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. ------- 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 Cincinnati OH 45268 Official Business Penalty for Private Use $300 PS 0000529 U t> t^VjK PWultCUUN REblUN S LittKAtn 230 6 UtAKtsutfiV S CniCAbU IL t>ObU4 ------- |