&EPA
United States
Environmental Protection
Agency
Environmental Monitoring and Support EPA-600 4-78-058
Laboratory October 1978
Research Triangle Park NC 27711
Research and Development
Collaborative Testing of
EPA Method 106
(Vinyl Chloride) that
Will Provide for a
Standardized
Stationary Source
Emission
Measurement Method
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on-the effects of pollution on humans, plant and animal spe-
cies, and materials. Problems are assessed for their long- and short-term influ-
ences. Investigations include formation, transport, and pathway studies to deter-
mine the fate of pollutants and their effects. This work provides the technical basis
for setting standards to minimize undesirable changes in living organisms in the
aquatic, terrestrial, and atmospheric environments.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
COLLABORATIVE TESTING OF EPA METHOD 106 (VINYL CHLORIDE)
THAT WILL PROVIDE FOR A STANDARDIZED STATIONARY SOURCE
EMISSION MEASUREMENT METHOD
by
George W. Scheil
Michael C. Sharp
Midwest Research Institute
Kansas City, Missouri 64110
FINAL REPORT
EPA Contract No. 68-02-2737
MR! Project No. 4420-L
EPA Project Officer
M. Rodney Midgett
Quality Assurance Branch
Environmental Monitoring and Support Laboratory
Research Triangle Park, North Carolina 27711
Prepared for
Environmental Monitoring and Support Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
-------
DISCLAIMER
This report has been reviewed by the Environmental Monitoring and Sup-
port Laboratory, U.S. Environmental Protection Agency, and approved for pub-
lication. Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does men-
tion of trade names or commercial products constitute endorsement or recom-
mendation for use.
-------
FOREWORD
Midwest Research Institute, under EPA Contract No. 68-02-2737, conducted
collaborative tests of Method 106, "Determination of Vinyl Chloride from Sta-
tionary Sources." A group of 10 collaborators at their own laboratories ana-
lyzed six simulated samples containing vinyl chloride and interferring com-
pounds. Three laboratories then obtained field samples and analyzed the samples,
This report describes the collaborative tests and includes statistical analyses
of the test results.
Approved for:
MIDWEST RESEARCH INSTITUTE
L. J./Shannon, Director
Environmental and Materials
Sciences Division
October 1978
iii
-------
ABSTRACT
A two-part collaborative test was conducted for Method 106, "Determina-
tion of Vinyl Chloride from Stationary Sources." A group of 10 collaborators
analyzed a set of synthetic samples, some of which contained interferences,
for vinyl chloride. Analytical results were reported by peak height and by peak
area. All samples were analyzed on both 2m Chromosorb 102 and 2m Chromosorb
102/2m SF-96 columns. Most of the collaborators correctly identified the vinyl
chloride peaks. Chromosorb 102/SF-96 performed better in the presence of
acetaldehyde and Chromosorb 102 alone was better for isobutane interferences.
In all cases the chromatograms showed proper responses. The errors that were
made were due to interpretation of the results. The skill of the analyst is
a major factor in the use of Method 106. The collaborators obtained values
which averaged 0.18 ppm (0.47 mg/m^) low with a standard deviation of 0.72 ppm
(1.86 mg/nH). There was no overall superiority noted for peak height versus
area. The bias found was entirely due to low results using only Chromosorb 102.
Chromosorb 102/SF-96 gave a bias that was 0.01 ppm (0.03 mg/m^) low.
A field test of the method was then conducted by three groups on the vent
from a carbon bed adsorber. The group of collaborators had a standard devia-
tion of 0.46 ppm (1.19 mg/nH) for sampling and analysis combined. The standard
deviation for sampling from the same source was 0.39 ppm (1.01 mg/nH) and 0.24
ppm (0.62 mg/m^) for the analysis of the samples obtained. A brief comparison
of a charcoal adsorption tube method gave results which were about 20% lower
than results obtained using Method 106.
This report was submitted in fulfillment of Contract No. 68-02-2737 by
Midwest Research Institute under the sponsorship of the U.S. Environmental
Protection Agency. This report covers a period from June 1977 to April 1978,
and work was completed as of May 1978.
IV
-------
CONTENTS
Foreword* iii
Abstract* « iv
Figures vi
Tables vi
Acknowledgments vii
1. Introduction 1
2. Conclusions* . 3
3* Recommendations* 4
4* Selection of Collaborators 5
5. Collaborative Test Design* 7
6. Laboratory Collaborative Test Results* 9
7. Statistical Analysis - Laboratory Test 13
8. Field Collaborative Test 18
9. Field Test Statistical Results . 26
Standards Data. 26
Field Samples 28
References. »»» 31
Appendices
A. Letter to Obtain Potential Collaborators ............ 32
B. Final Instructions to Collaborators. .............. 35
C. Method 106 - Determination of Vinyl Chloride from Stationary
Sources with Amendments. .............. 38
D. Letter to Collaborators. 44
E. Tentative Procedure for Sampling and Analysis of Vinyl
Chloride Using Charcoal Adsorption Tubes ........... 48
-------
FIGURES
Number Page
1 Field test sampling manifold* . 19
TABLES
Number - Page
1 Collaborators* Vinyl Chloride Analysis Results (mg/m^), . 10
2 Collaborators' Vinyl Chloride Analysis Results (ppm)« 11
3 AOV of Laboratory Data 15
4 . Biases in the Laboratory Test 16
5 . Sampling Time for Sample Identification 20
6 Analysis Sequences* 20
7 Vinyl Chloride Field Test Results 22
8 Vinyl Chloride Field Test Results 23
9 Charcoal Tube Sampling Results* 24
10 Results of Standards Data Analysis. 27
11 Data Analysis of Field Test 29
C-l Retention Indices for Possible Vinyl Chloride
Interferences 43
VI
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ACKNOWLEDGMENTS
This work was conducted under the technical direction of Mr. Fred J.
Bergman, Program Manager, Method Development Group of Midwest Research Insti-
tute's Environmental and Materials Sciences Division. Dr. George Scheil was
Project Leader. He was assisted by Messrs. John LaShelle and Michael Sharp of
Midwest Research Institute. The assistance of the personnel of Diamond Sham-
rock Corporation during the field test is gratefully acknowledged.
vii
-------
SECTION 1
INTRODUCTION
On December 24, 1975, under Section 112 of the Clean Air Act, as amended,
the Environmental Protection Agency (EPA) added vinyl chloride to the list of
hazardous air pollutantsi' because it has been implicated as the causal agent
of angiosarcoma and other serious disorders. A national emission standard has
been promulgated?.' that covers plants that manufacture ethylene dichloride,
vinyl chloride, and polyvinyl chloride. These regulations include a method for
determining vinyl chloride emissions from stationary sources, EPA Method 106.
The Quality Assurance Branch of the Environmental Monitoring and Support Labora-
tory at Research Triangle Park, North Carolina, has as its task the evaluation
and standardization of EPA source test methods. While participating in this
program, Midwest Research Institute (MRI) has undertaken a collaborative test
of EPA Method 106.
The objective of this project was to conduct a collaborative test of EPA
Reference Method 106 (vinyl chloride). A collaborative test is a procedure in
which a group of persons from different laboratories conduct sampling and
analysis under identical conditions using the same method. It provides infor-
mation on the variability of method results between laboratories as well as
the reproducibility of a single analyst's results. A properly designed col-
laborative test should demonstrate the reliability of the method being tested
under typical, realistic sampling and analysis conditions.
The first goal under this program was to contact potential collaborators
and determine their experience in gas chromatographic analysis and vinyl chlo-
ride sampling techniques.
Following the evaluation of potential collaborators, 10 participants were
selected for the collaborative tests. Each collaborator was supplied with six
samples for analysis. The samples consisted of a minimum of four levels of
vinyl chloride with at least two samples containing organic compounds that
are potential interferences. The samples were obtained from a reputable gas
supplier who ascertained that the samples were stable and of the correct con-
centration.
MRI analyzed one set of samples at periodic intervals during the duration
of the collaborative test. MRI also sent one set of samples to the National
Bureau of Standards (NBS) for certification of the stated concentrations.
-------
A source of vinyl chloride emission at or below 15 ppm (40 mg/nr) was lo-
cated by MRI. Arrangements were made for three collaborators to obtain repli-
cate and simultaneous samples from the selected source using Method 106. The
collected samples were analyzed within 24 hr after collection. Samples were
also collected using a charcoal tube absorption technique.
At the conclusion of the laboratory and field collaborative test of Method
106, MRI statistically evaluated the analytical results.
The following sections of this report include the results and statistical
analyses of the collaborative tests. General conclusions and recommendations
obtained from the study are also presented.
-------
SECTION 2
CONCLUSIONS
The major conclusions obtained from the collaborative tests are:
! For vinyl chloride concentrations < 10 ppm (25 mg/m^), a collaborator
has a repeatability of + 0,5 ppm (1.3 mg/m^) or better, but at 50 ppm (125
mg/m^) vinyl chloride this value is much larger (~ + 6 ppm, 15 mg/m^).
2. A set of collaborators will read a given low concentration vinyl
chloride sample to within approximately + 1.25 ppm (3 mg/nH) (except at 50
ppm (125 mg/m^) vinyl chloride it becomes + 10 ppm, 25 mg/m^).
3. The physical sample-sample contribution to collaborator variation is
comparable to the analytical contribution.
o
4» The biasses exhibited are on the order of -0.1 ppm (0.3 mg/nr) for
pure vinyl chloride and -0.2 ppm (0.5 mg/m^) for interferred vinyl chloride,
when reliable readings are produced. However, one (of 10) collaborator was
fooled by all interferences, and the set of collaborators failed to produce
reliable observations 40% of the time on the 45.1 ppm (82 mg/rn^) acetaldehyde
sample.
5. There is no distinction between height and area methods. The Chromo-
sorb 102/SF-96 measurements are unbiased, and therefore are to be preferred,
statistically, to the negatively biased Chromosorb 102 measurements. The Chromo-
sorb 102 bias (~ -0.3 ppm, 0.8 mg/m3), is, however, small compared to the re-
peatibility contributions.
6. The charcoal adsorption tube allows a much simplified sampling pro-
cedure compared to Method 106 but the analysis procedure is more difficult
and not as accurate.
-------
SECTION 3
RECOMMENDATIONS
Based upon the conclusions that have been obtained from this collabora-
tive test, it is recommended that:
1. Method 106 continue to be used in its present form as an acceptable
method for the analysis of vinyl chloride from stationary sources.
2. Further consideration be given to determining the equivalence of
Method 106 and a charcoal adsorption tube method.
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SECTION 4
SELECTION OF COLLABORATORS
A letter, which is shown in Appendix A, was sent to approximately 80
organizations to determine their interest and qualification for participating
in the collaborative test. Fifteen potentially qualified collaborators re-
sponded with bids. All 15 collaborators were considered technically acceptable.
The 10 firms submitting the lowest bids were therefore selected. The collab-
orators are:
Dr. Douglas S. Kendall
Commercial Testing and Engineering Company
14335 West 44th Avenue
Golden, Colorado 80401
Analyst: Dr. Douglas S. Kendall
Dr. Perry Lonnes
Interpoll, Inc.
1996 West County Road C
St. Paul, Minnesota 55113
Analyst: Mr. Harilal Patel
Dr. Joseph D. Banzer
Diamond Shamrock Corporation
T. R. Evans Research Center
P.O. Box 348
Painesville, Ohio 44077
Analyst: Dr. Joseph D. Banzer
Dr. David C. Kennedy
Ryckman, Edgerley, Tomlinson & Associates
12161 Lackland Road
St. Louis, Missouri 63141
Analyst: Dr. Carol Hammer
Mr. Robert D. Soule, P.E.
Clayton Environmental Consultants, Inc.
25711 Southfield Road
Southfield, Michigan 48075
Analyst: Mr. Kent Shoemaker
-------
Dr. Don L. Shull
Commonwealth Laboratory, Inc.
Chemists Building
2209 East Broad Street
Richmond, Virginia 23223
Analyst: Mr. Dryden Reno
Dr. Don Adams
The Graduate School
Washington State University
Pullman, Washington 99164
Analyst: Mr. Dave Harsch
Mr. Arthur Engelmen
CCA/Technology Division
Burlington Road
Bedford, Massachusetts 01730
Analyst: Mr. Michael Oliverio
Dr. Gene Dennison
Envirotest Laboratories
103 East Prospect Street
Hopewell, New Jersey 08525
Analyst: Mr. Robert Menichelli
Mr. Bernard J. DeWitt
PPG Industries, Inc.
P.O. Box 31
Barberton, Ohio 44203
Analyst: Mr. James Hendershott
-------
SECTION 5
COLLABORATIVE TEST DESIGN
Six different gas mixtures were prepared by Scott Specialty Gases for the
laboratory collaborative test. Twelve sets of these mixtures were then made
using 200 liter capacity low pressure cylinders. One set was for stability
checks by MRI. One set was shipped to the NBS to obtain reference values of
vinyl chloride assigned. Each collaborator would receive one of the remaining
10 sets.
Each collaborator analyzed each sample according to the instructions
given in Appendix B using the current version of Method 106 with amendments
(Federal Register, Vol. 41, pp. 46569-46571, October 21, 1976; amended Vol.
42, pp. 29007-29009, June 7, 1977) given in Appendix C. Each collaborator re-
ported both peak height and peak area results for both the 2m Chromosorb 102
column and for the 2m Chromosorb 102/2m SF-96 column combination. Thus, sys-
tematic differences in the methods were measurable.
The approximate compositions of the samples were:
1. 5 mg/nr (2 ppm) vinyl chloride
2. 20 mg/nr (8 ppm) vinyl chloride
3. 18 mg/m^ (7 ppm) vinyl chloride and 80 mg/m^ (50 ppm) acetaldehyde
4. 30 mg/m^ (12 ppm) vinyl chloride, 15 mg/m-* (10 ppm) methanol, and 50
mg/nr (20 ppm) isobutane
5. 18 mg/nr (7 ppm) vinyl chloride, 7 mg/nr (5 ppm) methanol, and 25
mg/nr (10 ppm) isobutane
6. 30 mg/nP (20 ppm) acetaldehyde
All samples have nitrogen as the balance gas.
-------
Samples 1 and 2 measure the accuracy of each collaborator's calibration
gases. Sample 3 is a mixture which should be difficult to resolve on Chromo-
sorb 102, but easy on the combined columns. Samples 4 and 5 are similar and
should be easier to resolve on Ghromosorb 102. Sample 6 contains no vinyl
chloride and indicates the skill of the analyst's recognizing a false vinyl
chloride peak.
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SECTION 6
LABORATORY COLLABORATIVE TEST RESULTS
The samples were prepared, aged, and checked for vinyl chloride stabil-
ity. They were then shipped to MRI, One set of cylinders was chosen at random
and the first analysis of the samples was completed by MRI on September 12.
After verifying that each mixture could be measured on at least one of the
columns, the collaborators' samples were shipped. One set was also shipped to
NBS.
Tables 1 and 2 summarize the results of the test. The tables include
analysis results by Scott, NBS, MRI, and the collaborators. Collaborator D
did not submit results until 4 months after the samples were shipped. All
other collaborators completed their analyses within the 1-month period al-
lowed. Since Collaborator D submitted results which demonstrated no obvious
anomalies, their results are included in the final data set. Vinyl chloride
in cylinders is normally stable for periods of more than 1 year without de-
tectable changes in concentration. The only component which is unstable is
acetaldehyde and it was still clearly present in Collaborator D's chromato-
grams.
Collaborators B and F found no acetaldehyde peaks in their samples. The
suspect cylinders were returned to MRI, Acetaldehyde was clearly detected in
all of the suspect samples by MRI, Neither collaborator has been able to sug-
gest any reason for the loss of acetaldehyde on a Chromosorb 102 column.
However, acetaldehyde is irreversibly retained by many polar materials
in addition to an SF-96 column. In many instances the collaborators reported
suspect values which they rejected due to the probable presence of interfer-
ences. Collaborators E, G, and K did not indicate that Sample 10673 was not
vinyl chloride. An examination of these data by MRI indicates that the dif-
ferences in retention time should have been sufficient to reject the peaks as
not vinyl chloride,
MRI conducted two analyses of the samples 1 month apart. As the data in
Tables 1 and 2 indicates, the samples were all stable. Samples 60106 and 4786
were pure vinyl chloride. Both columns performed equally well. Samples 4036
and 6800 are similar. On Chromosorb 102, two peaks are seen incompletely
-------
TABLE 1. COLLABORATORS' VINYL CHLORIDE ANALYSIS RESULTS (mg/m3)
1814 (17.6 Dg/ra3 vinyl chloride.
32 mg/a3 acctaldehyde)
Chromosorb 102 height
Chromosorb 102 area
Chromosorb 102 and SF-96 height
Chromosorb 102 and SF-96 area
4036 (33.7 mg/ra3 vinyl chloride.
9*4 mg/a3 root Hanoi, 51 tag/m3
isobulane)
Chroaosorb 102 height
Chroaosorb 102 area
Chroaosorb 102 and SF-96 height
Chroaosorb 102 and SF-96 area
6800 (18.2 ag/n3 vinyl chloride.
6*0 ng/o3 net Hanoi, 25.5 rag/ia3
Isobutane)
Chromosorb 102 height
Chroaosorb 102 area
Chrooosorb 102 and SF-96 height
Chrooosorb 102 and SF-96 area
10673 (34 og/m3 acctaldehyde)
Chroaosorb 102 height
Chroaosorb 102 area
Chromosorb 102 and SF-96 height
Chroaosorb 102 and SF-96 area
47JJ6 (22.6 mg/a3 vinyl chloride)
Chromosorb 102 height
Chromosorb 102 area
Chromosorb 102 and SF-96 height
Chromosorb 102 and SF-96 area
60106 (5.80 rag/m3 vinyl chloride)
Chromosorb 102 height
Chromosorb 102 area
Chroaosorb 102 and SF-96 height
Chromosorb 102 and SF-96 area
£/ Data received late .
b/ Data corrected for revised and
~
NBS Collaborator
(mn/r)3) A
17.5
19.frc7
17.2
Not raeii-
33.7
23.7
28.2
32.9
32.9
19.0
16.4
16.1
18.9
id. 7
< 0.13
12i£'
n.d.
n.d.
22.2
19.1
18.8
23.2
22.6
5.81
4.84
4.71
5.39
5.05
lyavs In vinyl chloride
Collaborator
fib/
12.4
12.4
15.3
15.8
24.9
24.9
30.0
31.6
15.3
15.5
16.8
17.6
n.d.
n.d.
n.d.
n.d.
16 3
17.1
19.7
19.9
3.9
4.1
4. 7
6.0
standards as
Collaborate
C
43. B£'
48.4~
18.6
17.9
35.5
36.0
34.7
35.0
19.7
21.8
20.7
19.7
10.U'
11. IS'
n.d.
n.d.
23.3
23.8
23.8
23.1
6.0
7.5
6.7
6.2
reported by
r Collaborator
rv/
f,
31.78£'
15.4
18.0
34.45
34.91
34.60
34.40
19.40
19.45
19.45
19.32
n.d.
n.d.
n.d.
n.d.
21.9
23.5
22.7
22.9
5.62
6.01
6.11
5.80
supplier.
Collaborator
E
28.0='
42. 2£'
14.2
39.95'
32.4
31.1
33. 4£'
34.2°.'
20.5
20.5
19. 9£/
22. 3£'
19.7
19.4
7.3S/
22. 3£'
22.5
22.0
23.8
23.1
6.0
5.7
6.2
7.0
Collaborator
r
15.3
15.3
14.5
16.1
31.6
30.3
31.3
30.0
17.6
16.8
16.8
16.8
n.d.
n.d.
n.d.
n.d.
20.2
20.2
19.4
20.5
6.5
4.7
5.4
4.9
Collaborator
C
50.71
52.783'
17.4
17.2
33.18
33.633'
34.34
34.34
18.9
18.93'
18.3
18.4
12.2
I3.0d/
n.d.
n.d.
21.7
21.83'
22.7
22.4
5.62
5.783'
6.40
6.48
Collaborator
H
37.B":'
72. OS.'
18.4
18.2
34.58
33.33
34.24
32.9
20.0
19.7
19.7
18.9
3.57£/
6.92?.'
n.d.
n.d.
22.9
22.9
22.9
23.0
7.23
6.89
7.23
6.89
Col laborator
J
24. (£.1
48. IS'
15.8
15.5
33.4
33.4
29. -£/
28. ?£'
18.6
18.4
19.4
19.2
n.d.
n.d.
n.d.
n.d.
21.0
21.0
19.7°'
19. IS.'
5.7
5.4
5.7
5.1
Collaborator
K
16.8
16.1
20.7
20.2
119
1SS
106
ISO
60
83
80
78
1.3
1.3
n.d.
n.d.
22.3
21.8
24.9
25.4
6.2
6.2
6.5
7.3
MRI
Sept. 12
20. 5
35.5
16.3
16.63'
28.2
30.33'
36. 5
cy
16.6
17.63'
20.5
.£.'
Oct. 13
9.1
C/
16.6
17.13'
31.1
32.43'
= '
o./
17.4
17.6
e/
e/
Wrong retention time-
not vinyl
n.d.
n.d.
20.2
19. 13'
20.5
20.53'
5.08
5.3*3'
5.46
5.3l3'
chloride
n.d.
n.d.
20.7
20.73'
20.7
21.23'
5.31
5.313'
5.49
5.543'
-------
TABLE 2. COLLABORATORS' VINYL CHLORIDE ANALYSIS RESULTS (PPM)
1816 (6.8 ppra vinyl chlorine,
65.1 ppm acctaldchydc)
Chromosorb 102 height
Chromosorb 102 area
Chromosorb 102 and 5F-96 height
Chromosorb 102 and SF-96 area
6036 (13.0 ppm vinyl chloride.
7.1 ppm octhanol, 21.1 ppm
isobutanc )
Chromosorb 102 height
Chramosorb 102 area
Chromosorb 102 and SF-96 height
Chroraosorb 102 and SF-96 area
6800 (7.06 ppra vin)l chloride,
6.5 ppo mcthanol, 10.6 ppo
Isobutanc)
Chromosorb 102 height
Chroraosorb 102 area
Chromosorb 102 and SF-96 height
Chromosorb 102 and SF-96 area
10673 (18.6 ppm acctaldchydc)
Chromosorb 102 height
Chromosorb 102 area
Chromosorb 102 and SF-96 height
Chromosorb 102 and SF-96 area
6786 (8.73 ppm vinyl chloride)
Chromosorb 102 height
Chromosorb 102 area
Chromosorb 102 and SF-96 height
Chromosorb 102 and SF-96 area
60106 (2.26 ppm vinyl chloride)
Chromosorb 102 height
Chromosorb 102 area
Chromosorb 102 and SF-96 height
Chromosorb 102 and SF-96 area
NBS Collaborator
(ppm) A
6.75
2 .!£'
75 7 .6°'
.66
H t raco-
s rablc£'
13.0
11.1
10.9
12.7
12.7
7.34
6.36
6.21
7.30
7.22
<0.05
I3.5S'
67. t£'
n.d.
n.d.
8.57
7.38
7.27
8.96
8.73
2.26
1.87
1.82
2.08
1.95
Col laborator
6.8
4.8
5.9
6.1
9.6
9.6
11.6
12.2
5.9
6.0
6.5
6.8
n.d.
n.d.
n.d.
n.d.
6.3
6.6
7.6
7.7
1.5
1.6
1.3
2.1
Col laborator
C
16. 9J;'
18. 7£/
7.2
6.9
13.7
13.9
13.4
13.5
7.6
8.6
8.0
7.6
3.9£'
4. IS'
n.d.
n.d.
9.0
9.2
9.2
8.9
2.3
2.9
2.6
2.6
Col laborator
Da'
c/
12.271'
5.94
6.95
13.30
13.48
13.36
13.28
7.49 '
7.51
7.51
7.66
n.d.
n.d.
n.d.
n.d.
8.47
9.06
8.77
8.85
2.17
2.32
2.36
2.24
Col laborator
E
10. a£'
16.3*'
5.5
15.4S'
12.5
12.0
12.91'
13. 2£'
7.9
7.9
7.7£'
8 65.'
7.6
7.5
2.8£'
B.6S'
8.7
8.5
9.2
8.9
2.3
2.2
2.4
2.7
Col laborator
F
5.9
5.9
5.6
6.2
12.2
11.7
12.1
11.6
6.8
6.5
6.5
6.5
n.d.
n.d.
n.d.
n.d.
7.8
7.8
7.5
7.9
2.5
1.8
2.1
1.9
Collaborator
C
19.58
20. 384'
6.71
6.66
12.81
12.833'
13.26
13.26
7.29
7.284'
7.08
7.12
4.72
5.024'
n.d.
n.d.
8.37
8.624'
8.77
8.66
2.17
2.234'
2.47
2.50
Collaborator
fl
16.61'
27.8='
7.11
7.04
13.35
12.87
13.22
12.7
7.71
7.62
7.60
7.30
1.38°'
2.671'
n.d.
n.d.
8.86
8.84
8.85
8.87
2.79
2.66
2.79
2.66
Collaborator
J
9. 5l'
18. 6='
6.1
6.0
12.9
12.9
11. IS'
ll.lc/
7.2
7.1
7.5
7.4
n.d.
n.d.
n.d.
n.d.
8.1
8.1
7.6='
7.5£'
2.2
2.1
2^2
2.1
Col laborator
K
6.5
6.2
8.0
7.8
46
60
41
58
23
32
31
30
0.5
0.5
n.d.
n.d.
8.6
8.6
9.6
9.8
2.6
2.4
2.5
2.8
MK1
Scot. 12
7.9
13.7
6.3
6.44'
10.9
11.74'
14.1
£'
6.4
6.84'
7.9
a/
Wrong ret
not vinyl
n.d.
n.d.
7.84'
7.64'
7.9
7.94'
1.96
2.08
2.11
2.054'
Oct. 13
3.5
c./
674
6.64'
12.0
12.54'
±1
£.'
6.7
6.8
S.I
intion tirac-
chloride
n.d.
n.d.
8.0
8.04'
8.0
8.24'
2.05
2.054'
2.12
2.164'
a/ Data received late
bl Data corrected for rovlscd jnolyscs In vinyl chloride standards as reported by supplier.
£/ Instruacn: malfunction; not ablt to obtain reading.
d/ Best value.
e/ lnt*r[cr^nco s-jsptcti.-d--r«sul C rejected by CO 11 aborator.
-------
separated but sufficient to accurately measure both height and area. On the
combined columns, vinyl chloride becomes a slight shoulder on the leading edge
of the interference peak. The peak height can be estimated but no information
on peak area is obtainable without complex peak shape analyses. Apparently,
the methanol peak has shifted and merged with the isobutane peak. Sample
10673, acetaldehyde only, shows normal peak shape but with a retention time
of about 0.3 min shifted on Ghromosorb 102. On the combined columns no peaks
are detectable indicating permanent retention of acetaldehyde by the SF-96
column. Sample 1814, vinyl chloride and acetaldehyde, shows a single peak with
nearly double normal peak width on Chromosorb 102. On the combined columns
only a single normal peak is present at the vinyl chloride retention time. The
values measured by MRI are slightly lower than those reported by Scott, but
may be due to small errors in the last comparison against permeation tube
standards*
12
-------
SECTION 7
STATISTICAL ANALYSIS - LABORATORY TEST
Structurally, this data set is.a 6 (levels of vinyl chloride (VC)) x 10
(collaborators) x 4 (methods) factorial analysis of variance (AOV). The pri-
mary objective of the analysis is to estimate the components of variance,
namely:
Oe = The variance of repeated measurements by a single collaborator at
a fixed level of VC.
*\
cr^ = The variance of VC measurements between collaborators (over and
above that which would arise due strictly to ae )
0^2 = xhe variance of VC measurements due to method-method differences.*
CTL? = The variance due to level-level differences.
acm2 = The variance due to differences in the collaborator differences due
to method changes, etc.
These components "add," e.g., the variance of repeated measurements by
a group of collaborators measuring a value of VC by a method is ae2 + ac2,
etc.
In practice, the number of levels actually analyzed was only four because:
(a) one level was a "control" level - zero VC and 18.4 ppm acetaldehydethis
level did not "fool" nine of the collaborators in any instance, although Col-
laborator E did report ~ 7.5 ppm by Methods 1 and 2; (b) the level consisting
of 6.8 VC + 45.1 ppm acetaldehyde produced unreliable measurements 40% (16/40)
of the time. It is felt that this result is more realistic than a formal numeri-
cal analysis of the values (the other 60% of which were reasonably close to
the nominal value).
'' Technically, "aL.2" and "o^ " are not variances, because the methods and
levels are fixed (not randomly selected from a population of methods or
levels). For convenience, however, the en notation will be used.
13
-------
One collaborator (K) produced obviously discrepant values* at both of the
other interfered levels. Therefore, only nine collaborators were incorporated
in the primary analysis of variance. Of course, it should be kept in mind dur-
ing all overall considerations of the method that one (of 10) collaborators
did produce unacceptably large errors.
Finally, in the remaining 4x4x9= 144 cells, eight values were "miss-
ing." These eight were all produced by two collaborators (Collaborators J and
E), and were all confined to the two SF-96 methods. The missing values were
replaced by a conventional procedure, i.e., by minimizing residual SS within
the VC level they fell in.
The analysis of variance results is shown in Table 3. The response (X)
is an individual bias, i.e., X = actual reading - NBS reference value.
The results can be summarized as:
* A single collaborator reads a fixed level of VC with a single method
within about +0.5 ppm** (+ 2 ae).
* A set of collaborators reads a fixed level of VC with a given method
within about + 1.26 ppm (+ 2 ^CTg2 + ac2).
* The method effect is quite small, e.g., the so-called "component
at variance" + 2 ^cre2 + ac2 + a^2 = + 1.30 ppm.
* A set of collaborators reads the various levels of VC in the experi-
ment to within about + 1.31 ppm (+ 2 \KTe2 + ac2 +
Of course, in addition to the dispersion of the measurements the accuracy
can also be evaluated with respect to the NBS values.*** Various biases of
interest are shown in Table 4. In terms of significance:
* Collaborator K's results for 13.0 ppm VC + 7.1 ppm methanol + 21.1 ppm
isobutane were ~ "50 ppm," and for 7.34 ppm VC + 4.5 ppm methanol +
10.6 ppm isobutane were ~ "30 ppm." Both of these results are, of course,
rejectable or outliers (Dixon-Massey R - 0.931, p < 0.005 and r = 0.942,
p < 0.005).
** This quantity, however, is never directly observed in the experiment.
*** The various biases across levels could be "integrated" via an analysis
of covariance with NBS values, a covariate with respect to collaborator
values. With only four levels, however, the "piecewise" approach em-
ployed is felt to be adequate.
14
-------
TABLE 3. AOV OF LABORATORY DATA
Source
Collaborator (C)
Level (L)
Method W)
CL
CM
LM
e
aF
8
3
3
24
24
9
64
SS
43.98
2.88
3.98
11.21
10.15
1.44
3.86
MS
5.50
0.96
1.33
0.47
0.43
0.16
0.0603
F
91.2ia/
2.04
3.09k/
7.135./
2.65k/
EMS (C) = o-2 + 16 o>2 CTe2 = 0.0603
C * ^
EMS (L) = o-e2 + 4 aCL2 + 36 aL2 ac2 = 0.3400
EMS (M) = ae2 + 4 aCL2 CTL2 = 0.0136
EMS (CL) = ae2 + 4 0-QM2 + 36 a^2 crM2 = 0.0250
EMS (CM) = C7e2 + 4 o-cM2 aCL2 = 0.1024
EMS (LM) = ae2 + aCLM2 + 9 ^LM2 CTCM2 = °'0924
EMS (CLM) = ae2 + crcLM2 °"LM2 = 0.0111
EMS (e) = ae2
a/ Significant at p = 0.01.
b/ Significant at p = 0.05.
15
-------
TABLE 4. BIASES IN THE LABORATORY TEST
Source (ppm)
LI (2.26 VC)
L2 (8.57 VC)
L3 (13.0 VC +7.1 methanol + 21.1 isobutane)
L4 (7.34 VC +4.5 methanol + 10.6 isobutane)
Ml Chromosorb 102 height
M2 Chromosorb 102 area
M3 Chromosorb 102 and SF-96 height
M4 Chromosorb 102 and SF-96 area
Coll. D
Coll. H
Coll. J
Coll. C
Coll. G
Coll. A
Coll. B
Coll. F
Coll. E
Avg. bias (ppm)
-0.012
-0.219
-0.386
-0.083
-0.339
-0.344
+0.014
-0.036
+0.200
+0.263
-0.044
+0.500
-0.019
-0.600
-1.325
-0.725
+0.163
Bias (%)
-0.53
-2.56
-2.97
-1.13
-4.35
-4.42
+0.18
-0.46
+2.57
+3.37
-0.56
+6.42
-0.24
-7.70
-17.01
-9.31
+2.09
All data
-0.176
-2.26
16
-------
" The bias at all levels was negative (-0,18 ppm overall average), but
Ll and L4 were the closest to true, while L2 was significantly more
negative, and L3 significantly the most negative* Since Ll and L2 are
the pure levels, it is not clear that the interferences cause an in-
crease in bias*
* The two Ghromosorb methods (Ml and M2) are significantly more biased
than the two Ghromosorb + SF-96 methods (-0,34 ppm versus -0.01 ppm).
In fact, Methods 3 and 4 are not biased at all. There is no discernible
difference between height and area determinations (in either case).
17
-------
SECTION 8
FIELD COLLABORATIVE TEST
The final part of this program was to conduct a test of Method 106 on an
actual vinyl chloride source*
A field test was arranged for February 14 through 16 at the Deer Park
plant of Diamond Shamrock. Three teams participated in the test. Diamond Sham-
rock and MRI were teams, and the third team was selected by MRI from the col-
laborators on the basis of cost.
The sampling was done at ground level from the outlet of a carbon adsorp-
tion system. The manifold was connected around a control valve so that a posi-
tive flow could be maintained through the manifold. A diagram of the sampling
system is shown in Figure 1. Since the line was at a moderate positive pressure,
the pumps were not used during sampling. A needle valve was inserted to con-
trol the flow into the bags with flow rates still measured by the air leaving
the bag enclosure. The expected vinyl chloride concentration was slightly
under 1 ppm.
A copy of the letter sent to the collaborators requesting bids for the
test is shown in Appendix D. The field test design is given in Tables 5 and 6.
The three teams analyzed each others' standards to determine the variability
of the different manufacturers' standards. Each team also analyzed some of the
other teams* samples to measure precision.
MRI also sampled using carbon adsorption tubes. The adsorption tube
procedure followed a modified form of the EPA ambient vinyl chloride method
as given in Appendix E. This procedure was compared with the Method 106 re-
sults. The method was modified to simplify the calibration procedure and im-
prove the reliability of the method by making the calibration and analysis
procedures similar.
The third collaborator selected was Envirotest Laboratories. The person-
nel who participated in the test were:
18
-------
Pressure
Regulator
Sampling
Valve
To Vcnl
Stack
=1 .Shutoff Valve »=r, Shutoff Valve t=< Shutoff Valve
Sampling
>T[1 Valve
inn)
Sampling
Valve
Figure 1. Field test sampling manifold.
-------
TABLE 5. SAMPLING TIME FOR SAMPLE IDENTIFICATION
Collaborator A
Collaborator B
Collaborator C
Day 1 Day 2
I II III IV I II III IV
Al A2 A3 A4 A5 Ae A7 AS
Bl B2 B3 B4 B5 B6 B7 B8
cl C2 C3 CA C5 C6 C7 C8
TABLE 6. ANALYSIS SEQUENCES
Day 1
Collaborator A
Collaborator B
Collaborator C
Day 2
Collaborator A
Collaborator B
Collaborator C
a/
SA- AI Ci A2 B2 A3 C3 A4 B4 SA
SB BI AI B2 C2 63 A3 B4 C4 SB
SQ C]^ B^ C2 A2 03 63 C4 A4 Sg
SC A5 B5 Ae Be A7 C7 AS BS SC
SA 65 GS Be ce B7 A7 BS cs SA
SB C5 A5 C6 A6 C7 B7 C8 A8 SB
a/ SA = Standard gas set belonging to A.
All standards are analyzed by all collaborators twice.
All samples are analyzed by two collaborators.
Each collaborator analyzes all of his samples and one-half of every other col-
laborators ' .
20
-------
Envirotest Laboratories
Mr. Robert Menichelli - analyst
Dr. Gene Dennison - sampler
Diamond Shamrock
Dr. Joseph Banzer - analyst
Mr. Don Myers - sampler
* Midwest Research Institute
Dr. George Scheil - analyst
Mr. John LaShelle - sampler
The field test of Method 106 was completed February 14 through 16, 1978,
at the Deer Park plant of Diamond Shamrock. On February 14 equipment was set
up and checked by the three teams.
The results of the test are summarized in Tables 7 and 8. On the morn-
ing of February 15 a fresh carbon bed was put on line and sampling started for
run No. 1 at 0940. Run No. 2 sampled the same carbon bed. The second carbon
bed was started prior to run No. 3. Run No. 4 was also made on the second bed.
The first three runs proceeded normally with each team analyzing their own
bag and one other team's bag during each run. Run No. 4 showed very high vinyl
chloride levels caused by intermittent bursts of steam entering the bed which
desorbed vinyl chloride. The three bag samples show wide variations in concen-
tration. The variations were probably due to the fact that (according to the
plant on-stream analyzer) one of the two steam brusts occurred at the start
of sampling when flow rates into the bags were unstable.
During the first test day each collaborator analyzed the other team's
standards. Due to the size of one collaborator's standard cylinders it was not
feasible to carry them from place to place. Instead, aluminized Mylar bags
were filled from each cylinder and analyzed by each collaborator. Thus, one
collaborator has different values for peak height and area for their own stan-
dards instead of the calibrated values.
On February 16 run Nos. 5 and 6 were made on the first bed after over-
night bed regeneration. Run No. 7 started on a fresh second bed but was immed-
iately stopped after another burst of steam. The bags were flushed, pumped
down, and checked for contamination. Run No. 7 was then restarted with no fur-
ther difficulty. No further runs were made since delays from the upsets left
no additional time in the test schedule without incurring unscheduled costs.
MRI also ran three charcoal tubes using the tentative procedure which op-
pears in Appendix E. The results of this comparison are given in Table 9.
21
-------
TABLE 7. VINYL CHLORIDE FIELD TEST RESULTS"
a/
Date
Time
Feb. 15
0940-1040
Feb. 15
1052-1152
Feb. 15
1404-1504
Feb. 15
1618-1718
Feb. 16
0943-1043
Feb. 16
1108-1208
Feb. 16
1458-1558
Feb. 15
Feb. 15
Feb. 15
Col laborator
Coll. A
analysis
Run 1 Ht
Area
Run 2 Ht
Area
Run 3 Ht
Area
Run 4 Ht
Area
Run 5 Ht
Area
Run 6 Ht
Area
Run 7 Ht
Area
Nominal level
5 ppm standard Ht
Area
10 ppm standard Ht
Area
50 ppm standard Ht
Area
2.72
2.47
1.55
1.46
1.05
0.97
63.7
7313
4.34
4.42
1.89
1.76
8.14
8.02
4.52>!/
4.6l£V
9.42^/
46.lt/
45.4k/
A Samples/stj
Coll. B
analysis
1.73
1.64
82.0
82.7
4.64
4.46
5.28
5.05
10.7
10.2
51.6
49.6
mdards
Coll. C
analysis
2.79
3.03
1.20
1.34
1.92
1.86
7.02
7.18
4.43
4.62
8.86
8.56
39.8
38.3
Collaborator
Coll. B
analysis
2.12
2.01
1.65
1.60
1.04
1.03
1,037
998
4.82
4.55
2.23
2.13
7.20
7.17
l'.&>
10. fff
10. &£/
49. Q£/
49. 0£/
B Samples/standards
Coll. A Coll. C
analysis analysis.
1.97
1.82
0.84
0.79
2.31
2.29
6.87
6.93
d/
5.0
I/
10.3
47.3
1.51
1.64
898
897
4.36
4.42
4.55
4.58
9.54
9.51
42.4
42.4
Col labor
Coll. C
ana lysis
1.87
2.02
1.52
1.68
0.90
1.03
1,280
1,280
3.85
3.86
1.93
1.88
5.74
5.78
4.79£/
4.79£/
9.07£/
9.07S/
41. 7£/
41. 7£/
itor C Samples/standards
Coll. A Coll. B
analysis analysis
2.14
2.05
1.47
1.44
1.15
1.09
1,207
1,362
3.71
3.75
1.99
1.89
6.26
6.17
Al 5 . 25
4.86 5.26
d/ 10.1
9.82 10.1
d/ 48.3
48.4 47.2
a/ All results arc reported as parts per million of vinyl chloride.
b_/ Manufacturer's measured value.
£/ Manufacturer's certified value.
d/ Collaborator A had instrument problems and height analysis
obtainable.
-------
TABLE 8. VINYL CHLORIDE FIELD TEST RESULTS-
a/
Date
Time
Feb. 15
0940-1040
Feb. 15
1052-1152
Feb. 15
1404-1504
Feb. 15
1618-1718
Feb. 16
0943-1043
Feb. 16
1108-1208
Feb. 16
1458-1558
Feb. 15
Feb. 15
Feb. 15
Col labora tor
Coll. A
analys is
Run 1 Ht
Area
Run 2 Ht
Area
Run 3 Ht
Area
Run 4 Ht
Area
Run 5 Ht
Area
Run 6 Ht
Area
Run 7 Ht
Area
Nominal level
12 ing/ra^ standard Ht
Area
25 rog/nP standard Ht
Area
120 mg/rn-* standard. He
Arco
7.04
6.40
4.01
3.78
2.72
2.51
165
190
11.2
11.4
4.90
4.56
21.1
20.8
1 1 . 7^'
11.9V
24^'
119*'
A Sample.
Coll. B
analys is
4.48
4.25
212
214
12.0
11.6
13.7
13.1
27.7
26.4
134
128
/standards
Coll. C
ana lysis
7.23
7.85
3.11
3.47
4.97
4.82
18.2
18.6
11.5
12.0
22.9
22.2
103
99
Collaborator
Coll. B
ana lysis
5.49
5.21
4.27
4.14
2.69
2.67
2686
2585
12.5
11.8
5.78
5.52
18.6
18.6
13. 5£'
13. 5£/
27. 5£/
27. 5£'
127£/
B Samples/standards
Coll. A Coll. C
analysis analysis
5.10
4.71
2.18
2.05
5.98
5.93
17. B
17.9
T3.0
26.7
723
3.91
4.25
2326
2323
11.3
11.4
11.8
11.9
24.7
24.6
110
109
Col laborator
Coll. C
ana lysis
4.84
5.23
3.94
4.35
2.33
2.67
3315
33'.5
9.97
10.0
5.00
6.87
14.9
15.0
12.4S/
12. 4£/
23. 5£'
23. 5£/
!$
C Samples/standards
Coll. A Coll. B
analysis analysis
3.81
3.73
3126
3528
9.61
9.71
12.6
25.4
d/
125
5.54
5.31
2.98
2.82
5.15
4.90
16.2
16.0
13.6
13.6
26.2
26.2
125
122
a_l All results a re reported as rcL 11 Igratns per cubic rooter of viny I ch lor id e .
b/ Manufacturer's measured value.
c_/ Manufacturer's certified value.
d/ Collaborator A had instrument problems and height analys LS was not obta inab le.
-------
TABLE 9. CHARCOAL TUBE SAMPLING RESULTS
Charcoal tube analysis'
a/
2 m SF-96 at 75°C
2 m Carbowax 1500 on
Carbopak at 75°C
Analysis of bag used for charcoal sampling
Run 3
Run 6
Run 7
0.75 ppm
(1.94 mg/m3)
1.75 ppm
(4.53 mg/m3)
4.85 ppm
(12.6 mg/m3)
0.68 ppm
(1.76 mg/m3)
1.55 ppm
(4.01 mg/m3)
4.88 ppm
(12.6 mg/m3)
0.90 ppm peak ht.
(2.33 mg/m3)
1.93 ppm peak ht.
(5.00 mg/m3)
5.74 ppm peak ht.
(14.9 mg/m3)
1.03 ppm peak area
(2.67 mg/m3)
1.88 ppm peak area
(4.87 mg/m3)
5.78 ppm peak area
(15.0 mg/m3)
a/ Charcoal tube results were by peak height only.
-------
Each charcoal tube sampled from one of the MRI integrated bag samples after
the Method 106 analyses were completed. The original intent of this sampling
was to use the same Chromosorb 102 column for the charcoal method analysis.
The characteristic doublet impurity peak from carbon disulfide completely
obscures the vinyl chloride peak on Chromosorb 102. The first 0,2% Carbowax
1500 on Carbopak column prepared was unusable due to crushing of the fragile
Carbopak. An attempt to use a Carbowax 400 column (which has McReynolds con-
stants similar to Carbowax 1500) failed when no vinyl chloride peak could be
identified. Finally, the SF-96 secondary column used in Method 106 did achieve
a separation of vinyl chloride from the carbon disulfide doublet. However, this
nonpolar column results in such a short retention time for vinyl chloride that
peak area was immeasurable and peak height was unstable with 20 to 30% varia-
tion in successive injections. The values reported are the averages for dupli-
cate injections, using peak height. The agreement is still quite acceptable
between Method 106 and the charcoal tube procedure using the SF-96 column. The
carbon disulfide extracts were saved and the results obtained on a new
Carbowax 1500/Carbopak column are also given in Table 9. The Carbowax column
gave more consistent results although the vinyl chloride retention time is
still short.
25
-------
SECTION 9
FIELD TEST STATISTICAL RESULTS
STANDARDS DATA
In this data set three standards (5, 10, and 50 ppm) were read by three
collaborators in the following way: three physical samples (one per collabo-
rator) were taken, and each bag was read by two collaborators. This plan was
executed in duplicate according to two methods (Ml = height, M2 = area)*
Structurally each method consists of three (one per level) balanced in-
complete block (BIB) analysis of variance models.
In practice, one-third of the height measurements were missing, so the
formal AOV was performed only for the area method. The height method was sep-
arately compared via regression analysis for the 15 cases in which a height
value existed.
Finally, casual inspection of the results shows that the magnitude of the
components of variance will vary according to the level. For this reason re-
sults are quoted separately per level (see Table 10). These results are preci-
sions only, i.e., no bias is included.
Results are:
1. A single collaborator reading a given standard will read within about
+ 0.32 ppm (at VC = 5 ppm), + 0.47 ppm (at VC = 10 ppm, and +6.0 ppm (at VC
= 50 ppm).
2. A set of collaborators will read a given standard within about + 0.59
ppm (at Ll), + 1.50 ppm (at L2), and + 10.2 ppm (at L3).
3. A set of collaborators will read a set of standards within about +
0.80 ppm (at Ll), + 1.92 ppm (L2), and + 12.9 ppm (at L3).
4. Roughly speaking, the standard-standard variation is about the same
size as the collaborator-collaborator variation.
26
-------
TABLE 10. RESULTS OF STANDARDS DATA ANALYSIS
A. Analyses of Variance (area method)
Level 1 (5 ppm)
Source df SS MS EMS
Collaborator (adj)
Sample (s)
Error (e)
Level 2 (10 ppm)
Collaborator (adj)
Sample (s)
Error (e)
Level 3 (50 ppm)
Collaborator (adj)
Sample (s)
Error (e)
B. Components of Variance
2
2
1
2
2
1
2
2
1
0.2353
0.5785
0.0253
1.6419
2.5375
0.0541
68.44
114.64
9.13
0.
0.
0.
0.
1.
0.
34
57
9.
1177
2916
0253
8210
2688
0541
.22
.32
13
ae2 + 3/2 ac2
22 ?
ae + ac +2 CTS^
CTe2
ae2 + 3/2 crc2
o'e + o~c + 2 o~g
CTe2
cre2 + 3/2 ac2
tfe2 + crc2 + 2 as2
-e2
LI: ae2 = 0.0253
crc2 = 0.0616
CTS2 = 0.0743
L2: ae2 = 0.0541
CTC2 = 0.5113
o-s2 = 0.3517
L3: o-e2 = 9.13
ac2 = 16.73
as2 = 15.73
27
-------
5. The 5 and 10 ppm results are more or less compatible with the lab-
oratory data; the uncertainties associated with 50 ppm VC are considerably
larger (even relatively). It was concluded that the 5, 10, and 50 ppm levels
were nominal only, so that quantitative biases were not evaluated.
The comparison of height versus area methods was undertaken via regres-
sion analysis of the 15 pairs of such measurements. Results were
Ht = -0.15 + 1.03 (Area), r = 0.9998, Se = 2.47.
In this equation the slope is not distinguishable from 1, and the inter-
cept is indistinguishable from zero. Also a t-test of the sample differences
is insignificant (t = 0.60). Therefore it again appears that there is no worth-
while difference between the two methods.
FIELD SAMPLES
This data set is organized on the same basis as the standards data, ex-
cept that seven runs (instead of three levels) were executed.
However, on run 4 an anomalous steam burst caused preposterous readings
on Samples 2 and 3, so the AOV was restricted to runs 1, 2, 3, 5, 6, and 7.
In these data, of course, there are no reference values, so variabilities are
the only quantities produced from the analysis. Also, run-run variability was
considered a nuisance (the block in a balanced incomplete block design) so
that quantification of "oR2" was not performed.
The 12 balanced incomplete blocks were analyzed individually (Table 11),
resulting in aggregate estimates of crc2, as2, and aQ2. The six runs varied
(evidently) in VC concentration from about 1 to 8 ppm. The components of var-
iance are significantly larger on R7 than on the otner tive runs.
A regression analysis of results by method (Ml = 0.03 + 1.00 M2, r =
0.998, and Se = 0.120) again fails to indicate any significant difference be-
tween them. The other components of variance indicate:
1. A single collaborator reads a single sample to within about + 0.33
ppm.
2. A set of collaborators read a given sample to within + 0.7 ppm.
3» A set of collaborators read a set of samples (taken "simultaneously")
to within about + 0.91 ppm.
4. Sampling variability contributes about + 0.58 ppm to the method's
error limits.
28
-------
TABLE 11. DATA ANALYSIS OF FIELD TEST
2
Run 1 (VC = 2.25) CTQ =
a!2 =
CTC2 =
s
2
Run 2 (VC =1.57) ag =
ac2 =
CTs =
Run 3 (VC = 1.04) ae2 =
a =
c2
CT =
S
2
Run 5 (VC = 4.27) ae =
CT =
C2
CT =
S
2
Run 6 (VC = 2.01) a
a62 =
Co
£.
a =
s
o
Run 7 (VC = 6.87) ag =
CT 2 =
CTs =
All Runs (VC = 3.00)
-------
Although qualitatively comparable, it can be seen that the field results
are somewhat more precise than the laboratory data (+ 0,91 ppm versus + 1.26
ppm). This is because the three collaborators used in the field test are much
more alike than the 10 collaborators used in the first test.
30
-------
REFERENCES
1. Federal Register 40:59477, December 24, 1975,
2. Federal Register 41:46564-46573, October 21, 1976.
31
-------
APPENDIX A
LETTER TO OBTAIN POTENTIAL COLLABORATORS
32
-------
MIDWEST RESEARCH INSTITUTE
425 Volker Boulevard
Kansas City. Missouri 64110
Telephone (816) 753-7600
You are invited to participate in a collaborative test of a modified ver-
sion of EPA Method 106 - "Determination of Vinyl Chloride From Stationary
Sources," a copy of which is enclosed. Midwest Research Institute (MRI)
is under contract to the U.S. Environmental Protection Agency to conduct
this collaborative test. The test will consist of two parts: a laboratory
test of the analysis procedure and a field test of the entire method.
For the laboratory test a minimum of eight collaborators will each receive
a set of six samples of vinyl chloride with various interferences present
in some of the samples. Each sample will be supplied in a 3-liter capacity
(at STP) aerosol-type can. A heated sampling valve must be used. Inject-
tion by syringe is not acceptable.
Samples will be introduced into the sample valve loop by inserting the
needle on the sample can through a septum mounted in the line going to the
valve. Since the sample flow is under positive pressure, no sample pump
is used. Each sample will be analyzed in triplicate using two different
columnsa 2 m x 3.2 mm OD stainless steel column packed with 60/80 Chrom-
osorb 102 and a composite column consisting of the Chromosorb 102 column
followed by a 2 m x 3.2 mm OD stainless steel column packed with 20% SF-96
on 60/80 mesh AW Chromosorb P. Vinyl chloride concentrations on each sam-
ple/column combination are to be calculated by both peak area and peak
height. The original strip chart recordings must be submitted to MRI with
the results.
The sample cans must be returned to MRI after the analyses with sufficient
pressure to allow a final check for stability.
Cylinders containing approximately 5, 10, and 50 ppm vinyl chloride in ni-
trogen are to be used as standards and will not be supplied by MRI. Each
cylinder must be certified by the manufacturer by comparison against (a) a
gravimetrically calibrated vinyl chloride permeation tube, (b) a vinyl chlo-
ride gas mixture analyzed by the National Bureau of Standards, or (c) stan-
dard gas mixtures prepared in accordance with Section 7.1 of Method 106.
33
-------
MIDWEST RESEARCH INSTITU1 -
425 Volker Boulevard
Kansas City, Missouri 641
Telephone (816) 753-76
If you are interested in participating in the laboratory test of the
method, you are asked to submit a firm, fixed price bid for the collabor-
ative test. The collaborators will be selected on the basis of the ana-
lyst's experience in the analysis of vinyl chloride, the analyst's exper-
ience in gas chromatography, the ability to supply the necessary equipment
for the test, and cost. The experience of the person who will perform the
analysis and the model numbers of the gas chromtograph and sample valve
that will be used should be submitted with your bid. The person perform-
ing the analysis is designated as Key Personnel. If this person does not
perform the analyses the contract may be declared void. Bids must be re-
ceived by April 15, 1977. The samples will be sent on or about June 15th
and results must be submitted to MRI within 1 month.
The field test of the method will consist of a smal-1 group of collabora-
tors obtaining samples and analyzing the samples at a vinyl chloride plant.
Collaborators will obtain duplicate samples with a minimum of three sets
of samples per day for 2 days of testing. For this test each collaborator
must be able to supply the necessary Tedlar bags and enclosures. All sam-
ples must be analyzed within 72 hr. This requires either a gas chromato-
graph which can be taken to the test area or provision for rapid shipment
and analysis after each test. A crew of two is anticipated for each col-
laborator. The site for the field test has not been selected. You are
asked to indicate your interest in participating in the field test. If
interested, please state the model number of the gas chromatograph which
would be used and the number of rigid leakproof containers with 100 liter
Tedlar baigs that you could supply for the test. MRI is not at this time
soliciting bids for the field test.
If you have any questions in regard to the test, please call George Scheil
or Paul Constant at (816) 753-7600.
Sincerely,
MIDWEST RESEARCH INSTITUTE
George W. Scheil
Associate Chemist
Enclosures
GWS:sw 34
-------
APPENDIX B
FINAL INSTRUCTIONS TO COLLABORATORS
35
-------
MIDWEST RESEARCH INSTITUTE
425 Volker Boulevard
Kansas City, Missouri 64110
Telephone (816) 753-7600
July 28, 1977
The EPA sponsored collaborative test of Method 106 - "Determination of Vinyl
Chloride from Stationary Sources," has now started. Your laboratory is one
of the 10 collaborators selected for the laboratory test of the procedure.
This letter is to inform you of the revised test schedule and other changes
in the test.
Each collaborator should receive six cylinders of vinyl chloride in nitrogen
during the week of September 12, 1977. These cylinders may or may not contain
vinyl chloride and interferences. The sample cylinders are moderate pressure
Freon-type canisters with a volume of about 8 ft 3 (at STP). An adapter to
connect the cylinders to 1/4 in. Swagelok fittings will be supplied. If you
prefer a different adapter, please contact MRI. The samples are introduced
into the sample valve loop via Teflon tubing by partially opening the cylin-
der valve. A stainless steel valve or capillary restrictor may be needed to
limit flow into the sample loop. A sample pump is not needed.
Each sample will be analyzed in triplicate using two different columns--a
2 m x 3.2 mm OD stainless steel column packed with 60/80 Chromosorb 102 and
a composite column consisting of the Chromosorb 102 column followed by a
2 m x 3.2 mm OD stainless steel column packed with 20% SF-96 on 60/80 mesh
AW Chromosorb P. Vinyl chloride concentrations on each sample/column combi-
nation are to be calculated by both peak area and peak height. The original
strip chart recordings must be submitted to MRI with the results. The chart
recordings and calculated results for all six samples must be mailed to MRI
by October 15, 1977.
The sample cylinders should be saved with sufficient pressure for additional
measurements until MRI has reviewed your results. After your results have
been examined at MRI you will be notified if the samples need to be returned
to MRI to resolve any questions. If your results are satisfactory you may
keep the sample cylinders.
Cylinders containing approximately 5, 10, and 50 ppm vinyl chloride in nitro-
gen are to be used as standards and will not be supplied by MRI. Each cylinder
must be certified by the manufacturer by comparison against: (a) a gravi-
metrically calibrated vinyl chloride permeation tube; (b) a vinyl chloride
gas mixture analyzed by the National Bureau of Standards; or (c) standard gas
mixtures prepared in accordance with Section 7.1 of Method 106.
36
-------
Page 2
July 28, 1977
These requirements have been published in the Federal Register and a copy is
attached together with a copy of the Method 106 procedure. The gas supplied
should provide a certificate stating compliance with the Federal Register
requirements. Please send MRI copies of the certificates with your data.
A check of several gas suppliers indicates that Matheson and Air Products
do not supply vinyl chloride standards. Airco in Riverton, New Jersey, Ana labs
in North Haven, Connecticut, and Scott Specialty Gases in Plumsteadville,
Pennsylvania, state that they can supply standards which conform to the
Federal Register requirements.
You will receive additional information regarding the field test at a later
date. If you have any questions in regard to the test, please call Dr. George
Scheil or Mr. Fred Bergman at (816) 753-7600.
Sincerely,
George W. Scheil
Associate Chemist
GWS:clk
Enclosure
37
-------
APPENDIX G
METHOD 106 - DETERMINATION OF VINYL CHLORIDE FROM STATIONARY
SOURCES WITH AMENDMENTS
38
-------
METHOD 108DCTCRMINATION or VINYL
CfTLORlDC FROM STAT1ONHRV SOL'RCZS
INTRODUCTION
Performance of this method should not oe
attempted by persons unfamiliar with the
operation of a gas chromatograph, nor by
those who are unfamiliar with source sam-
pling. »s there are many details that are
beyond the scope of this presentation. Care
muat be exercised to prevent exposure of
sampling personnel to vinyl chloride, a car-
cinogen.
1. Principle and Applicability.
1.1 An Integrated bap sample of stack gas
containing vinyl chloride (chloroethylenei
la subjected to chromatographlc analysis.
using a flame lonl/.atlon detector.
1.2 The method Is applicable to the meas-
urement of vinyl chloride In stack gases from
ethytene dlchlortde. vinyl chloride and poly-
vinyl chloride manufacturing processes, ex-
cept where the vinyl chloride Is contained in
participate matter.
2. Range and Sensitivity.
The lower limit of detection will vary ic-
cordlng to the chromatograph used. Values
reported Include 1 x 10-' ing and 4 x 10-'
mg.
3. Interferences.
Acetaldehyde. which can occur In some
vinyl chloride sources, will Interfere with the
vinyl chloride peak from the Chromosnrn 102
column. See sections 4.3.2 and 6.4. If resolu-
tion of the vinyl chloride peak Is still not
satisfactory for a particular sample, then
chromatograph parameters can he further
altered with prior approval of the Admin-
istrator. If alteration of the chromatoyraph
parameters fulls to resolve the vinyl chloride
peak, then supplemental confirmation of the
vinyl chloride peak through an absolute
analytical technique, such 0.1 mans spectro-
acopy, must be performed.
4. Apparatus.
4.1 Sampling (Figure 1).
4.1.1 ProbeStainless steel. Pvrer glass,
or Teflon tubing according to stack temper-
ature, each equipped with a glass wool plug
to remove partlculuic matter.
4.1.2 Sample lineTenon. 6.4 mm outside
diameter, of sufficient length to connect
probe to bag. A new unused piece Is employed
for each series of hog samples that constitutes
an emission test.
4.1.3 Male (2) and female (2) stainless
steel quick-connects, with ball checks (one
pair without) located as shown In Klgure 1.
4.1.4 Tctllar bags, 100 liter capacityTo
contain sample. Teflon bays are not accept-
able. AlumLnlzcd Mylar bays may be used.
provided that the samples are analyzed
within 24 hours of collection.
4.1.5 Rigid Icakproof containers for 4.1.4.
with covering to protect contents from sun-
light.
4.1.6 Needle valveTo adjust sample flow
rate.
4.1.7 PumpLeak-free. Minimum capac-
ity 2 liters per minute.
4.1.8 Charcoal tubeTo prevent admis-
sion of vinyl chloride to atmosphere in vicin-
ity of samplers.
4.1.9 Flow meterFor observing sample
flow rate: capable of measuring a now range
from 0.10 to 1.00 liter per minute.
4.1.10 Connecting tubingTeflon, 6.4 mm
outside diameter, to assemble sample train
(Figure 1).
4.1.11 Pilot tubeType S (or equivalent),
attached to the probe so that the sampling
flow rate can he regulated proportional to
the stack gas velocity.
4.2 Sample recovery.
4.2.1 TubingTefloo. 64 mm outside
diameter, to connect bag to gas chromato-
graph sample loop. A new unused piece Is
employed for each series of bag samples that
constitutes an emission test, and U to be dis-
carded upon conclusion of analysts of those
bags.
4.3 Analysis.
4.3.1 Gas c'.iromatographWith flame
lonlzatlon detector, potentiometric strip
chart recorder and 1.0 to 5.0 ml heated sam-
pling loop in automatic simple valve.
4.3.2 Chromatographlc columnStainless
steel. 2.0 x 3.2 mm, containing 80/100 mesh
Chromosorb 102. A secondary colum of OB
SF-96. 20% on 60'80 mesh AW Chromosorb
P, stainless steel. 2.0 m x 3.2 mm. will be
required u* acetaldehyde Is present. If used.
the SF-96 column is placed after the Chromo-
sorb 102 column. The combined columns
should then be operated at 110'C.
4.3.3 Flow meters (2)Rotameter type.
0 to 100 ml/mln capacity, with flow control
valves.
4.3.4 Gas regulatorsFor required gas
cylinders.
4.3 5 ThermometerAccurate to one de-
gree centigrade, to measure temperature of
heated sample loop at time of sample Injec-
tion.
4.3.6 BarometerAccurate to 5 mm Hg. to
measure atmospheric pressure around gas
chromatograph during sample analysis.
4.3.7 PumpLeak-free. Minimum capac-
ity 100 ml/mln.
4.4 Calibration.
4.4.1 TubingTeflon. 6.4 mm outside
diameter, separate pieces marked for each
calibration concentration.
4.4.2 Tedlar bagsSlxtcen-lnch square
size, separate bag marked for each calibra-
tion concentration.
4.4 3 Syringe0.5 ml. gas tight.
4.4.4 Syringe50/.1. gas light.
1 Mention of trade names on specific prod-
ucts does not constitute endorsement by the
Environmental Protection Agency.
4.4.6 Flow meter Rotaineter type, 0 to
1000 ml/mln range accurate to ±1%, to
meter nitrogen In preparation of standard
gas mixtures.
4.4.0 Stop watchOr Known accuracy, to
tlmo gas flow In preparation of standard gas
mixtures.
5. Reagents. It In necessary that all rea-
gents be of chromatographlc grade.
5 1 Analysis.
5.1.1 Helium gas or nitrogen g
-------
nd the attenuator getting. Record the lab-
oratory pressure. Krom the chart, select the
peak hAving the retention time correspond-
ing to vmyl chloride, cvs determined In Sec-
tion 72. Measure the peak aren. Am. by use
of H.I.. and a. dKc Integrator or n planlmeter.
Measure the peak height, II,,,. Record Am and
the retention time. Repeat the Injection at
lea«t two times or until two consecutive vinyl
chloride peaks do not vary In nrea more than
6';,. Til* murage value for these two areas
v;in be vi.'» il 10 compute the bag concenira-
tloit.
Comp.iie the ratio of H,., to Am for the vinyl
chloride sample with the came ratio for the
standard prnk which Is closest In height. As
a guideline, if these ratios dlfTer by more
tliiui 10', . Hie vinyl chloride peak may not
be pure ir>i M'M-'in o the ambient temperature and
b.ironirlri'.1 pressure near the bag. (Assume
'.lie reuti.e humidity to be 100 percent.)
From a writer saturation vapor pressure table,
determine the record nnd water vapor con-
tent of the bag.
7 Calibration and Standards.
7 1 PiepAi-atlon of vinyl chloride standard
gas mixtures. Evacuate a sixteen-lnch square
Tedlwr br.g that has passed a leak check
(described In Section 7.4) and meter In 5.0
liters of nitrogen. While the bag Is fllllng. use
the 05 ml syrmre to Inject 250jil of 99.9 + %
vinyl chloncle through the wall of the bag.
Upon withdrawing the syringe needle. Im-
mediately cover the resulting hole with a
piece of adhesive tape. This gives a concen-
tration of 50 ppm of 7inyl chloride. In a like
manner use the other syringe to prepare dilu-
tions haviri; 10 and 5 ppm vinyl chloride
concentrations Place each bag on a smooth
eurftce and alternately depress opposite
sides of the bng 50 times to further mix the
gases.
73 Determination of vinyl chloride re-
tention tliv.e This section can be performed
simultaneously with Section 7.3. Establish
chromatopraph conditions Identical with
those In Section 6.3, above. Set attenuator
to X 1 position. Flush the sampling loop
with zero helium or nitrogen and activate
the sample valve. Record the Injection time.
the sample loop temperature, the column
temperature, the carrier gas flow rate, the
chart speed and the attenuator setting
Record peaks and detector responses that
occur In the absence of vinyl chloride Main-
tain conditions With the equipment plumb-
ing arranged identically to Section 6.3, flush
the sample loop for 30 seconds at the rate of
100 ml mln with one of the vinyl chloride
calibration mixtures and activate the sample
valve. Record the Injection time. Select the
peak that corresponds to vinyl chloride.
Measure the distance on the chart from the
Injection time to the time at which the peak
maximum occurs This quantity, divided by
the chart speed, is den.ied as the retention
time Record
73 Preparnnon of chromatoyraph cali-
bration curve. Mnke a g;'.s chromatognphlc
measurement of cacn standard gas mixture
(described in Section 71) using conditions
Identical with those listed In Section 83
above Flush the sampling loop for 30 seconds
at the rate of 100 ml mln with each standard
gas mUture and activate the sample valve.
Record C.. the concentrations of vinyl chlo-
ride Injected, the attenuator setting, chart
speed, peak area, sample loop temperature.
column temperature, carrier gns flow rate.
and retention time. Record the laboratory
prensiire Calculate At, the peak area multl-
tucV hit
NntlM it tnd« ««« »« fM<:'<* ftcki.tti < MC c»»tltuce
tr ck« anil ul rntwIlM Acme?.
plied by the attenuator netting Repeat until
two Injection areas an within 5%, then plot
those points vs C,. When the other coaoeo-
traUons have been plotted, draw a smooth
curve through the points. Perform calibra-
tion daily, or before and after each set of
bag samples, whichever !» more Irequeut.
7.4 Bug leak checks. While performance
of this section Is required subsequent to bag
use. It Is also advised that It be performed
prior to bag use. After each use. make sure
a bag did not develop lealcs a* follows. To leak
check, connect a water manometer and pres-
surize the bag to 5-10 cm H.O (24 ui H.O).
AJlow to stand for 10 minute* Any displace-
ment In the water manometer Indicate* a
leak. Also check the rigid container lor leeks
In thl* manner.
(NOTE: An alternative leak check method
la to pressurize the bag to 5-10 cm H.O or
2-4 In. H.O and allow to stand overnight.
A deflated bag Indicates a leak.) For each
sample bag In Its rigid container, place a
rolametrr In-line between the bag and the
pump Inlet. Evacuate the bag Failure of the
rotame'.er to register zero flow when the bag
appears to be empty indicates a leak.
8. Calculations.
8.1 Determine the sample peak area a*
follows:
8.3 Tlnyl chloride concentrations. Prom
the calibration curve described In Section
7.3, above, select the value of C, that cor-
responds to A,., the sample peak are*. Cal-
culate Cb M follows:
c,r,r.
Equation 106-3
Where:
JJ.t-Tlio «3ter vapor cwiU-.m of the bag laniMv, u
The concentration of vinyl chloride 10 the b«f
sample in ppm.
The concenlrution of rlnyl chloride UidiomUd by
the gin chronifvU'craph, la ppm.
The reference pressure, the laboratory pnsvire
reoorded during cahhrivtlon. nun H%.
The sample loop temperature oo the
Kale at the tliuo of analysis. °K.
The laboratory prc&suro ut tune of aiialyiu. mm
Hg.
",-The referents t«nipcniUire, the wmple loop
temperature reeoruod diulnf oalibratlon, *R'
Ct
C.
p,
r.
p.
A,
where:
X.Tin* sninplo p^ik ivrna.
A . The mf^uro
-------
29008
RULES AND REGULATIONS
9: Section 1.1 of Test Method 106
is corrected as follows:
v 1-1. An . integrated bag sample of naek
ga> containing vinyl chloride (chloroeth«o»)
is subjected to chromatographlc analysl*. sift-
ing a flame ionlzailon detector.--;.
- 13. Section 4.1.10 of Test Method 106 Is
corrected as follows: '.."-.*
4.1.10 Connecting tuWny. Teflon. 6.4
mm outside diameter, to assemble sample
crain (Figure 10«-1). -
10. Section 3 «f Test
. corrected as follows:...:, .
3. Interferences. Aceialdehvde. which CAO
occur In tome vinyl chloride sources. will In-
terfere with .the vinyl chloride peak from
the Chromasorb 103 ' column. Se« sections
4.3-2 and 6.4. II resolution of the vinyl
chloride peak Is soil not satisfactory for a
particular sample, then cnromatograph pa-
rameters can be further altered -with prior
approval of the Administrator. If alteraaon
of the chromatograph parameters falls to
resolve the vinyl chloride peak, then sup-
plemental confirmation of the vinyl chloride
peak through an absolute analytical tech-
nique. such as mass spectroscopy. must b*
performed.
11. Section 4.1 of Test Method 106 is
corrected as follows:
4.1 Sampling < Figure 106-1).
12. SecUon 4.1.3 of Test Method 106 is
corrected as follows:
4.1.3 Male (2) and female (2) stainless
steel quick-connects, with ball checks (one
pair without) located as -shown In
106-1.
' -- 14. Section 4.3.2 of Test Method 108 is
108 is amended as follows:'
4.32 Chramatogra-phic column, stainless
st«el. 2 mx3J "»«. containing 80/100 mesh
Chromasorb 103. A secondary column of OE
SP-98, 20 percent on 60/80 mesh AW Chroma-
sorb P, stainless steeL 2 m x 3.3 mm or Pora-
pak T. 80/100 mesh, stainless steel. 1 mx3J
n-.m 15 required If acetaldehyde Is present. If
used, a secondary column-is placed after the
Chromasorb 103 column. The combined
should, then be operated at 120* C..
15. Section 5.2. of Test Method 108 Is
revised as follows: ..... .....:.
S3 Calibration, Use one of the following
options:- either 5J.1 and 3.2.3, or 3J2JJ... - -
3Ja -Vinyl. cWorule, . 99.S-t- percent. Pure
vinyl chloride gaa certified by tb» manufac-
turer to contain a minimum of 99.9 percent
vinyl, chloride for use In the preparation of
standard gas mixtures In Section 7.1. If-the
gta manufacturer maintains a bulk cylinder
supply of 99.9+ percent vinyl chloride, the-
certtflcaC"* analysis may have been per-
formed on this supply rather than on esch-
gm» cylinder prepared from thu hulk, supply.
Th« dat* of.gas cylinder preparation and the
certtfled analysis must havo been affixed to
tha cylinder before- shipment from Oe gas
manufacturer to the buyer. - .
3.2.2 Nitrogen gas. Zero grade, for prepa-
ration of standard gcs nurtures. .
S-3-3 Cylinder standards (3). Gas mix-
ture standards (SO. . 10. and 3 ppm vinyl.
chloride In nitrogen cylinders) for wnlch the
ga* composition haa been censed by the .
manufacturer. The manufacturer must have
recommended a maximum shelf life for each
cylinder i~ Uiat the concentration does not
change greater t.han =5 percent from, the
certified value. The date of gaa cylinder prep-
aration. certified nnyl chloride concentra-
tion and recommended maximum Jbelf Life
must have been afflxed to- the cy Under before
snip men: from the gas manufacturer to the
buyer. These gaa mixture standards may be
directly used to prepare a chromatograph
calibration curve as described In section 7.3.
5.2.3.1 Cylrmter Jtandordj certification:
Tie concentration of vinyl chloride In nitro-
gen In each cylinder must have been certified
by the manufacturer by a direct analysis of
each cylinder using an analytical procedure
that the manufacturer had calibrated, on the
day of cylinder analysis. The calibration of
the analytical procedure shall, as a minimum.
have utilized a three-point calibration curve.
It is recommended that the manufacturer
maintain two calibration standards and usa
these standards In. the following way: (1) a
high concentration standard (between 50 and
100 ppm) for preparation of a calibration
curve by in appropriate dilution technique:
(2) a low concentration standard (between
5 and 10 ppm) for venflcaclon of the dilution
technique used.
5.2.3.2 Establishment and verification of
calibration standards. The concentration of
each calibration standard must have been
established by the manufacturer using
reliable procedures. Additionally, each
calibration standard must have been 7erl-
Sed bv the manufacturer by one of tbe
following procedures, and tie agreement
becwees tie Initially deterT^iced concen-
tration value and the verification concen-
tration value n^ust he witritn 5 percent:
.':) -.r::±;atlon value dererzilzed iy csm-
par'-son w.:h a cailbra^d vinyl chlar'.ie
41
permeation tube. (2) verification value
determined by comparison with a gas mix-
ture prepared In accordance with the pro-
cedure described In section 7.1 and using
99.9+ percent vlnyle chloride, or (3) verifi-
cation value obtained by having the
calibration standard analyzed by the Na-
tional Bureau of Standards. All calibration
standards must be renewed on a time
Interval consistent with the shell life of
the cylinder standards sold.
' 16. Section 6.2 of Test Method 106 Is
amended as follows:
-8.2 Sam-pie storage. Sample bags must be
kept out of direct junllght. When at all
possible analysis is to be performed xlthln
24 hours, but In no- case in excess of 72
hours of sample collection.
17. Section 7.1 of Test Method 106 Is
'amended as follows:.- ' '
- 7.1 .Preparation of vinyl chloride stand-
ant gaa mtxrunj. Evacuate a sixt«en-lnch
square Tedlar bag that has passed i leak
check (described In Section 7.4) and meter
In. 5 liters of nitrogen. . While the bag is
fllllng, use the 0.3- ml syringe to Inject
250uJ of 99.94- percent vinyl chloride
through the wall of .the bag. Upon with-
drawing, the syringe needle, immediately
cover- the resulting hole with a piece of
. adhesive tape. Too bag now contains a
vinyl chloride concentration of JO-ppm. In
. a " tike manner use the other syringe- to
prepare gas mixtures having 10 and 5 ppm
vinyl chloride concentrations. Place each
bag on a smooth surface and alternately
depress opposite sides of the bag iO times
to further mix. the gases. These gas mixture
standards may be used for 13 days from the
date of preparation, after .which time prep-
aration of new gas - mixtures is- required.
fCADTtow.Contamination may be a prob-
lem when a bag is reused if tbe new gas
mixture standard contains a lower con-
centration than tbe previous gas mixture
standard did.)
_18. Section 7.3 of Test Method 106 is
amended as follows:
7.3 Preparation of Cfiromatograpti. cali-
bration curve. Make a ga»-cbroma:o?raphlc
measurement of *ach gas mixture standard
(described In section 5.2.2 or 7.1) using con-
ditions Identical with those listed In sections
8.3 and 8.4. Flush the sampling loop for 30
seconds at the race of 100 mi/min with each
standard gas mixture and activate the sam-
ple valve. Record C.. the concentration of
vinyl chloride Injected, the attenuator set-
ting, chart speed, peai area, sarr.ple loop
temperature, column temperature, carrier
gas flow rate, and retention time. Hecord trie
laboratory pressure. Calculate A«. the peax
area multiplied by the attenuator setting.
Repeat until two Injection areas are within
5 percent, then plot these points 7. Ce. TThen.
the other concentrations nave been plotted.
draw a smooth curve through the polnto.
Perform calibration dally, or before and a.'ter
each set of bag samples, wblchever is more
frequent.
-------
RETENTION INDICES FOR POSSIBLE VINYL CHLORIDE INTERFERENCES
42
-------
TABLE C-l. RETENTION INDICES FOR POSSIBLE VINYL CHLORIDE INTERFERENCES
U>
Methane*
Echylene
E thane *
Propane'"
Methyl chloride
Methanol
Acetaldehyde
Echylene oxide
Vinyl chloride
Isobutane
Isobutylene
1-Butene
n- Butane*
1,3-Butadiene
trans-2-Butene
Ethanol
Ethyl chloride
cis-2-Butene
1 , 1-Dichlo roe thy lone
trans- 1 , 2- Dichloroethy lene
2 m Chromosorb 102
100°C
100
180
200
300
320
330
355
355
360
380
395
395
400
400
400
415
415
415
480f
510f
2 m Chromosorb 102
4- 1 in Porapak T
120°C
100
180
200
300
340
395
400
395
375
380
395
395
400
410
410
475
430
415
490f
495f
2 m Chromosorb 102
+ 2 m SF-96
120°C
100
175
200
300
320
350
375
375
360
380
385
395
400
395
400
435
415
410
480f
505t
2 m Chromosorb 102
+ new 2 m SF-96
120°C
100
-
200
300
325
375
(low levels retained)
400
(low levels retained)
-
(low levels retained)
360
380
390
-
400
395
_
-
410
-
-
* Reference compounds for
t Column at 150°C.
indices.
-------
APPENDIX D
LETTER TO COLLABORATORS
44
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MIDWEST RESEARCH INSTITUTE
425 Volker Boulevard
Kansas City, Missouri 64110
Telephone (816) 753-7600
December 1, 1977
The results of the laboratory part of the collaborative test of EPA Method
106 are now complete. The preliminary analysis of the data indicates that
no serious errors occurred. A few chromatograms were misinterpreted and
two collaborators did not detect any acetaldehyde with the chromosorb 102
column. The contents of the samples are given in the the table attached.
Vinyl chloride and isobutane have proved to be stable. The acetaldehyde
concentration is decaying gradually in most samples and methanol has
either disappeared or is eluting with isobutane. The chromosorb 102 col-
umn should have resolved all samples except 1814, but acetaldehyde is
retained on the SF-96 column. The separation of isobutane is usually
reduced on SF-96. Analyses conducted by NBS was only for vinyl chloride.
Sample No.
1814
4036
4786
6800
10673
60106
Components (N Balance)
6.8 ppm vinyl chloride
45.1 ppm acetaldehyde
13.0 ppm vinyl chloride
7.1 ppm methanol
21.1 ppm isobutane
8.73 ppm vinyl chloride
7.04 ppm vinyl chloride
4.5 ppm methanol
10.6 ppm isobutane
18.4 ppm acetaldehyde
2.24 ppm vinyl chloride
Vinyl Chloride Found by
NBS (ppm)
6.75
13.0
8.57
7.34
0.05
2.26
45
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MIDWEST RESEARCH INSTITUTE
Page 2
December 1, 1977
The field part of the collaborative test of EPA Method 106 under MRI's
prime EPA Contract No. 68-02-2737 is scheduled for February 14-16, 1978.
The test will be conducted at the Diamond Shamrock facilities in Deer Park,
Texas. The participants in the laboratory test are requested to submit
fixed-price bids if they are interested in participating in the field test.
A total of three groups will conduct simultaneous sampling from a manifold.
Each collaborator must have two personnel on the site, a sampler and a
gas chromatograph operator. The person who preformed the original labor-
atory analyses must be the GC operator and shall be designated as key per-
sonnel for this test.
Each team must provide the following equipment for the test:
1. A gas chromatograph (FID) with gas sampling valve and recorder.
2. Three calibration gas cylinders (5, 10, and 50 ppm vinyl chloride).
3. A minimum of 2 tested 100 liter bags and enclosures as required
by Method 106. Tedler or aluminized Mylar bags are acceptable.
4. Rotameter, pump, and other necessary items to obtain samples from
the manifold and perform leak tests.
An area (indoors) will be provided for the chromatographs. Air, hydrogen,
and carrier gas will be provided to all teams as well as suitable 110 V
AC power. The samples will probably contain low levels of vinyl chloride.
The instrument used must have sufficient sensitivity to accurately measure
vinyl chloride as low as 0.5 ppm.
Since sampling will be done from a common (ground level) manifold, no pitot
or oxygen measuring equipment is needed. Sampling will be done at a constant
rate of about 0.5 pm for 1 hr periods. The manifold will probably be under
slight positive pressure so that the pump can be removed during sampling,
although it must be available for emptying bags and making leak checks.
The sampling will be done in a restricted access area where explosion-
proof pumps are required. If an AC pump is used it must be inside an ex-
plosion-proof or inert purged housing. Battery driven approved personnel
sampling-type pumps are also acceptable.
The tentative work schedule is:
February 14 - Set-up and test equipment.
February 15 - Sampling - each team will collect 4 samples. Analysis - each
team will analyze their own vinyl chloride standards and one of the other
teams' standards. Each team will also analyze their own 4 samples and 4
samples obtained by other teams.
46
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MIDWEST RESEARCH INSTITUTE
Page 3
December 1, 1977
February 16 - Same as February 15; pack equipment and clear the site.
Each test day should be completed within 8-10 hr. All samples and standards
will be analyzed in triplicate in the same manner as used in the laboratory
collaborative test, except that only one column will be used. Each team
must bring both the Chromosorb 102 and SF-96 columns to the test and the
column(s) to be used will be selected on the set-up day. All samples will
be measured by peak height and area, and the original recorder charts must
be sent to MRI.
The participants will be chosen on the basis of ability to meet the nec-
essary requirements, performance on the laboratory test, and cost. Firm,
fixed-price bids must be submitted to MRI by January 4, 1978 to be con-
sidered. Technical questions should be referred to Dr. George Scheil. Con-
tractual questions should be referred to Ms. Sequin Lukon. The MRI phone
number is (816) 753-7600.
Sincerely,
MIDWEST RESEARCH INSTITUTE
George Scheil
Associate Chemist
GSrsw
47
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APPENDIX E
TENTATIVE PROCEDURE FOR SAMPLING AND ANALYSIS OF
VINYL CHLORIDE USING CHARCOAL ADSORPTION TUBES
48
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December 1977
TENTATIVE METHOD FOR THE DETERMINATION OF
VINYL CHLORIDE
1. Principle and Applicability.
1.1 Vinyl chloride (chloroethene) is absorbed from air onto charcoal
adsorbers, which are subsequently extracted with carbon disulfide. The
resulting solutions are then measured chromatographically, using a flame
ionozation detector.
1.2 The method is applicable to the measurement of vinyl chloride
in ambient air using a 24-hour sampling period.*
2. Range and Sensitivity. The limit of detection is approximately
3 1
0.003 mg/m (1 ppb). The maximum of the range is 20 mg/m (8 ppm); it
may be increased by extending the calibration range or by diluting the
sample.
3. Interferences. At the present time, there are no known common pollu-
tants in the ambient atmosphere in sufficient concentrations to interfere
with the measurement of vinyl chloride. However, certain volatile hydro-
carbons and Freons have elution characteristics similar to vinyl chloride.
* Warning: Vinyl chloride is a suspected carcinogen. Care must be exercised
to protect operators from breathing vinyl chloride fumes. Carbon disulfide
is toxic and its vapors form explosive mixtures with air. Work with this
material in a well ventillated fume hood.
49
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Among the latter is Freon 12 (dichlorodifluoromethane). Under certain
conditions, a peak is associated with the injection and subsequent with-
drawal of the microsyringe into and from the G.C. septum. These peaks can
also give interferences with the vinyl chloride peak.
4. Precision and Accuracy. Replicate gas chromatographic analyses of
standard gas mixtures and sample aliquots should not deviate by more than
3 per cent relative standard deviation. When the entire analysis is
repeated, preliminary studies indicate that relative standard deviations
of 6 per cent are attainable. No information is presently available on
accuracy.
5. Apparatus.
5.1 Sampling - Air Monitoring materials.
5.1.1 Pump - Capable of maintaining an air pressure differential
greater than 0.5 atmospheres at the desired flow rate.
5.1.2 Critical Orifice - Twenty-seven gauge 3/8" hypodermic needle.
To control flow rate at approximately 200 ml/min.
5.1.3 Tubing - 18 cm length of 10 mm O.D. borosilicate glass with
tapered ends, to prepare adsorption tube.
5.1.4 Serum caps - 5 x 9 ram and 7 x 11 mm sizes.
5.1.5 Vibrator - To achieve close packing of the adsorption tube.
5.1.6 Air flow meter - Rotometer type; 1 - 260 ml/min range. To
calibrate critical orifice.
50
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5.1.7 Furnace, muffle - To operate at 400°C.
5.2 Sample recovery.
5.2.1 Graduated cylinder - Glass stoppered; capacity, 25 ml (TC).
5.2.2 Pipette, dropping - 2 ml.
5.2.3 Serum bottle - Narrow mouth for septum sealing; 2 ml.
5.2.4 Serum cap - With Teflon coating on the side of the septum
exposed to the sample 5 x 9 mm size. (Hewlett-Packard #5080-8713 has
been found to be satisfactory).
5.2.5 Aluminum serum cap seal.
5.2.6 Crimper - For use with aluminum serum cap seals.
5.3 Analysis.
5.3.1 Gas chromatograph - With flame ionization detector and
potentiometric strip chart recorder.
5.3.2 Chromatographic column - stainless steel, 2.5 m x 3.2 mm O.D.,
containing 0.4% Carbowax 1500 on Carbopak A packing, (w/w)
5.3.3 Microsyringe - 0 to 10 microliter range, graduated.
5.3.4 Gas regulator - 4 to 50 psig range.
5.3.5 Needle valve - to control standard gas flow.
5.3.6 Teflon tubing - 10 mm O.D.
5.3.7 Tygon tubing sleeve - 10 ram I.D.
Mention of trade names or specific products does not constitute endorsement
by the Environmental Protection Agency.
51
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6. Reagents
Unless otherwise indicated, it is intended that all reagents be chromato-
graphic grade or conform to the specifications established by the Committee
of Analytical Reagents of the American Chemical Society, where such speci-
fications are available; otherwise, use best available grade.
6.1 Sampling.
6.1.1 Charcoal - Activated coconut shell charcoal. (Fisher Scientific
Company, 6 to 14 mesh is effective.)
6.1.2 Glass wool - borosilicate
6.1.3 Aluminum foil.
6.2 Sample recovery.
6.2.1 Carbon disulfide.
6.3 Analysis.
6.3.1 Nitrogen gas - Zero grade, for chromatographic carrier gas
and for preparation of standard gas samples.
6.3.2 Vinyl chloride - 128, 25.6, and 12.8 mg/ra3 at 25 C, 1 atm
50 ppm v/v, in zero nitrogen. Analyzed. For calibration.
6.3.3 Combustion Air - Containing less than 1.3 mg/m^ hydrocarbons
(2 ppm as methane). To operate flame ionization detector.
7. Procedure.
7.1 Sampling.
7.1.1 Activation of charcoal - Heat charcoal to 400°C for one hour
to remove adsorbed gases. Store in a sealed container.
52
-------
7.1.2 Preparation of adsorption tube - Insert glass wool into tubing
(see Section 5.1.3) and tamp into position at one end to a depth of
approximately 2.5 cm. Mount tube on vibrator in a verticle position. Add
charcoal a little at a time and vibrate after each addition to prevent
channelling. Fill tube to a depth of 13 cm with charcoal. Insert glass
wool into remainder of tube. Prepare additional adsorption tubes in a
similar and uniform manner. Cover ends of tubes with serum caps. Wrap
with aluminum foil to protect tubes from light during storage and subsequent
use. Insert critical orifice through septum at one end of tube. Retain
until calibration, sampling and recalibration procedures have been completed.
Sufficient tubes should be prepared from a single lot of charcoal to complete
the sample analysis and associated calibration.
7.1.3 Sample collection. Remove serum cap from one end of the adsorp-
tion tube and mount it with open end downward. Connect critical orifice
to the sampling train. Begin drawing air through the tube. Record time
and adsorption tube number. Continue sampling for 1 hr. At end of sampling
interval, record time, disconnect adsorption tube from sampling train and
protect open end with serum cap. Remove sample to analytical area. Protect
tube from light.
7.2 Sample recovery. Fill the graduated cylinder to the 25 ml mark
with carbon disulfide, stopper and cool in an ice bath. Remove cap and
glass wool from one end of the adsorption tube and, with continued cooling,
rapidly add charcoal to the carbon disulfide. Stopper cylinder immediately.
(Note: the mixing of charcoal and carbon disulfide is an exothermic process
53
-------
that causes local boiling of the solution. The mixture must be cooled
and the container stoppered to prevent loss of vinyl chloride.) Mix
thoroughly. Allow mixture to stand for one half-hour in the ice bath.
Mix throughly and draw off 2 ml of the supernatant liquid. Completely fill
2 ml serum bottle, cap and seal.
7.3 Analysis.
7.3.1 Column preconditioning. Prior to its initial use, the chroma-
tographic column is heat treated to remove impurities. To do this,
establish a 40-60 ml/min flow of zero nitrogen through the column and raise
its temperature from ambient by 2°C/min to 200°C. Maintain these conditions
for 48 hours, or until base line drift is eliminated.
7.3.2 Chromatographic analysis. Set the column temperature to
60°C and the sample inlet port temperature to at least 170°C. Operate
the flame ionization detector at the temperature specified by the manu-
facturer. Using zero nitrogen as the carrier gas, establish a flow rate
in the range consistent with the manufacturer's requirements for the satis-
factory detector operation. A flow rate of 40 ml/min has been shown to
produce adequate separations. Observe the base line periodically and
determine that the noise level has stabilized and that base-line drift has
ceased. Inject a 2.5 microliter aliquot of the supernatant solution of
the sample into the gas chromatograph. Mark the injection point on the
chart. (The injection point is defined as the position of the pen on the
chart at the time of sample injection.) Record the sample number, the
column temperature, carrier gas flow rate, chart speed and the attenuator
54
-------
setting. From the chart, select the peak having the retention time
corresponding to vinyl chloride. (See Section 8.3 below). Measure the
peak height, IL., the distance in chart divisions from the average value
of the baseline to the maximum of the wave form. Record H and the reten-
tion time. Purge the column at 160°C for five minutes.
8. Calibration and Standards.
8.1 Calibration of absorption tube flow rates. Connect absorption
tube to sampling train as in 7.1.3, above. Connect flowmeter in series.
Turn on pump and measure flow rate. Record rate and adsorption tube
number. Repeat flow rate calibration procedure after sample collection.
Denote flow rate before sampling as F^; denote flow rate after sampling
as F2«
8.2 Preparation of vinyl chloride standard mixtures. Connect
o
regulator to the 12.8 mg/m standard gas cylinder as shown in Figure 12.2.
Put needle valve on regulator outlet. Remove serum caps from a fresh ad-
sorption tube. Connect needle valve to the adsorption tubes with 10 mm
Teflon tubing using an end-to-end sleeve joint at the inlet end of the
adsorption tube. Connect rotometer to outlet side of the adsorption tube.
Disconnect sleeve on inlet of adsorption tube. Purge sample line
briefly, venting gas in a safe area. Reconnect line and set flow rate to
200 ml/min. Sample cylinder gas for 1 hr, maintaining constant flow. Record
sampling start and stop times, inital and final flow rates, tube number,
and cylinder vinyl chloride concentration. Disconnect adsorption tube and
55
-------
replace serum caps. Repeat with fresh adsorption tubes using the 25.6 and
128 mg/nr standards. Recover the standard samples following the procedure
described in 7.2.
8.3 Determination of vinyl chloride retention time. Establish
chromatographic conditions identical with those in 7.3.2 above. Set
attenuator to X 1 position. Inject a 2.5 ^1 portion of carbon disulfide
into gas inlet port. Mark the injection point on the chart and record the
column temperature, the carrier gas flow rate, the chart speed and the
attenuator setting. Record peaks and detector responses that occur in the
absence of vinyl chloride. Maintain conditions. Inject 2.5 nl of the
12.8 mg/m3 standard into gas chromatograph. Mark the injection point on
the chart. Select the peak that corresponds to vinyl chloride. Measure
the distance on the chart in mm from the injection point to the peak maximum.
This distance, divided by the chart speed in mm/min, is defined as the
retention time. Record.
8.4 Preparation of chromatograph calibration curve. Make a gas
chromatographic measurement of each standard mixture described in Section 8.2
(12.8 through 128 mg/m3), using conditions identical with those listed in
Section 7.3.2, above. Record Wvc V x C x Vi/Vs, the attenuator setting,
chart speed, peak height and retention time. Calculate H , the peak height
multiplied by the attenuator setting. Plot W vs H . Repeat until
replicate measurements do not deviate by more than 370 relative standard
deviation and draw a smooth curve through the points. Check calibration
after every fifth analysis using the 12.8 mg/m3 (5 ppm) standard mixture
56
-------
and either the 25.6 or 128 mg/nr*, whichever exceeds the highest unknown
analyzed. Recalibrate daily, and whenever remeasurement of a standard gas
sample deviates from its calibration value by more than 6%.
9. Calculations.
9.1 Uncorrected volume. The volume of air sample is not corrected
to S.T.P., because of the uncertainty associated with 24-hr average
temperature and pressure values. Determine the air sample volume taken
for analysis.
F1 + F2
Vm ~ x T x 10'6,
where:
Vm = The volume of gas sampled (uncorrected), m^.
F^ = The measured flow rate before sampling, ml/min.
F2 = The measured flow rate after sampling, ml/min.
T = The sampling time, min.
9.2 Determine the sample peak height as follows:
HC HmAni>
whe re:
Hc = The sample peak height, chart divisions.
^ = The measured peak height, chart divisions.
^ = The attenuator setting.
57
-------
9.3 Vinyl chloride concentration.
9.3.1 Calculate the vinyl chloride concentration as mg/m3. From the
calibration curve described in Section 8.4, above, select the value of
Wyc that corresponds to HC, the sample peak height.
W V
vc s
Cvc =
V V.
m i
W
VC 4
V
m
where
Cvc = The concentration of vinyl chloride in the air sample, mg/m
Wvc = The quantity of vinyl chloride measured by gas chromatography, mg,
Vs = The total volume of carbon disulfide in which the vinyl chloride
sample is contained, 25 ml.
Vm = The uncorrected sample volume, from 9.1 above, m3.
V^ = The volume of carbon disulfide solution injected into the
chromatograph for analysis, 0.0025 ml.
9.3.2 If desired, the concentration of vinyl chloride may be calculated
as parts per million vinyl chloride,
ppm VC = mg VC/m3 x 0.3915.
10. Effects of storage. Charcoal tubes containing adsorbed vinyl
chloride have been found to be stable for more than seven days though
there is some evidence that they are adversely affected by strong sunlight.
Carbon disulfide solutions lose vinyl chloride to the atmosphere but have
been stored unchanged for more than a month in sealed serum bottles having
58
-------
minimum headspace. Gas standards may be kept in'poly (vinyl fluoride) gas
sample bags for several weeks without undergoing concentration changes.
However, present knowledge of the stability of vinyl chloride samples is
based on studies with pure substances. No information is available on the
storage of samples containing other active substances as are commonly
found in ambient air.
59
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11. References.
Lodge, J. P., Pate, J. B., Ammons, B. E. and Swanson, G. A.
"The Use of Hypodermic Needles as Critical Orifice in Air Sampling."
J. Air Pollution Control Association. 16:4, 197-200, (1966).
"Vinyl Chloride Monitoring Near the B. F. Goodrich Chemical Company in
Louisville, Kentucky." Region IV, U.S. Environmental Protection Agency,
Surveillance and Analysis Division, Athens, Georgia. June 24, 1974.
60
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SERUM CAP-
GLASS WOOL
GLASS WOOL
s^
wys?'.S
Vi'fi??-.
>CSV5?X-
>Vi.C^->>
AIR PUMP
-CRITICAL ORIFICE
CHARCOAL
61
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
1. REPORT NO.
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
COLLABORATIVE TESTING OF EPA METHOD 106 (VINYL CHLORID
THAT WILL PROVIDE FOR A STANDARDIZED STATIONARY SOURCE
EMISSION MEASUREMENT METHOD
6. REPORT DATE
E) August 1978
6. PERFORMING ORGANIZATION CODE
7. AUTHORI?'
8. PERFORMING ORGANIZATION REPORT NO.
George W. Scheil and Michael C.
Midwest Research Institute
Sharp
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Midwest Research Institute
425 Volker Blvd.
Kansas City, Missouri 64110
10. PROGRAM ELEMENT NO.
1HD621
11. CONTRACT/GRANT NO.
68-02-2737
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Monitoring and Support Laboratory
Office of Research and Development
U. S. Environmental Protection Agency
Research Triangle Park. N. C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES
To be published as an Environmental Monitoring Series report
16. ABSTRACT
Method 106 - Determination of Vinyl Chloride from Stationary Sources was
evaluated in a two-part collaborative test. Gaseous samples, prepared in cylinders
and containing interferences in some cases, were analyzed by a group of 10
collaborators. The results showed that Chromosorb 102/SF-96 columns performed
better when acetaldehyde interference was present, but Chromosorb 102 alone was
better when isobutane interference was present. Collaborator biases averaged
0.18 ppm (0.47 mg/mj) low with a standard deviation of 0.72 ppm (1.86 mg/m ).
Both peak height and area measurements yielded similar results and the bias found
was due entirely to low results from using Chromosorb 102 and not from the
Chromosorb 102/SF-96 column.
A three collaborator field test was conducted on the vent of a carbon bed
absorber at a vinyl chloride polymer facility. The group had a standard deviation
of 0.39 ppm (1.01 mg/m3) and 0.24 ppm (0.62 mg/m3) for sampling and analysis,
respectively. Analyst skill is a major factor in the use of Method 106.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Croup
Air pollution
Collaborative testing
Vinyl Chloride
Stationary Sources
13B
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report I
UNCLASSIFIED
21. NO. OF PAGES
61
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
62
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