Reactive Transport Modeling of Subaqueous Sediment Caps and Implications for the Long-Term Fate of Arsenic, Mercury, and Methylmercury.
A 1-D biogeochemical reactive transport model with a full set of equilibrium and kinetic biogeochemical reactions was developed to simulate the fate and transport of arsenic and mercury in subaqueous sediment caps. Model simulations (50 years) were performed for freshwater and estuarine scenarios with an anaerobic porewater and either a diffusion-only or a diffusion plus 0.1-m/year upward advective flux through the cap. A biological habitat layer in the top 0.15 m of the cap was simulated with the addition of organic carbon. For arsenic, the generation of sulfate-reducing conditions limits the formation of iron oxide phases available for adsorption. As a result, subaqueous sediment caps may be relatively ineffective for mitigating contaminant arsenic migration when influent concentrations are high and sorption capacity is insufficient. For mercury, sulfate reduction promotes the precipitation of metacinnabar (HgS) below the habitat layer, and associated fluxes across the sediment-water interface are low. As such, cap thickness is a key design parameter that can be adjusted to control the depth below the sediment-water interface at which mercury sulfide precipitates. The highest dissolved methylmercury concentrations occur in the habitat layer in estuarine environments under conditions of advecting porewater, but the highest sediment concentrations are predicted to occur in freshwater environments due to sorption on sediment organic matter. Site-specific reactive transport simulations are a powerful tool for identifying the major controls on sediment- and porewater-contaminant arsenic and mercury concentrations that result from coupling between physical conditions and biologically mediated chemical reactions.
S.S. Papadopulos and Associates, 19215 SE 34th St., Suite 106-370, Camas, WA 98607 USA.
Brad A
BA
Bessinger
Anchor QEA, 421 SW Sixth Avenue, Suite 750, Portland, OR 97204 USA.
Dimitri
D
Vlassopoulos
School of Natural Sciences, University of California, 5200 North Lake Rd, Merced, CA 95343 USA ; Institute for Agricultural Sciences, Consejo Superior de Investigaciones Científicas (CSIC), Serrano 115-dup, 28006 Madrid, Spain.
Susana
S
Serrano
School of Natural Sciences, University of California, 5200 North Lake Rd, Merced, CA 95343 USA.
Peggy A
PA
O'Day
Biogeochemical kinetics; Reactive transport; Remediation; Sediment cap