xvEPA
United Slates
Environmental Protection
Agency
Office of
Toxic Substances
Washington DC 20460
EPA-560/5-82-005
October. 1982
Toxic Substances
Methods of Analysis
for By-Product PCBs
Literature Review
and Preliminary
Recommendations
1000
100-0
1000
I T
280 285 290 295 300 305 310 315 320 325
Daltons
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DISCLAIMER
This document has been reviewed and approved for publication by the
Office of Toxic Substances, Office of Pesticides and Toxic Substances, U.S.
Environmental Protection Agency. Approval does not signify that the contents
necessarily reflect the views and policies of the Environmental Protection
Agency, nor does the mention of trade names or commercial products constitute
endorsement or recommendation for use.
-------
METHODS OF ANALYSIS FOR BY-PRODUCT PCBs—LITERATURE
REVIEW AND PRELIMINARY RECOMMENDATIONS
By
Mitchell D. Erickson and John S. Stanley
Midwest Research Institute
425 Volker Boulevard
Kansas City, MO 64110
TASK 51
INTERIM REPORT NO. 1
EPA Contract No. 68-01-5915
MRI Project No. 4901-A(51)
October 12, 1982
For
U.S. Environmental Protection Agency
Office of Toxic Substances
Field Studies Branch
TS-798
Washington, DC 20460
Attn: Dr. Frederick W. Kutz, Project Officer
Mr. David P. Redford, Task Manager
-------
PREFACE
This report presents the results of a literature review and preliminary
methods recommendations accomplished on MRI Project No. 4901-A, Task 51, "PCB
Analytical Methodology Task," for the Environmental Protection Agency (EPA
Prime Contract No. 68-01-5915). The review was performed and the document
prepared by Drs. Mitchell D. Erickson and John S. Stanley, with assistance
from Elliot Hirsch, Scott Meeks, Betty Jones, Kay Turman, Kathy Funk, Lanora
Moore, Cindy Melenson, Carol Shaw, and Gloria Sultanik.
MRI would like to thank the people listed in Appendix A for their co-
operation. We are especially indebted to Phillip W. Albro, Thomas A. Bellar,
Michael D. Crouch and associates, Ralph C. Dougherty, Larry F. Hanneman, Edo D.
Pellizzari, James D. Petty, and David L. Stalling, J. Lawrence Robinson, and
the CMA PCB Analytical Task Group through Robert J. Fensterheim who provided
valuable written peer review comments on the draft document. In addition, the
helpful comments of John Smith, DDB, OTS, EPA; Dave Redford and Ann Carey, FSB,
OTS, EPA; and the members of the PCB Analytical Task Force of CMA are
especially appreciated.
MIDWEST RESEARCH INSTITUTE
<- rfa-b—
John Going, Head
Environmental Analysis Section
Approved:
James L. Spigarelli, Director
Analytical Chemistry Department
iii
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CONTENTS
Preface iii
Figures vi
Tables vii
List of Terms, Abbreviations, and Symbols viii
1. Summary 1
2. Introduction 3
3. Literature Review 5
Sources of Information 5
Review Procedure 6
Review Articles on PCBs 6
Standard Methods 7
Sampling 10
Extraction 11
Cleanup 15
Determination 20
Data Reduction 45
Confirmation 55
Screening Techniques 56
Quality Assurance 57
By-Product Analyses 59
4. Applicable Techniques 62
Extraction. . . , 62
Cleanup 64
Determination 64
Data Reduction 66
Limit of Quantitation 70
Data Reporting 70
Confirmation Techniques 71
Screening/Equivalent Methods 71
5. Possible Analytical Schemes 73
Issues to be Addressed 73
Quality Assurance 74
Appendices
A. Personal Contacts 76
B. Bibliography 81
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FIGURES
Number
1 Comparison of packed column gas-liquid chromatography and
and capillary column gas-liquid chromatography with
Aroclor standards 24
2 Comparison of packed column gas-liquid chromatography and
capillary column gas-liquid chromatography with a milk
extract 25
3 Comparison of PCB resolution on different columns 27
4 Electron capture detection of Aroclors 1242, 1260, and 5460
(400 pg each) chromatographed on an Apiezon L (WCOT)
silanized Pyrex glass capillary, 0.20 mm i.d. x 50 m in
length 29
5 Electron capture detection of PCB in an extract of yellow
perch 29
6 Scanning capillary column gas-liquid chromatography/mass
spectrometry analysis of a mixed Aroclor standard used to
establish retention windows for the CGC/MS-SIM analysis of
PCBs 30
7 Detection limits/dynamic range for several instrumental
methods 32
8 Packed column gas-liquid chromatography/electron capture de-
tector chromatograms illustrating potential interferences
between pesticides and PCBs 36
0 Total ion current profiles for negative chemical ionization
data (upper) and electron impact data (lower) obtained on
a Finnigan 4000 glass capillary GC/MS system for Ashtabula
River fish sample 43
10 Partial high resolution mass spectrum obtained from 2.5 x
10 10 g TCDD plus matrix from 10 g human milk, illustrat-
ing potential interferences in low resolution MS 44
vi
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TABLES
Number Page
1 Standard Methods of Analysis for PCBs 8
2 Reported Limits of Detection for PCBs 33
3 Relative Molar Responses of Electron Capture and Flame
lonization Detectors to Some Chlorobiphenyls 37
4 Comparison of Relative Response Factors Between (GC)2-ECD,
GC-EIMS (Molecular Ion) and (GC)2-NICIMS (m/z 35) for
Homologous Series of PCBs 38
5 Summary of Laboratory Techniques Used for the CMA
Round-Robin Study 46
6 Summary of Laboratory Techniques Used for the CMA
Round-Robin Study 47
vii
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Accuracy
Aroclor
Askarel
By-product PCBs
CGC
CI
CIMS
Congener
Cutoff
DDE
DDT
ECD
El
EIMS
Equivalent method
External standard
FFAP
LIST OF TERMS, ABBREVIATIONS, AND SYMBOLS
Closeness of analytical result to "true" value.
Trade name (Monsanto) for a series of commercial PCB
mixtures marketed in the United States.
Nonflammable synthetic chlorinated hydrocarbon insu-
lating liquids used in capacitors, transformers, etc.;
often containing PCBs.
PCBs generated as by-products or impurities in syn-
thesis of other products (as opposed to commercial
PCBs).
Capillary column gas-liquid chromatography (includes
WCOT, SCOT, fused silica, glass, and metal).
Chemical ionization (mass spectrometry).
Positive chemical ionization mass spectrometry.
One of 209 PCBs, not necessarily the same homolog.
Lowest PCB concentration of regulatory concern.
l,l-Dichloro-2,2-bis(j>-chlorophenyl)ethylene.
1,1, l-Trichloro-2,2-bis(p_-chlorophenyl) ethane.
Electron capture detector.
Electron impact ionization (mass spectrometry).
Electron impact mass spectrometry.
Any method, certified against the primary method,
which can be used for routine analysis of samples.
Also, termed screening method.
Standards for calculation not added to the sample ex-
tract.
Free fatty acid phase.
viii
-------
FID
FUR
GC
GC/MS
GPC
HECD
HEETP
Homolog
HPLC
HREIMS
Internal standard
IR
Isomer
KOH
LMS
LOD
LOQ
MDL
Mean
MS/MS
m/z
Flame ionization detector.
Fourier transform infrared spectrometry.
Gas-liquid chroma tography (column type unspecified).
Gas-liquid chromatography/mass spectrometry (ioniza-
tion mode unspecified).
Gel permeation chromatography.
Hall electrolytic conductivity detector (other sim-
ilar detectors such as the Coulson are included) .
Height equivalent to an effective theoretical plate.
One of the 10 degrees of chlorination of PCBs (C12H9C1
through
High performance liquid chromatography.
High resolution electron impact mass spectrometry.
Standards used expressly for quantitation added to
sample extract immediately prior to the analytical
determination.
Infrared spectrometry.
One of up to 46 PCBs possessing the same degree of
chlorination (3,4- and 4,4'-dichlorobiphenyl are
different- isomers).
Potassium hydroxide.
Limited mass scanning (mass spectrometry) .
Lower limit of detection (also MDL) . Lowest concen-
tration which an analyte can be identified as present
in the sample at a stated statistical confidence level.
Lower limit of quantitation. Lowest concentration to
which a value can be assigned at a stated statistical
confidence level .
Method detection limit.
Arithmetic mean.
Mass spectrometry/mass spectrometry.
Mass-to-charge ratio.
ix
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NAA
NCI
NCIMS
NMR
PBB
PCB
PCN
PCT
PGC
ppb
ppm
Precision
QA
QC
Remand Rule
RI
RIA
RIC
RMR
RSD
SCOT
Neutron activation analysis.
Negative chemical ionization (mass spectrometry).
Negative chemical ionization mass spectrometry.
Nuclear magentic resonance spectrometry.
Polybrominated biphenyl.
Polychlorinated biphenyl (including monochlorobiphenyl,
but excluding biphenyl).
Polychlorinated napthalene.
Polychlorinated terphenyl.
Packed column gas-liquid chromatography.
Parts per billion (10 9).
Parts per million (10~6).
Reproducibility of an analysis, measured by SD of
replicates.
Quality assurance. An organization's program for as-
suring the integrity of data it produces or uses.
Quality control. The specific activities and pro-
cedures designed and implemented to measure and con-
trol the quality of data being produced.
Rulemaking for new PCB regulations for inclusion in
40 CFR, Part 761 in response to orders from the U.S.
Court of Appeals from the District of Columbia on
October 30, 1980 and April 13, 1981.
Retention index.
Radioimmunoassay or radio isotope dilution assay.
Reconstructed ion chromatogram.
Relative molar response.
Percent relative standard deviation (SD/mean x 100).
Support coated open tubular (CGC column).
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SD
Sensitivity
SIM
Surrogate
TCD
TCDD
TIC
TLC
WCOT
Standard deviation.
The slope of instrument response with respect to the
amount of analyte. Also used colloquially in refer-
ence to lowest detectable amount of analyte.
Selected ion monitoring (also mid or mass fragmentog-
raphy).
Standard compounds added to the sample prior to any
analytical manipulations for the express purpose of
measuring recovery through extraction, cleanup, etc.
Thermal conductivity detector.
Tetrachlorodibenzo-j>-dioxin.
Total ion current chromatogram.
Thin-layer chromatography.
Wall coated open tubular (CGC column).
xi
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SECTION 1
SUMMARY
The published literature on PCB analysis is critically reviewed. Sev-
eral hundred references are cited in a bibliography. The review is subdi-
vided into extraction, cleanup, determination, data reduction, confirmation,
screening, quality assurance, and by-product analysis sections. The deter-
mination section includes TLC, HPLC, GC (PGC and CGC), GC detectors (ECD,
FID, HECD, EIMS, and other MS) and nonchromatographic analytical methods
(NMR, 1R, electrochemistry, NAA, and RIA).
Based on the review of the literature, personal communications with re-
searchers in the field, and the authors' judgment, techniques applicable to
analysis of commercial products, air, and water for by-product PCBs under the
Remand Rule are discussed. Each individual analytical component (extraction,
cleanup, determination, etc.) is separately discussed. The final section of
this report presents the recommended overall primary analytical scheme:
1. Homogenize sample and subsample if necessary.
2. Incorporate surrogate compounds (e.g., four 13C PCB congeners).
3. Dilute, extract, or clean up as required.
4. Concentrate or dilute to a known volume.
5. Analyze a known aliquot by GC/EIMS.
6. Identify PCBs by relative retention time and mass spectral charac-
teristics.
7. Integrate the PCBs by homolog and calculate amounts of each homolog
by normalizing the responses to responses for the surrogate compounds, using
one or more homolog response factors.
8. Sum all 10 homolog concentrations to obtain a total PCB value.
9. Report on standard reporting form.
10. Follow specified routine QC (blanks, controls, duplicates, standard
condition, instrument performance criteria, etc.).
11. Maintain appropriate records.
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Several details in this scheme are subject to revision, as discussed in
the report. Several unresolved issues are discussed, including the permissi-
ble flexibility in the method, the use of equivalent methods, and quality as-
surance .
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SECTION 2
INTRODUCTION
PCBs have been manufactured as commercial products since 1929 and mar-
keted under trade names such as Aroclor (United States), Chlophen (Germany),
and Kanechlor (Japan). These were all complex mixtures of many congeners and
several homologs. They were used as dielectric fluids in capacitors and trans-
formers, hydraulic fluids, fire retardants, plasticizers, and many other appli-
cations . Their manufacture and use have been frequently reviewed (Hutzinger
et al., 1974; and many other reviews listed in "Review Articles on PCBs"
section below).
Beginning in 1966 (Jensen, 1972; anonymous, 1966), PCBs were found in
environmental samples as interferents with chlorinated pesticides (e.g., DDT)
analysis with increasing frequency. As the magnitude of the problem grew,
the emphasis on PCBs gradually shifted from interferents to analytes. Con-
comitant ly, their toxicology was being studied. While their toxicity varies
among isomers and species, PCBs have been sufficiently implicated in animal
and human toxicity to warrant their ban in the United States (Toxic Substances
Control Act (TSCA), Public Law 94-469, October 11, 1976). The public outcry
prior to TSCA and enforcement of the law thereafter have prompted increased
scientific interest in all aspects of PCBs.
Central to the environmental studies of PCBs is their analysis. Most of
the early methods were direct adaptations of chlorinated pesticide procedures.
As interest grew, analytical techniques improved and methods of analysis be-
came increasingly sophisticated. However, PCB analysis is plagued by the fact
that PCBs are not one specific compound like most pesticides, but in fact are
a class of 209 congeners. Until very recently, all of the PCB analyses were
directed toward commercial (e.g., Aroclor) products or their derivatives (me-
tabolites, weathered samples, etc.). The complexity of the raw data (chro-
matograms) and lack of other standards have led scientists to report PCB find-
ings in terms of Aroclor (or other products) calibration standards. This pro-
cedure is at best approximate when the sample resembles the standard and
becomes hopeless if the sample does not "match" standards.
The problem of PCB analysis has recently become more complex due to con-
cern over incineration products and by-product PCBs, where the PCB mixture in
no way resembles an Aroclor pattern. Incinerator products are of concern
since U.S enforcement efforts have recently concentrated on destruction of
existing PCB products rather than on landfill disposal. The concern over
by-product PCBs may be traced to the opinion of U.S. courts that PCBs gen-
erated as impurities in other products are subject to the TSCA ban on PCB
manufacture.
-------
This document presents a review of analytical techniques used for the
analysis of PCB and discusses which of these may be applicable to determiner
tion of by-product PCBs. A general analytical scheme is proposed with sev-
eral options in areas where there is no clear best available technology.
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SECTION 3
LITERATURE REVIEW
This section is a critical review of the published literature on analyt-
ical techniques for PCBs. Where possible, comments have been made regarding
the quality of the work and the utility of the technique. However, discussion
of the relevance of techniques toward the PCB Remand Rule has been left to
Sections 4 and 5.
SOURCES OF INFORMATION
Computerized and manual searches and relevant references in recent arti-
cles were used. Many documents were obtained from the personal files of MRI
employees. Recent issues of several key journals (Analytical Chemistry,
Journal of Chromatography, Journal of the Association of Analytical Chemists,
Environmental Science and Technology, etc.) were searched manually to pick up
any recent references not yet in the computer data bases. In addition, several
known PCB researchers (Appendix A) were called to discuss approaches to the
Remand Rule. In these discussions, they were asked to send copies or give
references to any recent publications or preprints.
The computer searches were done using DIALOG. Chemical Abstracts (CA)
files were searched back to 1972, printing all references containing "PCB"
and synonyms and keywords beginning with the following letters: "anal,"
"chromatogr," "mass spectr" and synonyms. A similar search was performed on
the National Technical Information Service data base (now including Smithsonian
Science Information Exchange). These searches printed out 349 citations, of
which 188 were judged sufficiently relevant to obtain at least the CA abstract.
In addition to nonanalytical articles, articles where PCBs were mentioned but
were clearly not the major focus of the article, and articles which clearly
contained only analytical results and not methods, the majority of citations
not obtained were in obscure foreign language journals and apparently were
similar to other available references.
Once the primary search data had been digested, it became apparent that
several authors were of primary interest and all of their recent (1980 and
1981) publications were retrieved by a CA search on their name. These authors
were P. W. Albro, T. F. Bidleman, U. A. Th. Brinkman, 0. Hutzinger, R. G.
Kaley, S. Safe, D. L. Stalling. Most of the new citations retrieved by this
search were irrelevant (metabolism studies, synthesis, etc.) to this report.
An additional manual cross-check was made with the document "Polychlori-
nated Biphenyls, Polybrominated Biphenyls, and Their Contaminants: A Litera-
ture Compilation 1965-1977" (Winslow and Gerstner, 1978). This document con-
tains 1,880 PCB citations, although not all pertain to analytical methods.
-------
References contained in review articles and primary literature were also
checked to assure that no important articles were missed by the computer
search. Several articles were added to the files by these searches.
REVIEW PROCEDURE
All articles cited in the bibliography (Appendix B) were surveyed for
relevant analytical details. The salient features of each article were noted
and any key subject areas were listed. Each citation was cross filed in any
of 33 applicable key subject areas (PGC, CGC, EIMS, Review, etc.).
REVIEW ARTICLES ON PCBs
Any class of chemical compounds as often studied and as subject to regu-
latory pressure as PCBs has been the subject of review articles. A total of
27 books and articles were characterized as PCB reviews. The PCB review most
often cited is probably the book The Chemistry of PCBs by Hutzinger et al.,
(1974). This book characterizes commercial PCBs; synthesis routes; chemical
and photochemical reactions; metabolism; mass spectrometry; NMR, UV, and IR
spectral properties; determination methods, and recent developments. Although
dated, this review covers the general subject and the analysis of PCBs (in
1974) comprehensively.
Reynolds (1969) reviewed the problems of PCB interference with the analy-
sis of pesticide residues and later expanded on this in Residue Reviews
(Reynolds, 1971). Risebrough (1971) reviewed analytical techniques for PCBs
in environmental samples. Fishbein's (1972) review of the chromatographic
and biological aspects of polychlorinated biphenyls discussed column chroma-
tography, TLC, GC, and GC/EIMS in some detail. DeVos (1972) reviewed the
methods for pesticides and PCBs in wildlife samples used by various labora-
tories in the Netherlands. Lincer (1973) reviewed PCBs, again as interferents
with pesticide residue analysis. - Safe (1976) reviewed the analytical problems
and methods for PCBs as part of a national conference on PCBs (Ayer, 1976)
which covered all aspects of the PCB issue (biology, metabolism, destruction,
regulatory, etc.).
Sherma (1975) reviewed GC of PCBs, including extraction, cleanup, GC sys-
tems, identification, confirmation, and quantitation. Chau and Sampson (1975),
in an attempt to standardize quantitation, surveyed and reviewed the various
methods for PGC/ECD quantitation. lao et al. (1976) reviewed the application
of GC/MS to PCB analysis. Extraction, chromatographic separation (cleanup),
GC/ECD, and computer-aided data interpretation were discussed by Krull (1977).
Brinkman et al. (1978) discussed various literature procedures for discrimi-
nation between PCBs and polychlorinated naphthalenes (PCN). Lawrence and
Turton (1978) included PCBs in a tabulation of HPLC data for 166 pesticides.
Environmental Health Perspectives devoted an entire issue (Rail, 1978)
to PCBs. Pomerantz et al. (1978) reviewed the chemistry of PCBs; Matthews
et al. (1979) reviewed metabolism and toxicity; Cordle et al. (1978) reviewed
human exposure; Kimbrough reviewed animal toxicology; and the DHEW Subcommittee
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of Health Effects of PCBs and PBBs (1978a, 1978b) provided general recommenda-
tions and general summary and conclusions which included discussions of the
analytical aspects of PCBs.
Stalling et al. (1979) reviewed PCB analysis with particular emphasis on
their own work of automating the extraction and cleanup processes.
The sampling and analysis of PCBs in air have been reviewed by Lao et al.
(1976), Margeson (1977), and Fuller et al. (1976).
The analytical aspects of PCBs have also been reviewed by Sherma (1981),
Nose (1976), and Tanabe (1973). Finlay et al. (1976) reviewed PCB levels in
the environment but did not discuss analysis. Other reviews not discussing
analysis include Resource Planning Commission (1982), Fishbein (1979), and
Kimbrough (1980).
None of the review articles discussed above is current (the most recent
was 1979), nor do they discuss the problems of determination of incidentally
generated PCBs. In response to the PCB Remand Rule, the Chemical Manufacturers
Association (1981) critically reviewed the PCB analytical techniques potentially
applicable to the rule and recommended that GC/EIMS be the method of choice
for analysis under this rule.
STANDARD METHODS
Table 1 lists the standard analytical methods available for PCBs. It
should be noted that not all of the methods listed are sanctioned at this
point. Many have interim status and some have been proposed but never en-
dorsed by an organization. The standard methods provide analytical approaches
for the measurement of PCBs in a variety of materials including water, waste-
waters, soils, sediments, sludges, air, combustion and incinerator emissions,
capacitor askarels, transformer-fluids, waste oils, mixtures of chlorinated
benzenes, pigments, food, milk, and adipose tissues.
Table 1 summarizes each of the standard methods. Extraction and cleanup
procedures are presented in terms of the materials and reagents required for
analysis. Less than half of the methods comment on the criteria required to
make qualitative determinations for the presence of PCBs in sample extracts.
The method of quantitation for each of the analysis schemes is presented along
with the limit of detection (LOD), if specified. Additional analytical proce-
dures to confirm the levels or presence of PCBs are also indicated. More than
half of the standard methods mention quality assurance in some respect. The
quality assurance steps include analysis of blanks, replicates, control sam-
ples, spiked additions, and accuracy, precision, and instrumental performance
criteria.
All of the methods, except those provided by DCMA (1981) and Dow (1981)
are directed to the analysis of PCBs as Aroclors or similar mixtures. The
DCMA (1981) and Dow (1981) methods were developed for the analysis of by-
product PCBs in commercial products.
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TABLE 1. STAHDARD METHODS OF ANALYSIS FOR PCBs
00
Method
ANSI
ANSI
ANSI
AOAC (29)
D3303-74
D3306-74
DCHA
Devenlsh
DOW
EPA
(Halocarbon)
EPA (PP)
EPA (304h)
EPA (BIOO)
Matrix
Air
(toluene
impinger)
Water
Sediment
soil
Food
Paper and
paperboard
Capacitor
Askarels
Air
Water
Soil,
sediment
3 pigment
types
Water
Chlorinated
benzenes
Sludge
Sludge
Water
Sludge
(3
Extraction
-
llexane
CI13CN/
hexane
CHjCN/Pet.
ether
saponlfica-
tion
DIb
DI
Hexane
H20/CH3CN
A. Hexane/
H2SO«
B. CH2C12
Hexane
DI
Hexane/
CII2Clj/
acetone
(83/15/2)
CH2C12
(base/
neutral
and acid
fractions)
Hexane/
CH2Cla
(85/15)
CH2C12
fractions)
Cleanup
(H2S04)
(Saponification)
(Alumina)
(II2S04)
(Saponification)
Alumina
II2S04
Saponify/
alumina
Florisil MgO/
Celite
Saponification
None
(H2S04)
(Saponification)
(alumina)
None
Florisil
Alumina
None
CPC
5 removed
GPC
Florisil/
silica gel
(CH3CN)
(S removal)
GPC
Silica gel
Determination
method
PGC/ECD
PGC/ECD
PGC/ECD
PGC/ECD
SCOT CGC/FID
PGC/ECD
PCC/ECD
PGC/ECD
PGC/EIHS
PGC/ECD
PGC/EIHS
PGC/ECD
or HECD
CCC/EIHS
or PGC/EIHS
dual.
No
No
No
No
No
No
No
No
Yes
Yes
Yes
Yes
Yes
Quant.
method LOD Confirmation QA
Single peak 2 pph None Yos
Single peak 2 ppra None Yes
or summed
peaks
Single peak 2 ppm None Yes
or summed
peaks
Total area NSa TLC paper No
or Ind. chrora.
peaks
Total area 2.8 x 10~* mol/i None No
Total area NS None Yes
10 isomers -v 1 ppm/homolog PGC/MS Yes
NS 106 ng/£ None No
Total peak NS None Yes
height/
honolog
Peak area NS GC/HS Yes
or peak
height
NS NS None Yes
Summed NS None Yes
areas or
or Webh-
HcCall
NS NS None Yes
Reference
ANSI, 1974
ANSI, 1974
ANSI, 1974
AOAC, I980a
AOAC, I980b
ASTM, I980a
ASTH, I980b
DCHA, 1981
Devenish and
Harling-Rowen
1980
Dow, 1981
Rodriguez
et al , 1980
EPA, 1979e
EPA, 1978
Bal linger, 19)
(continued)
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I (continued)
VO
Method
EPA (HERD
EPA (HERD
EPA (oil)
EPA (gas)
608
625
EPA (stack)
EPA
NIOSH (air)
(P&CAH 244)
NIOSH (air)
(P&CAH 253)
Japan
PAH
Matrix
Milk
Adipose
Transformer
fluids or
waste oils
Natural gas
sampled with
Florisil
Water
Water
Incinerator
emissions
and ambient
air collected
on Florisil
Combustion
sources
collected
on Florisil
Air col-
lected on
Florisil
Air col-
lected on
Florisil
Food
Food
Extraction
Acetone/
hexane
Pet. ether/
CHjCN
DI
Hexane
CH2C12
CH2C12
Hexane
Pentane or
CH2C12
Hexane
Hexane
Several
CH3CN/Pet
ether
Cleanup
CH3CN
Florisil
Silica acid
Saponif ication
Florisil
(H2SO<)
(Florisil)
(Alumina)
(Silica gel)
(GPC), (CH3CN)
H2SO,
(Florisil)
(S removal)
None
(H2S04)
(Florisil/
silica gel)
None
None
Silica gel
Sapon if ication
(Florisil)
Silicic acid
(Saponif ication)
(Oxidation)
(Florisil)
Determination
method Qual .
PGC/ECD Tes
TLC Ho
PGC/HECD No
or /ECD or
/EIHS
(CGC)
PGC/F.CD
PGC/ECD No
PGC/EIHS Yes
(CGC) '
Perchlori- No
nation
PGC/ECD
PGC/HS Tes
PGC/ECD No
PGC/ECD No
Perchlorina-
tion
PGC/ECD Yes
PGC/ECD No
(PGC/HECD)
(NP-TLC)
(RP TLC)
Quant.
method LOD Confirmation QA
Ind peaks 50 ppb Perchlori- Yes
nation
Semlquant 10 ppm None No
Total area 1 mg/kg None Yes
or Webb-
HcCall
Total area 0 1-2 Mg/™3 None Ho
peak height
or Webb-HcCall
(Perchlorinatlon)
Area 0 04-0 15 MB/* None Yes
Area NS None Yes
Area 10 ng GC/MS No
Area/ 0 1 ng/inj None No
homolog
Peak height 0 01 mg/m3 Nono No
or area from
standard curve
or Webb-McCall
Peak height 0.01 rng/rn3 Perchlonna- No
or area from tion
standard curve
Sunned NS None No
areas
perchlorination
Area NS TLC No
Reference
Watts, 1980
Shrrma, 1981
Watts, 1980
EPA, 1981
Bellar and
Lichtenberg,
1981
Harris and
Mitchell, 19B1
EPA, 1979a
EPA, 1979h
Ha lie and
Baladi, 1977
Levins et al ,
1979
NIOSH, 1977a
NIOSH, 1977b
Tanabe, 1976
FDA, 1977
a No specific details
b Direct injection
c Techniques in parentheses are described as optional in the protocol
-------
The ANSI methods are based on techniques that were used by the Monsanto
Industrial Chemical Company for the isolation and determination of PCBs in
water, soil, sediment, and biological materials. Packed column gas chromatog-
raphy with electron capture detection (PGC/ECD) is the designated method for
quantitation of PCBs as Aroclors in the ANSI methods. Mass spectrometry, how-
ever, is recommended for each of the designated analysis schemes if confirma-
tion is required. The cleanup techniques are required only if interferences
are noted for the PGC/ECD determination. The quality assurance procedures in
the ANSI methods emphasize the number of theoretical plates and tailing factor
for the packed gas chromatography column.
The ASTM, AOAC, and EPA methods are generally designed for a particular
matrix. The level of quality assurance procedures varies from method to
method. The recent methods provide quality assurance programs of greater de-
tail and require reasonable effort to maintain the accuracy and precision of
the overall determination.
The EPA method for analysis of PCBs in transformer oils and crude oils
provides the most generalized approach with respect to sample preparation,
cleanup procedures, and instrumental analysis. Several cleanup procedures
are provided as optional approaches in this protocol, and instrumental analy-
sis by halogen specific, electron capture, or mass spectrometry detectors are
allowed, provided appropriate limits of detection can be achieved. A strong
quality assurance program including control samples, daily quality control
check samples, blanks, standard additions, accuracy and precision records,
and instrumental and chromatographic performance criteria is required to sup-
port all data generated by the method.
The Dow (1981) and DCMA (1981) procedures also require strong quality
assurance programs for analysis of by-product PCBs.
SAMPLING
The first step in any successful analysis is the collection of represen-
tative samples. The selection of sampling sites, frequency of sampling, num-
ber of samples, measurement of physical and chemical parameters of the sample,
and the overall statistical design of sampling methods have been provided in
extensive detail (Moser and Huibregtse, 1976; EPA, 1976). The sampling design
in most cases is directly related to the objectives of a specific research
program as a regulatory action.
The methods that are of interest in the context of this report are the
procedures practiced for obtaining representative specimen of air, water, and
solids. Aqueous and solid media are generally collected as grab samples, al-
though aqueous samples have been preconcentrated on solid adsorbents prior to
extraction.
Water Sampling
The solid adsorbents used for aqueous preconcentration methods include
macroreticular resins (Coburn et al., 1977; Seiber, 1974; Musty and Nickless,
1974; Webb, 1975; Picer and Picer, 1980), polyurethane foam and Chromosorb W
10
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coated with a mixture of undecane and Carbowax 4000 monostearate (Gesser et
al., 1971; Lawrence and Tosine, 1976; Bellar and Lichtenberg, 1975; Ahling
and Jensen, 1970; Osterroht, 1974; Musty and Nickless, 1976), as well as Tenax
(Leoni et al., 1976). Preconcentrating organic analytes from aqueous media
allows the analyst to work with large volumes of water and thus lowers the
method detection limit for the compounds of interest. The sorbent preconcen-
tration method also can be used as a continuous on-site sampling procedure.
Air Sampling
The PCBs in ambient air and flue gas emissions have been collected on
solid adsorbents including polyurethane foam plugs, Tenax, XAD-resins, Florisil,
Chromosorb, and Poropak and combinations of these materials (Bidleman and Olney,
1974; Bidleman et al., 1980; Bidleman, 1981; Bidleman et al., 1981; Billings
and Bidleman, 1980, 1982; Burdick and Bidleman, 1981; Simon and Bidleman, 1978,
1979; Lewis et al., 1977a, 1977b; Lewis and MacLeod, 1982; Lewis and Jackson,
1982; Williams et al., 1980; Haile and Baladi, 1977; Giam et al., 1975; Haile
et al., 1982; Stanley et al., 1982; Harris and Mitchell, 1981). The solid
adsorbents are effective for sampling PCBs in air although some problems have
been encountered with breakthrough of the lower molecular weight PCBs at high
flow rates for extended sampling periods.
Doskey and Andren (1979) evaluated polyurethane foam coated with DC 200,
Florisil, and Amberlite XAD-2 resin for their ability to sample airborne PCBs.
The collection efficiency of the adsorbents was studied using carbon-14 labeled
2,5,2',5'-tetrachlorobiphenyl. The XAD-2 resin was found to have an excellent
collection efficiency for the tetrachlorobiphenyl at a flow rate of 1 liter/min.
Their sampling system yielded 96.5% collection efficiencies for the tetrachloro-
biphenyl and 83.0% for Aroclor 1221. Further investigations demonstrated low
retention efficiencies for monochlorobiphenyl (72%) and dichlorobiphenyl (86%),
thus demonstrating that the sampling system was not equally effective for all
PCB congeners. The analytical recoveries for tetrachlorobiphenyl, Aroclor
1242, and Aroclor 1221 were 85.5%, 80.1%, and 64.9%, respectively.
Hanneman (personal communication, 1982) reported that PCBs were not re-
tained at acceptable levels on common solid adsorbents when the flue gas tem-
perature was greater than 150°C or in cases where the air contained an aerosol
of a nonpolar material in which PCBs are very soluble. Hanneman reported suc-
cessful collection of PCBs in these instances using polyurethane foam plugs
coated with liquid polydimethylsilocane. Several plugs of the coated polyure-
thane were placed in a water-cooled jacket to sample the air at elevated tem-
peratures. A PCB isomer was added to the surface of the foam plugs as a sur-
rogate prior to sampling. A second PCB isomer was added to the foam plugs
after sampling to monitor surrogate recovery and collection efficiency.
EXTRACTION
Reliable PCB analysis begins with the quantitative extraction of the ana-
lytes from the sample matrix. The extraction method is dependent on the sample
type and the complexity of the matrix encountered. In general, the extraction
methods require the use of solvents such as petroleum ether, hexane, methylene
chloride, acetone, and acetonitrile. Digestion of the sample matrix with sul-
furic acid or saponification with alcoholic potassium hydroxide is necessary
11
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in some instances to effectively extract incorporated PCBs. Dilution with
suitable organic solvents prior to gas chromatography and even direct injec-
tion of some PCB-contaminated samples have provided suitable quantitative
analysis. PCBs in air and flue gas emissions are typically collected on solid
adsorbents and removed by extracting with a suitable solvent.
Standard Methods
A number of standard extraction methods for specific sample types are
listed in Table 1. The standard methods include extraction techniques for
transformer and capacitor oils, food, soils, sediments, dyes, milk, adipose
tissue, sludge, wastewater, natural waters, emissions from combustion sources,
and ambient air.
Review Articles
Extraction methods have been reviewed previously (Hutzinger et al., 1974;
Sherma, 1975; Krull, 1977). Factors and problems that should be considered
for a given extraction procedure (Albro, 1979) include the following: (a)
each extraction method must be validated for each different matrix; (b) the
nature of the sample matrix influences the effectiveness of a given extrac-
tion procedure through various matrix properties. These properties include
the solubility of the matrix in solvent, the ease of homogenizing the sample
for subsampling, the water content of the sample which greatly affects the
extraction efficiency of the solvent, and the lipid content of tissue samples
that governs the volume of solvent required for quantitative extraction; and
(c) the incorporation of the analyte in a sample matrix and the most effective
means of adding spikes to the sample for method evaluation and quality assur-
ance measurements.
Primary Literature
A large number of extraction techniques provide quantitative recovery of
PCBs from widely different matrices. The application of the various extrac-
tion procedures to specific sample types is discussed below.
Air-
Simple and straightforward extraction procedures are used for extraction
of adsorbents from air sampling. Ambient air and flue gas emissions have been
collected on adsorbents including polyurethane filter plugs (Bidleman and Olney,
1974; Bidleman et al., 1980; Bidleman, 1981; Bidleman et al., 1981; Billings
and Bidleman, 1980, 1982; Simon and Bidleman, 1977a, 1977b, 1977c; Lewis and
MacLeod, 1982; Lewis and Jackson, 1982), Florisil (Harris and Mitchell, 1981;
Williams et al., 1980; Haile and Baladi, 1977; Giam et al., 1975), and Amber-
lite XAD-2 resin (Haile and Lopez-Avila, 1981; Stanley et al., 1982). PCBs
were quantitatively recovered from these adsorbent materials via extraction
with hexane, petroleum ether or benzene in a Soxhlet apparatus or as small
chromatographic columns.
Water and Wastewater--
PCBs in aqueous samples, including natural waters, potable supplies, sew-
age effluents and industrial wastewaters, have been extracted by a number of
12
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procedures. Liquid-liquid extraction with hexane, cyclohexane or methylene
chloride provide quantitative isolation of PCBs from aqueous samples (Brownrigg
et al., 1974; Devinish and Harling-Bowen, 1980; EPA, 1979a, 1979b; Haque et al.,
1974; Adams et al., 1979; Bellar and Lichtenberg, 1975; Caragay and Levins,
1979). In principle it is possible to extract all PCBs present in any water
sample without large scale solvent extraction (Krull, 1977). Lower levels of
detection of PCBs in aqueous samples have been achieved through the applica-
tion of solid adsorbents for large volumes that cannot be effectively handled
by classical liquid-liquid extraction procedures. The adsorbents are extracted
with hexane, petroleum ether, and diethylether to recover the PCBs. Macro-
reticular resins (XAD-2, -4, -7, and -8) have been evaluated in a number of
studies (Coburn et al., 1977; Seiber, 1974; Musty and Nickless, 1974; and Webb,
1975; Picer and Picer, 1980). Polyurethane foams and Chromosorb W coated with
a mixture of undecane and Carbowax 4000 monosterate as a reversed liquid-liquid
partition method have also demonstrated successful isolation of PCBs from
aqueous matrices (Gesser et al., 1971; Lawrence and Tosine, 1976; Bellar and
Lichtenberg, 1975; Ahling and Jensen, 1970; Osterroht, 1974; Musty and Nickless,
1976).
Two studies (Bellar and Lichtenberg, 1975; Webb, 1975) compared various
extraction methods including batch liquid-liquid extraction, vortex stirring
with an organic solvent, and adsorbent concentration on polyurethane and am-
berlite macroreticular resins. Extraction efficiencies of PCBs were greatest
with liquid-liquid extraction.
Continuous liquid-liquid extractors (Leoni, 1971; Ahnoff and Josefsson,
1973, 1974; Ahnoff et al., 1979) and steam distillation of aqueous samples
with simultaneous liquid-liquid extractions of the distillate into pentane
(Godefroot, 1982) have been studied as alternate means to lower detection lim-
its for specific organic compounds including PCBs present in water.
Wastewaters from some industrial processes have posed some interesting
problems in measurement of total PCBs released. In particular, the cellulose
fibers collected from paper mill effluents required hydrolysis with alcoholic
potassium hydroxide and extraction with hexane or methylene chloride as well
as extraction of the aqueous phase to effectively quantitate total PCBs
(Delfino and Easty, 1979; Easty and Wabers, 1978). Dissolution of the resid-
ual fibers in paper mill effluents with 72% H2S04 followed by dilution with
water and extraction with hexane was demonstrated to promote quantitative iso-
lation of PCBs.
Colenutt and Thorburn (1980) have discussed the application of gas strip-
ping or purge and trap techniques for the analysis of PCBs in water. Spiked
PCBs were removed from water samples by purging with nitrogen at ambient tem-
perature. The PCBs were concentrated on activated charcoal and desorbed with
a minimum volume (50 pi-1.0 ml) of organic solvent. Recoveries of greater
than 90% were reported for Aroclors 1221, 1248, and 1254. The efficiency of
this extraction technique is dependent on the gas flow rate, the time of strip-
ping, adsorbent particle size, and the desorbing solvent.
13
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Soils, Sediments, and Sludges—
Soxhlet extraction of soils and sediments with hexane-acetone, petroleum
ether-acetone, or hexane has been a common method of isolating the PCBs (Bellar
and Lichtenberg, 1975; Eder, 1976a; Goerlitz and Law, 1974; Jensen et al.,
1977; Macleod, 1979; Seidl and Ballschsmiter, 1976; Adams et al., 1979;
Hutzinger et al., 1974). Other methods that have been used for soils, sedi-
ments, and sewage sludges have included silica sonication (Chau and Babjak,
1979), blending with suitable solvent such as methylene chloride with centri-
fugation for separation of the phases (Rodriguez et al., 1980), and a column
technique that required mixing sediment with Florisil and eluting with 10%
water in acetonitrile. Ethanolic potassium hydroxide reflux prior to extrac-
tion of the sediment has been reported in at least one instance (Wakimoto et
al., 1971).
Soxhlet extraction, solvent shakeout, solvent blending, two column elu-
tion methods, and high frequency dispersion (Tissumizer) extraction techniques
were compared for the same bottom sediment (Bellar and Lichtenberg, 1975).
The results indicated that the highest recovery of PCBs was achieved by Soxhlet
extraction of dried samples. The authors concluded that this should be the
technique of choice for bottom sediments and sludges.
Bellar et al. (1980) extended this study using Soxhlet extraction, soni-
fication, and steam distillation for the recovery of PCBs from environmentally
contaminated lake and river bottom materials. The high frequency dispersion
extraction technique was not used in this study because of excessive and rapid
wearing of parts of the device and excessive breakage of glassware. Bottom
sediments were spiked with Aroclor 1254 and extracted by the three techniques.
The mean recovery of PCBs for spiked samples was 81-109% for the different
methods, indicating that any of the three might be used for quantitative ex-
traction. However, the Soxhlet extraction method yielded higher levels of
PCBs from environmentally contaminated sediments than either steam distilla-
tion or sonification. The results of this study are not conclusive since only
one solid sample matrix was considered.
Seidl and Ballschmiter (1976a) studied the recovery rates of PCBs from
soil using Soxhlet extraction with hexane, acetone/acetonitrile, or ultrasonic
extraction with acetone. Carbon-14 labeled Clophen A-30 was added to the soil
to simplify the extraction studies. The authors concluded that Soxhlet extrac-
tion with acetone/acetonitrile yielded the best recoveries (greater than 95%)
and Soxhlet extraction with hexane or ultrasonic extraction with acetone was
not suitable for good recoveries of PCBs from soil.
Biological Matrices--
Considerable emphasis has been placed on the analysis of biological mate-
rials for the presence of PCBs. Tissues are generally homogenized and ground
with sodium sulfate, sand, or Florisil and are either Soxhlet extracted (Bagley
et al., 1970; Curley et al., 1971; deVos, 1972; Hattula, 1974; Holden, 1971;
Kuehl et al., 1980; Stalling et al., 1972) or packed into a chromatographic
column and the PCBs are eluted with an appropriate solvent (Bowes and Lewis,
1974; Call et al., 1974; Donkin et al., 1977; Erney, 1974b; Ernst, 1974;
Hattula, 1974; Stalling, 1971; Wardall, 1977; Hutzinger et al., 1974; Stalling
et al., 1972; Sawyer, 1973; Armour and Burke, 1970). Recently, microcontinuous
14
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liquid-liquid extraction combined with steam distillation has been shown to
be an effective extraction procedure for tissues (Kuehl et al., 1980).
Other tissue extraction techniques have included blending with chloroform
and methanol mixtures followed by centrifugation (Sherma, 1975) and saponifica-
tion of fat and animal tissue with methanolic potassium hydroxide followed by
liquid-liquid extraction with hexane (Adams et al., 1979). PCBs in serum and
blood samples have been extracted by dilution with methanol followed by liquid-
liquid extraction with either hexane or diethylether.
Miscellaneous—
The other materials that have been analyzed for PCB content include trans-
former oil, silicone fluids, chlorinated benzenes, paper, packaging materials,
and pigments. Generally, transformer oils, silicone fluids, and chlorinated
benzenes are simply diluted with solvent prior to cleanup or direct analysis
(Adams et al., 1979; ASTM, 1980a; EPA, 1981; Bellar and Lichtenberg, 1981;
Klimisch and Ingebrigtson, 1980; Dow, 1980). The paper and packaging materials
have required homogenization by grinding before Soxhlet extraction with hexane
or acetone (Kurastune and Masuda, 1972; Giacin and Gilbert, 1973; Serum et al.,
1973) or hydrolysis with refluxing alcoholic potassium hydroxide and final
extraction with petroleum ether (Burke et al., 1976; Easty, 1973; Shahied et
al., 1973).
In a method published by the DCMA (1980), extraction of phthalocyanine
blue pigment required dissolution with sulfuric acid prior to hexane extrac-
tion to isolate incorporated PCBs. The PCBs in other pigments, such as
phthalocyanine green and diarylide yellow are quantitatively extracted by high
speed homogenization with methylene chloride (DCMA, 1980).
Only the extraction methods described for the colored pigments (DCMA,
1980) were developed for PCBs as nonAroclor chlorinated compounds. All other
methods were used in studies that considered the environmental impacts of the
commercially distributed PCBs as Aroclors.
CLEANUP
In addition to PCBs, a large number of chlorinated compounds, lipid ma-
terials, and sulfur are extracted from aqueous, oil, tissue, sludge, and sedi-
ment samples by the methods described above. Hence, it is necessary in many
cases to provide an additional sample preparation step or cleanup to remove
the coextractants that may act as interferences. Cleanup techniques vary con-
siderably according to the particular sample matrix and needs for final instru-
mental analysis.
Review Articles
Sample extract cleanup procedures for PCB analyses have been partially
reviewed previously (Holden, 1971; Fishbein, 1972; deVos, 1972; Hutzinger et
al., 1974; Krull, 1977; Albro, 1979).
15
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Standard Methods
Table 1 listed the cleanup procedures that are typically used with a num-
ber of standard methods for these materials. These cleanup procedures include
liquid-liquid partition of the sample extract, saponification with alcoholic
potassium hydroxide, addition of concentrated sulfuric acid, gel permeation
chromatography, and oxidation of interferences in the sample matrix.
Primary Literature
Adsorption Chromatography Cleanup—
Perusal of the literature indicates that adsorption column chromatography
is the most often practiced method of sample extract cleanup prior to instru-
mental analyses. The extent of sample cleanup required is dependent, in many
cases, on the specificity of the detector used for identification and quanti-
tation. Electron capture and halogen specific detectors (i.e., Hall electro-
lytic conductivity detector) require clean extracts since so many other com-
pounds can interfere.
Chromatographic column cleanup procedures have been used extensively with
adsorbents such as Florisil, silica gel, and alumina. Cleanup procedures may
require the use of only one column, combinations of adsorbent materials, use
of an adsorbent following liquid-liquid partition, or cleanup after matrix
destruction by sulfuric acid or saponification. Proper activation of adsorbed
materials and the characterization of the degree of activation is essential
for effective and reproducible cleanup of sample extracts by a particular chro-
matography procedure (Edwards, 1974; Zitko, 1972). Reproducibility of a column
method requires avoidance of overloading the column, accidental deactivation
of the adsorbent during cleanup, and use of pure solvents (Edwards, 1974).
Optimum cleanup and separation of PCBs from interferences require fully acti-
vated adsorbents, and large eluent volumes (Edwards, 1974; Albro and Parker,
1980). The alternative to large, eluent volumes is to use only a fraction of
the extract with microcolumn adsorbent procedures. A notable example is the
Sep Pak marketed by Waters Associates. Several investigators have reported
the application of Sep Pak for PCB cleanup as discussed below.
The most commonly used adsorbents are Florisil and silica gel at various
levels of activation. Florisil has been used to remove gross interferences
from sample extracts from air, water, wastewater, tissues, and dairy products
as well as paper, paperboard, and paper mill effluent (AOAC Methods, 1980;
Adams et al., 1979; Delfino and Easty, 1979; Easty, 1973; EPA, 1979a; EPA,
1979b; EPA, 1978; EPA, 1980; Kamops et al., 1979; Kuehl et al., 1980; Modi et
al., 1976; Price and Welch, 1972; Reynolds, 1971; Reynolds, 1969; Robbins and
Willhite, 1979; Rodriguez et al., 1980; Stijve et al., 1974; Swift and Settle,
1976; Tessari and Savage, 1980; Yakushiji et al., 1978; Bagley et al., 1970;
Bagley and Cromartie, 1973; Bellar and Lichtenberg, 1976; Chau and Babjak,
1979). Florisil has also been used to provide additional separation of sample
extracts following initial cleanup of matrices by low temperature precipita-
tion, acetonitrile partitioning, oxidation, sulfuric acid digestion, alumina
chromatography, or gel permeation chromatography (Eden, 1976; Ernst et al.,
1974; Kohli et al., 1979; Mes et al., 1977a, Mes et al., 1977b; Mulhern et
al., 1972; Stanovick et al., 1973; Swift and Settle, 1976; Tessari and Savage,
16
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1980; Trotter, 1974; Uk et al., 1972; Bagley et al., 1970; Bagley and Cromartie,
1973; Copeland and Gohmann, 1982).
Seidl and Ballschmiter (1976b) investigated the recovery and efficiency
of cleanup methods for the isolation of PCBs from vegetable oils. Column chro-
matography on Florisil, matrix destruction via saponification and sulfuric
acid treatment, and liquid-liquid partition with hexane/acetonitrile or hexane/
dimethylformamide were compared as cleanup techniques. The Florisil chromato-
graphic column with hexane/methylene chloride (80:20) as the eluent and liquid-
liquid partition with hexane/dimethylformamide were shown to be the methods
of choice with recoveries of greater than 90%.
Silica gel or silicic acid has also been used for a large number of sam-
ple matrices including water, sediments, sludges, foodstuffs, tissues, and
transformer fluids (Armour and Burke, 1970; Devinish, Harling-Bowen, 1980;
Erickson and Pellizzari, 1977, 1979; Ernst, 1974; Giacin and Gilbert, 1973;
MacLeod, 1979; Masumoto, 1972; Mes et al., 1976; Mes and Campbell, 1977; Nose,
1973; Ogata et al., 1980; Picer and Abel, 1978; Price and Welch, 1972; Sawyer,
1973; Stalling, 1971; Steichen et al., 1981, 1982; Balya and Farrah, 1980;
Beezhold, 1973; Bellar and Lichtenberg, 1975; Coburn et al., 1977).
Many applications have utilized the excellent separation properties of
silica gel to remove other halogenated interferences from PCB fractions. The
separation of a number of halogenated pesticides has been accomplished by using
silica gel after preliminary cleanup of gross interferences and controlling
the degree of activation and size of the column or by slightly modifying the
adsorbent with silver nitrate or an oxidizing agent (Erney, 1974a; Erney, 1974b;
EPA, 1978; Herzel, 1971; Huckins et al., 1976; Kreiss et al., 1981; Kveseth
and Brevick, 1979; Leoni, 1971; Mitzutani and Matsumoto, 1973; Musial et al.,
1974; Needham et al., 1980; Public Health Services, CDC, Atlanta, 1980; Serum,
1973; Snyder and Reinert, 1971; Stratton, 1977, Swift and Settle, 1976;
Trevesani, 1980; Underwood, 1979; United Kingdom, Department of Environment,
1979; Wakimoto et al., 1975; Bidleman et al., 1978).
Cleanup and separation of interferences from PCBs has been accomplished
with Sep Pak miniature silica gel cartridges for transformer (Gordon et al.,
1982; Steichen et al., 1981), mineral, phosphate ester, glycol base, and sul-
fonated mineral oils (Balya and Farrah, 1980).
Alumina has been used as an adsorbent in more recent applications for
cleanup of matrices from oils, fats, and tissues (Donkin et al., 1977; Hattula,
1974; Kohli et al., 1979; Kveseth and Brevick, 1979; Ofstad et al., 1978;
Teichman et al., 1978; Wardall, 1977; Zitko, 1976) and other biological ma-
terials such as blood and human milk (Musial et al., 1972; Siyali, 1973;
Tuinstra and Traag, 1979a, 1979b; Welborn et al., 1974) and from oil, water,
sediments, and vegetable materials (Goerlitz and Law, 1974; Lewis et al., 1977;
Tuinstra et al., 1981; United Kingdom, Department of Environment, 1979).
Dispersion of activated carbon on polyurethane foam, termed carbon foam
chromatography, and use of activated charcoal have also proven to be effective
means of isolating PCBs from complex matrices such as tissues and sediments
(Chau and Babjak, 1979; Jensen and Sundstrom, 1974; Stalling et al., 1979a;
Stalling et al., 1979b; Stalling et al., 1978; Stalling et al., 1975; Tiechman
et al., 1978).
17
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Gel Permeation Chromatography--
Gel permeation chromatography (GPC) has arisen as a popular cleanup pro-
cedure for complex matrices, especially samples containing macromolecular in-
terferents such as biological materials containing high levels of lipid ma-
terials. The GPC method has been fully automated for large numbers of sample
extracts. However, it is necessary to fully validate the GPC method for each
different sample matrix as with other cleanup procedures.
Gel permeation chromatography has been successfully used as a cleanup
for matrices of high molecular weight content and has provided a cost effec-
tive approach towards automation of large numbers of samples (Albro, 1979;
Caragay and Levins, 1979; Griffitt and Craun, 1974; Haile and Lopez-Avila,
1981; Hopper and Hughes, 1976; Kohli et al., 1979; Kuehl et al., 1980a, 1980b;
Rodriguez et al., 1980; Stalling, 1971, 1976; Stalling et al., 1972, 1979;
Tessari, 1980). Gel permeation chromatography of tissue and vegetable material
extracts followed by carbon-foam chromatography provides a cleanup that is
exceptionally selective for planar aromatic hydrocarbons and the chlorinated
analogs such as PCBs (Dougherty et al., 1980). Lipidex was shown to separate
PCBs and other semivolatile halocarbons from water, fat, butter, and milk
(Egestad et al., 1982). Elution conditions could be adjusted to separate the
halocarbons from steroids and fatty acids. The authors noted that a combina-
tion of partition, molecule sieving, and aromatic adsorption was involved in
the separation.
High Performance Liquid Chromatography and Thin Layer Chromatography--
High performance liquid chromatography (Aitzetmiiller, 1975; Dolphin and
Willmott, 1978; Rohleder, 1976) and thin-layer chromatography (Fishbein, 1971;
Hattula, 1974; Koeniger, 1975) have also received limited attention as chro-
matographic cleanup methods. Recently, an HPLC cleanup method for determina-
tion of PCBs in oils and waste oils has been devised (Chesler et al., 1982).
Acid Cleanup—
Sulfuric acid is added as the first step of many cleanup procedures to
remove gross interferences, although a number of studies found sulfuric acid
cleanup alone sufficient for PCB analysis (Ahling and Jensen, 1970; Becker
and Schulte, 1976; Haile and Baladi, 1977; Hattula, 1974; Mattson and Nygren,
1976; Murphy, 1972; Veierov and Aharonson, 1980; Harris and Mitchell, 1981).
Losses of the mono- to trichlorobiphenyls were reported in two studies (DCMA,
1981; Lincer, 1973) which used a heated sulfuric acid cleanup. No losses were
observed at room temperature (Haile and Baladi, 1977). The chemical destruc-
tion cleanup methods are extremely useful but care must be taken to ensure
valid recoveries of the particular PCB isomers of interest. For example, mono-,
di-, and trichlorobiphenyl isomers were not quantitatively removed from pigment
matrices that were treated with concentrated sulfuric acid (DCMA, 1981; Lincer,
1973). Low recoveries were presumed to be due to sulfonation of the biphenyl
ring (Lincer, 1973).
Liquid-liquid Partitioning--
Liquid-liquid partition is also used to remove large amounts of inter-
ferences from water, wastewater, milk, food products, packaging materials,
silicone fluids, oil, and tissue extracts before final cleanup by a chromatog-
raphy technique (EPA, 1978; Gordon et al., 1982; Leoni et al., 1973; Mulhern
18
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et al., 1972; Siyali, 1973; Swift and Settle, 1976; Tessari, 1977; Tessari
and Savage, 1980; Klimisch and Ingebrigtson, 1980; Welborn et al., 1974).
Large amounts of an interference in a sample extract, such as the lipid con-
tent of a tissue extract, has a pronounced effect on the efficiency of liquid-
liquid partition cleanups (Albro, 1979). Validation of a cleanup procedure
using spiked blanks provides much better recovery values than can be achieved
for an actual sample. Therefore, it is necessary to spike actual sample ex-
tracts to fully characterize the limitations of this type of cleanup step.
Seidl and Ballschmiter (1976b) have demonstrated PCB recoveries of greater
than 90% for cleanup of vegetable oil extracts by liquid-liquid partition with
hexane and dimethylformamide.
Saponification—
Saponification of the sample matrix has been discussed as a method for
extracting PCBs from certain materials. Saponification may also be considered
a cleanup procedure (Lincer, 1973; Tatsukawa and Wakimoto, 1972; Trotter, 1974).
Saponification of sample matrices with ethanolic potassium hydroxide has been
accomplished without chemical change to the PCBs present (Young and Burke,
1972).
Miscellaneous—
Other cleanup procedures that have been shown to be effective but have
limited use are low temperature precipitation of lipids from tissues and hu-
man milk samples prior to solvent extraction or liquid-liquid partitioning
(Mes et al., 1977a, 1977b; Mes and Campbell, 1976). Oxidation of interfering
chloronaphthalenes and chlorinated pesticides such as DDT and DDE with chro-
mium trioxide or chromic acid has been shown to be effective when used in con-
junction with a final chromatographic cleanup (Holmes and Waller, 1972; Mulhern
et al., 1972; Underwood et al., 1979). However, Szelewski et al. (1979) have
questioned the reliability of the chromium trioxide oxidation of interferences
in sample extracts. Fish extracts, spiked with Aroclor 1016, 1221, and 1254,
were treated with the chromium trioxide oxidation technique. Recoveries of
Aroclor 1016 from this oxidation step ranged from 30 to 90% for eight repli-
cates, while Aroclor 1254 recoveries ranged from 40 to 80% for eight replicates.
Aroclor 1221 was reported to have 0% recovery from this oxidation step for
six replicate samples. Szelewski et al. (1979) theorized that PCBs in the
extracts were lost by oxidation, by volatilization due to the highly exothermic
nature of the oxidative process, or a combination of the two. Steam distilla-
tion of water, sediments, and tissues provides relatively clean extracts that
require little or no additional cleanup (Veith and Kiwus, 1977; Dougherty et
al., 1980). Interference from elemental sulfur is a serious problem, espe-
cially for electron capture detector methods of analysis. The sulfur inter-
ference in water, wastewater, sewage sludges and sediments can be effectively
removed by precipitation of sulfur with mercury (Bellar and Lichtenberg, 1976;
Goerlitz and Law, 1974; Rodriguez et al., 1980) or by converting sulfur to
thiosulfate by addition of tetrabutylammonium sulfate (Jensen et al., 1977).
Recovery Measurement
Regardless of the cleanup procedure required for PCB analysis from a par-
ticular sample, it is of utmost importance to document recovery of PCBs from
the method. Routine quality assurance governs that the recovery be determined
19
-------
for each different sample matrix encountered. Also, recovery of the PCBs
should be determined each time a given parameter of an established cleanup
procedure is changed. For example, different batches of an adsorbent may dif-
fer greatly with respect to activation. Cleanup steps should be monitored
with spiked samples to support overall quality of the data. In some instances,
a visible marker such as azulene can be used as a real time monitor to deter-
mine the performance of column chromatography methods (Nowicki, 1981).
DETERMINATION
Thin-Layer Chromatography
In addition to its use as a cleanup technique, thin-layer chromatography
(TLC) has been used extensively as a determination technique. TLC was used
early (latter 1960s, early 1970s) because HPLC was not readily available and
the GC techniques were not well-developed. Most of the early TLC reports were
normal phase (silica gel) and included elaborate cleanup steps to remove in-
terferents (e.g., oxidation of DDE to a benzophenone derivative).
In the mid-1970s when packed column gas-liquid chromatography/electron
capture detection (PGC/ECD) became the method of choice, emphasis on TLC meth-
ods dwindled. Several articles have been published which take advantage of
modern TLC techniques: high performance TLC, two-dimensional TLC, reverse
phase TLC, and new detection methods.
TLC has been shown to be an effective technique for determination of
(Aroclor) PCBs in a wide variety of matrices. The advantages included its
ease of use and the simplicity of the apparatus. The disadvantages include
lack of resolution, moderate sensitivity, and specificity.
Review Articles--
TLC analysis of PCBs was reviewed by Fishbein (1972).
Standard Methods—
TLC is included as an alternate technique for "semiquantitation" analysis
of PCBs in human adipose tissue in EPA manuals (Watts, 1980; Sherma, 1981).
It is also included in the Association of Official Analytical Chemists methods
for confirmation of identity (AOAC, 1980).
TLC is mentioned by the Food and Drug Administration (1977) as a tech-
nique which they feel may also be useful in dealing with particular resin com-
binations.
Primary Literature—
Since the publication of a TLC method for PCBs by Mulhern (1968) and
Mulhern et al. (1971), several researchers have used a similar method for anal-
ysis of PCBs in food (Stijve and Cardinale, 1974), animal feeds (Westoo and
Noren, 1970), food packaging (Zimmerli et al.), bald eagles (Bagley et al.,
1973), Aroclor mixtures (Willis and Addison, 1972), animal tissue (Collins et
al., 1972; Koeniger et al., 1975; Bush and Lo, 1973; Hattula, 1974; Mes et
al., 1977), human adipose tissue (Price and Welch, 1972; Lucas et al., 1980),
and human milk (Savage et al., 1973a, 1973b; Mes and Davies, 1979).
20
-------
Many of these researchers employed TLC in conjunction with other tech-
niques such as GC/ECD. Often, TLC was used as a confirmation technique.
Several publications have reported developments claimed to improve the
technique. Circular TLC reportedly improves sensitivity by an order of mag-
nitude with a PCB limit of detection of about 0.05 M8 (Koch, 1979). Fused
glass TLC has been reported as yielding longer plate life (Okamura et al.,
1973). Reverse phase TLC has been reported to yield better separation of PCBs
from interferences (deVos and Peet, 1971; deVos, 1972; Stalling and Huckins,
1973; Brinkman et al., 1976a). An impregnated silica gel plate has been re-
ported (Bergman et al., 1976) which improves selectivity apparently on the
basis of ion-pairing. The use of surfactant micellar solutions as the mobile
phase is certainly novel and reportedly has potential for separation of chlo-
rinated aromatics, including decachlorobiphenyl (Armstrong and Terrill, 1979).
Improvements in detection have included an AgN03 spray followed by UV irradia-
tion (deVos and Peet, 1971; deVos, 1972; Kawabata, 1974) and fluorescence (Kan
et al., 1973; Ueta et al., 1979). A two-dimensional TLC method was developed
which barely separated the DDT analogs from PCBs (Fehringer and Westfall, 1971).
This last reference points to one of the major problems with TLC deter-
mination of PCBs. Many common interferences (e.g., DDE in biological tissues)
have similar elution characteristics and are not easily resolved. One common
technique for removal of DDE prior to TLC is oxidation of the DDE to dichloro-
benzophenone with chromium trioxide or other oxidant (Biros et al., 1972;
Sherma, 1981; Watts, 1980; Collins et al., 1972).
Two studies (Bush et al., 1971; Collins et al., 1972) compared TLC and
GC/ECD. In both studies the PCB values obtained were generally comparable,
although in the study by Bush et al., the TLC results were generally lower
than GC/ECD.
Lucas et al. (1980) reported a statistical analysis of semiquantitative
determinations of PCBs in human adipose tissue generated by the EPA's National
Human Monitoring Program during FY 1972 to 1976. Results were reported only
as ranges (not determined, < 1, 1 to 3, and > 3 ppm) for 5,259 samples. The
EPA TLC technique (Watts, 1980; Sherma, 1981) was used in this study through
November 1974 and a GC/ECD technique involving a single PCB peak quantitation
was used thereafter. A total of 3,802 TLC results and 1,457 PGC/ECD results
were compared and not found significantly different.
High Performance Liquid Chromatography
High performance liquid chromatography (HPLC), with ultraviolet and other
detectors, has been reported in the characterization of commercial PCBs as a
cleanup technique and as an analytical technique. Despite its general applica-
bility in analytical chemistry, HPLC has not been as popular as gas chromatog-
raphy (GC) for PCB analysis. The major reason is that GC detectors, especially
those selective toward halogens, exhibit much lower limits of detection.
Since HPLC is basically an instrumental version of the column chromato-
graphic cleanup techniques, described above, it is applicable both as a cleanup
21
-------
and a determination technique. Some researchers have exploited this and com-
bined cleanup and determination into one step with HFLC (Hanai and Walton,
1977; Van Vliet et al., 1979).
Review Articles—
Krull (1977) mentioned HPLC in a review of PCB analysis. Lawrence and
Tuiton (1978) reviewed the HPLC data on pesticides, including PCBs in their
tabulation.
Standard Methods--
No standard methods utilize HPLC.
Primary Literature—
Several authors (Brinkman et al., 1976a, 1976b; Veith and Austin, 1976;
Albro and Parker, 1979; Brinkman and deVries, 1979) have used HPLC in char-
acterization of commercial PCB products or establishing the chemical behavior
of PCBs.
HPLC has been used as a cleanup technique prior to gas chromatographic
determination (Aitzenmiiller, 1975; Dark and Grossman, 1973; Rohleder et al.,
1976; Krupcik et al., 1977; Dolphin and Willmott, 1978). More recently it
has been used on a preparative scale to clean up waste and transformer oils
prior to CGC/ECD determination (Anonymous, 1982; Chesler et al., 1981). In
the course of these investigations, the researchers noted that the CGC/ECD
limit of detection was about 100 times lower than the HPLC/UV limit of detec-
tion.
As HPLC became increasingly popular in the early 1970s, Eisenbeiss and
Sieper (1973) performed preliminary investigations of the use of HPLC for pes-
ticide (and PCB) analysis. They concluded that HPLC can be regarded as an
alternative or supplementary method to conventional methods such as gas chro-
ma tography.
Hanai and Walton (1977) developed an HPLC/UV method for determining PCBs
in water. No LOD was determined, but good recoveries were obtained for 250-|Jg/
liter Aroclor 1232 spiked into distilled water. The water was pumped directly
through the HPLC system and the PCBs subsequently eluted by gradient elution.
A similar application (Van Vliet et al., 1979) used an HPLC precolumn to con-
centrate PCBs from water and then elute them onto the analytical column for
separation and determination.
Belliardo et al. (1979) developed an HPLC/UV procedure for PCBs in oil
and compared it with a PGC/ECD method. The HPLC method was judged suitable
to approximate, but not quantitate, the PCB content.
Seidl and Ballschmiter (1979) used HPLC/UV to detect biphenyl after de-
hydrochlorination of PCBs.
Electron capture detection of HPLC effluents has been described (Willmott
and Dolphin, 1974) for the analysis of PCBs. The LOD of HPLC/ECD is reported
to be about 10 times higher than for GC/ECD (Brinkman et al., 1978). Stalling
et al. (1980) gave a preliminary description of an HPLC/MS (presumably the
chemical ionization MS mode) system for rapid screening for PCBs.
22
-------
Gas Chromatography
Gas chromatography (GC), in combination with various detectors, has been
by far the most popular and useful analytical procedure for PCBs. In recent
years, capillary column GC (CGC) has been used increasingly, although most
investigators still use packed column GC (PGC). The popularity of GC lies in
its resolution and speed (most PGC analyses take less than 30 min) and the
sensitivity (ECD), selectivity (ECD, HECD), and specificity (electron impact
mass spectrometry) of the available detectors.
Separation—
Packed column GC (PGC)—Over 215 references were abstracted which used
PGC as the analytical separation technique. The vast majority of these used
PGC in a routine manner with a common liquid phase. The quality of the chro-
matography (resolution and tailing) was generally adequate for low resolution
separation of Aroclor-derived samples into a "fingerprint" for identification
or quantitation. Since the Aroclor mixtures are too complex for resolution,
little or no emphasis was placed on improving resolution by PGC.
The most common PGC detector has been ECD. ECD has historically required
isothermal GC operation (not so with modern instruments). Figures 1 and 2
present some PGC/ECD chromatograms (Mullin and Filkins, 1981).
Review articles—By 1971 sufficient work in PCB analysis by PGC had
been completed to merit a review (Reynolds, 1971). This was followed by sev-
eral other reviews (Fishbein, 1972; Hutzinger et al., 1974; Fuller et al.,
1976; Krull, 1977; Margeson, 1977; and CMA, 1981). One review by Sherma
(1975) was devoted to PGC analysis of PCBs and related chlorinated aromatic
pollutants.
Standard methods—PGC is the recommended analytical separation
method in all but one of the 11 standard methods listed in Table 1.
Primary literature—Since over 215 citations on the use of PGC in
the analysis for PCBs have been abstracted, a complete discussion of the pri-
mary literature would be a formidable task. Most of these citations used PGC
in a routine manner and included little or no discussion as to why a liquid
phase or GC condition was chosen (if they were even mentioned). Several
articles are worth noting.
Albro et al. (1977) evaluated 13 packed columns ranging in polarity
from Apiezon L to OV-225. The number of observed theoretical plates ranged
from 491 to 3,833. None of the columns could successfully resolve all PCBs.
In the best case, it was calculated that of the 21,945 theoretically possible
pairs of PCB congeners, 465 would be indistinguishable using the best column
tested. The researchers discussed the use of multiple columns for resolving
indistinguishable pairs and concluded that five columns were necessary to re-
solve all isomers. Thus, using this scheme, each sample would have to be
analyzed once on each of five PGC columns to resolve all congeners.
23
-------
LU
z
o
Q.
c/3
LU
cc
er
O
O
LU
I-
LU
Q
34
TIME, min
ii(Hi) - A3
CO
1
CO
tr
O
u
120
60
TIME, min
INJ
Figure 1. Comparison of packed column gas-liquid chromatography (top)
and capillary column gas-liquid chromatography (bottom) with Aroclor
1242 and 1260 standards (Mullin and Filkins, 1981).
24
-------
UJ
w
O
85
LU
£T
CC
O
u
LU
H
LD
Q
34
TIME, min
INJ
:I(]|.,P • 4o i-
• 1
1
100
/SIT
I I
id
. ML
i| |
i
1
•z
i
--
-T
y
k
i i
70 30
|
i
i
;
1
UJ
Z
O
8s
LU
CC
CC
O
0
LU
LU
Q
INJ
TIME, min
Figure 2. Comparison of packed column gas-liquid chromatography (top)
and capillary column gas-liquid chromatography (bottom) with a milk
extract (Mullin and Filkins, 1981).
25
-------
Albro and Parker (1979) applied this technique to the identifica-
tion of the components in Aroclor 1016 and 1242. The identity of 44 congeners
was reported.
A report by Jensen and Sundstrb'm (1974) presents what may be the
highest resolution PGC chromatogram of PCBs. Even though it was operated iso-
thermally, this 5.2-m Apiezon L column resolved 59 peaks in a Chlophen mixture.
Capillary column gas chromatography--CGC has not been nearly so popular
as PGC, although 42 citations have been abstracted. In recent years the qual-
ity of the CGC separations reported have been truly impressive. Despite these
advances, no CGC method reported or predicted will separate all 209 PCB con-
geners. As an example of the overlap problem, Pellizzari (1982a) reported
CGC/ECD and CGC/NCIMS identification of PCB congeners in an Aroclor 1016/1254/
1260 mixture. Of the 103 peaks listed, 73 were identified, but only 43 corre-
sponded to a single congener. The others were possibly two (19 peaks), three
(9 peaks), four (1 peak), or even six (1 peak) co-eluting congeners.
In addition to the problem of congener separation, interferences may co-
elute. EIMS can readily discriminate against non-PCBs; however, co-eluting
major components may affect the mass spectral response of PCBs.
Review articles--CGC was briefly cited (five references) in one re-
view (Sherma, 1975). An Aroclor CGC/ECD chromatogram was included in a CGC
monograph (Jennings, 1978) as an application of CGC.
Standard methods—One of the 11 standard methods in Table 1 recom-
mends CGC, specifically a support coated open tubular (SCOT) column coated
with FFAP (free fatty acid phase) for analysis of PCBs in capacitor Askarels.
EPA Method 625 (EPA, 1979b) recommends PGC or if desired, capillary or SCOT
columns may be used. Capillary gas chromatography is also allowed, if desired,
for the analysis of PCBs in transformer fluids or waste oils (EPA, 1981).
Primary literature—CGC was utilized in 43 articles abstracted for
this review. The level of detail and column specifications span a wide range.
Sissons and Welti (1971) published an early article which characterized many
of the PCB isomers in Aroclor 1254. Using an Apiezon L packed column, 23
peaks were resolved, while the same phase on a SCOT column (24,000 to 27,000
plates) separated 65 peaks. The next year, Webb and McCall (1972) performed
similar experiments using an SE-30 SCOT column. Although the resolution was
poor by today's standards, Biros et al. (1970) used CGC/EIMS to determine PCBs
in human adipose even earlier.
Krupcik et al. (1971) evaluated metal WCOT columns coated with
Apiezon L or OV-101 and found them unsuitable. However, OV-101 on a glass
WCOT column gave good results. An example of the separations obtained by CGC
using liquid phases of different polarity is shown in Figure 3 (Krupcik et
al., 1977). The quality of the chromatography is less than optimal because
the GC was operated isothermally. Krupcik et al. (1982) have also reported
on the optimization of experimental conditions for the analysis of complex
mixtures by capillary gas chromatography. The optimization procedure for com-
plex materials was demonstrated with Aroclor 1242. Forty PCBs were separated
26
-------
I! f
Separation of a PCB mixture by GLC on a glass capillary column coated with OV-101 at
200 °C (column E).
T '
LlJU
JO *•
Separation of PCB mixture by GLC on a glass capillary column coated with Carbowax 20M
at 200 °C (column F),
Figure 3. Comparison of PCB resolution on different columns
(Krupcik et al., 1977).
27
-------
at 170°C using a 40.0 m Carbowax 20M glass capillary column connected to a
75.6 m Apiezon L glass capillary column.
Using a 50-m Dexsil 410 glass capillary Albro et al. (1981) have
achieved 175,000 effective theoretical plates for 2,3,5,2',3',5'-hexachloro-
biphenyl. Resolution of Aroclor 1260, which required an isothermal chromato-
gram of 5 h, generated 110 peaks, of which only 4 were unidentified. Even at
this resolution, the Dexsil 410 did not resolve all congener pairs. Less ef-
ficient columns coated with Silar 5 C, Apiezon L, and OV-25 were used to pro-
vide different separations which resolved the congener pairs not previously
resolved.
Although no column performance parameters were given, Mullin and
co-workers have achieved impressive resolution by temperature-programmed CGC/
ECD on C-87 columns (Mullin and Filkins, 1981; Mullin et al., 1981) and SE-54
columns (Safe et al., 1982).
Pellizzari et al. (1981) have compared a number of capillaries (cap-
illary material, pretreatment, and liquid phase). Apiezon L was judged to be
the best of the liquid phases tested (SE-54, C-87, SP-2100, and Apiezon L),
for PCB analysis, based on resolution, separation number, and HEETP. Two ex-
amples of this column's performance are shown in Figures 4 and 5. This con-
clusion supports that of several other investigators who have used and recom-
mend Apiezon L (Sissons and Welti, 1971; Albro et al., 1977; Stalling et al.,
1978; Albro et al., 1981; Jensen and Sundstrom, 1974; Nakamuna and Kashimato,
1977; United Kingdom Department of the Environment, 1979) or similar hydro-
carbon phases for PCB analysis (Mullin and Filkins, 1981).
Tuinstra and coworkers (Tuinstra and Traag, 1979a, 1979b; Tuinstra
et al., 1980; Tuinstra et al., 1981) have explored the automation of CGC/ECD
analysis with autoinjection onto a splitless injector. This approach, although
not thoroughly presented in Tuinstra (no mention of sample throughput or auto-
mation of data recording and reduction is mentioned), should be pursued by
laboratories facing large sample loads.
Recently, bonded liquid phases have been made available on capillary
GC columns. These exhibit low bleed and background and have long lifetimes.
Figure 6 presents a CGC/EIMS chromatogram of a PCB standard on a DB-5 column.
It is interesting to note that J&W Scientific, Analabs, and Supelco
present CGC/ECD chromatograms of Aroclor mixture in their catalogs. This in-
dicates that CGC is commercially available and that the capillary manufacturers
consider their PCB separations good enough to advertise.
Comparison of PGC and CGC—The relative merits of PGC and CGC are
well-known and apply to the separation of PCBs. CGC provides better resolu-
tion, retention time precision, and higher qualitative reliability. PGC
yields a simple chromatogram (less data reduction), permits higher sample
loading (and therefore possibly lower LOQs), and is generally considered easier
to use. Historically, PGC quantitation has been more precise, although it
has not been established how much of the imprecision attributed to CGC has
been due to poor technique on the part of the analyst.
28
-------
Figure 4. Electron capture detection of Aroclors 1242, 1260, and 5460
(400 pg each) chromatographed on an Aoiezon L (WCOT) silanized
Pyrex glass capillary, 0.20 ram i.d. x 50 m in length. The carrier
was 53 cm/s; capillary was temperature-programmed from 150 to 390°C
at l°C/min (Pellizzari et al., 1981).
Figure 5. Electron capture detection of PCB in an extract of yellow perch.
See Figure 4 for chromatographic conditions (Pellizzari et al., 1981).
29
-------
Sample: Combined Aroclor 1248,1254,1260
250ng/>l & DCB 100ng//il, 1/il Injection
10
800 1000
20:00 25:00
1200
30:00
2000
50:00
2200 SCAN
55:00 TIME
Figure 6. Scanning capillary column gas-liquid chromatography/mass
spectrometry analysis of a mixed Aroclor standard used to
establish retention windows for the CGC/MS-selected
ion monitoring analysis of PCBs.
Instrumental parameters: column, 15-m, fused silica, DB-5; column
temperature, 80°C for 2 min, 8°C/min to 300°C; helium carrier at
2.5 psi; J&W on column injector. (J. S. Stanley and C. L. Haile,
Midwest Research Institute, personal communication, 1982).
30
-------
Figures 1 and 2 (Mullin and Filkins, 1981) present graphic compari-
sons of PGC and CGC results for PCBs. Similar results have been presented by
Onsuka and Comba (1978).
Detectors—
GC detectors are classified as either universal or selective. The ECD
and HECD are highly selective toward halogenated compounds. This selectivity,
coupled with its extreme sensitivity, has made ECD very popular for analysis
of trace levels (residues) of pesticides and PCBs and has, in fact, had a sig-
nificant role in regulatory actions on these classes of compounds. FID is
the most common GC detector and is a universal detector, giving similar re-
sponses for most organic compounds. Thus, FID would be unsuitable for detec-
tion of PCBs in a complex matrix.
Mass spectrometry and Fourier transform infrared spectrometry (FTIR) are
in essence both universal and selective GC detectors. By focusing on a spec-
tral property characteristic of a compound or class of compounds, these de-
tectors can be quite specific. However, by using the full spectral range,
nearly any compound eluting from the GC will be detected. Due to the much
higher information content of mass and infrared spectra, identifications by
GC/MS or GC/FTIR are generally made with greater certainty than by other de-
tectors .
The analysis of PCBs generally requires selectivity and sensitivity.
Usually, even after cleanup, PCBs are a minor component of the sample, mixed
in with other halocarbons (e.g., DDE), hydrocarbons, lipids, etc. Thus, the
detector must selectively detect PCBs in the presence of other compounds pres-
ent at orders of magnitude higher concentration. Furthermore, the levels typ-
ically observed in food, biota, tissue, soil, and other matrices of interest
are in the parts per billion range. These levels strain the capabilities of
even the most sensitive detection device such as ECD, resulting in a large
number of "not detected" values in many reports.
The choice of detector often depends upon the level of analytes. Low
concentrations demand a detector capable of detecting low amounts (high sensi-
tivity) . Figure 7 presents the typical range and detection limits for most
of the GC detectors used in analysis for PCBs. The detection limit of the
HECD is 10"11 g with a linear range up to about 10 2 g, as measured for lin-
dane (Anderson and Hall, 1980). As can be seen, ECD exhibits the lowest limit
of detection (LOD).
The reported LOD for PCBs in a variety of matrices are listed in Table 2.
Comparison of the reported LODs is difficult because no standard definition
of LOD was used. Glaser et al. (1981) followed a rigorous definition and ex-
perimentally determined the LOD with a fair degree of confidence, while other
investigators clearly guessed at the LOD based on this work. The issue is
further clouded by inconsistency in discussing the LOD with respect to the
instrumental determination versus the entire procedure. Some LODs are re-
ported for standard solutions, while others take into account the interfer-
ences in the matrix which often raise the LOD considerably.
31
-------
Detection
Mode Selectivity Crams
10
-|J 10"17 10-" 10'10 10'9 10"* IO'7 10-* 10"s 10"* 10'3 10"
Thermal Eneigy +
Analyzei
Photoionization ±
Election Capture +
Mass Spectromelry
Election Impact
Multiple lanDet. +
Neg. Chemical Ion. +
Fluorescence +
Flame lonization
Thermal Conductivity
FT/1R *
UV
Figure 7. Detection limi'tsydynamic range for several ins'trumental methods (Pe-llizzari, 1981).
-------
TABLE 2. REPORTED LIMITS OF DETECTION FOR PCBs
to
10
Instrument
GC/ECD
GC/HECD
GC/EIMS
HREIMS
Reported LOD
0.065 JJg/JH
0.5 ppb
6.5 ppb
50 ppb
1-0.1 ppb/isomer
0.5 ppm
1 ppm
0.5 ppm
0.6 yg/£
1 ng/m3
0.1 ng/m3
3 pg/2
1 ppm
1 mg/kg
30 pg/£
36 pg/£
0.01-0.2 pg/£
5 ppm
10 ppb
Converted
LODa
(ug/g or ppm)
0.000065
0 . 0005
0 . 0065
0.05
0.001-0.0001
0.5
1.0
0.5
0.0006
D
NA
0.003
1 ppm
1.0
0.030
0.036
0.01-0.2
5
0.01
Substance
Aroclor 1242
Aroclors
Aroclors
Aroclors
Isomers
Aroclors
Total PCB
Total PCB
Perchlorinated
Perchlorinated
Theoretical
per isomer
Aroclor 1260
10 homo logs
Aroclors
Aroclor 1221
Aroclor 1254
Single isomer
Single isomer
Aroclors
Matrix
Dist. water
River water
Pure solution
Milk
Vegetable
Transformer fluid
Oil
Oils
Ground water
Air
Air
Blood serum
Pigments
Oil
Dist. water
Dist. water
Industiral sample
extract
Chlorinated
hydrocarbons
Biological
extracts
Reference
Glaser et al. , 1981
Kuehl et al. , 1980
Teichman et al., 1978
Tessari and Savage, 1980
Tuinstra et al. , 1981
Kirshen, 1981
Chesler et al. , 1981
Balya and Farrah, 1980
Stratton et al. , 1979
Stratton et al., 1978
Lewis et al. , 1977
Kreiss et al., 1981
DCMA, 1980
EPA, 1981
Glaser et al. , 1981
Glaser et al., 1981
Tindall and Winninger,
1980
Collard and Irwin,
1982
Safe et al., 1975
GC/NCIMS
None
(continued)
-------
TABLE 2 (continued)
Instrument
Dir. Probe
NCIMS
TLC
Reported LOD
** 1 ppb
0.5 ppm
< 0.04 ppm
0.1 jjg
0.05 M8
0.2 |Jg
1 M8
Converted
LODa
(pg/g or ppm) Substance
0.001 NSC
0.5 Aroclor
< 0.04 Aroclor
Aroclor
Aroclor
Aroclor
Aroclor
Matrix
Biological
extracts
Adipose
Milk
Animal tissue
NS
Animal tissue
NS
Reference
Dougherty et al.,
1980
Bush and Lo, 1973
Savage, 1973
deVos and Peet, 1971
Koch, 1979
Mulhern et al. , 1971
Ismail and Bonne r,
1974
a Converted to common units of micrograms per gram (parts per million) assuming 1 ml = 1 g density.
x-
b NA = not applicable.
c NS = not specified.
-------
Reviews Articles—
Every review article abstracted covered the subject of ECD detection of
GC effluents (Riseborough, 1971; Reynolds, 1971; Fishbein, 1972; Linear, 1973;
Hutzinger et al, 1974; Sherma, 1975; Fuller et al., 1976; Margeson, 1977; Krull,
1977; Safe, 1976). Fishbein (1972), Sherma (1975), and Hutzinger et al. (1974)
all reviewed the use of electrolytic conductivity detectors for PCB determina-
tion. Safe (1975) and Hutzinger et al. (1974) discussed the use of flame ion-
ization detection (FID), mostly with respect to calibration of ECD or estab-
lishing ECD response factors. Hutzinger et al. (1974) did mention that for
the mono- and dichlorobiphenyls FID and ECD sensitivities are comparable.
Standard Methods—
As noted in Table 1, most of the standard methods specify ECD as either
the detector or one of the options. FID is the detector prescribed in the
American Society for Testing and Materials (1980a) procedure for determining
PCBs in capacitor Askarels. In this case, the matrix is well-characterized
and generally contains no other compounds in the PCB retention window. HECD
is permitted as an alternate detector in three procedures (EPA, 1978; EPA,
1981; FDA, 1977).
Electron capture detection—Based on literature citations and number of
samples processed, the electron capture detector (ECD) has been the most com-
mon detector for GC analysis of PCBs. ECD is extremely sensitive for PCBs.
It does, however, detect many nonPCB compounds (halogenated pesticides, PCNs,
chloroaromatics, phthalate and adipate esters, and other compounds) which may
be differentiated from PCBs only on the basis of retention time. Figure 8
illustrates:the potential interferences from chlorinated pesticides.
A major disadvantage of ECD is the range of response factors (Tables 3
and 4) which different PCB congeners exhibit. This seriously inhibits relia-
ble quantitation. The opposite trends in the two tables presumably result
from differences in the equations used (i.e., whether the PCB response is in
the denominator or numerator). The earlier PGC/ECD work (Table 3) has a range
of about 1,400, while the later CGC/ECD work (Table 4) has a range of only
about 120. This may be a function of the differences in detector design and
GC column throughput. In addition, the CGC is temperature-programmed, while
PGC data were presumably obtained isothermally. Despite these differences,
both tables clearly illustrate that, even within a homolog, the % RSD is very
large and would result in poor accuracy if quantitation involves extrapolation
from one isomer to another. A recent report of the ECD relative response fac-
tors for all 12 octachlorobiphenyls showed a range from 0.007 to 2.644 with a
RSD of 35% (Mullin et al., 1981). This also illustrates the problem of PCB
quantitation by ECD. This subject is treated in more detail in the Quantita-
tion section.
Over 175 references were abstracted in which ECD was used as a GC detec-
tor. Any novel aspects of the articles dealt with qualitative or quantitative
aspects of ECD and will be treated in the appropriate subsections below.
35
-------
4%SE-30/6%OV-210
Chromatograms of three AROCLORS on column of
1£ SB-30 / 656 OV-210. Column temp. 200°C.,
carrier flow 60 ml/min., -^H detector, electroou
attenuation on an E-2 10 x 16; dotted line a
rdxture of chlorinated pesticides, identity and
injection concentration given below:
AROClOa 1248
1. Diazinon
2. Heptachlor
3. Aldrin
h, Hept.Epox.
5. p,p'-DDE
6. Dieldrin
1.5 ng 7. o,p'-DIJT — 0.2l»
0.03 8. p,p'-DDD ~ .?U
.OU5 9. p,p'-CDT — .30
.09 10. Dilan — .75
.0? 11. Methoxychlor .60
.12
ng
~ .12
AROaOR 1260
4 n» i
AtOQOI IIS4
Figure 8. Packed column gas-liquid chromatography/electron capture detector
chromatograms illustrating potential interferences between
pesticides and PCBs (Watts, 1980).
-------
TABLE 3. RELATIVE MOLAR RESPONSES OF ELECTRON CAPTURE AND FLAME IONIZATION
DETECTORS TO SOME CHLOROBIPHENYLS3
Chlorobiphenyl
2-
3-
4-
2,2'-di
2,4-di
2,6-di
3,3'-di
3,4-di
4,4'-di
2,4,4'-tri
2,2',4,4'-tetra
2,2',6,61-tetra
3,3',4,4'-tetra
3,3',5,5'-tetra
2,3,4,5-tetra
2,3,5,6-tetra
2,21,4,4',6,6t-hexa
3,3', 4,4' ,5,5'-hexa
2,21>3,31,4,4l,6,6-octa
2>21,3,3I,5,5l,6,61-octa
deca
N
Mean
SD
RSD (%)
Relative molar
Electron capture
1.00
0.20
1.10
5.16
17.7
32.0
6.10
15.2
5.97
135
106
20.6
396
320
367
259
347
726
1,180
1,150
1,410
21
310
438
140
response
Flame ionization
1.00
0.92
0.87
0.99
0.86
0.91
0.94
0.86
0.81
0.78
0.87
0.90
0.87
0.85
0.87
0.71
16
0.88
0.07
8.3
a Taken from Hutzinger et al., 1974, and Safe, 1975.
37
-------
TABLE 4. COMPARISON OF RELATIVE RESPONSE FACTORS BETWEEN (GC)2-ECD, GC-EIMS (MOLECULAR ION)
AND (GC)2-NICIMS (ro/z 35) FOR HOMOLOGOUS SERIES OF PCBs*
U)
oo
Homolog
secies
1C1(3)
2C1(12)
3C1(24)
4CK42)
5C1(46)
6C1(42)
7C1(24)
8C1(12)
9C1(3)
10C1(1)
Range
15 089-39.342
0.425-10.641
0.328-2.136
0.385-2.229
0.462-8.481
0.391-1.912
0.402-2.432
0.925-2.602
1.005-1.816
-
Overall:
(GC)2 -BCD"
Mean ± S.D. (% RSD)
29.589 ± 12.78 (43)
4.271 t 3.83 (90)
1.193 ± 0.68 (58)
1.074 ± 0.41 (38)
1.266 ± 1.29 (102)
0.973 ± 0.335 (35)
1.220 i 0.419 (34)
1.514 ± 0.679 (45)
1.291 ± 0.45 (35)
1.168
0.328-39.342
(•»• 120:1)
(GC)2-NICIMS°
NC
3
9
9
31
35
37
21
10
3
1
Range
0.456-1.787
2. 881-21. 199
0.721-10.901
0.102-4.267
0.465-1.216
0.369-1.440
0.236-1.192
0.241-1.116
0.066-0.565
-
Overall:
Mean ± S.D. (X
0.924 ± 0.75
8.343 ± 6.17
2.921 ± 3.64
2.058 ± 1.02
0.805 i 0.27
0.817 t 0 29
0.703 ± 0.30
0.573 ± 0.26
0.354 ± 0.26
0.418
0.066-21.199
(•>• 320:1)
RSD)
(81)
(74)
(125)
(50)
(33)
(36)
(43)
(46)
(73)
N
3
8
7
16
12
16
13
8
3
1
Range6
.000-1.090
000-2 062
.000-1.627
.000-2.146
000-1 013
.000-1.321
-
1 000-1.359
-
-
GC-EIMSb
Mean i S.D.
.050 ± 0.
.736 ± 0.
.400 ± 0
.549 ± 0.
.004 + 0.
153 ± 0
-
1.179 i 0
-
-
tt RSD)
04 (3 8)
30 (17)
24 (17)
33 (21)
01 (0.7)
11 (9 6)
25 (22)
N
3
10
9
11
3
7
0
2
0
0
* From Pellizzari et al. (1982).
a RT1 data.
b Martelli et al., 1981.
c N = number of PCB isomers included in measurement.
d All values are relative to octachloronaphthalene.
e Responses were relative to lowest response for each group.
f ( ) = number of theoretical isomers possible.
-------
Flame ionization detection—Flame ioaization detection (FID) is the most
commonly used GC detector because of its sensitivity and universality. Al-
though some investigators have used FID for PCB determination in samples, it
has generally been used only for calibration of response factors or other
method development work.
FID has been used for determination of PCBs in environmental samples
(Mizutani and Masayoshi, 1972; Modi et al., 1976; Lao et al., 1976; Onsuka
and Comba, 1978). Biros (1971) split the GC effluent to FID for quantitation
and EIMS for identification. Cook et al. (1978) and Zimmerli (1974) used FID
to detect biphenyl following dehydrochlorination of PCBs; a technique termed
carbon skeleton chromatography.
Most of the FID applications have been in establishing response factors,
characterizing Aroclors, or other method development areas (Webb and McCall,
1972; Ugawa et al., 1973; Dexter and Pavlou, 1976; Boe and Egaas, 1979; Albro
and Parker, 1980; Albro et al., 1981; Stalling et al., 1982). An example of
the use of FID is presented in Table 3, where the molar responses of FID and
ECD were compared (Hutzinger et al., 1974; Safe, 1975).
Thermal conductivity (TCP)—Hirwe et al. (1974) used TCD to characterize
Aroclor mixtures. This application is similar to many of the FID applications.
Electrolytic conductivity—The Hall (and its predecessor, the Coulson)
electrolytic conductivity detector (HECD) has been used often in PCB analysis.
It is much less subject to interference from nonhalogenated compounds than
ECD and the response is proportional to the number of chlorines. The high
limit of quantitation and difficulty of operation are the disadvantages of
this detector. Webb and McCall (1973) and Sawyer (1978) used Hall detection
in the characterization of Aroclor standards. Serum et al. (1973) used it,
ECD, and electron impact mass spectrometry as PGC detectors in analysis of
paper products for PCBs and other compounds. Hofstaedter et al. (1974) de-
termined that sulfur compounds in certain petroleum oils gave positive inter-
ferences in PGC/ECD determinations of PCBs. Flame photometric, microcoulo-
metric, and Hall detectors were used to characterize the PCBs and interferences.
Chesler et al. (1981) characterized oil products in the preparations of National
Bureau of Standards standard reference materials for PCBs in oil. They used
both ECD and HECD as CGC detectors. The ECD was found to be more sensitive
than the HECD by two orders of magnitude and easier to maintain in a non-
contaminated state. However, ECD response factors varied for different PCB
isomers, whereas the molar response to chlorine which is obtained from the
HECD appeared to be constant. The HECD exhibited a wider linearity range
and is more selective as it responded only to halogenated compounds.
An interesting, though tangential, use of HECD was presented by Dolan et
al. (1972), Dolan and Hall (1973), and Su and Price (1973). By adjusting the
HECD operating parameters they selectively detected organochlorine pesticides
in the presence of PCB interferences.
Electron impact mass spectrometry—Electron impact mass spectrometry
(EIMS) ranks second only to ECD in popularity as a GC detector for PCBs.
39
-------
Electron impact has been and continues to be the most widely used MS ioniza-
tion technique. While the chemical ionization (CI) and negative chemical ion-
ization (NCI) techniques are often more sensitive, their operation is more
complicated and variation in the spectra and response are higher.
EIMS has been applied to PCB determination using both direct probe and
gas chromatography for sample introduction. Early work generally employed
the then-exotic technique as a confirmation technique. In recent years, as
GC/ EIMS has become more routine, more and more analysts have chosen GC/EIMS
as the primary technique.
Review articles--The application of EIMS to analysis for PCBs has
been reviewed by Fishbein (1972), Oswald et al. (1974), Hutzinger et al.
(1974), and Safe (1975).
Standard methods--As listed in Table 1, several of the standard
methods use GC/EIMS, either as the primary analytical technique or as the con-
firmatory technique.
Primary literature—In 69 articles abstracted, EIMS was used. The
applications ranged from confirmation to routine use, from direct probe to
CGC, and from Aroclor characterization to analysis of dirty samples.
Among the pioneers, Biros et al. (1970) used CGC/EIMS to determine
PCBs in human adipose tissue; Sissons and Welti (1971) used CGC/EIMS in the
characterization of Aroclor 1254; and Bonelli (1972) presented PGC/EIMS data
for an Aroclor 1254/chlorinated pesticide mixture.
In addition to Sissons and Welti (1971), Webb and McCall (1972,
1973), Ugawa et al. (1973), and Oswald (1974) employed GC/EIMS in characteri-
zation of commercial PCB products. Using both electron impact and chemical
ionization mass spectrometry, Oswald et al. (1974) were able to differentiate
some isomers in complex mixtures from their spectra.
While full spectra provide the most qualitative information, the
use of selected ion monitoring enhances the instrument sensitivity and selec-
tivity and simplifies data interpretation. Examples of this technique have
been presented by Beggs and Banks (1976), Eichelberger et al. (1974), Martelli
et al. (1981), Collard and Irwin (1982), Erickson and Pellizzari (1977, 1979)
and Tressl and Wessely (1976). Especially with the more highly chlorinated
homologs, several m/z values are available for monitoring. Eichelberger et
al. (1974) addressed the criteria for selection—intensity and probability of
interference from higher homologs or other compounds.
A compromise between full scan and SIM techniques is mass chroma-
tography. Full spectra are collected and then ion intensity versus file po-
sition plots are extracted from the data by the computer. Thus, mass chro-
matography has the ease of interpretation of SIM but higher LOQs since full
spectra are collected. These full spectra are available for qualitative use
if needed. Canada and Regnier (1976) presented a technique which used mass
chromatography to monitor the ion ratios in the PCB isotopic clusters.
40
-------
Another compromise technique, limited mass scanning (LMS), involves
(as the name implies) scanning the spectrometer only over the mass range of
interest (e.g., molecular ion cluster). This permits the spectrometer to
spend more time on the ions of interest and thus achieve better sensitivity
than the full scan mode. Tindall and Wininger (1980) utilized LMS in their
PGC/CIMS analysis of commercial products for incidental PCBs.
Albro and Parker (1980) utilized PGC/EIMS as part of a general an-
alytical scheme for chlorinated aromatic pollutants.
Positive chemical ionization mass spectrometry—Positive chemical ioni-
zation (CI) mass spectromery (CIMS) is one of the "soft" ionization techniques
which tend to produce fewer fragments. Thus, the spectra are simple and the
molecular ion is generally one of the most intense peaks. However, with PCBs,
the electron impact spectra generally exhibit good molecular ions, reducing
the advantages of CI. Another problem with CI is that the ionization process
depends on a reagent gas introduced with the sample into the source. Slight
changes in gas pressure, source temperature, and electronic conditions can
affect the reaction conditions and thus the spectrum (both fragmentation pat-
terns and overall intensity). Thus, CI is not as reproducible as electron
impact, either qualitatively or quantitatively.
Several researchers have utilized GC/CIMS for determination of PCBs.
Oswald et al. (1974a), Sawyer (1978), and Cairns and Siegmund (1981) char-
acterized standard samples. Oswald et al. (1974b), lida and Kashiwagi (1975),
Stalling (1976), and Caims and Jacobsen (1977) applied GC/CIMS to PCB me-
tabolites, environmental samples, and food samples.
Dougherty et al. (1973) reported the use of direct probe positive and
negative CIMS for the analysis of human adipose tissues for PCBs. Stalling
et al. (1980) reported an HPLC/MS technique for PCBs which is presumed to use
the CI mode. This preliminary report speculated that HPLC/MS could be useful
as a screening technique for environmental samples.
A related but often defined as separate technique, atmospheric pressure
chemical ionization has been reported for PCB determination. Dzidic et al.
(1975) reported subpicogram detection of 2,3,4,5,6-pentachlorobiphenyl, and
Thomson and Roberts (1980, 1982) used the technique for in situ detection of
PCBs in clay and soil.
Negative chemical ionization mass spectrometry—Negative chemical ioniza-
tion (NCI) mass spectrometry (NCIMS) is similar to both CIMS and ECD. The
basic difference between negative and positive CI is the polarity of the vari-
ous voltage potentials in the spectrometer and the detector. Many of the
chemical reactions in the NCI source and the ECD are the same. NCI and ECD
exhibit similar detection limits and selectivities toward chlorinated com-
pounds, thus the interest in NCI. The reproducibility problems of CI are also
present in NCI. The range of response factors found with ECD are also found
with NCI. NCIMS, a relatively recent technique, is still considered to be a
research technique.
41
-------
The group led by Dougherty has published extensively on the methods and
application of (direct probe) NCIMS (Dougherty et al., 1973; Kuehl et al.,
1980; Dougherty et al., 1980; and Dougherty, 1981a, 1981b). The technique is
described as rapid and highly selective toward halogenated compounds. The
latter advantage reduces the need for cleanup and, according to Dougherty
(198la), permits the analysis without the customary GC separation.
Kuehl et al. (1980) used both CGC/EIMS and CGC/NCIMS to analyze fish sam-
ples for a variety of chloroorganics, including PCBs. The electron impact
spectra were used for primary identification, although the NCI spectra were
also of great value. Figure 9 presents the NCI and electron impact TICs for
comparison. The NCI is much more selective toward the halogenated compounds,
eliminating the broad hump which is presumably a complex mixture of lipids
and oils from the fish matrix.
Pellizzari et al. (1981) have used CGC/NCIMS for analysis of PCBs and
have characterized the instrument operation parameters. The choice of reagent
gas and its pressure markedly affect the relative intensities of the major
peaks (m/z 35 and 37, molecular ion, etc.).
The response factors for several PCB congeners are presented in Table 4
(Pellizzari et al., 1982). As with BCD, the range of the response factors is
broad. This would probably make quantitation by extrapolation from a single
calibration isomer inaccurate.
While not directly used for PCB determination, CGC/atmospheric pressure
negative chemical ionization mass spectrometry was shown to be both sensitive
and selective for PCDDs in the presence of PCBs (Mitchum et al., 1982). With
proper selection of masses and ionization conditions, this technique may be
highly selective for PCBs.
High resolution electron impact mass spectrometry—HREIMS is capable of
obtaining precise and accurate mass measurements of a peak. This known mass
can correlate with only a few possible molecular formulas. As reviewed by
Safe (1975), HREIMS is particularly useful for chlorinated compounds because
the chlorine mass defect clearly distinguishes a halocarbon from a molecule
containing only carbon, hydrogen, nitrogen, and oxygen. Safe (1976) and Safe
et al. (1975) have reported the application of HREIMS to the analysis of crude
goat urine extracts and other biological samples for PCB and PCT metabolites.
The reported 10-ppb detection limit and the rapid analysis time (no GC separa-
tion is used) would appear to make this technique a suitable technique for
rapid screening of samples for the presence of PCBs. The lack of work in this
area, however, suggests that other considerations must reduce the applicability
of HREIMS.
Hass and Friesen (1979) illustrated the need for HREIMS to separate in-
terferences (if not chromatographically separated). The spectrum in Figure 10
shows that DDE, TCDD, and PCB would have given one peak under low resolution
conditions.
-------
£
O
I
NEGATIVE CHEMICAL IONIZATION
\J
L
1000 2OOO
Spectrum Number
3000
ELECTRON IMPACT
IOOO 2OOO
Spectrum Number
3000
Figure 9. Total ion current profiles for negative chemical ionization
data (upper) and electron impact data (lower) obtained on a
Finnigan 4000 glass capillary GC/MS system for
Ashtabula River fish sample
(Kuehl et al., 1980).
43
-------
DDE
•-! • • 1 1 1
322.000 321.900 321.800
Figure 10. Partial high resolution mass spectrum obtained from
2.5 x 10"10 g TCDD plus matrix from 10 g human milk,
illustrating potential interferences in
low resolution mass spectrometry
(Hass and Friesen, 1979).
Nonchromatographic Methods—
This section presents a variety of miscellaneous methods reported for
the determination of PCBs.
Nuclear magnetic resonance (NMR) spectrometry--Wilson and Anderson (1973)
used both 13C and 1H nuclear magentic resonance (NMR) to characterize the chem-
istry of selected PCBs. No attempt at analysis of real samples was made.
Levy and Hewitt (1977) reported the analysis of PCB mixtures by 13C NMR, but
noted that the technique was not as useful for higher homologs. Hutzinger et
al. (1974) included a discussion of the NMR characteristics of PCBs in their
review book. Synthetic congeners have been characterized by proton NMR (Mullin
et al., 1981).
Infrared (IR) spectrometry—Hutzinger et al. (1974) discussed the infrared
(IR) spectral properties of PCBs. Webb and McCall (1972) used IR and other
techniques to identify 24 PCB congeners in Aroclor 1221.
Radioimmunoassay—Albro and coworkers have reported preliminary results
in the development of a radioimmunoassay (RIA) method for PCBs (Albro et al.,
1979; Kohli et al., 1979; Luster et al., 1979, 1981). Suggestive evidence is
presented indicating the feasibility of employing radioimmunoassays for deter-
mining the Aroclor product number and concentration in environmental samples
(Luster et al., 1979). The assay requires an antiserum for each isomer but is
termed fairly specific.
Other techniques—Interrupted-sweep voltametry has been applied to the
identification of PCBs, yielding positive identifications (Farwell et al.,
1975). Plasma chromatography has been reported to give characteristic quali-
tative data for PCBs (Karasek, 1971). One report utilized neutron activation
analysis for the determination of PCBs in dosed rats (Mamri et al., 1971).
44
-------
identification and quantitation of PCBs (EPA, 1972; Brownrigg et al., 1974;
Brownrigg and Hornig, 1974). The limit of detection was reported to be as
low as 0.01 ppm.
DATA REDUCTION
Depending on the detection and output system, data may be presented to
the analyst as strip chart recorder chromatograms, digitized chromatograms,
numerical peak integrations, mass spectra, MS selected ion monitoring plots,
MS total ion current plots, etc. Computers can easily reduce the analyst's
work in data reduction and should be used for MS data acquisition and reduc-
tion. However, excessive reliance on data system output without interaction
by a qualified analyst can yield spurious results.
The first task in data reduction is to qualitatively identify the analyte.
Quantitation can be attempted only after a positive qualitative identification.
Qualitative
The qualitative aspects of the analysis are all too often overlooked.
Especially with PCBs, differences in the qualitative assessment of a sample
can dramatically affect the quantitative results. In standard methods or
other work where two or more analysts are expected to produce comparable re-
sults, the qualitative assessment of the data must be carefully specified.
As an example of how qualitative interpretation of results can affect
quantitation, a round robin study was recently conducted to assess the inter-
laboratory variability of PCB analysis in commercial products (Pittaway and
Homer, 1982). Eleven data sets, generated by PGC/ECD, PGC/ EIMS, PGC/EIMS
SIM, CGC/EIMS, and PGC/FID, were acquired (see Tables 5 and 6). While most
of the techniques were sufficiently specific to differentiate PCBs from inter-
ferences, the PGC/FID was not. Since no attempt was made by the analyst to
differentiate PCBs from interferences in this case, the PGC/FID quantitation
was 28 times higher than the mean of the other analyses.
Qualitative assessment of results depends to a large extent on sample
type and its pretreatment. In samples where the presence of PCBs has been
well-established (e.g., adipose tissue) the qualitative burden is not nearly
so great as for samples in which PCBs are not expected. In many PCB proce-
dures, the cleanup involves a rather specific liquid chromatographic separa-
tion which separates PCBs from most organochlorine pesticides. In addition,
the use of specific detectors (ECD, HECD) reduces the probability of inter-
ferences and increases the confidence in identification. Better still, MS
provides spectra of the eluent which may be compared with those of authentic
compounds to give high confidence identifications. Finally, the retention
time of the eluent should match that of a standard. CGC, and better yet high
precision CGC, gives much more precise retention times than PGC and increases
confidence.
In the case of Aroclor (or similar mixtures) derived PCBs, a pattern of
isomers usually resembles the pattern of a standard. This has been a common
qualitative technique in residue analyses, especially when PGC/ECD is the ana-
lytical procedure.
45
-------
TABLE 5. SUMMARY OF LABORATORY TECHNIQUES USED FOR THE CMA ROUND-ROBIN STUDY (Erickson, 1982)
Lab
A
B & J
C
D
E
F
G
H
I
K
Work- up
technique
DIa
Dil/Inje
Sonication/Inj
(some diluted)
Sonication/Inj
(some diluted)
DI and Dil/Inj
Heat/Inj;
Dil/Inj; DI
DI
Dil/Inj
Dil/Inj
Acid Digest/
Extract/Inj ;
Some heated
Analysis MS calibration GC calibration
technique method method
PGC/EC , Confirmation ?
PGC/EIMS only
PGC/EIMS SIMf Autotune EG8 (3 pts)
PGC/MS^ PFTBA^ ES
PGC/FID - ES
FCC/MS-* SIM PFTBA ES (3 pts)
PGC/EIMS SIM ? ES, RFk
PGC/EIMS SIM ? ES (1 pt)
PGC/EIMS SIM ? RF
CGCn/EIMS SIM ? RF
CGC/MSj DFTPP IS, RF°
Integration Calculation
technique equations
PHC No
Areas Yes
Ion Intensities No
? No
Areas No
Area No
Area Yes
Area Yes
Area Yes
Summed Area** No
LOD
presented
Yes
Yes1
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
See footnotes for Table 6.
-------
TABLE 6. SUMMARY OF LABORATORY TECHNIQUES USED FOR THE CMA ROUND-ROBIN STUDY (Erickson, 1982)
Lab
A
B & J
C
D
E
F
No.
ions/homolog
9
1
1
mm
3
21
Isotope
ratio
mentioned
»
No
No
•
Yes
No
Reporting
units
ppm
mg/kg
mg/2; ppm
018/25 PPm
Mg/g (?)
M8/g
QA
discussed?
No
Yes
No
No
Yes
Yes
No.
standard
isomers
18
24
10
5
25
iom
Comments
Too many significant figures. Very
little discussion.
Some full scan confirmation; good
discussion, good work overall.
Sample preparation is good.
Major interferences suspected—no caveats
or discussion of divergent data with
"Lab C."
No individual isomers reported.
Standard addition attempted but failed;
H
I
K
4-5
> 3s
Yes
ppra
No ppm
No ppm
No
ppm
Yes
No
No
Yes
use of Aroclor mixtures as standards
is of dubious value.
20 Good ion/retention time table; % recovery
calculated from standard addition (were
results corrected?)
10 H and I are same organzation; no discus-
10 cussion of differences observed in two
methods.
12 Limited recovery study (•>• 100% recovery);
injection precision measured for one
sample.
-------
FOOTNOTES FOR TABLES 5 AND 6
a Direct injection.
b Packed column GC/electron capture detector.
c Peak height.
d Packed column GC/electron impact mass spectrometry (full scan).
e Dilute and inject.
f Selected ion monitoring.
g External standard.
h Details presented—two integration methods used, one designated "B"; one designted "J.1
i Estimated, no details.
j Unspecified operating mode.
00
k Response factor.
1 One ion from parent cluster and one ion from fragment cluster.
m Aroclor mixtures.
n Capillary column GC.
o Internal standard (details unclear).
p Areas of three (two for C10H9C1) most intense ions in parent cluster summed.
q Limited scan technique used; all ions in j>arent cluster were observed.
-------
Review Articles—
Only five reviews mentioned the qualitative aspects of PCB analysis
(Reynolds, 1971; Sherma, 1975; Safe, 1976; Fuller et al., 1976; and Margeson,
1977). Generally, the qualitative discussion was cursory. Reynolds (1971)
advised use of pattern recognition (against the Aroclor standards). Sherma
(1975) recommended a slightly more formal approach—comparison of retention
times in samples and standards.
Standard Methods—
As noted in Table 1, less than half of the standard methods discuss qual-
itative analysis. In the PGC/ECD methods pattern recognition is the qualita-
tive procedure. Often chromatography on two GC colums of different polarity
is used to enhance the confidence of the verification. An example of good
qualitative guidance for the analyst is found in the EPA protocol for analysis
of PCBs in transformer fluids and waste oils (EPA, 1981).
Locate each PCB in the sample chromatogram by comparing the reten-
tion time of the suspect peak to the retention data gathered from analyz-
ing standards and interference free Quality Control Samples. The width
of the retention time window used to make identifications should be based
upon measurements of actual retention time variations of standards over
the course of a day. Three times the standard deviation of a retention
time for each PCB can be used to calculate a suggested window size; how-
ever, the experience of the analyst should weigh heavily in the interpre-
tation of chromatograms.
In methods where GC/EIMS is specified, both mass and retention time may
be used for identification. None of the standard methods adequately address
the selection of ions and the permissible abundance ratios.
Primary Literature—
Less than half of the 38 articles abstracted contained mention of the
qualitative criteria used in identification of PCBs. A representative qual-
itative criterion was that the chromatogram exhibits a "typical Aroclor pat-
tern" (Gordon et al., 1982; Giam et al., 1972; Ofstad et al., 1978; Kirshen,
1981).
Several publications dating back to the landmark work of Sissons and Welti
(1971) concentrated on the identification of PCB isomers in commercial (Aroclor,
Chlophen, etc.) mixtures (Tas and deVos, 1971; Tas and Kleipool, 1972; Armour,
1972; Willis and Addison, 1972; Paasivirta and Pitkanen, 1975; Jensen and
Sundstrom, 1974; Stalling et al., 1978; Neu et al., 1978; Zell et al., 1978;
Ballschmiter and Zell, 1980; Pellizzari et al., 1981; Tuinstra et al., 1981).
The objective of most of these papers was to characterize the commercial mix-
ture as an aid to quantitation in environmental samples or for toxicological
information.
Several researchers mentioned the comparison of retention times or rela-
tive retention time in the sample and an Aroclor standard for PCB identifica-
tion (Webb and McCall, 1972; Onsuka and Comba, 1978; Pellizzari, 1982;
49
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Tuinstra et al., 1980). A much more specific identification scheme involves
use of one of the retention index (RI) (e.g., Kovats) schemes. Several publi-
cations contain tabulations of RIs (Sissons and Welti, 1971; Zell et al., 1978;
Neu et al., 1978; Ballschmiter and Zell, 1980; Albro et al., 1981; Albro and
Fishbein, 1972a, 1972b). Since all 209 PCB congeners are not available, a
scheme of predicting RIs has been developed based on the half-RI values for
the various chlorination positons on one of the benzene rings. Sissons and
Welti (1971) first proposed this system, which was expanded upon and further
validated by Albro and Fishbein (1972) and Albro et al. (1977). The use of
half RIs permits the analyst to qualitatively identify all 209 PCBs on the
basis of their retention time, although the level of confidence in this iden-
tification is low. Using state-of-the-art chromatography, RI measurement pre-
cision of ± 0.05% has been reported for PCBs (Neu et al., 1978), and with full
optimization, precision of ± 0.01% has been predicted (Neu and Zinburg, 1979).
Recently Dunn et al. (1982) used a computerized pattern recognition tech-
nique to evaluate CGC/ECD data on PCBs in sediments, water, benthos, and fish.
The computer program can detect incorrect assignments (i.e., Aroclor 1242 in-
stead of 1260) and abnormal samples. This appears to be a most promising tech-
nique for interpretation of large numbers of PCB determinations.
When a mass spectrometer is used as the GC detector, an additional qual-
itative dimension is available. The mass spectra of a PCB are distinctive
due to the cluster of masses generated by the presence of two chlorine iso-
topes in nature. If sufficient material is present to obtain full mass spec-
tra, the unknown can be reliably identified by comparison with spectra of
standards or spectral compilations (Stenhagen et al., 1974; Mass Spectrometry
Data Centre, 1970; Heller and Milne, 1978). The quality of the spectrum re-
quired for identification needs to be defined (Christman, 1982).
As mentioned above, the natural isotopic abundance ratios yield a char-
acteristic pattern. The use of these ratios in selected ion monitoring can
provide qualitative information when full mass spectra are not obtained. The
actual ratios have been tabulated for PCBs (Rote and Morris, 1973) or may be
readily calculated. This approach has been utilized (Canada and Regnier, 1976)
with complex samples (Erickson and Pellizzari, 1977, 1979). Even though the
natural isotopic abundance ratios are constant, instrumental variances and
interferences can affect the observed ratio. Thus, tolerance criteria need
to be utilized by the analyst.
Tindall and Wininger (1980), in a method designed to determine PCBs even
if they are not "Aroclor-derived," established qualitative criteria:
Each peak in the chromatogram is evaluated to determine if it is a
PCB peak. Peaks must meet these criteria to be labeled PCB peaks for
quantitation: (1) the peaks of the characteristic ions must maximize at
the same retention time; (2) the peak must be in the proper retention
time window; and (3) the relative peak intensities of the molecular ions
must be within ± 15% of the theoretical ratio. This tolerance is arbi-
trary and can be made larger for very low concentrations of PCBs where
statistical variations in peak intensity become large.
50
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Work by Collard and Irwin (1982) and Dow (1981) established similar qual-
itative criteria:
Identify the chlorinated biphenyl homologs by their mass ion response,
relative retention time, and ion intensity ratio (± 20% relative). Secon-
dary confirmation of trichloro-through decachlorobiphenyl may rely upon
the M-70+ ion response.
These two works suggest a new awareness that qualitative criteria must be stip-
ulated in any method if the results are to have any significance.
In addition to the various gas chromatographic identification methods,
thin-layer chromatography and high performance liquid chromatography yield
qualitative information, as discussed above. More exotic techniques such as
other mass spectrometric techniques, Fourier transform infrared spectrometry,
and nuclear magnetic resonance spectroscopy are not used routinely in most
laboratories, so have been included as confirmatory techniques which will be
discussed below.
Quantitative
With most organic compounds, the quantitation is relatively straightfor-
ward. The instrumental response is calibrated using standards. The amount
of unknown is measured by comparison of the signal it generates with the cali-
bration factor or curve. Quantitation of PCBs is not nearly so simple because
the analyte is not a single compound but rather a complex mixture of 209 possi-
ble congeners and standards of all 209 congeners are not available for calibra-
tion. Given these problems, analysts have devised alternate quantitation meth-
ods generally based on the similarity of the sample PCB mixture to a commercial
product (e.g., Aroclor).
Review Articles—
Most review articles mention quantitation of PCBs briefly. Safe (1976)
discussed the problems of ECD response variability discussed in detail above
and suggested that perchlorination would be more consistently accurate.
Hutzinger et al. (1974) reviewed the quantitation methods to that date, most
of which involved relating the unknown to Aroclor standards. Sherma (1975)
provided a similar, but more detailed, review which included a positive as-
sessment of the Webb and McCall (1973) procedure. The other reviews
(Riseborough, 1971; Fuller et al., 1976; Reynolds, 1971; Margeson, 1977) dis-
cussed quantitation in similar but less detailed fashion.
Standard Methods--
As shown in Table 1, all standard methods give at least cursory in-
structions on quantitation. At one extreme, the general purpose protocols
(EPA, 1979a, 1979b; Ballinger, 1978; EPA, 1978) contain vague direction to
"integrate the area under the peak." Much more complete quantitation guide-
lines are given in EPA's (Bellar and Lichtenberg, 1981; EPA, 1981) protocol
for analysis of PCBs in transformer fluids and waste oils.
Primary Literature—
It is obvious from the data presented that PCBs were quantitated in most
of the references abstracted. However, many articles neglect to mention how
51
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the PGC/ECD signal was converted into a concentration value. Some 80 articles
abstracted mentioned the quantitation technique, although many only made a
brief mention of "integration" or "comparison with Aroclor 1260 standard."
Packed column gas liquid chromatography/electron capture detector--As
noted in Table 3, the response factors for the individual PCB congeners vary
widely, even within a homolog. This fact has typically been overlooked in
quantitation procedures based on the use of Aroclor (or other commercial mix-
tures) standards.
The most prominent GC/ECD quantitation method was originated by Webb and
McCall (1973). The weight percent and homolog identification (relative pro-
portions where more than one homolog was present) were determined for several
Aroclors, and retention times relative to £,p_'-DDE were specified. The general
procedure is as follows:
Chromatograph known amounts of the standards and measure the area
for each peak. Using the tables of data determine the response factor
(ng PCB/cm2) for each peak. Chromatograph the sample and measure the
area of each peak. Multiply the area of each peak by the response factor
for that peak. Add the nanograms of PCB found in each peak to obtain
the total nanograms of PCB present. Samples containing one Aroclor or
more than one Aroclor can be quantitated by comparison with appropriate
standards.
Following an interlaboratory survey, Chau and Sampson (1975) recommended
that the Webb and McCall method be adopted as the uniform quantitation method.
They cited the general applicability, elimination of mixed standards, the more
realistic results, and simplicity of the method as reasons for their recom-
mendations.
Exact replication of the method requires reproducing the chromatography
and using the same lot of Aroclor standards as Webb and McCall used. These
stringent requirements have led most researchers to characterize their quanti-
tation practice as a modified Webb and McCall (Erickson et al., 1981; Kreiss
et al., 1981; Harris and Mitchell, 1981; Steichen et al., 1980; Sawyer, 1978a).
The calculations required can be easily automated using common GC integrators
or data systems (Erickson et al., 1981; Kirshen, 1981).
Ugawa et al. (1973) devised a quantitation method similar to a Webb-McCall
except it was based on the Japanese commercial PCB, Kanechlor.
Unfortunately, most samples are exposed to weathering, metabolism, dif-
ferential adsorption, etc., and the PCB pattern, though originally one or more
Aroclors, does not closely resemble that of the standard. This has been noted
repeatedly and certain correction procedures have been proposed (Beizhold and
Strout, 1973; Webb-McCall, 1973).
Several researchers (Collins et al., 1972; Rote and Murphy, 1971; Bellar
and Lichtenberg, 1975) and standard methods (AOAC, 1980; ASTM, 1980a, 1980b)
advocate comparison of the total areas under the "Aroclor region" in the sample
and standard chromatograms. This is a simple approach and has been recommended
52
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by Sawyer (1973) as the most reliable method for obtaining interlaboratory
precision. In a later collaborative study (Sawyer, 1978b), the individual
peak height (Webb and McCall, 1973; Sawyer, 1978a), total peak height and
total peak area methods were all compared and gave similar results, although
the individual peak method was judged slightly better. On this basis, AOAC
(1980) permits either individual peak (Webb-McCall) or total area quantita-
tion of PCBs. Bellar and Lichtenberg (1975) used either the total peak height
for samples closely resembling Aroclors or Webb-McCall for patterns "not repre-
senting a single Aroclor."
Wolff et al. (1982) used 2,4,4'-trichlorobiphenyl, 2,4,5,2',5'-penta-
chlorobiphenyl; and 2,A,5,2',4",5'-hexachlorobiphenyl as standards for CGC/
BCD quantitation of PCBs in plasma and adipose samples of occupationally ex-
posed people. Quantitation by this sum of individual peaks method gave com-
parable results to the Webb-McCall method using PGC/ECD. Both methods gave
lower values than the sum of peak areas method using PGC/ECD data.
Zobel (1974) devised a computer fit routine which matched the sample chro-
matogram with various "co-added" Aroclor chromatograms to obtain a best fit.
"Spuriously large or small peak heights, caused by interfering compounds or
metabolism, are automatically sorted and rejected." The method reports results
in terms of the different Aroclors and can be modified to generate an estimate
of "premetabolism" PCB content.
While providing no details on how the PCBs were quantitated, Giam et al.
(1973) required at least 50% of the peaks in the sample chromatogram to match
those in an Aroclor standard when analyzing marine biota for PCBs.
Capillary column gas liquid chromatography/electron capture detection—
The application of CGC to PCB determination complicates the already difficult
quantitation problems: more peaks are present. Since the peaks are ostensi-
bly single congeners instead of the mixture obtained by PGC, much emphasis
has been placed on quantitation of single congeners. Boe and Egaas (1979)
devised a calibration factor system that permits the analyst to calculate the
ECD response factor for a given congener, once its structure is known. More
recently, the response factors for 159 congeners were measured (Table 4). As
discussed above, the ranges over homologs and within a homolog indicate that
calibration with each congener would be necessary for accurate results.
Despite the higher resolution with CGC and therefore more available in-
formation, simplistic quantitation routines are still used. Gordon et al.
(1982) used three peaks from each Aroclor standard as their method for quan-
titating PCBs in transformer oil by CGC/ECD. While PCBs do not weather ex-
tensively in transformer oil and are thus more likely to resemble the parent
Aroclor, this method utilizes only a small portion of the available informa-
tion. Schulte et al. (1976) recommend quantitation of CGC/ECD chromatograms
based on two selected charactistic peaks in food extracts.
Albro et al. (1981) determined the relative molar percentages of the in-
dividual components of about 100 different PCB congeners in Aroclors 1248,
1254, and 1260. They recommend using the Aroclor mixtures as secondary stan-
dards to calibrate CGC/ECD responses.
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Gas liquid chromatography/electron impact lonization mass spectrometry--
The ability of EIMS to easily sort PCBs by homolog has led to a tendency among
GC/EIMS users to quantitate by homolog (e.g., summing all homolog peaks).
Another major difference from analog (ECD) detector quantitation is the abil-
ity to quantitate using either a single PCB-specific m/z peak or the total
ion current which corresponds to the analog detector output.
The first reported GC/EIMS quantitation was a simple translation of clas-
sical PCB GC/ECD quantitation: comparison of "the area under one or more of
the eight peaks to the area of a known amount of a standard" (Bonelli, 1972a,b).
Eichelberger et al. (1974) chose what they termed the conventional ap-
proach and assumed that the PCB mixture was identified as one of the commercial
mixtures. The total peak area for each SIM mass in the sample and standard
were compared using an internal standard to normalize the peak areas.
Erickson and Pellizzari (1977, 1979) quantitated PCBs in sludge based on
a relative molar response (RMR) of each homolog. Using SIM techniques, the
RMR for one isomer of each homolog was determined. Standards of hepta- through
monochlorobiphenyl were too impure to use and RMRs for these homologs were
interpolated. The RMR decreased dramatically (logarithmically) with increasing
degree of chlorination, presumably due to the decreasing lonization cross-
section.
Williams and Benoit (1979) compared the summed total integrated area for
six to eight selected peaks in samples and standard for quantitation of PCBs
in several household products.
Tindall and Wininger (1980), in one of the few papers addressing analy-
sis of non-Aroclor PCBs, established homolog response ratios using an unspe-
cified number of isomers per homolog. The highest and lowest response factors
for a homolog were averaged to give the average response factor used in the
calculation of PCB concentration in the unknown. An internal standard (tri-
bromobiphenyl) was used to get relative responses.
Martelli et al (1981) reported the EIMS relative response factors for 45
PCB congeners (Table 4). The relative standard deviation per homolog ranged
from 0.7% (3 of 46 isomers) to 21% (11 of 42 isomers). They propose using
these average response factors on GC/EIMS quantitation of PCBs by homolog.
Collard and Irwin (1982) used an unspecified number of isomers per homo-
log to establish response factors for each homolog. A daily calibration plot
at three concentrations was used for comparison of the summed peak heights
for one homolog.
Dow (1981), in a related protocol, specified 22 congeners to be used in
a similar calculation. For homologs with more than one isomer in the standard
a summed intensity was used.
Miscellaneous--Cairns and Jacobsen (1977) advocated the quantitation of
PGC/EIMS because of the reduction in interferences by other halogenated com-
pounds such as DDE. Eichelberger et al. (1974) also mentioned PGC/EIMS as an
alternate technique for dirty samples but did not discuss quantitation.
54
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As discussed in a separate section, perchlorination and dehydrochlorina-
tion, followed by PGC/ECD and PGC/FID determinations, respectively, have been
proposed as PCB quantitation methods which eliminate the congener variability
problems.
TLC and HPLC have also been employed as quantitative techniques and are
discussed in separate sections above.
CONFIRMATION
Confirmatory techniques have been frequently used in PCB analysis. The
term confirmation may be loosely defined as any operation performed to in-
crease the confidence of the results beyond the primary analysis. Qualita-
tive confirmation is much more often reported than quantitative confirmation.
Confirmatory techniques involve variation of the same technique (PGC/ECD on
two dissimilar columns), confirmation by a lesser technique (PGC/ECD with TLC
confirmation), or confirmation by a more advanced technique (PGC/ECD with PCG/
EIMS confirmation).
Review Articles
Hutzinger et al. (1974) devoted about two pages to the subject of con-
firmation. While mass spectrometry was briefly mentioned, most of the dis-
cussion centered on perchlorination.
Standard Methods
Table 1 listed all of the standard methods and notes the type of confir-
mation suggested. All of these confirmations are optional and qualitative.
Primary Literature
As early as 1969, the need for confirmation of findings was discussed
(Reynolds, 1969). An exchange of comments following a presentation by
Riseborough (1971) led to a proposal for confirmation by P. L. Diosady, cover-
ing, mass spectrometry, dechlorination, and perchlorination. Price and
Welch (1972) are typical of many early investigators who backed up their PGC/
ECD analysis with a TLC confirmation (see also the standard methods: AOAC,
1980; FDA, 1977). Hannan et al. (1973) utilized a cumbersome ultraviolet ir-
radiation method to confirm PGC/ECD results.
Mes and coworkers have utilized a variety of confirmatory techniques,
generally in concentration, in the analysis of adipose and milk samples (Mes
et al., 1977; Mes and Davies, 1979; Mes et al., 1980). The methods include
two dissimilar GC columns, perchlorination, and GC/EIMS.
GC/EIMS was used by Biros et al. (1972) to confirm TLC results. GC/EIMS
confirmation has also been reported (Musial et al., 1979; Teichman et al.,
1978; Lucas et al., 1979; Rodriguez et al., 1980; Haile and Baladi, 1977;
Erickson et al., 1981). HREIMS has been reported as a confirmatory technique
(Safe et al., 1975; Safe, 1976; Musial et al., 1974). Kuehl et al. (1980)
used CGC/NCIMS to qualitatively confirm their CGC/EIMS PCB identifications in
55
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fish. Mass and Friesen (1979), placing particular emphasis on polychlorinated
dibenzodioxins, reviewed the advanced mass spectrometric techniques for both
high sensitivity and high reliability analysis: HREIMS and NCIMS.
SCREENING TECHNIQUES
Screening techniques in this text are defined as methods used to identify
the presence of PCBs qualitatively, semiquantitatively, or quantitatively with-
out specification of the homologs in a sample extract. Screening techniques
under this definition could include thin-layer chromatography, high perform-
ance liquid chromatography, and gas-liquid chromatography. These methods
have been discussed in detail earlier in this review. Perchlorination and
carbon-skeleton chromatography, however, are screening methods that have not
been mentioned, although Table 1 indicates that perchlorination has been used
as a quantitative method or PCB confirmation technique in several of the stan-
dard procedures.
Perchlorination
Perchlorination methods are based on the exhaustive chlorination of the
biphenyl ring of the PCB congeners. The major disadvantage of the perchlorin-
ation reactions is that biphenyl can also be perchlorinated. Thus, the pres-
ence of biphenyl can lead to erroneously high levels of quantitation. Quan-
titative analysis is typically accomplished by GC/ECD systems although GC/MS
identification has been used in some instances. Perchlorination reactions
are reportedly troublesome because of contamination of reagents with deca-
chlorobiphenyl or brominated compounds (Trotter and Young, 1975).
Perchlorination reaction methods were first studied using antimony penta-
chloride (Berg et al., 1972; Matsumoto, 1972; Armour, 1973) and thionyl chlo-
ride in the presence of aluminum chloride (Nose, 1972). Armour (1973) re-
ported greater than 90% recovery of PCBs by perchlorination and found the
technique comparable to PGC/ECD comparison with Aroclor standards. Nose (1972)
reported approximately 100% conversion of tri-, tetra-, and hexachlorobiphenyls
to decachlorobiphenyl with the thionyl chloride system. Antimony perchloride
is apparently the most frequently used reagent as indicated by a review of
the literature. Hutzinger et al. (1973) studied trichlorosulfur-tetrachloro-
aluminate to quantitatively convert Aroclor 1254 to decachlorobiphenyl. One
of the major disadvantages of perchlorination arises from blank problems
(Trotter and Young, 1975). This has resulted in the need to carefully char-
acterize perchlorination reagents prior to reaction (Huckins et al., 1974).
The other major disadvantage of perchlorination is the conversion of biphenyl
to decachlorobiphenyl. Chlorine-37 labeled perchlorination reagents have been
studied as a means to clarify this problem and at the same time distinguish
the contribution of various PCB homologs to the final decachlorobiphenyl by
computer assisted isotope dilution interpretation (Burkhard and Armstrong,
1982). This technique, although unique in approach, requires optimum reac-
tion and MS conditions for successful analysis. Perchlorination has been used
successfully for numerous studies in recent years (Kohli et al., 1979; Sherma,
1981; Stratton et al., 1978; Fulton et al., 1979; Crist and Moseraan, 1977;
Robbins and Willhite, 1979; Mes et al., 1977; Mes and Davies, 1979; Haile and
Baladi, 1977; Vannuchi et al., 1976; Margeson, 1977; Brinkman et al., 1978;
Kohli et al., 1979; Albro et al., 1980; Leoni et al., 1976; Trevisani, 1980).
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Carbon Skeleton Chromatography
Carbon skeleton chromatography is based on the dechlorination of PCBs to
biphenyl. Catalysts for the dechlorination are typically platinum or palla-
dium. The disadvantage of carbon skeleton chromatography is that background
levels of biphenyl in the sample extract will yield erroneously high concen-
trations of total PCBs as noted for perchlorination. Also, since the product
of dechlorination is biphenyl, mass spectrometry must be used to reliably
identify the compound, especially in extracts from complex matrices.
Quantitative carbon skeleton chromatography by catalytic decomposition
of the PCBs over platinum or palladium to biphenyl has been discussed in three
articles (Berg et al., 1972; Zimmerli, 1974; Cooke et al., 1978). Zimmerli
(1974) and Cooke et al. (1978) studied conversion of PCBs as well as halogen-
ated terphenyls, napthalenes, dioxins, furans, and DDT. Effective catalysts
were found to be effective as 3% palladium at 305°C and 5% platinum at 180°C.
Reaction products for the various compounds were identified by GC/MS. On the
other hand, false negative results have been observed using this technique
for analysis of chlorinated bottoms (personal communication, M. D. Crouch,
Toxicon Laboratories, Baton Rouge, Louisiana, 1982).
QUALITY ASSURANCE
A strong quality assurance (QA) program for PCB analysis should include
use of pure standards, solvents, and glassware; an evaluation of method blanks
for background PCB and interference levels; calibration of instrumental equip-
ment; validation of the individual method steps as well as the overall method;
and an evaluation of the overall performance of a method through replicates,
interlaboratory comparisons, and/or standard reference materials. The data
that should be provided by a strong QA program should include at a minimum,
precision and accuracy measurements for each sample matrix.
These parameters have been previously outlined by MacDougall et al. (1980)
in an attempt to clarify needs for general data quality evaluation for com-
parison of trace organic results among numerous laboratories. The guidelines
for data acquisition and data quality evaluation presented by MacDougall et
al. (1980) were provided under the direction of the Americal Chemical Society
Committee on Environmental Improvement and the Subcommittee on Environmental
Analytical Chemistry. The guidelines were based on good analytical practices
to assist analysts in obtaining data of requisite quality and to aid in the
evaluation of the quality of the reported data. In addition to the QA param-
eters previously listed, MacDougall et al. (1980) have presented requirements
for sampling to adequately characterize a sample and enhance reliability in
the final result. These guidelines also discuss the necessity of detailed
documentation of sample preparation and actual analysis such that other quali-
fied analysts may duplicate the work. The demonstration of precision and ac-
curacy of measurements through good laboratory practices, proven methodologies,
low noise instrumentation, the use of standard reference materials, and partici-
pation in collaborative studies were also discussed as essential to strong QA
programs. The guidelines also presented definitions of and criteria to estab-
lish limits of detection (LOD) and limits of quantisation (LOQ). Method vali-
dation, qualitative confirmation of validated measurements, risks in data in-
terpretation from low recovery methods, reporting of interferences, and the
57
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appropriate presentation of the analytical results were discussed with respect
to evaluation of data quality.
Quality assurance in some form has been practiced in many of the studies
abstracted for the PCB analysis literature review. However, few of the stud-
ies have implemented enough QA to allow comparison of the data from one matrix
to the next.
The EPA has taken steps to implement strong QA programs in various stan-
dard methods of analysis and as part of long-term project goals (EPA, 1979a,
1980a, 1980b, 1981; Bellar and Lichtenberg, 1981). Table 1 lists the stan-
dard methods that acknowledge the need to follow some type of QA program.
Other than the standard methods and EPA guidelines, QA programs have been
practiced for collaborative method studies for PCBs in different matrices
(DCMA, 1981; Sawyer, 1973, 1978; Delfino and Easty, 1979; Devenish and
Harling-Bowen, 1980).
The QA program for the Dry Color Manufacturers Association (DCMA, 1981)
round robin study included instrument calibration specifications, performance
evaluation of the gas chromatography column with a standard mixture of PCBs,
and measurement of sensitivity for PCBs by serial dilution of the standard,
methods blanks, specification of quantitation procedures and validation of
sample preparation procedure. The validation of sample extraction, cleanup
and analysis included workup of blind and known spike samples. The results
of the DCMA study indicate that variance in reported PCB levels between la-
boratories was signficantly reduced when a commercially prepared quantitation
standard was used by all participating laboratories. Data from the DCMA re-
port indicated relative standard deviations of 3.1 to 9.1% within a labora-
tory, 2.4 to 40% between laboratories, and values ranging from 7.3 to 41%
representing the total reproducibility for analysis of three different pigments.
The Chemical Manufacturers Association sponsored a round-robin study of
PCB concentrations in five different samples that are indicative of matrices
that will be regulated by the PCB Remand Rule (Pittaway and Horner, 1982).
Eight different laboratories participated in the study. In contrast to the
DCMA study, no defined protocol or QA programs were specified for analysis of
the matrices. Each laboratory was allowed to choose the method of extraction,
cleanup, instrumental determination and quantitation, and QA program if de-
sired. This study indicated that there are many sources of potential error
in the quantitative analysis of PCBs. A comparison of the reported levels of
PCBs and precision of measurements between laboratories indicated a true need
for a strong QA program that might allow some normalization of the data.
The collaborative study reported by Delfino and Easty (1979) focused on
the analysis of PCBs in paper mill effluents. The study consisted of two
phases. The first phase was used to determine the comparability of PCB meth-
odologies between six different laboratories and the abilities of the parti-
cipating analysts to perform the basic operations required for PCB analysis.
These factors were determined by direct injection and quantitation of a per-
formance standard and the simple extraction and analysis of a spiked aqueous
solution. The second phase required an actual validation of a sample method
using known and blind samples. A modified EPA wastewater analysis protocol
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was followed by all participating laboratories. Some flexibility to the
method protocol was allowed for column materials and exact quantitation pro-
cedures. The results of the first phase extraction from distilled water
yielded an average recovery of 95.6% with a relative standard deviation of
14.7%. The relative standard deviation for direct injection of a standard
solution was 15.6%, thus indicating that gas chromatographic analysis was the
principle source of variance. The results for paper mill effluent yielded
similar results with 93.6% average recovery with a 16.0% relative standard
deviation, and indicated that the method was satisfactory for paper mill ef-
fluents .
Sawyer (1978) conducted a collaborative study of PCB quantitation with
ECD as the detector. Ten independent laboratories took part in the study and
used existing AOAC methodology to study three ECD quantitation procedures.
The average combined recovery in this study was approximatley 85% with a co-
efficient of variation of 15%. No significant difference was noted for the
three different quantitation operations.
A large void in most QA programs has been filled by the provision of stan-
dard reference materials of known FCB concentration (Chesler et al., 1982).
Although the standard reference material will only be available as an oil, it
leads the way in establishing further QA criteria for the analysis of PCBs in
other media. The preparation of additional PCB standard reference materials
as wet and dry reference materials has been discussed by Chau and Lee (1980),
Chau et al. (1979), and Addison and Hearing (1982), although these materials
are not currently available.
Other policies that are of considerable concern and reflect the current
attitudes toward QA have been presented by Glaser et al. (1981) concerning
method detection limits based on confidence levels and the guidelines pre-
sented by Environmental Science and Technology (Christman, 1982) outlining
information required to label compounds identified by mass spectrometry as
"tentative" or "confirmed."
BY-PRODUCT PCB ANALYSES
Historically, analysis of PCBs has been concerned with commercial mix-
tures, such as Aroclors, and their dispersal in the environment and certain
commercial products (packaging materials, paper products, transformer oils,
etc.). The analytical approaches to identification and quantitation of these
commercial PCB mixtures has already been discussed in this literature review.
Health and environmental concerns have resulted in an increasing number of
federal regulations (EPA, 1979d) controlling the manufacture, use, and dis-
posal of PCBs. A recent report prepared by the Chemical Manufacturers Asso-
ciation for EPA (Pittaway et al., 1981) documents numerous commercial pro-
cesses that will be affected by proposed federal regulation of by-product PCBs.
These by-product PCBs are produced by diverse processes, few of which resemble
the commercial PCB synthesis routes. Thus, the resultant PCB mixtures do not
resemble the familiar Aroclors. The analysis of by-product PCBs was reviewed
by Hodges et al. (1982).
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An extremely limited number of articles are available for review of by-
product analysis (Tindall and Wininger, 1980; Collard and Irwin, 1982;
Pittaway and Horner, 1982; DCMA, 1981; Dow, 1981). These few references,
however, describe some of the problems encountered in by-product analysis of
commercial products as discussed below.
Dry Color Manufacturers Association Pigment Analysis
A major study was conducted by the Dry Color Manufacturers Association
(1981) for the analysis of by-product PCBs in three different pigments. This
study concluded that a universal cleanup procedure was not possible for accu-
rate PC8 analysis from all of the pigments. The use of GC/MS was recommended
for establishing positive identification of the PCBs. Two of the pigments
studied contained only one PCB isomer, while the third pigment was contam-
inated with several different isomers of the penta- and hexachlorobiphenyl
homologs. A thorough quality assurance program was developed for the purpose
of reducing interlaboratory variability. The quality assurance program in-
cluded validation of each step of sample preparation, gas chromatographic per-
formance standards, and mass spectrometer calibration and performance ap-
praisal, as well as requirements for analysis of spiked blanks, replicates,
and standard additions.
Round-robin experiments were conducted under this study. The DCMA found
that a large portion of the interlaboratory variance was due to the differ-
ences in preparation of the standard mixtures of PCB isomers used for estab-
lishing response factors. A calibration mixture obtained from a single source
was found to greatly reduce interlaboratory variance. In addition, specifi-
cation of PGC criteria with respect to retention tiroes and resolution of spe-
cific isomers was required to promote comparability of results between labora-
tories.
Chemical Manufacturers Association Round-Robin
The Chemical Manufacturers Association has conducted a round-robin ex-
periment for analysis of by-product PCBs (Pittaway and Horner, 1982) in chlo-
rinated benzene waste streams, mixtures of chlorinated benzenes, blind spikes
in the chlorinated benzenes, composite waste streams from a chlorinated ali-
phatic process, and a benzene column bottom sample. The round-robin studies
defined some of the problems of by-product PCB analysis in commercial products
and process waste streams.
Many sources of potential error in the quantitative analysis of these
samples were identified and include unknown interferences, inappropriate use
of reference standards, inappropriate protocols, day-to-day variations in in-
strumental responses, calibration, and execution of analytical procedures,
inappropriate collection of samples, contamination of samples, and limita-
tions in instrumental methods.
The round-robin study measured differences in analytical results between
laboratories, differences due to variation in analytical methods, limitations
of instrumental methods, and impact of analysis by random laboratories
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(Pittaway and Horner, 1982; Hodges et al., 1982). A total of eight laborator-
ies (six industrial and two EPA) participated in the study, using a variety
of techniques as shown in Tables 5 and 6. Guidelines were not given for meth-
ods of sample preparation, instrumental analysis, quantitation measurements
or quality assurance practices. The results from the round-robin study showed
a significant variance in data among laboratories, which one might expect from
the lack of written protocol and quality assurance. This study demonstrated
that there is a need for a common denominator in analytical protocol for anal-
ysis of by-product PCBs from a wide variety of simple to complex matrices.
Other Studies
Tindall and Wininger (1980), Collard and Irwin (1982), and Dow (1981)
studied PGC/MS methods for analysis of by-product PCBs in commercial and en-
vironmental samples. The MS analysis method was based on limited mass scan
ranges to qualitatively identify and quantitate any of the possible 209 PCB
congeners by horaologs. Tindall and Wininger (1980) reported that the criteria
for PCB quantitation must include matching of characteristic ions at proper
retention time windows. In addition, characteristic ions must maximize at
the same retention time and the relative peak intensities must be within ± 15%
of the theoretical ratio.
The accuracy limiting step of the PGC/MS (limited mass scan range) meth-
ods (Tindall and Wininger, 1980; Dow, 1981; Collard and Irwin, 1982) is the
selection of standards. In each case response factors were determined for a
limited number of isomers for each PCB homolog with the underlying assumption
that all PCBs of the same homolog have nearly the same response factor.
Quantitation procedures varied between the studies. Tindall and Wininger
(1980) used an internal standard, tribromobiphenyl, which responded to MS
source changes much like a PCB. In addition, its molecular weight was great
enough that interferences were rarely encountered. Collard and Irwin (1982)
and the Dow method (1981) quantitated versus a calibration curve established
at various concentrations using 10 congeners to represent each PCB homolog.
No internal standards were used. The accuracy and precision of these PGC/MS
methods are dependent on frequency of instrumental calibration and the extent
that other compounds in the ion source of the MS affect the sensitivity during
the course of an analysis.
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SECTION U
APPLICABLE TECHNIQUES
The objective of this section is to outline the best possible approaches
for by-product PCB analysis in commercial products that will be regulated
under the PCB Remand Rule. The proposed procedures are a result of the re-
view of the available literature presented in the previous section. The an-
alytical approaches provide versatility in terms of the wide spectrum of ma-
trices represented by the proposed regulated products. The success of the
proposed rule will rely heavily on a strong quality assurance (QA) program to
monitor sample preparations and instrumental analysis. The proposed QA pro-
gram will provide sufficient data to determine the quality of the quantitation
data for each specific sample matrix encountered. Sample extraction, cleanup,
instrumental determination, quantitation and data reduction, confirmation,
screening, and the overall quality assurance program are discussed.
EXTRACTION
The literature review of extraction techniques describes several ap-
proaches to isolation of PCBs from various matrices. The extraction may be
as simple as dilution of an organic liquid, batch extraction of aqueous solu-
tions, or Soxhlet extraction of solids; or as complex as matrix destruction
via saponification or with concentrated acid before extraction of the PCBs
with an appropriate organic solvent. However, the analyst must keep in mind
that totally unexpected reactions produced the trace levels of the by-product
PCBs being determined. Hence, the use of vigorous or harsh chemical reactions
may generate or destroy PCBs (L. F. Hanneman, Dow Corning Corporation, per-
sonal communication, 1982). Suitable organic solvents will include petroleum
ether, hexane, and methylene chloride. The exact extraction procedure, how-
ever, is dependent on the specific matrix. The alternative to designating a
specific extraction procedure for all solid and liquid samples that are of
highly dissimilar matrices both chemically and physically is to formulate a
rigid QA protocol before the extraction step and to continue it through all
aspects of analysis. The QA protocol will require extensive homogenization
of samples (solids, suspensions, liquids) by grinding and mixing. An aliquot
of each homogenized sample will be spiked with a series of surrogate compounds.
Final analysis of the sample extract for the surrogate compound recoveries
will provide sufficient quantitative information to evaluate the effective-
ness of the extraction procedure and or cleanup technique.
The choice of surrogate compounds is critical for exact performance mea-
sures of any method. The surrogate compounds must maintain the exact chem-
ical characteristics of the PCBs for extraction, cleanup, and quantitation
purposes. The surrogates may be either a series of PCB congeners representing
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each of the chlorinated homologs or a selected number of stable mass-labeled
(carbon-13 or chlorine-37) PCB isomers. The series of unlabeled PCB congeners
surrogates would necessitate independent measures of spike recovery and ana-
lyte concentration, whereas the mass-labeled PCB surrogates would allow simul-
taneous determination and quantitation of the analyte PCBs and the surrogate
compounds if EIMS is used as the GC detection. The implementation of the use
of the mass-labeled surrogates would provide a strong QA program since recovery
could be monitored for each sample analyzed and consistency between analytical
laboratories and different sample matrices could be compared more readily by
a regulatory agency.
Mass-labeled PCB isomers as surrogates could be provided at a reasonable
cost per sample analyzed (W. Duncan, Midwest Research Institute, personal com-
munication, 1982). A series consisting of mono-, tetra-, octa-, and decachlo-
robiphenyl mass-labeled isomers would provide a sufficient set of surrogates.
Carbon-13 labeled isomers of 99% purity for these homologs would provide suf-
ficient differences in mass spectra patterns for differentiation from isomers
of natural abundance.
The major problem to consider in adding surrogate compounds is whether
the incorporation of these compounds in a matrix will mimic the true analytes.
Incorporation cannot always be achieved, especially with matrices that require
exhaustive extraction methods. However, the measured recovery of surrogates
from an extraction and cleanup procedure will provide information on degrada-
tion of PCBs by the analytical procedure.
It may be desirable to design small scale experiments to incorporate the
surrogate PCBs during a product process (I. F. Hanneman, Dow Corning, personal
communication, 1982). Solid matrices, expecially those that may be intractable,
should be of prime interest for this approach. The surrogate compounds could
be incorporated before polymerization, vulcanization, curing, precipitation,
or other processes. The recoveries of the surrogates could be used to deter-
mine if the proposed extraction technique is applicable for routine analysis
of particular solid matrices.
Exact extraction protocols could be designated for air and simple aqueous
samples as shown in Table 1. Exact extraction protocols for commercial pro-
ducts could also be designated, but optimum performance for all matrices is
highly unlikely. A specified extraction protocol would require rigorous meth-
ods for all samples and must consider possible adverse reactions of certain
products to sulfuric acid digestions and alkaline saponification.
Independent extraction procedures for different matrices combined with
the use of surrogate compounds and thus validation of the method would be an
effective alternative. Each independent laboratory, however, must certify
that an effective extraction procedure is practiced.
The level of recovery considered sufficient and method of addition of
internal standards for final quantitation are yet to be determined.
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CLEANUP
Many cleanup techniques are applicable to commercial products. The na-
ture of the sample, complexity of the matrix, and the chemical characteristics
of other components dictate the requirements for any sample preparation.
Cleanup for air and aqueous samples in effluents from commercial production
facilities is achievable by applying standard methods (Table 1). However,
cleanup of a wide range of product matrices will require application of many
different techniques. A generic cleanup procedure may not suffice or be nec-
essary in the majority of analyses because of the different chemical character-
istics in the sample matrix. For example, sulfuric acid may provide sufficient
cleanup and quantitative recovery of one product that contains only decachloro-
biphenyl. However, this procedure will not be sufficient for a matrix that
contains mono- through trichlorobiphenyl isomers, which may not be recovered
quantitatively. Likewise, designated adsorbent columns may not provide the
separation of interferences necessary for good quantitative analysis for a
large majority of matrices.
As with the extraction step, one alternative is to allow the individual
laboratory to develop the necessary cleanup procedure. Each laboratory, how-
ever, must follow the stringent QA program using spiked samples or surrogate
compounds to validate the method at a determined level of proficiency. This
will meet the special analytical needs of the individual analyst and at the
same time provide the data necessary to determine analytical proficiency of
the method and consistency between laboratories and matrices.
DETERMINATION
Gas-liquid chromatography is judged to be the only acceptable primary
separation method. Capillary GC is preferred over packed GC. The injection
system, type of liquid phase, column dimensions and operating conditions
should not be specified, but performance should be maintained within estab-
lished criteria.
Electron impact mass spectrometry is the primary detection candidate.
Operating conditions (SIM, full-scan, or limited mass scan), performance cri-
teria, and other variables are still to be specified. Other detection options,
ECD and HECD are considered too nonspecific for these matrices or too uncommon
for general application (NCIMS, MS/MS, FTIR).
Separation
As clearly evidenced in the review of the literature, GC is by far the
most popular technique for PCS determination. The relative merits of PGC and
CGC are well-known and apply to the separation of PCBs. CGC provides better
resolution, retention time precision, and higher qualitative reliability.
PGC yields a simple chromatogram (less data reduction), permits higher sample
loading (and therefore possibly lower LOQs), and is generally considered easier
to use. Historically, PGC quantitation has been more precise, although it
has not been established how much of the imprecision attributed to CGC was
due to poor technique on the part of the analyst.
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The high resolution of CGC is not required in this application for sepa-
ration and identification of the individual PCB congeners since the final re-
sult needed is total PCB. However, the high resolution of CGC should aid the
analyst in separating PCBs from interferences. In this respect, CGC is pref-
erable. In many cases when the sample is amenable to "dilute and shoot" tech-
niques, very high levels of matrix materials may be present, which will over-
load the column. Although CGC is more sensitive to column overloading, both
CGC and PGC will overload with percent levels of matrix materials. The advan-
tages of CGC, therefore, make it the technique of choice. However, PGC should
also be allowed.
Nearly every GC phase has been reported in PCB analysis. The most satis-
factory separations have been achieved on nonpolar and semipolar phases
(Apiezon L, methyl silicone, Dexsil, etc.). Since enforcement of very spe-
cific column parameters is difficult and since rigorous stipulations do not
appear warranted, it is recommended that any nonpolar and semipolar capillary
column be permitted.
The choice of CGC injector (split, splitless or "Grob," and on-column)
can substantially affect the amount of material transmitted through the sys-
tem. Since enforcement of use of a particular injection would be difficult
and since no clear choice is presented, any injector which meets performance
criteria should be permitted.
As part of the quality assurance program, a set of GC performance cri-
teria should be established. The criteria should include number of effective
plates, separation number (Tz), resolution, and peak asymmetry. Since PCBs
are neutral, the acid/base characteristics of a column are of little interest;
however, some measure of compound transmission through the system must be used.
This may be achieved by monitoring the overall system response. Other options
would entail additional work and are thus less favored.
Detection
The electron capture detector is the most sensitive candidate detector.
However, it suffers from large differences in response factors for PCB con-
geners, which would result in very poor precision (Tables 3 and 4). Even more
serious is its lack of specificity. Since many of the sample matrices will
contain large amounts of halogenated nonPCB compounds, ECD would be overloaded
throughout much of the chromatogram, making PCB identification and quantita-
tion impossible. In certain cases, ECD may be a satisfactory detector, espe-
cially as a semiquantitative technique for screening samples prior to CGC/EIMS
analysis.
Electron impact mass spectrometry (EIMS) appears to be the method of
choice. Mass spectrometry has sufficient selectivity that a chlorinated or-
ganic matrix will not generally interfere with PCB determination. While the
El mode is not the most sensitive (NCI is much more sensitive), it is the most
common ionization technique for GC/MS and, most importantly, is the most repro-
ducible quantitatively. The precision of the EIMS depends upon the precision
of the response factors. The most thorough evaluation of PCB response factors
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(Martelli et al., 1981) found up to ± 20% RSD in selected isomers of one homo-
log. Since only 45 of the 209 congeners were characterized, the magnitude of
the variation in the remaining response factors is not known.
DATA REDUCTION
Qualitative
Since most matrices subject to regulatory analysis contain substantial
amounts of halogenated compounds in addition to PCBs and since an "Aroclor
pattern" will not usually be present, identification of PCBs is very important.
Any misidentification of a nonPCB as a PCB will yield an erroneously high
value. From the EPA's viewpoint, this poses no regulatory problem. However,
it may result in needless effort and cost to the regulated manufacturers.
In most cases, the EIMS data should provide sufficient confidence in the
identification of PCBs for action. For those laboratories which choose to
employ an equivalent technique for routine analysis, any samples with PCB
values near the regulatory cutoff ("near" has not been defined) would have to
be reanalyzed by the primary technique before a regulatory decision could be
made.
In cases where there are some doubts as to the identity of a peak as PCB
by CGC/EIMS, any available confirmatory technique should be allowed, provided
that the LOQ is equivalent to or lower than the CGC/EIMS LOQ. Positive con-
firmations present no regulatory problems to EPA. Any confirmations which
show that a peak is not PCB must be well-documented with appropriate QA (for
example, a spectrum of a PCB standard spiked into the matrix). In many cases,
instrument responses are highly dependent on the matrix, so the response to
standards in clean solvent cannot be equated with the response in the sample.
In cases where a peak is shown to contain both a PCB and an interference,
regulations should state that the entire peak must be quantitated as PCB un-
less the level of the interference can be precisely shown.
The qualitative criteria for the EIMS data should address the following
points:
1. Full spectra
a. Number of ions which must be present.
b. Background subtraction techniques permitted.
c. Ion intensity tolerances.
d. Relative retention time windows.
2. SIM
a. Number and mass of ions to be monitored per homolog.
b. Tolerance of ion intensity ratios.
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c. Relative retention time windows.
d. Signal-to-noise ratio.
3. LMS
a. Mass range to be scanned.
b. Tolerance of ion intensity ratios.
c. Relative retention time windows.
d. Signal-to-noise ratios.
Quantitative
Assuming that GC/EIMS is to be used, digitized data will be obtained for
use in quantitation. The areas or intensities of individual mass ions must be
measured, compared with those for a standard, and converted to a concentration
value. This process is complicated in PCB analysis by several factors:
1. Previous schemes based on Aroclor standards are not applicable to
incidentally generated PCBs.
2. PCBs are a complex mixture, so the problem really involves up to 209
separate quantitations.
3. All 209 congeners are not available as standards.
4. Two or more congeners may co-elute.
The ions for quantitation, selection of standards, and calculation proce-
dures are discussed below.
Quantitation Ions—
The highest signal-to-noise ratio and therefore precision is a compromise
between absolute ion intensity and background signal. Most analysts have
chosen an ion in the molecular cluster for quantitation. Even though other
ions may be more intense, the molecular cluster is at the highest mass and the
background is generally lower. The use of the most intense ion in the molecu-
lar cluster is recommended for quantitation, with options of less intense ions
from that cluster if interferences are encountered for the primary ion.
Calibration—
Four calibration methods are available: external standard, internal
standard response factors, internal standard multi-point calibration, and
direct use of the surrogates.
External standard calibration—Calibration of the analysis system versus
an external standard and then quantitation using the absolute intensities or
areas of the peaks lacks precision (Haefelfinger, 1981) and is not recommended
for gas chromatographic analysis. Often, the greatest source of imprecision
is the reproducibility of injection volume.
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Internal standard response factors — In this method, internal standard(s)
are added to the sample extract immediately prior to the instrumental deter-
mination, and the analytes are quantitated using the ratio of the peak height
or area of the analyte and internal standard. A previously determined response
factor (essentially a two-point calibration curve, with an assumed intercept
at the origin) is used in converting the response ratio to mass.
For PCBs, which can span a large chromatographic range, three or four
internal standards are recommended since the precision of the response factors,
and therefore the final quantitation, is related to how close the analyte peak
and internal standard elute (Haefelfinger, 1981; Bickford et al., 1980). Other
factors to be considered in the selection of internal standards are chromato-
graphic resolution from analytes and interferences, different mass spectral
properties to assure identification in GC/MS analysis, chemical similarity to
analytes (to minimize effects of changes in system selectivity), very low
probability of occurring in samples, and chemical stability. Candidates for
internal standards in PCB analysis include other halobiphenyls (e.g., fluoro-
nonachlorobiphenyl or dibromobiphenyl), related haloaromatics (e.g., chloro-
naphthalenes), and isotopically labeled PCBs (e.g., d6-3,4,3',A'-tetrachloro-
biphenyl). Given the complexity of the matrices in which by-product PCBs may
need to be determined, related chloroaromatics should not be used and halobi-
phenyls must be selected judiciously.
Since this technique is in essence a one-point calibration, the response
factors must be determined at a concentration close to that of the analyte.
Differences of more than one order of magnitude may induce significant error.
Recovery surrogates added prior to any sample treatment may also be quan-
titated against the internal standard and, since the amount added is known,
their recovery can be calculated. Knowledge of the percent recovery is useful
in monitoring extraction/cleanup performance. The final number reported may
be corrected for recovery if desired (or required), or the value found and
percent recovery reported separately. It should be noted that if the recovery
surrogates and analytes are not, in fact, equally recovered, then the reported
recovery is meaningless. This will happen if the surrogates are not fully in-
corporated into the matrix.
Internal standard multi-point calibration—This technique is essentially
the same as the response factor technique, above, except multiple calibration
points (typically three, spanning up to two orders of magnitude) are used to
establish a calibration curve. This has the potential for greater precision,
but requires much more time and several solutions. In cases where detector
sensitivity (signal response versus amount or concentration) is either non-
linear or the curve does not intercept close to the origin, a multi-point
curve is advisable.
Surrogate calibration—Surrogates may be used as internal standards for
quantitation. Using previously determined response factors (or calibration
curves), the response ratio of the analyte and surrogate, and known masses and
volumes, the mass of the PCBs may be calculated. When the surrogate recovery
is less than 100%, this method automatically corrects for this loss and pro-
vides a built-in recovery correction. This method has the advantage of simpler
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calculation and requires fewer solutions. This technique is often referred
to as isotope dilution. As with the internal standard technique, the surro-
gates must be incorporated into the matrix to assure equivalent recovery be-
tween the surrogate and analyte.
Selection of Compounds for Calibration-
Clear ly, most of the reported quantitation methods which rely on rela-
tion of the sample peaks to those in an Aroclor standard are not applicable
to by-product PCB determination.
The options for compounds to be used in calibration are:
1. Establish and use relative responses for all 209 congeners.
2. Establish and use relative responses for all available (about 80)
congeners and extrapolate the responses for the other isomers.
3. Establish and use relative responses for several congeners and ex-
trapolate the responses for the other congeners.
4. Characterize a secondary standard using all available congeners.
The secondary standard would be prepared from commercial mixtures to span the
range of congeners.
Option 1 is the ultimate technique. However, all 209 congeners are not
available and synthesis/acquisition would be extremely expensive and require
well more than a year for completion. Thus, even if this approach is to be
pursued, an interim approach must be specified. Options 2 and 3 are compro-
mises. Option 2 could be termed the best available method. Option 3 is
easier to implement and utilizes a reasonable number of quantitation congeners.
Option 4 would generate a well-characterized mixed Aroclor or similar mixture.
This has the advantages of low cost (once the characterization has been com-
pleted) and uniformity. The disadvantages are that (a) the concentrations of
the congeners range over two or more orders of magnitude, so calibration of
the instrument would be difficult and (b) many users will have only a limited
range of FCB homologs (e.g., only dichlorobiphenyls) and would not want to
use a standard requiring a full GC temperature program.
Options 2 and 3 appear to be the most applicable. Whether Option 2 or 3
is more appropriate depends on the variability of the response factors and
the precision desired by EPA. This area needs to be further investigated.
Assuming that all 209 congeners are not characterized and used as cali-
bration standards, analysts will have to extrapolate response factors from
the standards used to other isomers. Guidelines for these extrapolations must
be specified. A preliminary investigation by at least one laboratory to de-
fine the response factor variability among all available congeners is recom-
mended. An estimate of the error associated with the extrapolation would be
available from statistical evaluation of the resulting data.
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LIMIT OF QUANTITATION
Extrapolation of the data in Table 2 to a proposed LOQ for the PCB Remand
Rule is difficult because of several uncharacterized variables. The levels
of interferences will vary widely. In addition, recoveries will vary, also
affecting the LOQ. A major variable is the concentration factor in the workup
(number of grams of sample concentrated or diluted to a given sample volume
for injection on the GC). If the method works with a 1-g sample, an order of
magnitude decrease in LOQ can be effected by using a 10-g sample. This re-
quires additional effort and therefore cost. Taken to the extreme, it is pos-
sible to use very large samples (many kilograms) to lower the LOQ. On the
other hand, the customary volume to concentrate a sample extract is 1 ml.
One can, with some difficulty and loss of volume precision, further concen-
trate the extract to 100 pi, effecting a 10-fold decrease in LOQ. However,
if the sample is still dirty, this further concentration can lead to solidifi-
cation, which prevents injection onto a GC column.
DATA REPORTING
The final data report should list total PCB as the bottom line number,
since this is the value of regulatory interest. The analytical reporting for-
mat should be specified to eliminate any ambiguity and should address the fol-
lowing issues:
1. Tabulation of individual congener quantitation. This may be difficult
to achieve since congener identifications may not be available for more than
a few congeners.
2. Tabulation of individual homolog quantitation. This should be re-
quired so that data reviewers can assess the data.
3. Reporting units. These must be specified. Units such as micrograms
per gram (solids), micrograms per liter (water), and micrograms per cubic meter
(air) are recommended.
4. Recovery correction. If the final protocol specifies use of surro-
gates to monitor recoveries and if the method is validated, then recovery cor-
rection would be appropriate. While this conflicts with the customary prac-
tice in pesticide residue, priority pollutant, and other analyses, it is con-
sistent with the practice in many other fields (e.g., clinical analyses).
Since near quantitative (> 70%) recovery cannot be assumed, recovery correc-
tion is strongly recommended. Although high recoveries may not be guaranteed,
very low recoveries cannot be tolerated. The lower the recovery, the higher
the overall method LOQ. In addition, very low recoveries are generally ac-
companied by poor precision. If, for instance, 10 ± 5% recovery is achieved,
the uncertainty in the nominal 10X correction factor is huge (6.7-20X). Thus,
a lower acceptable limit of recovery (e.g., 30%) must be stipulated for ac-
ceptable data.
5. Standard reporting format. A standard reporting form, including all
equations to be used, intermediate calculations, etc., should be required.
This improves quality assurance since the chance for error (e.g., using the
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wrong conversion factor) is reduced, and any errors would be detected more
easily. In addition, data presented to regulatory personnel on standard
forms are much easier to review.
6. Internal standards. If no recovery surrogates are available, inter-
nal standards would most certainly be advocated. Their use generally improves
precision, and thus data quality, over the use of external standards. If sur-
rogates are used, the need for internal standards is not so clear. One can
use the surrogate response in the calculation of unknown concentrations. In
this case, instrument response variability, losses in the instrument, and
workup recovery are taken into account, all in one calculation. Thus, recov-
eries are corrected without any real knowledge of the percent recovery. On
the other hand, the use of both internal standards and recovery surrogates
would yield a fairly accurate assessment of the recovery and permit the ana-
lyst (or regulator) to decide if the recovery is unacceptably low. While
knowledge of recoveries is not of central regulatory concern, it does provide
the analyst with an estimate of the method performance. Therefore, if no in-
ternal standards are used, a semiquantitative estimate of recovery must be
made using the CGC/EIMS response (area counts or similar measure) to the sur-
rogates. If this is below a certain threshold (say 30% of expected), then
the sample preparation must be repeated or changed. The use of the surrogate
compounds as standards for both workup and instrumental analysis is simple;
and since it is one step instead of two, it should be more precise. The
price paid for this simplicity is that recoveries are not well characterized.
In the interest of simplicity and better precision, the use of internal stan-
dards in addition to recovery surrogates is not recommended.
CONFIRMATION TECHNIQUES
Qualitative
Alternate columns, detectors (HREIMS, FTIR, NCIHS, HECD, etc.), and
techniques such as MS/MS, direct probe HREIMS, NHR, FTIR, HPLC, etc., will be
permitted for confirmation of PCBs. Proper validation and demonstration of
comparable or lower detection limit must be provided with any confirmation
which overrules the GC/EIMS identification and eliminates the compound from
quantitation as a PCB.
Quantitative
As part of the overall QA, quantitative confirmation is required. The
options proposed include duplicate analyses and standard addition. Acceptance
criteria for these confirmatory techniques are discussed in more detail in
the Quality Assurance subsection.
SCREENING/EQUIVALENT METHODS
Alternate procedures to the designated protocol may be necessary to ob-
tain rapid estimates of PCB concentration for commercial facilities operating
on a continuous process basis or for small businesses relying on contract la-
boratories for analyses. The alternate procedures could possibly include per-
chlorination, dechlorination, TLC, PGC/ECD, PGC/HECD, CGC/ECD, CGC/HECD, etc.
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The data generated by these methods would be for the individual industry's
use to determine if changes in process design or initial reactants are neces-
sary to lower the levels of PCBs in the final product.
However, compliance with the regulations must still be determined with
the designated protocol unless EPA accepts the screening technique as equiva-
lent to the protocol.
Equivalency must be demonstrated in terms of sensitivity and selectivity
for PCBs, limits of detection and quantitation, and interferences. A strong
QA program must be implemented to establish and monitor the equivalency of an
alternate method. The quality control program should include measurements of
blanks, spiked blanks, and spiked samples (blind and known) to establish lim-
its for precision, accuracy, and recovery of analyses from the sample matrix.
Equivalent methods would be most applicable to continuous process opera-
tions with little system variance. Gross changes in any parameter of a con-
tinuous operation process should require further verification of equivalency
of the alternate method. The levels of PCBs in a fraction of all samples
should still be analyzed according to the proposed primary protocol for qual-
ity assurance.
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SECTION 5
POSSIBLE ANALYTICAL SCHEMES
The purpose of this section is to discuss how all the analytical com-
ponents presented in Section 3 can be integrated to produce an effective
overall protocol.
For discussion purposes, it is presumed here that a primary protocol will
be established and that it will contain the following steps:
1. Homogenize sample and subsample if necessary.
2. Incorporate surrogate compounds (e.g., four 13C PCB congeners).
3. Dilute, extract, or clean up as required.
4. Concentrate or dilute to a known volume.
5. Analyze a known aliquot by CGC/EIMS.
6. Identify PCBs by relative retention time and mass spectral charac-
teristics.
7. Integrate the PCBs by homolog and calculate amounts of each homolog
by normalizing the responses to responses for the surrogate compounds, using
one or more homolog response factors.
8. Sum all 10 homolog concentrations to obtain a total PCB value.
9. Report on standard reporting form.
10. Follow specified routine quality assurance (blanks, controls, dupli-
cates, standard addition, instrument performance criteria, etc.).
11. Maintain appropriate records.
ISSUES TO BE ADDRESSED
If this or a similar protocol is specified, several issues must be ad-
dressed.
Method Flexibility
Some flexibility must be permitted in the method details (GC columns,
solvent evaporation techniques, etc.) to accommodate different apparatus and
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laboratory practices. However, excessive flexibility will adversely affect
the data quality since many operations are uncontrolled. With proper QA
practices, the method can be flexible while still generating acceptable re-
sults. Thus, it appears that the best approach is to provide options and
suggest rather than require for most method details. As long as the labora-
tory demonstrates it is within the performance boundaries specified by the QA
guidelines, the optional approaches should be allowed.
Substitute Methods
Except when validated and routinely confirmed by CGC/EIMS, no substitute
methods should be permitted.
Equivalent Methods
Equivalent methods should be permitted. Equivalent methods (TLC, GC/ECD,
etc.) are defined as methods which have been validated against the primary
method and yield comparable quantitative results and have LOQs comparable to
the primary method or lower LOQ than the regulatory cutoff. Results obtained
by an equivalent method must be confirmed by the primary method if significant
interferences are suspected or the levels found are near the regulatory cutoff
("near" must be defined). Any use of an equivalent method would be subject
to the additional QA provision that a specified number (e.g., every tenth) of
samples be routinely run by the primary method and that the two results agree
within specified tolerances (the agreement should be specified by homolog,
not simply by total PCB, to avoid any method bias toward one end of the homo-
log lines).
Since an equivalent method would be subject to validation and additional
QA, it would be applicable only to routine monitoring of a process. Obviously
any single batches or one-shot analyses would have to be done by the primary
method. The major application of equivalent methods is projected for the com-
pany with a process at several plants which must be monitored periodically.
Since most plants do not have GC/MS instrumentation and a slow turnaround from
central research would either delay product shipping or permit untested pro-
duct to be released to customers, use of an equivalent method appears to be
the only acceptable alternative.
QUALITY ASSURANCE
The QA options to be addressed include:
1. Round robins: One or more round robins appear to be a good mechanism
for improving the methodology and predicting the data quality. The objectives
and execution of the round robin need to be addressed. Whether periodic round
robins should be required is also of interest.
2. QA organization: Some organization must be designated to administer
QA. The responsibilities and authority of the organization need to be speci-
fied. At one extreme, the QA organization periodically reviews the data sub-
mitted. On the other extreme, the QA organization would have laboratory
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facilities and confirm results on selected samples, prepare and send out
performance audit samples, organize and execute round robins, conduct systems
audits, and conduct method development efforts when necessary. Clearly the
data quality and cost are roughly proportional to the amount of QA. A sensi-
ble compromise must be reached.
3. Systems audits; One standard QA practice is the systems audit.
This is especially valuable in that the QA officer observes the personnel and
facilities in operation and assesses their competence and performance. This
is the only way the QA office can monitor the laboratory practices and review
the raw data (chromatograms, mass spectra, magnetic tapes, etc.). The use of
systems audits is desirable, but it requires personnel and travel fund commit-
ments .
4. Performance audits: A performance audit is a quantitative analysis
with a material of known PCB content. Performance audits consist of blanks
and samples, blind or known, submitted by the QA lab and are generally ana-
lyzed along with routine samples. A performance audit system is mandatory as
part of the overall laboratory certification program.
5. Laboratory certification; A laboratory certification program is
recommended. The quality of the data and therefore the laboratory capabili-
ties and performance must be assured. There are several methods for labora-
tory certification: round robin participation, performance audit participa-
tion, or submission to a systems audit. Most likely a combination of the
three would be the most reasonable certification route. Following initial
certification, all participating laboratories must be periodically recertified.
Performance audits and systems audits are the most appropriate recertification
methods.
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APPENDIX A
PERSONAL CONTACTS
Note: In preparation of this document, telephone, written, or personal
discussions were held with the individuals listed.
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Ahmed, Karim. Natural Resources Defense Council, 122 E. 42nd Street,
New York, New York 10169.
Alford-Stevens, Ann. Environmental Monitoring and Support Laboratory,
U.S. Environmental Protection Agency, Cincinnati, Ohio 45268
Bell, Robert A. Corporate Research and Development, General Electric
Company, 1 River Road, K-l, 3B15, Schenectady, New York 12301, (518) 385-8505.
Albro, Phillip. NIEHS, Research Triangle Park, North Carolina 27711,
FTS 629-3264.
Bellar, Thomas A. Environmental Monitoring and Support Laboratory, U.S.
Environmental Protection Agency, Cincinnati, Ohio 45268, FTS 684-7311.
Bidleman, Terry F. Department of Chemistry, University of South Carolina,
Columbia, South Carolina 29208, (803) 777-4239.
Breen, Joseph J. Office of Toxic Substances, U.S. Environmental Protection
Agency, 401 M St., Washington, D.C. 20640, FTS 382-3569.
Budde, William. Environmental Monitoring Support Laboratory, U.S. Environ-
mental Protection Agency, Cincinnati, Ohio 45268, FTS 684-7309.
Burgess, Ken. Dow Chemical Company, 1803 Building, Midland, Michigan, 48640,
(517) 636-3177.
Bursey, Joan T. Analytical Sciences Division, Research Triangle Institute,
Research Triangle Park, North Carolina 27709, (919) 541-5928.
Bumgarner, Joseph. Environmental Monitoring and Systems Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina 27711,
FTS 629-2434.
Carey, Ann E. Office of Toxic Substances, U.S. Environmental Protection
Agency, 401 M St., Washington, D.C. 20460, FTS 382-3569.
Carra, Joseph. Office of Toxic Substances, U.S. Environmental Protection
Agency, 401 M St., Washington, D.C. 20460, FTS 382-3900.
Caspers, Horst. Stauffer Chemical Company, Dobbs Ferry, New York 10522,
(914) 673-1200.
Chesler, Stephen N. Organic Analytical Research Division, National Bureau of
Standards, Washington, D.C. 20234, (301) 921-2153.
Christman, Mark H. E. I. DuPont de Nemours, Wilmington, Delaware 19898,
(202) 774-6443.
Crouch, Michael D. Toxicon Laboratories, 3213 Monterrey Boulevard,
Baton Rouge, Louisana 70814, (504) 925-5012.
DaRoche, Maria. Sun Chemical Corporation, 441 Tompkins Avenue, Staten Island,
New York 10305, (212) 981-1600 ext. 215-
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Dougherty, Ralph C. Department of Chemistry, Florida State University,
Tallahassee, Florida 32306, (904) 644-5725.
Ewald, Fred. PPG Industries, Inc., P.O. Box 31, Barberton, Ohio 44203,
(216) 848-4600.
Fensterheim, Robert J. CMA, 2501 M Street, NW, Washington, D.C.,
(202) 887-1189.
Gebhart, Judy. Battelle Columbus Laboratories, 505 King Avenue, Columbus,
Ohio 43201.
Gunter, Bill. CCD, Office of Toxic Substances, U.S. Environmental Protection
Agency, 401 M Street, SW, Washington, B.C. 20460, (202) 382-3933.
Haile, Clarence L. Midwest Research Institute, 425 Volker Boulevard,
Kansas City, Missouri 64110, (816) 753-7600.
Hanneman, Larry F. Dow Corning, P.O. Box 1592, Midland, Michigan 48640,
(517) 496-5003.
Hass, J. Ronald. NIEHS, Research Triangle Park, North Carolina 27711,
FTS 629-3463.
Heggem, Daniel T. Field Studies Branch, Office of Toxic Substances, U.S.
Environmental Protection Agency, TS-798, Washington, D.C. 20460,
(202) 382-3584.
Hensler, Charles. DuPont, Jackson Lab, Deepwater, New Jersey 08023,
(609) 299-5000, ext. 3611.
Hodges, Kent L. Dow Chemical Company, 574 Building, Midland, Michigan 48640,
(517) 636-6544.
Johnson, Larry. Industrial Environmental Research Laboratory, U.S. Environ-
mental Protection Agency, Research Triangle Park, North Carolina 27711,
FTS 629-7943.
Kaley, Robert. Monsanto Company, 800 North Lindbergh Boulevard, St. Louis,
Missouri 63166, (314) 694-4964.
Kingsley, Barbara. SRI International, 333 Ravenswood Avenue, Menlo Park,
California 94025, (415) 326-6200.
Kleopfer, Robert D. Region VII, U.S. Environmental Protection Agency, 1735
Baltimore Avenue, Kansas City, Missouri 64108, (816) 374-4285.
Kutz, F. W. Field Studies Branch, Office of Toxic Substances, U.S. Environ-
mental Protection Agency, TS-798, Washington, D.C. 20460, (202) 382-3569.
Lewis, Robert G. Environmental Monitoring and Systems Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina 27711,
FTS 629-3065.
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Lopez-Avila, Viorica. Acurex, 485 Clyde Avenue, Mountain View, California
94042, (415) 964-3200.
Moll, Amy. Regulatory Impacts Branch, Office of Toxic Substances, U.S.
Environmental Protection Agency, TS-779, Washington, D.C. 20460
(202) 382-3715.
Mullin, Michael D. U.S. Environmental Protection Agency, Large Lakes Research
Station, 9311 Groh, Grosse lie, Michigan 48138, FTS 226-7011.
Parris, Reenie. Organic Analytical Research Division, National Bureau of
Standards, Washington, D.C. 20234, (301) 921-2153.
Pellizzari, Edo D. Analytical Sciences Division, Research Triangle Institute,
Research Triangle Park, North Carolina 27709.
Petty, James D. Fish-Pesticide Research Laboratory, Fish and Wildlife Service,
U.S. Department of Interior, Columbia, Missouri 65201, FTS 276-5399.
Pfaffenberger, Carl D. Division of Chemical Epidemiology, School of Medicine,
University of Miami, 15655 S.W. 127th Avenue, Miami, Florida 33177,
(305) 255-3300.
Redford, David. Office of Toxic Substances (TS-798), U.S. Environmental
Protection Agency, Washington, D.C. 20460, FTS 382-3583.
Robinson, J. Lawrence. Dry Color Manufacturers' Association, Suite 100,
1117 North 19th Street, Arlington (Rosslyn), Virginia 22209, (703) 525-9483.
Robinson, Thomas. Vulcan Materials Company, P.O. Box 7689, Birmingham,
Alabama 35253, (205) 877-3556.
Ronan, Richard. Versar, Inc., 6621 Electronic Drive, Springfield, Virginia
22151, (703) 750-3000.
Safe, Stephen, Department of Physiology and Pharmacology, College of
Veterinary Medicine, Texas A & M University, College Station, Texas 77843.
Sawyer, Leon D. Food and Drug Administration, 240 Hennepin Avenue,
Minneapolis, Minnesota 55401, FTS 725-2121.
Slevon, Larry. Battelle Columbus Laboratories, 505 King Avenue, Columbus,
Ohio 43201
Smith, John. DDB, Office of Toxic Substances, U.S. Environmental Protection
Agency, Washington, D.C. 20460, FTS 382-3900.
Sonchik, Susan. Versar, Inc., 6621 Electronic Drive, Springfield, Virginia
22151, (703) 750-3000.
Stalling, David L. Fish-Pesticide Research Laboratory, Fish and Wildlife
Service, U.S. Department of Interior, Columbia, Missouri 65201, FTS 276-5399.
79
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Underwood, Joseph. Food and Drug Administration, 1009 Cherry Street,
Kansas City, Missouri 64106, (816) 374-5524.
Warren, Jackie. Natural Resources Defense Council, 122 East 42nd Street,
New York, New York 10168.
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APPENDIX B
BIBLIOGRAPHY
81
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TECHNICAL REPORT DATA
{Please read Instructions on the reverse before completing)
1 REPORT NO
EPA-560/ 5-82-005
4 TITLE AND SUBTITLE
Methods of Analysis for By-
Review and Preliminary Reco
7 AUTHORIS)
Mitchell D. Erickson
John S. Stanley
2
Product PCBs — Li
mmendations
3. RECIPIENT'S ACCESSION NO.
5 REPORT DATE
horat-nr* October 1982
6. PERFORMING ORGANIZATION CODE
4901-A(51)
8. PERFORMING ORGANIZATION REPORT NO.
Interim Report No. 1
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Midwest Research Institute
A 25 Volker Boulevard
Kansas City, Missouri 64110
12 SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Toxic Substances
Field Studies Branch, TS-798
Washington, D.C. 20460
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO
68-01-5915 Task 51
13 TYPE OF REPORT AND PERIOD COVERED
Interim (March-April 1982)
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
Frederick W. Kutz, Project Officer
David P . Redf ord , Task Manager
16. ABSTRACT
A review of the literature on polychlorinated biphenyl (PCB) analysis and
recommendations for methods to determine by-product PCBs in commercial products and
other matrices is presented. This report was prepared to assist EPA in formulating
a rule regulating by-product PCBs. The published literature on PCB analysis is
critically reviewed. Several hundred references are cited in a bibliography. The
review if subdivided into extraction, cleanup, determination, data reduction, con-
firmation, screening, quality assurance, and by-product analysis sections. The
determination section includes TLC, HPLC, GC (PGC and COC) , GC detectors (ECD, FID,
HECD, EIMS, and other MS) and nonchromatographic analytical methods (NMR, IR, elec-
trochemistry, NAA, and RIA) . Techniques applicable to analysis of commercial prod-
ucts, air, and water for by-product PCBs are discussed. The final section of this
report presents a recommended overall primary analytical scheme.
17
KEY WORDS AND DOCUMENT ANALYSIS
II DESCRIPTORS
PCBs
Polychlorinated Biphenyls
Analysis
By-product PCBs
Review
18 DISTRIBUTION STATEMENT
Unlimited
b. IDENTIFIERS/OPEN ENDED TERMS
IB. SECURITY CLASS (TMt Report)
Unclassified
20 SECURITY CLASS (This page)
Unclassified
c. COSATI l-'ield/Group
21. NO. OF PAOES
135
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
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