Degradation of chlorinated solvents with reactive iron minerals in subsurface sediments from redox transition zones

Reactive iron (Fe) mineral coatings found in subsurface reduction-oxidation transition zones (RTZs) contribute to the attenuation of contaminants. An 18.3-m anoxic core was collected from the site, where constituents of concern (COCs) in groundwater included chlorinated solvents. Reactive Fe mineral coatings were found to be abundant in the RTZs. This research focused on evaluating reaction kinetics with anoxic sediments bearing ferrous mineral nano-coatings spiked with either tetrachloroethylene (PCE), trichloroethylene (TCE), or 1,4-dichlorobenzene (1,4-DCB). Reaction kinetics with RTZ sediments followed pseudo-first-order reactions for the three contaminants with 90% degradation achieved in less than 39 days. The second-order rate constants for the three COCs ranged from 6.20 × 10^-4 to 1.73 × 10^-3 Lg^-1h^-1 with pyrite (FeS₂), 4.97 × 10^-5 to 1.24 × 10^-3 Lg^-1h^-1with mackinawite (FeS), 1.25 × 10^-4 to 1.89 × 10^-4 Lg^-1h^-1 with siderite (FeCO₃), and 1.79 × 10^-4 to 1.10 × 10^-3 Lg^-1h^-1 with magnetite (Fe₃O₄). For these three chlorinated solvents, the trend for the rate constants followed: Fe(II) sulfide minerals > magnetite > siderite. The high reactivity of Fe mineral coatings is hypothesized to be due to the large surface areas of the nano-mineral coatings. As a result, these surfaces are expected to play an important role in the attenuation of chlorinated solvents in contaminated subsurface environments.