United States
Environmental Protection
Agency
Atmospheric Research and
Exposure Assessment Laboratory
Research Triangle Park NC 27711
Research and Development
EPA/600/S4-89/018 Mar. 1990
&EPA Project Summary
Second Supplement to
Compendium of Methods for the
Determination of Toxic Organic
Compounds in Ambient Air
W. T. Winberry, Jr., Norma T. Murphy, and R. M. Riggin
The Compendium of Methods for
the Determination of Toxic Organic
Compounds In Ambient Mr was com-
piled to provide current, written, peer-
reviewed procedures in a stan-
dardized format for determining con-
centrations of toxic organic com-
pounds of importance in ambient air.
This Second Supplement to the Com-
pendium adds 5 new methods, bring-
ing the number of procedures con-
tained in the Compendium to 14. A
complementary document titled
Technical Assistance Document (TAD)
for the Determination of Toxic Organic
Compounds In Ambient Air provides
general guidance for ambient moni-
toring of organic compounds.
The sampling procedures in the
Compendium Include liquid im-
plngers, passivated steel canisters,
and various adsorbent, cryogenic,
and foam trapping technology. Ana-
lytical procedures include gas and
liquid chromatography with various
detectors including mass spec-
troscopy techniques. Many toxic or-
ganic compounds can be sampled
and analyzed by several techniques,
often with different interferences and
detection limitations. This allows flex-
ibility in selecting procedures to
complement the user's expertise and
laboratory capability.
This Project Summary was devel-
oped by EPA's Atmospheric Research
and Exposure Assessment 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
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 control
of source categories which emit pollu-
tants that "may reasonably be anticipated
to result in an increase in mortality or an
increase in serious irreversible, or in-
capacitating reversible, illness."
Likewise, public concern for protection
from exposure to toxic substances has in-
tensified over the last decade. Evidence
of the presence of these substances in
ambient air across the United States has
been increasing for some time. Although
many of these substances are presently
controlled through occupational, con-
sumer protection, water or waste disposal
regulations, control of air pollution in-
volving specific toxic substances has
been limited. This is due, in part, to a
lack of information on ambient air levels
of these substances and the uncertainty
of the sampling and analysis methods for
their measurement.
Over the last several years, state and
local air pollution control agencies have
increased their efforts to measure the
concentrations of toxic pollutants in am-
bient air. These activities have included
monitoring around abandoned hazardous
waste dump sites and solid waste land
-------
fills, as well as other point source and
urban area monitoring. For the most part,
network design, siting, sampling, and
analysis procedures used were based on
professional judgments rather than ad-
herence to any documented, uniform pro-
cedures and guidelines. The absence of
standardized procedures raises serious
concerns about the adequacy of the data
collected for their intended use. Ensuring
data adequacy is critical, since major
decisions on control actions, health
effects, and other significant issues could
be based on the interpretation of such
data.
To address the need for standardized
measurement procedures, EPA has es-
tablished a Compendium of Methods for
the Determination of Toxic Organic Com-
pounds in Ambient Air. This Com-
pendium contains current, peer-reviewed
sampling and analytical procedures in a
standardized format for analysis of
selected toxic organic pollutants of
primary importance in ambient air. The
original Compendium (EPA 600/4-84-041,
1984) contained five methods, and a
Supplement (EPA 600/4-87-006, 1986)
added four more procedures. This
Second Supplement adds five new meth-
ods to the Compendium, bringing the
total number of methods in the Compen-
dium to 14, covering a variety of toxic
organic air pollutants. The five new pro-
cedures are applicable to pesticides
(Method T010), formaldehyde (Method
T011), total non-methane organic
compounds (Method T012), benzo(a)py-
rene and other polynuclear aromatic
hydrocarbons (PAHs) (Method T013), and
various toxic volatile organic compounds
(VOCs) (Method T014). General guidance
regarding monitoring of ambient organic
compounds is contained in a companion
document titled Technical Assistance
Document (TAD) for ff»e Determination of
Toxic Organic Compounds in Ambient
Air.
Structure of the Compendium
Each procedure of the Compendium is
written to be used independently from the
others. In general, the procedures are
divided into the following twelve sections:
• 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 stan-
dardized format used by the American
Society for Testing and Materials
(ASTM). Each procedure has been identi-
fied with a revision number and date to
allow future modifications. Additional pro-
cedures, which may be compound-
specific or of multiple analyte design, will
be added to the compendium as they be-
come available.
Nearly all the procedures have
siderable flexibility and assume th<
analyst has substantial expertise. C
quently, users are responsible for
paring certain standard operating p
dures (SOPs) to be employed in
particular laboratory. Each procedu
dicates those operations for which
are required.
The Second Supplement contain!
new methods to be added to the
pendium and an update/correctic
Method T09 (published in the first
plement). It also contains instruction:
updated pages for merging the
Second Supplement information wit
previously published material, an
eludes a revised Table of Content:
updated Tables 1 and 2 to include
the previous methods and the new t
ods. When so combined, the use
have a fully integrated Compendium
ering all 14 methods. Updated Tal
gives a brief description of each m<
and the types of compounds to whicl
applicable. Updated Table 2 provic
partial listing of toxic organic compc
that can be determined and
applicable method or methods. Mai
the procedures may be used to c
mine other toxic organics not indicat
Table 2. The user must be caution*
evaluate the applicability of the me
for other organic substances before i
-------
'able 1. Brief Method Description and Applicability
Description
)thod
lumber
Types of
Compounds Determined
'01 Tenax GC Adsorption and GC/MS Analysis
'02 Carbon Molecular Sieve Adsorption and
GC/MS Analysis
'03 Cryogenic Trapping and GC/FID or ECO Analysis
'04 High volume PUF Sampling and GC/ECD Analysis
'05 Dinitrophenylhydrazine Liquid Impinger Sampling
and HPLC/UV Analysis
'06 High Performance Liquid Chromatography (HPLC)
'07 Thermosorb/N Adsorption
'08 Sodium Hydroxide Liquid Impinger with High
Performance Liquid Chromatography
'09 High Volume Polyurethane Foam Sampling with
High Resolution Gas Chromatography/High
Resolution Mass Spectrometry (HRGC/HRMS)
'010 Low Volume Polyurethane Foam (PUF) Sampling
With Gas ChromatographylElectron Capture Detector
(GC/ECD)
'11 Adsorbent Cartridge Followed by High Performance
Liquid Chromatography (HPCL) Detection
'012 Cryogenic Preconcentration and Direct Flame
lonization Detection (PDFID)
'013 PUF/XAD-2 Adsorption with Gas Chromatography
(GC) and High Performance Liquid Chromatography
(HPLC) Detection
'014 SUMMA* Passivated Canister Sampling with Gas
Chromatography
Volatile, nonpolar organics (e.g., aromatic hydrocarbons, chlorinated
hydrocarbons) having boiling points in the range of 80' to 200"C.
Highly volatile, nonpolar organics (e.g., vinyl chloride,
vinylidene chloride, benzene, toluene) having boiling points in the range
of -15" to
Volatile, nonpolar organics having boiling points in the range of -10"
to +200"C.
Organochlorine pesticides and PCBs
Aldehydes and Ketones
Phosgene
N =Nitrosodimethylamine
Cresol/Phenol
Dioxin
Pesticides
Formaldehyde
Non-methane Organic Compounds (NMOC)
Polynuclear Aromatic Hydrocarbons (PAHs)
Semi-Volatile and Volatile Organic Compounds
(SVOC/VOCs)
-------
Table 2. Method Applicability to Compounds of Primary Interest
Applicable
Compound Method(s) Comments
Acenaphthene 7014
Acenaphthylene T014
Acetaldehyde T05, T011 Extension of T011.
Acetone T011 Extension of T011.
Acrolein 705,707? Extension of T011.
Acrylonitrile T02, 703 T03 yields better recovery data than T02.
Aldrin T010
Ally! Chloride T02, T03 T03 yields better recovery data than T02.
Aroclor 1242, 1254 and 1260 TOW
Benzaldehyde T05
Benzene T01, T02, T03, T014 T014 yields better recovery data.
Benzyl Chloride T01, T03, T014
Benzo(a)anthracene T013
Benzo(a)pyrene T013
Benzo(b)fluoranthene T013
Benzo(e)pyrene T013
Benzo(g,h,i)perylene T013
Benzo(k)fluoranthene T013
Butyraldehyde T011 Extension of T011.
Captan TOW
Carbon Tetrachloride T01, 702, T03, T014 Breakthrough volume is very low using T01.
Chlordane TOW
Chlorobenzene T01, T03, T014
Chloroform T01, 702, T03, T014 Breakthrough volume is very low using T01.
Chloroprene
(2-Chloro-l,3-butadiene) T01, 703 The applicability of these methods for chloroprene has not been document*
Chlorothalonil TOW
Chlorpyrifos TOW
Chrysene T013
Cresol T08
Crotonaldehyde T011 Extension ofTOH.
4,4'-DDE T04
4,4'-DDT T04
1,2-Dibromomethane T014
1,2-Dichlorobenzene T014
1,3-Dichlorobenzene T014
1,4-Dichlorobenzene T01, T03, T014
1,1-Dichloroethane T014
1,2-Dichloroethylene T014
1,2-Dichloropropane T014
1,3-Dichloropropane T014
Dichlorovos TOW
Dicofol TOW
Dieldrin TOW
2,5-Dimethylbenzaldehyde T011 Extension of T011.
Dioxin 709
Endrin TOW
Endrin Aldehyde TOW
Ethyl Benzene T014
Ethyl Chloride T014
Ethylene Dichloride
(1,2-Dichloroethane) T01, T02, T03, T014 Breakthrough volume very low using TOT.
4-Ethyltoluene T014
Fluoranthene T013
Fluorene T013
Folpet TOW
Formaldehyde T05, T011
Freon 11 T014
Freon 12 T014
Freon 113 T014
Freon 114 T014
Heptachlor T010
Heptachlor Epoxide TOW
Hexachlorobenzene and
a-Hexachlorocyclohexane T010
-------
Table 2. (Continued)
Compound
Applicable
Method(s)
Comments
Hexacholobutadiene
Hexachlorocyclopentadiene
Hexan-aldehyde
lndeno(i,2,3-cd)pyrene
Isovaleraldehyde
Undane (a-BHC)
Methoxychlor
Methyl Benzene
Methyl Chloride
Methyl Chloroform
(1,1,1 -Trichloroethane)
Methylene chloride
Mexacarbate
Mirex
Naphthalene
Nitrobenzene
N-Nitrosodimethylamine
trans-Nonachlor
Non-methane Organic Compounds
Oxychlordane
Pentachlorobenzene
Pentachlorphenol
p,p'-DDE
p,p'-DDT
Perchloroethylene
(tetrachloroethylene)
Phenanthrene
Phenol
Phosgene
Polychlorinated biphenyls (PCBs)
Propanal
Propionaldehyde
Pyrene
Ronnel
1,2,3,4- Tetrachlorobenzene
1,1,2,2-Tetrachloroethane
o-Tolualdehyde
m-Tolualdehyde
p-Tolualdehyde
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,2-Trichloroethane
Trichloroethylene
2,4,5-Trichlorophenol
1,2,4-Trimethylbenzene
1,3,5-Trimethylbenzene
Valeraldehyde
Vinyl Benzene
Vinyl Chloride
Vinyl Trichloride
Vinylidine Chloride
(1,1 -dichloroethene)
o,m,p-Xylene
T014
T010
T011
T013
T011
T010
T010
T014
T014
T01, T02, T03, T014
T02, T03, T014
TOW
T010
T013
707, T03
T07
T010
T012
TOW
TOW
TOW
TOW
TOW
T01, (T02?), T03, T014
T013
T08
706
704, 709
705
T011
T013
TOW
TOW
T014
T011
T011
T011
T01, 702, 703, 7074
7070, 7074
7074
7074
707, 702, 703, 7074
7070
7074
7074
7077
7074
702, 703, 7074
7074
702, 703, 7074
707, 703, 7074
Extension of 7077.
Extension of 7077.
Breakthrough volume very low using 707.
702 performance has not been documented for this compound.
Estension of 7077.
Using PUF in combination with Tenax* GC solid adsorbent.
Extension of 7077.
Extension of 7077.
Extension of 7077.
Using PUF in combination with Tenax* GC solid adsorbent.
Extension of 7077.
-------
W. T. Winberry, Jr., and Norma T. Murphy are with Engineering-Science, Gary, NC
27513; R. M. Riggin was formerly with Battelle-Columbus Laboratories,
Columbus, OH 43201.,
L Purdue and F. McElroy are the EPA Project Officers (see below).
The complete report, entitled "Second Supplement to Compendium of Methods for
the Determination of Toxic Organic Compounds in Ambient Air," (Order No. PB
90-1169971 AS; Cost: $39.00, 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 Officers can be contacted at:
Atmospheric Research and Exposure Assessment Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Official Business
Penalty for Private Use $300
EPA/600/S4-89/018
U.S.OFFICIAL MAIL*
«.S.POSTA6£"
-:: 0 3 5 :
------- |