United States Environmental Monitoring Systems
Environmental Protection Laboratory
Agency Research Triangle Park NC 27711
Research and Development EPA/600/4-77/027b August 1988
vvEPA Quality Assurance
Handbook for
Air Pollution
Measurement
Systems:
Volume III. Stationary
Sources Specific
Methods
Section 3.16
-------
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
3.04 Procedure for NBS-Traceable Certification 14 6-09-87
of Compressed Gas Working Standards
Used for Calibration and Audit of
Continuous Source Emission Monitoring
(Revised Traceability Protocol No. 1
305 Specific Procedures to Assess 58 9-23-85
Accuracy of Reference Methods Used for
SPNSS
306 Specific Procedures to Assess 14 9-23-85
Accuracy of Reference Methods Used foi
NESHAP
307 Calculation and Interpretation of 14 11-05-85
Accuracy for Continuous Emission
Monitoring Systems (CEMS)
308 Audit Materials Available from / 1 1 04-85
U.S.E.P.A.
309 Continuous Emission Monitoring 47 6-01-86
Systems (CEMS) Good Operating
Practices
3010 Guideline for Developing Quality 11 1126-85
Control Procedures for Gaseous
Continuous Emission Monitoring
Systems
3 1 Method 2 Determination of Stack Gas
Velocity and Volumetric Flow Rate
31 1 Procurement of Apparatus and Supplies lb 1 15-80
312 Calibration of Apparatus 21 1 15-80
313 Presamplmg Operations 7 1-15-80
31.4 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
3111 References 2 1 15-80
3112 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
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August 1988
Table of Contents (continued)
Section Pages Date
3.2.4 On-Site Measurements 12 1-15-80
3.2.5 Postsampling Operations 2 1-15-80
3.2.6 Calculations 3 1-15-80
3.2.7 Maintenance 1 1-15-80
3.2.8 Auditing Procedure 5 1-15-80
3.2.9 Recommended Standards for i 1-15-80
Establishing Traceability
3.2.10 Reference Method 3 1-15-80
3.2.11 References .1 1-15-80
.3.2.12 Data Forms 6 1-15-80
3.3 Method 4—Determination of Moisture
in Stack Gases
3.3.1 Procurement of Apparatus and Supplies 9 1-15-80
3.3.2 Calibration of Apparatus 19 1-15-80
3.3.3 Presampling Operations 7 1-15-80
3.3.4 On-Site Measurements . 10 1-15-80
3.3.5 Postsampling Operations 4 1-15-80
3.3.6 Calculations . 8 1-15-80
3.3.7 Maintenance 3 1-15-80
3.3.8 Auditing Procedure 4 1-15-80
3.3.9 Recommended Standards for 1 1-15-80
Establishing Traceability
3.3.10 Reference Method 5 1-15-80
3.3.11 References 1 1-15-80
3.3.12 Data Forms 14 1-15-80
3.4 Method 5—Determination of Paniculate
Emissions from Stationary Sources
3.4.1 Procurement of Apparatus 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
Table of Contents (continued)
Section Pages Date
3.9.1 Procurement of Apparatus and Supplies 20 1-04-82
3.9.2 Calibration of Apparatus 25 1-04-82
3.9.3 Presampling Operations 6 1-04-82
3.9.4 On-Site Measurements 21 1-04-82
3.9.5 Postsampling Operations 19 1-04-82
3.9.6 Calculations 7 1-04-82
3.9.7 Maintenance 3 1-04-82
3.9.8 Auditing Procedure 8 1-04-82
3.9.9 Recommended Standards for 1 1-04-82
Establishing Traceability
3.9.10 Reference Method 2 1-04-82
3.9.11 References 1 1-04-82
3.9.12 Data Forms 22 1-04-82
3.10 Method 1 3A—Determination of Total
Fluoride Emissions from Stationary
Sources (SPADNS Zirconium Lake
Method)
3.10.1 Procurement of Apparatus and Supplies 13 1-04-82
3.10.2 Calibration of Apparatus 5 1-04-82
3.10.3 Presampling Operations 3 1-04-82
3.10.4 On-Site Measurements 3 1-04-82
3.10.5 Postsampling Operations 18 1-04-82
3.10.6 Calculations 7 1-04-82
3.10.7 Maintenance 2 1-04-82
3.10.8 Auditing Procedure 1 1-04-82
3.10.9 Recommended Standards for 1 1-04-82
Establishing Traceability
3.10.10 Reference Method 5 1-04-82
3.10.11 References 1 1-04-82
3.10.12 Data Forms 6 1-04-82
3.11 Method 1 7—Determination of Paniculate
Emissions from Stationary Sources
(In-Stack Filtration Method)
3.11.1 Procurement of Apparatus and Supplies 9 1-04-82
3.11.2 Calibration of Apparatus 2 1-04-82
3.11.3 Presampling Operations 3 1-04-82
3.11.4 On-Site Measurements 6 1-04-82
3.11.5 Postsampling Operations 1 1-04-82
3.11.6 Calculations 1 1-04-82
3.11.7 Maintenance 2 1-04-82
3.11.8 Auditing Procedure 2 1-04-82
3.11.9 Recommended Standards for 1 1-04-82
Establishing Traceability
3.11.10 Reference Method 11 1-04-82
3.11.11 References 1 1-04-82
3.11.12 Data Forms 1 1-04-82
3.12 Method 9--Visible Determination of
the Opacity Emissions from
Stationary Sources
3.12.1 Certification and Training of Observers 5 4-20-83
3.12.2 Procurement of Apparatus and Supplies 2 4-20-83
3.12.3 Preobservation Operations 2 4-20-83
3.12.4 On-Site Field Observations 18 4-20-83
3.12.5 Postobservation Operations 2 4-20-83
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August 1988
Table of Contents (continued)
Section Pages Date
3.12.6 Calculations 7 4-20-83
3.12.7 Auditing Procedure 2 4-20-83
3.12.8 Reference Method 5 4-20-83
3.12.9 References and Bibliography 1 4-20-83
3.12.10 Data Forms 9 4-20-83
3.1 3 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
-------
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
3.1 6.9 Recommended Standards for Establishing
Traceability 1 6-30-88
3.16.10 Reference Methods 22 6-30-88
3.16.11 , References 5 6-30-88
3.16.12 Data Forms 21 6-30-88
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Section No. 3-16
Date June 30, 1988
Page 1
Section 3«l6
METHOD 18 — MEASUREMENT OF GASEOUS ORGANIC COMPOUND
EMISSIONS BY GAS CHROMATOGRAPHY
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 METHODS
11. REFERENCES
12. DATA FORMS
Documentation
3.16
3.16
3.16.1
3.16.2
3.16.3
3-16.4
3.16.5
3.16.6
3-16.7
3.16.8
3-16.9
3.16.10
3.16.11
3.16.12
Number
of Pages
3
19
16
15
44
33
39
6
3
8
l
22
5
21
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Section No. 3.16,
Date June 30, 1988
Page 2
To assist the Handbook user in applying Section 3-16 to particular sampling
and analytical techniques, the following table provides a quick cross reference to
each of the subsections dealing with each of the sampling and analytical
approaches.
CROSS REFERENCES TO SUBSECTIONS RELATED TO SAMPLING APPROACHES
Activity
Procurementof equipment
Sampling
Analytical
Reagents
Calibration
Sampling equipment
Presampling operations
Survey measurements
Survey preparations
Sample collection
Sample analysis
Interpretation of data
Preparation for test:
equipment
reagents
Packing equipment
On-site Measurements
Sampling
Postsampling Operations
Prepartion of calibration
s tandards
Audit sample analysis
Sample analysis
Calculations
Emission calculations
Auditing Procedures
Performance audits
System audits
All
Methods
l.lpl"
1.2p8
1-3P9
2.1pl
3-lpl
3-2pl
3-3P10
3-4pl3
3-4pl9
3-5P21
3-&P30
3-7P32
4.3P2
S.lpl
5-2p22
5-3P22
6.0pi
S.lpl
8.2p5
Flask
Sampling
1.1P3
1.2p8
1.3P9
2.1pl
3-lpl
3-2p8.
3-3P11
3-4pl7
3- ''Pig
3-5P28
3-6p30
3-7P32
N/A
• ••
5-lpl
N/A
N/A
6.1pl
N/A
N/A
Rigid
Container
Sampling
I.lp4
1.2p8
1-3P9
2.1pl
3-lpl
3-2 P9
3-3P12
3.4pl8
3-4pl9
3-5P28
3.&P30
3-7P32
4-3P2
5-ipl
5.2p22
5-3P22
6.lpl
8.1P4
8.2p5
Direct
Bag
Sampling
l.lpft
1.2p8
1-3P9
2.1pl
3-lpl
3-2p9
3-3P12
3.AP18
3-*pi9
3-5P28
3-6p30
3-7P32
1-3P9
S.lpl
5.2p22
5-2p22
6.1pl
S.lpA
8.2P5
Direct
Interface
Sampling
I.lp6
1.2p8
1-3P9
2.1pl
3-lpl
N/A
N/A
N/A
3-tpl9
3-5P29
3.6P30
3-7P32
4-3P13
S.lpl
5-2p22
5-2p23
6.1pl
8.1p/(
8.2p5
Dilution
Interface
Sampling
1.1P7
1.2p8
1-3P9
2.2P9
3-lpl
N/A
N/A
N/A
S-'ipig
3-5P29
3-&P30
3-7P32
A.3pi*
S.lpl
5-2p22
5.2P25
6.lpi
8. IpS
8.2p5
Adsorption
Tube
Sampling
1.1P3
1.2p8
1-3P9
2.1pl
3-ipl
3-2plO
3-3P12
3-4pi9
3-1pl9
3-5P28
3-6p30
3-7P32
4.3P17
5.1pl2
5-2p22
5.2p26
6.2p2
8. IPS
8.2p5
"l.lpl" - Means that the procurement of the sampling equipment is dicussed in Section
beginning on page 1 of Section 3-16.1.
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Section No. 3.16
Date June 30, 1988
Page 3
SUMMARY
Method 18 is a generic method for measuring gaseous organic compounds. The
method is based on separating the major gaseous organic components of a gas mixture
with a gas chromatograph (GC) and measuring the separated components with a
suitable detector. The gas samples are analyzed immediately as taken from the
stack or within a set period of time after being collected in a Tedlar bag or on an
adsorption tube.
To identify and quantify the major components, the retention times of each
separated component are compared with those of , known compounds under identical
conditions. Therefore, the analyst must identify approximate concentrations of the
organic emission components beforehand. With this information, the analyst can
then prepare or purchase commercially available standard mixtures to calibrate the
GC under physical conditions identical to those that will be used for the samples.
The analyst must also have some presurvey information concerning interferences
arising from other compounds present and indicating the need for sample dilution to
avoid detector saturation, gas stream filtration to eliminate particulate matter,
and prevention of sample loss in moisture condensation in the sampling apparatus.
This method is structured to analyze approximately 90 percent of the total
gaseous organics emitted from an industrial source. It does not include techniques
to identify and measure trace amounts of organic compounds, such as those found in
building air and fugitive emission sources.
This method will not determine compounds that 1) are polymeric (high molecular
weight), 2) polymerize before analysis, or 3) have very low vapor pressures at
stack or instrument conditions.
The range of this method is from about 1 part per million (ppm)* to the upper
limit governed by GC detector saturation or column overloading. The upper limit
can be extended by diluting the stack gases with an inert gas or by using smaller
gas sampling loops. The sensitivity limit for a compound is defined as the minimum
detectable concentration of that compound, or the concentration that produces a
signal-to-noise ratio of three to one. The minimum detectable concentration and
limit of quantitation are determined during the presurvey calibration for each
compound. . _
The method descriptions given herein are based on the method ' promulgated
October 8, 1983, and on corrections and additions published on May 30, 1984
(Section 3-16.10). Revisions to the method were promulgated February 19, 198? and
these are also described. Blank forms for recording data are provided in the
Method Highlights and in Section 3-3-12 for the convenience of Handbook users.
*Note: Selective detectors may allow detection and quantitation of far smaller
concentrations of certain types of gaseous organic compounds.
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Section No. 3.16
Date June 30, 1<588
Page 4
METHOD HIGHLIGHTS
Section 3-16 describes procedures and specifications for determining gaseous
organic compounds from stationary sources. A gas sample is extracted from the
stack at a rate proportional to the stack velocity using one of four techniques:
(1) integrated bag sampling, (2) direct interface sampling, (3) dilution interface
sampling, and (4) adsorption tube sampling. For the first three techniques, the
sample or diluted sample is introduced directly into the sample loop of the gas
chromatograph (GC). The measured sample is then carried into the GC column with a
carrier gas where the organic compounds are separated. The organic compounds then
are each measured quantitatively by the GC detector. The qualitative analysis is
made by comparing the retention times (from injection to detection) of known
standards to the retention times of the sample compounds. Once sample compounds
are identified, quantitative analysis is made by comparing the detector response
for the sample compound to a known quantity of corresponding standard. Gas samples
collected on adsorption tubes are desorbed from the adsorption media using a
solvent. A measured volume of the desorption solution is injected into a heated
injection port where the mixture vaporizes and is carried into the GC column with a
carrier gas. The sample is separated into the individual components, then
qualitatively and quantitatively analyzed in the same manner as a gas sample.
Because of the number of different combinations of sampling, sample prepar-
ation, calibration procedures, GC column materials and operating procedures, and GC
detectors covered under this method, a set of tables (appearing at the end of the
Method Highlights section) has been developed to assist the tester in selecting and
the test observer in approving an acceptable sampling and analytical technique.
The compounds listed in these tables were selected based on their current status as
either presently regulated or being evaluated for future regulations by EPA and
state and local agencies. Table A lists selected organic compounds for Method 18
and provides the user with: (1) the Chemical Abstracts (CA) name, any synonyms, the
chemical formula, the Chemical Abstracts Service (CAS) number; (2) method
classification and corresponding references for more^information; and (3) whether
EPA currently has an audit cylinder for this compound.
For a given compound, the sampling and analytical techniques described in
Tables B, C, D and E are classified in Table A (Status of Selected Organic
Compounds for Method 18 Sampling and Analysis Techniques) into one of five classes
as follows:
1. Reference (R). This is a method promulgated by EPA as the compliance
test method for one or more EPA emission regulations.
2. Tentative (T). This is a method where EPA method development is
completed and documented, but the method has not been promulgated.
3- Development (D). This is a method currently under development by EPA.
4. Other (0). This is a method developed and documented by an organization
other than EPA.
5. None (N). This is a method that has not been developed or validated but
should work based on experience with similar situations.
Table B shows all the sampling techniques described in Method 18. For each
compound, each of the allowed sampling techniques is rated either: (1) recommend-
ed, (2) acceptable, (3) theoretical, (4) not recommended, or (5) unknown. The
rating codes for sampling are based on the extent of method validation. A particu-
lar sampling technique is rated based on current EPA methodology. Where EPA meth-
odology does not exist, methodology provided by organizations other than the EPA is
used for rating. As an example on how to use Table B, the rating for benzene is
"T" for direct interface, "R-12" for Tedlar bags, and "A-9,13" with carbon disul-
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Section No. 3.16
Date June 30, 1988
Page 5
fide for adsorbent tubes. This means that for sampling, there is no documented
experience with the direct interface method, but in theory it could be valid; a
Tedlar bag is recommended as a sampling technique and Reference 12 provides further
description; and charcoal tubes using carbon disulfide as the desorption liquid are
acceptable and References 9 and 13 provide further description.
Before a final sampling technique is selected, the source tester will need to
consider the general strengths and weaknesses of each technique.in addition to the
guidance provided in Table B. The strengths and weaknesses for the sampling
techniques described in Method 18 are as follows:
Direct Interface or Dilution Interface
Strengths:
Weaknesses:
1.
2.
3-
4.
1.
2.
3.
Tedlar Bag
Strengths:
Weaknesses:
2.
3-
4.
1.
Adsorbent Tubes
Strengths: 1.
2.
3-
Can immediately determine if analysis is successful.
Samples collected are in a form that approximates the form in
stack emissions and minimizes the time for degradation through
polymerization, condensation, etc.
No loss or alteration in compounds due to sampling since a sample
collection media (bag or adsorbent) is not used.
Method of choice for steady state sources when duct temperature is
below 100°C and organic concentrations . are suitable for the GC
detector.
GC must be located at the sampling site.
A GC equipped with a flame ionization detector
(FID) cannot be
operated at a sampling site if the presence of the H_ flame will
be hazardous.
Cannot sample proportionally or obtain a time integrated sample.
Because results represent only instantaneous values, they are not
totally indicative of non-steady state processes.
Samples collected are in a form that approximates the form in
stack emissions.
Samples may be returned to the laboratory for GC analysis.
Multiple analyses, if necessary, may be performed on each
collected sample.
Samples can be collected proportionally.
Unless protected, Tedlar bags are awkward and bulky for shipping
back to the laboratory. Caution must be taken to prevent bag
leaks.
Stability of compound(s) of interest in Tedlar bags with time must
be known. (Maximum permissible storage time(s) must be known or
determined, and must not be exceeded.)
Polar compounds generally should not be collected due to bag
adsorption. There are some exceptions (i.e., ethylene oxide).
Samples may not be collected when the concentration of any
component present is within explosive limits. • . - •.-.'•
Samples collected are compact and easy to return to the laboratory
for analysis.
Samples may be returned to the laboratory for GC analysis.
Sample storage time generally can be extended to a week by keeping
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Section No. 3.16
Date June 30, 19*88
Page 6
samples at 0 C. However, the migration of the collected com-
pound^) through the charcoal to the backup portion may be a
problem.
Weaknesses: 1. Quantitative recovery percentage of each organic compound from the
adsorbent material must be known.
2. Breakthrough sample gas volume for organic compounds as present in
the source matrix must be known for the adsorbent material.
3- Any effect of moisture (in the stack gas) on the adsorbent
material collection capacity must be known. Moisture in the
sample above 2 to 3 percent may severely reduce the adsorptive
capacity.
4. Generally, samples can be collected conveniently only at a
constant rate.
5. Samples must be returned to the lab for analysis.
Table C lists the recommended GC detectors commonly used with Method 18. For
each compound, each GC detector is rated either: R - recommended, A - acceptable,
T - theoretical, N - not recommended, or U - unknown. A particular GC detector is
rated based on current EPA methodology. Where EPA methodology does not exist,
methodology provided by organizations other than the EPA is used for rating. As an
example on how to use Table C, the rating for benzene is "R-4,12" for a flame
ionization detector (FID), "N" for an electron capture detector (ECD), "T-38" for a
photoionization detector (PID), and "N" for an electrolytic conductivity detector
(ELCD). This means an FID is recommended as the GC detector and References 4 and
12 provide further description, an ECD and an ELCD are not recommended, and there
is no documented experience with a PID for benzene, but its use is theoretically
possible based on the ionization potential found in Reference 38.
Table D presents information on packed columns suitable for GC analysis of the
selected compounds. Items covered include column type and conditions, Kovats
Retention Indices (KRI's), if available, and associated literature references. The
recommended column appears first, the others are acceptable. Specifically, any
column or condition that meets the Method 18 criteria for peak resolution is
considered acceptable. A particular GC column is recommended based on current EPA
methodology; where EPA methodology does not exist, methodology provided by
organizations other than the EPA is used for rating. Kovats Retention Indices were
previously used to identify unknown compounds by comparison of the measured KRI(s)
for a compound to catalogued KRI's for the various columns. In performing Method
18, KRI's can be useful in selecting a GC column which will effectively separate
two (or more) target compounds and/or interferents in an air sample. In Table D,
the first number shown for each compound refers to the literature reference for the
column and column conditions suggested for the recommended sampling method (when
available); the letter(s) associated with this number cross-references the List of
Referenced Columns following Table D. Listed next for each compound are the
columns and conditions suggested for sampling methods with an acceptable rating;
additional references are provided for columns used for analysis of the selected
compounds under laboratory conditions. Supplementary references provide KRI's (in
parentheses) for certain compounds. As an example of how to use Table D, the entry
for' benzene is "12-s, t; 9-k; 13~u; 4-p; 39-d(658), e(557), i(1039),- h(1104),
v(963)." This means that the column described in citations s and t in the Table D
List of Referenced Columns was specified in the method described in Reference 12;
the column described in citation k in the List of Referenced Columns was specified
in the method described in Reference 9; the column described in citation u in the
List was specified in the method described in Reference 13; the column described in
citation p in the List was specified in the method described in Reference 4; and
-------
Section No. 3.16
Date June 30, 1988
Page 7
the columns described in citations d, e, i, h, and v in the List were specified in
the method described in Reference 39- The KRI's for each column under the
conditions given in the List are shown in parentheses.
The user should be aware that interfering compounds may exist in source
samples. Some method development work, using the required presurvey sample, may be
necessary to optimize separation of the compounds of interest from the interfering
compounds present in a source sample. As discussed later in Section 3-16.5. any
column that will provide an acceptable resolution of the compounds can be used.
Only packed columns are described in Table D since these are more commonly
available to source test analysts than capillary columns. However, capillary
columns are permitted in Method 18 for analysis.
Table E shows the GC calibration preference for each compound based on the
technique used for sampling. Where appropriate, the source of calibration
standards is also shown. For each compound, the calibration technique shown is
rated either: (1) recommended, (2) acceptable, (3) theoretical, (4) not
recommended, or (5) unknown. A particular calibration technique is rated based on
current EPA methodology. Where EPA methodology does not exist, methodology
provided by organizations other than the EPA is used for rating. As an example on
how to use Table E, the rating for benzene is "R-12 (1806)" for gas cylinders, "N"
for gas injection into a Tedlar bag, "A-12" for liquid injection into a Tedlar bag,
"R-9,13" f°r preparation of the standard in desorption liquid, and "T" for
preparation of the standard on an adsorption tube followed by desorption. This
means that gas cylinders assayed and certified against National Bureau of Standards
(NBS) gaseous Standard Reference Material (SRM) 1806 using EPA Traceability
Protocol No. 1 (Reference 5) are recommended as the calibration standard for direct
interface and Tedlar bag samples with Reference 12 providing further information on
the source of the calibration standard; preparation of calibration standards by gas
injection into a Tedlar bag is not recommended; preparation of calibration
standards by liquid injection into a Tedlar bag is acceptable and Reference 12
provides further information; preparation of calibration standards in the
desorption liquid is the recommended procedure for use with the adsorption tube
methods described in References 9 and 13; and preparation of calibration standards
on adsorption tubes followed by desorption is theoretically valid for use with
adsorption tube samples.
Because the number of organic compounds of interest to EPA and state and local
agencies is increasing, and since EPA plans to conduct methods development arid
validation studies for many of the organic compounds identified here as well as for
additional compounds identified in the future, the Method Highlights portion of
Section 3-16 will be updated every two or three years. As with all other revisions
of Volume III of the Quality Assurance Handbook, those individuals whose names are
in the Record Distribution System will automatically receive the updated Method
Highlights section.
For compounds not currently listed in the tables, Figure 0.1 may be used as a
general guide in selecting appropriate sampling techniques. However, any technique
used must meet the criteria described in detail in the subsequent sections.
The Method Description (Sections 3.16.1 to 3.16.9) is based on the detailed
specifications in the Reference Method (Section 3-16.10) promulgated by EPA on
October 18, 1983 and corrections and revisions promulgated February 19, 1987- '
1. Procurement of Apparatus and Supplies
Section 3-16.1 gives specifications, criteria, and design features for the
-------
NONPOLAR
LOW-TEMPERATURE
LOW MOISTURE (< 1%)
CONCENTRATION
>1PPMV
CHARACTERIZE
STATIONARY
SOURCE
ORGANIC
COMPOUND
EMISSIONS
TEDLAR BAG
ADSORPTION TUBE
POLAR
DIRECT INTERFACE
DILUTION INTERFACE
ADSORPTION TUBE
DIRECT INTERFACE
DILUTION INTERFACE
NONPOLAR
MEDIUM TEMPERATURE
MEDIUM MOISTURE (> 3%)
POLAR
HIGH CONCENTRATION
HIGH TEMPERATURE
HIGH MOISTURE (> 10%)
HEATED TEDLAR BAG
ADSORPTION TUBE
DIRECT INTERFACE
DILUTION INTERFACE
ADSORPTION TUBE (SILICA)
DIRECT INTERFACE
DILUTION INTERFACE
DILUTION INTERFACE
LOW CONCENTRATION
SEMIVOLATILE
CONCENTRATION
<1PPMV
MM5
VOLATILE
VOS.T
DIRECT INTERFACE
T3 O C/>
(0 P CD
oq n- o
CD CD
CD 21
O
Figure 0.1. General scheme for selection of appropriate sampling techniques,
oo
-------
Section No. 3.16
Date June 30, 1988
Page 9
required equipment and materials. The sampling apparatus for Method 18 is divided
according to the different sampling approaches. This section can be used as a
guide for procurement and initial checks of equipment and supplies. The activity
matrix (Table 1.1) at the end of the section is a summary of the details given in
the text and can be used as a quick reference.
2. Presampling Preparations
Section 3-16.2 describes the required calibration procedures for the Method 18
sampling equipment. Section 3-16.3 describes, the presampling operations and the
acquisition of supplies and equipment needed for the sampling. Preliminary survey
sampling is discussed, including a description of classes of organic compounds and
the presurvey sampling techniques that are generally used to obtain a sample for
evaluation purposes. The presurvey sampling and analytical methods are then
described. Finally, how to select the proper sampling and analytical equipment
based on the presurvey data is discussed. The preliminary survey and presampling
preparation forms (Figures 3-2 and 3-5 of Section 3-16.3) can be used as equipment
checklists. Suggestions for packing the equipment and supplies for shipping are
given to help minimize breakage and reduce contamination.
Activity matrices for the calibration of equipment and the presampling
operations (Tables 2.1 and 3-1) summarize the activities detailed in the text.
3. On-Site Measurements :
Section 3-16.4 describes several sampling techniques. The use of the presur-
vey sample analyses and the sampling matrix tables (Tables A through E) provides
the user with the required information to select the proper sampling technique. A
checklist (Figure 4.8) is an easy reference for . field personnel rto use in all
sampling activities. Sampling and analyses using the direct interface and the
dilution interface methods are both conducted on-site; however, to provide for
greater consistency of presentation, the analytical procedures are presented in the
Posttest Operations Section with those for the other sampling techniques.
4. Posttest Operations
Section 3-16.5 describes the analytical procedures and the posttest activities
for checking the equipment. The initial analytical procedure of sample preparation
is shown based on the sampling technique used and includes the procedures for
preparation of the calibration standards. The second procedure discussed is the
method of introducing a known volume of sample into the GC and this is followed by
a discussion of GC operations. The detailed analytical procedures can be removed
for use as an easy reference in the laboratory. An activity matrix (Table 5.1)
summarizes the postsampling operations.
Section 3-16-6 describes calculations, nomenclature, and significant digits
for the data reduction. A programmed calculator is recommended to reduce
calculation errors.
Section 3-16.7 recommends routine and preventive maintenance programs. The
programs are not required, but their use should reduce equipment downtime.
5- Auditing Procedures
Section 3-16.8 describes performance and system audits. Performance audits
for both the analytical phase and the data processing are described. A checklist
-------
Section No. 3-16
Date June 30, 1988
Page 10
(Figure 8.2) outlines a system audit.
Section 3-16.9 lists the primary standards to which the working standards or
calibration standards should be traceable.
6. References
Section 3-16.10 contains the promulgated Method; .Section 3.16.11 contains the
references used throughout this text; and Section 3-16.12 lists all the data forms
in Section 3-16 and contains copies of blank data forms for those shown completed
in the text. These may be removed from the Handbook, copied, and used in
performing the method. Each form has a subtitle [e.g., M18-2.5 (Figure 2.5)] to
assist the user in locating the same completed form in the text. Several
checklists are not completed in the text and and therefore not reproduced in this
section.
-------
Section No. 3.16
Date June 30, 1988
Page 11
TABLE A. STATUS OF SELECTED ORGANIC COMPOUNDS FOR METHOD 18
SAMPLING AND ANALYSIS TECHNIQUES
= = = = = ~ = = = = = = := = = = = = = = = = = ==:=s = = = = = =
Chemical Abstracts Name
Synonyms
Formula
CAS No.
|Method| EPA Audit
[Class | Cylinder(ppm)
Alcohols
Methanol
Ethanol
Isopropyl Alcohol
n-Propyl Alcohol
n-Butyl 'Alcohol
Methyl Alcohol
Ethyl Alcohol
2-Propanol
1-Propanol
1-Butanol
Alkanes
CH.O
c J6o
C?H8°
SH8°
CHo°
(67-56-1)
(64-17-5)
(67-63-0)
(71-23-8)
(71-3&-3)
0-6
0-7
0-7
0-8
0-8
30-80
No
No
No
No
Cyclohexane
Hexane
c6"12
C6H14
(110-82-7) | 0-9 | 80-200
(110-54-3) j 0-9 |20-90.1000-3000
Alkenes
Ethylene
Propy lene
| Ethene
1 Propene
l«$
| (74-85-1) |
| (115-07-1) |
N
N
| 5-20,300-700
I 5-20,300-700
Dienes
1,3-Butadiene
Hexachlorocyclopentadiene
| Butadiene |
| Perchlorocyclopentadiene|
=============================
Aromatic
C.H,
c:ci
| (106-99-0)
j (77-47-/O
D-io
5-60
No
Benzene
Mesi tylene
Ethylbenzene
Cumene
Xylene (m- , o- . p- )
Toluene
Styrene
2-Naphthylamine
Benzol
1,3,5-Trimethylbenzene
1-Methylethylbenzene
Dime thy Ibenzene
Methylbenzene
E t he ny Ibenzene
2-Naphthylenamine
C6H6
C9H12
C8H 0
r H
9 12
r 'u
8 10
r u
78
C8H8
c?oY
(71-43-2)
(108-67-8)
(100-41-4)
(98-82-8)
(1330-20-7)
(108-88-3)
(100-42-5)
(91-59-8)
T-12
N
0-13
0-13
0-13
0-9,13
0-13
0-14
5-20,6o-4oo
No
No
No
5-20,300-700
5-20,100-700
No
No
Ke tones
Acetone
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
| 2-Propanbne
I 2-Butanone
| 4-Methyl-2-pentanone
C H,0
C4H8°
C6»12°
(67-64-1) | 0-15 | No
(78-93-3) I 0-16 j 30-80
(108-10-1) I 0-15 j 5-20
Epoxides
Ethylene Oxide
Propylene Oxide
I Epoxy Ethane |
j 1,2-Epoxy Propane j
Sulfides
C H.O
C H&0
==_=====
| (75-21-8) | 0-17 | 5-20
I (75-56-9) I 0-18 j 5-20,75-200
: = = = = =: = = = = = = = = = = = = = = = = ss- = = s = = = = = = = =: =
bis(2-Chloroethyl) Sulfide
| Mustard Gas
(505-60-2) | N
No
-------
Section No. 3.16
Date June 30, 1*988
Page 12
TABLE A. (Continued)
Chemical Abstracts Name
Synonyms
| Formula
CAS No.
|Method| EPA Audit
jdass j Cylinder(ppm)'
Halogenated
Ethylidene Chloride
Ethylene Dibromide
Ethylene Dichloride
Propylene Dichloride
1,1,1-Trichloroethane
Bromodichloronethane
Chi o rod ibromome thane
Chloroform
Carbon Tetrachloride
Dichlorodifluoromethane
Methyl Bromide
Methyl Chloride
Methylene Chloride
Tetrachloroethylene
Bromof orm
Trichloroethylene
Trichlorotrifluoroethane
Vinylidene Chloride
Ethyl Chloride
Chlorobenzene
Vinyl Chloride
l,2-Dibromo-3-chloropropane
1,1-Dichloroethane
1 , 2-Dibromoe thane
1 ,2-Dichloroethane
1,2-Dichloro propane
Methyl chloroform
Trichlorome thane
Tetrachloromethane
Freon 12
Bromomethane
Chloromethane
Dichloromethane
Perchloroethylene
Tribromome thane
Trichloroethene
Freon 113
1,1-Dichloroethene
Chloroethane
Monochlorobenzene
Chloroethylene
DBCP
C2H4C12
C2H4Br2
£ H £.
C^H?cl2
C^H^Cl2
CHBTC1
CHBr C?
CHC1
CC1,3
CC1 F
CH Jr2
CHr,Cl
CH~CI_
2 2
CHBr
CUP T
2 ^
C Cl F
C2H2^12
C H Cl
C6H>C1
r u-V i
0 l^1
2 Jn ri
(5-3*-3)
(106-93-4)
(107-06-2)
(78-87-5)
(71-55-6)
(75-27-4)
(124-48-1)
(67-66-3)
(56-23-5)
(75-71-8)
(74-83-9)
(74-87-3)
(75-09-2)
(127-18-4)
(75-25-2)
(79-01-6)
(76-13-1)
(75-35-4)
(75-00-3)
(108-90-7)
(75-01-4)
(96-12-8)
0-19
0-20
T-21
0-22
T-21
N
N
T-23
T-23
0-24
0-25
0-26
T-27
T-21
0-19
T-21
T-21
0-28
0-29
0-19
R-30
0-37
No
5-20,50-300
5-20,100-600
3-20,300-700
5-20
No
No
5-20,300-700
5-20
No
No
No
1-20
5-20,300-700
No
5-20.100-600
5-20
5-20, 100-600
No
5-20
5-30
No
Method Classification Code
R = Reference - EPA promulgated method.
Tentative -
T
D
0 = Other -
N = None -
EPA method development complete; EPA reference available.
= Development - EPA method currently under development.
Method development completed by organizations other than EPA; reference available.
No reference available; recommendation based on experience.
The codes in the method classification column describe the current status of a sampling and analysis
method for each selected compound. For example, the method classification code for benzene is: T-12.
This means the current method for benzene is a tenative EPA method with development complete and the
reference for the method is citation number 12 in Section 3.16.11.
* The availability of EPA audit cylinders is shown in this column where:
( ) = Audit cylinders for this particular compound are available from EPA in the concentration ranges
indicated (Reference 4).
No = Audit cylinders for this particular compound are not available from EPA. The source tester must
obtain audit gas cylinders from commercial gas vendors certified by independent analysis to be
within 5 percent of the concentration claimed by the vendor.
-------
Section No. 3.16
Date June 30, 1988
Page 13
TABLE B. METHOD 18 SAMPLING TECHNIQUES FOR SELECTED ORGANIC COMPOUNDS . ,
===BS======== ======================================================================= ==========-=======::==
| | | Adsorbent Tubes and Desorption Liquid
| Direct j Tedlar j ------------------------------ •=• ------------------------
Selected Compounds |lnterface j Bag* | Charcoal* | Other ** | Desorption Liquid***
Alcohols
Methanol
Ethanol
Isopropyl Alcohol
n-Propyl Alcohol
n-Butyl Alcohol
T
T '
T
T
T
N
N
N
N
N
N
T-7 .
T-7
T-8
T-8
|A-6; Silica Gel|
1 ~ 1
1 ~ 1
j - j
1 ~ 1
Distille.d Water
IX 2-Butanol in CS
IX 2-Butanol in CS2
Carbon Disulfide
Carbon. Disulfide
Alkanes
Cyclohexane
Hexane
= = = s = = = = = = = = = = ss = = = = = = = = = = = = = = =. = = = = = = = = = =
U I T-9
U j T-9
===================
Alkenes
Carbon Disulfide
Carbon Disulfide
Ethylene
Propy1ene
I T
I T
N
U
u I u
==============
Dienes
===============================================
1,3-Butadiene | T
Hexachlorocyclopentadiene | T
j A-ll; Porapak
Carbon Disulfide
Hexane
===================================
Aromatic
Benzene
Mesitylene
Ethylbenzene
Cumene
Xylene (m- , o- , p- )
Toluene
Styrene
2-Napthylamine
T | R-12
T | U
T | U
T | U
T | U
T. | U
T | U
T | U
T-9. 13
U
T-13
T-13
T-13
T-9, 13
T-13
T-lA
-
-
-
-
-
-
-
.
Carbon Disulfide
U
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide.
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
= s = = = = = = = = = =.= = = = = = = = =
Ketones
Acetone
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
========s==========s====================
I N | T-15
! N | N
I N I T-15
Epoxides
|A-l6; Ambersorbj
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Ethylene Oxide
Propylene Oxide
T-17
T-18
| 99:1 BenzeneiCS.,
. Carbon Disulfide
=========================================
=================
Sulfides
bis(2-Chloroethyl) Sulfide | T
====================================
(continued)
-------
Section No. 3.16
Date June 30, 1$88
Page 14
TABLE B. (Continued)
Selected Compounds
| | | Adsorbent Tubes and Desorption Liquid
j Direct j Tedlar |
(interface | Bag* j Charcoal* | Other **
Desorption Liquid*
Halogenated
Ethylidene Chloride
Ethylene Dibromide
Ethylene Dichloride
Propylene Dichloride
1,1,1-Trichloroethane
Bromodichloromethane .
Chlorodibromome thane
Chloroform
Carbon Tetrachloride
Dichlorodifluoromethane
Methyl Bromide
Methyl Chloride
Methylene Chloride
Tetrachloroethylene
Broraoform
Trichloroethylene
Trichlorotrifluoroethane
Vinylidene Chloride
Ethyl Chloride
Chlorobenzene
Vinyl Chloride
1 , 2-Dibromo-3-chloropropane
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
U
N-31
R-21
U
R-21
U
U
R-23
R-23
U
U
U
R-27
R-21
U
R-21
R-21
U
U
U
R-30
U
T-19
T-20
T-19
T-22 ,
T-ig
U
U
T-19
T-19 ,
T-24
T-25
T-26
T-32
T-33
T-19
T-34
T-35
T-28
T-29
T-19
T-36
T-37
_
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
Carbon Disulfide
99:1 BenzeneiMeOH
Carbon Disulfide
15J! Acetone in Cyclohexane
Carbon Disulfide
U
U
Carbon Disulfide
Carbon Disulfide
Methylene Chloride
Carbon Disulfide
Methanol
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Carbon Disulfide
Rating Code
R - Recommended.
A = Acceptable.
Theoretical.
Based on actual source tests experience (sampling
valid and is the method of choice among Method 18
and analysis) this method is
users .
Based on actual source tests or similar source test experience (sampling and
analysis), this method is valid. The tester must evaluate for specific test.
Method has no documented experience, but in theory could be valid.
N = Not Recommended. Based on actual source tests or similar source test experience and/or theory, this
method is invalid.
Unknown.
Method has no documented experience and the theoretical aspects of sampling by this
method are inconclusive. The tester must demonstrate that this sampling method is
valid. . .
The rating codes for sampling are based on the extent of method validation. For example, the rating
code for benzene is: T; R-12; A-9,13- This means that direct interface is theoretically possible for
benzene, but no documented experience has been found; Tedlar bags are the recommended sampling method for
benzene by the tenative EPA method referenced in citation 12 in Section 3.16.11; and sampling with
charcoal adsorption tubes is acceptable following the two methods referenced in citations 9 and 13 in
Section 3.16.11.
* = If condensibles exist, use the procedure described in Section 3-l6.ll.
** = Solid sorbents other than charcoal recommended.
*"* = The recommended desorption solution is given in this column. Analyst should consult the appro-
priate reference for details.
-------
Section No. 3.16
Date June 30, 1988
Page 15
TABLE C. GC DETECTORS FOR SELECTED ORGANIC COMPOUNDS BY METHOD 18
3s3333::333 = = 333a = = 3:=33333ss3333a3aa::t=33333:: = 3S3333s = 33333 = 333B33sss
| Gas Chromatograph Detector *
1
Selected Compounds | FID
Methanol R-4,6
Ethanol R-7
Isopropyl Alcohol R-7
n-Propyl Alcohol R-8
n-Butyl Alcohol R-8
Cyclohexane R-4,9
Hexane R-4,9
Ethylene A-4
Propylene A-4
1 ,3-Butadiene | R-4.10
Hexachlorocyclopentadiene j R-ll
Benzene R-4,12
Mesitylene T
Ethylbenzene R-i;
Curaene R-i;
Xylene (o-,m-,p-) R-4,i;
Toluene R-4,9,1
Styrene R-i;
2-Napthylamine R-l/l
Acetone R-15
Methyl Ethyl Ketone R-4,l6
Methyl Isobutyl Ketone R-4,15
Ethylene Oxide R-4.17
Propylene Oxide R-4,l(
bis(2-Chloroethyl) Sulfide | U
| ECD PID
Alcohols
N T-38
N T-38
N T-38
N T-38
N T-38
Alkanes
N I T-38
N j T-38
Alkenes
N | T-38
N | T-38
Dienes
.41 N | T-38
T | U
Aromatic
N T-38
N T-38
N T-38
N T-38
N T-38
3 N T-38
N T-38
N U
333333333S3S3333S333333S3333SS33:
Ketones
N | T-38
N j T-38
N j T-38
Epoxides
N T-38
N | T-38
Sulfides
| U U
ELCD
N
N
N
N
N
N
N
N
N
N
T
N
N
N
N
N
N
N
N
=============
N
N
N
N
N
U
(continued)
-------
Section No. 3.16
Date June 30, 1988
Page 16
TABLE C. (Continued)
Selected Compounds
Gas Chromatograph Detector *
FID
BCD
PID | ELCD
Halogenated
Ethylidene Chloride
Ethylene Dibromide
Ethylene Dichloride
Propylene Dichloride
1,1, 1-Trichlo roe thane
Bromodichlorom ethane
Ch 1 o rod ibromom ethane
Chloroform
Carbon Tetrachloride
Dichlorodifluororae thane
Methyl Bromide
Methyl Chloride
Methylene Chloride
Tetrachloroethylene
Bromoforra
Trichloroethylene
Trichlorotrifluoroethane
Vinylidene Chloride
Ethyl Chloride
Chlorobenzene
Vinyl Chloride
1 , 2-Dibromo-3-chloropropane
R-19
A-A
R-A.21
A-A
Rr-A.21
U
U
R-A.23.
R-A.23
R-2A
R-25
R-26
R-A.27,32
R-A.21
R-19
R-A.21
R-A.21
R-A.28
R-29
R-A.19
R-A.30
U
T
R-20
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
U
U
T-38
T-38
U
U
U
T-38
T-38
N-38
T-38
T-38
T-38
T-38
T-38
T-38
N-38
T-38
T-38
T-38
T-38
R-37 | u
T
T
T
R-22
T
T
T
A-23
A-23
T
T
T
T
T
T
T
T
T
T
T
T
T
Rating Code
R = Recommended.
Based on actual source tests experience (sampling and analysis)
this method is valid an is the method of choice among Method 18
users.
A = Acceptable.
T = Theoretical.
Based on actual source tests or similar source test experience
(sampling and analysis), this method is valid. The tester must
evaluate for specific test.
Method has no documented experience, but in theory could be
valid.
N = Not Recommended. Based on actual source tests or similar source test experience
and/or theory, this method is invalid.
U = Unknown.
Method has no documented experience and the heoretical aspects
are not conclusive. The tester must demonstrate that this
detection method is valid.
The rating codes for GC detectors are based on the detector specified in the method
that is referenced. For example, the rating code for benzene is: R-A.12; N; T-38; N.
This means that the FID is recommended for detection of benzene by both references A and
12 cited in Section 3-16-H: the BCD and the ELCD are not recommended for benzene; and
detection of benzene with a PID is theoretically possible based on the ionization
potential found in reference J6.
* The following abreviations are used for the gas chromatography detectors:
FID = Flame Ionization Detector
ELCD = Electroconductivity Detector
(Hall Detector)
ECD = Electron Capture Detector
PID = Photoionization Detector
(with lamps up to 11.7 electron
volts)
-------
Section No. 3.16
Date June 30, 1988
Page 17
TABLE D. PACKED COLUMNS SUITABLE FOR ANALYSIS OF SELECTED ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY
Selected Compounds ' | Column Reference, Type and Conditions, and Kovats Retention Indices*
' Alcohols
Me thanol
Ethanol
Isopropyl Alcohol
n-Propyl Alcohol
n-Butyl Alcohol
6-a; 4-b, c; 39-d(3?0). e(331), f(426)
7-g
7-g; 39-d(477), e<396>. f(5?6),
8-j; 39-e(387). f(533)
8-J; 39-d(649)
S3S33Sse38BBecsaBB3aassBB33B8SBaBsasB3B3ssasssB3B33SasB3ssE3SBBB3=
Alkanes
Cyclohexane | 9-k; 4-1; 39-d(66?), e(5U), f(6l9)
Hexane I <)-k; 4-m; 39-d(600), e(600). f(600)
Alkenes
Ethylene | 4-n '
Propylene j 4-n
Dienes
1 , 3-Butadiene | lO-o; 4-p. q, 4l-nnn
Hexachlorocyclopentadiene j 11-r
Aromatic
13-u: t-d(869). e(573).
13-u; 4-1(13-18)
13-w; 4-x; 39-d(ra = 876, p = 877. o = 900), i(m = 1297. P = 1312, o = 1353)
9-k; 13-w; A-p; 39-d(76l). h(1136), i(1201), v(1060)
i3-w: s
14-y
Benzene | 12-s, t; 9-k; 13-u; 4-p; 39-d(6s8), e(557), 1(1039), h(1104), v(9&3)
Mesitylene
Ethylbenzene
Cumene
Xylene (o-,n-,p-)
Toluene
Styrene
2-Napthylamine '
Ketones
Acetone | 15-z; 4-e(380), f(636), h(1009), h(1091)
Methyl Ethyl Ketone j 16-aa: 4-bb; 39-d(579). e(476), f(6A4), h(1087), i(1158), v(92?)
Methyl Isobutyl Ketone j 15-z; 4-cc; 39-d(722) • •
Epoxides
Ethylene Oxide | l?-dd; 4-ee; 4o-mmm
Propylene Oxide j 18-ff; A-ee
Sufides
bis(2-Chloroethyl) Sulfide | ' '
=====BBaa===aaaaa3a=a=i;=333B333a3============aaa=a=aa3as3a==s=saa=aa33a3a3333a=3sa===3a33aa3aaaaaa3aaaaa
(continued)
-------
Section No. 3.16
Date June 30, 1§88
Page 18
TABLE D. (Continued)
Selected Compounds
Column Reference, Type and Conditions, and Kovats Retention .Indices*
= = = = = ss = a = = = = = =!s = s = = = = =s = = s = = = = = = = = = cs = = = = s = = = = = = = = s = s£a» = = = sssass = = =
Halogenated
Ethylidene Chloride
Ethylene Dibromide
Ethylene Dichloride
Propylene Dichloride
1,1,1-Trichloroethane
Bromodlchlorome thane
Chlorodibromome thane
Chloroform
Carbon Tetrachloride
Dichlorodifluoromethane
Methyl Bromide
Methyl Chloride
Methylene Chloride
Tetrachloroethylene
Bromoform
Trichloroethylene
Trichlorotrifluoroethane
Vinylidene Chloride
Ethyl Chloride
Chlorobenzene
Vinyl Chloride
1 , 2-Dibromo-3-chloropropane
19-88
20-hh
21-ii
22-kk
21-ii
23-11
23-11
24-pp
25-qq
26-rr
27-88.
21-11;
19-ww
21-ii ;
21-ii;
28-zz;
29-11
19-bbb
30-ccc
37-888
39-d(565), e(427). f (604) , h(g4
4-(hhh)
19-jj; 4-1; 39-d(636), e(46o),
4-(vv)
19-JJ; 4-oo; 39-6(568), v(897)
19-mm; 4-iii; 39-d(6o6) , e(443)
19-nn; 4-oo; 39-d(665), e(502).
0), 1(994). v(896)
f (666) ,
. f(625)
f(553).
h(113D, 1(1205), v(1078)
, h(1022), 1(1090), v(1025)
h(897), i(938), v(893)
111; 32-tt; 4-oo: 39-d(5l6), h(.956), 1(1013), v(934)
33-uu; 4-vv; 39-d(8l3) , e(5?4),
34-xx; 4-1; 39-d(695), e(546),
35-yy; 4-oo
f(736).
f(665),
h(l05&), 1(1105). v(l039)
h(1009), 1(1068), v(1004)
4-jjj; 39-h(7&0). 1(792). v(738)
; 4-kkk; 39-d(842), h(1347)
, ddd; 36-eee; 4-fff
= = sa = = = = = = ss = = = = = = = sss:s = = = = = = = = s
1
The GC column references, column types and conditions, and Kovats Retention Indices (if available) are
shown in this column. The first reference shown for each compound is for the column and conditions
suggested for the recommended sampling method (when available), followed by the column and conditions
suggested for sampling methods with an acceptable rating. Additional references are given when
available for columns used for analysis of the selected compound under laboratory conditions. Some
additional references provide Kovats Retention Indices for selected compounds. For example, the
reference code for benzene is: 12-s, t; 9-k; 13-u; 4-p; 39-d(6s8), e(557), 1(1039), h(HOA), v(9&3).
This means that for benzene the columns described in citations s and t in the List of Referenced
Columns (following Table D) were specified in the method described in citation 12 in Section 3.16.11;
the column described in citation k in the List of Referenced Columns was specified in the method
described in citation 9 in Section 3.16.11; the column described in citation u was specified in the
method descibed in citation 13 in Section 3.16.11; the column described in citation p was specified in
the method described in citation U in Section 3.16.11; and the columns described in. citations d, e. i,
h.and v were specified in the method described in citation 39 in Section 3-l6.ll. Where available, the
Kovats Retention Indices for each of the columns under the conditions given in their respective
references are given in parentheses.
Note: Any column or conditions that meet the Method 18 criteria for peak resolution are considered
acceptable.
-------
Section No. 3.16
Date June 30, 1988
Page 19
APPENDIX I to TABLE D.
LIST OF REFERENCED COLUMNS WITH SUGGESTED OPERATING CONDITIONS
(a). 60/80 mesh Tenax, operated isothermally at 80 C.
(b) . Chromasorb 101, operated isothermally at 50 C.
(c). 0.2% Carbowax 1500/0.1$ SP-2100 on Carbopack C, operated isothermally at
60°C.
(d). 20% SP-2100/0.1% Carbowax 1500 on 100/200 mesh Supelcoport, operated
isothermally at 70°C.
(e). Carbopak C-HT 80/100 mesh, operated isothermally at 90 C.
(f). Porapak T 80/100 mesh, operated isothermally at l40°C.
(g). 0.2% Carbowax 1500 on 60/80 mesh Carbopack C, temperature programmed from 65°
to 70°C.
(h). 15% tetracyanoethylated pentaerythritol on 60/80 mesh Chromasorb P-AW,
operated isothermally at 80 C.
(i). 15% tetracyanoethylated pentaerythritol on 60/80 mesh Chromasorb P-AW,
operated isothermally at 100 C.
(j). 10% SP-1000 on 80/100 mesh Chromasorb WHP, temperature programmed from 75 C.
(k). 20% SP-2100' on. 80/100 mesh Supelcoport, operated isothermally at 40° or
70 C or temperature programmed from 50 C, depending on other anal-
ytes of interest. See referenced method for details.
(1). 10% OV-101 on Chromasorb WHP, operated isothermally at 100°C.
(m), 10% OV-101 on Chromasorb WHP, operated isothermally at 60° or 100°C.
(n). Durapak n-octane on Porasil C, operated isothermally at 30 C.
(o). 1% SP-1000 on Carbopack B, operated isothermally at 55°C for 12 minutes.
(p) . 10% OV-101 on Chromasorb WHP, operated isothermally at 60°C.
(q) . 0.12 SP-1000 on Carbopack C, operated isothermally at 90°C.
(r). 3% OV-1 on 100/120 Gas Chrom Q, operated isothermally at 135°C.
(s). For benzene in the presence of aliphatics, 10% 1,2,3-tris (2-cyanoethoxy)
propane (TCEP) on 80/100 Chromasorb P AW.
(t). For benzene with separation of xylene isomers, 5% SP-1200/1.75% Bentone 34 on
100/120 mesh Supelcoport, operated isothermally at 75°C.
(u). 10% OV-275 on 100/120 mesh Chromasorb W-AW, operated isothermally at 50°C or
temperature programmed starting at 50 C for 3 minutes followed by
15°C/min increase to 200°C.
(v). 10% FFAP on 80/100 Acid-washed Chromasorb W, operated isothermally at 125°C.
(w). 10% OV-275 on 100/120 mesh Chromasorb W-AW, operated isothermally at 50°
or 100 C or temperature programmed starting at 50 C for 3 minutes followed
by 15°C/min increase to 200 C.
(x). For meta-xylene, 10% OV-101 on' Chromasorb WHP, operated isotheramlly at 60°,
120°, or 140°C.
(y). 3% OV-225 on 80/100 mesh Supelcoport, operated isothermally at l63°C.
(z). 10% SP-2100/0.1% Carbowax 1500 on 100/120 mesh Supelcoport, temperature
programmed from 50° to 170°C at 10°C/min.
(aa). 20% SP-2100/0.1% Carbowax 1500 on 100/120 mesh Supelcoport, operated isother-
mally between 55° and 75°C.
(bb). Chromasorb 101, operated isothermally at l80°C.
(cc). 0.1% SP-1000 on Carbopack C, operated isothermally at 180°C.
(dd). 50/80 mesh Porapak Q, operated isothermally at 135°C.
(continued)
-------
Section No. 3-16 „
Date June 30, 1988
Page 20
APPENDIX I to TABLE D. (Continued)
(ee). 80/100 mesh Porapak QS, operated isothermally at 150°C.
(ff). 50/80 mesh Porapak Q, operated isothermally at 1^5 C.
(gg) . 10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 50°C.
(hh). 3% OV-210 on 80/100 mesh Gas Chrom Q, operated isothermally at 50 C.
(ii). 20% SP-2100/0.1% Carbowax 1500 on 100/200 mesh Supelcoport, operated
isothermally at 100°C.
(jj). , 10'% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 70°C.
(kk) . 3% Carbowax 1500 on 60/80 mesh Chromasorb WHP, operated isothermally at
50°C.
(11). 1% SP-1000 on Carbopack B, operated isothermally at 120°C.
(mm). 10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 75°C.
(nn) . 10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 60°C.
(oo). 10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 100°C.
(pp) . 80/100 mesh Chromasorb 102, operated isothermally at 110°C.
(qq) . 10% FFAP on 100/120 mesh Chromasorb WHP, operated isothermally at 65°C.
(rr). 80/100 mesh Chromasorb 102, operated isothermally at 100°C.
(ss). 5% OV-101 on 80/100 Chromasorb WAP, operated isothermally at 35°C-
(tt). 10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally between 60°
and 90°C. ' . .
(uu) . 10% OV-101 on 100/120 mesh Supeleoport, operated isothermally at 90 C.
(w). 10% OV-101 on Chromasorb WHP, operated isothermally at 50° or 100 C.
(ww). 10% SP-1000 on 80/100 mesh Supelcoport., operated isothermally at 130°C.
(xx) . 10% OV-101 on 100/120 mesh Supelcoport, operated isothermally at 70°C.
(yy) • 50/80 mesh Porapak Q, operated isothermally at 150 C.
(zz). 100/120 mesh Durapack OPN in silanized glass, operated isothermally at 65 C.
(aaa). 10% FFAP on 100/120 mesh Chromasorb WHP, operated isothermally at 110°C.
(bbb). 10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 105 C.
(ccc). 80/100 mesh Chromasorb 102, operated isothermally at 100°C.
(ddd) . For sources where acetaldehyde is present, use column cited in (ccc)
followed by a column of 20% GE SF-96 on 60/80 mesh Chromasorb P AW or
80/100 mesh Porapak T connected in series, operated isothermally at 120°C.
(eee). 10% SE-30 on 80/100 Chromasorb W, operated isothermally at 60°C.
(fff). 0.4% Carbowax on Carbopack C, operated isothermally at 50°C.
(ggg). 1.5 OV-17 plus 1.95% OV-210.
(hhh) . 5% OV-101 on Chromasorb WHP, operated isothermally at 60 C.
(iii). 10% OV-101 on Chromasorb WHP, operated isothermally at 50° or 100°C.
(jjj). 10% OV-101 on Chromasorb WHP, operated isothermally at 100°C or 10% SP-2100
on Supelcoport, operated isothermally at 100 C.
(kkk). 10% SP-1000 on 80/100 mesh Supelcoport, operated isothermally at 150 C.
(111). 1% SP-1000 on 60/80 mesh Carbopack, temperature programmed- starting at 40 C
for 3 minutes, followed by 8 C/min increase to 200 C.
(mmm) . 15% FFAP on Anakrom A. .
(nnn) . 10% FFAP on 80/100 mesh Chromosorb W AW-DMCS, operated isothermally at 52°C.
-------
Section No. 3-16
Date June 30. 1988
Page 21
TABLE E. RECOMMENDED CALIBRATION TECHNIQUES FOR SELECTED ORGANIC COMPOUNDS BY METHOD 18
===============================================================================================
Methods for Direct Interface
and Tedlar Bag Samples
Selected Compounds
===========================
Gas
Cylinders
Gas | Liquid
Injection | Injection
into | into
Tedlar Bag | Tedlar Bag
Methods for Adsorption
Tube Samples
Prepare | Prepare
Standard in | Standard
Desorption | on Tube
Liquid | and Desorb
================================================================
Alcohols
Methanol i
Ethanol
Isopropyl Alcohol
n-Propyl Alcohol
n-Butyl Alcohol
T-4
U
U
u
, u
N •
N
N
N
N
U
U
U
' U
U
R-6 | T
R-7 | T
R-7 | T
R-8 | T
R-8 | T
Alkanes
Cyclohexane
Hexane
T-4
T-4
R-9
R-9
Alkenes
Ethylene
Propylene
T-4
T-4
Dienes
1,3-Butadiene
Hexachlorocyclopentadlene
A-10
U
IN |
1===========
Aromatics
R-10
N
==============
R-41
R-ll
Benzene
Mesi tylene
Ethylbenzene
Cumene
Xylene (m- , o- , p- )
Toluene
Styrene
2-Napthylamine
|R-12(SRM 1806)
1 • "
. . "I "
1 u
1 T-4
| T-4
1 • "
1 "
• N'
N .
N
N
N
N
N
U
A-12
U
U
U
u
u
u
u
R-9. 13
u
R-13
R-13
R-13
R-9. 13
R-13
R-14
T
U
T
T
T
T
T
T
====================================================
Ketones
===============================
Acetone
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
U
T-4
T-4
R-15
R-16
R-15
| T
I T
| T
===============
Cpoxides
=========================================
Ethylene Oxide
Propylene Oxide
T-4
T-4
R-17
R-18
=============================================
==================================
Sulfides
==================
bis(2-Chloroethyl) Sulfide |
u I u
(continued)
-------
Section No. 3.1§
Date June 30, 1988
Page 22
TABLE E. (Continued)
Selected Compounds
Methods for Direct Interface
and Tedlar Bag Samples
Gas
Cylinders
Gas
Injection
into
Tedlar Bag
Liquid
Injection
into
Tedlar Bag
Methods for Adsorption
Tube Samples
Prepare | Prepare
Standard in ( Standard
Desorption | on Tube
Liquid 1 and Desorb
Halogenated
Ethylidene Chloride
Ethylene Dibromide
Ethylene Dichloride
Propylene Dichloride
1,1, 1-Trichloroe thane
Bromodichlorome thane
Chlorodibrornome thane
Chloroform
Carbon Tetrachloride
Dichlorodifluoromethane
Methyl Bromide
Methyl Chloride
Methylene Chloride
Tetrachloroethylene
Bromoform
Trichloroethylene
Trichlorotrifluoroethane
Vinylidene Chloride
Ethyl Chloride
Chlorobenzene
Vinyl Chloride
1 ,2-Dibromo-3-chloropropane
U
T-4
R-21
T-4
R-21
U
U
R-23
R-23
U
U
U
R-21
R-2KSRM 1809)
U
R-21
R-21
T-4
U
T-4
R-30
U
N
N
N
N
N
U
U
N
N
U
U
U
N
N
N
N
N
N
N
N
A-30
N
U
N-31
A-21
U
A-21
U
U
A-23
A-23
N
N
N
A-21
A-21
U
A-21
A-21
U
U
U
N
U
R-19
R-20
R-19
R-22
R-19
U
U
R-19
R-19
R-24
R-25
R-26
R-32
R-33
R-19
R-34
R-35
R-28
R-29
R-19
R-3&
R-37
T
T
T
T
T
U
U
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
Rating Code
R = Recommended.
A = Acceptable.
T = Theoretical.
Based on actual source test experience (sampling and analysis) this method
is valid and is the method of choice among Method 18 users.
Based on actual source tests or similar source test experience (sampling and
analysis), this method is valid. The tester must evaluate for specific
test.
Method has no documented sampling and analysis experience, but in theory
could be valid.
N = Not Recommended. Based on actual source tests or similar source test experience and/or
theory, this method is invalid.
U = Unknown.
Method has no documented experience and the theoretical aspects are not
conclusive. The tester must demonstrate that this calibration method is
valid.
The rating codes for calibration procedures are based on procedures specified in applicable
sampling and/or analytical methods. For example, the rating code for benzene is: R-12(SRM 1806);
N; A-12; R-9,13; T. This means that for benzene, the recommended calibration procedure for direct
interface and Tedlar bag samples involves the use of gas cylinders with the procedures described
in citation 12 in Section 3.16.11 and Standard Reference Material 1806 (available from the
National Bureau of Standards. Gaithersburg, MD); calibration standards for benzene prepared by gas
injection into Tedlar bags is not recommended; calibration standards prepared by liquid injection
into Tedlar bags is acceptable following the procedures described in citation 12 in Section
3.16.11; preparation of calibration standards in desorption liquid is the recommended procedure
for the adsorption tube methods described in citations 9 and 13 in Section 3-l6.ll; preparation of
calibration standards on adsorption tubes followed by desorption is theoretically valid for use
with adsorption tube samples.
-------
Section No. 3.16.1
Date June 30, 1988
Page 1
1.0 PROCUREMENT OF APPARATUS AND SUPPLIES
For Method 18, a number of different sampling and analytical'procedures are
considered acceptable for the identification and measurement of the majority of
gaseous organic compounds emitted from industrial sources. Persons attempting to
apply these procedures are advised to consult the tables presented in the Method
Highlights Section. The Method Highlights Section is intended to provide guidance,
based on current EPA methodology, for selection of the most suitable sampling and
analytical protocols for organic compounds of interest to Federal, State, and local
agencies. For situations where EPA methodology is not applicable, guidance for
selection of sampling and analytical protocols based on methodology from other
reputable organizations is provided. Once a suitable sampling and analytical
protocol has been selected, then procurement of the necessary apparatus and sup-
plies can begin.
A number of the sampling and analytical methodologies covered by Method 18
are common to both presurvey sampling and analysis and final sampling and analysis.
Presurvey sample collection can employ either glass sampling flasks (not employed
for final sampling), Tedlar bags, or adsorption tubes. Apparatus to determine the
moisture content, temperature, and static pressure of the source emissions may be
required during presurvey sampling if this information is not available from plant
personnel. Method 18 also describes several different calibration techniques for
use depending on the available calibration materials and the sampling and
analytical techniques used. Confirmation of target compounds in presurvey samples
may require analysis by means other than GC alone, such as GC/mass spectrometry
(GC/MS) or GC/infrared spectrometry (GC/IR). For the final sampling, in addition
to Tedlar bags and adsorption tubes, direct interface sampling and dilution inter-
face sampling are described. Analysis of the final samples utilizes the procedures
developed and optimized during presurvey sample analysis.
The descriptions of the apparatus and supplies that follow apply to items
needed for both presurvey and final sampling and analysis, except as noted. As
described above, all of the following equipment may not be required. The following
procedures and descriptions are only provided as guidance to the tester and are not
requirements of the method. Table 1.1 at the end of this section contains a
summary of quality assurance activities for procurement and acceptance of apparatus
and supplies.
1.1 Sampling
Guidance for the selection of a suitable sampling technique for a particular
compound can be found in Table B of the Method Highlights Section.
1.1.1 All Sampling Procedures - The following apparatus will be required for all
presurvey and final sampling procedures.. Use of alternative equipment requires
the approval of the Administrator.
Sampling System Check - Because of the number of sampling systems, volatile
organic compounds, and process operating conditions, the exact criteria for check-
ing the sampling system can only be determined using the presurvey sampling data.
Upon receipt of all the components to construct the sampling system, the system
should be assembled and checked over the intended range of use (i.e., sample flow
rate, duct temperatures).
-------
Section No. 3.16^.1
Date June 30, 1988
Page 2
. Sampling Probe - The sampling probe should (1) be constructed of stainless
steel, Pyrex glass, or Teflon tubing, (2) exhibit an outside diameter (OD) of 6.4
mm, (3) be enlarged at the duct end to contain a glass wool plug, and (4) possess a
heating system capable . of maintaining the sample temperature at 0° to 3°C above
duct temperature. The expanded section of the probe must be packed with glass wool
prior to sampling. The probe outlet must have a fitting suitable for attachment to
the sample line. A probe approximately 1.1 m (4 ft) long is usually sufficient;
the exact length can be determined during the preliminary survey. The selected
probe material should be nonreactive toward with the sample gas constituents so
that it will not bias the analysis, as well as appropriate to withstand the duct
temperature...•". .
Upon receiving a new probe, visually check it for adherence to
specifications (i.e., the length and composition ordered). Check for breaks,
cracks; and leaks. Leak check the probe and check the probe heating system during
the.sampling system check described above. The probe should be able to maintain
the required temperature at the desired flow rate and remain leak free.
.Sample Line and Connecting Tubing - The sample line is generally 6.4-mm OD
Teflon tubing. Sample lines will require heat-tracing to prevent condensation of
sample constituents during sampling at some sources. The sample temperature must
be maintained at 0°C. to -3°C above the source temperature. The capacity of the
heating system should be sufficient, for its intended use. Upon receipt or during
the system check, the sample line should be checked to ensure that it is leak free
and will maintain . the desired temperature at the desired flow rate. It should be
noted that heat-traced sample lines require a significant amount of electrical
current to maintain the higher, temperature levels. The electrical requirements and
the weight of the heat-traced line, .should be taken into, account when designing the
sample train. . .
Quick Connects - For connections on the sample lines, gas sampling valve,
the pump unit, .cylinders,' sample bags, and calibration gas bags, quick connects or
the equivalent are needed. . When the connects come into contact with the sample
gas, they should be constructed of stainless steel. It is also useful to have
self-sealing quick connects on the sampling bags. The quick connects can be leak
checked during.the system check.
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
eases the> absolute -barometric pressure can be obtained from a nearby weather
service station.., If-the elevation of the sampling point is higher than that of the
weather station, .the reported barometric pressure is reduced at a rate of 2.5 mm
Hg/30 m (0.1 in. Hg/100 ft) of elevation difference; if the sampling point is lower
than the weather station, the pressure is increased at the same rate. Note: The
barometric pressure from the .weather service station should not be corrected to sea
level.
.-, . Check 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 and should be repaired or replaced.
Moisture Determination - A moisture determination may be required. Two
techniques can generally be ..used: (1) Method 4 or .(2) wet bulb/dry bulb
thermometers. If Method 4 is used, the tester should refer to Section 3-3 of this
Handbook. If the wet bulb/dry bulb thermometers are used, both thermometers should
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Section No. 3.16.1
Date June 30, 1988
Page 3
be accurate to within 1°C. Upon receipt, the thermometers should be checked
against a mercury-in-^glass thermometer to ensure that they are reading properly.
Flow Rate Determination - The flow rate in the duct may have to be deter-
mined for some emission standards. If the flow rate is to be determined, the
tester should refer to Section 3-1 of this Handbook and meet the requirements and
follow the procedures of this method.
1.1.2 Glass Sampling Flask Sampling Technique - The following apparatus and rea-
gents will be required for the .collection of samples (presurvey only) using glass
sampling flasks. Use of alternative equipment requires the approval of the
Administrator.
Purged or Evacuated Glass Sampling Flasks - Presurvey samples can be
collected in precleaned double ended glass sampling flasks possessing minimum
capacities of 250 ml. Teflon stopcocks, without grease, are preferred. Upon
receipt, flasks should be checked to ensure that they are not broken. Flasks must
be cleaned prior to use. The cleaning procedures are described later in Subsection
3.2. If the flasks do not meet these requirements, replace or reclean.
1.1.3 Tedlar Bag/Evacuated Container and Adsorption Tube Sampling - The following
apparatus will be required for the collection of presurvey or final samples using
adsorption tubes or Tedlar bags housed in evacuable containers. If the apparatus
are purchased separately, each item should be checked individually as described
below. Following this, all components should be assembled, as they will be used in
the field and then checked using the following procedures:
1. Assemble the sample train as described in Subsection 4.3-1•
2. Leak check the train as described in Subsection 4.3-1-
3. Attach a primary gas test meter to the inlet of the sample train and
pull the desired flow rate through the sample train for the typical
sample run time. The measured volume should be within 10% of the
calculated volume or rate. If the system does not meet these
requirements, replace or repair and then recalibrate.
Tedlar Bags (For Sampling and to Prepare Gaseous Calibration Standards)-
Bags used to collect field samples and prepare gaseous calibration standards must
be constructed of a suitable material, be leak free, and have the proper fittings.
Typically, self-sealing quick disconnects are used on the sample bags. Tedlar is
the material of choice for the sample bags, however other materials may be used
successfully. If the sample bags are constructed by the tester, they are generally
double-sealed. The exact bags to be used in the field test or for making calibra-
tion standards must pass three criteria as follows:
1. Bags must pass the leak check as described in Subsection 4.3-1-
2. The organic components that are to be collected in the bags should be
placed in a bag at about the same concentration for which it will be
used, and the organic concentration in the bag determined as soon as
possible after this. The organics should then remain in the bag for a
period equal to the time anticipated between field sampling and
analysis. The concentration, upon reanalysis, must be within 10% of
the original concentration.
3. Next, the bag should be emptied and refilled with zero air or nitrogen.
It should be allowed to sit for at least 2 hours and then be
reanalyzed; the concentration of the organic(s) in the bag must be
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Section No. 3-16..1
Date June 30, 1988
Page 4
less than 10% of the original concentration.
If the bags do not pass the leak check, they must be reconstructed. If they do not
pass the second and third criteria, a different material of construction or a
different sampling technique must be used. If the bags do not meet these require-
ments, replace, use an alternative technique or use a different sampling technique.
Rigid Leak-Proof Container - Rigid leak-proof containers must be of the
proper size to fit the bags and are generally made of rigid plastic. However, the
material of construction is typically not important since the container does not
come into contact with the sample gas. Containers usually have a clear top or
window in them to check that the bag does not overfill during testing. The top of
the container must have connections to attach the sample probe to the outside and
the sample bag to the inside. A connection for the sample pump must also be
available on the container. Upon receipt or construction of the container,
assemble the system as it will be used in the field and then leak check it at the
maximum vacuum anticipated. Inflate a bag to the degree it will be filled in the
field and check that the bag can be removed after it has been filled to allow
external heating. If the bag system is designed to keep the bag at a specified
temperature, then the heating system must be checked as described below in
Subsection 1.1.6. If the container does not meet these requirements, modify,
repair, or replace it.
Pump - For the indirect sampling technique (pump after the bag or charcoal
tube) , any pump of proper capacity can be used. If the pump is to be used for a
direct sampling technique (pump in the sample line), the pump internals must be
leakless and made of stainless steel or, preferably, Teflon. Upon receipt, check
for proper specifications. If the pump does not meet the specifications, repair or
replace it.
Flowmeter - The flowmeter must be of the proper flow rate range. Upon
receipt, check the specifications and then calibrate as described in Subsection
2.1.3. If the flowmeter does not meet the requirements, replace or recalibrate it.
Adsorption Tube - An absorption tube must (1) be of adequate capacity, (2)
contain the proper adsorption material, and (3) consist of a primary and secondary
section. The selection of the proper type and size of adsorption tube should be
based on previous experience (including the literature and tables in the Method
Highlights) or laboratory evaluation. The selection and/or evaluation of the
proper adsorption tube is described in detail in Subsection 3-4. The criteria
shown in Subsection 3-4 must be met or the tubes must be replaced or modified.
Personnel Sampling Pump - A personnel sampling pump can be used for
collecting adsorbent tube samples. It must sample at or be adjustable to the
proper flow rate range. Upon receipt, check the specifications and calibrate as
described in Subsection 2.1.4. If it does not meet the specifications, replace or
calibrate it.
1.1.4 Direct Pump Sampling Procedure - The direct pump sampling procedure will
require the same apparatus described in Section 1.1.3 for bag and adsorption tube
sampling. The only difference is that the pump internals must be constructed of
materials that will not interfere in the analysis (i.e., Teflon or stainless steel)
and the rigid container does not have to be leak free. The system should be
assembled, leak checked and then the flow rate checked as described above. If the
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Section No. 3.16.1
Date June 30, 1988
Page 5
system does not meet the criteria, then it must be replaced or repaired and then
leak checked and recalibrated.
1.1.5 Explosion Eisk Bag Sampling Procedure - The following apparatus, in addition
to the apparatus described in Subsection 1.1.3, will be required for collection of
bag samples in areas where there is any possibility of explosion. These procedures
assume that the sample gas collected is not above the lower explosive limit. If it
is, a complete safety plan should be developed and reviewed by the plant and
tester. This Handbook will not attempt to describe the procedures used to collect
explosive gases.
The major concern in most areas having an explosion potential is that no open
flames or non-intrinsically safe electrical equipment be used. The first approach
to sampling in these areas is to remove the electrial systems (i.e., pumps) to an
area that is not explosive. This can be accomplished by running the vacuum line
from an area that is not explosive to the sample bag or charcoal tube in the
explosive area. The vacuum line can be run up to 200 to 300 feet with no problems.
Sampling is then conducted in the normal manner.
Another approach described in Method 18 uses a steel canister to provide the
vacuum source. This approach is difficult and can still be hazardous because it
involves handling a steel container, and possibly a stainless steel probe, in an
explosive area. Another alternative is the use of an intrinsically safe pump, such
as a personnel sampling pump, with adsorption tubes or Tedlar bags housed in
evacuable containers. Any system that is purchased or constructed must be
leakless, be able to control the flow rate properly, and meet all plant safety
requirements.
1.1.6 Heated Bag Sampling Procedure - This procedure must be used in the event
that condensation is observed in the bag and/or sample line during testing or if
the sample bag retains more than 10% of the sample concentration based on the post-
test sample bag retention check. The apparatus described below will be required,
in addition to the apparatus described in Subsection 1.1.3- Both the sample line
and container must be heated to maintain the bag at a specified temperature (i.e.,
0°C to 3°C above source temperature). The sampling system is checked in the manner
described above, except that the heating system must also be considered; check
procedures should consider use of the system at ambient temperatures less than the
laboratory temperature (including wind chill factors). The entire surface of the
sample probe and the sample bag must be maintained at the specified temperature.
A possible alternative to maintaining the bag at the specified temperature is the
addition of external heating with heat lamps prior to analysis. The exact system
that will be suitable for any given source should be determined prior to testing,
if possible. The operation and checks of heated sampling systems are described in
Subsection 4.3- If the system does not meet all the criteria, use a different
approach or repair the system and recalibrate.
Heated Bag Sample Container - The heated bag sample container must be
capable of maintaining the entire bag at the specified temperature. If an
electrical source is used to heat the container, the tester must be aware of the
additional explosion potential that is created. One check on the system can be
made with a thermocouple in the sample cavity; this check of the system will not,
however, demonstrate that all the surfaces are maintained at the required
temperature. All external surfaces of the container should be well insulated. A
visual check of the system should reveal if the system appears to be sufficiently
insulated. If the system allows the bag to have cooler surfaces, the posttest
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Section No. 3.l6vl
Date June 30, 1988
Page 6
retention check on the bag will probably fail.
Heated Sample Lines and Probe - The sample probe and sample line must also
be capable of maintaining the specified temperature. They should also not have any
cooler surfaces. These can be checked by pulling the desired flow rate through
them and then checking the temperature in the line and/or probe with a
thermocouple. Proper insulation is necessary to maintain the temperature
throughout the entire length. If the temperature cannot be maintained, replace or
repair the-line and/or probe and then recheck.
1.1.7 Prefilled Tedlar Bag Sampling Procedure - This procedure is an alternative
to the heated bag sampling procedure. The following apparatus and reagents are
required for this procedure, in addition to the apparatus described in Subsections
1.1.3 and 1.1.4. The prefilled bag sampling system is used to dilute the
concentration of the condensibles below saturation. This system can also be used
to dilute the gases to below the lower explosive limit. The major difference
between the prefilled bag sampling system and the other bag sampling systems is
that the volume of diluent gas added to the sample bag and the volume of gas
sampled must be accurately measured. The dilution must be accounted for in the
calculation of the measured gas concentration. Therefore, the diluent gas must be
added with a calibrated dry gas meter or a calibrated flowmeter; then, during
sample collection, the gas collected must be accurately measured using a flowmeter
or a metered pump. To obtain the required accuracy, the flowmeter and pump are
placed in the sample line prior to the sample bag. Since condensation may occur,
the flowmeter and pump must be housed in a heated box. This system is checked in
the same manner as a dilution system (see Subsection 1.1.9). The check for the
prefilled system is described in Subsection 4.3-4.
Heated Flowmeter - A calibrated heated flowmeter is required to accurately
determine the volume of gas sampled. The flowmeter should be housed in a heated
box that will maintain the specified temperature. The flowmeter should be
calibrated as described above in Subsection 2.1.3- If the criteria are not met,
replace or repair and then recalibrate. A metering type pump may be used to
replace the flow rate meter and the pump.
'Positive Displacement Teflon-Lined Pump - A positive displacement pump lined
with Teflon or constructed of stainless steel, of proper capacity and contained in
a heated box is required. A Teflon-coated diaphram-type pump that can withstand
120°C and delivers 1.5 liters/minute is typically used. Upon receipt, check the
pump for capacity and then conduct a leak check on the pump. The pump must be
leak free at all vacuum settings. The heating system will be checked during the
sampling system check. If the pump is not of the correct capacity and not leak
free, then replace or repair it.
Heated Box for Flowmeter and Pump - The flowmeter and pump must be contained
in a heated box to maintain the proper temperature. Construct the box such that
the temperature can be controlled and monitored. After construction, check the
system to ensure that it will maintain the desired temperature(s). If it will not
maintain the temperature(s), repair the unit.
1.1.8' Direct Interface Sampling Procedure - A heated probe, heated sample line,
heated gas sampling valve, needle valve, and charcoal adsorber are required for
direct interface sampling. The required apparatus and reagents pertaining to the
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Section No. 3.16.1
Date June 30, 1988
Page 7
gas chromatograph are described below in Subsection 1.2. After the individual
components are checked as shown below, the sampling system should be assembed as
shown in Subsection 4.3-6 and checked using the following procedures:
1. Turn on the heating system and adjust to the maximum temperature at
which it is to be used.
2. Connect the inlet to the sampling probe. After the heating system has
stabilized at the temperature setting, turn on the pump and evacuate
to about 10 in. of H20. The system must be leak free; no flow should
be observed from the charcoal adsorber system. If the system is not
leak free, repair the system.
3. After the system has been shown to be leak free, adjust the needle
valve until the flow rate that will be used in the field is obtained.
The temperature at the discharge of the heated sample valve should be
at the set temperature. Insert a thermocouple into the inlet of the
probe to insure that the first several feet of the probe and line are
properly heated. If the set temperature is not obtained, repair the
system or use the temperature obtained for a recalibration of the
temperature setting.
Heated Probe and Sample Lines - The sample probe and sample line must be
equipped with a heating system and insulation. All of the interior surfaces must
be maintained at the temperature setting. Although all the interior surfaces can
not be easily checked, installing proper insulation and following the system check
shown above should be sufficient to determine the adequacy of the probe and sample
line heating system.
Heated Gas Sampling Valve - A heated sampling valve (which includes the
sample loops) is required to maintain the sample injected into the GC at the
desired temperature. The sample valve and loop are generally enclosed in an oven
in which the temperature can be controlled and monitored. Upon receipt, check the
temperature controller.
Charcoal Adsorber - The charcoal adsorber is required to remove the organics
from the excess flow through the system. Since the charcoal adsorber is used only
for tester safety, there are no requirements on the adsorber. However, since the
charcoal will be spent with time, the tester should change it periodically.
Alternatively, the flow can be vented at a safe distance away from any personnel.
1.1.9 Dilution Interface Sampling Procedure - In addition to the apparatus des-
cribed in Subsection 1.1.8, dilution pumps, flowmeters and valves which are con-
tained in a heated box, and diluent gases are required for the dilution interface
system. The calibration of the dilution system is described in Subsection 2.2.
The individual components should be checked as shown below and then the system
should be calibrated as described in Subsection 2.2. If the system does not meet
the calibration requirements, it should be replaced, or repaired and recalibrated.
Dilution Pumps - Two Model A-150 Komhyr Teflon positive displacement-type
pumps, or equivalent models capable of delivering 150 cc/minute, are required.
Alternatively, calibrated flowmeters can be used in conjunction with Teflon-coated
diaphram pumps. Upon receipt calibrate the pumps or flowmeter and pump as
described in Subsection 2.1. If the pumps do not meet the calibration
requirements, replace or repair and then recalibrate.
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Section No. 3.16.1
Date June 30, 1988
Page 8
Flowmeters - Two flowmeters are required to measure the diluent gas, at a
rate of about 1350 cc/minute. Upon receipt, the flowmeters should be calibrated as
described in Subsection 2.1. If the flowmeters do not meet the calibration
critera, replace or repair and then recalibrate.
Diluent Gas - Diluent gas in cylinders fitted with regulators are required
for sample dilution. Nitrogen or hydrocarbon-free air can be used depending on the
nature of the source gases. Alternatively, ambient air can be cleaned and dried
with charcoal and silica gel. The organics in the dilutent gas must be below the
detection limit.
Heated Box for Sample Dilution System - The pumps and control valves must be
housed in a heated box to control and monitor the temperature. After construction
or receipt, check the temperature control system. If the box cannot maintain the
desired temperature, replace or repair and recheck.
1.2 Sample Analysis
The analysis of Method 18 samples requires the use of a gas chromatograph
(GC) regardless of the technique used for either presurvey or final sampling.
Guidance for the selection of suitable GC detectors is provided in Table C in the
Method Highlights Section. As a starting point for the analysis of the presurvey
sample, Table D in the Method Highlights Section provides guidance for the
selection of a suitable packed GC column. Any interferences with the GC analysis
may be source-specific, so the most suitable analytical system must be established
using the presurvey samples. The following apparatus will be required for the GC
analysis.
1.2.1 Gas Chromatograph - A GC equipped with a suitable detector as specified in
Table C in the Method Highlights Section. The GC shall be equipped with a
temperature-controlled sample loop and valve assembly for analysis of gas samples
or a temperature-controlled injection port for analysis of liquid samples from
adsorption tubes. Use of alternative techniques for introducing samples into the
GC requires the approval of the Administrator. The GC should be equipped with a
temperature-controlled oven, while a temperature-programmable oven may also be
required for some analyzers. Method 18 may be used to quantify gaseous organic
compounds at concentrations ranging from about 1 part-per-million (ppm) to the
upper range governed by detector saturation or column overloading. For the
combination of GC options chosen, the lower limit of quantitation, as defined by
Knoll'12 , for the target organic compounds should be less than the emission limit
for the particular source being tested.
1.2.2 GC Column - Guidance for the selection of the appropriate GC column is
provided in Table D in the Method Highlights Section. The columns listed in
Appendix I to Table D have been found to work for analysis of the corresponding
organic compounds under certain conditions. Since interfering compounds may be
source-specific, Method 18 permits the use of any GC column, provided the following
precision and accuracy are achieved:
Precision: Duplicate analyses within 5 percent of their mean value.
Accuracy: Analysis results of an audit sample within 10 percent of the
prepared value.
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Section No. 3.16.1
Date June 30, 1988
Page 9
In addition, resolution of interfering compounds from target compounds should be
achieved. For determining whether acceptable resolution has been achieved, follow
the procedures described in Appendix C "Quality Assurance Procedures"', Procedure 1
"Determination of Adequate Chromatographic Peak Resolution."'*3
1.2.3 Recorder - A linear strip chart recorder is required, as a minimum, to
record the GC detector output. Alternatively, an electronic integrator may be
used and is generally recommended.
1.2.4 Recorder or Electronic Integrator Paper - Consult operator's manual or
manufacturer for correct type.
1.2.5 Regulators - Gas cylinder regulators will be required for use of the gas
cylinders described in Subsections 1.3-1, 1.3-2, and 1.3-3- Consult with suppliers
of gas cylinders to determine the proper type of regulator required.
1.2.6 Tubing and Fittings - Tubing and fittings will be required to connect the
gas cylinder regulators to the GC.
1.3 Reagents and Glassware
The exact reagents and glassware required depend on the sampling procedure
chosen, the calibration techniques to be used, and the particular requirements of
the GC system.
1.3.1 GC Carrier Gas - The carrier gas selected must be hydrocarbon-free. The
type of carrier gas depends on the type of GC detector and GC column being used.
Consult the GC operator's manual, the GC manufacturer, and/or the column
manufacturer for recommendations on the optimum carrier gas for a particular appli-
cation.
1.3.2 Auxiliary GC Gases - Certain GC detectors will require auxiliary gases for
proper operation. Consult the GC operator's manual or the GC manufacturer for
recommendations on a particular application.
1.3-3 Calibration Gases - These include cylinder gases containing known
concentrations of target organic compounds for preparation of GC calibration
standards, direct use as GC calibration standards, or calibration of a dilution
interface system. If gases are not available in the required concentrations for GC
calibration, procure the reagents and glassware described in Subsections 1.3*4
through 1.3.7.
1.3-4 Zero Gas - Hydrocarbon-free air or nitrogen, for preparing gaseous cali-
bration standards from calibration gas cylinders or liquid organic compounds.
1.3.5 Liquid Organic Compounds - Pure or high purity liquid (occasionally gaseous)
samples of all the organics for which calibration standards will be prepared.
1.3.6 Syringes - Calibrated, gas tight 500-, 10-, and 1.0-microliter sizes with
maximum accuracy, for preparing gaseous calibration standards, for preparing
adsorption tube standards, and for injection of liquid standards and samples into
the GC. Other size gas tight syringes may be appropriate.
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Section No. 3.16.4
Date June 30, 1988
Page 10
1.3-7 Midget Impinger/Hot Plate Assembly - To prepare gaseous standards in Tedlar
bags from liquid organic compounds requires a midget impinger equipped with a
septum and a tee on the inlet stem and a boiling water bath on a hot plate. A dry
gas meter, previously described in Subsection 1.1.1, is also required.
1.3-8 . Screw Top Septum Vials - For preparation of adsorption tube standards and
samples, J-ml amber screw top septum vials with Teflon-lined septa are required.
1.3.9 Desorption Liquid - For preparation of adsorption tube standards and
samples, desorption liquid is required. For the correct desorption liquid, refer
to the appropriate NIOSH method for the target compound(s) referenced in Table B in
the Method Highlights Section.
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Section No. 3-16.1
Date June 30, 1988
Page 11
Table 1.1. ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS AND SUPPLIES
Apparatus
All Sampling
Procedures
Sampling system
check
Sampling probe
Sample line and
connecting tubing
Quick connects
Barometer
Moisture
determination
Flow rate
determination
Glass Sampling
Flask Technique
Purged or evacu-
ated sampling
flasks
Acceptance limits
Maintain proper
flow rate and
temperature
Proper material
of construction
and capable of
maintaining proper
temperature
Constructed of
Teflon and capable
of maintaining
proper temperature
Stainless steel
construction and
leak free
Capable of measuring
atmospheric pressure
to within 2.5 mm
(0.1 in.) Hg
See Section 3-3 of
this Handbook
See Section 3.1 of
this Handbook
Double ended glass
flask with Teflon
stopcocks
Frequency and method
of measurement
Upon receipt, conduct
check in specified
subsection
Visually check and
then run heating
system checkout
Visually check and
then run heating
system checkout
Visually check and
conduct leak check
Check against mercury
in-glass barometer or
equivalent
(Sec. 3-5.2)
Same as in Section 3 • 3
Same as in Section 3 • 1
Visually check upon
receipt
Action if
requirements
are not met
Repair or return
to manufacturer
Repair or return
to manufacturer
Repair or return
to manufacturer
Repair or return
to manufacturer
Determine cor-
rection factor,
or reject
Same as Sec. 3.3
Same as Sec . 3-1
Return to
manufacturer
(Continued)
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Table 1.1 (Continued)
Section No. 3.16.1
Date June 30, 1988
Page 12
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Evacuated Con-
tainer and Adsorp-
tion Tube
Sampling
Tedlar bag
Constructed of
material in which
organics remain
stable and are not
retained; leak free
Upon receipt, leak
check and conduct
stability and
retention check
Return to man-
facturer, change
material, or
use different
sampling tech-
nique
Rigid leak-
proof container
Leak free and
of proper size
Upon receipt,
visually check and
then conduct leak
check
Repair or return
manufacturer
Pump
Leak free and of
proper capacity
Visually check and
then conduct leak
check and flow rate
check
Repair or return
to manufacturer
Flowmeter
Proper flow rate
range and cali-
brated
Upon receipt, check
specifications, check
visually, then
calibrate
Return to manu-
facturer or
repair and then
recalibrate
Adsorption
tube
Proper material,
adequate capacity,
and consisting of a
primary and second-
ary section
Conduct laboratory
evaluation or consult
literature
Replace or make
modification and
recheck
Personnel sampling
pump
Proper flow rate
range and calibrated
Upon receipt, check
specifications, then
calibrate
Return to manu-
facturer or
repair and then
recalibrate
(Continued)
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Table 1.1 (Continued)
Section No. 3.16.1
Date June 30, 1988
Page 13
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Direct Pump
Sampling
Pump
Stainless steel or
Teflon-lined, proper
capacity, leak free,
and heated
Visually check, then
conduct leak check,
flow rate check, and
system heating check
Return to manu-
facturer or
repair and
recalibrate
Flowmeter
Proper flow rate
range, leak free,
and heated
Visually check, then
conduct leak check,
flow rate check, and
heating check
Return to manu-
facturer or
repair and
recalibrate
Explosion Risk
Bag Sampling
Nonexplosive
vacuum source
Proper flow rate
capacity and
intrinsically safe
Check with plant
safety rules and
check flow rate
capacity
Return to manu-
facturer or
repair and
recheck
Heated Bag
Sampling
Sampling bag
Same as above
Same as above
Same as above
Heated bag
container
Leak free, adequate
capacity, and
heat system
capable of main-
taining proper
temperature
Visually check,
then conduct
leak check and
heating check
Return to manu-
facturer or
repair and
recheck
Heated sample
lines and probe
Constructed of
Teflon and/or
stainless steel
Visually check,
then conduct
heating check
Return to manu-
facturer or
repair and
recheck
Prefilled
Bag Sampling
Heated flowmeter'
(Continued)
Same as above
Same as above
Same as above
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Section No. 3-16.1
Date June 30, 19*88
Page 14
Table 1.1 (Continued)
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Stainless steel or
Teflon-lined pump
Same as above
Same as above
Same as above
Heated box for
flowmeter and
pump
Proper flow rate
range and capacity;
heating system
capable of main-
taining the proper
temperature
Visually check,
then conduct
leak check, flow
rate check, and
heating check
Return to manu-
facturer or
repair and
recheck
Direct
Interface
Sampling
Heated probe, pump
and sample
lines
Same as above
Same as above
Same as above
Heated GC sample
valve
Proper valve and
heating system;
consult owner's
manual
Visually check,
then conduct
check of heating
Return to manu-
facturer or
repair and
recheck
Dilution
Interface
Sampling
Stainless steel or
Teflon-lined pump
Same as above
Same as above
Same as above
Dilution pump
Teflon-lined
metering pump
with capacity
of 150 cc/min
Visually check,
then calibrate
Return to manu-
facturer or
repair and
recalibrate
Flowmeters
Proper flow rate
range and
calibrated
Visually check,
then calibrate
Return to manu-
facturer or
repair and
recalibrate
Diluent gas
Hyrocarbon-free
air, nitrogen, or
dry cleaned air
Visually check cylin-
der; check cylinder
pressure; run a blank
to monitor impurities
Return to
manufacturer
(Continued)
-------
Section No. 3.16.1
Date June 30, 1988
Page 15
Table 1.1 (Continued)
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Heated box for
sample dilution
system
Heating system with
temperature con-
troller and monitor
Conduct heating
check
Return to manu-
facturer or
repair and
recheck
Sample Analysis
Gas chromatograph
Suitable detector,
precision of ^ 5%,
and accuracy of
+ 10%
Refer to Table C
in Method Highlights
then check GC with
applicable organics
Return to manu-
facturer or
repair and
recheck
GC column
Adequate peak
resolution
Upon receipt, use
procedure described
in 40 CFR 60, App. C
or Method 625
Return to manu-
facturer or
change con-
ditions and
recheck
Strip chart re-
corder or elec-
tronic integrator
See owner's manual
Upon receipt, check
as recommended by
manufacturer
Repair or
return to
manufacturer
Regulators
Proper CGA fittings
and pressure
control
Upon receipt, attach
to cylinder and leak
check
Return to manu-
facturer or
repair or
replace fitting
and recheck
Reagents and
Glassware
GC carrier gas
As specified by GC
owners manual and
hydrocarbon-free
Visually check upon
receipt; check cyl-
inder pressure
Return to
manufacturer
Auxiliary gas
As specified by
owners manual
Visually check upon
receipt; check cyl-
inder pressure
Return to
manufacturer
Calibration gas
(Continued)
Proper compounds
and known concen-
tration in proper
range
Upon receipt, check
cylinder tag and
certification; check
cylinder pressure
Return to manu-
facturer or
remake or rename
-------
Section No. 3-16.1
Date June 30, 19£8
Page 16
Table 1.1 (Continued)
Apparatus
Zero gas
Acceptance limits
Hydrocarbon- free
air or nitrogen
Frequency and method
of measurement
Visually check upon
receipt; check cyl-
inder pressure
Action if
requirements
are not met
Return to
manufacturer
-------
Section No. 3.16.2
Date June 30, 1988
Page 1
2.0 CALIBRATION OF APPARATUS
Calibration of the apparatus is one of the most important functions in
maintaining data quality. The detailed calibration procedures included in this
section were designed for the sampling equipment specified in Method 18 and de-
scribed in the previous section. The calibration of the analytical equipment is
described in the section detailing the analytical procedures, Section 3-16.5-
Table 2.1 at the end of this section summarizes the quality assurance functions for
the calibrations addressed in this section. All calibrations including the analyt-
ical equipment should be recorded on standardized forms and retained in a calibrat-
ion log book.
2.1 Metering Systems
2.1.1 Net Test Meter - The wet test meter must be calibrated and have the proper
capacity. For Method 18, the wet test meter should have a capacity of about 1
L/min. No upper limit is placed on the capacity; however, the 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 manufacturers to an accuracy of +_ 2%.
Calibration of the wet test meter must be checked upon receipt and yearly there-
after. A liquid positive displacement technique can be used to verify and adjust,
if necessary, the accuracy of the wet test meter to +_ 2%. This technique is de-
scribed in Sections 3-5.2, 3.8.2, and 3-15-2 of the Handbook.
2.1.2 Dry Gas Meter - A dry gas meter is required for gas and liquid injection
calibrations, to prefill bags prior to sampling using the prefilled bag dilution
technique, and/or to calibrate the flow rate meters. For Method 18, the dry gas
meter is the same size or smaller than the dry gas meter typically used for Method
6. The meter must have an accuracy of +_ 3$ for the flow rate and sample volume
used. Calibration of the dry gas meter must be conducted initially upon receipt,
quarterly when utilized to make laboratory calibration standards, and following
each field test series for field use. The calibration procedures are described in
Section 3-5-2 of this Handbook.
2.1.3 Flow Pate Meter(s) - Flow rate meters are needed for (1) sampling and (2)
making calibration standards. Since they are used to determine flow rate and for
total volume determinations, the flow rate meter(s) selected must have an accuracy
of +_ 3% for the flow rate and total sample volume for which they are used.
Acceptable flow rate meters include rotameters, critical orifices, mass
flowmeters, and dry gas meters. If data from the flow rate meter is used only as
an indicator of the flow rate and is not used in any of the emission calculations,
then the accuracy of +_ 3% does not apply. While it is desirable to calibrate the
gas flowmeter with the cylinder gas to be measured, the quantity available and cost
may preclude it. The error introduced by using the diluent gas for calibration in
place of the actual gas to be measured is insignificant for gas mixtures of up to
1,000 to 2,000 ppm.
Initial Calibration - The flow metering system should be calibrated when
first purchased and at any time the posttest calibration yields a calibration
factor that does not agree within 5% of the pretest calibration factor. A
-------
Section No. 3-16.2
Date June 30, 1988
Page 2
calibrated wet test meter, calibrated dry gas meter, or a properly sized bubble
meter should be used to calibrate the metering system.
The flow rate meter should be calibrated in the following manner before its
initial use in the field.
1. Leak check the flow rate meter and pump as follows:
a. Temporarily attach a suitable rotameter (e.g., 0-40 cm3/min) to
the outlet of flow rate system. The pump should be placed either
before or after the flow rate meter based on where it will be used.
Place a vacuum gauge at the inlet to the drying tube.
b. Plug the flow rate system inlet. Evacuate to a pressure at least
equal to the lowest pressure that will be encountered during use. If
the system usually operates at or near atmospheric conditions, then
pull a vacuum of 25 mm (1 in.) Hg.
c. Note the flow rate as indicated by the rotameter.
d. A leak of <0.02 L/min must be recorded or leaks > 0.02 L/min must be
eliminated.
2. Attach the wet test meter, bubble meter, or calibrated dry gas meter to
the inlet of the flow rate metering system.
3. Run the pump for 15 minutes with the flow rate set at the midrange flow 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 2.1A
(English units) or 2.IB (metric units) when calibrating a dry gas meter ,
rotameter, or mass flow meter, and Figure 2.2A (English units) or 2.2B
(metric units) when calibrating a critical orifice} using sample volumes
equivalent to at least five revolutions of the dry test meter. Three
independent runs must be made.
a. For critical orifices, runs will be conducted at the single flow rate
of the orifice meter. The runs should be at three different vacuums
that are greater than one half an atmosphere (i.e., 18, 19 and 20 in.
Hg.). This is to demonstrate that the orifice yields the same
flowrate at all critical vacuums.
b. For rotameters, mass flow meters, and dry gas meters, runs will be
conducted at three different flow rates over the range to be used
(top, middle, and bottom of range).
5. Calculate the YA for each run for the dry gas meter, rotameter and mass
flowmeter or calculate the K' for the critical orifice as shown on the
data forms. Adjust and recalibrate or reject the dry gas meter,
rotameter, or mass flow meter if one or more values of Yt fall outside the
interval Y _+ 0.03Y, where Y is the average for three runs. Otherwise, the
Y (calibration factor) is acceptable and is to be used for future checks
and subsequent test runs. The K' should be within 3% of the average for
all three runs. If this is not true, reject the orifice or repeat the
calibration until acceptable results are obtained. The completed form
should be forwarded to the supervisor for approval, and then filed in the
calibration log book.
Posttest Calibration Check - After each field test series, conduct a calibra-
tion check as described above in Subsection 2.1 concerning the initial calibration
with the following exceptions:
-------
Date /
/ // /
ric p
_^_^_^ Calibrated by /4?^ Meter system no.
Barometric pressure, Pm = SJl^ite in. Hg Ambient temperature
, dry gas
Primary meter no.
X
,
Type of primary meter: wet test
Type of flowmeter calibrated: rotameter
, or bubble meter
, dry gas meter
, or mass flowmeter
Primary meter readings
Initial
reading
(V . ),a
• pi'*
ft3
0
0
0
Final
reading
(V ) a
v vpf ' •
ft3
0.70G,(s
0.1 Obb
1. 0(f04
Initial
temp , ° F
(tpl)
OF
^1
90
•j-o
Final
temp , ° F
(tpf)
op
Co
6.0550
Final
reading
(vs?)b
ft3 or
ft3 /min
O.OIJJ
0.035"3
O.OS30
Initial
temp
(tsi)
oF
(ol
To
^o
Final
temp
(t.f)
op
(,1
70
?0
Press
drop
(Ds),c
in.
H20
0
0
0
Time
min
(9) d
min
40
lJO
2JO
Calibration
factors
(Y,),6
6.W3
o.w.
0.^5-
(Y)
i — .
—
a
-------
Calibrated by A' Meter system no. feO ' '(*> Primary meter no. £\d IM ~\
Date _
Barometric 'pressure, Pm =
Type of primary meter: wet test X,
Type of flowmeter calibrated: rotameter
Ktl
mm Hg Ambient temperature
_, dry gas
or bubble meter
, dry gas meter
or mass flowmeter
Primary meter readings
Initial
reading
(vpi),a
m3
0
0
0
Final
reading
(V ) a
v vpf ' •
*!>•
20-13
to.fr
30- 2(0
Initial
temp , ° F
(tpl)
°C
TJD.S
1O b
•2-0. (*
Final
temp , ° F
(tpf)
°C
ZO.'Z
1.0.5
10 '.(P
Pres
drop
(DP)C
mm
H20
-136
-130
-/-50
Flowmeter readings
Initial
reading
l. rr
H-
«-i O
(D 2!
O
UJ •
O
- OJ
CO
oo
-------
Date
Calibrated by
Meter system no. \J}~~
Barometric pressure, Pm = 2-1. ^ G-
in. Hg Ambient temperature
Primary meter no.
°F
Type of primary meter: wet test
>C . dry gas
Type of critical orifice: capillary glass X , needle or tubing
, or bubble meter
, or adjustable
Primary meter readings
Initial
reading
(vpi),a
ft3
0
D
0
Final
reading
(V).a
ft3
0.7-J3
0.??3
0.??3
Initial
temp,°F
oF
M
70
T-o
Final
temp,°F
(tpf)
op
Of
To
*to
Pres
drop
-------
///
Date ///ft Calibrated by
Barometric pressure, P_ = 7 (ft
Meter system no. CD ~/Z- Primary meter no.
mm Hg Ambient temperature ,2-Q. <£~ °C
Type of primary meter: wet test
X- dry gas
Type of critical orifice: capillary glass X . needle or tubing
, or bubble meter
, or adjustable
Primary meter readings
Initial
reading
(vpi),a
L
0
0
0
Final
reading
(V ) a
v P f ' *
L
^^•n^
ZZ-.I3
Z2./2.
Initial
temp , ° F
(tpl)
°C
zo.z
2.0. 1,
2,0. L,
Final
temp,°F
(tpf)
°C
Z.0.^
Z0.lt
2^0. (,
Pres
drop
<°P>
mm
H20
-/3o
-73o
-fbO
Critical orifice readings
Initial
setting
b
L or
L/min
fl-iL-rJ-
fi*ed
f>7<*cL
Final
setting
b
L or
L/min
HIA
s//4
rflA
Press
drop
c
mm
Hg
4-80
570
£50
Time
min
(e),d
min
Zo
££
2J>
Calculated
flow rate
CQ(std)]e
L/min
/. 042,
/.on
/.04Z,
Calibration
factor6
(K'J
J.OZHt,
O.DZ
-------
Section No. 3-16.2
Date June 30, 1988
Page 7
1. The leak check is not conducted because a leak may have been corrected
that was present during testing.
2. .Three or more revolutions•of the dry gas .meter may be used.
3. Only two runs need be conducted at the average flow rate during the test.
4. Record the calibration check data on the appropriate posttest calibration
check data form, Figure 2.2A (English units) or Figure 2.2B (metric
units).
5. If the posttest Y or K' factor agrees within 5$ of the pretest factor, the
flow meter .is acceptable. If the factor does not agree due to a leak,
correct the leak and recalibrate the flow rate device. The reported
results should then be calculated using both the factor obtained with the
leak and the factor obtained without the leak. If the flowmeter does not
pass the calibration check, the metering system must be recalibrated as
described above for the initial calibration. Either calculate the
emission results for the test report using both factors or consult with
• the Administrator.
2.1.4 Personnel Sampling. Pump - Personnel .sampling pumps are used to collect
samples using adsorption tubes. They should be calibrated before and after the
field trip using a soap bubble meter as follows:
1. Set up the calibration apparatus as shown in Figure 2.3-
2. Check the pump battery with a voltmeter to assure adequate voltage;
charge, if necessary.
3- Turn the pump on and moisten the inner surface of the soap bubble meter
with soap solution; draw bubbles upward until they travel the entire
length of the bubble meter without breaking.
4. Adjust the pump to desired nominal flow rate. Check the manometer; the
pressure drop should not exceed 25mm Hg (13 in.) water.
5. Start a soap bubble and measure the time with a stopwatch that it takes to
traverse at least 500 ml. Repeat at least twice more. Average the results
and calculate the flow rate by dividing the calibration volume by the
.average time.
6. Record the following data:
a. volume measured
b. elapsed time
c. pressure drop
d. air temperature
e. atmospheric pressure
f. serial number and model of the pump
g. date and name of operator
7- If the pump used for sample collection uses a rotameter, the calibrated
flow rate must be adjusted for the ambient pressure and temperature during
sampling:
Vc0rr = Q 8(Pc T8 / Ps Tc) °-5
Equation 2-17
where
V = Corrected sample volume, liters,
Q = Indicated flow rate, liters/min,
6 = Sampling time, min,
Pc = Pressure during calibration, mm Hg,
P = Pressure during sampling, mm Hg,
-------
Tubing
Soap
Bubble
Meter
(1-Liter)
Beaker
Containing
Soap
Solution
Personnel
Sampling
Pump
TJ O CO
to to n>
m rt- o
0) (D rt
c-i O
OOC 3
O
- l-O
Figure 2.3- Personnel pump calibration apparatus.
OO
ON
-------
Section No. 3.16.2
Date June 30, 1988
Page 9
T = Temperature during calibration, °K, and
Ts = Temperature of sample gas, °K.
2.2 Dilution System
2.2.1 Dynamic Dilution System - A dynamic dilution system may be required for (1)
preparation of low concentration standards from high concentration standards or (2)
for measuring high concentrations of organic emissions. The dynamic dilution
system must be initially calibrated in the laboratory and then checked during each
use. To prepare the diluted calibration samples, calibrated rotameters are
normally used to meter both the high concentration calibration gas and the diluent
gas. Other types of flowmeters and commercially available dilution systems can
also be used provided they meet the performance criteria described below.
The following steps should be used to conduct the laboratory calibration of
the dynamic dilution system:
1. Assemble the dilution system (see Figure 2.4) as a unit using a calibrated
rotameter or mass flow meter for the calibration or stack gas in combina-
tion with a calibrated rotameter, mass flowmeter or dry gas meter for the
diluent gas. It is recommended for dilutions up to 20 to 1 that a single
dilution system be used. For dilutions greater than 20 to 1, a double
dilution system should be used. It is also recommended that the system be
assembled as a unit and not be disassembled between uses. The rotameters
should be calibrated for the range in which they will be used following
the calibration procedures described above.
2. Leak check the system by plugging the inlet line to both rotameters,
placing the dilution system discharge line in a container of water, and
turning on the sample pump. The system is leakless if no bubbles are
released from the discharge line.
3. The dilution system can be calibrated over the range that it will be used,
however, if the exact dilution to be used is known, it is better to
conduct a triple calibration at the desired dilution setting. Attach the
dilution system to the diluent and calibration gases. Set the flowmeters
to the desired rate and fill the bag with sufficient gas for GC analysis.
Be careful not to overfill the bag and cause the bag to apply additional
pressure on the dilution system. Record the flow rates of both flowmet-
ers , and the laboratory temperature and atmospheric pressure on the
dynamic dilution calibration form, Figure 2.5 or an equivalent form.
4. Analyze the diluted calibration gas and a calibration gas that is in the
same range as the diluted gas. The two gases must agree within 10% for
the calibration point to be acceptable. Repeat the calibration runs until
acceptable results are obtained at all desired settings.
2.2.2 Static Dilution System - The static dilution system can be used for (1) the
bag sampling technique and (2) for preparation of low concentration calibration
gases from high concentration cylinder gases. The dilution method for the bag
sampling technique is used to reduce the concentration of organics or water vapor
in a gas sample below the condensation point or for safe handling, below the lower
explosive limit. Static dilution involves filling a bag with a diluent gas using a
calibrated dry gas meter or mass flowmeter and using a syringe or a rotameter to
add the calibration gas or a sample of stack gases to make a lower concentration
calibration or sample gas.
The following steps should be used to calibrate a static dilution system in
the laboratory before use:
-------
Vent to Charcoal Adsorbers
Heated Line
from Probe
Quick
Connect
Quick
Connects to
Gas Sample
Valve
Source
Gas Pump
1.5L/Min
150 cc/Min
Pump
150 cc/Min
Pump
3-Way
Valves
in 100:1
Position
Flowmeters
(On Outside
of Box)
Flow Rate of
1350 cc/Min
Check Valve
Quick Connects
for Calibration
CO
Heated Box at 120° C or Source Temperature
To Heated GC Sampling Valve
Figure 2.4. Schematic of heated box required for dilution of samples.
O CO
CO (D
ct O
CD rt
H-
§§
0> Z
o
oo •
o
- 00
VD ON
CO •
osro
-------
Section No. 3.16.2
Date June 30, 1988
Page 11
P-
g-c,
AI/A
Date -*-/ II /0D Calibrated by
Date source meter calibrated I/ £&/6G>
Date stage 1 meter calibrated / / 26>/ 8
Date stage 2 meter calibrated
Heated box temperature
Leak check for total system
Certified concentration 22,1d> ppmv(X) Date of calibration curve <2-Jl116&
Source flowmeter number
Stage 1 flowmeter number
Stage 2 flowmeter number
Barometric press /6>/ mm Tin.) Hg
Organic compound
STAGE 1 RUN 1
Emission gas flowmeter reading, ml/min (qc i} / 5"d
Diluent gas flowmeter reading, ml/min (qdl) I OOP
Dilution ratio ~
Injection time, 24h
Distance to peak, cm
Chart speed, cm/min AJfA
Retention time, min
Attenuation factor
Peak area or units
Peak area X attenuation factor
Measured concentration,3 ppmv
Calculated concentration,15 ppmv (Cs) Z6fe
Percent difference,0 % -/. 3
RUN 2
looo
1112.
JI4A
A//A
3.5-^
Z9OO
^600
2.0V
II . (sDO
•&
ZSft
-*- 0. 3
STAGE 2 (if applicable)
Emission gas flowmeter reading, ml/min (qc2)
Diluent gas flowmeter reading, ml/min (qd2)
Dilution ratio
Injection time, 24h
Distance to peak, cm
Chart speed, cm/min
Retention time, min
Attenuation factor
Peak area or units
Peak area X attenuation factor
Measured concentration,3 ppmv
Calculated concentration,d ppmv
Percent difference,0 %
RUN 1
Ail A-
RUN2
AllA
RUN3
A//A
\
See Figure 5-1 for calculation.
106 x (X x qc)
= Calculated concentration for single stage
Calculated Concentration - Measured Concentration
0 Percent Difference =
d C = 106 x X
x 100%
Measured Concentration
x
,)
= Calculated cone, for two stage
^02 + 3d
Figure 2.5- Dynamic dilution data form.
-------
Section No. 3.16.2.
Date June 30, 1988
Page 12
1. Assemble the static dilution system (see Figure 4.3) and leak check the
system by plugging inlet to the dilution system, placing the discharge
line in a container of water, and pulling a vacuum of about 1 in. of Hg.
The system is leakless if no bubbles are released from the discharge line.
If the system is not leakless, find the leak and correct it.
2. Calculate as the amount of diluent gas needed to obtain the desired
dilution or calibration gas concentration. Meter the desired amount of
gas into the bag. If the purpose of the static dilution is to prepare a
lower concentration of calibration gas, the calibration gas should be
added to the bag using a gas tight syringe. Record the data on the .static
dilution system data form, Figure 2.6 or similar form. If the purpose of
the static dilution system is to collect a diluted stack sample, the
calculated amount of diluent gas is added to the bag and the stack gas is
metered into the bag from the stack. To calibrate this system, the
calculated amount of diluent gas should be metered into the bag and then a
calibration gas should be metered into the bag with the flowmeter that is
to be used in the field. Record the data on the static dilution system
data form, Figure 2.6 or similar data form.
3. Analyze the diluted calibration gas and analyze a different calibration
gas that is in the range of the diluted calibration gas. The two gases
must agree within 10% of each other for the system to be acceptable.
2.3 Thermometer
The thermometers(s) on the metering systems and the sample probes and lines
should be initially compared with a mercury-in-glass thermometer that meets ASTM E-
1 No. 63C or 63F specifications:
1. Place the thermometer to be calibrated and the mercury-in-glass thermo-
meter in a bath of boiling water. Compare the readings after the bath
stabilizes and then record on the calibration data form. Figure 2.7 or
equivalent.
2. Allow both thermometers to come to room temperature. Compare the readings
after the thermometers stabilize.
3- The thermometer is acceptable if the values agree within 3°C (5-4°F) at
both points.
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 metering system. If the values are not within 6°C (10.8°F)
of each other, replace or recalibrate the meter thermometer.
2.4 Barometer
The field barometer should be adjusted initially and before each test series
to agree within 2.54 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 correct-
ed for elevation. The tester should be aware that the National Weather Service
readings are normally corrected to sea level; 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/30 m (-0.1 in.
Hg/100 ft) elevation increase, or vice versa for elevation decrease.
-------
Section No. 3.16.2
Date June 30, 1988
Page 13
Date , .
Source flowmeter number p-
Dry gas meter number
Ambient temperature
Barometric press
Organic compound
Certified concen. (X) 2-2-/Q I
'C (°F)
mm (in.) Hg
ppmv
Calibrated by
Date source meter calibrated _
Date dry gas meter calibrated
Dry gas meter calib factor (Y)
Leak check for total system
Vacuum during leak check ^
Date of calibration curve p-
83
Initial 'dry gas meter reading, L (ft3)
Final dry gas meter reading, L (ft3)
Volume of diluent gas metered, L (ft3)
Gas metered X calibration factor (Y),{V2
Flowmeter sampling rate, L/min (cfm)
Sampling time, min
Sampling rate X sample time, L (ft3),{V1
Dilution ratio
Injection time, 24h
Distance to peak, cm
Chart speed, cm/min
Retention time, min
Attenuation factor
Peak area or units
Peak area X attenuation factor
Measured concentration,3 ppmv
Calculated concentration,1" ppmv, {Cs}
Percent difference,0 %
RUN 1
RUN 2
/3 Z. 31 (,
/3>-*>
O. 151-
2.O
z-o
7.4-12
8>.//0
2-6, (*
D
10
I J- 2-00
//'Z-66
3-3-0
- /.&
a See Figure 5-1 for calculation.
b Calculated concentration (Cs) =
X (V,)
V)
ppmv
Percent difference, %d =
Measured concent - Calculated concent
Measured concentration
X 100 =
The percent difference must be less than 10 % absolute.
Figure 2.6. Static dilution data form.
-------
Date
bv/ffi
/iv/M
Reference
thermometer
type
A S7"A^
6$F
forty
60 F
Calibr
thermc
type
£3T
CeufiUi,
f
ated
meter
use
5^
hj&kr-
bo?
no.
TAJ -12.
9-1
Ambier
refer8
rfr
-dl'F
it temper
calibrb
7l°f
lor
Measured
•ature
differ0
*2V
*-!'/=
values
Bod
refer8
1I1°F
urF
ling wat
calibr5
*a-F
3.11'F
er
differc
W
-/ •/=
Calibrator's
initials
ATM
A771/
•now
(B 03 (D
oq ct n
(D (0 ct
p-
t-i O
*-* c y
4=- 3
ID Z
O
VD O\
00 •
COM
Temperature reading of the reference thermometer in °C or °F.
Temperature reading of the thermometer being calibrated in °C or °F.
Difference between the reference thermometer and the calibrated thermometer. This difference must
be less than 3°C (5.4°F) for than initial calibration and 6°C (10.4°F) for the calibration check.
Figure 2.7- Thermometer calibration form.
-------
Section No. 3.16.2
Date June 30, 1988
Page 15
Table 2.1. ACTIVITY MATRIX FOR CALIBRATION OF EQUIPMENT
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Wet test meter
Capacity of about 2
L/min and accuracy
within 1%
Calibrate initially,
then yearly by
liquid displacement
Adjust until
specs are met, or
return to vendor
Dry gas meter,
mass flow meter,
and rotameters
Y. = Y + 0.03Y at a
point greater than
the flow rate range
to be used
Calibrate vs. wet,
dry, or bubble meter
upon receipt and
after each test
Repair and
then recalibrate,
or replace
Critical orifice
K'i = K ± 0.03K'
Calibrate vs. wet,
dry, or bubble meter
upon receipt and
after each test
Repair and
then recalibrate,
or replace
Dilution system
Measured value for
diluted and undi-
luted calibration
gas must agree
within 10%
Calibrate upon
receipt and prior to
each field test using
calibration gases
Correct problem
and rerun cali-
bration
Thermometers
Within 3°C (5.
of true value
Calibrate initially
as a separate com-
ponent with mercury-
in-glass thermometer;
check before each
test against mercury-
in-glass thermometer
Adjust or replace
Barometer
Within 2.5 mm
(0.1 in.) Hg of
mercury-in-glass
barometer or weather
station value
Calibrate initially
using mercury-in-
glass barometer;
check before and
after each test
Adjust to
agree with
certified
barometer
-------
Section No. 3-16.3
Date June 30, 1988
Page 1
3.0 PRESAMPLING OPERATIONS
This section addresses two major areas of presampling operations for Method
18: (1) preparation for, performance of, and interpretation of results for the
preliminary survey and (2) preparation for the final sampling. This section de-
scribes the preliminary survey as it applies to Method 18; for additional general
information on preliminary surveys, see Section 3-0 of this Handbook. The quality
assurance activities for the preliminary survey activities and the presampling
activities for final testing are summarized in Tables 3-1 and 3-2, respectively, at
the end of this section.
3-1 Preliminary Survey Measurements
The preliminary survey measurements are needed to properly design the final
emission test sampling and analysis protocol. The primary objective of the prelim-
inary survey is to collect a preliminary survey sample for determining which sampl-
ing procedure is most appropriate and for developing the optimum analytical pro-
cedures. Using the preliminary survey sample, estimates of the source concentra-
tion are made and the major organic components in the gas stream are identified.
Also, any compounds that may interfere with the quantitation of the target anal-
yte(s) are identified and the appropriate changes in the analytical procedures are
made. Other measurements made during the preliminary survey include sampling site
dimensions and gas stream properties. The preliminary survey is also used to
obtain a description of the process being sampled, to determine sampling logistics,
and, when possible, to collect bulk process samples and use emission screening
techniques. Use the data form shown in Figure 3-1 to record the preliminary survey
information.
3.2 Preliminary Survey Preparation
This section addresses the equipment and preparatory activities needed to
conduct the preliminary survey. Figure 3-2 can serve as an equipment checklist,
packing list, and/or equipment status form for the preliminary survey.
3.2.1 Measurement of Flue Gas Properties - The apparatus that may be required to
supplement information obtained from plant personnel during the preliminary survey
concerning the moisture level, temperature, and static pressure of the source
should be prepared for the preliminary survey as follows:
Barometer - The field barometer should be compared with a mercury-in-glass
barometer or with a National Weather Service Station (see Subsection 2.4) reading
prior to each field test.
Met Bulb/Dry Bulb Thermometers - It is recommended that for sources with stack
temperatures at or below 59° C, wet bulb/dry bulb thermometers be used to determine
stack gas moisture content. The thermometers should be compared with a mercury-in-
glass thermometer at room temperature prior to each field trip. The wet bulb/dry
bulb measurement may also be used, with the prior approval of the Administrator, to
determine stack gas moisture for sources where the stack temperature exceeds 59°C.
Method 4 Equipment - For sources with stack temperatures above 59°C, Method k
equipment is recommended to determine stack gas moisture content. Prepare the
-------
Section No. 3.16L.3
Date June 30, 1988
Page 2
I. Name of company Date_
Address
Contacts Phone
Process to be sampled
Duct or vent to be sampled_
II. Process description
Raw material
Products
Operating cycle
Check: Batch Continuous Cyclic
Timing of batch or cycle
Best time to test
III. Sampling site
A. Description
Site description
Duct shape and size_
Material
Wall thickness inches
Upstream distance inches diameter
Downstream distance inches diameter
Size of port
Size of access area
Hazards Ambient temp °F
Properties of gas stream
Temperature °C °F, Data source
Velocity , Data source
Static pressure inches H20, Data source_
Moisture content %, Data source_
Particulate content , Data source
Gaseous components
N2 % Hydrocarbons (ppm) Toxics/Acids (ppm)
02 % H2S
CO % HC1
C02 % HF
SO., % Other
Figure 3-1. Preliminary survey data sheet.
(Continued)
-------
Section No. 3.16.3
Date June 30, 1988
Page 3
Figure 3-1 (Continued)
Hydrocarbon components
ppm
ppm
ppm
ppm
ppm
ppm
C. Sampling considerations
Location to set up GC
Special hazards to be considered_
Power available at duct
Power available for GC
Plant safety requirements
Vehicle traffic rules
Plant entry requirements_
Security agreements_
Potential problems
Safety equipment (glasses, hard hats, shoes, etc.)
D. Site diagrams. (Attach additional sheets if required).
IV. On-site collection of preliminary survey samples
A. Evacuated flasks
Flasks have been cleaned, heated in furnace and purged
with nitrogen?
Flask evacuated to the capacity of pump?
Filter end of. probe placed at center of stack, probe
purged and sampled collected into flask until flask is at
stack pressure?
Stopcocks closed and taped?
Duct temperature and pressure recorded?
Purged flasks
Flasks cleaned and purged with nitrogen?
Filter end of probe placed into stack, sample purged for
2 to 5 min and then stopcocks closed?
Stopcocks taped to prevent leakage?
Duct temperature and pressure recorded?
Stability and adsorption checks conducted?
(Continued)
-------
Section No. 3-16..3
Date June 30, 1988
Page 4
Figure 3-1 (Continued)
C. Flexible bags
Bags have been blanked checked and leak checked?
Sampling system leak checked?
Filter end of probe placed into center of stack and sample
obtained at a proportional rate for appropriate amount of
time? •
Duct temperature, barometric pressure, ambient temperature,
flow rate, static pressure, and initial and final sampling
time recorded?
Analysis performed within 2 hr?
Stability and adsorption checks conducted?
D. Adsorption tubes
Proper adsorption tube(s) selected based on the likely
analytes?
Probe or adsorption tube placed into center of stack and
sample obtained at a constant rate with a calibrated
system for appropriate time based on the expected concen-
trations of analytes?
Total sample time and sample flow rate (or the number of
pump strokes), the barometric pressure, and ambient
temperature recorded?
Water vapor was less than 2% or measures were taken to
protect or increase the adsorption capacity of the
adsorption tube(s)?
E. Quality assurance performance audit samples
Quality assurance audit samples collected in the same
manner as the emission samples?
F. Bulk samples and screening techniques
Bulk emission sample(s) collected?
Bulk liquid sample(s) collected?
Detector tubes or other screening techniques used?
-------
Section No. 3.16.3
Date June 30, 1988
Page 5
Apparatus check
Moisture Determination
W Bulb/D Bulb
Checked
Barometer
Calibrated*
Method 4
Probe, heated &
leak checked
Impingers
Meter system
calibrated*
Velocity Determination
Pi tot Tube
Number
Length
Pressure Gauge
Manometer
Other
Stack Thermometer
Calibrated
Evacuated Flask
Evacuated Flasks
Number
Cleaned
Oven heated
N2 purged
Probes
Number
Cleaned
Glass wool
Suction bulb
Pump
Purged Flask
Flask
Number
Cleaned
Oven heated
N2 purged
Acceptable
Yes
No
Quantity
Required
Ready
Yes
No
Loaded and Packed
Yes
No
*Most significant items/parameters to be checked.
Figure 3-2. Preliminary survey preparations
(Continued)
-------
Section No. 3-16.3
Date June 30, 19*88
Page 6
Figure 3-2 (Continued)
Apparatus check
Purged Flask (continued)
Probe
Number
Cleaned
Glass wool
Vacuum Source
Pump
Squeeze bulb
Bag Sampling
Probe Liner
S steel
Glass
Teflon tube
Length
Meter System
Flowmeter*
Pump
Evacuated can
Charcoal tube
Sample line
Tedlar Bags
Number
Blank checked
Leak checked*
Heated Box
Number
Heat checked
Adsorption Tube
Probe
Heated
Checked
Nonheated
Glass
S steel
Filter
Sample Line
Tupe
Length
Checked*
Acceptable
Yes
No
Quantity
Required
Ready
Yes
No
Loaded and Packed
Yes
No
*Most significant items/parameters to be checked.
(Continued)
-------
Section No. 3-16.3
Date June 30, 1988
Page 7
Figure 3-2 (Continued)
Apparatus check
Adsorption Tube (continued)
Pump and Meters
Pump
Orifice
Calibrated*
Rotameter
Calibrated*
Timer
Adsorption Tubes
Type
Bulk Samples
20-ml Jars
Cleaned
Acceptable
Yes
No
Quantity
Required
Ready
Yes
No
Loaded and Packed
Yes
No
*Most significant items/parameters to be checked.
-------
Section No. 3-16.3
Date June 30, 1<588
Page 8
equipment for sampling following the procedures described in Section 3-3-3 of this
Handbook. Method 4 equipment may also be used to determine the stack gas moisture
for sources where the stack temperature is at or below 59°C.
S-Type Pitot Tube and Differential Pressure Gauge - Prepare the S-type pitot
tube and the differential pressure gauge for sampling following the procedures de-
scribed in Section 3-1-3 of this Handbook.
3.2.2 Glass Flask Sampling - The apparatus and reagents required for the collec-
tion of preliminary survey samples using glass sampling flasks are prepared as
described below- Alternative equipment found suitable may be used subject to the
approval of the Administrator.
Probe - If a heated probe is to be used for sampling, then the probe's heating
system should be checked to see that it is operating properly. The probe should be
cleaned internally by brushing first with tap water, then with deionized distilled
water, and finally with acetone. Allow the probe to air dry. The probe should be
sealed at the inlet end and checked for leaks by applying a vacuum of 380 mm (15
in.) Hg. See Subsection 1.0 for leak check procedure. The probe is considered
leak free under these conditions if no loss of vacuum is seen after one minute.
Any leaks detected should be corrected or the probe should be rejected. If the
probe has an external sheath, the integrity of the seal between the sheath and the
probe liner should be checked to ensure ambient air does not dilute the gas sample.
Teflon Tubing - Prepare sections of tubing for connections between the probe
and each flask (or bag or tube) that constitutes a preliminary survey sample col-
lection device. Clean the tubing using the procedure described above for the
probe.
Quick Connects - The quick connects should be new or cleaned according to the
manufacturer's recommendations. Leak check the quick connects as described in
Subsection 1.0.
Glass Sampling Flasks - Prepare the glass sampling flasks for collecting
preliminary survey samples as follows: Remove the stopcocks from both ends of the
flasks, and wipe the parts to remove any grease. Clean the stopcocks, barrels, and
receivers with chloroform. Clean all glass parts with a soap solution, then rinse
with tap water followed by deionized distilled water. Place the flasks in a cool
glass annealing furnace and heat the furnace to 550°C. Maintain the flasks in the
oven at this temperature for one hour. After one hour, shut off and open the
furnace to allow the flasks to cool. Return the Teflon stopcocks to the glass
flasks (if glass stopcocks are used, apply a light coating of vacuum grease to the
stopcocks before returning to the flasks.) With both stopcocks open, purge each
assembled flask with high purity nitrogen for 2 to 5 minutes. Close off the outlet
stopcock followed by the inlet stopcock to maintain a slight positive nitrogen
pressure in the flask. Secure the stopcocks with tape to prevent them from opening
accidentally.
High-Vacuum Pump - A high-vacuum pump will be required for preliminary survey
sample collection using the evacuated flask procedure. Check the operation of the
pump prior to going to the field as follows: Check for minimum pump vacuum of 75
mm (3 in.) Hg absolute by attaching a Hg-filled U-tube manometer to the pump inlet
-------
Section No. 3.16.3
Date June 30, 1988
Page 9
and turning on the pump. If the minimum vacuum cannot be reached, then repair or
replace the pump.
Rubber Suction Bulb - A rubber suction bulb will be required for preliminary
survey sample collection using the purged flask procedure. The rubber suction bulb
should be checked for proper operation prior to going to the field as follows:
Attach the bulb to a water manometer, or equivalent, and squeeze the bulb until a
vacuum of at least 250 mm (10 in.) H20 is reached. Repair or replace the squeeze
bulb if sufficient vacuum cannot be developed.
3.2.3 Flexible Bag Procedure - A flexible bag of Tedlar or aluminized Mylar can be
used to collect preliminary survey samples. If it is anticipated that Tedlar bags
will be selected as the final sampling method, then it is recommended that the
preliminary survey sample be collected using a Tedlar bag. In addition to the
apparatus described in Subsection 3-2.2 for the glass flasks (with the exception of
the flasks and the high-vacuum pump) the apparatus listed below will be required
and should be prepared as follows:
Tedlar or Aluminized Mylar Bags - Prepare new bags for preliminary survey
sampling by leak checking the bags before going to the field. The bags should also
be checked for contamination by filling with hydrocarbon-free air or nitrogen
during the leak check. The bags are checked as follows: Connect a water manome-
ter, or equivalent, using a tee connector, between the check valve quick connect on
the bag and a pressure source (or hydrocarbon-free air or nitrogen for conducting
the contamination check). Pressurize the bag to 5 to 10 cm (2 to 4 in.) H20. Loss
of pressure over a 30-second period indicates a leak. Alternatively, leave the bag
pressurized overnight: a deflated bag the following day is indicative of a leak.
Reject or repair any bags with leaks. After the hydrocarbon-free air or nitrogen
has remained in the bag for 24 hours, analyze the bag contents using a GC with a
flame ionization detector on the most sensitive setting. The bag should be re-
jected if any organic compounds are detected. If any organic compounds are
detected, the bags may be used if they are not the compounds to be sampled and
analyzed.
Etgid Leak-Proof Containers - Rigid containers can be used with the bags for
collecting preliminary survey samples. The rigid containers used to contain the
Tedlar bags during sampling should be checked for leaks prior to going to the
field. The container should be leak checked with the bag in place as follows:
Using a tee connector, connect a water manometer or equivalent, between a pressure
source and the container outlet. Pressurize the container to 5 to 10 cm (2 to 4
in.) Hg. Any loss of pressure after 30 seconds indicates a leak. Reject or repair
the rigid container if a leak is indicated.
Direct Pump Sampling System - A direct pump sampling system can be used in
place of the rigid containers for collecting preliminary survey samples. If this
method is selected, then the system should be assembled and leak checked prior to
going to the field as follows: Assemble the system (see Figure 4.5). Bypass the
Tedlar bag and its protective container by attaching the vacuum line directly after
the rotameter using the quick connects on the sample and vacuum lines. Plug the
probe inlet and turn on the vacuum pump. If the system is leak free, the
rotameter should eventually indicate no flow. Alternatively, the sample line that
is attached to the sample bag can be placed in water. If bubbling stops, then the
system is leak free.
-------
Section No. 3.16.3
Date June 30, 19B8
Page 10
Needle Valve and Rotameter - Prior to each field trip or at any sign of er-
ratic behavior, the flow control valve and the rotameter should be cleaned accor-
ding to the maintenance procedure recommended by the manufacturer.
3.2.4 Adsorption Tube Sampling - The adsorption tube sampling procedure can also
be used to collect the preliminary survey sample. If it is anticipated that ad-
sorption tubes will be selected as the final sampling method, then it is recom-
mended that the preliminary survey samples be collected using tubes containing each
potential type of adsorbent. In addition to the apparatus described in Section
3.2.1 for the glass flasks (with the exception of the flasks and a high-vacuum
pump) the apparatus listed below will be required and should, be prepared as fol-
lows :
Adsorption Tubes - Check to see that the proper type of tube has been obtained
for collecting the target organic compounds. Refer to Table B in the Methods High-
lights Section to determine the proper adsorption material. Check to see that the
supply of adsorption tubes is sufficient to conduct the emission test, including
field blanks and desorption efficiency determinations. . .. •
Personnel Sampling Pump - A personnel sampling pump is used to collect the
adsorption tube samples. The pump should be calibrated following the procedures
described in Subsection 2.1.4.
Extraction Solvents - An extraction solvent will be required to prepare the
preliminary survey adsorption tube sample(s) for analysis. Refer to Table B in the
Methods Highlights Section to determine the proper extraction solvent.
3-3 Preliminary Survey Sample Collection
The preliminary survey sample collection includes flue gas or duct moisture
and velocity determinations in addition to collection of actual flue gas or duct
samples. . .
3-3-1 Preliminary Survey Moisture Determination - If the moisture content of the
flue gas in the duct to be tested cannot be obtained from the plant personnel, it
is determined using either wet bulb/dry bulb thermometers or Method 4 sampling
apparatus, depending on the flue gas temperature. If the flue gas temperature
cannot be obtained from plant personnel, then determine the flue gas temperature
using a calibrated thermocouple, thermometer, or equivalent temperature measuring
device.
Net Bulb/Dry Bulb Procedure - For flue gas' streams at or below 59°C, the
moisture content of the flue gas should be determined using wet bulb/dry bulb
thermometers and the partial pressure equation shown below. Obtain the wet
bulb/dry bulb temperatures as follows:
1. Moisten the wet bulb thermometer wick with deionized distilled water.
2. Insert the thermometers into the flue gas stream and monitor the wet bulb
temperature.
3. When the wet bulb temperature has stabilized, record both the wet bulb and
dry bulb thermometer temperatures.
4. Calculate the flue gas moisture content using the equations below.
-------
Section No. 3.16-3
Date June 30, 1988
Page 11
10(6.69H-(3iA4/(Tw + 390.86)» Equation 3-1
w2 =
Pb
%U20 = w2 - (0.00036? x (Td-Tw) x (l+(Tw-32)/157D) * 100 Equation 3-2
where
w2 = Calculated constant, saturation % H20 at Tw ,
Tw = Wet bulb temperature, °F,
Td = Dry bulb temperature, °F,
Pb = Barometric pressure, in. Hg, and
Ps = Static pressure of duct, in. H20.
Method 4 Moisture Procedure - Follow the procedure for Method 4 described in
Section 3-3 of this Handbook.
Method 2 Velocity Procedure - Follow the procedure for Method 2 described in
Section 3-1 of this Handbook to determine the flue gas or duct velocity at the
sampling point. If the velocity varies by more than 10$ during the projected
sample run time, then proportional sampling will be required as described in Sub-
section 4.0. Because of the small size of some ducts, Methods 2A, 2C, or 2D may
have to be used. Follow the criteria and procedures described in the applicable
method.
3-3-2 Collection of Samples with Glass Sampling Flasks - Using the precleaned
glass sampling flasks, preliminary survey samples are collected using the evacuated
flask procedure or the purged flask procedure.
Evacuated Flask Procedure - Collect preliminary survey samples using the
evacuated flask procedure as follows :
1. Using a high-vacuum pump which is connected to one stopcock while the
other stopcock remains closed, evacuate each precleaned flask to the
capacity of the pump. A mercury manometer can be connected between the
pump and the flask using a tee connector to indicate when the maximum
vacuum is achieved. At this point, record the vacuum, and close off the
stopcock leading to the pump.
2. Remove the tubing leading to the pump and attach a glass tee (6-mm out-
side diameter, or equivalent) to the flask inlet with a short piece of
Teflon tubing.
3. Connect the end of the sampling probe to the glass tee using a short
length of Teflon tubing. The tubing must be of sufficient length to
reach the sampling point at the centroid of or no closer than 1 meter to
the duct wall.
4. Connect the rubber suction bulb to the third leg of the tee with a piece
of Teflon tubing or suitable flexible tubing.
5- Place a plug of glass wool in the probe inlet, enlarged to approximately
12-mm outside diameter, to serve as a filter to remove particulate mat-
ter.
6. Place the inlet (filtered) end of the probe at the sampling point and
purge the probe and sample line by repeatedly squeezing the rubber suc-
tion bulb until at least 7 air changes of the probe and sample line have
occurred.
-------
Section No. 3-16.3
Date June 30, 19B8
Page 12
7- After the probe and the sample line are completely purged, leave the
squeeze bulb in place, and open the inlet stopcock of the sampling flask
8. Leave the inlet stopcock open until the pressure in the sampling flask.
reaches the duct pressure. This should take about 15 seconds. Close the
inlet stopcock.
9. Remove the probe from the duct and disconnect the glass tee from the
flask.
10. Tape the stopcocks closed and label the flask with the plant name, date,
and sampling location, time, and sampling personnel.
11. Immediately after sampling, determine the flue gas temperature with a
calibrated thermocouple, thermometer, or equivalent temperature measuring
device, and determine the static pressure of the duct and the velocity
over a period of time equal to the predicted sample run time following
the procedures described in Section 3-1 in this Handbook.
Purged Flask Procedure - Collect preliminary survey samples using the purged
flask procedure as follows:
1. Connect the small end of the sampling probe, of sufficient length to
reach the centroid of the duct to be sampled, to the inlet stopcock of a
precleaned glass sampling flask a sufficient length of Teflon tubing.
2. Connect the rubber suction bulb to the other stopcock with a piece of
Teflon tubing or suitable flexible tubing.
3- Place a plug of glass wool in the probe inlet, enlarged to approximately
12-mm OD, to serve as a filter to remove particulate matter.
4. Place the inlet (filtered) end of the probe at the centroid of or no
closer than 1 meter to the duct wall.
5. Purge the probe, sample line, and sample, flask by repeatedly squeezing
the rubber suction bulb until approximately 7 air changes of the system
have occurred.
6. After the probe, sample line, and flask are completely purged, close off
the stopcock near the suction bulb, and then close off the stopcock con-
nected to the probe.
7. Remove the probe from the duct, and disconnect both the probe and the
suction bulb from the flask.
8. Tape the stopcocks closed and label the flask with the plant name, date,
and sampling location, time, and sampling personnel.
9. Immediately after sampling, determine the flue gas temperature with a
calibrated thermocouple, thermometer, or equivalent temperature measuring
device, and determine the static pressure of the duct and the velocity
over a period of time equal to the predicted sample run time following
the procedures described in Section 3-1 in this Handbook.
3.3.3 Flexible Bag Procedure - The flexible bags used to collect preliminary
survey samples must be leak checked and demonstrated to be free of contamination
following the procedure described in Subsection 3-2.2. The preliminary survey
sample collection using flexible bags can be conducted at a constant rate following
the procedure described in Subsection 4.3 for the evacuated container sampling
procedure, the direct pump sampling procedure, or, in explosive areas, the explo-
sion risk area sampling procedure. The flue gas or duct velocity and other
process parameters should be determined for designing the final sampling proced-
ures .
-------
Section No. 3.16.3
Date June 30, 1988
Page 13
3.3.4 Adsorption Tube Procedure - The adsorption tubes used to collect the pre-
liminary survey sample(s) should contain the adsorbent specified in Table B of the
Method Highlights Section for the target analyte(s). The sampling time or total
sample volume for the adsorption tube should be calculated based on expected con-
centration^) of the volatile organic(s) present and the recommended capacity of
the adsorption media. Refer to the appropriate reference given in Table B to
determine the recommended sample volume taking into consideration the amount of
adsorbent to be used. For compounds not referenced in Table B, use a reference for
a compound with similar chemical characteristics. If the target analytes require
different adsorption media, then it is recommended that preliminary survey samples
be collected using each type of adsorbent. In the case where the compound is
unlike any other documented compounds, use two adsorption tubes connected in ser-
ies. Once a recommended volume is established, it is recommended that two
additional samples be collected with sample volumes one half and twice the
recommended volume. The procedure for collecting preliminary survey adsorption
tube samples is as follows:
1. Open the adsorption tube, and connect the primary tube section (large
section of adsorbent) to the sampling probe using a minimum length of
Teflon tubing or other nonreactive tubing.
2. Connect the outlet (backup section) of the tube to the next tube in
series, if additional adsorption capacity is required.
3. Connect the outlet of the last tube to the inlet of the calibrated per-
sonnel sampling pump using a sufficient length of tubing.
4. Insert the probe into the stack or duct and turn on the pump. Maintain
the adsorption tubes in a vertical position during sampling to prevent
channeling. Sample the gas stream for the time required to obtain the
optimal volume determined from the referenced method.
5. Immediately after sampling is completed, disconnect the tubes from the
tubing and seal the tube ends with teflon tape and plastic caps. Label
the tubes and store each tube in a screw cap culture tube or similar
container to protect them during shipment.
6. Record the total sampling time, the sample flow rate, the barometric
pressure, and the ambient temperature.
3-4 Preliminary Survey Sample Analysis and Interpretation
With the exception of the analysis of the glass sampling flasks, the analysis
of preliminary survey samples should follow the procedures described in Subsection
5.0. The analysis of the glass sampling flasks are described below (see Subsection
3.4.2). The analysis of preliminary survey samples is used to optimize the
analytical procedures and select the most appropriate sampling technique for final
sampling. Using Table C the Method Highlights Section, choose appropriate GC
detector(s). Based on the sampling technique(s) used to collect the preliminary
sample, choose a GC column from the selections listed in Table D of the Method
Highlights Section; the technical service department of column manufacturers or
plant laboratory personnel may also be consulted for additional suggestions on
column type(s). For glass flask samples and Tedlar or Mylar bag samples, use
calibration gas cylinders or calibration standards prepared in Tedlar bags. For
adsorption tube samples, prepare the calibration standards directly in the
desorption liquid(s) or on adsorption tube material(s) used to collect the samples.
3.4.1 Calibration Standards for Preliminary Survey Samples - Prepare a minimum of
three calibration standards for each compound of interest. The standards should
-------
Section No. 3.16.3
Date June 30, 1988
Page 14
cover a linear range for the particular GC detector, with the lowest standard and
the highest standard bracketing and a midrange standard approximating the expected
sample concentration. To estimate the sample concentration, prepare a preliminary
survey sample and perform a single analysis of the sample following the procedure
in the appropriate subsections below. During this sample analysis, determine if
adequate resolution has been achieved for each peak with a peak area greater than
5# of the total chromatographic peak area (excluding the desorption solvent peak)
using one of the procedures described in Subsection 3-4.1. Adequate resolution of
sample peaks will only be necessary in the chromatographic region(s) where the
target compound(s) are expected to elute. The GC analysis conditions and/or column
can be changed to achieve adequate resolution. The use of two different columns
may be necessary to ensure accurate identification of the gases. For analysis of
more than one target compound in very complex sample matrices, more than one
analysis using different GC conditions and/or columns may be required to achieve
adequate resolution for all target compounds.
For analysis of flask samples or bag samples, (1) use cylinder gases directly
(if available) or by dilution following the procedures described in Subsection
5.1.1 and 5.1.2, respectively, or (2) prepare standards in Tedlar bags following
the procedure described in Subsection 5.1-3 for gaseous materials or the procedure
described in Subsection '5-1.4 for liquid materials. For analysis of adsorption
tube samples, prepare calibration standards following the procedure described in
Subsection 5-1.6. Data forms should be used for recording calibration standard
preparation and analysis data (see Figures 5-4, 5-6, 5-8, and 5«9) and preliminary
survey sample analysis data (see Figure 5-1)•
The gaseous calibration standards for bag samples must be injected into the GC
using a gas sampling valve equipped with a stainless steel or Teflon sample loop
following the procedures described in Subsection 5-1 appropriate for the particular
type of gaseous standard used. Liquid calibration standards for adsorption tube
analysis must be injected into a heated sample injection port following . the proced-
ure described in Subsection 5-1.6. The gaseous standards for glass flask samples
can be injected into the GC using either a gas sample valve, following the
appropriate procedure in Subsection 5-1 for the particular gaseous standard used,
or a heated injection port using a gas tight syringe following the procedure
described below; the same injection procedure used for the standards must be used
for the flask samples.
The procedure for injecting gaseous calibration standards using a gas tight
syringe is as follows:
1. Attach a GC septum to a. piece of Teflon tubing and attach the tubing to
the outlet of the calibration gas cylinder regulators or the Tedlar bags
containing the calibration gases.
2. Insert the needle of the syringe through the septum, and repeatedly purge
the syringe by repeatedly filling and emptying the syringe 7 times.
3. After purging the syringe, fill .the syringe past the mark corresponding
to the desired amount to be injected, and withdraw the syringe from the
septum. Stick the needle into a rubber stopper or a thick septum to
prevent dilution of the standard by ambient air.
4. Immediately before injecting the standard, remove the needle from the
stopper or septum, adjust the syringe to the desired volume, and inject
the standard into the heated injection port on the GC. Note the time of
injection on the strip chart and/or actuate the electronic integrator.
5- Repeat the injection of the standard until the peak areas from consecu-
tive injections agree within 5% of their average value.
-------
Section No. 3-16.3
Date June 30, 1988
Page 15
Perform initial tests using the calibration standards to determine the optimum
GC conditions to minimize analysis time while still maintaining sufficient resolu-
tion. Sufficient resolution can be determined following the procedure described by
Knoll42 or in EPA Method 625^* where the baseline to valley height between two
adjacent peaks must be less than 25% of the sum of the two peak heights (see Figure
3-3).
Analyze the calibration standards, starting with the lowest concentrations
first. Repeat each standard analysis until two consecutive injections give indi-
vidual area counts within 5% of their average. Multiply the average of the re-
sponse for the two acceptable consecutive injections of each standard by the detec-
tor attenuation to determine the calibration area value for each standard. Record
the retention time for each compound and the calibration area for each standard.
Record the detector settings, the recorder/integrator attenuation for each
standard, the chart speed, the GC temperature settings, the column parameters (type
and length) , and the carrier gas flow rate. Plot the concentration of the stan-
dards on the abscissa (x-axis) and the calibration area for each standard on the
ordinate. Perform a regression analysis, and draw the least squares line on the
plot. It is recommended, but not required for preliminary survey sample analysis,
that the validity of the calibration curve be checked using the audit procedures
described in Section 8.0. The audit sample may be analyzed at this time in lieu of
analysis during the final sample analysis with the prior approval of the
Administrator.
If positive identification of a target compound cannot be made by comparison
of the compound retention time to the retention time of one of the standards, then
use of a different type of column may be helpful. If positive identification still
cannot be achieved, then GC/mass spectrometry (GC/MS) or GC/infrared (GC/IR) tech-
niques should be used, with GC/MS recommended. In addition, any compounds, not
identified as target compounds, with peak areas greater than 5# of the total chro-
matographable peak area (excluding the solvent peak area for adsorption tubes)
should be identified by comparison to known standards or by using GC/MS.
3-4.2 Glass Flask Preliminary Sample Analysis - Since glass sampling flasks are
only used for preliminary survey samples, the analysis of the flasks is described
in this section. Glass sampling flasks require some pressurization prior to analy-
sis to withdraw the sample.
Using the ideal gas law, the amount of dilution of the sample that results
from pressurization can be estimated with enough accuracy to permit interpretation
of the preliminary survey sample results. The procedure for pressurizing a flask
is as follows:
1. Note if any condensation has collected in the flask. If it has, heat the
flask to the flue gas or duct temperature with an oven, heating tape, or
• a heat lamp. Note: The pressurization of sealed glass containers by
heating is an inherently hazardous process. The use of a protective
shield to protect personnel from flying glass in the event of an
explosion is highly recommended. In addition, the flask should be
wrapped in cloth or other cushioning media during these operations.
2. Connect one end of the flask to a mercury manometer, open the stopcock,
and determine the initial pressure of the flask (P.). Record Pi and the
initial absolute flask temperature (T. ) in °R or °K.
3. Connect the other end of the flask to a source of hydrocarbon-free nitro-
gen or air, and open the stopcock. Slowly pressurize the flask to a
maximum of 15 psig, and close the stopcock. Determine the final pressure
of the flask (Pf) and the final absolute temperature of the flask (T. ) .
-------
I
p
r
p
r
V
O 0>
CD CD
ct O
CD ct
H-
t-i O
'§*
O
- 00
Figure 3.3. Diagram showing EPA Method 625 criterion for adequate resolution of
overlapping compounds with similar mass spectra.
OQ •
O3OJ
-------
Section No. 3.16.3
Date June 30, 1988
Page 17
Note: The pressurization of sealed glass containers is an inherently
hazardous process. The use of a protective shield to protect personnel
from flying glass in the event of an explosion is highly recommended. In
addition, the flask should be wrapped in cloth or other cushioning media
during these operations.
4. Calculate the first dilution factor (D1) using the following formula:
Pf xT,
D, = Equation 3~2
Tf x PI
5. Allow the flask to equilibrate for 10 minutes. Note if any condensation
has formed. If condensation has formed in the flask and the flask did not
initially required heating, heat the flask to a temperature sufficient to
vaporize the condensate. If the condensate cannot be vaporized or if the
flask was already heated and more condensate formed during pressuriza-
tion, the sample cannot be analyzed accurately.
6. Close the stopcocks and disconnect the manometer and dilution gas.
Analyze the contents of a pressurized flask using a sample introduced into the
GC via a gas sampling valve by the following procedure:
1. Connect the sample flask to the injection valve with the valve in the
load position.
2. Open the stopcock connected to the valve, and allow the gas sample to
flow through the sample loop at 100 ml/min for 30 seconds (determined
with a rotameter connected to the outlet of the sample loop) or purge
with 5 times the sample loop volume, whichever is less. Close the stop-
cock, and allow the sample loop to return to ambient pressure.
3. Actuate the sample valve to inject the sample and record the injection
time.
4. Examine the chromatogram and determine if adequate resolution has been
achieved between individual target compound peaks and between target
compound peaks and any interfering compound peak with an area greater
than 5$ of the total area of all peaks (excluding the desorption solvent
peak) using the procedure described in Subsection 3-4-1-
5. Determine the retention time for each peak by dividing the distance of
the peak maximum from the injection point by the chart speed.
6. Repeat the analysis, and determine the peak area and retention time for
each target compound identified during the second analysis. Although not
required for the preliminary survey sample analysis, the peak areas for
each target compound from consecutive injections should agree within 5%
of the average peak area. The retention times between the two injections
should agree within 0.5 seconds or \% of the adjusted retention time
(compound retention time minus the time of elution of unretained peaks),
whichever is greater.
Analyze the contents of a pressurized flask using a sample introduced into the
GC via a gas tight syringe and a heated injection port sample by the following
procedure:
1. Attach a GC septum to one of the stopcocks on the glass flask. (Note:
Glass sampling flasks can be purchased with an integral septum port.)
2 Insert the needle of the syringe through the septum, and purge the sy-
ringe by repeatedly filling and emptying the syringe 7 times.
3. After purging the syringe, fill the syringe past the mark corresponding
to the desired amount to be injected, and withdraw the syringe from the
-------
Section No. 3.16.3
Date June 30, 1988
Page 18
septum. Stick the needle into a rubber stopper or a thick septum to
prevent dilution of the standard by ambient air.
4. Immediately before injecting the sample, remove the needle from the
stopper or septum, adjust the syringe down to the desired volume, and
inject the sample into the heated injection port on the GC. Note the
injection time on the strip chart and/or actuate the electronic integra-
tor.
5- Determine the retention time for each peak by dividing the distance of
the peak maximum from the injection point by the chart speed.
6. Repeat the analysis, and determine the retention times for each peak for
the second analysis. The retention times of successive injections should
agree within 0.5 seconds or within 1% of the mean of the adjusted
retention times, whichever is greater.
3.4.3 Analysis of Preliminary Survey Bag Samples - Follow the procedures described
in Subsection 5-3-1 for the analysis of bag samples. To assess the stability of
the gas sample in Tedlar bags, perform a second analysis after a time period equal-
ling the period between sample collection and the first analysis. If the concen-
tration of the sample collected in a Tedlar bag decreases by more than 10% between
the first and second analysis, then an accepted sampling method other than Tedlar
bags should be considered..
Perform a retention check on the bag sample by successively evacuating the bag
and refilling it with hydrocarbon-free air or nitrogen one or more times. Analyze
the bag contents for the target compound(s), allow the gas to sit in the bag
overnight, and reanalyze bag contents for the target compound(s). If any target
compound is detected in the bag at a concentration greater than 5/» of the original
concentration, then an accepted sampling method other than Tedlar bags should be
considered.
3.4.5 Analysis of Preliminary Survey Adsorption Tube Samples - Follow the proced-
ures described in Subsection 5-3-4 for the analysis of adsorption tube samples. A
minimum desorption efficiency of 50# must be obtained. If 50% desorption effici-
ency cannot be achieved using the referenced procedures from Table. B in the Method
Highlights Section, then try longer desorption times, more vigorous desorption
techniques and/or other desorption solvents. If 50% desorption efficiency still
cannot be accomplished, then an accepted sampling method other than adsorption
tubes should be considered.
3.4.6 Interpretation of Preliminary Survey Eesults - To select the most suitable
sampling and analytical method for the final field test, the results of the prelim-
inary survey must be properly interpreted. The major points to consider are (1)
the sampling location, (2) the parameters of the process being tested, (3) the flue
gas moisture and temperature and the flue or duct static pressure, (4) stability of
the gas sample in bags, (5) the desorption efficiency of the target compounds from
adsorption tubes, and (6) the resolving capability, precision, accuracy, and speed
of the GC analysis. Thus, flue gas or duct parameters and components present
determine which sampling and analytical methodologies will be the most appropriate.
Sampling Location - The hazards associated with the sampling location will .
influence the type of sampling methodology which can be used. In explosion risk
areas where use of pumps, heated probes, or a GC with a flame ionization detector
(FID) would be prohibited, the explosion risk area sampling procedure can be used
safely. Close attention must be paid to maintaining the proper sampling rate when
-------
Section No. 3-16.3
Date June 30, 1988
Page 19
using the evacuated canister as a vacuum source. It may be possible at certain
hazardous locations, to locate the collection device (bag or adsorption tube) in
the explosion risk area near the source and operate the sampling pump a safe dis-
tance away. Also, intrinsically safe personnel sampling pumps could be used in
certain hazardous areas provided the required sampling rate can be maintained.
Hazardous sampling locations may not be suitable for direct or dilution interface
sampling when using an electrically-heated probe and sample line.
Other physical factors concerning the sampling location will also influence
which sampling method is most suitable. These factors will be site-specific and
are beyond the scope of this Handbook.
Process Parameters - The particular process parameters pertaining to the
generation of the organic emissions and the effect the operation has on the
emission levels will influence which sampling technique will be most suitable. In
the case of a continuous process where emission levels are constant, each of the
Method 18 sampling techniques should be suitable with regard to the process
parameters. For processes operating 'in a batch or cyclic mode, the bag or adsorp-
tion tube integrated sampling techniques may be more suitable compared to the
interface techniques where grab samples are analyzed.
Flue Gas or Duct Conditions - The flue gas or duct moisture and temperature
will have a major influence on selecting the most suitable sampling technique.
High moisture will affect both bag samples and adsorption tube samples. For situa-
tions where moisture may be a problem, the interface techniques are recommended
provided the 5% criteria for consecutive injections, described in Subsections 5-3-2
and 5-3-^ • can be met. Condensation in bag samples may result in the target organ-
ic compounds being absorbed into the condensate, or, at extremely high concen-
trations, being the condensate itself. The heated bag sampling technique may be
suitable provided on-site analysis is conducted when it is not practical to keep
the bags heated until analysis at the base laboratory. Condensation may also be
avoided by using a diluted bag sample collected by prefilling the bag with a known
quantity of hydrocarbon-free air or nitrogen prior to sampling and accurately
metering the gas sample into the bag during sampling.
Moisture reduces the adsorptive capacity of certain types of adsorbents (pri-
marily charcoal). For sampling with adsorption tubes at sources with moisture
above 3$. a silica gel tube may be inserted in front of the primary adsorption
tube; otherwise, two or more adsorption tubes connected in series should be used.
The first tube becomes a sacrificial tube and should be positioned vertically
during sampling. A disadvantage of this approach is that the additional tubes will
also require analysis. Alternatively, a moisture knock-out jar can be used in
front of the adsorption tube. As varying amounts of the organic emissions will
also condense (the amount of each organic removed from the gas stream will largely
depend on the individual compound's volatility and solubility characteristics), the
liquid collected must be retained for analysis. Accurate quantitation of various
organics in the condensed liquid(s) may involve several steps and is generally
problematic.
The flue gas temperature may also dictate which sampling technique can be used
due to limitations of the sampling equipment.
Bag Sample Stability and Target Compound Retention - IF on-site analysis of
bag samples is not feasible and the samples are returned to the base laboratory for
analysis, then the stability of the gas sample in the bag will be a factor and
should be determined. While the stability of organics in bags has been demonstra-
-------
Section No. 3-16.3
Date June 30, 1988
Page 20
ted in numerous laboratory evaluations, an actual source sample could contain other
unknown components which may affect sample stability. If the preliminary survey
sample analysis indicates that the gas sample is not stable, then one of the alter-
native sampling procedures should be used. The check should be conducted at an
elevated temperature if the bag is to be heated during sampling.
The retention of the target compounds by the Tedlar bag should also be check-
ed. This check will indicate any sample loss not determined by the stability
check. If the retention of a target compound by the Tedlar bag is unacceptably
high, then the bag sampling technique is not suitable for that target compound and
one of the alternative sampling procedures should be used. Heating of the bag
during sampling and analysis may reduce the retention.
Adsorption Tube Desorption Efficiency - The desorption efficiency determined
for the adsorption tubes must be >50#. If >50# desorption efficiency cannot be
achieved with the referenced procedure, then more vigorous desorption techniques
and/or solvents should be evaluated. The desorption efficiency, as determined by
the procedures described in Subsection 5-1.6, will not indicate if the gas sample
matrix will affect the desorption of the target compounds. If acceptable
desorption efficiency cannot be achieved, then one of the alternative sampling
procedures should be used. Also, the adsorption efficiency must be greater than
90%. The breakthrough volume must not be exceeded.
Calibration Standards and GC Analysis - The availability of calibration stan-
dards may dictate which sampling technique can be used. The GC analysis may also
dictate which sampling technique will be the most suitable. For accurate analysis,
adequate resolution must be achieved between target compounds and between any
interfering compounds and target compounds. During preliminary survey sample
analysis, acceptable resolution may not be achievable on a gas sample but may be
accomplished with the adsorption tube sample, or vice versa. Thus, the sampling
technique which gives acceptable resolution during sample analysis must be select-
ed. In some situations where analysis of more than one target compound is requir-
ed, two or more analyses of the same sample under different GC conditions and/or
with different columns may be necessary to achieve adequate resolution.
Acceptable accuracy, as demonstrated by audit sample analysis, must also be
achieved for sample analysis by either gas or liquid injection. Again the sampling
technique that gives acceptable accuracy during sample analysis must be selected.
The sampling technique that gives acceptable precision, as demonstrated by consecu-
tive replicate injections, must be selected. Minimizing the analysis time is par-
ticularly important for the interface techniques. As discussed above, the preci-
sion limits may be hard to achieve with the interface techniques with a long analy-
sis time under variable or cyclic emission conditions.
3-5 Apparatus Check and Calibration
Figure 3-^ summarizes the pretest apparatus checks and calibration and can be
used as a pretest operations checklist. Figure 3-5 can serve as an equipment
packing list and status report form.
3-5•! Probe - If a heated probe is required for the selected sampling procedure,
then the probe's heating system should be checked to see that it is operating prop-
erly. The probe should be cleaned internally by brushing first with tap water,
then with deionized distilled water, and finally with acetone. Allow the probe to
air dry, then the probe should be heated and purged with air or nitrogen. The
-------
Section No. 3.16.3
Date June 30, 1988
Page 21
Date Calibrated by
Check Sampling Technique To Be Used
Direct Bag , Dilution Bag , Direct Interface , Dilution Interface ,
or Adsorption Tube .
Sampling Checks (Check only applicable methods)
Velocity and Water Vapor Content
Pitot tube dimension specifications checked? yes no (specification of Method
2, Handbook Section 3.1)
Differential pressure gauge pretest calibration acceptable? yes no N/A
(specifications of Method 2, Handbook Section 3-2)
Stack temperature sensor calibrated against a reference thermometer?* yes no
(within 5°F of reference thermometer)
Barometer pretest field barometer reading correct? yes no (within 2.5 mm
(0.1 in.) Hg of the mercury-in-glass barometer)
Wet bulb/dry bulb thermometers accuracy acceptable? yes no (within 1°F of
true value, manufacturer's specifications)
Method 4 sampling equipment acceptable?* yes no (Handbook Section 3.3, PRE
TEST SAMPLING CHECKS, Method 4, Figure 2.5)
Direct Bag
Pretest calibration of flowmeter acceptable? yes no (within 10 percent of
0.5 liter/min for single check)
For heated box system, pretest calibration of the temperature sensor in the box is
acceptable? yes no N/A (within 5 percent of reference value at
temperature of expected use)
Dilution Bag
Pretest calibration of flowmeter acceptable? yes no (within 3 percent of wet
test meter)
Pretest calibration factor of dry gas meter acceptable? yes no (within 2
percent of wet test meter)
*Most significant items/parameters to be checked.
(Continued)
Figure 3.4. Pretest sampling checks.
-------
Section No. 3.16.3
Date June 30, 1988
Page 22
Figure 3.4 (Continued)
Direct Interface and Dilution Interface
Pretest calibration of stack temperature sensor acceptable?* yes no (within
2°F of reference value)
Pretest calibration of probe and heated sample line temperature sensor acceptable?*
yes no (within 2°F of reference value)
For dilution interface only, pretest calibration of dilution system acceptable?*
yes no (within 10 percent of expected dilution factor)
Pretest calibration of gas chromatograph acceptable?* yes no (specifications
shown in POSTSAMPLING OPERATIONS CHECKLIST, Figure 5.10)
Adsorption Tubes
Pretest calibration of limiting orifice acceptable?* yes no (compared to
bubble meter) . ,,.-.,.
*Most significant items/parameters to be checked.
-------
Section No. 3-16.3
Date June 30, 1988
Page 23
Apparatus check
Moisture Determination
N Bulb/D Bulb
Checked
Barometer
Calibrated*
Method 4
Probe, heated &
leak checked
Impingers
Meter system
calibrated*
Velocity Determination
Pi tot Tube
Number
Length
Pressure Gauge
Manometer
Other
Stack Thermometer
Calibrated
Bag Sampling
Probe Liner
S steel
Glass
Teflon tube
Length
Meter System
Flowmeter*
Pump
Evacuated can
Charcoal tube
Sample line
Tedlar Bags
Number
Blank checked
Heated Box
Number
Heat checked
Acceptable
Yes
No
Quantity
Required
Ready
Yes
No
Loaded and Packed
Yes
No
*Most significant items/parameters to be checked.
Figure 3-5' Pretest preparations.
-------
Section No. 3.16..3
Date June 30, 1988
Page 24
Figure 3-5 (Continued)
Apparatus check
Bag Sampling (continued) •
Dilution
Inert gas
Meter
Gas Chromatograph
On- site
(check below)
N/A
Direct or Dilution
Interface
Probe Liner
Glass
S steel
Teflon
Heated Line
Length
Heat checked
Temperature Sensors
Stack
Probe
Calibrated*
Sample Pump
Dilution System
Dilution pumps
Flowmeters
Dilution gas
Heated box
Dilution factor
checked*
Gas Chromatograph
(shown below)
Adsorption Tube
Probe
Heated
Checked
Nonheated
Glass
S steel
Filter
Acceptable .
Yes
i
\
:
\
NO ;
f
>
i
t
I
Quantity
Required
Ready
Yes
No
Loaded and Packed
Yes
No
*Most .significant items/parameters to be checked.
-------
Section No. 3.16.3
Date June 30, 1988
Page 25
Figure 3-5 (Continued)
Apparatus Check
Adsorption Tube (continued)
Sample Line
Type
Length
Checked*
Pump and Meters
Pump
Orifice
Calibrated*
Rotameter
Calibrated*
Timer
Adsorption Tubes
Time
Gas Chromatograph
Cylinder Standards
Ana lute
PPM
PPM
Regulators
Bags
Size
Dilution system
Calibrated*
Diluent gas
Bag Standards
Analyte
Syringes
Imptnger/hot
plate assembly
Gas meter
N2 gas
Regulator
Bags
Size
Other Gases
Fuel
Carrier
Zero
Co lumns
Type
Acceptable
Yes
No
Quantity
Required
Ready
Yes
No
Loaded and Packed
Yes
No
*Most significant items/parameters to be checked.
-------
Figure 3-5 (Continued)
Section No. 3.16-3
Date June 30, 1988
Page 26
Apparatus Check
Gas Chromatograph
Type
Temp/con oven
Bulk Samples
Bottles
Type
Size
Acceptable
Yes
No
Quantity
Required
Ready
Yes
No
Loaded and Packed
Yes
No
*Most significant items/parameters to be checked.
-------
Section No. 3-16.3
Date June 30, 1988
Page 27
probe should be sealed at the inlet end and checked for leaks by applying a vacuum
of 10 in. H20. See Subsection 1.0 for the probe leak check procedure. The probe
is considered leakfree under these conditions if no loss of vacuum is seen after
one minute. • Any leaks should be corrected or the probe should be rejected. If the
probe has an external sheath, the integrity of the seal between the sheath and the
probe liner should be checked to ensure ambient air does not dilute the gas sample.
3.5.2 Teflon Tubing - Prepare enough sections of tubing for connecting the probe
to bag or tube samples .
3.5.3 Quick Connects or Equivalent - The quick connects, or their equivalents,
should be new or cleaned according to the manufacturer's recommendations. Leak
check the quick connects as described in Subsection 1.0.
3.5.U 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
test.
3-5-5 Wet Bulb/Dry Bulb Thermometers - For sources with stack temperatures below
59° C where wet bulb/dry bulb thermometers will be used to determine stack gas
moisture content, the thermometers should be compared with the mercury-in-glass
thermometer at room temperature prior to each field trip.
3-5-6 Method 4 Equipment - Where Method 4 will be used to determine stack gas
moisture content, prepare the equipment for sampling following the procedures
described in Section 3-3-3 of this Handbook.
3-5-7 S-type Pitot Tube and Differential Pressure Gauge - Prepare the S-type pitot
tube and the differential pressure gauge for sampling following the procedures de-
scribed in Section 3-1-3 of this Handbook.
3-5-8 Sampling Pump - Check the sampling pump for delivery rate and leaks before
going to the field as follows: Attach a 0 to 5 liter/minute rotameter to the
outlet of the pump and turn on the pump. Check the flow rate indicated by the
rotameter. Reject or repair the pump if the flow rate is not at least 1 liter/mi-
nute. If the flow is adequate, then conduct a leak check by plugging the inlet of
the pump. If the pump is leak free then the rotameter should eventually indicate
no flow. Repair or replace the pump if a leak is indicated.
3-5-9 Tedlar Bags - Prepare new Tedlar bags for sampling by leak checking the bags
before going to the field. The bags should also be checked for contamination by
filling with hydrocarbon- free air or nitrogen during the leak check. The bags are
checked as follows: Connect a water manometer, or equivalent, using a tee con-
nector between the check valve quick connect on the bag and a pressure source (or
hydrocarbon- free air or nitrogen for conducting the contamination check) . Pres-
surize the bag to 5 to 10 cm (2 to 4 in.) H20 and disconnect the quick connect.
Loss of pressure over a 10 minute period indicates a leak. Alternatively, leave
the bag pressurized overnight; a deflated bag the following day is indicative of a
leak. Reject or repair any bags with leaks. After the hydrocarbon- free air or
nitrogen has remained in the bag for 24 hours, analyze the bag contents using a GC
with a flame ionization detector on the most sensitive setting. The bag should be
rejected if any organic compounds are detected that may interfere with the analysis
of any of the target compound(s).
-------
Section No. 3.16.3
Date June 30, 1988
Page 28
3-5-10 Etgld Leak-Proof Containers - The rigid containers used to contain the
Tedlar bags during sampling should be checked for leaks prior to going to the
field. The container should be leak checked with the bag in place as follows:
Connect a water manometer, or equivalent, using a tee connector between a pressure
source and the container outlet. Pressurize the container to 5 to 10 cm (2 to 4
in.) Hg. Any loss of pressure after 10 minutes indicates a leak. Reject or repair
the rigid container if a leak is indicated.
3.5-H Direct Pump Sampling System - If the direct pump sampling system is select-
ed, then the system should be assembled and leak checked prior to going to the
field as follows: Assemble the system (see Figure 4.5). Attach a vacuum line and
a rotameter to the inlet quick connect. Plug the probe inlet and turn on the
vacuum pump. If the system is leakfree up to the pump, the rotameter should even-
tually indicate no flow. An alternate procedure to leak check the system up to the
male inlet check valve quick connect is as follows: Connect a water manometer, or
equivalent, using a tee connector between a pressure source and the inlet end of
the probe. Pressurize the system to 5 to 10 cm (2 to 4 in.) Hg. Any loss of
pressure after 30 seconds indicates a leak. Reject or repair the sampling system
if a leak is indicated. Check to see if the pump is contaminating the sampling
system by filling a second contamination-free Tedlar bag with hydrocarbon-free air
or nitrogen, and with the system assembled pull the hydrocarbon-free air or nitr-
ogen from the second Tedlar bag into the first Tedlar bag using the pump. Analyze
the first bag contents using a GC with a flame ionization detector on the most
sensitive setting. The pump should be rejected or repaired, cleaned, and checked
again if any organic compounds are detected that may interfere with the analysis of
any of the target compound(s).
3-5-12 Needle Valve and Rotameter - Prior to each field trip or at sign of erratic
behavior, the flow control valve and the rotameter should be cleaned according to
the maintenance procedure recommended by the manufacturer.
3.5-13 Teflon Probe - For bag sampling in an explosion risk area, prepare a new
Teflon probe or clean a used Teflon probe following the procedure described in
Subsection 3-5-1- Leak check the Teflon probe as follows: Attach a mercury manome-
ter, with a tee connector, and a vacuum pump to the outlet of the probe. Plug the
inlet end of the probe and apply a vacuum of 10 in. H20. The probe is considered
leak free under these conditions if no loss of vacuum is seen after one minute.
Any leaks should be corrected or the probe should be rejected.
3-5-14 Explosion Risk Area Sampling System - The explosion risk area sampling
system should be leak checked as follows: Evacuate the steel drum. Assemble the
system (see Figure 4.6), with the pinch clamp open, the sample bag leak checked and
evacuated, and directional needle valve closed. Attach a mercury manometer to the
inlet of the Teflon probe. Open the needle valve. The rotameter should eventually
indicate no flow. Once there is no flow, note the manometer reading. The system
is considered leak free under these conditions if no loss of vacuum is seen after
one minute. Any leaks should be corrected or the system should be rejected. It is
recommended that an explosion-proof pump be used in the explosion risk area or a
regular pump be used outside the risk area. Follow the procedures described for
these pumps.
3-5-15 Heated Bag Sample Container and Sample Lines - If other modified bag sampl-
ing techniques are selected due to condensation observed during sampling, heated
-------
Section No. 3-16.3
Date June 30, 1988
Page 29
bag sample containers and sample lines will be required. The heating systems of
this equipment should be checked prior to going to the field to see that they are
operating properly. The sample lines should be cleaned following the procedure
described for the sampling probe in Subsection 3-5-1- The heated sampling system
should be assembled and leak checked prior to going to the field as follows:
Assemble the system (see Figure 4.5). Attach a vacuum pump and a rotameter to the
inlet quick connect. Plug the probe inlet and turn on the vacuum pump. If the
system is leak free, the rotameter should eventually indicate no flow. An alter-
nate procedure to leak check the system up to the female outlet check valve quick
connect on the bag container is as follows: Connect a water manometer, or equiva-
lent, using a tee connector between a pressure source and the inlet end of the
probe. Pressurize the system to 5 to 10 cm (2 to 4 in.) Hg. Any loss of pressure
after 30 seconds indicates a leak. Reject or repair the sampling system if a leak
is indicated.
3.5-16 Direct Interface Sampling System - The heating system of the sampling
probe should be checked prior to going to the field if heating is required to
maintain the gas sample above the duct temperature and/or to prevent condensation.
The probe should also be cleaned and leak checked following the procedures describ-
ed in Subsection 3-5-1- If the probe has an external sheath, the integrity of the
seal between the sheath and the probe liner should be checked to ensure ambient air
does not dilute the gas sample. The sample line should be cleaned following the
procedure described for the sampling probe in Subsection 3-5-1- The heating system
of the sample line should be checked before going to the field to see that it is
operating properly. The direct interface sampling system should be assembled and
leak checked prior to going to the field as follows: Assemble the system (see
Figure 4.5). Switch the gas sampling valve to the inject position, and plug the
outlet from the sample valve. Connect a water manometer, or equivalent, using a
tee connector between a pressure source and the inlet end of the probe. Pressurize
the system to 5 to 10 cm (2 to 4 in.) Hg. Any loss of pressure after 30 seconds
indicates a leak. Reject or repair the sampling system if a leak is indicated.
3-5-17 Dilution Interface Sampling System - The equipment required for dilution
interface sampling is the same as required for direct interface sampling, with the
addition of a heated dilution system and a larger heated sample pump. The heating
systems should be checked to see that they are operating properly. Prior to each
field trip or at sign of erratic behavior, all flowmeters should be cleaned accord-
ing to the maintenance procedure recommended by the manufacturer. The flowmeters
should also be calibrated following the procedures described in Subsection 2.1.3-
The dilution interface sampling system should also be checked for leaks as follows:
Assemble the system (see Figure 4.6). Connect a water manometer, or equivalent,
using a tee connector between a pressure source and the inlet end of the probe.
Plug the three outlet vents to the charcoal adsorbers and the outlet of the two
flowmeters. Pressurize the system to 5 to 10 cm (2 to 4 in.) Hg. Any loss of
pressure after 30 seconds indicates a leak. Reject or repair the system if a leak
is indicated. It is advisable to verify the operation of the dilution system prior
to going to the field following the procedures described in Subsections 4.3-7 and
5-3-3-
3.5.18 Gas Chromatography System - Refer to Table C in the Method Highlights
Section to ensure that the proper detector has been selected for the target organic
compounds. Prior to taking the gas chromatography system to the field, check that
all systems are operating properly. Consult the operator's manual for procedures
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Section No. 3-16.3
Date June 30, 19*88
Page 30
to verify that the equipment is operating properly. Check to see that all cylinder
gas regulators, connections, and tubing are functioning properly and are leak free.
This is particularly important when using hydrogen and oxygen. Consult with the
regulator manufacturer for procedures on checking pressure regulators. Connections
and tubing can be checked for leaks by pressurizing with the gas and wetting with a
soap solution or other commercially available solutions. Any bubbles forming on
the connections indicate a leak. Tighten or replace any leaking connections. An
alternative leak check procedure for carrier gas is as follows: Plug the outlet of
the analytical column. Pressurize the tubing and connections. Turn off the cylin-
der valve and note pressure on the regulator gauge and, if equipped, the GC pres-
sure gauge. Any loss of pressure indicates a leak. Locate the leak using a soap
solution or work backwards through the carrier gas flow path disconnecting each
component and plugging the carrier gas flow until the leak is located. a similar
check should be made of the gas sampling valve, sample loop, and connections.
It is advisable to take to the field an adequate supply of spare parts, sep-
tums, different size sample loops, extra analytical columns, and other related
equipment that may fail or deteriorate during the emission test. The generation of
response factors for each target organic compound, relative to a single organic
compound, should be confirmed in the laboratory prior to going to the field. The
confirmation procedure involving preparation and analysis of calibration standards
containing multiple organic compounds is described in Section 5-1.6.
3.6 Reagents and Equipment
The following reagents and equipment may be required to conduct the emission
test depending on the sampling method selected. These materials are generally ac-
quired from commercial vendors. Certification of purity and/or analysis should be
obtained for adsorption tubes, calibration and zero gases, and liquid organic com-
pounds .
3.6.1 Charcoal Adsorber - Check to see that the supply of charcoal adsorbent is
sufficient to last for the entire field test period.
3.6.2 Adsorption Tubes - If adsorption tube sampling is to be conducted, check to
see that the proper type of tube has been obtained for collecting the target or-
ganic compounds. Refer to Table B in the Methods Highlights Section to determine
the proper adsorption material. Check to see that the supply of adsorption tubes
is sufficient to conduct the emission test, including field blanks and for desorp-
tion efficiency determinations.
3.6.4 GC Carrier Gas - Check the GC operator's manual and the GC column manufac-
turer to see that the GC carrier gas type and grade are compatible with the GC and
the column. Check to see that the supply of carrier gas is sufficient to last the
entire field test period.
3.6.4 Auxiliary GC Gases - Check to see if the proper type and grade of auxiliary
gases required by the GC detector have been obtained. Consult with the GC detector
manufacturer to determine the proper type and grade of auxiliary gases required.
Check to see that the supply of auxiliary gases is sufficient to last the entire
field test period.
3.6.5 Calibration Gases - Check to see if the correct calibration gases in the re-
quired range have been obtained. If available, commercial cylinder gases may be
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Section No. 3-16.3
Date June 30, 1988
Page 31
used if their concentrations have been certified by direct analysis; cylinder gases
with tighter tolerances on their concentrations are preferred. Check to see that
the supply of calibration gases is sufficient to last the entire field test period.
3.6.6 Calibration Gas Dilution System - Prior to each field trip or at the sign of
erratic behavior, any flow control valves or rotameters used in the dilution system
should be cleaned according to the maintenance procedure recommended by the manu-
facturer. The rotameters or other metering devices used with a single-stage or
two-stage dilution system should be calibrated prior to going to the field follow-
ing the procedures described in Subsection 2.2. It is advisable to check the
dilution ratio of the dilution system prior to going to the field following the
procedures described in Subsections 4.3.7 and 5*3-3-
3.6.7 Zero Gas - Check to see that the zero gas meets the requirements for being
hydrocarbon-free (less than 0.1 ppmv of organic material as propane or carbon equi-
valent) . Check to see that the supply of zero gas is sufficient to last the entire
field test period.
3-6.8 Audit Gases - Check to see that the required audit gases in the proper range
have been acquired. Consult Table A in the Method Highlights Section for audit
gases available from the EPA for the target organic compounds. The availability
and ranges of audit gases can be determined by contacting:
Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77B)
Research Triangle Park, North Carolina 27711
Attention: Audit Cylinder Gas Coordinator
For audit gases obtained from a commercial gas manufacturer, check that the manu-
facturer has (1) certified the gas in a manner similar to the procedure described
in 40 CFR Part 61, Appendix B, Method 106, Section 5.2.3.1 and (2) obtained an
independent analysis of the audit cylinder that verifies that the audit gas concen-
tration is within 5% of the manufacturer's stated concentration.
3.6.9 Organic Compounds for Preparing Gaseous Standards - If gaseous standards are
to be prepared in the field, check to see if the organic compounds to be used are
at least 99-9# pure or, if less than 99-9#. of known purity necessary to calculate
the gaseous standard concentration. Record the manufacturer's lot number for each
standard compound.
3-6.10 Equipment for Preparing Gaseous Standards by Liquid or Gas Injection-
Confirm that the Tedlar bags to contain the gaseous standards have been leak check-
ed following the procedures described in Subsection 3-5-9- Check to see that the
syringes selected are gas-tight, cover the range needed (1.0- to 10-microliters for
liquids and 0.5 ml for gases), and are accurate to within 1#. Confirm that the dry
gas meter and temperature gauge have been calibrated following the procedures
described in Subsection 2.0. Clean the midget impinger assembly with detergent and
tap water, and then rinse with deionized distilled water. Check the system for
leaks as follows: Assemble the appropriate system for preparing standards (see
Figure 5-5 for gaseous materials or Figure 5.6 for liquid materials). Fit the
injection port with a new septum. Fill the Tedlar bag and pressurize the system
to 5 to 10 cm (2 to 4 in.) Hg. Any loss of pressure after 10 minutes indicates a
-------
Section No. 3.1^-3
Date June 30, 1988
Page 32
leak. • Reject or repair the system if a leak is indicated.
3-7 Packing Equipment for Shipment
The packing techniques described in this section are not requirements, but are
suggestions based on previous field experience. The type of packaging for equip-
ment going to the field depends on the mode of transportation. Typically, packing
equipment for transport by a common carrier will require the greatest degree of
effort to ensure the equipment arrives on-site in its original condition. When
possible, delicate equipment should be packed in the original shipping containers.
For convenience, label all containers with the contents for easy identification in
the field. The most common mode of packing will be in a van or trailer, where the
equipment will remain during transport. More sophisticated test firms have trai-
lers or trucks dedicated to the type of sampling being conducted. These units are
often designed to allow the test equipment and instruments to remain set up during
transport. This approach minimizes the time and effort required to set up before
and breakdown after a test. A dedicated test vehicle provides a working environ-
ment that greatly enhances the quality of work that can be performed.
3.7-1 Probe - Pack the probe in a rigid case protected by polyurethane foam, poly-
ethylene bubble-pack, or other suitable packing material. Seal the inlet and
outlet of the probe with tape or other suitable material. Protect any protruding
glass ends from breakage by insertion into rigid plastic pipe lined with foam or
other packing material.
3.7.2 Teflon Tubing, Sample Lines, and Vacuum Lines - All tubing, sample lines,
and vacuum lines should be coiled and secured with tape. Coils should be large
enough not to crimp tubing or excessively strain the heat sheath. Seal all open-
ings with tape.
3-7-3 Quick Connects, Flow Control Valves and other Connectors - All connectors,
valves, and other small parts should be packed in small parts cabinets, trays with
divided compartments, or storage chests with labeled drawers to provide quick and
easy access to the desired part.
3-7-4 Barometer - The field barometer should be packed in a rigid container,
securely mounted in rigid foam. The barometer case should be packed in a larger
box designated to contain delicate or fragile equipment.
3.7.5 Thermometers and Thermocouple Readouts - Thermometers and thermocouple read-
outs should be packed in the original carrying case, if possible. Glass thermome-
ters should be packed in a rigid tube to prevent breakage. These items, in their
smaller packing, should also be packed in a larger box designated to contain deli-
cate or fragile equipment.
3.7.6 Method 4 Equipment - Method 4 equipment should be packed following the pro-
cedures recommended in Section 3-3-3 of this Handbook.
3.7.7 S-type Pitot Tube and Differential Pressure Gauge - The S-type pitot tube,
when not mounted on the sampling probe, should packed in a rigid case and wrapped
with polyurethane foam, polyethylene bubble-pack, or other suitable type of packing
material. Seal all openings with tape or other suitable material. The differen-
tial pressure gauge, if not part of a meter box, should be mounted in a rigid
-------
Section No. 3.16.3
Date June 30, 1988
Page 33
housing. The gauge should be wrapped with polyurethane foam, polyethylene bubble-
pack, or other suitable material, and packed in a larger box designated for deli-
cate and fragile equipment.
3.7.8 Glassware - All glassware should be packed in the original shipping contain-
ers, if available, and stored together in a larger rigid container marked "Fragile!
Glass." Otherwise, wrap the glassware with polyurethane foam, polyethylene bubble-
pack, or other suitable material, and pack in a rigid foam-lined container marked
"Fragile! Glass."
3.7.9 Tedlar Bags - Preferably, transport the Tedlar bags to the field in individ-
ual rigid containers used for sampling. If this is not possible, pack the bags,
individually, in corrugated cardboard boxes with the connectors secured such that
they do not contact and puncture the bags.
3.7-10 Sampling Pumps - Sampling pumps, if not mounted in a rigid housing suitable
for transport, should be packed in a rigid foam-lined container.
3.7.11 Dilution Interface System - The dilution interface system should be built
into in a rigid container suitable for shipment.
3.7.12 Gas Chromatograph System - The gas chromatograph and ancillary systems
should be packed in the original shipping container for transport. Although it is
not recommended, the GC can be transported with out additional packaging in a van
or trailer provided the GC is secured properly against movement and other equipment
is not packed in a manner where it could fall on the instrument. For transport in
dedicated test vehicles, the instruments should be mounted in shock absorbing
devices. All gas lines and analytical columns should be capped to prevent con-
tamination and/or oxidation during shipment.
3-7^13 Gas Cylinders - All gas cylinders should be transported with their protec-
tive cylinder heads securely attached. The cylinders should be secured horizontal-
ly so that they do not roll together or vertically in a specially designed cylinder
rack. Be aware of and adhere to all Federal, State, and local regulations involv-
ing the transport of compressed and flammable gases, particularly through tunnels.
3.7.1^ Liquid Organic Compounds - Liquid organic compounds should be shipped with
the container top sealed with electricians tape and stored in a sealed plastic bag.
Packed each container in its original shipping box, if available. Otherwise, wrap
each container individually with polyurethane foam, polyethylene bubble-pack, or
other suitable material and place in a box designated for chemicals.
3.7.15 Dry Gas Meters - Dry gas meters not housed in a rigid meter box suitable
for transport should be wrapped with polyurethane foam, polyethylene bubble-pack,
or other suitable material, and packed in a larger box designated for delicate or
fragile equipment.
-------
Section No.- 3.16,3
Date June 30, 1988
Page 34
Table 3.1. ACTIVITY MATRIX FOR PRELIMINARY SURVEY SAMPLING AND ANALYSIS
Characteristic
Apparatus Check
Barometer
Wet bulb/dry bulb
thermometers
Method 4 equipment
S-type pitbt tube
and differential
pressure
Probe
Teflon tubing
Quick connects
Glass flasks
High- vacuum pump
Tedlar or alumi-
nized Mylar bags
Acceptance limits
Within 2.5 mm
(0.1 in.) Hg of
mercury-in-glass
barometer
Within 1°C (2°F) of
a mercury-in-glass
thermometer
See Section 3.3-3
of this Handbook
See Section 3.1.3
of this Handbook
1. Clean; glass
liner, stainless
steel, or Teflon
inert to organics
2. Heating properly
if equipped with
heating system •
3. Leak free
New and unused
New or clean
Clean
Vacuum of 75 mm
(3 in . ) Hg absolute
Leak free; no
loss of pressure
after 30 seconds
Frequency and method
of measurement
Before each field trip
As above
Same as Section 3-3-3
Same as Section 3- 1-3
Before each field trip
following the proced-
ures described in Sub-
section 3 • 5 • 1
As above
As above
As above
As above
As above
As above
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20
Action if
requirements
are not met
Repair or replace
Replace
Same as Section
3-3.3
Same as Section
3.1-3
Repeat cleaning
Repair or replace
As above
Obtain new tubing
Clean according
to manufacturer ' s
recommendation
Repeat cleaning
of flasks
Repair or replace
As above
(Continued)
-------
Table 3.1 (Continued)
Section No. 3-16.3
Date June 30, 1988
Page 35
Characteristic
Apparatus Check
Rigid containers
Direct pump
sampling system
Needle valve and
rotameter
Adsorption Tube
Procedure
Adsorption tubes
Personnel sampling
pump
Extraction solvent
Teflon tubing
On-site Measure-
ments and Sampling
Wet bulb/dry bulb
measurement
Acceptance limits
Leak free; no
loss of pressure
after 30 seconds
Leak free; no
loss of pressure
after 30 seconds
Clean
Proper type of
adsorption material
Calibrated
Proper type of
extraction solvent
New and unused
1 . Wet bulb wick .
moistened
2. Wet bulb temper-
ature stabilized.
3. Record wet bulb
and dry bulb
temperature
Frequency and method
> of measurement
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20
As above
Prior to each trip or
at the sign of erratic
behavior
Before each field trip
As above
Prior to extraction
of tubes for analysis
Before each field trip
Prior to each
measurement
During measurement .
.Immediately after wet
bulb temperature
stabilizes
Action if
requirements
are not met
Repair or replace
As above
Clean following
manufacturer ' s
recommendations
Replace with
proper type
Repair or replace
Replace with
proper type
Obtain new tubing
Moisten
Allow to
stabilize
Repeat
measurement
(Continued)
-------
Table 3.1 (Continued)
Section No. 3.1^-3
Date June 30, 1988
Page 36
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
On-site Measure-
ments and Sampling
Evacuated glass
flask sampling
1. Flask evacuated
to pump capacity
2. Assemble; no
leakage
3- System purged up
to flask inlet
4. Stopcocks closed
and taped; flask
labeled
5- Flue gas tempera-
ture and static
pressure determined
Prior to sample
collection
Before sample col-
lection, visually and
physically inspect
all connections
Immediately prior to
sampling
Immediately after
sampling
Immediately after
sampling
Evacuate flask
Check for leaks;
repair system;
repeat test
Purge system up
to flask inlet
Close and tape
stopcock; label
flask
Determine flue
gas temperature
and static
pressure
Purged glass
flask sampling
1. Assemble; no
leakage
3. Entire system
purged for 2 minutes
3. Stopcocks closed
and taped; flask
labeled
4. Flue gas tempera-
ture and static
pressure determined
Before sample col-
lection, visually and
physically inspect
all connections
Immediately prior to
sampling
Immediately after
sampling
Immediately after
sampling
Check for leaks;
repair system;
repeat test
Purge entire
system for 2
minutes
Close and tape
stopcock; label
flask
Determine flue
gas temperature
and static
pressure
(Continued)
-------
Section No. 3-16.3
Date June 30, 1988
Page 37
Table 3.1 (Continued)
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
On-site Measure-
ments and Sampling
Flexible bag sam-
pling procedure
1. Assemble using
Figure 4.4; no
leakage
2. Flow rate set to
0.5 1pm; purge sy-
stem up to bag inlet
3. Flue gas tempera-
ture and static
pressure determined
4. Bag labeled and
protected from
sunlight
Before sample col-
lection, visually and
physically inspect
all connections
Immediately prior to
sampling
Immediately after
sampling
Immediately after
sampling
Check for leaks;
repair system;
repeat test
Set flow rate
Purge system up
to flask inlet
Determine flue gas
temperature and
static pressure
Label bag and
protect from
sunlight
Adsorption tube
sampling procedure
1. Assemble using
Figure 4.9; no
leakage
2. Tubes capped,
labeled and stored
3. Flue gas tempera-
ture and static
pressure determined
Before sample col-
lection, visually and
physically inspect
all connections
Immediately after to
sampling
Immediately after
sampling
Check for leaks;
repair system;
repeat test
Cap, label and
store tubes
Determine flue
gas temperature
and static press,
Preliminary Survey
Sample Analysis
Calibration
standards
(Continued)
1. Minimum of three
standards prepared
for each analyte
2. Sufficient peak
resolution achieved
(valley height <25%
of the sum of the 2
peak heights)
Prior to sample
analysis
During multiple
component standard
analysis
Prepare three
standards for
each analyte
Vary GC operating
conditions and/or
change column
type
-------
Section No. 3.16.,3
Date June 30, 1988
Page 38
Table 3.1 (Continued)
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Preliminary Survey
Sample Analysis
Calibration
standards
3- Response for
consecutive repli-
cate injections of
each standard agree
within 5# of their
average response
4. Calibration curve
generated
5- Audit sample
(optional) analysis
results within 10%
of true value
During calibration
standard analysis
Repeat injections
After calibration
standard analysis
As above
Perform regres-
sion analysis and
plot curve
Repeat audit;
remake and
reanalyze
standards
Glass flask sample
analysis
1. Condensation in
sample flask
2. Flask not
pressurized
3. Condensation in
pressurized flask
after 10 minute
equilibration
4 . Adequate resolu-
tion between peaks
achieved for peaks
of total area
Before sample analysis
As above
As above
(Continued)
5. Retention times
of consecutive in-
jections determined
and agree within 0.5
seconds or 1%
During sample analysis
After sample analysis
Heat flask to
flue gas or duct
temperature
Pressurize flask
Heat flask to
vaporize conden-
sate; if flask
already heated,
release pressure
and repressurize
Vary GC operating
conditions and/or
change column
type
Repeat analysis
-------
Table 3.1 (Continued)
Section No. 3.16.3
Date June 30, 1988
Page 39
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Preliminary Survey
Sample Analysis
Flexible bag
samples
1. Response for
consecutive repli-
cate injections of
each sample agree
within 5% of their
average response
2. Stability of bag
samples acceptable
(second analysis
conducted an equal
number of days cor-
responding to the
the time elapsed
between sample col-
lection and first
analysis within 10%)
During sample analysis
Repeat analysis;
diagnose GC
problem
After second analysis
Consider one
of the alternate
sampling methods
Adsorption tube
samples
1. Samples desorbed
for period specified
in referenced method
2. Response for
consecutive repli-
cate injections of
each sample agree
within 5% of their
average response
3- Desorption effi-
ciency >50%
Before sample analysis
During sample analysis
After sample analysis
Check referenced
method; desorb
for specified
period
Repeat analysis;
diagnose GC
problem
Evaluate more
vigorous desorp-
tion techniques;
Consider one of
the alternative
sampling methods
-------
Section No. 3.16.3
Date June 30, 19"88
Page 40
Table 3.2. ACTIVITY MATRIX FOR PRESAMPLING PREPARATION
Characteristic
Apparatus Check
Barometer
Wet bulb/dry bulb
thermometers
Method 4 equipment
S-type pitot tube
and differential
pressure
Probe
Teflon tubing
Quick connects
Sampling pump
Tedlar bags
Rigid containers
Acceptance limits
Within 2.5 nun
(0.1 in.) Hg of
mercury-in-glass
barometer
Within 1°C (2°F) of
a mercury-in-glass
thermometer
See Section 3. 3- 3
of this Handbook
See Section 3.1.3
of this Handbook
1. Clean; glass
liner, stainless
steel, or Teflon
inert to organics
2. Heating properly
if equipped with
heating system
3. Leak free
New and unused
New or clean
Leak free; adequate
delivery (> 1 Lpm)
Leak free; no
loss of pressure
after 10 minutes
Leak free; no
loss of pressure
after 30 seconds
Frequency and method
of measurement
Before each field trip
As above
Same as Section 3-3-3
Same as Section 3- 1-3
Prior to each trip
follow the cleaning
procedure described
in Subsection 3.5.1
Prior to each trip
As above
As above
As above
Prior to each trip
check with a rotameter
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20
Action if
requirements
are not met
Repair or replace
Replace
Same as Section
3.3.3
Same as Section
3-1.3
Repeat cleaning
Repair or replace
As above
Obtain new tubing
Clean according
to manufacturer's
recommendation
Repair or replace
As above
As above
(Continued)
-------
Section No. 3-16.3
Date June 30, 1988
Page 41
Table 3.2 (Continued)
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Apparatus Check
Direct pump
sampling system
Leakfree; no
loss of pressure
after 30 seconds
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20
As above
Needle valve and
rotameter
Clean
Prior to each trip or
at the sign of erratic
behavior
Clean following
manufacturer's
recommendations
Explosion risk
area sampling
system
Leakfree (no vacuum
loss after 1 minute)
Prior to each trip
Repair or replace
Heated bag
sampling container
1. Leakfree; no
loss of pressure
after 30 seconds
2. Heating properly
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20
As above
As above
As above
Direct interface
sampling system
1. Heating properly
2. Leakfree (no
flow at rotameter
with probe plugged)
As above
As above
As above
As above
Dilution interface
sampling system
1. Heating properly
2. Flowmeters cali-
brated
3- Leakfree; no
loss of pressure
after 30 seconds
As above
Calibrate prior to
each test against a
bubble meter or
spirometer
Prior to each test
pressurize to 5 to 10
cm (2 to 4 in.) H20
As above
Calibrate
Gas chromatograph
equipment
Leakfree, opera-
tional, and suffi-
cient spare parts
for the duration of
the field test
Prior to field test
check system for
leaks, access opera-
tional condition, and
inventory spare parts
Consult the
operator's
manual
(Continued)
-------
Section No. 3.16.3
Date June 30, 1^88
Page 42
Table 3.2 (Continued)
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Reagents and
Equipment
Charcoal adsorber
Sufficient supply
Check supply prior to
each field test
Procure more
adsorbent
Adsorption tubes
Proper adsorbent,
tube size, and
quantity for test
Prior to field test
refer to Method
Highlights Section and
preliminary survey
results
Procure proper
adsorbent, tube
size, and
quantity
Gas chromatograph
carrier gas
Carrier gas compat-
ible to GC and
column; sufficient
quantity for test
Prior to field test
refer to operator's
manual or consult
with manufacturer
Procure compat-
ible carrier gas
in sufficient
quantity
Auxiliary GC gases
Proper type and
grade for GC detec-
tor; sufficient
quantity for test
Prior to field test
refer to operator's
manual or consult
with manufacturer
Procure proper
type and grade
of gases in suf-
ficient quantity
Calibration gases
Proper component(s)
and range; suffi-
cient quantity for
any on-site calibra-
tions
Prior to field test
refer to the prelim-
inary survey results
Obtain gases with
the proper compo-
nents in the
necessary range
and quantity
Calibration gas
dilution system
1. Rotameters clean
and calibrated
2. Dilution ratio
known (optional)
Prior to field test
examine and calibrate
following procedures
in Subsection 2.2
Prior to field test
establish the ratio
following the proced-
ures in Section 5-0
Clean and
calibrate
Check dilution
ratio prior to
analysis
(required)
Zero gas
Hydrocarbon-free
(<0.1 ppmv as pro-
pane or carbon equi-
valent) ; sufficient
supply for test
Analyze or consult
manufacturer
Procure hydro-
carbon-free gas
in sufficient
quantity for test
(Continued)
-------
Section No. 3.16.3
Date June 30, 1988
Page 43
Table 3.2 (Continued)
Characteristic
Audit gases
Organic compounds
for preparing
gaseous standards
Equipment for
preparing gaseous
standards
Packing Equip-
ment for Shipment
Probe
Teflon tubing,
sampling lines,
and vacuum lines
Quick connects ,
flow control
valves, and other
connectors
Barometer
Thermometers and
thermocouple read-
outs
Method 4 equipment
S-type pitot tube
and differential
pressure gauge
Acceptance limits
Required audit gases
in proper range
Target compound(s)
99.9$ pure or of
known purity
See Subsection
3.6.10
Protect with suit-
able packing
material
Coiled and taped;
openings taped
Stored organized
in containers
Packed in rigid foam
in a rigid container
Packed in original
container, if pos-
sible, or rigid
container
See Section 3-3.3 of
this Handbook
See Section 3.1.3 of
this Handbook
Frequency and method
of measurement
Prior to field test
contact EPA or vendor
(see Subsection 3-6.8)
Prior to field test
contact manufacturer
or vendor
See Subsection 3-6.10
Prior to each shipment
As above
As above
As above
As above
As above
As above
Action if
requirements
are not met
Acquire required
audit gas(es)
Procure 99-9$
pure compound(s)
or compound(s) of
known purity
See Subsection
3.6.10
Repack
Coil and tape
Repack
As above
As above
See Section 3.3.3
of this Handbook
See Section 3.1.3
of this Handbook
(Continued)
-------
Section No. 3.16.3
Date June 30, 1988
Page 44
Table 3.2 (Continued)
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Packaging Equip-
ment for Shipment
Glassware
Packed in original
shipping containers,
if available, or
suitable packing
material and marked
"Fragile"
Prior to each shipment
Repack
Tedlar bags
Packed in rigid sam-
pling containers, if
possible, or packed
individually in cor-
rugated boxes with
connectors secured
As above
As above
Sampling pumps
and dry gas meters
Mounted in a rigid
housing or packed in
rigid foam-lined
containers
As above
As above
Dilution interface
system
Built into a rigid
container suitable
for shipment
As above
Rebuild into
rigid container
or pack in suit-
able material
Gas chromatograph
system
Packed in original
shipping container,
secured properly in
van or trailer, or
mounted in a desig-
nated test vehicle
As above
Repack
Gas cylinders
Protective heads on,
secured in van or
trailer; transported
in compliance with
Federal, state, and
local regulations
As above
Repack; check
Federal, state,
and local regu-
lations concern-
ing transport of
compressed gases
Liquid organic
compounds
Top sealed and pack-
ed in original ship-
ping container
As above
Tape and repack
-------
Section No. 3.16.4
Date June 30, 1988
Page 1
4.0 ON-SITE MEASUREMENTS
On-site activities include transporting the equipment to the test site,
unpacking and assembling the sampling and/or analytical equipment, then conducting
the sampling and/or analysis for the predetermined organic compound(s). The qual-
ity assurance activities for the on-site measurements are summarized in Table 4.1
at the end of this section. Copies of all field data forms mentioned in this
section are in Subsection 3-16.12. The on-site measurements checklist, Figure 4.10
at the end of this section, provides the tester with a quick method for checking
requirements during sampling.
4.1 Transportation of Equipment to the Sampling Site
The most efficient means of transporting the equipment from ground level to the
sampling site (often above ground level) should be decided during the preliminary
survey or by prior correspondence. Care should be taken to prevent damage to the
equipment or injury to test personnel during the moving. A clean "laboratory" type
area free of excessive dust and organic compounds should be located and designated
for preparing the sampling systems and conducting sample recovery and analysis, if
applicable.
4.2 Preliminary Measurements and Setup
Method 18 strongly recommends that a preliminary survey and/or laboratory
evaluation be conducted prior to sampling and analysis. Unless adequate prior
knowledge of the source or information is available, the presurvey procedures
described in Subsection 3-0 on presampling operations should be followed to select
an acceptable sampling and analytical approach.
The accuracy of the sampling system(s) following handling and transportation to
the sampling site is determined using a cylinder gas audit. The integrity of the
system(s) is confirmed after setup by conducting the individual system check
described below for the applicable sampling method. Preliminary measurements will
always include determining the stack dimensions and the flue gas moisture. Other
measurements which may be made depending upon the requirements of the applicable
regulations and the source operations include a flow rate determination, velocity
check, and stack gas temperature range measurement.
One of the primary concerns for any organic sampling program must be safety.
The tester should always question the facility representative concerning general
plant safety requirements and safety in regard to sampling at the selected
sampling site. Every sampling and analysis protocol should address the safety
considerations involved in performing the protocol. Because there are numerous
safety considerations involved in organic sampling, it is beyond the scope of this
Handbook to discuss each one in detail. However, it cannot be over-emphasised that
the tester must always be aware of the safety hazards.
4.3 Sampling
The following subsections discuss the procedures for each Method 18 sampling
technique. At this point, the tester has selected the proper sampling technique
and checked the selected sampling system. If this has not been accomplished, the
user should refer to Subsection 3.0 prior to conducting the field test.
-------
Section No. 3.16.4
Date June 30, 1988
Page 2
Because of the complexity in sampling organic compounds from the variety of
potential source types, only the more common problems are addressed for each sam-
pling method. Recommended quality assurance/control checks and procedures are
provided to assess the suitability of the sampling technique for the samples to be
collected. Because of the relative compactness of the equipment and the low cost
of many of the sampling techniques, the tester may be able to utilize two different
sampling techniques at the same time with little additional effort. The samples
from the backup or secondary technique are not analyzed if the primary technique
proves satisfactory. For example, the tester might easily run an adsorption tube
system as a backup to an evacuated bag system. At some facilities, it may be
necessary to conduct two techniques simply to accurately measure all the organic
compounds of interest. The tester should always be aware that a change in process
operations such as raw materials, moisture content, operation mode, and temperature
can render a previously acceptable sampling technique unacceptable.
The specific sampling system descriptions are provided below.
4.3.1 Evacuated Container Sampling (Heated and Unheated) - In this procedure,
sample bags are filled by evacuating the rigid air-tight containers that hold them.
The suitability of the bags for sampling should have been confirmed by permeation
and retention checks using the specific organic compounds of interest during the
presurvey operations. The means of transporting the bags to the laboratory for
analysis within the specified time should also have been determined. Delays in
shipping and/or analysis can result in significant changes in concentration for
many compounds.
On-site sampling includes the following steps:
1. Conducting preliminary measurements and setup.
2. Preparation and setup of sampling system.
3. Preparation of the probe.
4'. Connection of electrical service and leak check of sampling system.
5. Insertion of probe into duct and sealing of port.
6. Purging of sampling system.
7- Proportional sampling.
8. Recording data.
9- Recovering sample and transportion to laboratory.
Preliminary Measurements and Setup - The sampling site should be checked to
ensure that adequate electrical service is available. The stack dimensions are
measured and recorded on a data sheet similar to the ones shown in Figures 4.1, 4.2
and 4.3. The moisture content of the flue gas is used to correct the measured
concentrations to a dry basis. It is typically measured prior to sampling using
wet bulb/dry bulb thermometers or Method 4 (see Subsection 3-2); the determination
should be performed at a time when process operations are like they will be during
final sampling. If the process utilizes and emits ambient air, a sling psychro-
meter may be used to measure the moisture content of the ambient air in the area of
process air uptake. The moisture content value is also used to confirm that the
sampling approach selected is acceptable.
Prior to final sampling, the tester must determine if the final results are to
be presented on a concentration basis or a mass emission basis. If they will be
presented only on a concentration basis, only the concentrations of the specified
organics and the stack gas moisture content must be measured. If the mass emission
rate of any compound is to be presented, the flow rate of the stack gas using a
velocity traverse must also be determined. In this case, although not required by
Method 18, it is preferable that the sampling location be selected in accordance
-------
Plant Kubh&s C^IWm Co-
City Tt+sh'cr. *c.
Operator Ar}/)^> C^sse^
Date 3i-i -!»/&&
Run number' R'c.-l
Stack dia.
mm (in.) £ ;M.
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Average (AP) 0.
Sample box number A//A
Pitot tube (Cr)
^).<&4-
Static press Q mm (in.) H20
Sampling
time,
min
0
£~
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30
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to
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Total ifO
Clock
time,
24 h
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Velocity head
mm (in. ) H20,
(AP)
0.
0.4(*
0.4b
OA(,
Avs 0>$?-
Initial flowmeter setting
Average stack temp (04
Barometric press
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setting
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r(in.) HO Vacuum d
• /.02.
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Hg <&r>&r- o/^tf&tcjr
mm (in.) H20
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Temperature
sample line
°C (°F)
A//A
\
(
\
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Avg
readings
flowmeter box
°C (°F)
A//A
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)
(
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container
°C (°F)
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Figure 4.1. . Field sampling data form for container sampling.
T) O CO
(0 p (D
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(D (D ct
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c y
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Plant Kubke-^ Cfa]L#\^ Co
City Tl^^i^ic flfC
Operator A~rjn* C &r\ter
Date / /^(, fbft
Run number^
Stack dia.
/yd i w, /> a i -\
mm (in. ) (0 in.
Barometric
press ^f>T mm (iff.
Initial probe setting "°C
Sampling rate, £>./5~<
Sampling point locat
C£^?^y Of £>
7 Hg Sample loop volum
(°F) Sample loop temp
e /. O ml
nig "Q^(°V)
Z..,. L/min. (cfm) Column temperature:
ion
initial C,o/isf-»r)k /
/OO °C/min
{MC£~ . program rate fl//A . / °C/min
Dilution system: final — / /O0' °C/min
source flowrate £>. /5"2. L/min (cfm) Carrier gas flow
Meter box number A// A
Stack temp
/&D
2€"(°F)
Static press Q mm (in.) H20
Time of
injection
24 h
1011*
/04-7-
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number
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diluent flowrate fiJ/A L/min (cfm) Final leak check
Dilution ratio 7-6" 2-5"
meter(s) s
diluent
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Figure 4.2. Field sampling data form for direct interface sampling.
O
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CO •
OO 4=-
-------
Plant
City
Operator
TVjj/7'c .
Run number
Stack dia, mm (in.) (0 //?
Flowmeter calib.(Y) /. / 2 J//m /i
Adsorption tube type:
charcoal tube X
silica gel
other
Dilution system: (dynamic)
emission flowsetting A//A
diluent flowsetting
Meter box number
Pitot tube (C)
PN-IZ.
Adsorp tion tube number
Average (aP) Q.j- mm (in.) H20
A/2.
Static press () mm (in.) H20
Initial flowmeter setting
Average stack temp 7O
Barometric press 23. (/S mm (in.) Hg
Dilution system: (static)
emission flowsetting A//A
Final leak check (? m3/min (cfm)
Vacuum during leak check /Q
mm (in.) H20
C (°F) Sampling point location
Sampling
time.
min
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Figure 4.3- Field sampling data form for adsorption tube sampling.
MD <
00
CO
-------
Section No. 3.16.4
. , Date June 30, 19§8
Page 6
with Method 1. If this is impractical, it should be selected to minimize flow
disturbances. The number and locations of sampling points for .the velocity traverse
are selected according to Method 1 (see Section 3-0.1 of this Handbook); the trav-
erse is conducted according to Method 2 (see Section 3-1 of this Handbook). Note:
The Method 18 sampling will be conducted at a single point.
Method 18 requires that samples be collected proportionally, meaning that the
sampling rate must be kept proportional to the stack gas velocity at the sampling
point during the sampling period. If the process has a steady state flow (con-
stant) , then the flow rate does not have to be varied during sampling. The major-
ity of sources of organic emissions are of this type because they use constant rate
fans. If the tester can confirm from the facility that-;'the source of interest has a.
steady state flow (e.g., it uses a constant rate fan), then sampling can be conduc-
ted at a constant rate and no concurrent velocity measurements need to be made.
If it is not known whether the process is steady state or if it is not steady
state, then velocity measurements (the velocity head) must be made at the point to
be sampled. This can be done during the preliminary survey or before final
sampling, but should be done when the process operations are like they will be
during the final sampling. The average velocity head (pitot reading) and range of
fluctuation is determined and then utilized to establish the proper flow rate
settings during sampling. If it is found that the process is not steady state,
then the velocity head must be monitored during sampling to maintain a constant
proportion between the sample flow rate and the flow rate -in the duct.
Select a total sampling time greater than or equal to the minimum total samp-
ling time specified in the applicable emission standard. The number of minutes
between readings while sampling should be an integer. It is desirable for the time
between readings to be such that the flow rate does not change more than 20% during
this period.
If it was determined from the literature or the preliminary survey laboratory
work that the sampling system must be heated during sample collection and analysis,
the average stack temperature is used as. the reference temperature for the initial
heating of the system and should be determined. .Then, the stack temperature at the
sampling point is measured and recorded during sampling to adjust the heating
system just above the stack temperature or the dew point. In addition, the use of
a heated sampling system typically requires that the analysis be conducted on-site
since it is not practical to maintain the sample bag at elevated temperatures for
long periods of time. •
Sampling System Preparation - Prepare the probe and sampling train in the
laboratory area (see Figure 4.4). First, place a loosely packed filter of glass
wool in the end of the probe. Attach a sample bag that has been previously leak
checked to the sample container lid. Seal the inlet to the probe and the sample
container lid to the container body. Transport the container and probe to the
sampling site.
Proportional Sampling - Sampling must be conducted at a rate in constant
proportion to the stack gas flow at the sampling point. Thus, for a steady state
operation, the sampling flow rate is not varied during the run. For a non-steady
state process, the sampling flow rate is varied in proportion to the changing
velocity. The velocity is monitored by measuring the velocity head (AP) which is
linearly related to the square of the velocity. A recommended method for deter-
mining proportional sampling rates is as follows:
1. Conduct a single point velocity check as previously specified, and determine
the average velocity head" (APav ) to be sampled.
-------
VENT
STACK
WALL
FILTER
(GLASS WOOL)
I
REVERSE
(3") TYPE
PITOT TUBE
TEFLON
SAMPLE LINE
VACUUM LINE
MALE QUICK
CONNECTORS
NEEDLE
VALVE
FLOWMETE
PUMP
CHARCOAL
TUBE
NO CHECK
PITOT MANOMETER
RIGID LEAKPROOF CONTAINER
Figure 4.4. Integrated bag sampling system.
*"0 U C/3
(0 (B (D
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00 J^
-------
Section No. 3-l6v4
Date June 30, 1988
Page 8
2. The average sampling flow rate for the test is determined prior to the start
of the run. Typically, the average sampling flow rate is about 0.5 L/min
which will yield approximately 30 liters of sample. The flow rate chosen in
the laboratory should fill the bag to about three fourths of its capacity
during the sample run. The average flow rate chosen is then assigned to the
average velocity head measured.
3. The flow rate to be used during sampling when the velocity head varies from
the average is calculated using the following equation.
(—J
» a v cr *
/2 Equation 4-1
a v g '
where
Q^ = Average sampling rate, L/min (ft3/min),
Qs = Calculated sampling rate, L/min (ft3/min),
AP = Actual velocity head, mm (in.) H20, and
APavg = Average velocity head, mm (in.) H20.
4. Determine the rotameter setting for the sampling rate (Qs ) from the rota-
meter calibration curve, and adjust the rotameter accordingly.
Using this procedure will provide for the correct sampling rate and the proper
filling of the sample bag. Follow the procedure below to obtain an integrated
sample.
1. If a heating system is required, turn on the heating system and set at
average stack temperature determined from the pretest measurements.
2. Leak check the sampling train just prior to sampling by connecting a U-
tube, inclined manometer, or equivalent at the probe inlet and pulling a
vacuum of >_ 10 in. H20. Close the needle valve and then turn the pump off.
The vacuum should remain stable for at least 30 seconds. If a leak is
found, repair before proceeding; if not, slowly release the vacuum gauge.
This leak check is optional.
3. If the system is being heated, wait for it to come to the proper tempe-
rature. Place the probe in the stack at the sampling point: centroid of the
stack or no closer to the walls than 1 meter. Seal 'the sampling port to
prevent dilution of the stack gas by inleakage of ambient air.
4. Disconnect the flexible bag. Purge the system by turning on .the pump and
drawing at least 5 times the sampling system volume through the train, or
purge for 10 minutes, whichever is greater.
5. Adjust the flow rate to the proper setting based on the velocity pressure
(during the purging, for non-steady state processes).
6. Connect the flexible bag to the sampling train (the connections should
ensure a leakfree system), and begin sampling. The rate must remain propor-
tional to the stack gas velocity for the total sampling time specified by the
standard of performance for the industry being sampled.
7. Record all data required (5 minute intervals, miniumum) on the field samp-
ling data form (see Figure 4.1). The flow rate and sample train heating
system should be adjusted after every pitot and temperature reading to the
correct level.
8. Disconnect and seal the flexible bag upon completion of sampling. Take care
not to dilute the contents with ambient air.
9. Label each bag clearly and uniquely to identify it with its corresponding
data form and/or run. If the system is a heated system, the sample bag must
-------
Section No. 3.16.4
Date June 30, 1988
Page 9
be maintained at the stack temperature through sample analysis.
Sample Eecovery and Transport to Laboratory - Sample recovery should be
performed so as to prevent contamination of the bag sample and maintain sample
integrity. The bag should remain leakfree, protected from direct sunlight, main-
tained at a temperature that will prevent condensation of any of the gases, and
stored in a safe place to prevent damage or tampering prior to analysis. It is
recommended that bag samples be analyzed within two hours of sample collection,
however, many.of the organic compounds are stable enough to allow a few days prior
to analysis. Upon completion of the testing and sample recovery, all the data
forms should be checked for completeness and the sample bags reexamined for proper
identification.
Common Problems - The most common problems encountered with bag sampling
techniques are (1) adsorption of the gases on the bag, (2) permeation of the gases
through the bag, (3) reaction of gases in the bag, (4) condensation of the gases or
water vapor in the bag, and (5) leaks developing in the bag during testing, trans-
port, and/or analysis. As described previously in Subsection 3-0, the bags must be
checked for stability and retention of the compound in the bag. If the compound's
concentration significantly diminishes between the time the sample run is completed
and the time of analysis, then the bag technique will have to be modified or rejec-
ted. One modification that can be used to reduce both retention and/or condensa-
tion is addition of a heating system. Heating is generally applied during sample
collection and maintained through analysis. However, heating may increase the
permeation rate. Another option is the use of heat lamps applied to the sample
bags after sample collection and during sample analysis. Two other techniques
that have been used to prevent condensation are (1) addition of a knockout trap to
remove water vapor and heavy organics from the sample stream, and (2) use of
sorbents such as Tenax to remove the high boiling point organics. The tester must
demonstrate that the organic compound(s) of interest are not removed.
Alternatively, sample and/or water vapor condensation may be reduced by the use of
the prefilled- bag technique. The prefilling of the bag lowers the concentration
of the organic and/or water vapor, thereby eliminating condensation.
If the gases are reacting in the bag, then the bag material can be changed, the
time between sample collection and analysis reduced, or a different technique used
such as direct interface sampling. Methods to reduce bag leak problems are proper
construction of the sample bags, conducting additional runs, using a backup sample
collection technique such as an another bag sampling system or an adsorption tube
sampling system, and care with handling the sampling bags. Also, steel canisters
can be used in place of the bags. If the organic compounds are stable with time,
the use of steel canisters may better ensure the safety of the sample especially if
the samples must be air freighted to the laboratory for analysis.
4.3-2 Direct Pump Sampling - Direct pump sampling is conducted in a manner similar
to evacuated container sampling, with the exception that the needle valve and the
pump are located .between the probe and sample bag and the sample exposed surfaces
of both must be constructed of stainless steel, Teflon or other material not affec-
ted by the stack gas (see Figure 4.5). Due to the additional likelihood that
sample may be lost in the needle valve and pump, it is recommended that the probe,
sample line, needle valve, and pump be heated. If it has or can be shown that this
not a concern, then the heating may be eliminated. All precautions, procedures,
data forms and criteria from Subsection 4.3-1 above can be applied. Ensure that
the system has been adequately purged before attaching the bag and sampling.
-------
Stainless
Needle Valve
Rotameter
Filter
(Glass Wool)
Reverse
(3") Type
Pilot Tube
Teflon-Lined
Diaphragm
Pump
\
Protective Container
Figure 4.5- Direct pump sampling system.
*TJ C3 C/3
(D p] (D
Oq rt O
(D (D rr
H-
M c_i o
O C 3
(D 21
O
LO •
O
- UO
Oo
CO
-------
Section No. 3.16.4
Date June 30, 1988
Page 11
4.3.3 Explosion Risk Area Bag Sampling - Explosion risk area bag sampling is also
similar to evacuated container sampling. The major difference is that no electri-
cal components can be used in the explosion risk -area. As previously mentioned in
Subsection 1.0, the first option of the tester is to locate the electrical equip-
ment (e.g., the pump) outside the explosion risk area and run a long flexible line
to the container. If that option is not possible, an evacuated steel container may
be used as shown in Figure 4.6. This option may involve a potential spark hazard
and must be checked though the plant safety officer. No electrical heating of the
system will likely be allowed. If an evacuated steel container is used, the leak
check can be conducted outside the explosion risk area and the probe can be purged
with a hand squeeze pump. The tester may wish to consider an alternative method of
sampling such as adsorption tubes and an intrinsically safe personnel sampling pump
or the syringe method. The primary concern must be safety in an explosion risk area
and all operations must be outlined in writing and cleared through the Plant Safety
Officer. The same, criteria as described above "for suitability of the bag will
apply and must be met.
4.3.4 Prefilled Bag Sampling - The prefilled bag sampling technique is similar to
the heated direct pump sampling method. The major difference is that the sample
bag is prefilled with a known volume of nitrogen, hydrocarbon-free air, or cleaned,
dried ambient air prior to sampling and the volume of gas sampled must be accu-
rately determined (see Figure 4.5). When using a flowmeter or metering pump, the
maximum dilution that should be attempted is 10 tol. Alternatively, a heated, gas
tight syringe may be used to collect the gas at the source and inject it into the
sample bag. A heated, gas tight syringe can be used for dilutions of 5 to 1 when
the dilution is performed in the syringe and 50 to 1 when performed in the bag.
The use of a heated, gas tight syringe should follow the procedures shown below in
Subsection 4.3-5. Both techniques should be verified in the laboratory using
higher concentrations of calibration.... gases and must be within 10# of the calculated
value. The technique is verified in the field by diluting-the audit gases in the
same manner as the stack gases (see Subsection 8.0 for auditing procedures).
Following are the recommended steps to conduct prefilled bag sampling:
1. The sampling should be conducted proportionally as described above in Sub-
section 4.3-1- Calculation of the average sampling rate vs. the average P
will be the same with the exception that the volume of. the prefilled inert
gas must be taken into account.
2. The suitability of the prefilled bag sampling- technique should have been
checked in the laboratory. This would include calculating the dilution
factor required to obtain an acceptable sample concentration.
3. In the laboratory area, fill the sample bag (previously leak checked) with
the calculated volume of inert gas. Because of the potential for leaks,
bags should be filled the, same day ithey are used. The inert gas volume
must be determined with a calibrated dry gas meter or mass flowmeter. The
bag should be sealed and taken to the sampling site.
4. At the sampling site, the sampling system is leak checked without the
sampling bag attached. Turn oh .the heating system and heat the system to
the stack temperature. Connect a U-tube H20 manometer or equivalent to the
inlet of the probe. After the system comes to the desired temperature, turn
on the pump and pull a vacuum of about 10 in. of H20. Turn off the needle
valve and shut off the pump. If; there is no noticeable leak within 30
seconds, then the system is leak free.
5. Place the probe in the stack at the sampling point (centroid or no less
-------
PVC Tubing-
Directional
Needle
Valve
Quick Disconnectors
Air Tight Steel Drum
Sample Bag
Figure 4.6. Explosion risk area sampling system option using an
evacuated steel container.
VD ON
00-
oo -c=-
-------
Section No. 3.16.4
Date June 30, 1988
Page 13
than 1 meter from the wall) and seal the port so there will be no inleakage
of ambient air. Turn on the pump and purge the system for 10 minutes.
During the time that the system is purging, determine and set the proper
flow rate based on the Ap.
6. Turn off the pump and attach the sample bag. Compare the heating system
7. The sampling will be conducted proportionally. The stack temperature and
heating system temperature should be monitored and recorded. Record the
data on the sampling data form (Figure 4.1).
8. At the conclusion of the run, turn off the pump and remove the probe from
the duct. Remove the bag and seal it.
9. Conduct a final leak check. The system should pass the leak check; if it
does not pass, repeat the run.
4.3-5 Heated Syringe Sampling - The heated syringe technique can be used with the
prior approval of the Administrator. This technique should only be used when other
techniques are impractical. The heated syringe technique requires on-site analysis
with three syringes collected and analyzed for each run. The requirements for the
use of the syringes are the same as for the bag with regard to the reaction of the
gases with time and the retention of the gases in the syringe.
Following are the procedures recommended for the syringe sampling technique:
1. If heating is required, then the syringe must be encased in material that
has a high density to maintain the proper temperature. Alternatively, an
external heating system can be used that keeps the syringe at the proper
temperature until just before use and to which the syringe can be immedi-
ately returned.
2. The access port should be extremely small to prevent inleakage of ambient
air. The port may be covered with Teflon or other nonreactive material
that will allow the syringe to penetrate the material for sampling.
3. For the direct injection method (no dilution), place the syringe needle
into the stack and fill and discharge the full volume that will be sampled
three times. Then, draw the emission sample into the syringe, immediately
seal the syringe and return to the heating system, if applicable. The
second and third syringes are sampled at equal time intervals spanning the
required sample (run) time. The syringe samples must not be taken one
immediately after another.
4. For the diluted syringe method, .the inert gas is introduced into the
syringe three times and discharged. Following this, the proper volume of
inert gas is pulled into the syringe. The syringe is then placed into the
duct and the proper volume of stack gas is added. Immediately remove the
syringe needle from the duct, seal the syringe, and return to the heating
system, if applicable.
5. For the bag diluted syringe method, the bag should be prefilled with the
proper volume of inert gas. The sampling is conducted as described above
and the sample injected into the bag through a septum.
6. Record the data on a field sampling data form (can adapt Figure 4.1).
7. Since the method requires a proportional sample to be collected, the
velocity head (AP) should be recorded at about the same time that each
sample is collected. The concentrations can then be mathematically
corrected to provide an integrated value. If the process is a constant
source operation (less than 10% change in flow over the sampling period),
it is not necessary to correct the measured values.
-------
Section No. 3.16..4
Date June 30, 1988
Page 14
4.3.6 Direct Interface Sampling - The direct interface procedure can be used
provided that the moisture content of the stack gas does not interfere with the
analysis procedure, the physical requirements of the equipment can be met at the
site, and the source gas concentration is low enough that detector saturation is
not a problem. Adhere to all safety requirements when using this method. Because
of the amount of time the GC takes to resolve the organic compounds prior to their
analysis, the GC can only typically make three analyses in a one-hour period.
Therefore, the number of injections in the direct interface method is greatly lim-
ited by the resolution time. At least three injections must be conducted per
sample run.
Following are the procedures recommended for extracting a sample from the
stack, transporting the sample through a heated sample line, and introducing it to
the heated sample loop and the GC. The analysis of the sample is described in
Subsection 5«0.
1. Assemble the system as shown Figure 4.7, making all connections tight.
2. Turn on the sampling system heaters. Set the heaters to maintain the stack
temperature as indicated by the stack thermocouple. If this temperature is
above the safe operating temperature of the Teflon components, adjust the
heating system to maintain a temperature adequate to prevent condensation of
water and organic compounds.
3- Turn on the sampling pumps and set the flow rate at the proper setting.
Typically 1 L/min is used.
4. After the system reaches the same temperature as the stack, connect a U-
tube H20 manometer or eqivalent to the inlet of the probe. Pull a vacuum
of about 10 in. of H20, and shut off the needle valve and then the pump.
The vacuum should remain stable for 30 seconds. If the system leaks,
repair and then recheck the system.
5. Calibrate the system as described in Subsection 5-0. Repeat until
duplicate analyses are within 5% of their mean value (Subsection 5-0).
6. Conduct the analyses of the two audit samples as described in Subsection
8.1. The results must agree within 10% of the true value (or greater, if
specified on the cylinder). If the results do not agree, repair the system
and repeat the analyses until agreement is met or until approval is given by
the representative of the Administrator.
7. After the audit has been successfully completed, place the inlet of the
probe at the centroid of the duct, or at a point no closer to the walls
than 1 meter, and draw stack gas into the probe, heated line, and sample
loop. Purge the system for a least 10 minutes.
8. Record the field sampling data on a form such as Figure 4.2.
9- Conduct the analysis of the sample as described in Subsection 5-0. Record
the data on the applicable data form (Figure 5-1. Subsection 5-0). Ensure
that the probe and sample lines are maintained at 0°C to 3°C above the
stack temperature (or a temperature which prevents condensation).
10. Conduct the posttest calibration as described in Subsection 5-0.
4.3.7 Dilution Interface Sampling - Source samples that contain a high concentra-
tion of organic materials may require dilution prior to analysis to prevent
saturating the GC detector. The apparatus required for this direct interface
procedure is basically the same as described above, except a dilution system is
added between the heated sample line and the gas sampling valve. The apparatus is
arranged so that either a 10:1 or 100:1 dilution of the source gas can be directed
to the chromatograph. The description of the apparatus is presented in Subsection
-------
MANOMETER
GLASS 1/2-in.
WOOL TUBING
TC
READOUT
TC READOUT
OR CONTROLLER
STACK WALL
NEEDLE
VALVE
tMPERATURE
CONTROLLER
HEATED
EFLON I INF
HEATED GAS
SAMPLING VALVE
INGC
AUDIT
SAMPLE
IN
CHARCOAL
ADSORBER
PUMP
TO GC INSTRUMENT
FLOWMETER
CARRIER IN
Figure 4.7- Direct interface sampling system.
Tl O CO
03 CD ft)
OD, rr O
(D (D rt
H-
h-1 <-4 O
Ul C D
3
(D Z
O
oo •
O
- OJ
OO
00
ON
-------
Section No. 3.16..4
Date June 30, 1988
Page 16
1.1.9 and the pretest calibration of the apparatus is presented in Subsection
2.2.1.
Following are the procedures recommended for extracting a sample from the
stack, diluting the gas to the proper level, transporting the sample through a
heated sample line, and introducing it to the heated sample loop and the GC. The
analysis of the sample is described in Subsection 5-0.
1. Assemble the apparatus by connecting the heated box, as shown in Figure
4.8, between the heated sample line from the probe and the gas sampling
valve on the chromatograph. Vent the source gas from the gas sampling
valve directly to the charcoal filter, eliminating the pump and rotameter.
2. Measure the stack temperature, and adjust all heating units to a temper-
ature 0°C to 3°C above this temperature. If the temperature is above the
safe operating temperature of the Teflon components, adjust the heating to
maintain a temperature high enough to prevent condensation of water and
organic compounds.
3. After the heaters have come to the proper temperature, connect a U-tube H20
manometer or eqivalent to the inlet of the probe. Turn on the pump and pull
a vacuum of about 10 in. of H20. Shut off the needle valve and then turn
off the pump. The vacuum reading should remain stable for 30 seconds. If a
leak is present, repair and then recheck the system.
4. Verify operation of the dilution system by introducing a calibration gas at
the inlet of the probe. The diluted calibration gas should be within 10% of
the calculated value. If the results for the diluted calibration gas are
not within 10% of the expected values, determine whether the GC and/or the
dilution system is in error. If the analyses are not within acceptable
limits because of the dilution system, correct it to provide the proper
dilution factors. Make this correction by diluting a high concentration
standard gas mixture to adjust the dilution ratio as required.
5. Verify the GC operation using a low concentration standard by diverting the
gas into the sample loop and bypassing the dilution system as described in
Subsection 5-1- If these analyses are not within acceptable limits, correct
the GC by recalibration, etc.
6. Conduct the analyses of the two audit samples as described in Subsection
8.1 using either the dilution system or directly connect the gas sampling
valve as required. The results must agree within 10$ of the true value or
greater value if specified on the cylinder. If the results do not agree,
repair the system and repeat the analyses until agreement is met or until
approval is given by the representative of the Administrator.
7- After the dilution system and GC operations are properly verified and the
audit successfully completed, place the probe at the centroid of the duct
or at a point no closer to the walls than 1 meter, and purge the sampling
system for at least 10 minutes at the proper flow rate. Conduct the analy-
sis of the sample as described in Subsection 5-0- Record the field and
analytical data on the applicable data forms (Figures k.2 and 5-1)- Ensure
that the probe, dilution system, and sample lines are maintained at 0°C to
3°C above the stack temperature (or a temperature which prevents conden-
sation) .
8. Conduct the posttest calibration and verification of the dilution system as
described in Subsection 5-0.
If the dilution system is used for bag sampling, the procedures for verifying
operation of the dilution system will be the same as shown above. The diluted
calibration gas will be collected in a bag and then verified. Also the audit
samples will be collected in a bag and analyzed. Acceptable results must be
-------
Vent to Charcoal Adsorbers
i
Heated Line
from Probe X" \
Quick /" — ^\
Connect
Source
Gas Pump
1.5L/Min
Check Valve
Quick Connects
k i
Hoa
k 1
10:1
1
\
150 cc/Min
Pump
^— 3-Way
Valve:
) in 100:
' Positio
100:1
— Quick
Connects to
Gas Sample
Valve
-\ f
F
i
>,
3
150 cc/Min
Pump
• 1
X^
lorl Rnv at 19fl° P. nr "^niirr-o Tamnaraturo
I
1
.s— Flowmeters
.X"^ (On Outside
Jr of Box)
Flow Rate of
1350 cc/Min
TJ O
CD pi (D
1 | "(B ft) rt
O
3
To Heated GC Sampling Valve
Figure 4.8. Schematic diagram of the heated box required for
dilution interface sampling.
OO
00
-------
Section No. 3-16..4
Date June 30, 1988
Page 18
obtained for the audit samples prior to analysis of the field samples.
4.3.8 Adsorption Tube Sampling - Adsorption tube sampling can be used for those
organics specified in the Method Highlights Section, Table B, and for other com-
pounds as specified in the National Institute of Occupational Safety and Health
(NIOSH) methods. The selection and use of adsorption tubes must be validated in
the laboratory as discussed in Subsections 3-3 and 3-^ °r through the use of the
literature. This check will include selecting the proper adsorption material, and
then checking the capacity, breakthrough volume, adsorption efficiency, and desorp-
tion efficiency. The adsorption efficiency can be greatly affected by the presence
of water vapor and other organics in, and temperature of the stack gas. If sam-
pling is conducted for more than one organic compound, the adsorption and desorp-
tion efficiency checks must consider each. Because changes in process and control
equipment conditions can greatly affect all of the parameters stated above, it is
recommended as a standard operating procedure that more than one adsorption tube be
used. The first tube is analyzed as described in Subsection 5-0. If no problems
are found, then the second tube can be discarded. If problems with the first
tube's adsorption efficiency are discovered, then the primary section of the second
tube can still be analyzed and the results included with those of the primary
portion of the first tube.
Following are the recommended procedures for adsorption tube sampling:
1. The sampling system is assembled as shown in Figure 4.9- The adsorption
tube(s) must be maintained in a vertical direction for sampling. This is
done to prevent channeling of the gases along the side of a tube. It is
recommended that the sampling probe be eliminated when possible. If a
sample probe is used, it should be cleaned prior to its initial use with
the extraction solvent. Teflon tubing should be used for the probe and
sample line.
2. Just prior to sampling, break off the ends of the adsorption tubes to
provide an opening at least one-half of the internal diameter. Audit
samples must be collected on the adsorption tubes during the test program
as described in Subsection 8.0. Since on-site analysis is typically not
conducted when using adsorption tubes, it is recommended that two samples
be collected from each of the two audit cylinders. This allows the tester
a second chance to obtain the proper value for each audit cylinder.
3. Prior to sampling and the collection of the audit samples, the sampling
system must be leak checked by connecting a U-tube H20 manometer or
equivalent to the inlet of the sample probe or adsorption tube. Turn the
pump on and pull a vacuum of about 10 in. of H20. Shut off the needle
valve and then turn off the pump. The vacuum must remain stable for 30
seconds. If a leak is present, repair and recheck the system.
4. If the flow rate in the duct varies by more than 10% during the sampling
period, the sample should be collected proportionally. The proportional
sampling procedures will be the same as described for the bag sampling. The
only difference is that instead of using the volume of the bag as the
limiting factor to determine the average sampling rate, the breakthrough
volume is the limiting factor. If the source is a constant rate source
(less than a 10% change in flow rate for the sampling period), the samples
can be collected at a constant rate.
5. Prepare the field blank just prior to sampling. The field blank will be
handled in be same manner as the field samples and should be from the same
lot as the other adsorption tubes.
6. The flow rate meter must have been calibrated in the laboratory prior to
-------
Supplemental
Adsorption
Tube
as required)
Probe
Soap Bubble
Flowmeter
(for calibration)
T3 O C/3
(a PJ (0
OQ rt O
fl> fl> ct
H-
H* CH O
v^ C t3
g ^
O
uo •
O
Figure 4.9. Adsorption tube sampling system.
CO
CO
ON
-------
Section No. 3.16.4
Date June 30, 198&
Page 20
the field trip as described in Subsection 2.1. The volume of sample coll-
ected must be accurately known for adsorption tube sampling.
7. The sample run time must be equal to or greater than that specified by the
applicable regulation. During each sample run, the data should be recorded
on the sample data form (Figure 4.3 or equivalent).
8. At the conclusion of each run, conduct another leak check as described
above. If the system does not pass the leak check, the run should be
rejected, the leak located and repaired, and another run conducted.
9. After completing a successful leak check, remove the adsorption tube from
the holder and seal both ends with plastic caps. The tubes should be
packed lightly with padding to minimize the chance of breakage. If the
samples are to be held for an extended period of time, they should be kept
cool to reduce the amount of migration of the organic from the primary
section to the secondary section. Note: Pack the tubes separately from
bulk samples to avoid possible contamination.
10. It is recommended, that at the conclusion of the test, the sample probe (if
used) be rinsed into a 20-ml glass scintillation vial with about 5 to 10 ml
of the desorption solvent. This sample will be analyzed as a check on the
loss of the organic in the probe during sampling. If more than 10$ of the
total sample collected in the adsorption tubes is present in the probe, the
samples should be rejected or the sample catch adjusted to account for the
loss. Alternatively, the probe can be rinsed after each run and the rinse
added to the desorption solvent prior to analysis.
11. At the conclusion of the test program, check all samples to ensure that
they are uniquely identified and check all data sheets to ensure that all
data has been recorded.
-------
Section No. 3.16.4
Date June 30, 1988
Page 21
WATER VAPOR CONTENT
Method 4
Reference Method conducted in proper manner (Handbook Section 3-3i Method
4, Figure 4.1)
Wet Bulb/Dry Bulb
Temperature readings taken when stabilized ;
WB Temp °C (°F) DB Temp °C (°F) '
DIRECT OR DILUTION BAG SAMPLING
Apparatus
Pitot tube: Type S Other k, Properly attached
Pressure gauge: Manometer ' Other , Sensitivity
Probe liner: Borosilicate ' Stainless steel Teflon ._
Clean ,_, Probe heater (if applicable) on Glass wool filter
(if applicable) in place .Stainless steel or Teflon unions used
to connect to sample line
Sample line: Teflon , Cleaned , Heated (if applicable)
Tedlar Other , Blank checked , Leak checked
Reactivity check , Retention check
Flowmeter: Proper range , Heated (if applicable) , Calibrated
Pump: Teflon coated diaphram , Positive displacement pump ,
Evacuated canister , Personnel pump
Heated box with temperature control system: Maintained at proper temperature
Charcoal adsorption tube to adsorb organic vapors: Sufficent capacity
Dilution equipment: N2 gas , Hydrocarbon-free air . Cleaned and
dried ambient air , Dry gas meter
Barometer: Mercury , Aneroid , Other
Stack and ambient temperature: Thermometer , Thermocouple ,
Calibrated
Procedures
Recent calibration (if applicable): Pitot tube , Flowmeter ,
Positive displacement pump* , Dry gas meter* , Thermometer
Thermocouple , Barometer
Sampling technique: Indirect bag , Direct bag , Explosion risk bag
Dilution bag , Heated syringe , Adsorption tube .
Proportional rate , Constant rate , Direct interface
Dilution interface
*Most significant items/parameters to be checked.
Figure 4.10. On-site measurements checklist.
-------
Section No. 3.16.4
Date June 30, 1988
Page 22
Figure 4.10 (Continued)
Filter end of probe (if applicable) and pitot tube placed at centroid of duct (or
no closer than 1 meter to stack wall) and sample purged through the probe and
sample lines*
Vacuum line attached to sample bag and system evacuated until the flowmeter
indicates no flow (leakless)*
Heated box (if applicable) same temperature as duct*
Velocity pressure recorded and sample flow set
Proportional rate sampling maintained during run*
Stack temperature, barometric pressure, ambient temperature, velocity pressure
at regular intervals, sampling flow rate at regular intervals, and initial and
final sampling times recorded*
At conclusion of run, pump shut off, sample line and vacuum line disconnected
and valve on bag closed __
Heated box (if applicable) maintained at same temperature as duct until analysis
conducted
No condensation visible in bag* •-
Sample bag and its container protected from the sunlight
Audit gases collected in bags using sampling system*
Explosive area bag sampling: (with following expections same as above)
Pump is replaced with an evacuated canister or sufficient additional line is added
between the sample bag container and the pump to remove the pump from the
explosive area
Audit gases collected in bags using sampling system*
Prefilled bag: Proportional rate Constant rate
Dilution factor determined to prevent condensation* '
Proper amount of inert gas mete red. into bag through a properly calibrated dry gas
meter* ' _ • . .
Filter. end of probe (if applicable) and pitot tube placed at centroid of duct (or
no closer than 1 meter to stack wall) and sample purged through the. heated probe,
heated sample line, and heated flowmeter or positive displacement pump* _
Leak checked and- partially filled bag attached to sample line _
Stack temperature, barometric pressure, ambient temperature, velocity pressure at
regular intervals, sampling rate at regular intervals, and initial and final sam-
pling times recorded* _
Probe, sample line, and properly calibrated flowmeter or positive displacement pump
maintained at the stack temperature* ___ _
Sampling conducted at the predetermined rate, proportionally or constant for entire
*
run
No condensation visible in probe, sample lines, or bag* _
At conclusion of run, pump shut off, sample line disconnected and valve on bag
closed _
Sample bag and its container protected from sunlight _ _
Audit gases collected in bags using dilution system* _
Sample Recovery and Analysis
(As described in "Postsampling operations checklist," Figure 5-10)
*Most significant items/parameters to be checked.
-------
Section No. 3.16.4
Date June 30, 1988
Page 23
Figure 4.10 (Continued)
DIRECT AND DILUTION INTERFACE
Apparatus
Probe: Stainless steel , Glass , Teflon , Heated system (if
applicable) , Checked • •
Heated sample line: Checked*
Thermocouple readout devise for stack and sample line: Checked*
Heated gas sample valve: Checked*
Leakless Teflon-coated diaphram pump: Checked* '
Flowmeter: Suitable range
Charcoal adsorber to adsorb organic vapors ___
Gas chromatograph and calibration standards (as shown in "Postsampling operations
checklist," Figure 5.10)*^ » '
For dilution interface sampling only:
Dilution pump: Positive displacement pump or calibrated flowmeter with Teflon-
coated diaphram pump checked* •
Valves: Two three-way attached to dilution system-
Flowmeters: Two to measure dilution gas, checked*
Heated box: Capable of maintaining 120°C and contains three pumps, three-way
valves, and connections, checked*
Diluent gas and regulators: N2 gas , Hydrocarbon-free air , Cleaned air _,
Checked
Procedures
All gas chromatograph procedures shown in "Postsampling operations checklist"
(Figure 5.10)
Recent calibration: Thermocouples • , Flowmeter _, Dilution system
(for dilution system only)*
Filter end of heated probe placed at centroid of duct (or no closer than 1 meter to
stack wall), probe and sample line heat turned on and maintained at a temperature
of 0°C to 3°C above the source temperature while purging stack gas
Gas chromatograph calibrated while sample line purged*
After calibration, performance audit conducted and acceptable* '_
Sample line attached to GC and sample analyzed after thorough flushing*
With probe removed from stack for 5 min, ambient air or cleaned air analysis is
less than 5# of the emission results*
Probe placed back in duct and duplicate analysis of next calibration conducted
until acceptable agreement obtained*
All samples, calibration mixtures, and audits are analyzed at the same pressure
through the sample loop*
Sample Analysis
(As shown in "Postsampling operations checklist," Figure 5.10)
*Most significant items/parameters to be checked.
-------
Section No. 3.16.if
Date June 30, 1988
Page 24
Figure 4.10 (Continued)
If a dilution system is used, check the following:
With the sample probe, sample line, and dilution box heating systems on, probe and
source thermocouple inserted into stack and all heating systems adjusted to a
temperature of 0°C to 3°C above the stack temperature
The dilution system's dilution factor is verified with a high concentration gas of
known concentration (within 10%)
The gas chromatograph operation verified by diverting a low concentration gas into
sample loop
The same dilution setting used throughout the run
The analysis criteria is the same shown as for the direct interface and in the
"Postsampling operations checklist," Figure 5.10
ADSORPTION TUBES
Apparatus
Probe: Stainless steel , Glass , Teflon , Heated
system and filter (if applicable)
Silica gel tube or extra adsorption tube used prior to adsorption tube when
moisture content is greater than 3 percent
Leakiess sample pump calibrated with limiting (sonic) orifice or flowmeter
Rotameter to detect changes in flow
Adsorption tube: Charcoal (800/200 mg), Silica gel (1040/260 mg) .
Stopwatch to accurately measure sample time •
Procedures
Recent calibration of pump and flowmeter with bubble meter
Extreme care is taken to ensure that no sample is lost in the probe or sample line
prior to the adsorption tube
Pretest leak check is acceptable (no flow indicated oh meter)
Total sample time, sample flow rate, barometric pressure, and ambient temperature
recorded
Total sample volume commensurate with expected concentration and recommended sample
loading factors
Silica gel tube or extra adsorption tube used prior to adsorption tube when
moisture content is greater than 3 percent '
Posttest leak check and volume rate meter check is acceptable (no flow indicated on
meter, posttest calculated flow rate within 5 percent of pretest flow rate)
Sample Analysis
(As shown in the "Postsampling operations checklist," Figure 5.10)
*Most significant items/parameters to be checked.
-------
Section No. 3.16.4
Date June 30, 1988
Page 25
Table 4.1. ACTIVITY MATRIX FOR ON-SITE MEASUREMENTS
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Preliminary de-
terminations
and measure-
ments
If final results on
concentration basis,
determine the. mois-
ture content of stack
gas
If final results on
emission rate basis,
determine moisture
content and flow
rate of stack gas
If process has >IQ%
variation in APa v e,
sampling must be con-
ducted proportionally
If preliminary survey
or information showed
a heating system nec-
essary for sampling,
determine stack gas
temperature, Ts
Determine stack
dimensions
Select sampling time
>^ minimum total
sampling time in
applicable emission
standard; number or
minutes between
readings should be an
integer
Once each field test;
use wet bulb/dry bulb
thermometer, Method 4,
or sling psychrometer
See above for moisture
content; for flow
rate, once each field
test using Method 1
location, if possible,
and Method 2 proce-
dures
Determine before
test by measuring
APaye and range of
fluctuation; if re-
quired, use APave and
AP measured during
sampling to vary
sampling flow rate to
sample proportionally
• Prior to and during
sampling
Prior to sampling,
using tape measure
Prior to sampling
Complete
Complete
Complete or
repeat sampling
Complete or
repeat sampling
Complete
Complete
(Continued)
-------
Table 4.1 (Continued)
Section No. 3.16.4
Date June 30, 198*
Page 26
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Evacuated con-
tainer sampling
1. Assemble system
using Fig. 4.4;
leakage
no
2. Minimum vacuum
of 10 in. of H20;
stable for 30 s
3. Heating system, if
used, between 0°
and 3°C above
4. Locate probe tip
at centroid of
stack or no closer
than 1 meter to
walls of stack
5. Purge probe and
sample system,
5 times system
volume or 10
minutes , which-
ever is greater
6. Sample propor-
ionally based on
AP0.,_ and moni-
3 V C
tored AP
Before sample collec-
tion, visually and
physically inspect
all connections
Before sample collec-
tion; use a H20-
filled U-tube
manometer or equiva-
lent
Confirm prior to and
monitor during sam-
pling using tempera-
ture sensor(s)
Prior to sampling;
determine using stack
dimensions
Before sample collec-
tion; with bag
unattached, turn on
pump
Throughout sampling
Check for leaks,
repair system;
repeat check
Check system
for leaks;
check pump,
joints, and
valves for source
of leak; repair
and recheck
Adjust heating
system
Reposition
Repeat purge
Repeat test
Direct pump
sampling
(Continued)
1. Assemble system
using Fig. 4.5;
sample exposed
components of
Teflon, stain-
less steel, etc;
no leakage
Before sample col-
lection, visually
and physically in-
spect all equipment
and connections
Check for leaks,
repair system;
replace inappro-
priate components
-------
Table 4.1 (Continued)
Section No. 3.16.4
Date June 30, 1988
Page 27
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Direct pump
sampling (cont)
2. Follow steps 2-6
for evacuated bag
sampling
As above
As above
Explosion risk
area bag
sampling
1. Assemble system,
Figure 4.6 is one
option; no elec-
trical compo-
nents in explo-
sion risk area;
no leakage
2. Leak check as
above outside
explosion risk
area
3. Purge probe with
a hand squeeze
pump changing
volume at least
5 times
4. Follow steps 4
and 6 for evac-
uated bag samp-
ling
5. Clear all oper-
ations in writ-
ing through
Plant Safety
Officer
As above
As above
As above
As above
As above
As above
As above
As above
Prior to working
in explosion risk
area
Complete
Prefilled bag
sampling
(Continued)
1. Assemble system
using Fig. 4.5;
need calibrated
flowmeter in-line
2. Calculate accept-
able dilution
factor
3- Leak check bag
As above for
evacuated bag
sampling
Prior to sampling
Prior to filling
As above for
evacuated bag
sampling
Complete
Repair or replace
-------
Table 4.1 (Continued)
Section No. 3.16.4
Date June 30, 19*88
Page 28
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Prefilled bag
sampling (cont)
4. Fill bag with
known volume of
inert gas
5- Leak check system
at stack temper-
ature , minimum
vacuum of 10 in.
of H20, stable
for 30 s
6. Follow steps 3~6
for evacuated bag
sampling
7• Determine volume
of gas sampled
accurately
Prior to sampling;
use calibrated dry gas
meter or mass flow-
meter
Before sample collec-
tion without bag
attached; use U-tube
H20-filled manometer
or equivalent
As above
During sample collec-
tion; use flowmeter
or metering pump (max.
dilution 10 to 1) or
heated syringe, (see
below (max. dilution
50 to 1)
Complete
Locate leak,
repair or
replace compo-
nents , and
recheck
As above
Complete
Heated syringe
sampling -
direct injec-
tion
1. Check syringes
for compound re-
tention and re-
action
2. Seal port to pre-
vent inleakage
of ambient air
3- Place needle in
stack at sample
point, pull and
discharge sample
volume three
times
See Subsection 1.0
Visually check
Prior to sampling
Complete
Reseal and re
check
Complete
(Continued)
-------
Table 4.1 (Continued)
Section No. 3.16.4
Date June 30, 1988
Page 29
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Heated syringe
sampling - dir-
ect injection
(cont)
Seal after pull-
ing sample vol-
ume, return to
heating system,
if necessary;
monitor heating
system tempera-
ture
Choose sample
volumes to sample
proportionally;
monitor AP, if
necessary (>10#
change in flow
over sampling
period)
Take second and
third syringe
samples at equal
time intervals
spanning the
required sampling
time in applica-
ble emission
standard
For each sample
collection; use
temperature sensor
Complete
During sample collec-
tion; use pitot tube
Repeat sampling
During field test
Repeat sampling
Heated syringe
sampling -
dilution
method
(Continued)
1. Follow same steps
as for heated
syringe - direct
injection, except
prefill bag (see
steps 2-4 in pre-
filled bag samp-
ling) and inject
gas in heated
syringe through
bag septum
As above
As above
-------
Table 4.1 (Continued)
Section No. 3.16.4
Date June 30, 1988
Page 30
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Direct interface
sampling
1. Assemble system
using Fig. 4.7;
no leakage
2. Heating system
between 0° and
3°C above T
3. Set flow rate at
1 L/min
4. Leak check system
at stack temper-
ature at minimum
vacuum of 10 in.
of H20; stable
for 30 s
5- Calibrate system;
duplicate analy-
ses within 5# of
their mean
6. Analyze audit
cylinders;
results within
10% of true value
7. Follow steps 4
and 5 of evacu-
ated bag
sampling
8. Analyze samples
and conduct
posttest
calibration
Before sample collec-
tion visually and
physically inspect
all connections
Confirm prior to and
monitor during
sampling using temper-
ature sensors
Prior to sampling
Check for leaks;
repair system;
repeat check
Adjust
During sampling; use
a U-tube H20 mano-
meter or equivalent
See Subsection 5.0
See Subsection 8.0
As above
See Subsection 5.0
Complete
Check system for
for leaks; repair
and recheck
Identify
problems; recal-
ibrate and check
Reject samples
and rerun test
As above
Complete
(Continued)
-------
Table 4.1 (Continued)
Section No. 3.16.4
Date June 30, 1988
Page 31
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Dilution inter-
face sampling
1. Follow all steps
for direct inter-
face sampling
with addition
of steps below
2. Assemble with
dilution system
in line, see
Figure 4.8
3. If Teflon com-
ponents cannot
withstand stack
temperature,
heating system
should be set to
prevent conden-
sation
4. Verify dilution
system to within
10% of expected
value
As above
As above
As above
As above
Prior to and during
sampling
Adjust
Prior to sampling; use
a calibration gas
Pinpoint problem
to dilution
system or GC;
repair and
recheck; adjust
dilution, if
necessary
Adsorption tube
sampling
1. Assemble system
using Figure 4.9
2. Break off ends of
adsorption tubes;
maintain in ver-
tical position
for sampling
3. Follow step 4 for
direct interface
for leak check
Before sample coll-
ection, visually and
physically check all
connections
Just prior to samp-
ling; during sampling
As above
Check for leaks,
repair, and
recheck
Complete and
check
As above
(Continued)
-------
Table 4.1 (Continued)
Section No. 3.16.4
Date June 30, 1988
Page 32
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Adsorption tube
sampling (cont)
4. Conduct sampling
proportionally,
if the flow rate
varies more than
10%
5- Determine samp-
ling time, >^ re-
quirement of
applicable
emission standard
6. Run field blanks
7. Perform posttest
leak check as
above
During sampling
Repeat test
Prior to sampling
Complete
Once each set of
samples
As above
Complete
Reject sample,
rerun test
Sample
recovery
(Continued)
1. If applicable,
remove samples
from sampling
system
2. Protect bag samp-
les from sunlight
and maintain at a
temperature which
will prevent con-
densation
3- Analyze bag sam-
ples within two
hours of sampling
4. For adsorption
tube samples,
perform at least
one probe rinse
with desorption
solvent to con-
firm that <10% of
sample is col-
lected in probe
Following sampling
Following sampling
Complete
Complete
Following sampling
Following sampling;
analyze sample with
GC
Complete
Adjust sample
values to
account for probe
catch
-------
Section No. 3.16.4
Date June 30, 1988
Page 33
Table 4.1 (Continued)
Characteristic
Acceptance Limits
Frequency and method
of measurement
requirements
are not met
Sample
logistics
Properly label
all bags, contain-
ers, tubes, etc.
Record all data on
forms in Figs. 4.1,
4.2, and 4.3 and
5-1
Visually check
each sample
As above
Complete the
labeling
Complete the
data records
-------
Section No. 3-16.5
Date June 30, 1988
Page 1
5.0 POSTSAMPLING OPERATIONS
The postsampling operations for Method 18 include preparation of calibration
standards appropriate for the sampling technique used, determination of desorption
efficiency and collection efficiency for adsorption tubes (if used), adsorption
tube sample preparation, sample analysis, and determination of acceptable resolu-
tion and precision. See Subsection 3-1-5 for postsampling operations related to
velocity determinations and Subsection 3-3-5 for postsampling operations related to
determination of the flue gas or duct moisture. Figure 5-10 at the end of this
section provides a checklist for monitoring the postsampling operations. Table 5-1
at the end of the section summarizes the quality assurance activities associated
with the postsampling operations.
5.1 Preparation of Calibration Standards
Calibration standards are to be prepared prior to sample analysis following
the procedures described in the following subsections. Refer to Table E in the
Method Highlights Section for recommendations on the procedures suitable for selec-
ted compounds. Note that there are two basic types of standards, gaseous or liq-
uid; the type prepared depends on the type of sample collected. Gaseous cali-
bration standards will be needed prior to the analysis of preliminary survey sam-
ples collected in glass flasks or bags, and final samples collected in bags or by
direct and dilution interface sampling. There are three techniques for preparing
gaseous standards, depending on availability and the chemical characteristics of
the standard compound(s); gas cylinder standards may also be used directly, if the
proper concentration ranges are available. Liquid calibration standards are re-
quired for the analysis of adsorption tube samples from the preliminary survey
and/or the final sampling, as well as to determine the desorption efficiency; there
are two techniques for preparing liquid calibration standards. The concentrations
of the calibration standards should bracket the expected concentrations of the
target compound(s) at the source being tested. Specific procedures for preparing
and analyzing each type of standard are described below.
For each target compound, a minimum of three different standard concentra-
tions are required to calibrate the GC. An exception to this requirement involves
developing relative response factors for each compound to be tested as compared to
a single organic compound. Once in the field, the GC is calibrated for all target
compounds using the single organic. The validity of this procedure must be first
be proven in the laboratory prior to the test. To save time, multiple component
standards can be prepared and analyzed provided the elution order of the components
is known.
It is recommended that the linearity of the calibration curve be checked
comparing the actual concentration of the calibration standards to the concentra-
tion of the standards calculated using the standard peak areas and the linear re-
gression equation. The recommended criteria for linearity is for the calculated
concentration for each standard be within J% of the actual concentration.
After establishing the GC calibration curve, an analysis of the audit cyl-
inder is performed as described in Subsection 8.1. For an instrument drift check,
a second analysis of the calibration standards and generation of a second
calibration curve is required following sample analysis. The area values for the
first and second analyses of each standard must be within 5% of their average. If
this criterion cannot be met, then the sample values obtained using the first and
second calibration curves should be averaged. In addition, if reporting such
-------
Section No. 3.16.5
Date June 30, 1988*
Page 2
average values for the samples is warranted, an additional analysis of the audit
.cylinder should be performed. The average of the audit values obtained using the
two calibration curves should be reported.
5.1.1 Commercial Gas Cylinder Mixtures - Commercial gas cylinder mixtures can be
used provided that the cylinders have . been certified by direct analysis and the
proper concentrations for the emission test can be obtained. Calibrate the GC
using gas cylinders by the following procedure:
1. Secure the three cylinders near the GC and remove their protective caps.
Attach an appropriate regulator that is equipped with a flow control valve
to the lowest concentration standard.
2. For preliminary survey sample analysis, establish the proper GC conditions
based on the referenced conditions in Table D in the Method Highlights
Section, previous experience, or possibly, if the plant being tested has a
laboratory, the laboratory personnel. For final sample analysis, establish
the optimum GC conditions determined during the preliminary survey sample
analysis.
3. Attach a quick connect or equivalent, compatible to the connection on the
Tedlar bag or the interface sample line, to the gas sampling valve on the
GC.
4. Connect a length of Teflon tubing to the flow control valve on the regula-
tor and connect the other end, using a compatible connector, to the gas
sample valve.
,5. With the gas sampling valve in the load position and the flow control valve
open, open the valve on the cylinder and adjust the pressure regulator to
deliver a flow of lOOcc/min through the sample loop, determined by a rota-
meter or other flow sensing device on the loop outlet.
6. Allow the sample loop to be flushed for 30 seconds, then turn off the flow
control valve.
7. Allow the sample loop to return to the same pressure that will be exper-
ienced during sample analysis, determined with a. manometer or equivalent
connected to a tee on the outlet of the loop, and immediately switch the
valve to the inject position.
8. Note the time of the injection on the strip chart recorder and/or actuate
the electronic integrator. Also, record the standard concentration, detec-
tor attenuation factor, chart speed, sample loop temperature, column tem-
perature and identity, and the carrier gas type and flow rate on the data
form shown in Figure 5-1- It is also recommended that the same information
be recorded directly on the chromatogram. Record the operating parameters
for the particular detector being used.
9. After the analysis, determine the retention time of each standard component
and determine the peak area. Repeat the injection of the first cylinder gas
standard until the area counts from two consecutive injections are within 5
percent of their average.
10. Multiply the average area count of the consecutive injections by the atten-
uation factor to get the calibration area value for that standard concen-
tration. NOTE: Attenuation factors which affect the plot traced, but not
the area count returned by an electronic integrator should not be
multiplied by the average area count. Observe the effect of attenuation
changes made at the console of a specific electronic integrator to
determine the appropriate course of action.
-------
Section No. 3.16.5
Date June 30, 1988
Page 3
Analysis of Method 18 Field Samples
Date: 2-/Z /&& Analyst: JT 6n>od/i "ok. Plant:
Location: PAs/7C . //£ _ Sample Type:
C*Ji** C-
•/"£.*//<»»-
Type of Calibration Standard: t-i^meLin-h
Number of Standards: 3 Date Prepared:
Target Compound:
•2-/Z. /3g Prepared By:
A-
Column Used: P
4. -Lit
IZ.4-2.
J.1.7-
A/4-/ AM
10 I /O '
2- / 2.
£.&3/ J-.&i
0.01
/ 4-2.01.
4/6Z
/oo
-1.0
Linear regression equation; slope (m): 4/, BO y-intercept (b) : _
Sample Analysis Data
First analysis/second analysis
Sample identification
Interface dilution factor
Flow rate through loop (ml/min)
Liquid injection volume (tubes)
Injection time (24-hr clock)
Chart speed (cm/min)
Detector attenuation
Peak retention time
Peak retention time range
Peak area
Peak area x atten. factor (At/A2
Average peak area value (Y)
% deviation from average (#Dav )
Calculated concentration (Cs)
Sample 1
A/A
-LOO/ 2J3Q
V4/ A/A-
15:11,11$: W
/O / 10
L- I 2-
^.g^/^.g3
Q.OI
004-/
Sample 2
ygg-2
A/A
2oo/ 2,0 Q
A/A/ A/A-
rt I /O
2- I 7-
Sample 3
2,00/2.00
A/A-/ A/A
1
Z. 1 2-
H.+Z.
1*14-0
0.4-
3^3
S7.2,
4-3.1
(Y - b)
or
*D,
avg
m
_ p
ltd act
Figure 5-1. Data form for analysis of Method 18 field samples.
-------
Section No. 3-16.5
Date June 30, 1988"
Page 4
11. Repeat the procedure for the other standard concentrations, with the high-
est concentration analyzed last.
12. Prepare a plot with the standard concentration (Cs) along the abscissa (x-
axis) versus the corresponding calibration area value along the ordinate
(y-axis). Perform a regression analysis to calculate the slope and the y-
intercept. Draw the least squares line on the plot.
5.1.2 Preparation and Analysis of Gaseous Standards from High Concentration Cylin-
ders - Gaseous standards can be prepared from high concentration cylinder gases by
dilution with hydrocarbon-free gas and collection of the diluted gas mixture in a
Tedlar bag (10 liters or larger). A single-stage dilution system is used for
dilutions up to about 20-fold. For greater dilutions, a two-stage dilution system
should be used. It is recommended that a check of the dilution system be made by
analyzing a low concentration cylinder standard that is in the range of one of the
standards prepared by dilution. Prepare the gaseous standards, by the dilution
technique, using the procedures that follow:
1. Assemble the single-stage dilution system, as shown in Figure 5-2 and/or
the two-stage dilution system, as shown in Figure 5-3, using rotameters
(flowmeters) calibrated following the procedures described in Subsection
2.1.3- (More precise dilutions may be possible if the dilution system
utilizes mass flow controllers and mass flowmeters in place of the
rotameters.)
2. Connect the primary flowmeters on the single-stage system to the calibra-
tion gas mixture and the diluent gas (hydrocarbon-free). On the two-stage
system, connect the secondary flowmeters to the two diluent gas cylinders.
3- Connect a leakfree evacuated Tedlar bag fitted with a quick connect or
equivalent, compatible to the connection on the actual sample bags or the
interface sample line, to the tee connector on the single-stage system or
following the second stage of the two-stage system.
4. Open the gas cylinders, adjust all the pressure regulators to the same
pressure, and adjust the gas flows to achieve the desired dilution ratio
using the flow control valves. On the two-stage system, adjust the needle
valve on the high concentration waste outlet so that 30% of the high con-
centration gas is wasted and 10% goes to the second stage. NOTE: Divert
high concentration waste to a fume hood or pass it through an appropriate
adsorption media to protect personnel from exposure' to harmful
concentrations of organic vapors.
5- Take periodic readings of the pressure difference between the first and
second stages of the two-stage system, as indicated by a water manometer or
equivalent, to..correct the flow reading from the first stage to the second
stage. If the flow rates of the two stages can be balanced so that the
pressures are equal, then no correction will be necessary.
6. Disconnect the Tedlar bag from the dilution system before the bag is total-
ly full, and turn off the gases. Label the bag to indicate the contents,
the time and data when it was prepared, the identity of the high concentra-
tion gas cylinder, and the dilution ratio(s) used.
7- Record the ambient temperature, the flow meter readings, the barometric
pressure, and the average first stage pressure on the data form shown in
Figure 5•^•
8. Calculate the concentration (Cs ) , in ppmv , of the component in the final
gas mixture by the following formulas for single-stage and two-stage
dilution.
-------
COMPONENT
GAS
CYLINDER
o
"T" CONNECTOR
CALIBRATED ROTAMETERS
WITH FLOW CONTROL
VALVES
DILUENT
GAS
CYLINDER
TEDLAR BAG
CO CD
(0 (B
Ul CH
O
rt
H-
UJ .
O
• UJ
Figure 5-2. Single-stage calibration gas dilution
system.
>x> ON
oo •
00 U1
-------
MANOMETER
HIGH
CONCENTRATION
WASTE
NEEDLE VALVES
ROTAMETERS-
LOW
CONCENTRATION
GAS
PRESSURE
REGULATOR
+ ( PR
DILUENT AIR
DILUENT AIR
PURE SUBSTANCE OR
PURE SUBSTANCE/N, MIXTURE
Figure 5.3. Two-stage calibration gas dilution system.
T3 O C/3
0 (0 0)
TO rt O
(D (D rt
H-
CT\ C-i O
§ 3
(D 2
O
OJ •
o
co •
Oovjl
-------
Section No. 3.16.5
Date June 30, 1988
Page 7
Preparation of Standards by Dilution of Gas Cylinder Standards
Date: 2/2-1^
Preparer:
Purpose:
Cylinder Component; /^<^g/?/0 ppm.. Certification Date: //12. I ft&
Stage 1
Standard'gas flowmeter reading
Diluent gas flowmeter reading
Laboratory'temperature (°K)
Barometric pressure (Pb) (mm Hg)
Flow'rate of cylinder gas (qcl)
standard conditions (ml/min)
Flow rate of diluent gas (qdl)
standard conditions (ml/min)
Calculated concentration (Cs )
Mixture 1
Mixture 2
4O
Mixture 3
at
at
40
/OO
(Xxqcl)
Stage 2 (if used) Mixture 1
Standard gas flowmeter reading
from stage 1
Diluent gas flowmeter reading
into stage 2
Average differential pressure (Pd)
between stage 1 and 2 (mm H20) '
Flow rate of diluted gas
tec2 actual) at standard
conditions to stage 2 (ml/min)
Flow rate of diluted gas
tec 2 corr) at corrected
standard conditions to
stage 2 (ml/min)
/O
10
0
lo
/o
Mixture 2 Mixture 3
2-7- A/-4
0
Flow rate of diluent gas (qd2) at' ' . /
standard conditions to /
stage 2 (ml/min) /& (00 \
Calculated concentration (Cs )
IO.D
30.0 l
actual
c. = x
ci + qdl)
^c 2 corr
Figure
Calibration standard preparation data form for diluted gas cylinders.
-------
For single-stage dilution:
Section No. 3.16.5,
Date June 30, 1988*
Page 8
(X x qc)
Cs = ' Equation 5"!
where
X = Mole or volume fraction of the organic in the calibration gas
that was diluted, ppmv,
qc = Flow rate of the calibration gas that was diluted, and
qd = Diluent gas flow rate.
For two-stage dilution:
Sc2 corr,3 ^c 2 actual X Equation 5~2
where
qc2 corr = Corrected flow rate from the first stage to the second stage,
qc2 actual = Actual flow rate from the first stage to the second stage,
Pd = Average differential pressure between the first and second
stage, mm or in. H20, and
Pb = Barometric pressure, mm or in. H20.
and
"c 1 ^c 2 c o r r
Cs = X x x : Equation 5-3
(qcl + qdl) (qc2 corr + 9d2)
where
X = Mole or volume fraction of the organic in the calibration gas
that was diluted,
qcl = Flow rate of the calibration gas diluted in the first stage,
qdl = Flow rate of the diluent gas in the first stage,'and
qd2 = Flow rate of the diluent gas in the second stage.
9- Prepare two more calibration standards from the high concentration cylin-
der gas sufficient to bracket the expected concentration in the source
samples.
10. Analyze the calibration standards following the procedures described in
Subsection 5-1-1 for commercial gas cylinder mixtures. Use a pump on the
outlet side of the sample loop to flush the standards through the loop at
100 cc/min for 30 seconds. Using '-a manometer connected to a tee on the
outlet of the sample loop, make certain that the sample loop pressure
during analysis of the calibration standards is equal to the loop pressure
during actual sample analysis.
11. Once the calibration curve is established, it is recommended, if available,
that an undiluted cylinder standard in the range of the standard curve be
analyzed to verify the dilution ratio. Analyze the cylinder and calculate
the sample area value by multiplying the peak area by the attenuation
-------
Section No. 3-16.5
Date June 30, 1988
Page 9
factor. Use the slope and the y-intercept derived from the linear regres-
sion equation and the sample area value to calculate the cylinder concen-
tration (Cs) by the following formula:
Y - b
Cs = Equation 5~l
where
Y = Sample peak area, area counts,
b = y-intercept of the calibration curve, area counts, and
S = Slope of the calibration curve, area counts /ppmv .
The calculated concentration of the undiluted cylinder standard, based on the
analysis and the calibration curve generated from the diluted standards, should be
within 10% of the true value of the undiluted cylinder. If this criteria cannot be
met, then the GC calibration should be checked, the diluted sample may be outside
the calibration range, or there is a problem with the dilution system used to
prepare the standards (e.g. the rotameters are out of calibration, etc.). Identify
the problem and correct it, or use one of the other approaches for preparing cali-
bration standards.
5.1.3 Preparation of Calibration Standards by Direct Gas Injection - This proce-
dure is applicable to organic compounds that exist entirely as a gas at ambient
conditions. The standards are prepared by direct injection of a known quantity of
a "pure" gas standard into a 10-liter Tedlar bag containing 5-0 liters of hydrocar-
bon-free air or nitrogen. If there is more than one target compound then multiple
component standards can be prepared by this method provided the relative elution
pattern for the compounds is known for the GC column being used. The following
procedures are used to prepare standards by direct gas injection:
1. Evacuate a previously leak checked, leakfree 10-liter Tedlar bag (also
checked for zero retention) equipped with a quick connect or equivalent
compatible to the connection on the Tedlar bag or the interface sample line
and preferably fitted with a septum-capped tee at the bag inlet (see Figure
5-5).
2. Fit a septum to the outlet of the gas cylinder containing the standard
component .
3- Meter 5-0 liters of hydrocarbon- free air or nitrogen into the bag at a rate
of 0.5 liter/min using a dry gas meter that has been calibrated in a manner
consistent with the procedure described in Subsection 2.1.2. At the start,
record dry gas meter pressure and temperature.
4. While the bag is filling, fill and purge a 0.5-ml gas-tight syringe with
the standard gas by withdrawing the gas from the cylinder through the
septum. Repeat the .fill and purge of the syringe seven times before final-
ly filling the syringe and capping the needle. with a GC septum. Allow the
syringe temperature, to equilibrate with the ambient temperature.
5. Immediately before injecting the gas into the bag through the septum,
remove the septum cap, and adjust the syringe to the desired volume by
expelling the excess gas. The syringe should now be at ambient pressure.
Inject the gas into the bag through the septum (through the side of the bag
if it has not been fitted with a septum), withdraw the syringe, and imme-
diately cover any resulting hole with a piece of masking tape or the equi-
valent.
-------
Septum
Tedlar Bag
Capacity
10 Liters
Dry Gas Meter
Nitrogen
Cylinder
no O C/D
(B PJ 0>
-------
Section No. 3.16-5
Date June 30, 1988
Page 11
6. Record the final dry gas meter temperature and pressure, turn off the
dilution gas, and disconnect the Tedlar bag; record the ambient
temperature and pressure on a data form such as the one shown in Figure
5.6.
7- Place the bag on a smooth surface, and alternatively depress opposite
sides of the bag 50 times to mix the gases in the bag.
8. Calculate the organic standard concentration in the bag (Cs) in ppmv using
the following formula.
' 293 x P, Ps x Tm
G. x IO6 x G.. x IO3 x
Ts x 760 Ts x Pm
Cs = - = - Equation 5~5
293 x P • v x y
~^ n> _ fn
v x y x - x io3
T x 760
where
G = Gas volume of organic compound injected into the Tedlar bag,
ml.
IO6 = Conversion to ppmv, ul/liter,
PS = Absolute pressure of syringe before injection, mm Hg,
Ts = Absolute temperature of the syringe before injection, °K,
Vm = Gas volume indicated by dry gas meter, liters,
? = Dry gas meter correction factor, dimensionless,
Pm = Average absolute pressure of the dry gas meter, mm Hg,
Tm = Average absolute temperature of dry gas meter, °K, and
IO3 = Conversion factor, ml/L.
Note: The syringe pressure and absolute temperature should equal the baro-
metric pressure and the absolute ambient temperature.
9- Prepare two more calibration standards sufficient to bracket the expected
concentration in the source samples.
10. Analyze the calibration standards following the procedures described in
Subsection 5-1-1 for commercial gas cylinder mixtures. Use a pump on the
outlet side of the sample loop to flush the standards through the loop at
100 cc/min for 30 seconds. Using a manometer connected to a tee on the
outlet of the sample loop, make certain that the sample loop pressure
during analysis of the calibration standards is equal to the loop pressure
during actual sample analysis.
5.1.4 Preparation of Calibration Standards by Liquid Injection - This procedure is
used to prepare gaseous standards in Tedlar bags from liquid organic compounds.
The liquid compounds used must be 99-9% mole pure or the purity must be known to
calculate the gaseous standard concentrations. If there is more than one target
compound, then multiple component standards can be prepared by this method provided
the relative elution pattern for the compounds is known for the GC column being
used. Use the procedure that follows to prepare standards by this technique.
1. Assemble the equipment shown in Figure 5-7 using a dry gas meter calibrated
following the procedure described in Subsection 2.1.2 and a water manometer
for the pressure gauge. All connections should be glass, Teflon, brass or
stainless steel with quick connects or equivalent, compatible to the con-
-------
Section No. 3.16.5
Date June 30, 1988
Page 12
Preparation of Standards in Tedlar Bags by Gas and Liquid Injection
Date:
Preparer: >77-
','ck
Purpose:
he Id
Organic Compound: rc^o^/./T^r^&'H^Le^i^
Compound Source: Fi^kt*- '• Compound Purity (P) : f?i
Gas: or Liquid: «-^''
t-% Compound Mole Weight (M) : /^iTg
Gas Injecti6n Mixture 1 Mixture 2 Mixture 3
Bag number or identification A// A
A//A A/
/A
Dry gas meter calibration factor (Y) . ' \ ' ' \ \
Final gas meter reading, liters / ) /
Initial -gas meter reading, liters /
Volume metered (Vm ) , liters
Ambient temperature, °C
Average gas meter temperature, °C
Absolute' gas meter temp. ; (T.m.) ,• °K
Barometric pressure (Pb ) , mm Hg
Average gas meter pressure, , mm Hg
Absolute gas meter press. (Pm)<, mm Hg
Gas volume injected (Gv), ml
Syringe -temperature (Tg ) , °K
Absolute, syringe pressure (P ) , mm Hg
Calculated concentration (Cs )
P x T
s rn
("!' V 1 0^ M
uv x iu x
*T v D
N 1s X ^m
c - -
Us
V x Y
Liquid Injection Mixture 1
Bag number or identification S - 1
Dry gas .meter calibration factor (Y)
Liquid volume injected (Lv), ul 2..OO
Calculated concentration (C ) 3-1, 7-
P ^ i/i v i n* v
°s b"-' X 1U "
M x V x Y x P
/ 1
(
\
\ \
}
/r
\
Q
s c a 1 c .
C - x 10
~s c o r r . " "w
P
\
I
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Mixture 2 Mixture 3
3-Z S
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-3
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00
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Cs calc.
r - v 1 n
Us corr. - X 1U
P
Q%
Figure 5.6. Calibration data form for preparation of standards in Tedlar bags by
gas and liquid injection.
-------
SYRINGE
11
BOILING
WATER
BATH
-^-SEPTUM
MIDGET IMPINGER
ETER
NITROGEN CYLINDER
TEDLAR BAG
CAPACITY
50 LITERS
Figure 5-7. Apparatus for preparation of calibration standards by liquid
injection.
no o co
» 0)
ft O
(D rr
H- «-( O
OJ C 3
(0 -Z
o
oo .
O
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OOU1
-------
Section No. 3.16.5
Date June 30, 1988
Page 14
nection on the Tedlar bag or the interface sample line, for connection to
the Tedlar bag.
2. Allow the liquid organic compound to come to ambient temperature, and
determine the density of the liquid by weighing the liquid in a tare-
weighed ground-glass stoppered 25~ml volumetric flask or ground-glass
stoppered specific gravity bottle. Calculate the density in terms of
g/ml. As an alternative, use a literature value of the density of the
liquid at 20 °C.
3.. Leak check the system by pressurizing it to 5 to 10 cm (2 to 4 in.) H20
and shutting off the diluent gas supply. The system is leakfree if there
is no change in the pressure after 30 seconds. If the leak check is
good, release the pressure. If the system fails the leak check, locate
the leak using a soap solution and repair the leak.
4. Connect a quick connect or equivalent, compatible to the connection on
the Tedlar bag or the interface sample line, to a leakfree uncontaminated
50-liter Tedlar bag. Evacuate the bag.
5. Turn on the hot plate and bring the water to a boil. :
6. Connect the bag to the impinger outlet.
7. Record the initial meter reading and temperature. Open the diluent
supply valve, and adjust the flow rate to about 3 liters/minute so that
the bag will fill in about 15 minutes. .Record the meter pressure and
temperature and the barometric pressure at the start on a form such as
the one shown in Figure 5-5-
8. Use a clean 1.0- or 10-microliter syringe with a needle of sufficient
length to inject the liquid below the air inlet branch of the tee on the
midget impinger.
9. Fill the syringe to the desired volume with the organic liquid, and
inject the liquid by inserting the needle through the septum until the
needle is below the air inlet. Depress the syringe plunger completely
over a period of about 10 seconds and withdraw the needle. NOTE: When
dispensing liquid from a syringe, take care to account for the volume of
liquid present in the syringe needle. In general, the potential error
resulting from the volume of the needle is most conveniently avoided by
ensuring that the needle volume is completely full of liquid upon
filling the syringe and dispensing from it. If air pockets exist in the
.syringe after filling, this will be almost impossible.
10. When the bag is almost filled, record the water manometer pressure. Turn
off the diluent gas supply, and disconnect the bag. To equilibrate the
contents in the bag, either set the bag aside for an hour or massage the
bag by alternately depressing opposite sides of the bag 50 times.
11. Record the final meter reading and temperature. Calculate the con-
centration of the calibration standard (Cs) in the bag in ppmv using the
following formula.
Lv
— x p x 24.055 x 106
M Lv x p x Tm
Cs = = 6.24 x 10A x Equation 5-6
293 x Pm M x Vm x y x Pm
V x Y x x 103
Tm x 760
-------
Section No. 3-16.5
Date June 30, 1988
Page 15
where
V = Gas volume indicated by dry gas meter, liters,
L = Volume of liquid organic injected, ul,
M = Molecular weight of the organic compound, g/g-mole,
p = Organic liquid density, g/ml,
24.055 = Ideal molar gas volume at 293 °K and 760 mm tig, liters/g-
mole,
106 = Conversion to ppmv, ul/liter,
103 = Conversion factor, ul/ml, and
y = Conversion factor for dry gas meter.
12. When using a liquid standard that is not 99-9$ pure, use the following
formula to correct the calculated concentration of the calibration standard
(Cs corr) in PPmv.
Cs calc
Cs corr = x P Equation 5-7
100%
where
Cs corr = Corrected calibration standard concentration, ppmy ,
Cs calc = Calculated calibration standard concentration (Cs), ppmv ,
and
P = Purity of liquid organic compound, percent.
13. Prepare two more calibration standards sufficient to bracket the expected
concentration in the source samples.
14. Analyze the calibration standards following the procedures described in
Subsection 5-1-1 for commercial gas cylinder mixtures. Use a pump on the
outlet side of the sample loop to flush the standards through the loop at
100 cc/min for 30 seconds. Make certain that the sample loop pressure
during analysis of the calibration standards is equal to the loop pressure
during actual sample analysis.
An alternative procedure, subject to the approval of the Administrator, for
preparing gaseous standards from liquid organics substitutes a heated GC injection
port for the midget impinger setup and, due to the high back pressure of the injec-
tion port, a calibrated mass flowmeter for the dry gas meter.
5.1.5 Development of Relative Response Factors and Relative Retention Factors-
For emission tests where on-site GC analysis involving more than one organic com-
pound will be conducted, the development and use of relative response factors and
relative retention times is recommended. In the laboratory, gaseous calibration
standards are prepared for each target organic compound and analyzed by one of the
techniques described in the previous subsections. Choose one of the target com-
pounds or prepare and generate another calibration curve for a different organic
compound to be used to calculate the relative response factors and retention times.
The compound selected should exhibit a retention time comparable to the other
target compounds, should be stable, and/or easy to prepare and use in the field.
This procedure must be verified in the laboratory prior to field testing.
The relative response factors are calculated by dividing the slopes of the
target compound calibration curve by the slope of the selected organic calibration
curve. The y-intercept from the regression equation is ignored in calculating the
relative response factors. It should be noted that a very large y-intercept
-------
Section No. 3.16.5
Date June 30, 1988
Page 16
(greater than 5% of the slope) for any compound may adversely affect the validity
of this calibration technique. During analysis of field samples, the selected
organic compound can be used to calibrate the GC detector response and column
performance. The response factor determined in the field for the selected organic
is used to calculate the field response factors for the other target compounds
using the relative response factors determined previously in the laboratory. The
same approach is used, to predict the retention times of target compounds in the
field using the selected compound retention time determined in the field and the
relative retention times for the target compounds determined in the laboratory. Use
the following procedures to develop relative response factors and relative reten-
tion times.
1. Generate, at the minimum, a three-point calibration curve for each target
organic compound using gaseous standards following the procedures described
in the preceding subsections. Record the retention time of each compound.
2. Select one of the target compounds, preferably with a retention time be-
tween the other target compounds, or generate another calibration curve,
with a minimum of three points, for a non- target organic compound with a
comparable retention time. Select the standard compound to be used in the
field based primarily on the ease of use. Determine the retention time of
the selected compound (if not already determined) . Measure the carrier gas
flow rate using a bubble-type flowmeter or other suitable flowmeter.
3- Inject a sample of the diluent gas, and determine the retention time of the
unretained diluent peak. This is needed to calculate the relative reten-
tion by the following formula:
rx/s = - Equation 5-8
(tRsi - fcMi)
where
rx/s = Relative retention time based on adjusted retention volumes of the
target compounds and the selected compound, cc/cc,
tRxi = Initial retention time of compound x, seconds,
tMi = Initial retention time of unretained diluent gas peak, seconds,
and
tRsl = Initial retention time of selected organic compound, seconds.
4 . Calculate the relative response factor for each target compound relative to
the compound selected in step 2 using the following formula.
ms
FRx = — . Equation 5-9
mx
where
FRx = Relative response factor for compound x, dimensionless ,
ms = Slope from the calibration curve regression equation for the
selected organic compound, area counts/ppmv , and
mx = Slope from the calibration curve regression equation for
compound x, area counts/ppm .
-------
Section No. 3.16.5
Date June 30, 1988
Page 17
5. To verify that the relative response factors are correct, simulate the
' transportation of the GC to the field by turning off the detector, the GC
oven and the carrier gas flow overnight or longer. After the simulated
period has elapsed, turn on the GC, the carrier gas, and the detector, and
establish the analytical conditions that were used to generate the relative
' response factors. Measure the carrier gas flow rate. . ... .. ..-
6: Recalibrate the GC by generating a three-point calibration curve using the
selected organic compound, analyze each of the target compound calibration
standards, and a diluent gas sample. Calculate the concentration of each
target compound using the relative response factor for the compound and the
slope from the new calibration curve determined for the selected organic
compound with the following formula.
Yx
C = x FD Equation 5~10
X K X
ID
where
C = Calculated concentration of compound x calibration standard,
Yx = Detector response for compound x calibration standard, area
counts,
ms t d = Slope from new calibration curve generated for selected
organic standard compound, area counts/ppmv, and
FRx = Relative response factor for compound x, dimensionless.
The calculated value for each target compound using the compound's relative
response factor must be within 5% of the actual standard concentration for
• this technique to be used for that compound.
7. Determine the predicted retention times for the target compounds using
their relative retention times and the retention time determined for the
selected organic compound using the following formula:
rrxf = ((rTsf - tMf ) x rx/s) + fcMf Equation 5-11
where
rTxf = Calculated retention time for compound x using the relative
retention time factor, seconds,
rTsf = Measured retention for selected organic compound during
second analysis, seconds, and
tMf = Measured retention time of unretained diluent gas peak during
second analysis, seconds.
The calculated retention time for the target compounds should agree within
• one second or 2%, whichever is greater, of the actual retention time seen
for the target compounds during the second analysis.
8. Record all data on a form such as the one shown in Figure 5-8.
5.1.6 Calibration Standards for Adsorption Tube Samples - The calibration stan-
dards necessary for the analysis of adsorption tube samples differ from the stan-
dards described in the previous subsections in that the adsorption tube standards
are liquid rather than gaseous. The liquid standards can be prepared directly in
the desorption solvent following the procedures described in the methods refer-
enced in Table F or, subject to the approval of the Administrator, on blank adsorp-
-------
Section No. 3.16.5
Date June 30, 1988
Page 18
Development of Relative Response Factors and Relative Retention Factors
Date: 2-/2~b /&& Preparer: \7- 0?oo
Target Compound: Perchloroe'ttwitA**?-
Surrogate Compound: -Lsobnifje-
Target Compound Calibration Data
First analysis/verify analysis
Standard concentration
Flow rate through loop (ml/min)
Liquid injection volume (tubes)
Injection time (24-hr clock)
Chart speed
Detector attenuation
Peak retention time (tRxi/tRxf)
Peak retention time range
Peak area
Peak area x atten. factor (Yi/Yx
Verification analysis conc.(Cx)
Percent deviation from actual
Calculated retention time (rTxf)
Percent deviation from actual
Linear regression equation; slope
Surrogate Calibration Data
First analysis/second analysis
Standard concentration
Flow rate through loop (ml/min)
Liquid injection volume (tubes)
Injection time (24-hr clock)
Chart speed
Detector attenuation
Peak retention time (tRsi/tRsf)
Peak retention time range
Peak area
Peak area x attenuation factor
dri £^ Purpose
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Type of Standard
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Data form for development of relative response and relative retention
factors.
-------
Section No. 3.16.5
Date June 30, 1988
Page 19
tion tubes and then desorbed. Both methods require similar preparation and analy-
sis of standards and desorption efficiency samples, but the way the calibration
curve is generated is different.
For calibration standards prepared directly in the desorption solvent, the
standards are used to generate the calibration curve, and the desorption efficiency
is determined separately. The calculated desorption efficiency is then used to
correct the analytical results for the emission test samples. The disadvantage of
this method is that the desorption efficiency may not be constant for each level.
This can result from a constant amount of analyte being retained by the adsorbent,
instead of an amount proportional to the total amount of analyte on the adsorbent.
When using the desorption efficiency to correct each analytical result, the analyst
must use the desorption efficiency determined for the concentration level closest
to that of the sample.
For calibration standards prepared on absorbent material, the desorbed solu-
tions are used to generate the calibration curve. By this procedure, the desorp-
tion efficiency is already taken into account when calculating the organic compound
catch of the adsorption tube samples. Liquid calibration standards must also be
prepared to calibrate the GC to determine if the desorption efficiency is greater
than 50%- The advantage of this method is that both level-dependent or absolute
amounts of organic compounds not desorbed from the adsorbent are automatically
taken into consideration.
For maximum accuracy, preparation of standards directly in the desorption
liquid or on adsorbent will require the preparation of a relatively large volume of
a high concentration working standard from which the calibration standards are
prepared. The working standard should be 100 times more concentrated than the
highest concentration calibration standard. Three levels of calibration standards
should be prepared to bracket the expected concentration of the liquid resulting
from desorption of actual samples. The concentration of the sample desorption
liquid will depend on the catch weight of the target organic compound(s) and the
amount of desorption liquid used (1.0 ml per 100 mg of adsorbent material). The
catch weight will in turn depend on the sample volume of flue or duct gas drawn
through the tubes and the concentration of the emission source. Use the following
formula to estimate the concentration (Cs), in ug/ml, of the midrange liquid stan-
dard that will be approximately equal to the actual samples:
V.d X Cc X M
Cs = Equation 5-12
24.055 x Ld
where
V ed = Predicted gas sample volume, liters,
Cc = Concentration of the organic compound at the source, ppmv
(ug-moles/g-mole),
M = Molecular weight of organic compound, ug/ug-mole,
24.055 = Ideal molar gas volume at 293 °K and 760 mm Eg, liters/g-mole, and
Ld = Volume of desorption liquid, ml.
The preliminary survey sample results should be used to calculate the required
calibration standard concentrations.
To prepare adsorption tube standards, use the procedure described in the refer-
enced method or the alternative procedure, subject to the prior approval of the
Administrator. Regardless of which type of calibration standard is selected, use
the following procedures to prepare the standards:
-------
Section No. 3-16.5
Date June 30, 1988
Page 20
1. Prepare a working standard for each organic compound by weighing each com-
pound into an individual tare-weighed ground-glass stoppered 250-ml volume-
tric flask. Dissolve the compound in the proper desorption solvent speci-
fied by the referenced method in Table E of the Method Highlights Section.
Dilute the solution to volume. Refrigerate the working standard when not
being used. '
2. Using a clean microliter syringe, transfer the required amount of working
standard to a vial equipped with a Teflon-lined septum top, and add suffi-
cient desorption solvent to achieve a final volume equal to the volume of
desorption solvent required for actual samples. Cap the vial with the
top, shake the vial to mix the contents. NOTE: When dispensing liquid from
a syringe, take care to account for the volume of liquid present in the
syringe needle. In general, the potential error resulting from the volume
of the needle is most conveniently avoided by ensuring that the needle
volume is completely full of liquid upon filling the syringe and dispensing
from it. If air pockets exist in the syringe after filling, this will be
almost impossible.
3. Establish the optimum GC conditions determined during the analysis of the
• preliminary survey samples.
4. Select a suitably sized injection syringe (5~ or 10-ul), and flush the
syringe with acetone (or some other suitable solvent if acetone is the
standard component) to clean the syringe.
5. Flush the syringe with standard solution by withdrawing a syringe full of
the solution from the septum vial, and dispensing the solution into a
beaker containing charcoal adsorbent.
6. Refill the syringe with standard solution, withdraw the syringe from the
vial, and wipe the syringe needle with a laboratory tissue.
7. Adjust the syringe volume down to the desired amount (see NOTE under Step
2) , and inject into the GC. Note the time of the injection on the strip
chart recorder and/or actuate the electronic integrator. Also, record the
standard concentration, detector attenuation factor, chart speed, injection
port temperature, column temperature and identity, and the carrier gas type
and flow rate on the form shown in Figure 5-9- It is also recommended that
the same information be recorded directly on the chromatogram. Record the
operating parameters for the particular detector being used.
8. After the analysis, determine the retention time of the standard component
and determine the peak area. Repeat the injection of the first liquid
standard until the area count from two consecutive injections yield area
counts within 5 percent of their average.
9. Multiply the average area count of the consecutive injections by the atten-
uation factor to get the calibration area value for that standard concen-
tration.
10. Repeat the procedure for the other standard concentrations.
11. Prepare a plot with the standard concentration (Cs) along the abscissa (x-
axis) versus the corresponding calibration area values along the ordinate
(y-axis). Perform a regression analysis to calculate the slope and the y-
intercept. Draw the least squares line on the plot.
To determine the desorption efficiency for the target organic compound(s)
requires spiking the target organic compound(s) onto the absorbent material and
desorbing the compound (s) using the same procedures that will be used for actual
samples; the desorption solution is then analyzed. The spikes should be prepared
at three levels in the range of the source samples. The following procedures are
used to determine the desorption efficiency:
-------
Section No. 3.16.5
Date June 30, 1988
Page 21
1. Place an amount of adsorbent material equivalent to the amount used for
actual tube samples in a vial with a Teflon-lined septum cap. Prepare ten
vials (three sets of triplicates and one blank).
2. Using a clean microliter syringe, aliquot from the working standard solu-
tion, in triplicate into each set of vials, an amount of spike equal to
each level of calibration standard.
3. Cap each vial immediately after spiking, and- allow the vials to sit undi-
sturbed for the 30 minutes.
4. To desorb the spiked organic compound(s), dispense the appropriate volume
of desorbent solvent and treat the vials as specified by the referenced
method (Table E). Prepare a blank vial containing adsorbent and desorption
solvent only.
5. Analyze the desorption solutions following steps 4 through 8 used above for
the calibration standards. Record the data on the form shown in Figure
5-9.
6. Multiply the average area count of the consecutive injections by the atten-
uation factor to get the area value for that sample. NOTE: Attenuation
factors which affect the plot traced, but not the area count returned by
an electronic integrator should not be multiplied by the average area
count. Observe the effect of attenuation changes made at the console of a
specific electronic integrator to determine the appropriate course of
action.
7. If the desorption solutions are to be used to generate the calibration
curve, then plot the expected standard solution concentrations on the ab-
scissa (x-axis) and corresponding area value on the ordinate (y-axis).
Perform a regression analysis and draw the least squares line on the plot.
NOTE: If the desorption efficiencies of the selected solvent vary with
concentration for any of the organics to be analyzed, the relationship
between the expected standard solution concentrations and the corresponding
area value will not be strictly linear. Evaluate the linearity of the
resulting plot using control samples, and obtain the prior approval of the
Administrator before utilizing a least squares line generated from such
data.
8. Calculate the desorption efficiency (DE), in percent, for each level of
spike using the calibration area for the corresponding standard prepared
directly in the desorption solvent using the following formula:
As - Ab
DE = x 100% Equation 5-13
AC .
where
AS = Average area value for desorption carried out at given concentration
level, area counts,
Ad = Average area value for desorption carried out on blank sample, area
counts, and
AC = Average calibration area value for the corresponding standard level
prepared directly in the desorption solvent, area counts.
The desorption efficiency achieved at each level must be greater than $0% for
the adsorption tube sampling and analytical method to be acceptable. If adsorption
tubes have become the only remaining sampling option, and the 50% criteria cannot
-------
Section No. 3.16.5
Date June 30, 1988
Page 22
Preparation of Liquid Standards and Desorption Efficiency Samples
Date: Z/23/68 Preparer: xT".
*
Purpose:
Organic Compound:
Compound Source:
Adsorbent Material:
Gas:
or Liquid:
_ _
Compound Purity (P) : f*?f- % Compound Mole Weight- (M) :
Batch No: /^o Desorption Solvent: £//•,
Standards in Solvent
Desorption solvent volume (Vs), ml
Compound spike amount (Vo), ul
Organic compound density (p), ug/ul /. fc2-S
Standard concentration (C ), ug/ml
Mixture 1
4.00
4.00
Mixture 2
R.OO
3.
Mixture 3
4-. 00
/Z. 00
Standards on Adsorbent Mixture 1
Adsorbent amount, g
Compound spike amount (V0), ul
Organic compound density (p) , ug/ul
Desorption solvent volume (Vs ) , ml
Desorption time, min.
Standard concentration (Cs ) , ug/ml
6.&DD
A-.OO
/, 0>23
4. no
30
/•t>2-
Mixture 2
0-800
6.00
1, (p2"b
4-. oo
30
3.E5"
Mixture 3
0-800
/3-.OO
1 . 6>23
•4. 00
5O
^ 4«f
Blank
Q.60D
4.00
O
GC Operating Conditions
Injection port temperature, .°C
Carrier gas flow rate, ml/min
Column temperature:
Initial, °C
Program rate, °C/min
Final, °C
70 -A
/ CO
P^
Chromatographic Results
Injection time, 24-hr clock
Distance to peak, cm
Chart speed, cm/min
Retention time, min
Attenuation factor
Standards in desorption solvent:
Peak area (Ac), area counts
Standards and blank from
adsorbent material:
Peak area (As and Ab),
area counts
Mixture 1 Mixture 2
H: ^(* /5-'04-
Mixture 3 Blank
/5V 5?
/£>
/O
/O
4.7^
4.73
3-
701
544
Desorption Efficiency Calculation
Desorption Efficiency (DE), %
Mixture 1 Mixture 2 Mixture 3
g2.8
77.
'Vo x p x P
C =
As - Ab
DE = x 100#
Vs x 100%
Figure 5-9- Data form for preparation of liquid standards and desorption
efficiency samples for adsorption tube analysis.
-------
Section No. 3.16.5
Date June 30, 1988
Page 23
be met, then, subject to the prior approval of the Administrator, explore more
vigorous desorption techniques such as longer desorption times, sonification of the
vials during desorption, and/or other desorption solvents.
5.2 Audit Sample Analysis
After analysis of the calibration standards, and generation of a calibration
curve, conduct the analysis of the audit cylinder(s). Audit samples should be
introduced into the GC by the same procedure used for the calibration standards. If
possible, the audit sample should be introduced into the probe for the direct and
dilution interface techniques. The audit sample analysis must agree within 10$ of
the actual concentration of the audit sample before sample analysis can begin. If
the audit criteria is not met, first try recalibrating the GC with the existing
standards, and then reanalyze the audit sample(s). If the 10$ criteria still
cannot be met, remake the standards, recalibrate the GC, and reanalyze the audit
sample until the criteria is met or a representative of the Administrator decides
differently.
5.3 Sample Analysis
After the GC has been calibrated and the analysis of the audit sample (s) has
been conducted successfully, the samples can be analyzed. Use the same procedures
for sample analysis that were used to analyze the calibration standards. Record
the GC conditions and the analytical data on the form provided in Figure 5-1- The
following subsections describe the procedures for analyzing Tedlar bag samples,
direct and dilution interface samples, adsorption tube samples, and heated syringe
samples.
5.3-1 Analysis of Bag Samples - The following procedures are to be used to analyze
emission samples collected in Tedlar bags using a GC calibrated with gaseous cali-
bration standards prepared following one or more of the procedures described in
Subsection 5-1-
1. Attach a quick connect, or similar connecting device that is compatible
with the connection on the Tedlar bag to the gas sampling valve on the GC.
Attach a manometer connected to a tee on the outlet of the sample loop.
2. With the gas sampling valve in the load position, attach the first Tedlar
bag sample to the valve. Use a pump on the outlet side of the sample loop
to flush the sample through the loop at 100 cc/min for 30 seconds.
3. Turn off the pump, allow the sample loop to return to the same pressure
used during calibration standard analysis, and immediately switch the valve
to the inject position.
4. Note the time of the injection on the strip chart recorder and/or actuate
the electronic integrator. Also, record the sample identity, detector
attenuation factor, chart speed, sample loop temperature, column tempera-
ture and identity, and the carrier gas type and flow rate on a data form
such as Figure 5-1- It is also recommended that the same information be
recorded directly on the chromatogram. Record the operating parameters for
the particular detector being used.
5. Examine the chromatogram to ensure that adequate resolution is being
achieved for the major components of the sample. If adequate resolution is
not being achieved, vary the GC conditions until resolution is achieved,
and reanalyze the standards to recalibrate the GC at the new conditions.
6. After conducting the analysis with acceptable peak resolution, determine
the retention time of the sample components and compare them to the reten-
-------
Section No. 3.16.5
Date June 30, 1988
Page 24
tion times for the standard compounds. To qualitatively identify an indi-
vidual sample component as a target compound, the retention time for the
component must match within 0.5 seconds or 1%, whichever is greater, of the
retention time of the target compound determined with the calibration
standards.
7. Repeat the injection of the first sample until the area count for each
identified target compound from two consecutive injections give area counts
within 5 percent of their average.
8. Multiply the average area count of the consecutive injections by the atten-
uation factor to get the area value for that sample, and record the area
value on the data form provided in Figure 5-1- NOTE: When dispensing
liquid from a syringe, take care to account for the volume of liquid
present in the syringe needle. In general, the potential error resulting
from the volume of the needle is most conveniently avoided by ensuring
that the needle volume is completely full of liquid upon filling the
syringe and dispensing from it. If air pockets exist in the syringe after
filling, this will be almost impossible.
9- Repeat the procedure for the other two samples collected at the same sampl-
ing location.
10. Immediately following the analysis of the last sample, reanalyze the cali-
bration standards, and compare the area values for each standard to the
corresponding area values from the first calibration analysis. If the
individual area values are within 5# of their mean value, use the mean
' values to generate a final calibration curve for determining the sample
concentrations. If the individual values are not within 5# of their mean
values, generate a calibration curve using the results of the second analy-
sis of the calibration standards, and report the sample results compared to
both standard curves.
Determine the bag sample water content by measuring the temperature and the
barometric pressure'near the bag. Use water saturation vapor pressure chart, assum-
ing the relative humidity of the bag to be 100% unless a lower value is known, to
determine the water vapor content as a decimal figure (% divided by 100). If the
bag has been heated during sampling, the flue gas or duct moisture content should
be determined using Method 4.
5-3-2 Analysis of Direct Interface Samples - Prior to analysis of the direct
interface sample, the GC should be calibrated using a set of gaseous standards
prepared by one of the techniques described in Subsection 5-1 and a successful
analysis of an audit sample should be completed. If possible, the audit samples
should be introduced directly into the probe. Otherwise, the audit samples are
introduced into the sample line immediately following the probe. The calibration
is done by disconnecting the sample line coming from the probe, from the gas sampl-
ing valve sample loop inlet, and connecting the calibration standards to the loop
for analysis. During the analysis of the calibration standards and the audit
sample(s), make certain that the sample loop pressure immediately prior to the
injection of the standards is at the same pressure that will be used for sample
analysis. To analyze the direct interface samples after GC calibration, use the
following procedures:
1. Reconnect the sample line to the inlet of the gas sample loop, switch the
valve to the load position, and turn on the sampling pump. Adjust the
sampling rate to at least 100 cc/minute, and, for the first sample, purge
the sample line long enough to flush the sample loop and the preceding
volume of tubing a minimum of 7 times.
-------
Section No. 3.16.5
Date June 30, 1988
Page 25
2. After purging the sampling system and the sample loop, decrease the sample
flow using the needle valve downstream of the loop until the loop pressure,
measured by a water manometer connected to a tee at the outlet of loop, is
equal to the pressure used during calibration.
3- Once the loop is at the correct pressure, immediately switch the sample
valve to the inject position. Note the time of the injection on the strip
chart recorder and/or actuate the electronic integrator. The flow through
the sample line can be returned to lOOcc/min after sample injection, and,
after the unretained compounds are detected, the gas sample valve can be
switched back to the load position. The system will then be ready to
inject the second sample as soon as the first analysis is completed.
4. Record the sample identity, detector attenuation factor, chart speed,
sample loop temperature, column temperature and identity, and the carrier
gas type and flow rate on a form such as Figure 5-1- It is also recom-
mended that the same information be recorded directly on the chromatogram.
Record the operating parameters for the particular detector being used.
5- Examine the chromatogram to ensure that adequate resolution is being
achieved for the major components of the sample. If adequate resolution is
not being achieved, vary the GC conditions until resolution is achieved,
and reanalyze the standards to recalibrate the GC at the new conditions.
6. Immediately after the first analysis is complete, repeat steps 2 and 3 to
begin the analysis of the second sample.
7. After conducting the analysis of the first sample with acceptable peak
resolution, determine the retention time of the sample components and
compare them to the retention times for the standard compounds. To quali-
tatively identify an individual sample component as a target compound, the
retention time for the component must match, within 0.5 seconds or 1%,
whichever is greater, the retention time of the target compound determined
with the calibration standards.
8. At the completion of the analysis of the second sample, determine if the
area counts for the two consecutive injections give area counts within 5
percent of their average. If this criterion cannot be met due to the
length of the analysis, and the emissions are known to vary because of a
cyclic or batch process, then the analysis results can still be used with
the prior approval of the Administrator.
9. Analyze a minimum of three samples collected by direct interface to consti-
tute an emissions test.
10. Immediately following the analysis of the last sample, reanalyze the cali-
bration standards, and compare the area values for each standard to the
corresponding area values from the first calibration analysis. If the
individual area values are within 5% of their mean value, use the mean
values to generate a final calibration curve to determine the sample
concentrations. If the individual values are not within 5# of their mean
values, generate a calibration curve using the results of the second analy-
sis of the calibration standards, and report the sample results compared to
both standard curves.
5-3-3 Analysis of Dilution Interface Samples - For the analysis of dilution inter-
face samples, the procedures described for direct interface sampling in Subsection
5-3-2 should be followed, with the addition of a check of the dilution system.
-------
Section No. 3-16.5
Date June 30, 1988
Page 26
Prior to any sample analysis, the GC must first be calibrated, followed by the
dilution system check and an analysis of the audit sample(s). The audit sample(s)
are introduced preferably into the inlet to the dilution system or directly into
the gas sampling valve. Use the following procedures to conduct the check of the
dilution system:
1. Heat the dilution system to the desired temperature (0° to 3°C above the
source temperature) or, if the dilution system components can not tolerate
that temperature, to a temperature high enough to prevent condensation.
2. Adjust the dilution system to achieve the desired dilution rate, and intro-
duce a high concentration target gas into the inlet of the dilution system.
After dilution through the stage (s) to be used for actual samples, the
target gas should be at a concentration that is within the calibration
range.
3. Purge the gas sample loop with diluted high concentration target gas at a
rate of 100 cc/min for 1 minute, adjust the loop pressure measured by a
water manometer connected to a tee at the outlet of the loop, to the loop
pressure that was used during calibration and will be used during sample
analysis. The procedure for pressure adjustment for the sample loop will
vary with the type of dilution system that is used. In general, the loop
pressure can be lowered by reducing the flow into the loop and raised by
restricting the flow from the loop.
4. After achieving the proper loop pressure, immediately switch the gas sample
valve to the inject position.
5- Note the time of the injection on the strip chart recorder and/or actuate
the electronic integrator. Also, record the sample identity, detector
attenuation factor, chart speed, sample loop temperature, column tempera-
ture and identity, and the carrier gas type and flow rate on a form such as
Figure 5-1- It is also recommended that the same information be recorded
directly on the chromatogram. Record the operating parameters for the
particular detector being used.
6. Determine the peak area and retention time for the target compound used for
the dilution check, and calculate the area value using the detector attenu-
ation. Compare the retention time to the retention time of the target
compound calibration standard. The retention times should agree within 0.5
seconds or 1%, whichever is greater. If the retention times do not agree,
identify the problem and repeat the dilution check.
7- Calculate the concentration of the dilution check gas (Cd) using the fol-
lowing formula.
Y - b
Cd = x d Equation 5-1^
where
Y = Dilution check target compound peak area, area counts,
b = y-intercept of the calibration curve, area counts,
S = Slope of the calibration curve, area counts/ppmv, and
d = Dilution rate of the dilution system, dimensionless.
-------
Section No. 3.16.5
Date June 30, 1988
Page 27
8. If the calculated value for the dilution check gas is not within 10% of the
actual dilution check gas, then determine if the GC or the dilution system
is in error. Check the calibration of the GC by analyzing one of the cali-
bration samples directly bypassing the dilution system. If the GC is
properly calibrated, then adjust the dilution system, and repeat the analy-
sis of the dilution check gas until the calculated results are within 10%
of the actual concentration.
Once the dilution system and the GC are operating properly, analyze the audit
sample(s). Upon completion of a successful audit, the system is ready to analyze
samples following the procedures described in Subsection 5-3-2. To load the sample
from the dilution system may not require a pump on the outlet of the sample loop,
but calibration of the GC using standards prepared in Tedlar bags will require a
pump. The system should be configured so that the pump can be taken off line when
it is not needed.
5-3-4 Analysis of Adsorption Tube Samples - Prior to the analysis of adsorption
tube samples, the target compounds adsorbed on the adsorption material must be
desorbed. The procedures found to give acceptable desorption efficiencies deter-
mined in Subsection 5-1-4 should be used. The procedures for the analysis of the
sample desorption solutions are the same as those used for the standards. During
sample analysis, the sample collection efficiency must be determined. Use the
following procedures to determine the collection efficiency:
1. Desorb the primary and backup sections of the tubes separately using the
procedures found to give acceptable (50%) desorption efficiency for the
spiked adsorption material. Use the same final volume of desorption solu-
tion for the samples as was used for the standard solutions. If more than
one adsorption tube was used in series per test run, delay desorbing the
additional tubes until the analysis of the primary and backup section of
the first tube is complete, and the collection efficiency for the first
tube determined. Select the samples from the sampling run when the flue
gas or duct moisture was the highest and, if known, when the target com-
pound concentrations were the highest and analyze them first.
2. Calibrate the GC using standards prepared directly in desorption solvent or
prepared on adsorbent and desorbed.
3- Select a suitably sized injection syringe (5- or 10-ul), and flush the
syringe with acetone (or some other suitable solvent if acetone is a target
compound) to clean the syringe.
4. Flush the syringe with the desorption solution from the tube's backup
section by withdrawing a syringe full of the solution from the septum vial,
and dispensing the solution into a beaker containing charcoal adsorbent.
5- Refill the syringe with the backup section desorption solution, withdraw
the syringe from the vial, and wipe the syringe needle with a laboratory
tissue.
6. Adjust the syringe volume down to the amount used for injecting standards
and inject the sample into the GC. Note the time of the injection on the
strip chart recorder and/or actuate the electronic integrator. Also,
record the sample identity, detector attenuation factor, chart speed,
injection port temperature, column temperature and identity, and the carri-
er gas type and flow rate on the data form shown in Figure 5.1. It is also
recommended that the same information be recorded directly on the chromato-
-------
Section No. 3-16.5
Date June 30, 1988
Page 28
gram. . Record the operating parameters for the particular detector being
used.
7- After the analysis, determine the retention time of the major sample
components, and compare these retention times to the retention times deter-
mined for the target compounds during analysis of the standards. To quali-
tatively identify an individual sample component as a target compound, the
retention time for the component must match, within 0.-5 seconds or 1%,
whichever is greater, the retention time of the target compound determined
with the calibration standards. Determine the peak area for each target
compound identified in the sample. ,
8. Repeat the injection of the first sample until the area counts for each
identified target compound from two consecutive injections are within 5
percent of their average.
9. Multiply the average area count of the consecutive injections by the atten-
uation factor to get the area value for that sample.
10. Next analyze the desorption solution from the primary section of the same
adsorption tube following steps 4 through 9 above.
11. For each target compound, calculate the total weight (W), in ug, present in
each section, taking into account the desorption efficiency using the
formula below.
Wp or Wb = x — Equation 5~15
(Y - b) 1
- x —
S DE . . • .- '
where
Y = Average value for the target compound in the section (primary or
backup), area counts, • .
b = y-intercept from the three-point calibration curve for the target
compound, area counts,
S = Slope from the three-point calibration curve for the target
compound, area/ug, and
DE = Desorption efficiency (if standards prepared directly in
desorption solvent are used for calibration) .
12. Determine the percent of the total catch found in the primary section for
each target compound identified using the following formula.
px
E - - x 100$ Equation 5-16
cx
where
Ecx =
x, percent,
Catch of co
mbx = Catch of compound x in the backup section, ug.
Ecx = Collection efficiency of the primary section for target compound
mpx = Catch of compound x in the primary section, ug, and
-------
Section No. 3.16.5
Date June 30, 1988
Page 29
If the collection efficiency for the primary section for each target com-
pound identified is >_ 90%, then the collection efficiency for that compound
is acceptable. If the collection efficiency for all the target compounds
identified in the sample is acceptable, then the analysis of any additional
tubes used in series behind the first tube will not be necessary. Proceed
with the analysis of the other adsorption tube samples.
12. If the collection efficiency for any identified target compound is not
acceptable, then analyze the second tube (if used) connected in series and
determine the collection efficiency for that tube using the steps described
above. If the second tube does not exhibit acceptable collection and a
third tube was used, analyze the third tube. If acceptable collection
efficiency cannot be demonstrated for the sampling system, then the emis-
sion test using adsorption tubes will not be acceptable.
13. Immediately following the analysis of the last sample, reanalyze the cali-
bration standards, and compare the area values for each standard to the
corresponding area values from the first calibration analysis. If the
individual area values are within 5% of their mean value, use the mean
values to generate a final calibration curve for determining the sample
concentrations. If the individual values are not within 5# of their mean
values, generate a calibration curve using the results of the second analy-
sis of the calibration standards, and report the sample results compared to
both standard curves.
5.3-5 Analysis of Heated Syringe Gas Samples by Direct Injection - For the analy-
sis of samples collected in heated syringes, the GC will have to be equipped with
an injection septum fitted to the gas sampling valve sample loop inlet. Calibrate
the GC following one of the procedures described in Subsection 5 • 1 for gaseous
calibration standards. Analyze the heated syringe samples by the following proce-
dures :
1. Attach a GC septum to a quick connect, or equivalent, compatible with the
connector on the gas sampling valve, and attach this connector to the gas
sampling valve.
2. Insert the needle of the heated syringe through the septum, and purge the
sample loop by injecting a volume of the gas sample at least ten times
greater than the sample loop volume.
3. Allow the sample loop pressure, measured by a water manometer connected to
a tee on the outlet of the sample loop, to reach the same loop pressure
seen during analysis of the calibration standards, and immediately switch
the gas sample valve to the inject position.
4. Note the time of the injection on the strip chart recorder and/or actuate
the electronic integrator. Also, record the sample identity, detector
attenuation factor, chart speed, sample loop temperature and volume, column
temperature and identity, and the carrier gas type and flow rate on a form
such as Figure 5-l« It is also recommended that the same information be
recorded directly on the chromatogram. Record the operating parameters for
the particular detector being used.
5. Examine the chromatogram to ensure that adequate resolution is being
achieved for the major components of the sample. If adequate resolution is
not being achieved, vary the GC conditions until resolution is achieved,
and reanalyze the standards to recalibrate the GC at the new conditions.
-------
Section No. 3.16.5
Date June 30, 1988
Page 30
6. After conducting the analysis with acceptable peak resolution, determine
the retention time of the sample components and compare them to the reten-
tion times for the standard compounds. To qualitatively identify an indi-
vidual sample component as a target compound, the retention time for the
component must match, within 0.5 seconds or 1%, whichever is greater, the
retention time of the target compound determined with the calibration
standards.
7. Repeat the injection of the first sample until the area counts for each
identified target compound from two consecutive injections are within 5
percent of their average.
8. Multiply the average area count of the consecutive injections by the atten-
uation factor to get the area value for that sample.
9. Repeat the procedure for the other two samples collected at the same sampl-
ing location.
10. Immediately following the analysis of the last sample, reanalyze the cali-
bration standards, and compare the area values for each standard to the
corresponding area values from the first calibration analysis. If the
individual area values are within 5% of their mean value, use the mean
values to generate a final calibration curve for determining the sample
concentrations. If the individual values are not within 5% of their mean
values, generate a calibration curve using the results of the second analy-
sis of the calibration standards, and report the sample results compared to
both standard curves.
-------
Section No. 3.16.5
Date June 30, 1988
Page 31
Date Plant Name ' Sampling Location
Checks for Analysis of All Calibration Standards
A minimum of three concentration levels used for each target compound?
yes no. (The concentration used should bracket the expected
concentrations of the actual field samples.)
. Proper GC conditions established prior to standard analysis? yes no.
(For initial conditions use analytical conditions found to be acceptable
during preliminary survey sample analysis.)
Individual peak areas for consecutive injections within 5% of their mean for
each target -compound? yes no. (Repeat analysis of standards
until 5% criteria is met.)
Second analysis-, of standards after sample analysis completed? yes no.
Peak areas for repeat analysis of each standard within 5% of their mean peak
. area? yes no. (If no, then report sample results compared to both
standard curves.)
Checks for Calibrations using Commercial Cylinder Gases
Vendor concentration verified by direct analysis? yes no.
Sample loop purged for 30 seconds at 100 ml/min prior to injection of calibra-
tion standards? yes no.
Checks for Preparation and Use of Calibration Standards Prepared by Dilution
Dilution system flowmeters calibrated? yes no. (Calibrate following
procedure described in Subsection 2.1.3.)
Sample loop purged for 30 seconds at 100 ml/min prior to injection of calibra-
tion standards? yes no.
Dilution ratio for dilution system verified? yes no. (Analysis of
low concentration cylinder gas after establishing calibration curve
recommended to verify dilution procedure, but hot required, since audit
sample will also verify dilution ratio.)
Figure 5-10. Postsampling operations checklist.
-------
Section No. 3-16.5
Date June 30, 1988
Page 32
Figure 5.10 (Continued)
Checks For Preparation and Use of Calibration Standards by Direct Injection of
Gaseous Compounds or Liquid Injection
Tedlar bag used to contain prepared standard leak and contamination free?
yes no .
Dry gas meter used to fill bag calibrated? yes no. (Calibrate meter
following procedure described in Subsection 2.1.2.)
Organic standard material used for injection 99-9$ pure? yes no. (If
no, then determine purity and use to correct calculated calibration
standard concentration.)
Prepared standard allowed to equilibrate prior to injection? yes no.
(Massage bag by alternately depressing opposite ends 50 times.)
Sample loop purged for 30 seconds at 100 ml/min prior to injection of calibra-
tion standards? yes no.
Development of Relative Response Factors and Retention Times
Suitable target organic or surrogate compound selected? yes no.
(Select compound that is stable, easy to prepare in the field, and has a
retention time similar to the target organic compounds.)
Relative response factors and retention times verified in the laboratory prior
to actual field use? yes no. (If no, verify following the
procedure described in Subsection 5-1-4-)
Checks for Preparation, Use, and Determination of Desorption Efficiency for Adsorp-
tion Tube Standards
Organic standard material used for injection 99-9% pure? yes no. (If
no, then determine purity and use to correct calculated calibration
standard concentration.)
Correct adsorbent material and desorption solvent selected? yes no.
(Refer to Table B in Method Highlights Section for proper adsorbent
material and desorption solvent.)
Desorption efficiency determined for adsorbent to be used for field sampling?
yes no. (If no, follow the procedure described in Subsection
5.1.5.)
-------
Section No. 3.16.5
Date June 30, 1988
Page 33
Figure 5.10 (Continued)
Checks'for All GC Analysis of Field Samples
Check type of carrier gas used: helium , nitrogen , other
Carrier gas flow rate and pressure set correctly? yes no. (Carrier
gas flow rate and pressure set according to conditions developed during
.presurvey/ sample analysis and within limitations of the GC as specified
by GC manufacturer.)
Oxygen and hydrogen flow rate and pressure for FID correct? •_. yes _. no
. (Oxygen and-hydrogen gas flow.rate and pressure for FID set according to
conditions developed during presurvey sample analysis and within
limitations of the GC as specified by GC manufacturer.)
Individual peak areas.. for consecutive injections within 5% of their mean for
each target compound? yes no. (Repeat analysis of standards
until 5?» criteria is met.) , -...- . • •, \
Audit sample analyzed and results within 10% of actual value? yes no.
(If no, recalibrate GC and/or reanalyze audit sample.)
Checks Type of Standard Used for Tedlar Bag Sample Analysis
; '
Gas cylinders ._, dilution of gas cylinders , direct.gas injection ,
direct liquid injection• _. , and/or relative response factors and
retention times .
Checks.For GC Analysis Of Tedlar Bag Samples • • '
Sample loop purged for 30 sec. at 100 ml/min prior to injection of calibration
standards? yes no.
Stability of gas sample in Tedlar bag determined? yes- no. -..-. (Deter-
mine stability by conducting a second analysis after the first at a time
period equal to the,time between collection and the first analysis. The
change in concentration- between, the first and second analysis should be
less than 10%.) • , . :
Retention of- target compounds in Tedlar bag determined? yes no. (If
•no, then follow.the procedure described in Subsection 5.3.1.)
Check GC Interface Technique Used
J i " ' * : ' ' t " ' '
Direct Interface .•, 10:1 Dilution Interface , 100:1 Dilution Interface
-------
Section No. 3.16.5
Date June 30, 1988*
Page 34
Figure 5-10 (Continued)
. Checks For Suitability ,of GC Interface Technique
Analytical interference due to moisture content of source gas? yes no.
(Moisture in the source gas must not interfere with analysis in regard
to peak resolution according to EPA Method 625 criterion where the
baseline-to-valley height between adjacent peaks is less than 25$ of the
sum of the two adjacent peaks.)
Physical requirements for equipment met on-site? yes no. (The
physical requirements for the equipment include sheltered environment,
"clean", uninterrupted power source suited for equipment, and adherence to
safety aspects related to explosion risk areas.)
Source gas concentration below level of GC detector saturation? yes no.
(Concentrations delivered to the detector can be reduced by using smaller
gas sample loops and/or dilution interface.)
Sampling systems purged with 7 changes of system volume prior to sample
analysis? yes no.
Check Type(s) of Standards Used for Interface Techniques
Gas cylinders , dilution of gas cylinders , direct gas injection ,
direct liquid injection , and/or relative response factors and
retention times .
Checks For Dilution Interface Analytical Apparatus
Dilution rate verified (within 10%) by introducing high concentration gas
through dilution system and analyzing diluted gas? yes no.
(If dilution rate not verified, then first check calibration of GC by
reanalyzing a calibration standard and then adjust dilution system to give
desired ratio).
Sampling systems purged with 7 changes of system volume prior to sample
analysis? yes no.
Check Type of Standard Used for Adsorption Tube Analysis
Prepared directly in desorption solvent , and/or prepared on adsorbent and
desorbed .
Checks for GC Analysis of Adsorption Tube Samples
Desorption procedure used identical to procedure used to determine the
desorption efficiency? yes no.
-------
Section No. 3.16.5
Date June 30, 1988
Page 35
Figure 5-10 (Continued)
Collection efficiency determined for adsorption tubes used for actual field
sampling? yes no. (If no, then determine collection efficiency
following the procedures described in Subsection 5-3-4.)
Check Type of Standard Used for Analysis of Heated Syringe Samples
Gas cylinders , dilution of gas cylinders , direct gas injection ,
direct liquid injection , and/or relative response factors and
retention times
-------
Section No. 3.16.5
Date June 30, 1988
Page 36
Table 5.1. ACTIVITY MATRIX FOR SAMPLE ANALYSIS.
Characteristic
Acceptance limits
Frequency and method
of measurement
Action..if . .
requirements
are not met
Calibration
Standards
All calibrations
1) Standard analysis
performed under, same
GC conditions to be
used for,samples
2) Three-point
(minimum), calibra-
tion .curve generated
for each .target
compound
3) .Sufficient amount
of each standard to'
recalibrate after
samples are analyzed
Before analysis of
calibration standards
determine .samplei.ana- .
lysis conditions
Before analysis Ac-
quire or prepare stan-
dards for each target
•compound at three, •
levels
Prior to initial • ,
calibration and sample
analysis, determine-
amount needed
Reanalyze stan-
dards under con-
ditions to be
used for samples
Acquire or pre-
pare standards at
at three levels
to bracket
samples
Acquire..,or
prepare
enough :
standards
Commercial gas
cylinder mixtures
Certified by .direct
analysis (within 5$
of manufacturer,' s
value); three levels
bracketing samples
Prior ,to use,, check if
''independent analysis
conducted and accept-
able and standards,
will bracket samples
Procure certified
gas cylinders in
proper range
Gas standards from
high concentration
gas cylinders
Dilution ratio, of .:
dilution system i
verified .(optional)
with calculated val-
ue using calibration
curve within 10%
of actual cone,.
Prior to sample analy-
sis ; calibration curve
from standards verif-
ied by analysis of an
undiluted sample •
• Identify, and
correct problems
with dilution
system, and
remake, reana-
lyze, and re-
verify, standards
Standards prepared
by direct gas
injection
Gas injected 99-9%
pure, or calculated
standard concentra-
tion corrected for
gas impurity
When calculating stan-
dard concentration,
determine purity of
gas standard >
Use pure gas or
determine purity
Standards prepared
by liquid
injection ,
(Continued)
Liquid injected
99-9$ pure, or.
calculated standard
corrected 'for
liquid impurity
•When calculating.stan-
dard concentration,
determine purity of
liquid standard.
Use pure liquid
or determine
purity
-------
Table 5.1 (Continued)
Section No. 3.16.5
Date June 30, 1988
Page 37
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Calibration
Standards
Relative response
factors and rela-
tive retention
times
Proper target or
surrogate standard
selected for on-site
calibration; method
verified (calculated
results within 10%
of actual concentra-
tion)
When selecting stan-
dard choose stable,
easy to prepare stan-
dard with retention
time near or between
target compounds; ver-
fied following proced-
ures described in
Subsection 5-1-5
Select different
target or
surrogate
compound; if
procedure cannot
be verified
use calibration
standard for each
target compound
Standards prepared
for adsorption
tube samples'
1) Liquid injected
99.92 pure, or
calculated standard
corrected for
2) Acceptable
desorption effici-
ency for target com-
pounds on adsorbent
material (>50#)
When calculating stan-
dard concentration,
determine purity of
liquid standard
During calibration
standard analysis
determine desorption
efficiency for each
target compound (see
Subsection 5.1.5)
Use pure liquid
or determine
purity
Try longer de-
sorption times,
more vigorous
desorption condi-
tions , and/or
other desorbents
Audit sample
analysis
Analytical result
for audit sample
within 10% of actual
concentration
After initial cali-
bration and prior to
sample analysis, ana-
lyze audit sample
Reanalyze audit
sample, if not
acceptable, re-
make and reana-
lyze standards
Sample Analysis
All samples
1) Audit sample
analysis within
of actual cone.
2) Sample analysis
conditions the same
as conditions used
for analysis of
standards
Prior to sample ana-
lysis, analyze audit
sample
Prior to sample ana-
lysis check that ana-
lytical conditions are
the same as those used
for standard analysis
Analyze audit
sample
Establish the
same analytical
conditions used
during analysis
of standards
(Continued)
-------
Table 5.1 (Continued)
Section No. 3-16.5.
Date June 30, 1988
Page 38
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Sample Analysis
All samples
3) Retention times
for target compounds
identified in sample
within 0.5 seconds
or 1% of standards
4) Area counts for
consecutive injec-
tions of samples
within 5% of their
average for each
target compound
identified in sample
5) All three samples
constituting a test
analyzed together
6) After sample ana-
lysis , repeat analy-
sis of standards;
area counts for each
standard analysis
within 5# of their
mean
After analysis, deter-
mine retention times
for major components
in sample and compare
to standard retention
times
After second analysis
of a sample, calculate
average area for first
and second analysis
and percent difference
of single analysis
from the average
During sample analysis
After analysis of last
sample repeat standard
analysis; calculate
mean area counts and
percent difference for
each standard
Qualitative
identification
requires reten-
times within 0.5
seconds or 1%;
repeat analysis
Repeat sample
injections until
consecutive in-
jections are
achieved meeting
the 5% criteria
for each target
compound
Analyze remaining
samples
Report sample
results using
both curves, if
5# criteria not
met
Bag samples
1) Bag sample moist-
ure content deter-
mined
2) Stability check
conducted on bag
content (
-------
Table 5.1 (Continued)
Section No. 3.16.5
Date June 30, 1988
Page 39
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Sample Analysis
Direct interface
samples.
Two consecutive
injections give
area counts within
5# of their mean
After second analysis,
calculate average area
counts and percent
difference
Due to cyclic or
batch processes
and analysis
time, emission
levels may vary;
use results with
the prior appro-
val of the Ad-
ministrator
Dilution interface
samples
1) Dilution ratio
verified (results
from analysis of
high concentration
standard through
dilution system
within 10% of actual
concentration
2) Two consecutive
injections give
area counts within
5# of their mean
Prior to sample ana-
lysis analyze high
concentration gas
introduced through
dilution system
After second analysis,
calculate average area
counts and percent
difference
Identify problem;
recalibrate GC or
adjust dilution
system and repeat
analysis of high
concentration
gas
Due to cyclic or
batch processes
and analysis
time, emission
levels may vary;
use results with
the prior ap-
proval of the
Administrator
Adsorption tube
samples
Collection effici-
ency determined for
adsorption tubes
OQ% of each target
compound identified
caught on primary
section)
Desorb and analyze
primary and backup
sections separately
Analyze addi-
tional tube(s) if
used as backups
to first tube; if
criteria cannot
be met, test is
not valid
-------
Section No. 3.16.6
Date June 30, 1988
Page 1
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 per-
formed 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
entered should be included in the printout so it can be reviewed; 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 of numbers should be
performed in accordance with the ASTM 380-76 procedures. All calculations should
then be recorded on a calculation form such as the ones in Figures 6.1 and 6.2 for
analysis by gas or liquid injection, respectively.
6.1 Calculations for GC Analysis Using Gas Injection
The same equation can be used to calculate the concentration of each organic
in Method 18 samples whenever the sampling technique used yields a gaseous sample
which can be injected into the GC. These techniques are: (1) the integrated bag
sampling technique, (2) the heated bag sampling technique, (3) the prefilled bag
sampling technique, (4) the direct interface sampling technique, and (5) the dilu-
tion interface sampling technique. This equation is used to calculate the sample
concentration (Cc) in ppm on a dry basis as follows:
Cs Pr T, Fr K
Cc = Equation 6-1
Pi Tr (1 - Bws/K)
where
Cs = Concentration of organic from calibration curve, ppm,
Pr ~ Reference pressure, the barometric pressure or absolute sample loop
pressure recorded during calibration, mm Hg,
Ti = Sample loop temperature at time of sample analysis, °K,
Pi = Barometric or absolute sample loop pressure at time of sample analysis,
mm Hg,
Tr = Reference temperature, the temperature of the sample loop recorded
during calibration, °K,
Bws = Water vapor content of the stack gas, proportion by volume,
Fr = Relative response factor, if applicable (see Subsection 5.1.5), and
K = Dilution factor (applicable only for dilution interface and prefilled
bag sampling; for a 10 to 1 dilution, K = 10).
-------
Section No. 3.16.6
Date June 30, 1^88
Page 2
6.2 Calculations for GC Analysis by Liquid Injection
For Method 18, liquid injection GC analyses are used in conjunction with the
adsorption tube sampling procedure. The same general equations are typically used
to calculate the concentration of each organic in a sample collected on an adsorp-
tion tube. However, the tester is referred to the National Institute of Occupa-
tional Health and Safety (NIOSH) method (see Table B in the Method Highlights
Section) for specifics on calculations for particular organics. The general equa-
tions are shown below.
6.2.1 Sample Volume Corrected to Standard Conditions on a Dry Basis - The correct-
ed sample volume (V8td idry) is calculated as shown.
T P V P V
std rbar vm ^ rbar vm
vs = - = 0.3858 -
Pstd Ts (1 - Bws/K)' Ts (1 - BWS/K)'
Equation 6-2
where
Tstd/pstd = °-3858 °K/mm Hg,
Vm = Sample volume measured, L,
Pbar = Barometric pressure during sampling, mm Hg,
Ts = Temperature of sample gas, °K,
Bws = Water vapor of stack gas, proportion by volume, and
K = Dilution factor, if applicable.
'Note: Only apply this correction if a dessicant is not used.
6.2.2 Desorption Efficiency - Desorption efficiency (DE) for recovery of a speci-
fic compound using a certain solvent from an adsorption tube is calculated using
the following equation.
Q - B
r
DE = - Equation 6-3
where
Qr = Average peak area for spiked tubes,
Qa = Average peak area for spiked solutions, and
B = Average peak area for media blanks.
6.3.3 Concentration of Organic in Sample - The concentration (C) of the organic in
the sample in milligrams per dry standard cubic meter or micrograms per dry stand-
ard liter (mg/dscm or ug/dsL) is calculated using the following equation.
-------
Section No. 3.16.6
Date June 30, 1988
Page 3
(W, + Wb - Bf - BJK
C = Equation 6-4
Vstd * DE
where - .
W ' • = Mass of organic found in primary sorbent section, ug,
Wb = Mass of organic found in backup sorbent section, ug,
B = Mass of organic found in primary section of average media
blank, ug,
Bb = Mass of organic found in backup section of average media
blank, ug,
K = Dilution factor, if applicable (for a 10 to 1 dilution, K = 10),
vstd dry = Sample volume corrected to standard conditions and a dry
basis, L, and
DE = Desorption efficiency, decimal value.
6.2.4 Conversion to ppm - To convert the concentration in milligrams per dry
standard cubic meter (micrograms per dry standard liter) to ppm, the following
equation can be used.
r - 24.055 (dsL/g-mole gas) x C . ,
C = Equation 6-5
MW
where
C = Concentration of organic, ug/dsL or mg/dscm, and
MW = Molecular weight of organic, ug/ug-mole.
-------
• '<" Section No. 3.16.6
Date June 30, 1§88
Page 4
SAMPLE CONCENTRATION
Cs = l_ _£_ 0_ ppm, Pr = _?• JT3^ . SL mm Hg, T. = . 2>_ _7 0_ . _O °K,
K* = A/ _A . _, F/ = fi/A_ _
Cs Pr T. Fr K
Cc = - = __ _7^ _4 ppm Equation 6-1
pi Tr (1 - Bws/K)*
*If applicable.
Figure 6.1. Calculation form for GC analysis by gas injection.
-------
Section No. 3.16.6
Date June 30, 1988
Page 5
SAMPLE VOLUME, DRY BASIS AT STANDARD CONDITIONS
Vm = __ 2-5^ . 2- L, Pbar = J7 J[~+_ • j[ mm Eg,
P V
V = 0.3858 - — — - - = 2-^.0 L Equation 6-2
s t d i d r y _ - ^~^~ ^— _^_
Ts (1 - Bws/K)*
'If applicable.
DESORPTION EFFICIENCY
Qr = _# "L .1 • Qa = -1 _T_^ , B = ^
DE = (Qr - B)/Qa = 0 . _f_ _^ . Equation 6-3
SAMPLE CONCENTRATION
Wp = _6 1_ _k . 0_ ug, Wb = _/_ _£ ^ . _^ ug, Bp = ^_ ug,
B. = ^ ug, V .. = Z^.^L, DE = 0 . ^ 2- . .
(Wp + Wb - Bp - Bb)K
C = - = __ ^ J2_ • _*L mg/dscm or ug/dsL Equation 6-H
CONVERSION TO PPM
C = ___ . _ mg/dscm or ug/dsL, MW = __ ;£ _^ . _/ ug/ug-mole,
_ 24.033 (dsL/g-mole gas) x C / -Z_ -? _ t . £ _
Cppm = - =i^J - La - s - = __ LTL • ±Z PPm Equation 6-5
MW
Figure 6.2. Calculation form for GC analysis by liquid injection.
-------
Section No. 3.16.6
Date June 30, 1988
Page 6
Table 6.1. ACTIVITY MATRIX FOR CALCULATION CHECKS
Characteristic
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Analysis data
form
All data and calcu-
tions are shown
Visually check
Complete the
missing data
Calculations
Difference between
check and original
calculations should
not exceed round-off
error
Repeat all calcula-
tions starting with
raw data for hand
calculations; check
all raw data input
for computer calcu-
lations; hand calcu-
late one sample per
test
Indicate errors
on calculation
form, Figure 6.1
or 6.2
-------
Section No. 3.16.7
Date June 30, 1988
Page 1
7.0 MAINTENANCE
The normal use of emission-testing equipment subjects it to corrosive gases,
extremes in temperature, vibration, and shock. Keeping the equipment in good
operating order over an extended period of time requires knowledge of the equipment
and a program of routine maintenance which is performed quarterly or after 2830 L
(100 ft3) of operation, whichever is greater. In addition to the quarterly main-
tenance, a yearly cleaning of pumps and metering systems is recommended. Main-
tenance procedures for the various components are summarized in Table 7.1 at the
end of the section. The following procedures are not required, but are recommended
to increase the reliability of the equipment.
7.1 Pump
Several types of pumps may be used to perform Method 18; 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 translu-
cent; 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 a fiber
vane pump starts to run erratically or during the yearly disassembly, the head
should be removed and the fiber vanes changed. Erratic operation of a diaphragm
pump is normally due to either a bad diaphragm (causing leakage) or to malfunctions
of the valves, which should be cleaned annually by complete disassembly.
7.2 Dry Gas Meter
Dry gas meters should be checked for excess oil or corrosion of the components
by removing the top plate every 3 months. Meters 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
Rotameters should be disassembled and cleaned according to the manufacturer's
instructions using only recommended cleaning fluids every 3 months or upon erratic
operation.
7 A Manometer
The fluid in the manometers should be changed whenever there is discoloration
or visible matter in the fluid, and during the yearly disassembly.
7-5 Sampling Train
All remaining sampling train components should be. visually checked every 3
months and completely disassembled and cleaned or replaced yearly. Many items,
such as quick disconnects, should be replaced whenever damaged rather than checked
periodically. Normally, the best procedure for maintenance in the field is to have
on hand another entire unit such as a pump, Tedlar bags and containers, or heated
sample line rather than replacing individual components.
-------
Section No. 3.14-7
Date June 30, 1988
Page 2
7.6 Gas Chromatograph
Maintenance activities and schedules for gas chromatographs are make and model
specific. It is therefore recommended that the analyst consult the operator's
manual for instructions relative to maintenance practices and procedures.
-------
Section No. 3-16.7
Date June 30, 1988
Page 3
Table 7.1. ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE CHECKS
Apparatus
Fiber vane
pump
Diaphragm
pump
Dry gas meter
Rotameter
Manometer
Sampling
train
components
Gas chroma-
tograph
Acceptance limits
In-line oiler
free of leaks
Leak- free valves
functioning properly
No excess oil,
corrosion, or er-
ratic rotation of
the dial
Clean and no erra-
tic behavior
No discoloration or
visible matter in
the fluid
No damage
See owner ' s manual
Frequency and method
of measurement
Periodically check
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 the
top plate; check
valves and diaphragm
yearly and whenever
meter dial runs erra-
tically or whenever
meter will not cal-
ibrate
Clean every 3 mo. or
whenever ball does
not move freely
Check periodically
and during disassemb-
ly
Visually check every
3 mo.; completely
disassemble and
clean or replace
yearly
See owner ' s manual
Action if require-
ments are not met
Replace as
needed
Replace when
leaking or mal-
functioning
Replace parts as
needed, or replace
meter
Replace
Replace parts
as needed
If failure noted,
replace appro-
priate components
See owner ' s manual
-------
Section No. 3.16.8
Date June 30, 1988
Page 1
8.0 AUDITING PROCEDURES
An audit is an independent assessment of data quality. Independence is
achieved if the individual(s) performing the audit and their standards and
equipment are different from the regular field team and their standards and
equipment. Routine quality assurance checks by a field team are necessary to
generate 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 requirements of Method 18 and the results of collaborative test-
ing of other Reference Methods, two specific performance audits are recommended:
1. An audit of the sampling and analysis of Method 18 is required for NSPS
and recommended for other purposes.
2. And audit of the data processing is recommended.
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 conducted to evaluate quantitatively the quality of
data produced by the total measurement system (sample collection, sample analysis,
and data processing). It is required that cylinder gas performance audits be
performed once during every NSPS test utilizing Method 18 and it is recommended
that a cylinder gas audit be performed once during any enforcement source test
utilizing Method 18 conducted under regulations other than NSPS.
8.1.1 Performance Audit of the Field Test - As stated in Section 6.5 of 40 CFR 60,
Appendix A, Method 18, immediately after the preparation of the calibration curves
and prior to the sample analysis, the analysis audit described in 40 CFR 61, Appen-
dix C, Procedure 2: "Procedure for Field Auditing GC Analysis," should be per-
formed. The information required to document the analysis of the audit sample(s)
has been included on the example data sheets shown in Figures 8.1 and 8.2; the
complete text of the procedure is reproduced in Section 3•16.10. The audit anal-
yses shall agree within 10 percent (or other specified value, as explained below)
of the true value. When available, the tester may obtain audit cylinders by
contacting: U.S. Environmental Protection Agency, Atmospheric Research and Exposure
Assessment Laboratory, Quality Assurance Division (MD-77B), Research Triangle Park,
North Carolina 27711• Audit cylinders obtained from a commercial gas manufacturer
may be used provided that (1) the gas manufacturer certifies the audit cylinder in
a manner similar to the procedure described in 40 CFR 61, Appendix B, Method 106,
Section 5-2.3-1. and (2) the gas manufacturer obtains an independent analysis.
Independent analysis is defined as an analysis performed by an individual other
than the individual who performs the gas manufacturer's analysis, while using
calibration standards and analysis equipment different from those used for the gas
manufacturer's analysis. Verification is completed and acceptable when the
independent analysis concentration is within 5 percent of the gas manufacturer's
concentration.
Responsibilities of the Audit Supervisor - The primary responsibilities of
the audit supervisor are to ensure that the proper audit gas cylinder(s) are or-
-------
Section No. 3.16.8,,
Date June 30, 1988
Page 2
dered and safe-guarded, and to interpret the results obtained by the analyst.
When auditing sampling systems that do not dilute the stack gases during samp-
ling, the audit gases ordered must consist of the same organic compound(s) that are
being tested; for emission standards on a concentration basis, the audit gas
concentration(s) must be in the range of 25% to 250% of the applicable standard. If
two cylinders are not available, then one cylinder can be used. If the audit
cylinder value is between 5 and 20 ppm, the agreement should be within 15 percent
of the stated audit cylinder value. It is strongly recommended that audit cylinder
values below 5 PPm not be used. For emission standards which specify a control
efficiency, the concentration of the audit gases should be in the range of 25% to
250% of the expected stack gas concentration. If ttoo cylinders are not available,
the audit can be conducted using one cylinder.
The audit supervisor must ensure that .the audit gas cylinder(s) are shipped to
the correct address, and to prevent vandalism, verify that they are stored in a
safe location both before .and after the audit. Also, the audit cylinders should
not be analyzed when the pressure drops below 200 psi. The audit supervisor then
ensures that the audits are conducted as described below.
The audit supervisor must also interpret the audit results. When the measured
concentration agrees within 10 percent (or 15 percent for cylinders between 5 and
20 ppm) of the true value, he directs the analyst to begin analyzing the source
samples. When the measured concentration does not agree within the specified
criterion, the analyst should first recheck the analytical system and calculations,
and then repeat the audit. If the analyst fails the second audit, the audit
supervisor should have knowledge of the agency's policy for failure. If the
result(s) are close to the allowed percentage or a consistent bias is present, the
supervisor may wish to allow the analyst use of a correction factor to be applied
at a later date; however, the analyst must make a significant effort to find the
discrepancy and correct it. If.the error cannot be found, the audit supervisor
should allow analysis of the samples, and then conduct the audit again.
During the audit, the audit supervisor should record the appropriate cylinder
number(s), cylinder pressure(s) (at the end of the. audit), and the calculated con-
centrations on the "Field audit report form", Figure 8.1. The individual being
audited must not, under any circumstances, be told the actual audit concentrations
until the calculated concentration(s) have been submitted to the audit supervisor
and are considered acceptable.
... -When auditing sampling systems that dilute the emissions during collection,
the-audit, gas concentration value used in the calculations can either be based on
(!•)' the undiluted concentration using the criteria discussed above or (2) the
expected concentration of the gases following dilution during collection using the
same dilution factor as used for the emission samples.
The audit procedures that follow are presented according to the type of samp-
ling system used to collect the organic emissions and whether the samples are
analyzed on-site or at the base laboratory at a.later date.
Container (Bag, Syringe, and Canister) Sampling with On-site Analysis - The
cylinder gas performance audit for rigid-container bag, syringe, or canister samp-
ling with on-site analysis consists of an on-site audit just prior to the analysis
of the emission samples. The recommended procedures for conducting the audit are
as follows:
1.. The audit samples should be collected in the type of container that
will be used during the sample collection. However, to conserve on the
use of the audit gas(es), it is usually not necessary to use the rest
of the sampling system to collect the samples for unheated container
-------
Section No. 3.16.8
Date June 30, 1988
Page 3
FIELD AUDIT REPORT
Part A. - To be filled out by organization supplying audit cylinders.
1. Organization supplying audit sample (s) and shipping address
4.
5-
6.
j
2. Audit supervisor', organization, and phone number
Shipping instructions: Name, Address, Attention
100 Pn>ke Ave,
Guaranteed arrival date for cylinders -
Planned shipping date for cylinders -
Details on audit cylinders from last analysis
a. Date of last analysis
b. Cylinder number
c . Cylinder pressure psi
d. Audit gas (es) /balance gas..
e. Audit gas(es) , ppm
f . Cylinder construction
Low cone.
Iz-Jitofoft
IQb'k
[S'LrO
.£•+&, /Jf/2~
A4
High cone
.C.+.h'/^i
Zi'so
A&
Part B. - To be filled out by audit supervisor.
1. Process sampled
2. Audit location $,fe.
3. Name of individual audit
4. Audit date
5. Audit Results:
a. Cylinder number
b. Cylinder pressure before audit, psi
c. Cylinder pressure after audit, psi
d. Measured concentration, ppm
Injection #1* Injection #2* Average
e. Actual audit concentration, ppm
f. Audit accuracy:1
Low Cone. Cylinder
High Cone. Cylinder
Percent1 accuracy =
Measured Cone. - Actual Cone. x 100
Actual Cone.
g. Problems detected (if any)
Low
cone.
cylinder
/Od>^
/57>£>
/S7?0
#l/*#>
+S.$%
hM
High
cone.
cylinder
/%&
p^IDD
2^?*®
2lx>/V4v
£>?*>
n^
1 Results of two consecutive injections that meet the sample analysis
criteria of the test method.
Figure 8.1. Field audit report form.
-------
Section No. 3.16.8
Date June 30, 1988
Page 4
sampling. Problems related to the reaction or retention of the organic
compounds will still occur in the container. Other interferents in the
stack gas such as water vapor and other organics will not be present in
the audit cylinders and thus, related problems will not be assessed.
For heated container systems, it may be necessary to use the sampling
• v system to collect the audit gas. However, if the gases must-be heated
to prevent condensation, it is likely that an audit gas cylinder will
not be available.
2. The audit samples should remain in the appropriate container approx-
imately the same length of time that the source samples will stay
prior to analysis. After the preparation of the calibration curve, a
minimum of two consecutive analyses of each audit cylinder gas should
be conducted. The analyses must agree within 5% of the average. The
audit results should be calculated by the analyst (or representative)
and given to the audit supervisor. The audit supervisor will record
all the information and data on the"Field audit report form" and then
inform the analyst of the status of the audit. The equations for
calculation of error are included on the form.
Container (Bag and Canister) Sampling with Off-site Analysis - For cylinder gas
performance audits associated with rigid-container bag or canister samples that
are analyzed off-site, it is recommended that the audit be conducted off-site just
prior to the emission test (if the agency desires) and then repeated during the
off-site sample analysis as a quality control measure. The use of the pretest
audit will help ensure that the analytical system will be acceptable prior to
testing. Alternatively, the audit gas can be collected in the appropriate con-
tainer on-site or off-site, and then analyzed just prior to the analysis of the
field samples. It is recommended that the tester fill at least two containers with
the audit gas to guard against a leak causing a failed audit. Since the use of the
performance audit is to both assess and improve the data quality, the use of the
pretest audit will provide the tester/analyst with a better chance of obtaining
acceptable data. The recommended procedure for conducting the audit is the same as
above with the exception that the audit supervisor will likely not be present
during the audit and the data will be reported by telephone.
Direct Interface Sampling - Since direct interface sampling involves on-site
analysis, the performance audit is conducted on-site after the calibration of the
GC and prior to sampling. The audit gas cylinder is attached to the inlet of the
sampling probe. Two consecutive analyses of the audit gas must be within 5% of
the average of the two analyses. The tester/analyst then calculates the results
and informs the audit supervisor. The audit supervisor records all information and
results on the "Field audit report form" and then informs the tester/analyst as to
the acceptability of the results.
Dilution Interface Sampling - Since dilution interface sampling involves on-
site analysis, the performance audit is conducted on-site after the calibration of
the GC and prior to sampling. If the audit gas cylinder obtained has a concentra-
tion '-near the diluted sample concentration, the audit gas is introduced directly
into the sample port on the GC. If the audit gas cylinder obtained has a concen-
tration close to the expected sample concentration, then the audit gas is intro-
duced into the dilution system. The audit supervisor may wish to order one cylin-
der to assess both the dilution system and the analytical system and another cylin-
der to assess only the analytical system. Follow the same procedures described
-------
Section No. 3.16.8
Date June 30, 1988
Page 5
above for recording the information and reporting the results.
Adsorption Tube Sampling - The analysis for adsorption tube sampling is usually
conducted off-site. Therefore, the audit analysis is conducted off-site. Again,
the recommended procedure is to conduct the audit once prior to the test and again
following the test. Though the audit sample could be analyzed by direct
injection, the inclusion of the chromatogram printout in the report will prove that
the audit results were obtained through adsorption tube sampling and a solvent
extraction. Alternatively, the audit samples can be collected on-site or off-site
and then analyzed just prior to the analysis of the field samples. Since the audit
supervisor will likely not be present during the analysis, the results are reported
by telephone.
To collect the audit gas with the adsorption tube sampling train, connect a
sample "T" to the line from the audit gas cylinder. Place the adsorption tube
sampling system on one leg of the "T"; connect a rotameter to the other leg. With
the sampling system off, turn on the audit gas flow until the rotameter reads 2
1pm. Turn on the sampling system and sample the audit gas for the specified run
time. Approximately 1 1pm should be discharged through the rotameter.
8.1.2 Performance Audit of Data Processing - Calculation errors are prevalent in
processing data. Data processing errors can be determined by auditing the recorded
data on the field "and laboratory forms. The original and audit (check) calcula-
tions 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. 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, etc.). Initially, a
systems audit is recommended for each enforcement source test, defined here as a
series of three runs at one source. After the test team gains experience with the
method, the frequency of auditing may be reduced — for example, to once 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 collec-
tion.
3- Check/verify records of apparatus calibration checks and quality control
used in the laboratory analysis of control samples from previous source
tests, where applicable.
4. Record the results of the audit, and forward them with comments to the
test team management so that appropriate corrective action may be
initiated.
While on site, the auditor observes the source test team's overall perfor-
mance, including the following specific operations:
-------
Section No. 3-16.8
Date June 30, 1988
Page 6
1. Conducting the GC calibration and conducting the performance audit (if the
analysis is conducted on-site).
2. Setting up and leak testing the sampling train.
3. Collecting the sample at a proportional rate (if applicable) or constant
rate at the specified flow rate.
4. Conducting the final leak check and recovery of the samples.
5. Conducting the initial and final check on the dilution system (if appli-
cable) .
6. Sample documentation procedures, sample recovery, and preparation of
samples for shipment (if applicable).
7. Conducting sample analyses (if conducted on-site).
Figure 8.2 is a suggested checklist for the auditor.
-------
Section No. 3-16.8
Date June 30, 1988
Page 7
Yes
No
Comments
Operation
A//4
PRESAMPLING PREPARATION
1. Knowledge of process operations
2. Results of pretest audit (_+ 10% or other value)
3. Calibration of pertinent equipment, in
particular, dry gas meters and other flowmeters
4. Selection and checkout of equipment for proper
sampling and analytical techniques
BAGS - reactivity, condensation, & retention
ADSORPTION TUBES - adsorption & desorption
efficiency
DILUTION SYSTEM - dilution ratio
GC/COLUMN - adequate resolution
GC/DETECTOR - acceptable accuracy & precision
V/4
N/A
V/A
ON-SITE MEASUREMENTS
5. Results of on-site audit (*_ 10% or other value)
6. Sampling system properly assembled
7. Based on pitot tube check, is proportional
sampling required (more than 10% flow change)
8. Dilution system check acceptable (if applicable)
9. Sampling system leak check acceptable
10. Proportional sampling properly conducted
11. Constant rate sampling properly conducted
12. Heater systems maintained at proper temperatures
13. Proper number of samples & sampling time
14. GC properly calibrated
15. Duplicate injections had acceptable precision <5%
16. Recording of pertinent process conditions during
sample collection, samples properly identified,
and calculations properly conducted
rilA
V/A
A//*
POSTSAMPLING
17. Results of off-site audit (+_ 10% or other value)
18. GC properly calibrated
19. Duplicate injections had acceptable precision <5%
20. Adsorption efficiency acceptable,>90% on primary
21. Desorption efficiency acceptable,>50% recovery
22. Adequate peak resolution
23. Bags passed reaction check, less than 10% change
24. Bags passed retention check,less than 5% retained
25. Flowmeters recalibration acceptable
26. Temperature sensor recalibration acceptable
COMMENTS
a-
Figure 8.2. Method 18 checklist to be used by auditors.
-------
Section No. 3.16.8
Date June 30, 1988
Page 8
Table 8.1. ACTIVITY MATRIX FOR AUDITING PROCEDURES
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Performance
audit of
analytical phase
Measured relative
error of audit
samples less than
10% (or other stated
value) for both
samples
Frequency; Once during
every enforcement
source test*
Method: Measure audit
samples and compare
results to true values
Review operating
technique and
repeat audit
Data processing
errors
Original and checked
calculations agree
within round-off
error
Frequency: Once during
every enforcement
source test*
Method: Independent
calculations starting
with recorded data
Check and correct
all data for the
audit period
represented by
the sampled data
Systems audit—
observance
of technique
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,
Figure 8.1
Explain to team
their deviations
from recommended
techniques and
note on Fig 8.1
*As defined here, a source test for enforcement of the NSPS comprises a series of
runs at one source. Source test for purposes other than enforcement of NSPS may
be audited at the frequency determined by the applicable group.
-------
Section No. 3-16.9
Date June 30, 1988
Page 1
9.0 RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY
To achieve data of desired quality, two essential considerations are
necessary: (1) the measurement process must bu 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 measurment), must result in an acceptable
uncertainty. As evidence in support of good quality data, it is necessary to
perform qulaity control checks and independent audits of the measurement process;
to document these data; and to use materials, instruments, and measurement
procedures that can be traced to an apropriate standard of reference.
Data must be routinely obtained by repeat measurements of standar 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.
Audit samples (as discussed in Section 3-16.8) must be used to validate test
results for compliance determination purposes and are recommendeed as an
independent check on the measurement process when the method is performed for other
purposes.
-------
Section No. 3-16.10
Date June 30, 1988
Page 1
10.0 REFERENCE METHOD'
Since the initial promulgation of Method 18 in 1983 (48 FR, 48344 - 48360,
10/18/83), there have been a number of revisions and additions to the method. In
the interest of consistency and clarity, the version of Method 18 reproduced here
from the most recent edition of the Code of Federal Regulations which
is
incorporates all promulgated changes to this date.
METHOD 18—MEASUREMENT OF GASEOUS OR-
GANIC COMPOUND EMISSIONS BV GAS Ciiso-
MATOGRAPHY
Introduction
This method should not be attempted by
persons unfamiliar with the performance
characteristics of gas chromatography. nor
by those persons who are unfamiliar with
source sampling. Particular care should be
exercised In the area of safety concerr.'r.g
choice of equipment and operation In poten-
tially explosive atmospheres.
1. Applicability and Principle
1.1 Applicability. This method applies to
the analysis of approximately 90 percent of
the total gaseous organics emitted from an
Industrial source. It does not Include tech-
niques to identify and measure trace
amounts of organic compounds, such as
those found In building air and fugitive
emission sources.
This method will not determine com-
pounds that (1) are polymeric (high molecu-
lar weight). (2) can polymerize before analy-
sis, or (3) have very low vapor pressures at
stack or Instrument conditions.
1.2 Principle.
The major organic components of a gas
mixture are separated by gas chromatogra-
phy (GO and individually quantified by
flame ionization, photoionization, electron
capture, or other appropriate detection
principles.
The retention times of each separated
component are compared with those of
known compounds under identical condi-
tions. Therefore, the analyst confirms the
identity and approximate concentrations of
the organic emission components before-
hand. With this information, the analyst
then prepares or purchases commercially
available standard mixtures to calibrate the
GC under conditions identical to those of
the samples. The analyst also determines
the need for sample dilution to avoid detec-
tor saturation, gas stream filtration to elimi-
nate particulate matter, and prevention of
moisture condensation.
2. Range and Sensitivity
2.1 Range. The range of this method is
from about 1 part per million (ppm) to the
upper limit governed by GC detector satura-
tion or column overloading. The upper limit
can be extended by diluting the stack gases
with an inert gas or by using smaller gas
sampling loops.
2.2 Sensitivity. The sensitivity limit for a
compound Is defined as the minimum de-
tectable concentration of that compound, or
the concentration that produces a signal-to-
nolse ratio of three to one. The minimum
detectable concentration Is determined
during the presurvey calibration for each
compound.
3. Precision and Accuracy
Gas chromatographlc techniques typically
provide a precision of 5 to 10 percent rela-
tive standard deviation (RSD). but an expe-
rienced GC operator with a reliable Instru-
ment can readily achieve 5 percent RSD.
For this method, the following combined
GC/operator values are required.
(a) Precision. Duplicate analyses are
within 5 percent of their mean value.
(b) Accuracy. Analysis results of prepared
audit samples are within 10 percent of prep-
aration values.
4. Interferences
Resolution Interferences that may occur
can be eliminated by appropriate GC
column and detector choice or by shifting
the retention times through changes in the
column flow rate and the use of tempera-
ture programming.
The analytical system Is demonstrated to
be essentially free from contaminants by pe-
riodically analyzing blanks that consist of
hydrocarbon-free air or nitrogen.
Sample cross-contamination that occurs
when high-level and low-level samples or
standards are analyzed alternately, is best
dealt with by thorough purging of the GC
sample loop between samples.
To assure consistent detector response.
calibration gases are contained In dry air.
To adjust gaseous organic concentrations
when water vapor Is present In the sample,
water vapor concentrations are determined
for those samples, and a correction factor Is
applied.
5. Presurvey and Presurvey Sampling.
Perform a presurvey for each source to be
tested. Refer to Figure 18-1. Some of the In-
formation can be collected from literature
surveys and source personnel. Collect gas
samples that can be analyzed to confirm the
identities and approximate concentrations
of the organic emissions.
S.I Apparatus. This apparatus list also
applies to Sections 6 and 7.
*40 CFR 60, Appendix A, Method 18, July 1, 198?, pages ?40 - 769.
-------
Section No. 3.16.10
Date June 30, 1988
Page 2
5.1.1 Teflon Tubing. (Mention of trade
names or specific products does not consti-
tute endorsement by the U.S. Environmen-
tal Protection Agency.) Diameter and
length determined by connection require-
ments of cylinder regulators and the GC.
Additional tubing is necessary to connect
the GC sample loop to the sample.
S.I.2 Gas Chromatograph. GC with suit-
able detector, columns, temperature-con-
trolled sample loop and valve assembly, and
temperature programable oven, if necessary.
The GC shall achieve sensitivity require-
ments for the compounds under study.
5.1.3 Pump. Capable of pumping 100 ml/
mln. For flushing sample loop.
5.1.4 Flowmeters. To measure flow rates.
5.1.5 Regulators. Used on gas cylinders
for GC and for cylinder standards.
5.1.6 Recorder. Recorder with linear strip
chart Is minimum acceptable. Integrator
(optional) is recommended.
5.1.7 Syringes. 0.5-ml, 1.0- and 10-mlcro-
llter sizes, calibrated, maximum accuracy
(gas tight), for preparing calibration stand-
ards. Other appropriate sizes can be used.
5.1.8 Tubing Fittings. To plumb GC and
gas cylinders.
5.1.9 Septums. For syringe injections.
5.1.10 Glass Jars. If necessary, clean-col-
ored glass jars with Teflon-lined lids for
condensat.3 sample collection. Size depends
on volume of condensate.
5.1.11 Soap Film Flow Meter. To deter-
mine flow rates.
5.1.12 Tedlar Bags. 10- and 50-liter capac-
ity, for preparation of standards.
5.1.13 Dry Gas Meter with Temperature
and Pressure Gauges. Accurate to ±2 per-
cent, for perparatlon of gas standards.
5.1.14 Midget Implnger/Hot Plate As-
sembly. For preparation of gas standards.
5.1.15 Sample Flasks. For presurvey sam-
ples, must have gas-tight seals.
5.1.16 Adsorption Tubes. If necessary,
blank tubes filled with necessary adsorbent
(charcoal. Tenax, XAD-2, etc.) for presur-
vey samples.
5.1.17 Personnel Sampling Pump. Cali-
brated, for collecting adsorbent tube presur-
vey samples.
5.1.18 Dilution System. Calibrated, the
dilution system Is to be constructed follow-
ing the specifications of an acceptable
method.
5.1.19 Sample Probes. Pyrex or stainless
steel, of sufficient length to reach centroid
of stack, or a point no closer to the walls
than 1 m.
5.1.20 Barometer. To measure barometric
pressure.
5.2 Reagents.
5.2.1 Delonlzed Distilled Water.
5.2.2 Methylene DIchloride.
5.2.3 Calibration Gases. A series of stand-
ards prepared for every compound of inter-
est.
5.2.4-'Organic Compound Solutions. Pure
(99.9 percent), or as pure as can reasonably
be obtained, liquid samples of all the organ-
ic compounds needed to prepare calibration
standards.
5.2.5 Extraction Solvents. For extraction
of adsorbent tube samples in preparation
for analysis.
5.2.6 Fuel. As recommended by the man-
ufacturer for operation of the GC.
5.2.7 Carrier Gas. Hydrocarbon free, as
recommended by the manufacturer for op-
eration of the detector and compatabllity
with the column.
5.2.8 Zero Gas. Hydrocarbon free air or
nitrogen, to be used for dilutions, blank
preparation, and standard preparation.
5.3 Sampling.
5.3.1 Collection of Samples with Glass
Sampling Flasks. Presurvey samples can be
collected In precleaned 250-ml double-ended
glass sampling flasks. Teflon stopcocks,
without grease, are preferred. Flasks should
be cleaned as follows: Remove the stopcocks
from both ends of the flasks, and wipe the
parts to remove any grease. Clean the stop-
cocks, barrels, and receivers with methylene
dlchloride. Clean all glass ports with a soap
solution, then rinse with tap and delonlzed
distilled water. Place the flask in a cool
glass annealing furnace and apply heat up
to 500* C. Maintain at this temperature for
1 hour. After this time period, shut off and
open the furnace to allow the flask to cool.
Grease the stopcocks with stopcock grease
and return them to the flask receivers.
Purge the assembly with high-purity nitro-
gen for 2 to 5 minutes. Close off the stop-
cocks after purging to maintain a slight
positive nitrogen pressure. Secure the stop-
cocks with tape.
Presurvey samples can be obtained either
by drawing the gases Into the previously
evacuated flask or by drawing the gases Into
and purging the flask with a rubber suctloi.
bulb.
5.3.1.1 Evacuated Flask Procedure. Use a
high-vacuum pump to evacuate the flask to
the capacity of the pump; then close off the
stopcock leading to the pump. Attach a 6-
mm outside diameter (OD) glass tee to the
flask Inlet with a short piece of Teflon
tubing. Select a 6-mm OD borosilicate sam-
pling probe, enlarged at one end to a 12-mm
OD and of sufficient length to reach the
centroid of the duct to be sampled. Insert a
glass wool plug in the enlarged end of the
probe to remove particulate matter. Attach
the other end of the probe to the tee with a
short piece of Teflon tubing. Connect a
rubber suction bulb to the third leg of the
tee. Place the filter end of the probe at the
centroid of the duct, or at a point no closer
to the walls than 1 m. and purge the probe
with the rubber suction bulb. After the
probe is completely purged and filled with
duct gases, open the stopcock to the grab
flask until the pressure in the flask reaches
duct pressure. Close off the stopcock, and
remove the probe from the duct. Remove
the tee from the flask and tape the stop-
cocks to prevent leaks during shipment.
Measure and record the duct temperature
and pressure.
5.3.1.2 Purged Flask Procedure. Attach
one end of the sampling flask to a rubber
suction bulb. Attach the other end to a 6-
mm OD glass probe as described in Section
-------
Section No. 3-16.10
Date June 30, 1988
Page 3
5.3.1.1. Place the filter end of the probe at
the centroid of the duct, or at a point no
closer to the walls than 1 m. and apply suc-
tion with the bulb to completely purge the
probe and flask. After the flask has been
purged, close off the stopcock near the suc-
tion bulb, and then close the stopcock near
the probe. Remove the probe from the duct,
and disconnect both the probe and suction
bulb. Tape the stopcocks to prevent leakage
during shipment. Measure and record the
duct temperature and pressure.
5.3.2 Flexible Bag Procedure. Tedlar or
aluminlzed Mylar bags can also be used to
obtain the presurvey sample. Use new bags,
and leak check them before field use. In ad-
dition, check the bag before use for con-
tamination by filling it with nitrogen or air,
and analyzing the gas by GC at high sensi-
tivity. Experience indicates that it Is desira-
ble to allow the Inert gas to remain In the
bag about 24 hours or longer to check for
desorptlon of organics from the bag. Follow
the leak check and sample collection proce-
dures given in Section 7.1.
5.3.3 Determination of Moisture Content.
For combustion or water-controlled process-
es, obtain the moisture content from plant
personnel or by measurement during the
presurvey. If the source Is below 59' C,
measure the wet bulb and dry bulb tempera-
tures, and calculate the moisture content
using a psychrometric chart. At higher tern
peratures, use Method 4 to determine the
moisture content.
5.4 Determination of Static Pressure.
Obtain the static pressure from the plant
personnel or measurement. If a type S pilot
tube and an Inclined manometer are used,
take care to align the pltot tube 90* from
the direction of the flow. Disconnect one of
the tubes to the manometer, and read the
static pressure: note whether the reading is
positive or negative.
5.5 Collection of Presurvey Samples with
Adsorption Tube. Follow Section 7.4 for pre-
survey sampling.
6. Analysis Development
6.1 Selection of GC Parameters.
6.1.1 Column Choice. Based on the initial
contact with plant personnel concerning the
plant process and the anticipated emissions,
choose a column that provides good resolu-
tion and rapid analysis time. The choice of
an appropriate column can be aided by a lit-
erature search, contact with manufacturers
of GC columns, and discussion with person-
nel at the emission source.
Most column manufacturers keep excel-
lent records of their products. Their techni-
cal service departments may be able to rec-
ommend appropriate columns and detector
type for separating the anticipated com-
pounds, and they may be able to provide in-
formation on interferences, optimum oper-
ating conditions, and column limitations.
Plants with analytical laboratories may
also be able to provide information on ap-
propriate analytical procedures.
6.1.2 Preliminary GC Adjustment. Using
the standards and column obtained in Sec-
tion 6.1.1, perform initial tests to determine
appropriate GC conditions that provide
good resolution and minimum analysis time
for the compounds of interest.
6.1.3 Preparation of Presurvey Samples.
If the samples were collected on an adsorb-
ent, extract the sample as recommended by
the manufacturer for removal of the com-
pounds with a solvent suitable to the type
of GC analysis. Prepare other samples In an
appropriate manner.
6.1.4 Presurvey Sample Analysis. Before
analysis, heat the presurvey sample to the
duct temperature to vaporize any condensed
material. Analyze the samples by the GC
procedure, and compare the retention times
against those of the calibration samples
that contain the components expected to be
in the stream. If any compounds.; cannot be
identified with certainty by this procedure,
identify them by other means such as GC/
mass spectroscopy (GC/MS) or GC/lnfrared
techniques. A GC/MS system is recom-
mended.
Use the GC conditions determined by the
procedures of Section 6.1.2 for the first in-
jection. Vary the GC parameters during
subsequent injections to determine the opti-
mum settings. Once the optimum settings
have been determined, perform repeat injec-
tions of the sample to determine the reten-
tion time of each compound. To inject a
sample, draw sample through the loop at a
constant rate (100 ml/min for 30 seconds).
Be careful not to pressurize the gas In the
loop. Turn off the pump and allow the gas
In the sample loop to come to ambient pres-
sure. Activate the sample valve, and record
Injection time, loop temperature, column
temperature, carrier flow rate, chart speed.
and attenuator setting. Calculate the reten-
tion time of each peak using the distance
from injection to the peak maximum divid-
ed by the chart speed. Retention times
should be repeatable within 0.5 seconds.
If the concentrations are too high for ap-
propriate detector response, a smaller
sample loop or dilutions may be used for gas
samples, and. for liquid samples, dilution
with solvent is appropriate. Use the stand-
ard curves (Section 6.3) to obtain an esti-
mate of the concentrations.
Identify all peaks by comparing the
known retention times of compounds ex-
pected to be in the retention times of peaks
in the sample. Identify any remaining un-
identified peaks which have areas larger
than 5 percent of the total using a GC/MS.
or estimation of possible compounds by
their retention times compared to known
compounds, with confirmation by further
GC analysis.
6.2 Calibration Standards. Prepare or
obtain enough calibration standards so that
there are three different concentrations of
each organic compound expected to be
measured in the source sample. For each or-
ganic compound, select those concentrations
that bracket the concentrations expected In
the source samples. A calibration standard
may contain more than one organic com-
pound. If available, commercial cylinder
gases may be used If their concentrations
have been certified by direct analysis.
If samples are collected in adsorbent tubes
(charcoal, XAD-2, Tenax, etc.). prepare or
obtain standards in the same solvent used
for the sample extraction procedure. Refer
to Section 7.4.3.
-------
Section No. 3.16.10
Date June 30, 1988
Page 4
Verify the stability of all standards for
the time periods they are used. If gas stand-
ards are prepared in the laboratory, use one
or more of the following procedures.
6.2.1 Preparation of Standards from
High Concentration Cylinder Standards.
Obtain enough high concentration cylinder
standards to represent ail the organic com-
pounds expected in the. source samples.
Use these high concentration standards to
prepare lower concentration standards by
dilution, as shown by Figures 18-5 and 18-6.
To prepare the diluted calibration sam-
ples. calibrated rotameters are normally
used to meter both the high concentration
calibration gas and the diluent gas. Other
types of flowmeters and commercially avail-
able dilution systems can also be used.
Calibrate each flowmeter before use by
placing it between the diluent gas supply
and suitably sized bubble meter, spirometer.
or wet test meter. Record all data shown on
Figure 18-4. While it is desirable to calibrate
the cylinder gas flowmeter with cylinder
gas, the available quantity and cost may
preclude it. The error introduced by using
the diluent gas for calibration is insignifi-
cant for gas mixtures of up to 1,000 to 2,000
ppm of each organic component.
Once the flowmeters are calibrated, con-
nect the flowmeters to the calibration and
diluent gas supplies using 6-mm Teflon
tubing. Connect the outlet side of the flow-
meters through a connector to a leak-free
Tedlar bag as shown in Figure 18-5. (See
Section 7.1 for bag leak-check procedures.)
Adjust the gas flow to provide the desired
dilution, and fill the bag with sufficient gas
for GC calibration. Be careful not to overfill
and cause the bag to apply additional pres-
sure on the dilution system. Record the flow
rates of both flowmeters, and the laborato-
ry temperature and atmospheric pressure.
Calculate the concentration C. in ppm of
each organic in the diluted gas as follows:
106 (X q
)
Eq . 18-1
where:
10" = Conversion to ppm.
X=Mole or volume fraction of the organic
In the calibration gas to be diluted.
qc=Flow rate of the calibration gas to be di-
luted.
qd= Diluent gas flow rate.
Single-stage dilutions should be used to pre-
pare calibration mixtures up to about 1:20
dilution factor.
For greater dilutions, a double dilution
system is recommended, as shown in Figure
18-6. Fill the Tedlar bag with the dilute gas
from the second stage. Record the laborato-
ry temperature, barometric pressure, and
static pressure readings. Correct the flow
reading for temperature and pressure. Cal-
culate the concentration C, in ppm of the
organic in the final gas mixture as follows:
Eq. 18-2
Where:
10'=Conversion to ppm.
X=Mole or volume fraction of the organic
in the calibration gas to be diluted.
q,i=Flow rate of the calibration gas to be di-
luted In stage 1.
qd=Flow rate of the calibration gas to be di-
luted in stage 2.
q«i=Flow rate of diluent gas In stage 1.
q,n=Flow rate of diluent gas in stage 2.
Further details of the calibration methods
for flowmeters and the dilution system can
be found In Citation 21 in the Bibliography.
6.2.2 Preparation of Standards from
Volatile Materials. Record all data shown on
Figure 18-3.
6.2.2.1 Gas Injection Technique. This
procedure is applicable to organic com-
pounds that exist entirely as a gas at ambi-
ent conditions. Evacuate a 10-liter Tedlar
bag that has passed a leak-check (see Sec-
tion 7.1), and meter in 5.0 liters of air or ni-
trogen through a dry gas meter that has
been calibrated in a manner consistent with
the procedure described In Section 5.1.1 of
Method 5. While the bag is filling use a 0.5-
ml syringe to inject a known quantity of
"pure" gas of the organic compound
through the wall of the bag. or through a
septum-capped tee at the bag inlet. With-
draw the syringe needle, and Immediately
cover the resulting hole with a piece of
masking tape. In a like manner, prepare di-
lutions having other concentrations. Pre-
pare a minimum of three concentrations.
Place each bag on a smooth surface, and al-
ternately depress opposite sides of the bag
50 times to mix the gases Record the aver-
age meter temperature and pressure, the
gas volume and the barometric pressure.
Record the syringe temperature and pres-
sure before Injection.
Calculate each organic standard concen-
tration C. in pom as follows:
r in6 293
by x 10
P
760
Vm Y 291
Gv x ID"
1000
Eq. 18-3
-------
Section No. 3.16.10
Date June 30, 1988
Page 5
where:
O,=Gas volume or organic compound In-
jected, ml.
,o*= Conversion to ppm.
P.=Absolute pressure of syringe before in-
jection, mm Hg.
T.=Absolute temperature of syringe before
Injection. 'K.
Va-Gas volume Indicated by dry gas meter.
liters.
Y=Dry gas meter calibration factor, dlmen-
slonless.
?„=Absolute pressure of dry gas meter, mm
Hg.
Tm=Absolute temperature of dry gas meter,
•K.
1000=Conversion factor, ml/liter. .
6.2.2.2 Liquid Injection Technique. Use
the equipment shown in Figure 18-8. Cali-
brate the dry gas meter as described in Sec-
tion 6.2.2.1 with a wet test meter or a spi-
rometer. Use a water manometer for the
pressure gauge and glass. Teflon, brass, ot
stainless steel for all connections. Connect a
valve to the inlet of the 50-liter Tedlar bag.
To prepare the standards, assemble the
equipment as shown In Figure 18-8, and
leak-check the system. Completely evacuate
the bag. Fill the bag with hydrocarbon-free
air, and evacuate the bag again. Close the
Inlet valve.
Turn on the hot plate, and allow the
water to reach boiling. Connect the bag to
the Implnger outlet. Record the initial
meter reading, open the bag inlet valve, and
open the cylinder. Adjust the rate, so that
the bag will be completely filled in approxi-
mately IS minutes.'Record meter pressure
and temperature, and local barometric pres-
sure.
Allow the liquid organic to equilibrate to
room temperature. Fill the 1.0- or 10-micro-
llter syringe to the desired liquid volume
with'the organic. Place the syringe needle
Into the impinger inlet using the septum
provided, and inject the liquid into the flow-
Ing air stream. Use a needle of sufficient
length to permit Injection of the. liquid
below the air inlet branch of the tee.
Remove the syringe.
When the bag is filled, stop the pump, and
close the bag inlet valve. Record the final
meter reading, temperature, and pressure.
Disconnect the bag from the impinger
outlet, and either set It aside for at least 1
hour, or massage the bag to Insure complete
mixing.
Measure the solvent liquid density at
room temperature by accurately weighing a
known volume of the material on an analyt-
ical balance to the nearest 1.0 milligram. A
ground-glass stoppered 25-mil volumetric
flask or a glass-stoppered specific gravity
bottle Is suitable for weighing. Calculate the
result in terms of g/ml. As an alternative,
literature values of the density of the liquid
at 20 *C may be used.
Calculate each organic standard concen-
tration C. in ppm as follows:
(24.055 x 10)
6.24 x 10
293 P
Y P
750
100°
Eq. 18-4
where:
L.= Liquid volume of organic injected. pi.
p.l= Liquid organic density as determined, g/
ml.
M= Molecular weight of organic, g/g-mole.
24.055 = Ideal gas molar volume at 293 *K
and 760 mm Hg, llters/g-mole.
10'= Con version to ppm.
1000= Con version factor,
6.3 Preparation of Calibration Curves.
Establish proper GC conditions, then flush
the sampling loop for 30 seconds at a rate of
100 ml/min. Allow the sample loop pressure
to equilibrate to atmospheric pressure, and
activate the Injection valve. Record the
standard concentration, attenuator factor,
Injection time, chart speed, retention time,
peak area, sample loop temperature, column
temperature, and carrier gas flow rate.
Repeat the standard Injection until two con-
secutive Injections give area counts within 5
percent of their average. The average value
multlpled by the attenuator factor is then
the calibration area value for the concentra-
tion.
Repeat this procedure for each standard.
Prepare a graphical plot of concentration
(C.) versus the calibration area values. Per-
form a regression analysis, and draw the
least squares line.
6.4 Relative Response Factors. The cali-
bration curve generated from the standards
for a single organic can usually be related to
each of the individual GC response curves
that are developed in the laboratory for all
the compounds in the source. In the field,
standards for that single organic can then
be used to "calibrate" the GC for all the or-
ganics present. This procedure should first
be confirmed in the laboratory by preparing
and analyzing calibration standards contain-
ing multiple organic compounds.
6.5 Quality Assurance for Laboratory
Procedures. Immediately after the prepara-
tion of the calibration curves and prior to
the presurvey sample analysis, the analysis
audit described in 40 CFR Part 61, Appen-
dix C, Procedure 2: "Procedure for Field Au-
diting GC Analysis," should be performed.
The information required to document the
analysis of the audit samples has been in-
cluded on the example data sheets shown in
Figures 18-3 and 18-7. The audit analyses
should agree with the audit concentrations
within 10 percent. When available, the
tester may obtain audit cylinders by con-
tacting: U.S. Environmental Protection
Agency, Environmental Monitoring Systems
-------
Section No. 3.16.10
Date June 30, 19&8
Page 6
Laboratory. Quality Assurance Division
(MD-77), Research Triangle Park. North
Carolina 27711. Audit cylinders obtained
from a commercial gas manufacturer may
be used provided that (a) the gas manufac-
turer certifies the audit cylinder in a
manner similar to the procedure described
in 40 CFR Part 61. Appendix B. Method 106,
Section 5.2.3.1, and (b) the gas manufactur-
er obtains an independent analysis of the
audit cylinders to verify this analysis. Inde-
pendent analysis is defined as an analysis
performed by an individual other than the
individual who performs the gas manufac-
turer's analysis, while using calibration
standards and analysis equipment different
from those used for the gas manufacturer's
analysis. Verification is complete and ac-
ceptable when the independent analysis
concentration is within 5 percent of the gas
manufacturer's concentration.
7. Final Sampling and Analysis Procedure
Considering safety (flame hazards) and
the source conditions, select an appropriate
sampling and analysis procedure (Section
7.1, 7.2, 7.3, or 7.4). In situations where a hy-
drogen flame Is a hazard and no Intrinsical-
ly safe GC is suitable, use the flexible bag
collection technique or an adsorption tech-
nique. If the source temperature Is below
100'C, and the organic concentrations are
suitable for the detector to be used, use the
direct Interface method. If the source gases
require dilution, use a dilution Interface and
either the bag sample or adsorption tubes.
The choice between these two techniques
will depend on the physical layout of the
site, the source temperature, and the stor-
age stability of the compounds if collected
in the bag. Sample polar compounds by
direct Interfacing or dilution Interfacing to
prevent sample loss by adsorption on the
bag.
7.1 Integrated Bag Sampling and Analy-
sis.
7.1.1 Evacuated Container Sampling Pro-
cedure. In this procedure, the bags are filled
by evacuating the rigid air-tight containers
that hold the bags. Use a field sample data
sheet as shown in Figure 18-10. Collect trip-
licate sample from each sample location.
7.1.1.1 Apparatus.
7.1.1.1.1 Probe. Stainless steel, Pyrex
glass, or Teflon tubing probe, according to
the duct temperature, with 6.4-mm OD
Teflon tubing of sufficient length to con-
nect to the sample bag. Use stainless steel or
Teflon unions to connect probe and sample
line.
7.1.1.1.2 Quick Connects. Male (2) and
female (2) of stainless steel construction.
7.1.1.1.3 Needle Valve. To control gas
flow.
7.1.1.1.4 Pump. Leakless Teflon-coated
diaphragm-type pump or equivalent. To de-
liver at least 1 liter /tain.
7.1.1.1.5 Charcoal Adsorption Tube. Tube
filled with activated charcoal, with glass
wool plugs at each end. to adsorb organic
vapors.
7.1.1.1.6 Flowmeter. 0 to 500-tnl flow
range; with manufacturer's calibration
curve.
7.1.1.2 Sampling Procedure. To obtain a
sample, assemble the sample train as shown
in Figure 18-9. Leak check both the bag and
the container. Connect the vacuum line
from the needle valve to the Teflon sample
line from the probe. Place the end of the
probe at the centroid of the stack, or at a
point no closer to the walls than 1 m, and
start the pump with the needle valve adjust-
ed to yield a flow of 0.5 liter/minute. After
allowing sufficient time to purge the line
several times, connect the vacuum line to
the bag, and evacuate until the rotameter
indicates no flow. Then position the sample
and vacuum lines for sampling, and begin
the actual sampling, keeping the rate pro-
portional to the stack velocity. As a precau-
tion, direct the gas exiting the rotameter
away from sampling personnel. At the end
of the sample period, shut off the pump,
disconnect the sample line from the bag,
and disconnect the vacuum line from the
bag container. Record the source tempera-
ture, barometric pressure, ambient tempera-
ture, sampling flow rate, and initial and
final sampling time on the data sheet shown
in Figure 18-10. Protect the Tedlar bag and
Its container from sunlight. When possible,
perform the analysis within 2 hours of
sample collection.
7.1.2 Direct Pump Sampling Procedure.
Follow 7.1.1, except place the pump and
needle valve between the probe and the bag.
Use a pump and needle valve constructed of
stainless steel or some other material not af-
fected by the stack gas. Leak check the
system, and then purge with stack gas
before the connecting to the previously
evacuated bag.
7.1.3 Explosion Risk Area Bag Sampling
Procedure. Follow 7.1.1 except replace the
pump with another evacuated can (see
Figure 18-9a). Use this method whenever
there Is a possibility of an explosion due to
pumps, heated probes, or other flame pro-
ducing equipment.
7.1.4 Other Modified Bag Sampling Pro-
cedures. In the event that condensation is
observed in the bag while collecting the
sample and a direct interface system cannot
be used, heat the bag during collection, and
maintain it at a suitably elevated tempera-
ture during all subsequent operations.
(Note: Take care to leak check the system
prior to the dilutions so as not to create a
potentially explosive atmosphere.) As an al-
ternative, collect the sample gas, and simul-
taneously dilute it In the Tedlar bag.
In the first procedure, heat the box con-
taining the sample bag to the source tem-
perature, provided the components of the
bag and the surrounding box can withstand
this temperature. Then transport the bag as
rapidly as possible to the analytical area
while maintaining the heating, or cover the
box with an insulating blanket. In the ana-
lytical area, keep the box heated to source
temperature until analysis. Be sure that the
method of heating the box and the control
for the heating circuit are compatible with
the safety restrictions required in each area.
-------
Section No. 3.16.10
Date June 30, 1988
Page 7
To use the second procedure, preflll the
Tedlar bag with a known quantity of Inert
gas. Meter the Inert gas into the bag accord-
Ing to the procedure for the preparation of
gas concentration standards of volatile
liquid materials (Section 6.2.2.2). but elimi-
nate the midget Implnger section. Take the
partly filled bag to the source, and meter
the source gas Into the bag through heated
sampling lines and a heated flowmeter, or
Teflon positive displacement pump. Verify
the dilution factors periodically through di-
lution and analysis of gases of known con-
centration.
7.1.5 Analysis of Bag Samples.
7.1.5.1 Apparatus. Same as Section 5. A
minimum of three gas standards are re-
quired.
7.1.5.2 Procedure. Establish proper QC
operating conditions as described In Section
6.3, and record all data listed In Figure 18-7.
Prepare the GC so that gas can be drawn
through the sample valve. Flush the sample
loop with gas from one of the three calibra-
tion mixtures, and activate the valve.
Obtain at least two chromatograms for the
mixture. The results are acceptable when
the peak areas from two consecutive injec-
tions agree to within 5 percent of their aver-
age. If they do not, run additional analyses
or correct the analytical techniques until
this requirement is met. Then analyze the
other two calibration mixtures In the same
manner. Prepare a calibration curve as de-
scribed In the same manner. Prepare a cali-
bration curve as described In Section 6.3.
Analyze the source gas samples by con-
necting each bag to the sampling valve with
a piece of Teflon tubing identified for that
bag. Follow the specifications on replicate
analyses specified for the calibration gases.
Record the data listed in Figure 18-11. If
certain items do not apply, use the notation
"N.A." After all samples have been ana-
lyzed, repeat the analyses of the calibration
gas mixtures, and generate a second calibra-
tion curve. Use an average of the two curves
to determine the sample gas concentrations.
If the two calibration curves differ by more
than 5 percent from their mean value, then
report the final results by comparison to
both calibration curves.
7.1.6 Determination of Bag Water Vapor
Content. Measure and record the ambient
temperature and barometric pressure near
the bag. From a water saturation vapor
pressure table, determine and record the
water vapor content as a decimal figure.
(Assume the relative humidity to be 100 per-
cent unless a lesser value Is known.) If the
bag has been maintained at an elevated tem-
perature as described In Section 7.1.4. deter-
mine the stack gas water content by Method
4.
7.1.7 Quality Assurance. Immediately
prior to the analysis of the stack gas sam-
ples, perform audit analyses as described In
Section 6.5. The audit analyses must agree
with the audit concentrations within 10 per-
cent. If the results are acceptable, proceed
with the analyses of the source samples. If
they do not agree within 10 percent, then
determine the reason (or the discrepancy,
and take corrective action before proceed-
ing.
7.1.8 Emission Calculations. From the av-
erage calibration curve described In Section
7.1.5., select the value of C. that corresponds
to the peak area. Calculate the concentra-
tion C, in ppm, dry basis, of each organic In
the sample as follows:
Cr =
WlFr
iTr U-BWS)
• -
C.=Concentration of the organic from the
calibration curve, ppm.
P,=Reference pressure, the barometric
pressure or absolute sample loop pres-
sure recorded during calibration, mm
Hg.
T,=Sample loop temperature at the time of
sample analysis, *K.
F,=Relative response factor (If applicable.
see Section 6.4).
P,=Barometric or absolute sample loop
pressure at time of sample analysis, mm
Hg.
Tr=Reference temperature, the tempera-
ture of the sample loop recorded during
calibration/K.
8.,!= Water vapor content of the bag sample
or stack gas, proportion by volume.
7.2 Direct Interface Sampling and Analy-
sis Procedure. The direct Interface proce-
dure can be used provided that the moisture
content of the gas does not Interfere with
the analysis procedure, the physical require-
ments of the equipment can be met at the
site, and the source gas concentration is low
enough that detector saturation Is not a
problem. Adhere to all safety requirements
with this method.
7.2.1 Apparatus.
7.2.1.1 Probe. Constructed of stainless
steel, Pyrex glass, or Teflon tubing as re-
quired by duct temperature, 6.4-mrn OD, en-
larged at duct end to contain glass wool
plug. If necessary, heat the probe with heat-
Ing tape or a special heating unit capable of
maintaining duct temperature.
7.2.1.2 Sample Lines. 6.4-mm OD Teflon
lines, heat-traced to prevent condensation
of material.
7.2.1.3 Quick Connects. To connect
sample line to gas sampling valve on GC In-
strument and to pump unit used to with-
draw source gas. Use a quick connect or
equivalent on the cylinder or bag containing
calibration gas to allow connection of the
calibration gas to the gas sampling valve.
7.2.1.4 Thermocouple Readout Device.
Potentiometer or digital thermometer, to
measure source temperature and probe tem-
perature.
7.2.1.5 Heated Gas Sampling Valve. Of
two-position, six-port design, to allow
sample loop to be purged with source gas or
to direct source gas into the GC Instrument.
7.2.1.6 Needle Valve. To control gas sam-
pling rate from the source.
-------
Section No. 3.16.10
Date June 30, 198B
Page 8
7.2.1.7 Pump. Leakless Teflon-coated dia-
phragm-type pump or equivalent, capable of
at least 1 liter/minute sampling rate.
7.2.1.8 Flowmeter. Of suitable range to
measure sampling rate.
7.2.1.9 Charcoal Adsorber. To adsorb or-
ganic vapor collected from the source to
prevent exposure of personnel to source gas.
7.2.1.10 Gas Cylinders. Carrier gas
(helium or nitrogen), and oxygen and hy-
drogen for a flame ionization detector (FID)
if one is used. •
7.2.1.11 Gas Chromatograph. Capable of
being moved into the field, with detector.
heated gas sampling valve, column required
to complete separation of desired compo-
nents, and option for temperature program-
ming.
7.2.1.12 Recorder/Integrator. To record
results.
7.2.2 Procedure. To obtain a sample, as-
semble the sampling system as shown in
Figure 18-12. Make sure all connections are
tight. Turn on the probe and sample line
heaters. As the temperature of the probe
and heated line approaches the source tem-
perature as indicated on the thermocouple
readout device, control the heating to main-
tain a temperature of 0 to 3*C above the
source temperature. While the probe and
heated line are being heated, disconnect the
sample line from the gas sampling valve,
and attach the line from the calibration gas
mixture. Flush the sample loop with cali-
bration gas and analyze a portion of that
gas. Record the results. After the calibra-
tion gas sample has been flushed into the
GC Instrument, turn the gas sampling valve
to flush position, then reconnect the probe
sample line to the valve. Place the Inlet of
the probe at the centrold of the duct, or at a
point no closer to the walls than 1 m, and
draw source gas into the probe, heated line.
and sample loop. After thorough flushing,
analyze the sample using the same condi-
tions as for the calibration gas mixture.
Repeat the analysis on an additional
sample. Measure the peak areas for the two
samples, and if they do not agree to within 5
percent of their mean value, analyze addi-
tional samples until two consecutive analy-
ses meet this criteria. Record the data.
After consistent results are obtained,
remove the probe from the source and ana-
lyze a second calibration gas mixture.
Record this calibration data and the other
required data on the data sheet shown in
Figure 18-11, deleting the dilution gas infor-
mation.
(NOTE: Take care to draw all samples, cali-
bration mixtures, and audits through the
sample loop at the same pressure.)
7.2.3 Determination of Stack Gas Mois-
ture Content. Use Method 4 to measure the
stack gas moisture content.
7.2.4 Quality Assurance. Same as Section
7.1.7. Introduce the audit gases in the
sample line immediately following the
probe.
7.2.5 Emission Calculations. Same as Sec-
tion 7.1.8.
7.3 Dilution Interface Sampling and
Analysis Procedure. Source samples that
contain a high concentration of organic ma-
terials may require dilution prior to analysis
to prevent saturating the GC detector. The
apparatus required for this direct interface
procedure is basically the same as that de-
scribed in the Section 7.2, except a dilution
system is added between the heated sample
line and the gas sampling valve. The appa-
ratus is arranged so that either a 10:1 or
100:1 dilution of the source gas can be di-
rected to the Chromatograph. A pump of
larger capacity is also required, and this
pump must be heated and placed in the
system between the sample line and the di-
lution apparatus.
7.3.1 Apparatus. The equipment required
in addition to that specified for the direct
interface system is as follows:
7.3.1.1 Sample Pump. Leakless Teflon-
coated diaphragm-type that can withstand
being heated to 120'C and deliver l.S liters/
minute.
7.3.1.2 Dilution Pumps. Two Model A-1SO
Komhyr Teflon positive displacement type
delivering 150 cc/minute. or equivalent. As
an option, calibrated flowmeters can be used
in conjunction with Teflon-coated dia-
phragm pumps.
7.3.1.3 Valves. Two Teflon three-way
valves, suitable for connecting, to 6.4-mm
OD Teflon tubing.
7.3.1.4 Flowmeters. Two, for measure-
ment of diluent gas, expected delivery flow
rate to be 1,350 cc/mln.'
7.3.1.5 Diluent Gas with Cylinders and
Regulators. Gas can be nitrogen or clean
dry air. depending on the nature of the
source gases.
7.3.1.6 'Heated Box. Suitable for being
heated to 120'C. to contain the three
pumps, three-way valves, and associated
connections. The box should be equipped
with quick connect fittings to facilitate con-
nection of: (1) The heated sample line from
the probe, (2) the gas sampling valve, (3)
the calibration gas mixtures, and (4) diluent
gas lines. A schematic diagram of the com-
ponents and connections is shown in Figure
18-13.
(NOTE: Care must be taken to leak check
the system prior to the dilutions so as not to
create a potentially explosive atmosphere.)
The heated box shown in Figure 18-13 is
designed to receive a heated line from the
probe. An optional design is to build a probe
unit that attaches directly to the heated
box. In this way, the heated box contains
the controls for the probe heaters, or, if the
box is placed against the duct being sam-
pled, it may.be possible to eliminate the
probe heaters. In either case, a heated
Teflon line is used to connect the heated
box to the gas sampling valve on the Chro-
matograph.
-------
Section No. 3.16.10
Date June 30, 1988
Page 9
7.3.2 Procedure. Assemble the apparatus
by connecting the heated box. shown in
Figure 18-13. between the heated sample
line from the probe and the gas sampling
valve on the chromatograph. Vent the
source gas from the gas sampling valve di-
rectly to the charcoal filter, eliminating the
pump and rotameter. Heat the sample
probe, sample line, and heated box. Insert
the probe and source thermocouple to the
centrold of the duct, or to a point no closer
to the walls than 1 m. Measure the source
temperature, and adjust all heating units to
a temperature 0 to 3'C above this tempera-
ture. If this temperature Is above the safe
operating temperature of the Teflon compo-
nents, adjust the heating to maintain a tem-
perature high enough to prevent condensa-
tion of water and organic compounds.
Verify the operation of the dilution system
by analyzing a high concentration gas of
known composition through either the 10:1
or 100:1 dilution stages, as appropriate. (If
necessary, vary the flow of the diluent gas
to obtain other dilution ratios.) Determine
the concentration of the diluted calibration
gas using the dilution factor and the cali-
bration curves prepared in the laboratory.
Record the pertinent data on the data sheet
shown in Figure 18-11. If the data on the di-
luted calibration gas are not within 10 per-
cent of the expected values, determine
whether the chromatograph or the dilution
system is In error, and correct It. Verify the
OC operation using a low concentration
standard by diverting the gas into the
sample loop, bypassing the dilution system.
If these analyses are not within acceptable
limits, correct the dilution system to provide
the desired dilution factors. Make this cor-.
rectlon by diluting a high-concentration
standard gas mixture to adjust the dilution
ratio as required.
Once the dilution system and GC oper-
ations are satisfactory, proceed with the
analysis of source gas. maintaining the same
dilution settings as used for the standards.
Repeat the analyses until two consecutive
values do not vary by more than S percent
from their mean value are obtained.
Repeat the analysis of the calibration gas
mixtures to verify equipment operation.
Analyze the two field audit samples using
either the dilution system, or directly con-
nect to the gas sampling valve as required.
Record all data and report the results to the
audit supervisor.
7.3.3 Determination of Stack Oas Mois-
ture Content. Same as Section 7.2.3.
7.3.4 Quality Assurance. Same as Section
7.2.4.
7.3.5 Emission Calculations. Same as Sec-
tion 7.2.5, with the dilution factor applied.
7.4 Adsorption Tube Procedure (Alterna-
tive Procedure). It is suggested that the
tester refer to the National Institute of Oc-
cupational Safety and Health (NIOSH)
method for the particular organics to be
sampled. The principal Interferent will be
water vapor. If water vapor is present at
concentrations above 3 percent, silica gel
should be used In front of the charcoal.
Where more than one compound is present
In the emissions, then develop relative ad-
sorptlve capacity information.
7.4.1 Additional Apparatus. In addition
to the equipment listed in the NIOSH
method for the particular organic(s) to be
sampled, the following items (or equivalent)
are suggested.
7.4.1.1 Probe (Optional). Boroslllcate
glass or stainless steel, approximately 6-mm
ID, with a heating system If water conden-
sation Is a problem, and a filter (either in-
stack or out-stack heated to stack tempera-
ture) to remove paniculate matter. In most
Instances, a plug of glass wool Is a satisfac-
tory filter.
7.4.1.2 Flexible Tubing. To connect probe
to adsorption tubes. Use a material that ex-
hibits minimal sample adsorption.
7.4.1.3 Leakless Sample Pump. Flow con-
trolled, constant rate pump, with a set of
limiting (sonic) orifices to provide pumping
rates from approximately 10 to 100 cc/mln.
7.4.1.4 Bubble-Tube Flowmeter. Volume
accuracy within ± 1 percent, to calibrate
pump.
7.4.1.S Stopwatch. To time sampling and
pump rate calibration.
7.4.1.6 Adsorption Tubes. Similar to ones
specified by NIOSH. except the amounts of
adsorbent per primary /backup sections are
800/200 mg for charcoal tubes and 1040/260
mg for silica gel tubes. As an alternative.
the tubes may contain a porous polymer ad-
sorbent such as Tenax OC or XAD-2.
7.4.1.7 Barometer. Accurate to 5 mm Hg.
to measure atmospheric pressure during
sampling and pump calibration.
7.4.1.8 Rotameter. 0 to 100 cc/mln, to
detect changes in flow rate during sampling.
7.4.2 Sampling and Analysis. It Is sug-
gested that the tester follow the sampling
and analysis portion of the respective
NIOSH method section entitled "Proce-
dure." Calibrate the pump and limiting ori-
fice flow rate through adsorption tubes with
the bubble tube flowmeter before sampling.
The sample system can be operated as a "re-
circulating loop" for this operation. Record
the ambient temperature and barometric
pressure. Then, during sampling, use the ro-
tameter to verify that the pump and orifice
sampling rate remains constant.
Use a sample probe. If required, to obtain
the sample at the centroid of the duct, or at
a point no closer to the walls than 1 m. Min-
imize the length of flexible tubing between
the probe and adsorption tubes. Several ad-
sorption tubes can be connected in series. If
the extra adsorptlve capacity is needed. Pro-
vide the gas sample to the sample system at
a pressure sufficient for the limiting orifice
to function as a sonic orifice. Record the
total time and sample flow rate (or the
number of pump strokes), the barometric
pressure, and ambient temperature. Obtain
a total sample volume commensurate with
the expected concentration(s) of the volatile
organic(s) present, and recommended
sample loading factors (weight sample per
weight adsorption media). Laboratory tests
prior to actual sampling may be necessary
to predetermine this volume. When more
than one organic is present in the emissions,
then develop relative adsorptlve capacity in-
formation. If water vapor is present in the
sample at concentrations above 2 to 3 per-
cent, the adsorptlve capacity may be severe-
-------
Section No. 3.16.10
Date June 30, 1988
Page 10
ly reduced. Operate the gas chromatograph
according to the manufacture's instructions.
After establishing optimum conditions.
verify and document these conditions
during all operations. Analyze the audit
samples (see Section 7.4.4.3), then the emis-
sion samples. Repeat the analysis of each
sample until the relative deviation of two
consecutive injections does not exceed 5 per-
cent.
7.4.3 Standards and Calibration. The
standards can be prepared according to the
respective NIOSH method. Use a minimum
of three different standards; select the con-
centrations to bracket the expected average
sample concentration. Perform the calibra-
tion before and after each day's sample
analyses. Prepare the calibration curve by
using the least squares method.
7.4.4 Quality Assurance.
7.4.4.1 Determination of Desorption Effi-
ciency. During the testing program, deter-
mine the desorptlon efficiency In the ex-
pected sample concentration range for each
batch of adsorption media to be used. Use
an Internal standard. A minimum desorp-
tlon efficiency of 50 percent shall be ob-
tained. Repeat the desorptlon determina-
tion until the relative deviation of two con-
secutive determinations does not exceed 5
percent. Use the average desorptlon effi-
ciency of these two consecutive determina-
tions for the correction specified in Section
7.4.4.5. If the desorptlon efficiency of the
compound(s) of Interest is questionable
under actual sampling conditions, use of the
Method of Standard Additions may be help-
ful to determine this value.
7.4.4.2 Determination of Sample Collec-
tion Efficiency. For the source samples, ana-
lyze the primary and backup portions of the
adsorption tubes separately. If the backup
ponton exceeds 10 percent of the total
amount (primary and backup), repeat the
sampling with a larger sampling portion.
7.4.4.3 Analysis Audit. Immediately
before the sample analyses, analyze the two
audits in accordance with Section 7.4.2. The
analysis audit shall agree with the audit
concentration within 10 percent.
7.4.4.4 Pump Leak Checks and Volume
Flow Rate Checks. Perform both of these
checks immediately after sampling with all
sampling train components in place. Per-
form all leak checks according to the manu-
facturer's instructions, and record the re-
sults. Use the bubble-tube flowmeter to
measure the pump volume flow rate with
the orifice used in the test sampling, and
the result. If it has changed by more than 5
but less than 20 percent, calculate an aver-
age flow rate for the test. If the flow rate
has changed by more than 20 percent, reca-
librate the pump and repeat the sampling.
7.4.4.5 Calculations. All calculations can
be performed according to the respective
NIOSH method. Correct all sample volumes
to standard conditions. If a sample dilution
system has been used, multiply the results
by the appropriate dilution ratio. Correct all
results by dividing by the desorptlon effi-
ciency (decimal value). Report results as
ppm by volume, dry basis.
' 7.5 Reporting of Results. At the comple-
tion of the field analysis portion of the
study, ensure that the data sheets shown in
Figure 18-11 have been completed. Summa-
rize this data on the data sheets shown In
Figure 18-15.
8. Bibliography
1. American Society for Testing and Mate-
rials. Ci Through C. Hydrocarbons in the
Atmosphere by Gas Chromatography.
ASTM D 2820-72, Part 23. Philadelphia. Pa.
23:950-958. 1973.
2. Corazon, V. V. Methodology for Collect-
ing and Analyzing Organic Air Pollutants.
U.S. Environmental Protection Agency.
Publication No. EPA-600/2-79-042. Febru-
ary 1979.
3. Dravnieks, A., B. K. Krotoszynski, J.
Whitfield, A. O'Donnell, and T. Burgwald.
Environmental Science and Technology.
5(12):1200-1222. 1971.
4. Eggertsen. F. T., and F. M. Nelsen. Gas
Chromatographlc Analysis of Engine Ex-
haust and Atmosphere. Analytical Chemis-
try. 30(6): 1040-1043. 1958.
5. FeairheUer, W. R., P. J. Marn. D. H.
Harris, and D. L. Harris. Technical Manual
for Process Sampling Strategies for Organic
Materials. U.S. Environmental Protection
Agency. Research Triangle Park. NC. Publi-
cation No. EPA 600/2-76-122. April 1976.
172 p.
6. FR. 39 FR 9319-9323. 1974.
7. FR, 39 FR 32857-32860. 1974.
8. FR, 41 FR 23069-23072 and 23076-
23090. 1976.
9. FR, 41 FR 46569-46571. 1976.
10. FR, 42 FR 41771-41776. 1977.
11. Fishbein. L. Chromatography of Envi-
ronmental Hazards, Volume II. Elsevier Sci-
entific Publishing Company. NY. NY. 1973.
12. Hamersma. J. W.,' S. L. Reynolds, and
R. F. Maddalpne. EPA/IERL-RTP Proce-
dures Manual: Level 1 Environmental As-
sessment. U.S. Environmental Protection
Agency. Research Triangle Park. NC. Publi-
cation No. EPA 600/276-160a. June 1976.
130 p.
13. Harris, J. C.. M. J. Hayes. P. L. Levins.
and D. B. Lindsay. EPA/IERL-RTP Proce-
dures for Level 2 Sampling and Analysis of
Organic Materials. U.S. Environmental Pro-
tection Agency. Research Triangle Park,
NC. Publication No. EPA 600/7-79-033. Feb-
ruary 1979. 154 p.
14. Harris. W. E.. H. W. Habgood. Pro-
grammed Temperature Gas Chromatogra-
phy. John Wiley & Sons, Inc. New York.
1966.
15. Intersociety Committee. Methods of
Air Sampling and Analysis. American
Health Association. Washington, DC. 1972.
16. Jones, P. W., R. D. Grammar, P. E.
Strup, and T. B. Stanford. Environmental
Science and Technology. 70:806-810. 1976.
17. McNair Han Bunelli, E. J. Basic Gas
Chromatography. Consolidated Printers.
Berkeley. 1969.
18. Nelson, G. O. Controlled Test Atmos-
pheres, Principles and Techniques. Ann
Arbor Ann Arbor Science Publishers. 1971.
247 p.
-------
Section No. 3.16.10
Date June 30, 1988
Page 11
19. NIOSH Manual of Analytical Methods.
Volumes 1, 2, 3. 4. 5, 6, 7. U.S. Department
of Health and Human Services National In-
stitute for Occupational Safety and Health.
Center for Disease Control. 4676 Columbia
Parkway, Cincinnati. Ohio 45226. April
1977-August 1981. May be available from
the Superintendent of Documents, Govern-
ment Printing Office, Washington, DC
20402. Stock Number/Price: Volume 1—017-
033-00267-3/$13, Volume 2-017-033-00260-
6/$ll, Volume 3—017-033-00261-4/S14,
Volume 4-017-033-00317-3/S7.25, Volume
5-017-033-00349-1/S10, Volume 6-017-033-
00369-6/$9, and Volume 7-017-033-00396-
5/$7. Prices subject to change. Foreign
orders add 25 percent.
20. Schuetzle, D.. T. J. Prater, and S. R.
Ruddell. Sampling and Analysis of Emis-
sions from Stationary Sources; I. Odor and
Total Hydrocarbons. Journal of the Air Pol-
lution Control Association. 25(9):925-932.
1975.
21. Snyder. A. D.. F. N. Hodgson, M. A.
Kemmer and J. R. McKendree. Utility of
Solid Sorbents for Sampling Organic Emis-
sions from Stationary' Sources. U.S. Envi-
ronmental Protection Agency. Research Tri-
angle Park. NC Publication No. EPA 600/2-
76-201. July 1976. 71 p.
22. Tentative Method for Continuous
Analysis of Total Hydrocarbons in the At-
mosphere. Intersociety Committee. Ameri-
can Public Health Association. Washington.
DC 1972. p. 184-186.
23. Zwerg, G.. CRC Handbook of Chroma-
tography, Volumes I and II. Sherma. Joseph
(ed.). CRC Press. Cleveland. 1972.
-------
I. Nut of aonpany
Mdrtss
Contacts
Oat*
Phone
Process to be sampled
Duet or vint to be sampled_
II. Process description
lUw material
Products
Operating cycle
Check: Batch Continuous
Timing of batch or cycle
Best time to test
.Cyclic
Figure 18-1. Preliminary survey data sheet.
Component! to be analyzed
expected concentration
Suggested chromatographic column
Column flow rat* ml/min Bead pressure gon Hg
Column temperatore<
Isothermal *C
Programmed from *C to *C at •C/min
Injection port/sample) loop temperature *C
Detector temperature *C
Detector flow ratea: Hydrogen ml/min.
head pressure mm Hg
Air/Oxygen ml/min,
head preaaure mn Hg
Chart speed __^______> inches/minute
Compound data*
Compound Retention time Attenuation
Figure 18-2. Chromatographic conditions data sheet.
T) O W
03 SO 0)
Ot} rt D
(D (D rt
p.
I-1 t-i O
M C 3
£3
n> -z.
uo
o
OJ
U) CT\
CD*'
CO H-
O
-------
Preparation of Standards In Tedlar Bags
and Calibration Curve
Standards
Mixture Mixture
Standards Preparation Data:
Organic: __^^_^_
Bag number or Identification
Dry gas meter calibration factor
Final meter reading (liters)
Initial meter reading (liters)
Mete red volume (liters)
Average meter temperature CK)
Average meter pressure, gauge (mm Hg)
Average atmospheric pressure (mm Hg)
Average meter pressure, absolute (mm Hg)
Syringe temperature CK)
(Section 6.2.2.1)
Syringe pressure, absolute (mm Hg)
(Section 6.2.2.1)
Volume of gas In syringe (ml)
(Section 6.2.2.1)
Density of liquid organic (g/ml)
(Section 6.2.2.2)
Volume of liquid In syringe ({!)
(Section 6.2.2.2)
GC Operating Conditions:
Sample loop volume (ml)
Sample loop temperature CO
Carrier gas flow rate (ml/mln)
Column temperature
Initial CO
Rate change CC/m1n)
Final CO
Organic Peak Identification and
Calculated Concentrations:
Injection time (24-hr clock)-
Distance to peak (cm)
Chart speed (cm/mln)
Organic retention time (mini
Attenuation factor
Peak height (mm)
Peak area (mm2)
Peak area x attenuation factor (rm2)
Calculated concentration (ppm)
(Equation 18-3 or 18-4)
Plot peak area x attenuation factor against calculated concentration
to obtain calibration curve.
Figure 18-3. Standards prepared In Tedlar bags
and calibration curve.
Flow»et*r Calibration
Flowneter number or Identification
Flowmeter type
Calibration device Ix):Bubble meter_
Readings at laboratory conditions:
Laboratory temperature (T)a[))
Laboratory barometric pressure
Flow data:
Flowmeter
Sp1rometer_
Wet test meter
Hg
Calibration device
reading I
(as narked)!
temp.
CK)
1 pressure
((absolute)
Time I I
(mln) I gas volume* I flow rateb
a * Volume of gas measured by calibration device, corrected to standard
conditions (liters).
b • Calibration device gas volume/time.
Plot flowmeter reading against flow rate (standard conditions), and draw a
smooth curve. If the flowmeter being calibrated 1s a rotaaeter or other
flow device that Is viscosity dependent, It may be necessary to generate a
'fully* of calibration curves that cover the operating pressure and
temperature ranges of the flowneter.
While the following technique should be verified before application. It may
be possible to calculate flow rate readings for rotameters at standard
conditions Q$td « follows:
Qstd. • Qlab
/760M
VTalT
* "
1/2
Flow rate
(laboratory conditions)
Flow rate
(standard conditions)
Figure 18-4. Flowneter calibration.
T3 U C/>
0 pj CD
(jq rt O
CD CD rt
H-
H" C_, O
OJ C 3
CD "Z
O
00
OO (
-------
Section No. 3.16.10
Date June 30, 1988
Page 14
COMPONENT
CAS
CYLINDER
\
CALIBRATED ROTAMETERS
WITH ROW CONTROL
VALVES
DILUENT
CAS
CYLINDER
Figure 18-5. Single-stage calibration gas dilution systea.
HIGH
CONCENTRATION
WASTE
I.
—NEEDLE VALVES
ROTAMETERS ~
m
m
LOW
•CONCENTRATION
GAS
PRESSURE
'PR ' REGULATOR
DILUENT AIR
DILUENT AIR
PURE SUBSTANCE OR
PURE SUBSTANCE/N2 MIXTURE
Figure 18-6. Two-stage dilution apparatus.
-------
Section No. 3.16.10
Date June 30, 1988
Page 15
Preparation of Standards by Dilution of Cylinder Standard
Cylinder standard: Organic Certified concentration ppn
Standards Preparation Data: Date
Mixture 1 Mixture 2 Mixture 3
Standard gas flowmeter reading
Diluent gas flowraeter reading
Laboratory temperature CK)
Barometric pressure (mm Hg)
Flowmeter gage pressure (mm Hg)
Flow rate cylinder gas at
standard conditions (ml/mln)
Flow rate diluent gas at
standard conditions (ml/mini
Calculated concentration (ppn)
Stage 2 (If used)
Standard gas flowmeter reading
Diluent gas flowmeter reading
Flow rate stage 1 gas at
standard conditions (ml/mln)
Flow rate diluent gas at
standard conditions (ml/mini
Calculated concentration (ppn)
GC Operating Conditions:
Sample loop volume (ol)
Sample loop temperature (*C)
Carrier gas flow rate (ml/mln)
Column temperature:
Initial CO
Program rate CC/min)
Final CO
Organic Peak Identification and
Calculated Concentrations:
Injection time (24-hr clock)
Distance to peak (cm)
Chart speed (cm/mln)
Retention time (m1n)
Attenuation factor
Peak area (mm2)
Peak area x attenuation factor
Plot peak area x attenuation factor against calculated concentration to
obtain calibration curve.
Figure 18-7. Standards prepared by dilution of cylinder standard.
-------
Section No. 3.16.10
Date June 30, 19§8
Page 16
BOILING -*
WATER
BATH
SYRINGE
SEPTUM
14- MIDGET
IMPINGER
HOTPLATE
NITROGEN
CYLINDER
Figure 18-8. Apparatus for preparation of liquid Materials.
VENT
STACK
WAIL
\
REVERSE
0"IIYPE
P1TOTTUBE
PITOT MANOMETER
RIGID LEAKPROOF CONTAINER
Figure 18-9. Integrated bag sampling train.
-------
Section No. 3.16.10
Date June 30, 1988
Page 17
WC Tubing
FloMHtter
MractlMl
HtHIt falw
Mr Tight Stetl On* ,
; "*"•••.
' t
• *
• ^. *
'•% ;
\ /
j
* •
« /
-VfVf
CVBCVBtAQ StGCI
Droi
Figure 18-9a. Explosion risk g«s sailing «ethod.
Plant.
S1t«
Date
Sample 1
Seurci twperatura (*C)
Barantrlc prissurt(nn Hg)_
Ambltnt tcop«riturt (*C) _
Sanplt flow r»te(appr.) _
Bag nunber
Start tine
Finish tine
Sample 2
Sample 3
Figure 18-10. Field sample data sheet - Tedlar
bag collection method.
-------
Section No. 3.16V10
Date June 30,
Page 18
riant ; Date_
Location
1. General information
Source temperature (*C)
Probe temperature (•«
Ambient temperature (*C)
Atmospheric pressure (am)
Source pressure ('Eg)
Absolute source pressure (an)
Sampling rate (liter/min)
•ample loop volume (ml)
Sample loop temperature (*C)
Columnar temperature i
initial (*C)/tiM (min)
Program nu CC/min)
Final (*C)/tlM
Carrier gas flow rate (ml/min)
Detector temperature (*C)
Injection time (24-hour buls)
Chart speed (mm/min)
Dilution gas flow rate (ml/min)
Dilution Cas used (symbol)
Dilution ratio
Figure 18-11. Field tnilysls dtti shttts.
2. Tield Analysis Data - Calibration Gas
tan MO. Time
ments Area Attenuation A « A factor Cone, (mm)
JU-n He. Ti»e
Cempcnents Area Attenuation A K A Factor Cone, (ppm)
»un Mo. Time
Components Area Attenuation A « A Factor Cone, (ppm)
Figure 18-11 (tontlmttd). Field antlytls dtU »httt».
-------
Section No. 3.16.10
Date June 30, 1988
Page 19
TC
KAOOUT
M
T C RMKU1
OR
ONitoun
UUIUlllUUUI.
. I1BULATKM
mm ots
SMVUNCVM.W
met
Figure 18-52. Direct Interface sampling syste*.
Vent to Charcoal Adsorbers
Heated Line
From Probe
t
t
=X»E
Quick
Connect
-Q~
Source
Gas Pump
i
IbU
cc/M1r
Pun
—t-
1.5 L/M1n "
i
10:1 100:1
'VJ^
'-&
)
-4
3-Uay Valves
In 100:1
Position '
^—^
-i
)
Quick Connects
To Gas Sample
Valve
J 150 cc/MIn
i Pump
Check Valve I
' Quick Connects 1
> For Calibration t
||
FloMneters
(On Outside
Of Box)
Flow Rate Of
1350 cc/MIn
Heated Box at 120 C Or Source Temperature
Figure 18-13. Schematic diagram of the heated box required
for dilution of sample gas.
-------
Section No. 3.1640
Date June 30, 1988
Page 20
OAUOUI OBOAKIC Bummo AJTD AHALTBU
CHECKLIST
(Respond with Initials or number u £2JK
appropriate) i
1. General
Information:
Source-
temperature
Da«« CO
1. Praumrdau: Probe
A. Grab ample collected... D temperature
B. Onto ample analyzed i—hi—i.
for compoaltlan a Ambient
CO-
mblex
temperature
a D
Method OC D D ....
a D 'c>
Atmospheric
C. OC-FTD analysis per- {mTa?)
(onned a ._
Source
2. laboratory calibration data:
A. Calibration curvea pre-
Number of oompo- (ml/mln)-
nenU a O Sample loop
volume (ml).. _
Sample loop
temperature
CO-
Sample
collection
time (24-hr
basis)...
Column
tempera.
OK obtained for tun:
field work..——... O ,,,, - i^mai
3. Sampling, procedures: , CO.—
A. Method: Prosram
Bas ample O D rate CC/
Direct Interface O D mini..
Dilution Interface— D O Final CC)...
B. Number of aampla col- Carrier iss
leeud ___... _.. 1O ..._..__ low rate
4. Field analysis: (ml/mln)
A. Total hydrocarbon Detector
analysts performed—— O temperature
B. Calibration curve pre-
CO..
*"'""" »"""' *»•«- |-tl»rt ••..•1
pared _________ Q —____.. Chart
-------
Section No. 3.16.10
Date June 30, 1988
Page 21
APPENDIX C—QUALITY ASSURANCE
PROCEDURES *
Procedure 1—Determination of Adequate
Chromatographic Peak Resolution
In this method of dealing with resolution,
the extent to which one Chromatographic
peak overlaps another is determined.
For convenience, consider the range of the
elution curve of each compound as running
from -2cr to +20-. This range is used in
other resolution criteria, and it contains
95.45 percent of the area of a normal curve.
If two peaks are separated by a known dis-
tance, b, one can determine the fraction of
the area of one curve that lies within the
range of the other. The extent to which the
elution curve of a contaminant compound
overlaps the curve of a compound that is
under analysis is found by integrating the
contaminant curve over the limits b-2cr. to
b-f-2cr,, where a-, is the standard deviation of
the sample curve.
This calculation can be simplified in sever-
al ways. Overlap can be determined for
curves of unit area; then actual areas can be
introduced. Desired integration can be re-
solved into two integrals of the normal dis-
tribution function for which there are con-
venient calculation programs and tables. An
example would be Program 15 In Texas In-
struments Program Manual ST1, 1975,
Texas Instruments, Inc., Dallas, Texas
75222.
In judging the suitability of alternate GC
columns or the effects of altering Chromato-
graphic conditions, one can employ the area
overlap as the resolution parameter with a
specific maximum permissible value.
The use of Gaussian functions to describe
Chromatographic elution curves is wide-
spread. However, some elution curves are
highly asymmetric. In cases where the
sample peak is followed by a contaminant
that has a leading edge that rises sharply
but the curve then tails off. it may be possi-
ble to define an effective width for tc as
"twice the distance from the leading edge to
a perpendicular line through the maxim of
the contaminant curve, measured along a
perpendicular bisection of that line."
Procedure 2—Procedure for Field Auditing
GC Analysis
Responsibilities of audit supervisor and
analyst at the source sampling site include
the following:
A. The audit supervisor verifies that audit
cylinders are stored in a safe location both
before and after the audit to prevent van-
dalism.
B. At the beginning and conclusion of the
audit, the analyst records each cylinder
number and pressure. An audit cylinder is
never analyzed when the pressure drops
below 200 psi.'
C. During the audit, the analyst performs
a minimum of two consecutive analyses of
each audit cylinder gas. The audit must be
conducted to coincide with the analysis of
source test samples, normally immediately
after GC calibration and prior to sample
analyses.
D. At the end of audit analyses, the audit
supervisor requests the calculated concen-
trations from the analyst and compares the
results with the actual audit concentrations.
If each measured concentration agrees with
the respective actual concentration within
±10 percent, he directs the analyst to begin
analyzing source samples. Audit supervisor
judgment and/or supervisory policy deter-
mine action when agreement is not within
±10 percent. When a consistent bias in
excess of 10 percent is found, it may be pos-
sible to proceed with the sample analysis.
with a corrective factor to be applied to the
results at a later time. However, every at-
tempt should be made to locate the cause of
the discrepancy, as it may be misleading.
The audit supervisor records each cylinder
number, cylinder pressure (at the end of the
audit), and all calculated concentrations.
The individual being audited must not
under any circumstance be told actual audit
concentrations until calculated concentra-
tions have been submitted to the audit su-
pervisor.
CFR-61, Appendix C, Quality Assurance Procedures, July 1, 198?, pages 157 - 161.
-------
Section No. 3.16.10
Date June 30,
Page 22
b»2o
b-2o, b-2as b+2os
~°T ' ~
The following calculation steps are required:*
1. 2os = tt/A In 2
2. oc = tc/2V2 In 2
3. x, = (b-2of)/oc
4. x, = (b+2oj)/oc
dx
6. Q(x2)
m
'dx
7- L
*»
- Q(XI)
Ao •
9. Percentage overlap = A x 100 ,
where:
A = Area of the sanple peak of Interest determined by electronic Inte-
gration or by the formula AS = hftt-
A * Area of the contaminant peak, determined in the same manner as A$.
b « Distance on the chrooatographlc chart that separates the maxima of
the two peaks.
H = Peak height of the sanple compound of Interest, measured from the
average value of the baseline to the maximum of the curve.
ts =• Width of sample peak of Interest at 1/2 peak height.
tc = Width of the contaminant peak at 1/2 of peak height.
o - Standard deviation of the sanple compound of Interest elutlon
curve.
a « Standard deviation of the contaminant elutlon curve.
Q(X|) = Integral of the normal distribution function from x, to Infinity.
Q(XJ) = Integral of the normal distribution function from x2 to Infinity.
I = Overlap Integral.
AO * Area overlap fraction.
*In s»st Instances, Q(x2) Is very snail and nay be neglected.
FIELD AUDIT REPORT
Part A.—To be filled out by organization
supplying audit cylinders.
1. Organization supplying audit sample(s)
and shipping address
2. Audit supervisor, organization, and
phone number
3. Shipping instructions: Name, Address.
Attention
4. Guaranteed arrival date for cylin-
5. Planned shipping date for cylin-
6. Details on audit cylinders from last
analysis
a. Date of last analysis
b Cytinder number
c. Cylinder pressure, psi
d. Audit gas(es)/balance gas -.
f. Cylinder construction
Low cone.
High cone.
Part B.—To be filled out by audit supervi-
sor.
1. Process sampled-
2. Audit location-
3. Name of individual audit-
4. Audit date
5. Audit results:
d. Measured concentration, ppm Injection
#1" Injection #2' Average ..
e. Actual audit concentration, ppm (Part A.
So)
1. Audit accuracy:1
High Cone Cylinder ....
Percent' accuracy -
Measured Cone. - Actual Cone.
Actual Cone.
Low
cone.
cylin-
der
High
cone.
cylin-
der
1 Results of two consecutive infections that meet the
sample analysis cntena of the test method.
[47 PR 39178. Sept. 7. 1982]
-------
Section No. 3-l6.ll
Date June 30, 1988
Page 1
11.0 REFERENCES
1. Method 18 - Measurement of Gaseous Organic Compound Emissions by Gas
Chromatography. Federal Register. Volume 48, No. 202, October 1-8, 1983,
page 48344.
2. Amendments to Method 18. Federal Register. Volume 49, No. 105, May 30,
1984, page 22608.
3. Miscellaneous Clarifications and Addition of Concentration Equations to
Method 18. Federal Register. Volume 52, No. 33, February 19, 198?, page
5105-
4. Stability of Parts-Per-Million Organic Cylinder Gases and Results of
Source Test Analysis Audits, Status Report #8. U. S. Environmental
Protection Agency Publication No. EPA-600/2-86-117, January 198?. Also
available from NTIS as Publication No. PB 8?-l4l46l.
5. Traceability Protocol for Establishing True Concentration of Gases Used
for Calibration and Audits of Continuous Source Emission Monitors
(Protocol No. 1). Section 3-0.4, Quality Assurance Handbook, Volume
III, Stationary Source Specific Methods, U. S. Environmental Protection
Agency Publication No. EPA-600/4-77-027b, June 15, 1978.
6. Methanol, Method 2000. NIOSH Manual of Analytical Methods, Volume 2,
Third Edition, U. S. Department of Health and Human Services, February
1984.
7. Alcohols I, Method 1400. NIOSH Manual of Analytical Methods, Volume 1,
Third Edition, U. S. Department of Health and Human Services, February
1984.
8. Alcohols II, Method 1401. NIOSH Manual of Analytical Methods, Volume 1,
Third Edition, U. S. Department of Health and Human Services, February
1984.
9. Hydrocarbons, BP 36 - 126° C, Method 1500. NIOSH Manual of Analytical
Methods, Volume 2, Third Edition, U. S. Department of Health and Human
Services, February 1984.
10. Development of Methods for Sampling 1,3-Butadiene. Interim Report
prepared under U. S. Environmental Protection Agency Contract Number
68-02-3993, March 1987.
11. Hexachlorocyclopentadiene, Method 2518. NIOSH Manual of Analytical
Methods, Volume 2, Third Edition, U. S. Department of Health and Human
Services, February 1984.
12. Method 110 - Determination of Benzene from Stationary Sources, Proposed
Rule. Federal Register, Volume 45, No. 77, April 18, 1980, page 26677.
-------
Section No. 3.16.11
Date June 30, 1988
Page 2
13. Hydrocarbons, Aromatic, Method 1501. NIOSH Manual of Analytical Methods,
Volume 2, Third Edition, U. S. Department of Health and Human Services,
February 1984.
14. Naphthylamines, Method 264. NIOSH Manual of Analytical Methods, Volume
4, Second Edition, U. S. Department of Health and Human Services, August
:. 1978.
15. Ketones I, Method 1300. NIOSH Manual of Analytical Methods, Volume 2,
Third Edition, U. S. Department of Health and Human Services, February
1984.
16. 2-Butanone, Method 2500. NIOSH Manual of Analytical Methods, Volume 1,
Third Edition, U. S. Department of Health and Human Services, February
1984.
17..- Ethylene Oxide, Method 1607. NIOSH Manual of Analytical Methods, Volume
1, Third Edition, U. S. Department of Health and Human Services, February
1984.
18. Propylene Oxide, Method 1612. NIOSH Manual of Analytical Methods, Volume
2, Third Edition, U. S. Department of Health and Human Services, February
1984.
19. Hydrocarbons, Halogenated, Method 1003. NIOSH Manual of Analytical
Methods, Volume 2, Third Edition, U. S. Department of Health and Human
Services, February 1984.
20. Ethylene Dibromide, Method 1008. NIOSH Manual of Analytical Methods,
Volume 1, Third Edition, U. S. Department of Health and Human Services,
February 1984.
21. Method 23 - Determination of Halogenated Organics from Stationary Sources
(proposed method). Federal Register, Volume 45, No. 114, June 11, 1980,
page 39766.
22. 1,2-Dichloropropane, Method 1013. NIOSH Manual of Analytical Methods,
Volume 1, Third Edition, U. S. Department of Health and Human Services,
February 1984.
23. Development of Methods for Sampling Chloroform and Carbon Tetrachloride.
Interim Report prepared for U. S. Environmental Protection Agency under
EPA Contract Number 68-02-3993, November 1986.
24. Dichlorodifluoromethane, Method 111. NIOSH Manual of Analytical Methods,
Volume 2, Second Edition, U. S. Department of Health and Human Services,
April 1977-
-------
Section No. 3.16.11
Date June 30, 1988
Page 3
25. Methyl Bromide, Method 2520. NIOSH Manual of Analytical Methods, Volume
2, Third Edition, U. S. Department of Health and Human Services, February
1984.
26. Methyl Chloride, Method 99. NIOSH Manual of Analytical Methods, Volume
4, Second Edition, U. S. Department of Health and Human Services, August
1978.
27. Butler, F. E., E. A. Coppedge, J. C. Suggs, J. E. Knoll, M. R. Midgett,
A. L. Sykes, M. W. Hartman, and J. L. Steger. Development of a Method
for Determination of Methylene Chloride Emissions at Stationary Sources.
Paper for presentation at 80th Annual Meeting of Air Pollution Control
Association, New York, NY, June 1987.
28. Vinylidene Chloride, Method 266. NIOSH Manual of Analytical Methods,
Volume 4, Second Edition, U. S. Department of Health and Human Services,
August 1978.
29. Ethyl Chloride, Method 2519. NIOSH Manual of Analytical Methods, Volume
1, Third Edition, U. S. Department of Health and Human Services, February
1984.
30. Method 106 - Determination of Vinyl Chloride from Stationary Sources.
Federal Register, Volume 47, No. 173, September 7, 1982, page 39168.
31. Knoll, J. E., M. A. Smith, and M. R. Midgett. Evaluation of Emission
Test Methods for Halogenated Hydrocarbons, Volume II, U. S. Environmental
Protection Agency Publication No. EPA-600/4- 80-003, January 1980.
32. Methylene Chloride, Method 1005. NIOSH Manual of Analytical Methods,
Volume 2, Third Edition, U. S. Department of Health and Human Services,
February 1984.
33. Tetrachloroethylene, Method 335. NIOSH Manual of Analytical Methods,
Volume 3, Second Edition, U. S. Department of Health and Human Services,
April 1977-
34. Trichloroethylene, Method 336. NIOSH Manual of Analytical Methods,
Volume 3, Second Edition, U. S. Department of Health and Human Services,
April 1977-
35. 1,1,2-Trichlorotrifluoroethane, Method 129. NIOSH Manual of Analytical
Methods, Volume 2, Second Edition, U. S. Department of Health and Human
Services, April 1977.
36. Vinyl Chloride, Method 1007- NIOSH Manual of Analytical Methods, Volume
2, Third Edition, U. S. Department of Health and Human Services, February
1984.
37- Mann, J. B., J. J. Freal, H. F. Enos, and J. X. Danauskas. Development
and Application of Methodology for Determining 1,2 Dibromo-3-
Chloropropane (DBCP) in Ambient Air. Journal of Environmental Science
and Health, B15(5), 519-528 (1980).
-------
Section No. 3.16.11
Date June 30, 19S8
Page 4
38. VOC Sampling and Analysis Workshop, Volume III. U. S. Environmental
Protection Agency Publication No. EPA-340/1-84-001C, September 1984.
39. Knoll, J. E., M. A. Smith, and M. R. Midgett. Evaluation of Emission Test
Methods for Halogenated Hydrocarbons, Volume I. U. S. Environmental
Protection Agency Publication No. EPA-600/4-79-025, March 1979.
40. Binetti, R. et al. Headspace Gas Chromatographic Detection of Ethylene
Oxide in Air. Chromatographia, Vol. 21, December 1986.
4l. Butadiene, Method 591. NIOSH Manual of Analytical Methods, Volume 2,
Second Edition, U. S. Department of Health and Human Services, April 1977-
42. Knoll, J. E. Estimation of the Limit of Detection in Chromatography.
Journal of Chromatographic Science, Vol. 23, September 1985.
43. Procedure 1 - Determination of Adequate Chromatographic Peak Resolution.
Code of Federal Regulations, Title 40. Part 6l, Appendix C, July 1, 1987.
44. Method 625 - Base/Neutrals and Acids. Code of Federal Regulations, Title
40, Part 136, Appendix A, July 1, 1987.
45. C. through C,_ Hydrocarbons in the Atmosphere by Gas Chromatography. ASTM D
2Q20-72, Part 23. American Society for Testing and Materials,
Philadelphia, PA, 23:950-958, 1973.
46. Corazon, V. V. Methodology for Collecting and Analyzing Organic Air
Pollutants. U. S. Environmental Protection Agency Publication No.
EPA-600/2-79-042, February 1979.
47. Dravnieks, A., B. K. Krotoszynski, J. Whitfield, A. O'Donnell, and T.
Burgwald. Environmental Science and Technology, 5(12):1200-1222, 1971.
48. Eggertsen, F. T., and F. M. Nelson. Gas Chromatographic Analysis of Engine
Exhaust and Atmosphere. Analytical Chemistry, 30(6): 1040-1043, 1958.
49. Feairheller, W. R., P. J. Marn, D. H. Harris, and D. L. Harris. Technical
Manual for Process Sampling Strategies for Organic Materials, U. S.
Environmental Protection Agency, Publication No. EPA 600/2-76-122, April
1976.
50. FR, 39 FR 9319-9323, 1974.
51. FR, 39 FR 32857-32860, 1974.
52. FR, 41 FR 23069-23072 and 23076-23090, 1976.
53. FR, 41 FR 46569-46571, 1976.
54. FR, 42 FR 41771-41776, 1977-
-------
Section No. 3.16.11
Date June 30, 1988
Page 5
55. Fishbein, L. Chromatography of Environmental Hazards, Volume II. Elsevier
Scientific Publishing Company, New York, New York, 1973-
56. Hamersma, J. W., S. L. Reynolds, and R. F. Maddalone. EPA/IERL Procedures
Manual: Level 1 Environmental Assessment, U. S. Environmental Protection
Agency Publication No. EPA 600/276/l60a, June 1976.
57. Harris, J. C., M. J. Hayes, P. L. Levins, and D. B. Lindsay. EPA/IERL
Procedures for Level 2 Sampling and Analysis of Organic Materials. U. S.
Environmental Protection Agency Publication No. EPA 600/7-79-033, February
1979.
58. Harris, W. E., H. W. Habgood. Programmed Temperature Gas Chromatography.
John Wiley & Sons, Inc. New York, 1966.
59. Methods of Air Sampling and Analysis. Intersociety Committee, American
Health Association, Washington, D. C., 1972.
60. Jones, P. W., R. D. Grammer, P. E. Strup, and T. B. Stanford.
Environmental Science and Technology, 10:806-810, 1976.
6l. McNair Han Bunelli, E. J. Basic Gas Chromatography. Consolidated Printers,
Berkeley, 1969.
62. Nelson, G. 0. Controlled Test Atmospheres, Principles and Techniques. Ann
Arbor, Ann Arbor Science Publishers, 1971-
63. Schuetzle, D., T. J. Prater, and S. R. Ruddell. Sampling and Analysis of
Emissions from Stationary Sources; I. Odor and Total Hydrocarbons.
Journal of the Air Pollution Control Association, 1975-
64. Snyder, A. D., F. N. Hodgson, M. A. Kemmer, and J. R. McKendree. Utility
of Solid Sorbents for Sampling Organic Emissions from Stationary Sources.
U. S. Environmental Protection Agency Publication No. EPA 600/2-76-201,
July 1976.
65. Tentative Method for Continuous Analysis of Total Hydrocarbons in the
Atmosphere. Intersociety Committee, American Public Health Association,
Washington, D.C., 1972.
66. Zwerg, G. CRC Handbook of Chromatography, Volumes I and II. CRC Press,
Cleveland, 1972.
-------
Section No. 3.16.12
Date June 30, 1988
Page 1
12.0 DATA FORMS
Blank data forms are provided on the following pages for the convenience of
the Handbook user. Each blank form has the 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 M18-2.5 indicates that the form is Figure 2.5 in
Section 3.18.2 of the Method 18 section. Future revisions of these forms, if any,
can be documented by 2.5a, 2.5b, etc. Nineteen of the blank forms listed below are
included in this section. Six have been left blank in the text as shown following
the form number.
Form
2.1A & B
2.2A & B
2.5
2.6
2.7
3.1 (Text)
3.2 (Text)
3.4 (Text)
3.5 (Text)
4.1
4.2
4.3
4.8 (Text)
5-1
5-4
5-6
Title
Flowmeter Calibration Data Form
(English and metric units)
Critical Orifice Calibration Data Form
(English and metric units)
Dynamic Dilution Data Form
Static Dilution Data Form
Thermometer Calibration Form
Preliminary Survey Data Sheet
Preliminary Survey Preparations
Pretest Sampling Checks
Pretest Preparations
Field Sampling Data Form for Container Sampling
Field Sampling Data Form for Direct Interface Sampling
Field Sampling Data Form for Adsorption Tube Sampling
On-site Measurements Checklist
Data Form for Analysis of Method 18 Samples
Calibration Standard Preparation Data Form for Diluted
Gas Cylinders
Calibration Data Form for Preparation of Standards in
Tedlar Bags by Gas and Liquid Injection
-------
Section No. 3-16.12
Date June 30, 1988
Page 2
5.8 Data Form for Development of Response and Relative
Retention Factors
5.9 Data Form for Preparation of Liquid Standards and
Desorption Efficiency Samples for Adsorption Tube Analysis
5.10 (Text) Postsampling Operations Checklist
6.1 Calculation Form for GC Analysis by Gas Injection
6.2 Calculation Form for GC Analysis by Liquid Injection
8.1 Field Audit Report Form
8.2 Method 18 Checklist to be Used by Auditors
-------
FLOWMETER CALIBRATION DATA FORM (English units)
Date
Calibrated by
Meter system no.
Primary meter no.
op
Barometric pressure, Pn = in. Hg Ambient temperature
Type of primary meter: wet test , dry gas , or bubble meter
Type of flowmeter calibrated: rotameter
, dry gas meter
, or mass flowmeter
Primary meter readings
Initial
reading
(V } a
vvpi ' •
ft3
Final
reading
(vpf),a
ft3
Initial
temp , ° F
(tpl)
oF
Final
temp,°F
(tpf)
op
Press
drop
(DP)C
in.
H20
Flowmeter readings
Initial
reading
(V ),»
ft3 or
ft3 /min
Final
reading
(V"
ft3 or
ft3 /min
Initial
temp
(tsi)
op
Final
temp
(tsf)
op
Press
drop
(Ds),c
in.
H20
Time
min
(e)_d
min
Calibration
factors
(YJ,'
(Yj
a Volume passing through the meter using the initial and final readings; requires a minimum of at
least five revolutions of the meter.
b Volume passing through the meter using the initial and final readings or the indicated flow rate
using the initial and final flow rate setting.
c Pressure drop through the meter used to calculate the meter pressure.
d The time it takes to complete the calibration run.
e With Y defined as the average ratio of volumes for the primary meter compared to the flowmeter
calibrated, Yj = Y +_ 0.03Y for the calibration and Yf = Y ^ 0.05Y for the posttest checks; thus:
Y, =
For calibration of the dry gas meter:
+ tsf)/2 + 460°F][Pm + (Dp/13.6)]
-(Eq.2-l),Y =
-(Eq.2-2)
[<*.! + tsf)/2 + 160°F][Pm + (DpA3.6)]
[(Vsf * Vs.)/2]0[(t + t )/2 + 460°F][Pra * (D.A3-6)]
-(Eq. 2-3),Y =
-(Eq.2-4)
Quality Assurance Handbook M18-2.1A
-------
FLOWMETER CALIBRATION DATA FORM (metric units)
Date
Calibrated by
Meter system no.
Barometric pressure, Pm =
Type of primary meter: wet test •
Type of flowmeter calibrated: rotameter
mm Hg Ambient temperature
Primary meter no.
°C
, dry gas
, or bubble meter
, dry gas meter
, or mass flowmeter
Primary meter readings
Initial
reading
(vpl),a
m3
Final
reading.
(vpf),a
m3
Initial
temp,°F
(tpl)
°C
Final
temp,°F
(tpf)
°C
Pres
drop
(Dp)c
mm
H20
Flowmeter readings
Initial
reading
(v?i),b
m* or
m3/min
Final
reading
H20
Time
min
(e)_d
min
Calibration
factors
(YJ,6
(Y)
8 Volume passing through the meter using the initial and final readings and requires a minimum of at
least five revolutions of the meter.
b Volume passing through the meter using the initial and final readings or the indicated flow rate
using the initial and final flow rate setting.
c Pressure drop through the meter used to calculate the meter pressure.
d . The time it takes to complete the calibration run.
e With Y defined as the average ratio of volumes for the primary meter compared to the flowmeter
calibrated, Y. = Y + 0.03Y for the calibration and Yt = Y + 0.05Y for the posttest checks; thus,
For calibration of the dry gas meter: - .
. + tsf)/2 + 273°K][Pm + (Dp/13.6)]
.(Eq. 2-5) •, Y =
K 273°K][Pm +- I
For calibration of the rotameter and mass .flowmeter:
-------
CRITICAL ORIFICE CALIBRATION DATA FORM (English units)
Date
Calibrated by
Meter system no.
Barometric pressure, Pm =
Type of primary meter: wet test
Type of critical orifice: capillary glass
in. Hg Ambient temperature
, dry gas
Primary meter no.
op
needle or tubing
, or bubble meter
, or adjustable
Primary meter readings
Initial
reading
(vpi),a
ft3
Final
reading
(V ) a
*vpf ' •
ft3
Initial
temp , ° F
(tpi)
op
Final
temp , ° F
(tpf)
op
Pres
drop
<°P>
in.
H20
Critical orifice readings
Initial
setting
b
ft3 or
ft3 /min
Final
setting
b
ft3 or
ft3 /min
Press
drop
c
in.
Hg
Time
min
(e) d
min
Calculated
flow rate
[Q(std)]e
ft3 /min
Calibration
factor*
(K'J
(K')
a Volume passing through the meter using the initial and final readings and requires a minimum of at
least five revolutions of the meter.
b Volume passing through the orifice using the initial and final readings or the indicated flow rate
using the initial and final flow rate setting (for variable setting orifice only).
0 Pressure drop through the meter used to calculate the meter pressure.
d The time it takes to complete the calibration run.
e With K1 defined as the average orifice calibration factor based on the volumes of the primary test
meter, K'A = K' + 0.03K' for the calibration and K'j = K1 + 0.05K1 for the posttest checks: thus,
Flow rate of the primary meter at standard conditions:
Vp
( s td )
l7.7Kvpf - vpi)(Pm * Dp/13.6)
[
-------
CRITICAL ORIFICE CALIBRATION DATA FORM (metric units)
Date
Calibrated by
Meter system no.
Barometric pressure, Pm =
Type of primary meter: wet test
Type of critical orifice: capillary glass
Primary meter no.
°C
mm Hg Ambient temperature '
, dry gas , or bubble meter
needle or tubing
, or adjustable
Primary meter readings
Initial
reading
(vpi).a
L
Final
reading
(V ) a
i%f ' •
L
Initial
temp , ° F
(tpt)
°C
Final
temp,°F
(tpf)
°C
Pres
drop
-------
DYNAMIC CALIBRATION DATA FORM
Date •
Source flowmeter number
Stage 1 flowmeter number
Stage 2 flowmeter number
Barometric press mm (in.) Hg
Organic compound
Calibrated by ,
Date source metee calibrated
Date stage 1 meter calibrated
Date stage 2 meter calibrated
Heated box temperature
Leak check for total
system
Certified concentration
ppmv(X) Date of calibration curve
STAGE 1
Emission gas flowmeter reading, ml/min (qcl).
Diluent gas flowmeter reading, ml/min (qdl)
Dilution ratio
Injection time, 2kh
Distance to peak, cm
Chart speed, cm/min
Retention time, min
Attenuation factor
Peak area or units
Peak area X attenuation factor
Measured concentration,8 ppmv
Calculated concentration,6 ppmv (Cs)
Percent difference,"1 %
STAGE 2 (if applicable)
Emission gas flowmeter reading, ml/min (qc2).
Diluent gas flowmeter reading, ml/min (qd2)
Dilution ratio
Injection time, 24h
Distance to peak, cm
Chart speed, cm/min
Retention time, min
Attenuation factor
Peak area or units
Peak area X attenuation factor
Measured concentration,3 ppmv
Calculated concentration,d ppmv
Percent difference,0 %
RUN 1
RUN 2
RUN 1
RUN2
RUN3
See Figure 5-1 for calculation.
C. =
106 x (X x qj
= Calculated concentration for single stage
Calculated Concentration - Measured Concentration
Percent Difference =
x 1002
Measured Concentration
C, = 106 x X
(q
cl
qdl)
= Calculated cone, for two stage.
Quality Assurance Handbook M18-2.5
-------
STATIC DILUTION DATA FORM
Date Calibrated by
Source flowmeter number Date source meter calibrated _
Dry gas meter number Date dry gas meter calibrated
Ambient temperature °C (°F) Dry gas meter calib factor (Y)
Barometric press mm (in.) Hg Leak check for total system __
Organic compound Vacuum during leak check
Certified concen, (X) ppmv Date of calibration curve
RUN 1 RUN 2
Initial dry gas meter reading, L (ft3)
Final dry gas meter reading, L (ft3)
Volume of diluent gas metered, L (ft3)
Gas metered X calibration factor (Y),{V2}
Flowmeter sampling rate, ml/min (cfm)
Sampling time, min
Sampling rate X sample time, L (ft3),{V1}
Dilution ratio
Injection time, 24h
Distance to peak, cm
Chart speed, cm/min
Retention time, min
Attenuation factor
Peak area or units
Peak area X attenuation factor
Measured concentration,3 ppmv '
Calculated concentration,13 ppmv, {Cs}
Percent difference,0 %
a See Figure 5•1 for calculations. _
X (VJ
b Calculated concentration (C ) = = ppmv
Measured concent - Calculated concent
Percent difference, %d = ; X 100 =
Measured concentration
The percent difference must be less than 10 % absolute.
Quality Assurance Handbook M18-2.6
-------
THERMOMETER CALIBRATION FORM
Date
Reference
thermometer
type
Calibr
thermc
type
•ated
imeter
use
no.
" •
Ambier
refer8
it temper
calibr?
Measurec
•ature
differ0
values
Boi
refer8
ling wat
calibr"
,er
differ0
Calibrator's
initials
Temperature reading of the reference thermometer in °C or °F.
Temperature reading of the thermometer being calibrated in °C or °F.
Difference between the reference thermometer and the calibrated thermometer. This difference must
be less than 3°C (5.4°F) for than initial calibration and 6°C (10.4°F) for the calibration check.
Quality Assurance Handbook M18-2.7
-------
FIELD SAMPLING DATA FORM FOR CONTAINER SAMPLING
Plant
City
Operator
Date
Flowmeter calib.(Y)
Container type: bag
Run number
Stack dia, mm
(in. )
syringe
canister
Container volume,
Container number
Average ( P)
Dilution system: (dynamic)
emission flowsetting
diluent flowsetting
liters
mm (in.) H2 0
Sample box number
Pitot tube (Cp) _
Static press
mm (in.) H20
Initial flowmeter setting
Average stack temp
Barometric press
mm
°C (°F)
'(in.) Hg
Dilution system: (static)
emission flowsetting
Final leak check m3/min (cfm)
Vacuum during leak check
mm (in.) H20
Sampling point location
Sampling
time,
min
Total
Clock
time,
24 h
Velocity head
mm ( in . ) H2 0 ,
( P)
Avg
Flowmeter
setting
L/min (ft3 /min)
Avg
stack
°C (°F)
Avg
probe
°C (°F)
Avg
Temperature
sample line
°C (°F)
Avg
readings
flowmeter box
°C (°F)
Avg
container
°C (°F)
Avg
Quality Assurance Handbook M18-4.1
-------
FIELD SAMPLING DATA FORM FOR DIRECT INTERFACE SAMPLING
Plant
City
Operator
Date
Barometric press
Initial probe setting
Sampling rate
mm
Hg
(in.)
_ °C (°F)
L/min (cfm)
Run number
Stack dia,
Sampling point location
mm (in.)
Meter box number
Stack temp
Static press
mm (in.)
H20
Dilution system:
source flow rate
diluent flow rate
diluent flow rate
Dilution ratio
L/min (cfm)
L/min (cfm)
L/min (cfm)
Sample loop volume
Sample loop temp
Column temperature:
initial /
program rate /
final /
Carrier gas flow
ml
Ci O T?\
\ " 1
°C/min
°C/min
°C/min
ml/min
Dilution system check
Final leak check
Vacuum @ check
mm (in.)
H,0
Time of
injection
24 h
Injection
number
Flov
source
ml/min
raieter(s) s
diluent
ml/min
>ettings
diluent
ml/min
1)
stack
°C (°F)
Temporal
probe
°C (°F)
;ure readings
sample line
°C (°F)
injection port
°C (°F)
Quality Assurance Handbook M18-4.2
-------
FIELD SAMPLING DATA FORM FOR ADSORPTION TUBE SAMPLING
Plant
City
Operator
Date
Run number
Stack dia,
Flowmeter calib.(Y) _
Adsorption tube type:
charcoal tube
silica gel
other
mm (in.)
Meter box number
Pitot tube (Cp)
Static press
mm (in.)
H20
Adsorption tube number
Average ( P) mm
Initial flowmeter setting
Average stack temp
Barometric
(in.)
H20
press
mm
°C (
"(in.)
Dilution system: (dynamic)
emission flowsetting
diluent flowsetting
Dilution system: (static)
emission flowsetting
Final leak check m3/min (cfm)
Vacuum during leak check
mm (in.)
Sampling point location
H20
Hg
Sampling
time,
min
Total
Clock
time,
24 h
Velocity head
mm ( in . ) H2 0 ,
( P)
Avg
Flowmeter
setting
L/min (ft3 /min)
Avg
stack
°C (°F)
Avg
Temperature i
probe , line
°C (°F)
Avg
•eadings
adsorp . tube
°C (°F)
Avg
meter
°C (°F)
Avg
Vacuum
mm ( in . ) Hg
Avg
Quality Assurance Handbook M18-4.3
-------
ANALYSIS OF METHOD 18 FIELD SAMPLES
Date:
Location:
Analyst:
Plant:
Sample Type:
Type of Calibration Standard:
Number of Standards: Date Prepared:
Target Compound:
Prepared By:
GC Used:
Carrier Gas Used:
Column Temperatures, Initial:
Sample Loop Volume:
Detector Temp.:
Column Used:
Carrier Gas Flow Rate:
Program Rate:
Loop Temperature:
Final:
Inject. Port Temp.:
Auxiliary Gases:
Calibration Data
First analysis/second analysis
Standard concentration (Cact)
Flow rate through loop (ml/min)
Liquid injection volume (tubes)
Injection time (24-hr clock)
Chart speed (cm/min)
Detector attenuation
Peak retention time (min)
Peak retention time range (min)
Peak area
Peak area x attenuation factor
Average peak area value (Y)
Percent deviation from average
Calculated concentration (Cstd)
% deviation from actual
Standard 1
Standard 2
Standard 3
Linear regression equation; slope (m) :
y-intercept (b) :
Sample Analysis Data Sample 1
First analysis/second analysis
Sample identification
Interface dilution factor
Flow rate through loop (ml/min) /
Liquid injection volume (tubes) /
Injection time (24-hr clock) /
Chart speed (cm/min) /
Detector attenuation /
Peak retention time (min) /
Peak retention time range (min)
Peak area /
Peak area x atten. factor (At/A2) /
Average peak area value (Y)
% deviation from average (%Vav )
Calculated concentration (C )
Sample 2
Sample 3
(Y - b)
C
C. =
m
act
Quality Assurance Handbook M18-5-1
-------
PREPARATION OF STANDARDS BY DILUTION OF GAS CYLINDER STANDARDS
Date:
Preparer:
Purpose:
Cylinder Component:
Component Concentration (X-) :
Source:
ppm Certification Date:
Stage 1 Mixture 1 Mixture 2 Mixture 3
Standard gas flowmeter reading •
Diluent gas flowmeter reading
Laboratory temperature (°K) .
Barometric pressure (Pb) (mm Hg) •
Flow rate of cylinder gas (qcl) at
standard conditions (ml/min) •
Flow rate of diluent gas (qdl) at '
standard conditions (ml/min)
Calculated
Stage
concentration (Cs )
«
2 (if used)
Xxqcl
3d + 3dl
Mixture 1
Mixture 2 Mixture 3
Standard gas flowmeter reading
from stage 1
Diluent gas flowmeter reading
into stage 2
Average differential pressure (Pd )
between stage 1 and 2 (mm H20)
Flow rate of diluted gas
tec2 actual) at standard
conditions to stage 2 (ml/min)
Flow rate of diluted gas
at corrected
to
stage 2 (ml/min)
Flow rate of diluent gas (qd2) at
standard conditions to
stage 2 (ml/min)
Calculated concentration (C )
c2 corr)
standard conditions
= 3
c 2 actual
Cs = X x
: 2 c o r r
(3d + 3dl) (q
c 2 c o r r
Quality Assurance Handbook M18-5-4
-------
PREPARATION OF STANDARDS IN TEDLAR BAGS BY GAS AND LIQUID INJECTION
Date: Preparer: Purpose:
Organic Compound: • Gas: or Liquid:
Compound Source: Compound Purity (P): % Compound Mole Weight (M):
Gas Injection Mixture 1 Mixture 2 Mixture 3
Bag number or identification
Dry gas meter calibration factor (y)
Final gas meter reading, liters
Initial gas meter reading, liters
Volume metered (Vm), liters
Ambient temperature, °C
Average gas meter temperature, °C
Absolute gas meter temp. (Tm), °K
Barometric pressure (Pb), mm Hg
Average gas meter pressure, mm Hg
Absolute gas meter press. (Pra)t nun Hg
Gas volume injected (Gv), ml
Syringe temperature (T8), °K
Absolute syringe pressure (Ps), mm Hg
Calculated concentration (Cs)
ps * Tn
"• vs calc
Ts x Pm Cs corr = x 100*
cs = P
vm * y
Liquid Injection Mixture 1 Mixture 2 Mixture 3
Bag number or identification
Dry gas meter calibration factor (y)
Final gas meter reading- liters
Initial gas meter reading, liters .
Volume metered (Vm), liters
Average gas meter temperature, °C .
Absolute gas meter temp. (Tm ), °K
Barometric pressure (Pb), mm Hg
Average gas meter pressure, mm Hg
Absolute gas meter press. (Pm)t mm Hg
Liquid organic density (p), ug/ml
Liquid volume injected (Lv), ul
Calculated concentration (Cs)
' Lv * P * Tm Cs calc
Cs = 6.24 x 10" x Cs co.rr = x 100*
M x Vm x y x Pm P
Quality Assurance Handbook M18-5.6
-------
DEVELOPMENT OF RELATIVE RESPONSE FACTORS AND RELATIVE RETENTION FACTORS
Date: Preparer:
Target Compound:
Surrogate Compound:
Purpose:
Type of Standard:
Type of Standard:
Target Compound Calibration Data Standard 1
First analysis/verify analysis
Standard concentration
Flow rate through loop (ml/min) /
Liquid injection volume (tubes) /
Injection time (24-hr clock) /
Chart speed (cm/min) /
Detector attenuation /
Peak retention time (tRxl/tRxf) /
Peak retention time range
Peak area (_
Peak area x atten. factor (Yi/Yx) /
Verification analysis conc.(Cx)
Percent deviation from actual
Caculated retention time (rTxf)
Percent deviation from actual
Linear regression equation; slope (m ):
Standard 2
Standard 3
y-intercept (b) :
Surrogate Calibration Data
First analysis/second analysis
Standard concentration
Flow rate through loop (ml/min)
Liquid injection volume (tubes)
Injection time (24-hr clock)
Chart speed (cm/mni)
Detector attenuation
Peak retention time (tRsl/tRsf)
Peak retention time range
Peak area
Peak area x attenuation factor
Linear regression equation; slope (m
Standard 1
Standard 2 Standard 3
(mf)
y-intercept (b) :
Nonretained peak retention time (tM1/tMf):
Relative Response Factor (FRv):
Rx
Relative Retention Factor (rv/Q):
X / 5
ms
FRX = —
-x/s
c =
^Mi
"std
x F
Rx
°Mf
Quality Assurance Handbook M18-5-8
-------
DATA FORM FOR PREPARATION OF LIQUID STANDARDS AND DESORPTION EFFICIENCY SAMPLES
Date:
Preparer:
Purpose:
Organic Compound: _
Compound Source:
Adsorbent Material:
Gas:
Compound Purity (P):
Batch No:
or Liquid:
% Compound Mole Weight (M):
Desorption Solvent:
Standards in Solvent Mixture 1 Mixture 2 Mixture 3
Desorption solvent volume (Vs), ml
Compound spike amount (V0), ul
Organic compound density (p), ug/ul
Standard concentration (C ), ug/ml
Standards on Adsorbent
Adsorbent amount, g
Compound spike amount (V0), ul
Organic compound density (p), ug/ul
Desorption solvent volume (Vs), ml
Desorption time, min
Standard concentration (C8), ug/ml
Mixture 1 Mixture 2 Mixture 3 Blank
GC Operating Conditions
Injection port temperature, °C
Carrier gas flow rate, ml/min
Column temperature:
Initial, °C
Program rate, °C/min
Final, °C
Chromatographic Results
Injection time,24-hr clock
Distance to peak, cm
Chart speed, cm/min
Retention time, min
Attenuation factor
Standards in desorption solvent:
Peak area (Ac), area counts
Standards and blank from
adsorbent material:
Peak area (As and Ab),
area counts
Mixture 1 Mixture 2 Mixture 3 Blank
Desorption Efficiency Calculation
Desorption Efficiency (DE), %
Mixture 1 Mixture 2 Mixture 3
C. =
V0 x p x P
V0 x 100%
As - Ab
DE = x
Quality Assurance Handbook M18-5.9
-------
CALCULATION FORM FOR GC ANALYSIS BY GAS INJECTION
SAMPLE CONCENTRATION
ppm, Pr = . _ mm Hg, Ti = . _ °K,
. _ mm Hg, Tr = . _ °K, Bws = 0 . ,
, F/ =
F K
r
PI Tr (1 - BW8K)
= ___ ppm Equation 6-1
If applicable.
Quality Assurance Handbook M18-6.1
-------
CALCULATION FORM FOR GC ANALYSIS BY LIQUID INJECTION
SAMPLE VOLUME, DRY BASIS AT STANDARD CONDITIONS
amb
K. B* - 0
P V
r v
v td d = 0-3858
"If applicable.
- B
DESORPTION EFFICIENCY
B =
Equation 6-2
DE = (Qr - B)/Qa = 0 . __
Equation 6-3
W
B
K' = 0 .
SAMPLE CONCENTRATION
ug, Wb = ____ ug, Bp = ____ ug,
ug, Vstd = ___ -_L, DE = 0. __ ,
C =
V
= ____ mg/dscm or ug/dsL Equation 6-
std
CONVERSION TO PPM
C = ____ mg/dscm or ug/dsL, MW = ___ . _ ug/ug-mole,
Cppm = 24.055 C (MW)
ppm Equation 6-5
Quality Assurance Handbook M18-6.2
-------
FIELD AUDIT REPORT
Part A. - To be filled out by organization supplying audit cylinders.
1. Organization supplying audit sample(s) and shipping'address
]
2. Audit supervisor, organization, and phone number
3. Shipping instructions: Name, Address, Attention
4.
5-
6.
Guaranteed arrival date for cylinders -
Planned shipping date for cylinders -
Details on audit cylinders from last analysis
a. Date of last analysis
b. Cylinder number.
c. Cylinder pressure psi.
d. Audit gas (es) /balance gas .
e. Audit gas(es) ppm
f . Cylinder construction
Low cone.
High cone
., ...
Part B. - To be filled out by audit supervisor.
1. Process sampled '
Audit location
2.
3.
4.
5.
Name of individual audit
Audit date
Audit Results:
d. Measured concentration, ppm
Injection #1* Injection #2* Average
e. Actual audit concentration, ppm
f. Audit accuracy:1
High Cone Cylinder
Percent1 accuracy =
Measured Cone. - Actual Cone. ^ 100
Actual Cone.
Low.
cone :
cylinder
High
cone.
cylinder
1Results of two consecutive injections that meet"the'sample analysis
criteria of the test method.
Quality Assurance Handbook M18-8.1
-------
METHOD 18 AUDIT CHECKLIST
Yes
No
Comments
Operation
PRESAMPLING PREPARATION
1. Knowledge of process operations
2. Results of pretest audit (+ 10% or other value)
3- Calibration of pertinent equipment, in
particular, dry gas meters and other flowmeters
4. Selection and checkout of equipment for proper
sampling and analytical techniques
BAGS - reactivity, condensation, & retention
ADSORPTION TUBES - adsorption & desorption
efficiency
DILUTION SYSTEM - dilution ratio
GC/COLUMN - adequate resolution
GC/DETECTOR - acceptable accuracy & precision
ON-SITE MEASUREMENTS
5- Results of on-site audit {+ 10% or other value)
6. Sampling system properly assembled
7. Based on pitot tube check, is proportional
sampling required (more than 10% flow change)
8. Dilution system check acceptable (if applicable)
9- Sampling system leak check acceptable
10. Proportional sampling properly conducted
11. Constant rate sampling properly conducted
12. Heater systems maintained at proper temperatures
13. Proper number of samples & sampling time
14 . GC properly calibrated
15. Duplicate injections had acceptable precision <5#
16. Recording of pertinent process conditions during
sample collection, samples properly identified,
and calculations properly conducted
POSTSAMPLING
17. Results of off -site audit (+ 10% or other value)
18. GC properly calibrated
19. Duplicate injections had acceptable precision <5#
20. Adsorption efficiency acceptable, >90# on primary
21. Desorption efficiency accep table, >50# recovery
22. Adequate peak resolution
23. Bags passed reaction check, less than 10% change
24. Bags passed retention check, less than 5% retained
25. Flowmeters recalibration acceptable
26. Temperature sensor recalibration acceptable
COMMENTS
Quality Assurance Handbook M18-8.2
ft U.S. GOVERNMENT PRINTING OFFICE: 1989-648-163/87062
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