Global airborne bacterial community-interactions with Earth's microbiomes and anthropogenic activities.

Airborne bacteria are an influential component of the Earth's microbiomes, but their community structure and biogeographic distribution patterns have yet to be understood. We analyzed the bacterial communities of 370 air particulate samples collected from 63 sites around the world and constructed an airborne bacterial reference catalog with more than 27 million nonredundant 16S ribosomal RNA (rRNA) gene sequences. We present their biogeographic pattern and decipher the interlacing of the microbiome co-occurrence network with surface environments of the Earth. While the total abundance of global airborne bacteria in the troposphere (1.72 × 1024 cells) is 1 to 3 orders of magnitude lower than that of other habitats, the number of bacterial taxa (i.e., richness) in the atmosphere (4.71 × 108 to 3.08 × 109) is comparable to that in the hydrosphere, and its maximum occurs in midlatitude regions, as is also observed in other ecosystems. The airborne bacterial community harbors a unique set of dominant taxa (24 species); however, its structure appears to be more easily perturbed, due to the more prominent role of stochastic processes in shaping community assembly. This is corroborated by the major contribution of surface microbiomes to airborne bacteria (averaging 46.3%), while atmospheric conditions such as meteorological factors and air quality also play a role. Particularly in urban areas, human impacts weaken the relative importance of plant sources of airborne bacteria and elevate the occurrence of potential pathogens from anthropogenic sources. These findings serve as a key reference for predicting planetary microbiome responses and the health impacts of inhalable microbiomes with future changes in the environment.

New Insights into MeHg Accumulation in Rice (Oryza sativa L.): Evidence from Cysteine.

The intake of methylmercury (MeHg)-contaminated rice poses immense health risks to rice consumers. However, the mechanisms of MeHg accumulation in rice plants are not entirely understood. The knowledge that the MeHg-Cysteine complex was dominant in polished rice proposed a hypothesis of co-transportation of MeHg and cysteine inside rice plants. This study was therefore designed to explore the MeHg accumulation processes in rice plants by investigating biogeochemical associations between MeHg and amino acids. Rice plants and underlying soils were collected from different Hg-contaminated sites in the Wanshan Hg mining area. The concentrations of both MeHg and cysteine in polished rice were higher than those in other rice tissues. A significant positive correlation between MeHg and cysteine in rice plants was found, especially in polished rice, indicating a close geochemical association between cysteine and MeHg. The translocation factor (TF) of cysteine showed behavior similar to that of the TF of MeHg, demonstrating that these two chemical species might share a similar transportation mechanism in rice plants. The accumulation of MeHg in rice plants may vary due to differences in the molar ratios of MeHg to cysteine and the presence of specific amino acid transporters. Our results suggest that cysteine plays a vital role in MeHg accumulation and transportation inside rice plants.

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.

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.

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.

Fate and Transport of Mercury through Waterflows in a Tropical Rainforest.

Knowledge gaps of mercury (Hg) biogeochemical processes in the tropical rainforest limit our understanding of the global Hg mass budget. In this study, we applied Hg stable isotope tracing techniques to quantitatively understand the Hg fate and transport during the waterflows in a tropical rainforest including open-field precipitation, throughfall, and runoff. Hg concentrations in throughfall are 1.5-2 times of the levels in open-field rainfall. However, Hg deposition contributed by throughfall and open-field rainfall is comparable due to the water interception by vegetative biomasses. Runoff from the forest shows nearly one order of magnitude lower Hg concentration than those in throughfall. In contrast to the positive Δ199Hg and Δ200Hg signatures in open-field rainfall, throughfall water exhibits nearly zero signals of Δ199Hg and Δ200Hg, while runoff shows negative Δ199Hg and Δ200Hg signals. Using a binary mixing model, Hg in throughfall and runoff is primarily derived from atmospheric Hg0 inputs, with average contributions of 65 ± 18 and 91 ± 6%, respectively. The combination of flux and isotopic modeling suggests that two-thirds of atmospheric Hg2+ input is intercepted by vegetative biomass, with the remaining atmospheric Hg2+ input captured by the forest floor. Overall, these findings shed light on simulation of Hg cycle in tropical forests.

Determination of the Isotopic Composition of Aqueous Mercury in a Paddy Ecosystem Using Diffusive Gradients in Thin Films.

Measuring the isotopic composition of Hg in natural waters is challenging due to the ultratrace level of aqueous Hg (ng L-1). At least 5 ng of Hg mass is required for Hg isotopic analysis. Given the low Hg concentration in natural waters, a large volume of water (>10 L) is typically needed. The conventional grab sampling method is time-consuming, laborious, and prone to contamination during transportation and preconcentration steps. In this study, a DGT (diffusive gradients in thin films) method based on aminopropyl and mercaptopropyl bi-functionalized SBA-15 nanoparticles was developed and extended to determine the concentration and isotopic composition of aqueous Hg for the first time. The results of laboratory analysis showed that Hg adsorption by DGT induces ∼ -0.2‰ mass-dependent fractionation (MDF) and little mass-independent fractionation (MIF). The magnitude of MDF exhibits a dependence on the diffusion-layer thickness of DGT. Since Hg-MDF can occur in a broad range of environmental processes, monitoring the δ202Hg of aqueous Hg using the DGT method should be performed with caution. Field results show consistent MIF signatures (Δ199Hg) between the DGT and conventional grab sampling method. The developed DGT method serves as a passive sampling method that effectively characterizes the MIF of Hg in waters to understand the biogeochemical cycle of Hg at contaminated sites.

Mercury Accumulation and Sequestration in a Deglaciated Forest Chronosequence: Insights from Particulate and Mineral-Associated Forms of Organic Matter.

Understanding mercury (Hg) complexation with soil organic matter is important in assessing atmospheric Hg accumulation and sequestration processes in forest ecosystems. Separating soil organic matter into particulate organic matter (POM) and mineral-associated organic matter (MAOM) can help in the understanding of Hg dynamics and cycling due to their very different chemical constituents and associated formation and functioning mechanisms. The concentration of Hg, carbon, and nitrogen contents and isotopic signatures of POM and MAOM in a deglaciated forest chronosequence were determined to construct the processes of Hg accumulation and sequestration. The results show that Hg in POM and MAOM are mainly derived from atmospheric Hg0 deposition. Hg concentration in MAOM is up to 76% higher than that in POM of broadleaf forests and up to 60% higher than that in POM of coniferous forests. Hg accumulation and sequestration in organic soil vary with the vegetation succession. Variations of δ202Hg and Δ199Hg are controlled by source mixing in the broadleaf forest and by Hg sequestration processes in the coniferous forest. Accumulation of atmospheric Hg and subsequent microbial reduction enrich heavier Hg isotopes in MAOM compared to POM due to the specific chemical constituents and nutritional role of MAOM.

Quantifying Mercury Distribution and Source Contribution in Surface Soil of Qinghai-Tibetan Plateau Using Mercury Isotopes.

Long-range transport and atmospheric deposition of gaseous mercury (Hg0) result in significant accumulation of Hg in the Qinghai-Tibetan Plateau (QTP). However, there are significant knowledge gaps in understanding the spatial distribution and source contribution of Hg in the surface soil of the QTP and factors influencing Hg accumulation. In this study, we comprehensively investigated Hg concentrations and isotopic signatures in the QTP to address these knowledge gaps. Results show that the average Hg concentration in the surface soil ranks as follows: forest (53.9 ± 36.9 ng g-1) > meadow (30.7 ± 14.3 ng g-1) > steppe (24.5 ± 16.1 ng g-1) > shrub (21.0 ± 11.6 ng g-1). Hg isotopic mass mixing and structural equation models demonstrate that vegetation-mediated atmospheric Hg0 deposition dominates the Hg source in the surface soil, with an average contribution of 62 ± 12% in forests, followed by 51 ± 10% in shrub, 50 ± 13% in steppe, and 45 ± 11% in meadow. Additionally, geogenic sources contribute 28-37% of surface soil Hg accumulation, and atmospheric Hg2+ inputs contribute 10-18% among the four types of biomes. The Hg pool in 0-10 cm surface soil over the QTP is estimated as 8200 ± 3292 Mg. Global warming, permafrost degradation, and anthropogenic influences have likely perturbed Hg accumulation in the soil of QTP.

Mercury and Sulfur Redox Cycling Affect Methylmercury Levels in Rice Paddy Soils across a Contamination Gradient.

Methylmercury (MeHg) contamination in rice via paddy soils is an emerging global environmental issue. An understanding of mercury (Hg) transformation processes in paddy soils is urgently needed in order to control Hg contamination of human food and related health impacts. Sulfur (S)-regulated Hg transformation is one important process that controls Hg cycling in agricultural fields. In this study, Hg transformation processes, such as methylation, demethylation, oxidation, and reduction, and their responses to S input (sulfate and thiosulfate) in paddy soils with a Hg contamination gradient were elucidated simultaneously using a multi-compound-specific isotope labeling technique (200HgII, Me198Hg, and 202Hg0). In addition to HgII methylation and MeHg demethylation, this study revealed that microbially mediated reduction of HgII, methylation of Hg0, and oxidative demethylation-reduction of MeHg occurred under dark conditions; these processes served to transform Hg between different species (Hg0, HgII, and MeHg) in flooded paddy soils. Rapid redox recycling of Hg species contributed to Hg speciation resetting, which promoted the transformation between Hg0 and MeHg by generating bioavailable HgII for fuel methylation. Sulfur input also likely affected the microbial community structure and functional profile of HgII methylators and, therefore, influenced HgII methylation. The findings of this study contribute to our understanding of Hg transformation processes in paddy soils and provide much-needed knowledge for assessing Hg risks in hydrological fluctuation-regulated ecosystems.

Antimony Isotope Fractionation Revealed from EXAFS during Adsorption on Fe (Oxyhydr)oxides.

A lack of knowledge about antimony (Sb) isotope fractionation mechanisms in key geochemical processes has limited its environmental applications as a tracer. Naturally widespread iron (Fe) (oxyhydr)oxides play a key role in Sb migration due to strong adsorption, but the behavior and mechanisms of Sb isotopic fractionation on Fe (oxyhydr)oxides are still unclear. Here, we investigate the adsorption mechanisms of Sb on ferrihydrite (Fh), goethite (Goe), and hematite (Hem) using extended X-ray absorption fine structure (EXAFS) and show that inner-sphere complexation of Sb species with Fe (oxyhydr)oxides occurs independent of pH and surface coverage. Lighter Sb isotopes are preferentially enriched on Fe (oxyhydr)oxides due to isotopic equilibrium fractionation, with neither surface coverage nor pH influencing the degree of fractionation (Δ123Sbaqueous-adsorbed). Limited Fe atoms are present in the second shell of Hem and Goe, resulting in weaker surface complexes and leading to greater Sb isotopic fractionation than with Fh (Δ123Sbaqueous-adsorbed of 0.49 ± 0.004, 1.12 ± 0.006, and 1.14 ± 0.05‰ for Fh, Hem, and Goe, respectively). These results improve the understanding of the mechanism of Sb adsorption by Fe (oxyhydr)oxides and further clarify the Sb isotope fractionation mechanism, providing an essential basis for future application of Sb isotopes in source and process tracing.

Using Mercury Stable Isotopes to Quantify Bidirectional Water-Atmosphere Hg(0) Exchange Fluxes and Explore Controlling Factors.

In this study, exchange fluxes and Hg isotope fractionation during water-atmosphere Hg(0) exchange were investigated at three lakes in China. Water-atmosphere exchange was overall characterized by net Hg(0) emissions, with lake-specific mean exchange fluxes ranging from 0.9 to 1.8 ng m-2 h-1, which produced negative δ202Hg (mean: -1.61 to -0.03‰) and Δ199Hg (-0.34 to -0.16‰) values. Emission-controlled experiments conducted using Hg-free air over the water surface at Hongfeng lake (HFL) showed negative δ202Hg and Δ199Hg in Hg(0) emitted from water, and similar values were observed between daytime (mean δ202Hg: -0.95‰, Δ199Hg: -0.25‰) and nighttime (δ202Hg: -1.00‰, Δ199Hg: -0.26‰). Results of the Hg isotope suggest that Hg(0) emission from water is mainly controlled by photochemical Hg(0) production in water. Deposition-controlled experiments at HFL showed that heavier Hg(0) isotopes (mean ε202Hg: -0.38‰) preferentially deposited to water, likely indicating an important role of aqueous Hg(0) oxidation played during the deposition process. A Δ200Hg mixing model showed that lake-specific mean emission fluxes from water surfaces were 2.1-4.1 ng m-2 h-1 and deposition fluxes to water surfaces were 1.2-2.3 ng m-2 h-1 at the three lakes. Results from the this study indicate that atmospheric Hg(0) deposition to water surfaces indeed plays an important role in Hg cycling between atmosphere and water bodies.

Isotopic Characterization of Mercury Atmosphere-Foliage and Atmosphere-Soil Exchange in a Swiss Subalpine Coniferous Forest.

To understand the role of vegetation and soil in regulating atmospheric Hg0, exchange fluxes and isotope signatures of Hg were characterized using a dynamic flux bag/chamber at the atmosphere-foliage/soil interfaces at the Davos-Seehornwald forest, Switzerland. The foliage was a net Hg0 sink and took up preferentially the light Hg isotopes, consequently resulting in large shifts (-3.27‰) in δ202Hg values. The soil served mostly as net sources of atmospheric Hg0 with higher Hg0 emission from the moss-covered soils than from bare soils. The negative shift of δ202Hg and Δ199Hg values of the efflux air relative to ambient air and the Δ199Hg/Δ201Hg ratio among ambient air, efflux air, and soil pore gas highlight that Hg0 re-emission was strongly constrained by soil pore gas evasion together with microbial reduction. The isotopic mass balance model indicates 8.4 times higher Hg0 emission caused by pore gas evasion than surface soil photoreduction. Deposition of atmospheric Hg0 to soil was noticeably 3.2 times higher than that to foliage, reflecting the high significance of the soil to influence atmospheric Hg0 isotope signatures. This study improves our understanding of Hg atmosphere-foliage/soil exchange in subalpine coniferous forests, which is indispensable in the model assessment of forest Hg biogeochemical cycling.

Elevated Mercury Deposition, Accumulation, and Migration in a Karst Forest.

The karst forest is one of the extremely sensitive and fragile ecosystems in southwest China, where the biogeochemical cycling of mercury (Hg) is largely unknown. In this study, we investigated the litterfall deposition, accumulation, and soil migration of Hg in an evergreen-deciduous broadleaf karst forest using high-resolution sampling and stable isotope techniques. Results show that elevated litterfall Hg concentrations and fluxes in spring are due to the longer lifespan of evergreen tree foliage exposed to atmospheric Hg0. The hillslope has 1-2 times higher litterfall Hg concentration compared to the low-lying land due to the elevated atmospheric Hg levels induced by topographical and physiological factors. The Hg isotopic model suggests that litterfall Hg depositions account for ∼80% of the Hg source contribution in surface soil. The spatial trend of litterfall Hg deposition cannot solely explain the trend of Hg accumulation in the surface soil. Indeed, soil erosion enhances Hg accumulation in soil of low-lying land, with soil Hg concentration up to 5-times greater than the concentration on the hillslope. The high level of soil Hg migration in the karst forest poses significant ecological risks to groundwater and downstream aquatic ecosystems.

Deposition and Re-Emission of Atmospheric Elemental Mercury over the Tropical Forest Floor.

Significant knowledge gaps exist regarding the emission of elemental mercury (Hg0) from the tropical forest floor, which limit our understanding of the Hg mass budget in forest ecosystems. In this study, biogeochemical processes of Hg0 deposition to and evasion from soil in a Chinese tropical rainforest were investigated using Hg stable isotopic techniques. Our results showed a mean air-soil flux as deposition of -4.5 ± 2.1 ng m-2 h-1 in the dry season and as emission of +7.4 ± 1.2 ng m-2 h-1 in the rainy season. Hg re-emission, i.e., soil legacy Hg evasion, induces negative transitions of Δ199Hg and δ202Hg in the evaded Hg0 vapor, while direct atmospheric Hg0 deposition does not exhibit isotopic fractionation. Using an isotopic mass balance model, direct atmospheric Hg0 deposition to soil was estimated to be 48.6 ± 13.0 µg m-2 year-1. Soil Hg0 re-emission was estimated to be 69.5 ± 10.6 µg m-2 year-1, of which 63.0 ± 9.3 µg m-2 year-1 is from surface soil evasion and 6.5 ± 5.0 µg m-2 year-1 from soil pore gas diffusion. Combined with litterfall Hg deposition (∼34 µg m-2 year-1), we estimated a ∼12.6 µg m-2 year-1 net Hg0 sink in the tropical forest. The fast nutrient cycles in the tropical rainforests lead to a strong Hg0 re-emission and therefore a relatively weaker atmospheric Hg0 sink.

Predominant contributions through lichen and fine litter to litterfall mercury deposition in a subalpine forest.

Litterfall, typically referring to needles/leaves, may stand for >50% of the total mercury (Hg) deposition in forest ecosystems. By detailed categorisation, we reveal for the first time that the contributions through lichens and fine litter, together 9.98 µg Hg m-2 yr-1, could be as high as that in needle litter (9.96 µg m-2 yr-1) to the annual total Hg deposition (44.6 µg m-2 yr-1) in a subalpine forest in Switzerland. Noticeably, needle litter had the highest contribution (53%) to total Hg in the autumn litterfall but lichens and fine litter together predominated in other seasons (47-59%). Such a seasonal pattern is caused by the high ability of lichens and fine litter to accumulate Hg and the high needle litterfall in autumn, which is related to a good rainfall in summer followed by a dry period in autumn. The constantly higher Hg levels in lichens and fine litter than in needle litter together with similar seasonal patterns of litterfall during 2009-2019 and rainfall during 1980-2019 suggest that our finding can be generally valid. Here, we highlight not only the considerable role of non-needle litterfall in Hg deposition but also the association with weather for seasonal Hg dynamics in different litterfall components.

Global warming accelerates uptake of atmospheric mercury in regions experiencing glacier retreat.

As global climate continues to warm, melting of glaciers releases a large quantity of mercury (Hg) originally locked in ice into the atmosphere and downstream ecosystems. Here, we show an opposite process that captures atmospheric Hg through glacier-to-vegetation succession. Our study using stable isotope techniques at 3 succession sites on the Tibetan Plateau reveals that evolving vegetation serves as an active "pump" to take up gaseous elemental mercury (Hg0) from the atmosphere. The accelerated uptake enriches the Hg pool size in glacier-retreated areas by a factor of ∼10 compared with the original pool size in the glacier. Through an assessment of Hg source-sink relationship observed in documented glacier-retreated areas in the world (7 sites of tundra/steppe succession and 5 sites of forest succession), we estimate that 400 to 600 Mg of Hg has been accumulated in glacier-retreated areas (5‰ of the global land surface) since the Little Ice Age (∼1850). By 2100, an additional ∼300 Mg of Hg will be sequestered from the atmosphere in glacier-retreated regions globally, which is ∼3 times the total Hg mass loss by meltwater efflux (∼95 Mg) in alpine and subpolar glacier regions. The recapturing of atmospheric Hg by vegetation in glacier-retreated areas is not accounted for in current global Hg models. Similar processes are likely to occur in other regions that experience increased vegetation due to climate or land use changes, which need to be considered in the assessment of global Hg cycling.

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

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

Mercury Isotope Fractionation during the Exchange of Hg(0) between the Atmosphere and Land Surfaces: Implications for Hg(0) Exchange Processes and Controls.

Atmosphere-surface exchange of elemental mercury (Hg(0)) is a vital component in global Hg cycling; however, Hg isotope fractionation remains largely unknown. Here, we report Hg isotope fractionation during air-surface exchange from terrestrial surfaces at sites of background (two) and urban (two) character and at five sites contaminated by Hg mining. Atmospheric Hg(0) deposition to soils followed kinetic isotope fractionation with a mass-dependent (MDF) enrichment factor of -4.32‰, and negligible mass-independent fractionation (MIF). Net Hg(0) emission generated average MDF enrichment factors (ε202Hg) of -0.91, -0.59, 1.64, and -0.42‰ and average MIF enrichment factors (E199Hg) of 0.07, -0.20, -0.14, and 0.21‰ for urban, background, and Hg mining soils and cinnabar tailing, respectively. Positive correlations between ε202Hg and ambient Hg(0) concentration indicate that the co-occurring Hg(0) deposition (accounting for 10-39%) in a regime of net soil emission grows with ambient Hg(0). The MIF of Hg(0) emission from soils (E199Hg range -0.27 to 0.14‰, n = 8) appears to be overall controlled by the photochemical reduction of kinetically constrained Hg(II) bonded to O ligands in background soils, while S ligands may have been more important in Hg mining area soils. In contrast, the small positive MIF of Hg(0) emission from cinnabar ore tailing (mean E199Hg = 0.21‰) was likely controlled by abiotic nonphotochemical reduction and liquid Hg(0) evaporation. This research provides critical observational constraints on understanding the Hg(0) isotope signatures released from and deposited to terrestrial surfaces and highlight stable Hg isotopes as a powerful tool for resolving atmosphere-surface exchange processes.

Mercury Uptake, Accumulation, and Translocation in Roots of Subtropical Forest: Implications of Global Mercury Budget.

Plant roots are responsible for transporting large quantities of nutrients in forest ecosystems and yet are frequently overlooked in global assessments of Hg cycling budgets. In this study, we systematically determined the distribution of total Hg mass and its stable isotopic signatures in a subtropical evergreen forest to elucidate sources of Hg in plant root tissues and the associated translocation mechanisms. Hg stored in roots and its isotopic signatures show significant correlations to those found in surrounding soil at various soil depths. The odd mass-independent fractionation (MIF) of root Hg at a shallow soil depth displays a -0.10‰ to -0.50‰ negative transition compared to the values in aboveground woody biomass. The evidence suggests that root Hg is predominantly derived from surrounding soil, rather than translocation of atmospheric uptake via aboveground tissues. The cortex has a more negative mass-dependent fractionation (MDF) of -0.10‰ to -1.20‰ compared to the soil samples, indicating a preferential uptake of lighter isotopes by roots. The similar MDF and odd-MIF signals found in root components imply limited Hg transport in roots. This work highlights that Hg stored in plant roots is not a significant sink of atmospheric Hg. The heterogeneous distribution of Hg mass in roots of various sizes represents a significant uncertainty of current estimates of Hg pool size in forest ecosystems.