Hg Cycling Research Articles

The Hg behaviors in mangrove ecosystems revealed by Hg stable isotopes: a case study of Maowei mangrove.

As one of the most productive marine ecosystems in the tropics and subtropics, mangroves are an important part of the global mercury (Hg) cycling. The environmental processes and effects of Hg in mangroves are complex and affect human Hg exposure, and it is crucial to understand Hg behaviors in the mangrove ecosystem. However, clarifying Hg behaviors in the mangrove ecosystem remains difficult because of an insufficient understanding of the dominant pathways. In this study, measurements of mercury (Hg) concentration and isotope ratios in sediment and plant tissues from a mangrove wetland were used to investigate Hg isotope fractionation in mangrove plants and sediments. Spatial patterns in Hg concentration and isotope signatures indicate that Hg re-emission in the sediment was suppressed by mangrove plants. The ratio of Δ199Hg/Δ201Hg was 0.93 for all sediments, indicating that Hg mass-independent fractionation in the mangrove ecosystem was primarily affected by photoreduction, while the ratios of Δ199Hg/Δ201Hg and Δ199Hg/δ202Hg for plant tissues suggested that natural organic matter reduction of Hg(II) was occurred in the plants. The distinct positive Δ199Hg values found in mangrove plants were supposed to be the results of the unique physiological characteristics of mangroves. The exterior Hg sources from atmosphere and seawater emphasize the role of mangrove ecosystems in the global Hg biogeochemistry. Our study highlights the distinct Hg isotope signatures in the mangrove from that in forests and indicates unique Hg behaviors in the mangrove ecosystem.

Processes affecting the transformation of mercury in the coastal zone in the vicinity of two river mouths in the southern Baltic Sea

Rivers play an important role in the coastal biogeochemical cycling of mercury (Hg), however, the fate of Hg in these environments remains poorly understood. In this study, we determine how processes such as mixing, flocculation, and settling of particles in the river mouths of the Vistula and the Reda rivers in the southern Baltic Sea, affect the transformation and migration of mercury. The most important process was the mixing of river water with seawater. This process led to a decrease in the concentration of total mercury and particulate mercury with increasing distance from the river mouth. The second most important process affecting the distribution of Hg was flocculation and particle settling. This process most effectively occurred in the middle part of the mouth, where the highest salinity gradient was observed. It was responsible for approximately 32% loss of Hg from the water column with a simultaneous increase in Hg concentration in sediments. In consequence, it significantly limited the transport of Hg to the open Baltic Sea. The assimilation of Hg by marine plankton was also observed. As riverine organic matter stimulated the growth of marine plankton, they actively accumulated Hg and then transferred this metal to the higher trophic level. In both of the river mouths the processes affected the fate of Hg in a similar way. We therefore concluded that the size of the river did not affect the Hg transformation in the river mouth. However, the area of the river catchment, depth of the mouth and hydrological conditions had a significant impact on Hg cycling in the coastal zone in the vicinity of the river mouth.

Coprecipitation of Mercury from Natural Iodine-Containing Seawater for Accurate Isotope Measurement.

Oceans play a key role in the global mercury (Hg) cycle, but studies on Hg isotopes in seawater are rare due to the extremely low Hg concentration and the lack of a good preconcentration method. Here, we introduce a new coprecipitation method for separating and preconcentrating Hg from seawater for accurate isotope measurement. The coprecipitation was achieved by sequential addition of 0.5 mL of 0.5 M CuSO4, 1 mL of 0.5 M Na2S, and 1 mL of 0.5 M CuSO4 reagents, which allowed for quantitatively precipitating Hg from up to 10 L of seawater. The protocol was validated by testing synthetic solutions with varying Hg and iodide (I-) concentrations and by comparing the reaction times of various reagents added. The method resulted in a quantitative recovery of 98 ± 12% (n = 32, two standard deviations, 2 SD) and a relatively low procedure blank (103 pg of Hg, n = 8). The precipitates were filtrated and analyzed for Hg isotopes. Repeated measurements of synthetic seawaters spiked with certificated standard materials (NIST 3133 and 3177) using the entire method gave identical Hg isotope ratios with near-quantitative Hg recovery, indicating no isotope fractionation during preconcentration. A total of six nearshore seawater samples from the Yellow Sea and the Bohai Sea (China) were analyzed using the coprecipitation method. The data showed a large fractionation of Hg isotopes and revealed the possible impact of both atmospheric and anthropogenic inputs to the coastal seawater Hg budget, implying the potential application of this method in studying marine Hg systematics and global Hg cycling.

Identification of mercury-containing nanoparticles in the liver and muscle of cetaceans

Natural mercury-containing nanoparticles (Hg-NPs) have been found in the environment, but the information for Hg-NPs in organisms was still limited. Clarifying the unique roles of Hg-NPs in organisms is crucial to fully understand the health risks of Hg. Herein, liver and muscle tissues of cetaceans were collected to identify the presence and characteristics of Hg-NPs. We found that methylmercury (MeHg) was the dominant species of Hg in muscles, while inorganic Hg (IHg) accounted for 84.4–99.0% (average 94.0%) of Hg in livers. By using transmission electron microscopy (TEM), size exclusion chromatography coupled with inductively coupled plasma mass spectrometry (SEC-ICPMS) and single particle ICPMS (sp-ICPMS), large amounts (9–161 μg/g) of Hg-NPs in livers and small amounts (0.1–0.4 μg/g) in muscles were observed, indicating that Hg-NPs was an important form of Hg in livers. Both small sized (5–40 nm) and large sized (>100 nm) Hg-NPs were identified, which were mainly complexed with selenium (Se) and sulfur (S) as well as a few cadmium (Cd), lead (Pb) and silver (Ag). This study provided direct evidence of Hg-NPs in marine mammals as well as their chemical form and size distribution, which are helpful for further understanding the biogeochemical cycle and health risk of Hg.

Characterization of potential mercury contamination in the ASGM area of Mandailing Natal, North Sumatera

A large amount of Hg is used for gold extraction through the amalgamation process in the Mandailing Natal derived from artisanal and small-scale gold mining (ASGM) area located in the North Sumatera Province, Indonesia. The objective of this work was to characterize the potential contamination of total Hg in water, sediments, and soil in this ASGM area. Sampling was done in two locations in West Panyabungan and Huta Bargot Districts using grab sampling method. Results showed that accumulation of Hg in the studied soils and sediments was the highest, but Hg in aquatic solution was below the detection limit of the analytical method of the studied community wells and rivers. The highest concentration of Hg was found in the river sediments of the Saba Padang irrigation (1,63 mg/kg), and in the soil of the plantation area of Huta Bargot (1,62 mg/kg) respectively. These concentrations may pose a serious problem for aquatic and land life, related ecosystems, and human health. For further study, there is a need to study Hg availability in riverine biota to better understand the cycling of Hg in this ASGM area. Understanding the ecological impacts can assist in the prioritizing of impact mitigation efforts.

Mangrove sediments as long-term mercury sinks: Evidence from millennial to decadal time scales

The mercury (Hg) cycle in estuaries has been globally discussed, although Holocene deposition in mangrove sediments remains unknown. Herein, a sediment core from a mangrove system in southeastern Brazil was 14C-dated to evaluate millennial Hg deposition. The highest Hg concentrations (1010–2540 ng g−1) in surface sediments were explained by emissions from a chlor-alkali industry (1964 CE). However, Hg levels were also high in pre-industrial periods, associated to fine grain-size and algal organic deposition. Less anomalous Hg concentrations in bottom sediments indicate Holocene ages (~1940–3324 cal yr BP), potentially associated to Serra do Mar mountains weathering. This study reveals the capacity of mangrove to retain Hg over millennial time scales, acting as significant and long-term Hg sinks. Therefore, the use of Hg as an Anthropocene marker must be considered cautiously in coastal systems that act as Hg sinks in times when environmental changes were not caused by human activities.

Characteristics of Hg concentrations and isotopes in terrestrial and marine facies across the end-Permian mass extinction

The end Permian mass extinction (EPME) is the greatest among the “Big Five” extinctions of the Phanerozoic, and is believed to have been triggered primarily by the Siberian Traps Large Igneous Province (STLIP). This hypothesis is supported by the temporal correlation of STLIP with the EPME by radiometric ages and Hg enrichments in sedimentary rocks. However, how signatures of volcanic Hg emissions are preserved in sediments, and how this may vary from deep basin to shelf to terrestrial successions, remain unclear. To examine variability in the Hg record in different environments, we systematically measured organic carbon isotopes, Hg concentrations and isotopes, major elements, and total organic carbon (TOC) contents from: 1) a terrestrial section at Chahe, 2) a marine-nonmarine transitional section at Jinzhong both in Guizhou Province, Southwest China. Results show that Hg versus TOC and Hg versus Al exhibit no correlation through the terrestrial section at Chahe, whereas there is positive correlation in the transitional Jinzhong section. These relationships indicate that organic matter and clay minerals would not affect Hg fluctuations on land, but dominates Hg sequestration in transitional settings. Thus, Hg/TOC along with Hg/Al ratios were able to be employed to recognize abnormal Hg deposition in Jinzhong, and Hg concentrations were utilized to examine records of Hg enrichments in Chahe. The studied sections all show synchronous changes between carbon isotopic perturbations and Hg deposition events with first Hg enrichment and associated negative carbon isotopic negative excursion coinciding with terrestrial ecological disturbance and with a second Hg enrichment corresponding to the largest carbon isotopic negative excursion and marine biological crisis. These trends across the Permian-Triassic boundary are also observed in other 13 sections around the world, indicating a common source that injected massive CO 2 and Hg, impacting the global C and Hg cycles. Hg isotope (Δ 199 Hg values) of the first peak in Hg concentrations have similar characteristics in the terrestrial Chahe and transitional Jinzhong sections along with other sections (e.g., Shangsi and Chaohu in South China, Guryul Ravine section in India and Buchanan Lake section in Canada), all showing positive values, indicative of predominantly atmospheric-derived volcanic Hg. In contrast, Δ 199 Hg values at the second Hg peak, corresponding to the marine extinction horizon in Chahe and Jinzhong, are negative. This relationship indicates an elevated involvement of terrestrial sourced Hg into the terrestrial or nearshore aquatic realm due to increased weathering after the collapse of terrestrial ecosystem. Our study suggests that the STLIP could have two pulses of volatile eruptions that released massive CO 2 and Hg, resulting in two pulses of Hg enrichments coupled with negative carbon isotopic excursions coinciding with end Permian terrestrial and marine extinction events. • Two pulses of Hg enrichments coinciding with the end Permian terrestrial and marine extinction events • Positive Δ 199 Hg values at the first Hg enrichment, indicate a predominant atmospheric-derived signature of volcanic Hg • Δ 199 Hg values at the second Hg peak are negative, indicating an elevated involvement of terrestrial sourced Hg.

Gaseous Elemental Mercury Exchange Fluxes over Air-Soil Interfaces in the Degraded Grasslands of Northeastern China.

Simple SummaryThis study investigated the gaseous elemental mercury exchange fluxes over Artemisia anethifolia coverage and removal and bare soil using a dynamic flux chamber attached to the LumexR RA915+ Hg analyzer during the growing season from May to September of 2018, in which the interactive effects of plant coverage and meteorological conditions were highlighted. The results showed that the net emissions from the soil to the atmosphere, which varied diurnally, with releases occurring during the daytime hours and depositions occurring during the nighttime hours. Significant differences were observed in the fluxes between the vegetation coverage and removal during the growing months. In addition, it was determined that the mercury fluxes were positively correlated with the solar radiation and air/soil temperature levels and negatively correlated with the air humidity and soil moisture. The grassland soil served as both a source and a sink for atmospheric mercury, depending on the season and meteorological factors. The plants played an important inhibiting role in the mercury exchanges between the soil and the atmosphere. This research will potentially assist in the development of more accurate local and regional estimates of mercury emissions from degraded grassland areas and the terrestrial environment as a whole.Mercury (Hg) is a global pollutant that may potentially have serious impacts on human health and ecologies. The gaseous elemental mercury (GEM) exchanges between terrestrial surfaces and the atmosphere play important roles in the global Hg cycle. This study investigated GEM exchange fluxes over two land cover types (including Artemisia anethifolia coverage and removal and bare soil) using a dynamic flux chamber attached to the LumexR RA915+ Hg analyzer during the growing season from May to September of 2018, in which the interactive effects of plant coverage and meteorological conditions were highlighted. The daily mean ambient levels of GEM and the total mercury concentrations of the soil (TSM) were determined to be 12.4 ± 3.6 to 16.4 ± 5.6 ng·m−3 and 32.8 to 36.2 ng·g−1, respectively, for all the measurements from May to September. The GEM exchange fluxes (ng·m−2·h−1) during the five-month period for the three treatments included the net emissions from the soil to the atmosphere (mean 5.4 to 7.1; range of −27.0 to 47.3), which varied diurnally, with releases occurring during the daytime hours and depositions occurring during the nighttime hours. Significant differences were observed in the fluxes between the vegetation coverage and removal during the growing months (p < 0.05). In addition, it was determined that the Hg fluxes were positively correlated with the solar radiation and air/soil temperature levels and negatively correlated with the air relative humidity and soil moisture under all the conditions (p < 0.05). Overall, the results obtained in this study demonstrated that the grassland soil served as both a source and a sink for atmospheric Hg, depending on the season and meteorological factors. Furthermore, the plants played an important inhibiting role in the Hg exchanges between the soil and the atmosphere.

Oceanic mercury recycled into the mantle: Evidence from positive Δ199Hg in lamprophyres

Due to mercury (Hg) is a global pollutant, the biogeochemistry of Hg in Earth's surface environment has been well studied. However, the cycling of Hg in interior reservoirs remains less clear, limiting our understanding of the global Hg geochemical cycle. Here, we use Hg isotopes to constrain the sources of Hg in typical alkaline lamprophyres in South China: the Early Ordovician lamprophyres in the Zhenyuan area and the Late Cretaceous lamprophyres in the Zhenfeng area. Lamprophyres from both areas are enriched in large-ion-lithophile elements (LILEs) and light rare earth elements (LREEs) but depleted in high-field-strength elements (HSFEs), typical of subduction-related igneous rocks. The Early Ordovician and Late Cretaceous lamprophyres show significantly positive to near-zero Δ199Hg values of 0.18 to 0.37‰ and − 0.08 to 0.36‰, respectively. The positive Δ199Hg values are consistent with that reported for marine sediments and seawaters, suggesting Hg in these lamprophyres was sourced from marine reservoirs. This study suggests a heterogeneous distribution of Hg in the mantle and demonstrates that subducted marine materials can have contributed a substantial amount of Hg into the mantle.

Relationships between atmospheric mercury and optical properties of spring outflow aerosols from Southeast Asia

Southeast Asia is a major biomass burning (BB) source area and BB has been identified as an important source of mercury (Hg) and aerosols to the atmosphere. Previous studies found correlations between atmospheric Hg and Delta-C (BC370–BC880) during the BB episodes in low-elevation BB source areas; however, whether this relationship persists during long-range transport remains unknown. Lulin Atmospheric Background Station (LABS), a high mountain background site in central Taiwan, has monitored the impact of BB long-range transports from Southeast Asia on atmospheric Hg and aerosols in downwind areas since 2006 and 2008, respectively. As such, these data provide an opportunity to investigate the relationship between atmospheric Hg (PBM and GOM) and aerosol optical properties, such as Delta-C and absorption Ångström exponent (AAE370-880). In this study, three long-range transport BB events were observed at LABS in the springtime during 2014–2016. Significant positive correlations with PBM/GOM were observed for Delta-C and (R2 = 0.34–0.51) and AAE370-880 (R2 = 0.41–0.54) during the BB events, while poor correlations were shown under non-BB episodes. Additionally, the positive correlation between PBM and AAE370-880 suggests that the Hg(II) may be preferably absorbed onto organic aerosols or originated from the same emission sources. This study demonstrated that AAE370-880 can be used to identify the source of Hg(II) from BB long-range transport. In addition, our results also indicated the influences of aerosol chemical compositions on the partitioning of Hg(II), which is important to further the understanding of atmospheric Hg cycling.

Mercury accumulation response of rice plant (Oryza sativa L.) to elevated atmospheric mercury and carbon dioxide

New observations and updated models now suggest terrestrial ecosystems are net sink of atmospheric mercury (Hg), and the critical constrained process to identify the strengths of terrestrial sink is whether the large amount of Hg stored in vegetation originates from the soil as well as from the atmosphere. In this study, field open top chambers (OTCs) experiments reveal that rice plant can assimilate gaseous elemental mercury (GEM, Hg0) from the atmosphere through stomata, and Hg concentrations in rice leaves, upper and bottom stalks and grains increased with Hg0 levels in air, showing significantly quadratic linear relationships. Coupling field stable isotope soil amendment experiments, atmospheric source of Hg in rice plant is quantified with more than 90% of Hg accumulation in rice aboveground biomass from air and approximately 80% of rice root Hg from soil. Furthermore, elevated atmospheric carbon dioxide (CO2) exposure led to lower Hg concentration in rice tissues through reduction stomatal conductance of rice leaf, and subsequently impact the capacity of Hg storage in rice aboveground parts from the atmosphere. The findings from experiments provide a foundation for future quantification of atmospheric sink of crops in local and larger scales and comprehensive evaluation atmosphere - terrestrial processes and exposure risks in the global Hg cycling.

Critical Observations of Gaseous Elemental Mercury Air‐Sea Exchange

AbstractAir‐sea exchange of gaseous elemental mercury (Hg0) is not well constrained, even though it is a major component of the global Hg cycle. Lack of Hg0 flux measurements to validate parameterizations of the Hg0 transfer velocity contributes to this uncertainty. We measured the Hg0 flux on the Baltic Sea coast using micrometeorological methods (gradient‐based and relaxed eddy accumulation [REA]) and also simulated the flux with a gas exchange model. The coastal waters were typically supersaturated with Hg0 (mean ± 1σ = 13.5 ± 3.5 ng m−3; ca. 10% of total Hg) compared to the atmosphere (1.3 ± 0.2 ng m−3). The Hg0 flux calculated using the gas exchange model ranged from 0.1–1.3 ng m−2 h−1 (10th and 90th percentile) over the course of the campaign (May 10–June 20, 2017) and showed a distinct diel fluctuation. The mean coastal Hg0 fluxes determined with the two gradient‐based approaches and REA were 0.3, 0.5, and 0.6 ng m−2 h−1, respectively. In contrast, the mean open sea Hg0 flux measured with REA was larger (6.3 ng m−2 h−1). The open sea Hg0 flux indicated a stronger wind speed dependence for the Hg0 transfer velocity compared to commonly used parameterizations. Although based on a limited data set, we suggest that the wind speed dependence of the Hg0 transfer velocity is more consistent with gases that have less water solubility than CO2 (e.g., O2). These pioneering flux measurements using micrometeorological techniques show that more such measurements would improve our understanding of air‐sea Hg exchange.

Atmospheric particle-bound mercury in the northern Indo-Gangetic Plain region: Insights into sources from mercury isotope analysis and influencing factors

Lumbini is a world heritage site located in the southern plains region of Nepal, and is regarded as a potential site for evaluating transboundary air pollution due to its proximity to the border with India. In this study, 82 aerosol samples were collected between April 2013 and July 2014 to investigate the levels of particulate-bound mercury (PBM) and the corresponding seasonality, sources, and influencing factors. The PBM concentration in total suspended particulate (TSP) matter ranged from 6.8 pg m−3 to 351.7 pg m−3 (mean of 99.7 ± 92.6 pg m−3), which exceeded the ranges reported for remote and rural sites worldwide. The Hg content (PBM/TSP) ranged from 68.2 ng g−1 to 1744.8 ng g−1 (mean of 446.9 ± 312.7 ng g−1), indicating anthropogenic enrichment. The PBM levels were higher in the dry season (i.e., winter and the pre-monsoon period) than in the wet season (i.e., the monsoon period). In addition, the δ202Hg signature indicated that waste/coal burning and traffic were the major sources of Hg in Lumbini during the pre-monsoon period. Meanwhile, precipitation occurring during photochemical processes in the atmosphere may have been responsible for the observed Δ199Hg values in the aerosol samples obtained during the monsoon period. The PBM concentration was influenced mostly by the resuspension of polluted dust during dry periods and crop residue burning during the post-monsoon period. The estimated PBM deposition flux at Lumbini was 15.7 μg m−2 yr−1. This study provides a reference dataset of atmospheric PBM over a year, which can be useful for understanding the geochemical cycling of Hg in this region of limited data.

Mass-Independent Fractionation of Even and Odd Mercury Isotopes during Atmospheric Mercury Redox Reactions.

Mass-independent fractionation (MIF) of stable even mass number mercury (Hg) isotopes is observed in rainfall and gaseous elemental Hg0 globally and is used to quantify atmospheric Hg deposition pathways. The chemical reaction and underlying even-Hg MIF mechanism are unknown however and speculated to be caused by Hg photo-oxidation on aerosols at the tropopause. Here, we investigate the Hg isotope composition of free tropospheric Hg0 and oxidized HgII forms at the high-altitude Pic du Midi Observatory. We find that gaseous oxidized Hg has positive Δ199Hg, Δ201Hg, and Δ200Hg and negative Δ204Hg signatures, similar to rainfall Hg, and we document rainfall Hg Δ196Hg to be near zero. Cloud water and rainfall Hg show an enhanced odd-Hg MIF of 0.3‰ compared to gaseous oxidized HgII, potentially indicating the occurrence of in-cloud aqueous HgII photoreduction. Diurnal MIF observations of free tropospheric Hg0 show how net Hg0 oxidation in high-altitude air masses leads to opposite even- and odd-MIF in Hg0 and oxidized HgII. We speculate that even-Hg MIF takes place by a molecular magnetic isotope effect during HgII photoreduction on aerosols that involves magnetic halogen nuclei. A Δ200Hg mass balance suggests that global Hg deposition pathways in models are likely biased toward HgII deposition. We propose that Hg cycling models could accommodate the Hg-isotope constraints on emission and deposition fluxes.

Patterning total mercury distribution in coastal podzolic soils from an Atlantic area: Influence of pedogenetic processes and soil components

Soils are the main Hg reservoir in the terrestrial ecosystems where it is deposited via wet or dry deposition and litterfall. Once on the soil surface, different biogeochemical routes will determine the fate of Hg and the role of terrestrial ecosystems as a Hg source or sink. The specific chemical and physical characteristics of Podzols and podzolic soils contribute to the accumulation of Hg in their illuvial horizons, avoiding its leaching to groundwater. The geographical location, state of pedogenesis, soil age, abundance of carrier phases and physical properties can affect the presence and distribution of Hg in soils. Therefore, understand and relate these factors with the behavior of Hg in Podzols and podzolic soils is key to define the role of this type of soil in the terrestrial Hg cycle. In this work, ten podzolic soil profiles were collected in an Atlantic coastal forest area of Portugal and analyzed for the main physico-chemical properties and Hg content to assess the influence of the intensity of podzolization in the Hg depth distribution. Three different patterns of Hg distribution in the studied Podzols, depending on the predominance of atmospheric deposition or the intensity of podzolization, have been defined. The pattern I showed the maximum Hg contents in the surface A horizons (12.9–23.5 µg kg−1), pattern II exhibited the highest peaks in the subsurface illuvial horizons (2.3–17.3 µg kg−1) and pattern III presented an even distribution of Hg through the soil profile. We found that dissolved organic matter (DOM) is the main carrier of Hg in the A and E horizons, whereas metal(Al, Fe)-humus complexes and/or oxyhydroxides contribute to immobilizing Hg in the illuvial horizons (Bh, Bs and Bhs). The principal component regression (PCR) analysis predicted satisfactorily the Hg distribution through soil organic matter and Al and Fe oxyhydroxides. The Hg immobilized in the subsurface layers of Podzols is retained in the long term, avoiding its migration to other components of terrestrial ecosystems where it could cause serious environmental damage such as groundwater and superficial waters.

Biogeochemical influences on net methylmercury formation proxies along a peatland chronosequence

A geographically constrained chronosequence of peatlands divided into three age classes (young, intermediate and old) was used to explore the role of biogeochemical influences, including electron donors and acceptors as well as chemical speciation of inorganic mercury (Hg(II)), on net formation of methylmercury (MeHg) as approximated by the fraction of MeHg to total mercury (THg) in the peat soil. We hypothesized that removing vascular plants would reduce availability of electron donors and thus net MeHg formation. However, we found no effect of the vascular plant removal. The sum of the potential electron donors (acetate, lactate, propionate and oxalate), the electron donation proxy organic C/Organic N, and the potential electron acceptors (Fe(III), Mn and sulfate) in porewater all showed significant correlations with the net MeHg formation proxies in peat soil (MeHg concentration and %MeHg of THg). Thus differences in both electron donor and acceptor availability may be contributing to the pattern of net MeHg formation along the chronosequence. In contrast, Hg(II) concentrations in peat porewater showed small differences along the gradient. A chemical speciation model successfully predicted the solubility of Hg and MeHg in the porewater. The modeling pointed to an enhanced concentration of Hg-polysulfide species in the younger peatlands as a potential factor behind increased Hg(II) solubility and methylation in the more nutrient-rich peatlands. This work contributes to the understanding of Hg and MeHg cycling in peatlands which can help guide mitigation measures to reduce aquatic MeHg biomagnification in peatland dominated landscapes.

Mercury cycling during acid rain recovery at the forested Lesní potok catchment, Czech Republic

AbstractFrom 2011 to 2019, mercury (Hg) stores and fluxes were studied in the small forested catchment Lesní potok (LES) in the central Czech Republic using the watershed mass balance approach together with internal measurements. Mean input fluxes of Hg via open bulk deposition, beech throughfall and spruce throughfall during the periodwere 2.9, 3.9 and 7.6 μg m−2 year−1, respectively. These values were considerably lower than corresponding deposition Hg fluxes reported in the early years of the 21st century from catchments in Germany. Current bulk precipitation inputs at unimpacted Czech mountainous sites were lower than those in Germany. The largest Hg inputs to the catchment were via litterfall, averaging 22.6 and 17.8 μg m−2 year−1 for beech and spruce stands. The average Hg input, based on the sum of mean litterfall and throughfall deposition, was 23.0 μg m−2 year−1, compared to the estimated Hg output in runoff of 0.5 μg m−2 year−1, which is low compared to other reported values. Thus, only ~2% of Hg input is exported in stream runoff. Stream water Hg was only weakly related to dissolved organic carbon (DOC) but both concentrations were positively correlated with water temperature. The estimated total soil Hg pool averaged 47.5 mg m−2, only 4% of which was in the O‐horizon. Thus Hg in the O‐horizon pool represents 72 years of deposition at the current input flux and 3800 years of export at the current runoff flux. Age‐dating by 14C suggested that organic soil contains Hg from recent deposition, while mineral soil at 40–80 cm depth contained 4400‐year old carbon, suggesting the soil had accumulated atmospheric Hg inputs through millennia to reach the highest soil Hg pool of the soil profile. These findings suggest that industrial era intensification of the Hg cycle is superimposed on a slower‐paced Hg cycle during most of the Holocene.

Mercury stable isotopes reveal the sources and transformations of atmospheric Hg in the high Arctic

The Arctic plays a critical role in the global Hg cycle as both a sink of Hg and, in response to rapid global warming, an emerging source of Hg due to release from permafrost and glaciers. Human activities have led to significant mercury (Hg) contamination in the Arctic over many decades, potentially impacting the health of Arctic ecosystems and indigenous people. Thus, it is crucial to understand the sources and transformations of Hg in the Arctic in order to predict how Hg behaves as emissions and the global climate change. Here we examine Hg stable isotopes in atmospheric particulate Hg (PHg), gaseous elemental Hg (GEM) and surface snow in the high Arctic (Alert, Canada) during polar spring from 2011 to 2015, in order to trace the sources of atmospheric Hg and its fate in Arctic surface environment. Isotope signatures of GEM (δ202Hg = 0.67 ± 0.24‰, Δ199Hg = −0.23 ± 0.04‰, Δ200Hg = −0.06 ± 0.04‰, 2SD) are similar to the average Northern Hemisphere background, suggesting that GEM in the high Arctic atmosphere is well mixed with those from lower latitudes. Surprisingly, the isotope composition of PHg has negative Δ199Hg, which is similar to GEM but distinct from the positive Δ199Hg typically observed for oxidized Hg species elsewhere. Furthermore, Hg in surface snow shows more negative MIF than PHg, indicating post-depositional loss of Hg via photoreduction. We suggest that PHg is primarily sourced from in situ oxidation of GEM and subsequent scavenging by particles, and thus inherited the isotope composition of GEM when the oxidation is near-complete. The photoreduction re-emission of Hg from snow is strongly affected by Hg speciation, but the overall extent of re-emission (20 ± 31%) is lower than previous estimations for other locations, suggesting potentially a greater loading of Hg to Arctic ecosystem via snowmelt.

Katabatic Wind and Sea-Ice Dynamics Drive Isotopic Variations of Total Gaseous Mercury on the Antarctic Coast.

Clarifying the sources and fates of atmospheric mercury (Hg) in the Antarctic is crucial to understand the global Hg circulation and its impacts on the fragile ecosystem of the Antarctic. Herein, the annual variations in the isotopic compositions of total gaseous Hg (TGM), with 5-22 days of sampling duration for each sample, were presented for the first time to provide isotopic evidence of the sources and environmental processes of gaseous Hg around the Chinese Great Wall Station (GWS) in the western Antarctic. Different from the Arctic tundra and lower latitude areas in the northern hemisphere, positive δ202Hg (0.58 ± 0.21‰, mean ± 1SD) and negative Δ199Hg (-0.30 ± 0.10‰, mean ± 1SD) in TGM at the GWS indicated little impact from the vegetation-air exchange in the Antarctic. Correlations among TGM Δ199Hg, air temperature, and ozone concentrations suggested that enhanced katabatic wind that transported inland air masses to the continental margin elevated TGM Δ199Hg in the austral winter, while the surrounding marine surface emissions controlled by sea-ice dynamics lowered TGM Δ199Hg in the austral summer. The oxidation of Hg(0) might elevate Δ199Hg in TGM during atmospheric Hg depletion events but have little impact on the seasonal variations of atmospheric Hg isotopes. The presented atmospheric Hg isotopes were essential to identify the transport and transformation of atmospheric Hg and further understand Hg cycling in the Antarctic.

Isotope Fractionation from In Vivo Methylmercury Detoxification in Waterbirds

Author(s): Poulin, BA; Janssen, SE; Rosera, TJ; Krabbenhoft, DP; Eagles-Smith, CA; Ackerman, JT; Stewart, AR; Kim, E; Baumann, Z; Kim, JH; Manceau, A | Abstract: The robust application of stable mercury (Hg) isotopes for mercury source apportionment and risk assessment necessitates the understanding of mass-dependent fractionation (MDF) as a result of internal transformations within organisms. Here, we used high energy-resolution X-ray absorption near edge structure spectroscopy and isotope ratios of total mercury (δ202THg) and methylmercury (δ202MeHg) to elucidate the chemical speciation of Hg and the resultant MDF as a result of internal MeHg demethylation in waterbirds. In three waterbirds (Clark's grebe, Forster's tern, and south polar skua), between 17 and 86% of MeHg was demethylated to inorganic mercury (iHg) species primarily in the liver and kidneys as Hg-tetraselenolate [Hg(Sec)4] and minor Hg-dithiolate [Hg(SR)2] complexes. Tissular differences between δ202THg and δ202MeHg correlated linearly with %iHg [Hg(Sec)4 + Hg(SR)2] and were interpreted to reflect a kinetic isotope effect during in vivo MeHg demethylation. The product-reactant isotopic enrichment factor (ϵp/r) for the demethylation of MeHg → Hg(Sec)4 was -2.2 ± 0.1‰. δ202MeHg values were unvarying within each bird, regardless of Hg(Sec)4 abundance, indicating fast internal cycling or replenishment of MeHg relative to demethylation. Our findings document a universal selenium-dependent demethylation reaction in birds, provide new insights on the internal transformations and cycling of MeHg and Hg(Sec)4, and allow for mathematical correction of δ202THg values as a result of the MeHg → Hg(Sec)4 reaction.