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.

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

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

Isotopic 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.

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.

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 investigation of sources and processes affecting gaseous and particulate bound mercury in the east coast, South Korea.

Understanding sources and processes affecting atmospheric mercury (Hg) are key to enabling targeted Hg managements under the Minamata Convention on Mercury. We employed stable isotopes (δ202Hg, Δ199Hg, Δ201Hg, Δ200Hg, Δ204Hg) and backward air trajectories to characterize sources and processes affecting total gaseous Hg (TGM) and particulate bound Hg (PBM) in a coastal city, South Korea, subjected to atmospheric Hg sources of a local steel manufacturing industry, coastal evasion from the East Sea, and long-distance transport from East Asian countries. Based on the simulated airmasses and the isotopic comparison with TGM characterized from other urban, remote, and coastal sites, TGM evaded from the coastal surface of the East Sea (warm seasons) and from the land surface in high latitude regions (cold seasons) act as important sources relative to local anthropogenic emissions at our study location. Conversely, a significant relationship between Δ199Hg and concentrations of PBM (r2 = 0.39, p < 0.05) and a seasonally uniform Δ199Hg/Δ201Hg slope (1.15), except for summer (0.26), suggest that PBM is generally sourced from local anthropogenic emissions and subjected to Hg2+ photo-reduction on particles. The striking isotopic similarity between our PBM (δ202Hg; -0.86 to 0.49 ‰, Δ199Hg; -0.15 to 1.10 ‰) and those previously characterized along the coastal and offshore regions of the Northwest Pacific (δ202Hg; -0.78 to 1.1 ‰, Δ199Hg; -0.22 to 0.47 ‰) infer that anthropogenically emitted PBM from East Asia and those processed in the coastal atmosphere serves as a regional isotopic end-member. The implementation of air pollution control devices can reduce local PBM, while regional and/or multilateral efforts are required to manage TGM evasion and transport. We also anticipate that the regional isotopic end-member can be used to quantify the relative influence of local anthropogenic Hg emissions and complex processes affecting PBM in East Asia and other coastal regions.

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.

Mercury transformation processes in nature: Critical knowledge gaps and perspectives for moving forward.

The transformation of mercury (Hg) in the environment plays a vital role in the cycling of Hg and its risk to the ecosystem and human health. Of particular importance are Hg oxidation/reduction and methylation/demethylation processes driven or mediated by the dynamics of light, microorganisms, and organic carbon, among others. Advances in understanding those Hg transformation processes determine our capacity of projecting and mitigating Hg risk. Here, we provide a critical analysis of major knowledge gaps in our understanding of Hg transformation in nature, with perspectives on approaches moving forward. Our analysis focuses on Hg transformation processes in the environment, as well as emerging methodology in exploring these processes. Future avenues for improving the understanding of Hg transformation processes to protect ecosystem and human health are also explored.

The interplay between atmospheric deposition and soil dynamics of mercury in Swiss and Chinese boreal forests: A comparison study.

Taking advantage of the different histories of Hg deposition in Davos Seehornwald in E-Switzerland and Changbai Mountain in NE-China, the influence of atmospheric deposition on Hg soil dynamics in forest soil profiles was investigated. Today, Hg fluxes in bulk precipitation were similar, and soil profiles were generally sinks for atmospherically deposited Hg at both sites. Noticeably, a net release of 2.07 µg Hg m-2 yr-1 from the Bs horizon (Podzol) in Seehornwald was highlighted, where Hg concentration (up to 73.9 µg kg-1) and soil storage (100 mg m-3) peaked. Sequential extraction revealed that organic matter and crystalline Fe and Al hydr (oxide)-associated Hg decreased in the E horizon but increased in the Bs horizon as compared to the Ah horizon, demonstrating the coupling of Hg dynamics with the podzolisation process and accumulation of legacy Hg deposited last century in the Bs horizon. The mor humus in Seehornwald allowed Hg enrichment in the forest floor (182-269 µg kg-1). In Changbai Mountain, the Hg concentrations in the Cambisol surface layer with mull humus were markedly lower (<148 µg kg-1), but with much higher Hg soil storage (54-120 mg m-3) than in the Seehornwald forest floor (18-27 mg m-3). Thus, the vertical distribution pattern of Hg was influenced by humus form and soil type. The concentrations of Hg in soil porewater in Seehornwald (3.4-101 ng L-1) and in runoff of Changbai Mountain (1.26-5.62 ng L-1) were all low. Moreover, the pools of readily extractable Hg in the soils at both sites were all <2% of total Hg. Therefore, the potential of Hg release from the forest soil profile to the adjacent aquatic environment is currently low at both sites.

Mercury pollution in China: implications on the implementation of the Minamata Convention.

Mercury (Hg) is a toxic metal released into the environment through human activities and natural processes. Human activities have profoundly increased the amount of Hg in the atmosphere and altered its global cycling since the Industrial Revolution. Gaseous elemental Hg is the predominant form of Hg in the atmosphere, which can undergo long-range transport and atmospheric deposition into the aquatic systems. Hg deposition elevates the methylmercury (MeHg) level in fish through bioaccumulation and biomagnification, which poses a serious human health risk. Acute poisoning of MeHg can result in Minamata disease, while low-level long-term exposure in pregnant women can reduce the intelligence quotient of infants. After five sessions of intergovernmental negotiation, the Minamata Convention on mercury entered into force in August 2017 to protect human health and the environment from Hg pollution. Currently China contributes the largest quantity of Hg production, consumption, and emission globally. However, the status of Hg pollution in the environment in China and its associated health risk remains relatively unknown, which hinders the development of implementation plans of the Minamata Convention. In this paper, we provide a comprehensive review on the atmospheric release of Hg, distribution of air Hg concentration, human exposure to MeHg and health impacts caused by Hg pollution in China. Ongoing improvement of air pollution control measures is expected to further decrease anthropogenic Hg emissions in China. Air Hg concentrations in China are higher than the background values in the Northern Hemisphere, with spatial distribution largely influenced by anthropogenic emissions. Long-term observations of GEM in China show a decline in recent years. The net Hg transport outflow from China in 2013 is estimated to be 511 t year-1, and ∼60% of such outflow is caused by natural surface Hg emissions. Hg concentrations in fish and rice in China are relatively low and therefore the associated risks of human Hg exposure are low. Future research needs and recommendations for the implementation of the Minamata Convention are also discussed in this paper.

Sources and Transformation Mechanisms of Atmospheric Particulate Bound Mercury Revealed by Mercury Stable Isotopes.

This study examined the isotopic composition of particulate bound mercury (PBM) in 10 Chinese megacities and explored the associated sources and transformation mechanisms. PBM in these cities was characterized by negative δ202Hg (mean: -2.00 to -0.78‰), slightly negative to highly positive Δ199Hg (mean: -0.04 to 0.47‰), and slightly positive Δ200Hg (mean: 0.02 to 0.06‰) values. The positive PBM Δ199Hg signatures were likely caused by physiochemical reactions in aerosols. The Δ199Hg/Δ201Hg ratio varied from 0.94 to 1.39 in the cities and increased with the increase in the corresponding mean Δ199HgPBM value. We speculate that, in addition to the photoreduction of oxidized Hg, other transformation mechanisms in aerosols (e.g., isotope exchange, complexation, and oxidation, which express nuclear volume effects) also shape the Δ199HgPBM signatures in the present study. These processes are likely enhanced in the presence of strong gas-particle partitioning of gaseous oxidized Hg (GOM) and elevated levels of redox active metals (e.g., Fe), halides, and elemental carbon. Based on Δ200HgPBM data presented in this and previous studies, we estimate that large proportions (∼47 ± 22%) of PBM were sourced from the oxidation of gaseous elemental Hg followed by the partitioning of GOM onto aerosols globally, indicating the transformation of Hg(0) to PBM as an important sink of atmospheric Hg(0).

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.

Mass-Independent Fractionation of Even and Odd Mercury Isotopes during Atmospheric Mercury Redox Reactions.

Mass-independent fractionation (MIF) of stable even mass number mercury (Hg) isotopes is observed in rainfall and gaseous elemental Hg0 globally and is used to quantify atmospheric Hg deposition pathways. The chemical reaction and underlying even-Hg MIF mechanism are unknown however and speculated to be caused by Hg photo-oxidation on aerosols at the tropopause. Here, we investigate the Hg isotope composition of free tropospheric Hg0 and oxidized HgII forms at the high-altitude Pic du Midi Observatory. We find that gaseous oxidized Hg has positive Δ199Hg, Δ201Hg, and Δ200Hg and negative Δ204Hg signatures, similar to rainfall Hg, and we document rainfall Hg Δ196Hg to be near zero. Cloud water and rainfall Hg show an enhanced odd-Hg MIF of 0.3‰ compared to gaseous oxidized HgII, potentially indicating the occurrence of in-cloud aqueous HgII photoreduction. Diurnal MIF observations of free tropospheric Hg0 show how net Hg0 oxidation in high-altitude air masses leads to opposite even- and odd-MIF in Hg0 and oxidized HgII. We speculate that even-Hg MIF takes place by a molecular magnetic isotope effect during HgII photoreduction on aerosols that involves magnetic halogen nuclei. A Δ200Hg mass balance suggests that global Hg deposition pathways in models are likely biased toward HgII deposition. We propose that Hg cycling models could accommodate the Hg-isotope constraints on emission and deposition fluxes.

Source identification of atmospheric particle-bound mercury in the Himalayan foothills through non-isotopic and isotope analyses.

This study reports on the sources of atmospheric particle-bound mercury (HgP) in less studied regions of Nepal based on the analysis of stable mercury (Hg) isotopes in aerosol samples from two neighboring areas with high and low anthropogenic emissions (Kathmandu and Dhulikhel, respectively) during 2018. Although the Indian monsoon and westerlies are generally regarded as the primary carriers of pollutants to this region via the heavily industrialized Indo-Gangetic Plain, the concentrations of total suspended particles (TSP) and HgP in Kathmandu were higher than those in Dhulikhel, thus suggesting a substantial contribution from local sources. Both isotopic (δ200Hg and Δ199Hg) and non-isotopic evidence indicated that dust, waste burning, and industrial byproducts (without Hg amalgamation) were the major sources of Hg in Kathmandu during the study period. Mercury may have been transported via air masses from Kathmandu to Dhulikhel, as indicated by the similar organic carbon/elemental carbon ratios and seasonal trends of TSP and HgP in these two locations. Local anthropogenic sources were found to contribute significantly to atmospheric Hg pollution through dust resuspension. Therefore, dust resuspension should be considered when evaluating the long-range transport of air pollutants such as Hg, particularly in anthropogenically stressed areas.

Use of mercury isotopes to quantify sources of human inorganic mercury exposure and metabolic processes in the human body.

The pathways of human mercury (Hg) exposure are complex and accurate understanding of relative contributions from different pathways are crucial for risk assessment and risk control. In this study, we determined total Hg concentration and Hg isotopic composition of human urine, dietary components, and inhaled air in the Wanshan Hg mining area (MA), Guiyang urban area (UA), and Changshun background area (BA) to understand Hg exposure sources and metabolic processes in human body. At the three studied sites, total gaseous mercury (TGM) showed negative δ202Hg (-3.11‰ to + 1.12‰) and near-zero Δ199Hg (-0.16‰ to + 0.13‰), which were isotopically distinguishable from Hg isotope values of urine (δ202Hg: -4.02‰ to - 0.84‰; Δ199Hg: -0.14‰ to 0.64‰). We observed an offset of -1.01‰ to -1.6‰ in δ202Hg between TGM and urine samples, and an offset of -1.01‰ to 0.80‰ in δ202Hg between rice and urine samples, suggesting that lighter isotopes are more easily accumulated in the kidneys and excreted by urine. We proposed that the high positive Δ199Hg in urine samples of UA was derived from fish consumption. The results of a binary mixing model based on Δ199Hg were compared with those from a classic dietary model. The results from the MIF binary model showed that fish consumption accounted for 22% of urine Hg in the families at UA, whereas fish consumption contributed limited Hg to MA and BA. This study highlighted that Hg isotopes can be a useful tracer in understanding the sources and fates of Hg in human bodies.

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

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

Underestimated Sink of Atmospheric Mercury in a Deglaciated Forest Chronosequence.

Mercury (Hg) deposition through litterfall has been regarded as the main input of gaseous elemental mercury (Hg0) into forest ecosystems. We hypothesize that earlier studies largely underestimated this sink because the contribution of Hg0 uptake by moss and the downward transport to wood and throughfall is overlooked. To test the hypothesis, we investigated the Hg fluxes contributed via litterfall and throughfall, Hg pool sizes in moss covers and woody biomass as well as their isotopic signatures in a glacier-to-forest succession ecosystem of the Southeast Tibetan Plateau. Results show that Hg0 depositional uptake and pool sizes stored in moss and woody biomass increase rapidly with the time after glacier retreat. Using the flux data as input to a Hg isotopic mixing model, Hg deposition through litterfall accounts for 27-85% of the total accumulation rate of Hg0 in organic soils of glacial retreat over 20-90 years, revealing the presence of additional sources of Hg0 input. Atmospheric Hg0 accounts for 76 ± 24% in ground moss, 86 ± 15% in tree moss, 62-92% in above ground woody biomass (branch-bark-stem), and 44-83% in roots. The downward decreasing gradient of atmospheric Hg0 fractions from the above ground woody biomass to roots suggests a foliage-to-root Hg transport in vegetation after uptake. Additionally, 34-82% of atmospheric Hg0 in throughfall further amplifies the accumulation of Hg0 from atmospheric sources. We conclude that woody biomass, moss, and throughfall represent important Hg0 sinks in forest ecosystems. These previously unaccounted for sink terms significantly increase the previously estimated atmospheric Hg0 sink via litterfall.

Significant Seasonal Variations in Isotopic Composition of Atmospheric Total Gaseous Mercury at Forest Sites in China Caused by Vegetation and Mercury Sources.

In this study, isotopic compositions of atmospheric total gaseous mercury (TGM) were measured in the Mt. Changbai (MCB) temperate deciduous forest and the Mt. Ailao (MAL) subtropical evergreen forest over a 1-year period. Higher δ202HgTGM values were observed under the forest canopy than above the forest canopy in the MCB forest. The vertical gradients in δ202HgTGM and Δ199HgTGM are positively correlated with the satellite-based normalized difference vegetation index (NDVI, representing the vegetation photosynthetic activity), suggesting that a strong vegetation activity (high NDVI) induces both mass-dependent and mass-independent fractionation of TGM isotopes. The observed δ202HgTGM and Δ199HgTGM showed seasonal variations. Mean δ202HgTGM and Δ199HgTGM in summer were 0.35-0.99‰ and 0.06-0.09‰ higher than those in other seasons in the MCB forest. In contrast, the highest seasonal δ202HgTGM in the MAL forest was observed in winter at 0.07-0.40‰ higher than the values found in other seasons. The variability of δ202HgTGM and Δ199HgTGM in MCB was attributed to vegetation activities, whereas the seasonal δ202HgTGM in the MAL forest was driven by the exposure of air masses to anthropogenic emissions. Using the data in this study and in the literature, we concluded that vegetation activity and anthropogenic Hg release are the main drivers for the spatial variations in TGM isotopic compositions in the northern hemisphere.

Correction to: Measurements and Distribution of Atmospheric Particulate­Bound Mercury: A Review.

The original version of this article unfortunately contained a mistake in units.

Measurements and Distribution of Atmospheric Particulate-Bound Mercury: A Review.

Atmospheric particulate-bound mercury (PBM) plays an important role in the geochemical cycling of mercury (Hg). This study reviewed research progress of the PBM, including the possible emission and deposition pathways, measurement methods and the global distribution. The primary PBM sources are anthropogenic sources, but natural sources could be also a considerable contributor, for instance, chemical transport and dust in the arid and desert area. Different filter methods, such as quartz fibre filters, have been applied to the PBM measurement, and PBM can also be real-time monitored automatically. Generally, the average PBM concentrations were higher in the Northern Hemisphere than in the Southern Hemisphere. However, the PBM level of Antarctica is quite high. PBM concentrations were higher in the urban areas than in the remote areas, and there was a high PBM level in the developing countries. Moreover, high PBM concentrations were observed in the range 20°-60° of northern latitude.