable
2.0 Summary of Method Glass probes or other types of stainless regulation. Other timer sequences may
steel, e.g., Hasteloy or Carpenter 20, are be used with the restriction that the
2.1 A gas sample is extracted from recommended for long-term use. total sample volume collected is
the sampling point in the stack Note: For applications downstream of wet between 25 and 60 liters (0.9 and 2.1
intermittently over a 24-hour or other scrubbers, a heated out-of-stack filter (either ft 3) for the amounts of sampling
specified time period. The SO2 fraction borosilicate glass wool or glass fiber mat) is reagents prescribed in this method.
is measured by the barium-thorin necessary. Probe and filter heating systems
8.1.3 Add cold water to the tank
titration method. Moisture and CO2 capable of maintaining a sample gas
temperature of between 20 and 120 °C (68 until the impingers and bubblers are
fractions are collected in the same
and 248 °F) at the filter are also required in covered at least two-thirds of their
sampling train, and are determined
these cases. The electric supply for these length. The impingers and bubbler tank
gravimetrically.
heating systems should be continuous and must be covered and protected from
3.0 Definitions. [Reserved] separate from the timed operation of the intense heat and direct sunlight. If
sample pump. freezing conditions exist, the impinger
4.0 Interferences
solution and the water bath must be
Same as Method 6, Section 4.0. 7.0 Reagents and Standards protected.
5.0 Safety Same as Method 6A, Section 7.0, with Note: Sampling may be conducted
the following exceptions: continuously if a low flow-rate sample pump
5.1 Disclaimer. This method may [20 to 40 ml/min (0.04 to 0.08 ft3/hr) for the
involve hazardous materials, operations, 7.1 Isopropanol is not used for
sampling. reagent volumes described in this method] is
and equipment. This test method may used. If sampling is continuous, the timer-
not address all of the safety problems 7.2 The hydrogen peroxide switch is not necessary. In addition, if the
associated with its use. It is the absorbing solution shall be diluted to no sample pump is designed for constant rate
responsibility of the user to establish less than 6 percent by volume, instead sampling, the rate meter may be deleted. The
appropriate safety and health practices of 3 percent as specified in Methods 6 total gas volume collected should be between
and determine the applicability of and 6A. 25 and 60 liters (0.9 and 2.1 ft3) for the
regulatory limitations prior to 7.3 If the Method 6B sampling train amounts of sampling reagents prescribed in
is to be operated in a low sample flow this method.
performing this test method.
5.2 Corrosive Reagents. Same as condition (less than 100 ml/min or 0.21 8.2 Sampling Train Leak-Check
Method 6, Section 5.2. ft3/hr), molecular sieve material may be Procedure. Same as Method 6, Section
substituted for Ascarite II as the CO2 8.2.
6.0 Equipment and Supplies absorbing material. The recommended 8.3 Sample Collection.
Same as Method 6A, Section 6.0, with molecular sieve material is Union 8.3.1 The probe and filter (either in-
the following exceptions and additions: Carbide 1⁄16 inch pellets, 5 A°, or stack, out-of-stack, or both) must be
6.1 The isopropanol bubbler is not equivalent. Molecular sieve material heated to a temperature sufficient to
used. An empty bubbler for the need not be discarded following the prevent water condensation.
collection of liquid droplets, that does sampling run, provided that it is 8.3.2 Record the initial dry gas meter
not allow direct contact between the regenerated as per the manufacturer’s reading. To begin sampling, position the
collected liquid and the gas sample, instruction. Use of molecular sieve tip of the probe at the sampling point,
may be included in the sampling train. material at flow rates higher than 100 connect the probe to the first impinger
6.2 For intermittent operation, ml/min (0.21 ft3/hr) may cause (or filter), and start the timer and the
include an industrial timer-switch erroneous CO2 results. sample pump. Adjust the sample flow to

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61902 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

a constant rate of approximately 1.0 most recent calibration factor for achievable by qualified testers following
liter/min (0.035 cfm) as indicated by the succeeding test runs. the procedures in this method. The
rotameter. Observe the operation of the results of the studies evolve from 145
11.0 Analytical Procedures
timer, and determine that it is operating field tests including comparisons with
as intended (i.e., the timer is in the ‘‘on’’ 11.1 Sample Loss Check and Methods 3 and 6. For measurements of
position for the desired period, and the Analysis. Same as Method 6, Sections emission rates from wet, flue gas
cycle repeats as required). 11.1 and 11.2, respectively. desulfurization units in (ng/J), the
8.3.3 One time between 9 a.m. and 11.2 Quality Assurance (QA) Audit repeatability (intra-laboratory precision)
11 a.m. during the 24-hour sampling Samples. Analysis of QA audit samples is 8.0 percent and the reproducibility
period, record the dry gas meter is required only when this method is (inter-laboratory precision) is 11.1
temperature (Tm) and the barometric used for compliance determinations. percent.
pressure (P(bar)). Obtain an audit sample set as directed
in Section 7.3.6 of Method 6. Analyze 14.0 Pollution Prevention. [Reserved]
8.3.4 At the conclusion of the run,
turn off the timer and the sample pump, the audit samples at least once for every 15.0 Waste Management. [Reserved]
remove the probe from the stack, and 30 days of sample collection, and report 16.0 Alternative Methods
record the final gas meter volume the results as directed in Section 11.3 of
reading. Conduct a leak-check as Method 6. The analyst performing the Same as Method 6A, Section 16.0,
described in Section 8.2. If a leak is sample analyses shall perform the audit except that the timer is needed and is
found, void the test run or use analyses. If more than one analyst operated as outlined in this method.
procedures acceptable to the performs the sample analyses during the 17.0 References
Administrator to adjust the sample 30-day sampling period, each analyst
volume for leakage. Repeat the steps in shall perform the audit analyses and all Same as Method 6A, Section 17.0,
Sections 8.3.1 to 8.3.4 for successive audit results shall be reported. with the addition of the following:
runs. Acceptance criteria for the audit results 1. Butler, Frank E., et. al. The Collaborative
8.4 Sample Recovery. The are the same as those in Method 6. Test of Method 6B: Twenty-Four-Hour
procedures for sample recovery Analysis of SO2 and CO2. JAPCA. Vol. 33,
12.0 Data Analysis and Calculations No. 10. October 1983.
(moisture measurement, peroxide
solution, and CO2 absorber) are the same Same as Method 6A, Section 12.0, 18.0 Tables, Diagrams, Flowcharts,
as those in Method 6A, Section 8.3. except that Pbar and Tm correspond to and Validation Data. [Reserved]
the values recorded in Section 8.3.3 of
9.0 Quality Control this method. The values are as follows: * * * * *
Same as Method 6, Section 9.0., with Pbar = Initial barometric pressure for the Method 7—Determination of Nitrogen
the exception of the isopropanol-check. test period, mm Hg. Oxide Emissions From Stationary
Tm = Absolute meter temperature for the Sources
10.0 Calibration and Standardization
test period, °K.
Same as Method 6, Section 10.0, with Note: This method does not include all of
the addition of the following: 13.0 Method Performance the specifications (e.g., equipment and
supplies) and procedures (e.g., sampling and
10.1 Periodic Calibration Check. 13.1 Range.
analytical) essential to its performance. Some
After 30 days of operation of the test 13.1.1 Sulfur Dioxide. Same as material is incorporated by reference from
train, conduct a calibration check Method 6. other methods in this part. Therefore, to
according to the same procedures as the 13.1.2 Carbon Dioxide. Not obtain reliable results, persons using this
post-test calibration check (Method 6, determined. method should have a thorough knowledge
Section 10.1.2). If the deviation between 13.2 Repeatability and of at least the following additional test
initial and periodic calibration factors Reproducibility. EPA-sponsored methods: Method 1 and Method 5.
exceeds 5 percent, use the smaller of the collaborative studies were undertaken to
two factors in calculations for the determine the magnitude of 1.0 Scope and Application
preceding 30 days of data, but use the repeatability and reproducibility 1.1 Analytes.

Analyte CAS No. Sensitivity

Nitrogen oxides (NOX), as NO2, including:
Nitric oxide (NO) ...................................................................................... 10102–43–9
Nitrogen dioxide (NO2) ............................................................................ 10102–44–0 2–400 mg/dscm

1.2 Applicability. This method is sulfuric acid-hydrogen peroxide 5.0 Safety
applicable for the measurement of absorbing solution, and the nitrogen
5.1 Disclaimer. This method may
nitrogen oxides (NOX) emitted from oxides, except nitrous oxide, are involve hazardous materials, operations,
stationary sources. measured colorimetrically using the and equipment. This test method may
1.3 Data Quality Objectives. phenoldisulfonic acid (PDS) procedure. not address all of the safety problems
Adherence to the requirements of this 3.0 Definitions. [Reserved] associated with its use. It is the
method will enhance the quality of the responsibility of the user to establish
data obtained from air pollutant sample 4.0 Interferences appropriate safety and health practices
methods. and to determine the applicability of
Biased results have been observed
2.0 Summary of Method regulatory limitations prior to
when sampling under conditions of
performing this test method.
high sulfur dioxide concentrations
A grab sample is collected in an 5.2 Corrosive Reagents. The
(above 2000 ppm).
evacuated flask containing a dilute following reagents are hazardous.

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 61903

Personal protective equipment and safe 6.1.5 Vacuum Line. Tubing capable standard KNO3 solution), and 1000-ml
procedures are useful in preventing of withstanding a vacuum of 75 mm (3 (one).
chemical splashes. If contact occurs, in.) Hg absolute pressure, with ‘‘T’’ 6.3.8 Spectrophotometer. To
immediately flush with copious connection and T-bore stopcock. measure at 410 nm.
amounts of water for at least 15 minutes. 6.1.6 Vacuum Gauge. U-tube 6.3.9 Graduated Pipette. 10-ml with
Remove clothing under shower and manometer, 1 meter (39 in.), with 1 mm 0.1-ml divisions.
decontaminate. Treat residual chemical (0.04 in.) divisions, or other gauge 6.3.10 Test Paper for Indicating pH.
burns as thermal burns. capable of measuring pressure to within To cover the pH range of 7 to 14.
5.2.1 Hydrogen Peroxide (H2O2). 2.5 mm (0.10 in.) Hg. 6.3.11 Analytical Balance. To
Irritating to eyes, skin, nose, and lungs. 6.1.7 Pump. Capable of evacuating measure to within 0.1 mg.
5.2.2 Phenoldisulfonic Acid. the collection flask to a pressure equal 7.0 Reagents and Standards
Irritating to eyes and skin. to or less than 75 mm (3 in.) Hg
5.2.3 Sodium Hydroxide (NaOH). Unless otherwise indicated, it is
absolute.
Causes severe damage to eyes and skin. intended that all reagents conform to the
6.1.8 Squeeze Bulb. One-way.
Inhalation causes irritation to nose, 6.1.9 Volumetric Pipette. 25-ml. specifications established by the
throat, and lungs. Reacts exothermically 6.1.10 Stopcock and Ground Joint Committee on Analytical Reagents of
with limited amounts of water. Grease. A high-vacuum, high- the American Chemical Society, where
5.2.4 Sulfuric Acid (H2SO4). Rapidly temperature chlorofluorocarbon grease such specifications are available;
destructive to body tissue. Will cause is required. Halocarbon 25–5S has been otherwise, use the best available grade.
third degree burns. Eye damage may 7.1 Sample Collection. The
found to be effective.
result in blindness. Inhalation may be following reagents are required for
6.1.11 Barometer. Mercury, aneroid,
fatal from spasm of the larynx, usually sampling:
or other barometer capable of measuring 7.1.1 Water. Deionized distilled to
within 30 minutes. May cause lung atmospheric pressure to within 2.5 mm conform to ASTM D 1193–77 or 91 Type
tissue damage with edema. 1 mg/m 3 for (0.1 in.) Hg. See NOTE in Method 5, 3 (incorporated by reference—see
8 hours will cause lung damage or, in Section 6.1.2. § 60.17). The KMnO4 test for oxidizable
higher concentrations, death. Provide 6.2 Sample Recovery. The following organic matter may be omitted when
ventilation to limit inhalation. Reacts items are required for sample recovery: high concentrations of organic matter
violently with metals and organics. 6.2.1 Graduated Cylinder. 50-ml
are not expected to be present.
5.2.5 Phenol. Poisonous and caustic. with 1 ml divisions. 7.1.2 Absorbing Solution. Cautiously
Do not handle with bare hands as it is 6.2.2 Storage Containers. Leak-free add 2.8 ml concentrated H2SO4 to a 1-
absorbed through the skin. polyethylene bottles. liter flask partially filled with water.
6.2.3 Wash Bottle. Polyethylene or
6.0 Equipment and Supplies Mix well, and add 6 ml of 3 percent
glass.
6.1 Sample Collection. A schematic hydrogen peroxide, freshly prepared
6.2.4 Glass Stirring Rod.
of the sampling train used in performing 6.2.5 Test Paper for Indicating pH. from 30 percent hydrogen peroxide
this method is shown in Figure 7–1. To cover the pH range of 7 to 14. solution. Dilute to 1 liter of water and
Other grab sampling systems or 6.3 Analysis. The following items mix well. The absorbing solution should
equipment, capable of measuring are required for analysis: be used within 1 week of its
sample volume to within 2.0 percent 6.3.1 Volumetric Pipettes. Two 1-ml, preparation. Do not expose to extreme
and collecting a sufficient sample two 2-ml, one 3-ml, one 4-ml, two 10- heat or direct sunlight.
ml, and one 25-ml for each sample and 7.2 Sample Recovery. The following
volume to allow analytical
standard. reagents are required for sample
reproducibility to within 5 percent, will
6.3.2 Porcelain Evaporating Dishes. recovery:
be considered acceptable alternatives, 7.2.1 Water. Same as in 7.1.1.
subject to the approval of the 175- to 250-ml capacity with lip for 7.2.2 Sodium Hydroxide, 1 N.
Administrator. The following items are pouring, one for each sample and each Dissolve 40 g NaOH in water, and dilute
required for sample collection: standard. The Coors No. 45006 to 1 liter.
6.1.1 Probe. Borosilicate glass (shallowform, 195-ml) has been found to 7.3 Analysis. The following reagents
tubing, sufficiently heated to prevent be satisfactory. Alternatively, and standards are required for analysis:
water condensation and equipped with polymethyl pentene beakers (Nalge No. 7.3.1 Water. Same as in 7.1.1.
an in-stack or heated out-of-stack filter 1203, 150-ml), or glass beakers (150-ml) 7.3.2 Fuming Sulfuric Acid. 15 to 18
to remove particulate matter (a plug of may be used. When glass beakers are percent by weight free sulfur trioxide.
glass wool is satisfactory for this used, etching of the beakers may cause HANDLE WITH CAUTION.
purpose). Stainless steel or Teflon solid matter to be present in the 7.3.3 Phenol. White solid.
tubing may also be used for the probe. analytical step; the solids should be 7.3.4 Sulfuric Acid. Concentrated,
Heating is not necessary if the probe removed by filtration. 95 percent minimum assay.
remains dry during the purging period. 6.3.3 Steam Bath. Low-temperature 7.3.5 Potassium Nitrate (KNO3).
6.1.2 Collection Flask. Two-liter ovens or thermostatically controlled hot Dried at 105 to 110 °C (221 to 230 °F)
borosilicate, round bottom flask, with plates kept below 70 °C (160 °F) are for a minimum of 2 hours just prior to
short neck and 24/40 standard taper acceptable alternatives. preparation of standard solution.
opening, protected against implosion or 6.3.4 Dropping Pipette or Dropper. 7.3.6 Standard KNO3 Solution.
breakage. Three required. Dissolve exactly 2.198 g of dried KNO3
6.1.3 Flask Valve. T-bore stopcock 6.3.5 Polyethylene Policeman. One in water, and dilute to 1 liter with water
connected to a 24/40 standard taper for each sample and each standard. in a 1000-ml volumetric flask.
joint. 6.3.6 Graduated Cylinder. 100-ml 7.3.7 Working Standard KNO3
6.1.4 Temperature Gauge. Dial-type with 1-ml divisions. Solution. Dilute 10 ml of the standard
thermometer, or other temperature 6.3.7 Volumetric Flasks. 50-ml (one solution to 100 ml with water. One ml
gauge, capable of measuring 1 °C (2 °F) for each sample and each standard), of the working standard solution is
intervals from ¥5 to 50 °C (23 to 122 100-ml (one for each sample and each equivalent to 100 µg nitrogen dioxide
°F). standard, and one for the working (NO2).

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61904 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

7.3.8 Phenoldisulfonic Acid (3 in.) Hg absolute pressure, or less. conversion of NO to NO2 (e.g., an
Solution. Dissolve 25 g of pure white Evacuation to a pressure approaching applicable subpart of the standards may
phenol solid in 150 ml concentrated the vapor pressure of water at the require taking a sample of a calibration
sulfuric acid on a steam bath. Cool, add existing temperature is desirable. Turn gas mixture of NO in N2), then introduce
75 ml fuming sulfuric acid (15 to 18 the pump valve to its ‘‘vent’’ position, oxygen into the flask to permit this
percent by weight free sulfur trioxide— and turn off the pump. Check for conversion. Oxygen may be introduced
HANDLE WITH CAUTION), and heat at leakage by observing the manometer for into the flask by one of three methods:
100 °C (212 °F) for 2 hours. Store in a any pressure fluctuation. (Any variation (1) Before evacuating the sampling flask,
dark, stoppered bottle. greater than 10 mm (0.4 in.) Hg over a flush with pure cylinder oxygen, then
7.3.9 Concentrated Ammonium period of 1 minute is not acceptable, evacuate flask to 75 mm (3 in.) Hg
Hydroxide. and the flask is not to be used until the absolute pressure or less; or (2) inject
7.3.10 Quality Assurance Audit leakage problem is corrected. Pressure oxygen into the flask after sampling; or
Samples. When making compliance in the flask is not to exceed 75 mm (3 (3) terminate sampling with a minimum
determinations, and upon availability, in.) Hg absolute at the time sampling is of 50 mm (2 in.) Hg vacuum remaining
audit samples may be obtained from the commenced.) Record the volume of the in the flask, record this final pressure,
appropriate EPA Regional Office or from flask and valve (Vf), the flask and then vent the flask to the
the responsible enforcement authority. temperature (Ti), and the barometric atmosphere until the flask pressure is
Note: The responsible enforcement pressure. Turn the flask valve almost equal to atmospheric pressure.
authority should be notified at least 30 days counterclockwise to its ‘‘purge’’
prior to the test date to allow sufficient time position, and do the same with the 8.2 Sample Recovery. Let the flask
for sample delivery. pump valve. Purge the probe and the sit for a minimum of 16 hours, and then
vacuum tube using the squeeze bulb. If shake the contents for 2 minutes.
8.0 Sample Collection, Preservation, condensation occurs in the probe and 8.2.1 Connect the flask to a mercury
Storage and Transport the flask valve area, heat the probe, and filled U-tube manometer. Open the
8.1 Sample Collection. purge until the condensation valve from the flask to the manometer,
8.1.1 Flask Volume. The volume of disappears. Next, turn the pump valve and record the flask temperature (Tf),
the collection flask and flask valve to its ‘‘vent’’ position. Turn the flask the barometric pressure, and the
combination must be known prior to valve clockwise to its ‘‘evacuate’’ difference between the mercury levels
sampling. Assemble the flask and flask position, and record the difference in in the manometer. The absolute internal
valve, and fill with water to the the mercury levels in the manometer. pressure in the flask (Pf) is the
stopcock. Measure the volume of water The absolute internal pressure in the barometric pressure less the manometer
to ±10 ml. Record this volume on the flask (Pi) is equal to the barometric reading. Transfer the contents of the
flask. pressure less the manometer reading. flask to a leak-free polyethylene bottle.
8.1.2 Pipette 25 ml of absorbing Immediately turn the flask valve to the Rinse the flask twice with 5 ml portions
solution into a sample flask, retaining a ‘‘sample’’ position, and permit the gas to of water, and add the rinse water to the
sufficient quantity for use in preparing enter the flask until pressures in the bottle. Adjust the pH to between 9 and
the calibration standards. Insert the flask and sample line (i.e., duct, stack) 12 by adding 1 N NaOH, dropwise
flask valve stopper into the flask with are equal. This will usually require (about 25 to 35 drops). Check the pH by
the valve in the ‘‘purge’’ position. about 15 seconds; a longer period dipping a stirring rod into the solution
Assemble the sampling train as shown indicates a plug in the probe, which and then touching the rod to the pH test
in Figure 7–1, and place the probe at the must be corrected before sampling is paper. Remove as little material as
sampling point. Make sure that all continued. After collecting the sample, possible during this step. Mark the
fittings are tight and leak-free, and that turn the flask valve to its ‘‘purge’’ height of the liquid level so that the
all ground glass joints have been greased position, and disconnect the flask from container can be checked for leakage
properly with a high-vacuum, high the sampling train. after transport. Label the container to
temperature chlorofluorocarbon-based 8.1.3 Shake the flask for at least 5 identify clearly its contents. Seal the
stopcock grease. Turn the flask valve minutes. container for shipping.
and the pump valve to their ‘‘evacuate’’ 8.1.4 If the gas being sampled
positions. Evacuate the flask to 75 mm contains insufficient oxygen for the 9.0 Quality Control

Section Quality control measure Effect

10.1 ..................... Spectrophotometer calibration ................................... Ensure linearity of spectrophotometer response to standards.
11.4 ..................... Audit sample analysis ................................................ Evaluate analytical technique, preparation of standards.

10.0 Calibration and Standardization Calibration materials are available recalibrate the spectrophotometer. Once
commercially and from the National the wavelength scale of the
10.1 Spectrophotometer. spectrophotometer is in proper
Institute of Standards and Technology.
10.1.1 Optimum Wavelength Specific details on the use of such calibration, use 410 nm as the optimum
Determination. wavelength for the measurement of the
materials should be supplied by the
10.1.1.1 Calibrate the wavelength vendor; general information about absorbance of the standards and
scale of the spectrophotometer every 6 calibration techniques can be obtained samples.
months. The calibration may be from general reference books on 10.1.1.2 Alternatively, a scanning
accomplished by using an energy source procedure may be employed to
analytical chemistry. The wavelength
with an intense line emission such as a determine the proper measuring
scale of the spectrophotometer must
mercury lamp, or by using a series of wavelength. If the instrument is a
glass filters spanning the measuring read correctly within 5 nm at all double-beam spectrophotometer, scan
range of the spectrophotometer. calibration points; otherwise, repair and the spectrum between 400 and 415 nm

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 61905

using a 200 µg NO2 standard solution in 11.0 Analytical Procedures 11.4.2 Concurrently analyze the
the sample cell and a blank solution in 11.1 Sample Loss Check. Note the audit sample and the compliance
the reference cell. If a peak does not level of the liquid in the container, and samples in the same manner to evaluate
occur, the spectrophotometer is confirm whether any sample was lost the technique of the analyst and the
probably malfunctioning and should be during shipment. Note this on the standards preparation.
repaired. When a peak is obtained analytical data sheet. If a noticeable 11.4.3 The same analyst, analytical
within the 400 to 415 nm range, the amount of leakage has occurred, either reagents, and analytical system must be
wavelength at which this peak occurs void the sample or use methods, subject used for the compliance samples and
shall be the optimum wavelength for the to the approval of the Administrator, to the audit sample. If this condition is
measurement of absorbance of both the correct the final results. met, duplicate auditing of subsequent
standards and the samples. For a single- 11.2 Sample Preparation. compliance analyses for the same
beam spectrophotometer, follow the Immediately prior to analysis, transfer enforcement agency within a 30-day
scanning procedure described above, the contents of the shipping container to period is waived. An audit sample set
except scan separately the blank and a 50 ml volumetric flask, and rinse the may not be used to validate different
standard solutions. The optimum container twice with 5 ml portions of sets of compliance samples under the
wavelength shall be the wavelength at water. Add the rinse water to the flask, jurisdiction of separate enforcement
which the maximum difference in and dilute to mark with water; mix agencies, unless prior arrangements
absorbance between the standard and thoroughly. Pipette a 25-ml aliquot into have been made with both enforcement
the blank occurs. the porcelain evaporating dish. Return agencies.
10.1.2 Determination of 11.5 Audit Sample Results.
any unused portion of the sample to the 11.5.1 Calculate the audit sample
Spectrophotometer Calibration Factor polyethylene storage bottle. Evaporate
Kc. Add 0 ml, 2.0 ml, 4.0 ml, 6.0 ml, and concentrations and submit results using
the 25-ml aliquot to dryness on a steam the instructions provided with the audit
8.0 ml of the KNO3 working standard bath, and allow to cool. Add 2 ml
solution (1 ml = 100 µg NO2) to a series samples.
phenoldisulfonic acid solution to the 11.5.2 Report the results of the audit
of five 50-ml volumetric flasks. To each dried residue, and triturate thoroughly samples and the compliance
flask, add 25 ml of absorbing solution with a polyethylene policeman. Make determination samples along with their
and 10 ml water. Add 1 N NaOH to each sure the solution contacts all the identification numbers, and the
flask until the pH is between 9 and 12 residue. Add 1 ml water and 4 drops of analyst’s name to the responsible
(about 25 to 35 drops). Dilute to the concentrated sulfuric acid. Heat the enforcement authority. Include this
mark with water. Mix thoroughly, and solution on a steam bath for 3 minutes information with reports of any
pipette a 25-ml aliquot of each solution with occasional stirring. Allow the subsequent compliance analyses for the
into a separate porcelain evaporating solution to cool, add 20 ml water, mix same enforcement authority during the
dish. Beginning with the evaporation well by stirring, and add concentrated 30-day period.
step, follow the analysis procedure of ammonium hydroxide, dropwise, with 11.5.3 The concentrations of the
Section 11.2 until the solution has been constant stirring, until the pH is 10 (as audit samples obtained by the analyst
transferred to the 100-ml volumetric determined by pH paper). If the sample must agree within 5 percent of the
flask and diluted to the mark. Measure contains solids, these must be removed actual concentration. If the 5 percent
the absorbance of each solution at the by filtration (centrifugation is an specification is not met, reanalyze the
optimum wavelength as determined in acceptable alternative, subject to the compliance and audit samples, and
Section 10.2.1. This calibration approval of the Administrator) as include initial and reanalysis values in
procedure must be repeated on each day follows: Filter through Whatman No. 41 the test report.
that samples are analyzed. Calculate the filter paper into a 100-ml volumetric 11.5.4 Failure to meet the 5-percent
spectrophotometer calibration factor as flask. Rinse the evaporating dish with specification may require retests until
shown in Section 12.2. three 5-ml portions of water. Filter these the audit problems are resolved.
10.1.3 Spectrophotometer three rinses. Wash the filter with at least However, if the audit results do not
Calibration Quality Control. Multiply three 15-ml portions of water. Add the affect the compliance or noncompliance
the absorbance value obtained for each filter washings to the contents of the status of the affected facility, the
standard by the Kc factor (reciprocal of volumetric flask, and dilute to the mark Administrator may waive the reanalysis
the least squares slope) to determine the with water. If solids are absent, the requirement, further audits, or retests
distance each calibration point lies from solution can be transferred directly to and accept the results of the compliance
the theoretical calibration line. The the 100-ml volumetric flask and diluted test. While steps are being taken to
difference between the calculated to the mark with water. resolve audit analysis problems, the
concentration values and the actual 11.3 Sample Analysis. Mix the Administrator may also choose to use
concentrations (i.e., 100, 200, 300, and contents of the flask thoroughly, and the data to determine the compliance or
400 µg NO2) should be less than 7 measure the absorbance at the optimum noncompliance status of the affected
percent for all standards. wavelength used for the standards facility.
10.2 Barometer. Calibrate against a (Section 10.2.1), using the blank
solution as a zero reference. Dilute the 12.0 Data Analysis and Calculations
mercury barometer.
sample and the blank with equal Carry out the calculations, retaining at
10.3 Temperature Gauge. Calibrate
volumes of water if the absorbance least one extra significant figure beyond
dial thermometers against mercury-in-
exceeds A4, the absorbance of the 400- that of the acquired data. Round off
glass thermometers.
µg NO2 standard (see Section 10.2.2). figures after final calculations.
10.4 Vacuum Gauge. Calibrate 11.4 Audit Sample Analysis. 12.1 Nomenclature.
mechanical gauges, if used, against a 11.4.1 When the method is used to A = Absorbance of sample.
mercury manometer such as that analyze samples to demonstrate A1 = Absorbance of the 100-µg NO2
specified in Section 6.1.6. compliance with a source emission standard.
10.5 Analytical Balance. Calibrate regulation, an audit sample must be A2 = Absorbance of the 200-µg NO2
against standard weights. analyzed, subject to availability. standard.

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61906 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

A3 = Absorbance of the 300-µg NO2 absorbance into the range of the Tf = Final absolute temperature of flask,
standard. calibration). °K (°R).
A4 = Absorbance of the 400-µg NO2 Kc = Spectrophotometer calibration Ti = Initial absolute temperature of flask,
standard. factor. °K (°R).
C = Concentration of NOX as NO2, dry m = Mass of NOX as NO2 in gas sample, Tstd = Standard absolute temperature,
basis, corrected to standard µg. 293 °K (528 °R).
conditions, mg/dsm3 (lb/dscf). Pf = Final absolute pressure of flask, mm Vsc = Sample volume at standard
Cd = Determined audit sample Hg (in. Hg). conditions (dry basis), ml.
concentration, mg/dscm. Pi = Initial absolute pressure of flask,
Vf = Volume of flask and valve, ml.
Ca = Actual audit sample concentration, mm Hg (in. Hg).
mg/dscm. Pstd = Standard absolute pressure, 760 Va = Volume of absorbing solution, 25
F = Dilution factor (i.e., 25/5, 25/10, etc., mm Hg (29.92 in. Hg). ml.
required only if sample dilution RE = Relative error for QA audit 12.2 Spectrophotometer Calibration
was needed to reduce the samples, percent. Factor.

A1 + 2 A 2 + 3A 3 + 4 A 4
K c = 100 Eq. 7-1
A12 + A 2 2 + A 32 + A 4 2

12.3 Sample Volume, Dry Basis, Corrected to Standard Conditions.

 Pf Pi 
Vsc = (Vf − Va )
Tstd
 −  Eq. 7-2
Pstd  Tf Ti 
P P 
= K1 (Vf − 25)  f − i 
 Tf Ti 

Where: 12.6 Relative Error for QA Audit 3. Jacob, M.B. The Chemical Analysis of
Samples. Air Pollutants. New York. Interscience
K1 = 0.3858 °K/mm Hg for metric units, Publishers, Inc. 1960. Vol. 10, pp. 351–356.
K1 = 17.65 °R/in. Hg for English units.
RE = 100 (C d − C a ) / C a Eq. 7-5 4. Beatty, R.L., L.B. Berger, and H.H.
12.4 Total µg NO2 per sample. Schrenk. Determination of Oxides of
Nitrogen by the Phenoldisulfonic Acid
m = 2 K c AF Eq. 7-3 Method. Bureau of Mines, U.S. Dept. of
13.0 Method Performance Interior. R.I. 3687. February 1943.
5. Hamil, H.F. and D.E. Camann.
13.1 Range. The analytical range of Collaborative Study of Method for the
Where: the method has been determined to be Determination of Nitrogen Oxide Emissions
2 = 50/25, the aliquot factor. 2 to 400 milligrams NOX (as NO2) per from Stationary Sources (Fossil Fuel-Fired
Note: If other than a 25-ml aliquot is used dry standard cubic meter, without Steam Generators). Southwest Research
for analysis, the factor 2 must be replaced by having to dilute the sample. Institute Report for Environmental Protection
a corresponding factor. Agency. Research Triangle Park, NC. October
14.0 Pollution Prevention. [Reserved] 5, 1973.
12.5 Sample Concentration, Dry 6. Hamil, H.F. and R.E. Thomas.
15.0 Waste Management. [Reserved]
Basis, Corrected to Standard Conditions. Collaborative Study of Method for the
16.0 References Determination of Nitrogen Oxide Emissions
C = K 2 ( m / Vsc ) Eq. 7- 4 1. Standard Methods of Chemical Analysis. from Stationary Sources (Nitric Acid Plants).
6th ed. New York, D. Van Nostrand Co., Inc. Southwest Research Institute Report for
1962. Vol. 1, pp. 329–330. Environmental Protection Agency. Research
Where: 2. Standard Method of Test for Oxides of Triangle Park, NC. May 8, 1974.
Nitrogen in Gaseous Combustion Products 7. Stack Sampling Safety Manual (Draft).
K2 = 103 (mg/m3)/(µg/ml) for metric U.S. Environmental Protection Agency,
(Phenoldisulfonic Acid Procedure). In: 1968
units, Office of Air Quality Planning and Standards,
Book of ASTM Standards, Part 26.
K2 = 6.242 × 10¥5 (lb/scf)/(µg/ml) for Philadelphia, PA. 1968. ASTM Designation D Research Triangle Park, NC. September 1978.
English units. 1608–60, pp. 725–729. BILLING CODE 6560–50–P

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17.0 Tables, Diagrams, Flowcharts, and Validation Data

BILLING CODE 6560–50–C

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61908 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

Method 7A—Determination of Nitrogen supplies) and procedures (e.g., sampling and of at least the following additional test
Oxide Emissions From Stationary analytical) essential to its performance. Some methods: Method 1, Method 3, Method 5,
Sources (Ion Chromatographic Method) material is incorporated by reference from and Method 7.
other methods in this part. Therefore, to
Note: This method does not include all of obtain reliable results, persons using this
1.0 Scope and Application
the specifications (e.g., equipment and method should have a thorough knowledge 1.1 Analytes.

Analyte CAS No. Sensitivity

Nitrogen oxides (NOX), as NO2, including:
Nitric oxide (NO) ...................................................................................... 10102–43–9
Nitrogen dioxide (NO2) ............................................................................ 10102–44–0 65–655 ppmv

1.2 Applicability. This method is tissue damage with edema. 3 mg/m3 will intervals to purge possible sulfate
applicable for the determination of NOX cause lung damage in uninitiated. 1 mg/ buildup in the guard column.
emissions from stationary sources. m3 for 8 hours will cause lung damage 6.3.4.2 Pump. Capable of
1.3 Data Quality Objectives. or, in higher concentrations, death. maintaining a steady flow as required by
Adherence to the requirements of this Provide ventilation to limit inhalation. the system.
method will enhance the quality of the Reacts violently with metals and 6.3.4.3 Flow Gauges. Capable of
data obtained from air pollutant organics. measuring the specified system flow
sampling methods. rate.
6.0 Equipment and Supplies
2.0 Summary of Method 6.3.4.4 Conductivity Detector.
6.1 Sample Collection. Same as in 6.3.4.5 Recorder. Compatible with
A grab sample is collected in an Method 7, Section 6.1. the output voltage range of the detector.
evacuated flask containing a dilute 6.2 Sample Recovery. Same as in
sulfuric acid-hydrogen peroxide Method 7, Section 6.2, except the 7.0 Reagents and Standards
absorbing solution. The nitrogen oxides, stirring rod and pH paper are not Unless otherwise indicated, it is
excluding nitrous oxide (N2O), are needed. intended that all reagents conform to the
oxidized to nitrate and measured by ion 6.3 Analysis. For the analysis, the specifications established by the
chromatography. following equipment and supplies are Committee on Analytical Reagents of
3.0 Definitions [Reserved] required. Alternative instrumentation the American Chemical Society, where
and procedures will be allowed such specifications are available;
4.0 Interferences
provided the calibration precision otherwise, use the best available grade.
Biased results have been observed requirement in Section 10.1.2 and audit 7.1 Sample Collection. Same as
when sampling under conditions of accuracy requirement in Section 11.3 Method 7, Section 7.1.
high sulfur dioxide concentrations can be met. 7.2 Sample Recovery. Same as
(above 2000 ppm). 6.3.1 Volumetric Pipets. Class A; Method 7, Section 7.1.1.
5.0 Safety 1-, 2-, 4-, 5-ml (two for the set of 7.3 Analysis. The following reagents
standards and one per sample), 6-, 10- and standards are required for analysis:
5.1 This method may involve , and graduated 5-ml sizes.
hazardous materials, operations, and 7.3.1 Water. Same as Method 7,
6.3.2 Volumetric Flasks. 50-ml (two Section 7.1.1.
equipment. This test method may not
per sample and one per standard), 200- 7.3.2 Stock Standard Solution, 1 mg
address all of the safety problems
ml, and 1-liter sizes. NO2/ml. Dry an adequate amount of
associated with its use. It is the
responsibility of the user of this test 6.3.3 Analytical Balance. To sodium nitrate (NaNO3) at 105 to 110 °C
method to establish appropriate safety measure to within 0.1 mg. (221 to 230 °F) for a minimum of 2
and health practices and to determine 6.3.4 Ion Chromatograph. The ion hours just before preparing the standard
the applicability of regulatory chromatograph should have at least the solution. Then dissolve exactly 1.847 g
limitations prior to performing this test following components: of dried NaNO3 in water, and dilute to
method. 6.3.4.1 Columns. An anion l liter in a volumetric flask. Mix well.
5.2 Corrosive reagents. The separation or other column capable of This solution is stable for 1 month and
following reagents are hazardous. resolving the nitrate ion from sulfate should not be used beyond this time.
Personal protective equipment and safe and other species present and a 7.3.3 Working Standard Solution, 25
procedures are useful in preventing standard anion suppressor column µg/ml. Dilute 5 ml of the standard
chemical splashes. If contact occurs, (optional). Suppressor columns are solution to 200 ml with water in a
immediately flush with copious produced as proprietary items; however, volumetric flask, and mix well.
amounts of water at least 15 minutes. one can be produced in the laboratory 7.3.4 Eluent Solution. Weigh 1.018 g
Remove clothing under shower and using the resin available from BioRad of sodium carbonate (Na2CO3) and 1.008
decontaminate. Treat residual chemical Company, 32nd and Griffin Streets, g of sodium bicarbonate (NaHCO3), and
burns as thermal burns. Richmond, California. Peak resolution dissolve in 4 liters of water. This
5.2.1 Hydrogen Peroxide (H2O2). can be optimized by varying the eluent solution is 0.0024 M Na2CO3/0.003 M
Irritating to eyes, skin, nose, and lungs. strength or column flow rate, or by NaHCO3. Other eluents appropriate to
5.2.2 Sulfuric Acid (H2SO4). Rapidly experimenting with alternative columns the column type and capable of
destructive to body tissue. Will cause that may offer more efficient separation. resolving nitrate ion from sulfate and
third degree burns. Eye damage may When using guard columns with the other species present may be used.
result in blindness. Inhalation may be stronger reagent to protect the 7.3.5 Quality Assurance Audit
fatal from spasm of the larynx, usually separation column, the analyst should Samples. Same as Method 7, Section
within 30 minutes. May cause lung allow rest periods between injection 7.3.8.

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8.0 Sample Collection, Preservation, 8.2 Sample Recovery. Same as in more than 4 days between collection
Storage, and Transport Method 7, Section 8.2, except delete the and analysis.
8.1 Sampling. Same as in Method 7, steps on adjusting and checking the pH
9.0 Quality Control
Section 8.1. of the sample. Do not store the samples

Section Quality control measure Effect

10.1 ........................................... Ion chromatograph calibration ......................... Ensure linearity of ion chromatograph response to standards.
11.3 ........................................... Audit sample analysis ...................................... Evaluate analytical technique, preparation of standards.

10.0 Calibration and Standardizations void the sample or use methods, subject 12.2.1 Calculate the sample
10.1 Ion Chromatograph. to the approval of the Administrator, to concentration C (in mg/dscm) as
10.1.1 Determination of Ion correct the final results. Immediately follows:
before analysis, transfer the contents of
( )
Chromatograph Calibration Factor S.
Prepare a series of five standards by the shipping container to a 50-ml C = (H)(S)(F) 10 4 / Vsc Eq. 7A-1
adding 1.0, 2.0, 4.0, 6.0, and 10.0 ml of volumetric flask, and rinse the container
working standard solution (25 µg/ml) to twice with 5 ml portions of water. Add
a series of five 50-ml volumetric flasks. the rinse water to the flask, and dilute Where:
(The standard masses will equal 25, 50, to the mark with water. Mix thoroughly.
H = Sample peak height, mm.
100, 150, and 250 µg.) Dilute each flask 11.1.2 Pipet a 5-ml aliquot of the
sample into a 50-ml volumetric flask, S = Calibration factor, µg/mm.
to the mark with water, and mix well.
Analyze with the samples as described and dilute to the mark with water. Mix F = Dilution factor (required only if
in Section 11.2, and subtract the blank thoroughly. For each set of sample dilution was needed to
from each value. Prepare or calculate a determinations, prepare a reagent blank reduce the concentration into the
linear regression plot of the standard by diluting 5 ml of absorbing solution to range of calibration), dimensionless.
masses in µg (x-axis) versus their peak 50 ml with water. (Alternatively, eluent 104 = 1:10 dilution times conversion
height responses in millimeters (y-axis). solution may be used instead of water factor of: (mg/103 µg)(106 ml/m3).
(Take peak height measurements with in all sample, standard, and blank 12.2.2 If desired, the concentration
symmetrical peaks; in all other cases, dilutions.) of NO2 may be calculated as ppm NO2
calculate peak areas.) From this curve, 11.2 Analysis. at standard conditions as follows:
or equation, determine the slope, and 11.2.1 Prepare a standard calibration
calculate its reciprocal to denote as the curve according to Section 10.1.1. ppm NO 2 = 0.5228C Eq. 7A-2
calibration factor, S. Analyze the set of standards followed by
10.1.2 Ion Chromatograph the set of samples using the same
Calibration Quality Control. If any point injection volume for both standards and Where:
on the calibration curve deviates from samples. Repeat this analysis sequence 0.5228 = ml/mg NO2.
the line by more than 7 percent of the followed by a final analysis of the
concentration at that point, remake and standard set. Average the results. The 13.0 Method Performance
reanalyze that standard. This deviation two sample values must agree within 5 13.1 Range. The analytical range of
can be determined by multiplying S percent of their mean for the analysis to the method is from 125 to 1250 mg
times the peak height response for each be valid. Perform this duplicate analysis NOX/m3 as NO2 (65 to 655 ppmv), and
standard. The resultant concentrations sequence on the same day. Dilute any higher concentrations may be analyzed
must not differ by more than 7 percent sample and the blank with equal by diluting the sample. The lower
from each known standard mass (i.e., volumes of water if the concentration detection limit is approximately 19 mg/
25, 50, 100, 150, and 250 µg). exceeds that of the highest standard. m3 (10 ppmv), but may vary among
10.2 Conductivity Detector. 11.2.2 Document each sample instruments.
Calibrate according to manufacturer’s chromatogram by listing the following
specifications prior to initial use. 14.0 Pollution Prevention. [Reserved]
analytical parameters: injection point,
10.3 Barometer. Calibrate against a injection volume, nitrate and sulfate 15.0 Waste Management. [Reserved]
mercury barometer. retention times, flow rate, detector
10.4 Temperature Gauge. Calibrate 16.0 References
sensitivity setting, and recorder chart
dial thermometers against mercury-in- speed. 1. Mulik, J.D., and E. Sawicki. Ion
glass thermometers. Chromatographic Analysis of Environmental
11.3 Audit Sample Analysis. Same
10.5 Vacuum Gauge. Calibrate Pollutants. Ann Arbor, Ann Arbor Science
as Method 7, Section 11.4.
mechanical gauges, if used, against a Publishers, Inc. Vol. 2, 1979.
mercury manometer such as that 12.0 Data Analysis and Calculations 2. Sawicki, E., J.D. Mulik, and E.
specified in Section 6.1.6 of Method 7. Wittgenstein. Ion Chromatographic Analysis
10.6 Analytical Balance. Calibrate Carry out the calculations, retaining at of Environmental Pollutants. Ann Arbor, Ann
against standard weights. least one extra significant figure beyond Arbor Science Publishers, Inc. Vol. 1. 1978.
that of the acquired data. Round off 3. Siemer, D.D. Separation of Chloride and
11.0 Analytical Procedures figures after final calculations. Bromide from Complex Matrices Prior to Ion
12.1 Sample Volume. Calculate the Chromatographic Determination. Anal.
11.1 Sample Preparation.
sample volume Vsc (in ml), on a dry Chem. 52(12):1874–1877. October 1980.
11.1.1 Note on the analytical data 4. Small, H., T.S. Stevens, and W.C.
sheet, the level of the liquid in the basis, corrected to standard conditions, Bauman. Novel Ion Exchange
container, and whether any sample was using Equation 7–2 of Method 7. Chromatographic Method Using
lost during shipment. If a noticeable 12.2 Sample Concentration of NOX Conductimetric Determination. Anal. Chem.
amount of leakage has occurred, either as NO2. 47(11):1801. 1975.

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61910 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

5. Yu, K.K., and P.R. Westlin. Evaluation 17.0 Tables, Diagrams, Flowcharts, analytical) essential to its performance. Some
of Reference Method 7 Flask Reaction Time. and Validation Data. [Reserved] material is incorporated by reference from
Source Evaluation Society Newsletter. 4(4). other methods in this part. Therefore, to
November 1979. 10 pp. Method 7B—Determination of Nitrogen obtain reliable results, persons using this
6. Stack Sampling Safety Manual (Draft). Oxide Emissions From Stationary method should have a thorough knowledge
Sources (Ultraviolet of at least the following additional test
U.S. Environmental Protection Agency,
Spectrophotometric Method) methods: Method 1, Method 5, and Method
Office of Air Quality Planning and Standard,
7.
Research Triangle Park, NC. September 1978.
Note: This method does not include all of
the specifications (e.g., equipment and
1.0 Scope and Application
supplies) and procedures (e.g., sampling and 1.1 Analytes.

Analyte CAS No. Sensitivity

Nitrogen oxides (NOX), as NO2, including:
Nitric oxide (NO) ................................................................................................... 10102–43–9
Nitrogen dioxide (NO2) .......................................................................................... 10102–44–0 30–786 ppmv

1.2 Applicability. This method is throat, and lungs. Reacts exothermically 7.1 Sample Collection. Same as
applicable for the determination of NOX with limited amounts of water. Method 7, Section 7.1. It is important
emissions from nitric acid plants. 5.2.3 Sulfuric Acid (H2SO4). Rapidly that the amount of hydrogen peroxide in
1.3 Data Quality Objectives. destructive to body tissue. Will cause the absorbing solution not be increased.
Adherence to the requirements of this third degree burns. Eye damage may Higher concentrations of peroxide may
method will enhance the quality of the result in blindness. Inhalation may be interfere with sample analysis.
data obtained from air pollutant fatal from spasm of the larynx, usually 7.2 Sample Recovery. Same as
sampling methods. within 30 minutes. May cause lung Method 7, Section 7.2.
2.0 Summary of Method tissue damage with edema. 3 mg/m 3 7.3 Analysis. Same as Method 7,
will cause lung damage in uninitiated. Sections 7.3.1, 7.3.3, and 7.3.4, with the
2.1 A grab sample is collected in an 1 mg/m 3 for 8 hours will cause lung addition of the following:
evacuated flask containing a dilute damage or, in higher concentrations,
sulfuric acid-hydrogen peroxide 7.3.1 Working Standard KNO3
death. Provide ventilation to limit Solution. Dilute 10 ml of the standard
absorbing solution; the NOX, excluding inhalation. Reacts violently with metals
nitrous oxide (N2O), are measured by solution to 1000 ml with water. One
and organics. milliliter of the working standard is
ultraviolet spectrophotometry.
6.0 Equipment and Supplies equivalent to 10 µg NO2.
3.0 Definition. [Reserved]
6.1 Sample Collection. Same as 8.0 Sample Collection, Preservation,
4.0 Interferences. [Reserved] Storage, and Transport
Method 7, Section 6.1.
5.0 Safety 6.2 Sample Recovery. The following 8.1 Sample Collection. Same as
5.1 This method may involve items are required for sample recovery: Method 7, Section 8.1.
hazardous materials, operations, and 6.2.1 Wash Bottle. Polyethylene or 8.2 Sample Recovery.
equipment. This test method may not glass. 8.2.1 Let the flask sit for a minimum
address all of the safety problems 6.2.2 Volumetric Flasks. 100-ml (one of 16 hours, and then shake the contents
associated with its use. It is the for each sample). for 2 minutes.
responsibility of the user of this test 6.3 Analysis. The following items 8.2.2 Connect the flask to a mercury
method to establish appropriate safety are required for analysis: filled U-tube manometer. Open the
and health practices and to determine 6.3.1 Volumetric Pipettes. 5-, 10-, valve from the flask to the manometer,
the applicability of regulatory 15-, and 20-ml to make standards and and record the flask temperature (Tf),
limitations prior to performing this test sample dilutions. the barometric pressure, and the
method. 6.3.2 Volumetric Flasks. 1000- and difference between the mercury levels
5.2 Corrosive reagents. The 100-ml for preparing standards and in the manometer. The absolute internal
following reagents are hazardous. dilution of samples. pressure in the flask (Pf) is the
Personal protective equipment and safe 6.3.3 Spectrophotometer. To barometric pressure less the manometer
procedures are useful in preventing measure ultraviolet absorbance at 210 reading.
chemical splashes. If contact occurs, nm. 8.2.3 Transfer the contents of the
immediately flush with copious 6.3.4 Analytical Balance. To flask to a leak-free wash bottle. Rinse
amounts of water at least 15 minutes. measure to within 0.1 mg. the flask three times with 10-ml
Remove clothing under shower and portions of water, and add to the bottle.
decontaminate. Treat residual chemical 7.0 Reagents and Standards
Mark the height of the liquid level so
burn as thermal burn. Note: Unless otherwise indicated, all that the container can be checked for
5.2.1 Hydrogen Peroxide (H2O2). reagents are to conform to the specifications leakage after transport. Label the
Irritating to eyes, skin, nose, and lungs. established by the Committee on Analytical container to identify clearly its contents.
5.2.2 Sodium Hydroxide (NaOH). Reagents of the American Chemical Society, Seal the container for shipping.
Causes severe damage to eyes and skin. where such specifications are available.
Inhalation causes irritation to nose, Otherwise, use the best available grade. 9.0 Quality Control

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 61911

Section Quality control measure Effect

10.1 ........................................... Spectrophometer calibration ............................ Ensures linearity of spectrophotometer response to stand-
ards.
11.4 ........................................... Audit sample analysis ...................................... Evaluates analytical technique and preparation of standards.

10.0 Calibration and Standardizations Measure the absorbance by ultraviolet n

Same as Method 7, Sections 10.2
spectrophotometry at 210 nm, using the ∑ MiAi
blank as a zero reference. Prepare a i =1
through 10.5, with the addition of the Kc = n Eq. 7B-1
standard curve plotting absorbance vs.
following: µg NO2. ∑ Ai 2

10.1 Determination of i =1
Note: If other than a 20-ml aliquot of
Spectrophotometer Standard Curve. sample is used for analysis, then the amount Where:
Add 0 ml, 5 ml, 10 ml, 15 ml, and 20 of absorbing solution in the blank and Mi = Mass of NO2 in standard i, µg.
ml of the KNO3 working standard standards must be adjusted such that the
Ai = Absorbance of NO2 standard i.
solution (1 ml = 10 µg NO2) to a series same amount of absorbing solution is in the
of five 100-ml volumetric flasks. To blank and standards as is in the aliquot of n = Total number of calibration
each flask, add 5 ml of absorbing sample used. standards.
solution. Dilute to the mark with water. 10.1.1 Calculate the 10.1.2 For the set of calibration
The resulting solutions contain 0.0, 50, spectrophotometer calibration factor as standards specified here, Equation 7B–
100, 150, and 200 µg NO2, respectively. follows: 1 simplifies to the following:

A1 + 2 A 2 + 3A 3 + 4 A 4
K c = 50 Eq. 7B-2
A12 + A 2 2 + A 32 + A 4 2

10.2 Spectrophotometer Calibration zero reference, read the absorbance of Occupational Exposure to Nitric Acid. In:
Quality Control. Multiply the the sample at 210 nm. Occupational Safety and Health Reporter.
absorbance value obtained for each 11.4 Audit Sample Analysis. Same Washington, D.C. Bureau of National Affairs,
standard by the Kc factor (reciprocal of as Method 7, Section 11.4, except that Inc. 1976. p. 149.
the least squares slope) to determine the a set of audit samples must be analyzed 2. Rennie, P.J., A.M. Sumner, and F.B.
distance each calibration point lies from with each set of compliance samples or Basketter. Determination of Nitrate in Raw,
the theoretical calibration line. The once per analysis day, or once per week Potable, and Waste Waters by Ultraviolet
difference between the calculated when averaging continuous samples. Spectrophotometry. Analyst. 104:837.
concentration values and the actual September 1979.
concentrations (i.e., 50, 100, 150, and 12.0 Data Analysis and Calculations
200 µg NO2) should be less than 7 Same as Method 7, Section 12.0, 17.0 Tables, Diagrams, Flowcharts,
percent for all standards. except replace Section 12.3 with the and Validation Data. [Reserved]
following:
11.0 Analytical Procedures Method 7C—Determination of Nitrogen
12.1 Total µg NO2 Per Sample.
Oxide Emissions From Stationary
11.1 Sample Loss Check. Note the
level of the liquid in the container, and
m = 5 Kc A F Eq. 7B-3 Sources (Alkaline Permanganate/
Colorimetric Method)
confirm whether any sample was lost Where:
during shipment. Note this on the 5 = 100/20, the aliquot factor. Note: This method does not include all of
analytical data sheet. If a noticeable the specifications (e.g., equipment and
Note: If other than a 20-ml aliquot is used
amount of leakage has occurred, either supplies) and procedures (e.g., sampling and
for analysis, the factor 5 must be replaced by
void the sample or use methods, subject a corresponding factor. analytical) essential to its performance. Some
to the approval of the Administrator, to material is incorporated by reference from
correct the final results. 13.0 Method Performance other methods in this part. Therefore, to
11.2 Sample Preparation. obtain reliable results, persons using this
13.1 Range. The analytical range of
Immediately prior to analysis, transfer method should have a thorough knowledge
the method as outlined has been
the contents of the shipping container to of at least the following additional test
determined to be 57 to 1500 milligrams
a 100-ml volumetric flask, and rinse the methods: Method 1, Method 3, Method 6 and
NOX (as NO2) per dry standard cubic
container twice with 5-ml portions of Method 7.
meter, or 30 to 786 parts per million by
water. Add the rinse water to the flask, volume (ppmv) NOX. 1.0 Scope and Application
and dilute to mark with water.
14.0 Pollution Prevention. [Reserved]
11.3 Sample Analysis. Mix the 1.1 Analytes.
contents of the flask thoroughly and 15.0 Waste Management. [Reserved]
pipette a 20 ml-aliquot of sample into a 16.0 References
100-ml volumetric flask. Dilute to the
mark with water. Using the blank as 1. National Institute for Occupational
Safety and Health. Recommendations for

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61912 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

Analyte CAS no. Sensitivity

Nitrogen oxides (NOX), as NO2, including:
Nitric oxide (NO) ................................................................................................... 10102–43–9
Nitrogen dioxide (NO2) .......................................................................................... 10102–44–07 ppmv

1.2 Applicability. This method and health practices and to determine impingers can be fabricated by a glass
applies to the measurement of NOX the applicability of regulatory blower if not available commercially.)
emissions from fossil-fuel fired steam limitations prior to performing this test 6.1.3 Glass Wool, Stopcock Grease,
generators, electric utility plants, nitric method. Drying Tube, Valve, Pump, Barometer,
acid plants, or other sources as specified 5.2 Corrosive Reagents. The and Vacuum Gauge and Rotameter.
in the regulations. following reagents are hazardous. Same as in Method 6, Sections 6.1.1.3,
1.3 Data Quality Objectives. Personal protective equipment and safe 6.1.1.4, 6.1.1.6, 6.1.1.7, 6.1.1.8, 6.1.2,
Adherence to the requirements of this procedures are useful in preventing and 6.1.3, respectively.
method will enhance the quality of the chemical splashes. If contact occurs, 6.1.4 Rate Meter. Rotameter, or
data obtained from air pollutant immediately flush with copious equivalent, accurate to within 2 percent
sampling methods. amounts of water for at least 15 minutes. at the selected flow rate of between 400
2.0 Summary of Method Remove clothing under shower and and 500 ml/min (0.014 to 0.018 cfm).
decontaminate. Treat residual chemical For rotameters, a range of 0 to 1 liter/
An integrated gas sample is extracted burns as thermal burns. min (0 to 0.035 cfm) is recommended.
from the stack and passed through 5.2.1 Hydrochloric Acid (HCl). 6.1.5 Volume Meter. Dry gas meter
impingers containing an alkaline Highly toxic and corrosive. Causes
potassium permanganate solution; NOX (DGM) capable of measuring the sample
severe damage to skin. Vapors are volume under the sampling conditions
(NO + NO2) emissions are oxidized to highly irritating to eyes, skin, nose, and
NO2 and NO3. Then NO3¥is reduced to of 400 to 500 ml/min (0.014 to 0.018
lungs, causing severe damage. May cfm) for 60 minutes within an accuracy
NO2¥with cadmium, and the NO2¥is cause bronchitis, pneumonia, or edema
analyzed colorimetrically. of 2 percent.
of lungs. Exposure to vapor 6.1.6 Filter. To remove NOX from
3.0 Definitions. [Reserved] concentrations of 0.13 to 0.2 percent can ambient air, prepared by adding 20 g of
be lethal in minutes. Will react with 5-angstrom molecular sieve to a
4.0 Interferences
metals, producing hydrogen. cylindrical tube (e.g., a polyethylene
Possible interferents are sulfur 5.2.2 Oxalic Acid (COOH)2. drying tube).
dioxides (SO2) and ammonia (NH3). Poisonous. Irritating to eyes, skin, nose,
4.1 High concentrations of SO2 6.1.7 Polyethylene Bottles. 1-liter,
and throat. for sample recovery.
could interfere because SO2 consumes 5.2.3 Sodium Hydroxide (NaOH).
MnO4 (as does NOX) and, therefore, 6.1.8 Funnel and Stirring Rods. For
Causes severe damage to eye tissues and
could reduce the NOX collection sample recovery.
to skin. Inhalation causes irritation to
efficiency. However, when sampling 6.2 Sample Preparation and
nose, throat, and lungs. Reacts
emissions from a coal-fired electric Analysis.
exothermically with small amounts of
utility plant burning 2.1 percent sulfur 6.2.1 Hot Plate. Stirring type with
water.
coal with no control of SO2 emissions, 5.2.4 Potassium Permanganate 50- by 10-mm Teflon-coated stirring
collection efficiency was not reduced. In (KMnO4). Caustic, strong oxidizer. bars.
fact, calculations show that sampling Avoid bodily contact with. 6.2.2 Beakers. 400-, 600-, and 1000-
3000 ppm SO2 will reduce the MnO4 ml capacities.
concentration by only 5 percent if all 6.0 Equipment and Supplies 6.2.3 Filtering Flask. 500-ml
the SO2 is consumed in the first 6.1 Sample Collection and Sample capacity with side arm.
impinger. Recovery. A schematic of the Method 7C 6.2.4 Buchner Funnel. 75-mm ID,
4.2 Ammonia (NH3) is slowly sampling train is shown in Figure 7C– with spout equipped with a 13-mm ID
oxidized to NO3¥ by the absorbing 1, and component parts are discussed by 90-mm long piece of Teflon tubing to
solution. At 100 ppm NH3 in the gas below. Alternative apparatus and minimize possibility of aspirating
stream, an interference of 6 ppm NOX procedures are allowed provided sample solution during filtration.
(11 mg NO2/m3) was observed when the acceptable accuracy and precision can 6.2.5 Filter Paper. Whatman GF/C,
sample was analyzed 10 days after be demonstrated to the satisfaction of 7.0-cm diameter.
collection. Therefore, the method may the Administrator. 6.2.6 Stirring Rods.
not be applicable to plants using NH3 6.1.1 Probe. Borosilicate glass 6.2.7 Volumetric Flasks. 100-, 200-
injection to control NOX emissions tubing, sufficiently heated to prevent or 250-, 500-, and 1000-ml capacity.
unless means are taken to correct the water condensation and equipped with 6.2.8 Watch Glasses. To cover 600-
results. An equation has been developed an in-stack or heated out-of-stack filter and 1000-ml beakers.
to allow quantification of the to remove particulate matter (a plug of 6.2.9 Graduated Cylinders. 50- and
interference and is discussed in glass wool is satisfactory for this 250-ml capacities.
Reference 5 of Section 16.0. purpose). Stainless steel or Teflon 6.2.10 Pipettes. Class A.
tubing may also be used for the probe. 6.2.11 pH Meter. To measure pH
5.0 Safety 6.1.2 Impingers. Three restricted- from 0.5 to 12.0.
5.1 Disclaimer. This method may orifice glass impingers, having the 6.2.12 Burette. 50-ml with a
involve hazardous materials, operations, specifications given in Figure 7C–2, are micrometer type stopcock. (The
and equipment. This test method may required for each sampling train. The stopcock is Catalog No. 8225–t–05, Ace
not address all of the safety problems impingers must be connected in series Glass, Inc., Post Office Box 996,
associated with its use. It is the with leak-free glass connectors. Louisville, Kentucky 50201.) Place a
responsibility of the user of this test Stopcock grease may be used, if glass wool plug in bottom of burette. Cut
method to establish appropriate safety necessary, to prevent leakage. (The off burette at a height of 43 cm (17 in.)

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Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations 61913

from the top of plug, and have a blower dilute to volume, and mix well. Store in 8.0 Sample Collection, Preservation,
attach a glass funnel to top of burette a glass-stoppered bottle. Storage, and Transport
such that the diameter of the burette 7.2.8 Sulfanilamide Solution. Add 8.1 Preparation of Sampling Train.
remains essentially unchanged. Other 20 g of sulfanilamide (melting point 165 Add 200 ml of KMnO4/NaOH solution
means of attaching the funnel are to 167 °C (329 to 333 °F)) to 700 ml of (Section 7.1.2) to each of three
acceptable. water. Add, with mixing, 50 ml impingers, and assemble the train as
6.2.13 Glass Funnel. 75-mm ID at concentrated phosphoric acid (85 shown in Figure 7C–1. Adjust the probe
the top. percent), and dilute to 1000 ml. This heater to a temperature sufficient to
6.2.14 Spectrophotometer. Capable solution is stable for at least 1 month, prevent water condensation.
of measuring absorbance at 540 nm; 1- if refrigerated. 8.2 Leak-Checks. Same as in Method
cm cells are adequate. 7.2.9 N-(1-Naphthyl)- 6, Section 8.2.
6.2.15 Metal Thermometers. Ethylenediamine Dihydrochloride 8.3 Sample Collection.
Bimetallic thermometers, range 0 to 150 (NEDA) Solution. Dissolve 0.5 g of 8.3.1 Record the initial DGM reading
°C (32 to 300 °F). NEDA in 500 ml of water. An aqueous and barometric pressure. Determine the
6.2.16 Culture Tubes. 20-by 150- sampling point or points according to
solution should have one absorption
mm, Kimax No. 45048. the appropriate regulations (e.g.,
peak at 320 nm over the range of 260 to
6.2.17 Parafilm ‘‘M.’’ Obtained from § 60.46(b)(5) of 40 CFR Part 60). Position
400 nm. NEDA that shows more than
American Can Company, Greenwich, the tip of the probe at the sampling
one absorption peak over this range is
Connecticut 06830. point, connect the probe to the first
impure and should not be used. This
6.2.18 CO2 Measurement
solution is stable for at least 1 month if impinger, and start the pump. Adjust
Equipment. Same as in Method 3,
protected from light and refrigerated. the sample flow to a value between 400
Section 6.0.
7.2.10 Cadmium. Obtained from and 500 ml/min (0.014 and 0.018 cfm).
7.0 Reagents and Standards Matheson Coleman and Bell, 2909 CAUTION: DO NOT EXCEED THESE
Unless otherwise indicated, it is Highland Avenue, Norwood, Ohio FLOW RATES. Once adjusted, maintain
intended that all reagents conform to the 45212, as EM Laboratories Catalog No. a constant flow rate during the entire
specifications established by the 2001. Prepare by rinsing in 2 N HCl for sampling run. Sample for 60 minutes.
Committee on Analytical Reagents of 5 minutes until the color is silver-grey. For relative accuracy (RA) testing of
the American Chemical Society, where Then rinse the cadmium with water continuous emission monitors, the
such specifications are available; until the rinsings are neutral when minimum sampling time is 1 hour,
otherwise, use the best available grade. tested with pH paper. CAUTION: H2 is sampling 20 minutes at each traverse
7.1 Sample Collection. liberated during preparation. Prepare in point.
7.1.1 Water. Deionized distilled to an exhaust hood away from any flame Note: When the SO2 concentration is
conform to ASTM Specification D 1193– or combustion source. greater than 1200 ppm, the sampling time
77 or 91 Type 3 (incorporated by 7.2.11 Sodium Sulfite (NaNO2) may have to be reduced to 30 minutes to
reference—see § 60.17). Standard Solution, Nominal eliminate plugging of the impinger orifice
with MnO2. For RA tests with SO2 greater
7.1.2 Potassium Permanganate, 4.0 Concentration, 1000 µg NO2¥/ml. than 1200 ppm, sample for 30 minutes (10
Percent (w/w), Sodium Hydroxide, 2.0 Desiccate NaNO2 overnight. Accurately minutes at each point).
Percent (w/w) solution (KMnO4/NaOH weigh 1.4 to 1.6 g of NaNO2 (assay of 97
solution). Dissolve 40.0 g of KMnO4 and percent NaNO2 or greater), dissolve in 8.3.2 Record the DGM temperature,
20.0 g of NaOH in 940 ml of water. water, and dilute to 1 liter. Calculate the and check the flow rate at least every 5
7.2 Sample Preparation and exact NO2-concentration using Equation minutes. At the conclusion of each run,
Analysis. 7C–1 in Section 12.2. This solution is turn off the pump, remove the probe
7.2.1 Water. Same as in Section stable for at least 6 months under from the stack, and record the final
7.1.1. laboratory conditions. readings. Divide the sample volume by
7.2.2 Oxalic Acid Solution. Dissolve the sampling time to determine the
7.2.12 Potassium Nitrate (KNO3)
48 g of oxalic acid [(COOH)2·2H2O] in average flow rate. Conduct the
Standard Solution. Dry KNO3 at 110 °C
water, and dilute to 500 ml. Do not heat mandatory post-test leak-check. If a leak
(230 °F) for 2 hours, and cool in a
the solution. is found, void the test run, or use
desiccator. Accurately weigh 9 to 10 g
7.2.3 Sodium Hydroxide, 0.5 N. procedures acceptable to the
of KNO3 to within 0.1 mg, dissolve in
Dissolve 20 g of NaOH in water, and Administrator to adjust the sample
water, and dilute to 1 liter. Calculate the
dilute to 1 liter. volume for the leakage.
exact NO3¥ concentration using
7.2.4 Sodium Hydroxide, 10 N. 8.4 CO2 Measurement. During
Equation 7C–2 in Section 12.3. This
Dissolve 40 g of NaOH in water, and sampling, measure the CO2 content of
solution is stable for 2 months without
dilute to 100 ml. the stack gas near the sampling point
preservative under laboratory
7.2.5 Ethylenediamine Tetraacetic using Method 3. The single-point grab
conditions.
Acid (EDTA) Solution, 6.5 percent (w/ sampling procedure is adequate,
v). Dissolve 6.5 g of EDTA (disodium 7.2.13 Spiking Solution. Pipette 7 ml provided the measurements are made at
salt) in water, and dilute to 100 ml. of the KNO3 standard into a 100-ml least three times (near the start, midway,
Dissolution is best accomplished by volumetric flask, and dilute to volume. and before the end of a run), and the
using a magnetic stirrer. 7.2.14 Blank Solution. Dissolve 2.4 g average CO2 concentration is computed.
7.2.6 Column Rinse Solution. Add of KMnO4 and 1.2 g of NaOH in 96 ml The Orsat or Fyrite analyzer may be
20 ml of 6.5 percent EDTA solution to of water. Alternatively, dilute 60 ml of used for this analysis.
960 ml of water, and adjust the pH to KMnO4/NaOH solution to 100 ml. 8.5 Sample Recovery. Disconnect
between 11.7 and 12.0 with 0.5 N 7.2.15 Quality Assurance Audit the impingers. Pour the contents of the
NaOH. Samples. Same as in Method 7, Section impingers into a 1-liter polyethylene
7.2.7 Hydrochloric Acid (HCl), 2 N. 7.3.10. When requesting audit samples, bottle using a funnel and a stirring rod
Add 86 ml of concentrated HCl to a 500 specify that they be in the appropriate (or other means) to prevent spillage.
ml-volumetric flask containing water, concentration range for Method 7C. Complete the quantitative transfer by

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rinsing the impingers and connecting clear to light pink, and add the rinsings the solution level. Seal and identify the
tubes with water until the rinsings are to the bottle. Mix the sample, and mark sample container.

9.0 Quality Control

Section Quality control measure Effect

8.2, 10.1–10.3 ........................... Sampling equipment leak-check and calibra- Ensure accurate measurement of sample volume.
tion.
10.4 ........................................... Spectrophotometer calibration ......................... Ensure linearity of spectrophotometer response to standards.
11.3 ........................................... Spiked sample analysis ................................... Ensure reduction efficiency of column.
11.6 ........................................... Audit sample analysis ...................................... Evaluate analytical technique, preparation of standards.

10.0 Calibration and Standardizations weeks; thus, analysis must occur within 11.2.4 Allow the samples to cool to
10.1 Volume Metering System. Same 4 weeks of collection. near room temperature, being sure that
as Method 6, Section 10.1. For detailed 11.2 Sample Preparation. the samples are still clear. Adjust the pH
instructions on carrying out these 11.2.1 Prepare a cadmium reduction to between 11.7 and 12.0 with 10 N
calibrations, it is suggested that Section column as follows: Fill the burette with NaOH. Quantitatively transfer the
3.5.2 of Reference 4 of Section 16.0 be water. Add freshly prepared cadmium mixture to a Buchner funnel containing
consulted. slowly, with tapping, until no further GF/C filter paper, and filter the
10.2 Temperature Sensors and settling occurs. The height of the precipitate. Filter the mixture into a
Barometer. Same as in Method 6, cadmium column should be 39 cm (15 500-ml filtering flask. Wash the solid
Sections 10.2 and 10.4, respectively. in). When not in use, store the column material four times with water. When
10.3 Check of Rate Meter Calibration under rinse solution. filtration is complete, wash the Teflon
Accuracy (Optional). Disconnect the Note: The column should not contain any tubing, quantitatively transfer the
probe from the first impinger, and bands of cadmium fines. This may occur if filtrate to a 500-ml volumetric flask, and
connect the filter. Start the pump, and regenerated cadmium is used and will greatly dilute to volume. The samples are now
reduce the column lifetime. ready for cadmium reduction. Pipette a
adjust the rate meter to read between
400 and 500 ml/min (0.014 and 0.018 11.2.2 Note the level of liquid in the 50-ml aliquot of the sample into a 150-
cfm). After the flow rate has stabilized, sample container, and determine ml beaker, and add a magnetic stirring
start measuring the volume sampled, as whether any sample was lost during bar. Pipette in 1.0 ml of 6.5 percent
recorded by the dry gas meter and the shipment. If a noticeable amount of EDTA solution, and mix.
sampling time. Collect enough volume leakage has occurred, the volume lost 11.3 Determine the correct stopcock
to measure accurately the flow rate. can be determined from the difference setting to establish a flow rate of 7 to 9
Then calculate the flow rate. This between initial and final solution levels, ml/min of column rinse solution
average flow rate must be less than 500 and this value can then be used to through the cadmium reduction
ml/min (0.018 cfm) for the sample to be correct the analytical result. column. Use a 50-ml graduated cylinder
valid; therefore, it is recommended that Quantitatively transfer the contents to a
to collect and measure the solution
the flow rate be checked as above prior 1-liter volumetric flask, and dilute to
volume. After the last of the rinse
to each test. volume.
solution has passed from the funnel into
10.4 Spectrophotometer. 11.2.3 Take a 100-ml aliquot of the
the burette, but before air entrapment
10.4.1 Dilute 5.0 ml of the NaNO2 sample and blank (unexposed KMnO4/
can occur, start adding the sample, and
standard solution to 200 ml with water. NaOH) solutions, and transfer to 400-ml
collect it in a 250-ml graduated
This solution nominally contains 25 µg beakers containing magnetic stirring
cylinder. Complete the quantitative
NO2¥/ml. Use this solution to prepare bars. Using a pH meter, add
calibration standards to cover the range concentrated H2SO4 with stirring until a transfer of the sample to the column as
of 0.25 to 3.00 µg NO2¥/ml. Prepare a pH of 0.7 is obtained. Allow the the sample passes through the column.
minimum of three standards each for solutions to stand for 15 minutes. Cover After the last of the sample has passed
the linear and slightly nonlinear the beakers with watch glasses, and from the funnel into the burette, start
(described below) range of the curve. bring the temperature of the solutions to adding 60 ml of column rinse solution,
Use pipettes for all additions. 50 °C (122 °F). Keep the temperature and collect the rinse solution until the
10.4.2 Measure the absorbance of the below 60 °C (140 °F). Dissolve 4.8 g of solution just disappears from the funnel.
standards and a water blank as oxalic acid in a minimum volume of Quantitatively transfer the sample to a
instructed in Section 11.5. Plot the net water, approximately 50 ml, at room 200-ml volumetric flask (a 250-ml flask
absorbance vs. µg NO2¥/ml. Draw a temperature. Do not heat the solution. may be required), and dilute to volume.
smooth curve through the points. The Add this solution slowly, in increments, The samples are now ready for NO2-
curve should be linear up to an until the KMnO4 solution becomes analysis.
absorbance of approximately 1.2 with a colorless. If the color is not completely Note: Two spiked samples should be run
slope of approximately 0.53 absorbance removed, prepare some more of the with every group of samples passed through
units/µg NO2¥/ml. The curve should above oxalic acid solution, and add the column. To do this, prepare two
pass through the origin. The curve is until a colorless solution is obtained. additional 50-ml aliquots of the sample
slightly nonlinear from an absorbance of Add an excess of oxalic acid by suspected to have the highest NO2-
1.2 to 1.6. dissolving 1.6 g of oxalic acid in 50 ml concentration, and add 1 ml of the spiking
of water, and add 6 ml of this solution solution to these aliquots. If the spike
11.0 Analytical Procedures to the colorless solution. If suspended recovery or column efficiency (see Section
11.1 Sample Stability. Collected matter is present, add concentrated 12.2) is below 95 percent, prepare a new
samples are stable for at least four H2SO4 until a clear solution is obtained. column, and repeat the cadmium reduction.

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11.4 Repeat the procedures outlined Note: Some test tubes give a high blank Tm = Average dry gas meter absolute
in Sections 11.2 and 11.3 for each NO2¥ value but culture tubes do not. temperature, °K.
sample and each blank. 11.6 Audit Sample Analysis. Same Tstd = Standard absolute temperature,
11.5 Sample Analysis. Pipette 10 ml as in Method 7, Section 11.4. 293 °K (528 °R).
of sample into a culture tube. Pipette in Vm(std) = Dry gas volume measured by
12.0 Data Analysis and Calculations the dry gas meter, corrected to
10 ml of sulfanilamide solution and 1.4
ml of NEDA solution. Cover the culture Carry out calculations, retaining at standard conditions, dscm (dscf).
least one extra significant figure beyond Vm = Dry gas volume as measured by the
tube with parafilm, and mix the
that of the acquired data. Round off dry gas meter, scm (scf).
solution. Prepare a blank in the same
manner using the sample from treatment
figures after final calculation. x = Analysis of spiked sample, µg
12.1 Nomenclature. NO2¥/ml.
of the unexposed KMnO4/NaOH
solution. Also, prepare a calibration B = Analysis of blank, µg NO2¥/ml. X = Correction factor for CO2 collection
C = Concentration of NOX as NO2, dry = 100/(100 ¥ %CO2(V/V)).
standard to check the slope of the
basis, mg/dsm3. y = Analysis of unspiked sample, µg
calibration curve. After a 10-minute E = Column efficiency, dimensionless
color development interval, measure the NO2¥/ml.
K2 = 10¥3 mg/µg. Y = Dry gas meter calibration factor.
absorbance at 540 nm against water. m = Mass of NOX, as NO2, in sample,
Read µg NO2¥/ml from the calibration µg.
1.0 ppm NO = 1.247 mg NO/m3 at STP.
curve. If the absorbance is greater than Pbar = Barometric pressure, mm Hg (in. 1.0 ppm NO2 = 1.912 mg NO2/m3 at
that of the highest calibration standard, Hg). STP.
use less than 10 ml of sample, and Pstd = Standard absolute pressure, 760 1 ft3 = 2.832 × 10¥2 m3.
repeat the analysis. Determine the mm Hg (29.92 in. Hg). 12.2 NO2 Concentration. Calculate
NO2¥concentration using the s = Concentration of spiking solution, µg the NO2 concentration of the solution
calibration curve obtained in Section NO3/ml. (see Section 7.2.11) using the following
10.4. S = Analysis of sample, µg NO2¥/ml. equation:

µg NO 2− purity, % 46.01
= g NaNO 2 × × 10 3 × Eq. 7C-1
ml 100 69.01
12.3 NO3 Concentration. Calculate the NO3 concentration of the KNO3 solution (see Section 7.2.12) using the following
equation:

µg NO3−
ml
= g KNO3 × 10 3 ×
62.01
10110
.
( ) Eq. 7C-2

12.4 Sample Volume, Dry Basis, Corrected to Standard Conditions.

Tstd Pbar
Vm (std ) = Vm X Y Eq. 7C-3
Tm Pstd
Pbar
= K1 X Y Vm
Tm

Where:
K1 = 0.3855 °K/mm Hg for metric units.
K1 = 17.65 °R/in. Hg for English units.
12.5 Efficiency of Cadmium Reduction Column. Calculate this value as follows:

200 (x − y) 269.6 (x − y)
E= = Eq. 7C- 4
46.01 s
1.0 s
62.01
Where:
200 = Final volume of sample and blank after passing through the column, ml.
1.0 = Volume of spiking solution added, ml.
46.01 = µg NO2¥/µmole.
62.01 = µg NO3¥/µmole.
12.6 Total µg NO2.

 500   1000   (S − B)  (2 × 10 )(S − B)
4
m = 200 = Eq. 7C-5
 50   100   E  E
Where:
500 = Total volume of prepared sample, ml.
50 = Aliquot of prepared sample processed through cadmium column, ml.
100 = Aliquot of KMnO4/NaOH solution, ml.

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61916 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

1000 = Total volume of KMnO4/NaOH solution, ml.
12.7 Sample Concentration.

m method has been found to collect NOX Division, Environmental Monitoring Systems
C = K2 Eq. 7C-6 emissions quantitatively up to 1782 mg Laboratory, to The Record, EPA. March 30,
Vm (std ) 1983. NH3 Interference in Methods 7C and
NOX/m3, as NO2 (932 ppm NOX).
7D.
13.0 Method Performance 14.0 Pollution Prevention. [Reserved] 3. Margeson, J.H., J.C. Suggs, and M.R.
Midgett. Reduction of Nitrate to Nitrite with
13.1 Precision. The intra-laboratory 15.0 Waste Management. [Reserved] Cadmium. Anal. Chem. 52:1955–57. 1980.
relative standard deviation for a single
16.0 References 4. Quality Assurance Handbook for Air
measurement is 2.8 and 2.9 percent at Pollution Measurement Systems. Volume
201 and 268 ppm NOX, respectively. 1. Margeson, J.H., W.J. Mitchell, J.C. Suggs, III—Stationary Source Specific Methods. U.S.
13.2 Bias. The method does not and M.R. Midgett. Integrated Sampling and Environmental Protection Agency. Research
exhibit any bias relative to Method 7. Analysis Methods for Determining NOX Triangle Park, NC. Publication No. EPA–600/
13.3 Range. The lower detectable Emissions at Electric Utility Plants. U.S. 4–77–027b. August 1977.
Environmental Protection Agency, Research 5. Margeson, J.H., et al. An Integrated
limit is 13 mg NOX/m3, as NO2 (7 ppm Triangle Park, NC. Journal of the Air
NOX) when sampling at 500 ml/min for Method for Determining NOX Emissions at
Pollution Control Association. 32:1210–1215. Nitric Acid Plants. Analytical Chemistry. 47
1 hour. No upper limit has been 1982.
established; however, when using the (11):1801. 1975.
2. Memorandum and attachment from J.H.
recommended sampling conditions, the Margeson, Source Branch, Quality Assurance BILLING CODE 6560–50–P

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17.0 Tables, Diagrams, Flowcharts, and Validation Data

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BILLING CODE 6560–50–C supplies) and procedures (e.g., sampling and methods: Method 1, Method 3, Method 6,
Method 7D—Determination of Nitrogen analytical) essential to its performance. Some Method 7, and Method 7C.
Oxide Emissions From Stationary material is incorporated by reference from
other methods in this part. Therefore, to 1.0 Scope and Application
Sources (Alkaline-Permanganate/Ion
Chromatographic Method) obtain reliable results, persons using this
method should have a thorough knowledge
1.1 Analytes.
Note: This method is not inclusive with of at least the following additional test
respect to specifications (e.g., equipment and

Analyte CAS No. Sensitivity

Nitrogen oxides (NOX), as NO2, including:
Nitric oxide (NO) ................................................................................................... 10102–43–9
Nitrogen dioxide (NO2) .......................................................................................... 10102–44–0 7 ppmv

1.2 Applicability. This method 5.2.2 Sodium Hydroxide (NaOH). 77 or 91 Type 3 (incorporated by
applies to the measurement of NOX Causes severe damage to eye tissues and reference—see § 60.17).
emissions from fossil-fuel fired steam to skin. Inhalation causes irritation to 7.1.2 Potassium Permanganate, 4.0
generators, electric utility plants, nitric nose, throat, and lungs. Reacts Percent (w/w), Sodium Hydroxide, 2.0
acid plants, or other sources as specified exothermically with limited amounts of Percent (w/w). Dissolve 40.0 g of
in the regulations. water. KMnO4 and 20.0 g of NaOH in 940 ml
1.3 Data Quality Objectives. 5.2.3 Potassium Permanganate of water.
Adherence to the requirements of this (KMnO4). Caustic, strong oxidizer. 7.2 Sample Preparation and
method will enhance the quality of the Avoid bodily contact with. Analysis.
data obtained from air pollutant 7.2.1 Water. Same as in Section
6.0 Equipment and Supplies 7.1.1.
sampling methods.
6.1 Sample Collection and Sample 7.2.2 Hydrogen Peroxide (H2O2), 5
2.0 Summary of Method Recovery. Same as Method 7C, Section Percent. Dilute 30 percent H2O2 1:5 (v/
An integrated gas sample is extracted 6.1. A schematic of the sampling train v) with water.
from the stack and passed through used in performing this method is 7.2.3 Blank Solution. Dissolve 2.4 g
impingers containing an alkaline- shown in Figure 7C–1 of Method 7C. of KMnO4 and 1.2 g of NaOH in 96 ml
potassium permanganate solution; NOX 6.2 Sample Preparation and of water. Alternatively, dilute 60 ml of
(NO + NO2) emissions are oxidized to Analysis. KMnO4/NaOH solution to 100 ml.
NO3¥. Then NO3¥ is analyzed by ion 6.2.1 Magnetic Stirrer. With 25- by 7.2.4 KNO3 Standard Solution. Dry
chromatography. 10-mm Teflon-coated stirring bars. KNO3 at 110°C for 2 hours, and cool in
6.2.2 Filtering Flask. 500-ml a desiccator. Accurately weigh 9 to 10
3.0 Definitions [Reserved] capacity with sidearm. g of KNO3 to within 0.1 mg, dissolve in
4.0 Interferences 6.2.3 Buchner Funnel. 75-mm ID, water, and dilute to 1 liter. Calculate the
with spout equipped with a 13-mm ID exact NO3¥ concentration using
Same as in Method 7C, Section 4.0. by 90-mm long piece of Teflon tubing to Equation 7D–1 in Section 12.2. This
5.0 Safety minimize possibility of aspirating solution is stable for 2 months without
5.1 Disclaimer. This method may sample solution during filtration. preservative under laboratory
6.2.4 Filter Paper. Whatman GF/C, conditions.
involve hazardous materials, operations,
7.0-cm diameter. 7.2.5 Eluent, 0.003 M NaHCO3/
and equipment. This test method may 6.2.5 Stirring Rods.
not address all of the safety problems 0.0024 M Na2CO3. Dissolve 1.008 g
6.2.6 Volumetric Flask. 250-ml. NaHCO3 and 1.018 g Na2CO3 in water,
associated with its use. It is the 6.2.7 Pipettes. Class A.
responsibility of the user of this test 6.2.8 Erlenmeyer Flasks. 250-ml. and dilute to 4 liters. Other eluents
method to establish appropriate safety 6.2.9 Ion Chromatograph. Equipped capable of resolving nitrate ion from
and health practices and to determine with an anion separator column to sulfate and other species present may be
the applicability of regulatory separate NO3¥, H3∂ suppressor, and used.
limitations prior to performing this test necessary auxiliary equipment. 7.2.6 Quality Assurance Audit
method. Nonsuppressed and other forms of ion Samples. Same as Method 7, Section
5.2 Corrosive reagents. The chromatography may also be used 7.3.10. When requesting audit samples,
following reagents are hazardous. provided that adequate resolution of specify that they be in the appropriate
Personal protective equipment and safe NO3¥ is obtained. The system must also concentration range for Method 7D.
procedures are useful in preventing 8.0 Sample Collection, Preservation,
be able to resolve and detect NO2¥.
chemical splashes. If contact occurs, Transport, and Storage.
immediately flush with copious 7.0 Reagents and Standards 8.1 Sampling. Same as in Method
amounts of water for at least 15 minutes. 7C, Section 8.1.
Note: Unless otherwise indicated, it is 8.2 Sample Recovery. Same as in
Remove clothing under shower and intended that all reagents conform to the
decontaminate. Treat residual chemical Method 7C, Section 8.2.
specifications established by the Committee
burns as thermal burns. on Analytical Reagents of the American 8.3 Sample Preparation for Analysis.
5.2.1 Hydrogen Peroxide (H2O2). Chemical Society, where such specifications Note: Samples must be analyzed within 28
Irritating to eyes, skin, nose, and lungs. are available; otherwise, use the best days of collection.
30% H2O2 is a strong oxidizing agent; available grade. 8.3.1 Note the level of liquid in the
avoid contact with skin, eyes, and 7.1 Sample Collection. sample container, and determine
combustible material. Wear gloves when 7.1.1 Water. Deionized distilled to whether any sample was lost during
handling. conform to ASTM specification D 1193– shipment. If a noticeable amount of

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61920 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

leakage has occurred, the volume lost magnetic stirring bar. Adjust the stirring the mixture to a Buchner funnel containing
can be determined from the difference rate to as fast a rate as possible without GF/C filter paper, and filter the precipitate.
between initial and final solution levels, loss of solution. Add 5 percent H2O2 in The spout of the Buchner funnel should be
and this value can then be used to increments of approximately 5 ml using equipped with a 13-mm ID by 90-mm long
correct the analytical result. a 5-ml pipette. When the KMnO4 color piece of Teflon tubing. This modification
Quantitatively transfer the contents to a appears to have been removed, allow minimizes the possibility of aspirating
1-liter volumetric flask, and dilute to the precipitate to settle, and examine sample solution during filtration. Filter the
the supernatant liquid. If the liquid is mixture into a 500-ml filtering flask. Wash
volume.
the solid material four times with water.
8.3.2 Sample preparation can be clear, the H2O2 addition is complete. If
When filtration is complete, wash the Teflon
started 36 hours after collection. This the KMnO4 color persists, add more
tubing, quantitatively transfer the filtrate to a
time is necessary to ensure that all H2O2, with stirring, until the 250-ml volumetric flask, and dilute to
NO2¥ is converted to NO3¥ in the supernatant liquid is clear. volume. The sample and blank are now ready
collection solution. Take a 50-ml aliquot Note: The faster the stirring rate, the less for NO3¥analysis.
of the sample and blank, and transfer to volume of H2O2 that will be required to
250-ml Erlenmeyer flasks. Add a remove the KMnO4.) Quantitatively transfer 9.0 Quality Control

Section Quality control measure Effect

8.2, 10.1–10.3 ........................... Sampling equipment leak-check and calibra- Ensure accurate measurement of sample volume.
tion.
10.4 ........................................... Spectrophotometer calibration ......................... Ensure linearity of spectrophotometer response to standards.
11.3 ........................................... Spiked sample analysis ................................... Ensure reduction efficiency of column.
11.6 ........................................... Audit sample analysis ...................................... Evaluate analytical technique, preparation of standards.

10.0 Calibration and Standardizations individual values versus concentration then re-inject a water sample and
in µg NO3¥/ml. observe the chromatogram. When no
10.1 Dry Gas Meter (DGM) System. NO3¥ is present, the instrument is ready
10.3.2 Do not force the curve
10.1.1 Initial Calibration. Same as in through zero. Draw a smooth curve for use. Inject calibration standards.
Method 6, Section 10.1.1. For detailed through the points. The curve should be Then inject samples and a blank. Repeat
instructions on carrying out this linear. With the linear curve, use linear the injection of the calibration standards
calibration, it is suggested that Section regression to determine the calibration (to compensate for any drift in response
3.5.2 of Citation 4 in Section 16.0 of equation. of the instrument). Measure the NO3¥
Method 7C be consulted. peak height or peak area, and determine
10.1.2 Post-Test Calibration Check. 11.0 Analytical Procedures the sample concentration from the
Same as in Method 6, Section 10.1.2. 11.1 The following chromatographic calibration curve.
10.2 Thermometers for DGM and conditions are recommended: 0.003 M 11.3 Audit Analysis. Same as in
Barometer. Same as in Method 6, NaHCO3/0.0024 Na2CO3 eluent solution Method 7, Section 11.4
Sections 10.2 and 10.4, respectively. (Section 7.2.5), full scale range, 3
10.3 Ion Chromatograph. µMHO; sample loop, 0.5 ml; flow rate, 12.0 Data Analysis and Calculations
10.3.1 Dilute a given volume (1.0 ml 2.5 ml/min. These conditions should Carry out calculations, retaining at
or greater) of the KNO3 standard give a NO3¥ retention time of least one extra significant figure beyond
solution to a convenient volume with approximately 15 minutes (Figure 7D– that of the acquired data. Round off
water, and use this solution to prepare 1). figures after final calculation.
calibration standards. Prepare at least 11.2 Establish a stable baseline. 12.1 Nomenclature. Same as in
four standards to cover the range of the Inject a sample of water, and determine Method 7C, Section 12.1.
samples being analyzed. Use pipettes for whether any NO3¥ appears in the 12.2 NO3¥ concentration. Calculate
all additions. Run standards as chromatogram. If NO3¥ is present, the NO3¥ concentration in the KNO3
instructed in Section 11.2. Determine repeat the water load/injection standard solution (see Section 7.2.4)
peak height or area, and plot the procedure approximately five times; using the following equation:

µg NO3− 62.01
= g of KNO3 × 10 3 × Eq. 7D-1
ml 10110
.
12.3 Sample Volume, Dry Basis, Corrected to Standard Conditions. Same as in Method 7C, Section 12.4.
12.4 Total µg NO2 Per Sample.

m = 250 
1000   46.01
(S − B) Eq. 7D-2
 50   62.01
= 3710 (S − B)
Where:
250 = Volume of prepared sample, ml.
1000 = Total volume of KMnO4 solution, ml.
50 = Aliquot of KMnO4/NaOH solution, ml.
46.01 = Molecular weight of NO3¥.
62.01 = Molecular weight of NO3¥.
12.5 Sample Concentration. Same as in Method 7C, Section 12.7.

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13.0 Method Performance
13.1 Precision. The intra-laboratory relative standard deviation for a single measurement is approximately 6 percent
at 200 to 270 ppm NOx.
13.2 Bias. The method does not exhibit any bias relative to Method 7.
13.3 Range. The lower detectable limit is similar to that of Method 7C. No upper limit has been established;
however, when using the recommended sampling conditions, the method has been found to collect NOX emissions
quantitatively up to 1782 mg NOX/m3, as NO2 (932 ppm NOx).
14.0 Pollution Prevention. [Reserved]
15.0 Waste Management. [Reserved]
16.0 References
Same as Method 7C, Section 16.0, References 1, 2, 4, and 5.

BILLING CODE 6560–50–P

17.0 Tables, Diagrams, Flowcharts, and Validation Data

BILLING CODE 6560–50–C Method 8—Determination of Sulfuric supplies) and procedures (e.g., sampling and
* * * * * Acid and Sulfur Dioxide Emissions analytical) essential to its performance. Some
From Stationary Sources material is incorporated by reference from
other methods in this part. Therefore, to
Note: This method does not include all of obtain reliable results, persons using this
the specifications (e.g., equipment and method should have a thorough knowledge

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61922 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

of at least the following additional test methods: Method 1, Method 2, Method 3, 1.0 Scope and Application
Method 5, and Method 6.
1.1 Analytes.

Analyte CAS No. Sensitivity

Sulfuric acid, including: Sulfuric 7664–93–9, 7449–11–9 ................................... 0.05 mg/m3 (0.03 × 10¥7 lb/ft3).
acid (H2SO4) mist, Sulfur tri-
oxide (SO3).
Sulfur dioxide (SO2) .................. 7449–09–5 ....................................................... 1.2 mg/m3 (3 × 10¥9 lb/ft3).

1.2 Applicability. This method is method is shown in Figure 8–1; it is 6.3.3 Erlenmeyer Flask. 250-ml (one
applicable for the determination of similar to the Method 5 sampling train, for each sample, blank, and standard).
H2SO4 (including H2SO4 mist and SO3) except that the filter position is 6.3.4 Graduated Cylinder. 100-ml.
and gaseous SO2 emissions from different, and the filter holder does not 6.3.5 Dropping Bottle. To add
stationary sources. have to be heated. See Method 5, indicator solution, 125-ml size.
Note: Filterable particulate matter may be Section 6.1.1, for details and guidelines 7.0 Reagents and Standards
determined along with H2SO4 and SO2 on operation and maintenance.
(subject to the approval of the Administrator) 6.1.1.1 Probe Liner. Borosilicate or Note: Unless otherwise indicated, all
by inserting a heated glass fiber filter quartz glass, with a heating system to reagents are to conform to the specifications
between the probe and isopropanol impinger prevent visible condensation during established by the Committee on Analytical
(see Section 6.1.1 of Method 6). If this option Reagents of the American Chemical Society,
sampling. Do not use metal probe liners. where such specifications are available.
is chosen, particulate analysis is gravimetric
6.1.1.2 Filter Holder. Borosilicate Otherwise, use the best available grade.
only; sulfuric acid is not determined
separately. glass, with a glass frit filter support and
a silicone rubber gasket. Other gasket 7.1 Sample Collection. The
1.3 Data Quality Objectives. materials (e.g., Teflon or Viton) may be following reagents are required for
Adherence to the requirements of this used, subject to the approval of the sample collection:
method will enhance the quality of the Administrator. The holder design shall 7.1.1 Filters and Silica Gel. Same as
data obtained from air pollutant provide a positive seal against leakage in Method 5, Sections 7.1.1 and 7.1.2,
sampling methods. respectively.
from the outside or around the filter.
7.1.2 Water. Same as in Method 6,
2.0 Summary of Method The filter holder shall be placed
Section 7.1.1.
between the first and second impingers. 7.1.3 Isopropanol, 80 Percent by
A gas sample is extracted
Do not heat the filter holder. Volume. Mix 800 ml of isopropanol
isokinetically from the stack. The H2SO4
6.1.1.3 Impingers. Four, of the with 200 ml of water.
and the SO2 are separated, and both
Greenburg-Smith design, as shown in
fractions are measured separately by the Note: Check for peroxide impurities using
Figure 8–1. The first and third
barium-thorin titration method. the procedure outlined in Method 6, Section
impingers must have standard tips. The
7.1.2.1.
3.0 Definitions. [Reserved] second and fourth impingers must be
modified by replacing the insert with an 7.1.4 Hydrogen Peroxide (H2O2), 3
4.0 Interferences Percent by Volume. Dilute 100 ml of 30
approximately 13-mm (1⁄2-in.) ID glass
4.1 Possible interfering agents of this tube, having an unconstricted tip percent H2O2) to 1 liter with water.
method are fluorides, free ammonia, and located 13 mm (1⁄2 in.) from the bottom Prepare fresh daily.
dimethyl aniline. If any of these 7.1.5 Crushed Ice.
of the impinger. Similar collection 7.2 Sample Recovery. The reagents
interfering agents is present (this can be systems, subject to the approval of the
determined by knowledge of the and standards required for sample
Administrator, may be used. recovery are:
process), alternative methods, subject to 6.1.1.4 Temperature Sensor.
the approval of the Administrator, are 7.2.1 Water. Same as in Section
Thermometer, or equivalent, to measure 7.1.2.
required. the temperature of the gas leaving the 7.2.2 Isopropanol, 80 Percent. Same
5.0 Safety impinger train to within 1 °C (2 °F). as in Section 7.1.3.
5.1 Disclaimer. This method may 6.2 Sample Recovery. The following 7.3 Sample Analysis. Same as
involve hazardous materials, operations, items are required for sample recovery: Method 6, Section 7.3.
and equipment. This test method may 6.2.1 Wash Bottles. Two 7.3.1 Quality Assurance Audit
not address all of the safety problems polyethylene or glass bottles, 500-ml. Samples. When making compliance
associated with its use. It is the 6.2.2 Graduated Cylinders. Two determinations, and upon availability,
responsibility of the user of this test graduated cylinders (volumetric flasks audit samples may be obtained from the
method to establish appropriate safety may be used), 250-ml, 1-liter. appropriate EPA Regional Office or from
and health practices and determine the 6.2.3 Storage Bottles. Leak-free the responsible enforcement authority.
applicability of regulatory limitations polyethylene bottles, 1-liter size (two for Note: The responsible enforcement
prior to performing this test method. each sampling run). authority should be notified at least 30 days
5.2 Corrosive reagents. Same as 6.2.4 Trip Balance. 500-g capacity, prior to the test date to allow sufficient time
Method 6, Section 5.2. to measure to ± 0.5 g (necessary only if for sample delivery.
a moisture content analysis is to be
6.0 Equipment and Supplies done). 8.0 Sample Collection, Preservation,
6.1 Sample Collection. Same as 6.3 Analysis. The following items Storage, and Transport
Method 5, Section 6.1, with the are required for sample analysis: 8.1 Pretest Preparation. Same as
following additions and exceptions: 6.3.1 Pipettes. Volumetric 10-ml, Method 5, Section 8.1, except that filters
6.1.1 Sampling Train. A schematic 100-ml. should be inspected but need not be
of the sampling train used in this 6.3.2 Burette. 50-ml. desiccated, weighed, or identified. If the

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effluent gas can be considered dry (i.e., test, observe the connecting line probe to cool. Treat the samples as
moisture-free), the silica gel need not be between the probe and first impinger for follows:
weighed. signs of condensation. If condensation 8.8.1 Container No. 1.
8.2 Preliminary Determinations. does occur, adjust the probe heater 8.8.1.1 If a moisture content analysis
Same as Method 5, Section 8.2. setting upward to the minimum is to be performed, clean and weigh the
8.3 Preparation of Sampling Train. temperature required to prevent first impinger (plus contents) to the
Same as Method 5, Section 8.3, with the condensation. If component changes nearest 0.5 g, and record this weight.
following exceptions: become necessary during a run, a leak- 8.8.1.2 Transfer the contents of the
8.3.1 Use Figure 8–1 instead of check shall be performed immediately first impinger to a 250-ml graduated
Figure 5–1. before each change, according to the
8.3.2 Replace the second sentence of cylinder. Rinse the probe, first impinger,
procedure outlined in Section 8.4.3 of all connecting glassware before the
Method 5, Section 8.3.1 with: Place 100 Method 5 (with appropriate
ml of 80 percent isopropanol in the first filter, and the front half of the filter
modifications, as mentioned in Section holder with 80 percent isopropanol.
impinger, 100 ml of 3 percent H2O2 in 8.5 of this method); record all leak rates.
both the second and third impingers; Add the isopropanol rinse solution to
If the leakage rate(s) exceeds the the cylinder. Dilute the contents of the
retain a portion of each reagent for use specified rate, the tester shall either
as a blank solution. Place about 200 g cylinder to 225 ml with 80 percent
void the run or plan to correct the isopropanol, and transfer the cylinder
of silica gel in the fourth impinger. sample volume as outlined in Section
8.3.3 Ignore any other statements in contents to the storage container. Rinse
12.3 of Method 5. Leak-checks the cylinder with 25 ml of 80 percent
Section 8.3 of Method 5 that are immediately after component changes
obviously not applicable to the isopropanol, and transfer the rinse to
are recommended, but not required. If the storage container. Add the filter to
performance of Method 8. these leak-checks are performed, the the solution in the storage container and
Note: If moisture content is to be procedure in Section 8.4.2 of Method 5 mix. Seal the container to protect the
determined by impinger analysis, weigh each (with appropriate modifications) shall solution against evaporation. Mark the
of the first three impingers (plus absorbing be used.
solution) to the nearest 0.5 g, and record level of liquid on the container, and
8.6.2 After turning off the pump and identify the sample container.
these weights. Weigh also the silica gel (or
silica gel plus container) to the nearest 0.5 g, recording the final readings at the 8.8.2 Container No. 2.
and record.) conclusion of each run, remove the 8.8.2.1 If a moisture content analysis
probe from the stack. Conduct a post- is to be performed, clean and weigh the
8.4 Metering System Leak-Check test (mandatory) leak-check as outlined
Procedure. Same as Method 5, Section second and third impingers (plus
in Section 8.4.4 of Method 5 (with contents) to the nearest 0.5 g, and record
8.4.1. appropriate modifications), and record
8.5 Pretest Leak-Check Procedure. the weights. Also, weigh the spent silica
the leak rate. If the post-test leakage rate gel (or silica gel plus impinger) to the
Follow the basic procedure in Method 5, exceeds the specified acceptable rate,
Section 8.4.2, noting that the probe nearest 0.5 g, and record the weight.
either correct the sample volume, as
heater shall be adjusted to the minimum 8.8.2.2 Transfer the solutions from
outlined in Section 12.3 of Method 5, or
temperature required to prevent the second and third impingers to a 1-
void the run.
condensation, and also that verbage liter graduated cylinder. Rinse all
8.6.3 Drain the ice bath and, with connecting glassware (including back
such as ‘‘* * * plugging the inlet to the the probe disconnected, purge the
filter holder * * * ’’ found in Section half of filter holder) between the filter
remaining part of the train by drawing and silica gel impinger with water, and
8.4.2.2 of Method 5 shall be replaced by clean ambient air through the system for
‘‘ * * * plugging the inlet to the first add this rinse water to the cylinder.
15 minutes at the average flow rate used Dilute the contents of the cylinder to
impinger * * * ’’. The pretest leak-check for sampling.
is recommended, but is not required. 950 ml with water. Transfer the solution
8.6 Sampling Train Operation. Note: Clean ambient air can be provided by to a storage container. Rinse the
Follow the basic procedures in Method passing air through a charcoal filter. cylinder with 50 ml of water, and
5, Section 8.5, in conjunction with the Alternatively, ambient air (without cleaning) transfer the rinse to the storage
following special instructions: may be used. container. Mark the level of liquid on
8.6.1 Record the data on a sheet 8.7 Calculation of Percent Isokinetic. the container. Seal and identify the
similar to that shown in Figure 8–2 Same as Method 5, Section 8.6. sample container.
(alternatively, Figure 5–2 in Method 5 8.8 Sample Recovery. Proper
9.0 Quality Control
may be used). The sampling rate shall cleanup procedure begins as soon as the
not exceed 0.030 m3/min (1.0 cfm) probe is removed from the stack at the 9.1 Miscellaneous Quality Control
during the run. Periodically during the end of the sampling period. Allow the Measures.

Section Quality control measure Effect

7.1.3 .......................................... Isopropanol check ............................................ Ensure acceptable level of peroxide impurities in isopropanol.
8.4, 8.5, 10.1 ............................. Sampling equipment leak-check and calibra- Ensure accurate measurement of stack gas flow rate, sample
tion. volume.
10.2 ........................................... Barium standard solution standardization ........ Ensure normality determination.
11.2 ........................................... Replicate titrations ............................................ Ensure precision of titration determinations.
11.3 ........................................... Audit sample analysis ...................................... Evaluate analyst’s technique and standards preparation.

9.2 Volume Metering System 10.0 Calibration and Standardization 10.2 Barium Standard Solution.
Checks. Same as Method 5, Section 9.2. Same as Method 6, Section 10.5.
10.1 Sampling Equipment. Same as
Method 5, Section 10.0.

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61924 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

11.0 Analytical Procedure 11.3.3 The same analyst, analytical that of the acquired data. Round off
11.1. Sample Loss. Same as Method reagents, and analytical system shall be figures after final calculation.
used for the compliance samples and 12.1 Nomenclature. Same as Method
6, Section 11.1.
the EPA audit samples. If this condition 5, Section 12.1, with the following
11.2. Sample Analysis.
is met, duplicate auditing of subsequent additions and exceptions:
11.2.1 Container No. 1. Shake the
compliance analyses for the same Ca = Actual concentration of SO2 in
container holding the isopropanol
enforcement agency within a 30-day audit sample, mg/dscm.
solution and the filter. If the filter breaks period is waived. Audit samples may
up, allow the fragments to settle for a Cd = Determined concentration of SO2 in
not be used to validate different
few minutes before removing a sample audit sample, mg/dscm.
compliance samples under the
aliquot. Pipette a 100-ml aliquot of this CH2SO4 = Sulfuric acid (including SO3)
jurisdiction of separate enforcement
solution into a 250-ml Erlenmeyer flask, concentration, g/dscm (lb/dscf).
agencies, unless prior arrangements
add 2 to 4 drops of thorin indicator, and have been made with both enforcement CSO2 = Sulfur dioxide concentration, g/
titrate to a pink endpoint using 0.0100 agencies. dscm (lb/dscf).
N barium standard solution. Repeat the 11.4 Audit Sample Results. N = Normality of barium perchlorate
titration with a second aliquot of 11.4.1 Calculate the audit sample titrant, meq/ml.
sample, and average the titration values. concentrations in mg/dscm and submit RE = Relative error of QA audit sample
Replicate titrations must agree within 1 results using the instructions provided analysis, percent
percent or 0.2 ml, whichever is greater. with the audit samples. Va = Volume of sample aliquot titrated,
11.2.2 Container No. 2. Thoroughly 11.4.2 Report the results of the audit 100 ml for H2SO4 and 10 ml for
mix the solution in the container samples and the compliance SO2.
holding the contents of the second and determination samples along with their Vsoln = Total volume of solution in
third impingers. Pipette a 10-ml aliquot identification numbers, and the which the sample is contained, 250
of sample into a 250-ml Erlenmeyer analyst’s name to the responsible ml for the SO2 sample and 1000 ml
flask. Add 40 ml of isopropanol, 2 to 4 enforcement authority. Include this for the H2SO4 sample.
drops of thorin indicator, and titrate to information with reports of any Vt = Volume of barium standard
a pink endpoint using 0.0100 N barium subsequent compliance analyses for the solution titrant used for the sample,
standard solution. Repeat the titration same enforcement authority during the ml.
with a second aliquot of sample, and 30-day period. Vtb = Volume of barium standard
average the titration values. Replicate 11.4.3 The concentrations of the solution titrant used for the blank,
titrations must agree within 1 percent or audit samples obtained by the analyst ml.
0.2 ml, whichever is greater. shall agree within 5 percent of the
actual concentrations. If the 5 percent 12.2 Average Dry Gas Meter
11.2.3 Blanks. Prepare blanks by
specification is not met, reanalyze the Temperature and Average Orifice
adding 2 to 4 drops of thorin indicator
compliance and audit samples, and Pressure Drop. See data sheet (Figure 8–
to 100 ml of 80 percent isopropanol.
include initial and reanalysis values in 2).
Titrate the blanks in the same manner
as the samples. the test report. 12.3 Dry Gas Volume. Same as
11.3 Audit Sample Analysis. 11.4.4 Failure to meet the 5 percent Method 5, Section 12.3.
11.3.1 When the method is used to specification may require retests until 12.4 Volume of Water Vapor
analyze samples to demonstrate the audit problems are resolved. Condensed and Moisture Content.
compliance with a source emission However, if the audit results do not Calculate the volume of water vapor
regulation, EPA audit samples must be affect the compliance or noncompliance using Equation 5–2 of Method 5; the
analyzed, subject to availability. status of the affected facility, the weight of water collected in the
11.3.2 Concurrently analyze audit Administrator may waive the reanalysis impingers and silica gel can be
samples and the compliance samples in requirement, further audits, or retests converted directly to milliliters (the
the same manner to evaluate the and accept the results of the compliance specific gravity of water is 1 g/ml).
technique of the analyst and the test. While steps are being taken to Calculate the moisture content of the
standards preparation. resolve audit analysis problems, the stack gas (Bws) using Equation 5–3 of
Administrator may also choose to use Method 5. The Note in Section 12.5 of
Note: It is recommended that known Method 5 also applies to this method.
quality control samples be analyzed prior to
the data to determine the compliance or
noncompliance status of the affected Note that if the effluent gas stream can
the compliance and audit sample analyses to
facility. be considered dry, the volume of water
optimize the system accuracy and precision.
These quality control samples may be vapor and moisture content need not be
12.0 Data Analysis and Calculations calculated.
obtained by contacting the appropriate EPA
regional Office or the responsible Carry out calculations retaining at 12.5 Sulfuric Acid Mist (Including
enforcement authority. least one extra significant figure beyond SO3) Concentration.

[ ]
C H 2SO 4 = K 3 N (Vt − Vtb )(Vsoln / Va ) / Vm (std ) Eq. 8-1

Where:
K3 = 0.04904 g/meq for metric units,
K3 = 1.081 × 10¥4 lb/meq for English units.
12.6 Sulfur Dioxide Concentration.

[ ]
C SO2 = K 4 N (Vt − Vtb )(Vsoln / Va ) / Vm (std ) Eq. 8-2

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Where: 12.9 Relative Error (RE) for QA (35.3 ft3) gas sample is about 12,000 mg/
K4 = 0.03203 g/meq for metric units, Audit Samples. Same as Method 6, m3 (7.7 × 10¥4 lb/ft3). The upper limit
Section 12.4. can be extended by increasing the
K4 = 7.061 × 10¥5 lb/meq for English
units. 13.0 Method Performance quantity of peroxide solution in the
impingers.
12.7 Isokinetic Variation. Same as 13.1 Analytical Range. Collaborative
Method 5, Section 12.11. tests have shown that the minimum 14.0 Pollution Prevention. [Reserved]
12.8 Stack Gas Velocity and detectable limits of the method are 0.06 15.0 Waste Management. [Reserved]
Volumetric Flow Rate. Calculate the mg/m3 (4 × 10¥9 lb/ft3) for H2SO4 and
average stack gas velocity and 1.2 mg/m3 (74 × 10¥9 lb/ft3) for SO2. No 16.0 References
volumetric flow rate, if needed, using upper limits have been established.
data obtained in this method and the Based on theoretical calculations for 200 Same as Section 17.0 of Methods 5
equations in Sections 12.6 and 12.7 of ml of 3 percent H2O2 solution, the upper and 6.
Method 2. concentration limit for SO2 in a 1.0 m3 BILLING CODE 6560–50–C

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61926 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

17.0 Tables, Diagrams, Flowcharts, and Validation Data

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BILLING CODE 6560–50–C

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61928 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

Method 10A—Determination of Carbon supplies) and procedures (e.g., sampling and methods: Method 1, Method 4, and Method
Monoxide Emissions in Certifying analytical) essential to its performance. Some 5.
Continuous Emission Monitoring material is incorporated by reference from
Systems at Petroleum Refineries other methods in this part. Therefore, to 1.0 Scope and Application
obtain reliable results, persons using this
Note: This method does not include all of method should have a thorough knowledge 1.1 Analytes.
the specifications (e.g., equipment and of at least the following additional test

Analyte CAS No. Sensitivity

Carbon monoxide (CO) .................................................................................. 630–08–0 3 ppmv

1.2 Applicability. This method is taken with regard to the analytical 6.1.9 Volume Meter. Dry gas meter,
applicable for the determination of CO procedure. capable of measuring the sample
emissions at petroleum refineries. This 5.2 Corrosive reagents. The volume under calibration conditions of
method serves as the reference method following reagents are hazardous. 300 ml/min (0.01 ft3/min) for 10
in the relative accuracy test for Personal protective equipment and safe minutes.
nondispersive infrared (NDIR) CO procedures are useful in preventing 6.1.10 Pressure Gauge. A water filled
continuous emission monitoring chemical splashes. If contact occurs, U-tube manometer, or equivalent, of
systems (CEMS) that are required to be immediately flush with copious about 30 cm (12 in.) to leak-check the
installed in petroleum refineries on amounts of water for at least 15 minutes. flexible bag.
fluid catalytic cracking unit catalyst Remove clothing under shower and 6.2 Sample Analysis.
regenerators (§ 60.105(a)(2) of this part). decontaminate. Treat residual chemical 6.2.1 Spectrophotometer. Single- or
1.3 Data Quality Objectives. burns as thermal burns. double-beam to measure absorbance at
Adherence to the requirements of this 5.2.1 Sodium Hydroxide (NaOH). 425 and 600 nm. Slit width should not
method will enhance the quality of the Causes severe damage to eyes and skin. exceed 20 nm.
data obtained from air pollutant Inhalation causes irritation to nose, 6.2.2 Spectrophotometer Cells. 1-cm
sampling methods. throat, and lungs. Reacts exothermically pathlength.
6.2.3 Vacuum Gauge. U-tube
with limited amounts of water.
2.0 Summary of Method mercury manometer, 1 meter (39 in.),
An integrated gas sample is extracted 6.0 Equipment and Supplies with 1-mm divisions, or other gauge
from the stack, passed through an 6.1 Sample Collection. The sampling capable of measuring pressure to within
alkaline permanganate solution to train shown in Figure 10A–1 is required 1 mm Hg.
remove sulfur oxides and nitrogen 6.2.4 Pump. Capable of evacuating
for sample collection. Component parts
oxides, and collected in a Tedlar bag. the gas reaction bulb to a pressure equal
are described below:
The CO concentration in the sample is to or less than 40 mm Hg absolute,
6.1.1 Probe. Stainless steel, sheathed
measured spectrophotometrically using equipped with coarse and fine flow
Pyrex glass, or equivalent, equipped
the reaction of CO with p- control valves.
with a glass wool plug to remove 6.2.5 Barometer. Mercury, aneroid,
sulfaminobenzoic acid. particulate matter. or other barometer capable of measuring
3.0 Definitions. [Reserved] 6.1.2 Sample Conditioning System. atmospheric pressure to within 1 mm
Three Greenburg-Smith impingers Hg.
4.0 Interferences connected in series with leak-free 6.2.6 Reaction Bulbs. Pyrex glass,
Sulfur oxides, nitric oxide, and other connections. 100-ml with Teflon stopcock (Figure
acid gases interfere with the 6.1.3 Pump. Leak-free pump with 10A–2), leak-free at 40 mm Hg, designed
colorimetric reaction. They are removed stainless steel and Teflon parts to so that 10 ml of the colorimetric reagent
by passing the sampled gas through an transport sample at a flow rate of 300 can be added and removed easily and
alkaline potassium permanganate ml/min (0.01 ft3/min) to the flexible bag. accurately. Commercially available gas
scrubbing solution. Carbon dioxide 6.1.4 Surge Tank. Installed between sample bulbs such as Supelco Catalog
(CO2) does not interfere, but, because it the pump and the rate meter to No. 2–2161 may also be used.
is removed by the scrubbing solution, its eliminate the pulsation effect of the 6.2.7 Manifold. Stainless steel, with
concentration must be measured pump on the rate meter. connections for three reaction bulbs and
independently and an appropriate 6.1.5 Rate Meter. Rotameter, or the appropriate connections for the
volume correction made to the sampled equivalent, to measure flow rate at 300 manometer and sampling bag as shown
gas. ml/min (0.01 ft3/min). Calibrate in Figure 10A–3.
according to Section 10.2. 6.2.8 Pipets. Class A, 10–ml size.
5.0 Safety 6.1.6 Flexible Bag. Tedlar, or 6.2.9 Shaker Table. Reciprocating-
5.1 Disclaimer. This method may equivalent, with a capacity of 10 liters stroke type such as Eberbach
involve hazardous materials, operations, (0.35 ft3) and equipped with a sealing Corporation, Model 6015. A rocking arm
and equipment. This test method may quick-connect plug. The bag must be or rotary-motion type shaker may also
not address all of the safety problems leak-free according to Section 8.1. For be used. The shaker must be large
associated with its use. It is the protection, it is recommended that the enough to accommodate at least six gas
responsibility of the user of this test bag be enclosed within a rigid container. sample bulbs simultaneously. It may be
method to establish appropriate safety 6.1.7 Valves. Stainless-steel needle necessary to construct a table top
and health practices and determine the valve to adjust flow rate, and stainless- extension for most commercial shakers
applicability of regulatory limitations steel three-way valve, or equivalent. to provide sufficient space for the
prior to performing this test method. 6.1.8 CO2 Analyzer. Fyrite, or needed bulbs (Figure 10A–4).
The analyzer users manual should be equivalent, to measure CO2 6.2.10 Valve. Stainless steel shut-off
consulted for specific precautions to be concentration to within O.5 percent. valve.

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6.2.11 Analytical Balance. Capable NaOH with shaking. The resultant first two impingers and 250 ml in the
of weighing to 0.1 mg. solution should be clear and colorless. third. Connect the pump to the third
This solution is acceptable for use for a impinger, and follow this with the surge
7.0 Reagents and Standards
period of 2 days. tank, rate meter, and 3-way valve. Do
Unless otherwise indicated, all 7.2.7 Standard Gas Mixtures. not connect the Tedlar bag to the system
reagents shall conform to the Traceable to National Institute of at this time.
specifications established by the Standards and Technology (NIST) 8.2.2 Leak-check the sampling
Committee on Analytical Reagents of standards and containing between 50 system by plugging the probe inlet,
the American Chemical Society, where and 1000 ppm CO in nitrogen. At least opening the 3-way valve, and pulling a
such specifications are available; two concentrations are needed to span vacuum of approximately 250 mm Hg
otherwise, the best available grade shall each calibration range used (Section on the system while observing the rate
be used. 10.3). The calibration gases must be
7.1 Sample Collection. meter for flow. If flow is indicated on
certified by the manufacturer to be the rate meter, do not proceed further
7.1.1 Water. Deionized distilled, to within 2 percent of the specified
conform to ASTM D 1193–77 or 91, until the leak is found and corrected.
concentrations. 8.2.3 Purge the system with sample
Type 3 (incorporated by reference—see
§ 60.17). If high concentrations of 8.0 Sample Collection, Preservation, gas by inserting the probe into the stack
organic matter are not expected to be Storage, and Transport and drawing the sample gas through the
present, the potassium permanganate system at 300 ml/min ± 10 percent for
8.1 Sample Bag Leak-Checks. While
test for oxidizable organic matter may be 5 minutes. Connect the evacuated
a bag leak-check is required after bag
omitted. Tedlar bag to the system, record the
use, it should also be done before the
7.1.2 Alkaline Permanganate starting time, and sample at a rate of 300
bag is used for sample collection. The
Solution, 0.25 M KMnO4/1.5 M Sodium ml/min for 30 minutes, or until the
bag should be leak-checked in the
Hydroxide (NaOH). Dissolve 40 g Tedlar bag is nearly full. Record the
inflated and deflated condition
KMnO4 and 60 g NaOH in sampling time, the barometric pressure,
according to the following procedure:
approximately 900 ml water, cool, and and the ambient temperature. Purge the
8.1.1 Connect the bag to a water
dilute to 1 liter. system as described above immediately
manometer, and pressurize the bag to 5
7.2 Sample Analysis. before each sample.
7.2.1 Water. Same as in Section 7.1.1. to 10 cm H2O (2 to 4 in H2O). Allow the
bag to stand for 60 minutes. Any 8.2.4 The scrubbing solution is
7.2.2 1 M Sodium Hydroxide adequate for removing sulfur oxides and
Solution. Dissolve 40 g NaOH in displacement in the water manometer
indicates a leak. nitrogen oxides from 50 liters (1.8 ft3) of
approximately 900 ml of water, cool, stack gas when the concentration of
and dilute to 1 liter. 8.1.2 Evacuate the bag with a
leakless pump that is connected to the each is less than 1,000 ppm and the CO2
7.2.3 0.1 M NaOH Solution. Dilute
downstream side of a flow indicating concentration is less than 15 percent.
50 ml of the 1 M NaOH solution
device such as a 0- to 100-ml/min Replace the scrubber solution after
prepared in Section 7.2.2 to 500 ml.
rotameter or an impinger containing every fifth sample.
7.2.4 0.1 M Silver Nitrate (AgNO3)
Solution. Dissolve 8.5 g AgNO3 in water, water. When the bag is completely 8.3 Carbon Dioxide Measurement.
and dilute to 500 ml. evacuated, no flow should be evident if Measure the CO2 content in the stack to
7.2.5 0.1 M Para-Sulfaminobenzoic the bag is leak-free. the nearest 0.5 percent each time a CO
Acid (p-SABA) Solution. Dissolve 10.0 8.2 Sample Collection. sample is collected. A simultaneous
g p-SABA in 0.1 M NaOH, and dilute to 8.2.1 Evacuate the Tedlar bag grab sample analyzed by the Fyrite
500 ml with 0.1 M NaOH. completely using a vacuum pump. analyzer is acceptable.
7.2.6 Colorimetric Solution. To a Assemble the apparatus as shown in 9.0 Quality Control
flask, add 100 ml of 0.1 M p-SABA Figure 10A–1. Loosely pack glass wool
solution and 100 ml of 0.1 M AgNO3 in the tip of the probe. Place 400 ml of 9.1 Miscellaneous Quality Control
solution. Mix, and add 50 ml of 1 M alkaline permanganate solution in the Measures.

Section Quality control measure Effect

8.1 ............................................. Sampling equipment leak-checks and calibra- Ensure accuracy and precision of sampling measurements.
tion.
10.3 ........................................... Spectrophotometer calibration ......................... Ensure linearity of spectrophotometer response to standards.

9.2 Volume Metering System volume on the bulb. Alternatively, mark determine the volume of gas that passed
Checks. Same as Method 5, Section 9.2. an identification number on the bulb, through the system.
10.0 Calibration and Standardization and record the volume in a notebook. 10.3 Spectrophotometer Calibration
10.2 Rate Meter Calibration. Curve.
Note: Maintain a laboratory log of all Assemble the system as shown in Figure 10.3.1 Collect the standards as
calibrations.
10A–1 (the impingers may be removed), described in Section 8.2. Prepare at least
10.1 Gas Bulb Calibration. Weigh the and attach a volume meter to the probe two sets of three bulbs as standards to
empty bulb to the nearest 0.1 g. Fill the inlet. Set the rotameter at 300 ml/min, span the 0 to 400 or 400 to 1000 ppm
bulb to the stopcock with water, and record the volume meter reading, start range. If any samples span both
again weigh to the nearest 0.1 g. the pump, and pull ambient air through concentration ranges, prepare a
Subtract the tare weight, and calculate the system for 10 minutes. Record the calibration curve for each range using
the volume in liters to three significant final volume meter reading. Repeat the separate reagent blanks. Prepare a set of
figures using the density of water at the procedure and average the results to three bulbs containing colorimetric
measurement temperature. Record the reagent but no CO to serve as a reagent

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blank. Analyze each standard and blank at 600 nm if the concentration is above value, and calculate a new average using
according to the sample analysis 400 ppm. the two remaining values.
procedure of Section 11.0 Reject the Note: This may be accomplished with
standard set where any of the individual multiple bulb sets by sequentially collecting
As =
(A − A r ) (Pb ) Eq. 10A-1
(Vb − Vr ) (Pb − Pv )
bulb absorbances differs from the set sets and adding to the shaker at staggered
mean by more than 10 percent. intervals, followed by sequentially removing
10.3.2 Calculate the average sets from the shaker for absorbance
Note: A and Ar must be at the same
measurement after the two-hour designated
absorbance for each set (3 bulbs) of intervals have elapsed. wavelength.
standards using Equation 10A–1 and 12.3 CO Concentration in the Bag.
Table 10A–1. Construct a graph of 11.4 Use a small portion of the
Calculate Cb using Equations 10A–2 and
average absorbance for each standard sample to rinse a spectrophotometer cell
10A–3. If condensate is visible in the
against its corresponding concentration. several times before taking an aliquot for
Tedlar bag, calculate Bw using Table
Draw a smooth curve through the analysis. If one cell is used to analyze
10A–2 and the temperature and
points. The curve should be linear over multiple samples, rinse the cell with
barometric pressure in the analysis
the two concentration ranges discussed deionized distilled water several times
room. If condensate is not visible,
in Section 13.3. between samples. Prepare and analyze
calculate Bw using the temperature and
standards and a reagent blank as
11.0 Analytical Procedure barometric pressure at the sampling site.
described in Section 10.3. Use water as
11.1 Assemble the system shown in the reference. Reject the analysis if the Pw
Figure 10A–3, and record the blank absorbance is greater than 0.1. All Bw = Eq. 10A-2
conditions should be the same for Pb
information required in Table 10A–1 as
it is obtained. Pipet 10.0 ml of the analysis of samples and standards.
colorimetric reagent into each gas Measure the absorbances as soon as
reaction bulb, and attach the bulbs to possible after shaking is completed. Cg
11.5 Determine the CO Cb = Eq. 10A-3
the system. Open the stopcocks to the
reaction bulbs, but leave the valve to the concentration of each bag sample using (1 − Bw )
Tedlar bag closed. Turn on the pump, the calibration curve for the appropriate 12.4 CO Concentration in the Stack.
fully open the coarse-adjust flow valve, concentration range as discussed in
and slowly open the fine-adjust valve Section 10.3. C = C b (1 − F) Eq. 10A-4
until the pressure is reduced to at least 12.0 Calculations and Data Analysis 13.0 Method Performance
40 mm Hg. Now close the coarse adjust
Carry out calculations retaining at 13.1 Precision. The estimated
valve, and observe the manometer to be
least one extra decimal figure beyond intralaboratory standard deviation of the
certain that the system is leak-free. Wait
that of the acquired data. Round off method is 3 percent of the mean for gas
a minimum of 2 minutes. If the pressure
figures after final calculation. samples analyzed in duplicate in the
has increased less than 1 mm Hg,
12.1 Nomenclature. concentration range of 39 to 412 ppm.
proceed as described below. If a leak is
present, find and correct it before A = Sample absorbance, uncorrected for The interlaboratory precision has not
proceeding further. the reagent blank. been established.
11.2 Record the vacuum pressure Ar = Absorbance of the reagent blank. 13.2 Accuracy. The method contains
(Pv) to the nearest 1 mm Hg, and close As = Average sample absorbance per no significant biases when compared to
the reaction bulb stopcocks. Open the liter, units/liter. an NDIR analyzer calibrated with NIST
Tedlar bag valve, and allow the system Bw = Moisture content in the bag standards.
to come to atmospheric pressure. Close sample. 13.3 Range. Approximately 3 to
the bag valve, open the pump coarse C = CO concentration in the stack gas, 1800 ppm CO. Samples having
adjust valve, and evacuate the system dry basis, ppm. concentrations below 400 ppm are
again. Repeat this fill/evacuation Cb = CO concentration of the bag analyzed at 425 nm, and samples having
procedure at least twice to flush the sample, dry basis, ppm. concentrations above 400 ppm are
manifold completely. Close the pump Cg = CO concentration from the analyzed at 600 nm.
coarse adjust valve, open the Tedlar bag calibration curve, ppm. 13.4 Sensitivity. The detection limit
valve, and let the system fill to F = Volume fraction of CO2 in the stack. is 3 ppmv based on a change in
atmospheric pressure. Open the n = Number of reaction bulbs used per concentration equal to three times the
stopcocks to the reaction bulbs, and let bag sample. standard deviation of the reagent blank
the entire system come to atmospheric Pb = Barometric pressure, mm Hg. solution.
pressure. Close the bulb stopcocks, Pv = Residual pressure in the sample 13.5 Stability. The individual
remove the bulbs, record the room bulb after evacuation, mm Hg. components of the colorimetric reagent
temperature and barometric pressure Pw = Vapor pressure of H2O in the bag are stable for at least 1 month. The
(Pbar, to nearest mm Hg), and place the (from Table 10A–2), mm Hg. colorimetric reagent must be used
bulbs on the shaker table with their Vb = Volume of the sample bulb, liters. within 2 days after preparation to avoid
main axis either parallel to or Vr = Volume of reagent added to the excessive blank correction. The samples
perpendicular to the plane of the table sample bulb, 0.0100 liter. in the Tedlar bag should be stable for at
top. Purge the bulb-filling system with least 1 week if the bags are leak-free.
12.2 Average Sample Absorbance
ambient air for several minutes between per Liter. Calculate As for each gas bulb 14.0 Pollution Prevention. [Reserved]
samples. Shake the samples for exactly using Equation 10A–1, and record the 15.0 Waste Management. [Reserved]
2 hours. value in Table 10A–1. Calculate the
11.3 Immediately after shaking, average As for each bag sample, and 16.0 References
measure the absorbance (A) of each bulb compare the three values to the average. 1. Butler, F.E., J.E. Knoll, and M.R. Midgett.
sample at 425 nm if the concentration If any single value differs by more than Development and Evaluation of Methods for
is less than or equal to 400 ppm CO or 10 percent from the average, reject this Determining Carbon Monoxide Emissions.

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U.S. Environmental Protection Agency, Analytical Chemistry. 46(7):929–930. June 6. Smith, F., D.E. Wagoner, and R.P.
Research Triangle Park, N.C. June 1985. 33 1974. Donovan. Guidelines for Development of a
pp. 4. Levaggi, D.A., and M. Feldstein. The Quality Assurance Program: Volume VIII—
2. Ferguson, B.B., R.E. Lester, and W.J. Colorimetric Determination of Low Determination of CO Emissions from
Mitchell. Field Evaluation of Carbon Concentrations of Carbon Monoxide. Stationary Sources by NDIR Spectrometry.
Industrial Hygiene Journal. 25:64–66.
Monoxide and Hydrogen Sulfide Continuous U.S. Environmental Protection Agency.
January-February 1964.
Emission Monitors at an Oil Refinery. U.S. Research Triangle Park, N.C. Publication No.
5. Repp, M. Evaluation of Continuous
Environmental Protection Agency, Research Monitors For Carbon Monoxide in Stationary EPA–650/4–74–005–h. February 1975. 96 pp.
Triangle Park, N.C. Publication No. EPA– Sources. U.S. Environmental Protection
600/4–82–054. August 1982. 100 pp. Agency. Research Triangle Park, N.C.
17.0 Tables, Diagrams, Flowcharts,
3. Lambert, J.L., and R.E. Weins. Induced Publication No. EPA–600/2–77–063. March and Validation Data
Colorimetric Method for Carbon Monoxide. 1977. 155 pp.

TABLE 10A–1.—DATA RECORDING SHEET FOR SAMPLES ANALYZED IN TRIPLICATE
Partial
Reagent pressure
Room Bulb Shaking Abs
Sample Stack Bulb vol. in of Pb,
temp vol. time, versus A–Ar As Avg As
No./type %CO2 No. bulb, gas in mm Hg
°C liters min water
liter bulb,
mm Hg

blank

Std. 1

Std. 2

Sample 1

Sample 2

Sample 3

TABLE 10A–2.—MOISTURE CORRECTION
Vapor Vapor
Temperature
Temperature °C pressure of pressure of
°C
H2,O, mm Hg H2, mm Hg

4 ................................................................................................................................................... 6.1 18 15.5
6 ................................................................................................................................................... 7.0 20 17.5
8 ................................................................................................................................................... 8.0 22 19.8
10 ................................................................................................................................................. 9.2 24 22.4
12 ................................................................................................................................................. 10.5 26 25.2
14 ................................................................................................................................................. 12.0 28 28.3
16 ................................................................................................................................................. 13.6 30 31.8

BILLING CODE 6560–50–P

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BILLING CODE 6560–50–C supplies) and procedures (e.g., sampling and methods: Method 1, Method 4, Method 10A,
Method 10B—Determination of Carbon analytical) essential to its performance. Some and Method 25.
Monoxide Emissions From Stationary material is incorporated by reference from
other methods in this part. Therefore, to 1.0 Scope and Application
Sources
obtain reliable results, persons using this
Note: This method is not inclusive with method should have a thorough knowledge 1.1 Analytes.
respect to specifications (e.g., equipment and of at least the following additional test

Analyte CAS No. Sensitivity

Carbon monoxide (CO) .................................................................................. 630–08–0 Not determined.

1.2 Applicability. This method 2.0 Summary of Method identical to applicable sections in
applies to the measurement of CO Method 25 detailing CO measurement.
emissions at petroleum refineries and 2.1 An integrated gas sample is
extracted from the sampling point, 3.0 Definitions. [Reserved]
from other sources when specified in an
applicable subpart of the regulations. passed through a conditioning system to 4.0 Interferences
remove interferences, and collected in a
1.3 Data Quality Objectives. Tedlar bag. The CO is separated from 4.1 Carbon dioxide (CO2) and
Adherence to the requirements of this the sample by gas chromatography (GC) organics potentially can interfere with
method will enhance the quality of the and catalytically reduced to methane the analysis. Most of the CO2 is removed
data obtained from air pollutant (CH4) which is determined by flame from the sample by the alkaline
sampling methods. ionization detection (FID). The permanganate conditioning system; any
analytical portion of this method is

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61936 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

residual CO2 and organics are separated (Method 25, Section 6.3) are acceptable permanently recording the analytical
from the CO by GC. alternatives when calibrated for CO and results.
operated in accordance with the Method
5.0 Safety 7.0 Reagents and Standards
25 analytical procedures (Method 25,
5.1 Disclaimer. This method may Section 11.0).] 7.1 Sample Collection. Same as in
involve hazardous materials, operations, 6.2.1 Separation Column. A column Method 10A, Section 7.1.
and equipment. This test method may capable of separating CO from CO2 and 7.2 Sample Analysis.
not address all of the safety problems organic compounds that may be present. 7.2.1 Carrier, Fuel, and Combustion
associated with its use. It is the A 3.2-mm (1⁄8-in.) OD stainless steel Gases. Same as in Method 25, Sections
responsibility of the user of this test column packed with 1.7 m (5.5 ft.) of 7.2.1, 7.2.2, and 7.2.3, respectively.
method to establish appropriate safety 60/80 mesh Carbosieve S–II (available 7.2.2 Calibration Gases. Three
and health practices and determine the from Supelco) has been used standard gases with nominal CO
applicability of regulatory limitations successfully for this purpose. concentrations of 20, 200, and 1,000
prior to performing this test method. 6.2.2 Reduction Catalyst. Same as in ppm CO in nitrogen. The calibration
The analyzer users manual should be Method 25, Section 6.3.1.2. gases shall be certified by the
consulted for specific precautions 6.2.3 Sample Injection System. Same manufacturer to be ± 2 percent of the
concerning the analytical procedure. as in Method 25, Section 6.3.1.4, specified concentrations.
equipped to accept a sample line from 7.2.3 Reduction Catalyst Efficiency
6.0 Equipment and Supplies
the Tedlar bag. Check Calibration Gas. Standard CH4
6.1 Sample Collection. Same as in 6.2.4 Flame Ionization Detector.
gas with a nominal concentration of
Method 10A, Section 6.1. Meeting the linearity specifications of
1,000 ppm in air.
6.2 Sample Analysis. A GC/FID Section 10.3 and having a minimal
analyzer, capable of quantifying CO in instrument range of 10 to 1,000 ppm 8.0 Sample Collection, Preservation,
the sample and consisting of at least the CO. Storage, and Transport
following major components, is required 6.2.5 Data Recording System. Analog
Same as in Method 10A, Section 8.0.
for sample analysis. [Alternatively, strip chart recorder or digital integration
complete Method 25 analytical systems system, compatible with the FID, for 9.0 Quality Control

Section Quality control measure Effect

8.0 ....................... Sample bag/sampling system leak-checks ............... Ensures that negative bias introduced through leakage is minimized.
10.1 ..................... Carrier gas blank check ............................................ Ensures that positive bias introduced by contamination of carrier gas
is less than 5 ppmv.
10.2 ..................... Reduction catalyst efficiency check .......................... Ensures that negative bias introduced by inefficient reduction catalyst
is less than 5 percent.
10.3 ..................... Analyzer calibration ................................................... Ensures linearity of analyzer response to standards.
11.2 ..................... Triplicate sample analyses ........................................ Ensures precision of analytical results.

10.0 Calibration and Standardization each gas, as well as the overall mean of 12.0 Calculations and Data Analysis
10.1 Carrier Gas Blank Check. the response factor values. The Carry out calculations retaining at
Analyze each new tank of carrier gas instrument linearity is acceptable if the least one extra significant figure beyond
with the GC analyzer according to average response factor of each that of the acquired data. Round off
Section 11.2 to check for contamination. calibration gas is within 2.5 percent of results only after the final calculation.
The corresponding concentration must the overall mean value and if the 12.1 Nomenclature.
be less than 5 ppm for the tank to be relative standard deviation (calculated
A = Average sample area.
acceptable for use. in Section 12.8 of Method 25) for each
Bw = Moisture content in the bag
10.2 Reduction Catalyst Efficiency set of triplicate injections is less than 2 sample, fraction.
Check. Prior to initial use, the reduction percent. Record the overall mean of the C = CO concentration in the stack gas,
catalyst shall be tested for reduction response factor values as the calibration dry basis, ppm.
efficiency. With the heated reduction response factor (R).
catalyst bypassed, make triplicate Cb = CO concentration in the bag
injections of the 1,000 ppm CH4 gas 11.0 Analytical Procedure sample, dry basis, ppm.
(Section 7.2.3) to calibrate the analyzer. F = Volume fraction of CO2 in the stack,
11.1 Preparation for Analysis. Before fraction.
Repeat the procedure using 1,000 ppm
CO gas (Section 7.2.2) with the catalyst putting the GC analyzer into routine Pbar = Barometric pressure, mm Hg.
in operation. The reduction catalyst operation, conduct the calibration Pw = Vapor pressure of the H2O in the
operation is acceptable if the CO procedures listed in Section 10.0. bag (from Table 10A–2, Method
response is within 5 percent of the Establish an appropriate carrier flow 10A), mm Hg.
certified gas value. rate and detector temperature for the R = Mean calibration response factor,
10.3 Analyzer Calibration. Perform specific instrument used. area/ppm.
this test before the system is first placed 11.2 Sample Analysis. Purge the 12.2 CO Concentration in the Bag.
into operation. With the reduction sample loop with sample, and then Calculate Cb using Equations 10B–1 and
catalyst in operation, conduct a linearity inject the sample. Analyze each sample 10B–2. If condensate is visible in the
check of the analyzer using the in triplicate, and calculate the average Tedlar bag, calculate Bw using Table
standards specified in Section 7.2.2. sample area (A). Determine the bag CO 10A–2 of Method 10A and the
Make triplicate injections of each concentration according to Section 12.2. temperature and barometric pressure in
calibration gas, and then calculate the the analysis room. If condensate is not
average response factor (area/ppm) for visible, calculate Bw using the

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temperature and barometric pressure at C = C b (1 − F) Eq. 10B- 3 Quality Assurance Division, Environmental
the sampling site. Monitoring Systems Laboratory, U.S.
13.0 Method Performance. [Reserved] Environmental Protection Agency, Research
P Triangle Park, NC. June 1985. 33 pp.
Bw = w Eq. 10B-1 14.0 Pollution Prevention. [Reserved]
Pbar 15.0 Waste Management. [Reserved] 17.0 Tables, Diagrams, Flowcharts,
and Validation Data. [Reserved]
16.0 References
Method 11—Determination of Hydrogen
A
Cb = Eq. 10B-2 Same as in Method 25, Section 16.0, Sulfide Content of Fuel Gas Streams in
R (1 − Bw ) with the addition of the following: Petroleum Refineries
1. Butler, F.E, J.E. Knoll, and M.R. Midgett. 1.0 Scope and Application
12.3 CO Concentration in the Stack Development and Evaluation of Methods for
Determining Carbon Monoxide Emissions. 1.1 Analytes.

Analyte CAS No. Sensitivity

Hydrogen sulfide (H2S) .................................................................................. 7783–06–4 8 mg/m3—740 mg/m3, (6 ppm—520 ppm).

1.2 Applicability. This method is data obtained from air pollutant sulfate (CdSO4) solution; H2S is
applicable for the determination of the sampling methods. absorbed, forming cadmium sulfide
H2S content of fuel gas streams at (CdS). The latter compound is then
2.0 Summary of Method
petroleum refineries. measured iodometrically.
1.3 Data Quality Objectives. 2.1 A sample is extracted from a
Adherence to the requirements of this source and passed through a series of 3.0 Definitions. [Reserved]
method will enhance the quality of the midget impingers containing a cadmium

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4.0 Interferences 5.2 Corrosive reagents. The silica gel, or equivalent, to dry the gas
following reagents are hazardous. sample and protect the meter and pump.
4.1 Any compound that reduces Personal protective equipment and safe If the silica gel has been used
iodine (I2) or oxidizes the iodide ion procedures are useful in preventing previously, dry at 175 °C (350 °F) for 2
will interfere in this procedure, chemical splashes. If contact occurs, hours. New silica gel may be used as
provided it is collected in the CdSO4 immediately flush with copious received. Alternatively, other types of
impingers. Sulfur dioxide in amounts of water for at least 15 minutes. desiccants (equivalent or better) may be
concentrations of up to 2,600 mg/m3 is Remove clothing under shower and used, subject to approval of the
removed with an impinger containing a decontaminate. Treat residual chemical Administrator.
hydrogen peroxide (H2O2) solution. burns as thermal burns. Note: Do not use more than 30 g of silica
Thiols precipitate with H2S. In the 5.2.1 Hydrogen Peroxide. Irritating gel. Silica gel adsorbs gases such as propane
absence of H2S, only traces of thiols are to eyes, skin, nose, and lungs. 30% H2O2 from the fuel gas stream, and use of excessive
collected. When methane-and ethane- is a strong oxidizing agent. Avoid amounts of silica gel could result in errors in
thiols at a total level of 300 mg/m3 are contact with skin, eyes, and combustible the determination of sample volume.
present in addition to H2S, the results material. Wear gloves when handling. 6.1.6 Sampling Valve. Needle valve,
vary from 2 percent low at an H2S 5.2.2 Hydrochloric Acid. Highly
or equivalent, to adjust gas flow rate.
concentration of 400 mg/m3 to 14 toxic. Vapors are highly irritating to
Stainless steel or other corrosion-
percent high at an H2S concentration of eyes, skin, nose, and lungs, causing
resistant material.
100 mg/m3. Carbonyl sulfide at a severe damage. May cause bronchitis,
concentration of 20 percent does not pneumonia, or edema of lungs. 6.1.7 Volume Meter. Dry gas meter
interfere. Certain carbonyl-containing Exposure to concentrations of 0.13 to (DGM), sufficiently accurate to measure
compounds react with iodine and 0.2 percent can be lethal in minutes. the sample volume within 2 percent,
produce recurring end points. However, Will react with metals, producing calibrated at the selected flow rate
acetaldehyde and acetone at hydrogen. (about 1.0 liter/min) and conditions
concentrations of 1 and 3 percent, actually encountered during sampling.
6.0 Equipment and Supplies The meter shall be equipped with a
respectively, do not interfere.
6.1 Sample Collection. The temperature sensor (dial thermometer or
4.2 Entrained H2O2 produces a equivalent) capable of measuring
following items are needed for sample
negative interference equivalent to 100 temperature to within 3 °C (5.4 °F). The
collection:
percent of that of an equimolar quantity 6.1.1 Sampling Line. Teflon tubing, gas meter should have a petcock, or
of H2S. Avoid the ejection of H2O2 into 6- to 7- mm (1⁄4-in.) ID, to connect the equivalent, on the outlet connector
the CdSO4 impingers. sampling train to the sampling valve. which can be closed during the leak-
5.0 Safety 6.1.2 Impingers. Five midget check. Gas volume for one revolution of
impingers, each with 30-ml capacity. the meter must not be more than 10
5.1 Disclaimer. This method may The internal diameter of the impinger liters.
involve hazardous materials, operations, tip must be 1 mm ± 0.05 mm. The 6.1.8 Rate Meter. Rotameter, or
and equipment. This test method may impinger tip must be positioned 4 to 6 equivalent, to measure flow rates in the
not address all of the safety problems mm from the bottom of the impinger. range from 0.5 to 2 liters/min (1 to 4 ft3/
associated with its use. It is the 6.1.3 Tubing. Glass or Teflon hr).
responsibility of the user of this test connecting tubing for the impingers.
method to establish appropriate safety 6.1.4 Ice Water Bath. To maintain 6.1.9 Graduated Cylinder. 25-ml
and health practices and determine the absorbing solution at a low temperature. size.
applicability of regulatory limitations 6.1.5 Drying Tube. Tube packed 6.1.10 Barometer. Mercury, aneroid,
prior to performing this test method. with 6- to 16- mesh indicating-type or other barometer capable of measuring

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atmospheric pressure to within 2.5 mm 6.3.2 Burette. 50-ml. light. Reagent bottles and flasks must be
Hg (0.1 in. Hg). In many cases, the 6.3.3 Erlenmeyer Flask. 125-ml. kept tightly stoppered.
barometric reading may be obtained 6.3.4 Volumetric Pipettes. One 25- 7.3 Sample Analysis. The following
from a nearby National Weather Service ml; two each 50- and 100-ml. reagents and standards are needed for
station, in which case, the station value 6.3.5 Volumetric Flasks. One 1000- sample analysis:
(which is the absolute barometric ml; two 500-ml. 7.3.1 Water. Same as in Section
pressure) shall be requested and an 6.3.6 Graduated Cylinders. One each 7.1.3.
adjustment for elevation differences 10- and 100-ml. 7.3.2 Standard Sodium Thiosulfate
between the weather station and the Solution, 0.1 N. Dissolve 24.8 g of
7.0 Reagents and Standards sodium thiosulfate pentahydrate
sampling point shall be applied at a rate
of minus 2.5 mm Hg (0.1 in Hg) per 30 Note: Unless otherwise indicated, it is (Na2S2O3·5H2O) or 15.8 g of anhydrous
m (100 ft) elevation increase or vice- intended that all reagents conform to the sodium thiosulfate (Na2S2O3) in 1 liter
versa for elevation decrease. specifications established by the Committee of water, and add 0.01 g of anhydrous
6.1.11 U-tube Manometer. 0-; to 30- on Analytical Reagents of the American sodium carbonate (Na2CO3) and 0.4 ml
cm water column, for leak-check Chemical Society, where such specifications of chloroform (CHCl3) to stabilize. Mix
procedure. are available. Otherwise, use the best thoroughly by shaking or by aerating
6.1.12 Rubber Squeeze Bulb. To available grade.
with nitrogen for approximately 15
pressurize train for leak-check. 7.1 Sample Collection. The minutes, and store in a glass-stoppered,
6.1.13 Tee, Pinchclamp, and following reagents are required for reagent bottle. Standardize as in Section
Connecting Tubing. For leak-check. sample collection: 10.2.2.
6.1.14 Pump. Diaphragm pump, or 7.1.1 CdSO4 Absorbing Solution. 7.3.3 Standard Sodium Thiosulfate
equivalent. Insert a small surge tank Dissolve 41 g of 3CdSO48H2O and 15 ml Solution, 0.01 N. Pipette 50.0 ml of the
between the pump and rate meter to of 0.1 M sulfuric acid in a 1-liter standard 0.1 N Na2S2O3 solution into a
minimize the pulsation effect of the volumetric flask that contains volumetric flask, and dilute to 500 ml
diaphragm pump on the rate meter. The approximately ⁄4 liter of water. Dilute to with water.
3

pump is used for the air purge at the end volume with deionized, distilled water. Note: A 0.01 N phenylarsine oxide
of the sample run; the pump is not Mix thoroughly. The pH should be 3 ± (C6H5AsO) solution may be prepared instead
ordinarily used during sampling, 0.1. Add 10 drops of Dow-Corning of 0.01 N Na2S2O3 (see Section 7.3.4).
because fuel gas streams are usually Antifoam B. Shake well before use. This 7.3.4 Standard Phenylarsine Oxide
sufficiently pressurized to force sample solution is stable for at least one month. Solution, 0.01 N. Dissolve 1.80 g of
gas through the train at the required If Antifoam B is not used, a more labor- (C6H5AsO) in 150 ml of 0.3 N sodium
flow rate. The pump need not be leak- intensive sample recovery procedure is hydroxide. After settling, decant 140 ml
free unless it is used for sampling. required (see Section 11.2). of this solution into 800 ml of water.
6.1.15 Needle Valve or Critical 7.1.2 Hydrogen Peroxide, 3 Percent. Bring the solution to pH 6–7 with 6 N
Orifice. To set air purge flow to 1 liter/ Dilute 30 percent H2O2 to 3 percent as HCl, and dilute to 1 liter with water.
min. needed. Prepare fresh daily. Standardize as in Section 10.2.3.
6.1.16 Tube Packed with Active 7.1.3 Water. Deionized distilled to 7.3.5 Starch Indicator Solution.
Carbon. To filter air during purge. conform to ASTM D 1193–77 or 91, Suspend 10 g of soluble starch in 100
6.1.17 Volumetric Flask. One 1000- Type 3 (incorporated by reference—see ml of water, and add 15 g of potassium
ml. § 60.17). The KMnO4 test for oxidizable
6.1.18 Volumetric Pipette. One 15- hydroxide (KOH) pellets. Stir until
organic matter may be omitted when dissolved, dilute with 900 ml of water,
ml. high concentrations of organic matter
6.1.19 Pressure-Reduction Regulator. and let stand for 1 hour. Neutralize the
are not expected to be present. alkali with concentrated HCl, using an
Depending on the sampling stream 7.2 Sample Recovery. The following indicator paper similar to Alkacid test
pressure, a pressure-reduction regulator reagents are needed for sample recovery: ribbon, then add 2 ml of glacial acetic
may be needed to reduce the pressure of 7.2.1 Water. Same as Section 7.1.3.
the gas stream entering the Teflon acid as a preservative.
7.2.2 Hydrochloric Acid (HCl)
sample line to a safe level. Note: Test starch indicator solution for
Solution, 3 M. Add 240 ml of decomposition by titrating with 0.01 N I2
6.1.20 Cold Trap. If condensed water concentrated HCl (specific gravity 1.19)
or amine is present in the sample solution, 4 ml of starch solution in 200 ml
to 500 ml of water in a 1-liter volumetric of water that contains 1 g of KI. If more than
stream, a corrosion-resistant cold trap flask. Dilute to 1 liter with water. Mix 4 drops of the 0.01 N I2 solution are required
shall be used immediately after the thoroughly. to obtain the blue color, a fresh solution must
sample tap. The trap shall not be 7.2.3 Iodine (I2) Solution, 0.1 N. be prepared.
operated below 0 °C (32 °F) to avoid Dissolve 24 g of potassium iodide (KI)
condensation of C3 or C4 hydrocarbons. in 30 ml of water. Add 12.7 g of 8.0 Sample Collection, Preservation,
6.2 Sample Recovery. The following resublimed iodine (I2) to the KI solution. Storage, and Transport
items are needed for sample recovery: Shake the mixture until the I2 is 8.1 Sampling Train Preparation.
6.2.1 Sample Container. Iodine flask,
completely dissolved. If possible, let the Assemble the sampling train as shown
glass-stoppered, 500-ml size. in Figure 11–1, connecting the five
6.2.2 Volumetric Pipette. One 50-ml. solution stand overnight in the dark.
6.2.3 Graduated Cylinders. One each Slowly dilute the solution to 1 liter with midget impingers in series. Place 15 ml
25- and 250-ml. water, with swirling. Filter the solution of 3 percent H2O2 solution in the first
6.2.4 Erlenmeyer Flasks. 125-ml. if it is cloudy. Store solution in a brown- impinger. Leave the second impinger
6.2.5 Wash Bottle. glass reagent bottle. empty. Place 15 ml of the CdSO4
6.2.6 Volumetric Flasks. Three 1000- 7.2.4 Standard I2 Solution, 0.01 N. solution in the third, fourth, and fifth
ml. Pipette 100.0 ml of the 0.1 N iodine impingers. Place the impinger assembly
6.3 Sample Analysis. The following solution into a 1-liter volumetric flask, in an ice water bath container, and place
items are needed for sample analysis: and dilute to volume with water. water and crushed ice around the
6.3.1 Flask. Glass-stoppered iodine Standardize daily as in Section 10.2.1. impingers. Add more ice during the run,
flask, 500-ml. This solution must be protected from if needed.

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61940 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

8.2 Leak-Check Procedure. should precede the leak-check of the 8.6 Disconnect the impinger train
8.2.1 Connect the rubber bulb and sampling train described immediately from the sampling line. Connect the
manometer to the first impinger, as above; if performed after the sampling charcoal tube and the pump as shown
shown in Figure 11–1. Close the petcock run, the pump leak-check should follow in Figure 11–1. Purge the train [at a rate
on the DGM outlet. Pressurize the train the sampling train leak-check. of 1 liter/min (0.035 ft3/min)] with clean
to 25 cm water with the bulb, and close 8.3 Purge the connecting line ambient air for 15 minutes to ensure
off the tubing connected to the rubber between the sampling valve and the first that all H2S is removed from the H2O2.
bulb. The train must hold 25 cm water impinger by disconnecting the line from For sample recovery, cap the open ends,
pressure with not more than a 1 cm the first impinger, opening the sampling and remove the impinger train to a clean
drop in pressure in a 1-minute interval. valve, and allowing process gas to flow area that is away from sources of heat.
Stopcock grease is acceptable for sealing through the line for one to two minutes. The area should be well lighted, but not
ground glass joints. Then, close the sampling valve, and exposed to direct sunlight.
8.2.2 If the pump is used for reconnect the line to the impinger train. 8.7 Sample Recovery.
sampling, it is recommended, but not Open the petcock on the dry gas meter 8.7.1 Discard the contents of the
required, that the pump be leak-checked outlet. Record the initial DGM reading. H2O2 impinger. Carefully rinse with
separately, either prior to or after the 8.4 Open the sampling valve, and water the contents of the third, fourth,
sampling run. To leak-check the pump, then adjust the valve to obtain a rate of and fifth impingers into a 500-ml iodine
proceed as follows: Disconnect the approximately 1 liter/min (0.035 cfm). flask.
drying tube from the impinger assembly. Maintain a constant (±10 percent) flow Note: The impingers normally have only a
Place a vacuum gauge at the inlet to rate during the test. Record the DGM thin film of CdS remaining after a water
either the drying tube or the pump, pull temperature. rinse. If Antifoam B was not used or if
significant quantities of yellow CdS remain
a vacuum of 250 mm Hg (10 in. Hg), 8.5 Sample for at least 10 minutes. in the impingers, the alternative recovery
plug or pinch off the outlet of the flow At the end of the sampling time, close procedure in Section 11.2 must be used.
meter, and then turn off the pump. The the sampling valve, and record the final
8.7.2 Proceed to Section 11 for the
vacuum should remain stable for at least volume and temperature readings.
analysis.
30 seconds. If performed prior to the Conduct a leak-check as described in
sampling run, the pump leak-check Section 8.2 above. 9.0 Quality Control

Section Quality control measure Effect

8.2, 10.1 .............. Sampling equipment leak-check and calibration ....... Ensure accurate measurement of sample volume.
11.2 ..................... Replicate titrations of blanks ..................................... Ensure precision of titration determinations.

10.0 Calibration and Standardization and average the results. If any Y value 10.2 Standardization.
deviates by more than 2 percent from 10.2.1 Iodine Solution
Note: Maintain a log of all calibrations. the average, the DGM is unacceptable Standardization. Standardize the 0.01 N
10.1 Calibration. Calibrate the for use. Otherwise, use the average as I2 solution daily as follows: Pipette 25
sample collection equipment as follows. the calibration factor for subsequent test ml of the I2 solution into a 125-ml
10.1.1 Dry Gas Meter. runs. Erlenmeyer flask. Add 2 ml of 3 M HCl.
10.1.1.1 Initial Calibration. The 10.1.1.2 Post-Test Calibration Check. Titrate rapidly with standard 0.01 N
DGM shall be calibrated before its initial After each field test series, conduct a Na2S2O3 solution or with 0.01 N
use in the field. Proceed as follows: calibration check as in Section 10.1.1.1, C6H5AsO until the solution is light
First, assemble the following above, except for the following two yellow, using gentle mixing. Add four
components in series: Drying tube, variations: (a) three or more revolutions drops of starch indicator solution, and
needle valve, pump, rotameter, and of the DGM may be used and (b) only continue titrating slowly until the blue
DGM. Then, leak-check the metering two independent runs need be made. If color just disappears. Record the
system as follows: Place a vacuum gauge the calibration factor does not deviate volume of Na2S2O3 solution used, VSI, or
(at least 760 mm Hg) at the inlet to the by more than 5 percent from the initial the volume of C6H5AsO solution used,
drying tube, and pull a vacuum of 250 calibration factor (determined in Section VAI, in ml. Repeat until replicate values
mm Hg (10 in. Hg); plug or pinch off the 10.1.1.1), then the DGM volumes agree within 0.05 ml. Average the
outlet of the flow meter, and then turn obtained during the test series are replicate titration values which agree
off the pump. The vacuum shall remain acceptable. If the calibration factor within 0.05 ml, and calculate the exact
stable for at least 30 seconds. Carefully deviates by more than 5 percent, normality of the I2 solution using
release the vacuum gauge before recalibrate the DGM as in Section Equation 11–3. Repeat the
releasing the flow meter end. Next, 10.1.1.1, and for the calculations, use standardization daily.
calibrate the DGM (at the sampling flow the calibration factor (initial or 10.2.2 Sodium Thiosulfate Solution
rate specified by the method) as follows: recalibration) that yields the lower gas Standardization. Standardize the 0.1 N
Connect an appropriately sized wet-test volume for each test run. Na2S2O3 solution as follows: Oven-dry
meter (e.g., 1 liter per revolution) to the 10.1.2 Temperature Sensors. potassium dichromate (K2Cr2O7) at 180
inlet of the drying tube. Make three Calibrate against mercury-in-glass to 200 °C (360 to 390 °F). To the nearest
independent calibration runs, using at thermometers. milligram, weigh 2 g of the dichromate
least five revolutions of the DGM per 10.1.3 Rate Meter. The rate meter (W). Transfer the dichromate to a 500–
run. Calculate the calibration factor, Y need not be calibrated, but should be ml volumetric flask, dissolve in water,
(wet-test meter calibration volume cleaned and maintained according to and dilute to exactly 500 ml. In a 500–
divided by the DGM volume, both the manufacturer’s instructions. ml iodine flask, dissolve approximately
volumes adjusted to the same reference 10.1.4 Barometer. Calibrate against a 3 g of KI in 45 ml of water, then add
temperature and pressure), for each run, mercury barometer. 10 ml of 3 M HCl solution. Pipette 50

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ml of the dichromate solution into this directly to the iodine flask. Once the NS = Normality of standard (ù0.1 N)
mixture. Gently swirl the contents of the acidified I2 solution has been poured Na2S2O3 solution, g-eq/liter.
flask once, and allow it to stand in the into any glassware containing CdS, the NT = Normality of standard (ù0.01 N)
dark for 5 minutes. Dilute the solution container must be tightly stoppered at Na2S2O3 solution, assumed to be 0.1
with 100 to 200 ml of water, washing all times except when adding more NS, g-eq/liter.
down the sides of the flask with part of solution, and this must be done as Pbar = Barometric pressure at the
the water. Titrate with 0.1 N Na2S2O3 quickly and carefully as possible. After sampling site, mm Hg.
until the solution is light yellow. Add adding any acidified I2 solution to the Pstd = Standard absolute pressure, 760
4 ml of starch indicator and continue iodine flask, allow a few minutes for mm Hg.
titrating slowly to a green end point. absorption of the H2S before adding any Tm = Average DGM temperature, °K.
Record the volume of Na2S2O3 solution further rinses. Repeat the I2 extraction Tstd = Standard absolute temperature,
used, VS, in ml. Repeat until replicate until all CdS is removed from the 293 °K.
values agree within 0.05 ml. Calculate impingers. Extract that part of the VA = Volume of C6H5AsO solution used
the normality using Equation 11–1. connecting glassware that contains for standardization, ml.
Repeat the standardization each week or VAI = Volume of standard C6H5AsO
visible CdS. Quantitatively rinse all the
after each test series, whichever time is solution used for titration analysis,
I2 from the impingers, connectors, and
shorter. ml.
the beaker into the iodine flask using VI = Volume of standard I2 solution used
10.2.3 Phenylarsine Oxide Solution water. Stopper the flask and shake
Standardization. Standardize the 0.01 N for standardization, ml.
briefly. VIT = Volume of standard I2 solution
C6H5AsO (if applicable) as follows: 11.3 Allow the iodine flask to stand
Oven-dry K2Cr2O7 at 180 to 200 °C (360 used for titration analysis, normally
about 30 minutes in the dark for
to 390 °F). To the nearest milligram, 50 ml.
absorption of the H2S into the I2, then Vm = Volume of gas sample at meter
weigh 2 g of the dichromate (W). complete the titration analysis as
Transfer the dichromate to a 500–ml conditions, liters.
outlined in Sections 11.5 and 11.6. Vm(std) = Volume of gas sample at
volumetric flask, dissolve in water, and
dilute to exactly 500 ml. In a 500–ml
Note: Iodine evaporates from acidified I2 standard conditions, liters.
solutions. Samples to which acidified I2 has VSI = Volume of ‘‘0.1 N Na2S2O3
iodine flask, dissolve approximately 0.3 been added may not be stored, but must be solution used for standardization,
g of KI in 45 ml of water, then add 10 analyzed in the time schedule stated above. ml.
ml of 3 M HCl. Pipette 5 ml of the
11.4 Prepare a blank by adding 45 VT = Volume of standard (ù0.01 N)
dichromate solution into the iodine
ml of CdSO4 absorbing solution to an Na2S2O3 solution used in
flask. Gently swirl the contents of the
iodine flask. Pipette exactly 50 ml of standardizing iodine solution (see
flask once, and allow it to stand in the
0.01 N I2 solution into a 125-ml Section 10.2.1), ml.
dark for 5 minutes. Dilute the solution VTT = Volume of standard (∼0.01 N)
with 100 to 200 ml of water, washing Erlenmeyer flask. Add 10 ml of 3 M
HCl. Stopper the flask, shake briefly, let Na2S2O3 solution used for titration
down the sides of the flask with part of
stand 30 minutes in the dark, and titrate analysis, ml.
the water. Titrate with 0.01 N C6H5AsO W = Weight of K2Cr2O7 used to
until the solution is light yellow. Add with the samples.
standardize Na2s2O3 or C6H5AsO
4 ml of starch indicator, and continue Note: The blank must be handled by
solutions, as applicable (see
titrating slowly to a green end point. exactly the same procedure as that used for
the samples. Sections 10.2.2 and 10.2.3), g.
Record the volume of C6H5AsO used, Y = DGM calibration factor.
VA, in ml. Repeat until replicate 11.5 Using 0.01 N Na2S2O3 solution
12.2 Normality of the Standard (ù0.1
analyses agree within 0.05 ml. Calculate (or 0.01 N C6H5AsO, if applicable),
N) Sodium Thiosulfate Solution.
the normality using Equation 11–2. rapidly titrate each sample in an iodine
Repeat the standardization each week or flask using gentle mixing, until solution 2.039 W
after each test series, whichever time is is light yellow. Add 4 ml of starch NS = Eq. 11-1
shorter. indicator solution, and continue VS
11.0 Analytical Procedure titrating slowly until the blue color just Where:
disappears. Record the volume of 2.039 = Conversion factor
Conduct the titration analyses in a Na2S2O3 solution used, VTT, or the = (6 g-eq I2/mole K2Cr2O7) (1,000 ml/
clean area away from direct sunlight. volume of C6H5AsO solution used, VAT, liter)/(294.2 g K2Cr2O7/mole) (10
11.1 Pipette exactly 50 ml of 0.01 N in ml. aliquot factor)
I2 solution into a 125-ml Erlenmeyer 11.6 Titrate the blanks in the same
flask. Add 10 ml of 3 M HCl to the 12.3 Normality of Standard
manner as the samples. Run blanks each Phenylarsine Oxide Solution (if
solution. Quantitatively rinse the day until replicate values agree within
acidified I2 into the iodine flask. applicable).
0.05 ml. Average the replicate titration
Stopper the flask immediately, and values which agree within 0.05 ml. 0.2039 W
shake briefly. NA = Eq. 11-2
11.2 Use these alternative 12.0 Data Analysis and Calculations VA
procedures if Antifoam B was not used Carry out calculations, retaining at Where:
or if significant quantities of yellow CdS least one extra significant figure beyond 0.2039 = Conversion factor.
remain in the impingers. Extract the that of the acquired data. Round off = (6 g-eq I2/mole K2Cr2O7) (1,000 ml/
remaining CdS from the third, fourth, figures only after the final calculation. liter)/(294.2 g K2Cr2O7/mole) (100
and fifth impingers using the acidified 12.1 Nomenclature. aliquot factor)
I2 solution. Immediately after pouring CH2S = Concentration of H2S at standard
the acidified I2 into an impinger, 12.4 Normality of Standard Iodine
conditions, mg/dscm. Solution.
stopper it and shake for a few moments, NA = Normality of standard C6H5AsO
then transfer the liquid to the iodine solution, g-eq/liter. N T VT
flask. Do not transfer any rinse portion NI = Normality of standard I2 solution, NI = Eq. 11-3
from one impinger to another; transfer it g-eq/liter. VI

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61942 Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / Rules and Regulations

Note: If C6H5AsO is used instead of standard conditions (20 °C and 760 mm 12.6 Concentration of H2S. Calculate
Na2S2O3, replace NT and VT in Equation 11– Hg). the concentration of H2S in the gas
3 with NA and VAS, respectively (see Sections stream at standard conditions using
10.2.1 and 10.2.3). Tstd Pbar
Vm (std ) = Vm Y Eq. 11-4 Equation 11–5:
12.5 Dry Gas Volume. Correct the Tm Pstd
sample volume measured by the DGM to

(VIT N I − VTT N T )sample − (VIT N I − VTT N T )blank
C H 2S = 17.04 × 10 3 Eq. 11-5
Vm (std )

Where: interferences cited in Section 4.0, the 2. Tentative Method of Determination of
bias was positive at low H2S Hydrogen Sulfide and Mercaptan Sulfur in
17.04 × 103 = Conversion factor
concentration and negative at higher Natural Gas. Natural Gas Processors
= (34.07 g/mole H2S) (1,000 liters/m3) Association, Tulsa, OK. NGPA Publication
(1,000mg/g)/(1,000 ml/liter) (2H2S concentrations. At 230 mg H2S/m3, the
level of the compliance standard, the No. 2265–65. 1965.
eq/mole) 3. Knoll, J.D., and M.R. Midgett.
bias was +2.7 percent. Thiols had no
Note: If C6H5AsO is used instead of Determination of Hydrogen Sulfide in
effect on the precision. Refinery Fuel Gases. Environmental
NaS22O3, replace NA and VAT in Equation
11–5 with NA and VAT, respectively (see 14.0 Pollution Prevention. [Reserved] Monitoring Series, Office of Research and
Sections 11.5 and 10.2.3). Development, USEPA. Research Triangle
15.0 Waste Management. [Reserved] Park, NC 27711. EPA 600/4–77–007.
13.0 Method Performance 16.0 References 4. Scheil, G.W., and M.C. Sharp.
Standardization of Method 11 at a Petroleum
13.1 Precision. Collaborative testing 1. Determination of Hydrogen Sulfide, Refinery. Midwest Research Institute Draft
has shown the intra-laboratory precision Ammoniacal Cadmium Chloride Method. Report for USEPA. Office of Research and
to be 2.2 percent and the inter- API Method 772–54. In: Manual on Disposal Development. Research Triangle Park, NC
laboratory precision to be 5 percent. of Refinery Wastes, Vol. V: Sampling and 27711. EPA Contract No. 68–02–1098.
13.2 Bias. The method bias was Analysis of Waste Gases and Particulate August 1976. EPA 600/4–77–088a (Volume 1)
shown to be ¥4.8 percent when only Matter. American Petroleum Institute, and EPA 600/4–77–088b (Volume 2).
H2S was present. In the presence of the Washington, D.C. 1954. BILLING CODE 6560–50–P

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