Surface Reactions Limiting Chromium(VI) Generation from Naturally Derived Chromium(III) Minerals

Abstract:

Chromium(III)-bearing minerals, commonly found in serpentinite and ultramaphic rocks, are ubiquitous in California soils and along convergent plate boundaries worldwide. Elevated concentrations of carcinogenic Cr(VI) have been measured in groundwater throughout the state, even in aquifers untouched by anthropogenic contamination. In most natural systems, manganese oxides are the only known, kinetically viable, oxidant of Cr(III). Numerous laboratory studies have demonstrated a finite capacity of Mn-oxides to generate Cr(VI) before surface alterations inhibit further Cr-oxidation. The extent to which these processes dictate the inhibition, and subsequent regeneration, of Mn-oxidation capacity within structured soils and sediments is not well understood. Here we use artificial soil aggregates made of Fe(III),Cr(III)-hydroxide-coated quartz sand and surrounded by aerated solute flow (pH 8, 30mM HEPES, 10mM HCO₃^-) to investigate C(VI) generation within ultramafic rock derived sediment and processes inhibiting manganese reactivity. We found that while Cr(VI)-production scaled with Cr-mineral solubility; Cr(VI) effluent concentrations from aggregates of both lower and higher solubility Cr(III)-minerals peaked very soon after reaction with birnessite (within 2 days and 4 days, respectively). Once Cr(VI) production plateaued (t=22 days) aggregate influent was acidified (pH 5, 30mM C₂H₃O₂^-). Despite increasing Cr(III) solubility at lower pH, aqueous Cr(VI) production further decreased. A secondary pulse of Cr(VI) generation was seen only after the surrounding solute returned to initial conditions (pH 8). As with the initial pulse, Cr(VI) concentration scaled with mineral solubility. Collectively, our results demonstrate the extent that natural fluctuations in groundwater composition, both as a result of irrigation or precipitation events, have the potential to both regenerate and inhibit Mn-oxide surfaces. These synthetic soil aggregates provide insight into how fluctuating hydrologic and redox conditions can impact Cr and Mn cycling within structured soils.