Toxaphene determination

The total-chlorine method for determining residues of benzene hexachloride, chlordan, and toxaphene has also been used 55) in experiments where it was known that these insecticides had been applied. With benzene hexachloride, which is known to give off-flavor to some crops, it has not been demonstrated that a relation between organic chlorine values and off-flavor exists. In fact, in most cases where off-flavor was attributed to benzene hexachloride, it has not been possible to detect organically bound chlorine. 

Recently it was shown that when DDT, benzene hexachloride, or toxaphene is fed or applied to cattle, such organic chlorine residue as may be present in the fatty tissues consists essentially of unchanged insecticide. Carter (12) demonstrated their presence by separating the fats and other oxygenated products with sulfuric acid-sodium sulfate mixture and determining total chlorine. In experiments with DDT Schechter (46) demonstrated its presence in fatty tissue and in butterfat by the Schechter-Haller colorimetric method (47). The residues were then tested for toxicity to houseflies in comparison with the known insecticides of the same concentration. In both cases the known insecticide gave the same mortality as the residue. 

The commonly used organic insect toxicants do not interfere in the analysis of Compound 118 by this new procedure. Hexane solutions of chlordan, DDT, methoxychlor, hexachlorocyclohexane (BHC), and toxaphene treated according to the procedure for determining Compound 118 gave a pale yellow color similar to that of the blank. 

Determination of organically bound chlorine is shown to be in general agreement with fly mortality tests of insecticide residues in agricultural products. Alfalfa hay that had received applications of toxaphene and beef fat from animals fed alfalfa hay containing toxaphene residues or sprayed with benzene hexa-chloride or DDT were used for tests. 

Colorimetric methods (3, 6-10), some of which are specific, have been developed for the determination of DDT in small amounts. For benzene hexachloride (hexachloro-cyclohexane), chlordan, and toxaphene, however, specific analytical methods have not been developed, and their residues have been evaluated by the determination of organically bound chlorine. The procedure comprises extraction of the insecticide residue from the sample with benzene or other suitable organic solvent, evaporation of the solvent, treatment of the residue with isopropyl alcohol and metallic sodium, and finally determination by standard methods of the amount of chloride ion formed. 

Portions of the treated hay were extracted with benzene, and aliquots of the benzene solution were evaporated to dryness on the steam bath, with a gentle air current to remove the last traces of solvent. The residues were then taken up in deodorized kerosene and tested against houseflies by the turntable method. For comparison, extracts were made up to contain the same amounts of technical toxaphene as were indicated by the chlorine determinations to be present in the treated hay. 

The kills obtained from the residues from the sprayed alfalfa and from the known technical toxaphene are in close enough agreement to support the assumption that the chemically determined material was toxaphene and that the concentrations determined were essentially correct. 

Wilson and co-workers [332, 333] have discussed the determination of aldrin, chlordane, dieldrin, endrin, lindane, o,p and p,p isomers of DDT and its metabolites, mirex, and toxaphene in seawater and molluscs. The US environmental Protection Agency has also published methods for organochlo-rine pesticides in water and wastewater. The Food and Drug Administration (USA) [334] has conducted a collaborative study of a method for multiple organochlorine insecticides in fish. Earlier work by Wilson et al. [333, 335] in 1968 indicated that organochlorine pesticides were not stable in seawater. 

Seiber, N.J., S.C. Madden, M.M. McChesney, and W.L. Winterlin. 1979. Toxaphene dissipation from treated cotton field environments component residual behavior on leaves, and in air, soil and sediments determined by capillary gas chromatography. Jour. Agric. Food Chem. 27 284-290. 

Fowler, B. The Determination of Toxaphene in Environmental Samples by Negative Ion Electron Capture (EC) HR-MS. Chemosphere 2000,41,487-492. 

Toxaphene caused a dose-related increase of hepatocellular carcinomas in mice fed 98 or 198 ppm for 80 weeks. In rats, there was a significantly increased incidence of neoplastic thyroid lesions at the high dose." The lARC has determined that there is sufficient evidence in experimental animals for the carcinogenicity of toxaphene and that it is possibly carcinogenic to humans. ... 

To determine if either side of the interface controls transport of toxaphene across the interface, we need to look at the ratio of transfer coefficients on either side. Mackay and Yuen (1983) suggest that Kq/Kl values of between 50 and 300 are reasonable. We will use Kg/Kj = 150. Then, the resistance to transfer is given as... 

Lower toxaphene concentrations have been found in smaller lakes within the Great Lakes watershed. Muir et al. [77] found toxaphene levels averaging 95 pg L 1 in Lake Nipigon (Table 5). Total toxaphene in Lake Siski-wit (Isle Royale) surface water sampled in May 1998 was 210 pgL-1 [74]. Chlorobornane congeners were not determined in this sample however, the heptachlorobornanes were the predominant homolog group (110 pgL-1) followed by octachlorobornanes (76 pg L 1). 

In studies of toxaphene in Lakes Superior [46] and Ontario [51,67], two persistent congeners, B8-1413 and B9-1979, were determined in air and six other congeners in water. B8-1413 and B9-1979 were of particular interest because they were among the most prominent chlorobornanes in Great Lakes fish [74,81,82], It should be noted that although peaks matching the retention... 

In a unique study, Rapaport and Eisenreich [100] determined the time trends in accumulation of toxaphene in dated peat cores collected in 1982-1984 from ombrotrophic bogs (deriving nutrients solely from the atmosphere and isolated from ground water flow) in eastern North America. Three of their peat... 

Results from Kidd et aL [148,149] include unpublished data on concentrations of B8-1413 and B9-1679. In these studies toxaphene, B8-1413 and B9-1679 were determined by GC-ECD and confirmed by GC-negative ion MS... 

Often, many simultaneously occurring pollutants or contaminants determine an environmental problem. In industry, agriculture, and households, products are often mixtures of many compounds. The process of production and consumption is accompanied by emissions and consequently by contamination. One example is the use of toxaphene in the past, a very complex mixture of polychlorinated camphenes, as a pesticide. Technical toxaphene consists of more than 175 individual compounds. A second example is industrial and domestic emissions resulting from the combustion of fossil fuels. The emissions contain both a mixture of gases (SO2, NOx, CO2, etc.) and airborne particulate matter which itself contains a broad range of heavy metals and also polycyclic aromatic hydrocarbons (PAH). 

Fisk, A T., Bosenberg, B., Cymbalisty, C.D, Stem, G.A., Muir, D.C.G. (1999) Octanol/water partition coefficients of toxaphene congeners determined by the slow-stirring method. Chemosphere 39, 2549-2562 Fisk, AT., Norstrom, R.J., Cymbalisty, C.D, Muir, D.C.G. (1998) Dietary accumulation and depuration of hydrophobic oiganochlo-rines bioaccumulation parameters and their relationship with the octanol/water partition coefficient. Environ. Toxicol. Chem. 17, 951-961. 

Fisk, A.T., Bosenberg, B., Cymbalisty, C.D., Stem, G.A., Muir, D.C.G. (1999) Octanol/water partition coefficients of toxaphene congeners determined by the slow-stirring method. Chemophere 39, 2549-2562. 

The American Public Health Association [97,98] published an early gas chromatographic method for the solvent extraction and gas chromatographic determination of 11 chlorinated insecticides in water samples in amounts, down to 0.005mg L 1 p,p -DT)E, p,p -DDT, Aldrin, Dieldrin, Endrin, Heptachlor, Heptachlor epoxide, Lindane, Isodrin and Methoxychlor. The insecticides Carbophenothion, Chlordane, Dioxathion, Diazinon, Ethion, Malathion, Parathion methyl, methyl Trithion, Parathion, Toxaphene and VC-13 may be determined when present at higher levels. Also, the chemicals chlordane, hexachlorobicycloheptadiene and hexachlorocyclopentadiene, which are pesticide manufacturing precursors, may be analysed by this method. 

Wilson and Forester [499] discussed the determination of Aldrin, Chlordane, Dieldrin, Endrin, Lindane, o,p and p,p isomers of DDT and its metabolites, Mirex and Toxaphene in sea water. The concentrated solvent extracts were analysed by electron capture gas... 

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