Environmental Protection Technology Series
DEVELOPMENT OF
ANALYTICAL TECHNIQUES FOR
MEASURING AMBIENT ATMOSPHERIC
CARCINOGENIC VAPORS
Environmental Sciences Research Laboratory
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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
five series. These five broad categories were established to
facilitate further development and application of environmental
technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in
related fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to
develop and demonstrate instrumentation, equipment and methodology
to repair or prevent environmental degradation from point and non-
point sources of pollution. This work provides the new or improved
technology required for the control and treatment of pollution
sources to meet environmental quality standards.
This document is available to the public through the National
Technical Information Service, Springfield, Virginia 22161.
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EPA-600/2-75-076
November 1975
DEVELOPMENT OF ANALYTICAL TECHNIQUES FOR
MEASURING AMBIENT ATMOSPHERIC CARCINOGENIC VAPORS
by
Edo D. Pellizzari, Ph.D.
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-02-1228
Project Officer
Dr. Eugene Sawicki
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 27711
U. S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
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, developed during the
previous contract year, were perfected and evaluated for the collection
and analysis of carcinogenic and mutagenic vapors occurring in ambient
air. The areas of investigation included (a) the performance of a
sorbent cartridge sampler for hazardous vapors occurring at concentra-
3
tions of ng/m ; (b) the design, fabrication, and performance of a
portable field sampler; and (c) the identification of hazardous and
background pollutants from several geographical areas in the Continen-
tal U. S.
iii
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CONTENTS
Page
Abstract iii
List of Figures v
List of Tables vii
Acknowledgements x
Sections
I Conclusions 1
II Recommendations 3
III Introduction 5
IV Program Objectives 9
V Performance of Sorbent Cartridge Sampler
for Hazardous Vapors 10
VI Design and Performance of a Portable
Field Sampler 41
VII Identification of Hazardous and Background
Pollutants from Several Geographical Areas.
in the Continental U.S. 50
VIII References 89
IX Appendix 94
iv
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FIGURES
No. Page
1 Linear regression of the elution volume vs_ temperature
for vapors on Tenax GC. 31
2 Relationship between flow rate and theoretical power
requirements at various tube diameters and par-
ticle size. 43
3 Nutech Model 221-A AC-DC Sampler. 45
4 Map of Houston, Texas and Vicinity depicting sampling
sites. 51
5 Map of Los Angeles, CA and Vicinity depicting sampling
sites. 52
6 Map of the Kanawha Valley in West Virginia depicting
sampling sites. 53
7 Total ion chromatogram of Tenax GC cartridge blank. 60
8 Total ion chromatogram of ambient air sample from South
Charleston, WV. 63
9 Total ion chromatogram of ambient air sample from Pasadena,
TX. 65
10 Total ion chromatogram of ambient air sample from Pasadena,
TX. " 67
11 Total ion chromatogram of ambient air sample from Glendora,
CA. 69
12 Total ion chromatogram of ambient air sample from Glendora,
CA. 71
13 Total ion chromatogram of ambient air sample near Burlington
Industries and Mallinckrodt in Raleigh, NC. 82
14 Mass spectrum of chromatographic Peak No. 84 eluting at 194°C
for previous figure. 83
15 Mass spectrum of an authentic sample of biphenyl. 84
16 Mass fragmentograms of unique ions representing carbon tetra-
chloride (m/e 117), tetrachloroethylene (m/e 166) and
m-dichlorobenzene (m/e 146) in ambient air from Glendora,
CA. 86
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FIGURES CONT'D
No.
17 Mass fragmentograms of unique ions representing methylene
chloride (m/e 49) and chloroform (m/e 83) in ambient
air from Glendora, CA. 87
18 Total ion current plot during gas-liquid chromatography
mass spectrometry of air sample from Santa Monica,
CA. 95
19 Total ion current plot during gas-liquid chromatography
mass spectrometry of air sample from West Covina, CA. 99
20 Total ion current plot during gas-liquid chromatography
mass spectrometry of air sample from Glendora, CA. 107
21 Total ion current plot during gas-liquid chromatography
mass spectrometry of air sample from Anaheim, CA. 109
22 Total ion current plot during gas-liquid chromatography
mass spectrometry of night air sample from Anaheim, CA. Ill
23 Total .ion current plot during gas-liquid chromatography
mass spectrometry of air samples from Garden Grove, CA. 113
24 Total ion current plot of ambient air sample taken at May
Street, Houston, TX. 153
25 Total ion current plot of ambient air sample taken at Shaw
Drive, Pasadena, TX. 156
26 Total ion current plot of ambient air sample from Baytown,
TX. 159
27 Total ion current plot of ambient air sample taken in Texas
City, TX. 161
28 Total ion current plot of ambient air sample taken at
Stuebner Airline, Houston, TX. 162
vi
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TABLES
No."
1 Relationship Between Temperature, Water Vapor Pressure,
and Humidity in a Closed Vessel Containing Water. 12
2 Effect of Humidity on Percent Collection Efficiency for
Tenax GC. 15
3 Effect of Humidity on Breakthrough Volumes of Hazardous
Vapors for Tenax GC. 15
4 Volatile Organic Vapor Mixture for Determining Effect of
Repeated Thermal Desorption on Collection Efficiency
of Tenax GC. 17
5 Effect of Repeated Desorption on Percent Collection
Efficiency of Tenax GC Cartridge Samplers. 18
6 Organic Vapors Employed for Study on the Effect of
Transportation and Storage on Sample from Tenax GC. 20
7 Experimental Design for Studying the Effect of Transpor-
tation and Storage on Tenax Cartridges. 21
8 Effect of Transportation and Storage on the Percent
Recovery of Vapors from Tenax GC Cartridges. 23
9 Effects of Transportation and Storage on the Percent
Recovery of Carcinogenic Vapors from Tenax GC. 24
10 Effects of Transportation and Storage on the Percent
Recovery of Carcinogenic Vapors from Tenax GC. 25
11 Effects of Transportation and Storage on the Percent
Recovery of Carcinogenic Vapors from Tenax GC. 26
12 Composition of Mixtures I and II for Evaluating Sorbent
Media. 28
13 Comparison of Collection Efficiency and Breakthrough for
Several Sorbents. 29
14 • Comparison of Breakthrough Volumes Obtained from Two
Different Techniques for Tenax GC. 33
15 Breakthrough Volumes for Several Highly Volatile Com-
pounds on Tenax GC (35/60 Mesh) Cartridges. 34
16 Breakthrough Volumes for Chromosorb 104. 36
17 Comparison of Breakthrough Volumes for Tenax GC and
Chromosorb 104. , 36
vii
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TABLES CONT'D
No. . Page
18 Breakthrough Study of Organic Vapors During Field Sampling. 38
19 Breakthrough Study of Hazardous Vapors During Field
Sampling. 39
20 Breakthrough Volume of Hazardous Vapors for Tenax GC
(35/60) Obtained During Field Sampling. 40
21 Relationship Between Flow Rate, Pressure Differential, and
Cartridge Dimensions for Nutech Model 221-A Portable
Samplers (AC Mode). 46
22 Relationship Between Flow Rate, Pressure Differential, and
Cartridge Dimensions for Nutech Model 221-A Portable
Samplers (DC Mode). 48
23 Performance of Nutech Model 221-A Portable Field Samplers
Under Battery Operation. 49
24 Sampling Protocol for Kanawha Valley, W. VA. 55
25 Sampling Protocol for Houston, Texas and Vicinity. 56
26 Sampling Protocol for Los Angeles Basin Area. 57
27 Operating Parameters for GLC-MS-COMP System. 59
28 Halogenated Hydrocarbons Identified in Ambient Air by
Capillary Gas-Liquid Chromatography/Mass Spectrometry/
Computer. 73
29 Oxygenated Organic Vapors in Ambient Air by Capillary
Gas-Liquid Chromatography/Mass Spectrometry Computer. 75
30 Aromatic Hydrocarbons Identified in Ambient Air by
Capillary Gas-Liquid Chromatography/Mass Spectrometry/
Computer. 77
31 Aliphatic Hydrocarbons Detected and/or Identified in
Ambient Air by Capillary Gas-Liquid Chromatography/
Mass Spectrometry/Computer. 79
32 Pollutants Identified in Ambient Air from Santa Monica, CA. 97
33 Pollutants Identified in Ambient Air from West Covina, CA. 101
34 Pollutants Identified in Night Ambient Air from West Covina,
CA. 104
35 Pollutants Identified in Ambient Air from Santa Monica, CA. 115
36 Pollutants Identified in Ambient Air from West Covina, CA. 118
viii
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TABLES CONT'D
No. Page
37 Pollutants Identified in Ambient Air from Glendora, CA. 121
38 Pollutants Identified in Ambient Air from Garden Grove, CA. 124
39 Pollutants Identified in Ambient Air from Anaheim, CA. 127
40 Pollutants Identified in Night Ambient Air from Santa
Monica, CA. 131
41 Pollutants Identified in Night Ambient Air from Anaheim, CA. 136
42 Pollutants Identified in Night Ambient Air from Anaheim, CA. 140
43 Pollutants Identified or Detected in Ambient Air from Santa
Monica, CA. 144
44 Pollutants Identified or Detected in Ambient Air from
Glendora, CA. 148
45 Pollutants Identified in Ambient Air from May Street in
Houston, TX. 154
46 Pollutants.Identified in Ambient Air from Pasadena, TX. 157
47 Pollutants Identified in Ambient Air from Baytown, TX. 160
48 Pollutants Identified in Ambient Air from Pasadena, TX. 163
49 Pollutants Identified in Ambient Air from Baytown, TX. 168
50 Pollutants Identified in Ambient Air from Texas City, TX. 171
51 Pollutants Identified in Ambient Air from Pasadena, TX. 176
52 Pollutants in Ambient Air from Dunbar, W. VA. 181
53 Pollutants.in Ambient Air from South Charleston, W. VA. 183
ix
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ACKNOWLEDGEMENTS
The valuable assistance of Mr. J. Bunch, J. McRae and Dr. R. E.
Berkley for interpreting mass spectra and executing laboratory and
field experimentation is gratefully appreciated. Mr. L. Retzlaff pro-
vided expert machining and construction of experimental devices used
in this research, a sincere thanks for his support. The design and
fabrication of temperature controllers was by Mr. R. L. Marquard and
his help is also appreciated. The author wishes to also acknowledge
the computer program made available by Dr. D. Rosenthal for single ion
plotting and the gas chromatography/mass spectrometry/computer data
acquisition by Dr. J. Bursey. The helpful suggestions of Dr. M. E. Wall
throughout the program are appreciated.
The personnel at the CHAMP stations in Santa Monica, West Covina,
Glendora, Garden Grove and Anaheim are thanked for their help while
field samples were acquired at these sites. Mr. J. Davis and B. Hoshide
at Rockwell International Science Center (Newbury Park facility) in
Thousand Oaks, CA are thanked for making available these facilities and
their extended courtesy during the author's stay. Approval for use of
CHAMP sites was given by Mr. Walter Crider of the Health Effects Research,
EPA, Research Triangle Park, NC. The author also wishes to thank the
personnel at the Fire Departments in the Kanawha Valley (Belle, South
Charleston, Dunbar and Nitro, WV). The author is especially grateful to
Captain Weaver of the South Charleston Fire Department. Drs. Dick
Flannery and Lloyd Stewart, are acknowledged for their helpful suggestions
in selecting sites in the greater Houston area as well as the use of the
Connie stations in Baytown, Pasadena and Texas City, TX.
The fabrication of custom-built portable field samplers according
to design criteria uncovered during the previous contract period was
engineered by Dr. L. Ballard, President of Nutech Corp.; his adroit
expertise is acknowledged.
The constant encouragement and helpful criticisms of Dr. E. Sawicki
and Mr. K. Crost of NERC, RTP, NC are deeply appreciated.
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SECTION I
CONCLUSIONS
The performance of sorbents for the collection and analysis of
hazardous vapors from ambient air utilizing primarily two criteria,
collection efficiency and breakthrough volumes, was studied. Exten-
sive examination of the performance of Tenax sorbent cartridge samplers
indicated that (1) there was relatively little effect of humidity on
the collection efficiency and breakthrough volumes for acrolein, di-
ethyl sulfate, propylene oxide, methyl ethyl ketone, nitromethane,
glycid aldehyde, and bis-(chloromethyl)ether. The collection effi-
ciencies in all cases were quantitative, and the breakthrough volumes
were identical to those obtained under arid conditions; (2) the effect
of repeated thermal desorption was found not to effect the collection
efficiency of Tenax GC even after 15 cycles; (3) the retaining effi-
ciency of Tenax GC for 29 hazardous vapors studied indicated that a
decrease in the quantitative recovery (10-30%) had gradually after
four weeks of storage; (4) the collective efficiency and breakthrough
volumes for several vapors on Tenax GC was related to the molecular
structure and volatility of the compound. The lowest breakthrough
volume was observed for acrolein (4.5 £/g of Tenax) and the highest
3
for styrene oxide (3.5 m /g of sorbent). Comparison of Tenax GC to
Chromosorb 104 revealed that Chromosorb 104 had a higher retention
index (4-9 times); however, Chromosorb 104 also trapped more water
and exhibited a lower temperature stability. Breakthrough studies
conducted in areas regarded as to having low and high background
pollution levels indicated that displacement of acrolein, trichloro-
ethylene, 2-chloroethyl ethyl ether, bis-(chloromethyl)ether, chloro-
benzene, phenyl methyl ether, toluene, and nitrobenzene had not occurred,
Using the criteria and design specifications undercovered during
the previous contract period, a portable field sampler was fabricated.
The testing of two portable field samplers yielded performance data
which were well within the design specifications (6.7 £/min using a
35/60 mesh sorbent in a cartridge 1.5 cm i.d. x 6 cm bed-depth). Port-
able field samplers operated in the DC mode required 2-2.5 amps depen-
ding on the cartridge size, sorbent mesh, and flow rates employed. It
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was concluded that for a standard 12-V 50 amp-hr battery, the maximum
sampling period attainable would be approximately 20 hours.
Many hazardous and background pollutants were identified in three
major geographical areas in the Continental United States, the Kanawha
Valley, W. VA., Houston, Texas area, and the Los Angeles Basin. A com-
bined total of 21 halogenated compounds were identified. Amongst them
were two known carcinogens, vinyl chloride and trichloroethylene. Others
may be classified as cocarcinogens (chloroform, carbon tetrachloride,
and bromoform). A combined total of 27 oxygenated compounds were identi-
fied. Two epoxides (styrene oxide and epoxyheptane) were tentatively
characterized. Several aldehydes, ethers, alcohols, ketones, and a
phenolic compound were detected. Background constituents which were
either identified or detected in ambient air consisted of over 40 aro-
matic and approximately 113 aliphatic compounds. It was concluded that
this may represent only a small percentage of the hazardous pollutants
present in the atmosphere. Improved methods of resolution are needed.
Future studies should also estimate the quantity of carcinogenic and
mutagenic pollutants in ambient air.
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SECTION II
RECOMMENDATIONS
Three major phases of research should be expanded and pursued:
(1) Extensive Sampling of Numerous Sites for Hazardous Atmospheric
Pollutants -
The methodology for collection, resolution and identification
of hazardous vapors in ambient air which was developed and im-
proved during the past two years under Contract No. 68-02-1228,
should be applied to field sampling of numerous sites within the
Continental U.S. with a major thrust toward the characterization
and identification of carcinogenic and mutagenic vapors.
(2) Identification of Hazardous Vapors in Atmospheric Samples -
Further research should be undertaken on the resolution of back-
ground and hazardous vapors collected at field sites. The
resolution and characterization studies of air samples should be
achieved by using glc-ms-comp techniques employing a set (3-4)
of glass capillary columns of 100-300 m in length containing non-
polar, semi-polar and polar stationary phases.
(3) Development of Pollution Profile Indicative of Individual Sites -
Pollution profiles should be constructed for the various geogra-
phical areas postulated to contain hazardous vapors. These
profiles should consist of the following: (a) total ion current
plots representative of individual sites sampled based primarily
on the hazardous vapors identified; (b) total ion current plots
representative of all sites sampled which will include the
general background incurred in ambient air; (c) mass fragmento-
grams representative of individual sites sampled using mass ions
characteristic of hazardous vapors, and aliphatic and aroma-
tic compounds, and (d) mass fragmentograms representative of
all site samples using mass ions which constitute general
background and interferences. In all cases the profiles should
be constructed using high resolution capillary columns contain-
ing non-polar, semi-polar or polar stationary phases. The
chromatographic parameters (carrier flow rates, temperature
program rates, etc.) should be standardized for each case so
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that comparisons can be made between geographical area, sites,
locations and seasons.
(4) Estimation of the Levels of Hazardous Vapors Present in Ambient
Atmosphere -
The level of hazardous vapors and background pollutants occurring
at the various geographical sites should be estimated by gc-ms
computer techniques. Gas chromatography with selective detectors
should also be employed for quantitating specific chemical classes
of compounds in combination with high resolution columns.
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SECTION III
INTRODUCTION
CARCINOGENIC VAPORS IN AMBIENT ATMOSPHERES
Several investigators have postulated the presence of carcinogenic
vapors in ambient atmosphere . However, until this program was initia-
ted (EPA Contract 68-02-1228) no serious endeavor had been made to
sample ambient air to establish their presence and identity. Many hazar-
dous agents are suspected to be introduced directly into the environment
Q
via industrial pollution . Potential sources of hazardous vapors such as
alkylating agents are ubiquitous. This entity of organic compounds may be
associated with textile plants that utilize aziridines and processes such
as crease or flame-proofing of textiles, dyeing and printing (e_.£. ethyl-
enimine or triethylenemelamine). Alkylating agents are also used in the
manufacture of resin products and the finishing of rayon fabrics, and the
curing and vulcanizing of rubber (nitrosamines). Carcinogenic and mutagenic
vapors are frequently used as intermediates in organic synthesis, £.£. in
the preparation of polyvinyl chloride (vinyl chloride), high energy fuel
plastics and hydroxyethylated cellulose of fibers (ethylene oxide), sur-
factants, urethane elastomas, cosmetics (propylene oxide), cellulose acetate
(ethylene chlorohydrin), curing of polymers, Pharmaceuticals (1,2:3,4 di-
epoxybutane) and as catalysts for polymerization [diethylsulfate, bis-
(chloromethyl)ether]. Organics employed in bulk form for manufacturing such
as organic solvents (chloroform, carbon tetrachloride, ethylene oxide, etc.)
are also potential sources for high ambient levels of hazardous vapors.
In addition to industrial pollution, photochemical reactions in the
9—13
atmosphere have been postulated to produce hazardous vapors . Because
unsaturated hydrocarbons constitute a large fraction of organic air pollu-
tants it is reasonable to assume that carcinogenic and mutagenic products are
formed from ozonization, oxidation, substitution or addition reactions (S02,
NO, NO., SO , NO , etc.) whether spontaneously or photochemically induced.
£, X X
Epoxides, peroxides, aldehydes, ketones, lactones, sulfonates, sultones, and
nitro compounds have been in fact isolated in laboratory experiments on ole-
9
fin oxidation, sulfonation, nitrosation, nitration and ozonization .
There is a strong indication nitrosamines are present in the atmosphere;
their identification in cigarette smoke has been confirmed . Alkylating
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compounds resulting from limited-aeration smoldering of plastics, paper
and cellulose as well as auto exhaust gases have beer, demonstrated to
2
occur and have been postulated as a health hazard in industrial areas .
In contrast to the above potential sources of pollution, photochemical
processes are also important in the production of hazardous vapors. For
the Los Angeles area, the photodissociation of nitrogen dioxide into nitric
oxide and atomic oxygen is thought to be the most important primary photo-
chemical process . Although this may be true for most modern urban
areas, it is possible that under different patterns of emission, the dominant
role of nitrogen dioxide may be taken over by other primary absorbers. For
example, organic compounds which produce hazardous vapors. The free radical
reactions are another important feature of atmospheric reactions yielding a
variety of products including alkyl nitrates, peroxides, epoxides and hydro-
peroxides .
On the basis of the current knowledge of air pollution, most of the
potentially deleterious vapors which could be formed and/or expelled into
the atmosphere could be therefore classified as epoxides, 8-lactones,
peroxides, hydroperoxides, sulfonates, sultones, niL.osamines, a-chloroalkyl
ethers and chlorinated compounds. Some of these pollutants may of course
have a very short lifetime in the atmosphere.
PREVIOUS ACCOMPLISHMENTS ON THE DEVELOPMENT OF METHODS FOR CARCINOGENIC
VAPOR ANALYSIS IN AMBIENT ATMOSPHERES
During the previous contract period (6/22/73 - 6/21/74) analytical
techniques were developed for evaluating collection efficiencies of
candidate sorbents during the concentration of hazardous vapors from a
flowing stream. The polymeric beads Tenax GC, Porapak Q, Chromosorb 101
and 104 were >90% efficient in trapping hazardous vapors such as epoxides,
g-lactones, sulfonates, sultones, n-nitrosamines, chloroalkyl ethers,
aldehydes and nitro compounds from synthetic air-vapor mixtures at 0.25 £/
min. Tenax GC and Chromosorb 101 were also tested at sampling rates up to
9 £/min and efficiencies of >90% were maintained. Carbowax 400 and 600 and
oxypropionitrile coated or chemically bonded to supports and activated car-
bons were also highly efficient.
A thermal desorption inlet-manifold for recovering and transferring
hazardous substances from sorbents to a gas-liquid chromatograph or a gas-
liquid chromatograph/mass spectrometer was developed. The interface
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consisted of a desorption chamber, a six-port two position high tempera- **
ture/low volume valve, a nickel-capillary trap and a temperature con-
troller. This unit was utilized to determine the temperature rise times
in the center of cartridge samplers for a variety of sorbents under iso-
thermal chamber temperatures. The relative heating rates were PCB and
BPL activated carbons > oxopropionitrile and Carbowax 400 chemically
bonded to Poracil C > Chromosorb 104 > Tenax GC > Chromosorb 101. The
heating rates were linear for all sorbents up to 65% of the set desorption
chamber (in 60-90 sec) but required several minutes thereafter to reach
the final temperature. Since the percent recovery of several hazardous
vapors adsorbed on Tenax GC using this inlet-manifold was >90% at the
50 ng level, it was concluded that the designed system was satisfactory
for analysis of cartridge samplers.
Design criteria were also developed for a field sampling system for
collecting pollutants using a cartridge containing a solid sorbent. The
relationship between the ambient vapor concentration, the total volume of
air required and the time required for sampling at various flow rates were
important considerations in the design specifications. The power required
to pump air through sorbent packed tubes was a function of pressure dif-
ferential (AP) across the tube under flow conditions. The AP was found to
be related to (1) sampling rate, (2) diameter and length of cartridge, (3)
particle size distribution and (4) particle shape. Based upon AP the power
requirements for a pumping system were calculated and applied to the fabri-
cation of a field sampler.
During the previous project period, the methodology and instrumentation
developed was also applied to the analysis of air samples from the Los
Angeles Basin area. Using glc-ms-comp techniques, many aliphatic and aroma-
tic compounds were identified in these preliminary studies. The relative
intensities of single ion plots for ions representing aliphatic and aromatic
cracking patterns revealed that Tenax did not efficiently retain background
aliphatic constituents (i.e. the breakthrough volume was considerably lower
than other compounds), a desirable feature since most hazardous vapors of
interest are semi-polar/polar compounds. It was concluded that improved
techniques for.resolving background pollutants occurring at high concentra-
tions from trace hazardous vapors needed to be developed.
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One oxygenated compound of significant interest (in air from West ..*'*
Covina and Santa Monica, CA.) was tentatively identified as styrene oxide.
The perfection of the methodology for collection and analysis of
mutagenic and carcinogenic vapors in ambient air was pursued during this
project year (6/22/74 - 6/21/75) as well as the application of these tech-
niques for determining the presence of any hazardous vapors in the atmos-
phere.
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SECTION IV
PROGRAM OBJECTIVES
The general scope of this research program was to continue to develop
and perfect methodology for reliable and accurate collection and analysis
of mutagenic and carcinogenic vapors (collectively termed hazardous com-
3
pounds) present in trace quantities in the atmosphere down to ng/m amounts.
Once the physiologically active vapors present in polluted atmospheres have
been determined, researchers can then ascertain which substances need to be
routinely analyzed, studied epidemiologically and, eventually, controlled.
The major objectives were:
(1) To determine the performance characteristics of a cartridge sampler,
specifically the effects of transportation and storage on adsorbents
and reliability and accuracy of analysis for collected pollutants,
and potential sources of contamination;
(2) To acquire experimental data for optimum performance of adsorbents;
(3) To examine an alternative backup sampling device;
(4) To improve sampling devices and the miniaturization of the system
for portability;
(5) To determine and develop techniques for the separation of hazardous
substances under study from the many hundreds of organic pollutants
which are of secondary interest at this stage;
(6) To determine the identity and relative quantities of background
organic pollutants which interfere with major goals of the program;
(7) To undertake a concerted effort to collect field samples at geogra-
phical sites postulated to contain hazardous (mutagens, carcinogens,
and other alkylating agents) compounds;
(8) To characterize unequivocally the atmospheric pollutants of
interest and those hazardous to living organisms using methodology
and instrumentation developed under this research program, and
(9) To characterize background atmospheric pollutants which are of
secondary interest to this research program.
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SECTION V
PERFORMANCE OF SORBENT CARTRIDGE SAMPLER FOR HAZARDOUS VAPORS
Because the concentrations of hazardous vapors sought were anti-
3 14
cipated to be in ng/m amounts or less, it was recognized that the major
problems would arise with the development of an adequate collection system
for concentrating sufficient quantities of material. The relationship
between the sampling parameters for collection from ambient air has been
14
previously discussed . To accumulate sufficient quantities of vapors from
the atmosphere for qualitative and quantitative analysis, an efficient col-
14
lection device must be employed
The performance of many sorbents as to their ability to extract and
retain hazardous vapors from a moving air stream had not been adequately
studied until this program. The parameters which are involved in deter-
mining the performance of sorbents can be divided into two categories.
There are those on the one hand which are related to sampling environment
such as flow rate, air temperature and humidity and those, on the other
hand related to the physico-chemical properties of sorbents such as sur-
face area, particle size and porosity, solute capacity, sorption mechanism,
degree of solute affinity, etc. Furthermore, some of these factors which
influence sorbent performance are not independent of each other. We have
previously defined collection efficiency and breakthrough volumes as cri-
14
teria in order to assess the collection performance of sorbents . Col-
lection efficiency was defined as the fraction of solute vapor in the pol-
luted gas which was retained by the sorbent when a discrete quantity is en-
countered. On the other hand, when polluted gas enters a sorbent bed, an
equilibrium zone is established near the point of entry which, as more
pollutant vapor is introduced, may expand through the packing length
until the capacity of the sorbent is exceeded. However, if after an
initial period of time no additional polluted vapors are introduced
and the purging of the packing bed continues, the zones of vapors will
move through the packing bed. When the mass zones reach the end of
the available packing bed and the vapors begin to leave breakthrough
has occurred. Thus, breakthrough volume is simply the elution volume (EV)
which can be calculated if the time required for the zone to traverse and
10
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elute from the sorbent bed and the sampling rate are known. In an ideal
collection system, EV has an infinite value at ambient temperature.
The relationship which describes the amount of vapor adsorbed to a
given quantity of adsorbent as a function of pressure, temperature and
concentration of the solute vapor is given by the Langmuir equation
14
which has been previously discussed
This section describes further studies on the performance of sorbents
for the collection and analysis of hazardous vapors from ambient air uti-
lizing primarily two criteria, collection efficiency and breakthrough
volume. Utilizing these two criteria, the performance of Tenax GC is
related to environmental factors such as sampling location, temperature
and possible interferences from humidity and other gaseous pollutants.
EFFECTS OF HUMIDITY ON COLLECTION EFFICIENCY AND BREAKTHROUGH VOLUME
FOR TENAX GC
Different climatic factors are experienced during field sampling
which may affect the performance of the Tenax GC cartridge sampler.
Because the relative humidity varies considerably between different
geographical areas, the ability of Tenax GC to extract hazardous vapors
at different humidities was studied. Even though one of the unique fea-
tures of porous or recrystallized polymers is their low retentive index
for water, the collection efficiency or breakthrough volume for some
compounds might be altered by the presence of trace amounts of adsorbed
water on the surface of the particle. In order that a cartridge sampler
may extract vapors from ambient air in a quantitative fashion, it is im-
portant that relative humidity does not significantly change adsorption
affinity.
We have investigated the effect of water vapor on the quantitative
parameters of Tenax GC (collection efficiency and breakthrough volume)
for trapping trace amounts of hazardous vapors. The primary objective
of this study was to measure the breakthrough volume for a series of
hazardous vapors of differing polarities on Tenax GC at defined levels
of water vapor in ambient air.
Experimental
The monitoring system described by Pellizzari et al. was used in
order to demonstrate the effect of relative humidity on the collection
11
-------
efficiency and breakthrough volume for Tenax GC. This system was modi-
fied to incorporate a humidity generator in line with the air flow to the
glove box. Because carcinogenic vapors were used in this study, the
experiments were executed in a glove box which was evacuated by vacuum
through cryogenic safety traps . The desired humidities were generated
from a 2 £ closed vessel containing 200 ml of water. A refrigeration
unit (Type FEN, Haake, Inc., Saddle Brook, NJ) was used to cool the
vessel to various calculated temperatures in order to achieve the desired
vapor pressures of water (Table 1). Air (breathing quality, Linde
Division, Union Carbide, East Brunswick, NJ) from a pressurized reservoir
Table 1. RELATIONSHIP BETWEEN TEMPERATURE, WATER VAPOR PRESSURE,
AND HUMIDITY IN A CLOSED VESSEL CONTAINING WATER
Temperature
(°C)
25
23
20
16
13
10
Vapor Pressure
(mm Hg)
23.76
21.07
17.54
13.63
11.23
9.20
Absolute Humidity
(g/m3)
21.6
19.8
16.2
12.9
11.3
8.8
Relative Humiditya
(Percent)
100
92
75
60
50
41
SAt 25°C.
was purified and dehumidifed by passing it through a scrubbing tower
(5 cm i.d. x 30 cm in length) which contained layers of calcium chlo-
ride dessicant and BPL activated carbon (12 x 30 mesh, Calgon Corp.,
Pittsburgh, PA) and was delivered first to the humidity generator and
then to the glove box arrangement at a rate of 4 £/min. The air stream
passed from the humidity generator through the glove box into a 2 £
sperical chamber fitted with an injection port where known quantities
of hazardous vapors were introduced. The chamber delivered synthetic
air-vapor mixtures to the cartridge sampler which contained the sorbent
under study . The effluent stream from the sampler was split and a flow
of 50-100 ml/min was directed to a flame ionization detector (Model 1200,
12
-------
Varian Instruments Corp., Walnut Creek, CA). Hydrogen and air flow to
the flame ionization detectors were 35 and 250 ml/min, respectively. The
detector output signal was amplified (Varian Model 520) and recorded with
an Omniscribe strip chart recorder (Houston Instruments, Houston, TX).
This apparatus monitored total hazardous vapors in the cartridge sampler
effluent.
Sorbents were packed in glass tubes (1.056 cm i.d. x 10 cm in length)
using 1 cm of silanized glass wool plugs for support. The cartridge sam-
plers were inserted in canisters constructed from "tube L" 3/4 in copper
fitted with 3/8 in Swagelock unions. The entrance and exit lines in the
monitoring system were 3/8 in o.d. Teflon (Comco Plastics Corp., Raleigh
NC).
To synthesize known concentrations of air/solute/vapor mixtures,
microliter quantities of each organic compound were injected in to a 2 £
sperical flask. The flask was heated to 50° and the air vapor mixture
was continuously stirred. An aliquot from this stock reservoir was trans-
ferred to the chamber in the monitoring system. By continuously monitor-
ing the cartridge sampler effluent with the flame ionization detector, the
collection efficiency of each sorbent was determined. Decay curves which
represented the concentration of air/hazardous vapor mixture leaving the
chamber per unit time were established for each compound and purging rate
by using empty cartridge samplers. The percent collection efficiency was
estimated by comparing the areas under curves obtained for samplers with
and without sorbent.
Results and Discussion
The relationships between temperature, water vapor pressure and humi-
dity are given in Table 1. At a relative humidity of 50% a cubic meter of
air at 25°C contained 11.3 g of water. Thus, when sampling ambient air the
cartridge sampler will encounter significant amounts of water during sampling.
A large variation in the amount of water present in ambient air is expected
when sampling in the various regions throughout the continental United
States. For example, in arid regions (Southern California), the relative
humidity may be as low as 20%, while in high humidity regions (Gulf Coast),
it often exceeds 90%. Therefore, the amount of water vapor can vary as much
as four-fold between low and high relative humidity areas. In order to
achieve reproducible results it is important that the variation in humidity
13
-------
experienced during sampling does not affect the collection efficiency or
breakthrough volume of the sorbent used for extracting hazardous vapors
from air.
The effect of humidity on collection efficiency for Tenax GC is
depicted in Table 2. The results indicate that for the nine test com-
pounds selected for evaluation, no apparent decrease in the collection
efficiency was experienced by increasing the relative humidity from 41-
92%. Likewise, the effect of humidity on breakthrough volumes for a
number of hazardous vapors was also determined (Table 3). Again in all
cases the breakthrough volume did not significantly change when the per-
cent relative humidity was increased from 41-92%. Based upon these ex-
periments, the ability of Tenax GC to collect and retain hazardous vapors
in ambient air is relatively unaffected by humidity conditions commonly
encountered in field sampling.
These results are consistent with those observations reported by
Janak e£ al. "who studied the effect of water vapor and the quantitative
collection of trace components on Tenax GC from headspace of aqueous
samples. The- specific gas chromatographic retention volume of model com-
pounds (methanol, ethanol, propanol, ethyl acetate, acetone and benzene)
on Tenax GC were measured with the use of a carrier gas saturated with
water vapor. They found differences between the retention values measured
with and without water in the carrier gas to vary approximately + 10%
of the values measured. From this viewpoint, the effect of water can
be considered to be insignificant.
EFFECT OF REPEATED THERMAL DESORPTION ON COLLECTION EFFICIENCY OF
TENAX GC
One of the outstanding features of Tenax GC is its high operating
temperature ' . At temperatures up to 350° very little back- .
ground bleeding is observed. Even though this sorbent has a high tempera-
ture limit, relatively little is known about the effect of repeated tempera-
ture programming on its adsorption affinity for hazardous vapors. Prolonged
repeated use of this sorbent at high temperatures might alter its physico-
chemical properties which in turn could change its collection efficiency
and/or breakthrough volume characteristics. In order to further estab-
lish the performance characteristics of the Tenax GC cartridge sampler,
14
-------
Table 2. EFFECT OF HUMIDITY ON PERCENT COLLECTION
EFFICIENCY FOR TENAX GCa
Percent Humidity in
Compound
Acrolein
Diethyl sulfate
Propylene oxide
Methyl ethyl ketone
Nitromethane
Glycidaldehyde
Bis- (chloromethyl) ether
41
100
100
100
100
100
100
100
50
100
100
100
89
-
-
-
60
100
100
100
87
-
-
-
Ambient Air
75
100
100
100
100
-
-
-
92
98
100
100
100
100
100
100
aAll values are in percent and relative to 41% humidity; a sampling
rate of 4 £/min was used.
Table 3. EFFECT OF HUMIDITY ON BREAKTHROUGH VOLUMES OF
HAZARDOUS VAPORS FOR TENAX GC*
Percent Humidity in Ambient Air
Compound
Acrolein
Diethyl sulfate
Propylene oxide
Methyl ethyl ketone
Nitromethane
Glycidaldehyde
Bis- (chloromethylether
41
3.2
3.0
4.0
19.5
14.0
53.0
172
50
3.2
3.5
4.3
20.0
-
-
-
60
3.2
3.5
4.0
20.0
-
-
'-
75
3.2
3.5
4.5
20.0
-
-
-
92
3.2
3.5
4.5
20.5
15.0
55.0
172
values are in &/g; a sampling rate of 4 £/min was used.
15
-------
the effect of repeated thermal desorption on its collection efficiency
was examined.
Experimental
Glass cartridges (1.0 cm i.d. x 3.0 in length) containing virgin
Tenax GC (35/60) were used. Prior to this study the sorbent was purified
by extracting in a soxhlet apparatus with methanol as previously described .
A standard mixture of vapor (Table 4) was passed into four identical
sampling cartridges. Each loaded cartridge was thermally desorbed and
the mixture resolved by gas/liquid chromatography.
Gas-liquid chromatography (glc) was conducted on a Perkin-Elmer 900
series chromatograph (Perkin-Elmer Corp., Norwich, CN) equipped with dual
flame ionization detectors. A 2.5 mm i.d. x 3.6 m silanized glass column
containing Tenax GC (60/80) sorbent was used for resolving the mixture of
hazardous vapors obtained by thermal desorption of loaded cartridges. The
column was programmed from 55-250° @ 10°/min with an initial and final iso-
thermal period of 2 and 10 min, respectively. Carrier gas (N ), hydrogen
and air flow were 45, 30 and 250 ml/min, respectively. The injection port,
manifold and detector temperature were maintained at 250°.
Peak areas were obtained for each component and an average value
was calculated from the four cartridges. Subsequently, two of the four
cartridges were emptied and refilled with virgin Tenax GC. The four
cartridges were then again loaded with the same standard mixture of vapor
and analyzed again by thermal desorption glc. A comparison was made of
the average peak area of the two cartridges containing virgin Tenax with
the two cartridges which had been previously desorbed. Peak area ratios
and the percent recovery were calculated as follows:
AR
% recovery of vapor = — x 100
\
where A^ = area of component from sorbent undergoing repeated thermal
desorption
A_r = area of component from virgin sorbent
Results and Discussion
The results obtained from repeated thermal desorption of vapors from
Tenax GC cartridges are shown in Table 5. These data (and the remaining
16
-------
Table 4. VOLATILE ORGANIC VAPOR MIXTURE FOR DETERMINING
EFFECT OF REPEATED THERMAL DESORPTION ON
COLLECTION EFFICIENCY OF TENAX GC&
Chemical Family Compounds
amines Cyclohexylamlne
Aniline
N-ethyl aniline
n-Decylamine
ketones 2-Butanone
Cyclohexanone
2,5-Hexanedione
4'-Fluoroacetophenone
Propiophenone
ethers 2-Chloroethyl ethyl ether
Phenyl methyl ether
halogenated substances Chlorobenzene
4'-Fluoroacetophenone
2-Chloroethyl ethyl ether
Nitro compounds Nitropropane
Nitrobenzene
aAn aliquot of vapor containing approximately 100 ng of each component
was loaded onto each Tenax GC cartridge.
17
-------
Table 5. EFFECT OF REPEATED DESORPT.ION ON PERCENT COLLECTION
EFFICIENCY OF TENAX GC CARTRIDGE SAMPLERS3
oo
Desorption
No.
1
2
10
11
12
13
14
15
chlorobenzene
89
95
75
78
78
92
101
93
1-nitropropane
80
87
79
80
74
93
97
86
Compound
phenyl methyl ether
87
93
84
92
78
93
97
74
cyclohexyl amine
110
61
79
90
88
89
103
75
aniline
70
110
73
84
86
95
97
82
A 1.0 cm i.d. x 3.0 cm bed of 35/60 mesh Tena.: GC was used for the entire study. All desorptions
were at 265°. Within each set of desorption steps values were + 5% for replicate cartridges.
-------
vapors used) indicate that repeated use of Tenax GC does not produce a
decrease in the collection efficiency even after recycling the cartridges
fifteen times.
A STUDY OF TRANSPORTATION AND STORAGE ON THE PERFORMANCE OF TENAX GC
The use of a cartridge sampler for qualitative and quantitative
analysis requires different specifications to ensure the sample which
is collected is representative of the ambient air pollutant at a par-
ticular site. For the purpose of defining a cartridge sampler in terms
of qualitative and quantitative analysis, it is important that the in-
tegrity of the hazardous vapors be maintained during collection, trans-
portation and storage of that sample. The purpose of this study was to
anticipate and avoid problem areas which might occur during transportation
of cartridge samples. The method of packing and transporting the car-
tridges should prevent contamination of the cartridge or loss of collected
vapors during storage.
Experimental
Sets of glass cartridge samplers containing Tenax GC (1.0 cm i.d. x
3.0 cm in length) were used. All cartridges were loaded with approximately
300 ng of each compound (Table 6) using the previously reported monitoring
14 15
system ' . The experimental design for studying the effect of transporta-
tion and storage on Tenax GC cartridges is shown in Table 7. The percent
recovery of each hazardous vapor for each set of glass cartridges was
compared with that of the cartridges analyzed immediately after loading
(reference control). This was accomplished by calculating peak area
ratios between the experimental and reference cartridge for each solute.
Gas-liquid chromatography (glc) was conducted on a Perkin-Elmer 900
series chromatograph (Perkin-Elmer Corp., Norwich, CN) equipped with dual
flame ionization detectors. A 2.5 mm i.d. x 3.6 m silanized glass column
containing Tenax GC (60/80) sorbent was used for resolving the mixture of
hazardous vapors thermally desorbed from cartridges. The column was
programmed from 55-250° at 10°/min with an initial and final isothermal
period of 2 and 10 min, respectively. Carrier gas (N~), hydrogen, and
air flow rates were 45, 30 and 250 ml/min, respectively. The injection
port, manifold, and detector temperatures were maintained at 250°.
All cartridge samplers were shipped to Houston, TX and San Francisco,
CA ±>y air freight.
19
-------
Table 6. ORGANIC VAPORS EMPLOYED FOR STUDY ON THE EFFECT OF
TRANSPORTATION AND STORAGE ON SAMPLE FROM
TENAX GC
Test Vapor
Test Vapor
Glycidaldehyde
g-Propiolactone
Bis-(2-chloroethyl)ether
Ethyl methanesulfonate
Nitromethane
Bis-(chloromethyl)ether
Butadiene diepoxide
N-nitrosodiethylamine
Styrene oxide
Cyclohexene oxide
1-Bromopropane
2-Butanone
Trichloroethylene
2-Chloroethyl ethyl ether
Nitroethane
Chlorobenzene
1-Nitropropane
Cyclohexylamine
Phenyl methyl ether
Propane dithiol
Aniline
2,5-Hexanedione
N-Ethyl aniline
Nitrobenzene
4'-Fluoroacetophenone
Propiophenone
n-De cylamine
Diphenyl ether
Sulfolane
20
-------
Table 7. EXPERIMENTAL DESIGN FOR STUDYING THE EFFECT OF TRANSPORTATION AND
STORAGE ON TENAX CARTRIDGES
Set No. Experimental Condition No. of Cartridges
1 A set of cartridges was analyzed immediately after 3
loading with hazardous vapors (reference controls).
2 A set of cartridges was loaded and stored in the 3
laboratory for one week and then analyzed concurrently
with Case No. 4.
3 A set of cartridges was loaded and stored in the 3
laboratory for 2-4 weeks and then analyzed concurrently
with Case No. 5.
4 A set of cartridges was prepared, transported and 3
upon return immediately analyzed.
5 A set of cartridges was prepared, transported, and
then stored in the laboratory 2-4 weeks prior to analysis.
6 A set of unloaded cartridges was transported and upon 2-3
return analyzed for possible contamination.
-------
Results and Discussion
The effects of transportation and storage on the retaining efficiency
of Tenax GC for several hazardous vapors are given in Tables 8-11. Car-
tridge samplers which were either transported or stored for a period of one
week gave essentially quantitative recoveries of each of the hazardous
vapors examined. A slight decrease in the percent recovery was observed
when the cartridges were stored an additional week after transportation
(Tables 8-11). Further storage (3-5 weeks) of the cartridge samplers yielded
additional decreases in the recovery which can be correlated to the volati-
lity of each of the vapors (Table 8). For example, a recovery of 50% was
observed for 1-nitropropane after five weeks of storage.
Quantitative recoveries were obtained in all cases when cartridge sam-
plers were either shipped or stored in the laboratory for a period of up to
three weeks. No significant differences were observed between sampling
cartridges stored for a period of time with those cartridges which were
transported:.and then stored for the same length of time.
Since all of the vapors were loaded onto cartridges using ambient air
which contained <40% relative humidity, the effects of trace quantities of
water vapor trapped on the sorbent was not significant. However, experi-
ments which used lab air (relative humidity of approximately 80%) for
loading cartridge samplers, we observed a significant decrease in the
percent recovery of bis-(chloromethyl)ether (BCME) after a period of
a few days. For example, when 50 ng of BCME was loaded onto a Tenax
cartridge, only a 50% recovery was obtained the following day. After
one week of storage, only trace quantities of bis-(chloromethyl)ether
could be detected. This is consistent with the observations of previous
25
investigators who demonstrated that bis-(chloromethyl)ether and mono-
(chloromethyl)ether undergo rapid hydrolysis in atmospheres of relatively
high humidity. Perhaps an alternative approach to collecting bis-(chloro-
methyl)ether in ambient air should be investigated, £•£. the collection
of the carcinogen as a derivative on the cartridge to stabilize it from
further decomposition.
Cartridges (blanks or loaded cartridges) transported in standard
cardboard mailing tubes or plastic screw-cap containers developed a high
background. In contrast, when cartridge samplers were placed in heavy
22
-------
Table 8. EFFECT OF TRANSPORTATION AND STORAGE ON THE PERCENT
RECOVERY OF VAPORS FROM TENAX GC CARTRIDGES*
Compound
1-Nitropropane
Chlorobenzene
Pheny line thy 1 ether
N-Ethyl aniline
Nitrobenzene
Aniline
4 ' -Fluoroacetophenone
0
95 + 2
95 + 2
95 + 2
95+2
95 + 2
95 + 2
95 + 2
Weeks Expired
3
93 + 3
80 + 4
95 + 2
95 + 2
95 + 3
95 + 2
80 + 4
5
50 + 9
50 + 8
70 + 8
70 + 6
50 + 9
80 + 5
90 + 4
a
shipped air freight to Houston, TX and returned after two weeks;
0-3 week period includes transport, 3-5 represents additional storage.
23
-------
Table 9. EFFECTS OF TRANSPORTATION AND STORAGE ON THE
PERCENT RECOVERY OF CARCINOGENIC VAPORS
FROM TENAX GC&
Compound
Glycidaldehyde
g-propiolactone
Bis- (2-chloroethyl) ether
Ethyl methanesulfonate
Nitromethane
Bis-(chloromethyl) ether
Butadiene diepoxide
N-nitrosodiethylamine
Styrene" oxide
Weeks
Nontransported
0
95
100
90
100
-
100
100
100
100
1
95 + 3
-
-
-
97 + 3
83 + 5
93 + 4
94 + 4
67 + 8
Expired
Transported
0
95
100
90
100
-
100
100
100
100
1
90 + 4
77 + 4
97 + 2
105 + 3
90 + 5
98+2
82 + 4
83 + 4
75 + 10
Tenax GC cartridges were loaded with vapors (900 ng/component),
shipped by air freight to San Francisco, CA and immediately returned,
Total transportation time was 7 days.
24
-------
Table 10. EFFECTS OF TRANSPORTATION AND STORAGE ON THE
PERCENT RECOVERY OF CARCINOGENIC VAPORS
FROM TENAX GC*
Weeks Expired
Compound
Glycidaldehyde
8-propiolactone
Bis-(2-chloroethyl) ether
Ethyl methanesulfonate
Nitromethane
Bis- ( chlor omethyl) ether
Butadiene diepoxide
N-nitrosodiethylamine
Styrene oxide
Nontransported
0
95
100
90
100
-
100
100
100
100
1
92 + 4
95 + 4
86 + 6
85 + 5
92 + 3
65 + 5
76 + 6
82 + 4
71+5
0
95
100
90
100
-
100
100
100
100
Transported
1
87 + 4
90 + 5
87 + 5
83 + 6
95 + 3
58 + 5
75 + 4
84 + 3
68 + 6
2
50 + 8
85 + 2
>95 + 2
>95 + 2
85+2
41 + 4
64 + 5
62 + 3
70 + 7
a
by air freight to San Francisco, CA and immediately returned. Total
transportation time was 6 days.
25
-------
Table 11. EFFECTS OF TRANSPORTATION AND STORAGE ON THE
PERCENT RECOVERY OF CARCINOGENIC VAPORS
FROM TENAX GCS
Weeks Expired
Compound
8-Propiolactone
Bis- (2-chloromethyl) ether
Ethyl methanesulfonate
Nitromethane
Bis- (chloromethyl) ether
Butadiene diepoxide
N-nitrosodiethylamine
Styrene oxide-
Cyclohexene oxide
Tenax GC cartridges were
Nontransported
0
100
90
100
100
100
100
100
100
100
loaded
by air freight to San Francisco
1
100 + 2
100 + 3
73 + 7
100 + 1
100 + 3
100 + 4
98 + 2
100 + 3
77 + 7
with 300 ng
Transported
0
100
90
100
100
100
100
100
100
100
of each
, CA and immediately
1
95 + 3
100 + 3
-
100 + 3
90 + 2
91 + 3
100 + 1
100 + 1
80 +
compound,
returned .
2
90 + 2
95 + 3
90 + 3
85 + 4
90 + 3
85 + 2
96 + 4
88 + 5
80 + 4
shipped
Total
transportation time was 6 days.
26
-------
duty Corex^-'glass screw cap (Teflon^ lined) centrifuge tubes (50 ml,
Corning Glass Works, Corning, New York), the background was negligible.
During flight the baggage compartment of an airplane undergoes depres-
surization (ca. 530 mm Hg) followed by repressurization and this could
lead to contamination of the cartridge. Therefore, they should be shipped
in containers which are vacuum tight and impermeable to gases. Corex^
glass centrifuge tubes satisfied the requirements that a container be
durable to avoid damage during shipment and have a vacuum tight seal.
DETERMINATION AND COMPARISON OF BREAKTHROUGH VOLUME AND COLLECTION
EFFICIENCY FOR SORBENTS
Because the sorbent Tenax GC exhibits low breakthrough volumes for
some of the more volatile hazardous vapors, such as acrolein, propylene
oxide, diethyl sulfate, nitromethane and glycidaldehyde, we examined
alternate collection media for inclusion as a possible backup material.
i . ,14-16,22-24,26-46
Several sorbents have been previously reported as col-
lection media, for trapping ambient air pollutants. These sorbents were
selected for further testing of collection efficiency for mixtures of
hazardous vapors.
Experimental
Collection efficiency and breakthrough volumes were determined by
14
the previously described monitoring system . Glass sampling cartridges
packed with Tenax GC (1.0 cm i.d. x 3 cm in length) were used. The flow
rate through the cartridge was 4 £/min. Mixtures I and II shown in Table
12 were used to assess collection efficiency and breakthrough volume.
Three hundred nanograms of each compound were used.
Tenax GC (35/60), Chromosorb 101 (60/80), Chromosorb 102 (60/80),
Chromosorb 104 (60/80), and Porapak-Q (100/200) were purchased from Ap-
plied Science, State College, PA. Carbon derived from coke (PCB/BPL,
1230) was acquired from Pittsburgh Activated Carbon Div. of Calgon Corp.,
Pittsburgh, PA. Cocoanut derived carbons (SAL9190 and 580-26) were pur-
chased from Barneby Cheney, Columbus, OH. Graphtizied carbon (MT) was
purchased from Cabot Corp., Boston, MA.
Ethyl methane sulfonate, g-propiolactone, N-nitrosodiethylamine,
nitromethane and methyl ethyl ketone were from Fisher Chemicals, Pitts-
burgh, PA. Glycidaldehyde and cyclohexene oxide were obtained from
27
-------
Aldrich Chemicals, Milwaukee, WI. From Eastern Organic Chemicals, Roch-
ester, NY, butadiene diepoxide and propylene oxide were purchased. Styrene
oxide, bis-(chloromethyl)ether and bis-(2-chloroethyl)ether were from K&K
Labs, Plainview, NY.
Table 12. COMPOSITION OF MIXTURES I AND II
FOR EVALUATING SORBENT MEDIA
Mixture I Mixture II
Propylene oxide Methyl ethyl ketone
Nitromethane Glycidaldehyde
Bis-(chloromethyl)ether 8-Propiolactone
Butadiene diepoxide Cyclohexene oxide
N-Nitrosodiethylamine Bis-(2-chloroethyl)ether
Styrene oxide Ethyl methanesulfonate
Results and Discussion
The collection efficiencies and breakthrough volumes for several
sorbents are shown in Table 13. Contrary to the results obtained by
28
Ramond and Guiochon , we found that graphitized carbon was inferior as
a sorbent for collecting volatile hazardous vapors. The collection effi-
ciency for Mixture I and II was only 27% and 20%, respectively. In a
separate experiment, the collection efficiency of graphitized carbon
was determined for each compound listed in Table 13. The collection ef-
ficiency for'nitromethane and butadiene diepoxide was only 50%. The
remaining compounds in Mixture I exhibited 0% collection efficiency. In
contrast, the collection efficiencies for the remaining carbons, Tenax GC,
Porapak-Q and the Chromosorbs were all 100% (Table 13).
The breakthrough volumes for propylene oxide and methyl ethyl ketone
were determined for these sorbents since they were the most volatile com-
pounds in the series studied. As shown in Table 13, higher breakthrough
volumes were experienced with the carbon sorbents than with Tenax GC,
Porapak-Q, Chromosorb 101 and 102. On the other hand, breakthrough had
not occurred on Chromosorb 104 even after 36 £ of air had been purged
28
-------
Table 13. COMPARISON OF COLLECTION EFFICIENCIES AND
BREAKTHROUGH VOLUMES FOR SEVERAL SORBENTS
Sorbent
Graphitized carbon
PEL Carbon
PCB Carbon
SAL9190
M1808
Tenax (35/60)
Porapak Q (100/120)
Chromosorb 101 (60/80)
Chromosorb 102 (60/80)
Chromosorb 104 (60/80)
Collection
I
27
100
100
100
100
100
100
100
100
100
Efficiency (%)
II
20
100
100
100
100
100
100
100
100
100
Breakthrough Volume i
Propylene oxide
-
36
40
40
24
4
4
4
8
>36
(JO
MEK
-
20
16
28
12
6
6
10
>28
>36
-------
through the cartridge sampler. On the basis of these experiments it was
concluded that the candidate sorbents which may serve as backup material
to Tenax GC are Chromosorb 104, BPL and PCB carbons and SAL19190 and M1808
cocoanut carbons.
ESTIMATION OF BREAKTHROUGH VOLUMES FOR SEVERAL HAZARDOUS VAPORS ON TENAX
GC AND CHROMOSORB 104
Estimation of breakthrough volumes, i.e. the volume of air sampled
which is required to move the mass transfer zone to the end of the
available packing bed, provides a further assessment of the performance
of sorbents as to their utility for quantitative collection of hazardous
vapors from ambient atmosphere. This section describes and compares
three methods for the determination of breakthrough volumes for several
highly volatile carcinogenic compounds on Tenax GC and Chromosorb 104.
A comparison was made between values obtained under laboratory and field
conditions. The possible effects of displacement chromatography by back-
ground pollutants and premature breakthrough was determined.
Experimental
Estimation of breakthrough volumes was determined using three com-
pletely independent methods. The first method (No. 1) consisted of
determining the elution volume for an organic vapor on a gas chromato-
graphic column packed with the sorbent Tenax GC. A column with the
dimensions of 2.5 mm i.d. x 3.6 m in length was used. Each hazardous
vapor (approximately 900 ng) was injected onto this column and the elu-
tion volume was determined as the product of flow rate and elution time.
After injecting vapors under a series of increasing temperatures, a plot
was made as the log of the reciprocal of the elution volume vs_ temperature
(Fig. 1). Using a linear regression analysis, the breakthrough volume
(50% loss) for ambient conditions was determined by extrapolating to 25°C.
At the end of the experiment, the Tenax sorbent in the chromatographic
column was removed and weighed. The breakthrough volume was expressed in
terms of &/g of sorbent.
The second method (No. 2) for determining breakthrough volume was to
observe the disappearance of hazardous vapors from a Tenax GC cartridge
sampler. Sampling cartridges containing sorbent (1.5 cm x 6.0 cm in
length) were loaded with hazardous vapors and then purged with known
30
-------
QO
5.2-,
4.8-
4.4-
4.0-
3.6-
3.2-
2.8—
2.4-
2.0—
1.6-
1.2-
0.8_
0.
ambient
glycidaldehyde
-propiolactone
©
©
N-nitrosodiethylamine
cyclohexene oxide
0 10 20 30 40 50
T 1 1 1 1 1 1 1 1 1 1 1 1 1 1
60 70 80 90 100 110 120 130 140 150 160 170 180 190 200
T(°C)
Figure 1. Linear regression of the elution volume vs temperature for vapors on Tenax GC.
-------
volumes of air at a rate of 4 £/min. A calibrated volume of air was
passed through the cartridge, after which it was thermally desorbed and
analyzed by glc.
Gas-liquid chromatography (glc) was conducted on a Perkin-Elmer 900
series chromatograph (Perkin-Elmer Corp., Norwich, CN) equipped with dual
flame ionization detectors. A 2.5 mm i.d. x 3.6 m silanized glass column
containing 2% DECS on Supelcoport (80/100 M) was used for resolving the
mixture of hazardous vapors obtained by thermal desorption of cartridge
samplers. The column was programmed from 55-200° @ 10°/min with an
initial and final isothermal period of 2 and 10 min, respectively. Car-
rier gas (N-), hydrogen and air flow were 45, 30 and 250 ml/min, respec-
tively. The injection port, manifold and detector temperatures were
maintained at 250°.
By comparing cartridges which were loaded with known quantities
(100 ng) of hazardous vapors with cartridges which had been purged with
known volumes of air, the amount of each carcinogen which had disappeared
was determined. That volume of air which, decreased the concentration of
carcinogen by 50% constituted the breakthrough volume.
Another technique (No. 3) for measuring breakthrough volumes for
hazardous vapors under laboratory conditions employed a monitoring system
14
described elsewhere
To determine the elution volume of vapors under field sampling condi-
tions, a dual tandem cartridge arrangement (No. 4) was used. The Universal
Sampler 51068 (Research Appliance Co., Allison, PA) was used. The sampler
and multiple-port chamber which accommodated the use of several cartridges
simultaneously during a sampling period have been previously described .
At the beginning of each sampling period a known quantity of vapor (phenyl
methyl ether, nitrobenzene, acrolein, trichloroethylene, 2-chloroethyl ethyl
ether, bis-(chloromethyl)ether and chlorobenzene, approximately 150 ng each)
was loaded onto cartridge samplers. Periodically the back cartridge in the
tandem arrangement was replaced with a vargtn one and sampling was continued
for a brief period (1-5 min, with up to 40 £ passing through it) and then
the backup cartridge was examined by thermal desorption gas-liquid chroma-
tography. Peak areas for each standard vapor were calculated to determine
the amount of vapor disappearing from the front cartridge and appearing in
32
-------
the backup cartridge. At the maximum response observed by flame ioniza-
tion detection, the elution volume was calculated from the elution time
and sampling rates. Breakthrough occurred when 50% of the vapor had
passed through the front cartridge.
Results and Discussion
A comparison of the breakthrough volumes obtained by Methods No. 1
and 2 for a series of vapors on Tenax GC is given in Table 14. All the
Table 14. COMPARISON OF BREAKTHROUGH VOLUMES
OBTAINED FROM TWO DIFFERENT TECHNIQUES
FOR TENAX GC3
Test Compound
Propylene oxide.
Nitromethane
Glycidaldehyde: .
B-Propiolactone
Bis- (chloromethyl) ether
Butadiene diepoxide
Breakthrough
Method No. 1
7
40
70
158
189
306
Volume H/g
Method No. 2
9
42
51
130
186
270
aSee text for description of two methods employed; each value is an
average of duplicate determinations.
breakthrough volumes obtained for each of the hazardous vapors were in
good agreement between the two methods employed. Of the compounds tested,
the lowest breakthrough volume (approximately 7-9 i/g of Tenax GC) was
exhibited by propylene oxide. Since a typical glass sampling cartridge
contained 2.2 g of Tenax sorbent (1.5 cm i.d. x 6.0 cm in length) the
breakthrough volume is approximately 16 £. Because the determination of
breakthrough volumes utilizing method No. 1 was in good agreement with
the second method which is more laborious, the first method was used for
determining the breakthrough volume of several additional hazardous vapors,
These results are shown in Table 15. These results clearly indicate that
the elution volume for a compound on Tenax GC sorbent is highly dependent
33
-------
Table 15. BREAKTHROUGH VOLUMES FOR SEVERAL HIGHLY VOLATILE COMPOUNDS
ON TENAX GC (35/60 MESH) CARTRIDGES
Compound
Ac role in
Propylene oxide
Diethyl sulfate
Nitromethane
Glycidaldehyde
3-propiolactone
Bis- (r.hloromethyl) ether
Butadiene diepoxide
Cyclohexene oxide
Diethylnitrosamine
Aniline
Ethyl raethanesulfonate
Styrene oxide
Acetophenone
2.15 g Tenax
(1.5 cm i.d. x 6.0
9.7
15.0
19.1
23.8
147.0
333.0
400.0
646.0
1,040.0
1,220.0
2,100.0
2,420.0
7,550.0
2,880.0
Q
Breakthrough Volume (£)
2.87 g Tenax
cm) (1.5 cm i.d. x 8.0 cm)
13.0
20.0
25.4
31.7
195.0
440.0
530.0
860.0
1,380.0
1,620.0
2,800.0
3,220.0
10,000.0
3,830.0
aVolume required to elute one-half of adsorbed vapor at 25°C.
-------
upon the molecular structure. The elution volume for acrolein on a stan-
dard glass sampling cartridge (1.5 cm i.d. x 6 cm in length) was 9.7 &.
By increasing the cartridge length from 6 to 8 cm, the elution volume is
increased from 9.7 to 13.0 £ (for acrolein) which is predicted from the
1.34 ratio of bed depths. The increase in the breakthrough volume is also
apparent in the case of styrene oxide which for a 6 cm length cartridge
o
was 7.5 m whereas on an 8 cm cartridge the elution volume increased to
10 m3.
The breakthrough volumes were also determined for Chromosorb 104 using
method No. 1 (analysis on a gas chromatographic column). Extrapolation of
the linear regression analysis to 25° yielded the breakthrough volumes
shown in Table 16. Table 17 compares the breakthrough volumes for Tenax GC
and Chromosorb 104. On Chromosorb 104, the breakthrough volume for pro-
pylene oxide was four times greater than on Tenax GC. For nitromethane,
it was nine times larger. These data indicate that Chromosorb 104 indeed
has a much higher retentive volume for the volatile hazardous compounds
employed in this study. Thus it may serve as a backup sorbent material
for trapping 'the more volatile hazardous vapors which may pass through
the Tenax GC sorbent bed; however, the retention index for water on
Chromosorb 104 is larger and preliminary observations indicate that the
quantity of water vapor retained is an order of magnitude greater. Fur-
ther investiations are warranted on the performance of Chromosorb 104
and the carbons as potential alternate collecting media for hazardous
vapors.
Since all of the results thus far were obtained under laboratory
conditions which do not include the background pollution profile normally
encountered under field sampling condition's, these results represent the
maximum expected breakthrough volume. Under field sampling conditions,
it is conceivable that the elution volume may decrease via displacement
chromatography by other pollutants. Breakthrough volumes under field
sampling conditions were also determined ir order to compare these values
to those obtained under ideal or laboratory conditions.
We had previously reported studies on the breakthrough volume under
14
field sampling conditions . These studies had indicated that premature
breakthrough had not occurred under field sampling conditions in locations
35
-------
Table 16. BREAKTHROUGH VOLUMES FOR CHROMOSORB 104*
Test Compound
Nitromethane 246
Diethyl Sulfate 113
Acrolein 40
Propylene Oxide 32
Determined by Method No. 1, see text for explanation.
Table 17. COMPARISON OF BREAKTHROUGH VOLUMES
FOR TENAX GC AND CHROMOSORB 104
a
Test Compound Tenax" GC * Chromosorb 104
Propylene oxide 8 32
Nitromethane 27 246
Average of two techniques.
36
-------
14
where the magnitude of the pollution profile was small (Table 18) . Fur-
ther breakthrough studies were executed in an area which was regarded as
having a high pollution background (Beltline-U.S. 1 and Western Blvd.,
Raleigh, NC). The breakthrough for five hazardous vapors is given in Table
19. For a cartridge with the dimensions of 1.5 cm i.d. x 3 cm in length,
the breakthrough volumes for acrolein, trichloroethylene, 2-chloroethyl
ether, bis-(chloromethyl)ether and chlorobenzene were 5, 52, 112, 302 and
352 &, respectively (Table 19). Calculation of the breakthrough volume on
a Jl/g basis is shown in Table 20. Also given is the breakthrough volume
for a standard glass sampling cartridge of 1.5 cm i.d. x 6.0 cm in length.
Comparison of the breakthrough volumes obtained under laboratory condi-
tions (Table 15) and under field sampling conditions (Table 20) for acro-
lein and bis-(chloromethyl)ether indicates that field sampling for these
two constituents under a heavy pollution profile did not induce premature
breakthrough. We are currently determining the breakthrough volume for
trichloroethylene, 2-chloroethyl ethyl ether and chlorobenzene using
method no. 1 under laboratory conditions in order to compare these values
with those obtained under field sampling conditions. In general, massive
premature breakthrough does not seem to occur when sampling is performed
under a high pollution profile which is primarily auto exhaust.
37
-------
Table 18. BREAKTHROUGH STUDY OF ORGANIC VAPORS
DURING FIELD SAMPLING3
Sampling Time
(min)
30
60
90
150
210
270
300
330
360
390
420
480
540
570
600
660
720
750
810
870
930
960
Volume Air
Sampled (£)
350
710
1060
1770
2480
3190
3540
3tf90
4250
4600
4960
5660
6370
6730
7080
7790
8500
8850
9560
10270
10970
11330
Phenyl methyl
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
10.8
3.0
0
0
0
2
Peak Areas (cm )
ether Toluene
0
0
0
4.5
5.4
5.5
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Nitrobenzene
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
aTenax GC (35/60) cartridge (1.5 cm i.d. x 6 cm in length); sampling
was 24 £/min. Sampling was in the Research Triangle Park, N. C.
Vi *^
Breakthrough volume was >12 m .
38
-------
Table 19. BREAKTHROUGH STUDY OF HAZARDOUS VAPORS DURING FIELD SAMPLINGa
OJ
VO
2
Peak Area (cm )
Sampling Time
(min)
0.3
0.5
0.6
1.2
1.7
2.2
5.2
8.2
11.2
16.2
18.2
20.2
22.2
30.2
35.2
40.2
Volume Air
Sampled (£,)
3
5
7
12
17
22
52
82
112
162
182
202
222
302
352
402
Acrolein
15.0
16. 6b
13.2
0
0
0
0
0
0
0
0
0
0
0
0
0
Trichloro-
ethylene
0
0
0
0
0
0
9.8b
6.5
3.1
1.9
0
0
0
0
0
0
2-Chloroethyl-
ethyl ether
0
0
0
0
0
0
5.8
7.2
9.5b
9.0
8.0
2.5
0
0
0
0
Bis-(chloromethyl) -
ether
0
0
0
0
0
0
0
0
0
0
0
3.0
5.2
14. 2b
12.4
5.8
Chlorobenzene
0
0
0
0
0
0
0
0
0
0
2.5
2.6
3.1
6.2
7.3b
6.0
aTenax GC (35/60) cartridge (1.5 cm i.d. x 3 cm in length). Field sampling was at Beltline-U.S. 1 and
Western Boulevard, Raleigh, NC. Vapors were resolved on a 200 ft OV-101 SCOT programmed from 30-220°
@ 4°/min.
Represents 50% breakthrough point.
-------
Table 20. BREAKTHROUGH VOLUME OF HAZARDOUS VAPORS FOR
TENAX GC (35/60) OBTAINED DURING FIELD SAMPLING
Breakthrough Volume
Compound Jl/g 1.5 cm i.d. x 6.0 cm cartridge
Acrolein 2.8 10
Trichloroethylene 51.6 104
2-Chloroethyl ethyl ether 104.2 224
Bis-(chloromethyl)ether 280.9 604
Chlorobenzene 325.6 700
40
-------
SECTION VI
DESIGN AND PERFORMANCE OF A PORTABLE FIELD SAMPLER
Collection of pollutants by other investigators has been performed
at modest flow rates (20-2000 ml/min), because the concentrations of
these substances were relatively high (ppm). In contrast, the sampling
rates and time required for this research program were larger, since
3
the hazardous vapors were anticipated to occur at the low ng/m levels
14
(ppb) . This relationship between sampling rate, sampling time and the
14
concentration of pollutants in ambient air was previously discussed
In order to collect sufficient quantities of each atmospheric car-
cinogen for qualitative and/or quantitative analysis, the field sampling
unit had to meet several requirements. These were: (1) a sampling rate
3
adjustable from 0-3 m /hr at the pressure drop generated with a sampler
cartridge in-line, (2) a capability of multiple cartridges on-line during
a sampling period, (3) uninterrupted 24 hr operation, and (4) the option
to push or pull air samples through the cartridge sampler. All of these
factors ultimately determined the power (milliamps/A/min) required for
sampler operation.
Also, these and additional factors were found not to be independent
14
of each other . Other limitations were found to be imposed by: (1) the
collection efficiences of the packing, (2) sorbent breakthrough charac-
teristics, (3) the lowest detectable concentrations of the carcinogenic
compounds by the instrumental technique, and (4) the size and shape of the
cartridge sampler and how pressure differential increases with increased
flow through it. Because contamination of a sample was to be avoided, the
pump design was also an important characteristic. Of these criteria
considered in designing a field sampling unit, the pressure differential
developed across a cartridge at a specified flow rate was deemed the
most important criterion and was treated in some detail in the previous
14 '
report
The power required to pump air through sorbent-packed tubes is a
function of pressure differential (AP) across the tube under flow con-
ditions. The AP is related to: (1) sampling rate, (2) diameter and
length of cartridge, (3) particle size distribution, and (4) particle
shape. A mathematical expression was derived for calculating AP using
41
-------
14
the physico-chemical properties of the sorbent . Based upon AP, the
power requirements for a pumping system were calculated and applied to
the fabrication of a portable field sampler.
In this section the power requirements, the fabrication of a portable
sampler, and the testing of portable field samplers is described.
POWER REQUIREMENT
From the value of AP, the theoretical power (watts) required for com-
pression or expansion of the air and its delivery through the sampler was
estimated using a formula derived from the Moss and Smith equation for
47
adiabatic horsepower . The formula employed was:
k-1
Power (Watts) = £/min x 5.968 x [(P1/P2) k -1]
where p. and p~ are the high and low pressures across the sampler, respec-
tively and k is a ratio of specific heats for air, C and C . This formula
is based upon air at 14.7 psi, 23°C and 36% relative humidity. Its density
3
was taken at 0.075 Ib/ft , k was set at 1.3947.
Figure 2 depicts the theoretical power required to pump air through a
5 cm depth of sorbent packing. For a flow rate of 20 £/min, the change
from 60/80 mesh particles to 18/20 in the 1.06 cm tube, reduces power
requirements by a factor almost of 5 (30.4 watts to 6.4). Increasing
the tube diameter from 1.06 cm to 1.82 cm decreases power for the 60/80
mesh packing from 30.4 to 21 watts. It was concluded that tube dia-
meters of approximately 1.5 cm, particles of about 35/60 mesh and bed
depths of about 5 cm would allow sampling rates of 20 &/min for a theo-
retical power consumption of 15 watts (0.02 horsepower). However,
practical power requirements are expected to be at least twice the theo-
retical values to allow for power losses in the pump itself. For example,
a cartridge of Tenax GC 35/60 mesh in a 1.82 cm tube would require
twice the theoretical 7.4 watts or 14.8 watts to sample air at 20 £/min.
It is apparent that most of the sampling for qualitative analysis would
therefore require the use of storage batteries which have the necessary
capacity.
FABRICATION OF PORTABLE SAMPLERS
In conjunction with Dr. Lou Ballard of Nutech Corp., (Durham, NC),
two portable field samplers were custom-built according to the criteria
42
-------
100 r-
10
_e
°*
o
Dp (Cm)
-U.S. Mesh Tube i.d. (cm)
A 0.0211
Q0.0211
Ao.035
DO.093
• 0.035
60/80
60/80
35/60
18/20
35/60
1.06
1.82
1.82
1.06
1.49
0.1
10
100
Figure 2. Relationship between flow rate and theoretical power requirements
at various tube diameters and particle size.
-------
outlined under the power requirements as well as additional general re-
quirements. These were: (a) an AC/DC converter for 115 V AC/12 V DC
operation, (b) capability of flow rates up to 15 &/min, (c) capable of
pulling 7-8 Ji/min at a pressure of 5 in of mercury, (d) a power require-
ment of 15 watts at 5 in of mercury pressure drop, (e) capable of operating
for 8 hr on a 12 V storage battery (50 amp-hr), (f) a gas meter for regis-
3
tering a total of up to 10,000 ft , (g) a flow meter for regulating flow
rates of 0-10 £/min under sampling conditions, (h) a quarter inch quick
connect to the vacuum line for attaching cartridge samplers, and (i) a
vacuum gauge and a diaphragm pump with a dampening chamber.
The portable samplers which were fabricated according to these
design criteria are shown in Figure 3. The present design allowed
AC/DC operation and while in the AC mode, the DC power supply was
used to recharge 12 V storage batteries while simultaneously operating
the diaphragm pump as a field sampler. The AC/DC (Model No. 221A) sam-
pler consisted of a pump, flow meter, gas meter, and quick connect fittings
and .is depicted in Figure 3. Air was drawn through the cartridge samplers
which were attached to a quarter-inch connect fitting. A drying tube
packed with Drierite^was interposed between the cartridge samplers, in
order to remove excess amounts of moisture and protect the diaphragm pump.
A Whitey valve (Whitey, Co., Oakland, CA) is used for regulating the samp-
ling rate. A vacuum gauge which is not shown in the figure can be located
between the cartridge sampler and the regulating valve. A baffle chamber
is interposed between the pump and flow meter in order to provide non-
pulsed flow through the flow and gas meters so that more accurate gas flow
measurements may be obtained.
The portable field samplers weighed approximately 23 Ib. The carrying
case was 39 cm x 37 cm x 27 cm (w x h x d). Located on the front panel
were the AC/DC and pump power switches, the gas volume meter, vacuum gauge,
flow regulating valve, and an amp meter and a flow meter.
EXAMINATION OF PORTABLE SAMPLER PERFORMANCE
The two portable Nutech Model 221A samplers were examined under field
sampling conditions. The relationship between flow rate, pressure dif-
ferential, and cartridge dimensions for the samplers operated in the AC
mode are depicted in Table 21. Two cartridge dimensions (1.0 and 1.5 cm
i.d.) and two particle sizes of Tenax GC were examined at various flow rates
44
-------
POWER SWITCH
VALVE
VAC.
PUMP
GAS VOLUME
REMOVABLE FRONT
AND REAR PANELS
BATT. TERMINAL
AC SWITCH
110
CJX3O»-
12 VDC (AUXILIARY)
DC
POWER
SUPPLY
VALVE
AIR IN
1/4 QC
PUMP SWITCH
FLOW
METER
DRYING
TUBE
™TJ
B /
GAS
METER
Figure 3. Nutech Model 221-A AC-DC Sampler
45
-------
Table 21. RELATIONSHIP BETWEEN FLOW RATE, PRESSURE DIFFERENTIAL,
AND CARTRIDGE DIMENSIONS FOR NUTECH MODEL 221-A
PORTABLE SAMPLERS (AC MODE)
F, H/m:
Cartridge Size
(cm i.d. x cm in length) No. Mesh Sampler No.
1x6 1 60/80 2 (4)
4 (9.5)
4.5 (11.5)
2 60/80 2 (1)
4 (2.7)
7 (7)
1.5 x 6 1 60/80 2 (1.6)
4 (4.7)
6.2 (8.5)
2 60/80 2 (0.2)
4 (1.6)
8 (5.2)
1x6 1 35/60 2 (2)
4 (5.8)
5.5 (9.5)
2 35/60 2 (0.1)
4 (1.5)
7.7 (5.5)
1.5 x 6 1 35/60 2 (1)
4 (3)
6.7 (7.2)
2 35/60 2 (0.1)
4 (0.7)
8.7 (3)
Ln (AP, in Hg)
1 Sampler No. 2
2 (4)
4 (9.7)
4.7 (12)
2 (1.5)
4 (3.7)
7 (8)
2 (2.2)
4 (5.5)
6 (9.5)
2 (0.8)
4 (1.8)
8.2 (5.6)
2 (2.5)
4 (6.8)
5.5 (10.5)
2 (0.6)
4 (1.8)
8 (6.0)
2 (1.5)
4 (3.5)
6.7 (8.5)
2 (1.0)
4 (3.6)
9 (4.5)
46
-------
on samplers 1 and 2. For a single cartridge of 1.0 cm i.d. the maximum
flow rate obtainable was approximately 4.6 £/min at a pressure drop of
11.8 inches of mercury. This condition represented the lowest flow rate
and highest pressure drop experienced. In contrast a cartridge of 1.5 cm
i.d. containing 35/60 mesh sorbent allowed a flow rate of 6.7 i/min to be
achieved. These performance data using the portable samplers in the AC
mode are well within the design specifications.
The relationships between flow rate, pressure differential, and car-
tridge dimensions for these portable samplers were also examined in the DC
mode. These results are shown in Table 22. The relationships between flow
rate and pressure differential were similar to those observed when the sam-
plers were operated in the AC mode. However, in this case, we measured the
amperage required to operate the samplers under various flow rates. In gene-
ral the requirement was 2.0-2.5 amps, depending on the cartridge size, sor-
bent mesh, and flow rates employed. On the basis of the amperage values ob-
tained from this experiment, it can be concluded that for a standard 12-volt
50 ampere-hour storage battery, the maximum sampling period attainable is
approximately 20 hours.
The performance of the portable samplers under battery operation was
also examined over a typical sampling period. These results are shown in
Table 23. The sampling rate, pressure differential, and current drawn were
relatively constant for a 9-hour sampling period. At the end of the sampling
period the remaining battery charge was approximately 50%.
Based on the results obtained for the two samplers as shown in Tables
21-23, the performance of the portable field samplers was within the design
specifications described above.
47
-------
Table 22. RELATIONSHIP BETWEEN FLOW RATE, PRESSURE DIFFERENTIAL,
AND CARTRIDGE DIMENSIONS FOR NUTECH MODEL 221-A
PORTABLE SAMPLERS (DC MODE)3
oo
Cartridge Size
(cm i.d. x 3 m in length) No. Mesh
1x6 1 60/80
2 60/80
1.5 x 6 1 60/80
2 60/80
1x6 1 35/60
2 35/60
1.5 x 6 1 35/60
2 35/60
Sampler # 1
F, fc/min (AP)a
2 (3,5)'
4 (9.0)
4.7 (11.5)
2 (0.7)
4 (2.3)
7 (7.2)
2 (1.1)
4 (3.0)
7 (7.5)
2 (0.1)
4 (3.0)
8.0 (3.7)
2 (2.2)
4 (5.2)
5.7 (9.5)
2 (0.1)
4 (2.0)
8 (5.7)
2 (0.9)
4 (3.2)
7 (7.8)
2 (0.1)
4 (0.4)
9 (3.6)
Amp
2.0
2.1
2.2
2.0
2.1
2.4
2.0
2.1
2.3
2.0
2.1
2.4
2.0
2.2
2.3
2.0
2.1
2.4
2.0
2.1
2.3
2.0
2.1
2.5
Sampler #
F, A/min (AP)
2 (4.8)
4 (9.8)
4.5 (12)
2 (1.5)
4 (3.7)
7 (8)
2 (1.4)
4 (3.7)
7 (8.5)
2 (0.5)
4 (1.5)
8 (4.5)
2 (2.5)
4 (6.1)
5.5 (10.2)
2 (0.4)
4 (2.2)
8 (6.3)
2 (1.2)
4 (3.7)
7 (8.2)
2 (0.1)
4 (1.1)
9 (4.2)
2
Amp
1.9
2.0
2.1
1.8
2.0
2.2
1.8
1.9
2.2
1.9
2.0
2.2
1.9
2.0
2.1
2.0
2.1
2.4
1.8
2.0
2.1
1.8
2.0
2.3
A 12 V, 50 amp-hr storage battery was used; AP is in in. Hg.
-------
Table 23. PERFORMANCE OF NUTECH MODEL 221-A PORTABLE FIELD SAMPLERS
UNDER BATTERY OPERATION3
•t-
VO
Time Elapsed
(hr)
1
2
3
4
5
6
7
8
9
9.6
Flow (£/min)
9.0
9.0
9.2
9.2
9.5
9.5
9.5
9.5
9.5
9.5
Sampler No. 1
Vacuum (in Hg)
3.3
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.2
Volume (£)
511
980
1,480
1,940
2,300
2,940
3,420
3,930
4,330
4,600
Amp
2.3
2.2
2.2
2.2
2.2
2.2
2.2
2.1
2.1
2.1
Flow (Jl/min)
9.2
9.2
9.2
9.2
9.5
9.5
9.5
9.5
9.6
9.6
Sampler No.
Vacuum (in Hg)
3.7
3.7
3.7
3.7
3.7
3.7
3.7
3.7
3.7
3.7
2
Volume (£)
500
1,100
1,650
2,200
2,600
3,120
3,580
4,040
4,500
4,960
Amp
2.5
2.2
2.2
2.2
2.1
2-l
2.1
2.1
2.0
2.0
Two Tenax GC cartridges (1.5 cm i.d. x 6.0 cm in length) were employed; 12V, 50 amp-hr storage
battery was used.
-------
SECTION VII
IDENTIFICATION OF HAZARDOUS AND BACKGROUND POLLUTANTS FROM
SEVERAL GEOGRAPHICAL AREAS IN THE CONTINENTAL U.S.
Several sites within three geographical areas (Figures 4-6) were
selected for collection and analysis of hazardous and background ambient
air pollutants. The rationale for site selection was based upon the
presence of either a highly industrialized area and/or the presence of
photochemical smog. The three areas selected were: the Kanawha Valley
in West VA, greater Houston, TX area, and Los Angeles, CA Basin.
Located in the Kanawha Valley are many manufacturers of organic
and inorganic chemicals. DuPont (near Belle, West VA) has a large
ammonia organic cheir.ical complex for the synthesis of substances such
as substituted dianilines, methyl methacrylate, ethers and hydrides,
aldehydes, polyolefins, chloronethanes, epichlorohydrin, chlorine,
hydrogen peroxide, thiols, etc.
In South Charleston are production and consumption plants (Union
Carbide, and FMC). Plastics, PVC, antifreeze, molecular chlorine and halo-
genated organics, carbon disulfide, peroxides, etc. are the predominant
chemicals produced here. The major facility in Institute is Union Carbide
which also processes a broad spectrum of compounds, e_.£. viscose rayon, and
phthalate esters. There is also a large scale olefin processing complex
and a rubber accelerator plant. These potential sources of pollutants
may also be involved in photochemical reactions. Further down the Kanawha
Valley near Nitro, Monsanto and FMC have plants for the production of anti-
oxidants, rubber accelerators, and other materials.
Because of the combination of petroleum refineries, organic chemical
manufacturers, automobile exhaust, high humidity and strong sunlight,
nitrosation, ozonization and sulfonation of olefins and aromatics may
occur in the Houston, TX area. Located in Pasadena are Ethyl Corpora-
tion (PVC plant), Champion Paper Co., Crown Refinery, Arco Refinery,
Goodyear and Petrotex Chemicals, Charter International Refinery and
Stauffer Chemical Co. Ashland Oil, Exxon Refinery, and Chemical Corp.
are located in Baytown. Texas City is also highly industrialized and
includes Union Carbide (producing PVC), Amoco Refinery, Texas Refinery,
Marathon Oil Refinery, Monsanto, GAP, and Robinson Electric. Diamond
50
-------
HO
A « May Street
B = Stuebner Airline
C - Shaw Drive
D « Texas City
E • 7200 Bayway Drive
To-Texas City
Figure 4. Map of Houston, Texas and Vicinity depicting sampling sites
vex
I
I-IC
HOUSTON
AND VICINITY
o ! ? 3 1 s
tool* of
-------
WEST COV1NA
Figure 5. Map of Los Angeles, CA and Vicinity depicting sampling sites.
-------
Figure 6. Map of the Kanawha Valley in West Virginia
depicting sampling sites.
53
-------
Shamrock Corp. (PVC plant) and Shell Chemical Co. (PVC plant) are in
Deer Park, TX. Tenneco (Houston) synthesizes vinyl chloride.
The Los Angeles Basin area has been extensively studied and has
served as a model for air pollution studies. This location represents
an environment where photochemical smog is the predominant type of air
pollution. In addition, industrial firms are located along the coast
line between Long Beach and El Segundo, £.£. B. F. Goodrich Co. and
American Chemical Corp. who produce PVC and vinyl chloride. The pre-
sence of olefin and aromatic hydrocarbon manufacturers along this area
are potential sources for emission of primary uv absorbers which can par-
ticipate in the photochemical processes in the atmosphere to yield hazard-
ous vapors.
For these reasons, we have conducted during the past year extensive
sampling, collection and qualitative analysis of ambient air pollution
from these geographical areas. This section discusses these results.
Experimental
Field Sampling Protocol and Procedure
The sampling procedure employed consisted of concentrating organic
vapors on a 1.5 x 6.0 cm glass cartridge containing Tenax GC (35/60).
Tables 24-26 depict the sampling protocol used for the Kanawha Valley,
Houston, TX area and the Los Angeles Basin.
Ambient air samples were collected with a Universal Sampler 5-1068
equipped with a Teflon^* multiple-port head as previously described .
The glass cartridge samplers were prepared in the laboratory, transpor-
ted by air freight to the various geographical locations, and, after
sampling was completed, were returned also by air freight.
Sampling Analysis and Identification Techniques
The instrumental system (glc-ms-comp) used for the qualitative
analysis of ambient air pollutants and the inlet manifold used for re-
covering vapors trapped on Tenax GC cartridge samplers were as described
elsewhere ' . The desorbed vapors were resolved by capillary gas-
liquid chromatography and mass cracking patterns were automatically and
continuously obtained throughout the glc run with a Varian CH-7 gas
chromatograph/mass spectrometer. The cracking patterns and retention
time data were accumulated on a magnetic tape deck and further processed
54
-------
Table 24. SAMPLING PROTOCOL FOR KANAWHA VALLEY, WV
No.
1
2
3
Experiment
Siteb
Belle, WV
Belle, WV
4th & C St.
Sampling
Time
(hr)
2
8
2
Sampling
Rate
1/min
20.8
36.8
22.9
No. Cartridges
4
2
4
3
m /Cartridge
2
17
2
.50
.64
.66
Remarks
8:00 a.m
9/14/74,
5-10 mph
cast.
8:00 a.m
. - 6:00 p.m. ,
wind southeast
, partial over-
. - 6:00 p
.m. ,
South Charleston,
WV
4th & C St.
South Charleston,
WV
llth & Myers
Dunbar, WV
39.4
16.7
9/12/74, wind east,
10-12 mph, partial over-
cast, light rain last
15 min.
18.90
2.38
8:05 a.m. - 6:15 p.m.,
9/11/74, heavy over-
cast, visibility 3-400 yds.
6
7
8
llth & Myers
Dunbar, WV
20 St.
Nitro, WV
20th St.
Nitro, WV
8
2
8
25.9
20.6
38.8
3
4
2
12.40
2.47
18.60
8:00 a.m. - 6:00 p
9/13/74, foggy and
east 10-15 mph.
.m. ,
wind
Tenax GC cartridges (1.5 cm i.d. x 6.0 cm in length) were used.
All sampling locations were at Fire Departments in these cities.
-------
Table 25. SAMPLING PROTOCOL FOR HOUSTON, TEXAS AND VICINITY
01
Sampling
Time
Experiment Site (hr)
A May St. 24
Houston, TX
B Stuebner Airline Rd. 24
Houston, TX
Cb Shaw Dr . , 24
Pasadena, TX
Db Texas City, TX 24
E 7200 Bayway Dr. 24
Bay town, TX
Sampling
Rate
1/min
15
15
15
15
15
No' a 3
Cartridges m /Cartridge Remarks
4 21.6 4:30 p.m. - 4:30 p.m.,
11/16 - 11/7/74, heavy
overcast, rain, 50-70°F.
4 21.6 10:30 a.m. - 10:30 a.m.
11/8 - 11/9/74, cloudy,
70°F.
4 21.6 11:30 a.m. - 11:30 a.m.,
11/11 - 11/12/74, clear,
northwest wind 10-12
mph, 51-64° F.
4 21.6 2:15 p.m. - 2:15 p.m.,
11/12 - 11/13/74, clear,
northwest wind 8-10 mph,
48-64°F. .;
4 21.6 4:30 p.m. - 4:30 p.m.,
11/13 - 11/14/74, clear,
south wind 10-12 mph,
45-64°F.
Tenax GC cartridges (1.5 cm i.d. x 6.0 cm in length) were used.
These sites were at Connie stations operated by the State of Texas Pollution Control Agency.
-------
Table 26. SAMPLING PROTOCOL FOR LOS ANGELES BASIN AREA
o
Experiment Site
1 Arizona Ave.
Santa Monica, CA
2 Phillips Ave.
West Covina, CA
3 East Laurel
Glendora, CA
4 West Broadway
Anaheim, CA
5 Nelson St.
Garden Grove, CA
6 Arizona Ave.
Santa Monica, CA
7 West Broadway
Anaheim, CA
Sampling
Time
(hr)
8
6.25
11
7.5
7.5
15
15.25
Sampling
Rate
1/min
15
15
15
15
15
18
18
No.
Cartridges
4
4
4
4
4
3
3
3
m /Cartridge Remarks
7.2 8:50 a.m. - 5:00 p.m.,
- 3/31/75, clear, west
wind 10 mph, 55° F.
5.6 10:00 a.m. - 4:15 p.m.,
4/1/75, partly cloudy,
south wind 5 mph, 62°F.
13.5 10:00 a.m. - 9:00 p.m.,
4/2/75, sunny, no wind,
70°F.
6.75 9:30 a.m. - 5:00 p.m.,
4/3/75, sunny, no wind,
70°F.
6.75 9:00 a.m. - 4:30 p.m.,
4/4/75, cloudy, west
wind 5 mph, 58°F.
16.2 5:00 p.m. - 8:00 a.m.,
3/31 - 4/1/75, no wind,
55°F.
16.47 5:30 p.m. - 8:15 a.m.,
4/3 - 4/4/75, west wind
10 mph, 65° F.
Experiments 1-5 utilized 1.5 cm x 6.0 cm Tenax GC (35/60) cartridges; all samples taken during daylight
hours. Experiment 6 utilized a 1.5 x 4.0 cm front (Tenax) and a 1.5 cm x 2 cm back (Chrom 104) cartridge;
sampling was at night. Experiment 7 used a front and back cartridge of Chrom 104 (1.5 cm x 3.0 cm);
sampling was at night. Experiment 8 was identical to No. 6.
-------
by an on-line Varian 6201 computer. Computer programs (KOSB) were em-
ployed which converted the acquired spectra into a sequential series of
mass spectra and were correlated to peak retention time on a total ion
current plot. Data output from the 620i computer was provided in two
forms: (1) a teletype listing which contained the mass spectrum number,
the number of peaks in the cracking pattern, total maximum and minimum
m/e peak intensity and standard deviation from calibration m/e and (2) an
electrostatic plot of total ion current plots and/or normalized mass
spectra. After mass conversion of the mass cracking data, mass fragmen-
tograms were obtained from the 620i computer.
The operating parameters for the glc-ms-comp system for the analy-
sis of samples collected on glass cartridges from Charleston, WV, Houston,
TX and Los Angeles, CA are shown in Table 27. Ambient air samples were
analyzed on 200 or 400 ft SCOT columns coated with either OV-17 or
OV-101 stationary phase. The desorption of ambient air pollutants from
the Tenax cartridge sampler was at 265-270°C. A single stage glass jet
separator interfaced the SCOT capillary columns to the mass spectrometer
and was maintained at 200°C.
Identification of resolved components was achieved by comparing the
mass cracking pattern of the unknown mass spectra to an eight major peak
48
index of mass spectra . In several cases the identification was con-
firmed by comparison with authentic compounds of the mass spectrum and the
elution temperature on two different columns (OV-17 and OV-101 SCOT capil-
laries) . Particular note was made of the relationship of the boiling point
of the identified compound to its elution temperature and to its order of
elution of constituents in homologous series, since the OV-101 SCOT capil-
lary column separates primarily on the basis of boiling point.
Results and Discussion
Figure 7 represents a total ion current plot from the mass spectro-
meter for a Tenax GC cartridge blank which had been transported to and
from Los Angeles, CA. The cartridge sampler was sealed in a Corex^
centrifuge tube during transportation and served as a reference control
to ensure that cartridge samplers were not contaminated during shipment by
air freight. As shown in this figure, the background observed was low.
58
-------
Table 27. OPERATING PARAMETERS FOR GLC-MS-COMP SYSTEM
Parameter
Setting
Inlet-manifold
desorption chamber
valve
capillary trap - minimum
maximum
thermal desorption time
GLC
OV-101 SCOT (200 or 400 ft) or
OV-17 SCOT (200 ft)
column
carrier (He) flow
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
30 or 40-220°C, 4°C/min
4 ml/min
200°C
-2 x 10~ torr
300 yA
5.5
1 sec/decade
m/e 20 -»• 300
59
-------
Ul
a.
z
UJ
cc
a:
o
o
100
90
80
70-
60
50
40
30
20
I0h
0
2
JV
4
.A*.
54
H—
66
H-
78
—I—
12
90
102
114
IT
138
ISO
15
TIME (MIN)
18
24
27
30
7igure 7. Total ion chroma to gram of. Tenax GC cartridge blank. See Table 27
for glc-ms conditions. A 400 ft OV-101 SCOT was used.
-------
100,-
90
80
70
= 60
h-
UJ
o
50
| 40-
_l
30-
20
I0h
P
198
42
210
45
222
294
246
54
258
57
270
36
39
48
51
60
Figure 7 (cont'd)
-------
Figures 8-12 are representative of the total ion current plots ob-
tained for pollutants collected from the Kanawha Valley, Houston, TX area
and the Los Angeles Basin. The identity of the components in Figure 8
are given in Table 53 of the Appendix. It is evident from these pro-
files that use of high resolution columns is imperative in order to ob-
tain satisfactory separation of the many components in the sample. The
large, broad peak which, for example, in Figure 8 occurs between 13-17
minutes represents a trace amount of water which was trapped on the Tenax
cartridge. However, the presence of a small amount of water does not
interfere with the mass cracking patterns or the identification of the
constituents. The two SCOT columns employed in this study (OV-17 and
OV-101 stationary phases) provided sufficient difference in resolution of
the constituents to allow the identification of many more constituents in
the sample than would have been possible by utilizing either column alone.
Of the columns employed, the most useful was the 400 ft OV-101 SCOT. Addi-
tional ion current plots and the identity of the chromatographic peaks are
given in the?figures and tables in the Appendix to this report.
Tables 28-31 summarize the pollutants identified in air samples col-
lected from these three geographical locations. A total of 23 halogenated
hydrocarbons (Table 28) have been identified in ambient air by the de-
scribed techniques of capillary gas-liquid chromatography mass spectro-
5-7 49
metry computer. Among these two are known carcinogens, vinyl chloride '
and trichloroethylene . The majority of compounds identified were
chlorinated. To date one brominated compound (bromoform) was identified in
ambient air from Houston and Los Angeles.
Many oxygenated compounds have also been discovered. A mercaptan,
several alcohols, ketones, aldehydes, ethers, esters, and a phenol are
represented in Table 29. Furthermore, we have tentatively identified two
epoxides, epoxyheptane and styrene oxide.
Because of the generally high concentration of auto exhausts in these
areas, the majority of the background pollutants were aromatic and aliphatic
hydrocarbons. Tables 30 and 31 list the representative pollutants which we
have identified. Two particularly interesting compounds were benzonitrile
and a-cyanopyridine. The majority of the aliphatic hydrocarbons were not
completely identified since it was difficult to distinguish between the
62
-------
I
I
J
36
8
12
16 20
TIME (MIN)
24 28
32
I
I
I
30
46 62
78 94 110 126
COLUMN TEMPERATURE, °C
142 158 174
Figure 8. Total ion chromatogram of ambient air sample from South Charleston, WV.
See Table 27 for glc-ms conditions and Table 53 for identity of peaks.
-------
40
39
34
ON
-P-
1
28
1
32
1
36
1
40
1
44
1
48
1
52
1
56
TIME (MIN)
I
I
I
142 158 174 190 206 220 236
COLUMN TEMPERATURE, °C
252
Figure 8 (cont'd)
-------
Wi
90
80
P
2 70
5 60
£
g 40
«i 30
20
10
42
i&t
54
TEMPERATURE (°C)
66 78 90
i r
r
102
1r
114
+
126
21
Figure 9.
12 15
TIME (MINI)
Total ion chromatogram of ambient air sample from Pasadena, TX. See
Table 27 for glc-ms conditions and Table 48 for identity of peaks.
A 200 ft OV-17 SCOT was used.
24
-------
57 67 74
P
IT
3
TEMPERATURE (°C)
45
TIME ( MIN.)
Figure 9 (cont'd)
-------
100,
90
80
70
~~ 60
LJ
a:
cr
3
50
40
20
10
0
32
44
56
27
92
18
104
+
116
128
-4-
140
12
21
24
27
30
15
TIME (MIN)
Figure 10. Total ion chromatogram of ambient air sample from Pasadena, TX. See Table 27 for glc-ms
conditions and Table 51 for identity of peaks. A 400 ft OV-101 SCOT was used.
-------
35
55
78
oo
100
90
80
70
~ so
o
QC
O
40
30
20
10
0
61
72
96
152
164
H-
EMPERATURE (°C)
176 188 200
—I 1 1
'02
•8,
•»
33
36
39
42 45
TIME (MIN)
212
•4-
48
224
-t-
113
236
114
115
51
54
248
H
57
Figure 10 (cont'd)
-------
100
90
80-
P
5 70
£
LJ
£ eo
cc
o
50
§ 40
30
20
10
42
54
TEMPERATURE (°C)
66 78 90
102
49
114
12 15
TIME (MIN)
18
21
94
96
126
24
Figure 11. Total ion chromatogram of ambient air sample from Glendora, CA. See
iablt? 27 for glc-ms conditions and Table 37 for identity of peaks.
A 200 ft OV-17 SCOT was used.
-------
ui
cr
cc
o
lOOr
90-
80-
70-
60-
50-
40-
30-
4
10-
64
49
54
56
48
126
-I—
138
H—
27
ISO
TEMPERATURE (°C)
162 174
186
198
+
210
+
220
H
30
33 36
TIME (MINI)
39
42
45
48
Figure 11 (cont'd)
-------
Ul
100
90
80
70-
i
~ 60
UJ
£ 50
3
§ 40
| 30
20
10
0
42
54
*
78
23
TEMPERATURE
90
102
12 15 18
TIME (MIN)
¥ !t
138
ISO
21
24
27
30
Table 12,
Total ion chromatogram of ambient air sample from Glendora, CA. See Table 27 for glc-ms
conditions and Table 44 for identity of peaks. A 400 ft OV-101 was used.
-------
N5
100,
90
80|-
70
§60,
50
O
Z 4O
O
|30
20
10
0
5L57 63
76 83
162
33
174
186
TEMPERATURE (°C)
198 210 222
234
246
36
39
42 45 48
TIME (MIN)
51
54
120
JL
258
57
270
H
60
Figure 12 (cont'd)
-------
Table 28. HALOGENATED HYDROCARBONS IDENTIFIED IN AMBIENT AIR BY
CAPILLARY GAS-LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY/COMPUTER
Geographical Area
Compound
Kanawha Valley, WV Houston, TX and Vicinity
Los Angeles Basin
difluorochloromethane
trichlorofluoromethane
vinyl chloride
methyl chloride
ethyl chloride
1,2-dichloroethane
fluorochloromethane
methylene chloride
chloroform
carbon tetrachloride
trichloroethylene
1,1,1-trichloroethane
tetrachloroethylene
2-fluoro-2-methylpropane
chlorobenzene
m-dichlorobenzene
o-dichlorobenzene
x
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
x
x
x
X
X
X
X
X
X
X
X
X
X
X
-------
Table 28 (cont'd)
Geographical Area
Compound Kanawha Valley, WV Houston, TX and Vicinity Los Angeles Basin
trichlorobenzene x x
(probably 1,2,4)
trichlorobenzene (? isomer) x x x
bromoform x x
1,2,3,3-tetrachloropropene x
-------
Table 29. OXYGENATED ORGANIC VAPORS IN AMBIENT AIR IDENTIFIED BY
CAPILLARY GAS-LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY/COMPUTER
Geographical Area
Ul
Compound
Kanawha Valley, WV Houston, TX and Vicinity Los Angeles Basin
acetaldehyde
acetone
ethyl acetate
propanal
amyl acetate
furan
2-methylfuran
isopropanol
acetylacetone
styrene oxide (tent.)
cyclohexanol
p_-tolualdehyde
ethyl hexyl ketone
methyl isobutyl ketone
acetophenone
diethyl ether
methyl ethyl ketone
X
X
X
x
x
x
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
Table 29 (cont'd)
Geographical Area
Compound
Kanawha Valley, WV Houston, TX and Vicinity Los Angles Basin
epoxyheptane (tent.) (isomer)
benzaldehyde
methyl vinyl ketone (tent.)
n-butyl vinyl ether
4-phenylbutan-2-none
£-methylanisole
2-methylbenzo-(B)-furan
methyl phthalide
2,6-ditertiary-butyl-£-cresol
dimethyl disulfide
x
X
X
X
X
X
X
X
X
X
X
-------
Table 30. AROMATIC HYDROCARBONS IDENTIFIED IN AMBIENT AIR BY
CAPILLARY GAS-LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY/COMPUTER
Compound
benzene
toluene
jv-xylene
m-xylene
n-propylbenzene
isopropylbenzene
£-ethyltoluene
1,3, 5-trimethylbenzene
o-ethyltoluene
1,2, 4-trimethylbenzene
1,2, 3-trimethylbenzene
t-butylbenzene
iso-butylbenzene
sec-butylbenzene
g-methylstyrene
o-cymene
m-dlethylbenzene
m-propyltoluene
n-butylbenzene
£-propyl toluene
Kanawha Valley, WV
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Geographical Area
Houston, TX and Vicinity
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Los Angeles Basin
X
X
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
Table 30 (cont'd)
Geographical Area
Compound Kanawha Valley, WV
o-diethylbenzene x
p_-diethylbenzene x
styrene
o-propyltoluene x
l,3-dimethyl-5-ethylbenzene x
l,4-dimethyl-2-ethylbenzene x
l,3-dimethyl-4-ethylbenzene x
l,2-dimethyl-4-ethylbenzene x
l,2-dimethyl-3-ethylbenzene x
l,3-dimethyl-2-ethylbenzene x
l-phenyl-2-butene
l-methyl-3-t-butyl benzene
naphthalene x
8, B-dimethylstyrene
C^-alkyl benzenes (13 isomers) x
benzonitrile x
a-cyanopyridine
allylbenzene
phenylacetylene
Houston, TX and Vicinity
x
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Los Angeles Basin
x
x
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
Table 31. ALIPHATIC HYDROCARBONS DETECTED AND/OR IDENTIFIED IN AMBIENT AIR BY
CAPILLARY GAS-LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY/COMPUTER
Compound
2-methylpropane
2-methylpropene
2-methylbutane
n-butane
ri-butene
isopentane
n-pentane
2 , 3-trimethylbutane
methylcyclopentane
2,2, 3-trimethylbutane
2-pentyne
2-methylpentane
3-methylpentane
2 , 3-dimethylpentane
3-ethylpentane
3-methylhexane
n-hexane
C6%2
Geographical Area
Kanawha Valley, WV Houston, TX and Vicinity
X
X
X
X
X
X
X
X X
X
X X
X X
X X
X X
X X
X X
X (1) X (1)
Los Angeles Basin
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X (1)
-------
Table 31 (cont'd)
oo
o
Compound
C6H14
n-heptane
C7H14
C7H16
ri-octane
C8H16
C8H18
n-nonane
C9H18
C9H20
n-decane
C10H20
C16H22
C11H22
C11H24
C12H24
C12H26
C13H26
C13H28
C13H28
C14H30
Geographical Area
Kanawha Valley, WV Houston, TX and Vicinity
x (4)
x x
x (1) x (3)
x (3) x (4)
X X
x (12)
x (8)
X X
x (2) x (5)
x (6) x (8)
X X
x (2)
x (8)
x (11)
x (6) x (9)
x (2) x (5)
x (3)
x (3) x (1)
x (1)
x (1)
Los Angeles Basin
x
x (1)
x (5)
x
x (3)
x (8)
x
x (2)
x (8)
x
x (2)
x (10)
x (5)
x (9)
x (1)
x (1)
x (2)
-------
isomeric forms based solely on the mass cracking patterns and the reten-
tion index. Thus, in these tables we have often represented these com-
pounds primarily as imperical formulas and the number of isomers which we
detected are in parentheses.
Ambient air samples were also obtained from an area near Burlington
Industries and Mallinckrodt in Raleigh, NC. The purpose of this study was
to establish whether biphenyl could be collected and identified in ambient
air near these two industrial firms. Biphenyl was suspected to be present
in ambient air since it occurs as a by-product in a manufacturing process at
Burlington Industries. Research investigators at the North Carolina State
Air Pollution Agency suspect that biphenyl is responsible for the pine tree
kill in the immediate area. The results of this study are shown in Figures
13-15. A total ion chromatogram of an ambient air sample near these two indus-
tries is shown in Figure 13. In general, the majority of the components in
the ambient air...sample represented background pollutants from auto exhuast.
However, a new component appeared which is represented as peak 84 in Figure
13. The mass spectrum of this chromatographic peak is shown in Figure 14.
A comparison of this mass spectrum to that of an authentic sample of biphenyl
(Figure 15) was made. On the basis of these results we concluded that the
peak eluting at 194° was biphenyl. A second sample was collected two and
one-half months later. The chromatogram obtained utilizing a 200 ft SCOT
OV-101 column is shown in Figure 27 in the Appendix. The retention time
and the elution temperature of biphenyl were established in this case by
comparing to an authentic sample. The concentration of biphenyl was
found to be approximately 1-3 ppm at a location of one-half mile from
Burlington Industries. On this particular day (maximum of 55°F) the wind
speed was 10-15 mph with the sampler located down-wind from the industrial
complex.
Several methods are available using gc-ms systems to quantitate consti-
tuents and complex matrices. One common method is based upon alternating
the accelerating voltage (AVA) in the ion source whereby two selected m/e
ions are continuously monitored throughout the chromatographic process. This
technique provides an increase in sensitivity over the total ion current
generated from the mass spectrometer. However, it has a serious disadvantage
in that only two ions may be monitored at any particular time during gas
81
-------
85
i i i
COLUMN TEMPERATURE (°C)
135
I
185
i i i i i i i i i i i i i i i i i i i i i
CO
NJ
zr-fflffl
84
. I . I i I . I i I.I i I i I . I i 1 . I . 1 . I . I J . I . I . I . I .1.1 .1.1.1 .1,1 .1.1.1 .1.1 .1.1.1.1
1600 1650 1700 1750 1800 1850 1900 1950
Figure. 13. Total ion chromatogram of ambient air sample near Burlington Industries and Mallinckrodt
in Raleigh, NC. See Table 27 for glc-ms-comp conditions.
-------
lOOr
00
UJ
co
UJ
H
s
15
50-
100
m/e
Tn
160 170 180 190 I
150 200
Figure 14. Mass spectrum of chromatographic peak no. 84 eluting at 194°C
for previous figure.
-------
00
lOOr
- 50-
ui
I
d
cr
0
10 20 30 40
rao rro
m/e
I'igure 15. Mass .spectrum of an authentic sample of biphenyl.
-------
chromatography. One m/e ion usually represents the internal standard in
the sample and the second is an m/e for the constituent of unknown concen-
tration. This technique is not suitable for ambient air pollution analysis
since many constituents (100-200) are present in a sample. The AVA method
is generally utilized with magnetic sector mass filter instruments. For
this reason, the ions selected for monitoring are required to be less than
10 atomic mass units apart in order to maintain resolution and sensitivity.
A serious limitation of this technique is that the ions selected for the
internal standard and the constituent to be quantitated must be derived
from similar fragmentation patterns or molecular weight. Because of the
large number and diverse molecular weights of the pollutants in ambient
air, this technique is not feasible for quantitating more than one consti-
tuent per chromatographic run.
Another available method for quantitation is multiple ion detection
(m.i.d.). This technique is used primarily on instruments equipped with
quadrupole or: dodecapole mass filters. Multiple ion detection is an im-
provement over the AVA method since up to 12 ions may be monitored simul-
taneously. However, because of the large number of pollutants in air, the
quantitation of all constituents in the sample cannot be accomplished by
m.i.d., either.
The estimation of the level of pollutants in capillary gas chromatog-
raphy is not feasible utilizing the total ion current plot since baseline
resolution between peaks is not achieved. On the other hand, if full mass
spectra are obtained during the chromatographic separation steps and selected
ions are presented as mass fragmentograms, then it is possible to deconvolute
(resolve) constituents which were not resolved in the total ion current chro-
matogram by using software programs on the dedicated computer. Examples are
shown in Figures 16 and 17. Selected ions (m/e 117, 166, 146, 83, and 49)
are plotted as mass fragmentograms for an ambient air sample from Glendora,
CA (Figure 12). Even though the components depicted in Figure 12 were not
completely resolved into individual constitutents, it is possible to obtain
baseline resolution by representing each compound as a single ion plot.
In Figure 16 m/e 117 represents carbon tetrachloride (mass spectrum numbers
95-100). The m/e ions 166 and 146 represent tetrachloroethylene and m-
dichlorobenzene, respectively. In Figure 17 the m/e ions 83 and 49 repre-
sent chloroform (mass spectrum numbers 88-95) and methylene chloride (mass
85
-------
m/e 146
00
m/e 166
m/e 117.
,1,1,1,1,1,1,1,1,1,1,1,1,1,1,1,1,1,
50
100
150 200
MASS SPECTRUM NO.
250
300
Figure 16. Mass tragmentograms of unique ions representing carbon tetrachloride (m/e 117), tetra-
rliloroethylene (m/e 166) and m-dichlorobenzene (m/e 146) in ambient air from Glendora,
CA. See Figure 12 for total ion plot.
-------
m/e 49 I
\ II
IV
c»
m/e 83
I . I . I . I . I . I . I . I . I . I . I .
0 50 100
AAA^A^^^A/WlA - /U/-^
I . I . I . I . I . 'I . I . I . I . I . I .
. I . . I . I . I . I . I . I . I . I . 'I . I . I . I . I . I .
150 200 250
MASS SPECTRUM NO.
Figure 17. Mass t'ragraentograms of unique ions representing methylene chloride (m/e 49) and chloroform
(m/e 83) in ambient air from Glendora, CA.
-------
spectrum numbers 69-72), respectively. Even though in the total ion cur-
rent plot only partial resolution was observed between many of the peaks
associated with these compounds, baseline resolution with no interferences
was achieved utilizing the mass fragmentogram method. In our glc-ms comp
system we can request from the Varian 620i dedicated computer mass fragmen-
tograms for any combination of m/e ions when full mass spectra are obtained
during chromatography.
As other carcinogenic and mutagenic vapors are identified during the
continuing contract period, hazardous vapors will be quantitated utilizing
the described techniques.
88
-------
SECTION VIII
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89
-------
13. Gould, R. F. Advances in Chemistry Series 113: Photochemical Smog
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339-344, 1974.
19. Van Wijik, R. Advances in Chromatography, 1970. Ed. A. Zlatkis,
Houston, TX., p. 122, 1970.
20. Van Wijik, R. The Use of Poly-Para-2, 6-Diphenyl-Phenylene Oxide as a
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1970.
21. Applied Sci. Lab., Inc., Technical Bulletin No. 24, 4 pp., 1973.
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24. Versino, B., M. deGroot, and F. Geiss. Air Pollution - Sampling
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25. Tore, J. C. and G. J. Kallos. Kinetic Study of the Stabilities
of Chloromethyl Methyl Ether and Bis(Chloromethyl)Ether in Humid
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26. Ahlstrom, D. H., R. J. Kilgour, and S. A. Liebman. Trace Determina-
tion of Vinyl Chloride by a Concentrator/Gas Chromatography System.
Anal. Chem. 47/8):1411-2, 1975.
27. Williams, F. W. and M. E. Umstead. The Determination of Trace Con-
taminants in Air by Concentrating on Porous Polymer Beads. Anal.
Chem. 4^:2234-4, 1968.
28. Raymond, A. and G. Guichon. Gas Chromatographic Analysis of C0-C,0
O J.O
Hydrocarbons in Paris Air. Environ. Sci. Techn. £: 143-8, 1974.
29. Hollis, D. L. Separation of Gaseous Mixtures Using Porous Poly
Aromatic Polymer Beads. Anal. Chem. 38_: 309-16, 1966.
30. Brooman, D. L. and E. Edgeley. Concentration and Recovery of
Atmospheric Odor Pollutants Using Activated Carbon. J. Air
Pollution Cont. Assoc. 3.6:25-9, 1966.
31. Jones, W. M. The Absorption of Benzene Vapor from an Air Stream
by Beds of Charcoal. J. Appl. Chem. 16_: 345-9, 1966.
32. Jones, P. W. Analysis of Nonparticulate Organic Compounds in
Ambient Atmospheres. 67th Air Poll. Cont. Assoc. Mtg., Denver,
Colorado. Paper No. 74-265. June 1973.
33. Legget, D. C., R. P. Murrmann, T. J. Jenkins and R. Barriera.
Method of Concentrating and Determining Trace Organic Compounds
in the Atmosphere. Cold Regions Res. Eng. Lab., Hanover, N. H.
U. S. Nat. Tech. AD Rep. No. 745125, 1972. p. 14.
34. Haigh, D. H. Removal of Organic Vapors from Gases by Alkyl-styrene
Polymer Particles. U. S. Pat. 3,686,827.
35. Dravnieks, A., B. K. Krotaszynski, J. Burston, A. O'Donnel and T.
Burgwald. High Speed Collection of Organic Vapors from the
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36. Williams, I. H. Gas Chromatographic Techniques for the Identification
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1723-1732, 1965.
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37. Damico, J. N. Use of Activated Charcoal to Trap Gas Chromatographic
Fractions for Mass Spectrometric Analysis and to Introduce Volatile
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38. Malyarove, L. K. K. Determination of Aromatic Compounds in Air by
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39. Robel, A. J. Basic Studies of Gas-Solid Interactions III Considera-
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40. Jeltes, R. Sampling of Nonpolar Air Contaminants on Porapak Porous
Polymer Beads. Atm. Environ. 3_:587-8, 1969.
41. Tiggelbeck, D. Increasing Selective Efficiency in Cigarette Filter
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42. Saunders, R. A., M. E. Umstead, W. D. Smith and R. H. Gammon. The
Atmospheric Trace Contaminant Pattern of Sea Lab II. Proc. 3rd
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43. Duel, C. L. Collection and Measurement of Atmospheric Trace Con-
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Cont. NAS 1-8714, NASA Doc. No. 71-19636.
44. Saunders, R. A. Analysis of Spacecraft Atmospheres. NRL Rept.
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45. Chiantella, A. J., W. D. Smith, M. E. Umstead and J. E. Johnson,
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46. Saunders, R. A. Atmospheric Contamination in SEA-LAB I. Proc.
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92
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49. Marsteller, H. J., W. K. Lelbach, R. Muller and P. Gedigke. Unusual
Splenomegalic Liver Disease As Evidenced by Peritoneoscopy and Guided
Liver Biopsy Among Polyvinyl Chloride Production Workers. (Presented
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51. Chemical and Engineering News. Amer. Chem. Soc., Washington, D. C.,
p. 6, May 5, 1975.
93
-------
SECTION IX
APPENDIX
94
-------
27
3838 41
90r
80-
70-
v
I
O
O
a!
o
52
TEMPERATURE (°C)
76
18
21
24
3 6 9 12 15
TIME (min)
Figure 18. Total ion current plot during gas-liquid chromatography mass spectrotnetry of
air sample from Santa Monica, CA. A 200 ft OV-101 SCOT was used, see text for
conditions.
-------
41 42
51 52°° 55 99 63'
VO
89
TEMPERATURE (°C)
172
33 36
TIME (min)
Figure 18 (cont'd)
-------
Table 32. POLLUTANTS IDENTIFIED IN AMBIENT AIR FROM SANTA MONICA, CA°
Chromatographic
Peak No.
Compound
Chromatographic
Peak No.
Compound
vo
1
4
5
6
8
10
11
14
15
17
18
19
20
22
25
26
30
air (02, C02)
trichlorofluoromethane
2-methylbutane
/" methylene chloride + C H (alkene)
/ acetone +
I dimethylbutane +
methylpentane isomer
hexane
C6H12 (alkene)
chloroform
1,2-dichloroethane
methyl ethyl ketone
benzene
dimethylpentane isomer
2-methyl-l-hexane
3-methylhexane
dimethylcyclopentane isomer
n-heptane
C-jH.., (cyclic, branched)
dimethylpentene isomer
31 CQH1Q (branched)
O J.O
32 C,H, , (alkene, branched)
o ID
38 toluene
39 C 3-methylheptane +
l^trimethylpentane isomer
40 n-octane
41 tetrachloroethylene
42 dimethylheptane
43 methyloctane isomer
44 trimethylcyclopentane isomer
45 t rime thy Ihexane isomer
46 chlorobenzene
49 ethylbenzene
50 p_-xylene
51 m-xylene
53 dimethylheptane isomer
54 p_-xylene
58 n-nonane
59 C10H22
-------
Table 32 (cont'd)
vo
00
Chromatographic
Peak No.
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
Compound
C10H22
methylethylbenzene isomer
C10H22
C10H22
C10H20
B-pinene
isopropylheptane isomer
C10H20
isopropylbenzene
methylethylbenzene isomer
C10H22 (branched>
methylethylbenzene isomer
methylnonane isomer
n-propylbenzene isomer
Chromatographic
Peak No.
77
78
79
80
81
82
83
84
85
86
87
88
89
90
99
100
Compound
C10H20 (branched)
C^-alkyl benzene
n-decane
C10H20
dichlorobenzene isomer
C11H24 (branched>
C11H24 (branched>
trimethylbenzene isomer
methylstyrene isomer
C10H30
-------
90r
vO
VD
TEMPERATURE (°C)
54 78
122
12 15
TIME Imin)
18
21
24
Figure 19. Total ion current plot during gas-liquid chromatography mass spectrometry of air sample
from West Covina, CA. A 200 ft OV-17 SCOT was used, see text for conditions.
-------
54 55
c
c
90
27
30
33
36
TIME (°C)
39
42
46
Figure 19 (cout'ci)
-------
Table 33. POLLUTANTS IDENTIFIED IN AMBIENT AIR FROM WEST COVINA, CA=
Chromatographic Chromatographic
Peak No. Compound Peak No. Compound
1
2
• 3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
butane
butene isomer
trichlorof luoromethane
isopentane
methylene chloride
2-methyl-2-butene
acetone
C16H14
C,H.. .
6 14
4-methyl-l-pentane
n-hexane
chloroform
methylcyclopentane
methyl ethyl ketone
1,1, 1-trichloroethane
benzene
carbon tetrachloride
C6H12
dimethylpentane (Isomer ?)
dimethylcyclopentane (isomer ?)
3-methylhexane
dimethylcyclopentane (isomer ?)
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
dimethylcyclopentane (isomer ?)
trichloroethylene
n-heptane
C,H,2 isomer
dimethylpentene (isomer ?)
C0H, Q (branched alkane)
O J-O
C8H16
C8H16
toluene
methylheptane isomer
C8H14
ri-octane
tetrachloroethylene
unknown
C9H20
trimethylcyclopentane isomer
chlorobenzene
C9H18
ethylbenzene
p_-xylene
m-xylene
2,4, 4- trimethylhexane
-------
Table 33 (cont'd)
Chromatographic
Peak No.
45
46
47
48
49
50
51
— / J.
52
53
:>4
55
56
57
58
59
60
61 .
62
63
64
65
66
Compound
£-xylene
nj-nonane
3,5, 5-trimethylhex-l-ene
SH18
isopropylbenzene
C10H20
C H
9 18
C10H20
n-propyl benzene
m-echyltoiuene
p_-ethyltoluene
C10H22
acetophenone
1,3, 5- trimethylbenzene
benzaldehyde
1,2, 4-trimethylbenzene
n-decane
isobutylbenzene
m-dichlorobenzene
C, -alkyl benzene
1,2, 3-trimethylbenzene
C11H24
Chromatographic
Peak No.
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85,86
87
88
Compound
methylstyrene isomer
C10H20
o-dichlorobenzene
p_-diethylbenzene
p_-propyltoluene
dimethylethylbenzene (isomer ?)
C H
11 24
C11H24
C,-alkyl benzene
C11H24
C, -alkyl benzene
C,-alkyl benzene
C,-alkyl benzene
l-phenyl-2-butene
C,-alkyl benzene
n-undecane
C, -alkyl benzene
Ce-alkyl benzene
C,-alkyl benzene
C12H26
C_ -alkyl benzene
-------
Table 33 (cont'd)
o
GJ
Chromatcgraphic
Peak No.
89
90
91
92,93
94
95
96
97
98,99
100
101
Compound
ethylstyrene isomer
C,--alkyl benzene
C,-alkyl + C5~alkyl benzenes
C^-alkyl benzenes
unknown
trichlorobenzene isomer
naphthalene + n-dodecane
C13H28
Cp-alkyl benzenes
C10H_,
13 26
C,.-alkyl + C,-alkyl benzenes
Chromatographic
Peak No.
102
103
104,105
106
107
108
109
110
111
112
113
114
Compound
C,.-alkyl benzene
trichlorobenzene isomer
C,-alkyl benzenes
D
nj-tridecane
methylnaphthalene isomer
unknown
C13H26
unknown
unknown
C, / H__
14 30
unknown
unknown
See previous Figure.
-------
Table 34. POLLUTANTS IDENTIFIED IN NIGHT AMBIENT AIR FROM WEST COVINA, CA
Chromatographic
Peak No.
Compound
Chromatographic
Peak No.
Compound
1
2
3
4
5
6
6A
7
8
9
10
10A
11
12
13
13A
14
14A
15
16
carbon dioxide
methylcyclopropane (tent.)
n-pentane
2-methyl-2-butene
methylene chloride
2-pentene
2,3-dimethylpentane
acetone
3-methylpentane
methylethylcyclopropane
n-hexane
3-methylpentene
1-hexene
methylcyclopentane
1,1,1-trichloroethane
3-methylcyclopentene
benzene
carbon tetrachloride
2-methyIhexane
3-methylhexane
17
18
19
20
20A
21
22
23
24
25
26
26A
27
28
29
30
31
32
33
34
3,3-dimethyl-l-pentene
1,1-dimethylcyclopentane
trichloroethylene
n-heptane
5-methyl-2-hexene
1,1,2-2-tetramethylcyclopropane
2,5-dimethylhexene
2,5-dimethyl-3-hexene
toluene
2-methylheptane
3-methylheptane
2,3,4-trimethyl-2-pentene
unknown
2,4-dimethyIhexane
n-octane
tetrachloroethylene
hexamethylcyclotrisiloxane
1,2-dimethylcyclohexene
2,2,3,3-tetramethylpentane
unknown
-------
Table 34 (cont'd)
Chromatographic
Peak No.
Compound
Chromatographic
Peak No.
Compound
35
36
37
38
39
40
41
42
43
44
45
46
47
48
48A
49
50
51
52
53
54
55
chlorobenzene
ethylbenzene + 4-methyloctane
p_-xylene
m-xylene
3-methyloctane
unknown
4-ethylheptane
unknown
2,2,3, 3-tetramethylhexane
2 , 5-dimethyloctane
unknown
unknown
unknown
n-propy Ibenzene
m-ethyltoluene
C.,-alkyl benzene
unknown
C»-alkyl benzene
o-ethyltoluene
unknown
octamethylcyclotetrasiloxane
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
1,2,4-trimethyIbenzene
2,6-dimethyloctane
m-dichlorobenzene
unknown
unknown
1,2,3-trimethyIbenzene
unknown
3-methylstyrene or indan (?)
unknown
unknown
o^-diethy Ibenzene
Pj-diethy Ibenzene
unknown
unknown
unknown
unknown
1,4-dimethyl-2-ethyIbenzene
1,3-dimethyl-4-ethylbenzene
1,2-dimethyl-4-ethylbenzene
n-undecane
5-methyldecane (tent.)
1,2-dlmethy1-3-ethyIbenzene
-------
Table 34 (cont'd)
Chromatographic
Peak No.
Compound
Chromatographic
Peak No.
Compound
78
79
80
81
82
83
84
85
(1-methyIbutyl)benzene (tent.)
ri-dodecane
1,3-dimethyl-2-ethylbenzene
2-methyldecalln (tent.)
decamethylcyclopentasiloxane
l-phenyl-2-butene (tent.)
2-phenyl-2-methylbutane
(2-methylpropenyl)benzene
86
87
88
89
90
91
92
92A
1,2,4,5-tetramethylbenzene
unknown
unknown
tetradecamethylhexasiloxane
unknown
unknown
2-methyl-3-heptanone (tent.)
l-methyl-3-t-butylbenzene (tent.)
A 200 ft OV-101 SCOT programmed from 30-220°C @ 4°/min was used.
-------
o
-4
90 r
TEMPERATURE (°C)
96
120
12 15
TIME (min)
18
21
134
24
Figure 20. Total ion current plot during gas-liquid chromatography mass spectrometry of air sample
iirom Gleudora, CA. A 200 ft OV-17 SCOT was used, see text for conditions.
-------
90r
o
00
27
82
158
TEMPERATURE (°C)
182
206
230
30
33
36 39
TIME (min)
42
45
48
52
Figure 20 (cont'd)
-------
37 40
90
80
70-
£
£
LJ
tr
u
z
o
50
40-
30-
20-
10-
TEMPERATURE (°C)
12 15
TIME (min)
18
21
24
27
Figure 21. Total ion current plot during gas-liquid chromatography mass spectrometry of air sample
from Anaheim, CA. A 200 ft OV-101 SCOT was used, see text for conditions.
-------
50 56
90r
36 39
TIME (min)
Figure 21 (cont'd)
-------
21
90r
80-
70
§ 60
*
LJ
tr
CL
3
o
50-
40
30
20-
10
10
56
19
TEMPERATURE (°C)
80
30
194
I2B
0
12 15
TIME (min)
18
21
24
27
'•"igure 22. Total ion current plot during gas-liquid chromatography mass spectrometry of night air
sample from Anaheim, CA. A 200 ft OV-101 SCOT was used, see text for conditions.
-------
36 39
TIME (min)
Figure 22 (cont'd)
-------
90
80-
70-
60
UJ 50
40
30
20-
10-
o
o
<
Q
64
TEMPERATURE (°C)
88
43
102
i
126
0
12 15
TIME (min.)
18
21
24
27
Figure 23. Total ion current plot during gas-liquid chromatography mass spectrometry of air samples
from Garden Grove, CA. A 200 ft OV-101 SCOT was used, see text for conditions.
-------
50 57
UJ
a:
tr
90r
80
70
60
50
40
30
20
10
150
174
TEMPERATURE (°C)
198
105
27
30
33
36
39 42
TIME (min)
45
48
51
Figure 23 (cont'd)
-------
Table 35. POLLUTANTS IDENTIFIED IN AMBIENT AIR
FROM SANTA MONICA, CA&
Chromatographic
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
31-33
Compound
n-butane
2-butene
isopentane
n-pentane + trichlorofluoromethane
2-pentyne
2 , 3-dimethylbutane
3-methylpentane
n-hexane
methylene chloride
diethyl ether
acetone
methylcyclopentane
C7H16
2,3 dimethylpentane
3-methylhexane
dimethylcyclopentane (isomer ?)
n-heptane + chloroform
1,1, 1- tr ichloroethane
carbon tetrachloride
C8H16
dimethylhexane (isomer ?)
benzene
dimethylpentane (isomer ?)
C7H14
2 , 5-dimethylhexane
2,3, 3-trimethylpentane
3-methylheptane
n-octane
C0H.., (isomers)
o ID
CQHon (isomers)
115
-------
Table 35 (cont'd)
Chroma tographic
Peak No.
34
34-37
38
39
40
41
42-46
47
48
49
50,51
52
53
54
55
56-60
61
62
63
64-66
67
68
69
70
71
72-75
76
77
78
79
80
Compound
toluene
C9H20 (lsomers)
tetrachloroethylene
C9H18
n-octane
C9H18
C10H22 (isomers)
ethylbenzene
p_-xylene + m-xylene
2 , 6-dimethyloctane
C10H22 (isomers)
o-xylene
phenylacetylene
n-decane + styrene
isopropylbenzene
C11H24 (isomers)
n-propylbenzene
m-ethyltoluene
p_-ethyltoluene
C11H24 (isomers)
o-ethyltoluene
C11H24
1 , 2 , 4-trimethylbenzene
ii-undecane
£-cymene
C11H22 (isomers)
1,2,3 trimethylbenzene
sec-butylbenzene
isobutylbenzene + dichlorobenzene (isomer)
C, -alkyl benzene
methylstyrene (isomer ?)
116
-------
Table 35 (cont'd)
Chromatographic
Peak No.
81,82
83
84-86
87
88
89
90
91-94
94-100
101
102
103
104
105
106
107
Compound
C, -alkyl benzenes
C11H22
C, -alkyl benzenes
C,.-alkyl benzene
C,-alkyl benzene
n-dodecane
ethylstyrene (isomer)
C, -alkyl benzenes
C,. -alkyl benzenes
ethylstyrene (isomer)
tetramethylbenzene (isomer ?)
C,.-alkyl benzene
ethylstyrene (isomer)
C^-alkyl benzene
naphthalene
2 , 6-ditertiarybutyl-p_-cresol
a
Resolution was achieved on a 200 ft OV-17 SCOT column, programmed from
30-220°C @ 4°/min.
117
-------
Table 36. POLLUTANTS IDENTIFIED IN AMBIENT AIR
FROM WEST COVINA, CAS
Chromatographic
Peak No. Compound
1 n-butane
2 isopentane
3 n-pentane + trichlorofluoromethane
4 2,3-dimethylbutane
5 3-methylpentane
6 ri-hexane
7 methylene chloride
8 acetone
9 meth/lcyclopentane
10 2,2,3-trimethylbutane
11 2,3-dimethylpentane
12 3-ethylpentane
13 3-methylhexane
14 dimethylpentene (isomer ?)
15 dimethylcyclopentane (isomer ?)
16 chloroform + n-heptane
17 dimethylcyclopentane (isomer ?)
18 dimethylhexane (isomer ?)
19 benzene
20 dimethylpentane (isomer)
21,22 C8H18 (isoniers)
23 n-octane
24 siloxane isomer
25,26 C9H20 (isomers)
27 toluene
28,29 C9H20 (isomers)
30 tetrachloroethylene
31 C9H2Q
32 n-nonane
33 C9H18
118
-------
Table 36 (cont'd)
Chromatographic
Peak No.
34-36
37
38
39
40-2
43
44
45
46-48
49,50
51
52
53
54,55
56
57
58
59
60
61
62
63
64
65
66
67-70
71
72
73-75
76-84
85
Compound
C10H22 (isomers)
ethylbenzene
£-xylene
m-xylene
C10H22 (isomers)
£-xylene
C11H24
n-decane
C11H24
C10H20
n-propylbenzene
m-ethyltoluene
p_-ethyltoluene
C11H24 (isomers)
o-ethyltoluene
C11H24
1,2, 4-trimethy Ibenzene
n-undecane
£-cymene
C12H26
C11H22
1,2, 3-trimethylbenzene
dichlorobenzene (isomer) + C.-alkyl benzene
C,-alkyl benzene
methylstyrene isomer
C,-alkyl benzenes
n-dodecane
ethylstyrene isomer
C, -alkyl benzenes
C(--alkyl benzenes
ethylstyrene isomer
119
-------
Table 36 (cont'd)
Chromatographic
Peak No. Compound
86-88 C5-alkyl benzenes
89 Cfi-alkyl benzene
90 C.-alkyl benzene
90A trichlorobenzene isomer
91 naphthalene
92 C13H2g
93,94 C14H30
Resolution was on a 200 ft OV-17 SCOT programmed from 30-220° @ 4°/min.
120
-------
Table 37. POLLUTANTS IDENTIFIED IN AMBIENT AIR
FROM GLENDORA, CA3
Chromatographic
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
Compound
n-butane
2-butene
unknown
isopentane
n-pentane + trichlorofluoromethane
unknown
unknown
2-methylpentane
3-methylpentane
n-hexane
methyl n-propyl ether + methylene chloride
acetone
methylcyclopentane
C_H_, (isomers)
/ lo
2 , 3-dimethylpentane
3-methylhexane
diraethylcyclopentane (isomer)
n-heptane
chloroform
1,1,1-trichloroethane + carbon tetrachloride
C8H18
C8H16
benzene
dimethylpentene (isomer ?)
C7H14
C8H18
trichloroethylene + CQH..
o lo
rx-octane
C8H16
C9H20
121
-------
Table 37 (cont'd)
Chromatographic
Peak No.
33
34
35-37
38
39
40
41
42-47
48
49
50
51-3
54
55
56
57-61
62
63
64
65
66
67
68
69
70
71
72
73
74,75
76
77
Compound
toluene
2 , 3-dimethylheptane
CgH?n (isomers)
tetrachloroethylene
C9H18
n-nonane
C9H18 + C10H22
Cnr.H00 (isomers)
1U 12.
ethylbenzene
p_-xylene
m-xylene
C1rvH0/, (isomers)
ID 22
o-xylene
C11H24
n-decane
C, nH0. (isomers)
11 i">
bromoform + C^H^,
n-propylbenzene
m-ethyltoluene
p_-ethyltoluene
C11H24
C10H20
C11H24
o-ethyltoluene
C11H22
1,2, 4-trimethylbenzene
n-undecane
C,-alkyl benzene
C1nH00 (isomers)
11 22
cyclopentylcyclopentane ( tent . )
1,2, 3- trimethylbenzene
122
-------
Table 37 (cont'd)
Chromatographic
Peak No.
78
79
80,81
82
83
84
85
86
87
88
89
90
91
92,93
94-98
99
100
101
102-104
105
106
107
108
109
110
111
Compound
isobutylbenzene + benzaldehyde
m-dichlorobenzene
C,-alkyl benzenes
C H
12 26
methylstyrene isomer
C,-alkyl benzene
V> « « li A *V
11 22
C, -alkyl benzene
£-dichlorobenzene + C, -alkyl benzene
C, -alkyl benzene
Cc-alkyl benzene + ethylstyrene
j
n-dodecane
C,. -alkyl benzene
C, -alkyl benzenes
C (.-alkyl benzenes
C13H26
C,.-alkyl benzene
acetophenone
C- -alkyl benzenes
ethylstyrene isomer
r H
^14 30
Cr -alkyl benzene + C..,H, ,
5 11 14
C, -alkyl benzene
o
C -alkyl benzene + C H ,
naphthalene
C- -alkyl benzene
r* H
L14n30
Resolution was on a 200 ft OV-17 SCOT programmed from 30-220°C @ 4°/min.
123
-------
Table 38. POLLUTANTS IDENTIFIED IN AMBIENT AIR
FROM GARDEN GROVE, CA*
Chromatographic
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
Elution Temperature
48
52
53
56
57
59
60
61
63
67
68
68
70
71
72
72
73
76
77
78
83
85
89
93
96
98
102
104
108
Compound
n-butane
unknown
isopentane
unknown
2 , 3-dimethylbutane
jn-hexane
methylene chloride
methyl isopropyl ether
acetone
C7H16
2 , 3-dimethylpentane
3-methylhe..ane
C7H16
chloroform
dimethylcyclopentane
(isomer ?)
dimethylcyclopentane
(isomer ?)
1,1, 1-trichloroethane
C8H18
benzene
dimethylpentene (isomer ?)
C8H18
3-methylheptane
n-octane
hexamethylcyclotrisiloxane
C8H16
toluene
CqH2n (isomers)
tetrachloroethylene
n-nonane
124
-------
Table 38 (cont'd)
Chromatographic
Peak No.
31
32-34
35
36
37-39
40
41
42
43
44
45-48
49
50
51
52-54
55
56
57
58
59
60
61
62
63 .
64
65,6
67
68
69
Elution Temperature
(°C)
112
113,115,116
117
118
119,121,122
124
125
126
128
129
130,131,132,133
134
135
136
137,138,139
140
141
142
143
144
146
148
149
150
151
152,153
154
155
156
Compound
C9H18
C10H22 (isomers)
ethylbenzene
p_-xylene
C10H22 (isomers>
£-xylene
phenylacetylene
n-decane
isopropylbenzene
C10H20
C11H24 (isomers)
n-propylbenzene
m-ethyltoluene
p_-ethyltoluene
C11H24 (isomers)
p_-ethyl toluene
unknown
1,2, 4-trimethylbenzene
n-undecane
unknown
C, -alkyl benzene
C11H22
1,2, 3-trlmethylbenzene
benzaldehyde
m-dichlorobenzene
C, -alkyl benzenes
methylstyrene (isomer ?)
C, -alkyl benzene
o-dichlorobenzene + C.-
70
157
alkyl benzene
C,-alkyl benzene
125
-------
Table 38 (cont'd)
Chromatographic
Peak No.
71
72
73
74
75
76
77
78-83
84
85
86
87
88
89
Elution Temperature
(°C)
158
159
160
161
163
164
165
166,167,168,169,
170
171
172
173
175
177
178
Compound
C^-alkyl benzene
ethylstyrene (isomer ?)
GI *iH,« f
12 26
C,.-alkyl benzene
C, -alkyl benzene
C -alkyl benzene
C, -alkyl benzene
CL -alkyl benzenes
tolualdehyde
C,.-alkyl benzenes
ethylstyrene (isomer ?)
C,. -alkyl benzene
C. «H~ n
13 28
trichlorobenzene (isomer)
Resolution was on a 200 ft OV-17 SCOT column programmed from 30-220°C
@ 4°/min.
126
-------
Table 39. POLLUTANTS IDENTIFIED IN AMBIENT AIR
FROM ANAHEIM, CA3
Chromatographic
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
Compound
ri-butane
2-butene
isopentane
n-pentane + trichlorofluoromethane
unknown
fur an
2 , 3-dimethylbutane
3-methylpentane
n-hexane
methylene chloride
methyl n-propyl ether
acetone
methylcyclopentane
C7H16
2 , 3-dimethylpentane
3 -methy Ihexane
C7H16
chloroform
dimethylcyclopentanes
1,1, 1-tr ichlor oethane
carbon tetrachloride
C8H18
C8H16
benzene
dimethylpentene (isomer ?)
3-methyl-l-hexene
C7H12 + C8H18
dimethylfuran (isomer ?)
n-octane
hexamethylcyclotrisiloxane
127
-------
Table 39 (cont'd)
Chr omatogr aphic
Peak No.
32
33
34,35
36
37
38
39-42
43
44
45,46
47
48
49
50
51
52-55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
Compound
C9H20
toluene
C9H20 (isomers)
tetrachloroethylene
n-nonane
C9H18
C10H22 (isomers)
ethylbenzene
p_-xylene
C10H22 (isomers)
£-xylene
phenylacetylene
n-decane
C10H20
isopropylbenzene
C11H24 (isomers)
n-p ropylbenzene
m-ethyl toluene
p_-ethyltoluene
C11H24
C10H20
C11H24
£-ethyltoluene
unknown
1,2, 4-trimethylbenzene
n-undecane
C,-alkyl benzene
C11H22
C12H26
C11H22
1,2, 3-tr imethylbenzene
128
-------
Table 39 (cont'd)
Chromatographic
Peak No. Compound
71
72,73
74
75
76
77
78
79
80
81
82
83
84
85-87
88-91
92
93
94
95
96
97
98
99
100
101,102
103
104-106
107
benzaldehyde + m-dichlorpbenzene + C,-
alkyl benzene
C,-alkyl benzene
C12H26
methylstyrene isomer
C, -alkyl benzene
C11H22
C, -alkyl benzene
o-dichlorobenzene + C, -alkyl benzene
C, -alkyl benzene
C_-alkyl benzene
C12H26
C_-alkyl benzene
C12H24
C, -alkyl benzene
C,. -alkyl benzenes
tolualdehyde isomer
Cj. -alkyl benzene
acetophenone
ethylstyrene (isomer)
C, -alkyl benzene
C,. -alkyl benzene
ethylstyrene isomer
C13H28
tetrahydronapthalene (isomer)
C_ -alkyl benzenes
trichlorobenzene isomer
C, -alkyl benzenes
D
naphthalene
129
-------
Table 39 (cont'd)
Chromatographic
Peak No. Compound
108 Cfi-alkyl benzene
109 C14H30
Resolution was on a 200 ft OV-17 SCOT programmed from 30-220°C @ 4°/min
130
-------
Table 40. POLLUTANTS IDENTIFIED IN NIGHT AMBIENT AIR
FROM SANTA MONICA, CA*
Chromatographic
Peak No.
-
1
2
2A
3
3A
4
4A
4B
5
6
7
8
9
10
11
12
12A
13
14
15
16
17
17A
18
19
20
21
Elution Temperature
(°C)
52
53
55
56
58
59
60
62
63
65
67
68
70
71
-
-
73
74
76
76.5
77
79
81
82
82.5
83
85
85
Compound
chlorodifluoromethane
(Freon 22)
isobutane
n-butane + 1-butene
sulfur dioxide
isopentane
C6H12
trichlorofluoromethane
(Freon 11)
2-methylbutane
furan
2-methylpentane
C6H12
n-hexane
methylene chloride
trans-3-hexene
unknown
unknown
methylcyclopentane
acetone
acetylacetone
C5H10
2 , 3-dimethylpentane
chloroform
n-heptane
C7H14
carbon tetrachloride
C9H18
C7H14
C8H18
131
-------
Table 40 (cont'd)
Chromatographic
Peak No.
22
23,24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
40A.41
41A.44
45
46
47
48
49
50
51
52
53
54
55
Elution Temperature
86
87,89
90
91
92.5
95
97
99
-
102
103
104
108
108
109
109
110
114
115,116.5
117,118,119.5,120
-
-
122
123
124
124.5
126
126
128
130
131
Compound
benzene
C7H. , (isomers)
2 , 5-dimethylhexane
trichloroethylene
3-methylheptane
C8H16
3-methyl-3-ethylpentane
hexamethylcyclotrisiloxane
unknown
\^ — H rt f\
9 20
3 , 3-diethylpentane
toluene
W /• Hi r*
6 12
3 , 3-dimethylheptane
C0Hon
9 20
("*1 si fin f\
10 22
tetrachloroethylene
n-nonane
C0H1Q
9 18
C10H22
unknown
unknown
ethylbenzene
p_-xylene
(_< - _ fi_ -.
10 22
CnH10
9 18
Li ... tl- ,.
8 16
0 -, r*. il_ -•
10 16
m-xylene
phenylacetylene
2 , 6-dimethyloctane
132
-------
Table 40 (cont'd)
Chromatographic
Peak No.
56
57
58
59
60
61
62
63
63A
64
65
66
67
67A
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
Elution Temperature
(°C)
131.5
132.5
-
134
135.5
136
137
137
138
139.5
140.5
142
142
143
143.5
-
146
147.5
-
-
149
151
152
152.5
154
154
154.5
155
-
156.5
Compound
C10H20
isopropylbenzene
unknown
vinyl 2-ethylhexyl ether
C11H24
C10H20
unknown
C11H24
bromoform
n-propylbenzene
m-ethyltoluene
p_-ethyltoluene
C10H20
C11H22
C11H24
o-ethyltoluene
unknown
1,3, 5-tr imethylbenzene
n-undecane
unknown
unknown
£-cymene
C10H18
C11H22
1,2, 4-tr imethylbenzene
sec -bu ty Ib en z ene
m-dichlorobenzene
isopropylbenzene
l,2-dimethyl-2-ethylbenzene
unknown
o-methylstyrene
133
-------
Table 40 (cont'd)
Chromatographic
Peak No.
85
86
87
88
89
90
91
92
93
94
95
96
96A
97-99
100
101
102
103
104
105
106
107
108,109,109AS110
111
111A
112 '
113
114
115
116
Elution Temperature
157
-
159
159.5
160.5
162
-
163.5
164
165
-
166.5
166.5
168,169,169.5
-
171.5
172
172.5
173
174
174.5
175.5
178,179,179.5
181
181
182
182
182
183.5
184.5
Compound
l-methyl-2-n-propylbenzene
unknown
C, -alkyl benzene
C, -alkyl benzene
1 , 4-dimethyl-2-ethylbenzene
C,. -alkyl benzene
unknown
n-dodecane
p_-ethylstyrene
CTJ
i rt »rt /
12 24
unknown
C, -alkyl benzene
C, -alkyl benzene
C^-alkyl benzene
unknown
(1-methylbutyl) benzene
n-tetradecane
C,.-alkyl benzene
4-methylindan
C, -alkyl benzene
C^ -alkyl benzene
p_-ethylstyrene
C^-alkyl benzenes
CTJ
i i fl/\ f\
11 20
C, -alkyl benzene
C,. -alkyl benzene
C6~alkyl benzene
Cr-alkyl benzene
C, -alkyl benzene
D
C^-alkyl benzene
134
-------
Table 40 (cont'd)
Chromatographic Elution Temperature
Peak No. (°C) Compound
117 186 C6~alkyl benzene
118 187 naphthalene
118A,119 188,191 C5-alkyl benzene
Resolution was on a 200 ft OV-17 SCOT programmed from 30-220 @ 4°/min.
1.35
-------
Table 41. POLLUTANTS IDENTIFIED IN NIGHT AMBIENT AIR
FROM ANAHEIM, CA&
Chromatographic
Peak No.
1
2
3
4
4A
5
5A
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
Elution Temperature
-
54
56.5
57
58
59.5
60
61.5
63
64.5
-
65
66
66.5
68
69
71
72
73
74
75
77
78
79.5
80
81.5
83
-
86
Compound
unknown
1-butene
ii-pentane
trichlorofluoromethane
1-pentane
C5H10
furan
2 , 3-dlmethylbutane
3-methylpentane
n-hexane
unknown
methylene chloride
propanol (tent.) (isomer)
1-methyl-l-ethylcyclopropane
acetone
C6H12
unknown
'acetylacetone
C6H10
n-heptane
chloroform
3 , 3-dimethylpentane
carbon tetrachloride
C6H14
C9H14
C8H18
benzene
dimethylpentene (isomer ?)
unknown
2, 5-dimethylhexane
136
-------
Table 41 (cont'd)
Chromatographic
Peak No.
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
Elution Temperature
(°C)
87
88
-
91.5
94.5
97.5
98
98.5
101
103.5
105
106
110
113.5
115.5
117
118
119
120.5
121
121.5
124
126.5
127
128.5
130.5
131
132
_
Compound
trichloroethylene
3-methylheptane
unknown
3-methylheptene (isomer ?)
hexamethylcyclotrisiloxane
1-octene
C9H20
n-propyl acetate
toluene
C9H20
C7H16
tetrachloroethylene
4-ethylheptane
l-methyl-cis-2-ethyl-
cyclohexane
2 , 6-dimethyloctane
C10H22
C9H18
unknown
ethylbenzene
p_-xylene
C9H18
C10H22
C8H16
m-xylene
phenylacetylene
styrene
isopropylbenzene
C11H24
4-methyldecane
unknown
137
-------
Table 41 (cont'd)
Chroma to graphic
Peak No.
59
60
60A
61
62
63
64
64A
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)
133.5
135
135
136
138.5
139.5
140.5
141
141.5
142
143.5
144.5
146
147
148
148.5
150
150.5
151.5
153
154
154
156
156.5
158
158
159,160
161
161.5
162
162.5
Compound
C10H20
vinyl-2-ethylhexyl ether
(tent.)
bromoform
n-propylbenzene
m-ethyltoluene
p_-ethyltoluene
C10H20
C8H16
C11H24
o-ethyltoluene
2,2, 4-trimethylheptane
1,3,5-trr. 2thylbenzene
n-undecane
m-methyl styrene
^-butyl benzene
4-ethyl-l-octyn-3-ol (tent.)
n-dodecane
1-undecene
1,2, 3-trimethylbenzene
m-dichlorobenzene
n-butylbenzene
dimethylethylbenzene (isomer)
o-methylstyrene
p_-propyltoluene
C11H22
C, -alkyl benzene
C,-alkyl benzenes
(2-methylpropenyl) benzene
C12H26
1-methylindan
Cc-alkyl benzene
138
-------
Table 41 (cont'd)
Chromatographic
Peak No.
89
90
91
92-94
95
96-98
Elution Temperature
(°C)
—
165
166
167,168,168.5
171.5,172,173
Compound
unknown
C12H24
C,-alkyl benzene
C -alkyl benzenes
Cc-alkyl benzenes
Resolution was on a 200 ft OV-17 SCOT programmed from 30-220°C @ 4°/min.
139
-------
Table 42. POLLUTANTS IDENTIFIED IN NIGHT AMBIENT AIR
FROM ANAHEIM, CA*
Chromatographic
Peak No.
1
2
3
3A
4
5 /
6 y 7
7 /
8
9
10
11
11A
12
13
14
14A
15
16
17
18
19
20
21
22
22A
23
24
25
25A
26
Elution Temperature
50
/ ~
55
/ *
57
58
59.5
62
63.5
66
67
67.5
68
69.5
71.5
75
75
77
77
78.5
78.5
80
82
83
84
84.5
84.5
89.5
93
95
96
Compound
co2
-
n-pentane
trichlorofluoromethane
pentene isomer
C5H10
methylene chloride
acetone
n_-hexane
isbpropanol
C6H12
C6H14
3-methylpentene (isomer)
chloroform
methylcyclopentane
1,1, 1-tr ichloroethane
3-methyl-cis_-2-pentene
benzene
carbon tetrachloride
2-methylhexane
C7H14
C5H10
3 , 3-dimethyl-l-pentene
1 , 1-dimethylcyclopentene
trichloroethylene
n-heptane
3-heptyne
2 , 5-dimethylhexane
C8H16
C6H14
n-propyl acetate
140
-------
Table 42 (cont'd)
Chromatographic
Peak No.
27
28
29
30
31
32
33
34
35
36
37
37A
38
38A
39
40
40A
40B
40C
41
42
43
44
45
46
47
48
49
50
51
52
Elution Temperature
97.5
99
101
105.5 .
106
107
111
113
114
115
116
116.5
119
119.5
120
122
124
124
124
125.5
126.5
131
132
133
-
134
135
138
140
141.5
Compound
toluene
2-methylheptane
3-methylheptane
2 , 4-dimethylhexane
n-octane
tetrachloroethylene
hexamethylcyclotrisiloxane
C7H16
1 , 2-dimethylcyclohexane
n-nonane
2-methyl-l-octene
chlorobenzene
ethylbenzene
3-methyloctane
p_-xylene
m-xylene
bromoform
phenylacetylene
cyclooctatetraene
o-xylene
4-ethylheptane
C9H18
C8H18
isopropylbenzene
unknown
C9H18
C10H22
unknown
n-propylbenzene
m-ethyltoluene
1 , 3 , 5-trimethylbenzene
141
-------
Table 42 (cont'd)
Chromatographic
Peak No.
53
54
54A
55
55A
56
57
58
59
60
61
62
63
63A
64
65
66
67
68
69
70
71
72
73
73A
74
75
76
77
78
79
Elution Temperature
143
145.5
146
147
147.5
150
150.5
151
152
153
155
155.5
156
156.5
157
158
159
159.5
160
161
162
162.5
163
164.5
165
167
167.5
169
170
170.5
171.5
Compound
o-ethyl toluene
octamethylcyclotetrasiloxane
1,2, 4-trimethylbenzene
n-decane
acetophenone
m-dichlorobenzene
sec-butylbenzene
o-cymene
1,2, 3-trimethylbenzene
m-cymene
3-methylstyrene
2,4, 4-trimethylhexane
m-diethylbenzene
p_-propyl toluene
C, -alkyl benzene
n-undecane
C, -alkyl benzene
C9H18
C, -alkyl benzene
C, -alkyl benzene
1-methylindan
m-n-propyl toluene
5-methyldecene (isomer)
(1-methylbutyl) benzene
1-dodecene
1,2,3 , 4-tetramethylbenzene
C.-alkyl benzene
C, -alkyl benzene
C. .. H« ~
11 20
C . *n « i
12 24
C.-alkyl benzene
142
-------
Table 42 (cont'd)
Chrotnatographic
Peak No.
80
81
82-85
•Elution Temperature
(°C)
172
174
174.5,175,177
Compound
(2-methyl-propenyl) benzene
C,-alkyl benzene
C.-alkyl benzenes
Resolution was on a 200 ft OV-17 SCOT programmed from 30-220°C @ 4°C/min.
-------
Table 43. POLLUTANTS IDENTIFIED OR DETECTED IN AMBIENT AIR
FROM SANTA MONICA, CAa
Chromatographic
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
(°C)
-
77
79
81
82
86
88
91
92
93
94
96
96,97
98
100
104,106
110
111
111
112
113
115
117
118
120
121
122
124
124
125
Compound
co2
unknown
2-methylpropane
1-butene
2-butene
chloroethane
n-butylamine ( tent . )
isopentane
trichlorofluoromethane
C5H10
n-pentane
cyclopente..e
pentenes
methylene chloride
acetone
C,H-, (isomers)
3-methylpentane
C6H12
C6H14
ii-hexane
C6H12
chloroform
C6H12
methylcyclopentane
C6H10
methyl ethyl ketone
1,1, 1-trlchloroethane
C7H16
benzene
carbon tetrachlorlde
144
-------
Table A3 (cont'd)
Chromatographic
Peak No.
33-35
36
37
38
39
40
41
42
43
44
45
46
47
48,49
50
51
52
53,54
55
56
57
58-61
62
63
64
65,66
67
68
69
70,71
Elution Temperature
127,128,130
130
131
131
132
133
135
136
137
138
141
142
144
146
146
148
150
153,154
154
156
157
159,160,162,163
164
165
165
166,167
168
170
172
173,174
Compound
C-,Hn, (isomers)
/ ID
C_H-.
7 14
3-methylhexane
C_H.,
7 16
C7H1
n-heptane
C..H-.
7 14
dimethylfuran (isomer ?)
C,H17
7 14
C-H..
7 14
C0H1Q
8 18
C-.H- .
7 14
CcHn,0
5 16
C0H, , (isomers)
o ID
CQH1Q
8 18
toluene
C8H18
C8H18
n-octane
C.H.,
8 16
tetrachloroethylene
CqH20 (isomers)
CQH1£
8 16
C..I1.. f.
9 18
chlorobenzene
CoH1 „ (isomers)
ethylbenzene
CQH1Q
9 18
phenylacetylene
C_H1Q (isomers)
-------
Table 43 (cont'd)
Chromatographic
Peak No.
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
100
101-103
104
105-107
Elution Temperature
174
175
178
179,180
181
182
183
184
184
186
187
189
189
190
- 192 -
192
193
194
195,197
197
198
198
200
201
201
202
203
204,205
206
207,209
Compound
o-xylene
n-nonane
CQH1Q
9 18
C-»H00 (isomers)
1U 2.2.
isopropylbenzene
C H
16 22
CQH1Q
9 18
C* TT
10 22
C H
10 20
n-propylbenzene
m-ethyltoluene
p_-ethyltoluene
acetophenone
C H
10 20
1,3, 5-trimethylbenzene
P TJ
10 22
n-decane
1,2, 4-trimethylbenzene
C10H20
isobutylbenzene
C11H24
m-dichlorobenzene
C,-alkyl benzene
1,2, 3-tr imethylbenzene
C10H20
C11H24
methylstyrene (isomer ?)
C,-alkyl benzene
C H
11 24
C , -alkyl benzene
146
-------
Table A3 (cont'd)
Chromatographic
Peak No.
108,109
110,111
112
113-115
116
117
118
119
Elution Temperature
210,211
212,213
214
214,216,217
218
219
222
227
Compound
C....H,,, (isomers)
ll /4
C,-alkyl benzene
C,.-alkyl benzene
C,-alkyl benzene
C.-alkyl benzene
ethylstyrene (isomer ?)
unknown
L»- rt tin /*
12 26
Resolution was on a 400 ft OV-101 SCOT programmed from 30-220° C
@ 4°C/min.
147
-------
Table 44. POLLUTANTS IDENTIFIED OR DETECTED IN AMBIENT AIR
FROM GLENDORA, CAE
Chromatographic
Peak No.
1
2
3
4
5
6
6A
7
7A
8
9
10
11
12
13
14
15
ISA
16
17
18
18A
19
20
21
22
22A
23
23A
Elution Temperature
(°C)
86
92
93
-
-
100.5
103
103.5
104.5
105
106
107
108
109
-
-
115
117
118.5
121
122
122.5
123.5
127.5
129
129.5
130
131.5
132
Compound
difluorochloromethane
1-butene
isobutane
unknown
unknown
i sop en tan e
trichlorofluoromethane
1-pentene
C5H8
n-pentane
isoprene
methylene chloride
propanal
acetone
unknown
unknown
2-methylpentane
2-fluoro-2-methylpropane
3 -methy Ip entane
C6H12
3-methyl-2-pentene + n-hexane
2-methylfuran
chloroform
C6H14
C6H12
methyl vinyl ketone (tent.)
methyl ethyl ketone
1,1, 1-trichloromethane
ethyl acetate
148
-------
Table 44 (cont'd)
Chromatographic
Peak No.
24
25
26
27
28
29
30
31
31A
31B
31C
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
Elution Temperature
(°C)
134
134.5
136
137
138.5
140
-
141.5
142
142
143
143.5
146
147
148
149
151.5
152
154
155.5
157.5
158
161
162.5
163.5
165
167
168
_
Compound
benzene
carbon tetrachloride
C6H12
2 , 3-dlmethylpentane
1,1,3, 3- tetramethylcyclo-
pentane
cyclohexenol isomer
unknown
1 , trans-2-dimethyl-
cyclopentane
C7H16
C7H12
trichloroethylene
n-heptane
C7H12
C6H14
2,2,3, 3-tetramethylbutane
4 , 4-dimethyl-2-pentene
2 , 5-dimethylhexane
3-heptene
C8H16
1-octene
2 , 3-dimethylhexane
toluene
2 , 4-dimethylhexane
2 , 2-dimethyl-3-ethylpentane
trimethylcyclopentane isomer
n_-octane
hexamethylcyclotrisiloxane
tetrachloroethylene
unknown
149
-------
Table 44 (cont'd)
Chromatographic
Peak No.
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64,65
65A
66
67
67A
68
69
70
71
72
73
74
75
76
77
78
Elution Temperature
(°C)
172
173
174.5
175
176
177.5
179
181
182
182.5
184
-
185
185
189,190
191
191.5
192.5
192.5
193
194.5
195.5
196
-
197
197.5
197.5
198
200
201
Compound
2,3, 4-trimethylhexane
C8H16
C9H20
n-butyl acetate
C9H18
chlorobenzene
ethylbenzene
p_-xylene
m-xylene
2,2,5, 5-tetramethylhexane
C9H18
unknown
C9H20
p_-xylene
C10H22 (isomers>
C9H18
C10H22
isopropylbenzene
C9H16
2 , 6-dimethyloctane
C10H20
n_-propylcyclohexane
4-ethyl-3-octene
unknown
2-methyl-3-ethylheptane
4-methylnonane
5-methyldecane
n-propylbenzene
2, 6-dimethyloctane
octamethylcyclotetrasiloxane
150
-------
Table 44 (cont'd)
Chroma tographic
Peak No.
79
80
81
82
82A
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
95,99
100
101
102
103
104
105
106
106A
107
10 7 A
Elution Temperature
201.5
202
203
-
205
205.5
-
-
207
208
209
209.5
210
211
-
-
213
214
215.5
216
217,218
219
221
221.5
202
222
223
224
224
225.5
226
Compound
V i i tin /
11 24
m-ethyltoluene
C. -.H--.
10 20
unknown
n-decane
1,3, 5-trimethylbenzene
unknown
unknown
isobutylbenzene
sec-butylbenzene
m-dichlorobenzene
v 1 1 n rt i
11 24
C,-alkyl benzene
1,2, 4- trimethylbenzene
unknown
unknown
4-ethyl-l-octyn-3-ol
o-diethylbenzene
p_-propyltoluene
m-diethylbenzene
CinH0, (isomers)
11 24
sec-butylbenzene
1 , 4-dimethyl-2-ethylbenzene
C H
11 22
l,2-dimethyl-3-ethylbenzene
n-undecane
C,.-alkyl benzene
CTJ
1 .. LI A n
11 22
C11H20
C12H26
T T ^>/\
11 20
151
-------
Table 44 (cont'd)
Chromatographic
Peak No.
108
109
110
111
111A
112
113
113A
114
115
116
1-17
118
119
Elution Temperature
(°C)
226.5
227
228.5
229.5
229.5
230
230
230
230
230
230
230
230
230
Compound
n-dodecane
2 , 5-dimethyldecane
column background
C11H20
C12H24
C11H20
C12H24
C12H26
C11H24
C12H26
column background
C11H24
C12H26
naphthalene
Resolution was on a 400 ft OV-101 SCOT programmed from 20-230°C @
4°C/min. See Figure 12.
152
-------
COLUMN TEMPERATURE (C°)
I I I I 1 I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I
I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I . I I I I I I I I I I I I I I I . I I I . I . I . I . I . I . I
500
550 600 650 700 750 800 850
MASS SPECTRUM NO.
Figure 24. Total ion current plot of ambient air sample taken at May Street, Houston, TX.
A 200 ft OV-101 SCOT was used, see text for conditions.
-------
Table 45. POLLUTANTS IDENTIFIED IN AMBIENT AIR FROM MAY STREET IN HOUSTON, TX.
Peak No.'
Compound
Peak No.
a
Compound
tn
1
3
6
7
8
9
11
12
13
16
21
24
26
29
31
33
34
35
37
41
ethylene oxide
acetone
n-hexane
methylcyclopentane
benzene
n-butyl vinyl ether
trimethylcyclopentane isomer
cis-2-heptene
ri-heptane
tetramethylcyclopropane isomer
toluene
octene-1
ii-octane
p_-xylene
m-xylene
benzonitrile
£-xylene
3-methyl-2-ethylhexane
isopropylbenzene (cumene)
ii-propylbenzene
46
48
49
51
53
54
56
58
57
58
59
60
63
65
66
67
69
71
73
trimethylbenzene isomer
dichlorobenzene isomer
trimethylbenzene isomer
indan
methylpropylbenzene isomer
dimethylethylbenzene (isomer ?)
methyldecane isomer
diethylbenzene isomer
methyldecane isomer
dimethylethylbenzene (isomer?)
£-cymene
4-phenylbutan-2-one + ii-undecane
tetramethylbenzene isomer
2-phenyl-2-methylbutane
2-methylbenzo-(B)-furan
methylstyrene
dimethyldecane isomer
a-cyanopyridine (tent.) + 2-methyl-
undecane + 2-methylbenzimidazole
methylphthalide isomer
-------
Ln
l/i
Table 45 (cont'd)
Peak No.'
Compound
Peak No.
a
Compound
42,45 C -alkylbenzene
76 n-dodecane
83 n-tridecane
See previous Figure.
-------
25° 75°
I i i i i i i i i i I i
COLUMN TEMPERATURE (C°)
125°
i i i i i i i i I i i i i i i i i
I75e
225*
86..
. I . I . I . I . I . I . I . I I I . I . I . I . I . I . I . I . I . I . I . I I , I I I , I , I . I , I , I , I | I , I , 1 , I , I , I , I I I , I . I . I
1400 1450 1500
1550 1600 1650
MASS SPECTRUM NO.
1700 1750 1800
Figure 25. Total ion current plot of ambient air sample taken at Shaw Drive, Pasadena, TX.
A 200 ft OV-101 SCOT was used, see text for conditions.
-------
Table 46. POLLUTANTS IDENTIFIED IN AMBIENT AIR FROM PASADENA, TX.'
Ui
-vl
Peak No.
2
7
8
9
10
12
13
14
15
18
20
36
38
39
40
41
42
43
44
Compound
acetone
chloroform
dimethyl pentane
benzene
4-methyl-l-pentene
2 , 2-dimethylcyclobutanone
n-heptane
dimethylcyclopentane (isomer) + tetramethyl-
cyclopropane (isomer)
4-methyl-l-hexane
toluene
n-octane
chlorobenzene + xylene (isomer)
C10H22
dichlorobenzene (isomer)
trimethylbenzene (isomer) + cymene (isomer)
limonene
methylstyrene (isomer)
sec-butylcyclohexane
1 , 2-diethylbenzene
C11H24
Peak No.
21
23
24
25
26
29
32
33
34
35
63
64
76
Compound
benzaldehyde + xylene
(isomer)
a -cy anopyr id ine
xylene (isomer)
C9H20
l-methyl-3-ethylbenzene
n-propylbenzene
C_-alkylbenzene
C H + isopropylbenzen
C10H20
C_-ralkylbenzene
C20H22
n-dodecane
n-tridecane
-------
See previous Figure.
Table 46 (cont'd)
Peak No.
50
53
58
60
Compound
1 , 3-diethylbenzene
C~-alkylbenzene
C12H22
C20H24
Peak No . Compound
Ul
CO
-------
80
I I I I I I
COLUMN TEMPERATURE (°C)
140
I I I I I I I
200
16 17
Ui
VO
26
1
00
1
1
1
1
«
1
o
1
1
'I1
17
'I1
00
1
1
1
J
1
0
1
1
1
1
18
1
OO
1
1
1
1
f
\
ft
1
1
1
1
19
'I'M
00
1
£
1
0
1
MASS SPECTRUM NO.
Figure 26. Total ion current of ambient air sample from Baytown, TX. A 200 ft OV-101 SCOT was used,
see text for conditions.
-------
Table 47. POLLUTANTS IDENTIFIED IN AMBIENT AIR FROM BAYTOWN, TX*
Peak No.
Compound
Peak No.
Compound
ON
O
1
2
3
5
7
8
10
12
14
16
17
18
19
20
21
22
0_ + N_ + CO
ethylene oxide
butene isomer + n-pentane
acetone
4-methyl-l-pentene
benzene
cis-1 , 3-dimethylcyclopentane
n-heptane
2 , 4-dimethyl-2-pentene
toluene
tetrachloroethylene
chlorobenzene
xylene (isomer)
dimethylethylpentane (isomer)
xylene (isomer)
methylethylbenzene (isomer)
phenylacetaldehyde
methylethylbenzene (isomer)
trimethylbenzene (isomer)
24
26
27
28
31
33
34
38
40
50
53
56
methylethylbenzene (isomer)
trimethylbenzene (isomer)
n-decane
dichlorobenzene (isomer)
methylstyrene (isomer)
diethylbenzene (isomer)
sec-butylbenzene
acetophenone
diethylbenzene (isomer)
ethylstyrene (isomer)
naphthalene
n-dodecane
See previous Figure.
-------
30e
75C
j I
COLUMN TEMPERATURE (°C)
125°
I75<
225e
2.3
77
110
109
I 108
ice "or
109 106
W4IOS
III
111 .1 1-1 ll 1 I 1 1 ll I 1 I I . I . I I I I I . I . I I I I 1 . I . I . I . I I I . I ll 1 I I 1 . I . I I I . L I . i I I I I I I I I I I I I I i I.I
1900
I960
2000
2050 2100 2150
MASS SPECTRUM NO.
2200
2250
2300
Figure 27. Total ion current plot of ambient air sample taken in Texas City, TX. A 200 ft OV-101 SCOT
was used, see text for conditions.
-------
COLUMN TEMPERATURE (°C)
30°
80°
i i i i i i i i I i i i i
130°
i i i I i i i
180° 200°
I i i i i
N>
900
950
1000
1050 MOO
MASS SPECTRUM NO.
1150
1200
Figure 28. Total ion current plot of ambient air sample taken at Stuebner Airline, Houston, TX.
A 200 ft OV-101 SCOT was used, see text for conditions.
-------
Table 48. POLLUTANTS IDENTIFIED IN AMBIENT AIR
FROM PASADENA, TX*
Chromatographic Elution Temperature
Peak No. (°C) Compound
1
2
3
4
5
6
7
8
8A
9
10
11,12
13
14
14A
15
16
17
18
19
20
20A
21
22,23
24
24A.25
26,27
28
28A
29
53
54
56
57
60
61
61
64
64
68
70
70,71
73
75
75
77
78
80
80
81
83
83
84
85,6
87
87,9
89,91
92
92
94
2-methylpropane
2-methylpropene
2-methylbutane
n-pentane
ethanol (tent.)
furan (tent.)
2-methylpentane
acetone
methylene chloride
methylcyclopentane
3 , 3-dimethylpentane
C_Hn , (isomers)
/ lo
C7H14 + C7H16
C7H16
chloroform
carbon tetrachloride
ethyl acetate
C8H18
C8H16
benzene
C7H14
C8H16
C7H14
CoH,o (isomers)
trichloroethylene
C_H1R (isomers)
C8H16
C8H18
C8H16
C8H16
163
-------
Table 48 (cont'd)
Chromatographic
Peak No.
30
31,32
33
34
35
36
37
37A
38,39
39A.40
41
42
42A
43
44
44A
44B-47
48
49
50
50A
50B
51,52
53
54
55
56
56A
57
57A
58
Elution Temperature
94
95,6
97
98
99
100
101
101
101,4
104,6
107
108
108
110
114
114
114-117
118
119
120
120
120
121,2
123
124
124
126
126
128
128
130
Compound
hexamethylcyclotrisiloxane
CqH20 (isomers)
CQH.,
8 16
C H
9 20
CQH,,
8 16
C H
9 20
C H
9 18
toluene
C_HIR (isomers)
C9H2Q (isomers)
tetrachloroethylene
C H
9 18
methyl isobutyl ketone (tent.)
V f\ Lift f\
9 20
L> f\ £T_ f
9 16
C_H- 0
9 18
C9H22 (isomers)
C0Hon
9 20
ethylbenzene
p_-xylene
chlorobenzene
octamethylcyclotetrasiloxane
C._H-0 (isomers)
ID 2.2.
C11H24
C10H22
a-phellandrene (tent.)
m-xylene
phenylacetylene
styrene
P H
10 22
isopropylbenzene
164
-------
Table 48 (cont'd)
Chromatographic
Peak No.
59
60
61
61A
61B
62
62A.63
63A
64
65,66
67
68
69-71 .
72
73
74
74A
75
75A
76
77,78
79
79A
• 80
80A
81.81A
82
82A
83
84
85
Elution Temperature
131
132
133
133
133
134
134,5
135
136
137
137
139
139-41
142
144
144
144
146
146
148
149,150
151
152
153
153
153
154
154
155
156
156
Compound
C10H20
C11H0/
11 24
C,-alkyl benzene
*-*i -i "« §
11 24
C.H-C1.
424
C- _.£!,. o
10 20
C11H24 (isomers)
bromoform
n-propylbenzene
Ci «H« ,
12 26
m-ethyltoluene
1,3, 5- trlmethylbenzene
C..H_. (isomers)
11 24
p_-ethyltoluene
C10H0.
12 24
£-ethyltoluene
limonene
C,-alkyl benzene
CH
11 24
C,-alkyl benzene
C, r,H. ,
12 26
trimethylbenzene (isomer)
C^ r>H_ ,
12 24
C,-alkyl benzene
dichlorobenzene (isomer)
C,-alkyl benzenes
VM> _ A lio f
12 26
p_-methylanisole
C^ nH., f
12 16
indan
C,-alkyl benzene
165
-------
Table 48 (cont'd)
Chromatographic
Peak No.
86
87
87A
88,89
89A,90
90A
91
91A
91B
92,93
93A
94
94A.95
95A
96
96A
96B
97
97A
98,99
100
100A.101
102
102A,103
103A
104
104A
105
105A
106
10 6 A
Elution Temperature
(°C)
157
158
158
159,160
160,1
161
162
162
162
163,4
164
165
165
165
167
167
167
168
168
168,9
170
170,171
171
171,172
172
173
173
173
173
174
174
Compound
C. ., nn «
11 22
C,-alkyl benzene
dichlorobenzene (isomer)
C,-alkyl benzene
C,.-alkyl benzenes
L.. nii,* f
13 26
C- />H_ *
12 26
8,3-dimethyl styrene
C,.-alkyl benzene
C. Aii~ ~.
13 28
C,.-alkyl benzene
C- f. Rn n
13 28
C, -alkyl benzenes
C.. nil. n
13 28
CL-alkyl benzene
C,-alkyl benzene
C. ^H. /
12 24
C,. -alkyl benzene
Cl nH« /
12 24
C,.-alkyl benzene
L* niln rt
13 28
C(.-alkyl benzenes
C. / H_ _
14 30
C_ -alkyl benzene
5-methylindan (tent.)
C,. -alkyl benzene
C, -alkyl benzene
0
C, -alkyl benzene
C,_-alkyl benzene
C. /xii. f
13 26
C,-alkyl benzene
166
-------
Table 48 (cont'd)
Chromatographic
Peak No.
107
108
108A
109,110,111
111A
112
113
114
114A
115
116-118
119
Elution Temperature
175
177
177
178,9
179
180
181
182
183
183
184-6
187
Compound
C_-alkyl benzene
C. -Hn/-
13 26
C.. oHf^ n
13 28
C,--alkyl benzenes
Cn/H00 (tent.)
14 28
C .. ~ H— f
13 26
C,-alkyl benzene
C,-alkyl benzene
Ci rjAr\f
13 26
C,-alkyl benzene
unknowns
naphthalene
Resolution was on a 200 ft OV-17 SCOT column; 30-220° @ 4°/min.
167
-------
Table 49. POLLUTANTS IDENTIFIED IN AMBIENT AIR
FROM BAYTOWN, TXS
Chromatographic
Peak No.
1
2
3
4
5
6
6A
7
8
9
10
10A.1L
12
13
13A
14
14A
15
16,17
18
19
19A
20
21,22
23
23A.24
25-27
27A
28
29
Elution Temperature
52
53
57
58
61
63
63
65
66
70
72
72,73
75
77
77
77
80
80
82
82
84
84
86
87,88
88
88,89
90,92,93
93
96
96
Compound
2-methylpropane
2-methylpropene
2-methylbutane
n-pentane
acetaldehyde
furan
2-methylpentarie
acetone
methylene chloride
methylcyclopentane
3 , 3-dimethylpentane
C7HTt
7 16
C,H- .
7 14
C-FL,
7 16
C_H, .
7 14
carbon tetrachloride
CQH1Q
8 18
ethyl acetate
C_H.Q (isomers)
C*n£i., f
8 16
benzene
C-IL.
7 14
C0Hn,
8 16
CoH,.R (isomers)
trichloroethylene
CRH1 R (isomers)
CRH . (isomers)
CQH1Q
8 18
CQH1£
8 16
hexamethylcyclotrisiloxane
168
-------
Table 49 (cont'd)
Chromatographic
Peak No.
30
31
32
33
34
35
36
37
38,38A,39
39A
40
40A
41,42
43
44-47
48
49
50
51
52
53
53A
54
54A
55-57
58,59
60
61
62
63
64
Elution Temperature
96
97
97
100
100
100
102
103
104,105,106
106
107
109
112
114
115,116,117,118
120
122
123
124
126
128
128
130
130
131,132,133
133,134
135
136
137
137
138
Compound
CQIL,
8 16
CQH0_
9 20
C-jH,,
8 16
CQH1t
8 16
CQH.n
9 20
C_H1Q
9 18
toluene
CQH1Q
9 18
C_H_0 (isomers)
C10H22
tetrachloroethylene
C0HnQ
9 18
CQH0_
9 20
C_H10
9 18
Cir.H__ (isomers)
1U //
ethylbenzene
C10H22
C11H24
C - «Hrt n
10 22
p_-xylene
\^ _ -. rirt —
10 22
C10H20
isopropylbenzene
C10H20
CniH0, (isomers)
11 24
C....H,,,, (isomers)
11 2.L
n-propylbenzene
C12H26
m-ethyltoluene
p_-ethyltoluene
1,3, 5-trimethylbenzene
169
-------
Table 49 (cont'd)
Chromatographic
Peak No.
65
66
67
68
69
70
70A
71
72
73
74
75
76
77
78
78A
79
79A
80
81
82
82A
83
84
85
86
87
Elution Temperature
(°C)
138
139
140
141
142
143
143
145
145
146
147
148
150
152
152
152
153
153
155
155
157
157
158
159
160
161
162
Compound
C- ., HM i
11 24
C10H_.
12 24
\J- - £ln A
11 22
C_-alkyl benzene
hexamethylcyclopentasiloxane
1,2,4-trimethyl benzene
C»- /-itl. f
12 26
C. , H_ .
11 24
C. i £1. -
11 22
C,-alkyl benzene
C^ r|H/« f
12 26
unknown
1,2, 3-trimethylbenzene
C,-alkyl benzene
dichlorobenzene (isomer)
C,-alkyl benzene
C,-alkyl benzene
C^ ^H. f
12 26
indan
C,-alkyl benzene
C12H26
C. nil. .
12 24
C,-alkyl benzene
C,-alkyl benzene
C.-alkyl benzene
C. 0"i r
12 26
1-methylindan ( tent . )
Resolution was on a 200 ft OV-17 SCOT column programmed from 30-220°
@ 4°/mln.
170
-------
Table 50. POLLUTANTS IDENTIFIED IN AMBIENT AIR
FROM TEXAS CITY, TX*
Chromatographic
Peak No.
2
3
4
4A
5
6
7
8
8A
9
10,11
12
13
13A
13B
14
15
15A
16-16A.17
17A
18
19
19A,20
21,22
22A
23,24
25
25A
26
26A
Elution Temperature
51
53
54
54
56
57
58
59
60
64
65,67
69
71
71
71
73
73
73
75
75
75
78
78,80
81,3
83
84,86
88
88
88
88
Compound
2-methylpropene
2-methylbutane
n-pentane
L» r cl^ f\
5 10
ethanol (tent.)
furan (tent.)
2-methylpentane
acetone
methylene chloride
methylcyclopentane
C-,H.. , (isomers)
/ ID
C7H14
C..H..,
7 16
C7H14
chloroform
C?H16
ethyl acetate
carbon tetrachloride
CoH, Q (isomers)
C8H16
benzene
C-H.. .
7 14
CoH-, (isomers)
C H
8 18
trichloroethylene
C8H16 '
C0H1Q
8 18
CQH1Q
8 18
CDH1Q
8 18
C8H16
171
-------
Table 50 (cont'd)
Chromatographic Elution Temperature
Peak No. (°C) Compound
27'
27A
27B,28
28A
29
29A
30
30A.31
32
32A
33
34
35
36
37
38
39
40
41
42
43,44
45,46
46
46A
47
48
48A
49
50
51
52
90
90
90,1
91
92
92
93
93,4
96
96
97
99
100
102
104
105
106
107
111
111
113,4
114,6
116
116
117
118
118
120
121
122
124
hexamethylcyclotrisiloxane
C8H18
C0H.., (isomers)
0 J.D
C9H20
C8H16
C9H20
C8H16
C.H9n (isomers)
C8H16
C9H20
toluene
C9H18
C9H20
C9H20
tetrachloroethylene
C9H18
methyl isobutyl ketone
C9H20
C9H18
C10H22
C-rtH-- (isomers)
ID 2.2.
C10H22
C9H18
iso-amyl acetate (tent.)
ethylbenzene
p_-xylene
octamethylcyclotetrasiloxane
C10H22
C11H24
C10H22
m-xylene
172
-------
Table 50 (cont'd)
Chromato graphic
Peak No.
53
53A
53B
53C
54
55
56-8
59
60
60A
61
62
62A
63
64,65,66
67
68
69
69A
70
71
72
73
74
75
76
77
78
78A
79
80
Elution Temperature
(°C)
126
126
127
128
128
129
130-2
133
134
134
135
136
136
137
138,140
141
143
145
145
146
147
147
149
150
152
152
152
153
153
155
156
Compound
phenylacetylene
styrene
C10H22
C10H20
isopropylbenzene
C10H20
C11H24 (isomers)
C11H22
bromoform
n-propylbenzene
C11H22
C12H24
m-ethyltoluene
1,3, 5-trimethylbenzene
C11H24 (isomers)
o_-ethyl toluene
1,2, 4-trimethylbenzene
sec-butyl benzene
C11H24
o-cymene (tent.)
m-cymene ( tent . )
C12H26
C10H18
1,2, 3-tr imethylbenzene
C,-alkyl benzene
dichlorobenzene (isomer)
C,-alkyl benzene
C,-alkyl benzene
C12H26
indan
C, -alkyl benzene
173
-------
Table 50 (cont'd)
Chromatographic
Peak No.
81-4
84A
85
86
87
87A
88,89
89A
90
90A
90B
91.
92
92A
92B-95
95A
95B
96
96A
97
98
98A
98B
99
100
101
102
103
104
104A
105
Elution Temperature
157-160
161
161
162
163
163
165
165
166
166
166
167
168
168
168-170
170
170
171
171
172
172
172
172
173
174
176.
177
178
.179
179
180
Compound
C,-alkyl benzenes
C,.-alkyl benzene
C- nil/* -
12 26
Cj.-alkyl benzene
1-methylindan
^1
13 28
C,--alkyl benzenes
C. -H_n
13 28
C. -Hn,.
13 26
C- / n*. 0
14 30
C,.-alkyl benzene
2-methylindan (tent.)
C,.-alkyl benzene
C,-alkyl benzene
D
C^ ^H0 n
13 28
Cc-alkyl benzene
_>
4 (or 5)-methylindan
C. n^/i n
13 28
C,.-alkyl benzene
C_-alkyl benzene
Cn ^H« n
13 28
C,-alkyl benzene
D
C,.-alkyl + C,-alkyl benzene
174
-------
Table 50 (cont'd)
Chromatographic
Peak No.
106
107
108
109
110
111
112
113
113A
114
Elution Temperature
(°C)
181
182
184
185
186
186
188
189
189
191
Compound
C--alkyl benzene +
C,-alkyl benzene +
unknown
C..-alkyl benzene
D
unknown
napthalene
C,-alkyl benzene
0
C^Hp-benzene
Cfi-alkyl benzene
C- / H~ -.
14 30
C13H26
C13H26
Resolution was on a 200 ft OV-17 SCOT column; 30-220° @ 4°/min.
175
-------
Table 51. POLLUTANTS IDENTIFIED IN AMBIENT AIR
FROM PASADENA, TX*
Chromatographic
Peak No.
1
2
3
4
4A
5
5A
6
6A
6B
7
7A
8
9
10
11
12
13
13A
14
15
16
17
17A
18
19
19A
20-23
24,25
Elution Temperature
(°C)
75
76
77
78
78
80
80
85
85
85
90
90
95
97
103
106
108
110
110
112
115
116
116
120
122
123
123
123,124,125,126
128
Compound
propene
so2
chloromethane
2-methylpropane
vinyl chloride
2-methylpropene
n-butane
ethyl chloride
acetaldehyde
tetramethylsilane (tent.)
ii-pentane
acetone
methylene chloride
isopropanol
2-methylpentane
3-methylpentane
C6H12
n-hexane
2-methylfuran (tent.)
chloroform
C7H16
C6H12
ethyl acetate
1 , 1 , 1-tr ichloroethane
3 , 3-dimethylpentane
benzene
carbon tetrachloride
C-.H-, (isomers)
/ lo
C7H1A (isomers)
176
-------
Table 51 (cont'd)
Thromatographic
Peak No.
26
26A
27
28,29
30
31
31A
32,33
33A
34
35
35A
36
37
38,39,40
41
42
43
44
44A
45,46
47
48
49,50
51
52
53
54
55
56
Elution Temperature
130
131
137
138,139
139
141
141
143
143
144
145
146
148
150
150,151,152
153
155
156
156
157
158
160
162
162,164
164
166
166
167
168
171
Compound
trichloro ethyl ene
C-.H.,
7 16
C-H-,
7 14
C_H-_ (isomers)
Vj-j ti_ /
7 14
C0H,,
8 16
dimethyl disulfide
C.H,,
8 16
C-H-,
8 14
methyl isobutyl ketone
C-H,0
8 18
toluene
C H
8 18
l-trans-cis-4-trimethyl-
cyclopentane
C0H, , (isomers)
o ID
C.H, .
8 18
C H
8 16
hexamethyltrisiloxane
tetrachloroethylene
C0H.,
8 16
C-H-- (isomers)
y 2u
C.Hno
9 18
C.H--
9 20
C H (isomers)
y lo
chlorobenzene
C -H
9 20
ethylbenzene
p_-xylene
m-xylene
phenylacetylene
177
-------
Table 51 (cont'd)
Chromatographic
Peak No.
57
57A
58
59
60
61
62-64
65
65A
66
67
67A
68
68A
69
69A
70
71
72
73
74
75
76
77
78
78A
79
80,81
81A
82
82A
Elution Temperature
(°C)
171
171
172
173
173
174
177,178,179
180
180
181
182
182
183
184
185
185
186
186
186
188
189
189
190
191
192
192
194
195,196
196
196
196
Compound
C10H22
2,5-dlethylfuran (tent.)
C10H22
styrene
o-xylene
C9H20
C10H22 (isomers)
isopropylbenzene
1,2,3, 3-tetrachloropropene
C10H22
C9H18
C10H22
a-pir.ene
C10H20
C10H22
n-propylbenzene
C10H22
m-ethyltoluene
C11H24
1,3, 5-trimethylbenzene
C11H24
C11H24
o-ethyltoluene
C10H20
C10H22
1 , 2 , 4-trimethylbenzene
C10H22
C11H24 (isomers)
isobutylbenzene
C11H24
sec-butylbenzene
178
-------
Table 51 (cont'd)
Chromatographic
Peak No.
83
83A
83B
84
84A
84B
85
85A
86
87
88
89
89A
90
90A
91
91A
91B
92
93
94
95
96,97
97A
98
99
99A
100
100A
100B
101
Elution Temperature
197
197
197
199
199
199
200
200
200
201
202
203
203
203
203
204
204
204
204
206
206
207
208,209
210
211
212
212
213
213
213
214
Compound
^11 **n /
11 24
m-dichlorobenzene
o-cymene
C11H24
1,2, 3-trimethylbenzene
m-cymene
L»- . ri/i /
11 24
limonene
C- i H~ ,
11 24
C- /viirt rt
10 20
indan
p_-cymene
C ., ^ Hn i
11 24
m-diethylbenzene
C.. ^Hn f
12 26
m-propyl toluene
n_-butylbenzene
p_-propyltoluene
Ci ~H~ *.
12 26
v> n i its-* /
11 24
o-propyltoluene
C ^ ^H« ,
12 24
C, -alkyl benzene
L- . HA .
11 24
C,. -alkyl benzene
C^ ^H. .
12 21
C,_-alkyl benzene
Cj _ rt-tirt jf
12 26
C;. -alkyl benzene
C, -alkyl benzene
C12H26
179
-------
Table 51 (cont'd)
Chromatographic Elution Temperature
Peak No. (°C) Compound
102
103
104
105
105A
106
107
108
109
110
111
112
112A
115
215
216
218
219
219
219
220
221
222
225
226
229
229
230
C,-alkyl benzene + C,.-
alkyl benzene + C 2^?fi
C,-alkyl benzene
C,.-alkyl benzene
C11H22
C^-alkyl benzene
C12H26
C..-alkyl benzene + C-.H-,
D I/ /D
C12H26
C,-alkyl benzene + C.0H_,
D 1Z Zt)
unknown
C12H26
C H
13 28
naphthalene
C H
13 28
Resolution was on a 400 ft OV-101 SCOT programmed from 30-230°C @
4°C/min.
180
-------
Table 52. POLLUTANTS IN AMBIENT AIR FROM DUNBAR, W VA°
oo
Peak No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
n -i
21
22
23
RRT
0.482
0.490
0.713
0.740
0.767
0.896
1.000
1.030
1.200
1.240
1.270
1.320
1.360
1.455
1.520
1.590
1.640
1.690
1.810
1.830
1r\ i f\
.920
2.050
2.100
Compound
N2
co2
CFC13
methylene chloride
acetone
hexane
methyl ethyl ketone
chloroform
benzene
dimethylpentene
methylhexane
(isomer)
heptane (isomer ?)
ii-heptane
dimethylpentene
(isomer)
n-octane
1-octene
toluene
epoxyheptane
ethylbenzene
p-xylene
Peak No.
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RRT
2.130
2.190
2.230
2.320
2.400
2.450
2.480
2.490
2.500
2.520
2.536
2.555
2.630
2.650
2.715
2.740
2.750
2.800
2.815
Compound
CQ branched alkane
m-xylene
o-xylene
methylethylbenzene
(isomer)
C. branched alkane
n-propylbenzene
methylethylbenzene
(isomer)
Cin branched alkane
benzaldehyde
unknown
2 , 6-dimethyloctane
acetophenone
trimethylbenzene
(isomer)
n-decane
dichlorobenzene
(isomer)
C,-alkyl benzene
die thy Ib enz ene
(isomer)
methylstyrene
(isomer)
C- . branched alkane +
chlorinated aromatic
-------
Table 52 (cont'd)
00
Is)
Peak No.
43
44
45 .
46
47
48
49
50
51
52
53
54
55
56
57
58
59
RRT
2.845
2.870
2.885
2.910
2.920
2.945
2.955
2.980
3.030
3.075
3.110
3.130
3.140
3.175
3.205
3.240
3.260
Compound
diethylbenzene
(isomer)
methyl-n-propyl-
benzene
methyldecane
(isomer)
diethylbenzene
(isomer)
C. 1 branched alkane
C2~alkyl benzene
C_-alkyl benzene
C_-alkyl benzene
n-undecane
dimethylethyl
benzene (isomer)
dimethylethyl-
benzene (isomer)
methylisopropyl-
benzene (isomer)
Cn9 branched alkane
C,.-alkyl benzene
C,--alkyl benzene
C,.-alkyl benzene
n-dodecane
Peak No.
60
61
62
63
64
65
66
67
68
69
70
71
72
RRT
3.280
3.295
3.360
3.380
3.400
3.415
3.450
3.540
3.585
3.610
3.655
3.730
3.800
Compound
C_-alkyl benzene
C_-alkyl benzene
trichlorobenzene
(isomer)
C1 2 branched alkane
naphthalene
C,.-alkyl benzene
C1 1 branched alkane
C1~ branched alkane
n-tridecane
methylnaphthalene
(isomer ?)
unknown
unknown
n-tetradecane
Resolution was on a 200 ft OV-101 SCOT programmed from 30-200°C @ 4°C/min.
-------
Table 53. POLLUTANTS IN AMBIENT AIR FROM SOUTH CHARLESTON, W VAC
eo
Peak No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
RRT
0.520
0.530
0.736
0.735
0.784
0.813
0.922
1.000
1.030
1.245
1.273
1.322
1.394
1.432
1.530
1.600
1.725
1.785
1.920
1.960
2.040
2.195
Compound
N2
CO
z
CFC13
unknown
diethyl ether
methylene chloride
acetone
methyl ethyl ketone
chloroform
benzene
unknown
unknown
unknown
n-heptane
dimethylpentane
(isomer) ,
unknown
toluene
dimethylhexane
(isomer)
n-octane
tetrachloroethylene
unknown
ethylbenzene
Peak No.
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
RRT
2.262
2.275
2.335
2.340
2.372
2.432
2.470
2.490
2.530
2.590
2.618
2.655
2.690
2.710
2.745
2.770
2.790
2.825
2.870
2.920
Compound
p_-xylene
unknown
m-xylene
unknown
o-xylene
unknown
unknown
methylethylbenzene
(isomer)
unknown
unknown
n-propylbenzene
methylethylbenzene
(isomer)
methylethy Ib enz ene
(isomer)
2,6-dimethyloctane +
benzaldehyde
acetophenone
trimethylbenzene
(isomer)
n-decane
C, -benzene
-------
Table 53 (cont'd)
00
Peak No.
43
44
AS
*T^
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
RRT
2.920
2.940
2 Q60
^ t J \J\J
2.990
3.000
3.020
3.050
3.070
3.075
3.090
3.110
3.120
3.140
3.155
3.175
3.200
3.210
3.235
Compound Peak No.
C, -benzene
diethylbenzene
(isomer)
methylstyrene
(Isomer)
diethylbenzene
(isomer)
l-methyl-2-n-
propyl benzene
dimethylethyl-
benzene (isomer)
C .. alkane + diethyl-
-L J.
benzene (isomer)
unknown
unknown
unknown
unknown
dimethylethylbenzene
(isomer)
unknown
unknown
unknown
unknown
61
62
63
64
65
66
67
68
69
70
71
72
73
74
78
79
80
81
82
83
84
85
86
RRT
3.260
3.285
3.342
3.340
3.342
3.361
3.395
3.410
3.421
3.440
3.450
3.470
3.500
3.510
3.600
3.610
3.630
3.665
3.690
3.710
3.730
3.765
3.790
Compound
n-undecane
unknown
unknown
unknown
unknown
unknown
unknown
unknown
methylvinylbenzene
unknown
C,.-alkyl benzene
C12~alkane
unknown
trichlorobenzene
unknown
naphthalene
unknown
unknown
unknown
unknown
unknown
unknown
unknown
-------
Table 53 (cont'd)
00
Cn
Peak No.
87
88
89
90
91
92
93
94
95
RRT
3.820
3.845
3.865
3.890
3.900
3.920
3.940
3.955
3.990
Compound
unknown
unknown
unknown
unknown
unknown
unknown
unknown
unknown
n-tridecane
Peak No.
96
97
98
99
103
104
105
106
RRT
4.020
4.050
4.080
4.120
4.250
4.330
4.520
4.660
Compound
methylnaphthalene
(isomer ?)
unknown
methylnaphthalene
(isomer ?)
unknown
unknown
n-tetradecane
unknown
unknown
Resolution was on a 200 ft OV-101 SCOT programmed from 30-220°C @ 4°C/min, see Figure 8.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-75-076
3. RECIPIENT'S ACCESSIOWNO.
4. TITLE ANDSUBTITLE
DEVELOPMENT OF ANALYTICAL TECHNIQUES FOR MEASURING
AMBIENT ATMOSPHERIC CARCINOGENIC VAPORS
5. REPORT DATE __
November 1975
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Edo D. Pellizzari
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P. 0. Box 12194
Research Triangle Park, N. C. 27709
10. PROGRAM ELEMENT NO.
1AA010
11. CONTRACT/GRANT NO.
68-02-1228
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory
Office of Research and Development
U. S. Environmental Protection Agency
Research Triangle Park. N. C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final 6/74 - 6/75
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Analytical techniques and instrumentation, developed during the previous
contract year, were perfected and evaluated for the collection and analysis of
carcinogenic and mutagenic vapors occurring in ambient air. The areas of
investigation included (a) the .performance of a sorbent cartridge sampler for
hazardous vapors occurring at concentrations of ng/m3; (b) the design, fabrication,
and performance of a portable field sampler; and (c) the identification of hazardous
and background pollutants from several geographical areas in the continental U.S.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Evaluation
Collecting Methods
Air Pollution
*Vapors
*Carcinogens
Gas Chromatography
Mass Spectrometry
14G
14B
13B
7D
6E
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
196
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
186
------- |