Effect of oxygen, nitrate and aluminum addition on methylmercury efflux from mine-impacted reservoir sediment.

Extensive contamination of aquatic ecosystems with mercury (Hg) has led to a growing interest in developing in situ management strategies to repress Hg bioaccumulation in aquatic biota in reservoirs. This study used experimental chamber incubations to assess the impact of three potential treatments, oxygen addition, nitrate addition and aluminum addition, to reduce the flux of toxic methylmercury (MeHg) from profundal reservoir sediment. The study sites, Almaden Lake and Guadalupe Reservoir, are located downstream of the historic New Almaden mining district in Santa Clara Valley, California, USA. In the first experiment (experiment 1), replicate chambers from both sites were incubated sequentially under aerobic and anaerobic conditions. At both sites, mean anaerobic fluxes of MeHg were higher than aerobic fluxes (Almaden: 11.0 vs. -2.3 ng/m2·d; Guadalupe: 22.3 vs 5.5 ng/m2·d), and anaerobic MeHg fluxes correlated with rates of sediment sulfate uptake, highlighting the linkage between MeHg production and microbial sulfate reduction. Under aerobic conditions, sediment from Guadalupe Reservoir released Hg(II), iron and sulfate, suggesting the oxidative dissolution of Hg-bearing sulfide minerals. A follow-up study at Almaden Lake (experiment 2) found that mean MeHg fluxes under aerobic conditions (5 ng/m2·d) and anoxic (nitrate-rich) conditions (1.7 ng/m2·d) were lower than anaerobic conditions (174 ng/m2·d), but aluminum addition had little effect (105 ng/m2·d) on MeHg flux. In both anaerobic and aluminum treated chambers, MeHg flux turned negative during the second half of the incubation, suggesting that highly reduced, sulfidic conditions lowered net methylation, possibly by enhancing demethylation or repressing Hg(II) bioavailability for methylation.

Effects of nitrate addition on water column methylmercury in Occoquan Reservoir, Virginia, USA.

Mercury bioaccumulation in aquatic biota poses a widespread threat to human and environmental health. Methylmercury (MeHg), the toxic form of mercury, tends to build up under anaerobic conditions in the profundal zones of lakes. In this study we performed a two-year assessment of spatial and temporal patterns of dissolved oxygen, nitrate, MeHg, manganese (Mn) and iron (Fe) in Occoquan Reservoir, a large run-of-the-river drinking water reservoir in Virginia, USA. A tributary to the reservoir receives input of nitrate-rich tertiary-treated wastewater that enhances the oxidant capacity of bottom water. Multiple lines of evidence supported the hypothesis that the presences of nitrate and/or oxygen in bottom water correlated with low MeHg in bottom water. Bottom water MeHg was significantly lower in a nitrate-rich tributary (annual mean of 0.05 ng/L in both 2012 and 2013) compared to a nitrate-poor tributary (annual mean of 0.58 ng/L in 2012 and 0.21 ng/L in 2013). The presence of nitrate and oxygen in bottom water corresponded with significantly lower bottom water MeHg at an upstream station in the main reservoir (0.05 versus 0.11 ng/L in 2013). In 2012 the reservoir exhibited a longitudinal gradient with nitrate and oxygen decreasing and MeHg and Mn increasing downstream. In both study years, there was a clear threshold of oxygen equivalent (3-5 mg/L), a metric that combines the oxidant capacity of nitrate and oxygen, above which MeHg (<0.05 ng/L), Mn (<0.3 mg/L) and Fe (<0.5 mg/L) were low. Results indicated that the addition of nitrate-rich tertiary-treated wastewater to the bottom of anaerobic reservoirs can reduce MeHg concentrations, and potentially decrease mercury bioaccumulation, while increasing the safe water yield for potable use.