United States
Environmental Protection
Agency
National Exposure
Research Laboratory
Research Triangle Park, NC 27711
Research and Development
EPA/600/SR-96/091
August 1996
EPA Project Summary
Evaluation of CAAA Compounds:
Approaches for Stationary
Source Method Development
Denny E. Wagoner, Raymond G. Merrill, Jr., James F. McGaughey and Joan T.
Bursey
Abstract
A literature search-based study was
performed to evaluate a selected sub-
set of the 189 analytes listed in Title III
of the Clean Air Act Amendments of
1990 for certain criteria. The overall
objective of this program was to ac-
quire sufficient information about physi-
cal properties and chemical character-
istics of the compounds to suggest a
technical approach for the sampling
and analysis of these compounds from
stationary sources. A database of the se-
lected Clean Air Act Amendments com-
pounds was prepared in spreadsheet for-
mat with detailed physical properties,
chemical characteristics, and a sum-
mary categorizing the compounds in
terms of potential sampling and ana-
lytical approaches. Recommendations
for the sampling and analytical meth-
odology for selected compounds or
compound classes are also included
where no methods have been docu-
mented or evaluated.
This Project Summary was developed
by the National Exposure Research
Laboratory's Air Methods Research Di-
vision, 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
Title III of the Clean Air Act Amend-
ments (CAAA) of 1990 contains 189 en-
tries as substances to be regulated. Far
more than 189 individual chemicals are to
be regulated, for some of the entries en-
compass hundreds of individual com-
pounds: e.g., dibenzofurans as a category
include 135 individual compounds, and
polychlorinated biphenyls include more
than two hundred individual compounds.
The EPA has developed or is evaluating
methods for many of the major chemical
classes of these 189 compounds. Station-
ary source sampling and analytical meth-
ods for these compounds are under vari-
ous stages of development or evaluation.
In this program, compounds requiring fur-
ther investigation have been identified and
searches of the literature have been per-
formed to gather information and evaluate
a selected subset of the 189 CAAA en-
tries for certain criteria. Physical proper-
ties and chemical characteristics of the
compounds have been evaluated in order
to propose a technical approach for the
sampling and analysis of these compounds
form stationary sources.
The CAAA analytes fall into several cat-
egories:
Compounds which should perform
reasonably well with existing method-
ologies because they meet the sug-
gested method criteria such as boil-
ing point. However, minimal method
evaluation data are available for the
CAAA analytes, so the performance
of the methodology for the analytes
must be evaluated.
Compounds which should perform
reasonably well when existing meth-
odology is modified (i.e., compounds
which must be derivatized before gas
chromatographic analysis, compounds
which require a specialized gas chro-
matographic column, or compounds
which will require use of high perfor-
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mance liquid chromatography rather
than gas chromatography for analy-
sis).
Compounds for which a completely
new sampling and analytical approach
must be developed and evaluated.
The study of the literature and evalua-
tion of existing data clearly indicate that
the general sampling and analytical tech-
niques that are commonly utilized (i.e.,
VOST, Method 18, Method 0010/Method
8270, Method 0011) provide adequate
monitoring capability for many of the vola-
tile and semivolatile organic compounds
listed in the CAAA. However, the com-
plexity of the chemical behavior of CAAA
compounds will require the development
of many new and/or modified sampling
and analytical techniques for successful
monitoring.
The mandate of this study was restricted
to selected compounds from the total of
189 entries from the Clean Air Act Amend-
ments. The families of metallic compounds
were excluded from consideration, as were
the families of compounds such as poly-
cyclic organic matter (POM). Also excluded
from consideration were compounds for
which development of specific methods is
presently in progress under EPA Contract
68-D1-0010, including the application of
VOST to volatile halogenated organic com-
pounds and Method 0010/8270 for
semivolatile halogenated organic com-
pounds.
Procedure
The information used to develop the
spreadsheet of chemical information was
derived from a variety of sources, includ-
ing:
Internal sources such as various in-
vestigators who have been involved
in the development and evaluation of
sampling and analytical methodology
for a wide variety of organic and inor-
ganic compounds;
"Screening Methods for the Develop-
ment of Air Toxics Emission Factors,"
an EPA report prepared under EPA
Contract number 68-D9-0054 (EPA-
450/4-91-021);
"Handbook of GC/MS Data and Infor-
mation for Selected Clean Air Act
Amendments Compounds," an EPA re-
port prepared under Contract number
68-D1-0010;
CRC Handbook;
NIOSH;
HON Database;
Merck Index;
The Environmental Monitoring Meth-
ods Index System (EMMI), which in-
cludes information on more than 2,600
analytes from over 80 regulatory and
nonregulatory lists and more than 900
analytes from the Clean Water Act
(CWA), Comprehensive Environmen-
tal Response, Compensation and Li-
ability Act (CERCLA), Superfund
Amendments and Reauthorization Act
(SARA), Resource Conservation and
Recovery Act (RCRA), Safe Drinking
Water Act (SDWA), the Clean Air Act
(CAA), and analytes from other EPA
and State lists;
Material Safety Data Sheets for indi-
vidual compounds;
Agrochemical Handbook;
Environmental Science and Technol-
ogy; and
Handbook of Toxic and Hazardous
Chemicals.
An Appendix to the report includes a
summary of physical and chemical prop-
erties for the compounds of interest, in-
cluding structures for the compounds.
When sampling or analytical methodol-
ogy is required for a compound, there are
usually several choices:
On the basis of physical parameters
such as boiling point, an analyte is
assigned to a methodology, and the
performance of this methodology for
this analyte has been demonstrated
to be effective in previous evaluation
of the methodology;
An analyte is conditionally assigned
to a methodology on the basis of
physical parameters, chemical judg-
ment, and experience, but no data
are available to define the perfor-
mance of the assigned methodology;
An existing methodology does not
work or does not work well for a given
analyte, but a modification of the
methodology (i.e., substitution of
HPLC/MS for GC/MS, substitution of
basic impingers for sorbent in a sam-
pling train) can produce acceptable
performance for a given analyte when
the modified methodology is evalu-
ated; or
No known sampling/analytical meth-
odology has a reasonable expecta-
tion of successful performance; a com-
pletely new sampling/analytical
method must be developed to obtain
test data for the analyte.
Existing methodology must be evalu-
ated for a wide variety of Clean Air Act
Amendments analytes, to determine the
range and limitations of existing method-
ology. To evaluate existing methodology
the following steps are required:
Establish a successful analysis. The
applicability of the sampling method-
ology and the sample recovery can-
not be evaluated until a given com-
pound can be analyzed accurately and
reproducibly.
Evaluate the recovery of the com-
pound of interest from the proposed
collection media. Once the compound
analysis is established, the ability to
recovery the compound from the col-
lection media can be evaluated and
new recovery procedures developed,
if required.
Establish the collection ability of the
proposed collection media. For ex-
ample, if a sorbent is proposed as
the collection medium and successful
recovery from the sorbent and suc-
cessful analysis of the analyte have
been established, the ability of the
sorbent to quantitatively collect the
compound of interest must be evalu-
ated. The collection ability of the me-
dium can be established by dynamic
spiking of the sampling train, incorpo-
rating as many of the characteristic
source variables as possible. For ex-
ample, if hot, wet, acidic sources are
expected, this source environment can
be created in the laboratory or lo-
cated in the field, and dynamic spik-
ing into replicate sampling trains with
recovery and analysis will demonstrate
that the sampling train does indeed
collect the compound of interest quan-
titatively.
Results and Discussion
Compounds expected to be amenable
to existing methods are shown in Table 1.
Compounds expected to require develop-
ment of specialized methodology or major
modification of existing methodology are
shown in Table 2, with the expected prob-
lem areas. Other analytes are discussed
on an individual basis, to formulate sug-
gestions for sampling and analytical ap-
proaches which may provide effective sam-
pling/analysis for the analyte, e.g.,
diethanolamine.
Diethanolamine
Diethanolamine is a water-soluble com-
pound used as an emulsifier and dispers-
ing agent. Diethanolamine should be col-
lected in a Method 0010 XAD-2ฎ/water
collection system. Because of the water
solubility of diethanolamine, aqueous
impingers may constitute a better collec-
tion system. Extraction of diethanolamine
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Table 1. Compounds Expected to be Amenable to Existing Methods without Modification Currently Being Tested in the Methodology Indicated
SemiVOST
(Method 0010/82701)
VOST
(Method 0030/5041)
Method 0011
acetophenone
2-acetylaminofluorene
benzidine
biphenyl
b9s(2-ethylhexyl) phthalate
catechol
chlordane
2-chloracetophenone
cresols
o-cresol
m-cresol
p_-cresol
cumene
DDE
dibenzofuran
di-n-butyl phthalate
dichlorvos
N,N-dimethylaniline
N,N-diethylaniline
3,3'-dimethoxybenzidine
dimethylaminoazobenzene
3,3'-dimethylbenzidine
dimethyl phthalate
4,6-dinitro-o-cresol
2,4-dinitrophenol
2,4-dinitrotoluene
1,4-dioxane
ethylbenzene
ethyl carbamate
ethylene thiourea
heptachlor
hexamethylene-1,6-diisocyanate
hexamethylphosphoramide
hydroquinone
acetonitrile
acrylonitrile
benzene
carbon disulfide
1,1-dimethylhydrazine
1,4-dioxane
1,2-epoxybutane
ethyl acrylate
ethyl imine
hexane
methyl ethyl ketone
methyl isobutyl ketone
methyl methacrylate
methyl tert-butyl ether
propylene oxide
1,2-propyleneimine
triethylamine
2,2,4-trimethylpentane
vinyl acetate
acetaldehyde
acetophenone
acrolein
2-chloroacetophenone
formaldehyde
hydroquinone
isophorone
methyl ethyl ketone
methyl isobutyl ketone
propionaldehyde
quinone
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Table 1. Compounds Expected to be Amenable to Existing Methods without Modification Currently Being Tested in the Methodology Indicated (continued)
SemiVOST VOST
(Method 0010/82701) (Method 0030/5041) Method 0011
isophorone
lindane
maleic anhydride
methoxychlor
4,4'-methylene bis(2-chloroaniline)
4,4'-methylenedianiline
naphthalene
nitrobenzene
4-nitrobiphenyl
4-nitrophenol
N-nitrosodimethylamine
N-nitrosomorpholine
parathion
phenol
p_-phenylenediamine
phthalic anhydride
1,3-propane sultone
propoxur
quinoline
quinone
styrene
styrene oxide
2,4-toluenediamine
o-toluidine
trifluralin
xylenes
m-xylene
o-xylene
p_-xylene
quantitatively extracted from XADฎ. Method 8270 analytical conditions are applicable to a far wider range ofanalytes than the analytes amenable to the
SemiVOST method.
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Table 2. Compounds Expected to
Compound
Perform Poorly in Existing Methodology
Problem
acetamide
2-acetylaminofluorene
acrylamide
acrylic acid
acrylonitrile
4-aminobiphenyl
benzidine
bis(chloromethyl)ether
1,3-butadiene
caprolactam
captan
carbaryl
carbon disulfide
carbonyl sulfide
catechol
chloroacetic acid
2,4-D, salts and esters
DDE
diazomethane
3,3'-dichlorobenzidine
dichlorvos
diethanolamine
diethyl sulfate
3,3'-dimethoxybenzidine
dimethylaminoazobenzene
3,3'-dimethylbenzene
dimethyl carbamoyl chloride
N, N-dimeylformamide
1,1-dimethylhydrazine
dimethyl sulfate
4,6-dinitro-o-cresol and salts
2,4-dinitrophenol
1,2-diphenylhydrazine
epichlorohydrin
Very polar; chromatographs poorly
Polar; high molecular weight; solubility problems
Very polar
Polar and reactive; does not chromatograph well on most GC columns
Very polar
Polar; high molecular weight; solubility problems
Polar and reactive; does not chromatograph well on most GC columns
Polar, reactive; reacts with water
Very volatile, very reactive
Very polar; chromatographs poorlyy using GC techniques
Polar; chromatographs poorly by GC
Polar; reactive; chromatographs poorly; poor GC/MS response
Volatile; polar; water-soluble
Reactive gas
Very polar and water-soluble; chromatographs very poorly on most GC columns
Polar; reactive; reacts with water; chromatographs very poorly on most GC columns
Not all amenable to GC techniques; polar and reactive
Very reactive
Very reactive; polar; cannot be chromatographed as diazomethane
Very polar; chromatographs poorly on most GC columns
Polar; chromatographs poorly on most GC columns
Very polar; chromatographs poorly on most GC columns
Very reactive; chromatographs poorly on most GC columns
Very polar: high molecular weight; chromatographs poorly on most GC columns
Very polar; chromatographs poorly on most GC columns
Very polar; chromatographs poorly on most GC columns
Very polar; not amenable to GC techniques
Very polar; chromatographs very poorly on most GC columns
Very polar; reactive; chromatographs very poorly on most GC columns
Very polar; reactive; chromatographs poorly
Very polar; not all amenable to GC techniques
Very polar; reactive; chromatographs poorly on most GC columns
Very polar; reactive; decomposes to azobenzene in the injector port of the GC
Very polar; water-soluble; reacts with water; chromatographs poorly on most GC columns
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Table 2. Compounds Expected to Perform Poorly in Existing Methodology (continued)
Compound Problem
1,2-epoxybutane
ethyl acrylate
ethyl carbamate
ethylene glycol
ethyleneimine
ethylene oxide
ethylene thiourea
hexamethylphosphoramide
maleic anhydride
methanol
methoxychlor
methyl hydrazine
methyl methacrylate
4,4'-methylene bis (2-chloroaniline)
4,4'-methylenedianiline
4-nitrobiphenyl
4-nitrophenol
2-nitropropane
N-nitrosodimethylurea
N-nitrosodimethylamine
N-nitrosomorpholine
p_-phenylenediamine
phthalic anhydride
1,3-propane sultone
K-propiolactone
propoxur
propylene oxide
1,2-propyleneimine
styrene
2,4-toluenediamine
o-toluidine
toxaphene
triethylamine
trifluralin
vinyl acetate
Polar; water-soluble
Polar; water-soluble
Polar; chromatographs poorly; poor MS response
Polar; water-soluble; chromatographs poorly on most GC columns
Polar; water soluble; reactive
Polar; water-soluble; reac ive; mass 44 difficult to analyze by GC/MS
Polar; water-soluble; chromatographs poorly on most GC columns
Polar; chromatographs poorly on most GC columns; poor MS response
Polar; water-soluble; chromatographs poorly on most GC columns
Polar; water-soluble; volatile; mass 32 is difficult to analyze by GC/MS; requires a special column for good chromatography
Polar; chromatographs poorly on most GC columns
Polar; water-soluble; reactive
Polar; water-soluble; volatile
Polar; chromatographs very poorly on most GC columns
Polar; chromatographs very poorly on most GC columns
Polar; chromatographs very poorly on most GC columns
Polar; chromatographs very poorly on most GC columns
Polar; not amenable to GC analysis
Very polar; chromatographs poorly on most GC columns
Very polar
Very polar; chromatographs poorly on most GC columns
Polar; chromatographs poorly on most GC columns
Very polar; reacts with water; chromatographs poorly on most GC columns; poor MS response
Very polar; chromatographs poorly on most GC columns
Polar; reactive
Polar; chromatographs poorly on most GC columns
Polar; water-soluble; volatile
Polar; water-soluble; volatile
Semivolatile, butstyrene is a component of the XAD-2ฎ polymer. Sampling styrene with Method 0010 may require
a special polymer.
Polar; water-soluble; chromatographs poorly on most GC columns
Polar; water-soluble; chromatographs poorly on most GC columns
Multicomponent pesticide (at least 50-60 components);willrequireverysensitiveandspecificanalysis,withpattern recognition
Polar; water-soluble; volatile; chromatographs poorly on most GC columns
Polar; chromatographs poorly on most GC columns; poor MS response
Polar; water-soluble; volatile
6
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from water by either an organic solvent or
solid phase extraction techniques should
be explored as an alternative to analysis
by direct aqueous injection, because di-
rect aqueous injection has high detection
limits. The inability to perform GC/MS
analysis of diethanolamine under Method
8270 analytical conditions has been dem-
onstrated. Use of a polar gas chromato-
graphic column may improve the analysis,
or HPLC or HPLC/MS may be required
for analysis of this analyte.
Individual evaluations of more than 90
Clean Air Act Amendments analytes are
provided.
Conclusions and
Recommendations
The following conclusions can be drawn
from the literature studied for this program
and from available method evaluation data:
Performance of a given sampling/ana-
lytical methodology for a given analyte
is strongly matrix-dependent. Avail-
ability of excellent method evaluation
data at one particular source category
does not establish that the methodol-
ogy will always perform successfully
for the analyte at any source. The
only way to establish with complete
certainty that a given methodology
will perform successfully for a given
analyte at a particular source is to
demonstrate the efficacy of the meth-
odology for the analyte, using some
kind of field spiking technique.
Because of the chemical properties
of many of the Clean Air Act Amend-
ments analytes (such as polarity or
water solubility), standard analytical
conditions such as those used in
Method 8270 or Method 5041 will not
provide an adequate analysis. New
analytical approaches must be con-
sidered and evaluated.
Multistep analytical procedures will be
required for the broadest possible ex-
tension of the applicability of a given
sampling methodology. For example,
analytes collected on XAD-2ฎ may
be extracted by use of a sequence of
solvents, extracts may be divided so
an aliquot can undergo a derivatization
procedure, sequential analysis on dif-
ferent chromatographic columns may
be required, analysis by both GC/MS
and HPLC/MS may be required. The
alternative to multistep analytical pro-
cedures is the collection of multiple
samples for individual analytical pro-
cedures.
Alternative extraction techniques such
as supercritical fluid extraction should
be considered for Tenaxฎ and XAD-
2ฎ, the most commonly used collec-
tion sorbents.
Creative new sampling and analytical
approaches are required to resolve
the sampling and analytical problems
posed by polar water-soluble com-
pounds.
The ultimate demonstration of a suc-
cessful overall sampling/analytical
method is the application of dynamic
spiking procedures in a field test. The
analyte(s) must be introduced as close
to the tip of the probe of the sampling
train as possible throughout the dura-
tion of the sampling process. In many
cases for the compounds of interest,
dynamic spiking procedures need to
be developed and/or evaluated be-
fore they can be applied in the field.
The applicability of broad-based meth-
ods such as VOST and Method 0010/
8270 should be evaluated for the wid-
est possible range of analytes to de-
termine the range and limitations of
these methods prior to the develop-
ment of multiple methods for individual
analytes.
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Denny E. Wagoner, Raymond G. Merrill, Jr., James F. McGaughey, and Joan T.
Bursey are with Radian Corporation, Research Triangle Park, NC 27709.
Merrill D. Jackson is the EPA Project Officer (see below).
The complete report, entitled "Evaluation of CAAA Compounds Approaches for
Stationary Source Method Development," (Order No. PB96-193206; Cost:
$41.00, 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:
Air Methods Research Division
National Risk Management Research Laboratory
U. S. Environmental Protection Agency
Research Triangle Park, NC 27711
United States
Environmental Protection Agency
National Risk Management Research Laboratory (G-72)
Cincinnati, OH 45268
Official Business
Penalty for Private Use $300
BULK RATE
POSTAGE & FEES PAID
EPA
PERMIT No. G-35
EPA/600/SR-96/091
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