Anal. Chem. 1981, 53, 77R-88R (582) Tsagarell, K. K., Bokeriya, N. M.. Maslo-Zhir. Prom-st., (ll), 24 (1979);Chem. Abstr., 92,8221 If (1980). (583) Tsankova, E., Ognyanov, I., Izv. Khim., 10(4), 593 (1977);Chem. Abstr.., 89. 11978). . ~203994n , (584) Tsankova, E., Ognyanov, I., Tetrahedron, 34(5),603 (1978). (585) Tsirgvava, A. G., Sardzhveladze, G. P., Kharebava, L. G., Subtrop. Kul't., (4),20 (1977);Chem. Abstr., 89, 106128a (1978). (586) Tsuneya, T., Ikeda, N., Shiga, M., Ichikawa, N., Int. Congr. Essent. oils, [Pap.], 7th, 7,454 (1979);Chem. Abstr., 92,994302 (1980). Ponomareva, N. G., IbM., 221 (1979);Chem. Abstr., (587) Tyutyunnk, V. I., 92, 135098h (1980). (588) Uchio, Y., Bull. Chem. SOC. Jpn., 51(8),2342 (1978);Chem. Abstr., 89, 21556211 (1978). (589) Uchlo, Y., Nakayama, M., Matsuo, A., Hayashi, S., Int. Congr. Essent. oils, [Pap.] 7th, 7, 477 (1979);Chem. Abstr., 92, 135101d (1980). (590) United States Pharmacopeia1 Convention, Inc., "The United States ~
~~~
Pharmacopeia Twentieth Revision-The National Formulary Fifteenth Edition". Mack Printing Co.: Easton, Pa., 1980. (591) Umemto, K., Nagasawa, T., N@pon NogeiKagaku Kaishi, 52(4),191 (1978);Chem. Abstr.. 89, 152562k (1978). (592) Umemoto, K., Nagasawa, T., IbM., 53(8),269 (1979);Chem. Abstr.,
92,82195d (1980). (593) Uyehara, T., Ohnuma, T., Suzukl, T., Kato, T., Yoshlda, T., Takahashi, K., Koen Yoshishu-Tennen Yuki Kagobufsu Toronkai, 22nd, 235 (1979); Chem. Abstr., 93,8308x (1980). (594) Valdeig, K., Nahrung, 22(8), 745 (1978);Chem. Abstr., 90, 37696r (1979). (595) Van den Broucke, C. O., Lemll, J. A., PIanta Med., 38(3),264 (1980); Chem. Abstr., 92,211852s (1980). (596) Varga, T., Kerpel, T., Gulyas, A,, Hung. Teller 14432 (CI. A61K), 28 Jan 1978, Appl. 1311, 17 Apr 1973; 9 pp; Chem. Abstr., 89, 94888h (1978). (597)Vetma, V. P. S., Suri, R. K., Indian Perfum., 22(3),179 (1978);Chem. Abstr., 92,82219q (1980). (598) Verin, G.,Bianchini, J. P., Sbuffi, A., Parfums, Cosmef.,Aromes, 30, 49 (1979);Chem. Abstr., 92,203400~(1980). (599) Vernon, F., Richard, H., Sandret, F., IbM., 21, 85 (1978);Chem. Abstr.. 89. 203993m 11978). (600) Verzar-Petri, G.,Bakos,'P., Meres Autom., 27(3),104 (1979);Chem. Abstr., 91, 112325~(1979). (801) Verzar-Petri, G.,Banh Nhu Cuong, Radlcs, L., Ujszaszi, K., Herbe Hung., 18(2),83 (1979);Chem. Abstr., 93,53745y (1980). (602) Verzar-Petri, G.,Nagy, E., Lemberkovlcs, E., Sci. Pharm., 47(1),8 (1979);Chem. Abstr., 91,52690y (1979). (603) Vlnogradov, M. G.,Nlkishin, 0.I., Kovalev, I. P., Verenchlkov, S. P., Paylychev, V. N., Masyutin, V. N., Markevich, V. S., Strel'chik, B. S., Gringo1 ts, M. L., U.S.S.R. 725021 from Oncryrive, Izobret., Prom. Obrazfsy, Tovarnye Znaki, (12),189 (1980);Chem. Abstr., 93,36490u (1980). (604) Virmanl, 0.P., Srivastava, G. N., Datta, S. C., Indian Perfum., 22(3), 103 (1977);Chem. Abstr., 89, 94868b (1978). (605) Wamura, J.. Hosono. M., Hirao, N., Koen Yoshishu-Koryo, Terupen oyobi Sewu Kagaku ni kansuru Toronkai, 23rd, 60 (1979);Chem. Abstr.,
92, 169033~(1980). (606) Wang, C.-P., Kameoka, H., Nippon Nogei Kagaku Kaishi, 52(7),297 (1978);Chem. Abstr.. 89, 1689462 (1978).
(607) Wang, D.J.. K ' o Hsueh Fa Chan Yueh K e n , 7(10), 1036 (1979); Chem. Abstr., 92, 124929d (1980). (608)Warnecke, H. U., Dragoco Rep. (Ger. Ed.). 25(9), 192 (1978);Chem. Abstr., 90, 61065e (1979). (609) Wasyllshen, R. E., Graham, M. R., M I . Crysf.Liq. Cryst., 49(7), 225 (1979);Chem. Abstr., 91,20737c (1979). (610) Watanabe, I., Yanai, T., Tamogami. S., Nakamura, M., Habu. T., Int. Congr. fssent. Oils, [Pap.]. 7th, 7, 442 (1979); Chem. Abstr., 92, 40060a (1980). (611) Watanabe, I., Yanai. T., Tamogami, S., IbM., 461 (1979);Chem. Absfr., 92, 2033961 (1980). (612) Watson, H. R., Hems, R., Rowsell. D. G., Spring, D. J., J . Soc. Cosmet. Chem., 29(4), 185 (1978). (613) Wden, K. G.,Seppa, E. L., phytochemistry, 18(7), 1226 (1979). (614) Winter, M., Schulte-ERe, K. H.,Velluz, A., Llmacher. J., Pickenhagen, W., Ohloff, G., He&. Chim. Acta, 62(1), 131 (1979);Chem. Abstr., 90. 164719a . _11979). ,. ., (615) Yallma, I., Yanai, T., Nakamura, M., Sakakibara. H.,Habu, T., Agrk. Biol. C b m . , 42(8),1229 (1978);Chem. Abstr., 89, 106122~(1978). Yanai, T., Nakamva, M., Sakakibara, H.,Hayashi, K., Ibid., (616) Yajima, I., 43(2), 259 (1979);Chem. Abstr., 90, 192373b (1979). (617) YakobashvUi, N. Z.,Zeituridze, Ts. Sh.,Shvangiradze, 0. E., Kadzhaya, L. V., Slnatashvill. L. A.. Kharshliadze, A. A., Meslo-Zhir. Prom-sf., (4), 28 (1979);Chem. Abstr., 91, 27171x (1979). (618) Yamaguchi, K., Mihara, S., ARoku, A., Shibamto, T., LO. Chromatogr. Anal. Food Beverages, [ R o c . Symp. AM/. Foods Beverages], 2, 303 (1979);Chem. Abstr., 92,4765a (1980). (619) Yamaguchi, K., Shibamoto, T., J. Agric. Food Chem., 27(4), 847 (1979). (620) Yamanishi, T., Fukawa, S., Takei, Y., Nippon Nogei K a p k u Kaishl, 54(l),21 (1980);Chem. Abstr., 92, 179263n (1980). Iino, K.. Yoshkawa, S., Nippon Shokuhin Kogyo Gek(621) Yamashtta, I.. kaishi, 26(6). 256 (1979);Chem. Absb., 91, 137220~(1979). (622) Yang, S.D., Ghen, J.-M., Ghen, Y.H., Yao Hsueh Hsueh f a o , l4(6), 356 (1979);Chem. Abstr., 91, 1371522 (1979). (623) Yankulov, I., Stoeva, T., Ivanov, I., Zuzulova, A., Doki. Bob. Akad. Nauk, 32(7),981 (1979);Chem. Abstr.. 92, 1350970 (1980). (624) Yoshida, T., Koen Yoshishu-Koryo, Terupen oyobl Selyu Kagaku ni kansuru Toronkai, 23rd, 184 (1979);Chem. Abstr., 92, 143282d (1980). (625) Yoshida, T., NetteiNogyo, 23(1),6 (1979);Chem. Abstr., 91,717132 (1979). (626) Yunusov, A. I., Sidyakin, G. P., Nigmatuilaev, A. M., Khim. Prir. Soedin, (l),101 (1979);Chem. Abstr., 91,71687~(1979). (627) Zamureenko, V. A.. Klyuev, N. A., Dmttriev, L. B., Grandberg, I.I., Izv. nmiryazevsk. S-kh. Akad., (I), 156 (1979); Chem. Abstr., 90, 127387~(1979). (6281,Zamureenko, V. A., Klyuev, N. A,, Dmitriev, L. B., Grandberg, I. I., Ibd., 169 (1980);Chem. Abstr., 92, 152870~(1980). (629) Zaynoun, S. T., J . Soc. Cosmet. Chem., 29(5), 247 (1978). (630) Zlegler, E., Vorkommen Anal. Aetherischer oele, frgeb. Int. Arbeitstag., w1976-7978, 124 (1979);Chem. Abstr., 91, 198778e (1979). (631) Zlokowsky, B., Seifen, Oele, Fette, Wachse, 104(15),421 (1978); Chem. Abstr., 89, 185892~(1978). (632) Zob, A., Le Vanda, J. P., Parfums, Cosmef., Aromes, 60 (1979); Chem. Abstr., 90, 174496q (1979).
Pesticides Joseph Sherma Chemistry Department, Lafayetfe College, Easton, Pennsylvania 18042
Gunter Zweig
'
Office of Pesticide Programs, Environmental Protection Agency, Washington, D.C. 20460
This review covers the selective search of the literature on pesticide analysis for the period September 1978 to September 1980. The main sources of this search were Pesticides Abstracts (Volumes 12 and 13), a cross-check with Chemical Abstracts during the same period, and thorough reading of the following journals: Journal of the Association of Official 'Present address: School of fornia, Berkeley, CA 94720.
Public Health, University of Cali0003-2700/81/0353-77R$01.25/0
Analytical Chemists, Journal of Agricultural and Food Chemistry, Pesticide Monitoring Journal, and Pesticide Science. In addition, specific and ertinent chapters are cited from important books on pesticig analysis which appeared during 1979 and 1980. The present authors wish to express their appreciation and admiration to Wayne Thornburg who single-handedly and tirelessly covered the field of pesticide residue analysis for the past 10 years and who deserves a well-earned res ite. The authors want to congratulate Milton Schechter, tge winner 0 1981
American Chemical Society
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of the 1980-Burdick and Jackson International Pesticide Award of the Pesticide Division of the American Chemical Society; Milton Schechter was one of the pioneers of sticide analysis who developed the first colorimetric a n a l y t i ~ m e t h o d for DDT, bearing his name, the Schechter-Haller method (Anal. Chem. 19,51, 1947 and Ind. Eng. Chem., Anal. Ed. 17, 704, 1945). During the past 2 ears, several trends in the development of analytical methodrs for pesticides have become apparent: the increasing use of high-performance liquid chromatography (HPLC); greater interest in the analysis of metabolites and con’ugates; the attempt to include polar compounds in mu tiresidue schemes; noted advances in gas chromatography-mass spectrometry interface analysis and automated analyses, including sam le preparations. There has also been an increase in method evelopment for a relatively new class of pesticides, the synthetic pyrethroids; a review of these methods will be found in Section L. As will be seen from the biblio raphy a t the end of this review, the literature has been iivided into subsections, making it easier for the reader to locate the cited articles of his articular interest. Finally, the authors want to invite the reaiers of this article to send in any comments and suggestions in order to improve the coverage and format for the 1983 Review.
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GENERAL Books and Reviews. A sym ium on pesticide analytical
methodology held in 1979 has E n published (19A) and individual chapters are cited in this review. Volume X I of “Analytical Methods for Pesticides and Plant Growth Regulators” appeared at the end of 1980 (43A) and covers automation, HPLC, quantitative TLC, and analytical methods for pesticides recently introduced into commerce. Individual chapters are cited in their respective sections below. The EPA has published the 4th edition of “Acceptable Common Names...” (3A),which is useful to find cross reference for trade names, common or generic names, Chemical Abstracts numbers, and chemical names for all registered pesticides. Two other EPA publications are useful for pesticide analytical chemists: a description of several hundred reference esticide standards available from the EPA Laboratory a t iesearch Triangle Park (42A)and a manual for quality control for the analysis of pesticides in human and environmental samples (35A). Update I1 of “Metabolism of Pesticides” has been published (27A) and together with the two previously published volumes serves as a useful guide for pesticide chemists enga ed in the analysis of parent compounds and their metaboktes. A review has been written on selective detection in chromatographic anal sis in general but may have special application to the anacsis of pesticides (15A). A critical review on analytical testin procedures covers subjects of collaborative analysis and stanfardized methods, including multiresidue analyses (12A). The challenging problem of measuring toxicants at or near the limit of detection is discussed (11A);an example is the unproved presence of TCDD in ronnel. The use of mass spectrometry to determine trace quantities of toxicants, including DDT and DDE, in food has been reviewed (34A). As in previous years, the Association of Official Analytical Chemists reports a t its annual meeting on the progress of developing official methods for various classes of pesticides: organochlorine pesticides (5A, 7A);organophosphorous pesticides ( S A ,26A);carbamates, fumigants, and miscellaneous compounds (%A, 39A);and fungicides, herbicides, and plant growth regulators (28A, 29A). A selected bibliography of the extraction methods and analysis of phenoxy herbicides has been collected (4A). The occurrence of N-nitroso compounds in the environment and as terminal residues from the agricultural use of certain pesticides has been reviewed in two papers (16A, 23A). Sampling and Cleanup Procedures. A review of some of the procedures for extraction and determination of pesticides in plant materials, soil, and fat has been made (41A). The largest source of error in pesticide residue analysis is claimed to be found in the sampling technique (21A);this error might be reduced by increasing the number of samples. The same author discusses sampling techniques in analytical food chemistry, giving specific examples of pesticides, aflatoxins, 78R
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and nitrosamines (20A). Another review covers the influence of sampling methods and other field techniques on the results of esticide residue analysis (2A). +he pre aration of stable dilute insecticide standard solutions is &scribed (40A). Sample handling, extraction, and cleanup of mirex from fish muscle and partitionin of DDT between hexane rind a polar solvent are discussecf(1A). A graphic representation of extraction efficiencies is presented (33A). The modular approach for the automation of extraction and cleanup of pesticides in environmental samples has been utilized (17A). Automated gel chromatography has been developed for the purification of plant extracts for the determination of pesticide residues (30A). The new technology for esticide residue cleanup procedures has been discussed in &tail (18A). Sweep codistillation as a rapid cleanup procedure has been reviewed (31A)and tested for a large number of chlorinated and organophosphorus compounds with a variet of different samples of vegetable and animal foods (13A). double-reservoir rotoevaporation vessel for residue analysis eliminates a number of quantitative transfer steps in the final step of s a m le preparation frQm gel permeation eluates (%A). Small d - 2 microreticular resin columns have been evaluated for the recovery of ambient levels of pesticides and other toxic compounds from water (32A). Cleanu of foods and feeds for multiresidue pesticide analysis has gee, accomplished by gel-permeation and mini-silica gel column chromatogra hy (36A). A cellulose column procedure has been develope for the cleanup of oreanovhosvhorus insecticides in a mixed feed sample (37A). Quality Control. Several national and international interlaboratory programs have been set up to study the reproducibility of “check” and unknown samples for esticide residues. The following studies have been reporte8 a multiresidue pro am involving extraction and GC anal sis (IOA); reliability anrperformance of Canadian check samp e program (9A);the reproducibility in esticide analysis with unknown samples (22A);a Codex stufy on organochlorine compounds in butterfat (14A);interlaboratory quality control in routine determinations of chlorinated pesticide residues (8A);and a discussion of interlaboratory studies in pesticide residue analysis (6A).
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GAS CHROMATOGRAPHY The application of gas chromatography in food analysis, especially of pesticide residues, has been reviewed (4B). A multimethod for the simultaneous analysis of 75 pesticides in plant material by electron capture gas chromatography has been developed (1B). Improved resolution b ca illary GC with open tubular columns has been achievelin t i e case of chlorinated pesticides by deactivating the inner surfaces of the glass columns (9B); separation of tetrachlorophenols on deactivated glass capillary column coated with OV-101 (12B);the use of an activated charcoal vrefilter to traD out interfering.,substances from the carrier gas (5B). Detector sensitivity and selectivity have been studied by a number of methods: develoDment of a linearized 3HSc electron capture detector which proved to be linear over a larger range than the 63NiEC detector (8B);a comparative study of linearity and sensitivity of electron capture and flame photometric detector using chloropyrifos as standard ( 3 4 7B); the production of a pure Rb/quartz source for alkali flame ionization detector (6B);the reported development of a highly stable and sensitive thermaerosol detector for the analysis of P- and N-containing compounds (2B). The molar response of phosphorus-containing compounds with the flame photometric detector was found to be linear only within a homologous series (14B);this is contrary to other reports in the literature. Interfering substances in rice bran when analyzing for pesticide residues by GC with EC, thermionic, and electrolytic detectors were identified as free fatty acids but could not be removed by classical chromatoea hic techniques (15B). Application of GC to pesticide resi8,e anal sis has been reported in a number of publications: pestici e residues in tobacco (13B);polar organophosphorus pesticides if extracts were dissolved in acetone (10B);and the analysis of organochlorines, organophosphates, pyrethrins, and pyrethroids in cereal products ( I l l ? ) .
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Ovntn zvelg is visning scholar and lecturer at
me SchoDi of Public Heslih. University of
Caiitmla. Berkeley. He was Chief. Enviorv menlai Fate Branch. Hazard EmiUation Divisbn. Oflice 01 Pesticide RBSMU~Sst EPA until 1980. Dr. Zweig received his B.S. da gree in Chemistry and his Ph.D. degree in biochemistry from the University 01 Maryland. He has wide experience in bbchemisby and chromatography of pesticides and has published many research articles and boaks in the areas of his speciaky For some years. Or. Zweig wim Or. Sherma have covered paper and thin-layer chromatwraDhy tor ALIUIIC*L CKMISTRY'S Fundamenhi Reviews issues Joseph S h a n a received a B.S. in chemistry from Upsah College. East Orange. NJ. in 1955 and a Ph.D. in analyticai chemistry hom Rutgem university in 1958. His thesis research in ion exchange Chromatography was under the direction of me late Wm. Rieman 111. Dr. Sherma joined the tacuity of Latayene Coiiege in Sept 1958 and is presently fuii professor there in charge of two courses in analyticai Chemistry. Dr. Sharma independently and With others has wrinen many chapters. b d s . and reviews covering chamatographic and analyticai melhcds for pesticides. His Current research interests are in quantitative n C . mainly applied to clinical analysis and DestiCMe residues.
HIGH-PERFORMANCELIQUID CHROMATOGRAPHY (HPLC) Significant rogress has been made on the chromatographic separation anzdetection of pesticides by HPLC. General and s ecific methods have been reviewed and developed and incrude the following: a general review of pesticide analysis by HPLC (6C);a fast LC concept for automated ticide analysis (2C);pesticide metabolism studies by HPLG4C); the separation of insecticides by reversed-phase HPLC (30. Two useful tabulations of HPLC data of several hundred pesticida are found in recent publications (8C,110. HPLC has been utilized for the determination of halogenated anilines and related compounds, many of them being pesticide metabolites (9C).HPLC has been applied to determine pesticide residues on fruit and vegetable included in the EECD directive (5C). Improved detection of HPLC eluates has been accomplished with the electrochemical detector, which was found suitable for phenolic residues, aromatic amines (dinitroaniline herbicides), dinitrophenols, nitrophenyls, bipyridilium herbicides, azomethine-bond insecticides (Cytrolane and Cyolane), nitrosamines, and drazaxolon fungicide ( 7 0 . Fluorescence and UV ahsorhance detection of pesticides and naturally occurring chemicals in agricultural products have been accomplished after separation on a bonded CN polar phase column (IC). Pre- and postcolumn fluorogenic labeling for the HPLC analysis of pesticides has been critically compared (IOC). An ion-pair extraction detector for the fluorescence detection of some basic drugs, pesticides, and metabolites has been developed (12C). The addition of the ion-pairing reagent dimethoxyanthracenesulfonate (DAS) prior to the column simplifies the detector design. This method has been applied to the determination of hydroxyatrazine in urine. The enrichment of analytes for HPLC can he accomplished by using a very short precolumn of an apolar chemically bonded stationary phase (5-pm LiChrosorb RP-18), followed by a column of LiChroriorh RP-180 with a methanol-gradient mobile phase (13C). The method has been applied to the enrichment of PCBs and chloroanilines.
THIN-LAYER CHROMATOGRAPHY (TLC) Three recent cha ters dealt with different aspects of the TLC of pesticides. 6uantitative TLC of pesticides including in situ fluorometry ( 6 0 ) has been shown to yield acceptable quantitative results for submicrogram quantities of pesticides with relatively inexpensive equipment. Similar methods have been used in forensic chemistry to estimate the distribution
of pesticides in human cadavers following poisoning episodes (70) and the determination of pesticide residues in fruits and ve etahles (80) Or anophosphorus and carbamate insecticites can he d e d a n d separated by TLC with a sensitivity of 0.5 pg ( 4 0 ) . Pesticides in water have been analyzed on preadsorbent TLC plates (containing a preadsorbent sample-dispensing area) without cleanup (50). Quantitative determination was accomplished by in situ densitometry; water samples did not require prior cleanup. Chlorinated pesticides and PCB have been separated by TLC with micellar solutions (aqueous solutions of sodium dodecyl sulfate); advantages of this solvent system over the more traditional solvents are discussed (ID).
MICELLANEOUS ANALYTICAL TECHNIQUES A description is given of an automated pesticide analytical laboratory in which all steps of the residue analyses, e.g., extraction, cleanup, the determinative step, are mechanized and controlled by microprocessors (1E) Although it appears that the totally automated laboratory is not feasible at this time, certain unit operations are and may he eventually combined for "total" automation. Several novel spectrophotometric methods have been developed for general and specific urposes. Single ion mass spectrometry has been employe to quantitatively confirm dimethoate residues in wheat (2OE). Negative ion mass s ectrometry has been used to identify parathion and tetraJ f o n (16E). 2,4,6-Substituted s-triazines have been examined by combination GC-MS (31E). Field desorption mass spectrometry has been applied to the analysis of phenylurea, carbamate, and thiocarhamate pesticides (23E) and organochlorine insecticides (28E). Fourier-transform infrared spectrometry has been ap lied to the analysis of thiofanox and ita impurities WE). &panocblorine pesticides from water have been separated hy TLC and the resolved components extracted from the plates and identified by IR (2E). A bibliography on the use of IR in pesticide and residue studies has been published (12E). A nuclear double rmnance spectrograph has been designed and used to detect organochlorine, carbamate, and triazine pesticides a t concentrations of 15-100 pg/L (17E). The olarographic determination of azomethine-containing pesticigs has been reported (26E) and applied to the analysis of drazoxiline in a grain formulation. Applications of polarographic and other voltammetric methods of analysis have been reviewed (27E). Chemical derivatization techniques in pesticide analysis have been reviewed (3E,4E). Organothio hosphorus insecticide residues in fruit and vegetables have gee, analyzrd and confirmed by oxidative derivatization (25E). Trace amounts of phenols in water have been converted to the heptafluorobutyryl derivatives and analyzed by GC with electron capture detection a t a sensitivity of 20-2M) ppb (19E). Carbon skeleton GC results in hydrodechlorination of parent chlorinated pesticides, Le., to their respective hydrocarbons; the catalyst may he placed in the injection port and the resultant hydrocarbons swept onto the GC column for identification (6E). Similarly, catalytic dechlorination of organochlorine compounds, followed hy GC and MS, has led to the identification of DDT and heptachlor (7E)and aldrin and dieldrin @E). Photochemical irradiation of 33 organochlorine pesticides under UV light has led to the identification of these pesticides after GC of the degradation products (SEI. An improved method was developed to detect mirex and chlordane in the presence of PCB (15E); the modification consists of the addition of sulfuric fuming nitric acid to the cleaned-up extract. A method has een developed to confirm organochlorine pesticide residues in wildlife (22E); the procedure consists of hexane-extraction of the sample, column cleanup on Florisil and charcoal, and dechlorination with sodium ethoxide; the determinative step is by GC. Certain pesticides have been observed to form characteristic degradation products within the electron capture detector; this observation could he potentially used to identify pesticide residues io the lower picogram range (18E). Specific detection techniques for N-nitroso compounds have been reviewed in detail (30E) and applied to the analysis of these toxic impurities in the workplace (11E) and pesticide products (5E). Another technique for N-nitroso analysis has been described and utilizes GC mass fragmentography (1OE).
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Immunochemical assays have been developed for cyclodienes, parathion, S-bio-allethrin (29E),diflubenzuron, juvenile hormone (13E);parathion has been analyzed by an enzymelinked-immunosorbent assay (ELISA). A personal air sampler specifically for pesticides has been constructed and uses Chromosorb 102 as adsorbent (14E). Analytical techniques for measuring pesticidal residues in the air near agricultural treatment sites have been reviewed (24E).
CHLORINATED PESTICIDES General Procedures. Recoveries of 80-96’90 were reported for organochlorine (OC1) pesticides and PCBs from water using a gas stripping-carbon adsorption concentration technique (13F). Polyurethane foam and Tenax GC were found generally equivalent for hi h-volume sampling of chlorinated hydrocarbons in air (5f’) The cleanup of lhge lipid samples for electron capture GC and confirmation by GC-MS was based on extraction of the lipid with concentrated sulfuric acid from a 2-5% solution of light petroleum ether (56F). Potassium permanganate oxidation was used for cleanup of vegetable extracts (51F). A simplified extraction and cleanup procedure for fishery products was presented in laboratory manual style (5OF). A cleanup procedure on Woelm silica gel for extracts from biological samples separated PCBs from DDT (31F). A micro cleanu method employed silica gel deactivated with 30% water h8F). A modified Florisil cleanup method involving prewashing the column with a specified quantity of ethyl ether allowed elution of many compounds in one step (49F). Silver nitrate coated Florisil was used for simultaneous cleanup of chlorinated pesticides and phthalate esters in food extracts (52F). Sweep co-distillation cleanup was improved by nitric acid cleaning of distillation tubes and use of a larger U-tube (24F);various parameters were studied for optimization of sweep-co cleanup of animal fats (23F);and sweep co-distillation was not successful with tobacco samples unless a precleanup step with a micro Florisil column was used (43F). A six-unit cleanup and concentration apparatus for environmental samples was described (45F). A transfer technique between nonpolar and polar GC columns was used to separate OC1 insecticides from polychlorinated biphenyls and naphthalenes (42F). High-resolution WCOT capillary GC columns were used for analysis of pesticides in river and drinking water (8F). Graphitized capillary columns were studied for the separation of OC1 compounds (3F). Silica gel TLC with the mobile phase hexanexylene-benzene-toluene-cyclohexane-meth lcyclohexane (1:l:l:l:l:lv/v) was used to separate OC1 and 6 P insecticides ( 2 7 0 . Carbon-13 NMR s ctra of chlorinated polycyclodiene pesticides were reported &F), as were the NMR parameters of some chlorinated tricyclic hydrocarbons of the Clo series: chlordanes, chlordenes, and nonachlors (60F). OC1 residue determinations by GC were re rted as follows: in fluid milk a t 10 ppb levels ( 5 7 0 ;in driegugar beet pulp and molasses (28F);a rapid screening method for milk (53F); in animal fats and eggs (38F); chlorinated benzenes and phenols in biological matrices ( 3 3 0 ;in tobacco and tobacco products (44F);and in urine ( 1 7 0 . The sum of nonvolatile and volatile OC1 com ounds in water was determined by microcoulometry ( 2 1 8 . Specific Procedures. Cleanup of biological samples for determination of p,p’-DDT and its metabolites was carried out by extraction with hexane-acetone and hydrolysis of fat and protein with aqueous NaOH ( I F ) . o,p’-DDD in plasma was determined by electron ca ture GC ( 1 8 0 . DDT and metabolites were identified in tge presence of PCBs by alumina TLC with detection by tolidine reagent (32F). The analysis of the @-glucuronideof anti-12-h droxyendrin in human urine by chemical oxidation and G 8 was used as an indicator of exposure to endrin (40. Fuchsin basic was a specific chromogenic reagent for identification of endrin after silica gel TLC (26F). Endrin, aldrin, and dieldrin in biological material were derivatized (isomerized) on TLC plates by ZnClz in HC1 ( 2 9 0 . Five TLC spray reagents were compared for detection of lindane on thin-layer plates ( 5 4 0 . BHC isomers were separated on silica gel layers and detected with diphenyl reagent (55F). Toxaphene was determined in milk, butter, and meat by electron capture GC after extraction and cleanup by oxidation and chromatography on Bio Beads SX3 and Florisil columns BOR
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
(66F). Toxaphene in soil was determined by GC using a dehydrochlorination technique with KOH-methanol reagent (150. Soxhlet extraction with acidified acetone for 44 h was most effective of the several methods tested for recovery of pentachlorophenol (PCP) and tetrachlorophenol from carrots and potatoes (SF). Hydrolysis prior to extraction was important for reliable determination of PCP in urine by electron capture GC (16F). PCP was determined in milk by extraction, reaction with acetic anhydride to form the acetate derivative, and electron capture GC (19F). PCP in marine biota and seawater was determined b electron capture GC and HPLC (2UF). Electron capture 8 C was used to monitor urine and plasma of wood processing industry workers exposed to PCP (22F). Differential pulse polarography was applied to the direct determination of PCP (58F). PCP in rainbow trout was determined by mass fragment0 aphy (61F). Evaporation of aqueous sogtions containing mirex leads to losses not noted with organic solvents (46F), A column of Norit C-170 charcoal-polyurethane foam quantitatively s e p arated mirex and hotomirex from Aroclor 1254 (2F),and this method was useffor analyses of fish tissue (25F). An interlaborator study was conducted of the determination of mirex and pgotomirex in the presence of PCBs by nitration with fuming HNO and removal of nitrePCBs on an alumina microcolumn ( 4 0 4 . This cleanup approach was used in the analysis of lake sediments (12F). A reduction step was used to detect mirex in the presence of PCBs in ocean perch fillet ( 3 5 0 . Florisil column cleanup was used for the GC determination of mirex in plasma, liver, and fat from mice and monkeys (47F). Mirex in fish was determined by computerized GC-MS (34F). A simplified method for Kepone in blood was based on extraction with benzene followed by electron capture GC (I1F). Ether extraction and Florisil cleanup were used for the GC analysis of Kepone in biological samples (36F). Kepone in eel was determined by GC after extraction, partition, and column chromatography (37F). The GC analysis of 4,4’-dichlorobenzophenonein urine was used as an indicator of chlorobenzilate residues (7F). Dichlorvos was determined in air by P-mode FPD-GC ( I O F ) . Picrolam was determined by pulse polarography (59F). The decomposition of captafol in homogenized fruits and vegetables was studied (41F),and a GC procedure for residues of captafol in apple, wood, leaves, and fruit was described (39F). o , p ’-and p , p ’-Dicofol and their dichlorobenzo henone degradation products were separated by CIS reversexphase HPLC (300.
ORGANOPHOSPHORUS PESTICIDES General Procedures. Lyophilization was used to concentrate organophosphorus (OP) insecticides without evaporation loss prior to GC analysis of water samples (6G). High-speed stirring with hexane efficiently recovered OP pesticides from water (8G). Preservation methods for OP pesticides in water samples were compared, and chloroform field extraction was most satisfactory (IOG). XAD-2 resin was used to collect and stabilize OP pesticides in air (21G) and in water (26G). Organophosphorus pesticides and metabolites have been separated by glass capillary GC (18G). Five ionization methods were tested for producing mass spectra of OP pesticides, and negative ionization techniques were most sensitive (12G). The Abbott et al., Sissons and Telling, and Storherr and Watts cleanup methods were compared for determination of OP residues in vegetables, and no significant differences were found (32G). Automated gel permeation chromatography was used for cleanup of ve etables, fruits, and crops for OP determinations by FPD-8C (4G). Multiresidue rocedures for food analysis using Florisil cleanup (16G) a n a programmed temperature GC (22G) have been reported. Intact OP pesticides have been assayed in human blood by GC immediately after exposure (17G). However, the high1 reactive nature of these compounds usually requires the G 8 determination of metabolites in tissue and urine to measure the level of exposure (27G). Metabolites have been analyzed on an ion exchange resin (19G) and by derivatization with l-(4-nitrobenzyl)-3-(4-tolyl)triazine(33G)and 3-benzyl-1-ptolyltriazine (15G) reagents. Nitrophenol metabolites of OP
PESTICIDES
pesticides in rat urine were determined by polarography (34G). Dialkyl phosphate metabolites were shown not to break down or disappear in urine samples stored frozen for up to 20 weeks (20G). Seventeen mobile phases were evaluated for TLC separation of 13 OP pesticides (14G). Ammonium molybdate reagent detected 1W200-ng levels of OP residues on thin-layer plates (29G),and mercurous nitrate reagent differentiated p-phenyl organothiophosphate insecticides from other OP pesticides (31G). OP pesticides were determined in pigment-rich foods a t 2 ppb-1 ppm levels b silica gel TLC after carbon-silica gel column cleanup (24z). Specific Procedures. XAD-4 resin recovered fenitrothion quantitatively from water samples under a variety of conditions (28G). Phorate and its metabolites were separated by mixed phase GC (9G). p-Nitrophenol as a human urinary metabolite was confirmed by GC as p-ethoxynitrobenzene (23G). A thorough study of the colorimetric method for determinin malathion recommended the use of a bismuth(I1) complex 713G). HPLC was used to determine Abate in water at ppb levels (30G)and pirimiphos methyl and five metabolites in plasma and urine (11G) and for separation of methyl parathion and fenitrothion metabolites (I G). Extraction of chlorpyriphos methyl residues from aqueous solutions was made by hi h-speed stirrin with hexane, followed by analysis by FPD-Ge at 1 ppb levefs (7G). TLC was applied to the determination of Cyanox in plant sam les (5G) and pirimiphos methyl in water, soil, and plants (258). The separation and detection of lepto hos (2G) and EPN (3G) from related compounds were maie by TLC. General information, formulation analysis, and residue analysis for the insecticides etrimfos, quinalphos, and terbufos (Counter) have been presented in chapters included in Volume XI of “Analytical Methods for Pesticides and Plant Growth Regulators” (35G).
CARBAMATE PESTICIDES General Procedures. Amberlite XAD-m2 resin was used to extract carbamate insecticides from water prior to GC determination using an N-P detector (21H). Extracts of vegetables containing residues were cleaned-up prior to determination by elution from a Waters C18 Sep-Pak with methanol (14H). A rapid procedure for preparation of support-bonded Carbowax 20M GC column packings, which allow the separation of intact, underivatized carbamate pesticides, was described (13H). These columns in combination with an electrolytic conductivity detector and CI-MS were used to determine carbamate residues in soil (6H). Derivatization of carbamates with methanesulfonyl chloride followed by GC with an S-mode FPD detector was used to determine residues in lentil straw (11H). Because of the heat lability of carbamate pesticides, HPLC is becoming increasingly important for their determination. Analysis of fruits and vegetables at 0.025-0.25 pm involved only extraction and direct injection into the Lzcolumn. For complex mixtures, a second column with a different stationary phase was used (3H, 4H). Carbamate, thiocarbamate, and phenylurea pesticides were determined at 10-20 ppt concentrations by HPLC, with subse uent identification by field desorption mass spectrometryq2OH). N-Methylcarbamate insecticides and carbamate metabolites were separated on C8, C18,, and cyanopropyl silane columns by elution with an acetonitrile-water gradient and detected at ng levels with a fluorescence detector after in-line NaOH hydrolysis to methylamine and subsequent reaction with o-phthalaldehyde and 2-mercaptoethanol to form the fluorophore (7H, 8H). Carbamate esticides in ostmortem material were separated and detectefby silica gerTLC at 0.5 pg levels (23H). Detection limits for several carbamate and phenylurea pesticides on HPTLC silica gel layers with a variety of detection methods were reported, and the method was applied to the analysis of fruits and vegetables (2H). Specific Procedures. Carbaryl in poisoned honey bees was determined by HPLC after cleanup of extracts on a Florisil column (10“). Carbaryl was determined at 5 ppm on forest foliage and from stream water and soil at 0.1 ppm by HPLC (17H). Carbaryl residues in apples (0.02 ppm) were determined by silica gel TLC after charcoal cleanup (1623. Ultrasonic, Lourdes, and Waring blenders were all found to be adequate for extraction of carbofuran from radishes
(24H). Carbofuran residues in soil and water (0.10 ppm) were determined by methanol-water extraction, base hydrolysis, and HPLC separation and UV (280 nm) detection of the phenol moiety (15H). Aminocarb residues in natural water (0.01-1 pg/L) and foliage (0.002-1 pg/g) were determined b extraction, coagulation and partition cleanu , and GC w i d a dual N-P detector (12H). Aminocarb a n f i t s major metabolites were separated by TLC on silica gel with hexaneacetone (1:lv/v) and ethyl ether-hexane-ethano1(77:203 v/v) mobile phases and ninhydrin or enzyme inhibition detection (22H). Bendiocarb was determined on wool by C18 reversed-phase HPLC with UV detection a t 280 nm (25H). Carbendazim was separated and semiquantitated by silica el G TLC (1823). Propoxur and 2-isopropoxyphenol were etermined in blood, urine, and tissues by GC with electron capture detection (9H). HPLC and mass spectrometry were combined to study metabolic products of chloropropham in extracts of rat urine and plants (5H). GC MS was used to determine the quantity of ethyl carbamate ormed in tobacco and tobacco smoke after treatment of tobacco with maleic hydrazide (19H). Cleanup by alumina column chromatography was applied to the GC determination of carbophenothion residues (0.002 ppm) in mice samples (1H).General information, formulation analysis, and residue analysis for promacyl are presented in Volume XI of “Analytical Methods for Pesticides and Plant Growth Regulators” (26H).
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HERBICIDES See also the previous section on carbamate pesticides. General Procedures. Silica gel and XAD-4 resin provided efficient collection of herbicides in air monitoring studies (181). Field desorption mass spectrometry was applied to the determination of herbicides in surface water samples (521). Sweep co-distillation was used for the multiresidue analysis of herbicides in vegetables and fruits (151). Gas chromatography was used in the analysis of s-triazine herbicides as follows: at the ng level as silyl derivatives (471); on capillary columns (271,281);in urine using an N-mode Hall electrolytic conductivity detector (161);and as he tafluorobut ryl derivatives in food analysis (31). The 8 C / M S of bis&lkylamino)-s-triazines was studied (241), and the gas chromatographic, spectrophotometric, and electrochemical behavior of substituted s-triazines were compared for analytical use (301). HPLC data on 5-pm silica gel with 2-4% 2-propanol in n-pentane mobile phase was reported for 23 s-triazine derivatives (111). .+Triazines were separated on “24141) and CN-4441) chemically bonded HPLC stationary phases. HPLC on silica gel with UV (240 nm) detection was used for the determination of hydroxy s-triazine residues in plant material (351). Triazine residues in water (10 ppb) were determined by silica gel TLC separation, AgN08 (UV) detection, and densitometric quantitation (421). Triazine and urea herbicides were determined in water by TLC using the Hill-reaction inhibition detection technique (371). Potential degradation roducts of triazine herbicides were separated by paper a n a thin-layer chromatography (261). Chloroform was the best solvent tested for extraction of phenylurea herbicides from aqueous media (51). Eleven substituted ureas and related compounds were determined in soil at 0.01 ppm by acetone extraction, alkaline hydrolysis to anilines, steam distillation, bromination, and electron capture GC ( 6 0 . Phenylureas in water were determined by HPLC (Wdetection at 254 nm) after extraction and cleanup on silica gel and C8 columns (461)and in soil and foods directly on a C18 column (361). Retention values and UV absorption of 11urea herbicides on reversed-phase and silica gel columns were re orted (331). Urea herbicide residues were determined by TLE) in soil and water with detection by in situ catalytic hydrolysis followed b reaction of the corresponding anilines with dansyl chloride 611) to produce fluorescent spots. TLC se arated herbicidal thiocarbamates and their sulfoxide and suffone metabolites (201) and was used in the determination of thiocarbamate herbicides in foods after acetonitrile extraction and silica gel column cleanup (171). Specific Procedures. Reported studies on chlorophenoxy acid herbicides include the following: determination of 2,4-D at the 0.1 ppm level in urine by GC with XAD-2 resin cleanup (431);collection on XAD-2 resin and GC determination of the propylene glycol butyl ether esters of 2,4,5-T in air (221); sampling of 2,4,5-T and 2,4-D from air on Chromosorb 102 ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
81 R
PESTICIDES
lugs (190;separation of 2,4-D and its phenolic derivatives reversed-phase HPLC (130; separation of the amino acid conjugates of 2,4-D by ion-pair HPLC ( 2 0 ; and the TLC properties of amino acid conjugates of 2,4,5-T and the GC and MS s ectra of methyl ester derivatives (10. MCPA and its metagolites were determined in food grains and vegetables by electron capture GC ( 3 8 0 ;MCPA and terbacil in apples by densitometric TLC and electron capture GC, respectively (32Z);MCPA, mecoprop, and MCPB and metabolites in soil by GC of the pentafluorobenzyl esters (91,400;and MCPA and its soil metabolites b silica gel TLC ( 3 9 4 . Atrazine was determ i n d in runoff water by reversed-phase HPLC after preconcentration on XAD-2 resin (310. HPLC was proven superior to colorimetry for the determination of atrazine residues in soil (510. Drying and storage of soil samples caused loss of extractable atrazine (480. The presence of ammonium nitrate in soil sample extracts injected for GC analysis caused inconsistent peak heights of samples and standards by increasing column efficiency (100. Paraquat in blood and urine was determined by anion exchange cleanup combined with colorimetry using sodium dithionite rea ent (210, by radioimmunoassay (251,450,and by HPLC folfowing chloroform extraction (290 The following analyses of miscellaneous herbicide residues were reported: dalapon in plant tissues and water by GC as the 3-phenylpropyl ester (500; nitrofen and neburon in natural water extracts by GC (12Z);neburon and 3,4-dichloroaniline metabolite in natural water extracts by GC (80; linuron, diuron, and metoxuron and de radation products in soil by GC/MS after ethylation ( 2 3 0 ;%romacilin alfalfa hay, fruit, soil, and water by GC with an N-P thermionic detector (490; asulam and its metabolite in peaches by GC of the per Nmethylated sulfanilamide derivative with an N-P detector (44; dinoseb in fababeans by electron capture GC (70; and glyphosphate and its aminomethylphosphonic acid metabolite in water by cellulose TLC ( 3 4 0 . Volume XI of “Analytical Methods for Pesticides and Plant Growth Regulators” (530 contains chapters reporting general information, formulation analyses, and residue analyses for chloropropham, difenzoquat (Avenge), Drepamon, flurecol, oxyfluorfen, Quintex, and tebuthiuron.
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FUNGICIDES Triphenyltin hydroxide (fentin) and its degradation products were determined in water at 0.01 p m by electron capture GC after conversion to their hydride grivatives, while inorganic tin cation and oxide were determined by a previously described procedure (114. Fentin residues (0.05 ppm) in vegetables and cocoa products were determined by Soxhlet extraction with dichloromethane, cleanup on an alumina column, and spectrofluorometry with excitation at 415 nm and a 500 nm emission wavelength (14. Spectrofluorometry of the triphenyltin-3-hydroxyflavonecomplex was used to determine triphenyltin chloride in water a t concentrations of 0.004-2 ppm ( 2 4 . A common method for determination of diphenyl and 2phenylphenol in citrus fruits involves separation by distillation followed by GC, often using an internal standard (64. An improved steam distillation method for se aration of the two fungicides from citrus fruits involving non&aline and alkaline traps was reported (124. The two compounds were also quantitatively recovered from citrus fruits and apples using a Likens-Nickerson extraction instrument ( 9 4 . A silver-loaded alumina column has been used for cleanup of chlorothalonil, dichlofluanid, tolylfluanid, and vinclozolin prior to GC determination of multiresidues ( 7 4 . Vinclozolin in the presence of benomyl, BMC, and methyl thiophanate was determined after extraction from grapes by reversed-phase HPLC with UV detection at 221 nm ( 3 4 . The systemic fungicide bupirimate was determined in apples at 0.5-0.3 ppm levels by GC using either an N-mode N-P detector or an S-mode FPD ( 4 4 . Residues of 1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea (DPX-3217) in grapes, potatoes, and wine at 0.04 ppm were determined after ethyl acetate extraction and adsor tion chromatography cleanup by GC with an Nselective gtector ( 5 4 . Thiourea in citrus peels was determined a t concentrations of 1-10 ppm by GC after ethyl ether extraction and partition and alumina column cleanup (134. Transition-metal salts were applied as ion pair reagents in the HPLC of dithiocarbamate fungicides (104. Zineb, maneb, 82R
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
and tetramethylene thiuram disuflide (TMTD) were simultaneously determined by olarography (84. General information anlformulation and residue analyses for the fun icides i rodione and tricyclazole and for the ethylenebis&thiocarf ates and their degradation products were presented in chapters in Volume XI of “Analytical Methods for Pesticides and Plant Growth Regulators” (145).
CHLORINATED COMPOUNDS RELATED TO PESTICIDES (PCB, PCT, PCN, TCDD) Polychlorinated biphenyls (PCBs) were separated from DDT and its analo ues by using chromic acid reagent to convert DDE to DDF and a silica gel column to resolve the PCBs from DDT (23K). Chromic acid treatment used durin the analysis of freshwater and marine f i h for polychlorinate! biphenyls to eliminate or anochlorine pesticide interference caused losses of several PEB homologues, leading to chanqed GC peak patterns and areas (21K). Recovery and elution characteristics of 24 pesticides and metabolites and 2 PCBs on a silicic acid column were evaluated; all compounds studied, except toxaphene, Aroclor 1260, and technical chlordane, eluted in only one fraction (20K). Automated glass ca illary GC was used to analyze PCBs and OC1 pesticide resi&es in agricultural products (22K), and glass capillary GC/MS analysis of hydrox PCBs was re orted (14K). PCBs, olychlorinated na htxalenes (PCNsP, and polychlorinatefterphenyls (PCTsP were analyzed via carbon skeleton GC using hydrogen as the carrier gas and on-column catalytic reduction to biphenyl, naphthalene, and a mixture of 0-,m-,and p terphenyl, respectively (3K, 16K). PCBs were quantitated after dehydrochlorination to biphenyl by LiAlH4 using HPLC with UV (248 nm) detection (17K). PCBs in Swedish coastal waters were monitored by electron capture GC MS (1K). PCBs in drinking water a t low ng/L levels were etermined by capillary column electron capture GC after XAD-2 resin cleanup (13K). Polychlorinated terphenyls at trace levels in human adipose tissue were determined by GC/MS after sample preparation by a modified Mills-Onley-Gaither procedure and further cleanup on a BioBeads SX-3 column eluted with toluene-ethyl acetate (1:3 v/v) (24K). Radioisotope dilution assay was evaluated for the estimation of PCBs (11K). A neutral cleanup rocedures utilizing magnesia/Celite 545, alumina, and Florisircolumns for separation of 2,3,7,8-tetrachlorodibem -dioxin (TCDD) from li id in beef fat and milk extracts was &scribed and comparecf)to acid-base cleanup (15K). Analysis techniques for ppt TCDD detection in environmental samples after the industrial accident a t Seveso, Italy, were described (4K), and different quantitative MS techniques were compared (6K). TCDD was analyzed in the presence of PCBs by glass capillary column GC MS ( 2 K ) . High-resolution GC/MS determination of TCD in environmental samples had a detection limit of 8 ppt and accuracy within *15% (7K). Results of oxygen and methane negative ion chemical ionization MS and methane positive ion chemical ionization MS were described for dioxins (8K). Developments and applications of mass fragmentography in TCDD analysis were reviewed (9K). Low-resolution GC low resolution MS was a specific procedure for detection o TCDD in environmental samples if suitable control samples were available (1OK). TCDD was determined in fish at 10-100 ppt levels by a technique involving digestion and extraction of the Sam le followed by a series of adsorbent and chemically mo8fied adsorbent liquid column chromatography cleanup steps and finally an elevated temperature reversed-phase HPLC step before multiple ion monitoring GC/MS (12K). GC MS was also used to determine TCDD residues on metal sur aces such as barrels and tanks used for storage of 2,4,5-T products (5K). The toxic impurities 3,3’,4,4’-tetrachloroazobenzene and 3,3‘,4,4f-tetrachloroazoxybenzene in commercial diuron, linuron, and 3,4-dichloroaniline samples were determined by GC/MS after acetone extraction and partition and silica gel column cleanup (19K). Chlorinated benzyl phenyl ethers were identified as a possible interference in the determination of chlorinated dioxins in 2,4,5-T and its derivatives (18K).
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MISCELLANEOUS PESTICIDES Analytical methods for pesticides which were not easily classified in, or were omitted from, the sections above are reviewed in this space.
PESTICIDES
Recommended methods for the analysis of natural pyrethrins and the synergist piperonyl butoxide have been reviewed (26L). Naturally occurring esters of pyrethrum extract were analyzed by the combination GLC and chemical ionization (CI) mass spectrometry (28L). Synthetic pyrethroids have become very important commercial insecticides, and methods of residue anal sis have been developed: determination of permethrin by 8 L C (IOL); the cleanup of p ethroid extracts by adsorption chromato aphy, followed by Z C (7L); GLC determination of permetar in in bovine tissues (48L); cleanup of residue samples by adsorption chromatography followed by GLC of decamethrin ( B L , 39L) and the analysis of this synthetic pyrethroid by reversed- and normal-phase HPLC (43L);the HPLC analysis of sumicidin (fenvalerate) (42L). Several organophosphorus-containing insecticides and their metabolites have been analyzed by a variety of methods: acephate in garden vegetables by GLC (44L);acephate and methamidophos by GC and detected with an alkali flame detector (56L);GLC analysis of chlorphoxim in water and fiih (72L);the determination of phoxim (Baythion) by TLC (33L); development of a semiautomated system for the analysis of 4-nitrophenol metabolite in urine (50L). The insecticides methomyl and oxamyl have been determined as residues in cro s as trimethylsil 1 ethers using GC as determinative step (8 ). Carbaryl and fndane residues in potatoes originating from an insecticide mixture have been analyzed by TLC; carbaryl spop were vjsual+ed enzymatically and lindane with diphenylamine; sensitivities achieved were 0.1 ppm for carbaryl and 1 ppb for lindane (55L). A combined method for the determination of vinclozolin (Ronilan fungicide) and endosulfan residues in strawberries by GC has been accomplished (73L). Recommended formulation and residue analysis methods for Evisect (thiocyclam hydrogenoxalate insecticide) by GLC have been published (69L). HPLC has been used for the determination of rotenoids from plant extracts (40L) and soil and crops (31L). The moluscicide Bayluscide (clonitralid or niclosamide) has been determined as residues in water and aquatic or anisms by first hydrolyzing the parent compound to 2-cf~loro-4nitraniline (CNA) and analyzing the CNA directly by GC (3615) or colorimetrically by forming an azo dye (16L);residues of niclosamide in bananas have been found by gas chromatographing the heptafluorobutyryl derivative of CNA (30L). HPLC has been applied to the residue determination of the rodenticide brodifacoum in rat tissue (32L). When detecting carbamate insecticides on thin layers by cholinesterase enzyme spray, it has been found that warfarin also inhibited the enzyme and might give false results (6L). Analytical methods for the important class of fungicides ethylenebis(dithiocarbamates) (EBDC's) and their toxic impurity ethylenethiourea (ETU) have been the subject of a number of papers: a detailed treatment of recommended methods for EBDCs, ETU and other degradation products and impurities (45L);the extractive acylation of ETU from water and subsequent GC analysis (62L);high resolution of ETU without derivatization by capillary GLC (27L). ETU in air has been analyzed, after trapping on mixed cellulose esters, by a colorimetric method involving the complexing agent pentacyanoamine ferrate (51L). The fungicide thiabendazole and its metabolite 2-benzimidazole carbamate have been determined as residues in fruit and crops by as chromatographing the pentafluorobenzyl derivatives ( 6 4 f ) . Dinoseb residues in crops and soil have been analyzed by GC after hydrolysis of extract and thorou h column cleanup (21L). Ethoxyquin (discontinued use in t i e US.)has been determined in apples by HPLC (17L). The simultaneous extraction and analysis of the two herbicides trifluralin and nitrofen as residues in crucifers has been accomplished; the final determinative step is by GC-electron capture (EC) (71L). Oryzalin and prosulfalin residues in soil have been determined by HPLC at a sensitivity of 0.02 ppm (37L). It is significant that Raman spectrometry has been used to analyze some urea herbicides (monuron and diuron) a t a sensitivity of 2.4 X lo-' M, which, however, is not sensitive enough to adapt Raman spectrometry to residue analysis at submicrogram concentrations (2.55). The herbicide pyramin has been analyzed as residues in soil by TLC (68L);the detection limit was found to be 0.02 p m. Ioxynil residues in animal tissues have been determinefby
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TLC a t a sensitivity of 0.1 ppm (35L). Dacthal has been analyzed qualitatively and characterized by combination C&/MS at a sensitivity of 1ppb in water (54L). A simple TLC method has been devised for the determination of lyphosate and its metabolite aminoethylphos honic acid (53L.7. A direct method of solvent extraction of bipRenyl in citrus fruit is much simpler than conventional steam distillation; final analysis is by GC (15L). A surprisin ly large number of papers on the analysis of paraquat by iifferent methods in several substrates have appeared during this report period: the multiple development of TLC for paraquat and related compounds (415);a spectrophotometric method with the reagent tetraiodomercurate(I1) (20L);the quantitative determination in urine and serum by differential pulsed polarography (19L);the GC determination of paraquat reduced with sodium borohydride (61L);the spectrophotometric determination of araquat in blood following reduction with dithionite (9L);t e development of a radioimmunoassay for serum paraquat (18L). The determination of para uat in marijuana was accomplished by reversed-phase H P L 8 with an ion- airing reagent in the mobile phase; the limit of detectioniy this method is 2 ng of paraquat (24L). Another method for the detection of paraquat in marijuana was by TLC or spot tests usin dithionite reagent (11L). Paraquat in sunflower seeds was etected by reversed-phase HPLC (52L). HPLC has been used for the determination of residues of naphthaleneacetic acid (13L) and naphthaleneacetamide (14L) in apples. The plant growth regulator flurecol has been analyzed in formulations by UV absorption, as the butyl derivative by GC, or in aqueous salt concentrations by TLC and scanning densitometry (5L). Residue analysis has been performed by GC after convertin flurecol tQ fluorenone and using bromophos as internal staniard. Maleic hydrazide and its fl-Dglucoside in foods have been analyzed by cleaning up the extract on ion exchange columns and hydrolyzing the con'ugate with 8- lucosidase; the freed maleic hydrazide was determined by b L C (47L). Daminozide (Alar)residues in foods were determined by alkaline h drolysis of parent compound to dimethylhydrazine and analyzing the pentafluorobenzoyl derivative by GLC (46L). The active ingredients of the mothproofing agent Eulan W A New have been identified by NMR and MS after GLC; a method for the extraction, cleanup, and analysis of the isomers of the components of Eulan W A New and their metabolites in fish tissue has been accom lished b GC-MS (67L). Sodium fluoroacetate has been a n a L e d by 8 L C after extensive cleanup of animal tissues with silica gel, separation by microdistillation, and derivatization with pentatluorobenzyl bromide; the resultant PFB-fluoracetate is analyzed by GC-EC (49L). Juvenile hormones in insects have been determined by converting them to their respective 10-heptafluorobutyrate11-methoxy derivatives and analyzing these derivatives by capillary GC with EC detection; final identification was accomplished by IR, MS, and NMR (29L). Residues of boron-containing pesticides in citrus fruit have been determined by a colorimetric method using quinalizarin as com lexing rea ent for boron (41L). A review of the GC methocfs for the fetermination of organomercury(I1) compounds has been published (57L). The analysis of organotin pesticides has been developed by a number of researchers using the following techniques: formulation analysis of fentin hydroxide by titration with HCl after treatment with alkaline alumina or by GLC of the converted parent compound to butyltriphenyltin (66L);residues of fentin have been determined by the colorimetric anal sis of Sn(IV) with pyrocatechol violet or alternatively by dC-MS of the converted triphenylmethyltin (66L). Residues of DU-TER, Brestan, Plictran, and Vendex have been measured by GC-MS (6315); Vendex residues in apples have been analyzed by an atomic absorption apparatus coupled to a heated raphite atomizer (58L);organotin compounds in polyvinyl cfiloride have been analyzed by reacting the extracts containing the tin compounds with haemotoxylin; this method mi ht also be adaptable to residue analysis of fruits and fooifs (6515). The speciation and analysis of organic and inorganic arsenic compounds have been accomplished by a novel, recently reorted technique involving the separation of the species by k P L C on a low-capacity anion exchange column coupled to
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a graphite furnace and atomic absorption detector equipped with an automatic sampler (70L);the method was capable of separating and analyzin arsenite, arsenate, methanearsonic acid (MAA), and cacodyfic acid. Another approach by other researchers has been to volatilize the arsenic species to their corresponding arsines after reduction by sodium borohydride and forming different color complexes with silver diethyldithiocarbamate (34L). Methanearsonic acid (MAA) in soil and rice has been analyzed by TLC after reduction with KI (1L). Several modification of older methods and development of two methods for the analysis of fumigants have been reported: The official first action AOAC method for the determination of fumigants in grain has been modified by recommending the use of an OV-17 GC column and W i detector (12L). Total inorganic bromide resulting from the use of methyl bromide as a soil fumigant is converted to eosin by reacting on a TLC plate with fluorescein; quantitative TLC of the resultant eosin yields results that are comparable to an X-ray fluorescence spectroscopic technique (22L). Ethylene dibromide (EDB) from soil is distilled and decomposed by Schoeniger combustion, and the resultant HBr is injected into an Indium-lined cavity of a molecular emission cavity analysis instrument; Bris quantitated from the intensity of the InBr emission (376 nm) (3L). A similar technique has been ap lied to a number of chlorinated and brominated fumigants foBowing separation of the resultant ammonium halides by TLC (2L). As already mentioned in the previous section (K), there are a number of compounds that, althou h not classifiable as pesticides, are nevertheless covered in tiis review due to their strong relation to pesticides. The contaminant of 2,4,5-trichlorophenol derived pesticides 2,3,7,&tetrachlorodibenzop-dioxin (TCDD) is such a compound. The qualitative and quantitative methods for dioxin analysis have recently been reviewed (23L);the authors suggest that improvement of presently used methods could be achieved by increased specificity of screening methods and the replacement of electron impact (EI) mass spectrometry by negative ion (see also 16E) and chemical ionization MS. The determination of possible residues of TCDD in human milk involves multistep cleanu and final separation from interferences by reversed H P L 6 the final determinative step is low-resolution GC-MS (60L). LITERATURE CITED QENERAL (1A) Albro, P. W. Ann. NYAcad. Scl. 1979, 320,19-27. (2A) Ambrus, A. I n "Advances in Pesticide Science"; Geissbuehler, H., Ed.; Pergamon Press; Oxford, England, 1979; Vol. 3, pp 620-632. (3A) Elaiock, C. R., Shaughnessy, J. A,, Johnson, D. E., and Caswell, R. L. (ret.) "Acceptable Common Names and Chemical Names for the InqedC ent Statement of Pesticide Labels"; U S . Environmental Protection Agency, Washington, D.C. 20460; EPA 540/9-77-017, 1979, 247 pp, 4th ed. (may be obtained from NTIS, Springfield, VA 22161). (4A) Bovey, R. W., Diaz-Colon, J. D. rex. Agric. Exp. Stn. Mlsc. Publ. 1381 1978, 33 pp. (5A) Burke, J. A. J . Assoc. Off. Anal. Chem. 1979, 62(2), 376-9. (6A) Burke, J. A. I n "Advances in Pesticide Science"; Geissbuehler, Ed.; Pergamon Press: Oxford, England, 1979; Vol. 3, pp 633-42. (7A) Burke, J. A. J . Assoc. Off. Anal. Chem. 1980, 63(2), 277-82. (EA) Carl, M. I n "Advances in Pesticide Science"; Geissbuehler, H., Ed.; Pergamon Press: Oxford, England, 1979, Vol. 3, pp 660-3. (9A) Cochrane, W. P., Whitney, W. In "Advances in Pesticide Science"; Geissbuehler, H. Ed.; Pergamon Press: Oxford, England, 1979; Vol. 3, pp 664-7. (10A) Corneliussen, P. E. J . Assoc. Off. Anal. Chem. 1980, 63(2), 27577. (11A) Crummett, W. 6. Ann. NY Acad. Sci. 1979, 320,43-47. (12A) Egan, H. Ecotoxicoi. Environ. Saf. 1980, 4(1), 77-84. (13A) Eichner, M. 2.Lebensm.-Unters.-Forsch. 1978, 167(4), 245-9. (14A) Elgar, K. E. I n "Advances in Pesticide Science"; Geissbuehler, H.. Ed.; Pergamon Press: Oxford, England, 1979; Vol. 3, pp 668-72. (15A) Ettre, L. S. NBS Spec. Pub/. ( U . S . ) 1979, 519 (Trace Org. Anal.: New Front Anal. Chem.), 547-85. (16A) Fine, D. H. Adv. Environ. Sci. Techno/. 1980, 10, 39-123. (17A) Getz, M. E., Hanes, G. W., Hili, K. R. N8S Spec. Publ. ( U . S . ) 1979, 519 (Trace Org. Anal.: New Front. Anal. Chem.), 345-53. (16A) Getz, M. E., Hill, K. R. Chapt. 11 in "Pestickle Analytical Methoddogy". ACS Svmo. Ser. 136, Harvey. J. Jr., Zweig, G. Eds. ACS, Washinpton, D.C., f980, 209-29. (19A) Harvey, J., Jr., Zweig, G. Eds. Pesticide Analytical Methodology, ACS symp. Ser. 136, ACS, Washington, D.C., 1980, 406 pp. (20A) Horwkz, W., Howard, J. W. NSS(U.S.) Spec. Publ. 519, 1979, 231242. (21A) Horwitz, W. I n "Advances in Pesticide Science"; Geissbuehler, H. Ed.; Pergamon Press: Oxford, England, 1979; Vol. 3, pp 649-55. (22A) Kaiser, R. E. I n "Advances in Pesticide Science"; Geissbuehler, H. Ed.; Pergamon Press: Oxford, England, 1979; Voi. 3, pp 643-8. (23A) Kearney, P. C., Amundson. M. E., Eeynon, K. I., Drescher, N., Marco,
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0. J., Mlyamoto, J., Murphy, J. R., Oliver, J. E. Pure Appl. Chem. 1980, 52(2). 501-26. (24A) ' k y , T. W., Stalling, D. L. Anal. Chem. 1979, 51(1), 169-70. (25A) Mccuily, K. A. J . Assoc. Off. Anal. Chem. 1979, 62(2), 383-7. (26A) McCully, K. A. J . Assoc. Off. Anal. Chem. 1980, 63(2), 283-5. (27A) Menzle, C. M. U. S., Fish WMl. Sew. Spec. Scl. Rep., WMl. 1978, 212, 381 pp. (28A) Newsome, W. H. J . Assoc. Off. Anal. Chem. 1979, 62(2), 379-80. (29AJ Newsome, W. H. J . A u W . Off. Anal. Chem. 1980, 63(2), 273. (30A) PflUgmachet, J., Ebing, W. J . CbfOMfogf. 1978, 160(1), 213-20. J., Ebing, W. Landwirtscb. Forsch. 1979, 32(1-2), 82-7. (31A) Pfl~gmacher, (32A) Rees, G. A. V., Au, L. Bull. Envlron. Contam. Toxlcol. 1979, 22(4/5), 561-66. (33A) Robbins, W. K. Ana/. Cbem. 1979, 57(11), 1860-1. (34A) Self, R. Biomed. Mass Spectrom. 1979, 6(9), 361-73. (35A) Sherma, J., Beroza, M. U . S . MIS Pi3 Rep. P6-298,71 1, 1979, 413 PP. (36A) Specht, W., TilIkes M. Fresenius z. Anal. Chem. 1980, 301(4), 3007. (37A) Stahr, H. M., Gaul, M., Hyde, W., Moore. R. Mlcrochem. J . 1979, 24(1), 97-101. (38A) Storherr, R. W. J . Assoc. Off. Anal. Chem. 1979, 62(2), 376. (39A) St-rr, R. W. J . Assoc. Off. Anal. Chem. 1980, 63(2), 272. (40A) Suett, D. L., wheatley, G. A,, Padbury, C. E. Anavst(London) 1979, 104(1245), 1176-80. (41A) Taylor, 1. S.,Thler, H. P. Pure Appl. Chem. 1979, 51(7), 1605-13. (42A) Thompson, J. F., Watts, R. R., Eds. U . S . P8 Rep. PB-284224, 1978, 114 pp. (43A) Zweig, G., Sherma, J., Eds. "Analytical Methods for Pestlcldes and Plant Growth Regulators"; Academic Press: New York, 1980; Vol. XI, Updated General Techniques and Additional Pesticides, 408 pp.
Nrrs
GAS CHROMATOQRAPHY ( l e ) Becker, G. Dtscb. Lebensm. Rundsch. 1979, 75(5), 148-52. (26) Brazhnikov, V. V., Poshemanskil, V. M., Sakcdynskii, K. I., Chernyakin, V. N. J. Chromatogr. 1979, 175(1), 21-6. (36) Cochrane, W. P., Maybury, R. E.,Greenhalgh, R. G. J. Envlron. Scl. Health 8 1979, 14(2), 197-212. (46) Dickes, G. J. Taknta 1979, 26(12), 1065-1099. (56) Evrard, E., R a u w k , C., Roberhoid, M., Mercier, M. J . Chromatogr. 1978, 161(1),97-102. (66) Greenhaw, R., Mueller, J., Aue, W. A. J . Chromatcgr. Scl. 1978, 16(1), 8-11. (76) Greenhalgh, R., Cochrane, W. P. J. Cbfomatogr. 1980, 188(2), 305-13. (86) Hanisch, R. C., Lewis, R. G. Natl. tech. Inform. Sew. P8-276,990, 1980, 35 pp. (96) Houtermans, W. J., Boodt, C. P. J . H@h Resolut. Chromatogr. Chromatogr. Commun. 1979, 2(5), 249-50. (106) LeBel, G. L., Williams, D. T. J. Assoc. Off. Anal. Chem. 1979, 62(6). 1353-55. (116) Mestres, R., Atmawijaya, S., Chevallier, Ch. Ann. Falslf. Expert. Chem. 1979, 72(780), 577-589. Pest. Abstr. 1980, 13, 80-1162. (126) Onuska, F. I., Comba, M. E. J . H/gh Resolut. Chromatcgr. Cbomatogr. Commun. 1978, 1(4), 209-10. (136) Reff, H., Moser, F. Beitr. Tabakforsch. 1977, 9(3), 168-175. Pest. Abstr. 1979, 12, 79-0733. (146) Sass, S., Parker, G. A. J . Chromatogr. 1980, 189(3), 331-349. (156) Sonobe, H.. Carver, R. A., Kamps, L. R. J. Agrlc. FoodChem. 1980, 28(2), 265-9. HIGHPERFORMANCE L l W I D CHROMATOGRAPHY (HPLC) (1C) Argauer, R. J. Chapt. 7 in "Pesticide Analytical Methodology". Harvey, J., Jr., Zwelg, G., Eds., ACS Symp. Ser. 136, American Chemlcal Soclety, Washington, D.C. 1980, pp 103-26. (2C) Burns, D. A. Chapt. 2 in Ibid., pp 13-30. (3C) Cabras, P., Meioni, M., Pirisi, F. M. J . Chromatogr. 1979, 176(3), 4737. (4c) Harvey, J., Jr. Chapt. 1 in "Pesticide Analytical Methodology". Harvey, J. Jr., Zweig, G. Eds., ACS Symp. Ser. 136, American Chemical Soc., Washington, D.C. 1980, pp 1-14. (5C) Hoodless, R. A,, SMweii, J. A., Skinner, J. C., Treble, R. D. JChromatogr. 1978, 166(1), 279-86. (6C) Ivie, K. F. Chapt. 2 I n "Analytical Methods for Pesticides and Plant Growth Regulators", Voi. XI; Zweig, G., Sherma, J., Eds.; Academic Press: New York 1980; pp 55-78. (7C) Kissinger, P. T., Eratin, K., King, W. P., Rice, J. R. Chapt. 5 in "Pesticide Analyticai Methodology". Harvey, J. Jr., Zweig, G., Eds. ACS Symp. Ser. 136, American Chemical Society, Washington, D.C. 1980, 57-88 pp. (8C) Lawrence, J. F., Turton, D. J. Chromatcgr. 1978, 159(2), 207-26. (9C) Lores, E. M., Eristoi, D. W., Moseman, R. F. J . Chromatogr. Sci. 1978, I6(8), 358-62. (1OC) Moye, H. A. Chapt. 6 in "Pesticide Analytical Methodology". Harvey, J. Jr.. Zweia. G. Eds. ACS Svmo. Ser. 136. American Chem. SOC., Washington,-D.C. 1980, pp 89-102. (11C) Schooley, D. A., Quistad, G. G. Prog. Drug Res. 1979, 3, 1-113. (12C) VanEuuren, C., Lawrence, J. F., Brinkman, U. A. T., Honigberg, I. L., Frei. R. W. Anal. Chem. 1980. 52(4). 700-4. (13C) Van VIM, H. P. M., Bootsman, T. C.,Frei, R. W., Brinkman, U. A. T. J . ChrOmStogr. 1979, 185, 463-95. THIN-LAYER CHROMATOGRAPHY (TLC)
(ID) Armstrong, D. W., Terriil, R. Q. Anal. Chem. 1979, 51(13), 2160-3. (2D) Hauck. H. E., Amadori E. Chapt. 9 I n PesticMe Analytical Methodology", Harvey, J. Jr., Zweig, G. eds. ACS Symp. Ser. 136, 1980,
PESTICIDES American Chem. SOC.,Washington, D.C., pp 127-57. (3D) Mallet, V. N. Chapt. 8 I n Ibki.. 127-57 pp. (40) Rao, S. Govinda, Raju, I. S. S.,Oopalachari, N. C. Id.J. Agric. Chem. 1977, 10(1-2), 209-1 1. (50) Sherma, J. Am. Lab. 1978, 10(10), 105-9. (613) Sherma, J. Chapt. 3 I n "Analytical Methods for Pesticides and Plant Growth Regulators", Vol. XI; Zweig, G., Sherma, J.. Eds.; Academic Press: New York, 1980; pp 79-122. (7D) Tewari, S.N. Chapt. 14 in "Pesticide Analytical Methodology"; Harvey, J. Jr., Zweig, G. eds. ACS Symp. Ser. 136, 1980,pp 259-76. (ED) Ubiergo, G. O., Marracino, J. M., Mantovanl, V. E. Rev. Fac. Ing. Qulm. (Univ. Nac. Lnoral) 1977. 42. 109-17: Chem. Absfr. 1980. 93. 24580k. OTHER ANALYTICAL METHODS AND CONFIRMATORY TECHNIQUES (1E) Burns, D. A. Chapt. 1 in "Analytical Methods for Pesticides and Plant Growth Regulators". Zweig, G., Sherma, J., Eds.; Academic Press: New York, 1986 Vol. XI pp 3-53. (2E) Chmil, V. D. Zh. Anal. Khim. 1979, 34(10), 2067-70, Chem. Absfr. 1980. - - - - ,92. 169680. ---(3E) Cochrane, W. b: J. Chromafogr. Sci. 1979, 77(3), 124-37. (4E) Cochrane, W. P. Chapt. 12 I n "Pesticide Analytical Methodology". Harvey, J. Jr., Zweig, G. Eds., ACA Symp. Ser. 736, Amer. Chem. SOC., Washington, D.C. 1980,pp 231-49. (5E) Cohen, S. Z.,Zweig, G., Law, M., Wright, D., Bontoyan, W. R. IARC SCi. Pub/. 79, 1978,pp 333-42. (6E) Cooke, M., Nickless, G., Roberts, D. J. J. Chromafogr. 1980, 787(1), 47-55. (7E) Cooper, W. J., Dennis, W. H., Jr. Chemosphere 1978, 7(4), 299-305. (8E) Cooper, W. J., Dennis, W. H., Jr., DeLeon, I. R., Laseter, J. L. Chemosphere 1979, 8(4), 191-9. (9E) Erney, D. R. Anal. Lett. 1979, 72(A5), 501-22. (10E) Farnelli, R., Chiabrando, C., Airoldi, L. Anal. Lett. 1978. A 17(10), 845-54. (11E) Fine, D. H. ACS Symp. Ser. 94, 1979,247-54. (12E) Glang, P. A. Agric. Res. Serv. 1978, N E - 9 1 , 95 pp. (13E) Hammock, B. D., Mumma, R. 0. Chapt. 18 in "PestlcMe Analytical Methodology", Harvey, J. Jr., Zweig, G. Eds., ACS Symp. Ser. 136, American Chemical Society, washington, D.C. 1980,pp 321-52. (14E) Hill, R. H., Jr., Arnold J. E. Arch. Environ. Confam. Toxicol. 1979, 8(5), 621-28. (15E) Holdrinet. M. Bull. Environ. Contam. Toxicol. 1979, 21(1-2), 46-52. (16E) Homing, E. C.,Carroll, D. I., DzMic, I., Stillwell, R. N. Chapt. 19 in Pesticide Analytical Methodology". Harvey, J., Jr., Zweig, G. Eds. ACS Symp. Ser. 136, American Chemical Society, Washington, D.C. 1980,pp 353-66. (17E) Kadaba, P. K., Bhagat, P. K., Osredkar, R., Murthy, V. R. K. Report 1978,RR-116, W79-01981, OWRT-A-065-KY; Order No. PB-289370, 69 pp. Avail. NTIS; Chem. Absfr. 1979, 91, 112241q. (18E) Kapila, S.,Aue, W. A. J. Chromafogr. 1978, 748(2), 343-351. (19E) Lamparski, L. L., Nestrick, T. J. J. Chromafogr. 1978, 756(1), 143-51. (20E) Lee, Y. W., Westcott, N. D. J. Assoc. Off. Anal. Chem. 1979,62(4), 782-85. (21E) Lowry, S. R., Gray, C. L. Chapt. 17 I n "Pesticide Analytical Methodology", Harvey, J., Jr., Zweig, G. Eds., ACS Symp. Ser. 136, American Chemical Society, Washington, D.C. 1980,pp 299-320. (22E) Rosewell, K. T., Baker, B. E. Bull. Environ. Confam. Toxicol. 1979, 27(4-5), 470-7. (23E) Schulten, H. R. Fresenius 2. Anal. Chem. 1978, 293(4), 273-81. (24E) Seiber, J. N., Ferreira, G. A., Hermann, B., Woodrow, J. E. Chapt. 10 I n "Pesticide Analytical Methodology", Harvey, J., Jr., Zweig, G. Eds., ACS SYmp. Ser. 736, American Chemical Society, Washington, D.C. 1980,pp 177-208. (25E) Singh, J., Cochrane, W. P. J. Assoc. Off. Anal. Chem. 1979, 62(4), 751-6. (26E) Smyth, M. R., Osteryoung, J. G. Anal. Chem. 1978, 50(12), 1632-37. (27E) Smyth, M. R., Smyth, W. F. Analyst (London) 1978, 703(1227), 52967. (28E) Suzuki, M., Yamato, Y., Koga, M. Biomed. Mass Specfrom., 1978, 5(9), 518-23. (29E) Wing, K., Hammock, B. D. Ca. Agric. 1980, 34(3), 34-5. (30E) Wolf, M. H., Wing, C. Yu, Fine, D. H. Chapt. 20 I n "Analytical Methods for Pesticides and Plant Growth Regulators"; Zweig, G., Sherma, J. Eds.; Academic Press: New York 1980; Vol. XI, pp 363-87. (31E) Zeman, A., Woerie, R. Org. Mass Specfrom. 1978, 13(1). 43-50.
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CHLORINATED PESTICIDES (1F) Ahmad, N. J. Assoc. Off. Anal. Chem. 1979, 62(5), 1150-1154. (2F) Babjak, L. J.; Chau, A. S.Y. J. Assoc. Off. Anal. Chem. 1979, 62(5), 1174-1 176. (3F) Bacaloni, A.; Goretti, G.; Lagana, A,; Petronio. B. M. J. Chromafogr. 1979, 775( I), 169-173. (4F) Baklwin, M. K.; Hutson, D. H. Analyst (London) 1980, 105( 1146). 6065. (5F) Billings, W. N.; Bidieman, T. F. Environ. Sci. Technoi. 1980, 14(6), 679-683. (6F) Boshoff, P. R.; Pretorius, V. Bull. Environ. Confam. Toxicol. 1979, 2213). 405-412. (7F) -Braby, S. S.f Enos, H. F.; Levy, K. A. Bull. Environ. Confam. Toxicoi. 1980,24(5), 813-815. (8F) Brodtmann, N. V.; Koffskey, W. E. J. Chromafogr. Sci. 1979, 77(2), 97-1 10 (9Fj Brut% G. W.; Currie. R. A. J. Assoc. Off. Anal. Chem. 1980, 63( 7), 56-60.
(1OF) Bryant, R. J.; Mlnett, W. Pesfic. Scl. 1978, 9(6), 525-528. (11F) Caphn, Y. H.; Thompson, B. C.; Hebb, J. H., Jr. J. Anal. Toxbol. 1979, 3(5), 202-205. (12F) Chau. A. S. Y.; Babiak. L. J. J. Assoc. Off. Anal. Chem. 1979, 62( I), 107-113. (13F) Colenutt, B. A.; Thorburn, S. Inf. J. Envlron. Anal. Chem. 1980, 7(3), 231-244. (14F) Cox, R. H.; McKinney, J. D. Org. Magn. Reson. 1978, I f ( I f ) , 541546. (15F) Crist, H. L.; Harless, R. L.; Moseman, R. F.; Callls, M. H. Bull. Environ. Contam. Toxicoi. 1980, 24( f ) , 231-237. (16F) Edgerton, T. R.; Moseman, R. F. J. Agric. Food Chem. 1979, 27( 7), 197-199. (17F) Edgerton, T. R.; Moseman, R. F.; Linder, R. E.; Wrlght, L. H. J. Chromatogr. 1979, 170(2), 331-342. (18F) Enger, A.; Brunetaud, J. M.; Moschetto, Y.; Choisy, H. J. Chromafogr. 1978, 152( I), 234-239. (19F) Erney, D. R. J. Assoc. Off. Anal. Chem. 1978, 6 1 ( 7 ) . 214-217. (20F) Faas, L. F.; Moore, J. C. 1979. J. Agric. Food Chem. 1979, 27(3), 554-557. (21F) Fritschi, U.; Fritschi, G.; Kussmaul, H. 2. Wasser Abwasser-Forsch. 1978, 17(5), 165-167, 170. (22F) Oossler, K.; Schaller, K. H. Fresenius' 2.Anal. Chem. 1978,290(2), 111-112. (23F) Heath, A. 8.; Black, R. R. J. Assoc. Off. Anal. Chem. 1979, 62(4), 757-763. (24F) Heath, A. B.; Black, R. R. J. Assoc. OM.Anal. Chem. 1980, 63(3), 529-531. (25F) Insalaco, S. E.; Makarewicz, J. C.; Vestling, M. M. J. Agric. F m d Chem. 1980, 28(2), 261-265. (26F) Katkar, H. N.; Joglekar, V. D. Cum. Sci. 1980, 49(9), 350-351. (27F) Khan, M. A.; Paul, J. Microchem. J. 1979, 24(3), 333-340. (28F) Koster, P. B., Zuckerindusfrle 1978, 103(3), 200-202. (29F) Kuhekar, M. P.; D'Souza, F. C.; Meghal, S.K. J. Chromafogr. 1978, 747, 432-434. (30F) Kvahrag, J.; Iwata, Y.; Gunther, F. A. Bull. Environ. Contam. Toxicol. 1979, 21( 1-2),25-28. (31F) Kveseth, N. J.; Brevik. E. M. Bull. Envlron. Confam. Toxlcol. 1979, 21( f - Z ) , 213-218. (32F) Laitem, L.; Gaspar, P. Bull. Envlron. Contam. Toxlcol. 1978, 79(3), 264-265. (33F) Lamparski, L. L.; Langhorst, M. L.; Nestrick, T. J.; Cutie, S. J. Assoc. Off. Anal. Chem. 1980, 63( 7), 27-32. (34F) Laseter, J. L.; DeLeon, I. R.; Remele, P. C. Anal. Chem. 1978,50(8), 1169-1172. (35F) Lusbv. W. R.: Hill. K. R. Bull. Environ. Contam. Tox/co/. 1979. . 22(4. ' 5),567-569. (36F) Mady, N.; Smith, D.; Smith, J.; Wezwick, C. NBS(US) Spec. Publ. 1979,NO. 579, 341-343. (37F) MeiJs,A. W. H. M.; Ernst, G. F. J. Chromafogr.1979, 777, 486-489. (38F) Minis. Agric., Fish 8 Food, Plant Pathoi. Lab., Harpenden, Hertfordshire AL5 2BD, England. Analyst (London) 1979, 104( 7238), 425-433. (39F) Ngoran, N.; Ercegovich, C. D.; Hickey, K. D.; Mumma, R. 0. J. Agrlc. Food Chem. 1979, 27(6), 1167-1170. (40F) Nwstrom, R. J.; Won, H. T.; Holdrinet, M. V. H.; Calway, P. G.; Naftei, C. D. J. Assoc. Off. Anal. Chem. 1980, 63( f ) , 37-42. (41F) Nutahara, M.; Yamamto, M. Nippon Noyaku Gakkalshi (J. Pesfic. Sci.) 1978, 3(2), 101-107. (42F) Paramasigamani, V.; Kaplla, S.;Aue, W. A. J. Chromafogr. Scl. 1980, 18(4), 191-194. (43F) Ptlugmacher, J.; Ebing, W. 2. Lebensm. Unfers. Forsch. 1979, 16915). 343-345. (44F) Richter, M. Nahrung 1978, 22(9). 759-768. (45F) Solomon, J. Anal. Chem. 1979, 51( f f ) , 1861-1863. (46F) Stein, V. B.; Pnman. K. A. Bull. Environ. Confam. Toxicol. 1978. 19(6), 755-757. (47F) Stein, V. B.; Pittman, K. A. Bull. Environ. Confam. Toxicol. 1979, 23(3), 300-305. (48F) Steinwandter, H.; Schluter. H. Msch. Lebensm. Rundsch. 1978, 7414). 139-141. (49F) 'SGmac, R. M. J. Assoc. Off. Anal. Chem. 1979, 62(1), 85-88. (50F) Stout, V. F.; Beezhold, F. L. Fish. Bull. 1979, 76(4), 880-886. (51F) Suzuki, T.; Ishikawa, K.; Sato, N.; Sakai, K. I. J. Assoc. Off. Anal. Chem. 1979, 62(3), 685-688. (52F) Suzuki, T.; Ishikawa, K.; Sato, N.;Sakai, K. I. J. Assoc. Off. Anal. Chem. 1979, 62(3), 689-694. (53F) Suzuki, T.; Ishikawa, K.; Sato, N.: Sakai, K. 1. J. Assoc. Off. Anal. Chem: 1979, 62(3), 681-684. (54F) Thielemann, H. Scl. Pharm. 1978, 46(4), 320-322. (55F) Thieiemann, H. 2. Chem. 1978, 76(9), 155-156. (56F) Veierov, D.; Aharonson, N. J. Assoc. Off. Anal. Chem. 1980,63(2), 202-207. (57F) Veierov, D.; Aharonson, N. J. Assoc. Off. Anal. Chem. 1980, 63(3), 532-535. (58F)- Wade, A. L.; HawkrMge, F. M.; Williams, H. P. Anal. Chim. Acta. 1979, 105( f ) , 91-97. (59F) Whittaker, J. W.; Osteryoung, J. J. Agric. Food Chem. 1980, 28( f ) , 89-94. (60F) Wilson, N. K.;Sovocool, G. W. Org. Magn. Reson. 1977, 9(9), 536542. (81F) Wu, A.; Lech, J. J.; Glickman, A.; Pearson, M. L. J. Assoc. Off. Anal. Chem. 1978, 61(5), 1303-1306. ORGANOPHOSPHORUSPESTICIDES (1G) Abe, T.; Fujimoto, Y.; Tatsuno, T.; Fukami, J. Bull. Eniviron. Confam. roxicoi. 1979, 22(6), 791-795. ANALYTICAL CHEMISTRY, VOL.
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PESTICIDES
(2G) Abou-Donia, M. B. J . Chromatogr. 1978, 150( 7), 238-241. (3G) Abou-Donia, M. B.; Ashry, M. A. J . Chromatogr. 1978, 754( I),113116. (4G) Auk, J. A.; Schofield, C. M.; Johnson, L. D.; Waltz, R. H. J . Agrlc. Food Chem. 1979, 27(4), 825-828. (5G) Baida, T. A. Gig. Sanit 1979, 44(3), 47-48. (60) Bargnoux, H.; Pepin, D.; Chabard, J. L.; Vedrine. F.; Petii. J.; Beraer. J. A. Analusis 1980, 8(3), 117-1 18. (7G) Blanchet, P. F. J . Agric. Food Chem. 1979, 27(1), 204-206. (8G) Bianchet, P. F. J . Chromatogr. 1979, 179( I),123-129. (9G) Boshoff, P. R., Pretorius, V. J . Agrlc. FoodChem. 1979, 27(3), 826630. (10G) Bourne, S. J . Environ. Sci. Heath B 1978, 13(2),75-88. (11G) Breaiey, C. J.; Lawrence, D. K. J . Chromatogr. 1979, 768(2), 461-
."".
AAP
(12G) Busch, K. L.; Bursey, M. M.; Hass, J. R.; Sovocooi, G. W. Appl. Spectrosc. 1978, 32(4), 388-399. (13G) Clark, E. R.; Qazi, I. A. Ana/yst (London) 1979, 104( 7245), 11291134. (14G)- Curini, M.; Lagana, A,; Petronio, B. M.; Russo, M. V. Talenta 1980, 27( 1), 45-48. (15G) Daughton, C. G.; Cook, A. M.; Alexander, M. Anal. Chem. 1979, 51(12). 1949-1953. (16G) Ferreira, J. R.,; Silva Fernandes, A. M. J . Assoc. Off. Anal. Chem. 1980, 63(3), 517-522. (17G) Fournier, E.; Sonnier, M.; Dally, S. Clin. Toxicol. 1978, 72(4), 457462. (18G)-Hild, J.; Schulte, E.; Thier, H. P. Chromatographia 1978, 71(7), 397399. (19G) Houx, N. W. H.; Jongen, W. M. F.; de Vries, A. W.; Welling, W.; Dekker, A. Pestic. Sci. 1979, 10(3), 185-200. (20G) Ito, G.; Kiigore, W. W.; Seabury, J. J. Bull. Environ. Contam. Toxicol. 1979, 22(4-5), 530-535. (21G) Kaminski, F.; Melcher, R. G. Am. Ind. Hyg. Assoc. J . 1978, 39(8), 678-683. (220) Kawamura, Y.; Takeda, M.; Uchlyama, M. Shokuhin Eiseigaku Zasshi ( J . Food M g . SOC. Jpn.) 1978, 79(6), 511-517. (23G) Kirby, K. W., Keiser, J. E.; Groene, J.; Slach, E. F. J . Agric. Food Chem. 1979, 27(4), 757-759. (24G) Komives, T.; Marton, A. F.; Dutka, F. Etelmiszervizsgaleti Kozl. 1978, 24(5-6), 201-204; Chem. Absf. 92, 1 0 9 2 0 6 ~(1980). (25G) Krasnykh, A. A.. Khim. Sel'sk. Khoz. 1978. 16(11), 36-37. Chem. Abst. 90,.49428t (1979). (26G) LeBei, G. L.; Williams, D. T.; Grifflth, G.; Benoit, F. M. J . Assoc. Off. Anal. Chem. 1979, 62(2), 241-249. (27G) Lores, E. M.; Bradway, D. E.; Moseman, R. F. Arch. Envlron. Heath 1978. 33f5). ,. 270-276. ( 2 8 4 Mallet, V. N.; Francoeur, J. M.; Volpe, G. J . Chromatogr. 1979, 172, 388-393. (29G) Murty, A. S.; Rajabhushanam, B. R.; Christopher, K.; Ramani, A. V. J. Assoc. Off. Anal. Chem. 1980, 63(4), 756-757. (30G) Otsuki, A.; Takaku, T. Anal. Chem. 1979, 51(7), 833-835. (31G) Prasad, B. N.; Kawale, G. 6.; Jogiekar, V. D. Curr. Sci. 1978, 47(3), 77-79. (32G) Smart, N. A,; Hill, A. R. C.; Roughan, P. A. Ana/yst(London) 1978, 103( 1228),770-772. (33G) Takade, D. Y.; Reynolds, J. M.; Nelson, J. H. J . Agric. Food Chem. 1979, 27(4), 746-753. (34G) Zietek, M. Mickrochim. Acta 1979, 21( 7-2), 75-83. (35G) Zweig, G.; Sherma, J., Eds. "Analytical Methods for Pesticides and Piant Growth Regulators"; Academic Press: New York, 1980; Volume XI, Updated General Techniques and 408 pp. ~
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CARBAMATE PESTICIDES
(1H) Brown, P. M.; Uppai, G. S . J . Chromatogr. 1980, 190( 1), 201-202. (2H) Davies, R . D. J . Chromatog. 1979, 170(2), 453-458. (3H) Fogy. I.; SchmM. E. R.; Huber. J. F. K. 2. Lebensm. Unters. Forsch. 1980;.170(3), 194-199. (4H) Fogy, I.; Schmid, E. R.; Huber, J. F. K. Z . Lebensm. Unters. Forsch. 1979,- 169(6)8, 438-443. '
(5H) Games, D. E.,; Weerasinghe, N. C. A. J . Chromatcgr. Sci. 1980,
18(3), 106-107.
(6H) (7H) (8H) (9H)
Hail, R. C.; Harris, D. E. J . Chromatogr. 1979, 769, 245-259. Krause, R. T. J . Chromatogr. Sci. 1978, 16(7), 281-288. Krause, R. T., J . Chromatogr. 1979, 185, 615-624. Krechniak, J.; Foss, W. Bull. Environ. Contam. Toxlcol. 1979, 23(4-5),
531-535. (10H) Lord, K. A.; Cayiey, G. R.; Smart, L. E.; Manlove. R. Ana&st(London) 1980, 105( 1248). 257-261. (11H) Maitien, J. C.; McDonough, L. M. J . Agric. Food Chem. 1980, 28( I ) ,
78-82.
(12H) Mamarbachi, G. Bull. Environ. Contam. Toxicol. 1980, 24(3), 415-
422.
(13H) Moseman, R. F. J . Chromatogr. 1978, 166(2), 397-402. (14H) Muth, G. L.; Erro. F. Bull. Envlron. Contam. Toxicol. 1980, 24(5),
759-765. (15H) Neisen, T. R.; Cook, R. F. J . Agric. FoodChem. 1979, 27(6), 11881188. (16H) Piechocka, J. Metody Badania fozostalosci festyc. Srodkach Spozyw. 1978, 23-26; Chem. Abstr. 1980, 93, 245709. (17H) Pieper, G. R.; Bull. Environ. Contam. Toxicol. 1979, 22( 1-2), 167171. (18H) Prakash, S. R.; Vijayashankar, Y . N.; Visweswariah, K. Pesticides 1979, 8 ( 7), 49-50. (19H) Schmeltz, I.; Chiong. K. G.; Hoffmann, D. J . Anal. Toxicol. 1978, 2(6),265-268.
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(20H) Schulten, H. R.; Stoeber, I. Fresenlus' Z . Anal. Chem. 1978, 293(5),
370-376. (21H) Sundaram, K. M. S.;Sreto, S.Y.; Hindie, R. J . Chromtogr. 1979, 777( 1), 29-34. (22H) Sundaram, K. M. S.;Szeto, S.Y.; Hindle, R. J . Chromatogr. 1980, 194( 1), 100-103. (23H) Tewari, S. N.; Singh, R. J . Chromatogr. 1979, 172, 528-530. (24H) Wheeler, W. B.; Thompson, N. P.; Edelstein, R. L.; Krause, R. T. Bull. Environ. contam. roxlcoi. 1979, 23(3),387-390. (25H) Zehner, J. M.; Simonaltis, R. A.; Bty, R. E. J . Assoc. Off. Anal. Chem. 1980, 63( 7), 47-48. (26H) Zweig, G; Sherma, J., Eds. "Analytical Methods for Pesticides and Plant Growth Regulators"; Academic Press: New York, 1980; Volume XI, Updated General Techniques and Addhional Pesticides, 408 pp. HERBICIDES
(11) Arjmand, M.; Hamilton, R. H.; Mumma, R. 0. J . Agric. Food Chem. 1978, 26(4), 898902. (21) Arjmand, M.; Hamilton, R. H.; Mumma, R. 0. J . Agrlc. Food Chem. 1978, 26(4), 971-973. (31) Bailey, R.; LeBei, G.; Lawrence, J. F. J . Chromatogr. 1978, 761( I), 251-257. (41) Bardalaye, P. C.; Thompson, N. P.; Carlson, D. A. J . Assoc. Off. Anal. Chem. 1980, 63(3), 511-516. (51) Bazhenova, L. N.; Kirichenko, V. E.; Pashkevich, K. I. U I . Anal. Khlm. 1979, 34(3), 554-556. (61) Caveriy, D. J.; Denney, R. C. Ana/yst(London) 1978, 103( 1225), 368374. (71) Cessna, A. J. J . Agric. Food Chem. 1979, 27( 7), 191-193. (81) Copin, A.; Delmarceiie, J.; Deleu, R.; Renaud, A. Anal. Chim. Acta 1980, 716( I),145-152. (91) Cotterill, E. G. J . Chromatogr. 1979, 171, 478481. (101) COttWIll, E. 0. A/W/ySt(L~ndon)1979, 104( 1242), 878-680. (111) Defek, P.; Pacakova, V. J . Chromatogr. 1980, 787(2), 341-349. (121) Deleu, R.; Copin, A. J . Chromatogr. 1979, 171, 263-268. (131) Drinkwine, A. D.; Bristoi, D. W.; Fleeker, J. R. J . Chromatogr. 1979, 1 7 4 7), 284-268. (141) Dufek, P.; Pacakova, V.; Tesarova, E. J . Chromatogr. 1980, 197, 115-120. (151) Eichner, M.: Renner, R. Z . Lebensm. Unters. Forsch. 1980, 170( 7), 1-4. (161) Erickson, M. D.; Frank, C. W.; Morgan, D. P. J . Agric. Food Chem. 1979, 27(4), 740-743. (171) Fodor Csorba, K.; Komives, T.; Marton, A. F.; Dutka, F. flelmiszervlzsgaleti Kozi. 1978, 24(5-6), 205-209; Chem. Abst. 1980, 92, 109207~. (181) &over, R.; Kerr, L. A. J . Environ. Sci. Health B 1978, 73(3),311-321. (191) Jackson, J. W.; Thomas, T. C. J . Air Pollut. Control Assoc. 1978, 28( 11), 1145-1147. (201) Komlves, T.; Aprokovacs, V. A.; Marton, A. F. J. Chromatogr. 1979, 775( 7)- 222-223. (211) Kuo, T . I . T'ai-wan I Hsueh Hui Tsa Chih 1979, 78(3), 151-156; Chem. Abstr. 1979, 91, 69395d. (221) Langhorst, M. L. Am. Ind. Hyg. Assoc. J . 1980, 41(5), 328-333. (231) Lawrence, J. F.; van Buuren, C.; Brinkman, U. A. T.; Frei, R. W. J . Aaric. Food Chem. 1980. 2813).630-632. (241jLecbrcq, P. A.; Pacakova. V . ' J . Chromatogr. 1979, 178( 7), 193-207. (251) LevM, T. Proc. Anal. DiV. Chem. Soc. 1979, 16(2), 72-76. (261) Loos, M. A.; Kearney, P. C. J . Chromatcgr. Sci. 1978, 16, 86-89. (271) Matisova, E.; Krupcik, J.; Liska, 0. J. Chromatogr. 1979, 773( I),139146. (281) Matisova, E.; Krupcik, J.; Liska, 0.;Szentlvanyi, N. J . Chromatogr. 1979, 769, 261-269. (291) Miller, J. J.; Sanders, E.; Webb, D. J . Anal. Toxicol. 1979, 3( I ) , 1-3. (301) Packova, V.; Nemec, I. J . Chromatogr. 1978, 148( I), 273-281. (311) Paschal, D.; Blckneli, R.; Siebenmann, K. J . Envlron. Scl. Heath 6 1978, 13(2), 105-115. (321) Polzhofer, K. Z . Lebensm. Unters. Forsch. 1978, 187(3), 162-164. (331) Pribyi, J.; Herzei, F. J . Chromatogr. 1978, 166( I ) , 272-278. (341) Ragab, M. T. H. Chemosphere 1978, 7(2), 143-154. (351) Ramsteiner, K. A.; Hoermann, W. D. J . Agric. Food Chem. 1979, 27(5), 934-938. (361) Rus, V. Rev. Chim. (Bucharest) 1978, 29( I f ) , 1088-1089. (371) Sackmauerova, M.; Kovac, J. Fresenius' Z . Anal. Chem. 1978, 292(5),414-415. (381) Sattar, M. A.; Paaslvirta, J. Chemosphere 1979, 8(3), 143-149. (391) Sattar, M. A.; Paaslvirta, J. J . Chromatogr. 1980, 189( 7), 73-78. (401) Sattar, M. A.; Paasivirta, J. Anal. Chem. 1979, 51(6), 598-602. (411) SchoRen, A. H. M. 1.;Van Buuren, C.; Lawrence, J. F.; Brinkman, U. A. T.; Frei, R. W. J . Liq, Chromatogr. 1979, 2(4), 607-817. (421) Sherma, J.; Miller, N. 1. J . Llq. Chromatogr. 1980, 3(6), 901-910. (431) Smith, A. E.; Hayden, B. J. J . Chromatogr. 1979, 777, 482-485. (441) Smolkova, E.,Jr.; Packakova, V. Chromatographia 1978, 11( 12), 698702. (451) Stewart. M. J.; LevM, 1.;Jarvie, D. R. Clin. Chlm. Acta 1979, 94(3) 253-257. (461) Stoeber, I.; Reupert, R. Vom Wasser 1978, 51, 273-283. (471) Stoks, P. 0.;Schwartz, A. W. J . Chromatogr. 1979, 168(2), 455-460. (481) Swain, D. J. J. Agric. Food Chem. 1979, 27(4), 915-916. (491) Ting, K. C.; Root, G. A.; Tichelaar, G. R. J . Assoc. Off. Anal. Chem. 1980, 63( 1 ) , 43-46. (501) Van der Poll, J. M.; de Vos, R. H. J . Chromatcgr. 1980, 787( I), 244248. (511) Vickrey, T. M.; Kariesky, D. I.; Biackmer, G. L. J . Assoc. Off. Anal. Chern. 1980, 63(3), 506-510. (521) Yamato, Y.; Suzuki, M.; Watanabe. T. Biorned. Mass Spectrorn. 1979, 6(5). 205-207. '
PESTICIDES (531) Zweig, G.; Sherma, J., Eds. "Analytical Methods for Pesticides and Plant Growth Regulators"; Academic Press: New York, 1980; Volume XI, Updated General Techniques and Additional Pesticides, 408 pp. FUNGICIDES (1J) Baker, P. G.; Farrington, D. S.; Hoodless, R. A. Analyst (London) 1080, 705( 7248), 282-285. (2J) Blunden, S. J.; Chapman, A. H. Analyst (London) 1078, 703( 7233), 1266-1269. (3J) Cabras, P.; Meloni, M.; Pena, M.; Pirisi, F. M. J. Chromatogr. 1070, 780( I), 184-190. (4J) Ernst, G. F.; Heutink, R.; Verveld-Roedef, S. Y. J. Chromafogr. 1070, 779(2), 351-354. (5J) Holt. R. F. Pesfic. Sci. 1070, 70(6), 455-459. (6J) Isshiki, K.; Tsumura, S.; Watanabe, T. Agric. Blol. Chem. 1078, 42( 72),2375-2379. (7J) Lokke, H. J. Chromafogr. 1079, 779(2), 259-270. (8J) Nangniot, P.; Zenon-Roland, L.; Berlemont-Frennet, M. Analusis 1078, 6 ( 6 ) ,273-275. (9J) Pyysalo, H.;Kiviranta, A,; Lahtinen, S. J. Chromafogr. 1070, 768(2), 5 12-5 16. (1OJ) Smith, R. M.; Morarji, R. L.; Salt, W. G.; Stretton, R. J. Analyst (London) 1080, 705( 7247), 184-185, (11J) Soderquist, C. J.; Crosby, D. G. Anal. Chem. 1078, 50( 77), 143514.79
(12J)-?anaka, A.; Nose, N.; Suzuki, P.; Hlrose, A.; Watanabe, A. Analyst (London) 1078, 703( 7229), 851-855. (13J) Toyoda. M.; Ogawa, S.; Ito, Y.; Iwaida, M. J. Assoc. Off. Anal. Chem. 1070, 62(5). 1146-1149. (14J) Zweig, G., Sherma, J., Eds. "Analytical Methods for Pesticides and Plant Growth Regulators"; Academic Press: New York, 1980; Volume XI, Updated General Techniques and Additional Pesticides, 408 pp. CHLORINATED COMPOUNDS RELATED TO PESTICIDES (1K) Ahnoff. M.; Eklund, G.: Josefesson, E. Acta Hvdrochlm. Hvdrobbl. 1070 7(2), 171-178. (2K) Buser, H. R. "Dioxin: Toxicological and Chemical Aspects"; Cattabeni, F., Cavallaro, A,, Galli, G., Eds.; Spectrum Publ., Inc.: New York, 1978; Chanter 4. 27-41 (3K) &ke, k;Nickless, G.; ReScott, A. M.: Roberts, D. J. J. Chromafogr. 1078. 15612). 293-299. (4K) di Domenico, A.; Merli, F.; Boniforti, L.; Camoni, I.; Di Muccb, A.; Taggi, F.; Vergori, L.; Colli, G.; Elli, G.; Gorni, A,; Grassi, P.; Inverniui, G.; Jemma, A.; Luciani, L.; Cattabeni, F.; De Angelis, L.; Galli, G.; Chlabrando, C.; Fanelli, R. Anal. Chem. 1070, 5 1 ( 6 ) ,735-740. (5K) Erk, S. D.;Taylor, M. L.; Tiernan, T. 0. Chemosphere 1070, 8 ( 7), 7-14. (6K) Freudenthal, J. "Dioxln: Toxicological and Chemical Aspects"; Cattabeni, F., Cavallaro, A., Galli, G., Eds., Spectrum Publ., Inc.: New York, 1978; Chapter 5, 43-50. (7K) Harless, R. L.; Oswald, E. D. "Dioxin: Toxicological and Chemical Aspects"; Cattabeni, F., Cavallaro, A,, Galli, G., Eds.; Spectrum Publ., Inc.: New York, 1978, Chapter 6, 51-57. (8K) Hass, J. R.; Frlesen, M. D.; Hoffman, M. K. Org. Mess Spectrom 1070, 74( 7). 9-16. (9K) Holmstedt, B. "Dioxin: Toxicological and Chemical Aspects"; Cattabeni, F., Cavallaro, A., Galll, G., Eds.; Spectrum Publ., Inc.: New York, 1978; Chapter 3, 13-25. (10K) Hummel, R. A.; Shadoff. L. A. Anal. Chem. 1080, 52( 7), 191-192. (11K) Kohli, K. K., Albro, P. W.; McKinney, J. D. J. Anal. Toxicol. 1070, 3(3), 125-128. (12K) Lamparski, L. L.; Nestrick, T. J.; Stehl, R. H. Anal. Chem. 1070, 5 1(9), 1453-1458. (13K) LeBel, G. L.; Williams, D. T. Bull. Envlron. Contam. Toxicol. 1080, 2413). 397-403. (14K) 'Lotjonen, S.; Ayras, P.; Pyysalo, H. Finn. Chem. Len. 1070, (2), 5760;Chem. Absf. 1070. 97. 50435~. (15K) O'Keefe, P. W. "Dioxin: Toxicological and Chemical Aspects"; Cattabeni, F., Cavallaro, A.. Galli, G., Eds.; SDectrum Publ.. Inc.: New York, 1978; Chapter 7, 59-78. (16K) Prescott, A. M.; Cooke, M. Proc. Analyt. Div. Chem. SOC. 1070, 76( 7), 10-12. (17K) Seidl, G.; Ballschmlter, K. Fresenius' 2. Anal. Chem. 1070, 296(4), 281-284. (18K) Shadoff, L. A.; Blaser, W. W.; Kocher, C. W.; Fravel, H. G. Anal. Chem. 1078, 50( 7 7 ) , 1586-1588. (19K) Sundstrom, G.; Jansson, B.; Renberg, L. Chemsphere 1078, 7( 72), 973-979. (20K) Suprock, J. F.; Vinopal, J. H.; Heller, J. M. U . S . NTIS AD Rep. ADA0671070, 749, 21 pp. (21K) Szelewskl, M. J.; Hill, D. R.; Splegel, S. J.; Tim, E. C., Jr., Anal. Chem. 1070, 57( 14), 2405-2407. (22K) Tulnstra. L. G. M. Th.; Traag, W. A. J . H/gh Resoluf. Chromatogr. Chromafogr. Commun. 1070, 2( 72), 723-728. (23K) Underwood, J. C. Bull. Environ. Contam. Toxicol. 1070, 27(6),787790. (24K) Wright, L. H.; Lewis, R. G.; Crlst, H. L.; Sovocool, 0. W.; Slmpson, J. M. J. Anal. Toxicol. 1078, 2(3), 76-79. '
MISCELLANEOUS PESTICIDES (1L) Abe. H., Amma, K., Ishikawa, K., Asasaki, K. Bunseki Kagaku (Jpn. Anal.) 1980, 29(1), 44-8; Pest. Abstr. 1080, 73, 80-1165. (2L) AWel-Kader, M. H. K., Peach, K. E., Ragab, M. H. T., Stlles, D. A. Anal. Len. 1070, 72(A73), 1399-410. (3L) Abdei-Kader, M. H. K., Peach, M. E., Stiles D. A. J. Assoc. Off. Anal. Chem. 1070, 62(1), 114-8.
(4L) Abou-Donla, M. B., Komeil, A. A. J. Chromatogr. 1078, 152(2), 585-8. (5L) Amadori, E., Heupt, W. I n "Analytical Methods for Pesticides and Plant Growth Regulators" Zweig, G., Sherma J., Eds.; Academic Press: New York, 1980; Chapt. 16 , Vol. XI, 319-29. (6L) Brown, P. M., Chana, J. S. J. Chromafogr.1070, 769, 407-8. (7L) Chapman, R. A., Harris, C. R. J. Chromafogr. 1978, 766(2), 513-8. (EL) Chapman, R. A., Harrls, C. R. J. Chromatogr. 1070, 777, 249-62. (9L) Choe, M. K. N . 2.J. Med. Lab. Techno/. 1078, 32(3), 107. (1OL) Chlba, M. J. Envlron. Sci. HBakh 8 1078, 73(3), 261-8. (11L) Choulis, N. H. J. Chromfogr. 1070, 768(2), 562 (12L) Cbwer, M. Jr. J. Assoc. Off. Anal. Chem. 1080, 63(3), 539-45. (13L) Cochrane, W. P., Lanouette, M. J . Assoc. Off. Anal. Chem 1070, 62(1), 100-6. (14L) Cochrane, W. P., Lanouette, M., Grant, R. J. Assoc. Off. Anal. Chem. 1080, 63(1), 145-8. (15L) Davis, P. L., Munroe, K. A. J. Agric. FoodChem. 1970, 27(4), 9183n --.
(16L) Dawson, V. K., Harman, P. D., Schuh, D. P., Allen J. L. J. Fish. Res. Board Can. 1078, 35(9), 1282-5. (17L) Ernst, G. F., VetveldRoeder, S. Y. J. Chromtcgr. 1079, 774(1), 269-71. (18L)-Fatorl, D., Hunter, W. M. Clln. Chlm. Acfa 1080, 700(2), 81-90. (19L) Franke, G., Pietrulla, W., Preussner, K. Fresenius Z . Anal. Chem. 1070, 298(1), 38-42. (20L) Ganesan, M., Natesan, S., Ranganathan, V. Analyst (London) 1070, 704( 1236), 256-61. (21L) Gardner, R. C., McKellar, R. L. J. Agric. Food Chem. 1080, 28(2), 256-6 1. (22L) Gordts. L. A., Vandezande, A., Van Cauwenberge, P. P., Van Haver, W. J. Agric. FoodChem. 1070, 27(1), 132-4. (23L) Hass, J. R., Friesen, M. D. N . Y. Acad. Sci., Sci. Week, June 21-30, 1078. (24L) Heedham, L., Rollen, 2. J., Paschal, D., Liddle. J., Bayse, D. J. Chromatogr. Sci. 1070, 17(2), 87-90. (25L) Higuchl, S., Ako, O., Tanaka, S. Anal. Chim. Acfa 1080, 776(1), 1-6. (26L) Hill, K. R. Pure Appl. Chem. 1070, 57(7), 1617-23. (27L) Hlrvi, T., Pyysalo, H., Savolainen, K. J. Agrlc. Food Chem. 1070, 27(1), 194-5. (28L) Holmstead, Roy L., Soderlund, DavM M. Pyrethrum Post 1078, 74(3), 79-82. (29L) Hulbregtse-Mindehud, L., Van der Kerk Van Hoof, A. C., Wijkens, P., Blessels, H. W. A., Salemink, C. A. Red. Trav. Chim. Pays-Bas 1070, 98(6), 421-2; Chem. Absb. 1070, 97: 8 6 6 8 3 ~ . (30L) Johnson, J. S., Pickering, G. E. Pesfic. Sci. 1070, 70(6), 531-9. (31L) Kobayashi, H., Matano, O., Goto, S. Nlppon Noyaku Gakkaishi (J. Pesfic. Sci.) 1080, 5(1), 89-92; Pest. Absfr. 1080, 73, 80-2096. (32L) Koubek, K. G., Ussary, J. P., Haulsee, R . E. J. Assoc. Off. Anal. Chem. 1070, 62(6), 1297-301. (33L) Krasnykh, A. A., Shvets. D. A. Gb. Santi. 1070, 44(12), 50-1; Pest. Absfr. 1080, 73 80-1773. (34L) Lakso, J. U., Rose, L. J., Peoples, S. A., Shirachi, D. Y. J. Agrlc. Food Chem. 1070, 27(6), 1229-33. (35L) Luckow, V. Fresenius Z . Anal. Chem. 1070, 294(4), 288. (36L) Luhning, C. W., Harman, P. D., Sills, J. B., Dawson, V. K., Allen, J. L. J. Assoc. Off. Anal. Chem. 1070, 62(5), 1141-5. (37L) Macy, T. D., Loh, A. Anal. Chem. 1080, 52(8), 1381-3. (38L) Mestres, R., Chevallier, Ch., Espinoza, CI., Cornet, R. Trav. Soc. Pharm. Mnfpellbr 1078, 38(2), 183-91; Pest. Abstr. 1070, 72, 79-0500. (39L) Mestres, R., Espinoza, CI., Chevallier, Ch., Marti, G. IbM. 1070, 39(4), 329-36; Pest. Ab&. 1080, 73, 80-2400. (40L) Moring, S. E., McChesney, J. D. J. Assoc. Off. Anal. Chem. 1070, 62(4), 774-81. (41L) Mourille, M., Bentebc, R., Valade, J. Ann. Falslf. Expert. Chlm. 1078, 71(769), 361-7; Pest. Abstr. 1070, 12, 79-?219. (42L) Mourot, D. Delepine, B., Boisseau, J., Gayot, G. J. Chromatogr. 1070, 768(1), 277-9. (43L) Mourot, D., Delepine, B., Boisseau, J., Gayot, G. J. Chromfogr. 1070, 773(2), 412-4. (44L) Narain, N. K., Hanlf, M.,Latheef, M. A., Lewis, C. C. Anal. Len. 1080, 73(A3), 213-17. (45L) Newsome, W. H. I n "Analytical Methods for Pesticides and Plant Gowth Regulators"; Zweig, G., Sherma, J. Eds.; Academic Press: New York, 1980; Vol. XI, Chapter 9, pp 197-226. (46L) Newsome, W. H. J. Agric. Food Chem 1080, 28(2), 319-22. (47L) Newsome, W. H. J. Agric. Food Chem. 1080, 28(2), 270-2. (48L) Oehler, D. D. J. Assoc. Off. Anal. Chem. 1070, 62(6),1309-11. (49L) Okuno, I., Meeker, D. L. J. Assoc. Off. Anal. Chem. 1080, 63(1), 49-55. (50L) Ott, 0.E. J. Assoc. Off. Anal. Chem. 1070, 62(1), 93-9. (51L) Palassis, J. Am. Ind. Hyg. Assoc. J. 1080, 47(2), 91-7. (52L) Paschal, D. C., Needham, L. L., Rollen, Z. J., Liddle, J. A. J. Chromarogr. 1070, 177(1), 85-90. (53L) Pavoni, G. Boll. Lab. Chlm. Prov. 1978, 4 9 . h. 157-61. Pest. Absfr. 1980, 73, 80-0878. (54L) Picker, J. E., Yates, M. L., Pereira, W. E. Bull. Envlron. Contam. TOX~CO~. 1070. 27f4-5). 612-7. (55L) Plechocka; J. IPol:), Mer* Bedanla Pozostabscl Pesfyc. Srodkach Spozyw. 1078, 37-4; Chem. Absfr. 1080, 93, 24572j. (56L) Richmond, C. E., Crisp, C. E., Larson, J. E., Pieper, G. R. Bull. Envlron. Contam. Toxkol. 1070, 22(4-5), 512-6. (57L) Rodriguez-Vazquez, J. A. Talanfa 1078, 25(6), 299-310. (58L) %no, M., Fwukawa, M., Kourai, M., Tomb, I. J. Assoc. Off. Anal. Chem. 1070, 62(4), 764-8. (59L) Shadoff, L. A. Chapt. 15 I n "Pesticide Analytical Methodology" Harvey, J. Jr. and Zweig, G., e&., ACS Symp. Ser. 136, American Chemical Society, Washington, D.C. 1080, pp 277-85. ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
87 R
Anal. Chem. 1981, 53, 88R-142R (61L) Shimogata, M., Koyama, K., Ueda, K. Nippon Eiselgaku Zasshl(Jpn. J . M a . ) 1980. 35(1). 172: Pest. Abstr. 1980. 13. 80-1787. (62L) Sligh, J., Cochiane, W: P., Scott, J. Bull. Environ. Contam. Toxicol. 1979, 23(4-5), 470-4. (63L) Stewart, T. E., Cannizzaro, R. D. Chapt. 20 In "Pesticide Analytical Methodology", Harvey, J. Jr. and Zweig, G., Eds., ACS Symp. Ser. 136, American Chemical Society, Washington, D.C. 1980, 367-88. (64L) Tjan, G. H., Jansen, J. T. A. J . Assoc. Off. Anal. Chem. 1979, 62(4), 769-73. (65L) Vasundhara, T. S., Parihar, D. B. Fresenius Z . Anal. Chem. 1979, 294(5), 408. (66L) van Rossum, A., de Boer, F. G., Cannizzaro, R. D., van Mwrsehar, R., Stewart, T. E., de Wilde, P. C. Chapt. 10, in Vol. XI "Analytial Methods for Pesticides and Plant Growth Regulators", Zweig, G. and Sherma, J, ds.,
Academic Press, New York 1980, pp 227-46. (67L) Wells, D. E. Anal. Chim. Acta 1979, 104(2), 253-66. (68L) Wlslowska, E., Kostowska, B. Chem. Anal. (Warsaw) 1979, 24(4), 707-9, Pest. Abstr. 1980, 13, 80-0560. (69L) Wisson, M., van Hoek, C., Sauer, H. H. In Analytical Methods for PesticMes and Plant Growth Regulators"; Zweig, G., Sherma, J., Eds.; Academic Press: New York, 1980; Vol. XI, Chapter 8, pp 185-94. (70L) Woolson, E. A., Aharonson, N. J. Assoc. OM.Anal. Chem. 1980, 63(3), 523-6. (71L) Yu, T. C., Johnson, E. R., Montgomery, M. L. J . Agric. Food Chem. 1979, 27(6), 1413-4. (72L) Zakkis, L. H. Bull. Envlron. Contam. Toxlcol. 1979, 23(3), 391-7. (73L) Zanini, E., Barberis, E., Ronco, C. J . Agric. FoodChsm. 1980, 28(2), 464-6.
Petroleum R. E. Terrell Gulf Science & Technology Corporation, Pittsburgh, Pennsylvania 15230
This is the 15th review of analytical chemistry in the petroleum industry (1A-14A) sponsored by the Division of Petroleum Chemistry of the American Chemical Society. It covers, for the most part, papers abstracted in Chemical Abstracts, American Petroleum Institute Refining Literature Abstracts, and Analytical Abstracts (London) for the period July 1978 through June 1980. One area, asphalt, spans a 4-year period from July 1976 to June 1980. The format of the previous reviews has been followed in general. An input concerning improvin this format or the addition or Aletion of subsections woulf be greatly appreciated. The assistance of D. K. Albert, Standard Oil Co. (Indiana), Amoco Research Center, and C. A. Simpson, Mobil Research and Development Corp., in searching the abstracts is greatly appreciated, as is the additional screening and organization of the 16 authors of the following 11 subsections. The production of the review is due to their combined efforts.
methylenetetracosanic acid in the original source material (56B). Vorob'eva and others used GC MS to characterize the polycyclic Cl4-CZ6naphthenes o f t e 200-420 "C fraction of Siva crude oil. They also proposed a scheme for the formation of these compounds by the conversion of certain aliphatic hydrocarbons (88B). Grizzle and Coleman have reported a GC analysis for benzene and toluene in crude oil and other fossil fuels. The method employs two columns in series (OV-1 and TCEP), with provisions for back-flushing heavier material. Repeatability and accuracy are said to be f2% and f4% of the amount present (33B). Vo-Dinh has developed a method using room-temperature phosphorimetry for the rapid analysis of polynuclear aromatic compounds in fossil fuels (87B). Sultanov and others studied the content and distribution of nitrogen compounds in Baku crudes. The highest nitrogen content was found in the asphaltene fraction (76B). Mozzhelina and co-workers subjected West Surgut crude oil to acid hydrolysis and measured the resulting amino acids. Glycine and glutamic acid were the most abundant motein-derived amin'o acids (55B). Ferguson and Luke carried out a critical appraisal of flame photometric detectors for the determination of sulfur compounds. They discussed the problems of using a single FPD for the auantitative determination of trace level sulfur compounds in light naphtha, as well as using it for the qualitative comparison of the distribution of sulfur compounds in heavier fractions. Dual FPDs are also discussed (24B). Nuzzi and Casalini studied the variety of thio henic com ounds in the maltene fraction of the pentane Jeasphaltearesiduum of Kuwait crude (58B). Goncharov and others studied the phenols in eight West Siberian crudes and noted the trends in total phenol concentration and concentrations of individual compounds with increasing depth. They were unable to separate the effects of age and of temperature on these trends (3UB). Nametkin and co-workers determined the nature of the acids of normal and isoprenoid alkanes in diesel fuels and kerosines from a number of Baku and Mangyshlak crude oils (57B). Holstein and Severin concentrated carbonyl com unds from crude oils by extracting their complexes with irard-T reagent into water. The original compounds were recovered by acid hydrolysis and were separated by HPLC (44B). Brownrigg and Homing obbned total lurmnescence s of six topped crude oils, their vacuum distillates, anc/?i% residua and attempted to identify the principal emitting compound classes. They attributed the dominant fluorescence emissions to indoles and carbazoles, with weaker fluorescence coming from benzocarbazoles and three-ring aromatics. The
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CRUDE OILS F. C. Trusell Marathon Oil Company, Linleton, Colorado
The trend in this area toward analyses for a specific purpose (e.g., spill identification and geochemical studies) rather than characterization for its own sake continues unabated. Interest in syncrudes, as indicated by the number of references, is up sharply. Hydrocarbons a n d Hetero Compounds. Yashina and others used proton and 13C NMR techniques to study 22 Soviet crudes of a variety of com ositional types. The nalkane content, the degree of alip atic branching, and the extent of substitution on aromatic compounds were all calculated. Since the application of NMR is not limited by boilin range, such studies can be carried out on heavy fractions (%IB). Hajek and co-workers also studied Soviet crudes by use of 13C NMR (36B). Zhmykhova and Nekhamkina characterized three fractions of Marmovichi and Ladushkino crude oils boilin above 350 OC by mass spectrometry and predicted their ehavior as feedstocks for various refining processes (94B). Barabadze characterized the 350-500 OC fraction of Noriyskaya crude oil by IR and UV spectroscopy, calculating the contents of paraffins, naphthenes, and aromatic compounds (6B). Larskaya and others used GC and MS, ;e arately and in comof Sokolwa bination, to characterize the 200-500 arfo!(citn crude oil. They identified nearly 100 individual hydrocarbons (49B). Makushina and co-workers found the series o f ' 12methylalkanes (Cu-C30) and 13-methylalkanes (C26-C30) to be unusually abundant in East Siberian crude oils and proposed that these hydrocarbons are derived from 12,13-
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1981 American Chemical Society
