Distribution and Homogenization of Multiple Mercury Species Inputs to Freshwater Wetland Mesocosms.

Mercury (Hg)-impaired aquatic ecosystems often receive multiple inputs of different Hg species with varying potentials for transformation and bioaccumulation. Over time, these distinct input pools of Hg homogenize in their relative distributions and bioaccumulation potentials as a result of biogeochemical processes and other aging processes within the ecosystem. This study sought to evaluate the relative time scale for homogenization of multiple Hg inputs to wetlands, information that is relevant for ecosystem management strategies that consider Hg source apportionment. We performed experiments in simulated freshwater wetland mesocosms that were dosed with four isotopically labeled mercury forms: two dissolved forms (Hg2+ and Hg-humic acid) and two particulate forms (nano-HgS and Hg adsorbed to FeS). Over the course of one year, we monitored the four Hg isotope endmembers for their relative distribution between surface water, sediment, and fish in the mesocosms, partitioning between soluble and particulate forms, and conversion to methylated mercury (MeHg). We also evaluated the reactivity and mobility of Hg through sequential selective extractions of sediment and the uptake flux of aqueous Hg in a diffusive gradient in thin-film (DGT) passive samplers. We observed that the four isotope spikes were relatively similar in surface water concentration (ca. 3000 ng/L) immediately after spike addition. At 1-3 months after dosing, Hg concentrations were 1-50 ng/L and were greater for the initially dissolved isotope endmembers than the initially particulate endmembers. In contrast, the Hg isotope endmembers in surface sediments were similar in relative concentration within 2 months after spike addition. However, the uptake fluxes of Hg in DGT samplers, deployed in both the water column and surface sediment, were generally greater for initially dissolved Hg endmembers and lower for initially particulate endmembers. At one year postdosing, the DGT-uptake fluxes were converging toward similar values between the Hg isotope endmembers. However, the relative distribution of isotope endmembers was still significantly different in both the water column and sediment (p < 0.01 according to one-way ANOVA analysis). In contrast, selective sequential extractions resulted in a homogeneous distribution, with >90% of each endmember extracted in the KOH fraction, suggesting that Hg species were associated with sediment organic matter. For MeHg concentrations in surface sediment and fish, the relative contributions from each endmember were significantly different at all sampling time points. Altogether, these results provide insights into the time scales of distribution for different Hg species that enter a wetland ecosystem. While these inputs attain homogeneity in concentration in primary storage compartments (i.e., sediments) within weeks after addition, these input pools remain differentiated for more than one year in terms of reactivity for passive samplers, MeHg concentration, and bioaccumulation.

Utility of Diffusive Gradient in Thin-Film Passive Samplers for Predicting Mercury Methylation Potential and Bioaccumulation in Freshwater Wetlands.

Mercury is a risk in aquatic ecosystems when the metal is converted to methylmercury (MeHg) and subsequently bioaccumulates in aquatic food webs. This risk can be difficult to manage because of the complexity of biogeochemical processes for mercury and the need for accessible techniques to navigate this complexity. Here, we explored the use of diffusive gradient in thin-film (DGT) passive samplers as a tool to simultaneously quantify the methylation potential of inorganic Hg (IHg) and the bioaccumulation potential of MeHg in freshwater wetlands. Outdoor freshwater wetland mesocosms were amended with four isotopically labeled and geochemically relevant IHg forms that represent a range of methylation potentials (202Hg2+, 201Hg-humic acid, 199Hg-sorbed to FeS, and 200HgS nanoparticles). Six weeks after the spikes, we deployed DGT samplers in the mesocosm water and sediments, evaluated DGT-uptake rates of total Hg, MeHg, and IHg (calculated by difference) for the Hg isotope spikes, and examined correlations with total Hg, MeHg, and IHg concentrations in sediment, water, and micro and macrofauna in the ecosystem. In the sediments, we observed greater relative MeHg concentrations from the initially dissolved IHg isotope spikes and lower MeHg levels from the initially particulate IHg spikes. These trends were consistent with uptake flux of IHg into DGTs deployed in surface sediments. Moreover, we observed correlations between total Hg-DGT uptake flux and MeHg levels in periphyton biofilms, submergent plant stems, snails, and mosquitofish in the ecosystem. These correlations were better for DGTs deployed in the water column compared to DGTs in the sediments, suggesting the importance of vertical distribution of bioavailable MeHg in relation to food sources for macrofauna. Overall, these results demonstrate that DGT passive samplers are a relatively simple and efficient tool for predicting IHg methylation and MeHg bioaccumulation potentials without the need to explicitly delineate IHg and MeHg speciation and partitioning in complex ecosystems.