(628) Zola, A., Le Vanda, J. P., Parfums, Cosmet., Aromes, 7,31,39 (1976); Chem. Abstr., 85,51618~ (1976). (629) Zola, A., Le Vanda, J. P., Riv. ltal. Essenze, Profumi, Piante Off., Aromi, Saponi, Cosmet., Aerosol, 57(8), 467 (1975); Chem. Abstr., 84,
49722k (1976). (630) Zotov, E. P., Goryaev, M. I., Sharipova, F. S.,Khazanovich, R. L., Vandysheva, V. I., Khim. Prir. Soedin., 10(1), 101 (1974); Chem. Abstr., 81, 54278n (1974). (631) Zuercher, K., Hadorn, H., Strack, Ch., Mitt.
Geb. Lebensmittelunters. Hyg., 65(4), 440 (1974): Chem. Abstr., 84, 42157w (1976). (632) Zutshi, S. K., Bamboria, B. K., Bokadia, M. M., Curr. Sci., 44(16), 571 (1975); Chem. Abstr., 84, 35175x (1976).
Pesticide Residues Wayne Thornburg Del Monte Corporation Research Center, Walnut Creek, Calif. 94598
This selective review presents the developments in pesticide methodology covering the period from December 1974 through November 1976. Papers selected for this review were ublished in journals which are readily available in major liraries. This interval has seen the introduction and acceptance of new automated instrumentation, including automated gas chromatographs and computer controlled systems. This review follows the general format and pesticide nomenclature used in the 1975 biennial review of Thornburg (366). Frear’s “Pesticide Index” (124)lists the common, trade, and chemical names of many pesticides, and the author has tried to use names found therein. Common names that appear in the Environmental Protection Agency tolerance regulations have been used where possible. Another useful publication edited by Shepard (334)is the “1976 Pesticide Dictionary” 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. “Residue Reviews,” under the editorship of Gunther ( l 4 2 ) , continues to be an excellent source of information on pesticide methodology. A total of 62 volumes has now been published. Preston and Bowman (304)authored “Pesticide Residues by Chromatographic Methods, Reprints of Selected Articles” which is a collection of 65 articles reprinted from past issues of the Journal of Chromatographic Science. The ACS published a symposium on “Bound and Conjugated Pesticide Residues”, ACS Symposium Series 29 ( 1 ) . This review period has been characterized by improvements and automation of instrumentation with increased reliability. Karlhuber and Eberle (200) discussed advances toward automation of pesticide residue determinations. These authors noted that only slow progress is observed in automation of pesticide residue determinations. This publication discusses the automated or semi-automated systems that are in current use. Hess and co-workers (155)described an automated system for the analysis of nitro compounds in water using a Technicon Instruments AutoAnalyzer I. McLeod (248) described systems for automated multiple pesticide residue analysis. This author notes that it is not yet possible to completely integrate all steps in a multiresidue method into a fully automated configuration. Cleanup of sample extracts, concentration, and transfer of cleaned-up extracts are steps that are difficult to automate. Johnson and co-workers (193) described an automated gel permeation chromatographic cleanup of animal and plant extracts for pesticide residue determination. Elution characteristics using Bio-Beads SX-3 gel and a toluene-ethyl acetate (1 3) elution solvent were determined for 16 nonionic chlorinated pesticides, 3 PCR’s, 14 chlorophenoxy herbicide esters, and seven organophosphate insecticides. High performance liquid chromatography (HPLC) has become an important tool in analytical chemistry; however, the availability of suitable detectors for pesticide and other trace analysis, generally has lagged behind development in column packings and other equipment.
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Moye (270) reviewed the use of HPLC for the analysis of pesticides. I t was the intent of this article to provide a comprehensive review of pesticide related applications, suggest better utilization of existing columns, and describe approaches which could lead to practical analytical methods. Self and co-workers (331) discussed HPLC and its application to pesticide analysis. Julin and co-workers (198) described a selective flame emission detection of phosphorus and sulfur by HPLC. The instrument described in this article was custom built, but the technique should be applicable to detection of pesticides in HPLC eluates. Sampling, sample preparation, extraction, and cleanup of the extracts are still a very important part of successful pesticide analysis. A number of solvents and reagents, especially purified for pesticide analysis, are available and their use is highly recommended. Ford and co-workers (120) reviewed the sampling and analysis of pesticides in the environment. Lea (232)described a separation of pesticide residues from lipids prior to GLC analysis. Lipids were separated from dieldrin, endrin, and p,p’-DDE residues by saponification with ethanolic sodium hydroxide, acidification with dilute sulfuric acid, and adsorption chromatography on deactivated alumina, using petroleum ether as the eluant. This system will be successful only with pesticides that are stable to saponification. Dale and Miles ( 7 9 )described a simple partition chromatographic separation of pesticide residues from fats. The procedure used acetonitrile on a Florisil column. The fat was washed from the column with hexane and discarded. The pesticides were then eluted from the column with acetone. The efficiency of the cleanup column was between 97 and 100%. Kovac and co-workers (217) described the cleanup of extracts for pesticide analysis using the sweep codistillation method. Luke and co-workers (244) described an extraction and cleanup of or anochlorine, organophosphate, organonitrogen, and hydrocarion pesticides in produce, for determination by GLC. Leoni and co-workers (234)described preliminary results on the use of Tenax for the extraction of pesticides and polynuclear aromatic hydrocarbons from surfaces and drinking water. Tenax is a porous polymer based on 2,6-diphenyl-pphenylene oxide and appeared to be very satisfactory for the extraction of pesticides. Gunther and co-workers (143) described sampling and processing techniques for determining dislodgable pesticide residues on leaf surfaces. Popendorf and co-workers (303) presented a technique for collecting foliar dust samples that can be correlated to the fraction of pesticide residue which becomes airborne because of the activities of workers. Kearney and Kontson (204)described a simple system to simultaneously measure volatilization from and metabolism of pesticides in soils. Cochrane (67)described the confirmation of insecticide and herbicide residues by chemical derivatization. Finsterwalder (116)described a collaborative study of an extension of the Mills et al. method for the determination of pesticide residues in foods.
Wayne Thornburg is Associate Director, Chemistry, for the Del Monte Corporation. He received his BS from the University of California in 1943. His research interests include pesticide residue analytical methods, analysis of pesticides in food products, and nutritive analysis of foods. He has authored as well as coauthored several papers on paper chromatography, electrophoresis, and pesticide residue analysis. He is a member of the American Chemical Society.
MacNeil and Frei (253) reviewed the quantitative thinlayer chromatography (TLC) of pesticides. Surette and Mallet (357) described a method for the detection and quantification of pesticides on silica gel chromatograms by in situ fluorometry. Caissie and Mallet (54)described a fluorometric detection of pesticides on aluminum oxide layers. Matsumura (260)published a comprehensive survey of the toxicology of insecticides. This work critically reviews such topics as metabolism in animals, plants, and microorganisms. Zehner and Simonaitis (40Ei)described a procedure for the elimination of some integration errors in pesticide residue analysis. Nicholas and co-workers (283) recorded the reference Raman spectra of eleven miscellaneous pesticides. GAS CHROMATOGRAPHY Gas chromatography (GLC) and mass spectrometry (MS), continue to be the most satisfactory procedure for the separation, identification, and quantitation of pesticides and their metabolites. During the past two years, there has been a rapid trend to automation. Automatic sample injectors allow unattended operation and automatic data reduction systems provide quantitative results more rapidly and with greater precision and accuracy than manual techniques. Advances in MOS/LSI technology and microelectronic circuitry have led to the development of a number of practical, low cost, computing integrators which have provided computer-level performance a t a cost affordable by most laboratories. Gill (136) estimates that over 50% of the analytical results in quantitative GLC analyses are computed automatically, using an electronic integrator or a computer-based data reduction system. Fortunately most of this type of equipment can be added to existing chromatographs and has proved to be both time- and labor-saving in the author’s laboratory. Sev6ik (333)authored “Detectors in Gas Chromatography”. This book is not specifically about pesticides but contains information of the function and optimization of so-called specific detectors used for pesticide analysis. Thompson and co-workers (365)published relative retention ratios of 95 common pesticides and metabolites on nine GLC columns over a temperature range of 170 to 204 “C using an electron capture and a flame photometric detector. This article is of great importance to anyone working in the field of GLC pesticide analysis. Kapila and Aue (199)studied the effect of pressure on the response of a dc electron capture detector. McLeod and co-workers (249)described a GLC system with flame ionization, phosphorus, sulfur, nitrogen, and electron capture detectors operating simultaneously for pesticide residue analysis. Aue (19)discussed detectors used in GLC analysis of pesticides. Poole (301)studied the temperature dependence of electron capture response. Poole (302)discussed the operation of the electron capture detector for gas chromatography. Burgett and Clouser (45)described a processor-controlled electron capture detector for gas chromatography. Combining the electron capture detector with a processor-controlled
chromatograph resulted in a system with increased sensitivity, increased dynamic range, improved baseline stability, and dual compensation temperature programming. Hoodless and co-workers (172) reported on the sulfur response of the AFID detector. Moye (271)described the plasma chromatography of pesticides. Wilson and Cochrane (385)compared the Coulson and Hall electrolytic conductivity detectors for the determination of nitrogen-containing pesticides. These authors found that the Hall detector had about seven times the sensitivity of the Coulson detector. Lawrence and Sen (231) described a simple water flow control for the Coulson electrolytic conductivity detector. The approach of this technique was to decrease water flow by reducing the effective volume of the capillary tubing leading to the mixing chamber by inserting a fine stainless steel wire into the capillary. The thermionic detector first described in detail by Giuffrida (137) in 1964 has been used for the detection of organophosphorus compounds. It was later found to be useful for the detection of organonitrogen compounds. However, it lacked sensitivity. Currently a number of improvements are being made by several equipment manufacturers to dramatically increase its selectivity and sensitivity. Verga and Poy (374) described a GLC procedure for the quantification of nitrogen- and phosphorus-containing compounds using a new, high sensitivity detector. This new detector works on the principle of thermionic detection, showing high sensitivity toward phosphorus- and nitrogencontaining molecules. Mellor (262) described the selective detection of phosphorus, nitrogen, and sulfur compounds using a tuned commercial thermionic detector. Brazhnikov and Schmidel (36)reported on the mechanism of the selective sensitivity of the thermionic ionization detector for the analysis of phosphorus- and nitrogen-containing organic compounds. Chamberlain (57) described a simple method for rapid thermionic detector optimization. VanderVelde and Ryan (369)discussed gas chromatography-mass spectrometry as applied to pesticide analysis. Karlhuber and co-workers (201)described pesticide residue analysis by mass fragmentography. Using multiple ion monitoring, confirmation of a compound was achieved by the gas characteristic ion fragments of the compound, and by the ratio of the intensities of the fragments. Veith and co-workers (373)described a preparative method for gas chromatographic/mass spectral analysis of trace quantities of pesticides in fish tissue. CHLORINATED PESTICIDES General Procedure. During this two-year period, increasing efforts have been made to restrict the manufacture, distribution, and use of chlorinated pesticides. Since these pesticides and their metabolites and photodegradation products remain in ecosystem, interest in these compounds continues. Burke (46,47),a general referee for the AOAC, reported on chlorinated pesticides. Holloman and co-workers (163) studied the thermal degradation of selected chlorinated pesticides. Oller and Cranmer (290) reviewed the analysis of chlorinated insecticides. Musty and Nickless (272) described two extractants for organochlorine insecticides and polychlorinated biphenyls from water. Dolphin and co-workers (89) described a system for the analysis of organochloric pesticides in milk by HPLC. Sample cleanup, separation of the pesticides from milk fat, and quantification of both fat and pesticides were carried out on-column using column switching and back-flushing techniques. The combination of HPLC with electron capture detection resulted in a detection limit of about 0.1 ppm pesticide in milk fat. Peterson and co-workers (299) described a simplified extraction and cleanup for determining organochlorine pesticides in small biological samples. Erney (104)made a feasibility study of miniature Florisil columns for the separation of some chlorinated pesticides. ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
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Suzuki and co-workers (358) reported on gas chromatographic resolution of organochlorine insecticides on OV-l/ OV-17, OV-210/0V-17, and OV-225/0V-17 mixed phase systems. Onuska and Comba (295)described the GLC identification of some organochlorine pesticides and their photoalteration products by means of Kovats retention indices. Onley and co-workers (292) measured residues in broiler chick tissue from low level feedings of seven chlorinated hydrocarbon insecticides. Yamato and co-workers (392)studied the GLC resolution of organochlorine insecticides on mixed phase systems, OVl/OV-25,0V-210/0V-25, and OV-225/OV-25 systems. Specific Procedures. Cochrane and co-workers (69) described the GLC determination of technical chlordane residues in food crops. It was concluded that the total area under the chromatogram of the sample be compared with the total area under the chromatogram of a technical chlordane standard to be the best method of quantitation. Onuska and Comba (293) described the isolation and characterization of the photoalteration products of cis- and t runs- chlordane. Lu and co-workers (242) reported on the environmental distribution and fate of hexachlorocyclopentadiene, chlordene, heptachlor, and heptachlor epoxide in a laboratory model ecosystem. Cochrane and co-workers (70) described the structural elucidation of the chlorodene isomer constituents of technical chlordane. Juengst, Jr. and Alexander (197)reported on the conversion of DDT to water-soluble products by microorganisms. Forty-three percent of the bacteria isolated from seawater and marine sediments converted between 5 and 10% of the DDT supplied in vitro to water-soluble products. Nicholas and co-workers (281)recorded the Raman spectra of DDT and five structurally related pesticides and five pesticides containing the norbornene group. El Zorgani (101)determined residues of DDT in cottonseed after spraying with DDT. The DDT was extracted from cottonseed in a Soxhlet extractor using hexane-acetone and the extract cleaned up by TLC. Quantitation was by GLC using a ‘j3Ni detector. Beland and co-workers (22)studied the anaerobic degradation of TDE. Hearnsberger and co-workers (153)reported on degradation of DDT in beef by canning and cooking. Woods and Akhtar (389) studied radiation-induced dechlorination of chloral hydrate and DDT. Aitzetmuller ( 7 ) described the adsorption liquid chromatography of DDT and polychlorinated biphenyls. Feil and co-workers (112) reported on the metabolism of o,p’-DDT in chickens using o,p’-DDT-ring- U- 14C compound. A number of metabolites were isolated. A significant species difference was found in the metabolism of o,p’- DDT; chickens metabolized o,p’-DDT to four DDE-type compounds, whereas rats did not. Johnson and co-workers (194) reported on the effects of freeze-drying on residues of TDE, DDT, and endosulfan in tobacco. Taylor and co-workers (363) studied the volatization of dieldrin and heptachlor from a maize field. Franken and Luyten (123)compared extraction procedures for dieldrin, lindane, and DDT from serum. Hammock and co-workers (147) described the detection and analysis of epoxides with 4-(p-nitrobenzyl)-pyridine. Reddy and Khan (314) studied the fate of photodieldrin under various environmental conditions. Weisgerber and co-workers (380) isolated and identified three unreported p h ~ t o d i e l d r i n - ~metabolites ~c in soil. Reddy and Khan (315) studied the metabolism, excretion, and tissue distribution of (14C)photo-dieldrin in male rabbits, following single oral and intro-peritoneal administration. A number of metabolites were found along with photo-dieldrin. Kathpal and Dewan (202)described an improved clean-up technique for the estimation of endosulfan and endrin residues. Putnam and co-workers (306)identified endosulfan using the products of laboratory photolysls. MacNeil and Hikichi (254)reported on the degradation of 100R
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endosulfan and ethion on pears and pear and grape foliage. Mitchell (267) described a collaborative study of the determination of endosulfan, endosulfan sulfate, tetrasul, and tetradifon residues in fresh fruits and vegetables. Stewart and Cairns (352)measured endosulfan persistence in soil and uptake by potato tubers. Bong (32)determined hexachlorobenzene (HCB) and mirex in fatty products. The fat or oil was distributed on unactivated Florisil, and the HCB and mirex were eluted with acetonitrile. The pesticides were partitioned into petroleum ether and cleaned up with activated Florisil. Quantitation was by GLC using an electron capture detector. Crist and co-workers (78) determined low levels of hexachlorobenzene in adipose tissue using Florisil cleanup and electron capture GLC. Crist and Moseman (77)described the improved recovery of hexachlorobenzene in adipose tissues with a modified micro multiresidue procedure. Yang and co-workers (393)described a GLC method for the analysis of hexachlorobenzene and possible metabolites in monkey fecal samples. Isensee and co-workers (178) studied the persistence and aquatic bioaccumulation potential of hexachlorobenzene. Zepp and co-workers (406) reported on the light-induced decomposition of methoxychlor in aquatic systems. Khera and co-workers (213) studied tissue distribution, tetratogenicity, and dominant lethality of mirex in rats. Holloman and co-workers (164)identified the major thermal degradation products of the insecticide mirex by IR, MS, GLC, and UV data. Ivie and co-workers (187) described the photodecomposition of mirex on silica gel. chromatoplates exposed to natural and artificial light. Holmstead (166) studied the degradation of mirex on an iron(II)-porphyrin model system. Lewis and co-workers (236) described a simple photochemical confirmation of mirex in the presence of PCB’s. Stein and co-workers (351) characterized a mirex metabolite from monkeys. Hallett and co-workers (146) analyzed and confirmed the presence of mirex and photomirex in herring gulls from Lake Ontario. This publication details the separation of mirex and PCB’S. The separation, identification and quantitative determination of polybrominated biphenyls (PBB’s) and polychlorinated biphenyls (PCB’s) and chlorinated pesticides are problems of much current interest. Jacobs and co-workers (191) studied the fate of PBB’s in soil and their uptake by plants. Fehringer (111) described a new procedure for P B B residues in dry animal feeds. Finely ground feed was packed into a chromatographic column containing Celite and then eluted with methylene chloride. The concentrated eluate was cleaned up by elution with petroleum ether through Florisil and quantitation was by GLC using a 63Ni EC detector. Erney (105)described a confirmation procedure for (PBB’s) in feeds and dairy products using an ultraviolet irradiationGLC chromatographic technique. Chromatograms of P B B standards and sample extract solutions showed similar photodecomposition peak patterns dependent on time and intensity of UV irradiation. Ruzo and co-workers (323)studied the photodegradation of PBB’s. Fehringer (110) determined residues of P B B residues in dairy products. Fat was extracted by the AOAC procedure and the PBR’s were separated by gel permeation chromatography. The PBB’s were quantitated by GLC using a 63Ni detector. Gutenmann and Lisk (144)studied the tissue storage and excretion in milk of PBB’s in ruminants. Khan and co-workers (206) evaluated PCB solutions. Erney (103)made a feasibility study of miniature silica gel columns for the separation of some PCB’s, DDT, and analogues. Mattsson and Nygren (261) determined PCB’s and some chlorinated pesticides in sewage sludge using a glass capillary column and an electron capture detector. MacNeil and co-workers (256) examined the UV spectra of 29 chlorobiphenyls. Brinkman and co-workers (37) described the HPLC of PCB’s and related compounds. A system of silica gel-dry n-
hexane was used to characterize the behavior of a series of commercially available mixtures of chlorinated biphenyls. KrupEik and co-workers (219)described the use of capillary GLC and MS in the analysis of PCB’s. Brownrigg and Hornig ( 3 9 ) described a procedure for the determination of PCB and DDT concentrations a t sub-part per billion levels in water. The pesticides were extracted and estimated by luminescence measurement at 77 K. Ahnoff and Josefsson (6) described a clean-up procedure for PCB analysis on river water extracts. Five procedures are listed. Doguchi and Fukano (88) determined residue levels of polychlorinated terphenyls, PCB’s, and DDT in human blood using GLC and mass spectra. Iwata and Gunther (189)studied the translocation of the polychlorinated biphenyl, Archlor 1254 from soil into carrots under field conditions. Hansen and co-workers (149) determined residues of polychlorinated biphenyl components in broiler cockerels receiving two Arochlors in three dietary variations. Yoshimura and Yamamoto (397)studied the excretion of 2,4,3’,4‘-tetrachlorobiphenyl in rats. Safe and co-workers (324) studied the metabolism of chlorobiphenyls in the goat and cow. Ruzo and co-workers (322)described the photodecomposition of unsymmetrical PCB’s. Burse and co-workers (48)studied PCB metabolism in rats following prolonged exposure to Arochlor 1242 and 1016. Maass and co-workers (251) studied the metabolism of 4-chlorobiphenyls by lichens. Ruzo and co-workers (321) studied the metabolism of chlorinated naphthalenes in the pig. Zitko and co-workers (407)described the determination of pentachlorophenols and chlorobiphenylols in biological samples. Sieber and co-workers (330) described the isolation and GLC characterization of some toxaphene components. Column chromatography of toxaphene on activated alumina yielded eight major fractions. Reported toxaphene components were characterized by GLC retention relative to aldrin on packed columns of OV-lOl,OV-17,QF1, and on a capillary open-tubular column of OV-101. Holmstead and co-workers (168) determined the composition of toxaphene by combined gas chromatographychemical ionization mass spectrometry. Turner and co-workers (367) identified the more toxic component A in toxaphene by lH NMR studies as a mixture and 2,2,5of 2,2,5-endo,6-exo,8,8,9,l0-octachlorobornane, endo,6-exo,8,9,9,10-octachlorobornane. Nelson and Matsumura (276)described the separation and comparative toxicity of toxaphene components. Nelson and Matsumura (275) described a simplified approach to studies of toxic toxaphene components. Khalifa and co-workers (205) studied the degradation of toxaphene by iron(I1)-protoporphyrin systems. Ohsawa and co-workers (288) studied the metabolic dechlorination of toxaphene in rats.
ORGANOPHOSPHORUS PESTICIDES General Procedures. This two-year period has seen the continued use of organophosphorus pesticides. The flame photometric phosphorus- and sulfur-specific detectors continue to be the method of choice for quantitation of these compounds. Improvements have been made in the phosphorus-specific thermionic detector that have increased its sensitivity and reliability and made it easier to use. Nicholas and co-workers (282) published the Raman spectra of ten phosphorus-containing pesticides. Eto (108)was the author of “Organophosphate Pesticides: Chemistry and Biochemistry”. McCully (245,246)a general referee for the AOAC reported on phosphated pecticides. Szalontai (360) described the HPLC performance behavior of 23 organophosphorus insecticides on a silica gel column. Forbes and co-workers (119) described the confirmation of organophosphorus insecticides by chemical reaction. A number of techniques are described and they should be very useful when two pesticides have the same retention time and mass spectra equipment is unavailable. Stefanac and co-workers (349)described the quantitative
determination of organophosphorus pesticides by TLC densitometry. Greenhalgh and Kovacicova (138) described a chemical confirmatory test for organophosphorus and carbamate insecticides and triazine and urea herbicides with reactive NH moieties. Aoki and co-workers (11)reported on a comparative study of methods for the extraction of 11 organophosphorus pesticide residues in rice. Burchfield and Storrs (44) described an extraction and clean-up method for the analysis of organophosphorus insecticides and their metabolites. Lindgren and Jansson (240)described the support material effects in gas chromatographic analysis of organophosphorus compounds. Dauzhton and co-workers (811 described the analvsis of phosphYorus-containing hydrolytic products of organophosphorus insecticides in water. Blair and Roderick (29)described an improved method for the determination of urinary dimethyl phosphate. Dimethyl phosphate is a metabolite of some important organophosphate insecticides. Specific Procedures. Lawrence and McLeod (230) described the GLC analysis and chemical confirmation of azodrin residues in strawberries. Stein and Pittman (350)described the GLC determination of azinophos-ethyl, O,O-diethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)-ylmethyl)phosphorodithioate in animal tissue. Wieneke and Steffens (382)reported on the translocation and metabolism of azinoDhos-methvl in bean d a n t s after root and leaf absorption. Liang and Lichtenstein (237)studied the effects of soils and leaf-surfaces on the photodecomposition of 14C azinophosmethyl. Staiff and co-workers (347) measured the persistence of azinophos-methyl in soil. Bull and Ivie (42) studied the metabolism of Bay-NTN 9306, 0 -ethyl 0- [4-(methy1thio)phenyllS-propyl phosphorodithioate, by white rats. Ivie and Bull (185)studied the photodegradation of BayNTN 9306 using a W-labeled compound. Ivie and co-workers (186) studied the metabolic fate of Bay-NTN 9306 in a lactating cow. Bull and co-workers (43)studied the fate of Bay-NTN 9306 in cotton plants and soil. Zakrevsky and Mallet (403) determined Bayrusil, 0,Odiethyl-o-(2-quinoxalyl)phosphorothionate,on TLC plates using fluorometry. Luke and Dah1 (243) detected two organophosphorus residues in meat resulting from the use of bromophos and chlorpyriphos. Williams (384)studied the persistence of chlorfenvinphos in soils. McKellar and co-workers (247) determined residues of chlorpyrifos, its oxygen analogue, and 3,5,6-trichloro-2-pyridol in milk and cream from cows fed chlorpyriphos. Lueck and co-workers (235)determined residues of chlorpyrifos-methyl, 0,O- dimethyl 0-(3,5,6-trichloro-2-pyridyl) phosphorothioate and its 0 analogue and pyridinol h drolysis product in coastal bermuda grass and forage corn. 4esidues of the parent compound and its 0 analogue were analyzed by GLC using a phosphorus-sensitive flame photometric detector. The pyridinol was analyzed as the trimethylsilyl derivative using electron capture GLC. Gifkins and Jacobson (133) determined the crystal and molecular structure of the organophosphorus insecticide Coroxon, 0,O-diethyl-0-(3-chloro-4-methyl-2-oxo-(2H)-1benzopyran-7-y1)phosphate. Zakrevsky and Mallet (404) determined Coumaphos, 0 , O - diethyl 0-(3-chloro-4-methyl-2-oxo-(2H1 -benzopyran-7-yl)phosphorothioate, and its oxygen analogue in eggs by in situ fluorometry. Volpe and Mallet (376)identified metabolites of Coumaphos and some related compounds in water by heat induced fluorescence. Harned and Casida (150)studied the metabolites, photoproducts, and oxidative degradation products of Delnav, 2,3-p-dioxanedithiol-S,S-bis (0,O-diethy1)phosphorodithioate acaricide and insecticide. ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
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Iverson and co-workers (180)studied the diazinon metabfinity, reactivity, and overall potency for acetylcholinesterolism in the dog. ase. Holmstead and Casida (167) reported on the chemical Machin and co-workers (252) studied the hepatic metabolism of diazinon in a number of animals. ionization mass spectra with methane as the reagent gas was Sarna and co-workers (326)described the quantitative GLC reported for 25 N-methylcarbarnate insecticides, some of their analysis of dimethoate and several metabolites in rape, quail, metabolites and related compounds. and grasshopper tissues by derivatization. Moye (269)described the preparation of esters of sulfonic MacNeil and co-workers (255) studied the persistence of acids as derivatives for the GLC analysis of carbamate pestidimethoate and dimethoxon on cherries. cides. The esters were easily prepared by reacting benzene Ivey and Mann (182)determined ethion, ethion monooxon, sulfonyl chloride with carbamate pesticides. The sulfonates and ethion dioxon in tissues of turkeys and cattle using a gas were gas chromatographed and detected by a tritium detector chromatograph equipped with a flame photometric deteca t the 1-pg level. A sensitivity of 0.06 ppm was achieved. tor. Coburn and co-workers (66) described the analysis of N Ivey (181)determined residues of famphur, 0,O-dimethyl methylcarbamates in natural water and soil by chemical 0-( p -(dimethyl-sulfamoy1)phenyl)phosphorothioate and its derivatization. Holden (162) described a collaborative study of the 2,4oxygen analogue in reindeer and cattle tissue. With extraction and cleanup, 0.025 ppm famphur and 0.06 ppm oxygen anadinitrophenyl ether multiresidue method for use in deterlogue could be detected in body tissues. mining four carbamate pesticides in crops. Yule and Varty (402) studied the persistence and fate of Lawrence (227) described a procedure for the analysis of fenitrothion 0,0-dimethyl-0-(4-nitro-rn-tolyl)phosphoro- some carbamate insecticides by the formation of the heptathioate in a forest environment. fluorobutyryl derivatives. The reaction makes use of heptaGreenhalgh and Marshall (139)studied the ultraviolet irfluorobutyric anhydride with trimethylamine in benzene as radiation of fenitrothion. a catalyst. Quantitation was by GLC using a Coulson conIvey and Oehler (183) determined iodofenphos, 0-(2,5- ductivity detector in the reductive mode. Specific Procedures. Jones (195)studied the metabolism dichloro-4-iodophenyl)-O,O-dimethyl phosphorothioate and of aldicarb by five soil fungi. several related compounds in tissues and urine of cattle. Lin and co-workers (238) studied the metabolism of carBraun and co-workers (35)determined residues of leptobaryl in human embryonic lung cell cultures. phos and its metabolites following application to various crop Pretanik and Childs (305)studied the degradation of carplants. baryl following thermal processing. Cook and Moore (71) determined malathion and its meBlevins and Dunn (30)reported on the effects of carbaryl tabolites in fish, oyster, and shrimp tissue. and dieldrin on the growth, protein content, and phospholipid Wolfe and co-workers (386) studied the kinetics of malacontent of HeLa cells. thion degradation in water. Mirer and co-workers (266)compared GLC and anti-choAddison and co-workers ( 2 )studied the photochemistry of linesterase methods for measuring parathion metabolism in the carbamates, carbaryl and Phenmec, phenyl-N-methyl vitro. carbamate in aerated and degassed solutions. Suzuki and Uchiyama (359)studied the pathway of nitro Guirguis and Brindley (141) studied the carbaryl penetration into and metabolism by alfalfa leaf-cutting bees. reduction of parathion by spinach homogenate. Ernst and co-workers (107)developed a TLC and indirect Archer (13)studied the dissipation of parathion and related GLC determination of carbaryl, Mesurol, and propoxur. compounds from field-sprayed lettuce. Sikka and co-workers (339) studied the degradation of Archer (12)reported on the dissipation of parathion and carbaryl and 1-naphthol by marine organisms. related compounds from field-sprayed spinach. Bollag and co-workers (31) described the bacterial meKumar and co-workers (220) described the TLC of paratabolism of 1-naphthol. thion as paraoxon with cholinesterase inhibition detection. Wong and Fisher (388)determined carbofuran and its toxic Kliger and Yaron (216) studied parathion recovery from metabolites in animal tissue by GLC of their N-trifluoacetyl soil after a short contact period. Kishk and co-workers (215)reported on the hydrolysis of derivatives using an electron capture detector. Finlayson and co-workers (115)reported on the distribution methyl-parathion in soils. of carbofuran, ethion, and phorate in carrots grown in muck Brown (38)described an improved GLC procedure for the soil treated with these insecticides. determination of residues of phorate and its principal meArcher (14)studied the effects of light on the fate of cartabolites. bofuran during the drying of alfalfa. Manson and Meloan (258)studied the degradation prodRangaswamy and co-workers (313) described a sim le ucts of Phoxim, Bayer 77488, glyoxylonitrile phenyl oxime spectrophotometric method for the determination of carlo0,O-diethyl phosphorothioate on stored wheat. Two exfuran residues. tractable products were formed-the oxygen analogue and Nye and co-workers (285)determined the fate of Croneton, the S-ethyl isomer. 2-ethyl-thiomethylphenyl-N-methylcarbamate in the rat Wright (391) described a simple method for the determiusing I4C-labeled compounds. nation of ronnel and its oxygen analogue in eggs. Greenhalgh and co-workers (140) described the GLC Roberts and Stoydin (318)studied the degradation of SD analysis of Mesurol, 4-methyl-thio-3,5-xylyl-N-methylcar8280, 2-chloro-l-(2,4-dichlorophenyl)vinyldimethyl phosbamate, its sulfoxide, sulfone, and phenol analogues. phate following its application to rice. Krieger and co-workers (218) studied the absorption and Dejonckheere and Kips (83) studied the photodecompometabolism of the selective insecticide PSC, 2,2-dimethylsition of Supracide. 2,3-dihydrobenzofuranyl-7-N -dimethoxyphosphinothioylSellers and co-workers (332) determined residues of N-methylcarbamate in bean plants. Terbufos, 0 , O - diethyl-S- [ ( t e r t -butylthio)methyl] phosFrancoeur and Mallet (122)determined Quinomethionate, phorothioate in field corn, sweet corn, popcorn, and soil. 6 methylquinoline-2,3-diyldithiocarbamate, Morestan, resiTerbufos was quantitated by GLC using an alkali flame iondues in crops by TLC fluorometry. ization detector. Chin and co-workers (62)measured residues of thionofax, 3,3-dimethyl-l-(methylthio)-2-butanone-0-[(methylamiCARBAMATES no) -carbonyl]oxime in potatoes. Holm and co-workers (165) studied the metabolism of General Procedures. Storherr (354,355),a general referee thionofax in cotton plants using 35S-or 14C-labeled comfor the AOAC, reported on carbamate pesticides, fumigants, pounds. and miscellaneous. Chin and co-workers (63)described the GLC determination Dorough and Thorstenson (92)discussed the analysis for of thionofax in soil plants and water. carbamate insecticides and metabolites. An extensive bibliography is included. Hetnarski and O’Brien (156)studied 23 methyl carbamates HERBICIDES and the effects of variations in their hydrophobicity and Interest in herbicides during this two-year period continued ability to form charge-transfer complexes and upon their af102 R
ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
a t a high level. Herbicides belong to many classes of compounds and the reviewer has segregated, where possible, the reviewed articles according to type of herbicide. Chau and Terry (59) described a new procedure for the formation of 2-chloroethyl esters of ten herbicidal acids. Eberle and Gerber (98) made comparative studies of instrumental and bioassay methods for the analysis of herbicide residues. Lawrence (226)described the GLC separation of herbicides of major interest in Canada, with electrolytic conductivity detection in the nitrogen and chlorine modes. Chau and Terry (60)described the GLC characteristics and conditions for the formation of pentafluorobenzyl derivatives of ten herbicidal acids. Lawrence (223) reported on the confirmation of some organonitrogen herbicides and fungicides by chemical derivatization and gas chromatography. Buchert and Ldkke (41)described the gas chromatographic mass spectrometric identification of phenylurea herbicides after N-methylation. Lawrence (225) described an HPLC procedure for the analysis of urea herbicides in foods. Hsu and Bartha (174) studied hydrolyzable and nonhydrolyzable 2,3-dichloroaniline-humus complexes and their respective rates of biodegradation. A 190-day laboratory experiment with radiolabeled 3,4-dichloroaniline demonstrated that the hydrolyzable portion of the humus-bound residue declines with time while the nonhydrolyzable portion does not. Lawrence (224) evaluated an alkylation-GLC procedure for the determination of carbamate and urea herbicides in foods. Lawrence and Laver (228)described the analysis of some carbamate and urea herbicides in foods by GLC after alkylation. The compounds were extracted with ethanol and partitioned between water and chloroform. The organic extract was evaporated to dryness and alkylated with sodium hydridemethyl iodide. Polychlorinated Dibenzo-p-dioxins (PCDD’s). Chlorinated phenols are used as starting materials for a series of agricultural chemicals, especially chlorophenoxy herbicides. Many have been shown to contain polychlorinated dibenzop -dioxins (PCDD’s). These highly toxic PCDD’s are produced from chlorinated phenols a t high temperatures under alkaline conditions during the manufacturing process. For example, in the extremely toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin 2,4,5-trichlorophenol (117),and in 2,4,5T herbicides (51). Villanueva and co-workers (375) compared analytical methods for chlorodibenzo-p-dioxins in pentachlorophenol. Buser (49) described the analysis of polychlorinated dibenzo-p -dioxins and dibenzofurans in chlorinated phenols by mass fragmentography. Buser (50) described the separation and identification of isomers of polychlorinated dibenzo-p -dioxins by GLC-MS using glass capillary columns. Van Miller (370)studied tissue distribution and excretion of tritiated tetrachlorodibenzo-p -dioxin in non-human primates and rats. Fries and Marrow (125)studied the retention and excretion of 2.3.7.8-tetrachlorodibenzo-~ -dioxin bv rats. Bowes and co-workers (33)^describedi h e GLC characteristics of authentic chlorinated dibenzofurans. Retention times of 15 authentic standards of chlorinated dibenzofurans containing from three to six chlorine atoms were determined relative to dieldrin on GLC columns of four different polarities. Specific Procedures. Yu and co-workers (399)studied the fate of alachlor, 2-chloro-2’,6’-diethyl-N-(methoxymethyl) acetanilide and propachlor, 2-chloro-N-isopropylacetanilide in a model ecosystem. Ammann and co-workers ( 9 ) described a GLC procedure for the determination of alachlor. Khan and Foster (208)measured the residues of atrazine, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine and its metabolites in chicken tissue. Foster and Khan (121)studied the metabolism of atrazine by the chicken. Khan and co-workers (210) chemically derivatized hydroxyatrazine, a metabolite of atrazine, for gas chromato-
graphic analysis. The reaction conditions for silylation, methylation, and alkylation were examined and the resultant derivatives analyzed by GLC using an AFID detector. Hall and Mallen (145) described the separation of benetrifluoro-p-tolufin ( N -[n-butyl]-N-ethyl-2,6-dinitro-a,a,aidine) and trifluralin (2,6-dinitro-N,N-di-n-propyl-a,a,atrifluoro-p -toluidine) by gas chromatography using a liquid crystal column. Downer and co-workers (93) determined benefin and trifluralin residues by quantitative GLC-MS. Businelli and co-workers (53) studied the persistence of benfluralin in soil and its uptake by carrots. Wright and Mathews (390) developed methods for the analysis of crops and soils for residues of the herbicide benzoylprop-ethyl and its breakdown products in crops and soils. Stoller and co-workers (353) studied the leaching of bentazon, 3-isopropyl-l-H-2,1,3-benzothiadiazin-(4)3H-one 2,2-dioxide, a postemergence herbicide in soil. Easten (97) separated the herbicide bifenox, methyl 5(2,4-dichloro~henoxv)-2-nitrobenzoate and related compounds by T k . Nilles and Zabik (284)studied the Dhotodeeradation of the herbicide, basagran. Smith and Lord (345) described a method for determining trace quantities of the herbicide chlortoluron in soils by liquid chromatography. Yu and co-workers (400) studied the fate of the triazine herbicide Cyanazine in a model ecosystem. Khan and Lee (211) determined cyperquat, l-methyl-4phenyl-pyridinium chloride residues in soil by GLC. Larsen and Bakke (221) reported on the metabolism of cyprazine, 2-chloro-4-cyclopropylamino-6-isopropylaminos-triazine using a ringJ4C-labeled compound. Cotterill (74) described the determination of residues of dalapon in soil by gas chromatography of the 1-butyl ester. Anderson and Domsch (10) studied the microbial degradation of the thiolcarbamate herbicide, diallate, in soils and by pure cultures of soil microorganisms. Yu and co-workers (401) studied the fate of dicamba in a model ecosystem. Miyazaki and co-workers (268)reported on the metabolism of dichlobenil by microorganisms in the aquatic environment. Pik and Hodgson (300) determined 3,6-dichloropicolinic acid in soil by GLC. The method for the herbicide involves extraction of 1gram of soil with 1N NaCl at pH 7, methylation with diazomethane, and detection by electron capture GLC. Ldkke (241) determined free and bound chlorophenoxy acids in cereals. The problem of bound chlorophenoxy acids is very important in the analysis of these herbicides. This article presents a lucid interpretation of the problem. Clark and co-workers (64)determined residues of chlorophenoxy acid herbicides and their phenolic metabolites in tissues of sheep and cattle. Hattula and Raisanen (151) described the application of a new glass capillary chromatographic technique in the analysis of phenoxyacetic acid herbicides. Feung and co-workers (113) studied the metabolism of 2,4-dichlorophenoxyacetic(2,4-D)acid in five species of plant callus tissue cultures. Allebone and Hamilton (8)determined 2,4-D in plant tissue. Arjmand and Mumma (15)developed a GLC technique for the analysis of 19 metabolites of 2,4-D or potential metabolites. Arjmand and Mumma ( 1 6 ) studied the gas-liquid chromatography of methyl esters of the 2,4-D amino acid conjugates. Van Peteghem and Heyndrickx (371)reported on the GLC determination of 2,4-D by mass fragmentography with a deuterated internal standard. Feung and co-workers (114) identified the metabolites of 2,4-D in rice root callus tissue cultures. Que Hee and Sutherland (307) described a specific GLC method for the analysis of some amine salts of 2,4-D acid. Hazemoto and co-workers (152)constructed an ion selective electrode for 2,4-D. Dupuy, Jr., and co-workers (96) determined 2,4-D acid in
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wheat grain. and a number of articles on their analysis were published. Van Peteghem and Heyndrickx (372) described the specYip (394), a general referee for the AOAC, reported on troscopic properties of the methyl esters of chlorophenoxy acid fungicides, herbicides, and plant growth regulators. herbicides. The mass and infrared spectra of the methyl esters Sherma (335) prepared an extensive review of the analysis of nine chlorophenoxy acid herbicides were presented. of fungicides. The article should be very valuable to analysts Khan (207) developed an electron capture GLC method for engaged in the residue analysis of fungicides. the simultaneous analysis of 2,4-D, dicambia, and mecoprop Sinha and co-workers (342) described the separation and residues in soil, wheat, and barley. detection of some systemic fungicides by paper chromatogDekker and Selling (85) described the GLC analysis of the raphy. herbicide Dinoterb, 2,4-dinitro-6-tert-butylphenol in soil. Austin and co-workers (21) described the HPLC of benzSanti and Gozzo (325) studied the degradation and meimidazoles. These authors reported that the use of HPLC to measure benzimidazole residues awaits the development of tabolism of Drepamon herbicide, S-benzyl-N,N-di-secmethods of avoiding interferences by substances extracted butylthiolcarbamate, in rice and barnyard grass. from crops and soil. Sikka and co-workers (338) studied the uptake distribution Watkins (378) studied the analysis and transformation of and metabolism in fish using [14C endothall. benzimiazole pesticides. Ekstrom and Johansson (100 studied glyphosate, N Van Alfen and Kosuge (368) studied the metabolism of (phosphonomethyl)glycine, using an amino acid analyzer. botran in flooded soil using a I4C-labeled compound. Hance (148) studied the adsorption of glyphosate herbicide Farrow and co-workers (109) determined residues of the by soil. Agemian and Chau ( 4 ) developed a sensitive GLC procefungicide carboxin in grain by gas chromatography using a dure for the determination of MCPA and MCPB herbicides nitrogen-selective detector. after esterification with l-bromomethyl-2,3,4,5,6-pentaflu- Hoodless and Sargent (171 ) determined residues of chloorobenzene. raniformethan, N - [2,2,2-trichloro-1- (3,4-dichloroanilino) Cheng and Fuhr (61) developed an extraction of the herethyllformamide in grain and cucumbers. After extraction and bicide methabenzthiazuron, N-(2-benzothiazolyl)-N,N’- TLC cleanup on silica gel, the systemic fungicide was quandimethylurea, from soil. titated by electron-capture GLC. Khan and co-workers (209) determined linuron residue in Gilbert (134) investigated the fate of chlorothalonil, soil using gas chromatography. tetrachloroisothalonitrile, fungicide in apple foliage and Atallah and co-workers (17) reported on the metabolism fruit. of the herbicide methazole, 2-(3,4-dichlorophenyl)-4-methReeder (317 ) described a high-speed liquid chromatoyl-1,2,4-oxadiazolidine-3,5-dione in lactating cows and laying graphic determination of o -phenyl phenol residues in citrus hens. products. The limit of the analysis was
