It is shown that in homogeneous aqueous solution containing titanium(III) citrate or titanium(III)-NTA as bulk electron donor, cobalamin, cobinamide, and cobamide are effective electron transfer mediators for the reduction of tetrachloroethene (PCE), trichloroethene (TCE), and trichlorofluoroethene (TCFE). For a given chlorinated ethene, the reaction rate varied only slightly with pH and type of corrinoid present and was about 5 and 50 times faster for PCE as compared to TCFE and TCE, respectively. Evidence is presented that the first and rate-limiting step of the reduction of PCE, TCE, and TCFE by super-reduced corrinoids is a dissociative one-electron transfer yielding the corresponding vinyl radicals. Furthermore, the elimination of a chloride radical from the 1,1-dichlorovinyl radical yielding chloroacetylene and subsequently acetylene is proposed to account for the direct formation of acetylene out of TCE. Finally, it is demonstrated that at higher reduction potentials the corrinoid mediators may be blocked by the formation of addition products.

Since cobalamin is involved in the enzymatic reduction of halogenated ethenes by a variety of anaerobic bacteria and since cobalamin has been suggested as electron transfer mediator for the treatment of halogenated solvents, its reactions with such compounds are presently of great interest. In this paper, it is shown that, in homogeneous aqueous solution containing titanium(III) citrate as the bulk electron donor, superreduced cobalamin reductively dechlorinated cisand trans-dichloroethene (cis-DCE and trans-DCE), 1,1-dichloroethene (1,1-DCE), and vinyl chloride (VC) in pH-dependent reactions to ethene and ethane. Evidence is given that the initial step was the addition of cob(I)alamin to the chlorinated ethenes (CEs) with simultaneous protonation. Only for 1,1-DCE at high pH, a dissociative electron transfer mechanism as suggested for tetrachloroethene (PCE) and trichloroethene (TCE) in earlier work was important. 1,1-DCE reacted about 30 times faster than VC, 600 times faster than trans-DCE, and 3000 times faster than cis-DCE. Acetylene and ethene were found to react at similar rates as 1,1-DCE and VC, respectively. However, at more positive redox potentials, the reductive cleavage of the addition products, particularly of the adducts of acetylene, ethene, and VC with cob(I)alamin, may become very slow, thus preventing the regeneration of cob(I)alamin. The results of this study demonstrate that, at more negative potentials and at low pH, cobalamin is a potent electron transfer mediator for the complete dehalogenation of PCE and TCE without significant accumulation of VC.

Due to leakages, spills, improper disposal and accidents during transport, organic compounds have become subsurface contaminants that threaten important drinking water resources. One strategy to remediate such polluted subsurface environments is to make use of the degradative capacity of bacteria. It is often sufficient to supply the subsurface with nutrients such as nitrogen and phosphorus, and aerobic treatments are still dominating. However, anaerobic processes have advantages such as low biomass production and good electron acceptor availability, and they are sometimes the only possible solution. This review will focus on three important groups of environmental organic contaminants: hydrocarbons, chlorinated and nitroaromatic compounds. Whereas hydrocarbons are oxidized and completely mineralized under anaerobic conditions in the presence of electron acceptors such as nitrate, iron, sulfate and carbon dioxide, chlorinated and nitroaromatic compounds are reductively transformed. For the aerobic often persistent polychlorinated compounds, reductive dechlorination leads to harmless products or to compounds that are aerobically degradable. The nitroaromatic compounds are first reductively transformed to the corresponding amines and can subsequently be bound to the humic fraction in an aerobic process. Such new findings and developments give hope that in the near future contaminated aquifers can efficiently be remediated, a prerequisite for a sustainable use of the precious subsurface drinking water resources.

Pseudomonas sp. strain T and Pseudomonas sp. strain K172 grow with toluene under denitrifying conditions. We demonstrated that anaerobic degradation of toluene was initiated by direct oxidation of the methyl group. Benzaldehyde and benzoate accumulated sequentially after toluene was added when cell suspensions were incubated at 5°C. Strain T also grows anaerobically with m-xylene, and we demonstrated that degradation was initiated by oxidation of one methyl group. In cell suspensions incubated at 5°C 3-methylbenzaldehyde and 3-methylbenzoate accumulated after m-xylene was added. Tolueneor m-xylene-grown strain T cells were induced to the same extent for oxidation of both hydrocarbons. In addition, the methyl group-oxidizing enzyme system of strain T also catalyzed the oxidation of each isomer of the chloroand fluorotoluenes to the corresponding halogenated benzoate derivatives. In contrast, strain K172 only oxidized 4-fluorotoluene to 4-fluorobenzoate, probably because of the narrow substrate specificity of the methyl group-oxidizing enzymatic system. During anaerobic growth with toluene strains T and K172 produced two transformation products, benzylsuccinate and benzylfumarate. About 0.5% of the toluene carbon was converted to these products.

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