United States
Environmental Protection
Agency
Industrial Environmental
Research Laboratory
Research Triangle Park NC 27711
Research and Development
EPA-600/S7-84-078 Sept. 1984
Project Summary
Candidate Sampling and
Analysis Methods for 21
Suspect Carcinogens in
Combustion Emissions
W.M. Cooke, W.H. Piispanen, A.K. Wensky, G.A. Lutz, T.F. Cole, J.S. Ogden, A.
Levy, R.H. Barnes, B.W. Cornaby, and K.B. Degner
The report identifies candidate sam-
pling and analysis methods for 21
suspect carcinogens in conventional
coal and fuel oil combustion emissions.
The methods were selected from an
extensive review of existing techniques
used to determine the substances in air
and other matrices. In addition to
identifying specific methods for each
suspect carcinogen, the report describes
a comprehensive sampling and analysis
protocol which can be used to determine
13 of the suspect carcinogens. Costs
for the separate candidate methods and
for the comprehensive protocol are also
provided.
This Project Summary was developed
by EPA's Industrial Environmental
Research Laboratory. Research Triangle
Park, NC, to announce key findings of
the research project that is fully
documented in a separate report of the
same title (see Project Report ordering
information at back).
Introduction
The U.S. EPA's Office of Air Quality
Planning and Standards (OAQPS) has
listed 21 substances as having a high
probability of being carcinogenic. The
formation of these suspect carcinogens
in combustion processes could conse-
quently pose a significant health hazard.
The presence of the 21 substances in
combustion emissions must therefore be
evaluated. The substances are:
acrylonitrile
arsenic
asbestos
benzene
beryllium
cadmium
diethylnitrosamine
dimethylnitrosamine
2,3,7,8-tetrachlorodioxin
ethylene dibromide
ethylene dichloride
ethylene oxide
formaldehyde
nickel
N-nitroso-N-ethyl urea
N-nitroso-N-methyl urea
perchloroethylene
polynuclear aromatic hydrocarbons (PAH)
trichloroethylene
vinyl chloride
vinylidene chloride
This report identifies candidate sam-
pling and analysis methods which can be
used to determine 21 substances in
conventional coal and fuel oil combustion
emissions. The sampling and analysis
methods in this report provide an
excellent reference basis for conducting
this work.
The report presents a collaboration of
independent efforts conducted by Bat-
telle's Columbus Laboratories and Arthur
D. Little, Inc. Each contractor had
prepared a separate report describing the
findings of their individual investigation
to identify methods for determining the
suspect carcinogens in combustion
emissions. The information presented in
the two separate reports is compiled in
this report.
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The report presents an overview of
existing methodology used to determine
the 21 substances and identifies the
methods selected from this overview as
appropriate for the sampling and analysis
of the suspect carcinogens in combustion
emissions. Additional material presented
includes an evaluation of the combustion
formation potential of the suspect
carcinogens, a description of a compre-
hensive protocol for determining 13 of
the substances in a single field study,
and an estimation of costs for conducting
each separate method on a single
compound and for implementing the
comprehensive protocol for determining
13 of the substances. Appendices supple-
ment the overview of existing methodo-
logy in the body of the report by
individually describing specific sampling
and analysis procedures for the suspect
carcinogens.
Summary
Combustion Formation
Potential
The purpose of this initial effort was to
determine the potential of the 21 suspect
carcinogens for formation in combustion
processes. Eight of the substances
(trichloroethylene, formaldehyde, 2,3,7,8-
tetrachlorodibenzodioxin, PAH, arsenic,
beryllium, cadmium, and nickel) have
been reported as being present in coal
and fuel oil combustion emissions. The
combustion formation potential of the
remaining 13 substances was evaluated
on the basis of thermodynamic stability,
organic synthesis chemistry, and com-
bustion conditions. The presence of
acrylonitrile, benzene, vinyl chloride, and
vinylidene chloride in combustion emis-
sions was deemed reasonably or highly
probable. Asbestos was also assessed as
having a high probability of being present
in combustion emissions since many older
furnaces have exposed asbestos linings.
The remaining eight substances were
evaluated and determined to have a
minimal potential for formation in
combustion processes.
Overview of Existing
Methodology
Existing sampling and analysis method-
ology for the 21 suspect carcinogens
was reviewed to provide a basis for
selecting candidate procedures for
determining the substances in combus-
tion emissions. Based on general require-
ments for air sampling, the features and
previous applications of three major
methods—EPA's Source Assessment
Sampling System (SASS), EPA's Method
5 sampling train, and grab sampling—
were reviewed. Each method was found
to be successful for sampling one or more
of the substances under consideration.
Analytical methods reviewed included
EPA Level 1 Environmental Assessment
Procedures and other documented EPA
methods. Additional analytical techniques
reviewed included NIOSH procedures
and several literature methods. Numerous
methods were identified for determining
the suspect carcinogens in water, soil,
sediment, sludge, and other matrices.
Few methods, however, had been specifi-
cally designed or validated for application
to combustion emissions. Sampling and
analysis procedures for asbestos were
considered separately. Existing asbestos
techniques were found to be time-
consuming and often unvalidated.
Specific Sampling and
Analysis Recommendations
Comparison and evaluation of the
reviewed sampling and analysis tech-
niques led to the selection of candidate
methods for determining the 21 suspect
carcinogens in combustion emissions.
Precedence was given to previously
validated methods. Recommendations
for candidate sampling methods were
restricted to proven air sampling methods
since techniques for sampling water, soil,
or other matrices would not apply. Forthe
candidate analytical methods, techniques
successfully used to determine the
suspect carcinogens in other matrices
were recommended when techniques
had not been verified for analysis in air
emissions.
The specific sampling and analysis
methods recommended for the suspect
carcinogens are listed in Table 1.
Sampling recommendations primarily
involved variations of EPA's SASS train,
Method 5 train, and grab sampling
methods. Separate procedures were
recommended for arsenic and formalde-
hyde. Several sampling methods were
suggested for asbestos since the reliability
of any one method has yet to be proven.
For analysis of the organic compounds,
gas chromatography (GC), combined gas
chromatography/mass spectrometry
(GC/MS), and high performance liquid
chromatography (HPLC) methods were
included in the recommendations. Atomic
absorption spectroscopy (AAS) was
suggested for inorganic elements. For
asbestos, analysis with transmission
electron microscopy was recommended.
The recommended sampling and analysis
methods have not, in most cases, been
subjected to necessary laboratory and
field validations; however, the methods
should provide reliable analyses of the
concentrations of the suspect carcinogens
in combustion emissions if employed
with adequate quality control.
Comprehensive Sampling and
Analysis Protocol
The candidate sampling and analysis
methods are similar for several of the
suspect carcinogens. To reduce the
amount of effort required for determining
the complete group of substances in a
single source emission, combinations of
redundant techniques were considered.
A sampling and analysis protocol for a
comprehensive field study was developed
incorporating these combinations. The
comprehensive protocol only accom-
modates those 13 suspect carcinogens
which have been reported to exist or
which have a reasonable to high probabil-
ity of being formed in combustion
emissions as determined in this report.
The sampling system for the compre-
hensive field study protocol is shown in
Figure 1. The sampling system for the
comprehensive field study protocol
incorporates all EPA standard methods:
(1) a SASS train or a high volume Method
5 train with an organic adsorbent column,
(2) a midget impinger train similar to
Method 6, and (3) an evacuated Tedlar
bag sampling train similar to Method 106
with a bypass charcoal tube. Dioxin, PAH,
the four metals, and asbestos are
collected by the SASS or the Modified
Method 5 train. Subsequent analysis
would include combined GC/MS for
dioxin and PAH, AAS for the metals, and
electron microscopy for asbestos. The
midget impinger train collects formalde-
hyde by derivatization with 2,4-dinitro-
phenylhydrazine. Analysis is conducted by
GC or HPLC. The Tedlar sampling bag
train collects the volatile organics and
acrylonitrile. GC with flame ionization
detection (FID) would be used to analyze
these compounds.
An alternative to the comprehensive
field study sampling and analysis protocol
was also developed. This second protocol
incorporates features to provide Level 2
environmental assessment information.
The sampling system would be collected
in a Tenax-GC sampling tube instead of a
Tedlar bag. Analytical modifications
include the use of GC/MS(forthe volatile
organics and formaldehyde) and GC with
alkali flame detection, rather than FID (for
acrylonitrile). The alternative protocol
would provide a higher precision and
accuracy than the original comprehensive
field study protocol; however, the tech-
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Table 1, Recommended Sampling and Analysis Procedures for 21 Suspect Carcinogens in Combustion Emissions
Compound
Sampling Method
Analytical Procedure
ORGAN/OS
Acrylonitrile
Benzene
Diethylnitrosamine
Dimethylnitrosamine
Dioxin
Ethylene Dibromide
Ethylene Dichloride
Ethylene Oxide
Formaldehyde
Nitrosoethylurea
Nitrosomethylurea
Perchloroethylene
PAH
Trichloroethylene
Vinyl Chloride
Vinylidene Chloride
INORGANICS
Arsenic
Beryllium
Cadmium
Nickel
ASBESTOS
Charcoal Tube
Tedlar bag/Gas bulb
SASS Train/Sorbent
SASS Train/Sorbent
SASS/Modified Method 5 Train
SASS Train/Sorbent
Gas Bulb
Charcoal Tube
Impinger (DNPII)
SASS Train/Sorbent
SASS Train/Sorbent
SASS Train/Sorbent
SASS/Modified Method 5 Train
Tedlar bag/Gas bulb
Tedlar bag/Gas bulb
Tedlar bag/Gas bulb
Method 5 Train/Modified
Aerotherm HVSS system
Method 5 train
Method 5 train
Method 5 train
Filter
GC/FID or GC/MS for specificity
GC/FID
GC/FID
GC/FID
GC/MS
GC/FID
GC/ECD
GC/FID
HPLC, GC, or GC/MS for identification
HPLC with UV detection
HPLC with UV detection
GC/ECD
GC/MS
GC/FID
GC/FID
GC/FID
Hydride Generation AAS
AAS
AAS
AAS
Transmission Electron Microscopy
niques in the alternative protocol are not
all EPA-approved.
Cost Model
Separate costs were calculated for
individual analyses conducted on a single
sample. In addition, a detailed cost model
for the Level 2 comprehensive field study
protocol was developed. The model was
derived by establishing the labor, instru-
mentation, and laboratory capabilities
needed to conduct each activity of a
comprehensive field study such as
planning, pre-site survey, sampling,
sample delivery, data evaluation, and
reporting. A cost matrix of capabilities
versus activities was then generated
which itemized each cost element and
summarized the total costs.
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TC
Magnahelics
Asbestos
Metals
PAHs
Dioxin
t
Paniculate
Metals
Dioxin
POM
XAD-2.
Condensate
Sorbent Trap
As
Ni
4
Volatile Metals
in H2OS/APS
SASS Train
Impingers
Pump
High Volume
Modified
Methods
Train
Meters
Impingers
Pump
Formaldehyde
NaHS03 or DNPH/HCI
or MBTH
Midget
Impinger
Train
Impingers
Pump
Meters
Vinyl/dene Chloride
Vinyl Chloride
Trichloroethylene
Benzene
Optional
Gas Conditioner
t — T
Gas
Sample
Acrylonitrile
Vinyl Chloride
4
Trapped Volatiles
Glass
Wool
Probe
c
"^Bag Sample
J. Tube Sample
Bag Evacuate
Tube Sample
100 * Tedlar Bag
Meters
Figure 1. Sampling system for comprehensive field study protocol.
•&U. S. GOVERNMENT PRINTING OFFICE: 1984/759-102/10658
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W. M. Cooke, W. H. Piispanen. A. K. Wensky, G. A. Lutz, T. F. Cole. J. S. Ogden, A.
Levy, R. H. Barnes, B. W. Cornaby, andK. B. Degnerare withBattelle-Columbus
Laboratories, Columbus, OH 43201.
Michael C. Osborne is the EPA Project Officer (see below).
The complete report, entitled "Candidate Sampling and Analysis Methods for 21
Suspect Carcinogens in Combustion Emissions," (Order No. PB 84-224 401;
Cost: $17.50, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Industrial Environmental Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park. NC 27711
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Official Business
Penalty for Private Use $300
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