EPA-600/2-77-100
June 1977
environmental Protection Technology Seru-s
ANALYSIS OF ORGANIC AIR POLLUTANTS BY
GAS CHROMATOGRAPHY AND MASS
SPECTROSCOPY
Environmental Sciences Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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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 ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-77-100
June 1977
ANALYSIS OF ORGANIC AIR POLLUTANTS BY
GAS CHROMATOGRAPHY AND MASS SPECTROSCOPY
by
Edo D. Pellizzari
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-02-2262
Project Officer
Kenneth Krost
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 27711
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for publica-
tion. Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
ii
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ABSTRACT
Analytical methodology based on capillary gas chromatography/mass spec-
trometry/computer was developed for the collection and analysis of urban
organic pollutants. The areas of investigation included: (a) the prepara-
tion and evaluation of glass capillary columns for pollution analysis, (b)
the development of methodology for quantitative analysis of ambient air pol-
lutants, and (c) the identification and quantification of organic pollutants
in ambient air from several geographical locations within the continental
U.S.
iii
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iv
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CONTENTS
Abstract iii
Figures vi
Tables V vii
Acknowledgements x
1. Introduction 1
2. Conclusions 2
3. Recommendations 4
4. Program Objectives 5
5. Preparation and Evaluation of Glass Capillary Columns for
Pollution Analysis 6
6. Development of Methodology for Quantitative Analysis of
Ambient Air Pollutants 15
7. Identification and Quantification of Organic Pollutants in
Ambient Air from Several Geographical Locations 39
References 67
Appendix
A. Volatile Organics Identified and Quantified in Ambient Air. . 68
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FIGURES
Number Page
1 Map of sampling area in East Brooklyn, Baltimore, Maryland. ... 41
2 Standard linear regression curves for chlorinated hydrocarbons. . 45
3 Profile of ambient air pollutants from industrial site in
Baltimore, MD using high resolution gas chromatography/
mass spectrometry/computer. A 100 m glass SCOT coated
with OV-101 stationary phase was used; temperature pro-
grammed from 20-230° @ 4°C/min 46
4 Profile of ambient air pollutants from Patapsco Sewage Treatment
Plant in Baltimore, MD using high resolution gas chromato-
graphy/mass spectrometry/computer. A 100 m glass SCOT
coated with OV-101 stationary phase was used; temperature
programmed from 20-230°C @ 4°C/min 47
5 Resolution of standard mixture of chlorinated hydrocarbons
using a 90 m glass SCOT coated with OV-101 stationary
phase. Temperature programmed from 20-225°C @ 4°C/min ... 51
6 Plant map of DuPont in Belle, WV depicting sampling locations . . 53
7 Plant map of Union Carbide in South Charleston, WV depicting
sampling locations 54
8 Sampling location surrounding Kin-Buc Land-fill, Edison, NJ . . . 57
9 Map depicting sampling locations in Los Angeles, CA 64
10 Map depicting sampling site in Los Angeles, CA 65
11 Map depicting sampling location in Dominquez, CA 66
12 Total ion current profile of ambient air sample taken at
location No. 9 on Union Carbide property. See Tables
13 and 24 for protocol and listing, respectively 81
13 Total ion current profile of ambient air taken at Interstate
60 and WV 25 in Nitro, WV. See Tables 13 and 25 for
protocol and listings, respectively 84
vi
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TABLES
Number Page
1 Glass SCOT Capillaries Tested for Resolving Ambient Air
Pollutants 7
2 Test Mixture for Evaluating Glass Capillary Columns 9
3 Performance of Selected Glass Capillary Columns 10
4 Breakthrough Volumes for Several Atmospheric Pollutants 18
5 Estimation of Breakthrough Volumes for Vinyl Chloride and
Vinyl Bromide on SKC Charcoal (104) 28
6 Estimation of Breakthrough Volumes for Methyl Chloride and
Methyl Bromide on SKC Charcoal (104) 28
7 Relative Molar Response (RMR) Factors for Several Compounds
Based Upon Total Ion Current Monitor 31
8 Relative Molar Response Values for Several Organic Compounds
Based Upon Selected Ions 33
9 Overall Theoretical Sensitivity of High Resolution Gas
Chromatography/Mass Spectrometry/Computer Analysis
for Atmospheric Pollutants 36
10 Sampling Protocol for Baltimore Area 42
11 Operating Parameters for GLC-MS-COMP System 43
12 Sampling Conditions and Concentration of Halogenated
Hydrocarbons in Ambient Air 49
13 Ambient Air Sampling Protocol for Selected Areas in the
Kanawha Valley, WV 52
14 Ambient Air Levels of Several Pollutants in the Kanawha
Valley, WV 55
15 Ambient Air Sampling Protocol for Investigating Chemical
Dump/Landfill in Edison, NJ 58
16 Concentration of Organic Vapors Surrounding Kin-Buc Dump Area . . 60
17 Ambient Air Sampling Protocol for Los Angeles, CA Basin Area. . . 63
vii
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TABLES (continued)
Number Page
18 Volatile Organic Vapors Identified in Ambient Air from
Baltimore, MD 69
19 Volatile Organic Vapors Identified in Ambient Air from
Baltimore, MD 71
20 Volatile Organic Vapors Identified in Ambient Air from
Baltimore, MD 73
21 Volatile Organic Vapors Identified in Ambient Air from
Baltimore, MD 75
22 Volatile Organic Vapors Identified in Ambient Air from
Baltimore, MD 77
23 Volatile Organic Vapors Identified in Ambient Air from
Belle, WV 79
24 Volatile Organic Vapors in Ambient Air from South
Charleston, WV 82
25 Volatile Organic Vapors Identified in Ambient Air from
Nitro, WV 85
26 Volatile Organic Vapors Identified in Ambient Air Near
Kin-Buc Chemical Disposal Site, East Brunswick, NJ 86
27 Volatile Organic Vapors Identified in Ambient Air Near
Kin-Buc Disposal Site 88
28 Volatile Organic Vapors Identified in Ambient Air Near
Kin-Buc Disposal Site 89
29 Volatile Organic Vapors Identified in Ambient Air Near
Kin-Buc Disposal Site 90
30 Volatile Organic Vapors Identified in Ambient Air Near
Kin-Buc Disposal Site 91
31 Volatile Organic Vapors Identified in Ambient Air Near
Kin-Buc Disposal Site 92
32 Volatile Organic Vapors Identified in Ambient Air Near
Kin-Buc Disposal Site 94
33 Volatile Organic Vapors Identified in Ambient Air Near
Kin-Buc Disposal Site 96
viii
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TABLES (continued)
Number Page
34 Volatile Organic Vapors Identified in Ambient Air from
Los Angeles, CA 97
35 Volatile Organic Vapors Identified in Ambient Air from
Los Angeles, CA 99
36 Volatile Organic Vapors Identified in Ambient Air from
Dominquez, CA 101
ix
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ACKNOWLEDGEMENTS
The valuable assistance by Mr. R. N. Williams for laboratory and field
experimentation is gratefully appreciated. The interpretation of mass
spectra and the analysis of samples by high resolution gas-liquid chromato-
graphy/mass spectrometry/computer (glc-ms-comp) in this research was pro-
vided by Mrs. N. Pardow, D. Smith and Dr. J. T. Bursey, a sincere thanks for
their support. The helpful suggestions of Dr. M. E. Wall throughout the
program are appreciated.
The sampling of ambient air at various geographical locations was pos-
sible through the assistance of many individuals at the State Air Pollution
Agencies and regional EPA offices. The assistance provided by Mr. Walter
Cooney and Mr. George Ferrari of the State of Maryland Air Quality for
gaining access to the sites in the Baltimore, MD area is gratefully appre-
ciated. The author wishes to also thank Mr. G. A. DeMarrais (EPA, RTF, NC)
for the meterological data which was obtained during the Baltimore study.
The personnel of the State of West Virginia Air Pollution Control are also
acknowledged for their help in the acquisition of sampling sites during the
nitrosamine study in the Kanawha Valley. The success of the studies in the
New Jersey were primarily due to the helpful assistance of Dr. Paul Brown,
Mr. Joe Spatola, Ms. N. Krypel and Mr. Steve Rivar of the Region II, EPA in
Edison, NJ.
The encouragement and constructive criticisms of Drs. E. Sawicki, P.
Altschuller, A. Ellison and Mr. K. Krost of NERC, RTP, NC are deeply appre-
ciated. The author also acknowledges the valuable assistance provided by
Mr. J. Bauchman, J. 0'Conner and J. Padgett of EPA, RTP, NC for their
valuable help in acquiring permission and access to various plant sites.
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SECTION 1
INTRODUCTION
In order to ascertain whether a health-effect problem exists due to expo-
sure to hazardous organic gases and vapors, pollutants in ambient air should be
characterized and the identified chemicals quantified. In contrast to research
on criteria pollutants and particulates, investigations surrounding the volatile
organics has been meager. It is suspected that the major mass of organic
material in ambient air is composed of organic gases and vapors. This observa-
tion is not surprising in view of the emission rates from fossil fuel consump-
tion for energy and chemical syntheses.
Preliminary research at the Research Triangle Institute has revealed that
hazardous substances in fact do occur in the ambient air. Nitrosamines and
halogenated compounds have been identified, many of which are suspected mutagens
and carcinogens. The major effort in the past has been associated with the
characterization of halogen, oxygen, and nitrogen containing substances; how-
ever, the existence of hazardous sulfur materials are also suspected.
The main thrust of this program has been to adapt and perfect methodo-
(1-4)
l°gy f°r quantitative analysis of atmospheric pollutants by gas chroma-
tography/mass spectrometry/computer (gc-ms-comp). This report presents tech-
niques which were developed and integrated as a total method for obtaining
qualitative and quantitative information on organic vapors in ambient air.
Results obtained during characterization and quantification of pollutants
surrounding industrial activity are also discussed.
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SECTION 2
CONCLUSIONS
The preparation and evaluation of glass capillary columns for the
analysis of ambient air pollutants was performed. The four criteria of
efficiency, resolution, peak symmetry and capacity were used for evaluating
glass SCOT capillaries coated with OV-101, OV-17, Dexil 300 and OV-225. The
four criteria indicated a superior performance could be obtained for glass
capillaries over the stainless steel SCOT'S. Their evaluation also indica-
ted that complete resolution of a mixture by any one specific stationary
phase for the ambient air pollutants can not be achieved on SCOT's and it
was concluded that 2-3 different types of stationary phases will be neces-
sary for analyzing non-polar, semi-polar and polar ambient air pollutants.
Methods for quantitative analysis of ambient air pollutants were also
examined. Determination of breakthrough volumes for various chemical classes
of organic compounds on Tenax GC was studied. The chemical classes examined
were acids, alcohols, aldehydes, amines, aromatics, esters, ethers, haloge-
nated ethers and hydrocarbons, hydrocarbons, inorganic gases, ketones,
nitrogen and sulfur-containing compounds. It was concluded that for highly
volatile compounds, the breakthrough volumes were too small on Tenax GC and
a backup sorbent was necessary. Examination of an SKC carbon indicated that
the breakthrough volume for highly volatile materials could be increased by
1-2 orders of magnitude. The use of chemically bonded phases on silica
indicated that the breakthrough volumes were comparable to Tenax GC and that
these materials were not suitable as backups to Tenax. In the pursuit of a
method for the quantification of, organic vapors in ambient air, it was
concluded several criteria must be addressed. In addition to the break-
through volume, it was necessary to determine the relative molar response
ratios for several organics undergoing glc/ms/comp analysis. The concept of
relative molar response ratio (RMR) was delineated and the RMR's for several
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compounds based on the total ion current and selected single ions (m/e) as
obtained by glc/ms/comp were measured. It was concluded that the relative
molar response ratios vary significantly with the type of and substitution
frequency of heteroatoms in a molecule. The overall sensitivity of high
resolution glc/ms/comp for the analysis of ambient air pollutants was esti-
mated based on the breakthrough volumes and the relative molar response
ratios for several organic molecules. The results indicate that parts-per-
trillion to sub-parts-per-trillion sensitivity can be achieved for their
detection. However, 10-50 times this amount is required for quantification.
The characterization and quantification of ambient air pollutants in
the Baltimore area revealed the presence, in addition to N-nitrosodimethyl-
amine, of halogenated hydrocarbons. These were: l-chloro-2-methylpropene,
3-chloro-3-methylpropene, 2,3-dichlorobutane (meso) and 2,3-dichlorobutane
(one of the racemic pairs). The concentration of l-chloro-2-methylpropene
3
reached a level of 670,000 ng/m at a location on an industrial site in
Baltimore, MD. The results obtained for the characterization and quantifi-
cation of ambient air pollutants from Baltimore, MD, Kanawha Valley, WV, New
Jersey and Los Angeles, CA Basin areas indicated that the technique of high
resolution glc/ms/comp is a viable method of analysis. The method is capable
of characterizing and quantifying oxygen, sulfur and nitrogen containing
compounds as well as halogenated hydrocarbons and aromatics in the ambient
air.
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SECTION 3
RECOMMENDATIONS
Six major phases of research should be expanded and pursued: (1) a
system should be developed for urban air component separation which will
enable the identification and quantification of component mixtures of
ambient air pollutants collected at various geographical areas; (2) qualita-
tive identifications and quantitative estimation should be made of pollutant
compositions from various environments such as the chemical industry, the
products of photochemical reactions, and vehicular exhaust; (3) the sensi-
tivity, accuracy, and reproducibility of the overall analysis systems for
several classes of pollutant candidates should be further evaluated; (4) a
system for quantitative analysis of atmospheric organic vapors should be
developed concurrently with the qualitative identification of those com-
ponents occurring in automobile exhaust samples using the techniques of
gc/ms/comp; (5) organic chemical pollution profiles for the urban environ-
ments examined should be delineated into those pollutants unique to par-
ticular environment as contrasted to those pollutants commonly found as a
general pollutant throughout all urban environments in order that the
biological effects can be assessed, and (6) the hazardous organic vapor
pollutants in atmospheres which constitutes an immediate crisis situation
such as accidents occurring at industrial sites should be examined utilizing
these techniques in order to access whether a health problem exists.
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SECTION 4
PROGRAM OBJECTIVES
The main emphasis of this research program was to collect urban air
organic pollutants for complete characterization and quantification at the
parts-per-trillion level. The specific objectives were: (1) to formulate a
sample collection system of sufficient efficiency to permit as a minimum the
2
analysis of pollutants present at the low ng/m concentrations; (2) to
develop highly efficient glass capillary columns for the resolution of urban
air pollutants with emphasis on the elution of polar and semi-polar com-
pounds; (3) to demonstrate the overall sensitivity of the system for several
classes of potential pollutant candidates and to acquire quantitative
information on these substances and (4) to analyze ambient air pollutants by
the use of gas chromatography in tandem with mass spectrometry and provide
quantitative analysis for atmospheric organic vapors, concurrently with the
qualitative identification. Studies of automobile exhaust composition which
contributes to the atmospheric organic vapors were to be performed by gc/ms/
comp using the techniques previously developed for ambient air pollutants.
In essence, vehicle emissions from prototype vehicles were examined.
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SECTION 5
PREPARATION AND EVALUATION OF GIATS CAPILLARY COLUMNS
FOR POLLUTION ANALYSIS
The complexity of the pollutants in ambient air requires the use of
high resolution in order to effectively separate the constituents for identi-
(1 2)
fication and quantification of compounds of interest. ' Because these
compounds are highly volatile, their analyses precludes the use of chemical
purification methods since they would escape during processing. Thus, a
requirement for very high resolution gas chromatography exists in order to
achieve adequate resolution of these complex mixtures. The obvious approach
to this problem is to utilize glass capillary columns coated with appro-
priate phases which will achieve adequate resolution for various chemical
classes of interest. Although there are over 100 stationar^ phases avail-
able for gas-liquid chromatography, only a few of these effectively provide
significant differences in resolution. In general it can be stated that
stationary phases representative of non-polar, semi-polar and polar types
will effectively produce optimum differences in the resolution patterns.
This section discusses the preparation and evaluation of glass capil-
lary columns for the analysis of ambient air pollutants. It examines various
stationary phases with regard to definitive evaluation criteria and the
selection of phases which may be used for resolving, characterizing and
quantifying complex mixtures of ambient air pollutants.
EXPERIMENTAL
Glass support coated open tubular (SCOT) capillaries were prepared
(3)
according to a previously described procedure. SCOT capillaries con-
taining the stationary phases OV-101, OV-17, Dexil 300, Poly 1-110 and 0V-
225 were examined (Table 1).
Four criteria were used for evaluating SCOTS. These were: (1) effi-
ciency, which was determined in terms of the height equivalent to a theo-
retical plate
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Table 1. GLASS SCOT CAPILLARIES TESTED FOR
RESOLVING AMBIENT AIR POLLUTANTS
Stationary Phase
Carbowax 20M
OV-17
OV-225
Poly 1-110
Dexil 300 GC1
a
Surfactant
BTPPC1/0.1%
BTPPC1/0.1%
BTPPC1/0.1%
BTPPC1/0.1%
BTPPC1/0.1%
Percent Phase
Used
0.96
1.0
1.0
1.0
2.5
length
m
38
60
104
90
106
i.d.
(mm)
0.35
0.27
0.27
0.27
0.31
Benzyltriphenyl phosphonium chloride
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HETP = ^—
5.54 (^
Wl/2
L = length of column
RT = retention time (min)
W. ,» = width of peak at half height (mil. }
(2) resolution, which was determined for three isomeric pairs, 4-methyl-
pentene-1 vs 2-methylpentene-l; l-chloro-2-methylpropene vs 3-chloro-2-
methylpropene and p_-xylene vs_ m-xylene
2 A T
Wl + W2
AT = difference in retention between peaks 1 and 2
W = peak width at its base
(3) symmetry, which was determined for each peak as a percent ratio of the
area of the front portion of the peak to the back portion. The peak was
divided for this purpose by a line drawn perpendicular from the peak maxima
to the baseline. Areas were measured with a planimeter.
% S = |- x 100
D
f = area of front peak-half
b = area of back peak-half
and (4) capacity, which was evaluated by applying the above criteria to
objections of a test mixture at three different concentrations which spanned
a range of two orders of magnitude.
RESULTS AND DISCUSSION
The test mixture used for evaluating SCOT capillaries is summarized in
Table 2. The components selected provided a representative range of polari-
ties. They are compounds which have been previously identified in ambient
air. Three isomeric pairs are included for comparison of the resolution
obtained on the different capillary columns. These results are summarized
in Table 3. None of the columns prepared and tested proved capable of
completely resolving all isomers. Resolution of the olefins and chloro-
olefin isomeric pairs varied considerable with the polarity of the
8
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Table 2. TEST MIXTURE FOR EVALUATING GLASS
CAPILLARY COLUMNS
Relative Quantities
Compound (yg/ml)
j
4-Methylpentene-l 1.5 (0.49)
2-Methylpentene-l 1.5 (0.50)
l-Chloro-2-methylpropene 2.0 (0.92)
3-Chloro-2-methylpropene 2.0 (0.91)
Ethyl acetate 3.0 (1.35)
2-Butanone 3.0 (1.20)
Toluene 1.0 (0.43)
N,N-Dimethylformamide 3.0 (1.42)
Tetrachloroethylene 2.0 (1.60)
£-Xylene 1.0 (0.43)
m-Xylene 1.0 (0.43)
Acetophenone 3.0 (1.54)
Nitrobenzene 3.0 (1.80)
_q.-Undecane 1.0 (0.37)
Relative volumes used, concentration in parenthesis.
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Table 3. PERFORMANCE OF SELECTED GLASS CAPILLARY COLUMNS
Column
Criteria
/^•/•V/ •>/•*>/ "j
200 ft SS SCOT
OV-17 ,
100 ng
HETP
Tr 0.56 0.61 0.63 0.65 0.75
PS 42 42 47 47 a
R 3.22 0.54
4
liOOO ng
Tr 0.51 0.57 0.62 0.64 0.69
PS 37 37 38 38 a
R 4.40 0.50
5000 ng
Tr 0.50 0.56 0.61 0.63 a
PS 40 40 11 11
R 4.00 0.40
f'>'/
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Table 3 (cont'd)
105 m GSCOT
OV-101
95 m CSCOT
(silanized)
OV-101
100 ng
PS
R
1000 ng
PS
R
10,000 ng
Tr
PS
R
100 ng
PS
R
0.52 0.57
67 67
4.10
0.52 0.59
57 57
4.20
0.52 0.58
54 54
4.40
0.64 0.66 a
52 - 52
0.52
0.64 0.66
57 57
0.45
0.64 0.65
33 33
0.40
0.61
a
0.61
a
0.53 0.60 0.65 0.66 a
85 100 100 77
2.87 0.40
1.0
53
1.0
53
1.0
50
1.0
51
1.11
83
1.11
87
1.16
55b
1.10
50b
1.11
83
1.11
87
1.16
55b
1.10
50b
1.24
52
1.23
8lb
1.25
52
1.25 1.25
64b 64b
0
1.25 1.25
62b 62b
0
1.'23
81b
1.70
53
1.68
83
1.67
23
1.73
1.71
51
1.71
85
1.72
46
1.73
54b
1.74
100
1.74
101
1.76
179
1.73
54C
1000 ng
Tr
PS
R
0.53 0.59 0.65 0.66
65 86 98 98
2.77 0.39
a 1.0
58
(continued)
1.10
1.10
61b
1.24
72b
1.24
72b
1.71
166b
166b
1.73
42
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Table 3 (cont'd)
10,000 ng
0.53 0.60
68 78
2.88
0.64
60
0.65
0.25
0.62
a
0.62
a
1.0 1.11
61 66C
1.11
66C
1.24
62C
1.24
62
1.67
44
1.71
62
1.74
94
NJ
60 m GSCOT
OV-17
100 ng
HETP
Tr
PS
R
0.41 0.45
54 56
1.10
0.56 0.61
64 64
0.47
1.61
1.0 1.08
53
56°
1.08
56b
1.32
71b
1.32
7lb
2.29
84
2.29
b
2.J8
58
1000 ng
Tr
PS
R
10,000 ng
PS
R
106 m GSCOT 1000 ng
(silanlzed) Tr
Dexisil PS
9 D
0.40 0.46 0.57 0.61
46 64 46 47
0.60 0.52
0.40 0.45 0.57 0.62
26 28 53 66
0.59 0.51
0.49 0.55
58 75
2.00
0.64 0.65
b b
0.23
0.67
a
0.67
a
1.0 1.09 1.09 1.32 1.32 2.28 2.28 2.18
48 59b 59b 64b 64b 56b 56b 68
0
1.0 1.09 1.09 1.32 1.32 2.28 2.28 2.17
56 75b 75b 75b 75b 85b 85b 66
0
1.0 1.09 1.09 1.26 1.81 1.81 1.89 1.68
71 71b 71b 64b 64b 35b 74 84
0
(continued)
-------
Table 3 (cont'd)
Column
Criteria
10,000 ng
Tr
* L
PS
R
0.46
80
1.96
0.51
83
0.61
a
0.15
0.62
a
0.59
a
0.59
a
1.0
66
•1.10 1.10
83b 83b
1.30
68b
1.30
68b
0
1.95
84
2.06
89
1.82
i 107
104 m GSCOT
OV-225
100 ng
HETP
Tr
PS
R
1000 ng
Tr
PS
R
0.32
0.27
60
0.32
43b
0.29
89
1.23
0.37 0.41
36 52
2.19
0.40 0.45
54 48
0.94
0.43
a
0.48
51
0.45
a
0.56
59
d
1.0
51
1.0
54
0.77
70
0.73
b
0.80
56
0.76
53
1.45
73b
1.45
1.45 1.45
64b 64b
0
1.92
54
1.98
82
2,06
84
2.12
53
1.68
47
1.69
83
10,000 ng
Tr
PS
R
0.29 0.31
53 70
1.84
0.43 0.50
54 61
3.73
0.53
62
0.60 1.0
53 71
0.77 0.80 1.43 1.43
61b 6lb
0
57
32
1.65 2.04 1.90
67 55 73
Components were unresolved, PS not determined.
bPeak symmetry was determined on unresolved components.
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stationary phase. None of the columns evaluated showed extremely high effi-
ciency as measured in terms of height equivalent to a theoretical plate,
however their resolution was good. Peak symmetry was near ideal on glass
capillaries whereas, back tailing was clearly evident during chromatography on
stainless steel capillaries.
Using the test criteria HETP, separation efficiencies, peak symmetry,
and the relationship between the elution order ror a standard mixture, it
was possible t>. assess in a quantitative fashion the utility of these glass
capillaries for resolving ambient air pollutants. Ideally, the selection of
2-3 glass capillaries would be preferred for the resolution of ambient air
pollutants so that the identification of constituents and their quanti-
fication can be made.
14
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SECTION 6
DEVELOPMENT OF METHODOLOGY FOR QUANTITATIVE ANALYSIS OF
AMBIENT AIR POLLUTANTS
This chapter addresses a conceptual approach for obtaining quantitative
information on the atmospheric pollutants which are identified in ambient
air samples collected on Tenax GC. It also addresses the limitations of the
sorbent Tenax GC and examines alternate sources of backup materials for
collecting pollutants which are not efficiently trapped on Tenax GC.
The requirements for obtaining quantitative data with regard to the
performance of the Tenax GC sorbent and the methodology for the calibration
of instrumentation are described. This chapter presents studies on the
various parameters which are deemed necessary for obtaining quantitative
information concerning atmospheric pollutants. The subject of breakthrough
volumes of various chemical classes on Tenax GC, the examination of an
alternate backup sorbent and the concept of relative molar response ratios
are all addressed in this chapter.
THE DETERMINATION OF BREAKTHROUGH VOLUMES FOR VARIOUS CHEMICAL CLASSES OF
ORGANIC COMPOUNDS ON TENAX GC
The purpose of this study was to determine the breakthrough volumes for
several organic vapors which have either been identified or are anticipated
to be present in ambient air. Furthermore, the objectives were to examine
several compounds within various chemical classes in order to determine
whether an empirical relationship exists between a homologous series and to
what extent it may be possible to predict the breakthrough volumes for
compounds of similar structural types. With an empirical approach such as
this, the ability to predict the breakthrough will greatly facilitate the
ability to obtain quantitative information about the levels of atmospheric
pollutants.
15
-------
Experimental •
Breakthrough volumes were estimated for a number of organic vapors
which had been previously identified or anticipated to be present in ambient
(4)
air. The method employed consisted of determining the elution volume for
an organic va^or on a gas chromatographic column packed with a sorbent Tenax
GC. The column with the dimension of 3 mm x 1.76 m in length was used.
After injecting each vapor, the elution volume was determined as the product
of flow rate aud elution time. A series of injections were made at decrea-
sing temperatures and a plot of the log 1/v V£ temperature was constructed.
Using a linear regression analysis, the breakthrough volumes (50% loss) for
several ambient temperatures were determined by extrapolation. At the end
of the experiment, the Tenax GC sorbent in the chromatographic column was
weighed and the breakthrough volume was expressed in iL/2.2 g which is the
standard quantity which has been employed in field sampling.
The technique for determining breakthrough volumes has been previously
described and compared with other techniques which has established this
method as a viable rapid approach for the determination of breakthrough
T (1,2,4)
volumes. '
Results and Discussion
The breakthrough volumes of acids, alcohols, aldehydes, amines, aroma-
tics, esters, halogenated hydrocarbons, hydrocarbons, inorganic gases,
ketones, nitrosoamines, nitrogenous hydrocarbons, oxygenated hydrocarbons
and sulfur compounds are given in Table 4. The breakthrough volumes for the
more volatile organics such as the aldehydes (e.g. acetaldehyde) and alco-
hols are relatively low. Generally, the sorbent Tenax GC is not regarded to
be an adequate material for the collection of these substances with any
degree of reliability or sensitivity. The low molecular amines such as
dimethylamine also have low breakthrough volumes.
Examination of the breakthrough volumes for aromatic compounds indi
cates that the incorporation of an aromatic moiety into a molecule greatly
increases the affinity of Tenax GC for the organic vapor. For example, the
breakthrough volume for diphenyl vs benzene is increased by almost three
orders of magnitude.
Another important relationship which can be extracted from the infor-
mation presented in this table is the relationship between the breakthrough
16
-------
volumes at two different temperatures. The slope of the linear regressions
are parallel for the compounds within a given chemical class. Therefore, if
the breakthrough volume at one temperature is known, then the breakthrough at
the remaining temperatures for that unknown can be calculated since the
relationship is predictable.
The comparison of isobutylamine and t-butylamine breakthrough volumes
reveal that although the boiling of t-butylamine is higher, it had a signifi-
cantly lower retention volume on Tenax GC. In contrast, di-n-butylamine had
q
breakthrough volumes in the m range. Similar differences were observed
between pyridine and aniline. It was concluded that if the compound exhi-
bited a high degree of basicity, the retention volume would be correspon-
dingly high. However in thoses cases where steric hindrance plays an impor-
tant role in reducing the basicity of the compound (e.g. t-butylamine), then
the breakthrough volume will be decreased correspondingly.
Little differences are observed in the breakthrough volume between
methyl ethyl ketone and methyl vinyl ketone. Comparison of acetone and
acetophenone indicates again that the incorporation of an aromatic moiety
will significantly increase the breakthrough volume. This trend is also
observed when comparing acetaldehyde and benzaldehyde.
The breakthrough volumes for two nitrosamines, N-nitrosodimethylamine
and N-nitrosodiethylamine are also shown in Table 4. The incorporation of
two methylene units into the N-nitrosodimethylamine (to yield N-nitroso-
diethylamine) produces a marked increase in the breakthrough volume. In
fact, it increases by a factor of 9.
Surprisingly, the inorganic gases tested exhibited rather low or no
retention volume at all (NO, NO., C1-, Br., I., and SO-) on Tenax GC. The
low retention index for these inorganic gases is an important factor when
considering the formation of artifacts during the concentration of organic
pollutants from ambient air. For example, when high concentrations of
dimethylamine occur in ambient air, the possibility of artifact formation
during sampling with a cartridge sorbent such as Tenax GC via a reaction
between NO (NO + N0_) and dimethylamine is highly unlikely since NO does
X ^ X
not accumulate. Of particular importance is also the very low breakthrough
volume for water on Tenax GC; water accumulating on the substrate may
17
-------
Table 4. BREAKTHROUGH VOLUMES FOR SEVERAL ATMOSPHERIC POLLUTANTS'
00
Temperature °F (°C)
Chemical
Class
acids
alcohols
aldehydes
amines
aroma tics
i
Compound
n-butyric acid
methanol
n?-propanol
ethylene glycol
allyl alcohol
dibromopropanol
acetaldehyde
benzaldehyde
d ime thy lamine
isobuty lamine
Jt-buty lamine
di- (n-butyl)amine
pyridine
aniline
benzene
toluene
ethylbenzene
cumene
phenol
o-br omopheno 1
m-bromophenol
p_-bromophenol
biphenyl
b.p.
162
64.7
97.4
196-8
96-8
95-7
20
179
7.4
69
89
159
115
184
80.1
110.6
136.2
152.4
96-8
195
236
235-6
256
50 (10)
615
1
27
137
32
120
3
7,586
9
71
6
9,506
378
8,128
108
494
1,393
3,076
2,071
2,872
6,269
7,966
62,405
60 (15.5)
423
1
20
96
23
84
2
5,152
6
47
5
7,096
267
5,559
77
348
984
2,163
1,490
2.124
4,701
5,946
44,383
70 (21.1)
290
0.8
14
67
16
58
2
3,507
4
34
4
4,775
189
3,793
54
245
693
1,525
1,072
1,567
3,534
4,428
31,639
80 (26.7)
199
0.6
10
47
11
41
1
2,382
3
23
3
3,105
134
2,588
38
173
487
1,067
769
1,159
2,650
3,298
22,502
90 (32.2)
136
0.4
7
33
8
28
0.9
1,622
2
16
2
2,168
95
1,766
27
122
344
750
554
855
1,987
2,456
16,046
100 (37.8)
93
0.3
5
23
6
20
0.7
1,101
1
11
1
1,462
67
1,205
19
86
243
527
398
633
1,490
1,829
11,408
(continued)
-------
Table 4 (cont'd)
Temperature °F (°C)
Chemical
Class
esters
ethers
halogenated
ethers
halogenated
hydrocarbon
Compound
ethyl acetate
•methyl aery late
methyl methacrylate
diethyl ether
propylene oxide
2-chloroethyl ethyl ether
Bis- (chloromethyl) ether
methyl chloride
methyl bromide
vinyl chloride
vinyl bromide
methylene chloride
chloroform
carbon tetrachloride
1 , 2-dichloroethane
1,1, 1- tr ichloroethane
tetrachloroethylene
trichloroethylene
l-chloro-2-methylpropene
3-chloro-2-methylpropene
1 , 2-dichloropropane
1 , 3-dichloropropane
epichlorohydron (1-chloro-
2 , 3-epoxypropane)
b.p.
(°C)
77
80
100
34.6
35
108
—
-24
3.5
13
16
41
61
77
83
75
121
87
68
72
95
121
116
50 (10)
162
164
736
29
13
468
995
8
3
2
8
11
42
34
53
23
361
90
26
29
229
348
200
60 (15.5)
108
111
484
21
9
336
674
6
2
1.5
6
9
31
27
41
18
267
67
20
22
162
253
144
70 (21.1)
72
75
318
15
7
241
456
5
2
1.25
4
7
24
21
31
15
196
50
16
17
115
184
104
80 (26.7)
48
50
209
11
5
234
309
4
1
1.0
3
5
18
16
23
12
144
38
12
13
81
134
74
90 (32.2)
32
34
137
8
4
124
209
3
1
0.8
2
4
13
13
18
9
106
28
9
10
58
97
54
100 (37.8)
22
23
90
5
3
89
142
2.5
0.9
0.6
1.8
3
10
10
14
7
78
21
7
8
41
70
39
(continued)
-------
Table 4 (cont'd)
N>
o
Temperature °F (°C)
Chemical
Class
hydrocarbons
M
Compound
epibromohydrin (1-
bromo-2 , 3-epoxy propane)
trimethylene chloro-
bromide
3-chloro-l-butene
ally! chloride
4-chloro-l-bu tene
l-ehloro-2-butene
chlorobenzene
£-dichlorobenzene
m-dichlorobenzene
benzyl chloride
bromoform
ethylene dibromide
bromobenzene
n-hexane
n-heptane
1-hexene
1-heptene
2 , 2-dimethylbutane
2 , 4-dimethylpentane
4-methyl-l-pentene
cyclohexane
b.p.
(°C)
134-6
142-5
64
45
75
84
132
181
173
179
149
131
155
68.7
98.4
63.5
93.6
49.7
80.5
53.8
80.7
50 (10) 60
678
1,130
19
21
47
146
899
1,531 1,
2,393 1,
2,792 2,
507
348
2,144 1,
32
143
28
286
0.5
62
14
49
(continued)
(15.5)
479
927
15
16
36
106
653
153
758
061
386
255
521
23
104
20
196
0.4
44
10
36
70 (21.1)
337
656
12
12
27
77
473
867
1,291
1,520
294
188
1,079
17
75
15
135
0.3
31
8
26
80 (26.7)
237
465
9
9
20
56
344
656
948
1,125
224
138
764
12
55
11
93
0.2
22
6
19
90 (32.?)
168
329
7
6
15
40
249
494
697
330
171
101
542
9
39
8
64
0.2
15
4
14
100 (37.8)
118
233
6
5
12
29
181
372
510
612
130
74
384
6
29 '
6
44
0.1
11
3
10
-------
Table 4 (cont'd)
fO
Temperature °F (°C)
Chemical
Class
inorganic
ke tones
nitrosamines
nitrogenous
hydrocarbons
Oxygenated
hydrocarbons
Compound
nitric oxide
nitrogen dioxide
' chlorine
bromine
iodine
sulfur dioxide
water
acetone
methyl ethyl ketone
methyl vinyl ketone
acetophenone
-N-ni tr o s od ime thy lamine
N-nitrosodiethylamine
nitrome thane
aniline
acrolein
glycidaldehyde
propylene oxide
butadiene diepoxide
cyclohexene oxide
styrene oxide
phenol
acetophenone
6-propiolactone
b.p.
(°C)
^
-
-
58.7
184.3
-
100
56
80-2
81
202
151
177
101
184
53
-
34
-
132
194
183
202
57
50
0
0
5
2
3
1
2
5
2
3
(10)
0
0
0
.035
.037
0.06
0.06
25
82
84
,346
385
,529
45
,864
19
364
35
,426
,339
,370
,071
,191
721
60
0
0
3
1
2
1
1
3
1
2
(15.5)
0
0
0
.025
.025
0.05
0.05
17
57
58
,855
280
,836
34
,831
14
247
24
,009
,644
,926
,490
,382
514
70 (21.1)
0
0
0
0.020
0.022
0.03
0.04
12
39
40
2,767
204
1,330
25
2,075
10
168
17
714
1,153
2,870
1,072
1,778
366
80 (26,7)
0
0
0
0.015
0.021
0.02
0.03
8
27
28
2,000
163
966
19
1,520
8
114
11
506
811
2,094
769
1,327
261
90 (32.2)
0
0
0
0.010
0.015
0.02
0.01
6
19
19
1,439
148
700
14
1,114
6
77
8
358
570
1,531
554
991
186
100 (37.8)
0
0
0
0.010
0.010
0.01
0
4
13
14
1,037
107
508
11
817
4
52
5
253
400
1,119
398
740
132
(continued)
-------
Table 4 (cont'd)
N>
NJ
Temperature °F (°C)
Chemical
Class
sulfur
compounds
Compound
dlethyl sulfate
ethyl methane sulfate
J^-butyl mercaptan
n-propy Imer cap tan
sec-butylmercaptan
diethyl sulfide
£-amy Imer cap tan
sec-isoamylmercaptan
n-amy Imer cap tan
ii-hep ty Imercap tan
di-n-butylsulfide
thiophene
2-methylthiophene
2-e thy 1 thiophene
2-ac e ty 1 thiophene
2-mercaptoethanol
diethyl sulfite
dimethyl sulfoxide
b.p.
(°C)
208
86
62-5
68-8
84-5
92
99-105
117-8
126
173-6
182
84
113
132-4
214
157
157-9
189
59 (10)
40
5,093
3.5
104
217
324
180
399
262
10,098
7,537
199
526
910
5,665
610
2,319
524
60 (15.5)
29
3,681
3.0
71
151
227
129
286
182
6,954
5,373
138
371
659
4,132
418
1,641
391
70 (21.1)
21
2,564
2.5
49
106
159
92
204
127
4,789
3,830
96
262
478
3,021
286
1,162
292
80 (26.7)
15
1,914
2.0
34
74
111
65
146
88
3,305
2,730
67
184
346
2,204
196
823
218
90 (32.2)
11
1,384
1.9
23
52
77
47
104
61
2,276
1,946
46
130
251
1,608
134
582
163
100 (37.8)
8
998
1.5
16
36
54
33
74
43
1,567
1,387
32
91
182
1,175
92
411
122
Breakthrough volumes are based on 2.2 g of Tenax GC.
-------
otherwise provide a medium for reactions such as hydrolysis of reactive
species and/or formation of nitrous acid.
The breakthrough volumes for a number of sulfur containing compounds
are also given in Table 4. A series of mercaptans, thiophenes and other sulfur
containing compounds was studied. A direct relationship was observed between
an increase in the boiling point of each compound and its breakthrough volume.
EXAMINATION OF SKC CARBON AS A BACKUP SORBENT FOR TENAX GC
The principal difficulty encountered in field use of a backup sorbent
which has an affinity higher than Tenax GC has been the collection of exces-
sive quantities of water. Unfortunately those commerical sorbents which have
a higher affinity than Tenax GC for volatile organics also have a higher
affinity for water. Most of the water could be eliminated by desorbing the
backup cartridge with a low volume of carrier gas and trapping the vapors on
Tenax. This would be similar to the back flushing techniques that are used
in gas chromatography. In order for this to be an effective method of reduc-
ing the amount of water and to be a quantitative procedure for organic pollut-
ants, it is necessary that the breakthrough volume for water be exceeded
during purging without approaching the breakthrough volumes of the components
of interest.
There were four requirements which were deemed necessary for a satis-
factory material to be used as a backup sorbent: (1) the material must have
a higher affinity for the polar organic vapors than for Tenax GC, (2) even
though it may have a greater affinity for water, water must have a finite
elution volume at ambient temperature, i-e. it must not be strongly retained
to the sorbent so that adsorption properties for other compounds are not
altered; (3) the sorbent material must allow the recovery of vapors by
thermal desorption without introducing decomposition of the trapped cons-
tituents, and (4) during the thermal desorption cycle, the sorbent must not
be decomposed with the formation of volatile background components or be
altered such that its performance characteristics are also changed.
This section describes the examination of three silicones chemically
bonded to Spherosil (100 microns) and SKC Lot No. 104 carbon. The chemically
bonded stationary phases studied were an S1A075, S1B075, and S1C075 on 100-
200 M silica (Supelco, Inc., Beliefonte, PA).
23
-------
Experimental
An apparatus for transferring adsorbed vapors from backup cartridges to
Tenax cartridges was constructed which consisted of a cartridge holder mounted
(2)
on the exhaust line of the thermal desorption unit. The inlet line end of
the Tenax cartridge was attached to a Beckman (830511) 16-18 mm Teflon reduc-
ing union which was bored out to 8 mm i.d. and fitted with a Teflon insert
(i.d. 2 mm) to minimize dead volume. The effluent carrier gas passed from
the desorptior chamber into the Tenax GC cartridge and then through a soap
bubble flow meter followed by a carbon safety trap.
Results and Discussion
Preliminary experiments were conducted with Chromosorb 104 to test the
transfer procedure from one cartridge to another. The Chromosorb 104 cart-
ridges were desorbed at 280°C for 20 min and then a Tenax cartridge was
desorbed further 20 min at 50 ml/min at helium purge. The Tenax GC cartridge
was then removed from the line and desorbed at 270°C and analyzed by gc@fid.
The background eluting from Chromosorb 104 after a 20 min desorption period
at 200° was excessively high so desorption was continued for 15 hrs to
further condition the sorbent. Then a Tenax GC cartridge was loaded for 20
min with Chromsorb 104 cartridge at 200°C. This was repeated at 180°- Both
Tenax cartridges had approximately 10 times their normal background. Chromo-
sorb 104 could be used as a backup material for Tenax, but due to the exces-
sive background it would be impractical for use in quantitative analysis.
Accordingly, it was given no further consideration.
The first criteria evaluated for the chemically bonded silicones to
Spherosil was the determination of background occurring from the sorbent
during thermal desorption. Sorbents were loaded into cartridges (1.5 x 6 cm
bed) and desorbed in a 50 ml/min helium stream for 30 min. The chemically
bonded Spherosil were desorbed at 150° and the carbon at 270°. At the end of
the desorption period, the background was determined by either cryogenic
trapping of the effluent stream (-196°C) or 10 min or trapping vapors from
the effluent stream with a 1.5 x 6 cm bed of Tenax for 10 min. Desorption
was continued for a period of upto 110 min and the effluent was tested at 20,
40 and 90 min. The background for the chemically bonded phases on the
Spherosil was comparable to that of Tenax GC. On the otherhand, the ^
24
-------
background from SKC carbon which was much smaller, an initial desorption
time of approximately 30 min was necessary to minimize background.
Preliminary test of collection efficiency for silicone chemically bonded
to Spherosil was also run by sampling lab air with a Tenax GC cartridge in
tandem with a Spherosil cartridge. The Spherosil cartridge was then ther-
mally desorbed and analyzed. The results were compared with those from a
Tenax backup cartridge which had been loaded with laboratory air simulta-
neously under the same sampling conditions. The quantities of vapors col-
lected by the Spherosil backup cartridges were substantially smaller than
those collected on the Tenax backup cartridge. From this it concluded that
the affinity of organic vapors for the chemically bonded Spherosil tested was
substantially smaller than their affinity for Tenax GC. Thus, they would not
be suitable backup sorbents for Tenax and no further consideration was given
to them.
Experiments were conducted to examine the recovery of vinyl chloride
from SKC carbon and the possibility of transferring desorbed volatile organic
vapors from carbon to Tenax GC cartridges. One of the problems associated
with the use of carbon cartridges for sampling has already been mentioned
earlier, i.e. the accumulation of significant amounts of water. In order to
transfer the volatile organic vapors from the carbon cartridge to the analy-
tical system, the water which is desorbed must be eliminated. It has been
our experience that the direct interfacing of the SKC carbon cartridge to the
analytical system produces icing and plugging of the capillary trap on the
inlet manifold which is used to concentrate and transfer the organic vapors
to the SCOT capillary column.
Vinyl chloride standards were prepared from a standard source of concen-
tration of 10 ppm. A standard amount (250 ng) was loaded onto a cartridge
and experiments in which the desorption of the vinyl chloride from SKC
carbon was directly introduced into the analytical system. The desorption
unit was operated at 290°C with the helium purge range of 30 ml/min. The
desorbed vapors were trapped in a 0.5 ml i.d. x 0.5 m length, trans-axial Ni
capillary trap cooled with liquid nitrogen. Vinyl chloride vapors desorbed
and analyzed in this manner were compared to the response of an equivalent
amount loaded onto Tenax GC cartridges (1.5 x 6 cm).
25
-------
'
Analysis were performed on a Perkin-Elmer 900 gas-liquid chromatograph
equipped with a 400 ft OV-101 stainless steel SCOT capillary programmed from
30-240°C at 4°/min with a 4 min delay. The carrier gas flow was 4 ml/min.
The response obtained for the peak corresponding to vinyl chloride desorbed
from Tenax was taken as a reference response (250 ng).
A 1.5 cm i.d. x 4 cm bed of SKC carbon was loaded on one end with vinyl
chloride and placed into the thermal desorption unit so that it was "down".
The desorption of the cartridge and analysis indicated a response that was 95%
of the standard response. When the vinyl chloride vapor was loaded in the
middle of the cartridge with a hypodermic syringe, the response was 40% of the
i
standard. In the third case, the vinyl chloride was loaded at one end of the
carbon cartridge and introduced in the unit so that this end was "up". In
this case the response was 40% of the standard. The desorption time in each
case was 10 min.
The desorption of vinyl chloride from carbon onto a 6 cm Tenax GC car-
tridge was evaluated. Vinyl chloride was loaded onto carbon and the carbon
cartridge desorbed at 290° for 6 min onto Tenax at a 30 ml/min He purge rate.
The response of the detector obtained for the desorption of the Tenax GC
cartridge was 40% of the vinyl chloride standard.
When a carbon cartridge which has been utilized in field sampling was
desorbed for 10 min onto a Tenax cartridge, a considerable amount of water
condensed on a glass wool plug which held the Tenax GC bed. During the
desorption of the Tenax GC cartridge, the Ni capillary trap froze and the
purged gas flow dropped to zero. Thus it was decided that a desiccant was
needed in order to remove the water vapor.
A Tenax GC cartridge was then loaded with vinyl chloride and desorbed for
5 min onto another Tenax cartridge and when the backup Tenax cartridge was
analyzed, the vinyl chloride response was 95% of the standard. This experi-
ment was repeated using a 1.5 cm x 1 cm length of calcium sulfate bed placed
in-line prior to the backup Tenax GC cartridge. The backup cartridge was then
analyzed and the response was 40% of the standard. The Tenax GC cartridge was
then loaded with vinyl chloride and desorbed for 15 min through the calcium
sulphate plug and onto a backup Tenax GC cartridge. The response obtained in
this case was 90% of the standard. It was concluded that an additional purged
26
-------
volume through the calcium sulphate was necessary in order to exceed the
breakthrough volume for vinyl chloride.
A carbon cartridge which had been used in field sampling was desorbed
and purged for 15 min through the calcium sulphate drying tube and onto a
Tenax cartridge. Calcium sulphate effectively reduced the amount of water
vapor so that the capillary trap on the thermal desorption unit did not
freeze when the Tenax cartridge was desorbed.
Using a smaller cartridge packed with SKC Lot No. 104 carbon (0.5 cm x
4 cm in length), the collection and recovery by thermal desorption utilizing
the calcium sulphate drying tube and the desorption of the backup Tenax
cartridge yielded a 95% or better recovery of vinyl chloride.
Since the above experiments indicated that it was feasible to desorb
vinyl chloride from SKC carbon Lot 104 and transfer it to Tenax cartridges
for further analysis, we then investigated the breakthrough volumes of vinyl
chloride, vinyl bromide, methyl chloride and methyl bromide on this SKC
charcoal. The method for estimating the breakthrough volumes has been pre-
viously described. ' ' Tables 5 and 6 present the breakthrough volumes
for vinyl chloride, vinyl bromide, methyl chloride and methyl bromide on this
SKC charcoal (104). For vinyl chloride the breakthrough volume increased
from 0.9 £/g for Tenax to 104 £/g of SKC charcoal (50°F in both cases). Thus
the increase in the retention volume for the vinyl chloride was approximately
2 orders of magnitude greater than that of Tenax GC. Similar results were
observed with vinyl bromide whereby breakthrough volume on Tenax GC increased
from 3.6 8,/g to 388 £/g of SKC charcoal (also 50°F). Again, the increase in
the breakthrough volume was approximately 2 orders of magnitude. Comparison
of the breakthrough volumes between Tenax and SKC charcoal for methyl chlo-
ride and methyl bromide indicated a significant increase in the breakthrough
volume when using charcoal. These results indicate that the SKC carbon
provides an adequate sorbent material for the collection of vinyl chloride,
vinyl bromide, methyl chloride and methyl bromide with significantly higher
breakthrough volumes which will allow more sensitive analysis and possibly
quantification of these compounds in ambient air.
Based on the results of the breakthrough volumes of compounds on Tenax
GC and SKC charcoal Lot No. 104, it was concluded that the SKC charcoal could
serve as a backup to Tenax GC for those sampling strategies requiring the
27
-------
Table 5. ESTIMATION OF BREAKTHROUGH VOLUMES FOR
VINYL CHLORIDE AND VINYL BROMIDE ON SKC
CHARCOAL (104)
Temperature
°C (°F)
10 (50)
15.5 (60)
21.1 (70)
26.7 (80)
32.2 (90)
37.8 (100)
Vinyl
A/g
104
81
63
49
38
30
Chloride
a/2.52 ga
262
204
159
123
96
76
Vinyl
A/g
388
306
241
190
150
118
Bromide
A/2.52 ga
978
771
608
479
378
298
a
A 1.5 cm i.d. x 4.0 cm bed of charcoal weighs 2.52 g.
Table 6. ESTIMATION OF BREAKTHROUGH VOLUMES FOR
METHYL CHLORIDE AND METHYL BROMIDE ON
SKC CHARCOAL (104)
Temperature
°C (°F)
10 (50)
15.5 (60)
21.1 (70)
26.7 (80)
32.2 (90)
37.8 (100)
Methyl
A/g
14.3
11.1
8.7
7.5
5.6
4.4
Chloride
A/2. 52 g
¥ ?36
28
22
19
14
11
Methyl
A/g
98
75
57
43
32
25
Bromide
A/2.52 g
248
188
143
108
82
62
28
-------
collection and analysis of the more volatile compounds in ambient air. The
feasibility of thermally desorbing and transferring to Tenax GC cartridges to
eliminate the presence of high concentrations of water on the SKC charcoal
cartridges was demonstrated in these experiments.
ESTIMATION OF RELATIVE MOLAR RESPONSE RATIOS FOR SEVERAL ORGANIC VAPORS
In the pursuit of a method for the quantification of organic vapors in
the ambient air, several criteria must be addressed. The first is the
determination of breakthrough volume on the sorbent material which is being
utilized to trap the organic vapors from the ambient air. Secondly, the
process of transferring the organic vapors trapped on the sorbent to the
analytical system must be standardized in order to insure that quantitative
recoveries are obtained. Another aspect which must be addressed is instru-
ment calibration for determining the absolute quantity of each pollutant
originally on the sampling cartridge. The utilization of a standard curve for
all compounds to be quantified in ambient air is not feasible. One approach
which can be used to circumvent the preparation of standard curves is the use
of relative molar response ratios. Successful use of this method requires
information on the exact amount of standard added and the relationship of RMR
(unknown) to the RMR (standard). '
The use of the RMR method for quantifying ambient air pollutants is
described here.
Experimental Method
The method of calculation for RMR is as follows:
A , /Moles ,
X-JN pj^ = unk _ unk
unknown/standard A ,,/Moles . ,
sta sta
A = peak area, determined by integration or triangulation.
The value of RMR is determined from at least five independent analyses.
A . /g . /GMW .
unlc7 ?unk unk
A = peak area, as above
g = number of grams present
GMW = gram molecular' weight
Thus, in the sample analyzed:
29
-------
A . .GMW . .g ,
/0v unk unk std
(3) g
unk A _,.GMW , .RMR . , ,
std std unk/std
The standard may be added as an internal standard during sampling. However,
since the volume of air taken to produce a given sample is accurately known,
it is more practical to use the external standard method whereby the standard
is added to the cartridge after the sample has been collected in the field.
Two external standards were selected. These were hexafluorobenzene and
perfluorotoluene. The retention index for these external standards is such
that the elution from the glass capillary column (OV-101) occurs at a temper-
ature and time which does not interfere with the analysis of unknown com-
pounds in ambient air samples.
Results and Discussion
Since the volume of air taken to produce a given sample is accurately
known and an external standard was utilized, then grams (unknown)/volume
(air) can be determined. In order to successfully utilize this technique,
the RMR's for organic vapors must be determined either with authentic com-
pounds which were identified in the ambient air or with their analogs.
The relative molar response factors for several compounds based upon the
total ion current monitor of the GC/MS/COMP system is shown in Table 7. The
RMR's were calculated using the two external standards, perfluorobenzene
(PFB) and perfluorotoluene (PFT). The statistical variances and deviation
are also indicated. As might be expected, the RMR values for aromatic hydro-
carbons are quite similar to one another. Thus by choosing the appropriate
RMR in a homologous series it can be utilized for calculating concentrations
of constituents where the authentic compound is unavailable and its RMR is
not known.
The RMR factors for hydrocarbons also reveal a very close similarity in
a homologous series. The greatest variation occurs with the halogenated
hydrocarbons. They may vary several fold.
The relative molar response values for several compounds based on
selected ions are given in Table 8. In this case, a unique ion which is
characteristic of that compound was selected and a relative molar response
factor calculated relative to one of the ions selected for hexafluorobenzene
(m/e 186). A second ion for ,each compound was also utilized for calculating
30
-------
Table 7. RELATIVE MOLAR RESPONSE (RMR) FACTORS FOR SEVERAL
COMPOUNDS BASED UPON TOTAL ION CURRENT MONITOR
Chemical
Class
PFBa PFTa
b c
Compound RMR Var. S.D. RMR Var. S.D.
Aromatic
hydrocarbons
CO
Oxygenated
aromatic
Hydrocarbons
Toluene
£-"Xylene
Cumene
1,3,5-Trimethylbenzene
1,2,4-Trimethylbenzene
1,2,3-Trimethylbenzene
Phenylacetylene
Naphthalene
a-Methyls tyrene
Indan
Tetrahydronaphthalene
Anisole
Acetophenone
Styrene oxide
2-Methylbenzofuran
m-Tolualdehyde
ri-Heptane
ri-Nonane
n-Undecane
ri-Tridecane
1-Heptene
4-Vinyl-l-cyclohexene
2.38
2.90
1.56
1.48
1.47
1.26
1.25
1.34
1.88
1.54
0.020
0.170
0.050
0.050
0.025
0.040
0.001
-
0.001
0.024
0.15
0.42
0.22
0.22
0.16
0.19
0.03
-
0.01
0.16
2.48
2.33
1.76
1.63
1.47
1.45
1.45
1.53
2.04
1.76
0.110
0.200
0.026
0.037
0.006
0.013
0.010
-
0.004
0.027
0.33
0.41
0.16
0.19
0.08
0.11
0.12
-
0.06
0.16
1.98
1.72
1.77
0.58
0.35
1.46
0.56
0.290
0.040
0.030
0.003
0.020
0.54
0.20
0.16
0.06
0.15
2.14
0.79
0.35
1.32
0.54
0.040
0.007
0.020
0.030
0.003
0.20
0.08
0.14
0.18
0.06
1.39
1.85
1.71
1.31
1.84
1.59
0.150
0.020
0.048
0.130
0.001
0.040
0.39
0.14
0.22
0.36
0.04
0.22
1.66
2.04
1.94
1.44
2.01
1.84
0.080
0.008
0.016
0.110
0.001
0.010
0.29
0.09
0.12
0.34
0.04
0.10
(continued)
-------
Table 7 (cont'd)
u>
K)
Chemical
Class
Oxygenated
hydrocarbons
Halogenated
hydrocarbons
Chlorinated
aromatics
Miscellaneous
Compound
Di-n-butyl ether
2-Pentanone
2-Ethylfuran
Cyclohexene oxide
Trichloroethylene
Tetrachloroethylene
Bis- (chloromethyl)ether
2 , 3-Dichlorobutane (Rac . )
2 , 3-Dichlorobutane (Meso)
l-Chloro-2-bromoethane
Trimethylene chlorobromide
1 , 2-Dibromoethane
Bromoform
Chlorobenzene
o-Chlorotoluene
Benzyl chloride
m-Dichlorobenzene
Bromobenzene
£-Ethylaniline
RMR
5.90
2.84
2.59
1.28
2.08
2.76
3.70
1.80
2.01
—
-
3.34
3.68
2.10
2.06
2.00
2.21
3.90
1.62
PFBa
Var.b
0.300
0.260
0.230
0.020
0.14
0.21
0.10
0.03
0.03
-
-
0.14
—
0.007
0.04
0.03
0.14
-
0.170
S.D.°
0.55
0.41
0.48
0.13
0.38
0.46
0.32
0.17
0.18
—
-
0.37
—
0.03
0.19
0.18
0.38
-
0.41
RMR
6.40
2.94
2.68
1.32
2.41
3.10
3.57
2.07
2.16
5.34
6.55
2.78
3.31
2.47
2.31
1.68
2.51
3.08
1.28
PFTa
Var.
0.130
0.060
0.100
0.030
0.49
0.78
0.79
0.04
0.01
0.02
0.02
0.58
1.71
0.04
0.01
0.03
0.32
2.10
0.060
S.D.
0.36
0.240
0.320
0.17
0.70
0.83
0.89
0.21
0.12
0.14
0.40
0.76
1.31
0.20
0.11
0.18
0.56
1.45
0.25
fPFB = perfluorobenzene, PFT = perfluorotoluene which were external standards.
Var. = statistical variance.
c
S.D. = standard deviation.
-------
Table 8. RELATIVE MOLAR RESPONSE VALUES FOR SEVERAL ORGANIC COMPOUNDS BASED
UPON SELECTED IONS
Chemical
Class
Compound
1st Ion
M.W. m/e (I)
RMR
2nd Ion
m/e (I)
RMR
Halogenated
hydrocarbons
CO
CO
Aromatics
Allyl bromide
Bromobenzene
Bromod ichloromethane
Bromoform
1 or 2-Bromopropane
1-Chloro-2-bromoe thane
l-Chloro-3-bromopropane
l-Cb.loro-2,3-dibromopropane
1,l-Dibromo-2-chloropropane
Dibromochloromethane
1,2-Dibromoethane
1,2 or 1,3-Dibromopropane
Methyl chloride
Methyl bromide
Vinyl bromide
Toluene
£-Xylene
Cumene
1,3,5-Trimethylbenzene,
1,2,4-Trimethylbenzene,
1,2,3-Trimethylbenzene
m-Tolualdehydeb
Anisole
Acetophenone
Naphthalene
120
156
162
250
122
142
156
234
234
206
186
200
50
94
106
120
156
129
173
124
144
158
157
157
129
109
123
50
94
108
(25)
(78)
(12)
(100)
(20)
(15)
(60)
(100)
(100)
(100)
(95)
(99)
(100)
(90)
(75)
3.
2.
1.
2.
3.
1.
4.
9.
9.
6.
3.
3.
1.
1.
2.
25
18
54
78
25
12
48
46
46
53
34
37
7
9
2
122
158
85
252
122
63
160
159
159
208
188
202
52
81
110
(25)
( )
(60)
(10)
(20)
(100)
(12)
(25)
(25)
(10)
(2)
(65)
(32)
(78)
(10)
3.25
6.16
0:30
3.25
7.39
1.12
2.37
2.37
0.70
0.50
2.21
0.66
0.30
92
106
120
120
120
120
120
108
120
128
91 (100)
105 ( 26)
120 ( 28)
120 ( 67)
120 ( 58)
120 ( 52)
91 (100)
108 (100)
105 (100)
128 (100)
2.37
3.46
1.98
2.08
2.44
1.56
1.51
1.19
0.97
1.92
64 (13)
51 (10)
79 ( 9)
119 (15)
119 (14)
119 (11)
119 (71)
65 (76)
120 (29)
51 (12)
0.66
0.39
1.47
0.75
0.80
0.52
1.06
1.30
0.27
0.18
(continued)
-------
Table 8 (cont'd)
us
Chemical
Class
Oxygenated
hydrocarbons
Hydrocarbons
1st Ion
Compound
2-Ethylfuran
2-Pentanone
Cyclohexene oxide
n-Nonane ,
n.-Undecane ,
n-Tridecane
M.W.
96
86
96
128
156
184
m/e (I)
81 (100)
43 (100)
83 (100)
85 ( 22)
85 ( 21)
71 ( 41)
RMR
2.35
1.98
0.51
2.46
3.40
3.50
2nd Ion
m/e (I)
_
57 (26)
—
71 (20)
156 ( 4)
85 (23)
RMR
—
0.14
—
2.01
0.89
1.99
aRMR values relative to m/e 186 (100) for HFB.
RMR values relative to m/e 167 (18) for HFB.
-------
the RMR factor in the event that the first ion saturated the instrument or
was non-specific.
The relative response factors were in all cases calculated on the basis
of quadruplicate determinations between the authentic compound and the
external standard.
DETERMINATION OF THE OVERALL SENSITIVITY OF HIGH RESOLUTION GLC/MS/COMP FOR
THE ANALYSIS OF AMBIENT AIR POLLUTANTS
In order to determine the overall utility and sensitivity of the gc/
ms/comp technique for the quantification of the ambient air pollutants,
the theoretical sensitivity limits were estimated. Based upon the break-
through volumes for the compounds listed in Table 4 at an ambient air temper-
ature of 70°F, the theoretical sensitivity for the collection, transfer of
the organic pollutants from the cartridge to the analytical system and the
response of the analytical system to the organic vapor were calculated for
a number of compounds. These results are given in Table 9.
The estimated detection limit for a number of halogenated compounds
reveals a variation over several orders of magnitude (Table 9). The low
detection limits are directly proportional to the sensitivity of the instru-
mentation to the particular compound and to its breakthrough volume. Thus
the higher the breakthrough volume, the lower the anticipated limit of
detection for its analysis in ambient air. For example, the volatile com-
pound vinyl bromide has an estimated detection limit of approximately 250
3
ng/m of ambient air, whereas the estimated detection limit for bromobenzene
is 100 pg/m3 of air (Table 9).
The estimated detection limits for nitrosamines such as N-nitrosodi-
methylamine can be as low as 1.67 ppt (70°F).
35
-------
Table 9. OVERALL THEORETICAL SENSITIVITY OF HIGH RESOLUTION
GAS CHROMATOGRAPFS/MASS SPECTROMETRY/COMPUTER ANALYSIS
FOR ATMOSPHERIC POLLUTAHTS
OJ
Estimated Detection
Limita
Chemical
Class
Halogenated
hydrocarbon
Vinyl bromide
Bromoform
Bromodichloromethane
Dibromochlorome thane
l-Bromc-2-chloroethane
Ally! bromide
1-Bromopropa.ne
l-Chloro-3-bromopropan«?
l-Chloro-2 , 3-dibromopropane
1, l-Dibromo-2-chloropropane
1 , 2-Dibrotiioetbane
1 , 3-Dibromopropane
Epichlorohydrin
(l-Chlcro-2 , 3-epoxyprcpaue)
Ep ibr omohy d r in
(l-Bromo-2 , 3-epoxy Mfopane)
Bromobenztne
Methyl bromide
Ma thyl chloride
Vinyl chloride
Me thy 1 en e chloride
Chloroform
Carbon tetrachloride
ng/ra
250
0.340
1.300
0.667
1.00
5.00
5.200
0.150
-0.100
-0.100
0.530
-0.100
9.600
0.300
0.100
500
2000
800
700
200
250
ppt
57
0.03
0.22
0.07
0.67
"'1.04
1.06
0.01
<0.01
<0.01
0.07
-0.01
2.50
0.05
0.02
135
1000
333
200
420
400
(continued)
-------
Table 9 (continued)
Estimated Detection
Limit*
Chemical
Class
Halogenated
hydrocarbon
(cont'd)
Halogenated
ethers
Nitrosamines
Oxygenated
Compound
1 , 2-Dichlorcethane
1,1, 1-Tr ichloroethane
Tetrachloroethyleae
Trichloroethylfcna
l-Chloro-2-niethylpropene
3-Chloro-2-methylpropene
3-Chloro-l-buteue
Allyl chloride
4-Chloro-l-bu tene
l-Chloro-2-butene
Chlorobenzene
o~Dichlorobanzene
m-D i c hlor ob en z ene.
B'.ii5.zyichloride
?.-ChloroGr.hyl ethyl ether
Bis- (ctiloromethyl) ether
N-Kitrosodimethylamine
N-Mitrosodiethylaraine
Acrolein
Glycidaldehyde
Propylene oxide
Butadiene diepoxide
, 3
ng /m
32
66
2.5
10
62
62
83
83
38
13
2.10
1.00
0.75
0.65
A. 15
1.0
5.0
3.0
-100
-59
-60
-20
ppt
8.15
12.45
0.38
1.92
21.5
21.5
28.8
28.8
13.2
4.5
0.47
0.06
0.01
0,01
0.97
1.10
1.67
0.74
56.5
19.5
25.5
6.7
(continued)
-------
Table 9 (continued)
u>
00
Chemical
Class
Oxygenated
hydrocarbons
(continued)
Nitrogenous
Compounds
Sulfur
Compounds
Compound
Cyclohexene oxide
Styrene oxide
Acetophenonc
B-Propiolactone
Nitromethane
Aniline
Diethyl sulfate
Ethyl methane sulfate
Estimated Detection
Limit3
ng/m"
ppt
-10
2
-2
-3
8
3.0
-50
-5.0
2.5
0.415
-0.415
-.1.2
-2.4
0.78
_
_
a
Limits are calculated on the basis of the breakthrough volume for 2.2 g of Tenax GC, (at 70°F),
capillary column performance and sensitivity of the mass spectrometer to that compound in the
mass- fragmentography mode of most intense ion.
-------
SECTION 7
IDENTIFICATION AND QUANTIFICATION OF ORGANIC POLLUTANTS IN
AMBIENT AIR FROM SEVERAL GEOGRAPHICAL LOCATIONS
The overall purpose of this program has been to examine ambient air for
hazardous organic compounds, particularly those volatile vapors which pass
through the conventional Hi-Vol glass fiber filters. In the past very
little characterization has been performed on ambient air collected from
geographical areas throughout the Continental U.S.
Information on the composition of ambient air is of course particularly
important if we are to understand the health effects impact resulting from
organic pollutants. The information gathered with regard to the composition
and quantity of organic vapors will assist investigators in future studies
to determine the epidemiological implications of the pollution which is
occurring. Since to-date there is only a paucity of data available with
regard to the types of organic pollutants and their concentrations in ambient
air, this program was initiated in order to acquire a better understanding
of the potential pollution problems confronting the populated areas around
the U.S.
CHARACTERIZATION AND QUANTIFICATION OF AMBIENT AIR POLLUTANTS IN THE
BALTIMORE, MD AREA
Previous studies on the analysis of ambient air surrounding an indus-
trial site in Baltimore, MD revealed the presence of N-nitrosodimethyl-
/•q g1)
amine. ' The quantification of DMN was also performed in the cited
(3 7)
studies. ' However, the previous studies on nitrosoamines only represent
a small potential health problem since the complete characterization of the
ambient air for volatile organics had not been conducted. For this reason,
we undertook a study in order to obtain a more complete characterization of
the ambient air so as to better understand the health impact of the organic
vapor pollutants. Because nitrosoamines were found, it does not necessarily
follow that these are the only compounds responsible for the health problems
39
-------
(e.g. incidence of cancer) for the immediate populace since there is the
important aspect of other pollutants interacting antagonistically or syner-
gistically to exert the final health impact observed in humans.
This section presents the characterization and quantification of ambient
air pollutants near an industrial area in Baltimore, MD (Fig. 1).
Experimental
The sampling procedure employed for this study has been previously
(2)
described wLich consisted of concentrating ambient air pollutants on a
1.5 x 6 cm bed of Tenax GC (35/60) in a glass cartridge. All of the samp-
ling cartridges were preconditioned by heating to 275°C for a period of 20
min under helium purge (20-30 ml/min). Cartridges were cooled in precleaned
.. centrifuge tubes. The cartridge containers were immediately sealed
to prevent contamination. Cartridges prepared in this manner were carried
to the sampling site; 2-3 cartridges were designated as blanks to determine
whether any of the cartridges were contaminated by the packing and transpor-
tation procedure.
Ambient air samples were collected with a Nutech Model 221-AC/DC por-
table sampler (Nutech Corp., Durham, NC). In general a sampling rate of 1
£/min/cartridge was used throughout this study (Table 10).
The instrumental system (glc/ms/comp) used for the qualitative and
quantitative analysis of ambient air pollutants and the inlet manifold used
for recoverying vapors trapped on Tenax GC cartridge samplers were as des-
(2 3)
cribed elsewhere. ' The desorbed vapors were resolved by glass capil-
lary, gas-liquid chromatography and mass cracking patterns were automa-
tically and continuously obtained throughout the glc run with a Varian MAT
CH-7 gas chromatograph/mass spectrometer.
The operating parameters for the glc/ms/comp for analysis of samples
collected on Tenax GC cartridges from the Baltimore, MD area are shown in
Table 11. Ambient air samples were analyzed on a 100 m glass SCOT column
coated with OV-101 stationary phase. The desorption of ambient air pol-
lutants from the Tenax GC cartridge samplers was conducted at 265-270°C. A
single stage glass jet separator interfaced the SCOT capillary column to the
mass spectrometer and was maintained at 200°C.
Identification of resolved components was achieved by comparing the
mass cracking pattern of the unknown mass spectra to an 8 major peak index "l
40
-------
PATAPSCO AVEMMc
CHESSIE
COAL PIERS
CURTIS BAY
SCALE: ONE INCH =0.5 miles
Figure 1. Map of sampling area in East Brooklyn, Baltimore, Maryland
41
-------
Table 10. SAMPLING PROTOCOL FOR BALTIMORE AREA
ro
Wind
Date
10/14/75
10/15/75
10/16/75
11/19/75
Time
1100-1450
2300-0250
1000-1350
1400-1600
Location
FMC (Parking Lot)
FMC (Parking Lot)
Sewage Plant
FMC, 200 yd W-NW of
Temperature
83
65
72
65
RH
40-50
90-97
45-57
56
Direction
WNW
Calm
NNW
E
Speed
(KTS)
10
-
9-11
3
11/24/75
11/24/75
1150-1350
1355-1555
diamazine thermal
destructor
FMC, SW of dia-
mazine thermal
destructor
FMC, SW of dia-
mazine thermal
destructor
-------
Table 11. OPERATING PARAMETERS FOR GLC-MS-COMP SYSTEM
Parameter
Setting
Inlet-manifold
desorption chamber
valve
capillary trap - minimum
maximum
thermal desorption time
GLC
OV-101 glass SCOT (100 m)
carrier (He) flow
i
single stage glass jet separator
ion source vacuum
filament current
multiplier
scan rate, automatic cyclic
scan range
MS
265°-270°
175°
-195°C
+175°C
~4 min
30-225°C, 4°C/min
1.5 ml/min
200°C
~2 x 10~6 torr
300 pA
5.5
1 sec/decade
m/e 20 -»• 300
43
-------
(8 9)
of the mass spectra. ' In several cases the identification was confirmed
by comparing the mass spectrum and the elution temperature of the authentic
compound with the unknown substance. Particular attention was paid to the
relationship between the boiling point of the identified compound and its
elution temperature and to the elution of constituents in a homologous
series since the OV-101 SCOT capillary column separates primarily on the
basis of boiling point.
The halogeuated hydrocarbons in ambient air which were identified in
these samples were quantitated. Standard curves for the response of the
mass spectrometer v£ the concentration of each of the identified halogenated
hydrocarbons were prepared by introducing known quantities of vapor into the
glc/ms system. Synthetic air halogenated hydrocarbon vapor mixtures were
prepared in specified quantities trapped on Tenax GC cartridges. By ther-
mally desorbing the cartridges and monitoring the total ion current, res-
ponses vs_ concentrations were obtained (Fig. 2). Cartridge samplers contain-
ing unknown concentrations of each of the halogenated hydrocarbons were
analyzed by monitoring the total ion current and obtaining the quantity/
cartridge from the standard curve. In those cases where baseline resolution
was not achieved by the capillary column the technique of mass fragmen-
tography (Section VI) was used instead of the total ion current. Based on
the volume of air sampled and the breakthrough volume for each of the halo-
genated hydrocarbons (Section VI) the concentrations of the halogenated
hydrocarbons in ambient air were calculated.
Results and Discussion
Characterization of Samples.—Figures 3 and 4 depict the profiles observed
for ambient air samples taken near the FMC Corporation and the Patapsco
Sewage Treatment Plant. A majority of the components shown in Fig. X were
identified and are listed in Table 18 (Appendix I). In these samples,
several halogenated compounds were identified. Those of particular interest
were l-chloro-2-methylpropene (dimethyl vinyl chloride, peak No. 6), 3-
chloro-2-methylpropene (peak No. 7), 2,3-dichlorobutane (racemic, peak No.
33), and 2,3-dichlorobutane (meso, peak No. 35). The remaining halogenated
compounds were typically of those which have been previously identified at
other geographical areas within the Continental U.S.
44
-------
Ui
M
12
10-
.
tu
a
2,3-dlchtorobutane.
2,3-dichlorobutane
3-chloro -2-methylpropene
l-chloro-2- melhylpropene
6 10 12 14 16 18 20
/tg CHLORINATED HYDROCARBON
Figure 2. Standard linear regression curves for chlorinated hydrocarbons,
-------
TEMPERATURE (°C)
128 140 132 164 176 IBS 200 212 224 230
27 30 33 36 39 42 45
Figure 3. Profile of ambient air pollutants from industrial site in Baltimore, MD using
high resolution gas chromatography/mass spectrometry/computer. A 100 m glass
SCOT coated with OV-101 stationary phase was used; temperature programmed from
20-230°C @ 4°C/miri.
-------
100
90-
eo-
w 6°-
£ 50-
u
u «i
§ 301-
UJ
10-
o'—
H-
9
68
80
92
116
128
TEMPERATURE (°C)
140 152 164
188
200 212 222 230
12
15
18
21
27
30 ^33
TIME (MIN)
36
39
42
45
4B
51
54
57
60 63
Figure A. Profile of ambient air pollutants from Patapsco Sewage Treatment Plant in
Baltimore, MD using high resolution gas chromatography/mass spectrometry/
computer. A 100 m glass SCOT coated with OV-101 stationary phase was used;
temperature programmed from 20-230°C @ 4°C/min.
-------
The pollutants in Figure 3 are listed in Table 19 (Appendix I). In
contrast to the samples obtained near the industrial site, this sample did
not contain any of the previously described halogenated hydrocarbons.
Several additional samples were taken in this area, and each revealed the
presence of th«_ four halogenated hydrocarbons described above. Because of
the sampling strategy employed, it was not possible to attribute the emissions
to the most immediate industrial site. The mettrological conditions in com-
bination with tue sampling protocol employed did not allow differentiation in
the source of these compounds. Tables 19-22 (Appendix I) list additional
identified pollutants.
Quantification of Halogenated Hydrocarbons in Ambient Air.—Table 12 depicts
the sampling conditions and the concentrations of halogenated hydrocarbons
observed in ambient air from an industrial area in Baltimore, MD. On two
separate occasions during the month of October and November, the concen-
tration of the four identified halogenated hydrocarbons were determined.
The highest concentration observed was for dimethyl vinyl chloride which
occurred in samples taken on the FMC property during the evening hours.
o
Dimethyl vinyl chloride reached a level of 670,000 ng/m of ambient air.
The lowest levels were approximately 100,000 ng which were detected for the
month of November. The second most prominant halogenated hydrocarbon was an
isomer of dimethyl vinyl chloride, 3-chloro-2-methylpropene which obtained a
3
level of 400,000 ng/m . Inspection of the data reveals that a correlation
is evident between the concentrations of each of the halogenated hydro-
carbons and the particular sampling time. Since their levels appear to
increase and decrease simultaneously, this suggests that the same point
source of emission is responsible for all four of the compounds.
In contrast to the above observations for the halogenated hydrocarbons
near an industrial site, a sample of ambient air which was taken at the Patap-
sco Sewage Treatment Plant did not yield any measurable levels of the four
halogenated hydrocarbons.
An interesting observation is that 2,3-dichlorobutane may exist as a
racemic mixture and also as a meso pair. Although the racemic pair is
theoretically possible, we only observed one isomer in the samples in which
2,3-dichlorobutane was detected. Authentic compounds of the four halo- .*»
genated hydrocarbons were subjected to high resolution gas
48
-------
Table 12. SAMPLING CONDITIONS AND CONCENTRATION OF HALOGENATED HYDROCARBONS IN AMBIENT AIR
Date
10/14/75
10/14/75
10/16/75
11/24/75
11/25/75
Time
(EOT)
11:00 AM-2:
11:00 PM-2:
10:00 AM-1:
6:35 PM-8:
1:48 PM-3:
50 PM
50 AM
50 PM
35 PM
48 PM
Location
FMC (Parking Lot)
FMC (Parking Lot)
Sewage Plant
FMC
FMC
Temperature
(°F)
83
65
72
50
55
RH
40-50
90-97
45-75
70
73
Wind
Direction
WNW
Calm
NNW
S-SW
SW-S
Speed
(KTS)
10
-
9-11
4
3-6
Concentration
(yg/m3)a
1
200
670
ND
100
90
2
280
400
ND
110
175
3
50
156
ND
26
22
4
75
115
ND
32
47
vo
1 = l-chloro-2-methylpropene, 2 = 3-chloro-2-methylpropene, 3 = 2,3-dichlorobutane (meso), 4 = 2,3-
dichlorobutane (one of the racemic pairs).
-------
chromatography/mass spectrometry and the retention time and mass cracking
patterns were determined for the identity of each constituent (Fig. 5).
While establishing the retention time of the halogenated hydrocarbons, we
observed that au authentic sample of 2,3-dichlorobutane was a racemic
mixture. The high resolution glass capillary columns effected baseline
separation of the two racemic isomers as well as complete resolution from
the meso pair of 2,3-dichlorobutane. Since the various isomeric forms were
completely separated, we were able to then deduce whether the meso and
racemic pairs were present in the ambient air samples. Indeed the meso form
was observed, however only one isomer of the racemic pair was detected.
Figure 5 depicts the resolution of the four authentic halogenated hydro-
carbons .
ANALYSIS OF AMBIENT AIR FROM THE KANAWHA VALLEY, WV
A study had been conducted in the Kanawha Valley for the analysis of
nitrosoamines in ambient air. ' Concurrent with this analysis and under
this program, a broader more complete characeterization of the organic
pollutants in ambient air was also conducted. This section describes the
characterization and quantification of organic compounds in ambient air
taken from several sites within the Kanawha Valley.
Experimental
Ambient air sampling at several locations in the Kanawha Valley was
conducted in a similar manner as described for the Baltimore project. The
sampling protocol for selected sites in this valley is given in Table 13.
Figures 6 and 7 depict the sampling locations in Belle and South Charleston,
WV. The principal sites were on the E. I. DuPont Nemours property in Belle
and Union Carbide in South Charleston.
The characterization and quantification of organics were as previously
described.
Results and Discussion
The identification and estimation of several organic vapors are given
in Tables 23-25 (Appendix I). Many organic vapors were identified.
Those of particular interest were vinyl chloride, acetaldehyde, benzene,
dimethylformamide, hexyl methacrylate, alkyl amines, chloroform, ethyl
acetate, carbon tetrachloride, methyl chloroform, acetone, etc. The con-
centrations of some of these compounds are given in Table 14.
50
-------
21 24
TIME (MIN)
27
30
36
39
42
Figure 5. Resolution of standard mixture of chlorinated hydrocarbons using a
90 m glass SCOT coated with OV-101 stationary phase. Temperature
programmed from 20-225°C @ 4°C/min.
-------
Table 13. AMBIENT AIR SAMPLING PROTOCOL FOR SELECTED AREAS IN THE KANAWHA VALLEY, WV
Site
Location Sampling Period m /cartridge
Remarks
in
Belle, WV 1
Belle, WV 2
Belle, WV 4
S. Charleston, WV 9
S. Charleston, WV 10
S. Charleston, WV 14
Belle, WV ' 6
Belle, WV 7
Belle, WV 8
Nitro, WV 15
9:30 pm-2:17 am 0.247
9:30 pm-2:19 am 0.275
10:05 pm-3:00 am 0.406
2:41 pm-4:00 pm 0.248
3:12 pm-5:12 pm 0.350
8:47 pm-10:44 pm 0.324
3:26 pm-5:24 pm 0.256
4:00 pm-6:05 pm 0.280
7:06 pm-9:06 pm 0.348
11:58 am-3:48 pm 1.593
12/1/75
12/1/75
12/2/75
12/3/75
12/3/75
12/3/75
12/4/75
12/4/75
12/4/75
12/5/75
30°F -
30°F -
~40°F
55°F -
55°F -
44°F -
66°F -
65 °F -
65°F -
65 °F -
Wind NW - 5 mph
Wind NW - 5 mph
- Wind SE - 0-5 mph
Wind WSW+NW - 0-3 mph
Wind WSW+NW - 0-3 mph
Wind N-*-NNE - 3 mph
Wind NE - 2 mph
No wind
Wind NE - 0-3 mph
Wind S - 10 mph
-------
Ui
u>
V 1"
! PARKING LOT I
• 6rau<4 Iml ikrallon 10]' 0* /
• MMiyl onlM I MM CO!' 0"
mUl MM TSj' 0"
Wftl ncovttv
Hllhyl Amlnii Plonl
BARGE WADING
KANAWHA RIVER
BARGE WADING
Figure 6. Plant" map of DuPont in Belle, WV depicting sampling locations.
-------
Ul
TfMltyrlomlni
HotptallM
DlbulilomlM
Figure 7. Plant map of Union Carbide in South Charleston, WV depicting sampling
locations.
-------
Table 14. AMBIENT AIR LEVELS OF SEVERAL POLLUTANTS
IN THE KANAWHA VALLEY, WV*
Compound
Vinyl chloride
Acetaldehyde
Acetone
Methylene chloride
Chloroform
Carbon tetrachloride
Benzene
N, N-Dimethylf ormamide
y-Butyrolactone (tent.)
Ethyl acetate
Belle
-2-4,000
-9,800
trace
8,700
trace
trace
-400,000
-76,700
NDb
ND
Site
South Charleston
trace
trace
-100,000
trace
-105,000
-60,000
-140,000
ND
3,750
-70,000
Nitro
50,000
trace
>125,000
>75,000
>39,000
ND
-150,000
ND
ND
trace
values are in ng/m
ND = not detected
55
-------
QUALITATIVE AND QUANTITATIVE ANALYSIS OF VOLATILE ORGANIC POLLUTANTS NEAR
A CHEMICAL DISPOSAL SITE
The objective of this study was to determine the composition and concen-
trations of organic volatiles occurring in ambient air near a disposal site
in Edison, NJ. The landfill site was located on the north bank of the
Raritan River at the end of Mill Road. Large quantities of chemical waste
were known to be dumped at this location.
Experimental
The sampling strategy surrounding the disposal site incorporated up-
wind, downwind and crosswind sampling as well as on the dump mound itself,
in order to ascertain which organic vapors were eminating from the
landfill itself. Figure 8 depicts the sampling locations surrounding the
Kin-Buc landfill in Edison, NJ. Table 15 gives the sampling protocol for
investigating this site. The ambient air samples were collected according
(2 3)
to the previously described procedure. '
Collected samples were submitted to glc/ms/comp analysis for either
nitrosoamines or complete organic vapor characterization. The analytical
(3)
protocol for this analysis has also been previously described.
Results and Discussion
No nitrosoamines were detected in all samples examined. The identity
of the compounds in samples obtained from upwind and downwind positions as
well as on top of the chemical dump are listed in Tables 26-33 (Appendix I).
After comparing the results obtained for each of the samples surrounding the
chemical dump site, compounds were selected for quantification based on
their presence only in samples obtained either on the mound or downwind from
the chemical dump site or their extraordinarily high concentrations in
ambient air. The concentration of several organic vapors are given in Table
16. Very high concentrations of benzene, dichloromethane, toluene, vinyl
methyl ether, vinyl isopropyl ether and methyl chloroform were observed. In
addition to several chlorinated hydrocarbons, methylene bromide was identi-
fied. This represents the first case in which we have identified this
compound in ambient air.
COMPOSITION OF AMBIENT AIR FROM LOS ANGELES, CA BASIN
Sampling was performed in the Los Angeles basin area at locations near
major industrial sites. The primary type of industrial activity was the
56
-------
0.5
1.0
I
MILES
Figure 8. Sampling locations surrounding Kin-Buc Land-fill,
Edison, NJ
57
-------
Table 15. AMBIENT AIR SAMPLING PROTOCOL FOR INVESTIGATING CHEMICAL DUMP/LANDFILL IN EDISON, NJ
Sampling
Period Location (No.)'
Bearing0/distance Sampling Time 3
(mi) (min) m /cartridge
Remarks
Oi
00
Parkland (1)
180-260/0.25
36
Tower Marina (2) 065-909/^1
Schoolhouse Rd.
East Brunswick, NJ
Parkland (1)
Parkland (1)
Parkland (1)
180-260/0.25
Tower Marina (2) 065-090/^1
180-260/0.25
Tower Marina (2) 065-090/^1
160-275/^0.06
38
38
40
39
45
41
(continued)
0.317 3/24/76 - 12:47 pm-l:23 pm
65°F 35% RH
Clear 30.48" Hg
Wind ^230°, 3-8 mph
0.300 3/24/76 - 4:47 pm-5:25 pm
64°F 38% RH
Clear 30.42" Hg
Wind 200-230°, 5-13 mph
(upwind sample)
0.290 As above
0.032 (downwind samples)
0.300 3/25/76 - 11:15 am-ll:55 am
60°F 43% KH
3/4 Cloud 30.22" Hg
Wind 225°, 3-8 mph
(upwind sample)
0.300 As above
(downwind sample)
0.300 3/25/76 - 3:08 pm-3:53 pm
As above
(upwind sample)
0.300 3/25/76 - 3:05 pm-3:46 pm
As above
(downwind sample)
-------
Table 15 (cont'd)
Sampling
Period Location (No.)'
Bearing0/distance Sampling Time 3
(mi) (min) m /cartridge
Remarks
Top of KB Mound
Meadow Rd. (5)
(between Stauffer
and KB)
NJ Turnpike (3)
at Mill Rd.
11
Sayreville, NJ (4)
at St. Stanislaus
School Rd.
145°/O.5
140° M. 75
315-325/1.25
42
130
130
0.060
0.060
0.300
0.914
0.958
0.117
3/2576 - 3:06 pm-3:17 pm
64°F 38% RH
Overcast 30.11" Hg
Wind 265-285°, 5-10 mph
3/25/76 - 4:20 pm-5:02 pm
63°F 45% RH
9/10 Cloudy 30.14" Hg
Wind 245°, 2-8 mph
(upwind sample)
3/26/76 - 10:48 am-12:59 pm
60°F 34% RH
Clear 30.41" Hg
Wind 300-320°, 0-10 mph
Shifting to 230° at 12:45 pm
(upfield sample)
3/26/76 - 10:49 am-12:59 pm
As above
(downwind sample)
See map (Fig. 6) for location number.
'Relative to dump site.
-------
Table 16. CONCENTRATION OF ORGANIC VAPORS SURROUNDING KIN-BUG DUMP AREA
Location/Sampling Period
Compound
Acetaldehyde
Benzene
Bromoethane
Benzaldehyde
Carbon tetrachloride
Chloroform
l-Chloro-2-bromoe thane
Chlorobenzene
Dichloromethane
1, 2-Dichloroethane
Dibr omome thane
Diethyl ether
'Diisopropyl ether
Dimethyl naphthalene isomers
Ethyl acetate
4-methyl-2-pentanone
Methyl n-propyl ether
Phenol
TM/2
(UW)
249
200
ND
3
20
trace
ND
trace
125
ND
ND
ND
ND
100
ND
ND
ND
trace
TM/3
(UW)
trace
trace
ND
trace
trace
15
ND
trace
0.05
ND
ND
ND
ND
-
ND
ND
ND
trace
TM/4
(UW)
trace
0.90
ND
trace
ND
20
ND
trace
0.01
ND
ND
ND
ND
-
ND
ND
ND
8
TP/5
(UW)
ND
trace
ND
trace
trace
trace
ND
trace
15
ND
ND
35
ND
20
ND
trace
ND
10
ST/5
(UW)
trace
15
ND
trace
trace
45
ND
trace
trace
ND
ND
ND
ND
trace
ND
ND
-
trace.
M/4
trace
900
trace
ND
ND
266
27
trace
1,250
57
63
30
120
trace
trace
260
trace
ND
PL/1
(DW)
trace
1,550
1
ND
ND
74
25
50
375
35
ND
23
17
-6,100
20
813
ND
ND
SA/5
(DW)
trace
10
ND
56
trace
30
ND
4
0.042
ND
ND
ND
ND
trace
ND
trace
ND
trace
PL/2
(DW)
trace
1,210
ND
10
trace
128
5
trace
390
33
ND
25
ND
trace
ND
33
ND
ND
(continued)
-------
Table 16 (cont'd)
Location/Sampling Period
Compound
Toluene
Trichloroethylene
1,1, 1-Trichloroethane
Tetrachloroethylene
Vinyl methyl ether
Vinyl isopropyl ether
TM/2
(UW)
-
9
trace
trace
ND
ND
TM/3
(UW)
-
trace
0.03
trace
ND
ND
TM/4
(UW)
-
ND
ND
trace
ND
ND
TP/5
(UW)
-
trace
0.04
8
ND
ND
ST/5
(UW)
972
13
trace
trace
trace
trace
M/4
50
trace
500
142
5,000
13,000
PL/1
(DW)
2,600
93
25
trace
ND
ND
SA/5
(DW)
15.00
trace
0.03
60
ND
ND
PL/ 2
(DW)
1,500
82
5
26
ND
ND
fvalues are in Vg/m .
TM = Tower Marina, UW = upwind, TP
Stauffer and DW = downwind
= NJ Turnpike, M = mound, PL = Parkland, SA = Sayreville, ST =
-------
synthesis, storage and usage of organic chemicals. Because of these types
of activities sampling was performed near this industrial area in order to
ascertain whether emissions might occur of volatile organic compounds which
may have health effect implications.
Experimental
The sampling and analytical methods employed in this study were as
described earlier. The sampling protocol is listed in Table 17 and their
locations are given in Figures 9-11. In the first case, sampling was conduc-
ted at 15th and Emery Street in Los Angeles, which was a location downwind
from a chemical company and in the second case a location at 2055 203rd
Street. The second location was also downwind from an industrial chemical
area.
Results and Discussion
Tables 34-36 list the organic pollutants vapors which were identified
at the locations given in Table 17. The ambient air sample from the 15th
and Emery Street location contained several halogenated compounds of interest.
These were: methyl chloride, ethyl chloride, carbon tetrachloride, tri-
chloroethylene. Two esters were also identified: isobutyl acetate and n-
butyl acetate. In a second sample taken from this location, mono vinyl
glycol ether. An ambient air sample from Dominquez, CA contained several
halogenated compounds. These were methyl chloride, ethyl chloride, 1,1,-
dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, carbon tetra-
chloride, trichloroethylene, 1,1,2-trichloroethane and trichlorobenzene.
Generally these chlorinated compounds are not ubiquitous. Other halogenated
hydrocarbons were also detected, however these have occurred in many ambient
air samples analyzed from several different geographical areas around the
Continental U.S.
The concentrations of selected organic volatile pollutants in ambient
air samples from the Los Angeles Basin area are also given in Table 34-36.
62
-------
Table 17. AMBIENT AIR SAMPLING PROTOCOL FOR LOS ANGELES, CA BASIN AREA
Sampling Location
Bearing0/distance Sampling Time
(yd)
(min)
m /cartridge
Remarks
15th & Emery St.
Los Angeles, CA
2055 223 St.
Dominquez, CA
215-240°/~350
090-140°/~350
(Stauffer)
170°/165
(Witco)
52
54
0.300
0.300
5/14/76 - 3:34 pm - 4:24 pm
83°F 42% RH
Clear 29.92" Hg
Wind-215° @ 0-7 mph
5/14/76 - 1:22 pm - 2:16 pm
78° 49% RH
Clear 30.11"Hg
Wind-110-1400 @ 0-7 mph
-------
Figure 9. Map depicting sampling locations in Los Angeles, CA
-------
ON
Ui
MILES
Figure 10. Map depicting sampling site in Los Angeles, CA
-------
223 St.
Sampling
Stte
1-405 / SAN DIEGO // FREEWAY
Av
a*
A-C Chemical Industry
N
11/2
MILES
Figure 11. Map depicting sampling location in Dominquez, CA
-------
REFERENCES
1. Pellizzari, E. D., Development of Method for Carcinogenic Vapor Analysis
in Ambient Atmospheres. Publication No. EPA-650/2-74-121, Contract No.
68-02-1228, 148 pp., July, 1974.
2. Pellizzari, E. D., Development of Analytical Techniques for Measuring
Ambient Carcinogenic Vapors. Publication No. EPA-600/2-75-076, Contract
No. 68-02-1228, 187 pp., November, 1975.
3. Pellizzari, E. D., Development of Analytical Techniques for Measuring
Ambient Carcinogenic Vapors. Contract No. 68-02-1228, in preparation.
4. Pellizzari, E. D., Bunch, J. E., Berkley, R. E., McCrae, J., Anal.
Lett., 9, 45 (1976).
5. Gerke, C. W., Nakamoto, H. and R. W. Zumwalt, J. Chromatog., 45, 24
(1969).
6. Pellizzari, E. D., Bunch, J. E., Berkley, R. E., and J. Bursey, Biomed.
Mass Spec., 3, 196 (1976).
7. Pellizzari, E. D., Bunch, J. E., Bursey, J. T. and R. E. Berkley, Anal.
Lett., 9, 579 (1976).
8. Eight Peak Index of Mass Spectra, Vol. I (Tables 1 and 2) and II (Table
3), Mass Spectrometry Data Centre, Aldermaston, Reading, RG74PR, UK,
1970.
9. Registry of Mass Spectral Data, ed. by E. Stenhagen. 4 Vol., John
Wiley & Sons, New York, 1974.
67
-------
APPENDIX A
VOLATILE ORGANICS IDENTIFIED AND QUANTIFIED IN AMBIENT AIR
68
-------
Table 18. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
FROM BALTIMORE, MDa
Chromato-
graphic
Peak No.
1
2
3
4
5
6
7
8
9
10
10A
11
12
13
14
15
ISA
16
16A
17
18
19
20
21
22
23
23A
24
25
25A
26
26A
27
28
29
30
31
32
33
34
35
36
37
Elution
Temp. Compound
CO
73
75
80
89
96
98
99
101
103
106
110
110
111
113
114
116
118
118
119
119
124
126
127
129
131
132
134
135
136
138
140
142
142
144
146
149
151
155
156
158
160
162
163
166
tr ichlorof luor ome thane
C.H. , isomer
5 12
nethylene chloride
trimethylsilanol (BKG)
unknown
chloroform
l-chloro-2-raethylpropene
3-chloro-2-methylpropene
C.H., Isomer
1,1,1- tr ichloroethane
benzene
carbon tetrachloride
C5H16 isomer
C_H. , isomer
C-IL, isoraer
hexamethyldisiloxane
dibromome thane
trichloroethylene
C-H. , isomer
C,H, . isomer
7 14
C8H18 lsomer
CyHj, isomer
1 , l-dichloro-2-methylpropane
(tent.)
C0H, „ isomer
• 8 18
CglU, Isomer
2,3-dichlorobutane (racemic)
toluene
CgH.g isomer
2,3-dichlorobutane (meso)
CjjH.g Isomer
CgH.g Isomer
tv-octane
n-nitrosodlnethylamine
tetrachloroe thy lene
dichlorobutene isomer
l,3-dichloro-2-raethylene pro-
pane (tent.)
chlorobenzene
ethylbenzene
£-xylene
dibromochlorofluoromethane
styrene
p_-xylene
n-nonane
C1QH22 isomer
Chroma to-
graphic
Peak No.
38
39
40
41
42
43
43A
44
45
46
47
47A
48
49
49A
50
51
52
52A
53
53A
54
55
56
57
58
59
60
61
62
63
64
65
66
66A
66B
67
69
70
71
72
73 *
74
75
(continued)
69
Elution
Temp . Compound
167
170
171
172
173
174
174
176
178
180
181
181
185
186
186
187
188
190
190
191
191
191
192
193
194
196
197
198
199
201
202
204
205
207
207
208
208
210
211
212
213
214
215
216
isopropylbenzene
ClnH,, isomer
10 22
C_H.g isomer
trichloropropane isomer
(tent.)
trichlorobutane isomer (tent.)
C.-alkyl benzene
C10H22 lsomer
C.-alkyl benzene
C--alkyl benzene
C10H22 lsomer
n-decane
C.-alkyl benzene
m-dichlorobenzene
C11H24 isomer
C.-alkyl benzene
C,-alkyl benzene
C.-alkyl benzene
o-dichlorobenzene
CqHj. isomer
C.-alkyl benzene
trimethylphenoxysilane
C.-alkyl benzene
C.-alkyl benzene
C-.H-. isomer
11 24
C.-alkyl benzene
C.-alkyl benzene
C,— alkyl benzene
C10H12 lsomer
o-undecane
methylene dioxytoluene isomer
(cent.)
C.-alkyl benzene
C.-alkyl benzene
C.-alkyl benzene
C.-alkyl benzene
C11H22 lsomer
C12H26 lsomer
C^.H.g isomer
C10H12 isomer
C.-alkyl benzene
C.— alkyl benzene
^-butylcyclohexane
C,-alkyl benzene
trichlorobenzene isomer
n-dodecane
-------
Table 18 (.conf d)
Chromato- EluCion
graphic Temp. Compound
Peak No. (°C)
76
77
78
79
80
81
82
83
217
218
220
225
226
228
230
230
naphthalene
C. ,H,0 isomer
13 28
C,-alkyl benzene
o
C,-alkyl benzene
0
C, ,H-, isomer
13 26
C,,H_, isomer
13 26
C..H.. is oner
n-tridecane
isomer
isooer
Chrotnco- EluCion
graphic Temp . Comoound
Peak No. (°C)
Ambient air sampled at site 1 (Fig. 1) on 10/14/75 from 1100-145Q hr (Table
10).
70
-------
Table 19. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
FROM BALTIMORE, MDa
Ciiromaco-
graphic
Peak No.
5
5A
6
6A
6B
6C
7
8
9
10
12
12A
12B
13
14
15
16
17
19
20
21
22
23
24
25
26
27
28
30
31
32
33
34
35
36
37
38
39
40
41
41A
42
43
44
45
46
Elution
Temp . Compound
73
74
77
83
85
88
92
95
98
100
105
108
109
112
114
115
116
118
121
126
128
129
130
131
134
136
138
141
143
145
146
148
149
150
151
153
154
156
157
158
160
162
163
164
166
168
chloroethane
crichlorof luoromethane
n-pentane
CjHjn isomer
methylene chloride
acetone
triaethylsilanol
C,H, , isomer
C,H-4 isomer
chloroform
C,H,2 isomer
1,1, 1-tr ichloroethane
C_H. , isomer
benzene
C-H.g isomer
C7H., isomer
C-H. , isomer
hexamethyldisiloxane
C-Hj, isomer
C-jKj- isomer
dimethylpentene isomer
C-H., isomer
C-H1 , isomer
CgH. , isomer
hexanol isomer
toluene
CgH.g isomer
CgH. , isomer
n-oc tane
m/e 74 (DMN) trace
tetrachloroethylene
CgH.Q isomer
C.99. isomer
SH20 lsomer
CnH, , isomer
chlorobenzene
C9H18 isomer
ethylbenzene
CgH-g isomer
£-xylene
dlbromochloromethane
styrene
o_-styrene
n-nonane
C10H20 isomer
CgH.g lsomer
Chroma to-
graphic
Peak No.
47
48
49
50
51
52
53
54
56
57
57A
58
59
60
61
62
63
64
65
66
68
69
70
71
72
73
74
75
76
77
78A
79
80
81
83
84
85
86
87
89
90
91
92
93
94
95
(continued)
71
Elution
Temp . Compound
169
171
172
173
175
176
177
178
179
180
180
183
185
186
187
189
190
191
191.5
192
193
194
196
198
198
199
201
203
204
205
206
207
208
210
211
211
213
215
216
217
217.5
220
221
222
224
225
isopropylbenzene
C10H22 lsomer
CgH18 isomer
cyclohexanone (tent.)
ri-propylbenzene
m-ethyltoluene
£-ethyl toluene
1,3, 5- triiaethylbenzene
C10H20 lsomer
1,2,4-tricethylbenzene -'
o-ethyl toluene
o-decane
C.-alkyl benzene
C.-alkyl benzene
C11H24 isomer
1,2, 3- trimethy Ibenzene
C,,H,. isomer
11 24
m-dichlorobenzene
C. nH./. isomer
trlmethylphenoxysilane
C,-alkyl benzene
C.-alkyl benzene
acetophenone
C.-alkyl benzene
C,-alkyl benzene
C10H12 i30mer
n-undecane
C11H22 isomer
C12H26 lsolner
C.-alkyl benzene
C.-alkyl benzene
3,4-dimethoxyacetophenone
C.-alkyl benzene
C11H22 isol!ier
C12H26 isomer
C12H26 isomer
C10H12 tsoiaer
C.-alkyl benzene
C.-alkyl benzene
C,-alkyl benzene
o-dodecane
naphthalene
C13H28 I300ier
C.-alkyl benzene
C. oH_fl isomer
Cg-alkyl benzene
-------
Table 19 (cont'd)
Chfjmaco-
jrapnic
Peak No.
96
97
98
Eluclon
Teinp .
CO
228
230
230
Compound
C1AH30 isomcr
C13H26 isomer
n-Cridecane
Chromaco- Elution
graphic Temp. Compound
Peak No. (°C)
Ambient air sampled at Site 2 (Fig. 1), Patapsco Sewage Treatment Plant on
10/16/76 from 1000-1350 hr, see Table 10 for sampling protocol.
72
-------
Table 20. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
FROM BALTIMORE, MDa
Chroma co-
graphic
Peak No.
1
2
3
3A
3B
4
4A
5
5A
6
7
8
9
10
10A
11
11A
12
13
14
15
16
16A
17
18
19
20
21
21A
22
23
23A
24
24A
25
26
27
28
29
30
31
32
33
34
35
35A
Elution
temp.
53
56
59
60
62
63
64
72
73
75
76
78
80
81
82
87
87
88
90
94
95
97
98
99
101
103
105
107
107
110
111
111
113
113
116
117
119
120
123
124
126
128
129
131
133
134
Compound
£- propane
SO,
C4H10 ls°mer
chloroethane
2-methylpropane
n-butane
2-butene
isopentane
CFC13
C_Hin isomer
5 10
n-pentane
C5H10 isomer
C.H,. isomer
5 10
methylene chloride
acetone
isopropanol
t^butanol
C,H, . isomer
o 12
trlmechylsilanol (BKG)
3-methylpentane
C,H.- isomer
6 12
n-hexane
2-methyl-3-butyn-2-ol (tent.)
chloroform
l-chloro-2-methylpropene
3-chloro-2-methylpropene
methylcyclopentane
2-butanone
1,1, 1- trichloroethane
C,H isomer
o 10
benzene
cci4
cyclohexane
2 , 3-diamethylpentane
C_H.- isomer
C-Hj, isomer
trichloroethylene
n-heptane
C.H. , isomer
C.H, , isomer
7 14
CqH,8 isomer
C-H. , Isomer
C-H, , Isomer
7 14
CflH18 Isomer
C8H18 *somer
2, 3-dichlorobutane (rac.)
Chroma co-
graphic
Peak No.
36
37
37A
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
62A
62B
63
64
65
66
67
68
69
69A
70
71
72
73
74
75
76
(continued)
73
Elution
Temp . Compound
ro
134
137
138
140
142
143
144
145
147
148
149
150
151
152
156
157
160
161
162
163
165
166
168
169
170
171
172
173
173
173
174
175
176
177
178
179
182
182
184
185
186
188
189
190
190
toluene
CjjHjo isomer
2,3-dichlorobur.ane (meso)
C8H16 isomer
CgH,g isomer
ii-octane
CgH. ., isomer
tetrachloroethylene
C.Hj. Isomer
C.H.. isomer
9 20 .'
C.H2_ isomer
C9H18 lsomer
C.H.n Isomer
9 20
chlorobenzene
ethylbenzene
m_, p_-xylene
C.H.. isomer
cyclooctatetraene
o_-xylene
n-nonane
C.H. . Isomer
9 18
COHIO isomer
CgH.g isomer
isopropylbenzene
C10H22 ^soner
C10H22 lsomer
C9H18 ls°mer
1 , 4-dichloro- 2-butene
1,.2,3-trichloropropane (Cenc.)
1, 1, 3, 3-tetrachloro- 2-methyl-
propane (tent.)
o-propylbenzene
benzaldehyde
m-ethylcoluene
1,3, 5-trimethylbenzene
C10H20 Is0mer
^-ethylroluene
1,2, 4-trlmethylbenzene
£-decane
C10H20 lsomer
D-dichlorobenzene
C^-alkyl benzene isomer
1,2, 3-tr imethy Ibenzene
limonene
£-dichlorobenzene
C.H._ Isomer
-------
Table 20 (cont'd)
Chroraato-
graphic
Peak No.
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
Elation
Temp . Compound
CO •'
191 C,-alkyl benzene isomer
192 C -alkyl benzene isomer
193 C, -alkyl benzene isomer
194 C..H,, isomer
11 24
195 C.-alkyl benzene isomer
197 C.-alkyl benzene isomer
198 C10H18 isomer
199 C.-alkvl benzene isomer
4
200 n-undecane
201 cnH22 isomer
202 cuH22 isoner
203 C.-alkyl benzene isomer
204 C.-alkyl benzene isomer
205 C.-alkyl benzene isomer
207 C.-alkyl benzene Isomer
209 CXOH12 iaomel
210 cnH92 isomer
211 C.-alkyl benzene isomer
211 C.-alkyl benzene isomer
212 C.-alkyl benzene isomer
213 C.-alkyl benzene isomer
214 C.-alkyl benzene isomer
215 C,-alkyl benzene isomer
o
217 n-dodecane
218 naphthalene
220 Cg-alkyl benzene isomer
220 Cg-alkyl benzene Isomer
isothermal
104
105
107
Bkd
Bkd
220 Bkd
isothermal
108
109
110
111
112
Bkd
Bkd
Bkd
Bkd
Bkd
Chromato- Elucion
graphic Temp . Compound
Peak Mo. (°C)
Ambient air sampled at Site 1 (Fig. 1)
Table 10 for sampling protocol.
on 10/14/76 from 2300-0250 hr, see
74
-------
Table 21. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
FROM BALTIMORE, MDa
Chromato-
graphic
Peak No.
1
2
2A
2B
2C
2D
3
5
6
7
8
9
10
10A
11
12
12A
13
14
15
ISA
16
16A
17
18
18A
19
20
21
21A
22
23
23A
24
25
25A
25B
26
26A
27
27A
28
28A
29
29A
30
Elution
Temp.
67
73
75
76
76
77
78
82
86
92
96
97
99
100
101
103
104
105
106
107
108
109
110
113
114
115
117
118
119
120
122
123
124
125
126
126
128
129
130
131
132
132
133
134
135
136
Compound
acecaldehyde
isopentane
CrH.g isomer
furan
C-H,_ isomer
3 10
o-pentane
acetone
d Ichloromethane
carbon disulphide
2-methylpentane
3-nethylpentane
C,H._ isoner
D i£
iv-hexane
C,Hn isoner
6 12
chloroform
C?H16 isomer
3-methylfuran
C-H. , isomer
7 16
C-H, isomer
7 16
mechylcyclopentane
C-H. , isomer
/ JLo
cyclohexadiene or C£H10 isomer
O .Lo
1,1, 1-trichloroethane
hexadiene isomer
benzene
cci4
2-methylhexane and cyclohexane
2, 3-dimethylpentane
3-methylhexane
C,H1 , isomer
dlmethylcyclopentane isomer
C-H. isomer
/ lo
Cr ichloroe thy lene
it-hep cane
c7Hj, isomer
C7H.2 isomer
C7H. , isomer
C8H16 lsomer
CgH.g Isomer
CgH. - isoner
C8H16 lsomer
methylcyclohexane
C8H16 i30ttui*
CgH. s isomer .
C8H18 lsomer
CgH., Isomer
Chroma to-
graphic
Peak No.
31
32
33
33A
34
35
35A
36
36A
36B
37
37A
37B
38
39
40
40A
41
42
42A
43
43A
43B
44
45
46
46A
47
48
49
50
50A
SOB
51
52
53
54
55
56
56A
57
58
58A
(continued)
75
Elution
Temp . Compound
137
138
141
142
143
146
148
149
150
151
152
152
153
154
155
156
157
158
159
159
160
162
163
164
165
167
168
169
170
171
172
173
175
176
177
179
180
181
183
183
184
185
187
trimechylcyclopencane
isomer
CgH.g isomer and trimethylcyclo-
pentane isomer
toluene
C0H10 isomer
8 18
CgH.g Isomer
CgH., isomer
C8H16 lsomer
o-occane
N-niCrosodimechylamine
CgHj, isomer
tecrachloroechylene
CoH1 , isomer
CnH, „ isomer
9 18
C9H20 isolner
CgH20 isomer
C.H... isomer
C_H, 0 isomer
9 18
C-H,. isomer
9 20
ethylcyclohexane + CgH
isomer
chlorobenzene
CgH.g isomer
CgH2- isoner
CgH.g isomer
echylbenzene
£-xylene
m-xylene
CgH18 isomer
styrene
&-xylene
n-nonane
C-H^- Isomer
C10H22 lsomer
C10H22 isomer
C10H20 lsoiner
fcrace)
18
isopropylbenzene + cioH?2
isomer
C.-H-. isomer
C10H20 lsoiner
C10H20 isomer
n-propylbenzene
C10H22 l30mer
m-ethyltoluene
C._H.- isomer
C10H22 isomer
-------
Table 21 (cont'd)
Chroraj co-
graphic
Peak No.
59
59A
60
61
62
62A
63
64
65
66
67
68
Elucion
Temp.
188
190
191
192
193
194
195
196
197
199
201
204
Compound
C11H24 lsomcr
C10H20 ls°mer
1,2, 4-erimechylbenzene +
n-decane
C11H24 ls°mer
C. ,H-, isomer
C11H22 isoaer
Clia24 i*omer
C11H'2 lsomer
C11H24 isoiner
C.2H,, isorser
C12H26 isomer
C11H24 isomer
Chromaco- Elucion
graphic Temp. Compound
Peak So. (°C)
•'
f
Ambient air was sampled 15 ft from dimazine facility at Site 1 (Fig. 1) on
11/19/75 from 1400-1600 hr, see Table 10 for sampling protocol.
76
-------
Table 22. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
FROM BALTIMORE, MD*
Chroma co-
graphic
Peak No.
1
1A
2
2A
3
3A
4
5
5A
6
7
8
9
10
11
12
13
14
15
16
16A
17
17A
18
19
20
20A
21
22
23
23A
24
24A
25
25A
26
26A
26B
26C
27
27A
28
29
30
31
Elution
Temp.
58
65
66
67
72
74
76
77
79
80
81
84
88
94
93
99
101
103
105
106
108
109
111
112
114
115
116
117
118
119
121
122
122
123
123
124
125
126
127
128
129
130
132
133
134
Compound
co2
1-butene
n-butane
2-butene
acetaldehyde
CCH, „ isomer
5 10
isopentane
C,H1n isomer + furan
5 10
C.H.Q isomer
n-pentane
acetone
dichloromethane
carbon dilsulphide
methyl ethyl ketone
2-methylpentane
C6H12 lsotner
n-hexane
chloroform
C_H,g isoraer
C,H. , isomer
6 12
pentanone isomer
methylcyclopentane
methylcyclopentadiene
1, 1, 1-trichloroe thane
C.-H.,, isomer
benzene
carbon tetrachlorlde
2-methylhexane
cyclohexane
3-methylhexane
C-H.g isomer
dimethylcyclopentane isomer
2-pentanone
C,H, , isomer
/ xo
3-pentanone (tent.)
trlchloroethylene
it-heptane
C,H, . isomer
7 14
C-Hj. isomer
C7H14 lsonier
CgHj. isomer
methylpentanone Isomer and
C8H18 lsomer
me thy Icy c lohexane
CQH., Isomer
o lo
C8H16 lsomer
Chromato-
graphic
Peak No.
32
33
33A
333
34
34A
35
36
37
37A
37B
38
39
40
41
42
43
43A
44
44A
45
46
47
48
49
49A
50
51
52
53
53A
54
55
56
57
58
59
60
60A
61
62
62A
63
64
(continued)
77
Elation
Tenio . Compound
CO
136
137
138
139
140
140
142
145
148
149
149
151
152
153
154
156
157
158
159
160
161
163
166
167
168
169
170
174
175
176
177
178
179
180
181
183
185
186
187
188
189
189
190
192
trimethylcyclopentane
C..H-, isomer
C8H18 isomer
C-H „ isomer
toluene
C0H, „ isomer
8 18
CoH._ isomer
C0H,. isomer
8 16
n-octane
N-nitrosodimethylamine (trace)
C8H16 ls°mer
tetrachloroethylene
C9H18 lsomer
CqH7- isomer
C9H20 tsomer
CgH2Q isoraer
C9H20 isomer
CqHTfl isomer
chlorobenzene
C-H..- isomer
9 18
ethylbenzene
£-xylene
C9H20 tsoner
cyclooctatetraene
m-xylene
C9H18 isomer
£-xylene
C10H22 lsomer
isopropylbenzene
C10H20 lsoner
C10H22 isonier
C10H20 lsolner
C10H16 lsonier
^-propylbenzene
m-ethyltoluene
C10H22 i30mer
C10H22 lsomer
C10H22 lsomer
a-methylstyrene and C.-H,-
isomer
1,2, 4-trlmethylbenzene
Cj-H._ isomer or n^-decane
C11H24 lsomer
m-d ichlorobenzene
C11H24 iaomsT
-------
Table 22 (cont'd)
Chroma cc-
graphic
Peak No.
65
66
67
67A
68
69
70
71
71A
72
73
73A
73B
74
75
77
78A
79
80
Elucion
Temp.
193
194
196
197
198
199
200
202
203
204
205
205
206
207
208
211
215
217
219
Compound
C,.H,4 isomer and 1,2,3-
trinethylbenzene
C11H24 isoaier
C11H22 isomer
indane
C11H24 isomer and indene and
sec-bucylbenzene
isobutylbenzene and o-cymene
C11H24 lsomer
C11H24 isomer
C,-alkyl benzene isomer
C11H22 isomer
C11H24 isomer
C,-alkyl benzene isomer
ethylstyrene isomer and
C10H22 lsoBler
C11H24 isomer
C12H26 lsomer
C12H26 lsoner
C12H24 iaomcr
C. rJSi^f isomer
C12H26 isomer
Chromaco- Elucion
graphic Temp . Coaioound
Peak So. (°C)
t
Ambient air was sampled near dimazine facility at Site 1 (Fig. 1) on 11/24/75
from 1355-1555 hr, see Table 10 for sampling protocol.
78
-------
Table 23. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
FROM BELLE, WVa
Chromaco-
graphic
Peak No.
1
2
3
4
4A
5
6
7
8
8A
9
10
11
12
13 -
13A
14
14A
15
16
17
18
19
20
21
21A
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
Elution
Temp.
63
66
68
68
68
68
74
81
82
83
86
90
101
104
106
107
108
109
114
116
118
118
120
122
124
124
126
126
127
129
130
131
136
138
139
140
141
142
145
146
147
148
150
151
152
154
Compound 'Jg/m
CF2C12
chloromethane
£- propane
vinyl chloride -2-4,000
dimethyl ether
acetaldehyde -9,800
o-butane
isopentane
acetone
crichlorof luoromechane
diethyl ether
methylene chloride 8,700
trimethyl silanol
3-nethylpentane
ji-butanol
3, 3-dimethyl-2-butanol
iv-hexane
CHC13
C-H,, isomer
/ ID
C,H, . isomer
o L£
1,1, 1-trichloroethane
C.H.. isomer
m/e 73
benzene -.400,000
C_H,, isomer
CCl^
cyclohexane
silane compound (BKG)
silane compound (BKG)
C.IL, isomer
trichloroethylene
methyl methacrylate
C.H. „ isomer
8 18
CyHj, isomer
C8H18 is0lner
C-H, , isomer
C.H,, isomer
8 16
C8H16 ls°mer
toluene
CgH.g Isomer
CgH,8 isomer
dimethyl formamide -76,700
C-H,, Isomer
o lo
jn-oc tane
tetrachloroethylene
C9H20 lsomer
Chroaaco-
graphic
Peak Xo.
42
42A
43
44
45
46
47
48
48A
49
50
51
52
53
54
55
56
57
57A
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
(continued)
79
Elucion 3
Temp. Compound -g/n>
156
157
160
162
163
164
166
168
168
169
170
174
175
177
179
180
180
182
182
184
185
186
189
190
191
192
194
195
196
199
201
202
203
204
206
208
209
210
211
213
214
214
214
215
215
215
C-H OH isomer
CgH,,0 isomer
C8H12 isomer
ethylbenzene
CgH— isomer
2-xylene
C.H... isomer
cyclooctatetraene
styrene
£-xylene '
ii-nonane
C9H18 is°mer
isopropylbenzene
C10H20 *-soner
CgH..,. isomer
C-H.g isomer
CgHjo isomer
m-ethyltoluene
benzaldehyde
p_-ethyl toluene
hexyl methacrylate
C, -alkyl benzene isomer
o-ethyl toluene
jn-decane
C10H20 isomer
jn-dichlorobenzene
C11H24 isomer
C.-alkyl benzene Isomer
C11H24 isomer
C, -alkyl benzene Isomer
C,-alkyl benzene isomer
acetophenone
C,,H_. isomer
11 24
C,— alkyl benzene isomer
C,-alkyl benzene Isomer
n-undecane
C,_H_- isomer
12 26
C12H26 1SOlner
C,-alkyl benzene Isomer
C,-alkyl benzene isomer
Cr-alkyl benzene Isomer
C, -alkyl benzene isomer
C12H26 lsomer
C10H12 i30mer
C,-alkyl benzene Isomer
C12H24 l90mer
-------
Table 23 (cont'd)
Chromato-
graphic
Peak No.
85
86
87
88
89
£lucion
Temp.
216
216
217
220
220
C12H,4 is
Compound tg/a
iomer
Chromato- Elution
graphic Temp. Compound ^g/m
Peak No. (°C)
n-dodecane
naphthalene
Cg-alkyl
benzene isomer
J
ii-cridecane
Ambient air was sampled at location No. 8, see Table 13 for protocol,
80
-------
00
27 30
TIME (MIN)
Figure 12. Total ion current profile of ambient air sample taken at location
no. 9 on Union Carbide property. See Tables 13 and 24 for protocol
and listing, respectively.
-------
Table 24. VOLATILE ORGANIC VAPORS IN AMBIENT AIR
FROM SOUTH CHARLESTON, WVa
Chroaiato-
graphic
Peak No.
1
2
3
4
5
6
7
8
9
9A
9B
10
11
12
13A
14
15
16A
16B
16C
17
18
19A
19B
19C
20
21
22
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
Elation
Temp.
52
54
63
65
65
69
71
78
79
80
80
83
87
95
98
99
101
104
105
106
112
115
119
119
120
122
123
123
125
126
128
131
134
135
136
137
138
140
142
144
147
150
151
152
153
154
Compound ng/m
N2 + °2
4
propane
vinyl chloride
acetaldehyde
n- butane
methyl amine (tent.)
isopentane
diaethyl ether ~\
propanal \
acetone J
diethyl ether
methylene chloride
C,H. , Isomer
6 14
C,H. . isomer
trac =
>~ 200, 000
y-butyrolactone (tent.) 3,750
3-methylpentane
n-hexane
chloroform ^
ethyl acetate J
C,H,- isoaer
>-175,000
1,1, 1-Crichloroethane
benzene
carbon tetrachloride
cyclohexane
C-H., isomer
C-H.g isomer
CyHj, isomer
C7H14 lsomer
trichloroethylene
n-heptane
CgH-8 isomer
CgH.g isomer
C-H. . isomer
C8Hlfl isomer
C.H,, isomer
a lo
C-H,, isomer
o lo
C8H16 iaomer
toluene
C8H18 lsomer
CgH. , isomer
n-octane
C8H16 lsomer
CgH-- isomer
tetrachloroethylene
CgH2Q isomer
j >-200,000
.
tiroaato-
raphic
eak No.
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65A
65B
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
(continued)
82
Elution
Temp.
CO
155
156
158
160
161
163
164
165
167
169
170
170
172
175
176
178
180
181
182
183
184
186
187
190
190
193
194
195
196
197
198
199
200
201
202
203
205
206
207
208
209
211
212
213
214
215
Compound ' ng/n
CgHjo isomer
CgH-- isomer
C.H18 isomer
CgH. , isomer
C.H., isomer
ethylbenzene
CgH,- isomer
£-xylene
CgH-Q isomer
styrene
o^xylene
n-nonane
CgH18 Isomer
CQH10 isomer
9 18
cumene
C10H22 lsocer
C10H20 isoner
alpha-pinene
ii-propylbenzene
m-ethyltoluene
1,3, 5- tr imethylbenzene
C10H22 isomer
o-echylcoluene
1, 2, 4-tr imethylbenzene
n-decane
m-dichlorobenzene
C.-alkyl benzene isomer
1,2, 3- tr imethylbenzene
C11H24 lsoner
C11H22 lsomer
C10H20 lsoaier
C.-alkyl benzene isomer
C.-alkyl benzene Isomer
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C11H24 l80ner
C.-alkyl benzene Isomer
C10H18 lflomer
Cj-H.j isomer
n-undecane
C.-alkyl benzene isomer
C12H26 lsoner
C.-alkyl benzene isoner
C.-alkyl benzene isomer
C.-alkyl benzene Isomer
C,-alkyl benzene isoner
-------
Table 24 (cont'd)
Chroma co-
graphic
Peak No.
87
38
89
90
91
92
93
Elution
Temp.
217
219
220
220
220
220
220
Compound ng/m
Cj-alkyl benzene isocier
C10K12lisomer (cent.)
C_-alkyl benzene isomer
n-dodecane
C..H.,, isomer
C.-alkyl benzene isomer
n-tridecane
Chroma co- Elucion ,
graphic Temp. Compound ng/a
Peak No. ('C)
Ambient air sampling was at location No. 9, see Table 13 for protocol,
83
-------
oo
KX>r
a 21
44 06 68 8O 92 104
12 15 16 2i M
TEMPERATURE PC)
116 128 140 192
75
T4
T3
79
A
K4 ITS
200 212 220 22O 220
27 JO
TIME (MINI
M sr
Figure 13. Total ion current profile of ambient air taken at Interstate 60 and
WV 25 in Nitro, WV. See-Table 13 and 25 for protocol and listings,
respectively.
-------
Table 25. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
FROM NITRO, WVa
Chromato-
gr.iph.ic
Peak No.
1
2
3
3C
3D
4A
4B
5
6
7
8
9
9C
10
11
12
13
14
ISA
16
17
ISA
18B
19
20
21A
21B
22
23
24
25A
25B
26
27
28
29
30
31
32
33
34
35
36
37A
37B
38
ilucion
Temp.
55
56
62
64
65
68
68
69
70
71
75
79
82
84
85
86
89
92
100
103
106
108
111
113
116
120
123
124
125
127
128
128
129
135
137
138
140
142
145
146
149
152
153
155
160
165
Compound ng/a
N2
co2
S02
chloromethane
propane
winyl chloride -50,000
2-methylpropene
acetaldehyde
n- butane
2-butene
C.H.. isomer
isopentane
acetone ?~ 125, 000
C.H., isomer
5 12
diathyl ether
propanal
methylene chloride ^-75,000
carbon dilsulphide
C,H., isomer
3-methylpentane
n-hexane
chloroform -39,000
ethyl acetate
C,H, . isomer
6 12
1,1, 1-trichloroethane
benzene ?- 150, 000
cyclohexane
C,H,, isomer
7 16
C-H.g isomer
C-H. , isomer
C,H, , isomer
7 lo
trichloroethylene
tt-heptane
C.Hjo isomer
CyHj, isomer
C-H., isomer
C.H., isomer
C8H18 l30mer
toluene
CaH., isomer
8 16
CgH,, isomer
C8H18 lsomer
C8H16 l30qier
tetrachloroethylene
chlorobenzene -
ethylbenzene
Chroaaco-
graphic
Peak No.
39
40
41
42
43
44
45
46
47A
47B
4SA
48B
49A
49B
50
51
52A
52B
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
Elution 3
Temp. Compound ng/m
("Cl
167
170
172
173
175
176
178
180
181
181
181
184
185
185
187
189
192
192
195
196
197
198
200
200
202
203
204
205
207
207
208
209
211
212
215
215
217
218
220
74 isothermal
75
76
77A
77B
78
79
£-xylene
CgH.g isomer
£-xylene
ji-nonane
anisole
C10H22 isomer
curaene
C10H22 is0mer
C9H18 ls°ner
C10H20 isoner '
CgH.g isomer
benzaldehyde
C.-alkyl benzene isomer
C,-H,, isomer
10 22
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C^-alkyl benzene isomer
n-decane
m-dichlorobenzene
C.-alkyl benzene Isomer
C.-alkyl benzene isoner
C11H14 lsomer
o-dichlorobenzene
C,.H-. isomer
10 20
C.-alkyl benzene isomer
C,-alkyl benzene isomer
C.-alkyl benzene isomer
C..H.. isomer
11 24
C.-alkyl benzene Isomer
C.-alkyl benzene isomer
C.-alkyl benzene isomer
o-undecane
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C,-alkyl benzene isomer
C.-alkyl benzene Isomer
C.-alkyl benzene isomer
C12H26 lsomer
C.-H., Isomer
10 12
C12H26 lsoner
1,2,3, 4-tetrahydronaphthalene
ri-dodecane
naphthalene
C13H28 isomer
n-tridecane
Ambient air sampling was at location No. 15, see Table 13 for protocol.
85
-------
Table 26. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR NEAR
KIN-BUG CHEMICAL DISPOSAL SITE, EAST BRUNSWICK, NEW JERSEY3
Chroraaco-
graphic
Peak No.
X
2
3
3A
4
5
6
7
7A
8
9
10
10A
11
12
12A
13
14
15
16
17
17A
17B
18
ISA
18B
19
20
21
22
23
24
25
26
27
28
28A
29
30
30A
31
Elution
Temo. Compound ug/m
rc>
59 CO,
£
64-6 difluorodichloromethane
68 n-propane
72 1-butene
73 n-butane
78-82 acetaldehyde 249
84 isopentane
86 trichlorofluoromethane
89 n-pencane
90 C5H1Q isoner
93 dichloromethane 125
96 CfiHi4 isomer
104 2-methylpentane
104 3-methylpentane
107 C-H, , isomer
6 12
108-110 diethyl ether
108-111 perfluorobenzene (eS)
110 n-hexane
108-120 ethanol
112-113 chloroform
115-116 perfluorotoluene (eS)
118 methylcyclopentane
120 C,H100 isoaer
123 1, 1, 1-trichloroethane
124-5 benzene 200
125 CC14 20
126 cyclohexane
128 C7Hi6 isomer
129 allyl acetate (tent.)
130 C7Hi4 isomer
132 C-H, , isomer and trlchloro- 9
7 lo
ethylene
133 ti-heptane
135 C5H1Q0 isomer
138 C8His lsomer
140 methylcyclohexane
143 CgHlo isomer
145 caHi8 isomer
148 toluene
149 C8H18 isomer
152 C8H16 isomer
153 methyl isobutyl ketone
154 n-octane
156-7 hexamethylcyclotrisiloxane
157-8 tetrachloroethylene
158 C9H2Q isomer
hroinato-
raphic
>eak No.
32
33
34
35
36
36A
37
38
39
40
40A
41
42
42A
43
44
45
46
47
48
49
52
53
54
55
56
57
58
59
60
61
62
62A
63
64
67
68
69
70
71
72
73
(continued)
86
Elucion
Tenp.
Co
164
167-8
168-9
172-3
173-5
177
179
181
185
186
187
188-192
189
190
191
191
192-3
196
198
203
205
206-8
210
217
219
221
225
227
230
232
235
236
239
240
240
240
240
240
240
240
240
240
240
240
Compound .g:=
chlorobenzene
sthylbenzene
p_-xylene
styrene
o-nonane and o-xylene
C10H20 is°mer
isopropylbenzene
C10H22 lsomer
n-propylbenzene
m-ethyltoluene
C.gH,, isomer
benzaldehyde and phenol 3
silane conpound
o-ethyltoluene
C..H-. Isomer
11 22
1-d scene
a-decane and 1,2,4-trimethyl-
benzene
C11H22 isomer
C,-alkyl benzene isomer
C..H.. isomer
C.-alkyl benzene isomer
acetophenone
n-undecane
C.-alkyl benzene isomer
silane compound
ethyl phenol isomer
n-dodecane
naphthalene
methyl ethyl phenol isomer
4-isopropylphenol
C.-alkyl phenol isomer
methyl-l,2-dihydronaphthalene
isomer
C13H26 lsomer
ii-tridecane
C.-alkyl phenol
S-methylnaphthalene
a-methylnaphthalene
n-tetradecane and biphenyl
ethylnaphthalene isomer
dimethylnaphthalene Isomer "N
dimethylnaphthalene Isomer 1 ,QQ
dimethylnaphthalene isomer 1
dimethylnaphthalene isomer J
ii-pentadecane
-------
Table 26 (cont'd)
Chroraato- Elucion ,
graphic Temp. Compound -g/ra
Peak No. CO
74 240 6-phenylfulene (tent.)
Chroma co- Elution
graphic Temp.
Peak No. (°C)
Compound -g/n
Q
Ambient air was sampled during period No. 2, location No. 2, see Table 15 for
protocol.
87
-------
Table 27. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
NEAR KIN-BUG DISPOSAL SITEa
Chroaato-
graphic
Peak No.
1
2
2A
•4
4A
5
5A
6
7
3
8A
9
10
11
12
13
13A
14
15
16
17
18
ISA
19
20
21
22
23
24
25
26
26A
27
28
28A
28B
28C
29
30
31
32
Elucion
Temp.
64
72
73
78-82
84
86
88
89
92
94
97
100
104
108
110
113
114
116
121
125
126
128
130
131
133
140
144
145
148
150
152
153
153
156-7
159
161
163
165
168
169
170
Compound -g/m
difluorodichlorone thane
1-butene
n-butane
acetaldehyde
isopentane
trichlorofluorome thane
furan (tent.) and C_H.Q isomer
n-pentane
propanal (tent.)
dichloromethane 0.05
C-Hj. isomer and methyl •
disilane
C,Hn- isomer
6 12
2-eethylpentane
3-methylpentane
hexafluorobenzene and n-hexane
chloroform 15
diethyl ether
perf luorotoluene (eS)
1,1,1-trichloroethane 0.03
benzene and carbon tetra-
chlorlde
C-H., isomer and cyclohexane
3-methylhexane
allyl acetate (tent.) trace
C-H,, isomer
7 lo
trlchloroethylene and n-
heptane
methyl cyclohexane
CqH.g isomer
C8H16 isomet
toluene
C8H16 isomcr
C-H. , isomer and n-butyl
acetate (tent.)
2-hexanone
n-octane
hexamethylcyclotrisiloxane and trace
tetrachloroethylene
C9H18 isOI"er
CjHjQ isoner
C.U.g isomer
chlorobenzene
ethylbenzene
p_-xylene
CgH.,- isomer
hroraato-
raphic
eak Mo.
33
34
35
36
37
38
39
40
41
42
43
44
45
46
46A
47
48
49
50
51
52
53
54
55
55A
56
57
57A
58
59
60
62
63
64
65
67
68
69
70
71
72
73
74
Elucion
Temp.
ro
172
174
177
180
181
183
186
187
189
193-3
194
196
198
201
202
203
205
208
210
213
215
217
219
221
224
226
228
229
230
234
237
240
240
240
240
240
240
240
240
240
240
240
240
Compound -*.aj
cyclooctatetraene or styrene
o-xylene and n-nonane
silane compound
isopropylbenzene
C10H22 isomer
C.-alkyl cyclohexane isomer
n-propylbenzene
m-ethyltoluene
benzaldehyde and phenol and
silane compound <•
1,2,4-trimethylbenzene and 11-
decane
C..H,. isomer
11 24
dichlorobenzene (m or p_)
1,2, 3-tr ime thy Ibenz ene
o-dichlorobenzene
C11H22 isomer
C,-alkyl benzene isomer
C11H24 isODer
acetophenone
n-undecane
C12H26 isomer
C.-alkyl benzene isomer
silane compound
C12H24 isomer
C12H26 isomer
C12H24 isomer
rt-dodecane
naphthalene
C11H14 lsomer
dimethyl aniline (tent.)
C13H28 isomer
C,-alkyl benzene isomer
C13H26 tsomer
n-trldecane
8-me thy Inaphthalene
a-methylnaphthalene
C14H20 is
-------
Table 28. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
NEAR KIN-BUG DISPOSAL SITEa
Chromaeo-
graphlc
Peak No.
1
2
3
4
5
6
7
8
10
11
12
13
14
15
16
16A
17
18
19
19A
20
20A
21
21A
2 IB
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
Elution
Temp.
CO
64
73
75
81
84
87
89
94
104
107
110
113
116
121
125
126
128
131
132
135
140
143
147
148
151
153
155
160
164
166
167
169
171
172
175
178
181
184
185
186
187
188
190
Compound -g/n
dichlorodlf luoroir.echane
1-butene
n-butane
acetaldehyde
isopentane
trichlorof luoromechane
n-pentane and furan
dichloromethane 0.01
2-methylpentane
3-methylpentane
hexafluorobenzene and n-hexane
chloroform 20
perfluorotoluene (eS)
1,1,1-trichloroethane 0.05
benzene 0.90
cyclohexane and C-Hj. isomer
3-methylhexane
C,Hn . isomer
7 14
jn-heptane
CgH.gO Isomer
methylcyclohexane
n-propyl acetate (tent.) trace
toluene
CgH,g isomer
C.H., isoner
n-octane
hexamethylcyclotrisiloxane
and tetrachloroethylene
CgH2() isomer
chlorobenzene
ethylbenzene
£-xylene
C.H.. isomer
9 18
styrene
o-xylene and n-nonane
C10H22 isomer
isopropylbenzene
C..H-, isomer and C,-alkyl
10 22 J
cyclohexane
n-propylbenzene
n-ethyltoluene
benzaldehyde
silane compound
phenol ~8
1,2,4-trimathylbenzene and n-
decane
Chronaco-
graphic
Peak No.
40
41
42
43
44
45
46
47
48
49
50
50A
51
52
53
53A
54
54A
55
56
56A
57
57A
58
59
59A
60
61
61A
62
63
63A
64
66
67
69
70
Elution
Temo.
CO
194
196
199
200
201
201
203
203-5
206
207
208
209
210
212
215
216
217
217
219
221
222
224
225
226
229
230
232
234
235
237
240
240
240
240
240
240
240
Compound -5/0
m or £-dichlorobenzene and
ter-butylbenzene
1,2,3-trimethylbenzene
nethyl styrene isoner and sec-
butylbenzene
£-cymene
n-butylbenzene
C11H24 lsomer
£-propyltoluene
acetophenone and C.-alkjfl
benzene isomer
methyl indan isomer
n-undecane
C.-alkyl benzene isomer
C12H26 "lsomer
C^-alkyl benzene isomer
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C.-alkyl cyclohexane isomer
methyl Indan isoner
C12H24 lsomer
C.-alkyl benzene isomer and
C.-alkyl benzene isomer
C-2H0, isomer and Cg-alkyl
benzene isomer
Cg-alkyl benzene
n-dodecane
dimethyl indan isoxer
naphthalene
Cj-alkyl benzene and ci-t&2B
isomer
Cg-alkyl benzene isomer
C.-H,, isomer
13 26
C13H"6 lsoner and C.-alkyl
indan isomer
C11H16 isomer
C13H28 isomer
C13H2fi isomer
C.-alkyl indan isomer
jn-tridecane
S-me thy Inaph t ha lene
a-methylnaphthalene
C14H30 isomer
n_-cetradecane
Ambient air
protocol.
was sampled during period No. 3, location No. 2, see Table 15 for
89
-------
Table 29. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
NEAR KIN-BUG DISPOSAL SITEa
ChroTaato-
graphic
Peak No.
1
2
2A
3
3A
4
5
6
7
8
8A
9
10
11
12
13
14
15
16
17
18
ISA
19
20
21A
21
22
23
24
25
26
27
28
29
30
31
31A
32
33
34
35
36
Elucion
Temp.
68
72
74
76
77
80-6
88
90
92
93
96
98
99
100-3
108
111
113
114
116-7
120
122
124-6
128
129
130
131
132
134
135
137
142
144
147
149
150-4
156
158
160
161
164
168
170
172
174
176
Compound 'Jg/ra
dichlorodif luoromethane
so2
propane
1-butene
2- butane
acetaldehyde
isopentane
trichlorof luoromethane
C.HIO isomer
ii— pentane
C,H-_ isomer
dichloromethane trace
C,H. , isomer
3-methylpentane
2-methylpentane
CgH. - isomer
perfluorobenzene (eZ)
n-hexane
chloroform 45
perfluorotoluene (eS)
C6H12 lsomer
1,1,1-trichloroethane trace
benzene 15
CC1, trace
cyclohexane and C-H-, Isomer
C7H16 iSOlner
C7Hj< isomer
CyH.,, isoner
trichloroethylene 13
it-heptane
CgH18 isomer
methy Icyc lohexane
CgH16 isomer
C8Hig isomer
toluene 972
1-octene
n-octane
hexamethylcyclotrisiloxane
tetrachloroethylene
methyl ethyl cyclopentane
Isomer
chlorobenzene
ethylbenzene
£-xylene
CgH, , isomer
styrene or cyclooctatetraene
iromato-
raphic
eak No.
37
38
39
40
41
42
43
44
45
46
47
50
51
52
53
54
55
56
57
58
Elution
Temp.
CO
177
182
184
185
188
189
190
191
193
194-6
198
206
208
210
212
217
218
223
227
229
231-2
240
Compound ug/n
o-xylene and n-nonane
C10H22 lsomer
isopropylbenzene
n-propylbenzene
o-chlorotoluene 47
£-ethyltoluene
benzaldehyde
phenol
£-ethyltoluene
benzyl methyl ether '
benzyl chloride
C.-alkyl benzene
2,3-dihydrobenzaldehyde or
benzyl chloride
acetophenone and C.-alkyl
benzene and C.-H-.. isomer
ii-undecane and methyl benzoaee
dichlorotoluene isomer
silane compound
dichlorotoluene isomer
a-dodecane
naphthalene
methyl toluate isomer
methylnaphthalene isomer
*<*
Ambient air was sampled during period no.
for protocol.
90
4, location no. 5, see Table 15
-------
Table 30. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
NEAR KIN-BUG DISPOSAL SITE3
Chromato-
graphic
Peak No.
1
1A
IB
1C
2
3
3A
4
4A
5
6
6A
7
7A
8
9
9A
10
11
12
13
14
15
ISA
15B
16
17
18
19
20
21
21A
21B
22
22A
23
24
25
25A
26
27
27A
Elucion
Temp.
CO
64
73
74
75
77
80
84
86
88
89
90-2
92
92-6
98
100
101
102
104
105-8
109
110-11
112-114
116
117
117
118
119
120
124
126
128
129
130
131
132
133
134-6
137-8
139
140
141-4
144-6
Compound
ug/m3
dichlorodifluoromethane
1-butene
n-butane
2-butene
SO,
acetaldehyde
isopencane
trichlorofluoromethane
C-H10 isomer
n-pentane
vinyl methyl ether
bromoethane
dichlorome thane
l,l,l-trifluoro-2.2,2-
trichloroe thane
acetone
diethyl ether
methyl n-propyl ether
2-methylpentane
vinyl isopropyl ether
C6H14 isomer
perfluorobenzene (ej)
n— hexane
5,000
1,250
30
and 13,000
(ether)
chloroform and diisopropyl 266 (CHC1-)
ether
perfluoro toluene (eS)
methyl ethyl ketone
C,H, , isomer
6 12
ethyl acetate
1, 2-dichloroe thane
1, 1, 1-trichloroethane
benzene
cyclohexane and C..H.,
3-methylhe -ane
Isopropyl acetate
C,H. , isomer
/ ID
dibromomethane
trichloroethylene
ii- heptane
ethyl acrylate
l-chloro-2-bromoe thane
methyl mechacrylate
methyl cyclohexane and
propyl acetate
4-methy 1- 2-pentanone
1,1,2- trlchloroe thane
+120 (ether)
57
500
900
isomer
63
27
n-
260
Chromato-
graphic
Peak No.
28
29
30
30A
31
32
33
34
35
36
37
38
39
40
41
42
43
43A
43B
44
45
46
47
47A
48
48A
49
50
52
54
55
56
Elucion
Temp.
CO
147-50
152
154
155
157
160
163
164
167
168-9
171
173
174
176
176
178
180
181
183
184
185
186
187-8
189
190
192
193
195
197
198
202
206
208
210
240
Compound -g.z'
toluene 50
dimethylcyclohexane
n-octane
hexamathylcyclocrisiloxane
tetrachloroethylene 142
n-butyl acetate
methylethylcyclopentane isoner
chlorobenzene
ethylbenzene
£-xylene ,
CgH2Q isomer
styrene
o-xylene and n-nonane
C10H22 lsomer
C10H20 is0mer
C10H22 isORer
isopropylbenzene
C10H22 isomer
n_-propylcyclohexane
C10H22 isomer
C10H20 isomer
a-propylbenzene
m-ethyltoluene and trimethyl-
heptane isomer
C.-H,_ isomer and o-ethyl-
JLU if, ~~
toluene
C10H22 isomer
C..H-n isomer
10 20
ii-decane and 1,2,4-trimethyl-
benzene
C11H24 isomer
C,,H,. isomer and C.-alkyl
11 24 4 '
benzene
1,2,3-trimethylbenzene and
C..H-. isomer
11 24
C11H24 l30mer
C12H26 isomer
C,-alkyl benzene isomer and
acetophenone
C14H30 lsomer
naphthalene
Ambient air was sampled during period no. 4, location on the mound, see
Table 15 for protocol.
91
-------
Table 31. VOLATILE ORGANIC VAPORS IN AMBIENT AIR
NEAR KIN-BUG DISPOSAL SITE3
Chronaco-
graphic
Peak No.
1
3
3A
4
4A
4B
5
5A
5B
6
7
7A
8
8A
9
10
11
12
13
14
14A
15
16
16A
17
18
19
19A
20
21
21A
22
23
24
25
26
27
28
28A
29
30
31
31A
Elucion
Temp.
59
60
65
70
73
74
75
77
80
81
83
85
88
89
90
92
95
97
100
104
107
108
109
110
111
112
113
117
119
120
121
125
126
127
129
131
132
134
139
141
142
144
146
148
150
3
Compound ug/m
CO,
cyclopropane
dif luorodichloronethane
propane
1-butene
n-butane
2-butene
chloroethane
acetaldehyde
dichlorof luor oaethane
acetone (tent.)
isopentane
trichlorofluoromethane
C-H..- isomer
5 10
n-pentane
CgHj_ isomer
dichloromethane 15
2, 2-dlmethylbutane
C6H14 lsomer
2-methylpentane
dimethyl ether
3-methylpentane
CgHj. isomer
hexafluorobenzene (e5)
ri-hexane
diethyl ether 35
chloroform
perf luorotoluene (e§)
C7H14 isoner
C.H., isomer
7 lo
1,1,1-trichloroechane 0.04
benzene
carbon tetrachloride trace
cyclohexane and C-H, , isomer
C7H14 isomer
C-H, . isomer
7 14
1-heptane
trichloroerhylene and n-
heptane
CgHjo isomer
methylcyclohexane
CgH., isomer
CgH, 8 isomer
C8H16 i30mer
toluene
C8H18 lsonier
Chroma co-
graphic
Peak No.
32
33
34
35
36
36A
37
38
39
39A
40
41
41A
42
42A
•43
44
45
46
47
47A
47B
48
49
49A
50
50A
SOB
51
51A
52
53
54
54A
55
55A
57
58
60
(continued)
92
Elucion
Temp.
152
154
157
158
161
163
165
168
169
171
173
174
176
180
181
183
184
186
187
188
190
191
192
193
196
197
198
199
200
201
202
204
206
210
211
212
213
215
217
221
Cocpound -g/x
C8H,g isoner and 4-methyl-2-
pentanone
n-octane
hexamechy Icy c lo tr is i loxane
tetrachloroethylene 8
C9H20 lsomer
CgH.,8 isomer
chlorobenzene trace
ethylbenzene
£-xylene •.
C9**18 lsomer
cyclooctatetraene or styrene
o-xylene and n-nonane
C.-.H,, isomer
10 22
isopropylbenzene
C10H22 isomer
C.-alkyl cyclohexane isoner
C10H22 isomer
n-propylbenzene
m-ethyltoluene and ciiH2,
isomer
benzaldehyde
phenol -10
silane compound
1-decene
1,2,4-trimethylbenzene and
n-decane
m or p_-dichlorobenzene
C.-alkyl benzene isomer and
C11H24 isonier
1, 2, 3-trimethylbenzene
C11H24 isomer
o-dlchlorobenzene
methyl styrene
C.-alkyl benzene isomer
C11H24 isoiner
acetophenone
ii-undecane
C10H12 lsomer
C..H-- isomer and C..H-,
XX it. XZ £O
isomer
C11H20 lsoner
C,— alkyl benzene
silane compound
C.-alkyl benzene isomer and
C.-alkyl benzene isomer
-------
Table 31 (cont'd)
Chroraato-
graphic
Peak No.
61
62
63
67
68
69
70
72
73
74
75
76
77
78
Eluclon
Temp.
(°C)
223
226
228
240
240
240
240
240
240
240
240
240
240
240
Compound i-g/m
1-dodecane
n-dodecane
naphthalene
1-trldecane
£-trldecane
3-methylnaphthalene
a-methylnaphthalene
biphenyl
ii-tetradecane
echylnaphthalene isomer
dimethylnaphrhalene isomer~N
dimechylnaphthalene isomer \ -20
dlmechylnaphthalene isomer^
biphenylene
Chrorcaco- tluclon
graphic Temp. Co-pound ? =3
Peak ::o. CO
f
Ambient air sampled during period no. 5, location no. 3, see Table 15 for
protocol.
93
-------
Table 32. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
NEAR KIN-BUG DISPOSAL SITEa
Chroiaacc-
graphic
Peak No.
1
2
2A
3
4
iA
4B
5
6
-
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
22A
23
24
25
25A
26
27
28
29A
29
30A
30
31
32
Elucion
Terap.
CC)
83
85
38
91
92
93-5
101-4
105-108
108-110
111
113
114-5
116
118
119
122-4
125
126-8
103-3
133-4
135-6
137
138-144
144
145-50
151
152-6
155-8
159
160-1
162-4
165-7
167-70
171-2
172-6
177
178-9
Compound ug/n
difluorodichloromethane
acetaldehyde
isopentane
trichlorof luorooethane
j»-?encane
C5H10 isoner
bromoethane 1
dlchloromethane 375
2-nethylpentane
3-methylpentane and diethyl 23
ether
perfluorobenzene and ri-hexane
CHC1 74
diisopropyl ether 17
peri luorotluene (e?)
methylcyclopentane and 30
tv-butanal
ethyl acetate and 1,2- 20 + 35
dichloroethane
1,1,1-trichloroethane 25
benzene 1, 550
2, 3-dimethylpentane
isopropyl acetate and
C,H, , isomer
/ lo
trlchloroethylane and C_H, ,
Isomer and n-heptane
2,5-diaethylfuran (tent.)
and methyl methacrylate
l-chloro-2-bronoe thane 25
C,H, Isomer
7 14
4-methyl-2-pentanone 813
1,1,2-trichloroethane 17
toluene 2, 600
C-H., isomer
n-octane 15,000
tetrachloroethyleae
CgH.Q isomer
C8H18 lsomer
chlorobenzene 50
ethylbenzene
CgH. _0 Isomer and £-xylene
scyrene
c— xylene and ri-nonane and
C.H.. isomer
C10H22 isomeir
isopropylbenzene
nrooaco-
;raphic
'eaic No.
33
34
35
35A
35B
36
37A
37
37A
37B
37C
37D
37E
38A
38B
38
38C
38D
39
40
41
42
43
44
45
(continued)
94
Elution 3
Terno. Coisoound tg/a
(•c)
179-80 C1QH,2 isomer
181-2 propylcyclohexane and ciQH20
isomer
183-6 ii-propylbenzene and chloro- ~N
toluene and m-ethyltoluene \ 29,700
and C. _H,2 isomer J
186-8 cioHTn isoraer and silane
compound
188-89 c— ethyltoluene and a-methyl
styrene
190 C10H20 isOTier
190-93. £-decane and 1,2,4-trimethyl-
benzene
194 £-dichlorobenzene
194-196 CUH24 isoner and C^-alkyl
benzene
196-7 1,2,3-trimethylbenzene
197—8 C.-H.g isomer
198-200 o-dichlorobenzene
198-200 C.-alkyl cyclohexane isomer I -69,000
and 3-methylstyrene and
C.-alkyl benzene and
C11H22 laomer >
200-2 C..H,, isomer
202-4 C.-alkyl benzene isomer and
C11H24 isollier
C.-alkyl benzene
205-6 C1QH18 isomer ^
205-8 acetophenone 1 .. ,._
206 C10H16 I80mer and C11H22 [
isomer and C.-alkyl benzene 1
207-8 o-undecane
209-10 C.-alkyl benzene isomer
211 C.-alkyl cyclohexane isomer
and C.-alkyl benzene Isomer
and cj7H26 isomer
212-14 C^-alkyl benzene isomer
215 C.-alkyl benzene isomer and
C11H20 i30mer
216-7 Cg-alkyl benzene isomer
218-19 C.-alkyl benzene isomer
220-22 C,-alkyl benzene isomer and
o
C13H28 1SOIner
222-24 1,3,5-trichlorobanzene and
n-dodecane
225 naphthalene
-------
Table 32 (cont'd)
Chromj co-
graphic
Peak No.
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
Elucion
Temp. Compound ug/m3
226
228
232
235
237
239
240
240
C,,H,0 isomer and C..H.,
Lj bO 11 1-4
isomer
1,2, 4-trichlorobenzene
C. oH-g isoraer
C..H-- isomer
tridecane
ri-tridecane
C..H., isomer
B-methylnaphthalene 3,100
a-methylr.aphthalene 3,000
C7~alkyl benzene isomer
C13H18 isoner
C14H28 ls°mer
n-tecradecane
C13H18 lsomer
C13H18 isolner
8-ethylnaphthalene
a-ethylnaphthalene and
C15H30 lsomer
Chroma Co- Elucion
graphic Temp. Compound ug/m
Peak Mo. CO
f
Ambient air sampled during period No.
protocol.
1, location No. 1, see Table 15 for
95
-------
Table 33. VOLATILE' ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
NEAR KIN-BUG DISPOSAL SITEa
Chroma co-
graphic
Peak No.
1
2
3
4
6
7
8
8A
8B
8C
9
10
11
12
12A
13
14
15
ISA
15B
16
17
17A
18
18B
19
20
21
22
22A
23
24
24A
25
26
27
28
29
30
31
32
33
34
34A
35
36
Elucion
Temp.
CC)
64
69
71
73
81
85
88
90
91
92
96
100
105
108
109
111
113
117
118
120
122
125
126
127
128
129
132
134
140-2
144
148
152
153
155
157
153
161
163
165
168
169
173
175
176
179
180
Compound ug/ra
dichlorodif luoro:nethane
i\-pro?ane
1-butene
n— butane
acetaldehyde
isopentane
trichlorofluoromethane
fur an
C5H1(J isomer
n-pentane
C.H.rt isomer
5 10
dichloromethane 0 . 042
2-methylpentane
3-methylpentane
1-hexene
hexaf luorobenzene and n-hexane
trichloromethane (CHC1-) 30
perf luorotoluene (el)
methylcyclohexane
C7H14 lsomer
1,1,1-trichloroethane 0.03
benzene 10
carbon tetrachloride trace
2-nethylhexane
C7H14 is°mer
3-methylhexane
trichloroethylene
o-heptane
ti-propylbenzene
C8H18 1SO:aer
toluene 150
4-methyl-2-pentanone
C8H16 lsomer
n-octane
hexamethylcyclotrisiloxane
tetrachloroethylene 60
CgH.Q Isomer
dimechylheptane isomer
chlorobenzene 4
ethylbenzene
£-xylene
styrene
o-xylene and n-nonane
1,1,2,2-tetrachloroeehane 2
C10H20 lsoner
isopropylbeozene
hrosiato-
raphic
eak No.
37
38
39
40
41
41A
42
43
43A
44
45
46
47
48
49
50
50A
51
52
53
54
54A
55
56
56A
57
58
60
61
62
62A
62B
63
64
Elucion
Temp.
CC)
181
183
185
186
188
189
189-90
193
193
194
197
198
201
203
205
206
208
209
213
215
217
219
221
223
225
227
233
240
Compound -£/?.
C10H2"P isorner
C10H20 i3°*el
n-propylbenzene
m-ethyltoluene and C10H22
isomer
benzaldehyde 56
silane compound (BKG)
phenol and o_-ethyltoluene
l,2,4-trime:hylbenzene and
ti-decane '
C..H-. isomer
11 24
C,-alkyl benzene isomer
1, 2,3-trimethylbenzene and
C11H24 isoner
C..H.O isomer
dichlorobenzene (m or p)
C11H24 lsoner
C,-alkyl benzene Isomer
acetophenone
C^-alkyl benzene isomer
C10H16 lsomer and C12H26
isomer
C,-alkyl benzene isomer
C,— alkyl benzene isomer
C.-alkyl cyclohexane isomer
silane compound (BKG)
C12H26 lsoner
C,-alkyl benzene isoaer
C;-alkyl benzene isomer
1,3,5-triaethylbenzene
naphthalene
C13H28 lsomer
C,-alkyl benzene isomer
3-methylnaphthalene "^
, .... / traces
a-methylnaphthalene (
C14H28 lsoner
n-tetradecane
biphenyl
"''
Ambient air sampled during period no. 5, location no. 4, see Table 15 for
protocol.
96
-------
Table 34. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
FROM LOS ANGELES, CAa
Chroma co-
graphic
Peak No.
2
3
4
5
6
8
9
10
10A
11
13
14
15
16
17
19
21
23
23A
24
24A
25
26
26A
27
28
28A
29
29A
30
31
32
32A
33
34
35
36
37
37A
38
39
40
Elution
Temp.
("0
37
40
41
42
43
45
46
49
50
51
55
56
58
59
61
64
66
70
71
72
73
76
77
79
80
81
82
83
84
85
87
90
91
92
93
95
96
97
97
98
101
102
Compound ug/m
CO,
propylene
dichlorodif luoromethane
chloromethane
o-propane
1-butene
£- butane
2-butene
chloroethane
acecaldehyde
isopentane
trichlorof luoromethane
CjHj- isomer and furan
ii-pentane
C_HIQ isomer
dichlorome thane
propanal
C,H.n isomer
b 1U
C,H.- isomer
2-methylpentane
acetone (tent.)
3-methylpentane
4-methyl-l-pentane
hexafluorobenzene (eS)
n-hexane and 2-methylfuran
chloroform
3-methylfuran (tent.)
C.H.O isomer
CgH. 2 Isomer
perfluorotoluene (eS)
methyl cyclopentane and
C-H. , isomer
1 lo
1,1, 1-trichloroethane
C-H. , isomtr and CgH.. isomer
methyl ethyl ketone
benzene and carbon tetra-
chloride
cyclohexane
2-methylhexane
C.H. , isomer
C,H, , isomer
3-methylhexane
1, 3-dimethylcyclopentane
isomer
trichloroethylene and methyl
butanol isomer (tent.)
Chroma to-
graphic
Peak No.
41
41A
42
43
44
45
46
47
48
49
50
50A
51
52
52A
53
54
55
55A
56
57
58
59
59A
60
61
61A
62
62A
63
64
66
67
68
68A
69
70
71
72
73
74
74A
74B
75
(continued)
97
Elution 3
Tenp. Compound -g/ra
104
106
107
109
111
112
113
115
117
119
120
121
122
124
125
127
128
130
131
135
137-8
139
142
143
144
145
148
149
150
151
152
158
159
160
161
162
164
164
165
166
168
169
170
171
ii-heptane
2 , 5-dimethylf uran
2-pentanone
2 , 2-d imethylhexane
methylcyclohexane
C-H, . isomer
o lo
C-H,. isomer and C0H,, isoner
7 14 8 16
4-sethyl-2-pentanone and C0H.C
o Xo
isomer
4-methylheptane ,
toluene
C-H.g Isomer
isobutyl acetate (tent.)
2 , 4-diaethylhexane
dimethylcyclohexane isomer
dimethylhexadiene isomer
C8H16 lsomer
n-octane
tetrachloroethylene
ri-butyl acetate
C.H.Q Isomer
dimethylcyclohexane isomer
and chlorobenzene
CgH.g isoner
ethylbenzene
CgH20 isomer
£-xylene (or m)
2-methyloctane or CgH-,. isomer
styrene
o-xylene
CgH.g Isomer
a-nonane
C10H22 Is0mer
Isopropylbenzene
C10H22 isomer
C,-alkyl cyclohexane
C10H20 is°mer
n-propylbenzene
m-echyltoluene
C10H22 isomer
1,3,5-trimethylbenzene
C10H20 isomer
£-ethyltoluene
o-methylstyrene
C10H20 lsomer
1 , 2 , 4-trimethy Ibenzene
-------
Table 34 (cont'd)
Chroma to-
graphic
Peak So.
75A
76
77
78
79
80
81
81A
81B
82
83
84
85
86
87
87A
38
90
91
92
93
Eiucion
Temp.
171
172
174
176
177
178
180
181
181
182
183
185
186
188
189
190
191
196
198
204
210
Compound ug/m
C10H20 ls°mer
n-decane
£ (or ra)-dichlorobenzene
C.-alkyl benzene isomer
C11H24 isomer
^U.^24 isoiner
o-methylstyrene or indan
C.-alkyl cyclohexane is outer
C. ]H,_ isomer
sec-butylbenzene
o-cymene and C,-alkyl benzene
isomer
acetophenone
C.-alkyl benzene isomer
C^-alkyl benzene isomer and C.-H,.,
isomer
C.-alkyl benzene isomer and
methyl indan is oner
C11K'»2 lsomer
n-undecane
C,-alkyl benzene isomer
C11H20 isomer
C.-alkyl benzene isomer
n-dodecane and naphthalene
Chromaco- Elucion
graphic Temp. Compound -g/ra
Peak No. (°C)
•^
*
Ambient air was sampled at 15th and Emery St. (Fig. 10), see Table 17 for
protocol; volume of air was 0.1 of sample in Table 35.
98
-------
Table 35. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
FROM LOS ANGELES, CAa
Chroraaco-
graphic
Peak No.
1
2
3
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
Elution
Temp.
40
40
42
46
48
49
51
56
61
63
64
65
66
67
68
70
72
72
76
80
83
85
86
86
88
92
94
95
96
100
101
101
102
102
103
105
107
108
109
110
110
111
112
114
116
118
Compound ng/ra
s2
°2
co2
dichlorodifluororae thane
butene
butane
chloropropane (tent . )
acetaldehyde -125,000
isopentane
trichlorofluorometKane
furan
pentane
vinyl methyl ether
acrolein
ethanol
CH2C1,
freon 113 (BKG)
acetone
monovinyl glycol ether (tent.)
methylpentane
methyl pentane
perfluorobenzene (eS)
hexane
chloroform
methyl ethyl ketone
perfluorotoluene (eS)
methylcyclopentane
dimethyl ethylhexane (tent.)
1,1,1-trichloroethane 8,340
benzene 18,421
methylheptane
cci4
cyclohexane
dimethylheptane
C.H.g isomer
C-H,. Isomer
heptanol
C7H14 isomer
trichloroethylene
C7H., isomer
C,H, , isomer
7 12
C;HM isomer
dimethylfuran
CjH, . isomer
trimethylpentane
dimethylpentene
Chroma to-
graphic
Peak No.
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
(continued)
99
Elution ,
Temp. Compound ng/a
("0
119
119
120
120
121
122
123
123
124
126
127
128
129
132
132
133
135
136
137
138
140
142
144
145
146
146
149
150
151
152
152
153
155
156
157
157
160
162
163
163
164
164
165
166
166
167
bromofluoromethane (tent.)
CgH2Q isomer
dimethylhexane
C7H14 isoner
2-hexanone
C-H.., isomer
o lo
C.H., isomer
o lo
dihydropyran
dimethylhexane
toluene '
CgH,8 isomer
C0H, , isomer
o lo
CgH.g isomer
CgH., isoner
CjH.- isomer
CgH, , isomer
CgH,g isomer
o-propyl acetate
C8H16 isomer
tetrachloroethylene
C.H., isomer
o lo
CnH.Q isomer
CgH2- isomer
C_H,. isomer
o ID
chlorobenzene
Cgll./. isomer
ethylbenzene
CgH2n isomer
dimethylbenzene
CgH2Q isomer
CqH. , isomer
CgH-8 isomer
styrene
dimethylbenzene
C9H18 isoner
CgH2Q isomer
2,4-dibromo-l-butene (tent.)
CgH.jj isomer
methyl ethylbenzene
C10H22 isomer
C-H,.. isomer
9 16
CgH18 isomer
C.QH22 isoner
CgH.g isomer
C10H20 isomer
CgH2Q isomer
-------
Table 35 (cont'd)
Chroisaco-
graphic
Peak No.
95
96
97
93
99
100
101
102
103
104
105
106
108
109
110
111
112
113
114
115
116
117
113
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
Elucion
Temp.
CO
168
169
169
170
171
172
172
173
173
174
175
175
176
176
177
178
179
180
181
182
182
183
184
184
186
187
187
187
187
188
188
188
189
190
190
191
191
193
193
194
194
196
196
196
197
Compound ng/m
ClnH,. isomer
10 20
benzaldehyde
C10H20 isomer
trimachy Ibenzene
C.-.H., isomer
10 22
crimechy Ibenzene
C..H-. isomer
11 24
C10H20 is°Qer
C.nH,, Isoaer
10 22
C10H20 1SOner
benzonitrile
trimethy Ibenzene
C10H20 1SOner
methyl cyclopropyl ketone
(tent.)
C...H20 isomer
C.-alkyl benzene isomer
C.-H,, isomer
phenol
C.-alkyl benzene isomer
dichlorobenzene
C,-alkyl benzene isomer
C11H24 lsomer
C.-alkyl benzene isomer
C11H24 lsomer
C10H18 lsonier
C.,H_. isomer
11 22
d ichlorobenzene
C11H22 l30mer
C11H24 isomer
dihydroindene
C,.H,_ isomer
10 20
C11H22 is.omer
C.-alkyl benzene isomer
C.-alkyl benzene isomer
acecophenone
C11H22 lsomer
C11H24 isomer
C..H_. isooer
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C10H18 t30mer
C11H20 lsoner
C11H22 lsomer
d ime thy Is tyr ene
C..H-. isomer
11 24
Chromato-
graphic
Peak No.
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
Elucioa
Temp.
198
199
200
200
201
202
202
202
203
204
205
206
206
207
207
208
208
209
209
210
210
211
211
212
214
214
214
215
216
216
217
219
220
221
224
225
226
230
233
235
236
240
Compound ng/3
C..K.. isomer
11 22
C.-alkyl benzene isomer
C..H,2 isomer
C.-alkyl benzene isomer
C,,H-. isomer
11 22
C11H22 isomer
C12H26 isomer
C.-alkyl benzene isomer
C. ,H,. isomer
12 24
C.-alkyl benzene isomer.'
C11H20 is°mer
C, ,H, , isomer
12 2t
C.-alkyl benzene Isomer
methy lally Ib enz ene
C.-alkyl benzene isomer
phenylcyclohexylethane (tent.)
C12H->6 isomer
C,,H2Q isoner
C.-alkyl benzene
C12H26 lsomer
ethyls tyr ene
Cg-alkyl benzene isomer
C12H24 tsonier
C.-alkyl benzene isomer
C12H22 isomer
C12H24 lsoiner
C,,H-, isomer
13 26
trichlorobenzene
C12H26 isolner
naphthalene
C.-alkyl benzene isomer
C..H.0 isomer
13 28
C H isOD£C
11 24
C,-alkyl benzene isomer
D
C.-alkyl benzene isomer
C.-alkyl phenol (tent.)
cyclohexylphenol (tent.)
C13H26 lsomer
C13H28 isoiaer
C14H28 lsomer
methy Inaphthalene
C13H24 lsomer
methy Inaphthalene
C13H28 lsomer
biphenyl
C-.H-n isomer
14 30 . ^
aAmbient air was sampled at 15th and Emery St. (Fig. 10), see Table 17 for
protocol.
100
-------
Table 36. VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
FROM DOMINQUEZ, CAH
Chroma co-
graphic
Peak No.
1
2
2A
3
4
5
6
7
9
10
10A
11
12
13
13A
14
16
16A
16B
17
18
19
19A
20
21
21A
22
23
24
24A
24B
25
26
27
27A
28
29
30
31
32
33
34
35
36
Elution
Temp.
46
48
49
51
52
53
56
56
61
62
63
64
65
67
68
70
78
79
80
83
84
85
85
86
87
88-9
92
93
94
96
97
98
100
101
101
102
103
105
107
108
109
110
113
116
Compound ng/m
CO,
cyclopropane
dichlorodifluororaethane
chloromethane
propane
1-butene
n- butane
SO,
chloroethane
acetaldehyde
isopentane
trichlorofluoromethane
CjH1Q isomer
CeH.. isomer + furan
ri-pentane
propanal
d ic hlor one thane
acetone
1, 1-dichloroethane
2-methylpentane
3-methylpentane
C6H14 isoner
C6H12 isomer
hexafluorobenzene (eS)
2-methylfuran
n-hexane
chloroform
methyl ethyl ketone
perfluorotoluene (el)
methylcyclopentane
1,2-dichloroethane 14,814
1,1, 1-trichloroethane
CyHj, isomer
C,H.Q isomer
benzene 34,210
carbon tetrachlorlde
cyclohexane
2-methylhexane
2, 3-dlmethylpentane
3-methylhexane
diaethylcyclopentane isomer
dlmethylcyclopentane isomer
trichloroethylene 9,210
it-heptane
2, 5-dlmethylf uran
trlmethylpentane isomer
Chroma to-
graphic
Peak No.
37
37A
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
53A
54
55
55A
56
56A
57
57A
58
59
60
60A
61
61A
62
62A
63
64
65A
65
66
67
68
69
70
(continued)
101
Elution
Temp. Compound nz/3
ro
117
117
118
119
121
123
124
126
126
131
132
133
135
136
137
139
140
141
142
143
144
144
145
146
148
149
151
152
153
154
155
155
156
157
158
159
161
161
162
163
164
165
166
methylcyclohexane
CqH.. , isomer
C_H.o isomer
4-methyl-2-pentanone
C0H, - isomer
o lo
CgH. , isomer
1,1,2-trichloroethane 12,500
toluene + CQH, „ isomer
O Lo
3-methylheptane
dimethylcyclohexane isoeer
3-hexanone
C8H16 isomer
n-octane
ri-butyl acetate 1,670
tetrachloroethylene 20,000
CjjHj, isomer
C9H20 lsomer
C9H20 i90mer
C-H. o isomer
CgH20 isomer
methyl ethyl cyclopentane
isomer
chlorobenzene
trlmethylcyclohexane isoaer
ii-nonane
ethylbenzene
C.H._ isoaer
£-xylene
CgH-n isomer
2-heptanone
2-butylfuran + C0H. „ isoner
7 Lo
styrene
C9H18 lsoner
£-xylene
CqH.g isomer
Ti-nonane
C10H20 l30mer
methylethylcyclohexane isomer
C10H22 tsomer
isopropylbenzene
C10H20 Is0mer
2, 5-dlmethyloctane
3-methylnonane
n-propylcyclohexane +• C,0H-0
isomer
-------
Table 36 (cont'd)
Chromato-
graphic
Peak Mo.
71
72
73
73A
74
75
76
77
77A
78
79
80
81
82
83
83A
84
84A
85
85A
86
86A
87
88
89
89A
90
91
9 LA
92
92A
93
94
95
95A
96
97
98
98A
Elucion
Temp.
CO
167
168
169
170
171
171
172
173
173
174
175
176
176
178
179
179
180
180
181
181
182
182
183
184
185
185
186
187
188
189
189
190
191
191
192
193
195
196
196
Compound ng/n
octanone isomer + C.-H,,
isomer
C10H20 is°mer
benzaldehyde +• n-propylbenzene
C1QH22 isomer
m-ethyltoluene
C10H22 isOBier
1,3, 5-trlmethylbenzene
C,f)H22 isomer
cyanobenzene
6-methyl-2-heptanone (tent.).
£- ethy Ito luene
C10H18 iSOner
C10H20 1SOner
1,2, 4-trioethylbenzene
n-decane
phenol
C10H20 is°mer
isobutylbenzene
m-dichlorobenzene
sec-butylbenzene
C11H24 isomer
C,-alkyl benzene isomer
C11H24 isomer
4-oethyldecane +• 1.2,3-tri-
methylbenzene
C11H24 isomer
C11H22 isomer
C..H24 + o^dichlorobenzene
indan
n-butylcyclohexane +• C,.H22
isomer
diethylbenzene isomer
£-propyltoluene
m-propyltoluene + n-butyl-
benzene
acetophenone
C11H24 t90mer
C..H,, isomer
11 22
o-propyltoluene + ci i^st
isomer
C.-alkyl benzene + '"IQ^IS
isomer
C, -alkyl benzene + C,,H22
isomer
C1-H,n isomer
Chroaato-
graphic
Peak No.
99
100
101
101A
102
103
104
105
105A
106
107
108
108A
109
110
111
111A
111B
112
112A
113
113A
114
115
116
116A
117
118
120
121
121A
122
123
124
125
126
127
128
129
130
Elation
Temp.
197
198
200
200
201
202
203
203
204
205
206
206
207
208
208
209
210
210
211
211
212
213
213
214
215
216
217
219
220
224
225
225
226
227
228
229
230
231
233
235
237
Compound ng/n
C...H.. + nethyl indan isoaer
XX ££.
n-undecane
C_-alkyl benzene + C.,H,2
isomer
C,-alkyl benzene +• C._H,.
Isomer
C11H24 isomer
C12H26 isomer
tetramethylbenzene isomer
C..H,, isomer ,
H £.V >'
C11H20 Is0mer
C,-alkyl benzene isomer
C,-alkyl benzene isooer
Cc-alkyl cyclohexane isotcer
methylindan +• C.-H.. isomer
C,-alkyl benzene isomer
C12H26 lsomer
C11H20 isolner
C.— alkyl benzene isomer
C5~alkyl benzene + ci2H26
isomer
C, -alkyl benzene isomer
Ce-alkyl benzene + C,_H26
isomer
C12H24 + C12H22 1SOnerS
C,-alkyl benzene isomer
C13H26 lsomer
C12H24 isomer
trichlorobenzene + CX2H24 1,700
isomer
n-dodecane + naphthalene
C12H24 + trimethylindan isomers
C12H22 + C13H28 isomers
C13H26 is°°er
C13H26 ls°mer
C13H2fi isomer
C,-alkyl cyclohexane isomer
C13H28 lsomer
C- -H,, isomer
13 26
C14H30 iSOner
methyltridecane isomer
C14H30 lsoner
C13H26 lsoiner
ii-trldecane
C14H28 lsomer
S-methylnaphthalene
(continued)
102
-------
Table 36 (cont'd)
C!iri.'~.ato- El.icion
graphic Temp.
Pe.itt No. (°C)
131 238
131A 239
132 240
133 isothermal
135
136
137
138
140
142
143
144
145
Compound ng/m
C14H28 1SOmer
C.-H.,^ isomer
ct-methylnaphthalene
C13H28 isomer
C.-alkyl cyclohexane isomer
C14H30 isomer
C15H32 is0!Der
n-cetradecane
C. ,H,_ isomer
dimethylnaphchalene isomer
dimethylnaphchalene isomer
C16H34 isoner
n-pentadecane
Chronaco- Elucion
grjphic Temp. Conipound ng/a
Peak N'o. (°C)
'
Ambient air sampled at 2055 223 St., Dominquez, CA (Fig. 11) see Table 17
for protocol.
103
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-600/2-77-100
2.
3. RECIPIENT'S ACCESSIOI*NO.
4. TITLE AND SUBTITLE
ANALYSIS OF ORGANIC AIR POLLUTANTS BY GAS
CHROMATOGRAPHY AND MASS SPECTROSCOPY
5. REPORT DATE
June 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Edo D. Pellizzari
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P- 0. Box 12194
Research Triangle Park, N.C. 27709
10. PROGRAM ELEMENT NO.
1AD712 BB-08 fFY-77)
11. CONTRACT/GRAN
68-02-2262
(FY-;
T NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory - RTP, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Interim
14. SPONSORING AGENCY CODE
EPA/60n/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Analytical methodology based on capillary gas chromatography/mass spectrometry/
computer, was developed for the collection and analysis of urban organic pollutants.
The areas of investigation included; (a) the preparation and evaluation of glass
capillary columns for pollution analysis, (b) the development of methodology for
quantitative analysis of ambient air pollutants,and (c) the identification and quan-
tification of organic pollutants in ambient air from several geographical locations
within the continental U.S.
17.
KEY WORDS AND DOCUMENT ANALYSIS
a.
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/GlOUp
poYlutioh,
^Organic Compounds
*Gas chromatography
*Mass spectroscopy
^Computers
13B
07C
07D
14B
09B
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
114
S (This page)
22. PRICE
EPA Form 2220-1 (9-73)
104
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