Stochastic Framework for Addressing Chemical Partitioning and Bioavailability in Contaminated Sediment Assessment and Management.

Passive sampling to quantify net partitioning of hydrophobic organic contaminants between the porewater and solid phase has advanced risk management for contaminated sediments. Direct porewater (Cfree) measures represent the best way to predict adverse effects to biota. However, when the need arises to convert between solid-phase concentration (Ctotal) and Cfree, a wide variation in observed sediment-porewater partition coefficients (KTOC) is observed due to intractable complexities in binding phases. We propose a stochastic framework in which a given Ctotal is mapped to an estimated range of Cfree through variability in passive sampling-derived KTOC relationships. This mapping can be used to pair estimated Cfree with biological effects data or inversely to translate a measured or assumed Cfree to an estimated Ctotal. We apply the framework to both an effects threshold for polycyclic aromatic hydrocarbon (PAH) toxicity and an aggregate adverse impact on an assemblage of species. The stochastic framework is based on a "bioavailability ratio" (BR), which reflects the extent to which potency-weighted, aggregate PAH partitioning to the solid-phase is greater than that predicted by default, KOW-based KTOC values. Along a continuum of Ctotal, we use the BR to derive an estimate for the probability that Cfree will exceed a threshold. By explicitly describing the variability of KTOC and BR, estimates of risk posed by sediment-associated contaminants can be more transparent and nuanced.

Diverse Communities of hgcAB+ Microorganisms Methylate Mercury in Freshwater Sediments Subjected to Experimental Sulfate Loading.

Methylmercury (MeHg) is a bioaccumulative neurotoxin produced by certain sulfate-reducing bacteria and other anaerobic microorganisms. Because microorganisms differ in their capacity to methylate mercury, the abundance and distribution of methylating populations may determine MeHg production in the environment. We compared rates of MeHg production and the distribution of hgcAB genes in epilimnetic sediments from a freshwater lake that were experimentally amended with sulfate levels from 7 to 300 mg L-1. The most abundant hgcAB sequences were associated with clades of Methanomicrobia, sulfate-reducing Deltaproteobacteria, Spirochaetes, and unknown environmental sequences. The hgcAB+ communities from higher sulfate amendments were less diverse and had relatively more Deltaproteobacteria, whereas the communities from lower amendments were more diverse with a larger proportion of hgcAB sequences affiliated with other clades. Potential methylation rate constants varied 52-fold across the experiment. Both potential methylation rate constants and % MeHg were the highest in sediments from the lowest sulfate amendments, which had the most diverse hgcAB+ communities and relatively fewer hgcAB genes from clades associated with sulfate reduction. Although pore water sulfide concentration covaried with hgcAB diversity across our experimental sulfate gradient, major changes in the community of hgcAB+ organisms occurred prior to a significant buildup of sulfide in pore waters. Our results indicate that methylating communities dominated by diverse anaerobic microorganisms that do not reduce sulfate can produce MeHg as effectively as communities dominated by sulfate-reducing populations.

Effects of sulfate and sulfide on the life cycle of Zizania palustris in hydroponic and mesocosm experiments.

Under oxygenated conditions, sulfate is relatively non-toxic to aquatic plants. However, in water-saturated soils, which are usually anoxic, sulfate can be reduced to toxic sulfide. Although the direct effects of sulfate and sulfide on the physiology of a few plant species have been studied in some detail, their cumulative effects on a plant's life cycle through inhibition of seed germination, seedling survival, growth, and seed production have been less well studied. We investigated the effect of sulfate and sulfide on the life cycle of wild rice (Zizania palustris L.) in hydroponic solutions and in outdoor mesocosms with sediment from a wild rice lake. In hydroponic solutions, sulfate had no effect on seed germination or juvenile seedling growth and development, but sulfide greatly reduced juvenile seedling growth and development at concentrations greater than 320 µg/L. In outdoor mesocosms, sulfate additions to overlying water increased sulfide production in sediments. Wild rice seedling emergence, seedling survival, biomass growth, viable seed production, and seed mass all declined with sulfate additions and hence sulfide concentrations in sediment. These declines grew steeper during the course of the 5 yr of the mesocosm experiment and wild rice populations became extinct in most tanks with concentrations of 250 mg SO4 /L or greater in the overlying water. Iron sulfide precipitated on the roots of wild rice plants, especially at high sulfate application rates. These precipitates, or the encroachment of reducing conditions that they indicate, may impede nutrient uptake and be partly responsible for the reduced seed production and viability.

Biogeochemical changes and mercury methylation beneath an in-situ sediment cap.

In-situ capping has shown promise as a management strategy for contaminated aquatic sediments, however, little is known about how mercury methylation in underlying sediments will be affected. Changes to the location and extent of sulfate reduction and other biological processes were studied in estuarine sediment using laboratory microcosms. Observations in a model sediment showed increases of in situ total methylmercury concomitant with an upward extension of anaerobic bacterial activity beneath a sediment cap and under anoxic conditions. Increased methylmercury (up to 50%) was observed beneath a sediment cap in a region 2-3 cm higher than in an uncapped sediment. A 1-dimensional, unsteady, reaction transport model was used to simulate the transient response to mercury-related biogeochemical processes. The location, magnitude, and expected duration of the increased methylmercury was such that a significant impact on near cap-water interface methylmercury was not expected for the sediments studied. Explicit consideration of the biogeochemical effects of capping on mercury contaminated sediment, however, may be necessary for very thin or unstable capping layers where the physical sequestration provided by a cap may be compromised.

Cumulative Sulfate Loads Shift Porewater to Sulfidic Conditions in Freshwater Wetland Sediment.

It is well established that sulfide can be toxic to rooted aquatic plants. However, a detailed description of the effects of cumulative sulfate loads on sulfide and iron (Fe) porewater geochemistry, plant exposure, and ecological response is lacking. Over 4 yr, we experimentally manipulated sulfate loads to self-perpetuating wild rice (Zizania palustris) populations and monitored increases in the ratio of sulfur (S) to Fe in sediment across a range of sulfide loading rates driven by overlying water sulfate. Because natural settings are complicated by ongoing Fe and S loads from surface and groundwater, this experimental setting provides a tractable system to describe the impacts of increased S loading on Fe-S porewater geochemistry. In the experimental mesocosms, the rate of sulfide accumulation in bulk sediment increased linearly with overlying water sulfate concentration up to 300 µg-SO4 cm-3 . Seedling survival at the beginning of the annual life cycle and seed mass and maturation at the end of the annual life cycle all decreased at porewater sulfide concentrations between 0.4 and 0.7 µg cm-3 . Changes to porewater sulfide, plant emergence, and plant nutrient uptake during seed production were closely related to the ratio of S to Fe in sediment. A mass balance analysis showed that porewater sulfide remained a small and relatively transient phase compared to sulfate in the overlying water and Fe in the sediment solid phase. The results illuminate the evolution of the geochemical setting and timescales over which 4 yr of cumulative sulfate loading resulted in a wholesale shift from Fe-dominated to sulfide-dominated porewater chemistry. This shift was accompanied by detrimental effects to, and eventual extirpation of, self-perpetuating wild rice populations. Environ Toxicol Chem 2019;38:1231-1244. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Molecular evidence for novel mercury methylating microorganisms in sulfate-impacted lakes.

Methylmercury (MeHg) is a bioaccumulative neurotoxin that is produced by certain anaerobic microorganisms, but the abundance and importance of different methylating populations in the environment is not well understood. We combined mercury geochemistry, hgcA gene cloning, rRNA methods, and metagenomics to compare microbial communities associated with MeHg production in two sulfate-impacted lakes on Minnesota's Mesabi Iron Range. The two lakes represent regional endmembers among sulfate-impacted sites in terms of their dissolved sulfide concentrations and MeHg production potential. rRNA amplicon sequencing indicates that sediments and anoxic bottom waters from both lakes contained diverse communities with multiple clades of sulfate reducing Deltaproteobacteria and Clostridia. In hgcA gene clone libraries, however, hgcA sequences were from taxa associated with methanogenesis and iron reduction in addition to sulfate reduction, and the most abundant clones were from unknown groups. We therefore applied metagenomics to identify the unknown populations in the lakes with the capability to methylate mercury, and reconstructed 27 genomic bins with hgcA. Some of the most abundant potential methylating populations were from phyla that are not typically associated with MeHg production, including a relative of the Aminicenantes (formerly candidate phylum OP8) and members of the Kiritimatiellaeota (PVC superphylum) and Spirochaetes that, together, were more than 50% of the potential methylators in some samples. These populations do not have genes for sulfate reduction, and likely degrade organic compounds by fermentation or other anaerobic processes. Our results indicate that previously unrecognized populations with hgcAB are abundant and may be important for MeHg production in some freshwater ecosystems.

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. © 2017 SETAC.

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 sulfate's 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.