Steffen Ruppe

Anaerobic transformation of compounds of technical toxaphene. I. Regiospecific reaction of chlorobornanes with geminal chlorine atoms

Technical toxaphene (Melipax) and the single compounds of technical toxaphene (CTTs) 2,2,5-endo,6-exo,8,8,9,10-octachlorobornane (B8-806), 2,2,5-endo,6-exo, 8,9,9,10-octachlorobornane (B8-809), 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025), 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonochlorobornane (B9-1679), 2-endo,3-exo,5-endo,6-exo,8,9,10,10-octachlorobornane (B8-1414), 2-endo,3-exo,5-endo,6-exo,8,8,9,10-octachlorobornane (B8-1412), and 2-exo,3-endo,5-exo,9,9,10,10-heptachlorobornane (B7-1453) were treated with suspensions of the anaerobic bacterium Dehalospirillum multivorans. After 7 d, more than 50% of technical toxaphene was transformed, and the relative amount of early eluting CTTs increased. After 16 d, only 2-exo,3-endo,6-exo, 8,9,10-hexachlorobornane (B6-923), 2-endo,3-exo,5-endo,6-exo, 8,9,10-heptachlorobornane (B7-1001), and a few minor penta- and hexachloro-CTTs were detected in the samples. The result of the transformation was comparable with observations in naturally contaminated sediments and soil. However, the performance with D. multivorans was more simple and reproducible, as well as faster, than use of soil, sediment, or anaerobic sewage sludge. In agreement with reports in the literature, reductive dechlorination at geminal chlorine atoms (gem-C1s) was found to be the major CTT transformation pathway. Experiments conducted with CTTs and gem-C1s at both primary and secondary carbons clarified that the initial C1 --> H substitution takes place at the secondary carbon C2. Furthermore, the 2-endo-C1 position was preferably substituted with hydrogen. In the case of B8-806, the dechlorination at the secondary carbon C2 was approximately 20-fold faster than the subsequent, slow reduction at the primary carbon C8. The three different formerly unknown heptachloro-CTTs, 2-exo,3-endo,6-exo,8,9,9,10-heptachlorobornane (B7-1473), 2-exo, 3-endo,6-endo,8,9,9,10-hepatchlorobornane (B7-1461), and 2-exo, 3-endo,6-exo,8,8,9,10-heptachlorobornane (B7-1470) were found as intermediates of the B8-806/809 transformation. Treatment of B9-1679 with D. multivorans indicated that gem-C1s on the bridge (C8 and C9) are dechlorinated faster than gem-C1s on the bridgehead (C10).

Anaerobic transformation of compounds of technical toxaphene. 2. Fate of compounds lacking geminal chlorine atoms.

The major toxaphene metabolites in sediment and soils (2-exo,3-endo,6-exo,8,9,10-hexachlorobornane [B6-923] and 2-endo,3-exo,5-endo,6-exo,8,9,10-heptachlorobornane [B7-1001]) were incubated with the isolated gram-negative bacterium Dehalospirillum multivorans. Within 14 d, biotransformation of B7-1001 was nearly quantitative, resulting in two penta- and six hexachlorobornanes, as well as one unsaturated hexachloro compound of technical toxaphene. The major transformation product (approximately 50% of all metabolites) was identified as 2-exo,3-endo,5-exo,8,9,10-hexachlorobornane (B6-903). Abiotic dehydrochlorination of B7-1001 with methanolic KOH resulted in the formation and subsequent identification of the lone unsaturated compound as 2,5-endo,6-exo,8,9,10-hexachloroborn-2-ene. Thus, dehydrochlorination was found to be a minor process of the anaerobic transformation of toxaphene. Biotransformation of 70% of amended B6-923 within 14 d demonstrated that reductive dechlorination was not exclusively associated with geminal Cl atoms, as previously suggested. Three pentachlorobornanes were identified as transformation products, one of which was identical with a transformation product of B7-1001. This commonality unequivocally proves this metabolite to be 2-exo,3-endo,8,9,10-pentachlorobornane. Fifteen previously unknown metabolites of B6-923, B7-1001, and other toxaphene compounds identified in this study were detected in sediment from Lake Ontario (Canada), underscoring the importance of microbial toxaphene transformation in natural, aquatic environments.

Anaerobic transformation of four abundant organochlorine pesticide residues (B8-1413, B9-1679, oxychlordane, p,p‵-DDE) in extracts of Antarctic skua eggs by the isolated bacterium Sulfurospirillum multivorans

Residues of halogenated pollutants bioaccumulated in eggs of the south polar skua (Catharacta maccormicki) from the Antarctic were extracted, purified, and fractionated. The target fraction which contained the bulk of the chloropesticides was concentrated and incubated with cell suspensions of the isolated bacterium Sulfurospirillum multivorans (formerly Dehalospirillum multivorans). S. multivorans was previously identified as a good anoxic transformer of several halogenated compounds. The compounds of technical toxaphene 2-endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413, also known as P-26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679, also known as P-50) as well as 1,1-dichloro-2,2-bis(p-chlorophenyl)ethene (p,p′-DDE) and 1-exo,2-exo,4,5,6,7,8,8-octachloro-2,3-exo-epoxy-3a,4,7,7a-tetrahydro-4,7-methanoindene (oxychlordane) were present at a sufficiently high concentration and hence useful for studying the anaerobic transformation by the bacterium. When treated with S. multivorans, B8-1413 and B9-1679 were almost quantitatively transformed within 1 day. For B9-1679, the major metabolite was found to be 2-endo,3-exo,5-endo,6-exo,8,9,10-heptachlorobornane (B7-1001). Compared to the toxaphenes, transformation of oxychlordane and p,p′-DDE was significantly slower. Even after seven days, about 10% of the initial pool was detected in the extracts. 1-chloro-2,2-bis(p-chlorophenyl)ethene (p,p′-DDMU) was identified as a transformation product of p,p′-DDE. The four compounds in this study comprise some of the most persistent chloropesticide residues found in marine birds. In case there is sufficient transformation before they reach the top predators, the bioaccumulative potential can be significantly reduced.