United States Environmental Monitoring Systems
Environmental Protection Laboratory
Agency Research Triangle Park NC 27711
Research and Development EPA/600/4-77/027b August 1988
&EPA Quality Assurance
Handbook for
Air Pollution
Measurement
Systems:
Volume III. Stationary
Sources Specific
Methods
Sections 3.0.1, 3.0.2
3.0.3, 3.0.4,
3.5, 3.6, and
3.7
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Pollution Measurement Systems has been prepared under Document
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August 1988
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
x (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
Section
Table of Contents (continued)
Pages
Date
9
19
7
10
4
8
3
4
1
5
1
14
1-15-80
1-15-80
1-15-80
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1-15-80
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1-15-80
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1-15-80
1-15-80
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
3.2.7 Maintenance 1 1-15-80
3.2.8 Auditing Procedure 5 -15-80
3.2.9 Recommended Standards for 1 -15-80
Establishing Traceability
3.2.10 Reference Method 3 -15-80
3.2.11 References 1 -15-80
3.2.12 Data Forms 6 -15-80
3.3 Method 4—Determination of Moisture
in Stack Gases
3.3.1 Procurement of Apparatus and Supplies
3.3.2 Calibration of Apparatus
3.3.3 Presampling Operations
3.3.4 On-Site Measurements
3:3.5 Postsampling Operations
3.3.6 Calculations
3.3.7 Maintenance
3.3.8 Auditing Procedure
3.3.9 Recommended Standards for
Establishing Traceability
3.3.10 Reference Method
3.3.11 References
3.3.12 Data Forms
3.4 Method 5—Determination of Paniculate
Emissions from Stationary Sources
3.4.1 Procurement of Apparatus and 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
Section
Table of Contents (continued)
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
3.10.2 Calibration of Apparatus
3.10.3 Presampling Operations
3.10.4 On-Site Measurements
3.10.5 Postsampling Operations
3.10.6 Calculations
3.10.7 Maintenance
3.10.8 Auditing Procedure
3.10.9 Recommended Standards for
Establishing Traceability
3.10.10 Reference Method
3.10.11 References
3.10.12 Data Forms
3.11 Method 17—Determination of Paniculate
Emissions from Stationary Sources
(In-Stack Filtration Method)
Procurement of Apparatus and Supplies
Calibration of Apparatus
Presampling Operations
On-Site Measurements
Postsampling Operations
Calculations
Maintenance
Auditing Procedure
Recommended Standards for
Establishing Traceability
3.11.10 Reference Method
3.11.11 References
3.11.12 Data Forms
3.12 Method 9—Visible Determination of
the Opacity Emissions from
Stationary Sources
3.11
3.11
3.1
3.1
3.1
3.1
3.1
3.11.8
3.11.9
13
5
3
3
18
7
2
1
1
5
1
6
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1-04-82
1-04-82
1-04-82
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2
3
6
1
1
2
2
1
11
1
1
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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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Jan. 1982 vii
Purpose and Overview of the Quality Assurance Handbook
The purpose of this Quality Assurance Handbook for Air Pollution Measurement
Systems is to provide guidelines and procedures for achieving quality assurance in
air pollution measurement systems. It is intended to serve as a resource document
for the design of quality assurance programs and to provide detailed method
descriptions for certain measurement processes that can be used directly in
implementing the quality assurance program.
This Handbook should be particularly beneficial to operators, project officers, and
program managers responsible for implementing, designing, and coordinating air
pollution measurement studies. The contents of each volume are briefly described
in the following paragraphs.
Volume I - Principles
Volume I contains brief discussions of the elements of quality assurance.
Expanded discussions of technical points and sample calculations are included in
the Appendixes. The discussion of each element is structured to be brief and to
highlight the most important features. Organizations developing and implementing
their own quality assurance programs will find Volume I useful for general
guidance.
Volume II - Ambient-Air-Specific Methods
Volume II contains quality assurance guidelines on ambient air measurement
systems. Regardless of the scope and magnitude of ambient air measurement
systems, there are a number of common considerations pertinent to the production
of quality data. These considerations are discussed in Section 2.0 of Volume II, and
include quality assurance guidelines in the areas of:
1. Sampling network design and site selection - monitoring objectives and spatial
scales; representative sampling; meteorological and topographical
constraints; and sampling schedules.
2. Sampling considerations - environmental controls; probeand manifold design;
maintenance; and support services.
3. Data handling and reporting considerations - data recording systems, data
validation, and systematic data management.
4. Reference and equivalent methods.
5. Recommended quality assurance program for ambient air measurements.
6. Chain-of-custody procedure for ambient air samples - sample collection;
sample handling; analysis of the sample; field notes; and report as evidence.
7. Traceability protocol for establishing true concentrations of gases used for
calibrations and audits - establishing traceability of commercial gas cylinders
and of permeation tubes.
8. Calculations to assess monitoring data for precision and accuracy for SLAMS
and PSD automated analyzers and manual methods.
9. Specific guidance for a quality control program for SLAMS and PSD for
automated analyzers and manual methods - analyzer selection, calibration,
zero and span checks; data validation and reporting; quality control program for
gaseous standards and flow measurement devices.
10. EPA national performance audit program.
11. System audit criteria and procedures for ambient air monitoring programs.
12. Performance audit procedures for use by State and local air monitoring
agencies.
The remainder of Volume II contains method and/or principle description and
quality assurance guidelines for specific pollutants. Each pollutant-specific section
contains the following information.
1. Procedures for procurement of equipment and supplies.
2. Calibration procedures.
3. Step-by-step descriptions of sampling, reagent preparation, and analysis
procedures, as appropriate, depending upon the method or principle in the case
of equivalencies.
4. Method of calculation and data processing checks.
5. Maintenance procedures.
6. Recommended auditing procedures to be performed during the sampling,
analysis, and data processing.
7. Recommended procedure for routine assessment of accuracy and precision.
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viii Jan. 1982
8. Recommended standards for establishing traceability.
9. Pertinent references.
10. Blank data forms for the convenience of the Handbook user (data forms are
partially filled in within the text for illustration purposes).
Matrix tables at the ends of appropriate sections summarize the quality
assurance functions therein. Each matrix includes the activities, the acceptance
limits, method and frequency of each quality assurance check, and the
recommended action if the acceptance limits are not satisfied.
Volume II contains quality assurance guidelines for pollutant-specific
measurement systems. The measurement systems planned for Volume II include:
1. Reference Method for the Determination of Sulfur Dioxide in the Atmosphere
(Pararosaniline Method).
2. Reference Method for the Determination of Suspended Particulates in the
Atmosphere (Hi-Vol Method).
3. Reference Method for the Determination of Nitrogen Dioxide in the
Atmosphere (Chemiluminescence).
4. Equivalent Method for the Determination of Nitrogen Dioxide in the
Atmosphere (Sodium Arsenite).
5. Equivalent Method for the Determination of Sulfur Dioxide in the Atmosphere
(Flame Photometric Detector).
6. Reference Method for the Determination of Carbon Monoxide in the
Atmosphere (Nondispersive Infrared Spectrometry).
7. Reference Method for the Determination of Ozone in the Atmosphere
(Chemiluminescence).
8. Reference Method for the Determination of Lead in Suspended Paniculate
Matter Collected from Ambient Air (Atomic Absorption Spectrometry).
9. Equivalent Method for the Determination of Sulfur Dioxide in the Atmosphere
(Fluorescence).
As methods are added to Volume II, these will be sent to Handbook users through
the document control system, as described in Section 1.4.1 of Volume I of this
Handbook.
Volume III - Stationary-Source-Specific Methods
Volume III contains quality assurance guidelines on stationary-source-specific
methods. The format for Volume III is patterned after that of Volume II.
Regardless of the scope and purpose of the emissions-testing plan, there are a
number of general considerations pertinent to the production of quality data. These
considerations are discussed in Section 3.0 of Volume III and include quality
assurance guidelines in the areas of:
1. Planning the test program - preliminary plant survey; process information;
stack data; location of sampling points; cyclonic gas flow.
2. General factors involved in stationary source testing - tools and equipment;
standard data forms; and identification of samples.
3. Chain-of-custody procedures for source sampling - sample collection; sample
analysis; field notes; and report as evidence.
4. Traceability protocol for establishing true concentrations of gases used for
calibrations and audits of air pollution analyzers - establishing traceability of
commercial gas cylinders.
5. Specific procedures to assess accuracy of Reference Methods used for SPNSS.
6. Specific procedures to assess accuracy of Reference Methods used for
NESHAP.
7. Interpretation and application of CEM precision and accuracy data.
The remainder of Volume III contains quality assurance guidelines for specific
measurement methods. The measurement systems planned for Volume III include:
Method 2 - Determination of Stack Gas Velocity and Volumetric Flow Rate (Type-S
Pilot Tube).
Method 3 - Gas Ana lysis for Carbon Dioxide, Oxygen, Excess Air, and Dry Molecular
Weight.
Method 4 - Determination of Moisture in Stack Gases.
Method 5 - Determination of Paniculate Emissions from Stationary Sources.
Method 6 - Determination of Sulfur Dioxide Emissions from Stationary Sources.
Method 7 - Determination of Nitrogen Oxide Emissions from Stationary Sources.
Method 8 - Determination of Sulfuric Acid Mist and Sulfur Dioxide from Stationary
Sources.
Method 9 - Visual Determination of the Opacity of Emissions from Stationary
Sources.
Method 10-Determination of Carbon Monoxide Emissions from Stationary
Sources.
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Jan. 1982
Methods 13A and B - Determination of Fluoride Emissions from Stationary Sources
(SPADNS and Specific Ion Electrode).
Method 17- Determination of Paniculate Emissions from Stationary Sources (In-
Stack Filtration Method).
As methods are added to Volume III, these will be sent to the users through the
document control system used for the Handbook.
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5-01-79
1
Section 3.0.0
&EPA
United States
Environmental Protection
Agency
Environmental Monitoring Systems
Laboratory
Research Triangle Park NC 27711
Research and Development
Section 3.0
General Aspects of
Quality Assurance for
Stationary Source Emission
Testing Programs
Outline
Section
Summary
General Quality Assurance Guidelines
1. Planning the Test Program
2. General Factors Involved In
Stationary Source Testing
3. Chain-of-Custody Procedure
for Source Sampling
4. Traceability Protocol for
Establishing True Concentra-
tions of Gases Used for Cali-
brations and Audits of Con-
tinuous Source Emission Mon-
itors (Protocol No. 1)
Summary
Section 3.0 provides guidelines for
quality assurance in performance of
emission testing of stationary sources
by federally prescribed procedures. The
guidelines may be applied to all cate-
gories of sources commonly monitored.
The purpose of emission testing (also
called "source sampling" or "stack
sampling") is to extract from the stack or
duct a sample that is representative of
emissions from that source during a
time period in which the process is
under a desired operating condition.
The sampling methods prescribed by
Federal agencies are for specific sub-
stances and types of sources, and are
designed to provide representative and
reliable data. Since the Federal New
Source Performance Standards are
promulgated from data obtained by
these methods, adherence to these
standard procedures for sampling and
analysis is essential.
Although personnel engaged in
emission testing learn to perform these
Documentation
3.0.1
3.0.2
3.0.3
3.0.4
Number
of Pages
11
2
7
3
tests routinely, some of the procedures
may not be readily understood by
laymen who are involved in hearings or
litigations concerning an emission
source. When an enforcement agency
must rely on results of emissions
testing, the test results may be subjected
to the requirements of legal rules of
evidence. Emissions monitoring per-
sonnel, therefore, should not only
follow standard testing procedures but
should also document each step of the
test by maintaining complete and
accurate records.
The following guidelines for assurance
of high quality emissions test data are
presented in four major phases: planning
the test program, performing the test,
chain-of-custody procedure, and estab-
lishing the traceability of calibration
gases. Specific method descriptions are
given in subsequent sections of this
Handbook.
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5-01-79
Section 3.0.1
General Quality Assurance Guidelines
1.0 Planning the Test Program
Although a detailed and specific plan
will be developed for each test program,
the factors discussed here apply to all
cases and provide a basis for formulation
of a test plan.
The reason for conducting the emis-
sion test must first be carefully deter-
mined. Data may be required to check
for compliance with a specific regula-
tion, to measure process stream losses,
or to obtain engineering data for
designing control equipment. The
guidelines presented in this Handbook
are designed to provide more accurate
data regardless of the test purpose. The
test methods discussed here are those
used to determine compliance with U.S.
EPA emission regulations. These meth-
ods can also be used in other applica-
tions, but caution must be exercised
against overloading the equipment due
to higher pollutant concentrations or
introducing interferences.
For compliance testing, the first
planning step is to determine the
applicable emission control regulation.
Since most control regulations desig-
nate specific process conditions to be
monitored and recorded as part of a
valid emission test, a thorough under-
standing of the regulation is a pre-
requisite to formulating the sampling
plan. Monitoring personnel may be-
come familiar with specific
industry operations and the required
test data through inspection manuals
published by EPA.
1.1 Preliminary Plant Survey
The next step in developing the test
program is a preliminary survey of the
process and the test site. Except in the
most routine cases, an on-site inspec-
tion or presurvey should be performed
to determine process information,
emission parameters, and locations of
sampling points. The presurvey may be
made by telephone, particularly when
the monitoring personnel have had
experience with the specific industry/
process.
Considerable information concerning
the process to be monitored may be
gained in advance of the on-site survey
by consulting a registration form or
permit application pertaining to the
plant operations. These forms provide
valuable data on process throughput,
emission factors, material balances,
types and sizes of fans and motors, and
similar items. From these data, one can
often estimate gas flow rates and
compositions of effluents. For testing of
new sources, the plant's construction
permit may provide a guide to locations
of test ports and scaffolding.
A further step in preparing for the on-
site survey is to assemble the equip-
ment that may be required to obtain
preliminary data such as:
1. A 10°-to-650°C (50°-to-1200°F)
dial thermometer, 30-cm (12-in.)
stem.
2. Velocity meter (velometer, Pilot
tube, or anemometer).
3. A 15-m (50-ft) tape measure.
4. Set of basic shop tools.
5. Polaroid type camera.
6. Gas absorption colorimetric indi-
cator tubes for S02, CO, NOX, HC,
etc.
7. Survey data forms.
8. Safety equipment (hardhats, safety
shoes, goggles, etc.).
1.2 Process Information
One plant employee should be desig-
nated as the personal contact for
monitoring personnel. This person
should understand the process thor-
oughly and must have authority to
obtain information and to elicit the
cooperation of other plant personnel. A
member of the staff of the plant
manager or the plant engineer is often
an appropriate contact.
The on-site survey is greatly facilitated
by use of a survey form that lists the
process parameters. Figures 1.1 and 1.2
are example forms for use in the
presurvey of combustion and incinera-
tion sources. These forms are'general
guides; in many cases, additional
information will be available and should
be noted for possible future use.
When possible, the normal operation
of a process should be determined
during the survey. If a process varies
with time over a defined cycle, moni-
toring personnel should determine the
variation in emission parameters during
the cycle as a basis for deciding whether
to sample during part of a cycle, during
an entire cycle, or during several cycles.
If the process involves steady-state
operation, the level of operation to be
sampled should be determined. The
applicable control regulations may
indicate the process operating condi-
tions required for emissions tests. Most
regulations require sampling at rated
capacity. Any seasonal variations in
process conditions should be noted, as
should variations in feed stream com-
position or control device operation.
1.2.1 Stack Information - The sampling
site and the number of traverse points
designated will affect the quality of the
sample extracted. Site selection should
be simple for new installations, since in
most states one of the requirements for
obtaining a permit to construct is the
installation of an acceptable sampling
site. For new and existing installations,
acceptability of the sampling procedure
is generally determined by the distances
from the nearest upstream and down-
stream disturbances (obstruction or
change in direction) to gas flow. The
minimum requirements for an accep-
table sampling procedure are in Method
1, and are summarized herein.
In addition to flow considerations,
accessibility and safety are important.
Clearance for the probe and sampling
apparatus, availability of electricity,
exposure to weather or excessive heat,
presence of toxic or explosive gases,
and other safety factors must be
considered in selecting a site.
Detailed information is needed re-
garding the gas stream parameters at
the sampling site, especially in the
sampling of atypical processes. Figure
1.3 lists the stack data needed to
determine the required probe lengths
and any change in sampling equipment.
Most of the data can be obtained or
checked from plant blueprints or engi-
neering drawings, material-balance
calculations, process instrumentation
readings, or from comparable data
obtained for similar processes. When no
data can be obtained from these or other
sources, exit gas parameters may be
determined by inserting a velocity probe
(Pitot tube, anemometer, or velometer)
and a thermometer into the duct at or
near the test site to determine approxi-
mate velocity and temperature. Color-
change-type gas indicator tubes and a
squeeze bulb sampler can be used to
determine approximate concentrations
of a wide variety of gases, and are useful
if estimates based on process param-
eters cannot be made. These can also be
used for ambient air sampling to
determine any potential employee
exposure problems.
1.2.2 Location of Sampling Points -
As mentioned earlier, emission tests
-------
Section 3.0.1
5-01-79
Type ol Heat Exchanger
Coal fired
Oil fired
Gas fired
Primary Standby
D D.
D D
D D
If multiple fired, check appropriate boxes
Rfltprf input rnpncity
Maximum operating rate
Rfitffrl ftfifim ftf'tfU/t
Maximum steam output
Furnace volume width
nnerntinn srheriuln
ft y riaplh
h/rlay
Rlu/h
ain/h
Ih/h ffl
Ih/h (3>
ft x height
tiays/wk w/lt/yr
Rtn//t> steam
Coal Firing
Oil Firing
Type of firing D Grate Type
D Spreader stoker
O Pulverized coal D Dry bottom D Wet Bottom
D Cyclone
Fly ash reinjection Yes No
Soot blowing
Continuous Q Q
Intermittent D D
Time interval between blowing min
Duration min
Outside coal storage D Yes
Maximum amount stored outside
Outside storage sprayed D Yes
Coal consumption Range
Ash %to
Sulfur % to
Btu/lb as fired to
O No
tons
a NO
Average
Fuel consumption records kept D Yes
For stoker system. Coal size
For pulverized coal and cyclone system.
Firing method
O No
Firing method
D Front wall
D Front wall - rear wall
DA II wall
D Front wall
D Front wall - rear wall
O A/I wall
D Tangential
D Other
Type
D Tangential
D Cyclone
D Other
Type of fuel
O No. 1
D/Vo. 2
a No. 4
O No. 5
Type
Type
O No. 6
D Other
Figure 1.1. Example of a presurvey data form for fossil fuel-fired steam generators.
-------
5-01-79
Section 3.0.1
Facility name
Facility address
Name of plant contact .
Source code number _
Unit designation
Design charge rate .
Actual charge rate .
Inspection date —
A. Pre-entry Observations
Time
Stack plume fuse EPA plume observation procedures/
Opacity regulation D In compliance D Not in compliance
Weight scales
D Operating D Not operating
Trucks weighed and recorded before dump D Yes D No
Trucks weighed and recorded after dump Q Yes D No
B. Control Equipment
1) Electrostatic precipitator
Section
Primary current, A
Primary voltage, V
Secondary current, mA
Secondary voltage, kV
Spark rate, spk/min
2) Scrubber
Module
Liquid flow, gal/min
Pressure across scrubber, in. HiO
3) Fabric filter
Compartment
Pressure drop across fabric
filter, in. H2O
Figure 1.2. Example of a presurvey data form for municipal incinerators.
-------
Section 3.0.1
5-01-79
Additional observations:
C. Control Panel
Time
Secondary chamber temperature
APC device entry temperature
Underfire air draft
Overfire'air draft
Oi analyzer
COi analyzer
CO analyzer
Grate speed
Refuse measuring sensors
°F
°F
in. H2O
.in.
(indicate units)
(indicate units)
D. Incinerator
Charge cranes
Furnace grates (if visible)
Residue removal system (including quenching)
Time
Satisfactory Unsatisfactory
D D
D D
a a
E.
Records
Temperature charts (dated and filed by incineratory personnel)
Secondary chamber
APC device entry gas
Hours of operation
Satisfactory Unsatisfactory
a a
a a
Charging rate. T/h
Daily collection. T/day
Figure 1.2. (continued)
are based on the assumption that the
sample obtained at a given point is
representative of the concentration at
that point. Therefore, a system in which
concentrations are nonuniform with
respect to the stack cross-sectional area
will require more sampling points than
will a system with uniform concentra-
tions. Usually, gaseous concentrations
are fairly uniform across a duct's cross
section, and a single sampling point is
sufficient. To obtain representative gas
velocities and particulate concentra-
tions, traversing of the duct cross-
sectional area is required, as described
in the Reference Methods 1 and 2.
Figure 1.4 can be used as a basis for
determining the number of sampling
points required for representative
sampling of a given system for parti-
culate and nonparticulate emissions.
First, measure the distances (in duct
diameters) from the sampling port to the
nearest upstream and downstream
disturbances, and determine the cor-
responding number of traverse points
for each distance (Figure 1.4). Select
either the higher of the two numbers of
traverse points or a greater even value.
For round ducts, select a number that is
a multiple of four, andplace half of these
points along each of two diameters that
are at right angles to each other. The
exact sample point locations for round
ducts can then be determined by using
the percentage of stack diameter from
the duct's inside wall to the traverse
point, as shown in Table 1.1. Duct
diameters should be checked along two
directions. If the two measurements are
similar, use an average value. If they are
not similar, use each separate diameter
in determining point locations. Figure
1.5 may be used for calculating the
distances to each traverse point by
multiplying the percentage from Table
1.1 by the stack diameter. The total
distance to the point from the outside of
the stack or port is obtained by adding
the port length and stack wall thickness
to the calculated point location. No
sampling point should be either <1 in.
from an inner wall for stacks >24 in. in
diameter, or <0.5 in. (or a distance
equal to the sampling nozzle diameter
from the wall) in stacks <24 in. in
diameter.
For rectangular ducts, an equivalent
diameter is calculated from the following
equation to determine the distance to
disturbances in terms of duct diameters:
Equivalent diameter =
2 f length x width"!
(length + width J
The minimum number of traverse
points is then determined in the same
manner as it is for circular stacks, with
the use of Figure 1.4. The rectangular
cross section is then divided into equal
rectangular areas, according to the
values in Table 1.2. Studies referenced
in Method 1 show that velocity measure-
ment data quality is not significantly
increased by traversing 48 points
versus 24 points for acceptable flow
conditions. The studies also show that
four traverse points along a line
-------
5-01-79
Section 3.0.1
Stack (Vent) Number
Parameter
Process vented
Platform height, ft
Platform width, ft
Platform length, ft
Inside diameter, in. at. port
Wall thickness, in. at port
Material of construction
Ports: a. Existing
b. Size opening
c. Distance from platform
Straight distance before ports, ft
Type of restriction before ports
Straight distance after ports, ft
Type of restriction after ports
Environment at sampling site
Work space area
Ambient temperature. °F
Average Pilot reading, in. HiO
and range in A/3
Stack gas velocity, ft/min
Stack gas flow. ft3/min
Moisture. % by volume
Stack gas temperature, °F
Paniculate loading, gr/scf
Particle size
Gases present
Stack Pressure, in. W20
Water sprays prior to site
Dilution air prior to site
Elevator to site!'
Available electricity and distance, ft
Value
Comments
Figure 1.3. Stack and gas stream data requirements.
-------
Section 3.0.1
5-01-79
Table 1 . 1 . Location of Traverse Points in Circular Stacks
Example Showing Circular Stack Cross Section Divided Into 12 Equal Areas With Location of Traverse Points Indicated.
Traverse *" ~ 6
point
Distance,
% of diameter
1
2
3
4
5
6
4.4
14.6
29.6
70.4
85.4
95.6
Percent of Stack Diameter from Inside Wall to Traverse Point
Traverse
point
number
on a
diameter"
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Number of
2 4 6 8 10
14.6 6.7 4.4 3.2
85.4 25.0 14.6 10.5
75.0 29.6 19.4
93.3 70.4 32.3
85.4 67.7
95.6 80.6
89.5
96.8
-
2.6
8.2
14.6
22.6
34.2
65.8
77.4
85.4
91.8
97.4
traverse
12
2.1
6.7
11.8
17.7
25.0
35.6
64.4
75.0
82.3
88.2
93.3
97.9
points on
14
1.8
5.7
9.9
14.6
20.1
26.9
36.6
63.4
73.1
79.9
85.4
90.1
94.3
98.2
a diameter*
16
1.6
4.9
8.5
12.5
16.9
22.0
28.3
37.5
62.5
71.7
78.0
83.1
87.5
91.5
95.1
98.4
18
1.4
4.4
7.5
10.9
14.6
18.8
23.6
29.6
38.2
61.8
70.4
76.4
81.2
85.4
89.1
92.5
95.6
98.6
20
1.3
3.9
6.7
9.7
12.9
16.5
20.4
25.0
30.6
38.8
61.2
69.4
75.0
79.6
83.5
87.1
90.3
93.3
96.1
98.7
22
1.1
3.5
6.0
8.7
11.6
14.6
18.0
21.8
26.2
31.5
39.3
60.7
68.5
73.8
78.2
82.0
85.4
88.4
91.3
94.0
96.5
98.9
24
1.1
3.2
5.5
7.9
10.5
13.2
16.1
19.4
23.0
27.2
32.3
39.8
60.2
67.7
72.8
77.0
80.6
83.9
86.8
89.5
92.1
94.5
96.8
98.9
^Points numbered from outside wall toward opposite wall.
*The total number of points along two diameters would be twice the number along a single diameter.
generally are representative of that
traverse line. These two determinations
allowed EPA to reduce the number of
traverse points required for velocity
measurement (as shown in Figure 1.4)
and to require a more even matrix
arrangement of sample points in a
square or rectangular duct (as shown in
Table 1.2). For small ducts requiring
many points, a slot may have to be cut
into one side of each duct with a sliding
port to accommodate all of the points.
The sampling points should be located
at the center of each equal area,
according to Figure 1.6. Many studies
have been conducted on the Pilot tube
and Method 1. See References 1
through 14.
The calculation and marking of
sampling points on the probe or Pitot
tube are very critical. If marked incor-
rectly, the sample probe may hit the
opposite stack wall, and the emission
results will probably be nonrepresenta-
tive.
1.2.3 Cyclonic Gas Flow - Location of
a suitable sampling site for velocity
measurement or for particulate and
mist determinations requires that the
gas flow be essentially parallel to the
stack walls. If there is a possibility of
cyclonic or nonparallel flow as deter-
mined by observation of the duct
system, checks with a Pitot tube and
draft gauge (see Section 3.1, Method 2)
should be made as follows:
1. Connect an acceptable type-S Pitot
tube to a manometer, and leak
check as described in Section 3.1,
Table 1.2. Layout of Cross-Sectional
Subareas in Rectangular
Ducts
Number of
traverse points"
9
12
16
20
25
30
36
42
49
Subarea
layout matrix
3x3
4x3
4x4
5x4
5x5
6x5
6x6
7x6
7x7
"From Figure 1.4.
-------
Revision based on the August 30, 1983 Federal Register (48 FR 45034)
0.5
DUCT DIAMETERS UPSTREAM FROM DISTURBANCE (DISTANCE A)'
1.0 1.5
2.0
2.5
** V
1—
S 40
Q.
LU
O£
£ 30
^> *JW
0.01 m (24 in.)
12
8 or 9* -
STACK DIAMETER = 0.30 to 0.01 m (.12-24 in.)
1 1 1 1 1
234567
1 !
8 9 10
DUCT DIAMETERS DOWNSTREAM FROM FLOW DISTURBANCE (DISTANCE B)a *a t) o » w
Q) 0) 0) CD CD
aFrom point of any type of disturbance (bend, expansion, contraction, etc.) CD CD CD H- ft
v] VO ^ H- O
(D O 3
^3 o n z
rr n c z o
MI n < H- o> o •
O CD CD (Q H| •
h •-' H™' 3 ^ t^
C >- ft
Figure 1.4. Minimum number of traverse points for velocity 3 J< ^
(Particulate and Nonparticulate) traverse.
»rf V^ 'fc'
(D 00
d Ul
-------
5-01-79
Section 3.0.1
Method 2. Carefully zero the ma-
nometer and insert the Pitot tube so
that the planes of the face openings
are perpendicular to the stack area
cross-sectional plane — that is,
parallel to the expected gas flow.
The Pitot tube is thus 90° from its
usual position.
2. Traverse the stack area by meas-
uring the velocity head at each
sampling point with the Pitot tube
in this position. Keep the sampling
port opening sealed with a rag or
sponge while traversing. Tempera-
ture need not be measured at this
time.
3. When the gas flow is exactly
parallel to the stack walls and
therefore parallel to the Pitot tube
face openings, no reading will be
obtained on the manometer. If a
reading is obtained, rotate the Pitot
tube around its longitudinal axis
until a zero reading is indicated on
the manometer.
4. Record the angle of rotation (start-
ing with 0° in the Pitot tube's initial
position), required to obtain a zero
manometer reading. Record data
on the Method 2 gas velocity and
volume data form (Figure 1.7 ).
5. Obtain an arithmetic average of the
angles of rotation at each traverse
point, including angles of 0° (Figure
1.7). If the average angle of rotation
is <10°, the gas flow conditions at
the sampling site are acceptable. If
the average angle is >10°, the flow
conditions are not acceptable;
another test site must befound, the
flow pattern must be modified by
installing flow straighteners or
consult the Administrator.
To facilitate measurement of Pitot
tube rotation, a number of devices can
be made, depending on the ingenuity of
the user. Fabrication of a protractor that
will fit over the sampling port along with
a movable indicating arm clamped to the
Pitot tube will provide a measurement of
the angle of rotation. A level indicator
(available at most hardware stores)
calibrated in 5-degree increments can
also be mounted on the Pitot tube and
used to measure rotation.
The preferred device is a degree
indicating level (available at most
hardware stores) with 1° increments
which can be mounted on the end of the
Pitot tube (Figure 1.8). Its alignment
with the head of the Pitot tube can be
checked by one of two methods. (1) The
use of two indicating levels, one at the
front and one at the end or (2) by placing
the Pitot on a stable surface'then place
the indicating level at the front and then
the end and compare readings. The
readings do not have to be the same.
The differential, using the front as the
reference, or true value can be sub-
tracted or added to the corresponding
angular determinations of stack flow.
-------
Section 3.0.1
5-01-79
Plant.
Date .
Sampling location .
Inside of far wall to outside
of port (distance. X) —
Inside of near wall to outside
of port (distance. Y)
Stack I.D. (distance X-distance Y).
Port -H' ii
Schematic of Sampling
Location
1
Traverse point
number
--
2
Percent of
stack I.D.
3
Stack I.D.
inches
4
Product of Columns 2 and 3
(to nearest '/s in.)
5
Distance
Y
6
Traverse point location from
outside of port
(sum of Columns 4 & 5)
Figure 1.5. Traverse point location calculation form for round ducts.
-------
5-01-79
Section 3.0.1
D,/
\
[\
\
\
\
\
\
^
\\\\\\\\\\\\\\\
^1 1 ^1 t
7 A / A °2/ A2 -
^M / ^H ^A ^
A ! A A J
1
A ! A A
1
1 1
VVI I\\\M I\V\M IV V
»
\\\\\
,l
H A
I*
J
i
i .
i_
! A
I
AVI i\\
V
\
\
\
s
s
\
\
\
\
I
D
1
1
2
where:
A = sampling point
ri, = number of areas across flue width
d2 = number of areas across flue perpendicular to width
Figure 1.6. Example showing rectangular stack cross section divided into twelve equal
areas, with a traverse point at the centroid of each area.
References
1. 40CFR60. July 1. 1978.
2. Determination of the Optional Num-
ber of Traverse Points: An Analysis of
Method 1 Criteria. Final Report, EPA
Contract No. 68-01-3172. Entropy
Environmentalists, Inc., April 1977.
3. Hansen, H.A., R.I. Davis, et al.
Particulate Sampling Strategies for
Large Power Plants Including Nonuni-
form Flow. EPA-600/2-76- 120, June
1976.
4. Smith, Franklin, Denny E.
Wagoner, et al. Guidelines for
Development of a Quality Assurance
Program: Volume I - Determination
of Stack Gas Velocity and Volumetric
Flow Rate (Type-S Pitot Tube). EPA-
650/4-74-005-a, February 1974.
5. Source Sampling Reference
Manual - Supplemental Training
Material for Technical Workshop on
Evaluating Performance Tests. EPA,
Division of Stationary Source
Enforcement, January 1977.
6. Stack Sampling Technical Informa-
tion: A Collection of Monographs and
Papers (Vols. II, IV). EPA-450/2-78-
042-b,d, October 1978.
7. Standards of Performance for New
Stationary Sources - A Compilation.
EPA Contract No. 68-01-4147. PEDCo
Environmental, Inc., Cincinnati, OH,
November 1977.
8. Williams, J.C., III and F. R. DeJarnette.
A Study on the Accuracy of Type-S Pitot
Tube, EPA-600/4-77-030, June 1977.
9. Folson, R. G. Review of the Pitot
Tube. Trans. ASME, 78, 1447-1459,
1956.
10. Ower, E. and F. C. Johansen.
Design of Pilot-Static Tubes. R and M,
No. 981, British A.R.C., 1925.
11. Merriam, K. F., and E. R. Spaulding.
Comparative Tests of Pitot Static Tubes.
NACATN 546,1935.
12. Vollaro, R. F. Use of Type-S Pitot
Tubes for the Measurement of Low
Velocities. U.S. Environmental Protec-
tion Agency, Research Triangle Park,
N.C. In-house Report, January 19,
1977.
13. Vollaro, R. F. A Survey of Geometric
and Aerodynamic Factors Which Can
Affect Type-S Pitot Tube Accuracy. U.S.
Environmental Protection Agency,
Research Triangle Park, N.C., In-house
Report, February 17, 1978.
14. Leland, B. J., J. L. Hall, A. W.
Joensen, and J. M. Carroll. Correction of
S-Type Pilot-Static Tube Coefficients
When Used for Isokinetic Sampling
from Stationary Sources. ES&T, 7 7,
694-700, 1977.
-------
Section 3.0.1
10
5-01-79
Plant and city
Run date
|
/
|
/
|
Sampling location
Clock time
Run number
Operator
Amb. temp.,
°F
Bar press.,
in. Hg
Static press.,
in. H2O
Molecular
wt.
I I I I
Stack inside dimension, in.
Diam. or side 1
I I I I I
side 2
I I I I I
Pilot
tube (Cp)
I I
Field data
Traverse
point
number
Position,
in.
Velocity head
CA/*J.
in. HjO
Stack temp.,
°f
Cyclonic flow determination
A/JS at 0°
reference
A verage angle la)"
Angle (a)
which yields
a null Ap
"Average of (a) must be < 10 degrees to be acceptable.
Figure 1.7. Method 2 gas velocity and volume data form.
-------
6-01-79
11
Section 3.0.1
- Pilot tube
Degree indicating
level —v
\
Degree indicating level
(with 1° increments)
oo
Pilot tube
Figure 1.8. Angle determination with a degree indicating level.
-------
5-01-79
Section 3.0.2
2.0 General Factors Involved In Stationary Source Testing
It is essential to the production of valid
test data that the emissions measure-
ment prog ram be performed by qualified
personnel using proper test equipment.
Although the sampling team Qhi.ef need
not be a professional engineer, the chief
must be specially trained in source
sampling and must be experienced in
field test procedures. If the sampling
results are used in legal proceedings,
the team chief may be called as a
witness. Monitoring of a single sam-
pling station usually requires two
persons; monitoring of two stations
usually requires a minimum of three. In
all cases, there should be an adequate
staff to perform, the level of sampling
required.
Similarly, valid emission tests require
the use of appropriate and properly
functioning test equipment, which
consists basically of process-measuring
devices such as scales for weighing fuel
or raw materials and orifices and
gauges for measuring material flows
and temperatures. Process-weight
regulations may require the use of
scales which can be properly serviced
and calibrated only by trained personnel.
The scale manufacturer usually provides
this service. A stamp affixed to the scale
by the service crew should note the date
of calibration or inspection.
Sampling equipment, such as flow
meters and gauges, must be properly
calibrated and maintained. As standard
practice, the monitoring team should
check and record the dates of calibration
or servicing. Gas-sampling equipment
that requires maintenance and calibra-
tion includes the Pitot tube, manometers,
thermometers, flow meters, and dry gas
meters. Because calibration and main-
tenance of these instruments is subject
to close scrutiny in legal proceedings,
written records are required.
Emphasis is placed upon these
standard practices as means of ensuring
the validity of results. Deviations from
standard procedures must be kept to a
minimum and applied only when they
are absolutely necessary to obtain
representative samples. For compliance
testing, deviations from standard pro-
cedures may be used only with approval
of the regulatory agency. Any changes
in methodology must be based on sound
engineering judgment and must be
thoroughly documented.
The following procedures merit par-
ticular attention.
1. Locating the sampling site.
2. Determining the number of sam-
pling points in the duct,
3. Using recommended sampling equip-
ment and calibration methods,
4. Determining gas velocities,
5. Maintaining isokinetic sampling
conditions for particulates,
6. Handling the sample and main-
taining records, and
7. Sample analysis.
The remainder of this section de-
scribes procedures for stack sampling;
source sampling tools and equipment;
identification and handling of samples;
laboratory analysis; use of the sampling
data; and preparation of reports.
2.1 Source Sampling Tools and
Equipment
The needs for specific tools and
equipment will vary from test to test. A
listing of the most frequently used tools
and equipment given below is to serve
as a checklist; this equipment is useful,
but not mandatory.
1. Equipment transportation
a. Lightweight handtruck to
transport cases.
b. A 1.2-cm (0.5 in.) continuous
filament nylon rope with a snatch
block for raising and lowering
equipment on stacks and roofs.
c. Tarpaulin or plastic to protect
equipment in case of rain; sash cord
0.63 cm (1/4 in.) for securing
equipment and tarpaulin.
d. One strong metal or wooden box
for transporting small items up and
down the stack.
2. Safety equipment
a. First-aid kit.
b. Safety harness with nylon and
steel lanyards and large throat
snaphooks for use with lanyards for
hooking over guardrails or safety
lines on stacks.
c. Earplugs, H;>O, and quick-energy
food.
d. A fail-safe hook for use with
harness when climbing ladders
having safety cables.
e. Hardhats with chinstraps and
winter liners; gas masks, safety
glasses, and/or safety goggles.
f. Protective clothing including suits
for both hot and cold weather, both
asbestos and leather gloves, and
steel-toed shoes.
g. Steel cable 0.5 cm (3/16 in.) cable
clips, and turnbuckles for installing a
safety line or for securing equipment
to the stack structure.
3. Tools and spare parts
a. Electric and power equipment:
(1) Circular saw,
(2) Variable voltage transformer,
(3) Variable speed electrical drill
and bits,
(4) Ammeter-voltmeter-ohmeter
(VOM),
(5) Extension cords (light, #14
Awg; 2 @ 25 ft, 2 @ 50 ft),
(6) Two 3-wire electric adapters,
(7) 3-wire electric triple taps,
(8) Thermocouple extension
wire,
(9) Thermocouple plugs,
(10) Fuses,
(11) Electric wire,
(12) Jigsaw, and
(13) Small space heater for cold
weather.
b. Tools:
(1) Tool boxes (1 large, 1 small),
(2) Screwdriver sets (1 flat blade,
1 Philips), and
(3) Two C-clamps (6 in., 3 in.).
c. Wrenches:
(1) Open-end set (1 /4 in. -1 in.),
(2) Adjustable (12 in., 6 in.),
(3) A chain wrench,
(4) A 12-in. pipe wrench, and
(5) An Allen wrench set.
d. Miscellaneous:
(1) Silicone sealer,
(2) Silicone vacuum grease,
(3) Pump oil,
(4) Manometers (gauge oil),
(5) Antiseize compound, e.g.,
high temperature graphite
(6) Pipe fittings,
(7) Dry cell batteries,
(8) Flashlight,
(9) Valves,
(10) Thermometers (dial, 6 in. - 36
in., a remote-reading type),
(11) Vacuum gauge,
(12) Short SS-tubing (1/4 in., 3/8
in., 1/2 in.),
(13) Heavy duty wire (telephone
type),
(14) Adjustable packing gland,
(15) Nails,
(16) Spare swagelocks,
(17) Hammer,
(18) Hanging lamp, and
(19) Two-by-four's.
4. Data recording
a. Data forms or data notebook.
b. Carbon paper.
c. Slide rule or electronic calculator.
d. Psychrometric charts.
-------
Section 3.0.2
5-01-79
e. Combustion nomographs (Refer-
ence 1).
f. Pencils and pens.
2.2 Standard Data Forms
Recorded test data are part of the
physical evidence in legal proceedings.
Standardized forms are used to ensure
that all required information is obtained.
Example forms for use in the field, in the
laboratory, and for calculations are
included in later sections. Thefieldform
used when taking the sample identifies
the process tested; date and time;
location of test station; sampling
personnel; and the person who records
the data. Ink should always be used to
record the data. In the event of error, the
data-taker crosses through the
erroneous value with a single line,
records the correct value above it, and
initials the change.
2.3 Identification of Sampling
Materials
All samples must be marked to ensure
positive identification throughout the
test and analysis procedures. The legal
rules of evidence require systematic
identification of samples at all points in
their processing. Valid testimony
requires that a laboratory analyst be
able to relate the analytical data to a
specific sample by number. Analysts
also must provide positive identification
of filters. All identifying marks on the
filters should be made before weighing.
The filters should be serially numbered
to ensure their unique identification.
The ink used for marking must be
indelible and unaffected by gases,
temperatures, or other conditions to
which it is subjected. If any agency
specifies another method of
identification, that method must be
positive and must not impair the
capacity of the filter to function.
Finally, the monitoring personnel
must provide unique identification for
each container to preclude the
possibility of interchange. The number
of the container is recorded on the field
form and on the analysis data form so
that it is associated with the sample
throughout testing and analysis. See
Section 3.0.3 for further details
concerning the uses of source samples
as evidence.
2.4 Reference
Smith, Walter S., and D. James Groves.
Stack Sampling Nomographs for Field
Estimations. Entropy Environmentalists,
Inc., Research Triangle Park, NC.
-------
5-01-79
Section 3.0.3
3.0 Chain-of-Custody Procedure For Source Sampling
As part of the overall quality
assurance activities associated with the
collection and analysis of source
samples, particular attention should be
directed to the handling of the sample
and the analysis report.
Source test results, or possibly even
the sample itself, may be used to prove
the compliance status of a facility.
However, test results and samples will
not be admitted as evidence unless it
can be shown that they accurately
represent the conditions that prevailed
at the time the test was conducted. This
requires that:
1. the sample be collected properly,
2. the sample be handled properly,
3. the sample be analyzed in
accordance with documented test
procedure, and
4. the test report be prepared
completely and accurately and
then filed in a secure place.
Failure to comply with these require-
ments may void the results of a test or,
at least, diminish the credibility of the
test report.
3.1 Sample Collection
Proper sampling requires the use of
the correct method, the equipment
designated by the method, and
competent personnel. Prior to the test
date, the tester should determine that
the proposed test methods comply with
the appropriate testing regulations; in
some instances, it may be necessary to
deviate from the proposed methods. For
example, the only reasonable sample
site may be too close to an elbow or a
duct obstruction. In such cases, the
tester should make an engineering
analysis of the use of the test site and
then proceed only after obtaining the
approval of the regulatory authority.
This determination should be recorded
in the field notes. An after-the-fact site
analysis may suffice in many instances,
but good quality assurance techniques
dictate that this analysis be made prior
to spending the many man-hours
required to extract the sample. Once the
test method is selected, preparations for
the test should be made according to
documented guidelines.
3.1.1 Preparations When
conducting the test, it is necessary that
the sample be extracted in a manner to
ensure that it represents the actual
conditions at the time of the test. This
means that the process is operating in
its mode specified by the applicable
control regulation, the extracted sample
typifies the stack gas conditions, and the
instruments used in the sampling are
properly calibrated and maintained.
Because the results of source tests
are being used increasingly as proof of
compliance, the pretest preparation and
posttest scrutiny are becoming more
sophisticated. Thus, steps need to be
taken prior to the actual test to ensure
the integrity of the test data.
In many cases, reagents or filters are
prepared prior to sampling and become
an integral part of the sample itself. A
record should list the date, the person by
whom it was prepared, and the location
of these items at all times from
preparation until actual use for
sampling. Since these items become a
part of the sample itself, it is necessary
that their integrity be maintained from
preparation through analysis. For
example, a bulkquantityof solution may
be prepared and transported to the field
where the specified amount is used in
accordance with the test method. The
bulk solution ultimately becomes an
integral part of several samples during
the sampling process. For this reason,
one member of the sampling crew
generally serves as sample custodian
and should be responsible for entering
information on sample preparation
items in the field notebook. However, as
long as proper records are kept, more
than one individual may serve in this
capacity. This serves as a written record
for the sampling crew and also fulfills
chain-of-custody procedures.
3.1.2 Sample Handling - Once the
sample is procured it should be handled
in such a way as to ensure that there is
no contamination and that the sample
analyzed is actually the sample taken
under the conditions reported. For
example, each sample should be kept in
a secure place between the time it is
extracted and the time it is analyzed. If
further analysis may be required, the
sample should be returned to a secure
place. It is always best to keep a sample
secure up to the time, it is discarded.
These security measures should be
documented by a written record signed
by the handlers of the sample.
Identification - Care should betaken
to mark the samples to ensure positive
identification throughout the test and
analysis procedures. The evidence used
in legal proceedings requires positive
procedures for identification of samples
used in analyses as the basis for future
evidence. An admission that the
laboratory analyst could not be positive
whether sample No. 6 or sample No. 9
was analyzed could destroy the validity
of the entire test report.
Positive identification also should be
provided for the filters used in any
specific test before taring. If ink is used
for marking, it must be indelible and
unaffected by the gases and
temperatures to which it will be
subjected. Other methods of
identification can be used, if they
provide a positive means of
identification and do not impair the
function of the filter.
Finally, each container should have a
unique identification to preclude the
possibility of interchange. Grease
pencils may be used for this purpose. A
better method, however, is to affix an
adhesive-backed label to the container.
The number of the container should be
recorded on the analysis data form.
Figure 3.1 shows how a standardized
identification sticker can be used for
each of the four containers needed to
collect a sample for EPA Test Method 5.
Contamination and Tampering - To
reduce the possibility of invalidating the
results, all components of the sample
should be carefully removed from the
sampling train and placed in nonreactive
containers. The best method of sealing
depends on the container. Place con-
tainers in a place of limited access (i.e.,
locked van or locked sample box). This
will preclude accidental opening of the
container and should be a sufficient
safeguard if all other aspects of the
chain-of-custody procedure are observed.
However, if there is any possibility of
temporary access to the samples by
unauthorized personnel, the sample
jars and containers should be sealed
with a self-adhesive sticker that has
been signed and numbered by the test
supervisor or other responsible person.
This sticker should adhere firmly to
ensure that it cannot be removed
without destruction. The samples
should then be delivered to the labora-
tory for analysis. It is recommended that
this be done on the same day that the
sample is taken. If this is impractical, all
of the samples should be placed in a
carrying case or other place of limited
access (preferably locked) for protection
from breakage, contamination, and loss.
In transporting the sample to the
laboratory, it is important that precau-
tions be taken to eliminate the possibility
-------
Container No. ft * ^
Plant QB£ C*r** City Podunk
Site £*j+ K.i/f\£f-AcJi. Pollutant fh*±.
Date //- 18- 11 nun No. 2.
t/ Front hall Front titter no.
Back hall Back filter no.
Rinse A u^bne.
Volume: Initial f^/.A. Final «3dO /n/. 1
Cleanup by £2 JUAt. Field Chief A/- Qfk AAfCO
-------
5-01-79
Section 3.0.3
of tampering, accidental destruction,
and physical and/or chemical damage
to the sample. This practical considera-
tion should be dealt with on a case-by-
case basis. For example, samples
obtained from a rock crusher are
nonreactive but those from an asphalt
saturator may be reactive, and gaseous
samples may decay or react.
The person who has custody of the
samples should be able to testify that no
one tampered with them. Any handling
of samples by unauthorized persons can
result in contamination. For example, a
curious person with a cigarette in his
mouth may open a sample; the smallest
ash dropping into the container could
make a significant difference in the
analysis. Security should be continuous.
If the samples are put in a truck, lock it.
In the laboratory, the samples should be
kept in a secure place.
To ensure that none of the sample is
lost in transport, mark all liquid levels on
the side of the container with a grease
pencil. Thus any major losses that occur
will be readily ascertainable.
Chain-of-Custody - The chain-of-
custody is perhaps the most critical part
of the test procedure. The chain-of-
custody is necessary to make a prima
facie showing of the representativeness
of the sample. Without it, one cannot be
sure that the sample analyzed was the
same as the one purported to be taken at
a particular time. The samples should be
handled only by persons associated in
some way with the test. A general rule
to follow is "the fewer hands the
better," even though a sealed sample
may pass through a number of hands
without affecting its integrity. Ideally, all
sample containers should be transported
from the site to the vehicle and from the
vehicle to the laboratory by the same
person.
It is generally impractical for the
analyst to perform the field test. For this
reason, each person should remember
from whom the sample was received
and to whom it was delivered. This
requirement is best satisfied by having
each recipient sign the data form for the
sample or set of samples. Figure 3.2
shows a form for paniculate samples
which may be used to establish the
chain-of-custody from the test site to
the laboratory. This form is designed for
tests performed by EPA Method 5. Note
that the silica gel was weighed in the
field. If for some reason this is not done,
the silica gel must be returned with the
other containers, and an appropriate
notation made under "Remarks." Figure
3.3 shows another form which may be
used. A form of this type should
accompany the samples at all times
from the field to the laboratory. All
persons who handle the samples should
sign the form. It is important to realize
that the chain-of-custody procedures do
not stop with the sample analysis. If the
sample must be kept for future analysis,
it should be kept in a secure storage
area. Figures 3.2 and 3.3 reflect this.
3.2 Sample Analysis
For source samples to provide useful
information, laboratory analyses should
meet the following requirements:
1. Equipment should be adequate for
proper analysis;
2. Personnel should be qualified to
make analysis;
3. Analysis procedures should be in
accordance with accepted good
practice; and
4. Records should be complete and
accurate.
The first three requirements are dis-
cussed elsewhere in this Handbook and
need no further elaboration.
Complete and accurate records gener-
ally take the form of a laboratory
notebook. Where practical, standard
preprinted forms should be used. Do not
discard these records, since it is
possible that they will be needed in the
future to substantiate the final report.
Figures 3.4 and 3.5 are examples of
standardized forms that can be used in
the laboratory. Note that the entries on
these forms must agree with those
shown on the container labels (Figure
3.1) and on the chain-of-custody receipt
form (Figures 3.2 and 3.3).
3.3 Field Notes
Manual recording of data is required
for source tests. Standardized forms
should be utilized to ensure that all
necessary data are obtained. These
forms should be designed to clearly
identify the process tested, the date and
time, the test station location, the
sampling personnel, and the person
who recorded the data. During the
actual test period, the meter readings,
temperature readings, and other perti-
nent data should be recorded in the
spaces immediately upon observation.
These data determine the accuracy of
the test and should not be erased or
altered. Any error should be crossed out
with a single line; the corrected value
should be recorded above the crossed-
out number.
Do not discard the original field
records even if they become soiled. For
neatness, the field data may be tran-
scribed or copied for inclusion in the
final report, but the originals should be
kept on file. Copies are not normally
admissible as evidence, but since the
records may be subpoenaed, it is
important that all field notes be legible.
3.4 The Report as Evidence
In addition to samples and field
records, the report of the analysis itself
may serve as material evidence. Just as
the procedures and data leading up to
the final report are subject to the rules of
evidence, so is the report itself. Written
documents, generally speaking, are
considered hearsay and are not admis-
sible as evidence without a proper
foundation. A proper foundation consists
of testimonies from all persons having
anything to do with the major portions of
the test and analysis. Thus the chief of
the field team, the cleanup man, all
persons having custody of the samples,
and the laboratory analyst would be
required to lay the foundation for
introduction of the test report as
evidence.
Legal rules recognize that a record of
events is the result of input from many
persons who have no reason to lie and
that introduction of all these persons as
witnesses is onerous. These rules
recognize the complexity and mobility of
our society and are relatively liberal.
Indeed, in many cases the trial judge
will require the parties to verify the
authenticity of source test reports
during the pretrial proceedings. How-
ever, the party against whom the report
is offered still has the right, with
reasonable cause, to cross-examine the
test participants. In this area, the trial
judge may exercise discretion.
The relaxed attitude toward reports of
experiments made by persons in the
regular course of activity greatly sim-
plifies the introduction of the report as
evidence. Only the custodian of the
report (usually the supervisor or the test
team) need testify.
To ensure compliance with legal rules
all test reports should be filed in a
secure place by a custodian having this
responsibility. Although the field notes
and calculations are not generally
included in the summary report, this
material may be required at a future
date to bolster the acceptability and
credibility of the report as evidence in an
enforcement proceeding. Therefore, the
full report — including all original notes
and calculation forms — should be kept
in the file. Signed receipts for all
samples should also be filed with the
test data.
The original of a document is the best
evidence and a copy is not normally
admissible as evidence. Microfilm,
snap-out carbon copies, and similar
contemporary business methods of
producing copies are acceptable in
many jurisdictions if the unavailability
of the original course is adequately
explained and if the copy was made in
the ordinary course of business.
-------
Section 3.0.3
6-01-79
In summary, although all the original
calculations and test data need not be
included in the final report, they should
be kept in the files. It is a good rule to file
all reports together in a secure place.
location
Sample recovery by •
Filter number(s)
£ X/ T
/Y W7
Ohi
o
Sample date .
//-/7-T7
-Run number .
Moisture
Impingers
Fina/ un/i/mff (wt)
Initial volume (wt.)
Nat unlnma (art)
Total moistur
Color of silica gel
Description of impinger
3&0
30 O
80
• 98
•01 /I k. O.f
r T/
ml fyl
mllg)
mlfnl
id bluf—
imaLi/
J
Silica gel
Final wt *?d
_3
-------
5-01-79
Section 3.0.3
. fadunk. OH
Sample
number
Number of
container
Description
of samples
ftcdvm.
A-S
F-b
Person responsible for samples
O. /4/tf-C.
T
Tlme
V.'iO
Date H-I8-V7
Sample
number
Relinquished
by
Received
by
Time
Date
Reason for change
of custody
/I-/8-77
10 :<
Figure 3.3. (,'hain-of-custody receipt form - general form.
-------
Section 3.0.3
5-01-79
Plant
Sample location
Density of acetone I pa)
Podunk-. fl/i/a
. Run number
0,130
.g/mt
Sample
type
Acetone blank
Acetone rinse
Filter(s)
Container
number
A-S
4-V
r-6
Liquid level
marked
•
•
Container
sealed
iX"
•
•X
Acetone blank residue concentration (Ca)
Date and time of wt.
Filter number/s)
//- A/-77. 8
Weight oi
/v?^*/
J. 1 * IO~3
n*f> ,- O.&
oo A.#\. «„,«„,,
• AS A/H Grnss wt
A verage grn.vs vut
Tar? <*t
Less acetnns blank w/r (Wa)
f paniculate in acetnnpf rinsn
5M/O. 6
,r«*/0. (f
S2.IO. "7
SIOB' Cf
o.s
lOf.l*
mg/g
mg
mg
mg
mg
mg
mg
mg
Date and time of wt. (I'^O'Tl i 7-fQ A,/fl. Gross wt..
Date and time of wt. M"J»'/f7 ,' Q . /^* A-^- Gross wt.
Average gross wt.
Tare wt.
Weight of paniculate on filter/si
Weight of paniculate in acetone rinse
Total weight of paniculate
yso.o
. 3
-mg
-mg
- mg
- mg
-mg
- mg
Remarks
Signature
Signature of reviewer ^
Figure 3.4. Standard form for laboratory analysis of sample (EPA Test Method 5).
-------
5-01-79
Section 3.0.3
Plant //«C C0*/>v mZU»lK
, L//J/O Blank number
f-t ~^j
Sample location K.I/A. £)ClT \3l< &.CK.
Liquid level at mark IS
Density of acetone (pa) Q, f T 0
Acetone blank volume (Va) ±300
Date and time of wt. //-J O-77 ' 5 •'/«$"
Date and time of wt. ((-&! 0*77! ^3'A{
Container sealed
mg/ml
ml
f\
JVffO-7
JV80- *
O.S-
mg
mg
mg
mg
mg
Ca =
Va pa 1300 )
= 0-0031
mg/g
Remarks
Signature of Analyst
Signature of reviewer
Figure 3.5. Standard form for laboratory analysis of acetone blank.
-------
Section 3.0.4
Rev. 6/9/87
Page 1
3.0.4. PROCEDURE FOR NBS-TRACEABLE CERTIFICATION OF COMPRESSED
GAS WORKING STANDARDS USED FOR CALIBRATION AND
AUDIT OF CONTINUOUS SOURCE EMISSION MONITORS
(Revised Traceablllty Protocol No. 1)
CONTENTS
Subsection Title
3.0.4.0 General Information
3.0.4.1 Procedure Gl: Assay and Certification of
a Compressed Gas Standard Without Dilution
3.0.4.2 References
4.0 GENERAL INFORMATION
4.0.1 Purpose and Scope of the Procedure
Section 3.0.4 describes a procedure for assaying the concentration of gaseous
pollutant concentration standards and certifying that the assay concentrations are
traceable to an authoritative reference concentration standard. This procedure is
recommended for certifying the local working concentration standards required by the
pollutant monitoring regulations of 40 CFR Part 60^2 for the calibration and audit
of continuous source emission monitors. The procedure covers certification of com-
pressed gas (cylinder) standards for CO, C02, NO, N02, and $03 (Procedure Gl).
4.0.2 Reference Standards
Part 60 of the monitoring regulations1'2 require that working standards used
for calibration and audit of continuous source emission monitors be traceable to
either a National Bureau of Standards (NBS) gaseous Standard Reference Material
(SRM) or a NBS/EPA-approved Certified Reference Material (CRM)3. Accordingly, the
reference standard used for assaying and certifying a working standard for these
purposes must be an SRM, a CRM, or a suitable intermediate standard (see the next
paragraph). SRM cylinder gas standards available from NBS are listed in Table 7.2
at the end of subsection 4.0. A current list of CRM cylinder gases and CRM vendors
is available from the Quality Assurance Division (MD-77), Environmental Monitoring
Systems Laboratory, U. S. EPA, Research Triangle Park, NC 27711.
The EPA regulations define a "traceable" standard as one which "...has been
compared and certified, either directly or via not more than one intermediate stan-
dard, to a primary standard such as a...NBS [gaseous] SRM or...CRM"4|5. Certifica-
tion of a working standard directly to an SRM or CRM primary standard is, of course,
preferred and recommended because of the lower error. However, an intermediate
reference standard is permitted, if necessary. In particular, a Gas Manufacturer's
Intermediate Standard (see subsection 4.0.2.1) that has been referenced directly to
an SRM or a CRM according to Procedure Gl is an acceptable Intermediate standard and
could be used as the reference standard on that basis. However, purchasers of com-
-------
Section 3.0.4
Rev. 6,49/87
Page 2
«
merdal gas standards referenced to an Intermediate standard such as a GMIS should
be aware that, according to the above definition, such a standard would have to be
used directly for calibration or audit. Since a second Intermediate standard is not
permitted, such a standard could not be used as a reference standard to certify
other standards.
4.0.2.1 Gas Manufacturer's Intermediate Standard (GMIS). A GMIS 1s a compressed
(cylinder) gas standard that has been assayedwith direct reference to an SRM or
CRM and certified according to Procedure Gl, and also meets the following re-
quirements:
1. A candidate GMIS must be assayed a minimum of three (3) times, uniformly
spaced over a three (3) month period.
2. Each of the three (or more) assays must be within 1.0 percent of the mean
of the three (or more) assays.
3. The difference between the last assay and the first assay must not exceed
1.5 percent of the mean of the three (or more) assays.
4. The GMIS must be recertified every three months, and the reassay must be
within 1.5 percent of the previous certified assay. The recertified concentra-
tion of the GMIS is the mean of the previous certified concentration and the
reassay concentration.
4.0.2.2 Recertlfication of Reference Standards. Recertificatlon requirements
for SRMs and CRMs are specifiedbyNBSand NBS/EPA, respectively. See 4.0.2.1
for GMIS recertification requirements.
4.0.3 Using the Procedure
The assay/certification procedure described here 1s carefully designed to mini-
mize both systematic and random errors in the assay process. Therefore, the proce-
dure should be carried out as closely as possible to the way 1t is described. Simi-
larly, the assay apparatus has been specifically designed to minimize errors and
should be configured as closely as possible to the design specified. Good labora-
tory practice should be observed 1n the selection of Inert materials (e.g. Teflon,
stainless steel, or glass, if possible) and clean, non-contaminating components for
use 1n portions of the apparatus 1n contact with the candidate or reference gas
concentrations.
4.0.4 Certification Documentation
Each assay/certification must be documented 1n a written certification report
signed by the analyst and containing at least the following information:
1. Identification number (cylinder number).
2. Certified concentration of the standard, in ppm or mole percent.
3. Balance gas in the standard mixture.
-------
Section 3.0.4
Rev. 6/9/87
Page 3
4. Cylinder pressure at certification.
5. Date of the assay/certification.
6. Certification expiration date (see 4.0.6.3).
7. Identification of the reference standard used: SRM number, cylinder number,
and concentration for an SRM; cylinder number and concentration for a CRM or
GMIS.
8. Statement that the assay/certification was performed according to this Sec-
tion 3-.0.4.
9. Identification of the laboratory where the standard was certified and the
analyst who performed the certification.
10. Identification of the gas analyzer used for the certification, Including the
make, model, serial number, the measurement principle, and the date of the last
multipoint calibration.
11. All analyzer readings used during the assay/certification and the calcula-
tions used to obtain the reported certified value.
12. Chronological record of all certifications for the standard.
Certification concentrations should be reported to 3 significant digits. Certifica-
tion documentation should be maintained for at least 3 years.
4.0.5 Certification Label
A label or tag bearing the Information described 1n Items 1 through 9 of sub-
section 4.0.4 must be attached to each certified gas cylinder.
4.0.6 Assay/Certification of Compressed Gas (Cylinder) Standards
4.0.6.1 Aging of newly-prepared gas standards. Freshly prepared gas standard
concentrations and newly filled gascylindersmust be aged before being assayed
and certified. S02 concentrations contained 1n steel cylinders must be aged at
least 15 days; other standards must be aged at least 4 days.
4.0.6.2 Stability test for reactive gas standards. Reactive gas standards,
Including nitric oxide (NO),nitrogendioxide(NO^T, sulfur dioxide ($02), and
carbon monoxide (CO), that have not been previously certified must be tested for
stability as follows: Reassay the concentration at least 7 days after the first
assay and compare the two assays. If the second assay differs from the first as-
say by 1.5% or less, the cylinder may be considered stable, and the mean of the
two assays should be reported as the certified concentration. Otherwise, age the
cylinder for a week or more and repeat the test, using the second and third as-
says as If they were the first and second assays. Cylinders that are not stable
may not be solid and/or used for calibration or audit purposes.
-------
Section 3.0.4
Rev. 6V9/87
Page 4
4.0.6.3 Recert1f1cation of compressed gas standards. Compressed gas standards
must be recertified according to this Section 3.0.4 within the time limits speci-
fied in Table 7.13i6»7. The reassay concentration must be within 5% of the pre-
vious certified concentration. If not, the cylinder must be retested for stabil-
ity (subsection 4.0.6.2). The certified concentration of a recertified standard
should be reported as the mean of all assays, unless a clear trend or substantial
change suggests that previous assays are no longer valid.
Table 7.1 Recertification limits for compressed gas standards.
Propane
Maximum months until
recertification for
Pollutant
Carbon monoxide
Nitric oxide
Sulfur dioxide
Nitrogen dioxide
Carbon dioxide
Oxygen
Sulfur dioxide and
carbon dioxide
Balance
gas
N2 or air
N2
N2
N2 or air
N2 or air
N2
N2
Concentration
range
* 5 ppm
Z 10 ppm
£ 10 ppm
£ 10 ppm
£ 300 ppm
£ 2 percent
* 200 ppm S02,
£ 10 percent C02
cylinder material :
Al or SS other
18
18
18
6
18
18
18
6
6
6
6
18
18
6
N2 or air
5 ppm
Others not specifically listed
18
6
6
6
4.0.6.4 Minimum cylinder pressure. No compressed gas cylinder standard should
be used when its gas pressureIT" below 700 kPa (100 psi), as indicated by the
cylinder pressure gauge.
4.0.6.5 Assay/certification of multi-component compressed gas standards. Proce-
dure Gl may be used to assay and certify Individual components of multi-component
gas standards, provided that none of the components other than the component
being assayed cause a detectable response on the analyzer.
-------
Section 3.0.4
Rev. 6/9/87
Page 5
4.0.7 Analyzer Calibration
4.0.7.1 Basic analyzer calibration requirements. The assay procedure described
in this Section 3.0.4 employs a direct ratio referencing technique that Inherent-
ly corrects for minor analyzer calibration variations (drift) and DOES NOT depend
on the absolute accuracy of the analyzer calibration. What is required of the
analyzer 1s as follows: 1) it must have a linear response to the pollutant of
interest (see subsection 4.0.7.5), 2) it must have good resolution and low noise,
3) its response calibration must be reasonably stable during the assay/certifica-
tion process, and 4) all assay concentration measurements must fall within the
calibrated response range of the analyzer.
4.0.7.2 Analyzer multipoint calibration. The gas analyzer used for the assay/
certification must have had a multipoint calibration within 3 months of its use
when used with this procedure. This calibration is not used to quantitatively
Interpret analyzer readings during the assay/certification of the candidate gas
because a more accurate, direct ratio comparison of the candidate concentration
to the reference standard concentration 1s used. However, this multipoint cali-
bration is necessary to establish the calibrated range of the analyzer and its
response linearity.
The multipoint calibration should consist of analyzer responses to at least
5 concentrations, Including zero, approximately evenly spaced over the concentra-
tion range. Analyzer response units may be volts, millivolts, percent of scale,
or other measurable analyzer response units. The upper range limit of the cali-
brated range is determined by the highest calibration point used. If the analyz-
er has a choice of concentration ranges, the optimum range for the procedure
should be selected and calibrated. Plot the calibration points and compute the
linear regression slope and intercept. See subsection 4.0.7.5 for linearity re-
quirements and the use of a mathematical transformation, 1f needed. The inter-
cept should be less than 1 percent of the upper concentration range limit, and
the correlation coefficient (r) should be at least 0.999.
4.0.7.3 Zero and span check and adjustment. On each day that the analyzer will
be used for assay/certification, Its response calibration must be checked with a
zero and at least one span concentration near the upper concentration range lim-
it. If necessary, the zero and span controls of the analyzer should be adjusted
so that the analyzer's response (I.e. calibration slope) is within about ±5
percent of the response Indicated by the most recent multipoint calibration. If
a zero or span adjustment 1s made, allow the analyzer to stabilize for at least
an hour or more before beginning the assay procedure, since some analyzers drift
for a period of time following zero or span adjustment. If the analyzer is not
1n continuous operation, turn 1t on and allow it to stabilize for at least 12
hours before the zero and span check.
4.0.7.4 Pollutant standard for multipoint calibration and zero and span adjust-
ment. The pollutantstandardorstandardsused for multipoint calibration or
zero and span checks or adjustments must be obtained from a compressed gas stan-
dard certified traceable to an NBS SRM or a NBS/EPA CRM according to Procedure Gl
of this Section 3.0.4. This standard need not be the same as the reference stan-
dard used 1n the assay/certification. The zero gas must meet the requirements 1n
subsection 4.0.8.
-------
Section 3.0.4
Rev. 6/9/87
Page 6
4.0.7.5 Linearity of analyzer response. The direct ratio assay technique used
In Procedure Gl requires that the analyzer have a linear response to concentra-
tion. Linearity 1s determined by comparing the quantitative difference between a
smoothly-drawn calibration curve based on all calibration points and a straight
line drawn between zero and an upper reference point (see Figure 1). This dif-
ference 1s measured in concentration units, parallel to the concentration axis,
from a point on the calibration curve to the corresponding point for the same
response on the straight line.
For the general linearity requirement, the straight line is drawn between
zero and the highest calibration point (Figure la). Linearity is then acceptable
when no point on the smooth calibration curve deviates from the straight line by
more than 1.5 percent of the value of the highest calibration concentration. An
alternative linearity requirement 1s defined on the basis of the actual reference
and candidate concentrations to be used for the assay. In this case, the refer-
ence and candidate concentrations are plotted on the calibration curve, and the
straight line 1s drawn from zero to the reference concentration and extrapolated,
1f necessary, beyond the candidate concentration (Figure Ib). The deviation of
the smooth calibration curve from the straight line at the candidate concentra-
tion point then must not exceed 0.8 percent of the value of the reference concen-
tration. This latter specification may allow the use of an analyzer having
greater nonllnearlty when the reference and candidate concentrations are nearly
the same.
For analyzers having an Inherently non-linear response, the response can
usually be linearized with a simple mathematical transformation of the response
values, such as R'= square root(R) or R'= log(R), where R' 1s the transformed
response value and R 1s the actual analyzer response value. Using the trans-
formed response values, the multipoint calibration should meet one of the above
linearity requirements as well as the requirements for intercept and correlation
coefficient given 1n subsection 4.0.7.2.
4.0.8 Zero Gas
Zero gas used for dilution of any candidate or reference standard should be
clean, dry, zero-grade air or nitrogen containing a concentration of the pollutant
of Interest equivalent to less than 0.5 percent of the analyzer's upper range limit
concentration. The zero gas also should contain no contaminant that causes a de-
tectable response on the analyzer or that suppresses or enhances the analyzer's
response to the pollutant. The oxygen content of zero air should be the same as
that of ambient air.
4.0.9 Accuracy Assessment of Commercially Available Standards
Periodically, the USEPA will assess the accuracy of commercially available
compressed gas standards that have been assayed and certified according to this
Section 3.0.4. Accuracy will be assessed by EPA audit analysis of representative
actual commercial standards obtained via an anonymous agent. The accuracy audit
results, Identifying the actual gas manufacturers or vendors, will be published as
public Information.
-------
Section 3.0.4
Rev. 6/9/87
Page 7
c
o
a
i
Concentration difference
between calibration curve
and straight line must
not exceed 1.5% of
Cmax at any point
between 0 and
Smooth calibration
curve based on all
calibration
points
t. ^.
Straight line
between zero
and highest
calibration
point
I I I
Concentration
at highest
^calibration
point (Cmax)
Concentration, ppm or percent
a) General linearity requirement
Concentration difference
between calibration
curve and straight line
at candidate
concentration point
must not exceed 0.8%
of the reference
concentration
Candidate
concentration
Smooth calibration
curve based on all
calibration points
Calibration
points
Straight line
between zero
and reference
concentration
Reference
concentration
Concentration difference
between calibration
curve and straight line
at candidate concentration
point must not •—
exceed 0.8% of the 3^
reference concentration
Smooth calibration
curve based on all
calibration points
Candidate
concentration
Calibration
points
Reference
concentration
Straight line between zero and
reference concentration, extrapolated
to beyond the candidate concentration
Concentration, ppm or percent
Concentration, ppm or percent
b) Alternative linearity requirement
Figure 1. Illustration of linearity requirements.
-------
Table 7.2. NBS SRM reference gases.
For availability, contact:
Office of Standard Reference Materials
Chemistry Building, Room B311
NBS, Galthersburg, Maryland 20899
(301) 975-6776. (FTS 879-6776)
Section 3.0.4
Rev. 6/9/87
Page 8
SRM
number
2627
2628
2629
1683b
1684b
1685b
1686b
1687b
2630
2631
2653
2654
2655
2656
2612a
2613a
2614a
1677c
2635
1678C
1679C
2636
1680c
1681c
2637
2638
2639
2640
2641
2642
2657
2658
2659
NBS-SRM
Type
NO/N2
NO/N2
NO/N2
NO/N2
NO/N2
NO/N2
NO/N2
NO/N2
NO/N2
NO/N2
N02/A1r
N02/A1r
N02/A1r
N02/A1r
C0/A1r
C0/A1r
C0/A1r
CO/N2
CO/N2
CO/N2
CO/N2
CO/N2
CO/N2
CO/N2
CO/N2
CO/N2
CO/N2
CO/N2
CO/N2
CO/N2
02/N2
02/N2
02/N2
cylinders contain
Nominal
concentration
5
10
20
50
100
250
500
1000
1500
3000
250
500
1000
2500
10
20
45
10
25
50
100
250
500
1000
2500
5000
1
2
4
8
2
10
21
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
percent
percent
percent
percent
percent
percent
percent
SRM
number
1693
1694
1661a
1662a
1663a
1664a
1696
1670
1671
1672
2632
2633
2634
2619a
2620a
2621a
2622a
2623a
2624a
2625a
2626a
1674b
1675b
1665b
1666b
1667b
1668b
1669b
2643
2644
2645
2646
2647
2648
2649
2650
approximately 870 liters of
Type
S02/N2
S02/N2
S02/N2
S02/N2
S02/N2
S02/N2
S02/N2
C02/A1r
C02/A1r
C02/A1r
C02/N2
C02/N2
C02/N2
C02/N2
C02/N2
C02/N2
C02/N2
C02/N2
C02/N2
C02/N2
C02/N2
C02/N2
C02/N2
C3H8/A1r
C3H8/A1r
C3H8/A1r
C3H8/A1r
C3H8/A1r
C3H8/N2
C3H8/N2
C3H8/N2
C3H8/N2
C3H8/N2
C3H8/N2
C3H8/N2
C3H8/N2
gas at STP.
Nominal
concentration
50 ppm
100 ppm
500 ppm
1000 ppm
1500 ppm
2500 ppm
3500 ppm
330 ppm
340 ppm
350 ppm
300 ppm
400 ppm
800 ppm
0.5 percent
1.0 percent
1.5 percent
2.0 percent
2.5 percent
3.0 percent
3.5 percent
4.0 percent
7.0 percent
14.0 percent
3 ppm
10 ppm
50 ppm
100 ppm
500 ppm
100 ppm
250 ppm
500 ppm
1000 ppm
2500 ppm
5000 ppm
1 percent
2 percent
-------
Section 3.0.4
Rev. 6/9/87
Page Gl-1
4.1 PROCEDURE 61; ASSAY AND CERTIFICATION OF A COMPRESSED
GAS STANDARD WITHOUT DILUTION
4.1.1 Applicability
This procedure may be used to assay the concentration of a candidate compressed
gas (cylinder) pollutant standard, based on the concentration of a compressed gas
(cylinder) reference standard of the same pollutant compound, and certify that the
assayed concentration thus established for the candidate standard 1s traceable to
the reference standard. The procedure employs a pollutant gas analyzer to compare
the candidate and reference gas concentrations by direct measurement—without dilu-
tion of either gas--to minimize assay error,
4.1.2 Limitations
1. The concentration of the candidate gas standard must be between 0.3 and 1.3
times the concentration of the reference gas standard.
2. The analyzer must have a calibrated range capable of directly measuring both
the candidate and the reference gas concentrations.
3. The analyzer's response (or transformed response) must be linear with respect
to concentration.
4. The balance gas 1n both the candidate and reference standards must be Identi-
cal, unless it can be shown that the analyzer is Insensitive to any difference 1n
the balance gases.
5. A source of clean, dry zero gas is required.
4.1.3 Assay Apparatus
Figure Gl Illustrates the relatively simple assay apparatus. The configuration
is designed to allow convenient routing of the zero gas and undiluted samples of the
reference gas and candidate gases, 1n turn, to the analyzer for measurement, as
selected by three-way valves VI and V2. Pressure regulators and needle valves (V3
and V4) control the individual gas flows. The pollutant concentrations are deliv-
ered to the analyzer via a vented tee, which discharges excess flow and Insures that
the assay concentrations sampled by the analyzer are always at a fixed (atmospheric)
pressure. A small, uncalibrated rotameter monitors the vent flow to verify that the
total gas flow rate exceeds the sample flow rate demand of the analyzer so that no
room air 1s admitted through the vent. Valves VI and V2 could be replaced by a sin-
gle four-way valve (with 3 inputs and 1 output) or by manually moving the output
connection to each of the gases as needed. See also subsection 4.0.3.
4.1.4 Analyzer
See subsection 4.0.7.1. The pollutant gas analyzer must have a linear response
function and a calibrated range capable of measuring the full concentration of both
the candidate and the reference gas standards directly, without dilution. It must
-------
Section 3.0.4
Rev. 6/9/87
Page Gl-2
Zero Gas
(Air or N2)
Supply
Vent
1
Rotameter
JL
To Analyzer
Three-Way Valve
Reference
Gas
Candidate
Gas
Figure Gl. Suggested assay apparatus for Procedure Gl.
-------
Section 3.0.4
Rev. 6/9/87
Page Gl-3
have good resolution (readability), good precision, a stable response, and low out-
put signal noise. In addition, the analyzer must have good specificity for the
pollutant of interest so that it has no detectable response to any contaminant that
may be contained in either the candidate or reference gas. If the candidate and
reference gases contain dissimilar balance gases (air versus nitrogen or different
proportions of oxygen in the balance air, for example), the analyzer must be proven
to be insensitive to the two different balance gases. This may be accomplished by
showing no difference in analyzer response when measuring pollutant concentrations
diluted with identical flow rates of the two balance gases.
The analyzer should be connected to a suitable, precision chart recorder or
other data acquisition device to facilitate graphical observation and documentation
of the analyzer responses obtained during the assay.
4.1.5 Analyzer Calibration
4.1.5.1 Multipoint calibration. See subsections 4.0.7.2 and 4.0.7.4.
4.1.5.2 Calibration range. The calibrated range of the analyzer must Include
both the candidate and reference gas concentrations, such that the higher concen-
tration does not exceed 97 percent of the upper range limit, and the lower con-
centration 1s not below 25 percent of the upper range limit (assuming a lower
range limit of zero). Within these limits, select a calibrated analyzer range
that will produce the highest analyzer responses.
4.1.5.3 Linearity. The direct ratio assay technique used 1n this procedure
requires that the analyzer have a linear response to concentration (see subsec-
tion 4.0.7.5). High-concentration-range analyzers of the type that are required
for this procedure may not be Inherently linear, but they usually have a predic-
table, non-linear response characteristic that can be mathematically transformed
to produce a sufficiently linear response characteristic suitable for use 1n this
procedure. Any such response transformation should be verified by using 1t for
the multipoint calibration. Caution should be exercised 1n using a transformed
response curve because physical zero or span adjustments to the analyzer may
produce unexpected effects on the transformed characteristic.
4.1.5.4 Zero and span adjustment. See subsections 4.0.7.3 and 4.0.7.4. Prior
to carrying out the assay/certification procedure, check the calibration of the
analyzer and, 1f necessary, adjust the analyzer's zero and span controls to re-
establish the response characteristic determined at the most recent multipoint
calibration. Allow the analyzer to stabilize for an hour or more after any zero
or span adjustment. If there 1s any doubt that a transformed response character-
istic 1s still linear following a zero or span adjustment, verify linearity with
a multipoint calibration (subsection 4.0.7.2) using at least 3 known pollutant
concentrations, Including zero.
4.1.6 Assay Gases
4.1.6.1 Candidate gas standard. See subsections 4.0.6 and 4.1.2.
4.1.6.2 Reference gas standard. See subsections 4.0.2, 4.1.2, and 4.0.6.4. Se-
lect a reference standard such that the concentration of the candidate gas 1s not
-------
Section 3.0.4
Rev. 6/9/87
Page Gl-4
more than 30 percent above nor less than 70 percent below the concentration of
the standard.
4.1.6.3 Zero gas. See subsection 4.0.8. The zero gas should match the balance
gas used In the cylinder concentrations.
4.1.7 Assay Procedure
1. Verify that the assay apparatus Is properly configured, as described 1n sub-
section 4.1.3 and shown 1n Figure Gl.
2. Verify that the linearity of the analyzer has been checked within the last 3
months (see subsections 4.0.7.2, 4.0.7.5, and 4.1.4), that the zero and span are
adjusted correctly (subsection 4.0.7.3), that the candidate and reference gas
concentrations are within 25 and 97 percent of the upper range limit of the cali-
brated measurement range of the analyzer, and that the analyzer 1s operating
stably.
3. Adjust the flow rates of the three gases (reference, candidate, and zero) to
approximately the same value that will provide enough flow for the analyzer and
sufficient excess to assure that no ambient air will be drawn Into the vent.
4. Conduct a triad of measurements with the analyzer. Each triad consists of a
measurement of the zero gas concentration, a measurement of the reference gas
concentration, and a measurement of the candidate gas concentration. Use valves
VI and V2 to select each of the three concentrations for measurement. For each
measurement, allow ample time for the analyzer to achieve a stable response read-
Ing. Record the stable analyzer response for each measurement, using the same
response units (volt, millivolts, percent of scale, etc.) used for the multipoint
calibration and any transformation of the response readings necessary for linear-
ity. Do not translate the response readings to concentration values via the
calibration curve (see the footnote following Equation Gl). Do not make any
zero, span, or other physical adjustments to the analyzer during the triad of
measurements.
5. Conduct at least 2 additional measurement triads, similar to step 4 above.
However, for these subsequent triads, change the order of the three measurements
(e.g. measure reference gas, zero gas, candidate gas for the second triad and
zero gas, candidate gas, reference gas for the third triad, etc.).
6. If any one or more of the measurements of a triad 1s Invalid or abnormal for
any reason, discard all three measurements of the triad and repeat the triad.
7. For each triad of measurements, calculate the assay concentration of the
candidate gas as follows:
cc " cr RC " RZ Equation Gl
Rr ~ RT
-------
Section 3.0.4
Rev. 6/9/87
Page Gl-5
where:" Cc = Assay concentration of the candidate gas standard, ppm or
percent;
Cr = Concentration of the reference gas standard, ppm or percent;
Rc = Stable response reading of the Analyzer for the candidate
gas, analyzer response units;
Rz = Stable response reading of^the analyzer for the zero gas,
analyzer response units;*
Rr = Stable response reading of the Analyzer for the reference
gas, analyzer response units.
*Analyzer response units are the units used to express the direct response
readings of the analyzer, such as volts, millivolts, percent of scale, etc.
DO NOT convert these direct response readings to concentration units with the
multipoint calibration curve or otherwise adjust these readings except for
transformation necessary to achieve response linearity.
8. Calculate the mean of the 3 (or more) valid assays. Calculate the percent
difference of each assay from the mean. If any one of the assay values differs
from the mean by more than 1.5%, discard that assay value and conduct another
triad of measurements to obtain another assay value. When at least 3 assay val-
ues all agree within 1.5% of their mean, report the mean value as the certified
concentration of the candidate gas standard. For newly-prepared reactive stan-
dards, a reassay at least 7 days later 1s required to check the stability of the
standard; see subsection 4.0.6.2.
4.1.8 Stability Test for Newly-Prepared Standards
See subsections 4.0.6.1 and 4.0.6.2.
4.1.9 Certification Documentation
See subsections 4.0.4 and 4.0.5.
4.1.10 Recertlflcation Requirements
See subsections 4.0.6.3 and 4.0.6.4.
-------
Section 3.0.4
Rev. 6/9/87
References
4.2 References.
1. Code of Federal Regulations, Title 40, Part 60, "Standards of Performance for
New Stationary Sources," Appendix A, Method 20 (1982).
2. Standards of Performance for New Stationary Sources; Quality Assurance Re-
quirements for Gaseous Continuous Emission Monitoring Systems Used for Compliance
Determination, promulgated 1n the Federal Register. June 4, 1987, pp. 21003-
21010.
3. "A Procedure for Establishing Traceabllity of Gas Mixtures to Certain Nation-
.al Bureau of Standards Standard Reference Materials. EPA-600/7-81-010. Joint
publication by NBS and EPA, May 1981. Available from the U.S. Environmental
Protection Agency, Environmental Monitoring Systems Laboratory (MD-77), Research
Triangle Park, NC 27711.
4. Code of Federal Regulations, Title 40, Part 50, "National Ambient A1r Quality
Measurement Methodology".
^/
5. Code of Federal Regulations. Title 40, Part 58, "Ambient A1r Quality Surveil-
lance," Appendixes A and B.
6. Shores, R. C. and F. Smith, "Stability Evaluation of Sulfur Dioxide, Nitric
Oxide, and Carbon Monoxide Gases 1n Cylinders. NTIS No. PB 85-122646. Available
from the National Technical Information Service, 5285 Port Royal Road, Spring-
field, VA 22161.
7. Method 6A and 6B, "Determination of Sulfur Dioxide, Moisture, and Carbon
Dioxide Emissions from Fossil Fuel Combustion Sources," Quality Assurance Hand-
book for Air Pollution Measurement Systems. Volume III, Section 3.13.8, July
1986.Available from the U.S.Environmental Protection Agency, Center for Envi-
ronmental Research Information, Cincinnati, OH 45268.
8. "List of Designated Reference and Equivalent Methods." Current edition
available from the U.S. Environmental Protection Agency, Environmental Monitoring
Systems Laboratory, Quality Assurance Division (MD-77), Research Triangle Park,
NC 27711.
-------
5-01-79
Section 3.6.0
vvEPA
United States
Environmental Protection
Agency
Environmental Monitoring Systems
Laboratory
Research Triangle Park NC 27711
Research and Development
Section 3.5
Method 6—Determination of
Sulfur Dioxide Emissions from
Stationary Sources
Outline
Section
Summary
Method Highlights
Method Description
1. Procurement of Apparatus
and Supplies
2. Calibration of Apparatus
3. Presampling Operations
4. On-Site Measurements
5. Postsampling Operations
6. Calculations
7. Maintenance
8. Auditing Procedure
9. Recommended Standards for
Establishing Traceability
10. Reference Method
11. References
12. Data Forms
Summary
This Method 6 test procedure is
applicable to the determination of
sulfur dioxide emissions from
stationary sources. A gas sample is
extracted from the sampling point in
the stack. The sulfur dioxide is
separated from the sulfuric acid mist
(including sulfur trioxide) and is
measured 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, excess barium then reacts with
the thorin indicator to form a metal
salt of the indicator, resulting in a
color change.
The minimum detectable limit of the
method has been determined to be
3.4 mg SO2/m3 (2.12 x 10~7 Ib
SO2/ft3). Although no upper limit has
been established, tests have shown
Documentation
3.5
3.5
3.5.1
3.5.2
3.5.3
3.5.4
3.5.5
3.5.6
3.5.7
3.5.8
3.5.9
3.5.10
3.5.11
3.5.12
Number
of Pages
2
2
6
3
7
7
2
1
3
1
4
1
13
that concentrations as high as 80,000
mg SOz/m3 can be collected
efficiently in two midget impingers,
each containing 15 ml of 3%
hydrogen peroxide and the sampling
rate is 1.0 L/min for 20 min. Based
on theoretical calculations, the upper
concentration limit in a 20-L sample
is about 93,300 mg SOs/m3 if two
such impingers are used. The limits
may be extended by increasing the
number of impingers or by increasing
the peroxide concentration.
Interferences include free ammonia,
water-soluble cations, and fluorides.
The cations and fluorides are removed
by glass-wool filters and an initial
isopropanol bubbler, and hence do not
affect the S02 analysis. When
samples are being taken from a gas
stream with high concentrations of
very fine metallic fumes (such as from
inlets to control devices), a high-
efficiency glass-fiber filter must be
-------
Section 3.5.0
5-01-79
used in place of the glass-wool plug
in the probe to remove the cation
interferences. Free ammonia
interferes by reacting with S02 to
form particulate sulfite and thus
preventing it from reaching the
peroxide impingers, and by reacting
with the indicator. If free ammonia is
present (as indicated by white
particulate matter in the probe and
the isopropanol bubbler), an al-
ternative method, subject to the ap-
proval of the Administrator of the U.S.
Environmental Protection Agency, is
required.
The tester has the option of
substituting sampling equipment
described in Method 8 for the midget
impinger equipment of Method 6.
However, the Method 8 train must be
modified to include a heated filter
between the probe and the
isopropanol impinger and must be
operated at the flow rates defined in
Method 8. The heated filter will help
to eliminate the possibility of the SOz
reacting with the particulate matter.
The tester also has the option of
determining the emissions of SOj
simultaneously with particulate matter
and moisture determinations by (1)
replacing the water in a Method 5
impinger system with 3% peroxide
solution or (2) replacing the Method 5
water impinger system with a Method
8 isopropanol-filter-peroxide system.
The analysis for SC>2 and the
calibration of the metering system
must be consistent with the procedure
in Method 8.
The method description that follows
is based on the Reference Method
that was promulgated on August 18,
1977, and amended March 23, 1978.
Section 3.5.10 contains a complete
copy of the Reference Method, and
Section 3.5.12 provides blank data
forms for the convenience of the
Handbook user. References are in
Section 3.5.11. Reference 1 was used
in preparing the method description.
References 2, 3, and 4 are
collaborative test studies of this and
other related methods. Data from
these test studies were used in
establishing quality control limits
using the techniques of Reference 5.
References 6 through 12 are included
because of their potential value to the
user.
The accuracy of Method 6 was
checked using three standard gas
mixtures containing 224, 1121, and
2082 mg S02/m3 (14, 70, and 130 x
10~6 Ib SOz/scf), respectively. The
individual measurements by the
participating laboratories were all
within 24% of the true concentration.
The accuracy of the analytical phase
of Method 6 was checked using
standard sulfuric acid solutions of
three concentrations that were 2.
equivalent to sampled concentrations
of 281.9, 563.8, and 845.7 mg
SOz/m3 (17.6, 35.2, and 52.8 x 10~6
Ib SOz/scf), and a blank solution. The
individual measurements by all of the
participating laboratories were within
6% of the true concentration.
The estimated within-laboratory
precision (relative standard deviation)
was 4.0%. The between-laboratory
precision was 5.8%. The relative
standard deviation is the ratio of the
standard deviation of the measure-
ment to the mean measured value,
expressed as a percentage of this
mean value.
Method Highlights
Specifications described in this
Method 6 (Section 3.5) are only for
the uses of midget impingers and
midget bubblers with sample rates of
about 1 liter per minute (l/min). If the
tester opts to use the standard-sized
impingers, the Method 8 description
(Section 3.7) should be used as the
reference for equipment calibration,
sample setup, leak check, operation,
and sample recovery. The only
exceptions are that glass wool may be
put in the U-tube between the
isopropanol and peroxide impinger as
an option to the filter, the sampling is
to be conducted at a constant rate of
about 0.02 scm/min (0.75 scfm)
(AH@, orifice pressure differential
that gives 0.75 scfm of air at 70°F at
29.92 in. Hg); and the isopropanol
need not be analyzed.
The five blank data forms at the end
of this section may be removed from
the Handbook and used in the pretest,
test, and the posttest operations. Each
form has a subtitle (e.g., Method 6,
Figure 3.1) for helping the user find a
similar filled-in form in the method
description (Section 3.5.3). On the
blank and the filled-in forms, the
items/parameters that can cause the
most significant errors are starred.
1. Procurement of Equipment
Section 3.5.1 (Procurement of
Apparatus and Supplies) gives the
specifications, criteria, and design
features of the equipment and
material required to perform
Method 6 tests with the midget
impinger train. This section is
designed to provide the tester
with a guide for the procurement
and initial check of equipment and
supplies. The activity matrix (Table
1.1) at the end of Section 3.5.1
can be used as a quick reference,
and is a summary of the
corresponding written
descriptions.
Pretest Preparations
Section 3.5.2 (Calibration of
Apparatus) provides a step-by-step
description of the recommended
calibration procedures. The
accuracy and precision for the
equipment calibrations are the
same as those for Methods 5 and
8, with the exception that there is
no calibration requirement for the
rotameter. The lower sampling
rate required for the midget
impinger train allows the use of a
wet test meter with a capacity of
3 L/min or greater. The
calibration section can be
removed along with the
corresponding sections for the
other methods and used as a
separate quality assurance
reference manual by the
calibration personnel. The
calibration data are summarized
on the pretest sampling checks
form (Figure 2.5, Section 3.5.2).
Section 3.5.3 (Presampling
Operations) provides the tester
with a preparation guide for
equipment and supplies for the
field test. The pretest sampling
checks and pretest preparation
forms (Figure 3.1, Section 3.5.3)
or appropriate substitutes should
be used as equipment checkout
and packing lists. The sample im-
pingers may be charged in the
base laboratory if the testing is to
be performed within 24 h of
charging. The recommended
method described for packing the
containers should help protect the
equipment.
On-Site Measurements
Section 3.5.4 (On-Site
Measurements) contains step-by-
step procedures to perform the
sampling and sample recovery. A
checklist (Figure 4.4, Section
3.5.4) is provided to assist the
tester with a quick method of
checking that the procedures have
been completed satisfactorily.
Section 3.5.4 may be taken to the
field for reference but it would not
normally be needed by an
experienced crew. The most
common problem with the midget
impinger train is that the
hydrogen peroxide (HzOz) solution
can easily be backed up into the
isopropanol solution. This causes
the SOz to be removed in the first
impinger or in the glass wool. For
this reason, it is important to take
precautions in preventing this
-------
6-01-79
Section 3.5.0
occurrence, and it is suggested
that the isopropanol and glass-
wool plug be saved. The
isopropanol can then be analyzed
if any of the S02 data indicate
questionable results.
4. Posttest Operations
Section 3.5.5 (Postsampling
Operations) gives the posttest
equipment check procedures and
a step-by-step analytical pro-
cedure for determination of SQz
concentration. The two posttest
data forms (Figure 5.1, Section
3.5.5 and Figure 5.4, Section
3.5.5) or similar forms should be
used and the posttest sampling
checks form should be included in
the emission test report to docu-
ment the calibration checks. The
step-by-step analytical procedure
can be removed and made into a
separate quality assurance analyt-
ical reference manual for the
laboratory personnel. Analysis of
a control sample is required prior
to the analysis of the field
samples. This analysis of an inde-
pendently prepared known
standard will provide the labora-
tory with quality control checks on
the accuracy and precision of the
analytical techniques.
Section 3.5.6 (Calculations) pro-
vides the tester with the required
equations, nomenclature, and sig-
nificant digits. It is suggested that
a programmed calculator be used,
if available, to reduce the chance
of calculation error.
Section 3.5.7 (Maintenance)
provides the tester with a guide
for maintenance procedures;
these are not required, but should
reduce equipment malfunctions.
5. Auditing Procedure
Section 3.5.8 (Auditing Pro-
cedure) provides a description of
activities necessary for conducting
performance and system audits.
The performance audit of the
analytical phase can be performed
using aqueous ammonium sulfate
solution. Performance audits for
the analytical phase and the data
processing are described in
Section 3.5.8. A checklist for a
systems audit is also included in
this section.
Section 3.5.9 (Recommended
Standards for Establishing Tracea-
bility) recommends the primary
standards for establishing the
traceability of the working
standards. The volume measures
are compared to a primary liquid
displacement method, and the
analysis of the S02 is traceable to
primary standard grade potassium
acid phthalate.
Reference Material
Section 3.5.10 (Reference
Method) is the reference method
and thus the basis for the quality
assurance method description.
Section 3.5.11 (References) is a
listing of the references that were
used in this method description.
-------
Section 3.5.0 4 5-01-79
Pretest Samp/ing Checks
(Method 6, Figure 2.5)
Date Calibrated by.
Meter Box Number
Dry Gas Meter*
Pretest calibration factor = (within ±2% of average factor for each calibration run).
Impinger Thermometer
Was a pretest temperature correction used? yes ____^_ no
If yes. temperature correction (within ±.1°C (2° F) of reference values for calibration and within ±2°C(4°F)of
reference values for calibration check).
Dry Gas Meter Thermometer
Was a pretest temperature correction made? yes no
If yes, temperature correction (within ±3°C (S.4°F) of reference values for calibration and within
±6°C /10.8°F) of reference values for calibration check).
Barometer
Was the pretest field barometer reading correct? yes no
(within ±2.5 mm (0.1 in.) Hg of mercury-in-glass barometer).
'Most significant items/parameters to be checked.
-------
5-01-79
Section 3.5.0
Pretest Preparations
(Method 6, Figure 3.1)
Apparatus check
Probe
Type liner
GldffS
Stainless
,Vfr?p/
Q(h(?r
Heated properly
Leak checked on
sampling train
Filter
Glass wool
Other
Glassware
Midget bubbler
Midget impinger
Si">
Type
Meter System
Leak-free pumps*
Rate meter*
Dry gas meter*
Reagents
Distilled water
H202. 30%
Isopropanol. 100%*
Silica gel
Other
Barometer
Drying tube
Acceptable
Yes
No
Quantity
required
Ready
Yes
No
Loaded
and packed
Yes
No
•
*Most significant items /parameters to be checked.
-------
Section 3.5.0 6 5-01-79
On-Site Measurements
(Method 6. Figure 4.4)
Sampling
Bubbler and impinger contents properly selected, measured, and placed in impinger?'
Impinger Contents/Parameters'
t st: 15 ml of 80% isopropanol
2nd: 15mlof3%H20,
3rd: 15mlof3%H3C>2
Final impinger dry? __^____
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
System purged at least 15 min at test sampling rate?'
Contents of impingers placed in polyethylene bottles?
Fluid level marked?'
Sample containers sealed and identified?'
'Most significant items/parameters to be checked.
-------
6-01-79 7 Section 3.5.0
Posttest Sampling Checks
(Method 6. Figure 5.1)
Meter Box Number
Dry Gas Meter
Pretest calibration factor Y =.
Posttest check Y, = V8 = (±5% of pretest factor)*
Recalibration required? yes no
If yes, recalibration factor Y = (within ±2% of calibration factor for each
calibration run)
Lower calibration factor. Y = for pretest or posttest calculations
Rotameter
Pretest calibration factor Y, -
Posttest check Y, = (within ±10% of pretest factor)
Recalibration recommended? yes no
If performed, recalibration factor Y, =
Was rotameter cleaned? _____ yes _____ no
Dry Gas Meter Thermometer
Was a pretest meter temperature correction used? _____ yes ______ no
If yes. temperature correction ___________
Posttest comparison with mercury-in-glass thermometer within ±6°C
(10.8°F) of reference values
Recalibration required? _____ yes no
Recalibration temperature correction if used within ±3°C(5.4°F) of reference
values
If meter thermometer temperature is higher no correction needed
If recalibration temperature is higher, add correction to average meter temperature for
calculations
Barometer
Was pretest field barometer reading correct? yes no
Posttest comparison mm (in.) Hg within ±5.0 mm (0.2 in.) Hg of mercury-in-
glass barometer
Was recalibration required? yes ______ no
If field barometer reading is lower, no correction is needed
If mercury-in-glass reading is lower, subtract difference from field data readings for
calculations
'Most significant items/parameters to be checked.
-------
Section 3.5.0 8 5-01-79
Posttest Operations
(Method 6, 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
Volume of aliquot analyzed*
Do replicate titrant volumes agree within 1% 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%?*
All data recorded? Reviewed by
*Most significant items/parameters to be
checked.
-------
5-01-79
Section 3.5.1
1.0 Procurement of Apparatus and Supplies
A schematic diagram of an
assembled sulfur dioxide sampling
train with all components identified is
shown in Figure 1.1. 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 descriptive 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
3.5.12 for the Handbook user. If
calibration is required as part of the
acceptance check, the data are
recorded in the calibration log book.
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 capable of preventing water
condensation and with a filter (either
in-stack or heated out-stack) to
remove paniculate matter, including
sulfuric acid mist. 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 I.2 m (4 ft) total length
is usually sufficient for sampling.
However, the probe tip can be no
closer than 1 m (3.28 ft) from the
inner wall of stacks >2 m in diameter.
When stack gas temperatures exceed
480°C (900°F), a probe fabricated
from quartz (Vycon) should be used.
The main criterion in selecting a
probe material is that it be
nonreactive with the gas constituents
and therefore not introduce bias into
the analysis.
A new probe should be visually
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 described in
Section 3.5.3. The probe heating
system should be checked as follows:
1. Connect the probe (without filter)
to the inlet of the pump.
2. Electrically connect and turn on
the probe heater for 2 or 3 min.
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
temperature 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 Midget Bubbler/Impingers -
Each sampling train requires one
midget bubbler (30 ml) of medium
coarse glass frit, with glass wool
packed in the top to prevent carryover
of sulfuric acid mist. A midget
impinger may be used in place of the
midget bubbler.
Each sampling train requires three
midget impingers (30 ml) with glass
connections between the midget
bubbler and the midget impingers.
(Plastic or rubber tubing is not
permitted because these materials
absorb and 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 ab-
sorbers 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% 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 1% of the total S02.
1.1.3 Vacuum Pump - The vacuum
pump should be capable of
maintaining 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
standard 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.
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, clamp
the pump outlet line and turn off the
pump. The vacuum reading should
remain stable for 30 s.
1.1.4 Volume Meter - The dry gas
meter must be capable of measuring
total volume with an accuracy of
±2%, 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 temperature gauge
(dial thermometer, or equivalent)
capable of measuring the gas
temperature to within 3°C (5.4°F).
A new dry gas meter may be
checked for damage visually and by
performing a calibration according to
Section 3.5.2. Any dry gas meter that
is damaged, behaves erratically, or
does not give readings within ±2% of
the selected flow rate for each run is
unsatisfactory. Also upon receipt the
meter should be calibrated over a
varying flow range to see if there is
any effect on the calibration.
Dry gas meters that are equipped
with temperature compensation must
be calibrated over the entire range of
temperature that the meter
encounters under actual field
conditions. The calibration 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% of the calibrated value.
The wet test meter used to check
the dry test meter should be
calibrated using the primary
-------
Section 3.5.1
6-01-79
displacement technique explained in
Section 3.5.2. The wet test meter
must have a capacity of at least 0!003
mVmin (0.1 ftVmin) with an ac-
curacy of ±1%; otherwise at the high-
er flow rates, the water will not be
level and possibly will result in an in-
correct reading.
1.1.5 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 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 is performed at a
constant rate, which need not be
isokinetic, these changes do not affect
the sample volume measured by the
dry gas meter.
1.1.6 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.
1.1.7 Drying Tube - The drying tube
should be packed with 6- to 1 6-mesh
indicating-type silica gel, or
equivalent, to dry the sample gas and
protect the meter and pump. A drying
tube can be made by filling a 10-mm
polyethylene tube with silica gel and
packing glass wool in each end to
hold the silica gel and protect the
sampling system. Plastic tubing can
be utilized in any connections past the
collection system without affecting
the sampling results. The drying tube
should have a minimum capacity of
30 to 50 g of silica gel and should be
visually checked for proper size and
for damage.
If the silica gel has been used
previously, it must be dried at 1 75°C
(350°F) for 2 h. New silica gel may be
used, subject to approval of the Ad-
ministrator.
1.1.8 Thermometers • A dial ther-
mometer, 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-1 No. 63C or
63F. Damaged thermometers that
cannot be calibrated must be rejected.
1.1.9 Meter System - For ease of
use, the metering system — 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
1.3.
2. Shut off the needle valve and
insert positive pressure in the
system by blowing into the
rubber tubing until the inclined
manometer or magnehelic gauge
reads from 12.5 to 17.5 cm (5 to
7 in.) H20. 5^.
3. Pinch off the tube and observe
the manometer for 1 min. A loss
of pressure indicates a leak of
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 to the drying tube, and pull
a 250 mm Hg (10 in.) vacuum.
2. Pinch or clamp the outlet of the
flow meter. This can be accomp-
lished by closing the optional
shutoff valve if employed.
3. Turn off the pump. Any
deflection noted in the vacuum
reading within 30 s indicates a
leak.
4. Carefully release the vacuum
gauge before releasing the flow
meter end.
If either of these checks detects a
leak that cannot be corrected, the
meter box must be 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-1 No. 63C or
63F. The two ambient temperatures
used to calibrate the thermometer
must differ by a minimum of 10°C
(18°F). Damaged thermometers that
cannot be calibrated are to be
rejected.
1.1.10 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 differences 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.
1.1.11 Vacuum Gauge - At least
one 760-mm (29.92-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
(1.0in.)Hg.
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
polyethylene 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), including 5-, 10-,
20-, and 25-ml sizes, are required for
the analysis.
-------
5-01-79
Section 3.5.1
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.
1.3.5 Dropping Bottle - One 1 25-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.
1.4 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 01193-74, Type 3. At
the option of the analyst, the KMn04
test for oxidizable organic matter may
be omitted when high concentrations
of organic matter are not expected to
be present.
Isopropanol, 80% - Mix 80 ml of
reagent grade or certified ACS isopro-
panol (100%) 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%
potassium iodide (Kl) solution.
2. Prepare a blank by similarly
treating 10 ml of deionized
distilled water.
3. After 1 min, read the absorbance
of the alcohol sample against the
H2O blank at 352 nm on a
spectrophotometer. If absorbance
exceeds 0.1, reject the alcohol
for use. Peroxides may be
removed from isopropanol by
redistilling or by passing through
a column of activated alumina.
After peroxides are removed,
check for peroxide impurities
using the same method as above.
However, reagent grade
isopropanol with suitably low
peroxide levels may be obtained
from commercial sources. There-
fore, rejection of contaminated
lots may be a more efficient
procedure.
Hydrogen Peroxide, 3% - Dilute 30%
reagent grade or certified ACS
hydrogen peroxide 1:9 (v/v) with
deionized distilled water. Prepare
fresh daily. The 30% hydrogen
peroxide should be stored according to
manufacturer's directions.
Potassium Iodide Solution. 10% -
Dissolve 10.0 g of reagent grade or
certified ACS potassium iodide in
deionized distilled water and dilute to
100 ml. Prepare when needed. This
solution is used to check for peroxide
impurities in the isopropanol only.
1.4.2 Sample Recovery - The follow-
ing are required for sample recovery:
Water - Use deionized distilled
water, as in Subsection.1.4.1.
Isopropanol. 80% - Mix 80 ml of
reagent grade or certified ACS isopro-
panol with 20 ml of deionized distilled
water.
1.4.3 Analysis - The following are
required for sample analysis:
Water - Use deionized distilled
water, as in Subsection 1.4.1.
Isopropanol, 100% - Use reagent
grade or certified ACS isopropanol.
Thorin Indicator - Use reagent grade
or certified ACS 1-(o-
arsonophenylazo)-2-naphthol-3, 6-
disulfonic acid, disodium salt. Dissolve
0.20 g in 100 ml of deionized distilled
water.
Barium Perch/orate Solution.
0.0100N - Dissolve 1.95 g of reagent
grade or certified ACS barium
perchlorate trihydrate (BalCICuh
3M20) in 200 ml of distilled water and
dilute to 1 L with 100% isopropanol.
Alternatively, use 1.22 g of (BaCI2 •
2H2O) instead of the perchlorate.
Standardize, as in Section 3.5.5.
Sulfuric Acid Standard. 0.0 WON -
Either purchase the manufacturer's
certified or standardize the HaSOi at
0.01 OON +0.0002N against 0.01 OON
reagent grade or certified ACS 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 3.5.1
5-01-79
Probe (End Packed
.with Class Wool)
Midget ^— Thermometer
Impingers
Midget Bubbler \ \ Silica Gel
Glass Wool
nTmYTTTTmTTTYYITTnri
n
Stack Wall
\
(Fritted Tip)
Drying Tube
Heating Element
Surge Tank
Figure 1.1. SOi sampling train.
Procurement Log
Item description
Qty.
Purchase
order
number
Vendor
Date
Ord.
Rec.
Cost
Dispo-
sition
Comments
Metzr
r
far
vt
h J.8.
'A/"
IT T T T T T T 1
Figure 1.2. Example of a procurement log.
-------
5-01-79
Section 3.5.1
Blow into Tubing
Until Manometer
Reads 5 to 7 Inches
Water Column
Rubber
Tubing
T- Connector
Thermometer
Rate Meter
Needle Valve
(Closed}
Surge Tank
Figure 1.3. Meter box leak check.
Table 1.1. Activity Matrix for Procurement of Apparatus and Supplies
Apparatus and
supplies
Sampling
Sampling probe
with heating
system
Midget bubbler/
impinger
Vacuum pump
Dry gas meter
Wet test meter
Rotameter
Drying tube
Thermometers
Acceptance limits
Capable of maintaining
100°C(272°F)exitair
at flow rate of
1.0 L/min
Standard stock glass
Capable of maintaining
flow rate of 1 to 2
L/min; leak free
at 250 mm (10 in.) Hg
Capable of measuring
total volume within ±2%
at a flow rate of
1 L/min
Capable of measuring
total volume within ±1%
at a flow rate of
1 L/min
Within ±5% of manufac-
turer's calibration
curve (recommended)
Minimum capacity of
30 to 50 g of silica
gel
Within ±1°C(2°F) of
true value in the
range of 0° to 25°C
(32° to 77°F) for
impinger and ±3°C
(5.4°F) for dry gas
meter thermometer
Frequency and method
of measurement
Visually check and
run heating system
checkout
Visually check upon
receipt for breaks
or leaks
Check upon receipt
for leaks and capac-
ity
Check for damage upon
receipt and calibrate
fSec. 3.5.2) against
wet test meter
Upon assembly, leak
check all connections
and check calibration
by liquid displace-
ment
Check upon receipt
for damage and cali-
brate (Sec. 3.5.2)
against wet test
meter
Visually check upon
receipt for damage
and proper size
Check upon receipt
for damage (i.e..
dents and bent stem),
and calibrate
(Sec. 3.5.2) against
mercury-in-glass
thermometer
Action if
requirements
are not met
Repair or
return to
supplier
Return to manu-
facturer
As above
Reject if damaged,
behaves erratical-
ly, or cannot be
properly adjusted
As above
Recalibrate and
construct a new
calibration
curve
Return to
supplier
Return to
supplier if
unable to
calibrate
-------
Section 3.6.1
5-01-79
Table 1.1. (continued)
Apparatus and
supplies
Barometer
Vacuum gauge
Sample Recovery
Wash bottles
Storage
bottles
Analysis Glass-
ware
Pipettes, volu-
metric flasks.
burettes, and
graduated
cylinder
Reagents
Distilled
water
Isopropanol
Hydrogen
peroxide
Potassium
iodide solu-
tion
Thorin indica-
tor
Barium per-
chlorate
solution
Sulfuric acid
solution
Acceptance limits
Capable of measuring
atmospheric pressure
to within ±2.5 mm
(0. 1 in.) Hg calibrate
0 to 760 mm (0 to
29.92 in.) Hg range.
±2.5 mm (0. 1 in.) Hg
accuracy at 250 mm
(Win.)Hg
Polyethylene or glass,
500ml
Polyethylene. WO ml
Glass. Class A
Must conform to ASTM-
D1 193-74. Type 3
100% isopropanol. rea-
gent grade or certi-
fied ACS with no
peroxide impurities
30P/oHzOt, reagent grade
or certified ACS
Potassium iodide, re-
agent grade or certified
ACS
1 -(o-arsonophenylazo)-
2-naphthol-3. 6-disul-
fonic acid disodium
salt, reagent grade of
certified ACS
Barium perchlorate tri-
hydrate (BafCIO*)?
3HzO), reagent grade
or certified ACS
Sulfuric acid, 0.0100N
±0.0002N
Frequency and method
of measurement
Check against mer-
cury-in-glass barome-
ter or equivalent
(Sec. 3.5.2)
Check against U-tube
mercury manometer
upon receipt
Visually check for
damage upon receipt
\
Visually check for
damage upon receipt,
and be sure that caps
seal properly
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 perox-
ide impurities with
a spectrophotometer
Upon receipt, check
label for grade or
certification
As above
As above
As above
Have certified by
manufacturer or
Action if
requirements
are not met
Determine cor-
rection factor,
or reject if
difference is
more than ±2.5
Adjust or re-
turn to sup-
plier
Replace or re-
turn to sup-
plier
As above
As above
As above
Redistill or
pass through
alumina column,
or replace
Replace or re-
turn to manu-
facturer
As above
As above
As above
As above
standardize against
0.01 OONNaOH that
has been standard-
ized against potas-
sium acid phthalate
(primary standard
grade)
-------
5-01-79
Section 3.5.2
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 section. If
the tester opts to use Method 5 or
Method 8 sampling apparatus, then
the calibration procedures governing
that equipment will apply and must be
used. 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
2.1.1 Wet Test Meter - The wet test
meter must be calibrated and have
the proper capacity. For Method 6, the
wet test meter should have a capacity
of at least 3 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%. 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%:
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 calibra-
tion system as shown in Figure
2.1.
a. Fill the rigid-wall 5-gal jug
with distilled water to below
the air inlet tube. Put water in
the impinger or saturator 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 volu-
metric flask.
5. Check operation of the meter as
follows:
a. If the manometer reading is
<10 mm (0.4 in.) H20, the
meter is in proper working
condition. Continue to step 6.
b. If the manometer reading is
>10 mm (0.4 in.) H2O, 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 the inlet to the saturator. 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
saturator.
7. Read the initial volume (VJ 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-L mark. Record the final
volume on the wet test meter.
11. Steps 7 through 10 must be
performed three times.
Since the water temperature in the
wet test meter and reservoir 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 measurement
error and would not affect the final
calculations.
The error should not exceed ±1%;
should this error magnitude be
exceeded, check all connections
within the test apparatus for leaks,
and gravimetrically check the volume
of the 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 spe-
cifications are met.
2.1.2 Sample Meter System - The
sample meter system — consisting of
the drying tube, needle valve, pump,
rotameter, and dry gas meter — is
initially calibrated by stringent labora-
tory methods before it is used in the
field. The calibration is then
rechecked after each field test series.
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
calibration 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.
Initial Calibration - The metering
system should be calibrated when
first purchased and at any time the
posttest check yields a calibration
factor that does not agree within 5%
of the pretest calibration factor. A
calibrated wet test meter (properly
sized, with ±1% 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
(drying tube, needle valve, pump,
rotameter, and dry gas meter) as
follows:
a. Temporarily attach a suitable
rotameter (e.g., 0-40
cmVmin) to the outlet of the
dry gas meter, and place a
vacuum gauge at the inlet to
the drying tube.
-------
Section 3.5.2
5-01-79
b. Plug the drying tube inlet. Pull
a vacuum of at least 250 mm
(10in.)Hg.
c. Note the flow rate as
indicated by the rotameter.
d. A leak of <0.02 L/min must
be recorded or leaks must be
eliminated.
e. Carefully release the vacuum
gauge before turning off
pump.
2. Assemble the apparatus, as
shown in Figure 2.3, with the
wet test meter replacing the dry-
ing tube and impingers; that is,
connect the outlet of the wet test
meter to the inlet side of the
needle valve and the inlet side of
the wet test meter to a saturator
which is open to the atmosphere.
Note: Do not use a drying tube.
3. Run the pump for 1 5 min 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 of the three
runs using Equation 2-1. Record
the values in the form (Figure
2.4A or 2.4B).
Yi=.
13.6
(td + 460)
Vd Pm (tw + 460)
Equation 2-1
where
Yi = ratio for each run of volumes
measured by the wet test meter
and the dry gas meter, dimen-
sionless calibration factor,
Vw = volume measured by wet test
meter, m3 (ft3),
Pm = barometric pressure at the
meters, mm (in.) Hg,
Dm = pressure drop across the wet
test meter, mm (in.) H20,
td=average temperature of dry gas
meter, °C (°F),
V5% 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
calibration factor does deviate by
>5%, recalibrate the metering 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
impinger train should be initially
compared with a mercury-in-glass
thermometer that meets ASTM E-1
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 thermpmeters to
come to room temperature.
Compare readings after both
stabilize.
3. The dial type or equivalent ther-
mometer is acceptable if values
agree within ±1°C (2°F) at both
points. If the difference is greater
than ±1°C (2°F), either adjust or
recalibrate the thermometer until
the above criteria are met, or
reject it.
4. Prior to each field trip, compare
the temperature reading of the
mercury-in-glass thermometer
with that of the meter
thermometer at room
temperature. If the values are not
within ±2°C (4°F) of each other,
replace or recalibrate the meter
thermometer.
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-1 No. 63C or 63F
specifications:
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 ther-
mometer 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 reading 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.
2.3 Rotameter
The Reference Method does not
require that the tester calibrate the
rotameter. The rotameter should be
leaned and maintained according to
the manufacturer's instructions. For
-------
5-01-79
Section 3.5.2
this reason, it is recommended that
the calibration curve and/or rotameter
markings be .checked upon receipt and
then routinel'y checked with the
posttest meter system check. The
rotameter may be calibrated as
follows:
1. Ensure that the rotameter has
been cleaned as specified by the
manufacturer, and is not
damaged.
2. Use the manufacturer's
calibration curve and/or
markings on the rotameter for
the initial calibration. Calibrate
the rotameter 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 1.0 ±0.05 L/min. If,
however, the calibration point is
not within ±5%, 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% of the 1-L/min
setting, the rotameter can be
acceptable with proper mainte-
nance. If, however, the check is
not within ±10% of the flow
setting, disassemble and clean
the rotameter and perform a full
recalibration.
2.4 Barometer
The field barometer should be ad-
justed 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)
elevation increase, or vice versa for
elevation decrease.
The calibration checks should be
recorded on the pretest sampling form
(Figure 2.5).
Air Inlet j
Tube,
Impinger
or
Saturator
Air Inlet
Q X) Valve
2000-ml Line
Type^A
6 \Volumetric
Flask
Figure 2.1. Calibration check apparatus for wet test meter.
-------
Section 3.6.2
5-01-79
Wet Test Meter Calibration Log
Wet test meter serial number _
Range of wet test meter flow rate C/ " f AO
Volume of test flask V, = *?• 00 1
Satisfactory leak check?
Ambient temperature of equilibrate liquid in wet test meter and reservoir
Test
number.
1
2
3
Manometer
reading. *
mm HiO
4T
-------
5-01-79
Section 3.6.2
Data /-<£*' 70 ralihraterf hy <_/ t7 vTO
t*29 V/
Parameter pressure Pm- o*f•^J^
Meter temperature correction factor
in Hg
MA
Meter box number
Wet test meter number
°f
JT- I
101- A
Wet test
meter
pressure
drop (D^.'
in. HiO
O.JLS
0.-3.T
Q. «25-
Rota-
meter
setting
(R,i.
ft3/min
0-OBS-
0.03S-
o.o as
Wet test
meter gas
volume
^w/"
ft3
1.0 SB
I.OSl
I.Obl
Dry test meter
gas volume
fVoJ." ft3
Initial
W.MS
7ZI.1V
W-otB
Final
nd.tn
130-0^1
7J3.K6
Wet test
meter
gas temp
<,>.
°f
7«
8C
8C
Average
gas temp
(to).'
°F
v>
81
8i
Time
of run
(6)."
min
JO
JO
JO
A verage
ratio
IYJ.'
I.OIf
i.od
/.Of 8
<
Wet test
meter
gas temp
ftj.
°C
21
22.
Hi
Inlet
gas temp
(U).
°C
il
Z.6
it
Dry test meter
Outlet
gas temp
IttJ.
°C
Lit
ZT
it
A verage
gas temp
(U*
°C
l(r ST
ii-f
A».5-
Time
of run
(8),'
min
J0
3<3
JO
Average
ratio
fYJ.'
I.OIf
/.0/ and ta0 if using two thermometers; the actual reading if using one thermometer.
"The time it takes to complete the calibration run.
'With Y defined as the average ratio of volumes for the wet test and the dry test meters. Y,= Y ±0.02 Y for calibration and Yt= Y ±0.05 Y
for the posttest checks, thus,
Y( -
+ 273°C)[Pm ^ (Dm/13.6)]
-
Y, + Y2
-- 3
• (Eg. 2)
'With Y, defined as the average ratio of volumetric measurements by wet test meter to rotameter. tolerance Y, - 1 ±0.05 for calibration and Y
±0.1 for posttest checks.
Y,, =
,(t, + 273°C) lPm +(Dm/13.6)] (Eq3) gndYi=Y^
8 (t, + 273°C) Pm (0.035)
•
-------
Dare
Meter box number
Section 3.5.2
?- IS'- 1$
rm- i
6
Calibrated bv
AH©
5-01-79
USD
/.v/
Dry Gas Meter'
Pretest calibration factor = U- 7OV (within ±2% of average factor for each calibration run).
Impinger Thermometer
Was a pretest temperature correction used?.
yes
no
If yes, temperature correction.
, (within ±1°C(2°F) of reference values for calibration and within ±2°C(4°F) of
reference values for calibration check).
Dry Gas Meter Thermometer
Was a pretest temperature correction made?_
.Yes .
If yes, temperature correction
. (within ±3°C (5.4°F) of reference values for calibration and within
±6°C (W.8°F) of reference values for calibration check).
Barometer
Was the pretest field barometer reading correct?
yes
(within ±2.5 mm (0.1 in) Hg of mercury-in-glass barometer)
'Most significant items/parameters to be checked.
Figure 2.5. Pretest sampling checks.
Table 2. 1 . Activity Matrix for Calibration of Equipment
Apparatus Acceptance limits
Wet test meter
Dry gas meter
Impinger ther-
mometer
Dry gas meter
thermometer
Rotameter
Barometer
Capacity of at least 2
L/min and accuracy
within ±1.0%
Y,= Y±0.02Yata
flow rate of about
1 L/min
Within ±1°C(2°F)
of true value
Within ±3°C (5.4°F)
of true value
Clean and maintain ac-
cording to manufactur-
er's instructions
(required); calibrate
to ±5% (recommended)
Within ±2.5 mm •
(0. 1 in.) Hg of mer-
cury-in-glass
barometer or of weather
station value
rrequency and method
of measurement
Calibrate initially
and then yearly
by liquid displace-
ment
Calibrate vs. wet
test meter initially
and when the posttest
check is not within
Y±0.05
Calibrate each ini-
tially as a separate
component against a
mercury-in-glass
thermometer; after
train is assembled
before each field
test, compare with
mercury -in -glass
thermometer
As above
Initially and after
each field trip
Calibrate initially
using a mercury-in-
glass barometer;
check before and
after each field test
Action if
requirements
are not met
Adjust until
specifications
are met, or
return to
manufacturer
Repair and
then recali-
brate, or re-
p/ace
Adjust, deter-
mine a con-
stant correc-
tion factor, or
reject
As above
Adjust and
recalibrate,
or reject
Adjust to
agree with
certified
barometer
-------
6-01-79
Section 3.5.3
3.0 Presampling Operations
The quality assurance activities for
presampling preparation are sum-
marized in Table 3.1 at the end of this
section. See Section 3.0 of this Hand-
book for details on preliminary site
visits.
3.1 Apparatus Check and
Calibration
Figure 3.1 or similar form is recom-
mended 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 Reference 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 bubbler, 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 Drying tubes - Drying tubes
should be packed with 6- to 16-mesh
silica gel and sealed at both ends.
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 recommended by the
manufacturer.
3.1.6 Pump - The vacuum pump and
oiler should be serviced as recom-
mended by the manufacturer, every 3
mo, or every 10th test (whichever
comes first), or upon erratic behavior
(nonuniform or insufficient pumping
action).
3.1.7 Dry gas meter - A dry gas
meter calibration check should be
made in accordance with the
procedure in Section 3.5.2. An
acceptable posttest check from the
previous test is sufficient.
3.1.8 Thermometers - The ther-
mometers 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
the mercury-in-glass barometer or
with a National Weather Service
Station reading prior to each field trip.
3.2 Reagents and Equipment
3.2.1 Sampling - The midget
bubbler solution is prepared by mixing
80 ml of reagent grade or certified
ACS isopropanol (100%) with 20 ml of
deionized distilled water. The midget
impinger absorbing reagent (3%
hydrogen peroxide) is prepared by
diluting 100 ml of 30% hydrogen
peroxide to 1 L with deionized distilled
water. All reagents must be prepared
fresh for each test series, using ACS
reagent grade chemicals. Solutions
containing isopropanol must be kept
in sealed containers to prevent
evaporation.
3.2.2 Sample recovery - Deionized
distilled water is required on site for
quantitative transfer of impinger solu-
tions to storage containers. This water
and reagent grade 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 pro-
tected 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 in-
dividual devices. The case should be
equipped with handles or eye 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
h.
3.3.3 Drying tubes and volumetric
glassware - A rigid container lined
with polyethylene foam material
protects drying tubes and assorted
volumetric glassware.
3.3.4 Meter box - The meter box —
which contains the valve, rotameter,
vacuum pump, dry gas meter, and
thermometers — 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 con-
tainers - Storage containers and mis-
cellaneous glassware may be safely
transported, if packed in a rigid foam-
lined container. Samples being trans-
ported in the containers should be
protected from extremely high
ambient temperatures (>50°C or
about 120°F).
-------
Section 3.5.3
5-01-79
Apparatus Check
Probe
Type liner
Class lS
Stainless
steel
Other
Heated properly
Leak checked on
sampling train
Filter
Glass wool
Other
Glassware
Midget bubbler
Midget impinger
Size fllD&£T
Type STD,
Meter System
Leak-free pumps*
Rate meter*
Dry gas meter*
Reagents
Distilled water
W2Oa 30%
Isopropanol. 100%*
Silica gel
Other
Barometer
Drying tube
Acceptable
Yes
IS
S
s
,x
t
t
$
&
t
No
Quantity
Required
3
S*all$of
6
16
2.
?&
Ijal.
tft-
i
10
Loaded
Ready and Packed
Yes
IX
IX
•X
^
iX
iX
^
iX
iX
No
Yes
-------
6-01-79
Section 3.5.3
Table 3.1. Activity 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 250 mm (10 in.) Hg
1. Clean probe in-
ternally by brushing
with tap water, then
deionized distilled
water, then acetone;
allow to dry in air
before test
2. Visual check
before test
1. Retrace
cleaning pro-
cedure and
assembly
2. Replace
Midget bubbler.
midget impin-
ger, and
glass connec-
tors
Flow control
valve and
rotameter
Vacuum pump
Dry gas meter
Reagents
Sampling
Sample recovery
Package Equip-
ment for Ship-
ment
Probe
Midget bubbler,
impingers,
connectors.
and assorted
glassware
Drying tubes,
volumetric
glassware
Meter box
Wash bottles
and storage
containers
3. No moisture con-
densation
Clean and free of
breaks, cracks, etc.
Clean and without sign
of erratic behavior
(ball not moving freely)
Maintain sampling rate
of about 1 L/min up to
250 mm (10 in.) Hg
Clean and within ±2%
of calibration factor
Requires all ACS grade
reagents
Requires deionized dis-
tilled water on site
Protect with poly-
ethylene foam
Pack in rigid con-
tainers with poly-
ethylene foam
Sturdy container
lined with foam
Meter box case and/or
container to protect
components; pack spare
meter box and oil
Pack in rigid foam-
lined container
3. Check out heating
system initially and
when moisture appears
during testing
Clean with detergent,
tap water, and then
with deionized dis-
tilled water
Clean prior to each
field trip or upon
erratic behavior
Service every 3 mo or
upon erratic behav-
ior; check oiler
jars every 10th test
Calibrate according
to Sec. 3.5.2; check
for excess oil if
oiler is used
Prepare fresh daily
and store in seated
containers
Use water and reagent
grade isopropanol to
clean midget bubbler
after test and before
sampling
Prior to each ship-
ment
As above
As above
As above
As above
3. Repair or
replace
Repair or
discard
Repair or
return to
manufacturer
As above
As^bove
Prepare new
reagent
Prepare new
reagent
Repack
As above
As above
As above
As above
-------
6-01-79
Section 3.5.4
4.0 On-Site Measurements
On-site activities include transport-
ing the equipment to the test site,
unpacking and assembling, sampling
for sulfur dioxide, and recording the
data. The 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 trans-
porting the equipment from ground
level to the sampling site (often above
ground level) should be decided dur-
ing 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 bubbler and
impingers, and for sample recovery.
4.2 Preliminary Measurements
and Setup
The Reference Method outlines the
procedure used to determine the
concentration of sulfur dioxide in the
gas stream. The accuracy of the
equipment that has been transported
to the sampling site and that may
have been handled roughly 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., Vd = Vw). Yri
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 identifica-
tion number on the sampling data
form, Figure 4.1.
4.3 Sampling
The on-site sampling includes the
following steps:
1. Preparation and/or addition of
the absorbing reagents to the
midget bubbler and impingers.
2. Setup of the sampling train.
3. Connection to the electrical ser-
vice.
4. Preparation of the probe (leak
check of entire sampling train
and addition of paniculate 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 sampling.
4.3.1 Preparation and/or Addition of
Absorbing Reagents to Collection
System - Absorbing reagents can be
prepared on site, if necessary, accord-
ing to the directions in Section 3.5.3.
1. Use a pipette or a graduated
cylinder to introduce 15 ml of
80% 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.
Pipettes or graduated cylinders
should be marked for use of HzOz
or IPA to minimize any possibility
of introducing hydrogen peroxide
into the isopropanol.
2. Add 1 5 ml of 3% hydrogen per-
oxide to each of the first two
midget impingers; leave the final
midget impinger dry.
3. Pack glass wool into the top of
the midget bubbler to prevent
sulfuric acid mist from entering
the midget impingers and caus-
ing a high bias for SOz.
4.3.2 Assembling the Sampling
Train - After assembling the sampling
train as shown in Figure 1.1, perform
the following:.
1. Adjust probe heater to operating
temperature. Place crushed ice
and water around the impingers.
2. Leak check the sampling train
just prior to use at the sampling
site (not mandatory) by
temporarily attaching a rotameter
(capacity of 0 to 40 cmVmin) 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 net"
< 2% of the average sampling
rate is acceptable. Note -
Carefully release the probe inlet
plug before turning off the pump.
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 precede the leak
check of the sampling train. If
after, the pump leak check shall
follow the train leak check. To
leak check the pump, proceed as
follows: Disconnect the drying
tube from the probe impinger
assembly. Place a vacuum gauge
at the inlet to either the drying
tube or 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 s.
3. Place a loosely packed filter of
glass wool in the end of the
probe, and connect the probe to
the bubbler.
4.3.3 Sampling (Constant Rate) -
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:
1. 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 be sure that
no hydrogen peroxide has been
allowed to back up and wet the
glass wool.
2. 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 while
disconnected from the impinger,
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 contam-
inating the isopropanol.
3. Adjust the sample flow to a
constant rate of approximately
1.0 L/min as indicated by the
rotameter.
4. Maintain this constant rate
within 10% during the entire
sampling run, and take readings
(dry gas meter, temperatures at
-------
Section 3.5.4
5-01-79
dry gas meter and at impinger
outlet, and rate meter) at least
every 5 min. 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.
5. 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
min and a minimum sampling
volume of 20 L corrected to
standard conditions.) The total
sample volume at meter condi-
tions should be approximately 28
L (1 ft3). 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 min.
6. Turn off the pump at the conclu-
sion 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.
7. Conduct a leak check, as
described in Subsection 4.3.2
(mandatory).
8. If the train passes the leak check,
drain the ice bath and purge the
remainder of the train by draw-
ing clean ambient air through the
system for 15 min at the samp-
ling rate. To provide clean
ambient air, pass air through a
charcoal filter or through an
extra midget impinger with 15 ml
of 3% H202. The tester may opt
to use ambient air without
purification.
9. Calculate the sampling rate dur-
ing the purging of the sample.
The sample volume (AVm) for
each point should be within
±10% 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% of constant rate for a
single sample should not have a
significant effect on the final
results of the test for noncyclic
processes.
10. 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 SOa due to
reactions with particulate matter.
4.4 Sample Recovery
The Reference Method requires
transfer of the impinger contents and
the connector washings to a polyeth-
ylene storage container. This transfer
should be done in the "laboratory"
area to prevent contamination of the
test sample.
After completion of the purge, dis-
•connect the impingers and transport
them to the cleanup area. The
contents of the midget bubbler
(contains isopropanol) may be
discarded. However, it is usually
advisable to retain this fraction until
analysis is performed on the HzOz.
Analysis of the isopropanol may be
useful in detecting cleanup or samp-
ling errors. Cap off the midget
impinger section with the use of
polyethylene or equivalent caps before
transport to the cleanup area.
Transfer the contents of the midget
impingers into a labeled, leak-free
polyethylene sample bottle. Rinse the
three midget impingers a couple of
times and the connecting tubes with 3
to 15 ml portions of distilled water.
Add these washings to the same
sample bottle, and mark the fluid level
on the side. The total rinse and
sample volume should be <100 ml; a
100-ml mark can be placed on the
outside of the polyethylene containers
as a guide. Place about 100 ml of the
absorbing reagent (3% H&z) in a
polyethylene bottle and label it for use
as a blank during sample analysis. An
example of a sample label is shown in
Figure 4.2.
4.5 Sample Logistics (Data)
and Packing Equipment
The sampling and sample recovery
procedures are followed until the
required number of runs are
completed. Log all data on the Sample
Recovery and Integrity Data Form,
Figure 4.3. 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. A new
drying tube should be inserted into
the sampling train. At the completion
of the test:
1. Check all sample containers for
proper labeling (time, date, loca-
tion, number of test, and any
pertinent documentation). Be
sure that a blank has been taken.
2. Record all data collected during
the field test in duplicate by us-
ing carbon paper or by using data
forms and a field laboratory note-
book. One set of data should be
mailed to the base laboratory,
given to another team member or
to the Agency. Hand carrying the
other set (not mandatory) can
prevent a very costly and embar-
rassing 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 quick check of the samp-
ling and sample recovery proce-
dures using the-data form. Figure
4.4.
-------
Plant name
Sample location
Operator .
g>*
Barometric pressure, mm Hg
material
Meter box number
Ambient temperature, °C
Initial leak check
Final leak check
City
Date
Sample number
Probe length m
Probe heater setting
Meter calibration factor (Y) .
Sample point location /1»
Sample purge^tjme. min
Remarks
/
/*/,*/
'
/• & /
//?
Ol
6
to
Sampling
time,
min
XT
Total
Clock
time,
24 h
//**
Sample
volume,
L
SW.26
Total
Sample flow
rate setting,
L/min
Sample volume
metered (LVm),
L
y.f
avg
Percent
deviation"
dev
Dry gas
meter temp.
°C
3*
30
Avg
Impinger
temp,
°C
o
s.
o
Max
temp
'Percent deviation =
av9 inn
AV avgm
Figure 4.1. Field sampling data form for SO*
-------
Section 3. 5. 4
5-01-79
Sit,, &//**/%. 3 .<:„„,,,/„,„„/ cS0?
Data &/'^/f' Run number 5 (J "/
Front rinse D Front filter D Front solution D
Back rinse D Back filter D Back solution &r
//L./) ^
Snhitinn "% CX^ Level markeH WT
Volume- Initial m^0'& ^- Final ^~/0Oflf£^ m
g
Cleanup by . ft^UTL/ o-
Figure 4.2. Example of a sample label.
-------
5-01-79
Section 3.5.4
Plant
Sample location
3
Field Data Checks
Sample recovery personnel
Person with direct responsibility for recovered samples .
Sample
number
1
2
3
4
5
6
Blank
Sample
identification
number
SO-/
Date
of
recovery
&//0/??
Liquid
level
marked
/
-------
Section 3.5.4 6 5-01-79
Sampling
Bubbler and impinger contents properly selected, measured, and placed in impinger?* *
Impinger Contents/Parameters*
1st: 15 ml of 80% isopropanol *
'
2nd: 15mlof3%HtC>2
3rd: 15mlof3%HtOx
Final impinger dry? '
Probe heat at proper level?
Crushed ice around impingers? ____
Pretest leak check at 250 mm (10 in.l 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? i
Sample Recovery
System purged at least 15 min at test sampling rate?*
Contents of impingers placed in polyethylene bottles?
Fluid level marked?*
Sample containers sealed and identified?* *
'Most significant items/parameters to be checked.
Figure 4.4. On-site measurements.
-------
5-01-79
Section 3.5.4
Table 4.1. Activity
Activity
Preparation
and/ or addi-
tion of ab-
sorbing
reagents
Assembling the
sampling
train
Matrix for On-Site Measurement Checks
Acceptance limits
Add 1 5 ml of 80% iso-
propanol to midget
bubbler and 15 ml of
3% H202 to first two
midget impingers
1 . Assemble to speci-
fications in Fig. 1. 1
2. A leakage rate <2%
of the average sampling
Frequency and method
of measurement
Prepare 3% H2O2 fresh
daily; use pipette
or graduated cylinder
to add solutions
1. Before each sam-
pling
2. Leak check before
sampling (recommended)
Actiffn if
requirements
are not met
Reassemble
collection
system
1. Reas-
semble
2. Correct
the leak
rate
by attaching a rotame-
ter to dry gas meter
outlet, placing a
vacuum gauge at or
near probe inlet, and
pulling a vacuum of
>250 mm (10 in.) Hg
Sampling (con-
stant rate)
1. Within ±10% of a
constant rate
2. Minimum acceptable
1. Calculate % devi-
ation for each sample
using equation in
Fig. 4. 1
2. Make a quick cal-
1. Repeat the
sampling, or
obtain accept-
ance from a
representative
of the
Administrator
2. As above
time is 20 min and vol-
ume is 20 L corrected
to STP or as specified
by regulation
3. Less than 2% leakage
rate at 250 mm (10 in.)
4. Purge remaining SOz
from isopropanol
culation prior to
completion and an ex-
act calculation after
3. Leak check after
sample run (manda-
tory); use same pro-
cedure as above
4. Drain ice and
purge 15 min with
clean air at the
sample
3. All sample contain-
ers properly labeled
and packaged.
3. Visually check
upon completion of
test
3. As above
4. As above
Sample logis-
tics (data)
and packing
of equipment
1. All data are re-
corded correctly
2. All equipment ex-
amined for damage and
labeled for shipment
1. Visually check
upon completion of
each run and before
packing
2. As above
1. Complete
the data
form
2. Redo test
if damage
occurred
during testing
3. Correct
when possible
-------
5-01-79
Section 3.5.6
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 cleaning,
and/or the performance of routine
maintenance — should be made on
most of the sampling apparatus.
Cleaning and maintenance of the
sampling apparatus are discussed in
Section 3.5.7. Figure 5.1 should be
used to record the posttest checks.
5.1.1 Metering System - The meter-
ing system has three components that
must be checked: dry gas meter ther-
mometer(s), dry gas meter, and rota-
meter.
The dry gas meter thermometer
should be checked by comparison
with the ASTM mercury-in-glass ther-
mometer at room temperature. If the
readings agree within 6°C (10.8°F),
they are acceptable. When the
readings are outside this limit, the
thermometer must be recalibrated
according to Section 2.5.2 after the
posttest 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 correc-
tion 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 Sec-
tion 3.5.2, 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 posttest dry gas
meter calibration factor (Y) does
not deviate by >5% from the
initial calibration factor, the dry
gas meter volumes obtained
during the test series are
acceptable. If it deviates by >5%
recalibrate the metering system
as in Section 3.5.2, using the
calibration factor (initial or
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 deviate by >10% from the
initial calibration factor, the rotameter
operation is acceptable. If Y changes
by >10%, the rotameter should be
cleaned and recalibrated. No correc-
tions need be made for any calcula-
tions.
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.
5.2 Analysis (Base
Laboratory)
Calibrations and standardizations
are of the utmost importance to a
precise and accurate analysis. The
analysis is based on the insolubility of
barium sulfate (BaSCU) and on the
formation of a colored complex
between excess barium ions and the
thorin indicator, 1-(o-
arsonophenylazo)-2-naphthol-3, 6-
disulfonic 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.
S04
thorin (x+t) -
(yellow)
BaSC>4 + thorin (Ba+t)
(pink)
Equation 5-1
Upon completion of each step of the
standardization or of each sample
analysis, the data should be entered
on the proper 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:
1. Water. Deionized distilled water
that conforms to ASTM specifica-
tion D1193-74, Type 3. At the
option of the analyst, the KMnCu
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 concentration
rather than the sulfate ion con-
centration. 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
5.2.4.
2. Isopropanol. 100%, ACS reagent
grade. Check for peroxide impuri-
ties as described in Section
3.5.1.
3. Thorin indicator. Dissolve 0.20
±0.002 g of 1 -(o-
arsonophenylazo)-2- naphthol-
3,6-disulfonic acid, disodium salt,
or the equivalent, in 100 ml of
deionized distilled water.
Measure the distilled water in
the 100-ml graduated cylinder
(Class A).
4. Su If uric acid standard. 0.0 WON.
Either purchase manufacturer-
guaranteed or standardize the
H2SO< to ±0.002N against
0.01 DON NaOH that has been
standardized against potassium
acid phthalate (primary standard
grade) as described in Subsection
5.2.3. The 0.01 N H2SO« may be
prepared in the following
manner:
-------
Section 3.6.5
5-01-79
a. Prepare 0.5N H2S04 by adding
approximately 1500 ml of dis-
tilled water to a 2-L
volumetric flask.
b. Cautiously add 28 ml of con-
centrated sulfuric acid and
mix.
c. Cool if necessary.
d. Dilute to 2 L with distilled
water.
e. Prepare 0.01 N H2S04 by first
adding approximately 800 ml
of distilled water to a 1-L
volumetric flask and then
adding 20.0 ml of the 0.5N
H2SC>4.
f. Dilute to 1 L with distilled
water and mix thoroughly.
5. Barium perchlorate solution
0.01 DON. Dissolve 1.95 g of
barium perchlorate trihydrate
(Ba(CIO«)2 • 3H20) in 200 ml of
distilled water and dilute to 1 L
with isopropanol. Alternatively,
1.22 g of barium chloride
dihydrate (BaCI2 • 2H20) may be
used instead of the perchlorate.
Standardize, as in Subsection
5.2.4, with 0.01 N HzSO*. Note-
Protect the 0.01 OON 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 purchased. Pipette
10.0 ml of sulfuric acid (0.1N) into a
100-ml volumetric flask and dilute to
volume with deionized distilled water
that has been determined to be
acceptable as detailed in Subsection
5.2.4. When the 0.01 N sulfuric acid is
prepared in this manner, procedures
in Subsections 5.2.2 and 5.2.3 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% w/w NaOH
solution. Dilute 10 ml to 1 L with
deionized distilled water. Dilute
52.4 ml of the diluted solution to
1 L with deionized distilled
water.
2. Dry the primary standard grade
potassium acid phthalate for 1 to
2 h 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
deionized distilled water in a
250-ml Erlenmeyer flask.
4. Add two drops of
phenolphthalein indicator, and
titrate the phthalate solutions
with the NaOH solution. Observe
titrations 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
s.
5. Compare the endpoint colors of
the other two.titrations against
the first. The normality is the
average of the three values
calculated using the following
equation.
(ml
cid - ml
) x NNa
ml titrant * 204.23
where
NNaoH Calculated normality of
sodium hydroxide,
mgKHP= weight of the phthalate,
mg, and
ml titrant = volume of sodium
hydroxide titrant, ml
Equation 5-2
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.
NaOH + KHP + phenolphthalein -
(colorless)
KNaP + HOH + phenolphthalein.
(pink)
Equation 5-3
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 deionized distilled
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
deionized distilled water, using
the same technique as step 3.
The normality will be the average
of the three independent values
calculated using the following
equation:
25
Equation 5-4
where
NH^SQ, = calculated normality of
sulfuric acid,
ml NaOHacio = volume of titrant used for
H2S04, ml,
ml NaOHbiank= volume of titrant used for
blank, ml, and
NNBOH = normality of sodium
hydroxide.
5.2.4 Standardization of Barium
Perchlorate (0.0100N) - To standardize
barium perchlorate, proceed as
follows:
1. Pipette 25 ml of sulfuric acid
standard (0.01 OON) 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
0.01 OON 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
deionized distilled water. If a
blank requires >0.5 ml of titrant,
the analyst should determine the
source of contamination. If the
distilled water contains high con-
centrations of sulfate or other
polyvalent anions, then all rea-
gents made with the distilled
water will have to be remade us-
ing 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.
ml Ba(CI04>2
Equation 5-5
where
NBB(cio4i2 Calculated normality of
barium perchlorate,
Nnjso,, = normality of
standardized sulfuric
acid, and
ml Ba(CIO<)2= volume of barium per-
chlorate titrant, ml.
The chemical reaction for this
standardization was shown in Equa-
tion 5-1. The standardized barium
-------
5-01-79
Section 3.5.5
perchlorate should be protected from
evaporation of the isopropanol at all
times. /Vofe-,lt 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 H2SC>4 into
three 250-ml Erlenmeyer flasks.
2. Dilute to 25 ml with distilled
water.
3. Add a 100-ml volume of 100%
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 technique 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 pre-
pared and analyzed in the following
manner:
1. Dry the primary standard grade
ammonium sulfate ((NH^aSO^)
for 1 to 2 hat 110°C (230°F),
and cool in a desiccator.
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-L volumetric flask.
4. Dilute to the 2-L mark with
distilled water. The resulting
solution is 0.01 DON 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 distilled 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 s. All titrations should be
done against a white back-
ground.
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 com-
plete 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 two 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 techniques
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% of the stated value,
the technique and standard reac-
tions are acceptable, and the
field samples may be analyzed.
When the 5% 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. The accuracy limit of
±5% for intralaboratory control
samples is recommended based
on the control limit of ±7% for
interlaboratory audit results
discussed in Section 3.6.8.
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 documenta-
tion of the quality of the source
test analysis.
5.2.6 Sample Analysis - Check the
level of liquid in the container 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 flask (Vaoin), and dilute
to exactly 100 ml with deionized
distilled water.
3. Put water in the sample storage
container to the initial sample
mark, and measure the initial
sample volume (Vsoln.).
4. Put water in the sample storage
container to the mark of the
transferred sample, and measure
the final volume (Vsom,).
5. If V,0in, is
-------
Section 3.5.5
5-01-79
of barium perchlorate used in
titrating the sample (Vt).
4. Repeat the above analysis on a
new aliquot from the same
sample. Replicate titrant volumes
must be within 1% 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% or 0.2 ml, whichever
is larger, or until sample is spent.
5. Record all data on the data form,
Figure 5.2. Average the
consistent titrant volumes, and
use them as V, in subsequent
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 0.01 OON
barium perchlorate solution from
evaporation at all times.
Meter Box Number
Dry Gas Meter*
~ I
Pretest calibration factor Y = /.Of
Posttest check Y> = l*Dlf Y, = /
Recalibration required?
(±5% of pretest factor)"
// yes, recalibration factor Y =
calibration run)
(within ±2% of calibration factor for each
Lower calibration factor, Y = .
for pretest or posttest calculations
Rotameter
Pretest calibration factor Y, = /«
Posttest check Y, = (.OS (within ±10% of pretest factor)
Recalibration recommended? yes t^ no
If performed, recalibration factor Y, -
Was rotameter cleaned? lr yes • no
Dry Gas Meter Thermometer
Was a pretest meter temperature correction used? _____ yes ^ no
If yes. temperature correction _________
— *? */*
Posttest comparison with mercury-in-glass thermometer X *••» within ±6°C
(10.8°F) of reference values
Recalibration required?.
yes.
Recalibration temperature correction if used.
values
. within ±3°C(5.4°FJ of reference
If meter thermometer temperature is higher, no correction is needed
If recalibration temperature is higher, add correction to average meter temperature for
calculations
Barometer
Was pretest field barometer reading correct? Ir yes no
Posttest comparison '/*& mm (jnj Hg within ±5.0 mm (0.2 in.) Hg of mercury-in-
glass barometer
Was recalibration required? yes l^ no
If field barometer reading is lower, no correction is needed
If mercury-in-glass reading is lower, subtract difference from field data readings for
calculations
'Most significant items/parameters to be checked.
Figure S.I. Posttest sampling checks.
-------
5-01-79
Section 3.5.6
Plant
Sample location
Volume and normality of barium perch/orate
Alf>. 3
Date
Analyst
flfra/77
C.O/02N
'. avg
Sample
number
1
2
3
4
5
6
Blank
Sample
identification
number
S0-I
Total
sample
volume
(V^).
ml
too
N/A
Sample
aliquot
volume
(Val.a
ml
20
Volume of titrant (Vt).ti ml
1st
titration
lt,3/
O
2nd
titration
II.Z1
O
Average
11.30
v*=o
Volume for the blank must be the same as that of the sample aliquot.
1st titration _ Qgg (Q 1 Q1 Qf ^ /sf titration . 2nd titration \ & ml BafCIOdz (must be < 0.5-ml)
Control
sample
number
t
Time of
analysis,
24 h
01*0
Titrant volume. * ml
1st
tt>0
2nd
2f>0
3rd
Avg
2S^>
"Two titrant volumes must agree within 0.2 ml.
mlBa(CI04hxNBJCIOj2 25ml x 0.01 N
_— _ „ -y>k ., ^~s* (control sample) (control sample)
2S.O mi * O. O/O N=
Signature of analyst
(must agree within ±5%. i.e.. 0.238 to 0.262)
Does value agree? ^ yes no
Cx^g^ OJUox&Qy
v
. Signature of reviewer
Figure 5.3. Control sample analytical data form.
-------
Section 3.5.5 6 6-01-79
Reagents
Normality of sulfuric acid standard* Q^» £/ / iJ f fit
Dale purchased (U/2-&/7& Dale standardized tl/ffc/76
Normality of barium per chlorate titrant
Date stanHarrlirarl ff/fVl l8
* O» OO TO Al
Normality of control sample*
o.
Date prepared. II1101 fS
Volume of burette J CJ fflf Graduations
Sample Preparation
Has liquid level noticeably changed?*
fi.l
A/0
Original volume Corrected volume .
Samples diluted to 100 ml?* y<2S
Analysis
Volume of aliquot analyzed*
-^fc^/r/y
Do replicate titrant volumes agree within 1% or 0.2 ml?
. Br C/* /OO /\f
Number and normality of control samples analyzed
Are replicate control samples within 0.2 ml?
Is accuracy of control sample analysis ±5%?*
All data recorded? _ t» Reviewed by
U/GD
'Most significant items/parameters to be checked.
Figure 5.4. Posttest operations.
-------
6-01-79
Section 3.6.6
Table S. 1 . Activity Matrix for Postsampling Operations
Activity Acceptance limits
Sampling
Apparatus
Dry gas meter
Rate meter
Meter thermome-
ter
Barometer
Analysis
Reagents
Control sample
Sample analysis
Within ±5% of pretest
calibration factor
Within ±10% of desired
flow rate (recommended)
Within ±6°C (10.8°F) at
ambient temperature
Within ±5.0 mm (0.2 in.)
Hg at ambient pressure '
Prepare according to
requirements detailed
in Subsec. 5.2
Titrants differ by
-------
5-01-79
Section 3.5.6
6.0 Calculations
Calculation errors due to procedural
or mathematical mistakes can be a
part of total system error. Therefore, it
is recommended 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
'orm such as the ones in Figures 6.1A
and 6.1 B, at the end of this section.
6.1 Nomenclature
The following nomenclature is used
in the calculations:
Cso2 = concentration of sulfur di-
oxide, dry basis corrected to
standard conditions, g/dscm
(Ib/dscf).
N=normality of barium perchlo-
rate titrant, meq/ml.
Pbar = barometric pressure at the
exit orifice of the dry gas
meter, mm (in.) Hg.
Pstd = standard absolute pressure,
760 mm (29.92 in.) Hg.
Tm = dry gas meter average abso-
lute temperature, K (°R).
Tstd = standard absolute tempera-
ture, 293K (528°R).
Va = volume of sample aliquot
titrated, ml.
Vm=dry gas volume measured by
dry gas meter, dcm (dcf).
Vmistd) =dry gas volume measured by
dry gas meter, corrected to
standard conditions, dscm
(dscf).
Vgoin=total volume of solution in
which the sulfur dioxide
sample is contained, 100 ml.
Vt = volume of barium perchlo-
rate titrant used for the
sample (average of replicate
titrations), ml.
Vm=volume of barium
perchlorate titrant used for
the blank, ml.
Y=dry gas meter calibration
factor.
32.03 =equivalent weight of sulfur
dioxide.
6.2 Calculations
The following formulas for
calculating the concentration of sulfur
dioxide are to be used along with
example calculation forms shown in
Figures 6.1A and 6.1B.
6.2.1 Dry Sample Gas Volume, Cor-
rected to Standard Conditions -
TmPs
where
Equation 6-1
! =0.3858 K/mm Hg for metric
units, or
= 17.64 °R/in. Hg for English
units.
6.2.2 Sulfur Dioxide Concentration
(V,-Vtb) Nv°°ln
r -K Va
UsO2 ~~ "^2
Vmlstdl
Equation 6-2
where
K2 =32.03 mg/meq for metric
units, or
=7.061 x 10"5lb/meqfor
English units.
Table 6.1. Activity Matrix for Calculation Checks
Characteristics
Analysis data
form
Calculations
Acceptance limits
All data and calcula-
tions are shown
Difference between
check and original cal-
culations should not
exceed round-off error
Frequency and method
of measurement
Visually check
Repeat all calcula-
tions starting with
raw data for hand
calculations; check
all raw data input
for computer calcu-
lations; hand cal-
culate one sample per
test
Action if
requirements
are not met
Complete the
missing data
values
Indicate
errors on
sulfur
dioxide cal-
culation form.
Fig. 6.1 A or
6.1 B
-------
Section 3.5.6 2 5-01-79
Sample Volume*
-Q_.7_Q_6_ ft3. rm - _5 ± 4. 2_ °R, P»., - 2_9.8± in. Hg. Y =
Vml.a, -- 17.64 °fl x YVmP», = 0_.(o_9_0_1t*
in. Hg im
Equation 6- 1
SOi Concentration
Q_.0_1_0_2._ (g-eqi/ml. V, = J_ ]_. 3_ 0_ ml. Vn = _0 ._Q_ 0_ ml
Vmlmn
Equation 6-2
'Calculation form for data collected using Method 6 type equipment. The alternative use of
Method 5 or Method 8 equipment will change Vm and VmMat to l/mntoi = . ft3.
Figure 6.1 A. Sulfur dioxide calculation form (English units).
Sample Volume*
Vm = 2 0 • O O I x 0.001 = 0.02
3_O_2_ O_K. P»« = _Z_ JL JI
' "- '- 0 .0
Equation 6-1
SOz Concentration
N = = O / O £ (g-eq)/ml. V, = _/__/_• _^_ O_ mi_ y,B = Q . Q Q ml
I ^\ x*\ f\ ^ ^\ x^
y__i_ — f (^ (_/ 4 ^^ in/ Vit ~ £- ^^ ^*^ /n/
N(V< -VuJfV^/VJ O /? si /)
Cso2 = 32.03 = 7 •fr X . U mg/dscm
Vmlltd)
Equation 6-2
"Calculation form for data collected using Method 6 type equipment. The alternative use of
Method 5 or Method 8 equipment will change Vm and VmMa> to Vm<.to> = . m3.
Figure 6.1B. Sulfur dioxide calculation form (metric units).
-------
5-01-79
Section 3.6.7
7.0 Maintenance
The normal use of emission-testing
equipment subjects it to corrosive
gases, extremes in temperature, vibra-
tion, 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 L (100 ft3) of operation,
whichever is greater. In addition to
the quarterly maintenance, a yearly
cleaning of the entire meter box is
recommended. Maintenance proce-
dures 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 sample
train, several types of pumps are
used; the two most common are the
fiber vane pump with in-line oiler and
the diaphragm pump. The fiber vane
pump requires a periodic check of the
oiler jar. Its contents should be
translucent; the oil should be changed
if 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 shoufd
be removed and the fiber vanes
changed. Erratic operation of the
diaphragm pump is normally due to
either a bad diaghragm (causing leak-
age) 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 corrosion of
the components by removing the top
plate every 3 mo. 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 disassem-
bled and cleaned according to the
manufacturer's instructions using only
recommended cleaning fluids every 3
mo or upon erratic operation.
7.4 Sample Train
All remaining sample train compo-
nents should be visually checked
every 3 mo 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 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.
Table 7.1. Activity Matrix for Equipment Maintenance Checks
Apparatus
Routine main-
tenance
Fiber vane pump
Diaphragm pump
Dry gas meter
Rotameter
Sample train
Acceptance limits
No erratic behavior
In-line oiler free of
leaks
Leak-free valves func-
tioning properly
No excess oil, corro-
sion, or erratic rota-
tion of the dial
Clean and no erratic
behavior
No damage
Frequency and method
of measurements
Routine maintenance
performed quarterly;
disassemble and
clean yearly
Periodically check
oiler jar; remove
head and change fiber
vanes
Clean valves during
yearly disassembly
Check every 3 mo
for excess oil or
corrosion by removing
the top plate; check
valves and diaphragm
whenever meter dial
runs erratically or
whenever meter will
not calibrate
Clean every 3 mo or
whenever ball does
not move freely
Visually check every
3 mo; completely dis-
assemble and clean
or replace yearly
Action if
requirements
are not met
Replace parts
as needed
Replace as
needed
Replace when
leaking or
ma/function-
ing
Replace parts
as needed or
rep/ace meter
Replace
If failure
noted, use
another entire
meter box,
sample box,
or umbilical
cord
-------
Section No. 3.5.8
Revision No. 1
Date September 23,
Page 1
1985
8.0 AUDITING PROCEDURE
An audit is an independent assessment of data quality. In-
dependence is achieved if the individual(s) performing the audit
and their standards and equipment are different from the regular
field crew and their standards and equipment. In the case of a
compliance test, the required performance audit will be conducted
by the responsible enforcement agency. Routine quality assurance
checks by a field team are necessary in generation of good
quality data, but they are not part of the auditing procedure.
Table 8.1 at the end of this section summarizes the quality
assurance functions for auditing.
234
Based on the results of collaborative tests ' ' of Method 6,
two specific performance audits are recommended:
1. Audit of the analytical phase of Method 6.
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 generally made to quantitatively
evaluate the quality of data produced by the total measurement
system (sample collection, sample analysis, and data process-
ing). It is recommended 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. No performance audit is recommended at this time
for the sampling phase. 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 6 analysis and
should be performed at the discretion of the agency auditor, the
laboratory supervisor, source test company, or quality assurance
officer. The analytical phase of Method 6 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 Section 3.5.5 on control sample preparation.
-------
Section No. 3.5.8
Revision No. 1
Date September 23,'1985
Page 2
The pretest audit provides the opportunity for the te'sting
laboratory to check the accuracy of its analytical procedure.
This audit is especially recommended for a laboratory with little
or no experience with the Method 6 analysis procedure described
in this Handbook.
To obtain pretest audit samples only, the testing laboratory
should provide a notice 30 days prior to the time of the planned
pretest audit to EPA's Environmental Monitoring Systems
Laboratory, Quality Assurance Division, Source Branch, Mail Drop
77A, Research Triangle Park, North Carolina 27711. This request
for known quality control samples from the Source Branch is
different from and does not satisfy the required 30 day notice to
the applicable enforcement agency as to the intent to conduct a
compliance test. The laboratory can prepare their own quality
control sample. The testing laboratory supervisor or quality
assurance officer can then check the precision and accuracy of
the analytical system prior to a compliance test with the use of
the known value samples. All problems indicated by the audit
should be eliminated prior to the audit by the agency.
The accuracy for each of two samples should be within 5 per-
cent of true value. The relative error (RE) is a measure of the
bias of the analytical phase of Method 6. Calculate RE using
Equation 8-1.
r Equation 8-1
RE = cd " a x 100
r>
where: a
3
C. = Determined audit sample concentration, mg/dsm .
3
C = Actual audit sample concentration, mg/dsm .
a
8.1.2 Audit of Analytical Phase of the Field Test (Required) -
As stated in 40 CFR 60, Section 3.3.6 (49 FR 26522, 06/27/84),
the testing laboratory should provide the responsible agency/
organization requesting the performance test with a notification
of the intent to test 30 days prior to the enforcement source
test. The responsible agency obtains the audit samples from the
appropriate EPA Regional Quality Assurance Coordinator shown in
Table 5.1 of Section 3.0.5 of this Handbook. The responsible
agency then provides the testing laboratory with two audit
samples to be analyzed along with 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 two audit samples and the compliance samples should be
concurrently analyzed in the same manner to evaluate the
technique of the analyst and the standards preparation. (Note:
It is recommended that known quality control samples be analyzed
-------
Section No. 3.5.8
Revision No. 1
Date September 23, 1985
Page 3
prior to the compliance and audit sample analysis to optimize the
system accuracy and precision. One source of these samples has
been listed above.) The same analyst, analytical reagents, and
analytical system shall be used both for compliance samples and
the EPA audit samples; if this condition is met, auditing of
subsequent compliance analyses for the same enforcement agency
within 30 days 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 the
audit results in mg/dsm and compliance results in total mg NO2/
sample by telephone to the responsible enforcement agency.)
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 (see Note in first paragraph
of this section).
Failure to meet the 5-percent specification may require
retests until the audit problems are resolved. However, if the
audit results do not affect the compliance or noncompliance sta-
tus of the affected facility, the Administrator may waive the
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.
8.1.3 Audit of Data ^Processing - Calculation errors are
prevalent in Method 6. ' ' Data processing errors can be
determined by auditing the recorded data on the field and
laboratory forms. The original and audit (check) calculations
should agree within round-off error; if not, all of the remaining
data should be checked. The data processing may also be audited
by 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
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Section No. 3.5.8
Revision No. 1
Date September 23, 1985
Page 4
checking both computer programs and manual methods o*f 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 audit may be re-
duced- -for example, to 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 audits,
specifying any area(s) that need special attention or improve-
ment.
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 team management so that appropriate corrective
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. Purging the sampling train.
Figure 8.1 is a suggested checklist for the auditor.
-------
Section No. 3-5.8
Revision No. 1
Date September 23, 1985
Page 5
Yes
Nb
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
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. Audit results (+ 5%)
14. Calculation procedure/check
15. Calibration checks
16. Standardized barium perchlorate solution
Comments
Figure 8.1. Method 6 checklist to be used by auditors.
-------
Section No. 3.5.8
Revision No. 1
Date September 23," 1985
Page 6
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 sul-
fate solution
Measured RE of the
pretest audit samples
should be less than
+5% for both audit
results (optional)
Measured RE for
audit during test
should be less than
+5% for both audit
results (required)
Frequency; As consid-
ered necessary by the
testing firm
Method; Measure refer-
ence samples and compare
with true value
Frequency; Once during
every enforcement source
test (required)
Method; Measure audit
samples and compare
with true samples
Review opera-
ting techniques
1 Review opera-
ting technique
and repeat
both the audit
and field sam-
ple analyses
Data
processing
errors
(recommended)
Original and
check calculations
within round-off
error
Frequency: Once during
every enforcement
source test
Method; Independent
calculations, starting
with recorded data
System audit
(recommended)
Operation technique
described in this
section of the Hand-
book
Frequency: Once dur-
ing every enforcement
test until experience
gained, then every
fourth test
Method: Observation of
techniques, assisted by
audit checklist,
Fig. 8.1
Check and
correct all
data for the
source test
Explain to
team the devi-
ations from
recommended
techniques and
note on Fig.
8.1
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5-01-79 1 Section 3.6.9
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 statistical control at the time
of the measurement, and the
systematic errors, when combined
with the random variation (errors of
measurement), 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 appropriate; and to
use materials, instruments, and
measurement procedures that can be
traced to an appropriate standard of
reference.
Data must be routinely obtained by
repeat 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 displacement method (Sec-
tion 3.5.2) or by use of a
spirometer.
2. The barium perchlorate is stand-
ardized against sulfuric acid. The
sulfuric acid should have been
standardized with primary
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.
-------
5-01-79
Section 3.5.10
10.0 Reference Method*
Method 6—Determination of Sulfur Dioxide Emissions
from Stationary Sources
1. Principle and Applicability 2. Apparatus
1.1 Principle. A gas sample is ex-
tracted from the sampling point in
the stack. The sulfuric acid mist
(including sulfur trioxide) and the
sulfur dioxide are separated. The
sulfur dioxide fraction is measured by
the barium-thorin titration method.
1.2 Applicability. This method is
applicable for the determination of
sulfur dioxide emissions from sta-
tionary sources. The minimum
detectable limit of the method has
been determined to be 3.4 milligrams
(mg) of SO2/m3(2.12 x 10~7lb/fr).
Although no upper limit has been
established, tests have shown that
concentrations as high as 80,000
mg/rh3 of S02 can be collected
efficiently in two midget impingers,
each containing 15 milliliters of 3
percent hydrogen peroxide, at a rate
of 1.0 Lpm for 20 minutes. Based on
theoretical calculations, the upper
concentration limit in a 20-liter
sample is about 93,300 mg/m3.
Possible interferents are free am-
monia, water-soluble cations, and
fluorides. The cations and fluorides
are removed by glass wool filters and
an isopropanol bubbler, and hence
do not affect the SO2 analysis. When
samples are being taken from a gas
stream with high concentrations of
very fine metallic fumes (such as in
inlets to control devices), a high-
efficiency glass fiber filter must be
used in place of the glass wool plug
(i.e., the one in the probe) to remove
the cation interferents.
Free ammonia interferes by
reacting with SO? to form paniculate
sulfite and by reacting with the
indicator. If free ammonia is present
(this can be determined by
knowledge of the process and
noticing white particulate matter in
the probe and isopropanol bubbler),
alternative methods, subject to the
approval of the Administrator, U.S.
Environmental Protection Agency, are
required.
•40CFR60, July 1, 1978
2.1 Sampling. The sampling train is
shown in Figure 6-1, and component
parts are discussed below. The tester
has the option of substituting
sampling equipment described in
Method 8 in place of the midget
impinger equipment of Method 6.
However, the Method 8 train must be
modified to include a heated filter
between the probe and isopropanol
impinger, and the operation of the
sampling train and sample analysis
must be at the flow rates and solu-
tion volumes defined in Method 8.
The tester also has the option of
determining SO2 simultaneously with
particulate matter and moisture
determinations by (1) replacing the
water in a Method 5 impinger system
with 3 percent peroxide solution, or
(2) by replacing the Method 5 water
impinger system with a Method 8
isopropanol-filter-peroxide system.
The analysis for SOZ must be
consistent with the procedure in
Method 8.
2.1.1 Probe. Borosilicate glass, or
stainless steel (other materials of
construction may be used, subject to
the approval of the Administrator),
approximately 6-mm inside diameter,
with a heating system to prevent
water condensation and a filter
(either in-stack or heated out-stack)
to remove particulate matter,
including sulfuric acid mist. A plug of
glass wool is a satisfactory filter.
2.7.2 Bubbler and Impingers. One
midget bubbler, with medium-coarse
glass frit and borosilicate or quartz
glass wool packed in top (see Figure
6-1) to prevent sulfuric acid mist
carryover, and three 30-ml midget
impingers. The bubbler and midget
impingers must be connected in
series with leak-free glass
connectors. Silicone grease may be
used, if necessary, to prevent
leakage.
At the option of the tester, a midget
impinger may be used in place of the
midget bubbler.
Other collection absorbers and
flow rates may be used, but are
subject to the approval of the
Administrator. Also, collection
efficiency must be shown to be at
least 99 percent for each test run
and must be documented in the
report. If the efficiency is found to be
acceptable after a series of three
tests, further documentation is not
required. To conduct the efficiency
test, an extra absorber must be
added and analyzed separately. This
extra absorber must not contain more
than 1 percent of the total SC>2.
2.1.3 Glass Wool. Borosilicate or
quartz.
2.1.4. Stopcock Grease. Acetone-
insoluble, heat-stable silicone grease
may be used, if necessary.
2.1.5 Temperature Gauge. Dial ther-
mometer, or equivalent, to measure
temperature of gas leaving impinger
train to within 1°C (2°F).
2.1.6 Drying Tube. Tube packed
with 6- to 16-mesh indicating type
silica gel, or equivalent, to dry the
gas sample and to protect the meter
and pump. If the silica gel has been
used previously, dry at 175°C
(350°F) for 2 hours. New silica gel
may be used as received.
Alternatively, other types of
desiccants (equivalent or better) may
be .used, subject to approval of the
Administrator.
2.1.7 Valve. Needle valve, to
regulate sample gas flow rate.
2.1.8 Pump. Leak-free diaphragn
pump, or equivalent, to pull gas
through the train. Install a small
surge tank between the pump and
rate meter to eliminate the pulsation
effect of the diaphragm pump on the
rota,meter.
2.7.9 Rate Meter. Rotameter, or
equivalent, capable of measuring
flow rate to within 2 percent of the
selected flow rate of about 1000
cc/min.
2.1.10 Volume Meter. Dry gas
meter, sufficiently accurate to
measure the sample volume within 2
percent, calibrated at the selected
flow rate and conditions actually
encountered during sampling, and
equipped with a temperature gauge
-------
Section 3.6.10
5-01-79
(dial thermometer, or equivalent)
capable of measuring .temperature to
within 3°C (5.4°F).
2.1.11 Barometer. Mercury, aneroid,
or other barometer capable of
measuring atmospheric pressure to
within 2.5 mm Hg (0.1 in. Hg) In
many cases, the barometric reading
may be obtained from a nearby na-
tional weather service station, in
which case the station value (which
is the absolute barometric pressure)
shall be requested and an adjustment
for elevation differences between the
weather station and sampling point
shall be applied at a rate of minus
2.5 mm Hg (0.1 in. Hg) per 30 m
(100 ft) elevation increase or vice
versa for elevation decrease.
2.1.12 Vacuum Gauge and Rota-
meter. At least 760 mm Hg (30 in.
Hg) gauge and 0-40 cc/min
rotameter, to be used for leak check
of the sampling train.
2.2 Sample Recovery.
2.2.1 Wash Bottles. Polyethylene
or glass, 500 ml, two.
2.2.2 Storage Bottles. Polyethylene,
100 ml, to store impinger samples
(one per sample).
2.3 Analysis.
2.3.1 Pipettes. Volumetric type, 5-
ml, 20-ml (one per sample), and 25-
ml sizes.
2.3.2 Volumetric Flasks. 100-ml size
(one per sample) and 1000-ml size.
2.3.3 Burettes. 5- and 50-ml sizes.
2.3.4 Erlenmeyer Flasks. 250 mi-
size (one for each sample, blank, and
standard).
2.3.5 Dropping Bottle. 125-ml size,
to add indicator.
2.3.6 Graduated Cylinder. 100-ml
size.
2.3.7 Spectrophotorheter. To mea-
sure absorbance at 352 nanometers
3. Reagents
Unless otherwise indicated, all rea-
gents must conform to the specifica-
tions established by the Committee
on Analytical Reagents of the
American Chemical Society. Where
such specifications are not available,
use the best available grade.
3.1 Sampling.
3. /. 7 Water. Deionized, distilled to
conform to ASTM specification
D1193-74, Type 3. At the option of
the analyst, the KMnCu test for
oxidizable organic matter may be
omitted when high concentrations of
organic matter are not expected to be
present.
3.1.2 Isopropanol, 80 Percent. Mix
80 ml of isopropanol with 20 ml of
deionized, distilled water. Check each
lot of isopropanol for peroxide impur-
ities as follows: shake 10 ml of
isopropanol with 10 ml of freshly
prepared 10 percent potassium
iodide solution. Prepare a blank by
similarly treating 10 ml of distilled
water. After 1 minute, read the
absorbance at 352 nanometers on a
spectrophotometer. If absorbance
exceeds 0.1, reject alcohol for use.
Peroxides may be removed from
isopropanol by redistilling or by
passage through a column of
activated alumina; however, reagent
grade isopropanol with suitably low
peroxide levels may be obtained from
commercial sources. Rejection of
contaminated lots may, therefore, be
a more efficient procedure.
3.1.3 Hydrogen Peroxide, 3 Percent.
Dilute 30 percent hydrogen peroxide
1:9 (v/v) with deionized, distilled
water (30 ml is needed per sample).
Prepare fresh daily.
3.1.4 Potassium Iodide Solution, 10
Percent. Dissolve 10.0 grams Kl in
deionized, distilled water and dilute
to 100 ml. Prepare when needed.
3.2 Sample Recovery.
3.2.1 Water. Deionized, distilled, as
in 3.1.1.
3.2.2 Isopropanol, 80 Percent. Mix
80 ml of isopropanol with 20 ml of
deionized, distilled water.
3.3 Analysis.
3.3.1 Water. Deionized, distilled, as
in 3.1.1.
3.3.2 Isopropanol, 100 Percent.
3.3.3 Thorin Indicator. 1-(o-arsono-
phenylazo)-2-naphthol-3, 6-
disulfonic acid, disodium salt, or
equivalent. Dissolve 0.20 g in 100 ml
of deionized, distilled water.
3.3.4 Barium Perchlorate Solution,
0.0100 N. Dissolve 1.95 g of barium
perchlorate trihydrate [BafCICub-
3H2O] in 200 ml distilled water and
dilute to 1 liter with isopropanol.
Alternatively, 1.22 g of [BaCI2-2H20]
may be used instead of the
perchlorate. Standardize a*s in Sec-
tion 5.5.
3.3.5 Sulfuric Acid Standard,
0.0100 N. Purchase or standardize to
- 0.0002 N against 0.0100 N NaOH
which has previously been
standarized against potassium acid
phthalate (primary standard grade).
4. Procedure
4.1 Sampling.
4.1.1 Preparation of Collection
Train. Measure 15 ml of 80 percent
isopropanol into the midget bubbler
and 15 ml of 3 percent hydrogen
peroxide into each of the first two
midget impingers. Leave the final
midget impinger dry. Assemble the
train as shown in Figure 6-1. Adjust
probe heater to a temperature
sufficient to prevent water condensa-
tion. Place crushed ice and water
around the impingers.
4.1.2 Leak-Check Procedure. A leak
check prior to the sampling run is op-
tional; however, a leak check after the
sampling run is mandatory. The leak-
check procedure is as follows:
Temporarily attach a suitable (e.g.,
0-40 cc/min) rotameter to the outlet
of the dry gas meter and place a
vacuum gauge at or near the probe
inlet. Plug the probe inlet, pull a
vacuum of at least 250 mm Hg (10 in.
Hg), and note the flow rate as
indicated by the rotameter. A leakage
rate not in excess of 2 percent of the
average sampling rate is acceptable.
Note - Carefully release the probe
inlet plug before turning off the pump.
It is suggested (not mandatory) that
the pump be leak-checked separately,
either prior to or after the sampling
run. If done prior to the sampling run,
the pump leak-check shall precede the
leak-check of the sampling train
described immediately above; if done
after the sampling run, the pump
leak-check shall follow the train leak-
check. To leak-check the pump,
proceed as follows: disconnect the
drying tube from the probe-impinger
assembly. Place a vacuum gauge at
the inlet to either the drying tube or
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.
Other leak-check procedures may
be used, subject to the approval of the
Administrator, U.S. Environmental
Protection Agency.
-------
5-01-79
Section 3.5.10
4.1.3 Sample Collection. Record the
initial dry gas meter reading and
barometric (Wessure. To begin samp-
ling, position the tip of the probe at
the sampling point, connect the probe
to the bubbler, and start the pump.
Adjust the sample flow to a constant
rate of approximately 1.0 liter/min as
indicated by the rotameter. Maintain
this constant rate (= 10 percent)
during the entire sampling run. Take
readings (dry gas meter, temperatures
at dry gas meter and at impinger
outlet and rate meter) 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. At the conclusion of
each run, turn off the pump, remove
probe from the stack, and record the
final readings. Conduct a leak check
as in Section 4.1.2. (This leak check is
mandatory.) If a leak is found, void the
test run or use procedures acceptable
to the Administrator to adjust the
sample volume for the leakage. Drain
the ice bath, and purge the remaining
part of the train by drawing clean
ambient air through the system for 15
minutes at the sampling rate.
Clean ambient air can be provided
by passing air through a charcoal
filter or through an extra midget
impinger with 15 ml of 3 percent
H202. The tester may opt to simply
use ambient air, without purification.
4.2 Sample Recovery. Disconnect
the impingers after purging. Discard
the contents of the midget bubbler.
Pour the contents of the midget
impingers into a leak-free
polyethylene bottle for shipment.
Rinse the three midget impingers and
the connecting tubes with deionized
distilled water, and add the washings
to the same storage container. Mark
the fluid level. Seal and identify the
sample container.
4.3 Sample Analysis. Note level of
liquid in container, and confirm
whether any sample was lost during
shipment; note this on analytical data
sheet. If a noticeable amount of
leakage has occurred, either void the
sample or use methods, subject to the
approval of the Administrator, to
correct the final results.
Transfer the contents of the storage
container to a 100-ml volumetric flask
and dilute to exactly 100 ml with
deionized, distilled water. Pipette a
20-ml aliquot of this solution into a
250-ml Erlenmeyer flask, add 80 ml of
100 percent isopropanol and two to
four drops of thorin indicator, and
titrate to a pink endpoint using 0.0100
N barium perchlorate. Repeat and
average the titration volumes. Run a
blank with each series of samples.
Replicate titrations must agree within
1 percent or 0.2 ml, whichever is
larger.
(Note - Protect the 0.0100 N barium
perchlorate solution from evaporation
at all times.)
5. Calibration
5.1 Metering System.
5.1.1 Initial Calibration. Before its
initial use in the field, first leak check
the metering system (drying tube,
needle valve, pump, rotameter, and
dry gas meter) as follows: place a
vacuum gauge at the inlet to the
drying tube and 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 shall
remain stable for at least 30 seconds.
Carefully release the vacuum gauge
before releasing the flow meter end.
Next, calibrate the metering system
(at the sampling flow rate specified by
the method) as follows: connect an
appropriately sized wet test meter
(e.g., 1 liter per revolution) to the inlet
of the drying tube. Make three
independent calibration runs, using at
least five revolutions of the dry gas
meter per run. Calculate the calibra-
tion factor, Y (wet test meter calibra-
tion volume divided by the dry gas
meter volume, both volumes adjusted
to the same reference temperature
and pressure), for each run, and
average the results. If any Y value
deviates by more than 2 percent from
the average, the metering system is
unacceptable for use. Otherwise, use
the average as the calibration factor
for subsequent test runs.
5.1.2 Posttest Calibration Check.
After each field test series, conduct a
calibration check as in Section 5.1.1
above, except for the following varia-
tions: (a) the leak check is not to be
conducted, (b) three, or more revolu-
tions of the dry gas meter may be
used, and (c) only two independent
runs need be made. If the calibration
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. If the calibration factor
deviates by more than 5 percent,
recalibrate the metering system as in
Section 5.1.1, and for the calcula-
tions, use the calibration factor (initial
or recalibration) that yields the lower
gas volume for each test run.
5.2 Thermometers. Calibrate against
mercury-in-glass thermometers.
5.3 Rotameter. The rotameter need
not be calibrated but should be
cleaned and maintained according to
the manufacturer's instruction
5.4 Barometer. Calibrate 3 --.a
mercury barometer.
5.5 Barium Perchlorate Solution.
Standardize the barium perchlorate
solution against 25 ml of standard
sulfuric acid to which 100 ml of 100'
percent isopropanol has been added.
6. Calculations
Carry out calculations, retaining at
least one extra decimal figure beyond
that of the acquired data. Round off
figures after final calculation.
6.1 Nomenclature.
Csoz = Concentration of sulfur di-
oxide, dry basis corrected to
standard conditions,
mg/dscm (Ib/dscf).
N = Normality of barium perchlo-
rate titrant, milliequivalents/
ml.
Pbar = Barometric pressure at the
exit orifice of the dry gas
meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure,
760 mm Hg (29.92 in. Hg).
Tm = Average dry gas meter abso-
lute temperature, °K (°R).
Tsid = Standard absolute tempera-
ture, 293°K (528°R).
Va= Volume of sample aliquot
titrated, ml.
Vm = Dry gas volume as measured
by the dry gas meter, dcm
(dcf).
Vm(stdi = Dry gas volume measured by
the dry gas meter, corrected
to standard conditions, dscm
(dscf).
Vsoin = Total volume of solution in
which the sulfur dioxide
sample is contained, 100 ml.
Vt = Volume of barium perchlorate
titrant used for the sample,
ml (average of replicate titra-
tions).
Vtb = Volume of barium perchlorate
titrant used for the blank, ml.
Y = Dry gas meter calibration fac-
tor.
32.03 = Equivalent weight of sulfur
dioxide.
6.2 Dry Sample Gas Volume,
Corrected to Standard Conditions.
Vn
(!-)(*-) = KIY^
\ Tm / \ P5td / Tm
Equation 6-1
-------
Section 3.5.10
5-01-79
where
K, =0.3858 °K/mm Hg for metric
units.
= 17.64 °R/in. Hg for English
units.
6.3 Sulfur Dioxide Concentration
(VrVuWMsoin
Vmlstdl
Equation 6-2
where
Ka = 32.03 mg/meq. for metric units.
= 7.061x10'6 Ib/meq. for English
units.
7. Bibliography
1. Atmospheric Emissions from Sul-
furic Acid Manufacturing Pro-
cesses. U.S. DHEW, PHS,
Division of Air Pollution. Public
Health Service Publication No.
999-AP-13. Cincinnati, Ohio.
1965.
2. Corbett, P.P. The Determination
of SOz and SOa in Flue Gases.
Journal of the Institute of Fuel.
24: 237-243. 1961.
3. Matty, R.E. and E.K. Diehl.
Measuring Flue-Gas S02 and
S03. Power. 101: 94-97.
November 1957.
4. Patton, W.F. and J.A. Brink, Jr.
New Equipment and Techniques
for Sampling Chemical Process
Gases. J. Air Pollution Control
Association. 13: 162. 1963.
5. Rom, J.J. Maintenance, Calibra-
tion, and Operation of Isokinetic
Source-Sampling Equipment. Of-
fice of Air Programs, Environ-
mental Protection Agency. Re-
search Triangle Park, N.C.
APTD—0576. March 1972.
6. Hamil, H.F. and D.E. Camann.
Collaborative Study of Method for
the Determination of Sulfur Di-
oxide Emissions from Stationary
Sources (Fossil-Fuel Fired Steam
Generators). Environmental Pro-
tection Agency, Research
Triangle Park, N.C. EPA-650/4-
74-024. December 1973.
7. Annual Book of ASTM Standards.
Part 31; Water, Atmospheric
Analysis. American Society for
Testing and Materials.
Philadelphia, Pa. 1974. pp. 40-
42.
8. Knoll, J.E. and M.R. Midgett. The
Application of EPA Method 6 to
High Sulfur Dioxide Concentra-
tions. Environmental Protection
Agency. Research Triangle Park,
N.C. EPA-600/4-76-038. July
1976.
Probe lEnd Packed iff Stack Wall
with Quartz or \\ /
Pyrex Wool) y
Glass Wool
Midget Impingers
Midget Bubbler
Thermometer
Silica Gel
Drying Tube
Ice Bath
Thermometer
Pump
Surge Tank
Figure 6-1. SOz sampling train.
-------
5-01-79
Section 3.5.11
11.0 References
1. 40 Code of Federal Regulations
60. July 1, 1978.
2. Hamil, F. Laboratory and Field
Evaluations of EPA Methods 2, 6,
and 7. Report No. EPA- 650/4-
74-026. Southwest Research
Institute, San Antonio, Tex.
1974.
3. Hamil, F. and D. E. Camann.
Collaborative Study of Method for
the Determination of Sulfur Di-
oxide Emissions from Stationary
Sources. Report No. EPA-650/4-
74-024. National Environmental
Research Center, Environmental
Protection Agency, Research Tri-
angle Park, N.C. December 1973.
4. Hamil, F., D. E. Camann, and R.
E. Thomas. The Collaborative
Study of EPA Methods 5, 6, and
7 in Fossil Fuel-Fired Steam
Generators. Final Report No.
EPA-650/4-74-013. Southwest
Research Institute, San Antonio,
Tex. September 1974.
5. Quality Assurance Handbook for
Air Pollution Measurement Sys-
tems, Vol. I, Principles. EPA-
600/9-76-005. Environmental
Protection Agency, Research Tri-
angle Park, N.C. March 1976.
6. Guidelines for Development of a
Quality Assurance Program: Vol-
ume V - Determination of Sulfur
Dioxide Emissions from
Stationary Sources. EPA-650/4-
74-005. Research Triangle
Institute, Research Triangle Park,
N.C.November 1975.
7. McCoy, R. A., D. E. Camann, and
H. C. McKee. Collaborative Study.
Reference Method for
Determination of Sulfur Dioxide
in the Atmosphere
(Pararosaniline Method). EPA-
650/4-74-027. December 1973.
8. Smith, F., and C. Nelson, Jr.
Guidelines for Development of a
Quality Assurance Program.
EPA-R4-73-028d. August 1973.
9. Fuerst, R. G. Improved Tempera-
ture Stability of Sulfur Dioxide
Samples Collected by the Federal
Reference Method. EPA-600/4-
78-018, April 1978.
10. Knoll, J. E., and M.R. Midgett.
The Application of EPA Method 6
to High Sulfur Dioxide
Concentrations. EPA-600/4-76-
038. July 1976.
11. Osborne, M. C., and M. R.
Midgett. Survey of Continuous
Source Emission Monitors:
Survey No. 1 NOX and S02. EPA-
600/4-77-022. April 1977.
12. Buchanan, J.N., and D. E.
Wagoner. Guidelines for
Development of a Quality
Assurance Program: Volume VII -
Determination of Sulfuric Acid
Mist and Sulfur Dioxide
Emissions from Stationary
Sources. EPA-650/4-74-005g.
March 1976.
13. 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.
14.- 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.
-------
6-01-79 1 Section 3.5.12
Blank data forms are provided on
the following pages for the
convenience of the Handbook user.
Each blank form has the customary
descriptive title centered at the top of
the page. However, 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 M6-1.2
indicates that the form is Figure 1.2 in
Section 3.5.1 of the Method 6 Hand-
book. Future revisions of these forms,
if any, can be documented as 1.2A,
1.2B, etc. Thirteen 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 Calibra-
tion Log
2.4A and 2.4B Dry Gas Meter Sample
Calibration Data
(English and metric
units)
2.5 (MH) Pretest Sampling
Checks
3.1 (MH) Pretest Preparations
4.1 Sampling Data Form
for S02
4.2 Sample Label
4.3 Sample Recovery and
Integrity Data
4.4 (MH) On-Site Measurements
5.1 (MH) Posttest Sampling
Checks
5.2 Sulfur Dioxide Analyt-
ical Data
5.3 Control Sample Analyti-
cal Data
5.4 (MH) Posttest Operations
6.1 A and 6.1B Sulfur Dioxide
Calculation Forms
(English and
metric units)
8.1 Method 6 Check-
list to be Used
by Auditors
12.0 Data Forms
-------
Procurement Log
Item description
Qty.
Purchase
order
number
Vendor
Date
Ord.
Rec.
Cost
Disposition
Comments
v>
o>
2
§
w
01
6
Nj
to
Quality Assurance Handbook M6-1.2
-------
Wet test meter serial number
Wet Test Meter Calibration Log
— Date
CTI
b
Range of wet test meter flow rate
Volume of test flask V8 =
Satisfactory leak check?
Test
number
1
2
3
Manometer
reading, "
mm HiO
Final
volume (ViJ,
L
Initial
volume (VJ,
L
Total
volume (VmP.
L
Flask
volume (Va),
L
Percent
error. c
"Must be less than 10 mm (0.4 in.) H2O.
Calculations:
"Vm=V, - V-,.
c% error = 100 fVm - VJ/V, =
.(±1%).
. Signature of calibration person
M
CJ
bi
Quality Assurance Handbook M6-2.2
-------
Dry Gas Meter Sample Calibration Data
(English units)
Date
Barometer pressure, Pm = ,
Calibrated by.
Meter box number
.in. Hg
Wet test meter number
3
A
O
D/y test meter temperature correction factor.
Wet test
meter
pressure
drop ID W,°
in. H,O
Rota-
meter
setting
ffU
ft3/min
Wet test
meter gas
volume
(V*).*
ft3
Dry test meter
gas volume
(Vat." ft3
Initial
Final
Wet test
meter
gas temp
(t«;.
°F
Dry test meter
Inlet
gas temp
fta,J,
°F
Outlet
gas temp
(te0>.
°F
Average
gas temp
fUc
°F
Time
of run
(6)."
min
Average
ratio
fYJ.'
(Y,).'
'Dm expressed as a negative number.
"Volume passing through meter. Dry gas volume is minimum for at least five revolutions of the meter.
c The average of f
-------
Dry Gas Meter Sample Calibration Data
(metric units)
Date
Calibrated by_
Meter box number
Barometer pressure. Pm = .
Dry test meter temperature correction factor.
mmm Hg
°C
Wet test meter numbi
Wet test
meter
pressure
drop (D^).'
mm. HiO
Rota-
meter
setting
(RJ.
L/min
Wet test
meter gas
volume
fVJ."
L
Dry test meter
gas volume
fVot." L
Initial
Final
Wet test
meter
gas temp
(U.
°C
Dry test meter
Inlet
gas temp
(t*,).
°C
Outlet
gas temp
(taot.
°C
Average
gas temp
(to).0
°C
Time
of run
(6)."
min
Average
ratio
fYJ."
fYJ.'
01
b
sj
to
*Dm expressed as a negative number.
"Volume passing through meter. Dry gas volume is minimum for at least five revolutions of the meter.
c The average of t a ( and ta0 if using two thermometers; the actual reading if using one thermometer.
" The time it takes to complete the calibration run.
* With Y defined as the average ratio of volumes for the wet test and the dry test meters. Y,= Y±O.02Y for calibration and Y, = Y±0.05Y for the
posttest checks, thus.
y. = I/, ft* + 273°C)[Pm
Va(t*+273°C)(Pm>
rj , ,
w
0>
2
o
3
U
.
' With Y, defined as the average ratio of volumetric measurement by wet test meter to rotameter. Tolerance Y, = / ±0.05 for calibration and Y
±0. 1 for posttest checks
273°f) {/»m
0(t*+273°C).P^(0.03S)
fFl}
Quality Assurance Handbook M6-2.4.ti
-------
..-*
Sampling Data Form for SOz
Plant name
Sample location
Operator
Barometric pressure, mm fin.) 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)
-Sample point location
-Sample purge time, min _
o>
w
en
-Remarks
Sampling
time,
min
Total
Clock
time.
24 h
Sample
volume.
Lift3)
Total
Sample flow
rate setting,
L/min (ft3/min)
Sample volume
meter ed (& Vm).
Lift3)
AVm
avg
Percent
deviation. "
%
Avg
dev
Dry gas
meter temp.
°C(°F)
Avg
Impinger
temp.
°Cf°FJ
Max
temp
01
6
(D
'Percent deviation =
&V avg™
Quality Assurance Handbook M6-4.1
-------
5-01-79
Section 3.5.12
Plant
Site .
Dale
Front rinse D
Back rinse D
Solution
Volume: Initial.
Cleanup by
Sample Label
City
Sample type
Run number
Front filter D
Back filter D
Front solution D
Back solution D
Level marked D
.Final-
Quality Assurance Handbook M6-4.2
-------
Plant
Section 3.6.12 8
Sample Recovery and Integrity Data
Sample location
6-01-79
Field Data Checks
Sample recovery personnel
Person with direct responsibility for recovered samples
Sample
number
1
2
3
4
5
6
Blank
Sample
identification
number
Date
of
recovery
Liquid
level
marked
Stored
in locked
container
Remarks
Signature of field sample trustee.
' Laboratory Data Checks
Lab person with direct responsibility for recovered samples
Date recovered samples received
Analyst
Sample
number
1
2
3
4
5
6
Blank
Sample
identification
number
Date
of
analysis
Liquid
at marked
level
Sample
identified
Ramarks
Signature of lab sample trustee.
Quality Assurance Handbook M6-4.3
-------
6-01-79
Section 3.6,12
Sulfur Dioxide Analytical Data
Plant Date
Sample location Analyst
Volume and normality of barium perch/orate 1 ml N
2 ml N
3 ml N
N. avg
Sample
number
1
2
3
4
5
6
Blank
Sample
identification
number
Total
sample
volume
(VKln).
ml
N/A
Sample
aliquot
volume
(VJ.a
ml
Volume of titrant (Vt)." ml
1st
titration
2nd
titration
Average
Vt» =
"Volume for the blank must be the same as that of the sample aliquot.
" 1st lllrallon = o.S9 to 1.0] or | 1st titration - 2nd titration \
-------
Section 3.5.12
10
5-01-79
Control Sample Analytical Data Form
Plant.
Date analyzed
Analyst
N Ba(CIOt),
Weight of ammonium sulfate is 1.3214 g?
Dissolved in 2 L of distilled water?
Titration of blank
Control
sample
number
Time of
analysis.
24 h
Titrant volume. * ml
1st
2nd
3rd
Avg
*Two titrant volumes must agree within 0.2 ml
25.ml .* ,,
(control sample) (control sample)
. ml x.
(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 M6-5.3
-------
6-01-79 11 Section 3.5.12
Sulfur Dioxide Calculation Form
(English units)
Sample Volume*
= _- ft3. Tm= •_»/?, Pta, = __•__//?. Hg. / = _•
Vm**> = 17.64 °R xYv™p»*< = fti
in. Hg Tm Equation 6-1
SOz Concentration
N = _ • ____ (g-eqt/ml, V, = __•__ m/, l/,b = __•--
Vsom = ___ • - - ml, Va = _ _ • _ ml
Cso2 =7.06x1 n-s-lsan = _ . _ _ _ x , Q-* lb/dscf
l^mistdi Equation 6-2
"Calculation form for data collected using Method 6 type equipment. The
alternative use of Method 5 or Method 8 equipment will change Vm and Vm
-------
5-01-79 3 Section 3.6.0
Pretest Sampling Checks
(Method 7. Figure 3.1)
Date Calibrated by
Flask Volume
Flask volumes measured with valves? yes no
Volume measured within ±10 ml of actual volume?* yes no
Temperature Gauge
Was a pretest temperature correction used? yes no
If yes. temperature correction (within ±J°C (2°F) of
reference values for calibration and within ±2°C (4°F) of
reference values for calibration check)
Vacuum Gauge
Was gauge calibrated against a U-tube mercury manometer
(if it was a mechanical gauge)?* yes no not applicable
Barometer
Was the pretest field barometer reading within ±2.5 mm (0.1 in.)
Hg of the mercury-in-glass barometer? yes no
*Most significant items/parameters to be checked.
-------
Section 3.6.0
5-01-79
Pretest Preparations
{Method 7. Figure 3.2)
Apparatus check
Probe
Glass liner clean
Heated properly
Leak checked
Collection Flask
Clean
Leak checked
Temperature gauge
Evacuation System
Leak-free pumps
Manifold and tubing
U-tube manometer
Barometer
Reagents
Distilled water
Absorbing solution*
Sodium hydroxide. 1N
pH paper
Sample Recovery
Dropper or burette
Sample bottles
Pipette. 25 ml
Acceptable
Yes
No
Quantity
required
Ready
Yes
No
Loaded
and packed
Yes
No
"Most significant items/parameters to be checked.
-------
5-01-79 5 Section 3.6.0
On-Site Measurements
(Method 7, Figure 4.3)
Sampling
Volume of 25 ml of absorbing solution placed in flask? .
Flask valve stopper in purge position?
Sampling train properly assembled?
Leak free?* Stopcock grease used?
Type?
Flask evacuated to 75 mm (3 in.) Hg pressure?
Leakage from manometer observation
(e.g., maximum change in manometer of <10 mm (0.4 in.) Hg/min)?*
Initial pressure of flask recorded?*
Initial temperature of flask recorded?
Probe purged before sampling?
Sample collected properly?*
Flask shaken for 5 min after collection and disassembly from train?*
Oxygen introduced to flask? Method used?
Samples properly labeled and sealed and stored for shipment?
Sample Recovery
Samples allowed to remain in flasks for minimum of 16 h?*.
Final flask temperature and pressure recorded?*
Sample transferred to leak-free polyethylene bottle?
Flask rinsed twice with 5-mt portions of distilled water and rinse added to bottle containing sample?
pH adjusted to between 9 and 12?*.
*Most significant items/parameters to be checked.
-------
Section 3.6.0 6 6-01-79
Posttest Operations
(Method 7. Figure 5.3)
Reagents
Phenoldisulfonic acid stored in dark stoppered bottle? .
Sulfuric acid, concentrated, 95% minimum assay reagent grade?.
Ammonium hydroxide, concentrated reagent grade?
Sample Preparation
Was liquid level noticeably changed?*
Original volume Corrected volume
Analysis
Spectrophotometer calibrated?".
Setting for maximum absorbance of standard nm
Control sample prepared?*
Any solids in sample removed through Whatman No. 41 filter paper?
Absorbance measured at optimum wavelength used for the standards, using the blank solution as a
zero reference?
All analytical data recorded on checklist and laboratory form?
*Most significant items/parameters to be checked.
-------
5-01-79
Section 3.6.1
1.0 Procurement of Apparatus and Supplies
The activity matrix for apparatus is
given in Table 1.1 at the end of this
section. The required apparatus for a
Method 7 sampling train is shown in
Figure 1.1. Additional specifications,
criteria, and/or design features as
applicable are given here to aid in the
selection of equipment to ensure the
collection of good quality data. All
new items of equipment are to be
inspected visually for identification
and damage before acceptance. Also,
if applicable, new equipment is to be
calibrated according to Section 3.6.2,
as part of the acceptance check.
During the procurement of
equipment and supplies, it is
suggested that a procurement log be
used to record the descriptive title of
the equipment, identification number
(if applicable), and the results of
acceptance checks. An example of a
procurement log is shown in Figure
1.2. A blank copy of this form is given
in Section 3.6.12 for the Handbook
user. Calibration data generated in the
acceptance check are to be recorded
in the calibration log book. Alternative
grab sampling systems or equipment
capable of measuring sample volume
to within ±2% and collecting a
sufficient sample volume to allow
analytical repeatability to within ±5%
is acceptable, subject to approval. The
following equipment is specified in
the Reference Method.
1.1 Sampling
1.1.1 Sampling Probe - The
sampling probe should be made of
glass (borosilicate) encased in a
stainless steel sheath and equipped
with a heating system capable of
preventing water condensation and
with a filter (either in-stack or heated
out of stack) to remove paniculate
matter. A plug of glass wool in the
sample probe is satisfactory for the in-
stack filter. Stainless steel or Teflon"
tubing may also be used for the probe
liner. Heating is not required if the
probe remains dry during the purging
period, but it is recommended that the
probe have provision for heating. The
in-stack end of the probe should have
an expanded diameter for about the
first 4 cm to be used for the glass-
wool filter. A probe of approximately
1.2 m (4 ft) total length is usually
sufficient for sampling. However, the
"Trade name.
probe tip can be no closer than 1 m
(3.28 ft) from the inner wall of stacks
>2 m in diameter. When stack gas
temperatures exceed 480°C (900°F), a
probe fabricated from quartz (Vycor)
should be used along with quartz
wool for filter material. The main
criterion in selecting a probe material
is that it be nonreactive with the gas
constituents and therefore not
introduce a bias into the analysis.
A new probe should be checked
visually for specifications (i.e., the
length and composition ordered). It
should be checked for cracks, breaks,
and leaks on a sampling train. The
probe heating system should be '
checked as follows:
1. Connect the probe (without filter)
to the inlet of the pump.
2. Electrically connect and turn on
the probe heater for 2 or 3 min.
If functioning properly, it will
become warm to the touch.
3. Start the pump and adjust for a
flow rate of about 1.0 L/min.
4. Check the probe. It should
remain warm to the touch. The
heater must be capable of
maintaining the exit air
temperature at a minimum of
100°C (212°F) under the above
conditions. If it cannot, the probe
should be replaced. Any probe
not satisfying the acceptance
check should be repaired if
possible, or returned to the
supplier.
1.1.2 Collection Flask - A 2-L
borosilicate round bottom flask, with a
short neck and 24/40 standard taper
opening is required. The collection
flask should be protected from
implosion or breakage by using (1)
tape, (2) a commercial unit encased in
foam, or (3) a fabricated closed-cell
foam enclosure. Once the flask has
been connected to the flask valve,
both should be marked as a set and
neither should be used at random
with other flasks as this will cause
volume fluctuations with the sample.
1.1.3 Flask Valve - A T-bore
stopcock is connected to a 24/40
standard taper joint. Bores should be
numbered but not switched to prevent
leakage problems. The T-bore should
be marked to avoid turning the
stopcock in the wrong direction when
sampling. The flask valve should be
marked to identify its matched flask.
1.1.4 Temperature Gauge - A tem-
perature gauge should consist of a
dial-type thermometer, or equivalent,
capable of measuring 1°C (2°F)
intervals from -5°to 50°C (25° to
125°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-1 No. 63C or
63F. Damaged thermometers that
cannot be calibrated must be
replaced.
1.1.5 Vacuum Line - The vacuum
line should be of a nonreactive, thick
wall type and should be leak checked
at 75 mm (3 in.) Hg of absolute
pressure while connected to the
sampling train. The tubing should be
flexible and approximately 1 to 1.6 m
(3 to 5 ft) in total length. If the tubing
is found to leak, it should be rejected.
1.1.6 Vacuum Gauge - A U-tube
manometer should be about 1 m (36
in.) in length with 1-mm (0.1 in.)
divisions, or the equivalent, capable of
measuring pressure to within ±2.5
mm (0.1 in.) Hg. If a U-tube
manometer is used, no calibration is
required. Upon receipt, the user
should verify by reading the
instructions that the manometer was
designed to use mercury. If the mano-
meter is acceptable, it must then be
leak checked. When a mechanical
vacuum gauge is used, it must be
calibrated upon receipt by the
procedures described in Section 3.6.2.
If it fails to calibrate, it should be
replaced.
The vacuum gauge should be leak
checked as follows: (1) connect
vacuum line to the manometer at the
end that connects to the sampling
train, as shown in Figure 1.1, (2) pull
a vacuum of 75 mm (3 in.) Hg or less,
(3) shut off the valve between the
manometer and the pump, (4) shut off
the pump, (5) observe the vacuum
registered on the manometer for any
deviation over a 1-min period. If there
is.no deviation, the vacuum gauge is
acceptable; if there is a deviation, the
gauge is unacceptable and should be
corrected or replaced.
-------
Section 3.6.1
6-01-79
1.1.7 Vacuum Pump - The vacuum
pump should be capable of producing
a vacuum of 75 mm (3 in.) Hg or less.
The pump must be leak free when
running and when pulling a vacuum
(inlet plugged) of 75 mm (3 in.) Hg.
Two types of vacuum pumps are
commonly used—a modified sliding
fiber vane pump or a diaphragm
pump. For safety reasons, the pump
should be equipped with a three-wire
electrical cord. 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 75 mm (3 in.) Hg of vacuum.
The vacuum reading should remain
stable for 30 s.
1.1.8 Squeeze Bulb - A one-way,
hard rubber bulb with about a 50-ml
capacity is needed to purge the
sampling system.
1.1.9 Volumetric Pipette - A 25-ml
volumetric glass pipette (Class A) is
needed for addition of reagent to the
collection flask.
1.1.10 Stopcock Grease - An inert,
high-vacuum, high-temperature
chlorofluorocarbon grease should be
used. Halocarbon 25 - 5S has been
found to be effective.
1.1.11 Barometer - Mercury,
aneroid, or other barometers capable
of measuring atmospheric pressure to
within 2.5 mm (0.1 in.) Hg are
required. In many cases, the
barometric reading may be obtained
from a nearby National Weather
Service Station, in which case the
station value (which is the absolute
barometric pressure) should be re-
quested; and an adjustment for eleva-
tion differences between the weather
station and the sampling point should
be applied at a rate of -2.5 mm Hg per
30 m (0.1 in. Hg/100 ft) of elevation
increase, or vice versa for elevation
decrease. Upon receipt, check the
barometer against a mercury-in-glass
barometer. Replace it if it cannot be
calibrated to read correctly.
1.2 Sample Recovery
1.2.1 Graduated Cylinder - A 50-ml
glass or polyethylene graduated cyl-
inder with 1-ml divisions is required.
1.2.2 Storage Bottles - A minimum
of 12 leak-free polyethylene bottles
for recovery of samples are needed.
The bottles should be packed in a
cushioned, locked container (box or
footlocker) for shipment. The leak-free
seal can be initially checked by
putting water in each, sealing, and
then shaking the container upside
down.
1.2.3 Wash Bottle - Glass or poly-
ethylene wash bottles are needed for
rinsing (transferal) of the sample
solution to storage bottles.
1.2.4 Stirring Rod - A stirring rod
(glass or polyethylene) is required to
check the pH of the absorbing
reagent.
1.2.5 pH Indicating Paper - pH paper
with the range of 7 - 14 is required to
test the alkalinity of the samples.
1.3 Analysis
1.3.1 Pipettes - Several volumetric
pipettes are required (two 1 ml, two 2
ml, one 3 ml, one 4 ml, two 10 ml,
and one 25 ml); one transfer pipette
(10 ml with 0.1-ml divisions) is
required.
1.3.2 Volumetric Flasks - One 100-
ml volumetric flask is needed for each
sample and each standard. Two 1000-
ml volumetric flasks are required for
the blank and the standard nitrate.
Additional volumetric flasks (50 ml)
are required for aliquots for analysis
and for dilution of samples that fall
outside the calibration range
(absorbance >400-i/g standard).
1.3.3 Evaporating Dishes - Several
175- to 250-ml capacity porcelain
dishes with lip for pouring are
needed, one for each sample and one
for each standard. The Coors No.
45006 (shallow, 195 ml) has been
found to be satisfactory. Alternatively,
polymethylpentene beakers (Nalge
No. 1203, 150 ml) or glass beakers
(150 ml) may be used. When glass
beakers are used, etching of the
beakers may cause solid matter to be
present in the analytical step; the
solids should be removed by filtration.
For this reason, glass beakers should
be used only if necessary.
1.3.4 Steam Bath - A steam bath is
required to evaporate the absorbing
solution. Low-temperature ovens or
thermostatically controlled hot plates
kept below 70°C (160°F) are
acceptable alternatives.
1.3.5 Polyethylene Policeman - One
stirring rod (polyethylene policeman)
is required for each sample and
standard. A glass stirring rod is not
recommended.
1.3.6 Graduated Cylinder - A 100-
ml graduated glass cylinder (Class A)
with 1-ml divisions is required for
additions of distilled water.
1.3.7 Spectrophotometer - A
spectrophotometer capable of
measuring the absorption at 410 nm
(or the maximum peak)!* a set of
neutral density filters, and a filter for
wavelength calibration are required.
1.3.8 pH Paper • The paper should
cover the pH range of 7 - 14 with
intervals of 1 -pH unit.
1.3.9 Analytical Balance - One ana-
lytical balance that weighs to 0.1 mg
and a set of Class-S calibration
weights to check the accuracy of the
balance (±0.3 mg) upon receipt are
needed. The balance should be
serviced by or returned to the
manufacturer if agreement cannot be
met.
1.3.10 Dropping Pipette or Dropper
- A dropping pipette, or a dropper, or
its equivalent for addition of
ammonium hydroxide to the evapora-
tion dish is needed.
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, use the best
available grade.
1.4.1 Sampling - To prepare the
absorbing solution, cautiously add 2.8
ml of concentrated HjSO* to 1 L of
deionized distilled water and mix well.
Add 6 ml of 3% hydrogen peroxide,
freshly prepared from 30% hydrogen
peroxide (ACS reagent grade) solution.
The absorbing solution must be used
within 1 week of its preparation and if
possible within 24 h. Store in a dark-
colored bottle. Do not expose to
extreme heat or direct sunlight. Note:
The 30% hydrogen should be stored in
the refrigerator.
1.4.2 Sample Recovery - Two rea-
gents are required for sample
recovery.
Sodium hydroxide (IN) - Dissolve 40
g of NaOH ACS reagent grade in
deionized distilled water and dilute to
1 L.
Water - Use deionized distilled H20
to conform to ASTM specification
D1193-74, Type 3. At the option of
the analyst, the KMn04 test for
oxidizable organic matter may be
omitted whenever high concentrations
of organic matter are not expected to
be present.
1.4.3 Analysis - For the analysis,
the following reagents are required.
-------
5-01-79
Section 3.6.1
Fuming sulfuric acid - Use 15% to
18% by weight of free sulfur trioxide,
ACS reagent^grade. Note - Handle
with caution.
Phenol - Use white solid, ACS
reagent grade.
Sulfuric acid - Use concentrated,
'95% minimum assay, ACS reagent
grade. Note - Handle with caution.
Potassium nitrate - Dry at 105° to
110°C (220° to 230°F) for a minimum
' of 2 h just prior to preparation of
standard solution, ACS reagent grade.
Standard KNOy solution -Dissolve
exactly 2.198 g of dried potassium
nitrate (KNOs) in deionized distilled
water and dilute to 1 L with deionized
distilled water. One ml of the working
standard solution is equivalent to 100
/jg of nitrogen dioxide (NOa).
Water • Deionized distilled H20 as
'in Subsection 1.4.2.
Phenoldisulfonic acid solution -
Dissolve 25 g of pure white phenol in
150 ml of concentrated sulfuric acid
on a steam bath. Cool; add 75 ml of
fuming sulfuric acid; and heat at
100°C (212°F) for 2 h. Store in a dark,
stoppered bottle. Alternatively, this
solution may be purchased prepared,
if it meets the American Public Health
Association specification for nitrate-
nitrogen in water.
Ammonium hydroxide - Use
concentrated, ACS reagent grade.
Probe
\
f W Evacuate
Q Purge
Flask valve \. H) Sample
I
Filter
Squeeze bulb
Pump valve
.Pump
Purge
Thermometer
Figure 1.1. Evacuated flask sampling train.
Table 1.1 Activity Matrix for Procurement of Apparatus and Supplies
Apparatus/
reagents
Probe
Acceptance limits
Borosilicate glass
tubing, stainless steel or
Teflon capable of
removing paniculate and
preventing moisture
condensation
Frequency and method
of measurement
Upon receipt, visually
check for cracks
or flaws and heating
capability
Action if
requirements
are not met
Return to
supplier and
note in pro-
curement log
Collection flask
Two-liter borosilicate
glass round bottom,
short neck w/24/40
standard taper opening
Upon receipt visually
check and leak
check
As above
Flask valve
Borosilicate glass T-
bore stopcock w/24/40
standard taper male
joint (joint connection
to be made by glass-
blower)
Visually check upon
receipt
As above
Temperature
gauge
Vacuum line
tubing
Vacuum gauge
Vacuum pump
Squeeze bulb
Volumetric
pipettes
Dial -type, capable of
measuring from -5° to
+50°C within 1°C
Capable of withstanding
75 mm absolute
pressure .
U-tube manometer, open
end, 1 m with 1-mm
divisions
Pump capable of pulling
vacuum of 75 mm Hg or
less
Rubber, one-way
1-, 2-, 3-. 4-. 10-,
25-ml glass (Class A)
Visually check upon
receipt, and compare
against Hg-in-glass
thermometer
Upon receipt visually
check and leak
check
Visually check upon
receipt
Upon receipt check
with suitable
pressure gauge
Visually check upon receipt
As above
As above
As above
As above
As above
As above
As above
-------
Section 3.6.1
5-01-79
Table 1.1 (continued)
Apparatus/
reagents
Stopcock grease
Barometer (or
consult local
weather station)
Storage bottle
Wash bottle
Glass stirring
rod
pH paper
Volumetric
flasks \
Evaporating ,
dishes
Steam bath
Polyethylene
policeman
Graduated cylinders
Spectrophotometer
Dropping
pipette or
dropper
Sulfuric acid
Hydrogen peroxide
Sodium hydroxide
Sulfuric acid
Phenol
Potassium nitrate
Acceptance limits
High vacuum, high
temperature chloro-
fluorocarbon grease
Capable of reading
atmospheric pressure
to ±2.5 mm Hg
Polyethylene. 100-ml,
or greater capacity.
screw cap
Polyethylene or glass
As Above
Sensitive in pH range
7-14
50-. 100-. 1000-ml
glass (Class A)
Porcelain evaporating
dishes or polymethyl-
pentene beakers
Evaporate the sample
solution at a low
controlled temperature
Polyethylene stirring
rod
50. 100 ml (Class Aj
with 1 -ml divisions
Capable of measuring
absorbance at 4 10 nm
(such as Bausch & Lomb
Spectronic 70)
Able to add reagents
dropwise
Concentrated, ACS
reagent grade
3O% aqueous solution,
ACS reagent grade
ACS reagent grade
pellets
Fuming, 15-18% free
sulfur trioxide
White solid. ACS
reagent grade
ACS reagent grade
Frequency and method
of measurement
As above
Visually check;
calibrate against
mercury-in-glass
barometer
Visually check upon
receipt
Visually check label
upon receipt
As above
As above
As above
As above
As above
As above
As above
Upon receipt, either
check wavelength
with filters or ensure
optimum wavelength
is between 400
and 415 nm
Visually check upon
receipt
Visually check upon
receipt; check speci-
fications
As above
Visually check upon
re'ceipt; check speci-
fications
As above
As above
As above
Action if
requirements
are not met
As above
As above
Return to
supplier and
note in pro-
curement log
As above
As above
Return to
supplier
As above
Discard when
the bottoms
become
etched
Return to
supplier
As above
As above
Adjust, re-
calibrate as
per manu-
facturer's
instructions,
and note in
procurement
log
Return to
supplier
As above
As above
Return to
supplier
As above
As above
As above
-------
Procurement Log
Item description
•jyatc^oohoto/ncfer
Qty.
1
Purchase
order
number
I03S
Vendor
6au**\ + /.oW)
Date
Ord.
2-tl'Tt
Rec.
Z-/V-77
Cost
Azfoo.
Dispo-
sition
ok.
Comments
Ol
6
CD
W
9
Figure 1.2. Example of a procurement log.
-------
6-01-79
Section 3.6.2
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 are designed for the
equipment specified by Method 7 and
described in the previous section.
Table 2.1 at the end of this section
summarizes the quality assurance
functions for calibration. All
calibrations should be recorded on
standardized record forms and
retained in a calibration log book.
2.1 Collection Flask
Assemble the clean flasks and
valves and fill with water (room
temperature) to the stopcock. Measure
the volume to ±10 ml by transferring
the water to a 500-ml glass (Class A)
graduated cylinder. Do duplicate
volume determinations, and use the
mean value. Number and record the
volume mean value on the flask or
foam encasement and in the
laboratory log book. This volume
measurement is required only on the
initial calibration if the flask valves
are not switched.
2.2 Spectrophotometer
2.2.1 Determination of Optimum
Wavelength - Calibrate the
wavelength scale of the
Spectrophotometer every 6 mo. The
calibration may be accomplished by
using an energy source with an
intense line emission such as a
mercury lamp, or by using a series of
glass filters spanning the measuring
range of the Spectrophotometer. Cali-
bration materials are available com-
mercially and from the National
Bureau of Standards. Specific details
on the uses of such materials should
be supplied by the vendor.
In general, when using glass filters,
each filter is inserted into the light
path and the wavelength dial is
rotated until the instrument response
is greatest. Then the reading on the
dial is noted and can be compared
with the true value. When using an
alternate light source, the instrument
lamp is replaced by the alternate
lamp. The wavelength dial is rotated,
and the dial reading is noted at each
peak for comparison with the true
value. The wavelength scale of the
Spectrophotometer must read correctly
within ±5 nm of the true wavelength
at all calibration points; otherwise, the
Spectrophotometer should be repaired
and recalibrated. Once the
wavelength scale of the
Spectrophotometer is properly
calibrated, use 410 nm as the
optimum wavelength for the measure-
ment of the absorbance of the
standards and samples.
Alternatively, a scanning procedure
may be employed to determine the
optimum wavelength. If the
instrument is a double-beam
Spectrophotometer, scan the spectrum
between 400 and 41 5 nm using a
200 (jg N02 standard solution in the
sample cell and a blank solution in
the reference cell. If a peak does not
occur, the Spectrophotometer is
probably malfunctioning and should
be repaired. If a peak is obtained
within the 400- to 415-nm range, the
wavelength at which this peak occurs
should be the optimum wavelength
for the measurement of absorbance of
both the standards and the samples.
For a single-beam Spectrophotometer,
follow the scanning procedure
described, but scan the blank and the
standard solutions separately. The
optimum wavelength should be the
one at which the maximum difference
in absorbance between the standard
and the blank occurs. The data
obtained for this alternative optimum
wavelength determination should be
recorded on the data form as shown
in Figure 2.1.
2.2.2 Determination of Calibration
Factor - Kc - The calibration factor (Kc)
must be determined in the verification
of the analytical technique and
solution preparation prior to sample
analysis with the control sample.
After the analytical technique and
solutions have been verified as to
their accuracy and precision, a new
calibration factor should be
determined simultaneously with the
field sample analysis. Since a detailed
discussion of this procedure is
included in the sample analysis
Section 3.6.5, it is omitted here.
2.3 Barometer
The field barometer should be ad-
justed initially and before each test
series to agree within 2.5 mm (0.1 in.)
Hg of the mercury-in-glass barometer
or with the pressure value reported
from a nearby National Weather
Service Station and corrected for
elevation. The correction for elevation
difference between the station and
sampling point should be applied at a
rate of -2.5 mm Hg/30 m (-0.1 in.
Hg/100 ft) elevation increase, or vice
versa for elevation decrease.
2.4 Thermometer
The thermometers used to measure
the temperature of the sample flask
should be initially compared with a
mercury-in-glass thermometer that
meets ASTM E-1 No. 63C or 63F
specifications as follows:
1. Place both the mercury-in-glass
and the dial type or an equivalent
thermometer in an ice bath.
^ Compare readings after the bath
stabilizes.
2. Allow both thermometers to
come to room temperature.
Compare readings after both
stabilize.
3. The dial-type or equivalent ther-
mometer is acceptable if values
agree within 1°C (2°F) at both
room and ice bath temperatures.
If the difference is greater than
±1°C (2°F), the thermometer
should be either adjusted and
recalibrated until the above
criteria are met, or replaced.
4. Prior to each field trip the
temperatures should then be
compared at room temperature
with the thermometer in the
equipment. If the value is not
within ±2°C (4°F) of the mercury-
in-glass thermometer value, the
meter thermometer should be
replaced or recalibrated.
2.5 Vacuum Gauge
When a mercury U-tube manometer
is used, no calibration is required. The
U-tube manometer should be checked
initially to ensure that it is leak free.
When a mechanical gauge is used,
it must be calibrated against a
mercury U-tube manometer before the
field test unless otherwise specified
by the Administrator. The mechanical
gauge should be calibrated in the
following manner:
1. Connect the mechanical gauge
and the U-tube manometer in
parallel with the vacuum pump.
This can be accomplished with a
T-connection. One line should be
placed on the vacuum side of the
pump, and the other two lines
should be placed on the vacuum
side of the gauge and
manometer.
-------
6-01-79
Section 3.6.2
2. Turn the pump on, and pull a
vacuum of about 25 to 50 mm (1
to 2 in.) Hg. Shut off main pump
valve and then shut off pump.
3. Observe the U-tube manometer
to be sure that the system is leak
free. Any variation >10 mm (0.4
in.) Hg over a 1-min period is not
acceptable. The manometer and
gauge readings must agree
within ±2.5 mm (0.1 in.) Hg, or
the gauge should be repaired or
replaced.
4. Turn the pump on, and pull the
maximum vacuum for which the
pump is capable (must be within
75 mm (3 in.) Hg of absolute
pressure). , Shut off the main
valve, and then the pump.
5. Be sure that the system is leak
free and again compare readings.
6. The gauge must agree within 2.5
mm (0.1 in.) Hg at both vacuums,
or the gauge is not acceptable.
2.6 Analytical Balance
The analytical balance should
always be zeroed and calibrated
against a standard Class-S weight(s)
just before the potassium nitrate
(KIMOa) is weighed for the formulation
of the working standard. This
calibration should be done in the
following manner:
1. Zero the balance.
2. Place a 5-g and then a 10-g
standard weight on the balance.
3. Be sure the balance readings of
the standardized weights agree
within ±2 mg of the standard
weights.
Enter the data on the calibration
form, Figure 2.2.
The weight of the weighing boat
and the potassium nitrate should
be <10 g; if not, heavier
standard weights should be used
to calibrate the balance.
4.
-------
5-01-79
Section 3.6.2
Spectrophotometer number
Calibrated by
"
Date
2/IP17 7
Reviewed by
"7?
Spectrophotometer
setting, nm
399
400
401
402
403
404
405
406
407
405
409
4/0
411
412
413
414
415
416
Absorbance
of standard
ODa
t?ss
.93?
.920
.JOS'
.115
•*?/
.*«$
• Wf
.17?
.17?
.873
• **f
.$30
.*Z3
.*//
• VOb
• 7*f
• 777
Absorbance
of blank
OD*
./zs-
.'*7
• /3&
./ /t>
• 097
.0*t>
.010
.07?
.6t>6>
.ose>
.057
.0
.63/
.02$
.0/5
.oof
.000
Actual
absorbance of
ODC
• 7?0
•777
.7W
• 7*9
•7?*
• bos-
.to*
.3/0
.7/3
%z/
.%/&
•9fi/
,7W
.Vt*~
,7**>
• 7f/
• 7/6
.777
'Absorbance of the 200 fjg NOz standard in a single beam Spectrophotometer.
tiAbsorbance of the blank in a single-beam Spectrophotometer.
cFor a single-beam Spectrophotometer — absorbance of the standard minus absorbance of the blank.
For a double beam Spectrophotometer — absorbance of the 200 /jg NOz standard with the blank in the
reference cell.
Spectrophotometer setting for maximum actual absorbance of standard
If the maximum actual absorbance occurs at the Spectrophotometer setting of <399 or>416 nm,
the Spectrophotometer must be repaired or recalibrated.
Figure 2.1. Optimum wavelength determination data form.
-------
Section 3.6.2
5-01-79
Balance name
Analytical Balance Calibration Form
facto
Number.
*
Classification of standard weights
Date
0.5000 g
0.500+
1.0000 g
£>.
-------
5-01-79
Section 3.6.2
Table 2.1. Activity
Apparatus
Collection
flask
Spectropho-
tometer.
Barometer
Thermometer
Vacuum gauge
(mechanical
only)
Analytical bal-
ance
Matrix for Calibration of Equipment
Acceptance limits
Measure volume within
±10 ml
1 . Calibrate wave-
length scale3
2. Determine optimum
wavelength within 399
to 416 nm*
Reading agrees within
±2.5 mm (0.1 in.) Hg
of mercury-in-glass
barometer
Reading agrees within
±1°C(2°F) of mercury-
in-glass thermometer
Reading agrees within
±2.5 mm (0. 1 in.) Hg
of mercury U-tube man-
ometer
Weight within ±2 mg of
standard weights (Class
S)
Frequency and method
of measurement
On receipt, measure
with graduated cyl-
inder
1. Upon receipt and
every 6 mo, use glass
filters or light
source
2. Upon receipt and
every 6 mo scan be-
tween 400 and 415 nm
with 200 mg NOz stand-
ard solution
Upon receipt and be-
fore each field test
As above
As above
Use standard weight
before preparation
of working solution
Action if
requirements
are not met
Recalibrate
1. Return
to manufac-
turer for
repair
2. As above
Repair or
return
As above
As above
Repair or
return to
manufacturer
" The tester may opt to perform either step 1 or 2. both are not required.
-------
5-01-79
Section 3.6.3
3.0 Presampling Operations
The quality assurance functions for
presampling operations are
summarized in Table 3.1 at the end of
this section. See Section 3.0.1,
Planning the Test Program, of this
Handbook for details on preliminary
site visits.
3.1 Apparatus Check and
Calibration
Previously used equipment should
be visually checked for damage
and/or excessive wear before each
field test. Items should be repaired or
replaced (as applicable) if judged to be
unsuitable for use. A pretest checklist
(Figure 3.1) summarizes equipment
calibration. The pretest operations
form (Figure 3.2) can be used as an
equipment check and packing list. The
completed form should be dated,
signed by the field crew supervisor,
and filed in the operational log book.
The replacement of worn or damaged
items of equipment should be
initiated. Procedures for performing
the checks are given herein; a check
is placed in the proper row and
column as the check/operation is
completed. Each team will have to
construct its own checklist according
to the type of sampling train and
equipment it uses.
3.1.1 Probe (Filter) - Clean the probe
internally by brushing first using tap
water, then with distilled deionized
water, next with acetone, and finally
allow it to dry in the air. In extreme
cases, the glass liner can be cleaned
with stronger reagents. Note - Do not
use nitric acid to clean the probe
unless a thorough cleaning is
performed to remove all the nitrates.
In either case, the object is to leave
the glass liner chemically inert to
oxides of nitrogen. If the probe is
equipped with a heating system,
check to see whether it is operating
properly. The probe should be sealed
on the filter side and checked for
leaks at an absolute pressure of <380
mm (15 in.) Hg. The probe must be
leak free under these conditions. This
leak check may be performed
following the leak check of the sample
flask and using the same setup as
described below in Subsection 3.1.2.
The glass liner should be sealed
inside the metal sheath to prevent
ambient air from entering the duct.
3.1.2 Collection Flask, Flask Valve,
and Evacuation System - The collec-
tion flask and valve in contact with
sample gas should be cleaned with a
strong detergent and hot water, and
rinsed with tap water and deionized
distilled water. Periodically, the
glassware can be cleaned with a
grease remover such as
decahydronaphthalene (CioH,B),
followed with acetone, and then with
the cleaning agents named above. An
alternate procedure is to use dichro-
mate cleaning solution. Do not use
solutions containing nitrogen. Vapor
degreaser can be used to remove the
stale vacuum grease.
Stopcocks and joints should be
lubricated with a chemically inert
lubricant. An inert hydrogen-free
chlorofluorocarbon lubricant can be
used.
The evacuation system (Figure 1.1)
is assembled, and a minimum vacuum
of 75 mm (3 in.) Hg absolute pressure
is produced in each flask with the
flask valve in the "evacuation" posi-
tion. The vacuum should be held for
at least 1 min with the pump valve in
the "vent" position without apprecia-
ble fluctuation (<10 mm (0.4 in.) Hg);
if this is not possible, check for leaks.
If the leak check of the probe is to
be performed using the same setup,
the probe tip should be plugged with a
rubber stopper. Immediately after the
sample flask has been determined to
be leak free, turn the flask valve to
the "purge" position. The vacuum will
initially drop. After the vacuum
stabilizes there should not be any
appreciable fluctuation—that is <10
mm (0.4 in.) Hg over a 1-min period. If
stabilization is not obtained, check for
leaks and correct.
3.2 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, use the best
available grade.
Chloride is an interference in the
phenoldisulfonic acid method because
even rather low concentrations of
chloride result in nitrate losses. It is
important that the chloride content be
reduced to a minimum, preferably
below 10 mg/L
3.2.1 Sampling - The absorbing
reagent is prepared by adding 2.8 ml
of concentrated sulfuric acid (HzSCM
to 1 L of deionized distilled water. Mix
well, and add 6 ml of 3% hydrogen
peroxide (HzOz). Prepare a fresh
absorbing solution weekly, store in a
dark-colored pyrex container, and do
not expose to extreme heat or direct
sunlight. If the reagent must be
shipped to the field site, it is advisable
that the absorbing reagent be
prepared fresh on site.
3.2.2 Sample Recovery - A sodium
hydroxide solution (NaOH) is prepared
by dissolving 40 g NaOH in distilled
water and diluting to 1 L. This solu-
tion can be transferred to a
polyethylene 1000-ml (32-oz) jar for
shipment. Deionized distilled water
and pH paper are required to test for
basicity and for transferral of samples.
3.2.3 Analysis - The following rea-
gents are needed for analysis and
standardization:
Fuming sulfuric acid - 1 5% to 18%
(by weight) free sulfur trioxide (S03).
Phenol - White solid ACS reagent
grade.
Sulfuric acid - Concentrated
reagent, 95% minimum assay, ACS
reagent grade.
Standard solution - Dissolve 2.198
g of dried potassium nitrate (KNOa)
ACS reagent grade in distilled water,
and dilute to 1 L in a volumetric flask.
For the working standard solution,
pipette 10 ml of the resulting solution
into a 100-ml volumetric flask and
dilute to the mark. Note - One ml of
the working standard solution is
equivalent to 100 fjg of nitrogen
dioxide.
Water - Deionized distilled.
Phenoldisulfonic acid solution -
Dissolve 25 g of pure white phenol
(no discoloration) in 150 ml of
concentrated sulfuric acid on a steam
bath. Cool. Add 75 ml of fuming
sulfuric acid, and heat at 100°C
(212°F) on a steam bath for 2 h. Store
in a dark stoppered bottle. This acid
may also be purchased if it meets the
American Public Health Association
specification for nitrate-nitrogen in
water.
3.3 Packing Equipment for
Shipment
Equipment should be packed in rigid
containers to protect it against rough
-------
Section 3.6.3 2 5-01-79
handling during shipping and field
operations (not mandatory).
3.3.1 Probe - Pack the probe in a
case protected by polyethylene foam
or other suitable packing material. An
ideal container is a wooden case (or
the equivalent) lined with foam
material in which separate
compartments are cut to hold the
individual devices. This case can also
contain a Pilot tube for velocity
determinations. The case should have
handles that can withstand hoisting
and should be rigid enough to prevent
bending or twisting of the devices
during shipping and handling.
3.3.2 Collection Flask and Valve -
The collection flasks and valves
should be packed securely in a
suitable shipping container. An ideal
container is a case or footlocker of
approximately the following
dimensions: 30 in. X 15 in. X 15 in.
This container, when lined with foam,
will accommodate eight collection
flasks with the appropriate mated
flask valves.
3.3.3 Evacuation System, Tempera-
ture Gauges, Vacuum Lines, and
Reagents - A sturdy case lined with
foam material can contain the evacua-
tion manifold, squeeze bulb, mano-
meter, and reagents for sample
recovery. Special care should be taken
with mercury U-tube manometers to
avoid any spillages.
3.3.4 Evacuation Pump - The
vacuum pump should be packed in a
shipping container unless its housing
is sufficient for travel. Additional
pump oil and oiler jar should be
packed with the pump if oil is required
for its operation.
3.3.5 Glass Storage Containers - All
glass storage containers must be
packed with cushion material at the
top and bottom of the case, and with
some form of dividers to separate the
components.
-------
5-01-79 3 Section 3.6.3
Date
- 77 Calibrated by &.
Flask Volume
Flask volume measured with valves? r yes no
Volume measured within ±10 ml? yes no
Temperature Gauge
Was a pretest temperature correction used? yes no
If yes, temperature correction (within ±1°C !2°F) of reference values for calibration and within ±2°C (4°F) of reference
values for calibration check)
Vacuum Gauge
Was gauge calibrated against a U-tube mercury manometer (If it was a mechanical gauge)? yes no
^ not applicable?
Barometer
Was the pretest field barometer reading within ±2.5 mm (0.1 in.) Hg of the mercury-in-glass barometer? 1^ | yes
no
* 'Most significant items/parameters to be checked.
Figure 3.1 Pretest sampling checks.
-------
Section 3.6.3
5-01-79
Apparatus check
Probe
Glass liner clean
Heated properly
Leak checked
Collection Flask
Clean
Leak checked
Temperature gauge
Evacuation System
Leak-free pumps
Manifold and tubing
U-tube manometer
Barometer
Reagents
Distilled water
Absorbing solution"
Sodium hydroxide. 1 N
pH paper
Sample recovery
Dropper or burette
Sample bottles
Pipette 25 ml
Acceptable
Yes
I/
tX
^^
^^
^^X
^^^
•
^^r
^^^
wX
'
IX
|X
tx
iX
.^
IX
No
Quantity
required
3
H
Z
3
Z
'
/ li+t*.
i /»Vt<«.
I
/ /lf«*
/ fkq.
Z
H
Z
Ready
Yes
I/
iX
*
-------
6-01-79
Section 3.6.3
Table 3. 1 Activity Matrix for Presampling Preparation
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Apparatus
Check
Probe
ide, 3%
1. Clean; glass lin-
er inert to oxides of
nitrogen
2. Heating properly if
equipped with heating
system
1. Before each test
2. As above
Must be
replaced
Collection
flask
Evacuation
system
Absorbing
Reagents
Sulfuric acid.
concentrated
Hydrogen per ox -
3. Leak free
Clean; volume within
±10 ml
Vacuum of 75 mm (3 in.)
Hg absolute pressure
in each flask; leakage
rate
-------
5-01-79
Section 3.6.4
4.0 On-Site Measurements
The on-site measurement activities
include transporting the equipment to
the test site, unpacking and
assembling the equipment, confirming
duct measurements and traverse
points (if volumetric flow rate is to be
determined), velocity traverse,
molecular weight determination of the
stack gas, moisture content, sampling
for oxides of nitrogen, and data
recording. Table 4.1 at the end of this
section summarizes the quality
assurance activities relative to on-site
measurements.
4.1 Transport of Equipment
to the Sampling Site
The most efficient means of trans-
porting or moving the equipment from
ground level to the sampling site (as
decided during the preliminary site
visit) should be used to place the
equipment on site. Care should
always be exercised against damage
to the test equipment or injury to test
personnel during the moving phase. A
"laboratory" type area should be
designated for preparation of
absorbing reagent and charging of the
flasks. An acceptable alternative is to
charge the flasks in the home
laboratory. Utilization of plant
personnel or equipment (winches and
forklifts) in movement of the sampling
gear is highly recommended.
4.2 Preliminary
Measurements and Setup
The Reference Method outlines the
determination of the concentration of
oxides of nitrogen in the gas stream.
The volumetric flow rate must be
determined utilizing Method 2,
Section 3.1, and Method 4, Section
3.3 of this Handbook so that mass
emission rate may be determined.
'4.3 Sampling
The on-site sampling includes pre-
paration and/or addition of the
absorbing reagent to collection flasks
(if not performed at home laboratory),
setup of the evacuation system,
connection of the electric service,
preparation of the probe (leak check
and addition of particulate filter),
insertion of probe into the stack,
purging of the probe, sealing of the
port, evacuation of flasks, sampling
and recording of the data, and a final
leak check. In addition, EPA Reference
Methods 1, 2, 3, and/or 4 may have
to be performed simultaneously with
Method 7. This will be specified by
the applicable regulation, and the
applicable reference method should
be followed.
4.3.1 Preparation and/or Addition of
Absorbing Reagent to Collection
Flasks - If preparation of absorbing
reagent is necessary on site, follow
directions given in Section 3.6.3.
Pipette exactly 25 ml of absorbing
reagent into the sample flask. Place a
properly lubricated flask valve into the
collection flask with the valve turned
in the "purge" position. Lubrication of
joints is intended to prevent leaks and
should not seal the bore of the
stopcock or contaminate the sample.
4.3.2 Assembling Sampling Train -
Assemble the sampling train as
shown in Figure 1.1 and perform the
following:
1. Visually check probe for liner
separation (cracks, etc.).
2. Place a loosely packed filter of
glass or quartz wool in the inlet
end of the probe to trap any
particulates.
3. Insert the probe into the stack to
the sampling point, and seal the
opening around the probe.
4.3.3 Evacuation, Purge, and Samp-
ling - A sample is taken as follows:
1. Turn the pump and flask valves
to the "evacuate" positions and
evacuate to a minimum of 75
mm (3 in.) Hg absolute pressure
or until the apparent boiling point
is reached (bubbling of absorbing
solution).
2. Turn the pump valve to the
"vent" position, turn off the
pump and check the manometer
for fluctuations. The manometer
should stay stable (maximum -
deviation <10 mm (0.4 in.) Hg)
for at least 1 minute. If the
mercury level changes, check for
leaks and eliminate the problem.
Pressure in the flask should be
<75 mm (3 in.) Hg absolute
when sampling is commenced.
3. Record the volume of the flask
and valve (VF), the flask
temperature (ti), and the
barometric pressure (Pbar) on a
data form (see Figure 4.1 A or
4.1 B) or in a field laboratory
notebook.
4. Turn the flask valve
counterclockwise to the "purge"
position.
5. Turn the pump valve to the
"purge" position.
6. Purge the probe and the vacuum
line using the one-way squeeze
bulb.
7. If condensation occurs in the
probe or the flask valve, heat the
probe until (upon purging) the
condensation disappears.
8. Turn the pump valve to the
"vent" position.
9. Turn the flask valve clockwise to
its "evacuate" position, and
record the difference in the
mercury levels in the
manometer. The absolute
internal pressure in the flask (Pi)
is equal to the barometric
pressure less the manometer
reading (Leg A and Leg B).
10. Immediately turn the flask valve
to the sample position, and
permit the gas to enter the flask
until pressures in the flask and
sample line (i.e., duct, stack) are
equal. This will usually require
about 15 s; a longer period
indicates a "plug" in the probe,
which must be corrected before
sampling is continued.
11. After collecting the sample, turn
the flask valve to its "purge"
position.
12. Disconnect the flask and valve
from the sampling train and
shake the flask for at least 5 min.
4.3.4 Chemical Reactions of Sample
Collection - If the gas being sampled
contains insufficient oxygen for the
conversion of NO to N02 (e.g., an
applicable subpart of the standard
may require taking a sample of a
calibration gas mixture of NO in N2),
then oxygen should be introduced into
the flask to permit this conversion.
Oxygen may be introduced into the
flask by one of three methods: (1)
Before evacuating the sampling flask,
flush with pure cylinder oxygen, and
then evacuate flask to 75 mm (3.0 in.)
Hg absolute pressure or less; or (2)
inject oxygen into the flask after
sampling; or (3) terminate sampling •
with a minimum of 50 mm (2.0 in.) Hg
vacuum remaining in the flask, record
this final pressure, and then vent the
flask to the atmosphere until the flask
pressure is almost equal to
atmospheric pressure.
-------
Section 3.6.4
6-01-79
Chemical reactions which occur
during sampling adsorption are:
NO sample: NO + H202 - N02 + H20 -
2N02 + HzOz - 2HN03.
N02 sample: 2N02 + H202 - 2HN03.
NO sample: (2NO) gaseous + 02 — 2N02
+ H2O2 - 2HN03.
4.4 Sample Recovery
The Reference Method requires a
minimum sample absorption period of
16 h in the flask. If the laboratory is
close by, the sample may be left in
the flasks for return to the laboratory.
Otherwise, the appropriate data may
be taken in the field, solutions made
alkaline and transferred to leak-free
polyethylene bottles after the required
absorption period.
4.4.1 Flask Pressure, Temperature.
and Barometric Pressure • After the
absorption period is complete (>1 6 h),
record the barometric pressure and
the room temperature final
temperature (ti) on the integrity data
forms (Figures 4.2A or 4.2B).
1. Shake the flask and contents for
2 min.
2. Connect the flask to a mercury-
filled U-tube manometer.
3. Open the valve from the flask to
the manometer and record the
flask temperature (ti), the
barometric pressure, and the
difference between the mercury
levels in the manometer (Leg A
and Leg B). The absolute internal
pressure in the flask (P() is the
barometric pressure less the
manometer reading.
4. Transfer the contents of the flask
to a leak-free polyethylene bottle.
5. Rinse the flask three times with
5-ml portions of deionized
distilled water, and add the rinse
water to the bottle.
6. Adjust the pH to between 9 and
1 2 by adding sodium hydroxide
(1N) dropwise (about 25 to 35
drops). Check the pH by dipping a
stirring rod into the solution and
then touching the rod to the pH
test paper. Remove as little
material as possible during this
step. The pH adjustment is
mandatory. The NaOH changes
the sample, which is in the form
of HN03, to NaN03. If the pH is
not adjusted, the HN03 will be
liberated during the evaporation
phase of analysis.
4.5 Sample Logistics (Data)
and Packing of Equipment
The above procedures are followed
until the required number of runs are
completed. Log all data on the form
shown in Figure 4.2A or 4.28.
1. Check all sample containers for
proper labeling (time, date, loca-
tion, number of test, and any
pertinent documentation). Be
sure that a blank has been taken.
2. Record all data collected during
the field test and duplicate by the
best means available. One set of
data should be mailed to the
base laboratory, or given to
another team member or to the
Agency; the original data should
be hand carried.
3. Examine all sample containers
and sampling equipment for
damage, and pack them properly
for shipment to the base
laboratory. All shipping
containers should be properly
labeled to prevent loss of
samples or equipment.
4. The sampling procedures can be
reviewed after testing or during
the testing using an on-site mea-
surement checklist (Figure 4.3).
-------
Nitrogen Oxide Field Data Form
{English units)
Plant
Acsne
Sample location
Operator
City .
Date
/?6/r?e, Ohio
Barometric pressure (Pt>eil e?T- O *1
in. Hg
Sample
number
tf'l
At-*
Af-3
Sample
point
location
A- II
0-IO
Sample
time
24-hr
07 33
011S
080t
Probe
temperature.
°F
zio
Z./0
Flask
and valve
number
Pe-13
/>£--/O
Volume
of flask
and valve (Vr).
ml
ZOI3
2.0IO
too5
Initial pressure
in. Hg
Leg A,
13- b
13-1
13.1
LegB,
13.1
IZ-B
P?
l.$4
2.3V
Initial temperature
°F (t,J
13
73
°R (Tf
S3 3
5-33
01
b
-J
(D
o
3
u
0>
'Pi = />b.r - A4. + ^i/
b r, = tt + 460° f.
Figure 4.1A. Nitrogen oxide field data form (English units).
-------
A
Nitrogen Oxide Field Data Form
(metric units)
plant ft&ne~ rotuzK nosii atv rtcsne.* unto
Sample location ESP OM.+ GoHtA M/ Date Al*Q/11
Operator I' r(.OS€- Barometric pressure (P**,) fOlf'^. mm Hg
Sample
number
W-l
W-Z-
Sample
point
location
&-II
£-10
£-/0
Sample
time
24-hr
0733
Q1*JS~
0801
Probe
temperature.
°C
100
too
too
Flask
and valve
number
Pe-i3
PE -{O
Volume
of flask
and valve (Vf),
ml
ZOI3
20/0
2,0 OS
Initial Pressure
mm Hg
Leg A,
312
313
31Z.S
LegB,
311
310 S"
31O
P?
n-i
iit-i
Initial temperature
°C (tj
2.Z-Z
Zl.Z
°K (T\P
2«»^2.
2.9 V-^
z
-------
NO, Sample Recovery and Integrity Data Form
(English units)
Plant
Date
*/J//'
77
Sample recovery personnel \f- /f'OAff£Ln Barometric pressure. (P^,) 29-
V^ /> ^-..
sample recovery personnel \J- !• '\jr**nuur\ tsaroi
V^ £
Person with direct responsibility for recovered samples >'
in. Hg
Sample
number
fifi-l
AP~Z
Af>-3
Final Pressure,
in. Hg
Leg A,
1*1*
I.Z.
z-O
Leg B,
O.I*
0.8
I.O
p,a
*7.frV
«7.*V
2S.W
Final temperature.
°F(t,)
7J
72.
73
°R (T,)*
*33
rsi
f33
Sample
recovery
time.
24-h
131*
/3VO
/v/r
pH
adjusted
9 to 12
iX
•
f^
Liquid
level
marked
u>
(x
U
Samples
stored
in locked
container
iX
tx
t*r
01
6
en
"T, = t,+ 460°F.
Lab person with direct responsibility for recovered samples
Date recovered samples received
All samples identifiable? S/C-S
Remarks
M
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Analyst
J.
All liquids at marked level? .
ip
Signature of lab sample trustee
ML&UJ^. cj3od&^
Figure 4.2A. NO* sample recovery and integrity data form (English units).
-------
NO, Sample Recovery and Integrity Data Form
(metric units)
Plant
Pome*. fi/ar\t
Date
Z/J//77
Sample recovery personnel
yj«
Barometric pressure. (Pt&,)
Person with direct responsibility for recovered samples
. mm Hg
Sample
number
A-P'l
AP-2.
tf-3
Final pressure.
mm Hg
Leg A,
YO.b
30. &
SO.B
LegB,
IS.Z.
ZO.3
z*4
p,a
702
707
MZ
Final temperature.
°C (t,)
22.7
22.2
22.7
KfTf
iQf-f
2-W-Z
Z1S-7
Sample
recovery
time.
24-h
IJZi
1930
,3*1
pH
adjusted
9 to 12
tX
^
IX
Liquid
Level
marked
•
JX
^
Samples
stored
in locked
container
IX
iX
*P< = Pto, - (A, +fl,/
"7, = t, + 230°C.
Lab person with direct responsibility for recovered samples ^
Date recovered samples received—*^f *t ' ' Analyst
All samples identifiable? ^^ All liquids at marked level?
Remarks
J. Mo Ma
Signature of lab sample trustee.
CO
I
Ol
o
Figure 4.2B. NO* sample recovery and integrity data form /metric units).
-------
5-01-79 7 Section 3.6.4
Sampling
Volume of 25 ml of absorbing solution placed in flask? .
Flask valve stopper in purge position? **
Sampling train properly assembled? !
Leak free?" Stopcock grease used? .
Type? <••"*>
Flask evacuated to 75 mm (3 in.) Hg pressure? *^
0- Iftnin
Leakage from manometer observation?'
(e.g.. maximum change in manometer of<10mm (0.4 in.)
Hg/min.
Initial pressure of flask recorded?"
Initial temperature of flask recorded?:.
Probe purged before sampling?
Sample collected properly?"
Flask shaken for 5 min after collection and disassembly from train?*
M/A
Oxygen introduced to flask? ' ^ Method used?
Samples properly labeled and sealed and stored for shipment?
Sample Recovery
+1*3 *
Samples allowed to remain in flasks for minimum of 16 h?"
Final flask temperature and pressure recorded?" _ iX*
Sample transferred to leak-free polyethylene bottle?
Flask rinsed twice with 5-ml portions of distilled water and rinse added to bottle containing sample?
pH adjusted to between 9 and 12?" t^_
* Most significant items/parameters to be checked.
Figure 4.3. On-site measurements.
-------
Section 3.6.4
6-01-79
Table 4.1 Activity Matrix for On-Site Measurements
Characteristic
Apparatus
assembly
Operational
check
Sample recovery
Sample logistics
Acceptance limits
Assemble using Fig.
J.I; no leakage
Maximum vacuum of
75 mm (3 in.) Hg
absolute pressure
Leakage rate <10 mm
(0.4 in.) Hg/min
Shake flask for 5 min
Let flask set for a
minimum of 1 6 h
Shake flask for 2 min
Determine flask pres-
sure and temperature
Adjust pH of sample to
9-12 with NaOH
Mark sample level on
container
Record data on data
form (Fig. 4.2)
Properly label all
containers, etc.
Record all data on
field data forms
(Fig. 4. 1 and Fig.
4.2)
Frequency and method
of measurement
Before sample
collection, visually and
physically inspect
all connections
Before sample
collection, use
Hg-filled U-tube
manometer
As above
During each sample
collection, use
manometer, centigrade
thermometer, and pH
paper
Visually check
each sample
As above
Action if
requirements
are not met
Check for
leaks; repair
system; re-
pair test
Check system
for leaks;
check vac-
uum pump
Check all
joints and
valves for
source of
leakage
Reject
sample.
rerun test
Complete the
labeling
Complete the
data records
-------
5-01-79
Section 3.6.6
5.0 Postsampling Operations
Table 5.1 at the end of this section
summarizes the quality assurance
activities for sample analysis. If the
laboratory receives the samples in the
sample flask, laboratory personnel will
have to complete the sample recovery
procedures previously explained in
Section 3.6.4.
5.1 Procedures for Operating
a Spectrophotometer
The correct manipulations of blanks
and sample cells are critical. Careless
technique is unacceptable. The follow-
ing points are recommended and
should be adhered to.
1. Designate the cuvettes as either
a blank or a sample cell. Do not
interchange the cells during an
analysis because they are not
always matched.
2. Do not touch the bottom of the
cuvette with your fingers.
3. Rinse the cuvette at least twice
with the solution you are about
to measure.
4. Remove lint, liquid, and so forth
with a lens tissue or its
equivalent.
5.2 Base Laboratory
(Analysis)
5.2.1 Check of Field Sample
Integrity - If the field samples have
been snipped in sample containers, be
sure that all samples are identifiable
and that the liquid level of each is at
its mark. If a sample is not identifiable
or if a loss of liquid is detected, note it
on the data form, as shown in Figures
4.2A and 4.2B. When a noticeable
amount of leakage has occurred, use
an alternative method, subject to the
approval of the Administrator, to
correct the final value; approval
should have been requested prior to
testing. An alternative method is as
follows:
1. Mark the new level of the
sample.
2. Transfer the sample to a 50-ml
volumetric flask (V80m), along with
two 5-ml deionized distilled
water rinsings of the container.
3. Add water to the sample storage
container to the initial sample
mark, and measure the initial
sample volume (Vsanj) in ml.
4. Add water to the sample storage
container to the mark of the
transferred sample, and measure
the final volume (V80in,) in ml.
5. If (VSoin,)
-------
Section 3.6.6
5-01-79
steam bath and then cool. Note -
Do not evaporate on a hot plate
or in an oven unless it is
thermostatically controlled below
70°C (160°F). Remove samples
from steam bath just before
complete dryness is reached (the
bottom of the dish should be
covered with a smooth film), so
that the last droplet evaporates
as the dishes cool.
3. Add 2.0 ml of phenoldisulfonic
acid reagent to each dried
residue and either mix
thoroughly with a polyethylene
policeman or let the solution
stand for 5 min.
4. Add 1.0 ml of deionized distilled
water and four drops of concen-
trated sulfuric acid, and then
heat the solution on a steam
bath for 3 min with occasional
stirring.
5. Cool. Add 20 ml of deionized
distilled water, and mix well by
stirring.
6. Add concentrated ammonium hy-
droxide dropwise (a 50-ml
burette is suggested) with
constant stirring until the pH is
10, as determined either by pH
paper or by the first yellow color
that does not fade.
7. Transfer directly to a 100-ml
volumetric flask if the sample
does not contain solids. Rinse
the evaporating dish with at least
three 5-ml portions of deionized
distilled water, and then add the
washings to the contents of the
flask.
8. Remove any solids from the sam-
ple by filtering the sample
through a Whatman No. 41 filter
paper into a 100-ml volumetric
flask; rinse each evaporating dish
with three 5-ml portions of
deionized distilled water; filter
these three rinses. Wash the
filter with at least three 15-ml
portions of deionized distilled
water, and then add the filter
washings to the contents of the
volumetric flask.
9. Dilute to the 100-ml mark with
deionized distilled water and mix
the contents of the flask
thoroughly.
10. Measure the absorbance of the
standard solutions at the
optimum wavelength, using the
blank solution as a zero
reference. Note - The flasks
should not sit in warm'or light
areas for very long before
analysis because precipitates
may form.
11. Record the standard solutions
and control sample data on
Figure 5.1 or similar form.
12. Read the absorbance of the field
samples from Run 1 and then
one of the control samples; Run
2 and another control sample;
and Run 3 and the last control
sample.
13. If the absorbance reading of any
field sample is greater than the
absorbance reading of the
standard sample A4 (the
absorbance of the 400 /jg NOz
standard), then dilute the sample
and the blank with equal
volumes of deionized distilled
water using pipettes to get ratios
of 25/5, 25/10, and so forth.
14. Record all field sample analysis
data as shown in Figure 5.2, and
calculate the mass (m) of NO, for
each sample as /jg of NOz.
15. Perform the calculations and the
accuracy checks of the three
control samples as shown in
Figure 5.1. It is recommended
that the agreement for each
control sample be within ±15%.
The standard solution and control
sample analytical form should be
included in the emission test
report as a documentation of the
analytical accuracy. This
accuracy limit of ±1 5% for
intralaboratory control samples is
recommended based on the
control limit of ±20% for
interlaboratory audit results
discussed in Section 3.6.8.
16. When the above criteria cannot
be met, it is recommended that
the analytical techniques be
checked and then the field
sample and control sample
analysis be repeated using a
20.0-ml aliquot of the remaining
field samples.
17. The main parameters of the ana-
lytical procedures may be
checked during or after the
analysis, using a posttest opera-
tions form (Figure 5.3).
-------
6-01-79
Section 3.6.6
Plant
Standard Solution and Control Sample
Analytical Data Form
Analyst
Blank used as reference?
Date
3' 3 ~ 77
Optimum wavelength
nm
Sample
number
A1
A2
A3
A4
SI
S2
S3
Sample,
U9
100
200
300
400
too
200
300
Working
solution
X
X
X
X
Control
sample
X
X
X
Measured,
absorbance.
OD
0./7Z.
0. 3*O
0.S6O
0.7^0
0./90
o . 35 y
0-S7&
Calculated
absorbance"
OD
—
—
—
0./9/
0. "3% V
0-57S
Absorbance
comparison
error.°%
—
—
—
-0.6-
0.O
-0.2.
*«9caz
*OD = tfig)/K0;i.e., SI calculated absorbance = 100/Ke.
Kc=100
"Absorbance comparison errors:
=100x
" Average of absolute values.
(measuredabsorbance. OD)-{calculatedabsorbance, OD) \
calculated absorbance, OD
Figure 5.1. Standard solution and control sample analytical data form.
-------
Section 3.6.5
5-01-79
Plant
n>
>*/er
Date samples received
Aliquot factor %.
3/2/77
/VO* Laboratory Data Form
Run number(s)
_ Date analyzed'__
AP-/JL
/f f f
Blank absorbance
Calibration factor (KJ
5 ** 0
Samples analyzed by
Date reviewed by
Date of review
Sample
number
AP-/
Af>-3
Sample
absorbance.
A
o-yys
£t»
Dilution
factor.
F
/•o
2.0
Total mass of /VO,
as NO; in sample.
m
*y '&> ' £/
f ^5 ^r
^p £p yO
m - 2 Kc AF, Note - // other than a 25 ml aliquot is used for analysis, the factor 2 must be replaced by a corresponding
factor.
Figure 5.2. /V0« laboratory data form.
-------
5-01-79
Section 3.6.6
Reagents
Phenoldisulfonic acid stored in dark stoppered bottle?
Sulfuric acid, concentrated. 95% minimum assay reagent grade? .
Ammonium hydroxide, concentrated reagent grade?
Sample Preparation
Has liquid level noticeably changed?"
Original volume
Corrected volume
Analysis
Spectrophotometer calibrated?*
Setting for maximum absorbance of standard_
Control sample prepared?*
Any solids in sample removed through Whatman No. 41 filter paper? .
Absorbance measured at optimum wavelength used for the standards, using the blank solution as a zero reference?
All analytical data recorded on checklist and laboratory form? L.
'Most significant items/parameters to be checked.
Figure 5.3. Posttest operations.
Table 5.1 Activity for Sample Analysis
Characteristic
Control sample
analysis
(recommended)
Field sample
analysis
Data recording
Acceptance limits
Agree within 15% of
the working standards
for each sample
No sample volume lost,
or final results
corrected
Working standard
analyzed simultaneously
with field sample
No absorbance readings
outside working
standard solution
concentration
All pertinent data
recorded on Figs. 5. 1
and 5.2
Frequency and method
of measurement
Compare control sample
analysis to working
standards analysis
Compare liquid level
to mark before
analysis
Use same solutions
and techniques used
for control samples
Dilute sample and
blank with equal
amounts of deionized
distilled water
Visually check
Action if
requirements
are not met
Redo field
and control
samples and/
or seek
assistance
with analyti-
cal technique
Void sample
As above
Dilute and
reanalyze
Supply miss-
ing data
-------
5-01-79
Section 3.6.6
6.0 Calculations
Calculation errors due to procedural
or mathematical mistakes can be a
large component of total system error.
Therefore, it is recommended that
each set of calculations be repeated
or spot-checked, 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 checked,
and 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
at least one extra decimal figure
beyond that of the acquired data and
should be rounded after final calcula-
tion to two significant digits for each
run or sample. All rounding of
numbers should be performed in
accordance with the ASTM 380-76
procedures. All calculations are then
recorded on a form such as the one in
Figure 6.1 A or 6.1B, following the
nomenclature list.
6.1 Nomenclature
The following nomenclature is used
in the calculations.
A = Absorbance of sample.
C Concentration of NOX as NOa,
dry basis, corrected to
standard conditions,
mg/dscm (Ib/dscf).
F = Dilution factor (i.e., 25/5,
25/10, etc.) required only if
sample dilution was needed
to reduce the absorbance to
the range of calibration.
Kc = Spectrophotometer calibra-
tion factor.
m = Mass of NO, as N02 in gas
sample, fjg.
P( = Final absolute pressure of
flask, mm (in.) Hg.
PI = Initial absolute pressure of
flask, mm (in.) Hg.
Psm=Standard absolute pressure,
760 mm (29.92 in.) Hg
Tt = Final absolute temperature of
flask, K (°R).
Ti = Initial absolute temperature
of flask, K (°R).
Tstd = Standard absolute tempera-
ture, 293K (528?R).
Vsc = Sample volume at standard
conditions, dry basis, ml.
Vi = Volume of flask and valve,
ml.
Va = Volume of absorbing solution,
25ml.
6.2 Calculations
The following are the equations
used with example calculation forms
Figures 6.1 A and 6.1B to calculate the
concentration of nitrogen oxides.
6.2.1 Sample Volume - Calculate the
sample volume on a dry basis at
standard conditions (760 mm (29.92 in.)
Hg and 293K (528°R)) by-using the
following equation.
_Ts.d(V(-Va)/ Pf Pi^
Ps,d \ T, T,
= K, (V, -25ml) l.i
IT, T,
where
mg/m3
«2 = 1 03 — - for metric units, or
where
Equation 6-1
for metric units, or
Ki =0.3858
mmHg
K, =17.64 °R for English units,
in. Hg
6.2.2 Total vg of /VO2 Per Sample -
Calculate the total /ug of N02 per
sample by using Equation 6-2.
m = 2 KCAF
Equation 6-2
where
2 = 50/25, the aliquot factor (if other
than a 25-ml aliquot was used for
analysis, the corresponding factor
must be substituted).
6.2.3 Sample Concentration -
Calculate the sample concentration on
a dry basis at standard conditions
using Equation 6-3.
C = Ka
K2 = 6.243 x 1 0"5 '^Elfor English units.
/ug/ml
Equation 6-3
-------
Section 3.6.6
5-01-79
Nitrogen Oxide Calculation Form
(English units)
Sample Volume
v< =
p> =
p> =
VK = 77.64 (V,-25)
ml
Equation 6-1
Total fjg /V02 Per Sample
Equation 6-2
m — 2KC AF =
' W °f
Sample Concentration
C= 6.243
I -^-1 =2.
* ^0'5lb/dscf
Figure 6.1A. Nitrogen oxide calculation form {English units).
-------
5-01-79
Section 3.6.6
Nitrogen Oxide Calculation Form
(metric units)
Sample Volume
V, =
P> = 2. £-&•£>.
mm
=_-.. mm Hg. Tt = __
VK = 0.3858 (Vt-25)
Pj_. ^_
T, T,
= /77v5T
ml
Equation 6- 1
Total fjg NO2 Per Sample
m — 2KC AF =
of NO2
Equation 6-2
C = 10
[-7T- —
Vsc J
Sample Concentration
* 103mg/dscm.
Equation 6-3
Figure 6. IB. Nitrogen oxide calculation form (metric units/.
-------
Section 3.6.6
5-01-79
Tabled. 1 Activity Matrix for Calculations
Characteristic Acceptance limits
Sample volume
calculation
Sample mass
calculation
Sample concen-
tration
Calculation
check
Document and
report results
results
All data available;
calculations correct
within round- off error
As above
As above
Original and check
calculations agree
within round- off error
All data available;
calculations correct
within round- off error
Frequency and method
of measurement
For each sample,
examine the data form
As above
As above
For each sample,
perform independent
calculation using data
on Figs. 4. 1 , 4.2, and
4.3
For each sample.
examine the data form
Action if
^requirements
are not met
Complete the
data or void
the sample
As above
As above
Check and
correct
all data
Complete the
data or void
the sample
-------
5-01-79
Section 3.6.7
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 routine maintenance program
which should be performed quarterly
or upon improper functioning of the
apparatus. It is suggested that the
vacuum pump be disassembled and
cleaned yearly. A summary of the
components with maintenance
procedures is presented in Table 7.1
at the end of this section. The
following procedures are not required,
but are recommended to increase the
reliability of the equipment.
7.1 Pumps
Several types of pumps are used in
the present commercial sampling
trains. The two most common are the
fiber vane pump with in-line oiler and
the diaphragm pump. The fiber vane
pump requires a periodic check of the
oiler jar. The oil should be
translucent. During the yearly
disassembly or if the fiber vane pump
starts to run erratically, the head
should be removed and the fiber
vanes changed. The diaphragm pump
will show a leak when the diaphragm
needs changing. If the diaphragm
pump runs erratically, it is usually due
to a bad diaphragm (causing leakage)
or to malfunctions in the valves. The
valves should be cleaned annually by
complete disassembly of the pump.
7.2 Shipping Containers
Since the majority of the sampling
train is glassware, the shipping con-
tainers are very important for
protection and safety. All shipping
containers should be inspected
quarterly for their condition, and
repaired or modified to assure the
safety of the equipment.
Table 7.1. Activity Matrix for Maintenance
Apparatus
Routine main-
tenance
Fiber vane pump
Diaphragm pump
Shipping con-
tainer
Acceptance limits
Proper functioning
Oil translucent pump
leak/ess and capable
of pulling a vacuum of
less than 75 mm (3 in.)
Hg absolute pressure
Leak free, valves func-
tioning properly, and
capable of pulling a
vacuum of <75 mm
(3 in.) Hg absolute
pressure
Protect equipment
from damage
Frequency and method
of measurement
Perform routine
maintenance quarterly;
disassemble and clean
yearly
Check oiler jar
periodically; remove
head and change fiber
vanes
Clean valves during
disassembly; replace
diaphragm as needed
Inspect quarterly;
repair as needed
Action if
requirements
are not met
Replace parts
as' needed
Replace as
needed
Replace when
leaking or
ma/func-
tioning
Rep/ace
-------
Section No. 3.6.8
Revision No. 1
Date September 23,
Page 1
1985
8.0 AUDITING PROCEDURE
An audit is an independent assessment of data quality. In-
dependence is achieved if the individual(s) performing the audit
and their standards and equipment are different from the regular
field crew and their standards and equipment. In the case of a
compliance test, the required performance audits will be
conducted by the responsible enforcement agency. Routine quality
assurance checks by a field team are necessary in generation of
good quality data, but they are not part of the auditing
procedure. Table 8.1 at the end of this section summarizes the
quality assurance functions for auditing.
Of Method 7,
Based on the results of collaborative tests 'J
two specific performance audits are recommended:
I. Audit of the analytical phase of Method 7.
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 generally made to quantitatively
evaluate the quality of data produced by the total measurement
system (sample collection, sample analysis, and data process-
ing). It is recommended 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. No performance audit is recommended at this time
for the sampling phase. 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
Sul f ate ( 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 7 analysis
and should be performed at the discretion of the agency auditor,
the laboratory supervisor, source test company, or quality
assurance officer. The analytical phase of Method 7 can be
audited with the use of aqueous potassium nitrate samples pro-
vided to the testing laboratory before the enforcement source
test. Aqueous potassium nitrate samples may be prepared by the
procedure described in Section 3.6.5 on control sample prep-
aration.
-------
Section No. 3.6.8
Revision No. 1
Date September 23, 1985
Page 2
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
or no experience with the Method 7 analysis procedure described
in this Handbook.
To obtain pretest audit samples only, the testing laboratory
should provide a notice 30 days prior to the time of the planned
pretest audit to EPA's Environmental Monitoring Systems
Laboratory, Quality Assurance Division, Source Branch, Mail Drop
77A, Research Triangle Park, North Carolina 27711. This request
for known quality control samples from the Source Branch is
different from and does not satisfy the required 30 day notice to
the applicable enforcement agency as to the intent to conduct a
compliance test. The laboratory can prepare their own quality
control sample. The testing laboratory supervisor or quality
assurance officer can then check the precision and accuracy of
the analytical system prior to a compliance test with the use of
the known value samples. All problems indicated by the audit
should be eliminated prior to the audit by the agency.
The accuracy for each of two samples should be within 10
percent of true value. The relative, error (RE) is a measure of
the bias of the analytical phase of Method 7. Calculate RE using
Equation 8-1.
r r Equation 8-1
RE = ud " ua x 100
where: a
3
C, = Determined audit sample concentration, mg/dsm .
3
C = Actual audit sample concentration, mg/dsm .
a
8.1.2 Audit of Analytical Phase of the Field Test (Required) -
As statedIn40CFR 60, Section 3.3.9 (49 FR 26522, 06/27/84),
the testing laboratory should provide the responsible
agency/organization requesting the performance test with a
notification of the intent to test 30 days prior to the
enforcement source test. The responsible agency obtains the
audit samples from the appropriate EPA Regional Quality Assurance
Coordinator shown in Table 5.1 of Section 3.0.5 of this
Handbook. The responsible agency then provides the testing
laboratory with two audit samples to be analyzed along with 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 two audit samples and the compliance samples should be
-------
Section No. 3.6.8
Revision No. 1
Date September 23, 1985
Page 3
concurrently analyzed in the same manner to evaluate the tech-
nique of the analyst and the standards preparation. (Note: It is
recommended that known quality control samples be analyzed prior
to the compliance and audit sample analysis to optimize the sys-
tem accuracy and precision. One source of these samples has been
listed above.) The same analyst, analytical reagents, and
analytical system shall be used both for compliance samples and
the EPA audit samples; if this condition is met, auditing of sub-
sequent compliance analyses for the same enforcement agency
within 30 days 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 immediatelyby reporting the
audit results in mg/dsm and compliance results in total mg NO^/
sample by telephone to the responsible enforcement agency.)
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 10-percent of the actual concentra-
tions. If the 10-percent specification is not met, reanalyze the
compliance samples and audit samples, and include initial and
reanalysis values in the test report (see Note in first paragraph
of this section).
Failure to meet the 10-percent specification may require
retests until the audit problems are resolved. However, if the
audit results do not affect the compliance or noncompliance sta-
tus of the affected facility, the Administrator may waive the
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.
8.1.3 Audit of Data ^Processing - Calculation errors are
prevalent in Method 7. ' ' Data processing errors can be
determined by auditing the recorded data on the field and
laboratory forms. The original and audit (check) calculations
should agree within round-off error; if not, all of the remaining
data should be checked. The data processing may also be audited
by 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
-------
Section No. 3.6.8
Revision No. 1 «
Date September 23, 1985
Page 4
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 audit may be re-
duced- -for example, to 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
audits, 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 team management so that appropriate corrective
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 the absorbing solution and adding it to the
collection flasks.
3. Collecting the sample.
4. Sample absorption, recovery, and preparation for
shipment.
5. The spectrophotometer calibration should be checked for
every series of analyses. The calculated concentration values
should not differ from the actual concentrations by more than 7
percent for three of the four standards.
Figure 8.1 is a suggested checklist for the auditor.
-------
Section No. 3.6.8
Revision No. 1
Date February 25, 1985
Page 5
Yes
No
Comment
Presampling preparation
1. Information concerning combustion effluents that may
act as interferents
2. Plant operation parameters variation
3- Calibration of the flask and valve volume three
determinations
k. Absorbing reagent preparation
On-site measurements
5- Leak testing of sampling train
6. Preparation and pipetting of absorbing solution into
sampling flask
Postsampling
(Analysis and Calculation)
%
7. Control sample analysis
8. Sample aliquotting techniques
9. Evaporation and chemical treatment of sample
10. Spectrophotometric technique
a.. Preparation of standard nitrate samples
b. Measurement of absorbance, including blanks
c. Calibration factor (*_ 7 percent for 3 of U
standards)
d. Wavelength and absorbance, including blanks
e. Check for calibration of instrument wavelength
(once every six months)
11. Audit results (+ 10%)
a. Use of computer ^program
b. Independent check of calculations
Comments
Figure 8.1. Method 7 checklist to be used by auditors.
-------
Section No. 3.6.8
Revision No. 1 ,
Date February 25, 1985
Page 6
Table 8.1 ACTIVITY MATRIX FOR AUDITING PROCEDURE
Audit
Acceptance Limits
Frequency and method
of measurement
Action if
requirements
are not met
Spectrophoto-
meter anal-
ysis using
reference
samples of
dilute KNO
Measured RE of the
pretest audit samples
should be less than
^ 10?! for both audit
results (optional)
Measured RE of the
audit samples should
be less than +_ 10# for
both audit samples
(required)
Frequency; As consid-
ered necessary by the
testing firm
Method; Measure
reference samples
and compare their true
value
Frequency; Once during
every enforcement source
test* (required)
Method: Measure audit
samples and compare
their true values
Review operating
technique and/or
calibration curve
check
Review operating
technique and/or
calibration curve
check and repeat
the analysis of
the audit and
field samples
Data
processing
errors
(recom-
mended)
Original and check
calculations agree
within round-off
error
Frequency; Once during
every enforcement
source test*
Method; Independent
calculations starting
with recorded data on
Figures 4.1 and 5.1
Check and correct
all data for the
audit period rep-
resented by the
sampled data
Systems
audit-
observance
of tech-
nique
(recom-
mended)
Operational tech-
nique as described
in this section of
the Handbook
Frequency; Once during
every enforcement source
test* until experience
gained, then every
fourth test
Method; Observation of
techniques assisted by
audit checklist,
Fig. 8.1
Explain to team
their deviations
from recommended
techniques and
note on Fig. 8.1
*As defined here, a source test for enforcement comprises a series of runs
at one source. Source tests for purposes other than enforcement (e.g., a
research project) may be audited at a lower frequency.
-------
5-01-79 1 Section 3.6.9
9.0 Recommended Standards for Establishing Traceability
To achieve data of desired quality,
two essential considerations are
necessary: (1) the measurement
process must be in a state of
statistical control at the time of the
measurement and (2) the systematic
errors, when combined with the
random variation (errors or
measurement), must result in an
acceptable uncertainty. As evidence in
support of good quality data, it is
necessary to perform quality control
checks and independent audits of the
measurement process; to document
these data; and to use materials,
instruments, and measurement pro-
cedures that can be traced to an
appropriate standard of reference.
Data must be routinely obtained by
repeat measurements of standard
reference samples (primary,
secondary, and/or working standards)
and the establishment of a condition
of process control. The working
calibration standards should be
traceable to standards of higher
accuracy, such as that below.
Class-S weights (made to NBS spe-
cifications) are recommended for the
analytical balance calibration. See
Section 3.6.2 for details on balance
calibration checks.
-------
6-01-79
Section 3.6.10
10.0 Reference Method*
Method 7—Determination of Nitrogen Oxide
Emissions from Stationary Sources
1. Principle and Applicability
1.1 Principle. A grab sample is col-
lected in an evacuated flask
containing a dilute sulfuric acid-
hydrogen peroxide absorbing solution,
and the nitrogen oxides, except
nitrous oxide, are measured
colorimetrically using the phe-
noldisulfonic acid (PDS) procedure.
1.2 Applicability. This method is
applicable to the measurement of
nitrogen oxides emitted from
stationary sources. The range of the
method has been determined to be 2
to 400 milligrams NO, (as NOa) per
dry standard cubic meter, without
having to dilute the sample
2. Apparatus
2.1 Sampling (see Figure 7-1). Other
grab sampling systems or equipment,
capable of measuring sample volume
to within ±2.0 percent and collecting
a sufficient sample volume to allow
analytical reproducibility to within ±5
percent, will be considered acceptable
alternatives, subject to approval of the
Administrator, U.S. Environmental
Protection Agency. The following
equipment is used in sampling:
2.1.1 Probe. Borosilicate glass tub-
ing, sufficiently heated to prevent
water condensation and equipped
with an in-stack or out-stack filter to
remove particulate matter (a plug of
glass wool is satisfactory for this
purpose). Stainless steel or Teflon3
tubing may also be used for the probe.
Heating is not necessary if the probe
remains dry during the purging period.
2.1.2 Collection Ftask. Two-liter
borosilicate, round bottom flask, with
short neck and 24/40 standard taper
opening, protected against implosion
or breakage.
2.1.3 Flask Valve. T-bore stopcock
connected to a 24/40 standard taper
joint.
•40 CFR 60, July 1. 1978
'Mention of trade names or specific products does
not constitute endorsement by the Environmental
Protection Agency.
2.1.4 Temperature Gauge. Dial-type
thermometer, or other temperature
gauge, capable of measuring 1°C
(2°F) intervals from -5 to 50°C (25 to
125°F).
2.1.5 Vacuum Line. Tubing capable
of withstanding a vacuum of 75 mm
Hg (3 in. Hg) absolute pressure, with
"T" connection and T-bore stopcock.
2.1.6 Vacuum Gauge. U-tube mano-
meter, 1 meter (36 in.), with 1 -mm
(0.1 -in.) divisions, or other gauge
capable of measuring pressure to
within ±2.5 mm Hg (0.10 in. Hg).
2.7.7 Pump. Capable of evacuating
the collection flask to a pressure
equal to or less than 75 mm Hg (3
in.Hg) absolute.
2.1.8 Squeeze Bulb. One-way.
2.1.9 Volumetric Pipette. 25 ml.
2.1.10 Stopcock and Ground Joint
Grease. A high-vacuum, high-
temperature chlorofluorocarbon
grease is required. Halocarbon 25-5S
has been found to be effective.
2.1.11 Barometer. Mercury, aneroid,
or other barometer capable of
measuring atmospheric pressure to
within 2.5 mm Hg (0.1 in. Hg). In
many cases, the barometric reading
may be obtained from a nearby
national weather service station, in
which case the station value (which is
the absolute barometric pressure)
shall be requested and an adjustment
for elevation differences between the
weather station and sampling point
shall be applied at a rate of minus 2.5
mm Hg (0.1 in. Hg) per 30 m (100 ft)
elevation increase, or vice versa for
elevation decrease.
2.2 Sample Recovery. The following
equipment is required for sample
recovery:
2.2.1 Graduated Cylinder. 50 ml
with 1-ml divisions.
2.2.2 Storage Containers. Leak-free
polyethylene bottles.
2.2.3 Wash Bottle. Polyethylene or
glass.
2.2.4 Glass Stirring Rod.
2.2.5 Test Paper for Indicating pH.
To cover the pH range of 7 to 14.
2.3 Analysis. For the analysis, the
following equipment is needed:
2.3.1 Volumetric Pipettes. Two 1 ml,
two 2 ml, one 3 ml, one 4 ml, two 10
ml, and one 25 ml for each sample
and standard.
2.3.2 Porcelain Evaporating Dishes.
175- to 250-ml capacity with lip for
pouring, one for each sample and
each standard. The Coors No. 45006
(shallow-form, 195 ml) has been
found to be satisfactory. Alternatively,
polymethyl pentene beakers (Nalge
No. 1203, 150 ml), or glass beakers
(150 ml) may be used. When glass
beakers are used, etching of the
beakers may cause solid matter to be
present in the analytical step; the
solids should be removed by filtration
(see Section 4.3).
2.3.3 Steam Bath. Low-temperature
ovens or thermostatically controlled
hot plates kept below 70° C (160°F)
are acceptable alternatives.
2.3.4 Dropping Pipette or Dropper.
Three required.
2.3.5 Polyethylene Policeman. One
for each sample and each standard.
2.3.6 Graduated Cylinder. 100 ml
with 1-ml divisions.
2.3.7 Volumetric Flasks. 50 ml (one
for each sample and each standard),
100 ml (one for each sample and each
standard, and one for the working
standard KN03 solution), and 1000 ml
(one).
2.3.8 Spectrophotometer. To mea-
sure absorbance at 410 nm.
2.3.9 Graduated Pipette. 10 ml with
0.1 -ml divisions.
2.3.10 Test Paper for Indicating pH.
To cover the pH range of 7 to 14.
2.3.11 Analytical Balance. To mea-
sure to within 0.1 mg.
-------
Section 3.6.10
6-01-79
3. 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,
where such specifications are
available;votherwise, use the best
available grade.
3.1 Sampling. To prepare the
absorbing solution, cautiously add 2.8
ml concentrated HjSCu to 1 liter of
deionized, distilled water. Mix well
and add 6 ml of 3 percent hydrogen
peroxide, freshly prepared from 30
percent hydrogen peroxide solution.
The absorbing solution should be used
within 1 week of its preparation. Do
not expose to extreme heat or direct
sunlight.
3.2 Sample Recovery. Two reagents
are required for sample recovery:
3.2.1 Sodium Hydroxide (1N). Dis-
solve 40 g NaOH in deionized, distilled
water and dilute to 1 liter.
3.2.2 Water. Deionized, distilled to
conform to ASTM specification
D1193-74, Type 3. 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 to be
present.
3.3 Analysis. For the analysis, the
following reagents are required:
3.3.1 Fuming Sulfuric Acid. 15 to
18 percent by weight free sulfur
trioxide. HANDLE WITH CAUTION.
3.3.2 Phenol. White solid.
3.3.3 Sulfuric Acid. Concentrated,
95 percent minimum assay. HANDLE
WITH CAUTION.
3.3.4 Potassium Nitrate. Dried at
105 to 110°C (220 to 230°F) for a
minimum of 2 hours just prior to
preparation of standard solution.
3.3.5 Standard KN03 Solution. Dis-
solve exactly 2.198 g of dried
potassium nitrate (KNQs) in deionized,
distilled water and dilute to 1 liter
with deionized, distilled water in a
1,000-ml volumetric flask.
3.3.6 Working Standard KNO3 Solu-
tion. Dilute 10 ml of the standard
solution to 100 ml with deionized
distilled water. One milliliter of the
working standard solution is
equivalent to 100 jug nitrogen dioxide
(N02).
3.3.7 Water. Deionized, distilled as
in Section 3.2.2.
3.3.8 Phenoldisulfonic Acid
Solution. Dissolve 25 g of pure white
phenol in 150 ml concentrated
sulfuric acid on a steam bath. Cool,
add 75 ml fuming sulfuric acid, and
heat at 100° C (212° F) for 2 hours.
Store in a dark, stoppered bottle.
4. Procedures
4.1 Sampling
4.1.1 Pipette 25 ml of absorbing
solution into a sample flask, retaining
a sufficient quantity for use in
preparing the calibration standards.
Insert the flask valve stopper into the
flask with the valve in the "purge"
position. Assemble the sampling train
as shown in Figure 7-1 and place the
probe at the sampling point. Make
sure that all fittings are tight and
leak-free, and that all ground glass
joints have been properly greased
with a high-vacuum, high-
temperature chlorofluorocarbon-based
stopcock grease. Turn the flask valve
and the pump valve to their
"evacuate" positions. Evacuate the
flask to 75 mm Hg (3 in. Hg) absolute
pressure, or less. Evacuation to a
pressure approaching the vapor pres-
sure of water at the existing tempera-
ture is desirable. Turn the pump valve
to its "vent" position and turn off the
pump. Check for leakage by observing
the manometer for any pressure
fluctuation. (Any variation greater
than 10 mm Hg (0.4 in. Hg) over a
period of 1 minute is not acceptable,
and the flask is not to be used until
the leakage problem is corrected.
Pressure in the flask is not to exceed
75 mm Hg (3 in. Hg) absolute at the
time sampling is commenced.) Record
the volume of the flask and valve (V(),
the flask temperature (T,), and the
barometric pressure. Turn the flask
valve counterclockwise to its "purge"
position and do the same with the
pump valve. Purge the probe and the
vacuum tube using the squeeze bulb.
If condensation occurs in the probe
and the flask valve area, heat the
probe and purge until the
condensation disappears. Next, turn
the pump valve to its "vent" position.
Turn the flask valve clockwise to its
"evacuate" position and record the
difference in the mercury levels in the
manometer. The absolute internal
pressure in the flask (Pi) is equal to the
barometric pressure less the
manometer reading. Immediately turn
the flask valve to the "sample"
position and permit the gas to enter
the flask until pressures in the flask
and sample line (i.e., duct, stack) are
equal. This will usually'require about
15 seconds; a longer period indicates
a "plug" in the probe, which must be
corrected before sampling is
continued. After collecting the sample,
turn the flask valve to its "purge"
position and disconnect the flask from
the sampling train. Shake the flask for
at least 5 minutes.
4.1.2 If the gas being sampled con-
tains insufficient oxygen for the
conversion of NO to N02 (e.g., an
applicable subpart of the standard
may require taking a sample of a
calibration gas mixture of NO in N2),
then oxygen shall be introduced into
the flask to permit this conversion.
Oxygen may be introduced into the
flask by one of three methods; (1)
before evacuating the sampling flask
flush with pure cylinder oxygen, then
evacuate flask to 75 mm Hg (3 in. Hg)
absolute pressure or less; or (2) inject
oxygen into the flask after sampling;
or (3) terminate sampling with a
minimum of 50 mm Hg (2 in. Hg)
vacuum remaining in the flask,' record
this final pressure, and then vent the
flask to the atmosphere until the flask
pressure is almost equal to
atmospheric pressure.
4.2 Sample Recovery. Let the flask
set for a minimum of 16 hours and
then shake the contents for 2
minutes. Connect the flask to a
mercury filled U-tube manometer.
Open the valve from the flask to the
manometer and record the flask
temperature (Tf), the barometric
pressure, and the difference between
the mercury levels in the manometer.
The absolute internal pressure in the
flask (Pi) is the barometric pressure
less the manometer reading. Transfer
the contents of the flask to a leak-free
polyethylene bottle. Rinse the flask
twice with 5-ml portions of deionized,
distilled water and add the rinse
water to the bottle. Adjust the pH to
between 9 and 12 by adding sodium
hydroxide (1N), dropwise (about 25 to
35 drops). Check the pH by dipping a
stirring rod into the solution and then
touching the rod to the pH test paper.
Remove as little material as possible
during this step. Mark the height of
the liquid level so that the container
can be checked for leakage after
transport. Label the container to
clearly identify its contents. Seal the
container for shipping.
4.3 Analysis. Note the level of the
liquid in container and confirm
whether or not any sample was lost
-------
5-01-79
Section 3.6.10
during shipment; note this on the
analytical data sheet. If a noticeable
amount of leakage has occurred,
either void the sample or use
methods, subject to the approval of
the Administrator, to correct the final
results. Immediately prior to analysis,
transfer the contents of the shipping
container to a 50-ml volumetric flask,
and rinse the container twice with 5-
ml portions of deionized, distilled
water. Add the rinse water to the
flask and dilute to the mark with
deionized, distilled water; mix
thoroughly. Pipette a 25-ml aliquot
into the porcelain evaporating dish.
Return any unused portion of the
sample to the polyethylene storage
bottle. Evaporate the 25-ml aliquot to
dryness on a steam bath and allow to
cool. Add 2 ml phenoldisulfonic acid
solution to the dried residue and
triturate thoroughly with a
polyethylene policeman. Make sure
the solution contacts all the residue.
Add 1 ml deionized, distilled water
and four drops of concentrated
sulfuric acid. Heat the solution on a
steam bath for 3 minutes with oc-
casional stirring. Allow the solution to
cool, add 20 ml deionized, distilled
water, mix well by stirring, and add
concentrated ammonium hydroxide,
dropwise, with constant stirring, until
the pH is 10 (as determined by pH
paper). If the sample contains solids,
these must be removed by filtration
(centrifugation is an acceptable
alternative, subject to the approval of
the Administrator), as follows: filter
through Whatman No. 41 filter paper
into a 100-ml volumetric flask; rinse
the evaporating dish with three 5-ml
portions of deionized, distilled water;
filter these three rinses. Wash the
filter with at least three 15-ml
portions of deionized, distilled water.
Add the filter washings to the
contents of the volumetric flask and
dilute to the mark with deionized,
distilled water. If solids are absent,
the solution can be transferred
directly to the 100-ml volumetric flask
and diluted to the mark with
deionized, distilled water. Mix the
contents of the flask thoroughly, and
measure the absorbance at the
optimum wavelength used for the
standards (Section 5.2.1), using the
blank solution as a zero reference.
Dilute the sample and the blank with
equal volumes of deionized, distilled
water if the absorbance exceeds A«,
the absorbance of the 400 fjg N02
standard (see Section 5.2.2).
5. Calibration
5.1. Flask Volume. The volume of
the collection flask/flask valve
combination must be known prior to
sampling. Assemble the flask and
flask valve and fill with water, to the
stopcock. Measure the volume of
water to ±10 ml. Record this volume
on the flask.
5.2 Spectrophotometer Calibration.
5.2.1 Optimum Wavelength Deter-
mination. Calibrate the wavelength
scale of the Spectrophotometer every
6 months. The calibration may be ac-
complished by using an energy source
with an intense line emission such as
a mercury lamp, or by using a series
of glass filters spanning the measur-
ing range of the Spectrophotometer.
Calibration materials are available
commercially and from the National
Bureau of Standards. Specific details
on the use of such materials should
be supplied by the vendor; general in-
formation about calibration techniques
can be obtained from general
reference books on analytical
chemistry. The wavelength scale of
the Spectrophotometer must read
correctly within ±5 nm at all calibra-
tion points; otherwise, the Spectro-
photometer shall be repaired and
recalibrated. Once the wavelength
scale of the spectophotometer is in
proper calibration, use 410 nm as the
optimum wavelength for the measure-
ment of the absorbance of the
standards and samples.
Alternatively, a scanning procedure
may be employed to determine the
proper measuring wavelength. If the
instrument is a double-beam Spectro-
photometer, scan the spectrum be-
tween 400 and 415 nm using a 200
fjg NO2 standard solution in the
sample cell and a blank solution in
the reference cell. If a peak does not
occur, the Spectrophotometer is
probably malfunctioning and should
be repaired. When a peak is obtained
within the 400 to 415 nm range, the
wavelength at which this peak occurs
shall be the optimum wavelength for
the measurement of absorbance of
both the standards and the samples.
For a single-beam Spectrophotometer,
follow the scanning procedure de-
scribed above, except that the blank
and standard solutions shall be
scanned separately. The optimum
wavelength shall be the wavelength
at which the maximum difference in
absorbance between the standard and
the blank occurs.
5.2.2 Determination of Spectro-
photometer Calibration Factor Kc. Add
0.0 ml, 2 ml, 4 ml, 6 ml, and 8 ml of
the KN03 working standard solution (1
ml = 100 fjg N02) to a series of five
50-ml volumetric flasks. To each flask.
add 25 ml of absorbing solution, 10
ml deionized, distilled water, and
sodium hydroxide (1 N) dropwise until
the pH is between 9 and 12 (about 25
to 35 drops each). Dilute to the mark
with deionized, distilled water. Mix
thoroughly and pipette-a 25-ml aliquot
of each solution into a separate
porcelain evaporating dish. Beginning
with the evaporation step, follow the
analysis procedure of Section 4.3,
until the solution has been transferred
to the 100 ml volumetric flask and
diluted to the mark. Measure the
absorbance of each solution, at the
optimum wavelength, as determined
in Section 5.2.1. This calibration pro-
cedure must be repeated on each day
that samples are analyzed. Calculate
the Spectrophotometer calibration
factor as follows:
Kc=100 Ai+2A2+3A3+4A«
A,2+A22+A32+A<2
Equation 7-1
where
Kc = Calibration factor
Ai= Absorbance of the 100-/ug NO2
standard
A2=Absorbance of the 200-//g NO2
standard
A3=Absorbance of the 300-/JQ N02
standard
A« = Absorbance of the 400-fjg N02
standard
5.3 Barometer. Calibrate against a
mercury barometer.
5.4 Temperature Gauge. Calibrate
dial thermometer against mercury-in-
glass thermometers.
5.5 Vacuum Gauge. Calibrate
mechanical gauges, if used, against a
mercury manometer such as that
specified in 2.1.6.
5.6 Analytical Balance. Calibrate
against standard weights.
6. Calculations
Carry out the calculations, retaining
at least one extra decimal figure
beyond that of the acquired data.
Round off figures after final
calculations.
6.1 Nomenclature.
A = Absorbance of sample.
C = Concentration of N02 as N02,
dry basis, corrected to standard
conditions, mg/dscm (Ib/dscf).
F= Dilution factor (i.e., 25/5,
25/10, etc., required only if
sample dilution was needed to
reduce the absorbance into the
range of calibration).
-------
Section 3.6.10
6-01-79
Kc = Spectrophotometer calibration
factor.
m = Mass of N02 as N02 in gas
sample, y/g.
Pi = Final absolute pressure of
flask, mm Hg (in. Hg).
Pi = Initial absolute pressure of
flask, mm Hg (in. Hg).
Pstdr Standard absolute pressure,
760 mm Hg (29.92 in. Hg).
Tt = Final absolute temperature of
flask, °K (°R).
Ti = Initial absolute temperature of
flask, °K (°R).
T9to = Standard absolute
temperature, 293° K (528° R).
Vsc = Sample volume at standard
conditions (dry basis), ml.
Vf = Volume of flask and valve, ml.
Va = Volume of absorbing solution,
25 ml.
2 = 50/25, the aliquot factor. (If
other than a 25-ml aliquot was
used for analysis, the corre-
sponding factor must be sub-
stituted).
6.2 Sample Volume, Dry Basis, Cor-
rected to Standard Conditions.
JSMV.-Vjr *-£n
Paw [ TV Ti J
*-£i-|
T, T,J
= K,(V( - 25 ml)
where:
K, = 0.3858
= 17.64
mm Hg
°R
Equation 7-2
for metric units
7. Bibliography
1. Standard Methods of Chemical
Analysis. 6th ed. New York, D.
Van Nostrand Co., Inc. 1962. Vol.
1, p. 329-330.
2. Standard Method of Test for
Oxides of Nitrogen in Gaseous
Combustion Products (Phenoldi-
sulfonic Acid Procedure). In:
1968 Book of ASTM Standards,
Part 26. Philadelphia Pa. 1968.
ASTM Designation D-1606-60, p.
725-729.
3. Jacob, M.B. The Chemical Analy-
sis of Air Pollutants. New York,
Interscience Publishers, Inc.
1960. Vol. 10, p. 351-356.
4. Beatty, R.L., LB. Berger, and
H.H. Schrenk. Determination of
Oxides of Nitrogen by the
Phenoldisulfonic Acid Method.
Bureau of Mines, U.S. Dept. of
Interior. R.I. 3687. February
1943.
5. Hamil, H.F. and D.E. Camann.
Collaborative Study of Method for
the Determination of Nitrogen
Oxide Emissions from Stationary
Sources (Fossil Fuel-Fired Steam
Generators). Southwest Research
Institute report for Environmental
Protection Agency. Research Tri-
angle Park, N.C. October 5, 1973.
6. Hamil, H.F. and R.E. Thomas.
Collaborative Study of Method for
the Determination of Nitrogen
Oxide Emissions from Stationary
Sources (Nitric Acid Plants).
Southwest Research Institute
report for Environmental
Protection Agency. Research
Triangle Park, N.C. May 8,1974.
for English units
in. Hg
6.3 Total fjg NO2 Per Sample.
m = 2 KCAF
Equation 7-3
Note - If other than a 25 ml aliquot
is used for analysis, the factor 2 must
be replaced by a corresponding factor.
6.4 Sample Concentration, Dry
Basis, Corrected to Standard
Conditions.
m
where
K2=103
Equation 7-4
for metric units
= 6.243x1 0~s 'J/scf for English
//g/ml units
-------
6-01-79
Section 3.6.10
Probe
\
r
Filter
• Ground-Glass.socket,
9 No. 12/5
3-way Stopcock.
T-bore. J Pyrex.
2-mm bore, 8-mm OD
Flask Valve
Squeeze bulb
Pump valve
Pump
Flask
Flask shield
Thermometer
Ground-Class
cone, standard taper,
5 sleeve No. 24/40
T
210 mm
Ground-Glass socket.
3 No. 12/5
Pyrex
Foam encasement
Boiling flask -
2-liter, round-bottom, short
neck, with'gs/eeveNo. 24/40
Figure 7-1. Sampling train, flask valve, and flask.
-------
6-01-79
Section 3.6.11
11.0 References
1. Quality Assurance Handbook for
Air Pollution Measurement Sys-
tems, Volume I - Principles. U.S.
Environmental Protection
Agency, Office of Research and
Development, Environmental
Monitoring and Support
Laboratory, Research Triangle
Park, N.C. EPA-600/9-76-005,
March 1976.
2. Buchanan, J.W. and D.E.
Wagoner. Guidelines for
Development of a Quality
Assurance Program, Deter-
mination of Nitrogen Oxide Emis-
sions from Stationary Sources.
EPA.
3. Hamil, Henry F. et al. The
Collaborative Study of EPA
Methods 5, 6, and 7 in Fossil
Fuel Fired Steam Generators.
Final Report, EPA-650/4-74-013,
May 1974.
4. Hamil, H.F. and R.E. Thomas.
Collaborative Study of Method for
the Determination of Nitrogen
Oxide Emissions from Stationary
Sources (Nitric Acid Plants), EPA-
650/4074-028, May 1974.
' 5. Hamil, Henry F. Laboratory and
Field Evaluations of EPA
Methods 2, 6, and 7. Final
Report, EPA Contract No. 68-02-
0626. Southwest Research
Institute, San Antonio, Tex.,
October 1973.
6. Standard Methods of Chemical
Analysis, 6th Edition. D. Van
Nostrand Co., Inc., N.Y., 1962.
Vol. 1, pp. 329-330.
7. Standard Method of Test for
Oxides of Nitrogen in Gaseous
Combustion Products
(Phenoldisulfonic Acid Procedure)
In: 1968 Book of ASTM
Standards, Part 26. Philadelphia,
Pa. 1968. ASTM Designation D-
1608-60, pp.725-729.
8. Jacob, M.B. The Chemical Analy-
sis of Air Pollutants. Interscience
Publishers, Inc., N.Y., 1960. Vol.
10, pp. 351-356.
9. Beatty, R.L., L.B. Berger, and
H.H. Schrenk. Determination of
Oxides of Nitrogen by the
Phenoldisulfonic Acid Method.
Bureau of Mines, U.S.
Department of Interior, R.I. 3687.
February 1943.
10. Hamil, H.F. and D.E. Camann.
Collaborative Study of Methods
for the Determination of Nitrogen
of Nitrogen Oxide Emissions from
Stationary Sources (Fossil Fuel
Fired Steam Generators). South-
west Research Institute report for
EPA, Research Triangle Park,
N.C. Octobers, 1973.
11. Hamil, H.F. and R.E. Thomas.
Collaborative Study of Methods
for the Determination of Nitrogen
Oxide Emissions from Stationary
Sources (Nitric Acid Plants).
Southwest Research Institute
report for EPA, Research Triangle
Park, N.C. May 8, 1974.
12. 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. En-
vironmental Protection Agency,
Environmental Monitoring and
Support Laboratory (MD-77), Re-
search Triangle Park, N.C. 27711
13. Fuerst, R.G. and M.R. Midgett. A
Summary of Interlaboratory
Source Performance Surveys for
EPA Reference Methods 6 and 7-
1978. Report in preparation by
U.S. Environmental Protection
Agency, Environmental
Monitoring and Support
Laboratory (MD-77), Research
Triangle Park, N.C. 27711.
-------
5-01-79
Section 3.6.12
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 customary
descriptive title centered at the top of
the page. However, the section-page
documentation in the top right-hand
corner of each page 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 M7-1.2 indicates that
the form is Figure 1.2 in Section 3.6.1
of the Method 7 Handbook. Future
revisions of these forms, if any, can
be documented by 1.2A, 1.2B, etc.
Twelve of the blank forms listed below
are included in this section. Four are
in the Method Highlights subsection
as shown by the MH following the
form number.
Form
1.2
2.1
2.2
3.1 (MH)
3.2 (MH)
4.1Aand4.1B
4.2A and 4.2B
4.3 (MH)
5.1
5.2
5.3 (MH)
6.1Aand6.1B
8.1
Title
Procurement Log
Optimum Wavelength
Determination Data
Form •
Analytical Balance
Calibration Form
Pretest Checklist
Pretest Preparations
Nitrogen Oxide Field
Data Form (English
and metric units)
NOX Sample Recovery
and Integrity Data Form
(English and metric
units)
On-Site Measurements
Standard Solution and
Control Sample Analyt-
ical Data Form
NO, Laboratory Data
Form
Posttest Operations
Nitrogen Oxide Calcu-
lation Form (English
and metric units)
Method 7 Checklist to
be Used by Auditors
-------
Procurement Log
Item description
Qty.
Purchase
order
number
Vendor
Date
Ord.
Rec.
Cost
Dispo-
sition
Comments
CO
(»
o
F*
5'
3
U
b>
to
01
6
vj
CD
Quality Assurance Handbook M7-J.2
-------
6-01-79
Section 3.6.12
Optimum Wavelength Determination Data Form
Spectrophotometer number
Calibrated by
Date
Reviewed by
Spectrophotometer
setting, nm
399
400
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
Absorbance
of standard
OD*
Absorbance
of blank
00"
Actual
absorbance of
ODC
" Absorbance of the 200 ug NOz standard in a single beam Spectrophotometer.
bAbsorbance of the blank in a single-beam Spectrophotometer.
cFor a single-beam Spectrophotometer — absorbance of the standard minus absorbance of the blank.
For a double beam Spectrophotometer — absorbance of the 200 yg NOz standard with the blank in the
reference cell.
Spectrophotometer setting for maximum actual absorbance of standard
If the maximum actual absorbance occurs at the Spectrophotometer setting of <399 or >416 nm,
the Spectrophotometer must be repaired or recalibrated.
Quality Assurance Handbook M7-2.1
-------
Section 3.6.12
5-01-79
Analytical Balance Calibration Form
Balance name
Number.
Classification of standard \
Date
•
0.5000 g
weights
LOOOOg
W.OOOg
50.00OO g
WO.OOOO g
Analyst
Quality Assurance Handbook M7-2.2
-------
Nitrogen Oxide Field Data Form
(English units)
Plant Citv
Sample location Date
Sample
number
Operator
Baromet
Sample
point
location
Sample
time
24-hr
Probe
temperature,
°F
Flask
and valve
number
Volume
of flask
and valve (Vr).
ml
ric pressure
rPh«J in. Hg
Initial pressure
in. Hg
Leg A,
LegBi
P?
01
vl
Initial temperature *
°^ ft;J
°R (J,f
01
OT
a
o
3
'Pi = ^b«, - (A; + B,).
Quality Assurance Handbook M7-4.1A
-------
Nitrogen Oxide Field Data Form
(metric units)
Plant
Sample location
Operator
City
Date
Barometric pressure IPt,,,l
mm Hg
Sample
number
Sample
point
location
Sample
time
24-hr
Probe
temperature.
°C
Flask
and valve
number
Volume
of flask
and valve (Vf),
ml
Initial Pressure
mm Hg
Leg A,
LegB,
P*
Initial temperature
°C (tj
°K (Tf
CO
I
8
CJ
b>
01
6
vl
«D
'Pi = Pbar - (A, + BJ.
Quality Assurance Handbook M7-4.1B
-------
NO, Sample Recovery and Integrity Data Form
(English units)
Plant
Date
Sample recovery personnel
Barometric pressure.
in. Hg
Person with direct responsibility for recovered samples.
Sample
number
Final Pressure,
in.Hg
Leg A,
Leg Bt
P,'
Final temperature.
°FM
-
°R(T,f
_
Sample
recovery
time.
24-h
•— -
pH
adjusted
9 to 12
Liquid
level
marked
Samples
stored
in locked
container
"/. = t, + 46O°f.
Lab person with direct responsibility for recovered samples :
Date recovered samples received Analyst ______
AH samples identifiable? ; All liquids at marked level?.
Remarks •_ ' •
Signature of lab sample trustee .
tt>
o
Quality Assurance Handbook M7-4.2A
-------
NO, Sample Recovery and Integrity Data Form
(metric units)
Plant
Date
Sample recovery personnel
Barometric pressure,
. mm Hg
Person with direct responsibility for recovered samples .
Sample
number
Final pressure.
mm Hg
Leg At
Leg 8,
Pt"
Final temperature.
°CM
KfTj"
Sample
recovery
time.
24-h
pH
adjusted
9 to 12
Liquid
Level
marked
Samples
stored
in locked
container
w
u
0>
-M,
M
"P, = Pt», - (A, +B,).
br, = t, + 230°C.
Lab person with direct responsibility for recovered samples
Date recovered samples received
Altsamples identifiable? All liquids at marked level? .
01
6
VI
-------
5-01-79
Section 3.6.12
Plant
Standard Solution and Control Sample
i Analytical Data Form
Date
Analyst
Optimum wavelength
nm
Blank used as reference?
Sample
number
A1
A2
A3
A4
S}
S2
S3
Sample.
V9
100
200
300
4OO
WO
200
300
Working
solution
X
X
X
X
Control
sample
X
X
X
Measured.
absorbance,
OD
Calculated
absorbance."
OD
—
—
—
—
Absorbance
comparison
error,6%
—
—
—
—
Avgc
"Calculated absorbance: OD = (/jg)/Kc i.e.. SJ calculated absorbance = 100/KC.
"Absorbance comparison errors:
% = ion>f(measuredaDSOroance- OD) - (calculated absorbance, OD).
calculated absorbance. OD
'Average of absolute values.
Quality Assurance Handbook M7-5.1
-------
Section 3.6.12
10
5-01-79
NO, Laboratory Data Form
Plant
Date samples received
Aliquot factor
Blank absorbance
Calibration factor (KJ
Sample
number
Sample
absorbance.
A
Run numberfsj
Date analyreri.
Samples analyzed by
Date reviewed by
Date of review
Dilution
factor,
F
Total mass of NO,
as NOz in sample,
m fag)
m = 2 KCAF, Note - If other than a 25 ml aliquot is used for analysis, the factor 2 must be replaced by a corresponding
factor.
Quality Assurance Handbook M7-5.2
-------
6-01-79 11 Section 3.6.12
Nitrogen Oxide Calculation Form
(English units)
Sample Volume
V, = ml. P, = . in. Hg, T, = °R
P\ — . in. Hg, T, = °R
VK = 17.64 (Vt-25) \ — = ml Equation 6-1
Total fjg N02 Per Sample
Kc = ..A = . OD, F = .
m = 2KC AF = . pg of NO2
Equation 6-2
Sample Concentration
C= 6.243 x to'5 I ——I = . x10-*lb/dscf
. Quality Assurance Handbook M7-6.1A
-------
Section 3.6.12 12 6-01-79
Nitrogen Oxide Calculation Form
(metric units)
Sample Volume
V, = . ml. Pt = . mm Hg, T, = _. K
• mm Hg, T, • K
VK = 0.3858 (V,-25)
Pt_
T,
ml
Equation 6-1
m = 2KC AF =
Total ug N02 Per Sample
OD. F = .
rp of NO?
Equation 6-2
C = W3
Sample Concentration
-jy— = • x W3 mg/dscm.
Equation 6-3
> Quality Assurance Handbook M7-6. IB
-------
5-01-79 13 Section 3.6.12
Method 7 Checklist to be Used by Auditors
Presampling Preparation
Yes No
1. Information concerning combustion effluents that may act as
interferents
2. Plant operation parameters variation
3. Calibration of the flask and valve volume — three determinations
4. Absorbing reagent preparation
On-Site Measurements
5. Leak testing of the sampling train
6. Preparation and pipetting of absorbing solution into sampling
flask
Postsampling
(Analysis and Calculation)
7. Control sample analysis
8. Sample aliquotting technique
9. Evaporation and chemical treatment of sample
10. Spectrophotometric technique
a. Preparation of standard nitrate samples
b. Measurement of absorbance, including blanks
c. Calibration factor
d. Wavelength and absorbance, including blanks
11. Calculation procedure and checks
a. Use of computer program
b. Independent check of calculations
Comments
Quality Assurance Handbook M7-8. J
-------
6-01-79
1
Section 3.7.0
vxEPA
United States
Environmental Protection
Agency
Environmental Monitoring Systems
Laboratory-
Research Triangle Park NC 27711
Research and Development
Section 3.7
Method 8—Determination of
Sulfuric Acid Mist and
Sulfur Dioxide Emissions
from Stationary Sources
Outline
Sectjon
Summary
Method Highlights
Method Description
1. Procurement of Apparatus
and Supplies
2. Calibration of Apparatus
3. Presampling Operations
4. On-Site Measurements
5. Postsampling Operations
6. Calculations
7. Maintenance
8. Auditing Procedure
9. Recommended Standards
for Establishing
Traceability
10. Reference Method
11. References
12. Data Forms
Summary
A gas sample is extracted isokinet-
ically from the stack. The sulfuric acid
mist (including sulfur trioxide, or SOs)
and the S02 are separated, and both
fractions are 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.
This method is applicable for the
determination of sulfuric acid mist
(including SOs) emissions from
stationary sources. Collaborative tests
have shown that the minimum
detectable limits of the method are
Documentation
3.7
3.7
3.7.1
3.7.2
3.7.3
3.7.4
3.7.5
3.7.6
3.7.7
3.7.8
3.7.9
3.7.10
3.7.11
3.7.12
Number
of Pages
2
7
10
4
10
9
6
2
3
1
5
1
17
0.05 mg S03/m3 (0.03 x 10~7 Ib/ft3)
and 1.2 mg SO2/m3 (0.74 x 10~7
Ib/ft3). No upper limits have been
established. Based on theoretical
calculations for 200 ml of 3%
hydrogen peroxide solution, the upper
concentration limit in a 1.0 m3 (35.3
ft3) gas sample is about 12,500 mg
S02/m3 (7.7 x 10'4 Ib/ft3). The upper
limit can be extended by increasing
the quantity of peroxide solution in
the impingers.
Possible interferences with this
method are fluorides, free ammonia,
and dimethyl aniline. If any of these
interferents are present (as
determined by knowledge of the
process), alternative methods subject
to the approval of the Administrator,
U.S. Environmental Protection
Agency, are required. For example, if
-------
Section 3.7.0
5-01-79
free ammonia is present, white
particulates can be seen in the probe
and in the isopropanol impinger.
Filterable paniculate matter may be
determined along with SOs and SOa
(subject to the approval of the
Administrator); however, the
procedure used for particulate matter
must be consistent with the
specifications and procedures given in
Method 5.
The Method 8 description which
follows is based on the Reference
Method that was promulgated on
August 18, 1977. A complete copy of
the Reference Method is in Section
3.7.10. Data forms are provided in
Subsection 12 for the convenience of
the Handbook user.
Reference 1 was used extensively
in preparing the method description.
References 2 and 3 are the
collaborative test studies of this
method and other related methods;
data from these test studies were
used in establishing quality control
limits. References 4 and 5 were used
extensively in those sections which
include the description, calibration,
and maintenance of the sampling
train. All references are listed in
Section 3.7.11.
A collaborative test program was
conducted at a sulfuric acid (HaSO*)
plant to determine the accuracy of
Method 8. Six laboratories simultane-
ously sampled the same stack, using
two Method 8 sampling trains per
laboratory.6 The collaborative test
determined that the repeatability
(within-laboratory precision) of the
method was 7.19 mg HzSO^m3 and
22.30 mg S02/m3 and that
reproducibility (between-laboratory
precision) of the method was 8.03 mg
H2SO
-------
6-01-79
Section 3.7.0
Section 3.7.6 (Calculations) provides
the tester with the required equations,
the nomenclature, and the suggested
number of significant digits. It is
suggested that a programmed calcu-
lator be used if available to reduce the
chance of calculation error.
Section 3.7.7 (Maintenance)
provides the tester with a guide for a
routine maintenance program. This
program is not required, but should
reduce equipment malfunctions.
5. Auditing Procedure
Section 3.7.8 (Auditing Procedure)
provides a description of necessary
activities for conducting performance
and system audits. The performance
audit of the analytical phase can be
conducted using an aqueous ammoni-
um sulfate solution. Performance
audits for the analytical phase and the
data processing are described in
Section 3.7.8. A checklist for a
systems audit is also included in this
section.
Section 3.7.9 (Recommended
Standards for Establishing
Traceability) recommends the primary
standards to which the working
standards should be traceable.
6. References
Sections 3.7.10 and 3.7.11 contain
the Reference Method and the sug-
gested references.
Pretest Sampling Checks
(Methods. Figure 2.5)
Date
Meter box number.
-Calibrated by
AH@
Dry Gas Meter'
Pretest calibration factor -
. (within ±2% of the average factor for each calibration run)..
Impinger Thermometer
Was a pretest temperature correction used? — yes — no.
If yes, temperature correction (within ±; °C (2°F) of reference values for calibration and within ±2°C (4°F) of
reference values for calibration check).
Dry Gas Meter Thermometer
Was a pretest temperature correction made? — yes no.
If yes. temperature correction (within ±3°C (5,4°F) of reference values for calibration and 6°C (10.8°F) of
reference values for calibration check).
Barometer
Was the pretest field barometer reading correct (within ±2.5 mm (0.1 in.) Hg of mercury-in-glass barometer)? yes
—no.
'Most significant items/parameters to be checked
-------
Section 3.7.0
5-01-79
Pretest Preparations
(Method 8. Figure 3. It
Apparatus •
check
Probe
Type glass liner
fiorp$ilirate
Quart?
Heated
Leak checked
Nozzle
niass
Stainless steel
Other
Pilot Tube
Types
Other
Properly
attached
Mortifiratinns
CP
Differential
Pressure Gauge
Inclined manome-
ter
Cither
Filter Holder
Borosilicate glass
Glass frit
Gasket
Silirnne
Teflnn
Vitnn
Condenser
Impingers
Greenburg-Smith
Modified
Greenburg-Smith
Impinger Temperature
Sensor
Thermnmeter
nther
ralihrnteri
Acceptable
Yes
No
Quantity
required
Ready
Yes
No
Loaded and packed
-------
6-01-79
Section 3.7.0
Pretest Preparations
(Method 8. Figure 3.1)
(continued)
Apparatus
check
Other
Barometer
Mpm/ry
& ne>rni/i
ra,ihrat»H*
Stack Temperature Sensor
Tynf *
Reagents
Distilled water
Hydrogen peroxide
(30%)
Isopropanol (8O%)
(checked for
peroxides)
Silica gel
Meter System
Pump leak free*
Orifice meter*
Dry gas meter*
Acceptable
Yes
No
Quantity
required
Ready
Yes
No
Loaded and packed
' Most significant items/parameters to be checked.
-------
Section 3.7.0 6 6-01-79
On-Site Measurements
(Methods, Figure 4.4)
Sampling
Impingers properly assembled?
Contents:* 1st
2nd
3rd
4th
Cooling system
Filter between 1st and 2nd impinger?
Proper connections?
Silicone grease added to all ground-glass joints?
Pretest leak check? (optional) Leakage?.
Pitot tube lines checked for plugging or leaks?' .
Meter box leveled? Periodically?.
Manometers zeroed?* _____
Heat uniform along length of probe?*
AW@ from most recent calibration
Nomograph set up properly?
Care taken to avoid scraping sample port or stack wall?
Seal around in-stack probe effective?
Probe moved at proper time?
Nozzle and Pitot tube parallel to stack wall at all times?
Data forms complete and data properly recorded?
Nomograph setting changed when stack temperature changes significantly?
Velocity pressures and orifice pressure readings recorded accurately?
Posttest leak check performed?* (mandatory)
Leakage rate*
Sampling Recovery
System purged at least 15 min at test sampling rate?*
Filter placed in Jst impinger contents?
Ice removed before purging?
Contents of impingers placed in polyethylene bottles?
Glassware rinsed with distilled water?
Fluid level marked?*
Sample containers sealed and identified?*
Blanks obtained?*
* Most significant items/parameters to be checked.
-------
5-01-79 7 Section 3.7.0
Posttest Sampling Checks
(Method 8. Figure 5.1)
Meter Box Number *
Dry Gas Meter
Pretest calibration factor Y =
Posttest check X, = Y2 = (±5% of pretest factor}*
Recalibration required? yes no
If yes. recalibration factor Y (within ±2% of average)
Lower calibration factor. Y = for pretest or posttest calculations
Dry Gas Meter Thermometer
Was a pretest meter temperature correction used? yes no
If yes, temperature correction
Posttest comparison with mercury-in-glass thermometer (within ±6°C (10.8°F) of reference values)
Recalibration required? yes no
Recalibration temperature correction, if used (within ±3°C (5.4° F) of reference values)
If yes, no 'correction is needed whenever meter thermometer temperature is higher
If recalibration temperature is higher, add correction to average meter temperature for calculations
Barometer
Was pretest field barometer reading correct? yes no
Posttest comparison mm (in.) Hg (within ±5.0 mm (0.2 in.) Hg of mercury-in-glass barometer)
Was recalibration required? yes no
If yes, no correction is needed whenever the field barometer has the lower reading
If the mercury-in-glass reading is lower, subtract the difference from the field data readings for the calculations
"Most significant items/parameters to be checked.
-------
Section 3.7.0
5-01-79
Posttest Operations
(Methods, Figure 5.4)
Reagents
Normality of sulfuric acid standard*
Date of purchase
Date standardized.
Normality of barium perch/orate tit rant"
Date standardized
Normality of control sample*
Date prepared
Volume of burette*
Sample Preparation
Has liquid level noticeably changed?
Original volume
Graduations
Corrected volume
Sulfuric acid samples diluted to 250 ml?'
Sulfur dioxide samples diluted to WOO ml?'
Analysis
Aliquot analyzed*
Do replicate Mr am volumes agree within 1% or 0.2 ml?
Number of control samples analyzed
Are replicate control samples within 0.2 ml? .
Is accuracy of control sample analysis ±10%?*
AII data recorded?
Reviewed.
*Most significant items/parameters to be checked.
-------
5-01-79
Section 3.7.1
1.0 Procurement of Apparatus and Supplies
A schematic of the sampling train
used in Method 8 is shown in Figure
1.1. It is similar to the Method 5 train,
but the filter position is different and
the filter holder does not have to be
heated. Commercial models of this
train are available. For those who
desire to build their own, complete
construction details are described in
APTD-0581." Changes from the
APTD-0581 document and allowable
modifications to Figure 1.1 are
discussed in the following
subsections.
The operating and maintenance
procedures for the sampling train are
described in APTD-0576.5 Since
correct usage is important in
obtaining valid results, all users
should read the APTD-0576 document
and adopt the operating and
maintenance procedures therein,
unless otherwise specified. Further
details and guidelines on operation
and maintenance in Method 5 should
be read and followed whenever they
are applicable. Maintenance of
equipment is also covered in Section
3.7.7.
Specifications, criteria, and/or de-
sign features as applicable, are given
in this section to aid in the selection
of equipment to ensure the collection
of data 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 (Figure 1.2) be used
to record the descriptive title of the
equipment; the identification number,
if applicable; and the results of
acceptance checks. Also, if calibration
is required as part of the acceptance
check, the data are to be recorded in
the calibration log book. Table 1.1 at
the end of this section contains a
summary of the quality assurance
activities for procurement and
acceptance of apparatus and supplies.
Determination of filterable
paniculate matter simultaneously with
sulfuric acid mist (and with SO3 and
SOz) will not be discussed in this
subsection.
1.1 Sampling
1.1.1 Probe Liner - Borosilicate or
quartz glass tubing equipped with a
heating system capable of preventing
visible condensation during sampling
should be protected with an outer
sheath of stainless steel. Borosilicate
or quartz probe liners can be used for
stack temperatures up to about 480°C
(900°F). Quartz liners should be used
for high-temperature probes for stacks
with temperatures between 480° and
900°C (900° and 1650°F). Both types
of liners may be used at temperatures
higher than specified for short periods
of time, subject to the approval of the
Administrator. Metal probe liners may
not be used because of the
requirement that the liner material
must not react with the gas
constituents.
Upon receiving a new probe, it
should be visually checked for the
length and composition ordered and
for breaks or cracks and then leak
checked on a sampling train as shown
in Figure 1.1. Also, the probe heating
system should be checked as follows:
1. Connect the probe with a nozzle
attached to the inlet of the pump.
2. Electrically connect and turn on
the probe heater for 2 or 3 min.
It should become warm to the
touch.
3. Start the pump and adjust the
needle valve until a flow rate of
about 0.02 mVmin (0.75
ftVmin) is achieved.
4. Check the probe. It should
remain warm to the touch. The
heater should be capable of
maintaining the exit air at a
minimum of 100°C (212°F)
under these conditions. If it
cannot, the probe should be
repaired, returned to the
supplier, or rejected.
1.1.2 Probe Nozzle - Same as
Method 5, Section 3.4.2.
1.1.3 Pilot Tube - Same as Method
5, Section 3.4.2.
1.1.4 Differentia/ Pressure Gauge -
Same as Method 5, Section 3.4.2.
1.1.5 Filter Holder - A borosilicate
glass filter holder with a glass frit
filter support and a silicone rubber
gasket is required by the Reference
Method. Other gasket materials (e.g.,
Teflon or Viton) may be used, subject
to the approval of the Administrator.
The holder design must provide a
positive seal against leakage from the
outside or around the filter. A filter
holder should be durable, easy to
load, and leak free in normal
applications. The filter holder is placed
between the first and second
impingers, and the filter is located
toward the direction of flow. Do not
heat the filter holder.
1.1.6 Impingers - Four impingers
are required, as shown in Figure 1.1.
The first and third impinger must be
of the Greenburg-Smith design with
standard tips. The second and fourth
should be of the Greenburg-Smith
design, but modified by replacing the
insert with an approximately 13-mm
(0.5-in.) inside diameter (ID) glass
tube having an unconstricted tip
located 13 mm (0.5 in.) from the
bottom of the flask. Connections
between impingers should be of glass.
(Plastic or rubber tubing is not
permitted because of absorption and
desorption of gaseous species.)
Silicone grease may be used, if
necessary, to prevent leakage.
Upon receipt of a new Greenburg-
Smith impinger, fill the inner impinger
tube with water. If the water does not
drain through orifice within 6 to 8 s,
the impinger tip should be replaced or
enlarged to prevent an excessive
pressure drop in the sampling system.
Each impinger is checked visually for
damages such as breaks or cracks and
for manufacturing flaws such as
poorly shaped connections.
Collection absorbers and flow rates
other than the specified ones may be
used subject to the approval of the
Administrator. The collection
efficiency must, however, be shown to
be at least 99% for each test run to
obtain approval and must be
documented in the emission test
report. If the efficiency is found to be
acceptable after a series of three
tests, further documentation is not
required. To conduct the efficiency
test, extra absorbers must be added
for the sulfuric acid mist and the SC>2,
and then each must be analyzed
separately. These extra absorbers
must not contain more than 1% of the
total H2SCM or S02.
1.1.7 Metering System - Same as
Method 5, Section 3.4.1.
1.1.8 Barometer - Same as Method
5, Section 3.4.1.
1.1.9 Gas Density Determination
Equipment - Same as Method 5,
Section 3.4.1.
-------
Section 3.7.1
5-01-79
1.1.10 Temperature Gauge - Same
as Method 5, Section 3.4.1.
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 - Two 1000-
ml polyethylene bottles are required
for each sample run, plus one 100-ml
polyethylene bottle to retain a blank
for each absorbing solution used in
testing. Visually check wash bottles
and/or storage bottles for damage.
Also check each storage bottle seal to
prevent sample leakage during
transport.
1.2.3 Graduated Cylinders - One
250-ml and one 1000-ml glass
graduated cylinder (Class A) or
volumetric flasks are needed to
measure the impinger contents.
1.2.4 Trip Balance - A trip balance
with a 500-g capacity and an
accuracy of ±0.5 g is needed to weigh
the silica gel, only if a moisture
content analysis is to be done. A
moisture determination has to be
performed unless the gas stream can
be considered dry. Check the trip
balance by using a range of standard
weights, and adjust or return to
supplier if necessary.
1.3 Analysis Glassware
1.3.1 Pipettes - Several volumetric
pipettes (Class A), including 5-, 10-,
20-, 25-, and 100-ml sizes, should be
available for the analysis.
1.3.2 Volumetric Flasks -Volumetric
flasks (Class A) are required, and
should include 50-, 100-, and 1000-
ml sizes.
1.3.3 Burette - A 50-ml 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.
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 graduated cylinder (Class A)
is needed in the preparation of the
thorin indicator and the sample.
Check all glassware for cracks,
breaks, and discernible manufacturing
flaws.
1.3.7 Trip Balance - Same as
Subsection 1.2.4.
1.4 Reagents
Unless otherwise indicated, all rea-
gents should conform to the specifica-
tions established by the Committee on
Analytical Reagents of the American
Chemical Society (ACS), when such
specifications are available; otherwise
use best available grade.
1.4.1 Sampling - The following are
required for sampling:
Filters - Same as Method 5, Section
3.4.1.
Silica Gel - Same as Method 5,
Section 3.4.1.
Water - Deionized distilled water to
conform to ASTM specification
D1193-74, Type 3. At the option of
the analyst, the potassium
permanganate (KMn04) test for
oxidizable organic matter may be
omitted when high concentrations of
organic matter are not expected to be
present.
Isopropanol. 80% - Mix 800 ml
reagent grade or certified ACS isopro-
panol with 200 ml of deionized
distilled water. Check each lot of
isopropanol for peroxide (H202)
impurities as follows:
1. Shake 10 ml of isopropanol with
10 ml of freshly prepared 10%
potassium iodide (Kl) solution.
2. Prepare a blank by similarly
treating 10 ml of deionized
distilled water.
3. After 1 min, read the absorbance
of the alcohol sample at 352 nm
on a spectrophotometer; if the
absorbance exceeds 0.1, reject
the isopropanol.
Peroxides may be removed from
isopropanol by redistilling or by
passing the mixture through a column
of activated alumina; after peroxides
are removed, check for peroxide
impurities using the same method as
above. However, reagent grade
isopropanol with suitably low peroxide
levels may be obtained from
commercial sources. Therefore, rejec-
tion of contaminated lots may be a
more efficient procedure.
Potassium iodide solution, 10% -
Dissolve 10.0 g of reagent grade or
certified ACS Kl in deionized distilled
water, and dilute to 100 ml. Prepare
when needed. This solution is used to
check for peroxide impurities in the
isopropanol only.
Hydrogen peroxide, 3% - Dilute 30%
reagent grade or certified ACS H2O2
1:9 (v/v) with deionized distilled
water. Prepare fresh daily.
1.4.2 Sample Recovery - The
following are required for sample
recovery: '*
Water - Deionized distilled water, as
in Subsection 1.4.1 above.
Isopropanol, 100% - See Subsection
1.4.1.
1.4.3 Analysis • The following are
required for sample analysis:
Water - Use deionized distilled
water as described in Subsection
1.4.1.
Isopropanol, 100% - Use reagent
grade or certified ACS isopropanol,
and check for peroxide impurities, as
in Subsection 1.4.1 above.
Thorin indicator - Reagent grade or
certified ACS 1 -(o-arsonophenylazo)-
2-naphthol-3,6-disulfonic acid
disodium salt. Dissolve 0.20 g in 100
ml of deionized distilled water.
Barium perch/orate solution, 0.0WON
- Dissolve 1.95 g of reagent grade or
certified ACS barium perchlorate
trihydrate (BafCIO^- 3H20) in 200 ml
deionized distilled water, and dilute to
1 L with isopropanol. Alternatively,
1.22 g of (BaCI2 • 2H20) may be used.
Standardize as in Section 3.7.5.
Suit uric acid standard, 0.01OON -
Either purchase the manufacturer's
certified 0.01 OON H2S04, or
standardize the H2SO4 to 0.01 OON
±0.0002N against 0.01 OON reagent
grade or certified ACS sodium
hydroxide (NaOH) that has previously
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.
-------
5-01-79
Section 3.7.1
Temperature Sensor
Probe
Probe
V- Pilot Tube
Temperature Sensor
Filter Holder
Thermometer
Check Valve
Vacuum
Line
Vacuum
Gauge
Orifice-Inclined
Manometer
Main Valve
Dry Test Meter
Figure 1.1. Schematic of Method 8 sampling train.
-------
Procurement Log
Item description
(1) /Mef «r &>X
Pc/SHO MoqflQ-
hel/c &avqes
\/
*.
Qty.
/
Purchase
order
number
7JA2S
Vendor
48C
Tech/io/oqy
\Jf
Date
Ord.
afr/K
Rec.
/fit/??
Cost
fc">
Dispo-
sition
ftettc/yftr
^Sse
Comments
Calibrate*
by GJ- S.
to
a
o
5"
3
W
vl
01
6
Figure 1.2. Example of a procurement log.
-------
5-01-79
Section 3.7.1
»
Table 1 . 1 Activity
Apparatus
Sampling
Sampling probe
with heating
system
Probe nozzle
Pilot tube
Differential
pressure
gauge
(manometer)
Vacuum gauge
Vacuum pump
Orifice meter
Impingers
Filter holder
Filters
Matrix for Procurement of Apparatus
Acceptance limits
Capable of 100°C
<21 2°F) exit air at
flow rate of 20 L/min
Stainless steel (316);
sharp, tapered leading
edge (angle <30°);
difference between
measured ID's <0. 1 mm
(0.004 in.); no nicks.
dents, or corrosion;
uniquely identified
(Meth. 5. Sec. 3.4.2)
Type-S (Meth. 2.
Sec. 3. 1.2); attached
to probe with impact
(high pressure) opening
plane even with or above
nozzle entry plane
Criteria in Meth. 2.
Sec. 3. 1.2; agree
within 5% of gauge-oil
manometer used to
calibrate
0-760 mm Hg range;
±25 mm (1 in.) Hg
accuracy at 380 mm
(15 in.)Hg
Capable of maintaining
a flow rate of 0.03-
0.05 m3 /minfl -1.7 ft3/
min) for pump inlet
vacuum of 380 mm (15
in.) Hg with pump out-
let at 760 mm (29.92
in.) Hg; leak free at
380 mm (15 in.) Hg
&H@ of 46.74 ±6. 35 mm
(1.84 ±0.25 in.)
(recommended)
Standard stock glass;
pressure drop across
impingers not excessive
(Sec. 3. 7. 1)
Leak free
Glass fiber without
organic binder designed
to remove 99.95% (
-------
Section 3.7.1
6-01-79
Table 1.1 (continued)
Apparatus Acceptance limits
Dry gas meter
Wet test meter
Thermometers
Barometer
Sample Recovery
Wash bottles
Storage bottles
Graduated
cylinders
Trip balance
Analysis
Glassware
Pipettes, volu-
metric flasks,
burette, and
graduated
cylinder
Reagents
Distilled water
Isopropanol
Capable of measuring
total volume with
accuracy of ±2% at
flow rate of
0.02 m3/min
(0. 75 ft3/min)
Capable of measuring
total volume with
accuracy of ±1%
Within ±1°C(2°F) of
value in range of 0°C
to 25°C (32°F to 67°F)
for impinger thermome-
ter; ±3°C (6°F) of true
value in range of 0°C
to 90°C (32°F to 194°F)
for dry gas meter
thermometers
Capable of measuring
atmospheric pressure
to within 2.5 mm
(0. 1 in.) Hg
Polyethylene or glass,
50O ml
Polyethylene, WOO ml
and 100 ml
Glass (Class A), 250
ml and 1000 ml
500 -g capacity, ±0.5 g;
needed to weigh silica
gel only if moisture
measurement desired
Glass (Class A)
ASTM-D1 193-74, Type 3
100% isopropanol, re-
agent grade or certified
ACS with no peroxide
impurities; absorbance
-------
5-01-79
Section 3.7.1
•
Table 1 . 1 (continued)
Apparatus
Hydrogen
peroxide
Potassium
iodide
Thorin
indicator
Barium perch/or-
ate trihydrate
solution
SuHuric acid
solution
Acceptance limits
30% HzOz, reagent grade
or certified ACS
Kl reagent grade or
certified ACS
1 -(o-arsonophenylazo)-
2-naphthol-3.6 disul-
fonic acid disodium
salt, reagent grade or
certified ACS
BafCIOJz • 3H2O. re-
agent grade or
certified ACS
HzSO*. O.OWON ±0.0002 N
Frequency and method
of measurement
Upon receipt, check
label for grade or
certification
As above
Upon receipt, check
label for grade or
certification
As above
Certified by manufac-
turer, or standardize
against 0.01 DON NaOH
previously standard-
ized against potassium
acid phthalate (pri-
mary standard grade)
Action if
requirements
are not met
Replace or
return to
As above
As above
As above
As above
-------
5-01-79
Section 3.7.2
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 are designed for the
equipment specified by Method 8 and
described in the previous section. A
laboratory log book of all calibrations
must be maintained. Table 2.1 at the
end of this section summarizes the
quality assurance functions for
calibration.
2.1 Metering System
2.1.1 Wet Test Meter • Wet test
meters are calibrated by the manufac-
turer to an accuracy of ±0.5%. The
calibration of the wet test meter must
be checked initially upon receipt and
yearly thereafter. A wet test meter
with a capacity of 3.4 mVh (1 20
ftVh) will be necessary to calibrate
the dry gas meter. For large wet test
meters (>3L/rev), there is no
convenient method to check the
calibration. For this reason, several
methods are suggested, and other
methods may be approved by the
Administrator. The initial calibration
may be checked by any of the
following methods:
1. Certification from the manufac-
turer that the wet test meter is
within ±1% of true value at the
wet test meter discharge, so that
only a leak check of the system
is then required. Determine from
manufacturer if the air entering
the wet test meter should be
saturated.
2. Calibration by any primary air or
liquid displacement method that
displaces at least one complete
revolution of the wet test meter.
3. Comparison against a smaller
wet test meter that has
previously been calibrated
against a primary air or liquid
displacement method, as
described in Section 3.5.2.
4. Comparison against a dry gas
meter that has previously been
calibrated against a primary air
or liquid displacement method.
The calibration of the test meter
should be checked annually. The
calibration check can be made by the
same method as that of the original
calibration, with the exception that
the comparison method need not be
recalibrated if the calibration check is
.within ±1% of the true value. When
this agreement is not obtained, then
the comparison method or wet test
meter must be recalibrated against a
primary air or liquid displacement
method.
2.1.2 Sample Meter System - The
sample meter system—consisting of
the pump, vacuum gauge, valves,
orifice meter, and dry gas meter—is
initially calibrated by stringent
laboratory methods before it is used in
the field. After the initial acceptance,
the calibration is rechecked after each
field test series. This recheck is
designed to provide the tester with a
method that can be used more often
and with less effort to ensure that the
calibration has not changed. When
the quick check indicates that the
calibration factor has changed, the
tester must again use the complete
laboratory procedure to obtain the
new calibration factor. After recali-
bration, the metered sample volume
must be multiplied by either the initial
or the recalibrated calibration factor—
that is, the one that yields the lower
gas volume for each test run.
Before initial calibration of the
metering system, a leak check should
be conducted. The meter system
should be leak free. Both positive
(pressure) and negative (vacuum) leak
checks should be performed.
Following is a pressure leak-check
procedure that will check the
metering system from the quick
disconnect inlet to the orifice outlet
and will check the orifice-inclined
manometer:
1. Disconnect the orifice meter line
from the downstream orifice
pressure tap (the one closest to
the exhaust of the orifice), and
plug this tap.
2. Vent the negative side of the
inclined manometer to the
atmosphere. If the inclined
manometer is equipped with a
three-way valve, this step can be
performed by merely turning the
three-way valve that is on the
negative side of the orifice-
inclined manometer to the vent
position.
3. Place a one-hole rubber stopper
with a tube through its one hole
in the exit of the orifice, and
connect a piece of rubber or
plastic tubing to the tube, as
shown in Figure 2.1.
4. Open the positive side of the
orifice-inclined manometer to the
"reading" position. If the inclined
manometer is equipped with a
three-way valve, this will be the
line position.
5. Plug the inlet to the vacuum
pump. If a quick disconnect with
a leak-free check valve is used
on the control module, the inlet
will not have to be plugged.
6. Open the main valve and the
bypass valve.
7. Blow into the tubing connected
to the end of the orifice until a
pressure of 127 to 178 mm (5 to
7 in.) H20 has built up in the
system.
8. Plug or crimp the tubing to main-
tain this pressure.
9. Observe the pressure reading for
a 1-min period. No noticeable
movement in the manometer
fluid level should occur. If the
meter box has a leak, a bubbling-
type leak-check solution may aid
in locating the leak(s).
After the metering system is deter-
mined to be leak free by the positive
leak-check procedure, the vacuum
system to and including the pump
should be checked by plugging the air
inlet to the meter box. If a quick
disconnect with a leak-free stopper
system is presently on the meter box,
then the inlet will not have to be
plugged. Turn the pump on, pull a
vacuum within 7.5 cm (3 in.) Hg of
absolute zero, and observe the dry gas
meter. If the leakage exceeds 1.5 x
10"1 mVmin (0.005 ftVmin), the
leak(s) must be found and minimized
until the above specifications are
satisfied.
Leak checking the meter system
before initial calibration is not manda-
tory, but is recommended.
Note - For metering systems having
diaphragm pumps, the normal leak-
check procedure described above will
not detect leakages within the pump.
For these cases, the following leak-
check procedure is suggested: make a
10-min calibration run at 0.00057
mVmin (0.02 ftVmin); at the end of
the run, take the difference of the
measured wet test meter and dry gas
meter volumes; divide the difference
by 10, to get the leak rate. The leak
rate should not exceed 0.00057
mVmin (0.02 ftVmin).
-------
Section 3.7.2
5-01-79
Initial calibration - The dry gas
meter and orifice meter can be
calibrated simultaneously and should
be calibrated when first purchased
and any time the posttest check yields
a Y outside the range of the
calibration factor Y±0.05Y. A
calibrated wet test meter (properly
sized, with ±1% accuracy) should be
used to calibrate the dry gas meter
and the orifice meter.
The dry gas meter and the orifice
meter should be calibrated in the
following manner:
1. Before its initial use in the field,
leak check the metering system,
as described in Subsection 2.1.2.
Leaks, if present, must be elimi-
nated before proceeding.
2. Assemble the apparatus, as
shown in Figure 2.2, with the
wet test meter replacing the
probe and impingers— that is,
with the outlet of the wet test
meter connected to a needle
valve that is connected to the
inlet side of the meter box and
with the inlet side of the wet test
meter connected to an impinger
with water or to a saturator.
3. Run the pump for 15 min with
the orifice meter differential (AH)
set at 12.7 mm (0.5 in.) HaO to
allow the pump to warm up and
to permit the interior surface of
the wet test meter to be wetted.
4. Adjust the needle valve so that
the vacuum gauge on the meter
box will read between 50 and
100 mm (2 to 4 in.) Hg during
calibration.
5. Collect the information required
in the forms provided (Figure
2.3A or 2. 38). Sample volumes,
as shown, should be used.
6. Calculate Yi for each of the six
runs, using the equation in
Figure 2.3A or B under the Yi
column, and record the results
on the form in the space
provided.
7. Calculate the average Y for the
six runs using the following
equation:
Record the average on Figure 2.3A
or B in the space provided.
8. The dry gas meter should be
cleaned, adjusted, and recali-
brated, or rejected if one or more
values of Y fall outside the
interval Y ±0.02Y. Otherwise,
the average Y (calibration factor)
is acceptable and will be used for
future checks and subsequent
test runs.
9. Calculate AH@i for each of the
six runs using the equation in
Figure 2.3A or B under the AH@i
column, and record on the form
in the space provided.
10. Calculate the average AH@ for
the six runs using the following
equation:
AH@ =•
AH@,
AH@«
AH@2 + AH@3
AH@5 + AH@8
6
Record the average on Figure 2.3A
or B in the space provided.
11. Adjust the orifice meter or reject
it if AH@i varies by more than
±3.9 mm (0.15 in.) H20 over the
range of 10 to 100 mm (0.4 to
4.0 in.) H20. Otherwise, the
average AH@ is acceptable and
will be used for subsequent test
runs.
Posttest calibration check - After
each field test series, conduct a
calibration check of the metering
system, as in Subsection 2.1.2, except
for the following variations:
1. Three calibration runs at a single
intermediate orifice meter setting
may be used with the vacuum
set at the maximum value
reached during the test series.
The single intermediate orifice
meter setting should be based on
the previous field test. A valve
must be inserted between the
wet test meter and the inlet of
the metering system to adjust
the vacuum.
2. 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 during the
test series.
3. Use Figure 2.4A or 2.48, and
record the required information.
If the calibration factor Y devi-
ates by <5% 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 Y deviates by >5%,
recalibrate the metering system
(as in Subsection 2.1.2), and use
whichever meter coefficient
(initial or recalibrated) yields the
lower gas volume for each test
run.
Alternate procedures—for example,
using the orifice meter coefficients—
may be used, subject to the approval
of the Administrator.
2.2 Thermometers
The thermometers used to measure
the temperature of gas reaving the
impinger train should be initially
compared with a mercury-in-glass
thermometer that meets ASTM E-1
No. 3C or 3F specifications as follows:
1. Place both the mercury-in-glass
and the dial type or equivalent
thermometer in an ice bath.
Compare readings after the bath
stabilizes.
2. Allow both thermometers to
come to room temperature.
Compare readings after both
stabilize.
3. Accept the dial type or equivalent
thermometer if values agree
within ±1°C (2°F) at both points.
If the difference is greater than
±1°C (2°F), the thermometer
should be either adjusted and
recalibrated until the above
criteria are met, or rejected.
4. Prior to each field trip, compare
the temperature reading of the
mercury-in-glass thermometer at
room temperature with that of
the meter thermometer in the
equipment. If the readings are
not within ±2°C (4°F) the meter
thermometer should be replaced
or recalibrated.
The thermometers used to measure
the metered sample gas temperature
should also be initially compared with
a mercury-in-glass thermometer that
meets ASTM E-1 No. 3C or 3F
specifications:
1. Place the dial type or equivalent
thermometer and the mercury-in-
glass thermometer in a hot water
bath, 40°to50°C(105°to
122°F). Compare readings after
the bath stabilizes.
2. Allow both thermometers to
come to room temperature.
Compare readings after
thermometers stabilize.
3. Accept the dial type or equivalent
thermometer if: (1) values agree
within ±3°C (5.4°F) at both
points or (2) 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 pretest sampling checks
form (Figure 2.5).
4. Prior to each field trip, compare
the temperature reading of the
mercury-in-glass thermometer at
room temperature with that of
the meter system thermometer.
The values or corrected values
should be within ±6°C (10.8°F)
of one another, or the meter
thermometer should be replaced
-------
5-01-79 3 Section 3.7.2
or recalibrated. Record any
temperature correction factors on
Figure 2.5jor on a similar form.
2.3 Barometer
The field barometer should be ad-
justed initially and before each test
series to agree within ±2.5 mm (0.1
in.) Hg of the mercury-in-glass barom-
eter or the station pressure value re-
ported from a nearby National Weath-
er Service station, corrected for eleva-
tion. The tester should be aware that
the reported pressure is normally cor-
rected to sea level; the tester should
request the uncorrected reading. The
correction for elevation difference
between the weather station and the
sampling point should be applied at a
rate of minus 2.5 mm Hg per 30 m
(minus 0.1 in. per 100ft). Record re-
sults on Figure 2.5 or on a similar
form.
2.4 Probe Nozzle
The nozzle should be stainless steel
(316) or glass with sharp, tapered
leading edges. The angle of taper
should be <30°, and the taper should
be on the outside to preserve a
constant ID. Also the probe nozzles
should be calibrated before their
initial use in the field. Using a
micrometer, measure the ID of the
nozzle to the nearest 0.025 mm
(0.001 in.). Make three separate
measurements using different
diameters each time, and then
average the measurements. The
difference between the high and low
numbers should not exceed 0.1 mm
(0.004 in.).
When nozzles become nicked,
dented, or corroded, they should be
reshaped, sharpened, and recalibrated'
before use. Each nozzle should be
permanently and uniquely identified.
Figure 2.6 is an example sample
nozzle calibration data form.
2.5 Pitot Tube
The type-S Pitot tube assembly
should be calibrated according to the
procedure outlined in Method 2,
Section 3.1.2.
2.6 Trip Balance
The trip balance should be
calibrated initially by using Class-S
standard weights and should be
within ±0.5 g of the standard weight.
Adjust or return the balance to the
manufacturer if limits are not met.
-------
Section 3.7.2
6-01-79
Rubber
Rubber Stopper
Tubing
Orifice
Blow into Tubing
until Manometer Reads
5 to 7 in. H20
Water Column
Figure 2.1. Positive leak check of metering system.
Water Out
Level Adjust
Impinger
or Saturator
Figure 2.2, Sample meter system calibration setup.
-------
6-01-79
Section 3.7.2
n?f. S/ft/78
Barometric pressure, Pti- J»).
°F
*/
b (ta + 460)
Va (ft, + - ) ffw + 460)
f/2 9, 6 *S) (fff)
fl.HffW. & 7) t9*L f )
: 0.037 7 AW ! f
/°b /'fo + 460; L
(0-0'}/7 ) (O-f 7
(21'6'f) (?*/*?)
ft* + 460) Q 1
V
w J
r c f?f- rj ( fi'?fj'
i y
° If there is only one thermometer on the dry gas meter, record the temperature under ta.
Nomenclature:
l/w - Gas volume passing through the wet test meter, ft3.
Va = Gas volume passing through the dry test meter, ft3.
tw = Temperature of the gas in the wet test meter. °F.
tai - Temperature of the inlet gas of the dry test meter. °F.
tAo-Temperature of the outlet gas of the dry test meter. °C.
ta = Average temperature of the gas in the dry test meter, obtained by the average t^ and t
-------
Section 3.7.2
5-01-79
Date
Barometric pressure, Pb =.
. mm Hg.
, Meter box number
Calibrated by
Orifice
manometer
setting
(&H),
mm HiO
10
25
40
50
75
100
Gas volume-
Wet test
meter
tvj.
m3
0.15
0.15
0.30
0.30
0.30
0.30
Dry gas
meter
(VJ.
m3
2*632.0
*/.Btoo
Temperature"
Wet test
meter
M
°C
19
M
Dry gas meter
Inlet
(t*J.
°C
to
/9
Outlet
H'J.
°C
/0
n
A verage
(ta).e
°C
IB
Time
(Q).
min
»%
Y;
,<$(>
A verage
A/y@,
23
AW
10
25
40
50
75
100
AW
13.6
0.7
1.8
2.94
3.68
5.51
7.35
V»Pt,(ta + 273)
A//1
Va(Ph + 13.6)(t* + 273)
ft./r} 17*6) L11O
fO,JSZ)f1?7)f2.9/)
2
0.007 1 7 A// r ftw + 273;0 1
f\U(g, - "'""' '' "" l"» *-' L d. if 2. J
"If there is only one thermometer on the dry gas meter, record it under to-
Nomenclature:
V* = Gas volume passing through the wet test meter, m3.
Va = Gas volume passing through the dry test meter, m3.
Tw = Temperature of the gas in the wet test meter, °C.
ta, = Temperature of the inlet gas of the dry test meter, °C.
tao=Temperature of the outlet gas of the dry test meter, °C.
td = A verage temperature of the gas in the dry test meter, obtained by the average td, and ta0, °C.
AA/ = Pressure differential across orifice, mm HzO.
Y\ = Ratio of accuracy of wet test meter to dry test meter for each run. Tolerance Y, = Y ±0.02 Y.
Y = Average ratio of accuracy of wet test meter to dry test meter for all six runs. Tolerance Y =Y ±0.01 Y.
i = Orifice pressure differential at each flow rate that gives 0.021 m3 of air at standard conditions for each calibration
run. mm H20. Tolerance AW@i = AW@ ±3.8 mm H20 (recommended).
0 = Time of each calibration run, min.
Pt, = Barometric pressure, mm Hg.
Figure 2.38. Dry gas meter calibration data fmetric units).
-------
Test numbers
Date
Meter box number
~ r
?/*»+
Barometric pressure, Pt, =
in. Hg
Dry gas meter number
^ 7
Pretest Y
Orifice
manometer,
setting.
in. HZO
/•*//
Gas volume
wet test
meter
(VJ,
ft3
10
10
10
Gas volume
dry gas
meter
IV*).
ft3
B7L, ?2V
Temperature
Wet test
meter
°F
7£
Dry gas meter
Inlet
°F
Qt>
Outlet
°F
7?
Average
°F
74
Time
(QJ.
min
/?.&
Vacuum
setting
in. Hg
^
Y,
OW
vJPt, + A/ylftw +• 460)
I 13.6\
f> (28- 72)\7 f +44.O )
/ft223(28.72+/.4///3.6> (72+4&Q
Y=
Nl
to
1 // there is only one thermometer on the dry gas meter, record the temperature under to.
where
Vm = Gas volume passing through the wet test meter, ft3.
Va - Gas volume passing through the dry test meter, ft3.
ty» = Temperature of the gas of the wet test meter, °F.
to, = Temperature of the inlet gas of the dry test meter, °F.
t.
Y, = Ratio of accuracy of wet test meter to dry test meter for each run. •
Y=Average ratio of accuracy of wet test meter to dry test meter for all three runs.
Tolerance = Pretest Y +O.05Y
Pt, = Barometric pressure, in. Hg.
0 -Time of calibration run, min.
CO
CO
vl
k>
Figure 2.4A. Posttest meter calibration data form (English units).
-------
Date.
Test numbers
ABI-3
Meter box number.
FM-7
Plant
Acme.
Barometric pressure. Pt> - .
3^
Gas volume
wet test
meter
(VJ.
m3
0*6
Gas volume
dry gas
meter
m3
?0- /7*/2-
/^- ^72^
Temperature
Wet test
meter
(U
°C
a/
Dry gas meter
Inlet
°V
)}.?
Outlet
°C
•*/.r
Average
°C
*
Time
(Q).
min
I)ST>
Vacuum
setting
mm Hg
7r
Y,
0-&f0
Y V*Pt,(ta + 273)
[ Tzel
0*}0('***)t2f'*+m
0. joll f7*c +2£)(?/t2
•
Y=
CO
a
n
s.
o
3
w
vl
NJ
8 If there
where
l/w
Va
t „
ta j
ta0
t a
A//
= Gas volume passing through the wet test meter, m3.
= Gas volume passing through the dry test meter, m3.
= Temperature of the gas in the wet test meter. °C.
= Temperature of the inlet gas of the dry test meter, °C.
Temperature of the outlet gas in the drv test meter. °C.
Average temperature of the gas in the dry test meter, obtained by the average of ta, and ta
= Pressure differential across orifice, mm Hf>.
= Ratio of accuracy of wet test meter to dry test meter for each run.
= Aver age ratio of accuracy of wet test meter to dry test meter for all three runs.
Tolerance = Pretest Y +O.05Y
- Barometric pressure, mm Hg.
- Time of calibration run, min.
01
6
vl
«£>
Figure 2.4B. Posttest meter calibration data form (metric units).
-------
5-01-79 9 Section 3.7.2
Date 3-/S-7& Calibrated by
Meter box number &vn -'/ AW@ /. V/
Dry Gas Meter"
Pretest calibration factor = Q3&io. (within ±2% of the average factor for each calibration run).
Impinger Thermometer
Was a pretest temperature correction used? — yes
// yes, temperature correction _ (within ±1°C (2°F) of reference values for calibration and within ±2°C (4°F) of
reference values for calibration check).
Dry CBS Meter Thermometer
Was a pretest temperature correction made? — yes _*£. no.
If yes. temperature correction - (within ±3°C (5.4°F) of reference values for calibration and 6°C (10. 8°F) of
reference values for calibration check).
Barometer
Was the pretest field barometer reading correct (within ±2.5 mm(0. 1 in.)Hg of mercury -in -glass barometer)? _K£ yes
— no.
'Most significant items/parameters to be checked.
Figure 2.5. Pretest samp/ing checks.
-------
Section 3.7.2
10
6-01-79
Table 2.1. Activity
Apparatus
Wet test meter
Dry gas meter
Thermometers
Barometer
Probe nozzle
Trip balance
Type-S Pilot
tube
Matrix for Calibration of Equipment
Acceptance limits
Capacity of at least
3.4 m3/h (120 ft3/h)
and an accuracy within
±1.0%
Y, = Y±0.02 Yata
flow rate of 0.02-0.03
m3/min (0.66-1)
Impinger thermometer
±1°C (2°F); dry gas
meter thermometer
within ±3°C {5.4° f) over
range
±2.5 mm (0. 1 in.) Hg of
mercury-in-g/ass
barometer
Average of three ID
measurements of nozzle;
difference between high
and low not to exceed
0. 1 mm (0.004 in.).
ap r <30°
Standard weights mea-
sured within
-------
5-01-79
Section 3.7.3
3.0 Presampling Operations
The quality assurance functions for
presampling preparations 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 form, and packing list.
3.1.1 Sampling Train - The
schematic of the Method 8 sampling
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 reference
method, Section 3.7.10.
3.1.2 Probe and Nozzle - The probe
and nozzle should be cleaned
internally by brushing first with tap
water, then with deionized distilled
water followed by acetone, and finally
allowed to dry in the air. In extreme
cases, the glass probe liner can be
cleaned with stronger reagents. The
objective is to leave the glass liner
free from contaminants. The probe
heating system should be checked to
see that it is operating properly. The
probe must be leak free at a vacuum
of 380 mm (15 in.) Hg when sealed at
the inlet or tip.
3.1.3 Impingers. Filter Holder, and
Glass Connections - All glassware
should be cleaned first 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 Pump - The vacuum pump and
oiler should be serviced as recom-
mended by the manufacturer, every 3
mo, or after the 10th test (whichever
comes first), or upon erratic behavior
(nonuniform or insufficient pumping
action).
3.1.5 Dry Gas Meter - A dry gas
meter calibration check should be
made in accordance with the
procedure in Section 3.7.2.
3.1.6 Silica>Gel - Either dry the
used silica gel at 120° - 150°C (248°
-302°F) or weigh out fresh silica gel
in several 200- to 300-g portions in
airtight containers to the nearest 0.5
g. Record the total weight (silica gel
plus container) on each container. The
silica gel does not have to be weighed
if the moisture content is not to be
determined.
3.1.7 Filters - Check filters visually
against light for irregularities, flaws,
or pinhole leaks. The filters do not
have to be weighed, labeled, or
numbered.
3.1.8 Thermometers - The ther-
mometers 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
the mercury-in-glass barometer or the
weather station reading after making
an elevation correction, prior to each
field trip.
3.2 Reagents and
Equipment
3.2.1 Sampling - The first impinger
solution (80% isopropanol) is prepared
by mixing 800 ml of reagent grade or
certified ACS isopropanol (100%) with
200 ml of deionized distilled water.
The second and third impinger
absorbing reagent (H202, 3%) is
prepared by diluting 100 ml of 30%
H2O2 to 1 L (1000 ml) with deionized
distilled water. The 3% H20a should
be prepared fresh daily, using certified
ACS reagent grade components.
Solutions containing isopropanol must
be kept in sealed containers to
prevent evaporation and must be
prepared fresh for each test series.
3.2.2 Sample Recovery - Deionized
distilled water and 80% isopropanol
are required on site for quantitative
transfer of impinger solutions to
storage containers. The water and
isopropanol are used to clean the
sampling train in the process of
sample recovery.
3.3 Packing Equipment for
Shipment
The condition of equipment may
depend upon the careful packing of
equipment with regard to (1)
accessibility in the field, (2) care of
movement on site, and (3) optimum
functioning of measurement devices
in the field. Equipment should be
packed under the assumption that it
will receive severe treatment during
shipping and field operations. One
major consideration in shipping cases
is the construction materials.
3.3.1 Probe - Pack the probe in a
case protected by polyethylene foam
or other suitable packing material. The
inlet and outlet should be sealed and
protected from breakage. An ideal
container is a wooden case, or
equivalent, lined with foam material
in which separate compartments are
cut to hold individual devices. The
case, equipped with handles or eye-
hooks that can withstand hoisting,
should be rigid enough to prevent
bending or twisting of the devices
during shipping and handling.
3.3.2 Impingers, Connectors, and
Assorted Glassware - All impingers
and glassware should be packed in
rigid containers and protected by
polyethylene foam or other suitable
packing material. Individual
compartments for glassware help to
organize and protect each individual
item.
3.3.3 Volumetric Glassware - A
sturdy case lined with polyethylene
foam material protects drying tubes
and assorted volumetric glassware.
3.3.4 Meter Box - The meter box—
which contains the manometers,
orifice meter, vacuum gauge, pump,
dry gas meter, and thermometers—
should be packed in a rigid shipping
container unless its housing is
sufficient to protect components
during travel. Additional pump oil
should be packed if oil is required for
its operation. It is advisable to always
ship a spare meter box in case of
equipment failure.
3.3.5 Wash Bottles and Storage
Containers - Storage containers and
miscellaneous glassware should be
packed in rigid foam-lined containers.
-------
Section 3.7.3
5-01-79
Apparatus
check
Probe
Type glass liner
Rnrnsilirate
fjuartr
Heated
Leak checked
Nozzle
nioss
Stain/ess steel
Other
Pilot Tube
Type
Other
Properly
attar.herl
Mnrlifir.atinnK
r0
Differential
Pressure Gauge
Inclined manome-
ter
f)tr>er
Filter Holder
Borosilicate glass
Glass frit
Gasket
Kilirnne
Teflnn
Vitnn
Condenser
Impingers
Greenburg-Smith
Modified
Greenburg-Smith
Impinger Temperature
Sensor
Thermnmeter
nther
ralihraterl
Acceptable
Yes
IX
IX
IX
IX
«x
\x-
.««/
iX
»x
IX
\s
•
IX
\x
•X
No
\
Quantity
required
«-fc'^
3 *t?S
v-4"^
((S"
/
(?-0^5~
i"
<^
H
y
ffearfy
Ves
iX
I/
(X
IX
•
uX
tX
I*'
tX
No
Loaded and packed
w
«x-
iX
iX
ix-
IX
i/
iX
IX
•X*
Figure 3, /. Example of a pretest preparation checklist.
-------
5-01-79
Section 3.7.3
Apparatus
check
Other
Barometer
Mprriiry
Anerniii
Other
ralihratvrl*
Stack Temperature Sensor
Tyr>i>
ralihrateri*
Reagents
Distilled water
Hydrogen peroxide
(30%)
Isopropanol (8O%)
(checked for
peroxides)
Silica gel
Meter System
Pump leak free*
Orifice meter*
Dry gas meter*
Acceptable
Yes
IX
IX
»x
I/
^^
^/
tx
No
Quantity
required
I
*
lyJ
2.
Ready
Yes
-
-
IX
^
No
Loaded and packed
-
"
tx
(X
tx
* Mosf significant items/parameters to be checked.
figure 3.1. (continued)
-------
Section 3.7.3
5-01-79
Table 3.1. Activity
Operation
Apparatus
Probe
Impingers, fil-
ter holders.
and glass con-
nectors
Pump
Dry gas meter
Reagents and
Equipment
Sampling
Sample
recovery
Package Equip-
ment for Ship-
ment
Probe
Impingers, con-
nectors,' and
assorted
glassware
Pump
Meter box
Wash bottles
and storage
containers
Matrix for Presampling Operations
Acceptance limits
1. Probe liner should
be free of contaminants
and constructed of boro-
silicate glass, or
quartz, or the equiva-
lent (no metal liners)
2. Probe must be leak
free at 380 mm (15 in.)
Hg
3. Probe must prevent
condensation of mois-
ture
Clean, free of breaks,
cracks, leaks, etc.
Maintain a smooth sam-
pling rate of about
0.3-0.5 m*/ min(1 -1.7
ft3/min) at up to 380
mm (15 in.) Hg vacuum
at pump inlet
±2% of calibration
factor and clean
All reagents must be
certified ACS or reagent
grade
Deionized distilled wa-
ter on -site and leak-
free sample storage
bottles as specified in
Sec. 3.7.1
Pack in rigid contain-
er and protect with
polyethylene foam
Pack in rigid contain-
ers and protect with
polyethylene foam
Sturdy case lined with
polyethylene foam ma-
terial or as part of
meter box
Meter box case and/or
additional material to
protect train compon-
ents; pack spare meter
box
Pack in rigid foam-
lined containers
Frequency and method
of measurement
1 . Clean probe in-
ternally by brushing
with tap deionized
distilled water, then
acetone; allow to dry
in air before test
2. Visually check be-
fore test
3. Check out heating
system initially and
when moisture cannot
be prevented during
testing (Sec. 3. 7. 1)
Clean with detergent
and tap water, then
deionized distilled
water
Service every 3 mo or
upon erratic behavior;
check oiler jars every
10 tests
Calibrate according
to Sec. 3.7.2. and
check for excess oil
Prepare fresh daily
and store in sealed
containers
Water and reagent
grade isopropanol are
used to clean
impinger after testing
and prior to taking
sample.
Pack prior to each
shipment
Pack prior to each
shipment
As above
As above
As above
Action if
requirements
are not met
1. Retrace
cleaning pro-
cedure and
assembly
2. Replace
3. Repair or
replace
Repair or
discard
Repair or
return to
manufacturer
As above
Prepare new
reagent
Prepare new
reagent
Repack
Repack
As above
As above
As above
-------
5-01-79
Section 3.7.4
4.0 On-Site Measurements
The on-site measurement activities
include transporting the equipment to
the test site, unpacking and
assembling the equipment, making
duct measurements, velocity traverse,
determination of molecular weight
and stack gas moisture content (in
certain cases the moisture content
can be assumed to be zero), sampling
for sulfuric acid mist and sulfur
dioxide, and recording data. Table 4.1
at the end of this section summarizes
the quality assurance activities for on-
site measurements. A copy of all field
data forms mentioned are contained
in Section 3.7.12.
4.1 Transport of Equipment
to the Sampling Site
The most efficient means of trans-
porting the equipment from ground
level to the sampling site should be
decided during the preliminary site
visit (or prior correspondence). Care
should be exercised to prevent
damage to the test equipment or
injury to test personnel during the
moving phase. A laboratory type area
should be designated for preparation
of absorbing reagents, placing the
filter in the filter holder, charging of
the impingers, sample recovery, and
documentation. This area should be
fairly clean and should not have
excessive drafts.
4.2 Sampling
The on-site sampling includes the
following steps:
1. Preliminary measurements and
setup,
2. Preparation and/or addition of
the absorbing reagents to the im-
pingers,
3. Placement of the filter in the
filter holder,
4. Setup of the sampling train,
5. Preparation of the probe,
6. Leak check of entire train,
7. Insertion of the probe into the
stack,
8. Sealing the port,
9. Checking the temperature of the
probe,
10. Sampling at designated points,
and
11. Recording of the data.
A final leak check of the train must
always be performed upon completion
of sampling.
4.2.1 Preliminary Measurements
and Setup - The sampling site location
should be selected in accordance with
Method 2. If this is not possible due to
duct configuration or other reasons,
the sampling site location should be
approved by the Administrator. A 115-
V, 30-amp electrical supply is
necessary to operate the standard
sampling train. Measure the stack and
either determine the minimum
number of traverse points by Method
1 or check the traverse points
determined from the preliminary site
visit, Section 3.0 of this Handbook.
Record all data on the traverse point
location form, as shown in Section
3.0. These measurements will be
used to locate the Pilot tube and the
sampling probe during preliminary
measurements and actual sampling.
4.2.2 Stack Parameters - Check the
sampling site for cyclonic or
nonparallel flow as described in
Method 1 fSection 3.0). The sampling
site must be acceptable before a valid
sample can be made. Determine the
stack pressure, temperature, and the
range of velocity heads using Method
2; it is recommended that a leak
check of the velocity pressure system
(Method 2) be performed. Be sure that
the proper differential pressure gauge
is chosen for the range of velocity
heads encountered (see Method 2).
Determine the moisture content using
the approximation Method 4 or its
alternatives for the purpose of setting
the isokinetic sampling rate. If the
particular source has been tested
before or a good estimate of the
moisture is available, this should be
sufficient. The Reference Method uses
the condensate collected during
sampling to determine the moisture
content used in final calculations.
Note - For contact-process sulfuric
acid plants, the moisture can be
assumed to be zero if a scrubber is
not in use.
Determine the dry molecular weight
of the stack gas, as required in
Method 2. If an integrated gas sample
is required, follow Method 3
procedures and take the sample
simultaneously with, and for the same
total length of time as, the sulfuric
acid mist and SOz sample run.
Sampling and analytical data forms
for molecular weight determinations
are presented in Method 3.
Using the stack parameters
obtained by these preliminary
measurements, the nomograph can be
set up as outlined in APTD-0576. An
example of a nomograph data form is
presented in Method 5.
Method 8 sampling is performed
isokinetically like Method 5, but the
sampling rate is not to exceed 0.03
mVmin (1.0 ftVmin) during the test.
To accomplish this, select a nozzle
size based on the range of velocity
heads, so that it is not necessary to
change the nozzle size in order to
maintain isokinetic sampling rates.
Select also a nozzle that will not allow
the maximum sampling rate to exceed
0.03 mVmin (1.0 ftVmin) during the
run. Check the maximum AH, using
the following equation:
Maximum AH < 109P"MAH@
Tm
Equation 4-1
where
Maximum AH = pressure differential
across the orifice, in. HjO,
that will produce a flow of
1.0 ftVmin;
Pm = pressure of the dry gas
meter, in. Hg;
M = molecular weight of stack
gas;
AH@ = pressure differential across
the orifice that will produce a
flow of 0.75 scfm, in. H2O;
and
Tm = temperature of the meter, °R.
This maximum AH will limit the
sampling flow rate to <0.03 mVmin
(1.0 ftVmin).
During the run, do not change the
nozzle size. Install the selected nozzle
using a Viton-A o-ring when stack
temperatures are <260°C (500°F) and
using an asbestos string gasket when
temperatures are higher (see APTD-
0576 for details). Other connecting
systems such as Teflon ferrules may
be used. Mark the probe with heat re-
sistant tape or by some other
technique to denote the proper
distance into the stack or duct for
each sampling point.
Select a suitable probe liner and
probe length so that all traverse
points can be sampled. For large
stacks, consider sampling from
opposite sides of the stack to reduce
the length of the probe.
-------
Section 3.7.4
6-01-79
Select a total sampling time greater
than or equal to the minimum total
sampling time specified in the test
procedures for the specific industry so
that (1) the sampling time per point is
>2 min (or some greater time interval
specified by the Administrator) and (2)
the sample volume taken (corrected to
standard conditions) will exceed the
required minimum total gas sample
volume (normally 1.15 dscm (40.6
dscf)). The latter can be based on an
approximate average sampling rate.
It is recommended that the number
of minutes sampled at each point be
an integer or an integer plus one-half
min, in order to avoid timekeeping
errors.
In some circumstances (e.g., batch
cycles), it may be necessary to sample
for shorter times at the traverse
points and to obtain smaller gas
sample volumes. In these cases, the
Administrator's approval must first be
obtained.
4.2.3 Preparation and/or Addition of
Absorbing Reagents and Filter to
Collection System - Absorbing
reagents can be prepared on site if
necessary, according to the directions
given in Section 3.7.3. A pipette or
graduated cylinder should be used to
place 100 ml of 80% isopropanol into
the first impinger. Be sure that the
pipette or graduated cylinder was not
used previously to add the H202 solu-
tion. It is suggested that the
graduated cylinders or pipettes be
marked to reduce the chance of
interchanging. Place 100 ml of 3%
HaOz into the second impinger and
100 ml of 3% H202 into the third
impinger. Also, place approximately
200 g of silica gel into the fourth
impinger.
Note - If moisture content is to be
determined by impinger analysis,
either weigh each of the first three
impingers (plus absorbing solution) to
the nearest 0.5 g and record these
weights, or determine to the nearest 1
ml volumetrically. The weight of the
silica gel (or silica gel plus container)
must also be determined to the
nearest 0.5 g, and recorded.
Using tweezers or clean disposable
surgical gloves, place a filter in the
filter holder. Be sure that the filter is
properly centered and that the gasket
is properly placed in order to prevent
the sample gas stream from
circumventing the filter. Check the
filter for tears after assembly is
completed.
4.2.4 Assembling Sampling Train-
During preparation and assembly of
the sampling train, keep all sample
train surfaces that are to be exposed
to the sample covered until just prior
to assembly or until sampling is about
to begin.
Assemble the sampling train as
shown in Figure 1.1, using (if
necessary) a very light coat of silicone
grease on all ground-glass joints.
Apply grease only to the outer portion
of the glass joint to avoid the
possibility of contaminating the
sample. Place crushed ice and water
around the impingers.
4.2.5 Leak Checks - Leak checks are
necessary to assure that the sample
has not been biased low by dilution
air. The Reference Method specifies
that leak checks be performed at
certain times. These are discussed
below in this subsection.
Pretest leak check - A pretest leak
check is'fecommended, but not
required. If the tester opts to conduct
the pretest leak check, the following
procedure should be used:
1. After the sampling train has
been assembled, turn on the
probe heating system, set it at
the desired operating
temperature, and allow time for
the temperature to stabilize.
2. If a Viton A o-ring or other leak-
free connection is used in
assembling the probe nozzle to
the probe liner, leak check the
train at the sampling site by
plugging the nozzle and pulling a
380 mm (15 in.) Hg vacuum.
Note - A lower vacuum may be
used, if it is not exceeded during
the test.
If an asbestos string is used for
the probe gasket, do not connect
the probe to the train during the
leak check. Instead, leak check
the train by first plugging the
inlet to the first impinger and
pulling a 380mm (15 in.) Hg
vacuum (see note immediately
above). Then connect the probe
to the train and leak check at
about 25 mm (1 in.) Hg vacuum;
alternatively, the probe may be
leak checked with the rest of the
sampling train in one step at a
vacuum of 380 mm (15 in.) Hg.
Leakage rates in excess of 4% of
the average sampling rate or at
0.00057 mVmin (0.02 ft3/ min),
whichever is less, are not
acceptable.
The following leak-check
instructions for the sampling train
described in APTD-0576 and APTD-
0581 may be helpful:
1. Start the pump with the bypass
valve fully open and the coarse
adjust valve completely closed.
2. Partially open the coarse adjust
valve and slowly close the bypass
valve until the desired vacuum is
reached. Do not reverse the
direction of the bypass valve; this
will cause hydrogen peroxide to
back up into the filter holder. If
the desired vacuum is exceeded,
either leak check at this higher
vacuum or end the leak check as
shown below and start over.
When the leak check is completed,
first slowly remove the plug from the
inlet to the probe or the first impinger
and then immediately turn off the
vacuum pump. This prevents the ab-
sorbing solution in the impingers from
being forced backward into the filter
holder and prevents the silica gel from
being entrained backward into the
third impinger. Visually check to be
sure that Hz02 did not contact the
filter and that the filter has no breaks,
and so forth.
Leak checks during the sample run
If during the sampling run a
component (e.g., a filter assembly)
change becomes necessary, a leak
check should be conducted
immediately before the change is
made. The leak check should be done
according to the procedure outlined
above, except that it should be done
at a vacuum equal to or greater than
the maximum value recorded up to
that point in the test. If the leakage
rate is found to be no greater than
0.00057 mVmin (0.02 ftVmin) or 4%
of the average sampling rate
(whichever is less), the results are
acceptable, and no correction will
need to be applied to the total volume
of dry gas metered; if, however, a
higher leakage rate is obtained, the
tester either should record the
leakage rate and plan to correct the
sample volume (as shown in Section
3.7.6 of this method) or should void
the sampling run.
Note - Be sure to record the dry gas
meter reading before and after each
leak check performed during and after
each test run so that the sample volume
can be corrected.
Immediately after component
changes, leak checks are again
optional; if such leak checks are done,
the procedure outlined above should
be used.
Posttest leak check - A leak check is
mandatory at the conclusion of each
sampling run. The leak check should
be done in accordance with the
procedures previously outlined, except
that it should be conducted at a
vacuum equal to or greater than the
maximum value reached during the
sampling run. If the leakage rate is
found to be no greater than 0.00057
-------
6-01-79
Section 3.7.4
mVmin (0.02 ft3Aiin) or 4% of the
average sampling rate (whichever is
less), the results are acceptable, and
no correction will tieed to be applied
to the total volume of dry gas
metered. If, however, a higher leakage
rate is obtained, the tester should
record the leakage rate and should
correct the sample volume as shown
in Section 3.7.6 of this method.
Note - Be sure to record the dry gas
meter reading before performing the
leak check in order to determine the
sample volume.
4.2.6 Sampling Train Operation -
Just prior to sampling, clean the
portholes to minimize the chance of
sampling any deposited material.
Paniculate matter can interfere with
the wet chemical analysis for sulfuric
acid mist. Verify that the probe
heating system is at the desired
temperature and that both the Pilot
tube and the nozzle are located
properly. Follow the procedure
outlined below for sampling:
1. Record the initial dry gas meter
readings, barometer readings,
and other data as indicated in
Figure 4.1.
2. Position the tip of the probe at
the first sampling point so that
the nozzle tip is pointing directly
into the gas stream; then turn on
the pump.
3. Immediately adjust the sample
flow to isokinetic conditions.
4. Take other readings required by
Figure 4.1 at least once at each
sampling point during each time
increment.
5. Record the dry gas meter
readings at the end of each
sampling time increment.
6. Repeat steps 3 through 5 for
each sampling point.
7. At the conclusion of each
traverse, turn off the pump,
remove the probe from the stack,
and record the final readings.
8. Conduct a leak check, as
described in Subsection 4.2.4, at
the conclusion of the last
traverse. This leak check is
mandatory. Record all leakage
rates. Note - If the velocity
determination is required for the
emissions calculation, a leak
check of the Pitot-tube-
manometer system is mandatory.
The procedures are detailed in
Section 4 of Method 2.
9. Disconnect the probe and then
cap the nozzle and the end of the
probe with polyethylene caps or
the equivalent. See Subsection
4.3 on how to recover the probe
contents.
10. Drain the ice bath, and purge the
remaining part of the train by
drawing clean ambient air
through the system for 15 min at
the average sampling rate.
Provide clean ambient air by
passing the air through a
charcoal filter, or use ambient air
without purification. See
Subsection 4.3 for details on
how to protect the probe from
contamination during purging,
and so forth. Note - Ambient air
that is in compliance with normal
state or Federal ambient air
standards for SOs will have less
than a 0.5% effect on the final
results when not cleaned by
passing it through a charcoal
filter.
During the sampling run, maintain
an isokinetic sampling rate within
±10% unless otherwise specified by
the Administrator. Adjust the
sampling flow rates when a 20%
variation in the velocity head reading
occurs. Make periodic checks of the
manometer level and zero during each
traverse. Vibrations and temperature
fluctuations can cause the manometer
zero to drift.
Periodically during the test, observe
the connecting line between the probe
and the first impinger for signs of
condensation. If signs do occur, adjust
the probe heater setting upward to
the minimum temperature required to
prevent condensation.
4.3 Sample Recovery
The Reference Method requires the
sample to be recovered from the
probe, the impingers, all connecting
glassware, and the filter. Sample
recovery should be performed in a
laboratory type area to prevent
contamination of the test sample.
Upon completion of sampling, the
probe should have been disconnected
and capped off with polyethylene caps
or the equivalent. Also, the impinger
section should be capped off with
polyethylene caps or the equivalent
upon completion of purging with clean
ambient air. Then the impinger box
and the sampling probe can be
transported safely to the clean-up
area without contaminating or losing
the sample.
4.3.1 Sulfuric Acid Mist Sample
Recovery - The sulfuric acid mist
(including SOs) sample is collected in
the probe, the first impinger, all
connecting glassware before the filter,
the front half of the filter holder, and
the filter. To recover the sample:
1. Transfer the contents of the first
impinger into a 250-ml
graduated cylinder. (If a moisture
content analysis is to be done,
each impinger and its contents
should be weighed to the nearest
0.5 g and recorded before
transferring its contents.)
2. Rinse the probe, the first
impinger, all connecting
glassware before the filter, and
the front half of the filter holder
with 80% reagent grade or
certified ACS isopropanol.
3. Add the rinse solution to the
graduated cylinder and dilute to
250 ml with 80% reagent grade
or certified ACS isopropanol.
4. Remove the filter with a pair of
tweezers, and add to the
solution; mix; and transfer to the
1000-ml storage containers.
Protect the solution from
evaporation.
5. Mark the level of liquid on the
container, and identify the
sample container. An example of
a sample label is shown in
Figure 4.2.
6. Place about 100 ml of the 80%
isopropanol in a polyethylene
bottle, and label the bottle for
use as a blank during sample
analysis.
4.3.2 Sulfur Dioxide Sample Re-
covery - The S02 is captured in the
second and third impingers and in all
connecting glassware. To recover the
SOs sample:
1. Transfer the solutions from the
second and third impingers to a
1000-ml graduated cylinder. (If a
moisture content analysis is to
be done, each impinger and its
contents should be weighed to
the nearest 0.5 g and recorded
before transferring its contents.)
2. Rinse all connecting glassware
(including back half of the filter
holder) between the filter and the
silica gel impinger with deionized
distilled water; add this rinse
water to the graduated cylinder;
and dilute to a volume of 1000
ml with deionized distilled water.
3. Transfer the solution to a storage
container; mark the level of liquid
on the container; and seal and
identify the sample container.
4. Place 100 ml of the absorbing
reagent (3% H202) in a polyethyl-
ene bottle, and label the bottle
for use as a blank during sample
analysis.
4.4 Sample Logistics (Data)
and Packing of Equipment
The above procedures are followed
until the required number of runs are
-------
Section 3.7.4 4 5-01-79
completed. Log all data on the form
shown in Figure 4.3. If the probe and
the glassware (impingers, filter holder,
and connectors) are to be used in the
next test, rinse all of the glassware
and the probe with deionized distilled
water. Rinse the probe, the first
impinger, all connecting glassware
before the filter, and the front half of
the filter holder with 80% isopropanol.
The following are recommended at
the completion of the test series:
1. Check all sample containers for
proper labeling (time and date of
test, location of test, number of
test, and any pertinent
documentation). Be sure that a
blank has been taken.
2. All data recorded during the field
test should be recorded and
duplicated by the best means
available. One set of data can
then be either mailed to the base
laboratory or given to another
team member or to the Agency;
the original data should be hand-
carried.
3. All sample containers and samp-
ling equipment should be exam-
ined for damage, and then
properly packed for shipment to
the base laboratory. All shipping
containers should be properly
labeled to prevent loss of
samples or equipment.
4. A quick check of the sampling
and sample recovery procedures
can be made using the data
form, Figure 4.4.
-------
Method 8 Field Test Data Form
Riant jJj
Location UnJ"\. \
Operator B P
fi
Probe length
Probe liner material A
Probe heater setting
Sheet.
.of.
Run number .
Sample box number
Meter box number _
Meter A//@ _
Ambient temperature
Barometric pressure 2".
Assumed moisture O
Static pressure **
C factor
Nozzle identification number 37
Nozzle diameter
Final leak rate
Vacuum during leak check
Remarks:
3 in. H<
Meter calibration Y LAI to
Pilot tube CP.
O.84-
Reference A/5.
Maximum &H.
on
6
(0
Traverse point
number
Start
i
i
*.
*
i
'
6»
7
IO
II
12.
Total or
Avg
Sampling
time
(Q).
min
O
f
/z>
4
4
4
I
o
f
f
•
'
o
If
Ml
r
y
60
Clock
time
24 h
II 52
JZZ2.
/2.3Z
!2Sft
Vacuum.
mm Hg
(in. Hg)
— •
2.Q
2.5
f.f
2.f
3 G
2. f
H.f
%,<'
3.0
3O
$.O
1LO
30
Stack
temperature
(TJ.
or* /ori
L» f f f
— •
120
12.1
/2 3
121
12.2.
11$
I2\
l£i
/23
I2\
12.1
W.7
Velocity
head
mm H^O
(in. H20)
— —
O.1S"
I.Of
/.Of
/.of
* wS^
.•i.
.6'
nfit
^™mm
*
\
4
I.Of
I.QO
,9f
Pressure
differential
across
orifice
meter.
mm H^O
(in. H20)
—
/« 9
ft
.
Qi
O
2.0
1.9
i.A
t-7
hi
/.4
?•&
I.Qf
i. f
/.89
Gas sample
volume,
m3 (H3)
II 1.41
II'
(It
t2'
I2i
*,/t
.&
I
?
t. 7f
S. 6(
1
/30. 3f
/**.//
14
14,
14
7^A
J.6I
•6.3J
A.OI
If 2.7 A
If A. f//
145.080
Gas sample tempera-
ture at dry gas meter
Inlet,
°C f°F)
70
«
4
7A
7^
ft*
f
f
f
t
t
\
i\
•
4
<
,
t
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t
\o
Outlet.
°C (QF)
~rq
77
72.
~i*t*
"7Q
A2.
&1
Af
07
82.6
Tempt
of gas
leavin
conde
last in
°C (°Ft
vature
9
nser or
ipinger,
1
— —
foh
ft/If
25
£2.
C*C)
£»/
A/
2a
^
£>*
t>(
f
v>
a
2
Figure 4.1. Method 8 field test data form.
-------
Section 3.7.4 6 5-01-79
Plant Stj/fur/cfa/lJ T/ad. City /j&idvf '//&, US.A-
Site (Jtl/£ 2 £ytj&6: Samoletvoe fySdj.
Date 7//O/ 7& Run number Sflr" In
^ ' '
Front rinse m Front filter D Front solution D
Back rinse D Back filter D Back solution D
Solution 60 V» I PA Level marked \Sf
Vnlumn: Initial /DO HrjL Final 18I26O |
Cleanuo by If/G D £
Figure 4.2. Example of a sample label.
-------
5-01-79
Section 3.7.4
Sample Recovery and Integrity Data
Plant uu/ff/r/c rle/d r/atit sample i^tinn Unit 1 ft/
Field Data Checks
Sample recovery personnel.
U/.M.
Person with direct responsibility for recovered samples.
Sample
number
1
2
3
Blanks
Sample
identification
number
HiSO*
SAP-/A
SAP**
Blink
S02
SflP-tB
5/IP-P
Blank
Date
of
recovery
J//8/76
9/I8/7B
Liquid
level
marked
fe$
yes
Stored
in locked
container
Yes
Yes
Remarks
Signature of field sample trustee.
Laboratory Data Checks
Lab person with direct responsibility for recovered samples
Date recovered samples received.
Analyst.
fl IGlfWGICU OO
f/2//7£
Remarks
Signature of lab sample trustee.
Sample
number
1
2
3
Blanks
Sample
identification
number
HiSO*
SAP- //I
MP-fl
B/*ifJc
S02
SW-IB
S4P-B
B fail It
Date
of
analysis
9/XZ/78
1/22/78
Liquid
at marked
level
Yes
Y*s
Sample
identified
/«
Yes
Figure 4.3. Sample recovery and integrity data.
-------
Section 3.7.4 8 5-01-79
Sampling
Impingers properly assembled?
Contents:* 1st
3rd
!00g or Ji/icaoA.
I£.2 and mater
4th 2OOa of S//A
Cooling system
Filter between 1st and 2nd impinger?
Proper connections? Y-£^S.
Silicone grease added to all ground-glass joints?
Pretest leak check? _ Y&S _ (optional) Leakage? &
Pilot tube lines checked for plugging and leaks?* /
-------
5-01-79
Section 3.7.4
Table 4.1. Activity
Apparatus
Sampling
Preparation
and /or
addition of
absorbing
reagents to
collection
system
Filter
Assembling
samp/ing train
Matrix for On-Site Measurement Checks
Acceptance limits
100 ml of 80% isopro-
panol to first impinger
and TOO ml of 3% H20z
to each of the second
and third impingers
Properly centered; no
breaks, damage, or
contamination during
loading
1 . Assemble to speci-
fications in Fig. 1 . 1
2. Leakage rate <4% or
0.00057 m3/min (0.02
ft3/min)
Frequency and method
of measurement
Prepare H202 and 80%
isopropanol fresh
daily; use pipette or
graduated cylinder to
add solutions
Use tweezers or sur-
gical gloves to load
1. Before each
samp/ing
2. A leak check
before sampling is
recommended; plug
Action if
requirements
are not met
Reassemble
collection
system
Discard
filter and
reload
1. Reassemble
2. Correct
leak
the nozzle or inlet to
the first impinger
and pull a vacuum of
380 mm (15 in.) Hg
Sampling (iso- 1. Samp/ing must be
kinetic ally) performed within ±10%
of isokinetic
2. Check applicable
standard for minimum
sampling time and vol-
ume; minimum sampling
time/ point should be
2 min
3. Sampling rate should
not exceed 0.03 m3/min
(1.0 ft3 /min)
4. Minimum number of
points sampled, as
specified by Meth. 1
5. Leakage rate not to
exceed €.00057 m3/min
(0.02 ft3 '/mini or 4% of
average sampling rate;
apply correction to
sample volume if rate
is exceeded
6. Purge remaining SO?
from isopropanol
Sample recovery Noncontaminated sample
1. Calculate for each
sample run
2. Make a quick cal-
culation before and
an exact calculation
after testing
3. Select proper noz-
zle size. Sec. 3.7.4,
Eq. 4-1
4. Check before the
first test run by
measuring duct and
sampling site location
5. Leak check after
each test run or
before equipment re-
placement during a
run at maximum vacuum
occurring during the
run (mandatory)
6. Drain ice, and
purge with clean air
for 15 min
Transfer sample to
labeled polyethylene
container after each
test run. Mark level
of solution in the
container
1. Repeat
sample or
obtain accep-
tance from a
representative
of the
Administrator
2. As above
3. As above
4. As above
5. Correct
sample vol-
ume or repeat
sample
6. Repeat
sample
Repeat
sample
-------
Section 3.7.4
10
6-01-79
Table 4. 1 . {continued)
Apparatus
Sample logistics
(data) and
packing of
equipment
Acceptance limits
1. All data recorded
correctly
2. All equipment exam-
Frequency and method
of measurement
1 . Upon the comple-
tion of each sample
and before packing
for shipment
2. As above
Action if
requirements
are not met
1. Complete
data
2. Repeat
ined for damage and
labeled for shipment
3. All sample contain-
ers properly labeled
and packaged
3. Visually check up
on completion of each
sample
samp ling if
damage
occurred during
testing
3. Correct
when possible
-------
6-01-79
Section 3.7.5
5.0 Postsampling Operations
Table 5.1 at the end of this section
summarizes quality assurance
activities for postsampling operations.
5.1 Apparatus Checks
Posttest checks have to be
conducted on most of the sampling
apparatus. These checks include three
calibration runs at a single orifice
meter setting; cleaning; and/or
routine maintenance. The cleaning
and maintenance will be discussed in
Section 3.7.7, and is discussed in
APTD-0576.5 Figure 5.1 should be
used to record data from the posttest
checks.
5.1.1 Metering System - The meter-
ing system has two components that
must be checked — the dry gas meter
and the dry gas meter thermometer(s).
The dry gas meter thermometer(s)
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 acceptable; if not,
the thermometer must be recalibrated
according to Section 3.7.2 after the
posttest check of the dry gas meter.
For calculations, the dry gas meter
thermometer readings (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 should
be added to the average dry gas meter
temperature reading.
The posttest check of the dry gas
meter is described in Section 3.7.2. If
the posttest dry gas meter calibration
factor (Y) is within 5% of the initial
calibration factor, the initial
calibration is used for calculations; if
it deviates by >5%, recalibrate the
metering system (as shown in Section
3.7.2) and use for the calculations the
calibration factor (initial or
recalibrated) that yields the lesser gas
volume. For each test run, the lesser
calibration factor will give the lower
gas volume.
5.1.2 Barometer - The field barom-
eters are acceptable if they agree
within ±5 mm (0.2 in.) Hg when
compared with the mercury-in-glass
barometer. When they do not agree,
the lesser calibration value should be
used for the calculations. If the field
barometer reads lower, no correction
is necessary. If the mercury-in-glass
barometer reads lower, subtract the
difference from the field data readings
for the calculations.
5.2 Analysis (Base
Laboratory)
Calibrations and standardizations
are of primary importance to a precise
and accurate analysis. The analytical
method is based on the insolubility of
barium sulfate (BaS04) and the
formation of a colored complex
between barium ions and the thorin
indicator (1 -(o-arsonophenylazo)-2-
naphthol-3, 6-disulfonic acid disodium
salt). Aliquots from the impinger
solutions are analyzed by titration
with barium perchlorate to the pink
endpoint. The chemical reaction for
this standardization is shown in Equa-
tion 5-1. The barium ions (Ba+*) react
preferentially with sulfate ions (S04=)
in solution to form a highly insoluble
barium sulfate (BaSOo) precipitate.
After the Ba++ has reacted with all
S04=, excess Ba++ reacts with the
thorin indicator (x++) to form a metal
salt of the indicator and to give a color
change:
thorin(x++) —
(yellow)
thorin(Ba++)
(pink)
Equation 5-1
Ba" +
BaSO4
Upon completion of each step of the
standardization or of each sample
analysis, the data should be entered
on the proper 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
sulfuric acid mist (including SCb) and
the S02 samples.
Water - Deionized distilled water to
conform to ASTM specification
D1193-74, Type 3. 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 to be
present. Note - It is imperative that
the distilled water meet the ASTM
specifications since S04= and other
polyvalent ions present in distilled
water are not determined in the
normal standardization of the acid by
NaOH titration (which measures the
hydrogen ion (H+) concentration rather
than the S04= concentration). This
added S0«= concentration would
result in an erroneous standardization
of the BafCIO^lz titration, which
directly measures SO«= concentration
and not hT concentration. A check on
the acceptability of the distilled water
is detailed in Section 3.7.1.
Isopropanol. W0% - Certified ACS
reagent grade isopropanol. Check for
peroxide impurities as described in
Section 3.7.1.
Thorin indicator - 1-o-arsono-
phenylazo -2-naphthol-3, 6-disulfonic
acid disodium salt, or equivalent.
Dissolve 0.20 g ±0.002 g in 100 ml of
deionized distilled water. Measure the
distilled water in a 100-ml Class-A
graduated cylinder.
Barium perch/orate solution
0.0100N - Dissolve 1.95 g of barium
perchlorate trihydrate (Ba(CI04)2 •
3H20) in 200 ml of deionized distilled
water and dilute to 1 L with
isopropanol. Alternatively, 1.22 g of
banum chloride dihydrate (BaCI2 •
2H20) may be used instead of the
trihydrate. Standardize as in the
subsec- tion below with H2S04. Note-
Protect the 0.01 OON barium
perchlorate solution from evaporation
at all times by keeping the bottle
capped between uses.
Sulfuric acid standard. 0.01 OON -
Either purchase a standard
guaranteed by the manufacturer or
standardize to ±0.0002N H2S04
against 0.01 OON NaOH that has been
standardized against potassium acid
phthalate (primary standard grade), as
described in the subsection below.
The 0.01 N H2SO4 may be prepared
in the following manner:
a. Prepare 0.5N H2S04 by adding
approximately 1 500 ml of deion-
ized distilled water into a 2 L
volumetric flask.
b. Cautiously add 28 ml of concen-
trated H2SO4 and mix. Cool, if
necessary.
c. Dilute to 2 L with deionized
distilled water.
d. Prepare 0.01 N H2S04 by adding
approximately 800 ml of
deionized distilled water to a 1 L
volumetric flask.
e. Add 20.0 ml of the 0.5N H2S04.
f. Dilute to the 1 L with distilled
water and mix thoroughly. Note -
-------
Section 3.7.5
5-01-79
It is recommended that 0.1N
sulfuric acid be purchased.
Pipette 10.0 ml of H2S04 (0.1N)
into a 100-ml volumetric flask,
and dilute to volume with
deionized distilled water that has
been determined to be
acceptable as detailed in Sub-
section 5.2.4. When the 0.01 N
sulfuric acid is prepared in this
manner, procedures in Subsec-
tions 5.2.2 and 5.2.3 may be
omitted since the standardization
of the 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% w/w NaOH
solution. Dilute 10 ml to 1 L with
deionized distilled water. Dilute
52.4 ml of the diluted solution to
1 L with deionized distilled
water.
2. Dry the primary standard grade
potassium acid phthalate (KHP)
for 1 to 2 h 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
deionized distilled water in a
250-ml Erlenmeyer flask.
4. Add two drops of
phenolphthalein indicator, and
titrate the phthalate solutions
with the NaOH solution. All
titrations should be done against
a white background to facilitate
the detection of the endpoint -
the first faint pink color that
persists for at least 30 s.
5. Compare the endpoint colors of
the other two titrations against
the first one. The normality is the
average of the three individual
values calculated using Equation
5-1.
M mg KHP
NNBOH - 2
ml titrantx 204.23
Equation 5-1
where
NNaOH = calculated normality of
NaOH, N
mg KHP = the weight of KHP, mg,
and
mltitrant=the volume of NaOH
titrant, ml.
The chemical reaction for this stand-
ardization is» shown in Equation 5-2.
The NaOH is added to the KHP and
the colorless phenolphthalein solution
until an excess of sodium ions (Na*)
causes the phenolphthalein to change
to a pink color.
NaOH + KHP + phenolphthalein (H+)
(colorless)
- KNaP + HOH + phenolphthalein
(pink)
Equation 5-2
5.2.3 Standardization of Sulfuric
Acid - To standardize H2SO4, proceed
as follows:
1. Pipette 25 ml of H2S04 into three
250-ml Erlenmeyer flasks.
2. Add 25 ml of deionized distilled
water.
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
deionized distilled water, using
the same technique as step 3
above. The normality will be the
average of the three independent
values calculated using Equation
5-3.
(ml NaOHH2so4 - ml NaOHb,ank) x NNBOH
25
Equation 5-3
where
NH2so4 = calculated normality
of H2S04, N,
mlNaOHH2so4= volume of NaOH
titrant used for
H2S04, ml,
mlNaOHbiank= volume of NaOH
titrant used for blank,
ml, and
NNaOH = normality of NaOH, N.
5.2.4 Standardization of Barium
Perchlorate (0.0100N) - To standardize
Ba(CI04)2, proceed as follows:
1. Pipette 25 ml of standard
0.01 OON H2S04 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
0.01 OON Ba(CI04)2. All thorin
titrations should be done against
a white background to facilitate
the detection of the pink
endpoint.
3. Run a blank that contains 25 ml
of deionized distilled water and
100 ml of isopropanol. The blank
must not exceed 0.5 ml of titrant
to obtain the endpoint; otherwise
the distilled water has excess
S04=. If this 0.5-ml volume is
exceeded, all reagents made with
the distilled water will have to be
remade using acceptable distilled
water.
4. Use the endpoinfcof the first
titration as a visual comparator
for the succeeding titrations.
5. Record data on the form in
Figure 5.2. The normality of the
Ba(CI04)2 will be the average of
the three independent values
calculated using Equation 5-4.
NBa(CIO4>2 -
NH2so4 x 25
ml Ba(CI04)2
Equation 5-4
where
NBaicio4i2::calculated normality
of Ba(CI04)2, N,
Nn2so4- normality of standard
H2S04, N, and
ml Ba(CIO4)2 = volume of Ba(CIO4)2
required to titrate
H2S04, ml.
The chemical reaction for this stand-
ardization is shown in Equation 5-5.
The Ba++ reacts preferentially with
S04= in solution to form a highly
insoluble BaSO4 precipitate. When the1
Ba++ has reacted with all of the S04=,
the excess Ba+* reacts with the thorin
indicator (x++) to form a metal salt of
the indicator and to give a color
change.
Ba** + S04= + thorin (x+*) —
(yellow)
BaS04 + thorin (Ba")
(pink)
Equation 5-5
The standardized Ba(CI04)2 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 of low, medium, and high
concentrations in the following
manner:
1. Pipette 3.0-, 10.0-, and 20-ml
aliquots of 0.01 N H2S04 into
three 250-ml Erlenmeyer flasks.
2. Dilute each to 25 ml with
distilled water.
3. Add a 100-ml volume of 100%
isopropanol and two to four
drops of thorin indicator to each
flask.
4. Titrate with Ba(CIO4)2 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 analysis technique is
determined by control samples; the
precision, by duplicate analyses of
both the control and the field samples.
Acceptable accuracy and precision
should be demonstrated on the
analysis of the control samples prior
-------
5-01-79
Section 3.7.5
to the analysis for the field samples.
Each control sample should be
prepared and analyzed in the
following manner:
1. Dry the primary standard grade
ammonium sulfate ((NH^SO^
for 1 to 2 hat 110°C (230°F),
and cool in a desiccator.
2. Weigh, to the nearest 0.5 mg,
1.3214 g of primary standard
grade (NH4)2S04.
3. Dissolve the reagent in about
1800 ml of distilled water in a 2-
L volumetric flask.
4. Dilute to the 2-L mark with
distilled water. The resulting
solution is 0.01 N (NH4)2S04.
5. Enter all data on the form shown
in Figure 5.3.
6. Pipette 25 ml of the control
sample into each of four 250-ml
Erienmeyer flasks, and prepare a
25-ml blank of distilled water in
a fourth 250-ml Erienmeyer
flask. Note - Each control sample
will contain 16.5 mg of
ammonium sulfate.
7. Add 100 ml of reagent grade
isopropanol and two to four
drops of thorin indicator to each
flask.
8. Initially titrate the blank to a faint
pink endpoint using the stand-
ardized BafCIO-ib. The blank must
contain <0.5 ml of titrant; other-
wise, the distilled water is unac-
ceptable for use in this method.
9. Titrate two of the control
samples with the standardized
Ba(CI04)2 to a faint pink endpoint,
using the blank endpoint that
persists for at least 30s. All
titrations should be done using a
white background.
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 the agreement is
not within 0.2 ml, titrate the
third control sample. If the third
titrant 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.
When this criterion cannot be
met with the first set of two
control samples, the analyst
should 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 techniques
observed by a person
knowledgeable in chemical
analysis.
12. After consistent titrant volumes
are obtained, the calculation of
the analytical accuracy should be
completed, as shown in Figure
5.3. If the measured value is
within ±5% of the stated value,
the technique is considered
acceptable, and the field samples
may be analyzed. When the ±5%
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. The 5% accuracy limit
is based on the control limit from
EPA audits discussed in Section
3.5.8.
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 container, deter-
mine whether any sample was lost
during shipment, and note this on
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 prescribed below. Approval
should have been requested prior to
testing in case of subsequent leakage.
The alternative method is as follows:
1. Mark the new volume level of
the sample.
2. Transfer the sample to a 250-ml
or 1-L (whichever is appropriate),
volumetric flask (V,0m.).
3. Put water in the sample storage
container to the initial sample
mark, and measure the initial
sample volume (Vsom,).
4. Put water in the sample storage
container to the mark of the
transferred sample, and measure
the final volume (Vsom,).
5. Use Equation 5-6 to correct the
sample volume (V,oln) if the final
volume (V,0in() is >50% of the
initial volume.
Equation 5-6
where
Vsoin. = sample volume that will be
used for the sample
calculations, ml,
Vsom = total volume of solution in
which the sample is
contained, ml,
Vsoin = initial sample volume placed
in sample storage container,
ml, and
VSoin = final sample volume removed
from sample storage
container, ml.
6. Report both the corrected and
the uncorrected values to the
Agency, and proceed with the
applicable analysis lised below.
Sulfuric acid mist (including SOi)
analysis - Proceed with the analysis
as follows:
1. Shake the container holding the
isopropanol solution and the
filter. If the filter breaks up, allow
the fragments to settle for a few
minutes before removing a sam-
ple.
2. Pipette a 100-mi aliquot of this
solution into a 250-ml
Erienmeyer flask.
3. Add two to four drops of thorin
indicator, and titrate to a pink
endpoint using 0.0100N
Ba(CI04)2.
4. Repeat the titration with a
second aliquot from the same
sample. Replicate titrant volumes
should be within 1% or 0.2 ml,
whichever is greater. If the
titrant volumes do not meet this
criterion, repeat analyses on new
aliquots until two consecutive
titrations agree within 1% or 0.2
ml, whichever is greater.
5. Record all data on Figure 5.2.
The consistent titrant volumes
should be averaged and used at
V, in subsequent calculations. All
analytical data must then be
reviewed by an individual
familiar with procedures. The
review of the data will also be
noted on Figure 5.2. Note -
Protect the 0.01 DON Ba(CIO)2
solution from evaporation at all
times.
Sulfur dioxide analysis - Proceed
with the SOj analysis as follows:
1. Thoroughly mix the solution in
the container holding the
contents of the second and third
impingers.
-------
6-01-79
Section 3.7.5
2. Pipette a 10-ml aliquot of the
sample into a 250-ml Erlenmeyer
flask.
3. Add 40 ml of isopropanol and
two to four drops of thorin
indicator.
4. Titrate to a pink endpoint using
0.01 OON Ba(CI04)2. Note - Protect
the 0.01 OON Ba(CI04)2 solution
from evaporation at all times.
Repeat titration with a second
aliquot from the same sample.
Replicate titrant volumes should
be within 1 % or 0.2 ml,
whichever is greater. If the
titrant volumes do not meet this
criterion, repeat analyses on new
aliquots until two consecutive
titrations are within 1% or 0.2
ml, whichever is greater.
5. Record all data on the Method 8,
Figure 5.2. The consistent titrant
volumes should be averaged and
used as Vt in subsequent calcula-
tions. All analytical data must
then be reviewed by an
individual familiar with
procedures. The review of the
data should also be noted on
Figure 5.2.
Blanks - Prepare blanks by
adding two to four drops of
thorin indicator to 100 ml of 80%
isopropanol. Titrate the blanks in
the same manner as the
.samples. Record on Figure 5.2 in
the space provided.
To aid the analyst or reviewer
in a method of checking the
analytical steps or procedures,
the posttest operations form
Figure 5.4 is given.
-------
6-01-79 5 Section 3.7.6
Meter Box Number ~ I
Dry Gas Meter
/O ^#£»
Pretest calibration factory Y = . t*^' ' "
Posttest check X, = O-?o7 /2 = (±5% of pretest factor)*
Recalibration required? yes L no
If yes, recalibration factor Y = (within ±2% of average)
Lower calibration factor. Y =
-------
Section 3.7.6
5-01-79
Method 8 Analytical Data Form
P,ant
Date
Sample location
7* / A&t Ctl^t /
Analyst .
Volume and normality of
barium perch/orate
ml Ba
mlBa
Blank Q-O ml Ba
Sulfur Trioxide Analysis
in - Total volume of solution in which the sulfuric
acid sample is contained, ml
Va - Volume of sample aliquot, ml
Vt - Volume of barium perchlorate
titrant used for sample, ml
o* - Volume of barium perchlorate
titrant used for blank, ml
1st titration
2nd titration
to
°'\ 1st
1st titration
2nd titration
Average
1st titration
2nd titration
Average
- 2nd titration \ < 0.2 ml
Sulfur Dioxide Analysis
Total volume of solution in which the sulfuric
acid samle is contained, ml
Va • Volume of sample aliquot, ml
V> - Volume of barium perchlorate
titrant used for sample, ml
Vtt>* - Volume of barium perchlorate
titrant used for blank, ml
1st titration
2nd titration
Average
1st titration
2nd titration
Average
1st titration
= 0.95 to I'.Ot or\1st titration - 2nd titration\ < 0.2 ml
Run 1
Run 2
Run 3
Run 1
/OO6
/4
//.*>
/f-3
/'•3
O-O
6.0
6-0
Run 2
Run 3
2nd titration
Signature of analyst
Signature of reviewer or supervisor
* Volume of blank and sample titrated should be the same; otherwise a volume correction must be made.
Figure 5.2. Method 8 analytical data form.
-------
5-01-79
Section 3.7.5
Plant
Analyst.
Control Sample Analytical Data Form
_Date analyzed
Z/22/7&
/?.
Weight of ammonium sulfate is 1.3214 gram?
Dissolved in 2 L of distilled water?
Titration of blank *^' ^
(must be less than the 0.5 ml titrant)
. ml Ba (CIOJ*
Control
Sample
Number
Time of
Analysis
24 h
Titrant volume, ml
1st
xsr.o
2nd
3rd
Ave
(Two consecutive volumes must agree within 0.2 ml)
mlBa(CIOt)zxNat(CIO) - 25ml x 0.01 N
(control sample) (control sample)
(must agree within ±5%, i.e., 0.233 to 0.268)
Does value agree? _ yes _ no
Signature of analyst
. Signature of reviewer
Figure 5.3. Control sample analytical data form.
-------
Section 3.7.6
6-01-79
Reagents
Normality of sulfuric acid standard*.
Date of purchase
O.O IOO
Date standardized
Normality of barium perch/orate titrant
Date standardized
Normality of control sample*
Date prepared
Volume of burette* .
Sample Preparation
Has liquid level noticeably changed?
4 „
Original volume
Graduations
' '
/v*
Y
Sulfuric acid samples diluted to 250 ml?*
Sulfur dioxide samples diluted to 1000 ml?*
Analysis
Volume of aliquots analyzed* '
Do replicate titrant volumes agree within 1% or 0.2 ml?
Number of control samples analyzed
Corrected volume
r
L/
Are replicate control samples within 0.2 ml? '*
Is accuracy of control sample analysis ±4%?
All data recorded? ¥£-^ Reviewed by
"Most significant items/parameters to be checked.
Figure 5.4. Posttest operations.
-------
6-01-79
Section 3.7.6
Table 5. 1. Activity
Apparatus
Sampling
Apparatus
Dry gas meter
Meter thermome-
ter
Barometer
Analysis
Reagents
Control sample
Sample analysis
Matrix for Postsampling Operations
Acceptance limits
Within ±5% of pretest
calibration factor
Within ±6°C (10.8°F) at
ambient temperature
Within ±5.0 mm (0.2 in.)
Hg at ambient pressure
Prepare according to
Sec. 3. 7.5
Tit rants differ by
-------
6-01-79
Section 3.7.6
6.0 Calculations
Calculation errors due to procedural
or mathematical mistakes can be a
large component of total system error.
Therefore, it is recommended that
each set of calculations be repeated
or spot-checked, 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. Use a computer
program that prints the input data
back out so that it can be checked. If a
standardized computer program is
used, the original data entry should 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
retaining at least one decimal figure
beyond that of the acquired data and
should be rounded after final calcula-
tion to two significant digits for each
run or sample. All rounding of
numbers should be in accordance
with the ASTM 380-76 procedures.
Record all calculations on Figures
6.1 A or B and on Figures 6.2A or B,
or on similar forms, following the
nomenclature list.
6.1 Nomenclature
The nomenclature is used in the
calculations that follow this alpha-
betical list.
An = Cross-sectional area of noz-
zle, m2 (ft2).
Bws=Water vapor in the gas
stream, proportion by
volume.
CHJSO, = Sulfuric acid (including S03)
concentration, g/dscm (Ib/
dscf).
Cso2 = Sulfur dioxide
concentration, g/dscm
(Ib/dscf).
I = Percent of isokinetic samp-
ling, %.
N = Normality of BafCIO^z
titrant, g-eq/L.
Pbar = Barometric pressure at the
sampling site, mm (in.) Hg.
Ps = Absolute stack gas
pressure, mm (in.) Hg.
Psid = Standard absolute pressure,
760.mm (29.92 in.) Hg.
Tm= Average absolute dry gas
meter temperature, K (°R).
Ts= Average absolute stack gas
temperature, K (°R).
Tst(j=Standard absolute tempera-
ture, 293K (528°R).
Va=Volume of sample aliquot
titrated, 100 ml for HgSCu
and 10 ml for S02.
Vic = Total volume of liquid col-
lected in impingers and
silica gel, ml.
Vm= Volume of gas sample mea-
sured by dry gas meter, dcm
(dcf).
Vmistdi=Volume of gas sample mea-
sured by the dry gas meter
and corrected to standard
conditions, dscm (dscf).
V3=Average stack gas velocity
calculated by Method 2, us-
ing data from Method 8,
m/s (ft/s).
Vsom=Total volume of solution in
which the H2SO* or S02
sample is contained, 250 ml
or 1000 ml, respectively.
Vt=Volume of BafCIO^ titrant
used for the sample, ml.
V|b = Volume of barium perchlo-
rate titrant used for the
blank, ml.
Y = Dry gas meter calibration
factor.
AH = .Average pressure drop
across orifice meter, mm
(in.) H20.
0= Total sampling time, min.
13.6 = Specific gravity of mercury.
60 = s/min.
100 = Conversion to percent.
6.2 Calculations
The following are the formulas used
to calculate the concentrations of
sulfuric acid mist (including SOa and
SC"2) along with the calculation forms
(Figures 6.1A, 6.1B, 6.2A, and 6.2B)
used to record the data.
6.2.1 Dry Sample Gas Volume,
Corrected to Standard Conditions -
Correct the sample volume measured
by the dry gas meter to standard
conditions 20°C and 760 mm (68°F
and 29.92 in. Hg) by using Equation
6-1. The average dry gas meter
temperature and average orifice
pressure drop are obtained by
averaging the field data (see Figure
4.1).
Vcr
\ Tm
AH _
13.6
Pstd
=K,VmY
Equation 6-1
where
Kt = 0.3858 K/mm Hg for metric
units.or
= 17.64°R/in. Hg for English
units.
Note - If the leakage rate observed
during any mandatory leak check
exceeds the specified acceptable rate,
the tester should either correct the
value of Vm in Equation 6-1 (as de-
scribed in Reference Method 5) or
invalidate the test run.
6.2.2 Volume of Water Vapor and
Moisture Content - Calculate the
volume of water vapor and moisture
content of the stack gas as described
in Sections 6.4 and 6.5 of Method
5, respectively.
6.2.3 Sulfuric Acid Mist (Including
SO*) Concentration -
N (V, - V,b)
Vsoln
Va
Vmlstdl
Equation 6-2-
-------
Section 3.7.6
5-01-79
where
K2 = 0.04904 g/meq for metric
units, or
= 1.081 x 10"4lb/meq for
English units.
6.2.4 Sulfur Dioxide Concentration -
Cso2 -
[
N (V, - Vlb)
Vmlstdl
[
Pbar+
6.2.6 Isokinetic Variation (I) in
Intermediate Values -
Equation 6-3
where
K3 = 0.03203 g/meq for metric
units.or
= 7.061 x 10"5 Ib/meq for English
units.
6.2.5 Isokinetic Variation (I) in Raw
Data -
x 100
60 0 VsPsAn
Equation 6-4
where
= 0.003464 mm Hg-mVml-K
for metric units, or
= 0.002676 in. Hg-ftVml-°R for
English units.
TsVmistdlPstd I
= •= - =!
100
Tstd600VsPsAn[1-Bws]
0VsPsAn[1-Bws]
Equation 6-5
where
K5 = 4.320 for metric units, or
= 0.09450 for English units.
6.3 A cceptable Results
If 90% < I < 1 10%, the results are
acceptable. If the results are low in
comparison with the standards and if
the I is beyond the acceptable range,
the Administrator may opt to accept
the results. Otherwise, the results
may be rejected and the test repeated.
It is suggested that, for Method 8
tests, the data not be rejected only
because of noncompliance with
isokinetic requirements.
Table 6.1. Activity Matrix for Calculation Checks
Characteristics
Analysis data
form
Calculations
Isokinetic
variations
Acceptance limits
All data and calcula-
tions given
Difference between
check and original cal-
culations not to exceed
round-off error; retain
at least one decimal
figure beyond that of
acquired data
90% <\<110%
Frequency and method
of measurement
Visually check
Repeat all calcula-
tions, starting with
raw data for hand cal-
culations; check all
raw data input to com-
puter calculations;
hand calculate one
sample/test
For each traverse
point, calculate 1
Action if
requirements
are not met
Complete
missing
data values
Indicate
errors on
analysis data
form.
Fig. 6.3
Repeat test
and adjust
flow rates
to maintain
1 within 1O%
variation
-------
6-01-79 3 Section 3.7.6
Sulfuric Acid Mist (Including SOa/ Calculation Form
(English units)
Sample Volume
Vm =.> 0_ V. Tm = . °R, P*» = £ _£._£ £ in. Hg
in- H*°
rm J
Equation 6-1
Sulfuric Acid Mist (Including SOaJ Concentrations
g-eg/L.V< = .. ml. V* =_.. . ml
= 1.081x10-" < — > = -^ W* Ib/dscf
Equation 6-2
Figure 6.1A. Sulfuric acid mist (including SOa) calculation form (English units/.
-------
Section 3.7.6
5-01-79
Sulfuric Acid Mist (Including SOaJ Calculation Form
(metric units)
Sample Volume
A/Y
._ K. />ba, =
mm H20
-. mmHg
l/mstd =0.3858
^Li 2.0.
m3
Equation 6-1
Sulfuric Acid Mist (Including SOs) Concentrations
9-eg/L.Vt —_
ml. Va =
ml. Vtb =
ml. Vm=
CH2so4 = 0.04904
N (V, -
"std
g/dscm
Equation 6-2
Figure 6. IB. Sulfuric acid mist (including SOd calculation form (metric units).
-------
5-01-79
Section 3.7.6
Sulfur Dioxide Calculation Form
(English units)
Sample Volume
— 17.64VmY
Equation 6-1
Sulfuric Acid Mist (Including SOa/ Concentrations
N = ._ _ ^ _ g-eg/L.V< =__. ml. Vtb = _* _ ml
= 7.05/ x 10~*
N(V, -
r* Ib/dscf
Equation 6-2
Figure 6.2A. Sulfur dioxide calculation form (English units).
-------
Section 3.7.6
5-01-79
Sulfur Dioxide Calculation Form
(metric units)
Sample Volume
2. fa.m3• r™ =3. Q. L' J- K. p*« = 2. 4. L- 1L
£ mm H20
= 0.3858VmY
Equation 6-1
Concentration
N =.0_ /_ Q_
ml. V,t = Q . U ^ml
l/soln =
. ml.
Cso2 = 3.203x 10'
V,
"std
—j2.'^2 Z. & a/dscm
Equation 6-2
Figure 6.2B. Sulfur dioxide calculation form (metric units).
-------
5-01-79
Section 3.7.7
7.0 Maintenance
The normal use of emission testing
equipment subjects it to corrosive
gases, extremes in temperature, vibra-
tions, and shocks. Keeping the equip-
ment in good operating order over an
extended period of time requires a
knowledge of the equipment and a
program of routine maintenance
which is performed quarterly or after
28.4 m3 (1000 ft3) of operation,
whichever is greater. 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 this subsection.
The following procedures are not
required, but are recommended to
increase the reliability of the equip-
ment.
7.1 Pumps
In the present commercial sample
train, several types of pumps are
used. The two most common are the
fiber vane pump with in-line oiler and
the diaphragm pump. The fiber vane
pump requires a periodic check of the
oiler jar; its contents should be
translucent at the time of filling and
at each periodic check, and it is
recommended that the oil 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 should be changed. Erratic
operation of the diaphragm pump is
normally due either to a bad
diaphragm, which will cause leakage,
or to malfunction of the valves, which
should be cleaned annually by
complete disassembly of the train.
7.3 Sample Train
All remaining sample train com-
ponents should be checked visually
every 3 mo and disassembled com-
pletely and cleaned or replaced yearly.
Many of the items such as quick
disconnects should be replaced when
damaged rather than checked period-
ically. Normally, the best procedure
for maintenance in the field is to use
another entire unit such as a meter
box, sample box, or umbilical cord (the
hose that connects the sample box
and the meter box) rather than to
replace individual components.
7.4 Inclined Manometer
The fluid in the inclined
thermometer should be changed
whenever there is discoloration or
visible matter in the fluid and during
the yearly disassembly. No other
routine maintenance is required since
the inclined manometers will be leak
checked during both the leak check of
the Pilot tube and the leak check of
the entire control console.
7.2 Dry Gas Meters
The dry gas meter should be
checked for excess oil or corrosion of
the components by removing the top
plate every 3 mo. The meter should be
disassembled, and all components
should be cleaned and checked when
the rotation of the dials is erratic,
when the meter will not calibrate
properly over the required flow rate
range, and during yearly maintenance.
-------
Section 3.7.7
5-01-79
Table 7.1. Activity
Apparatus
Routine main-
tenance
Fiber vane pump
Diaphragm pump
Dry gas meter
Inclined mano-
meter
Sample train
Nozzle
Matrix for Equipment Maintenance Checks
Acceptance limits
No erratic behavior
In-line oiler free of
leaks
Leak-free valves func-
tioning properly
No excess oil. corro-
sion, or erratic rota-
tion of the dial
No discoloration or
visible matter in the
fluid
No damage
No dents, corrosion, or
other damage
Frequency and method
of measurement
Routine maintenance
quarterly. Disas-
semble and clean
yearly
Periodic check of
oiler jar; remove
head and change fiber
vanes
Clean valves during
yearly disassembly
Check every 3 mo for
excess oil or corro-
sion by removing top
plate. Check valves
and diaphragm when
meter dial runs
erratically or when
meter will not
calibrate
Check periodically
during yearly disas-
sembly
Visually check every
3 mo and completely
disassemble and clean
or replace yearly
Visually check before
and after each test
run
Action if
requirements
*are not met
Replace parts
as needed
Rep/ace as
needed
Replace
when leaking
or malfunc-
tioning
Rep/ace parts
as needed, or
replace meter
Replace parts
as needed
If failure
noted, use
another en-
tire control
console, sam-
ple box, or
umbilical
cord
Use another t
nozzle or
clean out,
sharpen, and
recalibrate
-------
5-01-79
Section 3.7.8
An audit is an independent assess-
ment of data quality. Independence is
achieved if the individual(s)
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 procedure. Table
8.1 at the end of this section
summarizes the quality assurance
functions for auditing.
Based on the results of a
collaborative test2 of Method 8, two
specific performance audits are
recommended:
1. Audit of the analytical phase of
Method 8, and
2. Audit of data processing.
It is suggested that a systems audit be
conducted as specified by the quality
assurance coordinator, in addition to
these performance 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
quantitatively evaluate the quality of
data produced by the total measure-
ment system (sample collection,
sample analysis, and data processing).
It is recommended 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 actual analysis
of the field samples which is required.
8.1.1 Pretest A udit of Analytical
Phase Using Aqueous Ammonium
Sulfate (Optional) - The pretest audit
described in this subsection can be
used to determine the proficiency of
the analyst and the standardization of
solutions in the Method 8 analysis
and should be performed at the
discretion of the agency auditor. The
analytical phase of Method 8 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
8.0 Auditing Procedure
prepared by the procedure described
in Section 3.7.5 on control sample
preparation.
The pretest audit provides the op-
portunity for the testing laboratory to
check the accuracy of its analytical
procedure. This audit is especially
recommended for a laboratory with
little or no experience with the
Method 8 analysis procedure
described in this Handbook.
The testing laboratory should
provide the agency/organization
requesting the performance test with
a notification of the intent to test 30
days prior to the enforcement source
test. The testing laboratory should
request that the agency/ organization
provide the following performance
pretest audit samples: two samples at
a low concentration (500 to 1000 mg
S02/dscm of gas sampled or
approximately 10 to 20 mg of
ammonium sulfate/sample) and two
samples at a high concentration (1500
to 2500 mg SOz/dscm of gas sampled
or about 30 to 50 mg of ammonium
sulfate/sample). At least 10 days prior
to the time of 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 below.)
The agency/organization
determines the percent accuracy, %A,
between the measured SOa
concentration and the audit or known
values of concentration. The %A is a
measure of the bias of the analytical
phase of Method 8. Calculate %A
using Equation 8-1.
0/oA = Cso2(M)-Cso2(A)y 100
Cso2(A)
Equation 8-1
where
Cso2(M) = concentration measured
by the lab analyst
mg/ml, and
Cso2(A) = audit or known concen-
tration of the audit
sample, mg/ml.
The recommended control limit for
the pretest audit is the 90th percentile
value for %A based on the results of
three audits (11/77, 5/78, and
10/78) performed by the
Environmental Monitoring and
Support Laboratory, USEPA, Research
Triangle Park, North Carolina.6'7 By
definition, 90% of the laboratory
participants in the audit obtained
values of %A less than the values
tabulated below. The control limit is
expected to be exceeded by 10% of
the laboratories to be audited, based
on these three audits. The 90th
percentile values and the known audit
concentrations are given below for
each concentration range, 500 to
1000 mg SOz/dscm and 1500 to
2500 mg S02/dscm.
Audit date
5/78
10/78
Audit date
11/77
11/77
5/78
5/78
10/78
10/78
500 to 1000 mg S02/dscm
Known audit
concentration,
mg S02/dscm
90th percentile for %A,
686
572
4.1
6.4
/500 to 2500 mg S02/dscm
Known audit
concentration, 90th percentile for %A,
mg SOa/dscm %
1411
2593
2479
1907
2555
1754
6.6
4.0
4.5
4.5
4.9
5.2
-------
Section 3.7.8
5-01-79
Based on the results of these audits,
the recommended 90th percentile
control limit for pretest audits is 7% for
both concentration ranges.
If the results of the pretest audit
exceed 7% the agency/organization
should provide the correct results to
the testing laboratory. After taking any
necessary corrective action, the
testing laboratory should then analyze
the two remaining samples and report
the results immediately to the
agency/organization before the
enforcement source test analysis.
8.1.2 Audit of Analytical Phase
Using Aqueous Ammonium Sulfate
(Required) - The agency should
provide two audit samples to be
analyzed along with 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 percent accuracy of the
audit samples is determined using
Equation 8-1. The results of the calcu-
lated %A should be included in the
enforcement source test report as an
assessment of accuracy of the ana-
lytical phase of Method 8 during the
actual enforcement source test.
8.1.3 A udit of Data Processing -
Calculation errors are prevalent in
Method 8. Data-processing errors can
be determined by auditing the data
recorded on the field and laboratory
forms. The original and audit (check)
calculation should agree within
roundoff; if not, all of the remaining
data should be checked. The data
processing may also be audited by
providing the testing laboratory with
specific data sets (exactly as would
occur 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 audit may be reduced—
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 in the following:
1. Inform the testing team of the
results of pretest audits,
specifying any area(s) that need
special attention or improvement.
2. .Observe procedures and tech-
niques 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 previoxis source
tests, where applicable.
4. Record the results of the audit
and forward them with
comments to the team
management so that appropriate
corrective action may be
initiated.
While on site, the auditor observes the
source test team's overall performance
including the following specific opera-
tions:
1. Setting up and leak testing the
sampling train.
2. Preparing and adding the absorb-
ing solution to the impingers.
3. Checking for isokinetic sampling.
4. Purging the sampling train.
Figure 8.1 is a suggested checklist
for the auditor.
Table 8.1. Activity Matrix for Auditing Procedure
Audit
Analytical phase
of Method 8
using aqueous
ammonium sul-
fate
Data-processing
errors
Systems audit —
observance of
technique
Acceptance limits
The measured value of
the pretest audit sam-
ple should be less than
the 90th percentile
value, 7%
The original and check
calculations should
agree within round-off
error
Operation technique de-
scribed in this section
of the Handbook
Frequency and method
of measurement
Once during every en-
forcement source test.
measure reference sam-
ples and compare with
their true values
Once during every en-
forcement source test,
perform independent
calculations, start-
ing with recorded
data
Once during every en-
forcement test until
experience gained;
then every fourth
test. Observation of
technique, assisted
by audit checklist.
Fig. 8. 1
Action if
requirements
are not met
Review
operating
technique
Check and
correct all
data for the
source test
Explain to
team its
deviations
from recom-
mended tech-
niques, and
note on
Fig. 8. 1
-------
5-01-79 3 Section 3.7.8
Method 8 Checklist To Be Used By Auditors
Yes No Comment Presampling Preparation
A/S
ix*^ 1 Knowledge of process conditions
OK
2. Calibration of pertinent equipment, in parti-
cular, 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 solu-
tions to impingers
J 5. Isokinetic sampling
6. Purging of the sampling train and rinsing of
the impingers and connecting tubes to recover
the sample.
7. Recording of pertinent process condition
during sample collection
8. Maintaining the probe at a given tempera-
ture
Postsampling
9. Control sample analysis - accuracy and precision
10. Sample aliquotting techniques
11. Tit rat ion technique, particularly endpoint
precision
12. Use of detection blanks in correcting field
sample results
13. Calculation procedure/check
14. Calibration checks
15. Standard barium perch/orate solution
General Comments
Figure 8.1. Method 8 checklist to be used by auditors.
-------
5-01-79 1 Section 3.7.9
*9.0 Recommended Standards for Establishing Traceability
To achieve data of desired quality,
two considerations are necessary: (1)
the measurement process must be in
a state of statistical control at the
time of the measurement, and (2) the
systematic errors, when combined
with the random variation (errors of
measurement), must result in a small
uncertainty.
To ensure good quality data, it is
necessary to perform quality control
checks and independent audits of the
measurement process; to document
these checks and audits by recording
the results on quality control charts,
as appropriate; and to use materials,
instruments, and measurement pro-
cedures that can be traced to an
appropriate standard of reference.
Data must be routinely obtained by
repeat measurements of control
standard samples and working
standards. The working calibration
standards should be traceable to
standards that are considered to be
primary. Two primary standards
recommended for establishing
traceability are:
1. Dry gas meter should be
calibrated against a wet test
meter that has been verified by
an independent liquid
displacement meter, as described
in Section 2.1.1.
2. Barium perchlorate should be
standardized against sulfuric acid
that has already been
standardized with primary grade
potassium acid phthalate. Then
standardized barium perchlorate
should be validated with an
aqueous ammonium sulfate to
make the titrant solution
traceable to two primary
standard grade reagents.
-------
6-01-79
Section 3.7.10
10.0 Reference Method*
Method 8—Determination of Sulfuric Acid Mist
and Sulfur Dioxide Emissions from
Stationary Sources
1. Principle and Applicability
1.1 Principle. A gas sample is ex-
tracted isokinetically from the
stack.The sulfuric acid mist (including
sulfur trioxide) and the sulfur dioxide
are separated, and both fractions are
measured separately by the barium-
thorin titration method.
1.2 Applicability. This method is
applicable for the determination of
sulfuric acid mist (including sulfur
trioxide, and in the absence of other
particulate matter) and sulfur dioxide •
emissions from stationary sources.
Collaborative tests have shown that
the minimum detectable limits of the
method are 0.05 milligrams/ cubic
meter (0.03 x 10~7 pounds/cubic foot)
for sulfur trioxide and 1.2 mg/m3
(0.74 x 10~7 Ib/ft3) for sulfur dioxide.
No upper limits have been
established. Based on theoretical
calculations for 200 milliliters of 3
percent hydrogen peroxide solution,
the upper concentration limit for
sulfur dioxide in a 1.0 m3 (35.3 ft3)
gas sample is about 12,500 mg/m3
(7.7 x 10~4 Ib/ft3). The upper limit can
be extended by increasing the
quantity of peroxide solution in the
impingers.
Possible interfering agents of this
method are fluorides, free ammonia,
and dimethyl aniline. If any of these
interfering agents are present (this
can be determined by knowledge of
the process), alternative methods,
subject to the approval of the
Administrator, U.S. EPA are required.
Filterable particulate matter may be
determined along with SOs and SOz
(subject to the approval of the Ad-,
ministrator) by inserting a heated
glass fiber filter between the probe
and isopropanol impinger (see Section
2.1 of Method 6). If this option is
chosen, particulate analysis is
gravimetric only; H2SO,i acid mist is
not determined separately.
2. Apparatus
2.1 Sampling. A schematic of the
sampling train used in this method is
shown in Figure 8-1; it is similar to
the Method 5 train except that the
filter position is different and the filter
•CFR60, July 1978.
holder does not have to be heated.
Commercial models of this train are
available. For those who desire to
build their own, however, complete
construction details are described in
APTD-0581. Changes from the APTD-
0581 document and allowable
modifications to Figure 8-1 are
discussed in the following subsec-
tions.
The operating and maintenance
procedures for the sampling train are
described in APTD-0576. Since
correct usage is important in
obtaining valid results, all users
should read the APTD-0576 document
and adopt the operating and
maintenance procedures outlined in it,
unless otherwise specified herein.
Further details and guidelines on
operation and maintenance are given
in Method 5 and should be read and
followed whenever they are
applicable.
2.1.1 Probe Nozzle. Same as
Method 5, Section 2.1.1.
2.1.2 Probe Liner. Borosilicate or
quartz glass, with a heating system to
prevent visible condensation during
sampling. Do not use metal probe
liners.
2.1.3 Pitot Tube. Same as Method
5, Section 2.1.3.
2.1.4 Differential Pressure Gauge.
Same as Method 5, Section 2.1.4.
2.1.5 Filter Holder. Borosilicate
glass, with a glass frit filter support
and a silicone rubber gasket. Other
gasket materials, e.g., Teflon or Viton,
may be used subject to the approval
of the Administrator. The holder
design shall provide a positive seal
against leakage from the outside or
around the filter. The filter holder
shall be placed between the first and
second impingers. Note • Do not heat
the filter holder.
2.1.6 Impingers. Four, as shown in
Figure 8-1. The first and third shall be
of the Greenburg-Smith design with
standard tips. The second and fourth
shall be of the Greenburg-Smith
design, modified by replacing the
insert with an approximately 13
millimeter (0.5 in.) ID glass tube,
having an unconstricted tip located 13
mm (0.5 in.) from the bottom of the
flask. Similar collection systems,
which have been approved by the
Administrator, may be used.
2.1.7 Metering System. Same as
Method 5, Section 2.1.8.
2.1.8 Barometer. Same as Method
5, Section 2.1.9.
2.1.9 Gas Density Determination
Equipment. Same as Method 5,
Section 2.1.10.
2.1.10 Temperature Gauge. Ther-
mometer, or equivalent, to measure
the temperature of the gas leaving the
impinger train to within 1°C (2° F).
2.2 Sample Recovery.
2.2.1 Wash Bottles. Polyethylene or
glass, 500 ml (two).
2.2.2 Graduated Cylinders. 250 ml,
1 liter. (Volumetric flasks may also be
used.)
2.2.3 Storage Bottles. Leak-free
polyethylene bottles, 1000 ml size
(two for each sampling run).
2.2.4 Trip Balance. 500-gram ca-
pacity, to measure to ±0.5 g •
(necessary only if a moisture content
analysis is to be done).
2.3 Analysis.
2.3.7 Pipettes. Volumetric 25 ml,
100ml.
2.3.2 Burette. 50 ml.
2.3.3 Erlenmeyer Flask. 250 ml.
(one for each sample blank and
standard).
2.3.4 Graduated Cylinder. 100 ml.
2.3.5 Trip Balance. 500 g capacity,
to measure to ±0.5 g.
2.3.6 Dropping Bottle. To add indi-
cator solution, 125-ml size.
3. Reagents
Unless otherwise indicated, all rea-
gents are to conform to the specifica-
tions established by the Committee on
Analytical Reagents of the American
Chemical Society, where such specifi-
-------
Section 3.7.10
5-01-79
cations are available. Otherwise, use
the best available grade.
3.1 Sampling.
3.1.1 Filters. Same as Method 5,
Section 3.1.1.
3.1.2 Silica Gel. Same as Method 5,
Section 3.1.2.
3.1.3 Water. Deionized, distilled to
conform to ASTM specification
D1193-74, Type 3. At the option of
the analyst, the KMn04 test for
oxidizable organic matter may be
omitted when high concentrations of
organic matter are not expected to be
present.
3.1.4 Isopropanol, 80 Percent. Mix
800 ml of isopropanol with 200 ml of
deionized, distilled water.
Note - Experience has shown that
only ACS grade isopropanol is
satisfactory. Tests have shown that
isopropanol obtained from commercial
sources occasionally has peroxide
impurities that will cause erroneously
high sulfuric acid •mist measurement.
Use the following test for detecting
peroxides in each lot of isopropanol:
Shake 10 ml of the isopropanol with
10 ml of freshly prepared 10 percent
potassium iodide solution. Prepare a
blank by similarly treating 10 ml of
distilled water. After 1 minute, read
the absorbance on a spectrophoto-
meter at 352 nanometers. If the
absorbance exceeds 0.1, the
isopropanol shall not be used.
Peroxides may be removed from
isopropanol by redistilling, or by
passage through a column of
activated alumina. However, reagent-
grade isopropanol with suitably low
peroxide levels is readily available
from commercial sources; therefore,
rejection of contaminated lots may be
more efficient than following the
peroxide removal procedure.
3.1.5 Hydrogen Peroxide, 3 Percent.
Dilute 100 ml of 30 percent hydrogen
peroxide to 1 liter with deionized,
distilled water. Prepare fresh daily.
3.1.6 Crushed Ice.
3.2 Sample Recovery.
3.2.1 Water. Same as 3.1.3.
3.2.2 Isopropanol, 80 Percent. Same
as 3.1.4.
3.3 Analysis.
3.3.1 Water. Same as 3.1.3.
3.3.2 Isopropanol, 100 Percent.
3.3.3 Thorin Indicator. 1-(o-arsono-
phenylazo)-2-naphthol-3, 6-disulfonic
acid, disodium salt, or equivalent.
Dissolve 0.20 g in 100 ml of
deionized, distilled water.
3.3.4 Barium Perchlorate (0.0100
Normal). Dissolve 1.95 g of barium
perchlorate trihydrate (Ba(CIC>4)2 •
3H20) in 200 ml deionized, distilled
water, and dilute to 1 liter with
isopropanol; 1.22 g of barium chloride
dihydrate (BaCI2 • 2H20) may be used
instead of the barium perchlorate.
Standardize with sulfuric acid as in
Section 5.2. This solution must be
protected against evaporation at all
times.
3.3.5 Sulfuric Acid Standard
(0.0100 N). Purchase or standardize to
±0.0002 N against 0.0100 N NaOH
that has previously been standardized
against primary standard potassium
acid phthalate.
4. Procedure
4.1 Sampling.
4.1.1 Pretest Preparation. Follow
the procedure outlined in Method 5,
Section 4.1.1; filters should be
inspected, but need not be desiccated,
weighed, or identified. If the effluent
gas can be considered dry, i.e.,
moisture free, the silica gel need not
be weighed.
4.1.2 Preliminary Determinations.
Follow the procedure outlined in
Method 5, Section 4.1.2.
4.1.3 Preparation of Collection
Train. Follow the procedure outlined
in Method 5, Section 4.1.3 (except for
the second paragraph and other
obviously inapplicable parts) and use
Figure 8-1 instead of Figure 5-1.
Replace the second paragraph with:
Place 100 ml of 80 percent
isopropanol in the first impinger, 100
ml of 3 percent hydrogen peroxide in
both the second and third impingers;
retain a portion of each reagent for
use as a blank solution. Place about
200 g of silica gel in the fourth
impinger.
Note - If moisture content is to be
determined by impinger analysis,
weigh each of the first three
impingers (plus absorbing solution) to
the nearest 0.5 g and record these
weights. The weight of the silica gel
(or silica gel plus container) must also
be determined to the nearest 0.5 g
and recorded.
4.1.4 Pretest Leak-Check Procedure.
Follow the basic procedure outlined in
Method 5, Section 4.1.4.1, noting that
the probe heater shall Bfe adjusted to
the minimum temperature required to
prevent condensation, and also that
verbage such as "... plugging the inlet
to the filter holder ...," shall be
replaced by "... plugging the inlet to
the first impinger..." The pretest leak-
check is optional.
4.1.5 Train Operation. Follow the
basic procedures outlined in Method
5, Section 4.1.5, in conjunction with
the following special instructions.
Data shall be recorded on a sheet
similar to the one in Figure 8-2. The
sampling rate shall not exceed 0.030
mVmin (1.0 cfm) during the run.
Periodically during the test, observe
the connecting line between the probe
and first impinger for signs of ;
condensation. If it does occur, adjust
the probe heater setting upward to
the minimum temperature required to
prevent condensation. If component
changes become necessary during a
run, a leak-check shall be done im-
mediately before each change, accord-
ing to the procedure outlined in
Section 4.1.4.2 of Method 5 (with
appropriate modifications; as
mentioned in Section 4.1.4 of this
method); record all leak rates. If the
leakage rate(s) exceed the specified
rate, the tester shall either void the
run or shall plan to correct the sample
volume as outlined in Section 6.3 of
Method 5. Immediately after
component changes, leak-checks are
optional. If these leak-checks are
done, the procedure outlined in
Section 4.1.4.1 of Method 5 (with
appropriate modifications) shall be
used.
After turning off the pump and
recording the final readings at the
conclusion of each run, remove the
probe from the stack. Conduct a
posttest (mandatory) leak-check as in
Section 4.1.4.3 of Method 5 (with
appropriate modification) and record
the leak rate. If the posttest leakage
rate exceeds the specified acceptable
rate, the tester shall either correct the
sample volume, as outlined in Section
6.3 of Method 5, or shall void the run.
Drain the ice bath and, with the
probe disconnected, purge the re-
maining part of the train, by drawing
clean ambient air through the system
for 15 minutes at the average flow
rate used for sampling.
Note - Clean ambient air can be
provided by passing air through a
charcoal filter. At the option of the
tester, ambient air (without cleaning)
may be used.
-------
6-01-79
Section 3.7.10
4.1.6 Calculation of Percent Iso-
kinetic. Follow the procedure outlined
in Method 5, Section 4.1.6.
*
4.2 Sample Recovery.
4.2.1 Container No. 1. If a moisture
content analysis is to be done, weigh
the first impinger plus contents to the
nearest 0.5 g and record this weight.
Transfer the contents of the first
impinger to a 250-ml graduated
cylinder. Rinse the probe, first
impinger, all connecting glassware
before the filter, and the front half of
the filter holder with 80 percent
isopropanol. Add the rinse solution to
the cylinder. Dilute to 250 ml with 80
percent isopropanol. Add the filter to
the solution, mix, and transfer to the
storage container. Protect the solution
against evaporation. Mark the level of
liquid on the container and identify
the sample container.
4.2.2 Container No. 2. If a moisture
content analysis is to be done, weigh
the second and third impingers (plus
contents) to the nearest 0.5 g and
record these weights. Also, weigh the
spent silica gel (or silica gel plus
impinger) to the nearest 0.5 g.
Transfer the solutions from the
second and third impingers to a 1000-
ml graduated cylinder. Rinse all con-
necting glassware (including back half
of filter holder) between the filter and
silica gel impinger with deionized,
distilled water, and add this rinse
water to the cylinder. Dilute to a
volume of 1000 ml with deionized,
distilled water. Transfer the solution
to a storage container. Mark the level
of liquid on the container. Seal and
identify the sample container.
4.3 Analysis.
Note the level of liquid in containers
1 and 2, and confirm whether or not
any sample was lost during shipment;
note this on the analytical data sheet.
If a noticeable amount of leakage has
occurred, either void the sample or
use methods, subject to the approval
of the Administrator, to correct the
final results.
4.3.1 Container No. 1. Shake the
container holding the isopropanol
solution and the filter. If the filter
breaks up, allow the fragments to
settle for a few minutes before
removing a sample. Pipette a 100-ml
aliquot of this solution into a 250-ml
Erlenmeyer flask, add 2 to 4 drops of
thorin indicator, and titrate to a pink
endpoint using 0.0100 N barium
perchlorate. Repeat the titration with
a second aliquot of sample and
average the titration values. Replicate
titrations must agree within 1 percent
or 0.2 ml, whichever is greater.
4.3.2 Container No. 2. Thoroughly
mix the solution in the container
holding the contents of the second
and third impingers. Pipette a 10-ml
aliquot of sample into a 250-ml
Erlenmeyer flask. Add 40 ml of
isopropanol, 2 to 4 drops of thorin
indicator, and titrate to a pink
endpoint using 0.0100 N barium per-
chlorate. Repeat the titration with a
second aliquot of sample and average
the titration values. Replicate
titrations must agree within 1 percent
or 0.2 ml, whichever is greater.
4.3.3 Blanks. Prepare blanks by
adding 2 to 4 drops of thorin indicator
to 100 ml of 80 percent isopropanol.
Titrate the blanks in the same manner
as the samples.
5. Calibration
5.1 Calibrate equipment using the
procedures specified in the following
sections of Method 5: Section 5.3
(metering system); Section 5.5
(temperature gauges); Section 5.7
(barometer). Note that the
recommended leak-check of the
metering system, described in Section
5.6 of Method 5, also applies to this
method.
5.2 Standardize the barium per-
chlorate solution with 25 ml of
standard sulfuric acid, to which 100
ml of 100 percent isopropanol has
been added.
6. Calculations
Note - Carry out calculations
retaining at least one extra decimal
figure beyond that of the acquired
data. Round off figures after final
calculation.
6.1 Nomenclature.
An = Cross-sectional area of noz-
zle, m3 (ft3).
Bws= Water vapor in the gas
stream, proportion by
volume.
CH2so4 = Sulfuric acid (including SO3)
concentration, g/dscm (Ib/
dscf).
Cso2= Sulfur dioxide
concentration, g/dscm
(Ib/dscf).
I = Percent of isokinetic samp-
ling.
N = Normality of barium per-
chlorate titrant, g equiva-
lents/liter.
Pbar = Barometric pressure at the
sampling site, mm Hg (in.
Hg).
Ps=Absolute stack gas
pressure, mm Hg (in. Hg).
P5td=Standard absolute pressure,
760 mm Hg (29.92 in. Hg).
Tm= Average absolute dry gas
meter temperature (see
Figure 8-2), °K (°R).
Ts= Average absolute stack gas
temperature (see Figure 8-
2), °K (°R).
Tst
-------
Section 3.7.10
5-01-79
(20°C and 760 mm Hg or 68°F and
29.92 in. Hg) by using Equation 8-1.
V,,
,=VmY
P- + I™. }
\ 113.6 I
Pstc
= K,VmY
Pbar + (AH/13.6)
Equation 8-1
where
Ki =0.3858 °K/mm Hg for metric
units.
= 17.64 °R/in. Hg for English units.
Note - If the leak rate observed
during any mandatory leak-checks
exceeds the specified acceptable rate,
the tester shall either correct the
value of Vm in Equation 8-1 (as
described in Section 6.3 of Method 5),
or shall invalidate the test run.
6.4 Volume of Water Vapor and
Moisture Content. Calculate the
volume of water vapor using Equation
5-2 of Method 5; the weight of water
collected in the impingers and silica
gel can be directly converted to
milliliters (the specific gravity of water
is 1 g/ml). Calculate the moisture
content of the stack gas, using
Equation 5-3 of Method 5. The
"Note"in Section 6.5 of Method 5 also
applies to this method. Note that if the
effluent gas stream can be considered
dry, the volume of water vapor and
moisture content need not be
calculated.
6.5 Sulfuric acid mist (including
SOa) concentration.
N(V, - Vu)
H4S02
= K2
V80,n
6.7 Isokinetic Variation.
6.7.1 Calculation from raw data.
I = 100 T. [K4VIC + (BmY/Tm) (Pto, + AH/13.6)]
60 6 v.P.An
Equation 8-4
where:
K« =0.003464 mm Hg-mVml-°Kfor
metric units.
= 0.002676 in. Hg-ftVml-°R for
English units.
6.7.2 Calculation from intermediate
values.
= TsVm(3ldl Pstd 100
PaV, Anfl (1-BW.)
Equation 8-5
where
K5=4.320 for metric units.
= 0.09450 for English units.
6.5 Acceptable Results. If 90
percent
-------
6-01-79
Section 3.7.10 >
Temperature Sensor
Probe
Thermometer
Probe
Reverse Type
Pilot Tube
Check
Valve
Vacuum
Gauge
Main Valve
Dry Test Meter
Figure 8.1. Sulfuric acid mist sampling train.
-------
Section 3.7.10
6-01-79
Plant
Location
Operator
Date
Run No.
Sample box no.
Meter box no. .
Meter AH@
C factor
Static pressure mm Hg tin. Hg)
Ambient temperature
Barometric pressure
Assumed moisture, %
Probe length, m (ft)
Nozzle identification no.
Average calibrated nozzle diameter, cm (in.)
Probe heater setting _
Pilot tube coefficient. Cp
Schematic of stack cross section
Leak rate. m3/min. (cfm)
Probe liner material
Filter no.
Traverse
Number
•Total
Sampling
Time
(Q). min
Average
Vacuum
mm Hg
(in. Hg)
Stack
Temperature
-------
5-01-79 1 Section 3.7.11
11.0 References
1. Buchanan, J.W., and D.E. Monitoring and Support
Wagoner. Guidelines for Laboratory (MD-77), Research
Development of a Quality Triangle Park, N.C. 27711.
Assurance Program: Volume VII -
Determination of Sulfuric Acid
Mist and Sulfur Dioxide
Emissions from Stationary
Sources. EPA-650/4-74-005-g.
Environmental Protection
Agency, Research Triangle Park,
N.C., March 1976.
2. Hamil, H. F., D. E. Camann, and
R. E. Thomas. Collaborative
Study of Method for the
Determination of Sulfuric Acid
Mist and Sulfur Dioxide
Emissions from Stationary
Sources. EPA-650/4-75-003,
Environmental Protection
Agency, Research Triangle Park,
N.C. 1974.
3. Driscoll, J., J. Becker, and R. "
Herbert. Validation of Improved
Chemical Methods for Sulfur
Oxide Measurements from
Stationary Sources. EPA-R2-72-
105. National Environmental
Research Center, Research
Triangle Park, N.C.
4. Martin, R. M. Construction
Details of Isokinetic Source
Sampling Equipment. Publication
No. APTD-0581. Air Pollution
Control Office, Environmental
Protection Agency, Research
Triangle Park, N.C. 1971.
5. Rom, J.J. Maintenance,
Calibration, and Operation of
Isokinetic Source Sampling
Equipment. Publication No.
APTD-0576. Office of Air
Programs, Environmental
Protection Agency, Research
Triangle Park, N.C. 1972.
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 Interlaboratory
Source Performance Surveys for
EPA Reference Methods 6 and 7
- 1978. Report in preparation by
U.S. Environmental Protection
Agency, Environmental
-------
5-01-79 1 Section 3.7.12
Blank data forms are provided on
the following pages for the
convenience of the Handbook user.
Each blank form has the customary
descriptive title centered at the top of
the page. However, 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 M8-1.2
indicates that the form is Figure 1.2 in
Section 3.7.1 of the Method 8 Hand-
book. Future revisions of these forms,
if any, can be documented by 1.2A,
1.28, etc. Sixteen 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
2.3A and 2.3B Meter Box Calibration
Data and Calculation
Form (English and
metric units)
2.4A and 2.4B Posttest Meter Calib-
ration Data Form
(English and metric
units)
2.5 (MH) Pretest Sampling
Checks
2.6 Nozzle Calibration Form
3.1 (MH) Pretest Preparations
4.1 Method 8 Field Data
Fotm
4.2 Sample Label
4.3 Sample Recovery and
Integrity Data
4.4 (MH) On-Site Measurements
5.1 (MH) Posttest Sampling
Checks
5.2 Method 8 Analytical
Data Form
5.3 Control Sample Analy-
tical Data Form
5.4 (MH) Posttest Operations
6.1 A and 6.1B Sulfuric Acid Mist
Calculation Form (Eng-
lish and metric units)
6.2A and 6.2B Sulfur Dioxide Calcul-
ation Form (English
and metric units)
8.1 Method 8 Checklist to
be Used by Auditors
12.0 Data Forms
-------
Procurement Log
Item description
Ctty.
Purchase
order
number
•
Vendor
Date
Ord.
Rec.
Cost
Dispo-
sition
Comments
M
i
5'
3
N>
M
Ol
6
vl
CO
Quality Assurance Handbook M8-1.2
-------
5-01-79
Section 3.7.12
Date
Barometric pressure. P» = .
Meter Box Calibration Data and Calculation Form
(English Units)
. in. Hg.
Meter box number
Calibrated by
Orifice
manometer
setting
(&H),
in. HzO
0.5
1.0
1.5
2.0
3.0
4.0
Wet test
meter
/VJ,
ft3
5
5
10
10
10
10
Gas volume
Dry gas
meter
(Va),
ft3
Temperature"
Wet test
meter
(tj.
°F
Dry gas meter
Inlet
M
°F
Outlet
(t*J.
°F
Average
(ta).a
°F
Time
(Q).
mm
Average
Y;
AW@i
AW
0.5
7.0
1.5
2.0
3.0
4.0
f\H
13.6
0.0368
0.0737
0.110
0.147
0.221
0.294
V» Pb (ta + 460)
AW
Va(Pt> + 13.6)ft» + 460f
A , ,^ 0.037 7 AW f ft* + 460) 0 "1
AW@i
Pt(ta+460) I Vw J
Meter Box Calibration Data and Calculation Form
Nomenclature:
yw = Gas volume passing through the wet test meter, ft3.
Va = Gas volume passing through the dry test meter, ft3.
fw = Temperature of the gas in the wet test meter, °F.
ta; = Temperature of the inlet gas of the dry test meter. °F.
to0= Temperature of the outlet gas of the dry test meter, °F.
ta = Average temperature of the gas in the dry test meter, obtained by the average
-------
Section 3.7.12 4 6-01-79
Meter Box Calibration Data and Calculation Form
(metric units)
Date
Barometric pressure. Pt,=-
. mm Hg.
. Meter box number.
Calibrated by
Orifice
manometer
setting
(MH
mm H20
JO
25
40
50
75
WO
Wet test
meter
(vj.
m3
0.15
0.15
0.30
0.30
0.30
0.30
Gas volume
Dry gas
meter
(Vat.
m3
Temperature*
Wet test
meter
M.
°C
Dry gas meter
Inlet
(taj,
°C
Outlet
(toj,
°C
A verage
ft a),'
°C
Time
(Q).
min
Y,
Average
AM§>i
A//
10
25
40
50
75
100
AW
13.6
0.7
1.8
2.94
3.68
5.51
7.35
v- V« P^fta + 273)
Va(Pt,+-fifa)(t* + 273)
2
^HtS>{=0-00117^H 1" (t»*273JQ "I
P*(ta + 273j [ yw J
"If there is only one thermometer on the dry gas meter, record it under to.
Meter Box Calibration Data and Calculation Form
Nomenclature:
V* = Gas volume passing through the wet test meter, m3.
Va = Gas volume passing through the dry test meter, m3.
TM = Temperature of the gas in the wet test meter, °C.
t ±3.8 mm W20 (recommended).
AW@= Average orifice pressure differential that gives 0.021 m3 of air at standard conditions for all six runs, mm
Tolerance AW@ = 46.74 ±6.3 mm H20 (recommended).
Pti= Barometric pressure, mm. Hg.
Quality Assurance Handbook M8-2.3B
-------
Date
Barometric pressure. Pi, =
in. Hg
Posttest Meter Calibration Data Form (English units)
Test numbers
Plant
Pretest Y
Meter box number
Dry gas meter number
Orifice
manometer
setting.
(W).
in. H&
Gas volume
wet test
meter
(VJ,
ft3
10
10
10
Gas volume
dry gas
meter
(V«),
ft*
Temperature
Wet test
meter
(tj.
°F
Dry gas meter
Inlet
ffd,>.
°F
Outlet
ftoj.
°F
A verage
fldT
°F
Time
(Q).
min
Vacuum
setting.
in. Hg
Y>
K =
VvPh(ta + 460)
l/dp'b+ A//Vfw + 4601
I 13.6\
Y=
01
6
where
Uw = Gas volume passing through the wet test meter, ft3.
Va = Gas volume passing through the dry test meter, ft3.
f« = Temperature of the gas of the wet test meter, °F.
fd; = Temperature of the inlet gas of the dry test meter. °F.
fd0 = Temperature of the outlet gas of the dry test meter. °F.
ta = Average temperature of the gas in the dry test meter, obtained by the average ta{ and t^ °F.
&H=Pressure differential across orifice, in. H&.
Y, = Ratio of accuracy of wet test meter to dry test meter for each run.
Y=Average ratio of accuracy of wet test meter to dry test meter for all three runs.
Tolerance=Pretest V ±0.05 /
Pt>=Barometric pressure, in. Hg.
R = Time of calibration run, min.
w
Quality Assurance Handbook M8-2.4A
-------
Posttest Meter Calibration Data Form (metric units)
Test numbers
Date.
Meter box number.
Plant
Barometric pressure, Ph -.
. mm Hg Dry gas meter number,
Pretest Y
Orifice
manometer
setting.
(m
mm HsO
0.3O
0.30
' 0.30
Gas volume
wet test
meter
fVU
'm3
Gas volume
dry gas
meter
(VJ.
m3
Temperature
Wet test
meter
(tj.
°C
Dry gas meter
Inlet
o
A
W
vl
1*
M
' If there
where
Gas volume passing through the wet test meter, m3.
Gas volume passing through the dry test meter, m3.
= Temperature of the gas in the wet test meter, °C.
Temperature of the inlet gas of the dry test meter, °C.
Temperature of the outlet gas of the dry test meter, °C.
=A verage temperature of the gas in the dry test meter, obtained by the average of fd, and ta
= Pressure differential across orifice, mm H^O.
= Ratio of accuracy of wet test meter to dry test meter for each run.
Average ratio of accuracy of wet test meter to dry test meter for all three runs.
Tolerance = Pretest Y ±O.05Y
P» = Barometric pressure, mm Hg.
0 = Time of calibration run, min.
t „ =
ta j =
t d<) =
ta
A//
Y,
Y
°C.
01
6
vl
to
Quality Assurance Handbook M8-2.4B
-------
5-01-79
Section 3.7.12
Nozzle Calibration
Date.
Calibrated by.
Nozzle
identification
number
01.
mm (in.)
02.
mm (in.)
03.
mm (in.)
A0,
mm (in.)
Oavfl
where
01,2.3, = nozzle diameter measured on a different diameter, mm (in.). Tolerance = measure within 0.25 mm (0.001.)
A ^maximum difference in any two measurements, mm (in.). Tolerance = 0.1 mm (0.004 in.).
0a»o =average of 0i, 0a 03.
Quality Assurance Handbook M8-2.6
-------
Method 8 Field Test Data Form
Plant
1 nratinn
Operatnr .
Date
Run number
Sample hnx number
Meter hnx number
Meter AM®
Meter calibration Y . ,
Pitot tube C.P
Probe length
Probe liner material
Probe heater setting
Ambient temperature
Barometric pressure
Assumed moisture
Static pressure
C factor
Reference AP
Maximum AH
Sheet
Nozzle identification
Nozzle diameter
Final leak rate
Vacuum during leak
Remarks:
of
number
check
w
o
o
5'
3
U
Traverse point
number
Total or Avg
Samp/ing
time
(QJ.
min
Clock
time
24 h
Vacuum,
mm Hg
/in. Hg)
Stack
temperature
(TJ.
°C (°F)
•
Velocity
head
(&P,J.
mm HzO
(in. H2O)
Pressure
differential
across
orifice
meter,
mm H2O
fin. H2OJ
Gas sample
volume,
m3 (ft3)
Gas sample tempera-
ture at dry gas meter
Inlet.
°C (°F)
Outlet,
°C (°F)
Temperature
of gas
leaving
condenser or
last impinger,
°C (°FJ
Ol
b
Quality Assurance Handbook MS-,4.1)
-------
6-01-79
Section 3.7.12
Plant City
Site Samole type
Date Run number
Front rinse D Front filter D Front solution D
Back rinse D Back filter D Back solution D
Solution . Level marked d
42
Vnlume: Initial Final jj
Cleanuo bv e?
Quality Assurance Handbook M6-4.2
-------
Section 3.7.12
10
6-01-79
Sample Recovery and Integrity Data
Plant
Sample location.
Field Data Checks
Person with direct responsibility for recovt
Sample
number
1
2
3
Blanks
Sample
identification
number
.HtSO*
soz
*rerl samples
Date
of
recovery
Liquid
level
marked
Stored
in locked
container
Remarks
Signature nf field sample trustee ,_ _
Laboratory Data Checks*:
Date recovered samples rece
Analyst
ived
Sample
number
1
2
3
Blanks
Sample
identification
number
H*0<
SO*
Date
of
analysis
Liquid
at marked
level
Sample
identified
Remarks
Signature of lab sample trustee.
Quality Assurance Handbook M8-4.3
-------
6-01-79
11
Section 3.7.12
Method 8 Analytical Data Form
Plant
Sample location
Volume and normality of
barium perch/orate
Date
Analyst
1 ml fla (rin^
P ml Pa (C.IO^2 N -
Rlank ml Ra friD,l*
Sulfur Trioxide Analysis
Vsoin - Total volume of solution in which the sulfuric
acid sample is contained, ml
Va - Volume of sample aliquot, ml
Vt - Volume of barium perch/orate
titrant used for sample, ml
l/tb* - Volume of barium perch/orate
titrant used for blank, ml
Jst tit rat ion
2nd titration
1st titration
2nd titration
A verage
1st titration
2nd titration
Average
Run 1
Run 2
Run 3
= 0.93 to 1.01 or \ 1st titration - 2nd titration \ < 0.2 ml
Sulfur Dioxide Analysis
Vsom - Total volume of solution in which the sulfur dioxide
sample is contained, ml
Ve - Volume of sample aliquot, ml
V, - Volume of barium perchlorate
titrant used for sample, ml
u* - Volume of barium perchlorate
titrant used for blank, ml
1st titration
2nd titration
Average
1st titration
2nd titration
Average
Run 1
Run 2
Run 3
1st titration
2nd titration
Signature of analyst
= 0.99 to 1.01 or \ 1st titration - 2nd titration\ < 0.2 ml
Signature of reviewer or supervisor.
* Volume of blank and sample titrated should be the same; otherwise a volume correction must be made.
Quality Assurance Handbook M8-5.2
-------
Section 3.7.12 12
6-01-79
Plant
Analyst.
Control Sample Analytical Data Form
Weight of ammonium sulfate is 1.3214 gram?_
Dissolved in 2 L of distilled water?
_Date analyzed.
. /VBa(CIO4lz
Titration of blank .
. ml Ba
(must be less than the 0.5 ml tit rant)
Control
Sample
Number
Time of
Analysis
24 h
Titrant volume, ml
1st
2nd
3rd
Ave.
(Two consecutive volumes must agree within 0.2 ml)
mlBa(CIO<)2xNBflao4>2 = 25ml x 0.0 JN
(control sample) (control sample)
ml x N =
(must agree within ±5%, i.e., 0.233 to 0.268)
Does value agree? yes no.
.Signature of analyst
. Signature of reviewer
Quality Assurance Handbook M8-5.3
-------
6-01-79
13
Section 3.7. 12
Sulfuric Acid Mist (Including SO3) Calculation Form
(English units)
Sample Volume
ft3, TV* 3=
. °R.
in. Hg
Y =
in. H20
= j7.64VmY
+ fA"/73.6;1
Tm J
. Equation 6-1
Sulfuric Acid Mist (Including SOa) Concentrations
N = .
VM,n =
g-eq/L. Vt = __ . __ ml, Vtt> =
ml. V, = . ml, Vm =
ml
ft3
CH2so4 = 1.081x10-
= . x 1.0'* Ib/dscf
Equation 6-2
Quality Assurance Handbook M8-6.1A
-------
Section 3.7.12
14
5-01-79
Sulfuric Acid Mist (Including 80s) Calculation Form
(metric units)
Sample Volume
m3, Tm =
_. ___ K. /'bar — __ __ __ • __ mm Hg
mm HZ0
= 17.64VmY
Equation 6-1
Sulfuric Acid Mist (Including SO*) Concentrations
N=.
g-eq/L. Vt —
ml, Va =
, ml. V,h == • ml
ml, Vm = m3
CH2so4 = 0.04904
N (V, •
I/.
"std
— • g/dscm
Equation 6-2
Quality Assurance Handbook M8-6. IB
-------
6-01-79 15
Sulfur Dioxide Calculation Form
(English units)
Section 3.7.12
Sample Volume
Vm =_
Y = .
— . in. Hg
in. HZ0
= 17.64VmY
+ (&H/13.6) _
rm J *
ft3
Equation 6-1
Sulfuric Acid Mist (Including SOs) Concentrations
N =.
g-eq/L, Vt —
_._ ml. I/. =
ml. f,B. =
ml
ml.
Cso3 = 7.061 x ;cr9
x 10'* Ib/dscf Equation 6-2
Quality Assurance Handbook M8-6.2A
-------
Section 3.7. 12 16
Sulfur Dioxide Calculation Form
(metric units)
6-01-79
Sample Volume
— • m3. Tm — • __ K. Ptm == • mm Hg
mm
= 0.3858 VmY
m3
Equation 6-1
SOz Concentration
N =•
l/soln =
g-eq/L, V, =_ . ml, V,h = ml
•. ml. Va ^= • ml.
Cso2 = 3.203x 10"
"std
— . g/dscm
Equation 6-2
Quality Assurance Handbook M8-6.2B
-------
6-01-79 17 Section 3.7.12
Method 8 Checklist To Be Used BY Auditors
Yes No Comment Presampling Preparation
1. Knowledge of process conditions
2. Calibration of pertinent equipment in partic-
ular, 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 solu-
tions to impingers
5. Isokinetic sampling
6. Purging of the sampling train and rinsing of
the impingers and connecting tubes to recover
the sample.
7. Recording of pertinent process condition
during sample collection
8. Maintaining the probe at a given tempera-
ture
Postsampling
9. Control sample analysis - accuracy and precision
10. Sample aliquotting techniques
11. Tit rat ion technique, particularly endpoint
precision
12. Use of detection blanks in correcting field
sample results
13. Calculation procedure/check
14. Calibration checks
15. Standard barium per chlorate solution
General Comments
*U.S.GOVERNMENTPRINT1NGOFFICERS 88 .5*8-15* 87022
Quality Assurance Handbook M8-8.1
------- |