EB85-22775S
EPA/600/4-85/045
June 1985
REVIEW OF SAMPLING AND ANALYSIS METHODOLOGY
FOR POLYNUCLEAR AROMATIC COMPOUNDS IN
AIR FROM MOBILE SOURCES
by
C. C. Chuang and 3. A. Petersen
Battelle Columbus Laboratories
Columbus, Ohio 43201-2693
Contract No. 68-02-3487
Project Officer
Nancy K. Wilson
Methods Development and Analysis Division
Environmental Monitoring Systems Laboratory
Research Triangle Park, North Carolina 27711
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
-------
DISCLAIMER
The information 1n this document has been funded wholly or in part by
the United States Environmental Protection Agency under Contract 68-02-3487 to
Battel!e Columbus Laboratories. It has been subject to the Agency's peer and
administrative review, and 1t has been approved for publication as an EPA
document. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
i i
-------
FOREWORD
Measurement and monitoring research efforts are designed to anticipate
environmental problems, to support regulatory actions by developing an in-
depth understanding of the nature of processes that impact health and the
ecology, to provide innovative means of monitoring compliance with
regulations, and to evaluate the effectiveness of health and environmental
protection efforts through the monitoring of long-term trends. The
Environmental Monitoring Systems Laboratory, Research Triangle Park, North
Carolina, has responsibility for: assessment of environmental monitoring
technology and systems for air, implementation of agency-wide quality
assurance programs for air pollution measurement systems, and supplying
technical support to other groups in the Agency including the Office of Air
and Radiation, the Office of Toxic Substances, and the Office of Solid Waste.
The determination of human exposure to toxic organic compounds is an
area of increasing significance to EPA. The state-of-the-art survey of
sampling and analytical methodology presented in this report provides an
initial step toward measurement of, and understanding the extent of human
exposure to, an important class of chemicals — the polynuclear aromatic
compounds — in air.
Thomas R. Hauser, Ph.D.
Director
Environmental Monitoring Systems Laboratory
Research Triangle Park, North Carolina 27711
-------
ABSTRACT
The objective of this program was to review and reconmend test compounds
and sampling and analysis methods for a future EPA study of polynuclear
aromatic hydrocarbons (PAH) in microenvironments.
A literature survey was performed by a computer search of nine data
bases: Chemical Abstracts (1967-1983), Enviroline (1971-1983), Pollution
Abstracts (1970-1983), APTIC (1966-1978), NTIS (1964-1SB3), Engineering Index
(1970-1983), BIOSIS (1970-1983), Excerpta Medica (1970-1983), and Medline
(1970-1983). Additional materials representing state-of-the art practice were
also reviewed.
Review of PAH profiles in ambient air indicated that concentrations of
PAH were generally higher in winter than summer and varied with climate and
between sampling sites within an urban area. Levels of several PAH were found
to be proportional to traffic density. Studies of the biological activity of
ambient air samples showed that some PAH and their nitrated derivatives are
extremely carcinogenic and mutagenic. The following compounds were determined
to be the most prevalent and mutagenic or carcinogenic in ambient air and were
recommended for the future EPA study: phenanthrene, pyrene,
cyclopenta(c,d)pyrene, benzo(a)pyrene, dibenz(a,h)anthracene, 1-nitropyrene,
fluoranthene, benz(a)anthracene, benzo(e)pyrene, benzo(g,h,i,)perylene,
coronene, and 3-nitrofluoranthene.
In the review of PAH sampling methods, collection of both gaseous and
particulate-bound PAH was determined to be necessary to accurately
characterize health effects of PAH in ambient air. Host studies have used
filters to sample particulate-bound PAH and adsorbents to collect vapor phase
PAH. The major sampling problems encountered 1n these studies were PAH losses
due to volatilization and reactivity. A modified high volume (Hi-Vol) sampler
which can remove large particulates (>10 nm) and collect both particulate and
vapor phase PAH was reconsnended for the EPA study.
Both screening and analytical methods for PAH determination were
reviewed. Luminescence techniques, thin layer chromatography, ultraviolet
(UV) spectroscopy, and a fluorescence spot test have been successfully applied
in previous PAH screening studies and were recomnended for the EPA study. For
PAH analysis, combined gas chromatography/mass spectrometry (GC/MS) with
either electron impact or negative ion chemical ionization was found to
provide higher sensitivity and specificity than other techniques reviewed and,
despite the high cost, was recommended for the future study.
This report was submitted in fulfillment of Contract 6B-02-3487 by
Battelle Columbus Laboratories under the sponsorship of the U.S. Environmental
Protection Agency. This report covers a period from March 1, 1983 to
September 30, 1983, and work was completed as of November 30, 1983.
iv
-------
CONTENTS
Foreword iii
Abstract iv
Tables vi
Abbreviations vii
Acknowledgement viii
1. Introduction 1
2. Conclusions and Recommendations 3
3. Polynuclear Aromatic Hydrocarbon Profiles and
Biological Activity from Ambient Air Samples 6
An Overview of Polynuclear Aromatic Hydrocarbon
Profiles in Ambient A1r 6
Contribution of Mobile Sources to Polynuclear
Aromatic Hydrocarbon Contamination in
Ambient Air 7
Biological Activity of Ambient Air Samples 9
Selection of Pertinent Polynuclear Aromatic
Hydrocarbons and Derivatives for an EPA
Experimental Exposure Study 12
4. Sampling Methodology for the Collection of
Polynuclear Aromatic Hydrocarbons 24
Introduction 24
Sample Considerations 25
Sampling Devices 27
5. Chemical Analysis Methodology 37
Introduction 37
Chemical Analysis Methods 37
Screening Methods 45
References
Section 3 17
Section 4 32
Section 5 47
v
-------
TABLES
Number Page
1 PAH Candidate Compounds for Measurement in the EPA
Pilot Study 16
vi
-------
LIST OF ABBREVIATIONS
BAP
benzo(a)pyrene
BEP
benzo(e)pyrene
BKF
benzo(k)fluoranthene
CI
chemical ionization
EI
electron impact
FID
flame ionization detection
FLNS
fluorescence line narrowing spectrometry
FT
Fourier transform
GC
gas chromatography
GC/MS
gas chromatography/mass spectrometry
HI-VOL
high volume sampler
HPLC
high performance liquid chromatography
HR
high resolution
IR
infrared
LO-VOL
low volume sampler
MS
mass spectrometry
NCI
negative ion chemical ionization
NMR
nuclear magnetic resonance
PAH
polynuclear aromatic hydrocarbon
RTP
room temperature phosphorimetry
SF
synchronous fluorescence
SIM
selected ion monitoring
SL
synchronous luminescence
TLC
thin layer chromatography
UV
ultraviolet
XEOL
X-ray excited optical luminescence
vii
-------
ACKNOWLEDGEMENT
The financial support of the U.S. Environmental Protection Agency and
the encouragement and direction of Dr. Nancy K. Wilson are gratefully
acknowledged.
vi i i
-------
SECTION 1
INTRODUCTION
The Methods Development Branch is developing sampling and analytical
methodology for an experimental study of human exposure to polynuclear
aromatic hydrocarbons (PAHs) and PAH derivatives in ambient air within
microenvironments, emphasizing those which originate from mobile sources. The
form and concentration 1n which these PAH materials appear in micro-
environments are matters of Increasing interest and importance because of the
increasing use of diesel powered vehicles. Of particular concern is the
presence of nitrated PAHs in diesel exhaust. PAHs, especially pyrene, have
been reported to react readily with nitrogen oxides to form nitrated
derivatives, which are powerful direct acting mutagens. Both the PAHs and
nitrogen oxides are present in combustion emissions; thus the formation of
nitroaromatics in these emissions or in subsequent atmospheric reactions is
possible. In recent studies conducted by Battelle Columbus Laboratories,
nitrated PAHs have been identified in urban air particulate samples. Reliable
sampling and analytical techniques need to be established before potential
effects of PAHs and PAH derivatives on the environment can be assessed.
The specific objectives of this project were to survey and review the
current knowledge of PAHs found in ambient air and to use the results of the
review to develop a design and analytical methodology for an experimental
study of human exposure to PAH found in ambient air within microenvironments.
The first phase of this project is a review of the available literature
to determine:
• Sampling and analysis methodology for PAHs in ambient air
• Specific PAH compounds and subclasses of the PAHs that are
potentially most important because of their long-term health risk
• PAH profiles from specific mobile sources that can be used to
relate the PAH concentrations in air to those sources.
A literature survey was performed by a computer search of nine data
bases:
Data Base Years Searched
Chemical Abstracts 1967-1983
Enviroline 1971-1983
Pollution Abstracts 1970-1983
APTIC 1966-1978
1
-------
Data Base
Years Searched
NTIS
1964-1983
1970-1983
1970-1983
1970-1983
1970-1983
Engineering Index
BIOSIS
Excerpta Medica
Medline
Because the citations obtained from Chemical Abstracts listed only the authors
and topics, a manual search of the abstracts of those topics of interest was
performed. To collect information that might have been missed in the computer
search, a manual review was also conducted .of other sources considered to
represent current state-of-the-art practice, such as handbooks, manuals, and
research reports published by the U.S. EPA and recognized professional organ-
izations. Over 1000 citations were obtained as a result of both computer and
manual searching. Abstracts and citations considered most relevant to the
subject area were reviewed and divided into two subsets, sampling methods and
analysis methods, for further evaluation. Photocopies of some important
articles were obtained to allow for a more critical review than abstracts
alone provided.
The results of this review are presented in the following three
sections:
• PAH profiles and biological activity from ambient air samples
• Sampling methodology for the collection of PAHs
• Chemical analysis methodology.
The relative importance of PAHs that are found in ambient air and that
originate from mobile sources, in terms of their long-terra health risk, is
addressed in the first section. Sanqsling, analytical and screening
methodologies for the measurement of PAHs and PAH derivatives that may be
suitable for a U.S. EPA proposed experimental study are identified and
evaluated in the other two sections. These methodologies will be used to
guide the development of an experimental plan for a human exposure study.
2
-------
SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
Several important characteristics of PAH profiles in ambient air and
their biological activity have been identified in this review. PAH
concentrations in ambient air vary widely and in general are higher in winter
than in summer. The concentrations of PAH compounds also vary between
sampling sites within an urban area and vary with climate. However, levels of
several PAHs such as cyclopenta(c,d)pyrene, benzo(g,h,i)perylene, and coronene
are directly proportional to traffic density. These compounds can be used,
therefore, as indicators to identify the origin of mobile source contamination
within microenvironments. Based on these characteristics, such compounds
sJiould be considered for monitoring in the EPA experimental study-
Several carcinogenic and mutagenic PAHs and PAH derivatives found in
ambient air should also be investigated in the EPA study. Benzo(a)pyrene,
benzoflucranthenes, cyclopenta(c,d)pyrene and dibenz(a,h)anthracene are known
carcinogens and therefore should be considered important compounds to be
monitored in the future study.
Nitropyrenes and nitrofluoranthenes are potent d.. jct-acting mutagens
and have been identified in both ambient air and automobile exhaust.
Dinitropyrene and hydroxynitropyrene are two materials with the highest
mutagenicity known to date and have been found in mobile sou.ce emissions.
While these two compounds have not yet been found in ambient air, they will
probably be found in microenvironments polluted by these sources.
Based on the available information, the following PAH compounds are
potential candidates to be monitored in the EPA experimental study:
phenanthrene
fluoranthene
pyrene
benz(a)anthracene
cyclopenta(c,d)pyrene
benzo(e)pyrene
benzo(a)py;sne
benzo(g,h,i)pery1ene
dibenz(a,h)anthracene
coronene
1-ni tropyrene
3-nitrofluoranthene
benzofluoranthenes
indeno(l,2,3-c,d)pyrene
3
-------
Monitoring for the above species would provide a general characterization of
PAH concentration in ambient air. The measurement of these compounds can be
used to assess the PAH profile in a wide variety of microenvironments,
including those containing emissions from mobile and stationary sources.
Furthermore, the same compounds can be used to assess the PAH concentration
within residential sites. For this application, it would be highly desirable
to correct for PAH contributed by tobacco smoke. This correction can be made,
1f a correlation exists between PAH compounds and several tobacco smoke pro-
ducts such as quinoline and isoquinoline. If such a correlation exists, then
an adjustment of the PAH concentration due to tobacco smoke can be made.
Thus, by including tobacco smoke marker compounds in the list of compounds to
be monitored, residences and work places can be included as microenvironments.
Sampling methods used in the EPA future study must collect repre-
sentative samples of potentially harmful PAHs in ambient air and must also
minimize sampling losses frequently encountered with PAHs. PAHs exist in
vapor and particulate phases In the atmosphere, and most particle-bound PAHs
are found in the submicron range. These small particles also produce a major
percentage of the mutagenic activity of airborne particulate matter (43,45).
Both the vapor and respirable particle-bound PAHs should be considered for
collection, and an appropriate sampling and analysis system should be designed
for the experimental study.
PAH losses in sampling are mainly due to volatilization and reactivity
with NO2, O3, and UV radiation. Volatilization of PAHs cannot be avoided, but
can be minimized by the use of back-up traps in the sampling system for
collection of vapor phase material. Some reactive PAHs are believed to
undergo atmospheric reaction, such as nitration, to convert PAHs to nitro
PAHs. Erroneous results will occur if these reactions continue during the
sampling and analysis procedure. In general, reactivity mechanisms of PAHs in
the atmosphere are not well defined, and a simple solution to eliminate
reactivity losses in sampling has not yet been demonstrated. A device to
remove O3 and NO2 prior to particle sampling should be considered to minimize
this degradation.
The recommended sampling device for the EPA experimental study is a
modified Hi-Vol sampler. With a properly designed sampler inlet, a modified
sampler can remove larger particles {>10 um) before passage of the air sample
through the collection system. The collection system should consist of a
filter medium to collect particulate matter and a solid sorbent cartridge to
trap vapors. Proper sampling procedures need to be designed and validated to
avoid volatilization losses and reduce reactivity problems.
The procedures to be developed should consider the following parameters:
¦ Sampler configuration
• Sampling time
« Sampling temperature
« Sampling flow rate
• Filter face velocity
• Frequency of samples
• Quantity of sample necessary for measurement
4
-------
Once ranges have been established, the operation of samplers can be optimized
for the specific site selected.
Rapid screening methods for PAHs identified in this review include
a sensitized spot test, UV spectroscopy, TLC with fluorescence and/or UV
detection, and luminescence techniques.
Several analytical techniques such as HPLC with UV and/or fluorescence
detection, GC/FID, and GC/MS have been used successfully to measure PAHs in
ambient air and can be considered for the EPA experimental study. The HPLC
technique is very sensitive and less expensive than GC/MS technique. It may
be possible to determine PAHs using HPLC methods without sample cleanup. If
so, it may be possible to perform HPLC analyses in the field. No reference
has been found describing the use of synchronous fluorescence (SF) detection
with HPLC for the determination of PAHs in air. This technique offers several
advantages in terms of improved sensitivity and specificity. Therefore,
development and evaluation of synchronous fluorescence detection with HPLC is
also suggested for the future study. It should be noted that single column GC
or HPLC analyses employing single detectors do not give unambiguous results,
and confirmation of these analytical results with specific techniques such as
GC/MS is necessary.
Capillary column GC/FID has been demonstrated to be useful as a routine
analytical tool for PAH determinations. A sample cleanup procedure is
required to remove the interference from aliphatic hydrocarbons. Few
analytical methods for detection of nitro PAHs are reported in the literature.
The negative ion CI GC/MS technique is very sensitive, but requires the use of
expensive and sophisticated equipment. Therefore, less expensive methods such
as GC and/or HPLC techniques should be developed and evaluated for the
determination of nitro compounds in the future study. In the future EPA
experimental study—for the most important sample types, which demonstrate
unusually high mutagenicity and/or carcinogenicity ~ more sophisticated
analytical techniques (such as EI GC/MS and NCI GC/MS) will be -equired to
provide a more complete chemical characterization.
5
-------
SECTION 3
POLYNUCLEAR AROMATIC HYDROCARBON PROFILES AND
BIOLOGICAL ACTIVITY FROM AMBIENT AIR SAMPLES
AN OVERVIEW OF PAH PROFILES IN AMBIENT AIR
Considerable infonnation(l~39) is available in the literature describing
the profiles* of PAHs from various sources in ambient air particulate
material. The results of a literature survey indicate that PAHs in ambient
air are generally found in greater amounts in winter than in summer. Only one
reference(l) cited conflicting results that coronene and 1,2,3,4-dibenzopyrene
in heavy traffic were relatively more abundant in sunnier than in winter. The
increased PAH concentrations in winter are mainly due to emissions from
residential heating systems, and the low summer concentrations of PAHs may be
due to photochemical degradation and/or^ sample loss from higher sampling
temperatures. Valori and coworkers(12) analyzed samples collected from
polluted air 1n Rome. These researchers observed that the highest PAH levels
occurred in winter months during morning rush hours. They attributed the PAH
to domestic heating and automotive traffic.
Another general trend observed was that the benzo(a)pyrene (BaP)
concentrations in air particulate matter appear to have declined in the past
several years. Faoro and Manning(^>3) investigated BaP and benzene-scluble
fraction (BSO) concentrations in ambient air particulate material collected by
the National Air Surveillance Network (NASN) for the 1960-1977 period. The
data indicated that concentrations of BaP and BSC declined consistently from
1960-1977 at most of the urban and background sites studied. For example,
average BaP concentrations declined about 50 percent, from 4 ng/m3 in 1S67 to
2 ng/m3 in 1972. The authors concluded that local open burning ordinances,
auto mobile emission controls, and decreasing coal usage are probable factors
contributing to the observed trend. It is possible that the large changes in
analytical methodology over this period may also have contributed to the
apparent decline in BaP and BSO concentrations.
Another observation of this survey was that the concentrations of
individual PAHs obtained from different sites varied widely, from 0.1 ng/m3
to 100 ng/m3. Several studies(4>10) have been conducted in Japan to evaluate
the PAH content in ambient air of various Japanese cities. In some
*The term profile in this report represents the value of the concentrations
of individual PAHs and/or the relative values of the concentrations of
individual PAHs vs time or location in a sample.
-------
studies,(4,6) average BaP concentrations in Osaka air (1968-1969) were found
to be 30-60 ng/m3, which is much higher than the concentrations found in
American cities. The concentration of BaP decreased to 24 ng/m3 in Osaka in
1970.(7) The characteristic seasonal concentration variation (high winter/low
Sumner) was also observed in these studies. One study(5) indicated that BaP
concentrations in the commercial district of a Japanese city were 14.0 ng/m3
in winter, 9.4 ng/m3 in autumn, 5.7 ng/m3 in spring, and 2.7 ng/m3 in simmer.
In another study,(10) averaqe BaP concentrations within the city of Wakayma
were found to be 4.6 ng/m3 in residential areas, 5.0 ng/m3 in industrial
regions, and 1.6 ng/m3 in agricultural areas. Several studies(14-22) have
also been conducted to measure PAHs in the air in other countries. The levels
of PAHs measured depended on the sites sampled.
PAH concentrations were observed to vary with different climatic
regions. One study(H) was performed to investigate the content of PAHs in
air 1n ten Polish towns situated in different climates. The PAH levels varied
during 1966 in the following ranges: BaP, 29-133 ng/m3; pyrene, 34-167 ng/m3;
benzo(e)pyrene, 14-80 ng/m3; and benzo(g,h,i)perylene, 34-124 ng/m3.
CONTRIBUTION OF MOBILE SOURCES TO PAH CONTAMINATION
IN AMBIENT AIR
The major emission sources of PAHs are heat-generation sources, such as
burning coal, oil, and gasoline; motor vehicle exhaust; and industrial
processes. Olsen and Haynes' review(-3) showed that heat generation accounts
for more than 85 percent of the PAHs in air. Similar conclusions were drawn
in a recent review by the National Research Council,(24) that pointed out that
data assembled by the U.S. EPA in 1974 led to the estimate that 97 percent of
the BaP emitted in the United States could be attributed to stationary fuel
combustion. The major contributors are coke ovens, refuse fires, and the
inefficient combustion of coal in residential furnaces. Mobile sources are
not the major sources of PAH contamination in ambient air. However, in a
microenvironment such as a parking lot, underground mine, tunnel, or heavy
traffic area, mobile sources may be the main contributors of PAH
contamination.
Bosco and coworkers(25-27) determined PAH levels in the atmospheric dust
of the city of Siena, Italy. The concentrations of most of the identified
PAHs showed a significant decrease when a part of Siena was closed to motor
traffic. Since the city of Siena does not have heavy industry, the reduction
of automotive traffic was the major reason for the decline of PAHs.
Characterizing the contributions of mobile sources to PAH contamination
in the air is complicated. According to the available information in the
literature, two methods can be used to identify mobile sources of PAHs in the
atmosphere. These methods are choosing characteristic compounds such as
cyclopenta(c,d)pyrene, benzo(g,h,i)perylene and coronene as indicators for
mobile sources; and using trace materials, such as lead, vanadium, and carbon
monoxide as indicators for mobile and non-mobile sources.
7
-------
Several references^,28-35) are available on the use of a specific PAH
as an indicator for mobile sources. Sawicki and coworkers(28) examined the
air of 14 American cities for the following PAHs: pyrene, BaP,
benzo(e)pyrene, benzo(k)fluoranthene, perylene, benzo(g,h,i)perylene,
anthanthrene and coronene. Based on their experimental data, the ratio of BaP
to benzo(g,h,i)perylene was 0.6 and the ratio of BaP to coronene was 1.0 in
the following types of samples: automobile exhaust soot from a tailpipe, air
from a Cincinnati automobile safety lane, and air from a Cincinnati downtown
garage. The same group also demonstrated that BaP concentrations in air
particles were elevated in urban and nonurban areas in and around the eastern
coal mining belt; for example, the BaP/coronene ratios were in the range of
1.7 to 8.3 for the winter months. The authors proposed that the ratios of BaP
to benzo(g,h,i)perylene and to coronene could be used as possible indicators
of air pollution due to automobile exhaust fumes or coal combustion pollution.
One study(13) showed that the profile of PAHs in Pittsburgh air was similar to
those reported by Sawicki for other American cities,(28) with the exception of
a high value of benz(a)anthracene (BaA), which ranged from 0.8 to 37 ng/m3.
A similar study was conducted by a Japanese group,(4) who investigated
PAHs in Osaka air. The BaP/benzo(g,h,i)perylene and BaP/coronene ratios for
urban air and automobile exhaust followed the same trend observed by Sawicki.
This group also suggested that these ratios can be considered as indicators of
air pollution sources. Average BaP concentrations were 30-60 ng/m^, which are
considerably higher than the BaP concentrations found in American cities.
Gordon and caworkers(29,30) evaluated the patterns in airborne
particulate matter at four Los Angeles sites. The concentrations of coronene
correlated well with traffic density. The PAH patterns, normalized to coro-
nene, were similar for three sites and resembled patterns for automotive
exhaust previously studied by the same group. The fourth site had a dis-
tinctly different pattern, reflecting, local sources of non-automotive PAHs.
Another study conducted by Katz and Chan(31) showed that in Hamilton,
Toronto, and several other Ontario cities, benzo(g,h,i)perylene was the most
abundant PAH where motor vehicle traffic was a major source of air pollution.
However, BaP represented an important fraction of the PAH content in urban
areas where the dominant source was coal combustion.
Suda and coworkers(32) obtained similar results, showing that mobile
sources were the major contamination source based on the ratio of the total
atmospheric PAH level to the benzo(g,h,i)perylene level. The result is in
fairly good agreement with that based on the average PAH levels in automotive
exhaust from 26 Japanese cars.
Recently, Masclet and colleagues(33) measured PAHs in the airborne
particulate material in Paris, in December 1981 and January 1982. They also
observed that the relative abundance of PAHs varied with the main particulate
source on each sampling day, i.e., automobile traffic in December and home
heating in January. In Sorensen and Vester's study,(34) it was expected that
the center of Copenhagen would be polluted mainly with PAHs of high molecular
weight, such as benzo(g,h,i)perylene discharged from motor vehicles. However,
8
-------
the ratio of BaP to benzo(g,h,i)perylene ranged from 0.2 to 4.4, benzo(g,h,i)-
perylene was considerably lower than expected, and no correlation was found
between the concentrations of PAH in the air of Copenhagen and meteorological
data. In addition, one single pollution source could not be identified.
Grimmer and coworkers(35) u$ed BeP measurements as a basis to construct
PAH concentration profiles of several areas. Profiles of PAHs from automobile
emissions and from measurements in a traffic tunnel were similar, with
cyclopenta(c,d)pyrene the most abundant PAH. Cyclopenta(c,d)pyrene can also
be an indicator for mobile source contamination.
The use of trace elements such as lead and vanadium to identify sources
of pollutants in the atmosphere was described in a recent National Research
Council review.(24) Colucci and Begeman(36-38) conducted several studies to
determine the contribution by automobiles to the PAHs in the air of cities
such as New York, Detroit and Los Angeles. They used tracer elements to
identify automotive and non-automotive sources and calculated correlation
coefficients of BaP with carbon monoxide (CO) (a motor vehicle tracer), with
lead (a gasoline vehicle tracer), and with vanadium (an oil tracer). Vanadium
concentrations were two times higher in winter than in summer, indicating that
the higher amount of BaP was contributed by the combustion of residual fuels
used for heating. In another study(39) of air pollution from automobile
exhaust, gases in an underground parking garage were measured. Levels of CO
exceeding 200 ppm were recorded and indicated that CO levels can be an
indicator for mobile source contamination.
BIOLOGICAL ACTIVITY OF AMBIENT AIR SAMPLES
The biological activities of PAHs and their derivatives present in
ambient air, diesel exhaust and other sources have been reviewed by the
National Research Council in 1972,(40) 1981,(43-) and 1983(24) an
-------
matter is in the smaller particle size range, below 10 wm. Several investi-
gators^,^) have shown that both metabolically-activated and direct-acting
mutagenic compounds are present in air particulate matter. These authors
agreed that PAHs are not the major mutagenic factors associated with air
particulate matter. In addition, they have shown that air particulate matter
is more mutagenic at industrial and urbanized sites than at rural sites.
Recently, Flessel and coworkers(47) compared the mutagenicity of air
samples from sites in Contra Costa County, California with different degrees
of industrialization and cancer rates. Contra Costa County is one of 39
counties in the U.S. that have been shown to have high cancer mortality rates.
These studies all indicated a higher mutagenic activity in samples from the
more urbanized or industrialized sites. However, detailed later studies found
there was no identifiable effect on cancer risk from air pollution in the
county.(47 a)
In a year-long study at a Chicago school site, Commoner and
colleagues(48) showed that a major parameter affecting airborne particulate
mutagenicity was the wind direction. In this study, a plot of wind directions
versus relative mutagenic activity showed that wind directions of either
northwest or east produced air particulate samples with the greatest
mutagenicity. Moller and Alfheim(49) studied the mutagenicity of airborne
particles from two locations in Oslo over a three-month period. They observed
higher mutagenicity in February (i.e., during the heating season) than in
March and April. They also reported that meteorological conditions may
influence the mutagenicity levels; for example, the mutagenicity
(revertants/cm^ of air sampled) was highest on cold clear days with little
wind.
In certain cases, studies can be designed to identify specific emission
sources that contribute to the mutagenicity of the ambient particulate organic
matter. Moller's group(50) conducted another study on the mutagenicity of
airborne particles in relation to traffic and air pollution parameters such as
CO, NOv, and PAHs. The results indicated that the mutagenicity of daytime
street-level samples, that originated in motor vehicle exhaust in an area with
dense traffic, was 4-20 times higher than that of simultaneously collected
samples at roof level or in the park. Furthermore, the mutagenicity at street
level varied with traffic density, while the activity of samples from roof
level and from the park showed no such correlation. Lewtas(51) also compared
the mutagenic activity of organic compounds from particles of less than 1.7 nm
diameter collected at Los Angeles freeway sites, both upwind and downwind.
The particles collected downwind, presumably from the automobiles and trucks
on the freeway, were significantly more mutagenic than those collected upwind
originating from the Pacific Ocean. These authors agreed that both gasoline
and diesel engine exhaust from automobiles, buses, and trucks contribute to
the mutagenicity of ambient air particles.
Recently, nitrated PAHs have been identified in extracts of parti-
culate material from diesel engine exhaust and urban air. Several of these
nitrated PAHs are strong direct-acting mutagens in Salmonella tests,(52-56)
10
-------
and are carcinogenic in animal experiments(57) as well as mutagenic in test
systems using mammalian cells.(58)
Certain nitrated PAHs (e.g., 1,8-dinitropyrene) are extremely potent
frameshift bacterial mutagens. Concern was expressed by Rosenkranz and
coworkers(59) that bacterial mutagenesis assays may overestimate the
mutagenicity of nitrated PAHs in diesel emissions. The importance of
evaluating the mutagenic activity of these emissions in eucaryotic organisms,
mammalian cells and whole animals was emphasized. Lewtas(*8) conducted a
review to compare the microbial mutagenicity, maircnalian cell mutagenicity, and
mouse skin tumorlgenicity of the extractable organic compounds from diesel
particles. The results indicated that there is generally good agreement among
the bacterial mutagenesis assays, mammalian cell assays, and skin
carcinogenesis assays. The author suggested that bacterial mutagenesis assays
do not overestimate the mutagenic activity of these nitro PAHs.
Fukino's group(53) studied the mutagenicity of airborne particles in the
Ames Salmonella system. The results suggested that emissions from auto-
mobiles, home heaters, and power plants may be primary sources of atmospheric
direct-acting mutagens. However, secondary direct-acting mutagens may be
partly formed by the nitration of PAHs with NOj in the atmosphere, because the
measured concentrations of BaP and NO2 were higher in the samples producing
the highest direct-acting mutagenicity. Madsen and coworkers(54,55) collected
air particulate material at three stations in central Copenhagen with
different contributions from automobile exhaust emissions. The three sampling
sites were street level, 22 m above street level, and within a hospital zone
at street level. Two classes of mutagens were identified: anon-polar
extract rich in PAHs as well as other metabolically-activated mutagens and a
polar extract containing direct-acting mutagens. Based on the covariance
between lead and mutagenicity, the authors suggested that at all stations the
mutagenicity of the nonpolar extract was dominated by automobile exhaust
products. The polar extract was relatively less Influenced by traffic
emissions. This may be because the activity of this polar fraction was mainly
attributed to non-automotive emissions and/or emissions from stationary
sources possibly transformed by atmospheric reactions.
Recently, Pitts(60) investigated the diurnal variations in the
mutagenicity of ambient particles collected at the same time at three sites in
southern California. At each sampling site five high-volume samplers were run
for 24 hours with filter changes every 3 hours, and a sixth sampler was
operated for the entire 24 hours without filter replacement. The data showed
good agreement between the activities of the experimental 24-hour samples and
the estimated 24-hour activities calculated from the corresponding three hour
samples. These data suggest thet chemical transformations of mutagenic
material collected on the filters are either very fast or very slow relative
to the time scale used in c^ese experiments. The three hour average mutagenic
densities correlated well >.ith CO, N0X, and lead levels.
11
-------
In a study by Dehren, Pitz, and Tomingas,(61) a chemical fractionation
scheme was used to separate crude air particulate material into cyclohexane
and methanol extractable frections. An alumina column was used to fractionate
the cyclohexane extract further into a purified cyclohexane fraction con-
taining PAHs and a 2-propanol fraction containing azo-heterocyclic compounds.
The highest mutagenic response was found in the 2-propanol and methanol
extracts, neither of which contained PAH compounds.
The combination of a chemical fractionation scheme with an Ames bioassay
system has been shown to be an increasingly powerful tool for the
identification of potential carcinogens in complex extracts of air particulate
material. Battelle(62) conducted a joint study with the U.S. EPA at Research
Triangle Park, NC, to develop a fractionation scheme to separate extracts of
air particulate matter from Washington, D.C. into acidic, basic, aliphatic,
aromatic, moderate polarity, and high polarity fractions. The acidic fraction
accounted for about 50 percent of the mutagenic activity with and without
activation of the total extracts. Mononitrated PAHs, including nitro-
naphthalene, nitrophenanthrene isomers, nitrofluoranthene, nitropyrene, and
2,7-dinitrofluorene, were found in the aromatic and polar neutral fractions.
The high activity in the acidic fraction indicated that, besides PAHs and
nitrated-PAHs, some other types of compounds were present in the extracts of
air particulate material that may be strong mutagens and/or carcinogens.
Recently, one group(63) reported that a strong mutagen, hydroxynitropyrene,
was present in diesel exhaust extracts. Because of the acidic properties of
the hydroxy group, these types of compounds may be present in the acidic
fraction of the extracts of air particulate material and contribute to the
mutagenicity. So far, no study has been performed to characterize these types
of compounds in air particulate material, and it would be worthwhile to pursue
such studies.
Several limitations to data interpretation were identified in the
mutagenicity studies. Air particles are complex mixtures and may contain hun-
dreds of compounds. In such a complex matrix, effects which inhibit or
increase the mutagenicity of an individual compound may occur. The mechanisms
for these effects are being studied.(64-66) Toxicity of compounds in the com-
plex mixture, as well as the nature or composition of the mixture itself, can
mask mutagenicity. Artifacts generated by sampling procedures and sample
handling can lead to erroneous results. Huisingh and coworkers(®^) have
shown that extracts of particulate material from diesel exhausts are more
mutagenic when extracted with dichloromethane than with cyclohexane. This
group also demonstrated a 50 percent loss of mutagenic activity as well as an
increase in toxicity for the extract upon storage (2 months at 4°C). In
general, quinones and ketoaromatics are toxic but not mutagenic. It is
possible that nitroaromatics may have originally accounted for a larger
percentage of the activity, but with storage, many of the nitroaromatics may
have been oxidized to quinones and ketoaromatics.
The results of a Battelle study(62) supported this postulate in that
the measured mutagenic activity of the stored diesel exhaust extract decreased
significantly while the toxicity increased over the two-year storage.
12
-------
Furthermore, it was demonstrated that the 1-nitropyrene concentration
decreased about 75 percent during this storage. For the other identified
nitro PAHs, half showed at least a 75 percent loss in concentration during the
storage period. It is recommended, therefore, that a standard procedure for
sample storage and handling be formulated and instituted. Post-collection
reactions cannot be eliminated, but by using standardized procedures can be
minimized.
SELECTION OF PERTINENT PAHS AND DERIVATIVES
FOR AN EPA EXPERIMENTAL EXPOSURE STUDY
Based on the available information about PAHs and their derivatives
present in air particulate matter, the following compounds are potential
candidates for measurement in the EPA experimental study of human exposure to
mobile source emissions found in ambient air within microenvironments:
Pyrene Benzo(e)pyrene
Fluoranthene Benzo(a)pyrene
1-Ni tropyrene Benzo(g,h,i)perylene
3-Nitrofluoranthene Indeno(l,2,3-c,d)pyrene
Benz(a)anthracene Di benz(a.h)anthracene
Coronene Dinitropyrenes
Chrysene Dinitrofluoranthenes
Cyclopenta fc,d)pyrene Hydroxyn i tropyrenes
Benzof1uoranthenes
A recent study by Grimmer and his group(68) showed that PAHs with more
than three rings accounted for a large percentage of the total carcinogenicity
in crankcase oil, automobile exhaust condensate and flue gas condensate as
shown by the mouse-skin painting test. Similar results obtained by another
group'") indicated that PAHs with four to six rings showed the strongest
experimental carcinogenicity. The experiments were conducted by subcutaneous
injection of extracts of automobile exhaust condensates, coal furnace emis-
sions and air-borne particles, and different fractions of these extracts. The
same trend was also reported in several review articles.(24,43) For this
reason, we suggest that emphasis should be placed on PAH with four or more
rings in the experimental study.
Both pyrene and fluoranthene, in relatively large amounts compared to
other PAH species, are found in air particulate matter and automobile exhaust
emissions. These compounds do not show carcinogenic activity, but have some
mutagenic activity in Jjn vitro animal tests.(24] Their derivatives, such as
nitrated pyrene and fluoranthene, are strong direct-acting mutagens and both
nitro compounds are present in extracts of air particulate material(62) and
diesel exhaust emissions.(71) These compounds are typically present, however,
at 0.01 to 0.1 times the levels of their parent PAHs. At this point, the
measurement of parent compounds is as important as is the measurement of their
nitro derivatives for the experimental study. This is particularly true if a
correlation can be obtained between the parent compounds and their nitro
13
-------
derivatives. It may be possible to infer the riitro PAH concentration based on
the measurement of parent compounds within the environment that is monitored.
Recently, Battelle(62,71) performed a joint study with the U.S. EPA in
which both 3-nitrofluoranthene and 1-nitropyrene were detected and quantified
in extracts of diesel exhaust particulate material, but the levels of 1-
nitropyrene were 10-20 times greater than the levels of 3-nitrofluoranthene.
It is noteworthy that 1-nitropyrene and 3-nitrofluoranthene were both detected
and quantified in extracts of ambient air particulate matter, but the 3-
nitrofluoranthene was present at levels approximately equal to or greater than
the levels of the 1-nitropyrene. This concentration difference between diesel
exhaust and ambient air samples suggests that 3-nitrofluoranthene is either
more stable than 1-nitropyrene or is more readily formed through atmospheric
transformation reactions than 1-nitropyrene. In at least one bacterial
mutagenesis test strain, TA98, 3-nitrofluoranthene elicited twenty-five times
the mutagenic activity level of 1-nitropyrene. Considering the relative
concentration levels and the relative mutagenicity levels, 3-nitrofluoranthene
may be the more significant nitro PAH for monitoring in ambient air.
The 1,3-, 1,5-, and 1,8-dinitropyrenes are strong direct-acting
mutagens, with the 1,8- species being the most potent. The presence of these
compounds in diesel exhaust extracts has been confirmed by several
studies.(72,73) Pedersen and Siak (73) estimated that 15-20 percent of the
total mutagenic activity of the extract may be contributed by these dinitro-
pyrenes, in addition to as much as 24 percent contributed by l-n1tropyrene.
So far, no evidence has been shown that dinitropyrenes are present in extracts
of ambient air particulate material. The presence of dinitrofluoranthenes in
either diesel exhaust or air particulate materials has not been reported in
the literature. It is likely that dinitrofluoranthenes are present in diesel
exhaust. More studies are needed in this area.
Recently, one group reported that hydroxynitropyrene had mutagenicity
equivalent to that of the dinitropyrenes and was identified in diesel exhaust
emissions.(74) it is essential to investigate whether hydroxynitropyrene is
present in ambient air particulate material.
Benz(a)anthracene (BaA) and chrysene are both present in air particulate
matter and automobile exhaust. These compounds are also carcinogenic in
mouse skin tests. Furthermore, the methyl derivatives of these compounds
(e.g., 6-, and 7-methyl BaA, 5-methylchrysene) have strong carcinogenic
activity. We suggest that BaA and chrysene be monitored in the EPA
experimental study. If an unusually high amount of BaA and chrysene were
found in a sample from a polluted microenvironment, it would be worthwhile to
search for the highly carcinogenic methyl and/or dimethyl derivatives of these
compounds.
CycIopenta(c,d)pyrene is a known carcinogen and also has strong
mutagenic activity. Benzo(g,h,i)perylene and coronene are either weak
carcinogens or noncarcinogens. These three compounds have been identified in
ambient air. Furthermore, according to the PAH profile which was discussed on
14
-------
pages 7 and 8, these compounds may be indicators for mobile source
contamination. For this reason, these three compounds are considered import-
ant in the pilot study.
Benzofluoranthenes and benzo(e)pyrene occur in both ambient air and
automobile exhaust emissions. In repeated skin paintings, benzo(b)fluor-
anthene produces skin tumors in mice, and benzo(j)fluoranthene causes a high
incidence of skin carcinoma. Benzo(e)pyrene has shown a weaker response than
either benzo(a)pyrene or dibenzo(a,h)anthracene in the skin painting experi-
ments in mice, and it appears to be a weak carcinogen. One study(24)
indicated that repeated application of the weak carcinogen BeP to mouse skin
three times weekly with the carcinogen BaP resulted in a cocarcinogenic
effect, which enhances remarkably the carcinogenicity of BaP. In addition,
BeP is relatively more stable than BaP and can be used as a reference compound
to generate PAH concentration profiles.
Benzo(a)pyrene is present in ambient air as well as in mobile source
particulate matter. BaP is a known carcinogen and has indirect-acting mutagen
activity (with S9 activation). It is an important compound to be studied.
Oibenz(a,h)anthracene has shown carcinogenic activity, and small doses
of dibenz(a,h)anthracene have a greater tumor promoting effect than do com-
parable doses of benzo(a)pyrene.('5) This compound is also found in ambient
air and automobile exhaust. A list of PAHs which are potential candidates for
measurement in the experimental exposure study is suninarized in Table 1.
15
-------
TABLE 1. PAH CANDIDATE COMPOUNDS FOR MEASUREMENT IN THE EPA PILOT STUDY
PAH
Molecular Formula
(Weight)
Occurrence(fl)
Mobile Ambient
Exhaust A1r
Carc1nogen1c(b)
Activity
Relative 1n v1tro(c)
Mutagenic Activity
Animal Bacteria
Pyrene
Ci6Hio (202)
Y
Y
0
+
0
Fluoranthene
CieHlO (202)
Y
Y
0
+
++
l-N1tropyrene
C16H9NO2 (247)
Y
Y
+++
3-Nitrofluoranthene
CieHgNO? (247)
Y
Y
+++
Benz(a)anthracene
Ci8Hi2 [228)
Y
Y
+
+
++
Chrysene
C18H12 228)
Y
Y
+
+
+
Cyclopenta(c,d)pyrene
c18h10 (226)
Y
Y
+
++
++
Benzofluoranthenes
C20H12 (252)
Y
Y
++
Benzo(e)pyrene
C20Hl2 (252)
Y
Y
0/+
+
+
Benzo(a)pyrene
C20H12 (252)
Y
Y
++
++
++
Benzo(g,h,1 )per.ylene
C22H12 (276)
Y
Y
+
Indeno(l,2,3-c,d)pyrene
C2?Hi2 276)
Y
Y
+
D1benzo(a,h)anthracene
C22H14 (278)
Y
Y
+
+
+
Coronene
c24h12 (300)
Y
Y
+
D1n1tropyrenes
C16H8N2O4 (292)
Y
N
++++
D1n1trofluoranthenes
C16H8N2O4 (292)
N
N
++++
Hydroxynltropyrenes
C16H9NO3 (263)
Y
N
++++
(a) Y - Compound occurs In samples from given source.
N = Compounds does not occur In samples from given source.
(b) 0, no tumor; +, tumor 1n up to 335I5 of animals, ++, tumors 1n over 33% of animals.
(c) Benzo(a)pyrene mutagenicity set at ++.
-------
REFERENCES
SECTION 3
1. Kertesz-Saringer, M., Z. Morlin, K. Kollar, and E. Rako. Pollution of
Air With Polycyclic Hydrocarbons Originating from Traffic in Budapest.
Enerq. Atomtech. 26(10):46l-489, 480, 1973.
2. Special Report: Trends in Concentrations of Benzene-Soluble Suspended
Particulate Fraction and Benzo(a)pyrene 1960-1972. Report EPA-450/274-
022; NTIS, PB 238504/AS, Office of Air and Waste Management, Research
Triangle Park, NC, Office of Air Quality Planning and Standards p. 48,
1974.
3. Faoro, R. B., and J. A. Manning. Trends in Benzo(a)pyrene 1966-1977.
J. Air Pollution Control Assoc.. 31(1)^62-64, 1981.
4. Fujie, K. Gas Chromatographic Analysis of Polycyclic Aromatic Hydro-
carbons Associated with Particulates in Osaka Air. J. Japan. Soc. Air
Pollution,. 3(2): 126-133, 1966.
5. Watanabe, H., and K. Tomita. Carcinogenic Hydrocarbons in the Atmosphere
of Osaka City. Proc. (Part I) Intern. Clean Air Cong., London, (Paper
VIII/5), 1966. pp. 226-228.
6. Okuno, T. Evaluation for the Measurement of Polycyclic Aromatic
Hydrocarbons in Air. Proc. Res. Sect. Osaka Environ. Pollution Control
Center, l(l):25-30, 1970.
7. Nishikawa, Y., T. Fujii, and T. Okuno. Studies on the Atmospheric
Concentration of Polynuclear Aromatic Hydrocarbons in Urban Air. Proc.
Res. Sect. Osaka Environ. Pollution Control Center , 2:9-14, 1971.
8. Nishikawa, Y. Studies on the Atmospheric Concentration of Polynuclear
Aromatic Hydrocarbons in Urban Air-Results Obtained in 1971 (January-
December) . Proc. Res. Sect. Osaka Environ. Pollution Control Center,
3:7-10, 1972.
9. Akiyama, K., C. Nagashima, R. Takashi, K. Fujiya, H. Noushi, and M.
Nagasaki. Gas Chromatographic Analysis of Atmospheric Polynuclear
Aromatic Hydrocarbons in Metropolitan Tokyo. Paper presented at the
Japanese Society of Public Health, 32nd Annual Meeting, Fukushima, Japan.
Oct. 16-18,1974. CA82:144355K.
17
-------
10. Koike, S., A. Sakamoto, K. Katsuyama, S. Sakata, and K. Nikai. On the
Measurement Result of Polynuclear Hydrocarbons in Ambient A1r—on BaP.
Paper presented at the Lecture Meeting on Environmental Protection and
Pollution Prevention, 2nd, Tokyo, Japan. March, 1976. APTIC:101365
11. Just, J., S. Maziarka, and H. Wyszynska. Estimation and Effect of
Carcinogenic Material in Airborne Particulate Matter Collected in Some
Cities of Poland. Part I. Content of Ber.zo{a)pyrene and Other Aromatic
Polycyclic Hydrocarbons in the Particulate Hatter of Ambient Air in Ten
Pollish Towns. Roczniki Panstwoweqo Zakladu Hiqi. 18(6):638-654, 1967.
12. Valori, P., A. Grella, C. Melchiorri, and N. Vescia. Spectrophotometry
Determination of Aromatic Polycyclic Hydrocarbons. Further Data on the
Atmosphere of Rome. Nuovi Ann. Iqiene Microbiol. (Rome). 17(5):383-
414, 1966.
13. DeMaio, L., and M. Corn. Polynuclear Aromatic Hydrocarbons Associated
With Particulates in Pittsburgh Air. J. Air Pollution Control Assoc..
16(2):67—71, 1966.
14. Cleary, G. 0., and 0. L. Sullivan. Pollution by Polycyclic Aromatic
Hydrocarbons in the City of Sydney. Med. J. Australia. 52:758-763, 1965.
15. Lindskog, A., and E. Brostroem. Determination of Polycyclic Aromatic
Hydrocarbons in Airborne Particulate Matter in Geoteborg. Report No.
NORDISK PAH-PROSJEKT-11 NTIS, PB83-135426, Sentralinstitutt for
Industriell Forskning, Oslo, Norway, p. 21, June 1981.
16. Katz, M., T. Sakuma, and A. Ho. Chromatographic and Spectral Analysis of
Polynuclear Aromatic Hydrocarbons-Quantitative Distribution in Air of
Ontario Cities. Environ. Sci. Techno!., 12(8):909-915, 1978.
17. Butler, J. D., and P. Crossley. An Appraisal of Relative Airborne Sub-
Urban Concentrations of Polycyclic Aromatic Hydrocarbons Monitored
Indoors and Outdoors. Sci. Total Environ., 11(1);53—58, 1979.
18. Olufsen, B., and I. Alfheim. Analyse av Polysykiske Aromatiske
Hydrokarboner i Oslo-Luft (Analysis of PAH in Oslo Air). Report No.
NORDISK PAH-PROSJEKT-6; ISBN-82-7267-147-6, NTIS, PB83-135 418, Sentral
institutt for Industriell Forskning, Oslo, Norway, p. 27, February 1980.
19. Peake, E., and K. Black. Carcinogenic Hydrocarbons as Pollutants in the
Atmosphere of the City of Galgary. Issued by Galgary Univ., Alberta,
Canada, Environmental Science Center, Sponsor: Alberta Environmental
Trust Fund Grant 93, p. 139, July 1975.
18
-------
20. Heinrich, G., and H. Guesten. Fluorescence Spectroscopic Determination
of Carcinogenic Polycyclic Aromatic Hydrocarbons in the Atmosphere. Text
in German in: Chemische Reaktionen Atmosphaerischer Schadstoffe.
Kernforschungszentrum Karlsruhe (West Germany), Inst. Fuer Radiochemi,
Report KFK 1975 UF, pp. 77-94, May 1974.
21. Gusten, H., and H. Gunther. Polycyclic Aromatic Hydrocarbons in the
Lower Atmosphere of Karlsruhe. Proceedings from Polynuclear Aromatic
Hydrocarbons 3rd r.ternationa1 Symposium, Edited by P. W. Jones and P.
Leber, Ann Arbor Science Publishers, Inc., Ann Arbor, Michigan, p. 357,
1979.
22. Funcke, W., J. Konig, E. Balfanz, and T. Romanowsi. PAH Profiles in
Airborne Particulate Matter of Five German Cities. Atmos. Environ.,
15(5):887-890, 1981.
23. Olsen, D., and 0. L. Haynes. Preliminary Air Pollution Survey or Organic
Carcinogens. A Literature Review. Contract PH 22-68-25, NAPCA Pub.
APTD 59-43, p. 117, 1959.
24. Polycyclic Aromatic Hydrocarbons: Evaluation of Sources and Effects,
National Research Council, National Academy Press, Washington, D. C.,
1983.
25. Bosco, G., and A. Grella. Determination of Polynuclear Aromatic
Hydrocarbons in the Atmospheric Dust of the City of Siena. Nuovi Ann.
Iqiene Microbiol. (Rome). 17:297-300, 1966.
26. Bosco, G., G. Barsini, and A. Grella. New Studies on the Presence of
Aromatic Polycyclic Hydrocarbons in the Atmospheric Dusts of the Historic
Center of the City of Siena. Nuovi Ann. Iqiene Microbiol. (Rome),
18(4):285-292, 1967.
27. Bosco, G., A. Grasso, and A. Grella. Third Series of Studies on the
Presence of Polycyclic Aromatic Hydrocarbons in the Atmospheric Dust of
the Historical Quarter of Siena. Nuovi Ann. Iqiene Microbiol. (Rome),
19(1):1-12, 1968.
28. Sawicki, E., T. R. Hauser, W. C. Elbert, F. T. Fox, and 0. E. Meeker.
Polynuclear Aromatic Hydrocarbon Composition of the Atmosphere in Some
Large American Cities. Am. Ind. Hyq. Assoc. J., 23:137-144, 1962.
29. Gordon, R. J., and R. J. Bryan. Patterns in Airborne Polynuclear
Hydrocarbon Concentrations at Four Los Anqeles Sites. Environ. Sci.
Technol., 7(11):1050-1053, 1973.
30. Gordon, R. J. Distribution of Airborne Polycyclic Aromatic Hydrocarbons
Throughout Los Angeles. Environ. Sci. Techno!., 10(4):370-373, 1976-
19
-------
31. Katz, M., and C. Chan. Comparative Distribution of Eight Polycyclic
Aromatic Hydrocarbons in Airborne Particulates Collected by Conventional
High-Volume Sampling and by Size Fractionation. Environ. Sci. Techno!.,
14(7):838-843, 1980.
32. Suda, K., T. Handa, Y. Fkato, T. Yamamura, and T. Ishii. Correlation
Between the Concentrations of Polynuclear Aromatic Hydrocarbons and Those
of Particulates in an Urban Atmosphere. Environ, Sci. Techno!.,
14(4):4l6-422, 1980.
33. Masclet, P., K. Nikolaou, and G. Mouvier. Optimization of a Method for
Sampling and Analysis of Polyaromatic Hydrocarbon at Hourly Intervals.
Pollut. Atmos.. 95:175-184, 1982.
34. Sorensen, A. K., and F. Vester. Analyses of Polycyclic Aromatic
Hydrocarbons in the Air of Copenhagen and South Langeland. Nordic PAH-
Project Report No. 9, 1981. Published by Central Institute for
Industrial Research Forskningsun, 1. Oslo 3, Norway.
35. Griirmer, G., K. W. Naujack, and D. Schneider. Changes in PAH Profiles in
Different Areas of a City During the Year in: Polynuclear Aromatic
Hydrocarbons. Chemistry and Biological Effects, edited by A. Bjorseth
and A.J. Dennis, Battelle Press, Columbus, Ohio, pp. 107-125, 1980.
36. Colucci, J. M., and C. R. Begeman. The Automotive Contribution to
Airborne Polynuclear Aromatic Hydrocarbons in Detroit. J. Air Pollution
Control Assoc., 15(3):113-122. 1965.
37. Colucci, J. M., and C. R. Begeman. Carcinogenic Air Pollutants in
Relation to Automotive Traffic in New York. General Motors Research
Labs., Warren, Michigan, Department of Fuels and Lubricants, RP-GMR-777,
p. 32, 1968.
38. Colucci, J. M., and C. R. Begeman. Polynuclear Aromatic Hydrocarbons and
Other Pollutants in Los Angeles Air. International Union of Air
Pollution Prevention Associations, Proc. 2nd Int. Clean Air Congr.,
Washington, D. C., pp. 28-35, 1970.
39. VuDuc, T., and C.M.P. Favez. Pollution in an Underground Parking Garage
and Exposure Risks. Soz.-Praeventivmed. 26(5):322- , 1981.
40. Biologic Effects of Atmospheric Pollutants: Particulate Polycyclic
Organic Matter, Division of Medical Sciences National Research Council,
National Academy of Sciences, Washington, D. C., 1972.
41. Impacts of Diesel-Powered Light Duty Vehicles: Health Effects of
Exposure to Diesel Exhaust, National Research Council, National Academy
Press, Washington, D. C., 1981.
20
-------
42. World Health Organization, International Agency for Research on Cancer
(IARC) Monographs on the Evaluation of Carcinogenic Risk of the Chemical
to Man, Volume 3, 1973.
43. Hughes, T. J., E. Pellizzari, L. Little, C. Sparacino, and A. Kolber.
Ambient Air Pollutants: Collection, Chemical Characterization and
Mutagenicity Testing. Mutation Research, 76:51-83, 1980.
44. Arashikani, K., M. Fukunaga, M. Yoshikawa, Y. Kodman, and Y. Mizuguchi.
Mutagenic Activities of Benzene Extract of Airborne Particulates. Sch.
Med. Techno. Univ. Environ. Health, Kitakyushu, Japan 807, J. UOEH
4(4):451-458, 1982- (Japan), CA98:12l059h.
45. Pitts, 0., D. Grosjean, T. Mischka, V. Simmon, and D. Poole. Mutagenic
Activity of Airborne Particulate Organic Pollutants. Toxicol. Lett.,
1:65-70, 1977.
46. Tokiwa, H., K. Morita, H. Tokeyoshi, K. Takahashi, and Y. Ohnishi,
Detection of Mutagenic Activity in Particulate Air Pollutants. Mutation
Research. 48:237-248, 1977.
47. Flessel, C. P., J. J. Wesolowski, S. Twiss, J. Cheng, J. Ondo, N. Monto,
and R. Chan. Integration of the Ames Bioassay and Chemical Analyses ir
an Epidemiological Cancer Incidence Study. Paper presented at the U.S.
EPA Second Symposium on the Application of Short-Term Bioassays in the
Fractionation and Analysis of Complex Environmental Mixtures,
Williamsburg, VA, 1980.
47a. Austin, D. F., V. Nelson, B. Swain, L. Johnson, S. Lum, and P. Flessel.
Epidemiological Study of the Incidence of Cancer as Related to Industrial
Emissions in Contra Costa County, California. EPA-600/51-S4-008, 1984.
NTIS:PB84-199785.
48. Consnoner, B., P. Madyastha, A. Bronson, and A. J. Vithayathil.
Environmental Mutagens in Urban Air Particulates. J. Toxicol. Environ.
Hlth., 4:59-77, 1978.
49. Moller, M., and I. Alfheim. Mutagenicity and PAH Analysis of Airborne
Particulate Matter. Atmos. Environ.. 14:83-88, 1980.
50. Moller, M., I. Alfheim, S. Larssen, and A. Mikaisen. Mutagenicity of
Airborne Particles in Relation to Traffic and Air Pollution Parameters.
Environ. Sci. Technol.. 16:221-225, 1982.
51. Huisingh, J. Lewtas. Bioassay of Particulate Organic Matter from Ambient
Air. Reprinted from: Short-Term Bioassay in the Analysis of Complex
Environmental Mixture, Edited by Michael D. Waters, Shahbeg S. Sandhu,
Joellen Lewtas Huisingh, Larry Claxton and Stephen Nesnow, Plenum Press,
New York, p. 9, 1980.
21
-------
52- Tokiwa, H., R. Nagawa, K. Morita, and Y. Ohnishi. Mutagenicity of N1tro
Derivatives Induced by Exposure of Aromatic Compounds to Nitrogen
Dioxide. Mutation Research, 85(4):195-206, 1981.
53. Fukino, H., S. Mimura, K. Inoue, and Y. Yamane. Mutagenicity of Airborne
Particles. Mutation Research. (Netherlands'). 10Z(103):237-247, 1982.
54. Madsen, E. S., P. A. Nielsen, and J. C. Pedersen. Atmospheric Air
Pollution and Cancer. A Review of Experimental Investigations. Uqeskr.
Laeq. (Denmark!. 144(23):1719-1721. 1982.
55. Madsen, E. S., P. A. Nielsen, and J. C. Pedersen. The Distribution and
Origin of Mutagens in Airborn Particulates, Detected by the
Salmonella/Microsonie Assay in Relation to Levels of Lead, Vanadium, and
PAH. Sci. Total Environ., 24(l):13-25, 1982.
56. Nielsen, T., B. Seitz, A. M. Hansen, K. Keiding, and B. Westerberg. The
Presence of Nitro-PAH in Samples of Airborne Particulate Matter. In:
Seventh International Symposium on Polynuclear Aromatic Hydrocarbons,
edited by M. Cooke and A. J. Dennis, Battelle Press, Columbus, Ohio,
pp. 951-970, 1983.
57. Ohgaki, H., N. Matsukura, K. Morino, T. Kawachi, T. Sugimura, K. Morita,
H. Tokiwa, and T. Kirota. Carcinogenicity in Rats of the Mutagenic
Compounds 1-Nitropyrene and 3-Nitrofluorene. Cancer Lett., 15:1-7, 1932.
58. Lewtas, J. Mutagenic Activity of Diesel Emissions. In: Toxicological
Effects of Emissions for Diesel Engines, J. Lewtas, Editor. Elsevier
Biomedical Press, pp. 243-264, 1982.
59. Rosenkranz, H. S., E. C. McCoy, R. Mermelstein, and T. Speck. A
Cautionary Note on the Use of Nitroreductase-Deficient Strains of
Salmonella Typhimurium for the Detection of Nitro-arenes as Mutagens in
Complex Mixtures including Diesel Exhausts. Mutation Research. 91:103-
105, 1981.
60. Pitts, J. N., Or. Formation and Fate of Gaseous and Particulate Mutagens
and Carcinogens in Real and Simulated Atmospheres. Environ. Health
Perspect.. 47:115-140, 1983.
61. Dehren, W., N. Pitz, and R. Tomlngas. The Mutagenicity of Airborne
Particulate Pollutants. Cancer Lett.. 4:5-12, 1977.
62. Chuang, C. C., M. G. Nishioka, and B. A. Petersen. Fractionation and
Analysis of Particulate Organic Matter from Ambient Air Samples, Final
Report for U.S. EPA, Contract No. 68-02-3169 (UA 20), 1984.
63. Schuetzle, D. Sampling of Vehicle Emissions for Chemical Analysis and
Biological Testing. Environ. Health Perspectives. 47:65-80, 1983.
22
-------
64. Ashby, J., and J. Styles. Comutagenicity, Competitive Enzyme Substrates,
and In Vitro Carcinogenicity Assays. Mutation Research, 54:105-112,
1978.
65. Guttenplan, J. Comutagenic Effects Exerted by N-Nitrosocompounds.
Mutation Research. 66:25-32, 1979.
66. Scribner, 0. Cocarcinoqens as Environmental Hazards. Med. Ped. Oncol.,
3:151-157, 1977.
67. Huisingh, J., R. Bradow, R. Jungers, L. Claxton, R. Zweidinger, S.
Tejada, J. Bumgarner, F. Duffield, M. Waters, V. Simmon, C. Hare, C.
Rodriguez, and L. Snow. Application of Bioassay to the Characterization
of Diesel Particle Emissions. In: Application of Short-Term Bioassays
in the Fractionation and Analysis of Complex Environmental Mixtures.
U.S. EPA-600/9-78-027, pp. 381-418, 1978.
68. Grimmer, G., K. W. Naujack, G. Dettbarn, H. Brune, R. Deutsch-Wenzel, and
J. Misfeld. Characterization of Polycyclic Aromatic Hydrocarbons as
Essential Carcinogenic Constituents of Coal Combustion and Automobile
Exhaust Using Mouse-Skin-Painting as a Carcinogen-Specific Detector.
Toxicol. Environ. Chem.. 6(2):97-107, 1983.
69. Pott, F., and W. Stober. Carcinogenicity of Airborne Combustion Products
Observed in Subcutaneous Tissue and Lungs of Laboratory Rodents.
Environ. Health Perspect., 47:293-303, 1983.
70. Candell, A., V. Mastradea, and A. Savino. The Problem of Carcinogenicity
from Air Pollution. II. Analysis of the Air from a Tunnel in Perugia.
Riv. Ital. Iqiene (Pisa). 27(3-4):165-174, 1967.
71. Nishioka, M. G., and B. A. Petersen, In: Comparative Analysis of
Combustion Emission Extracts for Nitro-Aromatics. Final Report for U.S.
EPA, Contract No. 68-02-3169 (WA-15), 1982.
72. Chuang, C. C., and B. A. Petersen. In: CCMC/ERMC-Round Robin Study,
Reported at the PAH Round Robin Meeting of the Committee of Common Market
Automobile Constructors (CCMC), Geneva, Switzerland, September, 1982.
73. Pedersen, T. C., and J-S Siak. Dinitropyrenes: Their Probable Presence
in Oiesel Particle Extracts and Consequent Effect of Mutagenic Activators
by NADPH-Dependent Sa enzymes. In: U.S./EPA Diesel Emissions Symposium,
Raleigh, NC, U.S. EPA, pp. 121-122, October 1981.
74. Ball, L. M., and J. Lewtas. Metabolism and Genotoxicity of 1-
Nitropyrene. In: Eighth International Symposium on Polynuclear Aromatic
Hydrocarbons, M. W. Cooke and A. J. Dennis, Editors, Battelle Press,
Columbus, Ohio, pp. 121-133, 1985.
75. Pfeiffer, E. H. Oncogenic Interaction of Carcinogenic and Non-
carcinogenic Polycyclic Aromatic Hydroacarbons in Mice. IARC Sci. Publ.,
16:69-77, 1977.
23
-------
SECTION 4
SAMPLING METHODOLOGY FOR THE
COLLECTION OF POLYNUCLEAR AROMATIC HYDROCARBONS
INTRODUCTION
Ambient air contains a complex mixture of hundreds of compounds present
at trace concentrations. In general, the chemical analysis methods are well
developed, but the sampling procedures can often reduce the validity of
analytical results.(1) In White and Vanderslice's(2) review of polycyclic
organic matter (POM), source and ambient concentration sampling techniques
were shown to contain uncertainties that limit the usefulness of the data in
an environmental assessment of POM. The uncertainties include the possibility
of incomplete capture of POM during sampling and the chemical degradation of
the collected samples.
The potential for loss of PAHs as a result of volatilization during the
sampling process has been recognized by several groups.(3-10) Recently,
Battelle(ll) conducted a study for the U.S. EPA, to assess the effects of
current air filtration sampling methods on the integrity of the collected
sample. A detailed literature review was performed to collect information on
the volatilization and reactivity of PAHs. The consensus of the articles
reviewed is that loss of PAH occurs due to volatilization during the sampling
process, but there is not universal agreement as to the magnitude of such
losses. Control of sampling temperature and the use of back-up traps can
reduce the loss of PAH during ambient air sampling.
Many studies(12-18) have been conducted to evaluate the loss of PAHs
through reactions during collection and storage. Recently a Battelle research
team(ll) has surveyed the literature concerning the reactivity of PAHs. The
results indicated that PAHs can undergo chemical transformation when exposed
to gases such as NOj and O3, especially in the presence of UV irradiation.
The magnitude of this degradation is difficult to assess. In several of these
studies,15) pah solutions were spiked onto the surface of glass fiber
filters, then exposed to N0^ and O3 gases. Since the PAHs studied were not
spiked onto ambient particulate material in a manner similar to that of
"natural PAHs", the decomposition problem may be more severe than that which
would actually occur during sampling. Indeed, some studies'.^'!?) showed that
particle-bound PAHs are more stable than are solvent-spiked PAHs. Recently,
Brorstrom's(18) group conducted a series of exposure studies that closely
simulated ambient air sampling. The exposure experiments were carried out in
a way similar to high volume sampling of atmospheric PAHs. Two high volume
samplers were run in parallel and collected ambient air particles for 24
hours. One sampler was equipped with a dosage system to increase the
concentration of NO2, O3, HNOg, and HNO3 during sampling. The other sampler
24
-------
system was used to determine background PAH measurements in ambient air
particulate matter. The results showed that either the addition of NO2 at 1
part per million (v/v) or HNO3 at 120 parts per billion (v/v) during ambient
air sampling caused degradation of reactive PAHs, such as pyrene, BaA, and
BaP, on particles. However, the authors did not mention the exposure
sampling temperature at these experiments. Although it was assumed to be
ambient tenperature, the influence of sampling temperature on PAH degradation
was not addressed in these studies. The most pronounced effect was found in
the experiment with HNO3 exposure at 120 ppb. For BaP, the loss was about 95
percent while the concentrations of BaA and perylene decreased by 55 percent
and benzo(g,h,i)perylene decreased by 20 percent. Evidence for this
degradation was observed when the mononitrated derivatives of these PAHs were
tentatively identified. Addition of HNO2 at 100 ppb had no detectable effect.
Since NO and NO2 are acid anhydrides and form HNO? and HNO3 with water, these
results indicate that NO does not react with adsorbed PAHs, but NO2 does cause
PAH degradation which is enhanced by the presence of acids and moisture. The
author also indicated that this degradation will probably take place in the
atmosphere during transportation with the range of NO? concentrations normally
found in urban air ( 0.2 ppm). In the case of O3 exposure at 200 ppb,
degradation was observed in only one of the experiments.
In view of the losses, reactivity and other potential difficulties
associated with the collection of PAHs in ambient air, a sampling system for
these compounds must be designed to minimize these problems. Specifically,
the system should be capable of sampling at a constant flow rate during the
sampling interval and providing representative samples with minimal
deterioration and contamination. For evaluation of health effects, the
sampling system must also generate samples that are truly representative of
the air that is actually inhaled by humans. Samples should also be collected
in sufficient quantity for the level of detection of the analytical methods
and/or bioassay analyses. Consideration of on-site analysis versus sample
stability is also important. When on-site analysis is impractical because of
the type of sample preparation and equipment required, sample handling and
storage should become an integral part of the sampling program. Proper
quality assurance procedures should be designed and implemented throughout
sampling efforts.
SAMPLE CONSIDERATIONS
Sample Size
In general, two main factors determine the amount of sample to be
collected:
(1) The extent to which the environment is polluted
(2) The number and types of analyses required for the sample.
The concentrations of PAHs in ambient air range from less than 1 ng/m3 in
relatively clean air to over 100 ng/m3 1n the polluted air of large cities.
Usually a minimum of about 100 liP of air must be sampled to collect a
sufficient amount of PAHs for chemical analysis. Larger sample sizes are
25
-------
often needed in order to carry out bioassay analyses. A typical sampling time
using a high-volume (Hi-Vol) sampler is 12 to 24 hours.
Sample Type
Polynuclear aromatic hydrocarbons (PAHs) exist in the atmosphere both as
vapors and as material either condensed or adsorbed on particles. Generally,
the majority of PAHs in the atmosphere are found to be adsorbed on suspended
particulate matter with average diameter less than 7 urn, which is in the
respirable range. It is important to note that PAHs are strongly associated
with particles in the submicron range.(3>19-24)
Miguel and Friedlander(22) found that 75 percent of BaP and 85 percent
of coronene were associated with particles having aerodynamic diameters less
than 0.26 m, and that one half of the total mass of these compounds was on
particles in the size range of 0.075 to 0.12 um. The mass distribution of
coronene and BaP with respect to particle size did not shift with season. A
similar study, however, carried out by VanVaeck and VanCauwenberghe(^)
indicated that the distribution of the PAHs bonded to particles shifts toward
the small particles in winter. In Vu Due and Favez's study(24) of motor
vehicle exhaust in an underground parking lot, more than 80 percent of the
PAHs was found to be adsorbed on particles smaller than 1.1 um. Similar work
done by Bjorseth(23) indicated that the largest amounts of PAHs adsorbed on
particles were on those of 0.9-3 um diameter, with less than 1 percent on non-
respirable particles ( 7 ^m). Particles of this small size tend to have long
residence times in the atmosphere, which may increase the probability of
atmospheric chemical and photochemical reactions to produce mutagenic and/or
carcinogenic compounds. Therefore small airborne particles should be
considered important for collection in the future study.
Only a few studies have been concerned with the collection of vapor
phase PAHs, and these studies have produced conflicting results. Dewiest and
Rondia(25) measured the particulate matter and gas phase BaP of the Liege
aerosol. The reported gas phase BaP concentrations were always less than 15
percent of the total BaP concentrations at air temperatures less than 25°C,
but increased to 44 percent at 41°C. Miguel and Fried!ander(22) found no
measurable pyrene and BaP in the gas phase in Pasadena air. Van
Cauwenberghe's groupw9) usec] a Tenax adsorption column mounted after a
filtration Hi-Vol sampler to collect gas phase PAHs. Significant amounts of
phenanthrene, anthracene, fluoranthene, pyrene, and their methyl derivatives
were found in the gas phase.
Recently, a study conducted by Thrane and Mikalsen(^) employed
polyurethane foam to collect vapor phase PAHs in a Hi-Vol sampler system. The
distributions of PAH on the foam (gas phase) and the filter (particulate
bound) agree with the results of the study by VanCauwenberghe(39) previously
described. With regard to health effects, the collection of gas phase PAHs in
air is as important as the collection of particulate-bound PAHs. Further
studies in this area are needed.
In a study by Moller, Alfheim and coworkers,(26) extracts of strset and
roof level airborne particulate matter showed mutagenic activity only from
26
-------
particles less than 3 m in diameter. Similar results were obtained by
Arashidani's group,(27) who showed that extracts of airborne particles from
Japan were mutagenic in Salmonella typhimurium, with the mutagenic response
increasing with decreasing particle size. More than 92 percent of the total
mutagenic response resulted from extracts of airborne particles less than
10 um in diameter.
This survey suggests that PAHs exist in the atmosphere in both vapor and
particulate phases. Furthermore, most particulate-bound PAHs found in air
samples are in the respirable size range (<10 um), and the major mutagenic
activity of extracts of air particulate samples is also in this range. For
the future microenvironment air sampling methodology, samples collected for
analysis should be representative of the air which is inhaled by the exposed
humans. The sampling device should be able to collect both gas and
particulate-phase PAHs, with a particle size cutoff less than 10 um.
SAMPLING DEVICES
The general practice in sampling PAHs in ambient air involves the
collection of suspended particulate matter by means of filters or impingers.
Vapor phase PAHs have been collected on absorbent materials such as XAD-2,
Tenax, and polyurethane foam. This section describes the devices which have
been used for ambient air sampling.
High and Low Volume Samplers
Many studies(24,30,43,44) have been conducted to collect particulate-
bound PAHs using high-volume sampling with glass fiber filters. In this
method, up to 100 m3/hr of air is drawn through 20 x 25 cm glass fiber filters
to allow the collection of up to one gram of particulate matter in 24 hours.
The advantage of using a high volume sampler is the high flow rate, which
allows the collection of milligram quantities of particulate matter in a day.
However, certain sampling problems may occur due to the high air flow rate.
In a study by Katz and Chan,(.29) airborne particulate samples were
collected by a conventional high volume sampler and by an Andersen cascade
impactor every month over a period of one year at two sampling sites in
Hamilton, Ontario. The results of this study showed that the size-
fractionated samples from the impactor contained much higher amounts of
soluble organic material than the corresponding extracts from the Hi-Vol
samples. Substantially higher levels of PAHs were also found in the cascade
impactor samples. It is reasonable to assume that continued air sampling flow
rates of 100 m^/hr through glass fiber filters over 24 hours may result in a
loss of PAHs by sublimation or vaporization from the particulate matter
deposited on the filter surface.
Handa and coworkers(30) measured the atmospheric levels of PAHs and the
concentrations of particulate matter with various particle size ranges at
several sites in Tokyo. A high volume sampler was used to collect air
particulate matter, and measurements were made on the particulate material to
determine the concentrations of pyrene, chrysene, BaP, and perylene. The
27
-------
concentration of particulate matter, ranging in size from 0.1 nm to 0.2 um,
was determined with an optical counter. Poor correlations between the
quantities of PAHs and of particulate matter were observed. To Improve the
capture of the missing four-ring PAHs (e.g., pyrene, fluoranthene), an
improved collection system with traps cooled by liquid nitrogen was developed.
The results showed that 13 percent of total BaA, 17 percent of total chrysene,
and 54 percent of pyrene were recovered in the second part of the sampling
system.
The sampler EPA(31) has developed to collect the total quantity of
pesticidal compounds in air may be used to improve the capture of PAHs. The
device uses a high volume sampler to collect particulate matter and a solid
sorbent cartridge to trap vapors.
There are few citations describing the use of low-volume (Lo-Vol}
samplers. A Lo-Vol sampler has a flow rate about one tenth that of a Hi-Vol
sampler. However, only a few studies were found in the literature that used a
Lo-Vol sampler to collect ambient air particles, and no study was found that
evaluated the distribution of PAHs between vapor and particulate phases.
Hence, the comparison of breakthrough values for Hi-Vol and Lo-Vol samplers
cannot be addressed. Due to its lower flow rate, breakthrough problems may be
less important in a Lo-Vol than in a Hi-Vol sampler. The limited flow rate,
however, also limits the sample size, which could be the reason for the few
applications of Lo-Vol samplers in ambient air studies.
Griraner and colleagues(32) used a Lo-Vol air sampler with a glass fiber
filter to collect PAHs in air in different areas of an industrial city of
700,000 inhabitants: Essen, West Germany. In Grimmer's study, the samples
were collected using a Lo-Vol sampler at the following four selected sites
that were polluted by various emissions:
(1) Residential coal heating
(2) Oil heating
(3) Car traffic in a tunnel
(4) Coke ovens.
The PAH concentration profiles were generated using benzo(e)pyrene as a
reference compound. BeP concentration was defined as one, and other PAHs were
given in ratio to BeP. However, since no absolute concentrations were
reported in this study, the comparison of PAH concentrations between Hi-Vol
and Lo-Vol samples cannot be addressed here. The results did indicate that
the PAH profile differed in many cases from area to area. Cyclopenta(c.d)-
pyrene was the predominant species measured in the traffic areas, but was
found to be a minor component 1n the other areas. The author suggested that
the different PAH profiles may be helpful to recognize the sources of air
pollution.
Impaction Devices
Impaction devices collect and retain particles from an aerosol stream on
a surface. Some loss of large particles occurs with high aerosol velocities.
It is believed that nearly all small particles of several micrometers or less
are retained on the impactor surface.
28
-------
Several impaction devices have been used in ambient air sampling to
collect air samples in different particle size fractions. For example, a
cascade impactor and an Andersen sampler are both multi-stage impactor
devices. The greatest limitation of the Andersen sampler is its relative low
flow rate, one cubic foot per minute. To overcome the low flow rate of the
Andersen sampler, a modified Andersen sampler has been devised.(33) The
Andersen cascade impactor fractionates particles in a series of six collection
stages according to the aerodyamic dimensions of the particles. The modified
sampler can operate at a flow rate of 5-6 cfm with removal of the sixth stage
of the Andersen sampler; a 4-inch diameter filter is placed downstream to
collect the small unimpacted particles. The particle size distributions of
suspended particulate matter in six urban areas were determined with this
modified sampler.(33) The results indicated that suspended particulate matter
in urban air was predominately in the submicron size range. No PAH
measurements were performed.
Another size-fractionating particulate sampler consists of a typical Hi-
Vol blower unit with an adapter comprised of four stages with successively
small slit openings. Behind each slit is a collection plate for retaining
particles. The small particles passing through this impaction device are
collected using a typical Hi-Vol sampler.
The Institut fur Lufthygiene in West Germany uses two devices known as
the BAT I and BAT TI to collect ambient air samples.(28) The BAT I and BAT II
are similar to a high volume sampler, except that particles larger than 10 um
are removed before passage of the air sample through the BAT I and BAT II
system. Only respirable particles are collected by the svstem. The air flow
rate of the BAT I is 10 m^/hr; that of the BAT II is 100 m*/hr.
Filter Media
A variety of materials has been used to filter air particles, including
cloth,(34) metal fibers,(35) paper,(36) molecular membranes,(37) and glass
fibers. Glass fiber filters are widely used in ambient air sampling because
these filters have a collection efficiency of a least 99.9 percent
for particles of 0.3 um and larger, low resistance to air flow, and low
affinity for moisture. However, several problems with the use of glass fiber
filters to collect PAHs in air have been identified by different
groups.(6>7»8) All the authors agree that PAHs collected on glass fiber
filters show breakthrough problems during long sampling periods. Konig,
Cavarkers and coworkers(T) found that during long collection periods, the more
volatile PAHs show significant losses; for example, 78 percent of fluoranthene
was lost during a 12 week collection. The evaporation of these PAHs is demon-
strated by comparing the reentrainment on subsequent filters. The losses can
be considerably reduced when the filters are impregnated with glyceroltri-
caprylate. Loss of fluoranthene was reduced to 13 percent during a 12 week
collection when the filters were treated this way. However, only a few
studies have investigated the effect of filter materials on collected PAHs.
Lee's group(8) has evaluated various candidate filter materials such as glass
fiber, quartz fiber, microglass fiber with Teflon binder, and Teflon membrane
filters. The evaluation was performed by spiking BaP onto filters two
different ways:
29
-------
(1) Directly spiking l^c-iabelled BaP solution onto clean filters or
air particulate filter samples, followed by exposure to filtered
urban air.
(2) Spiking 14C-BaP onto clean filters or air particulate samples,
followed by storage at room temperature in darkness.
In both experiments, better recovery of l^C-BaP was observed using Teflon-
coated and Teflon membrane filters compared to glass or quartz fiber filters.
Another study was conducted by Battelle(38) to evaluate five filter
types for collection effectiveness for particulate PAHs from diluted diesel
exhaust. The filters tested were glass fiber, silanized glass fiber, Pallflex
TX 40-HI-20-WW, Pallflex T60A20, and prototype Teflon filters. The results
indicated that the filter type does not strongly influence the quantity of
PAHs in the collected particulate material. It is noteworthy that the glass
fiber filters produced no decrease in the PAH concentrations and appeared to
function as well as, and in some cases better than, Teflon-coated filters. It
would be worthwhile to compare different types of filters such as glass fiber
and Teflon-coated filter material for collecting of PAHs in ambient air
santpl ing.
Adsorbent Media
Several adsorbent materials that have been considered for trapping of
PAH vapors are the following:
(a) Tenax-GC
(b) Chromosorb 101
(c) XAD-2
(d) polyurethane foam.
Cautreels and VanCauwenberghe(39) uSed a Tenax-GC adsorption column mounted
after a filtration Hi-Vol sampler to measure pollutants present either . as
gases or resulting from evaporation of the collected sample. Primarily the
lower aliphatic compounds (up to n-docosane and lower homologs), the lower
fatty acids (up to pentadecanoic acid), PAHs (up to 4 rings), and methylated
derivatives of these compounds are found on the adsorption column. However,
Tenax-GC is expensive and requires lengthy purification procedures before use.
Also, it hcs been known to degrade to several diphenylquinones if exposed to
hot, oxidizing climates such as those in stack gas emissions.(40) Both XAD-2
and Tenax-GC have been shown to have a high collection efficiency for
PAHs.(45>46)
XAD-2 and Chromosorb 101 are both styrene-divinyl benzene copolymers in
pellicular form and differ only in particle size. XAD-2 is available in 40/60
mesh, whereas Chromosorb 101 is available in 60/80 mesh. XAD-2 can be a
better choice than Chromosorb 101 because the large particle size of the XAD-2
produces a lower pressure drop across the trap, thus permitting a higher
sampling flow rate.
30
-------
Lindgren'sC^l) group compared two adsorbents (polyurethane plugs and
Bondpack-C]_8 plugs) for the collection of PAHs in ambient air. In this study,
glass fiber filters were not used to collect particulate matter; only
polyurethane plugs and/or Bondpack-Cis plu9s were used as the collection
devices. The polyurethane plugs were found to produce a large amount of
extractable UV-absorbing material, which contaminated the air sample during
extraction and made the chemical analyses difficult. The Bondpack-Cjg plugs
demonstrated a large resistance to air flow. However, the ease of desorption
from Cjs plugs and the minimal contamination problem suggest that Cig-bound
adsorbents may provide a viable alternative to the use of polyurethane plugs.
Recently, some other groups(4,5,42) ^ave used polyurethane foam plugs as
backup traps to collect vapor phase PAHs in ambient air. This work
demonstrated that the use of different solvents (e.g. acetone, cyclohexane,
and/or petroleum ether) to clean the polyurethane foam before sampling will
minimize the contamination problems observed by Lindgren. In Keller and
Bidleman's study,(42) high volume air samples were collected in urban and
rural locations using a glass fiber filter/polyurethane foam collection train.
Most of the three- and four-ring PAHs were found on the trap, while the higher
ring PAHs were retained by the filter. This study also indicated that
temperature is the most important consideration in designing collection
systems for trace organics. At 20°C and 600 m3 air, breakthrough to a backup
trap was 15 percent for the 3-ring PAHs, phenanthrene and anthracene, and 25
percent for the total organics C^g. The same volume of air sampled at 25°C
produced breakthrough of 40 percent or more. All the results from these
studies showed that polyurethane foams can be useful as adsorbents for PAH
vapors because these materials are easy to handle in the field and have good
air flow characteristics. No study has been conducted to compare the
collection effectiveness and breakthrough values of polyurethane foams with
XAD-2. It would be worthwhile to conduct this kind of study to learn which
adsorbent is best suited for collecting PAH vapors in ambient air sampling.
31
-------
REFERENCES
SECTION 4
1. Sievers, R. E. Sampling and Analyzing Airborne Organics. Environ. Sci.
Techno!.. 13(10):11B8-1189, 1979.
2. White, J. B., and R. R. Vanderslice. POM (Polycyclic Organic Matter)
Source and Ambient Concentration Data: Review and Analysis. Final
Report, Research Triangle Park, NC, Report No. U.S. EPA-600/7-80-044, p.
147, 1980.
3. VanVaeck, L., and K. VanCauwenberghe. Cascade Impactor Measurements of
the Size Distribution of the Major Classes of Organic Pollutants in
Atmospheric Particulate Matter. Atmos. Environ.. 12:2229-2239, 1978.
4. Thrane, K. E., and A. Mikalsen. High-Volume Sampling of Airborne
Polycyclic Aromatic Hydrocarbons Using Glass Fiber Filters and
Polyurethane Foam. Atmos. Environ.. 15(6):909-9l8, 1981.
5. Yamasaki, H., K. Kuwata, and H. Miyamoto. Collection of Atmospheric
Polycyclic Aromatic Hydrocarbons Using Polyurethane Foam Plugs. Bunseki
Kagaku, 27(6)t317-321. 1978.
6. DeWiest, F., and D. Rondia. On the Validity of Determinations for Benzo-
(a)pyrene in Airborne Particles in the Sumner Months. Atmos. Environ.,
10(6):487-489, 1976.
7. Konig, J., W. Funcke, E. Balfanz, B. Grosch, and F. Pott. Testing a High
Volume Air Sampler for Quantitative Collection of Polycyclic Aromatic
Hydrocarbons. Atmos. Environ., 14:609-613, 1980.
8. Lee, F. S., W. R. Pierson, and J. Ezike. The Problem of PAH Degradation
During Filter Collection of Airborne Particulates—an Evaluation of
Several Comnonly Used Filter Media. In: Polynuclear Aromatic
Hydrocarbons A. Bjorseth and A. 0. Dennis, editors, Battelle Press,
Columbus, Ohio, pp. 543-563, 1979.
9. Conmins, B. T. Interim Report of the Study of Techniques for Deter-
mination of Polycyclic Aromatic Hydrocarbons in Air. Nat. Cancer Inst.
Monograph, No. 9:255-233, 1962.
10. Tomingas, R. Remarks on the Sampling Procedures for Polycyclic Aromatic
Hydrocarbons from the Atmosphere. Fresenius' Z. Anal. Chem., 297(2-
3):97-l01, 1979.
32
-------
11. Coutant, R. W., and R. M. Riggin. Assessment of Sample Integrity and
Distribution of Gaseous Particulate-Sorbed Organics in Ambient Air,
Interim Report for U.S. EPA, Contract No. 68-02-3487 (WA-17), 1983.
12. Tipson, R. S. Review of Oxidation of Polycyclic Aromatic Hydrocarbons.
National Bureau of Standards, Washington, D. C., Division of Physical
Chemistry. NBS Report 8363, p. 89, May 1964.
13. Katz, N. M. Problems in Analysis of Air Contaminants. Preprint:
Association of the Official Analytical Chemists; Internation Union of
Pure and Applied Chemistry; Chemical Inst, of Canada; Agricultural Inst,
of Canada; and National Research Council of Canada. Presented at the
International Symposium on Identification and Measurement of Environ-
mental Pollutants, Ottawa, Ontario, pp. 124-129, 1971.
14. Pitts, J. N., Jr., K. A. VanCauwenberghe, D. Grosjean, J. P. Schmid, and
D. R. Fitz. Atmospheric Reactions of Polycyclic Aromatic Hydrocarbons:
Facile Formation of Mutagenic Nitro Derivatives. Science, 202:515-519,
1978.
15. Pitts, J. N., Jr., D. M. Lokensgard, P. S. Ripley, K. A. VanCauwenberghe,
L. V. Vaeck, S. D. Shaffer, A. J. Thill, and W. L. Belser, Jr.
Atmospheric Epoxidation of Benzo(a)pyrene by Ozone: Formation of the
Metabolite Benzo(a)pyrene-4, 5-0xide. Science, 202:1347-1349, 1980.
16. Pitts, J. N., Jr., A. M. Winer, D. M. Lokensgard, S. D. Shaffer, E. C.
Tuazon, and G. W. Harris. Interactions Between Diesel Emissions and
Gaseous Copollutants in Photochemical Air Pollution: Some Health
Implications. Environ. Int., 5(4-6):235-242, 1981.
17. Brorsvoem, E., and A. Lindskog. Degradation of Polycyclic Aromatic
Hydrocarbons During Sampling. Inst. Vatten-Luftvardsforsk., Goeteborg,
Swed., publ B, IVLB-594, p. 16, 1931.
18. Brorstroem, E.t P. Grennfelt, A. Lindskog, A. Sjoedin, and T. Nielsen.
Transformation of Polycyclic Aromatic Hydrocarbons During Sampling in
Ambient Air by Exposure to Different Oxidized Nitrogen Compounds and
Ozone. In: Seventh International Symposium on Polynuclear Aromatic
Hydrocarbons, edited by M. Cooke and A. J. Dennis, Battelle Press,
Columbus, Ohio, pp. 201-210, 1983.
19. Albagli, A., H. Oja, and L. Dubois. Size-Distribution Pattern of
Polycyclic Aromatic Hydrocarbons in Airborne Particulates. Environ.
Letters. 6(4):24l-251, 1974.
20. Katz, M., and R. C. Pierce. Quantitative Distribution of Polynuclear
Aromatic Hydrocarbons in Relation to Particle Size of Urban Particulates.
In: Carcinogeneses-A Comprehensive Survey. R. Freudenthal and P. W.
Jones, editors. Vol. 1., Raven, New York, p. 413, i976.
33
-------
21. Pierce, R. C., and M. Katz. Dependency of Polynuclear Aromatic
Hydrocarbon Content on Size Distribution of Atmospheric Aerosols.
Environ. Sci. Techno!.. 9(4):347-353, 1975.
22. Miguel, A. H., and S. K. Friedlander. Distribution of Benzo(a)pyrene and
Coronene with Respect to Particle Size in Pasadena Aerosols in the
Submicron Range. Atmos. Environ.. 12:2407-2413, 1978.
23. Bjorseth, A. Determination of Polynuclear Aromatic Hydrocarbons in the
Working Environment. In: Polynuclear Aromatic Hydrocarbons, edited by
P. VI. Jones and P. Leber, Ann Arbor, Michigan, p. 371, 1979.
24. Vu Due, T., and C.M,R. Favez. Characteristics of Motor Exhausts in an
Underground Car Park: Mass Size Distribution and Concentration Levels of
Particles. J. Environ. Sci. Health. A16(6):647-660, 1981.
25. DeWiest, F., and D. Rondia. Sur la Validite des Determinations du
Benzo(a)pyrene Atmospherique Pendant les Moisdete, Atmos. Environ.,
10:487-489, 1976.
26. Moller, M., I. Alfheim, S. Larssen, and A. Mikalsen. Mutagenicity of
Airborne Particles in Relation to Traffic and Air Pollution Parameters.
Environ. Sci. Techno!.. l6(4):22l-225, 1982.
27. Arashidani, K., M. Fukunaga, M. Yoshikawa, Y. Kodama, and Y. Mizuguchi.
Mutagenic Activities of Benzene Extract of Airborne Particulates. Sch.
Med. Techno!. Univ. Occup. Environ. Health Kitakyushu, Japan, 807, J.
UOEH, 4(4):45l-458, 1982.
28. Vaclav, M. Measurement cf Respirable Dust in the Work Areas of a Coking
Plant. Staub-Reinhalt. Luft, 37(12):464-467, 1977. CA(88):176334t.
29. Katz, M., and C. Chan. Comparative Distribution of Eight Polycyclic
Aromatic Hydrocarbons in Airborne Particulates Collected by Conventional
Hiqh-Volume Somplinq and by Size Fractionation. Environ. Sci. Technol..
14(7):838-843, 1980.
30. Handa, T., K. Yoshihiro, Y. Takai, I. Tadahiro, and S. Kyo. Correlation
Between the Concentrations of Polynuclear Aromatic Hydrocarbons and those
of Particulates in an Urban Atmosphere. Environ. Sci. Technol.,
14(4):416-422, 1980.
31. Lewis, R. G., M. D. Jackson, and K. E. MacLeod. U.S. EPA Users Guide
Protocol for Assessment of Human Exposure to Airborne Pesticides. U. S.
EPA-600/2-80-180, 1980.
32. Griiraner, G., K. W. Naujack, and D. Schneider. Changes in PAH Profiles in
Differenct Areas of a City During the Year. In: Polynuclear Aromatic
Hydrocarbons, edited by A. Bjorseth and A. J. Dennis, Battelle Press,
Columbus, Ohio, pp. 107-125, 1980.
34
-------
33. Lee, R. E., and S. Goransen. National Air Surveillance Cascade Impactor
Network I. Si2e Distribution Measurements of Suspended Particulate
Matter. Environ. Sci. Techno!.. 6:1019-1024, 1972.
34. Iinoya, K., and J. R. Orr. In: Source Control by Filtration, A. C.
Stern, editor. Academic Press, New York, pp. 5-44, 1968.
35. Rodman, C. A., and J. A. Staricenka. For Filters—Metalized Fiber.
Mech. Eng.. 85:54-57, 1963, CA58:86696.
36. Hendrickson, E. R. In: A1r Sampling and Quality Measurement. A. C.
Stern, Editor. Academic Press, New York, 2:26-27, 1968.
37. Lodge, J. P. An Automatic Air Sampler for Use with Membrane Filters. J.
Meteorol.» 13:406-408, 1956.
38. Petersen, B. A., T. A. Bishop, C. C. Chuang, T. L. Hayes, D. A. Trayser,
D. Hupp, and H. Leonard. In: Diesel Engine Emissions of Particulates
and Associated Organic Matter, 3rd Year Final Report, CRC-APRAC Project
No. CAPE-24-72, 1982.
39. Cautreels, W., and K. VanCauwenberghe- Experiments on the Distribution
of Organic Pollutants Between Airborne Particulate Matter and Corres-
ponding Gas Phase. Atmos. Environ.. 12:1133-1141, 1978.
40. Jones, P. W., J. E. Wilkinson, and P. E. Strup. Measurement of
Polycyclic Organic Materials and Other Hazardous Organic Compounds in
Stack Gases State-of-the-Art. U. S. EPA-600/2-77-202, U. S. EPA,
Research Triangle Park, NC, p. 62, 1977.
41. Lindgren, J. L., H. J. Krauss, and M. A. Fox. A Comparison of Two
Techniques for the Collection and Analysis of Polynudear Aromatic
Compounds in Ambient Air. 0. Air Pollution Control Assoc., 30(2):166-
168, 1980.
42. Keller, C. D., and T. F. Bidleman. Collection of Airborne Polycyclic
Aromatic Hydrocarbons and Other Organics with a Glass Fiber Filter
Polyurethane Foam System. Atmos. Environ.. 18:837-845, 1984.
43. Chatot, G., R. Dangy-Caye, and R. Fontanges. Study of Air Pollution Due
to Polycyclic Aromatic Hydrocarbons in the Lyon Region by Means of Two
Collectors with Different Principles of Operation. Atmos. Environ..
7(8):819-826, 1973.
44. Hargis, K. M., M. I. Tiller, M. Gonzales, and L. L. Garcia. Aerosol
Sampling and Characterization in the Developing U.S. Oil-Shale Industry.
Department of Energy, Washington, D. C., Report No. LA-UR-81-2715, Conf-
811167-1, p. 27, 1981.
35
-------
45- White, C. M., A. G. Sharkey, M. L. Lee, and D. L. Vassilaros. Some
Analytical Aspects of the Quantitative Determination of Polynuclear
Aromatic Hydrocarbons in Fugitive Emissions from Coal Liquefaction
Process. In: Polynuclear Aromatic Hydrocarbons, P. W. Jones and P.
Leber, editors. Ann Arbor Science Publication, Inc., Ann Arbor,
Michigan, pp. 201-275, 1979.
46. Grosser, Z. A., J. C. Harris, and P. L. Levins. Quantitative Extraction
of Polycyclic Aromatic Hydrocarbons and other Hazardous Organic Species
from Process Streams using Macroreticular Resins. In: Polynuclear
Aromatic Hydrocarbons. P.W. Jones and P. Leber, editors. Ann Arbor
Science Publication, Inc., Ann Arbor, Michigan, pp. 67-79, 1979.
36
-------
SECTION 5
CHEMICAL ANALYSIS METHODOLOGY
INTRODUCTION
Many studies have been conducted to characterize the PAH content in
airborne particulate matter by various analytical techniques. In this review,
emphasis will be placed on evaluating different analytical and screening
methods to identify suitable methods for the U.S. EPA proposed experimental
study.
The analytical techniques that have been used to determine PAHs in
ambient air include UV absorption spectroscopy, luminescence spectroscopy,
thin layer chromatography (TLC), high performance liquid chromatography
(HPLC), gas chromatography (GC}, gas chrornatography/mass spectrometry (GC/MS),
Fourier-transform infrared spectroscopy (FT/IR), and Fourier-transform nuclear
magnetic resonance spectroscopy (FT/NMR). Each method has distinct advantages
and limitations. Often methods car be combined to increase the advantages and
decrease the limitations for a specific application. A discussion of the
different chemical analysis methods is given in the following paragraphs.
CHEMICAL ANALYSIS METHODS
UV Absorption Spectroscopy
From 1960-1970, many studies(l~5) of PAH determinations were performed
using UV absorption techniques. Recently, applications of UV techniques for
PAH determination have been few, and the UV absorption techniques that have
been used are usually coupled with HPLC and/or GC for separation and
detection. The UV absorption technique has several disadvantages, including
poor sensitivity compared to other techniques such as luminescence, and
overlap of spectra for PAH isomers. Many of the quantitative data in the
literature for BaP in environmental samples are probably erroneous, especially
those data obtained before 1960, due to the interference of benzo(e)pyrene
and/or benzo(k)fluoranthene/benzo(b)fluoranthene. Few studies have been con-
ducted using more sophisticated UV methods to fully utilize the potential of
UV absorption spectroscopy. For example, low temperature and derivative
absorption spectra can offer more information than conventional UV spectra
recorded at room temperature. A prototype instrument has been developed(°~9J
for the monitoring of PAH vapors in the field with second-derivative UV
absorption spectra. This method is independent of sample capacity, light
intensity fluctuations, and source energy variations and does not require
sample preparation to remove particulate matter prior to analyses.
37
-------
Hawthorne and Thorngate have also investigated the analysis of a mixture of
PAHs with a least-squares data-analysis computer program.(9) This relatively
new technique appears to be successful for selected PAH analyses. Although
some additional development, optimization, and field evaluation are still
necessary before it can be applied to routine analysis for ambient air
samples, this technique may be an excellent screening method for micro-
environment site selection.
Luminescence Spectroscopy
Numerous studies(10-19) have been conducted using luminescence
techniques to determine PAHs in environmental samples. Sawicki(lO) has
reviewed the early applications of fluorescence in the analysis of polluted
air. He found that luminescence can provide greater specificity and sensi-
tivity than UV absorption techniques in the determination of PAHs, although
interferences from other compounds, including impurities in standards, can
make the analysis of mixtures difficult. Similar problems were identified by
another group(17) that indicated tha~ it is difficult to separate benz(a)-
anthracene, chrysene, and triphenylene species. Fluorescence methods(20,21)
for the determination of single PAH components in mixtures containing inter-
fering compounds are available, and many of these techniques have been applied
to identify BaP.
Luminescence cannot often be used alone to identify PAHs in mixtures
because choosing a single wavelength that is characteristic of a particular
PAH is net possible for all PAHs. Additional problems can occur when measuring
PAHs with luminescence techniques in real ambient air samples. Shifts in
wavelength maxima are observed in solution measurements as a function of
solvent strength. Increased solvent polarity often generates a bathochromic
shift ( transition). Another problem with solution optical spectroscopy is
the quenching effect observed when additional species in solution suppress the
fluorescence of the PAH species by intermolecular deactivation. Sawicki and
colleagues^) have observed this phenomenon with nitrobenzene and
nitromethane.
An approach(23-25) to minimize these problems is to use the Shpol'skii
effect, which involves the resolution of characteristic vibrational fine
structure in the luminescence emission spectra of PAHs in frozen solutions in
an n-alkane. The main disadvantage of this technique is that analyses are
limited to the determination of PAHs which are soluble in the n-alkane.
Another problem with this approach, that has been discussed by Shpol'skii and
Bolotnikova in a review,(26; is that the multiple site structure frequently
observed in Shpol'skii PAH spectra and the quasilinear (sharp line) effect
depend on the freezing rate, concentration of the PAH of interest, and the
presence of additional impurities.
Another current development in the use of luminescence for the
determination of PAHs is the X-ray excited optical luminescence (XEOL) of PAHs
in frozen solutions. One groupC27-30) applied the XEOL technique to obtain
profiles of PAHs in coal, shale, and fuel oil. These investigators indicated
that significant improvements in the clean up procedure to isolate PAH frac-
tions or subfractions will be necessary to obtain quantitative data on actual
38
-------
samples with this technique. However, no study has been conducted using this
technique to determine PAHs in ambient air samples.
Another relatively new technique is luminescence analysis using
selective laser excitation. Brown and coworkers(31-33) conducted several
studies involving the determination of PAHs by laser-induced fluorescence
line-narrowing spectrometry (FLNS) in glassy matrices. They analyzed a
solvent-refined coal sample without sample preparation by using two different
techniques, GC/MS and FLNS, and quantified three PAHs: pyrene,
benzo(e)pyrene, and benzo(a)pyrene. The GC/MS and FLNS data were 1030 ppm and
830 ppm for pyrene, 29 ppm and 56 ppm for BeP, and 84 ppm and 95 ppm for BaP,
respectively. However, when HPLC cleanup was used before analysis, both the
FLNS and GC/MS determination of pyrene yielded values four times higher (i.e.,
4000 ppm). The authors could not provide a reasonable explanation for this
discrepancy. Other studies(34-36) have also been conducted using laser-
induced luminescence for the determination of PAHs. In general, studies
indicate that this technique needs more evaluation and development before it
can be used for routine analysis of ambient air samples.
Recently, Vo-Dinh's(37,39-47) gr0Up conducted a series of studies to
evaluate room temperature phosphorimetry (RTP) and synchronous luminescence
(SL) spectrometry techniques for the determination of PAH in environmental
samples. Conventional methods in phosphorimetry usually involve the prepar-
ation of oxygen-free solutions and the use of rigid matrices of frozen organic
solvent to avoid inter-molecular deactivation. These techniques involve time-
consuming preparation and special experimental devices. RTP is a relatively
new technique, which can be used to detect the phosphorescence emitted from
organic compounds adsorbed on solid substrates such as silica, alumina, and
filter paper at room temperature. Vo-Dinh's group(37,40,42) devoted extensive
efforts to developing the use of RTP as a rapid, simple tool for monitoring
PAHs in fossil fuel and coal conversion products. The same group also
evaluated the use of heavy atom effects to increase the phosphorescence
intensities of specific compounds.
The work of Vo-Dinh and his colleagues(41) with synchronous luminescence
involved the characterization of naphthalene derivatives in waste water from a
coal conversion process. In the synchronous fluorescence techniques, the
excitation and emission wavelengths are scanned at the same time with a
constant wavelength interval between them which produces simplified spectra
of PAHs. However, Latz and coworkersC^a) pointed out the limitations of
synchronous luminescence in multicomponent analyses. The results indicate
that qualitative surveys can be in error because of wavelength coincidences
and/or weak fluorescence signals. For example, the largest peak in the
spectrum was attributed to an anthracene concentration of 1 g/ml with only a
small contribution from 40 g/ml phenanthrene which had its strongest peak at
the same wavelength. The loss of spectral Information when the synchronous
technique is used can cause misleading results. Vo-Dinh and coworkers(43-47)
also applied RTP and SL together as rapid screening tools for monitoring PAHs
in environmental samples. In one study.(46) rjp and SL were used to determine
PAHs in extracts of a particulate material sample collected on XAD-2 resin.
The authors found that fluorimetric and phosphorimetric techniques are
complementary In their capabilities for PAH measurements. Anthracene was
39
-------
easily detected by SF but could not be observed by RTP. BaP can be quantified
with SF while the RTP emission of the compound is disrupted by the intense
emission from pyrene. With more development and evaluation, SL and RTP
techniques can probably be applied for rapid screening of selected PAH
compounds in ambient air samples. It is recommended that progress on this
work be followed.
Thin Layer Chromatography (TLC)
Several investigators(48-67) have used TLC to separate PAHs and PAH
derivatives in ambient air particulate extracts, followed by UV absorption
and/or fluorescence spectrometry analyses. In general, TLC techniques are
simple, rapid, and less expensive than other separation methods. The main
disadvantage of TLC separation is that some active PAHs may adsorb onto an
active surface such as alumina and decompose. Elution problems may also occur
if compounds bond strongly to the adsorption surface.
For TLC separations, no single method is generally superior to another.
The choice of mobile and stationary phases depends on the matrix of the
mixture. For example, in one study(4^) a cellulose acetate adsorbent system
gave best results for the separation of the benzopyrene fraction obtained in
column chromatography (i.e., BaP is completely separated from B(k)F, BeP, and
perylene). The cellulose adsorbent system gave the best results for the
separation of the PAHs. The greatest range in retention values (RB-values)
was obtained with a cellulose adsorbent.
Sawicki's group(48-54) have used TLC techniques extensively for the
determination of PAHs and their derivatives in various samples (e.g., ambient
air particulate matter, coal-tar Ditch). They developed a simple method(50)
which allows a direct fluorescence analysis of TLC spots. The same group(54)
also applied various quenching effects in TLC for determining PAH derivatives.
In this study, eight fluorescence quenching techniques were used in the direct
analysis of spots on TLC plates. By using these techniques, the following
compounds were identified in ambient air particulates: benz(a)acridine,
benz(c)acridine, 7H-benz(d,e)anthracenone, benzo(f)quinoline, benzo(h)quino-
line, phenalen-l-one, and xanthen-9-one.
Two dimensional development(56,65,66,68) in TLC has been apolied and is
particularly valuable for complex mixtures such as extracts of airborne
particulate material and/or diesel exhaust particulate material. With this
technique, the sample extract Is applied to the TLC plate and Is developed in
one direction. Then the plate is rotated through 90° and developed in the
second direction. The solvents are varied in these two developments, so
different separation effects are obtained in the second dimension. After
separation, spots are extracted and determined by fluorescence spectrophoto-
metry. (56,65,66) Recently,(68) a direct fluorescence analysis has been used
after two-dimensional TLC chromatography.
In conclusion, TLC techniques have been widely used for the separation
of PAHs, even though more efficient and automated systems are available, such
as HPLC or GC. This can be attributed to the simplicity of operation and the
40
-------
reasonable detection limit of TLC.(59) with proper applications, such as the
selection of stationary and mobile phases based on the nature of air
particulate, TLC can be a reliable method for screening PAHs in extracts of
ambient air particulate material.
High Performance Liquid Chromatography (HPLC)
Recently, high performance liquid chromatography (HPLC) has been widely
applied for the determination of PAHs in environmental samples.(70-97) The
majority of PAH determinations conducted by HPLC involve the use of an
octadecylsi lane-coated (Cis) reverse-phase packing material. Numerous Ci8
materials are commercially available which differ significantly in selec-
tivity characteristics for PAH. Wise and coworkers(86) have evaluated the
retention and selectivity characteristics for PAHs on several commercial Ci8
columns. The authors indicated that the BaP/BeP selectivity ratio for one
specific commercial Ci8 column was significantly greater than that for any of
the other columns evaluated in their study, but the authors did not identify
the brand of this tested column.
UV monitors and fluorescence detectors are both widely used in HPLC
analyses. Usually, the less expensive UV detectors are employed in analyses
requiring a fixed wavelength within the range of 250-280 nm. Recently,
several studies(72,76,79,94; have used variable wavelength UV and fluorescence
detectors in series. With this technique, PAHs that are not sensitive to UV
detection are detected by the fluorescence detector, and those PAHs that are
not amenable to fluorescence detection are monitored by the UV detector,
producing a significant increase in sensitivity.
Several other types of detectors have been used in HPLC analyses. One
group(89,90) recently developed a two-dimensional fluorimetry detector which
seems promising, although this system has not been used to analyze PAHs in
ambient air. In another study, C91) room temperature liquid phosphorescence
detection was used with HPLC to determine PAHs. This technique does not
appear useful since, compared to fluorescence detection, the phosphorescence
was weak and difficult to obtain.
No reference has been found describing the use of synchronous
fluorescence (SF) detection with HPLC for the determination of PAHs in ambient
air. One groupC?) used reductive electrochemical detection with HPLC to
detect nitro PAHs in diesel extracts. By comparing retention times and
hydrodynamic voltammograms of unknown peaks with those of reference nitro
PAHs, the authors confirmed the presence of 1-nitropyrene in diesel extracts.
For complex matrices such as synthetic fuels or airborne particulate
material, HPLC can be used as a preparative procedure to initially(21) frac-
tionate the sample. Analytical scale HPLC or GC is then used to identify and
quantify the PAHs.(®7,95,9b,114)
Tomkins and colleagues,(95) using a semi-preparative scale normal phase
HPLC procedure, separated a wide variety of sample types (air particulate
matter, coal fly ash and crude oils) into fractions. The fraction with three-
41
-------
through six-ring PAHs was then analyzed by reversed phase HPLC with
fluorescence detection or by GC with flame ionization detection. The authors
claimed that the method offers a more rapid and facile approach than tra-
ditional procedures involving solvent partitioning and column chromatography
in the isolation step. However, some of the PAHs showed poor recoveries from
the fractionation scheme, indicating that preparative HPLC would r.ot be useful
in every application.
Another method developed by Sonnefeld and coworkers(93) was on-line
coupling of a normal phase HPLC system to a reverse phase HPLC system. The
on-line coupling system consists of a diamine column for on-column concen-
tration of a selected fraction from a normal phase column separation and a
solvent-exchanged procedure using a mobile phase of 10 percent acetonitrile in
water transferring the analyte species from the concentrator column onto the
head of a guard column. The analyte species were then transferred from the
guard column to a reversed phase column by using gradient elution. This on-
line multidimensional system produced repeatable determinations of PAH in
complex mixtures. These workers also found that an increase in the recovery
of most of the PAHs studied could be obtained when the concentration system
was purged at ambient temperatures without heating the concentrator column.
This procedure, however, required a longer purging time. In addition, certain
PAHs were lost in the system and could not be recovered. The extent of this
problem must be determined before this HPLC method can be used to obtain
quantitative information.
In general, HPLC with UV and/or fluorescence detection can be used for
the determination of PAHs in ambient air. Depending on the nature of the
mixture, HPLC analysis can be conducted without sample clean-up, choosing
optimum detection conditions. The semi-preparative and/or on-line HPLC frac-
tionation can be an alternative to the classical solvent partition/adsorption
column chromatographic procedure. However, these techniques still ha^e some
limitations such as incomplete recovery of PAHs and limited size of samples
which can be generated ( 100 mg). More studies are therefore required to
evaluate and improve these methods, before they can be applied to routine
analyses of ambient air.
Gas Chromatography (GC)
Several studies(98-110)
have been performed involving the determination
of PAHs in ambient air particulate samples and diesel exhaust samples by
capillary column GC. The results of these studies demonstrate that capillary
GC can be used as a routine analytical tool for the determination of PAHs.
However, a sample clean-up procedure is required to remove the interfering
compounds such as aliphatic hydrocarbons.
Bjtirseth(107,108) conducted several studies of the determination of PAHs
in workplace atmospheres. He concluded that the best stationary phase, from
the aspects of separation efficiency, column bleeding, and long-term
stability, was SE-54. Lee and coworkers(m) conducted a GC retention index
study to develop a retention index system for programmed temperature runs,
using naphthalene (200.00), phenanthrene (300.00), chrysene (400.00), and
picene (500.00) as retention standards. The average 95 percent confidence
42
-------
limits for four measurements on more than 200 compounds were +0.25 retention
index unit. The authors indicated that even column-to-column variations were
unimportant when using this retention measurement approach.
Several detectors are used in gas chromatography, including
UV (100,101,104) fluorescence,(106>n3) fiame ionization (FID),(9°,99,103,107,
108,110,111) and electron capture.(112) The UV and fluorescence detectors,
used in a stopped-flow mode with the addition of solvent, were used in earlier
PAH determinations. The flame ionization detector (FID) is now universally
used for PAH determinations. The advantages of FID are linear response,
sensitivity, and day-to-day quantitative reliability in routine determi-
nations. Typical detection limits for PAHs are below 1 ng; different detector
designs and instruments can cause some variations in this limit.
With proper sample preparation procedures to isolate a PAH fraction from
complex mixtures of ambient air extracts, the capillary column GC/FID
technique can be used for the routine determination of PAHs. Recently, a
study(114) was conducted to determine nitrated PAHs in ambient air samples
using GC with a nitrogen-selective detector. In this study, a method was
developed for isolating PAHs and their nitro derivatives by normal phase HPLC.
The nitrated PAH fraction was analyzed by GC with nitrogen selective detection
(NP detector). Compounds identified in airborne particulate matter included
9-nitroanthracene, 1-nitropyene, and 10-nitrobenz(a)anthracene.
It would be worthwhile to conduct a series of studies for the
determination of nitrated PAHs using GC with electron capture detection, Hall
detection in the nitrogen mode, and/or NP detection to address the possi-
bility of using GC for the routine determination of nitrated PAHs. It should
be noted that singla column/single detector GC and HPLC have only weak
specificity, and confirmation of compound identifications made by these
techniques is necessary.
Gas Chromatoqraphy/Mass Spectrometry (GC/MS)
Numerous applications using a GC/MS technique for determining PAHs in
air particulate matter were found in the literature.(H5-122) The advantages
of this technique are high sensitivity for trace level detection, specificity
for unequivocal identification, and versatility for the separation of large
numbers of compounds. The main disadvantage is that it is significantly more
expensive than GC/FID, HPLC/UV, fluorescence, or other techniques. For most
studies, the mass spectrometer was operated using either full scan or selected
ion monitoring (SIM) modes. A recent study(H3) used GC/MS in the SIM mode to
quantify five PAHs in diesel exhaust particulate material. In the SIM mode
the mass spectrometer concurrently monitors one or more ion peaks,
characteristic of a specific compound, during its expected elution time from
the gas chromatographic column. Because the ion peaks that are monitored are
specific to the PAH compounds being analyzed, ion peaks from other compounds
at non-monitored masses will not contribute to the monitored ion current
signal. Therefore other compounds will not interfere with the analysis, and
SIM will enhance the sensitivity compared to the full scan mode. The
quantification limit of this procedure was 175 pg of selected PAHs injected on
the GC column.
43
-------
Recently, 3attelle developed a gas chromatography/negative ion chemical
ionization mass spectrometry (NCI, HRGC/MS) method using on-column injection
to identify and quantify nitro PAHs in extracts of diesel exhaust particulate
material and air particulate material.(122,124) The NCI technique provides up
to a 100-fold increase in sensitivity and selectivity, compared to
conventional chemical ionization, for detection of nitro PAHs. The on-column
injection method provides significant benefits for the analysis of
nitroaromatics over the conventional heateu injection port methods. Nitrated
PAHs, especially dinitropyrenes, are thermally labile and will decompose at
injection port temperatures necessary for sample volatilization. With the NCI
GC/MS on-column injection technique, the san^jle can be injected into the
chromatographic system at a lower temperature (e.g., 40°C) to eliminate degra-
dation of the thermally labile nitroaromatics. Chemical ionization is much
less energetic than electron impact, which increases the ionization efficiency
and thus enhances the detection sensitivity. This is due to the
electronegative nature of the nitro substituent, which is highly susceptible
to attachment of a thermal electron from the reagent gas plasma. For the
reasons listed above, the NCI on-column injection GC/MS method is the most
sensitive and selective method for the determination of nitro PAHs. The
quantification limit for several nitro PAHs using this method is 0.1 ng on the
column.
For the future U.S. EPA experimental study, both EI GC/MS and NCI GC/MS
techniques can be used for determining PAHs and nitro PAHs respectively.
Fourier-Transform Nuclear Magnetic Resonance (FT-NMR)
and Infrared Spectroscopy (FT-IR)
Both FT-NMR and FT-IR have, been used to determine PAHs in various
matrices. Wehry and coworkers(125-128) have conducted detailed investigations
of the applicability of matrix isolation (Ml) FT-iR in the qualitative and
quantitative determination of PAHs. In one study,(126) these workers
demonstrated the application of this technique to the identification of PAHs
of coal-derived materials.
Bartle and coworkers(129) identified methyl derivatives of PAHs in air
particulate material and in tobacco and marijuana smoke condensates with FT-
NMR. The analytical method involved separating sample condensates into
fractions of similar ring types with chromatographic techniques and deter-
mining PAH compounds in the fractions with FT-NMR. The positions of substi-
tution in the rings were identified from the methyl chemical shifts in the FT-
NMR spectra. The authors indicated that for the lower relative molecular mass
fractions of anthracene-phenanthrene and f1uoranthene-pyrene the smaller
number of methyl derivatives makes identification possible from FT-NMR spectra
alone.
For the determination of PAHs in ambient air, both FT-IR and FT-NMR
techniques are not practical. Both techniques require larger sample sizes
than other techniques (HPLC, GC, and/or GC/MS). Also, the identification of
PAHs in mixtures is difficult with both FT-IR and FT-NMR techniques. However,
both FT-IR and FT-NMR can be useful tools for determining the structure of
unknown PAHs.
44
-------
SCREENING METHODS
Based on the review of available analysis methods for the determination
of PAHs in ambient air samples, several screening methods are selected for
possible application in the future EPA experimental study and described in the
following sections.
Sensitized Spot Test
A screening procedure based on naphthalene-enhanced fluorescence has
been extensively validated by the U.S. EPA Industrial Environmental Research
Laboratory at the Research Triangle Park, North Carolina.(130-133) in the
enhanced fluorescence spot test, a portion of the sample extract is trans-
ferred to filter paper along with a highly concentrated naphthalene solution.
After solvent vaporization, the unknown molecular species are entrained in a
crystalline naphthalene matrix. In the naphthalene matrix, the native PAH
analytes are excited by vibrational coupling with the more energetic excited
states of the naphthalene to produce an enhanced fluorescence. This enhanced
fluorescence is easily detected visually. For selected compounds, e.g.,
fluoranthene, a sensitivity of 10 pa was reported for this spot test.(132) Two
interferences were observed(in the spot test: highly colored samples
restricted viewing of the fluorescence level, and samples containing
substantial amounts of phthalate esters produced false positive results. No
false negative results were observed in this study. The color interference
problem can be easily eliminated by diluting the sample. However, the false
results obtained with phthalate esters are not as easily reconciled and can
pose a major deterrent for using the spot test to screen samples for content
PAH. A Battelle study(122) has identified phthalate esters as the major
component in the polar fraction of air particulate material. The phthalate
ester interference problem must be evaluated before the spot tests can be used
as a screening method for the determination of PAHs in ambient air.
Nevertheless, this technique is inexpensive, simple, and rapid and should be
useful as a screening procedure to identify samples to be carried forward for
more expensive analyses.
UV Spectroscopic Method
A surrogate method(134) for the determination of total PAH concentration
(fluoranthene equivalents) in industrial effluents was developed by Battelle.
This method employed solvent extraction, alumina column chromatographic
cleanup (optional), and UV absorbance determination. The UV detection step
utilized a bandpass filter in order to obtain more uniform response between
the various PAHs. In this method, the matrix can produce interferences that
are coextracted from the sample. The extent of these interferences varies and
depends upon the nature and diversity of the matrix. A cleanup procedure can
be used to overcome the interferences, but the cleanup procedure will offset
to some extent the simplicity of the method. Nevertheless, with modifications
and evaluation, the UV spectroscopic method may be very useful as a screening
method to determine PAHs in ambient air.
45
-------
TLC Procedure
Many studies (discussed in an earlier section) have used TLC with UV or
fluorescence detection for the determination of PAHs in ambient air samples.
TLC is rapid, reproducible, and inexpensive, and can be employed as a
screening method. One group(135) separated BaP from other chemical species
using an acetylated cellulose substrate and optical isolation of BaP by direct
reflectance fluorescence from the TLC plate. This group was able to
accurately screen 30-40 samples per day for BaP using this technique. A
screening TLC procedure can be developed for the measurements of selected PAHs
in the future experimental study.
Luminescence Technique
As mentioned in an earlier section, Vo-Oinh's group has investigated
synchronous fluorescence (SF) and room temperature phosphorescence techniques
for PAH determinations. However, few of their studies involved ambient air
samples. These techniques are applicable as screening tools for PAH measure-
ment in ambient air samples; however, further investigations and evaluations
are needed.
Recently, Battelle (136) studied the use of a pulsed tunable-dye laser
system to conduct fluorescence/phosphorescence measurements of PAHs. This
technique also has potential as a screening method in ambient air study, but
further studies are needed to evaluate the possibility of the use of this
system to obtain direct fluorescence and/or phosphorescence measurements on
the filters.
46
-------
REFERENCES
SECTION 5
1. Biological Effects of Atmospheric Pollutants: Particulate Polycyclic
Organic Matter. In: Detection, Identification and Quantification,
Division of Medical Sciences, National Research Council, National Academy
of Sciences, Washington, D. C., pp. 296-297, 1972.
2- Lee, M. L., M. V. Novotny, and K. D. Bartle. Analytical Chemistry of
Polycyclic Aromatic Compounds. Academic Press, New York, pp. 291-295,
1981.
3. McCallum, J. D. Ultraviolet Analysis c-.f Urban Airborne Particulates for
Polynuclear Aromatic Hydrocarbons. Beckman Instruments, Inc., Fullerton,
California, Scientific and Process Instruments Division, Application Data
Sheet UV-8097, 1961.
4. Dubois, L., A. Zdrojewski, P. Hennawar, and J. L. Monkman.
Identification of the Orqanic Fraction of Air Sample. Atmos. Environ.,
4(2):199-207, 1970.
5. Fischer, R. Spectrophotometry Procedure for a Quick Estimation of the
Amount of Polycyclic Aromatic Hydrocarbons in Soot Samples. Fresenius'
Z. Anal. Chem.. 249(2):110-115, 1970.
6. Gammage, R. B., T. Vo-Dinh, A. R. Hawthorne. A New Generation of
Monitors for Polynuclear Aromatic Hydrocarbons from Synthetic Fuel
Production. In: Polynuclear Aromatic Hydrocarbons. Carcinogenesis-A
Comprehensive Survey. Volume 3. edited by P. VI. Jones and R. I.
Freudenthal, Raven Press, New York, pp. 155-174, 1978.
7. Hawthorne, A. R., 0. H. Thorngate, R. B. Gammage, and T. Vo-Dinh. Trace
Organic Analysis Using Second-Derivative UV-Absorption Spectroscopy.
Symposium on Trace Organic Analysis, Gaithersburg, Maryland, p. 12, 1978.
8. Hawthorne, A. R. DUVAS: A Field Portable Second-Derivative UV-
Absorption Spectrometer for Monitoring PNA Vapors. Symposium on
Assessing the Industrial Hygiene Monitoring Needs for the Coal Conversion
and Oil Shale Industries, Upton, New York, NTIS C0NF-781150-2, p. 18,
1978.
9. Hawthorne, A. R., and J. H. Thorngate. Application of Second-Derivative
UV-Absorption Spectrometry to Polynuclear Aromatic Hydrocarbon Analysis.
Appl. Spectrosc., 33(3):301-305, 1979.
10. Sawicki, E. Talanta. 16:1231, 1969.
47
-------
11. Sawicki, E., T. R. Hauser, and T. W. Stanley. Ultraviolet, Visible, and
Fluorescence Spectral Analysis of Polynuclear Hydrocarbons. Intern. J.
Air Pollution. 2:253-272, 1960.
12. Sawicki, E., and H. Johnson. Characterization of Aromatic Compounds by
Low-Temperature Fluorescence and Phosphorescence: Application to Air
Pollution Studies. Microchem. J., 8(1):85-101, 1964.
13. Dikun, P. P. Detection of Polyryclic Aromatic Hydrocarbons in Polluted
Atmosphere and of Other Pollutants by Means of Quasi linear Fluorescence
Spectra. Zh. Prkl. Spektrii. 6(2):202-209, 1967, CA67:14647M.
14. Kropp, J. L., and W. R. Dawson. Fluorescence and Phosphorescence of
Aromatic Hydrocarbons in Poly(methylmethacrylate) as a Function of
Temperature. TRW Systems, Redondo Beach, California, Chemical Sciences
Department, Report No. 07126-60D4-R000, NTIS: AD-672 849, p. 16, 1969.
15. Matsushita, H., and Y. Esumi. Rapid Analyzing Method of Benz(a)pyrene in
Air Pollutants. Rodo Eisei Kenkyusho Nenpo, 1971:39-40, 1971.
16. Zdrojewski, A., L. Dubois, G. E. Moore, R. Thomas, and J. L. Monkman.
Fluorescence Spectroscopy in the Analysis of Air Samples. Am. Chem.
Soc., Div. Water, Air, Waste Chan., Preprint, 6(l):40-44, 1966.
17. Heinrich, G., and H. Guesten. Fluorescence Spectroscopic Determination
of Airborne Polynuclear Aromatic Hydrocarbons. Fresenius' Z. Anal.
Chem.. 278(4):257-262, 1976.
18. Hellmann, H. Change of the Fluorescence Intensity of Polycyclic
Aromatics on Thin-Layer Plates. Fresenius' Z. Anal. Chem., 295C1):24—29,
1979.
19. Jurgensen, A., E. L. Inman, Jr., J. D. Winefordner. Conprehensive
Analytical Figures of Merit for Fluorimetry of Polynuclear Aromatic
Hydrocarbons. Anal. Chim. Acta. 131(1):187—194, 1981.
20. Hutzinger, 0., S. Safe, and M. Zander. Polycylclic Aromatic
Hydrocarbons. Analabs Res. Notes, 13(3):1-11, 1973.
21. Dubois, L., A. Zdrojewski, and J. L. Monkman. Comparison of Three
Methods for Trace Analysis of Polycyclics, Mikrochim. Acta, '3:503-911,
1967.
22. Sawicki, E., T. W. Stanley, and W. C. Elbert. Quenchofluorometric
Analysis for Fluoranthenic Hydrocarbons in the Presence of Other Types of
Aromatic Hydrocarbons, Talanta, 11:1433-1441, 1964.
23. Kirkbright, G. F., and C. G. DeLima. Use of the Shpol'skii Effect for
the Determination of Trace Amounts of Polynuclear Aromatic Hydrocarbons.
Proc. Soc. Anal. Chen.. ll(3):55-60, 1974.
48
-------
24. Stenberg, U., and A. Colmsjoe. Identification of Polynuclear Aromatic
Hydrocarbons by Shpol'skii Low Temperature Fluorescence. Anal. Chem.,
51(1):145-150, 1979.
25. Lai, E. P., E. L. Inman, Jr., J. D. Winefordner. Conventional
Fluorescence Spectrometry of Polynuclear Aromatic Hydrocarbons in
Shpol'skii Matrixes at 77 K. Talanta, 29(7):60l-608, 1982.
26. Shpol'skii, E. V., and T. N. Bolotnikova. Pure Appl. Chem., 37:183,
1974.
27. D'Silva, A. P., G. 0. Oestreich, and V. A. Fassel. X-Ray Excited Optical
Luminescence of Polynuclear Aromatic Hydrocarbons. Anal. Chem..
48(6):915-917, 1976.
28. Fassel, V. A., C. S. Woo, A. P. D'Silva. Polynuclear Aromatic
Hydrocarbons in Coal-Identificatlon by Their X-Ray Excited Optical
Luminescence. Environ. Sci. Techno!., 12(2):173-174, 1978.
29. Oestreich, G. J. X-Ray Excited Optical Luminescence of Polynuclear
Aromatic Hydrocarbons. Ames Lab., IA. NTIS No. IS-T-856, p. 164, 1979.
30. Woo, C. S., A. P. D'Silva, and V. A. Fassel. Characterization of
Environmental Samples for Polynuclear Aromatic Hydrocarbons by an X-Ray
Excited Optical Luminescence Technique. Anal. Chem., 52(1):159—164,
1980.
31. Small, G. J., M. C. Edelson, and J. C. Brown. Fluorescence Line
Narrowing Spectrometry in Organic Glasses Containing Parts-per-Billion
Levels of Polycyclic Aromatic Hydrocarbons. Anal. Chem.. 50(9^:1394-
1397, 1978.
32. Small, G. 0., J. C. Brown, and J. A. Ouncanson, Jr. Fluorescence Line
Narrowing Spectrometry in Glasses for Direct Determination of Polycyclic
Aromatic Hydrocarbons in Solvent-Refined Coal. Anal. Chan., 52(11):1711-
1715, 1980.
33. Brown,J. C. Fluorescence Line Narrowing Spectrometry of Polycyclic
Aromatic Hydrocarbons in Organic Glasses. Diss. Abst. Int., Pt. B:Sci. &
Eng.. 43(4), 1982.
34. Bykovskaya, L. A., R. I. Personov, and V. Y. Romanovskii. Luminescence
Analysis of Complex Organic Materials 3ased on Resolved Line Spectra
Produced by Selective Laser Excitation. Anal. Chim. Acta. 125:1-11,
1981.
35. Maple, J. R., E. L. Hehry. Fluorescence Photoselection of Matrix
Isolated Polycyclic Aromatic Hydrocarbons. Anal. Chem.. 53(8):1224-1229.
1981.
36. Quigley, G. P. Synchronous Detection of Laser-Induced Fluorescence. Los
Alamos National Lab., NM. Report No. LA-UR-82-1929; C0NF-820734-1, NTIS,
DE 82019571, p. 17, 1982.
49
-------
37. Vo-Dinh, T. Recent Progress in Room Temperature Phosphorimetry for
Analysis of PNA. NTIS Report No. C0NF-770361-1, p. 9, 1977.
38. Latz, H. W., A. H. Ullman, and J. D. Winefordner. Limitations of
Synchronous Luminescence Spectrometry in Multicomponent Analysis. Anal.
Chem.. 50(14):2l48-2149, 1978-
39. Vo-Dinh, T., R. B. Gammage, and A. R. Hawthorne. Analysis of Organic
Pollutants by Synchronous Luminescence Spectrometry. NTIS Report No.
C0NF-781039-8, p. 14, 1978.
40. Vo-Dinh, T. Rapid Analysis of PNA Compounds in Complex Samples by Room
Temperature Phosphorimetry. NTIS Report No. CONF-781150-1, p. 11, 1978.
41. Vo-Dinh, T., R. B. Gammage, A. R. Hawthorne, and 0. H. Thorngate.
Synchronous Spectroscopy for Analysis of Polynuclear Aromatic Compounds.
Environ. Sci. Techno!.. 12(2):1297-1302, 1978.
42. Vo-Dinh, T., and R. 5. Gamr.iage. Room Temperature Phosphorimetry for the
Analysis of Environmental Systems. NTIS Report No. C0NF-791059-8, p. 16,
1979.
43. Gamnage, R. B., T. Vo-Dinh, and P. R. Martinez. Synchronous Fluorescence
and Phosphorescence at Room Temperature for Levels 1 and 2 Organic
Analysis. U.S. Environmental Protection Agency, Office of Research and
Development, U.S. EPA-600/9-81-018, Proc., 2nd Symp. Process Meas.
Environ. Assess., 119-133, 1981.
44. Vo-Dinh, T. Recent Developments in the Analysis of Air Samples by
Luminescence Techniques. Oak Ridge National Lab., TN. NTIS Report No.
C0NF-810346-1, p. 15, 1981.
45. Vo-Dinh, T. New Luminescence Techniques Simplify Air Analysis.
Instrument. Techno!., 28(5):45-48, 1981.
46. Vo-Dinh, T., R. B. Gammage, and P. R. Martinez. Analysis of a Workplace
Air Particulate Sample by Synchronous Luminescence and Roan-Temperature
Phosphorescence. Anal. Chem., 53(2):253-258, 1981.
47. Vo-Dinh, T. Rapid-Screening-Luminescence Techniques for Trace Organic
Analysis. NTIS Report No. C0NF-820381-2, p. 22, 1982.
48. Sawicki, E., T. W. Stanley, W. C. Elbert, and J. D. Pfaff. Application
of Thin Layer Chromatography to the Analysis of Atmospheric Pollutants
and Determination of Benzo(a)pyrene. Anal. Chem.. 36(3):497-502, 1964.
49. Sawicki, E., and H. Johnson. Thin-Layer Chromatographic Characterization
Tests for Basic Polynuclear Compounds- Application to Air Pollution.
Mikrochiro. Acta. (2-4):435-450, 1964.
50
-------
50. Sawicki, E., T. W. Stanley, and H. Johnson. Direct Spectrophoto-
fluorc-metric Analysis of Aromatic Compounds of Thin-Layer Chromatograms.
Microchem. J.. 8(3):257-284, 1964.
51. Sawicki, C. R., and E. Sawicki. In: Progress in Thin-Layer
Chromatography and Related Methods, edited by A. Niederwieser and G.
Pataki, Ann Arbor Sci. Publ., Ann Arbor, Michigan, Vol. Ill, p. 233,
1972.
52. Stanley, T. W., M. J. Morgan, and J. E. Meeker, Thin-Layer
Chromatographic Separtation and Spectrophotometry Determination of
Benzo[a)pyrene in Orqanic Extracts of A1r-Borne Particulates. Anal.
Chen., 39(11):1327-1329. 1967.
53. Sawicki, E., M. Guyer, and C. R. Engel. Paper and Thin-Layer
Electrophoretlc Separations of Polynuclear Aza Heterocyclic Compounds.
J. Chromatoq.. 30(2):522-527, 1967.
54. Sawicki, E., and H. Johnson. The Various Quenching Effects in Thin-Layer
Chromatography-Application to Air Pollution. J. Chromatoq., 23:142-148,
1966.
55. Lam, J., and A. Berg. Spectrophotometry Determination of Polycyclic
Aromatic Hydrocarbon Separated by Thin-Layer Chromatography, and
Evaluation of the Liqht Sensitivity of Hydrocarbon Spots. J. Chromatoq.,
20(1):163-171, 1965.
56. Koehler, M., and H. J. Eichhoff. Rapid Method for Determination of
Polynuclear Aromatic Hydrocarbons in Atmospheric Dust. Fresenius" Z.
Anal. Chem., 232(6):401-409, 1967.
57. Shlmp, G. J. The ApDlication of Thin Layer Chromatography to the
Analysis of Particulate Atmospheric Pollutants for the Presence of
Carcinogenic Compounds. Dust Topics, 4(4):5-12, 1967.
58. Abdoh, Y., N. Aghdaie, M. R. Darvich, and M. H. Korgami. Detection of
Some Polynuclear Aromatic Hydrocarbons and Determination of
Benzo(a)pyrene in Teheran Atmosphere. Atmos. Environ.. 6(12):949-952,
1972.
59. Toth, L. Spectrofluorometric Jn Situ Analysis of Polycyclic Aromatics
After Separation on Acetylated Cellulose Layers. I. Qualitative and
Quantitative Evaluation. J. Chromatoqr.. 50(l):72-82, 1970.
60- Matsushita, H., and K. Arashidani. Simple and Rap^'d Analysis of
Benzo(a)pyrene in Coal Tar Pitch. Bunseki Kaqaku 25(2): 76-80. 1976.
(Japan.) CA85:49096E.
61. British Coke Research Assoc. Determination of Polynuclear Aromatic
Hydrocarbons in Airborne Particulate Matter. Coke Res. Rep., 76:12.
1973.
51
-------
62. Bender, D. F., and W. C. Elbert. Thin-Layer Chromatographic Analysis in
Air Pollution (Chapter 5). Chromatogr. Anal. Environ., New York, Marcel
Dekker, Inc., pp. 193-243, 1975.
63. Fujie, K. Analysis of Polynuclear Aromatic Hydrocarbons. Bunseki
Analysis. 3:165-171, 1975.
64. Yamazaki, M., H. Shirayama, and 5. Okumura. Analysis of Polynuclear
Aromatic Hydrocarbons in Ambient Air. J. Japan. Soc. Air Pollution.
10(4):203, 1975.
65. Matsushita, H., F. Otsuka, and S. Yamada. A Simple Microanalytical
Method for Benzo(a)pyrene in Airborne Particulates. Bunseki Kaqaku
27(7):488-493, 1977 (Japan.) CA87:205727K.
66. Mainwaring, S. J., M. McGuirk. The Analysis of Benzpyrene. In:
Analytical Techniques in the Determination of Air Pollutants. Melbourne,
Australia, May 23-27, 1977. Published by South Yarra, Victoria,
Australia Clean Air Society of Australia and New Zealand, pp. 84-89,
1977.
67. Katz, M., T. Sakuma, and A. Ho. Chromatographic and Spectral Analysis of
Polynuclear Aromatic Hydrocarbons-Quantitative Distribution in Air of
Ontario Cities. Environ. Sci¦ Techno!.. 12(8):909-9l5, 1978.
68. Kraft, J., A. Hartung, K. H. Lies, and J. Schulze. Two Dimensional Tl_C
Determination of PAH in Diluted Automobile Exhaust Gases. J. High
Resolut. Chromatogr. Commun.. 5(9):489-494, 1982.
69. Zaner, M., U. Breymann, H. Dreeskairp. Complementary Quenchofluorimetry
with Electron Donors and Acceptors in the Analysis of Polycyclic Aromatic
Hydrocabons. Fresenius' Z. Anal. Chem.. 293(3):208-2l0, 1978.
70. Matsushita, H. Application of High Speed Liquid Chromatography and Thin-
Layer Chromatography to Environmental Carcinogens and Related Compounds.
New Methodol. Ecol. Chem. Res. Conf. Proc., edited by F. Coulston, Int.
Acad. Print Co., Ltd., Tokyo, Japan, pp. 1-10, 1973.
71. Fox, M. A., and S. W. Staley. Analysis of Polycyclic Aromatic
Hydrocarbons in Atmospheric Particulate Matter by High Pressure Liquid
Chromatography Coupled with Fluorescence Techniques. Anal. Chem..
48(7):992-998, 1976.
72. Krstulovic, A. M., D. M. Rosie, and P. R. Brown. Selective Monitoring of
Polynuclear Aromatic Hydrocarbons by High Pressure Liquid Chromatography
with a Variable Wavelength Detector. Anal. Chem.. 48(9):1383-1386, 1976.
73. Thomas, R., and N. Zander. High-Pressure Liquid Chromatography of
Polycyclic Aromatic Hydrocarbons. Fresenius' Z. Anal. Chem.. 282(5):443-
445, 1976.
52
-------
74. Golden, C., and E. Sawicki. Ceramic Alumina in the HPLC Determination of
Benzo(a)pyrene in Air Particulate Material. Anal. Lett., 9(10):957-973,
1976.
75. Lopez, M. C. High Pressure Liquid Chromatography and its Application to
the Separation of Polynuclear Aromatic Hydrocarbons in Atmospheric Dust
and Burning Residues. CEA Centre d'Etudes Nucleaires de Grenoble, 38
(France). Service de Protection et des Etudes d*Environment. NTIS
Report No. CEA-R-4678, p. 43, September 1975.
76. Christensen, R. G., and W. E. May. Detectors for Liquid Chromatographic
Analysis for Polynuclear Aromatic Hydrocarbons. National Bureau of
Standards, Washington, D. C., NTIS Report No. PB-282-867, p. 15, 1978.
77. Smillie, R. D., D. T. Wang, and 0. Meresz. The Use of a Combination of
Ultraviolet and Fluorescence Detectors for the Selective Detection and
Quantitation (sic) of Polynuclear Aromatic Hydrocarbons by High Pressure
Liquid Chromatography. o. Environ. Sci. Health-Part A. A13(l):47-59,
1978.
78. Thomas, R. S., R. C. Lao, D. T. Wang. Determination of Polycyclic
Aromatic Hydrocarbons in Atmospheric Particulate Hatter by Gas
Chromatography-Mass Spectrometry and High-Pressure Liquid Chromatography.
In: Polynuclear Aromatic Hydrocarbons, Carcinogenesis-A Comprehensive
Survey, Vol. 3, edited by P. W. Jones and R. I. Freudenthal. Raven
Press, New York, pp. 9-19, 1978.
79. Das, B. S., and G. H. Thomas. Fluorescence Detection in High Performance
Liquid Chromatographic Determination of Polycyclic Aromatic Hydrocarbons.
Anal. Chem.. 50(7):967-973, 1978.
80. Liao, J. C., and R. F. Browner. Determination of Polynuclear Aromatic
Hydrocarbons in Polyvinyl Chloride) Smoke Particulates by High Pressure
Liquid Chromatography and Gas Chromatoqraphy-Mass Spectrometry. Anal.
Chem., 50(12):1683, 1978.
81. Fechner, D. „ and B. Seifert. Determination of Polycyclic Aromatic
Hydrocarbons in Dust Deposits by High-Performance Liquid Chromatography
Using Multi-Wavelength Detection: Part 1: Qualitative Results.
Fresenius' Z. Anal. Chem.. 292(3):193-198, 1978.
82. Nielsen, T. Determination of Polycyclic Aromatic Hydrocarbons in Auto-
mobile Exhaust by Means of High Performance Liquid Chromatography with
Fluorescence Detection. J. Chromatoq.. 170(1):147-156, 1979.
83. Roumeliotis, P., K. K. Unger, G. Tesarek, and E. Muehlberg. Optimization
of the Phase System in the Analysis of Polynuclear Aromatics (PNA) from
Diesel Engine Exhaust by High Performance Liquid Chromatography.
Fresenius' Z. Anal. Chem., 298(4):241-249, 1979.
53
-------
84. Das, B. S., and G. H. Thomas. The Use of Fluorescence Detection in High
Performance Liquid Chromatographic Routine Analysis of Polycyclic
Aromatic Hydrocarbons in Environmental Polution and Occupational Health
Studies. Trace Org. Anal.: New Front. Anal. Chem.. 519:4-1-56, 1979.
CA91:150751P.
85. Roumeliotis, P., and K. K. Unger. Quantitative Analysis of Polynuclear
Aromatics from Diesel Exhaust by High Performance Liquid Chromatography
Using UV Photometric Detection. Anal. Chan. Symp. Ser.. 3:229-245, 1980.
86. Wise, S. A., K. J. Bonnett, and W. E. May, Normal and Reverse Phase
Liquid Chromatography Separations of Polycyclic Aromatic Hydrocarbons.
In: Polynuclear Aromatic Hydrocarbons: Chemistry and Biological Effects,
edited by A. Bjorseth and A. 0. Dennis, Battelle Press, Columbus, Ohio,
p. 791, 1980.
87. Tomkins, B. A., W. H. Friest, J. C. Caton, and R. R. Reagan.
Multicomponent Isolation and Analysis of Polynuclear Aromatics. Oak
Ridge National Lab., TN. NTIS Report No.: CONF-811086-4; DE 82002903, p.
12, 1981.
88- Konash, P. L., S. A. Wise, and W. E. Hay. Selective Quenchofluorometric
Detection of Fluoranthenic Polycyclic Aromatic Hydrocarbons in High-
Performance Liquid Chromatography. National Bureau of Standards,
Washington, D. C., NTIS Report No.: P382-130006, p. 11, 1981.
89. Fogarty, M. P., D. C. Shelly, and I. M. Warner. High Performance Liquid
Chromatography/Video Fluorometry. Part I. Instrumentation. Texas A and
M Univ., College Station, Department of Chemistry, NTIS Report No.: TR-2;
AD-A105868/4, p. 37, September 1981.
90. Shelly, D. C., M. P. Fogarty, and I. M. Warner. High-Performance Liquid
Chromatography/Video Fluorometry. Part II. Applications. Texas A and M
Univ., College Station, Department of Chemistry, NTIS Report No.: D0E-
EV; DE 81028458, p. 35, 1981.
91. Armstrong, D. W., W. L. Hinze, K. H. Bui, and H. N. Singh. Enhanced
Fluorescence and Room Temperature Liquid Phosphorescence Detection in
PseudoDhase Liquid Chromatography (PLC). Anal. Lett.. 14(A19):1659-1667.
1981.
92. Rappaport, S. M., Z. L. Jin, and X. B. Xu. High-Performance Liquid
Chromatography with Reductive Electrochemical Detection of Mutagenic
Nitro-Substituted Polynuclear Aromatic Hydrocarbons in Diesel Exhausts.
J. Chromatoq.. 240(1):145-154, 1982.
93. Sonnefeld, W. J., W. H. Zoller, W. E. May, and S. A. Wise. On-Line
Multidimensional Liquid Chromatographic Determination of Polynuclear
Aromatic Hydrocarbons in Complex Samples. Anal. Chem.. 54(4):723-727.
1982.
54
-------
94. Choudhury, D. P. Applications of On-Line High Performance Liquid
Chromatography Rapid Scanning Ultraviolet Spectroscopy to Character-
ization of Polynuclear Aromatic Hydrocarbons in Complex Mixtures in:
Polynuclear Aromatic Hydrocarbons, W. M. Cooke and A. J. Dennis, editors,
Battelle Press, Columbus, Ohio, pp. 265-276, 1981.
95. Tonkins, B. A., W. H. Griest, J. E. Caton, 0. S. Wike, and R. R. Reagan.
Multicomponent Isolation and Analysis of Polycyclic Aromatic Hydro-
carbons. In: Polynuclear Aromatic Hydrocarbons: Physical and Biolog-
ical Chemistry. M. Cooke, A. J. Dennis, and G. L. Fisher, editors.
Battelle Press, Columbus, Ohio, pp. 813-824, 1982.
96. Vandemark, F. L., and J. L. DiCesare. High Resolution Preparative Liquid
Chromatography, Its Application to the Analysis of Polynuclear Aromatic
Hydrocarbons. In: Polynuclear Aromatic Hydrocarbons: Physical and
Biological Chemistry. M. Cooke, A. J. Dennis, and G. L. Fisher, editors.
Battelle Press, Columbus, Ohio, pp. 835-843, 1982.
97. Chakraborty, B. B., and R. Long. Gas Chromatographic Analysis of
Polycyclic Aromatic Hydrocarbons in Soot Samples. Environ. Sci.
Techno!.. l(10):82B-834, 1967.
98. Kraft, K., K. H. Lies, and A. Hartung. Quantitative Determination of
Polycyclic Aromatic Hydrocarbons in Exhaust Gases of Automobiles by Means
of Glass Capillary Chromatography. Proc. Int. Syrup. Capillary
Chromatoqr.. 4:639-671, 1981.
99. Arito, H., R. Soda, and H. Matsushita. Gas Chromatographic Determination
of Polynuclear Hydrocarbons in Particulate Air Pollutants. Ind. Health.
5(3-4):243-259, 1967.
100. Brown, R. A., J. M. Kelliher, and W. H. King. Progress in Development of
Rapid Methods of Analysis for Trace Quantities of Polynuclear Aromatic
Hydrocarbons in Automobile Exhaust. Esso Research and Engineering Co.,
Linden, NJ. NTIS Report No.: PB-196-808, p. 36, 1970.
101. 3rown, R. A., T. D. Searl, W. H. King, Jr., W. A. Dietz, and J. M.
Kelliher. Rapid Methods of Analysis for Trace Quantities of Polynuclear
Aromatic Hydrocarbons and Phenols in Automobile Exhaust, Gasoline, and
Crankcase Oil. NTIS Report No.: CRC-APRAC-CAPEI2-68-3, December, p. 56,
1971.
102. Takada, S., T. Yamamoto, and K. Nishida. Determination of Polynuclear
Aromatics in Suspended Particles. Nippon Eiseiqaku Zasshi (Oap. J.
Hyg.), 26(1):147, 1971.
103. Grimmer, G. Determination of Total Content of Polycyclic Aromatic
Hydrocarbons in Air Pollution and Automobile Exhause Gas by Capillary Gas
Chromatography. Anal. Chew. (Berlin). 259(3):213-2l4, 1972.
55
-------
104. Sawicki, E. Tentative Method of Analysis for Polynuclear Aromatic
Hydrocarbons in Automobile Exhaust. Health Lab. Sci., 11(3):228-239,
1974.
105. Bartle, K. D., and M. L. Lee, and M. Novotny. High Resolution GLC (Gas-
Liquid Chromatography) Profiles of Urban Air Pollutant Polynuclear
Aromatic Hydrocarbons. Int. J. Environ. Anal. Chem., 3(4):349-35S, 1974.
106. Mulik, M. C. M. F. Guyer, G. M. Semeniuk, and E. Sawicki. A Gas Liquid
Chromatographic Fluorescent Procedure for the Analysis of Benzo(a)pyrene
in 24 Hour Atmospheric Particulate Samples. Anal. Lett.. 8(8):511-524,
1975.
107. Bjorseth, A. Analysis of Polycyclic Aromatic Hydrocarbons in Environ-
mental Samples by Glass Capillary Gas Chromatography. In: Polynuclear
Aromatic Hydrocarbons. Carcinogenesis-A Comprehensive Survey. Vol. 3,
edited by P. W. Jones and R. I. Freudenthal. Raven Press, NY, pp. 75-83,
1978.
108. Bjorseth, A. Measurement of PAH Content in Workplace Atmospheres. VDI-
Ber., 358:81-93, 1980. CA93:209410Y.
109. Szepesy, L., K. Lakszner, L. Ackermann, L. Podmaniczky, and P. Literathy,
Rapid Method for the Determination of Polycyclic Aromatic Hydrocarbons in
Environmental Samples by Combined Liquid and Gas Chromatography. J.
Chromatoqr.. 206(3):611-616, 1981.
110. Lee, M. L., D. L. Vassilaros, and D. W. Later. Capillary Column Gas
Chromatography of Environmental Polycyclic Aromatic Compounds. Int. J.
Environ. Anal. Chern.. 11(3-4):251-262, 1982.
111. Lee, M. L., D. L. Vassilaros, C. M. White, and M. Novotny. Retention
Indices for Progranraned-Temperature Capillary-Column Gas Chromatography of
Polycyclic Aromatic Hydrocarbons. Anal. Chem.. 51(5):768-774, 1979.
112. Harrison, E. K., and C.L.B. Powell. The Determination of Polynuclear
Aromatic Hydrocarbons by Gas-Liquid Chromatography. Ann. Occup. Hyq..
18(3):l99-206, 1975.
113. Thomas, L. C., and A. K. Adams. Detection of Fluorescent Compounds by
Modified Flame Photometric Gas Chromatoqraphy Detectors. Anal. Chem.,
54(14):2597-2599, 1982.
114. Nielsen, T. Isolation of Polycyclic Aromatic Hydrocarbons and Nitro
Derivatives in Complex Mixtures by Liquid Chromatography. Anal. Chem..
55(2):285, 1983.
115. Leo, R. C., R. S. Thomas, H. Oja, and L. Dubois. Application of a Gas
Chromatograph-Mass Spectrometer-Data Processor Combination to the
Analysis of the Polycyclic Aromatic Hydrocarbon Content of Airborne
Pollutants. Anal. Chem., 45(6):908-915, 1973.
56
-------
116. Lao, R. C., R. S. Thomas, and 0. L. Monkman. Computerized Gas
Chromatographic-Mass Spectrometric Analysis of Polycyclic Aromatic Hydro-
carbons in Environmental Samples. J. Chromatoq.. 112:681-700, 1975.
117. Petersen, B. A., C. C. Chuang, W. L. Margard, and D. A. Trayser.
Identification of Mutagenic Compounds in Extracts of Diesel Exhaust
Particulates. Presented at the 74th Annual Meeting of the Air Pollution
Control Association, Philadelphia, PA, June, 1981.
118. Cautreels, V., and K. VanCauwenberghe. Determination of Organic Com-
pounds in Airborne Particulate Matter by Gas Chromatography-Mass
Spectrometry. Atmos. Environ., 10(6):447-457, 1976.
119. Lao, R. C., R. S. Thomas, and J. L. Monkman. Application of GC-MS to the
Analysis of PAH in Environmental Samples. In: Carcinogenesis, Volume 1,
Raven Press, New York, pp. 271-281, 1975-
120. Lee, M. L., M. Nvotny, and K. D. Bartle. Gas Chromatography/Mass
Spectrometric and Nuclear Magnetic Resonance Determination of Polynuclear
Aromatic Hydrocarbons in Airborne Particulates. Anal. Chem.,
48(11) *.1566-1572, 1976.
121. Karasek, F. W., M. L. Parsons. Analysis of Houston Aerosol Samples by
GC/MS (Gas Chromatography/Mass Spectrometry) Methods. U.S. EPA-600/2-80-
071, Gov. Rep. Announce. Index, 80(21):4458, 1980.
122. Chuang, C. C., M. G. Nishioka, and B. A. Petersen. Fractionation and
Analysis of Particulate Organic Matter from Ambient Air Samples, Final
Report for U.S. EPA, Contract No. 68-02-3169 (WA-20), 1984.
123. Petersen, B. A., C. C. Chuang, T. L. Hayes, and D. A. Trayser. Analysis
of PAH in Diesel Exhaust Particulate by High Resolution Capillary Column
Gas Chromatography/Mass Spectrometry, SAE Technical Paper Series,
Passenger Car Meeting, Troy, MI, June, 1982.
124. Nishioka, M. G., and B. A. Petersen. Comparative Analysis of Combustion
Emission Extracts for Nitro Aromatics. Final Report for U.S. EPA,
Contract No. 68-02-3169 (WA-15), 1962.
125. Wehry, E. L., G. Mamantov, R. R. Kemmerer, H. 0. Brotherton, and R. C.
Stroupe. Low-Temperature Fourier Transform Infrared Spectroscopy of
Polynuclear Aromatic Hydrocarbons. In; Carcinogenesis, Volume 1, edited
by P. W. Jones and R. I. Freudenthal, Raven Press, New York, pp. 299-
309, 1976.
126. Hembree, D. M., A. A. Garrison, R. A. Crokcombe, R. A. Yokley, E. I.
Wehry, and G. Mamantov. Anal. Chem., 53(12):1783-1788, 1981.
57
-------
127. Wehry, E. L., G. Mamantov, R. R. Kerranerer, R. C. Stroupe, R. T.
Tokousbalides, E. R. Hinton, D. M. Hembree, R. B. Dickinson, Jr., A. A.
Garrison, P. V. Bilotta, and R. R. Gore. Analysis of Polynuclear
Aromatic Hydrocarbons by Matrix Isolation Fluorescence and Fourier
Transform Infrared Spectroscopy. In: Carcinogenesis-A Comprehensive
Survey, Vol. 3, edited by P. W. Jones and R. I. Freudenthal, Raven Press,
New York, d. 193, 1978.
128. Garrison, A. A., D. M. Hembree, Jr., R. A. Yokley, R. A. Crocombe, G.
Mamantov, E. L. Wehry. Use of Matrix Isolation Fourier Transform
Infrared (FTIR) in Gas Chromatographic Detection. Proc. SPIE-Int. Soc.
Opt. Eng., 289:150-153, 1981.
129. Bartle, K. D., M. L. Lee, and M. Novotny. Identification of
Environmental Polynuclear Aromatic Hydrocarbons by Pulse Fourier-
Transform Proton Nuclear Magnetic Resonance Spectroscopy. Analyst,
102(1219):731-738, 1977.
130. Levins, P. L., C. E. Rechsteiner, Or. and J. L. Stauffer. Measurement of
Polycyclic Organic Matter for Environmental Assessment. U.S. EPA-600/7-
79/191, 1979.
131. Smith, T. R. Evaluation of Sensitized Fluorescence for Polynuclear
Aromatic Hydrocarbon Detection. U.S. EPA-600/7-79/207, p. 79, 1979.
132. Smith, E. M., and P. L. Levins. Sensitized Fluorescence for the
Detection of Polycyclic Aromatic Hydrocarbons. U.S. EPA-600/7-78/182, p.
33, 1978.
133. Johnson, L. D., R. E. Luce, and R. G. Merrill. A Spot Test for
Polycyclic Aromatic Hydrocarbons. In: Polynuclear Aromatic Hydro-
carbons, edited by M. Cooke and A. J. Dennis, Battelle Press, Columbus,
Ohio, pp. 119-131, 1981.
134. Riggin, R. M., and P. E. Strup. Surrogate Methods for PAH Priority
Pollutants in Waste Water. Final Report for U.S. EPA, Contract No. 68-
03-2984, 1981.
135. Swanson, D., C. Morris, R. Hedgecoke, R. Jungers, R, Thompson, and 0.
Bumgarner. A Rapid Analytical Procedure for the Analysis of BaP in
Environmental Samples. Trends Fluoresc., 1(2):22-27, 1978.
136. Ivancic, W. A., L. L. Brown, R. M. Riggin, and R. H. Barnes. Analysis of
Polynuclear Aromatic Hydrocarbons in Particulate Matter by Luminescence
Techniques. EPA-600/54-84-033, 1984. NTIS: PB84-181 882.
58
-------
TECHNICAL REPORT DATA
(Please read Ins auctions on the revert* before completing)
1. REPORT NO. 2.
EPA/600/4-85/045
4. TITLE AND SUBTITLE
Review of Sampling and Analysis Methodology for
Polynuclear Aromatic Compounds in Air from Mobile
Sources
5. REPORT DATE
June 1985
B. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
C. C. Chuang and B. A. Petersen
8. PERFORMING ORGANIZATION REPORT NO.
9. performing organization name and ADDRESS
Battelle Columbus Laboratories
505 King avenue
Columbus, OH 43201
10 PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-3487, Task 25
12. SPONSORING AGENCY NAM" AND ADDRESS
EPA, Office of Research and Development
Environmental Monitoring Systems Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final, 3/1/83-11/30/83
14. SPONSORING AGENCY CODE
EPA/600/08
^15^CFPL6MENTARY NOTES
Iffi ABSTRACT
-The objective of this program was to review and recommend test compounds and sampling and
analysis methods for a future EPA study of polynuclear aromatic hydrocarbons (PAH) in
microenvironments.
Review of PAH profiles in ambient air indicated that concentrations of PAH were generally
higher in winter than summer and varied with climate and between sampling sites within an
urban area. Levels of several PAH were found tc ie proportional to traffic density.
Studies of the biological activity of ambient air sables showed that some PAH and their
nitrated derivatives are extremely carcinogenic Mutagenic. The following compounds
were determined to be the most prevalent and muta^a: ",: in ambient air and were recommendec
for the future EPA study: phenanthrene, pyrene, cyclopenta(c,d)pyrene, benzo(a)pyrene,
dibenz(a,h)anthracene, 1-nitropyrene, fluoranthene, benz(a)anthracene, benzo(e)pyrene,
benzo(g,h,i)perylene, coronene, and 3-nitrofluoranthene.
In the review of PAH sampling methods, collection of both gaseous and particulate bound PAh
was determined to be necessary to accurately characterize health effects of PAH in ambient
air. Most studies have used filters to sample particulate-bound PAH and absorbents tc
collect vapor phase PAH. The major sampling problems encountered in these studies were PAI-
losses due to volatilization and reactivity.^-^***
17. KEY WORDS AND DOCUMENT ANALYSIS
L DESCRIPTORS
b. IDENTIFIERS/OPEN ENOEO TERMS
C. COSATI Fldd/Cioup
18. DISTRIBUTION STATEMENT
19. SECURITY CLASS f This ReportJ
21. NO. OF PAGES
67
20. SECURITY CLASS (This page)
22. PRICE
$10. OG
EPA Foon 2220-1 (R»». 4-77) previous coition is obsolete
i
------- |