Anal. Chem. 1881, 63,118R-130R (E251 Ahifotoh, M. 0.; Cros, A.; Swnsson, B. G.; Tu, K. N. phys. Rev. 8 1990, 4 , 9819-27. (E28) H#e,M.; Maeda, H.; Kami, K.; Mori, H.; Sakakibara, A.; Takemota. Y. J . Non-QYSt. sdlds 1990, 177-778, 144-7. (E27) W,S. E.; Kim, K. H.; Skebn, E. F.; Fufdyana, J. K. J. Appl. phys. 1990, 87, 2158-7. (E281 Abruna, H. D. Mod. AspectsEktrochem. 1990, 20, 285-326. (E29) Panjan, P.; Navinsek, E.; Zabkar, A.; Mandrkro, D.; Godec, M.; Korelj, M.; Krhrokapic, A.; Zalar, A. Thln W Fihs 1990, 787, 35-41. (E30) Rastogi, R. S.; Vanker, V. D.; Chopra, K. L. J. Appl. Fhys. 1990, 87, 1888-73. (E31) Barrett. N. T.; Gibson. P. N.; Greaves, 0. N.; Roberts, K. J.; Scchl. M. ’ pirvsice 8 1989, 758, 890-1. (E321 Wang. S. Q.; Mayer. J. W. Appl. phys. 1990, 87, 2932-8. (E33) Seyers, D. E.; Stem, E. A.; Lytle, F. W. phys. Rev. Lett. 1971, 27,
(E40) Nelson, L. S., Jr.; Holt, C.; Hukins, D. W. L. physka 6 1989, 758, 103-1 04. (E41) Wang, Wencai; Chen, Yu. physlca 8 1990, 758. 829-30. (E42) Udun. M.; Kang, L.; Xladlang, S. physics B 1990, 758, 892-3. (E43) McOerth, R.; MacDowell, A. A.; Hashizame. T.; Sette, F.; CMn. P. H. Fhys. Rev. 8 1990, 40, 4857-63. (E44) Rossi, G.; Santanieilo, A.; De Padova, P.; Jln, X.; Chanderris, D. M . FhJ’S. Ac& 1989, 62. 888-70. (E45) Yokoyama, T.; Asakura. K.; Iwasawa. Y.; Kuroda. H. J. phys. Chem. 1989, 93, 8323-7. (E461 Johnson, G. W.; Brodie, D. E.;Crozier, E. D. Can. J. phys. 1989, 87, 358-64. (E47) Ghatikar, M. N. Physlca 6 1989. 758, 383-5. (E481 Sadoc, A.; Flank, A. H.; Lagarde, P. phys/ca 6 1989, 758, 80-4. (E491 Barrera, E. V.; Heald, S. M.; Marcus, H. L. Meter. Sc/. Eng. A 1989, 7 77. 45-9. (E50) Kuroda, H.;Iwasawa, Y. Int. Rev. W y s . Chem. 1990, 8 , 207-34. (E51) Penner-Hahn, J. E.; Tsang. H. T.; O’Halloran, T. V.; Wright, J. physlce 6 1989, 758, 117-18. (E52) Korystova, A. F.; Sheiestov, V. M.; Vazlna, A. A. “9.Instrum. Methods phys. Res. 1990. A282. 506-9. (E53) Maeyama, S.; Satow. Y.; Oshlma, M.; Katsui. A. Fhys/ca 8 1989, 758, 4723-4. (E54) Chen, D. H.; Sabatini, R. L.; Qiu, S. L.; Di Marrio, D.; Heald, S. M.; Wlesmann, H. AIPConf. Roc. 1989, 782, 74-81. (E59 Yang, C.; Wang. W.; Chen, Y.; Wen, 0.;Zheng. W. physlca 8 1989. 758, 490- 1. (E561 28,Konlshi, 2042-3.R.; Arioka, M.; Sasakura, H. Jpn. J. Appl. phys. Pari 7 1990.
1204-7. ..
(E34) Lee, P. A.; Cktln, P.; Elsenberger, P.; Kincaid. B. M. Rev. Mod. Fhys. 1988, 5 3 , 789-808. (E35) For example, Koninsberg, D. C.; Prims. R. X-ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES, Wiley: New York, 1988. Fay, M. J.; Hoffman, D. P.; Hercules, D. M. Anal. Chem. 1988, 80, 1225A-1243A. (E38) Islam,Shaheen M.; Bunker Burce, A. Fhyslce 8 1990, 758, 806-607. (E37) Dexpert-Ghys, J.; Charreire, Y.; Esteban-Puges. P.; Abert, L.; Dexpert, H. phys. Status solldl B 1990, 155, 571-79. (E38) Bauchspless, K. R.; Crozier, E. D.; Ingaib, R. physlca 6 1990, 758, 492-494. (E39) Yokoyama, T.; Satsukawa, T.; Ohta. T. Jpn. J. Appl. phys. Part 7 1990, 28, 1905-8.
Pesticides Joseph Sherma Department of Chemistry, Lafayette College, Easton, Pennsylvania 18042
INTRODUCTION This review covers the literature on pesticide analysis published or abstracted in the period between Dec 1, 1988, and Dec 1,1990. The major sources of information were the rimary abstracting journals Chemical Abstracts and Anabtical Abstracts. Journals that were searched direct1 include the Journal of the Association of Official Analytical zhemists, Journal of Agricultural and Food Chemistry, Bulletin of Environmental Contamination and Toxicology, Analytical Chemistry, Analyst, Chromatogra hia, and the Journal of Chromato raphy (including its biiliography issues). The review is dlevoted mainly to methods for the determination of residues of pesticides in a wide variety of sample matrices. Some covera e is iven to the analysis of related industrial chemicals, su& as %CBsand dioxins, but pesticide formulation analysis is not reviewed. The attem t was made to choose only the most important publicationsIkribing methodology, instrumentation, and applications that would be readily . citations are given availableto readers of thisJ O U ~ ~Abstract for references from the more obscure journals and those not published in English. At the present time, GC is the primary method used for pesticide residue analysis,but applicationsof HPLC, HPTLC, and SFC have been increasing steadily. Areas in which significant advances and/or promise for future development in pesticide analysis were noted during the past 2 years include capillary and two-dimensional capillary GC; ca illary and microbore HPLC; increased application of HPL8 detectors other than UV,such as the electrochemicaldetector; unproved sample preparation employing SPE, on-line extraction and Dreconcentration methods. and SFE: automated samde pre aration and identification rocedures; cou led methds sucE as GC MS MS, HPLCTMS, GC/FTI$ and radioGC/MS; an met ods involving enzyme inhibition. Perhaps
the most exciting research area, and the one with the most likelihood of significant progress, is the development of immunoassay methods for pesticide analysis. Most available residue methods have been devised for the analysis of only a single pesticide or pesticide class. Public health concerns require continued research aimed at extending the available multiclass, multiresidue methods, and finding new methods to include many more of the pesticides being used worldwide, as well as their olar and conjugated metabolites. This roblem was highighted in a feature article in Analytical Cfemistry,Vol. 81 (14), p 861A (1989),titled “The Great Fruit Scares of 1989”,which discussed the “near panic” that occured in America when residues of the plant growth regulator daminozide (Alar) were found in a ples and cyanide in grapes. The article states that mutiresidue methods used by the FDA to routinely check foods for contaminants “...can pick up 40% of the pesticides likely to leave residues...” and that daminozide is among those pesticides that “...slip ast the routine screens.” The article goes on to describe &e single residue methods used to detect and determine this compound and also elaborates efforts taken to devise and test new methods for analyzing cyanide in fruit. While multiresidue methods are used by state and federal agencies to monitor foods and the environment, more specific analytical methods are used by the agrochemical companies, and contract laboratories hired by these companies,in support of pesticide registration and reregistration. New anal ical methods for particular pesticides and metabolites are eing developed continuall by industry and contract laboratories and tested by the dPA, and many, if not most, of these methods are never published in the open literature. It would be very beneficial to pesticide scientists worldwide if these methods, which end up in governmentand industry files, could somehow be published.
6
dI,
BOOKS AND REVIEWS
Abbreviations used throughout this review are listed in Table I. Pesticide abbreviations, common names, and trade names are used according to the Pesticide Dictionary of the Farm Chemicals Handbook ’90,Meister Publishing Co., WIlloughby, OH.
118R
0003-270019 110363-118R$09.5010
Books on the principles and practice of plant hormone analysis ( A I ,A2), residue analysis of plant protection agents and their metabolites (A3),and good laboratory practices in 0
1991 American Chemical
Society
PESTICIDES
Jcmeph s)mnur recehred a B.S. in dremfstry from Upsala College, East Orange, KI, in 1955 and a Ph.D. in anatytkai chemistry from Rutgers Universfty in 1958. His thesis research In lon exchange chromatography was under the direction of the late Wm. Rieman 111. Dr. 9”joined the faculty of Lafayette Colk3ge in Sept 1958 and is pres-
entty Charles A. Dana Professor and Head of the Department of Chemistry and is in charge of three courses in analytical chemistry. Dr. S t ” a independentty and with others has written or edited over 320 papers, chapters, books, and revlews covering chromatographic and analytical methods. His current research interests are in quantitative TLC, mainly appiled to lipid analysis, pesticlde residues, and food additives. He is Editor for residues and d ” t s of JAOAC.
agrochemical analysis (A4) were published. Papers from a 1989ACS symposium on LC/MS applicationsin agriculture, pharmaceutical, and environmental chemistry (A5) and a compilation of negative ion maw spectra of 361 environmental contaminants, including OC pesticides, herbicides, and halogenated industrialchemicals (A6),were published. The 15th edition of the OfficialMethods of the Association of Official Analytical Chemists ( A7) includes validated analytical methods for pesticide residues. The FDA Pesticide Analytical Manual (A8)and NIOSH M a w 1 of Analytical Methods (A9) were revised. Two books published by CRC Press contained updated chemical, physical, analytical, toxicit and usage , ed., data: European Directory of Agrochemical F r o ~ c t s3rd Vols. 1-4, and Agrochemicals Handbook, 2nd ed. Three reviews of immunochemical methods of pesticide residue analysis were published (AIO-A12). The following aspects of water analysis were reviewed: accuracy and precision with reference to the EEC water quality directive (A13); modern methods and analytical trends (A14, A15): a review in tabular form with 292 references (A16);analysis from highly polluted surface waters (A17);and enzyme immunoassays for determination of pesticides in water ( A B ,A19). MS methods for identifjlngpesticide metabolites were reviewed (AZO).The TLC analysis of pesticides was reviewed in a book chapter (A21). Other reviews on specific methods or applicationsare cited in the appropriate sections below.
GENERAL AND MULTICLASS/MULTIRESIDUE METHODS Extraction, cleanup, and chromatographic determination of OP yrethroid, and carbamate insecticides were reviewed (BI).fnalytical quality assurance in the German food contamination monitoring program was discussed (B2,B3). The following multiclass multiresidue determinations were reported: carbaryl, dicam a, chlorothalonil,and glyphosate on apparel fabrics (B4);carbofuran, metalaxyl,and simazine in soils by acetonepH 2 buffer extraction,cleanup by solvent partitioning and silica gel SPE, and GC with an NPD (B5); alachlor, metolachlor, and atrazine in soil and maize by methanol extraction, cleanup on acidic alumina and Florisil, and GC-NPD/MS (B6);bromopropylate and coumaphos in honey and honeycomb by C-18 extraction and capillary GC (B7);screening of 21 pesticides in water by single extraction 34 pesticides by GC with C-18 columns and HRGC/MS (B8); after mini silica gel column cleanup (B9);triazines and OP pesticides in soil by packed and capillary column GC (BIO); fungicides, antis routing agents, and OP and OC pesticides in potatoes by Ei‘C and HPLC ( B I I ) ; 12 pesticides and 2 metabolites in fruits and vegetables using a modified Luke procedure and capillary GC with an ion trap detector (BIZ); several classes of pesticides, including a broad range of herbicides, in soils and feeds by HPLC-PCD (B13);nitrogeneous pesticides by photolysis and reaction with OPA-8-mercaptopolar ethanol for HPLC with fluorescence detection (B14); pesticides in water by GC after C-18 extraction and reaction with diazomethane (B15);OC, OP, and carbamate pesticides in water and air usin HPLC fractionation and selective-detector GC (B16);a n i 43 carbamate, urea, triazine, and OC pesticides in environmental samples by C-18 HPLC-W (B17).
l
Table I. Abbreviations
AFID AOAC aq “C C-8 C-18 CB CI CN 2-D DLI EEC ECD EIA ELISA EPA FDA fg FID FIIA FPD FT GC GPC HPLC HPTLC HR IR L mL MS N NH2 NI NIOSH ng nm NMR NP NPD
oc
ODS OP OPA P PAH PB PCB PCD PCDD PCDF Pg PI PPb PPm PPtr PTFE RIA RP S 8
SFC SFE SIM SPE TCDD TLC rcg
uv
-
alkali flame ionization detector Association of Official Analytical Chemists aqueous degrees centigrade C8 alkyl-bonded silica gel C18alkyl-bonded silica gel chlorobiphenyl chemical ionization cyano-bonded silica gel two dimensional direct liquid introduction European Economic Community electron capture detector enzyme immunoassay enzyme-linked immunosorbent assay Environmental Protection Agency Food and Drug Administration femtogram (s) flame ionization detector flow injection immunoanalysis flame photometric detector Fourier transform gas chromatography (gas-liquid chromatography) gel permeation chromatography high performance liquid chromatography high performance thin layer chromatography high resolution infrared liter milliliter(s) mass spectrometry nitrogen amino-bonded silica gel negative ion National Institute for Occupational Safety and Health nanogram($ nanometer(s) nuclear magnetic resonance normal phase nitrogen-phosphorus-selective (thermionic) detector organochlorine octadecylsilyl organophosph o w o-phthalaldehyde phosphorus polycyclic aromatic hydrocarbon particle beam polychlorinated biphenyl photoconductivity detector polychlorinated dibenzo-p-dioxin polychlorinated dibenzofuran picogram(s) positive ion parts per billion parts per million parts per trillion poly(tetrafluoroethy1ene) radioimmunoassay reversed phase sulfur second($ supercritical fluid chromatography supercritical fluid extraction selected ion monitoring solid phase extraction tetrachlorodibenzo-p-dioxin thin layer chromatography microgram(s) ultraviolet
Different multiresidue methods were compared for the determination of OC and OP pesticides in fruit samples by capillary GC-ECD + NPD (B18).OC and OP pesticides were determined in lanolin by using an Extrelut column for extraction and C-18 SPE for cleanup prior to GC-ECD + FPD (B19);in raw coffee by capillary GC-ECD + NPD (B20);and in cosmetics and skin-care products by ethyl acetate extraction, GPC cleanup, fractionation on a silica gel column, and ANALYTICAL CHEMISTRY, VOL. 63, NO. 12, JUNE 15, 1991
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PESTICIDES
double-column capillary GC-ECD + FID (B21). OC, OP, and pyrethroid pesticides were determined in cosmetics by us' GPC and k . ~ column y cleanup (B22); in seawater by3C-ECD after 18 cartridge enrichment (B23); and in cereals, cereal products, and animal feed b acetone-methanol extraction and GPC cleanup (B24). 0% compounds and carbamates were screened in drinking water at
