United States
Environmental Protection
Agency
Environmental Monitoring
Systems Laboratory
Research Triangle Park NC 27711
Research and Development
EPA/600/S4-87/006 July 1987
&EPA Project Summary
Supplement to
EPA/600/4-84/041:
Compendium of Methods for
the Determination of Toxic
Organic Compounds in
Ambient Air (Revised 9/86)
R. M. Riggin, W. T. Winberry, Jr., and N. V. Tilley
This supplement was developed to
expand upon the original compendium
(4/84), which covered twenty-nine (29)
air toxics that could be analyzed by five
(5) general methods. The supplement
now increases the number of air toxics
to thirty-six (36) and the number of pro-
cedures to nine (9). The Compendium
was developed to complement a previ-
ously published document entitled
"Technical Assistance Document (TAD)
for the Determination of Toxic Organic
Compounds in Ambient Air." The com-
pendium provides a standardized for-
mat for analytical procedures used in
determining toxic compounds in ambi-
ent air. Further supplements to the
Compendium will occur as suitable pro-
cedures become available. The current
methods may also be modified as ad-
vancements are made.
The compendium sampling proce-
dures range from utilizing liquid im-
pingers to cryogenic trapping to adsor-
bent technology. Likewise, analytical
procedures range from on-line gas
chromatography (GC) to high resolu-
tion gas chromatography/high resolu-
tion mass spectroscopy (HRGC/HRMS)
techniques. Consequently, many toxic
organic compounds can be sampled
and analyzed by several techniques,
often with different interferences and
detection limitations. This allows the
user latitude in selection so as to com-
plement his background and laboratory
capability.
This Project Summary was devel-
oped by EPA's Environmental Monitor-
ing Systems Laboratory, Research Tri-
angle 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
Toxic air pollutants have been of con-
cern for many years, primarily under
Section 112 of the Clean Air Act, which
establishes procedures for designating
National Emission Standards for Haz-
ardous Air Pollutants (NESHAP).
NESHAPs are intended to provide con-
trol of source categories which emit
pollutants that "may reasonably be an-
ticipated to result in an increase in mor-
tality or an increase in serious irre-
versible, or incapacitating reversible,
illness."
Likewise, public concern for protec-
tion from exposure to toxic substances
has intensified over the last decade. Ev-
idence of the presence of these sub-
stances in ambient air across the United
States has been increasing for some
time. Although many of these sub-
stances are presently controlled
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through occupational, consumer pro-
tection, water or waste disposal regula-
tions, control of air pollution involving
specific toxic substances has been lim-
ited. This is due, in part, to a lack of
information on ambient air levels and
the uncertainty of the sampling and
analysis methods for their detection.
Over the last several years, State and
local air pollution control agencies have
increased their efforts to measure the
concentrations of toxic pollutants in
ambient air. These activities have in-
cluded monitoring around abandoned
hazardous waste dump sites and solid
waste landfills, as well as other point
source and urban area monitoring. For
the most part, network design, siting
and sampling/analysis procedures used
were based on professional judgments
rather than adherence to any docu-
mented, uniform procedures and guide-
lines. The absence of standardized pro-
cedures raises serious concerns about
the adequacy of the data collected for
their intended uses. Ensuring data ade-
quacy is critical, since major decisions
on control actions, health effects, and
other significant issues could be based
on the interpretation of such data.
The objective of this project was to
develop a compendium that would pro-
vide regional, state and local environ-
mental regulatory agencies with
specific guidance on sampling and ana-
lytical procedures, in a standardized for-
mat, for selected toxic organic com-
pounds.
Structure of the Compendium
The current compendium consists of
nine (9) procedures covering thirty-six
(36) organic toxic compounds. Each
procedure is written to be used inde-
pendently from the others and is di-
vided into twelve (12) sections entitled:
• Scope
• Applicable Documents
• Summary of Method
• Significance
• Definitions
• Interferences
• Apparatus
• Reagents/Materials
• Assembly/Calibration
• Sampling
• Analysis
• Performance Criteria and Quality
Assurance
The procedures are written in a stand-
ardized format used by the American
Society for Testing and Materials
(ASTM). Each procedure has been iden-
tified with a revision number and dated
to allow future modifications. Addi-
tional procedures, which may be
compound-specific or of multiple ana-
lyte design, will be placed in the com-
pendium as they become available.
Nearly all the procedures have some
flexibility. Consequently, users are re-
sponsible for preparing certain stand-
ard operating procedures (SOPs) to be
employed in their particular laboratory.
Each procedure indicates those opera-
tions for which SOPs are required.
Table 1 lists the procedures contained
in the compendium and Table 2 pre-
sents a partial listing of toxic organic
compounds which can be determined
using those procedures. Many of the
procedures may be used to determine
other toxic organics not indicated in
Table 2. The user must be cautioned to
evaluate the applicability of the metho
for that specific organic toxicant in at
vance.
Table 1. List of the Procedures Presently in the Compendium
Description
Procedure
Number
Types of
Compounds Determined
TO-1
TO-2
TO-3
TO-4
TO-5
TO-6
TO-7
TO-8
TO-9
Tenax GC Adsorption and
GC/MS Analysis
Carbon Molecular Sieve
Adsorption and GC/MS
Cryogenic Trapping and
GC/FID or ECD Analysis
High Volume PUF Sam-
pling and GC/ECD Analysis
Dinitrophenylhydrazine
Liquid Impinger Sampling
and HPLC/UV Analysis
High Performance Liquid
Chromatography (HPLC)
Thermosorb/N Adsorption
Sodium Hydroxide Liquid
Impinger Sampling with
High Performance Liquid
Chromatography (HPLC)
Analysis
High Volume Polyurethane
Foam Sampling with High
Resolution Gas Chroma-
tography/High Resolution
Mass Spectrometry (HRGC/
HRMS) Analysis
Volatile, nonpolar, organics
(e.g., aromatic hydrocarbons,
chlorinated hydrocarbons)
having boiling points in the
range of 80° to 200°C.
Highly volatile, nonpolar or-
ganics (e.g., vinyl chloride,
vinylidene chloride, benzene,
toluene) having boiling point
in the range of - 15° to
+ 120°C.
Volatile, nonpolar organics
having boiling points in the
range of - 10° to +200°C.
Organochlorine pesticides an
PCBs.
Aldehydes and Ketones
Phosgene
N-Nitrosodimethylamine
Cresols/Phenols
Dioxins
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Table 2. Applicability of Specific Procedure to Selective Toxic Organics
Applicable
Compound Procedure
Acetaldehyde TO-5
Acrolein TO-5
Acrylonitrile TO-2, TO-3
Allyl Chloride TO-2, TO-3
Benzaldehyde TO-5
Benzene TO-7, TO-2, TO-3
Benzyl Chloride TO-7, TO-3
Carbon Tetrachloride TO-2, TO-3
Chlorobenzene TO-1, TO-3
Chloroform TO-2, TO-3
Chloroprene TO-7, TO-3
<2-Chloro-1, 3-Butadiene)
Cresol TO-8
4,4'-DDE TO-4
4,4'-DDT TO-4
1,4-Dichlorobenzene TO-1, TO-3
Dioxin TO-9
Ethylene dichloride TO-2, TO-3
(1,2-Dichloroethane)
Formaldehyde TO-5
Methyl Chloroform TO-2, TO-3
(1,1, 1-Trichloroethane)
Methylene Chloride TO-2, TO-3
Nitrobenzene TO-1, TO-3
N-Nitrosodimethylamine TO-7
Perchloroethylene TO-7, TO-3
(Tetrachloroethylene)
Phenol TO-8
Phosgene TO-6
Polychlorinated Biphenyls TO-4
(PCBs)
Propanol TO-5
Toluene TO-7, TO-2, TO-3
Trichloroethylene TO-7, TO-2, TO-3
Vinyl Chloride TO-2, TO-3
Vinylidine Chloride TO-3, TO-3
(1,1-dichloroethene)
o,m,p-Xylene TO-7, TO-3
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R. M. Riggin was formally with Battelle-Columbus Laboratories, Columbus. OH
43201-2693; William T. Winberry,.Jr., and Nor ma Til ley are with Engineering
Science. Gary. NC27511.
L. J. Purdue and H. G. Richter are the EPA Project Officers (see below).
The complete report and the most recent supplement are entitled:
"Compendium of Methods for the Determination of Toxic Organic Compounds
in Ambient Air," (Order No. PB 87-168 688/AS; Cost: $ 18.95)
"Supplement to EPA/600/4-84/041: Compendium of Methods for the
Determination of Toxic Organic Compounds in Ambient Air," (Order No
PB 87-168 696/AS; Cost: $18.95)
The above reports will be available only from: (cost subject to change)
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officers can be contacted at:
Environmental Monitoring Systems "Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
U.S. OFFICIAL MAI
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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