v>EPA
United States
Environmental Protection
Agency
Industrial Environmental Resear
Laboratory
Research Triangle Park NC 2771
Research and Development
EPA-600/S7-81-029 July 1981
Project Summary
Methods for Level 2 Analysis by
Organic Compound Category
K. E. Thrun, J. C. Harris, C. E. Rechsteiner, and D. J. Sorlin
This report presents the results of a
laboratory evaluation of specific
detailed methods for analysis of
organic chemicals in particular
compound categories. The report
supplements the earlier Level 2
procedures manual1 and provides an
initial experimental data base as a
resource for laboratories undertaking
Level 2 studies. The Level 2 methods
were designed to provide more
detailed and more accurate data
concerning specific compounds
whose presence in the sample could
be inferred on the basis of the
categorical analysis of Level 1 .
A systematic laboratory evaluation
of the methods for Level 2 analysis of
each major category of organic
compounds was conducted. Methods
were evaluated using sets of model
compounds spanning a range of
molecular weights and boiling points
in each category. Evaluation criteria
included: detection limit, retention
time, chromatographic resolution,
and precision and accuracy of the
methods.
Specific detailed Level 2 methods
have been recommended in the full
report for 25 categories of organic
compounds. Most of the primary
recommendations are based on
packed column gas chromatography/
mass spectrometry, with alternative
procedures suggested where
appropriate for particular sample
matrices or compound types.
Analytical data using the specified
example
illustrated
method.
conditions are usually
for each recommended
The strategy for application of the
recommended Level 2 methods to real
environmental samples is illustrated
by a partial Level 2 analysis of a
combustion effluent sample. The
Level 1 data on the sample are
reviewed to illustrate the Level 1 to
Level 2 transition process and
decision criteria. The Level 2 analysis
provided qualitative confirmation of
compound classes, subcategories,
and specific compounds identified at
Level 1. Level 2 quantitative data
agreed with expectations based on
Level 1 chromatographable organics.
However, comparison of the partial
Level 2 data with the total quantity of
organics found by Level 1 for this
sample illustrates that additional
types of analysis methods will need to
be developed to make possible
complete Level 2 analysis of the range
of organics identifiable at Level 1.
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
This report represents a step in the
development of a general methodology
for chemical and biological assessment
of environmental effects of industrial
effluents. It is a supplement to the Level
2 procedures manual1 for sampling and
analysis of organics which was
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published in 1979. The procedures
manual1 presented concepts and
general guidelines for Level 2 sampling
and analysis. It also suggested specific
analysis procedures that were
considered to be appropriate for
particular organic compound
categories
Level 1 /Level 2 in the Phased
Approach
Both this report and the earlier
procedures manual were prepared to
support lERL-RTP's phased approach to
the overall environmental assessment
program lERL-RTP's Process
Measurements Branch has developed a
three-phased approach to sampling and
analysis for environmental assessment.
The philosophy of this approach, which
has been described elsewhere2, is
briefly described here to provide a
context for the present document.
Level 1, the first phase of sampling
and analysis for environmental
assessment, is designed to provide
enough information about the
composition of effluent and process
streams to permit them to be ranked in
order of priority with regard to probable
environmental hazard The Level 1
assessment is intended to: (1) provide
preliminary environmental assessment
data, (2) identify principal problem
areas, and(3)formulatethedata needed
for ranking of energy and industrial
processes, streams within a process,
components within a stream, and
classes of materials for further
consideration in the overall
assessment The second phase of
sampling and analysis effort. Level 2, is
designed to provide additional
information that will confirm and
expand the information gathered in
Level 1 The third phase, Level 3,
involves quantitative monitoring of
specific pollutants to provide
information for control device design,
development, and evaluation
The objective of a Level 2 study will be
to obtain more detailed and accurate
data about the composition of a
particular process stream than is
available m the context of a Level 1
study The improved accuracy should be
either primarily quantitative in terms of
establishing a truly representative
emission rate, primarily qualitative m
identifying organic species, or both.
Level 2 inquiries are expected to be
directed primarily at the identification,
quantification, and confirmation of
specific compounds whose presence
could be inferred on the basis of the
categorical analysis of Level 1
Based on information available to
date, it appears that mass spectrometric
analysis of sample extracts, using the
direct insertion probe, is an attractive
approach to obtaining Level 2
information on the non-chromato-
graphable GRAV range materials
identified in Level 1 analysis. High
resolution mass spectrometry (HRMS)
can provide better qualitative
information than available from the
Level 1 low resolution mass
spectrometry (LRMS) The quantitative
estimates provided by Level 1 LRMS can
be improved by applying the method of
known addition to the LRMS (or HRMS)
analysis for particular compounds
suspected to be present at levels of
concern
If Level 1 analysisshowsacategoryto
be present at concentrations that
exceed the emission level criteria for a
particular environmental assessment,
then Level 2 information will generally
be needed to determine whether/which
particular members of that category are
present and to obtain better quantitative
data For most organic compound
categories, the specific organic
compounds that are known to be of
concern (with regard to potential
impacts on health and/or the
environment) are the lower molecular
weight numbers of the category, for
which lexicological and ecological
effects data exist. Therefore, the most
immediate need was to develop and
evaluate Level 2 methods that are
applicable to this molecular weight
range The analytical methods
presented in the report, which were
selected primarily to meet that need,
therefore rely heavily on gas
chromatography/mass spectrometry
(GC/MS) as a broad but selective
technique for analysis of low to
moderate molecular weight organics.
The report presents the results of a
laboratory investigation and evaluation
of the set of detailed procedures for
analysis of organic compounds by
category recommended in the February
1979 Level 2 procedures manual.
Those recommendations had evolved,
based on careful review of literature and
discussions with other workers
experienced m the chemical analysis of
organic pollutants, from a list of possible
procedures in the inttenm Level 2
manual 1 The laboratory evaluation of
the recommended procedures had two
objectives:
• To determine whether the
original recommendations were
appropriate with or without
minor modifications.
• To provide appropriate analytical
data to users of the Level 2
analytical techniques
The experimental detail for each
method evaluated is provided in the full
report. The basic approach was to
evaluate each method using a text
mixture of model compounds
representative of that category. Criteria
for method evaluation included, lower
limits of analysis, analysis time,
chromatographic resolution, precision
and accuracy. The result of these
experiments is a set of analytical
procedures with supporting data
available, including specific analytical
conditions, chromatographic retention
times, lower limits of analysis, and
precision and accuracy data. Relevant
data from other sources were also
included when available.
References ,
1 Harris, J C., M.J Hayes, P.L. Levins,^
and D.B Lindsay, "EPA/IERL-RTP
Procedures for Level 2 Sampling
and Analysis of Organic Materials",
EPA-600/7-79-033, February 1979
EPA-600/7-79-033, February
1979 and Harris, J.C., and P.L
Levins, "EPA/IERL-RTP Interim
Procedures for Level 2 Sampling
and Analysis of Organic Materials,
EPA-600/7-78-016, February
1978.
2. Dorsey, J , C.H Lochmuller, L.D
Johnson, and R. Statnick,
"Guidelines for Environmental
Assessment Sampling and Analysis
Programs - Level 1," U.S.
Environmental Protection Agency,
RTP
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K. E. Thrun. J. C. Harris, C. E. Rechsteiner, and D. J. Sorlin are with Arthur D.
Little, Inc., Cambridge, MA 02140.
Larry D. Johnson is the EPA Project Officer (see below).
The complete report, entitled "Methods for Level 2 Analysis by Organic Com-
pound Category," (Order No. PB 81-179 855; Cost: $24.50, 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
o U.S. OOVERNMENTPWNTINa OFFICE 1M1-757-OU/7162
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