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Metals and radionuclides Metals Greater solubility usually = greater toxicity Chromium (Cr) – Six oxidation states, +1, +2, +3, +4, +5, +6 • +3, +6 most common • used to prevent corrosion (stainless steel) • Cr(VI) is toxic (skin, lungs, kidneys) and carcinogenic • Hexavalent Cr(VI) is most toxic and most soluble • Induces free-radical formation • oxidative stress – DNA/membrane damage Erin Brockovich • PG&E used it as rust inhibitor • Migration into water supply Metals and radionuclides Radionuclides Radiotoxicity – from emitted particles – DNA damage Chemotoxicity – oxidative stress – DNA/membrane damage Uranium – heaviest natural element - 17 isotopes • Natural form % = U-238 (99.27), U-235 (0.72), U-234 (0.006) • U-238 (t1/2 = 4.5 billion years), U-235 (t1/2 = 7 million years) • Emit alpha, beta and gamma • Used in nuclear fuel – U-235 (readily fissionable) • Used in nuclear and conventional weapons • Uranium enrichment (increase percentage of U-235) • U-238 used as a precursor of Pu-239 • U-238 used to strengthen ammunition (depleted uranium) • 4 oxidation states (+4, +6 most common) • U(VI) water-soluble, U(IV) in-soluble Bioremediation Bioremediation strategies for metals and radionuclides are extremely varied and include both above ground and in situ treatments and many of the treatments already perfected for organic biodegradation. – Above ground strategies include bioreactors, biosorption, prepared beds, biopiles, bioleaching, phytoremediation, etc. – In situ strategies include bioimmobilization, biomobilization, soil washing, infiltration galleries, bioventing, etc. Bioimmobilization Direct reductive precipitation – using microbes to precipitate heavy metals by changing their valency Electrons from organic C (lactate, acetate, ethanol) or H2 eOxidation U(VI), Cr(VI) – soluble, toxic and mobile Reduction Metal reducing bacterium U(IV), Cr(III) – insoluble, less toxic, immobile Useful in above-ground and in situ treatments Bioimmobilization Indirect reductive precipitation microbial reduction of other TEAs (Fe3+ or SO4-) results in abiotic reduction and precipitation of heavy metals Electrons from organic C (lactate, acetate, ethanol) or H2 e- Ox Fe(III), SO4U(IV), Cr(III) insoluble, immobile Red Ox Red less toxic Metal reducing bacterium Fe(II), H2S U(VI), Cr(VI) soluble mobile toxic Useful in above-ground and in situ treatments Critical Biogeochemistry H2 Equivalents Chemical Species Fe (II) Organics SO4- H2S NO3- O2 O2 CH4 NO3- +10 Mn (IV) U (VI) Cr (VI) 0 Electron Acceptors Fe (III) SO4- CO2 PCE/TCE -10 Dominant Terminal Electron Accepting Process Aerobic Respiration Denitrification Iron (III) Reduction Sulfate Methanogenesis Reduction Time Distance from Source