EVALUATION OF POLYURETHANE FOAM CARTRIDGES
FOR MEASUREMENT OF POLYNUCLEAR
AROMATIC HYDROCARBONS IN AIR
C. C. Chuang, W. E. Bresler, and S. W. Hannan
Battelle Columbus Laboratories
Columbus, Ohio 43201
Contract Number 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
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DISCLAIMER
The information in this document has been funded wholly or in part by
the United States Environmental Protection Agency under Contract 68-02-3487
to Battelle Columbus Laboratories. It has been subject to the Agency's peer
and administrative review* and it has been approved for publication as an EPA
document. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
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FOREWORD
Measurement and monitoring research efforts are designated to anticipate
environmental problems, to support regulatory actions by developing an in-
depth understanding of the nature and 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 En-
vironmental Monitoring Systems Laboratory, Research Triangle Park, North
Carolina, has responsibility for assessment of environmental monitoring
technology and systems, 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 evaluation of polyurethane foam
cartridges for polynuclear aromatic hydrocarbon measurements provides
important information that can be applied to the measurement of the extent of
human exposure to the polynuclear aromatic compounds.
Thomas R, Hauser, Ph.D.
Director
Environmental Monitoring Systems Laboratory
Research Triangle Park, North Carolina 27711
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ABSTRACT
The objective of this project was to evaluate polyurethane foam (PUF)
cartridges as collection media for quantification of vapor phase polynuclear
aromatic hydrocarbons (PAHs) in air.
Two cleanup methods for PUF cartridges -- compression rinsing and
combined compression rinsing and Soxhlet extraction — have been evaluated.
Both methods successfully remove interfering material and background PAHs
from the PUF. The compression rinsing method is recommended because it is
easier, faster, and cheaper.
Two procedures for extraction of PAHs from the PUF matrix, Soxhlet
extraction and compression rinsing, were compared. Modified EPA medium
volume samplers having quartz fiber filters to collect particles and PUF
cartridges to trap vapors were used. Prior to sampling,.known quantities of
perdeuterated PAHs were spiked into each cleaned PUF cartridge. Eight
samplers were operated outdoors in parallel for 24 hours. After sampling,
four PUF samples were Soxhlet-extracted with 10 percent ether/hexane and the
other four PUF samples were extracted by alternate compression and
decompression fifty times in the same solvent. These sample extracts were
analyzed by on-column injection, electron impact gas chromatography/mass
spectrometry (El GC/MS) to determine PAHs. The results showed that
compression rinsing is comparable to conventional Soxhlet extraction, and
that both methods successfully remove PAHs from the PUF cartridges. The
compression rinsing method was then used in the stability study.
The stability study was carried out to determine the stability of PAHs
adsorbed on PUF cartridges as a function of storage time between collection
and extraction. Two sets of PUF samples were collected for this study. The
first set of samples was stored in the presence of light, and the second set
of samples was kept in the dark. The storage temperature for both sets of
samples was approximately 20°C, The samples were stored for one, ten,
twenty, or thirty days and then extracted with 10 percent ether/hexane.
Sample extracts were analyzed by El GC/MS. The levels of perdeuterated
benzo(a}pyrene decreased significantly during storage. The rate of decrease
was much faster when the PUF cartridges were stored in light. Other PAH
levels were not adversely influenced by the storage time.
Selected sample extracts obtained from the pilot study of previous work
(Task 35) were solvent exchanged into dimethylsulfoxide at eight different
concentration levels. These samples were packed in dry ice and sent to EPA,
HERL/ERC for microbioassay analysis.
This report was submitted in fulfillment of Contract No, 68-02-3487 by
Battelle Columbus Laboratories under the sponsorship of the U.S.
Environmental Protection Agency. This report covers the period of August 1,
1984 to December 31, 1984, and work was completed as of December 31, 1984.
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CONTENTS
Foreword iii
Abstract ...... .......... . . iv
Tables vi
Abbreviations , viii
Acknowledgment . ................. ix
1. Introduction ............... .... 1
2. Conclusions. 3
3, Recommendations 5
4. Experimental Procedures 7
5. Results and Discussions. 15
References 24
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TABLES
Number Page
4,1 Level of Deuterated PAHs In the spiking stock solution .... 9
4.2 Level of Non-deuterated PAHs in the stock standard solution. . 9
4.3 GC and HS operating conditions 12
4.4 Mass distribution of sample extracts for microbioassay .... 14
5.1 Levels of PAHs in PUF cartridges cleaned by two
different methods. . ...... ..... 16
5.2 Recoveries of PAHs from spiked PUF cartridges using two
extraction methods—compression and Soxhlet extraction .... 17
5.3 Levels of PAHs in PUF cartridges extracted by two
methods—compression and Soxhlet extraction. . 17
5.4 Recoveries of PAHs from PDF cartridges spiked prior to
sampling as a function of storage time. Storage conditions:
20°C, in the light 19
5.5 Recoveries of PAHs from PUF cartridges spiked prior to
sampling as a function of storage time. Storage conditions:
20°C, in the dark. . . 20
5.6 Levels of native PAHs found in PUF cartridges as a function of
storage time. Storage conditions: 20°C, in the light ... 21
5.7 Levels of native PAHs found in PUF cartridges as a function of
storage time. Storage conditions: 20°C, in the dark. ... 22
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LIST OF ABBREVIATIONS
BaP benzo(a}pyrene
CI chemical ionization
Dg-PAH native polynuclear aromatic hydrocarbons
DMSO dimethyl sulfoxide
Dn-PAH perdeuterated polynuclear aromatic hydrocarbons
El electron impact
GC/MS gas chromatography/mass spectrometry
PAC polynuclear aromatic compounds
PAH polynuclear aromatic hydrocarbons
PCB polychlorinated biphenyls
RIC recontructed ion chromatogram
PUF polyurethane foam
VII
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ACKNOWLEDGMENT
The financial support of the U.S. Environmental Protection Agency and
the thoughtful discussion of Dr, Nancy K. Wilson are gratefully acknowledged.
Technical assistance from Dr. Ralph Riggin and Mr. James E. Howes, Jr. is
appreciated.
viii
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SECTION 1
INTRODUCTION
Polynuclear aromatic compounds have been extensively studied and
have received increased attention in studies of air pollution in recent
years because some of these compounds are highly carcinogenic or
mutagenic. To understand the extent of human exposure to polynuclear
aromatic compounds, reliable sampling and analytical methodology must be
established for monitoring the concentrations of these compounds in air.
In general, the analytical methodology is well developed, but the
sampling procedures can often reduce the validity of analytical results.
Several studies {1-4} have shown that the three- to four-ring
polynuclear aromatic hydrocarbons (PAH) in air may be mainly in the
vapor phase and are not retained by filters because of volatilization.
A wide variety of adsorbents such as Tenax-GC, XAD-2 resin and
polyurethane foam (PUF) has been used to sample organic vapors (5). The
PUF cartridge is easy to handle in the field and has good airflow
characteristics', it has been successfully used for collection of
pesticide and polychlorinated biphenyl (PCB) vapors (6).
Recently, Battelle conducted a study {7} to collect ambient and
indoor air PAH using a sampler with a quartz fiber filter and a PUF
back-up trap. It was observed that the PUF cartridges changed from a
pale white to a light yellow color over a one week storage period. It
is not known whether this color change during storage is associated with
any change in the PUF cartridge's ability to retain PAHs. In a large
scale air monitoring program, placement of the samplers in the field and
the return of filters and traps after air collection to analytical
laboratories may involve several weeks. Therefore it is necessary to
conduct a study to assess the stability of PAHs adsorbed on the PUF
cartridges during storage.
-------
The objective of this project was to evaluate PUF cartridges for
collection and subsequent analysis of vapor phase PAH in air. Two
studies were performed:
(a) Extraction study to evaluate two extraction procedures,
Soxhlet extraction and compression rinsing, for removal
of PAH from the PUF matrix.
(b) Stability study to determine the stability of PUF traps
by examining the measured PAH concentration as a function
of storage time between collection and extraction.
The sample extracts were analyzed by electron impact gas
chromatography/mass spectrometry (El SC/MS) to determine both native
PAHs and spiked perdeuterated PAHs.
In addition, sample extracts obtained from the range-finding study
done under a previous work assignment [Task 35 (7)] were solvent
exchanged into dimethyl sulfoxide at eight different levels and sent to
EPA, HERL/ERC for microbioassay.
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SECTION 2
CONCLUSIONS
Two PUF cleanup methods, compression rinsing and combined com-
pression rinsing and Soxhlet extraction, have been evaluated for their
ability to remove interfering material and background PAHs from PUF
cartridges. The results showed that the compression-only technique is
comparable to the combined compression and Soxhlet extraction method.
Thus the compression method is recommended for use in the future for
time and cost savings.
The results of the extraction study indicated that levels of both
native and perdeuterated PAHs found in the PUF cartridges were similar
using either Soxhlet extraction or compression rinsing. It has been
demonstrated that both methods can successfully remove PAHs from the PUF
cartridges. Since significant time and cost savings can be achieved by
using compression rinsing, this method was used in the stability study.
Generally, good recoveries for the spiked perdeuterated PAHs were
obtained for PUF samples extracted immediately after collection, with
the exception of Da-naphthalene. This finding demonstrated that PUF
cartridges cannot quantitatively retain volatile two-ring PAHs under the
sampling conditions employed. Greater loss of volatile components would
be expected at higher sampling temperatures. It should be noted that
cyclopenta(c,d)pyrene and higher molecular weight (_>252) PAHs were not
detected in the PUF samples. 1-Nitropyrene was also not found in the
PUF samples.
The stabilities of PAHs adsorbed on PUF cartridges during storage
with and without light were investigated. The results indicated that
levels of BaP decreased significantly during storage. The rate of
decrease was much faster when PUF cartridges were stored in the
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presence of light. The levels of the remaining PAHs were not
significantly influenced by the storage time.
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SECTION 3
RECOMMENDATIONS
Both XAD-2 resin and polyurethane foam (PUF) are commonly used to
collect PAH vapors in ambient air sampling (8). A comparative study is
recommended to evaluate the flow characteristics and the collection
efficiency for PAH vapors by using these two adsorbents (XAD-2 and PUF)
as backup traps in ambient air sampling. Recently, several research
groups indicated that extracts of clean PUF plugs show mutagenic
activity and interfere with bioassay results (9). Therefore, bioassay
analysis is recommended for samples collected from these two adsorbents.
The bioassay results can provide information as to whether PUF plugs or
XAD-2 resin would interfere with bioassay. To characterize and to
compare these two adsorbents thoroughly, studies are also recommended to
determine the stability of PAHs captured on XAD-2 resin as a function of
time.
In this study, quartz fiber filters were used to collect air
particulate matter. However, there are other types of filters which can
be considered for collection of particles. Very few studies have been
conducted to evaluate filter material for collection of particle-bound
PAHs. Lee's group (10) has evaluated various candidate filter materials
such as glass fiber, quartz fiber, microglass fiber with Teflon binder
and Teflon membrane filters. Experiments were performed by liquid-
spiking BaP onto filters to determine the recoveries. However, the
liquid-spiking BaP does not represent the native adsorption state of BaP
in ambient air sampling. Therefore, it is recommended that an
evaluation study be conducted to compare different types of filters such
as quartz fiber, glass fiber, and Teflon-coated filters for collection
of PAHs in ambient air sampling. Several important filter
-------
characteristics such as flow characteristics and collection efficiency
should be addressed.
Studies to determine stabilities for different types of filters and
to determine the effects of storage time on PAH samples collected on
different types of filters are also recommended.
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SECTION 4
EXPERIMENTAL PROCEDURES
SAMPLING METHODOLOGY
In both the extraction and stability studies, eight EPA medium
volume samplers using General Metals bypass motors in place of the
original high volume blower motors were employed. Quartz fiber filters
were used to collect particulate matter and polyurethane foam (PUF)
cartridges were used to collect vapors. Samplers were located outside
Battelle away from any exhaust openings or heavy traffic. Two sets of
four samplers were placed in parallel approximately two feet apart. In
each set, the samplers were placed about one foot apart. A five foot
long exhaust hose was attached to each sampler leading away from the
sampler inlet to avoid recirculating the exhaust air to the filter and
the PUF trap. Prior to sampling, the sampler pump was turned on and the
flow rate was measured by means of a calibration head and a U-tube
manometer. Adjustments were made with a control and a bypass valve to
obtain a flow rate of 8 cfm. All the clean PUF traps were spiked with
100 ]iL of a methylene chloride solution containing nominally 50 ug/mL of
each of five perdeuterated PAHs. Then the spiked PUF cartridges and the
clean filters were placed in the sampling heads. Air was sampled for 24
hours. After 24 hours of sampling, a final flow check was conducted on
each sampler, and all PUF cartridges and filters were processed for
transport to the laboratory for analysis.
CHEMICAL ANALYSIS METHODOLOGY
Po lj> uret n_a_ne__Fo_am Ca rtr i dge __C1 ejinuj^ Method s
Two methods for cleanup of PUF cartridges were examined:
compression rinsing followed by Soxhlet extraction, and compression
-------
rinsing only. Two PUF plugs were cleaned by compression rinsing, which
consisted of placing a PUF plug in a beaker containing 800 ml of
toluene, compressing it and allowing it to expand 50 times, using the
base of a 250 ml graduate cylinder to compress the foam. This process
was repeated using acetone. The PUF cartridges were then Soxhlet-
extracted with acetone for 16 hours and dried in a vacuum oven using
water aspirator vacuum at room temperature. Another two PUF cartridges
were cleaned by compression rinsing and drying as above, but the Soxhlet
extraction with acetone was omitted. After drying, the four cleaned PUF
cartridges were Soxhlet-extracted with 10 percent ether in hexane for 16
hours. The extracts were concentrated to 1 ml and the internal
standard, 9-phenylanthracene, was added to give a final concentration of
5 ug/mt. These PUF extracts were analyzed by El GC/MS to determine the
background levels of PAHs found in the cleaned PUF cartridges.
Polyurethane foam cartridges to be used in the recovery study, the
extraction methods comparison, and the storage stability study were
cleaned by compression rinsing with toluene and acetone followed by
Soxhlet extraction with acetone and drying as above. Following cleanup,
the PUF cartridges were wrapped with hexane-rinsed aluminum foil and
placed in 32-ounce jars closed with Teflon-lined caps until they were
used. Typically, all the PUF cartridges were cleaned within 24 hours
prior to sampling.
Method ofPreparationof Standard Solutions
The spiking stock solution containing five Dn-PAHs was prepared in
methylene chloride and was stored in a 100 ml volumetric flask at a
nominal concentration level of 50 yg/mL for each compound. The actual
concentrations of this spiking solution are listed in Table 4.1. Four
1 ml aliquots of the spiking stock solution were transferred into four
2 ml GC vials for field use. Prior to sampling, exactly 100 yL of the
spiking solution was withdrawn into a 100 uL syringe, and the spike was
injected approximately 1 inch deep into the cleaned PUF cartridge.
Another stock solution containing selected native PAHs was prepared
at a nominal concentration of 100 yg/mL per compound, The
8
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TABLE 4.1. LEVEL OF DEUTERATED PAHs IN THE
SPIKING STOCK SOLUTION
Compound
Concentration of Standard,
yg/mL
Dg-Naphthalene
D^o-Phenanthrene
Dig-Pyrene
Di2-Benzo(a}pyrene
55
51
56
48
58
concentrations in this stock solution are given in Table 4.2. This
stock solution was used to prepare nominal 1, 5 and 10 yg/mL standard
solutions which also contained the spiked Dn-PAHs and the internal
standard, 9-phenylanthracene, at a constant concentration of 5 yg/mL.
TABLE 4.2. LEVEL OF NON-DEUTERATED PAHs IN
THE STOCK STANDARD SOLUTION
Compound
Concentration of Standard,
ug/mL
Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Benzo(e)pyrene
Benzo(a)pyrene
Benzo(g,h,i )perylene
Coronene
1-Nitropyrene
119
124
106
102
113
105
93
109
103
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Method of Extrac11 on Study
Eight PUF and filter samples were collected in the extraction
study. The filter samples were wrapped with aluminum foil, stored at
room -temperature, and were not analyzed in this program. Four PUF
samples were Soxhlet-extracted with 800 ml 10 percent ether/hexane for
16 hours. After extraction, the sample extracts were concentrated to
I ml and transferred into 2 ml sample vials.
Another four PUF samples were extracted with 800 ml of 10 percent
ether/hexane using the compression technique. The PUF plug was placed
in a beaker containing 800 ml of 10 percent ether/hexane and was
compressed fifty times using the base of a 250 ml graduate cylinder.
Then the sample extract was evaporated to 1 ml and transferred into a
2 ml sample vial. Prior to GC/MS analysis, the internal standard, 9-
phenylanthracene, was added to all the sample extracts to give a
constant concentration of 5 yg/rnL. The levels of Dg-PAHs and Dn-PAHs in
these PUF samples were determined using El GC/MS.
Method of Stability Study
Two sets of sampling were conducted in the stability study. The
first set of sampling employed eight EPA medium volume samplers, but the
motors of two samplers burned out during sampling. Because the total
volumes sampled for these two samples were not known, only six PUF
samples were available for the study. The sampling was repeated one
week later to obtain the second set of samples. After 24 hour sampling,
eight PUF samples were collected for the stability study.
Neither the first nor the second set of filter samples were
analyzed in this study. Only PUF samples were used in the stability
study, these were stored under different conditions. The first set of
PUF samples was stored in the presence of white fluorescent light (room
lights) at room temperature; the wavelengths and intensities of the
light were not measured. The second set of PUF samples was wrapped
individually with aluminum foil and stored in the dark at room
temperature. Two PUF samples from each set were extracted with 10
percent ether/hexane usingthe compression technique immediately after
10
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sampling. The remaining PDF samples were stored either in the light or
in the dark for ten-, twenty- or thirty-day intervals and extracted with
10 percent ether/hexane. Sample extracts were concentrated to 1 ml for
GC/MS analysis. The internal standard, 9-phenylanthracene, was added to
all sample extracts at a level of 5 pg/mL prior to GC/MS analysis.
Method of Analysis by Gas Chroma tography/
MassSpectrometry(GC/MS)
Electron impact gas chromatography/mass spectrometry (El GC/MS) in
the fyll mass scan mode was employed to determine Dg-PAHs and the spiked
Dn-PAHs in the PUF samples. The instrumental conditions used are listed
in Table 4.3. A Finnigan Model 4500 quadrupole mass spectrometer
equipped with an EI/C1 source was employed. The mass ranges were
scanned from 50 amu to 450 amu at 1 sec scan rate. The ion source
temperature was held at 160°C and the electron multiplier was operated
at approximately 10^ gain.
Gas chromatography employed an Ultra #2 fused silica capillary
column (50 m x 0.31 mm I.D., 0.17 urn film thickness, Hewlett-Packard
Co.) and methane carrier gas. The GC column interfaced directly to the
MS ion source. With on-column injection, the sample was injected at
45°C to prevent thermal degradation of thermally labile compounds such
as 1-nitropyrene. The GC column temperature was held at 45°C for 2 min,
programmed rapidly to 100°C in 5 min, and then programmed from 100°C to
320°C at 6°C/min.
The standard solutions and sample extracts were analyzed by El
GC/MS. Identification of the PAH compounds in the sample extracts was
based on the correct mass spectrum and the correct retention time
relative to the internal standard as determined from the standard
analyses. From the standard analyses, the response factor for each
compound relative to the internal standard was calculated over the
calibration range. The following equation shows the factors on which
quantification was based:
r - "y X C T t; X Fy
LX " A1s x Rf
11
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TABLE 4.3. SC AND MS OPERATING CONDITIONS
Chromatography
Column:
Carrier Gas:
Injection Volume:
Injection Mode:
Temperature Program
Initial Column Temperature:
Initial Hold Time:
Program:
Final Hold Time:
Mass Spectrometer'
Instrument:
lonization;
Emission Current:
Scan:
Preamplifier:
HP Ultra #2 cross!inked 51 phenyl methyl
silicone 50 m x 0.31 mm, 0.17 pm film
thickness
CH4 flow rate at 60 c«3/sec at 250°C
1 uL
On-column at 45°C
45°C
2 minutes
45° to- 100°C in 5 rain, then
100°C (5 min) to 320°C at 6°C/min
10 minutes
Finnigan 4500 GC/MS
Electron impact at 70 eV
0.3 ma
50-450 amu; 1.0 sec/scan
10~8 amp/volt
12
-------
where
Cx = Total pg of a target compound in the extract
Ax = Molecular Ion area of a target compound
CTS = Concentration of the internal standard
A-JS = Molecular ion area of the internal standard
Rf = Response factor of a target compound
Fv = Final volume of sample extract.
Method of Preparation of Sample Extracts for
Hicrobioassay
Since the microbioassay is conducted directly in the vials con-
taining the sample extracts, the vials must be clean and free of
chemical or biological interference. Therefore, prior to solvent
exchange, the vials to be used for shipping and bioassay were placed in
a 500°C oven heated overnight, and the screw caps were Soxhlet-extracted
with methane! for 16 hours. Sample extracts from the pilot study of the
previous work (7) were diluted with methylene chloride to a
concentration of 3.77 mg/mL. A one ml aliquot was removed from each
sample extract for further dilution to 1 mg/ml and the remaining
portions were stored in the dark at -70°C. The diluted extracts
(1 mg/mL) were then divided into 16 sample vials at eight different
levels of mass in duplicate. The conditions for sample division are
summarized in Table 4.4. The sample extracts were evaporated to near
dryness under a gentle nitrogen stream and 2 uL of dimethylsulfoxide
(DMSO) was added to each sample. The DMSO samples were mixed with a
Vortex mixer and evaporated under nitrogen for additional five minutes.
Then the sample vials were sealed with screw caps and immediately stored
under dry ice. The samples were packed in dry ice and sent to EPA at
HERL/ERC for microbioassay with and without metabolic activation (+S9,-
S9).
13
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TABLE 4.4. MASS DISTRIBUTION OF SAMPLE EXTRACTS FOR
MICROBIOASSAY
Level of Mass
in Sample V1al»
ug
Size of
Syringe Used,
yL
Number of Vials
Amount of
DMSO added,
PL
1000
500
200
100
50
20
10
5
1000
500
250
100
50
25
10
10
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
14
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SECTION 5
RESULTS AND DISCUSSION
The results of cleaning the PUF cartridges by two different methods
are summarized in Table 5.1. Only small quantities of naphthalene were
found in the PUF cartridges cleaned by either the compression method or
the combined compression and Soxhlet extraction method. However, as
shown in Figures 1 and 2, an unknown impurity peak which is about 90
percent of the total ehromatographic peaks was detected in the clean PUF
cartridges after both of these two different cleaning methods.
The results of the extraction study are presented in Table 5.2 and
5.3. As shown in Table 5.2, generally good recoveries (>85 percent)
were obtained for spiked Dn-PAHs with the exception of Dg-naphthalene
using either the Soxhlet extraction or the compression method. The loss
of Dg-naphthalene was anticipated since this compound is highly
volatile. The sampling temperature during this experiment was 0°C to
10°C. Even greater losses of this volatile compound can be expected at
higher sampling temperatures.
As shown in Table 5.3, the levels of native PAHs found in the PUF
cartridges were very similar using these two methods. The levels of
PAHs found in the PUF cartridges, expressed as ng per cubic meter of air
sampled, ranged from 0.10 ng/m^ to 29.39 ng/m^ and 0.17 ng/m^ to
28.41 ng/m3 using the Soxhlet-extraction and the compression methods,
respectively. These data demonstrate that the compression technique is
comparable to Soxhlet-extraction in removing PAHs from the PUF
cartridges. Since significant time and cost savings can be achieved by
using the compression method, this method was used in the stability
study.
Only volatile and semi-volatile PAHs were found in the PUF
cartridges. Higher molecular weight PAHs(^252), such as benzo(a)pyrene
and coronene, and 1-nitropyrene were not detected in the PUF
15
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100.0-1
5054460.
RIC_
500
8:20
1000
16:40
1500
25:00
2000
33:20
I
2509 SCAN
41:40 TIME
Figure 1. The total ion chromatogram of PUF blank cleaned by the compression method.
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100.0-1
RIC
3665910.
500
8:20
1000
16:40
1500
25:00
2009
33:20
I
2508 SCAN
41:40 TIME
Figure 2. The total ion chromatogram of PUF blank cleaned by the combined compression
and Soxhlet extraction method.
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cartridges, indicating that these compounds are predominantly retained
on the filter.
TABLE 5.1. LEVELS OF PAHs IN PUF CARTRIDGES CLEANED BY
TWO DIFFERENT METHODS
Compound
Method of Cleaning
Compression Method
Total Mass/PUF
Cartridge, \ig
Compression followed
by Soxhlet
Extraction Method
Total Mass/PUF
Cartridge, ug
Naphthalene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benz(a}anthracene
Chrysene
Cyclo pen ta(c,d)pyrene
1-Ni tropyrene
Benzo(e)pyrene
Benzo(a)pyrene
Benzo(g»h,i)perylene
Coronene
0.07
0.10
(1)
(1) Not detected.
18
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TABLE 5.2 RECOVERIES OF PAHs FROM SPIKED PUF CARTRIDGES USING TWO EXTRACTION
METHODS - COMPRESSION AND SOXHLET EXTRACTION
Soxhlet Extraction
Compound Name
Dg-Naphthalene
Dio-Phenanthrene
DiQ-Pyrene
Dj2-Chrysene
Di2-Benzo(a)pyrene
No. 1
0.83
92.62
107.62
106.57
92.18
TABLE 5
No. 2
0.69
91.20
101.13
102.42
87.53
No. 3
0.41
73.21
104.18
102.89
99.15
.3. LEVELS OF
METHODS -
. % Recovery
No.
2
84
103
93
103
, 4
.86
.14
.79
.60
.90
PAHs IN PUF
COMPRESSION
Soxhlet Extraction, Total Mass,
Compound Name
Naphthalene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Cyclopenta(c,d)pyrene
l-N1tropyrene
Benzo(e)pyrene
Benzo( a)pyrene
Benzo(g,h,1 Jperylene
Coronene
No. 1
4.14
30.18
2.33
7.58
5.06
..(1)
0.15
--
—
—
—
--
—
No. 2
3.87
26.93
2.02
6.66
4.33
0.03
--
--
--
—
—
—
No. 3
3.87
29.69
2.06
7.09
4.23
0.06
—
—
--
—
--
--
No
6.
30.
1.
7.
3.
0.
-
-
-
, nq/m3
. 4
56
74
57
12
56
15
-
-
-
-
-
-
Average
Value
1.20
85.29
104.18
101.37
95.69
No. 1
0.70
83.56
113.62
111.65
103.08
CARTRIDGES
AND SOXHLET
Average
Value
4.61
29.39
2.00
7.11
4.30
0.10
--
--
—
--
--
—
No. 1
3.40
26.35
1.72
6.75
4.39
0.12
—
--
--
--
--
--
Compression Method, %
No. 2
0.58
81.12
105.91
106.56
96.19
No. 3
1.16
89.33
108.13
102.32
93.76
Recovery
No. 4
0.67
86.57
99.90
92.17
90.40
Average
Value
0.78
85.14
106.89
103.18
95.86
EXTRACTED BY TWO
EXTRACTION
Compression
No. 2
3.77
26.17
1.54
6.60
3.90
0.15
—
--
--
—
--
—
Method, Total
No. 3
4.08
26.17
1.69
6.29
3.96
0.09
--
—
--
--
--
—
Mass, ng/m3
No. 4
4.94
34.94
2.39
7.94
5.40
0.31
—
—
--
--
--
--
Average
Value
4.05
28.41
1.84
6.90
4.41
0.17
--
--
—
--
—
--
(1) Not detected
-------
The stability study was conducted to determine whether a
significant loss of PAHs captured by PDF cartridges occurs during the
storage period. Two sets of PUF samples were obtained for this study.
The first set of PUF samples was stored at room temperature (~20°C) in
the light, and the second set of samples was stored at room temperature
in the dark. Average recoveries of the perdeuterated PAHs extracted
from the PUF samples are given in Tables 5.4 and 5.5. Concentrations of
native PAHs found in the PUF samples are calculated as ng/m^ and are
given in Tables 5,6 and 5,7.
Recoveries for the perdeuterated PAHs for the first set of PUF
samples (stored in the light) ranged from 0.6 percent for Dg-naphthalene
to 102.3 percent for Di2~Chrysene. Low recoveries were obtained for Dg-
naphthalene, which decreased from 2.6 percent to 0.4 percent after 20
days storage. The low recovery and the decreasing recovery trend for Dg
-naphthalene during storage are mainly due to the volatilization of this
compound. The storage time does not appear to have adverse effects on
the recoveries of DjQ-phenanthrene, D}Q-pyrene, and D^-chrysene. "^ne
variations of recovery for these compounds were less than 15 percent and
may be due to small variations in sampling and analysis procedures. It
should be noted that the recoveries of D|2-benzo(a)pyrene decreased
significantly with increased storage time:; the recoveries decreased
from 92.1 percent to 11.7 percent after storage for 20 days. It is
possible that oxidation or other degradation reactions of D^-BaP may
occur during storage.
In the second set of PUF samples (stored in the dark), the relative
recovery data are similar to those obtained with the first set of
samples. But the recovery of D^-BaP decreased less in the second set
of samples than in the first set. The recoveries decreased from 95.4
percent to 44.3 percent after 20 days storage. Even after 30 days, 29.5
percent of the D^-BaP was recovered. It appears that the PUF-adsorbed
Dj2-&aP is more stable in the absence of light.
20
-------
TABLE 5.4. RECOVERIES OF PAHs FROM PUF CARTRIDGES SPIKED
PRIOR TO SAMPLING AS A FUNCTION OF STORAGE TIME.
STORAGE CONDITIONS: 20°C» IN THE LIGHT
Compound Name
Percent Recovery
1
Storage Time Between Sampling
and Extraction, Days
10
20
2.6(2.4,2.9)(D 0.6(0.9,0.3)
87.8(85.5,90.1) 90.8(87.2,93.4)
98.6(95.7,101.5), 85.8(91.5,81.1)
102.3(103.2,101.4) 88.8(86.1,91.5)
Di2-Benzo(a)pyrene 92.1(94.6,89.6) 49.5(48.2,50.8)
Dg-Naphthalene
DjQ-Phenanthrene
DiQ-Pyrene
0.4(0.4,0.4)
84.1(86.8,81.4)
91.4(88.4,94.4)
91.7(96.8,86.5)
11.7(12.1,11.3)
(1) The first number given is the mean of the duplicate samples;
the second and third numbers are the range of the samples.
21
-------
TABLE 5.5, RECOVERIES OF PAHs FROM PUF CARTRIDGES SPIKED
PRIOR TO SAMPLING AS A FUNCTION OF STORAGE TIME.
STORAGE CONDITIONS: 20°C, IN THE DARK
Compound Name
Percent Recovery
Storage Time Between Sampling and Extraction, Days
1 10 20 30
D8-Naphthalene 1.2(1.3,1.1)U) 2.7(2.2,3.2) 1.1(0.8,1.4) 0.6(0.9,0.3)
DjQ-Phenanthracene 88.3(86.9,89.7) 88.5(95.1,81.9) 84.5(87.2,81.8) 85.1(87.6,84.6)
D10-Pyrene 97.6(100.1,95.1) 93.3(90.4,96.2) 87.1(80.4,93.8) 91.2(89.6,92.8)
Di2-Chrysene 100.0(97.2,102.8) 94.5(91.4,97.6} 101.1(103.9,98.3) 89.4(81.7,97.1)
D12-Benzo(a)Pyrene 95.4(94.1,96.6) 51.9(49.8,56.0} 44.3(42.2,46.4) 29.5(27.2,31.8)
(1) The first number given is the mean of the duplicate samples;
the second and third numbers are the range of the samples.
22
-------
TABLE 5.6. LEVELS OF NATIVE PAHs FOUND IN PUF CARTRIDGES
AS A FUNCTION OF STORAGE TIME.
STORAGE CONDITIONS: 2Q°C, IN THE LIGHT
Compound Name
Concentration, ng/m3(l)
Storage Time Between Sampling and Extraction, Days
1 10 20
Naphthalene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benz{a)anthraeene
Chrysene
Cyclo penta(c,d)pyrene
l-N1tropyrene
Benzo(e)pyrene
Benzo(a)pyrene
Benzo(g,h,i)perylene
Coronene
6.37(4.95,7.79)(2) 3.94(4.43,3.45} 2.95(2.73,3.17)
36.06(33.45,38.67)
0.61(0.71,0.51)
7.39(7.12,7.66)
5.46(5.43,5.49)
0.22(0.16,0.28)
0.79(0.89,0.69)
-(3)
29.41(26.80,32.02) 29.25(28.12,30.38)
0.70(0.77,0.63)
6.33(5.78,6.88)
6.02(6.63,5.41)
0.20(0.25,0.15)
0.66(0.69,0.63)
0.41(0.38,0.44)
6.79(7.30,6.28)
5.84(6.04,5.64)
0.23(0.34,0.12)
0.71(0.81,0.61)
(1) Expressed as ng per cubic meter of air sampled.
(2) The first number given is the mean of the duplicate samples;
the second and third numbers are the range of the samples.
(3) Not detected
23
-------
TABLE 5.7. LEVELS OF NATIVE PAHs FOUND IN PUF CARTRIDGES AS A FUNCTION OF
STORAGE TIME. STORAGE CONDITIONS: 2QOC, IN THE DARK
Compound Name
Concentration, ng/m^U)
Storage Time Between Sampling and Extraction, Days
10 20 30
Naphthalene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Cyclopenta(c,d)pyrene
1-Nitropyrene
Benzo(e)pyrene
Benzo(a)pyrene
Benzo(g,h,i)pery!ene
Coronene
9.80(9.41,10.19)(2) 9.04(9.43,8.65) 8.27(8.26,8.28) 6.17(6.47,5.87)
24.57(23.66,25.48)
1.87(2.18,1.56)
5.88(5.81,5.95)
6.13(6.12,6.14)
0.18(0.19,0.17)
0.19(0.18,0.19)
-(3)
29.72(32.96,26.48) 22.32(24.39,20.25) 29.38(29.91,28.85)
0.95(1.01,0.89)
6.03(6.52,5.53)
6.68(6.60,6.76)
0.17(0.22,0.12)
0.14(0.13,0.14)
0.67(0.70,0.04)
5.82(5.78,5.86)
4.89(4.53,5.25)
0.09(0.12,0.06)
0.20(0.15,0.25)
1.01(1.04,0.98)
6.61(6.54,6.68)
5.56(5.95,5.17)
0.16(0.15,0.17)
0.18(0.18,0.18)
(1) Expressed as ng per cubic meter of air sampled.
(2) The first number given is the mean of the duplicate samples; the second and
third numbers are the range of the samples.
(3) Not detected.
-------
Similar recovery trends were observed for the native PAHs, The
storage time does not significantly affect the levels of phenanthrene,
pyrene, and chrysene found in the PUF samples. Slightly decreasing
concentrations were detected for naphthalene. Similar decreasing levels
were observed for anthracene, an isomer of phenanthrene. The reactive
PAH, cyclopenta(c.d)pyrene, higher-molecular weight PAHs (>252), and 1-
nitropyrene were not detected in the PUF samples.
25
-------
REFERENCES
(1) Cautreels, W., and VanCauwenberghe, K., "Experiments on the
Distribution of Organic Pollutants Between Airborne Participate
Matter and Corresponding Gas Phase", Atmos. Environ., 12:1133-1141,
1978.
(2) Thrane, K. E., and Mikalsen, A., "High Volume Sampling of Airborne
Polycyclic Aromatic Hydrocarbons Using Glass Fiber Filters and
Polyurethane Foam", Atmos. Environ., 1.5:909-918, 1981.
(3) Feng, Y., and Bidleman, T. F., "Influence of Volatility on the
Collection of Polycyclic Aromatic Hydrocarbon Vapors with
Polyurethane Foam", Envir. Sci. Techno!., 18:330-333, 1984.
(4) Yamasaki, H., Kuwata, K., and Miyamoto, H., "Effects of Ambient
Temperature on Aspects of Airborne Polycyclic Aromatic
Hydrocarbons", Envir. Sci. Techno!.. 16:182-194, 1982.
(5) White, C. M., Sharkey, A. G., Lee, M. L., and Vassilaros, D. I.,
"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. 261-275, 1979.
(6) Billings, W. N., and Bidleman, T. F., "High Volume Collection of
Chorinated Hydrocarbons in Urban Air using Three Solid Adsorbents"s
Atmos. Environ.. 17:383-391, 1983.
(7) Chuang, C. C., Mack, G. A., Koetz, J. R., and Petersen, B. A,,
"Pilot Study of Sampling and Analysis for Polynuclear Aromatic
Compounds in Microenvironments", Final Report for U.S. EPA,
Contract No. 68-02-3487 (WA35), 1984.
(8) Keller, C. D.s and Bidleman, T. F., "Collection of Airborne Poly-
cyclic Aromatic Hydrocarbons and Other Organics with a Glass Fiber
Filter Polyurethane Foam System", Atmos. Environ., 1^:837-845,
1984.
(9) Alfheim, I., and Lindskog, A., "A Comparison Between Different High
Volume Sampling Systems for Collection Ambient Airborne Particles
for Mutagenicity Testing and for Analysis of Organic Compounds",
Sci. Total Environ., 34:203-222, 1984.
26
-------
(10) Lee, F. S., Pierson, W. R.f and Ezike, J. "The Problem of PAH
Degradation During Filter Collection of Airborne Participates -- an
Evaluation of Several Commonly Used Filter Media. In: Polynuclear
Aromatic Hydrocarbons", A Bjerseth and A. J. Dennis, Editors,
Battelle Press, Columbus, Ohio, pp. 543-563, 1979.
27
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO,
EPA/600/4-85/055
4, TITLE AND SUBTITLE
evaluation of Polyurethane Foam Cartridges For
Measurement of Polynuclear Aromatic Hydrocarbons
In Air.
3, RECIPIENT'S ACCESSION NO,
5, REPORT DATE
August 1985
6. PERFORMING ORGANIZATION CODE
7. AUTHORSS)
C. C. Chuang, W. E. Bresler, and S. W. Hannan
8. PERFORMING ORGANIZATION REPORT NO
9, PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-3487, Task 41
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Environmental Monitoring Systems Laboratory
Research Triangle Park, NC 27711
13. TYPi OF REPORT AMD PERIOD COVERED
Final 8/1/84 - 12/31/84
14. SPONSORING AGENCY CODE
EPA/600/08
15. SUPPLEMENTAH-Y NOTES
have been
and background
because it is
objective of this project was -to evaluate polyurethane foam (PUF)
cartridges as collection media for quantification of vapor phase polynuclear aromatic
hydrocarbons (PAHs) in air. Two cleanup methods for PUF cartridges -- compression
rinsing and combined compression rinsing and Soxhlet extraction
evaluated. Both methods successfully remove interfering material
PAHs from the PUF. The compression rinsing method is recommended
easier, faster, and cheaper.
Two procedures for extraction of PAHs from the PUF matrix, Soxhlet extraction
and compression rinsing, were compared. These sample extracts were analyzed by
on-column injection, electron impact gas chromatography/mass spectrometry (El GC/MS)
to determine PAHs. The results showed that compression rinsing is comparable to
conventional Soxhlet extraction, and that both methods successfully remove PAHs
from the PUF cartridges. The compression rinsing method was then used in the
stability study.
The stability study was carried out to determine the stability of PAHs adsorbed
on PUF cartridges as a function of storage time between collection and extraction.
The results indicated that the levels of the spiked perdeuterated benzo(a)pyrene
decreased significantly during storage. The rate of decrease was much, faster when
the PUF cartridges were stored in light. Other PAH levels were not "adversely
influenced hv the storage time. ^
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
8. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
36
20. SECURITY CLASS (This page)
UNCLASSIFIED
EPA Form 2220-1 (Re*. 4-77)
PREVIOUS EDI T!ON IS OBSOLET E
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