Hg Stable Isotope Research Articles

Review of stable mercury isotopes in ecology and biogeochemistry.

Due to the advent of cold vapor-multicollector-inductively coupled plasma mass spectrometry (CV-MC-ICP-MS) in the past two decades, many research groups studying mercury (Hg) biogeochemistry have integrated stable Hg isotopes into their research. Currently, >200 studies using this technique have been published and this has greatly enhanced our understanding of the Hg biogeochemical cycle beyond what Hg concentration and speciation analyses alone can provide. These studies are largely divided into two groups: (i) controlled experiments investigating fractionation of Hg isotopes and refining tools of isotopic analyses, and (ii) studies of natural variations of Hg isotopes. It is now known that Hg isotopes undergo both mass dependent fractionation (MDF; reported as the ratio of mass 202Hg to 198Hg) and mass independent fractionation (MIF), with MIF occurring at odd masses (199Hg, 201Hg) to a larger magnitude and at even masses (200Hg, 204Hg) to a much smaller magnitude. The two types of MIF are controlled by different photochemical processes. The range of isotopic variations of MDF, odd-MIF, and even-MIF are now well documented in a diverse set of environmental samples, and researchers are continuing to explore how the field of Hg isotope biogeochemistry can be further developed and taken to the next level of understanding. One application that has received considerable attention is the use of Hg isotopes to examine the environmental controls on the production and degradation of methylmercury (MeHg), the most toxic and bioaccumulative form of Hg. Since MeHg is efficiently assimilated and biomagnified along food chains, MeHg has the potential to be a robust ecological tracer. In this review, we give an updated overview of the field of Hg isotopes and focus on how Hg isotopes of MeHg can be used to address fundamental ecological questions, including energy transfer across ecosystem interfaces and as a tracer for animal movements.

Mercury source changes and food web shifts alter contamination signatures of predatory fish from Lake Michigan

To understand the impact reduced mercury (Hg) loading and invasive species have had on methylmercury bioaccumulation in predator fish of Lake Michigan, we reconstructed bioaccumulation trends from a fish archive (1978 to 2012). By measuring fish Hg stable isotope ratios, we related temporal changes in Hg concentrations to varying Hg sources. Additionally, dietary tracers were necessary to identify food web influences. Through combined Hg, C, and N stable isotopic analyses, we were able to differentiate between a shift in Hg sources to fish and periods when energetic transitions (from dreissenid mussels) led to the assimilation of contrasting Hg pools (2000 to present). In the late 1980s, lake trout δ202Hg increased (0.4‰) from regulatory reductions in regional Hg emissions. After 2000, C and N isotopes ratios revealed altered food web pathways, resulting in a benthic energetic shift and changes to Hg bioaccumulation. Continued increases in δ202Hg indicate fish are responding to several United States mercury emission mitigation strategies that were initiated circa 1990 and continued through the 2011 promulgation of the Mercury and Air Toxics Standards rule. Unlike archives of sediments, this fish archive tracks Hg sources susceptible to bioaccumulation in Great Lakes fisheries. Analysis reveals that trends in fish Hg concentrations can be substantially affected by shifts in trophic structure and dietary preferences initiated by invasive species in the Great Lakes. This does not diminish the benefits of declining emissions over this period, as fish Hg concentrations would have been higher without these actions.

Insights from mercury stable isotopes on terrestrial–atmosphere exchange of Hg(0) in the Arctic tundra

Abstract. The tundra plays a pivotal role in the Arctic mercury (Hg) cycle by storing atmospheric Hg deposition and shuttling it to the Arctic Ocean. A recent study revealed that 70 % of the atmospheric Hg deposition to the tundra occurs through gaseous elemental mercury (GEM or Hg(0)) uptake by vegetation and soils. Processes controlling land–atmosphere exchange of Hg(0) in the Arctic tundra are central, but remain understudied. Here, we combine Hg stable isotope analysis of Hg(0) in the atmosphere, interstitial snow air, and soil pore air, with Hg(0) flux measurements in a tundra ecosystem at Toolik Field Station in northern Alaska (USA). In the dark winter months, planetary boundary layer (PBL) conditions and Hg(0) concentrations were generally stable throughout the day and small Hg(0) net deposition occurred. In spring, halogen-induced atmospheric mercury depletion events (AMDEs) occurred, with the fast re-emission of Hg(0) after AMDEs resulting in net emission fluxes of Hg(0). During the short snow-free growing season in summer, vegetation uptake of atmospheric Hg(0) enhanced atmospheric Hg(0) net deposition to the Arctic tundra. At night, when PBL conditions were stable, ecosystem uptake of atmospheric Hg(0) led to a depletion of atmospheric Hg(0). The night-time decline of atmospheric Hg(0) was concomitant with a depletion of lighter Hg(0) isotopes in the atmospheric Hg pool. The enrichment factor, ε202Hgvegetationuptake=-4.2 ‰ (±1.0 ‰) was consistent with the preferential uptake of light Hg(0) isotopes by vegetation. Hg(0) flux measurements indicated a partial re-emission of Hg(0) during daytime, when solar radiation was strongest. Hg(0) concentrations in soil pore air were depleted relative to atmospheric Hg(0) concentrations, concomitant with an enrichment of lighter Hg(0) isotopes in the soil pore air, ε202Hgsoilair-atmosphere=-1.00 ‰ (±0.25 ‰) and E199Hgsoilair-atmosphere=0.07 ‰ (±0.04 ‰). These first Hg stable isotope measurements of Hg(0) in soil pore air are consistent with the fractionation previously observed during Hg(0) oxidation by natural humic acids, suggesting abiotic oxidation as a cause for observed soil Hg(0) uptake. The combination of Hg stable isotope fingerprints with Hg(0) flux measurements and PBL stability assessment confirmed a dominant role of Hg(0) uptake by vegetation in the terrestrial–atmosphere exchange of Hg(0) in the Arctic tundra.

Corn (Zea mays L.): A low methylmercury staple cereal source and an important biospheric sink of atmospheric mercury, and health risk assessment

In mercury (Hg) contaminated areas of Asia, human exposure to toxic methyl-Hg (MeHg) through a rice-based diet of locally produced crop may pose a health threat. Alternative cropping system to rice in such areas would be most desirable. In this study, corn, the leading cereal source in the world with large biomass, was demonstrated to accumulate an insignificant amount of MeHg from the soil in its edible portion compared to that in rice, suggesting corn being a very competitive alternative crop. By examining Hg stable isotope composition, Hg in the aerial parts of corn was found to be mostly from the atmosphere. Maize cropping worldwide is estimated to be a discemible sink of atmospheric Hg with approximately 44 Mg Hg accumulated in each growing season on a yearly basis, most of which is from foliar uptake of atmospheric Hg and this amount is comparable to litterfall Hg observed in North America and Europe. It is thus recommended to use corn as a replacement of rice in highly Hg-contaminated areas for remediation of Hg pollution in the food supply.

Mercury Cycling in the North Pacific Subtropical Gyre as Revealed by Mercury Stable Isotope Ratios

AbstractThe oceans are an important global reservoir for mercury (Hg), and marine fish consumption is the dominant human exposure pathway for its toxic methylated form. A more thorough understanding of the global biogeochemical cycle of Hg requires additional information on the mechanisms that control Hg cycling in pelagic marine waters. In this study, Hg isotope ratios and total Hg concentrations are used to explore Hg biogeochemistry in oligotrophic marine environments north of Hawaii. We present the first measurements of the vertical water column distribution of Hg concentrations and the Hg isotopic composition in precipitation, marine particles, and zooplankton near Station ALOHA (22°45′N, 158°W). Our results reveal production and demethylation of methylmercury in both the euphotic (0–175 m) and mesopelagic zones (200–1,000 m). We document a strong relationship between Hg isotopic composition and depth in particles, zooplankton, and fish in the water column and diurnal variations in Δ199Hg values in zooplankton sampled near the surface (25 m). Based on these observations and stable Hg isotope relationships in the marine food web, we suggest that the Hg found in large pelagic fish at Station ALOHA was originally deposited largely by precipitation, transformed into methyl‐Hg, and bioaccumulated in situ in the water column. Our results highlight how Hg isotopic compositions reflect abiotic and biotic production and degradation of methyl‐Hg throughout the water column and the importance of particles and zooplankton in the vertical transport of Hg.

Isotopic evidence for mercury photoreduction and retention on particles in surface waters of Central California, USA

Cache Creek (Coast Range, California) and the Yuba River (Sierra Nevada Foothills, California) are two river systems affected by extensive mercury (Hg) contamination due to legacy sources of Hg related to mining. Stable Hg isotope techniques have proven useful for elucidating the complex cycling of Hg within aquatic ecosystems, and we applied these techniques to improve understanding of Hg and methylmercury (MeHg) transformations in these watersheds. Total mercury (THg) concentrations and Hg stable isotope ratios were measured in filtered surface waters and suspended particulate matter collected from 14 sites within the Cache Cr. and Yuba R. watersheds. Filtered surface waters from both watersheds exhibited values of ∆199Hg (0.37‰ to 0.71‰), consistently elevated above those observed in sediments (∆199Hg average = 0.07‰). Associated suspended particulates from these surface water samples displayed a much greater range of values for ∆199Hg (−0.61‰ to 0.70‰), although suspended particulates from the Yuba R. exhibited mostly negative ∆199Hg values (−0.61‰ to 0.10‰). The relationship between ∆199Hg and ∆201Hg in the filtered surface waters and associated suspended particulates was calculated using a bivariate York regression, yielding a slope of 1.57 ± 0.49 (±2SE) for the Yuba R. and 1.40 ± 0.27 (±2SE) for Cache Cr., both within error of the previously reported experimentally-derived slopes for MeHg- and inorganic Hg(II)-photoreduction. This provides isotopic evidence that Hg photoreduction is occurring within these surface waters to a significant degree, and suspended particulate phases are retaining the reduced product of Hg photoreduction, particularly within the Yuba R. The isotopic compositions of filtered surface waters are consistent with the isotopic signatures recorded in biota at low trophic positions within these watersheds, suggesting that the reservoir of Hg incorporated within the biota of these systems is similar to the filter-passing Hg fraction in surface waters.

The river runs through it: The Athabasca River delivers mercury to aquatic birds breeding far downstream.

This study examined factors contributing to temporal variability (2009–2017) in total mercury (THg) concentrations in aquatic bird eggs collected in the Peace-Athabasca Delta and Lake Athabasca in northern Alberta. Factors examined included year of egg collection, site of collection, bird species, bird diets, annual surface-mineable oil sands production, forest fires, and flow of the Athabasca River. Surface mining activities associated with Alberta’s Athabasca oil sands are situated north of Fort McMurray, Alberta, adjacent to the northward-flowing Athabasca River. Previous studies have found that oil sands industrial operations release mercury into the local (within ~50 km) environment. An information-theoretic approach revealed that the best model for explaining egg THg levels included Athabasca River flow, bird food source, and bird species. Variability in egg THg levels was partly a reflection of differences in food sources, e.g. proportions of aquatic versus terrestrial food in bird diets. Annual fluctuations in maximal flow of the Athabasca River were also important with eggs collected following years of high maximal flow exhibiting higher THg concentrations. Furthermore, eggs collected in years of high versus low flow differed in their stable Hg isotope composition with less mass-independent fraction of 199Hg and 201Hg in years of high flow. Riverine processes associated with suspended sediment were likely critical in regulating Hg availability to nesting birds. This study highlights the importance of the Athabasca River as a conduit for Hg transport to ecologically-sensitive downstream ecosystems such as the Peace-Athabasca Delta and Wood Buffalo National Park (a UNESCO World Heritage Site). Human activities that increase atmospheric Hg deposition to the Athabasca River watershed, or that enhance Hg releases to the river through erosion of Hg-bearing soils, will likely increase the availability of Hg to organisms inhabiting downstream areas.

Mercury bioaccumulation in tilefish from the northeastern Gulf of Mexico 2 years after the Deepwater Horizon oil spill: Insights from Hg, C, N and S stable isotopes

Mercury (Hg) concentration in fish of the Gulf of the Mexico (GoM) is a major concern due to the importance of the GoM for U.S. fisheries. The Deepwater Horizon (DWH) oil spill in April 2010 in the northern GoM resulted in large amounts of oil and dispersant released to the water column, which potentially modified Hg bioaccumulation patterns in affected areas. We measured Hg species (methylmercury (MMHg) and inorganic Hg (IHg)) concentrations, and light (C, N and S) and Hg stable isotopes in muscle and liver tissues from tilefish (Lopholatilus chamaleonticeps) sampled in 2012 and 2013 along the shelf break of the northeastern GoM. Fish located close to the mouth of the Mississippi River (MR) and northwest of the DWH well-head (47 km) showed significantly lower Hg levels in muscle and liver than fish located further northeast of the DWH (>109 km), where 98% of tilefish had Hg levels in the muscle above US consumption advisory thresholds (50% for tilefish close to the DWH). Differences in light and Hg stable isotopes signatures were observed between these two areas, showing higher δ15N, and lower δ202Hg, Δ199Hg and δ34S in fish close to the DWH/MR. This suggests that suspended particles from the MR reduces Hg bioavailability at the base of the GoM food chains. This phenomenon can be locally enhanced by the DWH that resulted in increased particles in the water column as evidenced by the marine snow layer in the sediments. On the other hand, freshly deposited Hg associated with organic matter in more oligotrophic marine waters enhanced Hg bioaccumulation in local food webs. Comparing Hg isotopic composition in liver and muscle of fish indicates specific metabolic response in fish having accumulated high levels of MMHg.

Rapid pre-concentration of mercury in solids and water for isotopic analysis

The precise quantification of mercury (Hg) stable isotope compositions in low concentration or dilute samples poses analytical challenges due to Hg mass limitations. Common Hg pre-concentration procedures require extended processing times, making rapid Hg stable isotope measurements challenging. Here we present a modified pre-concentration method that combines commonly used Hg reduction and gold trap amalgamation followed by semi-rapid thermal desorption (less than 1 h) and chemical trapping. This custom designed system was demonstrated to perform adequately on multiple trapping matrices including a new bromine monochloride (BrCl) wet oxidant trap (40% 3HNO3:BrCl), capable of trapping consistently in 2 mL volume over a wide range of Hg masses (5–200 ng). The procedure was also shown to work effectively on natural matrices, waters and sediments, producing comparable isotope results to the direct digestion analyses. Here, we present a method that can effectively triple sample throughput in comparison to traditional procedures, and also access lower concentration matrices without compromising the accuracy or precision of Hg isotope measurements.

Evidence of Mercury Methylation and Demethylation by the Estuarine Microbial Communities Obtained in Stable Hg Isotope Studies

Microbial activity is a critical factor controlling methylmercury formation in aquatic environments. Microbial communities were isolated from sediments of two highly mercury-polluted areas of the Tagus Estuary (Barreiro and Cala do Norte) and differentiated according to their dependence on oxygen into three groups: aerobic, anaerobic, and sulphate-reducing microbial communities. Their potential to methylate mercury and demethylate methylmercury was evaluated through incubation with isotope-enriched Hg species (199HgCl and CH3201HgCl). The results showed that the isolated microbial communities are actively involved in methylation and demethylation processes. The production of CH3199Hg was positively correlated with sulphate-reducing microbial communities, methylating up to 0.07% of the added 199Hg within 48 h of incubation. A high rate of CH3201Hg degradation was observed and >20% of CH3201Hg was transformed. Mercury removal of inorganic forms was also observed. The results prove the simultaneous occurrence of microbial methylation and demethylation processes and indicate that microorganisms are mainly responsible for methylmercury formation and accumulation in the polluted Tagus Estuary.

Spatial and temporal variation in the isotopic composition of mercury in the South River, VA

Historic point source mercury (Hg) inputs from industrial processes on the South River (Waynesboro, Virginia) ended many decades ago, but sediment and surface water Hg concentrations remain elevated relative to the regional background. To understand Hg sources, mobility, and fate in the South River, we analyzed total Hg concentrations and Hg stable isotope compositions of streambed sediments, bank soils, suspended particles, filtered surface waters, and channel margin hyporheic zone pore waters. Hg isotopes allow for the identification of three distinct Hg end-member inputs to the South River, consisting of a regional background source and two isotopically distinct contaminant sources. Hydrologic conditions are demonstrated to have an influence on within-channel Hg isotope fractionation and Hg partitioning, with no observed isotopic discrimination between suspended particulate Hg and filtered surface water Hg during elevated flow conditions. Channel margin hyporheic zone porewaters had significantly higher δ202Hg values than surface waters (δ202Hg = −0.52 ± 0.44‰ and δ202Hg = −0.89 ± 0.20‰ respectively [mean ± 1SD]). A subset of porewaters exhibited mass independent fractionation signatures (Δ199Hg = 0.33 ± 0.06‰; Δ200Hg = 0.19 ± 0.03‰ [mean ± 1SD]) that are suggestive of a precipitation-derived origin for the dissolved Hg pool. Sediments from a floodplain profile were analyzed to explore the temporal variation in Hg isotopic composition within the South River, indicating brief excursions (up to δ202Hg = +0.61‰) from the average composition observed in modern samples (δ202Hg = −0.52 ± 0.09‰). By improving understanding of the spatial, temporal, and hydrologic conditions that contribute to variations in Hg isotopic composition, this study provides insights into the processes that control Hg isotopic end-member sources, Hg-loading to the channel during elevated flows, and Hg fate in the South River.

Compound specific stable isotope determination of methylmercury in contaminated soil

Rice is one of the main sources of methylmercury (MeHg) to humans, and soil is the main source of MeHg to rice grains. Determining the Hg isotope composition in environmental samples is a good way of characterizing sources of Hg pollution and investigating environmental processes. We developed a new compound-specific method for determining stable Hg isotopes in MeHg in contaminated soil and sediment. The method involved HNO3 leaching/solvent extraction, chemical ethylation, and separation by gas chromatography with a solenoid valve optimized to enrich MeHg. The method was optimized by using MeHg standard solution, certified reference materials and paddy soil samples. The δ202Hg precision for replicate MeHg isotope analyses was 0.14‰ (2 × standard deviation, n = 11), and no fractionation of Hg stable isotopes was found during the separation processes. The δ202Hg values for MeHg in paddy soils were −1.78‰ to −1.30‰, which were lower than the δ202Hg values for total Hg (−1.32‰ to −0.44‰). The results indicated that methylation (rather than demethylation) was the dominant process in the paddy soils. The method developed in this study can help us to better understand MeHg migration and transformation processes in paddy soil-rice ecosystem.

Hg Compound-Specific Isotope Analysis at Ultratrace Levels Using an on Line Gas Chromatographic Preconcentration and Separation Strategy Coupled to Multicollector-Inductively Coupled Plasma Mass Spectrometry.

Stable Hg isotope analyses are nowadays widely employed to discriminate Hg sources and understand its biogeochemical cycle. Until now, total Hg isotopic compositions have been mainly used but Hg compound-specific isotopic analysis (CSIA) methodologies are emerging. Online Hg-CSIA were limited to samples containing high concentrations, but in this work we overcome this limitation for the measurement of inorganic (IHg) and monomethylmercury (MMHg) by gas chromatography hyphenated to multicollector-inductively coupled plasma mass spectrometry (GC/MC-ICPMS) through the use of an automated online preconcentration strategy, allowing injection volumes up to 100 times larger than usual. The preconcentration of Hg species and subsequent transfer to the column were achieved by a programmed temperature vaporization (PTV) injector fitted with a packed liner. The PTV parameters were first optimized using a quadrupole ICPMS, and then its suitability for Hg-CSIA was evaluated with long-term replicate analysis of various standards and reference materials (RMs). The large preconcentration capability enables analyses with Hg concentrations in the organic solvent 2 orders of magnitude lower than the previous conventional GC/MC-ICPMS method, but a compound specific standard bracketing procedure was required for MMHg in order to correct for the differential behavior of Hg species in the liner. The external reproducibility of the method ranged from 0.19 to 0.39 ‰ for Δ199Hg and δ202Hg (as 2 SD, n = 143-167) depending on the species. The analysis of various RMs demonstrated the applicability to environmental samples with species concentrations down to about 150 ng g-1. This new methodology opens the way for a much wider range of online Hg-CSIA measurements that will improve our understanding of the Hg biogeochemical cycle.

Hg-Stable Isotope Variations in Marine Top Predators of the Western Arctic Ocean

Recent studies on mercury (Hg)-stable isotopes in Alaskan seabird eggs and ringed seal livers illustrated the control of sea ice cover on marine methyl-Hg photochemistry. Here, complementary marine mammal tissues have been analyzed to document variations in Hg-, carbon (C)-, and nitrogen (N)-stable isotope compositions of Arctic marine food webs. Hg-stable isotope ratios were measured in liver samples of 55 beluga whales (Delphinapterus leucas) and 15 polar bears (Ursus maritimus) collected since 1990. Large variations in δ202Hg (≈2.1‰) and Δ199Hg (≈1.7‰) are observed between species and within species stocks covering the Gulf of Alaska–Bering Sea–Arctic Ocean regions. Polar bears, mainly feeding on ringed seal (δ15N shift of 4.2‰), show identical liver Δ199Hg of 0.5‰, confirming the absence of metabolic mass-independent fractionation, and 0.33 ± 0.11‰ enrichment in heavy Hg isotopes. Beluga whale liver total Hg concentrations increase with age, reflecting lifetime bioaccumulation, while Hg speciation shi...

An investigation of mercury sources in the Puyango-Tumbes River: Using stable Hg isotopes to characterize transboundary Hg pollution

Mercury (Hg) concentrations and stable isotopes along with other trace metals were examined in environmental samples from Ecuador and Peru's shared Puyango-Tumbes River in order to determine the extent to which artisanal- and small-scale gold mining (ASGM) in Portovelo-Zaruma, Ecuador contributes to Hg pollution in the downstream aquatic ecosystem. Prior studies investigated the relationship between ASGM activities and downstream Hg pollution relying primarily on Hg concentration data. In this study, Hg isotopes revealed an isotopically heavy Hg signature with negligible mass independent fractionation (MIF) in downstream sediments, which was consistent with the signature observed in the ASGM source endmember. This signature was traced as far as ∼120 km downstream of Portovelo-Zaruma, demonstrating that Hg stable isotopes can be used as a tool to fingerprint and trace sources of Hg over vast distances in freshwater environments. The success of Hg isotopes as a source tracer in fresh waters is largely due to the particle-reactive nature of Hg. Furthermore, the magnitude and extent of downstream Hg, lead, copper and zinc contamination coupled with the Hg isotopes suggest that it is unlikely that the smaller artisanal-scale activities, which do not use cyanidation, are responsible for the pollution. More likely it is the scale of ores processed and the cyanide leaching, which can release other metals and enhance Hg transport, used during small-scale gold mining that is responsible. Thus, although artisanal- and small-scale gold mining occur in tandem in Portovelo-Zaruma, a distinction should be made between these two activities.

Factors Affecting Mercury Stable Isotopic Distribution in Piscivorous Fish of the Laurentian Great Lakes

Identifying the sources of methylmercury (MeHg) and tracing the transformations of mercury (Hg) in the aquatic food web are important components of effective strategies for managing current and legacy Hg sources. In our previous work, we measured stable isotopes of Hg (δ202Hg, Δ199Hg, and Δ200Hg) in the Laurentian Great Lakes and estimated source contributions of Hg to bottom sediment. Here, we identify isotopically distinct Hg signatures for Great Lakes trout ( Salvelinus namaycush) and walleye ( Sander vitreus), driven by both food-web and water-quality characteristics. Fish contain high values for odd-isotope mass independent fractionation (MIF) with averages ranging from 2.50 (western Lake Erie) to 6.18‰ (Lake Superior) in Δ199Hg. The large range in odd-MIF reflects variability in the depth of the euphotic zone, where Hg is most likely incorporated into the food web. Even-isotope MIF (Δ200Hg), a potential tracer for Hg from precipitation, appears both disconnected from lake sedimentary sources and comparable in fish among the five lakes. We suggest that similar to the open ocean, water-column methylation also occurs in the Great Lakes, possibly transforming recently deposited atmospheric Hg deposition. We conclude that the degree of photochemical processing of Hg is controlled by phytoplankton uptake rather than by dissolved organic carbon quantity among lakes.

A review of global environmental mercury processes in response to human and natural perturbations: Changes of emissions, climate, and land use

We review recent progress in our understanding of the global cycling of mercury (Hg), including best estimates of Hg concentrations and pool sizes in major environmental compartments and exchange processes within and between these reservoirs. Recent advances include the availability of new global datasets covering areas of the world where environmental Hg data were previously lacking; integration of these data into global and regional models is continually improving estimates of global Hg cycling. New analytical techniques, such as Hg stable isotope characterization, provide novel constraints of sources and transformation processes. The major global Hg reservoirs that are, and continue to be, affected by anthropogenic activities include the atmosphere (4.4–5.3 Gt), terrestrial environments (particularly soils: 250–1000 Gg), and aquatic ecosystems (e.g., oceans: 270–450 Gg). Declines in anthropogenic Hg emissions between 1990 and 2010 have led to declines in atmospheric Hg0 concentrations and HgII wet deposition in Europe and the US (− 1.5 to − 2.2% per year). Smaller atmospheric Hg0 declines (− 0.2% per year) have been reported in high northern latitudes, but not in the southern hemisphere, while increasing atmospheric Hg loads are still reported in East Asia. New observations and updated models now suggest high concentrations of oxidized HgII in the tropical and subtropical free troposphere where deep convection can scavenge these HgII reservoirs. As a result, up to 50% of total global wet HgII deposition has been predicted to occur to tropical oceans. Ocean Hg0 evasion is a large source of present-day atmospheric Hg (approximately 2900 Mg/year; range 1900–4200 Mg/year). Enhanced seawater Hg0 levels suggest enhanced Hg0 ocean evasion in the intertropical convergence zone, which may be linked to high HgII deposition. Estimates of gaseous Hg0 emissions to the atmosphere over land, long considered a critical Hg source, have been revised downward, and most terrestrial environments now are considered net sinks of atmospheric Hg due to substantial Hg uptake by plants. Litterfall deposition by plants is now estimated at 1020–1230 Mg/year globally. Stable isotope analysis and direct flux measurements provide evidence that in many ecosystems Hg0 deposition via plant inputs dominates, accounting for 57–94% of Hg in soils. Of global aquatic Hg releases, around 50% are estimated to occur in China and India, where Hg drains into the West Pacific and North Indian Oceans. A first inventory of global freshwater Hg suggests that inland freshwater Hg releases may be dominated by artisanal and small-scale gold mining (ASGM; approximately 880 Mg/year), industrial and wastewater releases (220 Mg/year), and terrestrial mobilization (170–300 Mg/year). For pelagic ocean regions, the dominant source of Hg is atmospheric deposition; an exception is the Arctic Ocean, where riverine and coastal erosion is likely the dominant source. Ocean water Hg concentrations in the North Atlantic appear to have declined during the last several decades but have increased since the mid-1980s in the Pacific due to enhanced atmospheric deposition from the Asian continent. Finally, we provide examples of ongoing and anticipated changes in Hg cycling due to emission, climate, and land use changes. It is anticipated that future emissions changes will be strongly dependent on ASGM, as well as energy use scenarios and technology requirements implemented under the Minamata Convention. We predict that land use and climate change impacts on Hg cycling will be large and inherently linked to changes in ecosystem function and global atmospheric and ocean circulations. Our ability to predict multiple and simultaneous changes in future Hg global cycling and human exposure is rapidly developing but requires further enhancement.

Mercury stable isotope compositions in magmatic-affected coal deposits: New insights to mercury sources, migration and enrichment

Mercury (Hg) is commonly present at trace levels in coal deposits. Geological processes, particularly magmatic intrusion and hydrothermal cycling in coal-bearing strata can significantly increase Hg levels in coals. However, the effects of thermal stress, magmatic components, magmatic-hydrothermal fluids, low-temperature hydrothermal fluids on Hg enrichment are confounded in a magmatic-affected coal basin. Here, we demonstrate the use of stable Hg isotopes to understand the controlling factors on Hg enrichment in two well-known Chinese coal deposits affected by magmatic activities: Wulantuga low-temperature hydrothermal-altered coal deposit and Wolonghu magmatic-intruded coal deposit.The Wulantuga No. 6 coal seam is extremely enriched in Hg, varying from 0.37μg/g in middle coal benches to 40–90μg/g in the upper most and lowest coal benches. Approximately 2.5‰ variation in mass dependent fractionation (MDF, −3.07‰ to −0.58‰ in δ202Hg) is observed. δ202Hg vs. 1/[Hg] diagram suggests a mixture of three Hg end-members: original hydrothermal fluids, fractionated hydrothermal fluids and native coal-forming materials. In addition, Wulantuga coals all show positive mass independent fractionation (MIF) of odd isotopes, up to 0.87‰ in Δ199Hg and 0.66‰ in Δ201Hg. The Δ199Hg/Δ201Hg ratios range from 1.3 to 3.3, suggesting that a large fraction of photodegraded methylmercury was likely incorporated into the coal deposit. The magmatic-intruded Wolonghu No. 8 coal seam is only slightly to intermediately enriched in Hg, varying from 0.10μg/g to 0.40μg/g. The coals near the contact sill (≤5cm, −1.81‰ to −1.52‰) have similar δ202Hg as the magmatic sill rocks (−2.05‰ to −1.80‰), both with insignificant MIF values. Coals far from the contact sill (≥15cm) have δ202Hg values varying from −3.40‰ to −1.61‰ and Δ199Hg varying from 0.26‰ to 0.58‰, which are significantly enriched in light and odd Hg isotopes compared to coals near the contact sill. Δ199Hg and Δ201Hg in Wolonghu coals far from the contact sill resemble those of meteoritic waters and seawater in both magnitude and Δ199Hg/Δ201Hg ratio. Our two case studies show significant MDF and MIF of Hg isotopes, which inform on Hg migration and sequestration in the magmatic rocks and coal deposits, and on the roles of meteoric water and hydrothermal fluid circulation.

Monomethylmercury degradation by the human gut microbiota is stimulated by protein amendments.

Monomethylmercury (MMHg) is a potent neurotoxicant that can be bioaccumulated and biomagnified through trophic levels. Human populations whose diets contain MMHg are at risk of MMHg toxicity. The gut microbiota was identified as a potential factor causing variation in MMHg absorption and body burden. However, little is known about the role of gut microbiota on Hg transformations. We conducted a series of in vitro experiments to study the effects of dietary nutrient change on Hg metabolism and the human gut microbiota using anoxic fecal slurry incubations. We used stable Hg isotope tracers to track MMHg production and degradation and characterized the microbiota using high throughput sequencing of the 16S rRNA gene. We show that the magnitude of MMHg degradation is individual dependent and rapidly responds to changes in nutrient amendments, leading to complete degradation of the MMHg present. Although the mechanism involved remains unknown, it does not appear to involve the well-known mer operon. Our data are the first to show a nutrient dependency on the ability of the simulated human gut microbiota to demethylate MMHg. This work provides much-needed insights into individual variations in Hg absorption and potential toxicity.

Mercury speciation and Hg stable isotope ratios in sediments from Amazon floodplain lakes—Brazil

AbstractHg concentrations and isotope ratios were measured to better characterize the mercury dynamics related to Hg cycling in Amazon floodplain lakes. We collected sediments, suspended particulate material (SPM), and plankton from floodplain lakes and compared then to sediments from rivers and soils of the central Amazon basin by measuring concentrations of total Hg (THg) and methylmercury (MMHg), and mercury isotope ratios. Concentrations of THg and MMHg in the lake sediments ranged to 69–109 ng g−1 and 0.62–4.78 ng g−1, respectively. A positive correlation between THg and MMHg in soils and sediments suggest that inorganic Hg in this system is highly bioavailable and readily converted to MMHg. δ202Hg values ranged from −1.40‰ to −0.89‰ and Δ199Hg from −0.34‰ to −0.18‰. These values were comparable to those measured in riverine sediments (−2.14‰ to −1.23‰ and −0.51‰ to −0.05‰), suggesting a contribution of riverine sediments to lake sediments, at least during the season of rising waters, during which lake samples were collected. SPM on the other hand was much elevated in THg (590–1066 ng g−1) and showed more negative δ202Hg (−3.00 to −2.15), similar to those found in soils (−2.99‰ to −2.17‰), suggesting that Hg in SPM may originate from erosion of floodplain soils.