The proposed research concentrates on the development of oxidative processes for remediation of groundwater and soils/sediments contaminated with halogenated and non-halogenated organics with suspected reproductive and developmental consequences. The treatment relies on catalytic iron reagents whose mode of operation is preferably mimicking that of biological oxygenases (P-450, sMMO), and are thus more selective than other advanced oxidative technologies that make use of indiscriminate hydroxyl radicals. Specifically, the proposed work will provide new and more robust members of a family of monoiron reagents (P-450 analogs), which are supported by electron-rich tripodal ligands designed to stabilize high-valent iron-oxo oxidants and ligand-centered radicals simultaneously. In addition, a new family of diiron reagents (sMMO analogs) will be introduced to afford highly electrophilic oxidants for use in oxygenations of persistent pollutant substrates. Suitable reagents will be investigated in the degradation of a wide range of substrates, including chlorinated solvents, BTEX, phthalates, MTBE and chlorophenols, as well as against recalcitrant lipophilic substrates such as polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls. Mechanistic studies associated with metal, ligand, and substrate-centered events will be pursued to report on the suitability of the reagents at hand and evaluate their biomimetic mode of action. The mechanistic work is also expected to provide insights in relation to the currently debated oxygenation pathways of biological oxygenases (P-450, sMMO). The most successful reagents will become the subject of bench-scale, column treatability studies in sequential reductive (Fe(0)) and oxidative treatment zones designed to effect complete degradation of organic contaminants. The oxidative zone will be composed of the oxygenation reagents developed in this study, suitably modified to afford heterogeriized versions of the catalysts supported on inert matrices. The effectiveness on chemical mixtures will be studied in detail.

Agency
National Institute of Health (NIH)
Institute
National Institute of Environmental Health Sciences (NIEHS)
Type
Hazardous Substances Basic Research Grants Program (NIEHS) (P42)
Project #
5P42ES007381-15
Application #
7799056
Study Section
Special Emphasis Panel (ZES1)
Project Start
Project End
2012-09-19
Budget Start
2009-04-01
Budget End
2013-03-31
Support Year
15
Fiscal Year
2009
Total Cost
$215,064
Indirect Cost
Name
Boston University
Department
Type
DUNS #
604483045
City
Boston
State
MA
Country
United States
Zip Code
02118
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