United States
Environmental Protection
Agency
Office of Environmental Sciences Research
Research and Laboratory
Development Research Triangle Park, North Carolina 27711
EPA-600/7-77-055
June 1977
THE MEASUREMENT OF
CARCINOGENIC VAPORS IN
AMBIENT ATMOSPHERES
Interagency
Energy-Environment
Research and Development
Program Report
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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 INTERAGENCY ENERGY^ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-77-055
June 1977
THE MEASUREMENT OF CARCINOGENIC VAPORS
IN AMBIENT ATMOSPHERES
by '
Edo D. Pellizzari
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-02-1228
Project Officer
Eugene Sawicki
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 reporc 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.
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ABSTRACT
Analytical techniques and instrumentation which had been developed
during the previous contract years were further evaluated for the collection
and analysis of carcinogenic and mutagenic vapors occurring in ambient air,
The areas of investigation included: (a) the development of a permeation
system for delivering precise quantities of organic vapors for calibration
of instrumentation, (b) the development of procedures for the preparation of
glass capillary columns for effecting the resolution of complex atmospheric
vapor mixtures, (c) the characterization of organic vapor emissions from
preset controlled fires, (d) the survey of ambient air samples taken at
various sites around the Continental U.S. for the detection of N-nitroso-
amines, (e) the identification and quantification of N-nitrosodimethylamines
at samples collected in Baltimore, MD and the Kanawha Valley, WV, and (f)
the characterization of ambient air for hazardous and background pollutants
from several geographical areas within the Continental U.S.
iii
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iv
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CONTENTS
Abstract iii
Figures vi
Tables ix
Acknowledgements xiii
1. Introduction 1
2. Conclusions 3
3. Recommendations 7
4. Program Objectives 9
5. Further Study on Inlet Manifold for Recoverying Organic
Vapors from Sampling Cartridges 11
6. Permeation System for Synthesizing Air/Organic Vapor Mixture
for Calibrating Instruments 19
7. Development of Technique for the Preparation of Glass
Capillary SCOT Columns 36
8. Characterization of Organic Vapor Emissions from Controlled
Pre-Set Fires 43
9. Identification and Quantitation of N-Nitrosodimethylamine
in Ambient Air by Capillary Gas-Liquid Chromatography/
Mass Spectrometry/Computer 77
10. Detection of N-Nitrosoamines Utilizing Selected M/E Ions Via
Computer Search of GC/MS/COMP Data Obtained on Ambient
Air Samples 119
11. Identification of Volatile Organic Vapors in Ambient Air
from Several Geographical Areas in the Continental
U.S 140
References 151
Appendix
A. Volatile Organic Vapors Identified in Ambient Air at
Various Geographical Locations within the Continental
United States 153
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FIGURES
Number Page
1 Capillary trap configurations for inlet-manifold 12
2 Permeation system for delivering constant concentrations of
organic vapors 21
3 Calibration curves for rotometers 22
4 Permeation rate for benzene in TFE Teflon^at 20.0°C. Tube
dimensions were 0.25 in o.d. x 0.188 in i.d. x 12.5 cm in
length 25
5 Linear regression of flame ionization response vs. weight of
substance 33
6 Linear regression of mass spectrometer response (single ion
mode) vs. weight of compound 34
7 Glass capillary coating oven 38
8 Profile of ambient air pollutants obtained for C. H. Milby
Park, Pasadena, TX using glass capillary gas chromato-
graphy/mass spectrometry/computer. A 42 m glass SCOT
coated with OV-101 stationary phase was used; temperature
programmed from 20-220°C @ 4°C/min 40
9 Profile of ambient air pollutants obtained for C. H. Milby
Park, Pasadena, TX using capillary gas chromatography/
mass spectrometry/computer. A 400 ft S.S. SCOT coated
with OV-101 stationary phase was used; temperature pro-
grammed from 20-240°C @ 4°C/min 4!
10 Profile of ambient air pollutants for Wood River, IL using
glass capillary gas chromatography/mass spectrometry/
computer. A 42 m glass SCOT coated with OV-101 sta-
tionary phase was used; temperature programmed from
20-220°C @ 4°C/min 42
vi
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FIGURES (continued)
Number Page
11 Organic vapor profile for Experiment 1A 48
12 Organic vapor profile for Experiment 1C 57
13 Vapor collection and analytical systems for analysis of
hazardous vapors in ambient air 80
14 Schematic of instrumentation and devices for examining in
situ formation of N-nitrosodimethylamine on Tenax GC
cartridges 84
15 Map of sampling area in East Brooklyn, Baltimore, Maryland. ... 86
16 Plant map of FMC 87
17 Plant map of DuPont in Belle, WV depicting sampling location. . . 88
18 Plant map of Union Carbide in South Charleston, WV depicting
sampling locations 89
19 Profile of ambient air pollutants from an industrial site in
Baltimore, MD. Sample was taken on 10/14/75 from
3:00 pm - 6:50 pm. A 100 m glass SCOT column coated with
OV-101 stationary phase was used to effect the separation:
see Table 15 for conditions. Peak No. 27 was established
as DMN 90
20 Profile of ambient air pollutants taken on 10/16/75 from
10:00 am - 1:50 pm at the Patapsco Sewage Treatment Plant.
Instrumental conditions were identical to Fig. 19 91
21 Chromatogram of pollutants from industrial site in Baltimore,
Maryland. A replicate sample of that used for Fig. 19.
A 55 m DEGS SCOT capillary was used; see Table 15 for
operating conditions 92
22 DEGS Glass SCOT column (55 m) was used in both analyses; 70-
205°C at 4°C/min 93
23 Mass cracking pattern for N-nitrosodimethylamine 97
24 Single ion (m/e 74) chromatogram for N-nitrosodimethylamine.
A, B, C, are traces for standard DMN, and replicate field
samples, respectively. Analysis on DEGS column, standard
conditions 98
vii
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FIGURES (continued)
Number Page
25 Standard curve for N-nitrosodimethylamine 99
26 Standard curve for N-nitrosodimethylamine 100
27 Single ion (m/e 74) current profile of ambient air sample
taken at locations No. 2 on DuPont property in Belle,
WV 104
28 Single ion (m/e 74) current profile of ambient air sample
taken at location No. 13 on Union Carbide property in
South Charleston, WV 105
29 Mass Fragmentogram of m/e 102 for N-nitrosodimethylamine 133
30 Map depicting sampling site in El Segundo, CA 144
31 Map depicting sampling site in Torrance, CA 145
32 Profile of ambient air pollutants from South Charleston, WV
using high resolution gas chromatography/mass spectro-
metry/computer. A 400 ft S.S. SCOT coated with OV-101
stationary phase and a temperature program of 20-230°C
@ 4°C/min were used. See Table 38 for listing 154
33 Profile of ambient air pollutants from Arvado, CO using high
resolution gas chromatography/mass spectrometry/computer.
A 400 ft S.S. SCOT coated with OV-101 stationary phase
was used; temperature programmed from 20-240°C @ 4°C/min.
See Table 52 for listing 224
viii
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TABLES
Number Page
1 Performance of Co-axial and Trans-axial Nickel Capillary Traps
on Inlet-Manifold System 14
2 Catalytic Activity of Nickel Capillary Trap on Inlet-Manifold
System 17
3 Approximate Permeation Rates of Ambient Air Pollutants from
Plastic Materials 24
4 Rate of Weight Loss for Permeation Tubes Determined Over An
Extended Period of Time 27
5 Experimental Protocol for Sampling Organic Vapors Emitted
From Fires 45
6 Operating Parameters for GLC-MS-COMP System 46
7 Organic Vapors Emitted from Head Fire During Flame Period .... 49
8 Organic Vapors Emitted from Head Fire During Smouldering Period . 53
9 Organic Vapors Emitted from Head Fire During Flame Period .... 58
10 Organic Vapors Identified in Emissions from Backfire During
Flame Period 63
11 Organic Vapors Emitted from Back Fire During Flame Period .... 67
12 Organic Vapors Identified in Emissions from Back Fire During
Fire Period 70
13 Organic Vapors Emitted from Pine Needles during Smouldering
Period 73
14 Cancer Mortality Statistics 77
15 Operating Parameters for GLC/MS Computer System 81
16 Samples Examined for N-Nitrosodimethylamine by Gas-Liquid
Chromatography/Mass Spectrometry/Computer 94
17 Breakthrough Volumes for DMN, DMA, NO, N02 and HJD 96
18 Sampling Conditions and Concentrations of N-Nitrosodimethyl-
amine in Ambient Air 101
ix
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TABLES (continued)
Number Page
19 Sampling Conditions and Concentrations of N-Nitrosodimethyl-
amine in Ambient Air in the Kanawha Valley, WV 106
20 Yield of DMN from In Situ Reaction(s) on Tenax GC Cartridges
During Sampling in the Presence of DMA, NO, N02 and
H20 109
21 Effect of Ozone, NO, N00 and DMA on In Situ Formation of
/ ••
DMN HI
22 Formation of DMN from Ozone, NO, NO- and DMN in a Flow Tube . . . 115
23 Operating Parameters for GLC/MS/COMP System 121
24 Nitrosamines and Their M/E Ions Selected for Detection in
Ambient Air Samples 123
25 Estimated Overall Sensitivity of GC/MS/COMP Technique for
Nitrosoamines in Ambient Air 125
26 Ambient Air Sampling Protocol for Houston, TX and Vicinity. . . . 126
27 Ambient Air Sampling Protocol for Los Angeles, CA and
Vicinity 127
28 Sampling Protocol for the Kanawha Valley, WV 128
29 Ambient Air Sampling Protocol for Houston, TX and Vicinity. . . . 129
30 Ambient Air Sampling Protocol for St. Louis, MO and Vicinity. . . 131
31 Ambient Air Sampling Protocol for Denver, CO and Vicinity .... 132
32 Ambient Air Sampling Protocol for Atlanta and Macon, GA 134
33 Sampling Protocol for Baltimore, MD and Vicinity 135
34 Ambient Air Sampling Protocol for Kanawha Valley, WV 137
35 Sampling Protocol for Central and Northern New Jersey and
Los Angeles, CA Basin 142
36 Concentrations of Ambient Air Near Industrial Sites in the
New Jersey Area ^4g
37 Concentration of Pollutants in Ambient Air in Torrance, CA. . . . 150
38 Organic Vapors Identified in Ambient Air in South Charleston,
W 155
39 Organic Vapors Identified in Ambient Air in S. Charleston, WV . . 160
40 Pollutants Identified in Ambient Air from South Charleston, WV. . 165
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TABLES (continued)
Number
41 Pollutants Identified in Ambient Air in C. H. Milby Park,
Pasadena, TX 171
42 Pollutants Identified in Ambient Air in C. H. Milby Park,
Pasadena, TX 175
43 Pollutants Identified in Ambient Air from Pasadena, TX 180
44 Pollutants Identified in Ambient Air from Pasadena, TX 186
45 Pollutants Identified in Night Ambient Air in Pasadena, TX. . . . 192
46 Pollutants Identified in Day Ambient Air in Pasadena, TX 197
47 Pollutants Identifed in Night Ambient Air in Texas City, TX . . . 201
48 Pollutants Identified or Detected in Ambient Air from Texas
City, TX 206
49 Organic Vapors Identified in Ambient Air in Pasadena, TX 210
50 Pollutants Identified or Detected in Ambient Air from May
Street, Houston, TX 215
51 Pollutants Identified in Day Ambient Air in Downtown St.
Louis, MO 219
52 Pollutants Identified in Ambient Air from Arvado, MO 225
53 Pollutants Identified in Ambient Air from St. Ann, MO 231
54 Organic Vapors Identified in Day Ambient Air at the Entrance
of the Eisenhower Tunnel in Colorado 236
55 Organic Vapors Identified in Day Ambient Air in Denver, CO. ... 240
56 Pollutants Identified in Ambient Air in Paterson, NJ. 245
57 Pollutants Identified in Ambient Air in Clifton, NJ 248
58 Organic Vapors Identified in Ambient Air in Passaic, NJ ..... 251
59 Organic Vapors Identified in Ambient Air in Hoboken, NJ 255
60 Organic Vapors Identified in Ambient Air Near Celanese Corpora-
tion, Newark, NJ 258
61 Organic Vapors Identified in Ambient Air in Staten Island, NY . . 261
62 Organic Vapors Identified in Ambient Air in Fords, NJ 264
63 Organic Vapors Identified in Ambient Air in Boundbrook, NJ. . . . 267
64 Organic Vapors Identified in Ambient Air in El Segundo, CA. . . . 270
xi
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TABLES (continued)
Number ?M
65 Organic Vapors Identified in Torrance, CA
66 Organic Vapors Identified in Ambient Air from Torrance, CA. . • • 282
xii
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ACKNOWLEDGEMENTS
The valuable assistance of Mr. J. E. Bunch and Dr. R. E. Berkley for
executing laboratory and field experimentation is gratefully appreciated.
Mrs. N. Pardow, D. Smith and Dr. J. T. Bursey provided the interpretation of
mass spectra and the analysis of samples by high resolution gas-liquid
chromatography/mass spectrometry/computer in this research program, a sin-
cere thanks for their support. The helpful suggestions of Dr. M. E. Wall
throughout the program are appreciated.
Mr. Bill Estes of the State Pollution Agency (EPD), Atlanta, GA and Mr.
Bill Weissenbaker of the Fulton County Health Department, Atlanta, GA are
thanked for assisting RTI personnel in the selection of sampling sites. The
personnel at the Forest Fire Laboratory, Dr. Paul Ryan and Mr. Charles Mahon
provided assistance in the sampling of fire emissions and their help is
deeply appreciated. The author also wishes to thank the personnel at the
Bibb County Regional (EDP) headquarters in Macon, GA and those at the DeKalb
County Health Department in Doraville, GA (Mr. Bob Dehart and Raymond Mc-
Queen). The author is especially grateful to Drs. Dick Flannery, Lloyd
Stewart and Mr. Jim Tarr for their assistance in selecting sites in the
greater Houston area as well as the use of Connie stations in Baytown,
Pasadena and Texas City, TX. The valuable assistance provided by Mr. Walter
Cooney and Mr. George Ferrari of the State of Maryland Air Quality for
gaining access to sites in the Baltimore, MD area is gratefully appreciated.
The author wishes to also thank Mr. G. A. DeMarrais for the meterological
data which was obtained during the Baltimore study. The success of the
studies in the New Jersey area were primarily due to the helpful assistance
of Dr. Paul Brown, Mr. Joe Spatola, Ms. Ann Krypel and Mr. Steve Rivar of
the Region II, EPA in Edison, NJ. A special thanks to the personnel at the
fire departments in the Kanawha Valley are in order. The author is espe-
cially grateful to Captain Weaver of the South Charleston fire department.
The personnel of the State of West Virginia Air Pollution Control are also
xiii
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acknowledged for their help in the acquisition of sampling sites during the
nitrosamine study.
The constant encouragement and constructive criticisms of Drs. E.
Sawicki, P. Altschuller, A. Ellison and Mr. K. Krost of NERC, RTF, NC are
deeply appreciated. The assistance provided by Mr. J. Bauchman, J. 0'Conner
and J. Padgett of EPA, RTP, NC are acknowledged for their valuable help in
acquiring permission and assess to various plant sites.
XiV
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SECTION 1
INTRODUCTION
This research program on the development of analytical techniques for
measuring ambient atmospheric carcinogenic vapors has attempted to furnish a
comprehensive and systematic approach to this problem. It has attempted to
develop and evaluate the sampling device, field collection methodology, and
the entire procedure of the data analysis of carcinogenic vapors in the
atmosphere. Until this research program was initiated, the ability to
collect and analyze a wide variety of chemical classes from the atmosphere
which contained toxic and/or carcinogenic organic compounds was not pos-
sible. For this reason, research programs to determine and evaluate the
health-impact of carcinogenic compounds in the environment had not been
conducted. The ability to execute comprehensive studies on the levels of
carcinogenic agents in all media in addition to air and the correlation of
this exposure to body burden and health effects on man, was also not pos-
sible. Thus, a well-defined epidemiological approach which is required in
this type of study, to establish whether an association of relationship
existed suffered from the lack of appropriate technology in order to achieve
these goals.
The main reasons for identifying and determining environmental carcino-
genic organics even at low concentrations are as follows:
(1) A knowledge of the presence and concentrations of mutagens and
carcinogen in the air is mandatory for a better understanding of
our genetic diseases and the future carcinogenic and mutagenic
problems which may arise after a long induction period.
(2) If the incidence of cancer in the US is to be understood and con-
trolled, it will be necessary to determine the concentrations of
environmental carcinogens. It is necessary to also understand the
complete organic composition of the atmosphere since there are
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antagonistic and synergistic relationships i.e. anti-and co-
carcinogenic factors which may occur and contribute to the observed
incidence of cancer. ,
(3) It is known that the higher cancer mortality rates have been shown
to occur near various sources of air pollution and in statistical
studies, it has been demonstrated that cancer associated with the
respiratory system is higher wheie hi^h air pollution occurs.
(4) Because the recent estimates indicate that chemical synthesis adds
some 1/4 of a million new chemical compounds each year to the
several million already in existance, these new compounds can be a
serious source of air pollution and may have a significant affect
on the health of the human populace.
and (5) The development of a analytical technique for measuring ambient
atmospheric carcinogenic vapors must provide a thorough analytical
approach which will measure a wide number of potential environ-
mental carcinogens and mutagens as well as their precursors and
various co-factors and anti-factors.
The development of analytical techniques for measuring ambient atmos-
pheric carcinogenic vapors has attempted to provide a conceptual approach
which will allow the answering of questions cited above.
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SECTION 2
CONCLUSIONS
The design specifications for the cryogenic capillary trap on the
inlet-manifold were delineated and evaluated for efficient transfer of
vapors from the sampling cartridge to the high resolution gas chromato-
graphic system. The results of this study indicate that a Ni capillary trap
of a trans-axial configuration with the dimensions of 0.5 m x 0.04 in i.d.
is an optimum design will yield a 100% trapping efficiency for highly vola-
tile vapors such as butane. The compatability of this capillary trap with
sample introduction into glass SCOT capillaries without degradation of
resolution was also demonstrated.
A permeation system for synthesizing air/organic vapor mixtures for
calibration of instruments was designed. The preparation of a series of
permeation tubes for calibrating the glc/ms/comp system for analysis of
field samples was also achieved. Permeation rates (g/min/cm) ranged from 1
x 10 to ~1 x 10 were achieved using plastic materials (TFE, FEP and
polyethylene). The permeation rate was highly dependent on the vapor pres-
sure, the chemical properties of the substance and the plastic material
chosen for the preparation of permeation tubes. The use of permeation tubes
appears to be a feasible technique for synthsizing accurate and reproducible
mixtures of organic/air vapors.
A technique was developed for the preparation of glass capillary SCOT
columns. The method increases the reproducibility of preparation of glass
SCOT columns while reducing the overall fabrication time to about a 2 day
procedure. The preparation of glass SCOT columns utilizes silanized fumed
silicon dioxide (6-8 Jd) suspended in a heavy density solvent (methylene
chloride or chloroform) containing the surfactant benzyl triphenylphos-
phonium chloride and a stationary phase (2-3%). A coating oven was designed
and fabricated in order to deposit the stationary phase and finally divided
support on the wall of the open tubular column. The coding procedures for
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OV-101, DECS, and Carbowax 20M stationary phases yielded capillaries with
HETP values of 0.7-0.9- One hundred meter capillaries can be easily pre-
pared utilizing this technique.
The organic vapors emitted from controlled preset fires were charac-
terized by high resolution glc/ms/comp techniques. The composition of the
organic vapors was highly dependent on the stages of burning. The major
constituents emitted from the fire during the o^en flame were benzene (320
ng/Jl), toluene (891 ng/£), furfural (627 ng/£), £-xylene (529 ng/A) and
limonene (622 ng/£). During the open flame period, the major emissions were
alkanes, alkenes, and a large distribution of oxygenated compounds (analogs
of furan). During the smouldering period, the predominant species were
alkanes, and alkyl aromatics. Fewer oxygenated compounds were evident. The
major constituents were benzene, toluene and xylene.
The identification and quantitation of N-nitrosodimethylamine (DMN) in
ambient air in the Baltimore, MD and Kanawha Valley, WV areas were also
conducted. Organic vapors in ambient air on or near an industrial site in
Baltimore, MD were collected by adsorption onto a sorbent (Tenax GC 35/60).
The pollutants were recovered by thermal desorption and analyzed by gas-
liquid chromatography/mass spectrometry/computer using glass SCOT columns.
N-nitrosodimethylamine was identified from its mass spectrum as a consti-
tuent of the atmosphere by comparison of its mass spectrum with that of
authentic DMN. Identical retention times were observed for the unknown and
DMN peak on three different capillary columns. N-nitrosodimethylamine levels
in ambient air were also determined for an area surrounding this industrial
site in Baltimore, MD. Using a Tenax GC cartridge for concentrating DMN and
glass capillary gas-liquid chromatography/mass spectrometry with specific ion
(m/e 74) monitoring, DMN was quantified. The limit of detection was ~0.3 ppt
at 25°C. On the industrial site, DMN levels reached 32,000 ng/m3 (10.6 ppb)
of ambient air. The concentrations of DMN in ambient air collected in the
Kanawha Valley were several orders of magnitude lower. The highest values
3
were ~980 ng/m at a location on the plant site in Belle, WV. Many in situ
reaction studies were conducted in order to demonstrate whether the formation
of DMN on the sampling cartridge could occur in the presence of high concen-
trations of dimethylamine, NO and ozone. Laboratory and field experiments
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indicated that trace amounts (<30 ppt) of DMN can be formed when very high
levels NO (>5 ppm), 600 ppb ozone, and 1-5 ppm of amine occur. The concen-
n
tration of DMN found in the atmosphere was higher than those levels which
could be attributed to any type of in situ reaction occurring on the sampling
Cartridge.
The detection of N-nitrosoamines in samples collected at many different
geographical locations within the Continental U.S. was conducted utilizing a
computer search of selected m/e ions on previous gc/ms/comp data. Ambient
air samples which had been collected over a period of 15 months were subjec-
; ted to mass fragmentography for N-nitrosodimethylamine, N-nitrosodi-
ethylamine, N-nitrosodi-n-butylamine, N-nitrosopiperdine, N-nitrosopyrroli-
dine, N-nitrosomorpholine, N-nitrosohexylmethylimine, N-nitrosocyclohexyl-
atnine, N-nitrosomethyIbenzylamine, and N-nitrosophenylamine. Of all these
samples which were examined, only those which were taken at the Eisenhower
Tunnel in Colorado indicated the presence of N-nitrosodiethyamine (DEN). N-
nitrosodimethylamine was tentatively identified. The concentration of DEN
was estimated to be ~100 ppt.
The characterization of a number of ambient air samples collected from
several geographical areas (Houston, TX and vicinity, Kanawha Valley, WV,
St. Louis, MO, Denver, CO, Central and Northern NJ, and Los Angeles, CA
Basin) were characterized for hazardous organics. Many halogenated, oxygena-
ted, and nitrogenous organics were detected. The presence of alkanes,
alkenes, and alkyl aromatics were ubiquitous in these samples and are probably
derived primarily from fossil fuel burning. Several halogenated compounds
£.g. freon 11, methyl chloride, methylene chloride, chloroform, methyl-
chloroform, trichloroethylene, tetrachloroethylene, monochlorobenzene,
dichlorobenzenes, and trichlorobenzenes are present as a general background
in all of the samples. The relative amounts however do vary with the sampling
site. It is believed that the atmosphere is widely contaminated with low
levels of these halogenated compounds. On the otherhand, many halogenated
compounds were also detected which were site specific.
The Tenax GC sampling cartridge has proven to be a viable approach for
the collection, characterization and quantification of organic vapors occur-
ring in ambient air. The performance of this sampling cartridge has been
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demonstrated by many studies in geographical areas where a variety of indus-
trial and photochemical types of pollution occur. The technique has per-
formed satisfactorily for the collection of organic vapors under a variety
of different meteorological conditions ranging from high to low humidity and
temperatures. Some limitations do exist for the highly volatile material
such as methyl chloride, methyl bromide, vinyl chloride, vinyl bromide and
vinylidine chloride. However, the many other advantages offset the minor
disadvantages.
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SECTION 3
RECOMMENDATIONS
Six major phases of research should be expanded and pursued: (1) the
sampling cartridge should be further examined for potential in situ reac-
tions which might occur during field sampling. This activity should deline-
ate any problems associated with the sampling of atmosphere containing
molecular chlorine, bromine or iodine in combination with olefins and NO ,
' x'
S0» and ozone. Other potential in situ reactions on the sorbent bed should
also be examined such as the ozonization of olefins by moderate to high
atmospheric concentrations of ozone. (2) The examination of alternate new
sorbent materials as a backup or substitute to Tenax GC should be pursued.
This may involve the synthesis of analogs or a modified polymer base of
Tenax in order to incorporate the desired retention volume properties for
organics without increasing the overall background contribution and reten-
tion of inorganic gases and water. (3) Further development of capillary
technology is recommended. New techniques for the modification of the glass
capillary wall to minimize adsorption properties of the semi-polar and polar
constituents should be developed. Techniques which circumvent the use of
silanization should be pursued. An overall improvement in resolution and
column capacity is recommended in order to improve the quantification of
complex air mixtures. (4) Extensive sampling of numerous sites for hazar-
dous atmospheric pollutants should be conducted. The methodology for collec-
tion, resolution, and identification of hazardous vapors in ambient air
which was developed during the past three years under Contract No. 68-02-
1228 should be applied to field sampling of numerous sites within the Con-
tinental U.S. with a major thrust toward the characterization and identifi-
cation of carcinogenic and mutagenic vapors. The selection of sites should
be based on the high incidence of cancer occurring in these areas, the types
of industrial activity or the unique photochemical atmospheric reaction
which take place. The selection of sites should include a wide variety of
-------
meteorological conditions in order to evaluate the overall techniques. (5)
Identification and quantification of hazardous vapors in atmospheric samples
should be performed. The identified hazardous vapors should be quantified
in ambient air samples and the technique should be evaluated as to its
accuracy and reproducibility for monitoring organic vapors in ambient air.
And (6) Pollution profiles indicative of individual sites should be deve-
loped. Pollution profiles should be assembled for the various geographical
areas postulated to contain hazardous vapors. These profiles should indi-
cate site specific pollutants and those vapors which are ubiquitous.
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SECTION 4
PROGRAM OBJECTIVES
The general aim of this research program has been to develop and per-
fect methodology for the reliable and accurate collection and analysis of
mutagenic and carcinogenic vapors (hazardous vapors) present in trace quan-
3
tities in the atmosphere down to ng/m amounts. This information is needed
to determine the physiologically active vapors present in polluted atmos-
pheres so that researchers can ascertain their biological impact on popula-
ted areas and their overall relationship to the incidence of cancer. The
major objectives were:
(1) To further evaluate the inlet-manifold for recoverying organic
vapors from sampling cartridges,
(2) The development of a permeation system for synthesizing air/
organic vapor mixtures for calibrating instruments which will be
used for the quantification of hazardous vapors in the atmosphere.
(3) The development of techniques for the preparation of glass capil-
lary SCOT columns for effecting the resolution of the complex
organic pollutants profiles which are observed in ambient air sam-
ples.
(4) The characterization of organic vapor emissions from controlled
preset fires to ascertain the presence of any hazardous organic
vapors.
(5) The identification and quantification of N-nitrosodimethylamine in
ambient air by capillary gas-liquid chromatography/mass spectro-
metry/computer in selected industrial areas suspected to be
involved in the production or use of DMN.
-------
(6) The detection of N-nitrosoamines utilizing selected m/e ions and
computer search techniques of gc/ms/comp data obtained on ambient
air samples over the past fifteen months.
and (7) The identification of hazardous organic vapors in ambient air from
several geographical areas in the Continental U.S.
10
-------
SECTION 5
FURTHER STUDY ON INLET MANIFOLD FOR RECOVERYING ORGANIC VAPORS
FROM SAMPLING CARTRIDGES
(1-4)
In previous reports, ' we have described an inlet-manifold and had
evaluated it in terms of the thermal desorption efficiency of the desorption
unit; however, the design specifications for the capillary trap which inter-
faces the vapors from the sampling cartridge to the chromatographic system
had not been thoroughly examined. Some questions about the performance of
this capillary trap were (1) the trapping efficiency for a given length and
diameter of the capillary, (2) the delineation of whether gold coated Ni
capillary or virgin Ni should be used as the fabrication material, (3) the
maximum volume of the capillary trap which would be compatible with discrete
sample introduction into the glass SCOT capillary column and (4) the con-
figuration of the capillary trap necessary for the cooling and heating cycles
in order to ensure efficient trapping and sample introduction into the
capillary system.
An experimental evaluation of the capillary trap on the inlet-manifold
system was performed and is described in this section.
EXPERIMENTAL
An inlet-manifold system as previously described^ ' ' was used to
evaluate the capillary trap. Capillary traps were constructed of Ni tubing
in length of 0.25, 0.5, 1.0, and 1.5 m with an internal diameter of 0.02".
Capillary traps were configurated as shown in Figure 1. Two configurations
were examined. The first was a co-axial type in which the tubing was wound
around the axis of entrance and exit of the purge gas stream and the second
was a trans-axial in which the tubing was wound parallel to the entrance and
exit of the purge gas.
Gas-liquid chromatography (glc) was conducted on a Perkin Elmer 900
series chromatograph (Perkin Elmer Corp., Norwich, CN) equipped with dual
11
-------
co-axial
tram-axial
Figure 1. Capillary trap configurations for inlet-
manifold .
12
-------
flame ionization detectors. A 400 ft stainless steel SCOT coated with 0V-
101 stationary phase was used for resolving synthetic air/vapor mixtures.
The column was programmed from ambient temperature to 220°C at 6°/min with
an initial and final isothermal periods of 2 and 10 min, respectively.
Carrier gas (nitrogen), hydrogen and air flow rates were 6, 30, and 250
ml/min, respectively. The operating parameters for the inlet-manifold were
as follows: The thermal desorption chamber temperature was at 270°C, the
valve temperature 220°C, and the capillary was cooled to -195°C for trapping
vapors and to 180°C for sample introduction into the capillary system. Two
purge gas rates were evaluated as to their effect on trapping efficiency (10
and 30 ml/min) during the thermal desorption cycle.
The sampling cartridges loaded with standard air/vapor mixtures con-
tained 1.5 x 6.0 cm of Tenax GC (35/60).
Air/vapor mixtures were loaded onto the Tenax GC sampling cartridges
using an exponential decay flask. Known amounts of each organic compound
were expanded into a fixed volume and then purged onto the sampling cartridge
Cl 3)
for capillary trap evaluation. '
RESULTS AND DISCUSSION
In order to ascertain whether the various trap length and configura-
tions efficiently trapped the organic vapors which were desorbed from the
Tenax GC cartridges, the exhaust gas from the capillary trap was routed into
a backup Tenax GC cartridge. Using this arrangement, it was determined
whether organic vapors had passed through the trap during the cryogenic
cooling step. Tenax GC cartridges were loaded with acetone, hexane, ben-
zene, heptane, toluene and chlorobenzene. The Tenax GC cartridges were then
desorbed with the vapors passing through the liquid nitrogen cooled capil-
lary traps of co-axial and trans-axial configurations. The backup Tenax GC
cartridges were then analyzed by thermal desorption and glc to determine the
trapping efficiency of the capillary during the desorption of the front
cartridge. By comparison of the quantity of vapors which were trapped in
the first step with those which were recovered from the backup Tenax GC
cartridge, it was possible to determine the percent trapping efficiency.
The results of this study are summarized in Table 1. The percent trap-
ping efficiency for capillary traps of 1 m and 0.5 m lengths were 100% when
the trans-axial trap was 50% submerged into liquid nitrogen. In contrast
13
-------
Table 1. PERFORMANCE OF CO-AXIAL AND TRANS-AXIAL NICKEL CAPILLARY TRAPS
ON INLET-MANIFOLD SYSTEM
Percent Trapping Efficiency
Capillary Trap Dimensions
0.625 o.d. x 0.020 i.d. x 1 mb
0.625 o.d. x 0.020 i.d. x 0.5 mb
0.625 o.d. x 0.020 i.d. x 0.25 mb
s*
0.625 o.d. x 0.020 i.d. x 0.5 m°
Test Compound
acetone
n-hexane
benzene
ja-heptane
toluene
chlorobenzene
acetone
n-hexane
benzene
n-heptane
toluene
chlorobenzene
acetone
n-hexane
benzene
n-heptane
toluene
chlorobenzene
acetone
n-hexane
benzene
n-heptane
toluene
chlorobenzene
Co-axial Trap
90
81
86
84
95
100
89
75
84
85
95
100
84
72
81
80
93
100
_
-
-
:
-
Trans-axial Trap
100
100
100
100
100
100
100
100
100
100
100
100
97
89
95
96
99
100
97
87
90
98
99
100
(continued)
-------
Table 1 (cont'd)
Capillary Trap Dimensions
0.625 o.d. x 0.020 i.d. x 0.25 mc
0.625 o.d. x 0.020 i.d. x 0.5 md
Test Compound
acetone
n-hexane
benzene
n-heptane
toluene
ch lor ob enz ene
acetone
n-hexane
benzene
n.- heptane
toluene
chlorobenzene
£»
Percent Trapping Efficiency
Co-axial Trap Trans-axial Trap
74
73
70
68
76
83
0
0
0
0
74
100
Inlet-manifold conditions were: thermal desorption chamber - 265°C, He purge range - 30 ml/min,
valve - 200°C, trap heat - 180°C.
Co-axial and trans-axial traps were completely and 50% submerged, respectively, in liquid N?.
°Trans-axial traps were completely submerged in liquid N-.
Trans-axial trap was 50% submerged in dry ice/isopropanol coolant.
-------
the percent trapping efficiency varied considerably for the co-axial trap
which had been completely submerged in liquid nitrogen (1 m length). The
lowest efficiency was observed for n-hexane (81%). For a trap length of 0.5
m, n-hexane vapor was only trapped to an extent of 75%. Non-polar compounds
exhibited the lowest trapping efficiency while polar compounds or relatively
non-volatile substances exhibited the highest trapping efficiency. In
another study, the trans-axial traps were completely submerged. For 0.5 m
or 0.25 m traps, the efficiencies were considerably reduced.
The efficiencies of a trans-axial trap cooled to liquid nitrogen and
dry ice temperatures were also compared (Table 1). The efficiencies were
highest when liquid nitrogen was used. Also when the trans-axial trap was
half-submerged the efficiency of trapping was maximum.
A second study was conducted in order to determine whether any decom-
position and/or elimination reactions might occur during desorption of
organics into the Ni capillary trap or during the heating and injection step
onto a gas chromatographic column. To test this possibility, several com-
pounds were selected which were particularly prone to elimination reactions
(dehydration or dehydrohalogenation) forming the corresponding olefin. The
compounds t-butyl alcohol, 2-bromopentane and cyclohexane iodide were used
for this evaluation. These compounds were introduced into the capillary
trap via the thermal desorption chamber and cryogenically trapped into the
capillary trap followed by heating the trap and injecting the vapor onto the
chromatographic column. The corresponding olefin (which might be formed by
dehydration or dehydrohalogenation during the cooling and heating cycle of
the capillary trap) was monitored on the capillary column. The percent
olefin formation and/or parent loss of the compound was determined. The
results of this study are shown in Table 2. No dehydration or dehydrohalo-
genation was observed as either in the loss of parent compound or as the
appearance of the corresponding olefin.
In another experiment, decomposition of bis-(chloromethyl)ether (BCME)
was studied. BCME was introduced into the capillary trap followed by water
(5)
since it was known to hydrolyze. ' As shown in Table 2, the presence or
absence of water vapor in the capillary trap during the cooling and heating
of BCME did not cause an appreciable loss of the parent compound.
16
-------
Table 2. CATALYTIC ACTIVITY OF NICKEL CAPILLARY TRAP
ON INLET-MANIFOLD SYSTEM*
Test Compound
Parent Loss
Product Formed
_t-amyl alcohol
bis- (chloromethyl) ether (-H20)0
bis- (chloromethyl) ether (+H?0)C
2-bromopentane
cyclohexane iodide
0
0
0
0
0
0
_
-
olefin (0)
cyclohexene (0)
Inlet-manifold parameters were: thermal desorption chamber - 265°C, He
purge rate - 30 ml/min, valve - 200°C, trap cooling cycle - -195°C, trap
heating cycle - +180°C.
Approximately 1 ug of each compound (except BCME) was tested for decompo-
sition.
Approximately 200 ng of BCME was tested, 1 mg H_0 was added to trap.
Gold coated Ni capillary traps did not exhibit better performance
characteristics using these experimental tests.
One of the problems that was evident in the use of a capillary trap
with an internal diameter of 0.02" was the freezing of the trap during the
introduction of vapors from a sampling cartridge which contained a rela-
tively high amount of water vapor as a result of sampling in areas with high
humidity. The problem of obstruction of purge gas flow through the trap was
enhanced when the trans-axial trap was 50% submerged in liquid nitrogen. In
separate experiments, the use of a larger diameter capillary (0.04") was
examined. The trapping efficiencies were repeated using lengths of 0.25,
0.5 and 0.75 m with an internal diameter of 0.04". The trapping efficiency
for the trans-axial remained unchanged when purge rates of 10 or 30 ml/min
were used. High humidity sampling was conducted (90%, 90°F) and thermal
desorption analysis was conducted utilizing these traps. Obstruction of gas
flow or complete plugging was not observed in these cases. However it was
found that a minimum trap length of 0.5 m was still necessary in order to
efficiently recover all the vapors desorbed from the Tenax GC sampling
17
-------
0.5 m length trap with a 0.04" diameter provided quantitative recoveries of
thermally desorbed vapors for thermal desorption periods of upto 15 min.
The use of 0.5 m x 0.04" i.d. capillary traps was also examined for
compatibility with the glass SCOT columns. Particular attention was addres-
sed to the proMem of band (peak) spreading which occurs when excessive dead
volume is present in sample introduction mode. Experiments utilizing 400 ft
stainless steel SCOT capillaries, or 100 m glass SCOT capillaries coated
with OV-101 indicated that no band spreading occurred when the larger i.d.
trap was employed. The possibility of using this inlet-manifold system with
wall coated open tubular (WCOT) columns remains to be demonstrated since the
low dead volume requirements for these capillaries are more stringent than
for SCOT capillaries.
18
-------
SECTION 6
PERMEATION SYSTEM FOR SYNTHESIZING AIR/ORGANIC VAPOR MIXTURE
FOR CALIBRATING INSTRUMENTS
There are four general factors which affect the sensitivity of an analy-
tical procedure for analysis of carcinogenic vapors in ambient air. These
are: (1) efficiency of the sorbent medium in trapping organic vapors, (2)
the efficiency of the thermal desorption manifold in delivering collected
samples to the column, (3) the efficiency of the chromatographic column in
transmitting the desorbed vapors through the glass capillary and (4) the
response of the mass spectrometer. Calibration for quantitative analysis
must systematically account for all of these factors. The response of the
glc-ms system to known quantities of specific compounds may be observed;
however, this does not take into account systematic errors in sample col-
lection. It is also difficult to deliver aliquots of concentrations (ppt)
near the lower detection limits so that calibration plots need to be extra-
polated out of their region of validity. Long term variation in sensitivity
of the analytical system could occur as well. To overcome this, numerous
compounds could be used for calibration. Sensitivities of vapor relative to
standard compounds in the glc-ms system may be measured. Aliquots used as
standards may be added to samples before analysis. Errors in desorbing and
transfering vapors to the analytical system are circumvented.
Sampling of air doped with known trace quantities of vapors would
account for errors inherent in collection and analysis procedures, but such
low concentrations are subject to rapid depletion by adsorption onto surfaces
of vessels used for providing calibration standards.. This problem could be
circumvented by the use of permeation tubes which at constant temperature
emit vapor at a constant low rate. A stream of air or nitrogen passing over
a group of permeation tubes in a thermostated chamber would pick up a low
concentration of vapor from each tube. Surfaces in the flow system should
become equilibrated with these compounds so that they would be delivered from
the system at the same rate that they were emitted by the permeation tubes.
19
-------
The permeation rate can be determined gravimetrically by weighing each tube
at periodic intervals.
A stream of nitrogen passing over a permeation tube could be used to
-7 -9
deliver a minute quantity (10 -10 g) of a typical pollutant vapor or a
standard compound to a cartridge. It also could be used to deliver very
small concentrations of vapor into a stream of air in order to imitate the
conditions which are obtained during sampling oT polluted air. Use of permea-
tion tubes for Calibration of instruments (e.g., glc-ms) should effectively
minimize systematic errors.
A flow system for the purpose of calibrating a glc-ms-comp system using
permeation tubes was designed and fabricated. Experiments have been con-
ducted to determine the most suitable materials for use as permeation tu:/cs
and this section discusses these results.
EXPERIMENTAL
The designed flow system is depicted in Figure 2. The components were
connected with 1/8" o.d. stainless steel tubing. The Pyrex permeation chamber
(25 mm i.d. x 44 cm in length) was enclosed in a jacket through which an
ethanol-water mixture was circulated from a constant temperature bath (Haake
Model FE circulating pump and thermostated heater coupled with Haake Model
Cll refrigeration unit). Before entering the permeation chamber, the nitro-
gen was passed through a temperature equilibration coil which was approxi-
mately 4 mm i.d. xlmin length. Upon leaving the chamber, the nitrogen
vapor stream passed through a 100 ml mixing chamber before being split. A
flame ionization detector (Varian Model 1440, Walnut Creek, CA) served to
demonstrate whether the rate of sample delivery was constant as well as
providing a means for discarding a constant fraction of sample. A pair of
rotometers (Brooks Instrument Div., Emerson Electric Co., Hatfield, PA, Type
1355, tube size R-2-15-AAA with glass float) were installed in each branch of
the flow system. A reproducibility of + 0.5 ml/min was observed throughout
its operating range for the rotometer which measured flow through the cart-
ridge. Reproducibility for the rotometer which was upstream of the flame
ionization detector was poor at flow rates >35 ml/min, due to the flow resis-
tance of the flame ionization detector and attached fittings. With the flame
ionization detector removed from the system, reproducibility for this roto-
meter was also +0.5 ml/min throughout its operating range (Fig. 3). A large
20
-------
OIL
MANOMETER
MOORE REGULATOR
PERMEATION
CHAMBER
A CONSTANT
T TEMPERATURE
NITROGEN SOURCE BATH
STORAGE
CHAMBER
NEEDLE;
VALVES'
SORBENT
CARTRIDGE
X
FLOW METERS
A
FLAME
IONIZATION
DETECTOR
Figure 2. Permeation system for delivering constant concentrations of
organic vapors.
-------
10 20 30 40 50 60 70 80 90 100 110 120 130 140 ISO
45
40
35
30
125 -
20 -
15
10 -
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Rotameter Reading (Arbitrary Units)
Figure 3. Calibration curves for rotometers.
22
-------
permeation chamber connected to the constant temperature bath and flushed
continuously by a 100 ml/min nitrogen stream was used to store permeation
tubes. This permitted calibration of the tubes without interfering with
operation of the flow system and immediate use of stored tubes without waiting
for equilibration of the permeation rate.
This system could be used either to load sorbent cartridges (Fig. 2) or
to deliver vapors to a stream of air entering a cartridge sampler (Nutech
Model 221, Durham, NC). The cartridge holder consisted of two Beckman Tef-
lon^ reducing unions (No. 830511) for holding sampling cartridges. The
upstream union was fitted with Teflon^-'plug which had a 2 mm i.d. bore to
minimize dead volume.
In order to access the range of permeation rates which might be encoun-
tered among organic vapors of varying polarity, permeation tubes for several
typical compounds were prepared. They were made of approximately 7-15 cm
lengths of plastic tubing. Four kinds of tubing were used. Surgical grade
polyethylene tubing of 0.082 in o.d. x 0.062 in i.d. was initially used, but
it gave permeation rates for most compounds which were too high compared with
the volume of the tube. Subsequently 0.25 in o.d. x 0.19 in i.d. tubing made
„ r j , „ , , -Jr— _- , tetrafluoroethylene (TFE)
and fluorinated ethylene and propylene (FEP), were used. The ends were
closed with glass plugs secured by stainless steel ferrules. This technique
was used with dimethylamine which has a vapor pressure well above one atmos-
phere at ambient temperatures. The plastic tubing and the end plugs with-
stood the pressure, but the permeation rate from the polyethylene tube (7 x
10 g/min) was too large to be useful. Many non-polar compounds of much
lower volatility also had extremely high permeation rates from polyethylene
tubes.
RESULTS AND DISCUSSION
Performance of Permeation Tubes
Permeation rates obtained for typical organic compounds at 25°C are
shown in Table 3. The tubes were weighed on a microbalance at intervals of
about one week. The plots of weights (grams) vs time (min) were linear (Fig.
4). Permeation rates were determined from such data by two methods: (1) by
dividing the weight loss (g) by the time interval (min) and (2) by applying
23
-------
Table 3. APPROXIMATE PERMEATION RATES OF AMBIENT AIR POLLUTANTS
FROM PLASTIC MATERIALS
,
Compound
methylene chloride
methylene chloride
chloroform
chloroform
carbon tetrachloride
carbon tetrachloride
phenylacetylene
phenylacetylene
toluene
toluene
m-dichlorobenzene
m-dichlorobenzene
1, 1, 1-trichloroethane
1, 1, 1-trichloroethane
acetonitrile
acetone
acetone
acetone
benzene
benzene
benzene
2-propanol
d imethy lamine
dimethylamine
trichloroethylene
aRates were obtained for 25°C.
PE = surgical grade polyethylene
Permeation Rate
(g/mi \/cm)
1.37 x 10~6
2.83 x 10~8
8.15 x 10~7
4.07 x 10~9
-in
8.57 x 10
-10
6.53 x 10
4.09 x 10~9
4.17 x 10~9
7.70 x 10~9
6.87 x 10~9
7.11 x 10~8
1.21 x 10~8
2.57 x 10~9
2.27 x 10~9
2.5 x 10~7
2.5 x 10~8
1.6 x 10~8
3.1 x 10~9
8.3 x 10~6
8.4 x 10~9
5.0 x 10~9
5.7 x 10~8
6.9 x 10~8
8.0 x 10~9
1.1 x 10~7
tubing (0.082 in o.d.
Material
TFE
FEP
TFE
FEP
TFE
FEP
TFE
FEP
TFE
FEP
TFE
FEP
TFE
FEP
PE
PE
TFE
FEP
PE
TFE
FEP
PE
TFE
FEP
TFE
x 0.062 in
i.d.), TFE and FEP = TefIons^ (0.25 in o.d. x 0.188 in i.d.)
24
-------
ro
11.460-
11.450
Wt = -2.57318 x 10 7 (time, min) + 11.460403 g
60
Time (min) x
Figure 4. Permeation rate for benzene in TFE Teflon*"'at 20.0°C. Tube dimensions
were 0.25 in o.d. x 0.188 in i.d. x 12.5 cm in length.
-------
linear regression analysis to the plot of weight vs time to obtain the nega-
tive slope of the least squares line. The first method was more rapid but
less precise. Linear regression analysis over a period of weeks was a slower
process, but the effects of uncertainties in weighting were minimized. A
disadvantage of the procedure was the weekly weighing of large numbers of
tubes which was very time-consuming. Thus it would be desirable to be able
to rely on the results of calibration over an *xtended period of time. The
literature on -ermeation tubes indicates that permeation rates remain stable
for a long time. However the reported experiences involved the use of in-
organic or light hydrocarbons which were under substantial pressure in the
plastic tube. Most of the permeation tubes used in this program contained
organic liquids with lower volatilities. Another uncertainty was the length
of time required by a new permeation tube to reach a stable permeation rate.
During calibration it was evident that some of the tubes did not reach stable
rates for more than a month. Accordingly, an investigation was made of the
length of the stabilization period and the reliability of previously deter-
mined permeation rates.
Several additional organic vapor permeation tubes were prepared in
January, 1976. These tubes and the one prepared in November, 1975 were
gravimetrically calibration during February and March, 1976. Results are
shown in Table 4. The first column of data gives the rate determined by
linear regression during the months of February and March. The second column
depicts the results obtained by extending the least square calculation to the
end of April. Where the results agreed closely, permeation rates had been
steady over the experimental period. For many of the tubes prepared in
January, the permeation rate had changed. In order to see whether the rate
had stablized by the end of the Feb.-Mar. calibration period, permeation
rates were determined from weight loss during a period of one week. The
third column shows the rate based on the weight loss during the final week of
the Feb.-Mar. calibration period. The fourth column shows the rate based on
weight lost from the end of the Feb.-Mar. calibration period to the end of
April. The latter figure was more reliable than the former because the
experimental interval was larger. If these rates were in substantial agree-
ment, the rate had stablized by the end of the Feb.-Mar. calibration period.
In many cases the rate had not stablized, and a new calibration period was
26
-------
Table 4. RATE OF WEIGHT LOSS FOR PERMEATION TUBES DETERMINED OVER
AN EXTENDED PERIOD OF TIME
Ni
Permeation Rate
By Linear Regression
Date
Started
11-75
11-75
11-75
11-75
11-75
1-76
1-76
1-76
11-75
1-76
11-75
1-76
1-76
1-76
1-76
1-76
1-76
1-76
1-76
Compound
acetone
benzene
benzene
benzene-d.
D
dichloromethane
chloroform
toluene
phenylacetylene
1, 1, 1-trichloroethane
tetrachloroethylene
Plastic Feb. -Mar.
PE
TFE
FEP
TFE
FEP
TFE
FEP
TFE
FEP
TFE
FEP
TFE
FEP
TFE
FEP
TFE
FEP
TFE
FEP
1.75
A. 15
6.00
2.48
2.43
1.03
24.6
6.43
3.02
1.14
2.43
0.617
4.49
2.76
23.0
13.8
7.19
0.248
11.6
(continued)
Extended to
April
1.74
3.97
4.87
2.44
2.47
1.64
9.48
2.28
3.01
1.14
2.47
1.07
4.07
4.12
9.54
8.75
2.03
1.50
6.52
g/min by
Interval Weight Loss
Feb. -Mar.
(1 week)
1.77
4.05
5.64
2.47
2.70
1.52
16.7
2.52
3.03
1.15
2.70
0.886
3.04
3.78
12.4
10.8
1.18
0.568
9.50
April
1.74 x 10~6
3.96 x 10~7
5.90 x 10~8
2.42 x 10~7
2.47 x 10~8
1.70 x 10~7
7.54 x 10~8
2.06 x 10~6
2.99 x 10~7
1.14 x 10~6
2.47 x 10~8
1.15 x 10~7
4.09 x 10~8
4.28 x 10~8
8.21 x 10~9
8.63 x 10~8
2.18 x 10~9
1.61 x 10~7
6.16 x 10~8
-------
Table 4 (cont'd)
to
CO
Permeation Rate
By Linear Regression
Date
Started
1-76
1-76
1-76
1-76
1-76
1-76
Compound
chlorobenzene
m-dichlorobenzene
methyl ethyl ketone
ethyl acetate
Plastic
TFE
FEP
TFE
FEP
PE
PE
Feb . -Mar .
0.823
2.78
3.75
5.56
1.94
3.75
Extended to
April
1.07
1.31
3.40
2.57
1.90
3.60
g/min by
Interval Weight Loss
Feb . -Mar .
(1 week)
0.892
1.68
2.74
3.68
1.94
3.71
April
1.10 x 10~7
1.18 x 10~6
3.45 x 10~7
2.29 x 10~8
1.83 x 10~6
3.59 x 10~6
-------
initiated to determine the eventual permeation rates that was attained.
Those tubes which had reached a stable permeation rate were to be subjected
to an additional test. They have been placed in cold storage. After two
weeks, they will be returned to storage in a thermostatic chamber at 20°C and
their ability to return quickly to their former permeation rate will be
assessed. These results will be presented in the next annual report.
The carbon tetrachloride tubes did not perform as reliably as the other
permeation tubes. The TFE and FEP tubes never reached a sustained permeation
—9
rate above 10 g/min. During some intervals they actually gained weight.
It was thought that this might have been caused by storage of dimethylamine
tubes in the same chamber, but the effects were later observed to be appa-
rently independent of the presence of dimethylamine tubes. The polyethylene
tube, on the otherhand was stablized within two weeks, but permeated at a
very high rate and was depleted in a short period of time.
In summary, organic vapor permeation tubes may require two months or
more to reach a steady permeation rate (particularly for <10 g/min rates).
Performance of Permeation System
A study was conducted to determine whether background contamination was
occurring either from the nitrogen carrier gas in the flow system or from the
emission of vapors by the plastic tubing. Empty 10 cm lengths of poly-
ethylene TFE and FEP tubing were placed in the permeation chamber, and sampling
with Tenax cartridges was conducted for a period of 3 hrs with gas passing
through the system. Tenax GC cartridges were then desorbed and analyzed by
glc-fid. No evidence of background from these plastic materials was observed.
In order to demonstrate the feasibility of the fabricated permeation
flow system, pilot experiments were conducted to test its ability to measure
and deliver aliquots of vapors to sampling cartridges. This ability depended
upon two assumptions: (1) that the delivery rate was a function of the
permeation rate from the tube and not on the flow rate of the carrier gas
(the flow rate being much larger than the permeation rate and constant) and
(2) that the carrier gas flow was split proportionately to the flow of entrai-
ned vapors. The validity of these two assumptions was examined for the flow
system and the effects of variations in pressure in the permeation chamber
and variations in room temperature were also investigated.
29
-------
During the operation of the system with the splitting of flow, a sinusoi-
dal signal from the flame ionization detector was observed. When most of the
flow was directed to the flame ionization detector, this variation never
exceeded +4% of the total signal, but when only a small fraction of the flow
passed through the FID, the variation approached +20%. Thus the variation
appeared to be pressure dependent. An oil monometer was placed upstream from
the permeation chamber (Santovac-5 diffusion pt.jp oil, 1.18 g/ml, 1 cm =
0.846 torr = 0 917 psi). In this manner it was discovered that the sinusoi-
dal variation in the flame ionization detector tracing could be minimized by
maintaining the system at a pressure substantially below 10 cm of oil. The
problem apparently resulted from a variation in the downstream pressure of
the nitrogen regulator, a common problem with such regulators.
The effect of pressure on the performance of the system was also inves-
tigated. With all of the flow directed to the flame ionization detector, the
20 turn needle valve (Hoke 1335G2Y) was abruptly closed two turns from half
opened position. There was a momentary deflection ~30 sec in the FID trace,
at which time it returned to its previous level, as did the rotometer float.
The oil mometer indicated a slight increase in pressure. When this process
was repeated until a pressure above 10 cm oil was reached, the flow rate
decreased and the flame ionization detector signal surged, then decreased and
become constant.
It was believed that the room temperature might also effect the flow
system by causing variations in the amount of material adsorbed on the walls
of the non-thermostated connecting tubing. Daily variations of room tempera-
ture as large as 13°C were observed and a continuous variation over a 2°C
range was normal. To test the possibility of adsorption/desorption a heat
gun was used to heat a section of the tubing leading to the flame ionization
detector. Although this would represent a more drastic variation than was
normally observed in the ambient temperature, the response of the flame
ionization detector to this was negligible.
The assumption (No. 1) that the rate of the delivery of vapors was
dependent on the permeation rate was tested by delivering a stream of nitro-
gen which had passed over a benzene permeation tube (2.57 x 10~7 g/min at
20°C) to 5 cartridges (one at a time for 5 min) at a rate of 49 ml/min. The
flow rate was then changed to 32.5 ml/min and after equilibration of the
30
-------
system 3 more cartridges (5 min per) were loaded. All the cartridges were
then thermally desorbed and analyzed by gc with flame ionization detector (a
200 ft OV-101 SCOT capillary was used on a Perkin-Elmer 900 programmed from
30-120° @ 4°/min). The peak areas were measured with a planimeter. The
results indicated that there was no significant change in the rate of benzene
delivered to the cartridges due to a 34% decrease in the flow rate, provided
that time was allowed for the concentration of vapor in the carrier gas to
equilibrate. Such variation as was observed in the peak areas was probably
due to continued small variations in the flow rate and to the uncertainty
(+5%) in the 5 min collection period.
When the flow was split ~1:1 between the cartridge and the flame ioniza-
tion detector, some inbalancing of the flow rate upon insertion of the cart-
ridge was observed. This was probably due to an additional contribution to
flow resistance as offered by the cartridge. Somewhat smaller peaks than
would have been anticipated from the benzene permeation tube were observed.
The ability of the flow system to deliver aliquots of vapors to sampling
cartridges was further tested by using it to calibrate a gas chromatograph
with flame ionization detection and a glc-ms-comp system. For the purpose of
calibrating a gc-fid system, dichloromethane, chloroform, benzene and toluene
were selected. Benzene and dichloromethane were used to calibrate the glc-ms
system.
Permeation tubes containing dichloromethane, chloroform, benzene and
toluene were placed together in the permeation chamber (Fig. 2). Nitrogen
carrier gas at a flow of ~6 ml/min was passed over the permeation tubes and
the effluent stream split. One portion of this stream was exhausted into a
fume hood and the other portion was passed through a Tenax cartridge.
Sampling cartridges were loaded with calculated amounts of each of the
vapors. The permeation rate and the loading time was related by the follo-
wing expression:
G - F P
a ~ F + B ' Pa
31
-------
where G = g of vapors a loaded on cartridge
F = ml/min of flow to cartridge
B = ml/min flow by-passed
P = permeation rate for vapor a (g/min)
Si
t = loading time
After the cartridges were loaded with known amounts of vapors, they were
thermally desorbed and analyzed by gc-fid vPerK'n-Elmer Series 900 gas
chromatograph quipped with a 200 ft C"-101 SCOT capillary). Peak areas for
each of the constituents were measured with a planimeter and a linear regres-
sion analysis of the data was performed. The linear regressions are shown
in Figure 5. Also included are the 95% prediction intervals, which indicate
that 1 out of 20 analyses would fall outside of this range.
Calibration of the glc-ms system was also performed for benzene and
dichloromethane. Single ion monitoring was used in both cases (benzene-m/e
78, dichloromethane-m/e 49); hpwever, in this case each compound was indivi-
dually examined. The calibration plots with the 95% prediction intervals are
shown in Figure 6.
The large prediction intervals indicated that improvements in the precision
of the method were required. There were two evident sources of uncertainty
which could be minimized: (1) the fluctuation in the flow rate and the split
ratio during loading of cartridges, (2) inaccurate measurements of the time
of loading because of the complicated procedure of replacing an empty tube
with a cartridge and fitting tjie connection to the sampling cartridge.
Three modifications to the system were made in order to improve its
precision: (1) The flow rate and pressure of nitrogen carrier gas to the
system was stablized. Use of prdinary nitrogen pressure regulator with a
needle valve to regulate the gas flow was inadequate. The flow was not
constant but varied sinusoiduly and this effect was multiplied by the method
used to split the gas stream. Stabilization of the flow delivered to the
system was achieved using a Moore regulator placed in line immediately up-
stream of the permeation chamber. This permitted rapid equilibration of
chamber pressure and afforded 9 maximum resistance to changes in pressure
caused by changes in the split ratio or the flow rate through the chamber.
(2) The oil monometer was replaced. The high viscosity of the oil precluded
rapid response to changes in line pressure. This often led to operation of
32
-------
2000 3000
NANOGRAMS
40OO
5000
— 1400
LU
g 1200
< BOO
UJ
o:
<
< 6OO
*
" 400
Q
U.
TOLUENE. NANOGRAMS (HUNDREDS)
ZOO 4OO 6OO '• BOO IOOO 1200
3000
IOQD
O
U.
O 200O 4000 60OO 8OOO 10000 12000
CHLOROFORM, NANOGRAMS (THOUSANDS)
Figure 5. Linear regression of flame ionization response vs.
weight of substance.
33
-------
< 5
UJ D
o:
<
UJ
Q.
CO
UJ
to
o
(X
o -
o
200 500 400 500 600 700 800
BENZENE, NANOGRAMS
900 1000 1100 1200
100 200 300 400 500 GOO 700 800 900 1000 1100 1200
METHYLENE CHLORIDE, NANOGRAMS
Figure 6. Linear regression of mass spectrometer response
(single ion mode) vs. weight of compound.
34
-------
the system under conditions of changing pressure (and therefore flow rate).
The monometer was replaced with a Matheson 63-3101 pressure gauge having a
range of 0-15 in water. (3) The process of introducing and removing cart-
ridges resulted in an uncertainty in the sampling time of about 20 sec. To
obtain acceptable precision longer sampling times were required. Reduction
in the uncertainty of the sample collection period was accomplished by
installing a by-pass (dashed lines in Fig. 2) to permit the flow to be
maintained while the cartridge is inserted. Reduction of the time
variation by a factor of about 10 was achieved. Teflon plug three-way
stopcocks were used. They were observed to operate without leaking at
the pressures prevailing in the system.
The precision of the system could be further improved by installing
a flow controller in place of the needle valve used to direct carrier
gas to the cartridges. In the present system small variations in flow
resistance of individual cartridges result in slight alterations in the
.- split ratio. This effect is not a serious source of error but its
elimination could effect a further increase in precision.
35
-------
SECTION 7
DEVELOPMENT OF TECHNIQUE FOR TL? PREPARATION OF
GLASS CAPILLARY SCOT COLUMNS
Glass open tubular columns have several advantages. They have superior
resolving power, generally require lower operating temperatures, are much
less apt to catalyze rearrangements and/or degradation of reactive subs-
tances and can be demonstrated to pass compounds that normally would fax! to
be transmitted through metal open tubular capillary columns. There are a
number of methods in the literature which have been reported for coating
capillaries which implies that the coating technique has remained a major
problem area. Most of the methods that have been suggested fall into two
general categories: (1) those which utilize a dynamic method in which a
relatively concentrated (~10%) solution of liquid phase and an appropriate
solvent is passed through the column under highly controlled flow condi-
tions , and (2) a static technique in which the column is completely
filled with a relatively dilute (~1%) solution of the liquid phase and as
the solvent is evaporated under vacuum and the residual phases deposited
hopefully as a thin uniform film on the inner column wall.
A new method has been developed for preparing glass open tubular columns
which allows the preparation of capillaries in a very routine and simple
manner. The procedures that have been developed are described here and are
based upon the modification of the procedures reported by Jennings, et
al./8) German, et al. /9>10) and Pellizzari.(11^
EXPERIMENTAL
A Hupe-Busch glass drawing machine (Hupe-Busch Karlsurhe Germany) was
used for preparing capillaries of various diameters and lengths.
Prior to drawing the glass capillary, the tubing (8 mm o.d., 4 mm i.d.,
and 2 m in length) was washed with acetone, methanol, methylene chloride and
dried. Prior to drawing short pieces (6-8 in) of tube are attached in order
to increase the effective drawing length. Lengths of up to 130 m can be
drawn for capillaries which have an internal diameter of 0.30 mm.
36
-------
After drawing the capillary, the capillary was washed with 50 ml of
acetone and methanol. Glass capillaries were silanized with a 10% solution
of dimethyldichlorosilane and toluene followed by rinsing with toluene,
methanol and acetone using ~20-30 ml of each solvent. The coating solution
consisted of 0.1% surfactant (benzyl triphenylphosphonium chloride), 0.1% of
^t>\
Silanoxv-/and 2.0-3.5% of stationary phase in methylene chloride. Prior to
filling the capillary with the coating solution, a 1-2 ml quantity of methy-
lene chloride was introduced as a wetting plug in front of the coating
solution. The coating solution was forced into the capillary using a pres-
surized reservoir. The glass capillary was entirely filled with the coating
solution and one end sealed with a flame.
(8)
A coating oven was fabricated as shown in Figure 7. The column was
placed on the drive shaft of the oven and the spring-loaded drive-follower
was positioned. Two coils of the open end of the filled column was rotated
into the oven. Then the oven temperature was raised to 150°C and the inlet-
coil tube which passes the capillary through the oven wall was heated to
200°C. The drive motor was then energized at a rate of 13 revolutions/
minute. The drive shaft on the apparatus had a diameter of ~12.7 mm. A
period of ~1.5 hr was required to drive a 100 m capillary into the coating
oven. All but the last two coils of the capillary was driven into the oven
and then the sealed end was broken. Through the capillary helium gas was
passed at a rate of ~4-6 ml/min for a period of 30 min. This step was neces-
sary to remove all residual solvent prior to cooling the capillary. The oven
was then cooled and the capillary removed. The first and last five coils of
the capillary were discarded and the column was then ready for use.
RESULTS AND DISCUSSION
During the developmental stages, some difficulty was encountered in the
drying step of the coating procedure. The deposition of the Silanox^which
served as a support material was often uneven. The position of the vapor
liquid interface did not always remain constant and some bumping occurred.
/T>\
Adjustment of the percent of Silanox^to 0.1% yielded a more evenly coated
capillary. Perhaps the use of higher density solvent such as Freon 113
which has a boiling point similar to methylene chloride but a density be-
tween chloroform and carbon tetrachloride would be more appropriate as a
medium for suspending the Silanox^S/ The density provided by Freon 113 may
37
-------
Oven window
Heated inlet
tube
Drive shaft Glass capillary
Motor
Figure 7. Glass capillary coating oven.
38
-------
ensure that the precipitation of the silanized fumed silicon dioxide (6-8 p)
would not occur and a more uniform deposition of the support could be achieved
on the inner capillary wall.
The mechanism for deposition of the silanized fume silicon dioxide and
liquid phase occurs during the introduction of the filled capillary into the
heated inlet zone of the coating oven where an aerosol is formed which
disperses the liquid phase and Silanox^onto the wall. Under these condi-
tions any liquid phase can be forced to coat the column, however whether it
remains as a thin coherent film probably depends upon the degree of attrac-
tion between the glass surface and the liquid phase as opposed to the cohe-
sive forces or surface tension of the liquid phase.
The procedures described here were used for preparing OV-101, OV-225,
DEGS, and Carbowax 20M stationary phase coated SCOT columns. The highest
success was observed for OV-101 and Carbowax 20M as judged from the observed
number of theoretical plates.
A comparison of a 42 m glass SCOT capillary prepared as described above
and a commercial 400 ft stainless steel SCOT capillary also coated with OV-
101 are shown in Figures 8 and 9, respectively. A duplicate set of Tenax GC
sampling cartridges which contained ambient air sampled in C. H. Milby Park
in Houston, TX was used for this evaluation. A higher intensity of lower
eluting materials was observed in the glass capillary than for the stainless
steel column. This implies that the percent transmission of the pollutants
from ambient air was better for the glass capillary column. Another example
is given in Figure 10.
Longer glass capillary columns need to be investigated for comparison
with the stainless steel SCOT capillaries. Various combinations of coating
solutions (semi-polar and polar) also need to be examined for the prepara-
tion of capillaries which will resolve ambient air pollutants of interest
using the new developed procedure.
39
-------
32 44 56 68
TEMPERATURE (°C)
92 104 116 128
•I-
164
36
—I—
42
48
12
18
21 24 27
TIME (MIN)
30
33
39
45
Figure 8. Profile of ambient air pollutants obtained for C. H. Milby Park, Pasadena,
TX using glass capillary gas chromatography/mass spectrometry/computer.
A 42 m glass SCOT coated with OV-101 stationary phase was used; temperature
programmed from 20-220°C @ 4°C/min.
-------
I00r
36 39 42
TIME (M1N)
Figure 9. Profile of ambient air pollutants obtained for C. H. Milby Park, Pasadena, TX using
capillary gas chromatography/mass spectrometry/computer. A 400 ft S. S. SCOT coated
with OV-101 stationary phase was used; temperature programmed from 20-240'C @ 4°C/min.
-------
ro
90|-
80
70-
60-
50-
40
30-
20-
10 _
0 —
S3
TEMPERATURE (°C)
104 116 128
192 164
15
21 24 27
TIME (WIN)
30
33
36
39
42
45
212
—(
48
Figure 10. Profile of ambient air pollutants for Wood River, IL, using glass
capillary gas chromatography/mass spectrometry/cotnputer. A 42 m
glass SCOT coated with OV-101 stationary phase was used; temperature
programmed from 20-220°C @ 4°C/min.
-------
SECTION 8
CHARACTERIZATION OF ORGANIC VAPOR EMISSIONS FROM1
CONTROLLED PRE-SET FIRES
The objective of this study was to apply a new technique which had been
developed for ambient air analysis to the identification of any hazardous
organic vapors which might be emitted from controlled deliberately set fires
of lobbly pine needles. In addition to the identification of organic com-
pounds in emitted vapors, an estimation of the quantities of each of the
constituents was made.
EXPERIMENTAL
Sampling Procedure
The sampling procedure employed consisted of concentrating organic
vapors on a 1.5 x 10.0 cm glass sampling cartridge containing the sorbent
^ „ -_ (35/60 mesh). All sampling cartridges were preconditioned by
heating to 275°C for a period of 20 min under a helium purge of 20-30 ml/
min. The sorbent used in the sampling cartridges was previously extracted
with acetone for a period of 18 hr in a Soxhlet apparatus. The precondi-
tioned sampling cartridges were then cooled in a Teflon^-'-lined capped
centrifuge tubes to prevent contamination of the cartridge. Samp-
ling cartridges prepared in this manner were carried by automobile to the
Southeastern Forest Exprimental Station in Macon, GA for sampling of vapors
from fires. Of this group of sampling cartridges, 2-3 cartridges were
designated as controls to establish whether contamination occurred by the
packing and transportation procedure.
Two portable field samplers (Model 221-A, Nutech Corp., Durham, NC)
were used. The portable field samplers were fabricated according to the
design criteria as outlined in previous reports which allowed sampling to be
conducted in either AC or DC mode. A glass fiber filter (Gelman type
A/E) was used to remove particulate material. Organic vapors which passed
through the glass fiber filter were collected on the Tenax GC^-'sampling
cartridge.
43
-------
The experimental protocol for sampling organic vapors emitted from
fires is given in Table 5. Two types of fires were set. One was a front
fire, the second a back fire. Organic vapors were collected on Tenax GC^-s
cartridges during the flame period and during the smouldering period from
each of these fires. The intention was to sample at a point above the flame
(n/m) as well as at the roof-top (~3-4 m). Since it began to rain during
the first experiment, a sample from the roof-toj during the smouldering
period was not ',aken, nor during any v2 the subsequent experiments. Thus
vapors were collected only indoors. In the third experiment the quantity of
lobbly pine needles was increased to 6 Ibs (head fire).
Characterization of Organics Emitted from Fires
The instrumental system (glc/ms/comp) used for the qualitative analyses
of organic vapors and the inlet-manifold used for recovering vapors trapped
on Tenax GC^'sampling cartridges has been previously described.
The operating parameters for the glc/ms/comp system for analysis of
samples are shown in Table 6. Samples were analyzed on a 100 m glass SCOT
capillary coated with OV-101 stationary phase. The desorption of vapors
from the sampling cartridges was achieved at 265-270°C. A single stage
glass jet separator interfaced the SCOT capillary columns to the mass spectro-
meter and was maintained at 220°C. The capillary column was programmed from
20-240°C @ 4°C/min.
Identification of resolved components was achieved by comparing the
mass cracking pattern of the unknown mass spectra to an 8 major peak index
(12) (13)
of mass spectra and to the Wiley collection. In several cases, the
identification was confirmed by comparison with authentic compounds of the
mass spectrum and the elution temperature. Particular note was made of the
relationship of the boiling point of the identified compound to its elution
temperature and to the order of elution of the constituents in a homologous
series since the OV-101 SCOT capillary column separates primarily on the
basis of boiling point. For estimation of the levels of each of the consti-
tuents that were identified, the relative molar response was used in order
to calculate an approximate value for the concentration of the constituent.
The concentration was expressed in ng/£ of air sampled above the fire. The
concentration was also based upon the breakthrough volume of the constituent
for the Tenax GC sampling cartridge.
44
-------
Ul
Table 5. EXPERIMENTAL PROTOCOL FOR SAMPLING ORGANIC VAPORS
EMITTED FROM FIRES
Experiment
No. Burn Type/Period
1A
IB
1C
2A
2B
3A
3B
Head
Head
Head
Back
Back
Head
Head
fire/ flame
fire/smouldering
fire/flame
fire/ flame
fire/smouldering
fire/flame
fire/smouldering
Sampling Sampling Time
Point (min)
above
above
flame
flame
at roof-top
above
above
above
above
flame
flame
flame
flame
7
12
7
7
8
7
20
.5
.0
.0
.0
.0
.0
Sampling Rate Total Volume/Cartridge
(a/mln) W
6.
6.
4.
5.
7.
6.
5.
7
2
6
8
4
2
8
50.
74.
32.
45.
59.
43
116
2
4
2
2
2
.4
.0
-------
Table 6. 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)
MS
single stage glass jet separator
ion source vacuum
filament current
multiplier
scan rate, automatic-cyclic
scan range
265°-270°
175°
-195°C
+175°C
~4 min
20-240°C
1.5 ml/min
200°C
~2 x 10~ torr
300 yA
5.5
1 sec/decade
m/e 20 •*• 300
46
-------
RESULTS AND DISCUSSION
The results of the experiment No. 1A (Fig. 11) are shown in Table 7.
This experiment consisted of a front burn and the sampling was done during
the flame period. The total volume collected on the Tenax GC sampling
cartridge was 50.2 £. Based upon the absolute quantity on the sampling
cartridge as determined by gc/ms/comp analysis and the breakthrough volume
for each of the constituents, an estimation was made of the concentration of
that vapor per liter of gas sampled. The major constituents emitted from
the fire were benzene (320 ng/A), toluene (891 ng/Jfc), furfural (627 ng/£),
g-xylene (529 ng/£), and limonene (622 ng/£). As can be seen in Table 7
there were many alkanes, alkenes and in particular oxygenated compounds
which were analogs of furan. Also indicated are those compounds which can
; be regarded as background vapors in the ambient air. Several background
peaks which constitute "bleed" from the chromatographic column are also
labelled. In many cases where there were peaks which were not homogeneous,
the identity of the constituents were designated by an alpha-numeric system.
For example, peak No. 3 contained n-butane, isobutane and 2-methylpropene
and the latter two were designated 3A and 3B. Also, it is important to note
that the numbering sequence is not in all cases complete. Where the chroma-
tographic peak number has been omitted, the identity of the constituent
could not be established.
The results of experiment IB are shown in Table 8. Sampling was per-
formed during the smouldering period, in contrast to the previous case which
was during the flame period. This sample contained acetamide and 4 phenols
(o-methoxyphenol, o-methallyphenol, phenol and o-cresol).
In experiment 1C (Fig. 12 and Table 9) vapors were collected at the
roof-top during the flame period. This sample in contrast to the one presen-
ted in Table 8 exhibited a larger number of carbonyl compounds. Also,
phenols were not detected during the flame period.
Experiment 2A and 2B represented a repeat of the experiment 1 except a
backfire was set. In this case sampling at the roof-top was complicated by
rain. When this sample was examined, there was an appreciable amount of
water which interferred with the gc/ms/comp analysis. Thus, the identi-
fication was possible of only those constituents present in the smouldering
sample taken indoors above the fire.
47
-------
00
100
90
80
2 «0'
O
-I JO
10
0
80
100
120
140
COLUMN TEMPERATURE (°C)
Figure 11. Organic vapor profile for experiment 1A.
-------
Table 7. ORGANIC VAPORS EMITTED FROM HEAD FIRE
DURING FLAME PERIOD3
Chroma tographic
Peak No.
1
2
3
3A
3B
4
5
6
7
7A
8
9
9A
10
11
11A
11B
12
13A
13
14
14A
15
15A
20
21
21A
Elution
Temperature
(°C)
54
62
62
63
64
74
77
79
80
80
81
82
82
85
89
91
91
92
94
94-102
97
99
100
101
102
109
111
Compound
unknown
chloromethane
n-butane
isobutane
2-methylpropene
1-pentene
isopentane
C.-H..Q isomer
furan
C-H-- isomer
n-pentane
acetone
isoprene
2-methyl-2-butene
cyclopentadiene
methyl ally ether
cyclopentane
glycerol
methoxymethylsilane
(BKG)
tr imethyls ilanol
(BKG)
diacetyl
1-hexene
2-pentanone
2-methylfuran
n-hexane
C,H1rt isomer
D 1U
C,Hg isomer
ng/fc
5
2
1
-
-
2
1
8
1
2
15
1
6
2
-
-
3
—
—
17
-
38
-
-
2
~
(continued)
49
-------
Table 7 (cont'd)
Chroma tographic
Peak No.
21B
23
24
25
26
27
28
29
31
34
36
38
43
45
46
47
48
49
51
53
54
55
56
57
58
59
60
Elution
Temperature
111
112
114
116
118
119
120.5
120-135
113
137
139
141
146
149
150
151
152
153
159
163
165
166-167
168
169
170
171
171.5
Compound
1, 1, 1-trichloroe thane
C,H-_ isomer
O 10
2 , 4-hexadiene
benzene
2-methyl-4,5-
dihydrofuran +
C.,H.., isomer
7 ID
2 , 5-dimethyltetra-
hydrofuran
ri-heptane
BKG peak
C7H14 isomer
3-methy Ihexane
CQHn, isomer
o ID
toluene
1-octene + C-H--.0
isomer
n-octane
furan-3-aldehyde
2,3, 5- tr imethy If uran
hexamethy Itr is iloxane
(BKG)
furfural
CgH.. , isomer
ethylbenzene
_p_-xylene
BKG peak
1-nonene
styrene
o-xylene
n-nonane
2-isopropylfuran
ng«
-
3
320
(83 + 64)
5
4
-
17
22
891
129
26
5
-
-
627
-
144
529
-
219
192
144
-
-
(continued)
50
-------
Table 7 (cont'd)
Chromatographic
Peak No.
61
63
63A
66
68
69
70
71
72
73
74
75
76
77
77A
78
79
79A
80
80A
81
82
83
84
84A
85
85A
87
Elution
Temperature
<°C)
172.5
175.5
176
180
182
182
183
185
186
187
189
189.5
190.5
191
192
193.5
194
195
196
197
198.5
200
200.5
201
201.5
202
202.5
205
Compound
anisole
o-methylanisole
isopropylbenzene
2-methylstyrene
benzaldehyde
5-methyl-2-furaldehyde
+ £-tolualdehyde
1,3, 5- trimethylbenzene
Cn -.Hn , isomer
10 16
a-methylstyrene
C Hn_ Isomer
10 18
1-decyne
m-methylstyrene
m-ethyltoluene
benzofuran
myrcene
dichlorobenzene
2-methyl-5-isopropyl-
furan
o-cymene
1,2, 3- trimethylbenzene
2-n-butyrylfuran
limonene
tr imethylphenoxys ilane
(BKG)
C,-alkyl benzene
indene
m-diethylbenzene
n-butylbenzene
1,1, 2-trichloropropane
(tent.)
1-undecene
ng/fc
-
-
-
32
18
-
6
9
19
_
158
-
161
2
-
16
2
-
232
-
622
-
2
1
-
-
-
3
(continued)
51
-------
Table 7 (cont'd)
Chromatographic
Peak No.
88
89
90
91
91A
91B
92
93
96
99
99A
100
101
102
105
108
109
Elution
Temperature
(°C)
207
208.5
209
210
211
212
213
215.5
220.5
225
226
227
228
230
236
240.5
242
Compound
unkrown
n-undecane
cyclododecene + o-
methoxybenzaldehyde
C,--alkyl benzene
7-methylbenzofuran
o-methyoxyphenol
^-methylacetophenone
C5-alkyl benzene
3-methylindene
1,2, 4-tr ichlorobenzene
n-dodecane
naphthalene
dimethyldihydroindene
l-methyl-3-t-butyl-
benzene
trimethyldihydroindene
1-tridecene
n-tridecane
ng/A
163
27
3
24
-
-
6
-
-
9
-
4
5
6
-
38
36
aSee Tables 5 and 6 for sampling and instrumental conditions, expt. 1A.
Vapors often present in ambient air sampled.
52
-------
Table 8. ORGANIC VAPORS EMITTED FROM HEAD FIRE
DURING SMOULDERING PERIOD3
Chroma tographic
Peak No.
2
2A
3
3A
3B
3C
4
5
5A
5B
6
6A
6B
6C
6D
7
8
8A
8B
9
10
11
12
13
14
15
ISA
15B
15C
Elution
Temperature
(°C) Compound
68
72
75
76
77
77
78
79
80
81
82
86
87
90
91
92
93
94
95
96
98
99
100
103
104 ,
105
106
107
108
1-pentene
C-H-.^ isomer
isopentane
C ,-H- - isomer
furan
2-pentene
n-pentane
isoprene
diethyl ether
acetone
2-methy 1- 2-but ene
dimethoxymethane
unknown
cyclopentene
ethyl vinyl ether
column background
column background
diacetyl
C,H, . isomer
6 14
1-hexene
2-methylfuran
n-hexane
chloroform
3-methyl- 2-pentene
3-methylpentane
methylcyclopentane
C,H,n isoraer
D 1U J
1,3, 5-hexatriene
C,Hno isomer
b Lf.
(continued)
53
ng/Jl
3
-
1
—
-
2
2
-
-
2
-
-
-
-
-
-
-
2
12
3
4
-
-
-
^
-
-------
Table 8 (cont'd)
Chroma to graphic
Peak No.
16
16A
16B
17
18
18A
19
20
20A
21
22
22
24
25
26
27
28
29
30
31
32
33
35
35A
35B
36
•37
38
Elution
Temperature
108
109
110
111
112
113
114
115
115
116
117
116-129
120
121
122
125
127
129
'• 132
134
137
139
142
143
144
145
146
148
Compound
1,1, 1-trichloroethane
C,-H1f.O isomer
2 , 4-hexadiene
2-pentanone
benzene
carbon tetrachloride
C-.H-, isomer
/ io
2, 4-dimethylpentane
3-methyl-hexane
C..H.., isomer
cycloheptane
hexamethyldisiloxane
(BKG)
2 , 5-dimethylf uran
n-heptane
2-vinylfuran
cyclohexylamine (tent . )
dimethylpentene isomer
2-hexenal
2-ethyl-l-hexene
l,trans-2,cis-3-tri-
methylcyclopentane
toluene
1-octene
trans-4-octene
CQH.. . isomer
o J.'*
2-octene
n-octane
2,3,5-trimethylfuran +
furan-3-aldehyde
hexamethylcyclotrisilo-
xane (BKG)
ng/Ji
1
-
-
-
77
-
27
21
-
18
-
-
8
29
-
-
6
92
11
9
97
6
7
-
-
9
(2 + 1)
_
(continued)
54
-------
Table 8 (cont'd)
Chromatographic
Peak No.
39
40
40A
41
42
42A
43
44
44A
45
46
46A
47
48
50
50A
51
52
53
54
56
Elution
Temperature
149
152
153
159
161
161
162
1
165
165
166
167
168
169
172
178
178.5
179
181
180-4
183
185
Compound
2-methyl-5-vinylfuran
furfural
2,5-diethylfuran
ethylbenzene
£-xylene
CQH Q isomer
7 -LO
octamethyltrisiloxane
(BKG)
1-nonene
styrene
o-xylene
n-nonane
CQH Q isomer
y JL.O
furyl methyl ketone
isopropylbenzene
CT^HT, isomer
1U ID
m-ethyltoluene
5-methy 1-2- fur aldehyde
+ benz aldehyde
_p_-ethyltoluene
acetamide
o-ethyltoluene
a-methylstyrene +
ng/£
2
31
-
8
101
-
7
-
22
3
_
-
^
—
Ill
123
96
-
57
187
57A
61
61A
62
62A
63
188
193
193
194
195
196
ti-(
O-l
l,:
cli
lii
£-1
(continued)
55
1-decene
1,3,5-trimethylbenzene
+ C10H18 ±SOmer
-decane
1,2,3-trimethylbenzene
H18 is°mer
jv-propyltoluene
31
33
75
-------
Table 8 (cont'd)
Chr oma togr aphic
Peak No.
64
65
66
68
68A
69
70
71
72
72A
72B
75
76
77
77A
78
78A
79
82
83
84
Elution
Temperature
198
199
201
204
205
206
207
210
212
213
214
220
221
223
224
225
226
227
237
239
241
Compound
indene
1 ,2-Jiethylbenzene
acetophenone
1-undecene
unknown
n-undecane
2-methy Ib enzo f ur an
dimethylethylbenzene
(isomer ?)
C,-alkyl benzene
o-methoxyphenol
o-methallylphenol
cyclododecane
unknown
n-dodecane
trimethylphenoxysilane
(BKG)
phenol
naphthalene
^-cresol
C10H0/. isomer
IJ
-------
100
9O
60
£t
or
fi «•
5 30
_j
3
K
10
0
4b CO 80 100
140 160 160 ZOO
COLUMN TEMPERATURE (°C )
Figure 12. Organic vapor profile for experiment 1C.
-------
Table 9. ORGANIC VAPORS EMITTED FROM HEAD FIRE DURING FLAME PERIOD3
Chromatographic
Peak Ko.
2
2A
'•
5
6
6A
7
8
8A
9
9A
10
10A
10B
11
12
13
13A
14
14A
15
17
18A
18
18B
19
20
21
22
Elution
Temperature
67.5
72
78
80
81
81
82
83
84
86
88
89
90
91
93
96
97
98
101
101
102
104
107
108
109
110
112
114
115
Compound
2-chloropropane
i-but >ne
isopentane
1-pentene
furan
2-methyl-2-butene
n-pentane
isoprene
acetone
C,-H..n isomer
C-H- isomer
J O
1, 3-pentadiene
cyclopentadiene
S02 (tent.)
vinyl ethyl ether
isopropanol + trimethyl
silanol (BKG)
C,H, , isomer
6 14
methyl vinyl ketone
methyl cyclopentane
methyl ethyl ketone
2-methyl furan
C,H.0 isomer
O L2.
C,H,- isomer
b
1,1, 1-tr ichloroethane
methyl propionate
(tent.)
2,4-hexadiene
1,3,5-hexatriene
3-methylbutanal (tent.)
C6H10 ls°mer
-ng/A
-
-
-
-
2
-
3
21
-
15
-
7
-
-
8
15
(alcohol)
23
-
45
-
97
7
3
-
id
15
9
8
(continued)
58
-------
Table 9 (cont'd)
Chromatographic
Peak No.
23
24
24A
25
26
27
28
29
30
30A
31
32
33
34
34A
35
35A
36
36A
37
38
39
40
41
42
44
45
Elution
Temperature
116
117
118
118-120
121
122
124
125
125
126
127
128
129
130
131
134
134.5
135
136
137
140
142
144
146
147
150
151
Compound
methyl isopropyl
ketone
benzene
C,H10 isomer
o i/
methyl isopropenyl
ketone
2-me t hy 1- 3-p ent anone
2 , 4-dimethylpentane
unknown
l-trans-2-dimethyl-
cyclopentane
2-methyl-2 , 4-hexadiene
(tent.) or C7H12
isomer
2, 5-dimethylfuran
n-heptane
trans-2-heptene
2 , 4-dimethylf uran
2-vinylfuran
C_H1- isomer
methylcyclohexane
2-methyl-4, 5-dihydro-
furan
d ihydr opyran ( tent . )
furan-3-aldehyde
C7H12 isomer
3-ethyl-2-pentene
toluene
C?H1 „ isomer
1-methylcyclohexadiene
1-octene
n-octane
2,3, 5-tr imethylf ur an
ng/£
33
330
-
50
54
12
-
240
-
-
280
-
3
21
-
24
-
23
-
4
8
704
22
15
321
25
7
(continued)
59
-------
Table 9 (cont'd)
Chromatographic
Peak No.
47
49
54
55
56
57
58
59
60
61
62
63
64
66
67
68
69
70
71
73
74
75
76
77
78
79
79A
Elution
Temperature
152
155-157
163
165
166
169
170
171
172
173
174
176
177
180
182
183
184
185
186
188
190
191
192
193
195
196
196
Compound
hexamethylcyclotrisi-
loxa^e (BKG)
furfural
ethylbenzene
_p_-xylene
1-nonene
styrene
o-xylene
n-nonane
2-isopropylfuran
(tent.)
anisole
furyl methyl ketone
(tent.)
2-isobutenylfuran or
o-methy laniso le
isopropylbenzene
n-propylbenzene
5-methyl-2-furfural
+ benzaldehyde
C9H12
1,3, 5-tr imethylbenzene
Clf)H fi isomer
C10H18 isomer
C,QH isomer
a-methylstyrene
C_-alkyl benzene
benzofuran
C8H1()0 + C1QH
isomers
1-decene
o-cymene
1,2, 3-tr imethylbenzene
„/*
-
2096
301
659
32
348
25
13
—
27
5
—
4
-
—
-
21
-
26
342
-
419
-
89
_
-
_
(continued)
60
-------
Table 9 (cont'd)
Elution
Chromatographic Temperature
Peak No. (°C) Compound ng/£
79B
80
80A
81
82
83
84
85
86
87
87A
88
95
97
98
100
101
104
105
106
107
110
111
197
198
199
199.5
201
202
204
205
206-7
208
208
209
220
223
225
228
230
238
240
242
245
261
263
2-n-butyrylfuran
C10H16 isomer
limonene
unknown
indene
diethylbenzene
C.-alkyl benzene
1-undecene
unknown
n-undecane
l-methyl-4-isopro-
penylbenzene
C,.-alkyl benzene
methyl indene
cyclododecane
n-dodecane
naphthalene
4, 7-dimethylbenzof uran
C,-H2, isomer
1-tridecene
n-tridecane
biphenyl
1-tetradecene
n-tetradecane
_
-
-
17
14
11
12
-
115
-
12
47
132
96
76
6
-
107
109
-
145
86
aSee Tables 5 and 6 for sampling and analysis conditions, expt. 1C,
Vapors often observed in ambient air.
61
-------
Table 10 lists the organic vapors identified for Experiment 2A. Again
the major constituents were benzene, toluene, and xylene. In this sample a
trace of acetaldehyde was detected. This experiment produced a fewer number
of oxygenated compounds during the flame period as compared to experiment
1A. The majority of vapors emitted during the smouldering period (Expt. 2B,
Table 11) were alkanes and alkenes (straight and branched).
Tables 12 and 13 list the compounds identified from the flame and
smouldering pe -iod, respectively, of a head fire for a 6 Ib. load of pine
needles. This experiment was not as successful since there had been larger
accumulation of fine carbon-like particles which passed through the glass
fiber filter and settled in the Tenax GC sorbent bed. The presence of
carbon apparently complicated the desorption of organic vapors from the
cartridge. The overall quantity of each organic compound was considerable
less than expected for the increased pine needle load (compared to Expt. 1A
and IB).
Future studies of this nature which utilized a Tenax GC sampling cart-
ridge can be improved by:
(1) employing a glass fiber filter (or equivalent) which will retain
fine carbon particles generated during burning,
(2) reducing the total volume of air sampled in order to avoid over-
loading the glass capillary column used for resolving the mixture of compo-
nents ,
and (3) sampling at ambient temperature of 50-70°C instead of cooling the
cartridge with ice in order to minimize accumulation of water.
62
-------
Table 10. ORGANIC VAPORS IDENTIFIED IN EMISSIONS FROM
BACKFIRE DURING FLAME PERIOD3
Chromatographic
Peak No.
1
1A
IB
1C
2
2A
3
3A
3B
3C
3D
3E
4
4A
4B
4C
4D
5
6
6A
6B
7
7A
10
11
11A
13
Elution
Temperature
( °C) Compound
68
72
73
74
77
76
81
82
82
84
86
88
92
92
93
94
96
96
97
98
98
100
102
108
112
113
115
acetaldehyde
isopentane
t r i f lu or ome t hane
1-pentene
furan
1 , 3-pentadiene
acetone
divinyl ether
methylene chloride
methylal (tent.)
cyclopentadiene (tent.)
carbon disulfide
dihydrofuran + CfiH..?
isomer
2-methylprop-2-en-l-al
trinethyl si.lsnol (BKG)
diacetyl
C,H10 isomer
D 12
methylcyclopentane
2-methylfuran + methyl
vinyl ketone
2-meth.ylpentane
methyl ethyl ketone
chloroform
3-me thy 1- 2-pent ene
bl,l,l-trichloroethane
benzene
carbon tetrachloride
4-iiiethyl pentana
(continued)
63
ng/2.
-
~
-
4
3
3
"
-
-
-
3
-
-
~
4
4
-
7
3
252
8
-------
Table 10 (cont'd)
Chroma tograpliic
Peak No .
14
14A
14B
16
17
17A
17B
17C
18
19
20
21
22
23
23A
24
24A
24B
25
26
27
28
30
31
32
34
35
Elution
Temperature
(°C) Compound
116
117
118
120
122
122
123
124
126
127
129
130
131
132
133
134
135
135
136
137
142
144
147
148
150
157
158-9
l-cis-3-dimethylcyclo-
pentan°
3-ethylpentane
3, 4-dimethyl-l-pentene
2 , 3-dihydrof ur an
1- trans- 2-dimethylcyclo-
pentane
2 , 5-dimethylf uran
n-heptane
2 , 4-diiuethylf uran
2-vinylfuran
2, 2,4-trimethylpentane
methyl cyclohexane
2 , 4-dime thy Ihexane
2,2, 3-tr imethylpentane
C..H.. , isomer
/ ID
l-cis-2,cis-3-trimethyl
cyclopentane
methyl propenyl ketone
l-trans-2,cis-3-trimethyl
cyclopentane
C?HI, isomer
toluene
C0Hn 0 isomer
o lo
C0Hn, isomer
o ±o
n-octane
hexamethy Icy clot ri-
siloxane (BKG)
furfural
3- fur aldehyde
ethylbenzcne
£-xylcne
(continued)
64
ng/fc
16
3
-
4
13
-
-
-
2
9
200
-
-
10
—
6
-
-
1021
8
19
4
-
87
3
79
338
-------
Table 10 (cont'd)
Chromatographic
Peak No.
37
38
39
39A
39B
40
42
43
44
46
47
48
50
51
52
53
53A
54
55
55A
55B
56
57
58
59
60
61
62
Elutlon
Temperature
(°C) Compound
163
164
166
167
168
170
174
175
177
178
179
180
182
183
184
185
186
187
189
189
190
191
193
194
200
202
203
203
styrene
o-xylene
n-nonane
2-iso-propylfuran (tent.)
anisole
isopropylbenzene
5-methyl-2-fur aldehyde
unknown
o-ethyltoluene
phenylisocyanid or 2-
etheuyl-pyridine (tent.)
a-methyl styrene
C,-alkyl benzene
1-decene
m-methylstyrene
1,3, 5-trimethylbenzene
benzofuran
C, -,!!,, isomer
1U ID
m-dichlorobenzene
c-cyiaene
1,2,3-trimethylbenzene
2-decyne
liir.onene
2,3-diliydroindene (tent.)
+ C HIO isomer
indene
unknown
unknown
unknown
C10li12 isoiueir
(continued)
65
ng/£
99
92
-
-
-
2
2
-
7
-
-
-
18
4
57
-
3
80
-
-
92
5
-
-
-
8
-------
Table 10 (cont'd)
Chroma tographic
Peak Wo.
62A
64
Elution
Temperature
<°C)
204
205
Compound
n-ui-decane
2-methylbenzofuran
ng/Jl
-
-
aSee Table 5 and 6, expt. 2A.
Probably background in ambient air.
66
-------
Table 11. ORGANIC VAPORS EMITTED FROM BACK FIRE DURING FLAME PERIOD3
Chromatographic
Peak No.
5
6
7
8
9
10
11
11A
12
13
13A
13B
13C
13D
14
15
15A
16
17
18
19
20
21
21A
23A
23
24
25
Elution
Temperature
(°C) Compound ng/&
98
101
102
104
105
106
110
111
112
114.5
115
115
116.5
117
117.5
119.5
119.5
120.5
122
122.5
126
127
127 . 5
131.5
134 . 5
135.5
136
137
2-methylpentane
trimethylsilanol (BKG)
1-hexene
2-methylfuran
C,H... isomer
, 6 14
chloroform
n-hexane
2,2, 3-tr imethy Ibutane
2-methyl-l-pentene
3-methylpentane
1, 1,1-trichloroethane
unknown
2,4-hexadiene
3-methylcyclopentane
benzene
carbon tetrachloricle
2 , 4-d imethy 1-1-pentene
cyclohexane
3-ethylpentane
3 , 4-dimethy 1-1-pentene
trichloroethylene
1- trans- 2-dimethyl-
cyclopentane
n-pentane
2-vinylfuran
1 , 3-dimethy Icyclopentane
2 , 3-d imethy 1-2-pentene
C9H20 isomer
4 , 4-d imethyl-1-pentane
(continued)
67
_
-
1
1
2
5
2
-
2
3
-
-
-
25
-
-
20
13
20
18
19
23
-
-
82
-
-------
Table 11 (cont'd)
Chroma tographic
Peak No-
26
26A
27
28
29
30
31
31A
32
33
34
35
36
37
38
38A
39
40
41
42
43
44
4AA
45
45A
46
46A
Elution
Tempera Lure
(°C) Compound
138
139
140
142-144
144-145
148
149.5
149.5
152
162-163
164-166
168
170
180-181
182
182
183
184
185-186
187
188.5
190
1.93
195
195
197.3
198.5
C-,11,, iTomer
/ ID
l-cis-2,cis-3-tri-
methy Icy clop entane
l-trans-2,cis-3-tri-
methylcyclopentane
toluene
3 , 4-dimethylhexane
1- trans- 2-dimathyl-
cyclohexane
1, 1-dimethylcyclohexane
n-octane
hexamethylcyclo-
trisiloxane (BKG)
ethylbenzene
p-xylene
styrene
o-xylene
terpene
n-propylbenzene
benzaldehyde
j>-ethyl toluene
C-inHoo
10 22
phenyl isocyanid or
3-ethyl-pyrldine
1,3, 5-trimethylbenzt'.nc
4-raethylstyrene
2,3-benzofuran
n^-d i ch lo r ob c.nz ene
o-cyniene
1 , 2, 3-trimot.hylbenzene
liraonene
ct-inethy Is ty rcne
(continued)
68
ng/£
19
-
5
240
6
7
4
~
-
20
76
6
40
1
1
-
-
—
-
-
7
_
&
5
4
-
-------
Table 11 (cont'd)
Chroma tographic
Peak No.
46B
46C
50
54
56
58
61
Elution
Temperature
(°C)
200
200
207-208
222
224
225-227
260
Compound
indene
js-diethylbenzene
n-undecane
1-dodecene
n-dodecane
naphthalene
4-methylazobenzene
ng/A
_
-
3
1
I
3
2
aSee Tables 5 and 6, expt. 2B.
Probably background vapors in ambient air.
69
-------
Table 12. ORGANIC VAPORS IDENTIFIED IN EMISSIONS FROM
BACKFIRE DURING FIRE PERIOD
Chroma tographic
Peak No.
1-4
5
6
7
8
9
10
11
11A
12
13
13 A.
13B
13C
13D
14
15
15A
16
17
18
19
,20
21
21A
23A
23
24
25
26
Elution Temperature
_
98
101
102
104
105
106^7
110-111
111
112
114.5
115
115
116.5
117
117.5-119
119.5
119.5
120.5
122
122.5
126
127
127.5
131.5
134.5
135.5
136
137
13S
(continued)
70
Compound
unknowns
2-rr.ethylpentane
CrimeLhylsilar.ol (BKG)
1-hexene
2-meth/lfuran
C,IL , isociar
h
chloroform
n-hexane
2, 2,3-triraethylbutane
2-rcethyl-l-pentene (tent . )
3-methylpentane
1, 1, 1-trichloroethane
C7H8 (?)
2,4-hexadierie
3-r.iethylcyclopentane
benzene
carbon tetrachloride
2,4-dimethyl-l-pentene
cyclohexane
3-ethylpentane
3 , 4-diniei:hyl-l-pentene
trichloroethylene
l-trsnE-2-dimethyleyc.lo-
pentane
ri-heptane
2-vinylfuran
1 , 3-dimcthy 1 cyclopentane
2 , 3-dimethyl-2-prntcne
C^H- isomer
4, 4-dimethyl-l-pentcne
C-H.. , isomer
-------
Table 12 (cont'd)
Chromatog,raphic Elution Temperature
Peak No. (°C)
26A
27
28
29
30
31
31A
32
33
34
35
36
37
38
38A
39
40
41
42
43
44
44A
45
46
46A
46B
139
140
142-144
144-145
148
149.5
149.5
152
162-3
164-6
168
170
180-1
182
182
183
184
185-6
187
188.5
190
193
195
197.5
198.5
200
(continued)
71
Compound
l-cis-2,cis-3-trimethylcyclo-
pentane
l-trans-2,cis-3-trimethyl-
cyclopentane
toluene
3, 4-diraethylhexane
l-trans-2-dimethylcyclo-
hexane
1 , 1-dimethylcyclohcxane
n-octane
hexamethylcyclotrisiloxane
(BKG)
ethylbenzene
p_-xylene
styrene
o-xylene
terpene
n-propylbenzene
benzaldehyde
p-ethyl toluene
C,QH - isomer
phenylisocyanid or 3-ethenyl-
pyridine (tent.)
1,3, 5-trimethylbenzene
4-methyl-styrene
2,3-benzof uran
m-dichlorobanzene
o-cymene
limonenc
a-mothylstyrene
indc.nc
-------
Table 12 (cont'd)
Chromatographic
Peak No.
46C
50
54
56
58
61
Elution Temperature
(°C)
200
207-8
222
224
225-7
260
Compound
£-diethylbenzene
n-undecane
1-dodecene
n-dodecane
naphthalene
4-methylazoebenzene
(tent.)
aSee Tables 5 and 6, expt. 3A.
Probably background vapors from ambient air.
72
-------
Table 13. ORGANIC VAPORS EMITTED FROM PINE NEEDLES
DURING SMOULDERING PERIOD3
Chroma to graphic
Peak No.
1
2
2A
2B
2C
2D
3
3A
3B
4
4A
4B
4C
5
6
6A
7
7A
8
8A
9
10
10A
11
12
13
13A
14
15
Elution Temperature
(°C)
65
74
75
77
73
78
79
79
81
83
84
85
86
89
92-3
94
94
97
97
98
99
99
101
102
104
105
.1.06
107
105
(continued)
73
Compound
C4H8
isopentane
tr ichlor of luoroine thane
1-pentene
furan
C5H10
n-pentane
isoprene
acetone
C5H-,~ isoraer +
bmethyiene chloride
isopropanol
cyclopentadiene
^carbon disulficle (tent.)
C/-H-,_ isomer
3-methyl-2-pent;ene +
2-methylpentaae
ctrimcthylsilanol (BKG)
diacetyl
^6^12 isomer
1-hexene
methyl vinyl ketone
2-mcthylft!ran
n-hex.ane
tr am; -methy 1 p i op eny 1
ketone (tent.)
chloroform
pent-2-pn-4-ona
j.-niet.hylcyciohcxane
2, 2,3-trimethy] hutane
2,2-dimethylpe:H-.ane
2,4-hK,v.ndieiuj.
-------
Table 13 (cont'd)
Cbromato graphic
Peak No.
16
16A
17
19
20
20A
21
21A
22
23
24
24A
25
26
26A
27
28
29
30
30A
31
32
32A
33
34
35
36
37
38
Elution Temperature
110
111
112
114
115
116
117
117
118
119
122
123
124
125
125
126
127
129
131
131
133
134
134
136
137
139
141
143
144
(continued)
74 '
Compound
1,3, 5-hexatr iene
1,1, 1-trichloroethane
3-methylbutanal
CgHi / isomer
benzene
carbon tetrachloride
cyclohexane
2-methylpent-l-en-3-one
(tent.) + CyH^g isomer
4-methylpentene
2, 4-dimethylpentane
l-trans-2-d imethylcyclo-
pentane
sorbaldehyde (tent.)
^trichloroethylene
2 , 5-dimethy If uran
n-heptane
cis-2-heptane
2 , 4-diiuethy If uran
2-vinylfuran
CgHj_4 isomer
2-ethylfuran (tent.)
2 , 3-dimethy 1-2-pentane
2, 4-dimethylhexane
methyj cyclopropyl/ketone
(tent.)
1-methyl-l , 3 -eye] ohexadiene
(tent.)
CgH^6 asomer
C7I112 ifiomer
toluene
CgHjy i a onicr
C7H12 isomer
-------
Table 13 (cont'd)
Chroma tographic
Peak No.
39
40
41
42
43
44
45
46
47
48
49
50
50A
51
52
53
54
55
56
57
57A
58
59
60
61
62
63
64
65
Elution Temperature
<°C)
145
147
148
150
152
153
156
158
161
162
162
165
166
167
168
169
170
172
174
176
177
177
180
182
183
183
184
186
187
(continued)
75
Compound
1-octene
2, 3-dimethylhexa-l , 4-diene
n-octane
2,3, 5-tr imethy If uran
chexamethylcyclotrisiloxane
(BKG)
furfural
^8^14 isomer
2,5-diethylfuran (tent.) +
CoHi c. isomer
y J- \J
CgH^g isomer
isobutyl acetate (tent.)
ethyl benzene
_p_-xylene
2-propionylfuran (tent.)
CnH-^g isomer
styrene
o-xylene
n-nonane + 2-isopropyl-
furan
anisole
2-methyl-5-isopropenylfuran
cumene
C8H18°
n-decane
camphene (tent.)
n-propylbenzene
m-cthyltoluene
£-ethyl toluene
C-11^24 isomer
C lo^i H isomer
C3-alkyl benzene
-------
Table 13 (cont'd)
Chromatographic
Peak No.
66
67
68
70
71
72
74
75
76
77
78
87
88
Elution Temperature
188
191
191
195
197
198
201
203
205
207
208
223
225
Compound
1-decene
benzofuran
CinH_7 isomer
n-propyltoluene
m-diethylbenzene
limonene
n-butylbenzene
p-propyltoluene
dimethyl ethyl benzene
(isomer ?)
p-a-d imethy Is ty r ene
n-undecane
C10H0/ (cyclododecane ?)
J.Z ^H
n-dodecane
Q
A 100 m glass SCOT capillary coated with OV-101 stationary phase was
used to separate organic vapors. Capillary was temperature programmed
from 20-230°C @ 4%nin. Helium flow was 1.7 ml/min.
These vapors have been commonly found in ambient air samples and may be
regarded as background in the air itself.
CBackground from stationary phase "bleed" from glass capillary.
76
-------
SECTION 9
IDENTIFICATION AND QUANTITATION OF N-NITROSODIMETHYLAMINE IN
AMBIENT AIR BY CAPILLARY GAS-LIQUID CHROMATOGRAPHY
MASS SPECTROMETRY COMPUTER
In the period from 1950-1969, cancer statistics indicate that the
incidence of death from certain types of cancer for Baltimore City and
adjacent Anne Arundel County are higher than the comparable rates for either
the state of Maryland or the continental United States (see Table 14).
Exposure to any known carcinogen usually initiates an induction period for
Table 14. CANCER MORTALITY STATISTICS
.a
Deaths per 100,000 population
Type
Tongue, mouth
Esophagus
Trachea,
bronchus , lung
Nasopharynx
Baltimore
City
7.3
7.0
61.1
0.9
Anne
Arundel Co.
6.2
5.8
51.0
0.1
Maryland
5.54
4.94
48.46
0.48
United
States
4.21
4.10
37.98
0.38
Statistics for white males.
several years before any effect is seen. The higher rates for cancer mor-
tality in areas of the respiratory system for these localities suggest that
airborne carcinogens may play an important role, at least in the Baltimore
City/Anne Arundel County area. The potency of N-nitrosodimethylamine (DMN)
as a carcinogen has been established repeatedly in experimental studies on
mice, hamsters, guinea pigs, rats, mink, rabbits and several species of
Inhalation of DMN has produced tumors of the nasal area in
NIOSH concludes that in view of this broad spectrum of
77
-------
carcinogenic activity in experimental animals , N-nitrosodimethylamine must
be regarded as potentially carcinogenic for man. Notwithstanding the potency
of DMN as a carcinogen, it is extremely unlikely that this compound alone
could be responsible for a high incidence of cancers since many hazardous
agents are introduced to the environment by industrial processes.
Previous analysis of the air in the area of Baltimore City utilized a
specific detection method for DMN. ^ ' Samples were collected cryogenically
and analyzed on a thermal energy analyzer (Thermo-Electron, Model 502).
Immediate and unequivocal identification of the molecular structure of DMN
was not possible by this technique; comparison with a standard was necessary
for empirical identification.
Under this research program, the emphasis has been upon obtaining a
complete characterization of organic vapors present in the ambient atmos-
phere to provide a chemical basis for epidemiological studies. This section
presents the first report of the unequivocal identification by gc/ms compu-
ter of N-nitrosodimethylamine in ambient air in Baltimore, Maryland.
In addition to identifying organic vapors present in the ambient atmos-
fl 2
phere, ' ' analysis by the same technqiues developed in this laboratory
has provided quantitative information. This section also describes the
quantification of N-nitrosodimethylamine in ambient air in Baltimore, MD and
the Kanawha Valley, WV using single ion monitoring (m/e^ 74) in conjunction
with glass capillary gas-liquid chromatography/mass spectrometry. Estima-
tion of DMN levels in ambient air was performed in several locations surround-
ing the FMC site in Baltimore, MD, and Union Carbide and DuPont in the
Kanawha Valley.
EXPERIMENTAL
Sampling and Analysis
Organic vapors were concentrated on a 1.5 x 6.0 cm bed of Tenax GC
(35/60) in a glass cartridge. All sampling cartridges were precon-
ditioned by heating to 275°C for a period of 20 min under a helium purge of
AipA
20-30 ml/min. After cooling in precleaned Kimax^ culture tubes, the
containers were sealed to prevent contamination of the cartridge. Sampling
cartridges prepared in this manner were carried by automobile or air freight
to the sampling site; 2-3 cartridges were designated as blanks to determine
whether any of the cartridges might have been contaminated by the packing
78
-------
and transportation procedure. Cartridges containing known quantities (100
and 300 ng) of N-nitrosodimethylamine were prepared and carried to and from
the field, stored and analyzed to determine recovery of N-nitrosodimethyl-
amine .
In conjunction with Dr. L. Ballard of Nutech Corp. (Durham, NC),
portable field samplers were custom-built to operate conveniently and
reliably under varying conditions of pressure and gas flow. Precise measure-
ment and regulation were essential/ ' A schematic of the vapor collection
and analytical system is depicted in Fig. 13.
Samples taken in replicate, as well as the blanks discussed above, were
subjected to analysis by a capillary gas chromatograph/mass spectro-
meter/computer (Fig. 13). Thermal desorption was used to transfer the
entire amount of trapped vapors from the cartridge sampler to the analytical
system and required a specially designed manifold. ' In a typical thermal
desorption cycle, a sampling cartridge was placed in the preheated (ca.
250°C) desorption chamber, and helium gas was channeled through the cart-
ridge (ca. 20 ml/min) to purge the vapors into the liquid nitrogen cooled
nickel capillary trap. After desorption, the six-port valve was rotated and
the temperature on the capillary loop was rapidly raised (>10°C/min); the
carrier gas introduced the vapors onto the glc column.
A Varian MAT CH-7 glc/ms/comp system was used to perform the analysis
(Fig. 13). Mass spectra and retention time data were accumulated on magnetic
tape and subsequently processed by a Varian 620/L computer. A reconstructed
gas chromatograph provided a correlation between mass spectrum number and
retention time. Operating parameters used on the glc/ms/comp system for
analysis of samples collected on glass cartridges from the Baltimore, Mary-
land and Kanawha Valley areas, are shown in Table 15- Ambient air samples
were analyzed on 55, 80 or 100 m glass SCOT columns coated with either DECS,
OV-101 or OV-225 stationary phase, respectively. Desorption of ambient air
pollutants (including nitrosamines) from the Tenax cartridges was achieved
at 265-270°C. A single stage glass jet separator interfaced the SCOT capil-
lary columns to the mass spectrometer and was maintained at 220°C.
Identification of DMN was achieved by comparison of the mass spectrum
to an eight peak index of mass spectra(12) and to the Wiley library collec-
tion.^13^ Identification was confirmed by comparison of mass spectra and
79
-------
GAS
METER
FLOW
METER
PUMP
CARTRIDGE
NEEDLE
VALVE
GLASS
FI8ES
FILTER
VAPOR COLLECTION SYSTEM
PURGE
GAS
GLASS
JET
SEPARATOR
TWO
POSITION
VALVE
THERMAL
DESORPTION
CHAMBER
HEATED
BLOCKS
EXHAUST
CARRIER
GAS
1 9"fMAGNETiq
TAPE
CAPILLARY
TRAP
ANALYTICAL SYSTEM
Figure 13. Vapor collection and analytical systems for analysis
of hazardous vapors in ambient air.
80
-------
Table 15. OPERATING PARAMETERS FOR GLC/MS COMPUTER SYSTEM
Parameter
Setting
Inlet-manifold
Desorption chamber
Valve
Capillary trap - minimum
maximum
Thermal desorption time
Gas-liquid Chromatography
OV-101 glass SCOT (100M)
OV-225 glass (80M)
DECS glass SCOT (55M)
Carrier (He)
Mass Spectrometry
Single stage glass jet separator
Ion source vacuum
Filament current
Multiplier
Scan rate, automatic-cyclic
Scan range
265-270°C
175°C
-195°C
+175°C
~4 min
30-225°C, 4°C/min
80-210°C, 4°C/min
70-205°C, 4°C/min
1.5 ml/min
220°C
~2 x 10"6 Torr
300 yA
5.5
1 s/decade
m/e 20 -> 300
81
-------
elution temperature on two different columns of DMN and an authentic sampl-
(Table 15).
Determination of Breakthrough Volume
Breakthrough volumes for DMN, NO, N02, and water were determined as
previously described. The vapor was injected onto a gas chromatographic
column packed with the sorbent Tenax GC and tL° elution volume determined at
a series of decreasing temperatures. The log of elution volume ys tempera-
ture was plotted and the breakthrough volume at ambient temperature (50-
90°F) was obtained by extrapolation. The volume of air sampled was less
than the breakthrough volume of DMN at the ambient temperature of sampling
which allowed quantitative collection.
In Situ Formation of DMN
In order to determine whether DMN may form in an atmospheric chemical
reaction it is first necessary to know the extent to which it may be formed
at trace levels as an artifact of the sample collection process. Since the
Tenax cartridge would concentrate dimethylamine (DMA) if present in ambient
air, it was conceivable that, in the presence of NO , DMA might be nitro-
X
sated to form DMA. Several laboratory and field experiments were conducted
to determine whether an in situ reaction could occur on the sampling cart-
ridge. In the first set of experiments, Tenax cartridges were prepared by
drawing through them 50 liters of air containing 5 ppm DMA. Then seven
liters of a synthetic mixture of NO, water vapor and air (1, 10 or 250 ppb
NO, 72% relative humidity) were drawn through the cartridges. The DMA was
purified prior to use by low temperature vacuum distillation since it had
been found to contain 10 ppm of DMN.
In a second set of experiments, 1, 5, and 10 ppm mixtures of NO in air
were introduced into a stream of laboratory air drawn at a rate of 10 liter/
min across a permeation tube containing DMA (~9 x 10 moles/min, 4.5
ppm) and into a Tenax GC cartridge. A third set of experiments consisted of
introducing equivalent amounts of NO and N02 into an air sampling stream
drawn across a DMA permeation tube (4.5 ppm) and into the Tenax cartridge.
All the cartridges were analyzed by single ion monitoring (m/£ 74) in the
capillary glc-ms mode.
Additional experiments were conducted during field sampling at the
Baltimore, MD industrial site to determine whether an enhancement in the
82
-------
concentration of DMN above the background level occurred when a Tenax
cartridge was preloaded with DMA. Thus, a blank and DMA preloaded cartridge
were used in parallel sampling and compared. Also, in a field experiment
air was drawn across a permeation tube containing DMA (-2.5 x 10~6 g/min)
and into the Tenax cartridge. In different experiments the DMA permeation
tube (~2.5 x 10 g/min) was placed before and after the glass fiber filter
used to remove particulates. All experiments were conducted in duplicate.
A volume of ~120 £ of ambient air was sampled in all cases.
Since urban air often contains substantial concentrations of ozone, a
series of laboratory experiments were done to determine whether air contain-
ing both N0x and ozone might be more effective in converting DMA to DMN than
air containing only NO . Conversion of DMA adsorbed on Tenax and conversion
a
of DMA at low concentrations in air in a glass flow tube were investigated
in two additional series of laboratory experiments were conducted. The
first focused on the possible conversion of dimethylamine trapped on a Tenax
cartridge by polluted air passing through the cartridge. The second was
concerned with DMN formation through atmospheric reaction(s) or reactions
which might take place on the walls of the sample inlet tube.
The apparatus used to conduct these experiments is shown in Fig. 14.
Through the reaction tube a 5 JfL/min air flow was maintained in all of the
experiments performed. Nitric oxide was measured into the stream with a
rotometer and a metering valve from a supply tank which contained 54.2 ppm
of NO in nitrogen. Ozone was generated by an ultra-violet lamp which had a
movable cover so that different concentrations could be obtained. Ozone
concentrations >1 ppm were generated with the aid of a Welsbach ozone genera-
tor which was inserted into the air-line between the scrubbers and the
metering valves (Fig. 14). The concentrations of NO, N02, and 03 were
monitored with a Bendix NO analyzer and a Bendix Ozone analyzer. The
A
intakes for these instruments were placed at the same point as the intake
for the Tenax cartridge sampler through which air was drawn by a Nutech
Model 221-A sampler. The sampling cartridge and analyzer inlet tubes were
centered in the air flow pattern in the reaction tube. Relative humidity of
the air stream was controlled by changing the temperature of the humidifier
bath.
83
-------
00
AIR —
supply
SCRUBBER
TRAIN
X
r^
NO SUPPLY
(54.2 ppm/Nz)
ACTIVATED
DRIERITE CARBON
MOLECULAR
SIEVES
ROTOMETER =
TENAX
CARTRIDGE (GELMAN A/E PREFILTER)
GLASS REACTION TUBE
(3.5cm i.d. xZ.2m)
SLIDING COVER ^UV LAMP
MIXING
CHAMBERS
PERMEATION
TUBE
Figure 14. Schematic of instrumentation and devices for examining in sJtu formation of
N-nitrosodimethylamine on Tenax GC cartridges.
-------
RESULTS AND DISCUSSION
Identification of DMN in Ambient Air
The sampling areas considered in this study are shown in Figures 15-18.
Site 1 is the FMC industrial firm, site 2 was a location at the Patapso
Sewage Treatment Plant, site 3 at the Chessie Coal Piers, site 4 was DuPont
in Belle, W, site 5 consisted of Union Carbide Corp., Charleston, WV, and
site 6 was in Nitro, W.
Figure 19 depicts the profile of ambient air pollutants in a sample
taken during the day in the parking lot area of an industrial site (site 1,
Fig. 16). The volume of air collected represents 75 &. A 100 m glass SCOT
column containing OV-101 stationary phase was used to effect this separa-
tion.
Figure 20 presents a profile of ambient air pollutants in a sample
taken during the daylight hours near the Patapsco Sewage Treatment Plant.
The sampling apparatus was upwind from the industrial site, but downwind
from the Sewage Treatment Plant.
The chromatographic separation of constitutents was also achieved by
use of a more polar stationary phase DECS, coated in a 55 m glass SCOT
column, and the results are shown in Fig. 21 (replicate sample of Fig. 19).
Semi-polar and polar phases are not well suited to resolution of non-polar
(e.g. hydrocarbon) pollutants. However, resolution of semi-polar and polar
constituents was significantly better.
Figure 22 shows the mass spectrum of an authentic sample of DMN chroma-
tographed on the 55 m DEGS SCOT column. Figure 22 also depicts a mass
spectrum taken at a retention time of 26 min for the ambient air sample
collected (Fig. 21) on the industrial site in Baltimore. Comparison of this
mass spectrum with that of authentic DMN shows that the two spectra are
essentially superimposable and confirms the identification of the unknown as
N-nitrosodimethylamine. The lower range (m/e 35) is uncalibrated, so exact
correspondence in this range is not observed. The retention time (26 min)
of authentic DMN was identical to that of the unknown in Fig. 21. Similar
confirmation of the presence of DMN has been obtained for the ambient air
profile using OV-225 and OV-101 capillaries (Table 16).
Approximately one month subsequent to the determinations discussed
above (November 19-25), the studies were repeated and the presence of DMN
85
-------
EAST BROOKLYN,
BALTIMORE, MARYLAND
CHESSIE
COAL PIERS
CURTIS BAY
SCALE: ONE INCH =0.5 miles
Figure 15. Map of sampling area in East Brooklyn, Baltimore, Maryland
86
-------
00
•-J
X= INCINERATOR STACK
SS= SAMPLING SITE
Figure 16. Plant map of FMC.
-------
00
OO
•* rg
| ' \[ ****** tar J [Q
W^^^
—OLD U.S. ROUTE GO ^
o Ground 1ml •Mvotlon 603' 0" J
• hUlhyl omtnt'i «
-------
M*'N
0V,
KANAWHA WE*
WA/ft
00
Figure 18. Plant map of Union Carbide in South Charleston, WV depicting
sampling locations.
-------
ID
O
20
0
L
3
1
6
'i
9
6,8
12
,
15
i
IS
21
116
24
i
27
TEMPERATURE (°c)
i i
30 33
164
36
39
" 42
45
2
2
48
51
250°
54
57
60
TIME (mini
Figure 19. Profile of ambient air pollutants from an industrial site in Baltimore, MD.
Sample was taken on 10/14/75 from 3:00 pm - 6:50 pm. A 100 m glass SCOT
column coated with OV-101 stationary phase was used to effect the separation:
see Table 15 for conditions. Peak No. 27 was established as DMN.
-------
VO
H1
TEMPERATURE (°c)
20
3
6
i
9
68
12
l
15
i
ia
i
21
116
i
24
i
27
i
30
l
33
/ :_\
164
36
_,
39
1
42
i
45
212
i
46
i
51
230
»
54
l
57
t
60
1
63
TIME (mini
Figure 20. Profile of ambient air pollutants taken on 10/16/75 from 10:00 am - 1:50 pm at the
Patapsco Sewage Treatment Plant. Instrumental conditions were identical to Fig. 19.
-------
N5
100
90-
2 80
O
cc
y TO
tr
cc
o
I
60
50-
40
30
20
10 «W.
DMN
26 mln
(I78°c)
Figure 21. Chromatogram of pollutants from industrial site in Baltimore, Maryland. A
replicate sample of that used for Fig. 19. A 55 m DECS SCOT capillary was
used; see Table 15 for operation conditions.
-------
m/e74
VO
LO
IUU
P 80
z
8
oc
UJ
<75
§ 40
z
UJ
p 20
0
-
—
•
~
1
1
1
,1
1
42
,
J
i
i
i
1 1 1 f w i ^
'1 I1!1
,L
'I1
1
J
42
M
i bid i M i
'I1
I'M
50
100
DMN (AUTHENTIC SAMPLE), ANALYZED
ON DEGS COLUMN
50
IOO
PEAK AT 26 MIN. IN SAMPLE
TAKEN 10/14/75, ANALYZED ON
DEGS COLUMN
Figure 22. DEGS Glass SCOT column (55 m) was used in both analyses; 70-205°C at 4°C/mln.
-------
Table 16. SAMPLES EXAMINED FOR N-NITROSODIMETHYLAMINE BY
GAS LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY/COMPUTER
SCOT Capillaries used for
Identification of DMNa
Date/Time
11/19/75
2:00 pm - 4:00 pm
11/24/75
11:50 pm - 1:50 pm
11/24/75
6:35 pm - 8:35 PM
Location
DECS
Site 1
Site 1
Site 1
NA
OV-225
NA
NA
NA
OV-101
10/14/75
11:00 am - 2:50 pm
3:00 pm - 6:50 pm
7:00 pm - 10:50 pm
11/15/75
11:00 pm - 2:50 pm
3:00 pm - 6:50 pm
11:00 am - 2:50 pm
3:00 pm - 6:50 pm
10/16/75
10:00 am - 1:50 pm
2:00 pm - 5:50 pm
10/17/75
9:56 am - 1:46 pm
2:10 pm - 6:00 pm
Site 1 +
Site 1 +
Site 1 +
Site 1 +
Site 1 +
Site 1 +
Site 1 +
Site 2 . -
Site 2
Site 3 +
Site 3 +
NA
NA
NA
NA
NA
-
NA
+
+
+
NA
NA
NA
NA
-
NA
NA
o
Analysis were on glass capillary columns coated with DECS, OV-225 or
OV-101 stationary phases; (+) = molecular confirmation of DMN '
established; (-) = DMN confirmation not established; (NA) = not
analyzed on this capillary.
94
-------
was again established (Table 16) in ambient air at the same Baltimore indus-
trial site.
Breakthrough Volumes
Breakthrough volumes for DMN, DMA, NO, N02 and H20 are shown in Table
17. It was evident from these data that the retention volume for DMN was
much larger than for the other four substances examined. The breakthrough
volumes for NO and N02 were extremely small (few ml to zero). This was an
important relationship in view of the possibility of in situ reactions
occurring on a sorbent bed. The breakthrough volumes (Table 17) indicated
that NO, NO- and water would not accummulate relative to dimethylamine, thus
making the in situ reaction kinetics unfavorable for nitrosation of DMA.
Quantitation of DMN
Since the most intense peak in the mass spectrum was the parent ion
(m/£ 74, Fig. 23), this ion was selected for quantitating DMN. The selec-
tion of m/e 74 proved to be highly specific for DMN when used in combination
with a glass capillary coated with DECS stationary phase and the surfactant
benzyl triphenylphosphonium chloride.
Figure 24 depicts a specific ion (m/e 74) chromatogram for an authentic
sample of N-nitrosodimethylamine. The retention time of DMN on this capil-
lary was 26 min.
Standard curves for DMN are presented in Figures 25 and 26. Concen-
trations of DMN ranging from 100 pg - 2,000 ng were prepared on Tenax GC
cartridges. Cartridges were desorbed and analyzed by capillary gc/ms with
selective ion monitoring. The response of the mass spectrometer was linear
over the entire range as shown in Figures 25 and 26. To estimate DMN levels
in ambient air, the quantity of DMN on a cartridge was determined and then
the concentration in air (ng/m3) was calculated based on the volume of air
sampled.
Concentrations of DMN in ambient air surrounding in industrial site in
Baltimore, MD are given in Table 18. Listed are the dates, time periods,
and the prevailing meterological conditions during the sampling period. The
highest concentration of DMN was 32,000 ng/m3 (November 19, 2-4:00 p.m.) at
the industrial site (IB). At the Chessie Coal Piers (site 3), the highest
concentration was -909 ng/m3. Upwind from the industrial site, only trace
levels of DMN were detected (sewage treatment plant). The recovery of DMN
95
-------
Table 17. BREAKTHROUGH VOLUMES FOR DMN, DMA, NO,
N02 AND H-0
Ambient Temperature
(°F)
50
55
60
65
70
75
80
85
90
100
105
110
DMN
385
332
280
242
224
204
163
156
127
107
93
79
DMA NO
60 0.025
55 0.020
50 0.015
45 0.010
40 -b
35
30
25
15
10
5
1
N02 H20
0.030 0.060
0.024 0.055
0.018 0.050
0.009 0.045
0.040
0.035
0.030
0.025
0.020
0.015
0.005
-
Breakthrough volume expressed as £/2.2 g of Tenax GC (35/60 mesh) in
a sampling cartridge.
The breakthrough volume was not distinguishable from the sweep volume
of the carrier gas.
96
-------
en.
CH,
N-NO
e
CH
3V
N-N=0
CH
m/e 74
-H, HNO
CH2 = N = CH
m/e 42
•T
Figure 23. Mass cracking pattern for N-nitrosodimethylamine
97
-------
VO
oo
40
20
40
2 20
UJ
40
20
Inject
x3
Inject
x3
Inject
x3
DMN(300)ng
26 min.
xl
26 min.
TIME (MIN.)
26 min.
Figure 24. Single ion (m/e 74) chromatogram for N-nitrosodimethylamine. A, B, C, are
traces for standard DMN, and replicate field samples, respectively. Analysis
on DECS column, standard conditions.
-------
300r-
20
60 80 IOO
ZOO
ng
400 600 8001000 ZOOO 3OOO
Figure 25. Standard curve for N-nitrosodimethylamine.
99
-------
10.0
8.0
6.0
4.0
2.0
1.0-
0.8-
E 0.6
u
§ 0.4
O.I
.08
.06
.04
.02
0.01
0.10
1.0
10.0
ng/cortridge
100
Figure 26. Standard curve for N-nitrosodimethylamine.
100
-------
Table 18. SAMPLING CONDITIONS AND CONCENTRATIONS OF N-NITROSODIMETHYLAMINE
IN AMBIENT AIR
Date
10/14/75
10/15/75
10/16/75
10/17/75
11/19/75
11/20/75
Time
11:00 am
3:00 pm
7:00 pm
11:00 pm
3:00 pm
11:00 am
3:00 pm
10:00 am
2:00 pm
9:56 am
2:10 pm
2:00 pm
3:45 pm
8:20 pm
(EOT)
- 2:50 pm
- 6:50 pm
- 10:50 pm
- 2:50 am
- 6:50 am
- 2:50 pm
- 6:50 pm
- 1:50 pm
- 5:50 pm
- 1:46 pm
- 6:00 pm
- 4:00 pm
- 5:45 pm
- 10:20 pm
Site3
la
la
la
la
la
la
la
2
2
3
3
Ib
Ic
Id
Temperature
(°F)
83
85
74
65
61
85
83
72
72
55
55
65
68
57
Relative
Humidity
(%)
40-50
45-50
65-85
90-97
97
40-50
40-50
45-57
45-50
88-94
94-100
56
57-73
71
Wind
Direction
WNW
WNW
WSW
calm
S
WSW
WSW
NNW
NNW
ENE
E
E
sw-s
s-sw
Speed
(KTS)
10
7
7
3
8-10
5-8
9-11
5-12
7-9
10-14
3
3-6
4
DMN
ng/m3
2,133
10,500 + 1,167
1,375 + 125
416
517
3,200
13,437 + 937
<0.6
<0.6
909
84
32,000 + 1,500
1,950
1,360 + 510
(continued)
-------
Table 18 (cont'd)
Date
ll/24/75b
11/25/75
Time (EOT)
11:50 am -
1:55 pm -
6:35 pm -
1:48 pm -
1:50 pm
3:55 pm
8:35 pm
3:48 pm
Sitea
le
le
le
If
Temperature
(°F)
62
64
59
65
Relative
Humiditv
(%)
72
74
68
Wind
Direction
NW
NNW
NNW
-
Speed
(KTS)
3
4
3
4
DMN
ng/m
20,000 + 4,000
14,000 + 200
26,000 + 500
7,600
a,
Sites were shown on Figure 1, letters indicate locations on the site.
Replicate cartridges were sampled in parallel except one for each time period was used to examine
potential in situ reactions; see text for details.
-------
from sampling cartridges which were transported to and from the field was
>95%.
Figure 24 also depicts single ion chromatograms for DUN for duplicate
sampling cartridges which were taken on October 14. The reproducibility of
the entire quantitation method was approximately +10%, as exemplified by
replicate determinations (Table 18).
The detection limit observed for the m/e 74 ion was approximately 0.2
parts-per-trillion when the ambient air temperature during field sampling
was 50°F. Thus the minimum amount of DMN which can be quantitated under
these field sampling conditions was approximately 2 parts-per-trillion.
Single ion plots for N-nitrosodimethylamine of samples taken from
DuPont and Union Carbide are shown in Figures 27 and 28. In separate experi-
ments, the retention time for N,N-dimethylformamide was determined in order
to assess whether the monitoring of m/e 74 ion for DMN would be contamined
by this compound. Although N,N-dimethylformamide has a molecular ion of 73,
if present in large quantities it is conceivable that the intensity of the
13
C isotope would increase until the 74 ion intensity would become signi-
ficant. The retention time for N,N-dimethylformamide was determined to be 2
min longer than that of DMN on the SCOT glass capillary. Therefore, this
compound does not interfere with the quantitation of DMN. No other inter-
ferences are known to occur with an identical retention time (27.2 min, Fig.
27 and 28) of DMN as well as an m/e 74 ion.
Using the above described techniques, the concentration of DMN in
ambient air was determined in the plant area of DuPont and Union Carbide.
Table 19 depicts these results. On December 1, the highest concentration of
2
DMN was observed as location No. 4 (38 ng/m ). During the early morning
3
hours of December 2, it reached a level of 68.5 ng/m . During the sampling
period on the evening of December 2 to 3:00 AM, the concentration of DMN
observed on the Union Carbide was extremely low or non-detectable. The
o
highest concentration of DMN was 40 ng/m at location 13 on December 13. ':.
December 4, further sampling was conducted on the DuPont property at loca-
tions 5, 6, 7 and 8. The highest levels of DMN observed for the entire week
occured at location 6 (980 ng/m3). These locations were along and near an
aeration system and waste treatment area. The temperature of the water at
103
-------
I00r
g 50
i!
XO.J
XO.I
2T.2 min
Figure 27. Single ion (m/e 74) current profile of ambient air sample taken at locations No. 2
on DuPont property in Belle, Wf.
-------
100
o
Ul
50
Figure 28. Single ion (m/e 74) current profile of ambient air sample taken at
location No. 13 on Union Carbide property in South Charleston, WV.
-------
Table 19. SAMPLING CONDITIONS AND CONCENTRATIONS OF N-NITROSODIMETHYLAMINE IN
AMBIENT AIR IN THE KANAWHA VALLEY, WV
Site
Location
Date
Time
Wind (Knocs)/Temperature
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
S. Charleston
S. Charleston
S. Charleston
S. Charleston
S. Charleston
S. Charleston
S. Charleston
S. Charleston
DuPont (1)
DuPont (2)
DuPont (3)
DuPont (4)
DuPont (1)
DuPont (2)
DuPont (3)
DuPont (4)
DuPont (2)
DuPont (3)
DuPont (4)
Union Carbide
Union Carbide
Union Carbide
Union Carbide
Union Carbide
Union Carbide
Union Carbide
Union Carbide
(9)
(10)
(11)
(12)
(11)
(9)
(13)
(14)
12/1/75 9:30 PM -
12/1/75 9:24 PM -
12/1/75 10:16 PM
12/1/75 10:07 PM
12/2/75 2:29 AM -
12/2/75 2:28 AM -
12/2/75 4:00 AM -
12/2/75 3:17 AM -
12/2/75 9:00 PM -
12/2/75 10:02 PM
12/2/75 10:05 PM •
12/3/75 2:41 PM -
12/3/75 3:12 PM -
12/3/75 3:36 PM -
12/3/75 3:38 PM -
12/3/75 6:33 PM -
12/3/75 6:16 PM -
12/3/75 5:51 PM -
12/3/75 6:15 PM -
2:17 AM NW (2)/30-35°F 10.1
2:19 AM NW (2)/30-35°F 4.2
- 3:09 AM NW (2)/30-35°F 3.9
- 3:97 AM NW (2)/30-35°F 38.0 + 6
6:52 AM SE (4)/30°F 26.0 + 4
6:53 AM SE (4)/30°F 12.9 + 2C
7:11 AM SE (4)/30°F 67.0
7:12 AM SE (4)/30°F 68.5 + 5
3:02 AM SE (2)-calm/40-50°F 59
3:18 AM SE (2)/40°F 77.6 + 6
3:00 AM. SE (2)/40°F 103.0
6:01 PM WNW+NW (2)/50-55°F <1
5:12 PM WNW->NW (2)/50-55°F NDb
6:27 PM WNW->NW (2)/50-55°F 13.6
5:28 PM WNW+NW (2)/50-55°F 11.6
8:53 PM NW->N (2)/45-50'F ND
8:19 PM NW+N (2)/45-50°F <1
7:56 PM NW->N (2)/45-50°F NDC
8:40 PM NW+N (3)/45-50°F ND
(continued)
-------
Table 19 (cont'd)
Site
Location
Date
Time
Wind (Knots)/Temperature ng/m"
S. Charleston
S. Charleston
S. Charleston
S. Charleston
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Nitro, WV
Nitro, WV
Union Carbide (11)
Union Carbide (11)
Union Carbide (13)
Union Carbide (14)
DuPont (5)
DuPont (6)
DuPont (7)
DuPont (8)
1-60 & WV25
1-60 & WV25
12/3/75 6:33 PM - 8:43 PM
12/3/75 8:28 PM - 10:30 PM
12/3/75 8:03 PM - 10:17 PM
12/3/75 8:47 PM - 10:44 PM
12/4/75 5:10 PM - 7:11 PM
121'4/75 3:26 PM - 5:24 PM
12/4/75 4:00 PM - 6:05 PM
12/4/75 7:06 PM - 9:06 PM
12/5/75 11:58 AM - 3:48 PM
12/5/75 11:59 AM - 3:49 PM
NW+N (3)/45-50°F
N->NNE (3)/40-45°F
N+NNE (3)/40-45°F
N->NNE (3)/40-45°F
NE (2)-calm/54-60°F
NE (2)-calm/60°F
calm (plutnes/60°F
straight up)
NE (2)-calm/60°F
SW (10)/65°F
SW (10)/64°F
56
ND
40+2
ND
ND
980
500
576
ND
ND
•^
See industrial plant map for precise location.
ND = not detected.
Part of Artifact Experiment.
-------
the aeration system was ~110°F. The sampler was located near this point .'or
a period of 2 hr (location 6).
DMN was not detected on December 5 when sampling was conducted in
Nitro, WV near the corner of Interstate 60 & WV 25.
In Situ Formation of DMN
An important species for nitrosation is ^itrous acid and since a small
retention volume for water was observed, it was conceivable that some of the
NO could have been converted to nitrous acid (NO + N00 + H~0 < > 2HONO).
x Li
In light of this possibility we examined the yield of DMN under a series of
various laboratory and field sampling conditions. Table 20 depicts the
yield of DMN from potential in situ reactions on Tenax GC during samplr'p.g in
the presence of DMA, NO, N0~ and/or water. Cartridges were prepared by
drawing through them 50 £ of air containing 5 ppm of DMA. Then an addi-
tional 15 i of air containing 1, 10 or 250 ppm of NO were sampled. No DMN
was detected. Also, when 50 & of air containing 4.5 ppm DMA were passed
through a cartridge and then equal molar quantities of NO and N02 (expt. 5)
were sparged into an air stream entering the cartridge at a relative humi-
dity of 75%, no DMN was detected. When the concentration of NO was increa-
sed to 1 ppm, ~10 ppt of DMN was observed. At a concentration of 10 ppm of
NO (75% relative humidity), the yield of DMN reached -300 ppt. Storing
cartridges at -20°C for a period of 2 weeks gave similar results as those
which were analyzed immediately after the in situ reaction experiment had
been completed (Table 20 expts. 10-13). These data show that at high con-
centrations of NO- it was possible to produce DMN; however, it is generally
recognized that the concentrations of NO in ambient air rarely exceed 1
A
ppm. Thus, under these circumstances the quantitation of DMN was possibly
down to a level of 10 ppt without an appreciable contribution from in situ
reactions.
In situ enhancement of DMN collection was not detected when dimethyl-
amine was introduced into the air sampling stream (Table 18, 11/24/75).
Analysis of cartridges which were sampled in parallel fashion (one was a
reference blank) indicated that the concentrations were within the experi-
mental reproducibility of the technique. It was concluded from these experi-
ments that any formation of DMN from an in situ reaction between dimethyl-
amine and NO was negligible and that the DMN measured in ambient air was
108
-------
Table 20. YIELD OF DMN FROM IN SITU REACTION(s) ON TENAX GC
CARTRIDGES DURING SAMPLING IN THE PRESENCE OF
DMA, NO, N02 AND H20
Experiment
No.a
1
2
3
4
5
6
7
8
9
10
11
12
13
Concentration Sampled
(ppb)
DMA
5,000
5,000
5,000
4,500
4,500
4,500
4,500
4,500
4,500
5,000
5,000
5,000
4,500
NO NO 2
1
10
,250
-
500 500
1,000
1,000 1,000
5,000
10,000
1
10
250
1,000
H2°b
(%RH)°
72
72
72
72
75
75
75
75
75
72
72
72
75
DMN Yield
(ppt)
ND°
ND
ND
ND
ND
10
15
35
-300
ND
ND
ND
15
o
See text for explanation of experimental design; experiments 10-13
were duplicates of 1-3 and 6 except cartridges were stored for 2
week at -208C.
Percent relative humidity at 26°C.
CDetection limit was ca. 0.3 ppt.
109
-------
originating from a point source. The industrial site was known to produce
DMN as an intermediate in a synthetic process. ,
Field experiments were also conducted at the Union Carbide and DuPont
sampling sites in order to either support or refute the possibility of an
in situ reaction. The rationale was to demonstrate whether an enhancement
in the quantity of DMN occurred during samplii s> since the preloaded dimethyl-
amine would become exposed to ambient levels of NO . Two sets of cart-
ridges were utilized for this artifact experiment at the DuPont (location
2) and Union Carbide (location 13) properties. In both cases we did not
observe an increase in the background level of DMN which was detected and
quantitated by monitoring m/e 74 ion.
Additional laboratory experiments were conducted whereby Tenax GC
cartridges (1.5 cm x 6.0 cm) were preloaded with dimethylamine (DMA) by
passing through them nitrogen gas which contained a known quantity of DMA
12
from a calibrated permeation tube ( H,-DMA or Hfi-DMA)* Each of these
cartridges was used to sample a 10 liter volume of air containing known
levels of NO, N09, 0,,, and water. Then the cartridges were thermally
1 2
desorbed and analyzed for H^-DMN or H,-DMN. The results are summaried in
6 6 2
Table 21. One cartridge, preloaded with H.--DMA was submitted for gc/ms
analysis (m/e 80) without further processing to determine the level of H,-
DMN present in the amine as a contaminant (Experiment No. 1). No IL.-DMN
was found in this sample- Samples of air containing 500 ppb NO were taken
at 50% and 90% relative humidity, also without producing any H,-DMN was
formed. Four experiments (Nos. 5-8) were run in which air with ~300 ppb NO
and ~200 ppb NO- was sampled. Two of these (Nos. 7 & 8) were run with low
humidity air. In two cases (Nos. 6 & 8) a very small volume of nitrogen
2
was used to preload the H>-DMA so that it would be confined to a rela-
tively narrow zone in the cartridge bed. In the other two cases (Nos. 5 &
7) a 10 liter volume of nitrogen was used to preload the EL-DMA so that it
o
was distributed in a much broader zone in the sorbent bed. The amounts of
o
Hfi-DMN formed did not fall into any definite pattern. Except for Experi-
ment No. 8 they are about the same as the amount formed in Experiment No.
4. The amount of ozone added to the air stream was increased so that most
of the NO was converted to NO,, leaving small residual amounts of NO and
ozone (Nos. 9-12). This resulted in formation of increased quantities of
110
-------
Table 21. EFFECT OF OZONE, NO, NO, AND DMA ON IN SITU FORMATION OF DMN
£.
Experiment
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
03
added
(ppb)
0
0
0
80
200
200
210
210
510
479
550
489
650
640
650
640
482
680
03
excess
(Ppb)
0
0
0
0
0
0
0
0
10
9
50
9
150
140
150
140
2
180
NOX
(ppb)
0
500
500
500
500
510
490
530
530
515
540
520
500
500
500
500
540
500
NO
(ppb)
0
500
500
420
300
310
280
320
30
45
40
40
0
0
0
0
60
0
NO 2
(ppb)
0
0
0
80
200
200
210
210
500
470
500
480
500
500
500
500
480
500
T°C
25
25
25
25
25
24
27
27
25
26
26
27
26
27
26
27
24
24
%RH
—
50
90
50
50
67
10
10
50
90
10
10
50
90
10
10
50
50
DMA
(nM)/ (liters)
202/10
202/10
202/0.151
202/10
202/10
202/0.151
202/10
202/0.151
202/10
202/0.151
202/10
202/0.151
202/10
202/0.151
202/10
202/0.151
404/0.42
404/0.42
DMN
(nM)
0
0
0
0.18
0.32
0.14
0.12
0.65
0.54
0.92
0.12
1.46
0.86
1.24
0.93
1.46
0.58
0.25
% yield
0
0
0
0.089
0.158
0.069
0.059
0.322
0.267
0.455
0.059
0.723
0.426
0..614
0.460
0.723
0.144
0.062
(continued)
-------
Table 21 (cont'd)
Experiment
No.
19
20
21
°3
added
(ppb)
-1500
-2500
-3000
03
excess
(ppb)
-1000
-500
-1000
NOX
(ppb)
500
-2000
-2000
NO
(ppb)
0
0
. o
NO 2
(Ppb)
500
-2000
-2000
T°C
26
26
26
%RH
50
50
50
DMA
(nM)/llt
202/0.
202/0.
202/0.
ars)
215
215
215
DMN
(nM)
2.78
1.16
1.04
% yield
1.376
0.574
0.515
ro
-------
H6-DMN in three of the experiments. More 2H6-DMN was formed on the cart-
ridges which had been loaded with 2H6-DMN concentrated in a small volume of
nitrogen (Hoi. 10 & 12) than was formed on cartridges loaded with the same
amount of H6~DMA in a large volume of nitrogen (Nos. 9 & 11). The ozone
was further increased so that there was no substantial excess of it at the
end of the flow tube and all of the NO was converted to NO (Nos. 13-16).
Again, the amount of Hg-DMN produced was generally larger and more was
produced on the cartridges which were loaded with concentrated zones of
H6~DMA (Nos. 14 & 16). Doubling the amount of ^-DMA on the cartridge
did not result in any increase in the amount of 2H,-DMN formed (Nos. 17 &
o
18). It was apparent that a high concentration of DMA in a small volume of
sorbent bed would produce more DMN than the same amount of DMA distributed
evenly through the entire bed.
There was no clear indication that the level of relative humidity had
any significant effect on the results. This was not surprising in view of
the very large excess of water over the concentrations of other potential
reactants at even the lowest levels of relative humidity. A constant,
convenient level of 50% relative humdity was adopted for further experi-
ments .
The concentrations of NO and ozone in these experiments were at
levels approximating the highest found in polluted air. In order to test
the possible effects of conditions that might prevail at extremely elevated
levels of NO in plumes coming from a point source, three experiments (Nos.
X
19-21) were conducted at much higher NO and ozone concentrations. There
A
was a substantial increase in the amount of DMN formed when the ozone level
was increased (No. 19), but no indication of any increase from higher
levels of N0£ (Nos. 21 & 21).
The principal result of this series of experiments is that under
extreme conditions of N02 and ozone pollution in the conversion of 202 nM
of DMA on a Tenax cartridge was small (Less than 1%). However it must be
remembered that the breakthrough volumes of DMA was not exceeded in these
experiments. Furthermore, the breakthrough volume of DMN is much larger
than that of DMA. If a volume of polluted air larger than the breakthrough
volume of DMA had passed through the cartridge, presumably even more of the
DMA would have been converted, and the resulting DMN would have been retained
113
-------
on the cartridge. Thus it would be misleading to attempt to extrapolate
these results to higher sample volumes. On the otherhand, the concen-
trations of DMA used to load the cartridges (0.5-33 ppm) were quite large,
approximating the levels that could be found in ambient air in the imme-
diate vicinity of a primary source. The results of this study suggest that
the efficiency of conversion of DMA to DMN wou'd be greatly dependent on
the concentration of DMA in the sorbent bed. This means that more DMN
would be formed on the cartridge if the DMA concentration fluctuated during
the sampling period than if the same amount of DMA were drawn into the
cartridge at a constant, low concentration.
The presence of N0_ was clearly necessary for formation of DMN. T is
suggests that the mechanism was formation of nitrous acid from NO, NO- aud
water with subsequent reaction between nitrous acid and DMA to form DMN.
The smaller yields of DMN in Experiment Nos. 17, 18, 20 and 21 in which
extremely high reactants levels were used were surprising. It would be
interesting to know the reactant concentrations at which DMN formation
would reach a maximum.
A permeation tube containing H,-DMA was placed in the upstream end of
the reaction tube (Fig. 14) so that the air passing down the tube would
carry with it a very low level of H^-DMA. Various concentrations of NO,
N0« and ozone were introduced into the air stream and samples of N0_,
ozone and organic vapors were taken at the downstream end of the reaction
tube. The results are summarized in Table 22. In one experiment (No. 22)
2
neither NO nor ozone was added to the air, and no H..-DMN was produced.
Air containing 500 ppb NO without ozone was passed through the tube, and
again no H..-DMN was found (No. 23). However, substantial quantities of
H,-DMN, somewhat larger than those formed in the comparable in situ experi-
ments, were found when ozone was added to the air stream (Nos. 24-26).
These experiments were conducted with the reaction tube covered with aluni-
mum foil. In order to test the effect of ultra-violet radiation on forma-
tion of DMN in the flow tube, a 22 cm length near the upstream end was
uncovered and irradiated with a Sylvania 110V, 275W sunlamp (Nos. 27-30).
The flow tube was constructed of 40 mm O.D. standard wall (~2 mm) Pyrex®
tubing. Light penetrates this thickness of Pyrex with 50% transmission at
o
\ = 3170A (1). Oxygen and NO photolyses occur only at lower wavelengths
114
-------
Table 22.
FORMATION OF DMN FROM OZONE, NO, NO- AND DMN IN A FLOW TUBE
Experiment
No.
22
23
24
25
26
27a
28a
29a
30a
31b
03
added
(ppb)
0
0
190
487
680
0
220
475
680
210
03
excess
(ppb)
_
-
0
7
180
-
0
15
180
0
NOX
(ppb)
0
500
500
520
500
500
510
510
500
530
HO
(ppb)
0
500
340
40
0
500
290
50
0
320
N02
(ppb)
0
0
190
480
500
0
220
460
500
210
T°C
25
24
24
25
25
26
27
26
26
26
^Hfi-DMA
%RH (nM) /(liters)
50
50
50
50
50
50
50
50
50
50
2H,-DMA
u
(nM)/(liters)
202/15.6
202/15.6
202/15.6
202/15.6
202/15.6
202/15.6
202/15.6
202/15.6
202/15.6
202/15.6
PMN DMN-dg
(nM) (nM)
0
0
1.14
-3.78
1.93
0.140
0.6
1.82
0.34
0.22
% yield
0.
1.
0.
0.
0.
0.
0.
0.
0
0
.564
,871
955
069
297
901
168
109
Ratio:
(Formed
In Tube):
(Formed on Cartridge)
32
33
34
35
36
690
690
690
700
700
190
190
190
200
200
500
500
500
500
500
0
0
0
0
0
SOO
500
•500
500
500
26
26
26
22
22
50 392/0. 422C
50 392/0. 422C
50 392/0.422°
50 -140/30
50 -140/30
-388/30
-420/32.5
-388/30
140/0.125°
140/0. 125C
2.67 8.63
2.67 8.24
2.44 7.06
lost lost
4.44 1.96
3.
3.
2.
2.
23
09
89
27
"irradiated with UV lamp, 22 cm zone centered 1.7M from downstream end of tube.
Irradiation zone centered 0.6 cm from downstream end of tube.
Preloaded on cartridge.
-------
than could have penetrated the tube, but NO- and 0« are photolyzed to
fc J
produce oxygen atoms under these conditions, so that formation of DMN by a
free radical mechanism might be possible. However some H,-DMN was found
even in the absence of added ozone. It could have formed in a photo-
chemical reaction, but it is more likely DMN formed in previous runs was
stripped from the walls of the tube as a result of its being heated by the
lamp (see below"*. Regardless whether DMN is formed by a second (photo-
chemical) mechanism, it appears significant that in general less of it was
found when part of the flow tube was exposed to ultra-violet light, espe-
cially when the irradiation was done near the downstream end (Nos. 31).
This indicates that the rate of DMN photolysis must be more rapid than tue
rates of its formation in any photochemical processes which might occur in
the flow tube under the prevailing conditions. In order to distinguish
between DMN formed in situ by conversion of DMA adsorbed on the Tenax
cartridge and DMN formed from DMA flowing through the tube, a series of
experiments were carried out in which air containing H,-DMA, NO , and
O X
ozone was passed through the flow tube and sampled with a cartridge which
had been preloaded with H,-DMA (Nos. 32-34). Approximately three times as
2 1
much H,-DMN as H,-DMN was found. This experiment was repeated in reverse
fashion, with Hg-DMA being collected on a cartridge preloaded with H,-DMA
(Nos. 35 and 36), and the amount of H,-DMN collected was more than double
2
the BL-DMA formed on the cartridge. In these experiments the amount of
DMA passing through the flow tube was not as precisely known as the amount
which was preloaded on the cartridges. The reason for this is that the
temperature at the upstream end of the flow tube was not thermostatically
controlled. Likewise, the room temperature permeation rates were not
determined under thermostatic control. However, the resulting uncertainty
in the concentration of DMA in the air flowing through the tube could not
account for the extent to which the quantity of DMN formed in the flow tube
exceeded the quantity formed on the cartridge. It is apparent that forma-
tion of DMN from N02, ozone, and DMA is less efficient in a Tenax cartridge
bed than it is in a glass flow tube. Unfortunately, these experiments did
not permit a clear distinction between homogeneous gas phase reactions such
as might occur in the open air and heterogeneous reactions occurring on the
wall of the flow tube.
116
-------
To determine the extent to which DMN that had formed in the reaction
tube might have adhered to the glass wall, samples were taken after the
flow tube experiments had been completed and the permeation tube had been
removed. In preparation, the reaction tube was cleaned by heating it from
ambient to 75°C over a period of 30 minutes while passing 5 £/min of air
through it. During this time a 30 & sample was taken on a Tenax cartridge
at the downstream end of the tube. 2H6-Dimethylamine had last been passed
through the tube eight days before. During the intervening time the tube
had been used for several other experiments. When the cartridge was desor-
bed and analyzed for Hg-DMN, 7.84 nM were found. A second 30 £ sample was
then taken (30 min sampling period) while the tube was maintained at 75°C
to confirm that it had been purged free of H,-DMN and none was found. The
2
tube was cooled to room temperature and Hg-DMA, N02 and ozone was passed
through it for one hour. Following this a 5 2/min stream of clean air was
again passed for 48 min while the temperature was raised to 75°C and a 45 £
sample was collected on a Tenax cartridge. On this cartridge only 0.20 nM
of H,-DMN were found. The amount of DMN that was retained during any of
the experiments in Table 22 was probably small, since only a small quantity
of DMN was recovered by stripping immediately after passing DMA through the
tube for an hour. Since a much larger quantity of DMN was accumulated on
the tube during four days of passing D^-DMN through it, and since a substan-
tial amount remained on the tube for eight days afterward, it would appear
that desorption of DMN from a glass surface is a very slow process at room
temperature. This means that (1) only a small amount of DMN is lost during
the course of an experiment by adsorption on the tube, and (2) desorption
of DMN from the tube at ambient temperature is too low to significantly
affect the results of subsequent experiments. This further implies that
either most of the DMN is formed in homogeneous, gas-phase reactions or
that heterogeneous formation of a molecule of DMN does not usually result
in its adsorption.
The results obtained in this study show that it is important to obtain
simultaneous data on atmospheric concentrations of N0x, (>3, and amines when
sampling for nitrosamines. This would be especially necessary to any
attempt to show that nitrosamines had been formed in the atmosphere from
reactants.
117
-------
SUMMARY
Although establishing the presence and quantity of DMN in ambient air
has been the first emphasis of this study, it is also important to realize
that this compound is one of many present in the pollution profile. Charac-
terization of the other components of the air mixture is of vital impor-
tance. The complete characterization of this mixture is essential for valid
epidemiological correlations between compound incidence and incidence of
neoplasm. Also essential for epidemiological correlations, in addition to
identification of compounds present, is an indication of their quantities
present and work on this important aspect of the problem is the subject of
future research.
118
-------
SECTION 10
DETECTION OF N-NITROSOAMINES UTILIZING SELECTED M/E IONS VIA
COMPUTER SEARCH OF GC/MS/COMP DATA OBTAINED
ON AMBIENT AIR SAMPLES
A computer search was conducted for N-nitrosoamine compounds in ambient
air samples which were collected over a period of 15 months from various
geographical areas within the continental U.S. Mass spectral data of organic
vapors in ambient air had been accumulated on magnetic tapes and these data
were examined for nitrosoamine compounds. Mass spectra were surveyed for
the following N-nitrosoamine compounds: N-nitrosodimethylamine, N-nitroso-
diethylamine, N-nitrosodi-n-butylamine, N-nitrosopiperidine, N-nitroso-
pyrrolidine, N-nitrosomorpholine, N-nitrosohexamethylimine, N-nitrosomethyl-
cyclohexylamine, N-nitrosomethylbenzylamine, and N-nitrosomethylphenylamine.
EXPERIMENTAL
Sampling Techniques
During a 15 month period, cartridges were used for concentrating organic
vapors on a 1.5 x 6.0 cm bed of Tenax GC (35/60) in a glass sampling cart-
ridge. All sampling cartridges were preconditioned by heating to 275°C
for a period of 20 minutes under a helium purge of 20-30 ml/min. After
cooling in precleaned Kimax^^ culture tubes, containers were sealed to
prevent contamination of the cartridge during transportation and storage.
Sampling cartridges prepared in this manner were carried by automobile or
air freight to the sampling site. Two to three cartridges were designated
as blanks to determine whether any of the cartridges might have been contami-
nated by the packing and transportation procedure. Cartridges containing
known quantities (100/300 ng) of N-nitrosodimethylamine were in some cases
prepared and carried to and from the field, stored and analyzed to determine
recovery of N-nitrosodimethylamine.
Samples were taken in replicate as well as blanks discussed above were
subjected to analysis by capillary gas chromatography/mass spectro-
metry/computer (Figure 6). Thermal desorption was used to transfer the
entire amount of trapped vapors from the cartridge sampler to the analytic?1
119
-------
systems and required a specially designed manifold. In a typical
thermal desorption cycle, a sampling cartridge was placed in the preheated
(/v-270°C) desorption chamber and helium gas was channeled through the cart-
ridge (^20 ml/min) to purge the vapors into the liquid nitrogen cooled
capillary trap. After desorption, the six-port valve was rotated and the
temperature on the capillary loop was rapiily ~aised (>10° per min). The
carrier gas introduced the vapors onto the glc column.
A Varian MAT CH-7 glc/ms/comp system was used to perform analysis
(Figure 13). The operating parameters used on the glc/ms/comp system for
analysis of samples collected at various geographical areas was given in
Table 23. Ambient air samples collected as described above were analyzed on
a 400 ft stainless steel SCOT or a 100 m glass SCOT both were coated with
OV-101. Desorption of ambient air pollutants (including nitrosoamines) from
the Tenax cartridges was achieved at 270°C. A single stage glass jet separa-
tor interfaced the SCOT capillary columns to the mass spectrometer and was
maintained at 220°C.
Typically the mass spectrometer was first set to operate in the repeti-
tive scanning mode. In this mode, the magnet was automatically scanned
upward from a preset low mass to high mass value. Although the scan range
may vary depending on the particular sample typically the range was from m/e
28 to m/e 400. The scan was completed in ^3 sec. The instrument then reset
itself to the low mass position in preparation for the next scan and the
information was accumulated by on-line 620/L computer onto magnetic tapes.
The reset period required -v-3 sec. Thus, a continuous scan cycle of ^6
sec/scan was maintained.
Prior to running known samples, the system was calibrated by intro-
ducing a standard substance, such as perfluorokerosene into the instrument
and determining the time of appearance of the known standard peaks in rela-
tion to the scanning magnetic field. The calibration curve which was genera-
ted was stored in the 620/L computer memory.
With the magnet continuously scanning the sample was injected and
automatic data acquisition was initiated. As each spectrum was acquired by
the computer, each peak which exceeds the preset threshold was recognized
and reduced to centroid time and peak intensity. This information was
stored in the computer core while the scan was in progress. In addition,
120
-------
Table 23. OPERATING PARAMETERS FOR GLC-MS-COMP SYSTEM
Inlet-manifold
desorptlon chamber
valve
capillary trap - minimum
maximum
thermal desorption time
GLC 100 m glass SCOT OV-101
400 ft SS SCOT OV-101
carrier (He) flow
transfer line to ms
MS
scan range
scan rate, automatic-cyclic
filament current
multiplier
ion source vacuum
Setting
270°C
220°C
-195°C
+180°C
4 min
20-240°C, 4/C° min
20-240°C, 4/C° min
~3 ml/min
240°C
m/e 20 -»• 300
1 sec/decade
300 viA
6.0
~4 x 10 torr
VJO TIC values and an equal number of Hall probe signals were stored in core
as they were acquired. During the 3 sec period between scans, this spectral
information, along with the spectrum number was written sequentially on the
magnetic tape and the computer was reset for the acquisition of the next
spectrum.
This procedure continued until the entire gc run was completed. By
this time, there were from 300-1000 spectra per chromatographic run which
were then subsequently processed. Depending on circumstances, the data was
either processed immediately or additional samples were run, stored on
magnetic tape and the results examined at a later time.
The mass spectral data was processed in the following manner. The
original spectra was scanned and the TIC information was extracted. Then
the TIC intensities were plotted against the spectrum number on the STATOS I
Recorder. The information was generally indicative of whether the run was
121
-------
suitable for further processing since it gave some idea of the number of
unknowns in the sample and the resolution obtained using the particular glc
column conditions.
The next stage of the processing was the mass conversion of the spec-
tral peak times to peak masses which was done directly by a computer disk
system. Mass conversion was accomplished by use of the calibration table
obtained previously. Normally one set of calibration data was sufficient
for an entire days data processing since the characteristics of the Hall
probe are such that variation and calibration was less than 0.2 atm/day. A
typical time required for this conversion process for 1,000 spectra was
approximately 45 minutes.
After the spectra were obtained in mass converted form, processing
proceeded either manually or by computer.
The technique of mass fragmentography was used for the resolution and
detection of N-nitrosoamines in ambient air samples. This method consists
of acquiring full mass spectra as described above during the chromatographic
separation step and then using selected ions which are presented as mass
fragmentograms with the aid of computer software programs. This allowed the
possibility of resolving and detecting constituents not visually apparent
from the total ion current chromatogram. In our gc/ms/comp system it is
possible to request from the Varian 620/L dedicated computer mass fragmen-
tograms for any combination of m/e when full mass spectra are obtained
during chromatography. Thus, selectivity can be achieved by selecting the
unique ion for that particular compound specifically nitrosamines which are
presented as intensity vs. time and using ion intensity for quantitation.
Table 24 depicts the nitrosamines and their m/e ions selected for detection
in ambient air samples. Listed in this table are the parent ions for each
of the compounds and then the ions of first, second, third and fourth choice
in decreasing order of importance which were utilized for the purpose of
detection and/or quantitation of the N-nitrosoamines. For example, N-
nitrosodimethylamine the parent ion (m/e 74) was selected as the first
choice ion for representation in mass fragmentography since it represents a
rather unique ion of high intensity. In this manner, mass fragmentograms
for each of the ions listed in Table 24 were generated by the computer
system and plotted in terms of ion intensity y_s chromatographic time. By
122
-------
Table 24. NITROSAMINES AND THEIR M/E IONS SELECTED FOR DETECTION IN AMBIENT AIR SAMPLES
N>
Compound
N-nitrosodimethylamlne
N-nitrosodiethylamine
N-nitrosodi-n-butylamine
N-nitrosopiperidine
N-nitrosopyrrolidine
N-nitrosomorpholine
N-nitrosohexamethyleneimine
N-nitrosomethylcyclohexylaraine
N-nitrosomethylbenzylamine
N-nitrosomethylphenylamine
Parent m/e
74
102
158
114
100
116
128
142
150
136
1st
74 (100)
102 (57)
84 (80)
114 (48)
100 (50)
116 (38)
128 (58)
142 (79)
150 (9.5)
79 (22)
m/e (I
2nd
42 (67)
56 (53)
158 (17)
42 (100)
69 (27)
56 (100)
69 (32)
67 (22)
63 (8)
104 (14)
)S
3rd
-
42 (98)
115 (16)
69 (5)
-
86 (28)
-
125 (13)
-
136 (11)
4th
-
44 (100)
70 (14)
-
-
-
-
-
-
-
Q
I = intensity of fragment ion in the mass spectrum.
-------
observing the retention time for standard, authentic nitrosamines chromatc-
graphed under similar operating conditions, a search for the nitrosamines in
the ambient air samples was made.
The overall sensitivity of the mass fragmentographic technique for
nitrosamines in ambient air is shown in Table 25. The sensitivity levels
depicted here are only approximations which ai_° based on (a) the detection
of the primary (first choice) selected m/e ion by the mass spectrometer, (b)
the breakthrough volume of each nitrosamine at the ambient air temperature
during sampling, and (c) other instrumental operating parameters.
RESULTS AND DISCUSSION
Tables 26-32 lists the ambient air samples from the various geogri
phical areas within the continental U.S. that were examined for nitrosamines
by mass fragmentography. These included the Houston, TX vicinity, Los
Angeles, CA basin, the Kanawha Valley, WV, St. Louis, MO, Denver, CO, Atlanta
and Macon, GA and Baltimore, MD. Although these samples had been primarily
collected at these various sites for the purpose of identifying other organic
vapor pollutants, mass fragmentography could and was applied to the detec-
tion of nitrosamines.
A survey of all of these samples indicated the presence of N-nitroso-
diethylamine in a sample taken from the Eisenhower Tunnel in Colorado (Table
31). A trace of N-nitrosodimethylamine was also tentatively detected.
Figure 29 depicts the mass fragmentogram for N-nitrosodiethylamine obtained
for this sample. It was estimated that the concentration of N-nitrosodi-
ethylamine was VLOO ppt. The examination of the remaining mass spectral
data obtained on ambient air from the other remaining sites did not reveal
the presence of N-nitrosoamines down to the levels of sensitivity for which
the instrumentation was capable.
N-nitrosodimethylamine was detected and quantitated in ambient air from
an industrial site in Baltimore, MD (Table 33) and the Kanawha Valley, WV
(Table 34). These data have been reported in Section IX. A search in these
samples for the presence of other nitrosamines was conducted and none were
found.
124
-------
Table 25. ESTIMATED OVERALL SENSITIVITY OF GC/MS/COMP TECHNIQUE
FOR NITROSAMINES IN AMBIENT AIR
Compound parts-per-trilliona
N-nitrosodimethylamine 150
N-nitrosodiethylamine 30
N-nitrosodi-n-butylamine 10
N-nitrosopiperidine 5
N-nitrosopyrrolidine <5
N-nitrosomorpholine <5
N-nitrosohexamethylene imine <5
N-nitrosomethylcyclohexylamine <5
N-nitrosomethylbenzylamine <5
N-nltrosomethylphenylamine <5
Values are based upon the detection of the primary selection ion, its
breakthrough volume (when known) at an ambient temperature of 70°F,
and other instrumental operating parameters.
125
-------
Table 26. AMBIENT AIR SAMPLING PROTOCOL FOR HOUSTON, TX AND VICINITY
Sampling Time Sampling Volume
Site Sampling Location (min) (£) Remarks
Houston, TX May St.
(SI)
Houston, TX Stuebner Airline
(S2)
Pasadena, TX Shaw Drive
(S3)
Texas City, TX
-------
Table 27. AMBIENT AIR SAMPLING PROTOCOL FOR LOS ANGELES, CA AND VICINITY
N>
Site
Santa Monica, CA
(SI)
West Covina, CA
(S2)
Glendora, CA
(S3)
Anaheim, CA
(S4)
Garden, Grove, CA
(S5)
Santa Monica, CA
(S6)
Sampling Location
2441 Arizona Ave.
820 Phillips St.
840 E. Laurel
1700 E. Broadway
12281 Nelson St.
2441 Arizona Ave.
Sampling Time
(tnin)
490
255
660
450
450
900
Sampling Volume
w
7,200
5,600
13,500
6,750
6,750
16,200
Remarks
3/31/75
55°F
4/1/75
58°F
4/2/75
70°F
4/3/75
70°F
4/4/75
58°F
3/31-4/1/75
55°F
0850-1700
W/10 mph
1000-1615
W/5 mph
1000-2100
calm
0930-1630
calm
0900-1630
W/5 mph
1700-0800
calm
-------
Table 28. SAMPLING PROTOCOL FOR THE KANAWHA VALLEY, WV
to
00
Site
S. Charleston
(SI)
S. Charleston
(S2)
Belle
(S3)
Belle
(S4)
Nitro
(S5)
Nitro
(S6)
St. Albans
(S7)
St. Albans
(S8)
S. Charleston
(S9)
S. Charleston
(S10)
Sampling Time
Sampling Location (min)
167 llth Ave.
314 4th Ave.
1511 W. Central St.
Marmet Locks
20th St. (Fire Station)
4019 40th St.
6500 MacCorkle Ave. S.W.
7124 1/2 MacCorkle Ave.
S.W.
314 4th Ave.
167 llth Ave.
480
480
480
480
540
540
720
480
510
450
Sampling Volume
(£) Remarks
2,097 8/4/75
85°F
2,036 8/4/75
85°F
2,040 8/5/75
85°F
2,026 8/5/75
82°F
2,170 8/6/75
76°F
2,240 8/6/75
78°F
2,310 8/7/75
77°F
2,222 8/7/75
77°F
2,086 8/8/75
70°F
1,652 8/8/75
70°F
0900-1700
calm
1000-1750
calm
1024-1830
calm
0931-1751
calm
1031-1948
WSW/2 mph
1100-1900
calm
1000-2000
N/5 mph
1042-2035
N/l-5 mph
0931-1800
ENE/2-3 mph
0852-1628
E/2-3 mph
-------
Table 29. AMBIENT AIR SAMPLING PROTOCOL FOR HOUSTON, TX AND VICINITY
Site Sampling Location
Pasadena, TX C. H. Milby Park
(SI)
Pasadena, TX Mae St.
-------
Table 29 (cont'd)
Sampling Time Volume Sampled
Site Sampling Location (min) (&) Remarks
Houston, TX May St. 720 2,002 8/23/75 1245-1200
(S9) 87°F 92% RH
SE/2-5 mph
w
o
-------
Table 30. AMBIENT AIR SAMPLING PROTOCOL FOR ST. LOUIS, MO AND VICINITY
Site
Alton, 11
(SI)
Wood River, 11
(S2)
Arvado , MO
(S3)
Arvado , MO
(S4)
St. Ann
(S5)
Webster Grove, MO
(S6)
Sampling Time
Sampling Location (min)
2421
2 mi
4400
4400
Chris Lisa St. 540
East of Shell Refinery 300
Lindell 360
Lindell 527
St. Charles Rd. and 415
Industrial Blvd.
Mary
St. 360
Sampling Volume
(£) Remarks
1,898 9/11/75
69 °F
966 9/11/75
79°F
1,130 9/10/75
81°F
1,582 9/9/75
82 °F
2,028 9/8/75
88°F
1,000 9/9/75
93 °F
2250-0750
NW/7-10 mph
1256-1756
W/10-20 mph
0650-1250
calm
2212-0635
calm
2035-0525
WS/2 mph
1114-1604
W/0-5 mph
-------
Table 31. AMBIENT AIR SAMPLING PROTOCOL FOR DENVER, CO AND VICINITY
Co
CO
Sampling Time
Site Sampling Location (min)
1-70, Colorado Eisenhower Tunnel
(SI)
1-70, Colorado Eisenhower Tunnel
(S2)
Rocky Mtn. Park, CO Trail Ridge Rd.
(S3)
Arvado, CO W. 57 Ave & Garrison
(S4)
Arvado, CO W. 47 Ave & Garrison
(S5)
Welby, CO 78th Ave. & Steele St.
(S6)
Denver, CO 16th Ave & Park
(S7)
566
405
484
481
470
300
360
Sampling Volume
W
3,360 9/18/75
40°F
2,116 9/18/75
65°F
2,590 9/17/75
49°F
2,968 9/16/75
72°F
2,780 9/16/75
~80°F
2,284 9/15/75
~63°F
2,105 9/15/75
91°F
Remarks
2024-0550
WNW/5 mph
1239-1924
SW/20 mph
0955-1759
WSW/30 mph .
2159-0700
SW/7 mph
1348-2138
WNW/1-7 mph
1230-0650
calm
1200-1800
WS/2 mph
-------
UJ
w
s-
z:
100^
90-
80-
70-
6Q_
50-
30-
20-
DEN
ra/e 102 I
50
100
150 200 250
Mass Spectrum No.
300
350
400
450
Figure 29. Mass fragmentogram at m/e 102 for N-nltrosodlethylamine.
-------
Table 32. AMBIENT AIR SAMPLING PROTOCOL FOR ATLANTA AND MACON, GA
Sampling Time
Site Sampling Location (min)
Atlanta, GA 248 Oakland Ave. S.E. 270
(SI)
Atlanta, GA Jefferson St. 310
(S2)
Macon, GA Mead St. 280
(S3)
Doraville, GA Dresden Dr. 305
(S4)
Sampling Volume
(£) Remarks
2,120 9/29/75
70°F
1,710 9/30/75
70°F
1,270 10/2/75
72'F
2,290 10/3/75
60°F
1130-1600
NE/15 mph
1045-1555
E, SE/15 mph
1120-1600
N, NE/15 mph
1010-1515
NE/5-10 mph
-------
Table 33. SAMPLING PROTOCOL FOR BALTIMORE, MD AND VICINITY
Site
Baltimore, MD
Baltimore, MD
Baltimore, MD
Baltimore, MD
Baltimore, MD
Baltimore, MD
Baltimore, MD
Baltimore, MD
Sampling Time
Sampling Location (min)
North Bridge and 210
Fairfield (Parking Lot)
North Bridge and 210
Fairfield (Parking Lot)
North Bridge and 210
Fairfield (Parking Lot)
North Bridge and 210
Fairfield (Parking Lot)
Patapsco Sewage Treat- 210
ment Plant (End of
North Bridge)
Patapsco Sewage Treat- 210
ment Plant (End of
North Bridge)
Chessie Coal Piers 210
North Bridge and 120
Fairfield) (WNW of
Sampling Volume
(£) Remarks
300 10/14/75
85°F
300 10/14/75
81°F
300 10/14/75
73°F
300 10/14-15/75
62°F
300 10/16/75
70°F
300 10/16/75
72°F
300 10/17/75
56°F
120 10/19/75
65 °F
1100-1450
W/8 kts
1500-1850
WNW-*WSW/5 kts
1900-2250
SW/Variable
2300-0250
Variable
1000-1350
NW/9 kts
1400-1750
NW/9 kts
1410-1800
ENE/7-14 kts
1400-1600
E/3 kts
Diamazine Plant)
(continued)
-------
Table 33 (cont'd)
Site
Fairfield, MD
Baltimore, MD
Sampling Location
Conoco Parking Lot
North of FMC
(Near Memirac Corp.)
Sampling Time
(min)
120
120
Sampling Volume
a>
120
120
11/20/75
66°F
11/20/75
57 °F
Remarks
1545-1745
SWS/3-6 kts
2020-2220
SSW/4 kts
LJ
-------
Table 34. AMBIENT AIR SAMPLING PROTOCOL FOR KANAWHA VALLEY, WV
LO
--J
Site
Belle,
Belle,
Belle,
Belle,
Belle,
Belle,
Belle,
Belle,
Belle,
Belle,
Belle,
WV
WV
WV
WV
WV
WV
WV
WV
WV
WV
WV
Location
DuPont
DuPont
DuPont
DuPont
DuPont
DuPont
DuPont
DuPont
DuPont
DuPont
DuPont
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
(1)
(2)
(3)
(4)
(1)
(2)
(3)
(4)
(2)
(3)
(4)
Sampling Time
(min)
285
292
293
300
261
263
191
235
362
320
295
(continued)
Volume Sampled
(&) Remarks
247
275
255
294
243
341
297
336
320
350
406
12/1/75
30-35°F
12/1/75
30-35°F
12/1/75
30-35°F
12/1/75
30-35 °F
12/2/75
30°F
12/2/75
30°F
12/2/75
30°F
12/2/75
30 °F
12/2/75
40-50°F
12/2/75
40°F
12/2/75
40°F
2132-0217
NW/1 kt
2127-0219
NW/2 kts
2216-0309
NW/2 kts
2207-0307
NW/2 kts
0229-0652
SE/4 kts
0228-0653
SE/4 kts
0400-0711
SE/4 kts
0317-0712
SE/4 kts
0900-0302
SE/2-calm
2202-0318
SE/2 kts
2205-0300
SE/2 kts
-------
Table 34 (cont'd)
oo
Site
S. Charleston, WV
S. Charleston, WV
S. Charleston, WV
S. Charleston, WV
S. Charleston, WV
S. Charleston, WV
S. Charleston, WV
S. Charleston, WV
S. Charleston, WV
Location
Union Carbide (9)
Union Carbide (10)
Union Carbide (11)
Union Carbide (12)
Union Carbide (11)
Union Carbide (9)
Union Carbide (13)
Union Carbide (14)
Union Carbide (11)
Sampling Time
(min)
232
120
171
120
200
182
122
140
150
(continued)
Volume Sampled
(£) Remarks
248
350
294
292
502
401
392
521
502
12/3/75
50-55°F
12/3/75
50-55°F
12/3/75
50-55°F
12/3/75
50-55°F
12/3/75
45-50°F
12/3/75
45-50°F
12/3/75
45-50°F
12/3/75
45-50°F
12/3/75
45-50°F
1441-1801
WNW-NW/2 kts
1512-1712
WNW-NW/2 kts
1536-1827
WNW-s-NW/2 kts
1538-1728
WNW+NW/2 kts
1833-2053
NW-N/2 kts
1816-2019
NW-s-N/2 kts
1751-1956
NW+N/2 kts
1815-2040
NW-*N/3 kts
1833-2053
NW->N/3 kts
-------
Table 34 (cont'd)
Sampling Time Volume Sampled
Site Location (min) (£) Remarks
S. Charleston, WV Union Carbide (13) 135 402
S. Charleston, WV Union Carbide (14) 117 325
Belle, WV DuPont Plant (5) 119 243
Belle, WV DuPont Plant (6) 118 256
Belle, WV DuPont Plant (7) 125 281
Belle, WV DuPont Plant (8) 120 348
Nitro, WV 1-60 and WV25 230 1,593
Nitro, WV 1-60 and WV25 240 1,800
12/3/75
40-45°F
12/3/75
40-45°F
12/4/75
54-60°F
12/4/75
60°F
12/4/75
60°F
12/4/75
60°F
12/5/75
65°F
12/5/75
65°F
2003-2217
N+NNE/3 kts
2047-2244
N+NNE/3 kts
1710-1911
NE/2 kts
1526-1724
NE/2 kts
1600-1805
calm
1906-2106
NE/2 kts
1158-1548
SW/10 kts
1159-1549
SW/10 kts
-------
SECTION 11
IDENTIFICATION OF VOLATILE ORGANIC VAPORS IN AMBIENT AIR
FROM SEVERAL GEOGRAPHICAL AREAS IN THE CONTINENTAL U.S.
The overall objective was to apply the sampling and analytical metho-
dology to the analysis of ambient air pollutants. Our specific objectives
has been to determine the viability of this technique for the collection
and analysis of various chemical classes occurring in the atmosphere. In
order to demonstrate the utility of this methodology, various geographical
areas within the Continental U.S. were selected for study. The selection
of these areas was based on two primary factors. The first was related to
the types of industrial activity which were cited in the Chemical Industry
Directory on a state by state basis which indicated the potential types of
organic vapors that might be present in the atmosphere due to the type of
chemical activity occurring at these sites. Selection of sites was based
on the activity in which the industry was engaged, e.g. whether it was
involved in the production, the use, or storage of volatile organic chemi-
cals. These activities were related to the storage, use or production of
chlorinated hydrocarbons, nitrogenous substances, oxygenated materials, and
sulfur compounds. A second criteria used in the selection of study areas
was the relationship between the heavy industrial activity and the high
incidence of cancer which has been demonstrated by statistical studies
Q4)
reported by the National Cancer Institute.
The geographical areas which were studied under this program were:
the Kanawha Valley in West Virginia, Houston, TX and vicinity, St. Louis,
MO, Denver, CO, Atlanta, GA and vicinity, Central and Northern New Jersey,
and the Los Angeles, CA Basin.
EXPERIMENTAL
Sampling Techniques
The sampling procedure employed has been previously described which
consisted of concentrating hazardous vapors and other organic compounds on
a 1.5 x 6 cm bed of Tenax GC (35/60) in a glass cartridge. All sampling
cartridges were preconditioned by heating to 275°C for a period of 20 rain
140
-------
under a Helium purge of 20-30 ml/min. After cooling in precleaned
culture tubes, the containers were sealed to prevent contamination of the
cartridge. Sampling cartridges were carried by air freight or automobile
to the sampling site with 2-3 cartridges designated as blanks to determine
whether any of the cartridges might be contaminated by the packing and
transportation procedure. Ambient air samples were collected with a Nutech
Model 221-A AC/DC portable sampler. In general, a sampling rate of 1-2
£/min/cartridge was used throughout this study.
Meterological conditions were recorded with hand held instruments.
The wind direction, velocity, temperature and humidity were all determined.
Wind direction was determined using a lensatic compass. The compass was
also used to describe the sampling location relative to major industrial
facilities. Wind velocity was estimated with a Dwyer wind meter (Dwyer
Instruments Inc., Michigan City, IN), a hand held rotameter with two scales,
2-10 mph and 4-66 mph. Barometric pressure was measured with a Pocket
Altimeter (Gischard, West Germany). This aneroid barometer was compared
with a mercury barometer and found to read to 0.1 in of mercury too high.
It was calibrated from 19-31" of mercury and 0-13,000 ft of altitude. Air
temperature and relative humidity were determined with a sling psychrometer
(Taylor Instruments Co., Rochester, NY). Precipitation was measured volume-
trically with a Nimbus Model 609-B rain gauge (Air Guide Instruments Co.,
Chicago, IL).
Distances from a suspected point source of pollution or for deter-
mining the location of sampling was estimated with a Rangematic Distance
Finder (Ranging Inc., Rochester, NY). The range finder was calibrated for
50-1,000 yds (also has indications for 1 and 2 miles). It was found to be
accurate to +1% at 100 yds.
The sampling protocols employed for ambient air analysis in the various
geographical areas within the Continental U.S. were given in Tables 26-35.
Sampling locations for the Los Angeles, CA basin are depicted in Figures 30
and 31.
Instrumental Methods of Analysis
The instrumental system (glc/ms/comp) used for the qualitative and
quantitative analysis of organic vapors and the inlet-manifold used for
recoverying vapors trapped on Tenax GC sampling cartridges has been
141
-------
10
Table 35. SAMPLING PROTOCOL FOR CENTRAL AND NORTHERN NEW JERSEY AND
LOS ANGELES, CA BASIN
Site
Paterson, NJ
(SI)
Clifton, NJ
(S2)
Passaic, NJ
(S3)
Hoboken, NJ
(S4)
Newark, NJ
(S5)
New York City, NY
(Staten Island)
(S6)
Edison, NJ
(S7)
Fords, NJ
(S8)
Sampling Time
Sampling Location (min)
12th St. & 4th Ave. 42
Dyer Ave. & 39
Wheeler St.
First St. & 39
Essex St.
New County Rd. 39
U. S. Post Office
Depot
552 Dor emus Ave. 38
Chelsea Rd. at 37
Bloomfield Ave.
Meadow Rd., directly 42
across from Stauffer
plant
North of Tenneco 44
plant
Sampling Volume
(£) Remarks
300 3/22/76
40°F
300 3/22/76
45°F
300 3/22/76
40°F
300 3/23/76
51°F
300 3/23/76
53°F
300 3/23/76
54°F
300 3/25/76
62°F
300 3/26/76
72°F
1231-1313 hr
300-360°/3 mph
1528-1607 hr
320 °/2 mph
1715-1754 hr
320 °/5 mph
1223-1302 hr
230°/0-10 mph
1400-1438 hr
2700/u-10 mph
1702-1739 hr
280°/0-5 mph
1720-1802 hr
225-240°/3-8 mph
1559-1643 hr
200° /0-2 mph
(continued)
-------
Table 35 (cont'd)
Site
Bound Brook, NJ
(S9)
El Segundo, CA
(SI)
Torrance, CA
(S2)
Los Angeles, CA
(S3)
Long Beach, CA
(S4)
Sampling Time
Sampling Location (min)
Eastern Turnpike 44
directly north of
American Cyanamid Co.
Illinois St. 54
(See Fig. 30)
19146 Van Ness Blvd. 55
20100 Normandie Ave. 54
63rd Avenue & 52
Paramount Blvd.
Sampling Volume
a)
300 3/26/76
68°F
300 5/12/76
76 °F
300 5/13/76
76°F
300 5/13/76
78°F
300 5/13/76
80°F
Remarks
1732-1816 hr
200° /0-7 mph
1329-1423 hr
220-240° /2-8 mph
1307-1412 hr
230-250° /2-7 mph
1357-1451 hr
270°/0-7 mph
1707-1759 hr
250°/3-8 mph
-------
mill
-EL
Pacific
Ocean
Standard Oil Co.
Refinery
RoMcrons Blvd.
I-
• Sampling Site
El Segundo Blvd.
Illinois St.
0 1/4 1/2
MILES
Figure 30. Map depicting sampling site in El Segundo, CA
11/2
-------
Ul
Mobil ; Dow
VRefinery | Chemical
MILES
Figure 31. Map depicting sampling site in Torrance, CA
-------
previously described. ' The operating parameters for the glc/ms/comp
system for the analysis of samples was given in Table 23. Samples were
analyzed on a 100 m glass SCOT capillary coated with OV-101 stationary
phase. The desorption of vapors from the Tenax sampling cartridges was
achieved at 270°C. A single stage glass jet separator interfaced with SCOT
capillary columns to the mass spectrometer wa*» maintained at 220°C. The
capillary column was programmed from 20-240°C at 4°/min.
Identification of the constituents in the samples was established by
comparing the mass cracking pattern of the unknown mass spectra to an 8
(12) (13)
peak index and to the Wiley collection. In many cases the identi-
fication was confirmed by comparing the mass cracking pattern of an authen-
tic compound with that of the unknown. Their elution temperatures were
also compared.
By utilizing either the total ion current monitor when the consti-
tuents were adequately resolved or when necessary the use of mass fragmen-
tograms, the concentrations of each substance was determined. In order to
eliminate the need to obtain complete calibration curves for each compound
for which quantitative information was desired, we used the method of
relative molar response (RMR) factors. This technique has been reported
i v, (20)
elsewhere.
RESULTS AND DISCUSSION
The volatile organic vapors which were collected and identified utili-
zing glc/ms/comp for samples collected in the Kanawha Valley, Houston, TX,
St. Louis, MO, Denver, CO, NJ, and Los Angeles Basin areas are listed in
Tables 38-40, 41-50, 51-53, 54-55, 56-63, and 64-66, respectively, in
Appendix I. In general, many of the organic vapors which were identified
probably can be attributed to background from fossil fuel burning. The
alkanes, alkenes, and alkyl aromatics constitued the predominant group of
compounds which were present and persisted in all samples. Several halo-
genated hydrocarbons were also frequently observed in these samples. These
compounds were methyl chloride, methylene chloride, chloroform, methyl
chloroform, tetrachloroethylene, monochlorobenzene, dichlorobenzenes and
trichlorobenzenes. Another halogenated compound though not as often obser-
ved was carbon tetracloride. Many oxygenated hydrocarbons were also detec-
ted, particularly analogs of furans.
146
-------
In ambient air samples from the C. H. Milby Park in Pasadena, TX, we
identified 2-chloro-l,3-butadiene (chloroprene) and l-chlorobutene-3-yne.
These samples were taken a location approximately 200 yds downwind from an
industrial complex. Ambient air samples collected at an upwind site during
the same sampling period, did not reveal the presence of these two chlori-
nated hydrocarbons. A third unique chlorinated hydrocarbon, 1,4-dichloro-
2-butene was tentatively identified in the sample collected at C. H. Milby
Park. Ambient air samples collected in Pasadena, XX at locations S2 and S3
(see Table 29) were found to contain dibromodichloromethane and bromoform.
The presence of dimethylnitrosoamine was tentatively identified in
ambient air samples collected at the entrance of the Eisenhower Tunnel in
Colorado. N-nitrosodiethylamine was also detected in these samples which
was previously described in Section X. An additional nitrogenous compound
dimethylformamide was also identified.
Samples from the Central and Northern NJ area contained many compounds
of particular interest. We identified several halogenated compounds.
These were: dibromomethane, vinyl chloride, 1,2-dichloroethane, 1,1-
dichloropropane, 2-chloroethyl acetate, N-decyl chloride and a chloro-
propane. Also many nitrogen containing compounds were detected. These
were: ethylamine, isoamyl nitrile, pyridine, aniline, N-methylaniline,
dimethylaniline, chloroaniline, a-naphthylamine and 2-ethylquinoline. The
concentrations of several ambient air pollutants near industrial sites in
the New Jersey area were quantitated. Their levels are given in Table 36.
3
The concentration of vinyl chloride was approximately 120,000 ng/m of
ambient air. The concentration of chloroaniline in a sample taken from
3
Bound Brook was 33 ng/m . In the same sample, a very high concentration of
3
chlorobenzene was detected (20,000 ng/m ). Whereas in many other samples
that have been analyzed at several different geographical locations, gene-
rally indicate a trace to non-detectable levels of chlorobenzene (<10
3
ng/m ). Table 36 presents a general trend which exemplifies the ubiquitous
nature of many of the halogenated hydrocarbons e.g. chloroform has been
consistently found at levels in the samples from New Jersey area to be in
3
the M8/m range. On the otherhand, the chlorobenzenes are in trace amounts.
The highest concentration of all of the pollutants measured was methyl
3
acrylate in Newark, NJ (4,545,000 ng/m ). The same sample had a high
147
-------
Table 36.... CONCENTRATIONS OF AMBIENT AIR POLLUTANTS NEAR INDUSTRIAL SITES
IN THE NEW JERSEY AREA3
oo
Compound
benzene
n-butyl acetate
«N chloroaniline
chlorobenzene
chloroform
dibromoethane
1 , 2-dichloroethane
a-methylnaphthalene
<„, nitrobenzene
tetrachloroethylene
1,2, 4-trichlorobenzene
•4 1,3,5-trichlorobenzene
1, 1, 1-trichloroethane
trichloroethylene
vinyl chloride
•« methyl acrylate
n-butyl acrylate
Bound
Brook
9,000
ND
33
20,000
4,167
ND
trace
134
126
trace
99
867
trace
trace
ND
trace
ND
Paterson
2,160
ND
ND
trace
3,750
130
trace
ND
ND
trace
ND
ND
trace
1,200
ND
ND
ND
Clifton
trace
ND
ND
trace
8,300
ND
64,516
ND
ND
trace
ND
ND
trace
trace
400
ND
ND
Fords
3,068
ND
ND
trace
16,700
ND
ND
ND
ND
trace
ND
ND
1,300
ND
ND
ND
ND
Newark
300,000
113,000
ND
trace
37,000
ND
ND
ND
ND
trace
ND
ND
trace
ND
ND
4,545,000
17,000
Passaic
2,045
ND
ND
ND
4,167
ND
ND
ND
ND
trace
ND
ND
13,000
trace
^120,000
ND
ND
Hobcken
trace
ND
ND
trace
2,083
ND
trace
ND
ND
trace
ND
ND
trace
trace
ND
ND
ND
Staten Is.
;NY)
2,270
ND
ND
trace
20,830
ND
ND
ND
ND
trace
ND
ND
trace
ND
ND
ND
ND
values,in ng/m
-------
3 3
concentration of benzene (300,000 ng/m ), n-butyl acetate (113,000 ng/m ),
3 3
chloroform (37,000 ng/m ) and n-butyl acrylate (17,000 ng/m ). Benzene has
been regarded as a ubiquitous pollutant since it has been detected at
measurable quantities in the majority of samples which we have collected
throughout the Continental U.S.
The concentrations of some pollutants which were identified in ambient
air from Torrance, CA are given in Table 37 (Fig. 31). A rather high
q
concentration of carbon tetrachloride was detected (38,095 ng/m ) and
3
methylene chloride (14,285 ng/m ). This sample also contained m-chloro-
benzaldehyde and chloral.
In Tables 38-66, many siloxane compounds have been indicated. These
compounds are generally derived as background constituents from the high
resolution capillary column used for effecting the separation of the mix-
tures . Also in some samples, the presence of ethylene oxide has been
noted. This compound is believed to be derived as background from the
sampling cartridge during the thermal desorption step.
149
-------
Table 37. CONCENTRATION OF POLLUTANTS IN AMBIENT AIR
IN TORRANCE, CA
, -- 3
Compound ng/m
benzene 13,640
carbon tetrachloride 38,095
chlorobenzene 20,670
m-chlorobenzaldehyde 334
chloral 660
methylene chloride 14,285
1,2,3,3-tetrachloropropene 100
trichlorobenzene 2,670
1,1,1-trichloroethane 1,000
trichloroethylene -1,000
150
-------
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1. Pellizzari, E. D. Development of Analytical Techniques for Measuring
Ambient Atmospheric Carcinogenic Vapors. Pub. No. EPA-600/2-75-075,
Cont. No. 68-02-1228, November 1975.
2. Pellizzari, E. D. Development of Method for Carcinogenic Vapor Analy-
sis in Ambient Atmosphere. Pub. No. EPA-520/2-74-121. Cont. No. 68-
02-1228, July 1974.
3. Pellizzari, E. D., Bunch, J. E., Carpenter, B. H. and E. Sawicki,
Environ. Sci. Technol., 9, 552 (1975).
4. Pellizzari, E. D., Carpenter, B. H., Bunch, J. E., and E. Sawicki,
Environ. Sci. Technol., 9, 556 (1975).
5. Tore, J. C. and G. J. Kallos, Anal. Chem., 46, 1866 (1974).
6. O'Keeffe, A. E. and Ortman, G. C., Anal. Chem., 38, 760 (1966).
7. Novotny, M. and A. Zlatkis, Chromatog. Reviews, 14, 1 (1971).
8. Jennings, W. G., Yabumoto, K. and R. H. Wohleb, J. Chromatog. Sci.,
12, 344 (1974).
9. German, A. L. and E. C. Horning, J. Chromatog. Sci., 11, 76 (1973).
10. German, A. L. Pfattenberger, C. D., Thenot, J.-P., Horning, M. G., and
E. C. Horning, Anal. Chem., 45, 930 (1973).
11. Pellizzari, E. D., J. Chromatog., 92, 299 (1974).
12. "Eight Peak Index of Mass Spectra", Vol. 1, (Tables 1 and 2) and II
(Table 3), Mass Spectrqmetry Data Centre, AWRE, Aldermaston, Reading,
RF74PR, UK, 1970.
13. Registry of Mass Spectra Data, ed. by E. Stenhagen, 4 Vol., John Wiley
& Sons, New York, 1974.
14. "U. S. Cancer Mortality by County: 1950-1969". U. S. Department of
Health, Education and Welfare, Public Health Service.
15. National Institutes of Health. National Cancer Institute, Bethesda,
Maryland. DHEW Publication No. (NIH) 74-614). Christensen, H. E.:
151
-------
Luginbyhl, T. T.: editors. Carroll, B. S.: project coordinator.
Suspected Carcinogens. Subfile of NIOSH Toxic Substances List. U. 3.
Department of Health, Education and Welfare, Public Health Service,
Center for Disease Control, NIOSH, Rockville, Maryland.
16. Fishbein, L. In Chromatography of Environmental Health, Vol. 1,
Carcinogens, Mutagens, and Teratogens. E]seview: New York, 1972, 499
pp.
17. Fine, D. H., Roundbebler, D. P., Belcher, N. M., and S. S. Epstein.
In Proceedings of the International Conference on Environmental
Sensing and Assessment Las Vegas. Nevada, October 1975. In press.
18. Pellizzari, E. D., Bunch, J. E., Berkley, R. E., and J. McCrae, Jr.,
Anal. Chem., 48, 803 (1976).
19. Pellizzari, E. D., Bunch, J. E., Berkley, R. E., and J. McCrae, Anal.
Lett., 9, 45 (1976).
20. Pellizzari, E. D. Identification and Analysis of Ambient Air Pollu-
tants Using the Combined Techniques of Gas Chromatography and Mass
Spectrometry. EPA Contract No. 68-02-2262, 1977, in preparation.
152
-------
APPENDIX A
VOLATILE ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR AT VARIOUS
GEOGRAPHICAL LOCATIONS WITHIN THE CONTINENTAL UNITED STATES
153
-------
90r
80-
70-
60-
50-
30-
10 •_
y-
56
TEMPERATURE (°C>
104 116 128 MO 152 164 176 188 SOO 212 224 230 23O 230 230 230
12
19 16 21 24
27
30 33 36
TIME (WIN)
39 42 45 48
54 57 60 63
Figure 32. Profile of ambient air pollutants for South Charleston, WV using high
resolution gas chromatography/mass spectrometry/computer. A 400 ft
S.S. SCOT coated with OV-101 stationary phase and a temperature pro-
gram of 20-230°C @ 4°C/min were used. See Table 38 for listing.
-------
Table 38. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR
IN SOUTH CHARLESTON, WVa
Chroraatographic
Peak No.
1A
IB
1C
ID
2
2A
3
3A
A
4A
4B
4C
5A
5
5B
6
6A
6B
7
8
9
9A
10
10A
10B
11
11 A
12
12A
12B
13
Elution Temperature
(°C) '
83
89
92
95
102
103
106
106
108
109
110
111
112
113
114
115-7
116
116
117
120
124
125
126
128
129
135
135
136
137
137
138
(continued)
155
Compound
co2
cyclopropane
chlorome thane
1-butene
isopentane
C.-H isomer
furan
jv-pentane
acetaldehyde
CCH0 isomer
J O
C H isomer
dichlorome thane
carbon disulfide
propanal
methylsilane (BKG)
acetone.
C,H.. „ isomer
O L
-------
Table 38 (cont'd)
Chroma tographic
Peak No .
14
15
16
17
18
20
20A
20B
20C
21
22
23
23A
24
25
25A
26
26A
27
28
29
30
31
32
33
34
35
35A
36
36A
37
Elution Temperature
139
140
141
142
143
145
146
147
148
149
150-2
152
153
154
156
156
157
158
159
160
161
164-5
166
167
169
170
172
172
174
174
175
(continued)
156
Compound
2 , 3-dimethylpentane
C..H, . isomer
7 14
3-methylhexane
C-.H.. . isomer and C^H.. , isomer
7 14 7 ID
dimethylcyclopentane isomer
n-heptane
2,5-dimethylfuran (tent.)
C?H1, isomer
2 , 4-dimethylf uran
2,2, 4-trimethylpentane
methylcyclohexane
C0Hn , isomer
o lo
2, 4-dimethylhexane
ethylcyclopentane
trimethylcyclopentane isomer
dimethyl disulfide
trimethylcyclopentane isomer
CpH,,. isomer
2, 3-dimethylhexane
toluene
3-methy Ihep tane
dimethylcyclohexane isomer and
4-methyl-2-pentanone
1-octene
n-octane
hexamethylcyclotrisiloxane (BKG)
tetrachloroethylene
3-hcxanone and isobutyl acetate
CgH , isomer
CJtly- isoiner
C H isomer
2-hexanone and dinitithylcyclo-
hexane isomer
-------
Table 38 (cont'd)
Chromatographic
Peak No.
38
39
40
41
42
42A
42B
42C
42D
43
44
45
46
47
48
49
49A
49B
50
51
51A
52
53
54
56
56A
57
58
59
60
60A
Elution Temperature
176
178
179
180
181
183
183
184
185
186
187
191
192
193
194
195
196
197
198
199
199
199-200
200.5
201
203
204
205
206
207
208
208
(continued)
157
Compound
jri-butyl acetate
chlorobenzene
C9H2Q isomer
ethylbenzene
j)-xylene
C-H isomer
phenyl acetylene
CqtLo isomer
C H n isomer
styrene
o-xylene and n-nonane
CqH, „ isomer
C10H22 isomer
isopropylbenzene
G10H22 isomer
C_-alkylcyclohexane isomer
C1()H22 isomer
GI nH_0 isomer
C* 10^22 isomer
n-propylbenzene
C10H22 isomer
m-ethyl toluene
1,3,5-trimethylbenzene and
silane compound
C11H_, isomer
_p_-ethyl toluene
1-decene
ii-decane
1,2, 4-tr imethylbenzene
C.,,H22 isomer
benzaldehyde
C11H?, isomer
-------
Table 38 (cont'd)
Chroma tographic
Peak No.
61
62
63
64
65
66
67
68
69
70
71
72
73
74
74A
75
76
76A
Elution Temperature
(°c)
209
210
210
212
213
214
215
215
216
217
218
219
220
221
221
222
223
223
Compound
m-dichlorobenzene or (_p_)
C11H24 isomer
C,-alkyl benzene isomer
1,2, 3-trimethylbenzene
C....H,,, isomer
11 24
C , -alkylcyclohexane isomer
a-me thyl s tyr ene
C,-alkyl benzene isomer
C,-alkyl' benzene isomer
C,-alkyl benzene isomer
C,,H«, isomer
11 24
C,-alkyl benzene isoiner
C,-alkyl benzene isomer
C_.,H_,. isomer
11 22
C,-alkyl benzene isomer
n-undecane
dimethylstyrene isomer
C.-alkyl benzene isomer and
Cn00- isomer
L£ iv
77 224 C5~alkyl benzene and C -.H-_
isomers
225 Cl2H26 isomer
78 225 Ci2H26 isoiner
79 226 C^-alkyl benzene isomer
81 227 C,-alkyl benzene isomer
228 silane compound and C,_HOC
isomer 12 26
82 228 C12H24 isomer
83 23° C13H28 ±soraer and C
benzene isomer
°* 230 C,.-cyclohexane isomer
85 230 C12H26 isomer
(continued)
158
-------
Table 38 (cont'd)
Chroma tographic
Peak No.
86
87
88
89
90
91
92
Elution Temperature
230
230
230
230
230
230
230
230
Compound
C.«Hn, isomer
12 2b
C.. 0H_ , .isomer
12 /b
silane compound (BKG)
C^-H^n isomer
13 28
C13H28 isomer
n-dodecane
C13H28 isomer
naphthalene
aSam\)ling site was 167 llth Ave. at. the Dept. of Health, State
Hygenic Laboratory. See Table 28 (SI) for sampling protocol.
159
-------
Table 39. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR IN
S. CHARLESTON, WV3
Chromatographic
Peak No.
1
2
2A
3
4
5
5A
6
6A
6B
7
7A
8
9
10
10A
11
12
13
14
14A
14B
15
ISA
16
16A
16B
17
18
18A
19
Elution Temperature
81
88
89
91
101
105
106
107
108
109
111
112
115
116
119
121
123
124
125
128
129
130
131
132
133
134
134
135
136
136
137
(continued)
160
Compound
co2
1-butene
n-butane
2-butene
isopentane
Cc-H, n isomer and furan
n-pentane
acetaldehyde
dichloromethane
carbon disulfide (tent.)
propanal
methylsilane
acetone
2-methylpentane
3-methylpentane
C6H12 isomer
n-hexane and 2-methylfuran
C ,H „ isomer
D 12
3-methylfuran and chloroform
C.-H-. , isomer
6 14
silane compound (BKG)
2, 2-dimethylpentane
2 , 4-diraethylpentane
2,2, 3-tr iinethylbutane
1,1,1-trichloroethane
C_H.^ isomer and methyl ethyl
ketoiie
3,3-dimethylpentaiie
benzene
carbon tetrachloride
cyclohexane
2-methylhexane
-------
Table 39 (cont'd)
Chromatographic
Peak No.
20
20A
21
21A
22
23
23A
24
25
25A
26
27
28
29
29A
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
Elution Temperature
138
139
140
141
142
143
144
145
149
150
150
152
152
153
154
155
156
157
157
158
159
161
164
167
169
170
172
173
175
176
(continued)
161
Compound
2 , 3-dimethylpentane
C_H, , isomer
7 14
3-methylhexane
C_H-j, isomer
l,cis-2-dimethylcyclohexane
1, trans-2-dimethylcyclohexane
C^H.., + CJrL „ isomer
n.-heptane
CgH18 isomer
dimethylcyclopentane isomer
methylcyclohexane
C0IL , isomer
8 10
2 , 4-dimethylhexane
C8H18 + C8H16 is°mer
C H R isomer
C_H1 R isomer
methylethylpentane isomer
+ C8H16
1, trans-2,cis-3-trimethylcyclo'
pentane
C0H10 isomer
o lo
2 , 3-dimethylhexane
toluene
3-methylheptane
4-methyl-2-pentanone +
dimethylcyclohexane isomer
n~octane
hexamethylcyclotrisiloxane
tctrachloroethylene
isobutyl acetate
CqH,,.. isomer
C9U20 isomer
2-hexanone
-------
Table 39 (cont'd)
Chromatographic
Peak No.
45
45A
46
47
48
48A
49
50
51
52
52A
53
54
55
55A
56
57
57A
58A
58
59
60
61
62
63
64
65
66
66A
67
68
Elution Temperature
177
178
179
180
181-4
184
185
186
189
191
191
192
193
194
194
195
196
197
197
198
198
199
200
201
201
201
202
203
204
205
205
206
(continued)
162
Compound
n-butyl acetate
chlorobenzene
°9H20 isomer
ethylbenzene
ja-xylene
phenyl acetylene
dibutyl ether
styrene
o-xylene + n-nonane
Cn..H«_ isomer
10 22
C0H, 0 isomer
y J.O
C, ~H,,,. isomer
10 22
isopropylbenzene
CinHn_ isomer
10 22
CinH__ isomer
10 20
C^-alkylcyclohexane isomer
C10H16 + C10H22 isomer
CT „!!„» isomer
10 20
C,-H-0 isomer
10 22
5-methylnonane
ri-propylbenzene
m-e thy 1 toluene
3-methylnonane
1,3,5- tr imethylbenzene
Cn,H0. isomer
11 24
C....H-- + silane compound
CinH00 isomer
10 22
^-ethyltoluene
C10H20 is°mer
n-decane
1, 2,4-trimethylbenzene
CniH isomer
11 22
-------
Table 39 (cont'd)
Chroma tographic
Peak No.
69
70
71
71A
72
73
73A
74
75
75A
76
77
77A
78
79
80
81
82
83
83A
84
85
86
87
88
89
90
91
92
93
94
95
Elution Temperature
208
209
209
210
210
211
211
212
213
213
214
215
215
216
216
217
217
218
219
220
220
221
222
223
225
226
227
227
229
230
230
230
(continued)
163
Compound
CinH_rt isomer
10 20
benzaldehyde -1- C,,H0. isomer
11 24
isobutylbenzene
C....H,,, isomer
11 24
m- or j>-dichlorobenzene
C,nH^. isomer
11 24
o-cymene
1, 2,3-trimethylbenzene
C-.-.H,,, isomer
C....H,.,, isomer
11 22
C,-alkyl cyclohexane isomer
a-methylstyrene
£-cymeae
p-propyltoiuene
C1^Rj, isomer
o-diethylbenzene
n-butylbenzene
C,_H«, isomer
12 26
o-propyl toluene
C.. nH,R isomer
dimethylet'.iylbenzene isomer
n-undecane
C12H25 isomer
C10H0,
12 26
C^-alkyl benzene isomer
C,0H_., isomer
12 2o
C12H26 isomer
C.-alkyl benzene isomer
C12H24 + C31H20 iEOmer
C,.-alkyl benzene isomer
C, -alkyl benzene isomer
C H iso"-"r
12 26 ' ""
-------
Table 39 (cont'd)
Chromatographic
Peak No.
96
97
98
100
101
102
103
Elution Temperature
230
230
230
230
230
230
230
Compound
C, ,,!!„, isomer
CT-H-J, isomer
U 2o
silane compound (BKG)
C13H28 isomer
C13H28 isomer
C _H_. isomer
n-dodecane
See Table 28 (S2) for sampling protocol.
164
-------
Table 40. POLLUTANTS IDENTIFIED IN AMBIENT AIR
FROM SOUTH CHARLESTON, WVa
Chromatographic
Peak No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
14A
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Elution Temperature
85
88
89
91
97
100
101
104
109
113
115
117
119
121
121
123
124
130
132
133
134
135
135
136
136
138
140
141
143
148
(continued)
165
Compound
carbon dioxide
chloromethane (tent.)
ethylene oxide (tent.)
2-methylpropene (tent.)
chloroethane (tent.)
C5H12
trichlorofluoromethane (tent.)
ethanol
propylene oxide (tent.)
acetone
CAH1/
6 14
2-propanol (tent.)
C,H17
6 14
C6H14
2-methylpropenal (tent.)
vinyl acetate
2-methylfuran
methyl vinyl ketone
methyl ethyl ketone
3 ,3-dimethylpentane
benzene
carbon tetrachloride
cyclohexane
C7H16
C7H16
C7H16
C7H14
C7H14
C7H16
C7H14
-------
Table 40 (cont'd)
Chromatographic
Peak No.
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
52A
53
54
55
56
57
58
59
Elution Temperature
<°C)
148
152
152
154
155
156
158
160
163
164
165
167
168
168
172
175
177
178
179
180
-182
184
185
185
191
192
193
194
196
197
198
(continued)
166
Compound
C7H14
C8H18
C7H14
C8H16
C8H16
C8H18
toluene
C8H18
C8H16
C8H16
C.H
8 18 v
dibromodichloromethane (tent.)
hexamethylcyclotrisiloxane
tetrachloroethylene
C8H16
chlorobenzene
C_Hori
9 20
ethylbenzene
£-xylene
m-xylene
phenylacetylene
C0H10
9 18
£-xylene
CnH0rt
9 20
CnH0/,
9 20
isopropylbenzene
€„!!„„
9 20
CnH, „
9 18
r H „
9 18
n-propylbenzene
m-ethyl toluene
-------
Table 40 (cont'd)
Chromatographic
Peak No.
60
61
62
63
64
65
66
67
68
69
70
71
72
73
73A
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
Elution Temperature
(°C)
198
199
199
200
202
202
203
203
206
207
208
208
209
211
211
212
212
212
213
213
213
214
215
215
216
217
218
218
219
220
(continued)
167
Compound
p_-e thy 1 to luene
1,3,5-trimethylbenzene
unknown m/e 133, 193, 191,
249, 251
C10H22
o-ethyl toluene
C10H20
C10H22
1 , 2 , 4-trimethylbenzene
benzaldehyde
C, -alkyl benzene
m-dichlorobenzene
C, -alkyl benzene
1 , 2 , 3-trimethylbenzene
acetophenone
p_-dichlorobenzene
C10H20
C, -alkyl benzene
indan
C, -alkyl benzene
o-dichlorobenzene
C,-alkyl benzene
C, -alkyl benzene
C, -alkyl benzene
C11H24
C11H24
C, -alkyl benzene
C,-alkyl benzene
C,-alkyl benzene
C, -alkyl benzene
C11H24
-------
Table 40 (cont'd)
Chromatographic
Peak No.
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
113A
114
115
116
117
118
Elution Temperature
(°C)
221
221
222
223
224
224
225
225
226
226
228
229
229
230
230
230
230
230
230
230
230
230
230
230
230
230
230
230
230
(continued)
168
Compound
methylindan ( tent . )
C -alkyl benzene
4
C<.-alkyl benzene
C,. -alkyl benzene
C, -alkyl benzene
C,. -alkyl benzene
C12H26
C.-alkyl benzene
C, -alkyl benzene
unknown, m/e 73
C,.-alkyl benzene
C,- -alkyl benzene
C12H26
methylindan (tent.)
unknown, m/e 105, 106
C.. 0Hn -
12 26
C,. -alkyl benzene
methylindan (tent.)
C^-alkyl benzene
L* _ -. ti — ,
12 26
C,. -alkyl benzene
C_-alkyl benzene
tetralin
C^-alkyl benzene
C^-alkyl benzene
t* . AtlH -
12 26
C «H
12 26
C nH
12 24
C^H -alkyl benzene
C^-alkyl benzene
C H
12 26
-------
Table 40 (cont'd)
Chromatographic Elution Temperature
Peak No. (°C)
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
Compound
naphthalene
C,.-alkyl benzene
unknown alkane
C,.-alkyl benzene
Cv-alkyl benzene
unknown
unknown
CTt
— A »n f
13 26
CTT
1 *1 **»•» n
13 28
C13H26
C13H28
C13H28
C13H28
C14H30
C--alkyl benzene
o
C,-alkyl benzene
C13H28
C14H28 (tent')
C14H30 (tent'>
unknown, m/e 73
Cn/H
14 30
C10H0.. (tent.)
13 26
unknown
2-methylnaphthalene
C ,/H-Q (tent.)
14 28
C14H28 (tent')
C14H30 (tent')
1-methylnaphthalene
C14H3Q (tent.)
C-.H.- (tent.)
14 30
C15H32
(continued)
169
-------
Table 40 (cont'd)
Chromatographic Elution Temperature
Peak No. (°C)
Compound
150
151
152
152
154
155
156
C14H28 (tent->
C14H30
C14H30
unknown
unknown, m/e 73
C15H32
unknown
See Table 28 (S9) for sampling protocol.
170
-------
Table 41. POLLUTANTS IDENTIFIED IN AMBIENT AIR IN
C. H. MILBY PARK, PASADENA, TXa
Chromatographic
Peak No.
1
2
3
4
5
6
7
8
9
9A
9B
10
11
12
13
13A
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Elution Temperature
32
33
34
38
39
41
43
47
48
49
49
51
52
53
55
55
56
57
57
58
60
62
64
66
68
70
72
73
76
77
78
79
(continued)
171
Compound
2-methylpropene
C,H isomer
chloroethane
furan
methylene chloride
acetone
C H. . isomer
6 14
isopropanol
chloroform
2-chloro-l , 3-butadiene
l-chlorobutene-3-yne «
C,H. . isomer
6 14
C,Hn _ isomer
6 12
methyl ethyl ketone
benzene
carbon tetrachloride
cyclohexane
C..H, , isomer
7 16
C..H, , isomer
7 16
C^H. . isomer
7 14
C-H, . isomer
7 14
C..H.. . isomer
7 14
ii-heptane
dimethylfuran isomer
C^H, , isomer
7 14
C0H1Q isomer
8 18
C..H, , isomer
8 16
CgHl6 isomer
toluene
. C0H10 isomer
8 18
C8Hlg isomer
C,-H, , isomer
-------
Table 41 (cont'd)
Chromatographic
Peak No.
30
31
32
33
34
35
36
37
37A
38
38A
39
39A
40
41
42
43
44
45
46
47
48
49
50
50A
51
52
53
54
55
56
57
Elution Temperature
82
84
89
90
92
95
98
99
99
102
102
105
105
106
108
110
112
114
115
116
118
120
122
124
124
126
127
128
130
131
132
134
(continued)
172
Compound
CRH1R isomer
n-octane
OgH2_ isomer
4-vinylcyclohexene
chlorobenzene
ethyl benzene
jj-xylene
m-xylene
phenyl acetylene
styrene
cyclooctatetraene
o-xylene
n-nonane
CqH, o isomer
cumene
CQHnQ isomer
9 18
C,nH-, isomer
10 16
ii-propylbenzene
benzaldehyde
C.-alkyl benzene
C_-alkyl benzene
C-..H-— isomer
10 20
C»-alkyl benzene
ii-decane
m-dichlorobenzene
C,-alkyl benzene
C.-H 0 isomer
10 18
£-dichlorobenzene
C...H-, isomer
C^-alkyl benzene
C^-alkyl benzene
C,-alkyl benzene
-------
Table 41 (cont'd)
Chromatographic
Peak No.
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
85
86
87
88
Elution Temperature
134
136
137
139
140
142
144
144
145
147
148
149
150
151
152
153
155
156
157
159
161
163
164
166
167
168
173
174
176
178
180
(continued)
173
Compound
C.-alkyl benzene
C f.H1 „ isomer
CIQH 2 isomer
C11H22 isoraer
n-undecane
C,_-alkyl benzene
C.-alkyl benzene
C12H26 lsomer
G- -alkyl benzene
j
C.QH 2 isomer
C,.-alkyl benzene
C12H26 is°mer
C HOQ isomer
13 28
C -alkyl benzene
C13H28 isomer
naphthalene
C qH?, isomer
n-dodecane
C ,H_fi isomer
C13H2g isomer
C13H26 isomer
C-.-H,,, isomer
13 25
C13H28 isomer
C _H s isomer
C13H26 isomer
C14H30 is°mer
n-tridecane
C14H28 lsomer
C15H32 isomer
C H 2 isomer
C15H32 isomer
-------
Table 41 (cont'd)
Chromatographic
Peak No.
89
90
91
92
93
94
95
Elution Temperature
182
183
185
194
198
199
210
Compound
C H isomer
Cn ,H00 isomer
14 /o
n-tetradecane
C15H32 is°mer
n-pentadecane
C1 ,-H.,,, isomer
n-hexadecane
Pollutants were resoled on a 42 m glass SCOT capillary coated with
OV-101 stationary phase programmed from 20-220°C @ 4°/min. Carrier
(He) gas was M..5 ml/min. Sampling protocol is given in Table 29 (SI)
174
-------
Table 42. POLLUTANTS IDENTIFIED IN AMBIENT AIR IN
C. H. MILBY PARK, PASADENA, TXa
Chromatographic
Peak No.
1
2
3
4
5
6
7
7A
8
9
10
11
12
13
14
15
15A
16
16A
17
18
19
20
20A
21
22
23
24
25
26
27
Elution Temperature
79
80
85
88
91
92
94
95
96
96
100
104
108
110
113
115
115
116
116
118
119
121
123
123
124
125
126
127
129
130
132
(continued)
175
Compound
methyl chloride
n-propane
C^Hg isomer
isopentane
trichlorof luoromethane
chlorof luoromethane »
acetaldehyde
furan
methylene chloride
carbon disulfide
acetone
isopropanol
3-methylpentane
2-methylfuran
chloroform
2-chloro-l , 3-butadiene
l-chlorobutene-3-yne
CyH^g isomer
CgH-^2 isomer
methyl ethyl ketone
1,1, 1- tr ichloroethane
CgH^Q isomer
benzene
carbon tetrachloride
cyclohexane
CyH^g isomer
C7H16 isomer
CyH^g isomer
C7H14 isomer
CgHig isomer
n-heptane
-------
Table 42 (cont'd)
Chroma tographic
Peak No.
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
58A
Elution Temperature
136
137
138
140
141
142
144
144
145
146
147
148
149
151
152
152
154
156
157
160
161
162
163
165
166
168
169
170
171
173
174
174
(continued)
176
Compound
dimethylfuran isomer
CgH,g isomer
CyHi^ isomer
C8H18 isomer
CgH^g isomer
CgH^g isomer
CgH-jc isomer
CgH^g isomer
CgH^g isomer
toluene
CgH-jg isomer
CgH^g isomer
CgHjg isomer
CgH-^g isomer
^6^12^ isomer
CgH^g isomer
ri-octane
tetrachloroethylene
CgH^g isomer
CgH20 isomer
CgH2o isomer
4-vinylcyclohexene
CgH^g isomer
chlorobenzene
ethylbenzene
£-xylene
m-xylene
phenyl acetylene
styrene
CgH2Q isomer
^-xylene
n-nonane
-------
Table 42 (cont'd)
Chromatographic
Peak No.
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
74A
75
76
77
78
79
80
81
82
83
84
85
86
87
88
Elution Temperature
(°C)
176
178
180
180
181
182
184
184
185
186
186
187
188
190
191
192
192
195
196
196
197
198
200
201
202
203
203
204
204
205
206
(continued)
177
Compound
CgH-jo isomer
l,4-dichloro-2-butene (tent.)
cumene
010^16 isomer
2-furaldehyde
oc-pinene
ClOK20 isomer
^10^22 isomer
n-propylbenzene
m-ethyltoluene
_£-ethyltoluene
benzaldehyde
C3~alkyl benzene
C3~alkyl benzene
^1f)^2f) isomer
n-decane
o-ethyltoluene
^10^20 isomer
m-dichlorobenzene
C^H-, isomer
C_-alkyl benzene
C,-alkyl benzene
C^H™, isomer
CnHin isomer
9 10
C_Hnr. isomer
9 10
o-dichlorobenzene
C,-alkyl benzene
C,,H2, isomer
C,-alkyl benzene
C^H-, isomer
C,-alkyl benzene
-------
Table 42 (cont'd)
Chromatographic
Peak No.
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
Elution Temperature
207
208
209
210
211
212
213
214
215
215
216
217
218
219
220
220
221
222
224
225
226
227
228
229
230
231
232
234
235
236
237
238
(continued)
178
Compound
C,-alkyl benzene
C12H24 isomer
C,-alkyl benzene
n-undecane
acetophenone
C --alkyl benzene
C --alkyl benzene
Cr-alkyl benzene
C, -alkyl benzene
C,-alkyl benzene
C,-alkyl benzene
C--alkyl benzene
C -alkyl benzene
C, -H- . isomer
10 11
C --alkyl benzene
C5~alkyl benzene
CT-.HTT isomer
10 11
C^-alkyl benzene
C --alkyl benzene
CnoH0. isomer
12 24
n-dodecane
1,3, 5-trichlorobenzene
naphthalene
C.-H-g isomer
C H28 isomer
C, -alkyl benzene
C, _H_, isomer
C.. ^H« , isomer
Cg-alkyl benzene
p rt j
^* -i o I/* isomer
lj 26
C,,H isomer
°14H30 lsomer
-------
Table 42 (cont'd)
Chromatographic
Peak No.
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
Elution Temperature
(°C)
239
240
240
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
isothermal
Compound
C. 0H~., isomer
13 26
n-tridecane
CT.H^O isomer
14 28
CT.HT-. isomer
14 30
3-methylnaphthalene
C, ,H0. isomer
14 30
Gn ,H-0 isomer
14 28
a-methylnaphthalene
C, ,ELrt isomer
14 30
Cn ,HnA isomer
14 30
C, ,H-^ isomer
14 30
C- _H»_ isomer
15 32
Cn ,Hno isomer
14 28
n-tetradecane
biphenyl
C1CH00 isomer
15 32
phenyl ether
C, _H „ isomer
15 32
C- rH__ isomer
15 30
C,,-H0T isomer
15 32
C, ,!!„„ isomer
14 28
C,._H_0 isomer
15 32
C,cH-rt isomer
15 30
n-pentadecane
C1CH__. isomer
15 30
n-hexadecane
3A 400 ft stainless steel SCOT capillary coated with OV-101 was used for
resolving pollutants. Capillary was programmed from 20-240°C @ 4°C/min
Carrier (He) was -3-0 ml/min. Sampling protocol is given in Table 29
(SI, duplicate sample).
179
-------
Table 43. POLLUTANTS IDENTIFIED IN AMBIENT AIR
FROM PASADENA, TXa
Chroma tographic
Peak No.
1
1A
2
3
4
5
6
7
8
9
10
11
12
13
14
15
15A
16
17
17A
18
19
20
21
22
23
24
25
26
27
28
Elution Temperature
(°C)
72
72
75
77
78
86
88
90
92
94
96
98
100
103
105
107
107
108
109
110
113
114
118
120
121
122
123
124
126
127
128
(continued)
180
Compound
propylene
propane
chlorome thane
butene isomer
n-butane
C^H - isomer :
chlorofluorome thane
C,.H „ isomer
methylene chloride '•
carbon disulfide
propanal (tent.)
acetone
C,H isomer
6 14
3-methyl pentane
C6H12 isomer
C,H isomer
6 14
2-methylfuran
C,H isomer
C5H10
methyl isopropyl ketone (tent.)
methylcyclopentane
C_H isomer
/ ID
l»2-dichloroethane
benzene
cyclohexane
C,H , isomer
,C_H isonier
/ lo
CyH isomer
dimethylcyclopentane isomer
dimethylcyclopentane isomer
trichloroethylene
-------
Table 43 (cont'd)
Chromatographic
Peak No.
29
29A
30
30A
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
45A
46
- 47
48
49
50
51
51A
52
53
54
55
Elution Temperature
129
130
132
132
133
136
137
138
140
142
143
143
144
146
148
150
150
151
153
153
154
156
158
159
160
161
161
163
164
164
165
(continued)
181
Compound
n_-hep tane
C-,H, , isomer
7 14
dimethylfuran
m/e 94
dimethylfuran isomer
dime thy Ipentene isomer
C^H., isomer
C0H.. , isomer
o lo
methylmethacrylate (tent.)
C<,H.. , isomer
o lo
C0Hn , isomer
o lo
CRH-a isomer
toluene
CRH „ isomer
C0H... isomer
a ID
C0H, , ispmer
o ID
C9H20 isoiner
n-octane
C0Hn£ isomer
o lo
dibromodichlorome thane
tetrachloroethylene
C0H, , isomer
o ID
C8H16 isomer
C9H20 isomer
C9H20 isomer
C0H. , isomer
o lo
CgH.g isomer
chlorobenzene
CQH9n isomer
C_H?n isomer
ethylbenzene
-------
Table 43 (cont'd)
Chromatographic
Peak No.
56
57
58
58A
59
60
61
62
63
64
65
66
67
68
69
70
70A
71
72
73
74
74A
75
75A
76
77
78
79
80
80A
81
Elution Temperature
166
167
168
170
170
171
171
172
174
176
177
178
179
180
182
182
183
183
184
184
185
185
186
186
188
189
190
191
192
192
193
(continued)
182
Compound
;p_-xylene
m-xylene
phenylacetylene
C_H _ isomer
9 18
bromoform
styrene
o-xylene
n-nonane
C.H.. Q isomer
9 18
CJtLQ isomer
9 18
CinH00 isomer
10 22
isopropylbenzene
C,_H,,- isomer
10 20
C-_H00 isomer
10 22
n_-propylcyclohexane
CnnH, ., isomer
10 16
cyclohexanone (tent.)
C^^H.,-. isomer
10 20
CinHor, isomer
10 22
ri-propylbenzene
m-ethyl toluene
Ej-ethyl toluene
£-ethyltoluene
C,,H0/ isomer
11 24
C10H20 lsomer
1,3,5-trimethylbenzene
C10H20 isomer
C H isomer
9 10
1,2, 4- trimethylbenzene
n-decane
CQH isomer
9 10
-------
Table 43 (cont'd)
Chromatographic
Peak No.
81A
82
83
83A
83B
84
85
86
87
88
89
89A
90
91
92
93
94
95
95A
96
97
98
98A
99
100
100A
101
102
103
104
105
Elution Temperature
193
195
195
195
195
196
197
198
199
200
200
200
202
202
203
203
204
205
205
207
207
208
208
209
211
211
212
214
214
214
215
(continued)
183
Compound
benzaldehyde
isobutylbenzene
sec-butylbenzene
m-d ichlo robenzene
C-...H,., isomer
11 24
C, .. Hn . isomer
11 24
1,2,3 -trimethy Ibenzene
C..-.H.,, iscmer
1U lo
C11H24 isomer
n-butylcyclohexane
CqH1 _ isomer
o-dichlorobenzene
C,-alkyl benzene
C,-alkyl benzene
C,-alkyl benzene
C,-alkyl benzene
C,-alkyl benzene
C, -alkyl benzene
C10H18 ls°mer
C, -alkyl benzene
C,-alkyl benzene
C. -alkyl benzene
C10H12 isomer
n-undecane
C,. -alkyl benzene
C11H22 isomer
C,-alkyl benzene
C12H24 lsomer
C,-alkyl benzene
C0HinN isomer
o 11
m/e 152
-------
Table 43 (cont'd)
Chromatographic
Peak No.
106
107
108
109
110
111
112
113
114
114A
115
116
116A
117
118
119
120
120A
121
121A
122
123
124
125
126
127
128
129
130
131
132
Elution Temperature
216
217
218
218
219
220
220
221
222
222
223
224
224
226
226
227
228
228
229
229
230
230
231
232
233
234
234
235
236
237
238
(continued)
184
Compound
C10H0, isomer
1- /o
C,.-alkyl benzene
C11H22 isomer
C,--alkyl benzene
C^-alkyl benzene
C1«H_f. isomer
C,-alkyl benzene
C--alkyl benzene :
C.-alkyl benzene
C,,H0/ isomer
11 24
Cj.-alkyl benzene
C10H_. isomer
12 24
C,-alkyl benzene
n-dodecane
C^-alkyl benzene
naphthalene
C...,H, . isomer
11 14
C,-alkyl benzene
C,.-alkyl benzene
C,-alkyl benzene
C,-alkyl benzene
C. ,HOC isomer
13 26
C--H,., isomer
13 26
C,-alkyl benzene
C._H0, isomer
13 26
C.nH0/ isomer
11 24
Cg-alkyl benzene
C._Hot isomer
J.J /O
C,.-alkyl benzene
C14H30 isomer
C13^26 *somer
-------
Table 43 (cont'd)
Chroma tograp hie
Peak No.
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
Elution Temperature
239
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
Compound
C,-alkyl benzene
GI H , isomer
n-tridecane
C--alkyl benzene
C14H28 isomer
C, ,H_0 isomer
14 30
C-.H-o isomer
14 28
C-.H,,.- isomer
14 30
2-methylnaphthalene
C14H30 isomer
C, ,H__ isomer
14 30
C, ,H,,0 isomer
14 28
1-methylnaphthalene
C14H28 isomer
Cn_H_, isomer
lj ZD
C, ,H__ isomer
14 30
C14H30 isomer
C15H32 isomer
C14H30 iSOiner
n-tetradecane
m/e 154
C15H32 isomer
C14H28 isomer
C15H32 isomer
C1 cHon isomer
C15H30 isomer
C15H32 isomer
C15H32 isomer
C15H32 isomer
C15H32 isomer
See Table 29 (S2) for sampling protocol.
185
-------
Table 44. POLLUTANTS IDENTIFIED IN AMBIENT AIR FROM PASADENA, TX
Chroma tographic
Peak No.
1
2
2A
3
4
5
6
7
7A
8
9
10
11
12
13
14
14A
15
16
17
18
19
20
21
22
23
24
25
26
27
Elution Temperature
(°C)
74
78
79
81
82
91
95
97
98
102
105
110
113
116
119
120
120
124
126
126
127
128
130
132
133
135
136
138
139
140
(continued)
186
Compound
propane
chlorome thane
isobutane
butene isomer
n-butane
chloroethane
C5H 2 isomer
chlorofluoromethane (tent.)
n-pentane
propanal (tent.)
acetone
C,H., . isomer
6 14
n_-hexane
chloroform
methylcyclopentane
C7H16
1, 2-dichloroethane
benzene
carbon tetrachloride
cyclohexane
C.,H , isomer
/ ID
C.,H r isomer
/ lo
C-H. , isomer
/ J.O
dimethylcyclopentane isomer
dimethylcyclopentane isomer
n-heptane
dimethylfuran isomer
dimethylfuran isomer
CgH isomer
dimethylpentene isomer
-------
Table 44 (cont'd)
Chroiaatographic
Peak No.
28
29
30
31
32
33
34
35
36
37
38
39
39A
40
41
42
43
44
45
46
47
48
49
50
51
52
52A
53
54
55
55A
Elution Temperature
141
142
144
146
147
148
150
152
152
153
154
155
157
158
159
160
162
163
163
164
165
166
167
168
169
170
171
173
174
175
176
(continued)
187
Compound
CoH-i o isomer
8 18
C-H.., isomer
8 16
C0H , isomer
8 16
C0H, 0 isomer
8 18
CgH isomer
toluene
CQH 0 isomer
8 18
C0H- f isomer
o ID
C6H120 (aldehyde ?)
C0H. 0 isomer
o lo
CQH _ isomer
o lo
n-octane
dibromodichloromethane (tent.)
tetrachloroethylene
CnHn .. isomer
o ID
C9H20 isomer
C9H20 isomer
CQHn , Isomer
o ID
C0H. , isomer
o ID
C9H20 lsomer
chlorobenzene
CpH2Q isomer
ethylbenzene
p_-xylene
m-xylene
phenylacetylene
bromoform 1 S
styrene
o-xylene
n-nonane
C9Hlg isomer
-------
Table 44 (cont'd)
Chromatographic
Peak No.
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
70A
71
71A
72
73
74
75
76
77
78
78A
79
80
81
82
83
Elution Temperature
179
180
180
181
182
183
184
185
186
186
187
189
190
191
192
192
193
193
194
195
196
196
197
198
199
199
200
200
201
201
202
1
(continued)
188
Compound
C10H22 isomer
C,~H,,,, isomer
10 22
isopropylbenzene
CgH18 isomer
C10H16 is°raer
C10H20 1S°mer
C10H22 isomer
n-propylbenzene
m-e thy 1 toluene
p_-ethyl toluene
£-ethyltoluene
C11H24 isomer
1,3, 5-trimethylbenzene
C10H20 isOIner
C10H2Q isomer
1,2,4-trimethylbenzene
n-decane
benzaldehyde
C9H10 isomer
C10H20 is°mer
C,-alkyl benzene
m-dichlorobenzene
C -jH^i isolner
C,-alkyl benzene
1,2,3-trimethylbenzene
C H isomer
C10H16 is°mer
C10H16 is°mer
C10H20 is°mer
CgH isomer
-------
Table 44 (cont'd)
Chroma tographic
Peak No.
83A
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
Elution Temperature
202
203
203
204
205
206
207
208
209
209
210
211
213
214
214
215
216
216
217
218
218
219
220
221
221
222
223
224
225
226
227
(continued)
189
Compound
£-dichlorobenzene
C,-alkyl benzene
C, -alkyl benzene
C,-alkyl benzene
Cir.H9_ isomer
C,-alkyl benzene
C,-alkyl benzene
C,-alkyl benzene
C,-alkyl benzene
n-undecane
Cc-alkyl benzene
.>
C11H22 isomer
C,--alkyl benzene
C11H22 isonier
C,-alkyl benzene
C , -alkyl benzene
4
m/e 152
m/e 73 (Bkd ?)
C,.-alkyl benzene
C11H22 isomer
€5- alkyl benzene
C5~alkyl benzene
C12H26 lsomer
C,. -alkyl benzene
C.-alkyl benzene
Cc-alkyl benzene
C, -alkyl benzene
C12H24 isomer
n-dodecane
C11H14 isomer
naphthalene
-------
Table 44 (cont'd)
Chroma tographic
Peak No.
114
115
116
117
117A
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
Elution Temperature
(°C)
228
229
230
230
230
231
232
232
233
234
234
235
236
237
238
239
239
240
240
240
240
240
240
240
240
240
240
240
240
240
240
(continued)
190
Compound
C.-alkyl benzene
C,-alkyl benzene
C.JH,,,, isomer
12 22
Cp-alkyl benzene
C,-alkyl benzene
C,--alkyl benzene
CnoHn., isomer
13 26
C,0Hnx. isomer
13 26
C,-alkyl benzene
C-..H,.. isomer
12 24
C--alkyl benzene
C, ~H_0 isomer
13 28
C,-alkyl benzene
C^.H..^ isomer
14 30
C,-alkyl benzene
C, ,H_,. isomer
14 30
C,,H00 isomer
14 28
n-tridecane
C-,oH fi isomer
^13^26 ^somer
C.. ,H isomer
C14H30 isomer
C14H30 isomer
2-methylnaphthalene
C14H30 isomer
1-methylnaphthalene
C14H30 ±soiner
C14H30 isomer
C14H30 isomer
C1 J.H,, isomer
JL«/ J £
C,cH»2 isomer
-------
Table 44 (cont'd)
Chroma tographic
Peak No.
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
Elution Temperature
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
Compound
C- ,-H_9 isomer
.L^ j £
C14H30 isomer
C14H28 isomer
iv-tetradecane
C14H28 isomer
biphenyl
C14H28 is°mer
Cni.H00 isomer
15 32
C, .-H_« isomer
15 32
C15H,Q isomer
C14H28 isomer
C15H32 isomer
C16H34 is°mer
C15H32 is°mer
C16H34 ls°mer
C15H30 is°mer
C15H32 isomer
C16H34 isomer
n-pentadecane
C-.H isomer
C15H30 isomer
C16H34 ±SOmer
aSee Table 29 (S3) for sampling protocol.
191
-------
Table 45. POLLUTANTS IDENTIFIED IN NIGHT AMBIENT AIR IN PASADENA, TX
Chroma tographic
Peak No . a
2
3
3A
4
4A
4B
5
5A
5B
5C
5D
7
9
10
10A
10B
11
11A
11B
11C
11D
12
12A
12B
12C
13
13A
13B
14
Elution Temperature
73
74
81
84
85
94
95
97
98
99
100
101
101
105-110
113
114
114
115
116
117
118
119
120
122
123
125
127
129
129
130
130
(continued)
192
Compound
co2
ethylene oxide \J
propane
1-butene
n-butane
isopentane
acetaldehyde
furan + C,.H n isomer
n-pentane
propionaldehyde
C,-H isomer
methylene chloride
CS2
acetone
2-methylpentane
3-methylpentane
sec-butanol
1-hexene
n-hexane
C6H10 + C6H12 is°mer
chloroform
C,H.. 2 isomer
C,Hn . isomer
6 14
methylcyclopentane
allyl acetate
C,H , isomer
C,H isomer
benzene
cci4
cyclohexane
2-methylhexane
-------
Table 45 (cont'd)
Chromatographic
Peak No.
15
16
17
17A
17B
17C
17D
18
ISA
18B
18C
18D
19
20
20A
21
22
22A
23
24
25
26
27
27A
27B
28
29
29A
30
30A
Elution Temperature
(°C)
131
132
133
134
134
135
135
137
138
139
140
141
142
144
144
146
148
148
149-150
150-151
152
154
156-158
158
158
159
162
163
164
164
(continued)
193
Compound
2 , 3-dlmethylpentane
3 -me thy Ihexane
C_H1 - isomer
CyH . isomer
C.jH isomer
/ lo
CyH.. , isomer
l-trans-2-dimethylcyclo-
pentane
n-heptane
C H isomer
C7H , isomer
C7H.. „ isomer
trimethylpentane isomer
4,4-dimethyl-2-pentene
2 , 4-dimethy Ihexane
cycloheptane
n-propylcyclopentane
2-methyl-trans-3-heptene
2 , 3-d imethy Ihexane
toluene
2-methylheptane
3-methylheptane
trimethyl-2-pentene isomer
rv-oc tane
C0H-, isomer
o ID
hexamethylcyclotrisiloxane
(BKG)
tetrachloroethylene
methyl isobutyl ketone
3-methyl-3-ethyl-pentane
2, 6-d imethy Iheptane
C9H20 isomer
-------
Table 45 (cont'd)
Chromatographic
Peak No.
31
32A
32
33
34
35
36
37
38
39
39A
40
41
41A
4 IB
42
43
44
45
46
47
48
49
50
51
51A
52
53
54
Elution Temperature
165
166
167
169
170-171
171-172
175
175-176
176-178
180
181
182
183
183
184
185
186
187
188
188
189
190
192
193-195
195
196
197
198
198
(continued)
194
Compound
ethylcyclohexane
7-methyl-octene-l
chlorobenzene
ethylbenzene
_p_-xylene
phenylacetylene
styrene
^-xylene
ri-nonane
methylethylcyclohexane isomer
C, r,H__ isomer
10 22
isopropylbenzene
3-me thy Inonane
C10H20 isomer
propylcyc lohexane
Cn nH , isomer
10 16
CinH0 isomer
10 20
n_-propylbenzene
£-ethyltoluene
C -alkyl benzene + GinH0_
isomer 10 2i
C_-alkyl benzene
CL-alky! benzene + C,-H
isomer 10 22
l-methyl-4-isopropylcyclo-
hexane
ri-decane + ^-ethyltoluene
benzaldehyde
C^-alkyl benzene isomer
dichlorobenzene isomer i
methyldecane isomer and
3-methylstyrene
£-cymene
-------
Table 45 (cont'd)
Chromatographic
Peak No-
55
56
57
58
58A
58B-
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
79A
79B
Elution Temperature
(°C)
199
200
201
202
203
203
204
205
205
206
207
209
210
211
212
213
214
215
216
216
217
218
219
220
220.5
221
222
223
223
(continued)
195
Compound
C,nH_. isomer
11 24
1,2, 3-trlmethy Ibenzene
C..H~. isomer
11 24
butylcyclohexane
o-me thy 1 s ty r ene
1 , 2-diethy Ibenzene
n-propyltoluene
p_-diethy Ibenzene
methyldecane isomer
C.,,H , isomer
11 24
o-propyltoluene
dimethylethy Ibenzene isomer
C10H12 + C11H22 is°mer
n-undecane
C5~alkyl benzene + C H^
isomer
acetophenone
C,_H,.^ isomer
12 26
C, „!!„,. isomer
12 26
pentamethylheptane isomer
C,-alkyl benzene
C,«H^. isomer + silane com-
12 24
pound
C,--alkyl benzene
Cj.-alkyl cyclohexane
C, 0H~, isomer
12 26
Cj--alkyl benzene
CroH isomer
12 26
(V-alkyl benzene + methylindan
dimethylundecane isomer
1,2,3, 4-tetrahydronaphthalene
+ C,--alkyl benzene
-------
Table 45 (cont'd)
Chromatographic
Peak No.
80
81
82
82A
82B
83
85
85A
86
90
92
93
96
97
99
Elution Temperature
(°C)
224
225
226
227
227.5
228-229
232
233
235
240
isothermal
isothermal
isothermal
isothermal
isothermal
Compound
C..,H0, isomer
lj Zo
C12H24 isoraer
n-dodecane
dimethylindan
C_-alkyl benzene
naphthalene
C,-alkyl benzene
silane compound (BKG)
C fi-cyc lohexane
n-tridecane
3-methylnapthalene
a-methylnaphthalene
1-tetradecene
n-tetradecane
n-pentadecane
A 400 ft stainless steel SCOT capillary coated with OV-101 stationary
phase was used for resolving pollutants. Capillary was programmed from
'20-240°C @ 4°C/min. Carrier (He) gas was -3.0 ml/min. See Table 29
(S5, duplicate) for sampling protocol.
196
-------
Table 46. POLLUTANTS IDENTIFIED IN DAY AMBIENT AIR IN PASADENA, TXS
Chroma tographic
Peak No. a
1
2
3
4
5
6
7
8
9
10
10A
11
12
12A
13
14
15
16
16A
17
18
19
20
21
22
23
24
25
26
27
28
Elution Temperature
34
37
39
41
43
46
48
50
51
54
56
57
58
58
59
60
62
64
65
66
70
72
77
78
80
82
84
86
89
90
91
(continued)
197
Compound
fl-propane
Eicetaldehyde
n-pentane
methylene chloride
acetone
3-methylpentane
C,H- . isomer
6 14
n-hexane
chloroform
C-,H, ,. isomer
/ ID
1,1,1-trichloroethane
2-butanone
benzene
carbon tetrachloride
cyclohexane
C-.Hn , isomer
/ lo
C_,H, ., isomer
7 ID
C-H . isomer
trichloroethylene
n-heptane
C7H14 isomer
C7H , isomer
toluene
2-methylheptane
3-methy Ihep tane
C0H, , isomer
o lo
n-octane
tetrachloroethylene
CqH2f. isomer
CqHp,. isomer
chlorobenzene
-------
Table 46 (cont'd)
Chroma tographic
Peak No.
29
30
31
32
33
34
35
36
37
38
39
40
40A
41
42
43
43A
44
45
46
47
48
49
50
51
52
53
54
55
56
57
Elution Temperature
94
96
98
100
100
103
106
108
109
112
113
114
115
116
119
121
122
124
125
126
127
128
130
131
132
133
134
136
137
139
140
(continued)
198
Compound
ethyl benzene
£-xylene
C_H«rt isomer
9 20
styrene
^-xylene
n-nonane
cumene
CQH „ isomer
a-pinene
n-propylbenzene
jn-ethyltoluene
1,3, 5-tritaethylbenzene
benzaldehyde
o-ethyltoluene
1,2, 4- trimethylbenzene
ii-decane
m-dichlorobenzene
1,2, 3-trimethylbenzene
C H isomer
11 24
CgH10 isomer
C10H20 lsomer
C^-alkyl benzene
C,-alkyl benzene
acetophenone
C^-alkyl benzene
C^-alkyl benzene
C,QH-2 isomer
C,-alkyl benzene
ii-undecane
C^-alkyl benzene
C^-alkyl benzene
-------
Table 46 (cont'd)
Chromatographic
Peak No.
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
85
86
87
88
Elution Temperature
(°C)
141
142
143
143
144
145
146
147
148
150
151
152
152
155
156
157
159
160
162
163
164
166
167
169
170
171
172
174
175
176
177
(continued)
199
Compound
C,-alkyl benzene
C--alkyl benzene
C,--alkyl benzene
C.. H..- isomer
C,--alkyl benzene
C1QH12 isomer
C,.-alkyl benzene
C,.-alkyl benzene
C,_-alkyl benzene
naphthalene
C....H, , isomer
C,--alkyl benzene
n-dodecane
C13H28 isomer
C-.-alkyl benzene
b
C,-alkyl benzene
C,-alkyl benzene
C13H28 isomer
C11H-, isomer
C,-alkyl benzene
C13H28 isomer
g-methylnaphthalene
n-tridecane
C13H26 iscmer
a-methylnaphthalene
C14H28 is°mer
0.,-alkyl benzene
C13H26 isomer
C14H30 iS°mer
C14H30 iS°mer
C14H28 1S°mer
-------
Table 46 (cont'd)
Chromatographic Elution Temperature
Peak No. (°C) Compound
89 178 C15H32 isomer
90 179 Cn.H_Q isomer
14 28
91 180 n.-tetradecane
aA 42 m glass SCOT capillary coated with OV-101 was used. Capillary was
programmed from 20-220°C @ 4°C/min. Carrier (He) was -1.5 ml/min. See
Table 29 (S5) for sampling protocol.
200
-------
Table 47. POLLUTANTS IDENTIFIED IN NIGHT AMBIENT AIR IN TEXAS CITY, TX£
Chromatographic
Peak No.
1
2
3
4
5
5A
5B
5C
6
' 7
10
12
13
14
15
ISA
15B
16
17
18
19
21
21A
22
23
24
25
26
27
28
Elution Temperature
(°C)
71
73
79
87
92
93
94
95
96
97-105
109
115
116
117
121
122
122
123
124
125
126
129
130
132
136-137
138
139
141
143
144
(continued)
201
Compound
C02
chlorodif luormethane
C^Hg isomer
isobutane
1 , 4-pentadiene
n-pentane
acetaldehyde
methylene chloride
propanal and CS?
acetone
chloroform
n-hexane
methyl cyclopentane
silane compound
C,Hn , isomer
7 lo
benzene
cyclohexane and CC14 and
methylcyclopropyl ketone
cyclohexene
2 , 4-dimethylpentane
2 , 3-dimethy Ipentane
3-methylhexane
1 , cis-3~dimethylcyclopentane
1 , trans-2-dimethylcyclopentane
n-heptane
dimethyl-2-pentene isomer
CgH]^ isomer
C8H18 *somer
^7H14 isomer
1 , trans-2 , cis-3-trimethy 1-
cyclopentane
2 , 3-dimethy Ihexane
-------
Table 47 (cont'd)
Chroma tographic
Peak No.
29
30
31
32
33
34
34A
35
38
39
40
41
42
42A
43
44
46
47
47A
48
49
50
51
52
53
54
55
56
57
58
Elution Temperature
i
144-146
147
148
150
152
153
154
155-156
161
162
165-166
167-168
169
170
172-173
173-175
180
181
181
182
184-185
185
186
187
188-189
190
190-195
192-193
194
195
(continued)
202
Compound
toluene
CgHig isomer
3-methylheptane
CgHi g isomer
CgHj6 isoiner
3-methyl-3-ethylpentane
n-octane
hexamethylcyclotrisiloxane
CoHi r isomer
8 16
CgH-^g isomer
ethyl benzene
j)-xylene
CJH20 isomer
phenyl acetylene
styrene and 2-methyl-l-octene
jo-xylene and n-nonane
isopropylbenzene
'"'9^20 i-somer
propylcyclohexane
C10H16 isomer
n-propylbenzene
m-ethyltoluene
_p_-ethyltoluene
3-methyl-nonane
1,3,5-trimethylbenzene and
^10^22 isomer
o-ethyltoluene
benzaldehyde
1,2,4-trimethylbenzene and
ri-decane
phenol \»-
isobutylbenzene
-------
Table 47 (cont'd)
Chromatographic
Peak No.
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
83A
84
85
86
87
88
Elution Temperature
(°C)
196
197
198
199
200
201
202
202
203
204
205
206
207
207
208
209
210
211
212-213
213
214
215
216
217
218
218
219
220
220
221
222
(continued)
203
Compound
dichlorobenzene isomer
t-butylbenzene
1,2, 3-tritnethylbenzene
^11^24 isome^
^10^20 isomer
6-methylstyrene
C-i-|H22 isomer
sec-butylbenzene
o-cymene
^11^24 isomer
C-, ,H24 isomer
C4~alkyl benzene isomer
m-cymene
_p_-cymene
C4~alkyl benzene isomer
n-undecane
acetophenone
C5~alkyl benzene isomer
C4~alkyl benzene isomer
Ci2^26 isomer
C^2^?6 isomer
C4~alkyl benzene isomer
C4-alkyl benzene isomer
Cc-alkyl benzene isomer
C11H22 isomer
C12H26 isomer
methylindan isomer
Cc-alkyl benzene isomer
methylundecane isomer
dimethylstyrene isomer
C12H26 isomer
-------
Table 47 (cont'd)
Chromatographic
Peak No.
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
117
119
120
121
Elution Temperature
224
224
225-226
227
228
228
229
231
234
235
236
237
238
239
241
242
244
246
249
251
251
252
253
255
256
257
261
264
266
267
(continued)
204
Compound
Cc-alkyl benzene isomer
C12H24 isomer
n-dodecane
dimethylindan isomer
naphthalene
Ci oH2g isomer
dimethylisopropylbenzene
Cg-alkyl benzene isomer
C5Hi --cyclohexane isomer
1,2, 4-tr ichlorobenzene
C13H28 isomer
silane compound
C13H28 isomer
Cg-alkyl benzene isomer and
methyl-1 , 2,3, 4-tetrahydronap-
thalene isomer
n-tridecane
^13^26 ant^ C5~alkyl benzene
isomer
silane compound
methyl naphthalene (3)
methyl naphthalene (a)
Cy-alkyl cyclohexane
C14H30 isomer
^14^30 isomer
C15H32 isomer
1-tetradecene
n-tetradecane
biphenyl
ethyl naphthalene isomer
dimethylnaphthalene isomer
dimethylnaphthalene isomer
C14H28 isomer
-------
Table 47 (cont'd)
Chromatographic Elution Temperature
Peak No. (°C) Compound
122 268 Cg-alkyl cyclohexane isomer
124 273 n-pentadecane
132 291 n-hexadecane
aA 400 ft stainless steel SCOT coated with OV-101 was used for resolving
the pollutants. Capillary was programmed from 20-240°C @ 4°C/min. Carrier
(He) gas was -3.0 ml/min. See Table 29 (S6) for sampling protocol.
205
-------
Table 48. POLLUTANTS IDENTIFIED OR DETECTED IN AMBIENT AIR
FROM TEXAS CITY, TX3
Chromatographic
Peak No.
1
1A
2
2A
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
17A
17B
18
19
19A
20.20A
21,21A
22
23
24,25
Elution Temperature
78
79
82
83
84
85
88
93
96
104
108
111
112
113
114
116
118
119
120
121
122
124
126
126
130,131
132
134
141
142
(continued)
206
Compound
carbon dioxide
sulfur dioxide
propane
1-butene
n-butane
2-butene
isopentane
n-pentane
acetone
methylene chloride
C..H, . isomer
6 14
C -H, „ isomer
D 1^
3-methylpentane
3-methylfuran
C,Hn , isomer
6 14
chloroform
C,H,2 isomer
C_H.. , isomer
7 ID
methylcyclopentane
ethyl acetate
n-butanol
1,1, 1-trichloroethane
C H isomer
/ lo
carbon tetrachloride
C?H16 isomer
C_H. , isomer
ji-heptane
C_H.| , isomer
C8H18 isomer
-------
Table 48 (cont'd)
Chroma to graphic
Peak No.
26
27,28
29
30
31-33
34
35
36
37
38
39
40
41
42
43,44
45
46
47
48
49
50
51
52,53
54
55
56
57
58,59
60
61
Elution Temperature
143
145,146
149
151
153,154
155
157
158
159
159
161
162
164
165
166,167
168
169
170
171
172
173
173
174,175
176
176
177
179
180,182
182
183
(continued)
207
Compound
C-jH.., isomer
C0H- , isomer
o ID
toluene
G,,HI „ isomer
CC.HT , isomers
o ID
C0H.. 0 isomer
O lo
n-octane
C0H., isomer
o lo
unknown
tetrachloroethylene
CRH16 isomer
CgH2Q isomer
CQH1R isomer
CQH.., isomer
o ID
CQH1 „ isomer
chlorobenzene
CQH1 Q isomer
C9H20 isomer
ethylbenzene
p-xylene
m-xylene
phenyl acetylene
CQH- R isomer
styrene
o-xylene
n-nonane
CQH,S isomer
ClnH_9 isomers
isopropylbenzene
C,nH99 isomer
-------
Table 48 (cont'd)
Chroma tographic
Peak No.
62
63
64
65
66
67
68
69
70
71
72
72A
73
74
74A
75
76
77
78
79
80
81,82,83
84
85-89
90
90A
91
92,93
93A
94-96
Elution Temperature
184
185
186
187
189
190
191
192
193
194
195
195
197
198
198
199
199
201
202
203
203
204,205,206
207
208,209,210,211
212
212
213
214,215
216
217,218
(continued)
208
Compound
CqH1R isomer
3-pinene
Cn_Hon isomer
10 20
n-propylbenzene
m-ethyltoluene
_p_-ethyltoluene
Cir.H00 isomer
10 22
benzaldehyde
1,3, 5-trimethylbenzene
C1rtHor. isomer
10 20
1,2, 4-trimethylbenzene
n-decane
C.,H~_ isomer
11 22
CnnH0. isomer
11 24
C,-alkyl benzene
m-dichlorobenzene
C,-alkyl benzene
1,2, 3-tr imethylbenzene
Cir.Hor. isomer
10 20
C,..H0_ isomer
11 22
methyl styrene
C,-alkyl benzenes
€"11^24 isomer
C,-alkyl benzenes
C11H_. isomer
11 24
Clf)H1? isomer
C^-alkyl benzene
C,-alkyl benzene
C^-alkyl benzene
C^-alkyl benzene
-------
Table 48 (cont'd)
Chromatographic
Peak No.
97-99
100
101-106
io?
108
109
109A
110
111
112,113
114
115
115A
116
117
118-120
121-123
124
Elution Temperature
218,219
221
222,223,224,225,226
227
228
230
230
230
230
230
230
230
230
230
230
230
230
230
Compound
C,.-alkyl benzenes
CinH10 isomer
10 12
Cc-alkyl benzenes
C,-alkyl benzene
n-dodecane
Cc~alkyl benzene
tetrahydronaphthalene
C,--alkyl benzene
naphthalene
C--alkyl benzenes
Cg-alkyl benzene
C,_-alkyl benzene
Cg-alkyl benzene
Cc-alkyl benzene
o
C_-alkyl benzene
5
C,-alkyl benzenes
C,,H28 isomers
C1.H-n isomer
14 30
Resolution was on a 400 ft OV-101 SCOT programmed from 20-230°C at
4°C/min, see Table 29 (S7) for sampling protocol.
209
-------
Table 49. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR IN PASADENA, TX*
Chroraatographic
Peak No.
1
2
2A
2B
2C
3
3A
3B
4
5
6
7
7A
7B
8
8A
9
10
10A
10B
11
12
13
14
14A
14B
14C
15
7.5A
Elution Temperature
86
87-92
92
93-100
98
101
101
102
103
106
109
111
112
112
113
113
114
11.6
117
117
118
120
121
123
124
125
125
128
129
130
(continued)
210
Compound
acetaldehyde
silane compound (BKG)
propanal
acetone
3-methylpentane
2-methylfuran
n-hexane
methylpentane isomer
3-methylfuran and CHC1-
j
methylcyclopentane and
C-H, . isomer
6 14
C-.H,, isomer
7 16
1,1,1-trichloroethane
methyl ethyl ketone
C^H, _ isomer
7 12
benzene
cci4
cyclohexane
C-,Hn , isomer
7 16
2, 3-dimethylpentane
C-,Hn . isomer
7 14
C H . isomer
7 14
dimethylcyclopentane
trichloroethylene
n-heptane
2 , 5- dimethylf uran
2,4-dimethylfuran
GO^I t isomer
8 16
C.,H isomer
/ 14
CcHic isomer
o lo
^0^10 isomer
o lo
-------
Table 49 (cont'd)
Chromatographic
Peak No.
16
16A
17
18
19
20
21
22
23
24
24A
25
26
26A
26B
27
27A
27B
28
29
30
31
32
33
34
35
36
37
38
Elution Temperature
(°C)
130
131
133
134
136
136-137
137-138
140
142
143
144
144-146
146-148
149
150
152
153
155
156-157
157-159
159
160
162
162-163
163-165
168
169
170
171
(continued)
211
Compound
2 , 4-dimelhylhcxane
1-me thy Icyc lohexane
CgH- , isoiner
1,2,3-triinethylcyclohexane
2-methyl-3-ethylpentane
toluene
2-methylheptane
3-methylheptane
dimethylcyclohexane isomer
CglLg isomer
dimethyl formamide and
C0H.., isomer
o ID
n-oc.tane
tetrachloroethylene and
hexainethyl cyclotrisiloxane
(BKG)
2-hexanone
4-vinylcyclohexane
C0H, , isomer
o ID
CgH2Q isomer
chlorobenzene
ethylbenzene
p-xylene
CgH2Q isomer
phenyl acetylene
CgH18 isomer
o-xylene
n-nonane
C9H18 isomer
isopropylbenzp.ne
2 , 3-dimethyloctane
n-propylcyclohexane a.nd_
C- ,,Hort isomor
10 20
-------
Table 49 (cont'd)
Chromatographic
Peak No.
38A
39
40
41
42
43
44
44A
45
46
47
48
49
50
51
52
53
54
55
56
56A
57
58
59
60
61
62
62A
Elution Temperature
172
173
174
175
176
177
177
178
178
179
180
181-183
183-190
185
185-186
186
187
188-189
189
190
190
191
191-192
192
193
194
194
195
(continued)
212
Compound
C1f,H,,0 isomer
10 22
diisoamylene
n-propyl benzene
m-ethyl toluene and CinH0,,
. • J.U t.~
isomer
£-ethyl tolene
1,3, 5-trimethylbenzene
Cn-H_0 isomer
10 22
octainethylcyclotetrasiloxane
(BKG)
C-..H-. isomer
11 24
o-ethyltoluene
C-i^H-.. iBomer
10 20
1, 2,4-trimethylbenzene arid
_n-decane
benzaldehyde and phenol
isobutylbenzene
sec-butylbenzene and m-
dichlorobenzene
C^E~, isomer and ter-butyl-
benzene
1, 2, 3-trimethylbenzene
CinH0_ isomer
10 20
sec-butylcyclohexane
methyl styrene isomer
^-dichlorobenzene and o-cymena
C^-alkyl benzene isomer
C,-alk'yl benzene isomer
ii-butyl benzene
methyl decane isomer
C- H0/ isomer
11 24
C^-alkyl benzene isomer
C, _H1 isomer
10 18
-------
Table 49 (cont'd)
Chroraatographic
Peak No.
63
64
65
66
66A
67
67A
67B
68
69
70
71
72
73
74
74A
76
76A
77
78
79
80
81
82
83
84
85
86
88
Elution Temperature
196
196
197
198-199
200-204
200
200
201
201-202
203
203-204
204
205
206
206
206
208
208
209
210
210
211
212
213
213-215
215-216
216
219
220
221
(continued)
213
Compound
C,-alkyl benzene isomer
C,-alkyl benzene isomer
dimethyl styrene isomer and
5-undecene
ri-undecane
acetophenone
C,.-alkyl benzene isomer
GI 1 !!„,, isomer
Cc-alkyl benzene isomer
C. nH- , isomer
C,-alkyl benzene isomer
C11H20 isoraer
silane compound
C^-alkyl benzene isomer
C.-.H.j, isomer
C,.-alkylcyclohexane isomer
ethylstyrene isomer
C12H24 isomer
C1 7H isomer
C^-alkyl benzene isomer
C11H24 is°mer
C12H24 isomer
Cp-alkyl benzene isomer
C12H24 isomer
1-dodecene
n-dodecane
naphthalene
C,.-allcyl benzene isomer
C,-a.lkyl cyclohexane isomer
6
C11H14 is°mer
C12H24 isonier
-------
Table 49 (cont'd)
Chromatographic
Peak No.
89
90
91
92
93
94
95
96
97
98
99
100
103
104
107
108
110
111
112
116
122
Elution
Temperature
C)
222
223
224
224
225
227
228-229
230
231
232
233
235
238
239
240
isothermal
>
f
Compound
C,-alkyl benzene isomer
C, o^oo isomer
C11H14 isomer
C,,H_Q isomer
13 28
C,-alkyl benzene isomer
C,,Hn/ isomer and C,-alkyl
J.J. J.4 O
benzene isomer
_n-tridecane
C,,HOQ isomer
14 28
CiyHon isomer
14 30
|3-methyl naphthalene
C?-alkyl benzene isomer
a-methyl naphthalene
benzothiazole
C, CH__ isomer
15 32
n-tetradecane
biphenyl
ethylnaphthalene isomers
dimethyl naphthalene isomer
dimethyl naphthalene isomer
ii-pentadecane
ii-hexadecane
See Table 29 (S8) for sampling protocol.
214
-------
Table 50. POLLUTANTS IDENTIFIED OR DETECTED IN AMBIENT AIR
FROM MAY STREET, HOUSTON, TXa
Chroma to graphic
Peak No.
1
2
2A
3
3A
4
5
6
7
8
8A
8B
9
10
11
11A
12
13
14
15
16
17
18
19
19A
19B
20
21
22,22A,22B
Elution Temperature
(°C)
76
79
79
80
81
82
83
84
87
91
91
91
92
96
97
98
104
107
108
109
111
113
116
117
118
119
123
124
126
(continued)
215
Compound
propene
cyclopropane
chloromethane
2-methylpropane
2-methylpropene
n-butane
trans- 2-butene
cis-2-butene
ethyl chloride
isopentane
trichlorofluoromethane
propanal
acetone
methylene chloride
isopropanol
C,H10 isomer
D 12
C,Hno isomer
o 12
3-methylpentane
4-methyl-l-pentene
C,HT , isomer
6 14
n-hexane
chloroform
C6H12 is0mer
ethyl acetate
C5H1Q isomer
1,1, 1-tr ichloroethane
C-,Hn, isomer
7 lo
carbon tetrachloride
C..H,, isomers
7 ID
-------
Table 50 (cont'd)
Chroma tographic
Peak No.
22C.23
23A.23B
24
25
25A
25B
25C
26,27
28
29
30
31,32,33,34
35
36
37
38
39,40,41
42
43
44,45,46
47
48
48A
48B
49,50
50A
51
52
52A
53
54
Elution Temperature
128,129
130,131
132
138
139
140
140
142,144
145
146
149
151,152,153
153
154
156
158
159,160
162
163
164,165,166
167
169
170
171
173
173
174
176
177
178
179
(continued)
216
Compound
C_Hn , isomers
7 14
C.,H, . isomers
7 14
n-heptane
dimethylpentene
C0H,0 isomer
8 18
C_Hn , isomer
8 16
C_H10 isomer
8 18
C_,Hn . isomers
7 14
C..H, , isomer
7 16
toluene
C_H, 0 isomer
8 18
C0Hn .. isomer
8 16
C0H- 0 isomer
8 18
n-octane
CnH- , isomer
8 16
tetrachloroethylene
C H isomers
9 20
C-H.. o isomer
9 18
CnH0rt isomer
9 20
C H1 _ isomers
9 18
C,.H0-. isomer
9 20
ethylbenzene
jg-xylene
m-xylene
CgH..,, isomers
bromoform (tent.)
CQH.. 0 isomer
9 18
o-xylene
_n-nonane
C-HT 0 isomer
9 18
C9H18 lsomer
-------
Table 50 (cont'd)
Chromatographic
Peak No.
55
56
57
58,59
60
61,62
63
63A
63B
63C.63D
63E
63F
64
65
66
67
67A
68
68A
69
70
71
72,72A,72B
72C
73,74,75,75A
76,76A
77.77A.78
79
80,81,82
83,84
Elution Temperature
(°C)
179
"
181
181
182,183
184
184,185
180
190
191
192,193
193
193
194
195
197
198
198
199
199
200
203
204
206,207
207
208,210
211
213,214,215
216
217,218
219,220
(continued)
217
Compound
C-.H.. Q isomer
9 18
CnriH00 Isomer
10 22
isopropylbenzene
C10H22 isomers
C0H1Q isomer
9 18
C10H20 ls°mer
n-propylbenzene
m-ethyltoluene
p_-ethyltoluene
C,-|H2, isomers
1,3, 5-trimethylbenzene
benzaldehyde
'C10H20 is°mer
1, 2,4-trimethylbenzene
C10H20 iS°mer
C. -alkyl benzene
m-dichlorobenzene
C,-alkyl benzene
unknown
1,2, 3-tr imethy Ibenzene
C10H20 is°mer
C9H10 isomer
C,-alkyl benzenes
C12H26 lsomer
C,-alkyl benzenes
C, -alkyl benzenes
Cs-alkyl benzenes
C12H24 isomer
C -alkyl benzenes
C -alkyl benzenes
-------
Table 50 (cont'd)
Chromatographic
Peak No.
85
86-90
91
9r.
93
94
95
95A
95B
96
97-100
101
102,103
104
105,106
107
Elution Temperature
<°C)
221
222,223,224,225,226
227
228
229
230
230
230
230
230
230
230
230
230
230
230
Compound
Ci-H10 isomer
10 12
C,.-alkyl benzenes
C,-alkyl benzenes
C,,,H0, isomer
12 26
C,.-alkyl benzene
C.. ~H_,. isomer
13 28
naphthalene
C^-alkyl benzene
C,-alkyl benzene
C,_H0, isomer
13 26
Cfi-alkyl benzenes
C,_H», isomer
13 26
C..-alkyl benzenes
C10H,,0 isomer
13 28
C,.-alkyl benzenes
C,~R~n isomer
13 28
3.
Resolution was on a 400 ft OV-101 SCOT programmed from 20-230°C at
40°C/min, see Table 29 (S9) for sampling protocol.
218
-------
Table 51. POLLUTANTS IDENTIFIED IN DAY AMBIENT AIR
IN DOWNTOWN ST. LOUIS, M0a
Chrotnatographic
Peak No.
1
2
4
4A
5
5A
6
7
8
9
9A
10
11
12
13
13A
14
15
16
16A
17
17A
17B
17C
18
19
19A
20
21
22
22A
Elution Temperature
(°C)
84
89
96
97
98
98
100
102
104
106
107
108
109
110
111
111
113
115
116
117
119
120
121
122
124
126
126
127
129
130
131
(continued)
219
Compound
methylsilane
acetone
2-methylfuran and n-hexane
3-methyl-2-pentene
3-methylfuran
chloroform
vinyl isopropyl ether
C-H-,. isomer
7 16
C H isomer
1 , 1, 1-trichloroethane
methyl ethyl ketone
benzene and CC1,
4
cyclohexane
2-methylhexane
C..H, , isomer
7 lo
C-,H, . isomer
7 14
3-methylhexane
C?H , isomer
dimethylcyclopentane isomer
trichloroethylene
n-heptane
C_,H., , isomer
/ ID
C7H-2 isomer
2 , 4-dimethylf uran
methylcyclohexane
C0H., , isomer
o J.O
CQH1Q isomer
O J.O
2 , 4-dimethylhexane
CQH..,. isomer
o ID
tr imethy Icyc lopentane
CQH isomer
o ID
-------
Table 51 (cont'd)
Chromatographic
Peak No.
23
24
25
26
26A
27
27A
28
29
29A
30
31
32
32A
33
33A
34
35
36
37
37A
37B
38
39
39A
40
41
42
43
44
45
46
Elution Temperature
132
132-133
133-134
136
137
138
138
140
141-143
143
144
146
148
149
150
151
152
153-154
154-156
157
158
159
160-161
161-163
164
166
168
169
170
171
172-173
173
(continued)
220
Compound
CftH isomer
toluene
2-methylheptane
3-methylheptane
dimethylcyclohexane isomer
CQH, , isomer
O ±0
dimethylf ormamide
l-methyl-3-ethylcyclop' ..tane
n-octane
tetrachloroethylene
hexamethylcyclotrisiloxane
2-hexanone
C9H20 isomer
C9H20 lsomer
C0H., , isomer
o lo
C0H.. 0 isomer
y J.O
chlorob enzene
ethylbenzene
jp_-xylene
C9H20 isomer
phenylacetylene
styrene and C H „ isomer
£-xylene
n-nonane
CgH..g isomer
C"10^22 isomer
isopropylbenzene
3-methylnonane
pr opy Icyc lohexane
C10H16 is°mer
it-propylbenzene
m-ethyltoluene
-------
Table 51 (cont'd)
Chromatographic
Peak No.
47
48
49
50
51
52
53
53A
53B
54
55
56
57
58
59
60
60A
61
62
63
64
65
66
67
68
69
70
71
72
Elution Temperature
174
175
176
177
178
179
180-181
181
182
183-184
184
185
186
187
188
188
189
190
190-191
191.5
192
192
193
194
195
195
196
197-198
199
(continued)
221
Compound
p-ethyltoluene
1,3, 5-tr imethylbenzene
C H isomer
octamethylcyclotetrasiloxane
o-ethyltoluene
l-methyl-4-isopropylcyclo-
hexane
1,2,4-trimethylbenzene and
n-decane
benzaldehyde
isobutylbenzene and C H
isomer
m-dichlorobenzene
methyldecane isomer
methyldecane isomer
1,2, 3- tr imethylbenzene and
o-cymene
C.. -.!!„, isomer
sec-butylcyclohexane
o-methylstyrene
o-dichlorobenzene and j>-cymene
C,-alkyl benzene isomer
m-diethylbenzene
n-bu ty Ib en z ene
C11H24 isomer
C H2, isomer
p_-propyltoluene
CinH1R isomer
C . -alkyl benzene isomer
C. -alkyl benzene isomer
C11H22 isomer
n-undecane
C -alkyl benzene isomer and
-------
Table 51 (cont'd)
Chroma tographic
Peak No.
73
74
74A
75
76
77
78
78A
78B
79
80
81
82
83
84
85
86
86A
87
88
89
89A
90
91
92
93
94
Elution Temperature
200-201
202
202
203
204
205
205
205
206
206
207
208
209
210
211
212
213
214
216
217
218
219
220
221
222
223
224
(continued)
222
Compound
C,.-alkyl benzene isomer
dimethylethylbenzene isomer
C10H0, isomer
12 26
dimethylethylbenzene isomer
tetramethylbenzene and C-.-H —
isomer
C,.-alkyl benzene isomer
C^-alky! cyclohexane isomer
C,. -alkyl benzene isomer
dimethylstyrene isomer
Cj.-alkyl benzene isomer
C, 0H- ., isomer
12 26
C, -alkyl benzene and C -alkyl
benzene isomer
C,0H0.. isomer
12 26
C^-alkyl benzene isomer
C .--alkyl benzene isomer and
C, 0H00 isomer
13 28
1-dodecene
n-dodecane
naphthalene
C,_H00 isomer
13 28
CnH00 isomer
13 28
C, -alkyl benzene isomer
1,3, 5-tr ichlorobenzene
C..-H-- isomer
C H isomer
12 24
C,-alkyl benzene isomer
C..-H isomer
C H isomer
13 28
-------
Table 51 (cont'd)
Chromatographic Elution Temperature
Peak No. (°C) Compound
95
96
103
225
228
240
C13H28 isomer
n-tridecane
n-tetradecane
SA 400 ft OV-101 stainless steel SCOT was programmed from 20-240°C @ 4°C/
min. Air samples were taken on balcony of 32nd floor apartment. See
Table 30 (S3) for sampling protocol.
223
-------
10
90r
P80
8 7(t
60-
KflU
50h
111
> 30-
10-
0
68
12
80
—I—
92
TEMPERATURE ("O
128 HO 152 164 ITS 188 200
18
24
27
30 33
TIME (MIN)
36
39
42
45
48
51
54
57
60
63
Figure 33.
Profile of ambient air pollutants from Arvado, CO using high resolution gas
chromatography/mass spectrometry/computer. A 400 ft S.S. SCOT coated with
OV-101 stationary phase was used; temperature programmed from 20-240°C @ 4°C/
rain. See Table 52 for listing.
-------
Table 52. POLLUTANTS IDENTIFIED IN AMBIENT AIR FROM ARVADO, M0£
Chromatographic
Peak No.
0
1
2
3
4
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
Elution Temperature
(°C)
62
69
71
82
86
88
92
96
98
101
104
106
107
110
114
116
117
118
120
122
123
124
125
128
130
132
134
135
136
137
(continued)
225
Compound
carbon dioxide
sulfur dioxide
2-butene
C5H12
acetaldehyde
furan
propionaldehyde
C,Hn ,
6 14
acetone
ctHi/
6 14
n-hexane
2-methylfuran
C6H12
C6H12
1,1, 1-trichlor oethane
benzene
C6H12
C7H12
C7H16
C7H14
C7H14
trichloroethylene
C7H16
2 , 4-dimethylf uran
C7H14
C8H18
C8H18
C8H16
C8H16
toluene
-------
Table 52 (cont'd)
Chromatographic
Peak No.
30
31
32
33
34
35
36
37
38
39
40
41
42 .
43
44
45
46
47
48
49
50
51
52
53
54
55
55A
56
57
58
59
Elution Temperature
138
140
142
142
143
144
145
146
147
149
150
151
152
153
153
154
155
155
156
156
157
158
159
160
161
162
162
163
164
167
168
(continued)
226
Compound
C8H18
C8H18
C8H16
C8H16
C8H16
C8H16
C8H18
hexamethylcyclotrisiloxane
tetrachloroethylene
4-methyl-pentan-2-one
C.H.-
9 20
C_H-_
9 20
C_H-,
8 16
C H
9 20
wnfi.- r
8 16
CQH1Q
9 18
CQH1$S
9 18
chlorobenzene
C9H18 (tent->
ethylbenzene
C_Hon
9 20
2.-xylene
m-xylene
phenylacetylene
^^ j^ri CtSTlt • )
10 22
styrene
C^H
9 18
o-xylene
C H
9 20
C^H
9 18
C H
10 22
-------
Table 52 (cont'd)
Chroma tographic
Peak No.
60
61
62
62A
63
64
65
65A
66
66A
66B
67
68
69
70
71
72
73
74
75
76
77
78
78A
79
80
81
82
82A
83
84
Elution Temperature
(°C)
169
169
170
170
170
171
171
171
172
172
172
173
174
174
175
175
176
177
177
178
179
180
181
181
183
184
185
186
186
187
188
(continued)
227
Compound
C10H22
C10H22
isopropylbenzene
C10H22
C10H22
C10H22
C9H18
C10H20
C10H22
C10H20
unknown
C10H20
C10H20
n-propylbenzene
m-ethyltoluene
p_-ethyltoluene
1,3, 5-trimethylbenzene
C10H22
unknown
C10H22 (tent°
o-ethyltoluene
C10H20
1,2, 4-trimethylbenzene
C10H22
benzaldehyde
sec-butylbenzene
m-dichlorobenzene
o-cymene
C11H24
1 , 2 , 3-tr imethylbenzene
C11H24
-------
Table 52 (cont'd)
Chromatographic
Peak No.
85
86
87
88
89
90
91
91A
92
93
93A
94
95
96
96A
97
98
t
99
100
101
102
103
104
104A
105
106
106A
107
108
109
110
Elution Temperature
189
191
193
194
195
196
197
197
198
200
200
201
204
207
207
209
210
211
213
214
215
216
218
218
219
221
221
223
224
226
227
(continued)
228
Compound
C10H20
B-methylstyrene
C11H22
C,-alkyl benzene
C,-alkyl benzene
C,-alkyl benzene
C,-alkyl benzene
CTJ
_ _ nn *
11 24
C-,-,H0,
11 24
C,-alkyl benzene
\j — f. rlj-. x-
12 26
C H
11 24
C,-alkyl benzene
C,-alkyl benzene
c* w
12 26
C,-alkyl benzene
C, -alkyl benzene
C,-alkyl benzene
C H
11 22
C H
11 24
f1 tl
11 24
C H
11 24
Cr-alkyl benzene
C H
Iln22
C,-alkyl benzene
C^-alkyl benzene
C H
12 26
C^-alkyl benzene
C H
12 26
C.-alkyl benzene
unknown Si cpd. m/e 267,
281, 341
-------
Table 52 (cont'd)
Chromatographic Elution Temperature
Peak No. (°C) Compound
111 228 C -alkyl benzene
112 229 CHH22
113 230 C -alkyl benzene
114 231 C,H7-alkyl benzene
115 232 C12H26
116 233 C -alkyl benzene
117 237 C,H -alkyl benzene
117A 237 , ci2H26
118 238 C,. -alkyl benzene
119 239 ci2H22
120 240 Ci2H26
121 isothe
122
123
124
125
126
127
128
129
130
131
132
13 2A
133
134
135
136
13 6A
137
138 ,
>rmal C,. -alkyl benzene
C12H24
C12H26
C H -alkyl benzene
C,--alkyl benzene
naphthalene
C13H28
C^-alkyl benzene
C13H28
C13H28
C, -alkyl benzene
6
C, -alkyl benzene
6
C13H26
C, -alkyl benzene
o
C13H26
C13H28
C13H28
C, -alkyl benzene
D
C13H28
r C13H26
(continued)
229
-------
Table 52 (cont'd)
Chromatographic Elution Temperature
Peak No- (°C) Compound
139 isothermal CnHoQ
1J Jio
140
141
142
143
144
145
146
147
148
149
150
I
C14H30
C13H28
C14H28
unknown, m/e 73
C14H30
C14H20
unknown
unknown
C14H30
C15H32 (tent.)
C14H30
See Table 30 (S4) for sampling protocol.
230
-------
Table 53. POLLUTANTS IDENTIFIED IN AMBIENT AIR FROM ST. ANN, M0a
Chroma tographic
Peak Ho.
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
.'11
32
33
34
35
36
Elution Temperature
<°C)
83
84
86
87
89
92
95
98
101
104
105
107
109
HI
112
113
113
114
115
116
117
118
120
121
126
128
128
130
132
132
133
(continued)
231
Compound
acetaldehyde
d i chl or omc thane
carbon disulfide
propionaldehyde
acetone
hexane isomer
hexane isomer
hexane isomer
chloroform
hexene isomer
heptane isomer
heptane isomer
1,1,1-trichloroettyane
benzene
cyclohexane
heptane isomer
heptane isomer
heptene isomer
heptane isomer
heptane isomer
heptene. isomer
heptene Lsocier
tri^.hloroethylene
heptane isomer
heptene iscmer
octane isomer
octane isomer
octcne isomer
heptene isi-iiiet
heptene isomer
octane isoniei.
-------
Table 53 (cont'd)
Chroma tographic
Peak No.
37
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
63
64
65
66
67
68
Elution Temperature
(°C)
134
135
137
139
141
142
144
145
146
148
149
150
151
153
153
154
154
155
157
158
158
160
161
162
165
166
167
168
168
169
169
170
(continued)
232
Compound
toluene
octane isomer
octane isomer
nonane isomer
nonene isomer
octane Isomer
tetrachloroethylene
unknown
unknown
unknown
nonane isomer
nonane isomer
octene isomer
nonene isomer
nonene isomer
chlorobenzene
ethylbenzene
j>-xylena
m-xylene
phenyl acetylene
decane isomer
nonene isoiner
oi-xylene
n-nonane
nonene isoiner
decane isoreer
decane isomer
isopropylbenzene
decane isomer
decane isomer
nonane isoiner
cyclof enchcne (tent . )
-------
Table 53 (cont'd)
Chromatographic
Peak No.
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
95
96
97
98
99
99A
Elution Temperature
171
172
173
174
175
175
177
178
179
180
180
181
183
184
184
186
187
188
188
189
190
190
190
191
191
192
193
194
195
196
197
197
(continued)
233
Compound
decene isomer
rt-propylbenzene
m-ethyltoluene
£-ethyltoluene
1,3, 5-tr imethy Ibenzene
decane isomer
unknown
o-ethyl toluene
decene isomer
1, 2,4-triraethylbenzene
n-decane
benzaldehyde
C.-alkyl benzene
m-dichlorobenzene
C.-alkyl benzene
1, 2, 3~tr imethy Ibenzene
undecane isomer
undecane isomer
o-methylstyrene (tent.)
undecene isomer
C,-alkyl benzene
C,-alkyl benzene
C.-alkyl benzene
C,-alkyl benzene
undecane isomer
dodecane isomer
C,-alkyl benzene
dodecane isomer
C.-alkyl benzene
C.-alkyl benzene
n-undecane
methyl indan isoRcr
-------
Table 53 (cont'd)
Chroma tographic
Peak No.
100
101
102
102A
103
104
105
106
107
108
108A
1C9
110
111
112
113
114
115
116
117
118
119
120
121
122
123
123A
124
125
126
127
128
Elution Temperature
(°C)
198
199
200
200
201
202
203
204
204
205
205
206
207
207
207
208
209
210
210
211
212
214
215
216
217
218
218
219
220
221
222
222
(continued)
234
Compound
Cc~3lkyl benzene
undecene isomer
Ur-alkyl benzene
dodecane isomer
C,-alkyl benzene
tridecane isomer
unknown
dodecane isomer
C_-alkyl benzene
undecene isomer
C,--alkyl benzene
methylindan isomer
C,--alkyl benzene
dodecene isomer
C,-alkyl benzene
dodecane isomer
Ct--alkyl benzene
C,.-alkyl benzene
Cr-alkyl benzene
dodecane isomer
n-dodecane
naphthalene
tridecane isomer
Cr-alkyl benzene
C,-alkyl benzene
tridecane isomer
tridecane isomer
C,-alkyl benzene
unknown
dodecene isoiaer
Cg-alkyl benzene
tridecane isomer
-------
Table 53 (cont'd)
Chromatographic
Peak No.
129
129A
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
Elution Temperature
223
223
223
224
22.5
226
22.7
229
230
231
232
234
235
236
236
237
238
240
240
240
240
240
240
240
Compound
tridecene isomer
C^-alkyl benzene
tridecane isomer
tridecane isomer
tridecene isomer
unknown
tridecane isomer
tridecene isomer
tetradecane isomer
6-methylnaphthalene
tetradecene isomer
a-methylnaphthaleiie
tetradecane isomer
tetradecane isomer
tetradecane isomer
pentadecane isomer
pentadecane isomer
tetradecene isomer
n- tetradecane
tetradecene isomer
tetradecene isomer
tetradecene isomer
hexadecane isomer
pentadecane isomer
*See Table 31 (S5) for sampling protocol.
235
-------
Table 54. ORGANIC VAPORS IDENTIFIED IN DAY AMBIENT AIR AT THE
ENTRANCE OF THE EISENHOWER TUNNEL IN COLORADO3
Chromatographic
Peak No.
1
2
2A
4
5A
5B
6
7
8
9
9A
10
11
12
13
14
15
16
18
20
21
22
23
23A
24
25A
2 SB
26
27
Elution Temperature
(°C)
100.5
103
104
107.5
111
112
113
114
115
116
116
117
119.5
121
122
128
130
131
134
136
137
137.5-9
140
140
141
143
143.5
144-6
147
(continued)
236
Compound
2-methylfuran
n-hexane
chloroform
methylcyclopentane
1,1, 1-trichloroethane
CcH-.O isomer
benzene + carbon tetra-
chloride
cyclohexane
2-methylhexane
2 , 3-dimethylpentane
1,1-dimethylcyclopentane
3-methylhexane
1 , cis-3-d imethylcyclopentane
1 , trans-2-d imethylcyclopen-
tane
n-heptane
4, 4-dimethyl-2-pentene
C0Hn 0 isomer
0 IB
2 , 4-d imethy Ihexane
1 , trans-2 , cis-3-tr imethyl-
cyclopentane
2 , 3-d imethy Ihexane
toluene
CG^-I „ isomer
3-methylheptane
dimethylnitrosamine (tent.)
2,3, 4-trimethyl-2-pentene
dimethyl formamide + CQH
isomer 8 18
l-methyl-3-ethylcyclopentane
n- octane
hexamethylcyclotrisiloxane
(BKG)
-------
Table 54 (cont'd)
Chromatographic
Peak No.
28
28A
29
30
31
32
33
33A
33B
33C
34
35
36
37
37A
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
Elution Temperature
(°C)
149.5
150
151
152
153
154
155
155.5
156
156.5
157
158
159
160
161
163.5
164-8
168.5
169
170
171
171-2
173
174
174.5
175.5
176.5
177
178
178-9
180
(continued)
237
Compound
tetrachloroethylene
C9H20 isomer
C9H20 isomer
2, 6-dimethylheptane
n-propylcyclopentane
C9H18 lsomer + C9H20 isomer
CgH _ isomer
1-nonene
2 , 3-dimethylheptane
4-methyloctane
ethylbenzene
£-xylene
3-methyloctane
o-xylene
phenyl acetylene
C9H18 isomer
n-nonane
l-methyl-2-ethylcyclohexane
C10H22 is°mer
2-methylnonane
C_-alkyl benzene
3-methylnonane
propylcyclohexane + ^0^22
isomer
C10H22 isomer
C10H20 iS°mer
C1QH22 isomer
4-methylnonane
£-ethyltoluene
C10H20 1S°mer
C10H22 isomer
diethylcyclohexane isomer
-------
Table 54 (cont'd)
Chroma tographic
Peak No.
55
56
57
58
59
60
60A
61
62
63
64
65
66
67
68
69
70
71
72
75
76
77
78
79
80
81
82
83
Elution Temperature
181
182
183-4
184.5
185
186
186
187
187-8
189
190
191
191
192
192.5
193
193.5
194
195-6
198
199
199.5
200
202
202
203
204.5
205
(continued)
238
Compound
o-ethyltoluene
l-methyl-trans-4-isopropyl-
cyclohexane
n-decane 4- 1,2,4-trimethyl-
benzene
C^..H__ isomer
10 20
benzaldehyde
5-methyldecane
2-phenylpropionaldehyde
(tent.) + C,-alkyl benzene
methyldecane isomer
methyldecane isomer
1,2, 3-trimethylbenzene
Jt-butylbenzene
C,,H0/ isomer
11 24
n-bu ty Icyc lohexane
Cn-H~_ isomer
11 22
CinH00 isomer
11 22
C,-alkyl benzene
m-diethylbenzene
n-undecane
_p_-propyltoluene
C,-alkyl benzene
C^-alkyl benzene -f- C H
isomer ^
C^-alkyl benzene + CnH22
isomer
^"11^22 "*" ^"11^24 ^-somer
C^-alkyl benzene
C H00 isomer
11 22
^12^26 isomer
acetophenone
C12H26 isomer
-------
Table 54 (cont'd)
Chromatographic
Peak No.
84
84A
85
86
87
88
89
90
91
92
93
94
96
97
100
105
109
111
112
113
Elution Temperature
206
207
208
208-9
209
210
210.5
211
212-3
214
215
216
218
219
224
231
240
240
240
240
Compound
b ipheny lene ( tent . )
C12H24 lsomer
C,.-alkyl benzene
C-i iH_ ,. isomer
12 26
C12H24 + C12H26 isomers
C^-alkyl benzene
C10H0/ isomer
12 24
C.«Hn, isomer
12 26
2 , 3-dihydro-2-methy Ibenzof uran
(tent.) + 2-phenyl-2-methyl-
butane
cyclodecane (tent.)
Cr-alkyl benzene
n-dodecane + decamethyltetra-
siloxane (BKG)
l-methyl-3-£-butylbenzene
naphthalene + 1,3,5-tri-
chlorobenzene
C.Jly, isomer
n-tridecane
7-methyltridecane
n-tetradecane
n-pentadecane
n-hexadecane
a
See Table 31 (SI) for sampling protocol.
239
-------
Table 55. ORGANIC VAPORS IDENTIFIED IN DAY AMBIENT AIR IN DENVER, CO3
Chromatographic
Peak No.
I
2
3
3A
4
4A
4B
4C
5
5A
5B
6
7
7A
8
9
9A
9B
10
11
12
13
13A
14
15
16
17
18
19
19A
20
21
Elution Temperature
(°C)
87
91
91
92
93
95
97
98
100
101
101
102
105
105
106
107
109
110
111
111
112
113
113
114
115
117
118
119
120
123
124-125
126
(continued)
240
Compound
methylene chloride
acetaldehyde
dimethylether
diethylether
acetone
C.,Hn , isomer
6 14
3-methylpentane
1-hexene
n-hexane
methyl furan
C,H, „ isomer
6 12
CHC13
C-,H, ., isomer
7 16
C -H- „ isomer
6 12
C_Hn , isomer
7 16
C-,Hn , isomer
7 16
n-butanal
1,1, 1-trichloroethane
benzene
CC1.
4
cyclohexane
C-H.,, isomer
7 16
2 , 3-dimethylpentane
C_H, . isomer
7 14
3-methylhexane
C_,Hn, isomer
7 16
1 , trans-2-dimethylcyclopen-
tane
CDH1, isomer
8 16
n-heptane
C_H „ isomer
7 12
methyl cyclohexane
CQH isomer
8 18
-------
Table 55 (cont'd)
Chroma tographic
Peak No.
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
38A
39
40
41
42
43
44
45
46
47
48
49
50
Elution Temperature
127
127
129
130
131
132
132-4
133-5
136
137
138
139
140-2
143
145
146
147
147
148
148
149
150
152
152-3
153-4
155
157
158
158-9
156-61
(continued)
241
Compound
CgH^g isomer
CyH-iA isomer
trimethylcyclopentane
isomer
trans-4-octene
trimethylpentane isomer
2 , 3-dime thy Ihexane
toluene
CfiH.jo isomer
3 -me thy Ihep t ane
dimethylcyclohexane isomer
trimethylpentane isomer
1-octene
n-octane
tetrachloroethylene and
trimethylcyclotrisiloxane
2-hexanone and CqH?n isomer
C9H20 isomer
Dimethylcyclohexene isomer
2, 6-dimethylheptane
CQH., isomer
JJ ID
C0Hn , isomer
o lo
C9H18 isomer
1-nonene
C9H20 isomer
ethyl benzene
p-xylene
phenyl acetylene and
CgH,g isomer
2,2, 5-tr imethy Ihexane
C9H18 isomer
o-xylene
n-nonane
-------
Table 55 (cont'd)
Chromatographic
Peak No.
51
52
53
54
55
56
57
57A
58
58A
59
59A
60
61
62
62A
63
63A
64
65
66
66A
67
68
69
70
71
72
73
Elution Temperature
163
164
165
165
166
167
168
168
169
169
170
171
171-2
173
174
174
175
176
176
177
178
179
181
181
182
182
183
184
185
(continued)
242
Compound
methylethylcyclohexane isomer
C1QH22 isomer
2,5-dimethyloctane
isopropylbenzene and CQH1fi
isomer
C1QH22 isomer
C,-alkyl cyclohexane isomer
a-pinene
4-propylheptane
C^-H™- isomer
C10H22 isomer
n-propylbenzene
C10H22 isomer
m-ethyltoluene
p-ethyltoluene and C,QH_2
isomer
C10H22 isomer
C.^Rj, isomer
jD-ethyltoluene
1-decene
l-methyl-4-isopropylcyclohexane
1 , 2 , 4- tr imethy Ib en z ene and
n-decane
benzaldehyde
isobutylbenzene
sec-butylbenzene
in-dichlorobenzene
C^.H., isomer
2-cymene
l»2,3-trimethylbenzene
C^-alkylcyclohexane isomer
3-methylstyrene
-------
Table 55 (cont'd)
Chromatographic
Peak No.
74
75
76
77
78
79
80
81
82
83
84
84A
85
85A
86
87
88
89
90
90A
91
92
93
94
Elution Temperature
. (°C)
185
187
188
188
189
189
190
192
193
194
196
196
197
198
198
199
199
200
200
201
201
202
203
204
205
(continued)
243
Compound
C11^22 •i-somer an<* m-diethyl-
benzene
£-propyltoluene
o^diethylbenzene
dime thy Inonane isomer
2-methy Id ecane
Cn,H0/ isomer
11 24
o-propyltoluene and
C10Hlg isomer
dimethylethylbenzene isomer
C1f,H17 isomer and 1-undecene
n-undecane
C,.-alkylbenzene and C.,H_~
isomer
C12H26 isomer
C.-alkylbenzene and Cc-alkyl-
benzene isomer
acetophenone
C,-alkylbenzene isomer
C12H26 isomer
C.-alkylbenzene isomer
C12H24 isomer
silane compound
C.-alkylcyclohexane isomer
Cc-alkyl benzene and Ci2H24
isomer
C10H22 is0mer and CHH20
isomer
Cc-alkylbenzene isomer and
CIQH 2 isomer
C,,-alkyl benzene isomer
C12H26 isomer
-------
Table 55 (cont'd)
Chromatographic
Peak No.
95
95A
96
97
97A
98
99
100
102
103
105
106
107
108
109
111
112
115
117
Elution Temperature
206
207
208
209
210
212
213
214
216
217
219
220
221
222
224
227
232
235
237
Compound
C,--alkyl benzene
C -H-, isomer
1-dodecene
n-dodecane
naphthalene
C,-H~o isomer
C. o^oo isomer
isomer
C,-alkyl benzene isomer
C13H26 isomer
Cfi-alkyl cyclohexane isomer
C--HLfl isomer
C13H28 isomer
C14H30 isomer
si lane compound
n-tridecane
C..,H-R isomer
methyl naphtalene
silane compound
n- tetrad ecane
isomer
See Table 31 (S7) for sampling protocol.
244
-------
Table 56. POLLUTANTS IDENTIFIED IN AMBIENT AIR IN PATERSON, NJa
Chromatogruphic
Peak No.
1
2
2A
3
3A
3B
3C
4
4A
4B
5
6
7
7A
8
8A
8B
9
10
11
11A
12
13
14
15
16
17
17A
18
18A
19
Elution Temperature
(°C)
72
74
76
80
84
86
90
91
92
93
95
100
103
104
105
106
107
108
109
112
113
123
126
128
129
131
134
135
137
138
139
(continued)
245
Compound
N2 + 02
co2
ethylerie oxide
CF2C12
propane
isobutane
1-butene
n-butane
2-butene
cyclobutane
acetaldehyde
silane compound (BKG)
isopentane
CC13F
1-pentene
furan
trans-2-pentene
n-pentane
cis-2-pentene
CH2C12
propanal
2-methylpentane
3-methylpentane
hexafluorobenzene (eS)
n-hexane
CHC13 •
perfluorotoluens (eS)
C6H14 isomer
methyl cyclope.ntane
1 , 2-dichlcroethane
Ijljl-trichloroethane
-------
Table 56 (cont'd)
Chromatographic
Peak No.
20
20A
20B
21
22
22A
23
24
24A
25
26
27
28
29
,30
31
32
33
34
34A
35
36
36A
36B
37
37A
37B
38
39
39A
40
Elution Temperature
143
143
144
145
147
148
151
152
153
160
164
167
168
171
173
175
177
181
184
185
187
189
191
192
193-194
195
193
199
201
202
203
(continued)
246
Compound
benz,ene
cci4
2-methylhexane
C..H.. , isomer
7 16
3-methylhexane
C-.H . isomer
7 14
dibromomethane
trichloroethylene
n-heptane
methylcyclohexane
CQHno isomer
O -Lo
toluene
2, 4-dimethylhexane
dimethylcyclohexane
n-octane
hexamethylcyclotrisiloxane
(BKG)
tetrachloroethylene
C^K., 0 isomer
9 18
chlorobenzene
CqH,R isomer
ethylbenzene
jj-xylene
m-xylene
styrene
o-xylene and ii-nonane
methyl1 ethyl cyclohexane isome;
r l' i
9 18 lsom^r
isopropylbenzene
methylnonane isomer
CQILC isomer
9 lo
C10H16 isornor
-------
Table 56 (cont'd)
Chroma tographic
Peak No.
41
42
43
44
44A
44B
45
46
47
47A
48
49
50
50A
51
52
53
53A
54
Elution Temperature
204
204-207
207-208
210
210
211
211-212
213
216
217
218
220
221
222
223
225
228
228
229
Compound
n-propylbenzene
m-ethyl toluene
j>-ethyltoluene
o-ethyl toluene
menthene or CnrtH,n isomer
10 18
methane or C.. -.!!_„ isomer
10 20
1 , 2, 4-trimethylbenzene
P H -i «rmi<=.T
\j _ «il__ JLOUlUcL
10 20
n-decane
o-cymene
1,2, 3-trimethylbenzene
C, -)H_-. isomer
C,-alkyl benzene isomer
C.,1I0, isomer
11 24
m-diethylbenzene
acetophenone and C^H., isomer
C,-alkyl benzene isomer
CinH-s isomer
n-undecane
See Table 35 (SI) for sampling protocol.
247
-------
Table 57. POLLUTANTS IDENTIFIED IN AMBIENT AIR IN CLIFTON, NJe
Chromatographic
Peak No.
1
1A
2
2A
2B
3
4
4A
5
5A
5B
6
7
7A
73
7C
8
9
9A
10
10A
10B
11
12
13
13A
14
14A
15
16
17
Elution Temperature
80
84
85
86
87
88
90
91
92-94
94
94-100
101-104
104
105
105
106
106
107
108
110-117
111
118
122
126
128
128
J.29
130
131
132
133-134
(continued)
248
Compound
dichlorodif luoromethane
CH3C1
propene
propane
vinyl chloride
1-butene
n-butane
2-butene
acetaldehyde
cyclobutane
methyl silane (BKG)
isopentane
CC13F
1-pentene
furan
2~methyl-l-butena
CCH, n isomer
5 10
n-pentane
cis-2-pentene
acetone
CH2C12
2 , 2-dimethylbutane
2-methylpentane
3-methylpcntane
hexaf luorobenzene (g)
2-methylfuran
n-hexane
C,H10 isomer
CHC1,
CcHR0 isomer
pcrflucrotolueno (g)
-------
Table 57 (cont'd)
Chromatographic
Peak No.
18
19
19A
20
20A
21
22
23
24
25
26
27
28
29
29A
30
30A
31
32
•J *•
33
34
34A
35
36
37
38
39
40
40A
41
43
Elution Temperature
(°C)
136
137-140
141
143
143.5
144-145
146-147
149
150
151-153
157
159
165
166-169
168
171
172
173-174
175
177
182
183
184
187
189
191
193
193-195
197
199
204
(continued)
249
Compound
methyl ethyl ketone
1, 2-dichloroethane
1,1,1-trichloroethane
benzene
cci4
2-methylhexane
3-methylhexane
C..IL . isomer
7 14
trichloroethylene
n-heptane
C_,H, , isomer
7 ID
methylcyclohcxane
C0H.., isomer
o ID
toluene
CgH g isomer
C0H, , isomer
o ID
dimethylcyclohexane isomer
n- octane
hexamethylcyclotrisiloxane
(BKG)
tetrachloroethylene
C9H20 isomer
methylethylcyclopentane isomer
chlorobenzene
ethylbenzene
£-xylene
1-nonerie
styrene
o-xylene and n-nonane
C9H18 isomer
isopropylbenzcne
C10H16 iS°mer
-------
Table 57 (cont'd)
Chroma to^raphic
Peak No.
43A
44A
44
45
46
47
48
48A
48B
49
50
51
51A
52
53
54
55
Elution Temperature
(°C)
205
206
207
208-209
211
213
217
218
219
222
224
226
227
229
230
237
240
Compound
n-propylbenzene
benzaldehyde
m-ethyltoluene
octamethylcyclotetrasiloxanc
(BKG)
o-ethyl toluene
n-decane and 1,2,4-trimethyl-
benzene
m-dichlorobenzene
C,-alkyl benzene isomer
1, 2,3-trimethylbenzene
C,-alkyl benzene isorr.er
C,-alkyl benzene isomer
acetophenone
C,-alkyl benzene isonier
n-undecane
C.-alkyl benzene isomer
silane compound (BKG)
n-dodecane
See Table 35 (S2) for sampling protocol.
250
-------
Table 58. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR IN PASSAIC, NJa
Chromatographic
Peak No.
2
2A
2B
2C
3
3A
3B
3C
4
4A
5
5A
6
6A
6B
6C
6C
7
8
8A
8B
9
9A
9B
10
10A
11
11A
12
13
Elution Temp erat are
(°C)
75
76
77
78
80-82
83
85
86
88-89
90
91
92
94-96
97
99
101
102
104
105
106
107
108-109
110
111
113
114-116
117-122
122
123-124
126 „
(continued)
251
Compound
co2
ethylene oxide
so2
propene
CF2C12
n-propane
CHC13
isobutane
vinyl chloride
1-butene
n-butane
2-butene (isomer)
acetaldehyde
chloroethane
°5H12 (iso"'er)
methyl ethyl ether
methyl silane (BKG)
isopentane
trichlorof luormethane
1-pentene
furan and C..H, n (isomer)
3 XU
_n-pentane
methylcyclobutane
propanal
C H 0 (isomer)
CH C12 (isomer)
acetone
isopropanol
2-methylppntcne
2-methylfurari
-------
Table 58 (cont'd)
Chroma tographic
Peak No.
13A
13B
14
14A
15
15A
16
17
18
18A
19
19A
20
20A
21
22
22A
23
23A
24
24A
25
26
27
28
29
30
31
32
Elution Temperature
127
127
128-129
129
129-131
131
131-133
134-136
137
138
140-141
142
144-145
145
146
146-149
149
150-154
156
,160-162
162
164
165-167
167-169
170
1 172-173
174-176
176-178
178-179
(continued)
252
Compound
3-methylpentane
C,IL „ (isomer)
b 12
hexaf luorobenzene (2)
C,H10 (isomer)
O 12
n.-hexane
C6H12 Cisomer)
CHC13
perfluorotoluene (2)
2 , 4-dimethylpentane
C?H1, (isomer)
1,1, 1-trichloroethane
methyl ethyl ketone
benzene
CCIA
2-me thy Ihexane
cyclohexane and dimethyl
pentane (isomer)
C-H,, (isomer)
C-Ji, , (isomer) and trichloroethylene
and n-heptane
CRH1 , (isomer)
CgH^g (isomer)
2, 4-dimethylhexane
C8H16 ^isomer)
2,3,4-trimethylpentane
toluene
3-methylheptane
dimcthylhexane i.somer
n-octane
hexamethylcyclotrisiloxane (BKG)
tctrachloroethylene
-------
Table 58 (cont'd)
Chroma tographic
Peak No.
32A
33
34
35
36
36A
36B
37
33
39
40
41
41A
42
42A
43
^ -J
43A
44
45
/.f.
HO
47
48
50
51
53
53A
54
Elution Temperature
(°C)
180
183
185
187-188
188-190
191
191
193
194-196
198
200
201
202
203
204
205-208
208
208-210
211
212-214
217
219
222
224
229
229
230
Compound
CQ1I20 (isomer)
C^H__ (isomer)
9 20
C9Hlg (isomer)
ethyl benzene and C H
i • \ ' y t-\>
(isomer)
ji-xylene
C9H18 (isomer)
1-nonene
styrene
n-nonane and o-xylene
C10H20 (isoraer)
isopropylbenzene
C10H22 (isorner)
C10H2() (isomer)
C10H20 (isomer)
C1QH20 (isomer)
n-propylbenzene and C]_QH22
isomer and m-ethyltoluene
C10H22 (isomer)
octamethylcyclotetrasiloxane (BKG)
and CinH9n (isomer)
J_ U Z U
1-decene
n-decane and trimethyl benzene
(isomer)
dichlorobenzene
C11H24
C -alkyl benzene (isomer)
C,-alky,l benzene (isomer)
and C1;LH22 (isomer)
C10H18 (iSO''n£r)
C, -alkyl benzene (isomer)
n-undecane
(continued)
253
-------
Table 58 (cont'd)
Chromatographic Elution Temperature
Peak No. (°C) Compound
55 233 ClQH20 (isomer)
55A 234 C;-alkyl benzene (isomer)
SSee Table 35 (S3) for sampling protocol.
254
-------
Table 59. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR IN HOBOKEN, NJa
Chromatographic
Peak No.
2
2A
3
3A
3B
3G
4
4A
5
7
8
9
9A
9B
9C
10
11
11A
12
12A
13
14
15
16
16A
16B
17 '
17A
18
19
Elution Temperature
(°C)
73
79
79-82
84
86
89
90
91
92-94
102
104
106-107
108
110
111
112
116-119
120
122-123
124
126-128
128-130
130-132
132-135
135
136
137
138
143-144
144-145
(continued)
255
Compound
co2
ethylene oxide
CF2C12
chlorcme thane
isobutane
1-butene
.n-butane
2-butene
acetaldehyde
isopentane
CC13F
CcHir. (isomer) and furan
;> ID
ji-pentane
propanal and C H, n (isoiuei")
J J-U
ethanol
CH2C12
acetone
isopropanol
2-methylpentane
3-methylpentane
C6F6
n-hexane and 1-hexene
CHC13
C7F8
methyl ethyl ketone
1 , 2-d.lchloi:oeth.JUie
l,l,l~v.richloroethane
1 , l-dlchloropr'ippne
benzene
cci4
-------
Table 59 (cont'd)
Chromatographic
Peak No.
19A
20
20A
21
22
22A
23
24
25
26
27
28
29
30
31
32
32A
33
33A
33B
34
35
36
36A
37
38
Elution Temperature
146
147
148
149
150-152
153
155
158
159
162
164
165-168
168-169
171
173
175
177
178
181
182
183
184
185
187
188
191
192
193
(continued)
256
Compound
2-me.thylhexane
3-methylhexane
C-.H., (isomer)
CRH, , (isomer)
trichloroethylene and 4,4-
dimethyl-1-pentene and
n-heptane
CnH, , (isomer)
o lo
methyl methacrylate and
CgH16 (isoraer)
C H,, (isomer)
C0H, o (isomer)
o lo
CpJL , (isomer)
CoK, R (isomer)
toluene
2 , ^'-dimethylhexane
CftH1 , (isoraer)
ji-octane
hexamethylcyclotrisiloxane (BKG)
tetrachloroethylene
CqH«,. (isomer)
C_H18 (isomer)
€(,11,0 (isomer)
chlorobenzene
CqH o (isomer)
C9H2Q (isomer)
ethylbenzene
_p-xylene
CQ!^ (isomer)
styrene
jr»-noriane &nd o-xylene
-------
Table 59 (cont'd)
Chromatographic
Peak No.
39
40
41
42
43
45
46
47
48
49
50
51
53
Elution Temperature
(°C)
199
200
202
205
206
207
208
212
213
216
218
223
225
228
229
235
Compound
Ci()H,2 (isomer)
C10H22 (isomer)
C10H2(J (isomer)
n-propyl benzene
benzaldehyde
ethyl toluene
oc.tamethylcyclotrisiloxane
n-decane
1,2,4-trimethyl benzene
m-dichlorobenzene
1,2,3-trimethyl benzene
C,-alkyl benzene
CliH20 (isomer>
C1,H00 (isomer)
ai L.L
n-undecane
C,-alkyl benzene
aSee Table 35 (S4) for sampling protocol.
257
-------
Table 60. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR NEAR
CELANESES CORPORATION, NEWARK, NEW JERSEY3
Chroma tographic
Peak No.a
1
2
2A
3
4
5
6
7
8
9
10
11
12
12A
12B
13
13A
14
15
16
17
18
19
20
21
22
23
24
25
25A
Elution Temperature
81
83
83
88
89
91
93
97
99
103
105
108
110
110
110
113
113
116
119
123
125
126
129
130
133
136
139
141
144
144
(continued)
258
Compound
CF2C12
methyl chloride
n-propane
1-butene
n-butane
2-butene
acetaldehyde
ethyl chloride
methyl bromide
isopentane
trichlorofluoromethane
n-pentane
propanal
furan
dimethyl ether
acetone
methylene chloride
C,H.. . isomer
6 14
isopropanol
CyH.., isomer
vinyl acetate
C,H . isomer
b
perfluorobenzene (I).1
n-hexane
chloroform
perfluorotoluene ($)
2-butanone
1 , 1, 1-trich lor oe thane
benzene
carbon tetrachloride
0
yg/m
57
;37
200
300
-------
Table 60 (cont'd)
Chromatographic
Peak No.a
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
41A
42
43
44
45
46
47
48
49
49A
50
51
52
53
54
Elution Temperature
<°C)
145
148
149-166
168
170
172
176
177
178
183
185
188
190
191
194
195
195
201
202
204
205
207
209
212
214
214
217
218
220
221
224
(continued)
259
3
Compound yg/m
cyclohexane
C..H..., isomer
/ ID
methyl acrylate 4,545
n-butyl acetate 113
toluene
C0Hn/. isomer
o ID
n-octane
CoH.,,. isomer
o ID
tetrachloroethylene
C9H20 lsomer
chlorobenzene
e thylb enz ene
£-xylene
n-butyl acrylate 17
styrene
o-xylene
n-nonane
cumene
C10H22 lsomer
C1()H22 isoiner
n-propylbenzene
m-ethyltoluene
1 , 3 , 5- trime thy Ibenzene
£-ethyltoluene
1,2, 4- trime thy Ibenzene
n-decane
m-dichlorobenzene
C,-alkyl benzene
1, 2, 3- trime thy Ibenzene
C11H24 isomer
C,-alkyl benzene
-------
Table 60 (cont'd)
Chroma tographic
Peak No.a
55
56
57
58
59
60
61
62
63
64
65
66
Elution Temperature
225
227
229
231
233
235
238
239
240
240
240
240
o
Compound yg/m
C,-alkyl benzene
c*cetophenone
C,-alkyl benzene
n-undecane
C11H22 lsomer
C.. ~H,,, isomer
C,-alkyl benzene
C,-alkyl benzene
C,.-alkyl benzene
^12H26 *somer
ri-dodecane
naphthalene
See Table 35 (S5) for sampling protocol.
260
-------
Table 61. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR IN STATEN ISLAND, NY'
Chroma to^raphic
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
Elution Temperature
(°C)
72
73
80
85
92
97
98
102
104
106
108
111
112
115
117
122
126
127
129
131
134
3.37
140
142
144
145
.146
147
149
151
153
(continued)
261
Compound
V °2
co2
CC12F2 (Freon 12)
iscbutane
acetaldehyde
CHFC12
CH NR2 or CHCH2NH2 (tent.)
Ct-H ~ isomer
CFC13 (Freon II)
acetone
methyl n-propy.L ether
CI12C12
2-met.byoxyel:hyl acetate
diraethyl butane iscr.ier
2-pentanol (tent.)
C,H.. , isomer
6 14
C H isomer
C6F6
C.,H, , isomer
CHC13
C7F8
n--butyl acetate
2-cbloroethyl acetate
1,1,1-trichloroethane
benzene
cci4
2, 3-din'.ethylpcrtnf.?
C,H10 isomer
D 1 I
C-,ni, isorrier
i lo
t rimetuy Ipcntane
C..H., ison'.er
/ lo
-------
Table 61 (cont'd)
Chroma tographic
Peak No.
33
33A
34
35
36
36A
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
51A
54
55
56
56A
56B
58
59
60
60A
61
Elution Temperature
154
154
160
162
163
163
165
166
168
170
172
174
176
178
186
188
190
193
195
196
201
201
208
212
214
214
214
220
222
223
223
225
Compound
isoamyl nitrile
C-.H- .. isomer
7 16
C Hn , isomer
7 14
CDHnQ isomer
8 18
CnHno isomer
9 18
C0H, Q isomer
9 18
C10H20 ls°mer
C0H, „ isomer
8 18
toluene
C^H., 0 isomer
8 18
C-.H-, , isomer
8 16
CnH.,0 isomer
8 18
hexamethylcyclotrisiloxane (BKG)
tetrachloroethylene
chlorobenzcne
ethylbenzene
j>- xylene
styrene
o-xylene
C10H20 is°mer
isopropylbenzene
n-decyl chloride
acetophenone
trimethylbenzene
:n-decane
trimethylbenzene
C....H isomer
C10H22 isomer
C^-H™ isomer
C- ,H, . isomer
11 j.4
C^-jH^ isomer
C.-alkyl benzeiife
(continued)
262
-------
Table 61 (cont'd)
Chromatographic
Peak No.
62
62A
63
64
65
65A
66
67
Elution Temperature
(°C)
227
227
228
230
231
231
238
240
Compound
C, ,H ,„ isomer
C,-alkyl benzene
decamethyl cyclopentasiloxane
acetoxypropyltridecaue (tent.)
C,-alkyl benzene
C11H20 isomer
C1]H20 isomer
phenoxydiphenylether (tent.)
1See Table 35 (S6) for sampling protocol.
263
-------
Table 62. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR IN FORDS,
Chroma tographic
Peak No.
1
2
3
4
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
Elution Temperature
60
62
68
72
77
81
88
90
94
98
100
101
104
108
112
114
116
118
119
121
126
130
133
137
138
145
146
148
150
152
157
158
(continued)
264
Compound
N2, O,
co2
CF2C12
isobutane
chloropropane (tent.)
acetaldehyde
isopentane
CC13F
r H
SU12
CH2C12
dimethylbutane
diethyl ether
acetone
methylpentane
trimethylpentane
perf luorobenzene
u_- il ._ *
7 14
CHC13
diethyl sulfide
perf luoro toluene
1,1, 1-trichloroethane
benzene
C-.H.. , isomer
7 16
C0H10 isomer
8 18
C H, ,. isomer
7 16
methylethylcyclopentane isomcr
CgH „ isomer
CQH isomer
9 18
Cf.ll , isomer
toluene
CjjlL . isomer
C0H isomer
8 18
-------
Table 62 (cont'd)
Cliromatographic
Peak No.
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
EC
61
62
63
64
Elution Temperature
159
161
165
169
172
173
178
179
179
180
182
184
188
189
190
191
193
197
200
202
206
207
208
209
211
211
213
214
215
217
218
220
(continued)
265
Compound
hexamethylcyclotrisiloxane (BKG).
tetrachloroethylene
CqH^ isomer
chlorobenzene
ethylbenzene
xylene
cyclooctatetraene
xylene
C-H^- isomer
9 20
CqH_.. isomer
ditolyl ether (?)
C_-alkyl benzene
CqH-,. isomer
C^-alkyl benzene
oc tame thy Icyclotetrasiloxane (BKG)
benzaldehyde
C, -alkyl benzene
C_-alkyl benzene
CqH o isomer
dichlorobenzene
C, -alkyl benzene
C -alkyl benzene
-3
C,-alkyl benzene
CqH1R isomer
C. -alkyl benzene
tolualdehyde
C -nlkyl styrene (tent.)
C11H24 is°mcr
methyl benzoate (tent.)
C, -alkyl benzene
dichlorotoluene (tent.)
t-butyl methyl ether (tent.)
-------
Table 62 (cont'd)
Chromatographic
Peak No.
65
66
67
68
69
70
71
Elution Temperature
224
225
226
229
232
233
237
Compound
C,-alkyl benzene
trimethyl-1-methylethoxy-
silane
Cp-alkyl benzene
C12H26 is°mer
naphthalene
methyl methyl benzoate
C13H28 isoraer
See Table 35 (S8) for sampling protocol.
266
-------
Table 63. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR IN BOUNDBROOK, NJa
Chromatographic
Peak No.
1
2
3
3A
3B
4
5
6
6A
6B
6C
7
8
9
10
11
12
13
1 L
J-H
15
15A
16
17
18
18A
19
20
2]
22
Elution Temperature
( C) Compound
63-4
68
74
75
76
80
86
87
90
91
92
96
100
106
110
112
115
118
123
127
128
130
132
133
134
135
139
141
144
dif luordichlorome thane
propane
1-butene
n-butane
2-butene
acetaldehyde
: isopentane
chloroethane and trichloro-
f luormethane
furan
CrH1f. isomer
n-pentane
dichlorome thane
propanal
2-methylpentane
ter-butanol and 3-methylpentane
f*
hexafluorobenzene and ri-hexane
chloroform
£
perf luorotoluene
1,2-dichloroethane and 1,1,
trichloroathane
benzene
carbon tetrachloride
1-
CyHig isoir-er and cyclohexane
isopropyl acetate
trichloroeLhylene and iv-heptane
ethyl aery late
2 , 2-diniethyl-3-hexane
diisobutylene
dimethylcyclohexane isoroer
C^IL, iscmer
/ 10
(continued)
267
-------
Table 63 (cont'd)
Chromatographic
Peak No.
23
24
25
26
26A
27
28
28A
29
30
30A
31
32
32A
33
34
34A
34B
35
37
38
39
40
41
42
42A
43
43A
44
Elution Temperature
145
148
150
153
155
156-7
158-60
160
165-8
169
168
171
172
173
175
176
177
178
181
185
187
188
189
191
194
197
198
199
200
(continued)
268
Compound
methyl methacrylate
dimethylcyclohexane isomer
toluene
dimethylcyclohexane isomer
C0H-. isomer
o J.4
n-octane
silane compound and tetra-
chloroethylene
2-hexanone
chlorobenzene
ethyl benzene
pyridine (tent.)
£-xylene
dibutyl ether
C0H10 isomer
y J.o
styrene
n-nonane and o-xylene
C_H „ isomer
CQH.., isomer
isopropylbenzene
n-propylbenzene
m-ethyl toluene
phenol
benzaldehyde
silarie compound
1,2,4-trimethylbenzene and
n-decane
aniline
m or p-dichlorobenzene
^11^24 i-somer
1,2,3-trimethylbenzene and
2-methyl-2-pentcnal (cent.)
-------
Table 63 (cont'd)
Chromatographic
Peak No.
44A
45
45A
46
46A
47
47A
48
48A
49
50
51
52
53
54
56
57
58
59
60
Elution Temperature
202
203
204
205
206 ,
207
208
211
212
214
217
218
222
227
229
233
240
240
240
240
Compound
CUH20 isomer
o-dichlorobcnzene
sec-butylbenzene
m-diethylbenzene
N-methylaniline
acetophenone
fluoranisole (tent.)
nitrobenzene and n-undecane
dimethylaniline isomer
C/-alkyl benzene isomer
chloroaniline isomer
silane compound
C12H24 isomer
1,3, 5-trichlorobenzene
naphthalene
1,2,4-trichlorobenzene
a-naphthylamine
3-methylnaphthalene
a-methylnaphthalene
2-ethyl quinoline
aSee Table 35 (S9) for sampling protocol.
269
-------
Table 64. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR IN EL SEGUNDO, CAC
Chromatographic
Peak No.
3
4
6
7
8
8A
9
12
14
15
16
16A
16B
17
18
18A
19
19A
20
21
22
22A
23
24
24A
25
26
27
28
Elution Temperature
42
45
48
50
51
51-3
52
55
60
61
62
63
63
64
65
66-76
68
69
77
80
81
82
83
84
85
86
87
88
89
(continued)
270
Compound
co2
dichlorodif luorme thane
propane
1-butene
n-butane
SO
2
2-butene
acetaldehyde
isopentane
trichiorofluormethane
CJH (isomer)
furan
Ci-H (isomer)
_> 1U
iv-pentane -h propanal
dimethyl ether
acetone
dichloromethane
C,H10 (isomer)
o 12
2-methylpentane
3-methylpentane
C-H., _ (isomer)
o 12
C,H . (isomer)
hexaf luorobenzene (S)
n-hexane
C,H-2 (isomer)
chloroform
C,}{.~ (isomer)
methyl ethyl ketone
C.-H. o (isoniGr)
D 12
-------
Table 64 (cont'd)
Chromatographic
Peak No.
29
30
31
32
33
34
35
36
37
39
40
41
41A
4 IB
42
43
43A
44
44A
45
46
46A
46B
46C
47
48
49
50
51
51A
Elution Temperature
90
92
93
94
97
98
101
102
103
105
106
107
108
108
109
111
112
113
114
116
117
117
118
118
119
120
112
124-5
125
126
(continued)
271
Compound
perf luorotoluene (S)
methylcyclopentane
1 , 2-dichloroethane
1,1, 1-trichloroethane
C,Hin (isomer) and C-H.. (isomer)
O JLU / J.4
benzene and carbon tetrachloride
cyclohexane and 2-methylhexane
isopropyl acetate
3-methylhexane
dimethylcyclopentane isomer
dimethylcyclopentane isomer
trichlorcethylene
C7H19 (isomer) and C7H.., (isomer)
/ J_^ / -L'r
3-methyl butanol (tent)
n-heptane
3-pentanone
2-pentanone
2,4-dimethyl furan
n-propyl acetate
methylcyclohexane
CoH,a (isomer)
C-H.. f (isomer)
8 lo
2,4-dimethylhexane
C H.J, (isomer)
4-methyl-2-pentanone
C0H1C (isomer)
8 16
CQHIA (isomer)
o J-0
toluene (isomer)
C0H,0 (isomer)
li IB
CQE., (isomer)
o 10
-------
Table 64 (cont'd)
Chromatographic
Peak No.
52
53
53A
54
55
56
57
58
59
60
61
62
62A
63
64
65
65A
65B
66
66A
67
68
69
70
71
71A
72
7? A
Elution Temperature
127
129
129
130
130-2
132
134
136
138
140
141
142
142
143
144
147
148
148
149
150
151
152
153
154
155
15G
157
158
Compound
3-:Tiethylheptane
3-hexanone
CnH. , (isomer)
o 14
dimethylcyclohexane isomur +
dimethylnitrosamine (tent.)
N,N-dimethyl formamide
CRH, , (isomer)
n-octane
tetrachloroethylene
hexamethylcyclotris iloxane ( BKG)
CqH.jn (isomer)
C..H, , (isomer)
CgH20 (isomer)
dimethylcyclohexane isomer
4-hydroxy-4-methyI-2-pentanone
(tent) + chlorobenzene
C9H18 (isomer)
ethylbenzene
CnK10 (isomer)
y lo
CgH2Q (isomer)
p-xylene
CgH2Q (isomer)
CgH?_ (isomer)
C-H,,. (isomer)
styrene
C-H, .. (Isomer)
y J-O
o-xylene
C9H18 (i-raer)
n-nonane
C.H10 (isomer)
(continued)
272
-------
Table 64 (cont'd)
Chromatographic
Peak No.
73
74
75
76
77
78
78A
78B
79
79A
80
81
82
83
84
85
86
87
88
89
90
91
92
93
93A
94
94A
95
95A
Elution Temperature
(°C)
159
160
161
162
162
163
163
164
164
165
165
166
168
170
170
171
172
173
174
175
176
177
178
179
179
180
181
181
182
Compound
CM IT Qom°Y" I
-I pv1**}/"* ^J_OWLU\^l. 1
-LU ZU
methylethylcyclohe::ane isoraar
C H?? (isomer)
isopropylbenzene
C « .. H/> ~ ( isomer )
10 22
Cn-Hnrv (isoroer)
10 20
CqH, „ (isomer)
CqHj-. (Isomer)
C1,.H«« (isomer)
10 22
propylcyclohexane + C H iscr.er
C,«H«n (isomer)
10 22
C1f)H20 (isomer^
benzaldehyde + n-propyl benzene
m-ethyl toluene + G ,!!„„ (isomer)
C10H22 (isomer)
1,3, 5-trimethylbenzene
C30H2'> ^isomer^
cyanobenzene or phenylisocyanide
o-e thy 1 toluene
Cir.Hor. + C H1Q (isomer)
10 20 10 18
C. -alkyl cyclohexane (isomer)
1,2,4-trime.thylbenzene
n-decane
phenol
C, nKon (isomer)
10 20
m-dichlorobenzene -1- C^H ,0 (isoraer
+ isobutylbensene
sec-butylbenzene
C11H24 (isomer)
o-cymene
(continued)
273
-------
Table 64 (cont'd)
Chroma tographic
Peak No.
96
97
98
98A
99
100
100A
101
102
103
104
105
106
107
108
108A
109
110
110A
111
112
113
114
11 4A
115
115A
116
116A
117
117 A
Elution Temperature
182
183
184
185
186
187
188
188
188
189
190
191
192
194
195
196
197
199
199
200
201
202
203
204
205
205
206
2.06
207
207
(continued)
274
Compound
CTJ / -i -» « •*•» \
, . H- , (.isomer )
11 24
1,2,3-trimethyl benzene
S.-H-, (isomer)
C H (iscmer)
11 22.
o-dichlorobenzene
indan + C.-alkyl cyclohexane
(isomer)
C11H22 (isomer)
C,-alkyl benzene (isomer)
C.-alkyl benzene (isomer)
C.-alkyl benzene (isomer)
acetophenone
C H (isomer)
11 il
C H-. (isomer)
11 24
C,-alkyl benzene (isomer)
C,-alkyl benzene (isomer)
C H (isomer)
11 il
n-undecane
C,.-alkyl benzene (isomer)
CnoH0, + C1 -H^,, (isomer)
1Z zt> 11 zz
C.^H,,- + C.-alkyl benzene (isomers)
C^H^, (isomer)
1,2,4,5-tetramethylbenzene
^i o^n - (isomer)
12 2o
C_-alkyl benzene (isomer)
C,_H1,0 (isomer)
lu ID
^12H22 (isoraer)
C^-alkyl benzene (isomer)
C5~alkyl cyclohexane (isomer)
methyl indan (isomer)
C,-alkyl benzene (isoraer)
-------
Table 64 (cont'd)
Chromatographic
Peak No.
118
119
119A
120
121
122
123
123A
124
125
125A
125B
126
127
128
130
131
133
133A
134
135
136
137
138
142
143
Elution Temperature
(°C)
208
209
209
210
211
212
213
213
214
216
217
217
218
220
221
225
226
229
230
231
233
235
236
239
240
240
Compound ;
C-nH-,,- (isomer)
12 2b
methyl indan (isomer)
C^-alkyl benzene (isomer)
CT 0H0 , (isomer)
12 24
^12H26 (isoiner)
C^-alkyl benzene (isomer)
C12H22 (isomer)
C,-alkyl benzene (isomer)
C 12H2A + dimethyl indan (isomers)
n-dodecane + naphtalene
C12H24 (isomer)
dimethyl indan (isomer)
C13H28 (isomer)
C13H28
-------
Table 65. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR IN TORRANCE, CAC
Chromatographic
Peak No.
1
2
3
4
5
6
*
7
8
9
10
11
1.1A
11B
12
12A
13
13A
14
14A
ISA
15B
15C
16
17
17A
18
19
20
20A
Elutiou Temperature
41
45
47
48
50
50
51
52
56
57-59
60
62
63
63
64
65
66
67
68
69-76
77
78
80
82
83
84
85
85
86
87
(continued)
276
Compound
co2
dichlorodifluormethane
chloromethane
n-propane
so2
1-butene
n-butane
2-butene
acetaldehyde
background
isopentane
trichlorof luormethane
C5H10 (isomar)
furan + C^H-,-. (isomer)
n-pentane
CrHin (isomer)
propanal
CcHin (isomer)
dichlororr.ethanc
acetone
C/^H..- (isomer)
2-methylpentane
C,-H, ~ (isomer)
3-methyl-pentane
C16H12 (isomer)
C^,R.j (isomer)
hexaf luorobenzene (30
•n-hexane
chloroform
C6H12 (isomer)
-------
Table 65 (cont'd)
Chroma tographic
Peak No.
21
21A
22
23
24
24A
25
26
27
28
28A
29
30
31
32
33
34
35
36
37
38
39
40
41
42
42A
43
44
45
Elution Temperature
(°C)
88
90
92
93
94
95
96
98
99
100
101
102
103
104
106
108
110
112-114
116
117
119
121
123
125
126
128
130
132
(continued)
277
Compound
methyl ethyl ketone
C H (isomer)
o 12
perf luorotoluene (3)
• methylcyclopentane
1 , 2-dichloroethane
C-.IL, (isomer)
/ ID
1,1 jl-trichloroethane
1,1-dichloropropene + C ,H.. ~ +
C9H14 (isomers)
benzene
carbon tetrachloride
cyclohexane
2-methyl hexane
C-.H,, (isomer)
/ ID
3-methyl hexane
trimethyl pentane + C^i^ (isonerr;)
unknown
trichloroethylene
n-heptane
2-pentanone + ethyl hydrazine
C0H1Q (isomer)
o io
methyl cyclohexane
C8H18 (isomer)
chloral
CQHT<; (isomer)
8 ID
toluene
C8H18
3-methy.lhenrane
dimethylcyclohexane isomer
4-methyl-2-pentanone + 2,5-
dimethyl-2 , 4-hexadiene
-------
Table 65 (cont'd)
Chrcmatographic
Peak No.
46
47
47A
48
49
50
51
52
52A
53
53A
53B
54
55
56
57
58
58A
59
59A
60
60A
61
62
62A
63
64
64 A
Elution Temperature
133
134
135
136
138
140
141
143-146
147
148
149
149
150
151
153
154
155
156
157
158
159
160
161
162
163
163
164
165
(continued)
278
Compound
1,1, 2-trichloropropene + C,H, r
/ • \ o ID
(isomer)
n-octane
CRH.. , (isomer)
tetrachloroethylene
silane compound
CqH20 (isomer)
C9H20 (isomer)
chlorobenzene
trichloropropene (isomer)
ethyl benzene
C9Hlg (isomer)
CgH2() (isomer)
p-xylene
dimethylheptane isomer
CqH.... (isomer)
styrene
o-xylene
CqH, o (isomer)
n-nonane
CqH, j, (isomer)
C ir,H_-. (isomer)
C0II1S (isomer)
ClOH22 isomer + 1,2,3,3-tetra-
chloropropene
isopropylbenzene + C1 H^o isor.u
-*- \J
C,_H00 (isomer)
J.U it.
tetrachloropropane (isomer) +
3 , 3 , 5-trinethylhopt r.ne
3-methylnonanc
Ci0H20 (isomer)
-------
Table 65 (cont'd)
Chromatographic
Peak No.
65
66
66A
67
68
69
69A
70
71
73 A
72
73
74
75
76
76A
77
78
79
80
80A
SOB
81
81A
82
82A
82
84
85
Elution Temperature
(°C)
165
166
167
168
169
170
170
171
172
173
174
175
176
177
178
179
181
182
183
184
184
185
186
187
188
188
189
190
191
(continued)
279
Compound
propylcyclohexaue
C10H22 (isomer)
C10H20 (isomer)
n-propylbenzene + benzaldehvde
m-ethyl toluene
C10^22 (isoraer)
1, 3, 5-trimethylbenzene
C _H__ (isomer)
C10H20 (isomer)
cyanobenzene (tent)
o- ethyl toluene
octamethylcyclotetrasiloxane
(BKG) + Cj_oH2o + cioH13 isomers
C10K2Q (isomer)
1, 2,4-trimethylbenzene
n-decane
C1()H20 (isomer)
m-dichlorobenzene
C,-alkyl benzene isomer
C11H24 (isomer)
1,2, 3-tr imethylbenzene
C11H24 (isomer)
C1;LH24 (isomer)
o-dichlorcbenzene
indan + C/,-alkyl cyclohexane isomer
o-cymene + C n^ (isomer)
sec-butylbenzene
C.-alkyl benzene isomer
acetophenone
C....H,,, (isomer)
ii. — H
-------
Table 65 (cont'd)
Chroma tographic
Peak No.
86
87
88
88A
89
89A
90
91
91A
92
93
93A
93B
94
95
95A
96
96A
97
97A
98
98A
98B
98C
99
99A
100
Elution Temperature
192
194
195
196
197
198
199
200
201
202
203
203
204
205
206
206
207
207
207
208
209
209
210
210
2.11
211
212
(continued)
280
Compound
C11H24 + C/j-alkyl benzene
isomers
C4~alkyl benzene + C H
isomers
methyl indan + C12H24 (is°mers)
C..,H22 (isorner)
n-undecane
C11H22 (lsomer)
C5~alkyl benzene + C H ,
(isomers)
C/,-alkyl benzene + C,?H isomers
C,/)H26 (isomer)
m-chlorobenzaldehyde
C,-alkyl benzene (isomer)
C..-H,,, (isomer)
12 Zb
C^H^A + C jH^j (isomers)
Chalky] benzene + C H (isomers)
trichlorobenzene isomer
C^-alkyl cyclohexane (isomer)
methyl indan + C-,2H2A (isomers)
C15-alkyl-benzene (isomer)
C,2-H2fi (isomer)
C12H24 + C -alky] benzene
isomers
methyl indan (isomer)
C^-alkyl-benzene (isomer)
C.. -H,., . (isomer)
C,-alkyJ benzene (isomer)
C^-alkyl benzene (isomer)
C- -.H ^ / (isomer)
12 24
^13^28 "*" ^5~a^ky-' benzer.e (isomers)
-------
Table 65 (cont'd)
Chroma tographic
Peak No.
101
102
103
103A
103B
104
105
106
106A
107
108
109
110
111
112
113
114
115
116
Elution Temperature
214
215
216
217
217
218
219
221
223
225
227
228
232
234
236
238
240
240
240
Compound
Uricblorobenzene isomer
n-dodecane
naphthalene
C -alkyl benzene (isomer)
dimethyl indan (isomer)
C..-H~O (isomer)
13 28
C -H , (isomer)
trichlorobenzene (isomer)
C...VL, (isomer)
GI H?, (isomer)
C13H28 (isomer)
C14H30
-------
Table 66. ORGANIC VAPORS IDENTIFIED IN AMBIENT AIR FROM TORRANCE, CAa
Chroma tographic
Peak No.
3
5
6
8
9
10
11
12
13
14
14A
14B
15
15A
16
17
17A
17B
18
19
20
21
22
23
23A
24
25
26
27
28
30
31
Elutiori Temperature
43
45
46
48
50
50
51
54
56
57
58
59
60
61
62
64
66
68
74
77
78
80
81
82
83
84
87
88
90
91
94
95
(continued)
282
Compound
CO,
cyclopropane
difluorodichlorome thane
propane
1-btitene
n-butane
2-butene
acetaldehyde
C,H0 iscmer
4 o
isopentane
trichlorof luoromethane
Cj-H-.-. iso;ner
furan and C_H1f. isomer
ii-pentane
propanal and dimethyl ether
acetone and dichloromethane
methyl silane
C,H.._ isomer
b 12
2-methylpentane
3-methylpentane
C,H, isomer and C-Hn , isomer
b 12 6 IM
he.xafluorobenzene (Std.)
n-hexane
chloroform
2-methylfuran
methyl ethyl ketoiie
per fluoro toluene (Std.)
methylcyclopentane
1, 2-dichlc'roethane
1,1, 1-tr ichloroethaue
^6^10 i^oniir and ^7^1 /. isomer
benzene
-------
Table 66 (cont'd)
Chroma tographic
Peak No.
32
33
34
35
35A
36
37
37A
38
38A
39
40
41
42
43
44
45
47
48
49
50
51
51A
52
53
54
55
56
57
58
Elution Temperature
(°C)
97
98
99
101
102
103
104
104
105
105
106
107
109
113
114
115
117
119
121
124
125
126
128
129
130
131
133
135
136
138
(continued)
283
Compound
carbon tetrachloride
2-methylhexane
2 , 3-dimethylpentane
C H isomer
3-methylhexane
C7H , isomer
1,2-dimethylcyclopentane
C^H- . isomer
trichloroethylene
C_H1 „ isomer
2-aminopentane (tent.)
n-heptane
2-pentanone and 2,4-dimethyl-
furan
2, 2,4-trimethylpentane
met.hylcyclohexane
C8Hlg isomer
C?H , isomer
4-methyl-2-pentanone
C0H , isomer
o ID
toluene
C0H10 isomer
o lo
2,4-dimethylhexane
C0H.., isomer
o lo
dimethylcyclohexane isomer
2-hcxanone and CgH^ isomer
methylcthylcyclopentane
isomer
n-octane
tetrachlorocthylene
hexaracthylcyclotrisiloxane
C9H18 isomer
-------
Table 66 (cont'd)
Chromatographic
Peak No.
59
59A
60
61
62
63
64
65
65A
66
67
68
68A
69
69A
70
70A
71
71A
72
73
73A
74
75
76
77
78
79
80
81
Elution Temperature
139
140
141
142
143
144
145
147
148
148-50
151
152
153
153
154
155
156
157
158
159
161
161
162
163
164
165
166
166
167
169
(continued)
284
Compound
C0Hor. isomer
9 20
C9H18 isomer
CnH,,n isomer
9 20
CnHori isomer
9 20
dimethylcyclohexane isomer
chlorobenzene
1,2, 3-trimethylcyclohexane
ethylbenzene
CnH.. , isomer and CnHn 0 isomer
9 16 9 18
^ and m-xylene
C_H^- isomer
9 20
N,N-dimethylformamide
C-,H, , 0 isomer
7 14
styrene
C^H., 0 isomer
9 18
jD-xylene
methylethylcyclohexane
isomer
n-nonane
C_H, „ isomer
9 18
C,^H-_ isomer
10 20
methy lethylcyc lohexane
isomer
^10^22 ^somer
isopropylbenzene
C10H22 isomer
C-H.. , isomer
9 16
€.._{}-„ isomer
propy] cyclohexanc
C.-H-., isomer
benzaldehyde
n.-propylbenzene
-------
Table
66 (cont'd)
Chromatographic Elution Temperature
Peak No. (°C) Compound
82 170
82A 171
83 172
84 173
84A 173
84B 174
85 175
86 176
87 177
88 178
89 179
90 180
91 181
91A I82
92 182
92A 183
93 183
94 "4
95 I85
95A I86
96 187
97 I87
97A ' 188
97B I88
98 189
99 189.5
100 19°
1 01
101 ±Jl
102 . I92
103 I93
m-ethyltoluene
C-^H^. isomer
10 22
1,3, 5-trimethylbenzene
C10H22 isorner
cyanobenzene (tent.) and
C-ir.Hor. isomer
10 20
2-octanone (tent.)
o-ethyltoluene
C10H20 isomer
1-decene
1, 2,4-trimethylbenzene
n-decane
phenol
isobutylbenzene and £-\^2Q
isomer
sec-butylbenzene
C11H22 isomer
C,-alkyl benzene isomer
C11H24 isomer
1,2,3-trimethylbenzene
C 11B24 i30rner
C11H22 is°mer
o-dichlorobenzene
indan
C,-alkylcyclohexane
C11H22 isomer
£-propyltoluene
diethylbenzene isomer
n-butylbenzene
acetophenone
C11H22 isonier
o-propyltoluene
(continued)
285
-------
Table 66 (cont'd)
Chroma to graphic
Peak No.
104
105
106
107
107A
108
109
110
111
112
113
114
115
116
117
118
118A
119
11 9A
120
120A
121
122
123
124
125
Elution Temperature
195
195
196
197
198
199
200
201
202
203
204
205
205
207
208
209
210
210
211
212
213
213
214
215
216
217
(continued)
286
Compound
dimethylethylbenzene isomer
C....H,.,,, isomer
dimethyl ethylbenzene isomer
methyl indan isomer
C11H22 isomer
n-undecane
C_-alkyl benzene isomer
C,-alkyl benzene isomer +
C,..H?? isomer
C12H24 isomer
C-.0H0, isomer
14. 2o
1,2,4, 5-tetramethylbenzene
C12H26 isOmer
C,--alkyl benzene isomer +
C....H-,. isomer
C,.-alkylcyclohexane isomer
methyl indan isomer or C H
+ C, 2^TA isomer
C12H26 is°mer
C H2 isomer
C QH 2 isomer or methyl indan
isomer
tetramethylbenzene isomer +
Cr-alkyl benzene isomer
C,--alkyl benzene isomer
CnoH0, isomer
12 zo
C^-alkyl benzene isomer
C,-allcyl benzene isomer
C-.-H.j. isomer
1-dodecene + dimethyl indan
isomer
ii-dodecane
-------
Table 66 (cont'd)
Chroma to graphic
Peak No.
126
126A
126B
127
128
129
130
131
132
134
135
136
137
138
139
140
141
142
143
144
145
146
148
150
J- -s \t
152
Elution Temperature
(°C)
218
218
219
220
221
223
224
225
227
228
229
230
231
232
234
236
237
237
238
240
240
240
240
240
240
240
Compound
naphthalene
Cr-alkyl benzene isomer
dimethylindan isomer
CR28 isomer
C,-alkyl benzene isomer
CnoH0, isomer
13 2o
C,-alkyl benzene isomer
benzothiazone (tent.)
C13H26 isomer
dimethylindan isomer
cnHi£ isomer
13 /b
C14H30 is°mer
C14H28 iS°mer
C13H26 is°mer
n-tridecane
trimethylindan isomer
B-methylnaphthalene
C14H30 ls°mer
C14H30 isomer
ct-methylnaphthalene
C14H30 iS°mer
C14H28 iS°mer
C14H30 iS°mer
C15H32 isomer
n-tetradecane
dimethylnaphthalene isomer +
Vi-t nhp.nvl
aSee Figure 31 and Table 35 (32, Van Ness
dimethylnaphthalene isomer
Blvd.) for sampling protocol
287
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
W7-77-055
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
THE MEASUREMENT OF CARCINOGENIC VAPORS IN AMBIENT
ATMOSPHERES
5. REPORT DATE
June 1977
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S)
Edo D. Pellizzari
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
Research Triangle Park
North Carolina 27711
10. PROGRAM ELEMENT NO.
1NE 625 EB-07 (FY-7.7)
11. CONTRACT/GRANT NO.
68-02-1228
12. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
Environmental Sciences Research Laboratory- RTP, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Final 6/75 - 6/7fi
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
^Analytical techniques and instrumentation, which had been developed during the ;
previous contract years, were further evaluated for the collection and analysis of
carcinogenic and mutagenic vapors occurring in ambient air. The areas of investigatioi
included (a) the development of a permeation system for delivering precise quantities
of organic vapors for calibrating instruments, (b) the development of procedures for
the preparation of glass capillary columns for effecting the resolution of complex
atmospheric vapor mixtures, (c) the characterization of organic vapor emissions from
preset controlled fires, (d) the survey of ambient air samples taken at various sites
around the continental U.S. for the detection of N-nitrosoamines, (e) the identificat-
ion and quantification of N-nitrosodimethylamines in samples collected in Baltimore,
MD and the Kanawha Valley, WV, and (f) the characterization of ambient air for hazard-
ous and background pollutants from several geographical areas within the continental
U.S.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. cos AT I Field/Group
Air pollution
Collection methods
Carcinogens
Vapors
Gas chromatography
Mass spectrometry
13B
06E
07D
14B
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
302
20. S
Tils page)
22. PRICE
EPA Form 2220T-1 (9-73)
288
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