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
                                          Date September 23,  1985
                                          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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                                          Section No. 3.0.5
                                          Date September 23,  1985
                                          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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                                          Section No. 3.0.5
                                          Date September 23, 1985
                                          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
                                          Date September 23,  1985
                                          Page 55

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
                                          Page 56

     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
                                          Date September 23,  1985
                                          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
                                          Date September 23, 1985
                                          Page 10
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
                                          Date September 23, 1985
                                          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).

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                                          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)

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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.

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                                                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.

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                                                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.

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                                                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.

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                                                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.

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                                                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.

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                                               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






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J ^
§t ^
1 A 1
i1 i
M
li I
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i1




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R "
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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
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ABSORBER


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r'
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=O^











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                                                                                       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.

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                                                              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  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)

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                                                                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.

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                                                                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

-------
                                          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

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           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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