Search

Mercury (Hg) methylation genes (hgcAB) mediate the formation of the toxic methylmercury and have been identified from diverse environments, including freshwater and marine ecosystems, Arctic permafrost, forest and paddy soils, coal-ash amended sediments, chlor-alkali plants discharges and geothermal springs. Here we present the first attempt at a standardized protocol for the detection, identification and quantification of hgc genes from metagenomes. Our Hg-cycling microorganisms in aquatic and terrestrial ecosystems (Hg-MATE) database, a catalogue of hgc genes, provides the most accurate information to date on the taxonomic identity and functional/metabolic attributes of microorganisms responsible for Hg methylation in the environment. Furthermore, we introduce "marky-coco", a ready-to-use bioinformatic pipeline based on de novo single-metagenome assembly, for easy and accurate characterization of hgc genes from environmental samples. We compared the recovery of hgc genes from environmental metagenomes using the marky-coco pipeline with an approach based on coassembly of multiple metagenomes. Our data show similar efficiency in both approaches for most environments except those with high diversity (i.e., paddy soils) for which a coassembly approach was preferred. Finally, we discuss the definition of true hgc genes and methods to normalize hgc gene counts from metagenomes., (© 2022 The Authors. Molecular Ecology Resources published by John Wiley & Sons Ltd.)

In situ amendment of activated carbon (AC) to sediments can effectively reduce the bioavailability of hydrophobic organic contaminants. While biochars have been suggested as low-cost and sustainable alternatives to ACs, there are few comparative sorption data especially for mercury (Hg) and methylmercury (MeHg) at the low porewater concentrations in sediments. Here we compare the ability of a wide range of commercially available and laboratory synthesized ACs and biochars to sorb PAHs, PCBs, DDTs, inorganic Hg, and MeHg at environmentally relevant concentrations. Compared to natural organic matter, sorption capacity for most organic compounds was at least 1-2 orders of magnitude higher for unactivated biochars and 3-4 orders of magnitude higher for ACs which translated to sediment porewater PCB concentration reductions of 18-80% for unactivated biochars, and >99% for ACs with 5% by weight amendment to sediment. Steam activated carbons were more effective than biochars in Hg sorption and translated to modeled porewater Hg reduction in the range of 94-98% for sediments with low native Kd and 31-73% for sediments with high native Kd values for Hg. Unactivated biochars were as effective as the steam activated carbons for MeHg sorption. Predicted reductions of porewater MeHg were 73-92% for sediments with low native Kd and 57-86% for sediment with high native K(d). ACs with high surface areas therefore are likely to be effective in reducing porewater concentrations of organics, Hg, and MeHg in impacted sediments. Unactivated biochars had limited effectiveness for organics and Hg but can be considered when MeHg exposure is the primary concern.

The Hg-methylating ability of dissimilatory iron-reducing bacteria in the genera Geobacter, Desulfuromonas, and Shewanella was examined. All of the Geobacter and Desulfuromonas strains tested methylated mercury while reducing Fe(III), nitrate, or fumarate. In contrast, none of the Shewanella strains produced methylmercury at higher levels than abiotic controls under similar culture conditions. Geobacter and Desulfuromonas are closely related to known Hg-methylating sulfate-reducing bacteria within the Deltaproteobacteria.

Results from pilot studies on colloidal phase transport of newly deposited mercury in lake water and overland runoff demonstrate that the combination of ultrafiltration, and stable isotope amendment techniques is a viable tool for the study of mercury partitioning to filterable carbon. Ultrafiltration mass balance calculations were generally excellent, averaging 97.3, 96.1 and 99.8% for dissolved organic carbon (DOC), total mercury (Hg(T)), and methylmercury (MeHg), respectively. Sub nanogram per liter quantities of isotope were measurable, and the observed phase distribution from replicate ultrafiltration separations on lake water agreed within 20%. We believe the data presented here are the first published colloidal phase mercury data on lake water and overland runoff from uncontaminated sites. Initial results from pilot-scale lake amendment experiments indicate that the choice of matrix used to dissolve the isotope did not affect the initial phase distribution of the added mercury in the lake. In addition there was anecdotal evidence that native MeHg was either recently produced in the system, or at a minimum, that this 'old' MeHg partitions to the same subset of DOC that binds the amended mercury. Initial results from pilot-scale overland runoff experiments indicate that less than 20% of newly deposited mercury was transported in the filterable fraction (<0.7 microm). There is some indication of colloidal phase enrichment of mercury in runoff compared to the phase distribution of organic carbon, but the mechanism of this enrichment is unclear. The phase distribution of newly deposited mercury can differ from that of organic carbon and native mercury, suggesting that the quality of the carbon (available ligands), not the quantity of carbon, regulates partitioning. Further characterization of DOC is needed to clarify the underlying mechanisms.

To help understand the mechanism and control of Hg uptake in Hg-methylating bacteria, we investigated the effect of sulfide on Hg methylation by pure cultures of the sulfate-reducing bacterium Desulfobulbus propionicus (1pr3). Our previous research in natural sediments has suggested that Hg methylation occurs most rapidly when sulfide concentrations favor formation of neutral dissolved Hg-S species. In this study, the chemical speciation of Hg in culture media was manipulated by growing D. propionicus across a range of sulfide concentrations, with inorganic Hg (HgI) added in the form of ground ores. A solid-phase, rather than a dissolved source of Hg, was used to simulate the controls on Hg partitioning between solid and aqueous phases found in natural sediments. Methylmercury (MeHg) production by cultures was not related to the absolute solid-phase concentration of Hg in the ores, and it was only weakly related to the dissolved HgI concentration in the medium. However, MeHg production was linearly related to the calculated concentration of the dominant neutral complex in solution, HgS degrees. Furthermore, the diffusive membrane permeability of HgS degrees, as estimated from its octanol-water partitioning coefficient, was found to be sufficient to support MeHg production by cells. The present paper expands on our previous work by providing experimental support of our hypothesis that sulfide influences methylation by affecting the speciation of dissolved HgI and its uptake via passive diffusion.

We have previously hypothesized that sulfide inhibits Hg methylation by decreasing its bioavailability to sulfate-reducing bacteria (SRB), the important methylators of Hg in natural sediments. With a view to designing a bioassay to test this hypothesis, we investigated a number of aspects of Hg methylation by the SRB Desulfobulbus propionicus, including (i) the relationship between cell density and methylmercury (MeHg) production, (ii) the time course of Hg methylation relative to growth stage, (iii) changes in the bioavailability of an added inorganic Hg (Hg(I)) spike over time, and (iv) the dependence of methylation on the concentration of dissolved Hg(I) present in the culture. We then tested the effect of sulfide on MeHg production by this microorganism. These experiments demonstrated that under conditions of equal bioavailability, per-cell MeHg production was constant through log-phase culture growth. However, the methylation rate of a new Hg spike dramatically decreased after the first 5 h. This result was seen whether methylation rate was expressed as a fraction of the total added Hg or the filtered Hg(I) concentration, which suggests that Hg bioavailability decreased through both changes in Hg complexation and formation of solid phases. At low sulfide concentration, MeHg production was linearly related to the concentration of filtered Hg(I). The methylation of filtered Hg(I) decreased about fourfold as sulfide concentration was increased from 10(-6) to 10(-3) M. This decline is consistent with a decrease in the bioavailability of Hg(I), possibly due to a decline in the dissolved neutral complex, HgS(0).

A survey of size-specific mercury (Hg) concentrations in game fish from a subset of Maryland fresh and estuarine waters was conducted, in which Hg concentrations in 112 fish from seven freshwater impoundments and three tidal and four estuarine locations in Chesapeake Bay and its tributaries were measured. Striped bass (Morone saxatilis) was the most intensively examined species. Of the fish examined, the largest freshwater sportfish contained the highest Hg concentrations. Striped bass and largemouth bass (Micropterus salmoides) from Chesapeake Bay and its tributaries contained less Hg at the same size than the same species in fresh waters. Large striped bass, chain pickerel (Esox niger), and walleye (Stizostedion vitreum) from Deep Creek Lake and Liberty Reservoir exceeded the FDA action level of 1 mg Hg/kg. Striped bass, largemouth bass, and white crappie (Pomoxis annularis) in other impoundments equaled or exceeded a common advisory level of 0.5 mg Hg/kg. Large differences in size-normalized Hg concentrations among lakes and particularly between fresh and salt waters highlight the large differences in MeHg production and bioaccumulation among ecosystems. This work indicates that a more comprehensive study of Hg in Maryland fish is warranted to protect human and wildlife health.

Microbial communities in water from Baltimore Harbor and from the mainstem of Chesapeake Bay were examined for sensitivity to mercuric chloride, monomethyl mercury, stannic chloride, and tributyltin chloride. Acute toxicity was determined by measuring the effects of [3H]thymidine incorporation, [14C]glutamate incorporation and respiration, and viability as compared with those of controls. Minimum inhibitory concentrations were low for all metals (monomethyl mercury, less than 0.05 microgram liter-1; mercuric chloride, less than 1 microgram liter-1; tributyltin chloride, less than 5 micrograms liter-1) except stannic chloride (5 mg liter-1). In some cases, mercuric chloride and monomethyl mercury were equally toxic at comparable concentrations. The Chesapeake Bay community appeared to be slightly more sensitive to metal stress than the Baltimore Harbor community, but this was not true for all treatments or assays. For culturable bacteria the opposite result was found. Thymidine incorporation and glutamate metabolism were much more sensitive indicators of metal toxicity than was viability. To our knowledge, this is the first use of the thymidine incorporation method for ecotoxicology studies. We found it the easiest and fastest of the three methods; it is at least equal in sensitivity to metabolic measurements, and it likely measures the effects on greater portion of the natural community.

The octanol-water partioning of inorganic mercury decreased with increasing sulfide, supporting a model that predicts decreased fractionsof neutral Hg-S species with increasing sulfide. These results help explain the decreased availability of Hg to methylating bacteria under sulfidic conditions, and the inverse relationship between sulfide and methylmercury observed in sediments. [ABSTRACT FROM AUTHOR]

Methylmercury (MeHg) concentrations and production rates were examined along with sulfur biogeochemistry in Everglades sediments in March, July and December, 1995, as part of a large, multi-investigator study, the Aquatic Cycling of Mercury in the Everglades (ACME) project. The sites examined constitute a trophic gradient, generated from agricultural runoff, across the Everglades Nutrient Removal (ENR) Area, which is a re-constructed wetland, and Water Conservation Areas (WCA) 2A, 2B and 3 in the northern Everglades. MeHg concentrations and %MeHg (MeHg as a percent of total Hg) were lowest in the more eutrophic areas and highest in the more pristine areas in the south. MeHg concentrations ranged from <0.1 ng gdw-1 sediment in the ENR to 5 ng gdw-1 in WCA3 sediments; and MeHg constituted <0.2% of total Hg (HgT) in ENR, but up to about 2% in two sites in WCA2B and WCA3. Methylation rates in surficial sediments, estimatedusing tracer-level injections of 203Hg (II) sediment cores, ranged from 0 to 0.12 d-1, or about 1 to 10 ng g-1 d-1 when the per day values are multiplied by the ambient total Hg concentration. Methylation was generally maximal at or within centimeters of the sediment surface, and was never observed in water overlying cores. The spatial pattern of MeHg production generally matched that of MeHg concentration. The coincident distributions of MeHg and its production suggest that in situ production controlsconcentration, and that MeHg concentration can be used as an analog for MeHg production. In addition, the spatial pattern of MeHg in Everglades sediments matches that in biota. suggesting that MeHg bioaccumulation may be predominantly a function of the de novo methylation rate in surficial sediments. Sulfate concentrations in surficial pore waters (up to 400 mu m), microbial sulfate-reduction rates (up to 800 nm cc-1 d-1) and resultant pore water sulfide con [ABSTRACT FROM AUTHOR]

An overview of a comprehensive study of the behavior and fate of mercury in the estuarine Patuxent River is presented. Total Hg (HgT) and methylmercury (MeHg) exhibited weakly non-conservative behavior in the estuary. Total Hg concentrations ranged from 6 ng L-1 in the upper reaches of the sub-urbanized tidal freshwater river to <0.5 ng L-1 in the mesohaline lower estuary. Filterable (0.2 mu m) HgT ranged from 0.2 to 1.5 ng L-1. On average, MeHg accounted for <5% of unfiltered HgTand <2% of filterable HgT. Dissolved gaseous Hg (DGHg) concentrations were highest (up to 150 pg L- 1) in the summer in the mesohaline section, but were not well correlated with primary production or chlorophyll a, demonstrating the complex nature of Hg0 formation and cycling in an estuarine environment. Organic matter content appeared to control the HgT content of sediments, while MeHg in sediments was positively correlated with HgT and organic matter, and negatively correlated with sulfide. MeHg in sediments was low (0.1 to 0.5% of HgT). Preliminary findings suggest that net MeHg production within sediments exceeds net accumulation. Although HgT in pore waters increased with increasing sulfide, bulk MeHg concentrations decreased. The concentration of MeHg in sediments was not related to the concentration of HgT in pore waters. These observations support the hypothesis that sulfide affects the speciation and therefore bioavailability of dissolved and/or solid-phase Hg for methylation. Comparison with other ecosystems, and the negative correlation between pore water sulfide and sediment MeHg, suggest that sulfide limits production and accumulation of MeHg in this system. [ABSTRACT FROM AUTHOR]