United States Environmental Protection Agency Environmental Monitoring and Support Laboratory Cincinnati OH 45268 Research and Development EPA/600/S4-85/050 Sept. 1985 v°/EPA Project Summary Evaluation of 10 Pesticide Methods T. M. Engel, J. S. Warner, and W. M. Cooke Ten pesticide analysis methods were evaluated. The compounds listed in each method were analyzed in tripli- cate at two concentration levels in reagent water and POTW effluent. Each method was performed as written with only minor modifications. If a cleanup procedure was included in the analysis method, all analyses were performed with and without the cleanup step. Resultant data reported included es- timated detection limits (EDLs) in reagent water and recovery data from reagent water and POTW effluent for each compound. Suggestions for method improvements were included in the report where necessary. This Project Summary was devel- oped by EPA's Environmental Monitor- ing and Support Laboratory, Cincinnati, OH, to announce key findings of the re- search project that is fully documented in a separate report of the same title (see Project Report ordering informa- tion at back). Introduction Ten pesticide analysis methods were evaluated; a description of the methods and the compounds included in those methods are listed in Table 1. The com- pounds included in each method were analyzed in triplicate at two concentra- tion levels in reagent water and POTW effluent. Each method was performed as written with only minor modifica- tions as approved by the EPA Project Officer. If a cleanup procedure was in- cluded in the analysis method, all analy- ses were performed with and without the cleanup step. Resultant data reported included esti- mated detection limits (EDLs) in reagent water and recovery data from reagent water and POTW effluent for each com- pound before and after the optional cleanup step. Suggestions for method improvements were offered where warranted. Results A summary of the EDL and recovery data obtained during the evaluation of the 10 pesticide methods is given in Table 2. Methods 641, 643, and 645 were found to yield acceptable results as written. Method 641.1 was not ac- ceptable due to low recoveries of ethoxyquin, presumably due to adsorp- tion of the ethoxyquin to paniculate ma- terial prior to filtration of the sample for HPLC analysis. Method 642 was mar- ginally acceptable; recoveries of bi- phenyl and o-phenylphenol were low, possibly due to the rigorous conditions needed to concentrate sample extracts. Method 632.1 was acceptable for two of the compounds, napropamide and propanil, but was not acceptable for the determination of carbaryl (carbaryl re- coveries were low and dependent upon sample matrix and carbaryl concentra- tion). Method 644 was not acceptable; picloram recoveries were low, pre- sumably due to incomplete extraction of the picloram from the water matrix. The extraction and analysis portions of Method 614.1 were found to be accept- able for dioxathion, EPN, ethion, and terbufos. The silica gel cleanup proce- dure included in Method 614.1 was not acceptable; compound recoveries were decreased by 50 percent or more when the cleanup procedure was used. Method 646 was found to be acceptable for the determination of basalin and marginally acceptable for the determi- nation of CDNB and dinocap. Method ------- Table 1. Pesticide Method Information Method Number 641 647.7 642 642 643 632.7 632.7 632.7 632.7 644 614.1 614.1 674.7 674.7 645 645 645 645 645 645 646 646 646 608.2 608.2 608.2 608.2 608.2 Compound(s) Thiabendazole Ethoxyquin Biphenyl 0-Phenylphenol Bentazon Carbaryl Napropamide Propanil Vacor Picloram Dioxathion EPN Ethion Terbufos Alachlor Butachlor Diphenamid Lethane Norflurazon Fluridone Basalin CDNB Dinocap Chlorothalonil DCPA Dichloran Methoxychlor Permethrin Extraction Method None None Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel None Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Separatory funnel Cleanup Method Filtration Filtration None None None None None None None Backextraction with base Silica gel Silica gel Silica gel Silica gel Florisil Florisil Florisil Florisil None None Florisil Florisil Florisil Silica gel Florisil Florisil Silica gel Silica gel Analysis Method HPLC-Fluorescence HPLC-Fluorescence HPLC-UV HPLC-UV HPLC-UV HPLC-UV HPLC-UV HPLC-UV None HPLC-UV GC-NPD GC-NPD GC-NPD GC-NPD GC-NPD GC-NPD GC-NPD GC-NPD GC-NPD GC-NPD GC-ECD GC-ECD GC-ECD GC-ECD GC-ECD GC-ECD GC-ECD GC-ECD A standard of vacor could not be obtained; Method 5 was not evaluated for vacor. 608.2 was found to be acceptable for cis- and trans-permethrin, but was not acceptable for the determination of DCPA, methoxychlor, chlorothalonil, and dicloran. Recoveries of DCPA and methoxychlor were low and concentra- tion and matrix dependent. Recoveries of chlorothalonil and dicloran could not be determined because of the presence of interferences. ------- Table 2. Summary of Data from Evaluation of W Pesticide Analysis Methods Recovery from Reagent Water. %ldl Recovery from POTW Effluentldl Method Number Compound 641 641.1 642 642 643 632.1 632.1 632.1 644 614.1 614.1 614.1 614.1 645 645 645 645 645 645 646 646 646 608.2 608.2 608.2 608.2 608.2 608.2 Thiabendazole Ethoxyquin Biphenyl O-Phenylphenol Bentazon Carbaryl Napropamide Propanil Picloram Dioxathion EPN Ethion Terbufos Alachlor Butachlor Diphenamid Lethane Norflurazon Fluridone Basalin CDNB Dinocap Chlorothalonil DCPA Dicloran Methoxychlor Cis-permethrin Trans-permethrin EDL, 1.7 6.3 0.04 0.01 1.1 1.2 0.02 0.3 0.3 0.5 12 0.3 0.02 0.2 0.2 0.2 0.1 0.02 0.6 0.0005 0.0005 0.1 0.001 0.003 0.002 0.4 0.2 0.2 Spike Level, pg/L Low 10 6.2 2.5 5.0 10 2.0 6.0 0.2 3.0 10 10 10 10 10 10 10 10 10 10 0.1 0.1 0.1 0.02 0.02 0.01 0.1 1.0 1.0 High 100 62 25 50 100 20 60 2 30 100 100 100 100 100 100 100 100 100 100 1 1 1 0.2 0.2 0.1 7 70 10 Before Cleanup Low 93 ± 3 100 + 32 74+2 73 ± 4 92+2 52+ 10 103 ± 2 79+6 N.D. 76+ 10 120+ 6 120+ 5 90+3 96+3 96+4 93+6 93 ± 6 69 ± 10 49 ± 76 738 ± 12 91+8 78+7 llcl 128 + 18 1 57+ 1 94+9 111 ± 4 High 81+5 82+6 51 + 11 60+5 81 + 10 83+ 13 102 + 2 99+3 N.D. 78+2 120+ 4 95+2 84+ 1 94+2 93+ 1 94+2 100+ 1 92+ 1 81 + 15 113+ 4 69+5 77+4 1 94+11 1 106 + 12 91+2 98+3 After Cleanup Low N.C.ia> N.C. N.C. N.C. N.C. N.C. N.C. N.C. N.D. 43+ 7 N.D. 54 ± 8 N.D. 96 ± 3 95+3 95+2 97+2 69 ± 6 N.C. 126 ± 8 89 ± 6 26+3 1 73 + 25 1 37+8 91+6 83+ 72 High N.C. N.C. N.C. N.C. N.C. N.C. N.C. N.C. N.D. 58+6 65+ 14 78+ 11 42+ 13 94+3 93+2 97 ± 3 99' ± 4 60+6 N.C. 109 ± 10 71 + 5 72+ 14 1 62+5 1 86+ 72 128 ± 77 108 ± 13 Before Cleanup Low 96+5 19 + 14 56+4 69+2 94+7 N.D. 96+7 85+11 52+9 87 ± 15 85+2 94+5 94 ± 5 109 ± 1 103+ 1 105+ 1 120 ± 2 107 ± 1 124+ 6 94+6 78+2 76 ±40 1 N.D. 1 47 + 72 89 ± 8 85+2 High 100 ± 58 + 61 + 82 + 76 + 28 + 94 + 77 + 71 ± 91 ± 110± 86 + 77 + 102 ± 100 ± 103 + 123 ± 108 ± 777 ± 773 ± 71 ± 72 + 1 62 + 1 99 + 85 + 90 ± 2 1 1 15 2 16 3 7 0 3 6 5 3 1 1 1 1 2 2 2 2 3 5 2 3 2 After Cleanup Low N.C. N.C. N.C. N.C. N.C. N.C. N.C. N.C. 58+4 67+6 N.D. 59+ 72 57+4 105 ± 3 104 ± 5 95+3 108+ 4 76 ±77 N.C. 74+3 76+4 123 ± 53 1 71 + 5 1 40 + 27 97 ± 14 41 + 11 High N.C. N.C. N.C. N.C. N.C. N.C. N.C. N.C. 68+3 74+3 62+4 79+3 54+8 97+3 95+2 94+4 106+ 3 65+ 17 N.C. 108+ 3 70+2 80+ 10 1 76+2 1 90 + 14 98 + 27 95 + 29 (alN.C. = No cleanup procedure included in this method. N.D. = Not detected. MI - Presence of interferences precluded determination of compound in sample. ld>Standard deviation is included. ------- Tina M. Engel, J. Scott Warner, and W. Marcus Cooke are with Battelle Columbus Laboratories, Columbus, OH 43201. Thomas A. Presshy is the EPA Project Officer (see below). The complete report, entitled "Evaluation of 10 Pesticide Methods," (Order No. PB 85-238 608/AS; Cost: $14.50, 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: Environmental Monitoring and Support Laboratory U.S. Environmental Protection Agency Cincinnati, OH 45268 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Official Business Penalty for Private Use $300 EPA/600/S4-85/050 0000329 PS AGENCY ------- |