Hg Isotopes Research Articles

Predicting Behavior and Fate of Atmospheric Mercury in Soils: Age-Dating METAALICUS Hg Isotope Spikes with Fallout Radionuclide Chronometry.

Soils accumulate anthropogenic mercury (Hg) from atmospheric deposition to terrestrial ecosystems. However, possible reemission of gaseous elemental mercury (GEM) back to the atmosphere as well as downward migration of Hg with soil leachate influence soil sequestration of Hg in ways not sufficiently understood in global biogeochemical models. Here, we apply fallout radionuclide (FRN) chronometry to understand soil Hg dynamics by revisiting the METAALICUS experiments 20 years after enriched isotope tracers (198Hg, 200Hg, 201Hg, and 202Hg) were applied to two boreal watersheds in northwestern Ontario, Canada. Hg spikes formed well-defined peaks in organic horizons of both watersheds at depths of 3-6 cm and were accurately dated to the year of spike application in 6 of 7 cases (error = -0.8 ± 1.2 years). A seventh site was depleted by ca. 90% of both the 200Hg spike and background Hg, and the spike was dated 16 years older than its application. Robust FRN age models and mass balances demonstrate that loss of Hg is attributable to its specific physicochemical behavior at this site, but more work is required to attribute this to reemission or leaching. This study demonstrates the potential of FRN chronometry to provide insights into Hg accumulation, mobilization, and fate in forest soils.

A Catalyst Tube-Equipped Dual-Stage Tube Furnace System for Accurate Hg Isotopic Determination of Ore Samples Using Neptune Plus Multicollector Inductively Coupled Plasma Mass Spectrometry.

Mercury (Hg) isotopes, which display mass-dependent fractionation and mass-independent fractionation, provide a multidimensional tracer to decipher the source of metals in mineral deposits. However, mineral ore samples usually contain abundant interfering elements (e.g., Te) that can cause inaccurate Hg isotopic analysis. Available acid digestion and combustion methods failed to remove these interfering elements, hindering the application of Hg isotopes for metallogenetic tracing. Here, we developed a new dual-stage tube furnace system employing a Mn-containing catalyst tube to pretreat mineral ore samples. This method yielded good Hg recoveries (100.5 ± 3.8%, 1SD, n = 15) and low levels of interfering elements in sample solutions, allowing for accurate analysis of a series of ore standard reference materials (GBW-11108v: coal; GSO-3: Cu-Ag sulfide ore; GBW 07859: Au-Te sulfide ore). The new method was also successfully applied to measure the Hg isotopic composition of magmatic and hydrothermal ore deposits, which yielded a large range in Δ199Hg value (-0.19 to 0.22‰) for ore deposits formed in different geological settings, highlighting the future applications of this method for metallogenic tracing, especially tracing the source of metals in mineral ore deposits.

A 14,000‐Year Sediment Record of Mercury Accumulation and Isotopic Signatures From Lake Malaya Chabyda (Siberia)

AbstractEurasian permafrost soils contain large amounts of organic carbon (OC) and mercury (Hg), sequestered by vegetation during past and present interglacial periods. Lake sediment archives may help understand past OC and Hg dynamics and how they interact with climate‐related variables. We investigated Hg accumulation, OC dynamics, and Hg and OC stable isotopes in a 14,000‐year sediment record from Lake Malaya Chabyda (Central Yakutia, Russia). Sediment Hg was correlated to OC (p value < 0.01), with lower OC and Hg accumulation rates (OCAR, HgAR) during the cold Younger Dryas (YD, 12,900–11,700 cal BP), when the lake level was low. Elevated sediment Δ200Hg (0.05‰ ± 0.11‰), representing dominant HgII deposition, and low δ13C, indicates low lake primary productivity during the YD. During the early Holocene, Δ200Hg and Δ199Hg decreased, while δ13C, δ202Hg, OCAR, and HgAR increased, suggesting enhanced algal primary productivity in deeper, more turbid waters. From 4,100 cal BP to present, Hg/OC ratios and HgAR increased at constant OCAR, indicating an additional Hg source to the lake. Analysis of Hg isotopes suggests direct Hg0 uptake into lake waters, potentially driven by primary production and efficient Hg burial. Our observations suggest that the gradual climate warming since the Last Glacial Termination and into the early Holocene led to enhanced OC and Hg burial in northern lakes and watersheds. Late Holocene enhanced Hg burial, but not OC, is possibly related to a renewed increase in lake primary productivity. Continued global warming may lead to further Hg sequestration in northern aquatic ecosystems.

Mercury isotope fractionation and mercury source analysis in coal

Understanding the sources of mercury (Hg) in coal is crucial for understanding the natural Hg cycle in the Earth's system, as coal is a natural Hg reservoir. We conducted analyses on the mass-dependent fractionation (MDF), reported as δ202Hg, and mass-independent fractionation (MIF), reported as Δ199Hg, of Hg isotopes among individual Hg species and total Hg (THg) in Chinese coal samples. This data, supplemented by a review of prior research, allowed us to discern the varying trend of THg isotope fractionation with coal THg content. The Hg isotopic composition among identified Hg species in coal manifests notable disparities, with species exhibiting higher thermal stability tending to have heavier δ202Hg values, whereas HgS species typically display the most negative Δ199Hg values. The sources of Hg in coal are predominantly attributed to Hg accumulation from the original plant material and subsequent input from hydrothermal activity. Hg infiltrates peat swamps via vegetation debris, thus acquiring a negative Δ199Hg isotopic signature. Large-scale lithospheric Hg recycling via plate tectonics facilitates the transfer of Hg with a positive Δ199Hg from marine reservoirs to the deep crust. The later-stage hydrothermal input of Hg with a positive Δ199Hg enhances coal Hg content. This process has resulted in an upward trend of Δ199Hg values corresponding with the increase in coal THg content, ultimately leading to near-zero Δ199Hg in high-Hg coals. Coal Hg reservoirs are affected by large-scale natural Hg cycling, which involves the exchange of Hg between continents and seas.

Atmospheric Mercury Concentrations and Isotopic Compositions Impacted by Typical Anthropogenic Mercury Emissions Sources.

Coal-fired power plants (CFPPs) and cement plants (CPs) are important anthropogenic mercury (Hg) emission sources. Mercury speciation profiles in flue gas are different among these sources, leading to significant variations in local atmospheric Hg deposition. To quantify the impacts of Hg emissions from CFPPs and CPs on local-scale atmospheric Hg deposition, this study determined concentrations and isotopes of ambient gaseous elemental mercury (GEM), particulate-bound mercury (PBM), and precipitation total Hg (THg) at multiple locations with different distances away from a CFPP and a CP. Higher concentrations of GEM and precipitation THg in the CFPP area in summer were caused by higher Hg emission from the CFPP, resulting from higher electricity demand. Higher concentrations of GEM, PBM, and precipitation THg in the CP area in winter compared to those in summer were related to the higher output of cement. Atmospheric Hg concentration peaked near the CFPP and CP and decreased with distance from the plants. Elevated GEM concentration in the CFPP area was due to flue gas Hg0 emissions, and high PBM and precipitation Hg concentrations in the CP area were attributed to divalent Hg emissions. It was estimated that Hg emissions from the CFPP contributed 58.3 ± 20.9 and 52.3 ± 25.9% to local GEM and PBM, respectively, and those from the CP contributed 47.0 ± 16.7 and 60.0 ± 25.9% to local GEM and PBM, respectively. This study demonstrates that speciated Hg from anthropogenic emissions posed distinct impacts on the local atmospheric Hg cycle, indicating that Hg speciation profiles from these sources should be considered for evaluating the effectiveness of emission reduction policies. This study also highlights the Hg isotope as a useful tool for monitoring environmental Hg emissions.

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.

Hair mercury isotopes, a noninvasive biomarker for dietary methylmercury exposure and biological uptake.

Background. Fish and rice are the main dietary sources of methylmercury (MeHg); however, rice does not contain the same beneficial nutrients as fish, and these differences can impact the observed health effects of MeHg. Hence, it is important to validate a biomarker, which can distinguish among dietary MeHg sources. Methods. Mercury (Hg) stable isotopes were analyzed in hair samples from peripartum mothers in China (n = 265). Associations between mass dependent fractionation (MDF) (δ202Hg) and mass independent fractionation (MIF) (Δ199Hg) (dependent variables) and dietary MeHg intake (independent variable) were investigated using multivariable regression models. Results. In adjusted models, hair Δ199Hg was positively correlated with serum omega-3 fatty acids (a biomarker for fish consumption) and negatively correlated with maternal rice MeHg intake, indicating MIF recorded in hair can be used to distinguish MeHg intake predominantly from fish versus rice. Conversely, in adjusted models, hair δ202Hg was not correlated with measures of dietary measures of MeHg intake. Instead, hair δ202Hg was strongly, negatively correlated with hair Hg, which explained 27-29% of the variability in hair δ202Hg. Conclusions. Our results indicated that hair Δ199Hg can be used to distinguish MeHg intake from fish versus rice. Results also suggested that lighter isotopes were preferentially accumulated in hair, potentially reflecting Hg binding to thiols (i.e., cysteine); however, more research is needed to elucidate this hypothesis. Broader impacts include 1) validation of a non-invasive biomarker to distinguish MeHg intake from rice versus fish, and 2) the potential to use Hg isotopes to investigate Hg binding in tissues.

Mercury isotope evidence for the importance of recycled fluids in collisional ore systems.

The sources of fluids and metals in porphyry systems of continental-collision settings are poorly constrained. Mercury isotopes display unique mass-independent fractionation (expressed as Δ199Hg) and may provide important constraints on metal and volatile sources given that Hg is a highly volatile metal. Here, we report Hg isotope data on ore-forming porphyries, barren magmatic rocks, and mantle-derived mafic magmas from southern Tibet. The fertile porphyries and coeval mafic magmas display mainly positive Δ199Hg values (up to +0.25 per mil), while Δ199Hg values in barren magmatic rocks and mafic magmas are largely negative (-0.54 to 0.00 per mil). The positive Δ199Hg values observed here are consistent with seawater and marine sediments, suggesting that the ultimate source of fluids involved in the genesis of post-subduction porphyry copper deposits was the mantle lithosphere metasomatized by previous oceanic plate subduction. Our Hg isotope data provide an alternative view to current metallogenetic models on collisional porphyry systems that focus on melting of the lower continental crust.

Spatiotemporal disparity of volcanogenic mercury records in the southwestern Neo-Tethys Ocean during the Permian–Triassic transition

The Permian–Triassic (P-Tr) transition marks a vital period in Earth's history, characterized by major environmental perturbations and the largest mass extinction event of the Phanerozoic, with volcanic activities playing a key role. Previous investigations of mercury (Hg) anomalies in over 50 marine and terrestrial sections spanning the P-Tr boundary (PTB) have suggested a predominant volcanogenic influence. However, there remains ongoing debate regarding the exact timing and primary sources of these anomalies in different regions. In this study, we present stratigraphically high-resolution (∼7× higher compared to the previous work in the same section) Hg records from the shallow marine strata of the Qubu section, located at the Himalayan Tethys Zone of southern Tibet, Southwest China. Our analysis reveals peak Hg concentrations of approximately 80 to 100 ng/g and Hg/TOC ratios of 111 to 263 (ppb/wt%) at the uppermost Permian. Notably, new measurements of Hg isotopes, characterized by ∼0‰ of Δ199Hg values, provide unambiguous evidence supporting the prevailing volcanic influence. Our results are consistent with similar observations of Hg anomalies in proximal shallow-marine sections around the Neo-Tethys Ocean, including those in northern India and western Australia. However, we found that relatively shallower marine settings (shelf, lagoon or inshore) tend to exhibit Hg spikes in the latest Permian, whereas deeper sections (outer-shelf or deep carbonate ramp) show peaks in the Early Triassic. Since Hg anomalies for all the sections have been verified to be volcanogenic based on their near-zero values of Δ199Hg, the discrepancies among them concerning timing and water depth may be attributed to prolonged volcanic influences extending into the Triassic period. Our findings underscore the complexity of sedimentary Hg records and further raise questions about the spatiotemporal consistency of Hg anomalies during the P-Tr transition. Additionally, the most negative Δ199Hg value (−0.20‰) in the uppermost black shale in the Qubu section likely resulted from photic zone euxinia consistent with globally developed P-Tr shallow-marine anoxic conditions, while other low values of Δ199Hg with low Hg concentrations were derived from some moderate terrestrial influx.

Involvement of Hg-bearing methane seeps in forming Ediacaran cap carbonate in South China

During the Cryogenian-Ediacaran transition, an extremely cold climate transitioned into a warm climate which was accompanied by the worldwide precipitation of cap carbonates showing striking negative carbonate carbon isotope (δ13Ccarb) anomalies. High mercury (Hg) contents up to 180 ppb have been reported from the Doushantuo cap carbonates, but the origin of Hg anomalies and its relationship with cap carbonate precipitation remain unclear. To address these issues, we measured Hg concentrations and isotopes along with total organic carbon (TOC) content and δ13Ccarb from the basal Ediacaran carbonates at the Jiulongwan section of western Hubei Province, South China. The results show that in laterally persistent intervals, Hg spikes (as high as 77 ppb) co-occur with decrease of Δ199Hg values (as low as 0.07‰), increase of δ202Hg values (−1.47‰), and conspicuous negative δ13Ccarb shifts (as low as ca. -17‰). Such Hg isotopic signature with high Hg concentration are comparable to those of natural gas hydrates and thus are ascribed to be an involvement of Hg-bearing methane seeps in precipitation of cap carbonate after melting of ice-sheets of the Marinoan glaciation (latest Cryogenian). Anaerobic oxidation of methane from hydrates via sulfate reduction may have produced bicarbonate (HCO3−), which was transformed into cap carbonate when combining with alkaline ions transported from continent to seawater via weathering process. This study provides the first evidence for Hg-bearing methane oxidation during cap carbonate precipitation.

Geographic Drivers of Mercury Entry into Aquatic Food Webs Revealed by Mercury Stable Isotopes in Dragonfly Larvae.

Atmospheric mercury (Hg) emissions and subsequent transport and deposition are major concerns within protected lands, including national parks, where Hg can bioaccumulate to levels detrimental to human and wildlife health. Despite this risk to biological resources, there is limited understanding of the relative importance of different Hg sources and delivery pathways within the protected regions. Here, we used Hg stable isotope measurements within a single aquatic bioindicator, dragonfly larvae, to determine if these tracers can resolve spatial patterns in Hg sources, delivery mechanisms, and aquatic cycling at a national scale. Mercury isotope values in dragonfly tissues varied among habitat types (e.g., lentic, lotic, and wetland) and geographic location. Photochemical-derived isotope fractionation was habitat-dependent and influenced by factors that impact light penetration directly or indirectly, including dissolved organic matter, canopy cover, and total phosphorus. Strong patterns for Δ200Hg emerged in the western United States, highlighting the relative importance of wet deposition sources in arid regions in contrast to dry deposition delivery in forested regions. This work demonstrates the efficacy of dragonfly larvae as biosentinels for Hg isotope studies due to their ubiquity across freshwater ecosystems and ability to track variation in Hg sources and processing attributed to small-scale habitat and large-scale regional patterns.

Sources of Particulate Bound Mercury in the Northwest Pacific Constrained by Hg Isotopes

Sources of Particulate Bound Mercury in the Northwest Pacific Constrained by Hg Isotopes

Mercury sources, transport, and transformation in rainfall-runoff processes: Mercury isotope approach

Mercury (Hg) in runoff water poses significant ecological risks to aquatic ecosystems that can affect organisms. However, accurately identifying the sources and transformation processes of Hg in runoff water is challenging due to complex natural conditions. This study provides a comprehensive investigation of Hg dynamics in water from rainfall to runoff. The Hg isotope fractionation in water was characterized, which allows accurate quantification of Hg sources, transport, and transformations in rainfall-runoff processes. Δ200Hg and corrected Δ199Hg values can serve as reliable tracers for identifying Hg sources in the runoff water and the variation of δ202Hg can be explained by Hg transformation processes. During runoff migration processes, Hg from rainfall is rapidly absorbed on the land surface, while terrestrial Hg entering the water by the dissolution process becomes the primary component of dissolved mercury (DHg). Besides the dissolution and adsorption, microbial Hg(II) reduction and demethylation of MeHg were dominant processes for DHg in the runoff water that flows through the rice paddies, while photochemical Hg(II) reduction was the dominant process for DHg in the runoff water with low water exchange rates. Particulate Hg (PHg) in runoff water is dominantly originated by the terrestrial material and derived from the dissolution and adsorption process. Tracking sources and transformations of Hg in runoff water during the rainfall-runoff process provides a basis for studying Hg pollution in larger water bodies under complex environmental factors.

Dynamics of mercury stable isotope compounds in Arctic seals: New insights from a controlled feeding trial on hooded seals Cystophora cristata

Accurate interpretation of mercury (Hg) isotopic data requires the consideration of several biotic factors such as age, diet, geographical range, and tissue metabolic turnover. A priori knowledge of prey-predator isotopic incorporation rates and Hg biomagnification is essential. This study aims to assess Hg stable isotopes incorporation in an Arctic species of Phocidae, the hooded seal Cystophora cristata, kept in human care for 24 months (2012–2014) and fed on a constant diet of Norwegian Spring Spawning herring Clupea harengus. We measured THg, MMHg and iHg levels, as well as Hg stable isotope composition with both mass dependent (MDF) and mass independent (MIF) fractionation (e.g. δ202Hg and Δ199,200,201,204Hg) in hooded seal kidney, liver, hair and muscle, in addition to herring muscle. We then calculated Hg MDF and MIF isotopic fractionation between hooded seals and their prey. We found a significant shift in δ202Hg between hooded seal hair (+0.80‰) and kidney (−0.78‰), and herring muscle. In hooded seals tissues δ202Hg correlated positively with MMHg percentage. These findings suggest that tissue-specific Hg speciation is the major driver of changes in Hg isotopic fractionation rates in this Arctic predator. Δ199Hg, Δ200Hg, Δ201Hg and Δ204Hg values did not vary between herring and hooded seal tissues, confirming their utility as tracers of Hg marine and atmospheric sources in top predators. To our knowledge, this represents the first attempt to assess complex Hg isotope dynamics in the internal system of Arctic Phocidae, controlling the effects of age, diet, and distribution. Our results confirm the validity of Hg stable isotopes as tracers of environmental Hg sources even in top predators, but emphasize the importance of animal age and tissue selection for inter-study and inter-species comparisons.

Using Mercury Stable Isotopes to Quantify Directional Soil-Atmosphere Hg(0) Exchanges in Rice Paddy Ecosystems: Implications for Hg(0) Emissions to the Atmosphere from Land Surfaces.

Gaseous elemental mercury [Hg(0)] emissions from soils constitute a large fraction of global total Hg(0) emissions. Existing studies do not distinguish biotic- and abiotic-mediated emissions and focus only on photoreduction mediated emissions, resulting in an underestimation of soil Hg(0) emissions into the atmosphere. In this study, directional mercury (Hg) reduction pathways in paddy soils were identified using Hg isotopes. Results showed significantly different isotopic compositions of Hg(0) between those produced from photoreduction (δ202Hg = -0.80 ± 0.67‰, Δ199Hg = -0.38 ± 0.18‰), microbial reduction (δ202Hg = -2.18 ± 0.25‰, Δ199Hg = 0.29 ± 0.38‰), and abiotic dark reduction (δ202Hg = -2.31 ± 0.25‰, Δ199Hg = 0.50 ± 0.22‰). Hg(0) exchange fluxes between the atmosphere and the paddy soils were dominated by emissions, with the average flux ranging from 2.2 ± 5.7 to 16.8 ± 21.7 ng m-2 h-1 during different sampling periods. Using an isotopic signature-based ternary mixing model, we revealed that photoreduction is the most important contributor to Hg(0) emissions from paddy soils. Albeit lower, microbial and abiotic dark reduction contributed up to 36 ± 22 and 25 ± 15%, respectively, to Hg(0) emissions on the 110th day. These novel findings can help improve future estimation of soil Hg(0) emissions from rice paddy ecosystems, which involve complex biotic-, abiotic-, and photoreduction processes.

C, N, Hg isotopes and elemental chemostratigraphy across the Ordovician–Silurian transition in the Argentine Precordillera: Implications for the link between volcanism and extinctions

Global geological processes that occurred during the Ordovician–Silurian transition (OST) were investigated exploring sections from the Argentine Precordillera (Cerro La Chilca, Baños de Talacasto and Villicum) which were deposited close to polar zones of Gondwana during the oldest Phanerozoic glaciation. C-N-Hg isotopes and redox-sensitive trace metal chemostratigraphy allowed to assess the relative importance of volcanism, glaciation, post-glacial sedimentation and extinction events during the OST. At Cerro La Chilca and Baños de Talacasto sections, Katian and early Hirnantian strata are missing. Hirnantian and Rhuddanian strata occur in the all three sections. At Cerro La Chilca, coeval positive δ13Corg shift, Hg spike and Δ199Hg ∼ 0 ‰ were recorded in the Sandbian Los Azules Formation, suggesting volcanic Hg loading. Coeval Hg/TOC spikes at the Baños de Talacasto and Villicum sections and Δ199Hg ∼ 0 ‰ in the late Hirnantian (M. persculptus Zone) recorded the second pulse of the Late Ordovician mass extinction (LOME 2), for which volcanism was postulated as the cause of warming and anoxia. Another Hg/TOC spike in the early Rhuddanian at Baños de Talacasto and Villicum is coeval with slightly positive Δ199Hg values, an enrichment related, perhaps, to an enhanced continental runoff that followed the Late Ordovician glacial cycle (LOGC-3). At the Cerro La Chilca, positive δ15N values in the Sandbian suggest less intense water-column denitrification while negative nitrogen isotope values in the LOME 2 period indicate denitrifying conditions. At the Baños de Talacasto and Villicum sections, sea-level fluctuations and nitrogen upwelling helped shaping the δ15N pathway within the LOME 2 and early Rhuddanian intervals, with negative δ15N values attesting that conditions became less reducing closer to the OST. The odd-MIF Hg isotope pattern within the LOME 2 time interval was probably induced by coeval volcanism, glaciation and sea-level fall, and in the early Rhuddanian by deglaciation and sea-level rise.

Mercury isotopes of the Late Ordovician to Middle Triassic tuff layers in South China link the fate of ancient volcanism and the mass extinction

Mercury (Hg) anomalies in sedimentary records are a newly developed proxy of large volcanism in the geological past. Tuff layers host abundant volcanic ash and record key information on the type of volcanic emission (e.g., arc volcanism and large igneous province eruptions). Here, we measured the Hg isotopic compositions of several tuff layers in South China. Tuff samples in the Late Ordovician Wufeng Formation and the Middle Triassic Guanling Formation mostly show positive Δ199Hg values of – 0.01 to 0.10‰ and – 0.06 to 0.16‰, respectively, suggesting arc volcanism occurred during these two periods. Tuff samples in the Middle Permian Dachang Layer mostly show near-zero Δ199Hg values (– 0.08 to 0.00‰), suggesting volcanism was driven by the Emeishan large igneous province eruption. Results of this study verify Hg isotopes as a useful proxy in revealing the type of volcanism in geological history.

Isotope Data Constrains Redox Chemistry of Atmospheric Mercury.

The redox chemistry of mercury (Hg) in the atmosphere exerts a significant influence on its global cycle. However, our understanding of this important process remains shrouded in uncertainty. In this study, we utilize three-dimensional atmospheric Hg isotope modeling to evaluate the isotopic composition of particle-bound mercury [HgII(P)] in the global atmosphere. We investigate various chemistry mechanisms and find that they induce remarkably disparate odd-number mass-independent fractionation (odd-MIF) in HgII(P) on a global scale. The observed odd-MIF data identify the essential role of sea salt aerosol debromination in the redox chemistry of atmospheric Hg and underscore the predominant influence of Br oxidation in the marine boundary layer. The odd-MIF signatures significantly narrow the uncertainty range of redox chemistry rates and constrain the photoreduction of HgII(P) at a magnitude of 10-3 JNO2 (local photolysis frequency of NO2) in the global atmosphere. This study advances our understanding of atmospheric Hg chemistry processes and provides insights into the potential impacts of climate change on Hg cycling.

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.