United States
Environmental Protection
Agency
Environmental Monitoring Systems -
Laboratory
Research Triangle Park NC 27711
Research and Development
EPA/600/S4-85/065 Jan. 1986
Project Summary
Evaluation of Sampling and
Analytical Methodology for
Polynuclear Aromatic
Compounds in Indoor Air
C. C. Chuang, G. A. Mack, P. J. Mondron, and B. A. Petersen
The objective of this project was to
develop a generic sampling and analyt-
ical methodology to characterize the
polynuclear aromatic hydrocarbon
(PAH) concentrations in air within
various microenvironments. The follow-
ing three studies were performed: eval-
uation of analytical methods, design of
a sampling method, and design of a
pilot study.
Two analytical methods, high per-
formance liquid chromatography with
ultraviolet absorption and fluorescence
detection and gas chromatography/
mass spectrometry, were evaluated for
the determination of PAHs and their
derivatives in air within microenviron-
ments. The results showed that gas
chromatography/positive chemical ion-
ization mass spectrometry with data
acquisition in the selected ion monitor-
ing mode is the preferred analytical
approach.
A modified EPA high volume sampler,
consisting of a quartz fiber filter and a
polyurethane foam (PDF) cartridge, is
proposed for use in a future experi-
mental study.
A literature review was conducted to
determine what is known about the
contribution of cigarette smoke to the
levels of PAHs in air within microenvi-
ronments and to evaluate the use of
quinoline and isoquinoline as possible
marker compounds for the levels of
cigarette smoke.
Based on the evaluation of analytical
and sampling methodology, a pilot
study was designed to assess PAH levels
in air in residences. A study using this
design was conducted in Columbus,
Ohio, during the winter of 1983/84.
The results can then be applied to a
future large-scale study involving the
measurement of human exposure to
PAH in air.
This Project Summary was developed
by £PA's Environmental Monitoring
Systems Laboratory, Research Triangle
Park, NC. to announce key findings of
the research project that is fully docu-
mented in a separate report of the same
title (see Project Report ordering infor-
mation at back).
Introduction
The overall objective of this project was
to develop sampling and analytical
methodology that can be used to study
human exposure to polynuclear aromatic
compounds and their derivatives in air in
microenvironments. The microenviron-
ments of greatest importance are those
where people spend most of their time.
They include residences, work places,
and commuting routes. Therefore, in this
work, generic sampling and analytical
methodology was designed to character-
ize the polynuclear aromatic compound
(PAH) concentrations in air within a wide
variety of microenvironments.
In the course of development of such
generic methodology, four aspects had to
be addressed: evaluation of the analytical
methodology for measurement of PAH in
air, development of sampling method-
ology, characterization of the influence of
cigarette smoke on the PAH concentration
in microenvironments, and design of a
pilot study.
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In the first three parts of this project,
investigations were conducted to select
analytical and sampling methods for an
experimental study. In the fourth part a
preliminary study was designed, the
results of which can be used to test the
generic monitoring procedure prior to
conducting a larger experimental study.
In the recently completed literature
review of sampling and analytical method-
ology for PAH in air, a series of poly-
nuclear aromatic hydrocarbons was
recommended for measurement to char-
acterize PAH in ambient air. Nitropyrene
was also selected for study because it is
extremely mutagenic and has been iden-
tified in extracts of urban air particle
samples. To assess the contributions of
PAH from tobacco smoke to the total PAH
levels, particularly within residences,
quinoline and isoquioline were selected
as possible markers. The target com-
pounds for this study are presented in the
following list.
Species
Class
Phenanthrene
Fluoranthene
Pyrene
Cyclopenta(c,d)pyrene
Benz(a)anthracene
Benzo(e)pyrene
Benzo(a)pyrene
Benzo(g,h,i)perylene
Coronene
1-Nitropyrene
Quinoline
Isoquinoline
PAH
PAH
PAH
PAH
PAH
PAH
PAH
PAH
PAH
Nitro-PAH
Nitrogen
heterocycle
Nitrogen
heterocycle
In the first part of this work, high
performance liquid chromatography with
ultraviolet absorption and fluorescence
detection (HPLC) and gas chromatog-
raphy/massspectrometry(GC/MS)were
evaluated for the determination of the
target compounds in the three compound
classes given above. In the second part,
generic sampling methodology for various
types of microenvironments was devel-
oped. Based on the results from the
analytical methodology evaluation, the
quantity of analyte necessary for an
accurate measurement was estimated.
Sampling parameters to collect the nec-
essary quantity of material for analysis
were then established. In the third part, a
literature survey was made to determine
what was known about the influence of
cigarette smoke on the PAH concentration
in microenvironments, and about the use
of quinoline and isoquinoline as evidence
of the level of PAH from cigarette smoke.
Only a few studies in the literature
involved the determination of PAH con-
centrations in air in residences. The work
performed in the fourth part of this study
was the design of a study to determine
the range of PAH contamination in resi-
dential air.
Results
The results of the evaluation of ana-
lytical methodology showed that the high
performance liquid chromatography with
ultraviolet absorption and fluorescence
detection (HPLC) did not detect all the
target compounds under one analytical
condition. At least two analyses, one
analysis for nitrogen heterocyclic com-
pounds and one analysis for nitropyrene
and PAHs, are required for the deter-
mination of all the target compounds by
the HPLC method. In addition, 'further
sample clean-up is necessary to perform
quantitative analysis using this method
on air particulate extracts. Although
negative chemical ionization gas chroma-
tography/mass spectrometry (NCI
GC/MS) has been demonstrated to be the
most sensitive technique for the deter-
mination of nitropyrene, this method does
not provide adequate sensitivity and
selectivity for all the target compounds. A
clean-up procedure is required for ana-
lyzing all the target compounds in an air
particulate extract using NCI GC/MS.
Both the positive chemical ionization (PCI)
andelectron impact(EI)GC/MS methods
are adequate for determination of all the
target compounds. The difference be-
tween the El and the PCI method is that
the PCI method is at least 10 times more
sensitive for nitrogen heterocyclic com-
pounds. Therefore, if the nitrogen hetero-
cyclic compounds are to be measured, the
HPLC, NCI GC/MS, and El GC/MS
methods are not appropriate to use for the
determination of the target compounds,
and the PCI GC/MS method is the
recommended analytical methodology for
the future experimental study.
Several important sampling parameters
were established in this study and are
summarized as follows:
Sampling volume
Sampling time
Sampling
temperature
Sampling flow rate
Filter face velocity
Filter capacity for
particles
Frequency of
sampling
Number of
sampling events
per site
and a PUF backup
trap
100 m3
8hr
<20°C
15-20mVhr
30-40 m/min
Very high
Depends on the
study design
Depends on the
study design
Parameter
Sampler
configuration
Conditions
A modified high
volume sampler
consisting of a filter
Based on these sampling parameters, a
generic sampling methodology has been
developed and can be used to collect PAH
compounds in various microenviron-
ments.
The results of the literature survey
showed that all the target compounds
except nitropyrene have been detected in
cigarette smoke condensate. The concen-
trations of PAHs in air within a micro-
environment in which cigarettes are being
smoked are higher than levels of PAHs
typically found in ambient air. Thus,
cigarette smoking may be a significant
contributor to PAHs found in air within
microenvironments. The survey also in-
dicated that quinoline and isoquinoline
are the most abundant aza-arene com-
pounds found in cigarette smoke con-
densate, but that these compounds also
have been detected in coal combustion
emission, ambient air particulate matter,
and automobile exhaust emission. There-
fore, quinoline and isoquinoline may not
be appropriate marker compounds for
cigarette smoking.
Conclusions and
Recommendations
The on-column injection, positive
chemical ionization, gas chromatog-
raphy/mass spectrometry (PCI GC/MS)
technique with data acquisition in the
selected ion monitoring mode has been
demonstrated to provide adequate sensi-
tivity, selectivity, specificity, and speed of
response for the determination of all the
target compounds. Therefore, use of the
PCI GC/MS method is strongly recom-
mended for analysis of the target com-
pounds in the future pilot study.
A modified high volume sampler,
consisting of a quartz fiber filter to collect
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paniculate matter and a polyurethane
foam cartridge to collect vapor is recom-
mended for evaluation and development
for use in the future study. Studies are
recommended to deter mine the retention
characteristics of PDF cartridges for PAHs
and to develop the analytical method to
remove PAHs from the PDF cartridges.
The results of the literature survey
showed that cigarette smoking may con-
tribute significantly to the levels of PAHs
in air within microenvironments. There-
fore, cigarette smoking is recommended
for consideration as an experimental
factor in the pilot study. The survey also
indicated that quinoline and isoquinoline
may not be appropriate marker com-
pounds for cigarette smoking. However,
these compounds should still be included
in the pilot study to determine whether
these two compounds can be used as
tracers for cigarette smoking.
C. C. Chuang, G. A. Mack, and P. J. Mondron are with Battelle Columbus Division,
Columbus, OH 43201; B. A. Peter sen is with Sciex. Inc.. Worthington, OH
43085.
Nancy K. Wilson is the EPA Project Officer (see below).
The complete report, entitled "Evaluation of Sampling and Analytical Methodology
for Polynuclear Aromatic Compounds in Indoor Air," (Order No. PB 86-120
326/AS; Cost: $11.95, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Environmental Monitoring Systems Laboratory
U.S. Environmental Protection Agency
Research Triangle Park. NC 27711
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