Manganese(iv) oxide amendments reduce methylmercury concentrations in sediment porewater.

Manganese(iv) oxide (pyrolusite, birnessite) mineral amendments can reduce dissolved MeHg concentrations in sediment theoretically by inhibiting microbial sulfate reduction, which is a major methylation pathway in sediments. Anaerobic sediment slurry microcosms in which Hg methylation was stimulated by addition of labile organic carbon (acetate) and HgCl2 showed that manganese(iv) oxide reduced the percent MeHg in slurry porewater (filtered), by 1-2 orders of magnitude relative to controls. Sediment-water mesocosms with pyrolusite or birnessite either directly mixed into the top 5 cm or applied in a thin (5 cm) sand layer over sediment showed reductions in percent MeHg in porewater of 66-69% for pyrolusite and 81-89% for birnessite amendment. A thin sand layer alone resulted in 65% reduction. CO2 respirometry experiments showed that the amendments stimulated microbial activity. Microbial community census by PCR and DNA sequencing indicated that the addition of Mn(iv) oxides did not significantly alter the indigenous sediment microbial community structure, although a small increase in abundance of iron and manganese reducers was observed after a 2 week incubation period. The mechanism of decreasing MeHg relative to Hg concentrations in porewater likely involved an increase in the importance of Mn(iv) reduction (relative to sulfate reduction) in heterotrophic microbial metabolism in the sediments amended with Mn(iv) oxides. Manganese reduction was confirmed as the predominant biogeochemical redox process by microelectrode voltammetry profiling of the sediment microcosms, although adsorption to Mn oxide surfaces, enhanced MeHg demethylation, and abiotic reduction of Mn(iv) also may have been involved in reducing percent MeHg and suppressing net MeHg production. These results represent a novel approach for mitigating MeHg impacts from sediments with potential applicability to a range of aquatic settings including intertidal zones, tidal marshes, seasonal wetlands, reservoirs, and lakes.

Persistent reductions in the bioavailability of PCBs at a tidally inundated Phragmites australis marsh amended with activated carbon.

In situ amendment of sediments with highly sorbent materials like activated carbon (AC) is an increasingly viable strategy to reduce the bioavailability of persistent, sediment-associated contaminants to benthic communities. Because in situ sediment remediation is an emerging strategy, much remains to be learned about the field conditions under which amendments can be effective, the resilience of amendment materials toward extreme weather conditions, and the optimal design of engineered applications. We report the results of a multiyear, pilot-scale field investigation designed to measure the persistence and efficacy of AC amendments to reduce the bioavailability of polychlorinated biphenyls (PCBs) in an intertidal Phragmites marsh. The amendments tested were granular AC (GAC), GAC with a layer of sand, and a pelletized fine AC. Key metrics presented include vertically resolved black carbon concentrations in sediment and PCB concentrations in sediment, porewater, and several invertebrate species. The results demonstrate that all 3 amendments withstood Hurricane Sandy and remained in place for the duration of the study, successfully reducing porewater PCB concentrations by 34 to 97%. Reductions in invertebrate bioaccumulation were observed in all amendment scenarios, with pelletized fine AC producing the most pronounced effect. The present findings support the use of engineered AC amendments in intertidal marshes and can be used to inform amendment design, delivery, and monitoring at other contaminated sediment sites. Environ Toxicol Chem 2018;37:2496-2505. © 2018 SETAC.

Biogeochemical controls on methylmercury in soils and sediments: Implications for site management.

Management of Hg-contaminated sites poses particular challenges because methylmercury (MeHg), a potent bio-accumulative neurotoxin, is formed in the environment, and concentrations are not generally predictable based solely on total Hg (THg) concentrations. In this review, we examine the state of knowledge regarding the chemical, biological, and physical controls on MeHg production and identify those most critical for contaminated site assessment and management. We provide a list of parameters to assess Hg-contaminated soils and sediments with regard to their potential to be a source of MeHg to biota and therefore a risk to humans and ecological receptors. Because some measurable geochemical parameters (e.g., DOC) can have opposing effects on Hg methylation, we recommend focusing first on factors that describe the potential for Hg bio-accumulation: site characteristics, Hg and MeHg concentrations, Hg availability, and microbial activity, where practical. At some sites, more detailed assessment of biogeochemistry may be required to develop a conceptual site model for remedial decision making. Integr Environ Assess Manag 2017;13:249-263. © 2016 SETAC.

Evidence for regulation of monomethyl mercury by nitrate in a seasonally stratified, eutrophic lake.

The accumulation of monomethyl mercury (CH3Hg+) in aquatic ecosystems is a redox sensitive process that is accelerated under sulfate-reducing conditions. While nitrate (NO3-) reduction is energetically favored over sulfate reduction, the influence of NO3 on the accumulation of CH3Hg+ has not been reported in the literature. We examined temporal and vertical patterns in redox constituents and CH3Hg+ concentrations in the hypolimnion of a dimictic lake, Onondaga Lake, prior to and following increases in NO3- inputs. Detailed water-column profiles and a long-term record revealed marked decreases in the accumulation of CH3Hg+ in the anoxic hypolimnion coinciding with long-term decreases in the deposition of organic matter coupled with recent increases in NO3-concentrations. CH3Hg+ concentrations in the hypolimnion were substantially abated when No3 was present above the sediment-water interface. A decrease in the peak hypolimnetic mass of CH3Hg+ and shortening of the period of elevated CH3Hg+ concentrations resulted in more than a 50% decline in the accumulated CH3Hg+. N03- regulation of CH3Hg+ accumulation may be a widespread phenomenon in oxygen-limited freshwater and terrestrial environments, and could have an important notpreviously recognized, effect on the biogeochemistry of mercury.