Polychlorinated biphenyl reductive dechlorination by vitamin B{sub 12s}: Thermodynamics and regiospecificity
- Oregon State Univ., Corvallis, OR (United States). Dept. of Civil, Construction, and Environmental Engineering
- Willamette Industries, Inc., Albany, OR (United States)
Microbial reductive dechlorination reactions play an important role in determining the environmental fate of polychlorinated biphenyls (PCBs), especially for PCB congeners with more than four chlorines. Powerful chemical catalysts such as vitamin B{sub 12s} provide an effective tool for the study of reductive dechlorination reactions. The reductive dechlorination of PCBs by titanium(III) citrate-reduced vitamin B{sub 12s} was studied in batch reactors. Long-term experiments demonstrated reductive dechlorination of aqueous and sediment-sorbed 2,3,4,5,6-pentachlorobiphenyl (2,3,4,5,6-PeCB) to tetra-, tri-, di-, and monochlorobiphenyl products. Approximately 10% chlorine removal was observed in 36 days in aqueous experiments at 20 C; the sediment experiment showed 40% chlorine removal in 42 days at 30 C. Nearly all possible intermediates were produced and reductively dechlorinated, with no apparent accumulation of individual congeners. Short-term experiments were conducted to determine the pathway for vitamin B{sub 12s}-catalyzed reductive dechlorination of aqueous 2,3,4,5,6-PeCB and its dechlorinated products; relative product distributions were measured for all possible tetra- and trichlorobiphenyl reductive dechlorination reactions. Theoretical product distributions based on free energies of formation agreed with observed product distributions for short- and long-term experiments. Reductive dechlorination was favored at positions with adjacent chlorines; on average, chlorines were removed equally from ortho, meta, and para positions.
- OSTI ID:
- 335342
- Journal Information:
- Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 6 Vol. 33; ISSN ESTHAG; ISSN 0013-936X
- Country of Publication:
- United States
- Language:
- English
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