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Grantee Research Project Results

Grantee Research Project Results

Mechanistic Studies of Vitamin B12 Mediated Dechlorination

EPA Grant Number: U915562
Title: Mechanistic Studies of Vitamin B12 Mediated Dechlorination
Investigators: Shey, Justin
Institution: University of Illinois at Urbana-Champaign
EPA Project Officer: Jones, Brandon
Project Period: June 1, 1999 through June 1, 2002
Project Amount: $102,000
RFA: STAR Graduate Fellowships (1999)
Research Category: Academic Fellowships , Engineering and Environmental Chemistry , Fellowship - Chemistry and Materials Science

Description:

Objective:

The objective of this research project is to elucidate the chemical mechanism by which certain enzymatic and non-enzymatic systems dechlorinate perchloroethylene (PCE) and trichloroethylene (TCE).

Approach:

To understand the mechanism of non-enzymatic dechlorination, the dechlorination of two radical probes (cis and trans-[2-trichlorovinyl-cyclopropyl]-benzene) will be synthesized and studied, and a stopped-flow UV-vis apparatus will be utilized. With the radical probes, the investigators intend to "trap" any radical that forms alpha to the cyclopropane ring during the dechlorination process. If the major products are opened using the ring, it would support a mechanism in which radicals are involved in the non-enzymatic dechlorination process. Because 2-propanol is a reliable hydrogen atom donor, the dechlorination of the trans radical probe also will be performed in deuterated water with 2-propan(ol-d) as well as water with 2-propan-2-d-ol. If the deuterated water system provides more deuterated products, it would suggest that the product obtains the hydrogen as a proton. Likewise, if the water system results in more deuterated products, it would support the hypothesis that the product obtains the hydrogen as a hydrogen atom. The stopped-flow methodology allows monitoring of the oxidation states of cobalt on the sub-second time scale. Because the three different oxidation states of cobalt in cobalamin offer very distinct UV-vis spectra, the mechanism of dechlorination could be followed by observing the cobalamin during the reaction. With the stopped-flow apparatus, activation parameters for these reactions also could be obtained.

Expected Results:

If the mechanism and rate limiting step(s) of dechlorination can be elucidated for the abiotic system, rational design and synthesis of remediation systems that are inexpensive and more effective can be realized.

Supplemental Keywords:

carcinogen, chemicals, chlorinated organics, environmental chemistry, remediation, vitamin B12., Scientific Discipline, Waste, Chemical Engineering, Remediation, Environmental Chemistry, Chemistry, Environmental Engineering, dechlorination, mechanistic studies, chlorinated organic compounds, TCE degradation, PCE

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The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.

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