United States
Environmental Protection
Agency
Environmental Monitoring
Systems Laboratory
Research Triangle Park NC 27711
Research and Development
EPA/600/S4-87/031 Ja n. 1988
SERA Project Summary
Evaluation of Sampling and
Analytical Methods for
Nicotine and Polynuclear
Aromatic Hydrocarbon in
Indoor Air
J. C. Chuang, M. R. Kuhlman, S. W. Hannan, and C. Bridges
The objective of this project was to
evaluate a potential collection medium,
XAD-4 resin, for collecting nicotine and
polynuclear aromatic hydrocarbon
(PAH) and to determine whether one
collection system and one analytical
method will allow quantification of
both compound classes in air.
The extraction efficiency study was
performed to determine the extraction
method to quantitatively remove nic-
otine and PAH from XAD-4 resin.
Various solvents were used with both
the solvent-spiking and XAD-4 matrix-
spiking methods. The results showed
that a two-step Soxhlet extraction
consisting of dichloromethane fol-
lowed by ethyl acetate resulted in the
best recoveries for both nicotine and
PAH.
In the sampling efficiency study,
XAD-2 and XAD-4 resin were com-
pared, in parallel, for collection of PAH
and nicotine. Quartz fiber filters were
placed upstream of both adsorbents to
collect particles. Prior to sampling,
both XAD-2 and XAD-4 traps were
spiked with known amounts (2/ug) of
perdeuterated PAH and D3-nicotine.
The experiments were performed with
cigarette smoking and non-smoking
conditions.
The spiked PAH were retained well
in both adsorbents after exposure to
more than 300 m3 of indoor air. The
spiked XAD-4 resin gave higher recov-
eries for Da-nicotine than did the spiked
XAD-2 resin. The collection efficiency
for PAH for both adsorbents is very
similar but higher levels of nicotine
were collected on XAD-4 resin.
This Project Summary was devel-
oped by EPA's Environmental Monitor-
ing Systems Laboratory. Research
Triangle Park, NC, to announce key
findings of the research project that is
fully documented in a separate report
of the same title (see Project Report
ordering information at back).
Introduction
Many polynuclear aromatic hydrocar-
bons (PAH) are mutagens, carcinogens,
or both. There is increasing concern over
human exposure to these compounds in
indoor air from the workplace, home and
school.
Several studies have identified envi-
ronmental tobacco smoke (ETS) as a
major contributor to levels of PAH in
indoor air pollution. Battelle conducted
a pilot study to determine PAH in
residential air. The results indicated that
cigarette smoking is one of the major
contributors to levels of PAH. The study
found higher levels of paniculate matter
and PAH in homes occupied by smokers.
Other studies have also indicated that
cigarette smoking can substantially
increase the mutagenicity of the indoor
air.
It appears that nicotine can be an
important marker for ETS because it is
unique to tobacco smoke and is a major
-------
constituent of the smoke. However, it is
not clear whether air sampling and
analytical methods typically used for PAH
can be applied to nicotine. Different
collection media such as treated filters,
which require separate sample prepara-
tion and analyses, are normally used to
determine nicotine in air. It is desirable
to determine both compound classes in
indoor air with only one collection system
and analysis method.
The following study was carried out to
evaluate a potential collection medium,
XAD-4 resin, for nicotine and PAH and
to determine if one collection system and
analytical method can be used to deter-
mine both compound classes. This study
consisted of the following subtasks:
1. Extraction efficiency studies to
determine the optimum procedure
for determination of nicotine and
PAH.
2. A sampling efficiency study under
cigarette smoking and non-
smoking conditions, using a filter
and either XAD-4 or XAD-2.
3. Evaluation of different analytical
methods to measure nicotine and
PAH to determine if nicotine and
PAH can be measured within one
analysis.
Procedure
Different solvents or combinations of
solvents were evaluated in the extraction
efficiency study for XAD-4 resin. Prior to
extraction, an aliquot of the spiking
solution which contains selected PAH
and nicotine was spiked into either the
solvent reservoir (solvent spike) or the
clean XAD-4 resin (matrix spike). The
extraction was carried out for 16 hr. Prior
to concentration, the extracts were
filtered through clean pre-wet quartz
fiber filters. The extract was concen-
trated to about 1 ml and was analyzed
by gas chromatography/mass spec-
trometry (GC/MS).
Two prototype indoor air samplers
were placed parallel to each other and
were separated from each other by about
1 ft. Quartz fiber filter and XAD-2 resin
in series was used in one sampler, and
quartz fiber filter and XAD-4 resin in
series was used in the other sampler.
Prior to sampling, an aliquot of the
perdeuterated solution was spiked onto
both XAD-2 and XAD-4 cartridges. Then
the air was sampled at approximately 8
cfm flow rate for about 24 hr.
The samplers were exposed to
cigarette smoke during the sampling
period at uneven intervals for the first
four tests. In the fifth test, the samplers
were not exposed to cigarette smoke.
After sampling, XAD-2 and XAD-4
samplers were Soxhlet extracted by
dichloromethane followed by ethyl ace-
tate and were concentrated to about 1
ml for GC/MS analysis.
Results
A cleanup method for XAD-4 resin was
developed including Soxhlet extraction
with methanol, ethyl acetate and dichlo-
romethane sequentially. The results of
the extraction solvent spike demon-
strated that good recoveries were
obtained for the spiked PAH and nicotine
from various solvents tested including
dichloromethane, ethyl acetate, and
0.01% trimethylamine in ethyl acetate.
This finding indicated that the losses of
target compounds through sample han-
dling and concentration are negligible.
We also noted that the precipitates were
formed during the concentration of
0.01% trimethylamine in dichlorome-
thane. This observation suggested that
ammonium salts were formed between
trimethylamine and dichloromethane
during concentration. Thus this solvent
system was excluded from the matrix
spike experiment.
The results of the extraction matrix
spike indicated that recoveries of PAH
and XAD-4 were generally good, but not
for nicotine (27%) when dichlorometh-
ane was used as the extracting solvent.
The recovery of nicotine improved to
greater than 90 percent with ethyl
acetate. But the recoveries of some PAH
such as acenaphthylene and anthracene
were only from 70 to 60 percent with
this solvent. The recoveries of these PAH
did not improve when basic ethyl acetate
was used. Thus two-step extractions
were evaluated which consisted of
dichloromethane followed by either
0.01% pyridine in ethyl acetate or 100%
ethyl acetate. Overall, good recoveries for
both PAH and nicotine were obtained
from these two-step extractions.
The results of the sampling efficiency
study revealed that most PAH levels
found in the XAD-2 and the XAD-4
samples are indistinguishable from each
other. This finding suggested that both
XAD-2 and XAD-4 resin have similar
sampling efficiency for PAH. But levels
of nicotine found in XAD-4 samples were
higher than those in the corresponding
XAD-2 samples indicating that XAD-4
resin has better sampling efficiency for
nicotine.
Both electron impact (El) and positive
chemical ionization (PCI) GC/MS
methods were employed to analyze the
standard solution containing PAH and
nicotine. As expected, the PCI method
provides better detection sensitivity for
nicotine than the El method. The detec-
tion for PAH with both methods is very
similar. Fused silica capillary columns
with two film thickness (0.17 //m and
0.50 /jm) were evaluated. Better detec-
tion sensitivity for nicotine was detected
with the thinner film column (0.17/um).
Conclusions and
Recommendations
The following conclusions are based
on the results of this study:
1. The collection system, a quartz
fiber filter and XAD-4 resin in
series, can be used to collect both
PAH and nicotine in indoor air.
2. The extraction method, Soxhlet
extraction with dichloromethane
followed by ethyl acetate can
quantitatively remove both PAH
and nicotine from XAD-4 resin.
3. The analysis method, positive
chemical ionization, gas chroma-
tography/mass spectrometry oper-
ated in the multiple ion mode, can
be used to determine both PAH and
nicotine.
Because XAD-4 resin has better sam-
pling efficiency for nicotine than does
XAD-2 resin and both adsorbents show
comparable sampling efficiency for PAH,
quartz fiber filters and XAD-4 resin are
recommended for future field studies.
The recommended sample preparation
procedure is Soxhlet extraction with
dichloromethane followed by ethyl ace-
tate. The positive chemical ionization gas
chromatography/mass spectrometry
(PCI GC/MS) method operated in the
multiple ion detection (MID) mode is also
recommended for use in future studies
to determine both PAH and nicotine.
-------
J. C. Chuang. M. R. Kuhlman, S. W. Hannan, and C. Bridges are with Battelle,
Columbus Division, Columbus. OH 43201-2693.
Nancy K. Wilson is the EPA Project Officer (see below).
The complete report, entitled "Evaluation of Sampling and Analytical Methods
for Nicotine and Polynuclear Aromatic Hydrocarbon in Indoor Air," (Order
No. PB 88-124 615/AS; Cost: $12.95; subject to change) will be available
only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
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
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
= 0 .2 Z =
Official Business
Penalty for Private Use $300
EPA/600/S4-87/031
------- |