Laboratory Development anci Field Evaluation of a Generic Method fol Santplirtg and Analy si~ of Zsocyanate~ Revised Final Reporl Prepared for Mr. Frank M'ilshirc National Exposure Research Laborator! Air Measurements Research Divisiol hlethods Brand US. Environmental Protect ion Agenc! Research Triangle Park, NC 2771: Prepared by J. F. McGaughe: S. C. Foste: R. G. Merril August 199: CCADLAN CORPORATION EPA Report Number Month Pod Year of Publidion Laboratory Development and Field Evaluation of a Generic Method for sampling and Analysis of Isocyanates Revised Final Report Prepared by: I. F. McGaughey S.C. Foster R. G. Merrill Rac!im Corporation P.O. Box 13000 Research Triangle Park, NC 27709 Project Officer Mr. FrdWilshire National Expswe Research L~horetory Air Masurernents Researcb Division Methods Branch US. Environmental Protection Agency Research Triangle P~rk,NC 2771 1 Disclaimer ?be information in this document has been funded wboUy by tbe United States Emironmedal Fjmtection Agency derEPA Contract Number 68-D1M)lO md 68-Dm22lo Radian. It bPs been subjected to tbe Agemy's peer md dminirtrniive review, and it bas bsen approved for pblication rs an EPA document. Mention of trade names or commercial products does mt constitute dorsement or recommendation for use. Acknowledgements We wish to acknowledge the contributions of the following individruls to the rucccss of tbis program: Mark Owens, Danny Hurison, Durell Doerle, Jorn Runey, Pbyllk O'Hara, Jim Soutberlad, SadGodfrcy, d Carol Hobson. Abstract Tbe U.S. Environmeatal Protection, dertbe .utbority of Title XU of tbe ChAir Act Amdmc& of 1990, requires tbe identification d evaluation of r umpling d dyr~method for tbe following bocymates: bexamethylene-1,6diisocymste;2,4-tolueoe diirsocymste; meLhyleoe dipbeDyl diisocyraate; d matbyl isocyanate. A laboratory rndy was performed to develop r sampling d dyrismabod. This effort wrs followed by three fiekl validation tests using tbe approach specified in the EPA Metbod 301 protocol. Tbe sampling matbod employed was r mcdification of the EPA Metbod 5, using r derivatizing agent to rtabilize tbe isocymstes for subsequent dysis. Samples were dyzed by high performance liquid chromatography derconditions sdquate to separate PDd quautLfy all four co-. Tbe metbod bias d precision met the 301 criteria for an acceptable method si tested at tbe specified source types. Contents Section 1 Introduction ......................................................... 1-1 Section 2 Conclusions IUKI Recomrnervlrrtions ..........................................2-1 2.1 Field Test #l (TDI) ................................................ 2-1 2.2 Field Test #2 (hlDI) ........................................ 2-1 2.3 Field Test #3 (HDI. hlDI. hll and TDI) .................................. 2-2 Section 3 Experimenfal Approach .................................................3-1 3.1 Laboratory .....................................................3-1 3.2 Field ......................................................... 3-2 Section 4 Results and Discussion .................................................. 4-1 4.1 Laboratory Development ............................................ 4-1 4.1.1 Literature Search and Background Information ......................... 4-1 4.1.2 Evaluation of Deriv~tizntionTechniques .............................44 4.1.3 Preparation of Derivatives ...................................... 4-9 4.1.4 Reaction Kinetics St~~dy........................................ 4-15 4.1.5 Stability of Isocyanate Urea Cryshls ...............................4-16 4.1.6 Lnter-Lhoratory Round Robin ................................... 4-17 4.1.7 Lnstn~mentConditions ..........................................4-18 4.1.8 Analysis of hll, HDI, TDI, MDI ...................................4-19 4.1.9 Instrument Daection Limit Study ..................................4-23 4.1.10 Lnterfermts ................................................4-24 4.1.11 Toluene as an Lnlpurity ..............: .........................4-25 4.1.12 Train Spiking Experiments .......................................4-28 4.2 Field Evaluation ..................................................4-35 4.2.1 Quad-Probe .................................................4-39 4.2.2 Quad-Train Assenlbly .........................................4-39 4.2.3 Preparation for Smpling .......................................442 4.2.4 Smple Recovery ............................................4-44 4.2.5 B1ds ...................................................445 4.2.6 Results of Field Tests .........................................4-46 Section 5 . Analytic~lhstn~ment Performmce Rnd Quality Control ............................ 5-1 5.1 Overview of Dah Quality ...........................................5-2 5.2 Smlple Stornge d Holding Time ...................................... 54 5.3 Annlyticnl Qualily Control ...........................................54 Contents (continued) Section 6 Metbod Quality Control d Metbod 301 Statistical Procsdurss ....................... 6-1 6.1 QualityCoatrol .................................................. 6-1 . 6.1.1 S.mplingQCROCddllrss ....................................... 6-1 6.1.2 Iaboratory QAfQC Procedurss ................................... 6-3 6.2 Metbod 301 Statistical Procedures ...................................... 6-4 6.2.1 Cdculation of tbe Amount of Isocyanate Collected ...................... 6-4 6.2.2 NormaliLation of the Amount of Isocyanate CoUbcted .................... 6-5 6.2.3 Precision of Spiked Samples ..................................... 6.6 6.2.4 Precision of Unspiked Samples ...................................6-7 6.2.5 Bias .....................................................6-7 Section 7 References .......................................................... 7-1 Figures 4-1 Stn~cturesof tbe icocy.nues. ................~.................................4-3 4-2 Reaction of szhPool witb 2.4.TDI ................................................ 4-5 4-3 Reaction of 1. 2.pp with methyl isocyanate .......................................... 4-5 44 Reaction of 2. 4.TDI with wrter ................................................. 44 4-5 HPLC chromatogram of underivatized 2. 4.TDI mobile phase .31:69 ACN:AAB (Isocratic) ......... 4-10 44 HPLC chromatogram of 2. 4.TDI urea mobile phase .31:69 ACN:AAB (isocratic) ............... 4-10 4-7 KPLC chromatopram of uoderivrtbed MDI Gradient Program .31:69 to 90:lO (ACN:AAB) ........ 4-11 4-8 HPLC chromatogram of MDI Urea Gredient Program . 31:69 to 90:lO (ACN:AAB) .............. 4-11 4-9 HPLC chromatogram of underivntued HDI mobile phase .31:69 ACN:AAB (Isocratic) ............4-12 4-10 HPLC chromatogram of KDI urea Mobile Phase .31:69 ACN:AAB (isocratic) .................4-12 4-1 1 HPLC chromatogram of 1.2.~~Mobile Phase .20:80 ACN:AAB (lsocratic) ................... 4-13 4-12 HPLC chromatogram of MDI Uree Mobile Phase .20:80 ACN:AAB (Isocratic) .................4-13 4-13 HPLC chromatogram of 2. 4.TDI .Dd 2. 6.TDI (80:20) Mobile Phase .31:69 ACN:AAB (ieocratic) ....4-20 4-14 HPLC chromatogram of mixture of 2.6.TD1. 24.TDI. HDI. md MDI Grdient Program .31:69 for 10 minutes to 5050 over 5 minutes ......................4-20 4-15 HPLC chromatogram of MI. 2.6.TDI. 2.4-TDI. HDI. d MDI gradient program .20:80 for 4 minutes to 60:40 over 16 minutes ...........................................4.22 4-16 Reaction of phosgene witb 1-(2-pyridyl) pipe6...................................... 4-26 4-17 HPLC chromatopram of a high level soIution of phosgene derivrtized with 1. 2.pp ................ 4-26 4-18 HPLC chromalogram of a low level sol ion of pbosg~ederivrtiLad with 1.2.~................ 4-27 4-19 HPLC chromatogram of a solution of tbe precipitate recovered from tbe derivrtization of phosgene with 1.29~.................................................... 4.27 4-20 Spiking system configuration number one ..........................................4-29 4-21 Spiking system confipration number two ..........................................4-33 Figures (continued) 4-22 Spiking configuration number three ..............................................4-34 4-23 HPLC chromatogram of contentb of first impinger ....................................4.36 4-24 HPLC chromatogram of contents of second impinger ................................... 4.36 4-25 HPLC chrom~ogramof contents of third second impinger ...............................4-37 4-26 Sampling train for isocyanates .................................................. 4-38 4-27 Qua~l-tminprobe and pitd arrangement ............................................440 4-28 Upper and lower sampling probes (side view) ........................................4-41 4-29 Sample location for ?PI ......................................................448 4-30 sample location for MDI ..................................................... 4-52 4-3 1 Schematic view of the sampling location for HDI ..................................... 4-57 Tables 1-1 tocygpplw Listed in the Clepn Air Act Amerdmeots of 1990 ............................. 1. 1 . 4-1 Physical Propertics of bocyrartw ............................................... 4-2 4-2 Reactivity Dais of 1socy.nate.s .................................................. 4-2 4-3 Recoveries for 2. 4.TDI Derivative Under Vqing Conditions of Moisture. pH rod Solvent .........4-16 4-5 Instrument Detection Limit d Limit of QlLantitationfor 2.4.TDI. HDI d MDI Ureas ............4-24 44 Recoveries of 2. 4 TDI Using Spiking Configuration Number One ..........................4-31