United States Environmental Monitoring Systems
Environmental Protection Laboratory
Agency Research Triangle Park NC 27711
Research and Development EPA/600/4-77/027b August 1988
oEPA Quality Assurance
Handbook for
Air Pollution
Measurement
Systems:
Volume III. Stationary
Sources Specific
Methods
Sections 3.0.5, 3.0.6,
3.0.8, and 3.13
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600477027 BC
August 1988 i v-rw
Volume III
Table of Contents
Section Pages Date
Purpose and Overview of the Quality 3 1-04-85
Assurance Handbook
3.0 General Aspects of Quality Assurance for
Stationary Source Emissions
Testing Programs
3.0.1 Planning the Test Program 12 5-01-79
3.0.2 General Factors Involved in Stationary 9 5-01-79
Source Testing
3.0.3 Chain-of-Custody Procedure for Source 7 5-01-79
Sampling
3.0.4 Procedure for NBS-Traceable Certification 14 6-09-87
of Compressed Gas Working Standards
Used for Calibration and Audit of
Continuous Source Emission Monitoring
(Revised Traceability Protocol No. 1
3.0.5 Specific Procedures to Assess 58 9-23-85
Accuracy of Reference Methods Used for
SPNSS
3.0.6 Specific Procedures to Assess 14 9-23-85
Accuracy of Reference Methods Used for
NESHAP
3.0.7 Calculation and Interpretation of 14 11-05-85
Accuracy for Continuous Emission
Monitoring Systems (CEMS)
3.0.8 Audit Materials Available from 7 11-04-85
U.S.E.P.A.
3.0.9 Continuous Emission Monitoring 47 6-01-86
Systems (CEMS) Good Operating
Practices
3.0.10 Guideline for Developing Quality 11 11-26-85
Control Procedures for Gaseous
Continuous Emission Monitoring
Systems
3.1 Method 2—Determination of Stack Gas
Velocity and Volumetric Flow Rate
3.1.1 Procurement of Apparatus and Supplies 15 1-15-80
3.1.2 Calibration of Apparatus 21 1-15-80
3.1.3 Presampling Operations 7 1-15-80
3.1.4 On-Site Measurements 12 1-15-80
3.1.5 Postsampling Operations 3 1-15-80
3.1.6 Calculations 4 1-15-80
3.1.7 Maintenance 1 1-15-80
3.1.8 Auditing Procedure 5 1-15-80
3.1.9 Recommended Standards for Establishing 1 1-15-80
Traceability
3.1.10 Reference Method 11 1-15-80
3.1.11 References 2 1-15-80
3.1.12 Data Forms 8 1-15-80
3.2 Method 3—Determination of Carbon
Dioxide, Oxygen Excess Air, and Dry
Molecular Weight
3.2.1 Procurement of Apparatus and Supplies 15 1-15-80
3.2.2 Calibration of Apparatus 4 1-15-80
3.2.3 Presampling Operations 6 1-15-80
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August 1988
Table of Contents (continued)
Section Pages Date
3.2.4 On-Site Measurements 12 1-15-80
3.2.5 Postsampling Operations 2 1-15-80
3.2.6 Calculations 3 1-15-80
32.7 Maintenance 1 1-15-80
3.2.8 Auditing Procedure 5 1-15-80
3.2.9 Recommended Standards for 1 1-15-80
Establishing Traceability
3.2.10 Reference Method 3 1-15-80
3.2.11 References 1 1-15-80
3.2.12 Data Forms 6 1-15-80
3.3 Method 4—Determination of Moisture
in Stack Gases
3.3.1 Procurement of Apparatus and Supplies 9 1-15-80
3.3.2 Calibration of Apparatus 19 1-15-80
3.3.3 Presampling Operations 7 1-15-80
3.3.4 On-Site Measurements 10 1-15-80
3.3.5 Postsampling Operations 4 1-15-80
3.3.6 Calculations 8 1-15-80
3.3.7 Maintenance 3 1-15-80
3.3.8 Auditing Procedure 4 1-15-80
3.3.9 Recommended Standards for 1 1-15-80
Establishing Traceability
3.3.10 Reference Method 5 1-15-80
3.3.11 References 1 1-15-80
3.3.12 Data Forms 14 1-15-80
3.4 Method 5—Determination of Paniculate
Emissions from Stationary Sources
3.4.1 Procurement of Apparatus arid Supplies 15 1-15-80
3.4.2 Calibration of Apparatus 22 1-15-80
3.4.3 Presampling Operations 20 1-15-80
3.4.4 On-Site Measurements 19 1-15-80
3.4.5 Postsampling Operations 15 1-15-80
3.4.6 Calculations 10 1-15-80
3.4.7 Maintenance 3 1-15-80
3.4.8 Auditing Procedure 7 1-15-80
3.4.9 Recommended Standards for 1 1-15-80
Establishing Traceability
3.4.10 Reference Method 6 1-15-80
3.4.11 References 2 1-15-80
3.4.12 Data Forms 21 1-15-80
3.5 Method 6—Determination of Sulfur
Dioxide Emissions from Stationary Sources
3.5.1 Procurement of Apparatus and Supplies 6 5-01-79
3.5.2 Calibration of Apparatus 6 5-01-79
3.5.3 Presampling Operations 3 5-01-79
3.5.4 On-Site Measurements 7 5-01-79
3.5.5 Postsampling Operations 7 5-01-79
3.5.6 Calculations 2 5-01-79
3.5.7 Maintenance 1 5-01-79
3.5.8 Auditing Procedure 6 9-23-85
3.5.9 Recommended Standards for 1 5-01-79
Establishing Traceability
3.5.10 Reference Method 4 5-01-79
3.5.11 References 1 '5-01-79
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August 1988
Table of Contents (continued)
Section Pages Date
3.5.12 Data Forms 13 5-01-79
3.6 Method 7—Determination of Nitrogen
Oxide Emissions from Stationary Sources
3.6.1 Procurement of Apparatus and Supplies 5 5-01-79
3.6.2 Calibration of Apparatus 5 5-01-79
3.6.3 Presampling Operations 5 5-01-79
3.6.4 On-Site Measurements 8 5-01-79
3.6.5 Postsampling Operations 5 5-01-79
3.6.6 Calculations 4 5-01-79
3.6.7 Maintenance 1 5-01-79
3.6.8 Auditing Procedure 6 9-23-85
3.6.9 Recommended Standards for 1 5-01-79
Establishing Traceability
3.6.10 Reference Method 5 5-01-79
3.6.11 References 1 5-01-79
3.6.12 Data Forms 13 5-01-79
3.7 Method 8—Determination of Sulfuric Mist
and Sulfur Dioxide Emissions from
Stationary Sources
3.7.1 Procurement of Apparatus and Supplies 7 5-01-79
3.7.2 Calibration of Apparatus 10 5-01-79
3.7.3 Presampling Operations 4 5-01-79
3.7.4 On-Site Measurements 10 5-01-79
3.7.5 Postsampling Operations 9 5-01-79
3.7.6 Calculations 6 5-01-79
3.7.7 Maintenance 2 5-01-79
3.7.8 Auditing Procedure 3 5-01-79
3.7.9 Recommended Standards for 1 5-01-79
Establishing Traceability
3.7.10 Reference Method 5 5-01-79
3.7.11 References 1 5-01-79
3.7.12 Data Forms 17 5-01-79
3.8 Method 10—Determination of Carbon
Monoxide Emissions from Stationary
Sources
3.8.1 Procurement of Apparatus and Supplies 13 1-04-82
3.8.2 Calibration of Apparatus 18 1-04-82
3.8.3 Presampling Operations 6 1-04-82
3.8.4 On-Site Measurements 12 1-04-82
3.8.5 Postsampling Operations 5 1-04-82
3.8.6 Calculations 3 1-04-82
3.8.7 Maintenance 2 1-04-82
3.8.8 Auditing Procedure 7 1-04-82
3.8.9 Recommended Standards for 7 1-04-82
Establishing Traceability
3.8.10 Reference Method 3 1-04-82
3.8.11 References 2 1-04-82
3.8.12 Data Forms 11 1-04-82
3.9 Method 13B—Determination of Total
Fluoride Emissions from Stationary
Sources (Specific-Ion Electrode Method)
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August 1988
Table of Contents (continued)
Section Pages Date
3.9.1 Procurement of Apparatus and Supplies 20 1-04-82
3.9.2 Calibration of Apparatus 25 1-04-82
3.9.3 Presampling Operations 6 1-04-82
3.9.4 On-Site Measurements 21 1-04-82
3.9.5 Postsampling Operations 19 1-04-82
3.9.6 Calculations 7 1-04-82
3.9.7 Maintenance 3 1-04-82
3.9.8 Auditing Procedure 8 1-04-82
3.9.9 Recommended Standards for 1 1-04-82
Establishing Traceability
3.9.10 Reference Method 2 1-04-82
3.9.11 References 1 1-04-82
3.9.12 Data Forms 22 1-04-82
3.10 Method 13A—Determination of Total
Fluoride Emissions from Stationary
Sources (SPADNS Zirconium Lake
Method)
3.10.1 Procurement of Apparatus and Supplies 13 1-04-82
3.10.2 Calibration of Apparatus 5 1-04-82
3.10.3 Presampling Operations 3 1-04-82
3.10.4 On-Site Measurements 3 1-04-82
3.10.5 Postsampling Operations 18 1-04-82
3.10.6 Calculations 7 1-04-82
3.10.7 Maintenance 2 1-04-82
3.10.8 Auditing Procedure 1 1-04-82
3.10.9 Recommended Standards for 1 1-04-82
Establishing Traceability
3.10.10 Reference Method 5 1-04-82
3.10.11 References 1 1-04-82
3.10.12 Data Forms 6 1-04-82
3.11 Method 17—Determination of Paniculate
Emissions from Stationary Sources
(In-Stack Filtration Method)
3.11.1 Procurement of Apparatus and Supplies 9 1-04-82
3.11.2 Calibration of Apparatus 2 1-04-82
3.11.3 Presampling Operations 3 1-04-82
3.11.4 On-Site Measurements 6 1-04-82
3.11.5 Postsampling Operations 1 1-04-82
3.11.6 Calculations 1 1-04-82
3.11.7 Maintenance 2 1-04-82
3.11.8 Auditing Procedure 2 1-04-82
3.11.9 Recommended Standards for 1 1-04-82
Establishing Traceability
3.11.10 Reference Method 11 1-04-82
3.11.11 References 1 1-04-82
3.11.12 Data Forms 1 1-04-82
3.12 Method 9—Visible Determination of
the Opacity Emissions from
Stationary Sources
3.12.1 Certification and Training of Observers 5 4-20-83
3.12.2 Procurement of Apparatus and Supplies 2 4-20-83
3.12.3 Preobservation Operations 2 4-20-83
3.12.4 On-Site Field Observations 18 4-20-83
3.12.5 Postobservation Operations 2 4-20-83
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August 1988
Table of Contents (continued)
Section Pages Date
3.12.6 Calculations 7 4-20-83
3.12.7 Auditing Procedure 2 4-20-83
3.12.8 Reference Method 5 4-20-83
3.12.9 References and Bibliography 1 4-20-83
3.12.10 Data Forms 9 4-20-83
3.13 Methods 6A and 6B—Determinations
of Sulfur Dioxide, Moisture, and Carbon
Dioxide Emissions from Fossil Fuel
Combustion Sources
3.13.1 Procurement of Apparatus and Supplies 18 7-01-86
3.13.2 Calibration of Apparatus 14 7-01-86
3.13.3 Presampling Operations 6 7-01-86
3.13.4 On-Site Measurements 25 7-01-86
3.13.5 Postsampling Operations 15 7-01-86
3.13.6 Calculations 9 7-01-86
3.13.7 Maintenance 3 7-01-86
3.13.8 Auditing Procedure 11 7-01-86
3.13.9 Recommended Standards for 1 7-01-86
Establishing Traceability
3.13.10 Reference Method 5 7-01-86
3.13.11 References 2 7-01-86
3.13.12 Data Forms 18 7-01-86
3.14 Method 7A—Determination of Nitrogen
Oxide Emissions from Stationary
Sources (Grab Sampling—Ion
Chromatographic Method)
3.14.1 Procurement of Apparatus and Supplies 10 7-01-86
3.14.2 Calibration of Apparatus 14 7-01-86
3.14.3 Presampling Operations 6 7-01-86
3.14.4 On-Site Measurements 7 7-01-86
3.14.5 Postsampling Operations 11 7-01-86
3.14.6 Calculations 6 7-01-86
3.14.7 Maintenance 2 7-01-86
3.14.8 Auditing Procedure 6 7-01-86
3.14.9 Recommended Standards for 1 7-01-86
Establishing Traceability
3.14.10 Reference Method 3 7-01-86
3.14.11 References 2 7-01-86
3.14.12 Data Forms 12 7-01-86
3.15 Method 7D—Determination of Nitrogen
Oxide Emissions from Stationary
Sources (Alkaline-Permanganate—Ion
Chromatographic Method)
3.15.1 Procurement of Apparatus and Supplies 18 7-01-86
3.15.2 Calibration of Apparatus 20 7-01-86
3.15.3 Presampling Operations 6 7-01-86
3.15.4 On-Site Measurements 10 7-01-86
3.15.5 Postsampling Operations 13 7-01-86
3.15.6 Calculations 5 7-01-86
3.15.7 Maintenance 3 7-01-86
3.15.8 Auditing Procedure 6 7-01-86
3.15.9 Recommended Standards for 1 7-01-86
Establishing Traceability
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August 1988
Table of Contents (continued)
Section Pages Date
3.15.10 Reference Method 9 7-01-86
3.15.11 References 2 7-01-86
3.15.12 Data Forms 11 7-01-86
3.16 Method 18—Measurement of Gaseous
Organic Compound Emissions by Gas
Chromatography
3.16.1 Procurement of Apparatus and Supplies 16 6-30-88
3.16.2 Calibration of Apparatus 15 6-30-88
3.16.3 Presampling Operations 44 6-30-88
3.16.4 On-Site Measurements 33 6-30-88
3.16.5 Postsampling Operations 39 6-30-88
3.16.6 Calculations 6 6-30-88
3.16.7 Maintenance 3 6-30-88
3.16.8 Auditing Procedure 8 6-30-88
3.16.9 Recommended Standards for Establishing
Traceability 1 6-30-88
3.16.10 Reference Methods 20 6-30-88
3.16.11 References 5 6-30-88
3.16.12 Data Forms 21 6-30-88
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Section No. 3.0.5
Date September 23, 1985
Page 1
5.0 SPECIFIC PROCEDURES TO ASSESS ACCURACY OF REFERENCE METHODS
USED FOR STANDARDS OF PERFORMANCE FOR NEW STATIONARY SOURCES
On May 30, 1979, the EPA Administrator stated in a memo "the
EPA must have a comprehensive quality assurance (QA) effort to
provide for the generation, storage, and use of environmental
data which are of known quality." The memo further stated that
participation in the QA effort was mandatory for all EPA sup-
ported or required monitoring activities. In a subsequent memo
(dated June 14, 1979), it was stated that the mandatory QA
program included all EPA grants, contracts, cooperative
agreements, and interagency agreements. On November 24, 1980,
the EPA Administrator approved a strategy to implement the QA
program. As part of this strategy, each Project Officer must
develop and obtain approval for a QA Project Plan if he/she
determines the project will result in "environmentally related
measurements." All source emission tests conducted for
compliance or enforcement purposes are considered "envir-
onmentally related measurements." Guidelines for the development
of a QA Project Plan are discussed in Section 1.4.23 and Appendix
M of Volume I of this Handbook. The most important part of any
QA Project Plan is a description of specific procedures to
routinely assess and document data precision, accuracy, and
completeness of specific measurement parameters involved.
The purpose of this Section is 'to briefly describe specific
procedures to routinely assess and document the accuracy of
reference and alternative methods for source test data under
SPNSS (Standards of Performance for New Stationary Sources).
Procedures for assessment of precision and completeness are not
given because compliance or enforcement tests are short-term
(only a few hours duration) and additional duplicate tests to
obtain precision data are costly. Accuracy is determined from
results of performance audits (i..e., measurements made by the
routine operator or analyst). The routine operator or analyst
must not know the concentration or value of the audit standard
used, and the results must be submitted to an immediate super-
visor or QA coordinator who does know the audit value.
Audit samples must have known or true values. They must be
prepared with materials similar to field samples and/or cali-
bration standards. Meticulous procedures and programs must also
be established to ensure audit sample values (1) are correct as
stated, (2) remain stable until used, (3) are properly coded and
recorded, and (4) are of the proper concentration range to be
audited.
Since a high degree of experience and planning is required
for audit sample preparation, and EPA has mandated that quality
assurance be an integral part of the agency measurement programs,
the EPA's Environmental Monitoring Systems Laboratory (EMSL) in
Research Triangle Park, North Carolina has been delegated the
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Section No. 3.0.5
Date September 23, 1985
Page 2
responsibility for preparation of audit samples and materials for
air measurements. Federal, State, and local agency personnel can
obtain audit samples and materials for any enforcement and com-
pliance measurement program directly from the Quality Assurance
Coordinator in each EPA Regional Office unless otherwise directed
in the following Reference Method subsections. When audit mater-
ials are unavailable from EPA or needed for nonagency use, com-
mercial suppliers should be sought. Table 5.1 lists the address
and telephone number for the Quality Assurance Coordinator in
each of the ten EPA Regional Offices.
Several of the EPA Reference Methods have no performance
audits because (1) they are specification methods or (2) no reli-
able or low cost procedures are currently available. The EPA
Reference Methods for which audits are recommended are shown in
Table 5.2 with their corresponding subsection number.
The specific assessment procedure for each promulgated Ref-
erence Method is approximately three pages in length. This brief
description of the assessment procedure includes the following:
1. Method description.
2. References for details on the method.
3. Performance audit program to assess the accuracy of sam-
pling and analytical procedures.
4. Recommended? frequency for performance audits of compli-
ance and enforcement tests. A frequency less than that
recommended for enforcement purposes may be acceptable when
testing for other purposes.
5. Recommended standards and levels for establishing audit
values.
6. Procedure to calculate accuracy.
7. Availability of audit materials.
8. Cost of the recommended audit.
The philosophy of these assessments is that relative error
calculations will be made of the accuracy (1) to determine errors
in the testers'/analysts' techniques and systems, (2) when possi-
ble, to correct errors in these techniques and systems, and (3)
for interpretation of the final reported emission test results by
the data user. The reported emissions test data should not be
corrected on the basis of these relative error calculations.
The general approach that has been developed for these
audits follow those already described in the Reference Methods
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Section No. 3.0.5
Date September 23, 1985
Page 3
TABLE 5.1. REGIONAL QUALITY ASSURANCE COORDINATORS (AIR)
Quality Assurance Coordinator (Air)
Central Regional Laboratory
Environmental Services Division
US EPA, Region 1
60 Westview Street
Lexington, MA 02173
FTS: 861-6700; COML: 617-861-6700
Quality Assurance Coordinator (Air)
Environmental Services Division
USEPA, Region 2
Edison, NJ 08837
FTS: 340-6766; COML: 201-321-6766
Quality Assurance Coordinator (Air)
Environmental Services Division
USEPA, Region 3
841 Chestnut Building, 8th Floor
Philadelphia, PA 19107
FTS: 597-6445; COML: 215-597-6445
Quality Assurance Coordinator (Air)
Environmental Services Division
USEPA, Region 4
College Station Road
Athens, GA 30613
FTS: 250-3390; COML: 404-546-3390
Quality Assurance Coordinator (Air)
Environmental Services Division
USEPA, Region 5
536 South Clark Street
Chicago, IL 60605
FTS: 353-9317; COML: 312-353-9317
Quality Assurance Coordina-
tor (Air)
Environmental Services Div.
US EPA, Region 6
First International Bldg.
1201 Elm Street
Dallas, TX 75270
FTS: 729-0728,
COML: 214-767-0728
Quality Assurance Coordina-
tor (Air)
USEPA, Region 7
25 Funston Road
Kansas City, KS 66115
FTS: 926-3881;
COML: 913-236-3881
Quality Assurance Coodina-
nator (Air
Environmental Services Div.
1860 Lincoln Street
Denver, CO 80295
FTS: 776-5064;
COML: 303-564-5064
Quality Assurance Coordina-
tor (Air)
USEPA, Region 9
215 Fremont Street
San Francisco, CA 94105
FTS: 454-7480;
COML: 415-974-0922
Quality Assurance Coordina-
tor (Air)
Environmental Services Div,
US EPA, Region 10
1200 Sixth Ave.,
Mail Stop 337
Seattle, WA 98101
FTS: 399-1675;
COML: 206-442-1675
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Section No. 3.0.5
Date September 23, 1985
Page 4
TABLE 5.2. EPA REFERENCE METHODS INCLUDED IN SECTION 3.0.5
Method
number
2
3
5, 5A, & 5D
6, 6A, & 6B
7, 7A, 7C, & 7D
8
10
11
12
13A & 13B
15
16
16A
17
18
19
Subsection
Description number
Volumetric Flow Rate
Carbon Dioxide and Oxygen
Particulate Matter
Sulfur Dioxide
Oxides of Nitrogen
Sulfuric Acid and Sulfur Dioxide
Carbon Monoxide
Hydrogen Sulfide
Inorganic Lead
Total Fluoride
Hydrogen Sulfide, Carbonyl Sulfide,
and Carbon Disulfide
Hydrogen Sulfide, Methylmercaptan,
Dimethyl Sulfide, and Dimethyl
Disulfide
Alternate Method for TRS
Instack Filterable Particulate
VOC, General GC Method
Sulfur Dioxide Removal Efficiency
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
5.10
5.11
5.12
5.13
5.14
5.15
and Particulate, Sulfur Dioxide,
and Nitrogen Oxide 5.16
20 Nitrogen Oxide, Sulfur Dioxide, and
Oxygen for Stationary Gas Turbines 5.17
25 Total Gaseous Nonmethane Organics 5.18
25A & 25B Total Gaseous Organics 5.19
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Section No. 3.0.5
Date September 23, 1985
Page 5
for EPA Method 6 and 7 (see Reference 1) and/or Method 18 (see
Reference 2). These audit procedures require the tester/analyst
to provide the auditor with the audit results, either prior to
the field sample analysis or prior to including the field sample
results in the test report. When large relative errors are
identified, the tester/analyst is allowed to correct his system.
If possible, this is accomplished prior to the taking of the
field samples or performing the final analysis on the field
samples; this approach works quite well when the auditor is
present for an on-site analysis. However, in the absence of the
auditor the tester/analyst must telephone the auditor with
results of the audit sample analysis in order to make necessary
corrections prior to analyzing the field samples. If the auditor
feels that is unwarranted, or if the tester/analyst does not wish
to take the possible opportunity to correct an error in the
system and/or techniques, the audit sample(s) would then be
prepared and analyzed in the same manner and at the same time as
the field samples. The approach of notifying the auditor prior
to field sample analysis can provide the source and agency with a
greater chance of more accurate data, may require the rejection
of less test results, and may improve the techniques and system
of the tester and/or analyst.
For compliance determination, the audit sample values should
be within the range of the allowable emission limit. The audit
sample concentration or value should be within 40 to 200 percent
of the value of interest for audits containing a single audit
sample. For audits containing two audit samples, the low con-
centration sample should be between 25 and 100 percent of the
value of interest and the high concentration between 100 and 250
percent.
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Section No. 3.0.5
Date September 23, 1985
Page 6
5.1 Method 2 (Stack Gas Velocity and Volumetric Flow Rate)
5.1.1 Method Description - Method 2 is applicable for measure-
ment of the average velocity of a gas stream and for quantifying
gas flow. This procedure is not applicable at measurement sites
which fail to meet the criteria of Method 1. Also, the Method
cannot be used for direct measurement in cyclonic or swirling gas
streams. Method 1 shows how to determine cyclonic or swirling
flow conditions. Therefore, when unacceptable conditions exist,
alternative procedures subject to the approval of the Adminis-
trator, U.S. Environmental Protection Agency, must be employed to
make accurate flow rate determinations; examples of such alter-
native procedures are: (1) to install straightening vanes; (2)
to calculate the total volumetric flow rate stoichiometrically;
or (3) to move to another measurement site at which the flow is
acceptable.
The average gas velocity in a stack is determined from the
gas density and from measurement of the average velocity head
with a Type S (Stauscheibe or reverse type) pitot tube.
Section 3.1.10 of this Handbook contains a detailed descrip-
tion of Method 2 (40 CFR 60, Appendix A, Method 2).
5.1.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures -
5.1.2.1 Sampling Accuracy - When an inclined manometer that
meets the specifications shown in Section 2.2 of Method 2 is used
to measure the velocity pressure of the stack gas velocity, no
audit is recommended. When another differential pressure gauge
is used (e.g., Magnahelic gauge), the gauge should be assessed
for accuracy against an inclined manometer for each test series.
The auditor should use an inclined manometer that meets the
specifications shown in Section 2.2 of Method 2, Appendix A,
40 CFR 60.
The following items are provided as guidance for a proper
audit and should be performed only when a differential pressure
gauge other than an inclined manometer is used. When an inclined
manometer that meets the specifications in Method 2 is used as
the differential pressure gauge, no audit is recommended.
1. The pitot tube/differential pressure system should have
been leak checked, leveled and zeroed.
2. After the velocity measurement system has been checked
and prepared for testing, the differential pressure gauge should
be audited by attaching an inclined manometer and "T" connections
and tubing to the measurement system as explained in Method 2,
Subsection 3.1.2 of this Handbook. The tubing may be slipped
over the end of the pitot tube if a leakless connection can be
made.
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Section No. 3.0.5
Date September 23, 1985
Page 7
3. Prior to the testing series, the differential pressure
gauge's accuracy must be checked at a value close to the average
Ap obtained from the preliminary velocity traverse. Check both
the negative and positive side. The readings should agree within
5 percent. If this agreement cannot be met, try to determine the
problem and repeat the audit.
4. The auditor should compute the % relative error (RE)
for each of the audits:
RE = CM ~ CA x 100
CA
where:
CM = Pressure measured by differential pressure gauge,
in. H20, and
CA = Pressure measured by inclined manometer, in. H^O.
5. When the initial and repeat audit does not meet the 5
percent relative error, the auditor may take actions deemed
appropriate, or may inform the tester that if the post-test cali-
bration of the differential pressure gauge does not meet the 5
percent agreement, the test may be voided.
6. The calculated RE should be included in the emission
test report as an assessment of the accuracy of Method 2.
The difference between the measured values is used to assess the
sampling accuracy. The significance of the error in the final
velocity measurement will be the square root of 1 + .
100
5.1.2.2 Analytical Accuracy - No analysis is in this Method.
5.1.3 Audit Frequency - When Method 2 is used for SPNSS pur-
poses, the following audit frequency is recommended for the com-
pliance and enforcement test. No audits are recommended for sam-
pling or analysis if an inclined manometer is used that meets the
specifications of Method 2. If a differential pressure gauge
other than an inclined manometer is used, the gauge should be
audited prior to the field test series (one audit per entire test
series). An additional audit should be performed when (1) the
differential pressure gauge is replaced or (2) the differential
pressure gauge is altered to the point that the mechanical work-
ings may be changed. A lesser frequency may be accepted when
Method 2 is used for other applications depending on the purpose
of the test.
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Section No. 3.0.5
Date September 23, 1985
Page 8
5.1.4 Availability of Audit Materials - The inclined manometers
are available commercially. The purchaser should ensure that the
manometer meets the specifications explained in Method 2, Subsec-
tion 2.2.
5.1.5 Cost of Audit - The audit for Method 2 should require less
than one additional technical hour of effort to complete. This
would generally represent less than 10 percent of the total
effort to conduct, calculate, and report the Method 2 testing.
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Section No. 3.0.5
Date September 23, 1985
Page 9
5.2 Method 3 (Carbon Dioxide and Oxygen)
Method 3 should be audited using the quality assurance
requirements in Method 3 (see Reference 3 for details).
*
5.2.1 Method Description - This Method is used for determining
CO 2 and O2 concentrations > 0.2 percent by volume and for
calculating excess air and the dry molecular weight of gas
streams from combustion sources. The Method may also be
applicable to other processes where it has been determined that
compounds other than C02, 02, CO, and nitrogen (N^) are not
present in concentrations sufficient to affect the results.
Section 3.2.11 of this Handbook contains a detailed description
of Method 3 (Method 3 is found in 40 CFR 60, Appendix A).
Limitations to the use of Method 3 are cited in the NOTE below.
5.2.2 Audits to Assess Accurcy of Sampling and Analytical
Procedures -
5.2.2.1 Sampling Accuracy - No audit is recommended for sampling
procedures at this time .
5.2.2.2 Analytical Accuracy - If. the data are to be used only
for molecular weight determination, no audit is recommended for
the analytical procedures. If the data are to be used for excess
air determination, concentration correction or F-factor calcu-
lation, an audit is recommended. This is the same audit that is
suggested by EPA Reference Method 3. No additional requirements
were included.
Although in most instances only C02 or 02 is required, it is
recommended that both CO2 and 02 be measured to provide a check
on the quality of the aata. Tne following performance audit is
suggested.
*
NOTE: Since the Method for validating C02 and 02 analyses is
based on combustion of organic and fossil fuels and dilution of
the gas stream with air, this Method does not apply to sources
that (1) remove C02 or 02 through processes other than
combustion, (2) add O2 (e.g., oxygen enrichment) and N~ in
proporations different from that of air, (3) add CO2 (e.g.,
cement or lime kilns), or (4) have no fuel factor, F , values
obtainable (e.g., extremely variable waste mixtures'). This
Method validates the measured proportions of C02 and 02 for the
fuel type, but the Method does not detect sample dilution
resulting from leaks during or after sample collection. The
Method is applicable for samples collected downstream of most
lime or lime flue-gas desulfurization units as the C0~ added or
removed from the gas stream is not significant in relation to the
total CO2 concentration. The C02 concentrations from other types
of scruobers using only water or basic slurry can be
significantly affected and would render the F check minimally
useful. °
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Section No. 3.0.5
Date September 23, 1985
Page 10
Calculate a fuel factor, F , using the following equation:
_
o "
20.9 - %0
%C0
where:
% O2 = Percent 02 by volume (dry basis).
% C02 = Percent C02 by volume (dry basis).
20.9 = Percent O2 by volume in ambient air.
If CO is present in quantities measurable by this Method,
adjust the 02 and C02 values before performing the calculation
for F as follows:
o
, + %CO
'- 0.5 %CO
.
, =
2 ( adj )
,
2
where: %CO = Percent CO volume (dry basis).
Compare the calculated F factor with the expected F
values. The following table may be used in establishing
acceptable ranges for the expected F if the fuel being burned is
known. When fuels are burned in combination, calculate the
combined fuel F, and F
Method 19) according0 to
5.2.3.
factors (as defined
the procedure in
Then calcuate the F factor as follows:
in EPA Reference
Method 19 Section
'„ -
where;:
F, and F have the units of scm/J or scf/million Btu; %H,
%C, %s, %N, %0, and %H.~0 are the concentrations by weight
(expressed in percent) or hydrogen, carbon, sulfur, nitrogen,
oxygen, and water from an ultimate analysis of the fuel; and GCV
is the gross calorific value of the fuel in kJ/kg or Btu/lb and
is consistent with the ultimate analysis. Follow ASTM 2015 for
solid fuels, D 240 for liquid fuels, and D 1826 for gaseous fuels
as applicable in determining GCV.
Fuel Type
Range
Coal.:
Anthracite and lignite 1.016 - 1.130
Bituminous 1.083 - 1.230
Oil:
Distillate 1.260 - 1.413
Residual 1.210 - 1.370
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Section No. 3.0.5
Date September 23, 1985
Page 11
Fuel Type F Range
Gas: ~~°
Natural 1. 600 - 1. 836
Propane 1.434 - 1.586
Butane 1.405 - 1. 553
Wood: 1.000 - 1.120
Wood bark: 1.003 - 1.130
Calculated F values beyond the acceptable ranges shown in
this table shou?d be investigated before accepting the test
results. For example, the strength of the solutions in the gas
analyzer and the analyzing technique should be checked by
sampling and analyzing a known concentration, such as air; the
fuel factor should then be reviewed and verified. An
acceptability range of ^12 percent is appropriate for the F
factor of mixed fuels with variable fuel ratios. The level o?
the emission rate relative to the compliance level should be
considered in determining if a retest is appropriate, i.e., if
the measured emissions are much lower or much greater than the
compliance limit, repetition of the test would not significantly
change the compliance status of the source and would be
unnecessarily time-consuming and costly.
It should be noted that this audit only checks the accuracy
relative to the ratio of CO2 to 02- If the sampling system had a
leak, this check would not detect the bias in the results.
5.2.3 Audit Frequency - When Method 3 is used for SPNSS pur-
poses, the following audit frequency is recommended for the
compliance and enforcement test. An audit for accuracy should be
conducted after each analysis. A lesser frequency may be accep-
table when Method 3 is used for other applications depending on
the purposes of the test (i.e., no audit would be recommended if
the data are to be used only to determine stack gas molecular
weight).
5.2.4 Availability of Audit Materials - No audit materials are
required.
5.2.5 Cost of Audit - The audit of Method 3 is a calculation
audit of the field sample analytical results. No additional
samples or analysis is required. The audit for Method 3 should
require less than one technical man hour of effort to complete.
This effort would generally represent less than 10 percent of the
total effort to conduct, calculate, and report Method 3 sampling
and analysis.
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Section No. 3.0.5
Date September 23, 1985
Page 12
5.3 Method 5) 5A and 5D (Particulate Matter)
Methods 5, 5A, and 5D should be audited using the quality
assurance requirements in Method 5 (see Reference 4 for details).
5.3.1 Method Description - These Methods, when used in conjunc-
tion with Methods 1, 2, 3, and 4, are applicable for the deter-
mination of particulate emissions from stationary sources.
A gas sample is extracted isokinetically from the stack.
Particulate matter is collected on an out-of-stack, glass fiber
filter maintained at 120 +14 C (248 +25 F) for Methods 5 and 5D
and 42° +10 C (108 +18^F) for Method 5A, or at another
temperature specified by an applicable subpart of the standard or
approved by the Administrator. The mass of particulate matter,
which includes any material that condenses at or above the
specified filter temperature, is measured gravimetrically after
removal of uncombined water. Section 3.4.10 of this Handbook
contains a detailed description of Method 5. Method 5 is found
in 40 CFR 60, Appendix A. Method 5A can be found in the Federal
Register Vol. 47, page 34137, August 6, 1982.
5.3.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures '-
5.3.2.1 Sampling Accuracy - The audit procedure for the sampling
phase is to determine the accuracy of the flow totalizing system
(dry gas meter) which is described below in this subsection and
the accuracy of any differential pressure gauge used to measure
velocity that does not meet the specifications in Section 2.2 of
Method 2, 40 CFR 60, Appendix A. The audit of the differential
pressure gauge is described in Subsection 5.1.2 (Method 2) in
this Section.
The audit of the flow totalizing system may be conducted by
two methods. The first method compares it to the flow rate sys-
tem (orificemeter) in the sample train as described in the
Reference Method and described below. The second method is with
the use of a calibrated orifice that has been certified by EPA.
The following items are provided to conduct a proper audit
of the flow totalizing system using the flow rate system. Using
the calibration data obtained during the calibration procedure
described in Section 5.3 of Method 5, determine the AH for the
metering system orifice. The AHQ is the orifice pressure
differential that correlates to 0.75 cfm of air at 528 R and
29.92 in. Hg in units of in. H20. The AH is calculated as
follows:
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Section No. 3.0.5
Date September 23, 1985
Page 13
e2
AH. = 0,0319 AH
(2
( P"' ) ( Y2 V2 )
bar . ra
where:
AH
T
,m
bar
m
Pressure drop reading from orifice meter, in. H~0.
Absolute average dry gas meter temperature, R.
Barometric pressure, in. Hg.
Total sampling time, min.
Dry gas meter calibration factor, dimensionless.
Volume of gas sample as measured by dry gas meter,
dcf.
0.0319 = (0.0567 in. Hg/wR) x (0.75 dscfm)"
Before beginning the field test (a set of three runs usually con-
stitutes a field test), operate the metering system (i.e., pump,
volume meter, and orifice) at the H pressure differential for
10 minutes. Record the volume collected, the dry gas meter tem-
peratures and the barometric pressure. Calculate the average dry
gas meter temperature. Calculate a dry gas meter calibration
check value, Y , as follows:
c'
Y =
c
10
Vm
0.0319 TV
m
bar
1/2
where:
Y = Dry gas meter calibration check value, dimensionless.
10 = 10 minutes of run time.
Compare the Y value with the dry gas meter calibration factor Y
to determine that :
0.97Y < YC < 1.03Y .
If the Y value is not within this range, the volume metering
system should be investigated before beginning the test and the
audit repeated. If the initial and repeat audit do not agree
with the range, the auditor may take actions deemed appropriate
or inform the tester that if the post test calibration does not
agree within the range stated by the Method, that the results may
affect the acceptability of the test.
Alternatively, the dry gas meter may be audited using a
calibrated flow orifice housed in a quick-connect coupling
certified by the EPA. The following recommendations are provided
as guidance:
1. Remove the calibrated orifice from its case and insert
it into the gas inlet quick-connect coupling on the source
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Section No. 3.0.5
..' '-v. Date September 23, 1985
Page 14
sampling meter box. Turn on the pump and adjust until 19 in.
Hg vacuum is being pulled on the calibrated orifice based on
the sampling meter box'vacuum gauge.
2. Make the quality assurance check prior to the start of
the field test. Record the initial and the final dry gas meter
volumes, the dry gas meter inlet and outlet temperatures, the
internal orifice pressure drop (AH), the ambient temperature,
and the barometric pressure. The duration of the run should be
slightly >15 min. The following procedure is recommended for
each quality assurance run: 15 min. after a run is started,
watch the dry gas meter needle closely. As the needle reaches
the zero (12 o'clock) position stop the pump and stopwatch
simultaneously. Record the dry gas meter volume and the time.
3. Calculate the corrected dry gas volume for the run using
the equation below. Record the collected dry gas volume (V ),
the sampling time in decimal minutes, the barometric pressure
(P, ) the average temperature (T ), the internal orifice
pressure drop (AH) and the dry gas meter calibration factor
CY).
AH
Vm(std) VmY
(+ AH
V 13'
—
where:
K- = 0.3858°K/mm Hg for metric units, or
= 17.64 R/in. Hg for English units.
The auditor should then calculate the percent relative error (RE)
between the measured standard volume and the audit or given
standard volume (calibrated orifice calculated volume). The
percent relative error is a measure of the bias of the volume
measurement in the sampling phase of Method 5. Calculate RE
using the equation below.
RE = VM ~ VA x 100
VA
where:
V = Volume measured by the3field crew, corrected to
standard conditions, m , and
V = Audit or given volume of the audit device, corrected
to standard conditions, m .
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Section No. 3.0.5
Date September 23, 1985
Page 15
4. The results of the calculated RE should be included in
the emission test report as an assessment of the accuracy of the
sampling phase of the Method 5 test.
Since the calibrated orifice is not a primary standard, the
auditor should always have at least two orifices available. When
the first orifice audit results deviate by more than +10 percent,
the second orifice should be used to validate this difference.
When a differential pressure gauge other than an inclined
manometer is used for velocity pressure measurement, an audit to
assess the accuracy of the velocity pressure measurement is rec-
ommended. The audit should follow the procedure and frequency as
described for Method 2 in Subsection 5.1.
5.3.2.2 Analytical Accuracy - None recommended.
5.3.3 Audit Frequency - When Method 5, 5A or 5D is used for
SPNSS purposes, the following audit frequency is recommended for
compliance and enforcement tests. An audit for accuracy of the
sampling procedures should be conducted prior to the field
testing series on all flow totalizing systems (dry gas meters)
and on all differential pressure gauges used for velocity
pressure determination that do not meet the specifications of
Section 2.2 of Method 2. An additional audit should be conducted
on the flow totalizing system when (1) a different flow total-
izing system is used or (2) repairs are made on the flow
totalizing system after auditing. An additional audit should be
conducted on the differential pressure gauge when (1) a different
differential pressure gauge is used or (2) when repairs are made
on the differential pressure gauge after auditing. A lesser fre-
quency may be acceptable when Method 5 is used for applications
other than compliance or enforcement.
5.3.4 Availability of Audit Materials - Control agencies respon-
sible for the compliance or enforcement test may obtain certified
calibrated orifices (when available) prior to each compliance or
enforcement test. By contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
Attention: Source Test Audit Coordinator
Alternatively, a calibrated orifice can be made as described
by Mitchell, et. al. in Reference 5 and sent to the USEPA for
certification.
5.3.5 Cost of Audit - The audit of Method 5, 5A or 5D is an
audit of the sampling phase. This audit should require less than
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Section No. 3.0.5
Date September 23, 1985
Page 16
two technical hours of effort to complete. This effort should
generally represent less than 2 percent of the total effort to
conduct, calculate, and report the Method 5 sampling and
analysis.
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Section No. 3.0.5
Date September 23, 1985
Page 17
5.4 Method 6, 6A, and 6B (Sulfur Dioxide)
Methods 6, 6A and 6B should be audited using the quality
assurance requirements in Method 6. (See Reference 1 for
details. )
5.4.1 Method Description - Method 6 is applicable to the
determination of sulfur dioxide (SO-) emissions from stationary
sources. A gas sample is extracted at a constant rate from the
sampling point in the stack. The S0~ is separated from the
sulfuric acid mist (including sulfur trioxide) and is measured by
the barium-thorin titration method. The barium ions react pref-
erentially with sulfate ions in solution to form a highly insolu-
ble barium sulfate precipitate. When the barium has reacted with
all sulfate ions, excess barium then reacts with the thorin indi-
cator to form a metal salt of the indicator, resulting in a color
change. Section 3.5.10 of this Handbook contains a detailed
description of Method 6. Methods 6, 6A and 6B are found in
40 CFR 60, Appendix A.
5.4.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures -
5.4.2.1 Sampling Accuracy - No audit is recommended when the
midget impingers are used. An audit to assess the accuracy of
the flow measuring device (dry gas meter) is recommended when the
standard size impingers (i.e., Method 5 or Method 8) are used.
The audit of the flow measuring device with the use of a critical
orifice is described in Subsection 5.3.2.
5.4.2.2 Analytical Accuracy - According to Method 6, when the
Method is used for compliance testing, the analyst must analyze
two audit samples along with the field samples. One of these
samples should be at a low concentration (500 to 1000 mg S02/m
of gas sampled when a EPA specified aliquot of the audit sample
is diluted to exactly^ 100 ml) and one at a high concentration
(1500 to 2500 mg S02/m when an EPA specified aliquot of the
audit sample is diluted to exactly 100 ml). This is based on an
emission standard of~l-2 Ib of S02 per million Btu which would be
about 1300 mg S02/m at 35 percent excess air. The percent
relative error (RE) of the audit samples is determined using the
following equation. The calculated RE must be included in the
emission test report as an assessment of the accuracy of the
analytical phase of the Method 6 test.
RE = Cd " Ca x 100
Ca
where:
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Section No. 3.0.5
Date September 23, 1985
Page 18
3
C, = Determined audit sample concentration, mg/m , and
C = Actual audit concentration, mg/m .
a
Method 6 states that the relative error (RE) should be less than
5 percent for both audit samples. When agreement is not met, the
audit samples and field samples must be reanalyzed and the
initial and r.eanalysis results included in the test report.
Nonagreement on the initial and reanalysis results of the audit
samples may void the test.
5.4.2.3 Combined Sampling and Analytical Accuracy - For Method
6B, a cylinder gas '(SO^/CO^ in N9) audit that addresses both
sampling and analytical accuracy is also available (refer to
Section 3.13.:8 of thiis Handbook for details). It is recommended
that this audit toe conducted in addition to the required liquid
sample audit when 'Method ;6B is used for compliance testing.
5.4.3 Audit Frequency - When Method 6 or Method 6A is used for
SPNSS purposes,, the .following audit frequency is recommended for
compliance and enforcement tests. An audit for accuracy of the
analytical procedures should be conducted simultaneously with the
analysis of field samples. The analytical series may contain
field samples from more than one stack or test. The audit sam-
ples should, be analyzed concurrently with the field sample anal-
ysis. An additional audit must be conducted when the analyst,
analytical reagents and/or analytical system is changed. If
acceptable results 'have toeen obtained on an audit performed
within 30 days of the date of the audit sample analysis and the
above conditions are met, the agency may not require an audit. A
lesser frequency may -be acceptable when Method 6 is used for
applications other than compliance and enforcement tests. Note;
When Method 6B is used for compliance with 60.47a (f) of 40 CFR
Part 60, Subpart Da, the analytical procedures must be audited on
a monthly basis (provided the analytical system and analyst do
not change). For the cylinder gas audit of Method 6B, audit
procedures are shown in Section 3.13.8 of this Handbook.
5.4.4 Availability of Audit Materials - Control agencies respon-
sible for the compliance or enforcement test may obtain SO,, audit
samples prior to each compliance or enforcement test, by
contacting the Quality Assurance Coordinator (shown in Table 5,1)
in his respective EPA "Regional Office. The SO~ audit samples are
prepared by EPA's Environmental Monitoring Systems Laboratory at
the Research Triangle Park, North Carolina. For purposes other
than compliance and enforcement tests, audit samples may be
prepared using primary standard grade ammonium sulfate by the
procedure described in this Handbook for control sample prepara-
tion. For details, see .Method 6, Section 3.5.5, Subsection
5.2.5.
5.4.5 Cost of Audit - The required audit for Methods 6, 6A and
6B is an audit of the analysis phase. The audit should require
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Section No. 3.0.5
Date September 23, 1985
Page 19
less than four technical hours of effort to complete. This
effort would generally represent less than 5 percent of the total
effort to conduct, calculate, and report the Method 6 sampling
and analysis.
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Section No. 3.0.5
Date September 23, 1985
Page 20
5.5 Methods 7, 7A, 7C, and 7D (Oxides of Nitrogen)
Methods 7, 7A, 7C, and 7D should be audited using the
quality assurance requirements in Method 7. (See Reference 1 for
details.)
5.5.1 Method Description - Methods 7, 7A, 7C, and 7D are
applicable to the measurement of nitrogen oxides emitted from
stationary sources. The range of the Methods has been determined
to be 2 to 400 mg NO , expressed as NO?' Per drY standard cubic
meter without having to dilute the sample. A gas sample is
extracted from the sampling point in the stack. The sample is
collected in an evacuated 2-liter round bottom borosilicate flask
containing 25 ml of dilute sulfuric acid-hydrogen peroxide
absorbing solution (7 and 7A) or in impingers containing
alkaline-potassium permanganate solution (7C and 7D). The nitro-
gen oxides, except nitrous oxide, are measured colorimetrically
for Method 7 and 7C, and by ion chromatography for Method 7A and
7D. Section 3.6 of the Handbook contains a detailed description
of Method 7. Methods 7, 7A, 7C, and 7D are found in 40 CFR, 60
Appendix A.
5.5.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures -
5.5.2.1 Sampling Accuracy - No audit recommended.
5.5.2.2 Analytical Accuracy - According to Method 7, when the
Method is used for compliance testing, the analyst must analyze
two audit samples along with the field samples. One of the
samples should be at a low concentration (250 to 500 mg N02/dsm
of gas sampled when an EPA specified aliquot of the audit sample
is diluted to exactly 1QO ml), and one at a high concentration
(750 to 1500 mg N02/dsm of gas sampled when an EPA specified
aliquot of the audit sample is diluted to exactly 100 ml). This
is based on an emission standard of 0.7 Ib NO2 per million Btu
which would be about 750 mg/dsm at 35 percent excess air.
The audit samples must be analyzed simultaneously with the
field samples. The percent relative error (RE) of the audit sam-
ples is determined using the equation below. The RE results must
be included with the emission test report as an assessment of the
accuracy of the analytical phase during the Method 7 test.
RE = Cd Ca x 100
ca
where:
3
C, = Determined audit sample concentration, mg/m , and
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Section No. 3.0.5
Date September 23, 1985
Page 21
3
C = Audit or given sample concentration, mg/m .
o
Method 7 states that the relative error (RE) should be less
than 10 percent for both audit samples. When the argument is not
met, the audit samples and field samples must be reanalyzed and
the initial and reanalysis results included in the test report.
Nonagreement on the initial analysis and reanalysis of the audit
samples may void the test.
5.5.3 Audit Frequency - When Method 7 is used for SPNSS
purposes, the following audit frequency is recommended for
compliance and enforcement tests. An audit for accuracy should
be conducted simultaneously with the analysis of the field
samples. The anlayses may contain samples from more than one
stack or test. An additional audit must be conducted when the
analyst, analytical reagents, and/or analytical system is
changed. If acceptable results have been obtained on an audit
performed within 30 days of the date of the audit sample analysis
and the above conditions are not met, the agency may not require
an audit. A lesser frequency may be acceptable when Method 7 is
used for applications other than compliance and enforcement.
5.5.4 Availability of Audit Materials - Control agencies respon-
sible for the compliance or enforcement test may 'obtain NO2 audit
samples prior to each compliance or enforcement test by
contacting the Quality Assurance Coordinator (shown in Table 5.1)
in their respective EPA Regional Office. The NO2 audit samples
are prepared by EPA's Environmental Monitoring Systems Laboratory
at the Research Triangle Park, North Carolina. For purposes
other than compliance and enforcement tests, audit samples may be
prepared using potassium nitrate by the procedure described in
this Handbook for control sample preparation. For details, see
Method 7, Section 3.6.5, Subsection 5.2.2.
5.5.5 Cost of Audit - The audit for Method 7, 7A, 7C, or 7D is
an audit of the analysis phase. This audit should require less
than four technical hours of effort to complete. This effort
would generally represent less than 5 percent of the total effort
to conduct, calculate, and report the Method 7 sampling and
analysis.
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Section No. 3.0.5
Date September 23, 1985
Page 22
5.6 Method 8 (Sulfuric Acid and Sulfur Dioxide)
5.6.1 Method Description - This Method is applicable for the
determination of sulfuric acid mist (including S03) emissions
from stationary sources. A gas sample is extracted isokinet-
ically from the stack. The sulfuric acid mist (including SO,,)
and the SO,, are separated; both fractions are then measured
separately By the barium-thorin titration method. The barium
ions react preferentially with sulfate ions in solution to form a
highly insoluble barium sulfate precipitate. When the barium has
reacted with all sulfate ions, the excess barium reacts with the
thorin indicator to form a metal salt of the indicator and to
give a color change. Section 3.7 of this Handbook contains a
detailed description of Method 8. The Method can be found in
40 CFR 60, Appendix A.
5.6.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures -
5.6.2.1 Sampling Accuracy - The audit for the sampling phase is
used to determine the accuracy of the flow totalizing system (dry
gas meter) of the Method 8 sampling train and the differential
pressure gauge used to measure the velocity when the gauge does
not meet the specifications in Section 2.2 of Method 2 (40 CFR
60, Appendix A). The flow totalizing system should be audited
using the same procedures and with the same frequency as
described in detail for Method 5 in Subsection 5.3.2 of this
Section. The differential pressure gauge should be audited using
the same procedures and with the same frequency as described in
detail for Method 2 in Subsection 5.1.2 of this Section.
5.6.2.2 Analytical Accuracy - The analytical procedures for both
the sulfuric acid and sulfur dioxide should be audited using the
procedure described for Method 6 in Subsection 5.4.2. An
emission standard of 0.15 Ib of sulfuric acid per ton of acid
produced is about 100 mg/dsm at 100 percent excess airland
4.0 Ib of SO2 per ton of acid produced is about 2500 mg/dsm at
100 percent excess air. Note: Separate audits are not necessary
for both the sulfuric acid and sulfur dioxide. The single audit
procedure will provide sufficient accuracy assessment for both
pollutants.
5.6.3 Audit Frequency - When Method 8 is used for SPNSS pur-
poses, the following audit frequency is recommended for compli-
ance and enforcement tests. An audit for accuracy of the
sampling procedures should be conducted prior to the field
testing series on all flow totalizing systems (dry gas meters)
and all differential pressure gauges used for velocity pressure
determination that do not meet the specifications of Section 2.2
of Method 2. An additional audit should be conducted on the flow
totalizing system when (1) a different flow totalizing system is
used or (2) repairs are made on the flow totalizing system after
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Section No. 3.0.5
Date September 23, 1985
Page 23
auditing. An additional audit should be conducted on the differ-
ential pressure gauge when (1) a different differential pressure
gauge is used or (2) repairs are made on the differential
pressure gauge after auditing. An audit for accuracy of the
analytical procedures should be conducted prior to the analysis
of the field samples for every field test series. The analytical
series may contain field samples from more than one stack or
test. A lesser frequency may be acceptable when Method 8 is used
for applications other than compliance and enforcement.
5.6.4 Availability of Audit Materials - Control agencies respon-
sible for the compliance or enforcement test may obtain certified
calibrated orifices (when available) prior to each compliance or
enforcement source test. Orifices may be obtained by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
Attention: Source Test Audit Coordinator
Alternatively, a calibrated orifice can be made as described
by Mitchell, et. al. in Reference I and sent to the USEPA for
certification.
Agencies may obtain SO,, audit samples prior to each
compliance or enforcement rest by contacting the Quality
Assurance Coordinator (Table 5.1) in his respective EPA Regional
Office. The SO2 audit samples are prepared by EPA's
Environmental Monitoring Systems Laboratory at the Research
Triangle Park, North Carolina. For purposes other than
compliance and enforcement tests, audit samples may be prepared
using primary standard grade ammonium sulfate by the procedure
described in this Handbook for control sample preparation. For
details, see Method 6, Section 3.5.5, Subsection 5.2.5.
5.6.5 Cost of Audit - The audit for Method 8 is an audit of por-
tions of both the sampling and analytical phases. These audits
should require less than five technical hours of effort to com-
plete. This effort would generally represent less than 5 percent
of the total effort to conduct, calculate, and report the Method
8 sampling and analysis.
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Section No. 3.0.5
Date September 23,
Page 24
1985
5.7 Method 10 (Carbon Monoxide)
5.7.1 Method Description - Method 10 is applicable to the deter-
mination of carbon monoxide (CO) from stationary sources. A gas
sample is extracted from the stack either at a constant rate
using a continuous sampling train (constant rate sampling) or at
a rate proportional to the stack gas velocity using an integrated
sampling train. The concentration of CO from both sampling meth-
ods is determined by a Luft-type nondispersive infrared (NDIR)
analyzer. The Method is applicable to stationary sources when
specified by a compliance regulation and/or when the CO concen-
tration is >_20 parts per million (ppm) for a O-to-1000-ppm
testing range. With this Method, interferences can result from
substances with strong infrared absorption energies. Major
interferences can be avoided using silica gel and Ascarite traps
to remove H20 and C02, respectively. If traps are used, the
sample volumes must be adjusted to account for the C02 removed.
Section 3.8 of this Handbook contains a detailed description of
Method 10. The Method can be found in 40 CFR 60, Appendix A.
Note: This audit is not applicable to 40 CFR 60, Subpart Z
(Ferroalloy Production Facilities).
5.7.2 Audits to Assess Accuracy of Sampling and Analysis Proce-
dures - The^ accuracy of the sampling and analytical procedure is
assessed by conducting a cylinder gas audit. An audit cylinder
of CO is needed. Use audit gas that has been certified by com-
parison with National Bureau of Standards (NBS) gaseous Standard
Reference Materials (SRM) or NBS/EPA approved gas manufacturer's
Certified Reference Materials (CRM) following EPA Traceability
Protocol No. 1 for audit gases (Section 3.0.4 of this Handbook).
CRM's may be used directly as audit gases; procedures for
preparation of CRM's are described in Reference 6.
The audit sample concentration should be within the range of
40 to 200 percent of the applicable regulation. A typical stan-
dard of 0.050 percent would require an audit cylinder of 0.02 to
0.1 percent CO. Note; The audit gas must not be the gas used
for normal calibration.
The following recommendations
conducting a proper audit.
are provided as guidance for
1. The analyzer should be at normal operating conditions.
No adjustment must be made during the audit.
2. For a continuous sampling train, attach a manifold or
vented bubbler to the probe tip. Be sure that the audit gas flow
to the manifold is kept under a slight positive pressure at all
times. For integrated sampling trains, fill a sample bag with
the audit gas, and attach the bag to the analyzer.
3. Challenge the analyzer prior to the first sample
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Section No. 3.0.5
Date September 23, 1985
Page 25
analysis and again after the last sample analysis.
4. Compute the percent relative error (RE) for the audit,
RE = CM ~ CA x 100
CA
where:
CM = Concentration measured by NDIR, ppm, and
C, = Audit or given concentration of the audit sample, ppm.
f\
5. An acceptable relative error of +^15% or +^50 ppm (which-
ever is greater) has been established for this~~method. These
relative errors are based on the SO2 and NO monitor's cylinder
gas audits as described in Reference 7, and on the collaborative
tests from Method 10 as described in Reference 8.
6. The results of the calculated RE should be included in
the emission test report as an assessment of the accuracy of the
sampling and analysis phase of Method 10.
5.7.3 Audit Frequency - When Method 10 is used for SPNSS pur-
poses, the following audit frequency is recommended for
compliance and enforcement tests. An audit for accuracy should
be conducted after the NDIR calibration and prior to and at the
conclusion of, the field sample analysis. A lesser frequency may
be acceptable when Method 10 is used for applications other than
compliance and enforcement.
5.7.4 Availability of Audit Materials - The given concentrations
of CO cylinder gases used for audits of Method 10 must be both
accurate and stable. Accurate and stable CO cylinder gases are
available from several commercial cylinder gas manufacturers.
They can be obtained by two methods:
1) Require the gas manufacturer to use Protocol 1 to estab-
lish the audit gas concentration. (The gas manufacturer should
also be required to guarantee in writing that Protocol 1 was
followed to certify the audit gas concentration.)
2) Obtain a CRM gas from a commercial gas manufacturer. A
list of commercial gas manufacturers who have CO CRM gases
approved for sale by NBS/EPA may be obtained by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
Attention: List of CRM Manufacturers
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Section No. 3.0.5
Date September 23, 1985
Page 26
5.7.5 Cost of Audit - The audit of Method 10 is an audit of both
the sampling and analysis phases. This audit should require less
than four technical hours of effort to complete. This effort
will generally represent less than 5 percent of the total effort
to conduct, calculate, and report the Method 10 sampling and
analysis.
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Section No. 3.0.5
Date September 23, 1985
Page 27
5.8 Method 11 (Hydrogen Sulfide)
5.8.1 Method Description - This Method is applicable for the
determination of hydrogen sulfide. The hydrogen sulfide is
collected from the source in a series of midget impingers and
reacted with acidified cadmium sulfate CdSO. to form cadmium
sulfide (CdS). The precipitated CdS is then dissolved in hydro-
chloric acid to regenerate H2S, which is absorbed in a known
volume of iodine solution. The iodine consumed is a measure of
the H^S content of the gas. An impinger containing hydrogen
peroxide is included to remove S0« as an interfering specie. The
sampling and analytical procedures are not described in this
Handbook. The promulgated Method is in the Federal Register.
Vol. 43, page 1494, January 10, 1978 and 40 CFR, Appendix A.
5.8.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures - The accuracy of the sampling and analytical pro-
cedure is assessed by conducting a cylinder gas audit. One audit
cylinder of H2S is needed. The audit cylinder will assess both
the sampling and analytical procedures. The range of the audit
gas should be within about 40 to 200 percent of the applicable
standard. An emission standard of 0.016 percent H,,S would
require an audit concentration between 64 to 320 percent H_S.
The following items are provided as guidance to conduct a proper
audit.
1. The tester should attach a manifold system or vented
bubbler to the sample train and keep the audit gas at a slightly
positive pressure through the manifold to ensure that the audit
sample is not diluted with ambient air. The vented H2S should be
discharged into a well ventilated area for safety reasons.
2. The tester should attach the manifold or bubbler to the
sample train and sample the audit gas using the standard sampling
procedures. The tester should ensure an undiluted transfer of
audit gas to the sample train.
3. The tester should then recover and analyze the audit
sample in the same manner and at the same time as the field
samples. This requires an additional sample collection run and
analysis to be performed.
4. Compute the percent relative error (RE) for the audit,
RE
c -
Si
x 100
where:
CM = Concentration measured by Method 11, ppm H2S, and
CV = Audit or given concentration of the audit sample, ppm
H2S.
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Section No. 3.0.5
Date September 23, 1985
Page 28
5. The results of the calculated RE should be included in
the emission test report as an assessment of the accuracy of the
sampling and analytical phase of the Method 11 test. An
acceptable relative error has been established as +15 percent for
this Method. This relative error has been established based on
the S02 and NO monitor's cylinder gas audits, as described in
Reference 7, and on the collaborative tests, as described in
Reference 9. Due to the cost of auditing and the analytical
procedures for this Method, a single audit sample is recommended
which is analyzed with the field samples.
5.8.3 Audit Frequency - When Method 11 is used for SPNSS pur-
poses, the following audit frequency is recommended for compli-
ance and enforcement tests. An audit for accuracy should be con-
ducted once during each field testing series and the collected
audit sample analysed with the field samples. A lesser frequency
may be acceptable when Method 11 is used for other applications,
depending on the purpose of the test.
5.8.4 Availability of Audit Materials - Control agencies
responsible for compliance and enforcement tests may obtain an
audit cylinder of H2S prior to each compliance or enforcement
test by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77B)
Research Triangle Park, North Carolina 27711
Attention: Audit Cylinder Gas Coordinator
If an audit cylinder is unavailable, commercial manufac-
turers should be sought to obtain the desired audit gas.
5.8.5 Cost of Audit - The audit for Method 11 is an audit of
both the sampling and analysis phase. This audit should require
less than four technical hours of effort to complete. This
effort will generally represent less than 5 percent of the total
effort to conduct, calculate, and report the Method 11 sampling
and analysis.
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Section No. 3.0.5
Date September 23, 1985
Page 29
5.9 Method 12 (Inorganic Lead)
5.9.1 Method Description - This Method applies to the determi-
nation of inorganic lead (Pb) emissions. Particulate and gaseous
Pb are withdrawn isokinetically from the source and collected on
a filter and in dilute nitric acid. The collected samples are
digested in acid solution and analyzed by atomic absorption spec-
trometry using an air acetylene flame. The sampling and analy-
tical procedures are not described in this Handbook. The Method
can be found in 40 CFR 60, Appendix A.
5.9.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures -
5.9.2.1 Sampling Accuracy - The audit for the sampling phase is
to determine the accuracy of the flow totalizing system (dry gas
meter) of the Method 12 sampling train and the differential pres-
sure gauge used to measure the velocity when the gauge does not
meet the specifications in Section 2.2 of Method 2 (40 CFR 60,
Appendix A). The flow totalizing system should be audited using
the same procedures and with the same frequency as described in
detail for Method 5 in Subsection 5.3.2 of this Section. The
differential pressure gauge should be audited using the same
procedures and with the same frequency as described in detail for
Method 2 in Subsection 5.1.2 of this Section.
5.9.2.2 Analytical Accuracy - The analytical procedures should
be audited using two audit samples. The audit samples are glass
fiber filters impregnated with lead nitrate. One audit sample
should be at a low concentration (between 100 yg and 600 yg total
weight of lead per audit sample) and one audit sample at a high
concentration (between 900 yg and 2000 yg total weight of lead
per audit sample). This requirement is based on emission
standards of 0.4 mg/dsm and 1.0 mg/dsm corresponding to about
400 and 1000 yg of lead per sample. These audit samples should
be prepared simultaneously with the field samples using the same
procedures, but analyzed prior to the source test filter. The
auditor should calculate the relative error (RE) of the audit
samples using the equation below. The calculated RE should be
included in the emission test report as an assessment of the
accuracy of the analytical phase of the Method 12 test.
RE = CM ~ CA x 100
CA
where:
CM = Concentration measured by the lab analyst, total yg
lead per audit sample, and
CA = Audit or given concentration of the audit sample
(glass fiber filter), total yg lead per audit sample.
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Section No. 3.0.5
Date September 23, 1985
Page 30
An acceptable relative error has been established as +15 percent
for this Method. The relative error was established based on the
collaborative tests, as described in Reference 10.
5.9.3 Audit Frequency - When Method 12 is used for SPNSS pur-
poses, the following audit frequency is recommended for com-
pliance and enforcement tests. An audit for accuracy of the
sampling procedures should be conducted prior to the field
testing series on all flow totalizing systems (dry gas meters)
and all differential pressure gauges used for velocity pressure
determination that do not meet the specifications of Section 2.2
of Method 2. An additional audit should be conducted on the flow
totalizing system when (1) a different flow totalizing system is
used or (2) repairs are made on the flow totalizing system after
auditing. An additional audit should be conducted on the differ-
ential pressure gauge when (1) a different differential pressure
gauge is used or (2) repairs are made on the differential pres-
sure gauge after auditing. An audit for accuracy of the analyses
of the field sample should be conducted after the preparation of
the calibration curve and just prior to the field sample anal-
ysis. The analyses may cover samples from more than one stack or
test. A lesser frequency may be acceptable when Method 12 is
used for applications other than compliance and enforcement.
5.9.4 Availability of Audit Materials - Control agencies respon-
sible for the compliance or enforcement test may obtain lead
audit samples (glass fiber filter strips impregnated with lead
nitrate) and a certified calibrated orifice prior to each
compliance or enforcement test by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
Attention: Source Test Audit Coordinator
Alternatively, a calibrated orifice can be made as described
by Mitchell, et. al. in Reference 5 and sent to the USEPA for
certification.
5.9.5 Cost of Audit - The audit for Method 12 is an audit of
portions of both the sampling and the analysis phase. This audit
should require less than five technical hours of effort to com-
plete. This effort will generally represent less than 5 percent
of the total effort to conduct, calculate, and report the Method
12 sampling and analysis.
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Section No. 3.0.5
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Page 31
5.10 Methods 13A and 13B (Total Fluoride)
5.10.1 Method Description - These Methods are applicable for the
determination of fluoride emissions from stationary sources.
Fluorocarbons, such as Freons, are not quantitatively collected
or measured by these procedures. Both Methods withdraw gaseous
and particulate fluorides from the source isokinetically using a
sample train with water-filled impingers and filter(s). Method
13A determines the weight of total fluoride by the SPADNS Zir-
conium Lake colorimetric method. If chloride ion is present, it
is recommended that Method 13B be used. Method 13B determines
the weight of fluorides by the specific ion electrode method.
Section 3.9 and Section 3.10 of this Handbook contain detailed
descriptions of Methods 13B and 13A, respectively. The Method
can be found in 40 CFR 60, Appendix A.
5.10.2 Audits to Access Accuracy of Sampling and Analytical
Procedures -
5.10.2.1 Sampling Accuracy - The audit for the sampling phase is
used to determine the accuracy of the flow totalizing system (dry
gas meter) of the Method 13 sampling train and the differential
pressure gauge used to measure the velocity when the gauge does
not meet the specifications in Section 2.2 of Method 2 (40 CFR
60, Appendix A). The flow totalizing system should be audited
using the same procedures and with the same frequency as des-
cribed in detail for Method 5 in Subsection 5.3.2 of this Sec-
tion. The differential pressure gauge should be audited using
the same procedures and with the same frequency as described in
detail for Method 2 in Subsection 5.1.2 of this Section.
5.10.2.2 Analytical Accuracy - The analytical procedures for
both Methods 13A and 13B should be audited using the same proce-
dure. The auditor should provide two audit samples to be anal-
yzed along with the field samples, one sample at a low concen-
tration (0.2 to 1.0 mg fluoride/dsm of gas sampled or approxi-
mately 1 to 5 mg NaF/liter of sample)3 and one at a high
concentration (1 to 5 mg of fluoride/dsm of gas sampled or
approximately 5 to 25 mg NaF/liter of sample). The above values
are typical for fertilizer plants with emission limits of 0.01
Ib/ton and 0.02 Ib/ton. Actual values can vary since the
allowable concentration is dependent on both process design and
operation.
The audit samples should be analyzed at the same time as the
field samples for Method 13A and after preparation of the cali-
bration curve and just prior to analysis for Method 13B. The
percent relative error (RE) of the audit sample is determined
using the equation below. The calculated RE should be included
in the emission test report as an assessment of the accuracy of
the analytical phase of the Method 13A or 13B test.
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Section No. 3.0.5
Date September 23, 1985
Page 32
RE = CM " CA x 100
CA
where:
C = Concentration measured by the lab analyst, rag/ml, and
CA = Audit or given concentration of the audit sample,
ing/ml.
An acceptable relative error has been established as +15
percent for this Method. The relative error has been established
based on the collaborative test described in Reference 11.
5.10.3 Audit Frequency - When Method 13A or 13B is used for
SPNSS purposes, the following audit frequency is recommended for
compliance and enforcement tests. An audit for accuracy of the
sampling procedures should be conducted prior to the field
testing series on all flow totalizing systems (dry gas meters)
and all differential pressure gauges used for velocity pressure
determination that do not meet the specifications of Section 2.2
of Method 2. An additional audit should be conducted on the flow
totalizing system when (1) a different flow totalizing system is
used or (2) repairs are made on the flow totalizing system after
auditing. An additional audit should be conducted on the dif-
ferential pressure gauge when (1) a different differential pres-
sure gauge is used or (2) repairs are made on the differential
pressure gauge after auditing.
An audit for accuracy of the analytical procedures should be
conducted simultaneously with the analysis of every series of
field samples for Method 13A and after the preparation of the
calibration curve and prior to field sample analysis for Method
13B. The analytical series may contain field samples from more
than one stack or test. A lesser frequency may be acceptable
when either Method 13A or 13B is used for other applications,
depending on the purpose of the test.
5.10.4 Availability of Audit Materials - Control agencies re-
sponsibleforthecomplianceorenforcement test may obtain
aqueous sodium fluoride (NaF) audit samples and a certified
calibrated orifice by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
Attention: Source Test Audit Coordinator
Alternatively, a calibrated orifice can be made as described
by Mitchell, et. al. in Reference 5 and sent to the USEPA for
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Section No. 3.0.5
Date September 23, 1985
Page 33
certification.
If audit samples are to be used for other purposes, aqueous
NaF audit samples may be prepared by the procedure described in
this Handbook for control sample preparation. This procedure is
described in Section 3.10.5, Subsection 5.2.6 for Method 13A and
Section 3.9.5, Subsection 5.2.6 for Method 13B.
5.10.5 Cost of Audit - The audit for Method ISA or 13B is an
audit for portions of both the sampling and analysis phase.
These audits should require less than five technical hours of
effort to complete. This effort will generally represent less
than 5 percent of the total effort to conduct, calculate and
report the Method 13 sampling and analysis.
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Section No. 3.0.5
Date September 23, 1985
Page 34
5.11 Method 15 (Hydrogen Sulfide, Carbonyl Sulfide, and Carbon
Disulfide)
5.11.1 Method Description - Method 15 is applicable for deter-
mination of hydrogen sulfide (H2S), carbonyl sulfide (COS), and
carbon disulfide (CS«) from tail gas control units of sulfur
recovery plants. A gas sample is extracted from the emission
source through a heated probe and diluted with clean dry air. An
aliquot of the diluted sample from the sample line is then
analyzed for H2S, COS, and CS2 by gas chromatographic (GC)
separation and flame photometric detection (FPD). The sampling
and analytical procedures are not described in this Handbook.
The promulgated Method is in the Federal Register, Vol. 43,
page 10866, March 15, 1978 and 40 CFR 60 Appendix A.
5.11.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures - The accuracy of the sampling and analytical proce-
dureis assessed by conducting a cylinder gas audit. Two audit
cylinders [one of hydrogen sulfide (Hos) and one of carbonyl
sulfide (COS)J are needed. The total concentration of the two
audit gases should be within about 40 to 200 percent of the
applicable standards. Tor an emissions standard of 0.030 percent
by volume reduced sulfur compound and 0.0010 percent by volume
hydrogen sulfide, audit gases of 100 to 500 ppm COS and 4 to 20
ppm H2S would typically be used. The following items are pro-
vided as guidance to conduct a proper audit:
1. The standard post-test procedure of determining the sam-
ple line loss should be run by the tester.
2. Prior to collection of the field sample, the tester
should attach either of the audit cylinders to the opening of the
probe. The audit gas should be fed to the probe in sufficient
quantity to ensure that the excess sample is vented to the atmos-
phere. The number of audit sample injections for analysis and
the time between sample injections is left to the discretion of
the tester.
3. After completion of one audit cylinder, the other audit
cylinder should then be attached in the same manner. The tester
is responsible for ensuring that the audit gas is introduced into
the sample train in an acceptable manner and at .an acceptable
rate.
4. The results of the audit sample results should be cal-
culated in the same manner used to calculate the field sample
results and should be included in the test report.
5. The auditor can then compute the percent relative error
(RE) for the audit.
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Section No. 3.0.5
Date September 23, 1985
Page 35
RE = °M " CA x 100
CA
where:
CM = Concentration measured by Method 15, ppm H_S or ppm
COS, and
CA = Audit or given concentration of the audit sample, ppm
H2S or ppm COS.
6. An acceptable relative error of +20 percent has been
established for this Method. This relative error has been estab-
lished based on the collaborative test described in Reference 12.
7. The calculated RE should be included in the emission
test report as an assessment of the accuracy of the sampling and
analytical phases of the Method 15 test.
5.11.3 Audit Frequency - When Method 15 is used for SPNSS pur-
poses, the following frequency is recommended for compliance and
enforcement tests. An audit for accuracy should be conducted
prior to each field test series at the conclusion of the sample
line loss determination. A lesser frequency may be acceptable
when Method 15 is used for other applications, depending on the
purpose ot the test.
5.11.4 Availability of Audit Materials - Control agencies re-
sponsible for the compliance or enforcement test may obtain audit
cylinders of H_S and COS prior to each compliance or enforcement
source test. The H-S and COS audit cylinders may be obtained by
contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77B)
Research Triangle Park, North Carolina 27711
Attention: Audit Cylinder Gas Coordinator
If the audit cylinders are unavailable, commercial manu-
facturers should be sought to obtain the desired audit gases.
5.11.5 Cost of Audit - The audit for Method 15 is an audit of
both the sampling and analysis phase. This audit should require
less than five technical hours of effort to complete. This ef-
fort will generally represent less than 5 percent of the total
effort to conduct, calculate, and report the Method 15 sampling
and analysis.
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Section No. 3.0.5
Date September 23, 1985
Page 36
5.12 Method 16 (Sulfur Emissions)
5.12.1 Method Description - Method 16 is applicable for deter-
mination of hydrogen sulfide (H2S), methyl mercaptan (MeSH),
dimethyl sulfide (DMS), and dimethyl disulfide (DMDS) from recov-
ery furnaces, lime kilns, and smelt dissolving tanks at kraft
pulp mills. The four compounds shown above are collectively
known as total reduced sulfur (TRS). A gas sample is extracted
from the emission source through a heated probe and diluted with
clean air. An aliquot of the diluted sample from the sample line
is then analyzed for H^S, MeSH, DMS, and DMDS by gas chromato-
graphic (GC) separation and flame photometric detection (FPD).
The sampling and analytical procedures are not described in this
Handbook. The promulgated Method can be found in the Federal
Register, Vol. 43, page 7568, February 23, 1978 and 40 CFR 60,
Appendix A.
5.12.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures - The accuracy of the sampling and analytical proce-
dure is assessed by conducting a cylinder gas audit. One audit
cylinder of hydrogen sulfide is needed. The hydrogen sulfide (H2
S) concentration should be within 40 to 200 percent of the
applicable standard. For an emission standard of 5 ppm by volume
of total reduced sulfur, an audit concentration of 2 to 10 ppm of
would typically be used. The following items are provided as
i A A i^> n wu-LXA tjijf^sj.wa^^jf i-^vx u^ w. • * AAV 4. i
guidance to conduct a proper audit.
1. The standard post-test procedure of determining the sam-
ple line loss should be run by the tester.
2. Prior to collecting the field samples, the tester should
attach the audit cylinder to the opening of the probe. The audit
gas should be fed to the probe in sufficient quantity to ensure
that an excess of sample is vented to the atmosphere. The gas
should be vented into a well-ventilated area for safety reasons.
The number of audit sample injections for analysis and the time
between sample injections is left to the discretion of the
tester.
3. The results of the audit gas sampling should be calcu-
lated in the same manner used to calculate the field sample re-
sults and should be included in the test report.
4. The auditor can then compute the percent
(RE) for the audit.
relative error
RE =
- c.
x 100
where:
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Section No. 3.0.5
Date September 23, 1985
Page 37
C = Concentration measured by Method 16, ppm H_S, and
C. = Audit or given concentration of the audit sample, ppm
H2S.
5. An acceptable relative error of +20 percent has been
established for this Method. This relative error has been
established based on the collaborative test described in
Reference 12.
6. The calculated RE should be included in the emission
test report as an assessment of the accuracy of the sampling and
analytical phase of the Method 16 test.
5.12.3 Audit Frequency - When Method 16 is used for SPNSS pur-
poses, the following frequency is recommended for compliance and
enforcement tests. An audit for accuracy should be conducted
prior to each field test, at the conclusion of the sample line
loss determination. A lesser frequency may be acceptable when
Method 16 is used for other applications, depending on the
purpose of the test.
5.12.4 Availability of Audit Materials - Control agencies re-
sponsible for the compliance or enforcement test may obtain audit
cylinders of H^S prior to each compliance or enforcement source
test. The H2S audit cylinder may be obtained by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77B)
Research Triangle Park, North Carolina 27711
Attention: Audit Cylinder Gas Coordinator
If the audit cylinders are unavailable, commercial manu-
facturers should be sought to obtain the desired audit gases.
5.12.5 Cost of Audit - The audit of Method 16 is an audit of
both the sampling and analysis phase. This audit should require
less than five technical hours of effort to complete. This ef-
fort should generally represent less than 5 percent of the total
effort to conduct, calculate, and report the Method 16 sampling
and analysis.
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Section No. 3.0.5
Date September 23, 1985
Page 38
5.13 Method 16A (Total Reduced Sulfur Emissions)
Method 16A should be audited using the quality assurance
requirements in Method 16A. (See Reference 13 for details.)
5.13.1 Method Description - Method 16A is an alternative method
to Method 16 for determining total reduced sulfur (TRS) compounds
from recovery furnaces, lime kilns, and smelt dissolving tanks at
kraft pulp mills. A gas sample is extracted from the sampling
point in the stack. S02 is selectively removed from the sample
using a citrate buffer solution. The reduced sulfur compounds
are then oxidized and analyzed as S02 using the barium-thorin
titration procedure of Method 6. The sampling and analytical
procedures are not described in this Handbook. The promulgated
Method can be found in the Federal Register, Vol. 50, page 9578,
March 8, 1985 and 40 CFR 60, Appendix A.
5.13.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures - The accuracy of the sampling and analytical
procedures is assessed by conducting a cylinder gas audit, and
the accuracy of the analytical procedures is assessed by analysis
of a set of aqueous audit samples.
5.13.2.1 Sampling and Analytical Accuracy - The procedures
described in detail in Section 4.2 "System Performance Check" of
Method 16A should be used to assess the sampling and analytical
accuracy. This audit should be conducted in accordance with the
Reference Method and will require a separate sample collection
and analysis. The hydrogen sulfide (H~S) concentration of the
audit gas should be between 40 and 200 percent of the applicable
standard. For an emission standard of 5 ppm by volume of total
reduced sulfur, an audit concentration of 2 to 10 ppm of H~S
would typically be used. The auditor should calculate tne
percent relative error (RE) for the audit as shown below.
RE = CM ~ CA x 100
CA
where::
CM = Concentration measured by Method 16A, ppm H^S, and
Ca = Audit or given concentration of the audit sample, ppm H-S.
A £
An acceptable relative error of +_ 20% has been established
for this Method. The calculated RE should be included in the
emission test report as an assessment of the accuracy of the
sampling and analytical phase of the Method 16A test.
5.13.2.2 Analytical Accuracy - According to Method 16A, when the
Method is used for compliance testing, the analyst must analyze
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Section No. 3.0.5
Date September 23, 1985
Page 39
two aqueous audit samples along with the field samples. The
percent relative error (RE) for each of the audit samples is
determined using the following equation. The calculated RE's
must be included in the emission test report as an assessment of
the accuracy of the analytical phase of the Method 16A test.
RE = Cd " Ca x 100
ca
where:
3
C, = Determined audit sample concentration, mg/m , and
C = Actual audit concentration, mg/m .
a
Method 16A states that the relative error shall be less than
5 percent for both audit samples. When this specification is not
met, the audit samples and field samples must be reanalyzed and
the initial and reanalysis results included in the test report.
Failure to meet the 5 percent specification on the initial and
reanalysis results of the audit samples may void the test.
5.13.3 Audit Frequency - When Method 16A is used for SPNSS pur-
poses, the following frequency is recommended for compliance and
enforcement tests. Audits for both sampling and analytical
accuracy and analytical accuracy should be conducted once for
each field test in accordance with the Method 16A. A lesser
frequency may be acceptable when Method 16A is used for other
applications, depending on the purpose of the test.
5.13.4 Availability of Audit Materials - Control agencies re-
sponsible for the compliance or enforcement test may obtain
aqueous audit samples prior to each compliance or enforcement
source test by contacting the respective EPA Regional Office
Quality Assurance Coordinator (shown in Table 5.1). Audit
cylinders of H2S may be obtained by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77B)
Research Triangle Park, North Carolina 27711
Attention: Audit Cylinder Gas Coordinator
If the audit cylinders are unavailable, commercial manu-
facturers should be sought to obtain the desired audit gases.
5.13.5 Cost of Audit - The audit of Method 16A is an audit of
both the sampling and analysis phase. This audit should require
less than five technical hours of effort to complete. This
effort should generally represent less than 5 percent of the
total effort to conduct, calculate and report the Method 16A sam-
pling and analysis.
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Page 40
5.14 Method 17 (Instack Filterable Particulate)
5.14.1 Method Description - This Method applies to the measure-
ment of particulate matter emissions from stationary sources.
This Method is not applicable when stack gases are saturated with
water vapor or when the projected cross-sectional area of the
probe emission-filter holder assembly covers more than 3 percent
of the stack cross-sectional area. For SPNSS, the Method should
only be used when (1) specified by the applicable subpart of the
standards and only within the temperature limits (if specified)
or (2) otherwise approved by the Administrator. Particulate
matter is withdrawn isokinetically from a gas stream and col-
lected on a glass filter maintained at stack temperature. The
particulate matter mass is determined gravimetrically after
removal of uncombined water. Subsection 3.11.10 of this Handbook
contains a detailed description of Method 17. The Method can
also be found in 40 CFR 60, Appendix A.
5.14.2 Audits to Assess Accuracy of Sampling and Analysis
5.14.2.1 Sampling Accuracy - The audit for the sampling phase is
used to determine the accuracy of the flow totalizing system (dry
gas meter) of the Method 17 sampling train and the differential
pressure gauge used to measure the velocity when the gauge does
not meet the specifications in Section 2.2 of Method 2 (40 CFR
60, Appendix A). The flow totalizing system should be audited
using the same procedures and with the same frequency as des-
cribed in detail for Method 5 in Subsection 5.3.2 of this Sec-
tion. The differential pressure gauge should be audited using
the same procedures and with the same frequency as described in
detail for Method 2 in Subsection 5.1.2 of this Section.
5.14.2.2 Analytical Accuracy - None recommended.
5.14.3 Audit Frequency - When Method 17 is used for SPNSS pur-
poses, the following audit frequency is recommended for compli-
ance and enforcement tests. An audit for accuracy of the sam-
pling procedures should be conducted prior to the field testing
series on all flow totalizing systems (dry gas meters) and on all
differential pressure gauges used for velocity pressure deter-
mination that do not meet the specifications of Section 2.2 of
Method 2. An additional audit should be conducted on the flow
totalizing system when (I) a different flow totalizing system is
used or (2) repairs are made on the flow totalizing system after
auditing. An additional audit should be conducted on the dif-
ferential pressure gauge when (1) a different differential
pressure gauge is used or (2) repairs are made on the dif-
ferential pressure gauge after auditing. A lesser frequency may
be acceptable when Method 17 is used for applications other than
compliance and enforcement.
5.14.4 Availability of Audit Materials - Control agencies
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Section No. 3.0.5
Date September 23, 1985
Page 41
responsible for the compliance or enforcement test may obtain
certified calibrated orifices (when available) prior to each
compliance or enforcement source test. Orifices may be obtained
by contacting:
U. S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
Attention: Source Test Audit Coordinator
Alternatively, a calibrated orifice can be made as described
by Mitchell, et. al. in Reference 5 and sent to the USEPA for
certification.
5.14.5 Cost of Audit - The audit of Method 17 is an audit of the
sampling phase. The audit should require less than three tech-
nical hours of effort. This effort will generally represent less
than 5 percent of the total effort to conduct, calculate and re-
port the Method 17 sampling and analysis.
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Section No. 3.0.5
Date September 23, 1985
Page 42
5.15 Method 18 (Gaseous Organic Compounds)
Method 18 should be audited using the quality assurance re-
quirements in Method 18. (See Reference 2 for details.)
5.15.1 Method Description - Method 18 is applicable to approx-
imately 90 percent of the total gaseous organics emitted from an
industrial source. It does not include techniques to identify
and measure trace amounts of organic compounds, such as those
found in building air and fugitive emission sources. The Method
will not determine compounds that (1) are polymeric (high mole-
cular weights), (2) can polymerize before analysis, or (3) have
very low vapor pressures at stack or instrument conditions. The
Method is based on separating the major components of a gas mix-
ture with a gas chromatograph (GC) and measuring the separated
components with a suitable detector. This sampling and ana-
lytical technique is not described in this Handbook. The prom-
ulgated Method can be found in the Federal Register, Vol. 48,
page 48344, November 18, 1983 and 40 CFR 60, Appendix A.
5.15.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures - The accuracy of the sampling and analytical pro-
ceduresis assessed by conducting a cylinder gas audit. Two
audit cylinders of an appropriate total gaseous organic are
needed. The organic compound should be one of the major organic
components being tested and the given concentration of the audit
gas should be between 25 to 100 percent of the applicable emis-
sion limit for the low concentration, and 100 to 250 percent of
the applicable emission limit for the high concentration
cylinder. The audit cylinder gas will assess both the sampling
and analytical procedures. The audit procedures should follow
those described in 40 CFR 61, Appendix C, Procedure 2: "Proce-
dure for Field Auditing GC Analysis" of the Federal Register,
Vol. 47, page 39179, September 7, 1982 (Reference 14). The
analysis of the audit samples shall be conducted after the
preparation of the calibration curve and prior to the final field
samp1e analysis.
The auditor should compute the percent relative error (RE)
for each audit.
RE = CM CA x 100
CA
where:
CM = Concentration measured by Method 18 in ppm of the
stated organic, and
C. = Audit or given concentration of the audit sample in
ppm of the stated organic.
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Section No. 3.0.5
Date September 23, 1985
Page 43
Method 18 requires that the calculated relative error be
less than +10 percent for both audit sample analyses. The cal-
culated RE should be included in the emission test report as an
assessment of the accuracy of the sampling and analytical phase
of the Method 18 test.
5.15.3 Audit Frequency - When Method 18 is used for SPNSS pur-
poses, the following audit frequency is recommended for com-
pliance and enforcement tests. An audit for accuracy should be
conducted after the preparation of the calibration curve and
prior to the field sample final analysis for every field test
series. A lesser frequency may be acceptable when Method 18 is
used for applications other than compliance and enforcement
tests.
5.15.4 Availability of Audit Materials - Control agencies re-
sponsible for the compliance or enforcement test may obtain EPA
Method 18 audit gas cylinders prior to each compliance or en-
forcement test. The audit gas cylinders may be obtained by
contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77B)
Research Triangle Park, North Carolina 27711
Attention: Audit Cylinder Gas Coordinator
If an audit gas cylinder is unavailable, commercial manu-
factureres should be sought to obtain the desired audit gas.
5.15.5 Cost of Audit - The audit of Method 18 is an audit of
both the sampling and analysis phase. This audit should require
less than six technical hours of effort to complete. This would
generally represent less than 10 percent of the total effort to
conduct, calculate, and report the Method 18 sampling and anal-
ysis.
A complete list of organic compounds for which audit cylin-
ders are available from the U. S. Environmental Protection Agency
is shown in Table 5.3 Audit cylinders are generally available at
a low concentration level (5 to 20 ppm) and a high concentration
level (50 to 700 ppm) for each organic shown in the table. The
table also shows those organic compounds which the U. S. Envir-
onmental Protection Agency has found to be unsuitable as audit
cylinders because of insufficient stability in compressed gas
cylinders.
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TABLE 5.3.
Section No. 3.0.5
Date September 23, 1985
Page 44
ORGANIC AUDIT CYLINDERS AVAILABLE FROM U. S. EPA
Low Concentration Range High Concentration Range
Compound**** Concentration
Range (ppm)
Benzene
Ethylene
Propylene
Methane/Ethane
Propane
Toluene
Hydrogen Sulfide
Meta-Xylene
Methyl Acetate
Chloroform
Carbonyl Sulfide
Methyl Mercaptan
Hexane
1 , 2-Dichloroe thane
Cyclohexane
Methyl Ethyl Ketone
Methanol
1 , 2-Dichloropropane
Trichloroethylene
1 , 1-Dichloroethylene
**1 , 2-Dibromoethylene
Perchloroethylene
Vinyl Chloride
1 , 3-Butadiene
Acrylonitrile
**Aniline
Methyl Isobutyl
Ketone
**Para-dichlorbenzene
**Ethylamine
**Formaldehyde
Methylene Chloride
Carbon Tetrachloride
Freon 113
Methyl Chloroform
Ethylene Oxide
Propylene Oxide
5-20
5-20
5-20
5-20
5-20
5-20
5-20
5-20
5-20
5-20
3-10
20-80
5-20
30-80
30-80
5-20
5-20
5-20
5-20
5-20
5-30
5-30
5-20
5-20
5-20
5-20
5-20
5-20
1-20
5-20
5-20
5-20
5-20
5-20
Cylinder Concentration Cylinder
Construe- Range (ppm Construc-
tion*** tion***
S
Al
Al
Al
S
Al
S
S
S
S
Al
Al
Al
S
Al
Al
Al
Al
LS
S
S
S
LS, Al
Al
Al
S
Al
Al
Al
Al
Al
Al
Al
60-400
300-700
3000-20,000
300-700
1000-6000 (M)
200-700 (E)
300-20,000
100-700
100-700
300-700
300-700
300-700
100-300
1000-3000
100-600
80-200
300-700
100-600
100-600
100-600
300-700
300-700
75-200
Al, S
Al
Al
Al
Al
Al
S
Al
LS
S
S
S
LS
Al
S
Al
Al
Al
LS
LS
LS, Al
Al
(continued)
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TABLE 5.3.
Section No. 3-0.5
Date September 23, 1985
Page 45
ORGANIC AUDIT CYLINDERS AVAILABLE FROM U. S. EPA
(continued)
Low Concentration Range
High Concentration Range
Compound****
Allyl Chloride
Acrolein
Chlorobenzene
Carbon Disulfide
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Section No. 3.0.5
Date September 23, 1985
Page 46
5.16 Method 19 (Sulfur Dioxide Removal Efficiency and
Particulate, Sulfur Dioxide and Nitrogen Oxides Emissions)
5.16.1 Methods Description - Method 19 is applicable for deter-
mining sulfur dioxide removal efficiencies of fuel pretreatment
and sulfur dioxide control devices and the overall reduction of
potential sulfur dioxide emissions from electric utility steam
generators. This Method is also applicable for the determination
of particulate, sulfur dioxide and nitrogen oxides emission
rates. Fuel samples from before and after fuel pretreatment sys-
tems are collected and analyzed for sulfur and heat content. A
sulfur dioxide emission reduction efficiency is calculated from
the efficiency of the fuel pretreatment system.
Sulfur dioxide and oxygen or carbon dioxide concentration
data obtained from sampling emissions upstream and downstream of
sulfur dioxide control devices are used to calculate sulfur diox-
ide removal efficiencies. As an alternative to sulfur dioxide
monitoring upstream of sulfur dioxide control devices, fuel sam-
ples may be collected in an as-fired condition and analyzed for
sulfur and heat content. An overall sulfur dioxide emission
reduction efficiency is calculated from the efficiency of fuel
pretreatment systems and the sulfur dioxide control devices.
Particulate, sulfur dioxide, nitrogen oxides, and oxygen or
carbon dioxide concentration data from downstream of sulfur diox-
ide control devices are used along with F factors to calculate
particulate, sulfur dioxide, and nitrogen oxides emission rates.
The sampling and analytical procedures are not described in this
Handbook for the sulfur dioxide removal efficiency. The Method
for determination of oxygen, particulate, sulfur dioxide and
nitrogen oxides is described in Sections 3.2, 3.4, 3.11, 3.5, and
3.6, respectively. The promulgated Method is in the Federal Reg-
ister, Vol. 44, page 33580, June 11, 1979 and 40 CFR 60, Appendix
A.
5.16.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures - When Methods 3, 5, 6, 7, and 17 are used in support
of Method 19, the same procedures and audit frequency should be
used as described in the individual subsections for each of those
Methods. When sulfur dioxide continuous emission monitors
(CEM's) are used in support of the determination of sulfur
dioxide removal efficiency, the audit procedures and frequency
described in Appendix F, Procedure 1, 40 CFR Part 60 are to be
used.
When fuel sample analysis is used to determine the sulfur
dioxide concentration on a ng/Joule or Ib/million Btu basis, an
audit of the analytical procedures should be performed. A coal
audit sample should be analyzed each quarter with the fuel sam-
ples. The coal audit sample should be analyzed at the same time,
by the same procedure and analysis as the coal samples from the
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Section No. 3.0.5
Date September 23, 1985
Page 47
pretreatment process and the furnace. The sample must be ana-
lyzed until the repeatability of two consecutive analyses of sul-
fur agree within 0.05% sulfur for coal containing less than 2%
sulfur or 0.10% sulfur for coal containing 2% or more of sulfur
as described in Reference 15. The auditor can then compute the
percent relative error (RE) from the results on a (Ib of soo)/
million Btu or (ng of SCO/Joule basis only.
RE ' CM - CA
where:
CM = Sulfur concentration or the gross calorific value
measured by Method 19, % S or Btu/lb, and
C = Audit or known sulfur concentration or the gross
calorific value of the audit sample, % S or Btu/lb.
An acceptable relative error for the audit sample, based on
reproducibility (between lab) criteria in Reference 15, is 0.10%
sulfur for coal containing less than 2% sulfur and 0.20% sulfur
for coal containing 2% or more of sulfur. For heating value, an
acceptable relative error has been established at 300 Btu/lb
based on the EPA coal audit data. The results of the calculated
RE from the coal audit plus the audit results from Methods 3, 6,
7 and either 5 or 17, if used in support of Method 19, should be
included in the quarterly emissions report as assessments of the
accuracy of the sampling and analytical phase during the Method
19 test. The acceptable relative error for Methods 3, 5, 6, 7
and 17 are the same as specified in their respective section.
5.16.3 Audit Frequency - When Method 19 is used for SPNSS pur-
poses, the following audit frequency is recommended for assessing
accuracy. Methods 3, 5, 6, 7, and 17 should be audited using the
same procedures and frequency as shown in the individual sub-
section for each Method. The S02 CEM should be audited on
aquarterly basis using the procedures and frequency described in
Appendix F, Procedure 1, 40 CFR Part 60 (see Reference 7 for
details). An audit for assessing accuracy of the coal sample
analysis should be conducted on a quarterly basis. A lesser
frequency may be acceptable when Method 19 is used for
applications other than compliance and enforcement.
5.16.4 Availability of Audit Materials - Control agencies re-
sponsible for the compliance or enforcement test, may obtain
audit materials for Methods 5, 6, 7, and 17 from the locations
described in these respective individual subsections. These
control agencies may obtain a coal audit sample by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
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Section No. 3.0.5
Date September 23, 1985
Page 48
Attention: Source Test Audit Coordinator
The coal audit sample may also be used to assess the accur-
acy of the moisture and/or ash content analysis. Alternatively,
coal audit samples may also be obtained from commercial coal
testing laboratories.
5.16.5 Cost of Audit - The audit for Method 19 is an audit of
the sampling phase for Method 5 and 17 and an audit of the ana-
lytical phase for Methods 6, 7, and coal sampling and analysis.
The audit of the initial performance test and performance speci-
fication procedures for the continuous emission monitors should
require less than 16 technical hours of effort to complete. The
effort would generally represent less than 10 percent of the
total effort to conduct, calculate and report Method 19 sampling
and analysis requirements. Since the allowable combinations of
testing analysis procedures for a continuous effort are numerous,
no estimate of cost is made. It is unlikely, however, that the
effort for the audits with the continuous monitoring would be
greater than 10 percent of the total effort.
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Section No. 3.0.5
Date September 23, 1985
Page 49
5.17 Method 20 (Nitrogen Oxide, Sulfur Dioxide and Oxygen
Emissions from Stationary Gas Turbines)
5.17.1 Method Description - Method 20 is applicable for the
determination of nitrogen oxides (NO ), sulfur dioxide (SO2), and
oxygen (02) emissions from stationary gas turbines. For the NO
and O2 determinations, this Method includes: (1) measurement
system design criteria; (2) analyzer performance specifications
and performance test procedures; and (3) procedures for emission
testing. A gas sample is continuously extracted from the exhaust
stream of a stationary gas turbine; a portion of the sample
stream is then conveyed to instrumental analyzers for
determination of NO- and 0~ content. During each NO and 0«
determination, a separate measurement of SO^ emissions is made by
using Method 6, or its equivalent. The 02 determination is used
to adjust the NO and SO2 concentrations to a reference
condition. The sampling and analytical procedures are not
described in this Handbook. The promulgated Method can be found
in the Federal Register, Vol. 44, page 52792, September 10, 1979
and 40 CFR 60, Appendix A.
5.17.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures - The accuracy of the sampling and analytical proce-
dure is assessed by conducting a cylinder gas audit. One audit
cylinder of NO in N2 and one cylinder of 02 in N2 are needed.
These audit gases must be certified by comparison to National
Bureau of Standards (NBS) gaseous Standard Reference Materials
(SRM) or NBS/EPA approved gas manufacturer's Certified Reference
Materials (CRM) following EPA Traceability Protocol 1 for audit
gases (Section 3.0.4 of this Handbook). CRM's may be used
directly as audit gases; procedures for preparation of CRM's are
described in Reference 6.
The NO audit sample concentrations should be within the
range of 40 to 200 percent of the applicable emissions limit. An
audit gas concentration of 60 to 300 ppm of NO would typically be
used for an emission standard of 0.015 percent NO at 15 percent
oxygen for stationary gas turbines. Note: The audit gas should
not be the same gas used for normal calibration.
The O2 audit gas cylinder concentration should be between 10
and 15 percent O2 in N2.
The following items are provided as guidance for conducting
a proper audit.
1. The monitors should be operating at normal conditions,
and no adjustments are permitted during the audit.
2. After the measurement systems calibration and valida-
tion, and just prior to the field sampling, the tester should
attach the NO audit cylinder to the opening of the probe. The
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Section No. 3.0.5
Date September 23, 1985
Page 50
audit gas should be fed to the probe in sufficient quantity to
ensure that an excess of sample is vented to the atmosphere. The
tester should record the analyzer readings when a stable value is
obtained.
3. The same procedure should be performed with the 02 audit
gas. The tester is responsible for ensuring that the auait gas
is introduced into the measurement system in an acceptable manner
and at an acceptable rate.
4. The results for the audit gas samples should be
calculated in the same manner used to calculate the field test
samples.
5. The auditor can then compute the percent relative error
(RE) for each audit point.
RE = CM ~ CA x 100
CA
where:
CM = Concentration measured by Method 20, ppm NO or percent
M 02, and
C = Audit or given concentration of the audit sample, ppm
NO or percent O2.
6. An acceptable relative error has been established as +15
percent for this Method. This relative error is based on the O-
and NO monitors' cylinder gas audits, as described in Reference
7. x
7. The calculated RE should be included in the emission
test report as an assessment of the accuracy of the sampling and
analytical phase of the Method 20 test.
The Method 6 tests performed in support of Method 20 should
be audited using the same procedures as described in the accuracy
audit procedures for Method 6 (Section 5.4). The acceptable
relative error for Method 6 audits is also shown in Section 5.4.
5.17.3 Audit Frequency - When Method 20 is used for SPNSS
purposes, the following audit frequency is recommended for the
compliance and enforcement test. An audit for accuracy of the
measurement system for NO and 0~ should be conducted before the
start of the field testing series. An audit for accuracy of the
analytical procedures for Method 6 tests should be conducted
simultaneously with the field samples as described in Subsection
5.4.3 of Method 6. A lesser frequency may be acceptable when
Method 20 is used for applications other than compliance and
enforcement.
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Section No. 3.0.5
Date September 23, 1985
Page 51
5.17.4 Availability of Audit Materials - The given concentra-
tions of 02 and NO cylinder gases used for audits of Method 20
must be both accurate and stable. Both 02 and NO are available
from several commercial gas manufacturers. These cylinder gases
may be obtained by two methods:
1. Require the gas manufacturer to use EPA Traceability
Protocol 1 to establish the audit gas concentration. (The gas
manufacturer should also be required to guarantee in writing that
EPA Traceability Protocol 1 was followed to certify the audit gas
concentration.)
2. Obtain a CRM gas from a commercial gas manufacturer. A
list of commercial gas manufacturers who have no CRM gases
approved for sale by NBS/EPA may be obtained by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77)
Research Triangle Park, North Carolina 27711
Attention: List of CRM Manufacturers
5.17.5 Cost of Audit - The audit for Method 20 is an audit of
both the sampling and analysis phase. This audit should require
less than five technical hours of effort to complete. This
effort should generally represent less than 5 percent of the
total effort to conduct, calculate, and report the Method 20
sampling and analysis.
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Page 52
5.18 Method 25 (Total Gaseous Nonmethane Organic Emissions as
Carbon)
5.18.1 Method Description - This Method applies to the measure-
ment of volatile organic compounds (VOC) as total gaseous non-
methane organics (TGNMO) analyzed in terms of carbon from source
emissions. Organic particulate matter will interfere with the
analysis and, therefore in some cases, an in-stack particulate
filter is required. An emission sample is withdrawn from the
stack at a constant rate through a chilled condensate trap by
means of an evacuated sample tank. TGNMO are determined by
combining the analytical results obtained from independent
analyses of the condensate trap and sample tank fractions. After
sampling is completed, the organic contents of the condensate
trap are oxidized to carbon dioxide (C02). The C02 is
quantitatively collected in an evacuated vessel, then a portion
of the C02 is reduced to methane (CH.) and measured by a FID.
The organic content of the sample fraction collected in the
sampling tank is measured by injecting a portion into a gas
chromatographic (GC) column to separate the nonmethane organics
from CO, C02/ and CH.; the nonmethane organic (NMO) material is
oxidized to C02/ reauced to CH. and measured by a flame
ionization detector (FID). In this manner, the variable response
of the FID associated with different types of organics is elimi-
nated. The sampling and analytical procedures are not described
in this Handbook. The promulgated Method can be found in the
Federal Register, Vol. 45, page 65956, October 3, 1980 and 40 CFR
60, Appendix A.
5.18.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures - The accuracy of the sampling and analytical proce-
dures is assessed by conducting a cylinder gas audit. One audit
cylinder of EPA Method 25 gas mixture is needed. The audit cyl-
inder will assess both the sampling and analytical procedure.
The EPA Method 25 gas mixture includes a combination of aliphatic
and aromatic organics plus carbon dioxide in a balance gas of
nitrogen. Use of this audit mixture will result in a collection
of organics in both the condensate trap and the evacuated sample
tank portions of the sampling apparatus. The audit gas should be
in the range of about 40 to 200 percent of the concentration of
the allowable emission rate.
The following items are provided as guidance to conduct a
proper audit.
1. The audit sample analysis should be conducted to coin-
cide with the analysis of source test samples. Normally, it will
be conducted after the nonmethane organic analyzer calibration
and concurrent with the sample analyses.
2. After a leak check of the sampling apparatus has been
completed, attach a manifold to the sample probe. Attach the
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Section No. 3.0.5
Date September 23, 1985
Page 53
audit gas cylinder to the manifold and collect the audit gas with
the Method 25 sampling system consistent with normal procedure
for the Method.
3. At the end of audit analyses, the auditor requests the
calculated concentration from the analyst and then compares the
results with the actual audit concentrations. The auditor com-
putes the percent relative error for the audit.
RE = CM ~ CA x 100
CA
where:
C = Concentration measured by Method 25, ppm as carbon,
n and
C. = Audit or given concentration of the audit sample,
ppm as carbon.
4. No acceptable relative error has been established for
this Method since major revisions to the Method are currently
underway. Due to the cost of the audit only a single audit is
recommended. The audit sample and field samples should be pre-
pared and analyzed in the same manner and at the same time.
5. The calculated RE should be included in the emission
test report as an assessment of the accuracy of the sampling and
analytical phase of the Method 25 test.
5.18.3 Audit Frequency - When Method 25 is used for SPNSS pur-
poses, the following frequency is recommended for compliance and
enforcement tests. An audit for accuracy should be conducted
once for every field test series. A lesser frequency may be
acceptable when Method 25 is used for applications other than
compliance and enforcement.
5.18.4 Availability of Audit Materials - Control agencies re-
sponsible for the compliance or enforcement test may obtain an
EPA Method 25 audit gas cylinder prior to each compliance or
enforcement source test by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77B)
Research Triangle Park, North Carolina 27711
Attention: Audit Cylinder Gas Coordinator
The concentration range of the EPA Method 25 audit gas cyl-
inder available is shown in Table 5.3.
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Section No. 3.0.5
Date September 23, 1985
Page 54
If an audit gas cylinder is unavailable, commercial manufac-
turers should be sought to obtain the desired audit gas.
5.18.5 Cost of Audit - The audit of Method 25 is an audit of both
the sampling and analysis phase. This audit should require less
than 10 technical hours of effort to complete. This would
generally represent less than 10 percent of the total effort to
conduct, calculate and report the Method 25 sampling and analysis.
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Section No. 3.0.5
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5.19 Method 25A and 25B (Total Gaseous Organic Concentration)
5.19.1 Method Description - Methods 25A and 25B are applicable
to the measurement of total gaseous organic concentration of
vapors consisting primarily of alkanes, alkenes, and/or arenes
(aromatic hydrocarbons). The concentration is expressed in terms
of propane (or other appropriate organic calibration gas) or in
terms of carbon. Both Methods extract a gas sample from the
stack through a heated sample line and, if necessary, a glass
fiber filter. Method 25A uses a flame ionization analyzer (FIA)
for analysis and Method 25B uses a nondispersive infrared ana-
lyzer (NDIR) for analysis. The sampling and analytical proce-
dures are not described in this Handbook. The promulgated Method
25A and 25B can be found in the Federal Register Vol. 48, pages
37595 and 37597, respectively, August 18, 1983 and in 40 CFR 60,
Appendix A.
5.19.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures - The accuracy of the sampling and analytical pro-
ceduresis assessed by conducting a cylinder gas audit. One
audit cylinder of an appropriate alkane or alkene is needed. The
organic compound in the audit cylinder should be one of the major
organic components being tested and the given concentration of
the audit gas should be between 40 and 200 percent of the appli-
cable emission limit. The audit cylinder gas will assess both
the sampling and analytical procedures. The audit procedures
(with the exception that only a single cylinder is recommended)
should follow those described in 40 CFR 61, Appendix C, Procedure
2: "Procedure for Field Auditing GC Analysis" or the Federal
Register Vol. 47, page 39179, September 7, 1982 (see Reference
14). The analysis of the audit sample should be conducted after
the preparation of the calibration curve and prior to the field
sample analysis.
The auditor should compute the percent relative error (RE)
for the audit:
RE = CM ~ CA x 100
CA
where:
CM = Concentration measured by Method 25A or 25B in ppm of
the stated organic, and
C. = Audit or given concentration of the audit sample in
ppm of the stated organic.
An acceptable relative error of +10 percent has been established
for this Method. This relative error is based on the audits
conducted by EPA in Reference 16.
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Section No. 3.0.5
Date September 23, 1985
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The calculated RE should be included in the emission test
report as an assessment of the accuracy of the sampling and ana-
lytical phase of Method 25A or 25B test.
5.19.3 Audit Frequency - When Method 25A or 25B is used for
SPNSS purposes, the following frequency is recommended for com-
pliance and enforcement tests. An audit for accuracy should be
conducted after the preparation of the calibration curve and
prior to the field sample analysis for every field test series.
A lesser frequency may be acceptable when Method 25A or 25B is
used for applications other than compliance and enforcement
tests.
5.19.4 Availability of Audit Materials - Control agencies re-
sponsible for the compliance or enforcement test may obtain an
appropriate alkane or alkene audit gas cylinder prior to each
compliance or enforcement source test by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77B)
Research Triangle Park, North Carolina 27711
Attention: Audit Cylinder Gas Coordinator
Table 5.3 shows organic compounds available from the U. S.
Environmental Protection Agency as audit gas cylinders. An
appropriate alkane or alkene audit gas should be selected from
this table for a Method 25A or 25B audit.
If an audit gas cylinder is unavailable, commercial manu-
facturers should be sought to obtain the desired audit gas.
5.19.5 Cost of Audit - The audit of Method 25A or 25B is an
audit of both the sampling and analysis phase. This audit should
require less than five technical hours of effort to complete.
This would generally represent less than 5 percent of the total
effort to conduct, calculate and report the Method 25A or 25B
sampling and analysis.
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Section No. 3.0.5
Date September 23, 1985
Page 57
5.20 References
1. "Quality Assurance and Quality Control Revisions to Methods
6 and 7," 40 CFR 60, Appendix A or Federal Register Vol. 49,
page 26522, June 27, 1984.
2. EPA Method 18 "Measurement of Gaseous Organic Compounds by
Gas Chromotography," 40 CFR 60, Appendix A or Federal Reg-
ister Vol. 48, page 48344, October 18, 1983.
3. "Quality Control Procedures for EPA Method 3," 40 CFR 60,
Appendix A or Federal Register Vol. 48, page 49458, October
25, 1983.
4. "Quality Control Procedures for EPA Methods 4 and 5," 40 CFR
60, Appendix A or Federal Register Vol. 48, page 55670, De-
cember 14, 1983.
5. Mitchell, W. J., Fuerst, R. G., Margeson, J. H., Streib, E.
W., Midgett, M. R., and Hamil, H. F., "New Orifice Opens Way
for Fast Calibration," Pollution Engineering, June 1981, pp.
45-57. A correction in this publication was printed in
Pollution Engineering, August 1981.
6. "A Procedure for Establishing Traceability of Gas Mixtures
to Certain National Bureau of Standards Standard Reference
Materials." Joint publication by NBS and EPA.
EPA-600/7-81-010. Available from U.S. Environmental
Protection Agency, Quality Assurance Division (MD-77A),
Research Triangle Park, North Carolina 27711.
7. "Quality Assurance Requirements for Gaseous Continuous
Emission Monitoring Systems Used for Compliance
Determination," 40 CFR 60, Appendix F, Procedure 1.
8. Constant, P. C., Scheil, G. W., and Sharp, M. C.,
"Collaborative Study of Method 10 - Reference Method for
Determination of Carbon Monoxide Emissions from Stationary
Sources - Report of Testing," EPA-650/4-75-001.
9. Scheil, G. W., and Sharp, M. C., "Standardization of Method
11 at a Petroleum Refinery," EPA-600/4-77-008a, January
1977.
10. Mitchell, W. J., and Midgett, M. R., "Evaluation of
Stationary Source Particulate Measurement Methods: Volume V,
Secondary Lead Smelters," EPA-600/2-79-116, June 1979.
11. Mitchell, W. J., Suggs, J. C., and Bergman, F. J.,
"Collaborative Study of EPA Method 13A and Method 13B,"
EPA-600/4-77-050, September 1977.
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Section No. 3.0.5
Date September 23, 1985
Page 58
12. Hamil, H. F., and Swynnerton, N. F., "A Study to Improve EPA
Methods 15 and 16 for Reduced Sulfur Compounds,"
EPA-600/4-80-023, April 1980.
13. Method 16A, Section 4.3 "System Performance Check," and
Section 4.4 "Sample Analysis" 40 CFR 60, Appendix A or
Federal Register Vol. 50, page 9578, March 8, 1985.
14. "Procedure for Field Auditing GC Analysis," 40 CFR 61,
Appendix C, Procedure 2 or Federal Register Vol. 47, page
39179, September 7, 1982.
15. "Total Sulfur in the Analysis of Coal and Coke," ASTM D
3177-84, page 413-417, 1984.
16. Jayanty, R. K. M., Gutknecht, W. F., and Decker, C. E.,
"Status Report #6 Stability of Organic Audit Materials and
Results of Source Test Analysis Audits," report by Research
Triangle Institute for U. S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory, under Contract
No. 68-02-3767, September 1984.
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Section No. 3.0.6
Date September 23, 1985
Page 1
6.0 SPECIFIC PROCEDURES TO ASSESS ACCURACY OF REFERENCE METHODS
USED FOR NESHAP
The purpose of this Section is to describe specific proce-
dures to routinely assess and document the accuracy of reference
and alternative methods for source test data under NESHAP
(National Emission Standards for Hazardous Air Pollutants).
Procedures for assessment of precision and completeness are not
given, because compliance or enforcement tests are short-term
(only a few hours duration), and additional duplicate tests to
obtain precision data are costly. Accuracy is determined from
results of performance audits (i.e., measurements made by the
routine operator or analyst). The routine operator or analyst
must not know the concentration or value of the audit standard
used, and the results must be submitted to an immediate
supervisor or QA coordinator who does know the audit value.
Since a high degree of experience and planning is required
for audit sample preparation, and EPA has mandated that quality
assurance be an integral part of all agency related measurement
programs, the EPA's Environmental Monitoring Systems Laboratory
(EMSL) in the Research Triangle Park, North Carolina has been
delegated the responsibility for preparation of audit samples and
materials for air measurements. Federal, state, and local agency
personnel can obtain audit samples and materials for any enforce-
ment and compliance measurement program directly from the Quality
Assurance Coordinator at each EPA Regional Office unless other-
wise directed in the following Reference Method subsections. The
address and telephone number for each EPA Regional Office Quality
Assurance Officer is shown in Table 5.1 of Section 3.0.5. When
audit materials are unavailable or needed for nonagency use,
commercial suppliers should be sought.
Performance audits are recommended here for the assessment
of accuracy for the EPA Reference Methods in 40 CFR 61, Appendix
B, when used for NESHAP purposes. Several of the methods have no
performance audits since there are no reliable and low cost audit
procedures available or the time and expense for an audit cannot
now be justified. The EPA Reference Methods for which audits are
recommended are shown in Table 6.1 with their corresponding
subsection number.
The brief description of specific assessment procedures for
each promulgated or proposed Reference Method is approximately
three pages in length. This brief description includes the
following:
I. Method summary (one paragraph).
2. Reference for details on the Method.
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Section No. 3.0.6
Date September 23, 1985
Page 2
TABLE 6.1. EPA REFERENCE METHODS INCLUDED IN SECTION 3.0.6
Method Subsection
number Description number
101, 101A Mercury Emissions in Air Streams from Chlor- 6.1
and 102 Alkali Plants, Mercury Emissions from
Sewage Sludge Incinerators, and Mercury
Emissions in Hydrogen Streams from Chlor-
Alkali plants
104 Beryllium 6.2
105 Mercury in Sewage Sludge 6.3
106 Vinyl Chloride 6.4
108 Arsenic 6.5
and 108A
3. Performance audit program to assess sampling and analyt-
ical procedures.
4. Recommended frequency for performance audits of compli-
ance and enforcement tests. A frequency less than that recom-
mended for enforcement could be acceptable when testing for other
purposes.
5. Recommended standards and levels for establishing audit
values.
6. Procedure to calculate accuracy.
7. Availability of audit materials.
8. Cost of the recommended audits.
The philosophy of these assessments is that relative error
calculations will be made of the accuracy (1) to determine errors
in the testers'/analysts' techniques and systems; (2) to, where
possible, correct errors in these techniques and systems; and (3)
for interpretation of the final reported emission test results by
the data user. The reported emissions test data are not to be
corrected on the basis of these relative error calculations.
The general approach that has been developed for these
audits follow those already described in the Reference Method for
EPA Methods 6 and 7 (see Reference 1) and/or Method 18 (see Ref-
erence 2). These audit procedures require the tester/analyst to
provide the auditor with the audit results, either prior to the
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Section No. 3.0.6
Date September 23, 1985
Page 3
field sample analysis or prior to including the field sample
results in the report. When large relative errors are iden-
tified, the tester/analyst is allowed to correct his system. If
possible, this is accomplished prior to the taking of the field
samples or performing the final analysis on the field samples;
this approach works quite well when the auditor is present for an
on-site analysis. However, in the absence of the auditor, the
tester/analyst must telephone the auditor with results of the
audit sample analysis in order to make necessary corrections
prior to analyzing the field samples. If the auditor feels that
this is unwarranted or the tester/analyst does not wish to take
the possible opportunity to correct an error in the system and/or
techniques, the audit sample(s) would then be prepared and
analyzed in the same manner and at the same time as the field
sample. The approach of notifying the auditor prior to the field
sample analysis can provide the source and agency with a greater
chance of more accurate data, may require the rejection of less
test results, and may improve the techniques and system of the
tester and/or analyst.
For compliance determination, the audit sample values should
be within the range of the allowable emission limit. The audit
sample concentration or value should be within 40 to 200 percent
of the value of interest for audits containing a single audit
sample. For audits containing two audit samples, the low concen-
tration sample should be between 25 and 100 percent of the value
of interest and the high concentration between 100 and 250 per-
cent.
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Section No. 3.0.6
Date September 23, 1985
Page 4
6.1 Method 101 (Mercury Emissions in Air Streams from Chlor-
Alkali Plants), Method 101A (Mercury Emissions from Sewage
Sludge Incinerators) and Method 102 (Mercury Emissions in
Hydrogen Streams from Chlor-Alkali Plants)
6.1.1 Methods Description - Method 101 is applicable for the
determination of particulate and gaseous mercury emissions when
the carrier gas stream is principally air. Method 101A is
applicable for determination of particulate and gaseous mercury
emissions from sewage sludge incinerators. Method 102 is
applicable for determination of particulate and gaseous mercury
emissions when the carrier gas stream is principally hydrogen.
These Methods are for use in ducts or stacks at stationary
sources. Unless otherwise specified, these Methods are not
intended to apply to gas streams other than those emitted
directly to the atmosphere without further processing.
Particulate and gaseous mercury emissions are isokinetically
sampled from the source and collected in acidic iodine mono-
chloride solution. The mercury collected (in mercuric form) is
reduced to elemental mercury. Mercury is aerated from the
solution and analyzed using spectrophotometry. The promulgated
Methods 101 and 102 are found in the Federal Register, Vol. 38,
page 8826, April 6, 1973. Methods 101 and 102 revisions and
Method 101A are found in the Federal Register, Vol. 47, page
4703, June 8, 1982. All Methods can also be found in 40 CFR 61,
Appendix B.
6.1.2 Audits to Assess Accurcy of Sampling and Analytical
Procedures -
6.1.2.1 Sampling Accuracy - The audit for the sampling phase is
used to determine the accuracy of the flow totalizing system (dry
gas meter) of the Methods 101 and 101A sampling train and the
differential pressure gauge used to measure the velocity when the
differential pressure gauge does not meet the specifications in
Section 2.2 of Method 2 (40 CFR 60, Appendix A). The flow
totalizing system should be audited using the same procedures and
with the same frequency as described in detail for Method 5 in
Subsection 5.3.2 of Section 3.0.5 in this Handbook. The differ-
ential pressure gauge should be audited using the same procedures
and with the same frequency as described in detail for Method 2
in Subsection 5.1.2 of Section 3.0.5 in this Handbook.
No audit is suggested for Method 102 because of the special
equipment or arrangement for sampling a hydrogen stream and the
risk of explosion.
6.1.2.2 Analytical Procedures - The analytical procedures should
be audited using two audit samples of aqueous mercury chloride.
The audit samples should be provided to the tester to be analyzed
just prior to the field samples analysis. For Method 101, one
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Section No. 3.0.6
Date September 23, 1985
Page 5
sample should be at a low concentration (1.0 to 5.0 yg/ml) and
one at a high concentration (5.0 to 10.0 yg/ml). For Method
101A, one sample should be at a low concentration (0.1 to 0.5
yg/ml) and one at a high concentration (0.5 to 1.0 yg/ml). This
is based on typical values at sludge dryers for an emission limit
of 3200 g/24 hr. This concentration is dependent on both process
design and operating conditions. Both concentrations should be
obtained by diluting a specified aliquot of the audit sample to
exactly 100 ml.
The audit samples should be analyzed after the preparation
of the calibration curve and prior to the analysis of the field
samples. The percent relative error (RE) of the audit samples is
determined using the equation below. The calculated RE should be
included with the emission test report as an assessment of the
analytical phase of that test.
RE = CM " CA x 100
CA
where:
CM = Concentration measured by Method 101, 101A, or 102,
yg/ml Hg, and
C, = Audit or given concentration of the audit sample,
yg/ml Hg.
An acceptable relative error of _+15 percent has been estab-
lished for this Method. This relative error is based on collab-
orative test results for Methods 101 and 101A (References 3 and
4).
6.1.3 Audit Frequency - When Methods 101 or 101A are used for
NESHAP purposes, the following audit frequency is recommended for
compliance and enforcement tests. An audit for accuracy of the
sampling procedures should be conducted prior to the field test-
ing series on all flow totalizing systems (dry gas meters), and
on all differential pressure gauges used for velocity pressure
determination that do not meet the specifications of Section 2.2
of Method 2. An additional audit should be conducted on the flow
totalizing system when 1) a different flow totalizing system is
used or 2) repairs are made on the flow totalizing system after
auditing. An additional audit should be conducted on the
differential pressure gauge when 1) a different differential
pressure gauge is used or 2) repairs are made on the differential
pressure gauge after auditing. An audit for accuracy of the
analytical procedures should be conducted after the preparation
of the calibration curve and prior to the analyses of the field
samples for every field test series. A lesser frequency may be
acceptable when Methods 101, 101A, or 102 are used for appli-
cations other than compliance and enforcement.
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Section No. 3.0.6
Date September 23, 1985
Page 6
6.1.4 Availability of Audit Materials - Control agencies re-
sponsible for the compliance or enforcement test may obtain
aqueous mercury chloride audit samples and certified calibrated
orifices by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
Attention: Source Test Audit Coordinator
Alternatively, a calibrated orifice can be made as described
by Mitchell, et. al. in Reference 5 and sent to the USEPA for
certification.
6.1.5 Cost of Audit - The audit of Methods 101 and 101A is an
audit for portions of both the sampling and analysis phase. The
audit of Method 102 is an audit of the analysis phase. Each
audit should require less than five technical hours of effort to
complete. This effort would generally represent less than 5
percent of the total effort to conduct, calculate and report the
Method 101, 101A or 102 sampling and analysis.
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Section No. 3.0.6
Date September 23, 1985
Page 7
6.2 Method 104 (Beryllium)
6.2.1 Methods Description - Method 104 is applicable for the
determination of beryllium emissions in ducts or stacks at
stationary sources. Unless otherwise specified, this Method is
not intended to apply to gas streams other than those emitted
directly to the atmosphere without further processing.
Beryllium emissions are isokinetically sampled from the
source, and the collected sample is digested in an acid solution
and analyzed by atomic absorption spectrophotometry. The prom-
ulgated Method can be found in the Federal Register, Vol. 48, page
55268, December 9, 1983 and 40 CFR 61 Appendix B.
6.2.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures -
6.2.2.1 Sampling Accuracy - The audit for the sampling phase is
to determine the accuracy of the flow totalizing system (dry gas
meter) of the Method 104 sampling train and the differential
pressure gauge used to measure the velocity when the differential
pressure gauge does not meet the specifications in Section 2.2 of
Method 2 (40 CFR 60, Appendix A). The flow totalizing system
should be audited using the same procedures and with the same
frequency as described in detail for Method 5 in Subsection 5.3.2
of Section 3.0.5 of this Handbook. The differential pressure
gauge should be audited using the same procedures and with the
same frequency as described in detail for Method 2 in Subsection
5.1.2 of Section 3.0.5 of this Handbook.
6.2.2.2 Analytical Accuracy - The analytical procedures should
be audited using two audit samples of aqueous beryllium salts.
The analyst should analyze the audit samples along with the field
samples. One sample should be a low concentration (5 to 20 yg of
beryllium per audit sample) and one sample should be a high
concentration (50 to 100 yg of beryllium per audit sample). This
is based on typical concentration values at beryllium processing
facilities that would be equivalent to an emission limit of
10 g/24 h.
The audit samples must be analyzed after the preparation of
the calibration curve and prior to the analysis of the field
samples. The auditor should calculate the percent relative error
(RE) of the audit samples using the equation below. The
calculated RE should be included in the emission test report as
an assessment of the analytical phase of that test.
RE = CM ~ CA x 100
CA
where:
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Section No. 3.0.6
Date September 23, 1985
Page 8
CM = Concentration measured by Method 104, total yg
beryllium, and
CA = Audit or given concentration of the audit sample,
total yg beryllium.
An acceptable relative error of +15 percent has been estab-
lished for this Method. This relative error is based on the
collaborative test results for Method 104 (Reference 6).
6.2.3 Audit Frequency - When Method 104 is used for NESHAP pur-
poses, the following audit frequency is recommended for compli-
ance and enforcement tests. An audit for accuracy of the sam-
pling procedures should be conducted prior to the field testing
series on all flow totalizing systems (dry gas meters) and on all
differential pressure gauges used for velocity pressure deter-
mination that do not meet the specifications of Section 2.2 of
Method 2. An additional audit should be conducted on the flow
totalizing system when (1) a different flow totalizing system is
used or (2) repairs are made on the flow totalizing system after
auditing. An additional audit should be conducted on the differ-
ential pressure gauge when (1) a different differential pressure
gauge is used or (2) repairs are made on the differential pres-
sure gauge, after auditing. An audit for accuracy of the ana-
lytical procedures should be conducted after the preparation of
the calibration curve and prior to the analysis of the field sam-
ples for each field test series. A lesser frequency may be
acceptable when Method 104 is used for applications other than
compliance and enforcement.
6.2.4 Availability of Audit Materials - Control agencies respon-
sible for the compliance or enforcement test may obtain aqueous
beryllium salt audit samples and certified calibrated orifices by
contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
Attention: Source Test Audit Coordinator
Alternatively, a calibrated orifice can be made as described
by Mitchell, et. al. in Reference 5 and sent to the USEPA for
certification.
6.2.5 Cost of Audit - The audit of Method 104 is an audit of
portions of both the sampling and analysis phase. This audit
should require less than six technical hours of effort to
complete. This effort should generally represent less than 10
percent of the total effort to conduct, calculate and report
Method 104 sampling and analysis.
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Section No. 3.0.6
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Page 9
6.3 Method 105 (Mercury in Sewage Sludge)
6.3.1 Methods Description - Method 105 is applicable for the
determination of total organic and inorganic mercury content in
sewage sludges, soils, sediments, and bottom-type materials. The
normal range of this Method is 0.2 to 5 yg/g. The range may be
extended above or below the normal range by increasing or de-
creasing sample size and through instrument and recorder control.
A weighted portion of the sewage sludge sample is digested
in aqua regia for 3 minutes at 95 C, followed by oxidation with
potassium permanganate. Mercury in the digested sample is then
measured by the conventional spectrophotometer cold vapor tech-
nique. An alternative digestion procedure involves the use of an
autoclave and is described in this Method. The promulgated
Method can be found in the Federal Register, Vol. 40, page 48299,
October 14, 1975 and 40 CFR 60 Appendix B.
6.3.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures -
6.3.2.1 Sampling Accuracy - No audit recommended.
6.3.2.2 Analytical Accuracy - The analytical procedures for
Method 105 should be audited using the same procedure and fre-
quency as detailed for Methods 101, 101A and 102 in Subsection
6.1.2.2.
6.3.3 Audit Frequency - When Method 105 is used for NESHAP pur-
poses, the following audit frequency is recommended for compli-
ance and enforcement tests. An audit for accuracy of the anal-
ytical procedures should be conducted after the preparation of
the calibration curve and prior to the analysis of the field
samples. A lesser frequency may be acceptable when Method 105 is
used for applications other than compliance and enforcement.
6.3.4 Availability of Audit Materials - Control agencies respon-
sible for the compliance or enforcement test, may obtain aqueous
mercury chloride audit samples by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
Attention: Source Test Audit Coordinator
6.3.5 Cost of Audit - The audit of Method 105 is an audit of the
analysis phase. This audit should require less than four techni-
cal hours of effort to complete. This effort generally repre-
sents less than 5 percent of the total effort to conduct,
calculate and report Method 105 sampling and analysis.
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Section No. 3.0.6
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6.4 Method 106 (Vinyl Chloride)
Method 106 should be audited using the quality assurance re-
quirements in Method 106. (See Reference 7 for details.)
6.4.1 Method Description - Method 106 is applicable to the meas-
urement of vinyl chloride in stack gases from ethylene dichlor-
ide, and vinyl chloride and polyvinyl chloride manufacturing
processes, except where the vinyl chloride is contained in par-
ticulate matter. An integrated bag sample of stack gas contain-
ing vinyl chloride (chloroethene) is subjected to chromatographic
analysis using a flame ionization detector.
Note: Performance of this Method should not be attempted by
persons unfamiliar with the operation of a gas chromatograph, nor
by those who are unfamiliar with source sampling, as there are
many details that are beyond the scope of the Method 106
description. Care must be exercised to prevent exposure of
sampling personnel to vinyl chloride, a carcinogen. The
promulgated Method can be found in the Federal Register, Vol. 47,
page 39168, September 7, 1982 and 40 CFR 61, Appendix B.
6.4.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures - The accuracy of the sampling and analytical proce-
dure is assessed by conducting a cylinder gas audit. Two audit
cylinders of vinyl chloride are needed. The audit cylinders are
'used to assess both the sampling and analytical procedures. The
audit cylinders should contain a vinyl chloride concentration
between 5 and 20 ppm for the low concentration cylinder and 20 to
50 ppm for the high concentration cylinder. This is based on an
emission limit of 10 ppm vinyl chloride. The following recom-
mendations are provided as guidance to conduct a proper audit.
1. The audit should be conducted to coincide with the
analysis of source test samples. Normally, it will be conducted
immediately after the GC calibration and prior to the sample
analyses.
2. After a leak check of the bag has been completed, fill
each bag approximately half full with the audit gases. Analyze
the bags in the normal manner specified for Method 106.
3. At the end of audit analyses, the auditor requests the
calculated concentrations from the analyst and then compares the
results with the actual audit concentrations. The auditor
computes the percent relative error (RE) for both audit values
using the equation below.
RE =
CM - CA
x 100
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Section No. 3.0.6
Date September 23, 1985
Page 11
where:
CM = Concentration measured by Method 106, ppm, and
C. = Audit or given concentration of the audit sample, ppm.
A
4. Method 106 has an established acceptable relative error
of less than +^.0 percent. If this agreement is not met the
tester/analyst should check the system to eliminate problems and
repeat the audit prior to field sample collection.
5. The RE should be included in the emission test report as
an assessment of the accuracy of the sampling and analytical
phases of the Method 106 test.
6.4.3 Audit Frequency - When Method 106 is used for NESHAP pur-
poses, the following audit frequency is recommended for compli-
ance and enforcement tests. An audit for accuracy should be
conducted prior to every field test series (but after analyzer
calibration). A lesser frequency may be acceptable, when Method
106 is used for applications other than compliance and
enforcement.
6.4.4 Availability of Audit Materials - Control agencies respon-
sible for the compliance or enforcement test may obtain an audit
cylinder of vinyl chloride prior to each compliance or enforce-
ment source test by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77B)
Research Triangle Park, North Carolina 27711
Attention: Audit Cylinder Gas Coordinator
If audit cylinders are unavailable, commercial manufacturers
should be sought to obtain the desired audit gases. These
commercial gases should meet the specifications described in
Section 5.2.3.1 of Method 106.
6.4.5 Cost of Audit - The audit of Method 106 is an audit of
both the sampling and analysis phase. This audit should require
less than five technical hours of effort to complete. This
effort should generally represent less than 5 percent of the
total effort to conduct, calculate and report Method 106 sampling
and analysis.
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Section No. 3.0.6
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Page 12
6.5 Method 108 and 108A (Arsenic)
6.5.1 Method Description - Methods 108 and 108A are applicable
to the determination of organic arsenic (As) emissions from
nonferrous smelters and other sources, as specified in the
regulations. Particulate and gaseous As emissions are withdrawn
isokinetically from the source and collected on a glass mat
filter and in water. The collected As is then analyzed by means
of atomic absorption spectrophotometry. The sampling and
analytical procedures are not included in this Handbook. The
promulgated Method can be found in 40 CFR 61, Appendix B.
6.5.2 Audits to Assess Accuracy of Sampling and Analytical
Procedures -
6.5.2.1 Sampling Accuracy - The audit for the sampling phase is
used to determine the accuracy of the flow totalizing system (dry
gas meter) of the Method 108 and 108A sampling train and the dif-
ferential pressure gauge used to measure the velocity when the
differential pressure gauge does not meet the specifications in
Section 2.2 of Method 2 (40 CFR 60, Appendix A). The flow total-
izing system should be audited using the same procedures and with
the same frequency as described in detail for Method 5 in Sub-
section 5.3.2 of Section 3.0.5 in this Handbook. The differen-
tial pressure gauge should be audited using the same procedures
and with the same frequency as described in detail for Method 2
in Subsection 5.1.2 of Section 3.0.5 in this Handbook.
6.5.2.2 Analytical Accuracy - The analytical procedures should
be audited using duplicate analysis of a single aqueous audit
sample. The audit sample should be at a concentration between 40
and 200 percent of the emission limit. The duplicate analysis of
the audit sample should be performed after the preparation of the
calibration curve and prior to the analysis of the field
samples. The auditor should calculate the percent relative error
(RE) of the audit samples:
RE =
CM - CA
x 100
where:
C., = Concentration measured by Method 108 or 108A,
total p g of As, and
C = Audit or given concentration of the audit sample,
total y g of As.
An acceptable relative error of +15% has been established
for this Method. The Relative error is based on the method
evaluation of Method 108 (Reference 8).
-------
Section No. 3.0.6
Date September 23, 1985
Page 13
The calculated RE should be included in the emission test
report as an assessment of the accuracy at the analytical phase
of the Method 108 or 108A test.
6.5.3 Audit Frequency - When Method 108 or 108A is used for
NESHAP purposes, the following audit frequency is recommended for
compliance and enforcement tests. An audit for accuracy of the
sampling procedures should be conducted prior to the field
testing series on all flow totalizing systems (dry gas meters)
and on all differential pressure gauges used for velocity pres-
sure determination that do not meet the specifications of Section
2.2 of Method 2. An additional audit should be conducted on the
flow totalizing system when (1) a different flow totalizing
system is used or (2) repairs are made on the flow totalizing
system after auditing. An additional audit should be conducted
on the differential pressure gauge when (1) a different differ-
ential pressure gauge is used or (2) repairs are made on the
differential pressure gauge after auditing. An audit for accur-
acy of the analytical procedures should be conducted after the
preparation of the calibration curve and prior to the analysis of
the field samples for each field test series. A lesser frequency
may be acceptable when 108 or 108A is used for applications other
than compliance and enforcement.
6.5.4 Availability of Audit Materials - Control agencies
responsible for compliance or enforcement test may obtain aqueous
audit samples and certified calibrated orifices by contacting:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
Attention: Source Test Audit Coordinator
Alternatively, a calibrated orifice can be made as described
by Mitchell, et. al. in Reference 5 and sent to the USEPA for
certification.
6.5.5 Cost of Audit - The audit for Method 108 or 108A is an
audit of portions of both the sampling and analysis phase. The
audit should require less than eight technical hours of effort to
complete. This effort should generally represent less than 10
percent of the total effort to conduct, calculate and report
Method 108 or 108A sampling and analysis.
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Section No. 3.0.6
Date September 23, 1985
Page 14
6.6 References
1. "Quality Assurance and Quality Control Revisions to Methods 6
and 7," 40 CFR 60, Appendix A or Federal Register, Vol. 49,
page 26522, June 27, 1984.
2. EPA Method 18, "Measurement of Gaseous Organic Compounds by
Gas Chromatography," 40 CFR 60, Appendix A or Federal
Register, Vol. 48, page 48344, October 18, 1983.
3. Mitchell, W. J. and Midgett, M. R., "Improved Procedure for
Determining Mercury Emissions from Mercury Cell Chlor-Alkali
Plants." APCA Journal, Vol. 26, No. 7, July 1976.
4. Mitchell, W. J., Midgett, M. R., Suggs, J. C., and Albrinck,
D, "Test Methods to Determine the Mercury Emissions from
Sludge Incineration Plants." EPA-600/4-79-058, September
1979.
5. Mitchell, W. J., Fuerst, R. G., Margeson, J. H., Streib,
E. W., Midgett, M. R., and Hamil, H. F., "New Orifice Opens
Way for Fast Calibration." Pollution Engineering, June 1981,
pp. 45-57. A correction in this publication was printed in
Pollution Engineering, August 1981.
6. Constant, Paul C. and Sharp, Michael C., "Collaborative Study
of Method 104 - Reference Method for Determination of
Beryllium Emission from Stationary Sources."
EPA-650/4-74-023, June 1974.
7. "Preparation of Standard Gas Mixtures, Calibration, and
Quality Assurance," EPA Method 106, 40 CFR 61, Appendix B, or
Federal Register, Vol. 47, page 39168, September 7, 1982.
8. Ward, T. E., Logan, T. J., Midgett, M. R., Jayanty, R. K. M.,
and Gutknecht, W. F., "Field Validation of EPA Proposed
Method 108 for Measurement of Inorganic Arsenic Emissions
from Stationary Sources." APCA Journal, Vol. 35, No. 8,
August 1985, pp. 822-827.
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Section No. 3.0.8
Date November 4, 1985
Page 1
8.0 AUDIT MATERIALS AVAILABLE FROM U. S. EPA
In a memo dated May 30, 1979, Douglas M. Costle, the EPA
Administrator, presented the Environmental Protection Agency
Quality Assurance Policy Statement. He made participation in the
quality assurance efforts mandatory for all EPA-supported or
required monitoring activities. Furthermore, in a June 14, 1979
memo, Mr. Costle made "quality assurance requirements" mandatory
for all environmental measurements conducted under extramural
funding. Continued support for the mandatory quality assurance
requirements was extended in a memo issued November 2, 1981 by
Anne M. Gorsuch, the EPA Administrator. Initially in response to
the policy statement and currently in response to the reference
method requirements, the Quality Assurance Division of the
Environmental Monitoring Systems Laboratory of the U. S.
Environmental Protection Agency (EPA) has developed reference
materials for performance audits of environmental measurements.
The purpose of the audit materials are two fold: (1) to
provide agencies with a means of assessing the relative error of
environmental measurements, and (2) to provide EPA with a
continuing index of the quality of data reported.
The preparation and distribution of all audit materials are
coordinated by the Quality Assurance Division of the Environ-
mental Monitoring System Laboratory, Research Triangle Park, NC.
The audit materials are available to all federal, state, and
local agencies in support of performance audits for all
enforcement testing. The audit materials are generally not
available for internal audits by the private sector, except when
requested by a federal, state, or local agency. However, the
audit materials are available to contractors of government
agencies. To request futher information about the source audit
materials, write to:
Source Test Audit Coordinator
Quality Assurance Division, MD-77A
Environmental Monitoring Systems Laboratory
Research Triangle Park, NC 27709
Commercial: (919) 541-7834
FTS: 629-7834
The available audit materials are shown in the following
three tables. Table 8.1 lists available organic gas audit
cylinders in the parts per million range. Table 8.2 lists
available organic gas audit cylinders in the parts per billion
range. Table 8.3 describes the solid samples, aqueous samples,
and other audit materials. The audit materials should be
requested at least thirty (30) days prior to their actual need.
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Section No. 3.0.8
Date November 4, 1985
Page 2
TABLE 8.1. PARTS PER MILLION LEVEL ORGANIC AUDIT CYLINDERS AVAILABLE
FROM U. S. EPA
Compound
»*»
Low
Concentration
Range (ppm)
High
Concentration
Range (ppm)
Benzene
Ethylene
Propylene
Methane/Ethane
Propane
Toluene
Hydrogen Sulfide
Meta-Xylene
Methyl Acetate
Chloroform
Carbonyl Sulfide
Methyl Mercaptan
Hexane
1,2-Dichloroethane
Cyclohexane
Methyl Ethyl Ketone
Methanol
1,2-Dichloropropane
Trichloroethylene
1,1-Dichloroethylene
**1,2-Dibromoethylene
Perchloroethylene
Vinyl Chloride
5-20
5-20
5-20
5-20
5-20
5-40
5-20
5-20
5-20
5-20
3-10
20-80
5-20
30-80
30-80
5-20
5-20
5-20
5-20
5-20
5-30
60-400
300-700
3000-20,000
300-700
1000-6000(M)
200-700(E)
300-700
300-700
100-700
300-700
300-700
300-700
100-400
1000-3000
100-600
80-200
300-700
100-600
100-600
100-600
300-700
(continued)
-------
TABLE 8.1 (continued)
Section No. 3.0.8
Date November 4, 1985
Page 3
Compound
«**
Low
Concentration
Range (ppm)
High
Concentration
Range (ppm)
1 , 3-Butadiene
Acrylonitrile
**Aniline
Methyl Isobutyl Ketone
**Para-dichlorbenzene
Ethylamine
**Formaldehyde
Methylene Chloride
Carbon Tetrachloride
****F-113
Methyl Chloroform
Ethylene Oxide
Propylene Oxide
Allyl Chloride
Acrolein
Chlorobenz ene
Carbon Disulfide
**Cyclohexanone
*EPA Method 25 Gas
Ethylene Dibromide
1,1,2, 2-Tetrachloroe thane
5-50
5-20
5-20
5-20
5-40
5-20
—
1-20
5-20
5-20
5-20
5-20
5-20
5-20
5-20
5-20
—
5-20
100-200
5-20
5-20
300-700
75
75-200
75-200
75-200
75-200
750-2000
75-^00
* The gas mixture contains an aliphatic, an aromatic and carbon dioxide
in nitrogen. Concentrations shown are reported in ppmC.
** Cylinders are no longer available in the repository since the compounds are
found to be unstable in the cylinders.
*** All organic compounds in audit cylinders are in a balance of N_ gas.
****F-113 is the compound 1,1,2-trichloro 1,2,2-trifluoroethane.
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Section No. 3.0.8
Date November 4, 1985
Page 4
TABLE 8.2 PARTS PER BILLION LEVEL ORGANIC AUDIT
CYLINDERS AVAILABLE FROM U. S. EPA
Concentration Range of
Group Each Compound (ppb)
Group I* 7-90
90-430
430-10,000
Group II** 7-90
90-430
Group III*** 7-90
90-430
Group IV**** 7-90
430-10,000
* Group I Compounds are carbon tetrachloride, chloroform,
perchloroethylene, vinyl chloride, and benzene in a balance
of N2 gas.
** Group II Compounds are trichloroethylene, 1,2-dichloro-
ethane, 1,2-dibromoethane, acetonitrile, trichlorofluor-
omethane (F-ll), dichlorodifluoromethane (F-12), bromo-
methane, methyl ethyl ketone,- and 1,1,1-trichloroethane in a
balance of N_ gas.
*** Group III Compounds are vinylidene chloride, 1,1,2-tri-
chloro 1,2,2-trifluorethane (F-113), 1,2-dichloro
1,1,2,2-tetrafluorethane (F-114), acetone, 1-4 dioxane,
toluene, and chlorobenzene in a balance of N£ gas.
**** Group IV audit cylinders are under development, and will be
available about December 1986. Group IV compounds are
acrylonitrile, 1,3-butadiene, ethylene oxide, methylene
chloride, propylene oxide and ortho-xylene.
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Section No. 3.0.8
Date November 4, 1985
Page 5
TABLE 8.3.
SOLID, LIQUID, AND OTHER AUDIT MATERIALS,
AVAILABLE FROM THE U. S. EPA
Material
Description
SO2 and C02 Gas Samples
CO2, O2, and CO Gas Samples
Calibrated Orifices
S02 Samples*
NO Samples*
Sulfuric Acid Samples*
Inorganic Lead Samples
SO2 and C02 in a balance of N2
are contained in gas cylinders in a
range of 200 to 400 ppm SO9 and 12
to 16% C00 for auditing EPA Method
6B i
CQ~, O«, and CO are contained in
a pressurized canister; one
canister per set with range of 5 to
8% for C09, 10 to 15% for 0,
0.5 to 4%^for CO
and
Calibrated critical orifices in
either of two standard quick
connects to check both rate and
volume meters at 0.5 to 1.0 cfm for
auditing EPA Methods 5, 5A, and 5D
Aqueous sulfuric acid solution in
glass ampoules; two per set in
three ranges with normal values of
750, 1500, and 2500 mg of S02 per
dscm for auditing EPA Methods 6,
6A, and 6B
Aqueous potassium nitrate solution
in glass ampoules; two per set in
three ranges with nominal values of
450, 900, and 1750 mg of N02 per
dscm for auditing EPA Methods 7,
7A, 7C, and 7D
Same as the SO2 samples; use
auditing EPA Method 8
for
Lead salts impregnated on a glass
fiber filter in the range of 100 to
600 ;ig and 900 to 2000 y g of lead
per audit sample for auditing EPA
Method 12
(continued)
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TABLE 8.3 (continued)
Section No. 3.0.8
Date November 4, 1985
Page 6
Material
Description
Total Fluoride Samples*
Coal Samples
Mercury Samples*
Arsenic Samples*
Beryllium Samples
Aqueous sodium fluoride in Nalgene
bottle; two per set in the ranges of 0.2
to 1.0 mg of fluoride per dscm and 1 to
5 mg of fluoride per dscm for auditing
EPA Methods 13A and 13B
Coal samples with known quantities of
Btu's per pound, %S content, and
moisture content; two per set in the
range of 11,000 to 14,500 Btu's per
pound for heating value, 0.5% to 4% for
sulfur content, and 2% to 12% moisture
content for auditing EPA Method 19
Aqueous mercury chloride in glass
ampoules; two per set in the ranges of
5 to 20 ug of mercury per ml and 50 to
100 y g of mercury per ml of sample for
auditing EPA Methods 101, 101A, 102,
and 105
Aqueous arsenic salts in glass
ampoules; one per set in the range of
10 to 50 y g/ml or 100 to 500 y g/ml of
arsenic for auditing EPA Methods 108
and 108A
Aqueous beryllium salts in glass
ampoules; two per set in the ranges of
5 to 20 yg of beryllium per audit
sample and 50 to 100 yg of beryllium
per audit sample for auditing EPA
Method 104
*Aqueous audit samples can be reduced to known concentration less
than the stated range by taking smaller aliquots and/or dilution.
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Section No. 3.0.8
Date November 4, 1985
Page 7
Audit gas cylinder samples can be obtained by contacting:
Audit Cylinder Gas Coordinator
Quality Assurance Division, MD-77B
Environmental Monitoring Systems Laboratory
Research Triangle Park, NC 27711
Commercial: (919) 541-4531
FTS: 629-4531
All other source audit materials can be obtained by contact-
ing the "Source Test Audit Coordinator", listed on Page 1 of this
section.
-------
Section No. 3.13
Date July 1, 1986
Page 1
Section 3.13
METHODS 6A AND 6B—DETERMINATIONS OF SULFUR DIOXIDE,
MOISTURE, AND CARBON DIOXIDE EMISSIONS FROM
FOSSIL FUEL COMBUSTION SOURCES
OUTLINE
Number
Section Documentation of Pages
SUMMARY 3.13 1
METHOD HIGHLIGHTS 3113 10
METHOD DESCRIPTION
1. PROCUREMENT OF APPARATUS
AND SUPPLIES 3.13.1 18
2. CALIBRATION OF APPARATUS 3.13.2 14
3. PRESAMPLING OPERATIONS 3.13.3 6
4. ON-SITE MEASUREMENTS 3.13.4 25
5. POSTSAMPLING OPERATIONS 3.13.5 15
6. CALCULATIONS 3.13.6 9
7. MAINTENANCE 3.13.7 3
8. AUDITING PROCEDURE 3.13.8 11
9. RECOMMENDED STANDARDS FOR
ESTABLISHING TRACEABILITY 3.13.9 1
10. REFERENCE METHODS 3.13.10 5
11. REFERENCES 3.13.11 2
12. DATA FORMS 3.13.12 18
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Section No. 3.13
Date July 1, 1986
Page 2
SUMMARY
For Method 6A a gas sample is extracted from the stack in
the same manner as for Method 6 except that CCX, is collected in
the sampling train in addition to the S02> For Method 6B a gas
sample is extracted from the sampling point in the stack inter-
mittently over a 24-hour or other specified time period. Samp-
ling may also be conducted continuously for Method 6B if the
apparatus and procedures are appropriately modified. The S0~ and
C02 are separated and collected in the sampling train. The S02
fraction is measured by the barium-thorin titration method, ana
C02 and moisture are determined gravimetrically.
This method applies to the determination of sulfur dioxide
(S02) emissions from combustion sources in terms of concen-
tration (mg/m ) and emission rate (ng/J), and for the determi-
nation of carbon dioxide (C02) concentration (percent). Method
6A gives results on an hourly basis and Method 6B gives results
on a daily (24 hour) basis.
The minimum detectable limit, upper limit, and the inter-
ferences for S02 measurements are ..the same as for Method 6.
EPA-sponsored collaborative studies were undertaken to determine
the magnitude of repeatability and reproducibility achievable by
qualified testers following the procedures in this method. The
results of the studies evolved from 145 field tests using 9 test
teams including comparisons with Methods 3 and 6. For measure-
ments of emission rates from wet, flue gas desulfurization units
in (ng/J), the repeatability (within-laboratory precision) is 8.0
percent and the reproducibility (between-laboratory precision) is
11.1 percent at a measured level of about 400 ppm of SO2.
The method Descriptions given herein are based on the
Reference Methods ' promulgated December 1, 1982, and cor-
rections and additions published on March 14, 1984 (Section
3.13.10), and on collaborative testing. Blank forms for
recording data are provided in the Method Highlights and in
Section 3.13.12 for the convenience of Handbook users.
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Section No. 3.13
Date July 1, 1986
Page 3
METHODS HIGHLIGHTS
Section 3.13 describes specifications for determination of
sulfur dioxide, moisture and carbon dioxide emissions from fossil
fuel-fired combustion sources. A gas sample is extracted from
the stack in the same manner as for Method 6 except that moisture
and C07 are collected in addition to the SO,, in the same train.
The Method 6A and 6B sampling trains are the same with the
exception that the Method 6B train includes an industrial
timer-switch for intermittent operation over the 24-hour sampling
time. The Method 6B sampling train may be modified to allow for
low flow rate continuous sampling.
The sulfuric acid and SCU are removed by the filter, probe
and midget bubbler with isopropanol with Method 6A. The sulfuric
acid is substantially removed by the filter and probe with Method
6B. The S02 (and SO3) are collected in the two midget impingers
containing 3 percent and 6 percent hydrogen peroxide for Methods
6A and 6B, respectively. For Method 6B, the S03 is collected in
the impingers also, and is included in the 5O~ results. The
moisture that leaves the last midget impinger containing hydrogen
peroxide is then collected by Drierite contained in the final
midget bubbler. The dried gases are then passed through a column
containing a CO2 absorber (Ascarite, Ascarite II or 5A molecular
sieves) to collect the CO2- The analysis of the collected
samples includes the barium-thorin titration for SG>2 (same as
analysis for Method 6) and a gravimetric determination for
moisture and C02- Method 6B, "Determination of S02 and CO,,
Daily Average Emissions from Fossil., Fuel Combustion Sources," was
examined by collaborative testing. There was no difference in
the precision estimates produced by the intermittent and
continuous modes of Method 6B. Averaged over the two modes of
operation and expressed as a percent of the average five day
values, the repeatability estimates are: S02/ 9.8 percent; C02,
9.9 percent; and Emission Rate (Ib per million Btu), 8.0
percent. The reproducibility estimates are: SO2, 12.9 percent;
C02, 13.2 percent; and Emission Rate, 11.1 percent. The
magnitude of both estimates of precision appeared to be
independent of the material being measured. In addition to the
above precision data, statistical tests indicated that there was
no real difference between the continuous, intermittent, and
alternative reference methods based on average five-day values.
The emission rate calculated by the collaborators for 145,
24-hour runs was within 2.5 percent of the emission rate of 240
Method 6 and 120 Method 3 analyses determined during the entire
period of collaborative sampling. Four separate sets of S02 data
were collected during the collaborative test. They were, for the
five-day average, Method 6 (387 ppm), plant monitor (387 ppm),
collaborators/Method 6B (393 ppm), and the prime contractor
analyst/Method 6B (394 ppm). The experienced analyst ran eight
samples each day for the five-day period using 5& molecular
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Section No. 3.13
Date July 1, 1986
Page 4
sieves in the low flow rate sampling train instead of Ascarite II
(used by collaborators) for C02 analysis. This test proved that
the molecular sieves absorbed the C02 quantitatively when the
molecular sieve was properly regenerated prior to its use. The
C02 methods and five-day averages were, Method 3 (12 percent),
collaborators/Method 6B (12.02 percent), and prime contractor
analyst/Method 6B (11.8 percent). Backup Ascarite II cartridges
after the molecular sieve cartridges absorbed no C02, further
showing that molecular sieve absorption of C02 was quantitative.
The collaborative test showed that Method 6B is a viable
alternative method for continuously monitoring S02 emission
rates. Quality data capture was achieved by personnel with
limited experience. All of the molecular sieves had sufficient
absorptive capability for C02 when used as prescribed in this
procedure. The need for regeneration of a new batch of molecular
sieves was noted in a private communication. For this reason,
the analyst should recognize the possibility that the molecular
sieves may require regeneration. The most frequent cause of
error was failure to pass the post run leak test required in the
method. Some other reasons were: broken glassware and spilled
solution, disconnected sample lines during collection, faulty or
uncalibrated dry gas meters, unusually high C02 weight gain which
the collaborator blamed on weighing errors, and low heat in the
flexible connector before the impingers.
The blank data forms at the end of the Highlights section may
be removed from the Handbook and used In the pretest, test, and
posttest operations. Each form has a subtitle (e.g., Method 6A
or 6B, Figure 5.1) to assist the user in finding a similar com-
pleted form in the Method Description (e.g., in Section 3.13.5).
On the blank and filled-in forms, the item/parameters that can
cause the most significant errors are indicated with an asterisk.
The Method Description (Section 3.13.1 to 3.13.9) is based on
the detailed specifications in the Reference Method (Section
3.13.10) promulgated by EPA on^December 1, 1982 and corrections
and additions on March 14, 1984. '
1. Procurement of Apparatus and Supplies
Section 3.13.1 gives specifications, criteria, and design
features for the required equipment and materials. The sampling
apparatus for Methods 6A and 6B has the same design features as
that of Method 6, except for the addition of a C02 absorption
column, an industrial timer-switch (for Method 6B), and tempera-
ture control in the sample probe when required. This section can
be used as a guide for procurement and initial checks of equip-
ment and supplies. The activity matrix (Table 1.1) at the end of
the section is a summary of the details given in the text and can
be used as a quick reference.
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Section No. 3.13
Date July 1, 1986
Page 5
2. Pretest Preparations
Section 3.13.2 describes the required calibration procedures
for the Method 6A and 6B sampling equipment (same as Method 6).
A pretest checklist (Figure 2.5 or a similar form) should be used
to summarize the calibration and other pertinent pretest data.
Section 3.13.3 describes the preparation of supplies and
equipment needed for the sampling. The pretest preparation form
(Figure 3.1 of Section 3.4.3) can be used as an equipment
checklist. Suggestions for packing the equipment and supplies
for shipping are given to help minimize breakage.
Activity matrices for the calibration of equipment and the
presampling operations (Tables 2.1 and 3.1) summarize the
activities detailed in the text.
3. On-Site Measurements
Section 3.13.4 describes procedures for sampling and sample
recovery. A checklist (Figure 4.7 or 4.8) is an easy reference
for field personnel to use in all sampling activities.
4. Posttest Operations
Section 3.13.5 describes the postsampling activities for
checking the equipment and the analytical procedures. A form
(Figure 5.1) is given for recording data from the posttest
equipment calibration checks; a copy of the form should be
included in the emission test final report. A control sample of
known (SO,) concentration should be analyzed before analyzing the
sample for a quality control check on the analytical procedures.
The detailed analytical procedures can be removed for use as an
easy reference in the laboratory. An activity matrix (Table 5.1)
summarizes the postsampling operations.
Section 3.13.6 describes calculations, nomenclature, and
significant digits for the data reduction. A programmed calcu-
lator is recommended to reduce calculation errors.
Section 3.13.7 recommends routine and preventive maintenance
programs. The programs are not required, but their use should
reduce equipment downtime.
5. Auditing Procedures
Section 3.13.8 describes performance and system audits.
Performance audits for both the analytical phase and the data
processing are described. A checklist (Figure 8.2) outlines a
system audit.
Section 3.13.9 lists the primary standards to which the
working standards or calibration standards should be traceable.
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Section No. 3.13
Date July 1, 1986
Page 6
6. References
Section 3.13.10 contains the promulgated Reference Method;
Section 3.13.11 contains the references used throughout this
text; and Section 3.13.12 contains copies of data forms recom-
mended for Method 6A and 6B.
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Section No. 3.13
Date July 1, 1986
Page 7
PRETEST SAMPLING CHECKS
(Methods 6A and 6B, Figure 2.5)
Date Calibrated by
Meter Box Number
Rotameter
Pretest calibration factor (Y ) acceptable? yes no
(within 10 percent of correct value).
*
Dry Gas Meter (If applicable)
Pretest calibration factor (Y) = (within 2 percent of
average factor for each calibration run).
Gas Meter Thermometer (If applicable)
Temperature correction necessary? yes no
(within 3 C (5.4 F) of reference values for calibration and
within 6 C (10.6 F) of reference values for calibration
check).
If yes, temperature correction
Barometer
Field barometer reading correct? yes no
(within 2.5 mm (0.1 in.) Hg of mercury-in-glass barometer).
Balance
Was the pretest calibration of balance correct? yes no
(within 0.05 g of true value using Class S weights).
Most significant items/parameters to be checked.
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Section No. 3.13
Date July 1, 1986
Page 8
PRETEST PREPARATIONS
(Methods 6A and 6B, Figure 3.1)
Apparatus check
Probe
Type liner
Glass
Stainless
steel
Other
Heated properly
Leak checked on
sampling train
Filter or Filter
Assembly
Glass wool
Other
Glassware
Midget bubbler
Midget impinger
Size
Type
Meter System
With timer
Without timer
Leak- free pump'
Rate meter*
Dry gas meter*
Reacrents
Distilled water
H2°2' ^ percent
Isopropanol, 100%*
(for Method 6A)
Drierite
Ascari^e
or 5A molecular
sieve*
Other
Barometer
CO 2 absorber
column
Balance
Acceptable
Yes
No
Quantity
required
Ready
Yes
No
Loaded
and packed
Yes
No
* Most significant items/parameters to be checked.
-------
Section No. 3.13
Date July 1, 1986
Page 9
ON-SITE MEASUREMENTS
(Method 6A, Figure 4.7)
Sampling
Bubbler and impinger contents properly selected, measured, and
placed in proper receptacle?*
Impinger Contents/Parameters
1st: 15 ml of 80 percent isopropanol*
2nd: 15 ml of 3 percent H2O2*
3rd: 15 ml of 3 percent ^2Q2*
4th: approx. 25 g of Drierite*
150 g of Ascarite in C02 absorber?*
Probe heat at proper level?
Crushed ice around impingers?
Pretest leak check at 250 mm (10 in.) Hg?
Leakage rate?
Probe placed at proper sampling point?
Flow rate constant at approximately 1.0 L/min?*
Posttest leak check at 250 mm (10 in.) Hg?*
Leakage rate?
Sample Recovery
Balance calibrated with Class S weights?*
Impingers cleaned and weighed to ^0.1 g at room temp?
Contents of impingers and rinsings placed in polyethylene
bottles?
Fluid level marked?*
C02 absorber cleaned and weighed to +0.1 g at room temp?
Sample containers sealed and identified?*
Samples properly stored and locked?
*
Most significant items/parameters to be checked.
-------
Section No. 3.13
Date July 1, 1986
Page 10
ON-SITE MEASUREMENTS
(Method 6B, Figure 4.8)
Sampling
Impinger contents properly selected, measured, and placed in
impingers?*
Impinger Contents/Parameters
1st: Empty*
2nd: 15 ml of ^6 percent H202*
3rd: 15 ml of >6 percent H^O,,*
4th: Approx. 25 g of Drierite*
Approx. 150 g of Ascarite II or 250 g 5A molecular sieve (contin-
uous flow rate train only) in C0« absorber?*
Probe heat at proper level?
Crushed ice around impingers?
Pretest leak check at 250 mm (10 in.) Hg?
Leakage rate? '
Probe placed at proper sampling point?
Flow rate intermittent at approximately 1.0 L/min?
Flow rate constant between 20 to 40 ml/min?
Posttest leak check at 250 mm (10 in.) Hg?
Leakage rate?
Sample Recovery
Balance calibrated with Class S weights?
Impingers cleaned and weighed to +0.1 g at room temp?
Contents of impingers and rinsings placed in polyethylene
bottles?
Fluid level marked?
C02 absorber cleaned and weighed to +0.1 g at room temp?*
Sample containers sealed and identified?*
Samples properly stored and locked?
*Most significant items/parameters to be checked.
-------
Section No. 3.13
Date July 1, 1986
Page 11
POSTTEST SAMPLING CHECKS
(Methods 6A and 6B, Figure 5.1)
Meter Box Number
Dry Gas Meter (If applicable)
Pretest calibration factor (Y) =
Posttest check YT = (+5 percent of pretest
factor)*
Recalibration required? yes no
If yes, recalibration factor (Y) = (within 2 percent of
calibration factor for each calibration run)
Lower calibration factor Y (pretest or posttest) =
for calculations
Rotameter
Pretest calibration factor (Y ) =
Posttest check (Y ) = (within 10 percent of pretest
factor)
Recalibration recommended? yes no
If performed, recalibration factor (Y ) =
Was rotameter'cleaned? yes no
Dry Gas Meter Thermometer (If applicable)
Was a pretest meter temperature correction used? yes no
If yes, temperature correction ~^^_ ^~~^_
Posttest recalibration required? yes no (recali-
brate when YT recalibrated)
Lt
Barometer
Was pretest field barometer reading correct? • yes no
Posttest recalibration required? yes no (recali-
brate when YT recalibrated)
LI
Balance*
Was the balance calibration acceptable? yes no
(HH 0.05 g checked against Class S weights)
If no, the balance should be repaired or replaced prior to
weighing field samples
* Most significant items/parameters to be checked.
-------
Section No. 3.13
Date July 1, 1986
Page 12
POSTTEST OPERATIONS
(Methods 6A and 6B, Figure 5.4)
Reagents
Normality of sulfuric acid standard*
Date purchased Date standardized
Normality of barium perchlorate titrant*
Date standardized
Normality of control sample*
Date prepared
Volume of burette Graduations
Sample Preparation
Has liquid level noticeably changed?*
Original volume Corrected volume
Samples diluted to 100 ml?*
Analysis
(Sulfur dioxide)
Volume of aliquot analyzed*
Do replicate titrant volumes agree within 1 percent or 0.2 ml?
Number and normality of control samples analyzed
Are replicate control samples within 0.2 ml?
Is accuracy of control sample analysis +5 percent?
Is the relative error of audit sample(s) within acceptable
limits?*
(Moisture and carbon dioxide)
Balance calibrated with Class S weights to within 0.05 g?*
Initial weight of each impinger to nearest 0.1 g*
Final weight of each impinger to nearest 0.1 g*
Initial weight of CO,, absorber to nearest 0.1 g*
Final weight of C02 absorber to nearest 0.1 g*
All data recorded? Reviewed by
* Most significant items/parameters to be checked.
-------
Section No. 3.13.1
Date July 1, 1986
Page 1
1.0 PROCUREMENT OF APPARATUS AND SUPPLIES
A schematic diagram of an assembled Method 6A and 6B sam-
pling train with all components identified is shown in Figure
1.1. An alternative sampling train is shown in Section 3.13.4,
page 11. This sampling train uses larger impingers and may be
more suitable for many facilities. Specifications, criteria, and
design features are given in this section to aid in the selection
of equipment and to ensure that the collected data are of good
quality. Procedures and, where applicable, limits for acceptance
checks are given.
During the procurement of equipment and supplies, it is
suggested that a procurement log be used to record the descrip-
tive title of the equipment, the identification number, if
applicable, and the results of acceptance checks. An example of
a procurement log is shown in Figure 1.2. A blank form is given
in Section 3.13.12 for the Handbook user. If calibration is
required as part of the acceptance check, the data are recorded
in the calibration log book. For facilities that currently have
Method 6A or Method 6B sampling trains that are operating in a
satisfactory manner, these procedural checks will not be
necessary. Table 1.1 at the end of this section summarizes the
quality assurance activities for procurement and acceptance of
apparatus and supplies.
1.1 Sampling
1.1.1 Sampling Probe - The sampling probe should be either a
borosilicate (Pyrex) glass or a type-316 seamless, stainless
steel tube of approximately 6-mm inside diameter (ID), encased in
a stainless steel sheath and equipped with a heating system cap-
able of preventing water condensation and with a filter (either
in-stack or heated out-of-stack) to remove particulate matter,
including sulfuric acid mist. Typically, an in-stack filter is
used at non-scrubber controlled power plants and a temperature
controlled out-of-stack filter is used at scrubber controlled
power plants. Stainless steel sampling probes, type-316, are not
recommended for use with Method 6B because of potential corrosion
and contamination of sample. Glass probes or other types of
stainless steel, e.g., Hasteloy or Carpenter 20, are recommended
for long-term use. When an in-stack filter is utilized, the
probe should have an expanded diameter (38-40 mm) for the first
4 cm on the in-stack end, and this expanded end should be packed
with glass wool prior to sampling. The probe's opposite end must
have a fitting suitable for attaching it to the midget bubbler.
A probe of approximately 1.2 m (4 feet) total length is usually
sufficient for sampling. However, the probe tip can be no closer
than 1 m (3.28 feet) from the inner wall of stacks >2 m in diame-
ter. When stack gas temperatures exceed 480 C (900°F), a probe
fabricated from quartz (Vycon) should be used. The main
-------
HEATED PROBE AND
OUT-OF-STACK FILTER
THERMOMETER _
(not required!
MIDGET IMPINGERS
MIDGET BUBBLERS
Method 6A
A - 15 ml of Isopropanol
B - 15 ml of 3% H909
C - 15 ml of 3%
D - approx 25 g or Drierite
E - approx 150 g of Ascarite
Method 6B
A - empty (glass wool not used)
B - 15 ml of >_6% H909
C - 15 ml of >6% H^O^
D - approx 25 g of Drierite
E - approx 150 g of Ascarite
CO- BREAKTHROUGH
- INDICATOR
(recommended)
PUMP
SURGE TANK
TIMER
(6B only)
>a o w
0> 0) (D
IQ rt O
(D (D d-
to
O
3
00
I-1 •
VO M
00 CO
Figure l.l. Sampling train.
-------
Item description
Qty.
Purchase
order
number
Vendor
Date
Ord.
Rec.
Cost
Disposition
Comments
774/31
/fee.
£*/*«. /v
Figure 1.2. Example of a procurement log.
»O O w
01 W (D
03 rt O
(D 0) rt
o
GO
VD M
00 GO
-------
Section No. 3.13.1
Date July 1, 1986
Page 4
criterion in selecting a probe material is that it be nonreactive
with the gas constituents so it does not introduce bias into the
analysis.
A new probe should be checked for specifications (i.e., the
length and composition ordered). It should be checked for cracks
and breaks, and then leak checked on a sampling train, as des-
cribed in Section 3.13.3. The probe heating system should be
checked as follows:
1. Connect the probe to the inlet of the pump.
2. Electrically connect and turn on the probe heater for 2
or 3 minutes. If functioning properly, it will become warm to
the touch.
3. Start the pump and adjust the needle valve until a flow
rate of about 1.0 L/min is achieved.
4. Check the probe. It should remain warm to the touch.
The heater must be capable of maintaining the exit air temper-
ature at a minimum of 100 C (212 F) under these conditions. If
it cannot, the probe should be rejected. Any probe not
satisfying the acceptance check should be repaired, if possible,
or returned to the supplier.
1.1.2 Filter - A heated out-of-stack filter to remove particu-
late, including sulfuric acid mist. The outlet filter temper-
ature should be monitored and controlled to maintain a
temperature sufficient to prevent condensation or to a maximum of
120 C (248 F). A plug of approximately 0.6 grams of borosilicate
glass wool with no heavy metals, practically free from fluorine
and alumina, low alkali content, and a fiber diameter between
0.005 and 0.008 mm is recommended for the filter media. The
filter holder may be constructed as shown in Figure 1.3. The
filter heater should be checked by connecting it to the probe and
following the procedures described above in Subsection 1.1.1.
Caution; Do not pack filter media too tightly, as this will
result in a high pressure drop across the filter.
1.1.3 Flexible Connector (optional) - A heated flexible con-
nector may be used between the exit of the heated filter and the
inlet of the first impinger. The heated flexible connector
should be Teflon (other construction materials may be used) and
heated to prevent condensation. The flexible connector can be
checked using the same procedure as for the probe with the
exception that it should be checked without connecting it to the
probe.
1.1.4 Midget Bubbler/Impingers - Each sampling train requires
two midget bubblers (30-ml) of medium coarse glass frit, with
-------
Section No. 3.13.1
Date July 1, 1986
Page 5
THERMOCOUPLE
TO TEMPERATURE
'CONTROLLER
^- OUTLET
4-in. LONG
ij-in. DIA.
316 STAINLESS STEEL TUBING
-in. SWAGELOK
FILTER HOLDER WITH THERMOCOUPLE TO MONITOR
EXIT TEMPERATURE.
INLET
3/8-in. SWAGELOK
FITTING
OUTLET
%-in. SWAGELOK
FITTING
4-in. LONG
ij-in. DIA.
316 STAINLESS STEEL
FILTER HOLDER WITHOUT TEMPERATURE MONITOR.
Figure 1.3. Out-of-stack filters.
-------
Section No. 3.13.1
Date July 1, 1986
Page 6
glass wool packed in the top of the first to prevent carryover of
sulfuric acid mist. A midget impinger may be used in place of
either midget bubbler. Larger impingers, such as the Mae West
design, may also be used.
Each sampling train requires two midget impingers (30-ml)
with glass connections between the midget bubblers and the midget
impingers. (Plastic or rubber tubing is not permitted because
these materials absorb or desorb gaseous species.) Silicone
grease may be used to prevent leakage.
Each bubbler/impinger is checked visually for damage, such
as breaks or cracks, and for manufacturing flaws, such as poorly
shaped connections.
Other nonspecified collection absorbers and sampling flow
rates may be used, subject to the approval of the Administrator,
but collection efficiency must be shown to be at least 99 percent
for each of three test runs and must be documented in the
emission test report. For efficiency testing, an extra absorber
must be added and analyzed separately and must not contain more
than I percent of the total S02-
1.1.5 C02 Absorber - A scalable stainless steel or plastic
cylinder or glass bottle with an inside diameter between 30 and
90 mm and a length between 125 and 250 mm and with appropriate
connections at both ends is required. The cylinder should be
checked for flaws or cracks and its ability to hold the required
150 g of Ascarite or 250 g of 5A molecular sieve. The ability to
remain leak free can be checked at the same time that the new lot
of Ascarite or 5A molecular sieve is checked for acceptability,
as later described in Subsection 1.4.1.
It is strongly recommended that a second, smaller C02 ab-
sorber containing Ascarite be added in-line downstream 01 the
primary C02 absorber as a breakthrough indicator. Ascarite turns
white when C02 is absorbed. Alternatively, a larger container
can be used witn the primary and secondary absorber separated by
glass wool. The thermometer following the C02 absorber is not
required.
1.1.6 Vacuum Pump - The vacuum pump should be capable of main-
taining a flow rate of approximately 1 to 2 L/min for pump inlet
vacuums up to 250 mm (10 in.) Hg with the pump outlet near stan-
dard pressure, that is 760 mm (29.92 in.) Hg. The pump must be
leak free when running and pulling a vacuum (inlet plugged) of
250 mm (10 in.) Hg. Two types of vacuum pumps are commonly
used—either a modified sliding fiber vane pump or a diaphragm
pump. For safety reasons, the pump should be equipped with a
three-wire electrical cord.
-------
Section No. 3.13.1
Date July 1, 1986
Page 7
To check the pump for leaks, install a vacuum gauge in the
pump inlet line. Plug the inlet line, and run the pump until the
vacuum gauge reads 250 mm (10 in.) Hg of vacuum, then clamp the
pump outlet line, and turn off the pump. The vacuum reading
should remain stable for 30 seconds.
1.1.7 Volume Meter - A volume meter is not required or needed
for many applications. The tester should check the need prior to
purchase. The dry gas meter must be capable of measuring total
volume with an accuracy of +2 percent, calibrated at the selected
flow rate of 1.0 L/min. and at the gas temperature actually
encountered during sampling, and must be equipped with a temper-
ature gauge (dial thermometer, or equivalent) capable of
measuring the gas temperature to within 3 C (5.4 F). A volume
meter is necessary if C02 and S02 concentrations are to be
measured.
A new dry gas meter may be checked for damage visually and
by performing a calibration according to Section 3.13.2. Any dry
gas meter that is damaged, behaves erratically, or does not give
readings within 2 percent of the selected flow rate for each run
is unsatisfactory. Also upon receipt, the meter should be cali-
brated over a varying flow range to see if there is any effect on
the calibration.
Dry gas meters that are equipped with temperature compensa-
tion must be calibrated over the entire range of temperature that
the meter will encounter under actual field conditions. The cal-
ibration must contain at least one data point at each 10 F
interval. All temperatures that are to be used in the field must
be within 2 percent of the calibrated value.
The wet test meter used to check the dry test meter should
be calibrated using the primary displacement technique explained
in Section 3.13.2. The wetgtest meter must have a capacity of at
least 0.003 m /min (0.1 ft /min) with an accuracy of +1 percent;
otherwise at the higher flow rates, the water will not be level
and this will possibly result in incorrect readings.
1.1.8 Rotameter - A rotameter, or its equivalent, with a range
of 0 to 2 L/min is used to monitor and control the sampling flow
rate. The rotameter is checked against the calibrated dry gas
meter with which it is to be used or against a wet test meter.
The rotameter should be within 5 percent of true value or be able
to be set to within 5 percent of true value. The rotameter flow
setting of about 1 L/min should be determined.
Changes in pressure, density, and viscosity of the sample
gas will affect the calibrated sample rate. However, since
sampling at a constant rate is the intent, these changes need not
be considered.
-------
Section No. 3.13.1
Date July 1, 1986
Page 8
1.1.9 Needle Valve - A metering valve with conveniently sized
fittings is required in the sampling train to adjust the sample
flow rate. It is recommended that the needle valve be placed on
the vacuum side of the pump.
1.1.10 Thermometers - A dial thermometer, or its equivalent, is
used to measure the temperature of gas leaving the impinger train
to within 1 C (2 F). Dial type thermometers are easily damaged,
so each new thermometer must be checked visually for damage such
as a dented or bent stem. Each thermometer should read within
1 C (2 F) of the true value when checked in an ice water bath
and at room temperature against a mercury-in-glass thermometer
that conforms to ASTM E-l No. 63C or 63F. Damaged thermometers
that cannot be calibrated must be rejected.
1.1.11 Metering System - For ease of use, the metering system
(if required)—which contains the dry gas meter, thermometer(s),
vacuum pump, needle valve, and rotameter--can be assembled into
one unit (meter box). After a meter box has been either
constructed or purchased, then positive and negative pressure
leak checks should be performed. The positive pressure leak
check, similar to the procedure described in Method 5 (Section
3.4), is performed as follows:
1. Attach rubber tubing and inclined manometer, as shown
in Figure 1.4.
2. Shut off the needle valve and blow into the rubber
tubing until the inclined manometer or magnehelic gauge reads a
positive pressure of 12.5 to 17.5 cm (5 to 7 in.) H20.
3. Pinch off the tube, and observe the manometer for 1
minute. A loss of pressure indicates a leak in the apparatus in
the meter box.
After the meter box apparatus has passed the positive leak
check, then the negative leak check should be performed as
follows:
1. Attach the vacuum gauge at the inlet, and pull a 250 mm
Hg (10 in.) vacuum.
2. Pinch or clamp the outlet of the flow meter. This can
be accomplished by closing the optional shutoff valve, if
employed.
3. Turn off the pump. Any deflection noted in the vacuum
reading within 30 seconds indicates a leak.
4. Carefully release the vacuum gauge before releasing the
flow meter end.
-------
BLOW INTO TUBING
UNTIL MANOMETER
READS 5 to 7 INCHES
WATER COLUMN
RUBBER
TUBING
THERMOMETER
T-CONNECTOR
VENT
INCLINED
MANOMETER
DRY
IGAS METER
NEEDLE VALVE
(CLOSED)
PUMP
SURGE TANK
Figure 1.4. Meter box leak check.
t> o w
0) 0) (D
(Q rt O
(D (D rt
H-
vo d O
C 3
co
M •
VO I-1
oo Co
en •
-------
Section No. 3.13.1
Date July 1, 1986
Page 10
If either of these checks detects a leak that cannot be
corrected, the meter box must be repaired, rejected, and/or
returned to the manufacturer.
The dry gas meter must be equipped with a temperature gauge
(dial thermometer or equivalent). Each thermometer is checked
visually for damage, such as dented or bent face or stem. Each
thermometer should read within 3 C (5.4 F) of the true value when
checked at two different ambient temperatures against a
mercury-in-glass thermometer that conforms to ASTM E-l No. 63C or
63F. The two ambient temperatures used to calibrate the thermom-
eter must differ by a minimum of 10 C (18 F). Damaged
thermometers that cannot be calibrated are to be rejected.
Note; The metering system may not be required or necessary for
many applications of Method 6A or 6B. The tester should deter-
mine the necessity of a dry gas meter. Both Method 6A and 6B
will determine an emission rate without the use of a metering
system. However, if concentration data are desired, a metering
system will be necessary.
1.1.12 Barometer - A mercury, aneroid, or other barometer
capable of measuring atmospheric pressure to within 2.5 mm
(0.1 in.) Hg may be used. However, in many cases, the barometric
reading can be obtained from a nearby National Weather Service
Station, in which case the station value (which is the absolute
barometric pressure) is requested. The tester should be aware
that the pressure is normally corrected to sea level. The
station value is the uncorrected reading. An adjustment for dif-
ferences in elevations of the weather station and sampling point
is applied at a rate of -2.5 mm Hg/30 m (-0.1 in. Hg/100 ft) of
elevation increase, or vice versa for elevation decrease.
Accuracy can be ensured by checking the field barometer
against a mercury-in-glass barometer or its equivalent. If the
field barometer cannot be adjusted to agree with the mercury-
in-glass barometer, it is not acceptable.
1.1.13 Vacuum Gauge - At least one 760-nun (30-in.) Hg gauge is
necessary to leak check the sampling train. An acceptable vacuum
gauge, when checked in a parallel leakless system with a mercury
U-tube manometer at 250-mm (10-in.) Hg vacuum, will agree within
25 mm (1.0 in.) Hg.
1.1.14 Industrial Timer (For Method 6B only) - An industrial
timer-switch designed to operate in the "on" position at least 2
minutes continuously and "off" the remaining period over a
repeating cycle. The cycle of operation is designated in the
applicable regulation. At a minimum, operation should include at
least 12 equal, evenly spaced periods of sampling per 24 hours.
Longer sampling durations greatly reduce the significance of
sampler timer error.
-------
Section No. 3.13.1
Date July 1, 1986
Page 11
Initially check the timer as follows:
1. Set the sampling sequence as it will normally be used
(i.e., 12 equally spaced, 2-minute samples for a 24-hour period).
2. Turn on the sample console (meter box) without the
impinger train.
3. Determine the exact volume that is metered for one of
the equally spaced sample times.
4. Operate the sample console for a 24-hour period.
5. The total sample volume collected should be within 10
percent of the number of times of the equal spacing.
If the industrial timer cannot meet these specifications it
should be repaired or rejected.
1.1.15 Other Sampling Apparatus - Other sampling equipment,
such as Mae West bubblers and rigid cylinders for moisture
absorption which require sample or reagent volumes other than
those specified in this procedure for full effectiveness, may be
used subject to the approval of the Administrator.
1.2 Sample Recovery Apparatus
1.2.1 Wash Bottles - Two 500-ml polyethylene or glass wash
bottles are needed for quantitative recovery of collected
samples.
1.2.2 Storage Bottles - One 100-ml polyethylene bottle is
required to store each collected sample. An additional poly-
ethylene bottle is necessary to retain a blank for each absorbing
solution used in testing. Wash and storage bottles should be
visually checked for damage. In addition, check each storage
bottle seal to prevent sample leakage during transport.
1.3 Analysis Glassware
1.3.1 Pipettes - Several volumetric pipettes (Class A), includ-
ing 5-, 10-, 20-, and 25-ml sizes, are required for the analysis.
1.3.2 Volumetric Flasks - Volumetric flasks (Class A) are
required in 50-, 100-, and 1000-ml sizes.
1.3.3 Burettes - A 50-ml standard burette (Class A) is required
for all titrations.
1.3.4 Erlenmeyer Flasks - One 250-ml Erlenmeyer flask is
required for each sample, blank, standard, and control sample.
-------
Section No. 3.13.1
Date July 1, 1986
Page 12
1.3.5 Dropping Bottle - One 125-ml glass dropping bottle is
needed to prepare the thorin indicator.
1.3.6 Graduated Cylinder - A 100-ml glass (Class A) graduated
cylinder is needed in the preparation of the thorin indicator and
the sample.
All glassware must be checked for cracks, breaks, and
discernible manufacturing flaws.
1.3.7 Balance - A field balance capable of weighing the midget
impingers and the C02 absorber column with an accuracy of 0.1 g
is needed. The balance may be checked upon initial receipt
against Class S weights.
1.4 Reagents
Unless otherwise indicated, it is intended that all reagents
conform to the specifications established by the Committee on
Analytical Reagents of the American Chemical Society (ACS), where
such specifications are available; otherwise the best available
grade is to be used.
1.4.1 Sampling -
Water - Use deionized distilled water to conform to ASTM
specification D 1193-74, Type 3. At the option of the analyst,
the KMnO4 test for oxidizable organic matter may be omitted when
high concentrations of organic matter are not expected to be
present.
Isopropanol, 80 Percent (Method 6A) - Mix 80 ml of isopro-
panol (100 percent) with 20 ml of deionized distilled water.
Check each lot of isopropanol for peroxide impurities as follows:
1. Shake 10 ml of isopropanol with 10 ml of freshly
prepared 10 percent potassium iodide (KI) solution.
2. Prepare a blank by similarly treating 10 ml of water.
3. After 1 minute, read the absorbance of the alcohol
sample against the H2
-------
Section No. 3.13.1
Date July 1, 1986
Page 13
Hydrogen Peroxide, 3 Percent (Method 6A) - Dilute 30 percent
hydrogen peroxide 1:9 (v/v) with water. Prepare fresh daily.
The 30 percent hydrogen peroxide should be stored according to
manufacturer's directions.
Hydrogen Peroxide, 6 Percent (Method 6B) - Dilute 30 percent
hydrogen peroxide 1:3 (v/v) with water. This mixture results in
7.5 percent H202; it should be acceptable for one week in a
closed container. The 30 percent hydrogen peroxide should be
stored according to manufacturer's directions.
Potassium Iodide Solution, 10 Percent - Dissolve 10.0 g of
potassium iodide in water, and dilute to 100 ml. Prepare when
needed. This solution is used to check for peroxide impurities
in the isopropanol only.
Drierite - Anhydrous calcium sulfate (CaSO.) desiccant, 8
mesh, indicating type is recommended. Do not use silica gel or
similar desiccant in this application. Manufacturer's specifica-
tions should be checked upon receipt.
o
Cp_2 Absorber - Ascarite, Ascarite II, or 5A molecular
sieve. Ascarite or Ascarite II is the recommended absorption
media to collect the C02 for both methods because it is an
indicating type of sorbant. The indicating type sorbant will
provide a visual check of whether the sorbant was spent prior to
the completion of the run. Ascarite may also be used for both
methods; the 5A molecular sieve may only be used with the Method
6B constant rate sampling (low flow rate). Because problems have
been detected with molecular sieve lots, it is necessary that new
lots of the molecular sieve material be regenerated upon
receipt. This can be accomplished by placing the molecular sieve
in an oven at 300 C for 4 hours and passing carbon dioxide-free
air through the molecular sieve (while it is in the oven) at a
flow rate equal to the volume of molecular sieve per minute. The
recommended0molecular sieve material is Union Carbide 1/16-inch
pellets, 5 A or equivalent. Note: Ascarite may be a skin irri-
tant, and protection should be taken not to breath the Ascarite
dust.
1.4.2 Sample Recovery - The following are required for sample
recovery:
Water - Use deionized distilled water, as specified in
Subsection 1.4.1.
Isopropanol, 80 Percent (Method 6A) - Mix 80 ml of isopro-
panol with 20 ml of water.
1.4.3 Analysis - The following are required for sample
analysis:
-------
Section No. 3.13.1
Date July 1, 1986
Page 14
Water - Use deionized distilled water, as in Subsection
1.4.1.
Isopropanol, 100 Percent (Method 6A) - As specified above.
Thorin Indicator - Dissolve 0.20 g of l-(o-arsonophenylazo)-
2-naphthol-3, 6-disulfonic acid, disodium salt in 100 ml of
water.
Barium Perchlorate Solution, 0.0100N - Dissolve 1.95 g of
barium perchlorate trihydrate (Ba(C104)2*3H20) in 200 ml of
deionized distilled water and dilute to 1 liter with 100 percent
isopropanol. Alternatively, use 1.22 g of (BaCl2 " 2H20) instead
of the perchlorate. Standardize, as in Section 3.13.5.
Sulfuric Acid Standard, 0.0100N - Either purchase the manu-
facturer's certified or standardize the H2SO. at 0.0100N +p.0002N
against 0.0100N NaOH that has been standardized against primary
standard grade potassium acid phthalate.
1.5 Analytical Equipment
A spectrophotometer is needed to check the isopropanol for
peroxide impurities. The absorbance is read at 352 nm on the
spectrophotometer.
-------
Section No. 3-13.1
Date July 1, 1986
Page 15
Table 1.1 ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS
AND SUPPLIES
Apparatus and
supplies
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Sampling
Sampling probe
with heating
system
Capable of maintaining
100° C (212°F) exit
air at flow rate of
1.0 L/min
Visually check and
run heating system
checkout
Repair or return
to supplier
Out-of-stack
filter
To remove particulate
and to prevent conden-
sation
As above
As above
Flexible
connector
(optional)
To connect the probe
to the midget bubbler
and to prevent conden-
sation
As above
As above
Midget bubbler/
impinger (large
impingers are
acceptable)
Standard stock glass
Visually check upon
receipt for breaks or
leaks
Return to manu-
facturer
C0_ absorber
Minimum capacity of
150 g of Ascarite
Visually check upon
receipt for damage
and proper size
Return to
supplier
Vacuum pump
Capable of maintaining
flow rate of 1 to 2
L/min; leak free at
250 mm (10 in.) Hg
Check upon receipt
for leaks and
capacity
As above
Dry gas meter
(if required)
Capable of measuring
total volume within
2% at a flow rate of
1.0 L/min
Check for damage upon
receipt and calibrate
(Sec. 3.13.2) against
wet test meter
Reject if damaged,
behaves erratical-
ly, or cannot be
properly adjusted
Wet test meter
(if dry gas
meter required)
(continued)
Capable of measuring
total volume within
1%
Upon assembly, leak
check all connections
and check calibration
by liquid displacement
As above
-------
Table 1.1 (continued)
Section No. 3-13.1
Date July 1, 1986
Page 16
Apparatus and
supplies
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Rotameter
Within 5# of manufac-
turer's calibration
curve (recommended)
Check upon receipt for
damage and calibrate
(Sec. 3-13-2) against
wet test meter
Recalibrate and
construct a new
calibration
curve
Thermometers
Within 1C
(2°F)
of true value in the
range of 0°C to
25°C (32° to 77°F)
for impinger and ^3 C
(5.4°F) for dry gas
meter thermometer
Check upon receipt
for damage (i.e., dents
and bent stem), and
calibrate (Sec. 3.13.2)
against mercury-in-
glass thermometer
Return to
supplier if un-
able to cali-
brate
Barometer
Vacuum gauge
Capable of measuring
atmospheric pressure
to within 2.5 mm
(0.1 in.) Hg
Check against mercury-
in-glass barometer or
equivalent (Sec. 3-13-2)
Determine; cor-
rection r'actoi,
or reject if
difference is
than +2.5
0 to 760 mm (0 to
29.92 in.) Hg range,
+25 mm (1.0 in.) Hg
accuracy at 250 mm
(10 in.) Hg
Check against U-tube
mercury manometer
upon receipt
Adjust or return
to supplir-
Industrial
timer (Method
6B only)
Properly operate pump
for specified sampling
cycle
Check the sample cycle
Repair or reject
Sample Recovery
Wash bottles
Polyethylene or glass,
500-ml
Visually check for
damage upon receipt
Replace or
return to
supplier
Storage bottles
(continued)
Polyethylene, 100-ml
Visually check for
damage upon receipt,
and be sure that caps
seal properly
As above
-------
Section No. 3.13.1
Date July 1, 1986
Page 17
Table 1.1 (continued)
Apparatus and
supplies
Balance
Analysis Glass-
ware
Pipettes,
volumetric
flasks , bur-
ettes , and
graduated
cylinders
Reagents
Distilled
water
Isopropanol
(Method 6A only)
Hydrogen
peroxide
Potassium iodide
solution
Drierite
Acceptance limits
Accurate to +0.05g
for weighing impin-
gers and CO-
absorber
Glass, Class A
Must conform to ASTM-
D1193-71*, Type 3
100% isopropanol, re-
agent grade or certi-
fied ACS with no per-
oxide
30% HpO-, reagent
grade or certified
ACS
Potassium iodide,
reagent grade or cer-
tified ACS
Anhydrous calcium sul-
fate (CaSOj.) desiccant,
8 mesh, indicating
type
Frequency and method
of measurement
Check accuracy with
Class S weights
Upon receipt, check
for stock number,
cracks, breaks, and
manufacturer flaws
Check each lot or
specify type when
ordering
Upon receipt, check
each lot for per-
oxide impurities
with a spectro-
photometer
Upon receipt, check
label for grade or
certification
As above
Check manufacturer's
specification upon
receipt
Action if
requirements
are not met
Repair or
reject
As above
As above
Redistill or
pass through
alumina col-
umn, or re-
place
Replace or
return to
manufac-
turer
As above
Reject
(continued)
-------
Section No. 3-13.1
Date July 1, 1986
Page 18
Table 1.1 (continued)
Apparatus and
supplies
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Ascarite or
Ascarite II
Capable of collecting
C0_ for each sample
run
Check out each new
lot with known amount
of CCU
Reject
Thorin indicator
1-(o-arsonophenylazo) -
2-naphthol-3,6-disul-
fonic acid, disodium
salt, reagent grade
or certified ACS
As above
As above
Barium perchlor-
ate solution
Barium perchlorate
trihydrate
As above
As above
reagent grade or
certified ACS
Sulfuric acid
Sulfuric acid,
0.0100N +0.0002N
Have certified by
manufacturer or stand-
ardize against 0.0100N
NaOH that has been
standardized against
potassium acid
phthaiate (primary
standard grade)
As above
-------
Section No. 3.13.2
Date July 1, 1986
Page 1
2.0 CALIBRATION OF APPARATUS
Calibration of the apparatus is one of the most important
functions in maintaining data quality. The detailed calibration
procedures included in this section were designed for the equip-
ment specified by Method 6 and described in the previous sec-
tion. Table 2.1 at the end of this section summarizes the
quality assurance functions for calibration. All calibrations
should be recorded on standardized forms and retained in a
calibration log book.
2.1 Metering System
As previously stated, the metering system may not be re-
quired. For Methods 6A and 6B trains that do not use the
metering system, no calibration is required.
2.1.1 Wet Test Meter - The wet test meter must be calibrated and
have the proper capacity. For Methods 6A and 6B, the wet test
meter should have a capacity of at least 2 L/min. No upper limit
is placed on the capacity; however, a wet test meter dial should
make at least one complete revolution at the specified flow rate
for each of the three independent calibrations.
Wet test meters are calibrated by the manufacturer to an
accuracy of +^0.5 percent. Calibration of the wet test meter must
be checked initially upon receipt and yearly thereafter.
The following liquid positive displacement technique can. be
used to verify and adjust, if necessary, the accuracy of the wet
test meter to +1 percent:
1. Level the wet test meter by adjusting the legs until the
bubble on the level located on the top of the meter is centered.
2. Adjust the water volume in the meter so that the pointer
in the water level gauge just touches the meniscus.
3. Adjust the water manometer to zero by moving the scale
or by adding water to the manometer.
4. Set up the apparatus and calibration system as shown in
Figure 2.1.
a. Fill the rigid-wall 5-gal jug with water to below
the air inlet tube, and allow both to equilibrate
to room temperature (about 24 h) before use.
b. Start water siphoning through the system, and
collect the water in a 1-gal container, located in
place of the volumetric flask.
-------
Section No. 3.13.2
Date July 1, 1986
Page 2
AIR INLET
TUBE
THERMOMETER
WATER
S IN
-I-
WATER J
LEVEL/
GAUGE/
WATER OUT
VALVE
OR PINCH CLAMP
2000-ML LINE
CLASS A
VOLUMETRIC
FLASK
LEVEL ADJUS
Figure 2.1. Calibration check apparatus for wet test meter.
-------
Section No. 3.13.2
Date July 1, 1986
Page 3
5. Check operation of the meter as follows:
a. If the manometer reading is <10 mm (0.4 in.) I^O,
the meter is in proper working condition. Continue
to step 6.
b. If the manometer reading is >10 mm (0.4 in.) Ho^'
the wet test meter is defective or the saturator
has too much pressure drop. If the wet test meter
is defective, return to the manufacturer for repair
if the defect(s) (e.g., bad connections or joints)
cannot be found and corrected.
6. Continue the operation until the 1-gal container is
almost full. Plug inlet to the wet test meter. If no leak
exists, the flow of liquid to the gallon container should stop.
If the flow continues, correct for leaks. Turn the siphon system
off by closing the valve, and unplug the inlet to the wet test
meter.
7. Read the initial volume (V.) from the wet test meter
dial, and record on the wet test meter calibration log, Figure
2.2.
8. Place a clean, dry volumetric flask (Class A) under the
siphon tube, open the pinch clamp, and fill the volumetric flask
to the mark. The volumetric flask must be large enough to allow
at least one complete revolution of the wet test meter with not
more than two fillings of the volumetric flask.
9. Start the flow of water, and record the maximum wet test
meter manometer reading during the test after a constant flow of
liquid is obtained.
10. Carefully fill the volumetric flask, and shut off the
liquid flow at the 2-liter mark. Record the final volume on the
wet test meter.
11. Perform steps 7 through 10 three times.
Since the water temperature in the wet test meter and reser-
voir has been equilibrated to the ambient temperature and since
the pressure in the wet test meter will equilibrate with the
water reservoir after the water flow is shut off, the air volume
can be compared directly with the liquid displacement volume.
Any temperature or pressure difference would be less than meas-
urement error and would not affect the final calculations.
The error should not exceed +1 percent; should this error
magnitude be exceeded, check all connections within the test
apparatus for leaks, and gravimetrically check the volume of the
-------
Wet test meter serial number T3 ~
Date
Range of wet test meter flow rate Q — (2.O
Volume of test flask V0 =
s —
Satisfactory leak check?
/.
Ambient temperature of equilibrate liquid in wet test meter and reservoir
'
Test
number
1
2
i
Manometer
reading, a
mm H2O
6~
6"
f
Final
volume (Vj),
L
A?f
2-00
z-#>
Initial
volume (V^,
L
a
0
0
Ototal
volume (Vm)b,
L
A?f
^2.00
z.oo
Flask
volume (Va),
L
2-00
1,00
^.oo
Percent
error, q
%
o.$
0
0
Must be less than 10 mm (0.4 in.)
m
vf - v±.
% error = 100 (Vm - Vg)As =
(+1%).
Signature of calibration person
Figure 2.2. Wet test meter calibration log.
•O O w
0) CD a> (t
CO
H •
VD h-1
00 CO
cn •
-------
Section No. 3.13.2
Date July 1, 1986
Page 5
standard flask. Repeat the calibration procedure, and if the
tolerance level is not met, adjust the liquid level within the
meter (see the manufacturer's manual) until the specifications
are met.
2.1.2 Sample Metering System - The sample metering system--
consisting of the needle valve, pump, rotameter, and dry gas
meter--is initially calibrated by stringent laboratory methods
before it is used in the field. The calibration is then re-
checked after each field test series for Method 6A and every 30
days of operation for Method 6B. This recheck requires less
effort than the initial calibration. When a recheck indicates
that the calibration factor has changed, the tester must again
perform the complete laboratory procedure to obtain the new cali-
bration factor. After the meter is recalibrated, the metered
sample volume is multiplied by the calibration factor (initial or
recalibrated) that yields the lower gas volume for each test
run. Both sets of calibration results should be reported.
Initial Calibration - The metering system should be cali-
brated when first purchased and at any time the posttest check
yields a calibration factor that does not agree within 5 percent
of the pretest calibration factor. A calibrated wet test meter
(properly sized, with +1 percent accuracy) should be used to
calibrate the metering system.
The metering system should be calibrated in the following
manner before its initial use in the field.
1. Leak check the metering system (needle valve, pump, rot-
ameter, and dry gas meter) as follows:
3
a. Temporarily attach a suitable rotameter (e.g., 0-40 cm /m
in) to the outlet of the dry gas meter (for the 1 L/min
sample train), and place a vacuum gauge at the inlet to
the sample train. Alternatively, for trains without a
dry gas meter, place the rotameter at the discharge of
the CO2 absorber.
b. Pull a vacuum of at least 250 mm (10 in.) Hg.
c. Note the flow rate as indicated by the rotameter for the
1 L/min sample train or time the movement of the dry gas
meter needle for 2 minutes on the low flow train.
d. A leak of less than 2 percent of the appropriate sample
rate must be recorded or leaks must be eliminated.
e. Carefully release the vacuum gauge before turning off
pump.
-------
Section No. 3.13.2
Date July 1, 1986
Page 6
2. Assemble the apparatus, as shown in Figure 2.3, with the
wet test meter replacing the C02 absorber and impingers; i.e.,
connect the outlet of the wet test meter to the inlet side of the
needle valve.
3. Run the pump for 15 minutes with the flow rate set at
1 L/min to allow the pump to warm up and to permit the interior
surface of the wet test meter to become wet.
4. Collect the information required in the forms provided,
Figure 2.4A (English units) or 2.4B (metric units), using sample
volumes equivalent to at least five revolutions of the dry test
meter. Three independent runs must be made.
5. Calculate Y. for each run of the three runs using
Equation 2-1. Record the values on the form (Figure 2.4A or
2. 4B).
V (t, + 460) fp + (D /13.6)1 . . „ n
Y _ w v d ' [ m v nr '} Equation 2-1
1 Vd (tw + 460) Pm
where
Y. = ratio for each run of volumes measured by the wet test
meter and the dry gas meter, dimensionless calibration
factor,
3 3
V = volume measured by wet test meter, m (ft ),
W
P = barometric pressure at the meters, nun (in.) Hg,
D = pressure drop across the wet test meter, mm (in.) H-O,
t, = average temperature of dry gas meter, °C (°F),
3 3
V, = volume measured by the dry gas meter, m (ft ), and
t = temperature of wet test meter, C ( F).
W
6. Adjust and recalibrate or reject the dry gas meter if
one or more values of Y. fall outside the interval Y ^0.02Y,
where Y is the average for three runs. Otherwise, the Y
(calibration factor) is acceptable and will be used for future
checks and subsequent test runs. The completed form should be
forwarded to the supervisor for approval, and then filed in the
calibration log book.
An alternative method of calibrating the metering system
consists of substituting a dry gas meter, which has been properly
-------
MANOMETER
THERMOMETER
THERMOMETER
/ DRY
[ GAS
V METER
SURGE TAN.
WATER IN
WATER LEVEL
GAUGE
WATER OUT
LEVEL ADJUST
•d o w
0) 0) 0)
(O rt o
(D
-------
Date /— ZS~—g$" Calibrated by
Barometer pressure, Pm =
Meter box number
Wet test meter number
in. Hg Dry gas meter temperature correction factor
Wet test
meter
pressure
drop
'a
in. H2O
o.ts
D.zr
O.Z6
Rota-
meter
setting
(Rs),
ft3/min
o.oyz
O.QZ?
o-o^
Wet test
meter gas
volume
,b
ft3
/•£>&&
/•CXf
/.CX.I
Dry test meter
gas volume
(vd),b ft3
Initial
~bS~.&3
7Z&.W
732..W
Final
724. (,72.
730. Oil
733. /SB
Wet test
meter
gas temp
IQ rt O
(D
Y2 + Y3
(Eq. 3)
and Yr =
1.02-to . (Eq. 4)
Figure 2.4A. Dry gas meter calibration data form (English units).
\O M
CD CO
to
-------
Date -
Barometer pressure, P
Calibrated by
746
Meter box number £• ~
Wet test meter number
I&I ~rr
in. Hg Dry gas meter temperature correction factor
Wet test
meter
pressure
drop
(D ) a
1 m' •
mm H2O
04
1.+
W
Rota-
meter
setting
Zl
21
Average
gas temp
(td),c
°C
2-(,,5~
275"
26.5-
Time
of run
4)
V D W
Q) 0) (D
U3 rt O
(D (0 rt
H-
vO Ui O
C 3
O
I-1 •
CO
!-• «
VD M
00 CO
0\ •
to
Figure 2.4B. Dry gas meter calibration data form (metric units)
-------
Section No. 3.13.2
Date July 1, 1986
Page 10
prepared as a calibration standard, in place of the wet test
meter. This procedure should be used only after obtaining
approval of the Administrator.
Posttest Calibration Check - After each field test series
for Method 6A and after every 30 days of operation for Method 6B,
conduct a calibration check as in Subsection 2.1.2 with the
following exceptions:
1. The leak check is not conducted because a leak should
not be corrected that was present during testing.
2. Three or more revolutions of the dry gas meter may be
used.
3. Only two independent runs need be made.
4. If a temperature-compensating dry gas meter was used,
the calibration temperature for the dry gas meter must be within
6 C (10.8 F) of the average meter temperature observed during the
field test series.
When a lower meter calibration factor is obtained as a
result of an uncorrected leak, the tester should correct the leak
and then determine the calibration factor for the leakless sys-
tem. If the new calibration factor changes the compliance status
of the facility in comparison to the lower factor, either include
this information in the report or consult with the administrator
for reporting procedures. If the calibration factor does not
deviate by >5 percent from the initial calibration factor Y
(determined in Subsection 2.1.2), then the dry gas meter volumes
obtained during the test series are acceptable. If the cali-
bration factor does deviate by >5 percent, recalibrate the meter-
ing system as in Subsection 2.1.2, and for the calculations, use
the calibration factor (initial or recalibration) that yields the
lower gas volume for each test run.
2.2 Thermometers
The thermometers used to measure the temperature of gas
leaving the C02 absorber should be initially compared with a
mercury-in-glass thermometer that meets ASTM E-l No. 63C or 63F
specifications:
1. Place both the mercury-in-glass and the dial type or an
equivalent thermometer in an ice bath. Compare the readings
after the bath stabilizes.
2. Allow both thermometers to come to room temperature.
Compare readings after both stabilize.
-------
Section No. 3.13.2
Date July 1, 1986
Page 11
3. The dial type or equivalent thermometer is acceptable if
values agree within 1C (2 F) at both points. If the difference
is greater than 1C (2 F), either adjust or recalibrate the
thermometer until the above criteria are met, or reject it.
4. The thermometer is used as an indicator and accuracy of
readings is not important for field use.
The thermometer(s) on the dry gas meter inlet used to measure
the metered sample gas temperature should be initially compared
with a mercury-in-glass thermometer that meets ASTM E-l No. 63C
or 63F specifications (if the dry gas meter is required, other-
wise, no calibration is required):
1. Place the dial type or an equivalent thermometer and the
mercury-in-glass thermometer in a hot water bath, 40 to 50 C
(104 to 122 F). Compare the readings after the bath stabilizes.
2. Allow both thermometers to come to room temperature.
Compare readings after the thermometers stabilize.
3. The dial type or equivalent thermometer is acceptable if
values agree within 3 C (5.4 F) at both points (steps 1 and 2
above) or if the temperature differentials at both points are
within 3 C (5.4°F) and the temperature differential is taped to
the thermometer and recorded on the meter calibration form
(Figure 2.4A or 2.4B).
4. Prior to each field trip, compare the temperature read-
ing of the mercury-in-glass thermometer at room temperature with
that of the thermometer that is part of the meter system. If the
values or the corrected values are not within 6 C (10.8°F) of
each other, replace or recalibrate the meter thermometer.
5. The thermometer must be recalibrated only when the volume
metering system does not pass the posttest calibration.
2.3 Rotameter
The Reference Method does not require that the tester cali-
brate the rotameter. The rotameter should be cleaned and main-
tained according to the manufacturer's instructions. For this
reason, it is recommended that the calibration curve and/or rota-
meter markings be checked upon receipt and then routinely checked
with the posttest meter system check or at the required frequency
for the posttest meter check when a dry gas meter is not used.
The rotameter may be calibrated as follows:
1. Ensure that the rotameter has been cleaned as specified
by the manufacturer, and is not damaged.
-------
Section No. 3.13.2
Date July 1, 1986
Page 12
2. Use the manufacturer's calibration curve and/or markings
on the rotameter for the initial calibration. Calibrate the rot-
ameter as described in the meter system calibration of Subsection
2.1.2, and record the data on the calibration form (Figure 2.4A
or 2.4B).
3. Use the rotameter for testing if the pretest calculated
calibration is within the range 1.0 +0.05 L/min. If, however,
the calibration point is not within 5 percent, determine a new
flow rate setting, and recalibrate the system until the proper
setting is determined.
4. Check the rotameter calibration with each posttest meter
system check. If the rotameter check is within 10 percent of the
1-L/min setting, the rotameter can be acceptable with proper
maintenance. If, however, the check is not within 10 percent of
the flow setting, disassemble and clean the rotameter and perform
a full recalibration.
2.4 Barometer
The field barometer should be adjusted initially and before
each test series to agree within 2.5 mm (0.1 in.) Hg with a
mercury-in-glass barometer or with the pressure value reported
from a nearby National Weather Service Station and corrected for
elevation. The tester should be aware that the pressure readings
are normally corrected to sea level. The uncorrected readings
should be obtained. The correction for the elevation difference
between the weather station and the sampling point should be
applied at a rate of -2.5 mm Hg/30m (-0.1 in. Hg/100 ft) ele-
vation increase, or vice versa for elevation decrease.
The calibration checks should be recorded on the pretest sam-
pling form (Figure 2.5).
2.5 Balance
The balance must be checked prior to each series of weigh-
ings, but not more than once a day. Place the C02 absorber or a
midget impinger on the balance. Record the weighr. Place a 5 g
Class S weight on the balance and record the weight. The
difference must be 5.0 +_ 0.1 g or the balance must be adjusted,
repaired, or rejected.
-------
Section No. 3.13.2
Date July 1, 1986
Page 13
Date /fl/2-5/55" Calibrated by gj£S
^ ~f
Meter box number g ~v»
Rotameter
Pretest calibration factor (Y ) acceptable? i/ yes no
(within 10 percent of correct value).
Dry Gas Meter (If applicable)
Pretest calibration factor (Y) = /.O2.I (within 2 percent of
average factor for each calibration run).
Gas Meter Thermometer (If applicable)
Temperature correction necessary? yes _^_no
(within 3 C (5.4 F) of reference values for calibration and
within 6 C (10.8 F) of reference values for calibration
check).
If yes, temperature correction
Barometer
Field barometer reading correct? r yes no
(within 2.5 mm (0.1 in) Hg of mercury-in-glass barometer).
Balance
Was the pretest calibration of the balance correct? _*^yes no
(within 0.05 g of true value using Class S weights).
Most significant items/parameters to be checked.
Figure 2.5. Pretest sampling checks.
-------
Section No. 3.13.2
Date July 1, 1986
Page 14
Table 2.1. ACTIVITY MATRIX FOR CALIBRATION OF EQUIPMENT
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Wet test meter
Capacity of at least
2 L/min and an accur-
acy within 1.0%
Calibrate initially and
then yearly by liquid
displacement
Adjust until
specifications
are met, or
return to man-
ufacturer
Dry gas meter
Y. = Y+0.02Y at a
flow rate of about
1 L/min
Calibrate vs. wet test
meter initially and when
the posttest check is
not within Y+0.05Y
Repair and
then recali-
brate or re-
place
CO- absorber
thermometer
Within 1°C (2°F)
of true value
Calibrate each ini-
tially as a separate
component against a
mercury-in-glass ther-
mometer
Adjust, deter-
mine a con-
stant correc-
tion factor,
or reject
Dry gas meter
thermometer
Within 3°C (5.4 F)
of true value
Calibrate initially
and recalibrate when
the meter system
does not pass the
posttest check
As above
Rotameter
Clean and maintain
according to manu-
facturer's instruc-
tions (required);
calibrate to +_ 5%
(recommended)
Initially and after
each field trip for
Method 6A and every
30 days of operation
for Method 6B
Adjust and re-
calibrate, or
reject
Barometer
^2.5 mm (0.1 in.)
Hg of mercury-in-
glass barometer or
of weather station
value
Calibrate initially
using a mercury-in-
glass barometer; check
before and after each
field test
Adjust to agree
with certified
barometer
Balance
Weigh impinger
and CO- absorb-
er to + 0.1 g
Check prior to each
series of weighings
Adjust to agree,
repair, or
reject
-------
Section No. 3.13.3
Date July 1, 1986
Page 1
3.0 PRESAMPLING OPERATIONS
The quality assurance activities for presampling preparation
are summarized in Table 3.1 at the end of this section. See
Section 3.0 of this Handbook for details on preliminary site
visits.
3.1 Apparatus Check and Calibration
Figure 3.1 or a similar form is recommended to aid the tester
in preparing an equipment checklist, status report form, and
packing list.
3.1.1 Sampling Train - The schematic of the SO2 train is given
in Figure 1.1. Commercial models of this system are available.
Each individual or fabricated train must be in compliance with
the specifications in the Method, Section 3.5.10.
3.1.2 Probe - The probe should be cleaned internally by brushing
first with tap water, then with deionized distilled water, and
finally with acetone. Allow probe to dry in the air. In extreme
cases, the glass or stainless steel liner can be cleaned with
stronger reagents; the objective is to leave the liner free from
contaminants. The probe's heating system should be checked to
see that it is operating properly. The probe must be leak free
when sealed at the inlet or tip and checked for leaks at a vacuum
of 250 mm (10 in.) Hg with the meter box. Any leaks should be
corrected. The liner should be sealed inside the metal sheath to
prevent diluent air from entering the source since most stacks
are under negative pressure.
3.1.3 Midget Bubblers, Midget Impingers, and Glass Connectors -
All glassware should be cleaned with detergent and tap water,
and then with deionized distilled water. Any items that do not
pass a visual inspection for cracks or breakage must be repaired
or discarded.
3.1.4 CO,, Absorber - The cylinders or bottles may be packed with
the Ascarite, numbered, weighed, and sealed in the laboratory
prior to the field trip. If molecular sieve material is used,
ensure that it has been regenerated as described in Subsection
1.4.1.
3.1.5 Valve and Rotameter - Prior to each field trip or at any
sign of erratic behavior, the flow control valve and rotameter
should be cleaned according to the maintenance procedure recom-
mended by the manufacturer.
3.1.6 Pump - The vacuum pump and oiler should be serviced as
recommended by the manufacturer, every 3 months, or upon erratic
behavior (nonuniform or insufficient pumping action).
-------
Section No. 3.13.3
Date July 1, 1986
Page 2
Apparatus check
Probe
Type liner
Glass X"
Stainless
steel
Other
Heated properly
Leak checked on
sampling train
Filter or Filter
Assembly
Glass wool X
Other
Glassware
Midget bubbler
Midget impinger
Size rJ/A
Type M/A
Meter System
With timer
Without timer x
Leak-free pump*
Rate meter*
Dry gas meter*
Reagents
Distilled water
H202/ 30%
isopropanol, 100%*
(for Method 6A)
Drierite
Ascarite X
or 5A molecular
sieve*
Other
Barometer
CO2 absorber
column
Balance
Acceptable
Yes
/
S
!/
s
I/
^
I/
s
s
s
t-
\s
S
S
\s
s
NO
Quantity
required
4-
4- on^-of-
Sfeot.
6
8
2-
2. 4+1
1 fr
1 3*1
10*
io#
I
f
I
Ready
Yes
i/
S
S
v^
^
\S
\^
\s
V
S
\s
iS
^
No
Loaded
and packed
Yes
^
^
(/
^
-
\/
t
i/
^
^
S
^
No
*Most significant items/parameters to be checked.
Figure 3.1. Pretest preparations .
-------
Section No. 3.13.3
Date July 1, 1986
Page 3
3.1.7 Dry Gas Meter - A dry gas meter calibration check should
be made in accordance with the procedure in Section 3.13.2. An
acceptable posttest check from the previous test is sufficient.
3.1.8 Thermometers - The thermometers should be compared with
the mercury-in-glass thermometer at room temperature prior to
each field trip.
3.1.9 Barometer - The field barometer should be compared with
either themercury-in-glass barometer or a National Weather
Service Station prior to each field trip.
3.1.10 Balance - Check balance with Class S weights using proce-
dures from Subsection 2.5 and pack in rigid foam container.
3.1.11 Other Sampling Apparatus - Other sampling equipment, such
as Mae West bubblers and rigid cylinders for moisture absorption,
which require sample or reagent volumes other than those speci-
fied in this procedure for full effectiveness, may be used sub-
ject to the approval of the Administrator.
3.2 Reagents and Equipment
3.2.1 Sampling - The midget bubbler solution (for Method 6A) is
prepared by mixing 80 ml of isopropanol (100 percent) with 20 ml
of water. The midget impinger absorbing reagent is prepared by
diluting 100 ml of 30 percent hydrogen peroxide to 1 liter with
water for Method 6A or 250 ml of 30 percent hydrogen peroxide to
1 liter with water for Method 6B. All reagents must be prepared
fresh for each test series, using ACS reagent grade chemicals.
Solutions containing isopropanol must be kept in sealed contain-
ers to prevent evaporation. Twenty five (25) g of Drierite is
needed for each sample collection. Sufficient quantity should be
brought in a sealed container.
3.2.2 Sample Recovery - Deionized distilled water is required on
site for quantitative transfer of impinger solutions to storage
containers. This water and isopropanol are used to clean the
midget bubbler after testing and prior to taking another sample.
3.3 Packaging Equipment for Shipment
Equipment should be packed in rigid containers to protect it
against rough handling during shipping and field operations (not
mandatory).
3.3.1 Probe - The inlet and outlet of the probe must be sealed
and protected from breakage. A suggested container is a wooden
case lined with polyethylene foam or other suitable packing
material; the case should have separate compartments for individ-
ual devices. The case should be equipped with handles or eye
-------
Section No. 3.13.3
Date July 1, 1986
Page 4
hooks that can withstand hoisting, and should be rigid to prevent
bending or twisting during shipping and handling.
3.3.2 Midget Bubblers, Impingers, Connectors, and Assorted
Glassware - All bubblers, impingers, and glassware should be
packed in a rigid container and protected by polyethylene foam or
other suitable packing material. Individual compartments for
glassware help to organize and protect each item. The impinger
train may be charged and assembled in the laboratory if sampling
is to be performed within 24 hours.
3.3.3 COg Absorber and Volumetric Glassware - A rigid container
lined wirh polyethylene foam material protects C02 absorber and
assorted volumetric glassware.
3.3.4 Meter Box - The meter box (if required)--which contains
the valve,rotameter, vacuum pump, dry gas meter, and thermom-
eters—should be packed in a rigid shipping container unless its
housing is strong enough to protect components during travel.
Additional pump oil should be packed if oil is required for
operation. It is advisable to ship a spare meter box in case of
equipment failure.
3.3.5 Wash Bottles and Storage Containers - Storage containers
and miscellaneous glassware may be safely transported, if packed
in a rigid foam-lined container. Samples being transported in
the containers should be protected from extremely high ambient
temperatures (>50°C or about 120 F).
-------
Section No. 3.13-3
Date July 1, 1986
Page 5
Table 3.1. ACTIVITY MATRIX FOR PRESAMPLING OPERATIONS
Operation
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Apparatus
Probe
1. Probe liner free
of contaminants
2. Probe leak free at
at 250 mm (10 in.) Hg
3. No moisture conden-
sation
1. Clean probe internal-
ly by brushing with tap
water, then deionized
distilled water, then
acetone; allow to dry in
air before test
2. Visual check before
test
Check out heating system
initialy and when mois-
ture appears during
testing
1. Retrace
cleaning pro-
cedure and
assembly
2. Replace
3. Repair or
replace
Midget bubbler,
midget impin-
ger, C0_ ab-
sorber, and
glass con-
nectors
Clean and free of
breaks, cracks, etc.
Clean with detergent,
tap water, and then
with deionized dis-
tilled water
Repair or
discard
Flow control
valve and
rotameter
Clean and without sign
of erratic behavior
(such as ball not
moving freely)
Clean prior to each
field trip or upon
erratic behavior
Repair or
return to
manufacturer
Vacuum pump
Maintain sampling rate
of about \ L/min up
to 250 mm (10 in.) Hg
Service every 3 mo or
upon erratic behavior;
check oiler jars every
10th test
As above
Dry gas meter
(if required)
Clean and within 2%
of calibration factor
Calibrate according to
Sec. 3.13.2; check for
excess oil if oiler is
used
As above
Balance
(continued)
Accurate to within
0.1 g
Check with Class S
weights
As above
-------
Section No. 3.13-3
Date July 1, 1986
Page 6
Table 3.1. (continued)
Operation
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Reagents
Sampling
1. Requires all ACS
grade reagents
2. New C02
absorber material
1. Prepare fresh daily
and store in sealed
containers
2. Purchase new
1. Prepare new
reagent
2. Reorder
Sample recovery
Requires deionized
distilled water on
site
Use water and reagent
grade isopropanol to
clean midget bubbler
after test and before
sampling
Prepare new
reagent
Package Equip-
ment for Ship-
ment
Probe
Protect with poly-
ethylene foam
Prior to each ship-
ment
Repack
Midget bubbler,
impingers, con-
nectors, and
assorted glass-
ware
Pack in rigid con-
tainers with poly-
ethylene foam
As above
As above
CO- absorber,
volumetric
glassware
Sturdy container
lined with foam
As above
As above
Meter box
Meter box case and/or
container to protect
components; pack spare
meter box and oil
As above
As above
Wash bottles
and storage
containers
Pack in rigid foam-
lined container
As above
As above
Balance
Pack in rigid foam-
lined container
As above
As above
-------
Section No. 3.13.4
Date July 1, 1986
Page 1
4.0 ON-SITE MEASUREMENTS
On-site activities may include transporting the equipment to
the test site, unpacking and assembling, sampling for sulfur
dioxide and carbon dioxide analyses, and recording the data. In
general for Method 6B, the equipment would be maintained at or
near the test site and testing would be on a more routine basis.
Since Method 6B is used to determine a daily average, facilities
should consider running duplicate Method 6B sampling trains. One
Method 6B sampling train would be designated as the primary and
the other would be the backup train. This would prevent the loss
of data, provide a check of sampling problems, provide sampling
precision data, and provide a complete backup sample system for
when the primary train is inoperable. The additional manpower
requirements should not be significant when compared to the
possible gain in emissions data recovery. The on-site quality
assurance activities are summarized in Table 4.1 at the end of
this section.
4.1 Transport of Equipment to the Sampling Site
The most efficient means of transporting the equipment from
ground level to the sampling site (often above ground level)
should be decided during the preliminary site visit or by prior
correspondence. Care should be taken to prevent damage to the
equipment or injury to test personnel during the moving. A
laboratory type area should be designated for preparation of the
absorbing reagents, for charging of the bubblers and impingers,
and for sample recovery and analyses.
4.2 Preliminary Measurements and Setup
The Reference Method outlines the procedure used to deter-
mine the concentration of sulfur dioxide in the gas stream in
terms of pounds of sulfur dioxide per million Btu's. The accu-
racy of the equipment after transport to the sampling site and
possible rough handling can be determined by making a one-point
check of the rotameter reading against the dry gas meter reading
at the test site. Use Equation 3 in Figure 2.4A or 2.4B and
substitute dry gas meter readings in place of wet test meter
readings (i.e., V, = V ). The value Y . should be between 0.9
and 1.1; if not, the meter box has lost its rate or volume
calibration. The tester can still use the meter box, but the
data should not be released for decision making until a posttest
recalibration has been made. If the dry gas meter calibration
factor did change, the dry gas meter volumes may have to be
corrected. Record the test identification number on the appro-
priate sampling form, Figure 4.1 (for Method 6A) or Figure 4.2
(for Method 6B).
-------
ro
Plant name
Sample location QeiUr /\/o. 3
Operator
Barometric pressure, mm (>rfT) Hg
Probe material
Meter box number
Ambient temperature, C
Initial leak check Q.D04-L/*in@
Final leak check Q.OQl, l,/iM>»(3>
Section No. 3-13.4
Date July 1, 1986
Page 2
City
Date
Sample number
Probe length m
2S&*
Probe heater setting
Meter calibration factor (Y) /.£>/
Sampling point location /.35V*i
Sample purge time, min
Remarks
/£"
tfavi^ff*.
Sampling
time,
min
0
$
lo
g
2o
tZ
Total
vs
Clock
time,
24 h
not
llo£
IUO
/lit
II w
//2T
Sample
volume,
L X#^T
/ ZO. 2-0
12^.30
130. 10
IIS. 2.0
140.20
11$. to
Total
2S. 00
Sample
flow rate
setting,
L/min
J^-hsi^T
—
1-0
Lo
l.o
ID
1-0
Sample
volume
metered
L &^j
—
5!/
4.6
$t
s.o
S~.D
Vm $.0
avg
Percent
deviation,
%
z
f
Z
0
0
Avg i r
dev '-^
Dry gas
meter
°ce^T
2-7
2.1
3o
30
5o
Avg
^c\
Impinger
temp,
°C J^T
11
2o
10
to
to
Max
temp^
Percent deviation = m m avg
x 100 (must be within 10 percent)
V avg
m
Figure 4.1. Field sampling data form for Method 6A.
-------
Section No. 3.. 13.4
Date July 1, 1986
Page 3
Plant Ac-*-* re>*>e+- Pl±*l-
Sample location ;8<»/'k»- No-
Operator /£?/4s
Run No. Af-l
Sampling period Start:
Stop:
Dry Gas Meter
Final reading 744. 14 L
Initial reading 7/^.32. L
Volume metered 2.7.62- L
Dry Gas Meter Calibration
Initial leak check G>t*J-/^<*-
3 Final leak check
Recovery date
Recovered by /
Date /O/12-IB^
Date /£>//3/£S~
f
Rotameter
Initial setting
Final setting
Factor, Y /.Ol7
Z *u
/Ol 131 i
«L£S>
Time
Time
l.O L
1.0 L
1 1 m it*—
*>$-
'30«**\ time
2^. 73
/o : 45"<*^
in. Hg
time
ure Filter Temperature Ascarite Column
F Initial 12.0 °F Final wt 3/2./ g
F Final itO °F
bubbler 2nd impinger
75./ g 69.3 g
737 g fo.O g
0.0 g 2-0 q
Total moisture 3.6
Inital wt
Net wt
3rd impinger
883 g
68-2- g
O.I g
g 20
303-6 g
8.5T g of co0
4th bubbler
9.T.2. g
l^~ g
% spent
H2°2
container no.
RECOVERED SAMPLE (If Applicable)
Liquid level
AP~
marked
Impinger contents
container no.
Liquid level
marked
H20 blank
container no.
Liquid level
marked
Samples stored and locked
Received by
Remarks
Date
Figure 4.2.
Method 6B sampling, sample recovery, and sample
integrity data form.
-------
Section No. 3.13.4
Date July 1, 1986
Page 4
4.3 Sampling
The on-site sampling includes the following steps:
1. Preparation and/or addition of the absorbing reagents
to the midget bubblers and impingers and CO.., absorber.
2. Setup of the sampling train.
3. Connection to the electrical service.
4. Preparation of the probe (leak check of entire sampling
train and addition of particulate filter).
5. Insertion of the probe into the stack.
6. Sealing the port.
7. Checking the temperature of the probe.
8. Sampling.
9. Recording the data in Figure 4.1.
A final leak check of the train is always performed after samp-
ling.
4.3.1 Preparation and/or Addition of Absorbing Reagents to Col-
lection System - Absorbing reagents can be prepared on site, if
necessary, according to the directions in Section 3.13.3.
For Method 6A
1. Use a pipette or a graduated cylinder to introduce 15
ml of 80 percent isopropanol (IPA) into the midget bubbler or
into a graduated impinger bottle. Do not use the pipette or
graduated cylinder that was used to add the hydrogen peroxide
solution without cleaning. Pipettes or graduated cylinders
should be marked for use of Ho^7 or I^>A ^° minimize anY pos-
sibility of introducing hydrogen peroxide into the isopropanol.
The accuracy of a pipette is not required but may be used for
convenience.
2. Add 15 ml of 3 percent hydrogen peroxide to each of the
two midget impingers (100 ml of 30 percent ^2°2 to 1 liter with
water).
3. Pack glass wool into the top of the first midget
bubbler to prevent sulfuric acid mist from entering the midget
impingers and causing a high bias for S02-
-------
Section No. 3.13.4
Date July 1, 1986
Page 5
4. Add about 25 g of Drierite to the last midget bubbler.
5. Calibrate the balance by initially placing a C02
absorber or midget impinger on the balance and recording the
weight. Then add a 5 g or 10 g Class S weight. The difference
must be accurate to within 0.05 g. (Calibrate only once a day.)
6. Weigh each impinger and bubbler, including contents, to
the nearest 0.1 g, and record the data on the sample recovery and
integrity form (Figure 4.3).
7. With one end of the CO2 absorber sealed, place glass
wool in the cylinder to a depth or about 1 cm. Place about 150 g
of Ascarite II in the cylinder on top of the glass wool, and fill
the remaining space in the cylinder with glass wool. Assemble
the cylinder as shown in Figure 4.4. With the cylinder in a
horizontal position, rotate it around the horizontal axis. The
C02 absorbing material should remain in position during the
rotation, and no open spaces or channels should be formed. If
necessary, pack more glass wool into the cylinder to make the
C02 absorbing material stable. Clean the outside of the cylinder
of loose dirt and moisture, and weigh at room temperature to the
nearest 0.1 g. Record this initial mass on the data form
(Figure 4.3). It is strongly recommended that a second, smaller
C0« absorber containing Ascarite or Ascarite ±1 be added in line
downstream of the primary C02 absorber as a breakthrough indi-
cator. Ascarite II turns white when C02 is absorbed. The C02
absorber may be pre-packed.
For Method 6B
1. The first midget bubbler remains empty or dry. It is
also advisable to break off the stem to prevent the solutions
from backing up into the probe.
2. Add 15 ml of X> percent hydrogen peroxide to each of the
two midget impingers (250 ml of 30 percent H909 to 1 liter with
distilled water).
3. Add about 25 g of Drierite to the last bubbler or more
to a cylinder.
4. Weigh each impinger or bubbler including contents, to
the nearest 0.1 g and record the data on the sample data form
(Figure 4.2). Note: If large impingers are used more solution
should be added and more Drierite used.
5. With one end of the C02 absorber sealed, place glass
wool in the cylinder to a depth of about 1 cm. Place about 150 g
of Ascarite II in the cylinder on top of the glass wool, and fill
the remaining space in the cylinder with glass wool. Assemble
-------
Section No. 3.13.4
Date July 1, 1986
Page 6
Final wt
Initial wt
Net wt
1st bubbler
_g
_g
_g
%>.Z
O.?>
Total moisture
2nd impinger
66. 2.
2.. 6
re 3-
g
g
3
3rd. impinger 4th bubbler
^^o» T* or / f • ^& o
81* g
0- S^ g
g /o
97.1 g
a£T g
% spent
Ascarite column:
Final wt
Initial wt
Net wt
30* 7 g
g
3oo. i
30
g of C02
% spent
Recovered Sample
H2°2
container no.
Liquid level
marked
Impinger contents ,
container no. Ar~~l
Liquid level
marked
H20 blank
container no.
Liquid level
marked
Samples stored and locked
Remarks
Received by
Remarks
Date
Figure 4.3. Method 6A sample recovery and integrity data form,
-------
Section No. 3.13.4
Date July 1, 1986
Page 7
the cylinder as shown in Figure 4.4. With the cylinder in a hor-
izontal position, rotate it around the horizontal axis. The CO.-
absorbing material should remain in position during the rotation,
and no open spaces or channels should be formed. If necessary,
pack more glass wool into the cylinder to make the C02 ab-
sorbing material stable. Clean the outside of the cylinder of
loose dirt and moisture, and weigh at room temperature to the
nearest 0.1 g. Record this initial mass on the data form (Figure
4.2). If Method 6B is to be operated in a low sample flow
condition (less than 100 ml/min), molecular sieve material may be
substituted for Ascarite II as the C02 absorbing material;
however, 250 g of sieve material should be used and it must have
been regenerated prior to use. The recommended molecular sieve
material is Union Carbide 1/16 inch pellets, 5&, or equivalent.
Molecular sieve material need not be discarded following the
sampling run provided it is regenerated. Use of molecular sieve
material at flow rates higher than 100 ml/min may cause erroneous
C02 results. It is recommended that a second, smaller CO-
absorber containing Ascarite II be added in line downstream of
the primary CO2 absorber as a breakthrough indicator. Ascarite
II turns whire when CO- is absorbed. The CO- absorber may be
pre-packed, however molecular sieve must be weighed the day of
testing.
4.3.2 Assembling the Sampling Train - After assembling the
sampling train as shown in Figure 1.1, perform the following:
1. Ensure that the C02 absorber is mounted in a vertical
position with the entrance at the bottom to prevent channeling of
gases.
2. Adjust probe heater to operating temperature. Place
crushed ice and water around the impingers and bubblers.
3. Leak check the sampling train just prior to use at the
sampling site (not mandatory) by temporarily attaching a rota-
meter (capacity of 0 to 40 ml/min) to the outlet of the dry gas
meter and placing a vacuum gauge at or near the probe inlet.
Plug the probe inlet, pull a vacuum of at least 250 mm (10 in.)
Hg, and note the flow rate indicated by the rotameter. A leakage
rate <2 percent of the average sampling rate is acceptable. The
Method 6B constant rate low flow sampling train (20 to 40 ml/min)
will be checked by placing a U-tube water manometer at or near
the probe inlet. A vacuum, of at least 20 in. H20 should be
pulled; the sample valve should be shut and then the pump should
be turned off. The system must not lose more than 0.25 in.
vacuum in 2 minutes. Note: Carefully release the probe inlet
plug before turning off the pump. Observe the impingers during
the leak check to ensure that none of the solution is transferred
to another impinger and that the glass wool (if applicable) is
not wetted. If this occurs, the impinger section of the train
-------
Section No. 3.13.4
Date July 1, 1986
Page 8
SAMPLE
GAS
.RUBBER STOPPER
-GLASS WOOL
ASCARITE
GLASS WOOL
RUBBER
STOPPER
OUTLET
Figure 4.4. (X>2 absorber.
-------
Section No. 3.13.4
Date July 1, 1986
Page 9
must be prepared again. It is suggested (but not mandatory) that
the pump be leak checked separately, either prior to or after the
sampling run. If prior to the run, the pump leak check shall
follow the train leak check. To leak check the pump, proceed as
follows. Place a vacuum gauge at the inlet to the pump. Pull a
vacuum of 250 mm (10 in.) Hg. Plug or pinch off the outlet of
the flow meter, and then turn off the pump. The vacuum should
remain stable for at least 30 seconds.
4. Place a loosely packed filter of glass wool in the end
of the probe, and connect the probe to the bubbler. Alternately,
if the out-of-stack filter is used, it should be packed prior to
attaching the probe filter assembly to the bubbler.
5. Other sampling equipment, such as Mae West bubblers and
rigid cylinders for moisture absorption, which requires sample or
reagent volumes other than those specified in this procedure for
full effectiveness, may be used subject to the approval of the
Administrator. An example of an alternative sampling train used
successfully in the collaborative testing program is shown in
Figure 4.5.
4.3.3 Sampling - For Method 6A, the sampling shall be conducted
at a constant rate of approximately 1.0 L/min. For Method 6B,
the sampling shall be conducted either (1) intermittently with at
least 12 equal flows (approximately 1.0 L/min), evenly spaced
sampling collections of between 2 to 4 minutes over a 24-hour
period, or (2) continuously at a rate of between 20 to 40 ml/min
for the 24-hour period. The intermittent Method 6B sampling
method is the recommended system for Method 6B testing because it
uses Method 6 sampling components. The detailed procedures for
each method are described below.
Note: For applications downstream of wet scrubbers, a
heated out-of-stack filter (either borosilicate glass wool or
glass fiber mat) is necessary. The filter may be a separate
heated unit or may be within the heated portion of the probe. If
the filter is within the sampling probe, the filter should not be
within 15 cm of the probe inlet or any unheated section of the
probe, such as the connection to the first S02 absorber. The
probe and filter should be heated to at least 20 C above the
source temperature, but not greater than 120 C. The filter
temperature (i.e., the sample gas temperature) should be moni-
tored to assure the desired temperature is maintained. A heated
Teflon connector may be used to connect the filter holder or
probe to the first impinger.
Constant Rate Sampling for Method 6A - Sampling is performed
at a constant rate of approximately 1.0 L/min as indicated by the
rotameter during the entire sampling run. The procedure is as
follows:
-------
HEATED
GLASS WOOL
FILTER
c=\ HI
m-M \
HEATED PROBE f{f j
— -\ i i
J ^
§t ^
1 A 1
i1 i
M
li I
]f — M
n nil
r M
i1
X
? ^
R "
1 II
'!
J J
C
MAE WEST IMPINGERS
D
J 1
J
->
*_
E
_J
DRIERITE
COLUMN
Method 6A* THERMOMETI
A - 15 ml of Isopropanol ;
B - 15 ml of 3% H?02 ' fj
C - 15 ml of 150 g of Drierite
E - approx 250 g of Ascarite
I
^
W
-A r^
_1
/ LJKY \
( GAS I
Method 6B \ METER J
A - Efipty V
B - 15 ml of >6% H202
C - 15 ml of >6% H202
D - approx 150 g of Drierite
E - approx 150 g of Ascarite
s \
L
RATE
METER
•J-IXI J
^-—
Jot
T
ABSORBER
NEEDLE VALVE
— i
<=
^
F
( o V
\
r'
>^-
V
*/
<*
\
(
Ni
°r
=O^
^^~*r
±__
1 /^Os
1 i* ^
^—^ ' PUMP | *f $
SURGE
TANK
i :
(optional)
1
TIMER
* This Method 6A train was
not used during collaborative
testing.
•now
0) 0) (D
(Q ft O
0>
-------
Section No. 3.13.4
Date July 1, 1986
Page 11
1. Place crushed ice and water around the impingers.
2. Record the initial dry gas meter readings, barometer
reading, and other data as indicated in Figure 4.1. Double check
the dry gas meter reading and check the midget bubbler to be sure
that no hydrogen peroxide has been allowed to siphon back and wet
the glass wool.
3. Position the tip of the probe at the sampling point,
connect the probe to the bubbler, and start the pump. Warning;
If the stack is under a negative pressure of >50 mm (2 in.) H_0
vacuum, the probe should be positioned at the sampling point, tne
sample pump started prior to probe connection, and then the probe
immediately connected to the impinger to prevent the impinger
solutions from being siphoned backwards and contaminating the
isopropanol and glass wool. Alternatively, the first impinger
stem may be broken off and/or a check valve placed in the system.
4. Adjust the sample flow to a constant rate of approxi-
mately 1.0 L/min as indicated by the rotameter.
5. Maintain this constant rate within 10 percent during
the entire sampling run, and take readings (dry gas meter; rate
meter; and temperatures at the dry gas meter and the CO.- absorber
outlet) at least every 5 minutes. Add more ice during the run to
keep the temperature of the gases leaving the last impinger at 20
°C (68°F) or less. Salt may be added to the ice bath to further
reduce the temperature.
6. Refer to emission standards for minimum sampling time
and/or volume. (For example, the Federal standard for fossil
fuel-fired steam generators specifies a minimum sampling time of
20 minutes and a minimum sampling volume of 20 liters corrected
to standard conditions.) The total sample volume at meter condi-
tions should be approximately 28 liters (1 ft ). Make a quick
calculation near the end of the run to guarantee that sufficient
sample volume has been drawn; if the volume is insufficient,
sample for an additional 5 minutes.
7. Turn off the pump at the conclusion of each run, remove
probe from the stack, and record the final readings. Warning;
Again, if the stack is under a negative pressure, disconnect the
probe first, and turn off the pump immediately thereafter or have
the first impinger modified and a check valve added.
8. Conduct a leak check, as described in Subsection 4.3.2
(mandatory).
9. If the train passes the leak check, drain the ice bath
and purge the remainder of the train by drawing clean ambient air
through the system for 15 minutes at the sampling rate. To
-------
Section No. 3.13.4
Date July 1, 1986
Page 12
provide clean ambient air, pass air through a charcoal filter
or through an extra midget impinger containing 15 ml of 3 per-
cent H202- The tester may opt to use ambient air without
purification or to use only a filter. Note; It is important to
drain or remove the ice and water to allow the isopropanol to
warm.
10. If the train fails the leak check, either void the run
or use an alternative procedure acceptable to the Administrator
to adjust the sample volume for leakage. An alternative proce-
dure that may be acceptable to the Administrator is described at
the end of this subsection.
11. Calculate the sampling rate during the purging of the
sample. The sample volume ( V ) for each point should be within
10 percent of the average sample volume for all points. If the
average of all points is within the specified limit, the sample
rate is acceptable. Noncompliance with the +^10 percent of
constant rate for a single sample should not have a significant
effect on the final results of the test for noncyclic processes.
However, the Administrator should be consulted as to the accept-
ability of the sample collection run results.
12. Change the particulate filter (glass-wool plug) at the
end of each test since particulate buildup on the probe filter
may result in a loss of S0? due to reactions with particulate
matter.
Intermittent Sampling for Method 6B - Sampling is performed
at a rate of approximately 1.0 L/min as indicated by the rota-
meter. It is conducted for 12 equally spaced intervals; the
sample collection periods are 2 to 4 minutes in length. The
Method 6B sample train has the same sample train components as
the Method 6A sample train with the exception of an addition of
an industrial timer switch, designed to operate in the "on"
position from 2 to 4 minutes on a 2-hour repeating cycle or other
cycle specified in the applicable regulation. At a minimum, the
sample operation should include at least 12 equal, evenly spaced
periods of sampling per 24 hours and, for the amount of sampling
reagents prescribed in this Method, the total sample volume
collected should be between 25 and 60 liters. The sample
procedure is as follows:
1. Add cold water to the container holding the impingers
until the impingers and bubblers are covered on at least two-
thirds of their length. The impingers, bubbler, and their con-
tainer must be covered and protected from intense heat and direct
sunlight. If freezing conditions exist, the impinger solution
and the water bath must be protected.
-------
Section No. 3.13.4
Date July 1, 1986
Page 13
2. Record the initial dry gas meter readings, probe/filter
temperatures, and other data as indicated in Figure 4.2. Double
check the dry gas meter reading and ensure the impinger and
bubbler container has the proper amount of cold water and is pro-
tected from extreme heat or cold.
3. Position the tip of the probe at the sampling point,
connect the probe to the bubbler, and turn on the time and start
the pump. Warning: If the stack is under a negative pressure of
>50 mm (2 in.) H20, the probe should be positioned at the
sampling point, tne sample pump turned on, and then the probe
immediately connected to the impinger to prevent the impinger
solutions from being siphoned backwards and contaminating the
system. The first impinger must be modified by breaking off the
stem and adding a check valve.
4. Adjust the sample flow to a constant rate of approx-
imately 1.0 L/min as indicated by the rotameter.
5. Observe the sample train operations until the con-
clusion of the first 2- to 4-minute sample collection period.
Determine the volume of sample collected and make a quick
calculation to ensure that the volume from the given number of
equal, evenly spaced sample collection periods will be within the
specified sample volume (i.e., 25 to 60 liters).
6. During the 24-hour sampling period, record the dry gas
meter temperature and barometric pressure one time between
9:00 a.m. and 11:00 a.m.
7. At the conclusion of the 24-hour period, turn off the
timer and the sample pump, remove the probe from the stack, and
record the final gas meter volume reading, the probe/filter
temperature and rotameter setting.
8. Conduct a leak check as described in Subsection 4.3.2.
If a leak is found, void the test run or use procedures accept-
able to the Administrator to adjust the sample volume for leak-
age. An alternative procedure that may be acceptable to the
Administrator is included at the end of this Subsection.
9. Check the final probe temperature, filter temperature,
and total sample volume to ensure that all systems are still
working properly.
10. For scrubbed units change the filter material prior to
the next sample run to ensure that the collected materials do not
scrub the SO2. For unscrubbed units change the filter weekly.
11. To conduct the next sample run repeat all the above
steps.
-------
Section No. 3.13.4
Date July 1, 1986
Page 14
Note: Method 6B does not require a purge at the completion
of the sample run since the train does not include isopropanol.
Constant Rate Sampling for Method 6B - Sampling is performed
at a constant rate of between 20 to 40 ml/min as indicated by the
rotameter during the entire sampling run. Lower flow rates and
longer sampling intervals have been more successful for some
applications. The procedure is as follows:
1. Add cold water to the container holding the impingers
until the impingers and bubblers are covered on at least two-
thirds of their length. The impingers and bubbler, and their
container, must be covered and protected from intense heat and
direct sunlight. If freezing conditions exist, the impinger
solution and the water bath must be protected.
2. Record the initial dry gas meter readings, probe/filter
temperature, and other data as indicated in Figure 4.2. Double
check the dry gas meter reading and ensure the impinger and
bubbler container has the proper amount of cold water and is
protected from extreme heat or cold.
3. Position the tip of the probe at the sampling point,
connect the probe to the bubbler, and start the pump. Warning;
If the stack is under a negative pressure of >50 mm (2 in.) H20,
the probe should be positioned at the sampling point, the sample
pump turned on, and then the probe immediately connected to the
impinger to prevent the impinger solutions from being siphoned
backwards and contaminating the system. The system may be
modified as mentioned above.
4. Adjust the sample flow to a constant rate of between 20
and 40 ml/min as indicated by the rotameter. Maintain this con-
stant rate during the entire test.
5. During the 24-hour sampling period, record the dry gas
meter temperature and the barometric pressure one time between
9:00 a.m. and 11:00 a.m.
6. At the conclusion of the 24-hour period, record the
rotameter setting, turn off the pump, remove the probe from the
stack and record the final gas meter volume reading and the
probe/filter temperatures. Warning: Again, if the stack is
under a negative pressure, disconnect the probe first, and turn
off the pump immediately thereafter.
7. Conduct a leak check in the following manner. Attach a
U-tube water manometer to the inlet to the probe. Turn on the
pump and pull a vacuum of 20 in. H2O. After the vacuum has
stabilized, shut off the main sample valve and then the pump.
The leakage rate must be less than 0.25 in. over a 2-minute
-------
Section No. 3.13.4
Date July 1, 1986
Page 15
period. If the leakage rate is in excess of 0.25 in. H_0, void
the test run or use procedures acceptable to the Administrator to
adjust the sample volume. An alternative procedure that may be
acceptable to the Administrator is included at the end of this
Subsection.
8. Check the final probe temperature, filter temperature
and total sample volume to ensure that all systems were func-
tioning properly.
9. For scrubbed units change the filter material prior to
the next sample run to ensure that the collected material does
not scrub the S02« For nonscrubbed units change the filter
weekly.
10. To conduct the next sample run repeat all the above
steps.
Note; Method 6B does not require a sample purge at the
completion of the sample run since the train does not include
isopropanol.
Alternative Leak Check Procedure for Unacceptable Leak Rates-
The leak check procedure for Method 6A and intermittent Method 6B
require that a vacuum gauge be placed at the probe inlet, a 10
in. Hg vacuum be pulled on the system (as read on the vacuum
gauge), and that the leak rate be checked with a more sensitive
rotameter (0 - 40 ml/min). This system provides a quick indica-
tion when the leak rate is over 4 percent (the rotameter ball
will be pegged). It provides the actual value when the leak rate
is under 4 percent. Thus, these procedures and equipment as
specified do not quantify the leakage rate greater than 4
percent.
In an effort to retain and make useful the maximum amount of
emissions data possible, the following alternative may be accept-
able to the Administrator when an unacceptable leak rate is de-
tected for the Method 6A and intermittent Method 6B trains. This
alternative procedure should be approved by the Administrator
prior to its use.
When an unacceptable post test leak check is detected the
following procedure may be used to compensate for the leak rate
(for Method 6A and intermittent Method 6B). This procedure
assumes that the leak occurred for the duration of the test run
and may bias the results high.
1. After the sample train leakage rate is found to be un-
acceptable at 10 in. Hg, release the vacuum in the proper manner
and shut-off the sampling train.
-------
Section No. 3.13.4
Date July 1, 1986
Page 16
2. If the emissions results are to be calculated in terms of
ppm S02 or Ib S02/million Btu without using the results of C02
collected by the sampling train, the vacuum gauge must be left on
the inlet to the probe. However, if the emissions results are to
be calculated in terms of Ib SO2 per million Btu using the grams
of C02 collected in the sampling train, the vacuum gauge may be
places on the inlet to the first impinger of H202. Alter-
natively, the gauge may be left at the probe inlet; nowever, the
leakage correction may then compensate for leakage rates that do
not affect the results in terms of Ib S02/million Btu.
3. Turn on the pump, and pull a vacuum of 2 in. Hg as shown
by the vacuum gauge.
4. After the vacuum stablizes determine the leak rate by
measuring the volume on the dry gas meter for at least 2 minutes.
5. The leak rate will be used to compensate only for the
mass of S02 in comparison to the C02 as shown in the equation
below.
Equation 4-1
M Sampling Rate
S02(corrected) " (S02) sampling Rate - Leak Rate
where
M-.,. , . ,v = mass of SO~ corrected to compensate
S02(corrected) for leakagj rate;
MSQ = mass of S02 determined for sample
2 analysis;
Sampling Rate = Sample volume divided by the sample time
(continuous sample methods), for the
intermittent method use 1.0 L/min; and
Leak Rate = leak rate determined by this alternative
procedure (metered leak volume divided by
the time checked).
When an unacceptable posttest leak check is detected for the
constant rate Method 6B train, the following procedure may be
used to compensate for the leak rate:
1. After the sampling train leakage rate is found to be
unacceptable at 10 in. of H20, release the vacuum in the proper
manner and shut off the sampling train.
-------
Section No. 3.13.4
Date July 1, 1986
Page 17
2. If the emission results are to be calculated in terms of
ppm S07 or Ib S0~/million Btu without using the results of C02
collected by the sampling train, the U-tube manometer must be
left on the inlet to the probe. However, if the emission results
are to be calculated in terms of Ib 50,,/million Btu using the
grams of C07 collected in the sampling train, the U-tube mano-
meter may be placed on the inlet to the first impinger of H202.
Alternatively, the manometer may be left at the probe inlet;
however, the leakage correction may then compensate for leakage
rates that do not affect the results in terms of Ib S02/million
Btu.
3. Attach a 10-ml graduated pipette with a "T" and a bulb
with soap solution to the outlet of the dry gas meter.
4. Turn on the pump and pull a vacuum of 20 in. of H20 as
shown by the manometer.
5. After the vacuum stabilizes, start a bubble up the
pipette.
6. Time the movement of the bubble over at least 1.0 ml of
the pipette with a stop watch. Use the integer markings of the
pipette.
7. The leakage rate will be determined by dividing the
volume by the time.
8. Use Equation 4-1 to determine the correction for the
determined leakage rate.
4.4 Sample Recovery
The Reference Method requires the weighing and transfer of the
impinger contents and the connector washings to a polyethy- lene
storage container. This weighing and transfer should be done in
the "laboratory" area to prevent contamination of the test
sample.
After completing the leak check (for Method 6B) or the purge
(for Method 6A), disconnect the impingers and transport them to
the cleanup area. The contents of the midget bubbler (contains
isopropanol for Method 6A only) may be discarded after the weight
is determined. However, it is usually advisable to retain this
fraction until analysis is performed on the H2
-------
Section No. 3.13.4
Date July 1, 1986
Page 18
1. Allow the impingers and C02 absorber to come to room
temperature (- 20 C), which should take approximately 10 minutes.
2. If the balance has not been calibrated or has been
moved within the past 24 hours, calibrate it as described in
Subsection 4.3.1 prior to the weighing of the samples.
3. Wipe the outside of the bubblers, impingers, and C0?
absorber.
4. Weigh the bubblers, the impingers, and CO- absorber
separately, and record their weights to the nearest 0.1 g on the
proper data sheet (Figure 4.3 for Method 6A and Figure 4.2 for
Method 6B).
5. Method 6A - Transfer the contents of the two impingers
containing solution to a labeled, leak-free, polyethylene sample
bottle. Wash the impingers and connection glassware with three
15 ml portions of water. Place the rinsings in the sample
bottle. The contents of the midget bubbler may be discarded or
saved for analysis if problems are detected in the subsequent
analysis of SO^.
Method 6B - Recover the sample contents from the midget
bubbler and the two midget impingers containing solution. Rinse
the bubbler, impingers, and connecting glassware with three 15 ml
portions of water. The impinger contents and rinsings should be
transferred to a labeled, leak-free polyethylene sample bottle.
Note: The total rinse and sample volume should be less than
100 ml; a 100-ml mark can be placed on the outside of the poly-
ethylene sample bottle as a guide. Alternatively, if the sample
recovery is conducted in the laboratory, the sample recovery may
be conducted directly into a 100 ml volumetric flask.
Warning; It has been demonstrated that the contamination of
the sample with Ascarite or Drierite will bias the results.
6. Place 100 ml of the absorbing reagent in a polyethylene
bottle, and label it for use as a blank during sample analysis.
An example sample label is shown in Figure 4.6.
7. Mark the liquid level on the outside of all sample
bottles, and ensure that the caps are on tightly providing a
leak-free container.
8. Discard the Ascarite and Drierite material.
4.5 Sample Logistics (Data) and Packing Equipment - The sampling
and sample recovery procedures are followed until the required
-------
Section No. 3.13.4
Date July 1, 1986
Page 19
Plant /4f>^ City fin (( u) *&*"£•
S±te /Qoiltr A
Date JO
Front rinse
Back rinse
Solution -^
I0. 3 Ou+trh
i
Sample Type 50^.^ c£>2__
-/0-~&S~ Run Number A(?-l
_
Front filter
Back filter
-/GO**,
Volume: Initial 3£>
Cleanup by
Aji^
Front solution
Back solution
Level marked
X
'
Final
/
•fi
to
0)
Figure 4.6. Example of a sample label.
number of runs are completed. Log all data on the Sample and
Sample Recovery Data Form, Figure 4.3 (Method 6A) and Figure 4.2
(Method 6B). If the bubbler, impingers, and connectors are to be
used in the next test, they should be rinsed with distilled
water, and the bubbler should be rerinsed with isopropanol (for
Method 6A only). A new or recharged C02 absorber column should
be inserted into the sampling train. At the completion of the
test:
1. Check all sample containers for proper labeling (time,
date, location, number of test, and any pertinent documenta-
tion). Be sure that a blank has been taken.
2. If data is to be removed from the source area, record
all data collected during the field test in duplicate by using
data forms and a field laboratory notebook. One set of data
should be mailed to the base laboratory, and one given to another
team member or to the Agency. Hand carrying the other set (not
mandatory) can prevent a very costly and embarrassing mistake.
3. Examine all sample containers and sampling equipment
for damage, and pack them for shipment to the base laboratory,
being careful to label all shipping containers to prevent loss of
samples or equipment.
4. Make a check of the sampling and sample recovery
procedures using the data form, Figure 4.7 (Method 6A) or Figure
4.8 (Method 6B).
-------
Section No. 3.13.4
Date July 1, 1986
Page 20
Sampling
Bubbler and impinger contents properly selected, measured, and
placed in proper receptacle?* _ r _
Impinger Contents/Parameters
1st: 15 ml of 80 percent isopropanol _ X _
2nd: 15 ml of 3 percent ^2°2* _ — _
3rd: 15 ml of 3 percent H2
-------
Section No. 3.13.4
Date July 1, 1986
Page 21
Sampling
Impinger contents properly selected, measured, and placed in
impingers? _ ^
Impinger Contents/Parameters
1st: Empty* _ S
2nd: 15 ml of >6 percent ^2°2* _ ^
3rd: 15 ml of >6 percent ^2°2*
4th: Approx. 25 g of Drierite*
Approx. 150 g of Ascarite II or 250 g 5A molecular sieve
(continuous flow rate train only) in CO2 absorber?*
Probe heat at proper level?
Crushed ice around impingers? _
Pretest leak check at 250 mm (10 in.) Hg? _ s
Leakage rate? ___ _ Q.O
Probe placed at proper sampling point? _ i
Flow rate intermittent at approximately 1.0 L/min?* ^
Flow rate constant between 20 to 40 ml/min? /V^/f
Posttest leak check at 250 mm (10 in.) Hg?*
Leakage rate? Q.&
Sample Recovery
Balance calibrated with Class S weights?*
Impingers cleaned and weighed to +0.1 g at room temp?
Contents of impingers and rinsings placed in polyethylene
bottles?
Fluid level marked?*
C02 absorber cleaned and weighed to +0.1 g at room temp?* ^
Sample containers sealed and identified?*
-------
Section No. 3.13.4
Date July 1, 1986
Page 22
Table 4.1. ACTIVITY MATRIX FOR ON-SITE MEASUREMENT CHECKS
Operation
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Preparation and/
or addition
of absorbing
reagents
Method 6A. Add 15 ml
80% isopropanol to
first midget bubbler,
15 ml of 3% H202
to two midget impin-
gers, approx 25 g of
Drierite to the last
bubbler, and 150 g of
Ascarite to column
Method 6B. Leave first
bubbler empty, add 15
to
impin-
Prepare 3% H_0_ fresh
daily; use pipette or
graduated cylinder to
add solutions
Reassemble
collection
system
ml of >6% H20,
the two midget
Prepare >6% H^
fresh daily; use pipette
or graduated cylinder to
add solutions
Reassemble
collection
system
gers, approximately
25 g of Drierite to the
last midget bubbler, and
150 g of Ascarite to
column
Assembling the
sampling train
1. Assemble to speci-
fications in Fig. 1.1
2. A leakage rate <2%
of the average samp-
ling rate
1. Before each sampling
2. Leak check before
sampling (recommended)
by attaching a rotameter
to dry gas meter outlet,
placing a vacuum gauge at
or near probe inlet, and
pulling a vacuum of
mm (10 in.) Hg
1. Reassemble
2. Correct
the leak
Sampling
(Method 6A
constant rate)
1. Method 6A
Within 10% of a
constant rate
1. Calculate %. deviation
for each sample using
equation in Fig. 4.1
1. Repeat
the sam-
pling, or
obtain ac-
ceptance
from a rep-
resentative
of the Admin-
istrator
(continued)
-------
Table 4.1. (continued)
Section No. 3.13.4
Date July 1, 1986
Page 23
Operation
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
2. Minimum accept-
able time is 20 min
and volume is 20
liters corrected to
STP or as specified
by regulation
3. Less than 2% leak-
age rate at 250 mm
(10 in.) Hg
4. Purge remaining
S0_ from isopropanol
2. Make a quick cal-
culation prior to com-
pletion and an exact
calculation after com-
pletion
3. Leak check after
sample run (mandatory);
use same procedure as
above
4. Drain ice, and purge
15 min with clean air
at the sample rate
2. As above
3- As above
4. As above
Sampling
(Method 6B
intermittent)
1. At least 12
equally and evenly
spaced intermittent
sample intervals at
about 1.0 L/min
2. Sample time is
24 hours and the
acceptable sample vol-
ume is between 25
and 60 liters
3. Less than 2% leak-
age rate at 250 mm
(10 in.) Hg
1. Check the volume of
the first sample inter-
val and the total vol-
ume should be within
IQ% of first sample
volume times the number
of intervals
2. Make a calculation
after each sample run
3. Leak check after
sample run (mandatory)
1. Repair or
recalibrate time
and/or rotameter
and repeat the
sampling or ob-
tain acceptance
from a represen-
tative of the
Administrator
2. As above
3- Void the
test, or use an
alternative
procedure
acceptable to
a represen-
tative of the
Administrator
(continued)
-------
Table 4.1 (continued)
Section No. 3.13-4
Date July 1, 1986
Page 24
Operation
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Sampling
(Method 6B
rate constant)
1. Sample at a con-
stant rate of between
20 and 40 ml/min
1. Calculate sample
rate at the completion
of run
2. Sample time is 24
hours and the accept-
able sample volume
is between 25 and 60
liters
3. Less than 2% leak-
age at 500 mm (20 in.)
H20
2. Calculate sample
volume at end of sample
run
3. Leak check after
sample run (mandatory)
1. Repair or
recalibrate
rotameter, and
repeat run or
obtain accept-
ance from a
representative
of the
Administrator
2. As above
3. Void the
test, or use an
alternative
procedure
acceptable to
a represen-
tative of the
Administrator
Sample Recovery
1. Balance accurate
to within 0.1 g
2. Determine mois-
ture collected in
impingers
1. Calibrate with
Class S weights
2. Wipe the outside
of the impingers and
bubblers clean, and
weigh each to the
nearest 0.1 g
1. Adjust, re-
pair, or
reject
2. Repeat run,
or use alter-
native mois-
ture determi-
nation technique
(continued)
-------
Table 4.1. (continued)
Section No. 3-13-4
Date July 1, 1986
Page 25
Operation
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
3. Recover SO,
sample
4. Determine CO,
absorber weight
3. Place contents of
the two midget
impingers and the rins-
ings in a marked poly-
ethylene bottle
(Method 6A); place con-
tents of the two midget
impingers, the first
midget bubbler, and the
rinsings in a marked
polyethylene bottle
(Method 6B)
4. Wipe clean the out-
side of the C0_ absor-
ber, and weigh to the
nearest 0.1 g
3- Repeat run,
or place con-
tents and rins-
ings directly
into the vol-
umetric flask
4. Repeat run,
or weigh ab-
sorber again
Sample logis-
tics (data)
and packing
1. All data are re-
corded correctly
2. All equipment ex-
amined for damage and
labeled for shipment
3- All sample con-
tainers properly
labeled and packaged
1. Visually check upon
completion of each run
and before packing
2. As above
3. Visually check upon
completion of test
1. Complete
the data
form
2. Redo test
if damage
occurred during
testing
3. Correct
when possible
-------
Section No. 3.13.5
Date July 1, 1986
Page 1
5.0 POSTSAMPLING OPERATIONS
Table 5.1 at the end of this section summarizes the quality
assurance activities for postsampling operations.
5.1 Apparatus Check
A posttest check—including a calibration check, the clean-
ing, and/or the performance of routine maintenance—should be
made on most of the sampling apparatus. Cleaning and mainte-
nance of the sampling apparatus are discussed in Section 3.13.7.
Figure 5.1 should be used to record the posttest checks.
5.1.1 Metering System - The metering system has three components
that must be checked: dry gas meter thermometer(s), dry gas
meter, and rotameter.
The dry gas meter thermometer should be checked by comparison
with the ASTM mercury-in-glass thermometer at room temperature.
If the readings agree within 6 C (10.8 F), they are accept-
able. When the readings are outside this limit, the thermometer
must be recalibrated according to Section 3.13.2 after the post-
test check of the dry gas meter. For calculations, the dry gas
meter thermometer reading (field or recalibration) that would
give the higher temperature is used. That is, if the field
reading is higher, no correction of the data is necessary; if the
recalibration value is higher, the difference in the two readings
is added to the average dry gas meter temperature reading.
The posttest checks of the dry gas meter and rotameter are
similar to the initial calibration, as described in Section
3.13.2, but they include the following exceptions:
1. The metering system should not have had any leaks
corrected prior to the posttest check.
2. Three or more revolutions of the dry gas meter are
sufficient.
3. Only two independent runs need be made. If the post-
test dry gas meter calibration factor (Y) does not deviate by >5
percent from the initial calibration factor, the dry gas meter
volumes obtained during the test series are acceptable. If it
deviates by >5 percent, recalibrate the metering system as in
Section 3.13.2 using the calibration factor (initial and
recalibration) that yields the lower gas volume for each test
run. The lesser calibration factor will give the lower gas
volume.
The rotameter calibration factor (Y ) can also be determined
during the calibration of the dry gas meter. If Y does not
-------
Section No. 3.13.5
Date July 1, 1986
Page 2
Meter Box Number
Dry Gas Meter (If applicable)
Pretest calibration factor (Y) = ,
Posttest check (Y) = /.g>33 (+5 percent of pretest
factor)* s
Recalibration required? yes * no
If yes, recalibration factor (Y) = (within 2 percent of
calibration factor for each calibration run)
Lower calibration factor Y (pretest or posttest) =
for calculations
Rotameter
Pretest calibration factor (Y ) = /•'
Posttest check (Y ) = /,/ (within 10 percent of pretest
factor)
Recalibration recommended? yes / no
If performed, recalibration factor (Y ) =
Was rotameter cleaned? yes no
Dry Gas Meter Thermometer (If applicable)
Was a pretest meter temperature correction used? yes ^ no
If yes, temperature correction
Posttest recalibration required? yes / no (recalibrated
when Y_ recalibrated)
LI
Barometer
Was pretest field barometer reading correct? * yes no
Posttest recalibration required? yes ^r\o (recalibrated
when Y_ recalibrated)
LI
Balance*
Was the balance calibration acceptable? iXyes no
(+_ 0.05 g checked against Class S weights)
If no, the balance should be repaired or replaced prior to
weighing field samples.
* Most significant items/parameters to be checked.
Figure 5.1. Posttest sampling checks.
-------
Section No. 3.13.5
Date July 1, 1986
Page 3
deviate by >10 percent from the initial calibration factor, the
rotameter operation is acceptable. If Y changes by >10 percent,
the rotameter should be cleaned and recalibrated. No corrections
need be made for any calculations.
5.1.2 Barometer - The field barometer readings are acceptable if
they agree within 5 mm (0.2 in.) Hg when compared with those of
the mercury-in-glass barometer. When the comparison is not
within this range, the lesser calibration value should be used
for the calculations. If the field barometer reads lower than
the mercury-in-glass barometer, the field data are acceptable;
but if the mercury-in-glass barometer gives the lower reading,
the barometric value adjusted for the difference in the two
readings should be used in the calculation.
5.1.3 Balance - The balance should have been calibrated as
described in Subsection 4.3.1.
5.2 Analysis (Laboratory)
The purpose of Method 6B is to provide an average daily
emission rate for each 24-hour sample. These emission rates are
used for decision making and determining rolling average
compliance status. As a result, the values must be determined in
a timely manner. It is therefore assumed that the Method 6B
analyses are performed either on-site or within a reasonably
short distance from the site. Both the analytical equipment and
techniques lend themselves, when performed in a clean area by
skilled technicians, to providing the necessary accuracy. A base
laboratory is not required.
Calibrations and standardizations are of the utmost impor-
tance to a precise and accurate analysis. The analysis is based
on the insolubility of barium sulfate (BaSO.) and on the for-
mation of the colored complex between excess barium ions and the
thorin indicator, l-(o-arsonophenylazo)-2-naphthol-3, 6-disul-
fonic acid, disodium salt. Aliquots from the impinger solution
are analyzed by titration with barium perchlorate to the pink
endpoint. The barium ions react preferentially with sulfate ions
in solution to form a highly insoluble barium sulfate
precipitate. When the barium has reacted with all of the sulfate
ions, the excess barium then reacts with the thorin indicator to
form a metallic salt of the indicator and to give a color change
as shown in Equation 5-1.
Ba + SO." + thorin(x ) -> BaSO. + thorin(Ba ) Equation 5-1
(yellow) (pink)
Upon completion of each step of the standardization or of
each sample analysis, the data should be entered on the proper
-------
Section No. 3.13.5
Date July 1, 1986
Page 4
data form. At the conclusion of the sample analysis, the data
form should be reviewed and signed by the laboratory person with
direct responsibility for the sample.
5.2.1 Reagents (Standardization and Analysis) - The following
reagents are required for the analysis of the samples:
Water - Deionized distilled water that conforms to ASTM
specification D1193-74, Type 3 is required. At the option of the
analyst, the KMnO. test for oxidizable organic matter may be
omitted when high concentrations of organic matter are not
expected. Note; The water must meet the ASTM specifications
since sulfate ions and many other anions present in distilled
water are not identified in the normal standardization of the
acid by NaOH titration, which measures the hydrogen ion concen-
tration rather than the sulfate ion concentration. This added
sulfate concentration will result in an erroneous standardization
of the barium perchlorate titration, which directly measures
sulfate ion concentration and not hydrogen ion concentration. A
check on the acceptability of the water is detailed in Subsection
5.13.4.
Isopropanol - 100 percent, ACS reagent grade is needed.
Check for peroxide impurities as described in Section 3.13.1
(Method 6A).
Thorin indicator - Dissolve 0.20 +0.002 g of l-(o-arsono-
phenylazo)-2-naphthol-3,6-disulfonic acid, disodium salt, or the
equivalent, in 100 ml of water. Measure the distilled water in
the 100-ml graduated cylinder (Class A).
Sulfuric acid standard, 0.0100N - Either purchase manufac-
turer-guaranteed or standardize the H2S04 to _+0.002N against
0.0100N NaOH that has been standardized against potassium acid
phthalate (primary standard grade) as described in Subsection
5.13.3. The 0.01N H2S04 may be prepared in the following manner:
a. Prepare 0.5N H2S04 by adding approximately 1500 ml of
water to a 2-liter volumetric flask.
b. Cautiously add 28 ml of concentrated sulfuric acid and
mix.
c. Cool if necessary.
d. Dilute to 2-liters with water.
e. Prepare 0.01N H^SO. by first adding approximately 800 ml
of distilled water to a 1-liter volumetric flask and then
adding 20.0 ml of the 0.5N H2S04.
f. Dilute to 1-liter with water and mix thoroughly.
-------
Section No. 3.13.5
Date July 1, 1986
Page 5
Barium perchlorate solution 0.0100N - Dissolve 1.95 g of
barium perchlorate trihydrate (Ba(C104)2.3H20) in 200 ml of
water, and dilute to 1-liter with isopropanol. Alternatively,
1.22 g of barium chloride dihydrate (BaCl2.2H20) may be used
instead of the perchlorate. Standardize, as in Subsection
5.13.4, with 0.0100N H2S04. Note; Protect the 0.0100N barium
perchlorate solution from evaporation at all times by keeping the
bottle capped between uses.
Note; It is recommended that 0.1N sulfuric acid be pur-
chased. Pipette 10.0 ml of sulfuric acid (0.1N) into a 100-ml
volumetric flask and dilute to volume with water that has been
determined to be acceptable as detailed in Subsection 5.13=4.
When the 0.0100N sulfuric acid is prepared in this manner,
procedures in Subsections 5.13.2. and 5.13.3 may be omitted since
the standardization of barium perchlorate will be validated with
the control sample.
5.2.2 Standardization of Sodium Hydroxide - To standardize NaOH,
proceed as follows:
1. Purchase a 50 percent w/w NaOH solution. Dilute 10 ml
to 1-liter with water. Dilute 52.4 ml of the diluted solution to
1-liter with water.
2. Dry the primary standard grade potassium acid phthalate
for 1 to 2 hours at 110 C (230 F), and cool in desiccator.
3. Weigh to the nearest 0.1 mg, three 40-mg portions of the
phthalate. Dissolve each portion in 100 ml of freshly boiled
water in a 250-ml Erlenmeyer flask.
4. Add two drops of phenolphthalein indicator, and titrate
the phthalate solutions with the NaOH solution. Observe titra-
tions against a white background to facilitate detection of the
pink endpoint. The endpoint is the first faint pink color that
persists for at least 30 seconds.
5. Compare the endpoint colors of the other two titrations
against the first.
6. Titrate a blank of 100 ml of freshly boiled distilled
water using the same technique as in step 4. (The normality is
the average of the three values calculated using the following
equation.)
M = mg KHP Equation 5-2
NaOH (ml Titrant - ml Blank) x (204.23)
-------
Section No. 3.13.5
Date July 1, 1986
Page 6
where
NNaOH = calculated normality of sodium hydroxide,
mg KHP = weight of the phthalate, mg,
ml Titrant = volume of sodium hydroxide titrant, and
ml Blank = volume of sodium hydroxide titrant for blank (ml).
The chemical reaction for this standardization is shown in
Equation 5-3. The sodium hydroxide is added to the potassium
hydrogen phthalate and colorless phenolphthalein solution until
there is an excess of diluted hydroxyl ions which causes the
phenolphthalein solution to change to a pink color.
Equation 5-3
NaOH + KHP + phenolphthalein -> KNaP + HOH + phenolphthalein
(colorless) (pink)
5.2.3 Standardization of Sulfuric Acid - To standardize sulfuric
acid, proceed as follows:
1. Pipette 25 ml of the H2SO4 into each of three 250-ml
Erlenmeyer flasks.
2. Add 25 ml of water to each.
3. Add two drops of phenolphthalein indicator, and titrate
with the standardized NaOH solution to a persistent pink
endpoint, using a white background.
4. Titrate a blank of 25 ml of water, using the same tech-
nique as step 3. The normality will be the average of the three
independent values calculated using the following equation:
(ml NaOHacid - ml NaOHblank) x NNaQH Equation 5.4
HS0 ~ 25
where
Nu c-rt = calculated normality of sulfuric acid,
H2S04
ml NaOH ., = volume of titrant used for H2SO., ml,
ml NaOH. . = volume of titrant used for blank, ml, and
NKT r>u = normality of sodium hydroxide.
NaUn
5.2.4 Standardization of Barium Perchlorate (0.01N) - To
standardize barium perchlorate, proceed as follows:
-------
Section No. 3.13.5
Date July 1, 1986
Page 7
1. Pipette 25 ml of sulfuric acid standard (0.0100N) into
each of three 250-ml Erlenmeyer flasks.
2. Add 100 ml of reagent grade isopropanol and two to four
drops of thorin indicator, and titrate to a pink endpoint using
0.0100 N barium perchlorate. Perform all thorin titrations
against a white background to facilitate the detection of the
pink endpoint color.
3. Prepare a blank by adding 100 ml of isopropanol to 25 ml
of water. If a blank requires >0.5 ml of titrant, the analyst
should determine the source of contamination. If the distilled
water contains high concentrations of sulfate of other polyvalent
anions, then all reagents made with the water will have to be
remade using distilled water that is acceptable.
4. Use the endpoint of the blank or the endpoint of the
first titration as a visual comparator for the succeeding
titrations.
5. Record data on analytical data form, Figure 5.2. The
normality of the barium perchlorate will be the average of the
three independent values calculated using Equation 5-5.
NH9SOA X 25
N 24
Ba(C10.)9 ~ Equation 5-5
(ml Ba(C104)2 - ml Blank)
where
No /r*-m \ = calculated normality of barium perchlorate,
oa\C1U . ) ~
Nu o<-» = normality of standardized sulfuric acid,
H2S04
ml Ba(Cl04)2 = volume of barium perchlorate titrant, ml, and
ml Blank = volume of barium perchlorate titrant for blank, ml.
The chemical reaction for this standardization was shown in
Equation 5-1. The standardized barium perchlorate should be
protected from evaporation of the isopropanol at all times.
Note; It is suggested that the analyst unfamiliar with this
titration carry out titrations on aliquots at low, medium, and
high concentrations in the following manner:
1. Pipette 2.0-, 10.0-, and 20.0-ml aliquots of 0.0100N H2SO4
into three 250-ml Erlenmeyer flasks.
2. Dilute to 25 ml with distilled water.
-------
Plant
fac
1*1
P)»*rt
Sample location Poikr M>. 3
Date
Analyst
Volume and normality of barium perchlorate
Standardization blank 0-0 ml (< 0.5 ml)
Section No. 3.13-5
Date July 1, 1986
Page 8
. £2. ml 0.0101*1 N
Q ml
3 2-fr.SQ ml p. Ql 020 N
Q.QI02. N, avg
Sample
number
1
2
3
4
5
6
Field
Blank
Sample
identification
number
Af>-l
Total
sample
volume
'
ml
100
N/A
Sample
aliquot
volume
(va)a
ml
Z-0
Volume of titrant (V ) , ml
1st
titration
//. 3/
0
2nd
titration
//. Z1
0
Average
II. BO
\*-o
Volume for the blank must be the same as that of the sample aliquot.
b 1st titration
2nd titration
Signature of analyst
= 0.99 to 1.01 or 1st titration - 2nd titration <0.2 ml.
O
Signature of reviewer or supervisor
Figure 5.2. Sulfur dioxide analytical data form.
-------
Section No. 3.13.5
Date July 1, 1986
Page 9
3. Add a 100-ml volume of 100 percent isopropanol and two to
four drops of thorin indicator to each.
4. Titrate with barium perchlorate to become familiar with
the endpoint.
5.2.5 Control Samples - The accuracy and precision of the sample
analysis should be checked. The accuracy of the analytical tech-
nique is determined by control samples. The precision is checked
by duplicate analyses of both the control and the field samples.
Acceptable accuracy and precision should be demonstrated on the
analysis of the control sample prior to the analysis of the field
samples.
The control sample should be prepared and analyzed in the
following manner:
1. Dry the
for 1 to 2 hours
primary standard grade ammonium sulfate ((NHA)9SO.
rs at 110 C (230°F), and cool in a desiccate?.
2. Weigh to the nearest 0.5 mg, 1.3214 g of primary standard
grade ammonium sulfate.
3. Dissolve the reagent in about 1800 ml of.distilled water in
a 2-liter volumetric flask.
4. Dilute to the 2-liter mark with distilled water. The
resulting solution is 0.0100N ammonium sulfate.
5. Enter all data on the form shown in Figure 5.3.
6. Pipette 25 ml of the control sample into each of three
250-ml Erlenmeyer flasks, and pipette a 25-ml blank of distilled
water into a fourth 250-ml Erlenmeyer flask. Note; Each control
sample will contain 16.5 mg of ammonium sulfate.
7. Add 100 ml of reagent grade isopropanol to each flask and
then two to four drops of thorin indicator.
8. Initially, titrate the blank to a faint pink endpoint using
the standardized barium perchlorate. The blank must contain
< 0.5 ml of titrant, or the water is unacceptable for use in this
method.
9. Titrate two of the control samples with the standardized
barium perchlorate to a faint pink endpoint using the blank
endpoint as a guide. The endpoint is the first faint pink
endpoint that persists for at least 30 seconds. All titrations
should be done against a white background.
-------
Section No. 3.13.5
Date July 1, 1986
Page 10
Plant
r
over
Analyst
ttrqu
Date analyzed
NBa(C104)2 —
Weight of ammonium sulfate is 1.3214 g?
Dissolved in 2 L of distilled water?
Titration of blank 0-0 ml Ba(Cl04)2 (must be <0.5 ml)
Control
sample
number
/
Time of
analysis,
24 h
0330
Titrant volume,3 ml
1st
zs.o
2nd
2.G.O
3rd
Avg
zs.o
Two titrant volumes must agree within 0.2 ml.
(ml Ba(C104)2 - ml Blank) x NBa( = 25 ml x 0.01N
(control) (control
sample) sample)
ml - 0-0 ml) x
N =
(must agree within 5%, i.e., 0.238 to 0.262)
Does value agree? ^ yes no
I A
Signature of analyst
Signature of reviewer
Figure 5.3. Control sample analytical data form.
-------
Section No. 3.13.5
Date July 1, 1986
Page 11
10. If the titrant volumes from the first two control samples
agree within 0.2 ml, the average of the two values can be used to
complete the calculations shown in Figure 5.3. If not within 0.2
ml, titrate the third control sample. If the titration volume
agrees within 0.2 ml of either of the first two samples, use the
two titrant volumes that are consistent for the remaining
calculations. If this criterion cannot be met with the first set
of control samples, follow the same procedure on a second set of
two control samples.
11. If the criterion cannot be met for the second set of
control samples, the analyst should have the analytical tech-
niques observed by a person knowledgeable in chemical analysis,
or should have all reagents checked.
12. After consistent titrant volumes are obtained, calculate
the analytical accuracy as shown in Figure 5.3. If the measured
value is within 5 percent of the stated value, the technique and
standard reactions are acceptable, and the field samples may be
analyzed. When the 5 percent accuracy cannot be met, the barium
perchlorate must be restandardized or the control sample must be
checked until the accuracy criterion of the control sample
analysis can be obtained.
13. The recommended frequency for analysis of control
samples is the following:
a. Analyze two control samples each analysis day immediately
prior to analysis of the actual collected source samples.
b. Analyze two control samples after the last collected
source sample is analyzed each analysis day.
14. Enter results from the control sample analyses on Figure
5.3, and submit Figure 5.3 with the source test report as
documentation of the quality of the source test analysis.
5.2.6 Sample Analysis - Check the level of liquid in the con-
tainer to determine whether any sample was lost during shipment,
and note this on the data form, Figure 4.3. Figure 5.4 can be
used to check analytical procedures. If a noticeable amount of
leakage has occurred, follow the alternative method described
below. Approval should have been requested prior to testing in
case of subsequent leakage. The alternative method is as
follows:
1. Mark the new level of the sample.
2. Transfer the sample to a 100-ml volumetric (V ) flask,
and dilute to exactly 100 ml with deionized distilled warer.
-------
Section No. 3.13.5
Date July 1, 1986
Page 12
Reagents
Normality of sulfuric acid standard* £>• 0100 N
Date purchased /&/ /&] &£ Date standardized /£>//£ /£ 5""
f jr f '
Normality of barium perchlorate titrant* Q . ()& *%, / ^ A/
Date standardized
Normality of control sample*
Date prepared _ A? //6 /£>£""
Volume of burette 5b >*-£ Graduations
Sample Preparation
Has liquid level noticeably changed?*
Original volume Corrected volume
Samples diluted to 100 ml?*
Analysis
(Sulfur dioxide)
Volume of aliquot analyzed*
Do replicate titrant volumes agree within 1% or 0.2 ml? uZt,
Number and normality of control samples analyzed 2.$ & IQQfJ
Are replicate control samples within 0.2 ml? h^
Is accuracy of control sample analysis ^5%?*
; the rel
limits?*
^
Is the relative error of audit sample(s) within acceptable
_ _
7
(Moisture and carbon dioxide)
Balance calibrated with Class S weights to within 0.05 g?*
Initial weignt of each impinger to nearest 0.1 g*
Final weight of each impinger to nearest 0.1 g* _ b
Initial weight of CO0 absorber to nearest 0.1 g*
z
Final weight of CO., absorber to nearest 0.1 g*
All data recorded? */ _ Reviewed by
*Most significant items/parameters to be checked.
Figure 5.4. Posttest operations.
-------
Section No. 3.13.6
Date July 1, 1986
Page 1
6.0 CALCULATIONS
Calculation errors due to procedural or mathematical mistakes
can be a part of total system error. Therefore, it is recom-
mended that each set of calculations be repeated or spotchecked,
preferably by a team member other than the one who performed the
original calculations. If a difference greater than typical
round-off error is detected, the calculations should be checked
step-by-step until the source of error is found and corrected. A
computer program is advantageous in reducing calculation errors.
If a standardized computer program is used, the original data
entry should be included in the printout to be checked; if
differences are observed, a new computer run should be made.
Table 6.1 at the end of this section summarizes the quality
assurance activities for calculations.
Calculations should be carried out to at least one extra
decimal figure beyond that of the acquired data and should be
rounded off after final calculation to two significant digits for
each run or sample. All rounding off of numbers should be
performed in accordance with the ASTM 380-76 procedures. All
calculations should then be recorded on a calculation form such
as the ones in Figures 6.2A and 6.2B, at the end of this section.
6.1 Nomenc1ature
The following nomenclature is used in the calculations:
C__ = concentration of CO0, dry basis, percent,
\*\j^ £
Cc_ = concentration of sulfur dioxide, dry basis
ovj^
corrected to standard conditions, mg/dscm (Ib/dscf),
C = concentration of moisture, percent,
w
Eg = emission rate of SO^, lb SCv/million Btu (ng/J),
F = volume of C00 liberated per million Btu of
C • U— Z
N = normality of barium perchlorate titrant, milliequi-
valents/ml,
-------
Section No. 3.13.6
Date July 1, 1986
Page 2
P. = barometeric pressure at the exit orifice of
the dry gas meter, mm Hg (in. Hg),
P 4-j = standard absolute pressure, 760 mm Hg (29.92 in. Hg),
o o
T = average dry gas meter absolute temperature, K ( R),
Tstd = standard absolute temperature, 293°K (528°R),
V = volume of sample aliquot titrated, ml,
O
VCO (std)= standard equivalent volume of C02 collected,
dry basis, m ,
V = dry gas volume measured by dry gas meter, dcm (dcf),
V /std\ = dry gas volume measured by dry gas meter, corrected to
standard conditions, dscm (dscf),
V . = total volume of solution in which the sulfur
dioxide sample is contained, 100 ml,
V. = volume of barium perchlorate titrant used for the
sample (average of replicate titrations), ml,
V.. = volume of barium perchlorate titrant used for the
blank, ml,
V , .,» = volume of water at standard conditions, dscm (dscf),
Y = dry gas meter calibration factor, and
32.03 = equivalent weight of sulfur dioxide.
6.2 Calculations for Concentration
The following formulas for calculating the concentration of
sulfur dioxide, using metric units, are to be used along with the
example calculation forms shown in Figures 6.1, 6.2A, and 6.2B.
6.2.1 C02 Volume Collected, Corrected to Standard Conditions -
VC02(std) " 5'467 x 10~4 (maf - mai) Equation 6-1
6.2.2 Moisture Volume Collected, Corrected to Standard Conditions -
Vw(std) = 1>336 X 10~3 (mwf ' mwi) Equation 6-2
-------
Section No. 3.13.5
Date July 1, 1986
Page 13
3. Put water in the sample storage container to the initial
sample mark, and measure the initial sample volume (V , ).
4. Put water in the sample storage container to the mark of
the transferred sample, and measure the final volume (V ).
5. If V , is < V , , correct the sample volume ,.. .
soln,. soln. c (V •. •)
. . _ . . r.-. f i soln
by using Equation 5-6,
V
V ' = V , ..80lni Equation 5-6
soln soln V , M
soln.;
where
V , ' = sample volume to be used for the calculations, ml,
soln
V , = total volume of solution in which the sulfur diox-
soln
ide is contained, ml,
V = initial sample volume placed in storage container,
ml , and
V , = final sample volume removed from storage container,
soln, mi
r ml .
6. Both the corrected and uncorrected values should be sub-
mitted in the test report to the Agency.
Proceed with the analysis as follows:
1. Transfer the contents of the sample bottle to a 100-ml
volumetric flask (VQril )/ an<3 dilute to the mark with deionized
distilled water.
2. Pipette a 20-ml aliquot (V ) of this solution into a
250-ml Erlenmeyer flask, and add 80 ml of 100 percent isopro-
panol .
3. Add two to four drops of thorin indicator, and titrate to
an orange-pink endpoint using standardized 0.0100N barium per-
chlorate. Record the volume of barium perchlorate used in
titrating the sample (V. ). If more than 100 ml of titrant is
required, then a smaller sample aliquot should be used (i.e.,
1.0 ml). If less than 5 ml of titrant is required, the analyst
may prepare the titrant with a normality of 0.0010 when a greater
precision is desired.
4. Repeat the above analysis on a new aliquot from the same
sample. Replicate titrant volumes must be within 1 percent or
0.2 ml, whichever is greater. If the titrant volumes do not meet
this criterion, repeat analyses on new aliquots of the sample
until two consecutive titrations agree within 1 percent or 0.2
ml, whichever is greater, or until sample is spent.
-------
Section No. 3.13.5
Date July 1, 1986
Page 14
5. Record all data on the data form, Figure 5.2. Average
the consistent titrant volumes, and use them as V. in subse-
quent calculations. All analytical data must then be reviewed by
a person familiar with procedures, and this review should be
noted on the data form, Figure 5.2. Note; Protect the 0.0010N
barium perchlorate solution from evaporation at all times.
Warning: Contamination of the sample with Ascarite or
Drierite will cause bias. The analyst should take precautions
when handling Ascarite or Drierite and the field sample or
absorbing solution so as not to introduce these materials into
the sample or absorbing solution.
Note; References 2 and 3 contain additional information on
improved temperature stability and application of Method 6 to
high sulfur dioxide concentration.
-------
Section No. 3.13-5
Date July 1, 1986
Page 15
Table 5.1. ACTIVITY MATRIX FOR POSTSAMPLING OPERATIONS
Activity
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Sampling
Apparatus
Dry gas meter
Within 5% of pretest
calibration factor
Make two independent
runs after each field
test
Recalibrate and
use calibration
factor that gives
lower sample
volume
Rate meter
Within 102 of desired
flow rate (recommended)
Make two independent
runs during the check
of the rate meter
Clean and
recalibrate
Meter thermom-
eter
Within 6°C (10.8°F)
at ambient temperature
Compare with ASTM
mercury-in-glass
thermometer after each
field test
Recalibrate and
and use higher
temperature value
for calculations
Barometer
Within 5.0 mm
(0.2 in.) Hg at
ambient pressure
Compare with mercury-
in-glass barometer
after each field test
Recalibrate and
use lower baro-
metric value for
calculations
Balance
Within 0.05 g
Compare against Class S
weights
Adjust, re-
pair, or re-
place
Analysis
Reagents
Prepare according to
requirements detailed
in Subsection 5.2
Prepare and/or stan-
dardize within 24 h of
sample analysis
Prepare new solu-
tions and/or re-
standardize
Control sample
Titrants differ by
£0.2 ml; analytical
results within 5# of
stated value
Before and after
analysis of field
samples
Prepare new solu-
tions and/or
restandardize
Sample
analysis
Titrant volumes differ
by <1% or £0.2 ml,
whichever is greater
Titrate until two or
more consecutive ali-
quots agree within 1%
or 0.2 ml, whichever is
greater, review all
analytical data
Void sample if
a set of two
titrations do
not meet
criterion
-------
Section No. 3.13.6
Date July 1, 1986
Page 3
6.2.3 SOX, Concentration -
soln
(V. - V..) N \ V / Equation 6-3
^t — OO ^^ ~ ~ *"^_ ^* —
2 m(std) + CO2(std)
6.2.4 C02 Concentration -
Vc°2(std) v im Equation 6-4
C - V + V
CC00 vm(std) vC00(std)
-------
vm = _ -21 • to...
Section No. 3.13.6
Date July 1, 1986
Page 4
METER VOLUME (metric to English)
m _ - to.®.. liter
V = V (in liters) x 0.03531 ft3/liter = / . / 8 f 2* ft3
III ^"~ *"~ *~~ ™™ •"•
METER TEMPERATURE (metric to English)
".-^••fc
tffl = [tm (°C) x 1.8] + 32 = _ _72- . 3^ °F
T = t (°F) + 460 = 5^32 . 3°R
mm — — — — -
BAROMETRIC PRESSURE (metric to English)
Pbar = ^5-T- ' Bim Hg :
Pbar = Pbar (mm Hg) x 0.03937 in. Hg/mm Hg = ^ ^ . 8 O_ in. Hg
METER VOLUME (English to metric)
vm = L • 1£1 £ _ ft3
V = V (ft3) x 0.02832 m3/ft3 = . 0 3 3 6 6 m3
m m — — — — —
METER TEMPERATURE (English to metric)
t = "72- 3 °F
m — -' — * —
t = [t (°F) - 32] x 5/9 = 1- 2. 4 °C
r> ^ /> — ~~ "~n ~~
T = t (°C) + 273 = 2-f 5^. 4 °K
mm — — — J—
BAROMETRIC PRESSURE (English to metric)
P. = 2-1? . BO in. Hg
bar — — — — 3
P. = P. (in. Hg) x 25.4 mm Hg/in. Hg = 75 I . mm Hg
oar oar — — —
Figure 6.1. Method 6A and 6B calculation form (conversion factors)
-------
Section No. 3.13.6
Date July 1, 1986
Page 5
STANDARD METER VOLUME (English units)
= L - I 61 2-
-1- — — — —
bar
- H9' Tm '
V(std) = 17.64 V Y
m
m
bar
m
= 7 . 2 f 7 6 dscf
C02 VOLUME COLLECTED, STANDARD CONDITIONS
(English units)
maf = 3 £ ^ . 3 g, mai = - - - * )- g
(std) = 0.01930 (maf - ma±) = 0 - /_ C®^L dscf
Equation 6-1
'CO,
CO2 CONCENTRATION (percent by volume)
x 10° • JL • LL *
Vm(std) + V (std)
Equation 6-4
SO2 CONCENTRATION (English units)
soln
ml, Vtb = 0 .
2 m1' V
ml, N = ^ . 0
ml
(g-eq)/ml
SQ
- 7.061 x 10"J (vt -
V(std) + Vrn (std)
m uu2
Q 2 £ x 10~4 Ib/dscf
Equation 6-3
Figure 6.2A. Method 6A and 6B calculation form (English units).
-------
Section No. 3.13.6
Date July 1, 1986
Page 6
MOISTURE CONCENTRATION (percent)
mwf = 1 1
-------
Section No. 3.13.6
Date July 1, 1986
Page 7
STANDARD METER VOLUME (metric units)
(using meter volumes)
V = 33.66 liter x 0.001 = O . O ?> 3
m — -** — — — — — — —
= 1 - 0 1_ \_, Pr = 7 5~7 • mm Hg, Tm ,2-7 ^ . 4_ °K
V (std) = 0.3858 V Y Pbar = . 0 3 £" 6 £ dscm
III 111 • • ^™ ~ "~ ~~" "
Tm
CO2 VOLUME COLLECTED, STANDARD CONDITIONS
(metric units)
maf = .2 £ • 9" mai="O" g="" vcq="" (std)="5.467" 10~4(maf="" )="." qo="" f-^^l="" dscm="" 6-1="" co2="" concentration="" (percent="" by="" vco2(std)="" t="" vm(std)="" 6-4="" c0="" s02="" (metric="" units)="" vt="_//_" 03="" ml,="" vtb="b" q_6="" 0_2:="" (g="" eq)="" vsoln="J-" m1'="" va="" "="" 2-°="" °-="" ml="" 32.03="" (vt="" vtb)="" ££&="" mg="" +="" z="" vc02(std)="" 6-3="" figure="" 6.2b.="" method="" 6a="" and="" 6b="" calculation="" form="" units).="" <="" pre="">
-------
Section No. 3.13.6
Date July 1, 1986
Page 8
MOISTURE CONCENTRATION (percent)
Vm(std) = 1'336 x 10~ (mwf ' mwi) = ' -0012 dscm
Equation 6-2
cu _ = _ YEUO_ _ x 100 = ((, . & 2- %
2 V + V + V -- ~~
vm(std) vH20(std) vC02(std)
Equation 6-5
EMISSION RATE OF S02 (metric units)
(using meter volumes)
= 0 . £ & k. x 10"? dscm of C0/ J
Eso, • cso, '„ -" 7JC • 3
(not using meter volumes)
Fc = Q • 4& 4 x 10~? dscm of C02/J
m__ = 32.03 (V. - V..,) N/Vs6In\= /'g . O Z. mg of SO,, collected
oU— t tu I rj 1 — — — — — ^
Z \ Va /
ESO = Fc t1-829 x 1()> mSQ 2__lC -3 ng/J
2 "2
Equation 6-6
Equation 6-7
Figure 6.2B. (continued)
-------
Section No. 3.13.6
Date July 1, 1986
Page 9
Table 6.1. ACTIVITY MATRIX FOR CALCULATION CHECKS
Characteristics
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Analysis data
form
All data and calcula-
tions are shown
Visually check
Complete the
missing data
values
Calculations
Difference between
check and original
calculations should
not exceed round-off
error
Repeat all calculations
starting with raw data
for hand calculations;
check all raw data in-
put for computer calcu-
lations; hand calculate
one sample per test
Indicate errors
on sulfur dioxide
calculation form,
Fig. 6.1A or 6.IB
-------
Section No. 3.13.7
Date July 1, 1986
Page 1
7.0 MAINTENANCE
The normal use of emission-testing equipment subjects it to
corrosive gases, extremes in temperature, vibration, and shock.
Keeping the equipment in good operating order over an extended
period of time requires knowledge of the equipment and a program
of routine maintenance which is performed quarterly or after 2830
liters (100 ft ) of operation, whichever comes first. In
addition to the quarterly maintenance, a yearly cleaning of the
entire meter box is recommended. Maintenance procedures for the
various components are summarized in Table 7.1 at the end of the
section. The following procedures are not required, but are
recommended to increase the reliability of the equipment.
7.1 Pump
In the present commercial sampling train, several types of
pumps are used; the most common are the fiber vane pump with
in-line oiler and the diaphragm pump. The fiber vane pump re-
quires a periodic check of the oiler jar. Its contents should be
translucent; the oil should be changed if it is not translucent.
Use the oil specified by the manufacturer. If none is specified,
use SAE-10 nondetergent oil. Whenever the fiber vane pump starts
to run erratically or during the yearly disassembly, the head
should be removed and the fiber vanes changed. Erratic operation
of the diaphragm pump is normally due to either a bad diaphragm
(causing leakage) or to malfunctions of the valves, which should
be cleaned annually by complete disassembly.
7.2 Dry Gas Meter
The dry gas meter should be checked for excess oil or corro-
sion of the components by removing the top plate every 3 months.
The meter should be disassembled and all components cleaned and
checked whenever the rotation of the dials is erratic, whenever
the meter will not calibrate properly over the required flow rate
range, and during the yearly maintenance.
7.3 Rotameter
The rotameter should be disassembled and cleaned according to
the manufacturer's instructions using only recommended cleaning
fluids every 3 months or upon erratic operation.
7.4 Sampling Train
All remaining sample train components should be visually
checked every 3 months and completely disassembled and cleaned or
replaced yearly. Many items, such as quick disconnects, should
be replaced whenever damaged rather than checked periodically.
Normally, the best procedure for maintenance in the field is to
-------
Section No. 3.13.7
Date July I, 1986
Page 2
use another entire unit such as a meter box, sample box, or
umbilical cord (the hose that connects the sample box and meter
box) rather than replacing individual components.
-------
Section No. 3.13-7
Date July 1, 1986
Page 3
Table 7.1. ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE CHECKS
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Routine main-
tenance
No erratic behavior
Routine maintenance
performed quarterly
or after 2830 liters
(100 ft ^) of opera-
tion; disassemble and
clean yearly
Replace parts
as needed
Fiber vane
pump
In-line oiler free
of leaks
Periodically check oil-
er jar; remove head
and change fiber vanes
Replace as
needed
Diaphragm
pump
Leak-free valves func-
tioning properly
Clean valves during
yearly disassembly
Replace when
leaking or mal-
functioning
Dry gas
meter
No excess oil, corro-
sion, or erratic rota-
tion of the dial
Check every 3 mo. for
excess oil or corrosion
by removing the top
plate; check valves and
diaphragm yearly and
whenever meter dial runs
erratically or whenever
meter will not calibrate
Replace parts as
as needed or re-
place meter
Rotameter
Clean and no erratic
behavior
Clean every 3 mo. or
whenever ball does not
move freely
Replace
Sampling
train
No damage
Visually check every
3 mo; completely dis-
assemble and clean or
replace yearly
If failure
noted, use
another entire
meter box, sam-
ple box, or
umbilical cord
-------
Section No. 3.13.8
Date July 1, 1986
Page 1
8.0 AUDITING PROCEDURE
An audit is an independent assessment of data quality. In-
dependence is achieved if the individuals) performing the audit
and their standards and equipment are different from the regular
field crew and their standards and equipment. Routine quality
assurance checks by a field team are necessary in generation of
good quality data, but they are not part of the auditing proce-
dure. Table 8.1 at the end of this section summarizes the qual-
ity assurance functions for auditing.
fi 7
Based on the results of performance audits ' and
collaborative tests of Method 6, two specific performance audits
are recommended:
1. Audit of the analytical phase of Method 6A, or an audit
of the sampling and analytical phase for Method 6B.
2. Audit of data processing for both Methods.
It is suggested that a systems audit be conducted as specified by
the quality assurance coordinator, in addition to these perform-
ance audits. The two performance audits and the systems audit
are described in detail in Subsections 8.1 and 8.2, respectively.
8.1 Performance Audits
Performance audits are made to evaluate quantitatively the
quality of data produced by the total measurement system (sample
collection, sample analysis, and data processing). It is recom-
mended that these audits be performed by the responsible control
agency once during every enforcement source test. A source test
for enforcement comprises a series of runs at one source. The
performance audit of the analytical phase is subdivided into two
steps: (1) a pretest audit which is optional, and (2) an audit
during the field sampling and/or analysis phase which is
required.
8.1.1 Pretest Audit of Analytical Phase Using Aqueous Ammonium
Sulfate (Optional) - The pretest audit described in this section
can be used to determine the proficiency of the analyst and the
standardization of solutions in the Method 6A or 6B analysis and
should be performed at the discretion of the agency auditor. The
analytical phase of Method.6A or 6B can be audited with the use
of aqueous ammonium sulfate samples provided to the testing
laboratory before the enforcement source test. Aqueous ammonium
sulfate samples may be prepared by the procedure described in
Subsection 3.13.5 on control sample preparation.
The pretest audit provides the opportunity for the testing
laboratory to check the accuracy of its analytical procedure.
This audit is especially recommended for a laboratory with little
-------
Section No. 3.13.8
Date July 1, 1986
Page 2
or no experience with the Method 6A or 6B analysis procedure
described in this Handbook.
The testing laboratory should provide the agency/organiza-
tion requesting the performance test with a notification of the
intent to test 30 days prior to the enforcement source test. The
testing laboratory should also request that the agency/organi-
zation provide the following performance audit samples: two
samples at a low concentration (500 to 1000 mg SO^/dsm of gas
sampled or approximately 10 to 20 mg of ammonium sulfate per
sample)3and two samples at a high concentration (1500 to 2500 mg
S02/dsm of gas sampled or about 30 to 50 mg of ammonium sulfate
per sample). This is based on an emission standard of 1.2 Ib of
SO2 per million Btu which would be about 1300 mg SCU/dsm at 35
percent excess air. At least 10 days prior to the enforcement
source test, the agency/organization should provide the four
audit samples. The concentration of the two low and the two high
audit samples should not be identical.
The testing laboratory will analyze one sample at the low
concentration and one at the high concentration, and submit their
results to the agency/organization prior to the enforcement
source test. (Note: The analyst performing this optional audit
must be the same analyst audited during the field sample analysis
described in Subsection 8.1.2).
The agency/organization determines the relative error (RE)
between the measured SO2 concentration and the audit or known
values of concentration. The RE is a measure of the bias of the
analytical phase of Method 6A or 6B. Calculate RE using Equation
8-1.
RE = Cd ~ Ca x 100 Equation 8-1
Ca
where
3
C. = Determined audit sample concentration mg S02/dsm , and
3
C = Actual audit concentration, mg 50,,/dsm .
a ^
The recommended control limit for the pretest audit is ^5
percent for both audit samples.
If the results of the pretest audit exceed 5 percent, the
agency/organization should have the tester/analyst check the
analytical system and repeat the audit sample analysis using a
second aliquot of the same audit sample. After taking any
necessary corrective action, the testing laboratory should then
analyze the same audit samples and report the results immediately
to the agency/organization before the enforcement source test
analysis.
-------
Section No. 3.13.8
Date July 1, 1986
Page 3
8.1.2 Audit of Analytical Phase Using Aqueous Ammonium Sulfate
for Method 6A - The audit described here is exactly the same
audit promulgated as part of Method 6 in the Federal Register,
Vol. 49, June 27, 1984. The agency responsible for the enforce-
ment source test should obtain the audit samples from the EPA
Quality Assurance Coordinator in the respective EPA Regional
Office.
The agency should provide the tester with two audit samples
to be analyzed at the same time as the field samples from the
enforcement source test. The purpose of this audit is to assess
the data quality at the time of the analysis. The relative error
(RE) for the audit samples results are determined using Equation
8-1. The results of the calculated RE should be included in the
enforcement source test report as an assessment of accuracy of
the analytical phase of Method 6A during the actual enforcement
source test.
The two audit samples should be analyzed concurrently with
and in the same manner as the set of compliance samples to
evaluate the technique of the analyst and the preparation of the
standards. The same analyst,, analytical reagents, and analytical
system must be used for both the compliance samples and the EPA
audit samples; if this condition is met, auditing of subsequent
compliance analyses within 30 days for the same enforcement
agency may not be required. An audit sample set may not be used
to validate different sets of compliance samples under the
jurisdiction of different enforcement agencies unless prior
arrangements are made with both enforcement agencies.
3
Calculate the concentrations in mg/dsm using the specified
sample volume in the audit instructions. (Note: Indication of
acceptable results may be obtained immediately by reporting by
telephone to the responsible enforcement agency the audit results
in mg/dsm and compliance results in total mg S02/sample.)
Include the results of both audit samples, their identification
numbers, and the analyst's name with the results of the
compliance determination samples in appropriate reports to the
EPA Regional Office or the appropriate enforcement agency.
Include this information with subsequent compliance analyses for
the same enforcement agency during the 30-day period.
The concentration of the audit samples obtained by the
analyst shall agree within 5 percent of the actual concentra-
tions. If the 5 percent specification is not met, reanalyze the
compliance samples and audit samples, and include initial and
reanalysis values in the test report.
Failure to meet the 5 percent specification may result in
retests until the audit problems are resolved. However, if the
audit results do not affect the compliance or noncompliance stat-
us of the affected facility, the Administrator may waive the
-------
Section No. 3.13.8
Date July 1, 1986
Page 4
reanalysis requirement, further audits, or retests and accept the
results of the compliance test. While steps are being taken to
resolve audit analysis problems, the Administrator may also
choose to use the data to determine the compliance or noncom-
pliance status of the affected facility.
Note: It is recommended that known quality control samples
be analyzed prior to the compliance and audit sample analysis to
optimize the system accuracy and precision. One source of these
samples is:
U. S. Environmental Protection Agency
Environmental Monitoring and Systems Laboratory
Quality Assurance Division (MD-77A)
Research Triangle Park, North Carolina 27711
Attention: Source Test Audit Coordinator
8.1.3 Audit of Sampling and Analytical Phase for Method 6B -
When Method 6B is used to demonstrate compliance with a 30-day
rolling average standard (e.g., 40 CFR 60, Subpart Da), the
following audits should be conducted:
Cylinder Gas Audit (CGA) - During the first 7 days of con-
tinous use of Method 6B at the same source, a CGA should be
conducted. Thereafter, a CGA should be conducted once every
calendar quarter that Method 6B is used at the same source. The
purpose of the CGA is to measure the RE for the SO2 and CO2
sampling and analyses. The RE should be within 15 percent. The
testers must obtain an audit gas in an aluminum cylinder that
meets the requirements of EPA Protocol No. 1 (Section 3.0.4 of
this Handbook) and contains SO- in the range of 200 to 400 ppm
and C02 in the range of 12 percent to 16 percent, with the
balance of the gas as N2. In addition, the tester must specify
that the gas manufacturer (I) blends moisture-free carbon dioxide
with the sulfur dioxide and (2) does not use a UV fluorescent
analyzer to determine the SO- concentration in the cylinder,
since a UV fluorescence S00 signal is quenched by the presence of
co2.§ 2
g
In a study conducted by EPA, audit cylinders containing
sulfur dioxide (200 to 400 ppm) and carbon dioxide (12 to 16
percent) were purchased from nine different commercial gas
manufacturers. All nine cylinders ordered were to be prepared
according to EPA Protocol No. 1. The purpose of this study was
to determine whether accurate mixtures of S02 and C02 could be
expected from commercial gas manufacturers following EPA Protocol
No. 1 and to determine if these mixtures were stable. The
accuracy for C02 was within 1.2 percent for all nine cylinders.
The accuracy for S02 was within 5.2 percent for seven cylinders
and within 9.8 percent for the remaining two cylinders. The
sulfur dioxide and carbon dioxide concentrations were were found
to be stable over the entire period of the study (473 days). In
another study conducted by EPA, three cylinders containing a
-------
Section No. 3.13.8
Date July 1, 1986
Page 5
nominal 250 ppm S02 and 10 percent C02 showed the SO2 to be
stable over the entire periocLof the study (22 months). Finally,
in a study conducted by EPA, cylinder gases of nominal 250 ppm
S02 and 10 percent C02 were used to audit three contractors using
Method 6B. These audits demonstrated that cylinder gases are an
effective means to assess the accuracy of Method 6B.
To conduct the CGA using the Protocol No. 1 gases, the
following procedures should be followed:
1. Attach the audit gas cylinder as shown in Figure 8.1.
2. Open the audit cylinder until 2 times the sample flow
rate is obtained on the discharge rotameter. This would be
approximately 2.0 L/min for the intermittent sampling train, and
approximately 60 ml/min for the continuous sampling train. Allow
the audit gas to flow through the manifold for 5 minutes to
condition the manifold.
3. Start the Method 6B sampling train, and adjust to de-
sired rate. The audit sample will be collected at a continuous
sampling rate for both the continuous and intermittent sampling
train. This is done in an effort to minimize the use of the
audit gas. The intermittent sampling train should be operated
for 30 minutes. The continuous train should be operated for 24
hours .
4. The sampling train should be set at the proper sampling
rate for the train; the audit gas flow rate should then be ad-
justed so that the discharge rotameter is reading at about equal
to the sampling rate. This will ensure that the audit gas is
collected properly from the glass manifold.
5. At the completion of the run, shut off the sampling
train, then shut off the audit gas flow.
6. The audit sample should be recovered and analyzed in
the same manner as the field samples.
7. Calculate Ib S02/million Btu for the Method 6B sampling
train (CM6B) using Equation 8.2.
where
CM6B = 1-141 x 10 c TT = Ib S0,/million Btu
C02
Equation 8-2
= Concentration measured by Method 6B, Ib SO-/
million Btu, 2
-------
REGULATOR
V MALE/FEMALE GLASS JOINT
S02
&
C02
in
N2
TEFLON
GLASS MANIFOLD
u
METHOD 6B
PROBE
TO METHOD 6B
SAMPLE TRAIN
V MALE/
FEMALE GLASS
JOINT
V
TEFLON
EXCESS TO
ATMOSPHERE
ROTAMETER
Figure 8.1. Cylinder Gas Audit of Method 6B.
BUBBLER
•a o OT
CD 0) (D rt
H-
en Q O
C D
OJ
M •
v£> M
00 00
0\ •
00
-------
Section No. 3.13.8
Date July 1, 1986
Page 7
F = F factor (use the actual F factor or assume
c F of 1800 for both calculations), scf of
c82/million Btu,
Mc~ = Mass of SO,, per total sample analyzed, mg of SO,,, and
o \J ** £ £
M = Mass of C02 per total sample analyzed, g of C02.
8. Calculate Ib S02/million Btu for the audit gas (C )
using Equation 8-3.
„ Equation 8-3
C = 1.66 x 10 S00 F 100
2ppm C
% C02
where
C = Concentration in audit cylinder, Ib S00/million
a Btu, 2
SO2 = Concentration of S02 in audit cylinder, ppm,
ppm
8-4,
% C02 = Concentration of C02 in audit cylinder, %, and
F = F factor (same as above), scf of C00/million Btu.
C ^
9. The auditor should then calculate the RE using Equation
RE = CM6B " Ca x 100 Equation 8-4
Ca
10. The RE should be within 15 percent. The results of the
audit should be included in the report as an audit of the
accuracy of the sampling and analysis phase of Method 6B.
S02 Analysis - During the first 7 days of continuous use of
Method 6B at the same source, an S02 analysis audit should be
performed. Thereafter, an S02 analysis audit should be conducted
once every 30 days that Method 6B is used at the same source.
The purpose of this audit is to measure the RE for S02 analysis.
The RE should be within 5 percent. The audit samples described
in Section 8.1.3 should be used. The CGA and the S02 analysis
should be conducted on the same day.
8.1.4 Audit of Data Processing - Data processing errors can be
determined by auditing the data recorded on the field and labor-
atory forms. The original and audit (check) calculation should
agree within roundoff error; if not, all of the remaining data
should be checked. The data processing may also be audited by
-------
Section No. 3.13.8
Date July 1, 1986
Page 8
providing the testing laboratory with specific data sets (exactly
as would appear in the field), and by requesting that the data
calculation be completed and that the results be returned to the
agency/organization. This audit is useful in checking both
computer programs and manual methods of data processing.
8.2 Systems Audit
A systems audit is an on-site qualitative inspection and
review of the total measurement system (sample collection, sample
analysis, data processing, etc.>. Initially, a systems audit is
recommended for each enforcement source test, defined here as a
series of three runs at one source. After the test team gains
experience with the method, the frequency of auditing may be re-
duced—once for every four tests.
The auditor should have extensive background experience in
source sampling, specifically with the measurement system being
audited. The functions of the auditor are summarized below:
1. Inform the testing team of the results of pretest aud-
its, specifying any area(s) that need special attention or
improvement.
2. Observe procedures and techniques of the field team
during sample collection.
3. Check/verify records of apparatus calibration checks
and quality control used in the laboratory analysis of control
samples from previous source tests, where applicable.
4. Record the results of the audit, and forward them with
comments to the test team management so that appropriate correc-
tive action may be initiated.
While on site, the auditor observes the source test team's over-
all performance, including the following specific operations:
1. Setting up and leak testing the sampling train.
2. Preparing and adding the absorbing solution to the
impingers.
3. Checking for constant rate sampling (for Method 6A
only).
4. Purging the sampling train (for Method 6A only).
Figure 8.2 is a suggested checklist for the auditor.
-------
Section No. 3.13.8
Date July 1, 1986
Page 9
Yes
No
Comment
Presampling Preparation
1. Knowledge of process conditions
2. Calibration of pertinent equipment, in particular, the
dry gas meter, prior to each field test
/
On-Site Measurements
3. Leak testing of sampling train after sample run
4. Preparation and addition of absorbing solutions to
impingers
5. Constant rate sampling (for Method 6A only)
6. Purging of the sampling train and rinsing of the
impingers and connecting tubes to recover the sample (for
Method 6A only)
7. Recording of pertinent process conditions during sample
collection
8. Maintaining the probe at a given temperature
/
_
/
/
/
/
Postsampling
9. Control sample analysis—accuracy and precision
10. Sample aliquoting techniques
11. Titration technique, particularly endpoint precision
12. Use of detection blanks in correcting field sample
results
13. Weighing of the C0_ absorbent
14. Calculation procedure/check
15. Calibration checks
16. Standardized barium perchlorate solution
17. Result of the audit sample
General Comments
f-
/
Figure 8.2. Method 6A and 6B checklist to be used by auditors.
-------
Section No. 3.13.8
Date July 1, 1986
Page 10
Table 8.1. ACTIVITY MATRIX FOR AUDITING PROCEDURE
Audit
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Analytical
phase using
aqueous ammon-
ium sulfate
(Method 6A)
Measured RE of the
pretest audit sample
should be less than
+5# of given value
(optional); RE for
audit during test +5
(mandatory)
Frequency: Once during
every enforcement source
test
Method; Analyze audit
samples and compare
with given values
Review operat-
ing technique
and repeat audit
and field sample
analysis
Analytical
phase using
aqueous ammon-
ium sulfate
(Method 6B)
Measured RE of the
pretest audit sample
should be less than
+5% of given value
(optional)
Frequency; Once prior to
setting up a new system
Method; Measure audit
samples and compare with
given value
Review operat-
ing technique
and repeat audit
sample analysis
Sampling and
analytical
phase using
cylinder gas
audit and
aqueous am-
monium sul-
fate (contin-
uous use of
Method 6B)
Measured RE of the
cylinder gas audit
should be less than
•t-15% (mandatory)
Measured RE of the
aqueous audit samples
should be less than
+5X (mandatory)
Frequency; Within the
first 7 days of initial
use and every 30 days
thereafter during
continued use
Method; Perform cylinder
gas audit and compare
with given value
Frequency; Same as above
and on the same day as
the cylinder gas audit
Method; Perform audit
sample analysis and
compare with given value
Review operat-
ing technique
and repeat audit
Same as above
CGA
Data processing
errors
The original and
check calculations
within round-off
error
Frequency; Once during
every enforcement source
test
Method; Independent
calculations, starting
with recorded data
Check and correct
all data for the
source test
(continued)
-------
Section No. 3.13.8
Date July 1, 1986
Page 11
Table 8.1 (continued)
Audit
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
System audit
Operation technique
described in this
section of the Hand-
book
Frequency; Once during
every enforcement test
until experience gained,
then every fourth test
Method: Observation of
techniques, assisted by
audit checklist.
Fig. 8.2
Explain to team
the deviations
from recommended
techniques; note
on Fig. 8.2
-------
Section No. 3.13.9
Date July 1, 1986
Page 1
9.0 RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY
To achieve data of desired quality, two considerations are
essential: the measurement process must be in a state of statis-
tical control at the time of the measurement, and the systematic
errors, when combined with the random variation (errors of meas-
urement), must result in an acceptable uncertainty. To ensure
good quality data, it is necessary to perform quality control
checks and independent audits of the measurement process; to
document these data by means of a quality control chart as appro-
priate; and to use materials, instruments, and measurement
procedures that can be traced to an appropriate standard of
reference.
Data must be routinely obtained by replicate measurements of
control standard samples and working standards. The working
calibration standards should be traceable to standards that are
considered primary, such as those listed below.
1. Dry gas meter must be calibrated against a wet test
meter that has been verified by an independent liquid displace-
ment method (Section 3.13.2) or by use of a spirometer.
2. The barium perchlorate is standardized against sulfuric
acid. The sulfuric acid should have been standardized with pri-
mary standard grade potassium acid phthalate. The standardized
barium perchlorate should then be validated with an aqueous
solution of primary standard grade ammonium sulfate. This makes
the titrant solution traceable to two primary standard grade
reagents.
3. The audit of Method 6B is conducted with a cylinder gas
that is traceable to an NBS gas Standard Reference Material
(SRM) or an NBS/EPA approved gas Certified Reference Material
(CRM) with the use of EPA Protocol No. 1.
-------
Section 3.13.10
Date July 1, 1986
Page 1
10.0 REFERENCE METHODS*
MrmoD 6A—DETERMINATION or SULTUR Di-
OXIDE. MOISTURE. AND CARSON DIOXIDE
EMISSION! FROM FOSSIL Fan. COMBUSTION
SOURCES
1. Applicability and Principle
1.1 Applicability. This method applies to
the determination of sulfur dioxide (SO.)
emissions from fossil fuel combustion
sources in terms of concentration (mg/m1)
and in terms of emission rate and to
the determination of carbon dioxide (CO.)
concentration (percent). Moisture, If de-
sired, may also be determined by this
method.
The minimum detectable limit, the upper
limit, and the interferences of the method
for the measurement of SO. are the same as
for Method a. For a 20-liter sample, the
method has a precision of 0.5 percent COi
for concentrations between 2.5 and 25 per-
cent CO. and 1.0 percent moisture for mois-
ture concentrations greater than 5 percent.
1.2 Principle. The principle of sample
collection is the same as for Method 6
except that moisture and CO. are collected
in addition to SO. In the same sampling
train. Moisture and CO, fractions are deter-
mined gravimetrtcally.
2. Xpparatiu
2.1 Sampling. The sampling train Is
shown In Figure 6A-1: the equipment re-
quired is the same as for Method 6. Section
2.1. except as specified below:
2.1.1 SO, Absorbers. Two 30-ml midget
Unptngers with a 1-mrn restricted tip and
two 30-ml midget bubblers with an unre-
stricted tip. Other types of Implngers and
bubblers, such as Mae West for SO, collec-
tion and rigid cylinders for moisture absorb-
ers containing Drierlte. may be used with
proper attention to reagent volumes and
levels, subject to the Administrator's ap-
proval.
2.1.2 CO, Absorber. A scalable rigid cylin-
der or bottle with an inside diameter be-
tween 30 and 90 mm and a length between
125 and 250 nun and with appropriate con-
nections at both ends.
Non: For applications downstream of wet
scrubbers, a heated oui-of-stack filter
(either borosillcate glass wool or glass fiber
mat) is necessary. The filter may be a sepa-
rate heated unit or may be within the
heated portion of the probe. If the filter is
within the sampling probe, the filter should
not be within 15 cm of the probe inlet or
any unheated section of the probe, such as
the connection to the first SO. absorber.
The probe and filter should be heated to at
least 20* C above the source temperature,
but not greater than 120* C. The filter tem-
perature (i.e.. the sample gas temperature)
should be monitored to assure the desired
temperature is maintained. A heated Teflon
connector may be used to connect the filter
holder or probe to the first impinscr.
Norr Mention of a brand name does not
constitute endorsement by the Environmen-
tal Protection Agency.
* Federal Register, Volume 47,
Volume 49, No. 51, March 14,
2.2 Sample Recovery and Analysis. The
equipment needed for sample recovery and
analysis is the same as required for Method
6. In addition, s balance to measure within
0.05 g is needed for analysis.
3. Reapenti
Unless otherwise indicated, all reagents
must conform to the specifications estab-
lished by the committee on analytical rea-
gents of the American Chemical .Society.
Where such specifications are not available.
use the best available grade.
3.1 Sampling. The reagents required for
sampling are the same as specified in
Method 6. In addition, the following rea-
gents are required:
3.1.1 Drtente. Anhydrous calcium sulfate
(CaSO.) deslccant. 8 mesh, indicating type Is
recommended. (Do not use silica gel or simi-
lar deslccant in the application.)
3.1.2 CO. Absorbing Material. Ascsrtte II.
Sodium hydroxide coated silica. 8 to 20
mesh.
3.2 Sample Recovery and Analysis. The
reagents needed for sample recovery and
analysis are the same as for Method 8. Sec-
tions 3.2 and 3.3. respectively.
4. Procedure
4.1 Sampling.
4.1.1 Preparation of Collection Train.
Measure 15 ml of 80 percent isopropanol
into the first midget bubbler and IS ml of 3
percent hydrogen peroxide into each of the
first two midget impingers as described in
Method 6. Insert the glass wool into the top
of the Isopropanol bubbler as shown in
Figure 6A-1. Into the fourth vessel In the
train, the second midget bubbler, place
about 26 g of Drierite. Clean the outsides of
the bubblers and impingers. and weigh at
room temperature (-20* C) to the nearest
.0.1 g. Weigh the four vessels simultaneous-
ly, and record this initial mass.
With one end of the COi absorber sealed.
place glut wool in the cylinder to a depth
of about 1 cm. Place about ISO g of CO. ab-
sorbing material in the cylinder on top of
the glass wool, and fill the ™"«'"«"g space
in the cylinder with glass wool. Assemble
the cylinder as shown In Figure &A-2. With
the cylinder in a horizontal position, rotate
It around the horizontal axis. The CCs ab-
sorbing inalitr**1 should remain in position-
during the rotation, and no open spaces or
<»frfrpw»l« yhniji^ be {ormed. If necessary,
pack more glass wool Into the cylinder to
make the CO, absorbing material stable.
Clean the outside of the cylinder of loose
No. 231, December 1, 1982 and
1984.
-------
Section 3.13.10
Date July 1, 1986
Page 2
dirt and moisture and weigh at room tem-
perature to the nearest 0.1 g. Record this
Assemble the train as shown in Figure 6A-
1. Adjust the probe heater to a temperature
sufficient to prevent condensation (see Note
in paragraph 2.1.1). Place crushed Ice and
water around the Impingers and bubblers.
Mount the COt absorber outside the water
bath In a vertical now position with the
sample gas inlet at the bottom. Flexible
tubing, e.g.. Tygon. may be used to connect
the last SO, absorbing bubbler to the Drier-
ite absorber and to connect the Drierite ab-
sorber to the COi absorber. A second, small-
er CO. absorber containing Ascarite n may
be added in line downstream of the primary
CO. absorber as a breakthrough indicator.
Ascarite n turns white when CO, Is ab-
sorbed.
4.1.2 Leak-Check Procedure and Sample
Collection. The leak-check procedure and
sample collection procedure are the same as
specified In Method 0. Sections 4.1J and
4.1.3. respectively.
4.2. Sample Recovery.
4.2.1 Moisture Measurement. Disconnect
the Isopropanol bubbler, the SO, Impingers.
and the moisture absorber from the sample
train. Allow about 10 minutes for them to
reach room temperature, clean the ouuidee
of loose dirt and moisture, and weigh them
simultaneously in the same manner as in
Section 4.1.1. Record this final i
4.U Peroxide Solution. Discard the con-
tents of the Isopropanol bubbler and pour
the contents of the midget Impingers into a
leak-free polyethylene bottle for shipping.
Rinse the two midget Impingers and con-
necting tubes with detained distilled water.
and add the washings to the same storage
container.
4.2.3 CO, Absorber. Allow the CO, ab-
sorber to warm to room temperature (about
10 minutes), clean the outside of loose din
and moisture, and weigh to the nearest 0.1 g
In the same manner as In Section 4.1.1.
Record this final mass. Discard used Ascar-
ite II material.
4.3 Sample Analysis. The sample analysis
procedure for SO, is the same as specified In
Method 6. Section 4J.
S. Calibration
The calibrations and checks are the same
as required in Method 6. Section S.
Figure 6A-1. Sampling train.
Figure 6A-2. C02 absorber.
-------
Section 3.13.10
Date July 1, 1986
Page 3
6. Calculation*
Carry out calculation!, retaining at lead
one extra decimal figure beyond that of the
acquired data. Round off figures after final
calculations. The r*'nilttt*nnn noinynrla-
ture. and procedures are the same as speci-
fied in Method 6 with the addition of the
following:
6.1 Nomenclature.
C.- Concentration of moisture, percent.
Co*-Concentration of COi. dry basis, per-
cent.
M«- Initial mau of tmpingers. bubblers.
and moisture absorber, g.
nu,-Final mass of impingers. bubblers, and
moisture absorber, g.
m.-Initial mass of COt absorber, g.
m*_ Final mass of COt absorber, g.
VCTHU^,-Equivalent volume of CCs collected
at standard conditions, dam'.
VMM,-Equivalent volume of moisture col-
lected at standard conditions, sm*.
5.487x10-'-Equivalent volume of gaseous
COi at standard conditions per gram, sm'/
g.
1.336xlO''-Equivalent volume of water
vapor at standard conditions per gram.
am'/g.
0.2 COt Volume Collected. Corrected to
Standard Conditions.
Veotu-i - 5.467 x 10"• (m*- m*) (Bq. 6A-1)
8.3 Moisture Volume Collected. Correct-
ed to Standard Conditions.
V^M, . 1.338 x 10-' (nur- m«> (Eq. 8A-2)
8.4 SO» Concentration.
7. Emiuion Rate Procedure.
U the only emission measurement desired
Is in terms of emission rate of SO, (ng/J).
an abbreviated procedure may be used. The
differences between the above procedure
and the abbreviated procedure are described
below.
7.1 Sample Train. The sample train Is
the same as shown in Figure 8A-1 and as de-
scribed In Section 4. except that the dry gas
meter Is not needed.
7.2 Preparation of the Collection Train.
Follow the same procedure as In Section
4.1.1. except do not weigh the iaopropanol
bubbler, the SO, absorbing impingers or the
moisture absorber.
7.3 Sampling. Operate the train as de-
scribed In Section 4.1.3. except that dry gas
meter readings, barometric pressure, and
dry gas meter temperatures need not be re-
corded.
7.4 Sample Recovery. Follow the proce-
dure In Section 4.2. except do not weigh the
Isopropanol bubbler, the SO, absorbing im-
olngers. or the moisture absorber.
7.5 Sample Analysis. Analysis of the per-
oxide solution is the same as described In
Section O.
7.6 Calculations.
7.8.1 80s Mass Collected.
-32.W (v,-
(Bo.eA-7)
c.0-
(Eq.eA-3)
8.5 CO, Concentration.
Where:
(&«••• Mass of SOi collected, mg.
7.6.2 Sulfur Dioxide Emission Rate.
Ea-F<(1.820X10*).
(Eq.8A-8)
-X100
Ceo.-
6.6 Moisture Concentration.
(Eq. 8A-5)
C.-
Where:
E^-Emission rate of SOi (ng/J).
P.-Carbon F Factor for the fuel burned.
mVJ. from Method IB.
8. BioUovrapfty
8.1 Same as for Method 6. citations 1
through 8. with the addition of the follow-
ing:
8.2 Stanley. Jon and P.R. WestUn. An Al-
ternate Method for Stack Oas Moisture De-
termination. Source Evaluation Society
Newsletter. VoL 3. No. 4. November 1978.
8J Whittle. Richard N. and PJl. Westlln.
Air Pollution Text Report: Development and
Evaluation of an Intermittent Integrated
SOi/COi T—*—«"" «M»pi««T Procedure. En-
vironmental Protection Agency. Emission
Standard and Engineering Division. Emis-
sion Measurement Branch. Beaeireh Trian-
gle Park. North Carolina. December 1979.14
-------
MXTBOD 8B—DnTMfDfATIOH OP SUITOR Dl-
OXIDE AMD CAJUOK Dionri DAILT Avnuoc
EMISSIONS PROM FOSSIL Pun. CoxBtrsnon
Sourness
Section 3.13.10
Date July 1, 1986
Page 4
I. Applicability and Principle
1.1 Applicability. This method applies to
the determination of sulfur dioxide (SO,)
emissions from combustion sources in terms
of concentration (ng/m*> and emission rate
(ng/J). and (or the determination of carbon
dioxide (COi) concentration (percent) on a
daily (24 hours) basis.
The Minimum detectable limits, upper
limit, and the Interferences for SO. meas-
urements are the same as for Method 6.
EPA-sponsored collaborative studies were
undertaken to determine the magnitude of
repeatability and reproduclbllity achievable
by qualified testers following the procedures
In this method. The results of the studies
evolve from 145 field tests itirtmMng com-
parisons with Methods 3 and 6. For meas-
urements of emission rates from wet. flue
gas desulfurtzation units in (ng/J). the re-
peatability (within laboratory precision) Is
8.0 percent and the reproduclbUlty (between
laboratory precision) Is 11.1 percent.
1.2 Principle. A gas sample is extracted
from the sampling point in the stack inter-
mittently over a 24-hour or other specified
tune period. Sampling may also be conduct-
ed continuously If the apparatus and proce-
dures are appropriately modified (see Note
in Section 4.1.1). The SO, and CO, are sepa-
rated and collected in the sampling train.
The SOi fraction Is measured by the
barlum-thonn tltration method, and COi is
determined gravimetrlcally.
2. Apparatus.
The equipment required for this method
Is the same as specified for Method 6A. Sec-
tion 2. except the isopropanol bubbler Is not
used. An empty bubbler for the collection of
liquid droplets and does not allow direct
contact between the collected liquid and the
gas sample may be included in the train. For
intermittent operation, include an industrial
timer-switch designed to operate in the "on"
position at least 2 minutes continuously and
"off" the remaining period over a repeating
cycle. The cycle of operation in designated
in the applicable regulation. At a m^Tiimiitfi
the sampling operation should Include at
least 12. equal, evenly-spaced periods per 24
hours.
For applications downstream of wet scrub-
bers, a heated out-of-stack filter (either Dor-
osilicate glass wool or glass fiber mat) is nec-
essary. The probe and filter should be
heated continuously to at least 20* C above
the sourced temperature, but not greater
than 120* C. The filter (I.e.. sample gas)
temperature should be monitored to assure
the desired temperature is maintained.
Stainless steel sampling probes, type 316.
are not recommended for use with Method
9B because of potential corrosion and con-
tamination of sample. Glass probes or other
types of stainless steel, e.g.. Hasteloy or Car-
penter 20 are recommended for long-term
use.
Other sampling equipment, such as Mae
West bubblers and rigid cylinders for mois-
ture absorption, which requires sample or
reagent volumes other than thoee specified
in this procedure for full effectiveness may
be used, subject to the approval of the Ad-
ministrator.
3. RtagenU.
All reagents for sampling and analysis are
the same as described In Method 6A. Sec-
tion 3. except isopropanol Is not used for
sampling. The hydrogen peroxide absorbing
solution shall be diluted to no less than 6
percent by volume, instead of 3 percent as
specified in Method 6. If Method 8B Is to be
operated in a low sample flow condition
(less than 100 ml/min). molecular sieve ma-
terial may be substituted for Ascartte n as
the CO, absorbing material. The recom-
mended molecular sieve material Is Union
Carbide W« inch pellets. SA. or equivalent.
Molecular sieve material need not be dis-
carded following the sampling run provided
It Is regenerated as per the manufacturer's
Instruction. Use of molecular sieve material
airflow rates higher than 100 ml/min may
cause erroneous CO, results.
4. Procedure
4.1 Sampling.
4.1.1 Preparation of Collection Train.
Preparation of the sample train is the same
as described In Method 6A. Section 4.1.4.
with the addition of the following:
The sampling train Is assembled as shown
In Figure 6A-1. except the Isopropanol bub-
bler is not Included. The probe must be
heated to a temperature sufficient to pre-
vent water condensation and must include a
filter (either in-stack. out-of-stack. or both)
to prevent paniculate entrainment in the
peroxide impingers. The electric supply for
the probe heat should be continuous and
separate from the timed operation of the
sample pump.
Adjust the timer-switch to operate in the
"on" position from 2 to 4 minutes on a 2-
hour repeating cycle or other cycle specified
in the applicable rrtiilttlTrn Other timer se-
quences may be used with the restriction
that the total sample volume collected is be-
tween 25 and 00 liters for the amounts of
sampling reagents prescribed In this
method.
Add cold water to the tank until the im-
pingers and bubblers are covered at least
two-thirds of their length. The Impingers
and bubbler tank must be covered and pro-
tected from intense heat and direct sun-
light. If freezing conditions exist, the im-
pinger solution and the water bath must be
protected.
None Sampling may be conducted' con-
tinuously If a low flow-rate sample pump (20
to 40 ml/min for the reagent volumes de-
scribed in this method) Is used. Then the
timer-switch Is not necessary. In addition, if
the sample pump Is designed for constant
rate sampling, the rate meter may be delet-
ed. The total gas volume collected should be
between 25 and 60 liters for the amounts of
-sampling reagents prescribed In this
method.
4.1.2 Leak-Check Procedure. The leak-
cheek procedure Is the same as described in
Method 6. Section 4.1.2.
-------
Section 3.13.10
Date July 1, 1986
Page 5
4.1.3 84mple Collection. Record the ini-
tial dry gas meter reading. To begin sam-
pling. position the Up of the probe at the
sampling point, connect the probe to the
tint Implnger (or filter), and start the timer
and the sample pump. Adjust the sample
now to a constant rate of approximately 1.0
llter/mln as Indicated by the rotameter.
Assure that the timer Is operating as intend*
ed. I.e.. in the "on" position for the desired
period and the cycle repeats as required.
^During the 24-hour sampling period.
record the dry gas meter temperature one
time between 9:00 ^m and 11:00 ^"« and
the barometric pressure.
At the conclusion of the run. turn off the
timer and the sample pump, remove the
probe from the stack, and record the final
gas meter volume reading. Conduct a leak,
check as described in Section 4.1.2. If a leak
Is found, void the test run or use procedures
acceptable to the Administrator to adjust
the sample volume for leakage. Repeat the
steps in this section (4.1.3) for successive
runs.
4.2 Sample Recovery. The procedures for
sample recovery (moisture measurement.
peroxide solution, and aacartte bubbler) are
the same as In Method 8A. Section 4.2.
4.3 Sample Analysis. Analysis of the per-
oxide impinger solutions is the same as in
Method 6. Section 4.3.
5. Calibration
S.I Metering System.
5.1.1 Initial 'Calibration. The initial cali-
bration for the volume metering system is
the same as for Method 6. Section 5.1.1.
5.1.2 Periodic Calibration Check. After
30 days of operation of the test train, con-
duct a calibration check as in Section 5.1.1
above, except for the following variations:
(1) The leak cheek is not to be conducted.
(2) three or more revolutions of the dry gas
meter must be used, and (3) only two Inde-
pendent runs need be made. If the calibra-
tion factor does not deviate by more than 5
percent from the initial calibration factor
determined in Section 5.1.1. then the dry
gas meter volumes obtained during the test
series are acceptable and use of the train
can continue. If the calibration factor devi-
ates by more than 5 percent, recalibrate the
metering system as in Section 5.1.1: and for
the calculations for the preceding 30 days of
data, use the calibration factor (initial or re-
callbratlon) that yields the lower gas
volume for each test run. Use the latest cali-
bration factor for succeeding tests.
5.2 Thermometers. Calibrate against
mercury-ln-glass thermometers t-'iiy gad
at 30-day Intervals.
5.3 Rotameter. The rotameter need not
be calibrated, but ThP'ild be cleaned ""*
r-..t-.r..-^r< according to the manufacturer's
5.5 Barium Perchlorate Solution. Stan-
darize the barium perchlorate solution
against 25 ml of standard sulfurtc add to
which 100 ml of 100 percent Isopropanol has
been added.
t. Caicuiatloru
The nomenclature and calculation proce-
dures are the same as In Method 8A with
the following exceptions:
PM,- Initial barometric pressure for the test
period, mm Hg.
T.» Absolute meter temperature for the
test period. 'K.
7. Emission Rate Procedure
The emission rate procedure Is the same
as described in Method 6A. section 7. except
that the timer Is needed and is operated as
described In this method.
«. .Bibliography
8.1 Same as for Method 6. citations 1
through 8. with the addition of the follow-
tor
8.2 Stanley. Jon and PJR. Westlin. An Al-
ternate Method for Stack Oas Moisture De-
termination. Source Evaluation Society
Newsletter. Vol. 3. No. 4. November 1078.
8.3 Whittle. Richard N. and P.R. Westlin.
Air Pollution Test Report: Development and
Evaluation of an Intermittent Integrated
SOi/COt Emission Sampling Procedure. En-
vironmental Protection Agency. Emission
Standard and Engineering Division. Emis-
sion Measurement Branch. Research Trian-
gle Park, North Carolina. December 1878.14
8/1- Butler. Prank E: J.E. KnolL J.C.
Suggs. M.R. Midgett. and W. Mason. The
Collaborative Test of Method 6B: Twenty-
Pour-Hour Analysis of SOi and CO
JAPCA. Vol. 33. No. 10. October 1983.
5.4 Barometer. Calibrate against a mer-
cury barometer Initially and at 30-day inter-
vals.
-------
Section No. 3.13.11
Date July 1, 1986
Page 1
11.0 REFERENCES
1. Butler, Frank E., Joseph E. Knoll, Jack C. Suggs, M.
Rodney Midgett, and Wade Mason. The Collaborative Test of
Method 6B: Twenty-Four-Hour Analysis of S02 and C02.
JAPCA, Volume 33, No. 10, October 1983, pp. 968-973.
2. Federal Register, Volume 47, No. 231, December 1, 1982.
Method 6A - Determination of Sulfur Dioxide, Moisture, and
Carbon Dioxide Emissions From Fossil Fuel Combustion
Sources and Method 6B - Determination of Sulfur Dioxide
and Carbon Dioxide Daily Average Emissions From Fossil
Fuel Combustion Sources.
3. Federal Register, Volume 49, No. 51, March 14, 1984.
Additions and Corrections to Methods 6A and 6B.
4. Fuerst, Robert G. Improved Temperature Stability of
Sulfur Dioxide Samples Collected by the Federal Refer-
ence Method. EPA-600/4-78-018, April 1978.
5. Knoll, Joseph E. and M. Rodney Midgett. The Applica- tion
of EPA Method 6 to High Sulfur Dioxide Concentra- tions.
EPA-600/4-76-038, July 1976.
6. Fuerst, R. G., R. L. Denny, and M. R. Midgett. A Summary
of Interlaboratory Source Performance Surveys for EPA
Reference Methods 6 and 7 - 1977. Available from U. S^
Environmental Protection Agency, Environmental Monitoring
and Support Laboratory (MD-77), Research Triangle Park,
N.C. 27711.
7. Fuerst, R. G. and M. R. Midgett. A Summary of Inter-
laboratory Source Performance Surveys for EPA Reference
Methods 6 and 7 - 1978. Report in preparation by U. S.
Environmental Protection Agency, Environmental Monitor-
ing and Support Laboratory (MD-77), Research Triangle
Park, N.C. 27711.
8. Zolner, W. J. Quenching in a Fluorescent Instrument.
Thermo Electron Corporation, 85 First Avenue, Waltham,
Mass. 17 pages.
9. Wright, R. J. and C. E. Decker. Analysis of EPA Protocol
No. 1 Gases for Use as EPA Method 6B Audit Materials.
Project Report under EPA Contract No. 68-02-4125, June
1986.
-------
Section No. 3.13.11
Date July 1, 1986
Page 2
10. Hines, A., EPA, Environmental Monitoring Systems Laboratory,
Research Triangle Park, NC 27711. Unpublished research.
11. Jayanty, R. K. M., J. A. Sokash, R. G. Fuerst, T. J. Logan,
and M. R. Midgett. Validation of an Audit Material for
Method 6B. Proceedings of APCA International Specialty
Conference on Continuous Emission Monitoring — Advances and
Issues, October 1985.
-------
Section No. 3.13.12
Date July 1, 1986
Page 1
12.0 DATA FORMS
Blank data forms are provided on the following pages for the
convenience of the Handbook user. Each blank form has the cus-
tomary descriptive title centered at the top of the page. How-
ever, the section-page documentation in the top right-hand corner
of each page of other sections has been replaced with a number in
the lower right-hand corner that will enable the user to identify
and refer to a similar filled-in form in a text section. For
example, Form M6A&B-1.2 indicates that the form is Figure 1.2 in
Section 3.13.1 (Methods 6A and B) of the Handbook. Future
revisions of these forms, if any, can be documented as 1.2A,
1.2B, etc. Fifteen of the blank forms listed below are included
in this section. Five are in the Method Highlights subsection as
shown by the MH following the form number.
Form Title
1.2 Procurement Log
2.2 Wet Test Meter Calibration Log
2.4 A&B Dry Gas Meter Calibration Data Form
(English and metric units)
2.5 (MH) Pretest Sampling Checks
3.1 (MH) Pretest Preparations
4.1 Field Sampling Data Form for
Method 6A
4.2 Method 6B Sampling, Sample Recovery,
and Sample Integrity Data Form
4.3 Method 6A Sample Recovery and
Integrity Data Form
4.6 Sample Label
4.7 (MH) On-Site Measurements for Method 6A
4.8 (MH) On-Site Measurements for Method 6B
5.1 (MH) Posttest Sampling Checks
5.2 Sulfur Dioxide Analytical Data Form
5.3 Control Sample Analytical Data Form
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Section No. 3.13.12
Date July 1, 1986
Page 2
5.4 (MH) Posttest Operations
6.1 Method 6A and 6B Calculation Form
(Conversion Factors)
6.2A & 6.2B Method 6A and 6B Sulfur Dioxide
Calculation Form (English and metric
units)
8.2 Method 6A and 6B Checklist to Be
Used by Auditors
-------
PROCUREMENT LOG
Item description
Qty-
Purchase
order
number
Vendor
Date
Ord.
Rec.
Cost
Disposition
Comments
Quality Assurance Handbook M6A&B-1.2
-------
WET TEST METER CALIBRATION LOG
Wet test meter serial number
Date
Range of wet test meter flow rate
Volume of test flask V_ =
O •••^•yi ,i !••»•.
Satisfactory leak check?
Ambient temperature of equilibrate liquid in wet test meter and reservoir
Test
number
1
2
3
Manometer
reading, a
mm H2O
Final
volume (V^ ) ,
L
Initial
volume (Vi),
L
Total
volume (Vm)b,
L
Flask
volume (V_),
5
L
Percent
error,0
%
Must be less than 10 mm (0.4 in.) H2O.
Vm = Vf - V,.
m f i
% error =• 100 (Vm - V0)/Ve =
m s s •••« ••••^•^•^ " •"'
(+1%).
Signature of calibration person
Quality Assurance Handbook M6A&B-2.2
-------
Date
DRY GAS METER CALIBRATION DATA FORM (ENGLISH UNITS)
Calibrated by Meter box number Wet test meter number
Barometer pressure, P =
in. Hg Dry gas meter temperature correction factor
Wet test
meter
pressure
drop
(Dm>'a
in. H-O
Rota-
meter
setting
(Rs),
ft3/min
Wet test
meter gas
volume
< V
and Yr =
(Eq. 4)
Quality Assurance Handbook M6A&B-2.4A
-------
DRY GAS METER CALIBRATION DATA FORM (METRIC UNITS)
Date
Calibrated by
Meter box number
Wet test meter number
Barometer pressure, P =
in. Hg Dry gas meter temperature correction factor
Wet test
meter
pressure
drop
'a
mm H2O
Rota-
meter
setting
»
°C
Dry test meter
Outlet
gas temp
|
-------
FIELD SAMPLING DATA FORM FOR METHOD 6A
Plant name
Sample location
Operator
Barometric pressure, mm (in.) Hg_
Probe material
Meter box number
Ambient temperature, C ( F)
Initial leak check
Final leak check
City
Date
Sample number
Probe length m (ft)
Probe heater setting
Meter calibration factor (Y)
Sampling point location
Sample purge time, min
Remarks
Sampling
time,
min
Total
Clock
time,
24 h
Sample
volume ,
L (ftj)
Total
Sample
flow rate
setting,
L/min
(ft3/min)
Sample
volume
metered
'M'
L (ft*)
V
m
avg
Percent
deviation , a
%
Avg
dev
Dry gas
meter
temp,
°C (8F)
Avg
Impinger
temp,
°C (°F)
Max
temp
a Percent deviation = m m avg x 100 (must be within 10 percent)
V avg
m
Quality Assurance Handbook M6A&B-4.1
-------
METHOD 6B SAMPLING, SAMPLE RECOVERY, AND
SAMPLE INTEGRITY DATA FORM
Plant
Sample location
Operator
Run No.
Sampling period
Dry Gas Meter
Final reading
Initial reading"
Volume metered
Initial leak check
Final leak check
Recovery date
Recovered by
Start:
Stop:
L
~L
L
Date
Date
Rotameter
Initial setting
Final setting
Time
Time
Dry Gas Meter Calibration Factor, Y
Meter Temperature
Barometric Pressure
"time
L or cc/min
L or cc/min
in. Hg
time
Probe Temperature
Initial °F
Final °F
Filter Temperature
Initial °F
Final °F
Ascarite Column
Final wt g
Inital wt g
Net wt g of CO,
Moisture
Final wt
Initial wt
Net wt
1st bubbler
9
g
g
Total moisture
2nd impinger
g
3rd impinger
g
4th bubbler
_g
_g
g
% spent
H2°2
container no.
RECOVERED SAMPLE (If Applicable)
Liquid level
marked
Impinger contents
container no.
H20 blank
container no.
Samples stored and locked
Received by
Remarks
Liquid level
marked
Liquid level
marked
Date
Quality Assurance Handbook M6A&B-4.2
-------
METHOD 6A SAMPLE RECOVERY AND INTEGRITY DATA FORM
1st bubbler
Final wt g
Initial wt
Net wt
g
g
2nd impinger
g
g
g
Total moisture
Ascarite
column:
Final wt
Initial wt
Net wt
3rd impinger
g
g
g
g
g
%
g
g
of C02
spent
4th bubbler
g
g
g
% spent
Recovered Sample
H202 blank
container no.
Impinger contents
container no.
H20 blank
container no.
Liquid level
marked
Liquid level
marked
Liquid level
marked
Samples stored and locked
Remarks
Received by
Remarks
Date
Quality Assurance Handbook M6A&B-4.3
-------
SAMPLE LABEL
Plant City
Site Sample Type
Date Run Number
Front rinse LJ Front filter LJ Front solution O
Back rinse LJ Back filter LJ Back solution LJ
Solution Level marked 1 — 1 Q
>_i
Volume: Initial Final a
••• " — £
Cleanup by $
Quality Assurance Handbook M6A&B-4.6
-------
Plant
SULFUR DIOXIDE ANALYTICAL DATA FORM
Date
Sample location
Volume and normality of
Standardization blank
Analyst
barium perchlorate
ml (< 0.5 ml)
1
2
3
ml
ml
ml
N
N
N
N, avg
Sample
number
1
2
3
4
5
6
Field
Blank
Sample
identification
number
Total
sample
volume
(Vsoln> '
ml
N/A
Sample
aliquot
volume
(va)a
ml
Volume of titrant (V ) , ml
t
1st
titration
2nd
titration
Average
Vtb =
Volume for the blank must be the same as that of the sample aliquot.
b 1st titration
titration _ 2nd titration <0.2 ml.
2nd titration
Signature of analyst
Signature of reviewer or supervisor
Quality Assurance Handbook M6A&B-5.2
-------
CONTROL SAMPLE ANALYTICAL DATA FORM
Plant
Analyst
Date analyzed
N,
'Ba(C104)2
Weight of ammonium sulfate is 1.3214 g?
Dissolved in 2 L of distilled water?
Titration of blank
ml Ba(Cl04)2 (must be <0.5 ml)
Control
sample
number
Time of
analysis,
24 h
Titrant volume, ml
1st
2nd
3rd
Avg
Two titrant volumes must agree within 0.2 ml.
(ml Ba(Cl04)2 - ml Blank) x NBa( = 25 ml x 0.01N
(control) (control
sample) sample)
ml -
ml) x
N =
(must agree within 5%, i.e., 0.238 to 0.262)
Does value agree? yes no
________ Signature of analyst
Signature of reviewer
Quality Assurance Handbook M6A&B-5.3
-------
METHOD 6A AND 6B CALCULATION FORM (CONVERSION FACTORS)
METER VOLUME (metric to English)
V = . liter
m 3 3
V = V (in liters) x 0.03531 ft /liter = . ft
m _____
METER TEMPERATURE (metric to English)
tm = [tm (°C) x 1.8] + 32 = . _ °F
T = t (°F) + 460 = . °R
mm — — — —
BAROMETRIC PRESSURE (metric to English)
pbar ' • nun Hg
Pbar = Pbar (mm Hg) x 0.03937 in. Hg/mm Hg = . in. Hg
METER VOLUME (English to metric)
vm = _ . _____ ft3
Vm = Vm (ft3) x °-02832 m3/"3 = . _____ m3
METER TEMPERATURE (English to metric)
tm = [tm (°F) - 32] x 5/9 = _ _ . _ °C
Tm ' *« <°C> + 273 - ___ - - °K
BAROMETRIC PRESSURE (English to metric)
p
bar _ _ • _ _ -
Pbar = Pbar ^in* Hg^ x 25*4 mm Hg/in. Hg = ___ . mm Hg
Quality Assurance Handbook M6A&B-6.1
-------
METHOD 6A AND 6B CALCULATION FORM (ENGLISH UNITS)
STANDARD METER VOLUME (English units)
Vm = _ • «, Y =
Pbar =__•__ in. Hg, Tm = . _ °R
V (std) = 17.64 V Y
m m
bar
Tm
dscf
C02 VOLUME COLLECTED, STANDARD CONDITIONS
(English units)
maf = • _ 9' mai = • _ 9
V.,-. (std) = 0.01930 (m _ - m . ) = . dscf
\^\J OI O.1 ~~ — "~~ — ~"~
Equation 6-1
C02 CONCENTRATION (percent by volume)
C- . Xctd) x 100 = __.__%
2 VStd> + VC02
Equation 6-4
S02 CONCENTRATION (English units)
Vt = . ml, Vtb = _. m1' N = _•__.__ (g-eq)/ml
V , = . ml, V = .ml
soln — — — — a — — —
c = 7.061 x IP"5 (Vt - Vtb)N/Vsoln\ _ ^ x 1Q-4 lb/dscf
S02 vm(std) + vro (std) a
m v-u2
Equation 6-3
Quality Assurance Handbook M6A&B-6.2A
-------
METHOD 6A AND 6B CALCULATION FORM (ENGLISH UNITS)
(continued)
MOISTURE CONCENTRATION (percent)
m f — . g, m . = . g
Vr £ '™~ ~~ """" ~~ Vr A ~~ ™~~ ^^ ™"
Vw(std) = °-04707 (mwf - mwi> = • dscf Equation 6-2
VH^O(std) x 100 = . %
mm£» . mm ~~ ~~ ^~* ^~
Equation 6-5
'H2° Vm(std) + VH20(std) + VCO2(std)
EMISSION RATE OF SO2 (English units)
(using meter volumes)
F = scf of C02/million Btu
E__ = C__ F^ 10° = . Ib S00/million Btu
oU~ £>\J~ C — — — — — Z
(not using meter sample volume)
FC = scf of CO2/million Btu
mso = 32.03 (Vt - Vtb)N /V8Ql \= . mg of S02 collected
2 \v /
Equation 6-6
Eco = F^ (1.141 x 10~3) mcri = . Ib S00/million Btu
Ow^ C O\JA "~" -"• £*
(maf ' ma7)
Equation 6-7
S02 CONCENTRATION (ppm)
CSQ (ppm) = CS02 v—/ —^ = . _ ppm
2 1.663 x 10~7
Quality Assurance Handbook M6A&B-6.2A
-------
METHOD 6A AND 6B CALCULATION FORM (METRIC UNITS)
STANDARD METER VOLUME (metric units)
(using meter volumes)
Vm = . liter x 0.001 = _ . m3
Y = _ - - Pbar = • mm Hg, Tm _ _ _ . _ °K
Vm(std) = 0.,3858 V Y Pbar = . dscm
in in —i — ~~ *^~ -~~ ~~ -"•••
Tm
C02 VOLUME COLLECTED, STANDARD CONDITIONS
(metric units)
VCQ (std) = 5.467 x 10~4(n»af - ma±) = . dscm
Equation 6-1
C02 CONCENTRATION (percent by volume)
VCO
-------
METHOD 6A AND 6B CALCULATION FORM (METRIC UNITS)
( continued )
MOISTURE CONCENTRATION (percent)
mwf = --- • _ 9- mwi = --- • _ 9
Vm(std) - 1-336 X 10 (mwf - VL* = • ----- dscm
Equation 6-2
Cu n = H-O _ x 100 = . %
U
V + V + V
vm(std) H20(std) C02(std)
EMISSION RATE OF S02 (metric units)
(using meter volumes)
_7
F = . x 10 dscm of C00/J
c ~~ ~~* ~~~ ™~ ^
Q
ES02 - CS02 Fc ^~= --- '
C02
(not using meter volumes)
F = x 10~7 dscm of C00/J
Equation 6-5
= 32.03 (Vt - Vtb) N/Vsoln\= ___ . __ mg of S02 collected
= FC (1.829 x 10') mSQ = . _ ng/J
(maf ~ mai)
dl. d.L
Equation 6-6
Equation 6-7
Quality Assurance Handbook M6A&B-6.2B
-------
METHOD 6A AND 6B CHECKLIST TO BE USED BY AUDITORS
Yes
No
Comment
Presampling Preparation
1. Knowledge of-process conditions
2. Calibration of pertinent equipment, in particular, the
dry gas meter, prior to each field test
On-Site Measurements
3. Leak testing of sampling train after sample run
4. Preparation and addition of absorbing solutions to
impingers
5- Constant rate sampling (for Method 6A only)
6. Purging of the sampling, train and rinsing of the
impingers and connecting tubes to recover the sample (for
Method 6A only)
7. Recording of pertinent process conditions during sample
collection
8. Maintaining the probe at a given temperature
Postsampling
9. Control sample analysis—accuracy and precision
10. Sample aliquoting techniques
11. Titration technique, particularly endpoint precision
12. Use of detection blanks in correcting field sample
results
13. Weighing of the CO- absorbant
14. Calculation procedure/check
15. Calibration checks
16. Standardized barium perchlorate solution
17. Result of the audit sample
General Comments
Quality Assurance Handbook M6A&B-8.2
•&U.S. GOVERNMENT PRINTING OFFICE: 1988 - 548-ISS/87028
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