δ202Hg Values Research Articles

Levels, sources, isotope signatures, and health risks of mercury in street dust across China

Spatial distribution and isotope signature of mercury (Hg) in street dusts across China were investigated by collecting dust samples from 14 cities and reviewing previously published data from an additional 46 cities. Potential sources of street dust and the associated health risks to humans were also assessed. The total Hg (THg) concentrations in street dust ranged from 0.020–39.1 mg kg−1 with an average of 0.433 ± 0.185 mg kg−1 in the 60 cities. Street dust samples collected from 14 cities were characterized by slightly negative δ202Hg (−0.61 ± 0.92‰) and near-zero Δ199Hg (−0.03 ± 0.08‰) values, and coal combustion and industrial activities were estimated to be the major sources of Hg in street dust. The estimated average probable daily intake (PDI) of THg from street dust exposure for adults and children (1.36E–03 and 1.27E–02 μg d−1 kg−1, respectively) were comparable to their respective exposures via rice consumption in China. Children being exposed to THg in dust is a major concern in mercury mining areas (e.g., Wangshan and Xunyang), and may also be a concern in cities with major coal-based industries and nonferrous metal smelting. Results from this study suggest that exposure to street dust is not a primary MeHg exposure pathway in China.

Mercury isotope compositions in large anthropogenically impacted Pearl River, South China.

Rivers integrate natural and anthropogenic mercury (Hg), and are important vectors of terrestrial Hg to the oceans. Here, we report the total Hg concentration and Hg isotope compositions of dissolved load in the Pearl River, the second largest river in China, in order to understand the processes and sources affecting Hg systematics in large anthropogenically-impacted river water. The dissolved Hg showed a concentration varying from 0.45 to 2.44ng/L, within the range reported for natural background lake and river waters. All river water samples showed significantly negative δ202Hg (-2.89‰ to -0.57‰), slightly positive Δ200Hg (-0.05‰ to 0.52‰), and mostly positive Δ199Hg (0.10‰ to 0.57‰), except for three extremely negative values (-2.25‰ to -0.76‰). Combined with other geochemical parameters, we suggest that the influence of in-river processes, such as sorption and reduction, on the Hg isotope compositions is very limited, and the dissolved Hg in the Pearl River mainly comes from atmospheric precipitation and surface soil weathering. Although the whole river basin is largely affected by urban, industrial and mining activities, unlike other heavy metals, their direct contributions to dissolved Hg seem limited. It is worth noting that the three samples with very negative Δ199Hg values (down to -2.25‰) are derived from special source which attribute to the input of Hg released from the local incineration of electronic wastes. This study demonstrates that isotope approach is a powerful tool for tracing sources and pathways of Hg in large complex river systems.

Study of mercury transport and transformation in mangrove forests using stable mercury isotopes

Mangrove forests are important wetland ecosystems that are a sink for mercury from tides, rivers and precipitation, and can also be sources of mercury production and export. Natural abundance mercury stable isotope ratios have been proven to be a useful tool to investigate mercury behavior in various ecosystems. In this study, mercury isotopic data were collected from seawater, sediments, air, and plant tissues in two mangrove forests in Guangxi and Fujian provinces, China, to study the transport and transformation of mercury in mangrove sediments. The mangroves were primarily subject to mercury inputs from external sources, such as anthropogenic activities, atmospheric deposition, and the surrounding seawater. An isotope mixing model based on mass independent fractionation (MIF) estimated that the mangrove wetland ecosystems accounted for <40% of the mercury in the surrounding seawater. The mercury in plant root tissues was derived mainly from sediments and enriched with light mercury isotopes. The exogenous mercury inputs from the fallen leaves were diluted by seawater, leading to a positive Δ199Hg offset between the fallen leaves and sediments. Unlike river and lake ecosystems, mangrove ecosystems are affected by tidal action, and the δ202Hg and Δ199Hg values of sediments were more negative than that of the surrounding seawater. The isotopic signature differences between these environmental samples were partially due to isotope fractionation driven by various physical and chemical processes (e.g., sorption, photoreduction, deposition, and absorption). These results contribute to a better understanding of the biogeochemical cycling of mercury in mangrove wetland ecosystems.

Mercury isotopes in frozen soils reveal transboundary atmospheric mercury deposition over the Himalayas and Tibetan Plateau

The concentration and isotopic composition of mercury (Hg) were studied in frozen soils along a southwest-northeast transect over the Himalaya-Tibet. Soil total Hg (HgT) concentrations were significantly higher in the southern slopes (72 ± 54 ng g−1, 2SD, n = 21) than those in the northern slopes (43 ± 26 ng g−1, 2SD, n = 10) of Himalaya-Tibet. No significant relationship was observed between HgT concentrations and soil organic carbon (SOC), indicating that the HgT variation was not governed by SOC. Soil from the southern slopes showed significantly negative mean δ202Hg (−0.53 ± 0.50‰, 2SD, n = 21) relative to those from the northern slopes (−0.12 ± 0.40‰, 2SD, n = 10). The δ202Hg values of the southern slopes are more similar to South Asian anthropogenic Hg emissions. A significant correlation between 1/HgT and δ202Hg was observed in all the soil samples, further suggesting a mixing of Hg from South Asian anthropogenic emissions and natural geochemical background. Large ranges of Δ199Hg (−0.45 and 0.24‰) were observed in frozen soils. Most of soil samples displayed negative Δ199Hg values, implying they mainly received Hg from gaseous Hg(0) deposition. A few samples had slightly positive odd-MIF, indicating precipitation-sourced Hg was more prevalent than gaseous Hg(0) in certain areas. The spatial distribution patterns of HgT concentrations and Hg isotopes indicated that Himalaya-Tibet, even its northern part, may have been influenced by transboundary atmospheric Hg pollution from South Asia.

Sources of mercury in deep-sea sediments of the Mediterranean Sea as revealed by mercury stable isotopes

Mercury (Hg) and its stable isotope composition were used to determine the sources of Hg in deep-sea sediments of the Mediterranean Sea. Surface and down-core sediment δ202Hg values varied widely between −2.30 and +0.78‰, showed consistently positive values for mass independent fractionation of odd Hg isotopes (with average values of Δ199Hg = +0.10 ± 0.04‰ and Δ201Hg = +0.04 ± 0.02‰) and near-zero Δ200Hg values, indicating either multiple Hg sources or a combination of different Hg isotope fractionating processes before and after sediment deposition. Both mass-dependent and mass-independent fractionation processes influence the isotopic composition of Hg in the Mediterranean Sea. Positive Δ199Hg values are likely the result of enhanced Hg2+ photoreduction in the Mediterranean water column before incorporation of Hg into sediments, while mass-dependent fractionation decreases δ202Hg values due to kinetic isotope fractionation during deposition and mobilization. An isotope mixing model based on mass-dependent and mass-independent fractionation (δ202Hg and Δ199Hg) suggests at least three primary Hg sources of atmospheric deposition in the surface sediments: urban, industrial and global precipitation-derived. Industry is the main source of Hg in Algerian and Western Basin surface sediments and at two sites in the Adriatic Sea, while the urban contribution is most prominent at the Strait of Otranto (MS3) and in Adriatic surface sediments. The contribution from precipitation ranged from 10% in Algerian to 37% in W Basin sediments. Overall, results suggest that atmospheric Hg deposition to Mediterranean surface sediments is dominated by gaseous elemental mercury (58 ± 11%) rather than wet deposition.

Mercury Cycling in the North Pacific Subtropical Gyre as Revealed by Mercury Stable Isotope Ratios

AbstractThe oceans are an important global reservoir for mercury (Hg), and marine fish consumption is the dominant human exposure pathway for its toxic methylated form. A more thorough understanding of the global biogeochemical cycle of Hg requires additional information on the mechanisms that control Hg cycling in pelagic marine waters. In this study, Hg isotope ratios and total Hg concentrations are used to explore Hg biogeochemistry in oligotrophic marine environments north of Hawaii. We present the first measurements of the vertical water column distribution of Hg concentrations and the Hg isotopic composition in precipitation, marine particles, and zooplankton near Station ALOHA (22°45′N, 158°W). Our results reveal production and demethylation of methylmercury in both the euphotic (0–175 m) and mesopelagic zones (200–1,000 m). We document a strong relationship between Hg isotopic composition and depth in particles, zooplankton, and fish in the water column and diurnal variations in Δ199Hg values in zooplankton sampled near the surface (25 m). Based on these observations and stable Hg isotope relationships in the marine food web, we suggest that the Hg found in large pelagic fish at Station ALOHA was originally deposited largely by precipitation, transformed into methyl‐Hg, and bioaccumulated in situ in the water column. Our results highlight how Hg isotopic compositions reflect abiotic and biotic production and degradation of methyl‐Hg throughout the water column and the importance of particles and zooplankton in the vertical transport of Hg.

Mercury Isotope Fractionation in the Subsurface of a Hg(II) Chloride-Contaminated Industrial Legacy Site.

To understand the transformations of mercury (Hg) species in the subsurface of a HgCl2-contaminated former industrial site in southwest Germany, Hg isotope analysis was combined with an investigation of Hg forms by a four-step sequential extraction protocol (SEP) and pyrolytic thermodesorption. Data from two soil cores revealed that the initial HgCl2 was partly reduced to metallic Hg(0) and that Hg forms of different mobility and oxidation state coexist in the subsurface. The most contaminated sample (K2-8, 802 mg kg–1 Hg) had a bulk δ202Hg value of around −0.43 ± 0.06‰ (2SD), similar to published average values for industrial Hg sources. Other sample signatures varied significantly with depth and between SEP pools. The most Hg-rich samples contained mixtures of Hg(0) and Hg(II) phases, and the water-extractable, mobile Hg pool exhibited heavy δ202Hg values of up to +0.18‰. Sequential water extracts revealed slow dissolution kinetics of mobile Hg pools, continuously releasing isotopically heavy Hg into solution. This was further corroborated by heavy δ202Hg values of groundwater samples. Our results demonstrate that the Hg isotope signature of an industrial contamination source can be significantly altered during the transformations of Hg species in the subsurface, which complicates source tracing applications but offers the possibility of using Hg isotopes as process tracers in contaminated subsurface systems.

High-precision isotopic analysis sheds new light on mercury metabolism in long-finned pilot whales (Globicephala melas)

Whales accumulate mercury (Hg), but do not seem to show immediate evidence of toxic effects. Analysis of different tissues (liver, kidney, muscle) and biofluids (blood, milk) from a pod of stranded long-finned pilot whales (Globicephala melas) showed accumulation of Hg as a function of age, with a significant decrease in the MeHg fraction. Isotopic analysis revealed remarkable differences between juvenile and adult whales. During the first period of life, Hg in the liver became isotopically lighter (δ202Hg decreased) with a strongly decreasing methylmercury (MeHg) fraction. We suggest this is due to preferential demethylation of MeHg with the lighter Hg isotopes and transport of MeHg to less sensitive organs, such as the muscles. Also changes in diet, with high MeHg intake in utero and during lactation, followed by increasing consumption of solid food contribute to this behavior. Interestingly, this trend in δ202Hg is reversed for livers of adult whales (increasing δ202Hg value), accompanied by a progressive decrease of δ202Hg in muscle at older ages. These total Hg (THg) isotopic trends suggest changes in the Hg metabolism of the long-finned pilot whales, development of (a) detoxification mechanism(s) (e.g., though the formation of HgSe particles), and Hg redistribution across the different organs.

Different circulation history of mercury in aquatic biota from King George Island of the Antarctic

To trace the circulation history of aquatic bioavailable Hg in the Antarctic, the species and isotopic compositions of Hg in sediment, Archaeogastropoda (Agas), Neogastropoda (Ngas), and fish collected from King George Island were studied in detail. Positive mass independent fractionation (MIF) was observed and positively correlated with the percentages of methylmercury (MeHg%) in Agas and Ngas, suggesting an effect of MeHg accumulation during trophic transfer on MIF signatures. However, both the ratios of Δ199Hg/δ202Hg and Δ199Hg/Δ201Hg indicated different circulation histories of Hg in Agas, Ngas, and fish. The microbial methylation in sediment was the primary source of MeHg in Agas and Ngas (Δ199Hg/δ202Hg ∼0, Δ199Hg/Δ201Hg ∼1.00). In contrast, the MeHg in fish (Δ199Hg/δ202Hg = 0.55 ± 0.06, Δ199Hg/Δ201Hg = 1.19 ± 0.17) came from the combined sources of residual MeHg which had sunk from the surface water and microbial-methylated MeHg in sediments, and the bioavailable Hg in the sediments contributed to approximately 44% of the total Hg in fish. Subsequently, the Δ199Hg values of bioavailable MeHg and IHg in sediments were quantitatively calculated, which provided key end-member information for future source apportionment in the Antarctic and other pelagic regions. It was also found that the Hg accumulated in Agas and Ngas had no history of MeHg photo-degradation, indicating that the methylated Hg in benthic zones suffered little photo-degradation and thus presented high bioavailability and environmental risk.

Tracking legacy mercury in the Hackensack River estuary using mercury stable isotopes.

Spatial redistribution of legacy mercury (Hg) contamination in the Hackensack River estuary (New Jersey, USA) was evaluated using mercury stable isotopes. Total Hg varied from 0.06 to 3.8 μg g-1 in sediment from the tidal Hackensack River and from 15 to 154 μg g-1 near historically contaminated sites in upper Berry's Creek, a tributary of the Hackensack River. δ202Hg values for total Hg from Berry's Creek and Hackensack River estuaries varied over a fairly narrow range (-0.44‰ to -0.21‰), but were highest for sediment from upper Berry's Creek. Isotope mixing plots show that residual legacy mercury from upper Berry's Creek is partially diluted by a low concentration and low δ202Hg pool of mercury associated with low organic matter content sediments similar to those in Newark Bay. Based on an isotope mixing model, we estimate that upper Berry's Creek contributes 21%-82% of the mercury in sediments in the Hackensack River estuary and its tidal tributaries, including upstream marsh habitats far from the primary source. Our results show that mercury stable isotopes can be used to track the redistribution of mercury in tidal ecosystems and highlight the potentially large areas which may be affected by legacy mercury contamination in estuaries.

Mercury speciation and mercury stable isotope composition in sediments from the Canadian Arctic Archipelago

Total mercury (THg) and monomethylmercury (MMHg) concentrations as well as mercury (Hg) isotope ratios were determined in sediment cores sampled from six locations from the Canadian Arctic Archipelago (CAA). At most sites, THg concentrations showed a decreasing trend with depth, ranging from 5 to 61 ng/g, implicating possible increased Hg deposition and/or riverine inputs in top sediment layers. MMHg values showed large oscillations within the top 10 cm of the cores. This variability decreased at the bottom of the cores with MMHg concentrations ranging from less than12 to up to 1073 pg/g. Average concentrations of THg and MMHg in the top 10 cm were linearly correlated, whereas no correlation was observed with organic matter (loss on ignition). Mercury isotope ratios showed negative values for both δ202Hg (−1.59 to −0.55‰) and Δ199Hg (−0.62 to −0.01‰). δ202Hg values became more negative with depth, while the opposite was observed for Δ199Hg. The former is consistent with predicted historical atmospheric Hg trends as a result of increased coal burning worldwide. Hg isotope ratio measurements in CAA sediments offer additional opportunities to trace Hg processes and sources in the Arctic.

Global mercury cycle during the end-Permian mass extinction and subsequent Early Triassic recovery

The end-Permian mass extinction (EPME) at ∼252 Ma was the most severe extinction in the Phanerozoic. Marine ecosystems devastated by the EPME had a highly prolonged recovery, and did not substantially recover until after the Smithian–Spathian substage boundary (SSB) of the Lower Triassic (5 to 9 Ma after the EPME). While the Siberian Traps large igneous province (STLIP) has been invoked as the driver of the mass extinction, there remains controversy as to the cause of the protracted Early Triassic recovery; although renewed STLIP volcanism has been suggested. These previous studies though have drawn conclusions based on geochemical records of sediments deposited in northern latitude settings. To investigate the relationship between STLIP and extinction/recovery processes on a global base, we examined mercury chemostratigraphy, including mercury concentrations and isotopes, from high southern latitude and equatorial sections that span the Late Permian Changhsingian to Early Triassic Spathian substage successions; the Guryul Ravine section, Kashmir in northern India, and the Chaohu section in southern China. Organic and inorganic carbon-isotope data define the EPME horizon in the Chaohu section and the SSB in the Guryul Ravine section, respectively. Hg/TOC values are dramatically elevated approaching the EPME horizon and maintain high values until the lower Isarcicella Isarcica conodont zone, the base of which is believed to be the end of the mass extinction. In the stratigraphically overlying beds, Hg/TOC generally displays lower values with slight fluctuations through the two sections. These fluctuations are likely related to the increased terrestrial Hg influx associated with strong chemical weathering in the Early Triassic, as shown by a positive correlation between the contents of Hg and Al, and by less positive Δ199Hg values in Early Triassic samples. Our data, presenting the first Southern Hemisphere Hg record from Guryul Ravine, in combination with previous results, indicates that anomalous high mercury deposition at the EPME occurred globally. The generally positive Δ199Hg values at this time reflects atmospheric-derived Hg, consistent with a volcanic Hg source which we suggest indicates global impact of STLIP eruption. In contrast, there is no evidence for a global Hg/TOC anomaly during the protracted Early Triassic biotic recovery, suggesting that potentially renewed STLIP volcanism had only a northern hemisphere influence on the global Hg cycle. This more limited impact, may still have played a role in the delayed Early Triassic recovery.

Mercury in marine Ordovician/Silurian boundary sections of South China is sulfide-hosted and non-volcanic in origin

Mercury (Hg) enrichment in stratigraphic successions is now widely used as a proxy for volcanic inputs, often for the purpose of documenting a relationship between large igneous province (LIP) magmatism and ecosystem perturbations. Earlier studies of Hg in Ordovician/Silurian boundary (OSB) sections in South China and Laurentia identified transient spikes in Hg/TOC ratios, on the basis of which a link between volcanism and the Late Ordovician mass extinction (LOME) was claimed. However, Hg enrichments must be tested based on normalization to their main host phase, and Hg/TOC is a suitable proxy only if Hg is mainly complexed by organic matter in the sediment. Here, we demonstrate that Hg in three OSB sections in South China (Qiliao, Yanzhi, and Jiaoye) is overwhelmingly associated with pyrite, as shown by r(Hg–TS) > 0.9 (versus r(Hg–TOC) < 0.1) and by EDS elemental mapping. This association requires that Hg concentrations be normalized to pyrite content as proxied by total sulfur [TS], rather than to total organic carbon [TOC]. The resulting Hg/TS profiles show no significant enrichments at any level within the Upper Ordovician–lower Silurian of the study sections. Also, mercury isotope data show constant mass-independent fractionation (Δ199Hg) values (+0.11 ± 0.03‰) that are inconsistent with volcanic inputs. We therefore infer that previous reports of Hg enrichments in OSB sections were due to the presence of Hg-rich sulfides, and that Hg data from both the present and earlier studies provide no evidence of any volcanic influences on the LOME. The results of the present study highlight the need for caution in applying the Hg proxy for volcanic inputs and the importance of evaluating the main host phase of Hg in paleo-marine sediments.

An Integrated Model for Input and Migration of Mercury in Chinese Coastal Sediments.

Coastal sediments are a major sink of the global mercury (Hg) biogeochemical cycle, bridging terrestrial Hg migration to the open ocean. It is thus of substantial interest to quantify the Hg contributors to coastal sediments and the extents to which the Hg sequestered into coastal sediments affects the ocean. Here, we measured concentrations and isotope compositions of Hg in Chinese coastal sediments and found that estuary sediments had distinctly higher δ202Hg and lower Δ199Hg values than marine sediments. Hg isotope compositions of marine sediments followed a latitudinal trend where δ202Hg decreases and Δ199Hg increases from north to south. An integrated model was developed based on a Hg isotope mixing model and urban distance factor (UDF), which revealed a significant difference in Hg source contributions among the estuary and marine sediments and a gradual change of dominant Hg sources from terrestrial inputs (riverine and industrial wastewater discharges) to atmospheric deposition with a decrease in urban impact. A UDF value of 306 ± 217 was established as the critical point where dominant Hg sources started to change from terrestrial inputs to atmospheric deposition. Our study helps explain the input and migration of Hg in Chinese marginal seas and provides critical insights for targeted environmental management.

Tracing Mercury Pollution along the Norwegian Coast via Elemental, Speciation, and Isotopic Analysis of Liver and Muscle Tissue of Deep-Water Marine Fish ( Brosme brosme).

Liver and muscle tissue of tusks ( Brosme brosme) have been analyzed for their THg and MeHg concentrations and Hg isotopic signatures for tracing Hg pollution along the Norwegian coast. Clear differences between tissue types and locations were established. At five of the eight locations, the Hg concentration in muscle exceeded the maximum allowable level of 0.5 mg kg-1 wet weight. δ202Hg values in both tissue types indicated that Hg speciation affects the bulk Hg isotopic signature. Tusk liver seems to be more sensitive to immediate changes and to anthropogenic inorganic Hg, while the muscle rather reflects the Hg accumulated over a longer period of exposure. The δ202Hg values of liver and muscle also enabled different sources of Hg and exposure pathways to be distinguished. δ202Hgmuscle-δ202Hgliver showed a clear correlation with the % MeHg in tusk liver for the coastal waters, but not for the fjords. The absence of significant differences in Δ199Hg values between both tissues of tusk from the same location suggests that in vivo metabolic processes are the underlying reason for the differences in Hg speciation and in δ202Hg values. This work highlights the importance of selecting different tissues of marine fish in future Hg monitoring programs.

Diel variation in mercury stable isotope ratios records photoreduction of PM&amp;lt;sub&amp;gt;2.5&amp;lt;/sub&amp;gt;-bound mercury

Abstract. Mercury (Hg) bound to fine aerosols (PM2.5-Hg) may undergo photochemical reaction that causes isotopic fractionation and obscures the initial isotopic signatures. In this study, we quantified Hg isotopic compositions for 56 PM2.5 samples collected between 15 September and 16 October 2015 from Beijing, China, among which 26 were collected during daytime (between 08:00 and 18:30 LT) and 30 during night (between 19:00 and 07:30 LT). The results show that diel variation was statistically significant (p &lt; 0.05) for Hg content, Δ199Hg and Δ200Hg, with Hg content during daytime (0.32±0.14 µg g−1) lower than at night (0.48±0.24 µg g−1) and Δ199Hg and Δ200Hg values during daytime (mean of 0.26 ‰±0.40 ‰ and 0.09 ‰±0.06 ‰, respectively) higher than during nighttime (0.04 ‰±0.22 ‰ and 0.06 ‰±0.05 ‰, respectively), whereas PM2.5 concentrations and δ202Hg values showed insignificant (p &gt; 0.05) diel variation. Geochemical characteristics of the samples and the air mass backward trajectories (PM2.5 source related) suggest that diel variation in Δ199Hg values resulted primarily from the photochemical reduction of divalent PM2.5-Hg, rather than variations in emission sources. The importance of photoreduction is supported by the strong correlations between Δ199Hg and (i) Δ201Hg (positive, slope = 1.1), (ii) δ202Hg (positive, slope = 1.15), (iii) content of Hg in PM2.5 (negative), (iv) sunshine durations (positive) and (v) ozone concentration (positive) observed for consecutive day–night paired samples. Our results provide isotopic evidence that local, daily photochemical reduction of divalent Hg is of critical importance to the fate of PM2.5-Hg in urban atmospheres and that, in addition to variation in sources, photochemical reduction appears to be an important process that affects both the particle mass-specific abundance and isotopic composition of PM2.5-Hg.

Characteristics of Stable Mercury Isotopic Compositions in the Food Web of the Caohai Lake

Caohai Plateau Wetland is a National Nature Reserve. The characteristics of stable mercury isotopic compositions in the food web were studied by comprehensively analyzing the concentrations of Hg species (MeHg, THg), δ13 C, and δ15N, and the isotopic compositions of Hg in different aquatic organisms. The main results are as follows:all samples of the food web show mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) and a negative δ202 Hg(-0.93‰±1.32‰, n=14)and positive △199 Hg(0.79‰±0.76‰, n=14). The δ199 Hg values are significantly positively correlated with δ15N (r=0.65, P<0.05) and the δ202 Hg values also exhibit a positive correlation with δ15N, except for Myriophyllum spicatum(δ15N=-1.88‰), indicating that the bioaccumulation of mercury leads to an enrichment with heavier isotopes. The △199 Hg values increase with δ15N(r=0.67, P<0.05). Nevertheless, the △199 Hg values correlate with% MeHg (r=0.58, P<0.05), indicating that the increase of the MIF level in the samples with the food web might be related to% MeHg.

Mercury in tundra vegetation of Alaska: Spatial and temporal dynamics and stable isotope patterns

Vegetation uptake of atmospheric mercury (Hg) is an important mechanism enhancing atmospheric Hg deposition via litterfall and senescence. We here report Hg concentrations and pool sizes of different plant functional groups and plant species across nine tundra sites in northern Alaska. Significant spatial differences were observed in bulk vegetation Hg concentrations at Toolik Field station (52 ± 9 μg kg−1), Eight Mile Lake Observatory (40 ± 0.2 μg kg−1), and seven sites along a transect from Toolik Field station to the Arctic coast (36 ± 9 μg kg−1). Hg concentrations in non-vascular vegetation including feather and peat moss (58 ± 6 μg kg−1 and 34 ± 2 μg kg−1, respectively) and brown and white lichen (41 ± 2 μg kg−1 and 34 ± 2 μg kg−1, respectively), were three to six times those of vascular plant tissues (8 ± 1 μg kg−1 in dwarf birch leaves and 9 ± 1 μg kg−1 in tussock grass). A high representation of nonvascular vegetation in aboveground biomass resulted in substantial Hg mass contained in tundra aboveground vegetation (29 μg m−2), which fell within the range of foliar Hg mass estimated for forests in the United States (15 to 45 μg m−2) in spite of much shorter growing seasons.Hg stable isotope signatures of different plant species showed that atmospheric Hg(0) was the dominant source of Hg to tundra vegetation. Mass-dependent isotope signatures (δ202Hg) in vegetation relative to atmospheric Hg(0) showed pronounced shifts towards lower values, consistent with previously reported isotopic fractionation during foliar uptake of Hg(0). Mass-independent isotope signatures (Δ199Hg) of lichen were more positive relative to atmospheric Hg(0), indicating either photochemical reduction of Hg(II) or contributions of inorganic Hg(II) from atmospheric deposition and/or dust. Δ199Hg and Δ200Hg values in vascular plant species were similar to atmospheric Hg(0) suggesting that overall photochemical reduction and subsequent re-emission was relatively insignificant in these tundra ecosystems, in agreement with previous Hg(0) ecosystem flux measurements.

Mercury Stable Isotope Fractionation During Coal Combustion in Coal-Fired Boilers: Reconciling Atmospheric Hg Isotope Observations with Hg Isotope Fractionation Theory.

Mercury (Hg) stable isotope is a useful tool to understand the transformation of atmospheric Hg. The observation on the enrichment of heavier isotopes in gaseous elemental Hg (GEM) relative to oxidized HgII species in atmosphere cannot be convincingly explained by isotope fractionation of Hg redox processes. This review shows that the large Hg isotope mass dependent fractionation (MDF) in coal-fired boilers is one of the underlying reasons. The reported Hg isotope data of feed coals and their combustion products are first summarized to give a general overview of how Hg isotopes fractionate before Hg discharge from coal-fired boilers. Then, predictive MDF models are discussed to simulate δ202Hg values of different Hg species in coal combustion flue gases. The discharged GEM is predicted to have the highest δ202Hg followed by gaseous HgII and particulate-bound HgII, which is in consistent with the observed MDF pattern of atmospheric Hg species.

Biotic responses to volatile volcanism and environmental stresses over the Guadalupian-Lopingian (Permian) transition

Biotic extinction during the Guadalupian-Lopingian (G-L) transition is actively debated, with its timing, validity, and causality all questioned. Here, we show, based on detailed sedimentary, paleoecologic, and geochemical analyses of the Penglaitan section in South China, that this intra-Permian biotic crisis began with the demise of a metazoan reef system and extinction of corals and alatoconchid bivalves in the late Guadalupian. A second crisis, among nektonic organisms, occurred around the G-L boundary. Mercury concentration/total organic carbon (Hg/TOC) ratios show two anomalies. The first Hg/TOC peak broadly coincides with the reef collapse and a positive shift in Δ199Hg values during a lowstand interval, which was followed by microbial proliferation. A larger Hg/TOC peak is found just above the G-L boundary and speculatively represents a main eruption episode of the Emeishan large igneous province (ELIP). This volatile volcanism coincided with nektonic extinction, a negative δ13Ccarb excursion, anoxia, and sea-level rise. The temporal coincidence of these phenomena supports a cause-andeffect relationship and indicates that the eruption of the ELIP likely triggered the G-L crisis.