Biogeochemical Cycling Of Hg Research Articles

Terrestrial input and biological processes drive varying mineral/organic matrix-related mercury sequestration and deposition in the East Siberian Arctic Shelf

Thawing Arctic permafrost is releasing massive amounts of terrestrial mercury (Hg) into the Arctic shelf, which is expected to form a Hg sink in sediments. Here we analyzed the coupling roles of terrestrial input and biological processes in varying mineral/organic matrix-related Hg sequestration and deposition on the East Siberian Arctic shelf (ESAS), using Pearson and partial correlation analysis. Results show that the occurrence of Hg in the Laptev Sea under the Lena River-dominated input exhibits strong correlations with the organic carbon (OC) content and sediment specific surface area. This indicates that the prolonged riverine loading processes facilitate Hg sequestration by organic/mineral matrices and these land-derived mineral-OC-Hg complexes remain stable during cross-shelf transportation. By contrast, the comparative samples with coastal erosion-dominated Hg input in the western East Siberian Sea shows limited Hg complexation, primarily due to the absence of regulation by riverine processes and/or the high sedimentation rates. The correlations between Hg and OC source proxies (δ13C and lignin) indicate that these matrix-free Hg could be more readily sequestrated by the marine OC, which facilitates its deposition via the biological pump. While unexpectedly low Hg abundance in the Chukchi Sea may indicate that the effective biological scavenging of Hg sequestration could be constrained by insufficient terrestrial Hg input. Our findings of the matrix-related Hg sequestration by mineral and/or OC association in this study may shed light on the biogeochemical cycle of Hg in the Arctic aquatic regime, which could reduce the methylmercury formation in water column, and the methylation within sediments needs further exploration.

Mediterranean Marine Mammals: Possible Future Trends and Threats Due to Mercury Contamination and Interaction with Other Environmental Stressors.

Despite decreasing anthropogenic mercury (Hg) emissions in Europe and the banning and restriction of many persistent organic pollutants (POPs) under the Stockholm Convention, Mediterranean marine mammals still have one of the highest body burdens of persistent pollutants in the world. Moreover, the Mediterranean basin is one of the most sensitive to climate change, with likely changes in the biogeochemical cycle and bioavailability of Hg, primary productivity, and the length and composition of pelagic food webs. The availability of food resources for marine mammals is also affected by widespread overfishing and the increasing number of alien species colonizing the basin. After reporting the most recent findings on the biogeochemical cycle of Hg in the Mediterranean Sea and the physico-chemical and bio-ecological factors determining its exceptional bioaccumulation in odontocetes, this review discusses possible future changes in the bioavailability of the metal. Recent ocean-atmosphere-land models predict that in mid-latitude seas, water warming (which in the Mediterranean is 20% faster than the global average) is likely to decrease the solubility of Hg and favor the escape of the metal to the atmosphere. However, the basin has been affected for thousands of years by natural and anthropogenic inputs of metals and climate change with sea level rise (3.6 ± 0.3 mm year-1 in the last two decades), and the frequency of extreme weather events will likely remobilize a large amount of legacy Hg from soils, riverine, and coastal sediments. Moreover, possible changes in pelagic food webs and food availability could determine dietary shifts and lower growth rates in Mediterranean cetaceans, increasing their Hg body burden. Although, in adulthood, many marine mammals have evolved the ability to detoxify monomethylmercury (MMHg) and store the metal in the liver and other organs as insoluble HgSe crystals, in Mediterranean populations more exposed to the metal, this process can deplete the biological pool of Se, increasing their susceptibility to infectious diseases and autoimmune disorders. Mediterranean mammals are also among the most exposed in the world to legacy POPs, micro- and nanoplastics, and contaminants of emerging interest. Concomitant exposure to these synthetic chemicals may pose a much more serious threat than the Se depletion. Unfortunately, as shown by the literature data summarized in this review, the most exposed populations are those living in the NW basin, the main feeding and reproductive area for most Mediterranean cetaceans, declared a sanctuary for their protection since 2002. Thus, while emphasizing the adoption of all available approaches to mitigate anthropogenic pressure with fishing and maritime traffic, it is recommended to direct future research efforts towards the assessment of possible biological effects, at the individual and population levels, of chronic and simultaneous exposure to Hg, legacy POPs, contaminants of emerging interest, and microplastics.

The coupling effect promotes superoxide radical production in the microalgal-fungal symbiosis systems: Production, mechanisms and implication for Hg(II) reduction

Redox transformation of mercury (Hg) is critical for Hg exchange at the air-water interface. However, the superoxide radicals (O2•─) contribution of microalgal-fungal symbiotic systems in lake water to Hg(II) reduction is mainly unknown. Here, we studied the enhanced potential for O2•─ production by the coupling effect between microalgae and fungi. The relationships between microenvironment, microorganisms, and O2•─ production were also investigated. Furthermore, the implication of O2•─ for Hg(II) reduction was explored. The results showed that the coupling effect of microalgae and fungi enhanced O2•─ generation in the symbiotic systems, and the O2•─ generation peaked on day 4 in the lake water at 160.51 ± 13.06–173.28 ± 18.21 μmol/kg FW (fresh weight). In addition, O2•− exhibited circadian fluctuations that correlated with changes in dissolved oxygen content and redox potential on the inter-spherical interface of microalgal-fungal consortia. Partial least squares path modeling (PLS-PM) indicates that O2•─ formation was primarily associated with microenvironmental factors and microbial metabolic processes. The experimental results suggest that O2•─ in the microalgal-fungal systems could mediate Hg(II) reduction, promoting Hg conversion and cycling. The findings highlight the importance of microalgae and fungal symbiotic systems in Hg transformation in aquatic environments.

Measurement of Atmospheric Mercury: Current Limitations and Suggestions for Paths Forward.

Mercury (Hg) researchers have made progress in understanding atmospheric Hg, especially with respect to oxidized Hg (HgII) that can represent 2 to 20% of Hg in the atmosphere. Knowledge developed over the past ∼10 years has pointed to existing challenges with current methods for measuring atmospheric Hg concentrations and the chemical composition of HgII compounds. Because of these challenges, atmospheric Hg experts met to discuss limitations of current methods and paths to overcome them considering ongoing research. Major conclusions included that current methods to measure gaseous oxidized and particulate-bound Hg have limitations, and new methods need to be developed to make these measurements more accurate. Developing analytical methods for measurement of HgII chemistry is challenging. While the ultimate goal is the development of ultrasensitive methods for online detection of HgII directly from ambient air, in the meantime, new surfaces are needed on which HgII can be quantitatively collected and from which it can be reversibly desorbed to determine HgII chemistry. Discussion and identification of current limitations, described here, provide a basis for paths forward. Since the atmosphere is the means by which Hg is globally distributed, accurately calibrated measurements are critical to understanding the Hg biogeochemical cycle.

Global Distribution of Mercury in Foliage Predicted by Machine Learning.

Foliar assimilation of elemental mercury (Hg0) from the atmosphere plays a critical role in the global Hg biogeochemical cycle, leading to atmospheric Hg removal and soil Hg insertion. Recent studies have estimated global foliar Hg assimilation; however, large uncertainties remained due to coarse accounting of observed foliar Hg concentrations, posing a substantial challenge in constraining the global Hg budget. Here, we integrated a comprehensive observation database of foliar Hg concentrations and machine learning algorithms to predict the first spatial distribution of foliar Hg concentrations on a global scale, contributing to the first estimate of global Hg pools in foliage. The global average of foliar Hg concentrations was estimated to be 24.0 ng g-1 (7.5-56.5 ng g-1), and the global total in foliar Hg pools reached 4561.3 Mg (1455.2-9062.8 Mg). The spatial distribution showed the hotspots in tropical regions, including the Amazon, Central Africa, and Southeast Asia. A range of 2268.5-2727.0 Mg yr-1 was estimated for annual foliar Hg assimilation accounting for the perennial continuous assimilation by evergreen vegetation foliage. The first spatial maps of foliar Hg concentrations and Hg pools may aid in understanding the global biogeochemical cycling of Hg, especially in the context of climate change and global vegetation greening.

Riparian trees in mercury contaminated riverbanks: An important resource for sustainable remediation management

Mining operations generate sediment erosion rates above those of natural landscapes, causing persistent contamination of floodplains. Riparian vegetation in mine-impacted river catchments plays a key role in the storage/remobilization of metal contaminants. Mercury (Hg) pollution from mining is a global environmental challenge. This study provides an integrative assessment of Hg storage in riparian trees and soils along the Paglia River (Italy) which drains the abandoned Monte Amiata Hg mining district, the 3rd former Hg producer worldwide, to characterize their role as potential secondary Hg source to the atmosphere in case of wildfire or upon anthropic utilization as biomass. In riparian trees and nearby soils Hg ranged between 0.7 and 59.9 μg/kg and 2.2 and 52.8 mg/kg respectively. In trees Hg concentrations were below 100 μg/kg, a recommended Hg limit for the quality of solid biofuels. Commercially, Hg contents in trees have little impact on the value of the locally harvested biomass and pose no risk to human health, although higher values (195–738 μg/kg) were occasionally found. In case of wildfire, up to 1.4*10−3 kg Hg/ha could be released from trees and 27 kg Hg/ha from soil in the area, resulting in an environmentally significant Hg pollution source. Data constrained the contribution of riparian trees to the biogeochemical cycling of Hg highlighting their role in management and restoration plans of river catchments affected by not-remediable Hg contamination. In polluted river catchments worldwide riparian trees represent potential sustainable resources for the mitigation of dispersion of Hg in the ecosystem, considering i) their Hg storage capacity, ii) their potential to be used for local energy production (e.g. wood-chips) through the cultivation and harvesting of biomasses and, iii) their role in limiting soil erosion from riparian polluted riverbanks, probably representing the best pragmatic choice to minimize the transport of toxic elements to the sea.

Granite weathering profiles accumulate vegetation-derived mercury

Weathering of silicate rocks, particularly granitic rocks, generates the pedosphere that is of crucial importance in functioning terrestrial ecosystems. The pedosphere hosts large amounts of mercury (Hg). The source of Hg in granite weathering products is currently poorly constrained, however. Here we conducted Hg isotopic analyses on two weathering profiles developed on granitic plutons in Central and South China. Soils from both profiles show a downward decrease in Hg concentration but consistently negative ∆199Hg values. Mercury in precipitation, granites, and vegetation display positive, near-zero, and negative ∆199Hg values, respectively. The negative ∆199Hg values in the two weathering profiles are consistent with estimates of vegetation-derived Hg, supporting that Hg in weathering profiles are dominantly sourced from vegetation. Hg in vegetation is transported into surface soil firmly bonded to organic matter and migrates downwards weathering profiles. This study provides insights into the biogeochemical cycle of Hg in the granite-weathering crust and helps to explain the negative ∆199Hg values observed in terrestrial-derived sedimentary rocks.

Light-induced degradation of dimethylmercury in different natural waters

Photo-induced degradation of dimethylmercury (DMHg) is considered to be an important source for the generation of methylmercury (MMHg). However, studies on DMHg photodegradation are scarce, and it is even debatable about whether DMHg can be degraded in natural waters. Herein, we found that both DMHg and MMHg could be photodegraded in three natural waters collected from the Yellow River Delta, while in pure water only DMHg photodegradation occurred under visible light irradiation. The effects of different environmental factors on DMHg photodegradation were investigated, and the underlying mechanisms were elucidated by density functional theory calculations and a series of control experiments. Our findings revealed that the DMHg degradation rate was higher in the tidal creek water compared to Yellow River, Yan Lake, and purified water. NO3-, NO2-, and DOM could promote the photodegradation with DOM and NO3- showing particularly strong positive effects. Different light sources were employed, and UV light was found to be more effective in DMHg photodegradation. Moreover, MMHg was detected during the photodegradation of DMHg, confirming that the photochemical demethylation of DMHg is a source of MMHg in sunlit water. This work may provide a novel mechanistic insight into the DMHg photodegradation in natural waters and enrich the study of the global biogeochemical cycle of Hg.

Foraging behavior and sea ice-dependent factors affecting the bioaccumulation of mercury in Antarctic coastal waters

To elucidate the potential risks of the toxic pollutant mercury (Hg) in polar waters, the study of accumulated Hg in fish is compelling for understanding the cycling and fate of Hg on a regional scale in Antarctica. Herein, the Hg isotopic compositions of Antarctic cod Notothenia coriiceps were assessed in skeletal muscle, liver, and heart tissues to distinguish the differences in Hg accumulation in isolated coastal environments of the eastern (Chinese Zhongshan Station, ZSS) and the antipode western Antarctica (Chinese Great Wall Station, GWS), which are separated by over 4000 km. Differences in odd mass-independent isotope fractionation (odd-MIF) and mass-dependent fractionation (MDF) across fish tissues were reflection of the specific accumulation of methylmercury (MeHg) and inorganic Hg (iHg) with different isotopic fingerprints. Internal metabolism including hepatic detoxification and processes related to heart may also contribute to MDF. Regional heterogeneity in iHg end-members further provided evidence that bioaccumulated Hg origins can be largely influenced by polar water circumstances and foraging behavior. Sea ice was hypothesized to play critical roles in both the release of Hg with negative odd-MIF derived from photoreduction of Hg2+ on its surface and the impediment of photochemical transformation of Hg in water layers. Overall, the multitissue isotopic compositions in local fish species and prime drivers of the heterogeneous Hg cycling and bioaccumulation patterns presented here enable a comprehensive understanding of Hg biogeochemical cycling in polar coastal waters.

Long-Range Atmospheric Mercury Transport from Across East Asia to a Suburban Coastal Area in Southern Vietnam.

Exports of atmospheric mercury (Hg) from continental East Asia, a major Hg emitter in the globe, have been reported by several studies in neighboring countries such as Japan and Korea. Nonetheless, studies concerning this topic in Southeast Asia (SEA) countries are still limited. Accordingly, gaseous elemental mercury (GEM) has been measured from Can Thanh High School (CTHS), a suburban coastal site in southern Vietnam to study its characterization and discover the evidence of Hg trans-boundary transport from regional sources (e.g., East Asia). Data collected in July, August, and October 2022 were used in this study, and the overall GEM concentration was 1.61 ± 0.32 ng m-3. The GEM levels were higher in October than in July and August, potentially due to the discrepancy in air mass transport patterns induced by tropical monsoon and source origins of Hg. MERRA-2, backward trajectories, and CALIPSO images revealed the trans-boundary air pollution from continental East Asia to southern Vietnam, evidenced by significantly elevated (> 30%) atmospheric Hg concentrations as well as other air pollutants when the plume arrived at CTHS. Furthermore, our results also imply that atmospheric Hg exported from East Asia could influence large areas in SEA, suggesting the need for more studies in various SEA countries in the upcoming future. This study illustrated the influence of regional Hg emissions on local atmospheric Hg pollution and provided data to improve knowledge of the Hg biogeochemical cycle in SEA.

Differential response of Hg-methylating and MeHg-demethylating microbiomes to dissolved organic matter components in eutrophic lake water

Methylmercury (MeHg) production in aquatic ecosystems is a global concern because of its neurotoxic effect. Dissolved organic matter (DOM) plays a crucial role in biogeochemical cycling of Hg. However, owing to its complex composition, the effects of DOM on net MeHg production have not been fully understood. Here, the Hg isotope tracer technique combined with different DOM treatments was employed to explore the influences of DOM with divergent compositions on Hg methylation/demethylation and its microbial mechanisms in eutrophic lake waters. Our results showed that algae-derived DOM treatments enhanced MeHg concentrations by 1.42−1.53 times compared with terrestrial-derived DOM. Algae-derived DOM had largely increased the methylation rate constants by approximately 1−2 orders of magnitude compared to terrestrial-derived DOM, but its effects on demethylation rate constants were less pronounced, resulting in the enhancement of net MeHg formation. The abundance of hgcA and merB genes suggested that Hg-methylating and MeHg-demethylating microbiomes responded differently to DOM treatments. Specific DOM components (e.g., aromatic proteins and soluble microbial byproducts) were positively correlated with both methylation rate constants and the abundance of Hg-methylating microbiomes. Our results highlight that the DOM composition influences the Hg methylation and MeHg demethylation differently and should be incorporated into future Hg risk assessments in aquatic ecosystems.

A high-resolution marine mercury model MITgcm-ECCO2-Hg with online biogeochemistry

Abstract. Mercury (Hg) is a global persistent contaminant. Modeling studies are useful means of synthesizing a current understanding of the Hg cycle. Previous studies mainly use coarse-resolution models, which makes it impossible to analyze the role of turbulence in the Hg cycle and inaccurately describes the transport of kinetic energy. Furthermore, all of them are coupled with offline biogeochemistry, and therefore they cannot respond to short-term variability in oceanic Hg concentration. In our approach, we utilize a high-resolution ocean model (MITgcm-ECCO2, referred to as “high-resolution-MITgcm”) coupled with the concurrent simulation of biogeochemistry processes from the Darwin Project (referred to as “online”). This integration enables us to comprehensively simulate the global biogeochemical cycle of Hg with a horizontal resolution of 1/5∘. The finer portrayal of surface Hg concentrations in estuarine and coastal areas, strong western boundary flow and upwelling areas, and concentration diffusion as vortex shapes demonstrate the effects of turbulence that are neglected in previous models. Ecological events such as algal blooms can cause a sudden enhancement of phytoplankton biomass and chlorophyll concentrations, which can also result in a dramatic change in particle-bound Hg (HgaqP) sinking flux simultaneously in our simulation. In the global estuary region, including riverine Hg input in the high-resolution model allows us to reveal the outward spread of Hg in an eddy shape driven by fine-scale ocean currents. With faster current velocities and diffusion rates, our model captures the transport and mixing of Hg from river discharge in a more accurate and detailed way and improves our understanding of Hg cycle in the ocean.

Isotopic Characterization of Mercury Atmosphere-Foliage and Atmosphere-Soil Exchange in a Swiss Subalpine Coniferous Forest.

To understand the role of vegetation and soil in regulating atmospheric Hg0, exchange fluxes and isotope signatures of Hg were characterized using a dynamic flux bag/chamber at the atmosphere-foliage/soil interfaces at the Davos-Seehornwald forest, Switzerland. The foliage was a net Hg0 sink and took up preferentially the light Hg isotopes, consequently resulting in large shifts (-3.27‰) in δ202Hg values. The soil served mostly as net sources of atmospheric Hg0 with higher Hg0 emission from the moss-covered soils than from bare soils. The negative shift of δ202Hg and Δ199Hg values of the efflux air relative to ambient air and the Δ199Hg/Δ201Hg ratio among ambient air, efflux air, and soil pore gas highlight that Hg0 re-emission was strongly constrained by soil pore gas evasion together with microbial reduction. The isotopic mass balance model indicates 8.4 times higher Hg0 emission caused by pore gas evasion than surface soil photoreduction. Deposition of atmospheric Hg0 to soil was noticeably 3.2 times higher than that to foliage, reflecting the high significance of the soil to influence atmospheric Hg0 isotope signatures. This study improves our understanding of Hg atmosphere-foliage/soil exchange in subalpine coniferous forests, which is indispensable in the model assessment of forest Hg biogeochemical cycling.

Mercury transport and methylmercury production in the lower Cedar River (Iowa) floodplain

Scant attention has been paid to cycling of total mercury (THg) and methylmercury (MeHg) in agriculturally intensive watersheds. Monitoring of Hg and MeHg in river basins provides valuable information on the efficacy of environmental policy and the impacts of land use and climate change on Hg fluxes and biogeochemistry. We report on Hg and MeHg yields in the Cedar River (Iowa), a major tributary of the Upper Mississippi River, and on Hg biogeochemistry in a floodplain of the lower Cedar River, with emphasis on Hg cycling in groundwater and wetland ponds. For the period 2016 to 2018, total Hg yields for the 21,000 km2 Cedar River watershed ranged from 2.6 to 6.9 μg m−2 yr−1, or 25% to 70% of estimated wet deposition, and MeHg yields ranged from 0.09 to 0.18 μg m−2 yr−1. High watershed transfer efficiencies for THg are driven by soil erosion and suspended sediment delivery. Policies and land management practices targeting soil conservation are thus likely to have significant impacts on downstream transport of Hg. Within alluvial groundwaters, Hg and MeHg concentrations were highly spatiotemporally variable, ranging from 0.5 to 2.0 ng/L for THg and 0.03–1.50 ng/L for MeHg. Microtopography exerted strong control on groundwater geochemistry and Hg biogeochemical cycling, with groundwater sampled from lower lying swales exhibiting less dissolved oxygen (DO), higher conductivity, higher dissolved organic carbon (DOC), and higher THg and MeHg. The alluvial aquifer exhibits high hydrologic connectivity with the river and groundwater THg and MeHg concentrations responded rapidly to hydrologic events, with MeHg concentrations increasing with a rising water table. Concentrations of THg and MeHg in wetland ponds were elevated compared to groundwater and most strongly correlated with DOC and UV-absorbance. Methylation potentials in pond sediments were among the highest reported for freshwater sediments, up to 0.15 d−1, which we hypothesize to be linked to high primary productivity associated with nutrient enrichment. Floodplain groundwaters and wetlands constitute important ecosystem control points for downstream MeHg delivery, the magnitude of which is sensitive to changing hydroclimate, especially flood frequency.

Gaseous mercury exchange between air and highly dynamic tidal flats: A laboratory incubation experiment

Gaseous mercury (mainly elemental mercury, Hg(0)) exchange between air and Earth's surfaces is one of the most critical fluxes governing global Hg cycle. As an important and unique part of intertidal ecosystem, tidal flat is characterized by periodic inundation and exposure due to tidal cycle, generating varying hydrological, photochemical and biogeochemical processes. However, quantitative and mechanistic understanding of Hg(0) dynamics between air and exceptionally dynamic tide flats has remained limited to date. In this study, we select five representative tidal flat sediments from typical coastal habits of Chinese coastlines to perform laboratory incubation experiments for deciphering the effect of the interaction of tidal cycle and solar radiation on Hg(0) dynamics over tidal flats with different sediment compositions. We show that sediment Hg concentration, tidal cycle and solar radiation collectively modulate the air−surface Hg(0) exchange over tidal flats and highlight that the photochemistry dominates the Hg(0) production and emission over tidal flats. We find that the daytime inundation presents highest Hg(0) emission fluxes for Hg-poor sediment, but the daytime exposure is the hot moment of Hg(0) emission from Hg-rich sediments and substantially contributes to daily Hg(0) emission fluxes. In the treatment to mimic semidiurnal tide, the daily Hg(0) fluxes are positively correlated to sediment Hg concentrations. Combining our mechanistic insights on air−surface Hg(0) exchange over tidal flats and related data and knowledge reported by other studies, we discuss the implications of our study for field measurement and model development of Hg(0) dynamics over highly dynamic tidal flats. We conclude that the air−surface Hg(0) dynamics over tidal flats are extremely complex and highly variable, and a greater understanding the interactions between natural processes, human impacts and climate forcings will better constrain current and future Hg biogeochemical cycle in global tidal flats.

Determination of the Isotopic Composition of Aqueous Mercury in a Paddy Ecosystem Using Diffusive Gradients in Thin Films.

Measuring the isotopic composition of Hg in natural waters is challenging due to the ultratrace level of aqueous Hg (ng L-1). At least 5 ng of Hg mass is required for Hg isotopic analysis. Given the low Hg concentration in natural waters, a large volume of water (>10 L) is typically needed. The conventional grab sampling method is time-consuming, laborious, and prone to contamination during transportation and preconcentration steps. In this study, a DGT (diffusive gradients in thin films) method based on aminopropyl and mercaptopropyl bi-functionalized SBA-15 nanoparticles was developed and extended to determine the concentration and isotopic composition of aqueous Hg for the first time. The results of laboratory analysis showed that Hg adsorption by DGT induces ∼ -0.2‰ mass-dependent fractionation (MDF) and little mass-independent fractionation (MIF). The magnitude of MDF exhibits a dependence on the diffusion-layer thickness of DGT. Since Hg-MDF can occur in a broad range of environmental processes, monitoring the δ202Hg of aqueous Hg using the DGT method should be performed with caution. Field results show consistent MIF signatures (Δ199Hg) between the DGT and conventional grab sampling method. The developed DGT method serves as a passive sampling method that effectively characterizes the MIF of Hg in waters to understand the biogeochemical cycle of Hg at contaminated sites.

Non-conservative mixing behaviors of mercury in subterranean estuary: Coupling effect of hydrological and biogeochemical processes and implications for rapidly changing world

Coastal ecosystem is an important zone of mercury (Hg) storage and hotspot of neurotoxic methylmercury (MMHg) production and bioaccumulation. The releases of Hg from coastal aquifer or subterranean estuary (STE) via submarine groundwater discharge (SGD) to coastal waters provide an important source of Hg from land to seas. However, the transport and biogeochemical transformation of Hg in STEs are less quantified. In this study, we documented total Hg (THg) and MMHg dynamics in two distinct STEs (a sandflat at an open coast versus a mudflat at a bay) during two different seasons (December versus August) in the temperate coast of northern China, and further applied the salinity‐based conservative mixing model (CMM) to quantify the coupling effect of hydrological and biogeochemical processes on STE Hg cycle. Our field data presented large variations of THg and MMHg concentrations and%MMHg/THg of groundwater and sediment in both STEs over time and space. The CMM results clearly displayed substantial divergences of dissolved THg and MMHg from salinity in groundwater between sites and seasons, and the concentration and percent deviations in the Hg-rich mudflat were significantly higher than those in the Hg-poor sandflat. Our findings indicate the non-conservative mixing behaviors of Hg along the groundwater flow paths of both STEs, and the Hg-rich intertidal zone could be hotspot for the production and source of dissolved THg and MMHg to coastal waters via SGD. Our results provide field evidence to highlight that the hydrological shifts and biogeochemical processes collectively drive complex transport and biogeochemical transformation of Hg in STEs. The non-conservative mixing behaviors of Hg in STEs also highlight that, for more accurately calculating SGD-derived Hg fluxes to coastal seas, we need to carefully select the groundwater zonation of STE to better represent the output endmember. Our findings also address that human activities and climate change will profoundly alter the Hg biogeochemical cycle and toxicology in global coastal aquifers.

Algal organic matter inhibits methylmercury photodegradation in eutrophic lake water: A dynamic study

Algal organic matter (AOM) is a major component of dissolved organic matter (DOM) in eutrophic lakes and could impact the photodegradation of neurotoxic methylmercury (MeHg) in water. Predicting these effects, however, is challenging, largely due to the dynamic changes of AOM during algal decomposition. Here, we investigated the effects of AOM on MeHg photodegradation throughout the algal decomposition process and elucidated these effects by characterizing dynamic changes of AOM and exploring the respective roles of various reactive oxygen species (ROS). Our results reveal that AOM derived from algal decomposition significantly inhibits MeHg photodegradation, and the extent of this inhibition varies depending on the specific lakes (8–21 %, p < 0.05) and their eutrophication states (16–28 %, p < 0.05). The inhibitory effect gradually weakened as the decomposition progressed, which may be attributed to the dynamic changes in the quantity and quality of AOM. Moreover, hydroxyl radical (·OH) was found to be the main contributor in driving MeHg photodegradation (15–23 %) during the early stages of decomposition (day 0–3), while in the later stage (day 12–24), the role of singlet oxygen (1O2, 15–20 %) and (3DOM*, 21–30 %) gradually strengthened and these three ROS jointly drove MeHg photodegradation. Based on our findings and recent studies, we propose that AOM derived from algal decomposition plays a vital role in increasing the risk of MeHg in eutrophic lakes. It promotes MeHg formation while simultaneously inhibiting its photodegradation. Integrating AOM-MeHg interactions into Hg biogeochemical cycling models would reduce uncertainties when predicting MeHg risks.

Mercury reduction by black carbon under dark conditions

An accurate depiction of mercury (Hg) reduction is important to predict Hg biogeochemistry in both aquatic and soil systems. Although the photoreduction of Hg is well documented, reduction in the dark is poorly known and is thus the focus of this work. Black carbon (BC), an important constituent of organic matter in environments, can reduce Hg2+ in dark and oxygen-deficient conditions. Fast removal of Hg2+ in BC/Hg2+ solution was observed, with 4.99–86.88 L mg−1h−1 of the reaction rate constant, which could be ascribed to the combined actions of adsorption and reduction. Meanwhile, slow Hg reduction was obtained, compared to Hg removal, with 0.06–2.16 L mg−1h−1 of the reaction rate constant. Thus, in the initial stage, Hg2+ removal was mainly triggered by adsorption, rather than reduction. Afterward, the adsorbed Hg2+ on black carbon was converted into Hg0. Dissolved black carbon and aromatic CH on particulate black carbon were dominant triggers of Hg reduction for black carbon. During Hg reduction, the intastable intermediate, formed in the complex between aromatic CH and Hg2+, behaved as persistent free radicals, which could be detected by in situ electron paramagnetic resonance. Subsequently, the intastable intermediate was mainly converted into CO on black carbon and Hg0. Corresponding results of the present study highlight the important role of black carbon in the Hg biogeochemical cycle.

Enhanced daytime atmospheric mercury in the marine boundary layer in the South Oceans

Understanding the spatial and temporal variations of atmospheric mercury (Hg) in the marine boundary layer could advance our knowledge on ocean evasion of Hg. Here, we conducted continuous measurements of total gaseous mercury (TGM) in the marine boundary layer during a round-the-world cruise from August 2017 to May 2018. We observed the highest and lowest TGM concentrations in Southern Indian Ocean (1.29 ± 0.22 ng m−3) and Southern Atlantic Ocean (0.61 ± 0.28 ng m−3), respectively. During the daytime, enhanced TGM was observed with the diurnal amplitude difference reaching its maximum in the range of 0.30–0.37 ng m−3 in Southern Indian Ocean and Southern Ocean. The positive correlation between TGM (R2 = 0.68–0.92) and hourly solar radiation in each ocean suggested that the daytime enhanced TGM was likely driven by Hg photoreduction in seawater, after excluding the influence of other meteorological factors. The diurnal amplitude of TGM in the marine boundary layer might be impacted by the microbial productivity and the ratio of ultraviolet radiation. Our study highlights that ocean acts as a net TGM source during the daytime in the Southern Hemisphere and aqueous photoreduction process may play an important role in the biogeochemical cycling of Hg.