seki KagakU, 21(9), 1223 (1972); Chem. Abstr., 78, 11275e (1973). (600) Yllera Camino A., /on(Madrid). 32(370). 273 (1972); Chem. Abstr., 77, 130484m (1972) (601) Yoshihara, K., Hirose, Y . , Phytochemistry, 12(2), 468 (1973). (602) YOUnOS, Ch., Lorrain, M., Pelt, J. M., Plant, Med. Phytofher., 6(3), 178 (1972); Chem. Abstr.. 78, 33785y (1973).
(603) /bid., (4), 251; Chem. Abstr., 78, 7 5 7 6 6 ~ (607) Zhelev. 2. G., Mezhdunar. Kongr. Efirnym Maslam, [Mater.]. 4th 1968, 1, 97 (1971); (1973). Chem. Abstr., 79, 83394m (1973). (604) Younos, Ch.. Mortier, F., Pelt, J. M., ibid., (3), (608) Zola, A,, Garnero, J., Parfums, Cosmet., Sa171; chem. Abstr., 78, 3 3 7 0 4 ~(1973). vons Fr., 3(1), 15 (1973); Chem. Abstr., 78, (605) Pabza, A . , Pr. Nauk. hst. Chem. Org. Fiz. Po/itech. Wroclaw, 1971(3), 1; Chem. Abstr., 115116v(1973). 78, 1 1 1 5 2 4 ~(1973). (609) Zweig, G., Sherma, J.. “CRC Handbook Of Chromatography”, CRC Press, Cleveland, (606) Zarghami, N. S., Russell, G. F.. Chem., MkroOhio, 1972, Vol. 1, 784 pp., Vol. 2, 343 pp. Mol., Techno/. Lebensm., 2(6). 184 (1973).
Pesticide Residues Wayne Thornburg D e l Monte Corporation Research Center, Walnut Creek, CA 94598
Publication in the field of pesticide methodology has continued a t a high level during the two-year review period from November 1972 through November 1974. The author has attempted to review articles which will be most useful to the residue analyst and, when possible, papers were selected that were published in journals which are readily accessible in major libraries. This review follows the general format and pesticide nomenclature used in the 1973 biennial review of Thornburg (323). Frear’s “Pesticide Index”( 103) 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 (284) 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. “Residue Reviews,” under the editorship of Gunther (124),continues to be an excellent source of information on pesticide methodology. A total of 54 volumes has now been published. Zweig has continued his editorship of “Analytical Methods for Pesticides, Plant Growth Regulators, and Food Additives” with the publication of Vol. VI, “General.” This volume contains the cumulative index to volumes I-VI (355). Zweig and Sherma have co-editored Vol. VI1 of this series, “Thin Layer and Liquid Chromatography and Analysis of Pesticides of International Importance” (356). The following symposia were published: ACS Symposium on “Pesticide Identification at the Residue Level,” Advances i n Chemistry Series 104 ( 3 ) ,and an ACS Symposium on “The Fate of Organic Pesticides in the Aquatic Environment,” Advances i n Chemistry Series 111 (4). The proceedings of the 2nd International Congress on Pesticide Chemicals (317) contains a number of excellent articles on pesticide residue analysis. Ebing (88) compiled the second volume of a comprehenAuthors have not been supplled with free reprlnts for dlstrlbutlon. Extra coples of the revlew issue may be oblalned from Speclal issues Sales, ACS, 1155 16th St.. N.W., Washington, DC 20036. Remlt $4 for domestlc U.S. orders; add $0.50 for additional postage for forelgn destinations.
sive reference book of the GLC pesticide literature of the world in “Gas Chromatography of Plant Protection Agents, Vol. 11”covering the period from 1970-72. Fishbein (100) published a book on the chromatography of pesticides. Bourke and coworkers (35) described a pesticide residue data information retrieval system. Safe and Hutzinger (273) described the up-to-date uses of mass spectrometry in “Mass Spectrometry of Pesticides and Pollutants.” This review period has been characterized by improvements and automation of instrumentation with increased reliability. Many improvements have been made in liquid chromatography, but it still lacks the ease of use and sensitivity that is expected of gas chromatography. However, research is under way to combine separation techniques of liquid chromatography with quantitation by gas chromatography. Eissenbeiss and Sieper (91) described the use of highperformance liquid chromatography in residue analysis. These authors concluded that high-performance liquid chromatography (HPLC) can be regarded as an alternative or a supplementary method to conventional methods such as GLC. Seiber (278) studied the reverse-phase liquid chromatographic retentions of 17 pesticides on Vydac reversedphase in water-methanol and mixed solvents. 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. Narayanaswami and coworkers (227) described the use of TLC in the detection of poisoning by pesticides. Mallet and Surette (208) investigated the fluorescence of pesticides by treatment with acid and base on TLC plates. Almost every pesticide residue analytical procedure requires at least one concentration step involving partial or complete removal of an organic solvent. Ott and Liebig (241) modified a commercial multi-tube solvent evaporator so that it could be used for the concentration of pesticide residue-containing solutions. Voss and Blass (332) developed a solvent-saving extraction-evaporation apparatus for residue analysis of pesticides. Suzuki and coworkers (323, 314) described a systematic separation and identification of pesticides using a combina-
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tion of column, thin layer, and gas chromatography. The basis of this system is the separation of about 100 pesticides into six preliminary divisions. This publication described interesting new techniques for pesticide separation and identification. Griffitt and Craun (122) evaluated a gel permeation chromatographic system (GPC) for the separation of fats and pesticides. The system was a reliable and efficient tool for fat-pesticide separations with more than 98% of the fat or oil being eluted from the column before the pesticide fraction began to elute. Suffet (309) described the p-value approach to quantitative liquid-liquid extraction of pesticides and herbicides from water, and the liquid-liquid extraction of phenoxy acid herbicides from water. Lawrence and Frei (185) described fluorometric derivatization procedures for pesticide residue analysis. This article discusses this technique in good detail and should be very useful. Balayannis (20) prepared surface-modified adsorbents for use in clean-up techniques for pesticide residue analysis. Levi and Nowicki (190) described a rapid screening method for simultaneous determination of organochlorine and organophosphate pesticide residues in wheat by GLC. Thomas and Seiber (322) found Chromosorb 102 to be an efficient medium for trapping pesticides from air. Al-Adil and coworkers (6) studied the translocation of pesticides as affected by plant nutrition. Tirosh and coworkers (324) described the recovery of pesticides from plasticized PVC and analysis by GLC.
GAS CHROMATOGRAPHY Gas chromatography and mass spectrometry continue to be the most satisfactory procedure for the separation, identification, and quantitation of pesticide residues. David (78) in “Gas Chromatographic Detectors” described in detail detectors which are used for pesticide quantitation. The Coulson conductivity detector has been used successfully for several years. Several investigators have described improvements in this technique. Dolan and Hall (83) described the enhancement of the sensitivity and selectivity of the Coulson electrolytic conductivity detector to chlorinated hydrocarbon pesticides. A tenfold increase in sensitivity was achieved by modification of the equipment. Laski and Watts (183) studied the gas chromatography of organonitrogen pesticides using a nitrogen-specific detection system. A total of 95 organonitrogen pesticides were chromatographed on 5 and 10% DC-200 on 80-100 mesh Chromosorb W (HP) using a Coulson electrolytic conductivity detector. Retention times relative to parathion and the amount of pesticide need to give 50% FSD were presented. Lawrence and Moore (187) described a new, compact, temperature controlled electrolytic conductivity detector with adjustable water flow rates. This cell is five times more sensitive than the Coulson cell. Hall (126) described a highly sensitive microelectrolytic conductivity detector for gas chromatography. The detector featured a new unitized gas-liquid separator-conductivity cell that is selfstarting and maintaining. The detector was used for the selective detection of halogen, sulfur, and nitrogen. Minimum detectability of chlorinated hydrocarbon pesticides was 10-20 picograms. The reviewer feels this is a very important article for those engaged in the use of a conductivity detector for pesticide analysis. 158R
Hartigan and coworkers (131) described the analytical performance of a novel nitrogen-sensitive detector and its application with glass open tubular columns. The new detector uses a glass bead with rubidium silicate as an alkali source. The bead is electrically heated, and thus freed from dependence upon the flame as a source of thermal energy. Kolb and Bischoff (176) in another publication described in detail this thermionic nitrogen and phosphorus detector. Gosselin and coworkers (115) studied contamination problems with 63Ni electron capture detectors. It appeared that the temperature difference between the detector and column is important. Furthermore, the detector polarization switch must always be off when no chromatogram is being run. Uhnftk and coworkers (328) studied the use of an electron capture detector for the determination of pesticides in water. Pellizzari (247) described electron capture detection in gas chromatography in a very detailed article with 93 references. This review should be very useful to any analyst engaged in pesticide residue analysis. Sullivan (312) studied electron capture response factors for highly electrophilic compounds. Burgett (41) described the use of electron capture detection including theory, operation, modes, radioactive sources, and carrier gas mixtures. Lovelock (196) described the theory and practice of the electron capture detector. A theoretical model was presented which accurately described the performance characteristics of the electron capture detector under practical conditions. Sugiyama and coworkers (310) studied the interference of Sz molecular emission in a flame photometric detector. The presence of gaseous nonsulfur-containing organic compounds in a carrier gas causes a decrease in the response of flame photometric detectors. The interference by organic compounds increased exponentially with increase in concentration of the substance. Burgett and Green (42) described an improvement in the flame photometric detector that prevents solvent flameout. By reversing the hydrogen gas and air-oxygen gas inlets, an oxygen-hyperventilated flame similar to the conventional FID was produced. The signal-to-noise ratio was increased, the base line has increased stability, and the dynamic working range and linearity were improved. Sugiyama and coworkers (311) studied the characteristics of Sz emission intensity with a flame photometric detector. Gavirlova and Vlasenko (108) evaluated Porochrom I as a support in GLC of pesticides. Gabica and coworkers (106) described a rapid GLC method for screening of pesticide residues in milk. Willmott and Dolphin (347) described a combination of HPLC and electron capture detection in the analysis of pesticides. In their procedure, the column eluent was vaporized and passed directly into an electron capture detector. This detection system was much more sensitive to organochlorine detectors than currently available LC detectors.
CHLORINATED PESTICIDES General Procedure. During this two-year period, further efforts have been made to reduce the use of chlorinated pesticides. However, the use of chlorinated pesticides for more than 30 years and PCB’s for more than 40 years has caused an accumulation of these compounds and their metabolites in the ecosystem. It has been estimated that more than 4 billion pounds of DDT alone have been used since 1940.
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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 lhe American Chemical Society.
Interest in these chlorinated compounds continues, and a number of publications have appeared on their analysis and metabolism. Schulten and Becky (277) applied low- and high-resolution field desorption mass spectrometry (FDMS) to chlorinated pesticidal compounds. These authors found that this new technique gave positive identification of those compounds and their metabolites. Bogusz and Borkowski (33) described the application of TLC-enzyme inhibition technique to organochlorine insecticides. Baird and coworkers (15) developed a procedure for the GLC separation of sulfur from chlorinated pesticide residues in wastewater samples. A column consisting of a mixture of 4.4% OV-17, 4.7% QF-1, and 1.0% DC-200 all on 80/ 100 mesh Gas-Chrom Q solid support shifted the sulfur peak to a position between o-p’-DDE and p,p’-DDE. Musty and Nickless (223) used Amberlite XAD-4 for extraction and recovery of chlorinated insecticides and polychlorinated biphenyls from water. Amberlite XAD macroreticular resinous adsorbents were used for the extraction and recovery of both chlorinated insecticides and polychlorinated biphenyls from water. The absorbed insecticides were eluted with a diethyl ether-hexane mixture. Woolson (350) described a collaborative study for the extraction of chlorinated hydrocarbon insecticides from soil. Nash and coworkers (229) studied comparative extraction procedures for chlorinated hydrocarbon insecticides from soils 20 years after treatment. Goerlitz and Law (114) determined chlorinated insecticides in suspended sediments and bottom material by extraction, purification by adsorption chromatography, and quantitation by GLC using an electron capture detector. Stretz and Stahr (304) determined chlorinated pesticides in whole blood using GLC equipped with an electron capture detector. Griffith, Jr., and Blanke (121) described a microcoulometric determination of organochlorine pesticides in human blood. Murphy (222) described a sulfuric acid cleanup of animal tissues for analysis for acid-stable chlorinated hydrocarbon residues. Claeys and Inman (61) described adsorption chromatographic separation of chlorinated hydrocarbons from lipids. Erney (94) described a rapid screening method for the analysis of chlorinated pesticide and polychlorinated biphenyl residues in fish using GLC. Hattula (134) described some aspects of the recovery of chlorinated residues from fish tissues by using different extraction methods. Adams and coworkers (1)determined insecticides in the tissues of four generations of rats fed different dietary fats
containing a mixture of chlorinated hydrocarbon insecticides. Porter and Burke (251) described an isolation and cleanup procedure for low levels of organochlorine pesticide residues in fats and oils. Farwell and coworkers (95) described the voltammetric identification of organochlorine insecticides, PCBs, and polychlorinated naphthalenes and polychlorinated benzenes. Smart and coworkers (291) determined chlorinated hydrocarbon pesticide residues in foodstuffs using a variety of methods. This detailed paper contains a great deal of information on the analysis of chlorinated pesticides. Sodergren (293) described a simplified clean-up technique for organochlorine residues at the microliter level. Chau (53) described the confirmation of pesticide residue identity using solid matrix derivation procedure for the simultaneous confirmation of heptachlor and endrin residues in the presence of polychlorinated biphenyls. Serum and coworkers (280) determined the electron capturing compounds in paper. Burke (43, 441, a general referee for the AOAC, reported on chlorinated pesticides.
Specific Procedures. Gegiou (109) reported the complete NQR spectrum of aldrin a t various temperatures. The six signals recorded were tentatively assigned to the specific chlorine atoms of aldrin utilizing spectra-structure correlation charts. Kohli and coworkers (175) studied the fate of aldrin-14C in sugar beets and soil under outdoor conditions. Bedford (24) listed the von Baeyer/IUPAC names and abbreviated chemical names of metabolites and artifacts of aldrin (HHDN), dieldrin (HEOD), and endrin. Lombard0 and coworkers (193) identified photoaldrin chlorohydrin as a photoalteration product of dieldrin. Crosby and Moilanen (70) studied the vapor phase photodecomposition of aldrin and dieldrin. Hannan and Bills (128) developed a procedure for the separation of aldrin from PCB 1254 using a GLC column. Klein and coworkers (174) studied the fate of aldrin-14C in potatoes and soil under outdoor conditions. Struble (305) described the analysis of aldrin in the presence of sulfur by electron capture GLC. Sulfur interference was removed by the use of an Apiezon L liquid phase. Weisgerber and coworkers (337) studied the fate of aldrin-14C in maize, wheat, and soils under outdoor conditions. Nelson and Matsumura (230) studied the metabolism of dieldrin (HEOD) in cockroaches and houseflies. Potter and coworkers (253) reported on total 14C residues and dieldrin residues in milk and tissues of cows fed dieldrin-1%. Ang and Dugan, Jr., (11)studied factors relating to completeness of solvent extraction of dieldrin in milk. Maybury and Cochrane (209) evaluated chemical confirmatory tests for the analysis of dieldrin residues. Suzuki and coworkers (315) studied photodieldrin residues in field soils. Visweswariah and Jayaram (331) described a rapid semiquantitative estimation of benzene hexachloride by micro TLC. Mahel’ovl and coworkers (206) determined BHC isomers in soils by GLC and TLC after extraction with light petroleum. Barnett and Dorough (22) studied the metabolism of chlordane in rats. Dorough and Hemken (85) determined chlordane residues in milk and fat of cows fed high purity chlordane in the diet.
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Wallcave and coworkers (334) excreted metabolites of l,l,l-trichloro-2,2-bis(p-chlorophenyl)ethane in the mouse and hamster. Metcalf (215) described a century of DDT. This article gives the history, degradative pathways of DDT in the environment, and some theories of the mode of action of DDT. An extensive bibliography on DDT is included. Fishbein (99) published an extensive review entitled “Chromatographic and Biological Aspects of DDT and Its Metabolites.” This extensive study of DDT and its metabolites should be very helpful for those studying any aspect of DDT or its metabolism. A bibliography of 254 references is included. Cranmer and Copeland (67) described an electron capture GLC procedure for DDA utilizing the 2-chloroethanol derivative. Zelenski and coworkers (354) developed a gas chromatographic method of quantitating DDT in the presence of interfering polychlorinated biphenyls using p-values. Rice and Sikka (265) studied the uptake and metabolism of DDT by six species of marine algae. Gothe (117) described an oxidation procedure using tetrabutylammonium permanganate for the quantitation of DDT residues in the GLC determination of chlorinated hydrocarbons. In this procedure, DDT and neutral metabolites are converted to p,p’-dichlorobenzophenone prior to quantitation by GLC. Feil and coworkers (96) studied the metabolism of o,p’DDT in rats. de Vos and coworkers (81) described a rapid automated GLC analysis for dichloran, lindane, PCNB, and TCNB on lettuce. Chau and Terry (56) confirmed the identity of a - and Bendosulfan by GLC using derivative formation in a solid matrix. Chau and Terry (57) described an alternative confirmation of a- and B-endosulfan by GLC using derivative formation in a solid matrix. El Zorgani and Omer (93) studied the metabolism of endosulfan isomers by aspergillus niger. Burton and Pollard (45) studied the rate of photochemical isomerization of endrin in sunlight. Chau and Terry (58) described derivative formation in solid matrix for confirmation of heptachlor and endosulfan isomers. Chau and coworkers (55) described chromous chloride reduction of heptachlor and its derivatives. Five pentachloro heptachlor derivatives were synthesized, and their nuclear magnetic resonance and mass spectra were presented and discussed. Graham and coworkers (118) studied the photochemical decomposition of heptachlor epoxide. Johnson and coworkers (162) determined hexachlorobenzene residues in fish. The samples were extracted, the extract extensively cleaned up, and the HCB quantitated by GLC using a “3Ni detector. Holdrinet (143) described the determination and confirmation of hexachlorobenzene in fatty samples in the presence of other residual halogenated hydrocarbon pesticides and polychlorinated biphenyls. Asai and coworkers (13) studied the influence of some soil characteristics on the dissipation rate of Landrin insecticide. Karapally and coworkers (167) studied the metabolism of lindane-14C in the rat. Larose (181) described a high-speed liquid chromatographic cleanup of environmental samples prior to the GLC determination of lindane. l6OR
MacNeil and Frei (202) studied the photolysis of methoxychlor. Alley and coworkers (9) studied the photochemistry of mirex, dodecachloropentacyclodecane. Medley and coworkers (210) reported on the cumulation and disappearance of mirex residues in tissues of roosters feed four concentrations of mirex in their feed. Ivie and coworkers (158) reported on the accumulation, distribution, and excretion of Mirex-14C in animals exposed for long periods to the Mirex in the diet. Gibson and coworkers (111) studied the fate of mirex and its major photodecomposition products in rats. Ivie and coworkers (156) studied the fate of mirex-14C in Japanese quail. Chau and Coburn (54) determined pentachlorophenol in natural and waste water. The PCP was extracted with benzene and the extract purified. The acetate derivative was formed and determined by GLC using an electron capture detector. Shafik (281) determined pentachlorophenol and hexachlorophene in human adipose tissue. 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. Oswald and coworkers (240) studied the differentiation and characterization of isomeric polychlorinated biphenyls (PCBs) by GLC coupled with electron impact and chemical ionization mass spectrometry. This comprehensive article should be of interest to anyone working in the field of PCB analysis and identification. Eichelberger and coworkers (90) investigated the analysis of PCBs using GLC-mass spectrometry with computer controlled repetitive data acquistion from selected specific ions. Ruzo and coworkers (272) studied the photoproducts and kinetics of PCBs when the parent compounds were irradiated a t 300 nm for different time periods. The reaction products were analyzed by gas chromatography and mass spectrometry. Su and Price (307) described an element specific gas chromatographic analyses of organochlorine pesticides in the presence of PCBs by selective cancellation of interfering peaks. Hattula (135) described the simultaneous cleanup of fish fat containing low levels of residues and separation of PCB from chlorinated pesticides by TLC. Beezhold and Stout (26) used mixed standards on the quantitation of PCBs. Call and coworkers (49) studied PCB residues in Japanese quail brain using GLC-MS as a detection system. The results were compared to an Arochlor standard. Ismail and Bonner (153) described a new, improved TLC procedure for PCBs, toxaphene, and chlordane components. Edwards (89) discussed some factors in the separation of PCBs from organochlorine pesticides by column chromatography combined with GLC. Crosby and Moilanen (69) studied the photodecomposition of PCBs and dibenzofurans. Bush and Lo (47) used TLC for quantitative PCB analysis. Huckins and coworkers (147) described the perchlorination of PCBs using antimony pentachloride to form decachlorobiphenyl which was then determined by GLC. Carnes and coworkers (50) determined PCBs in solid waste and solid-waste-related materials by GLC. Shahied and coworkers (283) determined PCB residues
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in grades of pulp, paper, and paperboard using GLC and electron capture detection. Sawyer (275)described a collaborative study of the recovery and gas chromatographic quantitation of polychlorinated biphenyls in chicken fat and PCB-DDT combination in fish. Armour (12)described quantitative perchlorination of PCBs as a method of confirmatory residue measurement and identification. Bache and Lisk (14)described a qualitative method for detecting hydroxylated metabolites of PCBs using GLC analysis of the methylated phenol group. Bush and coworkers (48)studied the toxicity and persistence of PCB homologs and isomers in the avian system. Lieb and coworkers (192)studied the accumulation of PCBs (Arochlor 1254) by rainbow trout. Greichus and coworkers (120)analyzed bird tissue for PCBs using GLC and mass spectrometry. Hannan and coworkers (129)analyzed PCBs by gas chromatography and ultraviolet radiation. Young and coworkers (353)determined PCBs in paper and paperboard. Thomas and Reynolds (321)determined polychlorinated terphenyls in paperboard samples by gas chromatography. Putnam and coworkers (257)described the gas chromatography and mass spectrometry of polychlorinated terphenyls (Arochlor 5460). Doguchi and coworkers (82)determined polychlorinated terphenyls in human fat using GLC. Gulan and coworkers (123)described the analysis of POlychlorinated naphthalenes by GLC and ultraviolet radiation. Teske and coworkers (320)determined residues of PCBs in products from poultry fed Arochlor 1254. Hirwe and coworkers (140)described the GLC and mass spectrometric characterization of Arochlor 1242 and 1254 components. Leib and Bills (191)studied the influence of storage temperature of florisil on analysis of PCBs. Hutzinger and coworkers (151) described the GLC behavior and spectroscopic properties of hydroxylated chlorobiphenyls. Hutzinger and coworkers (150) reported on the TLC and color reaction of some hydroxylated chlorobiphenyls. Crowder and Dindal (74)studied the fate of 36Cl-toxaphene in rats.
ORGANOPHOSPHORUS PESTICIDES General Procedures. This two-year period has seen the increasing use of organophosphorus pesticides. The phosphorus-specific thermionic detector and the flame photometric phosphorus and sulfur specific detectors continue to be methods of choice for quantitation of these compounds. McCully (198,199),a general referee for the AOAC, reported on phosphated pesticides. Ruzicka (270)reviewed recent progress on the separation and identification of organophosphorus and carbamate pesticides. Emphasis was placed on TLC and GLC procedures. Newer techniques, including high pressure liquid chromatography (HPLC) and the use of microwave-excited plasmas as detectors for GLC were discussed. Brun and Mallet (38)described a method for the detection of organophosphorus pesticides directly on thin layer chromatograms. Brun and coworkers (39)developed a new method for the detection of organophosphorus pesticides by in situ fluorometry on thin-layer chromatograms, Bellet and Casida (27)studied the products of peracetic
oxidation of organothiophosphorus compounds. This procedure provides a chemical means of generating possible oxidative metabolites and photoproducts from thiophosphorus insecticide chemicals. Poziomek and Crabtree (254) reviewed the Schoenemann reaction in the analysis and detection of organophosphorus compounds. Moye (221)studied on-column transesterification of organophosphates. Shafik and coworkers (282)described a modified procedure for the GLC analysis of alkyl phosphate metabolites in urine. Hussain and coworkers (149)studied the physical and chemical basis for systemic movement of organophosphorus esters in the cotton plant. Ripley and coworkers (266)described the multiresidue analysis of 14 organophosphorus pesticides in natural waters. Holmstead and Casida (144)described the chemical ionization mass spectrometry of organophosphorus insecticides. Specific Compounds and Procedures. Leary (188)determined acephate, 0,s-dimethyl acetylphosphoramidothioate, and a metabolite Ortho 9006, 0,s-dimethyl phosphoramidothioate, in a variety of crops using GLC. After extraction of the sample with ethyl acetate, the solvent was evaporated and an ether solution of the residue was passed through a silica gel column to remove interfering materials. The two pesticides were eluted from the column with 10% methanol in ether and measured simultaneously by programmed temperature GLC using an alkali flame ionization detector. Stanley and coworkers (298)described a GLC method for residues of Baygon and metabolites in plant tissues. Stanley and Thorton (297)described a gas chromatographic method for residues of Baygon and its major metabolite in animal tissues and milk. Ivey and coworkers (154)described the GLC determination of chlorfenvinphos in milk, eggs, and body tissues of cattle and chickens. Suett (308)studied the uptake of chlorfenvinphos and phorate from soil by carrots. Chlorfenvinphos and phorate residues were extracted with hexane-acetone and chloroform-methanol, respectively. After addition of 0.5 ml of decane, aliquots were concentrated almost to dryness and cleaned-up on carbon-cellulose. Residues of both insecticides were eluted with 100 ml of ethyl acetate. Final analysis was by GLC using alkali flame ionization detection. Braun (36)described the GLC determination of residual chlorpyriphos (Dursban), 0,O-diethyl 0-3,5,6-trichloro-2pyridyl phosphorothioate and leptophos, 0-(4-bromo-2,5dichloropheno1)O-methyl phosphonothioate, and their respective oxygen analogs and hydrolytic metabolites in field-treated vegetables. Maini and Collina (207)determined residues of chlorpyrifos in various crops using a sweep co-distillation method for cleanup. Struble (306)described the conditioning of a polyalkyl glycol liquid phase for the GLC analysis of chlorpyrifos and its oxygen analog. Tadjer and Egyed (316)described the determination of cyolane, 2-(diethoxyphosphinylimino)-1,3-dithiolane in alfalfa pellets and rumen content of a cow. Janes and coworkers (160)studied the toxic metabolites of diazinon in sheep. Machin and coworkers (201)described a rapid method for the GLC determination of diazinon and dichlorvos in blood using a thermionic detector.
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Potter and coworkers (252) studied the carbon-14 balance and residue of dichlorvos and its metabolites in pigs dosed with 14Cdichlorvos. Steller and Pasarela (299) described a GLC method for the determination of dimethoate and dimethoxon residues in plant and animal, tissues, milk, and eggs. The residues were extracted with methylene chloride, concentrated, cleaned up by silica gel chromatography, and quantitated by GLC using either a flame photometric or an alkali flame ionization detector. Recovery values for dimethoate or dimethoxon added a t the 0.002-1.0 ppm ranged from 56 to 112%.
Currie (76) determined leptophos, leptophos oxon, and a possible phenolic photoconversion metabolite in rapeseed grain. Lubkowitz and coworkers (197) determined residues of Monitor, 0,s-dimethyl phosphoroamidothioate in mature tomatoes using a flame photometric detector. Beynon and coworkers (28) determined neutral conjugates of N-hydroxymethyl derivatives of monocrotophos insecticides. Joiner and Baetcke (164) compared twelve TLC systems for the separation of photoalteration products of parathion. White and coworkers (339) investigated the extraction efficiency determination of labeled systemic parathion residues. Joiner and Baetcke (163) studied the persistence of parathion on cotton. Joiner and Baetcke (165) identified the photoalteration products formed from parathion by ultraviolet light. Iwata and coworkers (159) determined the persistence of parathion on California soils under laboratory conditions. Westlake and coworkers (338) determined the persistence of residues of the insecticide phosphamidon, 2chloro-N,N-diethyl-3-hydroxycrotonamide dimethyl phosphate, on and in oranges, lemons, and grapefruit, orange leaves, and in dried citrus pulp cattle feed. Maes and coworkers (205) described a GLC determination of quinalphos (Ekalux), 0,O-diethyl-0-[quinoxalinyl(2)]thionophosphate, and its P=O metabolite, quinalphos oxygen analog. The sample was extracted with ethyl acetate, the extract purified by use of a Sweep co-distillation apparatus. The Quinalphos was quantitated by GLC using a cesium bromide thermionic detector. Webber and Box (336) examined tetrachlorvinphos and its formulations for the presence of tetrachlorodibenzo-pdioxins by a GLC procedure. Devine (79) determined trichlorfon, 0,O-dimethyl(2,2,2-trichloro-l-hydroxyethyl) phosphonate in forest environmental samples using a GLC procedure. Aharonson and Ben-Aziz ( 5 ) studied the persistence of residues of Velsicol VCS-506, O-4(bromo-2,5-dichlorophenyl-0-methyl phenylphosphonothioate and two of its metabolites in tomatoes and grapes.
MacNeil and coworkers (203) determined dimethoate and malathion in lettuce by TLC and in situ fluorometry. The pesticides were separated by TLC and fluorescence was produced by spraying the developed chromatogram with a palladium chloride-calcein reagent. A ligand exchange occurs in which the palladium complexes preferentially with the sulfur in the pesticide, releasing the metalfluorochromic indicator calcein. Woodham and coworkers (348) determined residues of dimethoate and its oxygen analog on and in citrus leaves using GLC with a flame photometric detector. Woodham and coworkers (349) compared dimethoate and dimethoxon residues in citrus leaves and grapefruit following foliar treatment with dimethoate wettable powder with and without surfactant. Talekar and Lichtenstein (318) studied the influence of mineral nutrients on the penetration, translocation, and metabolism of Dyfonate, 0-ethyl S-phenyl ethylphosphonodithioate in pea plants. Saha and coworkers (274) compared three extraction and cleanup methods for determining carbon-14-labeled residues from wheat plants grown in soil treated with Dyfonate-ring-14C. Whiteoak and coworkers (342) described a gas chromatographic method for the residue analysis of soil exposed to fenazaflor. The residue was extracted from moistured soil with acidified aqueous methanol. After clean-up by partition, the residue was determined by GLC with electron capture detection. Williams and coworkers (346) determined residues of fensulfothion, 0,O-diethyl 0-[p-(methylsulfinyl)phenyl]CARBAMATES phosphorothioate and its sulfone in muck soil using Soxhlet extraction, a silica gel-alumina column cleanup Carbamate insecticides are of continuing importance. and determination by gas chromatography with flame-phoThey present difficult analytical problems due to their intometric detection. stability in GLC columns. A number of papers were pubAd-Adil and coworkers (7) studied the uptake and translished describing derivative preparation prior to GLC, and location of Guthion by beans and barley plants. it is sometimes possible to determine carbamates using miKuhr and coworkers (177) studied the dissipation of Gucrocoulometry or the Coulson nitrogen detector. thion, Carbaryl, Polyram, phygon, and Systox from apple Lorah and Hemphill (195) described the direct chromaorchard soil. tography of N-methylcarbamate pesticides on a ChromoBull and Borkovec (40) studied the metabolism of I4Csorb W surface modified with Carbowax 20M. The intact labeled HEMPA, hexamethylphosphoric triamide, by adult compounds were detected by means of the nitrogen or sulboll weevils. fur response of an alkali flame detector. Tanabe and coworkers (319) described the photochemisRamasamy (260) described a colorimetric method for the try of imidan in diethyl ether. The described research was a determination of eight carbamate insecticide residues. The laboratory study and was organized to give the maximum method is applicable to carbamates which on hydrolysis number of photolysis products. yield phenols with a free para-position suitable for coupling Holmstead and coworkers (145) studied the metabolism with a diazo reagent to yield colored solutions. of leptophos, O-(4-bromo-2,5-dichlorophenyl)-O-methyl MacNeil and coworkers (204) described the hydrolysis of phenylphosphonothioate, in white mice and on cotton some carbamate pesticides. plants using a 14C labeled compound. The major degradaMendoza and Shields (213) determined some carbamates tion products in the mouse are 4-bromo-2,5-dichlorophenby enzyme inhibition techniques using TLC and colorime01, 0-methyl phenylphosphonothioic a d d , methyl phenyltry. phosphonic acid, and phenylphosphonic acid. The major Holden (142) described a gas chromatographic determination of residues of methylcarbamate insecticides in crops portion of the leptophos was recovered unchanged from the as their 2,4dinitrophenyl ether derivatives. Residues were cotton plant. 162R
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determined at levels as low as 0.05 ppm. Recoveries generally range between 90 and 110%. Frei and coworkers (105) analyzed carbamate insecticides by fluorogenic labeling HSLC. The N-methyl carbamate insecticides were labeled with dansyl chloride. Detec1 was reported tion limits between 1-10 ng per 4 - ~ injection and the method was suitable for quantitative analysis. Environmental samples can be analyzed by this procedure. Storherr (302, 303), a general referee for the AOAC, reported on carbamate pesticides, fumigants, and miscellaneous pesticides. Rangaswamy and Majumder (262) described a colorimetric method for the estimation of carbaryl and its residues in grain based on its reaction with diazotized o-toluidine. The method is sensitive to 0.1 Wg carbaryl/20 gram sample. Cocks (63) described the metabolism of carbaryl in the cockroach. Pree and Saunders (255) studied the metabolism of carbofuran in Mugho pine using 14C-labeled compound. Caro and coworkers (51) studied the dissipation of soilincorporated carbofuran in the field. Carbofuran disappeared from soil by apparent first-order kinetics, the halflife ranging from 46 to 117 days. Van Middelem and Peplow (330) evaluated extraction procedures for the removal of l*C-carbofuran and its toxic metabolite from cabbage leaves. Williams and Brown (345) determined carbofuran and 3-hydroxy carbofuran residues in small fruits. Whitten and Bull (343) studied the fate of the carbamate pesticide, Diamond Shamrock DS-15647, 3,3-dimethyl-1(methylthio)-2-butanone 0-(methylcarbamoyl) oxime in cotton plants and soil. The pesticide was rapidly oxidized to its toxic sulfoxide derivative, which was further oxidized, but more slowly, to the more toxic sulfone form. Addison and coworkers ( 2 ) studied the photochemical solution reactions of matacil, 4-dimethyl-amino-m-tolylN-methyl carbamate, and Landrin, 3,4,5-trimethylphenylN-methyl carbamate. Frei and Lawrence (104) determined matacil and zectran by fluorigenic labeling, TLC, and in situ fluorimetry. Mendoza and coworkers (212) determined methomyl, 1(methy1thio)ethylideneamino methylcarbamate in rape seeds, oils, and meals by a thin-layer chromatographic-enzyme inhibition technique. Reeves and Woodham (263) described a GLC analysis of methomyl residues in soil, sediment, water, and tobacco utilizing the flame photometric detector. Methomyl was extracted from soil, sediment, and water with dichloromethane and the extract purified by use of a Florisil column. Quantitation was by GLC equipped with a flame photometric detector. Mendoza and Shields (214) determined methomyl by reaction and GLC. using l-fluoro-2,4-dinitrobenzene Harvey and coworkers (132) studied the metabolism of methomyl in the rat. Harvey and Reiser (233) studied the metabolism of methomyl in tobacco, corn, and cabbage. Miller and coworkers (216) described a method for the sampling and analysis of propoxun, o-isopropoxypheny1-Nmethylcarbamate in air. Cheng and Casida (59) studied the metabolism of Chevron RE 11775, 3-(2-butyl)-phenyl N-methylcarbamate. This paper is very detailed and discusses in depth the metabolic pathways of this compound. Ohkawa and coworkers (239) studied the metabolism of Tsumacide, m-tolyl N-methylcarbamate in rats, houseflies, and bean plants using 14C-Tsumacide. Meikle (211) studied the metabolism of Zectran.
HERBICIDES In this two-year review period, there was again an increase in the number of articles dealing with herbicide analysis. Herbicides belong to many classes of compounds and the reviewer has segrated, where possible, the reviewed articles according to type of herbicide. Dioxins continue to evoke considerable interest. Geike (110) described a TLC screening test for the detection of inhibiting properties of phenylurea herbicides on certain enzymes. Long and Thompson (194) determined herbicide residues in air-cured burley tobacco using GLC. Payne and coworkers (246) described an integrated method for the determination of admixed residues of the herbicides trifluralin, diphenamid, and paraquat in soil and runoff samples. A Coulson electrolytic conductivity detector permitted simultaneous GLC quantitation of trifluralin and diphenamid. The paraquat was determined by a modified colorimetric procedure. Lawrence and Laver (186) described the analysis of carbamate and urea herbicides in foods, using fluorogenic labe1in g. Dannals and coworkers (77) studied the dissipation and degradation of Alar in soils under greenhouse conditions.' Nilles and Zabik (235) studied the photodegradation of Basalin herbicide, N-(2-chloroethyl)-2,6-dinitro-N-propyl4-trifluoromethylbenzamine, in solution, as a thin film and on soil. Plimmer and Klingebiel (249) studied the photochemistry of N-sec-butyl-4-tert-butyl-2,6-dinitroaniline. Kearney and coworkers (169) described the soil persistence and metabolism of the herbicide N-sec-butyl-4-tertbutyl-2,6-dinitroaniline. Nakamura and coworkers (226) studied the uptake and translocation of benthiocarb herbicide, 4-chlorobenzyl N,N-diethylthiocarbamate, by plants. Beynon and coworkers (30) described the degradation of the herbicide benzoylprop-ethyl, ethyl (*)-2-(N-benzoylN-3,4-dichloroanilino)propionate, following its application to wheat. Beynon and coworkers (29) studied the fate of benzoylprop-ethyl in crops grown in treated soil. Beynon and coworkers (31) studied the degradation of benzoylprop-ethyl in soil. Crouch and Pullin (73) described an analytical method for residues of bromoxynil octanoate and bromoxynil in soil. The sample was extracted with ammoniacal methanol which, on standing, converted any octanoate present to bromoxynil. The bromoxynil was converted to methyl ester with diazomethane which was estimated by GLC. Moilanen and Crosby (219) studied the photodecomposition of bromacil. Still and Mansager (300) studied the metabolism of chloropropham in cucumber plants. Soderquist and coworkers (295) determined cacodylic acid, hydroxydimethylarsine oxide, by gas chromatography. Waldron (333) determined residues of Dacthal and 2,4-D in strawberries using gas chromatography. Khan (171) determined diquat and paraquat residues in soil by gas chromatography. Smith (292) studied the breakdown of the herbicide dicambia and its degradation product 3,6-dichlorosalicylic acid in prairie soils using 14C-ring- and 14C-carboxyl-labeled dicambia. Chang and coworkers (52) studied the effect of N,N-diallyl-2,3-dichloroacetamide on ethyl N,N-di-n-propylthiocarbamate uptake and metabolism by corn seedlings.
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Sikka and coworkers (286) studied the uptake and meWilliams and Blanchfield (344) described an improved tabolism of dichlobenil, 2,6-dichlorobenzonitrile, by emscreening method for chlorodibenzo-p-dioxins. ersed aquatic plants. Nilsson and coworkers (236) described chromatographic Newsom and Mitchell (231) determined residues of dinievidence for the formation of chlorodioxin from chloro-2tramine, ~,~,diethyl-2,4-dinitro-6-trifluoromethyl-m-phenoxyphenols. phenylene, a new selective herbicide, in soil and plant tisDorough (84) studied the metabolism of methazole, 2sue. The procedure involves methanol extraction, methy(3,4-dichlorophenyl)-4-methyl-l,2,4-oxadiazolidine-3,5lene chloride partitioning, Florisil column chromatography, dione, herbicide in wheat and onions. and measurement by electron capture GLC. Nakagawa and Crosby (225) described the photodecomNewsom and Woods (232) studied the photolysis of the position of nitrofen, 2,4-dichlorophenyl p-nitrophenyl herbicide dinitramine. The compound degraded rapidly ether. through reductive cyclization of a nitro group and an adjaMosier and Guenzi (220) studied the photolytic decomcent N-ethyl group to give a series of products. position of picloram. Bandal and Casida (21) studied the metabolism and phoMcKone and Cotterill (200) described the extraction of toalteration of 2-sec-butyl-4,6-dinitrophenol, DNBP herbipicloram residues from a sandy loam soil. cide, and its isopropyl carbonate derivative, dinobuton acaHilton and coworkers (138) studied the distribution of ricide. picloram residues in sugarcane. Parouchais (243) determined diuron residues in wheat by Paulson and Jacobsen (244) isolated and identified progas chromatography. pham, isopropyl carbanilate, metabolites from animal tisSikka and Rice (287) determined the persistence of ensue and milk. dothall, 7-oxabicylo(2.2.l)heptane-2,3-dicarboxylicacid, Paulson and coworkers (245) isolated and identified proby GLC. pham metabolites from the rat and the goat. Sikka and Saxena (288) studied the metabolism of enFisher (101) studied the metabolism of the herbicide dothall by aquatic-microorganisms. pronamide, 3,5-dichloro-N-(l,l-dimethyl-2-propynyl) Handa and coworkers (127) determined residues of lasso, benzamide, in soil under laboratory conditions using 14C2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethy1)acetalabeled pronamide. mide. Soderquist and Crosby (294) described a gas chromatoIvie and coworkers (157) studied the photodecomposition of the herbicide methazole, 2-(3,4-dichloropheny1)-4- graphed procedure for the determination of paraquat in water. methyl-1,2,4-oxadiazolidine-3,5-dione. Pope and Benner (250) described a colorimetric determiDorough and coworkers (86) studied the metabolism of the herbicide methazole, 2-(3,4-dichloropheny1)-4-methyl- nation of paraquat in soil and water. A modified colorimetric method was described making it more suitable for rou1,2,4-oxadiazolidine-3,5-dione in cotton and bean plants, tine analysis of a large number of samples. and the fate of certain of its polar metabolism in rats. Ramsteiner and coworkers (261) described a multiresiSirons (289) determined methyl isothiocyanate in soils due method for the determination of triazine herbicides in by GLC using either conductivity or flame photometric defield-grown agricultural crops, water, and soil. The method tectors. consisted of methanol extraction, cleanup on an alumina Hilton and coworkers (139) studied the absorption, column, GLC analysis using a Carbowax column with nitrotranslocation, and metabolism of metribuzin, (Bay-943371, gen-, sulfur-, and chloride-specific detectors. Extraction 4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4~)and recovery data were given. one herbicide in sugarcane using 14C-labeled compound. Purkayastha and Cochrane (256) compared electron capLakso and coworkers (179) determined monosodium ture and electrolytic conductivity detectors for the residue methanearsonate and arsenic acid in plants. analysis of s-triazine herbicides. Comparable sensitivities Renberg (264) described an ion exchange technique for were obtained for the range studied (0.02 to 2.0 ppm). the determination of chlorinated phenols and phenoxy Ruzo and coworkers (271) studied the photochemistry of acids in organic tissue, soil, and water. This procedure ofselected s-triazines in solution. fered a single and rapid clean-up for lipophilic substances Shimabukuro and coworkers (285) studied the chlorocapable of forming water soluble anions. form-soluble metabolites of atrazine found in sorghum. Crosby and Wong (71) studied the photodecomposition Glennie-Holmes (113) described a rapid determination of p-chlorophenoxyacetic acid. of atrazine residues in soil using infrared spectrophotomeCrosby and Wong (72) studied the photodecomposition try. of 2,4,5-T in water. Lamoureux and coworkers (180) studied the metabolism Feung and coworkers (98) studied the mass spectra and of atrazine in sorghum. chromatographic properties of amino acid conjugates of Huss and AdamoviC (148) determined ametrine and 2,4-dichlorophenoxyaceticacid. atrazine residues in soil by TLC. Horner and coworkers (146) compared three techniques Sirons and coworkers (290) determined residues of atrazfor the esterification of 2,4-dichlorophenoxyaceticacid. Esine, cyanazine, and their phytotoxic metabolites in a clay terification with BFs/alcohol mixtures produces esters in loam soil. The herbicides were extracted with a 65% acetogreater than 90% yield in 20 minutes with few byproducts. nitrile-water mixture and quantitated by a Coulson conLarose and Chau (182) described the relationship beductivity detection system. tween molecular structure and retention index of herbicidLau and coworkers (184) reported on the characterizaal chlorophenoxy acids. tion and microdetermination of a water-soluble metabolite Buser and Bosshardt (46) described a fast, highly selecfrom Bladex herbicide, propionitrile, 2-(4-chloro-6-ethylative gas chromatographic method for the determination of mino-s-triazine-2-ylamino)-2-methyl-, by conversion to 2,3,7,8-tetrachlorodibenzo-1,4-dioxin (TCDD) in technical 5,5-dimethylhydantoin. 2,4,5-trichlorophenoxyaceticacid (2,4,5-T), and also in Schroeder and coworkers (276) described an analytical 2,4,5-T alkyl ester and amine salt herbicide formulations method for the determination of residue levels of hydroxyusing quadrupole mass fragmentography. 164R
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ed to MBC. The MBC was trifluoroacetylated and the derivatized MBC was measured by GLC using an electron capture detector. Kirkland (172) developed a high-speed liquid chromatographic procedure for the analysis of benomyl and metabolites in cow’s milk, urine, feces, and tissues. White and coworkers (340) described thermal and basecatalyzed hydrolysis products of the systemic fungicide, benomyl. Kvalvag ( I 78) described a new colorimetric procedure for the determination of benomyl. The colorimetric procedure is based on the reaction of the hydrolysis product of benomyl with sodium hypochlorite to form a blue color. ACARICIDES Cox and coworkers (66)estimated surface residues of beBaker and Hoodless (17) determined residues of binapanomyl on treated bananas by rinsing the benomyl from the cry1 in selected fruits by gas chromatography. After extracbananas and quantitating by a microbiological and a UV tion with a mixture of hexane, diethyl ether and dimethylspectrophotometric assay. formamide, the binapacryl was separated from interfering Fernandes and Cole (97)compared solvents and methods co-extractives by chromatography on a silica gel column of extracting MBC, a metabolite of the fungicide, benomyl and quantitated by electron-capture GLC. in tobacco. St. John and Lisk (301)described metabolic studies with White and Kilgore (341) determined systemic MBC resichloropropylate acaricide in the dairy cow. dues in food crops treated with beomyl fungicide. Devine (80) determined D-048,1-(2-butynyl)-l-(p-tertThe ethylene bisdithiocarbamate (EBDC) fungicides are butyl phenoxy)-2-butyl sulfite, in cottonseed using a flame a most important and widely used group of the organic funphotometric detector in the sulfur mode. gicides. The EBCD fungicides have been shown by several Hawkins and Saggers (136)described the fate of dinobuinvestigators to be degraded to several compounds, one of isopropyl carbonate and ton, 2-s-butyl-4,6-dinitrophenyl these being ethylenethiourea (ETU). However, in 1972 dinoseb, on growing apples. Graham and Hansen (119) suggested that the presence of Johannsen and Knowles (161)studied the metabolism of ETU (2-imidazolidinethione) on food and food products fluenethyl (Flu),2-fluoroethyl(4-biphenylyl) acetate in the poses a potential hazard because of its effects on the thymouse, house fly, and twospotted spider mite using triroids of mammals. During the past two years, there has tium-labeled Flu. been continuing interest in this problem, and severol paKellner and coworkers ( 1 70) studied the absorption, dispers have been published on analytical techniques. tribution, and excretion of the 14C-labeled acaricide HoeBontoyan and Looker (34) studied the degradation of 2910, 0,O-diethyl - S - (5,7-dichlorobenzoxazol-2-ylmethyl)commercial ethylene bis-dithiocarbamate fungicides under dithiophosphate following oral application to milk-producelevated temperature and humidity. ing ruminants and dermal application to a calf. Haines and Adler (125) determined residues of ethylene Gauer and coworkers (107) determined organotin resithiourea (ETU) on food crops by extracting the samples dues from plictran, tricylohexyltin hydroxide and its dicywith methanol, partially purifying the extract on an alumiclohexyl metabolite in fruit crops by GLC following derivana column, and derivatizing the ETU with 1-bromobutanr, tization with aqueous hydrobromic acid. in the presence of dimethylformamide and sodium borohyClegg and Martin (62) determined residues of the carbadride. The derivative was measured by GLC using a flame mate acaricide, Promacyl, 3-methyl-5-isopropylphenyl-N- photometric detector. (n-butanoy1)-N-methylcarbamate, and two metabolites in Blazquez (32) developed a TLC procedure for the analythe tissues and milk of cattle, Analysis was by GLC using a sis of ETU from tomato foliage, soil, and water. Sensitivity derivative suitable for electron capture detection. was in the order of 1 ppm. Newsome (233) studied the excretion of ETU by rat and FUNGICIDES guinea pig. A number of articles were published on the metabolism Ross and Crosby (268) described the photolysis of ETU. and quantitation of systemic fungicides, especially those of Cruickshank and Jarrow (75) studied the degradation of the thiabendazole type. ETU. Baker and coworkers (16) described a TLC procedure for Nash (228) described an improved GLC method for determining ethylenethiourea in plants. In the improved the identification of systemic fungicides. Baker and Hoodless (18) described analytical methods method, pentafluorobenzoyl chloride was substituted for for the detection and determination of residues of systemic trifluoroacetic anhydride derivatization of S-benzylated fungicides. ETU. The resulting product [2- (benzylthio)- 1- (pentafluoChiba and Doornbos (60) studied the instability of berobenzoyl)-2-imidazoline] gave recoveries of near 100% and nomyl, methyl l-(butylcarbamoyl)-2-benzimidazolecarba- improved the GLC response. mate under various conditions. Newsome (234) described a method for determining ethMiller and coworkers (218) estimated benomyl in the ylenebis(dithi0carbamate) residues on food crops as bismilligram range using a colorimetric procedure. (trifluoroacetamido)ethane. Kirkland and coworkers ( I 73) determined benomyl resiVan Alfen and Kosuge (329) studied the microbial medues in soils and plant tissues using high speed cation extabolism of the fungicide 2,6-dichloro-4-nitroaniline. change liquid chromatography. Pack and coworkers (242) described a GLC method for Rouchaud and Decallonne (269) described a gas chromathe analysis of dichlozoline, 3-(3,5-dichloropheny1)-5,5tographic method for the analysis of benomyl and its medimethyloxazolidinedione-2,4,a new fungicide in grapes tabolite MBC, methyl 2-benzimidazolecarbamate. The funand grape products. gicides were extracted with benzene, the benomyl convertUchiyama and coworkers (326)studied the fate of Oryze-
cyprazine, 2-hydroxy-4-cyclopropylamino-6-isopropylamino-s-triazine in corn. Goswami and Green (116)described the extraction of hydroxyatrazine, atrazine, and ametryne from soil. Bakke and Price (19) identified nine rat urinary metabolites from I4C-ring labeled prometone, 2-methoxy-4,6-bis(isopropy1amino)-s- triazine. Crosby and Leitis (68) studied the decomposition of trifluralin in water. Leitis and Crosby (189) described the photodecomposition of trifluralin.
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mate, 3-allyloxy-1,2-benzisothiazole1,l-dioxide,a new fungicide used for controlling rice blast. Rivers (267) developed a GLC method for the determination of pentachlorophenol in human blood and urine. Beck and Hansen (23) reported on the degradation of quintozene, pentachlorobenzene, hexachlorobenzene, and pentachloroaniline in soil. After extraction the fungicide and its metabolites were quantitated by electron capture GLC. Rajzman (259) determined thiabendazole, 2-(4’-thiazo1yl)benzimidazole in citrus fruits by ultraviolet spectrophotometry. Tjan and Burgers (325) described the TLC detection of thiabendazole in fruits. Miller and coworkers (217) estimated thiabendazole in milligram and submilligram range using a colorimetric procedure. Norman and coworkers (237) determined thiabendazole residues on and in citrus. Norman and coworkers (238) described a TLC separation and spectrophotofluorometric determination of thiabendazole residues in and on citrus. Fleeker and coworkers (102) studied the persistence and metabolism of thiophanate-methyl (TM), 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene,a broad spectrum fungicide in soil using I4C-labeled compound.
residues in foodstuffs fumigated with methyl bromide and ethylene dibromide at low temperatures. Brown and coworkers (37) determined bromine residues in potato and wheat crops grown in soil fumigated with methyl bromide. Hargreaves and coworkers (130) described a method for the estimation of 1,2-dibromoethane and vegetables by Xray fluorescence. Heuser (137) determined pesticide residues arising from fumigation practices. Muthu and coworkers (224) described a paper strip detector for detecting maximum acceptable concentrations (0.05-0.3 ppm) of phosphine in air. Wasfy and coworkers (335) studied the metabolism of 14C-naphthaleneacetic acid in mandarin fruit. Gilbert and coworkers (112) studied the fate of neodecanoic acid in onion and soil using 14C-carboxy-labeled compound. This compound is used to dry onion tops. It was also immobile in the plant, but did decompose in the soil. El-Dib and Aly (92) described a colorimetric procedure for the analysis of phenylamide pesticides in natural waters. Kawano and coworkers (168) studied pyrethrin formulations by gas chromatography. Hoffman and coworkers (141) studied the metabolism of dimethyl-2R-20458, 1-(4’-ethyl-phenoxy)-6,7-epoxy-3,7 octene, in the rat. MISCELLANEOUS PESTICIDES AND Ueda and coworkers (327) studied the photodecomposiMISCELLANY tion of Resmethrin and related phrethroids. In this review, miscellaneous pesticides which were diffiPeters and Baxter (248) described an analytical procecult to classify and miscellany were combined in one secdure for the determination of Compound 1080, sodium flution. oro-acetate, residues in biological materials. The sample Beernaert (25) determined biphenyl and orthophenylwas degraded by oxygen combustion and the inorganic fluphenol by gas chromatography. oride determined by an ion specific electrode. Ivie and coworkers (155) studied the metabolic transforStahr and coworkers (296) described a GLC determinamation of disugran, methyl 3,6-dichloro-o-anisate, a plant tion of sodium fluoroacetate. growth regulant, by rumen fluid of sheep using 14C-labeled Jones and Isaac (166) described the determination of sulcompound. fur in plant material using a Leco Sulfur Analyzer. Ihnat and coworkers (152) determined maleic hydrazide Andrawes and coworkers (10) studied the metabolism residues in tobacco and vegetables. and residues of Temik aldecarb pesticide in cotton foliage Selim and Seiber (279) described a GLC method for resiand seed under field conditions. dues of metaldehyde, 2,4,6,8-tetramethyl-1,3,5,7-tetroxo- Allen and Sills (8) described a GLC determination of 3cane in crop tissues. trifluormethyl-4-nitrophenol residues in fish. Quistad and coworkers (258) studied the environmental Yip (351, 352), a general referee for the AOAC, reported degradation of the insect growth regulator methoprene, isoon fungicides, herbicides, and plant growth regulators. propyl (2E, 4E)-11-methoxy-3,7,11-trimethyl 2,4-dodecadCorneliussen (64, 65), a general referee for the AOAC, reienoate in alfalfa and rice as a function of time. ported on intra-laboratory studies of multiresidue methDumas (87) determined inorganic and organic bromide ods.
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(295) Soderquist, C. J., Crosby, D. G., Bowers, J. B., Anal. Chem.. 46, 155 (1974). (296) Stahr, H. M., Buck, W. B., Ross, P. F.. J. Ass. Offic. Anal. Chem., 57, 405 (1974). (297) Stanley, C. W., Thorton, J. S., J. Agr. Food Chem., 20, 1269 (1972). (298) Stanley. C. W., Thorton, J. S., Katague, D. B.. ibid., p 1265. (299) Steller, W. A,, Pasarela, N. R.. J. Ass. Offic. Anal. Chem., 55, 1280 (1972). (300) Still, G. G., Mansager, E. R., J. Agr. Food Chem., 21, 787 (1973). (301) St. John, L. E., Jr., Lisk, D. J.. ibid., 21, 644 (1973). (302) Storherr, R. W., J. Ass. Offic. Anal. Chem., 56, 296 (1973). (303) lbid., 57, 296 (1974). (304) Stretz, P. E., Stahr, H. M., ibid., 56, 1173 (1973). (305) Struble. D. L., Bull. Environ. Contam. Toxicol., 11, 231 (1974). (306) Struble. D. L., J. Ass. Offic. Anal. Chem., 56, 49 (1973). (307) Su, G. C. C., Price, H. A,. J. Agr. Food Chem., 21, 1099 (1973). (308) Suett, D. L., Pestic. Sci., 5, 57 (1974). (309) Suffet, I. H., J. Agr. Food Chem., 21, 591 (1973). (310) Sugiyama. T., Suzuki, Y.. Takeuchi. T., J. Chromatogr., 77, 309 (1973). (311) lbid., 80, 61 (1973). (312) Sullivan, J. J., ibid., 87, 9 (1973). (313) Suzuki, J., Nagayoshi, H., Kashiwa, T., Agr. Biol. Chem., 38, 279 (1974). (314) lbid., p 1433. (315) Suzuki, M., Yamato, Y., Watanabe, T., Bull. Environ. Contam. Toxicol., 12, 275 (1974). (316) Tadjer, G. S., Egyed, M. N., ibid., p 173. (317) Tahori, A. S., Ed., "Pestic. Chem. Proc. Int. Congr. Pestic. Chem. 2nd," Gordon and Breach, New York, N.Y. (318) Talekar, N. S., Lichtenstein, E. P., J. Agr. Food Chem., 21,851 (1973). (319) Tanabe, M., Dehn, R. L., Bramhall, R. R., ibid., 22, 54 (1974). (320) Teske, R. H., Armbrecht, B. H., Condon, R. J., Paulin, H. J., ibid., p 900. (321) Thomas, G. H., Reynolds. L. M.. Bull. Environ. Contarn. Toxicol., 10, 37 (1973). (322) Thomas, T. C., Seiber, J. N., ibid., 12, 17 (1974). (323) Thornburg, W., Anal. Chem., 45, 151R (1973). (324) Tirosh, N.. Siegmann, A,, Narkis, M., J. Chromatogr. Sci., 12, 149 (1974). (325) Tjan, G. H., Burgers, L. J., J. Ass. Offic. Anal. Chem., 56, 223 (1973). (326) Uchiyama. M., Abe, H., Sato, R., Shimura, M.. Watanabe, T., Agr. Biol. Chem., 37, 737 (1973). (327) Ueda, K., Gaughan, L. C., Casida. J. E., J. Agr. FoodChem., 22, 212 (1974). (328) Uhnak, J., Sackmauerova. M., Szokolay, A,, Pal'usova, 0..J. Chromatogr., 91, 545 (1974). (329) Van Alfen, N. K., Kosuge, T., J. Agr. Food Chem., 22, 221 (1974). (330) Van Middelem, C. H., Peplow, A. J., ibid., 21,
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Petroleum J. M. FRASER Union Oil Company of California,Brea, CA 9262 1
This, the twelfth in a series of reviews of analytical chemistry in the petroleum industry ( I A - I I A ) , is sponsored by the Division of Petroleum Chemistry of the American Chemical Society. Its objective is to cover the most important and relevant publications appearing essentially in 1972 and 1973. Specifically, it covers the papers abstracted in Chemical Abstracts, in the American Petroleum Institute Refining Literature Abstracts, and in Analytical Abstracts (London) for the period of July 1972 through June 1974. Thus, this review begins where the previous one left off and the general format which has evolved from the previous issues is being continued. References conform to the Chemical Abstracts "Guide for Abbreviating Periodical Titles." In addition where a reference publication might not be readily available, the abstract journal has been appended to that for the original
source. The abbreviations C.A., A.P.I.A., and B.A.A. are used to identify the abstract journals cited above. These abbreviations are followed by the volume number, the abstract number, and the year. The abstract searching was done by C. A. Simpson, Mobil Research and Development Corp., J. F. Hickerson, Exxon Co., U S A . , and R. W. King, Sun Oil Company. The collected abstracts were then screened and organized by subjects. Each collection of abstracts was then additionally reviewed, screened, and organized by fourteen authors of the eleven subjects or subsections which follow. The generous assistance of the abstractors and of the authors, many of whom have contributed to previous reviews, is very much appreciated and the production of this review is due to their combined efforts.
Crude Oils
oils (90B). Fabre et al. described a rapid gas chromatographic method for the determination of n-Clz-C32 hydrocarbons from rock extracts (34B). Kuklinskii and Pushkina examined the aromatic fractions boiling above 400 "F from Korobkov and Zhirnov crudes (51B). The benzene, naphthalene, and phenanthrene nuclei accounted for 58, 23, and 12%, respectively, of the total aromatic rings. Kajdas et al. separated the aromatic hydrocarbons from various high boiling fractions of Romashkino crude oil and tabulated their physical and chemical properties ( 4 5 B ) . Przybylski and Ligezowa fractionated the aromatic compounds from two different crude oils, examined the fractions by UV and IR spectrometry and discussed equations for calculating hydrocarbon fractions from spectrometric data (85B). Egiazarov et al. determined the amounts of all the possible c 6 - C ~aromatics, as well as n-propyl- and isopropylbenzene in the fractions of 5 Ostashkova crudes boiling below 300 "F, and the amounts of 60 individual aromatic compounds in the 300-400 O F fractions ( 3 0 B ) . Some correlations of aromatic content with the stratigraphy of the reservoirs were presented. Brodskii et al. fractionated the aromatic compounds boiling between 660-840 O F from Ro-
F. C.Trusell Marathon Oil Go, Littleton, Colo.
Hydrocarbons. Sergienko et al. determined the overall content and the distribution of the C5-C33 n-paraffins in 9 USSR crude oils (97B).The fields were selected as potential commercial sources of n-paraffins. The analytical procedure is fully described. Kurbskii et al. determined that the ratio of the Cll-C14 to C15-C18 n-paraffins from 5 Tartar crudes could be correlated with the degree of conversion of the crude in terms of the average cyclicity of the higher saturate fractions and in terms of an index derived by statistical treatment of data on the physical and chemical properties of the crude (55B). Rudakova and Timoshina determined the content of C9-CS1 n-paraffins in six crude Authors have not been supplied with free reprints for dlstrlbutlon. Extra copies of the review issue may be obtalned from Speclal Issues Sales, ACS, 1155 16th St., N.W., Washington, DC 20036. Remit $4 for domestlc U.S. orders; add $0.50 for addltlonal postage for forelgn destlnallons.
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