Contact between water vapor and silicate surface causes abiotic formation of reactive oxygen species in an anoxic atmosphere.

Spontaneous generation of reactive oxygen species (ROS) in aqueous microdroplets or at a water vapor-silicate interface is a new source of redox chemistry. However, such generation occurs with difficulty in liquid water having a large ionic strength. We report that ROS is spontaneously produced when water vapor contacts hydrogen-bonded hydroxyl groups on a silicate surface. The evolution of hydrogen-bonded species such as hydroxyl groups was investigated by using two-dimensional, time-resolved FT-IR spectroscopy. The participation of water vapor in ROS generation is confirmed by investigating the reaction of D2O vapor and hydroxyl groups on a silicate surface. We propose a reaction pathway for ROS generation based on the change of the hydrogen-bonding network and corresponding electron transfer onto the silicate surface in the water vapor-solid contact process. Our observations suggest that ROS production from water vapor-silicate contact electrification could have contributed to oxidation during the Archean Eon before the Great Oxidation Event.

Converting Nanotoxicity Data to Information Using Artificial Intelligence and Simulation.

Decades of nanotoxicology research have generated extensive and diverse data sets. However, data is not equal to information. The question is how to extract critical information buried in vast data streams. Here we show that artificial intelligence (AI) and molecular simulation play key roles in transforming nanotoxicity data into critical information, i.e., constructing the quantitative nanostructure (physicochemical properties)-toxicity relationships, and elucidating the toxicity-related molecular mechanisms. For AI and molecular simulation to realize their full impacts in this mission, several obstacles must be overcome. These include the paucity of high-quality nanomaterials (NMs) and standardized nanotoxicity data, the lack of model-friendly databases, the scarcity of specific and universal nanodescriptors, and the inability to simulate NMs at realistic spatial and temporal scales. This review provides a comprehensive and representative, but not exhaustive, summary of the current capability gaps and tools required to fill these formidable gaps. Specifically, we discuss the applications of AI and molecular simulation, which can address the large-scale data challenge for nanotoxicology research. The need for model-friendly nanotoxicity databases, powerful nanodescriptors, new modeling approaches, molecular mechanism analysis, and design of the next-generation NMs are also critically discussed. Finally, we provide a perspective on future trends and challenges.

Water-solid contact electrification causes hydrogen peroxide production from hydroxyl radical recombination in sprayed microdroplets.

Contact electrification between water and a solid surface is crucial for physicochemical processes at water-solid interfaces. However, the nature of the involved processes remains poorly understood, especially in the initial stage of the interface formation. Here we report that H2O2 is spontaneously produced from the hydroxyl groups on the solid surface when contact occurred. The density of hydroxyl groups affects the H2O2 yield. The participation of hydroxyl groups in H2O2 generation is confirmed by mass spectrometric detection of 18O in the product of the reaction between 4-carboxyphenylboronic acid and 18O-labeled H2O2 resulting from 18O2 plasma treatment of the surface. We propose a model for H2O2 generation based on recombination of the hydroxyl radicals produced from the surface hydroxyl groups in the water-solid contact process. Our observations show that the spontaneous generation of H2O2 is universal on the surfaces of soil and atmospheric fine particles in a humid environment.

Can Mercury Influence Carbon Dioxide Levels? Implications for the Implementation of the Minamata Convention on Mercury.

The Paris Agreement and the Minamata Convention on Mercury are two of the most important environmental conventions being implemented concurrently, with a focus on reducing carbon and mercury emissions, respectively. The relation between mercury and carbon influences the interactions and outcomes of these two conventions. This perspective investigates the link between mercury and CO2, assessing the consequences and exploring the policy implications of this link. We present scientific evidence showing that mercury and CO2 levels are negatively correlated under natural conditions. As a result of this negative correlation, the CO2 level under the current mercury reduction scenario is predicted to be 2.4-10.1 ppm higher than the no action scenario by 2050, equivalent to 1.0-4.8 years of CO2 increase due to human activity. The underlying causations of this negative correlation are complex and need further research. Economic analysis indicates that there is a trade-off between the benefits and costs of mercury reduction actions. As reducing mercury emission may inadvertently undermine efforts to achieve climate goals, we advocate for devising a coordinated implementation strategy for carbon and mercury conventions to maximize synergies and reduce trade-offs.

Transformation of Mercurous [Hg(I)] Species during Laboratory Standard Preparation and Analysis: Implication for Environmental Analysis.

Hg(I) may control Hg redox kinetics; however, its metastable nature hinders analysis. Herein, the stability of Hg(I) during standard preparation and analysis was studied. Gravimetric analysis showed that Hg(I) was stable in its stock solution (1000 mg L-1), yet completely disproportionated when its dilute solution (10 µg L-1) was analyzed using liquid chromatography (LC)-ICPMS. The Hg(I) dimer can form through an energetically favorable comproportionation between Hg(0) and Hg(II), as supported by density functional theory calculation and traced by the rapid isotope exchange between 199Hg(0)aq and 202Hg(II). However, the separation of Hg(0) and Hg(II) (e.g., LC process) triggered its further disproportionation. Polypropylene container, increasing headspace, decreasing pH, and increasing dissolved oxygen significantly enhanced the disproportionation or redox transformations of Hg(I). Thus, using a glass container without headspace and maintaining a slightly alkaline solution are recommended for the dilute Hg(I) stabilization. Notably, we detected elevated concentrations of Hg(I) (4.4-6.1 µg L-1) in creek waters from a heavily Hg-polluted area, accounting for 54-70% of total dissolved Hg. We also verified the reductive formation of Hg(I) in Hg(II)-spiked environmental water samples, where Hg(I) can stably exist in aquatic environments for at least 24 h, especially in seawater. These findings provide mechanistic insights into the transformation of Hg(I), which are indicative of its further environmental identification.

Effects of Temperature and DC Electric Fields on Perfluorooctanoic Acid Sorption Kinetics to Activated Carbon.

Sorption to activated carbon is a common approach to reducing environmental risks of waterborne perfluorooctanoic acid (PFOA), while effective and flexible approaches to PFOA sorption are needed. Variations in temperature or the use of electrokinetic phenomena (electroosmosis and electromigration) in the presence of external DC electric fields have been shown to alter the contaminant sorption of contaminants. Their role in PFOA sorption, however, remains unclear. Here, we investigated the joint effects of DC electric fields and the temperature on the sorption of PFOA on activated carbon. Temperature-dependent batch and column sorption experiments were performed in the presence and absence of DC fields, and the results were evaluated by using different kinetic sorption models. We found an emerging interplay of DC and temperature on PFOA sorption, which was linked via the liquid viscosity (η) of the electrolyte. For instance, the combined presence of a DC field and low temperature increased the PFOA loading up to 38% in 48 h relative to DC-free controls. We further developed a model that allowed us to predict temperature- and DC field strength-dependent electrokinetic benefits on the drivers of PFOA sorption kinetics (i.e., intraparticle diffusivity and the film mass transfer coefficient). Our insights may give rise to future DC- and temperature-driven applications for PFOA sorption, for instance, in response to fluctuating PFOA concentrations in contaminated water streams.

Bioconcentration of Inorganic and Methyl Mercury by Algae Revealed Using Dual-Mass Single-Cell ICP-MS with Double Isotope Tracers.

Algae are an entry point for mercury (Hg) into the food web. Bioconcentration of Hg by algae is crucial for its biogeochemical cycling and environmental risk. Herein, considering the cell heterogeneity, we investigated the bioconcentration of coexisting isotope-labeled inorganic (199IHg) and methyl Hg (201MeHg) by six typical freshwater and marine algae using dual-mass single-cell inductively coupled plasma mass spectrometry (scICP-MS). First, a universal pretreatment procedure for the scICP-MS analysis of algae was developed. Using the proposed method, the intra- and interspecies heterogeneities and the kinetics of Hg bioconcentration by algae were revealed at the single-cell level. The heterogeneity in the cellular Hg contents is largely related to cell size. The bioconcentration process reached a dynamic equilibrium involving influx/adsorption and efflux/desorption within hours. Algal density is a key factor affecting the distribution of Hg between algae and ambient water. Cellular Hg contents were negatively correlated with algal density, whereas the volume concentration factors almost remained constant. Accordingly, we developed a model based on single-cell analysis that well describes the density-driven effects of Hg bioconcentration by algae. From a novel single-cell perspective, the findings improve our understanding of algal bioconcentration governed by various biological and environmental factors.

Soil organic matter degradation and methylmercury dynamics in Hg-contaminated soils: Relationships and driving factors.

Biodegradation of soil organic matter (SOM), which involves greenhouse gas (GHG) emissions, plays an essential role in the global carbon cycle. Over the past few decades, this has become an important research focus, particularly in natural ecosystems. SOM biodegradation significantly affects contaminants in the environment, such as mercury (Hg) methylation, producing highly toxic methylmercury (MeHg). However, the potential link between GHG production from SOM turnover in contaminated soils and biogeochemical processes involving contaminants remains unclear. In this study, we investigated the dynamics of GHG, MeHg production, and the relationship between biogeochemical processes in soils from two typical Hg mining sites. The two contaminated soils have different pathways, explaining the significant variations in GHG and MeHg production. The divergence of the microbial communities in these two biogeochemical processes is essential. In addition to the microbial role, abiotic factors such as Hg species can significantly affect MeHg production. On the other hand, we found an inverse relationship between CH4 and MeHg, suggesting that carbon emission reduction policies and management could inadvertently increase the MeHg levels. This highlights the need for an eclectic approach to organic carbon sequestration and contaminant containment. These findings suggest that it is difficult to establish a general pattern to describe and explain the SOM degradation and MeHg production in contaminated soils within the specific scenarios. However, this study provides a case study and helpful insights for further understanding the links between environmental risks and carbon turnover in Hg mining areas.

Mechanisms of heating-electrokinetic co-driven perfluorooctanoic acid (PFOA) adsorption on zeolite.

Slow release of emerging contaminants limits their accessibility from soil to pore water, constraining the treatment efficiency of physio-chemical treatment sites. DC fields mobilize organic contaminants and influence their interactions with geo-matrices such as zeolites. Poor knowledge, however, exists on the joint application of heating and electrokinetic approaches on perfluorooctanoic acid (PFOA) transport in porous media. Here, we investigated electrokinetic PFOA transport in zeolite-filled percolation columns at varying temperatures. Variations of pseudo-second-order kinetic constants (kPSO) were correlated to the liquid viscosity variations (η) and elctroosmotic flow velocities (vEOF). Applying DC fields and elevated temperature significantly (>37%) decreased PFOA sorption to zeolite. A good correlation between η, vEOF, and kPSO was found and used to develop an approach interlinking the three parameters to predict the joint effects of DC fields and temperature on PFOA sorption kinetics. These findings may give rise to future applications for better tailoring PFOA transport in environmental biotechnology.

Superoxide-Mediated Extracellular Mercury Reduction by Aerobic Marine Bacterium Alteromonas sp. KD01.

Microbial reduction plays a crucial role in Hg redox and the global cycle. Although intracellular Hg(II) reduction mediated by MerA protein is well documented, it is still unclear whether or how bacteria reduce Hg(II) extracellularly without its internalization. Herein, for the first time, we discovered the extracellular reduction of Hg(II) by a widely distributed aerobic marine bacterium Alteromonas sp. KD01 through a superoxide-dependent mechanism. The generation of superoxide by Alteromonas sp. KD01 was determined using 3-bis(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide and methyl cypridina luciferin analogue as probes via UV-vis and chemiluminescence detection, respectively. The results demonstrated that Hg(II) reduction was inhibited by superoxide scavengers (superoxide dismutase (SOD) and Cu(NO3)2) or inhibitors of reduced nicotinamide adenine dinucleotide (NADH) oxidoreductases. In contrast, the addition of NADH significantly improved superoxide generation and, in turn, Hg(II) reduction. Direct evidence of superoxide-mediated Hg(II) reduction was provided by the addition of superoxide using KO2 in deionized water and seawater. Moreover, we observed that even superoxide at an environmental concentration of 9.6 ± 0.5 nM from Alteromonas sp. KD01 (5.4 × 106 cells mL-1) was capable of significantly reducing Hg(II). Our findings provide a greater understanding of Hg(II) reduction by superoxide from heterotrophic bacteria and eukaryotic phytoplankton in diverse aerobic environments, including surface water, sediment, and soil.

Transformation of Mercuric Ions to Mercury Nanoparticles in Diatom Chaetoceros curvisetus.

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

Unraveling Multiple Pathways of Electron Donation from Phenolic Moieties in Natural Organic Matter.

Natural organic matter (NOM) exhibits a distinctive electron-donating capacity (EDC) that serves a pivotal role in the redox reactions of contaminants and minerals through the transformation of electron-donating phenolic moieties. However, the ambiguity of the molecular transformation pathways (MTPs) that engender the EDC during NOM oxidation remains a significant issue. Here, MTPs that contribute to EDC were investigated by identifying the oxidized products of phenolic model compounds and NOM samples in direct or mediated electrochemical oxidation (DEO or MEO, respectively) using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). It was found that the oxidation of newly formed phenolic-OH (ArOH) and the oxidative coupling reaction of the phenoxy radical are the main MTPs that directly contribute to EDC, in addition to the transformation of hydroquinones to quinones. Notably, the oxidative coupling reaction of ArOH contributed at least 22-42% to the EDC. Ferulic acid-like structures can also directly contribute to EDC by incorporating H2O into their acrylic substituents. Furthermore, the opening of C rings can indirectly attenuate the EDC through structural alterations in the electron-donating process of NOM. Decarboxylation can either weaken or enhance the EDC depending on the structure of the phenolic moieties in NOM. These findings suggest that the EDC of NOM is a comprehensive result of multiple NOM MTPs, involving not only ArOH oxidation but also the addition of H2O to olefinic bonds and bond-breaking reactions. Our work provides molecular evidence that aids in the comprehension of the multiple EDC-associated transformation pathways of NOM.

Direct Uptake and Intracellular Dissolution of HgS Nanoparticles: Evidence from a Bacterial Biosensor Approach.

Mercury sulfide nanoparticles (HgSNPs), which occur widely in oxic and anoxic environments, can be microbially converted to highly toxic methylmercury or volatile elemental mercury, but it remains challenging to assess their bioavailability. In this study, an Escherichia coli-based whole-cell fluorescent biosensor was developed to explore the bioavailability and microbial activation process of HgSNPs. Results show that HgSNPs (3.17 ± 0.96 nm) trigger a sharp increase in fluorescence intensity of the biosensor, with signal responses almost equal to that of ionic Hg (Hg(II)) within 10 h, indicating high bioavailability of HgSNP. The intracellular total Hg (THg) of cells exposed to HgSNPs (200 µg L-1) was 3.52-8.59-folds higher than that of cells exposed to Hg(II) (200 µg L-1), suggesting that intracellular HgSNPs were only partially dissolved. Speciation analysis using size-exclusion chromatography (SEC)-inductively coupled plasma mass spectrometry (ICP-MS) revealed that the bacterial filtrate was not responsible for HgSNP dissolution, suggesting that HgSNPs entered cells in nanoparticle form. Combined with fluorescence intensity and intracellular THg analysis, the intracellular HgSNP dissolution ratio was estimated at 22-29%. Overall, our findings highlight the rapid internalization and high intracellular dissolution ratio of HgSNPs by E. coli, and intracellular THg combined with biosensors could provide innovative tools to explore the microbial uptake and dissolution of HgSNPs.

Exogenous Metals Atlas in Spermatozoa at Single-Cell Resolution in Relation to Human Semen Quality.

While exogenous metal/metalloid (metal) exposure has been associated with reduced human semen quality, no study has assessed the associations of exogenous metals in human spermatozoa with semen quality. Here, we developed a strategy to explore the associations between exogenous metals in spermatozoa at single-cell resolution and human semen quality among 84 men screened as sperm donors, who provided 266 semen samples within 90 days. A cellular atlas of exogenous metals at the single-cell level was created with mass cytometry (CyTOF) technology, which concurrently displayed 18 metals in more than 50 000 single sperm. Exogenous metals in spermatozoa at single-cell resolution were extremely heterogeneous and diverse. Further analysis using multivariable linear regression and linear mixed-effects models revealed that the heterogeneity and prevalence of the exogenous metals at single-cell resolution were associated with semen quality. The heterogeneity of lead (Pb), tin (Sn), yttrium (Y), and zirconium (Zr) was negatively associated with sperm concentration and count, while their prevalence showed positive associations. These findings revealed that the heterogeneous properties of exogenous metals in spermatozoa were associated with human semen quality, highlighting the importance of assessing exogenous metals in spermatozoa at single-cell resolution to evaluate male reproductive health risk precisely.

Dissolved metal ion removal by online hollow fiber ultrafiltration for enhanced size characterization of metal-containing nanoparticles with single-particle ICP-MS.

Single particle-inductively coupled plasma mass spectrometry (SP-ICP-MS) is a powerful tool for size-characterization of metal-containing nanoparticles (MCNs) at environmentally relevant concentrations, however, coexisting dissolved metal ions greatly interfere with the accuracy of particle size analysis. The purpose of this study is to develop an online technique that couples hollow fiber ultrafiltration (HFUF) with SP-ICP-MS to improve the accuracy and size detection limit of MCNs by removing metal ions from suspensions of MCNs. Through systematic optimization of conditions including the type and concentration of surfactant and complexing agent, carrier pH, and ion cleaning time, HFUF completely removes metal ions but retains the MCNs in suspension. The optimal conditions include using a mixture of 0.05 vol.% FL-70 and 0.5 mmol/L Na2S2O3 (pH = 8.0) as the carrier and 4 min as the ion cleaning time. At these conditions, HFUF-SP-ICP-MS accurately determines the sizes of MCNs, and the results agree with the size distribution determined by transmission electron microscopy, even when metal ions also are present in the sample. In addition, reducing the ionic background through HFUF also lowers the particle size detection limit with SP-ICP-MS (e.g., from 28.3 to 14.2 nm for gold nanoparticles). This size-based ion-removal principle provided by HFUF is suitable for both cations (e.g., Ag+) and anions (e.g., AuCl4-) and thus has good versatility compared to ion exchange purification and promising prospects for the removal of salts and macromolecules before single particle analysis.

Mass Budget of Mercury (Hg) in the Seawater of Eastern China Marginal Seas: Importance of the Sediment-Water Transport Processes.

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

Loss and Increase of the Electron Exchange Capacity of Natural Organic Matter during Its Reduction and Reoxidation: The Role of Quinone and Nonquinone Moieties.

Redox-active quinone and nonquinone moieties represent the electron exchange capacity (EEC) of natural organic matter (NOM), playing an important role in the electron transfer link of microbes and transformation of contaminants/metal minerals. However, the corresponding transformation of quinone/phenol and their respective influence on the EECs during reduction and reoxidation remain poorly characterized. Besides, it is still controversial whether nonquinones donate or accept electrons. Herein, we demonstrated that reoxidation of NOM after reduction can form new phenolic/quinone moieties, thus increasing the EEC. The assessment for the EEC, including the electron-donating capacity (EDC) and electron-accepting capacity (EAC), of nonquinones reflects the contribution of sulfur-containing moieties with considerable EDCs and EACs. In contrast, nitrogen-containing moieties donate negligible electrons even at Eh = +0.73 V. The contributions of both thiol and amine moieties to the EEC are greatly affected by adjacent functional groups. Meanwhile, aldehydes/ketones did not display an EAC during the electron transfer process of NOM. Furthermore, substantially increased EDC at Eh from +0.61 to +0.73 V could not be fully explained using thiol and phenolic moieties, suggesting the contribution of unknown moieties with high oxidation potential. The overall findings suggest that the roles of new quinones/phenol (derived from the addition of oxygen to condensed aromatic/lignin-like components) during redox dynamic cycling and thiol species should be considered in assessing the electron transfer processes of NOM.

Particle-Bound Hg(II) is Available for Microbial Uptake as Revealed by a Whole-Cell Biosensor.

Particle-bound mercury (HgP), ubiquitously present in aquatic environments, can be methylated into highly toxic methylmercury, but it remains challenging to assess its bioavailability. In this study, we developed anEscherichia coli-based whole-cell biosensor to probe the microbial uptake of inorganic Hg(II) and assess the bioavailability of HgP sorbed on natural and model particles. This biosensor can quantitatively distinguish the contribution of dissolved Hg(II) and HgP to intracellular Hg. Results showed that the microbial uptake of HgP was ubiquitous in the environment, as evidenced by the bioavailability of sorbed-Hg(II) onto particulate matter and model particles (Fe2O3, Fe3O4, Al2O3, and SiO2). In both oxic and anoxic environments, HgP was an important Hg(II) source for microbial uptake, with enhanced bioavailability under anoxic conditions. The composition of particles significantly affected the microbial uptake of HgP, with higher bioavailability being observed for Fe2O3 and lower for Al2O3 particles. The bioavailability of HgP varied also with the size of particles. In addition, coating with humic substances and model organic compound (cysteine) on Fe2O3 particles decreased the bioavailability of HgP. Overall, our findings highlight the role of HgP in Hg biogeochemical cycling and shed light on the enhanced Hg-methylation in settling particles and sediments in aquatic environments.

Administration of Silver Nasal Spray Leads to Nanoparticle Accumulation in Rat Brain Tissues.

The use of commercial products containing engineered nanomaterials in realistic scenarios may lead to the accumulation of exogenous particles in brain tissues. In this study, we simulated the use of silver (Ag) nasal spray in humans using Sprague-Dawley rats at 0.04 mg/kg/day. Silver-containing particles were explicitly identified in the rat brain after the administration of nasal sprays containing colloidal Ag or silver ions (Ag+) for 2 weeks using multiple methods. The accumulation of Ag-containing particles showed a delayed effect in different brain regions of the rats, with the mass concentration of particles increasing continuously for 1-2 weeks after the termination of administration. The size of the observed Ag-containing particles extracted from the brain tissues ranged from 18.3 to 120.4 nm. Further characterization by high-resolution transmission electron microscopy with energy-dispersive spectroscopy showed that the nanoparticles comprised both Ag and sulfur (S), with Ag/S atomic ratios of 1.1-7.1, suggesting that Ag-containing particles went through a series of transformations prior to or during their accumulation in the brain. Collectively, these findings provide evidence for the accumulation and transformation of Ag-containing particles in the rat brain, indicating a realistic risk to brain health resulting from the application of Ag-containing commercial products.

Tracing the Transboundary Transport of Mercury to the Tibetan Plateau Using Atmospheric Mercury Isotopes.

Deposition of atmospheric mercury (Hg) is the most important Hg source on the high-altitude Himalayas and Tibetan Plateau. Herein, total gaseous Hg (TGM) at an urban and a forest site on the Tibetan Plateau was collected respectively from May 2017 to October 2018, and isotopic compositions were measured to clarify the influences of landforms and monsoons on the transboundary transport of atmospheric Hg to the Tibetan Plateau. The transboundary transported anthropogenic emissions mainly originated over Indo-Gangetic Plain and carried over the Himalayas by convective storms and mid-tropospheric circulation, contributing over 50% to the TGM at the Lhasa urban site, based on the binary mixing model of isotopes. In contrast, during the transport of TGM from South Asia with low altitude, the uptake by evergreen forest in Yarlung Zangbo Grand Canyon largely decreased the TGM level and shifted isotopic compositions in TGM at the Nyingchi forest site, which are located at the high-altitude end of the canyon. Our results provided direct evidence from Hg isotopes to reveal the distinct patterns of transboundary transport to the Tibetan Plateau shaped by landforms and climates, which is critical to fully understand the biogeochemical cycling of Hg in the high-altitude regions.