Continuous Flow-Double Purge and Trap Method for Preconcentrating Mercury in Large Volumes of Seawater for Stable Isotope Analysis.

Mercury (Hg) isotopes provide a useful tool to understand Hg sources and processes in the environment. The Hg isotopic composition of seawater remains poorly constrained due to the lack of an efficient method to process large volumes of low-Hg-concentration seawater samples. Here, we develop a continuous flow-double purge and trap device for the in situ preconcentration of Hg in seawater. This method yielded a good Hg recovery of 91.7 ± 3.3% (n = 4, 1SD) for spiked seawater samples and gave reasonably similar Hg isotope ratios of NIST 8610, indicating a limited matrix effect and limited Hg isotope fractionation during processing of seawater. NIST 8610 δ202Hg (-0.55 ± 0.09‰, n = 4, 1SD) and Δ199Hg (0.07 ± 0.02‰, n = 4, 1SD) were similar to previously published data. The method was successfully applied to seawater collected from the Xiamen Bay and the South China Sea. The seawater samples showed a Hg recovery of 91.6 ± 5.4% (n = 12, 1SD). Seawater Δ199Hg (-0.04 ± 0.05‰, n = 7, 1SD) in the Xiamen Bay was different from seawater Δ199Hg (0.05 ± 0.07‰, n = 5, 1SD) in the South China Sea, which implies distinct Hg sources to coastal and open ocean areas and highlights the robustness of our method in understanding the Hg isotopic composition of seawater.

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.

Lake Sediment Archive Reveals a Distinct Response to Anthropogenic Pb and Zn Deposition with Historical Periods: Pb-Zn Isotope Evidence.

Anthropogenic activities release large quantities of heavy metals into the atmosphere. In China, the input of these heavy metals through local and trans-boundary atmospheric deposition is poorly understood. To assess this issue, herein, we use Pb and Zn isotopes to constrain the sources of Pb and Zn in a 210Pb-dated sediment core collected from the enclosed lake in South China. We observed a progressive shift toward higher 208Pb/206Pb and Pb fluxes (0.79-4.02 µg·cm-2·a-1) from 1850 to 1950 and a consistent decrease in δ66ZnIRMM (as low as -0.097 ± 0.030‰) coupled with an increase in Pb (1.74-3.36 µg·cm-2·a-1) and Zn (8.07-10.44 µg·cm-2·a-1) fluxes after 1980. These distinguished isotopic signals and flux variations reveal the presence of trans-boundary Pb since 1900, with the addition of local industrial Pb and Zn pollution after 1980. Up to 72.3% of Pb deposited at our site can be attributed to long-distance transportation from previously industrialized countries, resulting in a noteworthy legacy of Pb in China since 1900. Despite the phasing out of leaded gasoline, Chinese gasoline still contributes an average of 20.9%. The contribution of China's mining and smelting activities to Pb has increased steadily since 1980 and remained stable at an average of 25.1% since 2000.

Isotopic and Spectroscopic Investigation of Mercury Accumulation in Houttuynia cordata Colonizing Historically Contaminated Soil.

Houttuynia cordata Thunb (H. cordata) is a native vegetable colonizing mercury (Hg) mining sites in the southwest of China; it can accumulate high Hg concentrations in the rhizomes and roots (edible sections), and thus consumption of H. cordata represents an important Hg exposure source to human. Here, we studied the spatial distribution, chemical speciation, and stable isotope compositions of Hg in the soil-H. cordata system at the Wuchuan Hg mining region in China, aiming to provide essential knowledge for assessing Hg risks and managing the transfer of Hg from soils to plants and agricultural systems. Mercury was mainly compartmentalized in the outlayer (periderm) of the underground tissues, with little Hg being translocated to the vascular bundle of the stem. Mercury presented as Hg-thiolates (94% ± 8%), with minor fractional amount of nanoparticulate ß-HgS (ß-HgSNP, 15% ± 4%), in the roots and rhizomes. Analysis of Hg stable isotope ratios showed that cysteine-extractable soil Hg pool (δ202Hgcys), root and rhizome Hg (δ202Hgroot, δ202Hgrhizome) were isotopically lighter than Hg in the bulk soils. A significant positive correlation between δ202Hgcys and δ202Hgroot was observed, suggesting that cysteine-extractable soil Hg pool was an important Hg source to H. cordata. The slightly positive Δ199Hg value in the plant (Δ199Hgroot = 0.07 ± 0.07‰, 2SD, n = 21; Δ199Hgrhizome = 0.06 ± 0.06‰, 2SD, n = 22) indicated that minor Hg was sourced from the surface water. Our results are important to assess the risks of Hg in H. cordata, and to develop sustainable methods to manage the transfer of Hg from soils to agricultural systems.

Dissociation of Mercuric Oxides Drives Anomalous Isotope Fractionation during Net Photo-oxidation of Mercury Vapor in Air.

The atmosphere is the primary medium for long-distance transport and transformation of elemental mercury (Hg), a potent neurotoxin. The recent discovery of mass-independent fractionation (MIF) of even-mass Hg isotopes (even-MIF, measured as Δ200Hg and Δ204Hg) in the atmosphere is surprising and can potentially serve as a powerful tracer in understanding Hg biogeochemistry. Far-ultraviolet (UVC) light-induced gas-phase reactions have been suspected as a likely cause for even-MIF, yet the mechanism remains unknown. Here, we present the first experimental evidence of large-scale even-MIF caused by UVC-induced (wavelength: 254 nm) Hg oxidation in synthetic air at the pressure (46-88 kPa) and temperature (233-298 K) resembling those of the lower atmosphere. We observe negatively correlated Δ200Hg and Δ204Hg signatures with values as low as -50‰ and as high as 550‰, respectively, in the remaining atomic Hg pool. The magnitude of even-MIF signatures decreases with decreasing pressure with the Δ200Hg/Δ204Hg ratio being similar to that observed in global precipitation. This even-MIF can be explained by photodissociation of mercuric oxides that are photochemically formed in the UVC-irradiated Hg-O2 system. We propose that similar processes occurring in the atmosphere, where mercuric oxide species serve as intermediates, are responsible for the observed even-MIF in the environment.

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

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

Compound-Specific Stable Isotope Analysis Provides New Insights for Tracking Human Monomethylmercury Exposure Sources.

Monomethylmercury (MMHg) exposure can induce adverse neurodevelopmental effects in humans and is a global environmental health concern. Human exposure to MMHg occurs predominately through the consumption of fishery foods and rice in Asia, but it is challenging to quantify these two exposure sources. Here, we innovatively utilized MMHg compound-specific stable isotope analyses (MMHg-CSIA) of the hair to quantify the human MMHg sources in coastal and inland areas, where fishery foods and rice are routinely consumed. Our data showed that the fishery foods and rice end members had distinct Δ199HgMMHg values in both coastal and inland areas. The Δ199HgMMHg values of the human hair were comparable to those of fishery foods but not those of rice. Positive shifts in the δ202HgMMHg values of the hair from diet were observed in the study areas. Additionally, significant differences in δ202Hg versus Δ199Hg were detected between MMHg and inorganic Hg (IHg) in the human hair but not in fishery foods and rice. A binary mixing model was developed to estimate the human MMHg exposures from fishery foods and rice using Δ199HgMMHg data. The model results suggested that human MMHg exposures were dominated (>80%) by fishery food consumption and were less affected by rice consumption in both the coastal and inland areas. This study demonstrated that the MMHg-CSIA method can provide unique information for tracking human MMHg exposure sources by excluding the deviations from dietary surveys, individual MMHg absorption/demethylation efficiencies, and the confounding effects of IHg.

Monthly variations in mercury exposure of school children and adults in an industrial area of southwestern China.

Recent studies have shown that rice consumption can be the major pathway for human methylmercury (MeHg) exposure in inland China. However, few studies have considered the susceptible population of school children's exposure through rice ingestion. In this study, monthly variations in total Hg (THg)/MeHg concentrations in rice, fish, hair, and urine samples were studied to evaluate the Hg (both THg and MeHg) exposure in Guiyang, a typical industrial area with high anthropogenic emission of Hg. A total of 17 primary school (school A) students, 29 middle school (school B) students, and 46 guardians participated in this study for one year. Hair THg, hair MeHg, and urine THg concentrations ranged from 355-413 ng g-1, 213-236 ng g-1, and 469-518 ng g-1 Creatinine (ng·g-1 Cr), respectively, and no significant differences were observed between different genders and age groups. Hair and urine Hg concentrations showed slightly higher values in the cold season (October to February) than the hot season (March to September), but without significant difference. High monthly variability of individual hair and urine Hg concentrations suggested that long-term study could effectively decrease the uncertainty. The school students showed significantly higher urine THg concentrations than adults due to children's unique physiological structure and behaviors. Probable daily intake (PDI) of MeHg via rice and fish ingestion averaged at 0.0091, 0.0090, and 0.0079 µg kg-1 d-1 for school A students, school B students, and their guardians, respectively, which means that 86%, 84%, and 87% of the PDI were originated from rice ingestion, respectively. Therefore, more attention should be paid to children as a susceptible population. The results indicated low risk of Hg exposure via rice and fish consumption for urban residents in a Chinese industrial city.

Isotopic Fractionation and Source Appointment of Methylmercury and Inorganic Mercury in a Paddy Ecosystem.

Bioaccumulation of methylmercury (MeHg) in rice grains has been an emerging issue of human health, but the mechanism of bioaccumulation is still poorly understood. Mercury (Hg) isotope measurements are powerful tools for tracing the sources and biogeochemical cycles of Hg in the environment. In this study, MeHg compound-specific stable isotope analysis (CSIA) was developed in paddy soil and rice plants to trace the biogeochemical cycle of Hg in a paddy ecosystem during the whole rice-growing season. Isotopic fractionation was analyzed separately for MeHg and inorganic Hg (IHg). Results showed distinct isotopic signals between MeHg and IHg in rice plants, indicating different sources. δ202Hg values of MeHg showed no significant differences between roots, stalks, leaves, and grains at each growth stage. The similar Δ199Hg values of MeHg between rice tissues (0.14 ± 0.08‰, 2SD, n = 12), soil (0.13 ± 0.03‰, 2SD, n = 4), and irrigation water (0.17 ± 0.09‰, 2SD, n = 5) suggested that the soil-water system was the original source of MeHg in rice plants. Δ199Hg values of IHg in the paddy ecosystem indicated that water, soil, and atmosphere contributed to IHg in grains, leaves, stalks, and roots with varying degree. This study demonstrates that successful application of MeHg CSIA can improve our understanding of the sources and bioaccumulation mechanisms of MeHg and IHg in the paddy ecosystems.

Bioaccumulation of Hg in Rice Leaf Facilitates Selenium Bioaccumulation in Rice (Oryza sativa L.) Leaf in the Wanshan Mercury Mine.

Mercury (Hg) bioaccumulation in rice poses a health issue for rice consumers. In rice paddies, selenium (Se) can decrease the bioavailability of Hg through forming the less bioavailable Hg selenides (HgSe) in soil. Rice leaves can directly uptake a substantial amount of elemental Hg from the atmosphere, however, whether the bioaccumulation of Hg in rice leaves can affect the bioaccumulation of Se in rice plants is not known. Here, we conducted field and controlled studies to investigate the bioaccumulation of Hg and Se in the rice-soil system. In the field study, we observed a significantly positive correlation between Hg concentrations and BAFs of Se in rice leaves (r2 = 0.60, p < 0.01) collected from the Wanshan Mercury Mine, SW China, suggesting that the bioaccumulation of atmospheric Hg in rice leaves can facilitate the uptake of soil Se, perhaps through the formation of Hg-Se complex in rice leaves. This conclusion was supported by the controlled study, which observed significantly higher concentrations and BAFs of Se in rice leaf at a high atmospheric Hg site at WMM, compared to a low atmospheric Hg site in Guiyang, SW China.

Decoupling Natural and Anthropogenic Mercury and Lead Transport from South Asia to the Himalayas.

Mercury (Hg) and lead (Pb) accumulation since the Industrial Revolution has been generally observed to increase concurrently in lake sedimentary records around the world. Located downwind during the monsoon season from the rapidly developing South Asia, the Himalayas and the Tibetan Plateau are expected to receive direct anthropogenic Hg and Pb loadings, yet the source, pathway, and effects of such transport remain poorly known due to logistic challenges in accessing this region. When studying the sediment record from Lake Gokyo (4750 m above sea level (a.s.l.)) in the Himalayas, we find remarkably different Hg and Pb accumulation trends over the past 260 years. Although Hg accumulation has continued to increase since the Industrial Revolution, Pb accumulation peaked during that time and has been decreasing since then. Stable isotope analysis reveals that the decoupling trends between these two elements are due to different sources and pathways of Hg and Pb in the region. Both δ202Hg and Δ199Hg have been increasing since the Industrial Revolution, suggesting that anthropogenic Hg emissions from South Asia have been continuously increasing and that the Indian monsoon-driven wet deposition of atmospheric Hg is the dominant pathway for Hg accumulation in the sediments. In contrast, analysis of 206Pb/207Pb and 208Pb/207Pb ratios suggests that Pb accumulation in the sediments originates primarily from natural sources and that the decreasing trend of Pb accumulation is most likely due to a weakening input of atmospheric mineral dust by the westerlies. These decoupling trends highlight the ongoing issue of transboundary Hg transport to the Himalayas and the Tibetan Plateau that are source waters for major freshwater systems in Asia and calls for regional and international collaborations on Hg emission controls in South Asia.

Resolving Atmospheric Mercury Loading and Source Trends from Isotopic Records of Remote North American Lake Sediments.

The strongest evidence for anthropogenic alterations to the global mercury (Hg) cycle comes from historical records of mercury deposition preserved in lake sediments. Hg isotopes have added a new dimension to these sedimentary archives, promising additional insights into Hg source apportionment and biogeochemical processing. Presently, most interpretations of historical changes are constrained to a small number of locally contaminated ecosystems. Here, we describe changes in natural Hg isotope records from a suite of dated sediment cores collected from various remote lakes of North America. In nearly all cases, the rise in industrial-use Hg is accompanied by an increase in δ202Hg and Δ199Hg values. These trends can be attributed to large-scale industrial emission of Hg into the atmosphere and are consistent with positive Δ199Hg values measured in modern-day precipitation and modeled increases in δ202Hg values from global emission inventories. Despite similar temporal trends among cores, the baseline isotopic values vary considerably among the different study regions, likely attributable to differences in the fractionation produced in situ as well as differing amounts of atmospherically delivered Hg. Differences among the study lakes in precipitation and watershed size provide an empirical framework for evaluating Hg isotopic signatures and global Hg cycling.

Accumulation of Atmospheric Mercury in Glacier Cryoconite over Western China.

Cryoconite is a granular aggregate, comprised of both mineral and biological material, and known to accumulate atmospheric contaminants. In this study, cryoconite was sampled from seven high-elevation glaciers in Western China to investigate the spatial and altitudinal patterns of atmospheric mercury (Hg) accumulation in the cryoconite. The results show that total Hg (HgT) concentrations in cryoconite were significant with relatively higher Hg accumulation in the southern glaciers (66.0 ± 29.3 ng g-1), monsoon-influenced regions, than those in the northern glaciers (42.5 ± 20.7 ng g-1), westerlies-influenced regions. The altitudinal profile indicates that HgT concentrations in the northern glaciers decrease significantly with altitude, while those in the southern glaciers generally increase toward higher elevations. Unexpectedly high accumulation of methyl-Hg (MeHg) with an average of 1.0 ± 0.4 ng g-1 was also detected in the cryoconite samples, revealing the surface of cryoconite could act as a potential site for Hg methylation in alpine environments. Our preliminary estimate suggests a storage of ∼34.3 ± 17.4 and 0.65 ± 0.28 kg of HgT and MeHg from a single year of formation process in the glacier cryoconite. Therefore, glacier cryoconite could play an important role in Hg storage and transformation, which may result in downstream effects on glacier-fed ecosystems under climate warming scenario.

Estimating the social and ecological impact of community-based ecotourism in giant panda habitats.

Community-based ecotourism (CBET) is considered an efficient mechanism for alleviating conflicts between conservation and development. It is particularly important in the conservation of the giant panda population, which faces the primary threat of habitat fragmentation. Although studies have assessed livelihood changes of households participating in CBET, research on ecological effects is lacking. To address the gaps in the literature, we conducted propensity score matching on data from households at different altitudes in giant panda habitats in Sichuan Province, China. The results show that CBET has achieved desirable social outcomes, significantly increasing local households' income and well-being, especially for those at high altitudes. With respect to ecological impacts, CBET has significantly raised households' conservation attitudes, but has also increased natural resource extraction, especially at high altitudes. Overall, CBET in the giant panda habitat has not led to a win-win situation between social and ecological outcomes, especially at high altitudes. Our results indicate that the ecological impact of CBET is significant, and policies aimed at promoting the conservation of natural resources should account for this effect.

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

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

Use of Mercury Isotopes to Quantify Mercury Exposure Sources in Inland Populations, China.

Mercury (Hg) isotopic compositions in hair and dietary sources from Wanshan (WS) Hg mining area, Guiyang (GY) urban area, and Changshun (CS) rural area were determined to identify the major Hg exposure sources of local residents. Rice and vegetables displayed low δ202Hg and small negative to zero Δ199Hg, and are isotopically distinguishable from fish which showed relatively higher δ202Hg and positive Δ199Hg. Distinct isotopic signatures were also observed for human hair from the three areas. Shifts of 2 to 3‰ in δ202Hg between hair and dietary sources confirmed mass dependent fractionation of Hg isotopes occurs during metabolic processes. Near zero Δ199Hg of hair from WS and CS suggested rice is the major exposure source. Positive Δ199Hg of hair from GY was likely caused by consumption of fish. A binary mixing model based on Δ199Hg showed that rice and fish consumption accounted for 59% and 41% of dietary Hg source for GY residents, respectively, whereas rice is the major source for WS and CS residents. The model output was validated by calculation of probable daily intake of Hg. Our study suggests that Hg isotopes can be a useful tracer for quantifying exposure sources and understanding metabolic processes of Hg in humans.

Mercury Stable Isotopes Reveal Influence of Foraging Depth on Mercury Concentrations and Growth in Pacific Bluefin Tuna.

Pelagic ecosystems are changing due to environmental and anthropogenic forces, with uncertain consequences for the ocean's top predators. Epipelagic and mesopelagic prey resources differ in quality and quantity, but their relative contribution to predator diets has been difficult to track. We measured mercury (Hg) stable isotopes in young (<2 years old) Pacific bluefin tuna (PBFT) and their prey species to explore the influence of foraging depth on growth and methylmercury (MeHg) exposure. PBFT total Hg (THg) in muscle ranged from 0.61 to 1.93 µg g-1 dw (1.31 µg g-1 dw ±0.37 SD; 99% ± 6% MeHg) and prey ranged from 0.01 to 1.76 µg g-1 dw (0.13 µg g-1 dw ±0.19 SD; 85% ± 18% MeHg). A systematic decrease in prey δ202Hg and Δ199Hg with increasing depth of occurrence and discrete isotopic signatures of epipelagic prey (δ202Hg: 0.74 to 1.49‰; Δ199Hg: 1.76-2.96‰) and mesopelagic prey (δ202Hg: 0.09 to 0.90‰; Δ199Hg: 0.62-1.95‰) allowed the use of Hg isotopes to track PBFT foraging depth. An isotopic mixing model was used to estimate the dietary proportion of mesopelagic prey in PBFT, which ranged from 17% to 55%. Increased mesopelagic foraging was significantly correlated with slower growth and higher MeHg concentrations in PBFT. The slower observed growth rates suggest that prey availability and quality could reduce the production of PBFT biomass.

Effects of soil properties on production and bioaccumulation of methylmercury in rice paddies at a mercury mining area, China.

Rice paddy soil is recognized as the hotspot of mercury (Hg) methylation, which is mainly a biotic process mediated by many abiotic factors. In this study, effects of key soil properties on the production and bioaccumulation of Hg and methylmercury (MeHg) in Hg-contaminated rice paddies were investigated. Rice and soil samples were collected from the active Hg smelting site and abandoned Hg mining sites (a total of 124 paddy fields) in the Wanshan Mercury Mine, China. Total Hg (THg) and MeHg in soils and rice grains, together with sulfur (S), selenium (Se), organic matter (OM), nitrogen (N), phosphorus (P), mineral compositions (e.g., SiO2, Al2O3 and Fe2O3) and pH in soils were quantified. The results showed that long-term Hg mining activities had resulted in THg and MeHg contaminations in soil-rice system. The newly-deposited atmospheric Hg was more readily methylated relative to the native Hg already in soils, which could be responsible for the elevated MeHg levels in soils and rice grains around the active artificial Hg smelting site. The MeHg concentrations in soils and rice grains showed a significantly negative relationship with soil N/Hg, S/Hg and OM/Hg ratio possibly due to the formation of low-bioavailability Hg-S(N)-OM complexes in rhizosphere. The Hg-Se antagonism undoubtedly occurred in soil-rice system, while its role in bioaccumulation of MeHg in the MeHg-contaminated rice paddies was minor. However, other soil properties showed less influence on the production and bioaccumulation of MeHg in rice paddies located at the Wanshan Mercury Mine zone.

Stable Mercury Isotopes in Polished Rice (Oryza sativa L.) and Hair from Rice Consumers.

Mercury (Hg) isotopic signatures were characterized in polished rice samples from China, U.S., and Indonesia (n = 45). Hg isotopes were also analyzed in paired hair samples for participants from China (n = 21). For the latter, we also quantified the proportion of methylmercury intake through rice (range: 31-100%), and the weekly servings of fish meals (range: 0-5.6 servings/weekly). For these participants, 29% (n = 6) never ingested fish, 52% (n = 11) ingested fish < twice/weekly, and 19% (n = 4) ingested fish ≥ twice/weekly. In rice and hair, both mass-dependent fractionation (MDF, reported as δ202Hg) and mass-independent fractionation (MIF, reported as Δ199Hg) of Hg isotopes were observed. Compared to rice, hair δ202Hg values were enriched on average (±1 standard deviation) by 1.9 ± 0.61‰, although the range was wide (range: 0.45‰, 3.0‰). Hair Δ199Hg was significantly inversely associated with %methylmercury intake from rice (Spearman's rho = -0.61, p < 0.01, n = 21), i.e., as the proportion of methylmercury intake from rice increased, MIF decreased. Additionally, hair Δ199Hg was significantly higher for participants ingesting fish ≥ twice/weekly compared to those who did not ingest fish or ingested fish < twice/weekly (ANOVA, p < 0.05, n = 21); Overall, results suggest that Hg isotopes (especially MIF) in human hair can be used to distinguish methylmercury intake from rice versus fish.

Using Mercury Isotopes To Understand Mercury Accumulation in the Montane Forest Floor of the Eastern Tibetan Plateau.

Mercury accumulation in montane forested areas plays an important role in global Hg cycling. In this study, we measured stable Hg isotopes in soil and litter samples to understand Hg accumulation on the forest floor along the eastern fringe of the Tibetan Plateau (TP). The low atmospheric Hg inputs lead to the small Hg pool size (23 ± 9 mg m-2 in 0-60 cm soil horizon), up to 1 order of magnitude lower than those found at sites in Southwest China, North America, and Europe. The slightly negative Δ199Hg (-0.12 to -0.05‰) in the litter at low elevations (3100 to 3600 m) suggests an influence of local anthropogenic emissions, whereas the more significant negative Δ199Hg (-0.38 to -0.15‰) at high elevations (3700 to 4300 m) indicates impact from long-range transport. Hg input from litter is more important than wet deposition to Hg accumulation on the forest floor, as evidenced by the negative Δ199Hg found in the surface soil samples. Correlation analyses of Δ199Hg versus total carbon and leaf area index suggest that litter biomass production is a predominant factor in atmospheric Hg inputs to the forest floor. Precipitation and temperature show indirect effects on Hg accumulation by influencing litter biomass production in the eastern TP.