Emission Measurement Technical Information Center NSPS Test Method Method 10b Determination of Carbon Monoxide Emissions from Stationary Sources (EMTIC M 10b 8/16/94)


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EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER

NSPS TEST METHOD
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(EMTIC M-10B, 8/16/94)

Method lOB-Determination of Carbon Monoxide Emissions from
Stationary Sources

1. Applicability and Principle

1.1	Applicability. This method applies to the measurement of
carbon monoxide (CO) emissions at petroleum refineries and from
other sources when specified in an applicable subpart of the
regulations.

1.2	Principle. An integrated gas sample is extracted from the
sampling point and analyzed for CO. The sample is passed through a
conditioning system to remove interferences and collected in a
Tedlar bag. The CO is separated from the sample by gas
chromatography (GC) and catalytically reduced to methane (CH4)
prior to analysis by flame ionization detection FID. The analytical
portion of this method is identical to applicable sections in
Method 25 detailing CO measurement. The oxidation catalyst required
in Method 25 is not needed for sample analysis. Complete Method 25
analytical systems are acceptable alternatives when calibrated for
CO and operated by the Method 25 analytical procedures.

Note: Mention of trade names or commercial products in this
method does not constitute the endorsement or recommendation for
use by the Environmental Protection Agency.

1.3	Interferences. Carbon dioxide (C02) and organics
potentially can interfere with the analysis. Carbon dioxide is
primarily removed from the sample by the alkaline permanganate
conditioning system; any residual C02 and organics are separated
from the CO by GC.

2. Apparatus

2.1	Sampling. Same as in Method 10A, section 2.1.

2.2	Analysis.

2.2.1	Gas Chromatographic (GC) Analyzer. A semicontinuous

GC/FID analyzer capable of quantifying CO in the sample and
containing at least the following major components.

2.2.1.1 Separation Column. A column that separates CO from
C02 and organic compounds that may be present. A \l/8\-in. OD
stainless-steel column packed with 5.5 ft of 60/80 mesh Carbosieve
S-II (available from Supelco) has been used successfully for this

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Prepared by Emission Measurement Branch	EMTIC M-10B

Technical Support Division, OAQPS, EPA

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purpose. The column listed in Addendum 1 of Method 25 is also
acceptable.

2.2.1.2 Reduction Catalyst. Same as in Method 25, section
2.3.2.

2.2.1.3	Sample Injection System. Same as in Method 25,
section 2.3.4, equipped to accept a sample line from the Tedlar
bag.

2.2.1.4	Flame Ionization Detector. Linearity meeting the
specifications in section 2.3.5.1 of Method 25 where the linearity
check is carried out using standard gases containing 20-, 200-, and
1,0 0 0-ppm CO. The minimal instrument range shall span 10 to 1,000
ppm CO.

2.2.1.5	Data Recording System. Same as in Method 25, section
2.3.6.

3. Reagents

3.1	Sampling. Same as in Method 10A, section 3.1.

3.2	Analysis.

3.2.1	Carrier, Fuel, and Combustion Gases. Same as in

Method 25, sections 3.2.1, 3.2.2, and 3.2.3.

3.2.2	Linearity and Calibration Gases. Three standard
gases with nominal CO concentrations of 20-, 200-, and 1,000-ppm CO
in nitrogen.

3.2.3	Reduction Catalyst Efficiency Check Calibration Gas.
Standard CH4 gas with a concentration of 1,000 ppm in air.

4. Procedure

4.1	Sample Bag Leak-checks, Sampling, and C02 Measurement.
Same as in Method 10A, sections 4.1, 4.2, and 4.3.

4.2	Preparation for Analysis. Before putting the GC analyzer
into routine operation, conduct the calibration procedures listed
in section 5. Establish an appropriate carrier flow rate and
detector temperature for the specific instrument used.

4.3	Sample Analysis. Purge the sample loop with sample, and
then inject the sample. Analyze each sample in triplicate, and

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calculate the average sample area (A) . Determine the bag CO
concentration according to section 6.2.

5.	Calibration

5.1	Carrier Gas Blank Check. Analyze each new tank of carrier
gas with the GC analyzer according to section 4.3 to check for
contamination. The corresponding concentration must be less than 5
ppm for the tank to be acceptable for use.

5.2	Reduction Catalyst Efficiency Check. Prior to initial
use, the reduction catalyst shall be tested for reduction
efficiency. With the heated reduction catalyst bypassed, make
triplicate injections of the 1,0 0 0-ppm CH4 gas (section 3.2.3) to
calibrate the analyzer. Repeat the procedure using 1,000-ppm CO
(section 3.2.2) with the catalyst in operation. The reduction
catalyst operation is acceptable if the CO response is within 5
percent of the certified gas value.

5.3	Analyzer Linearity Check and Calibration. Perform this
test before the system is first placed into operation. With the
reduction catalyst in operation, conduct a linearity check of the
analyzer using the standards specified in section 3.2.2. Make
triplicate injections of each calibration gas, and then calculate
the average response factor (area/ppm) for each gas, as well as the
overall mean of the response factor values. The instrument
linearity is acceptable if the average response factor of each
calibration gas is within 2.5 percent of the overall mean value and
if the relative standard deviation (calculated in section 6.9 of
Method 25) for each set of triplicate injections is less than 2
percent. Record the overall mean of the response factor values as
the calibration response factor (R).

6.	Calculations

Carry out calculations retaining at least one extra decimal
figure beyond that of the acquired data. Round off results only
after the final calculation.

6.1 Nomenclature.

A=Average sample area.

Bw=Moisture content in the bag sample, fraction.

C=CO concentration in the stack gas, dry basis, ppm.

Cb=CO concentration in the bag sample, dry basis, ppm.

F=Volume fraction of C02 in the stack, fraction.

Pbar=Barometric pressure, mm Hg.

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Pw=Vapor pressure H20 in the bag (from Table 10A-2, Method
1 OA), mm Hg.

R=Mean calibration response factor, area/ppm.

6.2 CO Concentration in the Bag. Calculate Cb using Equations
10B-1 and 10B-2. If condensate is visible in the Tedlar bag,
calculate Bw using Table 10A-2 of Method 10A and the temperature
and barometric pressure in the analysis room. If condensate is not
visible, calculate Bw using the temperature and barometric pressure
at the sampling site.

See Table

Table 10A-2. Moisture Correction
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Temp.°C Vapor Press.H20 mm Hg Temp.°C Vapor Press.H20 mm HH
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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

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Eq. 10B-1

B„

P„

= ))))

P,

• bar

A

Eq. 10B-2	Cb = ))))

R(1-BJ

6.3 CO Concentration in the Stack,
Eq. 10B-3	C = Cb (1-F)

7. Bibliography

1.	Butler, F.E, J.E. Knoll, and M.R. Midgett. Development and
Evaluation of Methods for Determining Carbon Monoxide Emissions.
Quality Assurance Division, Environmental Monitoring Systems
Laboratory, U.S. Environmental Protection Agency, Research Triangle
Park, NC 27711. June 1985. 33p.

2.	Salo, A.E., S. Witz, and R.D. MacPhee. Determination of

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Solvent Vapor Concentrations by Total Combustion Analysis: A
Comparison of Infrared with Flame Ionization Detectors. Paper No.
75-33.2. (Presented at the 68th Annual Meeting of the Air Pollution
Control Association. Boston, MA. June 15, 1975.) 14 p.

3. Salo, A.E., W.L. Oaks, and R.D. MacPhee. Measuring the
Organic Carbon Content of Source Emissions for Air Pollution
Control. Paper No. 74-190. (Presented at the 67th Annual Meeting of
the Air Pollution Control Association. Denver, CO. June 9, 1974.)
25 p.

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