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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