Pesticide Residues Wayne Thornburg Del Monte Corporation Research Center, Walnut Creek, Calif. 94598
Publication in the field of pesticide methodology has continued a t a high level during the two-year review period from November 1970 through November 1972. In the preparation of this review, emphasis has been placed on publications readily available and on procedures which, in the opinion of the author, will be most useful to the residue analyst. This review follows the general format and pesticide nomenclature used in the 1971 biennial review of Thornburg (359). Frear’s “Pesticide Index” (127) lists the common, trade, and chemical names of many pesticides, and the author has tried to use names’ found therein. Common names which appear in the Environmental Protection Agency tolerance regulations have been used where possible. Another useful publication edited by Shepard (329) is the “Dictionary of Pesticides 71” which is a compilation of the pesticides available commercially in the United States and throughout the world. Trade names, common names, and chemical names are cross referenced wherever possible. Names of basic producers are also listed for each pesticide. Persistent chlorinated pesticides, and especially polychlorinated biphenyls which are widely distributed in the environment, have come under close scrutiny during this period. Most pesticides are now analyzed for the parent compound and its major metabolites, and many excellent metabolism studies have been reviewed. “Residue Reviews” under the editorship of Gunther (157) continues to be a n excellent source of information on pesticide methodology. A total of 43 volumes has now been published. Ebing (116‘) compiled a comprehensive reference book to the GLC pesticide literature of the world in “Gas Chromatography of’ Plant Protection Agents-Volume I.” This work is published in German, but has a partial English translation which is sufficient for English-speaking scientists. It summarizes references to 900 articles published throughout the world between 1959 and 1970. The references are numbered and organized in numeric order. Each reference includes pesticides analyzed, detector and carrier gas specifications, remarks, and the literature reference. Benson and Blalock (31) prepared a bibliography of “The Literature of‘ Pesticide Chemistry, Part 11.” This paper has been updated, added to and expanded on the paper published previously by Benson and Jones (32) in 1967. The references in the first paper are not duplicated in this paper. This excellent presentation should be of considerable help to workers in the field of residue chemistry. Bourke and coworkers (51) described a pesticide residue data information retrieval system using up to 16 search keys. The computer program was designed to run on a small computer using disk storage for all data. This review period has been characterized by both improvements in existing techniques and the development of new instrumentation. Thin-layer chromatography is now a standard technique and a n automatic instrument (J.T.
Baker’s Chromatape) has been developed, and research is being done on its application. A revival of interest in liquid chrom,itography has been spearheaded by improvements in column packing, use of high pressure, and new detection procedures. However, liquid chromatography has not yet found extensive use in pesticide analysis, and its widespread acceptance will probably await the development of riore specific detectors. A number of new pesticides have bcen introduced such as thiabenzadole fungicides which cannot be analyzed by gas chromatography, and theri is rencwed interest in colorimetric and fluorometric techniqu2s. Highly purified solvents and improved cleanup technl ques are now available making these procedures more attractive. Reliable automatic injection devices for gas chromatographs are now being produced. Howzver, completely automatic extraction, extract purification, and quantitation instrumentation is still not a reality. Sampling, sample preparation, exti-action, and cleanup of the extracts are a very important part of pesticide residue analysis. The use of solvents and reagents, especially prepared for pesticide residue analysis, is highly recommended. The quality of TLC plates i j somewhat variable; therefore, TLC plates from more than one manufacturer should be evaluated for use in a residue analysis. Lamberton and Claeys (211) described a large inexpensive oven to be used to decontaminate glassware for environmental pesticide analysis. These authors found that classical methods which use stron: oxidizing acids or methanol-base for cleaning glassware were frequently ineffective in removing chlorinated pesticide contaminants. Contamination was reduced to insignificant levels when glassware was baked inthe oven at 230 “C. Bevenue and coworkers (38) discussed potential problems with the use of distilled water in pesticide residue analysis. Preferably, an all-glass still unit which contains no plastic fittings of any type should be used. This article discusses some of the potential problems with distilled water that may occur if plastic or resin components are included in the distillation system. Bevenue and coworkers (36) discssed the problems in water analysis for pesticide residues. Organic solvents, glassware, plastic ware, filter paper, and silica gels may contribute contaminants to water samples, which may interfere with the subsequent GLC analysis for pesticides in the ppb range. Prior to their use, glassware and silica gel should be heat-treated. Plastic ware and filter paper should not be used in the analysis. Johnsen and Starr (188) described an ultra-rapid extraction of insecticides from soil using a new ultrasonic technique. The Polytron, a high specific intensity ultrasonic generator was used to extre ct insecticide residues from soil using acetone as a solvent. Extraction for only 30 seconds gave generally better recovery values than did other methods including eight-hour Soxhlet extraction. Hesselberg and Johnson (166) cescribed a column extraction of pesticides for fish, fish food, and mud. Woods and Castle (395) described a rapid procedure for
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determining the percentage of fat in egg yolk for a1)plication in pesticide residue analysis. Burke and coworkers (65) evaluated two extraction procedures for pesticide residues resulting from foliar application and root absorption. McLeod and Wales (245) described a low tempcl-ature cleanup procedure for pesticides and their metabolites in biological samples. Samples were extracted by rel'luxing with acetone-benzene (19 1) and extracts were cleaned up by a low temperature precipitation at -78 "C. A precipitation time of 30 minutes followed by fill ration through cellulose fiber was optimum. The cleaned-Jp extracts were suitable for GLC determination with eltictron capture and flame photometric detectors. Rogers (306) used a solid support for the extraction of pesticides from large quantities of fats and oils. Gore and coworkers (147) determined the infrare:l and ultraviolet spectra of 76 pesticides. Hutzinger and coworkers ( I 77) discussed the ele :trondonor-acceptor complexing reagents for the analysis of pesticides. Kennedy and coworkers (198) identified the chemi-a1 or thermal decomposition of 20 selected pesticides. Ivie and Casida (184) discussed the sensitized phctodecomposition and photosensitizer activity of pesticide chemicals exposed to sunlight on silica gel chromoplates. Johnson (189) described the analysis of pesticidss in water using silica gel column cleanup. Chisholm and Mac Phee (83) studied the long term persistence and effects of some pesticides in soil. Rankin (299) described the negative ion mass spectia of some pesticidal compounds. Versino and coworkers (374) compared some cleair-up columns for residue analysis of chlorinated and phos1)horus-containing pesticides. Eight widely used clean-up methods based on adsorption column chromatogriiphy used for chlorinated and phosphorus-containing cvmpounds were investigated. Getz (138) described a n automatic spotter for quantitative thin-layer and paper chromatographic analysis b> optical scanning. Sandroni and Schlitt (313) described a screening method for organochlorine and -phosphorus pesticide residues in vegetables using thin-layer chromatography. Mendoza and Shields (256) studied esterase specificity and sensitivity to organophosphorus and carbamate pcsticides. Studies with beef liver, pig liver, and bee brain esterases were used for the determination of a numbe- of common organophosphorus and carbamate pesticides. Sulfur, which is used as an antifungal agent and E B a diluent in many pesticidal dusts, often interferes arith pesticide quantitation. Two papers were presented wk ich described methods for its removal. Goerlitz and Law (245) described a method for the lemoval of sulfur interferences from sediment extracts for pesticide analysis. The hexane extracts are shaken from a drop of metallic mercury to remove the interference. Shutzmann and coworkers (331) described a procediire for the removal of sulfur in environmental samples prior to gas chromatographic analysis for pesticide residues. The sulfur was removed by refluxing the sample extr,ict with a copper-aluminum alloy. Recovery of chlorinal txd pesticides from desulfurized extract is >80%. Parathim and malathion gave recoveries of approximately 50%. Law and Goerlitz (214) described a microcolumn chi-omatographic cleanup procedure for the analysis of pesticides in water. Young and Burke (405) described a microscale alkdi
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treatment for use in pesticide residue confirmation and sample cleanup. Detailed directions were given for use of this long-standing procedure. Hall (162) discussed the variation of Florisil activity and described a method to increase retentive properties and improve recovery and elution patterns of insecticides. Tindle and Stalling (363) described an automated gel permeation cleanup for pesticide residue analysis which was applied to fish lipids. The automated system allowed unattended operation while processing up to 23 samples. Reproducibility was good and cross contamination w a s minimal. Giang (142) described a sandwich KBr disk for scanning volatile pesticides which prevents the loss of the material during scanning.
GAS CHROMATOGRAPHY Gas chromatography continues to be one of the most satisfactory procedures for the separation and quantitation of pesticide residues. These two years have seen continued improvement in techniques and equipment to allow more sensitive and accurate analysis of pesticide residues and pesticide metabolites. New detectors and new combinations of gas chromatography with other instruments promise much for the future. The most exciting prospects are likely to come from combinations with mass spectrometry with the help of the computer. Scheide and Guilbault (316) described a piezoelectric detector for organophosphorus compounds and pesticides. A quartz piezoelectric crystal coated with a substrate was used for the detection of small mass changes caused by the selective adsorption of organophosphorus compounds and pesticides. Incorporation of the crystal into a variable oscillator circuit and measurement of the change in frequency of the crystal due to the increase in mass allowed a highly sensitive indication of the amount of organophosphorus compounds present. New high temperature packings have been made available and may prove satisfactory for hard-to-chromatograph pesticides. Van de Wiel and Tommassen (372) studied the effect of oxygen on electron capture detection. These authors found that if the carrier gas does not contain electronegative contaminants, the electron concentration in the electron capture detector is virtually independent of the temperature and the gas flow rate. With oxygen in the carrier gas, the electron concentration decreases. Croll (98) discussed septum interference. It was found that septum contaminants were introduced into the chromatograph by deposition into the syringe needle during its passage through the septum. He found the quantity introduced could be reduced to acceptable proportions by using short syringe needles and acetone pre-extracted septa. Levi and Nowicki (225) described interfering GLC peaks from materials and chemicals used in pesticide residue analysis. Procedures were described for the elimination of these interfering peaks from extracts of reagents and apparatus. Kruppa and Henly (208) discussed GLC injection techniques. These authors stressed the importance of proper injection technique in accurate quantitative GLC analysis. Mendoza (25.5) investigated the significant difference in GLC response to insecticides injected at fast and slow rates. GLC responses were significantly higher when Dyrene, aldrin, p,p'DDT, malathion, and parathion were in-
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jected at a slower rate than when they were injected at a fast rate. Results were the same regardless of the pesticide concentration, detector foils, and detector temperature used. Fressler and Deml (131) presented a theoretical discussion of the reduction of detector noise in gas chromatography by means of an RC filter. Up to a 30-fold decrease in detector noise was shown to be possible.
CHLORINATED PESTICIDES General Procedures. During this two-year period, there has been an increasing effort to replace chlorinated hydrocarbon pesticides with less persistent materials, and the use of some chlorinated pesticides such as DDT and its analogs has greatly decreased. However, residues of these pesticides still persist in the environment, and a number of publications have appeared on their analysis and metabolism. Giam and Wong (141) reported on the problems of background contamination in the analysis of open ocean biota for chlorinated hydrocarbons. Contamination from chemicals, materials, and equipment used for the analysis of chlorinated hydrocarbons in the parts-per-billion range was a serious problem. Burke (63, 64) a general referee for the AOAC reported on chlorinated pesticides. Chen and Dority (81) presented 29 reference IR spectra for purified halogenated pesticides. The observed characteristic frequencies were tabulated in correlation tables, and their significance was interpreted in terms of the substituents and of the electromesomeric and mass effects of the substituents. Bellman and Barry (28) developed a system for the identification of multiple chlorinated pesticide residues by combined GLC-MS. Hutzinger and Jamieson (1 76) identified organochlorine pesticides in crude extracts by mass spectrometry. Collier and coworkers (89) described a relative retention time ruler for use in pesticide residue analysis. This ruler was used for the rapid qualitative identification of chlorinated hydrocarbon pesticides measured by their GLC peaks or for direct graphic determination of their relative retention times. Bowman and coworkers (53) described a sodium sulfatesensitized flame photometric detector for the GLC quantitation of compounds containing chlorine, bromine, and iodine. This detector is based on the 589-nm flame emission of a n NaZS04 thermionic detector. The detector is highly selective in its response to compounds containing halogens and the response is linear. French and Jefferies (130) studied the preservation of biological tissue for organochlorine insecticide analysis. A formaldehyde or 10% phenol solution was found to be satisfactory. Formaldehyde is probably more satisfactory because of less interference in subsequent GLC analysis. Holmes and Wood ( I 72) described the removal of interfering substances from vegetable extracts prior to the determination of organochlorine pesticide residues. McClure (235) described the preparation of precisely deactivated adsorbents to be used for the separation of chlorinated hydrocarbons. Mills and coworkers (261) described an elution solvent system for Florisil column cleanup in organochlorine pesticide residue analyses. Three eluants consisting of different mixtures of methylene chloride, hexane, and acetonitrile gave excellent cleanup for extracts of fats and oils and recovered pesticides with a wide polarity range. Chau and Wilkinson (79) described some separation
characteristics of an OV-101/OV-210 column for organochlorinated pesticides with particular reference to the separation of photoendrin and endrin. Kaufman and coworkers (194) described a procedure for the identification of nanogram amounts of certain organochlorine insecticides. Individual inseclicides eluting from a gas chromatographic column were detected with an electron capture detector and concuri*ently trapped in a Teflon (Du Pont) capillary tube. Fifty microliters of solvent was added, and the trapped comlDonent was irradiated with ultraviolet light. Following irradiation periods of 15 to 120 seconds, the contents of the Teflon tube were reinjected into the gas chromatograph and the UV-induced degradation pattern was noted. Characteristic “fingerprint” degradation patterns were obtained for nanogram quantities of a number of organochlorine insecticides. Bowman and coworkers (55) developed an indium sensitized flame photometric detector for :he gas chromatography of halogen compounds. This detector is based on light emission a t 360 nm when the halogon compounds in the column effluent are burned in a hydrogen-oxygen flame over a stainless steel screen coated with indium. The emitted light, after passing a 360-nni interference filter is monitored by a photomultiplier tube which registers its response on a strip-chart recorder. Response was linear with concentration in log-log plots over a usable range. Unfortunately, compounds contair ing sulfur interfere, while those containing phosphorus do not. Moseman and Aue (266) described a dual mode indium flame detector where the flame burned in contact with liquid indium. The detector can be used for compounds containing chlorine, bromine, or iodine. Ivie and Casida (185) described Fhotosensitizers for the accelerated degradation of chlorinated cyclodienes and other insecticide chemicals exposed to sunlight on bean leaves. Rotenone and other related substituted-4-chromanones acted as photosensitizers to accelerate the photoalteration of chlorinated cyclodiene insecticide chemicals exposed to sunlight on bean leaves. Sadar and Guilbault (311) studied a specific method for the assay of selected chlorinated pesticides. Twenty-one pesticides were tested on yeast hexokinase and the enzyme was inhibited by only four chlorinated pesticides: aldrin, chlordane, DDT, and heptachlor. As little as 0.1 ppm of these pesticides can be specifically detected in the presence of all other pesticides with a precision and accuracy of about 2%. St. John, Jr., and Bache (350) described a simplified Coulson electrolytic conductivity detector for chlorinated hydrocarbons. A simple plug of gars-Chrom Q as a gas flow restrictor inserted in the combustion tube eliminates the need for an expensive valve when the detector is used in the chlorine mode without a platinum catalyst. Hermanson and coworkers (165) investigated the installment application effect upon insecticide residue content of a California soil treated with eight organochlorine insecticides. Porter and coworkers (295) described a method for the analysis of fish, animal, and poultry tissue for chlorinated pesticide residues. Carr (72) described a collabordive study of a method for multiple chlorinated pesticide itesidues in fish. Levi and coworkers (224) described a rapid screening method for the determination of organochlorine pesticide residues in wheat by electron capture GLC. Ground wheat was extracted by grinding with ethyl ether-hexane (3 97). After filtration, the extract was cleaned up on a par-
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tially deactivated Florisil column, using a single e iiting system, ethyl ether-hexane (1 99). Sixteen organochlorine pesticides were recovered in excess of 80% from vheat samples fortified at the 0.010- and 0.200-ppm level. Iwata and coworkers (182) evaluated a rapid proci?dure for the determination of organochlorine insecticides ill raw and canned beef and in cheese fat by microcoulonu?tric GLC. Munson (270) quantitated chlorinated hydrocarbon :esidues in marine animals of Southern California. Smart and coworkers (336) determined the residu.s of some chlorinated hydrocarbon pesticides in milk and inilk products after their addition to the feed of cows. de Vos and coworkers (105) determined residues of o,+ganochlorine pesticides in broilers from feed fortified rrith known levels of these compounds. Glotfelty (144) described the identification of organochlorine pesticide residues by ultraviolet solid-phase rhotolysis. The electron capture GLC degradation patterns obtained by photolysis of these films with a germicidal lamp were reported by relative retention times on a 10% DC-200-15% QFI column. Stavric and Neville (346) re-examined the by-products obtained during the preparation of DDT metabolites. .4n extensive list of references is included. Chopra and Osborne (84) isolated and identified the degradation products of the pyrolysis of p,p’-DDT in a nitrogen atmosphere. This work was done in connection with their systematic studies on the breakdown of p,p’DDT in tobacco smokes. A series of breakdown prodLcts were identified by gas chromatography, IR spectromei ~ y , and colorimetric tests. Fehringer and Westfall (124) described a separation End identification of DDT analogs in the presence of ’polycklorinated biphenyl compounds by two-dimensional thinlayer chromatography. Bishara and coworkers (46) found that DDT and foiir metabolites were decomposed on commercially available pre-coated aluminum oxide TLC plates when exposed LO short wave light. Knowledge of decomposition is important if the plates are to be used for any multiple develcpment technique. Ernst (122) described the degradation of I4C DDT m Silica Gel G chromatograms under laboratory conditions. Miles (259) described the conversion of DDT and its metabolites to dichlorobenzophenones for analysis in tire presence of polychlorinated biphenyls. Bishara and coworkers (47) described the TLC analye is of DDT and related compounds on aluminum oxide chrimatoplates. Nash and Harris (278) investigated the influence of scil moisture on the treatment of extraction of DDT froiii soils. Lichtenstein and coworkers (226) reported on the vertical distribution of DDT, lindane, and aldrin residues 10 and 15 years after a single soil application. Dale and coworkers (100) described a quantitative method for the determination of DDT and DDT metabclites in blood serum. 14C-labeled DDT was used for this study. Chau and Lanouette (77) described a procedure for t h ? derivative formation in solid matrix for the confirmation of DDT, DDD, methoxychlor, Perthane, cis- and trans. Chlordane, heptachlor, and heptachlor epoxide pesticidi! residues by GLC. Wright and coworkers (396) determined DDT residues in chickens fed this insecticide. The chicken tissue was ground in a Thomas tissue grinder with petroleum ether
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The extract was dried with sodium sulfate, concentrated, and brought to volume with hexane. The DDT was determined by GLC using a nickel-63 detector. Sink and coworkers (332) studied the metabolism of I4C DDT by ovine rumen fluid i n vitro. Since the discovery of polychlorinated biphenyls in the environment, there has been increasing interest in their analysis and the interference they cause in the analysis of other chlorinated hydrocarbon pesticides. A number of publications described the identification of some polychlorinated biphenyl isomers. Tas and Kleipool (356) characterized three components of technically polychlorinated biphenyls. Addison and coworkers (2) analyzed chlorinated terphenyl (Aroclor 5460). Uthe and coworkers (371) described the extraction of organochlorine pesticides from water by porous polyurethane. Gesser and coworkers (137) described the extraction and recovery by PCB from water samples using porous polyurethane foam. Armour (13) compiled relative retention times and response data for polychlorinated biphenyl components in six Arochlors (Monsanto). Columns containing 10% DC200 and 1:l 15% QF-l/lO% DC-200 on 80-100 mesh Chromosorb W “HP” with electron capture detection were used for this study. Sissons and Welti (334) made structural identification of polychlorinated biphenyls in commercial mixtures by gas-liquid chromatography, nuclear magnetic resonance, and mass spectrometry. The retention indices of these compounds together with those of forty synthesized polychlorinated biphenyls have been used to predict the structures of the constituents of commercial biphenyls. Fishbein (126) presented a comprehensive discussion of the chromatographic and biological aspects of polychlorinated biphenyls. Hutzinger and coworkers (1 79) described the synthesis of 23 chlorobiphenyls using a number of different synthetic routes. All chlorobiphenyls prepared were homogeneous on thin-layer chromatograms and gave one peak when chromatographed on a 4% SE-30 column. Webb and McCall (382) identified polychlorinated biphenyl isomers in Aroclors. Albro and Fishbein (5) described the quantitative and qualitative analysis of polychlorinated biphenyls by gasliquid chromatography and flame ionization detection. Retention indices on six liquid phases were given for the mono-, di-, and trichloro-biphenyls. Shaw (328) described a procedure for the discrimination between PCB and DDT residues by a gas chromatographic-mass spectrometric technique. Holmes and Wallen (171) described a single procedure for the differentiation of PCB’s from chlorinated naphthalenes. Collins and coworkers (90) described methods of analysis of PCB in wild-life specimens. Rote and Murphy (308) described a method for the quantitation of polychlorinated biphenyl isomers. Tissue samples were digested by a perchloric-acetic acid mixture, the fat extracted in hexane. Acetonitrile partitioning was followed by a Florisil column cleanup. The PCB’s were separated from the pesticides by column chromatography on silicic acid-Celite. The PCB’s were quantitated by separation on a mixed Dow-200 and QF-1 column and a helium glow electron-capture detector. DoIan and coworkers (109) described a selective detection of chlorinated insecticides in the presence of poly-
APRIL 1973
chlorinated biphenyls. A Coulson electrolytic conductivity detector was modified to allow precise control of furnace temperature and hydrogen reaction gas flow. A furnace temperature of 600 “C and a gas flow of 1/2 ml/min were most advantageous for selective detection of chlorinated insecticides in the presence of polychlorinated biphenyls. de Vos and Peet (106) described the thin-layer chromatography of polychlorinated biphenyls. These authors prepared their own plates using “Kieselguhr G” and treated the plates with 8% liquid paraffin in petroleum. Leoni (221) described a separation of 50 pesticides and related compounds and polychlorobiphenyls into four groups by silica gel microcolumn chromatography. Berg and coworkers (35) described a column chromatographic separation of polychlorinated biphenyls from chlorinated hydrocarbon pesticides and their subsequent gas chromatographic quantitation in terms of derivatives. Asai and coworkers (15) differentiated polychlorinated biphenyls from DDT by carbon-skeleton chromatography. Russo and coworkers (309) studied the photolysis of 3,4,3’,4’-tetrachlorobiphenyland 4,4‘-dichlorobiphenyl in solution. Zitko and coworkers (41I ) tested the retention times and electron capture responses of some individual chlorobiphenyls. Data are presented relative top,p’-DDE. Stalling and coworkers (343) described the cleanup of pesticides and polychlorinated biphenyl residues in fish extracts by gel permeation chromatography. Recoveries were greater than 95% by this technique. Snyder and Reinert (339) described a rapid separation of polychlorinated biphenyls from DDT and its analog on silica gel. The PCB’s were eluted from a silica column with pentane and the DDT and its analogs were eluted with benzene. Schmidt and coworkers (31 7) studied the input of polychlorinated biphenyls into California coastal waters from urban sewage outfalls. Quantitation was by GLC using a nickel-63 electron capture detector. Zitko (409) determined levels of polychlorinated biphenyls and organochlorine pesticides in some freshwater and marine fishes. Zitko and coworkers (410) described the detection of polychlorinated terphenyls (PCT) in eggs and tissues. Platonow and coworkers (291) determined residues of PCB in cattle by GLC analysis. Grant and coworkers (148) studied the metabolism of a polychlorinated biphenyl (Aroclor 1254) mixture in the rat. These researchers found that all components of the mixture were not metabolized a t the same rate. Armour and Burke (14) studied the behavior of chlorinated napthalenes in analytical methods for organochlorine pesticides and polychlorinated biphenyls. A silicic acid column previously developed to separate PCB from pesticides also separated chlorinated naphthalene from the pesticides. Goerlitz and Law (146) discussed the chlorinated naphthalenes as a source of interference in the GLC analysis of organochlorine insecticides. GLC traces and mass spectra data were presented. McKinney and coworkers (240) described a procedure by which desired chlorinated polycyclodiene pesticide metabolites can be separated from interfering impurities by selective complexation. Europium nitrate was employed as a selective complexing agent which enabled the low levels of the metabolites which are normally masked by silylation procedural impurities in electron capture GLC analysis to be quantitated. Conder and coworkers (92) described a GLC column
which separated heptachlor epoxide, ox ychlordane, a- and y-chlordane. The column was packed with 80/100 mesh Chromsorb W “HP” coated with 1.5% OV 17 1.95% OV 210. Lester and Smiley (222) identified aldrin in the presence of sulfur by electron capture GLC using a 3% OV-17 on Chromsorb W “HP.” Yu and coworkers (406) studied the oxidative metabolism of aldrin and isodrin by bean root fi actions. Benson (30) described the photolysis of solid and dissolved dieldrin. Chau and Cochrane (75) identified the derivatives employed in the conformation of dieldrin ri3sidues. Caro (71) compared four extraction procedures for roottranslocated dieldrin in maize, kale, alfalfa, and wheat. Woodham and coworkers (393) described a procedure for the identification of the GLC (dieldrin and endrin peaks by chemical conversion. Lombard0 and coworkers (231) described the identification of photoaldrin chlorohydrin a s a photoalteration product of dieldrin. McKinney and coworkers (241) deccribed studies which elucidated the structure and chemistry of the major fecal metabolite of dieldrin, C-12 syn-hydroxy dieldrin, in the rat. Its structure was confirmed vicz NMR spectroscopy employing spin decoupling techniques. Matthews and coworkers (251) studied dieldrin metabolism, excretion, and storage in male and female rats. Dieldrin I4C was used in this study. Benson and coworkers (33) prepaied and identified the photoalteration products of chlordane. Structures were proposed for the photoisomers, and MS, NMR, GLC, and TLC data were presented. Poonawalla and Korte (294) studied the metabolism of t r u n s - c h l ~ r d a n e - ~ ~and C identification of its metabolites from the urine of rabbits. Polen and coworkers (293) chara 2terized oxychlordane, the animal metabolite of chlordane. Saha (312) compared several methods of extracting chlordane residues from soil. His work again confirms the necessity of adding water to soil prior to the extraction of pesticides. Dorough and Pass (111) determined residues in cdrn and soil treated with technical and high purity chlordane. Dorough and coworkers (112) determined residues of chlordane in alfalfa and soils following treatment with technical chlordane and high purity chlordane (HCS3260). Chau and Wilkinson (80) continued their study of the use of chromous chloride reduction in the confirmation of endrin degradation products. Chau and Cochrane (76) described a chromous chloride derivative formation for the simull aneous identification of heptachlor and endrin pesticide residues by gas chromatography. McGuire and coworkers (238) reported on the photochemical reactions of heptachlor. Chau and coworkers (78) desxibed the synthesis of known and suspected environmental products of heptachlor and chlordene. Matsumura and Nelson (250) identified the major metabolic product of heptachlor epoxide in rat feces. Carter and coworkers (73) analyzed Oregon soil previously treated with technical heptachlor for l-hydroxy2,3-epoxychlordene. Burrage and Saha (66) determined residues in pheasants which had been fed on wheiit seed treated with heptachlor and I4C-lindane.
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Ivie and coworkers (186) reported on the photoproducts of heptachlor epoxide, trans-chlordane, and trans- qonachlor. Nash and Beall (277) reported on the extractior and identification of endrin and heptachlor degradation products. The study was made using 14C-heptachlor and I4Cendrin and identification was made by multiple GLC! and TLC techniques. Chau (74) confirmed the photoproducts of endrin: Iiexachloro- and pentachloro-ketone pesticide residues bj' gas chromatography after formation of silyl derivatives. Baldwin and coworkers (23) studied the metabolism of endrin in the rat. Three major metabolites were found. One, found in the tissues and urine, is a ketone p r o d x e d by replacing the methylene group of endrin by a carbonyl group; the other two occur in the feces. The major OIN!of the fecal metabolites is a secondary alcohol formed bj the substituting of one hydrogen of the methylene group o ' endrin by a hydroxyl group. Matsumura and coworkers (249) studied the metiibolism of endrin by certain soil microorganisms. At l2ast seven metabolites were isolated. Taylor and Keenan (357) discussed the analysis of h n zene hexachloride in the ppb range in grains. The diffi:ulties of analysis were enumerated and partially resolved. Archer and coworkers (1 I ) studied the photodecompmition of endosulfan and related products in thin films by ultraviolet light irradiation. Greve and Wit (151) described a rapid identification method for endosulfan from GLC peak shifts under the influence of alkali. Uk and coworkers (369) described the mass specfial patterns of Kepone and Mirex. Uk and coworkers (370) identified Mirex residues in crude extracts and in the presence of polychlorinated hiphenyls by mass spectrometry. Mehendale and coworkers (253) studied the fate of 1 4 C Mirex in the rat and plants. Gibson and coworkers (143) studied the fate of Milex and its major photodecomposition product in rats using radiolabeled Mirex. Krause (207) described the quantitative dehydrochlorination of Perthane residues prior to quantitation by electron capture GLC. Zabik and Duggan (407) made an extensive study of the location of lindane, dieldrin, and DDT compounds in egzs taken from hens fed rations containing 25 ppm of the32 pesticides. Kapoor and coworkers (191) studied the comparatiw metabolism of DDT, methylchlor, 2,2-bis(p-methylphenyl)- l,l,l,-trichloroethane, ethoxychlor, and 2,:!bis(p-ethoxyphenyl)-l,l,l-trichloroethane in the mousi?, insects, and in a model ecosystem. Kapoor and coworkers (192) studied the comparath 6: metabolism of methoxychlor, methiochlor, 2,2-bis(p methylthiopheny1)-l,l,l- trichloroethane, and DDT i I mouse, insects, and in a model ecosystem. Rappe and Nilsson (300) analyzed commercial samples of pentachlorophenol by gas chromatography and mas3 spectrometry. Although these authors' procedures werc not performed on residue samples, data given should be ot' interest to anyone analyzing polychlorinated phenols. Williams and coworkers (389) described distribution and excretion studied by octachlorodibenzo-p-dioxin ir the rat. ORGANOPHOSPHORUS PESTICIDES General Procedures. This two-year period has seen the increasing use of organophosphorus pesticides. The phos156
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phorus-specific thermionic detector and the flame photometric phosphorus and sulfur specific detectors continue to be methods of choice for quantitation of these compounds. McCully (236, 237), a general referee for the AOAC, reported on phosphated pesticides. Pardue (286) described the recovery of organophosphorus compounds using the AOAC multiresidue method. Sixty organophosphorus compounds were studied using the official AOAC method. Recoveries of 13 compounds ranged from 80-110%. Nine additional compounds were partially recovered, and the remainder of the compounds were not recovered. Storherr and coworkers (353) presented a general method for the determination of organophosphorus pesticide residues in non-fat foods. The foods were extracted with acetonitrile and the extract cleanup was performed with a short charcoal column. The pesticides were quantitated by GLC using a potassium chloride thermionic or flame phatometric detector. Forty-one organophosphorus pesticides and/or metabolites were evaluated. Shafik and coworkers (325) developed a cleanup procedure for the determination of low levels of alkyl phosphates, thiophosphates, and dithiophosphates in rat and human urine. Antoine and Mees (10) described a routine method for the determination of organophosphorus insecticides by TLC. Silica gel and polyamide absorbents, six solvent systems, and three main visualization procedures were used. This paper is very comprehensive and should be very useful to analysts working in the field of organophosphorus insecticides. Watts (381) described three procedures for extracting 14C-labeled and unlabeled residues of organophosphorus pesticides from bean leaves and kale. Blending with ethyl acetate, or acetonitrile, or a Soxhlet extraction with 10% methanol in chloroform gave better than 90% recovery. Cowart and coworkers (94) studied the rate of hydrolysis of seven organophosphate pesticides. Suffet and Faust (355) described the p-value approach to quantitative liquid-liquid extraction of organophosphorus-containing pesticides in water. Shafik and coworkers (326) described a method for confirmation of organophosphorus compounds a t the residue level by preparation of derivations and subsequent analysis by GLC. Aue and coworkers ( I 7) determined the hetero-element content in organics by alkali flame GLC. Greenhalgh and coworkers (149) compared the response of organophosphorus compounds containing nitrogen and nitrogen with alkali flame and electrolytic conductivity detectors. The response of the AFI was greater for phosphorus than for nitrogen and the results obtained suggested that the magnitude of response was dependent on structural effects. The response of these two detectors to nitrogen compounds was of the same order. De Loach and Hemphill (102) discussed in detail the use of the alkali-flame detector with a rubidium sulfate source for the quantitation of phosphorus- and nitrogencontaining compounds. This comprehensive article will be very helpful both to analysts routinely using this detector and to analysts planning to set up a laboratory for the analysis of pesticide residues. Aue and Moseman (19) described the spectral response of the alkali flame detector. Bowman and Beroza (52) used Dexsil 300 on Chromosorb-W specially washed with HC1 for the multicomponent residue determination of phosphorus- and sulfur-con-
ANALYTICAL CHEMISTRY, VOL. 45, N O . 5, APRIL 1973
taining pesticides by flame photometric GLC. Retention times relative to parathion were given for a large number of sulfur- and phosphorus-containing pesticides. Bowman and coworkers (54) presented chromatograms of foods for multicomponent residue determination of pesticides containing phosphorus and/or sulfur by GLC with flame photometric detection. Ragab (296) described the use of methyl yellow as a single chromogenic reagent for TLC detection of organophosphorus and their breakdown products. Pesticides were made visible for exposure of the developed TLC plate to bromine with subsequent spraying with methyl yellow. Gardner (133) developed a new two-dimensional TLC technique for the confirmation of organophosphorus pesticide residues at the nanogram level. The pesticides were oxidized on the TLC plate with bromine vapor after onedimensional development before development in the second direction. Suett (354) studied the persistence and degradation of four organophosphate insecticides in soil and their uptake by carrots. Specific Compounds and Procedures. Miller and Funes A (260) described an alkali flame gas chromatographic procedure for the analysis of Abate, 0,0,Of, 0’tetramethyl- 0,0’-thio-p-phenylene phosphorothioate. A I/s-in. 0.d. X 10-in. column packed with 2.5% E-301 plus 0.25% EPON 1001 on SO/lOO mesh Gas-Chrom W “HP” was used. Column temperature was 235 “C. Henry and coworkers (164) combined high speed liquid chromatography for the evaluation and analysis of Abate in water. The samples were extracted with chloroform or n-heptane, concentrated by evaporation, and chromatographed without further cleanup. The ultraviolet photometer detector used in the study was sensitive to one nanogram of Abate. Thorton (360) determined residues of Nemacur, [ethyl 4-(methylthio)-m-tolyl isopropylphosphoramidate], a promising new nematicide, and its metabolite in plant and animal tissues. After initial extraction, the extract was oxidized with potassium permanganate to convert Nemacur and its sulfoxide to the sulfone. Final detection of the sulfone is by the phosphorus-sensitive alkali-flame detector, thereby allowing little interferences from tissue extractives. Waggoner (377) studied the metabolism of Nemacur I4C in plants. Two metabolites in plants were identified. Thornton and Stanley (362) determined Bay 93820, 0methyl phosphoramidothioate 0-ester with isopropyl salicylate, a promising new cotton insecticide and its oxygen analog in plant and animal tissues. After initial extraction, the parent compound was separated by solvent partitioning from the oxygen analog and was cleaned-up separately. The oxygen analog was deaminated and methylated to convert it to a more desirable derivative for gas chromatography. Final detection utilized the phosphorussensitive alkali flame detector. Bull and Whitten (62) studied the metabolism of 3aP labeled Bay-93820 in cotton plants. These studies demonstrated that the compound was apparently metabolized to a single secondary toxicant, the oxygen analog, and to several unidentified nontoxic products. Williams and coworkers (391) determined residues of Dasanit, 0,O-diethyl 0-[p-(methylsulfinyl)phenyl]phosphorothioate and three metabolites by gas chromatography with flame photometric detection in the phosphorus mode. Sensitivity was a t least 0.01 ppm and recoveries averaged a t least 90%. Bowman and Hill (56) determined Dasanit and three of
its metabolites in corn, grass, and milk. Extracts were separated by liquid chromatography on silica gel into three fractions which were concentrated and injected into a gas chromatograph equipped with a flame photometric detector sensitive to phosphorus. Westlake and coworkers (383) studiej the persistence of Torak, 0,O-diethyl S-(2-chloro-l-phthdimidoethyl) phosphorodithioate on and in lemons, oranges, and dried citrus pulp. The Torak was determined by GLC using a cesium bromide thermionic phosphorus detector. St. John, Jr., and coworkers (351) dcscribed metabolism studies with Torak insecticide in the da Iry cow. Kleinschmidt (201) determined the fate of Di-syston, 0,O-diethyl S-[2-(ethylthio)ethyl] pkosphorodithioate in potatoes during processing. Analysis lor Di-syston and its oxygen analog were made by GLC after oxidation to their corresponding sulfones. Uk and Himel (368) developed a GLC method for the analysis of Dursban and Thiodan insecticides in topically treated houseflies. Maini and coworkers (248) determined Dursban in a variety of crops by gas chromatography using a thermionic detector after extraction and clean-up by sweep co-distillation. Beynon and Wright (45) described the breakdown of I4C labeled monocrotophos, dimethyl S-k,ydroxy-N-methylciscrotonamide phosphate on several crops. Hogan and Knowles ( I 70) studied the metabolism of diazinon by fish liver microsomes. Yang and coworkers (398) studictd the metabolism in uitro of diazinon and diazoxon in suweptible and resistant houseflies. Yang and coworkers (397) studied the metabolism in uitro of diazinon and diazoxon in rat liver, Sherman and coworkers (330) studied chronic toxicity and residues from feeding Nemacide, 0-(2,4-dichloropheny1)O-0-diethyl phosphorothioiite to laying hens. A GLC electron capture method was developed to measure nanogram amounts of Nemacide and its metabolite, 2,4dichlorophenol. Leary (218) described the GLC determination of Monitor, 0,s-dimethyl phosphoramitlothioate residues in crops. The crop was extracted with ethyl acetate, the solvent evaporated, and the residue cleaned up by passage through silica gel. The Monitor WIS quantitated by GLC using a cesium bromide thermionic detector. Menzer and coworkers (258) studied the metabolism of Mocap, 0-ethyl S,S-dipropyl pho!;phorodithioate in bean and corn plants. Gabica and coworkers (132) determined methyl parathion in rat whole blood and brain tissue by flame photometric analysis. Leuck and Bowman (223) determined residues of phorate and five ofjts metabolites in fcrage corn and grass. Thorton and Schumann (361) described a photofluorometric procedure for the determination of residues of Mareten, N-hydroxynaphthalimitle diethyl phosphate, in meat and milk. Sensitivity is good to a t least the 0.1-ppm level in meat tissues and to 0.01 ppm in milk. Greenhalgh and coworkers (156) determined Crufomate, 4-tert-butyl-2-chlorophenylmethyl methylphosphoramidate in bovine blood. A gas chromatograph equipped with a cesium bromide thermionic dctector was employed for quan t it at ion. Eberle and Hormann (115) studied the fate of Supracide, S-[(2-methoxy-5-0xo-A’”-1,3,4-thiadiazolin-4-y1) methyl]-0, 0-dimethyl phosphorodithioate, and its oxygen analog in field grown crops and soil. Analytical methods
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were presented for routine determination of unchsnged Supracide by GLC using both sodium thermionic: and electrolytic detectors. Metabolites were detected on TLC plates. Polan and Chandler (292) studied the metabolis in of 14C-carbonyllabeled Supracide by lactating cows. Ivey and Claborn (183) described the GLC deterrnination of ronnel, 0,O-dimethyl 0-2,4,5-trichlorophenyl 3hosphorothioate in animal tissues. A flame photometri :: detector was used and with extraction and cleanup 0.002 ppm of ronnel and 0.005 ppm of the oxygen analog could be detected, and recoveries of 75-95% for ronnel ana 80100% for the oxygen analog were reached. Lucier and Menzer (233) studied the nature of neiiiral phosphorus ester metabolites of phosphamidon formed in rats and liver microsomes. Sauer (315) studied the fate of formothion, 0,O-dimsthyl S-(N-methyl N-formylcarbomoymethyl) phosphor3dithioate in bean plants in the green house using 14C labeled material. Guardigli and coworkers (156) determined Phosalone, 0,O-diethyl S-(6-chloro-2-oxobenzoxazolin-3-yl) methyl phosphorodithioate and its oxygen analog metabolite in citrus crops. The Phosalone was determined by 63Ni electron-capture GLC and the metabolite by TLC. Gauer and Seiber (134) determined residues of Phosalone on grapes. Bull and Stokes (60) studied the metabolism of G C 6506, dimethyl p(methy1thio)phenyl phosphate in ariimals and plants. El-Rafei and Hopkins (1 17) described the absorpticln, translocation, and conversion of malathion to malaoxon in bean plants. McBain and coworkers (234) reported on the metabolic degradation of Dyfonate, 0-ethyl S-phenyl ethylphosphonodithionate in plants. Seiber and Markle (324) studied the hydrolysis and sclvent partition of Phosdrin and related organophosphates. Schultz and coworkers (320) determined residues of dichlorvos and related metabolites in animal tissues and fluids. Beynon and coworkers (41) determined residues of tetrachlorvinphos and its breakdown products on a range of field crops. Menzer and Dauterman (257) studied the metabolism of dicrotophos, monocrotophos, phosphamidon, and di methoate. Beynon and coworkers (42) determined residues of tetrachlorvinphos and its breakdown products on apples. Burton (67) described the synthesis of 2,2-dichloroviny dimethyl phosphate labeled with 14C,36Cl,32P. Gutenmann and coworkers (159) studied the metabolism of Gardona in the dairy cow. Mollhoff (263) determined trichlorfon and fenthion residues in animals of different species. Crisp and Tarrant (95) determined residues of dichlorvos and malathion in wheat grain by GLC analysis using a phosphorus sensitive detector. Williams and coworkers (390) determined residues of Fensulfothion [0-diethyl 0-(p-[methylsulfinyl] phenyl) phosphorothioate] and its sulfone in muck. The Fensulfothion was extracted in a Soxhlet using 9 : l chloroformethanol, Cleanup and fractionation were on an alumina silica gel column and determination was by gas chromatography with flame-photometric detection. CARBAMATES Carbamate insecticides are of continuing importance and are being used to replace the more persistent chlori158 R
nated insecticides. Certain compounds present difficult analytical problems because of their instability on GLC columns. However, multi-halogenated acetate derivatives can usually be formed after which these compounds can be quantitated by GLC using one or more of several detectors. Kuhr (210) studied the metabolic fate of carbamate insecticide chemicals in plants and animals using 14C labeled compounds. Durden and Bartley (113) determined the mass spectra of 4-, 5-, 6-, and 7-hydroxy-1-naphthyl methylcarbamates as a n alternative method for the identification of these metabolites and potential metabolites of carbaryl. De Riveros and Vonesch (103) determined carbaryl in fruits and vegetables by a colorimetric procedure. The carbaryl was extracted with methylene chloride, concentrated, and cleaned up with zinc hydroxide. The carbaryl was reacted with diazotized 2,5-dichloroaniline to form a color which is measured a t 510 nm. Shafik and coworkers (327) determined 1-naphthol, a metabolite of carbaryl in urine. The 1-naphthol is treated with chloroacetic anhydride and the derivation purified by silica gel cleanup and quantitated by electron capture GLC . Andrawes and coworkers (9) studied the fate of naphthyl14Ccarbaryl in laying chickens. Khalifa and Mumma (200) described the GLC separation of the aglycone metabolites of carbaryl. Mumma and Khalifa (268) presented mass spectra of trifluoracetyl derivatives of carbaryl and its aglycone metabolites. Locke (228) described a TLC procedure for 1-naphthyl N-hydroxy, N-methyl-carbamate, a metabolite of carbaryl. Argauer and Webb (12) described a rapid fluorometric evaluation of the deposition and persistence of carbaryl in the presence of an adjuvant on bean and tomato leaves. Ott and coworkers (285) developed an automated steam distillation and fluorometry procedure for screening for carbaryl as 1-naphthol in fruits and vegetables. Kazano and coworkers (195) studied the metabolism of methylcarbamate insecticides in soil. Dorough (110) studied the metabolism of insecticidal methyl carbamates in animals. Locke and coworkers (230) studied carbamate pesticide metabolism utilizing plant and mammalian cells in culture. Nagasawa and coworkers (275) described the detection of 22 carbamates and related compounds on polyamide layers. Suitable solvent systems and the R, data obtained were reported. Moye (267) described a reaction gas chromatographic method for the on-column transesterification of N-methylcarbamates by methanol. Methyl N-methyl-carbamates were formed and chromatographed on Poropak P and detected by a RbZSO4 pellet alkali flame ionization detector. Seiber (323) analyzed N-perfluoroacyl derivatives of methylcarbamate insecticides by GLC. Stable compounds were formed by this derivatization and were detected by electron-capture and alkali-flame ionization detectors. Frei and Lawrence (128) described a fluorigenic labeling reagent, dansyl chloride, for carbamates. The carbamates are treated with this reagent prior to TLC analysis to form fluorescent derivatives. Lawrence and Frei (215) described the fluorigenic labeling of carbamate insecticides using dansyl chloride. Lawrence and coworkers (21 7) continued their study of the fluorigenic labeling of carbamates using dansyl chlo-
ANALYTICAL CHEMISTRY, VOL. 45, NO. 5, APRIL 1973
ride. In this paper, TLC properties of these derivatives were investigated. Frei and Lawrence (129) described the fluorigenic labeling of carbamates with dansyl chloride. These authors described the in situ quantitation of N-methyl carbamate insecticides on thin-layer chromatograms. Lawrence and Frei (216) described the fluorigenic labeling of N-methyl- and N , N-dimethylcarbamates with 4chloro-7-nitrobenzo-2,1,3-oxadiazole on TLC plates. Liu and Bollag (227) studied the metabolism of carbaryl by a soil fungus. Dhal and La1 (107) determined residues in field-treated corn by a colorimetric procedure. Bend and coworkers (29) identified water-soluble metabolites of carbaryl in mouse liver preparations and in the rat. Wheeler and Strother (386) studied the in vitro metabolism of the N-methylcarbamates, Zectran and Mesurol, by liver, kidney, and blood of dogs and rats. Butler and McDonough (68) determined residues of carbofuran and its toxic metabolites 3-hydroxycarbofuran and 3-ketocarbofuran. Samples were extracted with 0.25N HCI, partitioned into dichloromethane, and chromatographed on alumina. Liquid chromatography served the dual purpose of cleaning up the sample and separating the phenols from the carbamates. The carbamate residues were then converted to trichloroacetates and determined by electron capture GLC. Recoveries ranged from 67.2 to 139.5%. Tucker and Pack (366) studied the metabolism of Bux insecticide, 3 to 1 mixture of rn-(1 methylbuty1)-phenyl methylcarbamate and rn-(1-ethylpropy1)-phenylmethylcarbamate in soil. Andrawes and coworkers (7) studied the metabolism of Temik aldicarb pesticide, 2-methyl-2-(methylthio) propionaldehyde 0-(methylcarbamoy1)-oxime, in soil. Hicks and coworkers (168) reported on the metabolisms of aldicarb pesticide in the laying hen. Andrawes and coworkers (8) studied the metabolism of Temik aldicarb pesticide in potato plants. Carey and Helrich (69) developed a simplified method for the quantitative determination of aldicarb and its sulfoxide and sulfone in plant tissue. The method involved the quantitative extraction with acetone-methylene chloride, the separation of the three compounds on a liquid chromatographic column, and the oxidation of the separated compounds to the sulfone. This compound was then quantitated by GLC using a sulfur mode-flame photometric detector. The limit of detection was 0.005 ppm. Lee and Roughan (219) described improvements in the nitrite-diazo dye method for determining hydroxylamine as used in the determination of residues of Aldicarb. Westlake and coworkers (385) determined RE-11775, m-scc-butylphenyl N-methyl-N-thiophenylcarbamate in water, soil, and vegetation by flame photometric GLC. Van Middlelem and coworkers (373) determined carbofuran and 3-hydroxycarbofuran in lettuce by alkali-flame gas chromatography. Ashworth and Sheets (16) studied the metabolism of carbofuran in tobacco using I4C labeled compound. Stanley and Thorton (344) described a gas chromatographic method for residues of Baygon and its major metabolite in animal tissues and milk. Detection was by electron capture gas chromatography of the trichloroacetyl derivatives. Stanley and coworkers (345) described a gas chromatographic method for residues of Baygon, o-isopropoxyphenyl N-methylcarbamate, and its metabolites in plants.
HERBICIDES In this two-year review period, therc was again an increase in the number of articles dealing with herbicide analysis. Herbicides belong to many cle sses of compounds and the reviewer has segregated, where possible, the reviewed articles according to type of herbicide. Kratky and Warren (206) used three simple and rapid bioassays for the determination of fort y-two herbicides in soils. Guardigli and coworkers (154) determined acidic herbicides by TLC. After extraction and cleanup, the herbicide residues were converted to the nitro derivatives. These derivatives were then subjected to TLC and visualized by reducing the nitro to the amine followed by diazotization and coupling with N-( 1-naphthyl) ethylenediamine dihydrochloride. Hormann and coworkers (173) described an automated method for extraction, cleanup, and gas chromatographic determination of triazine herbicides in soil. Manually sieved soil samples are continuously delivered to the system, which presents cleaned up extracts to an automated GLC injection system. Peak areas are calculated by a digital electronic integrator and fed viii punch tape into a computer. Final analysis reports are printed out on a n attached typewriter. Cochrane and Wilson (87) described the electrolytic conductivity detection of some nitrogen containing herbicides. Bevenue and Ogata (37) studied the contributive error from analytical reagents in the analysis of chlorophenoxy acids and pentachlorophenol by eleclxon capture gas chromatography. Elvidge (I 18) described a gas chrcmatographic determination of 2,3,7,8-tetrachlorodiben~~o-p-dioxin in 2,4,5trichlorophenoxyacetic acid. Brenner and coworkers (58) determined Dioxin, 2,3,7,8tetrachloro-dibenzo-p-dioxin in chloro-substituted phenoxyalkane acids. The Dioxin was separated by extractive distillation of the potassium salts with n-hexane in the Bleidner apparatus. The Dioxin was quantitated by GLC analysis using a 60-m stainless-steel capillary coated with Dexsil300. Howard and Yip (174) reported on the diazomethane methylation of a mixture of chlorophenoxy acids and dinitrophenols. In an improved pro :edure, isooctane was added to the reaction flask to prevent the sample from evaporating to dryness and a 70 "C water bath was used to speed up the reaction. Conversion of these pesticides by the modified procedure was over 909'0. Meinard (254) described a new chromogenic reagent for the detection of phenoxyacetic a 5 d herbicides on thinlayer plates. Yip (402) described a method for the confirmation of chlorophenoxy acid herbicide residues by transesterification. Isensee and Jones (180) studied the absorption and translocation of root and foilage applied 2,4-dichlorophenol, 2,7-dichlorodibenzo-p-dioxin, and 2,3,7,8-tetrachlorodibenzo-p-dioxin. 14C labeled materials were used in this study. Yip (403) described an improved method for the determination of chlorophenoxy acid residues in total diet samples. Better recoveries, cleaner samples, and sensitivities down to 0.02 ppm were reported. Montgomery and coworkers (254) reported on the comparative metabolism of 2,4-D in bean and corn plants using 14C-carboxyl labeled 2,4-D. Feung and coworkers (125) studied the metabolism of
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2,4-dichlorophenoxy acetic acid by soy bean cotyledoii callus tissue cultures. Woodham and coworkers (394) described an improved gas chromatographic method for the analysis of 2,4-13 free acid in soil. The method includes an ether extraction of the acidified soil, an alkali wash to remove interl’ering substances, and an improved esterification procdure using a 10% BC13 in 2-chloroethanol. This method Wilii reported to be superior for the formation of methyl esler of 2,4-D. Hamilton and coworkers (163) studied the metabolism of 2,4-dichlorophenoxy acetic acid and 2,4,5-trichlorciphenoxy acetic acid by bean plants. Munro (269) determined 2,4-D and 2,4,5-T in toiirato plants and other crops by microcoulometric GLC. Wathana and Corbin (380) reported on the metabolism of 14C-ring labeled 4-(2,4-dichlorophenoxy) butyric acid in soybean and cocklebur. Chow and coworkers (85) described methodology for residues of MCP and 2,4,5-T in wheat. Bjerke and coworkers (48) studied residues of pheroxy herbicides in milk. McKone and Hance (243) determined residues of 2,$,5T i n soil by gas chromatography of the n-butyl ester. Clark and Palmer (86) determined residues of 2,4,j-T and an ester in sheep and cattle. The herbicide residlres were determined as the methyl ester by microcoulometry Barker and coworkers (25) studied the distribution rind metabolism of carboxyl-14C-2,3,5-triiodobenzoicacid tiid 2,3 (1251),5(1251)-triiodobenz~ic acid in the rat. Moseman and Aue (265) determined the herbicide piacid, in fescue hy cloram, 4-amino-3,4,5-trichloropicolinic GLC. Cheng (82) studied the adsorption and extraction of 3icloram in soil. Jensen (187) described an assay for 6-chloropicolir~ic acid (a metabolite of picloram) in milk and cream frcrn cows fed this compound. The samples were hydrolyzed with sulfuric acid and the 6-chloropicolinic acid was extracted with ether. Cleanup on a neutral alumina colunui was followed by esterification with diazomethane arid quantitative determination by gas chromatography employing a n LAC-446-H3P04 column and electron capture detection. Yih and Swithenbank (399) identified the metabolites I. of pronamide, (Kerb), N-(l,l-dimethylpropynyl)-3,5-d chlorobenzamide, a new herbicide, in soil and alfalfa. Walker (378) determined the persistence of Kerb in soil. Adler and coworkers (4) determined residues of Kerb i-1 milk, eggs, and tissues of dairy cows and laying hens fed this herbicide from field-aged residues on alfalfa. Adler and coworkers (3) determined residues from Kerb, by electron capture GLC. Yih and Swithenbank (400) identified the metaboliter; of Kerb in rat and cow urine and rat feces. Rogers (305) reported on the absorption, translocation and metabolism of C-6989, (Preforan) p-nitrophenyl. ( Y , ( Y , O ( - trifluoro-2-nitro-p-tolyl ether, in soy beans. Locke and Baron (229) studied Preforan metabolism by tobacco cells in suspension culture. Koons and Day (204) described a separation of benefin, p-toluiN-(n-butyl)-N-ethyl- 2,6-dinitro-a,a,a-trifluorodine and trifluralin, 2,6-dinitro-N,N-di- n-propyl-a,a,atrifluoro-p-toluidine by gas chromatography. A 6-ft X 2-mm i.d. glass column packed with Durapak-Carbowax 400/Poracil C 100/120 mesh held at 175 “C was used for separation. The herbicides were quantitated by a 63Ni electron capture detector. 160 R
Smith (337) described a simple and rapid method for the determination of trifluralin residues in soils using a electron-capture detector. Williams and Feil (392) identified trifluralin metabolites isolated from rumen microbial cultures. Several I4C preparations were used in this comprehensive study. Newsom and Mitchell (279) determined dinitramine N3,N3-diethyl-2,4- dinitro-6-trifluoro- methyl-m-phenylenediamine, an effective new herbicide in soil and plant tissue. Bowman and Leuck (57) determined the persistence of the herbicide phoxim, phenylglyoxylonitrile oxime, 0,Odiethyl phosphorothioate, Bay 77488 and its oxygen analog in forage corn and grass. Phoxim and its oxygen analog were determined by GLC using a flame photometric detector. Guardigli and coworkers (155) determined residues of carbetamide, [D(-)-phenylcarbamoyloxy-2- (N-ethylpropionamide)], a selective herbicide. The parent compound and its aniline metabolite were separated by liquid-liquid partition of the crop extract. After acid hydrolysis, the carbetamide afforded quantitative yields of ethylamine and aniline which were converted to the corresponding amides with 4-bromobenzoyl chloride. The amides were then separated by column chromatography on Florisil and quantitated by electron-capture GLC. Schultz and Tweedy (319) studied the uptake and metabolism of diphenamide, N,N-dimethyl-2,2-diphenylacetamide in resistant and susceptible plants. Krzeminski and coworkers (209) investigated the absorption of diphenamid-1-W, N, N - dimethyl-2,2-diphenylacetamide, from Hoagland solution by soybean plants. The metabolic pathway of the diphenamide was studied by chemical separation and high pressure liquid chromatography. Von Stryk (375) determined residues of the herbicide Bay 94337, 4-amino-3-methylthio-6- tert-butyl-1,2,4triazin-5-one in soil by a convenient flame photometric procedure. The soil was extracted with chloroform, the chloroform evaporated, the residue taken up in benzene and the Bay 94337 determined by GLC. The procedure was not tried on plant or animal tissue. Ott and coworkers (284) described a mechanized extraction and cleanup procedure of atrazine residues prior to GLC analysis. Spengler and Jumar (342) determined residues of carbamate and urea herbicides in soil. Onley and Yip (283) described the analysis of herbicidal carbamates. Each sample was extracted with ethanol or a n ethanol-water mixture followed by cleanup on a MgOcellulose column. Determinations were made by GLC using thermionic and electron capture detectors. A flame photometric detector was also used for confirmation for compounds containing sulfur. Recoveries a t fortification levels of 0.01 to 10 ppm exceeded 80%. Geike (135) described a TLC-enzymatic identification procedure for carbamate herbicides using bovine liver esterase. Paulson and Zehr (288) studied the metabolism of pchlorophenyl N-methyl carbamate in the chicken. Still and Mansager (347) studied the fate of metabolites of the herbicide isopropyl 3-chlorocarbanilate in soybeans. The major metabolite is isopropyl 5-chloro-2-hydroxycarbanilate which is degraded to pyrolytic degradation products during gas chromatography. Still and Mansager (348) described the metabolism of isopropyl 3-chlorocarbanilate in soybean plants. Paulson and coworkers (287) studied the metabolism of
A N A L Y T I C A L CHEMISTRY, VOL. 45, NO. 5, A P R I L 1973
isopropyl carbanilate, (propham), in the chicken. Knowles and Sonawane (203) studied the metabolism of the herbicide, EP-475, ethyl m-hydroxycarbanilate carbanilate in sugar beets using 14Clabeled compound. Still and Mansager (349) studied the metabolism of by soybean barban, 4-chloro-2-butynyl-3-chlorocarbanilate plants using a 14Clabeled compound. Bobik and coworkers (50) studied the fate of isopropyl 3-chlorocarbanilate herbicide, (chloropropham), in the rat using 14Clabeled material. Ercegovich and Witkonton ( I 19) described an improved colorimetric method for the analysis of residues of chloropropham in alfalfa. Ishikawa and coworkers (181) studied the behavior of Benthiocarb herbicide, 4-chlorobenzyl N,N-diethylthiolcarbamate in soil. The herbicide was steam distilled from the soil, the distillate extracted with hexane, and the hexane cleaned up with a charcoal column. Quantitation was by GLC using a flame photometric detector. Rosen and Siewierski (307) studied the photolysis of pyrazon, 5-amino-4-chloro-2-phenyl-3(2H)pyridazinone,a selective herbicide in both aqueous solution and on silica gel plates. Wheeler and coworkers (387) determined terbacil 3-tertbutyl-5-chloro-6-methyl uracil by electron capture gas chromatography. The extract was purified prior to quantitation by passage through a cellulose column. Guth and Voss (161) described an automated colorimetric procedure for the determination of total and unchanged urea herbicide residues in soils. By this procedure, manual work and working time was reduced by up to 50%. Mazzocchi and Rao (252) studied the photolysis of monuron and fenuron. Soboleva and coworkers (340) determined some N-chlorophenyl-N'-methoxy ureas using TLC. Lee and Fang (220) described the conversion of monuron to ethyl-N-p-chlorophenyl carbamate by Soxhlet extraction of plant tissue with ethanol. This conversion did not affect the accuracy of monuron analysis by the Bratton-Marshall reaction; however, it would affect the results of TLC or paper chromatography analysis. Certain other substituted urea herbicides can be converted to carbamates by refluxing with ethanol. Groves and Chough (153) described the extraction of 3amino-1,2,4-triazole and 2,6-dichloro-4-nitroanilinefrom soil. These authors found that concentrated ammonium hydroxide and glycol (1 4) gave much better recoveries of amitrole from soil than water extraction. Hydrochloric acid (lN), acetone, and glycol (1 + 1 + 8) were much better than hexane for the extraction of DCNA from soil. Bakke and coworkers (21) studied the metabolism of atrazine and 2-hydroxyatrazine in the rat using I4C ringlabeled materials. Bakke and coworkers (22) studied the metabolism of the triazine herbicide, GS-14254, 2-methoxy-4-ethylamino- 6-sec-butylamino-s-triazine in the dairy cow and goat using l4C-ring-labeledcompound. Lamoureux and coworkers (212) studied the conjugation of atrazine and four closely related 2-chloro-s-triazines in higher plants. McKone and coworkers (242) compared several methods for the determinations of residues of triazine herbicides in water. Beynon and coworkers (43) studied the breakdown of the triazine herbicide (Bladex), 2-chloro-4-(l-cyano-1methylethylamino)-6-ethylamino-1,3,5-triazine in soils and maize.
+
Schroeder and coworkers (318) descrl bed a n analytical method for the determination of residuc: levels of the herbicide hydroxcyprazine, 2-hydroxy-4-cyclopropylamino6-isopropyl-amino-s-triazinein corn. 'I he procedure was based on extraction and separation of hydroxycyprazine, followed by its conversion to cypazine, which subsequently was determined by GLC. Bandal and Casida (24) studied the metabolism and photoalteration of 2-sec-butyl-4,6-dinitrophenol,DNBP herbicide, and its isopropyl carbonate derivative, dinobuton acaricide. McKellar (239) determined 2-sec-butyl-4,F-dinitropheno1 and 2-amino-6-butyl-4-nitrophenol in milk and cream from cows fed 2-sec-butyl-4,6-dinitrophr!nol. Kearney and Plimmer (196) studied the metabolism of 3,4-dichloraniline in soil using 14Clabeled material. Groves and Chough (152) studied the fate of 2,6-dichloro-4-nitroaniline in plants and soil. Bartha (26) described the fate of herbicide-derived chloroanilines in soil. Skroch and coworkers (335) determined soil residues of dichlobenil, terbacil and DP-733, 3-tert-butyl-5-bromo-6met hyluracil. McKone and coworkers (244) determined residues of chlorthiamid and dichlobenil in gooseberries. Lamoureux and coworkers (213) studied the metabolism of propachlor, 2-chlor-N-isopropylacetanilidein the leaves of corn, sorghum, sugarcane, and barley. Nakagawa and coworkers (276) studied the metabolism of the herbicide 3-(2-methylphenoxy)-pyridazinein plants. Eastin (114) described the separation of the herbicide SAN-6706, 4-chloro-5-(dimethylamino)-2-(a,a.a-trifluoroin- tolyl)-3(2H)pyridazinone and sonie related compounds by TLC. Sachs and coworkers (310) determined arsenical herbicide residues in plant tissues. Moilanen and Crosby (262) studied the photodecomposition of the herbicide propanil. Gutenmann and coworkers (160) studied the metabolism of VCS-438 herbicide, 2-13,4-dichloropheny1)-4methyl-1,2,4- oxadiazolidine-3,5-dioiie in the dairy cow. Beynon and coworkers (40) reporfed the results of analysis of some crops and soils for residues of cyanazine. Beynon and coworkers (44) studied the breakdown of cyanazine in wheat and potatoes giown under indoor conditions in treated soils. Beynon (39) developed a procedure for the analysis of cyanazine and its metabolites in soil and crops. The full analytical procedure was describecr and quantitation was by GLC using an electron capture detector.
FUNGICIDES Several new systemic fungicides have come into general use and a number of articles on their analysis were published. Hutzinger and coworkers (178) tabulated the mass spectra of fifteen chlorinated aromatic fungicides. Wallnofer and coworkers (379) studied the metabolism of the systemic fungicide, BAS-3191, 2,5-dimethyl-3furancarboxylic acid anilide in fung,i. Sisken and Newel1 (333) determined residues of the systemic fungicide Carboxin (Vitavax), 5,6-dihydro-2methyl-1,4-oxathiin-3-carboxanilitleand its sulfoxide in seeds. The Vitavax was extracted from seed and oils and the extract cleaned up. The Vitavax was hydrolyzed to liberate aniline in a caustic reducing medium, and the aniline distilled, concentrated, and quantitated by a microcoulometric nitrogen detector.
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Erwin and coworkers (123) determined thiaberdazole residues, a post harvest fungicide, on and in citrus. Norman and coworkers (281) analyzed for resioiies of thiabendazole in citrus. Pease and Holt (289) described a n improved method for the determination of benomyl fungicide. White and Kilgore (388) determined systemic residues of MBC, methyl 2-benzimidazole carbamate, in food crops treated with benomyl fungicide. Zander and Hutzinger (408) described the phosphorimetry of chloro- and nitro-aromatic fungicides. Crosby and Hamadmad (99) studied the photorediiction of pentachlorobenzenes. Ultraviolet irradiation of yli:ntachlorobenzenes in organic solvents resulted primar ly in reductive dechlorination. Benson and coworkers (34) proposed a structure fca. the fungicide, ethylene thiuram monosulfide. Baker and Flaherty (20) described the simultaneous determination of Folpet, Captan, and Captafol in selixted fruits by GLC. After extraction into acetonitrile, hese fungicides were extracted into diethyl ether-heixne, subjected to column chromatography on silica gel and quantitated by electron capture GLC. Tomizawa and Usesugi (365) studied the metabolis 11 of the organophosphorus fungicide Kitazin P, S-benzy I 0diisopropyl phosphorothioate in the mycelial cells of 1 ice blast fungus. Uesugi and Tomizawa (367) studied the metabolisrri of the organophosphorus fungicide, Inezin, S-benzyl 0-ethyl phenylphosphonothioate in the mycelial cells of rice blast fungus. Soeda and coworkers (341) studied the fate of thiopkmate-methyl fungicide, dimethyl 4,4'-o-phenylenebi:;(3thioallophate) and its metabolites on plant leaves iknd glass plates using a radiolabeled compound. Smyth (338) described a procedure for the detectior of the fungicide hexachlorobenzene residues in dairy pr iducts, meat, fat, and eggs. A GLC column containink: a mixture of DC-200 and QF1 and an electron capture detector were used for this analysis. Rangaswamy and coworkers (298) described a new colorimetric method for the estimation of zineb. The zincb was reacted with cupric acetate in HC1. The copper s,ilt formed was measured a t 370 nm. Ghezzo and Magos (140) described an application of the carbon disulfide evolution method for the differentiation of bisdithiocarbamates from methyl-dithiocarbamatc 5 . The method is based on the use of either sulfuric or acetic acid as the hydrolyzing agent. Keppel (199) described a collaborative study of the dztermination of dithiocarbamate residues by a modific tl carbon disulfide evolution method. Howard and Yip (175) studied the stability of meta1l.c ethylene bisdithiocarbamates in chopped kale. Newsome (280) determined ethylenethiourea residues i ti apples in the 0.01- to 1-ppm range with an overall recocery of 94.7 5.9%. The procedure involved conversion t l the S-benzyl derivative followed by extraction, trifluoracetylation and quantitation by electron capture GLC. Onley and Yip (282) determined ethylene thiourea re&. dues in foods by TLC and GLC. This compound is a pos. sible metabolite of metallic ethylene bisdithiocarbamates. Yip and coworkers (404) determined residues of manel: and ethylene thiourea on field-sprayed lettuce and kale. v.Bruchhausen and Drandarevski (59) studied the transport of the systemic fungicide Cela W-524, N,N'-bis(1formamido-2,2,2-trichloroethyl)-piperazine in barley plants. plants. 162 R * ANALYTICAL CHEMISTRY, VOL. 45,
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Rhodes and coworkers (303) studied the fate of I4C labeled chloroneb 1,4-dichloro-2,5-dimethoxybenzenein plants and soils. Rhodes and Pease (302) studied the fate of chloroneb in animals. Daniel and Monks (101) studied the metabolism of the systemic fungicide dimethirimol, (Milcurb), 2-dimethylamino-4-hydroxy- 5-n-butyl-6-methylpyrimidine. Di Muccio and coworkers (108) described the GLC separation of the fungicide hexachlorobenzene and isomers of hexachlorocyclohexane. Collins and coworkers (91) identified hexachlorobenzene (HCB) fungicide residue by GLC analysis. Von Stryk (376) described the separation and determination of some systemic fungicides and their metabolites by TLC analysis.
ACARICIDES A number of articles were published on the analysis of acaricides. Ercegovich and coworkers (121) described an improved GLC method for the analysis of NC-2983, 5,6-dichloro-2trifluoromethylbenzimidazole in soil. This chemical is the major degradation product in soil of the acaricide fenazaflor. The NC-2983 was extracted with a mixture of methylene chloride and isopropyl alcohol. The interfering soil materials were removed by alkaline saline washing of the organic phase. Electron capture GLC employing a 3% OV 17 column was used for quantitation. Santi and coworkers (324) described the spectrophotofluorometric determination of fluenethyl, 2-fluoroethyl-4biphenylacetate in some fruits. The acaricide is extracted with methylene chloride and cleaned up by liquid-liquid partitioning and TLC. The compound was then hydrolyzed and determined spectrophotofluorometrically. As little as 1ppb could be determined. Bazzi and coworkers (27) described a GLC procedure for the determination of fluenethyl in/on apples and pears. The samples were extracted with acetone, and the extract was purified by means of solvent partition and by column chromatography. The purified fluenethyl was brominated and the derivative determined by GLC using an electron capture detector. Westlake and coworkers (384) studied the persistence of omite residues on and in oranges and lemons and in laboratory-processed citrus pulp cattle feed. Devine and Sisken (104) described the use of the flame photometric detector for the determination of omite residues in various crops. Crofts and coworkers (96) determined residues of the acaricide fenazaflor, 5,6-dichloro-l-phenoxycarbonyl-2trifluoromethylbenzinidazole and its major metabolites in apples and pears. Crofts and coworkers (97) described a procedure for analyzing fenazaflor and its hydrolysis product separately. Getzendaner and Corbin (139) described the residue analysis of apples and pears sprayed with Plictran. The samples were analyzed for total and organic tin. The comprehensive study should be of interest to analysts involved in the analysis of Plictran residues. Thomas and Tann (358) determined triphenyltin residue in potatoes by a colorimetric procedure. Knowles (202) studied the metabolism of two acaricidal chemicals, chlorphenamidine, Nt-(4-chloro-o- tolyl)-N,Ndimethylformamidine and formetanate, rn-([(dimethylamino) methylene]amino\phenyl methylcarbamate in mammals. Black and coworkers (49) described a new gas chroma-
5 , APRIL 1973
tographic method for the analysis of Kelthane and its minor impurities. The separation was made on a 6-ft glass column packed with 3% Oronite Polybutene 128 on GasChrom Q using temperature programming from 135 to 205 "C. Retention time data for all known components of Kelthane Technical were reported. Kellner and coworkers (197) studied the absorption, distribution, and excretion of the 14C labeled acaricide Hoe 2910 following oral application to milk-producing ruminants and dermal applications to a calf.
MISCELLANY In this review miscellaneous pesticides which were difficult to classify and miscellany were combined in one section. Johnson (190), a general referee for the AOAC, reported on multiresidue methods. Corneliussen (93), a general referee for the AOAC, reported on multiresidue methods. Yip (401), a general referee for the AOAC, reported on herbicides, plant growth regulators, and fungicides. Storherr (352) a general referee for the AOAC, reported on carbamate pesticides, fumigants, and miscellaneous pesticides. Abbott ( I ) discussed the fifth meeting of the IUPAC Commission on the development, improvement, and standardization of methods of pesticide residue analysis. Hill (169) discussed the fifth meeting of the IUPAC Commission on terminal residues. Carmen and coworkers (70) studied potential residue problems associated with low volume sprays on citrus in California. Murano (271) described the gas chromatographic separation and determination of optical isomers of chrysanthemic acid. The diastereoisomeric esters of chrysanthemic acid with I-menthol were separated on a column of 2% QF-1 coated on Chromosorb W. d-trans, 1-trans and dlcis chrysanthemic acids were resolved but d-cis and 1-cis were not separable from one another on any other column tested. Murano and coworkers (272) determined furamethrin, 5-propargyl-2-furymethyl dl-cis, trans-chrysanthemate by GLC. Murano and Nagase (274) quantitatively determined a new synthetic pyrethroid, furamethrin. Murano and coworkers (273) determined Resmethrin, 5-benzyl-3-furylmethyl-dl-cis,transchrysanthemate by colorimetry, UV spectrophotometry after TLC separation, and GLC. Albro and coworkers (6) described the purification and characterization of the pesticidal synergist, piperonyl butoxide by Florisil column chromatography, TLC and GLC. Secreast and Coil (322) described a sensitive chromatographic-colorimetric procedure for determining piperonyl butoxide residues in flour. McMillan and coworkers (247) determined residues of streptomycin on field grown tomatoes. A biological assay procedure was used for residue analysis. Bull and coworkers (61) determined the components of synthetic boll weevil sex pheromone by gas chromatography. Peterson (290) described a microanalytical method for 4-aminopyridine, used as a bird toxicant, in corn plant tissues. Coggins and coworkers (88) described disappearance and residue studies of naphthaleneacetic acid in citrus. Analysis was by a spectrophotofluorometric procedure.
Gutenmann and Lisk (158) described metaboli'c studies with Bexide, diethyldithiobis( thionoforme.te). Aue and Hill (18) described a tin-smsitive hydrogen flame detector that could be used for the quantitation of tin-containing insecticides. Tjan and Konter (364) described a ga!i chromatographic method for Morestan, 6-methyl-2,3-quinoxaline dithiol cyclic carbonate, residues in plants. Lopez-Roman and coworkers (232) de1,ermined the sorption of the fumigant hydrogen cyanide in mature lemons and oranges by gas chromatography using an electrolytic conductivity nitrogen detector cell. Kossmann and coworkers (205) described a specific determination of chlorphenamidine, N'-(4-chloro-o-tolyl)N,N-dimethylformamidine in plants aiid soil material by colorimetry and thin-layer and electron capture gas chromatography. Geissbuhler and coworkers (136) reported on the total residues of chlorphenamidine in plant ;ind soil material by colorimetry and thin-layer and electron capture gas chromatography. These two articles present a very comprehensive description of the analytical methods for chlorphenamidine. Ercegovich and coworkers (120) studied the disappearance of chlorphenamidine from six major fruit crops. Heuser and Scudamore (167) selectively determined ionized bromide and organic bromides in foodstuffs by gas-liquid chromatography. Special reference was made to fumigant residues. Rajzman and Heller (297) determined the fate of sodium-2-phenate and biphenyl applicd to citrus fruit in wax coatings. Robinson and Hilton (304) developed a rapid, sensitive, and specific gas chromatographic method for the analysis of traces of phosphine. Rauscher and coworkers (301) studied the sorption and recovery of phosphine added to cereal products. Scudamore and Heuser (321) determined residues of ethylene oxide and its persistent reaction products in wheat flour and other commodities. Analysis was by extraction followed by GLC. Karasz and Gantenbein (193) determined D-D, cis- and trans-1,3-dichloro-l-propeneand 1,2-dichloropropane in potatoes using a microcoulometric gas chromatographic technique. McMahon (246) described the analysis of commercially fumigated grains for residues of orzanic fumigants. Residues were isolated by an acid reflux procedure and determined by GLC. LITERATURE CITED (1) Abbott, D. C., J. Ass. OfficeAnal. Chem., 54, 1332 (1971). (2) Addison, R. F., Fletcher, G. L., Ray S.,Doane, J., Bull. Environ. Contam. Toxicol., 8, 52 (1972). (3) Adler, I . L., Gordon, C. F., Haines, L. D., Wargo. J. P., Jr., J. Ass. Offic. Anal. Chem., 55, 802 (1972). (4) Adler, I. L., Lindwood, D. H. Wa,go, J. P., Jr., J. Agr. Food Chem., 20, 1233 (1972). (5) Albro, P. W., Fishbein, L.,J. Chroma'ogr., 69,273 (1972). (6) Albro, P. W.. Fishbein, L., Fawkes, J , ibid., 65, 521 (1972). (7) Andrawes. N. R., Bagley, W. P., Herrett, R. A,, J. Agr. Food Chem., 19,727(1971). (8) /hid., p 731. (9) Andrawes, N . R., Chancey, E. L.,'Crabtree, R . J., Herrett, R. A,, Weiden, M . H . J.. ibid., 20, 608 (1972). (IO) Antoine, O., Mees, G., J. Chromatcigr., 58, 247 (1971). (11) Archer, T. E., Nazer, I. K., Croshy, 0 . G., J. Agr. Food Cbem., 20,954 (1972). (12) Argauer, R. J., Webb, R. E., ibid., I) 732. (13) Armour, J. A., J. Cbromatogr., 72,275 (1972).
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