United States
 Environmental Protection
 Agency
 Industrial Environmental Research
 Laboratory
 Research Triangle Park NC 27711
 Research and Development
 EPA-600/S7-84-057  June 1984
 Project  Summary
 Stable  Isotope Dilution  for
 Hazardous Waste  Incineration
 P. W. Ryan
  This research project was undertaken
with the general objective of evaluating
the potential utility of isotope dilution
gas chromatography/mass spectrom-
etry (GC/MS) in chemical analysis
related to incineration  of hazardous
waste materials. The specific objective
was to determine if a proposed catalytic
exchange procedure could be adapted
to produce the labeled analog materials
necessary for isotope dilution GC/MS
analysis.
  The proposed deuterium exchange
technique is  described along with ex-
periments designed to test its applica-
bility. Results of the experiments show
that the technique can be successfully
applied to certain limited classes of
hazardous waste materials, but they do
not indicate sufficient versatility to meet
the most general needs of hazardous
waste incineration programs.
  This Project Summary was developed
by EPA's Industrial Environmental Re-
search Laboratory, Research Triangle
Park. NC, to  announce key findings of
the research project that is fully docu-
mented in a separate report of the same
title (see Project Report ordering infor-
mation at back).

Introduction
  For purposes of evaluating and moni-
toring hazardous waste incineration pro-
cesses, the chemical analysis of influent
streams, effluent streams, and fugitive
emissions may  be frequently required,
and combined  GC/MS  is a suitable
analytical technique for  much of that
chemical analysis. Experience in  related
analytical  applications, for example
GC/MS determination  of priority pollu-
tants in wastewater, has demonstrated
that the highest quality GC/MS analytical
 data are obtained when isotope dilution
 techniques are employed.
   A major impediment to  the use of
 isotope dilution is the difficulty of obtain-
 ing isotopically labeled analogs of the
 target compounds for which analytical
 data are required. Analogs are commerci-
 ally available for about 50 of the priority
 pollutant compounds, but must be ob-
 tained by custom synthesis for use with
 other substances, which severely limits
 the extension  of isotope dilution tech-
 niques to new areas.
   A proposal for circumventing this limita-
 tion would  use a  catalytic exchange
 technique to prepare deuterium labeled
 materials  at considerably less expense
 than custom synthesis. There is evidence
 that certain catalytic exchange techniques
• will produce tritium labeling in a non-
 specific manner, that is not  selective by
 compound type, in complex organic mix-
 tures devised from oil shale processing.
   The object of this research project is to
 assess the potential utility  of catalytic
 exchange for producing deuterium labeled
 materials which are suitable for use as
 isotope dilution analogs to hazardous
 waste materials. If deuterium  labeling
 could be achieved starting with complex
 mixtures, perhaps even with  the inciner-
 ator influent itself, then an  inexpensive
 and broadly applicable means would have
 been found  to extend  isotope  dilution
 GC/MS analysis to a  number  of new
 areas.

 Conclusions
   Catalytic exchange is not a simple
 general technique that can  be  used to
 generate deuterium labeled analogs of
 hazardous wastes. It is, however, a tech-
 nique that could prove valuable in applica-
 tion to more limited  classes of materials.

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   The'technique shows a surprising capa-
   bility to produce  labeled analogs thor-
   oughly, extensively, and specifically for
   several  phenols,  polynuclear  aromatic
   hydrocarbons, and some other species.
     For the compounds that are deuterated,
   the product materials are suitable for use
   as isotope dilution GC/MS standards or
   as spiking materials for process character-
   ization.
     Based on the data generated  in this
   study for a selected set of compounds, the
   major limitation of the technique seems
   to be its  lack of generality. For most
   compounds and compound classes repre-
   sented in  the test  mixture, no useful
   labeled analogs were isolated  from the
   reaction vial.

   Recommendations
     This study has demonstrated that cata-
   lytic exchange can be successfully applied
   in specific cases, but without further
   development it is not applicable to waste
   materials in general. The unsuccessful
   applications  deserve  further  study  to
   determine whether  simple methodology
   revisions can resolve the problem. Time
   of exposure to catalyst and selection of
   extraction solvents are simple, potentially
   useful variations of techniques which
   might very well extend the list of suitable
   compound classes.
     This study has  addressed the labeled
   analog problem  only  in  very general
   terms, and has indicated some potentially
   fruitful applications of catalytic exchange
   in the area of hazardous waste analysis.
   Further work could focus on explicit needs
   of specific  programs, with emphasis  on
   optimizing experimental techniques for a
   specified, limited  set of materials. Poly-
   chlorinated biphenyl (PCB) incineration
   efficiency, phenol containing wastewater
        cleanup, or fugitive emissions of organic
        species from synf uels processes might be
        appropriate choices for areas of further
        study.
          P. W. Ryan is with S-Cubed. La Jolla. CA 92O38.
          Merrill D. Jackson is the EPA Project Officer (see below).
          The complete report, entitled "Stable Isotope Dilution for Hazardous Waste
            Incineration," (Order No. PB 84-189 828; Cost: $8.50, subject to change) will
            be available only from:
                  National Technical Information Service
                  5285 Port Royal Road
                  Springfield,  VA22161
                  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
                                             •&• U.S. GOVERNMENT PRINTING OFFICE. 1984 — 759-015/7719
United States
Environmental Protection
Agency
Center for Environmental Research
Information
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