Near surface oxidation of elemental mercury leads to mercury exposure in the Arctic Ocean biota.

Atmospheric mercury (Hg(0), Hg(II)) and riverine exported Hg (Hg(II)) are proposed as important Hg sources to the Arctic Ocean. As plankton cannot passively uptake Hg(0), gaseous Hg(0) has to be oxidized to be bioavailable. Here, we measured Hg isotope ratios in zooplankton, Arctic cod, total gaseous Hg, sediment, seawater, and snowpack from the Bering Strait, the Chukchi Sea, and the Beaufort Sea. The Δ200Hg, used to differentiate between Hg(0) and Hg(II), shows, on average, 70% of Hg(0) in all biota and differs with seawater Δ200Hg (Hg(II)). Since Δ200Hg anomalies occur via tropospheric Hg(0) oxidation, we propose that near-surface Hg(0) oxidation via terrestrial vegetation, coastally evaded halogens, and sea salt aerosols, which preserve Δ200Hg of Hg(0) upon oxidation, supply bioavailable Hg(II) pools in seawater. Our study highlights sources and pathways in which Hg(0) poses potential ecological risks to the Arctic Ocean biota.

Effects of hydrologic regimes on the loading and spatiotemporal variation of mercury in the microtidal river estuary.

The potential effect of hydrological conditions on distribution and loadings of Hg species was investigated in the microtidal Hyeongsan River Estuary (HRE). Dissolved Hg (DHg) and dissolved methylmercury (DMeHg) from the creek receiving industrial wastes were effectively settled to sediment during the post-typhoon period, while persistent input from the Hg-contaminated creek without settling was observed during the dry periods. The event-based mean approach was applied to explore the hydrological effects on the annual flux of Hg. The largest inputs of DHg and particulate Hg (PHg) were found in the Hg-contaminated creek, and DHg input was higher in the dry than wet periods whereas PHg input was higher in the wet than dry periods. In sediment, Hg and MeHg concentrations decreased after the typhoon, attributed to erosion of surface sediments. Overall, the HRE serves as an effective sink of Hg that reduces the degree of Hg contamination in coastal water.

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

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

Interspecific Variations in the Internal Mercury Isotope Dynamics of Antarctic Penguins: Implications for Biomonitoring.

Mercury (Hg) biomonitoring requires a precise understanding of the internal processes contributing to disparities between the Hg sources in the environment and the Hg measured in the biota. In this study, we investigated the use of Hg stable isotopes to trace Hg accumulation in Adélie and emperor penguin chicks from four breeding colonies in Antarctica. Interspecific variation of Δ199Hg in penguin chicks reflects the distinct foraging habitats and Hg exposures in adults. Chicks at breeding sites where adult penguins predominantly consumed mesopelagic prey showed relatively lower Δ199Hg values than chicks that were primarily fed epipelagic krill. Substantial δ202Hg variations in chick tissues were observed in both species (Adélie: -0.11 to 1.13‰, emperor: -0.27 to 1.15‰), whereas only emperor penguins exhibited the lowest δ202Hg in the liver and the highest in the feathers. Our results indicate that tissue-specific δ202Hg variations and their positive correlations with % MeHg resulted from MeHg demethylation in the liver and kidneys of emperor penguin chicks, whereas Adélie penguin chicks showed different internal responses depending on their exposure to dietary MeHg. This study highlights the importance of considering intra- and interspecific variations in adult foraging ecology and MeHg demethylation when selecting penguin chicks for Hg biomonitoring.

Atmospheric mercury uptake and accumulation in forests dependent on climatic factors.

The environmental and climatic factors dictating atmospheric mercury (Hg) uptake by foliage and accumulation within the forest floor are evaluated across six mountain sites, South Korea, using Hg concentration and Hg stable isotope analyses. The isotope ratios of total gaseous Hg (TGM) at six mountains are explained by local anthropogenic Hg emission influence and partly by mountain elevation and wind speed. The extent to which TGM is taken up by foliage is not dependent on the site-specific TGM concentration, but by the local wind speed, which facilitates TGM passage through dense deciduous canopies in the Korean forests. This is depicted by the significant positive relationship between wind speed and foliage Hg concentration (r2 = 0.92, p < 0.05) and the magnitude of δ202Hg shift from TGM to foliage (r2 = 0.37, p > 0.05), associated with TGM uptake and oxidation by foliar tissues. The litter and topsoil Hg concentrations and isotope ratios reveal relationships with a wide range of factors, revealing lower Hg level and greater isotopic fractionation at sites with low elevation, high wind speed, and high mean warmest temperature. We attribute this phenomenon to active TGM re-emission from the forest floor at sites with high wind speed and high temperature, caused by turnover of labile organic matter and decomposition. In contrast to prior studies, we observe no significant effect of precipitation on forest Hg accumulation but precipitation appears to reduce foliage-level Hg uptake by scavenging atmospheric Hg species available for stomata uptake. The results of this study would enable better prediction of future atmospheric and forest Hg influence under climate change.

Isotopic investigation of sources and processes affecting gaseous and particulate bound mercury in the east coast, South Korea.

Understanding sources and processes affecting atmospheric mercury (Hg) are key to enabling targeted Hg managements under the Minamata Convention on Mercury. We employed stable isotopes (δ202Hg, Δ199Hg, Δ201Hg, Δ200Hg, Δ204Hg) and backward air trajectories to characterize sources and processes affecting total gaseous Hg (TGM) and particulate bound Hg (PBM) in a coastal city, South Korea, subjected to atmospheric Hg sources of a local steel manufacturing industry, coastal evasion from the East Sea, and long-distance transport from East Asian countries. Based on the simulated airmasses and the isotopic comparison with TGM characterized from other urban, remote, and coastal sites, TGM evaded from the coastal surface of the East Sea (warm seasons) and from the land surface in high latitude regions (cold seasons) act as important sources relative to local anthropogenic emissions at our study location. Conversely, a significant relationship between Δ199Hg and concentrations of PBM (r2 = 0.39, p < 0.05) and a seasonally uniform Δ199Hg/Δ201Hg slope (1.15), except for summer (0.26), suggest that PBM is generally sourced from local anthropogenic emissions and subjected to Hg2+ photo-reduction on particles. The striking isotopic similarity between our PBM (δ202Hg; -0.86 to 0.49 ‰, Δ199Hg; -0.15 to 1.10 ‰) and those previously characterized along the coastal and offshore regions of the Northwest Pacific (δ202Hg; -0.78 to 1.1 ‰, Δ199Hg; -0.22 to 0.47 ‰) infer that anthropogenically emitted PBM from East Asia and those processed in the coastal atmosphere serves as a regional isotopic end-member. The implementation of air pollution control devices can reduce local PBM, while regional and/or multilateral efforts are required to manage TGM evasion and transport. We also anticipate that the regional isotopic end-member can be used to quantify the relative influence of local anthropogenic Hg emissions and complex processes affecting PBM in East Asia and other coastal regions.

Monitoring the impact of climate extremes and COVID-19 on statewise sentiment alterations in water pollution complaints.

The COVID-19 pandemic and associated prevention policies can directly or indirectly alter the sentiment of individuals while registering water pollution complaints, but observational evidence remains limited. Here, we conducted a sentiment analysis on over 10,000 water pollution complaints from residents in Alabama, USA (2012-2021) to better understand how and to what extent COVID-19 has altered emotion (polarity score-based) and attitude (subjectivity) of water pollution complaints. We found that the 2017 state-wise drought significantly increased the percentage of negative water pollution complaints by +35%, with no significant alternation in attitude before the COVID-19 pandemic. Since COVID-19, the percentage of negative and subjective water pollution complaints significantly decreased and increased by -30 and +20%, respectively, and these sentiment alternations were maintained by 2021. This study provides a new direction for environmental governance and management, requiring a timely response to changes in the public's emotions and attitudes during the next climate extremes and pandemics.

Observational evidence linking ocean sulfur compounds to atmospheric dimethyl sulfide during Icelandic Sea phytoplankton blooms.

In two Icelandic Sea spring blooms (May 2018 and 2019) in the North Atlantic Ocean (62.9-68.0°N, 9.0-28.0°W), chlorophyll-a and dimethylsulfoniopropionate (DMSP) concentrations and DMSP lyase activity (the DMSP-to-dimethyl sulfide (DMS) conversion efficiency) were measured at 67 stations, and the hourly atmospheric DMS mixing ratios were concurrently measured only in May 2019 at Storhofdi on Heimaey Island, located south of Iceland (63.4°N, 20.3°W). The ocean parameters for biology (i.e., chlorophyll-a, DMSP, and DMSP lyase activity) were broadly associated in distribution; however, the statistical significance of the association differed among four ocean domains and also between 2018 and 2019. Specifically, the widespread dominance of Phaeocystis, coccolithophores, and dinoflagellates (all rich in DMSP and high in DMSP lyase activity) across the study area is a compelling indication that variations in DMSP-rich phytoplankton were likely a main cause of the variations in statistical significance. For all the ocean domains defined here, we found that the DMS production capacity (calculated using the exposures of air masses to ocean biology prior to their arrivals at Heimaey and the atmospheric DMS mixing ratios of those air masses at Heimaey) was surprisingly consistent with in situ ocean S data (i.e., DMSP and DMSP lyase activity). Our study shows that the proposed computational approach enabled the detection of changes in DMS production and emission in association with changes in ocean primary producers.

Optimization and application of passive air sampling method for gaseous elemental mercury in Ulsan, South Korea.

We compared uptake rates and concentrations of gaseous elemental mercury (GEM) by passive sampling conditions and investigated the spatial distribution of GEM in Ulsan, the largest industrial city in South Korea. For the optimization of sampling conditions, two outer sampling containers (cylindrical polyethylene terephthalate and two stainless steel bowls), two different sulfur contents of the sorbent (16.3% and 26.3%), and three sampling periods (1, 2, and 3 months) were considered. The uptake rates of GEM were not statistically different by the sampling container, but they were increased with the sulfur contents of activated carbon. A sampling condition using two stainless bowls and lower sulfur contents of activated carbon for 2-3 months was preferred with the highest precision of GEM concentrations. With the same method, passive air samples were collected for 3 months in duplicate from 10 sites in Ulsan. The concentrations of GEM ranged from 3.13 to 11.2 ng/m3 (mean 4.65 ng/m3), and the highest concentration was measured at a non-ferrous industrial complex. A zinc smelter in the non-ferrous industrial complex was identified as a major mercury source in Ulsan. This study is the first passive air sampling study investigating the spatial distributions of GEM in different types of industrial areas as well as residential areas of Ulsan.

Total mercury in different egg tissues provides insights to mercury metabolisms in bird bodies.

Mercury (Hg) pollution in birds has been widely reported, but the metabolism of Hg in bird bodies remains unclear. Measurement of Hg concentrations in bird tissues (muscles and organs) could provide insights into the metabolism of Hg in bird bodies, however, this approach is often invasive. To avoid invasive procedures, we conducted feeding experiments using chickens and used eggs as a proxy for understanding Hg metabolism in chicken bodies. For the control group, various THg concentrations were observed in egg whites, egg yolks, and eggshells, but the THg concentration trends for different egg tissues were not statistically different (P > 0.05). For the Hg feeding group (0.3 mg/kg body weight, feeding once), Hg peaks were observed in egg yolks and egg whites at different time periods, suggesting different response time to dietary Hg in chicken body tissues. Mercury in egg yolks peaked at Day 6, suggesting their quick response to dietary Hg. Egg whites reached Hg peak at Day 20, exhibiting a slower response to dietary Hg. Eggshells did not show a Hg peak, perhaps due to their predominant inorganic components that do not trigger Hg bioaccumulation. We measured THgyolk/THgwhite ratios in various chicken eggs purchased from three areas in Guizhou, SW China. The THgyolk/THgwhite ratios for Huaxi, Hezhang and Wuchuan were 1.33 (0.57-2.41), 7.89 (4.27-19.47) and 2.64 (1.68-4.22), respectively, to suggest different exposure history for chickens. This study provides new insights into the metabolism and lifetime of Hg in bird bodies.

Ecological Traits of Fish for Mercury Biomonitoring: Insights from Compound-Specific Nitrogen and Stable Mercury Isotopes.

We coupled compound-specific isotopic analyses of nitrogen (N) in amino acids (δ15NGlu, δ15NPhe) and mercury stable isotopes (δ202Hg, Δ199Hg) to quantify ecological traits governing the concentration, variability, and source of Hg in largemouth bass (LB) and pike gudgeon (PG) across four rivers, South Korea. PG displayed uniform Hg concentration (56-137 ng/g), trophic position (TPcorrected; 2.6-3.0, n = 9), and N isotopes in the source amino acid (δ15NPhe; 7-13‰), consistent with their specialist feeding on benthic insects. LB showed wide ranges in Hg concentration (45-693 ng/g), TPcorrected (2.8-3.8, n = 14), and δ15NPhe (1.3-16‰), reflecting their opportunistic feeding behavior. Hg sources assessed using Hg isotopes reveal low and uniform Δ199Hg in PG (0.20-0.49‰), similar to Δ199Hg reported in sediments. LB displayed site-specific δ202Hg (-0.61 to -0.04‰) and Δ199Hg (0.53-1.09‰). At the Yeongsan River, LB displayed elevated Δ199Hg and low δ15NPhe, consistent with Hg and N sourced from the atmosphere. LB at the Geum River displayed low Δ199Hg and high δ15NPhe, both similar to the isotope values of anthropogenic sources. Our results suggest that a specialist fish (PG) with consistent ecological traits and Hg concentration is an effective bioindicator species for Hg. When accounting for Hg sources, however, LB better captures site-specific Hg sources.

Internal Dynamics and Metabolism of Mercury in Biota: A Review of Insights from Mercury Stable Isotopes.

Monitoring mercury (Hg) levels in biota is considered an important objective for the effectiveness evaluation of the Minamata Convention. While many studies have characterized Hg levels in organisms at multiple spatiotemporal scales, concentration analyses alone often cannot provide sufficient information on the Hg exposure sources and internal processes occurring within biota. Here, we review the decadal scientific progress of using Hg isotopes to understand internal processes that modify the speciation, transport, and fate of Hg within biota. Mercury stable isotopes have emerged as a powerful tool for assessing Hg sources and biogeochemical processes in natural environments. A better understanding of the tissue location and internal mechanisms leading to Hg isotope change is key to assessing its use for biomonitoring. We synthesize the current understanding and uncertainties of internal processes leading to Hg isotope fractionation in a variety of biota, in a sequence of better to less studied organisms (i.e., birds, marine mammals, humans, fish, plankton, and invertebrates). This review discusses the opportunities and challenges of using certain forms of biota for Hg source monitoring and the need to further elucidate the physiological mechanisms that control the accumulation, distribution, and toxicity of Hg in biota by coupling new techniques with Hg stable isotopes.

Import, export, and speciation of mercury in Kongsfjorden, Svalbard: Influences of glacier melt and river discharge.

The major sources and sinks of total mercury (THg) and methylmercury (MeHg) in Kongsfjorden were estimated based on spreadsheet-based ecological risk assessment for the fate of mercury (SERAFM). SERAFM was parameterized and calibrated to fit Kongsfjorden using the physical properties of the fjord, runoff coefficients of Hg, transformation rate constants of Hg, partition coefficients of Hg, Hg loadings from freshwater, and solid balance parameters. The modeled Hg concentrations in the seawater matched with the measured concentrations, with a mean bias of 12% and a calibration error of 0.035. The mass budget showed that the major THg sources were tidal inflow and glacial runoff, while the major MeHg sources were tidal inflow and in situ methylation in shallow halocline water, which agreed with the distributions of THg and MeHg in seawater. The coupling of observation and fate modeling in Kongsfjorden provides a basic understanding of Hg cycles in the Arctic fjords.

Elucidating sources of mercury in the west coast of Korea and the Chinese marginal seas using mercury stable isotopes.

Nearshore systems play an important role as mercury (Hg) sources to the open ocean and to human health via fish consumption. The nearshore system along East Asia is of particular concern given the rapid industrialization, which contributes to significant anthropogenic Hg emissions and releases. We used Hg stable isotopes to characterize Hg sources in the sediment and fish along the west coast of Korea, located at the northeast of the East China Sea. The Hg isotope ratios of the west coast sediments (δ202Hg; -0.89 to -0.27‰, Δ199Hg; -0.04 to 0.14‰) were statistically similar with other nearshore sediments (δ202Hg; -0.99 to -0.30‰, Δ199Hg; -0.04 to 0.19‰) and overlapped with the industrial Hg source end-member (δ202Hg; -0.5‰, Δ199Hg; 0.01‰) estimated from the Chinese marginal seas. Using a ternary mixing model, we estimated that industrial Hg sources contribute 83-97% in the west coast of Korea, and riverine and atmospheric Hg sources play minor roles in the Korean west coast and the Chinese marginal seas. The comparison between Hg isotope ratios of the sediment and nearshore fish revealed that the fish in the most west coast sites are exposed to MeHg produced in the sediment. At a few southwest coast sites, external MeHg produced in rivers and the open ocean water column appears to be more important as a source in fish. This is supported by much higher δ202Hg (0.74‰; similar to oceanic fish) and lower δ202Hg (-0.71‰; similar to riverine sources) compared to fish collected from other west coast sites influenced by sedimentary MeHg. The substantial Hg contributions from industrial activities suggest the national policies regulating anthropogenic Hg releases can directly mitigate human Hg exposure originating via local fish consumption. This study contributes to the growing regional and global inventories of Hg fluxes and sources exported into coastal oceans.

The beneficial and hazardous effects of selenium on the health of the soil-plant-human system: An overview.

Selenium (Se), which can be both hazardous and beneficial to plants, animals and humans, plays a pivotal role in regulating soil-plant-human ecosystem functions. The biogeochemical behavior of Se and its environmental impact on the soil-plant-human system has received broad attention in the last decades. This review provides a comprehensive understanding of Se biogeochemistry in the soil-plant-human system. The speciation, transformation, bioavailability as well as the beneficial and hazardous effects of Se in the soil-plant-human system are summarized. Several important aspects in Se in the soil-plant-human system are detailed mentioned, including (1) strategies for biofortification in Se-deficient areas and phytoremediation of soil Se in seleniferous areas; (2) factors affecting Se uptake and transport by plants; (3) metabolic pathways of Se in the human body; (4) the interactions between Se and other trace elements in plant and animals, in particular, the detoxification of heavy metals by Se. Important research hotspots of Se biogeochemistry are outlined, including (1) the coupling of soil microbial activity and the Se biogeochemical cycle; (2) the molecular mechanism of Se metabolic in plants and animals; and (3) the application of Se isotopes as a biogeochemical tracer in research. This review provides up-to-date knowledge and guidelines on Se biogeochemistry research.

Isotope investigation of mercury sources in a creek impacted by multiple anthropogenic activities.

To investigate mercury (Hg) sources responsible for contamination at Gumu Creek in South Korea, Hg concentration (THg) and Hg isotope ratios were measured in the soil and sediment of Gumu Creek and the samples from a hazardous waste landfill (HWL). The THg ranged between 0.29-327 mg kg-1 and 9.5-414 mg kg-1 in the soil and sediment, respectively, reflecting heterogeneous distribution and elevated levels across the entire Gumu Creek. Without the soil with the lowest THg (0.30 ± 0.01 mg kg-1, n = 3), the δ202Hg (-0.83 to -0.18‰) and Δ199Hg (-0.24 to 0.01‰) of the sediment and soil of Gumu Creek were within the ranges of the HWL samples (δ202Hg; -1.29 to -0.38‰, Δ199Hg; -0.31 to 0.01‰). The comparison with the literature reporting sediment Hg isotope ratios impacted by various anthropogenic Hg sources revealed a presence of diverse Hg sources at Gumu Creek, including commercial liquid Hg, phenyl-Hg, and fly ash, consistent with the types of waste deposited within the HWL. Using commercial liquid Hg, fly ash, and the soil with the lowest THg as end-members, the ternary mixing model yielded 25-88% and 12-57% contributions from commercial liquid Hg and fly ash to the Gumu Creek sediment, respectively. The results of our study suggest that Hg isotope ratios are an effective tool for screening potential Hg sources at sites where the distribution of Hg is heterogeneous and multiple anthropogenic activities exist.

Short-Term Legacy Effects of Mercury Contamination on Plant Growth and nifH-Harboring Microbial Community in Rice Paddy Soil.

Methylmercury (MeHg), which is formed in rice paddy soil, exhibits strong neurotoxicity through bioaccumulation in the food chain. A few groups of microorganisms drive both mercury methylation and nitrogen fixation in the rhizosphere. Little is known about how the shifted soil microbial community by Hg contamination affects nitrogen fixation rate and plant growth in paddy soil. Here, we examined how stimulated short-term Hg amendment affects the nitrogen fixing microbial community and influences plant-microbe interactions. Soil was treated with low (0.2 mg/kg) and high (1.1 mg/kg) concentrations of Hg for 4 weeks; then, rice (Oryza sativa) was planted and grown for 12 weeks. The nitrogen-fixation rate and rice growth were measured. The diversity and structure of the microbial community were analyzed by sequencing the nifH gene before and after rice cultivation. Hg treatments significantly decreased the nitrogen fixation rate and dry weight of the rice plants. The structure of the nifH-harboring community was remarkably changed after rice cultivation depending on Hg treatments. Iron- or sulfate-reducing bacteria, including Desulfobacca, Desulfoporosimus, and Geobacter, were observed as legacy response groups; their abundances increased in the soil after Hg treatment. The high abundance of those groups were maintained in control, but the abundance drastically decreased after rice cultivation in the soil treated with Hg, indicating that symbiotic behavior of rice plants changes according to the legacy effects on Hg contamination. These results suggested that Hg contamination can persist in soil microbial communities, affecting their nitrogen-fixation ability and symbiosis with rice plants in paddy soil.

Twenty-year trends and exposure assessment of polychlorinated dibenzodioxins and dibenzofurans in human serum from the Seoul citizens.

This study investigated polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) in air (n = 108) and human serum (n = 1802) samples collected over 20 years to evaluate the long-term exposure to PCDD/Fs and health effects on the Korean general population. The serum PCDD/F levels were higher in males than in females and were significantly correlated with age, body mass index, and manifestation of diabetes mellitus. From 2000 to 2019, the PCDD/F levels declined by 96% in the air, but only by 36% in the serum, because PCDD/Fs are relatively stable in the human body and are exposed to humans after PCDD/Fs are distributed and migrated in various environmental matrices. The PCDD/F levels in other environmental matrices have also decreased at rates that differed among the matrices due to the different retention times and changes in continuous input of contaminants. As PCDD/Fs migrate from environmental matrices to the human body, the fraction of PCDDs increased whereas that of PCDFs decreased because of their relatively short half-lives. This study provides a concrete evidence that PCDD/F emissions by national regulations can achieve long-term reduction in human exposure. To the best of our knowledge, this is the longest and largest study to evaluate the long-term trends and annual changes of PCDD/Fs in the atmosphere and human serum, simultaneously.