Toxaphene production

The history of toxaphene production and use in the United States has been chronicled by Li [17], who used a combination of production/use statistics... 

Since 1979, the output of toxaphene constantly reduced. In 1985, toxaphene production ceased due to its low efficiency in pest control, high toxicity to fish, and inconsistent quality. 

Table 2. Trade names of commercial toxaphene products [22-25]...

Fig. 1. Typical toxaphene product (here the East-German Melipax). This formulation was used against insects in fruit-growing and contained about 10% toxaphene. The recommended application amount was 20 g (i.e., 2 g toxaphene) per 10 m2. It was distributed in 500 g units at a price of about 1 /unit...

Chlorinated Terpenes. A group of incompletely characterized insecticidal compounds has been produced by the chlorination of the naturally occurring terpenes. Toxaphene [8001-35-2] is prepared by the chlorination of the bicycHc terpene, camphene [79-92-5] to contain 67—69% chlorine and has the empirical formula C QH QClg. The technical product is a yellowish, semicrystalline gum (mp 65—90°C, d 1.64) and is a mixture of 175 polychloro... 

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. 

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. 

Technical chlordane is a mixture of chlorinated hydrocarbons that has been used as an insecticide since its introduction in 1947. Chlordane was the first cyclodiene insecticide to be used in agriculture and was the second most important organochlorine insecticide in the United States in 1976/1977, behind toxaphene, with an estimated annual production of 9 million kg (Nomeir and Hajjar 1987). Chlordane is a leading insecticide in controlling termites, with about 1.2 million homes in the United States alone treated annually for this purpose (Nomeir and Hajjar 1987). 

Bush, P.B., J.T. Kiker, R.K. Page, N.H. Booth, and O.J. Fletcher. 1977. Effects of graded levels of toxaphene on poultry residue accumulation, egg production, shell quality and hatchability in white leghorns. Jour. Agric. Food Chem. 25 928-932. 

Terrence Collins is the Thomas Lord Professor of Chemistry at Carnegie Mellon University who contends that the dangers of chlorine chemistry are not adequately addressed by either academe or industry, and alternatives to chlorine and chlorine processors must be pursued. He notes, Many serious pollution episodes are attributable to chlorine products and processes. This information also belongs in chemistry courses to help avoid related mistakes. Examples include dioxin-contaminated 2,4,5-T, extensively used as a peacetime herbicide and as a component of the Vietnam War s agent orange chlorofluorocarbons (CFCs) polychlorinated biphenyls (PCBs the pesticides aldrin, chlordane, dieldrin, DDT, endrin, heptachlor, hexachlorobenzene, lindane, mirex, and toxaphene pentachlorophe-... 

A workshop participant reported that China has phased out the production and use of five of the POPs covered by the Stockholm Convention—aldrin, dieldrin, endrin, toxaphene and heptachlor. He explained that chlordane and mirex are still produced in limited quantities for termite protection and hexachlorobenzene (HCB) is still produced for use as a chemical feedstock. Mirex... 

With respect to C-parathion and Cl-toxaphene, protease-liberated flavoprotein was significantly more active than phosphate buffer in photodegrading these chemicals to ater-soluble products (Tables II and III). The amount of C-water-soluble products formed from parathion was 5-7 times greater in the presence than in the absence of flavoprotein. It should be noted that the presence of FMN in the mixture caused a slight grange in amount of water-soluble products formed (Table II). 

As was thf case with dieldrin, photodecomposition of C-parathion and Cl-toxaphene was relatively extensive, and the addition of FMN has almost no effect on the enhancing or decreasing the rate of degradation to water-soluble products. Since the organic-soluble products were not analyzed in the case of parathion and toxaphene, it is difficult to speculate on the type of degradation products formed and the pathways involved on... 

Chlorinated micropoUutants are harmful for man and environment due to their toxicity, persistence, and bioaccumulation. Persistent compounds are very stable and difficult to get metabolized and mineralized by biological and chemical processes in the environment, and as a result, they have become ubiquitous in water, sediments, and the atmosphere bioaccumulation is the result of the lipophilicity of these compounds. Polychlorinated dibenzodioxins and -furans (PCDD/F) are not produced purposely like many of other chlorinated technical products, such as chlorinated biocides DDT, lindane, and toxaphene. The production and use of persistent organic pollutants (POPs), the dirty dozen has now been banned worldwide by the Stockholm protocol. It should be mentioned that about 3000 halogenated products have now been isolated as natural products in plants, microorganisms, and animals," but the total amount of these products is much smaller compared to xenobiotics. 

Enhancement of metabolism of " C-toxaphene by several added cofactors was studied in 8 hrs aerobic cultures of washed Pseudomonas putida cells. The results of these experiments are summarized in Table 6. In the NAD group, NADH showed the greatest stimulatory effect on the production of total polar metabolites (1.2 times) over that of the 8 hrs incubate value. Similarly, FAD was responsible for a modest increase (1.1 times). The combination of NADH-FAD showed stimulation above that of either of the unpaired cofactors (2.0 times). Addition of mannitol to NADH-FAD stimulated this combination s total polar metabolite value from 2.0 to 2.3 times that of the 8 hrs incubate. In the sequence NADH to NADH-FAD to NADH-FAD-mannitol, the increase in the radioactivities in the ethyl acetate phase (moderately polar metabolites)... 

The Stockholm treaty completely banned the production and use of some TOCs (such as endrin and toxaphene), while permitting the use of other TOCs for specific purposes (such as aldrin as an insecticide and dieldrin in certain agricultural operations). In addition, a number of nations requested exceptions that would allow them to use otherwise-banned compounds in public health programs. By 2003, more than 20 nations had taken advantage of that exception and were using certain pesticides, usually DDT, to spray for the anopheles mosquito. Those 20 nations included Ethiopia, Eritrea, Madagascar, Mauritius, Morocco, Namibia, South Africa, Sudan, Swaziland, and Zambia. 

---