United States Environmental Protection Agency Air and Energy Engineering Research Laboratory Research Triangle Park NC 27711 Research and Development EPA/600/S8-87/037 Dec. 1987 &ERA Project Summary POHC Analysis Methods for Hazardous Waste Incineration Ruby H. James, Joe M. Finkel, H. Kenneth Dillon, Robert E. Adams, Herbert C. Miller, and Afaf K. Wensky This report describes the evaluation of generalized GC/FID, GC/MS, HPLC/UV. and HPLC/fluorescence analysis methods for measuring princi- pal organic hazardous constituents (POHCs) in various influent and effluent streams of incineration facilities. The report includes summary sheets that list relative retention times, on-column detection limits, molecular weights, relative ion abundances, and wave- lengths of detection for the POHCs. Reference chromatograms, calibration curves, mass spectra, key ions and rela- tive abundances, and UV absorption spectra of the POHCs are presented in report appendices. This Project Summary was developed by EPA's Air and Energy Engineering Research 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 As part of the Resource Conservation and Recovery Act of 1976, the U.S. En- vironmental Protection Agency has pro- posed regulations for owners and operators of facilities that treat hazardous wastes by incineration to ensure that these incinerators will be operated in an environmentally responsible manner. The primary criterion upon which the opera- tional specifications are based is the destruction and removal efficiency (DRE) of the incinerator. The DRE value, defined in terms of waste-input and stack-output levels of designated principal organic hazardous constituents (POHCs), must be equal to or greater than 99.99%. Approximately 400 compounds (desig- nated POHCs) are included in Appendix VIII, Part 261, 40 CFR. However, the survey/analysis portion of a waste- characterization scheme often targets specific compounds for determination in incinerator effluent that are not amenable to previously developed methods. There- fore, current research involves the development of specific GC/FID,* GC/ MS, HPLC/UV, and HPLC/fluorescence methods for the determination of several of these compounds. This work involved the evaluation of generalized GC/FID, GC/MS, HPLC/UV, and HPLC/fluore- scence methods for determining approxi- mately 200 compounds from this list of POHCs. This report presents preliminary data on methodology for candidate POHCs that represent a variety of compound types, including alcohols, esters, chlori- nated aliphatics and aromatics, carboxylic acids, aliphatic and aromatic amines, nitrated aromatics, nitrosamines, hydra- zines, nitriles, organosulfur compounds, polynuclear aromatics and heterocyclics, and organometallics. EPA's manual. Sampling and Analysis Methods for Hazardous Waste Combus- tion, EPA-600/8-84-002, is a resource document for the preparation and execu- tion of a sampling-and-analysis plan for hazardous-waste incinerators. Report EPA-600/8-84-002 recommends a vari- ety of analytical techniques for deter- mining POHCs. Methods were written to incorporate fused-silica capillary GC/MS and HPLC. These methods were designed to provide satisfactory qualitative and quantitative analyses on a cost effective basis for a variety of waste types and process chemistries. Generalized GC/MS GC = gas chromatography, FID = flame ionization detection, MS = mass spectro- metry, HPLC = high performance liquid chromatography, and UV = ultraviolet. ------- and HPLC techniques were developed to determine as many of the POHCs as possible. The laboratory work was structured to lead systematically from determining the feasibility of developing generalized test methods to standardizing the resulting methods for selected POHCs. Initially, standard solutions of mixtures of selected POHCs were analyzed to optimize instru- mental operating conditions. Then in- dividual chromatograms (GC/FID, GC/ MS, HPLC/UV, HPLC/fluorescence)were obtained, calibration curves were estab- lished, and detection limits were estimated. The following tasks supplemented the development of generalized test proce- dures and, in general, improved EPA- 600/8-84-002: • The evaluation of generalized analy- sis methods for approximately 100 POHCs by GC/FID and GC/MS. • The application of a selective GC column and GC/MS using selected- ion monitoring to determine 2,3,7,8- TCDD. • The evaluation of generalized analy- sis methods for approximately 100 POHCs by HPLC/UV. • The evaluation of generalized analy- sis methods for 13 POHCs by HPLC/fluorescence. • The development of a derivatization technique for three organometallic POHCs. • The evaluation of generalized analy- sis methods for five organometallic POHCs by GC/FID, GC/MS, and HPLC/UV. Experimental Description of Instruments and General Operating Conditions The GC/MS generalized test method was developed on a Hewlett-Packard (HP) Model 5985A GC/MS data system. Sys- tem components included a hyperbolic quadrupole mass filter with a convertible electron-impact (El) and positive-ion chemical-ionization source and a capillary and jet separator GC/MS interface. Its data system included an H2113 computer, a high-speed printer, a magnetic tape system, a 50-megabyte HP7920M disc- drive system, a communication interface, GC/MS operating software, and an un- abridged NBS special library. The supple- mental GC/FID work was performed on a HP Model 5840 GC equipped for use with capillary columns. The work with both the GC/MS and the GC/FID involved capillary-column chromatography with matched, cross- linked fused-silica SE-54 capillary columns 25 m long with a 0.31-mm ID. The initial operating conditions were a compromise of the conditions given for several capillary GC methods in EPA- 600/8-84-002. The initial starting column temperature was 40 °C; the temperature was then programmed at 10 °C/min 280 °C for 15 min. Alternate column tem- perature programs used rates of 20 and 30 °C/min. Injection and detection tem- peratures were 250 °C. The carrier gas (helium) was maintained at a flow rate through the column of about 2 mL/min. In both the GC/MS work and the GC/FID work, the "splitless" injection technique was employed. Consequently, essentially all of the injected sample reached the column. The determination of 2,3,7,8-tetra- chlorodibenzo-p-dioxin (2,3,7,8-TCDD) used a fused-silica capillary column capable of separating the 2,3,7,8-TCDD isomer from the other 21 TCDD isomers (Chrompack CP SIL 88, 0.22-mm ID, 60- m length). The initial column temperature was 45 °C for 3 minutes, then pro- grammed to 190 °C at 25 °C/min, then programmed to 240 °C at 5 °C/min, and held at 240 °C for 10 minutes. The injec- tion temperature was 290 °C. Helium at 2 mL/min was used as the carrier gas. Having established GC operating con- ditions by the GC/FID procedure, the method was applied to determine the candidate POHCs by GC/MS. The MS was operated in a full mass scanning range (41 to 450 amu) in the El mode. The scan time was maintained at <1 s to enable the collection of enough scans to characterize each capillary GC peak. The MS was used in the selected-ion moni- toring (SIM) mode to determine 2,3,7,8- TCDD. The ions monitored were m/z 257, 320, and 322 for native unlabeled 2,3,7,8-TCDD; 328 for 37C14-2,3,7,8- TCDD; and 332 and 334 for l:»C12-2,3,7,8- TCDD. HPLC Analysis Procedures The POHCs were grouped into classes of compounds and submitted for HPLC analysis. Initially, standard mixtures of candidate POHCs were analyzed to establish solvent programs suitable for determining a variety of compounds. The UV detector was set to monitor absorb- ances at 254 nm. Various chromato- graphic conditions were evaluated and modified until the evaluation rate and the resolution were optimized. Ten chromatographic conditions are described in the report. Three columns were used in this work: HC-ODS-SIL-X- 1, AiBondapak C18, and ^Bondapak CN. In subsequent work, the UV absorption spectra of the candidate POHCs were determined on a Gary Model 17 spectro- photometer to establish an absorption maximum in the range from 190 to 400 nm that would be a suitable alternate wavelength for quantifying each POHC by HPLC/UV. For HPLC/fluorescence, the excitation wavelength was 280 nm for the PAHs (polynuclear aromatic hydro- carbons) and 360 nm for the aflatoxins. Derivatization Procedure Standards were prepared by weighing small amounts (1.0 mg) of the three compounds (benzenearsonic acid, hydro- xydimethylarsine oxide, and phenylmer- cury acetate) into 50-mL centrifuge tubes, adding 1.0 mL of hydroiodic acid (HI) and shaking for 1 minute. The derivatives we re extra cted i nto 10 m L of hexa ne a nd diluted to make standards. Results and Discussion GC/FID and GC/MS Analysis The report summarizes the GC/MS determinations of approximately 100 candidate POHCs. The retention time and on-column detection limit are given for each compound. The compounds are listed in the order of their elution from the GC column. Retention times are relative to that observed for the internal standard, anthracene-d10. The on-column detection limit was estimated using the calibration curve as suggested in Appendix A of Methods for Organic Chemical Analysis of Municipal and Industrial Wastewater, EPA-600/4-82-057. Typical values were between 0.1 and 80.0 ng. HPLC/UV Analysis The report summarizes the HPLC deter- minations of approximately 100 candidate POHCs. The retention time, on-column detection limit, and wavelength of detec- tion are given for each POHC. The POHCs are listed by group in order of their elutior from the HPLC column and subdivided b\ procedural option. Detection limits were calculated by the same procedure used ir GC analyses. Detection limits ranged frorr 0.001 to 6 ng. The wavelength of detectior was 254 nm except where noted. Ar alternate wavelength was selected frorr the reference UV spectrum to optimize the detection of the POHCs. ------- HPLC/Fluorescence Analysis The determination of 13 POHCs was completed by HPLC/fluorescence. The retention time, on-column detection limit, and excitation/emission wavelengths are given for each POHC. The POHCs are listed by group in order of their elution from the column and subdivided by proce- dural option. The on-column detection limit was calculated in the same manner as used for GC/FID and GC/MS. Detec- tion limits ranged from 0.001 to 0.4 /^g. Conclusions Generalized GC/FID, GC/MS, HPLC/ UV, and HPLC/fluorescence procedures were developed to determine candidate POHCs. Initially, standard solutions of mixtures of selected POHCs were analyzed to optimize instrumental oper- ating conditions. Then individual chro- matograms (GC/FID, GC/MS, and HPLC/UV) were obtained, calibration curves were established, and detection limits were estimated. The technical approach in developing and evaluating the generalized instrumental methods is discussed in the report. The chromato- grams and data are provided in three report appendices. Appendix A contains the chromato- grams and calibration curves for the GC/FID determinations. Appendix B shows the mass spectra in addition to the chromatograms and calibration curves for GC/MS determinations. Appendix C contains the UV absorption spectra as well as the chromatograms and calibration curves for HPLC/UV determinations. A simple denvatization technique al- lows the determination of benzenearsonic acid, hydroxydimethylarsme oxide, and phenylmercury acetate by the generalized GC/FID and GC/MS procedures. These compounds were recovered quantitatively from sorbents, filters, and water. The derivatization procedure may be useful for other organometallic compounds. Compounds such as selenourea and tetraethyl lead may be determined by the HPLC/UV and GC/FID or GC/MS proce- dures, respectively, without major modifi- cations of the procedures. The deter- mination of 2,3,7,8-TCDD by the general GC/MS procedure provides a screening analysis and may be applicable for sur- vey/analysis of hazardous waste. How- ever, ultimate selectivity and sensitivity are provided by an isomer-specific GC column and SIM mass spectrometry. The developed generalized methods are suitable for inclusion in EPA-600/8-84- 002. The methods were standardized with selected organic compounds over con- centration ranges of interest and showed acceptable precision in determining most of the compounds. R. James. J. Finkel, and H. Miller are with Southern Research Institute, Birmingham, AL 35255; H. Dillon is with University of Alabama, Birmingham, AL 35294; R Adams is with Triangle Laboratories, Research Triangle Park, NC27713, andA. Wensky is with Battelle-Columbus Laboratories, Columbus, OH 43201. Larry D. Johnson is the EPA Project Officer (see below). The complete report consists of three volumes entitled "POHC Analysis Methods for Hazardous Waste Incineration." Volume 1, Part 1 (Order No. PB 87-227 286/AS, Cost $3095, subject to change). Volume 1. Part 2 (Order No. PB 87-227 294/AS, Cost $3695, subject to change). Volume 2 (Order No. PB 87-227 302/AS, Cost $24 95, subject to change) The above reports will be available only from. National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Officer can be contacted at. Air and Energy Engineering Research Laboratory U S. Environmental Protection Agency Research Triangle Park, NC 27711 ------- United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 -•"rTwTT^ w*w. \st i t\*fir\i~ i¥ /C? '^^ENALTV I JAN -S' 88 hafvATE — — - \ - / JSE $300 x / * * X ^ jc Xi.jmi_>i.u U.S.POST/ zQ2l Official Business Penalty for Private Use 5300 EPA/600/S8-87/037 62sOI09l 0000329 PS CHICAGO 60604 ------- |