SPA/600/4-78/048
EFft
ital Protection
Environmental Monitoring and Support . EPA-600 • 4-78-048
Laboratory August 1978
Research Triangle Park NC 27711
Research and Development
A Method for
Sampling and
Analysis of
Polychlorinated
Biphenyls (PCB's) in
Ambient Air
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4 Environmental Monitoring
5 Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL MONITORING series.
This series describes research conducted to develop new or improved methods
and instrumentation for the identification and quantification of environmental
pollutants at the lowest conceivably significant concentrations. It also includes
studies to determine the ambient concentrations of pollutants in the environment
and/or the variance of pollutants as a function of time or meteorological factors.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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A (lETi-iOO FOR THE SAMPLING MD ANALYSIS Of
POLYCHLORINATEO dlPHEMYLS (PCBs) IN AMBIENT AIR
Prepared by
Charles L. Stratton
Stuart A. Whitlock
J . r4ark Al 1 an
ENVIRONMENTAL SCIENCE AND ENGINEERING, INC.
P.O. BOX 13454, UNIVERSITY STATION
GAINESVILLE, FLORIDA 32604
EPA Contract No. 68-01-2978
January 3U, 1978
for
QUALITY ASSURANCE BRANCH
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NC 27711
and
OFFICE OF TOXIC SUBSTANCES
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
EPA PROJECT OFFICERS:
John H. Hargeson
EPA, EHSL Research Triangle Park
George E. Parris
Vincent J. JeCarlo
EPA Office of Toxic Substances
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This report has been reviewed by the Office of Research and Development,
EPA, and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names of commercial products
constitute endorsement of recommendation for use.
11
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TABLE OF CONTENTS
Page
ACKNOWLEDGEMENT iv
ABSTRACT v
1.0 INTRODUCTION 1
1.1 COMPLEXITY Of AIRBORNE PCB MEASUREMENT 1
1.2 REQUIREMENTS OF A METHOD TO MEASURE AIRBORNE PCB 3
2.U RESULTS AND DISCUSSION , 5
2.1 SELECTION OF THE SAMPLING METHOD 6
2.2 DESCRIPTION OF THE SAMPLING APPARATUS 8
2.3 ANALYTICAL PROTOCOL 14
2.3.1 CLEANUP OF MATERIALS AND APPARATUS 14
2.3.2 FIELD SAMPLING 17
2.3.3 SAMPLE EXTRACTION 21
2.3.4 SAMPLE CONCENTRATION 21
2.3.5 SAMPLE CLEANUP 22
2.3.6 GAS CHROMATOGRAPHIC ANALYSIS 22
2.3.7 PERCHLORINATION 27
2.3.8 PERCHLORINATION RUGGEDNESS TEST 38
3.0 RECOVERY STUDIES AND FIELD TESTS 44
3.1 RECOVERY STUDIES 44
3.2 PRELIMINARY FIELD TESTS 69
3.3 FIELD TESTS OF THE FINAL METHOD 78
3.3.1 TESTS IN GAINESVILLE, FLORIDA 78
3.3.2 TESTS IN NEW BEDFORD, MASSACHUSETTS 88
4.0 CONCLUSIONS AND RECOMMENDATIONS 103
5.0 REFERENCES 105
APPENDIX A--ANALYTICAL PROCEDURE 107
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ACKNOWLEDGEMENT
The authors wish to gratefully acknowledge the project direction and
valuable technical contributions of the Co-Project Officers, John H.
Margeson of the Environmental Monitoring and Support Laboratory, Quality
Assurance Branch, Research Triangle Park, and George E. Parris of the
Office of Toxic Substances. In addition, valuable technical advice was
provided by Robert G. Lewis, Analytical Chemistry Branch, Health Effects
Research Laboratory, Research Triangle Park, and Vincent J. DeCarlo of
the Office of Toxic Substances. Special thanks is extended to Terry F.
Bidleman who conceived of the use of porous polyurethane foam for
collection of airborne PCBs, and who provided invaluable assistance to
the authors in the early stages of this effort.
iv
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ABSTRACT
A method has been developed for the sampling and analysis of polychlo-
rinated biphenyls (PCBs) in air. An easily constructed, high-volume
sampling system is employed with porous polyurethane foam as the collec-
tion medium. The sample is collected at the rate of 0.6 to 1.0 m3
per minute. Laboratory procedures described in this document permit the
quantitative analysis of even the most volatile PCB species in an air
sample. A perchlorination technique for the quantitative analysis of
PCB has been adapted for use. The technique is shown to convert even
the most volatile PCB species to decachlorobiphenyl for simple and
direct quantitative analysis. Data is presented to show conversion
efficiencies of a variety of PCBs to decachlorobiphenyl of 101 _+
6 percent over the range of 0.103 to 10.0 ug. A ruggedness test was
conducted which indicates the proposed perchlorination technique can
yield reliable inter!aboratory results. The perchlorination technique
is generally necessary for the analysis of low (i.e., less than 25 ng/m3)
airborne levels of PCB. The analytical method is effective for the
analysis of airborne PCB levels within at least the range of 1 ng/m3 to
50 ug/m3. The mean collection efficiency for Aroclor 1016/1242 was
101 jf 10 percent for sampling periods of 20 minutes to 12 hours and air
volumes of 16 to 720 cubic meters. Field tests of the method under a
variety of ambient conditions are described. This report was submitted
as part of fulfillment of contract 68-01-2978 by Environmental Science
and Engineering, Inc. under sponsorships of the Environmental Protection
Agency.
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List of Tables
Table Pag_e
1 Perchlorination Recovery vs. Concentration
Test Resul ts 38
2 Eight Combinations of Seven Factors Used
to Test the Ruggedness of an Analytical Method 39
3 Perchlorination Ruggedness Test Conditions 41
4 Perchlorination Ruggedness Test Format and Data 42
5 Perchlorination Ruggedness Test Results 43
6 Molecular Composition of Some Aroclors (After
Hutzinger, Safe, and Zitko, 1974) 45
7 Results of Airborne PCB Collection Efficiency
Study Using Aroclor 1221 49
8 Results of Aroclor 1016 Recovery Studies 52
9 PCB Test Mi xture Composi tion 56
1U Results of Initial Recovery Study Using
PCB Test Mixture 57
11 Results of 2-Hour Recovery Studies Using TCB,
DiCB, and MCB 58
12 Results of 12-Hour Recovery Studies Using
Aroclor 1242, MCB, and DiCB 60
13 Results of 6-Hour Recovery Studies Using
Aroclor 1242 62
14 Results of 2-Hour Recovery Studies Using
Aroclor 1242 66
15 Summary of Recovery Tests 68
16 PCB in Ambient Urban Atmosphere 73
17 Results of High-Volume Ambient Air Sample Taken
in the Vicinity of an Electrical Substation and
Transformer Storage Facility 77
VI
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List of Tables (cont'd)
Table Page
18 Results of Field Tests Conducted in
Gainesville, Florida 79
19 Results of Field Tests Conducted in
New Bedford, Massachusetts, in June, 1977 89
20 Results of Field Tests Conducted in
New Bedford, Massachusetts in January, 1978 99
VII
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List of Figures
Figure Page
1 Assembled Sampler and Shelter With Exploded
View of the Filter Holder , 9
2 Exploded View of Hi-Vol Sampling Apparatus
Designed For Use With a Rotometer Showing
Modified Throat to Accomodate Polyurethane
Foam PI ugs 10
3 Analytical Scheme for PCB in Ambient Air 15
4 Apparatus for Drying Polyurethane Foam Plugs 18
5 Chromatogram of a Typical Unexposed Polyurethane
Foam Extract at Recorder Attenuation 4 x 1Q~9 19
b Chromatogram Of a Typical Glass Fiber Filter
(Gelman Type A) Extract at Recorder Attenuation
4 x 10-9. 20
7(a) Chromatogram of an Urban Air Sample, First
Polyurethane Foam Plug on OV-17/QF-1 Column 24
7(b) Chromatogram of Second Polyurethane Foam
Plug on OV-17/QF-1 Column 25
7(c) Chromatogram of Third Polyurethane Foam
Plug on OV-17/QF-1 Column 26
7(d) Aroclor 1221 on OV-17/QF-1 Column 27
8(a) Chromatogram of an Urban Air Sample, First
Polyurethane Foam Plug on SE-30/OV-210 Column 28
b(b) Chromatogram of Aroclor 1221 on SE-30/OV-210 Column 29
9 Chromatogram of a Perchlorinated Air Sample 32
10 Perchlorination Reaction Vial 34
11 Chromatograms of the Aroclor 1221
Collection Efficiency Study 47
12 Aroclor 1016 Recovery Experiment. 51
13 Chromatograms From an Aroclor 1016
Collection Efficiency Study 54
14 GC/EC Chromatogram of Aroclor 1242
Standard (Attn: 16 x lO"9) 63
VI 1 1
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List of Figures (cont'd)
Page
15(a) GC/EC Chromatogram of First PDF Plug Extract
(Attn: 16 x 10~9) from 6-Hour Aroclor 1242
Recovery Study 64
15 GC/EC Chromatogram of (b) Second and (c) Third
PUF Plug Extracts (Attn: 16 x 1CT9) from
6-Hour Aroclor 1242 Recovery Study 65
16 Minimum Ambient Airborne PCB Concentrations
in an Urban Environment 70
17 Chromatogram of an Urban Ambient Air Sample 72
18 (a) Standard Aroclor 1016; (b) Chromatograph
of Air Sample Taken in the Vicinity of a
Major Industrial User 75
19 GC/MS Analysis of an Ambient Air Sample Taken in
the Vicinity of a Major Industrial User of PCB 76
20 (a) GC/EC Chromatogram of an Unexposed PUF Plug
(b) GC/EC Chromatogram of the Glass Fiber Filter
Used During the Field Test on 7/26/77 60
21 GC/EC Chromatogram of an Aroclor 1242 Standard 81
22 GC/EC Chromatogram of the First PUF Plug Extract
(Attn: 8xlO-9) From the 2-Hour Ambient Air
Sample Taken 7/26/77 in Gainesville, Florida 82
23 GC/EC Chromatogram of (a) the Second and (b) the
Third PUF Plug Extracts (Attn: 8xlO'9) From
the 2-Hour Ambient Air Sample Taken 7/26/77 in
Gainesville, Florida 83
24 (a) GC/EC Chromatogram of the First PUF Plug Extract
(Attn: 4xlO~9) From tfie 2-riour Ambient Air Sample
Taken 10/31/77 in Gainesville, Florida; (b) GC/EC
Chromatogram of the Same Sample (Attn: 16xlO~9)
After Perch!orination 85
25 GC/EC Chromatogram (Attn: 16xlO"9) of 6-Hour
Ambient Air Sample (PUF #1) Taken 11/20/77 in
Gainesville, Florida 86
26 GC/EC Chromatograms of (a) Second PUF Plug, (b)
Third PUF Plug, and (c) Glass Fiber Filter
(Attn: 16xlU~9) of 6-Hour Ambient Air Sample
Taken 11/20/77 in Gainesville, Florida 87
IX
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List of Figures (cont'd)
Figure Page
27 GC/EC Chron,_togram of the Filter Extract
(Attn: 16xlO"9) From the 60-Minute Ambient Air
Sample Taken at New Bedford Landfill 90
28 GC/EC Chromatogram (Attn: 16xlQ-9) of an
Aroclor 1242 Standard 91
29 GC/EC Chromatogram of the First PUF Plug Extract
(Attn: 16xlO-9 Diluted to 1/8) of the 60-Minute
Ambient Air Sample Taken at New Bedford Landfill 92
30 GC/EC Chromatogram of the Second PUF Plug Extract
(Attn: 16xlO-9) of the 60-Minute Ambient Air
Sample Taken at New Bedford Landfill 93
31 GC/EC Chromatogram of the Third PUF Plug Extract
(Attn: 16x10-9) of the 60-Minute Ambient Air
Sample Taken at New Bedford Landfill 94
32 GC/FID Chromatogram of Biphenyl at 2.8 ng 96
33 GC/FID Chromatogram of the First PUF Plug Extract
From the 60-Minute Ambient Air Sample Taken at
New Bedford Landfi 11 97
34 GC/EC Chromatogram of Air Sample Taken over
New Bedford, Massachusetts, Landfill in
January, 1978 100
35 GC/EC Chromatogram of Ambient Air Samples Taken
(a) Upwind and (b) Downwind of a PCB User Facility
in New Bedford, Massaschuetts, in January, 1978 101
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l.U INTRODUCTION
Polychlorinated biphenyls (PCBs) have been detected by numerous research-
ers in all environmental media. Significant levels of contamination have
been detected in waters, aquatic sediments, soils, and biota. Data is
conspicuously limited, however, for the assessment of airborne PCB con-
tamination. Since the atmosphere may serve as both a transport medium
for PCB from a source to the environment and as a mechanism for direct
human exposure, it is important to evaluate airborne PCB levels. No com-
monly accepted method is presently available for the sampling of airborne
PCB. Investigations were, therefore, undertaken to identify and evaluate
a usable ambient air sampling method with adequate detection limit, sen-
sitivity and specificity to reliably assess airborne pollution by this
class of compounds. The purpose of this report is to describe one such
method for the measurement of airborne levels of PCB and to present data
documenting the performance of the method under laboratory and field
conditions.
1.1 COMPLEXITY OF AIRBORNE PCB MEASUREMENT
There exist a number of complicating factors which must be taken into
consideration in the measurement of airborne PCB levels. Principal among
these are:
a. The term "PCB" applies, not to a single chemical species, but to a
class of chemical compounds. These compounds are related by chemical
structure and by degrees of halogen substitution on the molecule.
PCB is seldom manufactured or used in the pure isomeric state. For
industrial application, PCBs are marketed in the form of mixtures,
each mixture containing a significant fraction of the 209 possible
isomeric species. For example, Aroclor® 1242, a commercial PCB
mixture, is comprised of 54 identified isomers (Hutzinger, Safe and
Zitko, 1974). Such mixtures have been detected in numerous environ-
mental media. The fact that a class of chemical compounds and not a
single identifiable chemical species is to be detected and measured
greatly multiplies the complexity of the chemical analysis in an
already complex environmental medium such as the ambient atmosphere.
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b. Our concern is with extremely low airborne concentrations of PCB.
Measurements reported to date indicate ambient levels are in the
ng/m3 or part per trillion (ppt) range.
c. Not only are airborne PCB levels expected to be low, but they must be
detected in the presence of a large number of other organic compounds
which may be present in much higher concentrations than the PCB.
Organic compounds from both natural and manmade sources will compli-
cate PCB collection and analysis.
d. Analytical methods have been developed for the analysis of PCB in
most environmental media. These methods generally employ gas-liquid
chromatography (GC). They have been developed after years of lab-
oratory work required to perfect extraction, concentration, cleanup,
and analytical techniques. There are numerous variations to each of
these techniques, but they all entail lengthy, exacting methods of
sample handling and treatment. Since the present interest is with
airborne PCB, it may be expected to be necessary to deal with the
more volatile species in this class of compounds. The more volatile
species have proven to be more difficult to handle analytically than
the less volatile, or more highly substituted, PCB species, and
hence, require even more attention to analytical detail.
e. The state-of-the-art of quantisation of PCB by gas chromatographic
analysis is not well-developed. Currently used methods are sub-
jective. This leads to considerable variability among analysts.
There has always been difficulty in accurately quantifying PCB present
in environmental media. In most cases, the multipeak GC elution pattern
observed after separation of pesticides and other interfering compounds
by extensive extract cleanup procedures is subjectively compared to the
elution pattern of a commercial PCB mixture. A decision is made as to
what commercial product the sample elution pattern most closely repre-
sents. The quantity of PCB present is then calculated by comparison of
several matching GC peaks between the sample and a known concentration of
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the commercial product. Inherent in this method of quantisation is the
assumption that all PCB isomers are present in the sample in the same
proportion as in the commercial mixture chosen for quantitation purposes.
There is no reason to believe the GC elution pattern of ambient airborne
PCB would closely resemble that of a commercial product. The more
volatile PCB species of a given commercial mixture would likely be
selectively enriched in the airborne phase as compared to the solvent
phase. This phenomenon of selective airborne enrichment of the lower-
substituted PCB isomer has been demonstrated by Mieure (1975) for vapors
above a standard Aroclor 1016 mixture. One would expect even greater
apparent enrichment of more volatile species as samples are collected
further from the source of the airborne contamination.
The most common method of PCB analysis, using the electron capture detec-
tor in conjunction with gas chromatography, introduces still another
complicating factor. The response factor or sensitivity of the various
PCB isomers in a given mixture will vary by several orders of magnitude
depending upon not only the degree of chlorination, but on the position
of the chlorine atom on the PCB molecule (Zitko, Hutzinger and Safe,
1971). Tne response is not linear with substitution. The analyst must,
therefore, be absolutely certain he is comparing, for quantitative
purposes, GC peaks generated by the identical isomer.
1.2 REQUIREMENTS OF A METHOD TO MEASURE AIRBORNE PCB
Any method wnich is selected for the measurement of airborne PCB must
conform to a demanding set of performance criteria. The most important
of these criteria are dictated by the anticipated difficulty in analyzing
airborne PCB. These criteria are:
a. The selected method must incorporate the sampling of large volumes of
air. To avoid excessively lengthy sampling periods, it was con-
sidered important that the sampling method chosen be a high-volume
technique. This is necessary to achieve the desired low detection
limit for the ambient atmosphere within a reasonable sampling period.
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b. The chosen sampling method must demonstrate a high collection
efficiency for airborne PCB. A sampling technique which approaches
quantitative collection of the airborne PCB is essential to achieve
the desired low detection limit, precision, and accuracy of the
measurement.
c. Since one of the complicating factors which must be overcome in the
measurement of ambient airborne PCB is the presence of other organic
materials in the atmosphere, many in much higher concentration than
the PCB, the sampling and analytical techniques must be specific to
PCB. The difficulties encountered in accurately quantifying PCB in
environmental media have been discussed. These difficulties are even
more greatly magnified when contaminants, which are not of immediate
interest, are present in the final analytical extract. When this is
the case, the multipeak chromatogram is increasingly difficult to
interpret.
d. It is desired to select a method that is relatively easy to perform
and that lends itself to standardization. This applies to both the
sampling activity in the field and to laboratory analytical
procedures.
e. The selected method should permit qualitative assessment of the PCB
present as well as quantitative assessment. It should be possible to
ascertain the general distribution of the total PCB present according
to species. For example, if the ambient PCB should resemble a
specific commercial mixture, this information is desired in order to
evaluate the potential source of the contamination and to assess the
potential health and environmental hazard.
f. It would be highly preferred that the selected method had been shown
by previous researchers to perform well. This would greatly reduce
the effort necessary to adapt the method of routine use.
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RESULTS AND OISCUSSIUN
A review was conducted of potential sampling and analytical techniques
tor airborne organic pollutants that would apply to PCB. A sampling
method and analytical methods were selected for evaluation based on the
reported experience of previous researchers. A high-volume sampling
method using polyurethane foam as the collection medium was considered to
be tne candidate method that most closely matched the desired criteria.
This sampling method was combined with analytical methods reported by
researchers to be effective in determining low concentrations of PCB in
environmental media, to arrive at a complete step-by-step procedure for
assessing airborne PCB concentrations.
The selected method was evaluated in the laboratory and in the field.
The evaluation consisted of an analytical recovery study, a sampling
efficiency study, an analytical ruggedness test, a number of preliminary
field tests, and a final field test. The analytical recovery study was
necessary to establish procedures and to overcome difficulties encounterd
in the laboratory analysis of the airborne samples collected on poly-
urethane foam so that quantitative results could be achieved. Collection
efficiency studies were conducted to identify the limits of the high-
volume sampling technique selected. Preliminary field tests were neces-
sary to obtain experimental samples of the ambient atmosphere during
method development. These field data were used to evaluate the method
from the standpoint of the practicality of application under field condi-
tions. A final field test was conducted to demonstrate the application
of the method.
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2.1 SELECTION OF THE SAMPLING METHOD
It was desired to select a sampling technique for airborne PCB that has
been evaluated by other researchers and that conforms as closely as
possible to the performance criteria set forth above. A review of pub-
lished literature indicated some experience had been reported in the use
of wet impingers, solid adsorbents, silicone oil, and polyurethane for
the collection of airborne PCB.
Harvey (1974) employed a sampling device consisting of a tube packed with
silicone-oil coated ceramic saddles through which a large volume of air
can be drawn at the rate of 0.6 m3/min. Harvey determined the coll lection
efficiency of this method using trichlorobiphenyl, hexachlorobiphenyl,
and Aroclor 1254. He tested the collection efficiency by applying known
quantities of these PCB species and the commercial mixture to a glass
fiber filter which preceeded the adsorbent medium in the collection sys-
tem. The average collection efficiency was 70 percent. Concentrations
in the ambient atmosphere over the western North Atlantic of 0.05 to
. 5.3 ng/m^ were reported by Harvey using this method. He expressed
the opinion that the method can only approximate PCB concentrations in
ambient air.
Giam, Chan, and Neff (1975) recommend a method for the detection of PCB
in air which makes use of a solid adsorbent, Florisil, packed in a short
glass column. Air is pumped through this column at the rate of 2 to
4 1/min. By placing several of these sample columns in series, it was
found that PCB spiked onto the first column was retained only on the
first column for sampling time as long as 60 hours. Using this arrange-
ment to sample laboratory atmosphere, Giam, Chan, and Neff reported
levels of 35 to 90 ng/m^ PCB. No attempt was made to identify the
PCB species present.
Bidleman and Olney (1974a) reported ambient concentrations of PCB over
the western North Atlantic and Rhode Island of 0.21 to 9.4 ng/m3.
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These researcners (Bidleman and Olney, 1974b) devised a high-volume
sampling method employing polyurethane foam as the collection medium.
Cylindrical polyurethane foam plugs, of 1U cm thickness, are placed in a
high-volume air sampler behind the standard filter holder. Air is drawn
through the sampling apparatus at the rate of 0.5 to 1.0 m^/tnin. The
authors evaluated the collection efficiency of this medium by placing the
sampling device near the source of tri-, tetra-, and pentachlorobiphenyl.
The device was equipped with two polyurethane foam plugs. A glass fiber
filter was placed in the filter holder. In this manner, these research-
ers determined less than 1 percent of the PCB isomers tested was trapped
on the glass fiber filter and 96 to 99 percent of the total collected was
trapped on the first polyurethane foam plug. Bidleman and Olney at the
same time, and in the same manner, evaluated the collection efficiency of
Greenburg-Smith impinger systems charged with ethylene glycol. They
found this impinger system trapped 75 to 82 percent of the total tetra-
and pentachlorobiphenyl while that remaining passed through the sampling
system. Bidleman and Olney concluded, based on this preliminary evalu-
ation, that the polyurethane foam was an effective collection medium for
airborne PCB.
The high-volume sampling method of Bidleman and Olney (1974b) was
selected for evaluation and application to assessing ambient airborne
levels of PCB. Of the methods investigated by previous researchers, this
one appeared to most closely meet the performance requirements set forth
above for the following reasons:
a. It is a high-volume method that should provide the capacity of
determining low ambient levels of airborne PCB without excessively
long sampling periods.
b. A high collection efficiency has been demonstrated for the tri-,
tetra-, and pentachlorobiphenyl species.
c. The polyurethane foam used as a collection medium has been used for
the concentration of PCB in natural waters. It was selected for this
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purpose, partly because it demonstrates a degree of selectivity for
PCB. If this proved to be true for airborne organic pollutants, it
would be of considerable advantage, since this technique would
provide a means to selectively increase the ratio of PCB to other
organic materials which may interfere analytically in the sample.
d. The apparatus and the manipulation required in the field are rela-
tively simple and straightforward, so that it has potential for
adaption to routine monitoring use.
e. The method should enable both a qualitative assessment of the species
distribution of the PCB present and a quantitative assessment of the
amount of PCB present.
f. Bidleman and Olney (1974b) have conducted a preliminary evaluation of
the method and expressed confidence in its application to assess
ambient airborne contamination.
Several authors (Rhoades, et aJL, 1977; Rice, et al_., 1976; Lewis, et
a1., 1977) have recently reported on experience they have gained in the
laboratory testing and application of polyurethane foam for the sampling
of PCB in ambient air. Margeson (1977) discusses the state of the art
for ambient airborne PCB measurement.
2.2 DESCRIPTION OF THE SAMPLING APPARATUS
A sampling apparatus similar to that used by Bidleman and Olney (1974b)
was designed using readily available equipment. A number of modifica-
tions were incorporated into the system to improve performance as a
result of laboratory and preliminary field evaluation. The sampling
apparatus, including all modifications, is illustrated in Figure 1.
Figure 2 is an exploded view of the sampler. This apparatus was used for
all evaluations reported in this document.
The basic sampling system is a modification of a standard high-volume
sampling apparatus. These units are commonly used for airborne
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Faceplate
Stainless Steel Throat Extensior
Polyurethane Foam
Plug Location
Throat Extension
Wire
Retainer
Motor Unit
Adapter
Exhaust Duct
(3m minimum length)
Figure 1. Assembled sampler and shelter with exploded view of the filter holder,
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Throat Modification
Figure 2. Exploded view of hi-vol sampling apparatus designed for use
with a rotometer showing modified throat to accomodate
polyurethane foam pluos.
10
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participate sampling. They consist of a stainless steel filter holder
and throat assembly coupled to a high capacity centrifigal blower. The
standard high-volume sampler used is manufactured by General Metal Works
of Cleves, Ohio. It was modified by removal of the 3 cm long by 8 cm
diameter cylindrical throat assembly between the filter holder and the
blower housing and replacement by a throat assembly of similar design but
3U cm in length. The extended throat assembly was welded to the filter
holder assembly. This provided a space for placement of the polyurethane
collection medium. The neoprene seal located on the backside of the
faceplate was removed and all adhesive material was scrupulously removed
with organic solvents. Teflon tape was then used to provide a seal
between the faceplate and the filter holder. These modifications
resulted in a high-volume sampling system which contained only stainless
steel and teflon components and surfaces ahead of the collection medium
in the air stream. This was considered important to eliminate the
potential for contamination of the sample by organic materials that may
leach from the seating gasket normally used.
Initially, a standard high-volume sampler housing was used to support the
apparatus. This proved unsatisfactory for two reasons. It was large,
cumbersom, and difficult to transport. The blower motor operates under
greater load than the conventional high-volume sampling use, and hence,
tended to heat the enclosed sampler housing to an excessive degree.
Elevated temperatures were considered potentially disadvantageous to the
capability of the adsorbent medium to retain the PCB. A simplified, open
construction sampler supporting stand was therefore designed. The basic
design of this supporting stand is shown in Figure 1. Four legs con-
structed of steel pipe are fitted into couplings welded to a rectangular
steel support ring. This support ring is fashioned to the dimensions of
the filter holder assembly. The sampling apparatus is suspended in this
support assemoly. An aluminum sheet cover is positioned over the filter
assembly and supported by threaded bolts welded to the support ring. The
cover is attached to these bolts with wing nuts. This cover protects the
glass fiber filter and the collection medium from rainfall in the same
manner a conventional high-volume sampler housing is used.
11
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High-volume samplers are normally operated from a conventional 60-cycle,
120-volt power supply. With a glass fiber filter in place, a typical
sampler will draw air at approximately 1.7 m^/min. The air flow rate
is reduced to approximately 1 m^/min with the polyurethane foam
inserted into the throat and the glass fiber filter in place. Better
flow control is achieved by use of a motor speed controller. A potentio-
metric controller or variac of suitable capacity should be used. A flow
rate curve is generated for each individual sampler using the various
size orifice plates supplied by the manufacturer. After this curve is
plotted, the flow may be determined at any time by measurement of the
exhaust pressure, in inches of water, using a manometer, rotometer, or
calibrated gauge. The flow calibration is described in the Code of
Federal Regulations (1975). For the purpose of sampling airborne PCB, a
flow rate of 0.8 m^/min was found to be suitable.
Some difficulty was experienced during initial sampler runs with the
movement of the polyurethane foam down the throat assembly and seating
against the inner housing assembly of the blower. The polyurethane foam
could not enter the blower, and hence, this was not an immediate problem.
However, it was considered a simple precaution to place a retainer in the
throat assembly to prohibit the polyurethane foam from moving. This
simple retainer device is shown in the exploded view in Figure 1. It
seats on the inner blower housing and keeps the polyurethane approxi-
mately 5 cm above the blower intake. A piece of rigid hardware cloth
would serve the same purpose.
Lewis and Zimmerman (1976) have reported the existence of a capacitor
containing polychlorinated naphthalenes (PCN) in the motor assembly of
certain standard high-volume samplers. When this unit is used for
sampling PCB, using polyurethane foam plugs, PCN is found on the plugs.
This implies the high-volume samplers used recirculate at least a portion
of the sampled air. Significant air recirculation will result in low
analytical results of the air sampled. In addition, PCN contamination
severely interferes with both qualitative assessment and quantitative
12
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analysis of PCB. Recirculation must be prevented. This is accomplished
by placing an exhaust duct three or more meters in length on the high-
volume motor housing, as shown in Figure 1. Collapsible ducting is ideal
for this purpose. In this way, the sampler exhaust can be located remote
from the sampler intake to prohibit any opportunity for recirculation.
The high-volume samplers used throughout the laboratory investigations
and field studies reported in this document do not contain the capacitor
discussed by Lewis and Zimmerman (1976). Only samplers without the
PCN-containing capacitor should be used.
A 20 cm x 25 cm glass fiber filter (Gelman Type A) is placed in the
filter holder assembly for each sample run. The purpose of this glass
fiber filter is not to separate particulate from gaseous PCB in ambient
air, since this is not considered possible with a compound of insuffi-
ciently low vapor pressure, but to keep airborne particulate from
embedding in the polyurethane foam. The glass fiber filter is normally
analyzed along with the polyurethane after sample collection. Experience
has shown, in most cases, that a significant amount of PCB is seldom
retained on the glass fiber filter. Once this is established, it is not
necessary to include the glass fiber filter in the analysis.
The collection medium used is a commercially available polyurethane foam
material. For purposes of this study, a 7.6 cm thick sheet of the
material of density O.U25 g/cc was obtained. Cylindrical plugs of 9 cm
diameter are cut from the foam sheet. The plugs are cut oversize so that
they fit snugly into the sampler in such a manner that air cannot bypass
them. Three polyurethane foam plugs, each 7.6 cm in thickness, were
used, for a total thickness of 23 cm, for most of the studies conducted.
The extensive polyurethane foam cleanup procedures that must be followed
before the material is used will be discussed in a later section of this
report.
13
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2.3 ANALYTICAL PROTOCOL
The step-by-step procedure recommended for the analysis of ambient air-
borne PCB is included as Appendix A to this report. This procedure is
drawn from the technical literature, personal contact with persons
knowledgeable in the field, and both laboratory and field experience.
The purpose of this chapter is to relate experience gained during
development of the method.
Figure 3 is a flow diagram of the analytical scheme. The procedure
consists of preparation of materials, field sampling, extraction, con-
centration, cleanup, and gas chromatographic analysis. To avoid the
difficulty and uncertainty in accurately quantifying the PCB present in a
sample, it is often necessary to employ the perchlorination technique
developed by Armour (1973). Considerable effort was applied to adopting
this technique for routine use in quantitation of ambient airborne PCB.
Some modifications of the perchlorination technique were necessary to
achieve quantitative derivization of ambient airborne PCB.
2.3.1 Cleanup of Materials and Apparatus
It has been emphasized many times by numerous researchers that PCB are
ubiquitous in the environment. They are present in the laboratory
atmosphere, on glassware, and occasionally as contaminants in chemical
reagents. Strict attention must be given to every detail of sample
handling in order to avoid PCB contamination. It was found necessary to
employ rather extensive cleanup measures to avoid PCB contamination from
materials and apparatus. All materials that come into physical contact
with the samples are sequentially cleaned by detergent wash, tap water
rinse, deionized water rinse, acetone rinse, petroleum ether rinse, and
heating to remove any residual organics. This applies to the sampling
system, to glassware, aluminum foil, and any items used to handle the
polyurethane foam.
The polyurethane foam that is used as an adsorbent medium requires exten-
sive cleanup by solvent extraction in a soxhlet extraction apparatus.
Extraction is performed with nanograde hexane for a period of 12 hours.
14
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CLEANUP OF POLYURETHANE
FOAM PLUGS, GLASS FIBER FILTERS
AND SAMPLING APPARATUS
Field Sampling
Soxhlet Extraction of
Polyurethane Foam Plugs
and Glass Fiber Filters
Silica Gel
Separation
Pesticides
Fraction
GC/EC Analysis
of PCB Mixture
1
GC/FID Analysis
of Biphenyl
Perchlorination
PCB Quantitation
by Pattern Matching
±
GC/EC Analysis of
Decachlorobiphenyl
Figure 3. Analytical scheme for PCB in ambient air.
15
-------
Following this, they are dried with organic-free nitrogen in a heated
vacuum desiccator and sealed in cleaned glass containers until use. This
is similar to the polyurethane foam cleanup procedure that is recommended
by Bidleman and Olney (1974b). If it becomes necessary to prepare a
larger number of polyurethane foam plugs, it has been found convenient to
use a glass apparatus similar to that shown in Figure 4 for drying rather
than the vacuum desiccator, which has a limited volume. It is important
to take every precaution to remove residual organics from the nitrogen
used for drying the plugs and for other steps in the analytical proce-
dure. An organic trap of the type shown in Figure 4 has been found to be
effective if the components are replaced at routine intervals when they
become saturated with organic gases. The polyurethane foam used in this
trap has been extracted with solvents as described above prior to use.
A typical polyurethane foan extract is depicted in Figure 5. This is an
electron capture chromatogram of an extract that has been prepared as
described above. It was selected randomly from plugs stored before use
in glass containers. The unexposed plug can be carried through the
analytical procedure in a manner identical to a sample in order to demon-
strate contamination-free laboratory procedures.
It is essential that the extensive pre-cleaning procedures for the poly-
urethane foam plugs as described in Appendix A be followed. All of the
foam materials tested contained PCB and other electron capture sensitive
contaminants that must be removed before use of the material as a collec-
tion medium. Shorter than 12-hour extraction periods did not adequately
reduce contaminant levels. A 5-hour extraction of plugs of the proper
dimensions cut from the stock foam material described in Appendix A
yielded a mean blank value of 113 ng as DCB with a range of 42 to 200 ng
and a standard deviation of 58 ng for five samples. Twelve-hour extrac-
tion of the same five plugs yielded blank values as follows:
Mean DCB residual 54 ng
Range of values 30-78 ng
Standard deviation 9 ng
16
-------
Both the mean residual DCB and the range of values from one plug to
another is reduced to manageable levels by 12-hour extraction. The
residual DCB level (blank value) for each lot of polyurethane foam plugs
that are prepared for sample collection must be determined before they
are used in order to validate the adequacy of the pre-cleaning procedure.
Polyurethane foam plugs may be reused after sample extraction for
collection of further samples by simply drying and returning to glass
containers for storage. It is not necessary to repeat the 12-hour
soxhlet extraction if the plug is not exposed to contamination.
The glass fiber filter (Gelman Type A) is pre-conditioned by heating for
several hours to remove any organics present. These filters should not
be stored in cardboard boxes or manila envelopes, since these materials
and other paper products sometimes have very high levels of PCB con-
tamination. A typical chromatogram of a filter blank is reproduced in
Figure 6.
2.3.2 Field Sampling
Field sampling procedures are sufficiently straightforward that they can
be performed without undue burden. It is necessary, however, that the
individual responsible for sampling be conscientiously aware of the
potential for PCB contamination and take routine precautions to avoid
it.
Recirculation of exhaust from the sampling apparatus to the intake has
been discussed. This is a problem that must be avoided by placement of
the end of the exhaust duct so that recirculation is unlikely to occur.
An exhaust duct 3 m in length has been found to be effective; however, if
there is any question concerning the possibility of recirculation in a
given situation, a longer exhaust duct is recommended. Collapsible
ducting of the type used to vent household clothes dryers is ideal for
this purpose.
The placement of pre-cleaned polyurethane foam plugs in the sampling
apparatus is done at the sampling location. Only pre-cleaned metal tongs
17
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18
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are used to handle the plugs. When plugs are placed in the apparatus,
the individual should assure they fit snugly to avoid any possibility of
leaks around them. There should be a minimum of exposure of the cleaned
plugs to the laboratory or ambient atmosphere. Immediately after
sampling is complete, the polyurethane foam plugs are removed from the
sampling apparatus and returned to the appropriately-labeled storage
container for transport back to the laboratory. The glass fiber filter
is handled in the same manner. When storage is necessary, it is prefer-
able to keep the exposed plugs in the dark and under refrigeration in
order to avoid any decomposition that may possibly take place.
2.3.3 Sample Extraction
Exposed polyurethane foam plugs are transferred to a soxhlet extraction
apparatus and extracted for 3 hours with nanograde hexane. The glass
fiber filter is extracted in the same manner as the plug. All plugs may
be extracted together; they may be extracted separately and combined; or
the glass fiber filter and the plugs may be analyzed separately. The
polyurethane foam plugs can be reused if they are immediately dried in
the proper manner and returned to storage in a sealed glass container.
Even high concentrations of PCB (e.g., 128 ug as DCB) spiked onto a plug
were quantitatively removed during a 3-hour extraction period.
Contamination of the sample was sometimes noted when the paper thimbles
normally used in a soxhlet extraction apparatus were employed. It was
found that the extractors performed satisfactorily without these thimbles
and they were subsequently eliminated. Another point of caution is worth
mentioning. An interference problem was encountered in the use of
boiling chips ("Boileezers" marketed by Fisher Scientific Co.) in the
soxhlet extraction step. Broken glass which has been heated to remove
organics serves as a most satisfactory boiling aid without causing
interference problems.
2.3.4 Sample Concentration
Larger volumes of sample extract are concentrated satisfactorily using a
Kuderna-Danish evaporator. When it is necessary to reduce extract volume
21
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to less than 5 ml, a modified micro-Snyder apparatus is used. Extreme
caution must be exercised to avoid evaporation of any sample to dryness.
In the early phases of evaluation of the laboratory procedures, excellent
recovery efficiencies (average 104 percent) were achieved with Aroclor
1260. Since airborne PCB is likely composed of more volatile species
than those present in Aroclor 1260, analytical recovery studies were con-
ducted using Aroclor 1016. This mixture contains principally di-, tri-,
and tetrachlorobiphenyls. Recovery efficiencies were found to be erratic
and poor. Step-by-step evaluation of the analytical technique isolated
the problem to two steps in the procedure where the sample extract was
evaporated to "near dryness." During these steps, it was found that a
significant amount of the dichlorobiphenyl present in Aroclor 1016 was
lost by volatilization resulting in modification of the chromatographic
pattern. This, of course, would introduce serious error in the quantita-
tion of airborne PCB. The analytical procedure was, therefore, modified
to eliminate procedural steps resulting in the evaporation of sample
extracts to dryness or "near dryness." Acceptable analytical recovery
efficiencies (average of 97 percent) were subsequently achieved with
Aroclor 1016 using the modified procedures.
2.3.5 Sample Cleanup
The silicic acid cleanup procedure developed by Snyder and Reinert (1971)
is employed to remove chlorinated pesticides and other interfering sub-
stances from the sample. This technique is not effective in eliminating
DDE or toxaphene.
The sulfuric acid cleanup procedure of Murphy (1972) was found to remove
a significant number of contaminants from certain of the sample extracts;
however, it was not found to be necessary to use a sulfuric acid cleanup
step routinely.
2.3.6 GAS CHROMATOGRAPHIC ANALYSIS
Analysis was conducted on a Varian 2760 gas chromatograph using a tritide
foil electron capture detector. A 1.5%/1.95% OV-17/QF-1 packed glass
column was found to be suitable. Confirmation was performed on a 4X/6X
22
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SE-30/OV-210 column. Operating conditions for both these columns are
described in the appendix. Several analyses were also confirmed by gas
chromatography/mass spectrometry (GC/MS) using a AEI 30 (Associated
Electronic Industries) instrument. The OV-17/QF-1 column was used with
this instrument under the same operating conditions as described in the
appendix, with the exception that helium was used as the carrier gas in
place of nitrogen.
The importance of confirmation of peaks cannot be overstressed. This
can be demonstrated by the following two figures. The sample is one of
the initial field samples of urban atmosphere. The chromatogram is
complicated by numerous peaks which could not be identified as PCB.
Figures 7(a), (b), and (c) are chromatograms of the first, second, and
third polyurethane foam plugs, respectively, as they are located in the
sampling apparatus. Figure 7(d) is a chromatogram of Aroclor 1221 on the
same column. Those peaks indicated by a 'V' match corresponding peaks in
Aroclor 1221 and/or Aroclor 1016. The first major apparent PCB peak,
eluting at 1.33 minutes, appears to be present in roughly equivalent
amounts on all three plugs indicating a poor collection efficiency. This
did not seem consistent with other data, so the sample was run on the
confirmatory GC column. Figure 8(a) is a chromatogram of the first plug
on the confirmatory column. Figure 8(b) is a chromatogram of Aroclor
1221 on the same column. 2-Monochlorobiphenyl (2-MCB), 4-monochlorobi-
phenyl (4-MCB), 2,2'-dichlorobiphenyl (2,2'-DCB) and 2,4-dichlorobiphenyl
(2,4-DCB) have been identified by comparison with these pure PCB isomers.
The peak which appeared to match 2-MCB on the OV-17/QF-1 column, was not
confirmed on the SE-30/OV-210 column. Its position falls between the
peaks eluting at 1.18 minutes and 1.49 minutes. 2-MCB was not present at
all. This was later confirmed by GC/MS analysis.
2.3.7 Perch!orination
Quantitation of PCB in environmental samples is sometimes an extremely
difficult and, unfortunately, often an inexact procedure. There exists
little difficulty in those cases where the GC elution pattern closely
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29
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resembles that of an Aroclor, but this is often not the case. With
ambient airborne PCB in particular, there is little reason to expect a
close correspondence with any single Aroclor unless the sample is taken
very near the source of the pollution. The more volatile PCB isomers
will likely be enriched in the atmosphere and airborne transport will not
likely be uniform for isomers of different volatility. Each of these
factors will alter the nature of the collected sample and distort the GC
elution pattern, making quantitation a difficult task. When peak-to-peak
area ratios in the sample are different from those in the standard used
for purposes of quantitation, results may be reported which are
significantly in error.
Another approach to the task of quantitation of PCB in ambient air is by
comparison of individual PCB isomers found to be present in the sample
with known concentrations of that isomer. Quantitation in this manner is
possible for the monochlorobiphenyl and dichlorobiphenyl species, since
there exists a manageable number of isomeric variations of these species
in commercial PCB mixtures. Three monochlorobiphenyl isomers and four
dichlorobiphenyl isomers have been detected in Aroclors (Hutzinger, Safe,
and Zitko, 1974). The task is rapidly complicated, however, when tri-
chlorobiphenyl isomers are present. There have been 17 trichlorobiphenyl
isomers detected in commercial PCB mixtures. Perhaps by use of capillary
column GC, quantitation in this manner would be feasible for more highly
substituted isomers. However, it would certainly entail a long, arduous
process when greater than trichloro isomers are present.
The most logical approach to accurate quantitation of airborne PCB is by
use of the perchlorination technique recommended by Armour (1973). This
technique permits derivitization of all PCB present to decachlorobiphenyl
(DCB). When this is done, the task of quantitation is greatly simplified
and the detection limit is improved, since DCB is a single isomeric
species. Confirmation of the PCB is also accomplished by this technique.
Armour (1973) achieved essentially quantitative conversion of Aroclors
1016, 1242, 1248, 1254, 1260, and 1262 to DCB using this technique at
microgram levels. If all PCB present in an ambient air sample could be
30
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chemically derivatized to DCB in this manner, quantisation would be
accurate, precise, and reproducible from one analyst to the next with
little variability due to subjective GC pattern interpretation. The
nature of the PCB present can be qualitatively assessed before
perchlorination.
Investigations were conducted into the use of the perchlorination tech-
nique for the analysis of ambient air samples for PCB collected on
polyurethane foam. The method of Armour (1973) was initially used. The
utility of this procedure is demonstrated by Figures 7(a) and 9.
Figure 9 is a chromatogram of the same air sample shown in Figure 7(a)
after perchlorination. Quantitation of PCB is obviously greatly simpli-
fied. The PCB is clearly separated in elution time from other materials
which are not removed by the extensive cleanup procedures applied to the
sample. The analytical detection limit is also greatly enhanced by per-
chlorination since the electron capture detector is much more responsive
to DCB than lower-substituted isomers. The first polyurethane foam plug,
shown in Figures 7(a) and 9, contained 1,790 ng of PCB as DCB; the
second, 920 ng. The concentration on the third plug was equivalent to
blank values observed for unexposed plugs.
Two problems in application of the Armour method had to be overcome,
however, to achieve satisfactory results for airborne PCB. First, the
method did not yield quantitative results when attempts were made to
perchlorinate PCB species of less than trichloro substitution. Secondly,
even for Aroclors, quantitative recovery was not achieved for less than
1 ug quantities of PCB. Both of these problems, it was discovered, were
the result of the volatile loss of PCB during one step in the procedure
where the extract is evaporated to near dryness. Furthermore, the recom-
mended reaction temperature appeared to be sufficiently high to result in
decomposition of the lower-substituted PCB species. After rather exten-
sive experimentation and several modifications to the original Armour
method, quantitative recovery was achieved for even the most volatile PCB
species in sub-microgram quantities.
31
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(a) Decachlorobiphenyl Standard
(b) Air Sample
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Figure 9. Chromatogram of a Perchlorinated Air Sample.
32
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The sample is extracted from the polyurethane foam with hexane, concen-
trated, and cleaned up using silica gel. Since the perchlorination
reaction cannot be carried out in hexane, all residual hexane must be
removed from the extract prior to perchlorination. Even small amounts
of residual hexane will result in the formation of a black, solid resi-
due upon the addition of the antimony pentachloride (SbC^). This
severely reduces PCB recovery. Attempts to remove the hexane by direct
evaporation, even when very carefully conducted, invariably resulted in
the volatile loss of dichlorobiphenyl and monochlorobiphenyl from test
sofutions. The hexane is, therefore, removed by azeotropic evaporation
from a hexane/chloroform mixture. To the 1.0 ml extract in a Kuderna-
Danish (K-D) apparatus, is added 10 ml of chloroform. This is concen-
trated by slow boiling to 4 ml. Repeat this azeotropic evaporation three
additional times by adding 10 ml increments of fresh chloroform in order
to remove all traces of hexane.
After removal of hexane, the chloroform extract is quantitatively trans-
ferred to a reaction vial, prepared as shown in Figure 10, using three
chloroform rinses. The reaction vial is a 16 x 100 mm glass screw top .
culture tube with teflon-lined screw cap which has been modified by
drawing the bottom into a cone shape. Reaction vials prepared in this
manner were found to be easier to work with and much more reasonable in
cost than the vacuum hydrolysis tubes recommended by Armour. The tapered
bottom of the vial allows the analyst to reduce solvent volume to 0.1 ml
without going to dryness. Add two boiling chips and immerse the reaction
vial upright in a 70°C water bath to a depth of 6 + 2 cm. Increase the
water bath temperature slowly until the solvent begins to boil at
72-76°C. Concentrate slowly to a volume of approximately 0.1 ml. Under
no circumstances should the water bath temperature be permitted to exceed
76°C nor should the solvent be evaporated to dryness. If either of these
occurs, PCB will be lost by volatilization and consequent recoveries will
be low. The final volume (0.1 ml) may be determined with sufficient
accuracy by comparison of the solvent remaining with another reaction
vial containing 0.1 ml of chloroform. Cap the reaction vial immediately
after concentration and allow to cool.
33
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Teflon-lined cap
mr
Figure 10. Perchlorination reaction vial
34
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Reagent grade SbCl^ from several commercial sources has been found
to contain DCB and bromononachlorobiphenyl (BNCB), as reported by
Trotter and Young (1975). The DCB contaminant results in a positive
blank value, and the BNCB interferes with the perch!orination of the
lower-substituted PCB species. The SbCl5 selected for use must first
be analyzed for these contaminants. SbCl^ manufactured by Cerac Pure
(Stock Number A1147, Lot Number 15-26A) was found to be suitable. DCB
contamination of this reagent is approximately 10 ng/ml. BNCB was not
detected.
The reaction vial containing the sample is placed into a preheated
(16U + 3°C) aluminum block heater for a period of 15 hours. It was found
that the use of higher reaction temperatures (185°C) as recommended by
Armour resulted in poor recovery of di- and mono-substituted PCB species.
Apparently these species were not stable at the higher temperatures.
Reaction temperatures less than 150°C also resulted in poor recovery due
to incomplete conversion of lower-substituted PCB species to DCB.
Shorter reaction periods may be adequate to affect quantitative deriva-
tization; however, the 15-hour period is convenient for overnight,
unattended use.
After the reaction period, the reaction vial is removed from the heater
and allowed to cool to room temperature. Then it is cooled in an ice
bath before the addition of 1 ml of 6 ^ HC1 to inactivate the excess
perchlorination reagent. Pressure from the reaction vial is cautiously
vented in a fume hood, directed away from the analyst, to avoid any
possibility of injury.
To extract the DCB from the reaction mixture, add 1 ml of hexane to the
reaction vial, shake vigorously for 3D seconds, and carefully draw off
the hexane layer with a disposable pi pet. Place this hexane extract on
the top of a 6 mm x 12 cm disposable pi pet packed with 2 g of anhydrous
This column is prewashed with hexane. Repeat hexane extraction
35
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of the reactants in this manner five times. Tests have shown this repe-
tition assures quantitative recovery of DCB. After passing all six
increments of the hexane extract through the ^$04 column, pass two
additional 1-ml portions of fresh hexane through the column. Collect
all fractions in a 10-ml graduated K-D apparatus. Connect a modified
micro-Snyder column to the K-D apparatus, add a single boiling chip,
and evaporate in a water bath (70°C) to less than 0.5 ml. Add fresh
hexane to oring the volume back to exactly 1.0 ml on the graduated K-D
receiver. Cap the receiver tightly or transfer the contents to a sealed
container to avoid evaporation of solvent prior to gas chromatographic
analysis. Store in a cold, dark location to avoid any possibility of
photodegradation.
It is recognized that biphenyl, if present in a sample extract, would
perchlorinate to OCB. Therefore, attempts were made to remove biphenyl
from the extract before the addition of the perchlorinating reagent. Two
approaches were taken without success. First, it was attempted to
selectively remove biphenyl from the reaction mixture by either hydroly-
sis or nitrification. ^SO^ and H2S04/FS03H treatment of a mixture of
biphenyl and PCB resulted in no effect. The use of concentrated FS03H
and 502/^504 each resulted in decomposition of both biphenyl and PCB.
HN03/H2$04 caused nitration of PCB and biphenyl. The use of an activated
alumina chromatographic column to selectively isolate biphenyl from a PCB
mixture was also evaluated. This method showed some promise; however, a
considerable amount of research would have been required to find the most
suitable conditions (e.g., column dimensions, eluting solvents, activity
grade, etc.) for effective isolation of biphenyl. Therefore, it was
decided not to pursue this technique further, but to develop GC condi-
tions for the analysis of biphenyl.
The GC conditions using a flame ionization detector that are described in
Appendix A (Section 12.u) were found to provide an adequate detection
limit for biphenyl in a sample extract. Hence, if the analyst suspects
36
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biphenyl may be present, the GC/FID analysis is conducted to determine
the amount present in the sample extract. The efficiency of conversion
of biphenyl to DCB using the method described in Appendix A is 43.3 +
8.8 percent. This conversion efficiency is based on ten replicate analy-
ses at 3.4 ug and U.7 ug biphenyl. The analyst may correct the results
obtained upon perch!orination by subtracting that amount resulting from
the conversion of biphenyl present in the extract to DCB. Biphenyl was
detected during preliminary field tests near a transformer storage
facility. Field tests at other locations did not yield detectable
levels of biphenyl.
After the modifications described above were incorporated into the per-
ch! ori nation method to eliminate the problems encountered with volatile
loss of PCB and thermal decomposition of the lower-substituted PCB
species, a series of method recovery studies were conducted. The modi-
fied perchlorination method, as described in detail in Appendix A, was
tested using Aroclor 1016, Aroclor 1254, and a test mixture of the most
volatile and least thermally stable PCB species. The test mixture con-
sisted of 25 percent monochlorobiphenyl (2-MCB), 55 percent dichlorobi-
phenyl (2,2'-DiCB, 2,4-DiCB, 2,4'-DiCB), and 20 percent trichlorobiphenyl
(2,2',5-TCB). The results of these recovery studies are summarized in
Table 1. Quantitative recovery was achieved for even the most volatile
species over the range of at least 100 ng to 10 ug concentration. The
overall mean recovery for all tests was 100+5 percent. The difficulties
with poor recovery of the lower-substituted species at sub-microgram
concentrations have, therefore, been overcome by the modifications to the
original procedure.
2.3.8 Perchlorination Ruggedness Test
A ruggedness test (Youden and Steiner, 1975) was performed on the final
modified perchlorination method to assess the likelihood of achieving
comparable inter!aboratory results for PCB at low concentrations. The
37
-------
TABLE 1
PERCHLORINATION RECOVERY VS. CONCENTRATION TEST RESULTS
PCB
Aroclor 1016
Aroclor 1016
Aroclor 1254
Test Mixture*
Aroclor 1016
Test Mixture*
Test Mixture*
PCB Concen-
tration
(ug)
10.0
5.0
3.0
1.18
0.750
0.412
0.103
Number of
Replicates
3
3
1
3
4
2
3
Percent
Recovery
103
105
113
98
93
101
101
Standard
Deviation
3.7
2.1
—
6.5
5.6
1.1
4.7
Consisting of 25% monochlorobiphenyl, 55% dichlorobiphenyl, and 20%
trichlorobiphenyl.
statistical theory underlying the ruggedness testing methodology is dis-
cussed by Youden and Steiner (1975). Seven parameters are chosen for
testing and their nominal values (the value specified in the procedure)
are denoted by A, B, C, D, E, F, and G.
A challenging value for each of those parameters is then selected and
denoted by a, b, c, d, e, f, and g. The challenging parameters should
represent differences that might be introduced as a result of different
analysts at different laboratories following the same procedure. A
series of eight experiments are then conducted using the combinations of
conditions specified in Table 2. Each of the eight experiments, which
may be performed in replicate, produces a result. The experimental
results are denoted as S, T, U, V, W, X, Y, and Z. The results can be
grouped as follows, for example, to determine the difference attributable
to variable A:
A - S + T + U + V U + X + Y + Z
A—a -
-------
TABLE 2
EIGHT COMBINATIONS OF SEVEN FACTORS USED TO TEST THE
RUGGEDNESS OF AN ANALYTICAL METHOD
Factor
Value
A or a
B or b
C or c
D or d
E or e
F or f
G or g
Observed
Result
Determination Number
1
A
B
C
D
E
F
G
S
2
A
B
c
D
e
f
g
T
3
A
b
C
d
E
f
g
U
4
A
b
c
d
e
F
G
V
5
a
B
C
d
E
F
g
W
6
a
B
c
d
e
f
G
X
7
a
b
C
D
E
f
G
Y
8
a
b
c
D
e
F
g
z
After Youden and Steiner (1975),
39
-------
The ruggedness test of the perchlon'nation method incorporated the seven
factors listed in Table 3. These factors varied from nominal (procedure
specified) conditions to the degree that might be expected of a competent
analyst following the written procedure. The ruggedness test format and
data are shown in Table 4. Each determination number consisted of
triplicate analysis of a PCB test mixture containing 25 percent monochlo-
robiphenyl, 55 percent dichlorobiphenyl (three isomers) and 20 percent
trichlorobiphenyl at a total concentration of 0.824 ug PCB. The test
involved 24 separate analyses and, hence, has statistical reliability.
The ruggedness test results are tabulated in Table 5. All factors showed
a difference of less than that of the blank. Hence, the challenging
conditions that were applied in no way affected the outcome of the
determination. Furthermore, the difference observed for the blank (no
variation) determination was +3.25 percent, which is satisfactorily low.
An estimate may be made of the analytical standard deviation as follows:
standard deviation = /2/7 Di 2
where Dj is the difference (Table 5) measured for each factor. When
the data from Table 5 are entered into this formula, an estimated analy-
tical standard deviation of 3.0 percent results. This is an acceptable
level of variance for gas chromatographic analytical procedures.
40
-------
TABLE 3
PERCHLORINATION RUGGEDNESS TEST CONDITIONS
Factor
Extract transfer
rinse volume
Reaction
temperature
SbCl5 reagent
volume
Final extract
vol time
Blank
Solvent evaporation
temperature
Water bath
immersion depth
Procedure
Step No.*
8.2.3
11.4.2
11.4.1
11.3.6
—
11.3.5
11.3.4
Nominal
A = 4 ml
B = 160°C
C = 0.2 ml
D = 0.1 ml
E = e
F = 72°C
G = 4 cm
Challenging
a = 1 ml
b = 165°C
c = 0.1 ml
d = 0.3 ml
e = E
f = 76°C
g = 9 cm
*As described in Appendix A.
41
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42
-------
TABLE 5
PERCHLORINATIOM RUGGEDNESS TEST RESULTS
Difference
Rank Factor
1
2
3
4
5
6
7
Blank
Reaction Temperature
SbCl5 Volume
Final Extract Volume
Water Bath Immersion Depth
Extract Transfer Method
Solvent Evaporation Temperature
+3.25
+2.95
-2.80
1.40
-1.30
0.75
0.15
The results of ruggedness testing of the modified perchlorination method
indicate the method is "rugged" and therefore immune to modest depar-
tures from habitual routine on the part of the analyst. Furthermore,
all method variables are in control. Variation within the specified
limits of the procedure should not affect the outcome of the analysis.
Competent trace analytical chemists following the above procedure in
different laboratories should therefore achieve comparable analytical
results.
43
-------
3.0 RECOVERY STUDIES AND FIELD TESTS
After development of suitable laboratory analytical techniques and dem-
onstration that these techniques permitted quantitative recovery of PCB
ranging from mixtures of low substitution (e.g., Aroclor 1221) to mix-
tures of a high degree of substitution (e.g., Aroclor 1260), and after
improvement of the perchlorination method, efforts were turned to an
evaluation of the selected sampling method for airborne PCB. This evalu-
ation was conducted in such a manner that it was, in fact, an evaluation
of the entire method, including both sample collection and laboratory
analysis. This chapter describes the results of collection efficiency
and recovery studies of the method, preliminary field tests, and field
tests of the final sampling and analytical method. The collection
efficiency and recovery studies were conducted to identify the capabili-
ties and limitations of the high-volume sampling method selected. The
preliminary field tests described below were conducted over the course of
development of the method. They provided valuable information pertinent
to development of the method for routine use. Finally, after method
development was complete and the method tested in the laboratory, it was
subjected to several thoroughgoing field tests.
3.1 RECOVERY STUDIES
PCB recovery studies were first conducted with Aroclor 1221 and, more
extensively, with Aroclor 1016. These two commercial mixtures were
selected for the initial studies for two reasons. First, they are
composed principally of the lower-substituted PCB species which are
generally the more volatile ones. Secondly, Aroclor 1221 and Aroclor
1016 are commonly used commercial products.
It would be anticipated, and has been shown by Mieure (1975), that the
more volatile PCB species are likely to be found in the atmosphere in
greater amounts than the less volatile species. The molecular composi-
tion of several Aroclors is tabulated in Table 6. Aroclor 1221 is com-
posed predominantly of biphenyl, monochlorobiphenyl, and dichlorobiphenyl.
44
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Aroclor 1016 is largely trichlorobiphenyl with significant amounts of
dichlorobiphenyl and tetrachlorobiphenyl. Approximately 48 percent of
the total domestic production of PCB in 1975 consisted of Aroclor 1016.
Another 25 percent consisted of the closely related product Aroclor 1242
(Monsanto Co., 1975). Aroclor 1221 production quantities were much
lower, comprising less than 1 percent of total annual production in 1975;
however, Aroclor 1221 was produced in considerably larger quantities
during the years 1957 to 1974.
The sampling system used for the collection efficiency studies is identi-
cal to that described earlier and illustrated in Figure 1. A Gelman
20 x 25 cm glass filter (Type A) which has been heated to remove any PCB
contaminant is placed in the stainless steel filter holder. Three pre-
cleaned polyurethane foam (PUF) plugs are fitted into the throat of the
sampler in the manner described in the method (Appendix A). A known
quantity of Aroclor, dissolved in isooctane or hexane, is quantitatively
transferred to the center of the filter using a volumetric pi pet. The
sampler is immediately turned on at an adjusted flow rate of 0.8 m3/min
and the sampling period is commenced. Samplers were run 20 minutes for
each of these initial recovery studies. Approximately 16 cubic meters of
air were drawn through the glass fiber filter and the three PUF plugs.
The tests were conducted in the laboratory using large enough PCB spike
concentrations and short enough sampling periods that background levels
could initially be ignored in computation of spike recoveries.
Figure 11 illustrates the first, second, and third PUF plug extract chro-
matograms and a chromatogram of the glass fiber filter extract after a
recovery experiment using Aroclor 1221. Note the recorder attenuation
factors indicated for these chromatograms. The first PUF plug chromato-
gram is shown at a recorder attenuation of 16 x 1Q~9, while the others
are shown at attenuation 4 x 10~9. Those peaks designated by a "•"
have been identified as peaks matching those present in Aroclor 1221;
those designated by an "x" are not present in Aroclor 1221. The labeled
peaks have been specifically identified using pure isomers of
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2-monochlorobiphenyl (2-MCB), 4-monochlorobiphenyl (4-MCB), 2,2'-
dichlorobiphenyl (2,2'-DCB), and 2,4-dichlorobiphenyl (2,4-DCB). It was
later determined that many of those peaks on the chromatograms which are
designated by an "x" originated with the sampler exhaust. Recirculation
from sampler exhaust to intake was apparently occurring. This problem
was eliminated on subsequent work.
As demonstrated in Figure ll(a), the Aroclor 1221 can be identified on
the first PDF plug, which comprises the first 7.6 cm of the total length
of 23 cm of PUF collection media. Figure ll(d), the chromatogram of the
glass fiber filter, demonstrates that the Aroclor 1221 spiked onto the
filter at the initiation of the study was quantitatively volatilized.
Very little of the PCB was detected on the second and third PUF plugs, as
shown in Figures 1Kb) and (c).
The quantitative results of the Aroclor 1221 collection efficiency study
are tabulated in Table 7. Since 51 percent and 32 percent of commercial
Aroclor 1221 is monochlorobiphenyl and dichlorobiphenyl, respectively, as
shown in Table 6, then the Aroclor 1221 spiked onto the glass fiber
filter contained 15,7UO ng of the monochlorobiphenyl species and 9,840 ng
of the dichlorobiphenyl species. Of the remainder, 11 percent of the
total composition is biphenyl and 6 percent is PCB of greater than
dichloro-substitution. A total of 98 percent of the Aroclor 1221 spike
was volatilized from the glass fiber filter. Over 97 percent of the
monochlorobiphenyl was captured on the first two PUF plugs. All of the
dichlorobiphenyl was captured on the first two PUF plugs. If biphenyl is
excluded from consideration, since the electron capture detector is not
sensitive to this species, a total of 92 percent of the PCB was captured
on the first PUF plug and 6 percent was captured on the second PUF plug,
for a total recovery of 98 percent.
This collection efficiency study with Aroclor 1221 demonstrated that the
sampling system is capable of quantitatively trapping even the most
48
-------
TABLE 7
RESULTS OF AIRBORNE PCB COLLECTION EFFICIENCY STUDY
USING AROCLOR 1221
3U,750 ng of Aroclor 1221 spiked on high-volume filter. Sampler run
20 minutes, total of 16 m3 air drawn.
Monochlorobiphenyl
ng (% of total)
Dichlorobiphenyl Total PCB*
ng (% of total) ng (% of total)
Spike
1st plug
2nd plug
3rd plug
Filter
15,700
13,600 (87%)
1,100 (7*)
500 (<3%)
550 (3%)
9,840
9,840 (100%)
500 (5%)
<100 (<1%)
<100 (0%)
27,400
25,300 (92%)
1,600 (6%)
<600 (<2%)
<650 (2%)
* Excluding biphenyl.
49
-------
volatile PCB species present in commercial products. It also demon-
strated the method, including both the sample collection and analysis,
has the capability of accurate measurement of airborne PCB.
Six recovery studies were then conducted using Aroclor 1016. These were
conducted in the same manner as the previously described recovery study.
Spike concentrations covered the range of 5.6 to 120 ug of Aroclor 1016.
Figure 12 is a series of typical chromatograms resulting from these
studies. The one depicted is the 20 ug spike. The peaks indicated by a
"•" match corresponding peaks in Aroclor 1016. The peaks designated by
an "x" are the result of contaminants present in the laboratory atmos-
phere. They do not interfere with the Aroclor 1016 chromatogram. As can
be seen by this figure, the PCB is quantitatively captured on the first
PUF plug; that is, on the first 7.6 cm of PUF adsorbing media.
The quantitative results of all six studies are tabulated in Table 8.
In general, over 95 percent of the Aroclor 1016 was volatilized from the
glass fiber filter during each test. The collection efficiency shown in
Table 8 is calculated as follows:
Collection efficiency (%) = I$_p J X 100;
where PI ,2, 3 ""s tne quantity of PCB found on the first, second, and
third PUF plugs, respectively; S is the amount of PCB spiked onto the
filter; and F is the PCB residue remaining on the filter at the conclu-
sion of the experiment. The calculated collection efficiency, therefore,
represents the recovery efficiency of the complete method, incorporating
both the collection efficiency of the sampling device plus the analytical
recovery of the laboratory procedure. The reported variance, likewise,
encompasses both sampling and laboratory analysis.
A mean collection efficiency of 102 percent was achieved for Aroclor 1016
during this short-term collection study. The range was 89 to 117 percent
and the standard deviation was 11 percent. This level of precision is
50
-------
XI*
(a) First polyurethene
foam plug
(d) Third polyurethene
foam plug
(b) Second polyurethene
foam plug
fc) Standard Aroclor 1016
(e) Filter
Figure 12. Aroclor 1016 recovery experiment.
51
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acceptable tor lengthy organic analysis techniques and should be repre-
sentative of results achievable during routine applications of the
method.
It is important to point out in these tests that an average of 85 percent
of the PCS captured was retained on the first PUF plug and 96 percent was
retained on the first two PUF plugs. Hence, three PUF plugs of the
dimensions described above have proved sufficient to retain over 100 ug
of airborne PCB. Furthermore, an average of only 4 percent of the PCB
captured was located on the third PUF plug. Independent analysis of the
third PUF plug extract would, therefore, permit the analyst to judge the
collection efficiency of the system for the particular application
desired without the necessity of conducting recovery studies.
Figure 13 shows the chromatograms of the highest spike recovery (112 ug)
study. Again, V indicates Aroclor 1016 peaks and "x" indicates uniden-
tified laboratory atmosphere contaminants. In this 20-minute test, a
clearly detectable amount of Aroclor 1016 was present on all three PUF
plugs. The entire chromatographic pattern is observed in the extract
from each PUF plug, and the peak-to-peak ratios appear to be largely
unchanged from one plug to another. From this it may be concluded, at
least for very short sampling periods (e.g., 20 minutes), that the chro-
matographic pattern is a reflection of true ambient conditions. Over the
short sampling period there seems to be little modification of the chro-
matographic pattern resulting from selected retention of individual PCB
species. It will be shown later that this is not the case for sampling
periods in excess of 6 hours.
These initial tests confirmed that polyurethane foam can be a highly
efficient collection medium under the conditions recommended in the pro-
posed high-volume sampling method. When two PUF plugs are used (15.2 cm
of adsorbent media) over 100 ug of PCB is retained with a high degree
of efficiency. The inclusion of a third section of PUF provides a
53
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54
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safety factor and a mechanise of estimating the collection efiiciency by
independent analysis of the third PDF plug in the samples. All PCB
species from mono-substituted to tetra-substituted are efficiently
retained on the adsorbing median. It is reasonable to expect penta-
substituted through deca-substituted PCB would, likewise, be effectively-
captured from the atmosphere.
Further testing of collection efficiency and recovery at lower PCR con-
centrations and for longer sampling periods had to await improvement of
the perchlorination method for PCB quant Station as described above, since
no method was readily available for producing large volumes of PCE-free
air to conduct the tests. It was apparent that unless the perchlorina-
tion method could be adapted for use, background levels of PCE and other
substances collected in the sample would obscure the test results. It
would be extremely difficult to discern a low-level Aroclor pattern and
nearly impossible to accurately measure the amount present by pattern
matching techniques. After improvement of the perchlorination method and
demonstration that it worked effectively for the full range of PCB
species, collection efficiency and recovery studies were conducted using
a synthetic PCB test mixture, three single volatile PCE isomers, and
Aroclor 1242.
The composition of the PCB test mixture is listed in Table 9. The test
mixture was spiked onto the ol?s° fiber filter immediately before the
test began in the same mariner as /Voder 1221 described above. The test
was run cut-of-doors in Gainesville, Floric-?.. Alon^ v/ith this and each
succeedirg test, a backgrounc sample was taken at the sar:e location
during the same period of tiro as the test spike sample. Background PCB
concentrations determined by analysis of the background sample glass
fiber filter anc each of the three P'JF plugs were subtracted from the
respective ar,a1ytical results cf the test spike sample to determine spike
recovery. The l.a^k'jrcunr! :..5n."1cs are described in a l?ter section.
-------
TABLE 9
PCB TEST MIXTURE COMPOSITION
PCB Concentration Percent Composition
2-MCB
2,4-DiCB
2,4'-DiCB
2,2'-DiCB
2,2',5-TCB
0.44 ug/ml
0.40 ug/ml
0.52 ug/ml
0.42 ug/ml.^— - —
0.57 ug/ml
18.7%
24.3%
The results of a 1-hour test using the volatile PCB test mixture (2.59 ug
spike) are tabulated in Table 10. These results are reported as DCB
after perchlorination. The collection efficiency is 90 percent based on
recovery of the spike. Of the total PCB collected on the PUF, 93 percent
was captured on the first PUF plug. This test showed even the most vola-
tile PCB species could be retained over a 60-minute period, and that
satisfactory results could be achieved using the perchlorination
technique.
In order to further define the behavior of the more volatile PCB species
in the system, even longer-term collection efficiency tests were run
using pure isomers of 2,2',5-TCB, 2,4'-DiCB, and 2-MCB. The results of
these 2-hour (120 m3) tests are tabulated in Table 11. TCB spike
recovery averaged 91+3 percent for two separate 0.48 ug spikes
(1,115 ng as DCB). DiCB showed a 103 percent recovery for a 1.08 ug
spike (2,080 ng as DCB). In the case of both TCB and DiCB, quantitative
capture was achieved on the first PUF plug alone. MCB demonstrated a
107 percent collection efficiency. Unlike the other species, however,
MCB penetrated beyond the first PUF plug to the second and the third PUF
56
-------
TABLE 1U
RESULTS OF INITIAL RECOVERY STUDY USING PCB TEST MIXTURE*
Sample Duration (mm) 6U
Flow Rate (mJ./mirt) u.76
Volume Air Sampled (m3) 45
Ambient Temperature (°C) 32.5
Ambient .-tumidity ('£) 39
Spike Concentration (ng 0 DC6) 2590
Coreted ^
_
PCb (ng D'CB)
Filter 373
HUT ffl 185U
HUF tit 0
PUF #3 147
Total - 2370
Percent of Total PCB
Col lee tea on PUF (%)
HUF n 93
PUF ff2 0
PUF #3 7
Collection Efficiency (%) 90
* Test mixture composition shown in Table 9. Sample date 4/22/77,
f Background levels are described in Table 18.
57
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plugs as indicated in Taole li. Twenty percent ot tie total MCB was
captured on tne third PDF plug and trie ^redt-^st amount (54 percent) was
detected on the second racier tnan toe first PUF plug. Apparently, the
more volatile MCB moves through the PUF at a significantly faster rate
than either DiC8 or TCii, The 2-hour sampling period is, therefore, aoout
the maximum duration tnat can be usea whi 1.3 achieving quantitative cap-
ture and retention of '1C6, out is entirely sjitaole for the capture and
retention of PC8 species of >)i<]h.:r substitution. Shorter sampling
periods would ue more suitable for the collection of MCB as demonstrated
by the quantitative recovery achieved during the 2l)-minute test using
Aroclor 1221 as described above.
A 12-hour test was then conducted using rlCB, DiCB, and Aroclor 1242 to
determine the maximum length of time that various PCBs could be expected
to De retained on tne PUF material. Tne results of this test are
reported in Taole 12. As expected, during this 12-hour sampling period
in which 634 m^ of air were drawn through the system, MCB was not
effectively retained. A collection efficiency of only 4 percent was
achieved for the 'J.52 ug spike. All ilCB residual */as located on the
second and tnira PUF plugs, with 54 percent of the total on the third
plug. Ninety-tnree percent of the DiCB spike (2.08 ug) was captured
during tni s test, but 2o percent ^as located on the third PUF plug,
b3 percent on the second, •jnd only ly percent on t;ie first. It is clear
from tnis anu tr.c- .jreceeanu tlat:1. fc^ tne 20-minute and 2-hour tests,
that eacr, PC3 species laove-s througn the PUF in a i)3id >nuch like it would
move tnrough a crirouiat^jre^tiic coljmi. Tr.t lower-substituted species
(e.g., MCB, DiCti) inovs inore rapidly through tne syst?n than the ninhor-
substituted species (e.o,, TCB). Tir's will, tkie^eroro, li^'t tne
duration of sampling tnat ":an be o-noloy-l.
Aroclor 1242 was offecti voV ca^tu^oc: '}: t >e cirst y!JF pi j • (Tabl3 12)
during a 12-hour test run usny 3 10.4 uj spi'ce. Aroclor i242 is
reported (Taole b) to contain 1 percent '!C;j, 1': percent OiC? and tne
remainder TCn an-1 more hi go ly-substi tut:c PCB sj'-iJes. H?nc;?, only MCG
limits tne sa,:iplinu aurati >n to ^ ess fon 12 nou-s.
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A 6-hcur n ro\'( ry test using Aroclor 1242 was run in duj. 1 icr.to. The
results of ihi 5 test a PC. tabulated in Table 13. The neon collection
efficiency was <'T? percent after background correction. Since relatively
large spire conc^iitrat iors (10.4 ug) tu r*_ employed, quantitafion of this
test could be accomplished by pattern matching methods, as demonstrated
in the following figures. In the case of both spike- samples and the
background sample, ever C9 percent of the total PCB Vv'as captured on the
first and second PIT f,lugs. The third plug in each case hao little or no
detectable PCB.
Figure 14 is the chromatogram of an Aroclor 1242 standard at the same GC
conditions as the recovery sample shown in Figure 15(a), (b), and (c).
^igure 15 (a) is the chronatcgram of the first PIT plug showing a com-
plete Aroclor 1242 pattern. Peaks matching those in the Aroclor 1242
standard are designated by a "•' . In addition to the Aroclor 1242 that
was captured, other earlier eluting compounds are evident. Two isomers
of DDE (o, p'-DDE and p, p'-DCE) have apparently been captured from the
ambient atmosphere on the first PIT plug, although these peaks have not
been confirmed. The first PIT plug retained a total of 11.6 ug of
Aroclor 1242, while the second ana thirc PIT plugs retained 0.27 jq and
C.C7 ug, respectively. The chromatcgrarrs for the second arc! third PUP
plug extracts are shown in Enure 15(b) and (c), respectively. Only
traces of PCB remained on the glass fiber- filter. In or> r>" t^ determine
the collection efficiency in this test, background PCt hoc to be
subtracted fron the filter and each PUF plug. Chroi'.atogrdi:;s of the back-
grouno sample taken during this test are discussed in a l^ter section
(sec Figures 25 and 26). After correction for the background residual
nCe, the first Plf plug extract contained 9.08 ug Aroclcr 1242 while the
second and thi^c! PUP pl.'C extracts contained background ccrn;<_ted concen-
trations of 0.17 ug and 0.07 ug Aroclor 1242, respectively.
A final series of recovery tests wen? conducted using Aroclor 1242 to
rier,orrn'ne if recovery was dependent on airborne PCE concentration. The
results are tabulated in Table 14. Spike concentrations of 10.4 ug,
61
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b.U ug, and 1.1 ug were used along with a 2-hour sampling period.
Collection efficiencies were 97, 96, and 111 percent, respectively, for
the three spike concentrations after subtraction of background levels.
These values lie within the normal range of analytical variability for
trie method, hence, there is no apparent interrelationship between
recovery and concentration over the range tested.
The results of all the recovery tests that were conducted to validate the
sampling and analytical method are summarized in Table 15. The following
conclusions may be drawn from these studies:
a. There is no apparent variation in either collection efficiency or
recovery as a result of variations in sample flow rate over the range
of 0.6 to 1.0 m^/min.
b. Ambient temperature and ambient humidity exerted no obvious influence
on collection efficiency. One test was conducted during heavy rain-
fall with satisfactory results.
c. The pattern matching method of quantitation is reasonably accurate
for the analysis of Aroclor concentrations in excess of 1 ug in the
PUF extract. Perchlorination is required for lower concentrations.
When the sample elution pattern does not closely resemble an Aroclor,
the perclorination method should be routinely used to achieve
accurate results.
d. The various PCB species move through the PUF collection medium much
like they would move through a chro
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total airborne RGB present in the atmospheric sample, as was found to
be the, case in the field tests discussed later, then it is estimated
from the recovery tests that up to a 6-hour sampling period can be
accommodated with satisfactory recoveries. TCB and more highly-
substituted species are retained for sampling periods in excess of
12 hours.
f. The mean collection efficiency for all the tests conducted for
Aroclor 1016/1242 was 101 + 10 percent with sampling periods ranging
from 20 minutes to 12 hours.
g. When the duration of sampling is within the limits specified in 'e'
above, independent assessment of the amount of PCB captured on the
third PUF plug will allow the analyst to confirm a high collection
efficiency for the airborne PCB without the necessity of conducting
recovery tests.
3.2 PRELIMINARY FIELD TESTS
During the course of development of the recommended method presented in
Appendix A, some preliminary field investigations were necessary.
Certain aspects of these preliminary field data have been previously
discussed in the appropriate section of this report. Brief mention will
be made at this point of the findings from those preliminary investiga-
tions which have not been discussed in an earlier chapter.
Samples were taken of urban ambient atmosphere in Jacksonville, Florida,
using a single polyurethane foam plug of the dimensions described in the
method in each high-volume sampler. Collection efficiency is, therefore,
not known, but it is expected to be less than the laboratory studies
where three polyurethane foam plugs were used in each sampler. Several
samples were collected periodically over a 24-hour period. Sample peri-
ods of 2 to 24 hours were selected. The volume of air sampled and the
analytical results are shown in Figure 16. No PCB was detected in the
glass fiber filters used in the sampling apparatus. These data are
considered to represent minimum ambient airborne PCB concentrations.
69
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Values observed ranged from lb ng/m^ to 25 ng/m^ at sample location A
and from 3 ng/m^ to 3G ng/m^ at sample location B. At sample location B,
there appears to be a greater variability with time of day than at sample
location A.
Figure 17 illustrates a typical chromatogram obtained during this test.
There are numerous extraneous peaks on the chromatogram which make
interpretation and quantisation difficult. At the time this sample was
taken, precautions were not used to prevent sampler recirculation since
the problem was not known. It appears that the PCB present falls in the
range of Aroclors 1242 and 1254. A "•" indicates peaks that clearly
match corresponding Aroclor peaks.
A second preliminary field evaluation was conducted at sample location B
in Jacksonville. Three polyurethane foam plugs were used this time and
the maximum sampling period was shortened to 6 hours. Unfortunately, all
analytical results were less than the detection limit. Ambient levels
were apparently significantly lower at this time.
A third sampling was conducted at this location to obtain additional
field samples for evaluation. Samples were collected at 4-hour intervals
over a 24-hour period. The results are tabulated in Table 16. A reason-
ably uniform PCS concentration was measured over the course of the 24-
hour period. Concentrations varied from 4 ng/ai^ to 9 ng/m . The
chrornatograms obtained have been discussed in a previous chapter of this
report.
71
-------
,CM
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-------
TABLE Ib
RGB IN AMBIENT URBAN ATMOSPHERE
Total PCB
Date Period Concentration (ng/m3)*
11/2U/75
11/2U/75
11/2U/75
11/20/75
11/21/75
11/21/75
^Reported as decachl
12UO-160U
1200-18UO
lbOU-2400
2UOO-24UO
24UO-0600
U600-120U
orobiphenyl .
9
8
9
7
4
6
Environmental Protection Agency (EPA) Region II personnel employed the
high-volume sampling method using polyurethane foam to assess ambient
airborne concentrations of PCB in the vicinity of a major industrial
user. The samples collected by EPA personnel were analyzed in this labo-
ratory. This sampling effort provided preliminary field test conditions
for relatively high airborne concentrations.
Two polyurethane foam plugs were used in the standard high-volume
sampler. Each sampler was operated for a period of 4 hours. Both
plugs were analyzed together, so collection efficiency cannot be
determined.
73
-------
Figure 18(b) shows the chromatogram of the polyurethane plug extracts.
A standard Aroclor 1016 pattern is shown in Figure 18(a). Those peaks
designated by a "•" match corresponding peaks in the Aroclor 1016
standard. Those designated by an "x" do not match Aroclor peaks. The
elution pattern closely resembles that of Aroclor 1016. Four peaks in
the pattern do not correspond with Aroclor peaks. Two of these resemble
PCN, but this has not been confirmed. Quantitation of the three samples
taken in the area yielded airborne concentrations of 498 ng/m3,
400 ng/m3, and 300 ng/m3 as Aroclor 1016.
Confirmation of the PCB present was obtained by gas chromatography/mass
spectrometry (GC/MS). An AEI Model 30 (Associated Electrical Industries)
GC/MS was used with the OV-17/QF-1 column under the operating conditions
described in the appendix, except helium was used in place of nitrogen
tor the carrier gas. The results of GC/MS analysis are depicted in
Figure 19. The GC/MS was operated in the peak monitoring mode at mass
values corresponding to each of the major PCB species. Good correspon-
dence may be seen between the patterns for Aroclor 1016 and the airborne
sample for trichlorobiphenyl and tetrachlorobiphenyl. Semi-quantitative
information can be gained by comparing peak heights of the sample and the
standard in this mode of operation. When this is done, it is apparent
that trichlorobiphenyl is enriched in the sample relative to Aroclor 1016
and tetrachlorobiphenyl is reduced in the sample relative to Aroclor
1016. That is, the ratio of trichlorobiphenyl concentration to tetra-
chlorobiphenyl concentration in the air sample is significantly greater
than the Aroclor 1016 standard. This indicates the effect of selective
transport of the trichlorobiphenyl species which are generally more vola-
tile than the tetrachlorobiphenyl species. GC/MS and GC/EC analysis also
indicated the absence of monochlorobiphenyl species and the presence of
trace amounts of the dichlorobiphenyl species.
High-volume air samples were collected near an electric power substation
and transformer storage facility operated by a small electric coopera-
tive in northern Florida. The sampler was placed approximately 20 meters
-------
(a)
(b)
Min
Figure 13. (a) Standard Aroclor 1016; (b) Chromatograph of air sample
taken in the vicinity of a major industrial user.
75
-------
(a)
Air sample;
(Mass 256)
trichlorobiphenyl
(b) Standard Aroclor 1016; trichloro-
biphenyl (Mass 256)
(c) Air sample; tetrachlorobiphenyl
(Mass 290)
(d) Standard Aroclor 1016; tetrachloro-
biphenyl (Mass 290)
10
15
Min
Figure 19. GC/MS analysis of ambient air sample taken
a major industrial user of PCB. All chromatograms are
monitoring mode at the mass indicated.
in the vicinity
taken in peak
of
76
-------
from tne transformer storage area and 1UO meters from the substation.
Analysis was by gas chrornatography using an electron capture detector
(GC/EC) and confirmation was obtained by GC/MS. The analytical results
are summarized in Table 17. Biphenyl was found to be present at an
estimated concentration of Ib ng/m3. This was detected by GC/MS.
Klonquantifiaole traces of monochlorobiphenyl and dichlorobiphenyl were
detected by GC/tC and confirmed by GC/MS. Most PCb present appeared by
both GC/EC and GC/MS analysis to be trichlorobiphenyl. A concentration
of 3U ng/m3 was estimated for this species. Tetrachlorobiphenyl was
also present at b ng/m3.
TABLE 17
RESULTS OF HIGH-VOLUME AMBIENT AIR SAMPLE TAKEN IN THE VICINITY
UF AN ELECTRICAL SUBSTATION AND TRANSFORMER STORAGE FACILITY
Species
biphenyl
monochlorobiphenyl
dichlorobiphenyl
trichlorobiphenyl
tetrachlorobiphenyl
Analytical
GC/EC
ND
X, trace
X, trace
X, strong
X
Method
GC/MS
X
X, trace
X, trace
X, strong
X
Concentration
(ng/m3)
15 ng/m3 (est.)
1 ng/m3 (est.)
no est.
30 ng/m3
6 ng/m3
Sampleu IbO minutes, total of 185 m3 of air drawn. No PCB was
present in substitution greater than tetrachlorobiphenyl.
X = detected
ND = not detected
Tnese preliminary field tests provided some experimental data that
applies to practical application of the method under field conditions.
The preliminary experimental field data were of value in development of
the method suitaDle for routine field use. These preliminary field data
do not, however, constitute a field test of the method since significant
77
-------
changes were incorporated into the method as a result of this field
experience. The following section describes valid field tests of the
final method for PCB in air as described in Appendix A.
3.3 FIELD TESTS OF THE FINAL METHOD
The sampling and analytical method, as described in Appendix A, was field
tested on several occasions in Gainesville, Florida, and on two occasions
in New Bedford, Massachusetts. The procedure was followed as written
without deviation. In each sample, the glass fiber filter and each of
the three polyurethane foam (PUF) plugs were analyzed separately. Air-
borne PCB concentrations were measured over the range of 4 ng/m^ to
1.4 ug/m3 during these field tests under a variety of ambient temperature
and humidity conditions.
3.3.1 Tests in Gainesville, Florida
Table 18 is a summary of the results of several field tests conducted
over a 9-month period in Gainesville, Florida. Sampling periods range
from 30 minutes to 12 hours. Measured airborne PCB concentrations varied
from 11 ng/m3 to 44 ng/m3 as DCB. On the average, 94+3 percent
of the PCB captured from the atmosphere was retained on the filter and
first two PUF plugs. There are no apparent effects of ambient temper-
ature or humidity on collection efficiency over the ranges encountered
during these field tests. There is also no statistically significant
correlation between collection efficiency and sample flow rate or
duration.
Figures 20 through 23 illustrate the CC/EC chromatograms for the test
conducted on July 26, 1977. Figure 20(a) shows the chromatogram of an
unexposed PUF plug from the set of plugs used in the tests. No detect-
able PCB is present. Figure 20(b) is a chromatogram of the glass fiber
filter extract from the 2-hour ambient sample taken on that date.
Perchlorination yielded a concentration of 74 ng PCB as DCR on this
filter, which is below the detection limit by pattern quantitation.
Figure 21 is a chromatogram of an Aroclor 1242 standard. Figure 22 is
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the chromatogram of the extract of the first PuF plug in the sampler.
Those peals de.nctec hy a V coincide with peaks in Aroclor 1242.
Figures 23(a) and (b) are chromatograms of the second and third PUV
plugs, respectively, from this test. Note that all compounds eluting
after 10.6 minutes are quantitatively captured on the first PUF plug and
all those eluting after C.2 minutes on the first two PUF plugs. The
third PUF plug extract contains no peaks matching Aroclor peaks. The
unidentified compounds eluting at 15.8 and 10.6 minutes are captured with
high efficiency in the system. The unidentified compound eluting at
3.6 minutes is also effectively captured. The unidentified compounds
eluting at 1.97, 2.5, and 3.0 m'nutes, respectively, appear to saturate
all three PUF plugs and, hence, are probably ineffectively captured. In
this test, the first PUF plug contained 2720 ng PCE as DCB upon
perchlorination, the second 763 ng, and the third 350 ng. The measured
airborne concentration was 35 ng/rn^ as DCB. Most of the PCB peaks
detected were in the elution range of tri-, tetra-, and pentachlorobi-
phenyl species. The 2-hour ambient air sample taken in the same location
on October 31, 1977, yielded the chromatogram shov;n in Figure 24(a).
Peaks in this chromatogram v,hich coincide with Aroclor peaks are
designated by a "•", but the pattern match is poor. After perchlori-
nation of the extract, as shown in Figure 24(b), quantitation is direct
and unequivocal. This sample contained 660 ng as OCR on the first PUF
plug, 110 ng on the second, and 84 ng on the third. The measured
airborne concentration was 11 ng/m3 as DCB. This is approximately
one-third the ambient level measured on July 26, 1977.
PCB collection efficiency remains high for longer than 2-hour sampling
periods. Therefore, it may be desired to obtain a longer time-integrated
sample. Figures 25 and 26(a), (b), (c) show the chromatograms of the
filter and three PUF plug extracts from a 6-hour air sample. PCB species
are found on the first and second PUF plugs (indicated by a "•"), but are
absent from the filter and the third PUF plug. MCB was not detected.
This sample was quantitated by pattern matching, yielding an airborne
concentration of 8.8 ng/nr as Aroclor 1242 or 17 ng/m3 as DCB. The
pattern most closely resembles Aroclor 1242, but not all peaks are
present. Hence, the concentration reported incorporates the uncertainty
inherent in the pattern quantitatiot: r.ethod.
-------
85
-------
Figure 25
GC/EC Chromatogram (Attn:
(PUF #1) Taken 11/20/77 in
) of 6-Hour
Gainesville, Flori
Ambient Air Sample
da.
86
-------
Figure 26. GC/EC Cnromatograms of (a) Second PUF Plug, (b) Third PUF Plug
and c) Glass Fiber Filter (Attn: 16xlQ-9) Of 6-Hour Ambient Air
Sample Taken 11/20/77 in Gainesville, Florida.
87
-------
It may be noted in Figure 25 that DDE is apparently present in this air
sample and is quantitatively captured (cf. Figure 26) on the first PDF
plug, although this peak has not been confirmed by mass spectrometry.
The sampling system would, therefore, serve as well for the measurement
of airborne DDE concentration.
3.3.2 Tests in New Bedford, Massachusetts
Two capacitor manufacturers are located in New Bedford, Massachussetts.
The New Bedford municipal landfill served as the site of the disposal of
reject capacitors and other PCB-containing wastes from these industries
for many years prior to 1975. Over 22,000 kg of PCB have been disposed
of in this landfill over the years (EPA, 1976). PCB wastes have not been
placed here since 1975. Air samples were taken at this landfill site on
June 28-30,1977, and again during January, 1978.
The results of the first field test conducted at the New Bedford landfill
are tabulated in Table 19. One-hour and 6-hour samples were taken at the
landfill site on June 28 and June 30, 1977, respectively. In this case,
quantitation of the PCB was easily accomplished by pattern matching tech-
niques, since relatively large amounts of PCB were collected and the
pattern closely resembled that of Aroclor 1242.
Figure 27 is a chromatogram of the glass fiber filter extract from the
60-minute air sample at this site. Marginally quantifiable traces of PCB
are present on the filter. Figure 28 is a chromatogram an Aroclor 1242
standard at the same GC operating conditions. Figure 29 shows the
chromatogram of the first PUF plug extract after an 8:1 dilution. The
pattern closely resembles that of Aroclor 1242. The full Aroclor pattern
is present and is easily quantifiable in the PUF plug extract. The
second and third PUF extracts, shown in Figures 30 and 31, respectively,
appear to be devoid of quantifiable amounts of Aroclor 1242. Collection
of PCB on the first PUF plug is, therefore, quantitative.
On Figure 29, the "x" denotes the retention times of o,p'-DDT and
p,p'-DDT. It appears, but has not been confirmed by mass spectrometry,
88
-------
TABLE ly
RESULTS OF FIELD TESTS CONDUCTED IN NEW BEDFORD, MASSACHUSETTS,
IN JUNE, 1977
Sample Date* 6/28/77 t
Sample Time 1059-1159
Sample Duration (iriin) 60
Wind Direction WSW
Wind Speed (mph)
Sample Flow Rate (m^/min)
Vol. Ai r Sampled (nr)
PCB Collected (ug Aroclor 1242)
Filter
PUF ,fl
PUF #2
PUF f3
Total
Percent of Total PC6 Collected
Filter
PUF #1
PUF ifZ
PUF #3
Filter + PUF #1 + PUF #2
Airborne PCB Cone, (ug/m^
Aroclor 1242)
Biphenyl Collected (ng/m^)
10
1.02
61
0.2
53. y
<0.2
<0.2
54.1
0.4
99.6
<0.4
-------
Figure 27. GC/EC Chromatogram of the Filter Extract (Attn: 16x10 )
from the 60-Minute Ambient Air Sample Taken at New Bedford
Landfill.
90
-------
rdtzrt:
J-4
Figure 28. GC/EC Chromatogram (Attn: 16xlO"9) of an Aroclor
1242 Standard.
91
-------
Figure 29. GC/EC Chromatogram of the First PUF Plug Extract (Attn: 15xlO~9
Diluted to 1/8) of the 60-Minute Ambient Air Sample Taken at
New Bedford Landfill.
92
-------
:!
" —41-
______ _(,__
Figure 30. GC/EC Chromatogram of the Second PUF Plug Extract (Attn: 16x10"
of the 60-Minute Ambient Air Sample Taken at New Bedford Landfi
93
-------
r-EE
31. GC/EC Chromatogram of the Third PUF Plug Extract (Attn: 16 x 10"9)
of the 60-Minute Ambient Air Sample Taken at New Bedford Landfill.
94
-------
that DDT is also present in these air samples and is quantitatively
captured on the first PUF plug.
The extracts from the 6U-minute air samples were then perchlorinated for
confirmation of the PCB. Tne results were as follows:
filter 173 ng DCB
PUF #1 72,800 ng DCB
PUF #2 129 ng DCB
PUF #3 43 ng DCB
PCb is confirmed and the high collection efficiency is validated by
perch!orination. The total amount of DCB in the filter and first PUF
plug extracts (73 ug) can be converted to equivalent Aroclor 1242 using
the conversion factor in Table 1 of Appendix A. Applying this conver-
sion, an equivalent of 0.62 ug/m^ of Aroclor 1242 is calculated. This
compares to 0.89 ug/m^ determined by pattern matching. The 30 percent
discrepancy in the amount measured by the two methods in this case may be
attributed to two factors: (a) the large amount of dilution required to
quantitate the first plug extract in effect results in a multiplication
of analytical variability; and (b) it is assumed, both for pattern quan-
titation and for conversion of perchlorination results to equivalent
Aroclor 1242, that Aroclor 1242 is present alone and in unmodified form.
These necessary assumptions limit the degree of agreement that may be
expected between pattern quantitation and perchlorination results. It
would not normally be necessary to perchlorinate such high level samples,
however, for purposes of quantitation.
The samples taken in the vicinity of the New Bedford landfill were also
checked tor the presence of biphenyl (BIPH) using the analytical method
described in Appendix A (Section 12.0). 3IPH was absent from all 1-hour
and 6-hour filter and PUF plug extracts. Hence, BIPH was collected in
concentrations below the detection limit of 0.5 ng/nr, if at all.
Figure 32 is a GC/FID (flame ionization detector) chroinatogram of a BIPH
standard. Figure 33 is a chromatog ram of the first PUF plug extract from
the 60-minute sample. Mote the absence of a BIPH peak in Figure 33.
-------
_. ;__ L~~
1
Figure 32.
GC/FID Chromatogram of Biphenyl
at 2.8 ng.
96
-------
1
^£
Figure 33. GC/FID Chromatogram of the First PUF Plug
Extract from the 60-Minute Ambient Air Sample
Taken at New Bedford Landfill
97
-------
Since relatively high airborne PCB levels were detected over the Mew
Bedford landfill, a second sampling trip was scheduled in January, 1973,
in an attempt to determine if the landfill itself was the source of the
airborne PCB, or if one or more of the other potential sources in the
area were emitting significant amounts of PCB. The samping was conducted
by EPA Region I personnel using the procedure in Appendix A. Sair.pl ing
was conducted upwind and downwind of the two PCC user facilities in the
area, the municipal sewage sludge incinerator, ano the landfill. Sam-
pling duration was 3 hours in each case. The ground was frozen at the
time of sampling and a light snow was falling. The analytical results
are summarized in Table 20. One may conclude from these data that the
landfill is a possible low-level PCB emitter during the winter months as
compared to the sunnier months. Some PCC is possibly emitted from the
municipal sewage sludge incinerator, but PCB user A is clearly a major
emitter in the area. PCB user B apparently had no significant emissions
at the time of sampling.
Figure 34 shows the GC elution pattern for the sample taken over the
landfill. The pattern closely resembles Aroclor 1016/1242. Each peak
designated by a "•" matches a peak in Aroclor 1242. At lower levels such
as this, it is not possible to unequivocally distinguish between these
two similar Aroclors.
Figure 35(a) shows the air sample taken upwind of PCB user A, v/hile
Figure 35(b) shows the sample taken downwind. The downwind sample
clearly contains a substantial amount of Aroclor 1016.
The field tests described above demonstrate the practical use of the
method described in Appendix A for the sampling and analysis of ambient
airborne PCB. The tests covered a wide range of ambient concentrations.
In the Gainesville location, the PCB was not generally recognizable by
pattern matching and perchlorination was required for quantitation,
while at the New Bedford location, the PCB pattern was clear. In all
field tests conducted, an average of 96 + 4 percent of the PCB collected
-------
TABLE 20
RESULTS OF FIELD TESTS CONDUCTED IN NEW BEDFORD, MASSACHUSETTS,
IN JANUARY, 1978
Date
Site
1/17 landfill
1/24
1/27
1/19
PCB user A
PCB user B
Location Concentration (ng/m3) Aroclor
upwind
on site
downwind
sewage sludge upwind
incinerator downwind
upwind
downwind
upwind
downwind
8.5
21
13
4.3
13
5.6
490
19
5.1
1242/1016
1242/1016
1242/1016
1242/1016
1242/1016
1242/1016
1016 only
1242/1016
1242/1016
-------
Figure 34. GC/EC Chromatogram of Air Sample Taken over New Bedford,
MA,Landfill. 0.5 ul Injection, Attn: 64 x 1Q-9
100
-------
O I
••- o
o
O) X
- C sj--
•p- UD
10
20
30
re
T3
Q.
cu
CO +->
O) -i-
E o
re re
co H-
i. i.
• i- O)
ro to
O CO
o
CO D_
o o
-t->
ro TD
E c
o -r-
S- 3
JC C
O 2
O
O 13
CIS
en
ro
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:3
en
101
-------
was captured on the first and second PUF plugs. Less than 4 percent was
detected on the third PUF plug. Several unidentified, non-PCB compounds
were also trapped with a high degree of efficiency while others passed
through the collection medium. Interferences were not, however,
encountered which inhibited quantisation of the PCB by perchlorination at
the lower levels or by pattern at the higher levels. Sample handling
techniques as described in Appendix A have been demonstrated to be ade-
quate to avoid unwanted PCB contamination in the field. Furthermore, it
has been demonstrated that the sampling procedure can be followed by
persons other than the authors with satisfactory results.
102
-------
.0 CONCLUSIONS AND RECOMMENDATIONS
A method has been developed for the sampling and analysis of polychlo-
rinated biphenyls (PCBs) in air. An easily constructed, high-volume
sampling system is employed with porous polyurethane foam as the collec-
tion medium. The sample is collected at the rate of 0.6 to 1.0 m^/min.
The method is described in detail in Appendix A.
Laboratory procedures have been developed, and are described in this
document, which permit the quantitative analysis of even the most vola-
tile PCB species in an air sample, A perchlorination technique for the
quantitative analysis of PCB has been adapted for use with air samples.
The technique is shown to convert even the most volatile PCB species to
decachlorobiphenyl for simple and direct quantitative analysis. Data is
presented to show conversion efficiencies of a variety of PCBs to deca-
chlorobiphenyl of 101 + 6 percent over the range of 0.103 to 10.0 ug. A
ruggedness test was conducted which indicates the proposed perchlorina-
tion technique can yield reliable interlaboratory results. The perchlo-
rination technique is a recommended optional method of quantitation of
PCB when the commonly used pattern matching techniques are found to be
unsuitable as a result of either low quantities of collection or poor
Aroclor pattern recognition. It is the opinion of the authors that the
use of the perchlorination technique is generally necessary for the anal-
ysis of low (i.e., less than 25 ng/m^) airborne levels of PCB. The
analytical metnod is effective for the analysis of airborne PCB levels
within at least the range of 1 ng/m^ to 50 ug/rn .
The total sampling and analytical method was subjected to rigorous spike
recovery tests under a variety of ambient conditions. The mean collec-
tion efficiency for Aroclor 1016/1242 was 101 + 10 percent for sampling
periods of 20 minutes to 12 hours and air volumes of 16 to 720 cubic
meters. It is demonstrated tnat monochlorobiphenyl is the most difficult
species to capture. A 2-hour sampling duration is the maximum that may
be employed to quantitatively capture monochlorobiphenyl.
103
-------
Dichlorobiphenyl and more highly substituted species may be quantita-
tively captured using up to 6-hour sampling periods. Data is presented
to show that the analysis of the final one-third section of the poly-
urethane foam collection medium is a direct and reliable method of
estimating system collection efficiency under specified system operating
conditions.
Field tests of the method were conducted under a variety of ambient con-
ditions including both low and high PC8 levels. Typical ambient airborne
PCB data is presented and discussed. In most locations the PCB that is
collected does not closely resemble a single or a simple mixture of
Aroclor;-hence, perchlorination is required for quantisation. In loca-
tions near known or suspected sources of PCB, where high ambient levels
are detected, Aroclor patterns are generally discernable and pattern
matching techniques of quantitation may be employed.
The proposed method is recommended for the analysis of ambient airborne
PCB. Both laboratory and field tests have demonstrated that the analyst
may apply this method with a reasonably high degree of confidence in the
resulting data. The accumulation of additional ambient data and addi-
tional experience in practical application will provide for a continuing
evaluation of the method under an ever expanding range of conditions.
104
-------
6.0 REFERENCES
Armour, J.S. 1973. Quantitative Perchlorination of Polychlorinated
Biphenyls as a Method for Confirmatory Residue Measurement and
Identification. Journal of the Association of Official Analytical
Chemists, 56(4) :987-993.
Bidleman, T.F. and Olney, C.E. 1974a. Chlorinated Hydrocarbons in the
Sargasso Sea Atmosphere and Surface Water. Science, 183:516-518.
Bidleman, T.F. and Olney, C.E. 1974b. High-Volume Collection of
Atmospheric Polychlorinated Biphenyls. Bulletin of Environmental
Contamination and Toxicology, 2:5.
Giam, C.S., Chan, H.S., and Neff, G.S. 1975. Rapid and Inexpensive
Method for Determination of Polychlorinated Biphenyls and
Phthalates in Air. Analytical Chemistry, 47(13) :2319-2320.
Harvey, G.R. and Steinhauer, W.G. 1974. Atmospheric Transport of
Polychlorobiphenyls to the North Atlantic. Atmospheric
Environment, 8:777-782.
Hutzinger, 0., Safe, S., and Zitko, V. 1974. The Chemistry of PCB's.
CRC Press, Cleveland, Ohio.
Lewis, R.G. and Zimmerman, N.J. 1976, Danger of Re-Circulation in
Hi-Vols. U.S. Environmental Protection Agency Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio. Analytical
Quality Control Newsletter #28.
Lewis, R.G., Brown, A.R., and Jackson, M.D. 1977. Evaluation of Poly-
urethane Foam for Sampling of Pesticides, Polychlorinated Biphenyls
and Polychlorinated Nephthalenes in Ambient Air. Analytical
Chemistry, 49(12) :1668-1672.
Margeson, J.H. 1977. Methodology for Measurement of Polychlorinated
Biphenyls in Ambient Air and Stationary Sources—A Review. U.S.
Environmental Protection Agency, Environmental Monitoring and
Support Laboratory, Research Triangle Park, North Carolina.
Mieure, J.P., Hicks, 0., Kaley, R.G., and Saeger, V.W. 1975.
Characterization of Polychlorinated Biphenyls. Paper presented at
National Conference on Polychlorinated Biphenyls, November 19-21,
1975, Chicago, Illinois.
Murphy, D.G. 1972. Sulfuric Acid for the Cleanup of Animal Tissue for
Analysis of Acid-Stable Chlorinated Hydrocarbon Residue. Journal
of the Association of Official Analytical Chemists, 55(6):
1360-1362.
105
-------
Rhoades, J.W., Johnson, D.E., and Lewis, R.G. 1977. Evaluation of
Collection Media for Measurement of Pesticides and Polychlorinated
Biphenyls in Ambient Air. 173rd National Meeting, American
Chemical Society. New Orleans, Louisiana, March 25, 1977, Paper
No. 77.
Rice, C.P., Olney, C.E., and Bidleman, T.F. 1976. Use of Polyurethane
Foam to Collect Trace Amounts of Chlorinated Hydrocarbons and Other
Organics From Air. Paper Presented at World Health Organization
Meeting, Gothenburg, Sweden, October, 1976.
Snyder, D. and Reinert, R. 1971. Rapid Separation of Polychlorinated
Biphenyls from DDT and Its Analogs on Silica Gel. Bulletin of
Environmental Contamination and Toxicology, 6(5):385-390.
Trotter, W.J. and Young, S.J.V., 1975. Limitation on the Use of
Antimony Pentachloride for Perchlorination of Polychlorinated
Biphenyls. Journal of the Association of Official Analytical
Chemists, 58:3.
U.S. Code of Federal Regulations. 1975. Procedures for the Measurement
of Total Suspended Airborne Particulate. Title 40, Part 50,
pp. 12-16.
U.S. Environmental Protection Agency. Region I. 1976. New England PCB
Waste Management Study. Boston, Massachusetts.
Youden, W.J. and Steiner, E.H. 1975. Statistical Manual of the Associ-
ation of Official Analytical Chemists: Statistical Techniques for
Collaborative Tests; Planning and Analysis of Results of Col-
laborative Tests. Association of Official Analytical Chemists,
Washington, D.C. 88 pp.
Zitko, V., Hutzinger, 0. and Safe, S. 1971. Bulletin of Environmental
Contamination and Toxicology, 6:160.
106
-------
APPENDIX A
METHOD FOR POLYCHLORINATED BIPHENYL (PCB) IN AIR
-------
METHOD FOR-
POLYCHLORINATED BIPHENYL (PCB) IN AIR
Prepared by
ENVIRONMENTAL SCIENCE AND ENGINEERING, INC.
P.O. BOX 13454, UNIVERSITY STATION
GAINESVILLE, FLORIDA 326U4
for
QUALITY ASSURANCE BRANCH
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NC 27711
and
OFFICE OF TOXIC SUBSTANCES
ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
Contract 68-01-2978
October, 1977
-------
The mention of trade names of commercial products and suppliers in
this procedure is for purposes of illustration only, and does not
constitute endorsement or recommendation for use by the U.S.
Environmental Protection Agency.
-------
METHOD FOR POLYCHLORINATED BIPHENYL (PCB) IN AIR
1.0 Principle of the Method
Airborne polychlorinated biphenyl (PCB) is collected on porous poly-
urethane foam by use of a modified high-volume (hi-vol) air sampling
device.d) The PCB is extracted from the polyurethane with an organic
solvent. Chlorinated pesticides and other interferences are removed by
column chromatography prior to gas chromatographic (GC) analysis using
an electron capture (EC) detector. When a typical PCB pattern is not
recognizable, analysis is performed by perchlorination of all PCB to
decachlorobiphenyl (DCB) and subsequent quantisation as DCB. When
biphenyl is present, or to demonstrate the absence of biphenyl, GC/FID
(flame ionization detector) analysis is required to correct the
analytical results for this non-chlorinated species. Figure 1
summarizes the steps this method entails.
2.0 Range of the Method
A detection limit of 1 ng/in^ of PCB reported as DCB is achievable
using a four-hour sampling period. The upper limit of the method is
in excess of 50 ug/m^ for short sampling periods (e.g., 20 minutes).
3.0 Interferences
Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts causing misinterpretation of gas
chromatograms. All of these materials must be demonstrated to be free
from interference under the conditions of this analysis. Specific
selection of reagents and purification of solvents by distillation in
all-glass systems is required.
3.2 Toxaphene, phthalate esters, DDE, and polychlorinated naphthalenes can
cause interferences with the determination of PCB if they are present.
-------
CLEANUP OF POLYURETHANE
FOAM PLUGS, GLASS FIBER FILTERS
AND SAMPLING APPARATUS
Field Sampling
Soxhlet Extraction of
Polyurethane Foam Plugs
and Glass Fiber Filters
Silica Gel
Separat ion
GC/EC Analysis
of PCB Mixture
GC/FID Analysis
of Biphenyl
PCB Quantitation
by Pattern Matching
Pesticides
Fraction
Perchlorination
GC/EC Analysis of
Decachlorobiphenyl
Figure 1. Analytical Scheme for PCB in Ambient Air
-------
4.U Precision and Accuracy
4.1 Analytical. A test of the perchlorination methodology using both
Aroclor lU16a and a PCB mixture containing monochlorobiphenyl,
dichlorobiphenyl, and trichlorobiphenyl was conducted over the range of
0.103 ug/ml to 10.0 ug/ml. Eighteen analyses were performed. The mean
percent conversion of PCB to DCB was 100 + 4 percent over this range. A
ruggedness test(2) Of the perchlorination method indicated inter!ab-
oratory results obtained by competent trace analytical chemists should
be readily comparable using this method.
4.2 Sampling. The recovery during tests of the method using Aroclor 1016
and Aroclor 1242 spiked onto the glass fiber filter that preceeds the
polyurethane foam (PUF) collection media in the sampling device (see
Figure 2), averaged 101 + 12 percent over the range of 1.25 ug to 112
ug employing sampling periods between 20 minutes and 12 hours. Three
PUF plugs were used at an average air flow rate of 0.8 m^/min.
5.0 Apparatus, Materials, Instrumentation, and Reagents
5.1 Sampling Apparatus and Materials.
5.1.1 Modified hi-vol air sampler described in Section 6.3 (Figures 2 and 3)^.
5.1.2 Variable voltage controller to adjust flow rate of hi-vol sampler.
5.1.3 Rotometer for measuring hi-vol flow rate0.
a. Aroclor 1016® is a commercial product containing dichlorobiphenyls
trichlorobiphenyls, and tetrachiorobiphenyls.
b. Basic unit may be obtained from General Metals Works, Cleves, OH.
This unit is recommended for total suspended particulate sampling
(Code of Federal Regulations, Title 40, Part 50, pp. 12-16,
July 1, 1975).
c. May be obtained from: Dwyer Instruments, Inc., P.O. Box 618,
Marietta, GA 30061
-------
Faceplate
Stainless Steel Throat Extension
Polyurethane Foam
Plus Location
Throat Extension
Wire
Retainer
Motor Unit
'\daptcr
Exhaust Duct
(3 in minimum length)
Figure 2. Assembled sampler and shelter with exploded view of the filter holder,
-------
Throat Modification
Figure 3. Exploded view of hi-vol sampling apparatus
designed for use with a rotometer showing
modified throat to accoraodate polyurethane foam
plugs.
-------
5.1.4 Glass fiber filters (Gelman Type A, 25 cm x 20 cm).
5.1.5 Polyurethane foam. Three inch thick sheet. Density of 0.025 g/ccd.
5.1.6 Glass jars (e.g., one pint fruit jars) suitable for storage and
transport of the polyurethane foam plugs.
5.1.7 Collapsible exhaust ducting.
5.2 Analytical Apparatus and Materials.
5.2.1 Soxlet extraction apparatus (5.5 cm x 20 cm) equipped with a 300 ml
florence flask and a reflux condenser (ground glass joint)— Kontes6
item #K-585000, or equivalent.
5.2.2 Hot plates or heating mantle.
5.2.3 Perchlorination reaction vial--16 x 100 mm glass screw top culture
tube with teflon-lined screw cap is modified by drawing the bottom
into a cone shape as depicted in Figure 4. This may be easily
accomplished by heating the bottom of the culture tube and pulling it
out to a uniformly tapered tip.
5.2.4 Disposable Pasteur pipets--5 3/4 inch long.
5.2.5 Glass boiling beads--2 mm diameter.
5.2.6 Aluminum block tube heater—capable of maintaining a temperature of
160 + 3°C. Suitable to receive reaction vials (Section 5.2.3).
d. May be obtained from: Flexible Foam Products, Grand Sheet
Metal Products Co., 1101 W. Wisdom St.,
Chattanooga, TN 37406, Product # 1636
e. Kontes Glass Co.
Vinland, NJ
-------
Teflon-lined cap
fl6 mm
Figure 4. Perchlorination reaction vial,
-------
5.2.7 Gas flow meter--range of 50-500 ml/min.
5.2.b N2 organic removal filter—organic contamination of compressed N£ has
been shown to be a problem. A filter constructed as shown in Figure 5
has been found to be effective in removing these organic contaminants.
5.2.9 Syringe--! to 10 ul.
5.2.10 Hypo-vials®—10 ml capacity with Teflon crimp-on septa. May be
obtained from Piercef (item # 12903).
5.2.11 Kuderna-Danish evaporating apparatus with modified micro-Snyder
condenser-Kontes item #K-569250, or equivalent.
5.2.12 Chromatographic column (13 mm OD x 250 mm) with 200 ml reservoir and
teflon stopcock (Kontes item # K-420280) for preparation of silica gel
column (10.21).
5.2.13 Kuderna-Danish evaporating apparatus with three-ball macro-Snyder
column--Kontes item # K-570000, or equivalent.
5.2.14 Hengar® granules, micro for boiling chips.
5.2.15 Miscellaneous laboratory glassware.
5.3 Analytical Instrumentation.
5.3.1 Gas chromatograph equipped with an electron capture detector.
5.3.2 Potentiometric strip chart recorder compatible with the gas Chromato-
graphic detector system.
f. Pierce
Box 117
Rockford, IL 61105
-------
. Hood
Nitrogen
Polyurethane
Foam
Activated
Charcoal
Polyurethane
Foam
Drying Agent
(Dri-Rite)
Glass Wool
Variable
Voltage
Control
Heating
Tape
Glass Tubing
120cm x 10 cm
Polyurethane
Foam Plug
* •
rigure 5. Apparatus for drying polyurethane foam plugs.
-------
5.3.3 The GC column used for both identification of the PCB isomers present
and pattern quantitation is 1.5%/1.95% OV-17/QF-1 on Chromosorb W-HP,
8U/10U mesh in glass 180 cm x 2 mm ID column.
5.3.4 A suitable confirmatory column is 4%/6% SE-30/OV-210 on Chromosorb
W-HP, 8U/100 mesh in 180 cm x 2 mm ID glass column.
5.3.5 The GC column used for quantitation of DCB after perchlorination is 3
percent SP-2401 on 80/100 Supelcoport® in glass column 90 cm x 2 mm
ID.
5.3.6 For biphenyl analysis a 10 percent SP-2100 on 80/100 Supelcoport®,
180 cm x 2 mm ID glass or stainless steel column may be used.
5.4 Reagents.
5.4.1 Antimony pentachloride, SbCl5--reagent grade SbCl5 from certain sources
has been found to contain DCB and bromonanochlorobiphenyl (BNCB). The
DCB results in a positive blank value. The BNCB interferes with per-
chlorination of the lower-substituted PCB isomers. The SbClg selected
for use must first be analyzed for these contaminants. Reagent grade
SbCl5 manufactured by Cerac Pure9 (stock no. A1147, lot 15-26A) has
been found to be suitable.
5.4.2 Hexane—nanograde or pesticide-grade solvent, distilled in glass.
5.4.3 Hydrochloric acid—reagent grade.
5.4.4 Sodium sulfate—reagent grade, anhydrous granular". Heated to
300°C prior to use in order to remove any interfering organics.
g. Cerac Pure
P.O. Box 1128
Milwaukee, WI 53201
h. Mallinckrodt, Inc.
St. Louis, MO 63147
10
-------
5.4.5 Compressed nitrogen--water pumped and pre-purified to 99.99% pure.
5.4.6 Decachlorobiphenyl (DCB)—pure DCB isomer for quantitation purposes may
be obtained from Analabs, Inc.1 (Stock #RCS-051) or from RFR
CorpJ (Stock ffRCP-28).
b.4.7 Chrornatographic grade silicic acid (10U mesh)—Woelm^ silica gel
.activity grade I.
5.4.8 Aroclor standards and biphenyl—may be obtained from Analabs, Inc. or
from EPA Pesticide Repository (MD-69), Research Triangle Park, North
Carolina 27711.
6.0 Preparation of Materials and Equipment
6.1 Polyurethane foam absorbent media.
6.1.1 Circular plugs of diameter 8.9 cm are cut from 7.6 cm thick sheet poly-
urethane foam. These plugs will fit snuggly into the throat of the
modified hi-vol sampler (Figure 2). A cutting device as depicted in
Figure 6 has been found suitable for cutting highly uniform polyurethane
foam plugs from the stock material. This device was manufactured by
removing the internals and bottom of an automobile oil filter of the
correct dimensions and buffing a cutting edge. A bolt is attached as
shown in Figure 6 to allow attachment to a drill chuck. Using a reason-
ably slow drill speed, this device is used to cut through the sheet
polyurethane foam. Lubricate the cutting edge constantly during cutting
with a fine stream of water.
i. Analabs, Inc. j. RFR Corporation
80 Republic Drive 1 Main Street
New Haven, CT 06473 Hope, RI 02831
K. May be obtained from: ICM Pharmaceuticals, Inc.
Life Science Group
26201 Miles Road
Cleveland, OH 44128
11
-------
i.
Figure 6. Polyurethane Foam Cutting Device
12
-------
fa.1.2 To remove contaminating organics, extract each polyurethane foam plug
for twelve hours with hexane in a soxhlet extraction apparatus
(Section 5.2.1).
6.1.3 Dry the extracted polyurethane foam plugs with organic-free N^- A
glass cylinder (10 crn diameter) wrapped with heating tape arid fitted
with a N^ inlet and exhaust as depicted in Figure 5 has worked well
for the drying of many plugs at one time.
6.1.4 Avoid exposure of cleaned foam plug to laboratory atmosphere to
prevent contamination with PCB.
6.1.5 Store each polyurethane foam plug in a wide-mouth, sol vent-rinsed
glass container with pre-cleaned aluminum foil between jar and cap.
The aluminum foil is heated to 200°C for at least one hour before use
to remove organics.
6.2 Glass Fiber Filters.
6.2.1 Gelman Type A (20 cm x 25 cm) glass fiber filters are heated to 200°C
for several hours to remove contaminating organics. They are then
wrapped in pre-heated aluminum foil until use. After use they are
returned to the aluminum foil wrappers for transport to the
laboratory.
6.3 Hi-vol Sampling Device.
6.3.1 Standard hi-vol air samplers are modified by the addition of a 30 cm
stainless steel extension to the throat section of the assembly as
shown in Figures 2 and 4. Air flow rate of this device can be varied
from approximately 0.5 m^/min to 1.5 m^/rnin by use of a
potentiometric speed controller.
13
-------
6.3.2 A wire or screen retainer as shown in Figure 2, is placed between the
polyurethane foam plugs in the throat of the apparatus and the motor
unit to prevent movement of the plugs during sampling.
6.3.3 To avoid the possibility of contamination of interfering organic
substances, the neoprene seal around the perimeter of the filter
faceplate is removed. A seal is maintained by wrapping the faceplate
with Parafilm®.
6.3.4 An exhaust duct 5 meters or more in length, of collapsible ducting
material is placed on the hi-vol exhaust and is positioned downwind
during sampling to avoid recirculation of air through the sampler.
7.0 Sample Collection
7.1 A 20 cm x 25 cm glass fiber filter (Gelman Type A) is mounted in the
high-volume sampling apparatus.
7.2 Three foam plugs (Section 6.1.1) are inserted into the 8.2 cm diameter
throat of the high-volume sampling apparatus, taking care to avoid
empty spaces between the plugs and cylinder wall.
7.3 The hi-vol air flow rate is adjusted to 0.8 + 0.2 m^/min using the
rotometer (see Figure 3). Flow is measured at the beginning and end
of each sampling period and the volume of air sampled is calculated as
follows:
Qn- + Qf
V - — x t
2
where, V - air volume sampled (uncorrected), m^
Q-j = initial air flow rate, m^/min.
Qf = final air flow rate, m3/min.
t = sampling time, min.
Rotometer calibration procedures are described in (3).
-------
7.4 A sampling period is selected which is commensurate with the expected
airborne PCB level. Under normal circumstances, a two-hour period is
appropriate for airborne levels of 2 ng/iu3 or greater. If levels
are expected to be lower (i.e., less than 2 ng/n:3), a six-hour
sampling period is recommended. If the sampling period is too long for
higher airborne levels, PCB may pass through the collection media with
consequently lower collection efficiency. y If the sampling period is not
long enough for the ambient levels present, detectable quantities may
not be collected. Tests have demonstrated that all PCBs, including
monochlorobiphenyl , are effectively retained over a two-hour sampling
period and that dichlorobiphenyl is effectively retained over a six-hour
sampling period. Aroclor 1242 is retained in excess of 12 hours at
normal sampling rates.
7.5 The sampling apparatus is rinsed between sample runs with hexane to
remove any PCB contamination.
8 . 0 Sample Extract Preparation
8.1 After sampling is completed, the filters are removed, and refluxed for
three hours with 300 ml hexane in a soxhlet extractor. The first and
second polyurethane foam plugs, as located in the sampler with respect
to air flow, are extracted for three hours (18 cycles) in a soxhlet
extractor (Section 5.2.1) with 200 nil hexane. The extracts are combined
and concentrated to 5 ml in a Kuderna-Canish apparatus (Section 5.2.13).
8.2 Chrornatographic Separation of Chlorinated Pesticides.
8.2.1 A silica gel column is prepared by wet packing in hexane about 3 g of
the dry activated absorbent previously cleaned in benzene and dried to
200°C for four hours. Draw off excess hexane used to make this slurry
and wash the column with 50 ml of hexane. A 250 mm x 13 mm column is
used (Section 5.2.12).
8.2.2 Place 2 g of anhydrous Na2S04 on top of the cilica gel column to
remove any water from the sample extract.
15
-------
8.2.3 The hexane extract of 5 ml is quantitatively transferred to the
column, rinsing the Kuderna-Danish receiver three times with a small
amount of hexane.
8.2.4 Allow the sample to drain through the column until the liquid level is
about 0.5 cm above the top of the
8.2.5 Elute the PCB fraction with 50 ml of hexane, collecting all hexane in
a clean, graduated Kuderna-Danish receiver (Section 5.2.13). Most
chlorinated hydrocarbon pesticides (except DDE) are retained on the
column and may be eluted with benzene if analysis is desired.
8.3 The eluate is concentrated to 5 ml in the Kuderna-Danish apparatus
(Section 5.2.13). A modified micro-Snyder column is then attached to
the receiver (Section 5.2.11) and the solution is evaporated to less
than 1.0 ml using the graduations on the evaporator receiver. Care
must be taken not to evaporate to dryness or the more volatile PCB
species will be lost.
8.4 Bring the volume up to the 1.0 ml graduation mark on the Kuderna-
Danish evaporator receiver with fresh hexane. The extract is now
ready for either GC/EC analysis and quantitation by Aroclor pattern
matching or derivitization to DCB followed by GC/EC quantitation.
8.5 If the sample is to be stored at this point, the extract should be
quantitatively transferred to a Hypo- vial without a significant
evaporative loss of solvent. Close the Hypo-vial with teflon septum
and aluminum cap (Section 5.2.10).
16
-------
9.0 Analysisand Quantitation of PCB
Two techniques are available for the quantisation of PCB; the Aroclor
pattern matching technique and perchlorination. The analyst must
decide which of these techniques to use based on the appearance of the
chromatograms. Airborne PCB may or may not exhibit a GC elution
pattern that matches an Aroclor elution pattern. Given a source of
Aroclor, the relative volatilities of the various species will vary
widely resulting, generally, in a bias of the GC pattern toward the
more volatile species as compared to an Aroclor standard prepared in
solvent.(4) This will be particularly true of ambient airborne
samples taken at a considerable distance from the source or sources,
since differential rates of transport among the various species can
exert a significant effect. Most ambient air samples exhibit a large
amount of apparent PCB which is early eluting. It is extremely diffi-
cult to match these early eluting peaks to a standard Aroclor elution
pattern. These early eluting peaks may represent a highly significant
amount of PCB. Hence, it is recommended in most cases that the per-
chlorination method be used for PCB quantitation and confirmation. If
it is of interest to know the PCB species present, the sample should
be analyzed by comparison with Aroclor or specific isomer PCB stan-
dards before perchlorination. Biphenyl, if present, may be analyzed
by GC/FID. In those cases where the chromatogram closely matches an
Aroclor pattern, the pattern matching technique is recommended.
Experience has shown this is a suitable method for the higher
ambient airborne levels observed near known sources of PCB.
17
-------
10.0 Identification and Quantitation of PCB Mixture by Pattern Matching
10.1 Analyze the hexane extract on a 1.5/1.95% OV-17/QF-1 column. The
following conditions have been found to be suitable:
Glass column, 180 cm length, 3 mm ID
1.5%/1.95% OV-17/QF-1 liquid phase
Chrom W-HP, 80/100 mesh support
N2, 35 psig inlet pressure
Detector temperature--220°C
Column temperature--200°C
Injector temperature--245°C
Detector—electron capture
10.2 The analyst may qualitatively assess the species distribution of the
PCB present by comparison of the GC elution pattern with that of an
Aroclor or a series of various Aroclor standards, or, if desired, with
individual PCB species.
10.3 Once the elution pattern is subjectively matched to a standard Aroclor
pattern, quantitation is conducted by integration of peak areas or
comparison of peak height. The methodology for quantitation by pat-
tern matching is described by Chan and Sampson (5) and by the U.S.
Environmental Protection Agency (6)(7). Care must be taken to insure
that the sample chromatogram and the standard chromatogram are close
to the same concentration (i.e., they may differ by no more than a
factor of 2). This is necessary to assure the EC detector is
operating in a linear range.
10.4 For purposes of confirmation of the PCB present, an SE-30/OV-210
column may be used with the following operating conditions:
Glass column 180 cm length, 2 mm ID
4X/6X SE-30/OV-210 liquid phase
Chromosorb W-(HP), 80/100 mesh support
N2, 38 psig inlet pressure
Detector temperature--225°C
Column temperature--200°C
Injector temperature--240°C
Detector—electron capture
18
-------
11.0 Method for Quantitation of PCB by Perchlorlnation
11.1 Principal. Perchlorination of a PCB mixture using antimony penta-
chloride (SbC^) as the active reagent results in conversion of
all PCB present to DCB which is a single isomeric, fully-substituted
species.(8) This species has a high electron capture (EC) detector
response. It can also be more readily separated from other compounds
by GC techniques than can the complex PCB mixture. Quantitation can
be accomplished by measurement of a single peak.
11.2 Sample Preparation. The sample extract (1.0 ml) prepared in the
method described above is quantitatively transferred to a Kuderna-
Danish apparatus with micro-Snyder column (Section 5.2.13).
11.3 Removal of Solvent. The extracted PCB must be quantitatively
exchanged from the hexane solvent to chloroform. All residual hexane
must be removed from the extract prior to perch!orination. Even small
amounts of residual hexane will result in the formation of a black
solid residue upon the addition of SbC^. This severely reduces
PCB recovery. The hexane is removed by azeotrophic evaporation from
the hexane/chloroform mixture.
11.3.1 Add 3 ml of nanograde chloroform to the Kuderna-Danish receiver con-
taining the sample extract in hexane and concentrate, using a micro-
Synder column, by slow boiling in a tube heater or water bath to about
U.2 ml. Do not allow to evaporate to dryness.
11.3.2 Repeat step 11.3.1 three additional times in order to remove all resi-
dual hexane. Rinse tne micro-Snyder apparatus with a minimum amount
of chloroform. Final volume should be approximately 1.0ml.
11.3.3 Quantitatively transfer to a reaction vial (Section 5.2.3) using three
chloroform rinses (Total rinse volume about 2 ml).
11.3.4 Add two micro-Hengar boiling chips and immerse reaction vial upright
in a 70°C water bath to a depth of 6 + 2 cm.
19
-------
11.3.5 Increase water bath temperature slowly until the solvent begins to
boil. Boiling temperature should be 72-76°C.
11.3.6 Concentrate slowly to a volume of approximately 0.1 ml. Under no cir-
cumstances should the water bath temperature be permitted to exceed
76°C or the solvent will be evaporated to dryness. If either of these
happen, PCB will be lost by volatilization and consequent recoveries
will be low. The final volume (0.1 ml) may be determined with suffi-
cient accuracy by comparison of solvent level with another reaction
vial containing 0.1 ml of chloroform.
11.3.7 When a volume of 0.1 ml is achieved, cap the reaction vial immediately
and allow to cool.
11.4 Sample Perch!orination.
11.4.1 To the concentrated sample extract in the reaction vial add 0.2 ml of
SbCls (Section 5.4.1) and immediately re-seal the vial tightly
with the Teflon-lined screw cap.
11.4.2 Place the reaction vial into a preheated (160 + 3°C) aluminum block
heater for a period of 15 hours.
11.4.3 After the reaction period, remove the reaction vial from the aluminum
block heater and allow to cool to room temperature. Then cool to 0°C
in an ice water bath.
11.4.4 Cautiously vent pressure from the vial in a fume hood, directing away
from the analyst. Add 1 ml of 6 IN HC1 to the cool reaction vial,
replace the cap tightly and shake for 30 seconds. The HC1 stops the
perchlorination reaction. CAUTION: IF THE REACTION VIAL IS NOT COOL,
THE ADDITION OF HC1 MAY CAUSE DANGEROUS SPLATTERING OF THE REAGENTS
FROM THE CONTAINER.
11.4.5 Add 1 ml hexane, shake vigorously for 30 seconds and carefully draw
off the hexane layer with a disposable pipet.
20
-------
11.4.6 Place this hexane extract on the top of a 6 mm x 12 cm disposable
pipet packed with 2 g of anhydrous Na2$Q4. ^nis co^umri is prewashed
with hexane.
11.4.7 Repeat steps 11.4.5 and 11.4.6 five times to assure complete
extraction of all DCB from the reaction vial.
11.4.8 Pass two 1 ml portions of .fresh hexane through the Na2$04 column
and collect all fractions in a 10 ml graduated Kuderna-Danish receiving
vial (Section 5.2.11 ).
11.4.9 Connect a modified micro-Snyder column to the Kuderna-Danish apparatus
(Section 5.2.11), add one Hengar boiling chip, and evaporate in a water
bath (70°C) to less than 0.5 ml. Care must be taken to avoid bumping
and loss of sample.
11.4.10 Cool the apparatus to room temperature and remove the micro-Snyder
column. Rinse the micro-Snyder column with sufficient fresh hexane to
bring the volume up to 1.0 ml as indicated on the graduated Kuderna-
Danish receiving vial. Remove the micro-Snyder column and mix by gentle
swirl ing.
11.4.11 Transfer the extract immediately (before significant solvent
evaporation) to a properly-labeled Hypo-vial.
11.4.12 Close the Hypo-vial with a Teflon septum and aluminum cap (Section
5.2.10). Ml PCB present in the sample has been converted to DCB in
1.0 ml hexane. The sample is now ready for GC analysis.
11.5 Analysis
11.5.1 Analyze the DCB present in the perchlorinated extract by GC/EC. The
following column conditions have been found to be suitable:
Glass column: length 6 ft., ID 1/8"
1.5% OV-17/1.95% QF-1 liquid phase
Chromosorb W-HP, 80/100 mesh support
N2> 35 psig inlet, approximately 40 ml/min
21
-------
Column temperature--220°C
Injection port temperature—240°C
Detector Temperature--200°C
Under these conditions, DCB will elute in approximately 20 minutes.
Figure 6 is a typical chromatogram.
11.5.2 A procedural blank value must be determined with which to correct low
level analytical results. Select two PUF plugs and a glass fiber
filter that have been cleaned-up and handled in the same manner as
the materials used for air sampling. Extract these PUF plugs and
filter in the same manner as described above for the samples. Per-
chlorinate the extracts in the same manner as an air sample. The
resulting blank concentration, if significant, must then be used in
the calculation of airborne PCB concentration. It has been found
that the lowest procedural blank value achievable is approximately 50
ng of DCB after perchlorination. This amount is readily detectable.
The minimum detectable airborne concentration should, therefore, be
considered to be in the range of 100 ng as DCB.
11.5.3 Quantitate as DCB by comparison of the peak area with that of a known
concentration of pure DCB (Section 5.4.6) taking into consideration
all concentration factors. Care must be taken to assure the sample
concentration and the standard concentration are near the same value
so the EC detector is operating in the linear range. Peak areas of
the standard and the sample should not differ by more than a factor
of two.
A - B
ng DCB/m3 = S x C
V
where A = area of the DCB peak of the sample
B = area of the DCB peak of the procedural blank (Section
11.5.2)
S = area of DCB standard peak
C = concentration of the DCB standard in ng
V = volume of air sampled in m3.
11.5.4 To convert DCB values to approximate equivalent PCB values, Table 1
may be employed.
22
-------
O
CXJ
l/l
O)
E
O
CD
s
c
c
s
c
4-
CC
c:
o_
O
E
ra
s_
en
o
6
o
Q
OJ
i.
to O
23
-------
Table 1. Factors to Mathematically Convert Decachlorobiphenyl to an
Equivalent Amount of Aroclor (8)
Aroclor
1221
1232
1242
1016
1248
1254
1260
1262
DCB
Av. No. Cl*
1
2
3
3
4
5
6
7
10
MWt
188.5
223
257.5
257.5
292
326.4
361
395.3
499
X**
0.38
0.45
0.52
0.52
0.59
0.65
0.72
0.79
1.00
* Average whole number of chlorines calculated from percent chlorine
substitution for a specific Aroclor
t Molecular weight of Aroclor based on the average whole number of
chlorines calculated from percent chlorine substitution
** X = molecular wt Aroclor/molecular wt DCB (499). To convert ppm
DCB to ppm of a specific Aroclor, multiply ppm x DCB by X for the
Aroclor.
24
-------
11.5.5 Confirmation may be accomplished by: a) gas chromatographic/mass
spectroscopy if sufficient DCB is present, or b) analysis on an
alternate GC column as suggested in Section 10.4.
*
12.0 Analysis of Biphenyl
12.1 Biphenyl is converted to DCB during the perchlorination step. If a
significant amount of biphenyl is present in a sample, the analyst
may want to correct the results for this. A separate GC analysis and
quantitation using a flame ionization detector (GC/FID) is required.
12.2 Biphenyl may be analyzed on an SP-2100 column using the following
operating conditions:
10% SP-2100 on 80/100 Supelcoport
180 cm x 2 mm ID stainless steel or glass column
Carrier gas: N2 @ 27 ml/min
Detector: flame ionization, \\2 @ 22 psi
Temperature program: 134°C for 8 min. then increase to 150°C
at 4°C/min. Elution temperature about
146°C. Elution time 10 min
12.3 If it is desired that the perchlorination result (total DCB) reflect
only PCB in a sample that contains biphenyl as well as PCB, the
analyst must correct the result as follows:
w
Corrected ng DCB/m3 - calculated ng OC8/m3 - Q 3(Jy(ng BIPH/rn3),
where Y is the conversion efficiency of biphenyl (BIPH) to DCB in the
perchlorination procedure. Tests (N=1G) nave shown the value of Y is
0.443 + O.o8b using the perchlorination technique described above.
13.0 Quality Control
13.1 The collection efficiency of the sampling system should be checked
by independent extraction and analysis of the third PUF plug (the
one farthest from the sampler intake). Comparison of the PCB
collected on this plug to the total on the other two plugs
provides an estimate of the collection efficiency of the sampling
system if the sampling guidelines described in Section 7.4 are
fol1 owed.
25
-------
13.2 Approximately 10 percent of the sample extracts are analyzed in
duplicate. Frequent material and reagent blank values are
determined.
13.3 Extraction technique may be evaluated by spiking and recovery of PCB
from the polyurethane foam.
13.4 The procedural blank value must be frequently determined (Section
11.5.2) and must be consistently low with respect to the PCB
collected during sampling.
13.5 Standards are frequently injected as a check of the stability of the
operating conditions, detector, and column.
26
-------
REFERENCES
(1) Bidleman, T.F. and Olney, C.E., 1974. High-Volume Collection of
Atmospheric Polychlorinated Biphenyls. Bull. Environ. Contam.
ana Tox., 11:5; 442-450.
(2) Youden, W.J. and Steiner, E.H., 1975. Statistical Manual of the
Association of Official Analytical Chemists.
(3) Code of Federal Regulations, Title 40, Part 50, pp. 12-16,
July 1, 1975. Procedures for the Measurement of Total Suspended
Airborne Particulate.
(4) Mieure, J.P.; Hicks, 0.; Kaley, R.G.; Saeger, V.W., 1975. Char-
acterization of Polychlorinated Biphenyls. Presented at National
Converence on Polychlorinated Biophenyls Nov. 19-21, 1975,
Chicago, IL.
(5) Chau, A.S.Y. and Sampson, R.C.J., 1975. Electron Capture Gas
Chromatographic Methodology for the Quantitation of Polychlorin-
ated Biphenyls: Survey and Compromise. Environmental Letters
8:2;89-101.
(6) U.S. Environmental Protection Agency, 1974. Method for Poly-
chlorinated Biphenyls (PCB's) in Industrial Effluents. Environ-
mental Monitoring and Support Laboratory, Cincinnati, OH.
(7) U.S. Environmental Protection Agency, 1974. Manual of Analytical
Methods for the Analysis of Pesticide Residues in Human and
Environmental Samples. Environmental Toxicology Division,
Research Triangle Park, NC 27711.
(8) Armour, J.A., 1973. Quantitative Perchlorination of Polychlori-
nated Biphenyls as a Method for Confirmatory Residue Measurement
and Identification. JAOAC, 56: 4; 987-993.
'27
-------
TECHNICAL INFORMATION CLEARANCE
1. DATE PREPARED
January 30, 1978
I -GENERAL
3. POLICY ISSUES
for Sampling and Analysis of
Polychlorinated Biphenyls (PCB's) in Ambient
Air.
DYES (Attach) KX.
4. PUBLIC AFFAIRS
DYES 0
6. AUTHOR, ORGANI2,' ." AND ADDRESi.
Charles L. Stratton, Stuart A. Whitlock and
J. Mark Allan, Environmental Sci. & Enq., INC.
P. 0. Box 13454, Univ. Stat., Gainsville, FA 32
II - EPA TECHNICAL REPORT SERIES
9 SERIES
10.
TYPE OF REPOFIT
a. PROJECT (-sOne)
b. SPECIAL
DISTRIBUTION (Check blocki)
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OPTIONAL (Specify keys)
IN-HOUSE
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EXTRAMURAL
PROJECT OFFICER/IN-HOUSE AUTHOR
25)STORAGE'
NTIS (Justify)'"
ADDITIONAL*
UNPUBLISHED ONLY (Justify)*
b. DAT,
'Indicate number of copies
"Attach complete lustification
COMMENT
EPA will print the
f-eport
ftnDtri?aArNgDe?unTtr.S. EPA
OAB/EMSL, MD-77, RTP, N.C. 27711
. TELEPHONE
541-2196
III - OTHER TECHNICAL MATERIAL
13. TYPE OF MATERIAL
I I
Q
D
JOURNAL PUBLICATION
ORAL PRESENTATION
PAPER FOR CONFERENCE
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17 TECHNICAL [XJYES
IN/A
a. TECHNICAL REVIEWERS NAME AND ADDRESS
18 EDITORIAL
DYES Q^IO.
Il9. FORMAT
[DvES DNO DN/A
20. POLICY
LJYES UNO
Dr. R. G. Lewis, ACB/ETD
Dr. William .1. Mitchell, QAB/EMSL/RTP, MD-77
21 COMMENT
TECHNICAL INFORMATION COORDINATOR
Mr. Thomas Hartledge, EMB/EMSL/RTP, MD-76
bWAME A'ND ADDRESS
Seymour Hochheiser, E'1SL/RTD, MD
75
d. TELEPHONE
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V - APPROVALS
LABORATORY SIGNATURES
HEADQUARTERS SIGNATURES
IMMEDIATE SUPERVISOR
IMMEDIATE SUPERVISOR
Dr. J.B. Clements,Chief. QAB/EMSL/
DATE
./n/78
SIGNATURE
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^TP 5/9/78
TYPED NAME AND ADDRESS
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SIGNA-TUR* '
SIGNATURE
EPA Form 5320-2 (11-761
-------
TECHNICAL REPORT DATA
ffleait read Inscrucnoru on the revene be/ort complennfl
REPORT NO.
EPA-600/4-78-048
3. RECIPIENT'S ACCESSION NO.
. TITLE AND SUBTITLE
A Method for the Analysis of Polychlorinated Biphenyl
(PCB) in Air
8. REPORT DATE
August 1978
8. PERFORMING ORGANIZATION COOE
. AUTHOR(S)
Charles L. Stratton, Stuart A. Whitlock, J. Mark Allan
8. PERFORMING ORGANIZATION REPORT NO.
i. PERFORMING ORGANIZATION NAME AND ADDRESS
Environmental Science and Engineering, Inc.
P. 0. Box 13454, University Station
Gainesville, Florida 32604
1O. PROGRAM ELEMENT NO.
1HD621
11. CONTRACT/GRANT NO.
68-01-2978
12. SPONSORING AGENCY NAME AND ADDRESS
Quality Assurance Branch, Environmental Monitoring and
Support Laboratory, U.S. EPA, Research Triangle Park,
NC 27711, and Office of Toxic Substances^ U.S. EPA,
Washington, D.C. 20460
13. TYPE OF REPORT ANO PERIOD COVERED
Final 8/75-12/77
14. SPONSORING AGENCY COOE
EPA-ORD
IS. SUPPLEMENTARY NOTES
16. ABSTRACT
A method has been developed for the sampling and analysis of polychlorinated biphen-
yls (PCBs) in air. An easily constructed, high-volume sampling system is em employed
with porous polyurethane foam as the collection medium. The sample is collected at
the rate of 0.6 to 1.0 m3 per minute. Laboratory procedures described in this
document permit the quantitative analysis of even the most volatile PCB species in an
air sample. A perchlorination technique for the quantitative analysis of PCB has
been adapted for use. The technique is shown to convert even the most volatile PCB
species to decachlorobiphenyl for simple and direct quantitative analysis. Data is
presented to show conversion efficiencies of a variety of PCBs to decachlorobiphenyl
of 101 _+ 6 percent over the range of 0.103 to 10.0 ug. A ruggedness test was con-
ducted which indicates the proposed perchlorination technique can yield reliable
interlaboratory results. The perchlorination technique is generally necessary for
the analysis of low (i.e., less than 25 ng/m3) airborne levels of PCB. The ana-
lytical method is effective for the analysis of airborne PCB levels within at least
the range of 1 ng/m3 to 50 ug/m3. The mean collection efficiency for Aroclor
1016/1242 was 101 _+ 10 percent for sampling periods of 20 minutes to 12 hours and air
volumes of 16 to 720 cubic meters. Field tests of the method under a variety of
ambient conditions are described.
KEY WORDS ANO DOCUMENT ANALYSIS
DESCRIPTORS
b.lOENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Croup
Polychlorinated biphenyl, PCB, high-volume
sampling, environmental contamination,
environmental studies
Methods Evaluation
Methods Development
Ambient Air
14B
13B
IB. DISTRIBUTION STATEMENT
Unlimited Release to public
19. SECURITY CLASS IT*ii Rtportf
Unclassified
21. NO. Of PAGES
20. SECURITY CLASS iThit pagt>
Unclassified
22. PRICE
EPA Perm 2230-1 (»-7J|
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