Experimental evidence for recovery of mercury-contaminated fish populations.

Anthropogenic releases of mercury (Hg)1-3 are a human health issue4 because the potent toxicant methylmercury (MeHg), formed primarily by microbial methylation of inorganic Hg in aquatic ecosystems, bioaccumulates to high concentrations in fish consumed by humans5,6. Predicting the efficacy of Hg pollution controls on fish MeHg concentrations is complex because many factors influence the production and bioaccumulation of MeHg7-9. Here we conducted a 15-year whole-ecosystem, single-factor experiment to determine the magnitude and timing of reductions in fish MeHg concentrations following reductions in Hg additions to a boreal lake and its watershed. During the seven-year addition phase, we applied enriched Hg isotopes to increase local Hg wet deposition rates fivefold. The Hg isotopes became increasingly incorporated into the food web as MeHg, predominantly from additions to the lake because most of those in the watershed remained there. Thereafter, isotopic additions were stopped, resulting in an approximately 100% reduction in Hg loading to the lake. The concentration of labelled MeHg quickly decreased by up to 91% in lower trophic level organisms, initiating rapid decreases of 38-76% of MeHg concentration in large-bodied fish populations in eight years. Although Hg loading from watersheds may not decline in step with lowering deposition rates, this experiment clearly demonstrates that any reduction in Hg loadings to lakes, whether from direct deposition or runoff, will have immediate benefits to fish consumers.

Mercury Isotope Variations in Lake Sediment Cores in Response to Direct Mercury Emissions from Non-Ferrous Metal Smelters and Legacy Mercury Remobilization.

Nature archives record atmospheric mercury (Hg) depositions from directly emitted Hg and re-emitted legacy Hg. Tracing the legacy versus newly deposited Hg is still, however, challenging. Here, we measured Hg isotope compositions in three dated sediment cores at different distances from the Flin Flon smelter, the largest Canadian Hg sources to the atmosphere during the 1930s-2000s. During the smelter's operative period, Hg isotope compositions showed limited variations in the near-field lake (<10 km) sediments but were rather variable in middle- (20-75 km) and far-field lake (∼800 km) sediments. Only the post-2000 sediments in middle/far-field lakes showed significantly negative Hg isotope shifts, while sediments from the 1970s-1990s had Hg isotope values resembling those of near-field lake post-1930 sediments. We suggest that the smelter's peak Hg emissions during the 1970s-1990s, which coincided with the deployment of a super stack in the mid-1970s, largely increased the long-range dispersion of smelter plumes. For the top post-2000 sediments, the fugitive dust from ore tailings and terrestrial legacy Hg re-emissions dominated Hg deposition in near-field lakes and middle/far-field lakes, respectively. Our study demonstrates that legacy Hg remobilization now exports substantial amounts of Hg to ecosystems, highlighting the need for aggressive remediation measures of Hg-contaminated sites.

Event-Based Atmospheric Precipitation Uncovers Significant Even and Odd Hg Isotope Anomalies Associated with the Circumpolar Vortex.

The determination of the mass-independent fractionation of even Hg isotopes (even-MIF, Δ200Hg) in atmospheric samples adds another intriguing feature to the Hg isotope system. Despite our lack of sufficient experimental verification and the momentary absence of a valid mechanism to explain its occurrence, even-MIF could be instrumental in understanding the cycle and deposition of atmospheric Hg. In contrast to slightly positive Δ200Hg values (<0.30‰) frequently observed in most atmospheric samples, large Δ200Hg values (up to 1.24‰) determined in precipitation from Peterborough (Ontario, Canada) stand out and could provide valuable information for the origin of the even-MIF mystery. We now report a systematic analysis of high-resolution rainfall and snowfall samples collected in winter during cold weather at Peterborough, Canada. Dissolved and particulate Hg both displayed large variations of odd-MIF (from -0.93‰ to 2.02‰ for Δ199Hg), which may result from long-range transportation, as the negative odd-MIF in particulate Hg is likely a result of long-distance transport of arctic atmospheric Hg(II). Dissolved Hg revealed significant even-MIF values (from 0.25‰ to 1.19‰ for Δ200Hg) and a negative relationship between Δ200Hg and Δ204Hg, which provide further evidence for the previously proposed conceptual model of Δ200Hg. Disconnected odd-MIF and even-MIF trends were detected in sequentially collected precipitation samples, which further suggests different sources or mechanisms for Δ199Hg and Δ200Hg. Particularly, the high Δ200Hg values highlight the transport of stratospheric Hg through a polar vortex to the sampling region, stimulating further systematic investigation. The new Δ200Hg data for particulate Hg add to existing information on atmospheric Hg(II) worldwide, suggesting a global distribution of Hg characterized by even-MIF in the atmosphere, and further constrain the model of atmospheric Hg deposition.

Discerning the Sources of Silver Nanoparticle in a Terrestrial Food Chain by Stable Isotope Tracer Technique.

The increasing use of silver-containing nanoparticles (NPs) in commercial products has led to NP accumulation in the environment and potentially in food webs. Identifying the uptake pathways of different chemical species of NPs, such as Ag2S-NP and metallic AgNPs, into plants is important to understanding their entry into food chains. In this study, soybean Glycine max L. was hydroponically exposed to Ag2S-NPs via their roots (10-50 mg L-1) and stable-isotope-enriched 109AgNPs via their leaves [7.9 µg (g fresh weight)-1]. Less than 29% of Ag in treated leaves (in direct contact with 109AgNP) was accumulated from root uptake of Ag2S-NPs, whereas almost all of the Ag in soybean roots and untreated leaves sourced from Ag2S-NPs. Therefore, Ag2S-NPs are phytoavailable and translocate upward. During trophic transfer the Ag isotope signature was preserved, indicating that accumulated Ag in snails most likely originated from Ag2S-NPs. On average, 78% of the Ag in the untreated leaves was assimilated by snails, reinforcing the considerable trophic availability of Ag2S-NPs via root uptake. By highlighting the importance of root uptake of Ag2S-NPs in plant uptake and trophic transfer to herbivores, our study advances current understanding of the biogeochemical fate of Ag-containing NPs in the terrestrial environment.

Increased Methylmercury Accumulation in Rice after Straw Amendment.

Consumption of rice has been shown to be an important route of dietary exposure to methylmercury (MeHg, a neurotoxin) for Asians having a low fish but high rice diet. Therefore, factors that increase MeHg production and bioaccumulation in soil-rice systems, could enhance the risk of MeHg exposure. On the basis of a national-scale survey in China (64 sites in 12 provinces) and rice cultivation experiments, we report that straw amendment, a globally prevalent farming practice, could increase MeHg concentrations in paddy soils (11-1043%) and rice grains (95%). By carrying out a series of batch incubation, seedling uptake and sand culture experiments, we demonstrate that these increases could be attributed to (1) enhanced abundances/activities of microbial methylators and the transformation of refractory HgS to organic matter-complexed Hg, facilitating microbial Hg methylation in soils; (2) enhanced MeHg mobility, and increased root lengths (35-41%) and tip numbers (60-105%), increasing MeHg uptake by rice roots; and (3) enhanced MeHg translocation to rice grains from other tissues. Results of this study emphasize fresh organic matter-enhanced MeHg production and bioaccumulation, and highlight the increased risk of MeHg after straw amendment and thus the need for new policies concerning straw management.

Accumulation of Silver in Yellow Perch ( Perca flavescens) and Northern Pike ( Esox lucius) From a Lake Dosed with Nanosilver.

A total of 15 kg of silver nanoparticles (AgNPs) was added continuously over two ice-free field seasons to a boreal lake (i.e., Lake 222) at the IISD Experimental Lakes Area in Canada. We monitored the accumulation of silver (Ag) in the tissues of yellow perch ( Perca flavescens) and northern pike ( Esox lucius) exposed to the AgNPs under environmentally relevant conditions. The greatest accumulation was observed in the liver tissues of pike, and a single pike sampled in the second year of additions had the highest concentration observed in liver of 5.1 micrograms per gram of wet weight. However, the Ag concentrations in gill and muscle tissue of both pike and perch did not exceed 0.35 micrograms per gram of wet weight. Following additions of AgNP, the Ag residues in fish tissues declined, with a half-life of Ag in pike liver of 119 days. Monitoring using passive sampling devices and single-particle inductively coupled plasma mass spectrometry during the AgNP addition phase confirmed that Ag nanoparticles were present in the water column and that estimated mean concentrations of Ag increased over time to a maximum of 11.5 µg/L. These data indicate that both a forage fish and a piscivorous fish accumulated Ag in a natural lake ecosystem dosed with AgNPs, leading to Ag concentrations in some tissues of the piscivorous species that were 3 orders of magnitude greater than the concentrations in the water.

Two Centuries of Coral Skeletons from the Northern South China Sea Record Mercury Emissions from Modern Chinese Wars.

The contemporary mercury (Hg) cycle in the world's oceans has been greatly affected by human activities. However, we are still lacking reliable, long-term, and continuous records of Hg in seawater. Here, we report for the first time on using annually banded Porites coral skeletons from the northern South China Sea (SCS) as an archive for recording changes of seawater dissolved Hg spanning the past two centuries. We developed a combustion-trapping method to preconcentrate ultratrace Hg concentrations from coral aragonitic skeletons for highly accurate total Hg measurements. Results show that Hg in the coral skeletons ranges from 0.3 to 5.1 pmol/g and is discriminated against Ca during coral skeletal calcification. Preindustrial (1798-1832) Hg levels in coral skeletons were found to be approximately 0.5 pmol/g. The highest Hg concentrations (3-5 pmol/g) were observed during the WWII period (1933-1942). Other distinct Hg maxima (∼3 pmol/g) are observed for the periods 1833-1847, 1858-1862, 1918-1927, 1978-1982, and 1988-1992, with the first four coinciding with contemporary Chinese wars. Our study suggests that the production and use of ammunitions in those wars likely account for the primary Hg emission sources in the northern SCS before 1950, and coral is potentially a robust indicator of historical, regional Hg contamination events.

Single particle ICP-MS as a tool for determining the stability of silver nanoparticles in aquatic matrixes under various environmental conditions, including treatment by ozonation.

Silver nanoparticles (AgNPs) are used in a large number of consumer products due to their antimicrobial and antifungal properties, and these materials may be discharged into municipal wastewater. Wastewater treatment, including advanced oxidation processes (AOPs), may modify the forms of silver in wastewater before they are discharged into surface waters. In addition, little is known about the changes in AgNPs that occur in natural waters under different environmental conditions. In this project, we utilized single particle ICP-MS (spICP-MS) and dynamic light scattering (DLS) analytical techniques to evaluate changes in the number and size of AgNPs in laboratory experiments with milliQ water under different environmental conditions, as well as during ozonation. Changes in the number and size of AgNPs determined by spICP-MS were evidence of altered stability of the nanoparticles. Increased rates of dissolution occurred under extremes of pH. Lower temperature decreased the rate of dissolution of AgNP relative to the dissolution in treatments at room temperature. The addition of chloride resulted in the loss of AgNPs from suspension due to agglomeration and precipitation. Ozonation led to a rapid decline in the number and size of AgNPs, as indicated by both spICP-MS and DLS analysis. An increase in the concentration of dissolved silver in the ozone treatments was evidence that changes in particle size were a result of oxidative dissolution of AgNPs to silver ion. Graphical abstract Single particle ICP-MS is used to evaluate dissolution of silver nanoparticles under different environmental conditions, including water treatment by ozonation.

Determination of monomethylmercury and dimethylmercury in the Arctic marine boundary layer.

Our understanding of the biogeochemical cycling of monomethylmercury (MMHg) in the Arctic is incomplete because atmospheric sources and sinks of MMHg are still unclear. We sampled air in the Canadian Arctic marine boundary layer to quantify, for the first time, atmospheric concentrations of methylated Hg species (both MMHg and dimethylmercury (DMHg)), and, estimate the importance of atmospheric deposition as a source of MMHg to Arctic land- and sea-scapes. Overall atmospheric MMHg and DMHg concentrations (mean ± SD) were 2.9 ± 3.6 and 3.8 ± 3.1 (n = 37) pg m(-3), respectively. Concentrations of methylated Hg species in the marine boundary layer varied significantly among our sites, with a predominance of MMHg over Hudson Bay (HB), and DMHg over Canadian Arctic Archipelago (CAA) waters. We concluded that DMHg is of marine origin and that primary production rate and sea-ice cover are major drivers of its concentration in the Canadian Arctic marine boundary layer. Summer wet deposition rates of atmospheric MMHg, likely to be the product of DMHg degradation in the atmosphere, were estimated at 188 ± 117.5 ng m(-2) and 37 ± 21.7 ng m(-2) for HB and CAA, respectively, sustaining MMHg concentrations available for biomagnification in the pelagic food web.

Environmental Fate of Silver Nanoparticles in Boreal Lake Ecosystems.

Silver nanoparticles (AgNPs) are currently the most commonly used nanoparticles in consumer products, yet their environmental fate in natural waters is poorly understood. In the present study, we investigated the persistence, transformations and distribution of polyvinylpyrrolidone (PVP) and citrate (CT) coated AgNPs in boreal lake mesocosms dosed either with a 6-week chronic regimen or a one-time pulse treatment at environmentally relevant dosing levels. In the chronic treatments, total Ag (TAg) concentrations reached ∼40% of target concentrations by the end of the experiment, and in the pulsed mesocosms, TAg dissipated slowly, with a half-life of ∼20 days. Sediments and periphyton on the mesocosm walls were an important sink for Ag. We found little effect of AgNP loading and surface coating on the persistence of TAg. There were also no differences between treatments in the degree of agglomeration of AgNPs, as indicated by the accumulation and distribution of Ag in the particulate and colloidal fractions. The low ionic strength and relatively high dissolved organic carbon concentrations in the lake water likely contributed to the relative stability of AgNP in the water column. The low concentrations of dissolved Ag (<1 µg L(-1)) in the size fraction <3 kDaA reflect the importance of natural ligands in controlling the concentrations of Ag released by dissolution of AgNPs. Overall, these data indicate that AgNPs are relatively stable in the tested lake environment and appear to result in quantities of highly toxic ionic Ag(+) that are below our limit of detection.

New insights into HgSe antagonism: Minor impact on inorganic Hg mobility while potential impacts on microorganisms.

Selenium (Se) is a crucial antagonistic factor of mercury (Hg) methylation in soil, with the transformation of inorganic Hg (IHg) to inert mercury selenide (HgSe) being the key mechanism. However, little evidence has been provided of the reduced Hg mobility at environmentally relevant doses of Hg and Se, and the potential impacts of Se on the activities of microbial methylators have been largely ignored. This knowledge gap hinders effective mitigation for methylmercury (MeHg) risks, considering that Hg supply and microbial methylators serve as materials and workers for MeHg production in soils. By monitoring the mobility of IHg and microbial activities after Se spike, we reported that 1) active methylation might be the premise of HgSe antagonism, as higher decreases in MeHg net production were found in soils with higher constants of Hg methylation rate; 2) IHg mobility did not significantly change upon Se addition in soils with high DOC concentrations, challenging the long-held view of Hg immobilization by Se; and 3) the activities of iron-reducing bacteria (FeRB), an important group of microbial methylators, might be potentially regulated by Se addition at a dose of 4 mg/kg. These findings provide empirical evidence that IHg mobility may not be the limiting factor under Se amendment and suggest the potential impacts of Se on microbial activities.

A hidden demethylation pathway removes mercury from rice plants and mitigates mercury flux to food chains.

Dietary exposure to methylmercury (MeHg) causes irreversible damage to human cognition and is mitigated by photolysis and microbial demethylation of MeHg. Rice (Oryza sativa L.) has been identified as a major dietary source of MeHg. However, it remains unknown what drives the process within plants for MeHg to make its way from soils to rice and the subsequent human dietary exposure to Hg. Here we report a hidden pathway of MeHg demethylation independent of light and microorganisms in rice plants. This natural pathway is driven by reactive oxygen species generated in vivo, rapidly transforming MeHg to inorganic Hg and then eliminating Hg from plants as gaseous Hg°. MeHg concentrations in rice grains would increase by 2.4- to 4.7-fold without this pathway, which equates to intelligence quotient losses of 0.01-0.51 points per newborn in major rice-consuming countries, corresponding to annual economic losses of US$30.7-84.2 billion globally. This discovered pathway effectively removes Hg from human food webs, playing an important role in exposure mitigation and global Hg cycling.

Soil Geobacteraceae are the key predictors of neurotoxic methylmercury bioaccumulation in rice.

Contamination of rice by the potent neurotoxin methylmercury (MeHg) originates from microbe-mediated Hg methylation in soils. However, the high diversity of Hg methylating microorganisms in soils hinders the prediction of MeHg formation and challenges the mitigation of MeHg bioaccumulation via regulating soil microbiomes. Here we explored the roles of various cropland microbial communities in MeHg formation in the potentials leading to MeHg accumulation in rice and reveal that Geobacteraceae are the key predictors of MeHg bioaccumulation in paddy soil systems. We characterized Hg methylating microorganisms from 67 cropland ecosystems across 3,600 latitudinal kilometres. The simulations of a rice-paddy biogeochemical model show that MeHg accumulation in rice is 1.3-1.7-fold more sensitive to changes in the relative abundance of Geobacteraceae compared to Hg input, which is recognized as the primary parameter in controlling MeHg exposure. These findings open up a window to predict MeHg formation and accumulation in human food webs, enabling more efficient mitigation of risks to human health through regulations of key soil microbiomes.

Mercury elimination by a top predator, Esox lucius.

Top-level piscivores are highly sought after for consumption in freshwater fisheries, yet these species contain the highest levels of the neurotoxin monomethylmercury (MMHg) and therefore present the greatest concern for MMHg exposure to humans. The slow elimination of MMHg is one factor that contributes to high levels of this contaminant in fish; however, little quantitative information exists on elimination rates by top predators in nature. We determined rates of MMHg elimination in northern pike (Esox lucius) by transferring fish that had naturally accumulated isotope-enriched MMHg (spike MMHg) through a whole-lake Hg loading study to a different lake. Over a period of ~7 y, pike were periodically recaptured and a small amount of muscle tissue was extracted using a nonlethal biopsy. Spike total mercury (THg) persisted in muscle tissue throughout the entire study despite discontinuing exposure upon transfer to the new lake. Spike THg burdens increased for the first ~460 d, followed by a decline to 65% of original burden levels over the next 200 d, and subsequently reached a plateau near original burden levels for the remainder of the study. We estimated the half-life of muscle THg to be 3.3 y (1193 d), roughly 1.2- to 2.7-fold slower than predicted by current elimination models. We advocate for further long-term field studies that examine kinetics of MMHg in fish to better inform predictive models estimating the recovery of MMHg-contaminated fisheries.

Use and legacy of mercury in the Andes.

Both cinnabar (HgS) and metallic mercury (Hg(0)) were important resources throughout Andean prehistory. Cinnabar was used for millennia to make vermillion, a red pigment that was highly valued in pre-Hispanic Peru; metallic Hg(0) has been used since the mid-16th century to conduct mercury amalgamation, an efficient process of extracting precious metals from ores. However, little is known about which cinnabar deposits were exploited by pre-Hispanic cultures, and the environmental consequences of Hg mining and amalgamation remain enigmatic. Here we use Hg isotopes to source archeological cinnabar and to fingerprint Hg pollution preserved in lake sediment cores from Peru and the Galápagos Islands. Both pre-Inca (pre-1400 AD) and Colonial (1532-1821 AD) archeological artifacts contain cinnabar that matches isotopically with cinnabar ores from Huancavelica, Peru, the largest cinnabar-bearing district in Central and South America. In contrast, the Inca (1400-1532 AD) artifacts sampled are characterized by a unique Hg isotopic composition. In addition, preindustrial (i.e., pre-1900 AD) Hg pollution preserved in lake sediments matches closely the isotopic composition of cinnabar from the Peruvian Andes. Industrial-era Hg pollution, in contrast, is distinct isotopically from preindustrial emissions, suggesting that pre- and postindustrial Hg emissions may be distinguished isotopically in lake sediment cores.

Dietary and waterborne mercury accumulation by yellow perch: a field experiment.

It is well accepted that the majority of monomethylmercury (MMHg) in fish originates in their food; however, the additional contribution of water as a source to fish MMHg levels remains unclear. We used isotope enriched mercury (Hg) in a controlled field experiment to quantify the uptake of Hg from ingested and aqueous sources by young-of-year yellow perch (Perca flavescens). Water and zooplankton from a lake that had received (202)Hg-enriched additions (called spike Hg) for 7 y during a whole-ecosystem loading study (METAALICUS) provided natural, low-level Hg exposure. We achieved separation of exposure pathways by housing perch in one of four treatments: clean water + clean food; clean water + Hg spiked food; Hg spiked water + clean food; Hg spiked water + Hg spiked food. Fish accumulated MMHg directly from water, and this source accounted for at least 10% of MMHg in fish during the 27-d trial. Accumulation of spike Hg from water and food was additive, with food providing the majority of spike MMHg taken in by fish. Predictions from a bioenergetics model that excludes water as a source underestimated Hg in perch by 11%. This study illustrates the importance of acknowledging both food and water as sources of Hg to fish and suggests that aqueous Hg should be included as a source of contamination in bioaccumulation models and experiments.

Sources of riverine mercury across the Mackenzie River Basin; inferences from a combined HgC isotopes and optical properties approach.

The Arctic environment harbors a complex mosaic of mercury (Hg) and carbon (C) reservoirs, some of which are rapidly destabilizing in response to climate warming. The sources of riverine Hg across the Mackenzie River basin (MRB) are uncertain, which leads to a poor understanding of potential future release. Measurements of dissolved and particulate mercury (DHg, PHg) and carbon (DOC, POC) concentration were performed, along with analyses of Hg stable isotope ratios (incl. ∆199Hg, δ202Hg), radiocarbon content (∆14C) and optical properties of DOC of river water. Isotopic ratios of Hg revealed a closer association to terrestrial Hg reservoirs for the particulate fraction, while the dissolved fraction was more closely associated with atmospheric deposition sources of shorter turnover time. There was a positive correlation between the ∆14C-OC and riverine Hg concentration for both particulate and dissolved fractions, indicating that waters transporting older-OC (14C-depleted) also contained higher levels of Hg. In the dissolved fraction, older DOC was also associated with higher molecular weight, aromaticity and humic content, which are likely associated with higher Hg-binding potential. Riverine PHg concentration increased with turbidity and SO4 concentration. There were large contrasts in Hg concentration and OC age and quality among the mountain and lowland sectors of the MRB, which likely reflect the spatial distribution of various terrestrial Hg and OC reservoirs, including weathering of sulfate minerals, erosion and extraction of coal deposits, thawing permafrost, forest fires, peatlands, and forests. Results revealed major differences in the sources of particulate and dissolved riverine Hg, but nonetheless a common positive association with older riverine OC. These findings reveal that a complex mixture of Hg sources, supplied across the MRB, will contribute to future trends in Hg export to the Arctic Ocean under rapid environmental changes.

Predicting net mercury methylation in sediments using diffusive gradient in thin films measurements.

Diffusive gradient in thin film (DGT) sediment probes for methylmercury (MMHg) were successfully deployed for up to 30 h in three mudflat sediments in San Francisco Bay for measuring labile fractions of dissolved MMHg in pore water. Our calculations show that the local DGT-induced depletion of MMHg in sediment pore waters should be fully compensated by the natural in situ MMHg production and its subsequent remobilization from the solid phase. DGT results were interpreted in terms of labile pore water concentration and provide MMHg concentration depth profiles with a centimeter resolution. Average concentrations of DGT-labile MMHg were 2.10 ± 0.29 and 1.64 ± 0.30 ng L(-1) at China Camp and Hamilton Army Airfield sediment pore waters, respectively, while the riverine location at Petaluma showed a distinct peak of 7.1 ng L(-1) near the sediment surface. Using isotope-enriched mercury species, high resolution depth profiles of MMHg net production rates ranging from 0.2 to 9.8 ng g(-1) d(-1) were obtained in parallel sediment cores sampled closely to DGT deployment sites. A positive, linear relationship between MMHg net production rates and labile MMHg concentrations acquired through DGT measurements was found and explained 79% of the variability in the data set. The latter illustrates that mercury methylation, a biogeochemical process, strongly affected the quantity of MMHg accumulated by the DGT device in the sediment and suggests that DGT measurements have the potential to predict net methylation rates.

Mercury methylation rates in Deception Island (Maritime Antarctica) waters and pyroclastic gravel impacted by volcanic mercury.

Deception Island is an active volcano in the Antarctica being volcanism a source of mercury. To improve the understanding of the Hg cycle in this remote ecosystem, pyroclastic gravel and water samples were collected and total (THg) and monomethylmercury (MMHg) concentrations were measured as well as the potential for Hg methylation. Gravel samples collected close to active fumaroles showed the highest THg levels (72 ng/g) while in water samples the highest concentrations of THg (1.2 ng/L) and MMHg (0.45 ng/L) where found. Methylation activity was barely observable in gravel samples. Biotic methylation rates in water were up to 13 times higher compared to those recorded previously in other polar waters. Abiotic methylation processes also play an important role, with up to 0.54 ± 0.43% of added Hg converted instantaneously to MMHg. These results suggest that Deception Island presents favourable conditions for MMHg explaining the elevated concentrations of both THg and MMHg in this ecosystem.

Isotope fractionation of mercury during its photochemical reduction by low-molecular-weight organic compounds.

Photochemical reduction of Hg(II) by various low-molecular-weight organic compounds (LMWOC) was investigated to evaluate the effect of specific functional groups that are typically encountered in natural dissolved organic matters (DOM) on the photoreactivity and isotope fractionation of Hg. LMWOC with reduced sulfur functional groups (e.g., cysteine, glutathione) resulted in slower photochemical reduction of Hg(II) than those without reduced sulfur groups (e.g., serine, oxalic acid). Reduction rate constants were specifically determined for two contrasting LMWOC: dl-serine (0.640 h(-1)) and l-cysteine (0.047 h(-1)). Different mass independent isotope effects of Hg were induced by the two types of LMWOC. S-containing ligands specifically enriched magnetic isotopes ((199)Hg and (201)Hg) in the product (Hg(0)) while sulfurless ligands enriched (199)Hg and (201)Hg in the reactant (Hg(II)), suggesting that opposite magnetic isotope effects were produced by different types of ligands. The nuclear field shift effect was also observed in the photochemical reduction by serine. These isotope effects are related to specific functional groups and reduction mechanisms, and may be used to distinguish between primary and secondary photochemical reduction mechanisms of Hg(II) and to explain isotope fractionation during the photochemical reduction of Hg(II) by natural DOM, which provides mixed bonding conditions.