MeHg Production Research Articles

Water level fluctuations influence microbial communities and mercury methylation in soils in the Three Gorges Reservoir, China

Reservoirs tend to have enhanced methylmercury (MeHg) concentrations compared to natural lakes and rivers, and water level fluctuations can promote MeHg production. Until now, little research has been conducted on the effects of microorganisms in soils for the formation of MeHg during different drying and flooding alternating conditions in the Three Gorges Reservoir (TGR). This study aimed to understand how water level fluctuations affect soil microbial composition and mercury concentrations, and if such microbial variations are related to Hg methylation. The results showed that MeHg concentrations and the ratios of MeHg to THg (MeHg%) in soils were higher in the seasonally drying and flooding alternating areas (DFAs, 175–155m) than those in the non-inundated (NIAs, >175m) and inundated areas (IAs, <145m). However, MeHg% in all samples was less than 1%, indicating that the Hg methylation activity in the soils of the TGR was under a low level. 454 high-throughput sequencing of 16S rRNA gene amplicons showed that soil bacterial abundance and diversity were relatively higher in DFA compared to those in NIA and IA, and microbial community composition varied in these three areas. At the family level, those groups in Deltaproteobacteria and Methanomicrobia that might have many Hg methylators were also showed a higher relative abundance in DFA, which might be the reason for the higher MeHg production in these areas. Overall, our results suggested that seasonally water level fluctuations can enhance the microbial abundance and diversity, as well as MeHg production in the TGR.

Seasonal changes in peryphytic microbial metabolism determining mercury methylation in a tropical wetland

Mercury (Hg) methylation, a key process in the biogeochemical cycle of Hg, is mainly attributed to sulfate-reducing bacteria and methanogenic Archaea. However, environmental regulation by these groups has not yet been ascertained in tropical environments, especially in respect to the seasonal flood flooding. This work evaluated the variation of net methylmercury production potential in relation to biological characteristics of the periphyton, environmental factors, and flood pulse seasons. Our results indicate that there is a seasonal change between metabolic groups as main Hg methylators, sulfate-reducing bacteria in the dry season and methanogenic Archaea in the flood season. In addition, there was a positive relationship between dissolved organic carbon (DOC), phosphorus, cyanobacteria biovolume, and periphytic Hg methylation potential. These results shed a new light on MeHg production plasticity, mediated by landscape and flood pulses in tropical wetlands, as well as on ecological relationships within the periphyton.

Carbon Amendments Alter Microbial Community Structure and Net Mercury Methylation Potential in Sediments.

ABSTRACTNeurotoxic methylmercury (MeHg) is produced by anaerobic Bacteria and Archaea possessing the genes hgcAB, but it is unknown how organic substrate and electron acceptor availability impacts the distribution and abundance of these organisms. We evaluated the impact of organic substrate amendments on mercury (Hg) methylation rates, microbial community structure, and the distribution of hgcAB+ microbes with sediments. Sediment slurries were amended with short-chain fatty acids, alcohols, or a polysaccharide. Minimal increases in MeHg were observed following lactate, ethanol, and methanol amendments, while a significant decrease (∼70%) was observed with cellobiose incubations. Postincubation, microbial diversity was assessed via 16S rRNA amplicon sequencing. The presence of hgcAB+ organisms was assessed with a broad-range degenerate PCR primer set for both genes, while the presence of microbes in each of the three dominant clades of methylators (Deltaproteobacteria, Firmicutes, and methanogenic Archaea) was measured with clade-specific degenerate hgcA quantitative PCR (qPCR) primer sets. The predominant microorganisms in unamended sediments consisted of Proteobacteria, Firmicutes, Bacteroidetes, and Actinobacteria. Clade-specific qPCR identified hgcA+ Deltaproteobacteria and Archaea in all sites but failed to detect hgcA+ Firmicutes. Cellobiose shifted the communities in all samples to ∼90% non-hgcAB-containing Firmicutes (mainly Bacillus spp. and Clostridium spp.). These results suggest that either expression of hgcAB is downregulated or, more likely given the lack of 16S rRNA gene presence after cellobiose incubation, Hg-methylating organisms are largely outcompeted by cellobiose degraders or degradation products of cellobiose. These results represent a step toward understanding and exploring simple methodologies for controlling MeHg production in the environment.IMPORTANCE Methylmercury (MeHg) is a neurotoxin produced by microorganisms that bioacummulates in the food web and poses a serious health risk to humans. Currently, the impact that organic substrate or electron acceptor availability has on the mercury (Hg)-methylating microorganisms is unclear. To study this, we set up microcosm experiments exposed to different organic substrates and electron acceptors and assayed for Hg methylation rates, for microbial community structure, and for distribution of Hg methylators. The sediment and groundwater was collected from East Fork Poplar Creek in Oak Ridge, TN. Amendment with cellobiose (a lignocellulosic degradation by-product) led to a drastic decrease in the Hg methylation rate compared to that in an unamended control, with an associated shift in the microbial community to mostly nonmethylating Firmicutes. This, along with previous Hg-methylating microorganism identification methods, will be important for identifying strategies to control MeHg production and inform future remediation strategies.

Methylmercury production in soil in the water-level-fluctuating zone of the Three Gorges Reservoir, China: The key role of low-molecular-weight organic acids.

As important parts of dissolved organic matter, low-molecular-weight organic acids (LMWOAs) typically play important roles in desorbing Hg(II) from the soil solid-phase, which may directly or indirectly impact methylmercury (MeHg) production. However, the mechanism of these processes remains unclear. To better understand the effects of LMWOAs on Hg methylation in the soil, a field study was conducted to investigate the distribution of LMWOAs and their relationship with soil MeHg in a seasonally inundated area in the Three Gorges Reservoir (TGR), China. Meanwhile, laboratory simulation experiments were performed to determine the potential mechanism of LMWOAs in Hg methylation. The field investigation detected considerable amounts of LMWOAs in soil, among which tartaric acid and oxalic acid were dominant components. Among which, tartaric acid and oxalic acid were dominant components. Also, a seasonally and spatially heterogeneous distribution of LMWOAs in soil was observed. Notably, a significant positive relationship was found between MeHg concentrations and LMWOA pools in soil (r = 0.969, p < .01), implying that LMWOAs could promote soil MeHg production. The simulation experiments confirmed that the MeHg levels in soil were largely elevated with the addition of LMWOAs, which occurred mainly in oxygen-deficient environment and was mediated by biotic factors. The soluble Hg-LMWOA complexes, which were formed by the enhanced desorption of Hg(II) from solid-phase, were mostly responsible for the elevated MeHg production in soil. Moreover, those LMWOAs with more carboxylic groups were believed to enhance the net production of MeHg. The generated MeHg in sediment could diffuse into the overlying water, which thus poses a potential threat to the aquatic food web. Therefore, the enhanced Hg methylation caused by LMWOAs should be given more attention, especially in a seasonally inundated ecosystem, where the MeHg exposure is usually related to fishery activities.

Comparison of mercury and methylmercury bioaccumulation in earthworms (Bimastus parvus) native to landfill-leachate-contaminated forest soil.

Total mercury (THg) and methylmercury (MeHg) bioaccumulation was explored in the Bimastus parvus species of earthworm (B. parvus) native to the leachate-contaminated forest soils around a Hg-polluted traditional landfill in Japan. General soil properties and concentrations of THg and MeHg in forest soils and in B. parvus were determined. The results indicated that the average THg concentrations in B. parvus and in forest soils in the leachate-contaminated sites were 10.21 and 14.90 times higher than those in the reference sites, respectively, whereas similar average MeHg concentrations were observed in forest soils (< 0.01 mg kg-1) and in B. parvus (0.100-0.114 mg kg-1) across all sampled sites. The average bioaccumulation factors of THg in B. parvus (BAFTHg) in forest soil were similar between the leachate-contaminated sites and the reference sites. Cluster and regression analyses demonstrated that the B. parvus Hg (THg and MeHg) and soil THg were positively correlated with each other and with soil organic matter (SOM) and clays, but were negatively correlated with sand and hardly correlated with silts and pH in leachate-contaminated forest soils. From these results, it was proposed that Hg exposure to food chains is possible through B. parvus, because B. parvus showed a high ability to accumulate THg and MeHg in both leachate-contaminated and reference forest soils. Together, these findings indicated that the role of B. parvus in MeHg production is not clear, and it is possible that the MeHg in B. parvus was firstly formed within forest soils and then accumulated in their tissues.

Water Column Distribution of Mercury Species in Permanently Stratified Aqueous Environments

Biogeochemical structures of three permanently stratified waterbodies were studied: a sea water basin (the Black Sea), an estuary (Hunnbunn fjord), and a freshwater lake (Nordbytjernet), with focus on the distributions of methylmercury (MeHg) and total mercury (THg). THg concentrations were similar in the sea water basin (0.2–1.8 ng/L) and the freshwater lake (0.8–1.2 ng/L), but significantly higher in the estuary (0.6–9.4 ng/L). An increase in the MeHg concentration and MeHg/THg ratio were found in the redox zone in all three basins, indicating bacterial production of MeHg in the aqueous phase. In the lake and estuary, the maximum MeHg concentration and MeHg/THg ratio were found in samples located closest to the bottom sediments, likely due to the formation of MeHg in surface sediments and subsequent diffusion to the overlying waters.

Mercury methylation in stormwater retention ponds at different stages in the management lifecycle.

Stormwater retention ponds effectively manage erosion, flooding, and pollutant loadings, but are also sources of methylmercury (MeHg), a bioaccumulative neurotoxin which is produced by anaerobic aquatic microorganisms. Stormwater retention ponds have a 10-15 year working life, after which they are dredged and reflooded. In this study, we related MeHg biogeochemistry to the different stages of the management lifecycle. In a new, a dredged, and a mature stormwater retention pond, we measured MeHg and inorganic mercury (IHg) concentrations, and the potential for MeHg formation (Kmeth), during the early summer, peak summer, and fall of 2013. In our study sites, MeHg concentrations appear to be driven by mercury (Hg) methylation, indicated by significant correlations between Kmeth values and MeHg concentrations and the percent of Hg present as MeHg. Relationships between Hg variables and ancillary biogeochemistry suggest that Hg methylation is carried out by sulfate reducing bacteria, but that the process is modulated by the supply of IHg substrate, sediment total and labile organic carbon, and possibly competition with nitrate reducers. Wetlands at different points in the management lifecycle differ in terms of their MeHg biogeochemistry. The organic matter-poor new wetland had low MeHg production (mean Kmeth 0.014 per day) and sediment concentrations (mean 0.015 ng g-1), while the mature wetland both produced and accumulated MeHg about five times more actively. Methylmercury production capacity was only temporarily reduced in the reflooded sediments of the dredged wetland, which experienced rapid increases in Kmeth values from low (mean 0.015 per day) immediately after dredging, to values similar to those in the mature wetland after five months. This pattern may have been related to recolonization of the sediments with mercury methylators or increased microbial activities in response to the addition of fresh organic matter. Additional studies should focus on the applicability of these patterns to stormwater retention ponds in other areas, and particularly investigate the effects of stormwater pond dredging on their microbial ecology and MeHg biogeochemistry.

Sources of Methylmercury to Snowpacks of the Alberta Oil Sands Region: A Study of In Situ Methylation and Particulates.

Snowpacks in the Alberta Oil Sands Region (AOSR) of Canada contain elevated loadings of methylmercury (MeHg; a neurotoxin that biomagnifies through foodwebs) due to oil sands related activities. At sites ranging from 0 to 134 km from the major AOSR upgrading facilities, we examined sources of MeHg by quantifying potential rates of MeHg production in snowpacks and melted snow using mercury stable isotope tracer experiments, as well as quantifying concentrations of MeHg on particles in snowpacks (pMeHg). At four sites, methylation rate constants were low in snowpacks (km = 0.001-0.004 d-1) and nondetectable in melted snow, except at one site (km = 0.0007 d-1). The ratio of methylation to demethylation varied between 0.3 and 1.5, suggesting that the two processes are in balance and that in situ production is unlikely an important net source of MeHg to AOSR snowpacks. pMeHg concentrations increased linearly with distance from the upgraders (R2 = 0.71, p < 0.0001); however, snowpack total particle and pMeHg loadings decreased exponentially over this same distance (R2 = 0.49, p = 0.0002; R2 = 0.56, p < 0.0001). Thus, at near-field sites, total MeHg loadings in snowpacks were high due to high particle loadings, even though particles originating from industrial activities were not MeHg rich compared to those at remote sites. More research is required to identify the industrial sources of snowpack particles in the AOSR.

Methylmercury and methane production potentials in North Carolina Piedmont stream sediments

Methylated mercury (MeHg) can be produced by all microbes possessing the genes hgcA and hgcB, which can include sulfate-reducing bacteria (SRB), iron-reducing bacteria (FeRB), methane-producing archaea (MPA), and other anaerobic microbes. These microbial groups compete for substrates, including hydrogen and acetate. When sulfate is in excess, SRB can outcompete other anaerobic microbes. However, low concentrations of sulfate, which often occur in stream sediments, are thought to reduce the relative importance of SRB. Although SRB are regarded as the primary contributors of MeHg in many aquatic environments, their significance may not be universal, and stream sediments are poorly studied with respect to microbial Hg methylation. We evaluated suppression of methanogenesis by SRB and the potential contributions from SRB, MPA and other MeHg producing microbes (including FeRB) to the production of MeHg in stream sediments from the North Carolina Piedmont region. Lower methanogenesis rates were observed when SRB were not inhibited, however, application of a sulfate-reduction inhibitor stimulated methanogenesis. Greater MeHg production occurred when SRB were active. Other MeHg producing microbes (i.e., FeRB) contributed significantly less MeHg production than SRB. MPA produced MeHg in negligible amounts. Our results suggest that SRB are responsible for the majority of MeHg production and suppress methanogenesis in mid-order stream sediments, similar to other freshwater sediments. Further investigation is needed to evaluate the generality of these findings to streams in other regions, and to determine the mechanisms regulating sulfate and electron acceptor availability and other potential factors governing Hg methylation and methane production in stream sediments.

Biochar and nitrate reduce risk of methylmercury in soils under straw amendment

There is growing evidence that incorporating crop straw into soils, which is being widely encouraged in many parts of the world, could increase net methylmercury (MeHg) production in soils and MeHg accumulation in crops. We explored the possibility of mitigating the risk of increased MeHg levels under straw amendment by transforming straw into biochar (BC). Greenhouse and batch experiments were conducted, in which soil MeHg concentrations, MeHg phytoavailability and accumulation in rice, dynamics of sulfate, nitrate and abundances of sulfate reducing bacteria (SRB) were compared in ‘Control’ (Hg contaminated soil), ‘Straw’ (soil with 1% rice straw), ‘Straw+BC’ (soil with 1% straw and 1% biochar), and ‘Straw+BC+N’ (soil with 1% straw, 1% biochar and 0.12% nitrate). Our results indicate that straw amendment increased MeHg concentrations in soils (28–136% higher) and rice plants (26% higher in grains, ‘Straw’ versus ‘Control’), while co-application of biochar with straw reduced grain MeHg levels (60% lower, ‘Straw+BC’ versus ‘Straw’). This could be mainly attributed to the reduced MeHg availability to rice plants (phytoavailability, extraction rates of MeHg by ammonium thiosulfate) under biochar amendment (64–99% lower, ‘Straw+BC’ versus ‘Straw’). However, biochar amendment enhanced soil MeHg levels (5–75% higher, ‘Straw+BC’ versus ‘Control’). Interestingly, nitrate addition helped reduce soil MeHg concentrations (11–41% lower, ‘Straw+BC+N’ versus ‘Straw+BC’) by facilitating nitrate reduction while inhibiting SRB activities. Subsequently, addition of nitrate with biochar, compared with biochar alone, further reduced grain MeHg levels by 34%. Therefore, straw biochar together with nitrate could possibly be effective in mitigating the risk of MeHg under straw amendment. Furthermore, the results evidence the impacts of straw management on the risk posed by MeHg in soils and emphasize the necessity to carefully consider the straw management policy in Hg-contaminated areas.

Accumulation of Methylmercury in Invertebrates and Masked Shrews (Sorex cinereus) at an Upland Forest-Peatland Interface in Northern Minnesota, USA.

Mercury (Hg) methylation is often elevated at the terrestrial-peatland interface, but methylmercury (MeHg) production at this "hot spot" has not been linked with in situ biotic accumulation. We examined total Hg and MeHg levels in peat, invertebrates and tissues of the insectivore Sorex cinereus (masked shrew), inhabiting a terrestrial-peatland ecotone in northern Minnesota, USA. Mean MeHg concentrations in S. cinereus (71ngg-1) fell between concentrations measured in spiders (mean 70-140ngg-1), and ground beetles and millipedes (mean 29-42ngg-1). Methylmercury concentrations in S. cinereus increased with age and differed among tissues, with highest concentrations in kidneys and muscle, followed by liver and brain. Nearly all Hg in S. cinereus was in the methylated form. Overall, the high proportional accumulation of MeHg in peat at the site (3.5% total Hg as MeHg) did not lead to particularly elevated concentrations in invertebrates or shrews, which are below values considered a toxicological risk.

The effects of aquaculture on mercury distribution, changing speciation, and bioaccumulation in a reservoir ecosystem.

A survey was conducted in a freshwater reservoir located in Guizhou province, south China, to investigate the influence of fish aquaculture activities on mercury (Hg) distribution, speciation change, and bioaccumulation. Water, sediment, and aquaculture fish samples were collected from aquaculture sites (AS) and the corresponding reference sites (RS). The results showed that total mercury (THg) concentration in overlying water in Wujiangdu reservoir reached 6.87±14.9ngL-1. THg concentration in a different layer follows the sequence: surface layer > bottom layer > three intermediate layers with significant difference. In addition, the total methylmercury (TMeHg) concentration in overlying water was 0.113±0.211ngL-1. The highest TMeHg was observed in the bottom layer. Both dissolved Hg (DHg) and dissolved methylmercury (DMeHg) accounted for more than 50% of THg and TMeHg in the top four layers of overlying water, respectively. In contrast, particulate Hg (PHg) and particulate methylmercury were the major portion of THg and TMeHg in bottom layer and reached to 67 and 58.7% of THg and TMeHg, respectively. Aquaculture activities were estimated to contribute an annual loading of approximately 69.8ngg-1of THg yearly in the top 1cm of sediment underneath the rafts due to unconsumed fish feed. The extra loading of THg in sediment may have potential to stimulate the release of Hg to the overlying water. Both DMeHg and DHg in sediment pore water and organic matter (OM) contents in the top 4cm of AS were noticeably higher than RS, which indicated that the accumulation of OM due to aquaculture activities promoted MeHg production in the top surface of sediment pore water. No significant difference was noted between THg in RS (296±104ngg-1) and AS (274±132ngg-1) in the solid phase. In addition, the sediments were net sources of both MeHg and inorganic Hg. For Hg in fish tissues, THg and inorganic Hg (IHg) in the liver were significantly higher (THg: p<0.001, F=9.98; IHg: p<0.001, F=13.1) than those in the other organs. In contrast, MeHg concentration in the muscle was significantly higher than (p<0.01, F=4.83) that in the other organs.

The influence of permanently submerged macrophytes on sediment mercury distribution, mobility and methylation potential in a brackish Norwegian fjord

Macrophytes are shown to affect the microbial activity in different aqueous environments, with an altering of the sediment cycling of mercury (Hg) as a potential effect. Here, we investigated how a meadow with permanently submerged macrophytes in a contaminated brackish fjord in southern Norway influenced the conditions for sulfate reducing microbial activity, the methyl-Hg (MeHg) production and the availability of MeHg. Historically discharged Hg from a chlor-alkali plant (60–80tons, 1947–1987) was evident through high Hg concentrations (491mgTot-Hgkg−1, 268μgMeHgkg−1) in intermediate sediment depths (10–20cm) outside of the meadow, with reduced concentrations within the meadow. Natural recovery of the fjord was revealed by lower sediment surface concentrations (1.9–15.5mgTot-Hgkg−1, 1.3–3.2μgMeHgkg−1). Within the meadow, vertical gradients of sediment hydrogen sulfide (H2S) Eh and pH suggested microbial sulfate reduction in 2–5cm depths, coinciding with peak values of relative MeHg levels (0.5% MeHg). We assume that MeHg production rates was stimulated by the supply and availability of organic carbon, microbial activity and a sulfide oxidizing agent (e.g. O2) within the rhizosphere. Following this, % MeHg in sediment (0–5cm) within the meadow was approximately 10× higher compared to outside the meadow. Further, enhanced availability of MeHg within the meadow was demonstrated by significantly higher fluxes (p<0.01) from sediment to overlying water (0.1–0.6ngm−2d−1) compared to sediment without macrophytes (0.02–0.2ngm−2d−1). Considering the productivity and species richness typical for such habitats, submerged macrophyte meadows located within legacy Hg contaminated sediment sites may constitute important entry points for MeHg into food webs.

Sulfurization of Dissolved Organic Matter Increases Hg-Sulfide-Dissolved Organic Matter Bioavailability to a Hg-Methylating Bacterium.

Reactions of dissolved organic matter (DOM) with aqueous sulfide (termed sulfurization) in anoxic environments can substantially increase DOM's reduced sulfur functional group content. Sulfurization may affect DOM-trace metal interactions, including complexation and metal-containing particle precipitation, aggregation, and dissolution. Using a diverse suite of DOM samples, we found that susceptibility to additional sulfur incorporation via reaction with aqueous sulfide increased with increasing DOM aromatic-, carbonyl-, and carboxyl-C content. The role of DOM sulfurization in enhancing Hg bioavailability for microbial methylation was evaluated under conditions typical of Hg methylation environments (μM sulfide concentrations and low Hg-to-DOM molar ratios). Under the conditions of predicted metacinnabar supersaturation, microbial Hg methylation increased with increasing DOM sulfurization, likely reflecting either effective inhibition of metacinnabar growth and aggregation or the formation of Hg(II)-DOM thiol complexes with high bioavailability. Remarkably, Hg methylation efficiencies with the most sulfurized DOM samples were similar (>85% of total Hg methylated) to that observed in the presence of l-cysteine, a ligand facilitating rapid Hg(II) biouptake and methylation. This suggests that complexes of Hg(II) with DOM thiols have similar bioavailability to Hg(II) complexes with low-molecular-weight thiols. Overall, our results are a demonstration of the importance of DOM sulfurization to trace metal and metalloid (especially mercury) fate in the environment. DOM sulfurization likely represents another link between anthropogenic sulfate enrichment and MeHg production in the environment.

Bacterial periphytic communities related to mercury methylation within aquatic plant roots from a temperate freshwater lake (South-Western France).

Macrophyte floating roots are considered as hotspots for methylmercury (MeHg) production in aquatic ecosystems through microbial activity. Nevertheless, very little is known about periphyton bacterial communities and mercury (Hg) methylators in such ecological niches. The ability to methylate inorganic Hg is broadly distributed among prokaryotes; however, sulfate-reducers have been reported to be the most important MeHg producers in macrophyte floating roots. In the present work, the periphyton bacterial communities colonizing Ludwigia sp. floating roots were investigated through molecular methods. Among the 244 clones investigated, anaerobic microorganisms associated with the sulfur biogeochemical cycle were identified. Notably, members of the sulfur-oxidizing prokaryotes and the anoxygenic, purple non-sulfur bacteria (Rhodobacteraceae, Comamonadaceae, Rhodocyclaceae, Hyphomicrobiaceae) and the sulfate reducers (Desulfobacteraceae, Syntrophobacteraceae, and Desulfobulbaceae) were detected. In addition, 15 sulfate-reducing strains related to the Desulfovibrionaceae family were isolated and their Hg-methylation capacity was tested using a biosensor. The overall results confirmed that Hg methylation is a strain-specific process since the four strains identified as new Hg-methylators were closely related to non-methylating isolates. This study highlights the potential involvement of periphytic bacteria in Hg methylation when favorable environmental conditions are present in such ecological micro-niches.

Organic matter drives high interannual variability in methylmercury concentrations in a subarctic coastal sea

Levels of neurotoxic methylmercury (MeHg) in phytoplankton are strongly associated with water MeHg concentrations. Because uptake by phytoplankton is the first and largest step of bioaccumulation in aquatic food webs many studies have investigated factors driving seasonal changes in water MeHg concentrations. Organic matter (OM) is widely accepted as an important driver of MeHg production and uptake by phytoplankton but is also known for strong interannual variability in concentration and composition within systems. In this study, we explore the role of OM on spatial and interannual variability of MeHg in a subarctic coastal sea, the northern Baltic Sea. Using MeHg (2014: 80 ± 25 fM; 2015: <LOD; 2016: 21 ± 9 fM) and OM measurements during late summer/early fall, we find that dissolved organic carbon (DOC) and humic matter content explain 60% of MeHg variability. We find that while labile DOC increases MeHg levels in the water, humic content reduces it. We propose that the positive association between MeHg and labile DOC shows that labile DOC is a proxy for OM remineralization rate in nearshore and offshore waters. This is consistent with other studies finding that in situ MeHg production in the water column occurs during OM remineralization. The negative association between water humic content and MeHg concentration is most likely due to humic matter decreasing inorganic mercury (HgII) bioavailability to methylating microbes. With these relationships, we develop a statistical model and use it to calculate MeHg concentrations in late summer nearshore and offshore waters between 2006 and 2016 using measured values for water DOC and humic matter content. We find that MeHg concentrations can vary by up to an order of magnitude between years, highlighting the importance of considering interannual variability in water column MeHg concentrations when interpreting both short and long term MeHg trends in biota.

The impact of an abandoned mercury mine on the environment in the Xiushan region, Chongqing, southwestern China

Mercury contamination is a serious problem in the Hg mining area of Xiushan County, Chongqing, southwestern China. The concentrations of total mercury (THg) and methylmercury (MeHg) in paddy soil, surface water, and rice (grain) samples were determined to investigate the regional distribution of Hg contamination. Simultaneously, gaseous elemental Hg (GEM) in ambient air near the sampling sites was measured. The total Hg concentrations in surface water were highly elevated, ranging from 13 to 2390 ng/L, and the total MeHg concentrations varied between 0.17 and 1.1 ng/L. The dissolved Hg and MeHg concentrations in surface water ranged from 4.7 to 470 ng/L and 0.14–0.35 ng/L, respectively. High THg and MeHg concentrations were also obtained in paddy soils from mining areas, ranging from 0.45 to 68 μg/g and 0.13–4.8 ng/g, respectively. Similar to the high concentrations in water and soil, the THg concentration in rice (grain) ranged from 4.7 to 550 ng/g and MeHg from 2.9 to 26 ng/g. Elevated Hg concentrations in rice, as a staple food of local residents, confirmed that rice consumption could be a vital pathway for MeHg exposure to native people. Humic acid and fulvic acid had significant correlations with soil MeHg, implying that they have important roles that influence MeHg production in soil. The spatial distribution characteristics of Hg and MeHg pollution in the local environment indicated their origins from historic Hg mining sites in the Xiushan area.

Vertical distribution of mercury and MeHg in Nandagang and Beidagang wetlands: Influence of microtopography

Wetlands often show different small-scale topography, such as riffle, habitat island, deep water, shallow water zone and dry zone. Core soils in different micro topographical landforms of Nandagang and Beidagang wetlands in North China were sampled for THg and MeHg to analyze the influence of microtopography. Results showed that THg content in surface soil (<2 cm) was little higher than that at depth 2–4 cm of all stations. There were several peaks in the profile, which reflected mercury pollution in past. High THg content in undisturbed natural wetland soil implied accumulation of mercury. Harvest of plant, drained water decreased the accumulation of mercury in wetlands. Water level caused by microtopography affected the production of MeHg. Depth of the highest MeHg content decreased from N1, N2, N6, N3 to N4 following the increase of water level. Plant type and coverage also affected the vertical distribution of MeHg. More detailed profiles of MeHg, organic matter and total phosphorus in different sites show strong differences in soil chemistry, suggesting a complex interplay among hydrology, biogeochemistry and microtopography.

Methylmercury Bioaccumulation in an Urban Estuary: Delaware River, USA

Spatial variation in mercury (Hg) and methylmercury (MeHg) bioaccumulation in urban coastal watersheds reflects complex interactions between Hg sources, land use, and environmental gradients. We examined MeHg concentrations in fauna from the Delaware River estuary, and related these measurements to environmental parameters and human impacts on the waterway. The sampling sites followed a north to south gradient of increasing salinity, decreasing urban influence, and increasing marsh cover. Although mean total Hg in surface sediments (top 4cm) peaked in the urban estuarine turbidity maximum and generally decreased downstream, surface sediment MeHg concentrations showed no spatial patterns consistent with the examined environmental gradients, indicating urban influence on Hg loading to the sediment but not subsequent methylation. Surface water particulate MeHg concentration showed a positive correlation with marsh cover whereas dissolved MeHg concentrations were slightly elevated in the estuarine turbidity maximum region. Spatial patterns of MeHg bioaccumulation in resident fauna varied across taxa. Small fish showed increased MeHg concentrations in the more urban/industrial sites upstream, with concentrations generally decreasing farther downstream. Invertebrates either showed no clear spatial patterns in MeHg concentrations (blue crabs, fiddler crabs) or increasing concentrations further downstream (grass shrimp). Best-supported linear mixed models relating tissue concentration to environmental variables reflected these complex patterns, with species specific model results dominated by random site effects with a combination of particulate MeHg and landscape variables influencing bioaccumulation in some species. The data strengthen accumulating evidence that bioaccumulation in estuaries can be decoupled from sediment MeHg concentration, and that drivers of MeHg production and fate may vary within a small region.

Role of Organic Carbon Sources and Sulfate in Controlling Net Methylmercury Production in Riverbank Sediments of the South River, VA (USA)

ABSTRACTMercury (Hg) transport and methylmercury (MeHg) production in riverbank sediments are complex processes influenced by site-specific physical and biogeochemical conditions. The South River watershed in VA, USA, contains elevated concentrations of Hg in riverbank and floodplain sediments, which has the potential to methylate. The role of specific organic carbon sources in promoting methylation reactions in natural sediments under dynamic flow conditions is not well understood. Four saturated column experiments were conducted, including a control column, which received South River water as an influent solution, and three columns that received South River water amended with: acetate (5.8 mM); lactate (5.7 mM); and lactate (5.7 mM) with SO42− (10.1 mM). The amendments were selected to promote growth of different microorganisms to gain an understanding of the microbial processes, controlling rates of methylation. The column receiving lactate and SO42− had the highest MeHg concentrations in the effluent and in the pore water near the effluent at 1.8 and 4.9 μg L−1, respectively. At the cessation of the column experiments, the lactate–sulfate column sediments contained the highest populations of enumerable sulfur-reducing bacteria and the highest solid-phase MeHg at 530 ± 100 ng g−1 dry wt. from the interval closest to the influent. The results suggest that the form and availability of electron donors and acceptors are primary factors controlling rates of methylation in the South River sediment.