Isotopic Fractionation Characteristics of Speciated Mercury from Local Biomass Combustion in the Tibetan Plateau.

As the Third Pole of the world, the Tibetan Plateau (TP) is sensitive to anthropogenic influences. Biomass combustion is one of the most important anthropogenic sources of mercury (Hg) emissions in the TP. However, due to the lack of knowledge about Hg emission characteristics and activity levels in the plateau, atmospheric Hg emissions from biomass combustion in the TP are under large uncertainties. Here, based on pilot-scale experiments, we found that particle-bound mercury (PBM; mean of 83.1-87.7 ng/m3) occupied 17.93-49.31% of the total emitted Hg and the PBM δ202Hg values (average -1.65‰ to -0.77‰) were significantly higher than those of the corresponding feeding biomass. The Δ200Hg values of total gaseous mercury and PBM were more negative (-0.08‰ to -0.05‰) than other anthropogenic emissions, providing unique isotopic fingerprints for this sector. Together with the investigated local activity levels, Hg emissions from biomass combustion reached 402 ± 74 kg/a, which were dozens of times higher than previous estimates. The emissions were characterized by conspicuous spatial heterogeneity, concentrated in the northern and central TP. Specialized Hg emissions and the Hg isotope fingerprint of local biomass combustion can aid in evaluating the influence of this sector on the fragile ecosystems of the TP.

Isotopic Constraints on Sources and Transformations of Nitrate in the Mount Everest Proglacial Water.

Glacier melting exports a large amount of nitrate to downstream aquatic ecosystems. Glacial lakes and glacier-fed rivers in proglacial environments serve as primary recipients and distributors of glacier-derived nitrate (NO3-), yet little is known regarding the sources and cycling of nitrate in these water bodies. To address this knowledge gap, we conducted a comprehensive analysis of nitrate isotopes (δ15NNO3, δ18ONO3, and Δ17ONO3) in waters from the glacial lake and river of the Rongbuk Glacier-fed Basin (RGB) in the mountain Everest region. The concentrations of NO3- were low (0.43 ± 0.10 mg/L), similar to or even lower than those observed in glacial lakes and glacier-fed rivers in other high mountain regions, suggesting minimal anthropogenic influence. The NO3- concentration decreases upon entering the glacial lake due to sedimentation, and it increases gradually from upstream to downstream in the river as a soil source is introduced. The analysis of Δ17ONO3 revealed a substantial contribution of unprocessed atmospheric nitrate, ranging from 34.29 to 56.43%. Denitrification and nitrification processes were found to be insignificant in the proglacial water of RGB. Our study highlights the critical role of glacial lakes in capturing and redistributing glacier-derived NO3- and emphasizes the need for further investigations on NO3- transformation in the fast-changing proglacial environment over the Tibetan Plateau and other high mountain regions.

Dramatic Carbon Loss in a Permafrost Thaw Slump in the Tibetan Plateau is Dominated by the Loss of Microbial Necromass Carbon.

Thaw slumps can lead to considerable carbon loss in permafrost regions, while the loss of components from two major origins, i.e., microbial and plant-derived carbon, during this process remains poorly understood. Here, we provide direct evidence that microbial necromass carbon is a major component of lost carbon in a retrogressive permafrost thaw slump by analyzing soil organic carbon (SOC), biomarkers (amino sugars and lignin phenols), and soil environmental variables in a typical permafrost thaw slump in the Tibetan Plateau. The retrogressive thaw slump led to a ∼61% decrease in SOC and a ∼25% SOC stock loss. As evident in the levels of amino sugars (average of 55.92 ± 18.79 mg g-1 of organic carbon, OC) and lignin phenols (average of 15.00 ± 8.05 mg g-1 OC), microbial-derived carbon (microbial necromass carbon) was the major component of the SOC loss, accounting for ∼54% of the SOC loss in the permafrost thaw slump. The variation of amino sugars was mainly related to the changes in soil moisture, pH, and plant input, while changes in lignin phenols were mainly related to the changes in soil moisture and soil bulk density.

Local temperature increases reduce soil microbial residues and carbon stocks.

Warming is known to reduce soil carbon (C) stocks by promoting microbial respiration, which is associated with the decomposition of microbial residue carbon (MRC). However, the relative contribution of MRC to soil organic carbon (SOC) across temperature gradients is poorly understood. Here, we investigated the contribution of MRC to SOC along two independent elevation gradients of our model system (i.e., the Tibetan Plateau and Shennongjia Mountain in China). Our results showed that local temperature increases were negatively correlated with MRC and SOC. Further analyses revealed that rising temperature reduced SOC via decreasing MRC, which helps to explain future reductions in SOC under climate warming. Our findings demonstrate that climate warming has the potential to reduce C sequestration by increasing the decomposition of MRC, exacerbating the positive feedback between rising temperature and CO2 efflux. Our study also considered the influence of multiple environmental factors such as soil pH and moisture, which were more important in controlling SOC than microbial traits such as microbial life-style strategies and metabolic efficiency. Together, our work suggests an important mechanism underlying long-term soil C sequestration, which has important implications for the microbial-mediated C process in the face of global climate change.

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.

Observation-Based Mercury Export from Rivers to Coastal Oceans in East Asia.

Globally, the consumption of coastal fish is the predominant source of human exposure to methylmercury, a potent neurotoxicant that poses health risks to humans. However, the relative importance of riverine inputs and atmospheric deposition of mercury into coastal oceans remains uncertain owing to a lack of riverine mercury observations. Here, we present comprehensive seasonal observations of riverine mercury and methylmercury loads, including dissolved and particulate phases, to East Asia's coastal oceans, which supply nearly half of the world's seafood products. We found that East Asia's rivers annually exported 95 ± 29 megagrams of mercury to adjacent seas, 3-fold greater than the corresponding atmospheric deposition. Three rivers alone accounted for 71% of East Asia's riverine mercury exports, namely: Yangtze, Yellow, and Pearl rivers. We further conducted a metadata analysis to discuss the mercury burden on seawater and found that riverine export, combined with atmospheric deposition and terrestrial nutrients, quantitatively elevated the levels of total, methylated, and dissolved gaseous mercury in seawater by an order of magnitude. Our observations support that massive amounts of riverine mercury are exported to coastal oceans on a continental scale, intensifying their spread from coastal seawater to the atmosphere, marine sediments, and open oceans. We suggest that the impact of mercury transport along the land-ocean aquatic continuum should be considered in human exposure risk assessments.

Seasonal Variation of Mercury and Its Isotopes in Atmospheric Particles at the Coastal Zhongshan Station, Eastern Antarctica.

Mercury (Hg) is a globally spread trace metal due to its long atmospheric residence time. Yet, our understanding of atmospheric processes (e.g., redox reactions and deposition) driving Hg cycling is still limited, especially in polar regions. The Antarctic continent, by virtue of its remoteness, is the perfect location to investigate Hg atmospheric processes in the absence of significant local anthropogenic impact. Here, we present the first 2 year record (2016-2017) of total suspended particulate mercury (PHg) concentrations along with a year-round determination of an Hg stable isotopic composition in particles collected at Zhongshan Station (ZSS), eastern Antarctic coast. The mean PHg concentration is 21.8 ± 32.1 pg/m3, ranging from 0.9 to 195.6 pg/m3, and peaks in spring and summer. The negative mass-independent fractionation of odd Hg isotopes (odd-MIF, average -0.38 ± 0.12‰ for Δ199Hg) and the slope of Δ199Hg/Δ201Hg with 0.91 ± 0.12 suggest that the springtime isotope variation of PHg is likely caused by in situ photo-oxidation and reduction reactions. On the other hand, the increase of PHg concentrations and the observed odd-MIF values in summer are attributed to the transport by katabatic winds of divalent species derived from the oxidation of elemental Hg in the inland Antarctic Plateau.

Vegetation Mediated Mercury Flux and Atmospheric Mercury in the Alpine Permafrost Region of the Central Tibetan Plateau.

Measurements of land-air mercury (Hg) exchanges over vegetated surfaces are needed to further constrain Hg fluxes over vegetated terrestrial surfaces. Yet, knowledge of land-air Hg dynamics in alpine grasslands remains poor. Hg fluxes over an alpine meadow were measured throughout a full vegetation period in the central Tibetan Plateau (TP). This TP grassland served as a small source of atmospheric total gaseous Hg (TGM) during vegetation period (0.92 µg m-2). Hg fluxes decreased logarithmically during plant growing season, resulting from the influence of vegetation by light shading and plant Hg uptake, although the latter might be minor due to low biomass at this site. Temporal patterns of TGM indicated the importance of land-air dynamics in regulating TGM levels. During the plant emergence, diel pattern of TGM covaried with Hg emission fluxes resulting in lower concentrations at night and higher concentrations in afternoon. During all other vegetation stages, TGM showed minima before dawn and "morning peak" shortly after sunrise, in conjunction with corresponding Hg fluxes showing sink before dawn and source after sunrise. Moreover, TGM concentrations showed a decreasing trend with plant growing, further indicating the role of vegetation in driving seasonal TGM variations by regulating land-air Hg dynamics.

Water-Soluble Brown Carbon in Atmospheric Aerosols from Godavari (Nepal), a Regional Representative of South Asia.

Brown carbon (BrC) has recently emerged as an important light-absorbing aerosol. This study provides interannual and seasonal variations in light absorption properties, chemical composition, and sources of water-soluble BrC (WS-BrC) based on PM10 samples collected in Godavari, Nepal, from April 2012 to May 2014. The mass absorption efficiency of WS-BrC at 365 nm (MAE365) shows a clear seasonal variability, with the highest MAE365 of 1.05 ± 0.21 m2 g-1 in premonsoon season and the lowest in monsoon season (0.59 ± 0.16 m2 g-1). The higher MAE365 values in nonmonsoon seasons are associated with fresh biomass burning emissions. This is further substantiated by a strong correlation ( r = 0.79, P < 0.01) between Abs365 (light absorption coefficient at 365 nm) and levoglucosan. We found, using fluorescence techniques, that humic-like and protein-like substances are the main chromophores in WS-BrC and responsible for 80.2 ± 4.1% and 19.8 ± 4.1% of the total fluorescence intensity, respectively. BrC contributes to 8.78 ± 3.74% of total light absorption over the 300-700 nm wavelength range. Considering the dominant contribution of biomass burning to BrC over Godavari, this study suggests that reduction in biomass burning emission may be a practical method for climate change mitigation in South Asia.

Emission Measurements from Traditional Biomass Cookstoves in South Asia and Tibet.

Traditional biomass stoves are a major global contributor to emissions that impact climate change and health. This paper reports emission factors of particulate matter (PM2.5), carbon monoxide (CO), organic carbon (OC), black carbon (EC), optical absorption, and scattering from 46 South Asian, 48 Tibetan, and 4 Ugandan stoves. These measurements plus a literature review provide insight into the robustness of emission factors used in emission inventories. Tibetan dung stoves produced high average PM2.5 emission factors (23 and 43 gkg-1 for chimney and open stoves) with low average EC (0.3 and 0.7 gkg-1, respectively). Comparatively, PM2.5 from South Asian stoves (7 gkg-1) was in the range of previous measurements and near values used in inventories. EC emission factors varied between stoves and fuels ( p < 0.001), without corresponding differences in absorption; stoves that produced little EC, produced enough brown carbon to have about the same absorption as stoves with high EC emissions. In Tibetan dung stoves, for example, OC contributed over 20% of the absorption. Overall, EC emission factors were not correlated with PM2.5 and were constrained to low values, relative to PM2.5, over a wide range of combustion conditions. The average measured EC emission factor (1 gkg-1), was near current inventory estimates.

Understanding Mercury Cycling in Tibetan Glacierized Mountain Environment: Recent Progress and Remaining Gaps.

Glacierized mountain environments can preserve and release mercury (Hg) and play an important role in regional Hg cycling. In the Tibetan Plateau (TP), most glaciers have been retreating at unprecedented rate in recent decades, acting as one of the most active factors in regional hydrological cycling. In this mini-review, we summarized recent studies on Hg distribution, transport, and accumulation in Tibetan glacierized environments. We highlight that melting glacier may represent a stimulator that exports Hg to glacier-fed ecosystems. We identified major knowledge gaps and proposed future research needs with several emphases, including quantifying Hg in glacier ablation zone, depicting Hg transport and transformation in glacial rivers during spring melt season, and better constraining glacier-export Hg and its environmental risks to the downstream. Besides, Hg isotopic technical, passive sampling and hydrological transport model should be utilized to improve the understanding of Hg cycling in high mountain regions in the TP.

Traditional Tibetan Medicine Induced High Methylmercury Exposure Level and Environmental Mercury Burden in Tibet, China.

Highly elevated concentrations of total mercury (THg) and methylmercury (MeHg) were found in the municipal sewage in Tibet. Material flow analysis supports the hypothesis that these elevated concentrations are related to regular ingestion of Hg-containing Traditional Tibetan Medicine (TTM). In Tibet in 2015, a total of 3600 kg of THg was released from human body into the terrestrial environment as a result of TTM ingestion, amounting to 45% of the total THg release into the terrestrial environment in Tibet, hence substantially enhancing the environmental Hg burden. Regular ingestion of TTM leads to chronic exposure of Tibetans to inorganic Hg (IHg) and MeHg, which is 34 to 3000-fold and 0-12-fold higher than from any other known dietary sources, respectively. Application of a human physiology model demonstrated that ingestion of TTM can induce high blood IHg and MeHg levels in the human body. Moreover, 180 days would be required for the MeHg to be cleared out of the human body and return to the initial concentration i.e. prior to the ingestion of 1 TTM pill. Our analysis suggests that high Hg level contained in TTM could be harmful to human health and elevate the environmental Hg burden in Tibet.

Increases of Total Mercury and Methylmercury Releases from Municipal Sewage into Environment in China and Implications.

As a globally transported pollutant, mercury (Hg) released from human activity and methylmercury (MeHg) in the food web are global concerns due to their increasing presence in the environment. In this study, we found that Hg released from municipal sewage into the environment in China is a substantial anthropogenic source based on mass sampling throughout China. In total, 160 Mg (140-190 Mg, from the 20th percentile to the 80th percentile) of Hg (THg) and 280 kg (240-330 kg) of MeHg were released from municipal sewage in China in 2015. The quantities of released THg and MeHg were the most concentrated in the coastal regions, especially in the East, North and South China regions. However, the per capita release of THg and MeHg was the highest in the Tibetan region, which is recognized as the cleanest region in China. THg released into aquatic environments was mitigated from 2001 to 2015 in China, but the amounts released into other sinks increased. This study provides the first picture of the release of Hg from municipal sewage into various sinks in China, and policy makers should pay more attention to the diversity and complexity of the sources and transport of Hg, which can lead to Hg accumulation in the food web and can threaten human health.

Insights into mercury in glacier snow and its incorporation into meltwater runoff based on observations in the southern Tibetan Plateau.

The Tibetan Plateau (TP) is recognized as "Water Tower of Asia". Yet our understanding of mechanisms influencing incorporation of mercury (Hg) into freshwater in mountain glaciers on the TP remains quite limited. Extensive sampling of environmental matrices (e.g., snow/ice) were conducted on the East Rongbuk glacier on Mt. Everest and Zhadang glacier on Mt. Nyainqentanglha for Hg speciation analysis. Speciated Hg behaved quite different during snowmelt: a preferential early release of DHg (dissolved Hg) was observed at the onset of snowmelt, whereas PHg (particulate-bound Hg) and THg (total Hg) become relatively enriched in snow and released later. Small fraction of Hg in snow was lost during a snowmelt day (18.9%-34.7%) with a large proportion (58.1%-87.3%) contributed by PHg decrease, indicating that the deposited Hg is most likely retained in glacier snow/ice. Furthermore, THg were positively correlated with PHg and crustal major ions (e.g., Ca2+, Mg2+) during snowmelt, indicating that Hg is mainly migrated with particulates. The main pathway of Hg loss during snowmelt was most probably associated with release of PHg with meltwater, which was greatly influenced by ablation intensity of snow/ice. This should be paid particular concern as Hg preserved in mountain glaciers will mostly enter aquatic ecosystem as climate warms, impacting on downstream ecosystems adversely. Obvious decrease of THg during the downstream transport from glacier was observed with a large proportion contributed by PHg decrease. The main removal mechanism of Hg was associated with sedimentation of PHg during the transport process.

Mercury Concentrations in the Fish Community from Indrawati River, Nepal.

This study quantified concentrations of mercury (Hg) and its trophic transfer along the fish community in the Indrawati River, Nepal. Stable isotope ratios of nitrogen (δ15N) and carbon (δ13C), complemented by stomach contents data were used to assess the food web structure and trophic transfer of Hg in 54 fishes; 43 Shizothorax richardsonii and 11 Barilius spp. [B. bendelisis (1), B. vagra (3) and B. barila (7)]. Sixty-one muscle samples (including six replicates) were used for the analysis of total mercury (THg) and stable isotopes. Mean THg concentrations in B. spp. and the more common species S. richardsonii was observed to be 218.23 (ng/g, ww) and 90.82 (ng/g, ww), respectively. THg versus total length in both S. richardsonii and B. spp. showed a decreasing tendency with an increase in age. Regression of logTHg versus δ15N among the fish species showed a significant positive correlation only in S. richardsonii indicating biomagnification along the trophic level in this species.

Recent Decline of Atmospheric Mercury Recorded by Androsace tapete on the Tibetan Plateau.

We combined the mercury passive sampling method and plant biomonitoring together to understand the long-term changes of atmospheric mercury concentrations on the Tibetan Plateau. Through the analysis of leaves of Androsace tapete that represent growing periods spanning the past decade, we explored the historical records of atmospheric mercury from 2006 to 2015. Mercury concentration was stable in the leaves of Androsace tapete during the period between 2006 and 2009, while a significant decrease occurred after the year of 2010. The decreasing trend is consistent with the monitoring data of the ground-based stations in other regions globally. Despite the potential uncertainties using a passive sampling method and biomonitoring technique, we suggest that Androsace tapete is a potential biomarker that could provide reliable and effective historical records of atmospheric mercury concentrations and offer new perspectives in monitoring mercury and perhaps other atmospheric pollutants in regions where long-term active monitoring was missing.

Atmospheric Mercury Depositional Chronology Reconstructed from Lake Sediments and Ice Core in the Himalayas and Tibetan Plateau.

Alpine lake sediments and glacier ice cores retrieved from high mountain regions can provide long-term records of atmospheric deposition of anthropogenic contaminants such as mercury (Hg). In this study, eight lake sediment cores and one glacier ice core were collected from high elevations across the Himalaya-Tibet region to investigate the chronology of atmospheric Hg deposition. Consistent with modeling results, the sediment core records showed higher Hg accumulation rates in the southern slopes of the Himalayas than those in the northern slopes in the recent decades (post-World War II). Despite much lower Hg accumulation rates obtained from the glacier ice core, the temporal trend in the Hg accumulation rates matched very well with that observed from the sediment cores. The combination of the lake sediments and glacier ice core allowed us to reconstruct the longest, high-resolution atmospheric Hg deposition chronology in High Asia. The chronology showed that the Hg deposition rate was low between the 1500s and early 1800, rising at the onset of the Industrial Revolution, followed by a dramatic increase after World War II. The increasing trend continues to the present-day in most of the records, reflecting the continuous increase in anthropogenic Hg emissions from South Asia.

Distribution and transportation of mercury from glacier to lake in the Qiangyong Glacier Basin, southern Tibetan Plateau, China.

The Tibetan Plateau is home to the largest aggregate of glaciers outside the Polar Regions and is a source of fresh water to 1.4 billion people. Yet little is known about the transportation and cycling of Hg in high-elevation glacier basins on Tibetan Plateau. In this study, surface snow, glacier melting stream water and lake water samples were collected from the Qiangyong Glacier Basin. The spatiotemporal distribution and transportation of Hg from glacier to lake were investigated. Significant diurnal variations of dissolved Hg (DHg) concentrations were observed in the river water, with low concentrations in the morning (8:00am-14:00pm) and high concentrations in the afternoon (16:00pm-20:00pm). The DHg concentrations were exponentially correlated with runoff, which indicated that runoff was the dominant factor affecting DHg concentrations in the river water. Moreover, significant decreases of Hg were observed during transportation from glacier to lake. DHg adsorption onto particulates followed by the sedimentation of particulate-bound Hg (PHg) could be possible as an important Hg removal mechanism during the transportation process. Significant decreases in Hg concentrations were observed downstream of Xiao Qiangyong Lake, which indicated that the high-elevation lake system could significantly affect the distribution and transportation of Hg in the Qiangyong Glacier Basin.

Mercury in wild fish from high-altitude aquatic ecosystems in the Tibetan Plateau.

Our understanding of the biogeochemistry of mercury (Hg) in high-altitude aquatic environments remains limited. The Tibetan Plateau (TP) is one of the Earth's most significant continental-scale high lands, yet much remains unknown about the Hg bioaccumulation and biomagnification in these pristine ecosystems. In this study, 166 wild fish samples of 13 species were collected from 13 rivers and lakes across the southern TP. Total Hg (THg) and methyl-Hg (MeHg) concentrations in the axial muscle of fish ranged from 25.1 to 1218 ng g(-1) of wet weight (median ± average deviation of 100.5 ± 149.2 ng g(-1)) and from 24.9 to 1196 ng g(-1) of wet weight (median ± average deviation of 90.7 ± 137.0 ng g(-1)), respectively. Hg concentrations varied greatly within and between species. The fish Hg concentrations were then linked to the limited available environmental Hg data and special geochemical characteristics in the region, such as Hg loading, pH, low temperature, and high ultraviolet (UV). The long lifespan and slow growth of the fish under the low-productivity environments may be the major biological factors that help to build up the fish Hg levels comparable to those observed in wild fish growing in human-impacted areas. δ(13)C signals suggested that pelagic fish had higher Hg concentrations, but no relationship was found between the Hg concentrations and the trophic levels. Zooplankton and benthic amphipods had typically higher percentages of MeHg compared to the previously reported values, suggesting the efficient transfer of MeHg from the base of the aquatic food web. This study sheds some light on the geochemical and biological controls of Hg bioaccumulation in fish and biomagnification in the aquatic food web in arid high-altitude environments.

Westerlies-driven transboundary transport of atmospheric mercury to the north-central Tibetan Plateau.

The transboundary mercury (Hg) pollution has caused adverse effects on fragile ecosystems of the Tibetan Plateau (TP). Yet, knowledge of transport paths and source regions of atmospheric Hg on the inland TP remains poor. Continuous measurements of atmospheric total gaseous mercury (TGM) were conducted in the central TP (Tanggula station, 5100 m a.s.l., June-October). Atmospheric TGM level at Tanggula station (1.90 ± 0.30 ng m-3) was higher than the background level in the Northern Hemisphere. The identified high-potential source regions of atmospheric TGM were primarily located in the northern South Asia region. TGM concentrations were lower during the Indian summer monsoon (ISM)-dominant period (1.81 ± 0.25 ng m-3) than those of the westerly-receding period (2.18 ± 0.40 ng m-3) and westerly-intensifying period (1.91 ± 0.26 ng m-3), contrary to the seasonal pattern in southern TP. The distinct TGM minima during the ISM-dominant period indicated lesser importance of ISM-transported Hg to Tanggula station located in the northern boundary of ISM intrusion, compared to stations in proximity to South and Southeast Asia source regions. Instead, from the ISM-dominant period to the westerly-intensifying period, TGM concentrations showed an increasing trend as westerlies intensified, indicating the key role of westerlies in transboundary transport of atmospheric Hg to the inland TP.