Nathan W. Johnson

Influence of porewater sulfide on methylmercury production and partitioning in sulfate-impacted lake sediments

In low-sulfate and sulfate-limited freshwater sediments, sulfate loading increases the production of methylmercury (MeHg), a potent and bioaccumulative neurotoxin. Sulfate loading to anoxic sediments leads to sulfide production that can inhibit mercury methylation, but this has not been commonly observed in freshwater lakes and wetlands. In this study, sediments were collected from sulfate-impacted, neutral pH, surface water bodies located downstream from ongoing and historic mining activities to examine how chronic sulfate loading produces porewater sulfide, and influences MeHg production and transport. Sediments were collected over two years, during several seasons from lakes with a wide range of overlying water sulfate concentration. Samples were characterized for in-situ solid phase and porewater MeHg, Hg methylation potentials via incubations with enriched stable Hg isotopes, and sulfur, carbon, and iron content and speciation. Porewater sulfide reflected historic sulfur loading and was strongly related to the extractable iron content of sediment. Overall, methylation potentials were consistent with the accumulation of MeHg on the solid phase, but both methylation potentials and MeHg were significantly lower at chronically sulfate-impacted sites with a low solid-phase Fe:S ratio. At these heavily sulfate-impacted sites that also contained elevated porewater sulfide, both MeHg production and partitioning are influenced: Hg methylation potentials and sediment MeHg concentrations are lower, but occasionally porewater MeHg concentrations in sediment are elevated, particularly in the spring. The dual role of sulfide as a ligand for inorganic mercury (decreasing bioavailability) and methylmercury (increasing partitioning into porewater) means that elucidating the role of iron and sulfur loads as they define porewater sulfide is key to understanding sulfates influence on MeHg production and partitioning in sulfate-impacted freshwater sediment.

Methylmercury production in a chronically sulfate-impacted sub-boreal wetland.

Increased deposition of atmospheric sulfate exacerbates methylmercury (MeHg) production in freshwater wetlands by stimulating methylating bacteria, but it is unclear how methylation in sub-boreal wetlands is impacted by chronically elevated sulfate inputs, such as through mine discharges. The purpose of our study is to determine how sulfate discharges to wetlands from iron mining activities impact MeHg production. In this study, we compare spatial and temporal patterns in MeHg and associated geochemistry in two wetlands receiving contrasting loads of sulfate. Two orders of magnitude less sulfate in the un-impacted wetland create significant differences in acid-volatile sulfide and porewater sulfide; however, dissolved and solid-phase MeHg concentrations and methylation rate potentials (Kmeth) are statistically similar in both wetlands. Permitted mine pumping events flood the sulfate-impacted wetland with very high sulfate waters during the fall. In contrast to observations in sulfate-limited systems, this large input of sulfate to a chronically sulfate-impacted system led to significantly lower potential relative methylation rates, suggesting a predominance of demethylation processes over methylation processes during the sulfate loading. Overall, short-term measurements of methylation and demethylation potential are unrelated to gross measures of long-term MeHg accumulation, indicating a decoupling of short- and long-term process measurements and an overall disequilibrium in the systems. High sulfide accumulation, above ∼600-800 μg l(-1) sulfide, in the sulfate-impacted system lowers long-term MeHg accumulation, perhaps as a result of less bioavailable Hg-S complexes. Although continued research is required to determine how sulfate-limited freshwater wetlands might respond to new, large inputs of high-sulfate runoff from mining operations, chronically impacted wetlands do not appear to continually accumulate or produce MeHg at rates different from wetlands unimpacted by mining.

Increase in Nutrients, Mercury, and Methylmercury as a Consequence of Elevated Sulfate Reduction to Sulfide in Experimental Wetland Mesocosms

Microbial sulfate reduction (MSR) in both freshwater and marine ecosystems is a pathway for the decomposition of sedimentary organic matter (OM) after oxygen has been consumed. In experimental freshwater wetland mesocosms, sulfate additions allowed MSR to mineralize OM that would not otherwise have been decomposed. The mineralization of OM by MSR increased surface water concentrations of ecologically important constituents of OM: dissolved inorganic carbon, dissolved organic carbon, phosphorus, nitrogen, total mercury, and methylmercury. Increases in surface water concentrations, except for methylmercury, were in proportion to cumulative sulfate reduction, which was estimated by sulfate loss from the surface water into the sediments. Stoichiometric analysis shows that the increases were less than would be predicted from ratios with carbon in sediment, indicating that there are processes that limit P, N, and Hg mobilization to, or retention in, surface water. The highest sulfate treatment produced high levels of sulfide that retarded the methylation of mercury, but simultaneously mobilized sedimentary inorganic mercury into surface water. As a result, the proportion of mercury in the surface water as methylmercury peaked at intermediate porewater sulfide concentrations. The mesocosms have a relatively high ratio of wall and sediment surfaces to the volume of overlying water, perhaps enhancing the removal of nutrients and mercury to periphyton. The presence of wild rice decreased sediment sulfide concentrations by 30%, which was most likely a result of oxygen release from the wild rice roots. An additional consequence of the enhanced MSR was that sulfate additions produced phytotoxic levels of sulfide in sediment porewater.

The utility of solid‐phase microextraction in evaluating polycyclic aromatic hydrocarbon bioavailability during habitat restoration with dredged material at moderately contaminated sites

The over- or underprediction of risk in moderately contaminated sediments can have a large impact on the nature of applied management strategies given that concentrations border on being toxic or not toxic. Project managers should give significant consideration as to how moderate levels of contaminants in native sediments and dredged material used for restoration will impact recovery of habitat. Total solid-phase (Ctotal ) and porewater (Cfree ) polycyclic aromatic hydrocarbons (PAHs) were quantified in native sediments and dredged material to determine if the predictions of risk from Ctotal are consistent with those based on Cfree . The sediment matrix phase in which PAHs were quantified resulted in disparate conclusions regarding the predicted reduction in contamination following restoration. Total solid-phase PAH concentrations suggested a significant decrease following restoration, whereas little to no change was observed in measured Cfree . Risk metrics based on Ctotal gave inconclusive estimates for toxicity, whereas measured Cfree suggested toxicity is unlikely, a conclusion consistent with toxicity testing. The incorporation of black carbon (BC) into model estimates for Cfree gave predictions more consistent with measured Cfree , suggesting that geochemical conditions (especially BC) play an important part in predicting toxicity at moderately contaminated sites. In addition to the use of Cfree in toxicity evaluation, in-situ Cfree measurements provided a constraint on diffusive PAH loads from sediment relative to ongoing stream loads. If passive sampling had been employed during the sampling designs and site evaluations, the costs of toxicity testing would not have been incurred, given that Cfree suggested little to no toxicity. The results from the project highlight the benefits to be gained by moving beyond inconclusive, screening-level Ctotal metrics and implementing more sensitive and accurate Cfree metrics in assessments of risk in moderately contaminated sediments. Integr Environ Assess Manag 2018;14:212-223.

The utility of SPME in evaluating PAH bioavailability during habitat restoration with dredged material at moderately contaminated sites

The over- or underprediction of risk in moderately contaminated sediments can have a large impact on the nature of applied management strategies given that concentrations border on being toxic or not toxic. Project managers should give significant consideration as to how moderate levels of contaminants in native sediments and dredged material used for restoration will impact recovery of habitat. Total solid-phase (Ctotal ) and porewater (Cfree ) polycyclic aromatic hydrocarbons (PAHs) were quantified in native sediments and dredged material to determine if the predictions of risk from Ctotal are consistent with those based on Cfree . The sediment matrix phase in which PAHs were quantified resulted in disparate conclusions regarding the predicted reduction in contamination following restoration. Total solid-phase PAH concentrations suggested a significant decrease following restoration, whereas little to no change was observed in measured Cfree . Risk metrics based on Ctotal gave inconclusive estimates for toxicity, whereas measured Cfree suggested toxicity is unlikely, a conclusion consistent with toxicity testing. The incorporation of black carbon (BC) into model estimates for Cfree gave predictions more consistent with measured Cfree , suggesting that geochemical conditions (especially BC) play an important part in predicting toxicity at moderately contaminated sites. In addition to the use of Cfree in toxicity evaluation, in-situ Cfree measurements provided a constraint on diffusive PAH loads from sediment relative to ongoing stream loads. If passive sampling had been employed during the sampling designs and site evaluations, the costs of toxicity testing would not have been incurred, given that Cfree suggested little to no toxicity. The results from the project highlight the benefits to be gained by moving beyond inconclusive, screening-level Ctotal metrics and implementing more sensitive and accurate Cfree metrics in assessments of risk in moderately contaminated sediments. Integr Environ Assess Manag 2018;14:212-223.