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Coastal wetland soils play a critical role in the global mercury (Hg) cycle, serving as both an important repository for total mercury (THg) and a hotspot for methylmercury (MeHg) production. This study investigated Hg pollution in soils dominated by Phragmites australis (PA) and Spartina alterniflora (SA) across five representative China's coastal wetlands (Yellow River (YR), Linhong River (LHR), Yangtze River (CJR), Min River (MR), and Nanliu River (NLR)). The THg concentrations ranged from 16.7 to 446.0 (96.3 ± 59.3 ng g -1 , dw), while MeHg concentrations varied from 0.01 to 0.81 (0.12 ± 0.12 ng g -1 , dw). We further evaluated Hg risk in these wetlands using potential ecological risk index (E r ) and geographical enrichment factor (I geo ). Most wetlands exhibited low to moderate ecological risk, except the PA habitat in the YR wetland, showing moderate to high risk. Soil organic matter significantly influenced THg and MeHg distribution, while MeHg% correlated well with soil salinity and pH. These findings highlight the importance of organic-rich coastal wetland soils in THg and MeHg accumulation, with the soil properties influencing net MeHg production. Furthermore, SA habitat generally exhibited higher MeHg%, suggesting its invasion elevates the ecological risk of MeHg in coastal wetlands. ENVIRONMENTAL IMPLICATION: Mercury (Hg), a global pollutant, poses great risks to wildlife and humans. Since industrialization, anthropogenic Hg release surpassed natural sources. Long-term exposure leads to biomagnification of Hg. This study assessed Hg and methylmercury pollution and risks in soils of five China's coastal wetlands dominated by Phragmites australis and Spartina alterniflora. Environmental factors (total carbon, total organic carbon, total nitrogen, salinity, pH) were analyzed to reveal key variables influencing Hg pollution and methylation. Essential for quantifying Hg pollution in coastal wetlands, the findings provide a scientific basis for effective wetland conservation policies and addressing environmental health in these regions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Mercury (Hg) emitted from East Asian has increased the risk of Hg in China Marginal Seas for decades. However, the speciation of Hg (especially the bioavailable Hg) in these regions remains unclear. To address this problem, we analyzed total Hg (THg) and methylmercury (MeHg) in the sediment and porewater of Yellow sea (YS) and East China Sea (ECS) and determined the speciation of Hg using both improved BCR sequential extraction and isotope dilution (ID) techniques. Nearshore areas of YS and ECS exhibited higher THg levels in sediments and porewater, suggesting the significant contribution of terrestrial inputs. The spatial distribution of MeHg showed similar trends with THg, but the sites with higher MeHg concentrations did not align with those of THg. The improved BCR sequential extraction method showed the residual fraction dominated Hg content (∼44 %) in both systems, with a minor bioavailable carbonate fraction (1 %). The Spearman correlation analysis indicates that E h and pH are the two factors significantly affected Hg bioavailability in the sediment. The bioavailability of Hg (estimated by the BCR method) showed a significant positive correlation with MeHg levels in the sediment (R²=0.47, P < 0.05), suggesting that BCR can be used to estimate the potential of Hg methylation in the sediment. However, the extent of bioavailable Hg in BCR and ID method were 1.15 ± 0.38 % and 29.5 ± 14.8 %, respectively, implying that Hg bioavailability may be underestimated by BCR techniques compared to ID methods (T-test, P < 0.01)., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Riverine mercury (Hg) is mainly transported to coastal areas in suspended particulate matter (SPM)-bound form, posing a potential threat to human health. Water discharge and SPM characteristics in rivers vary naturally with seasonality and can also be arbitrarily disrupted by anthropogenic regulation events, but their effects on Hg transport remain unresolved. Aiming to understand the confounding effects of seasonality and anthropogenic river regulation on Hg and SPM transport, this study selected the highly sediment-laden Yellow River as a representative conduit. Significant variations in SPM concentrations (108 - 7097 mg/L) resulted in fluctuations in total mercury (THg, 3.79 - 111 ng/L) in river water corresponding to seasonality and anthropogenic water/sediment regulation. Principal component analysis and structural equation model revealed that SPM was the essential factor controlling THg and particulate Hg (PHg) in river water. While SPM exhibited equilibrium state in the dry season, a net resuspension during the anthropogenic regulation and net deposition in the wet season demonstrated the impact of SPM dynamics on Hg distribution and transport to coastal regions. Combining water discharge, SPM, and Hg concentrations, a modified model was developed to quantify Hg flux (2256 kg), over 98% of which was in particulate phase., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Photodegradation is critical to reduce the potent neurotoxic methylmercury (MeHg) in water and its subsequent accumulation along food chains. However, this process has been largely ignored in rice paddies, which are hotspots of MeHg production and receive about a quarter of the world's developed freshwater resources. Here, we reported that significant MeHg photodegradation, primarily mediated by hydroxyl radicals, occurs in the overlying water during rice growth. By incorporating field-measured light interception into a rice paddy biogeochemistry model, as well as photodegradation rates obtained from 42 paddy soils stretching ∼3500 km across China, we estimated that photodegradation reduced MeHg concentrations in paddy water and rice by 82 % and 11 %, respectively. Without photodegradation, paddy water could be a significant MeHg source for downstream ecosystems, with an annual export of 178 - 856 kg MeHg to downstream waters in China, the largest rice producer. These findings suggest that photodegradation in paddy water is critical for preventing greater quantities of MeHg entering human food webs., Competing Interests: Declaration of competing interest None., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In the past few decades, mercury (Hg) discharged into the coastal bays of China has significantly increased; however, long-term trends regarding the pollution status and sources of Hg in these bays have yet to be clear. Focusing on this issue, surface sediments and core sediments were collected in the Jiaozhou Bay (JZB), a typical bay highly affected by human activities in China, to analyze the concentrations and stable isotopic composition of Hg. Total mercury (THg) concentrations in surface sediment varied from 7 to 163 ng/g, with higher levels located in the eastern JZB, possibly attributed to intensive industrial and population density. THg in sediment cores 14 and 20 displayed fluctuating increasing trends from 1936 to 2019, reflecting the deterioration of Hg pollution. In contrast, THg in sediment core 28 near the river mouth exhibited a declining trend, possibly due to the river dam construction. Using a stable isotope mixing model, contributions of various sources (atmospheric, riverine, and industrial emissions) to Hg in the JZB were estimated. The results showed that industrial emissions were the main source (over 50%) of mercury in the JZB in 2019. Sediment cores recorded an increase in industrial Hg due to early industrialization and Reform and Opening-up before 2000. In addition, sediment core 20 demonstrated a rise in the percentage of riverine Hg due to land reclamation at the bay's mouth during 2000-2007., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Mercury (Hg) is among the most concerned contaminants in the world due to its high toxicity, prevalent existence in the environments, and bioaccumulation via food chain. Methylmercury (MeHg) is the major form of Hg that accumulates along the food chain and poses threat to humans and wild life. Photodegradation is the dominant process that MeHg is eliminated from freshwater system and upper ocean. The formation of MeHg-dissolved organic matter (DOM) complexes and a variety of free radicals (FR)/reactive oxygen species (ROS) have been previously proposed to be involved in MeHg photodegradation. However, most of these studies were conducted in freshwater, and the mechanism of MeHg photodegradation in seawater remains unclear. In this study, the main pathways of MeHg photodegradation in the seawater of Yellow Sea (YS) and East China Sea (ECS) were investigated using FR/ ROS scavenger addition and DOM competing-ligand addition techniques. The results showed that direct photodegradation of MeHg-DOM complexes is the major pathway of MeHg photodegradation in the YS and ECS, while indirect photolysis of MeHg by hydroxyl radical (·OH) also plays a certain role at some sites. MeHg photodegradation was found to be mainly induced by ultraviolet (UV) light rather than visible light in YS and ECS seawater, and the contribution of UV-B was higher than UV-A which was opposite to that previously reported in freshwater. The energy for breaking the bond of CHg in MeHg-Cl complexes formed in seawater is higher than that in MeHg-DOM complexes and this may cause the relatively greater contribution of UV-B with higher energy to MeHg photodegradation in seawater. In addition, MeHg photodegradation in various fractions of natural DOM with different molecular weights, hydrophilicity/hydrophobicity and acid-base was tested. MeHg photodegradation rates (k d ) varied in these fractions and k d in high molecular weight DOM and hydrophobic Acid (HOA) fractions were faster than that in the other fractions. A significantly positive correlation was observed between k d and thiol concentrations while there was no significant correlation between k d and other measured parameters representing the composition of DOM (specific UV absorbance at 254 nm (SUVA 254 ), spectral slope (SR), chromophoric dissolved organic matter (CDOM), humification index (HIX), biological index (BIX) and fluorescent components). These results indicate that thiol may be the key functional group in DOM affecting the photodegradation of MeHg in the YS and ECS., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Microbial reduction plays a crucial role in Hg redox and the global cycle. Although intracellular Hg(II) reduction mediated by MerA protein is well documented, it is still unclear whether or how bacteria reduce Hg(II) extracellularly without its internalization. Herein, for the first time, we discovered the extracellular reduction of Hg(II) by a widely distributed aerobic marine bacterium Alteromonas sp. KD01 through a superoxide-dependent mechanism. The generation of superoxide by Alteromonas sp. KD01 was determined using 3-bis(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide and methyl cypridina luciferin analogue as probes via UV-vis and chemiluminescence detection, respectively. The results demonstrated that Hg(II) reduction was inhibited by superoxide scavengers (superoxide dismutase (SOD) and Cu(NO 3 ) 2 ) or inhibitors of reduced nicotinamide adenine dinucleotide (NADH) oxidoreductases. In contrast, the addition of NADH significantly improved superoxide generation and, in turn, Hg(II) reduction. Direct evidence of superoxide-mediated Hg(II) reduction was provided by the addition of superoxide using KO 2 in deionized water and seawater. Moreover, we observed that even superoxide at an environmental concentration of 9.6 ± 0.5 nM from Alteromonas sp. KD01 (5.4 × 10 6 cells mL -1 ) was capable of significantly reducing Hg(II). Our findings provide a greater understanding of Hg(II) reduction by superoxide from heterotrophic bacteria and eukaryotic phytoplankton in diverse aerobic environments, including surface water, sediment, and soil.

Transformations between dimethylmercury (DMHg) and other mercury (Hg) species have been one of the critical knowledge gaps in the Hg global biogeochemical cycle due to the lack of detailed studies. The preparation and measurement of DMHg are challenging due to the high toxicity and volatility of DMHg. In this work, we invented a new DMHg generator for successfully preparing high-purity DMHg in a highly controllable and safe way. The DMHg could be spontaneously volatilized and diffused from the original preparation solution to the solution to be studied. The parameters for generating DMHg were optimized to be the pH value of 4.0 with a MeCo/Hg 2+ molar ratio of 10 at 20 °C. The following measurement method of DMHg in the presence of various species of Hg was also investigated and optimized. Hg 0 and DMHg could be separated effectively with the carrier gas flow rate of 15 mL min -1 and the gas chromatography column temperature of 30 °C. The interferences of Hg 0 , monomethylmercury and other species were excluded by systematic control experiments. A sensitive and reliable approach for quantifying trace DMHg in water was developed. Under the optimal conditions, the limits of detection for Hg 0 , MMHg and DMHg were 0.03, 0.002 and 0.024 ng L -1 , respectively, with the relative standard deviation below 8.2%. The developed method was validated by the determination Hg species of different natural water samples. This work is expected to provide a new and safe strategy for DMHg preparation and a verified method for DMHg measurement., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Particulate HgS play crucial roles in the mercury (Hg) cycle. Approximately 20-90% of dissolved Hg can be transformed into particulate HgS by algae. However, detailed knowledge regarding these particles, including sizes and distribution, remains unknown. The present study explored the formation, distribution, and excretion of mercury nanoparticles (HgNPs) in diatom Chaetoceros curvisetus . The results demonstrated that HgNPs (HgS nanoparticles, 29.6-66.2 nm) formed intracellularly upon exposure to 5.0-100.0 μg L -1 Hg(II), accounting for 12-27% of the total Hg. HgNP concentrations significantly increased with increasing intracellular Hg(II) concentrations, while their sizes remained unaffected. HgNPs formed intracellularly and partly accumulated inside the cells (7-11%). Subsequently, the sizes of intracellular HgNPs gradually decreased to facilitate expulsion, 21-50% of which were excreted. These suggested the vital roles of HgNPs in comprehending marine Hg fate. Their unique physicochemical properties and bioavailability would influence Hg biotransformation in the ocean. Additionally, both intracellular and extracellular HgNPs contributed to Hg settling with cells, ultimately leading to Hg burial in sediments. Overall, these findings further deepened our understanding of Hg biotransformation and posed challenges in accurately estimating marine Hg flux and Hg burial.

There are increasing evidences that the biodilution effect can significantly reduce the biomagnification of mercury (Hg) in fish. The significant antagonism of selenium (Se) -Hg may have a potential diluting effect on Hg in fish; however, there is still lack of knowledge on such effect. To reveal the Se-Hg interaction and its role in controlling the biodilution effect of Hg, we investigated levels of Hg and Se in the muscle and liver of redlip mullet from Jiaozhou Bay, China, an urbanized semi-enclosed bay highly impacted by human activities. In general, Hg levels in fish muscle were significantly negatively correlated to the levels of Se in the liver and fish size for fish with a size of < 200 mm, indicating that the antagonistic effect of Se on Hg increased with fish growth. This relationship was not significant for fish with a size of > 200 mm, possibly because the normal metabolism of Hg in muscle was hindered by homeostatic regulation or physiological activities such as gonadal development in vivo. Furthermore, the molar ratio of Se in the liver/Hg in the muscle was significantly increasing with Se/Hg in the liver, suggesting that the liver may be the key organ involved in Se-Hg antagonism. Moreover, both ratios continued to decrease with increasing fish size, implying that the antagonistic effect weakens with fish growth. These results indicate that Hg sequestration by liver may be a key mechanism of Se-Hg antagonism in fish and function as a driver for the biodilution effect of Hg, especially at a size of < 200 mm. These findings are further supported by the established linear model of Se-Hg antagonism at different developmental stages., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Mercury sulfide nanoparticles (HgS NP ), as natural metal-containing nanoparticles, are the dominant Hg species in anoxic zones. Although the microbial Hg methylation of HgS NP has been previously reported, the importance of this process in Hg methylation has yet to be clarified due to the lack of knowledge on the internalization and transformation of HgS NP . Here, we investigated the internalization and transformation of HgS NP in microbial methylator Geobacter sulfurreducens PCA through total Hg analysis and different Hg species quantification in medium and cytoplasm. We found that the microbial uptake of HgS NP , via a passive diffusion pathway, was significantly higher than that of the Hg 2+ -dissolved organic matter (Hg 2+ -DOM) complex. Internalized HgS NP were dissolved to Hg 2+ in cytoplasm with a maximal dissolution of 41%, suggesting a "Trojan horse" mechanism. The intracellular Hg 2+ from HgS NP exposure at the initial stage (8 h) was higher than that in Hg 2+ -DOM group, which led to higher methylation of HgS NP . Furthermore, no differences in methylmercury (MeHg) production from HgS NP were observed between the hgcAB gene knockout (Δ hgcAB ) and wild-type strains, suggesting that HgS NP methylation may occur through HgcAB-independent pathways. Considering the possibility of a broad range of hgcAB -lacking microbes serving as methylators for HgS NP and the ubiquity of HgS NP in anoxic environments, this study highlights the importance of HgS NP internalization and methylation in MeHg production and demonstrates the necessity of understanding the assimilation and transformation of nutrient and toxic metal nanoparticles in general.

The Yellow Sea (YS) of China is facing severe mercury (Hg) pollution problems while the concentration of Hg in the sediment is relatively low compared to its high discharge intensity, whose mechanisms are still unclear. Here, we performed batch experiments to investigate the Hg adsorption capacity of the YS sediments. Freundlich isothermal adsorption simulation results showed that the parameters K F (adsorption capacity constant) of the sediments were varied from 3.33 to 2.88 × 10 4 . Correlation analysis of K F against the physicochemical properties and sequential extraction revealed that organic matter (OM) and particle size influenced the K F for Hg. In addition, the calculated smaller Kd (distribution coefficient) values in the YS compared to other coastal seas indicate that at the sediment-water interface, Hg tends to be more present in porewater. There is also a significant positive correlation between K F and Kd. We conclude that the low OM content of YS sediments is one of the main reasons for their weak adsorption capacity. These findings provide a scientific basis for the phenomenon that Hg entering the YS undergoes environmental behaviors to maintain low concentrations in the sediment, deepen the understanding of Hg cycling in the YS and improve long-term risk prediction capacity for Hg in marine environments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Understanding the speciation and related influence factors of Hg in wet deposition is important to predict the fate and transport of mercury in the atmosphere. In this study, event-based samples of rainwater were collected for one year in Jinan, a northern city in eastern China. The volume-weighted mean concentration of total mercury (THg) in rainwater was 34.8 ng L -1 , comparable to levels in some inland cities in China and were significantly higher than those in North America, Korea and Japan. Most of the Hg in rainwater was associated with particulates, accounted for 15.2-92.9% of THg with a mean of 66.9%, which might be attributed to the scavenging effects of high particulate-bound mercury concentrations in ambient air in urban Jinan. Dissolved mercury (DHg) accounted for 33.1% of THg, in which Hg(OH) 2 , HgClOH, HgCl 2 and Hg(NH 3 ) 2 2+ under the influence of rainwater pH. Positive matrix factorization (PMF) analysis suggested that the major sources of Hg in rainwater were combustion emissions, marine sources, industrial emissions, as well as complexation process, which contributed to 51.4%, 24.7%, 12.2%, and 11.7% of the THg, respectively. For the specific species, the main sources varied with different Hg species, in which combustion emissions contributed one third to one half of each species sum to particulate mercury (PHg), HgClOH, HgCl 2 under the influence of rainwater pH. Positive matrix factorization (PMF) analysis suggested that the major sources of Hg in rainwater were combustion emissions, marine sources, industrial emissions, as well as complexation process, which contributed to 51.4%, 24.7%, 12.2%, and 11.7% of the THg, respectively. For the specific species, the main sources varied with different Hg species, in which combustion emissions contributed one third to one half of each species sum to particulate mercury (PHg), HgClOH, HgCl 2 , HgBrOH and HgBrCl followed by marine sources and industrial emissions. Cluster analysis of backward trajectories revealed that polluted air masses, transported from southeast Shandong, Anhui and Jiangsu Provinces, as well as Beijing-Tianjin-Hebei region, contributed to high Hg concentration in rainwater in Jinan., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Methylmercury (MeHg), a potent neurotoxin, can be formed, migrated and transformed in environmental compartments, accompanying with unique mass-dependent and mass-independent fractionation of mercury (Hg). These Hg isotope fractionation signals have great potential to probe the transformation and transport of MeHg in aquatic environments. However, the majority of studies to date have focused on total Hg isotopic composition, with less attention to the isotopic fractionation of MeHg due to technical difficulties in analysis, which severely hinders the understanding of MeHg isotopic fractionation and its applications. This review a) evaluates the reported analytical methods for Hg isotopic composition of MeHg, including online and offline measurement techniques; b) summarizes the extent and characteristics of Hg isotopic fractionation during MeHg transport and transformation, focusing on methylation, demethylation, trophic transfer and internal metabolism; and c) briefly discusses several applications of MeHg isotopic fractionation signatures in estimating the extent of photodemethylation, tracing the source of Hg species, and diagnosing reaction mechanisms. Additionally, the existing problems and future directions in MeHg isotope fractionation are highlighted to improve the analytical protocol for Hg isotope fractionation and deepen our understanding of Hg isotope fractionation in the biogeochemical cycling of MeHg., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Mercury (Hg) is a global pollutant of health concern due to formation and bioaccumulation of methylmercury (MeHg) during its biogeochemical cycle. Coastal areas are important regions in the biogeochemical cycling of Hg (Liu et al., 2017), where often-occurring natural and anthropogenic perturbations affect Hg transport and transformation and the associated health risk from Hg. The rapidly growing mariculture associated with the rising global demand for food may have a profound effect on coastal Hg cycling, due to the environmental alterations (e.g., resuspension and sedimentation) caused by maricultural activities (e.g., bottom sowing and harvesting). Through simulating the effect of water scouring, a common harvesting method, this study investigated Hg migration and distribution in particulate and dissolved phases in Laizhou Bay of Bohai Sea, China, where mariculture exists extensively. Particulate total and methyl Hg (PTHg and PMeHg) in water (expressed as ng/L) increased sharply due to the resuspension of sediment, but decreased rapidly after a one-off scouring event. When normalized by particle mass, PTHg and PMeHg (ng/g) in suspended sediment particles were significantly higher than that in the initial sediment, suggesting a higher distribution coefficient and higher affinity to bind Hg in the suspended particles. This may be due to the smaller particle sizes, and higher contents of organic matter and Fe/Mn of suspended sediments compared to the initial sediment. While the concentrations of dissolved THg (DTHg) in water column showed minimum changes or decreased, dissolved MeHg (DMeHg) concentrations increased sharply after the perturbation, due to the possible release of MeHg from porewater and potential Hg methylation during the event. These results provide fundamental information needed for ecological and health risk assessment of Hg in mariculture, and highlights the increased mobility and bioaccumulation of MeHg during anthropogenic perturbations in these areas., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

The transformation of mercury (Hg) in the environment plays a vital role in the cycling of Hg and its risk to the ecosystem and human health. Of particular importance are Hg oxidation/reduction and methylation/demethylation processes driven or mediated by the dynamics of light, microorganisms, and organic carbon, among others. Advances in understanding those Hg transformation processes determine our capacity of projecting and mitigating Hg risk. Here, we provide a critical analysis of major knowledge gaps in our understanding of Hg transformation in nature, with perspectives on approaches moving forward. Our analysis focuses on Hg transformation processes in the environment, as well as emerging methodology in exploring these processes. Future avenues for improving the understanding of Hg transformation processes to protect ecosystem and human health are also explored., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

The Eastern China Marginal Seas (ECMS) have been facing a variety of environmental problems, including mercury (Hg) pollution. Although several previous studies have been focused on mass balance of Hg in the ECMS, the contribution of Hg transport at the sediment-water interface remains unclear. This study was aimed to access and quantify the importance of sediment-water transport processes in Hg cycling. Significantly positive correlations were observed between Hg concentrations in the overlying and bottom water and the diffusion rates of Hg from sediment to the water. Approximately 2-3 times higher of THg concentrations in the entire water column were observed in a winter cruise with strong waves which was supposed to strengthen the resuspension process. The mass budget of Hg in the ECMS further showed that diffusion and resuspension processes accounted for approximate 46%, 60%, and 16% of total input Hg in the BS, YS, and ECS, respectively. These results suggest that the sediment-water transport processes play an important role in Hg cycling in the ECMS. As an important "pool" of Hg in the ECMS, the transport of Hg at the sediment-water interface may affect the long-term risk assessment of Hg in these systems.

Mercury (Hg) and its compounds are a kind of worldwide concerned persistent toxic pollutants. As the major primary producer in the ocean, microalgae are expected to play an important role in the cycling and accumulation of Hg in marine ecosystems by either uptake Hg species from seawater or involving in the transformations of Hg species. However, there is still lack of clear knowledge on whether microalgae can induce the methylation and demethylation of Hg in aquatic environments. In this study, Hg isotope dilution and isotope addition techniques were utilized to determine the methylation and demethylation potential of Hg at concentrations comparable to that in natural environments by 15 common marine microalgae (8 species of Diatoms, 4 species of Dinoflagellates, 2 species of Chlorophyta and 1 species of Chrysophyte). Methylation of inorganic Hg was found to be negligible in the culture of all tested marine microalgae, while 6 species could significantly induce the demethylation of methylmercury (MeHg). The rates of microalgae mediated MeHg demethylation were at the same order of magnitude as that of photodemethylation, indicating that marine microalgae may play an important role in the degradation of MeHg in marine environments. Further studies suggest that the demethylation of MeHg by the microalgae may be mainly caused by their extracellular secretions (via photo-induce demethylation) and associated bacteria, rather than the direct demethylation of MeHg by microalgae cells. In addition, it was found that thiol groups may be the major component in microalgal extracellular secretions that lead to the photo-demethylation of MeHg., (Copyright © 2022. Published by Elsevier Ltd.)

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 CuSO 4 , 1 mL of 0.5 M Na 2 S, and 1 mL of 0.5 M CuSO 4 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.

Redox transformation of mercury (Hg) is critical for Hg exchange at the air-sea interface and it can also affect the methylation of Hg in marine environments. However, the contributions of microalgae and aerobic bacteria in oxic seawater to Hg 2+ reduction are largely unknown. Here, we studied the reduction of Hg 2+ mediated by microalgae and aerobic bacteria in surface marine water and microalgae cultures under dark and sunlight conditions. The comparable reduction rates of Hg 2+ with and without light suggest that dark reduction by biological processes is as important as photochemical reduction in the tested surface marine water and microalgae cultures. The contributions of microalgae, associated free-living aerobic bacteria, and extracellular substances to dark reduction were distinguished and quantified in 7 model microalgae cultures, demonstrating that the associated aerobic bacteria are directly involved in dark Hg 2+ reduction. The aerobic bacteria in the microalgae cultures were isolated and a rapid dark reduction of Hg 2+ followed by a decrease of Hg 0 was observed. The reduction of Hg 2+ and re-oxidation of Hg 0 were demonstrated in aerobic bacteria Alteromonas spp. using double isotope tracing ( 199 Hg 2+ and 201 Hg 0 ). These findings highlight the importance of algae-associated aerobic bacteria in Hg transformation in oxic marine water.

Globally, the consumption of coastal fish is the predominant source of human exposure to methylmercury, a potent neurotoxicant that poses health risks to humans. However, the relative importance of riverine inputs and atmospheric deposition of mercury into coastal oceans remains uncertain owing to a lack of riverine mercury observations. Here, we present comprehensive seasonal observations of riverine mercury and methylmercury loads, including dissolved and particulate phases, to East Asia's coastal oceans, which supply nearly half of the world's seafood products. We found that East Asia's rivers annually exported 95 ± 29 megagrams of mercury to adjacent seas, 3-fold greater than the corresponding atmospheric deposition. Three rivers alone accounted for 71% of East Asia's riverine mercury exports, namely: Yangtze, Yellow, and Pearl rivers. We further conducted a metadata analysis to discuss the mercury burden on seawater and found that riverine export, combined with atmospheric deposition and terrestrial nutrients, quantitatively elevated the levels of total, methylated, and dissolved gaseous mercury in seawater by an order of magnitude. Our observations support that massive amounts of riverine mercury are exported to coastal oceans on a continental scale, intensifying their spread from coastal seawater to the atmosphere, marine sediments, and open oceans. We suggest that the impact of mercury transport along the land-ocean aquatic continuum should be considered in human exposure risk assessments.

Mercury (Hg) is among contaminants of public concern due to its prevalent existence, high toxicity, and bioaccumulation through food chains. Elevated Hg has been detected in seafood from the East China Sea (ECS), which is one of the largest marginal seas and an important fishing region in the northwestern Pacific Ocean. However, there is still a lack of knowledge on the distribution of Hg species and their controlling factors in the ECS water column, thus preventing the understanding of Hg cycling and the assessment of Hg risks in the ECS. In this study, two cruises were conducted in October 2014 and June 2015 in order to investigate the distribution of total Hg (THg) and methylmercury (MeHg) and their controlling factors in the ECS. The concentrations of THg and MeHg were determined to be 4.2 ± 2.8 ng/L (THg) and 0.25 ± 0.13 ng/L (MeHg) in water from the ECS. The level of Hg in the ECS occupied the higher rank among the marginal seas, thus indicating significant Hg contamination in this system. Both the THg and MeHg presented complicated spatial distribution patterns in the ECS, with high concentration areas located in both the nearshore and offshore areas. Statistical analyses suggest that temperature (T) and Hg in sediment may be the controlling factors for THg distribution, while dissolved organic matter (DOM), T, and MeHg in the sediment may be the controlling factors for MeHg distribution in the seawater of the ECS. The relative importance of these environmental factors in Hg distribution depends on the water depth. T-salinity (S) diagram analyses showed that water mass mixing may also play an important role in controlling THg and MeHg distribution in the coastal ECS., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Elemental mercury (Hg 0 ) is the major form of mercury (Hg) emitted into the environment via anthropogenic activities, resulting in the distribution of Hg worldwide via atmospheric transport. Hg 0 in oceans plays an important role in global Hg cycling, mainly by affecting the oceanic-atmospheric exchange of Hg. Due to the large amounts of Hg that are released into Chinese coastal seas from rivers and other sources, Chinese coastal seas are thought to be important sources of Hg in open oceans and in the atmosphere. There have been some studies on the distribution of dissolved gaseous mercury (DGM) in Chinses coastal seas and their controlling factors. However, most of these studies were focused on the surface seawater. There is still a lack of comprehensive study on the DGM through the entire water column in Chinese coastal seas. In this study, two cruises were conducted in August 2017 and in December 2017 to January 2018 to identify the distribution of DGM and its controlling factors in the Yellow Sea (YS) and the Bohai Sea (BS). The concentrations of DGM were higher in summer (167.5 ± 121.4 pg/L) than in winter (41.5 ± 25.5 pg/L), reflecting a significant seasonal variation in DGM. DGM concentrations in the BS and the YS were higher than in open oceans and lower than in some coastal regions. DGM concentrations were generally highest in the BS, followed by the northern YS and the southern YS in summer, whereas the reverse trend was observed in winter. DGM in seawater presented a complicated spatial distribution pattern, with high DGM concentration areas present both nearshore and offshore areas. This result indicates that both terrestrial input and in situ production may play important roles in controlling the DGM distribution. Correlation and multiple regression analyses suggested that temperature (T) and wind speed may be important factors affecting the seasonal variation in DGM in the YS and the BS, and reactive Hg (RHg), dissolved Hg (DHg), dissolved oxygen (DO) and suspended particulate matter (SPM) play important roles in controlling the spatial distribution of DGM., (Copyright © 2019 Elsevier Inc. All rights reserved.)

With the rapid development of economy in surrounding land, the Pacific Ocean is facing a number of serious environmental challenges, including mercury (Hg) pollution. Over the past several decades, a number of studies have been conducted on investigating the cycling of Hg in this ecosystem. This review summarizes recent studies on the distribution of Hg species in the water, sediment, and biota and the important processes controlling Hg cycling in the Pacific Ocean. Although a lot of studies have been conducted in this system, more efforts should be made on Hg speciation and cycling in the Pacific Ocean, especially some areas that have rarely studied so far. There is a need to measure the rates of important biogeochemical processes in this ecosystem. Application of multiple methods expected to give a better estimation of the sources and sinks of Hg species in the Pacific Ocean in future studies.

Mercury (Hg) is among the most concerned contaminants in the world. It has three major chemical forms in the environment, including Hg 0 , Hg 2+ , and methylmercury (MeHg). Due to their differences in toxicity, mobility, and bioavailability, speciation analysis is critical for understanding Hg cycling and fate in the environment. SnCl 2 reduction-atomic fluorescence spectrometry detection is the most commonly used method for analyzing inorganic Hg. However, it should be noted that MeHg may also be reduced by SnCl 2 , which would result in the overestimation of inorganic Hg. In this study, the reduction of MeHg by SnCl 2 in both de-ionized (DI) water and four natural waters was investigated. The results showed that MeHg could be reduced by SnCl 2 in DI water whereas this reaction was hard to occur in tested natural waters. By investigating the effects of water chemical characteristics (dissolved organic matter, pH and common anions and cations) on this reaction, SO 4 2- was identified to be the dominant factor prohibiting SnCl 2 induced MeHg reduction in natural waters. SO 4 2- in natural waters was evidenced to be reduced to S 2- by SnCl 2 and the generated S 2- can complex with MeHg to form MeHgS - which is hard to be reduced by SnCl 2 . Findings of this study indicate that the effect of MeHg reduction by SnCl 2 on inorganic Hg analysis is negligible in natural waters; however, at simulated experimental systems without SO 4 2- , SO 4 2- should be added as protecting agents to prevent MeHg reduction when analyzing inorganic Hg if it would not cause any other unwanted effects., (Copyright © 2018. Published by Elsevier B.V.)

The role of macrophytes in the biogeochemical cycle of mercury (Hg) in the Florida Everglades is poorly understood. Stable isotope tracer techniques were employed to investigate Hg uptake by sawgrass ( Cladium jamaicense) from soil and atmospheric pathways and the fate of Hg after absorption. Our results suggest that soil spiked 201 Hg 2+ was rapidly taken up by roots and transported to aboveground parts. The spiked 201 Hg that was transported to the aboveground parts was trapped; no release of the spiked 201 Hg from the leaf to the air was detected. Atmospheric 199 Hg 0 exposure experiments revealed that the majority of the previously deposited 199 Hg 0 taken into the leaf was fixed, with a very limited proportion (1.6%) available for re-emission to the atmosphere. The percentage of 199 Hg 0 fixed in the leaf will help reduce the model uncertainty in estimating the Hg 0 exchange over the air-vegetation surface. We propose that sawgrass needs to be viewed as an important sink for atmospheric Hg 0 in the regional Hg mass balance; this would have important implications for the critical loads of Hg to the Everglades. The multi-isotope tracer technique could be an effective tool to identify the role of plants in biogeochemical cycling of Hg in other ecosystems.

Elemental mercury (Hg 0 ) has different behavior in the environment compared to other pollutants due to its unique properties. It can remain in the atmosphere for long periods of time and so can travel long distances. Through air-surface (e.g., vegetation or ocean) exchange (dry deposition), Hg 0 can enter terrestrial and aquatic systems where it can be converted into other Hg species. Despite being ubiquitous and playing a key role in Hg biogeochemical cycling, Hg 0 behavior in the environment is not well understood. The objective of this review is to provide a better understanding of how the unique physicochemical properties of Hg 0 affects its cycling and chemical transformations in different environmental compartments. The first part focuses on the fundamental chemistry of Hg 0 , addressing why Hg 0 is liquid at room temperature and the formation of amalgam, Hg halide, and Hg chalcogenides. The following sections discuss the long-range transport of Hg 0 as well as its redistribution in the atmosphere, aquatic and terrestrial systems, in particular, on the sorption/desorption processes that occur in each environmental compartment as well as the involvement of Hg 0 in chemical transformation processes driven by photochemical, abiotic, and biotic reactions., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Elemental mercury, Hg(0), is ubiquitous in water and involved in key Hg biogeochemical processes. It is extensively studied as a purgeable dissolved species, termed dissolved gaseous mercury (DGM). Little information is available regarding nonpurgeable particulate Hg(0) in water, Hg(0) bound to suspended particulate matter (SPM), which is presumably present due to high affinity of Hg(0) adsorption on solids. By employing stable isotope tracer and isotope dilution (ID) techniques, we investigated the occurrence and quantification of particulate Hg(0) after Hg(0) being spiked into natural waters, aiming to provide firsthand information on particulate Hg(0) in water. A considerable fraction of (201)Hg(0) spiked in water (about 70% after 4 h equilibration) was bound to SPM and nonpurgeable, suggesting the occurrence of particulate Hg(0) in natural waters. A scheme, involving isotope dilution, purge and trap, and inductively coupled plasma mass spectrometry detection, was proposed to quantify particulate Hg(0) by the difference between DGM and total Hg(0), determined immediately and at equilibration after spiking ID Hg isotope, respectively. The application of this newly established method revealed the presence of particulate Hg(0) in Florida Everglades water, as the determined DGM levels (0.14 to 0.22 ng L(-1)) were remarkably lower than total Hg(0) (0.41 to 0.75 ng L(-1)).

Methyl iodide or iodomethane (CH3I) has recently been registered as a fumigant in many countries, although its environmental impacts are not well understood. Here we report the results of a study on the methylation of mercury by CH3I in natural water by incubation experiments using both Hg ((199)HgCl2 and CH3(201)Hg(+))- and hydrogen (CD3I)-stable isotope addition techniques. We find that methylation of Hg(0), Hg2(2+) and Hg(2+) by CH3I can occur in natural water under sunlight, while only Hg(0) and Hg2(2+) can be methylated in deionized water. We propose that the methylation of Hg by CH3I in natural waters is mediated by sunlight and involves two steps, the reduction of Hg(2+) to Hg(0)/Hg2(2+) and the subsequent methylation of Hg(0)/Hg2(2+) by CH3I. Further quantitative assessment suggests that CH3I-involved methylation of inorganic Hg could be an important source of CH3Hg(+) in an environment where CH3I has been used in large amounts as a fumigant.

The role of macrophytes in mercury (Hg) cycling in the Florida Everglades ecosystem has not been fully understood. In this study, a stable isotope ((199)Hg(2+)) addition technique was used to trace the methylation, uptake, and translocation of Hg by sawgrass ( Cladium jamaicense ) and quantitatively evaluate the contribution of atmospheric and soil Hg to Hg in sawgrass leaves and below-ground biomass. The results showed that spiked (199)Hg(2+) could be rapidly methylated to monomethylmercury (Me(199)Hg) in the soil of the sawgrass pots. Only small portions of total Hg (THg) and monomethylmercury (MeHg) in the soil could be taken up by sawgrass, indicated by the ratios of T(199)Hg and Me(199)Hg (tracer) concentrations in the sawgrass below-ground biomass (BGBM) over that in the soil (6.50 ± 1.9% and 12.8 ± 3.6% for THg and MeHg, respectively). Concentrations of T(199)Hg (tracer) and Me(199)Hg (tracer) in sawgrass leaves only accounted for 5.50 ± 2.8% and 15.6 ± 4.0%, respectively, of that in the BGBM, implying that the fractions of mercury species transported upward by sawgrass were also small. Statistical analysis (t test) showed that sawgrass preferred MeHg over THg in both uptake and upward translocation. The majority (>90%) of THg in sawgrass leaves were estimated to be obtained from atmospheric Hg, rather than from soil, suggesting that assimilation of atmospheric Hg could increase the overall Hg stock in the Florida Everglades ecosystem. The finding about foliar uptake of Hg is especially important for a better understanding of mercury cycling in the Everglades, given the large amount of sawgrass biomass in this ecosystem.

Methylmercury (MeHg) is recognized as one of the major water quality concerns in the Florida Everglades. Degradation of MeHg in the water is thought to be one of the most important processes to the cycling of MeHg, but there is a lack of quantitative estimations of its effect on the distribution and cycling of MeHg in this ecosystem. Stable isotope (Me201Hg) addition method was implemented to investigate the degradation of MeHg in the Everglades. By combining these results with the field monitoring data, effects of photodegradation on MeHg distribution and its contribution to MeHg cycling were estimated. The results indicate that degradation of MeHg in Everglades water is mediated by sunlight and that UV-A and UV-B radiations are the principal driver. The spatial pattern of MeHg photodegradation potential (PPD) generally illustrated an increasing trend from north to south in the Everglades, which was opposite to the distribution of MeHg in water column. Correlation analysis shows that MeHg concentration in the water had a significant negative relation to PPD, suggesting that photodegradation could play an important role in controlling the distribution of MeHg in Everglades water. Furthermore, about 31.4% of MeHg input into the water body was removed by photodegradation, indicating its importance in the biogeochemical cycling of MeHg in the Everglades. This percent reduction is much lower than that reported for other ecosystems, which could be caused by the higher concentration of DOC in the Everglades. The relatively slower degradation of MeHg could be one of the main reasons for the high ratio of MeHg to total mercury (THg) in this ecosystem.

Mercury (Hg) is a global pollutant of public concern because of its high toxicity and capability for worldwide distribution via long-range atmospheric transportation. Wet atmospheric deposition is an important source of Hg in both terrestrial and aquatic environments. Concentrations of various Hg species in precipitation were monitored from March 2016 to February 2017 in a coastal urban area of Qingdao, and their wet deposition fluxes were estimated. The results showed that the volume-weighted mean (VWM) concentrations of total mercury (THg), reactive mercury (RHg), dissolved THg (DTHg), particulate THg (PTHg), total methylmercury (TMeHg), and dissolved and particulate MeHg (DMeHg and PMeHg) in Qingdao's precipitation were 13.6, 1.5, 5.4, 8.2, 0.38, 0.15, and 0.22 ng L −1 , respectively, and their annual deposition fluxes were estimated to be 5703.0 (THg), 666.6 (RHg), 2304.0 (DTHg), 3470.4 (PTHg), 161.6 (TMeHg), 64.0 (DMeHg), and 95.7 (PMeHg) ng m −2 y −1 , respectively. A relatively high proportion of MeHg in THg was observed in precipitation (3.0 ± 2.6%) possibly due to higher methylation and contributions from an oceanic source to MeHg in the precipitation. Obvious seasonal variations in Hg concentrations and deposition fluxes were observed in the precipitation in Qingdao. Correlation analyses and multiple regression analyses showed that SO 2 , pH, and NO 3 − were the controlling factors for THg in precipitation, whereas the MeHg concentration was primarily controlled by the SO 2 , WS, Cl − , and THg concentrations. PM2.5 and Cl − were the major controlling factors for PMeHg/TMeHg, whereas the TMeHg/THg ratio was mainly influenced by Cl − . The THg and MeHg fluxes were primarily controlled by precipitation, whereas Cl − was also an important factor for the MeHg wet deposition flux. The results of a 72-h backward trajectory analysis in the study region with the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model indicated that Hg deposition in Qingdao mainly originated from four major sources, i.e., the local area, northwestern China, southeastern China and an oceanic source. This oceanic source is an important source of Hg (especially MeHg) in the precipitation in Qingdao. [ABSTRACT FROM AUTHOR]

Mercury (Hg) and its compounds are a class of highly toxic and pervasive pollutants. During the biogeochemical cycling of Hg, methylmercury (MeHg), a potent neurotoxin, can be produced and subsequently bioaccumulated along the food chain in aquatic ecosystems. MeHg is among the most widespread contaminants that pose severe health risks to humans and wildlife. Methylation of inorganic mercury to MeHg and demethylation of MeHg are the two most important processes in the cycling of MeHg, determining the levels of MeHg in aquatic ecosystems. This paper reviews recent progress on the study of Hg methylation and demethylation in aquatic environments, focusing on the following three areas: (1) sites and pathways of Hg methylation and demethylation, (2) bioavailability of Hg species for methylation and demethylation, and (3) application of isotope addition techniques in quantitatively estimating the net production of MeHg. [ABSTRACT FROM AUTHOR]

Riverine mercury (Hg) is the largest global source of Hg in coastal oceans. The Yellow River delivers the majority of Hg to the semi-enclosed Bohai Sea, where Hg contamination adversely affects the surrounding heavily populated provinces in northern China. Mercury distribution patterns in the river-estuary interacting area provides essential information to understand the riverine Hg transport and biogeochemical cycling of Hg in the estuary. Analyzing the spatial distributions of total- (THg) and methyl-Hg (MeHg) in the lower end of Yellow River (∼105 km) and adjacent estuary, we found the dominant role of suspended particulate matter (SPM) in Hg transport, with 99.1% and 86.3% of THg and MeHg being in particulate phase. The SPM dynamics, such as transport, retention, sorting and sedimentation, governs Hg transport with water flow and particle-water partition of Hg. While THg decreased along the water flow to the river mouth with the settlement of particulate THg (about 27.5% onto the riverbed and the rest entering the sea), MeHg and particulate MeHg increased by 110% and 117%, respectively. This study highlights the distinct patterns in THg and MeHg distribution and transport and suggests potential Hg methylation and external MeHg input in the river-estuary mixed zone. [Display omitted] • Mercury distribution patterns were revealed in the river-estuary interacting area. • Particulate THg and MeHg played dominant roles in the surface water. • SPM dynamics governs the transport and particle-water partition of Hg. • The distinct patterns in THg and MeHg show Hg methylation and external MeHg input. [ABSTRACT FROM AUTHOR]