'U A U.S. Environmental Protection Agency Industrial Environmental Research
ii •» Office of Research and Development Laboratory
Research Triangle Park, North Carolina 27711
EPA-600/7-77-149
December 1977
ORGANIC EMISSIONS
FROM AUTOMOBILE INTERIORS
Interagency
Energy-Environment
Research and Development
Program Report
z
z
z
7
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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 seven series.
These seven 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 seven series
are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy—Environment Research and Development
This report has been assigned to the INTERAGENCY ENERGY—ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from
the effort funded under the 17—ageucy Federal Energy/Environment
Research and Development Program. These studies relate to EPA’s
mission to protect the public health and welfare from adverse effects
of pollutants associated with energy systems. The goal of the Program
is to assure the rapid development of domestic energy supplies in an
environmentally——compatible manner by providing the necessary
environmental data and control technology. Investigations include
analyses of the transport of energy—related pollutants and their health
and ecological effects; assessments of, and development of, control
technologies for energy systems; and integrated assessments of a wide
range of energy—related environmental issues.
REVIEW NOTICE
This report has been reviewed by the participating Federal
Agencies, and approved for publication. Approval does not
signify that the contents necessarily reflect the views and
policies of the Government, nor does mention of trade names
or commercial products constitute endorsement or recommen-
dation for use.
This document is available to the public through the National Technical
Information Service, Springfield, Virginia 22161.
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EPA-600/7-77-1 49
December 1977
ORGANIC EMISSIONS
FROM AUTOMOBILE INTERIORS
by
Ruth A. Zweidinger
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, N.C. 27709
Contract No. 68-02-1325, Task 46
Program Element No. EHE624A
EPA Project Officer: Joseph A. McSorley
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, N.C. 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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ABSTRACT
This research program was initiated to evaluate the potential for
exposure of the general population to organic emissions of automobile In-
teriors and specifically to vinyl chloride monomer (VCM). This program was
intended as a pilot study to evaluate (a) whether there exists a possible
hazard due to VCN or other hazardous organics and (b) the test conditions
and relevent parameters for further testing of a statistically significant
sample of automobiles should that be undertaken subsequent to this study.
Six subcompact automobiles (Ford Pinto, ANC Gremlin, GNC Vega, G 1C
Chevette, N 1C Datsun 710 and VW Rabbit) were evaluated in this study for the
emission of VCM and other organics into the passenger compartment. The
quantitation of VCM was achieved using Lot No. 104 SKC charcoal cartridges
interfaced with gas-liquid chromatography-mass spectrometry (GLC/MS) in the
single ion mode. The interiors of the automobiles were thermostatically
controlled at either 45 or 65°C for 3 hrs before sampling the car interior.
Each automobile was sampled for VCN at both temperatures. Levels of VCN in
the Ford Pinto, ANC Gremlin, GHC Vega and GMC Chevette were less than the
detection limit of 50 ppb. With improved instrumental parameters a limit of
detection of 2 ppb was attained. Under these conditions no VCN was detected
in the GNC Chevette. VCN was detected in the VW Rabbit at 4±3 ppb when
sampled at 65°C and less than 2 ppb at 45°C. The NNC Datsun 710 was found
to produce VCN levels of 7±2 ppb and 3±1 ppb at 65° and 45°C, respectively.
In accordance with E.P.A. proposed rules as set forth in the Federal
Register, Vol. 42, p. 28154, 1977, these low levels must be regarded as
unacceptable.
111
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Samples for qualitative GLC/HS analysis of each automobile for other
organics were taken at 65°C using Tenax GC sorbent. This analysis produced
a composited list of 147 organic compounds which were identified in the
automobiles but not in the ambient air in the vicinity of the test. Another
36 compounds were tentatively identified. Inclusion in the latter group
resulted when the compound was either in very small amounts or there were
possible interferences.
Of the compounds identified in automobile interiors, aniline, biphenyl,
1,2-dibromoethane (tentative identification), dichlorobenzene (tentative
identification), dimethyiphenol isomers (some isomers are carcinogenic),
isobutyl alcohol, maleic anhydride (tentative identification), naphthalene
and 1,1,1-trichioroethane are listed as having carcinogenic or neoplastic
effects according to the Registry of Toxic Effects of Chemical Substances ,
1976 Edition. Beuzene, carbon tetrachloride, chloroform and phenol are also
listed as carcinogenic or neoplastic; however, they were found in the back-
ground as well as in the automobile interiors.
Further investigation of these emissions seems warranted based upon
these preliminary results; however, it will have to be initiated by that
segment of the E.P.A. specifically responsible for automobile emissions.
This report was submitted in fulfillment of Contract No. 68-02-1325 by
Research Triangle Institute under sponsorship of the U. S. Environmental
Protection Agency. This report covers the period Hay 15, 1976 to December
22, 1976, and work was completed as of April 1, 1977.
iv
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CONTENTS
Abstract iii
Acknowledgments
1. Introduction 1
2. Conclusions 3
3. Recommendations 5
4. Experimental Procedures 7
Sample Design
Selection of Test Automobiles . . . . 7
Parameter Evaluation 7
Sampling for Qualitative Analysis . . . . . 9
Quality Control 9
Analytical Methods . . 1Q
Vinyl Chloride Monomer 10
Gas Liquid Chromatography/Mass Spectroscopic——Qualitative
Analysis of Organics 12
5. Results and Discussion 23
Quantitative Analysis 23
Qualitative Analysis of Organic Emissions 23
References 35
Appendix A 37
Sampling Port 38
Temperature Controls 38
Appendix B 43
Gas Liquid Chromatography—Mass Spectrometry Analysis of Organics in
Automobile Interiors
Appendix C 75
V
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P IGURES
Number Page
1 Mass spectrum of a chromatographic peak identified as vinyl
chloride monomer from an environmental sample 11
2 Gas chromatography/mass spectrometric analysis — single ion
mode (m/e = 62) of: (a) Air from the interior of a Datsun
710 automobile at 65°C (0.5 £ sample), (b) 50 ng standard
of VCM 13
3 Calibration curve for vinyl chloride monomer 14
4 Thermal desorption inlet manifold 16
5 Thermal desorption chamber 17
6 Instrumental outlay of the gas chromatography/mass spectrometry/
computer system 18
A-i Side window on driver’s side 39
A—2 Automobile interior temperature control 40
B—i Total ion current plot during gas liquid chromatography/mass
spectrometry of air sample from the interior of a Vega
(8/26/76) automobile 44
B—2 Total ion current plot during gas liquid chromatography/mass
spectrometry of air sample from the interior of a Datsun
(10/10/76) automobile 50
B-3 Total ion current plot during gas liquid chromatography/mass
spectrometry of air sample from the interior of a Chevette
(10/10/76) automobile 53
B—4 Total ion current plot during gas liquid chromatography/mass
spectrometry of air sample from the interior of a Chevette
(8/25/76) automobile 56
B—5 Total ion current plot during gas liquid chromatography/mass
spectrometry of air sample from the interior of a Pinto
(8/28/76) automobile 58
B—6 Total ion current plot during gas liquid chromatography/mass
spectrometry of air sample from the interior of a Gremlin
(8/26/76) automobile 65
vi
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FIGURES (con.)
Number
B—7 Total ion current plot during gas liquid chromatography/mass
spectrometry of air sample from the interior of a Rabbit
(10/9/76)
3—8 Total ion current plot during gas liquid chromatography/mass
spectrometry of a background air sample
1 8
2 20
3 24
4 25
B—i 47
B—2 51
B—3 54
B—4 57
B—5 61
B—6 66
3—7 70
B—8 73
76
Page
69
72
TABLES
Measurement Matrix
Operation Parameters for GLC—MS—COMP System
Vinyl Chloride Monomer Found in Test Vehicles
Organics Found in Automobile Interiors . .
Organic Compounds Identif led from Figure B—i
Organic Compounds Identified from Figure B—2
Organic Compounds Identif led from Figure B—3
Organic Compounds Identified from Figure B—4
Organic Compounds Identified from Figure B—5
Organic Compounds Identified from Figure B—6
Organic Compounds Identified from Figure B—7
Organic Compounds Identified from Figure 3—8
C—i Frequency—Prioritized List of Organics Found in Automobile
Interiors
vii
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ACKNOWLEDGMENTS
The valuable assistance of Hr. R. B. Keefe in executing the laboratory
and sampling experimentation is gratefully appreciated. ?ls. D. Smith, N.
Pardow and Dr. J. T. Bursey provided the interpretation of mass spectra and
the analysis by high resolution gas-liquid chromatography/mass spectrometry/-
computer in this research project; a sincere thanks for their support. The
helpful suggestions of Dr. E. D. Pellizzari throughout the project are
appreciated.
The assistance of Dr. T. Hartwell with the statistical design of the
experiment is gratefully acknowledged.
The encouragement and support of Project Officer, J. A. HcSorley, of
IERL-RTP is deeply appreciated.
viii
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SECTION 1
INTRODUCTION
The possibility of toxic or carcinogenic organic compounds being
volatilized into the interior of automobiles as a result of the extensive
use of plastics has aroused concern. A number of toxic compounds have
been postulated as arising from the pyrolysis of various plastics at
65°C, and these have been examined. However, even qualitative
information on the identity of these compounds actually occurring in the
automobile interiors is incomplete. Vinyl chloride monomer (VCN) would
be expected to be a likely offender due to the abundance of polyvinyl
chloride (PVC) in automobile interiors. Since VCN is a suspected carcino-
gen in man 6 ’ a very careful assessment of its presence and amount in
automobile interiors should be made using “worst case” conditions.
The “worst case” would provide an upper limit on the exposure to
the public, and an appropriately designed experiment should permit
estimation of levels under less extreme conditions. The inclusion of
qualitative information on other compounds in this study avoids omission
of other hazardous compounds.
Parameters which are likely to be relevant to the selection of
“worst case” conditions are newness of the automobile, plastic-content-
to-volume ratio, and temperature. The age of a test automobile is
expected to affect the amount of residual VCN in the PVC components.
Temperature and ventilation history may have a very substantial influence
on the residual VCM; however, these parameters were not controllable for
the period between the automobile’s manufacture and initiation of the
study. If extremes of temperature history are available that information
would certainly be useful, but not essential. Subcompact cars potentially
represent the “worst case” for plastic-content-to-volume-of-interior
1
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ratio and consequently should accumulate the highest concentrations over
a given interval. The last parameter for the “worst case” criteria is
temperature. The volatilization of VCM would be expected to be diffusion
controlled since it is a gas at normal ambient temperatures (boiling
point: —13°C). The temperature dependence of the diffusion rate will
depend upon the properties of the particular polymer. Numerous different
formulations and applications of PVC from foams to solid sheets are
found in automobile interiors; therefore, only actual measurement of the
resulting VCN levels as a function of temperature and time will yield
meaningful information.
The experimental design used in this study was selected to maximize
the information content for a manageable number of samples. The identi-
fication of other organics emitted into the automobile passenger compart-
ment was designed to probe the potential exposure to hazardous organic
compounds. In this case, only qualitative information at the highest
selected temperature was sought.
2
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SECTION 2
CONCLUSIONS
Six subcompact automobiles (Ford Pinto, ANC Gremlin, GNC Vega, GMC
Chevette, NNC Datsun 710 and VW Rabbit) were evaluated in this study for
the emission of vinyl chloride monomer (VCM) and other organics into the
passenger compartment. The quantitation of VCH was obtained using Lot
104 SKC charcoal cartridges interfaced with gas-liquid chromatography-
mass spectometry (GLC/NS) in the single ion mode. The interiors of the
automobiles were thermostatically controlled at either 45 or 65°C for 3
hrs before sampling the car interior. Each automobile was sampled for
VCH at both temperatures. Levels of VCN in the Ford Pinto, MC Gremlin,
GNC Vega and GMC Chevette were less than the detection limit of 50 ppb.
With improved instrumental parameters a limit of detection of 2 ppb was
obtained. Under these conditions no VCN was detected in the GMC Chevette.
Vinyl chloride monomer was detected in the VW Rabbit at 4±3 ppb (± 3
refers to standard deviation of duplicate samples) when sampled at 65°C
and less than 2 ppb at 45°C. The NNC Datsun 710 was found to produce
VCN levels of 7±2 ppb and 3±1 ppb at 65° and 45°C, respectively. Since
the analysis of VCN in the interiors of Ford Pinto, ANC Gremlin and GHC
Vega was not repeated with the lower limit of detection, no comparison
of their VCN levels with the other three automobiles can be made. In
accordance with EPA proposed rules as set forth in the Federal Register, 8
these low levels must be regarded as unacceptable.
An array of times as well as temperatures was originally proposed to
indicate aging effects and one automobile in the study, the Chevette,
was sampled at 1 month and 3 months of age. The VCN levels were below
the limit of detection at both sampling times. Although the limit of
3
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detection changed between the two times, no inference may be drawn from
the results except that the levels were below the limits of detection of
50 and 2 ppb at 1 and 3 months respectively. It should be pointed out
that 50 ppb is regarded as the usual limit of detection of VCM analyses
and that the levels found in the Rabbit and Datsun 710 would not normally
have been detected.
The selection of new compact automobiles sampled at elevated tempera-
tures was based on the assumption that this would represent the “worst
case” for accumulation of VCN in the passenger compartment. The results
of this study probably represent an upper range for VCN exposure due to
the use of polyvinyl chloride in automobile manufacture.
Samples for qualitative GLC/NS analysis of each automobile for
other organics were taken at 65°C using Tenax GC sorbent. This analysis
produced a composited list of 147 organic compounds which were identified
in the automobiles but not in the ambient air in the vicinity of the
test. Another 36 compounds were tentatively identified. Inclusion in
the latter group resulted when the compound was either in very small
amounts or there were possible interferences. Of the compounds identified
in automobile interiors, aniline, biphenyl, 1,2-dibromoethane (tentative
identification), dichlorobenzene (tentative identification), dimethyl-
phenol isomers (some isomers are carcinogenic), isobutyl alcohol, maleic
anhydride (tentative identification), naphthalene and 1,l,l-trichloro-
ethane are listed as having carcinogenic or neoplastic activity; however,
they were found in the background as well as in the automobile interiors.
4
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SECTION 3
RECOMNENDATIONS
Since the Environmental Protection Agency has set the goal of zero
emission for vinyl chloride tnonomer 8 the low levels found in this study
must be regarded as unacceptable. Further study of a larger, more statisti-
cally significant sample is recommended before any action is taken.
Several other compounds were found in the course of this study which
(9)
are listed as having carcinogenic or neoplastic effects. Further quanti-
tative evaluation of these compounds should be included in any vinyl chloride
evaluation which might be undertaken.
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6
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SECTION 4
EXPERIMENTAL PROCEDURE S
SAMPLE DESIGN
Selection of Test Automobiles
Subcompact model cars, potentially represent the worst case of all
models where the extent of plastic utilization to interior volumes is
concerned. For this reason the subcompact was used for all tests.
The selection of the manufacturers of the test automobiles is a
more complex problem. The number of cars to be evaluated was limited to
six; however, the number of manufacturers of subcompact cars substantially
exceeds this number. Initially a random selection was proposed with the
probability of selecting each manufacturer weighed according to their
percentage of the total subcompact sales. This selection would represent
a random sample of the subcompact car industry as a whole; however, the
practical matter of obtaining automobiles suitable for this study narrowed
the range of selection to those automobiles which represent the greatest
portion of subcompact sales (i.e., Ford Pinto, ANC Gremlin, GFIC Vega,
GMC Chevette, NNC Datsun 710 and VW Rabbit).
Parameter Evaluation
The evaluation of the VCM hazard requires knowledge of its concen-
tration in the interior of a representative sample of automobiles.
There are several parameters which would obviously affect the buildup of
VCM. The most prominent among these are the temperature of the automobile
interior and its age. The sampling matrix originally proposed for this
study evaluated these parameters.
The plan called for automobiles to be selected whose ages were
known to be between 30 and 90 days. This selection would have insured
that in a 60-day experiment the age dependence data for all of the cars
would overlap. If for some reason the necessary make, model and age
requirements were not met, the age requirement would be altered in one of
I
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the two following ways without substantial loss of information:
(1) sample over a 90-day period
selecting cars 30 to 120 days old, or
(2) sample over a 60-day period
selecting cars 60 to 120 days old.
Assuming the sample contaied cars 30 to 90 days old, the sampling
would be performed at 30-day intervals to obtain three time points for
each automobile. Although the age criterion was broader than planned
for cars in the study (30-120 days), the sample still represented a
group of fairly new automobiles.
The second controlled parameter, temperature, was to have been
evaluated at three levels, 25°C, 45°C and 68°C. These were selected as
representative of normal ambient (77°F), high ambient (113°F) and an
extremely high, but possible temperature (154°F).
A matrix of the temperature and age levels was selected which would
evaluate both parameters while minimizing the number of analyses. The
matrix of measurements which was originally planned is shown in Table 1.
Table 1
MEASUREMENT MATRIX
ys
a
t
t+30days
t+60days
25
45
68
X
X
X
X
X
X
a = age of car at beginning of study.
8
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Using this array, six automobiles may be evaluated for two para-
meters at three levels each with only 36 analyses. Of course, because
all three levels of temperature and age are not evaluated for each car,
this implies that some information is lost on the interactions between
these parameters.
In the actual experiment the sampling array was truncated after the
first period due to the very low to nondetectable amounts of VCM found.
The maximum temperature which could be satisfactorily maintained was
65°C; therefore, this temperature was substituted for 68°C in Table 1.
The detailed test procedure is in Appendix A.
SAMPLING FOR QUALITATIVE ANALYSIS
A detailed description of the sampling procedure is included in
Appendix A.
Samples from each automobile were collected at an interior tempera-
ture of 65°C using Tenax GC cartridges (2.2 g sorbent each). Blanks of
the purge gas were to be taken to pinpoint the car interior as the
source and to access the background due to transportation and handling.
Since the purge proved to be an impractical and uncertain method of
lowering and/or establishing the background, the ambient air adjacent to
the study site (outside of the Gremlin in a calm area) was sampled. The
analysis was qualitative in nature; hence, background compounds were
recognized on a present or absent basis. This qualitative basis does
not permit the recognition of enrichment of compounds in the auto interior.
The ambient air sample was typical for a nonindustrial urban area and
was used as baseline for the entire study.
QUALITY CONTROL
The value of any analytical procedure is substantially influenced
by the control data accumulated in the sampling and analysis process.
This factor becomes more important as lower concentrations or more
ubiquitous compounds are sought. Blanks (unsampled cartridges in the
case of charcoal, ambient air in the case of Tenax) were prepared for
each group of samples collected and subjected to the same rigors of
transportation and storage as the samples.
9
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In order to control both the effects of recent ventilation and ambient
levels of organic pollutants, it was proposed that the automobiles be purged
with clean air (charcoal filtered) before each experiment. This purge would
facilitate the evaluation of the GLC/MS analysis of the organic vapors
arising from the plastic materials by removing the normal ambient air hydro-
carbons. The purge proved to be impractical in several respects. First,
because the volume which needed to be exchanged was large, a long cycle time
would be required to dilute the interior compartment with “clean” air.
Second, infiltration of air into the passenger compartment was significant
and continued throughout the test. The cars were to be sealed after the
purge for a set equilibration period determined in a one-car pilot experiment,
perhaps 8-18 hours. In actual tests, the 65°C temperature could be maintained
for only 4 to 5 hours during the hottest portion of the day; therefore, this
period was used whether equilibrium was obtained or not. This approach
provided no control over artifacts from ambient air, except that provided by
control blanks. More significantly, no control could be obtained with an
assembled automobile which would correct for the contamination of the interior
by fuel vapors and auto exhaust.
ANALYTI CAL METHODS
Vinyl Chloride Monomer
The quantitative analysis of VCM was accomplished using cartridge
desorption interfaced to a capillary gas chromatograph/mass spectrometer.
This system had been used with success previously in the single ion monitor
mode for the quantitation of N-nitrosodimethylamine in complex mixtures.
The same technique is applicable to the analysis of VCM. Two important
factors are very favorable for the VCM analysis: chromatographic separation
and a unique ion (Figure 1). Limits of detection with this method were
controlled primarily by the sample volume collected on the cartridge.
Originally Tenax GC was proposed as the collection medium. However, for
good quantitation, the sample volume with the standard 2.2 g Tenax GC cartridge
should not exceed 0.5 2. This does not leave a large margin for such factors
as the effects of temperature on breakthrough volume. In view of this,
another sorbent, activated charcoal (Lot 104 Charcoal S.K.C., Philadelphia,
10
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I I I I I I I I I
II I III I III 1 II II III I I 111111 111111 I till II 11111 liii l iii tIll till iiitt titi ii 111111 liii titti tilt 11111111 11111111 iii i ti i iuti
6,
2
64
C H 2 = C H Cl
ir,i m inn
till i I I ‘ I I I I 4 1 1 I
I 11111 I I I I I I I I
i 10 20 30 40 ) 60 70
lIP 50
I lIP
I U 2111
e
i1li lIII,Ils1;i,II;,II ;lIlI llI rl2Is!1it I;I IIII1 Iltti:ilIl;itIl’I;I il :;ii:i,
I I I I I I I I I I I I I I
I I I I I I I
80 90 I 110 120 130 140 I
150
100
Figure 1. Nass spectrum of a chromatographic peak identified as vinyl
chloride monomer from an environmental sample.
11
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Pa.), was used. A cartridge, 6 mm o.d. x 10.5 cm length, was filled with
150 mg of charcoal. The breakthrough volume of this cartridge is “3 2 at
25°C; hence, samples of 0.2 or 0.5 2 were well below the breakthrough volume
or approximately 3 times that of Tenax. In the first group of analyses
(7/28/76 to 8/2/76), the charcoal cartridges were desorbed directly in the
capillary GLC/NS system. Although this procedure worked satisfactorily, as
far as the production of useful data, the large amount of water accumulated
on the charcoal caused excessive instrument deterioration. To avoid this
problem, a method for removing the water was devised for the second group of
samples. In this technique the charcoal cartridges were thermally desorbed
and the sample passed through a 2 cm bed of calcium chloride to remove the
water. The vinyl chloride was collected on a Tenax GC cartridge (2.2 g).
The Tenax GC cartridge was then thermally desorbed into the GLC/MS system in
the usual manner. The recovery from the charcoal to Tenax GC transfer was
found to be 95%. All calibration standards in this phase were carried
through the transfer procedure.
Sample chromatograms of a standard and a sample from the Datsun 710 at
65°C are shown in Figure 2. The calibration curve for the samples analyzed
9/29/76 and 9/30/76 and the control samples are shown in Figure 3. The
control samples were obtained by preparing 1.0 ppm and 0.5 ppm dilutions of
VCN in a Tedlar bag, placing them in an oven at 65°C and sampling 0.2 2
using charcoal cartridges. These samples were transferred to Tenax GC
cartridges and analyzed as described above.
Gas-Liquid Chromatography/Nass Spectroscopic--Qualitative Analysis
of Organics
A system for the collection, concentration and analysis of a broad
range of organic compounds at trace levels in ambient air was previously
developed and was used in this study without further modification. The
method is based upon collection on a Tenax GC cartridge and thermal de-
sorption analysis. The thermal desorption technique which is a refinement
(10)
of Duel s solvent-free sample inlet system has been used at RTI to
analyze organics in ambient air (EPA Contract No. 68-02-1228) as well as
those in energy—related wastes and effluents (EPA Contract No. 68-03-
12
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CoJ iiiin: 91H OV—101 capillary
1enipcr itiire l’rograiii T liii I Ia 1 20°C
p rograiiuned at 4°C/rn Iii
2 4
Time (mm.)
Figure 2.
Gas chromatography/mass spectrometric analysis — single ion mode
(m/e = 62) of: (a) Air from the interior of a Datsun 710 auto-
mobile at 65°C (0.5 2 sample), (b) 50 ng standard of VCM.
>-
U)
U)
c
C
0
VCM
VC M
Chroinatographic coiidlr tons
A
>.
U)
C
U)
C
C
0
-------
150
ioo
U )
CO
a)
C ’)
V
50
0 — Average values of standards
0 — Values obtained ircm control
experiments
100 200 300 400 0u bOO
VCM in sample (ng)
Figure 3.
Calibration curve for vinyl chloride monomer.
14
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2368). The system is designed so that the entire sample mixture can be
introduced onto the GLC column.
The inlet manifold (Figure 4) for introducing the sample into the
instrumental systems consists of four main components: a desorption
chamber (Figures 4 and 5); a six-port, two-position, high-temperature
low—volume valve; a nickel capillary trap and a temperature controller.
An aluminum sandwich serves as a thermal source. Two heating
cartridges are used to heat the aluminum sandwich, and the temperature
is monitored and controlled with a platinum sensor probe. The desorbed
vapors pass into a six-port, two-position valve which is also encased in
an aluminum heating bath. Temperature control is identical to the
thermal desorption chamber. The temperature is monitored directly on a
pyrometer. Control is ± 1°C.
A nickel capillary constitutes one loop of the valve proper which
is cooled with liquid nitrogen and serves as a trap for collecting and
concentrating desorbed vapors prior to their introduction into the high-
resolution GLC column. The vapors are released from the capillary trap
by rapidly heating to 175°C.
The multiport valve used on the inlet manifold was chosen for its
polyimide stem to minimize the contact of desorbed trace vapors with
reactive metal surfaces, therefore minimizing contamination and/or
decomposition of sample constituents.
In a typical thermal desorption cycle, a Tenax GC sampling cartridge
containing volatile organics was placed in the preheated (>270°C) chamber,
and helium gas was passed through the cartridge (>20 mi/mm) to purge
the vapors into the liquid-nitrogen-cooled capillary trap. This condition
constitutes the valve position A (Figure 4). After the thermal desorption
step was completed, the six-port. valve was rotated to position B (Figure
4): the temperature on the capillary loop rose rapidly, whereupon the
carrier gas carried the vapors onto the high resolution capillary column.
For the identification of volatile organic compounds, the combined
technique of gas-liquid chromatographyJmass spectrometry/computer (GC/ IS/-
CONP) was employed. The instrumental outlay is shown in Figure
Techniques previously developed by RTI for analysis of hazardous compounds
were applied to this research program.
15
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COMPRESS1ON SPRING
PURGE
GAS
TEMPERATURE
CONTROLLER
I—
LVE POSITiON A
(SAMPLE DESORPTION)
SAMPLING
ALUMINUM
HEATI NO
BAT H
ALUMINUM
HEATING
BATH
Six-PORT
TWO POSITION
VALVE
—
CARRIER
GA S
PURGE
GAS
TO
GLC
VENT
GAS
— 1
VALVE POSIflON B
(SAMPLE INJECTION)
TO GLC CAPILLARY
HEATING AND COOLING
BATH
Ni CAPILLARY TRAP
TO GLC
VENT I
I CARRIER
I GAS
I PURGE
I GAS
Thermal desorption inlet manifold.
L._ ——-- ---i
Figure 4.
16
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DESORPTION CHAMBER
TO VALVE
TEFLON INSERT
COMPRESSION SPRING
4 PURGE GAS
GLASS CARTRIDGE SAMPLER
13.0mm
10.5cm 1
15.0 cm
13.30 cm
II
O.56
Figure 5. Thermal desorption char:ber.
-------
SEPARATOR
CYPIIERNETICS
TIME SHARED
PDP/1O
Ei ure 6. Instrumental outlay of the gas chromatography/mass spectrometry/
00
SAMPLE
INLET
MAN TFOLD
T
computer system.
-------
The previously described inlet manifold was used for recovering vapors
trapped on Tenax GC cartridges, and it was interfaced to the GLC/ 1S/COMP
system. The desorbed vapors were subsequently resolved by gas-liquid chroma-
tography, and mass cracking patterns were automatically and continuously
obtained throughout the GLC run with a Varian CH-7 mass spectrometer.
Operating parameters, depicted in Table 2 for the GLC/NSJCONP system are
suitable for the volatile organic fraction. Analysis profiles from automobile
interiors are included in Appendix B, along with an unabridged list of
identified compounds. The high resolution capillary columns are capable of
resolving a multitude of compounds to allow their subsequent identification
by MS/COMP techniques.
The NS was first set to operate in the repetitive scanning mode. In
this mode, the magnet is automatically scanned exponentially upward from
preset low mass to high mass values. Although the scan range may be varied
depending on the particular sample, typical values would be from m/e 28 to
m/e 400. The scan is completed in approximately 5 seconds. At this time
the instrument automatically resets itself to the low mass position in
preparation for the next scan. The information is accumulated by an on-line
620/L computer on magnetic tapes. The reset period is approximately 2
seconds. Thus, a continuous scan cycle of 7 seconds per scan was maintained.
Depending on specific sample requirements, this scan cycle can be shortened
to as little as 5 seconds per cycle.
With the magnet continuously scanning, the sample was injected, and
automatic data acquisition was initiated. As each spectrum was acquired by
the computer, each peak which exceeded a preset threshold was recognized and
reduced by centroid time and peak intensity. This information was stored in
the computer core while the scan was in progress. In addition, approximately
30 TIC values and an equal number of Hall probe signals were stored in core
as they were acquired. During the 2 second period between scans, this
spectral information, along with the spectrum number, was written sequentially
on magnetic tape, and the computer was reset for the acquisition of the next
spectrum.
19
-------
Table 2. OPERATING PARAMETERS FOR GLC-MS—COMP SYSTEM.
Parameter Setting
Inlet manifold
desorption chamber 270°C
valve 180°C
capillary trap — minimum —195°C
maximum +175°C
GLC
200—700 ft SCOT glass capillary 20—30°C, 4/C° mm
carrier (He) flow ‘\‘3 mi/mm
transfer line to ms 210°C
MS
scan range m/e 20 - 300
scan rate, automatic—cyclic 1 sec/decade
filament current 300 hA
multiplier 6.0 6
ion source vacuum ‘\ 4 x 10 torr
a 0 101
20
-------
This procedure was continued until the entire GC run was completed.
By this time, there were from 300 to 1000 spectra on tape, which were
then used for subsequent data processing. Depending on circumstances,
either the tapes were then be processed immediately, or additional
samples run and the results determined later.
The mass spectral data was processed in the following manner.
First, the original spectra were scanned, and TIC information extracted.
This was done directly from the original tape immediately after data
acquisition. Then the TIC intensities were plotted against the spectrum
number on the Statos recorder. The information thus gained generally
indicated whether or not the run was suitable for further processing,
since it gave some idea of the number of unknowns in the sample and the
resolution obtained using the particular GLC column conditions.
The next stage of the processing involved the conversion of the
spectral peak times to peak masses. To accomplish this, the spectra was
read successively into the Varian computer core and then sent at high
speed to the PDP/8 disc by means of the intercomputer interface. Depen-
ding on the number of peaks in each spectrum, the disc capacity allowed
the storage of 200-500 spectra. After the spectra containing time
information were stored in the disc, the data was returned to the 620/L
for mass conversion and re-stored on magnetic tape. The mass conversion
was accomplished by use of the calibration table obtained previously.
Normally, one set of calibration data was sufficient for an entire day’s
processing since the characteristics of the Hall probe are such that the
variation was less than 0.2 atomic mass units per day. For very long
runs it was necessary to carry out several cycles of mass conversion
using the PDP/8 disc to complete the data processing. Time required for
the conversion process for 100 spectra was approximately 1 hour.
After the spectra were obtained in mass-converted form, processing
proceeded manually. In the manual mode, the full spectra of scans from
the GC run were recorded on the Statos plotter. The TIC information
available at this time was most useful for deciding which spectra to
analyze. At the beginning of the run, where peaks were very sharp,
nearly every spectrum was inspected individually. Later in the run,
when the peaks were broader, only selected scans were analyzed.
21
-------
Resolved components were identified by comparing the mass cracking
patterns of the unknown mass spectra to an eight major peak index of
mass spectra.(]2) Searches for individual difficult unknowns, using the
Cornell University STIRS and PMB systems were unnecessary. Unknowns may
also be submitted to the EPA MSSS system for identification; however,
this was not required. When feasible, the identifications may be
confirmed by comparing the unknown’s cracking pattern and elution tempera-
ture on two different columns (OV-l7 and OV-lOl SCOT capillaries) with
authentic compounds; e.g. benzothiazole was compared to an authentic
sample. Particular note was made of the boiling point of the identified
compounds with the elution temperature and the order of elution of
constituents in homologous series, since the OV-lOl SCOT capillary
separates primarily on the basis of boiling point.
22
-------
SECTION 5
RESULTS AND DISCUSSION
QUANTITATIVE ANALYSIS OF VINYL CHlORIDE NONONER
Briefly, the test conditions were an initially ventilated compart-
ment, closed and thermostatically maintained at either 45°C or 65°C for
3 hours before sampling. The results are shown in Table 3 with pertinent
information on the automobiles. The quantitation was performed using
charcoal cartridges for the collection of 0.2 or 0.5 £ air samples. The
vinyl chloride was recovered by thermal desorption and analyzed by
capillary GLC-uiS using single ion detection atm/e 62. This method is
sensitive and selective.
The instrumental operating parameters for the first test sequence
(June 29 - July 2, 1976), which included all the domestic automobiles
tested, did not permit the detection of VCM at levels below 50 ppb;
however, the General Motors Chevette in this group was included in the
second test sequence with the imported automobiles where the limit of
detection had been lowered to 2 ppb. Again, VCN was not detected in
the Chevette.
QUALITATIVE ANALYSIS OF ORGANIC EMISSIONS
The summarized list of the organics found in the six test automobile
interiors is given in Table 4. The list has been prepared by removing
compounds found in the background and collating the compounds found in
each car to remove redundancies. The combined list was then organized
according to structural characteristics for the convenience of evaluating
toxicity.
The list of hydrocarbons is long even with the background subtracted
and probably represents a significant background due to gasoline evapora-
tive emissions. The background sample was taken outside, next to the
Gremlin, in a calm area (protected on two sides).
23
-------
Table 3. VINYL CHLORIDE MONOMER FOUND IN TEST VEHICLES.
Manufacturer
Model
Description
of Upholstery
Temp. (°C)
Date of
Manufacture
Sampled
VCHa
ppb
Ford
Pinto
tan vinyl
45°
65°
6/76
7/30/76
7/29/76
<50
<50
AIIC
Gremlin
blue vinyl
45°
65°
4/76
8/20/76
7/30/76
<50
<50
GMC
Vega
tan vinyl
45°
65°
7/76
8/02/76
7/30/76
<50
<50
GMC
Chevette
dark blue vinyl
45°
65°
45°
65°
6/76
7/28/ 76
7/28/76
9/29/76
9/29-30/76
<50
<50
< 2 a
< 2 a
Nissen Motor
Corp.
Datsun
710
black vinyl
45°
65°
5/76
9/29-30/76
9/30/76
7
+
+
Volkswagen
Rabbit
black leatherette
45°
65°
7/76
9/29/76
9/29/76
4
< 2 a,c
+ 3 a,c
aBlanks were all below the limit of detection (2 ppb).
bTIte lowest standard which was analyzed was 40 ppb. The estimates here are obtained by extrapolation
of the calibration curve.
CAverage and standard deviation of duplicate determinations.
-------
Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS
Compounds Notes
Halogenated Compounds
1,2—dibromoethane (tent.) a
ehlorobutane (tent.) b
chlorocyclohexanol b
chiorostyrene (tent.) b
hexachioroethane (tent.) b
chloroethylbenzene (tent.) b
dichlorobenzene isomer c
trichlorobenzene isomer d
O gen Containing Compounds
Aldehydes and Ketones
propenal e,f
propanal e,f
2—methyipropanal e
2—methyipropenal (tent.) e,f
-butanal e,f
3—methylbutanal e
—hexanal e,f
hexanal isomer f
3—methylbutanal f
n—heptanal e
2—butenal f
ethylbutanal (tent.)
methoxybenzaldehyde b
methyl vinyl ketone e
methyl ethyl ketone e
4 —methvl—2—pentanone f
2 —heptanone f
octanone isomer (tent.)
25
-------
Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.)
Compounds Notes
Oxygen Containing Compounds (con.)
Aldehydes and Ketones (con.)
cedranone (C 15 H 4 0) (tent. ?) c
long chain propyl ketone c,d
Alcohols
2—propanol e
2—methyl—2—propanol e , a, f
2—methyl—l—propanol e
1—butanol e,f
2—methyl—l—butanol (tent.) f
undecenol (tent.) d
dimethyiphenol isomers e,a,f,b
ethylphenol isomer f
cresol c,b,g
di—t—butyl cresol b,d
Ethers
furari b,f
dimethyl ether e,f
diethyl ether e
vinyl methyl ether (tent.) c,d
ethyl vinyl ether c
m—cresyl ethyl ether c,b
diphenyl ether (tent.) c,d
benzyl phenyl ether (tent.) c,d
furfuryl methyl ether (tent.) b
dimethyl—l,4—dioxane (tent.) b
methyl anisole b
butyl methyl ether d
dihydropyran d
anisole d
26
-------
Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.)
Compounds Notes
Oxygen Containing ComDounds (con.)
Ethers (con.)
diphenoxybenzene g
methoxyanthracene (tent.) b
Other
ethyl acetate f
nialeic anhydride (tent.) b,g
hexenyl hexenate (tent.) b
phthalate g
Nitrogen Containing Compounds
N—methyl—2—butylamine (tent.) b
diethylamine (tent.) b
N-n—butylpiperidine (tent.) b
butylaminodiphenylamine (tent.) d
2—amino—2--methyl—l—propanol g
cyclohexylamine (tent.) c
aniline g
trimethylindoline (tent.) c
phenylindole (tent.) c
pyridine (tent.) b
N—ethylpyridine (tent.) c
phenylpyridine (tent.) c
dimethyiquinoline d
propene nitrile (tent.) a
propane nitrile (tent.) b
3,3—dimethylcyclobutane carbon nitrile (tent.) g
toluene diisocyanate (tent.) c
Sulfur Contain4D Compounds
carbon disulfide e,c,b
diethyl sulfide e
beuzothiazole e,d,g
diisobutylthiophene (tent.) b
d
27
-------
Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.)
Compounds Notes
Sulfur Containing Compounds (con.)
C 8 —alkyJ. thiophene (tent.) d
Aromatic Hydrocarbons
isopropylbenzene e, f
n—propylbenzene e,a,f,c,b ,d
1,2, 4—trimethylbenzene e , a, f
o—propylto luene e,a
diethYlbe e isomer e
ethy lbenzene a, f , c
—xy1ene a,f
1,3,5—trimethylbenzene a
—propylto1uene a
C 4 —alkyl benzene isomers e,a,f,c,b,d
C 5 —alkyl benzene isomers e,a,f,c,b,d
diiuethylethylbenzene isomers e,a
tetramethylbenzene isomer e
2 —ethy lto luene f
biphenylene c
C 6 —alkyl benzene isomers c,b,d
dimethy idihydroindene or
methyltetrahydronaphthalene c ,b ,d
C 7 —alkyl benzene isomers c,b,d
unsaturated C 6 —alkyl benzene isomers c
unsaturated C 7 —alkyl benzene isomers c
C 9 —alkyl benzene isomer c
biphenyl c,b,g
unsaturated C 8 —alkyl benzene isomer c
trimethy lisopropylbenzene b
phenylcyclohexene b
C 3 —alkyl benZene d
methyistyrene isomers c,b,d
28
-------
Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.)
Compounds Notes
Aromatic Hydrocarbons (con.)
dimethyistyrene a,d
C.,—alkyl styrene isomers c
diethyistyrene isomers b
di—t—butylphenanthrene (tent.) B
dimethylindane b ,d
naphthalene e,c,b
methyltetrahydronaphthalenes c
dimethylnaphthalene c ,b , d, g
dimethyldihydronaphthalenes c
tetrahydronaphthalene b
ethyltetrahydronaphthalene b
C 4 —alkyl tetrahydronaphthalene b
dimethyltetrahydronaphthalene d
Other Hydrocarbons
C 3
propene (tent.) b
C 4
1—butene e,a,f,c,b,d
2—butene a,b,c
n—butane a,f,c,d
C 4 H 10 isomer C
C 5
n—pentane a,f,b,d
cyclopentene a
pentyne b
CH isomer c
D 10
29
-------
Table 4. ORGA1’ ICS FOUND IN AUTOMOBILE INTERIORS (con.)
Compounds Notes
Other Hydrocarbons (con.)
C 6
C 6 H 10 isomers e,a,b,d
methylpentene a
C 7
C 7 H 12 b
methyl hexyne g
methyl cyclohexene isomers a
C 8
C 8 1 1 16 isomers e,f,b,d
ethylcyclohexane a
trimethylpentane isomer a
C 8114 isomers a,b
C 9
C 9 H 16 isomers e,f,c,b,d
C 9 H 18 isomers e,f,c,b,d
trimethylcyclohexane e
2, 3—dimethyiheptane e
propylcyclohexane e , f ,b
Cl 0
C 10 H 22 isomers e,a,b
isomers e,f,c,b
C 10 H 6 isomers e,f,b
butylcyclohexane e,f,b,d
terpinene isomers e,a,f,c,b,d
C H isomer a
10 12
C H isomers e,f
10 20
30
-------
Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.)
Compounds Notes
Other Hydrocarbons (con.)
Cli
C 11 H 22 isomers e,a,f,c,b,d
C 11 11 70 isomers a,f,c,b,d
pentylcyclohexane e , f
Cl 2
C 12 H 6 isomers e,f,c,b,d
C 12 H 24 isomers e,f,c,b,d
n—dodecane e,f
triisobutylene f
C 12 H 16 isomers c
C 12 H 22 isomers b,d
C 12 H 18 isomer b
hexyicyclohexane e
Cl 3
C 13 H 28 isomers e,f,c,b,d
C 3 H 26 isomers e,a,f,c,b,d
2—methyidodecane e
3—methyldodecane e
3—methyldodecane e
n—tridecane e
C 13 H 24 isomers c,b,d
dodecahydrofluorene (tent.) d
Cl 4
C ,H isomers e,c,b,d
l + 30
C H isomers e,c,b,d
14 28
CE isomers c,b
31
-------
Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.)
Compounds
Other Hydrocarbons (con.)
C
14 (con.)
C H isomers
14 24
C 14 H 22 isomers
Cl 5
C 15 H 32 isomers
C 15 H 30 isomers
C 15 H 28 isomers
C 15 H 26 isomers
C 15 11 24 isomers
C 15 H 22 isomers
Cl 6
C 16 H 34 isomers c,b,d
C 16 H 32 isomers c,b,d
C 16 H 28 isomers b
C 16 H 30 isomers b
C 17
C 17 H 36 isomers
Notes
c
C
c,b,d
d,c,b
c,b
C
c ,b
b
Notes:
b,c
a = Compound
found
in
1976
Datsun
—
9/24/76
b Compound
found
in
1976
Gremlin
—
7/30/76
c = Compound
found
in
1976
Pinto
—
7/29/76
d = Compound
found
in
1976
Vega
—
8/5/76
e = Compound
found
in
1976
Rabbit
—
9/22/76
f = Compound
found
in
1976
Chevette
—
9/13/76
g = Compound
found
in
1976
Chevette
—
7/28/76
32
-------
In the test procedure the automobiles were ventilated to outside air,
closed up in the normal manner and the interior temperature thermostated at
65°C. After 3 hours, samples of the interior air were collected on Tenax
cartridges and analyzed by GC/MS.
Some identifications are reported as tentative. This usually means
that the sample spectrum fits the reference compendium data for that identifi-
cation, but is equivocal due to the presence of background, other unresolved
components or an insufficient amount of the component.
Empirical formulae are reported for many hydrocarbons with occasional
further designation of branched or normal. The hydrocarbons reported as
empirical formulae could be expanded only in a few instances to indicate
that they were branched (the normal isomers appeared in the background).
Structural elucidation beyond this point is complicated by two factors: (1)
hydrocarbon isomers having the same empirical formula result in the same
array of in/e values with relative intensities being the only distinguishing
feature; and (2) compendia of mass spectra do not list all isomers, especially
as the molecular weight and number of isomers increase. This situation is
further complicated by incomplete chromatographic separation of hydrocarbons
and several hydrocarbons giving rise to the same ions. Such overlap can
seriously affect the relative intensities and can make this an unreliable
parameter for structural identification. Greater mass spectral resolution
does nothing to solve this problem since the ttinterferent? gives rise to the
same ion(s).
Quantitatation of the organics was not included in the scope of work.
Although information on specific compounds may be retrieved for the Datsun,
Rabbit and Chevette, this would be a project in itself. However, comparing
the number and size of peaks in the Datsun chromatogram with the perfluoro-
benzene external standard, shows the total concentration of organics to be
about 1-10 pg/. . The other automobiles were not sufficiently different for
this type of estimate not to apply to them. On the other end of the scale,
approximately 1 ng/2 . or more would have to be present for an identification
to be made.
33
-------
A frequency prioritized list of the same compounds is included in
Appendix C to facilitate inspection of the most commonly found compounds.
34
-------
REFERENCE S
1. J. V. Pustinger, F. N. Hodgson, and W. B. Ross. Identification of
Volatile Contaminants of Space Cabin Materials. Aerospace Medical
Research Laboratory, Wright-Patterson Air Force Base, Dayton, Ohio
AMRL-TR-66-53. 1966.
2. J. V. Pustinger and F. N. Hodgson. Identification of Volatile Conta-
minants of Space Cabin Materials. Aerospace Medical Research Labora-
tory, Wright-Patterson Air Force Base, Dayton, Ohio. AMRL-TR-67-58.
1967.
3. J. V. Pustinger and F. N. Hodgson. Identification of Volatile Contami-
nants of Space Cabin Materials. Aerospace Medical Research Laboratory,
Wright-Patterson Air Force Base, Dayton, Ohio. AMRL-TR-68-27. 1968.
4. J. V. Pustinger, F. N. Hodgson, and J. E. Strobel. Identification of
Volatile Contaminants of Space Cabin Materials. Aerospace Medical
Research Laboratory, Wright-Patterson Air Force Base, Dayton, Ohio.
ANRL-TR-69-l8. 1969.
5. J. V. Pustinger, F. N. Hodgson, J. E. Strobel, and R. L. Evers. Identi-
fication of Volatile Contaminants of Space Cabin Materials. Aerospace
Medical Research Laboratory, Wright-Patterson Air Force Base, Dayton,
Ohio. ANRL-TR-69-71. 1969.
6. International Agency for Research on Cancer, Monograph 7, 291 (1974).
7. I. J. Selikoff and E. C. Hammond. “Toxicity of Vinyl Chloride - Poly-
vinyl Chloride,” Ann. N. Y. Acad. Sci., 246, 1 (1975).
8. Federal Register, Vol. 42, p. 28154, 1977.
9. Registry of Toxic Effects of Chemical Substances , 1976 Edition.
10. C. L. Duel. Collection and Measurement of Atmospheric Trace Contami-
nants. Aerojet Electrosystems Co. , Azusa, CA. Final Report Cont.
NAS 1-8714, NASA Doc. No. 71-19636.
35
-------
11. E. D. Pellizzari. Development of Method for Carcinogenic Vapor
Analysis in Ambient Atmospheres. Research Triangle Institute
Reports prepared for Office of Research and Development, U.S.
Environmental Protection Agency, EPA-650/2-74-121, (NTIS No. PB
239770), Contract No. 68-02-1128, 162 pp., July 1974, and EPA-
600/2-75-076 (NTIS No. PB 250620), Contract No. 68-02-1128, 199
pp., November 1975, EPA 600/7-77-055 (NTIS No. PB 269582) Contract
No. 68-02-1128, 228 p. June 1977.
12. Eight Peak Index of Mass Spectra. Vol. I (Tables 1 and 2) and II
(Table 3), Mass Spectrometry Data Centre, AWRE, Aldermaston, Reading,
RG74PR, 13K, 1970.
36
-------
APPENDIX A
SA\NPLING PROCEDURE
37
-------
APPENDIX A
SANPLING PROCEDURE
Two design criteria were essential to the sampling of the interior
of each automobile. One was to be able to withdraw an air sample from
the compartment without adversely affecting the breakthrough volume of
the sorbent used in sampling. The other was to control the temperature
of the compartment. The experimental arrangement which was used to meet
these requirements is discussed below.
SANPLING PORT
A Plexiglas panel was designed to enable the sampling cartridges
to be inserted into the automobile window. A grooved edge on the panel
allowed it to fit snugly over the window glass, with the upper edge
inserted into the groove normally accepting the window glass. The areas
not covered by this panel were sealed using heavy weight aluminum foil
supported with cardboard. The foil extended beyond the opening to cm
and was pressed to conform to the window contours. This covering was
held in place with duct tape applied at intervals along the perimeter.
(see Figure A-l). Two ports were drilled in the panel: one 16 mm in
diameter for the Tenax cartridge; the other 6 mm in diameter for the
charcoal cartridge. When not in use these were filled with an aluminum
foil plug.
TENPERATURE CONTROLS
The temperature of the automobile interior was positvely controlled
using the arrangement shown schematically in Figure A-2. The temperature
38
-------
TEN AX
TO SPACE
H EATER
AIR TEMP.
P ROBE
PORT
CHARCOAL
CARTRIDGE
OPEN AREA COVERED
WITH FOIL
Fic ure A—i. Side window on driver’s side.
-------
0
THERMOMETER
CHARCOAL
OR TENAX
FRONT
SEAT
FRONT
SEAT
TEMP
CONTROLLER
0
THERM CM E T ER
Figure A—.. Au:c’ bi1e ericr e-. era: re c ::r .
-------
monitored at two points in the front and back of the compartment was
found to be constant within ±2°C. The desired temperature was maintained
for 3 hours before initiating the sample collection. The 200 to 500 ml
samples collected on SKC charcoal were collected at 50 ml/min for 4 and
10 minutes, respectively. The Tenax GC samples were collected at 100-
300 mi/mm for 1 to 2 hours. Samples were collected using either a
DuPont constant-flow personnel sampler (Pinto, Gremlin, Vega, and Chevette
[ 1st sequence]) or an SKC personnel sampler (Chevette [ 2nd sequencel,
Datsun and Rabbit). Air was pulled through a cartridge which protruded
just inside the car when placed in the Plexiglas sampling port (see
Figure A-i). The cartridge was attached to the sampler by a short
rubber tube. The charcoal cartridge consisted of 150 mg of SKC Lot 104
charcoal packed between two 1 cm glass wool plugs inside a glass tube 6
mm o.d. The Tenax cartridge consisted of an 8 cm length of Tenax GC
packed between two 1 cm glass wool plugs inside a glass tube 16 mm o.d.
All cartridge samples were sealed in culture tubes and stored at or
below —5°C until analyzed.
The sampling arrangement used here minimized the effect of the
elevated temperature of the automobile interior on the cartridge tempera-
ture and consequently maintained the breakthrough volume. Since the
cartridges were outside the car, they remained at ambient temperature
until sampling was initiated. The low flow rates used for sampling
minimized the temperature rise due to the temperature of the air sampled.
41
-------
42
-------
APPENDIX B
GAS LIQUID CHROMATOGRAPHY - MASS SPECTROMETRY
ANALYSIS OF ORGANICS IN AUTOMOBILE INTERIORS
43
-------
5 10 15 20
Ttine (mm)
Figure B—i. Total ion current plot during gas liquid chromatography/mass spectrometry ol air
sample from tiLe interior of a Vega (8/26/76) autoi .obile. A 100 m OV—101 SCU I7
Cal) ii thry column was te;c’1. See text for conditions. Sample volume 31.6 2.
(con.)
I
0
Is
10
:3,
25
30
-------
105
I
TenlperLltLlre (SC)
1 iru (ritn’
200
45
II
140
1
30
It lo 181)
35 40
220 240
50
55
Fi tire B—i. (con.)
-------
Ime (mlii)
Figure B—i. (con.)
-------
2 30
3 57
4 62
5 43
6 66
7 66
5 70
9 74
10 31
11 83
12 34
15 36
13 83
15 90
46 94
17 97
13 98
19 132
20 104
21 111
22 112
23 114
24 119
25 420
26 122
27 121
28 126
29 123
30 129
31 130
32 134
33 135
34 136
35 137
36 133
37 129
38 141
39 142
40 144
41 145
42 146
43 lb
41 147
45 147
46 143
Table B—i. ORGANIC CO OTJNDS IDENTIFIED FROM FIGURE B-i.
.7
- .3
49
30
51
45
53
34
43
55
57
53
59
60
61
62
63
64
03
00
67
68
69
70
71
73
74
75
76
77
78
79
30
SI
32
S3
34
85
36
37
83
39
90
91
150 C 9 -L 3 Ls.4oer
151 C.H, 0 Iscoer
153 anlsole
134 C H 13 Isor
155 C 0 H, Isorner
155 C_—be4zene
135 C 13 H, 0 iscrer
157 C H. 3 1so er
137 C 9 H, 5 lsc er
153 C 1 _ _ Iscrer
153 C H, 8 isooer
139 C. 3 H, 0 iscrer
150 ? ° °
161 C , H_ 3 iso er
161 C, 0 H 0 iso er
162 4—propy1be zane
162 c, 0 :-i 15 Isc er
162 C,H, . 4 scoer
1ó2 C 10 3_., Isomer
163 phenol
163 C 3 —Senzene
164 C, 0 H,, Isomer
155 C 10 H 20 isomer
166 methyl styrena
157 C, - H., Isoner
i_i ——
168 chiorostyrene (tent.)
163 C , 3 H 25 isomer
163 c 10 H 1 . isomer (tent.)
170 C 3 —ben:ene
171 C 10 H 2 , isomer
171 C 10 H 20 isomer
172 C 10 H 20 Isomer
173 dichlorobenzene (tent.)
173 C,—bem eoe
175 C 11 H, 2 isomer
175 C 11 H 2 , isomer
175 t—butthanol
175 C—Senzene
176 C—ben ene
.4
176 C ,H.,. iSOmer
177 C 4 -b nzene
178 terptosne
173
179 dipropy1ben ene
179 C 11 H,, Isomer
130 C,—5enze e
l ie a l i e ovde
Chromato-
Elution
Chromato-
Elution
graphic
Peak No.
Temp. Compound graphic
(°C) i Peak No.
Temp. Compound
(°C)
butene
C,H. Isomer
40
ISomer
4
C H., isomer
3.-—
C 7 H, 1 isomer
vinyl re:hvl ether (tent.)
methyl b.iryl etr er
C 6 . isomer
C.H Isomer
o 1..
CHC I 3
CH. isomer
0
isomer
o 1.-
CH ISczer
0
1.1.1—tc 1orcechane
benz s .s
C..H. - isomer
C_H,. icmer
C 7 H 14 Isomer
C_H, - isomer
5.0
C 7 H 1 , isomer
CH ,_i o mer
‘- - .3
C H - isomer
8 lo
to1 ene
C 3 H, 3 isomer
C H - isomer
S is
C H, Iscoer
3 5._S
C 3 H 13 Isomer
C H. - Isomer
35.4
C 3 H 5 Isomer
tetrach loroe thy lene
hexa:hy1cycbo:r5.s 1Ox3r1e (3KG)
C 9 H, 0 Isomer
C_H. - Isomer
S
C 9 H 13 Isomer
C 9 H 13 Isomer
d ihy ropyr3ri
e t by 15 en zeOe
n/p — xv lens
C 9 FL 0 Iscrer
C_H isomer
3
C H. isomer
9 43
C 9 H 16 isomer
Sryrene
C 9 H, 3 (cy 1ooctste seme (tent.)
0X) IlC4 5
47
-------
Table B—i. (con.)
Chromato-
Elution
Chromato-
Elution
graphic
Peak No.
Temp. Compound graphic
(°C) Peak No.
Temp. Compound
(°C)
93 130 C 11 H 1so er 1.33 211 C 13 H , isa er
94 132 C 11 ,, iao er 139 311 C 13 H, 6 isoner
95 133 C, 1 3.. Isoner 140 211 C 13 R, 3 tso er
96 133 C 1 2 E, 5 isoner 141 211 C—beozene
97 133 C,— eozene 142 212 C H, isomer
4 13 6
98 184 C 1 .,H,. is3mer 143 214 dthethy1tetrahydronaphc a1e e
99 136 Isoprcpyi nechvi phenyl 144 215 C 6 -benzem
chl3ride (rent.) 145 216 benzothiazo le
100 186 dj eth3xvbenzene 146 217 C 13 H, 6 iso ier
101 133 di ethv1styrene 147 218 C 6 H 11 beflZefle
102 188 C 1 H, 3 isomer 148 218 C 7 —benzerie
103 138 C ,IL, tso er 149 219 C •H, Isomer
104 138 C IL, isomer 150 219 C,, H lscoer
11 .. i. 30
105 190 C 11 3. isomer (branched) 151 220 C 13 H 26 isomer
106 192 C 5 —benzene 152 221 C 14 H 30 isomer
107 192 C 11 1L,, isomer 153 221 C 7 —be zerme
108 193 C 12 H.,, iso er 134 221 C 13 H, 5 isoer
109 193 C—ben:ene 155 221 dinethylirmdan
110 194 C 1 ,3 , isomer 156 223 undecermol (cenr.)
111 194 C 12 H ,. iscoer 157 224 C 13 H.. 3 Isorner
112 195 C 5 — en:ene 158 225 C 14 8 3 isomer
113 196 C 1 H, isomer 159 227 i—naphtha1ene
114 197 C.— snzene 160 228 C ,H, isomer
) 14 3
115 197 C 12 3, Isomer 161 229 C 15 H 30 Isomer
116 199 C 5 H 9 — enze e 162 229 C 7 —benzene
117 199 penrachlocoacerone (tent.) 163 230 3—mechylnapathalene
118 200 C 12 3,, isomer 164 230 dicechyltecrahydronaphchalene
119 200 C E .. isomer 165 230 C —be zene
12g. 7
120 200 C 12 L. 6 isomer 166 232 dlnethvlcecrahydronaphchalene
121 201 C 5 —b nzene 167 232 C 3 —benzene
122 202 C 13 H 26 Isomer 168 233 C 14 H 23 isomer
123 202 C 12 8,, isomer 169 234 C 15 H 0 Isomer
124 202 C 12 8, 6 isomer 170 234 C 7 —benzene
125 202 C 12 11, 4 isomer 171 234 C 14 H .. 5 isomer
126 203 C 12 3. , 6 isomer 172 234 C 1 H, 5 Isomer
127 204 C 13 H., 8 isomer 173 236 C 16 H 3 ., isomer
123 206 C 12 L, 4 isomer 174 239 C 15 H 32 isomer
129 206 trichlorobenzene 175 238 C 15 H 30 Isomer
130 206 C 6 —benze m e 176 238 C 16 M 34 isomer
131 207 methyltetrahydronaphthalene 177 239 C 14 H 30 isomer
132 208 C 12 H., 6 Isomer 178 239 C 15 H 30 Isomer
133 208 naphthalene 179 240 octamethyltrisiloxine
134 208 isomer 180 a C 15 H, 0 Isomer
135 209 C 6 —benzene 181 a’ dime yltsaphcha1.emte
136 210 C 13 11, 6 isomer 182 a C 16 H 34 isomer
137 210 nethyltetrahydronaphtha lene 183 di eChY1phCha1ate
48
-------
Table B—i. (con.)
Chromato. Elution
graphic Temp. Compound
Peak No. (°C)
Chromato- EltitioTi
graphic Temp. Con pound
Peak No. (°C)
a iyLn p cna1 191 a Cg—t 1 2hefle (:e t.)
195 a - - isc er 192 a octa yLtri1 a e
a dethvlqutholi 193 a dtphe v1et er ( e t.)
157 a UEtk OWLi 194 a icog ch. in pr y1 ke one
153 a C,.H, 1so er 195 a phenvi colyl ether
139 a isomer 196 a butyLa inodipheny1a ine (tent.)
190 a di—t—butylcresol
a Isother .i i
49
-------
I I
U i
0
A
UN)0U
II
-- r .-T----———— 1 1
2) 40 60 80 100 120 140
T eapt.rmture_(‘ç)
__- --
4) 5 20
10 15
25
160 180
30
204)
40
220
Time (.lii)
I I uri ’ I —2. Toi a I Ion ‘IIrrrnL 1)14)1 (IL IrI ng gas I Iqu Id ( ‘hronlolography/rnass spe( 1romct ry
of a I r sample from tIi(’ I Ut or I or of a I)at.sun (10/10/76) auloinob I Ic. A
100 in OV— 101 SCOT rai I I I a ry ( O Itirnil was usc(I . See t OX t for (‘011(1 I I 10115
Samp I V vol (1100 1 8. 3 . —
-------
Table B—2. ORGANIC CO ’tPOI.TNDS IDENTIFIED FROM FIGURE B—2.
03 ,
1—but ene
n—butane
2 —bu ten e
CH Isomer
10
L ao
tri1orofh orethane
C..H, 0 isomer
n—pen tone
C.H. isomer
)
aetone
propeme nitrlle
113 - CS,
ter—butonoj
cvc!opentene
C 6 H,. Isomer
2— e ry 17 ant ane
C H. isomer
6 jO
ber.zene
cyclohexa ne
2—metbyihexane
2, 3—d methv1pentane
3—thv lhe ,cacie
dImethv1 yc1opencar.e isomer
trit y1pentana isomar
C 7 H,, isomer
C 7 H, 2 isooer
n—heptane
C 7 H 1 , isomer
C 7 H 1 , isomer
methy1cy lohexene isomer
methyloyc lchex o ne
C 5 H , 5 Isomer
isomer
22A 31.
23 82
231 82
24 33
24 83
25 84
251 87
26 87-
27 83
28 89
29 90
291 91
30 92
301 92
31. 93
31A 94
32 95
33 97
34 93
35 98
36 100
361 101
37 102
371 103
38 104
39 106
391 108
40 111
401 113
41 114
411 117
42 117
421 117
43 119
431 120
44 121
441 121
45 122
46 123
47 125
43 126
431 126
49 127
50 1.23
51 1)0
52 1)2
C 5 H 13 isomer
trimetytoycinpen aoe isomer
Isomer
C H, isomer
S
trlmethylpencone isomer
toluene
2,5—d i chyihex one
2, 3—dithv lhexa ne
3—mechyiheptame
C H, Isomer
1.
C 9 H, 0 isomer
1,2—dibromoechame (teat.)
C 3 H 15 isomer
C 3 H 1 , isomer
n—ccta ne
C 3 H 16 Isomer
C_H,, isomer
P
C 9 H 20 Isom,r
silane c mtound (1Y C)
C 9 H_ 0 Isomer
ethv lcyc lohexaae
C H..,., isomer
9 u
C 9 H 13 isomer
C Si. - isomer
9 .5
athv1ben ene
‘.1ene
C 9 H, 0 soc er
o —xy1 ne
C 9 H 13 isomer
000ane
C 9 H, 3 isomer
isopropylbenrene
C 10 H 72 isomer
C 10 H 22 isomer
C 10 H.. 0 isomer
cerpineae isomer
C 1 QH, 2 isoi er
rt—p rop y lb ens ene
—echyl t oluene
1, 3,5—crimethylbeasene
0 10 H,_ Isomer
phenol (tent.)
0e thy It ol ueae
C 13 H 20 isomer
1,2, 4 —tr1methylb’ z e n s
n—de cane
Chromato- Elution
graphic Temp. Compound
Peak No. (°C)
Chromato- Elution
graphic Temp. Compound
Peak No. (°C)
(teOt.) ÷ fteon
1 39
2 41
Lk 41
3 42
4 42
A 44
5 45
6 46
7 46
8 47
9 43
10 50
101 50
103 52
100 52
100 5)
11 54
12 56
121 57
13 58
131 59
133 59
132 60
13 61
14 61
141 62
148 63
14C 65
15 65
151 67
16 68
17 69
171 70
18 71
I Sa. 72
1,33 73
1.3C 73
19 74
191 75
20 76
201 76
2 1 78
2L A 79
22 50
3—me t hvlpan:ane
C 6 H 15 .SOOCE
— hexafluorobeazene (e )
C H. - I scmer
7 .0
C H,., isomer
6
C.H, Isomer
0
me th’. lpentene
meyi cyclcpea:nne
perfluorotoluene + C 7 H 1 S
isomer (ei)
1,2—dichioroethane
51
-------
Table B—2. (con.)
Chromal
graphic
Peak No.
0 ElUtiOn
Temp.
(°C)
Compound
Chxomato- Elution
graphic Temp.
Peak No. (°C)
Compound
5A
323
53
1)3
133
135
C, , 0 1so er
C.—aL y1 e1ze isc er
-
,3—tri ethy1benzen
606
SOC
61
1 3
149
150
c 11 ,, isomr
C,—aL yL eaze ’.e is r
4
n—undecarie
53A
135
C -a1 y1 berizene i3o er
62
152
C.— 1ky1 benze e i cer
53
53
55A
553
56
57
33
136
137
133
139
140
131
133
C 11 .. isocer
ethv1styrene + C 11 H 2 , isocers
C 10 L 0 isomer
C 3 —alkyi benzene isonet
k 7ropy1co1ueae
n—bucylbenzene + propyltoluene
o—propyltoluene
63
6i .
633
63C
63D
63E
153
153
156
156.
153
159
C,— 1ky1 benzene so er
C11}423 isoner
C 10 , isoner
C 5 —slkyl benzene isouer
C 10 12 soner
di ethy1pheno1 + C,—alkyl
benzeoe tsoer
SSA
59
60
133
135
136
C 11 L, isoner
di ethy1 ethylbenzene isoner
dtethylstyrene or C 10 9, 0
isoner
63F
63C
63R
64
159
161
166
167
C 5 —alkyl beozene isorner
C 12 l 2 , Lscer
C 12 .,, isoner
— ooecsne
60A
137
C—slkyl benzeie isoner
64A
173
C 13 b, 6 isocer
52
-------
i ’ i ’ jI
It,oI,
;I .
_
40 It) 8)) I 00 I .0 14)) 160 180
1t iper.Itur& ( C )
— -- F —i - i—
S II) [ 5 20 5 3(1 3 5 4’)
I I int (In)
i gti r R—
rot a I luti (‘urrent p ot dun ng gas Ii quid (hromutogra )hy/mass sI)eeLI owe Lry oi
air ;ninp It from the I nt.er br t ;i Chevette (10/10/7() automohi it. A tOo in
OV— 101 SCOt’ cap ii I ary col own was tise(1 . Se. text k)r cond it i oils. a1U )1 e
V( 101111. I. ‘3. ‘3
UI
C .,
-------
Table B—3. ORGANIC COMPOUNDS IDENTIFIED FROM FIGURE B—3.
Chromato- Elution Chromato- Elutjon
graphic Temp. Compound graphic Temp. Compound
Peak No. (°C) Peak No. (°C)
2 .‘3 CO, CF..C1, 17C 91 C H 16 iao er
3 !.3 1 Sucar a 170 92 dL etht1cy1ohaxane isorner
It .3 cat .aj &wde 13 93 r —haxa aj
33 4 n— ur ne 13A 94 C H 1 is er
3 37 tso e :a e 183 95 C H. isorner
S 1.6
!.A 47 tri1orof1ur eth.ane 19 95 n—octane
43 43 1—pencane 19A 96 C_H, 6 isoner
4C 46 2—per.tene + fursa 20 100 hexanethylcyclotrisioxane (3KG)
5 49 n—oenra e 201 102 C H lso er
— 9 in
51 49 pro 3na2. + c 5 a,, 3 tso er 203 103 ethyicyclohexane
53 50 pro a a1 2CC 103 C 9 H, 3 + C 9 H, 3 isocers
SC 30 dich.orcaethane + C_L 0 lso er 21 105 2—hepta one
6 51 acetone 22 106 ethylbenzene
61 51 freon 113 (3KG) 221 107 C R. tsoaer
9 1.8
63 53 dinerhv l ether (tent.) 23 103 — c’:1ene
SC 54 ter—b ,tano1 24 109 C 9 H, 0 isoner
7 35 2—nenhyl7encaae 25 110 C 9 H 0 isoner
71 56 crotcnaidehvde 251 111 C H 15 _soner
73 57 3—net i9entane 26 111 styrene
7C 57 C.H. - isoner 261 112 C H iscner
916
70 53 2—neth ’1prooanaj 263 112 o—xylane + C 9 H 15 isoner
9 . 59 he caf1uorobe:izeae (er) 27 113 a he?ta1dehvde
9 59 n— ne 271 114 C 9 H 13 isoner
91 63 ch1orofor 28 115 n—noaarie
53 61 aerh,1 ethyl katone 29 117 C 9 H 18 isocer
10 54 erf1uoroto1uene (er) 291 118 iso ropy1ben:etie
101 65 ethylcyclopencane 30 119 C 10 H,, Isoner
103 66 ethyl acetate (teat.) 30A 121 propvicyclohexane
11 67 n— utana1 31 122 tar9inene 1soc er
12 69 benzer.e 32 123 benz 1 ehyd
121 69 carbon tetrachiotide 321 124 n—proo-,lbenzeae
123 70 cyclonaxace 33 125 —athy1to1u ne
12C 71 1—butanol (cant.) 34 127 n—echyltoluene + C 10 H ..., isoner
13 72 2— ethy1hexane 341 127 C 10 H_ 3 isoner
14 73 3—butar.aj 35 3.28 C H,, jsoner
11 ....
15 76 n—heptaae 36 129 o—ethyltoluene + C 10 H,, Isoner
151 78 C 8 H 1 . isomer 361 130 C 10 H 16 isoner
16 79 2—aethyl—l—butanol (tent.) 37 131 occanone (ter.t.) + C 10 H. , 0
161 30 nethvlcyclohexane isoners
153 32 C 3 B, 3 isoner 38 132 1,2,4—crinechylbeazene + C 10 H 20
1SC 53 4—oe chyl—2—pentanoae isorers
160 84 hexanal isoner 381 133 C 10 H, 0 isoner
liE 86 2,3—dlnechylhexane 39 133 n—decane
17 87 toluane 391 135 C 13 H_ 0 isoner
171 99 2, 4 —dtnethv lhexana 40 136 triisobutvleae
173 50 3—nec.’ ylhept ae 301 137 1,2, 3—trinethylbeozene
54
-------
Table B—3. (con.)
Chromato-
graphic
Peak No.
Elution
Temp.
(°C)
Compound
Chxomato-
graphic
Peak No.
Elution
Temp.
(°C)
Compound
303
137
—a1ky1 bei sn iaooe
513
154
C ,H,, isomer
31
133
C,,H,, isomer
4
52
155
C , H ,, isomer
—
42
139
C. H,, isomer
-
521
155
C,. H, isomer
-
..21
140
butyloyclohemar.e C. 1 H ,,
isomer
53
531
157
158
C, ,H, 5 isomer
C_—alkvl enzetie
43
141
C H,, isomer
11
54
159
Dentv1c- c1ohexane
.
34
142
C 12 H 26 isomer
541
160
C 1 ,H, :scmer
4 .A
142
C 1 H ,, isomer
55
151
C,—alkyl benzene
443
45
143
143
C.—alkvl benzene + C 11 H,,
isomers
acetop’nenone
53
55A
37
151
162
163
dimeth -,lphanol
C 17 H, 6 isomer
ethyl?nenol C—alkyl
5e zane
431
144
C 1 ,H 22 isomer
isomer
46
145
C H isomer
11 24
58
164
C. H, isomer
37
38
39
147
148
149
C,—alks -1 benrene 0,_H, 6
isomers
C, —a1 v1 benzene isomer
C, 3 H_ 5 isomer
59
60
61
62
165
167
169
171
C _H , isomer
C ,E,., isomer
n—dodeoarie
C 13 H, 3 4somer
50
150
C H., isomer
621
172
C 13 H 26 isomer
501
151
C 51 8 22 isomer
628
174
C, 3 H_ 5 isomer
303
131
0 11 H,, isomer
62C
175
0 12 H,, isomer
51
152
n—undecane
5L1
153
C. —a lkvl bemzeue isomer
.4
55
-------
idkX)
I I I
I i i
• )t)IUI
.)UU()
I l l
I n f l
I ;
I 2 11 1111 ,i 0
lO l IC) a I
— i\ .Ii !. , . i , , ,..IIlI )l ,ll1 l
,— —- n I
/ i’— ...j ! I I
41 — t o i ; — ioi 1 I 0 1 1 1 0 ç - . ‘J?O
‘Lempera r ure (°c)
F — I — I ——---i -- - “T -- l
5 1(1 15 .0 25 10 1’) ‘*0 45 So
Time (m m)
V igtire R---4 . ‘lot at ion turr*nI pini (ltlri tig ga -; I 1(1(11(1 Fl lro lllatTography/lIlass sln’rtromet ry of air
5 1119) 1 1 root t Ito mt t I or oF a Cltt’ve t to (8/25/76) an totoob lit’ . A 100 in OV— 101
SUYI’ (it I 1 lttry column was IIS&’tI . So c 1 0 )01 lot- cOhidi I tolls. Saitiple vol time 6.42 2..
No It ’: a = In to r I cr011 10 dtte to watt,t’
U I
0 ’
-------
Table B—4. ORGANIC COMPOUNDS IDENTIFIED FROM FIGURE B—4.
Chromato- Elutjon
graphic Temp. Compound
Pealc No. (°C)
Chromato-Elution
graphic Temp. Compound
Peak No. (°C
1 133 3.3—di ey1’,35u car o— 41 19 C,—benzene
tu:rt le 32 196 C 11 H_, iso er
2 113 43 193 C 5 —ber ze e
3 123 t 1uerta 44 199 d echy1 tyrene
4 133 exa: y1cyc1otris oxane (ter.t.) 75 199 3 3 —benzer,e
5 337 C H, 6 isoer 46 201 C 12 H,, 1ao er
6 140 a1kv1 ced cyclohexane 47 201 C 1 ,H isomer
7 143 C 2 —beozeoe 43 202 dimethyistyrene
8 149 cyc1coctetrae e (or s tvrenC) 49 202 C 5 —beizerte
9 150 C,—beozene 50 204 C 12 L 6 tsomer
10 151 C H_ :somer 51 204 C..—benzene
11 153 maleio anhy ride ) 52 206 C 12 H, 4 aomer
12 155 53 206 3 11 a 22 5Ooer
13 161 C H, isomer 54 207 C — enzeoe
9 .3 6
14 164 C 3 —beoreoe 55 203 C 12 H 26 isorer
15 165 6 n:s1 ehyde 56 208 aphtha1eoe
16 163 aoi1i e 57 209 C_—be ze e
17 168 2—ami o—2—methy1—1—?ropar.o1 53 211 C, 3 H 23 isomer
18 170 C 3 —bemzene 59 212 C 6 —ber.zene
19 171 C, 1soer 60 213 C—ben:ete
20 177 C,—6etzene 61 216 beozothiazole [ C 7 HNS]
21 178 C H,. isomer 62 217 C H, isor er
1 _3
22 179 C 6 H,, isorner 63 219 C 6 —benzene
23 181 C. isomer 64 221 C_—indoline
24 382 C, 0 H 22 isomer 65 225 C 13 H, 5 isomer
25 132 C — s e 66 225 C_—6eaze e
26 183 C, 0 H 22 isomer 67 226 C 6 —benze e
27 133 cresol 63 227 C 7 —beozeoe
28 183 C, 1 , 2 Isomer 69 228 S—methyi aphtha1ene
29 185 C,—bemzene 0 230 a—roethy1nazhthaie e
30 187 C 4 —ber.zene 71 232 di—r—bury1phenso rhy1e e (tent.)
31 187 C 10 H_ 3 isomer 72 233 C_—benzene
32 183 C 11 H, 2 isomer 73 234 C 13 H, 6 isomer
33 190 C 11 H_, isomer 74 235 C 7 —benzene
34 190 C 11 H isomer 75 236 d phe oxyber.zece
35 190 C 11 H. 0 isomer 76 240 biphenyl
36 191 C 11 H: 9 isoner 77 a octamethyltrisiloxane
37 192 C 5 —benzené 78 a C 11 H 2 , isomer
38 194 C,,H.,, Isomer 79 a dfrerhylnaphthaiene
39 194 isomer 80 a ?—phrhalote
40 193 C—benzene 31 a Imethy1oaphthalC 1e
a — Isothermal
-------
I i.gure B—s.
40
5
18
‘lemperature (°C)
60 8()
10 15
Time (mm)
ion current p tot do r i tig gas .1 Iquid di roinn tOgra )hy /I11aSS Spe(’ tro—
of a I r samp I from the inter i or of a Pinto (8/28/76) atitomobi I
in OV—101 SCOT capil 1 ry column was used. See text for condiLioi, ;.
lOt ill.
met ry
A 100
Satup I (‘ vol tifliC 32 Q
U’
15
5 10
I 20
III
U
25
30
1 00
(con.)
-------
12fl 1 0
25
70 00
II I I
20
“g il
tji
e (I
Ii
Teni cr ittire ( (:)
160
35
160
lime (,!ii)
200
1 .0
65
Figure B—5. (con.)
-------
Tempetiture ( C)
260
55
Time (miu )
-
0
0
I I
II I
II
220
Figure B—5. (con.)
-------
Table B—5. ORGANIC COMPOUNDS IDENTIFIED FROM FIGURE B—5.
Chromato- Elution
aphic Temp. Compound
Peak No. ( 0 C)
Chromato- Elution
graphic Temp. Compound
peak No. (°C)
£ 43 :3, 47 1-.) :c 1 r ( r 5/or
2 47 C,H, :so er 43 114 C H, 3 13o ,r
3 13 C -L c , er .9 14 . Cr-H iso er
3 2 C’ , 3 i o e 50 146 C 3 H 3 isc er
) i$o er 51 147 scyrene or cvcLo oc: e r ra ene
6 53 C_H. 1 tac e: 52 143 o— 1ene
7 59 CH,, isoaer 53 143 C H isoer
3 61 CH.._ iconer 54 149 C H 3 1sc er
9 63 C_H,. i c .er 53 149 C 9 M , 0 isoner
10 64 vinyl et v1 ether (rent.) 56 150 C 9 0 isoner
11 63 CH., tsoner 57 132 H erhy1pyrt51ne (tent.)
12 71 C.H 1 4soner 53 154 et .yL but3 ldehy5 (tent.)
13 7 C_ ,, isoner 59 155 C 9 H 18 scuer
14 73 C.H:, isoner 60 155 C 3 —alkvl bernzen Isoner
15 75 ace:cne 41 156 C H. isoner
9 13
15 73 CH, isorner 62 157 C H. - Isoner
o 9 10
17 73 CH. inner 63 157 C H, isoner
0 .0 9 i 3
15 33 CH isoner 64 133 C H isoer
913
19 82 CH isoner 65 160 0—ninane
23 83 et vl :mnvl e: er 66 161 C 13 H , 0 Isoner
21 84 net vlerne ch1 ride 67 162 C 3 —alkyl herzene isoner
22 53 C_H. jsoer 68 163 benza1deh’ de
23 94 C,H., isoner 69 163 C 3 -alkyl benzene isc er
24 95 bennena 70 163 phenol
25 96 CH., isoer 71 163 C —alkyl bennene isoner
3
26 98 C_it,, isorner 72 167 C 10 H , 3 isoner
27 99 C_H. 6 isoner 73 167 C 3 —alkvl beozene isoner
25 132 C 7 H, i ac er 74 167 oethylstyrene
29 104 C H, isc er 75 167 C H, isorer
716 9 0
30 107 C 7 H ,, t nner 76 167 C 10 H 13 isoner
31 111 cycict exv1a ine (rent.) 77 168 C 10 H , 3 isoner
32 113 C ii. ia oner 73 170 C —alkyl benzene iscoer
33 119 toluene 79 171 C, 0 H 2 , isoner
34 122 C H.. isooer 80 171 C H ., isoner
8 10 2
35 125 C 5 H:, Ssooer 81. 173 C 11 i1 ,, sooer
36 126 C.it, isoner 82 174 C. —alkyl bene
0 10 a
37 126 CsH:, isorner 83 1’S C 1 H 22 isomer
33 123 C 3 H, 3 tsona: 84 175 C 11 H 2 , isomer
39 130 C 3 H 15 Isomer 85 176 C,—alkyl bennoene 1so er
40 132 C 9 H, 3 Isomer 86 176 CUR,, isomer
41 133 C H,. Isomer 87 176 C,—alkyl beozene iscoer
S 10
42 135 C 8 H. 5 Isomer 38 177 C 1 ,H, , Isomer
43 133 C 9 H, 3 Isomer 89 177 C 12 H, 6 tsoc.et
44 139 ethylbennoene 90 178 m—cresyl ethyl ether
45 141 C_H,., isoner 91 173 C 11 H , , Isomer
46 141 C 9 H:, Isomer 92 173 dlchlorobenzene
61
-------
(con.)
Table B—5.
93 173 C.,:-L isomer
-i _6
94 179 C.,d, 6 isomer
95 130 C,—a1 -j1 beozene isomer
4 -
96 130 C,—alkyl benzane isomer
97 130 C H,. isomer
12 _o
98 131 C.—a1 y1 banzene tsomet
99 131 C 11 H,, isomer
100 151 C H,, isomer
11 _..
101 131 C 1 :’d, Isomer
102 132 cresol
103 183 C,—alkyl benzene isomer
104 183 C, H,, isomer
—
105 184 C,,H Isomer
106 185 C,—slkyl benrene isomer
107 185 C 1 ,H,, isomer
108 135 decah ’ drooap ths1eme (tent.)
109 136 C 4 —alkyl benzene isomer
110 137 C 12 H.,, isomer
111 118 C,—alkyl scyrene isomer
112 183 0116,2 isomer
113 188 C ,H, isomer
ii. _0
114 188 C H.,, isomer
12 —.
115 139 C 5 —alkvl benzene isomer
116 189 C 1 .,6 26 isomer
117 191 C H,. isomer
11 ..*
116 191 C 11 6 22 isomer
119 191 C 5 —alkyl benzene isomer
120 191 C 12 8., 4 Isomer
121 191 C 12 6 26 isomer
122 191 C H , isomer
12 24
123 193 C 5 —alkvl benzeme isomer
124 193 C 11 6 22 isomer
125 193 C H , isomer
126 193 0126,6 isomer
127 194 C 4 —alkyl benzeae isomer
128 196 C H , isomer
12 2*
129 196 C 12 H 26 isomer
130 196 C 5 —alkyl beazene isomer
131 197 C 5 —slkyl beozene isomer
132 197 C 1 ,,H.,, isomer
133 198 biphenylefle
134 199 C 5 —alkyl beozene isomer
135 199 C 12 H 24 isomer
136 201 C 2 —alkyl styrene Isomer
137 201 C 11 H_ 2 isomer
133 201 C 5 —alkyl benzene isomer
201 C 12 H, 6 isomer
201 C ,H,, isomer
—*
202 C,—alkvl stvrene Isomer
202 C 5 —alkyl beozene isomer
202 C H,, Isomer
12 .
204 C 5 —alkyi benzene isomer
204 C 2 —alkyl scyrene isomer
205 C 13 3, 6 isomer
206 C 13 6 23 isomer
206 C I3H.,6 Isomer
206 C H.,, isomer
13 *
206 C 1 .,H,, isomer
203 C 5 —alkyl beazene isomer
208 methvitecrahydronaphcha ler.e
208 C 13 H, 6 isomer
208 C 12 %,, isomer
208 C ,H,, isomer
1.,
208 C 12 H, 6 isomer
209 C 12 H., 6 Isomer
210 r aohcha1ene
210 C 5 —alkyl benzer.e isomer
211 mechyltetrahydronaphtha lene
211 C 6 —aikyl beozerie isomer
211 C H , isomer
12 2..
211 C 12 H, 3 isomer
211 C 13 6, 6 isomer
211 C 11 6 1 , (dimethyldihvdro im4ene
or ethyltetrahvdron . .phthaleme
212 C 13 6 2 . isomer
212 C 13 3, 3 isomer
212 C 6 —alkyl beozene isomer
213 C 13 H 28 isomer
214 C 6 —alkyl benzene isomer
214 C 13 H, 6 isomer
14 C 13 6 28 Isomer
214 0133,6 isomer
215 C 13 3., 4 isomer
215 C 11 6 14 isomer
216 C 13 H., 6 isomer
216 trimechylphenOxysilane (SKC)
214 benzothiazOle
217
217
218
218
219
C 13 3., 6 isomer
C 6 —alkyl bensene isomer
C 13 3, 3 isomer
C 7 —alkyl benrene isomer
C 11 H 14 isomer
Chromato- Elution
graphic Temp. Compound
Peak No. (°C)
Chromato- Elution
Temp. Compound
Peak No. (°C)
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
62
-------
Table B—5. (con.)
C i somer
- 5
p.en.i;yri. jne (tent.)
isomer
C - H. isor er
1 . 3
C..—sLkyl ben ene iso ser
C,.H . 3
trichy1Ind 1ine (tent.)
C, isomer
C , isomer
13 _..
C ,H ,, isomer
Is _
C 1 ,H, 9 isomer
Isomer
C 1 H, 6 Isomer
C, H. isomer
5-.
C 13 23 Isomer
C 1 ,H., isomer
uflsaturated C—aikyl benname
isomer
201 223 2—met y1napH:ha1ene
202 229 C 14 H, 5 isomer
203 229 C. Ii.. isomer
5 3
204 229 C isomer
ls 33
205 229 unsa:srated C 7 —slky l be mene
isomer
235 229 C , )L isomer
1s 3
207 229 C 13 .. , isomer
203 230 C 7 —aikyl benzene isomer
209 231 mechy1napHtha1e ie
210 231 C 12 H , isomer
211 232 C H, Isomer
is sO
212 232 C 1 , 3 isomer
213 232 C 14 H 26 isomer
214 232 C_—a1 v1 bennene isomer
215 232 unsaturated C 7 —alkvl benrene
isomer
216 234 C 16 H 3 , Isomer
217 234 C 5 —a1 y1 benzene Isomer
218 235 C rL isomer
15 0
219 235 C 15 H, 3 isomer
220 235 C H isomer
14 2.
221 235 C 7 —alkyl beozene isomer
222 235 unsaturated C..—alkyl berizene
isomer
223 235 C 14 H, 3 Isomer
224 235 C 16 H_, isomer
225 236 isomer
isomer
250 240 dimethy1 aphtha1ene
251 240 C 15 H 32 isomer
252 240 dithy1bvdronaphz aiene
253 240 toluene dlisoovsna:e (tent.)
254 240 dimethylnaphthalene
255 240 C 1 H 32 isomer
256 240 C 1 _H 30 isomer
257 240 C H , isomer
16 3s
253 240 unsaturated C 7 -alkyi. beneene
Isomer
259 240 phenviladole (tent.)
260 240 C 16 H 25 isomer
261 240 C 15 H 30 Isomer
262 240 C 15 H, 2 isomer
263 240 C 15 H 32 isomer
264 240 C 1 H 3 , isomer
265 243 o tamethylcyclotetrasL1oxane ( I C C)
266 240 cedranoae (C 15 H 2 .0) (tent.)
257 240 C H isomer
in 32
263 240 C 15 H, 5 Isomer
Chromato- Elution
aphic Temp. Compound
Peak No. (°C)
Chromato- Elution
graphic Temp. Compound
Peak No. (°C)
135
136
137
153
189
190
191
192
193
194
195
196
197
193
199
200
219
220
220
2:0
5’,
222
5 7
223
223
223
223
223
223
223
224
225
227
225 233 C —aL y1 ben ene Isomer
17 233 C, H , isomer
in
223 233 C H - isomer
is
229 233 C 17 H 35 Isomer
230 233 C 1 H 32 isomer
231 239 C,H, 3 isomer
232 239 unsaturated C 7 —slkyl benzene
isomer
233 239 C H isomer
1. 26
234 240 C H , isomer
16 3.
235 240 biphenyl
236 240 C 14 9. 30 Isomer
237 240 C ,H, isomer
1. z3
238 240 C 14 H 25 Isomer
239 230 C 17 H 2 , Isomer
240 240 C. ,H isomer
i. 22
241 240 C 15 H 33 isomer
242 240 C 12 H 16 isomer
243 240 C. , - isomer
244 240 C 15 H 30 Isomer
245 240 C 1 M, 6 isomer
246 240 C _H Isomer
is 26
247 240 C 15 H 5 , isomer
245 240 C 1 _H 33 isomer
249 233 unsaturared C 3 — Lky1 beozene
63
-------
TABLE B—5. (con.)
Qiromato- Elution
graphic Temp. Compound
Peak No. (°C)
Chromato- E1ution
graphic Temp. Compound
Peak No. (°C)
269 240 C 16 R 32 isouier
270 240 diphenyl ether (tent.)
271 240 phenyl phenol (tent.)
272 240 long chain propyl ketone
273 240 benryl phenol (tent.)
64
-------
30000
20000
U i
10000
2
J
0 4 O 6 O - 1Q Q -- .1210 _4 9_____ Iflip ithO
.l1l,r(• (1:)
5 . l 9 i 1 g__.. _ ___ _ai _ 4 j° .-. 50 .. iQ
Time (mIss)
Figure B—6. Total ion current plot during gas liquid chromatography/mass spectroinetry of
air sainpl.e from the interior of a Gremlin (8/26/76) automobile. A 100 m OV—1O1
SCOT capillary column was used. See text for condition . Sample volume 35.6 9..
l I
0
-
20JQ ‘ Zi’) . _ 211 Q U 1 b\ 1
-------
Table B—6. ORGANIC COMPOUNDS IDENTIFIED FROM FIGURE B—6.
Cbxomato- Elution
graphic Temp. Compound
Peak No. (°C)
Chromato- Elution --
graphic Temp. Compound
peak No. (°C)
1 37 pro v1ene 7 122 C M, 3 isoer
2 51 butane 48 125 C_H 1 . iso er
3 51 butane 39 127 dithv1—1, —d1oxoLane (cent.)
3 58 C_H 10 isomer 50 126 C H 1 , tso at
5 58 c 5 a 1 _ isomer 51 128 C 3 H 16 isomer
6 60 C_H, isomer 52 128 C H isonet
7 62 C 5 H, isomer 53 130 C 8 H 16 isomer
8 66 carbon disulfide 54 131 C 3 H 1 , isomer
9 66 ealeic anhydride (temt.) 55 132 hexamethylcyclotrisiloxane (BKC)
10 66 propane nitrile (tent.) 56 134 C 9 H, 0 isonet
11 67 pentyns 57 135 C H 15 isomer
12 69 chiorobutane (tent.) 58 137 C 8 H 16 isomer
13 70 diethylanine (tent.) 59 138 C 3 H 18 isomer
14 72 C H, isomer 60 138 C H isomer
6 . 18
15 74 C 6 H 1 , isomet 61 142 C 2 —benzene
16 78 Methylpentane 62 144 C,—benzene
17 80 C 6 H 12 isomer 63 145 chlorocyclohexanol (tent.)
18 81 methyl sec—butylamine (tent.) 64 165 C 9 H 18 isomer
19 82 C H isomer 65 149 styrerle
6 14
20 82 C 6 H 12 isomer 66 149 C 2 —benzene
21 85 C 6 H 14 isomer 67 149 C 9 H 13 isomer
22 85 C 6 11, 0 isomer 68 150 C 9 i1 20 isomer
23 87 C H • isomer 69 152 pyridine
6 lh
24 90 1,1,1—trichloroethane 70 153 C 3 —benzene
25 94 C 6 H 10 [ hezadiene] 71 153 C 9 H 16 isomer
26 95 benzeme 72 153 C 9 H 18 isomer
27 97 C 7 H 16 6somer 73 154 C 9 H 18 isomer
28 97 C 7 H 14 isomer 74 155 C 3 —benzene
29 99 Cia 16 isomer 75 156 C 10 H, 2 isomer
30 103 C_H isomer 76 156 hexenyl hexenoate
31 104 C 7 H 16 isomer 77 157 C 9 H 16 isomer
32 105 C_H 12 isomer 78 157 C 10 H 2 isomer
33 106 C H , isomer 79 158 n—propylcyclohexane
34 108 CiR isomer 80 159 a—pimene
35 109 c 5 a 16 isomer 81 160 C 10 H 20 isomer
36 111 C H , isomer 82 161 n—propylbenzene
7 14
37 113 C H, isomer 83 162 benzaldehyde
8 i6
38 113 C 8 H 18 isomer 8!. 163 phenol
39 116 C 8 H 16 isomer 85 164 C 10 R., 9 isomer
40 118 CJi 16 isomer 86 164 C 10 H, 2 isomer
41 118 C 7 H , 0 isomer 87 166 methylstyrene
42 118 furfuryl methyl ether (tent.) 88 167 ethyl toluene
43 120 toluene 89 168 C 10 H 13 isomer
44 120 C 8 H 15 isomer 90 169 C 10 a 16 isomer
65 121 C 8 H 16 isomer 91 170 C 3 —bemzene
46 122 C 3 H 16 isomer 92 170 C 30 H, 0 isomer
66
-------
Table B—6. (con.)
Chrontato- Elution Chromato- Elution —
graphic Temp. Compound graphic Temp. Compound
Peak No. (°C) Peak No. (°C)
93 170 C,,i_ 2 1 OOer 197 0. ,{,, t52 met
34 173 C,.d _ Isomer 1 .0 39 Jtmechvl ,:vreme
35 173 01,3:, tsooer 1-SI 199 C, 3,, 1s;m ,r
96 17; C—bemzene 102 203 .1irethyl pheaoi
97 174 C ,,H,, isomer 10) 200 C-benzene
93 176 C-a;nieme 144 :oo C._H, Isomer
99 177 C,,H_ 2 isomer 115 200 C.:H_, Isomer
100 173 cream! ethyl ether I;o 200 C,.,H,, isomer
101 179 C, 1 3,, Isomer 107 200 C;;H,; isomer
102 179 C ,H,. Isomer 143 200 0.23.3 thomer
103 180 aetnyistyrene 149 231 C—benzene
12; 130 C, 0 3, 3 isomer 130 202 hexmchlorce:oame [ rem:.)
105 180 C. ,H,, isomer 151 202 C_—benzerje
106 131 C.-benzene 152 202 C 11 H 4 isomer
107 181 C, 1 3 2 , isomer 133 203 chloroethylbertzeme tsm:.)
103 161 C,—Senzeme 15; 204 ter:ahydroms;hthaleme
109 131 C H,, isomer 155 :o; c. _ , Isomer
11 so
110 182 Isomer 156 204 Ci H :g isomer
111 132 cresol 157 205 dtmethyThhemol
112 132 C.H, isomer 153 206 C.,H isomer
— s 13
113 133 C 11 3,, isomer 159 207 C 5 —henmeme
1:4 133 C,—benmene 160 208 methvlte:rahodromophthmene
115 133 0123.6 isomer 161 203 naphthaleme
116 184 C .3 ,, Isomer 162 203 C H isomer
ls_ 1_6
117 155 C,—bemzene 163 209 C_—bemmene
118 135 chlomostvreme 16; 210 C.—benzene
a
119 135 C .3,, Isomer 165 210 merhy1tetrahvdroma h:hs1eme
1 5 — —
120 136 C 3, isoaer 166 211 C ,H,, Isomer
11 s Q 1 5
121 186 012324 isomer 167 211 012322 Isomer
122 188 die:hlstyrene 163 211 015326 isomer
123 139 C.iH.. isomer 169 211 013323 isomer
124 139 C ,H,, isomer 170 212 C 6 —benmene
125 139 isomer 171 212 C 6 -benzene
126 190 C.—bemzene 172 213 C ,H, - Isomer
S i i _o
127 192 C 5 —benzene 173 21; N—r.—burylditeridime (reot.)
123 192 C 1 1 H,, Isomer 17.1 215 C,—bertzene
129 192 0123.. isomer 175 216 methorçibemmsldehvde
130 193 C,,H, 6 Isomer 176 216 013325 isomer
131 193 dimerhylindane 177 217 d1methy1tstrahydromm htha1ene
132 194 C1 H.3 isomer 178 217 C 6 —benzene
133 194 C—benzene 179 213 013324 isomer
134 195 ciiH:o Isomer 130 213 C 13 H, 5 isomer
135 196 C, ,H,, Isomer 181 215 C 13 H, 3 Isomer
136 196 methyl antsole 132 213 methvlterrahvdronaphthalene
137 197 C 5 —benzene 153 220 C 7 —benmeme
133 197 0.1320 Isomer 154 221 C 13 H,, Isomer
67
-------
Table B—6. (con.)
1.
:37
159
130
191
192
193
194
195
196
197
193
139
200
201
202
203
204
205
206
207
203
209
210
211
212
213
214
- . 1 a .er
C. 5 - isorner
_3 —)
C— ,enzeae
0
. i .ethy1dLhvdroin3ene
C ..—5enze e
C , isoaer
C .H isoc er
1 3..
C. 3 L . 3 isooer
C 1 i., 3 isomr
ey1trah dro ap otha1e e
ethy1naphtha1e e
C. .— oenze te
C, JL,. iso oer
..,
iSOi er
ehy1 apha1eoe
:i echy1i a opropeny1benzene
isoaer
C..—benzene
diisobutylthiophene (2)
C 16 H 32 isoi:ier
er y1cyc1ohexeoe
C 15 H 30 iso oer
r5 ethy1isopropeny1benzene
C, 5 H 32 ismer
Siphenyl
C 1 ,E 30 iso ner
C 1 ,H 30 isomer
C,,H ., 3 isomer
C 1 , H, 6 isomer
C.H, —benzene
0
C, H 30 isoer
dinethy lpht h.3 le n e
isoner
di—t—buty lcreso l
C 15 H, 3 isomer
C. H isomer
.o 32
C,—tetrahydrottaphth a le me
C 1 32 isomer
C . { isomer
1 29
C 16 E 30 isomer
C, H 3 , isomer
C 15 H,, isomer
C 1 H, 9 isomer
C 1 i, 0 isomer
C I L., isomer
16 .
isorer
C 16 H 30 isomer
C 1 H 3 , isomer
Chromato- Elution
graphic Temp. Compoufld
?eak No. (°C)
Chromato- EluSion
graphic Temp. Compound
Peak No. (°C)
C . isomer
1 0
, imethvi o mthiie me
im thv Lrnspn ha1ene
dithy1pntr a1 ’me
C .3,. isomer
1) . 3
C (,, isomer
1, —*
C 15 H, 3 isomer
di=ethvinaphtha1e e
mechoxyanthracene (tar.t.)
223
223
223
226
226
227
223
228
229
230
231
232
232
233
233
234
235
236
238
239
240
a
a
a
a
115
216
217
213
219
220
221
223
224
225
226
227
228
229
230
231
232
233
234
235
236
237
239
239
240
241
a
a
a
a
a
3
a
a
a
a
a
a
a
a
a
a
a
a
a
3
a
a
a
a
a
a
a
a Isothermal
68
-------
0
ii uT
01
III
II
j I j1 lj 10
III
l!8 200
14 ()
45
Figure 11—7. Total ion current plot during gas liquid chromatography/mass spectrometry
of air sampl.e from the interior of a Rabbit (10/9/76) automobile. A 100 m
OV—101 SCOT capillary column was used. See text for conditions. Sample
volume 11.7 9..
II
20000
10000—
2
4d
C)
6()
80
l0
15
100 120
‘tenipe rat. ure ( C) —
20
4j)
25
Time (mm)
JO
is
-------
Table B—7. ORGANIC COMPOUNDS IDENTIFIED FROM FIGURE B—7.
1 .2 CO,
LA 42 - .ethylsilane
2 43 dichlorodifluorometh3ne
3 45 1—butane
4 46 acetaldehyde
5 50 isopentane
5A 50 trichiorofluormethane
53 51 propenal + propanal + furan
6 51 n—perttane
6A 52 acetome
63 52 dinethyl ether + diethyl ether
6C 53 dichioromerhane
7 54 freon 113 (3KG)
7A 54 CS,
75 55 isopropanol + ter—butanol
8 56 isobutyraldehyde
9 58 2—trethylpentane
9A 59 2—methyipropenal ( eut.)
93 59 diethyl sulphide
10 60 3—methylpenrane
1CA 60 n—butanal
103 61 methyl vinyl ketone
11 61 hexafluorobenzene (er)
12 62 n—hexane
13 63 chloroform
13A 64 methyl ethyl ketone
133 65 2,4—dimethylpentane
14 66 iethylcyclopentane + perfluoro—
toluene (€1)
14A 66 1,2—dichloroeth .ane 4- isobutyl
alcohol
n—butyl alcohol
C 6 H, 0 isomer
benzene
cyc lohexane
2— echy1hexane
2 • 3—dimethylhexane
3—nethylbexane
dimethylcyclopentane isomer
3—methylbutanal
trich loroethy lene
dimethylcyclopeotane isomer
n—heptane
C.,H. isomer
C 8 R isomer
24 92 mettvicyclohexane
25 54 C 3 5 19 isomer
25A 87 C,H - isomer
0 10
26 88 tri ethy1pentsne iso r
27 39 toluene
27A 91 C 8 H 13 isomer
28 92 2,4—dimethylbexane
23A 93 C 8 H 16 isomer
29 94 n—hexanal
29A 95 C 8 H 16 isomer
298 97 C 3 16 isomer
30 98 n—octane
31 98 tetrachloroethylene
31A 99 C H isomer
o 16
32 102 silane compound
33 104 C 9 !i, 0 isomer
34 105 ethylcyclohexane
35 106 tri ethy1cyc1ohexane + C 9 H, 0
isomers
35A 107 C 9 8 13 isomer
36 108 ethylbenzene
36A 109 trimethylcyclohexane isomer
363 110 2,3—dimethyiheptane
37 110 —xy1ene
38 111 2—methyloctane
38A 112 4—ethylheptane
39 113 3—ethy1hepta e
40 114 styrene or cyclooctatetraene
40A 114 C 9 i 18 isomer
41 115 o—xylene
41A 115 n—heptaldehyde
42 116 C 10 R, 0 isomer
42A 116 C 9 R 13 isomer-
43 118 n—nonane -
44 120 C 9 H 13 + C 10 W, 0 isomers
45 121 isopropylbeozene
45?. 122 C, 0 8, 2 isomer
46 122 C 9 8 16 + C 9 H 18 isomers
47 123 C 10 U 22 isomer
48 124 propycyclohexane
49 125 terpinene isomer
69?. 126 C 10 H 22 isomer
50 126 beozaldehyde
50?. 127 n—propylbenzene + C 10 H, 0
isomer
51 US n—ethyltoluene
ChromatO- Elution
graphic Temp. Compound
Peak No. (°C)
Chroniato- Elution
graphic Temp. Compound
No. (°C)
carbon tetrachioride
143 68
l4C 69
15 69
15?. 70
16 71
17 72
17?. 73
18 74
19 75
19?. 75
20 76
20?. 78
21 78
22 79
23 80
70
-------
TABLE B—7. (con.)
Chromato- iioE T omato Elution
graphic Temp. Compound graphic Temp. Compound
Peak No.(°C) ______________________ Peak No. ( 0 C) ______________
24 ._ .aoner 133 c,, ,
52 :: l,: .s:L e.,en e e 72 153 o er
1 2 0 iSomer 73 159 dime Let j e ze ’ e omer
53 131 i sc m r 7 159 C 11 H, 3 some
54 132 l oLu me 75 160 isomer
34A 132 C. . , Iso mer 75 161 dimechvlphenoj isomer
313 133 c,, . isomer 76A 162 C—slk1 benme e i omee
—J . 0 S
35 :33 C, , 5 Lsome 77 163 CpH 2 + C 11 H, 0 !so rs
53A 134 isomer 7 ’A 163 pent*jccleiexsne
56 135 1,2,1—tt6liemzeme 161 C 19 H_, isomer
55A 135 C 1 i 23 isomer 77C 155 te raet 5emeeme Isomer
8 dim y1? ieo.o! isomer
33 143 to so ut 10 79 166 C 1 1, 5 boor
53A 113 1,2 ,1— :imechv1bemzeme 30 167 c:
12 _o
39 141 C.—aikyl bore — C. :6:j 1 163 c 15 i 5 . iscoer
SIA 153 C 5 —a1yl benze er
39A 11.1 C 1 E... .. coer 82 169 C SL 5 isomer
“1:22 iSomer 83 170 r.a : a1eme
61 13 cd ., isomer 172 dodeceme
62 144 b: icyc5o6exaoe 85 175 i—do ecome
62A 145 C—a lkyl benzene + C, H,, 56 j77 C 13 ,
isomers 87 178 c, 3 73 isomer
63 155 — ropv1 o1uene 180 C 13 H 5 isomer
53A 136 isomer 91 132 he n1yc 5ex
633 146 o 5u::1benzene 9 180 C 13 H,, isomer
64 147 o—poo?v10 0luene 91 184 C, 5 3, 3 isomer
64A 147 C 1 1 H . isomer 9L4 134 C 13 H 18 1 50700
643 133 ,d 2 . Isomer 92 135 C 13 H, 8 smmer
65 148 o—prc?yltolueme 3 136 2—methyldodecame
63A 119 C 10 d 53 isomer 94 is;’ 3—methyidodecon
66 150 diethylbemmene isomer 95 189 C .
Is 33
SSA 150 C—sl yi benz r,e isomer 95A 193 C 13 H 26 isoner
67 151 C, H , iscner 953 194 C .H, iS0000
63 152 C,—alkvl benzene isomer 9 196 o—tridecane
4 —
69 154 C, d., isomer 96A 199 C ,i is o
-— 14 3
70 155 C — ic-,1 benrone + C 1 d,, 963 205 C ,H, isomer
S
isc ers 96C 203 C14 123 Isomer
71 156 is—ori000sne
71
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4b
6b
I
80
I
100
I
120
Temperature
I
(0 0
160
I
180
I
200
I
I
I
I
I
I
I
1
I
5
10
15
20
30
35
40
45
Figure B—8.
25
Time (mm)
Total ion current plot during gas liquid chromotography/mass spectrometry of
a background air sample. A 100 m OV—1O1 SCOT capillary column was used. See
text for conditions. Sample volume 35.6 .
6000 —
5000
4000 -
3000
2000
1000 -
0
0
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Table B—S. ORGANIC CO OUNDS IDENTIFIED IN ANBIENT AIR BACKGROUND
ADJACENT TO THE GRENLIN.
Chromato- Elution
apbic Temp. Compound
Peak No. (°C)
Chromato- Elution
graphic Temp. Compound
Peak No. (°C)
1 39 methylsilana (3KG) 18 90 C E 18 isomer
IA 42 CO 2 19 92 ri—octane
2 45 isopeotatoe 19k 93 tetrachioroerhylene
2k 46 CH 10 isomer 20 97 silane compound (3KG)
2B 47 acetaldehyda 20k 100 C 9 H 20 Isomer
2C 48 C 5 H 10 isomer 208 103 ethylbenzerie
3 49 acetone + freon 113 (5KG) 21 105 £—xylene
4 52 C 6 11 12 isomer ZLi . 101 C H 20 isomer
5 53 2—methylpentame 218 108 C 9 }1 20 isomer
5k 54 3—methylpenrane 21C 109 styrerie
6 55 hexafluorobenzene (es) 210 110 o—xylene
7 56 n—hexane 22 111 C 9 H 18 isomer
7k 57 chloroform 23 113 n—nonane
lB 58 C 6 H 12 isomer 24 117 silane compound (8KG)
8 59 perfluorotoluene (e’) 24A 121 C 10 H, 2 isomer
8A 60 methylcyclopentane 25 124 benzaldehvde
9 64 banzene 25k 125 m—ethyltoluene
9k 65 carbon tetrachioride 258 126 C 3 —alkylbenzene isomer
98 65 cvc lohexane 26 129 phenol
10 66 2—methylhexane 26k 131 o—ethyltoluene
10k 67 2,3—dimethylpentane 27 132 C 10 H 20 isomer
11 68 3—methylhexane 28 135 n—decame
hA 69 dimethylcyclopentane isomer 28k 137 1,2,3—trimethylbeozene
12 70 C 7 11 16 isomer 29 138 C 11 24 isomer
12k 71 isomer 30 143 C 11 H 2 , isomer
13 72 a—heptane 30k 145 acetophenone
13k 73 C 7 H 14 isomer 308 146 C 11 H 24 isomer
13B 76 C..H isomer 30C 148 C,—alkyl benzene isomer
i 14
14 77 methycyclohexane 31 151 C 11 Hn 4 Isomer
15 79 C 8 H 18 isomer 32 154 ri—uridecame
16 82 C 8 Hj 8 isomer 32k 165 silane compound (8KG)
17 84 to].uene 32B 170 C 12 }i 24 isomer
17k 85 C 3 H 13 isomer 32C 187 —methy1naphtha1ene
178 87 C H - isomer 320 190 ci.methylnaphthalene
8 in
17C 88 C 8 H 16 isomer
73
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74
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APPENDIX C
FREQUENCY—PRIORITIZED LIST OF ORGANICS
FOL ND IN AUTOMOBILE INTERIORS
-7-
-------
Table C—i. LIST OF ORGANICS
r
-
z
Comoound
.
E -
- .
Z
t,
<
>
=
0
-.
z
—
-
z
0
<
;a
>
n—propylbenzene x x x x x x
C 4 —alkvl beezene isomers x x x x x x
C 5 —alkyl benzene isomers x x x x x
1—butene x x x x x x
terpinene isomers x x x x X x
C 11 H 22 isomer x x x x x x
C 13 H, 5 isomer x x x x x x
C 9 H 15 isomer x x x x x
C 9 H 18 isomer x x x x x
C 11 H, 0 isomers x x x x x
C 12 H 26 isomers x x x x x
C H,isomers x x x x x
12 2-.
C 13 H., 3 isomers x x x x x
dimethyiphenol isomers x x x x
dimethy lstyrene x x x x
dimethy lnaphtha lenes x x x x
n—butane x x x x
n—pentane x x x x
C 6 N 10 isomers x x x x
C 8 3 16 isomers x x x
C H, isomers x x x x
10 LS
butylcyclohexane x x x x
C 14 H 30 isomers x x x x
C 14 H, 3 isomers x x x x
2—methy l—2—propano l x x x
cresol x x x
carbon disulfide x x x
beozothiazole x x x
ethy lbenzene x x x
C 5 —alkylbenzene isomers x x x
dimethyldihydroindene or
methy l tetrahydronaphtha lene x x x
C 7 —alkylbenzene isomers x x x
biphenyl X X X
methyistyrene isomers x x x
naphthalene x x x
2—butene x x x
76
-------
Table C—i (con.)
.
r’
—
Co moo nd
Z
=
C
z
.-,
-
propylcyclohexane x x x
isomers branched x x x
C 10 H 1 . isomers x x x
isomer-s x x x
C H 32 isomers x x x
C 15 H 30 isomers x x x
C 15 N 34 isomers x x x
C 16 H 32 isomers x x x
l,2,4—trimethylbenzene x x x
propenal x x
propanal x x
2—methylproperisl (tent.) x x
n —butanal x x
n—hexanal x
long chain propyl. ketone x x
di—t--butyl cresol X X
furan x x
dimethyl ether x x
vinyl methyl ether (tent.) x x
n —cresyl ethyl ether
diphenyl ether (tent.)
benzyl phenyl ether (tent.)
o—propyitoluene x x
—xylene x X
dimethylethylbenzene isomers x x
djmechylindane x x
r.ethyltetrahydronaphthalenes x x
maleic anhydride (tent.) x
C 3 R 14 isomers x x
C 10 H 20 isomers x x
pencylcyclohexane x x
ri—dodecane x x
C 12 H 27 isomers x x
C 14 H 26 isomers x x
C 15 .1 28 isomers x x
C 15 H 24 isomers x x
C 17 H isomers x x
l—bucanol x x
isopropylbenzerze x x
77
-------
Table C—i (con.)
: .
z
- .
—
Compound
z
n
i-.
.
t
U
-‘
z
-
—
-
U
.
1,2—dibromoethane (tent.) x
chiorobutane (tent.) x
chiorocyclohexanol x
chiorostyrene (rent.) x
hexachloroethane (tent.)
chloroethylbenzene (tent.) X
trjchlorobenzene isomer x
2—merhyipropanal x
3—methylburanal x
hexanal isomer x
3—methylbutanal x
n—heptarial x
2—butenal x
ethylbutanal (tent.) x
methoxybeazaldehyde x
methyl vinyl ketone x
methyl ethyl ketone x
4—methyl—2—peatanone x
2—heptanone X
octanone isomer (tent.) x
cedranone (C 15 H 24 0) x
2—propanol x
2—methyl—l—propanol x
2—methyl-l-butaaol (tent.) x
undecenol (tent.) x
ethyiphenol isomer x
ethyl acetate x
hexenyl hexenate (tent.) Z
dierhyl ether x
ethyl vinyl ether x
furfuryl methyl ether (tent.) x
diniethyl—l,4—dioxane (tent.) x
methyl anisole x
butyl methyl ether x
dihydropyran X
anisole x
diphenoxybenzene x
methoxyanthracene (tent.) X
phthalate X
78
-------
TABLE C—i. (con.)
-.
,
Compound
z
n
n
- ,
.
C
j
C
U
C
C
—
—
—
J
C
U
<
c
;
N—methyl—2—butylamine (tent.) x
diethyj.amine (tent.) x
N—n-butylpiperidine (tent.)
butylaminodiphenylamine (tent.) X
2—amino—2—methyl—1--propanol x
cyclohexylarnine (tent.) x
aniline x
trimethylindoline (tent.)
phenylindole (tent.) x
pyridine (cent.) X
N—ethylpyridine (tent.) x
pheziylpyridine (tent.) x
dimethyiquinolifle x
propane nitrile (tent.) x
propane nitrile (tent.) x
3, 3—dimethylcyclobutane carbonnitrile
(tent.) x
toluene diisocvanate (tent.)
diethyl sulfide
diisobutylthiopheCe (tent.)
C 8 —alkyl thiOphene (tent.) x
tri methylisopropylbenzene x
phenylcyclohexane X
C 8 —alkyl ben ene x
C 2 —alkyl styrene isomers x
diethyisryrene isomers x
di—t—bucylphenanthrene (tent.) x
dimerhyldihydronaphthalenes x
tetrahydronaphthaiene x
ethvltetrahydronaphthsisne x
C,—alkyl tecrahydronaphth3lene
dimethyltetrahydrOnaphthalefle
diethylbetizene isomer x
1,3,5—trimethyl benzene x
—propyltoluan e x
tetranethylbeuzene isomer x
—ethy1totuene x
79
-------
Table C—i (con.)
-. z -. —
s-I 0
Compound
biphenylene x
unsaturated C 6 —allcyl benzene isomers x
unsaturated C 7 ’-alkyl benzene isomers x
C 9 —alkyl benzene isomer x
unsaturated C 8 —alkyl benzene isomers x
propene (tent.) x
C 4 1 10 isomer x
cyclopentene x
pentyne x
c 5 a 10 isomer x
methylpentene x
C 7 H 12 isomer x
methyl hexyne x
methyl cyclohexene isomers x
e thylcyclohexane x
trimethylpentane isomer x
trimethylcyclohexane x
2,3—diinethylheptane x
C 10 11 12 isomer
decahydronaphthalene (tent.) x
triiaobutylene X
isomers x
C 12 H 18 isomer x
hexylcyclohexane x
2—methyldodecane x
3-inethyldodecane x
n—tridecane x
C 14 B 24 isomers
C 14 B 22 isomers x
C 15 H 26 isomers x
isomers x
c 16 a 28 isomers x
C 16 H 30 isomers X
80
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TECHNJCAL REPORT D,ATA
(?ic:se re3d f; r c::o :s o’ r e ‘c ’ r com .1le? 7;
1. REPORT NO. 2. 3. REC P ENTS ACCESSION’ NO.
EPA-600/7-77- 149
4. TITLE AND SUBTiTLE 5. REPORT DATE
Organic Emissions from Automobile Interiors
7. AUTHOR(S) S.PERFOR 1iNG ORG ZAflON REPORT NO
Ruth A. Zweidinger
9. PERFORMING OROANICATION NAME AND ADDRESS
Res earch Triangle Institute
P.O. Eox 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
EHE 62 4A
11. CONTRACT ORANT NO.
68-02-1325, Task 46
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT ND PERIOD COVERED
Task Final: 7/75-1/76
EPA/6 00/13
1S.SUPPLEMENTARY NOTES IERL—RTP project officer for this report is Joseph A. McSorley,
Mail Drop 63, 919/541-2745.
16. AESTRACT
The report gives results 0: an eva1uat on of six subcomnact automobiles
for the emission of vinyl chloride monomer (VCM) and other organics into the pas-
senger compartment. Evaluated were a Ford Pinto, AMC Gremlin, GMC Vega, GMC
Chevette, NMC Datsun 710, and VW Rabbit. VCM was quantified using charcoal car-
tridges interfaced with gas/liquid chromatography-mass spectrometry in the single-
ion detection mode. VCM levels in the Pinto, Gremlin, Vega, and Chevette were less
than the 50 ppb detection limit. With improved instrumental parameters, a 2 ppb
detection limit was obtained. Under these conditions, VCM was not detected in the
Chevette, but was detected in the Rabbit and the Datsun ‘710. Samples were taken for
qualitative gas’liquid chromatograohy-maSS spectrometric analysis of each automo-
bile, using Tenax G.C. sorbent. This analysis produced a composite list of 147
organic compounds which were identified in the automobiles and not in the ambient
air in the vicinity of the test. Another 36 compounds were tentatively identified.
17. KEY WORDS AND DOCU’.lENT ANALYSIS
Air Pollution Air Pollution Control l3B
Organic Compounds
Vinyl Chloride
Automobiles
Vapors
Carcinogens
Automobile interiors 07C
‘
13F
07D
lOSE
13. 3iS REUT ON STATEMENT 19, SECURITY CLASS port)
Unclassified
Unlimited 2O. SECURITY CLASS Th . s ze;
Unclassified
.—.-.—..-—.....- . .
2i.NO. PACES
09
22.
-
EPA Form 2220-1 (9-73)
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