Abiotic dechlorination in the presence of ferrous minerals

Laboratory batch experiments were performed to assess the reduction of trichloroethene (TCE) and oxygen via natural ferrous minerals. TCE reduction under anoxic conditions was measured via the generation of reduced gases, while oxygen reduction via the generation of hydroxyl radicals was measured as a surrogate for potential TCE oxidation. Results showed that TCE reduction under anoxic conditions was observed for ankerite, siderite, and illite, but not for biotite; acetylene was the primary identified dechlorination product. With the exception of biotite, first-order dechlorination rate constants increased with increasing ferrous content of the mineral, with rate constants ranging from 3.1 × 10^-8 to 4.8 10^-7 L g^-1 d^-1. Measured reduction potentials (mV vs SHE) ranged from -104 for illite to +84 for biotite. When normalizing measured first-order dechlorination rate constants to the estimated ferrous iron mineral specific surface area (where surface area was based on nitrogen adsorption analysis of the minerals), TCE dechlorination rate constants increased with increasing reduction potentials. Under oxic conditions, hydroxyl radicals were generated with each of the four minerals. However, mineral activity showed no readily apparent correlation to ferrous content or mineral surface area. In terms of TCE and oxygen reduced per mole of ferrous iron initially present in each mineral, illite was the most reactive of the four minerals. Together, these results suggest that several ferrous minerals may contribute to abiotic dechlorination in the natural environment, and (at least for TCE reduction under anoxic conditions) measurement of ferrous mineral content and reduction potential may serve as useful tools for estimating TCE first-order abiotic dechlorination rate constants.