Hg Isotopes Research Articles

Organ-specific mercury stable isotopes, speciation and particle measurements reveal methylmercury detoxification processes in Atlantic Bluefin Tuna

Identifying metabolism and detoxification mechanisms of Hg in biota has important implications for biomonitoring, ecotoxicology, and food safety. Compared to marine mammals and waterbirds, detoxification of MeHg in fish is understudied. Here, we investigated Hg detoxification in Atlantic bluefin tuna Thunnus thynnus using organ-specific Hg and Se speciation data, stable Hg isotope signatures, and Hg and Se particle measurements in multiple tissues. Our results provide evidence for in vivo demethylation and biomineralization of HgSe particles, particularly in spleen and kidney. We observed a maximum range of 1.83‰ for δ202Hg between spleen and lean muscle, whereas Δ199Hg values were similar across all tissues. Mean percent methylmercury ranged from 8% in spleen to 90% in lean muscle. The particulate masses of Hg and Se were higher in spleen and kidney (Hg: 61% and 59%, Se: 12% and 6%, respectively) compared to muscle (Hg: 2%, Se: 0.05%). Our data supports the hypothesis of an organ-specific, two-step detoxification of methylmercury in wild marine fish, consisting of demethylation and biomineralization, like reported for waterbirds. While mass dependent fractionation signatures were highly organ specific, stable mass independent fractionation signatures across all tissues make them potential candidates for source apportionment studies of Hg using ABFT.

Using Hg isotopes and trace elements to constrain the origin of the Ordovician Xiangquan Tl deposit, South China

Sediment-hosted stratiform sulfide (SHSS) deposits commonly contain large amounts of strategic metals, such as Tl, Hg, Cd, Ge and Ga, however, sources of these metals remain debate. Here we present new elemental and Hg isotopic data to constrain the metal sources for the Xiangquan Tl deposit (South China), a unique SHSS deposit with 250 t Tl at an average grade of 928 ppm. Stratiform pyrite orebodies are hosted in the Ordovician marine sedimentary succession of mostly limestone with minor mudstone. Pyrite, the dominant ore mineral, is rich in Hg (up to 1360 ppm). Bulk ores and pyrite separates from this deposit have significant variations of δ202Hg (−5.48 to −0.65 ‰) and Δ199Hg (−0.01 to 0.36 ‰). The Δ199Hg values are mostly positive, similar to those of seawater and marine sediments. Ore petrography, trace element enrichment coefficients, rare earth element patterns, Re-Os ages (478 ± 33 Ma) and S isotope compositions of pyrite indicate that Hg and other metals were derived from hydrothermal fluids venting at the seafloor. We suggest that the ore-forming fluids of the Xiangquan deposit were predominantly originated from large-scale circulation of evolved seawater, which leached Hg and Tl from the marine country rocks. These metal-rich fluids migrated upward, vented to the seafloor, and mixed with anoxic H2S-rich seawater to precipitate Hg- and Tl-rich pyrite. Our study highlights that the combined application of Hg isotopes and trace elements could be used to trace the sources of metals in hydrothermal ore deposits such as SHSS deposits.

Unveiling the Sources and Transfer of Mercury in Forest Bird Food Chains Using Techniques of Vivo-Nest Video Recording and Stable Isotopes.

Knowledge gaps in mercury (Hg) biomagnification in forest birds, especially in the most species-rich tropical and subtropical forests, limit our understanding of the ecological risks of Hg deposition to forest birds. This study aimed to quantify Hg bioaccumulation and transfer in the food chains of forest birds in a subtropical montane forest using a bird diet recorded by video and stable Hg isotope signals of biological and environmental samples. Results show that inorganic mercury (IHg) does not biomagnify along food chains, whereas methylmercury (MeHg) has trophic magnification factors of 7.4-8.1 for the basal resource-invertebrate-bird food chain. The video observations and MeHg mass balance model suggest that Niltava (Niltava sundara) nestlings ingest 78% of their MeHg from forest floor invertebrates, while Flycatcher (Eumyias thalassinus) nestlings ingest 59% from emergent aquatic invertebrates (which fly onto the canopy) and 40% from canopy invertebrates. The diet of Niltava nestlings contains 40% more MeHg than that of Flycatcher nestlings, resulting in a 60% higher MeHg concentration in their feather. Hg isotopic model shows that atmospheric Hg0 is the main Hg source in the forest bird food chains and contributes >68% in most organisms. However, three categories of canopy invertebrates receive ∼50% Hg from atmospheric Hg2+. Overall, we highlight the ecological risk of MeHg exposure for understory insectivorous birds caused by atmospheric Hg0 deposition and methylation on the forest floor.

Above- and belowground plant mercury dynamics in a salt marsh estuary in Massachusetts, USA

Abstract. Estuaries are a conduit of mercury (Hg) from watersheds to the coastal ocean, and salt marshes play an important role in coastal Hg cycling. Hg cycling in upland terrestrial ecosystems has been well studied, but processes in densely vegetated salt marsh ecosystems are poorly characterized. We investigated Hg dynamics in vegetation and soils in the Plum Island Sound estuary in Massachusetts, USA, and specifically assessed the role of marsh vegetation for Hg deposition and turnover. Monthly quantitative harvesting of aboveground biomass showed strong linear seasonal increases in Hg associated with plants, with a 4-fold increase in Hg concentration and an 8-fold increase in standing Hg mass from June (3.9 ± 0.2 µg kg−1 and 0.7 ± 0.4 µg m−2, respectively) to November (16.2 ± 2.0 µg kg−1 and 5.7 ± 2.1 µg m−2, respectively). Hg did not increase further in aboveground biomass after plant senescence, indicating physiological controls of vegetation Hg uptake in salt marsh plants. Hg concentrations in live roots and live rhizomes were 11 and 2 times higher than concentrations in live aboveground biomass, respectively. Furthermore, live belowground biomass Hg pools (Hg in roots and rhizomes, 108.1 ± 83.4 µg m−2) were more than 10 times larger than peak standing aboveground Hg pools (9.0 ± 3.3 µg m−2). A ternary mixing model of measured stable Hg isotopes suggests that Hg sources in marsh aboveground tissues originate from about equal contributions of root uptake (∼ 35 %), precipitation uptake (∼ 33 %), and atmospheric gaseous elemental mercury (GEM) uptake (∼ 32 %). These results suggest a more important role of Hg transport from belowground (i.e., roots) to aboveground tissues in salt marsh vegetation than upland vegetation, where GEM uptake is generally the dominant Hg source. Roots and soils showed similar isotopic signatures, suggesting that belowground tissue Hg mostly derived from soil uptake. Annual root turnover results in large internal Hg recycling between soils and plants, estimated at 58.6 µg m−2 yr−1. An initial mass balance of Hg indicates that the salt marsh presently serves as a small net Hg sink for environmental Hg of 5.2 µg m−2 yr−1.

Legacy Mercury Re-emission and Subsurface Migration at Contaminated Sites Constrained by Hg Isotopes and Chemical Speciation.

The re-emission and subsurface migration of legacy mercury (Hg) are not well understood due to limited knowledge of the driving processes. To investigate these processes at a decommissioned chlor-alkali plant, we used mercury stable isotopes and chemical speciation analysis. The isotopic composition of volatilized Hg(0) was lighter compared to the bulk total Hg (THg) pool in salt-sludge and adjacent surface soil with mean ε202HgHg(0)-THg values of -3.29 and -2.35‰, respectively. Hg(0) exhibited dichotomous directions (E199HgHg(0)-THg = 0.17 and -0.16‰) of mass-independent fractionation (MIF) depending on the substrate from which it was emitted. We suggest that the positive MIF enrichment during Hg(0) re-emission from salt-sludge was overall controlled by the photoreduction of Hg(II) primarily ligated by Cl- and/or the evaporation of liquid Hg(0). In contrast, O-bonded Hg(II) species were more important in the adjacent surface soils. The migration of Hg from salt-sludge to subsurface soil associated with selective Hg(II) partitioning and speciation transformation resulted in deep soils depleted in heavy isotopes (δ202Hg = -2.5‰) and slightly enriched in odd isotopes (Δ199Hg = 0.1‰). When tracing sources using Hg isotopes, it is important to exercise caution, particularly when dealing with mobilized Hg, as this fraction represents only a small portion of the sources.

Isotopic insights and integrated analysis for heavy metal levels, ecological risks, and source apportionment in river sediments of the Qinghai-Tibet Plateau

The research was carried out to examine the pollution characteristics, ecological risk, and origins of seven heavy metals (Hg, As, Pb, Cu, Cd, Zn, and Ni) in 51 sediment samples gathered from 8 rivers located on the Qinghai-Tibet Plateau (QTP) in China. The contents of Hg and Cd were 5.0 and 1.1 times higher than their background values, respectively. The mean levels of other measured heavy metals were below those found naturally in the local soil. The enrichment factor showed that the study area exhibited significantly enriched Hg with 70.6% sampling sites. The Cd contents at 19.6% of sampling sites were moderately enriched. The other sampling sites were at a less enriched level. The sediments of all the rivers had a medium level of potential ecological risk. Hg was the major ecological risk factor in all sampling sites, followed by Cd. The findings from the positive matrix factorization (PMF) analysis shown agricultural activities, industrial activities, traffic emissions, and parent material were the major sources. The upper, middle, and low reaches of the Quanji river had different Hg isotope compositions, while sediments near the middle reaches were similar to the δ202Hg of the industrial source. At the upstream sampling sites, the Hg isotope content was very close to the background level. The results of this research can establish a strong scientific sound to improve the safety of the natural circumstances of rivers on the QTP.

Lithospheric mantle as a metal storage reservoir for orogenic gold deposits in active continental margins: Evidence from Hg isotopes

Abstract The subcontinental lithospheric mantle (SCLM) is now suggested by many workers to play a role in the formation of orogenic gold deposits in active continental margins, given that the gold and volatiles may be introduced into the SCLM during plate subduction. The giant Cretaceous Jiaodong gold province within the North China block occurs in a convergent margin setting where there is no terrane accretion, thus eliminating from consideration the commonly accepted metal and fluid source reservoir for orogenic gold—the metamorphosed upper crust of an active orogenic belt. Thus, the auriferous fluids were released below the high-grade Archean cratonic rocks from either enriched SCLM or directly from the subducted oceanic slab. Mercury (Hg) isotopes allow fingerprinting of isotopically distinct reservoirs, discriminating between the two possibilities. We present Hg isotope data for a set of pyrite grains, native gold, and lamprophyres from six main gold districts in the Jiaodong gold province. These samples dominantly yielded near-zero Δ199Hg (0‰ ± 0.1‰), within uncertainty of the mantle Δ199Hg value. The results provide novel evidence that the SCLM predominantly controlled the Hg budget of the Jiaodong gold deposits, implying that the SCLM acted as a buffer for the crustal mass-independent fractionation Hg signatures and a storage reservoir for gold and volatiles. Consequently, during slab subduction, gold and volatiles were recycled and stored within the SCLM and were later released from the mantle during uplift and relaxation of compressional tectonics.

Properties influencing flux and diatom uptake of mercury and methylmercury from estuarine sediments

Mercury (Hg) is a conspicuous and persistent global pollutant. Ionic Hg can be methylated into noxious methylmercury (CH3Hg), which biomagnifies in marine tropic webs and poses a health risk to humans and organisms. Sediment Hg methylation rates are variable, and the output flux of created CH3Hg are dependent on sediment characteristics and environmental factors. Thus, uncertainties remain about the formation and flux of CH3Hg from sediment, and how this could contribute to the bioaccumulative burden for coastal organisms in shallow ecosystems. Cores were collected from 3 estuarine locations along the Eastern USA to examine how sediments characteristics influence the introduction of Hg and CH3Hg into the base of the food chain. Stable isotopes of inorganic 200Hg and CH3199Hg were injected into sediments of individual cores, with cultured diatoms constrained to overlying waters. Five different treatments were done on duplicate cores, spiked with: (1) no Hg isotopes (control); (2) inorganic 200Hg; (3) CH3199Hg; (4) both 200Hg and CH3199Hg isotopes, (5) both 200Hg and CH3199Hg into overlying waters (not sediment). Experimental cores were incubated for 3 days under temperature and light controlled conditions. These results demonstrate that upper sediments characteristics lead to high variability in Hg cycling. Notably, sediments which contained abundant and peaty organic material (∼28 %LOI), had the highest pore water DOC (3206 μM) and displayed bands of sulfur reducing bacteria yielded the greatest methylation rate (1.97 % day−1) and subsequent diatom uptake of CH3200Hg (cell quota 0.18 amol/cell) in the overlying water.

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.

Positive Δ199Hg anomalies in Mesozoic porphyry Mo deposits of Northeastern China and their implications to the metallogeny of arc-related hydrothermal systems at convergent margins

Mercury (Hg) isotopes display unique mass-independent isotope fractionation (MIF, reported as Δ199Hg), which is primarily generated via Hg photochemical processes in the land-ocean-atmosphere system. Magmatic and hydrothermal processes do not trigger MIF of Hg isotopes, therefore, Hg-MIF signals detected in deep reservoirs (mantle and crust) are theoretically sourced from recycled surface materials. Here, we observed positive Δ199Hg signals (0.10 ± 0.07‰, SD) in Mesozoic porphyry Mo deposits of NE China. These values correspond to the recently reported Δ199Hg signature of Mesozoic epithermal AuAg systems in NE China (Δ199Hg: 0.11 ± 0.07‰, SD), suggesting that both mineral systems receive large amounts of Hg from subducted marine materials, given that marine Hg has positive Δ199Hg composition. Our study thus provides novel geochemical evidence on the linkage between oceanic plate subduction and metallogeny of various hydrothermal systems at convergent margins. Subduction contributes large amounts of volatiles to arc magmas, which then release metal-rich magmatic-hydrothermal fluids of the porphyry to epithermal ore deposit spectrum.

Increased Contribution of Circumpolar Deep Water Upwelling to Methylmercury in the Upper Ocean around Antarctica: Evidence from Mercury Isotopes in the Ornithogenic Sediments.

Upwelling plays a pivotal role in supplying methylmercury (MeHg) to the upper oceans, contributing to the bioaccumulation of MeHg in the marine food web. However, the influence of the upwelling of Circumpolar Deep Water (CDW), the most voluminous water mass in the Southern Ocean, on the MeHg cycle in the surrounding oceans and marine biota of Antarctica remains unclear. Here, we study the mercury (Hg) isotopes in an ornithogenic sedimentary profile strongly influenced by penguin activity on Ross Island, Antarctica. Results indicate that penguin guano is the primary source of Hg in the sediments, and the mass-independent isotope fractionation of Hg (represented by Δ199Hg) can provide insights on the source of marine MeHg accumulated by penguin. The Δ199Hg in the sediments shows a significant decrease at ∼1550 CE, which is primarily attributed to the enhanced upwelling of CDW that brought more MeHg with lower Δ199Hg from the deeper seawater to the upper ocean. We estimate that the contribution of MeHg from the deeper seawater may reach more than 38% in order to explain the decline in Δ199Hg at ∼1550 CE. Moreover, we found that the intensified upwelling may have increased the MeHg exposure for marine organisms, highlighting the importance of CDW upwelling on the MeHg cycle in Antarctic coastal ecosystems.

Development and optimization of a triple quadrupole ICP-MS-based system for the quantification of pre-concentrated gaseous elementary mercury.

Understanding the redox reactions and transformation rates of mercury (Hg) species in the environment is important for predicting future gaseous elemental Hg (Hg0) levels and assessing the impacts of anthropogenic Hg0 emissions on human health. Stable Hg isotope tracers are a promising tool for estimating Hg0 production rates; however, traditional analytical approaches for quantifying Hg0, such as atomic fluorescence spectroscopy or atomic absorption spectrometry, cannot differentiate between Hg isotopes, and alternative approaches, such as inductively coupled plasma mass spectrometry (ICP-MS) with a typical aqueous sample introductory system, have relatively higher detection limit of Hg. Here, we developed and evaluated a custom-made thermal desorption unit coupled directly to a triple quadrupole ICP-MS (ICP-QQQ) for the quantification of Hg0 pre-concentrated on Au traps. The performance of the system was validated with measurements of a Hg standard gas and of Hg0 generated from aqueous Hg standards. Using our system, we were able to detect ultra-trace amounts of Hg0 and obtain precise Hg isotope measurements with an analytical error of ≤ 3.5%. Calibration curves with superb linearity (r2 > 0.999) were obtained for the Hg concentration range of 0-300pg. The method detection limit was approximately 0.01-0.03pg of Hg. Using the latest ICP-QQQ instrument (Agilent 8900; Agilent Technologies Ltd.) was far superior to using a previous model (Agilent 8800), with the Agilent 8900 showing approximately five times higher sensitivity than the Agilent 8800 as well as the ability to precisely and simultaneously analyze up to five Hg isotopes by time-resolved analysis.

Optimization of a pre-concentration method for the analysis of mercury isotopes in low-concentration foliar samples.

Hg isotope analysis in samples from background regions is constrained by the presence of low Hg concentration and therefore requires a pre-concentration method. Existing Hg pre-concentration methods are constrained by long sample processing time and limited sample loading capacity. Using foliar samples as a test case, an optimized Hg pre-concentration method is presented that involves the microwave-assisted digestion of samples for Hg isotope analysis with the addition of a pre-digestion step. Microwave-digested foliar samples and CRMs were transferred to an impinger, reduced with SnCl2, and collected in a 2.25 mL concentrated inverse aqua regia (3:1 HNO3:HCl, v/v). This resulted in an optimal acid concentration in the solution ideal for analysis on MC-ICP-MS. The time for purging with Hg-free N2 was optimized to 30 min and the efficiency of the pre-concentration method was tested using a combination of approaches. Tests performed on pure reagents and matrix of foliar samples spiked with 197Hg radiotracer showed recoveries averaging 99 ± 1.7% and 100 ± 3.0%, respectively. Mercury at concentrations as low as 1.83 ng g-1 was pre-concentrated by digesting aliquots of foliage samples in individual digestion vessels. Recoveries following their pre-concentration averaged 99 ± 6.0%, whereas recoveries of 95 ± 4.7% and 95 ± 2.5% were achieved for NIST SRM 1575a (pine needle) and reagents spiked with NIST SRM 3133, respectively. Analysis using multicollector-ICP-MS showed low fractionation of δ202Hg during sample pre-concentration with no significant mass-independent fractionation. The proposed method is a relatively simple and robust way to prepare Hg samples for Hg isotopic analysis and is suitable even for complex biological matrices.

Distribution and Homogenization of Multiple Mercury Species Inputs to Freshwater Wetland Mesocosms.

Mercury (Hg)-impaired aquatic ecosystems often receive multiple inputs of different Hg species with varying potentials for transformation and bioaccumulation. Over time, these distinct input pools of Hg homogenize in their relative distributions and bioaccumulation potentials as a result of biogeochemical processes and other aging processes within the ecosystem. This study sought to evaluate the relative time scale for homogenization of multiple Hg inputs to wetlands, information that is relevant for ecosystem management strategies that consider Hg source apportionment. We performed experiments in simulated freshwater wetland mesocosms that were dosed with four isotopically labeled mercury forms: two dissolved forms (Hg2+ and Hg-humic acid) and two particulate forms (nano-HgS and Hg adsorbed to FeS). Over the course of one year, we monitored the four Hg isotope endmembers for their relative distribution between surface water, sediment, and fish in the mesocosms, partitioning between soluble and particulate forms, and conversion to methylated mercury (MeHg). We also evaluated the reactivity and mobility of Hg through sequential selective extractions of sediment and the uptake flux of aqueous Hg in a diffusive gradient in thin-film (DGT) passive samplers. We observed that the four isotope spikes were relatively similar in surface water concentration (ca. 3000 ng/L) immediately after spike addition. At 1-3 months after dosing, Hg concentrations were 1-50 ng/L and were greater for the initially dissolved isotope endmembers than the initially particulate endmembers. In contrast, the Hg isotope endmembers in surface sediments were similar in relative concentration within 2 months after spike addition. However, the uptake fluxes of Hg in DGT samplers, deployed in both the water column and surface sediment, were generally greater for initially dissolved Hg endmembers and lower for initially particulate endmembers. At one year postdosing, the DGT-uptake fluxes were converging toward similar values between the Hg isotope endmembers. However, the relative distribution of isotope endmembers was still significantly different in both the water column and sediment (p < 0.01 according to one-way ANOVA analysis). In contrast, selective sequential extractions resulted in a homogeneous distribution, with >90% of each endmember extracted in the KOH fraction, suggesting that Hg species were associated with sediment organic matter. For MeHg concentrations in surface sediment and fish, the relative contributions from each endmember were significantly different at all sampling time points. Altogether, these results provide insights into the time scales of distribution for different Hg species that enter a wetland ecosystem. While these inputs attain homogeneity in concentration in primary storage compartments (i.e., sediments) within weeks after addition, these input pools remain differentiated for more than one year in terms of reactivity for passive samplers, MeHg concentration, and bioaccumulation.

Rapid determination of Hg isotopes in low concentration water samples by flow injection-plasma electrochemical vapor generation

A new strategy for determining the Hg isotopes in low Hg concentration samples is proposed, utilizing the flow injection plasma electrochemical vapor generation (FI-PEVG) sampling technique coupled with MC-ICPMS.

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

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

Mercury Isotope Composition in Open Water Corals of South China Sea: Implication for Atmospheric Mercury Deposition Pathways Into Tropical Oceans

AbstractThe deposition of different atmospheric mercury (Hg) species into oceans determines the atmospheric Hg lifetime and the production of neurotoxin methylmercury. Yet, the relative contribution of atmospheric Hg(II) and Hg(0) is largely unconstrained. Here, we report the concentrations of total Hg and methylmercury, as well as Hg isotope composition in living corals collected from the tropical South China Sea (SCS). The results show that the Hg in corals is mainly present as inorganic Hg, exhibiting slightly negative δ202Hg and small yet significant Δ199Hg and Δ200Hg. These isotope features closely resemble those of pelagic waters, suggesting that shallow‐water corals that are widely distributed in oligotrophic waters could be used to trace atmospheric Hg deposition pathways. A mixture model based on coral Δ200Hg indicates that approximately 49% of the seawater Hg in the tropical SCS, a region characterized by high rainfall, originates from atmospheric gaseous Hg(0), much larger than previous estimates.

Competition between Dissolved Organic Matter and Freshwater Plankton Control Methylmercury Isotope Fractionation during Uptake and Photochemical Demethylation.

Isotope fractionation related to photochemical reactions and planktonic uptake at the base of the food web is a major uncertainty in the biological application of mercury (Hg) stable isotopes. In freshwater systems, it is unclear how competitive interactions among methylmercury (MeHg), dissolved organic matter (DOM), and phytoplankton govern the magnitude of mass-dependent and mass-independent fractionation. This study investigated how DOM alters rates of planktonic MeHg uptake and photodegradation and corresponding Hg isotope fractionation in the presence of freshwater phytoplankton species, Raphidocelis subcapitata. Outdoor sunlight exposure experiments utilizing R. subcapitata were performed in the presence of different DOM samples using environmentally relevant ratios of MeHg-DOM thiol groups. The extent of Δ199Hg in phytoplankton incubations (2.99‰ St. Louis River HPOA, 1.88‰ Lake Erie HPOA) was lower compared to paired abiotic control experiments (4.29 and 2.86‰, respectively) after ∼30 h of irradiation, resulting from cell shading or other limiting factors reducing the extent of photodemethylation. Although the Δ199Hg/Δ201Hg ratio was uniform across experiments (∼1.4), Δ199Hg/δ202Hg slopes varied dramatically (from -0.96 to 15.4) across incubations with R. subcapitata and DOM. In addition, no evidence of Hg isotope fractionation was observed within R. subcapitata cells. This study provides a refined examination of Hg isotope fractionation markers for key processes occurring in the lower food web prior to bioaccumulation, critical for accurately accounting for the photochemical processing of Hg isotopes across a wide spectrum of freshwater systems.

Metasomatized mantle sources for orogenic gold deposits hosted in high-grade metamorphic rocks: Evidence from Hg isotopes

Abstract Investigation of Hg isotope ratios of gold-related sulfides and penecontemporaneous mafic dikes from four orogenic gold provinces on the margins of the North China Craton and Yangtze Craton identifies three orogenic gold deposit (OGD) groups from different tectonic regimes. Ore-related sulfides of group 1 OGDs and mafic dikes from the craton margin reworked via oceanic subduction mostly have positive Δ199Hg values. The group 2 OGDs and mafic dikes from the margin that witnessed complex oceanic and continental subductions have mixed positive to negative Δ199Hg values. The group 3 OGDs on the margin that experienced continental subduction have dominantly negative Δ199Hg values. These isotopic differences indicate subduction histories have a first-order control on the distinct sources for the OGDs. It indicates that OGDs were derived from fluids from the mantle lithosphere metasomatized by contrasting subduction components, not from metamorphic fluids as is widely accepted. Group 1 OGDs and dikes were sourced from metasomatized mantle, which inherited the positive Δ199Hg of both recycled marine sediments and seawater during oceanic subduction, whereas group 3 with negative Δ199Hg was derived from mantle lithosphere metasomatized by subduction of mainly continental components. This genetic model identifies regions with high-grade metamorphic rocks above metasomatized mantle lithosphere as promising new OGD exploration targets.

Odd-even shape staggering and kink structure of charge radii of Hg isotopes by the deformed relativistic Hartree–Bogoliubov theory in continuum

We examined the shape staggering of relative charge radii in 180−186Hg isotopes, which was first measured in 1977 and recently confirmed using advanced spectroscopy techniques. To understand the nuclear structure underlying this phenomenon, we employed the deformed relativistic Hartree–Bogoliubov theory in continuum (DRHBc). Our analysis revealed that the shape staggering can be attributed to nuclear shape transition in the Hg isotopes. Specifically, we demonstrated that prolate shapes of 181,183,185Hg lead to an increase in the charge radii compared to oblate shapes of 180,182,184,186Hg isotopes. We explained the nuclear shape staggering in terms of the evolution of occupation probability (OP) of ν1i13/2, ν1h9/2, π1h9/2, and π3s1/2 states. Additionally, we clarified the kink structure of the charge radii in the Hg isotopes near N=126 magic shell does not come from the change of the OP of π1h9/2 state, but mainly by the increase of the OPs of ν1i11/2 and ν2g9/2 states.