600/3-78-031
March 1978
ORGANIC CHARACTERIZATION OF AEROSOLS AND VAPOR
PHASE COMPOUNDS IN URBAN ATMOSPHERES
by
G. David Mendenhall, Peter W. Jones,
Paul E. Strup and Warner L. Margard
Battelle Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
Contract No. 68-02-1409
Task Nos. 30 & 43
Project Officer
Ronald K. Patterson
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 27711
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for publica-
tion. Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
N,
ii
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ABSTRACT
Organic pollutants in urban atmospheres were characterized by analyzing
particulate and/or vapor-phase samples collected by EPA in St. Louis,
Missouri; Miami, Florida; Denver, Colorado; Houston, Texas; and at the
General Motors Test Track in Milford, Michigan. The particulate samples
were extracted with solvents and the extractable materials analyzed by
elemental combustion analysis and infrared spectroscopic analysis. To
evaluate more than one solvent extraction technique, the particulate samples
were aliquoted and analyzed by several extraction procedures. Some of the
problems encountered with these procedures are discussed. Vapor-phase
samples were collected on Chromosorb 102 chromatographic traps and analyzed
using qualitative gas chromatography-mass spectrometry analysis. Individual
species tentatively identified are shown on reconstructed gas chromatograms
and individual mass spectra for all chromatographic peaks are included in
the appendix.
Ames Tests for mutagenicity on model aerosol products were also con-
ducted. Products tested were from toluene/NO , 1-heptene/NO , and ot-
pinene/NO systems. None of the aerosol products from these systems showed
mutagenic properties.
111
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CONTENTS
Abstract
Figures vi
Tables vii
1. Introduction 1
2. Methods and Procedures 2
Solvent Extraction of Particulate Matter 2
Elemental Analysis of Extractable Particulate Matter. 7
Infrared Analysis of Particulate Matter 7
3. Characterization of Urban Atmospheres 11
Analysis of Ambient Houston Organic Vapor 11
Analysis of Ambient Atmosphere Over Greater St. Louis 11
Analysis of Organic Vapors Adjacent to the GM
Test Site 23
4. Test of Model Atmospheric Aerosols for Mutagenicity ... 30
References 33
Appendices
A. Methane ionization mass spectra of ambient St. Louis
organic vapors unique to samples S5 and S7 34
B. Methane ionization mass spectra of ambient St. Louis
organic vapors unique to samples SI and S6 40
C. Methane ionization mass spectra of ambient St. Louis
organic vapors of sample SI 43
D. Methane ionization mass spectra of ambient St. Louis
organic vapors unique to samples S3 and S4 54
E. Methane ionization mass spectra of ambient St. Louis
organic vapors unique to samples S8, S9, and S10 56
F. Chemical ionization mass spectra for compounds
tentatively identified on the GC-MS analysis (Figure
14) of ambient organic vapors adjacent to the Milford,
Michigan, GM test track 62
G. Methane ionization mass spectra of ambient Houston
organic vapors, corresponding to GC-MS analysis of
samples NH1 (Figure 1) 67
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FIGURES
Number Page
1 Methane ionization GC-MS analysis of ambient Houston
organic vapors, sample HN1 12
2 Methane ionization GC-MS analysis of ambient Houston
organic vapors, sample HN3 13
3 Methane ionization GC-MS analysis ol a-.ibient Houston
organic vapors, sample HN4 . 14
4 RGC of methane ionization GC-MS of St. Louis sample S7 . . . 16
5 RGC of methane ionization GC-MS .1 St. Louis sample '">... 17
6 RGC of methane ionization GC-MS of St. Louis sample S6 . . . 18
7 RGC of methane ionization GC-MS of St. Louis sample SI ... 19
8 RGC of methane ionization GC-MS of St. Louis sample S3 ... 20
9 RGC of methane ionization GC-MS of St. Louis sample S4 . . . 21
10 RGC of methane ionization GC-MS of St. Louis sample S8 . . . 24
11 RGC of methane ionization GC-MS of St. Louis sample S9 . . . 25
12 RGC of methane ionization GC-MS of St. Louis sample S10 . . 26
13 Electron impact GC-MS analysis of ambient vapors at
Milford, Michigan, GM test track 28
14 Methane ionization GC-MS analysis of ambient vapor at
Milford, Michigan, GM test track 29
VI
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TABLES
Number Page
1 Urban Atmosphere Samples 3
2 Soxhlet Extraction of Atmospheric Particulate Matter 4
3 High-Frequency Dispersive Extraction of Atmospheric
Particulate Matter 6
4 Weight Percent Carbon, Hydrogen, Nitrogen, and Oxygen in
Extractable Matter Obtained by High-Frequency
Mechanical Dispersion with Solvent 8
5 Constituents of Atmospheric Particulate, Expressed as
Weight-Percent of Total Particulate 9
6 Infrared Spectroscopic Data on Benzene Extracts of
St. Louis Particulate 10
7 Compounds Tentatively Identified from Methane lonization
GC-MS Analysis of Ambient St. Louis Vapor Samples .... 22
8 Ames Test for Mutagenicity of Atmospheric Aerosols 32
VII
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SECTION 1
INTRODUCTION
Urban particulate and vapor-phase samples were collected by EPA during
a series of sampling and monitoring programs, and given to Battelle-Columbus
Laboratories for analysis. The Particulate and vapor-phase samples, collected
in certain urban atmospheres, were analyzed by solvent extraction followed
by elemental combustion analysis and infrared spectroscopic analysis. The
vapor-phase samples, collected from the ambient atmosphere over St. Louis
and in Milford, Michigan, adjacent to the General Motors (GM) test track
were analyzed by electron impact (El) and methane chemical ionization (CI)
gas chromatography-mass spectrometry (GC-MS).
In addition to ambient sample analyses, several model aerosol samples
were investigated for mutagenic properties. The results of the AMES
mutagenicity tests on model aerosols derived from toluene, a-pinene, and
1-heptene are presented.
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SECTION 2
METHODS AND PROCEDURES
SOLVENT EXTRACTION OF PARTICULATE MATTER
Urban particulate and vapor-phase samples were collected by EPA during
a series of sampling and monitoring programs, and submitted to Battelle-
Columbus Laboratories for analysis. Sample sites and collection dates are
shown in Table 1. The samples have been numbered to permit convenient
reference in the discussion to follow. Samples 1 through 6 represent particles
less than 1.1 pm; and were collected on .reated quartz filters, preceeded by
an Andersen-2000 High Volume Sampling Head. The particulate and vapor-phase
samples were analyzed by solvent extraction followed by elemental combustion
analysis and infrared spectroscopic a '1ysis. The procedures of analysis
and results of the analysis are discus, i in the following 2ctions.
In this project, the filters used in the sampling were extracted with
a solvent to remove the organic particulate for analysis. Solvent extrac-
tion of particulate matter was directed toward both the acquisition of data
and the evaluation of various extraction techniques and solvents. The most
frequently used technique was Soxhlet extraction. During this program, as
well as during the study "Haze Formation-Its Nature and Origin" (1), methylene
chloride was generally used in place of benzene. Methylene chloride (b.p.
40°C) is considerably more volatile than benzene (b.p. 80°C) and hence can
be removed with less risk of losing volatile samples compounds. Particularly
in cases where detailed analysis of extractable matter is to be conducted,
maintenance of sample integrity has dictated the use of the more volatile
solvent. Nevertheless, in view of the previous widespread use of benzene as
an extraction solvent, we undertook a comparison of the two solvents by
dually extracting samples 13, 14, 15, and 16. The 8-inch x 10-inch filters
were divided in half. One half was extracted first with benzene and then
with diethyl ether. The second half was extracted first with methylene
chloride and then with diethyl ether. Data for weight-percent solvent
extractable are shown in Table 2. For three of the four samples compara-
bility between benzene and methylene chloride extractions is extremely
close.
Diethyl ether was also L ed as a solvent so that it could be evaluated
for extraction of the relatively polar organic constituents of particulate
matter. Methanol has been used for this purpose, but is less than ideal
in that inorganic salts may be additionally extracted. Higher alcohols are
insufficiently volatile to permit their facile removal. During the haze
formation study (1) dioxane was evaluated for use as a polar solvent, and
proved unsatisfactory because of a high and variable solvent blank (residue).
This was observed even with re-distilled solvent, and was attributed to the
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TABLE 1. URBAN ATMOSPHERE SAMPLES
Sample
No. Site
Date Type
1 St. Louis, Missouri,
2 St. Louis, Missouri,
3 St. Louis, Missouri,
4 St. Louis, Missouri,
5 Miami, Florida, Site
6 Miami, Florida, Site
7 St. Louis, Missouri
8 St. Louis, Missouri
9 St. Louis, Missouri
10 St. Louis, Missouri
11 Denver, Colorado
13 St. Louis, Missouri
14 St. Louis, Missouri
15 St. Louis, Missouri
16 St. Louis, Missouri
HN1 Houston, Texas
HN2 Houston, Texas
HN3 Houston, Texas
HN4 Houston, Texas
SI St. Louis, Missouri
S2 St. Louis, Missouri
S3 St. Louis, Missouri
S4 St. Louis, Missouri
S5 St. Louis, Missouri
S6 St. Louis, Missouri
S7 St. Louis, Missouri
S8 St. Louis, Missouri
S9 St. Louis, Missouri
S10 St. Louis, Missouri
Ml Milford, Michigan
M2 Milford, Michigan
M3 Milford, Michigan
Site BH (Q-049)
Site MC (Q-050)
Site BH (Q-044)
Site MC (Q-046)
#10 (Q-009)
#10 (Q-003)
July 25, 1975
July 25, 1975
July 23, 1975
July 23, 1975
June 11, 1975
July 4, 1975
March 2, 1974
February 26, 1974
October 4, 1973
October 3, 1973
November, 1973
March 2, 1974
February 26, 1974
October 4, 1973
October 3, 1973
July 23-24, 1974
July 24, 1974
July 24-25, 1974
July 25-26, 1974
July 30, 1975
August 5, 1975
August 5, 1975
August 5, 1975
July 28, 1975
July 30, 1975
July 28, 1975
August 8, 1975
August 8, 1975
October, 1975
October, 1975
October, 1975
October, 1975
Particulate
Particulate
Particulate
Particulate
Particulate
Particulate
Particulate
Particulate
Particulate
Particulate
Particulate
Particulate
Particulate
Particulate
Particulate
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
Vapor-phase
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formation of peroxides. In view of various disadvantages associated with
the use of other solvents, the use of diethyl ether was evaluated. The
data indicates that only a small additional increment of material is
obtained during the second extraction with diethyl ether. These data may
be compared with data from the haze formation study (1) in which extraction
was conducted first with methylene chloride and then with dioxane. For
seven urban particulate samples from New York City, Columbus, Ohio, and
Pamona, California, the data averaged 13 weight-percent methylene chloride
extractable and 19 weight-percent dioxane extractable. The data suggest
that diethyl ether is not suitable for extraction of the desired polar
organics.
More fundamental than selection of extraction solvents is the question
of suitability of Soxhlet extraction for obtaining the organic constituents
of particulate matter. The technique has been criticized as leading to
incomplete extraction, irregular data, and the decomposition of some
sensitive organics (i.e. polynuclear aromatic hydrocarbons) during extended
periods of solvent refluxing.
In an alternative procedure devised by Sawicki and Golden (2), parti-
culate organics are extracted by ultrasonic agitation with solvent using
a horn-type sonicator. The authors describe the procedure as leading to
fine shielding of filter material and breakdown of cohesive clumps of
particulate matter, with improved overall extraction efficiency. Moreover,
the method is conducted entirely at room temperature or below. In the
published procedure 16 cm portions of filter material are extracted with
60 ml of solvent. However, an 8-inch x 10-inch filter has an area of
645 cm2. Private communication with Dr. Sawicki revealed that scale up of
the procedure has not proven feasible. Dr. Sawicki described an alternative
approach under investigation in his laboratory in which a high-frequency
mechanical disruption apparatus is substituted for a horn-type sonicator.
Such devices (3) combine high-frequency cavitation with efficient mechanical
disruption. In order to evaluate and gain experience with this technique,
we have utilized it is place of Soxhlet extraction for samples 1 through 6.
The instrument used in Dr. Sawicki's laboratory is the Polytron-45
(Brinkman Industries). The instrument used at Battelle was the closely
comparable Super Dispax-45 (Tekmar Company, Cincinnati, Ohio).
For the mechanical extraction procedure, the 8-inch x 10-inch filters
were divided in half. One half was extracted first with benzene, and then
with methanol. The second half was extracted with distilled water only.
The volumes required for the mechanical extraction procedure were relatively
large compared with those employed during Soxhlet extraction. Even after
filtration and centrifugation, the mechanical extracts contained quantities
of apparently colloidal material. Concentration of the extracts led to
agglomeration of most of the remaining colloidal material in a form that
could be filtered or removed after centrifugation.
Data for weight-percent solvent extractable are shown in Table 3.
Despite significantly lower mass-loading, the Miami samples average
approximately 19-percent greater content of benzene extractable matter
than the St. Louis samples. Among the St. Louis samples, those collected
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at the industrial BH site show significantly higher content of benzene
extractable matter. Finally, the blank value for benzene extractable
matter obtained using the mechanical disruption technique is approximately
100-fold greater than the corresponding value obtained when pre-extracted
quartz filter material is subjected to Soxhlet extraction.
ELEMENTAL ANALYSIS OF EXTRACTABLE PARTICIPATE MATTER
Benzene and methanol extractable matter were subjected to elemental
combustion analysis for carbon, hydrogen, and nitrogen. Values shown for
weight-percent oxygen were calculated by difference from the CHN (carbon,
hydrogen, and nitrogen) data. Water extracts were analyzed for total
organic carbon and for nitrate, sulfate, and ammonium. The data are shown
in Tables 4 and 5.
The analysis in these tables show several irregularities that are
probably due to systematic errors resulting from the small sample sizes.
Three of the hydrogen percentages in Table 5, for instance, are over 100
percent, probably because of water absorbed onto the filter. The carbon
analyses in Table 4 from the water extracts show an exceptionally wide
variation, again leading one to suspect analytical problems.
INFRARED ANALYSIS OF PARTICULATE MATTER
Infrared spectra were obtained on the benzene extractables of three
samples: two collected in St. Louis, Missouri (Q049 and Q050) and one
collected in Miami, Florida (Q003). These samples were chosen because they
represent an industrial and a metropolitan site in St. Louis, and for
comparison, the entirely different Miami site.
Sample Q003 contained large amounts of a phthalate ester (assumed
to be introduced in handling) which effectively prevented the measurement
of the absorption bands of interest (carbonyl peak at 1710 cm"-'-, percarbonyl
peak at 1770 cm"-'-, and the organic nitrate peak at 1630 cm"-'-). Therefore,
no data are presented for this sample.
Sample Q049 contained large amounts of a silicon grease (again assumed
to be introduced in handling), but the absorption bands of the silicon
grease do not obscure the sample absorption bands of interest. Table 6
lists the relative intensities for the carbonyl peak, the percarbonyl
band, and the organic nitrate absorption of Q049 and Q050. Relative
intensity is defined as:
P.P. at specified frequency
O.D. at 2920 cm~l
where O.D. = optical density or peak absorption.
The infrared spectra of the benzene extractables are much like the
spectra of the methylene chloride extractables presented in the report
"Haze Formation-Its Nature and Origin" (1). The haze formation report also
explains the nature of the absorption bands observed.
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and 0010) me lower i h.m most ot Liu? Jata ^ivcn In the ha/e formation
rtport ("with the t XL <- p'_ ion of rla.1 iMr.ver, Colorado sanp 1 e.i 1 . Tills inJicafi: t>
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ext.rac tables occpt that tin infrarec spf^L;a appeal to be qi,.i 11 tat ive ! v
sJnii lar.
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10
-------
SECTION 3
CHARACTERIZATION OF URBAN ATMOSPHERES
ANALYSIS OF AMBIENT HOUSTON ORGANIC VAPOR
Four ambient organic vapor samples were obtained from a sampling
location on May Drive, Jacinto City, Houston, during July 1974. The samples
were obtained sequentially using Chromosorb 102 chromatograpic traps. The
available details pertaining to these samples may be summarized as follows:
Sample Number HN1 HN2 HNS HN4
Starting date/hour 23/1700 24/0925 24/2050 25/1650
Ending date/hour 24/0900 24/2030 25/1636 26/1050
Sample Volume CF 480 300 600 540
Weather Haze Clear Clear Clear
Qualitative methane ionization GC-MS analysis was carried out in the
manner described in the next section. No analytical data was obtained for
Sample HN2; it appears that an unforseen error occurred either during
sampling or analysis of the corresponding chromatographic trap. Simi-
larities are evident between all three samples which were successfully
analyzed, although sample HN1 which was collected under hazy conditions
shows a greater number of detectable organic species. While the nature
of these survey analyses precludes accurate assessments of specie concen-
trations, it appears that the materials tentatively identified in Sample
HN1 are at somewhat higher concentrations than Samples HN3 and HN4, despite
the higher sample volumes of the latter two samples. Hydrocarbons appear
to be particularly abundant in all three Houston samples; the oxygen-
containing species present could presumably be formed by the combustion
or photooxidation of hydrocarbons. The individual species tentatively
identified in Samples HN1, HN3, and HN4 are shown on the reconstructed
gas chromatograms, Figures 1, 2, and 3, respectively. The individual mass
spectra for all chromatographic peaks in Sample HN1 (Figure 2) are included
in Appendix G.
ANALYSIS OF AMBIENT ATMOSPHERE OVER GREATER ST. LOUIS
Airborne sample collection of ambient atmosphere over St. Louis was
conducted using Chromosorb 102 chromatographic traps without the use of
filters. Approximately 300 liters of gas per sample were collected over
a period of about 20 minutes. Samples were collected on four different
days at four different sites near St. Louis.
11
-------
TOLUENE
DIMETHYL NAPHTHALENES
METHYLNAPHTHALENES
C2-STYRENE(ORISOMER)
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The collected samples were recovered by thermal desorbtion, followed
by freeze-out and then thermal inject ion onto a gas chromatographic
column similar to that described for analysis of model aerosols in Section
3. Gas chromatographic separation was achieved using a Silar 5CP chromato-
graphic column. Gas chromatographic-mass spectrometry analysis was
carried out by methane chemical ionization.
Wood River
Two samples, S7 and S5, were coLJected on July 28, 1975, 1/4 miles
upwind and downwind of Wood River, respectively. Each sample was analyzed
using GC-MS and the reconstructed gas chromatograms (RGC) are given in
Figures 4 and 5. Gas chromatographic peaks with the corresponding molecular
weights as determined from the mass spectra are indicated on the RGC;
tentative identification for some of these various compounds are listed in
Table 7. Compounds unique to each sample are indicated by a "U" on the
RGC and their mass spectra are included in Appendix A, referenced by the
spectrum number of the compound.
As indicated by Table 7, the only material that could be tentatively
identified in Sample S5 which was not found in Sample S7 was biphenyl.
Nevertheless, a compound having a molecular weight of 154 was indicated
in Sample S7. However, its GC retention time does not correspond to that
of biphenyl. It is interesting to note that both S5 and S7 contain a
large number of unique materials with S5 having the larger number of the
two. Since sampling site S5 is downwind from S7 this is not surprising
and indicates a major source of pollution upwind of both of these sites.
Baldwin and Hardin
Sample S6 was collected 1 mile southeast of Baldwin on the morning of
July 30, 1975 while Sample SI was collected 1 mile east of Hardin on the
afternoon of July 30, 1975. The RGCs of these two samples are given in
Figures 6 and 7. Table 7 indicates the compounds which were tentatively
identified in these samples and Appendix B includes the spectra found to
be unique.
Sample SI was chosen to illustrate the major types of materials
collected in Samples SI through S10. The mass spectra of these materials
are presented in Appendix C.
St. Louis
Sample 3 was collected 22 miles upwind from the edge of St. Louis
while Sample S4 was collected 20 miles downwind from the edge of St. Louis.
Sample S2 was obtained through the Labadie Plume 5 miles downwind from the
stack. Unfortunately, due to an error in our data acquisition system
while analyzing Sample S2, all data from Sample S2 was lost, and because
thexTual desorption is a once-only technique, S2 could not be reanalyzed.
The RGCs for Samples S3 and S4 are given in Figures 8 and 9. These
two samples are surprisingly similar with each sample containing only one
15
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TABLE 7. COMPOUNDS TENTATIVELY IDENTIFIED FROM METHANE
IONIZATION GC-MS ANALYSIS OF AMBIENT ST. LOUIS
VAPOR SAMPLES
Compound
Styrene
Allylbenzaldehyde
Benzaldehyde
Phenylacetate
Acetophenone
Naphthalene
Terephthaldehyde
Phenol
Me thylnaph thalene
C5-benzene
C2-naphthalene
Blphenyl
MW
104
132
106
136
120
128
134
94
142
148
156
154
S7
X
X
X
X
X
X
X
X
S5
X
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X
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X
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X
X
X
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S6
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X
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X
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X
X
X
X
X
X
X
X
X
X
X
X
S3
X
X
X
X
X
X
X
X
X
X
X
X
S4
X
X
X
X
X
X
X
X
X
X
X
X
S8
X
X
X
X
X
X
X
X
X
X
S9
X
X
X
X
X
X
X
X
X
X
S10
X
X
X
X
X
X
X
X
X
X
22
-------
unique compound, neither of which could be identified. The mass spectra
of these materials are included in Appendix D. It is also of interest to
note the relatively large amount of naphthalene found upwind of St. Louis
as compared to that found downwind. It appears that sampling site S3 is
adjacent to a localized source for this material.
Baldwin Power Plant, Granite City
Sample S8 was collected over Granite City along Interstate 64, S9 was
collected just south of Baldwin Power Plant, and SlO was collected on a
13-minute flight from Granite City to Smartt Field. The RGCs for these
samples are given in Figures 10, 11, and 12, and Table 7 lists the tenta-
tively identified compounds for these samples. Appendix E gives the mass
spectra of compounds unique to each sample or common to only two samples.
None of these unique materials have been identified except for MW 137,
tentatively identified as phenyl acetate, which was absent in sample SlO.
Summary
The qualitative survey analysis illustrated, not surprisingly, that
a large number of organic vapor species are common to most of the sampling
locations in St. Louis. However, it is possible to ascertain the presence
of species unique to specific areas, and thus it may be possible to
establish that a localized source for these specific compounds exists. A
more detailed sampling survey of locations such as those examined in this
study could facilitate both detection and location of the source of airborne
organic pollutants.
ANALYSIS OF ORGANIC VAPORS ADJACENT TO THE GM TEST TRACK
During road tests of catalytic converter equipped motor vehicles at
the Milford (Michigan) GM test track during October, 1975, a disagreeable
odor was noted. The vehicles were being operated with fuel containing
several organic sulfur compounds, and the preliminary reaction of EPA
personnel present was that organo sulfur compounds could be responsible for
the odor. Three samples of ambient organic vapors were subsequently
collected adjacent to the GM test tract (MD, M2, M3) during the automobile
test runs using Chromosorb 102 adsorbent traps (5). The collected vapor
samples were thermally desorbed (5) and subjected to both El and methane
CI GC-MS.
It was not possible to determine why the relative concentrations of
oxygenated species in the automobile exhaust were so abnormally high in this
GM test track experiment on the basis of our analyses; it is however
tempting to speculate that the catalytic converters fitted to the test
vehicles were not operating efficiently. In our opinion, the high relative
concentrations of oxygenated species, particularly benzaldehyde and phenol,
could have been responsible for the unpleasant exhaust odor noted.
Following El and CI GC-MS analyses, the individual components in the
collected vapor samples were assigned structures on the basis of CI molecular
weight determinations and fragmentation patterns and on the basis of El
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spectral matching with the Battelle data bank of approximately 27,000
reference spectra. Where several structural isomers were possible, no
attempt was made to identify each isomer since this was believed to be
beyond the scope of this experiment. Samples were analyzed by both CI and
El GC-MS; since all three samples were very similar, only data for Ml is
shown on Figures 13 and 14.
The major ambient species determined in the above manner are shown on
the El and CI reconstructed gas chromatograms (Figures 13 and 14, respec-
tively) and are listed below; the more abundant species are marked with an
asterisk. Individual mass spectra for the CI GC-MS analysis are given in
Appendix F.
*Xylenes *Acetophenone
*C2~Benzenes *Naphthalene
*Ct|-Benzenes *Vinylbenzylalcohol (or isomer)
Methylstyrene (or isomer) *C2~Benzaldehyde
Allyltoluenes (or isomer) *Phenol
*Benzaldehyde C2~Acetophenones
Tetralin Di-t-butylbenzoquinone
*Methylbenzoate *Dimethylphenol
No sulfur compounds were observed, although these species were
specifically sought.
It is noteworthy that the estimated relative concentrations of
oxygenated species appear to be abnormally high, particularly that of
benzaldehyde, for example. The concentration of benzaldehyde in automobile
exhaust is typically of the order of 0.5 percent of the concentration of
the aromatic hydrocarbons (6,7). Within the constraints prevailing in this
qualitative GC-MS analysis, it appears that the concentration of benzaldehyde
may be approximately comparable with that of the total alkyl benzenes, and
that the total of oxygenated species observed may in fact exceed the total
concentration of alkyl benzenes. Thus, the ratio of benzaldehyde to
alkyl benzenes, for instance, was found to be approximately 200 times
greater than that observed in "normal" vehicle exhaust.
27
-------
DI-T-BUTYLBENZOQUINONE
C2 ACETOPHENONES
PHENOL
C2-BENZALDEHYDE
VINYLBENZYLALCOHOL (OR ISOMER)
NAPHTHALENE
ACETOPHEIV»f.,rtE
METHYL BENZOA -
BENZALDEHYDE
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METHYL STYRENE (OR ISOMER)
C4-BENZENES
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(OR ISOMER)
C2ACETOPHENONE
PHENOL
—«==:
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ALLYL TOLUENES (OR ISOMERS)
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§ S § 15 S « *
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SECTION 3
TEST OF MODEL ATMOSPHERIC AEROSOLS FOR MUTAGENICITY
Several previous studies at Battelle-Columbus were concerned with the
composition of organic aerosols formed under simulated atmospheric condi-
tions. The amount of material in model atmospheric aerosols derived from
several hydrocarbons and NOX to which we could assign a structure was a
small fraction of the total aerosol collected. Since it was reasonable to
suspect that potential carcinogens, in rarticular hydroperoxides and
eposides, may have been present among *.ne unidentified components, we
investigated several aerosol samples _,_or mutagenic properties. A test was
performed that involves the use of srecial bacteria that under certain condi-
tions will multiply only after underg . g mutation in the presence of
chemicals or other agents.
The potential mutagens contained within each of the samples were
detected by means of a special set of Salmonella strains obtained from
Dr. Bruce Ames (Biochemistry Department, University of California, Berkeley,
California). The tester strains are histidine deficient and are used for
the purpose of detecting frameshift and base pair substitution mutations as
indicated by reversion to prototrophy. These systems were selected for
their sensitivity and specificity to be reverted back to the wild type by
particular mutagens (8).
The assay has been adapted for use in detecting compounds which may
be potential mutagens. Potential mutagens are compounds which are not in
themselves carcinogenic or mutagenic but are converted to active mutagens
by mammalian metabolism, especially by the TPNH dependent microsomal
enzymes of the liver. Since these specific bacteria do not have the
mammalian liver, homogenates are added to the system to activate the
non-mutagenic parental compounds to possible mutagens. This activation
system is derived from the rat liver microsome.
The experimental procedure used for detecting mutagens is as follows.
Into 2 ml of molten agar is added 0.1 ml of the bacterial tester strain,
a quantity of the potential ^utagen (100, 50, 20, 10, and 5 yl of the
solution supplied), and the liver microsome solution (when used). The
agar is then poured over the surface of a minimal agar plate and permitted
to solidify. Controls are included at all times, consisting of a sample
to measure the spontaneous reversion rate for each tester strain where the
mutagen is omitted, a sterility check of the mutagen solution and liver
microsome solution (5-9), and positive controls consisting of compounds
which do and do not require metabolic activation.
30
-------
The plates were incubated for 48 hours and observed. The number of
revertant colonies for each bacterial strain were counted and reported as
the number of revertants detected. A sample was considered negative if the
number of induced revertants obtained with the 100 percent sample analyzed
compared to the spontaneous revertants was less than twofold.
It is apparent from the results in Table 8 that none of the model
aerosols show mutagenic properties when the incidence of spontaneous
mutations is taken into account. This result, while reassuring, was
obtained with aerosols derived from simple hydrocarbons. Urban atmospheric
aerosols, on the other hand, are expected to contain organics derived from
a wide variety of hydrocarbon precursors, and may show very different
properties than those obtained in these experiments. Moreover, mutagenic
effects are not the only effects that aerosol components may have on
cellular components, as we have pointed out earlier (4).
31
-------
TABLE 8. AMES TEST FOR MUTAGENICITY
OF ATMOSPHERIC AEROSOLS
(Plate incorporation using induced S-9)
Aerosol sample
tested
1 (Toluene/NO )
M-400 X
Methanol extract
2 (Toluene/NO )
M-400 X
CH Cl extract
3 (1-Heptene/NO )
M-500 X
Methanol extract
4 (1-Heptene/NO )
M-500 X
CH Cl extract
5 (a-Pinene/NO )
M-200 X
Methanol
6 (a-Pinene/NO )
M-200 X
CH2C12
Tester Concentration of
strain 100
TA-100 364
TA-98 43
TA-1538 19
TA-100 391
TA-98 89
TA-1538 21
TA-100 300
TA-98 43
TA-1538 14
TA-100 330
TA-98 43
TA-1538 15
TA-100 340
TA-98 63
TA-1538 11
TA-100 371
TA-98 56
TA-1538 11
50
382
59
19
358
70
17
342
42
15
366
39
12
311
46
11
333
50
13
50-S-
334
52
10
331
85
11
280
40
9
295
43
13
315
27
11
333
24
10
Chemical
9 20
309
54
12
334
45
8
3 .,8
46
12
345
30
7
322
39
6
311
40
12
in ul.
10
323
38
12
302
45
10
302
40
16
300
47
7
313
33
14
347
42
5
5
291
55
16
295
39
9
310
38
8
289
55
5
277
44
13
355
43
10
Control Spontaneous Revertants
TA-100
+S-9 300-317
-S-9 279-234
TA-98
45-45
40-43
TA-1538
14-8
9-9
S-9 sterility = No colonies x2
compound sterility (100 ul nested):
123
NC
NC
NC
NC
NC
32
-------
REFERENCES
1. Miller, D.F., W.E. Schwartz, J.L. Gemma, and A. Levy. Haze Formation -
Its Nature and Origin. EPA-650/3-75-010, U.S. Environmental Protection
Agency, Research Triangle Park, North Carolina, 1975.
2. Golden, C, and E.J. Sawicki. Ultrasonic Extraction of Total Particulate
Aeromatic Hydrocarbon from Airborne Particles at Room Temperature.
International Journal of Environmental Analytical Chemistry, Vol. 4,
pp. 9-23, 1975.
3. Kuchta, K., and L.F. Witt, Jr. Mechanical High-Frequency Dispersion
Equipment for Laboratory and Production. American Laboratory, 5:63-64
and 66-67,1973.
4. Schwartz, W.E., G.D. Mendenhall, P.W. Jones, C.J. Riggle, A.P. Graffeo,
and D.F. Miller. Chemical Characterization of Model Aerosols.
EPA-600/3-76-085, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina, 1976.
5. Jones, P.W. Analysis of Non-Particulate Organic Contaminants in
Ambient Air. Presented at: 67th APCA Meeting, Denver, Colorado,
June 9-13, 1974. (Paper No. 74-265).
6. Wigg, E.E., R.J. Champion, and W.L. Peterson. The Effect of Fuel
Hydrocarbon Composition on Exhaust Hydrocarbon and Oxygenate Emissions.
Presented at: SAE Annual Meeting, Detroit, Michigan, January 10-14,
1972 (Paper No. 720251).
7. Levy, A., D.F. Miller, D. Hopper, C.W. Spicer, D. Trayser, and R.W.
Cote. Motor Fuel Composition and Photo-Chemical Smog: Final Report,
Parts 1 and 2. API Publ. No. 4247, February 1975.
8. Ames, B., J. McCann, and E. Yamasaki. Method for Detection Carcinogens
and Mutagens with the Salmonella/Mammalian-Microsome Mutagenicity
Test, Mutation Res., Vol. 31, 1975, pp. 349-364.
33
-------
APPE-.JIX A
METHANE lONIZA'j N MASS SPECTRA
OF AMBIENT ST. LOLIS ORGANIC VAPORS
UNIQUE TO SAMPLES S5 AND S7
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APPENDIX B
METHANE IONIZATION MASS SPECTRA OF
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APPENDIX C
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APPENDIX D
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APPENDIX G
METHANE IONIZATION MASS SPECTRA OF
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TECHNICAL REPORT DATA
/Please read Instructions on the reverse before completing)
1 REPORT NO
EPA 600/3-78-031
4 TITLE ANO SUBTITLE
ORGANIC CHARACTERIZATION OF AEROSOLS AND VAPOR
PHASE COMPOUNDS IN URBAN ATMOSPHERES
7 AUTHOR(S)
G.D. Mendenhall, P.W. Jones, P.E. Strup and
W.L. Margard
8. PERFORMING ORGANIZATION REPORT NO
3. RECIPIENT'S ACCESSION-NO.
5 REPORT DATE
March 1978
6, PERFORMING ORGANIZATION CODE
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
10. PROGRAM ELEMENT NO.
1AD712 BD-21 (FY-77)
11. CONTRACT/GRANT NO.
68-02-1409
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory - RTF, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Organic pollutants in urban atmospheres were characterized by analyzing
particulate and/or vapor-phase samples collected by EPA in St. Louis, Missouri;
Miami, Florida; Denver, Colorado; Houston, Texas; and at the General Motors Test
Track in Milford, Michigan. The particulate samples were extracted with solvents
and the extractable materials analyzed by elemental combustion analysis and
infrared spectroscopic. analysis. To evaluate more than one solvent extraction
technique, the particulate samples were aliquoted and analyzed by several extraction
procedures. Some of the problems encountered with these procedures are discussed.
Vapor-phase samples were collected on Chromosorb 102 chromatographic traps and
analyzed using qualitative gas chromatography-mass spectrometry analysis. Individual
species tentatively identified are shown on reconstructed gas chromatograms and
individual mass spectra for all chromatographic peaks are included in the appendix.
Ames Tests for mutagenicity on model aerosol products were also conducted.
Products tested were from toluene/NO , 1-heptene/NO , and a-pinene/NO systems.
None of the aerosol products from these systems showed mutagenic properties.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
"Air pollution
*Aerosols
'''Vapors
"''Organic compounds
^Chemical analysis
b.IDENTIFIERS/OPEN ENDED TERMS c. COSATI Field/Group
13B
07D
07C
3 DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
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UNCLASSIFIED
21. NO. Of PAGES
81
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
73
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Include a brief (200 words or less) factual summary of the most significant information contained in the report. If the report contains a
significant bibliography or literature survey, mention it here.
17. KEY WORDS AND DOCUMENT ANALYSIS
(a) DESCRIPTORS - Select from the Thesaurus of Engineering and Scientific Terms the proper authorized terms that identify the major
concept of the research and are sufficiently specific and precise to be used as index entries for cataloging.
(b) IDENTIFIERS AND OPEN-ENDED TERMS - Use identifiers for project names, code names, equipment designators, etc. Use open-
ended terms written in descriptor form for those subjects for which no descriptor exists.
(c) COSATI FIELD GROUP - Field and group assignments are to be taken from the 1965 COSATI Subject Category List Since the ma-
jority of documents are multidisciplinaiy in nature, the Primary Field/Group assignment(s) will be specific discipline, area of human
endeavor, or type of physical object. The application(s) will be cross-referenced with secondary l'ield/Group assignments that will follow
the primary posting(s).
18. DISTRIBUTION STATEMENT
Denote releasability to the public or limitation for reasons UL _>r than security for example "Release Unlimited." Cite an> availability to
the public, with address and price.
19. & 20. SECURITY CLASSIFICATION
DO NOT submit classified reports to the National Technical Information servi;e.
21. NUMBER OF PAGES
Insert the total number of pages, including this one and unnumbered pages, but exclude distribution list, if any.
22. PRICE
Insert the price set by the National Technical Information Service or the Government Printing Office, if known.
EPA Form 2220-1 (9-73) (Reverse)
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