Anal. Chem. 1983, 55, 57 R-70 R
Pesti(2 ides Joseph Siherma Chemistry Department, La fayette College, Easton, Pennsylvania 18042
Gunter Zwelg”’ Sanitaty Engineering and Environmental Health Research Laboratory, University of California, Richmond, California 94804
This review on the analysis of pesticide residues and formulations covers the literature from October 1980 till November 1982 with the following sources being utilized Chemical Abstracts, Analytical Abstracts, and Pesticide Abstracts. The last journal ceased to exist in 1981 leaving a gap in the coverage of the international pesticide literature. It is hoped that Chemical Abstracts will be able to supplement their pesticide coverage, so that valuable information will not be lost to the scientific community engaged in pesticide research. The followingjournals were also reviewed and appropriate abstracts prepared Journal of Agricultural and Food Chemistry: Journal of Association Official Analytical Chemists; Bulletin of Environmental Contamination and Toxicology; and the Journal of Chromatography. As in pr’evious reviews, the first sections are devoted to general topics applicable to most pesticides;the latter sections deal with analytical methods for specific or classes of pesticides. Literature citations are kept separate for each section and are annotated by numbers and capital letters. We believe, that this scheme simplifies the search for specific references and also eases the task of these two authors to consolidate their manuscript and meet the stringent deadline of the publisher. We have endeavored to keep the number of cited articles below 500 and to cite pertinent abstract journals for articles which appeiaed in obscure journals which may not be readily available at, all libraries. The trend in analytical methodology for pesticides during the past 2 years does not appear to have been trailblazing. There seems to have been an attempt to utilize tandem mass spectrometIy/mass spectrometry (MS/MS) as a complement to gas chromatography/mass spectrometry (GC/MS) to identify minute traces of pesticide metabolites and impurities (e.g., dioxins). Automated sample preparation and the use of capillary IGCand high-performance liquid chromatography (HPLC) have been reported in the reviewed literature. Some advances have been made on specific detection methods for HPLC and the use of coupled HPLC/MS, as commerical equipment is becoming available. The once promising technique of gas chromatography/infraed (GC/IR) interferometry and Fourier analysis has not received wide acceptance in pesticide analyses as judged by the published articles which were reviewed.
periodically published supplements; the 3rd edition of Preston’s guide on the analysis of pesticides by GC (23A); Worthing’s 6th edition of the pesticide manual (28A) and il;s predecessor, the 7th edition of the old Martin’s “Guide to Chemicals Used in Crop Protection” (26A), most recently written by E. Y. Spencer, who states in the Introduction that this will be his last authorship of this splendid and relatively low-cost, almost indispensable reference book. A useful review has been written on laboratory management in analytical methods development (27A) making I t a handy guide for the manager responsible for setting up a new laboratory or reorganizing an established one. The 1982 annual ASTM standards book covers, among other subjects,pesticides (1A). The proceedings of an annual workshop for pesticide residue analysts held in Canada, contains useful information (22A). An overview of modern analytical techniques for pesticides, impurities, metabolites, and degradation products has been published @A). Two provocative articles on the interpretation of analytical pesticide data have been written by recognized authorities W. Horwitz (16A) and F. A. Gunther (13A). The reasons for large variability among analytical samples of environmental origins are discussed (18A), and a statistical method for interpreting these data has been suggested (24A). Problems of solvent evaporation from reference standard pesticide solutions (15A) and the use of ultrapure reagents for trace analysis have been investigated (21A). The subject of chemical derivatization in pesticide analysis has been reviewed (4A). The application of the electroncapture detector in GC for the analysis of pesticides (5A) and dioxins (3A) has been the subject of two reviews. Chemical ionization mass spectrometry for hydrocarbons, including the chlorinated pesticides, has been reviewed (14A). Negative chemical ionization has been the subject of anothel. review (7A). Analytical methodology for human pesticide monitoring including urinalysis of metabolites has been discussed in two articles (12A, 2A). The analysis of pesticides in environmental samples (17A, 19A) and foodstuffs (IIA) has been recently reviewed. Analytical methods for two classes of pesticides have been1 thoroughly covered in two recent review articles, systemic fungicides (10A) and Bynthetic pyrethroids (20A).
BOOKS AND REVIEWS
The greatest interest appears to be on air sampling of pesticides and other environmental pollutants, as judged by the number of papers published on this subject. A highvolume air sampler for trapping pesticides and semivolatile industrial organic chemicals has been improved (15B). Personal sampling techniques in the workplace have been standardized and validated (9B).A portable, battery-powered personal sampler for air-borne pesticides and other chemicals has been developed and utilizes polyurethane foam as trapping agent (16B). Polyurethane foam has been evaluated as trapping agents fo; a number of pesticides, including herbicides OB, 8B, 13H. Bonded-phase silica columns have been utilized to concentrate chlorinated pesticides from water (4B). The retention behavior of chlorinated chemicals, including the insecticide aldrin, on four sorbent materials has been investigated (6B). These materials were Tenax-GC, Chromosorb 101, Florisil, and Carbopack C HT. Over 130 methods have been validated
Several useful new books and revised editions of established reference books on pesticides have appeared during the past reporting period. A multiauthored volume edited by E(. G. Das (6A) brings instrumental methods for pesticide analyses up-to-date, although certain techniques like NMR and polarography have never achieved the same popularity as chromatographic techniques. A valuable addition to the pesticide literature is the “Manual of Analytical Quality Control for Pesticides and Related Compounds in Human and Environmental Samples” written by J. Sherma (25A). Updated and revised editions of the following publications are recommended as desk reference material for most pesticide researchers: FDA “Pesticide Analytical Manual”, Vol. I (8A), which unfortunately requires secretarial help for inserting ‘Permanent address: U.S.Environmental Protection Agency, Office of Pesticide Programs, Washington, DC 20460. 0003-2700/83/0355-57R$O 1.5010
SAMPLING AND CLEANUP PROCEDURES
0 1983 American
Chemical Society
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for the use of solid adsorbents for workplace sampling of organic chemicals (1OB); Chromosorb 102 was found useful for the insecticides mevinphos and heptachlor (3B). The extraction and cleanup of pesticide residues found in plants, soil, and water have been studied (2B). An efficient device for collecting soil samples for pesticide residue analysis has been developed (5B). A glass apparatus has been constructed allowing the concentration of 4 mL of a dilute solution of pesticides a t mild temperatures in about 20 min (18B). Automated gel permeation chromatography has been successfully used to remove fats from foods prior to pesticide residue analysis (1lB, 12B). Continuous-flow centrifugation has been recommended for contaminant analysis of suspended sediments and is suitable for pesticide analysis (17B). Caution is advisable when using Soxhlet extraction of environmental samples with acetone (14B); artifacts from soil extracts include diacetone alcohol, mesityl oxide, phorone, and isophorone.
GAS CHROMATOGRAPHY Techniques. Recommended column packings for gas chromatography (GC) of pesticides are the following ( I C ) : OV-22,OV-101, NPGS, SE-30(3% Gas-Chrom Q), and 1.95% SP-2401/ 1.5% SP-2250 on Supelcoport. A high-temperature column-switch technique was found to be useful for pesticide residue analysis (19C);the precolumn and main column had ackings of different polarities, e.g., OV-225 and OV-101. erially coupled chromatographic columns at different temperatures (2C) or linearly programmed (3C) were found useful for the broad sprectrum analysis of complex mixtures of pesticides. A simple procedure, the addition of a small amount of nonflammable solvent, has been found to overcome base line fluctuations in GC, especially when injecting large volume samples (21C). The multiresidue pesticide method has been simplified by the elimination of a Florisil cleanup step (16C). Pesticides containing C1, N, and S were detected with a Hall conductivity detector and those Containing - P, . with a flame photometric detector. Capillary Column GC. Pesticide analysis by capillary GC has become more popular as attested by the large number of reports found during this period. Organochlorine and organophosphorus pesticides and their metabolites have been resolved by capillary GC (IOC, 14C, 27C). The split-splitless injection system has resulted in an overall 10- to 500-fold increase in the sensitivity of detection of environmental samples containing organochlorine and organophosphorus compounds (26C). Repeated in’ections of large volumes of samples containing p , p ’-DDD and o,p ’-DDT using the splitless injection system into wide-bore glass capillary columns did not significantly deteriorate the performance of the GC (4C). Detectors and Detection Systems. A critical assessment of gas chromatographic selective detectors has been made, including the evaluation of photometric, electrolytic conductometric, and thermionic N / P detectors (7C). A thermoaerosol detector for phosphorus and an ionization-resonance detector for sulfur have been tested with a reference sample containing phosphorus trichlorosulfide (24C). Several commerical, selective GC detectors used in conjunction with capillary columns have been compared for the analysis of sludge extracts (132). Methyl parathion was one of the compounds identified without extensive cleanup. Two high-resolution GC techniques were found to be comparable in the identification of priority pollutants, including several organochlorine esticides (20C);the two techniques were high-resolution G8/l?ourier transform IR spectroscopy and GC/MS. The sensitivity of the infrared method was improved by the use of wall-coated open tubular columns (WCOT). With electronic background subtraction, it was possible to identify parathion, fenthion, and bromophos from a mixture by GC/MS with a quadrupole system (23C). The electron capture detection threshold of 77 tested organohalogen pesticides was found to be proportional to a sensitivity factor (9C). The design and operation of the electron-capture detector (EC) have been discussed (18C). Nonhaloeenated com.oounds like warfarin. sulfonamides. and one pyrtthroid inseiticide can be quantified with the EC detector (2.97). A nonradioactive EC detector has been developed by the use of a thermionic emitter as an electron source (17C). An inexpensive electrometer has been designed for a flame
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photometer detector (FPD) (22C). Investigations were conducted on the optimization of the FPD (5C). The simultaneous identification of 14C-labeledpesticide metabolites was accomplished by combining FID and an anthracene flow cell (for radioactivity) after capillary GC (11C). Two selective detectors for sulfur-containingpesticides have been compared the flame photometric detector and the 700A Hall electrolytic conductivity detector (6C), and it was concluded that the latter detector had several performance advantages over the FPD. It has been demonstrated that pesticides containing C1, N, and P could be simultaneously analyzed by GC with an EC and N/P detector mounted in series (80 Two potentially promising detectors have been studied for the analysis of pesticides: one utilizes atmospheric pressure helium plasma as a GC detector for compounds of low volatility, e.g., lindane, aldrin, PCNB, DDT, dieldrin, and kepone (13C), while the other is a pizoelectric crystal detector for atmospheric pollutant gases and organophosphorus compounds (12C).
HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC) Two recent books by J. F. Lawrence are recommended as reference works for the practicing pesticide chemist: the first one (130)covers the field of organic trace analysis by HPLC; the second one covers specifically the application of HPLC to pesticide analysis (140). Pesticides like carbaryl, benomyl, carbendazim, carbofuran can be analyzed by reversed-phase HPLC using C-8 or C-18 chemically bonded columns (unpublished data by G.Z.). As mentioned earlier in the Introduction, the interfacing of HPLC and mass spectrometry has become the subject of a number of studies during the past 2 years and is in no small part due to the availability of commercial, yet expensive, equipment. The subject has been recently reviewed (70,80). The technique of a moving-belt interface between LC and MS and its application to the analysis of chlorpropham, a carbamate herbicide, have been the subject of a study (60). Another publication by the same group of researchers covers the application of LC/MS to the analysis of pesticides among other classes of chemicals (40). Eighteen organophosphorus pesticides have been studied by combined HPLC and negative chemical ionization mass spectrometry (160). Chromatography was by reversed-phase on C-8 bonded column and MS was performed on-line with a direct liquid-insertion probe. A drawback for applying HPLC to pesticide analysis has been the lack of selective detection systems. However, during the past 2 years, some advances have been reported to correct this deficiency. By choosing two UV lines, 214 and 229 nm, for the detection of a number of pesticides, the sensitivity was increased significantly, so that the backgroud noise could be lowered by injecting smaller aliquots (120). The subject of “reaction detectors” has been reviewed recently ( 5 0 ) . A nitrogen-selective detector for HPLC was constructed from a moving-wire transport system and a Hall electrolytic conductivity cell ( 9 0 ) . A phosphorus-sensitive molecular emission cavity analysis detector has been adapted to monitor organophosphorus compounds emerging from an HPLC column (2C). An electrochemical detector for LC is based on the use of a mercury film electrode and has been applied to the analysis of a reducible substance, like parathion (10).
Applications of HPLC and liquid chromatography (LC) of special interest to pesticide analysis are the analysis of phenylphosphonothioate esters, like EPN, cyanofenphos, and leptophos ( I I D ) and the analysis of pesticide residues from soil and plants (150). A patented stationary phase for gel and adsorption chromatography is composed of charcoal which adheres to the surface of individual particles of a molecular-size exclusion gel polymer (100). An ultraviolet detection system for use in automated size exclusion chromatographic cleanup has been applied to pesticide analysis (30).
THIN-LAYER AND PAPER CHROMATOGRAPHY The subject of thin-layer chromatography of pesticides, recent advances and applications for separation, detection,
Joa@ S h m u
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PESTICIDES
a 0.8. h
bv h a upsals colsos.~ a s t ~ n n gKI. s . in 1955 and a h.0. in a n a w l chembby horn Rvtgers UWersHy h 1958. His meSk
research in lon sxchangs chromatography was lnder mS m&n of me late Wm. R l a ma" 111. h.shenna billed me racuny Of Lafayem college in sapt 1958 and 18 we* Charles A. Dana Rofesyx 01 A n a W cai Chernioby. h. S k m a lndepandenny and wnh Omers has wmen many chapters. books. and reviews coverlng chromatwraDhic and anawcal methoda. HIS cmsni risearch inter& are in quantitative nc.mainly applied to ciinlCai analytative si. pesticide rermuts. and food mnives. HO k ednw tw pasticldd resmws sis. Of tha JAOAC.
em
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and metabolites (see also under gas chromatography and HPLC, above). The field of masa spectrometry of pesticides has been reviewed (14F).Field desorption masa spectrometry has been studied for different purposes: inorganic contaminants usually decrease the sensitivity of the method in biological samples (ZIF); mass spectra of field desorption of six pesticides have been determined ( 6 0 , and components of Mesoranil were identified; high-resolution field desorption mass spectrometry of OP-pesticides has been used to identify them in wastewaters (Z3F). Negative chemical ionization mass spectrometry has been applied for the analysis of polychlorinated chemical residues in biological samples (7F) and pentachlorophenol and its tetrachlorocontaminant in environmental samples (SF);the spectra of 17 OP-pesticides were obtained from dichloromethaoe-mediated negative chemical ionization MS (SF). Nuclear double resonance technique (NDR) has been applied for the detection of several pesticides (carbanolate, Barban, CIPC) in water (ZOF). Room-temperature and lowtemperature phosphorescence characteristics of several pesticides suggest that this might be used as an analytical technique for pesticide standards in the 10-50 ng range ( I F ) . Organophosphorus compounds in the atmosphere have been measured with a piezoelectric quartz crystal coated with 1n-dodecyl-3-(hydroximinomethyl)pyridiniumiodide (&PAD) for Gagente and bistidine HCI for malathion-type compounds (16F).
ORGANOCHLORINE PESTICIDES
and quantification, has been reviewed by J.S. (IOE). A book devoted to the subject of paper and thin-layer chromatography of environmental toxicants has appeared (3E). Two recent reviews on quantitative analysis of pesticides by TLC and in situ fluorometry have been published (SE, SE). TLC has been recommended as the choice method to study the purity of radiolabeled xenobiotics, their metabolic fate, and stability (7E). The Commission on Pesticide Chemistry (IUPAC) has concluded that TLC is useful in multiresidue determinations and quantitation of the most important elwes of pesticides (ZE). A general TLC method has been developed for the determination of pesticide residues in samples of plant origin, soil, and water (ZE). Eleven organophosphorus insecticides have been separated on TLC impregnated with metal salt or phenol ( I I E ) . Methoxychlor and methidathion have been identified in clinical samples by conventional and reversed-phase TLC (Z2E). Methamidopbos residues from potato tubers have been analyzed by TLC and visualized in situ by a modified cholinesterase technique (SEI. A fluorescent reagent for a variety of pesticides on solidstate supports, presumably includin TLC, contains 2-diphenylacetyl-1-3-indandion-1-imine TSE). A chromogenic paper prepared by treating it with a dilute solution of 0-tolidine is useful for spot-testing chlorinated pesticides (4E).
MISCELLANEOUS ANALYTICAL TECHNIQUES A simple bioassay technique employing two organisms, Daphnia or Hyalella have been employed as an alternative to chemical analyses, to determine safe reentry intervals for farm workers (3F). Another biological system, this one employing cholinesterase, has been developed for the rapid scnnning for organophosphorus insecticides in surface waters ( 4 0 . This method utilizes acetylthiocholine as substrate. A similar technique utilizes indoxylacetate as substrate for the reaction (Z2F). Three acetylcholinesterasemethods have been compared the modified Michel method, pH stat, and radiometric method (ZSF). The radiometric method is suitable for detecting sublethal exposure to cholinesterase inhibiting pesticides, requiring only 5 ,tL of blood. A radioimmunoassay for parathion has been developed (5F). Parathion-specific antibodies were developed in rabbits with bovine serum albumin conjugated with the reduced form of the pesticide. Mass spectrometry continues to receive wide attention for the analysis and identification of pesticides, contaminants,
Although the agricultural use of most organochlorine pesticides has diminished during the past decade, significant levels of these cornpounds are still encountered in the environment due to their persistence. This explains the large number of reports on analytical methods and monitoring studies for chlorinated pesticides and chemically related compounds, like PCBs. A system has been described to prepare organobalogen reference materials (pesticides) in a marine lipid matrix (29G). A method has been developed for the identification and quantitative determination of OCesticides by a combination of GC and TLC (4SG). Doule-column capillary GC arranged as a precolumn and main column has been effective in identifying hexachlorobenzene and the four isomers of BHC (Z6G). Molecular emission cavity analysishas been adapted to detect organochlorine compounds after GC elution (6G). A personal air sampler for the detection of three OC-compounds has been developed and evaluated (5G). Two independent studies have been reported on the chromatographic cleanup of crop extracts prior to analysis: a comparison of silver nitrate/alumina columns (2IG) and dry column chromatography vs. acetonitrile partitioning (27G). The sulfuric acid treatment for cleanup of fatty and nonfatty foods prior to the analysis of OC-pesticides has been evaluated (47G),and in another study it was found that dieldrin residues were reduced by the acid treatment (46G). The H,SO, solid phase matrix catalyzed reaction between heptachlor and various organic compounds (benzene, o-dichlorobenzene, etc.) has been studied and might be useful for the confirmation of pesticide residue identities ( I C ) by NMR. Graphitized carbon black (GCB) serves as an excellent sorbent material for chlorinated pesticides and is useful for the determination of these compounds in water (2G). A method is described for the determination of nanogramquantities per liter of water of hexachlorocyclopentadiene, involving extraction, column cleanup, and GC (3G). Gelpermeation chromatography has been shown to be a useful cleanup tool for OC-compounds in onions prior to GC analysis (4G). A rapid extraction of persistent OC-compounds from biological material with low fat content has been described (3.56). Aldrin can be confirmed by reacting it with Cr(I1) in dimethylformamide and analyzing the products by GC (IOG). A GC method for the determination of residues of cblordanes and related compounds in fish bas been described (34G). The collection efficiency of Chromosorb 102 and ethylene glycol for chlordane has been studied (61G). A gas chromatography method has been described for the analysis of organochlorine pesticides by the use of a mixed phase capillary column composed of OV-17and QF-1(IZC). A mixture of DDT and its analogues and P C B s have been
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analyzed b HPLC after converting DDT into the corresponding dkhlorobenzophenone (9G). The performance characteristics of a draft method for the analysis of OC-insecticides and PCBs were studied (14G);the method involves extraction by shaking or rolling techniques, followed by column chromatographic cleanup and final analysis by GC. Six li uid chromatography methods for the c termination of 0%-insecticides and PCB's were compared and evaluated, and a modified method was developed for the analysis of ocean fish (38G). A new method has been developed for the quantitative determination of OC-pesticides and PCB's in water by concentrating the sample in a micro steam liquid-liquid distillation extractor and performing the analysis by capillary GC (20G). Optimum experimental conditions for the separation of OC-pesticides by high-performanceTLC were an unsaturated chamber and a 10-pm siliga gel (19G). A new chromogenic spraying reagent for the detection of endrin on TLC plates is Sn"C1, in 50% HC1, followed by an aqueous fuchsin dye solution (24G). Dieldrin derivatives have been identified by TLC (26G). A new detection reagent for TLC of DDT is 1,4-dihydroxybenzene (59G). Organochlorine pesticide residues have been analyzed in a number of substrates, for example, animal feeds from the sugar industry (25G),in human bone marrow (15G),and in plant materials after automated gel chromatography cleanup ( 1 7G),and DDT and hexachlorocyclohexane have been analyzed in milk (23G). The interferences in the analysis of DDT in human serum have been identified as low molecular weight polymeric materials extracted from a Kel-F valve (22G). A simplified monitoring procedure for benzo[a]pyrene, HCB, and PCP in water has been described and utilizes HPLC for benzo[a]pyrene and GC for the other compounds (18G). The analysis of chlorinated pesticides in water and soil has been the subject of a number of investigations: the use of Carbopack B for solute enrichment (31C);the use of macroreticular resins for low concentrations of OC-compounds in seawater and tap water (39G);the determination of OC-pesticides and PCB's in water (33G) and wastewaters (32G, 41 G, 42G). An interlaboratory comparison study on the determination of OC-pesticide residues in water and wastewater has been carried out (48G). Two methods for the analysis of OCpesticide residues in marine organisms have been compared, one method involvin acid digestion and the other alumina chromatography (498). Another report has been published on the analysis of OC-pesticide and PCB residues in fish by capillary column GC/MS (55G). An on-line method for the extraction and isolation of OCpesticide and PCB residues from milk and dairy products has been perfected, followed by capillary column GC (53G). GC methods for the analysis of OC-pesticides in human semen (54G) and human milk (57G) have been developed. Other adaptations of GC methods have been for the analysis of OC-pesticideresidues in fat samples (63G) and crude vegetable oil and its refinery byproducts (68G). Extraction of bound lindane from soil (66G) and the determination of BHC isomers in root vegetables (62G) have been the subject of two reports. Partially dechlorinated DDT and DDE homologues have been identified by GC/MS (65G). Toxaphene residues have been difficult to quantify due to the many components which make up the technical grade of this pesticide. Yet, there have been some improvements of previously published methods and applications: quantitative determination of toxaphene in honey by TLC (58G), toxaphene residues in model solutions and surface waters by TLC (60G),an automatic data system for selection of peaks and quantitative analysis by capillary column GC/negative ion MS and its application for the analysis of toxaphene in fish (44G); quantitative determination of toxaphene in bovine blood by GLC and electron-capture detection (30G). An improved cleanup technique for the estimation of endosulfan residues from fish tissues has been reported (43G), and endosulfan and endosulfan sulfate have been identified in apples and carrots by GLC/MS (67G). Two deproteinization methods have been compared for the determination of DDT and metabolites in serum (50G). Simplified cleanup procedures have been developed for adipose tissue containing PCB's, DDT, and its metabolites (51G). 60R
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Two cleanup procedures (acetonitrile-Florisil vs. automated gel permeation) for residues of OC-pesticides and PCB's in human adipose tissue have been evaluated (56G). Three closely related pesticides, mirex, kepone, and kelevan have been the subject of several publications: the quantitative determination of mirex and degradation products by capillary GC/MS (36G);the critique of this method (28G) and the rebuttal (37G);the GC determination of kelevan and kepone in potatoes (12G)and in milk (40G);mirex in edible fish by MS (13G);mirex in whole blood (52G) and lake sediments (8G);mirex and HCB in adipose tissue (64G);and the analysis of all three compounds by combination LC/MS (7G).
ORGANOPHOSPHORUS INSECTICIDES [Note: In all remaining sections, the capitalization of a specific pesticide denotes a tradename; lower case, generic or common name; when the name does not appear in Farm Chemical Handbook, 1982 ed. (Meister Publ. Co. Willoughby, OH), the Chemical Abstracts notation will be given.] General Procedures. A chemically sensitive field-effect transistor for the detection of OP-compounds, including pesticides, in the atmosphere has been critically evaluated (27H, 1 6 9 . OP-compounds in water can be detected at M equivalent concentration of paraoxon by an immobilized acetylcholinesterase system (IOH). A multiresidue analysis of OP-pesticides has been developed by the use of MS and selective ion monitoring (SIM) (29"). A rapid field method for the estimation of OP-insecticide residues on citrus foliage and grove soil is based on the color produced by the reaction between OP-compounds and 4-O,-nitrobenzyl)pyridine (7H, 23H). OP-insecticide residues on oranges have also been determined with GC (14H). A GC analytical method has been developed for the determination of OP-insecticide residues in onions (26H). For nonfatty foods, an OP-pesticide residue method has been modified so that larger quantities of sample (100 mg) could be analyzed by GC using the N / P detector in the P mode (13H). HPLC has been applied to the analysis of residues of the most common OP-insecticides in fruits and vegetables (19H). OP-residuesin dried fruit have been analyzed by TLC. For the analysis of trace quantities of OP-compounds in water and wastewater, a miniature absorption cartridge has been useful for the initial concentration (16H). The determination of OP-pesticides in wastewater by gas chromatography has been standardized and evaluated; Method 614 (39H) and Method 622 (40H). Tris(l,3-dichloropropyl)phosphate, triphenyl phosphate, and tributoxyethyl phosphate have been identified as unknown artifacts during the analysis of OP-insecticides in drinking water (55H). Alkyl phosphate metabolites found in urine have been extracted as ion pairs with a lipophilic quaternary ammonium cation and then reacted with pentafluorobenzyl bromide to form the corresponding ester ( 1 1 H ) . The latter derivatives are chromatographed by GC and detected with a flame photometric or N / P detector. Specific Procedures. Trichlorometaphos-3 [2633-54-71 residues in grain have been analyzed by a TLC method (28H). Likewise, Curacron or Selecron residues in environmental samples have been determined by thin-layer chromatography (30H). Trichlorfon (chlorofos) in air has been analyzed spectrophotometricallyby a reaction with resorcinol (4H). The reaction between trichlorfon and diazomethane has been studied as a possible method for the determination of trichlorfon and desmethyltrichlorfon (3H). Phosfolan, mephosfolan, and related compounds have been analyzed by HPLC (2H) and TLC (5H). An in situ densitometric TLC method for the determination of tetrachlorvinphos (Gardona) in apples has been developed (36H). A similar method was used for residues of Gardona in water and fish tissues (50H). This insecticide has also been analyzed by GLC on an SE-30 column for residues in plant products (51H). Acephate and methamidophos have been analyzed in natural waters, fish, sediment, and asparagus by GLC using Ultra-Bond I1 or OV-225 columns and an alkali flame detector (47H). By use of GC and the selective N P detector, fensulfothion and its three metabolites have een analyzed in several vegetables. Fenitrothion and its metabolites have been analyzed by GC after derivatization with diazoethane (except for 3-methyl4-nitrophenol)using a flame photmetric detector (1H). Similar
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PESTICIDES
residues have been determined by a TLC technique usin p-dimethylaminobenzaldehyde as detection reagent (38H). third method for the analysis of fenitrothion and possible degradation products in water involves HPLC after recovery from XAI) resins (52H). Fenitrothion in water has also been analyzed by an enzymatic inhibition in situ method after thin-layer chromatography (8H). The hydrolysis product of fenitrothion, 4-nitro-3-methylpheno1, forms the basis of a spectrophotometric method of analysis for residues in grain (18H). Abate from environmental water samples has been analyzed by reversed-phase TLC and quantitative estimation using N,2,6-trichlorobenzoquinoneimine as spray reagent (45H). Bolstar residues from soil, plants, and water have been analyzed by TLC and GC (31H). Three TLC methods have been published on the analysis of parathion and paraoxon utilizing cholinesterase inhibition for visualization (9H, 12H, 6 0 . Another TLC method is suitable for the analysis of parathion, methyl parathion, and fenitrothion after reduction to the corresponding amino derivatives (3223). Decomposition products of diazinon have been identified by three types of MS and might be used as environmental markers for parent compound contamination (46H). A detailed procedure is given for the GC determination of disulfoton, phorate, oxydemeton-methyl, and their toxic metabolites in asparagus and soil samples (48H). To determine bromophos residues in peanut crops, the parent compound is first reaacted with dansyl chloride to form a fluorogenic derivative which is chromatographed on thin layers (49H) with a detection limit of 0.5 ng. Triazophos residues in rape seeds have been analyzed by GC on an OV-101 column and detected with an AFID detector (53H). Aphos [74548-80-41 in air, water, and soil has been determined first by GC and then TLC (33H). A novel method for the determination of phosalone residues in apples it3 based on the activation of the Cu(I1) catalyst by phosalone and its hydrolysis product for the oxidation of hyroquionone by H O2 (37H). Chlorpyrifos has keen analyzed by GLC from a variety of substrates: in pea vines after preparative gel chromatography (21H);in peaches and grass (2223;peppermint hay and oil for parent compound and the corresponding hydroxy metabolite (25H); in vegetables and fruits (34H);in cat food (43H). Two HPLC methods have been described for the analysis of chlorpyrifos in water, reversed-phase HPLC after solvent extraction or Sep-PAK C18 absorption (41H) and HPLC using a Porasil column (45H). Four alteration products from malathion have been observed in rice extracts as shown by GC on columns of different polarities (24H). GC methods have been applied to the analysis of malathion in seven vegetables (35H) and, simultaneouslv with DirimiDhos-methvl, in Deanuts and related products (44H).' Terbuphos (Counter) and its metabolites have been identified in soil bv GC/MS (54H). GLC has been used for the determinationof Supracide and its monoxone metabolite in safflower seed, meal, and oil (57H). Azinphos-methyl and its oxon-metabolite have been analyzed in fruits and vegetables by reversed-phase HPLC (56"). Pirimiphos-methyl has been identified in imported foods by GC/MS (6H). Dipterex has been determined in human organs by GC/MS for the analysis of the distribution of this toxic compound in a case of fatal poisoning (58H). Monocrotophos has been detected on thin-layer chromatograms with a spraying solution made up with K13 and KI resulting in violet spots (17H).
1
I
,
CARBAMATE PESTICIDES General Procedures. A one-step procedure with pentafluorobenzyk bromide was used to prepare drivatives of 23 carbamates for gas chromatography (191). Aniline metabolites of substituted urea and carbamate herbicides were determined in water and urine by GC of acetylated derivatives (171). Carbamate insecticides were determined in rice and rice straw (331) and in foliage, forest soil, and fish tissue (460 by direct GC using an N-P selective detector. Sixteen N-methylcarbamate iinsecticides were chromatographed on an SE-52 capillary GC column (511). The HPLC of carbamate pesticides was studied by use of electrochemical detection (21,271). General procedures were
described for the HPLC determination of all carbamates covered by Australian regulations on pesticide residues (51) and for 21 carbamate and urea pesticides in industrial and municipal wastewater (361). A multiresidue method was described for determining seven carbamate insecticides and four related metabolites in crops at 0.05-1.0 ppm (201). An HPLC procedure with two coupled columns was used to cletermine carbamate residues in fruits and vegetables (121). Carbofuran, aldicarb, and metabolites were determined at 1 ppb in water by HPLC with UV detection (101). Combined LC/MS (CN column) was used to determine carbamate pesticides 1533, and field desorption MS analyiais was applied to carbamate and urea pesticides (181). Urea, carbamate, and thiocarbamate derivatives in air (14,vernolate, Drepamon, benthiocarb, and Yalan in environmental samples (411),and N-phenylcarbamate residues in carrots, potatoes, and wine at 0.1 ppm (151, 161) were determined by TLC. Specific Procedures. Analytical methods for carbaryl were reviewed (291). Carbaryl was determined by GC in blood and tissues at 0.02 and 0.1 ppm, respectively, after derivatization with heptafluorobutyric anhydride (281)and on stored wheat by on-column transmethylation (RbS04AFID) (50~0. HPLC determination was applied to carbaryl residues in water (trace enrichment, 0.1 ppb sensitivity) (71) and food (40I). Carbaryl residues on fruit tree foliage (81) and in grains (0.3 ppm) (31)were determined by colorimetry after derivatization. A variety of chromatographic and spectrophotometricmethods for determination of carbaryl residues in cabbage were compared, and the latter were judged superior (41). Gas chromatography was applied to carbofuran residue determinations as follows: in plant materials with derivatiand an N-P detector zation by l-fluoro-2,4-dinitrobenzene (471);in potato, onion, and turnip as the HFB derivative with SIM-MS detection (391);in water (10 pg/L) using GC/MS (321);and carbofuran and atrazine in soil using a thermionic specific detector without cleanup of extracts (141). HPLC with a CIS column was used to separate carbofuran and five metabolites (421) and for analysis of carbofuran and 3hydroxycarbofuran residues in rape plants (0.2 ppm) (231)and drinking water (1ppb) (111). Carbofuran and metabolites in air (351)and biological samples (341) were determined by silica gel TLC. Carbofuran and quinalphos were determined in air by TLC (491). Loss of carbofuran and metabolites was shown to occur upon refluxing in acid solution for conjugate hydrolysis (381). Aldicarb and its sulfoxide and sulfone metabolites in potatoes (0.1 ppb) were determined by CIBHPLCafter Sep-PAK cleanup (91). These compounds were determined in water (1 ppb) by HPLC after recovery on an XAD-2 resin (314, and their isobutane CI mass spectra were studied (301). Aminocarb (Matacil) was determined in foliage, fish, soil, and H20 (1-10 ppb) by EC-GC of the l-fluoro-2,4-dinitrobenzenederivative (431),and the degradation of aminocarb and seven derivatives upon direct GC was studied (241). Aminocarb was determined in water by HPLC after collection on XAD-4 resin (60, and it was separated from its metabolites and detected by silica gel TLC (451). Methiocarb (Mesurol) and its sulfoxide and sulfone metabolites were determined in plant, animal, and soil samples (20 ppb) after hydrolysis and silylation (441) and in vegetables and fruits (50 ppb) after derivatization with methanesulfonyl chloride (261),in both cases using the sulfur mode FPD detector. Chlorpropham was determined in onions (50 ppb) by TLC (371)and in fruits and vegetables (0.12 ppm) by HPLC (520. Mecarbam and degradation products were determined in water and crops by GC and TLC (250, carbendazim residues in cereals (50 ppb) by CIBHPLC (210, formetanate in fresh fruit (20-50 ppb) by CISHPLC (221), propamocarb in peppers by silica gel TLC (139,and propoxw (Baygon) in plant tissue by direct alkali flame ionization GC with an Ultrabond column (481).
HERBICIDES See also the previous section for some references on carbamate herbicides. General Procedures. Solvent systems for the extraction of atrazine, benzoylprop, flamprop, and trifluralin from soil were compared (684. s-Triazine herbicides were separated on short GC columns with surface bonded supports ( 4 5 4 and on capillary GC columns (164, and the latter were used for determination of triazines in crops (10-20 ppb) ( 6 0 . HPLC ANALYTICAL CHEMISTRY, VOL. 55, NO.
5. APRIL 1983 61 R
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with UV detection (3J,4 4 and HPLC/MS (554 were used for separation and determination of triazines and ureas. RF values for 19 triazines on silica gel layers impregnated with 20% diethylene glycol were tabulated (534. GC methods were reported for determination of triazine residues in drugs (FID) (204 and industrial and municipal wastewater (N-P electrolytic conductivity detector) (584. N-Dealkylated metabolites of triazines were separated by Carbowax 20M capillary column GC (474 and determined in urine by GC on a support-bonded GC column (54. Eleven phenylurea herbicides were separated on an activated C-silica gel column (295). Phenylureas were analyzed by GC following catalytic hydrolysis on silica gel (144 and were separated on different kinds of capillary GC columns including fused silica (274. Phenylureas and corresponding anilines were determined by combined HPLC and capillary GC (154. Surface water was analyzed for phenylurea and carbamate pesticides a t 2-25 ppt levels by combined HPLC field desorption MS (714. Phenylureas were separated y partition TLC on impregnated layers (524 and phenoxyacetic acid herbicides on silica gel and alumina (634. Triazines,phenylureas, phenylcarbamates,uracils, and anilides were detected on thin layers by spraying with a mixture of spinach chloroplasts and the redox indicator 2,6-dichloroindophenol (394. Procedures were reported for the determination of chlorinated (565) and organonitrogen (574 herbicides in industrial and municipal wastewater by GC; nitrophenol herbicides in crops by reversed-phase ion-pair HPLC (614; rice-field herbicides by C8 HPLC ( 7 4 ; acid and hydroxybenzonitrile herbicide residues in soil by GC after ion-pair alkylation (114; acidic herbicides in human urine by EC-GC/MS after derivatization with diazomethane (17 4 ; 2,4-D related residues in irrigation water (30 ppb) by differential pulse polarography (444; 11phenoxyalkonic acids and esters in plant material by GC after GPC and silica gel minicolumn cleanup (694; acidic herbicides in tissues, soil, and water by GC using alkali metal silicates for chromatographic enrichment from organic solvents (704; and chloroanaline herbicide metabolites by HPLC with voltammetric detection (294. Results of a Canadian interlaboratory QC study on determination of eight acidic herbicides in natural freshwater were published (14. Specific Procedures. A quality assurance program was developed for determination of atrazine and linuron in estuarine water (224. Atrazine and degradation products were determined in soil (5 ppm) by C8 HPLC (744 and atrazine and simazine in water (10 ppb) by silica gel TLC with densitometry (644. Cyanuric acid, a degradation product of triazine herbicides, was determined by HPLC in a growth medium (325). Analyses of 2,4,5-T and associated herbicides were reviewed (794. The following determinations of phenoxyacetic acid herbicides were reported free and hydrolyzable residues of 2,4-D and 2,4-dichlorophenol in potatoes by GC (64; 2,4-D and bromoxynil in wheat (1-5 ppb) by EC-GC of methyl derivatives (84; 2,4-D and dichlobenil in water (0.1-50 ppm) by RP-HPLC (94; the propylene glycol butyl ether esters of 2,4-D in air by EC-GC (validated method) (255); 2,4-D butoxyethanol ether ester and degradation products in lake sediment (344; 2,4,5-T and metabolites in blood, feces, and urine (20-30 ppb) by HPLC and negative ion atmospheric pressure ionization MS (484; and 2,4-D and silvex in water (1-10 ppb) by HPLC (734. Studies were made of the adsorption of 2,4-D on glassware as a source of analytical error (334 and the efficiency of various solutions of pentafluorobenzyl bromide for derivatization of MCPA and metabolites for GC analysis of soil (624. The following analyses of miscellaneous herbicide residues were reported methazole and 2 metabolites in soil by HPLC (124; triallate and diallate in milk and plant tissue by steam distillation and GC ( 1 0 4 ;diuron in soil (comparison of GC and HPLC) (13V); pyrazon (Pyramin) in water (2 ppb-1 ppm) by HPLC (W,514 and in sugar beets (2 ppb) by N-P selective GC (374; norflurazon and the desmethyl metabolite in plant tissue (0.1 ppm) by HPLC (184 and in crops (0.01 ppm) by GC (785); asulam and degradation products in soil by TLC and colorimetry (194, in wheat by C8 HPLC (424, and in water and spinach (2-200ppb) by HPTLC with densitometry (654; amitrole in grain or meal (50 ppb) by colorimetry of coupled derivative (214 and in vegetables by ion-pair HPLC
l
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(464; bentazon in soil by GC of alkylated derivatives (234; oxadiazon and metabolites in hops by GC (244; betazon in soil and plants (30-50 ppb) by GC (354;benazolin in soil and plants by GC (364; chlorpropham, metobromuron, and chlorbromuron in drugs by GC or TLC (725); nitrofen and CNP in soil by single ion monitoring MS (384; bromoxynil octanoate and benzoylprop-ethyl in wheat products by GC and HPLC (comparison of methods) (405); barban in wheat (2 ppb) by C8 HPLC (414; difenzoquat in wheat products (0.1-10 ppm) by C8 HPLC (434; terbutryn and degradation products in water, sediments, aquatic plants, and fish by HPLC (494; methoxyphenone in crops (5 ppb) by HPLC (504; alloxydim-sodium and degradation products in crops and soil (10 ppb) by HPLC (544; glyphosate and its major metabolite in straw by HPLC after fluorescence labeling (594 and in blueberries b EC-GC (265); lenacil and pyrazon in water, soil, and sugar geets by silica gel TLC (664; bromoxynil and its octanoate in soil (1-5 ppb) by GC (674; fluridone in cottonseed (754 and water (774 by C18HPLC and in fish (10 ppb) by EC-GC (764;hexazinone and metabolite in plants, animal tissues, and soil (40-200 ppb) by N-selective GC (314; and 2,6- dichlorobenzonitrile in soil and water by direct GC (305).
FUNGICIDES GC was used to determine residues of captafol, dichlofluanide, folpet, iprodione, quintozene, vinclozolin, dithiocarbamates, and MBC (carbendazim) in lettuce (2-100 ppb) (39K). Bupirimate, fenarimol, and vinclozolin in grape juice and wine were determined by capillary GC (33K). Bitertanol, fluotrimazol, fuberidazole, imazalil, rebenzazole, triadimefon, and triadimenol were determined in plants and soil by GC after GPC and silica gel minicolumn cleanup (31K). Vinclozolin, iprodione, and procymidone were determined in grapes, grape must, and wine (10 ppb) by EC-GC (19K). The extraction efficiency of [ 14C]-benomylfrom mustard greens and radishes was studied (40K). A GC method with flash-heater methylation of benzimidazole fungicides using trimethylanilinium hydroxide was established (24K, 25K). Residues of MBC were determined as follows: in black walnuts by GC after pentafluorobenzylbromide derivatization (11K);with benomyl on apple foliage (200 ppb) by HPLC with benomyl on food crops by rawithout cleanup (IOK); dioimmunoassay (22K); with benomyl in industrial and municipal wastewater by HPLC (27K);from thiophanate methyl in onions and cabbage (80 ppb) by HPLC after ion exchange cleanup (4K); and with thiophanate methyl in fruits and vegetables by HPLC after C18Sep-PAK cleanup (38K). Dithiocarbamate fungicides were separated by C1 HPLC using transition metal salts as ion pair reagents ( 3 0 4 . They were determined in industrial and municipal wastewaters by evolution of CS2 and colorimetry (28K); in foods by a headspace method in which evolved CS2is measured by FPD (S)-GC (12K) or colorimetry (26K);and in water (10 ppb) and fruit (1ppm) by HPLC (15K). Dithiocarbamate salts were studied by ELMS (14K). Triphenyltin hydroxide derivatives were determined in water by capillary GC with a Sn-selective FPD (41K), butyltin species in water by FPD-GC and MS (2OK), trialkyltin homologues in biological materials by EC-GC (3K), and tri- and diorganotin compounds by spectrophotometry and fluorometry using dithizone and 3-hydroxyflavone (2K). An improved steam distillation procedure was applied to the visible spectrophotometric determination of 2-phenylphenol in citrus fruits (0.3 ppm) (37K). Thiabendazole was determined by UV or fluorescence spectrometry in strongly adsorbing soils (9K), in banana and citrus fruits (0.1 ppm) by direct C8 HPLC (16K), and in fruits by HPLC of the p nitrobenzyl derivative (35K). Metalaxyl (Ridomil) was determined in soils and sunflower (0.05-5 ppm) by N-selective GC after sweep codistillation (36K), in tobacco (0.1 ppm) by GC (32K), and in maize by TLC (29K). Captafol was determined in wheat (0.1 ppm) by GC after GPC cleanup (5K), and captan, captafol, and folpet residues in plants (20-50 ppm) by HPLC with a cyano bonded column (7K). Analytical methods for residues and formulations of fungicides for grey mold control were reviewed (13K). Gas chromatography was used to determine imazalil residues in grapefruit with EC detection (34K); furalaxyl and metalaxyl in nutrient solution, peat compost, and soil with an N-selective
PESTICIDES
detector (8K);vinclozolin in soil (0.01-10 ppm) with EC detection (6K);triforine in fruits (50 ppb) as N,N'-bis(pentafluorobenzoy1)piperazine with EC detection (21K); and triadimefon in grape juice and wine with a capillary column and FID (23K). Methomyl and methomyl oxime were determined in fruit and water by HPLC using UV and electrochemical detectors in series ( I K ) . Dithianon was determined in crops (0.2 ppm) by HPLC with postcolumn colorimetric detection (17K). N-selective and EC-GC and C8 HPLC were compared for determination of anilazine in potatoes and tomatoes (18K).
CHLORINATED COMPOUNDS RELATED TO PlESTICIDES (PCB, PCT, PBB, TCDI), IDIBENZOFURANS, AROMATICS) Reviews have been published of methods for analysis of polychlorinated biphenyls (PCBs) in transformer oil (2%); 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) at p t levels in biological and environmental samples (18L); and $oxins and polychlorodibenzofurans in phenoxyalkanoic acid herbicides (4L). A general approach to fractionation and class determination of mixtures of PCBs, polychlorinated terphenyls (PCTs), quadphenyls, naphthalenes, diphenyl ethers, dibenzofurans, dibenzo-p-dioxins, benzenes, and chlorinated pesticides was devised by using GC/MS, prefractionation on basic and acidic alumina columns, and perchlorination techniques (31,). Negative ion chemical ionization MS was applied to analyses of polychloronaphthalenes, styrenes, biphenyls, dibenzofurans, and dibenzodioxins (9L, 16L). Preparation and testing of PCB standard reference materials were described for determinations in sediments (2L, 12L). Aroclors were standardized for use in individual peak Calibration procedures (39L). Separation of PCBs from OC1 pesticides on a silica gel column was optimized, using azulene as a visual indicator (20L, 3%). Silver nitrate impregnated silica gel columns separated PCBs from DDT and metabolites in bovine serum (33L). PCBs were separated from toxaphene on a 2% water deactivated column of silicic acid eluted with hexane fodlowed by methylene chloride (40L). Analyses of transformer oils for PCBs were reported using EC-GC ( I L ) , capillary !302column EC-GC (19L), and automated EC-GC (29L). Individual PCBs were determined in milk fat (25 ppb) by splitless capillary GC (42L). PCBs were determined in plant tissue without need for GPC cleanup by inclusion of H2S04-silicagel adsorbent in the extraction column (3%). A portable GC MS system was used to screen soil for PCBs in the field (41 ). PCBs in sediments (0.5 ppb) were analyzed by capillary GC (26L). A packed column GC method for PCBs in complex matrices involved digestion with H2S04 and KMn04 and removal of products on a Florisil microcolumn (I3L). Preparation of an Apiezon-L capillary column and its use to characterize 72 peaks of a PCB mixture for use as a universal calibration standard were described (7L). Chemical ionization GC/MS of PCBs was studied, and it was found that a single molecular weight standard could be used to quantitate all of the standards of a single molecular weight group (8L). Limitations of perchlorination quantitation of PCBs were reported (14L). Mono- and dihydroxybiphenyls were gas chromatographed on various silicone phases (17L),and EC detector rt?sponsewas correlated with PCB structures (24L). Total PCEls were estimated in rat liver and cottonseed oil by radioisotope dilution assay (27L). PCBs and polybrominated biphenyls (PBBs) were quantitated in human serum by temperature-programmed EC-GC after adsorption chromatographic cleanup (32L). PBBs were separated by GC and monitored by a microwave-induced plasma emission detector (30L). Limitations to current analytical techniques for dibenzop-dioxins in environmental samples were reviewed (31L). An interlaboratory study was carried out on the low resolution multiple ion detection GC/MS determination of TCDD in fish using six different extraction-cleanup methods (5L). The separation of 22 synthesized TCDDs on different capillary columns was studied (6L). A high-resolution GC/low-resolution MS method analyzed vegetables for ppt levels of TCDD (IOL). The MS80/DS55 MS system and a new high-resolution selected ion monitoring scheme were applied to determination of trace levels of TCDD (1IL). Details of the GC/MS techniques use'd to assay TCDD at ppt levels following its accidental release at Seveso, Italy, were presented (15L). High-
i,
resolution GC/high-resolution MS procedures for quantitating TCDD residues in combustion processes and biological and human tissues were described, including validation of methodology, QA programs, and confirmation criteria (21L). GC/MS was used to detect traces of TCDD in air filter samples (23L), in goat milk and tissue (36L), in chemical wastes, aqueous effluents, and soils (43L), and in industrial and municipal wastewaters (44L). TCDD isomers were identified a t the 1-ne:level bv Dhotolvtic degradation and Dattern recognition t&hniqu&i(34L)." HPLC/MS was used to determine chlorinated dibenzodioxins and dibenzofurans in chicken liver and wood shaving samples at 25 ppt levels (37L). Three tetrachlorodibenzofwr& isomers were separated via fused silica capillary GC combined with API-MS (28L). Nine metabolites of di(2-ethylhexyl) phthalate (nonchlorinatedacaracide) were studied by MS with four ionization modes (22L). I
MISCELLANEOUS PESTICIDES Analytical methods for pesticides that were not easily classified in, or were omitted from, the sections above are reviewed in this part. The following determinations of residues were reported: ,the insect growth regulator EL-494 in alfalfa at 25 ppb by ICl8 HPLC after Florisil column cleanup (1M); some insecticides and fungicides in different grapes by C HPLC (9M); diclofop and diclofop-methyl in soil at 1ppm t y GC after treatment with pentafluorobenzyl bromide (18M);Fenazox on cucumbers and apples by GC and TLC (19M); oxamyl in peppers, tomatoes, and cucumbers (0.02-1 ppm) by thermionic (N-P) GC after ethyl acetate extraction and alumina column cleanup (21M); MCIA, a naturally occurring auxin, in canned and frozen peas by MS and microcoulometric GC (25M); the fungicide sec-butylamine in potatoes (0.1ppm) by RP HPlLC of its fluorescamine derivative (27M); ETU in smoke from tobacco containing dithiocarbamate pesticides by AFID-GC (29M); the nitrification inhibitor nitrapyrin in strawberry fruit and soil (31M); Plictran in plants and soil by silica gel-Al,O, (1:l)TLC (34M); Pyridate and metabolites in corn and rape crops (10ppb) by EC-GC and MS after reaction with pentafluorobenzoyl chloride (39M); piperonyl butoxide in cereal products (2 ppm) by FID-GC (49M); the acaracide benzomate in oranges and apples (40 ppb) by C8 HPLC (5"); sodium fluoroacetate (compound 1080)in canine gastric content (1-50 ppb) by HPLC (65M); binapacryl and dinobuton in applles and cucumbers (0.3-1ppm) by HPLC after neutral alumina column cleanup (72M); and Eulan WA New mothproofing agent in fish (5 ppb) by EC-GC after extractive methylation (91M). Styrene-divinylbenzene copolymer and chemically bonded CISsilica gel were compared for HPLC of gibberellins A3 and A7 (23M). The medfly attractant trimedlure was analyzed by GC on a Carbowax 20M capillary column (42hf). GPC was evaluated for cleanup of human adipose tissue samples for GC/MS analysis of OC1 pesticides, PCBs, and related compounds (43M). Chlormequat chloride was determined in environment a1 samples by silica gel TLC (89M) and in foods by TLC with densitometric quantitation (83M). Airborne residues of paraquat in treated cotton field environments were collected and determined by N-selective GC (78M). Residual diquat in sunflower seeds (20 ppb) was determined by silica gel TL,C (33M). Pentachlorophenol, a defoliant, wood preservative, and molluscicide, was determined in body fluids (1-2 ppb) by EC-GC after acetylation (56M);in fruits and vegetables by GC with an electrochemical detector (95M); in animal materials (0.1-10ppm) by HPLC with a silica gel column (53M); and in mason jar lids and home canned foods by EC-GC after methylation (26M). Steam distillation was used to differentiate inorganic Hg and alkylmercury determined by flameless AAS in river sediment (54M). An interlaboratory study was conducted on a simplified GC method (84M) for bromide residues in carrot flake and corn grits (4M). A series of benzenearsonic acids were determined by voltammetry at 104-10-6 M levels (3M'). As(III), As(V), monolmethylarsonate, and dimethylarsinaite were determined in lake water by ion exchange chromatography with flameless AAS detection (20M). Extraction and cleanup procedures for soil aresenical residues prior to HPLC-graphite furnace AAS were described (28M). The ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
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suitability of filtering media for collection of organoarsenicals in air were compared (70M). Extraction and separation of arsenic and aresnicals prior to flameless AAS analysis of runoff water were studied (9OM). A multiresidue method for synthetic pyrethroids in fruit and vegetables included extraction with hexane-acetone, cleanup by partition and silica gel column chromatography, and EC-GC or HPLC(UV) (5M). A procedure based on current AOAC multiresidue methods determined permethrin, cypermethrin, and fenvalerate in celery and animal products (8M). TLC and GC separated synthetic pyrethroid stereoisomers (57M). 13C NMR spectra were measured for 19 synthetic pyrethroids and related compounds (55M). A residue method involving acetone extraction, partitioning, Florisil chromatography, and EC-GC was used to determined six naturally occurring pyrethrins in fruits (10-30 ppb) (74M). EC-GC was used to determine pyrethrin residues in flour (1 ppm) (76M). A comparative study was made of analytical methods for bioresmethrin, fenothion, d-fenothrin, pyrethrum I, carbaryl, fenitrothion, methacrifos, primiphos-methyl, and dichlorvos in grain (14M). The synthetic pyrethroid fenvalerate was determined in grapes, peppers, apples, and cottonseed (22M);in grasshoppers and duck tissue by GC/MS (67M);in apple products by GC (82M);and with cypermethrin in wheat by GC (32M), Pyrethroid insecticides were determined in crops by TLC with dual wavelength densitometry (88M). Bioresmethrin and piperonyl butoxide were simultaneously estimated by GC/CI-MS (12M). Traces of biopermethrin and decamethrin in biological substrates were determined by GC after extraction and Florisil cleanup (60M). Permethrin was determined in environmental waters (0.05 ppb) by GC/SIM-MS using ion counting detection @OM). HPLC determinations of the following rodenticides were reported: multiresidues of coumarin-based compounds in animal materials (50-100 ppb) on porous silica (52M);brodifacoum in animal tissue (50 ppb) (35M);Castrix in animal tissues, cereal grains, soil, and water by RP-HPLC after silica gel Sep-PAK cleanup (50M);warfarin and metabolites with fluorescence detection by postcolumn acid/ base manipulation (40M);warfarin enantiomers in biological fluids (6M); and warfarin in plasma after extraction and solvent partitioning (71M). The following analytical methods for fumigants have been reported, most involving recovery of compounds from samples by distillation or solvent extraction: multiresidues of carbon disulfide, methyl bromide, carbon tetrachloride, ethylene dichloride, ethylene dibromide, and ethylene chlorohydrin in cereal products at 0.5-500 ppb by EC-GC with extraction by ; in potatotes (0.2 ppb) sweep distillation (48M)2-aminobutane by dansylation and RP-HPLC with fluorescence detection (77M);and ethylene dibromide in grapefruit (0.38 ppb) by EC-GC (38M), in ambient air with collection on Chromosorb 101 or a charcoal filter (45M),and in citrus fruit at 1-10 ppb (51M) and in biscuits and commercial flour at 0.5-8.0 ppb by EC-GC (64M). Residual methyl bromide was determined in fumigated commodities (10 ppb) after conversion into methyl iodide (17M) and in grapefruit (2 ppb) by a rapid, headspace assay (37M),both with EC-GC. 1,2-Dibromo-3-chloropropane was determined in ambient air by trapping on Chromosorb 101 and EC-GC (44M). Ethylene chlorohydrin was determined in foodstuffs by solvent extraction and capillary GC (94M). A method for measuring ambient levels of ethylene dichloride was developed and field tested (16M). The accuracy of different sampling pumps and detector tube combinations for determination of phosphine concentrations was evaluated (41M),and a portable gas chromatograph for field determinations of fumigants was described (7M). A radioimmunoassay for indole-3-acetic acid (IAA) agreed within 2% with results obtained by GC/SIM-MS (61M). A concentrator column of Amberlite XAD-7 was used for cleanup of IAA, ABA, gibberellic acid, zeatin, and N43-indoleacety1)aspartic acid with ethanol as solvent (2M). Bisazir, a mosquito chemosterilant, was determined in air by collection on porous polymer and FPD-GC (10M). Improved separations of olefinic aliphatic insect pheremones were obtained on cholesteryl cinnamate liquid crystal capillary columns (24M). Positional and geometric isomers of mono-, di-, and polyunsaturated insect pheremones were separated using RP-HPLC with a polar mobile phase containing silver nitrate (62M). Capillary GC was applied to analysis of the chemical com64R
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5, APRIL 1983
munications systems of Lepidoptera (86M). Juvenile hormones were determined by a HPLC system coupled to a mass spectrometer (10 pg sensitivity) (47M). CI8 HPLC with methanol-water (3:l) mobile phase separated precocenes-I, -11, antijuvenile hormones, and their derivatives (79M). N-Nitroso contaminants in pesticide products were surveyed with a thermal energy analyzer coupled with GC or HPLC (96M). A GC system consisting of a 15% PEG 20M, 10% KOH column and RbSOl thermionic detector was used to determine nitrosamines (92M). The AFID, TEA, and Hall conductivity detectors were compared for determination of nitrosamines in industrial and municipal wastewaters (68M, 69M). NDMA and NPYR were confirmed in bacon, beer, and malt by GC/low-resolution quadrupole MS (36M). Determination of volatile nitrosamines in cheese and pesticides was collaboratively studied; methods using adsorption of the sample on a column and GC/TEA were most suitable ( 1 I M ) . A GC method for determination of dinitroaniline pesticides in municipal and industrial wastewater was based on solvent extraction, concentration, and EC-GC (63M). The Bleidner technique was evaluated for analysis of soil-bound 3,4-dichloroaniline residues (93M). The following analyses of phenols and substituted phenols were devised: 11 phenols from water using acid-washed graphitized carbon black (15M); priority pollutant phenols in water by a two-step extraction procedure with methylene chloride and ion pair RP-HPLC (66M);nitrophenols in water (1ppb) by ion pair RP-HPLC (73M); chlorophenoxyphenols in soil and water by solvent extraction and field desorption MS (59M);eight chlorophenol standards were separated by HPLC (30M);chloro- and nitrophenols by FID-GC with direct acetylation in aqueous solution (46M);chlorinated phenols in poultry liver and meat contaminated with HCH and HCB by GC, GC/MS, and TLC, directly or after derivatization with methyl iodide (75M);PCP and 11 other polychlorinated phenols by microprocessorcontrolled HPLC (81M);PCP and 2,3,4,6-tetrachlorophenol in edible gelatins by alkaline hydrolysis, extraction, and direct EC-GC (85M); mono-, di-, tri-, and tetrachlorinated phenols were separated by HPLC on silica, aminoalkyl, and octadecyl columns (87M); and nitrophenols and 1-naphthol in environmental water (1 ppb) by GC with direct aqueous acetylation (13M). LITERATURE CITED GENERAL
(IA) ASTM "Book of ASTM Standards Pt.46:End Use Products"; American Society for Testing and Materials: Philadelphia, PA 1982; 1434 pp. (2A) Bradway, D. E.; Lores, E. M.; Edgerton, T. R. Residue Rev. 1980, 75, 51-65. (3A) Bruner, F. J. Chromatogr. Libr. 1981, 20, 241-254. (4A) Cochrane, W. P. Chem. Deriv. Anal. Chem. 1981, 1, 1-97. (5A) Cochrane, W. P.; Maybury, R. B. J. Chromatogr. Libr. 1981, 2 0 , 205-240. (6A) Das, K. G., Ed. "Pesticide Analysis"; Marcel Dekker; New York, 1981; 467 pp. (7A) Dougherty, R. C. Biomed. Mass Specfrom. 1981, 8 , 283-292. (8A) FDA "Pesticide Analytical Manual"; U.S. Food and Drug Administration: Washington, DC, 1982; Voi. I . , 591 pp. (9A) Fishbein, L. ACS Symp. Ser. 1981, No. 160 (CH 22), 349-385. (10A) Gorbach, S. Pure Appl Chem. 1980, 52, 2569-2590. (11A) Gustafsson, K. Haakan , Lebensm, Untersuch Forsch. 1982, 174, 294-295. (12A) Gunther. F. A. Residue Rev. 1980, 75, 113-128. (13A) Gunther, F. A. Residue Rev. 1980, 76, 155-171. (14A) Harrison, A. G. Environ. Sei. Res. 1980, 16, 265-283. (15A) Hodgson, D. W.; Watts, R. R. J. Assoc. Off. Anal. Chem. 1982, 65, 89-93. (16A) Horwitz, W.ACS Symp. Ser. 1981, No. 160(CH24), 411-438. (17A) Hyiin, J. W. Resldue Rev. 1980, 76, 203-210. (18A) Huggett, R. J. Biomed. Mass Spectrom. 1981, 8 , 416-418. (19A) IUPAC Pure Appl. Chem. 1981, 53, 1039-1049. (20A) IUPAC Pure Appl. Chem. 1981, 53, 1967-2022. (21A) Malaiyandi, M.; Benoit, F. M. J. Environ. Sci. Health A 1981, 16, 2 15-250. I (22A) Muir, Derek C. G, Ed. "Proceedings of the 16th Annual Workshop for Pesticide Residue Analysts and the 9th Annual Workshop on the Chemistry and Biochemistry of Herbicides"; Dept. Nati. Health Welf., Health Prot. Br.: Winnipeg, 1981; 197 pp. (23A) Preston, S. T., Jr.; Pankratz, R. "A Guide to the Analysis of Pesticides by Gas Chromatography. 3rd Ed.;" Preston: Niles, IL, 1981; 436 pp. (24A) Schmitt, C. J. ASTM Spec. Tech. Publ. 1981, 737, 270-298. (25A) Sherma, Joseph "Manual of Analytical Quality Control for Pesticides and Related Compounds in Human and Environmental Samples", 1981; EPA-600/2-81-059, NTIS t PB81-222721, 468 PP. (26A) Spencer, E. Y. "Guide to the Chemicals Used in Crop Protection, 7th ed.;" Research Branch, Agriculture Canada; avail. from Canadian Govern-
.
PESTICIlDES ment Publlshing Centre: Ottawa, 1982. (27A) TayLDr, J. H.; Jackson, C.; Mlller, M.; Rushneck, D. R. J . Environ. Scl. Health A 1980, 15, 393-411. (28A) Worthing, C. R., "The Pesticide Manual. A World Compendium. 6th ed;" British Crop Council: Croydon, 1980 655 pp. SAMPLING AND CLEANUP ( l a ) Adams, J. D.; Caro, J. H. U.S. NTIS PB Rep.PB-80-159, 502, 1980, 83 PP. (28) Ambrus, A.; Lantos, J.; Visi, E.; Csatlos. I.; Sarvarl, L. J. Assoc. Off. Anal. Chem. 1981, 64, 733-742. 138) Anderson, C. C.; Gunderson. E. C.; Coulson. D. M. ACS SvmD. . . Ser. . 1981,No. 149, 3-19. (48) Andraws, J. 8.; Good, T. J. Am. Lab (Falrfleld, Conn.) 1982, 14, 70, 73-75. (58) Apperson, C. S.; Leidy, R. 8.; Eplee, R.; Carter, E. Bull. Envlron. Contam. Toxlcol. 1980,2 5 , 55-58. (8B) Eicernian, G. A.; Karasek, F. W. J . Chromatogr. 1980,200, 115-124. (78) Gearhart, H. I-.; Cook, R. L.; Whltney, R. W. Anal. Chem. 1980, 52, 2223-2225. (8B) Grovor, R.; Kerr, L. A. J . Envlron. Sci. Health 6 1981, 76, 59-66. (9B) Gunderson, E. C. ACS Symp. Ser. 1981,No. 149, 301-315. (IOB) Gunderson, E. C.; Fernandez. E. L. ACS Symp. Ser. 1981,No. 149, 179-19:). ( I l B ) Hopper, M. L. J . Assoc. Off. Anal. Chem. 1981,6 4 , 720-723. (128) Hopper, M. 1.. J. Agric. FoodChem. 1982,30, 1038-1041. (138) Jackson, M. D.; Lewls, R. 0. ASTM Spec. Tech. Pub/. 1980, 727, 36-47. (148) Lafleur. A. L,; Pangaro, N. Anal.Left. 1981, 14, 1613-1624. (158) Lewis, R. G.; Jackson, M. D. Anal. Chem. 1982,54. 592-594. (16B) Macl-eod, K. E.; Lewis, R. G. Anal. Chem. 1982,5 4 , 310-315. (178) Ongley, E. D.; Blachford, D. P. Envlron. Technol. Left. 1982, 3. 219-228. (18B) Puchwein, G Anal. Chem. 1981,5 3 , 544-546. GAS CHROMATOGRAPHY (1C) Ambrus, A.; Visi, W.; Zakar, F.; Hasrgltal, E.; Szabo, L.; Papa, A. J.Assoc. Oft. Anal. Chem. 1981, 6 4 , 749-768. (2C) Boshoff, P. R.; Smuts, T. W. J . Chromatogr. Scl. 1980, 18, 315-323. (3C) Boshoff, P. R. J. Chromatogr. Scl. 1981, 19, 238-244. (4C) Broetull, H.; Ahnfeit, N. 0.; Ehrsson, H.; Eksborg, S. J . Chromatogr. 1979, 176, 19-24. (5C) Cardwell, T. J.; Marriott, P. J. J. Chromatogr. Sci. 1982,2 0 , 83-90. (6C) Ehrllch, B. J.; Hall, R. C.; Anderson, R. J.; Cox, H. G. J. Chromatogr. Scl. 1981, 19, 245-249. (7C) Farwell, S . 0.; Gage, D. R.; Kagel, R. A. J . Chromatogr. Scl. 1981, 79, 358-376. (8C) Fuchsbichler, 6.; BIOS,G. Landwltfsch. Forsch. Sonderh. 198 1 1982, 3 8 , 774-80. Chem. Abstr. 1982,9 7 , 176785b. (9C) Golovkin, G. V.; Smoi'chenko, A. I.Zh. Anal. Khim. 1981, 36. 2013-2019. Chem. Abstr. 1982,96. 29799k. (1OC) Roseboom, H.; Groenemeijer, G. S. Meded Fac. Landbouwwet., Rljksunlv. Gent 1981, 46, 325-330. Chem. Abstr. 1981, 95, 218938~. (11C) Gross, D.; Gutekunst, H.; Blaser. A.; Hamboeck, H. J . Chromatogr. 1980, 198, 389-386. (12C) Guilbault. G. G. Int. J. Environ. Anal. Chem. 1981, 10, 89-98. (13C) Hanre, T.; Coulombe, S.; Moisan, M.; Hubert,J. "Dev. At. Plasma Spectrochem. Anal. Proc. Int. Winter Conf. 1980"; Barnes, R. M., Ed.; Heyden: London, 1981; pp 337-344. (14C) Hermann, B. W.; Seiber, J. N. Chromatogr. Scl. 1981, 15, 175-202. (15C) Lopez-Avila, V. HRC CC,J. High Resol. Chromatogr. Chromatogr. Commun. 1980,3 , 545-550. (16'2) Luke, M. A.; Froberg, J. E.; Doose, G. M.; Masumoto, H. T. ,I. Assoc. Off. Anal. Chem. 1981,64, 1187-1195. (17C) Neukermans, A.; Kruger, W.; McManlgill, D. J . Chromatogr. 1982, 235, 1-20. (18'2) Poolel, C. F.; Zlatkis, A. J. Chromatogr. Llbr. 1981,2 0 , 13-28. (19C) Seeftsld, F.; Tunkei, W. Chem. Tech. (Leiprig) 1981,33, 470-473. Chem. Abstr. 1981,9 5 , 198845g. (20C) Shafer, K. H.; Cooke, M.; DeRoos, F.; Jakobsen, R. J.; Rosario, 0. Mulik, J. i3. Appl. Spectrosc. 1981,3 5 , 469-472. (21C) Simonaitis, R. A.; Zehner, J. M. Anal. Chem. 1982,54, 1244-1245. (22C) slu, I
