Mercury Isotopes Research Articles

Deglacial volcanism and reoxygenation in the aftermath of the Sturtian Snowball Earth.

The Cryogenian Sturtian and Marinoan Snowball Earth glaciations bracket a nonglacial interval during which Demosponge and green-algal biomarkers first appear. To understand the relationships between environmental perturbations and early animal evolution, we measured sulfur and mercury isotopes from the Datangpo Formation from South China. Hg enrichment with positive Δ199Hg excursion suggests enhanced volcanism, potentially due to depressurization of terrestrial magma chambers during deglaciation. A thick stratigraphic interval of negative Δ33Spy indicates that the nonglacial interlude was characterized by low but rising sulfate levels. Model results reveal a mechanism to produce the Δ33S anomalies down to -0.284‰ through Rayleigh distillation. We propose that extreme temperatures and anoxia contributed to the apparent delay in green algal production in the aftermath of the Sturtian glaciation and the subsequent reoxygenation of the iron-rich and sulfate-depleted ocean paved the way for evolution of animals.

Mercury isotopes record development and attenuation of photic zone euxinia during the earliest Cambrian

Mercury isotopes record development and attenuation of photic zone euxinia during the earliest Cambrian

The mercury flow through a terrestrial songbird food chain in subtropical pine forest: Elucidated by Bayesian isotope mixing model and stable mercury isotopes

In order to comprehend the transfer of inorganic mercury (IHg) and methylmercury (MeHg) within food chains in terrestrial pine forests, we collected samples of Great Tit nestlings, common invertebrates, plants, and soil in a subtropical pine forest and used Bayesian isotope mixing model analysis, Hg daily intake, and stable Hg isotopes to elucidate the flow of MeHg and IHg in these food chains. Results indicate that caterpillars and cockroaches are the predominant prey items for nestlings, accounting for a combined contribution of 81.5%. Furthermore, caterpillars, cockroaches, and spiders were found to contribute the most (∼80%) of both IHg and MeHg that dietary accumulated in nestlings. The provisoned invertebrates tend to supply more IHg and diluting the proportion of MeHg as total Hg (MeHg%). Notably, nestling feathers displayed the highest Δ199Hg values but a relatively lower MeHg%, suggesting an imbalanced incorporation of Hg from maternal transfer and dietary accumulation during the nestling stage. This study highlights the efficacy of nestlings as indicators for identifying Hg sources and transfers in avian species and food chains. However, caution must be exercised when using Hg isotope compositions in growing feathers, and the contribution of maternally transferred Hg should not be ignored.

Mercury isotope compositions in seawater and marine fish revealed the sources and processes of mercury in the food web within differing marine compartments.

Anthropogenic activities and climate change have significantly increased mercury (Hg) levels in seawater. However, the processes and sources of Hg in differing marine compartments (e.g. estuary, marine continental shelf (MCS) or pelagic area) have not been well studied, which makes it difficult to understand Hg cycling in marine ecosystems. To address this issue, the total Hg (THg) concentration, methylmercury (MeHg) concentration and stable Hg isotopes were determined in seawater and fish samples collected from differing marine compartments of the South China Sea (SCS). The results showed that the estuarine seawater exhibited substantially higher THg and MeHg concentrations than those in the MCS and pelagic seawater. Significantly negative δ202Hg (-1.63‰ ± 0.42‰) in estuarine seawater compared with that in pelagic seawater (-0.58‰ ± 0.08‰) may suggest watershed input and domestic sewage discharge of Hg in the estuarine compartment. The Δ199Hg value in estuarine fish (0.39‰ ± 0.35‰) was obviously lower than that in MCS (1.10‰ ± 0.54‰) and pelagic fish (1.15‰ ± 0.46‰), which showed that relatively little MeHg photodegradation occurred in the estuarine compartment. The Hg isotope binary mixing model based on Δ200Hg revealed that approximately 74% MeHg in pelagic fish is derived from atmospheric Hg(II) deposition, and over 60% MeHg in MCS fish is derived from sediments. MeHg sources for estuarine fish may be highly complex (e.g. sediment or riverine/atmospheric input) and further investigations are warranted to clarify the contribution of each source. Our study showed that Hg stable isotopes in seawater and marine fish can be used to identify the processes and sources of Hg in different marine compartments. This finding is of great relevance to the development of marine Hg food web models and the management of Hg in fish.

Separaton Efficiency and Separation Time of Mass Separator MASHA Measured for Radon and Mercury Isotopes

Separaton Efficiency and Separation Time of Mass Separator MASHA Measured for Radon and Mercury Isotopes

Climatic regulation of atmospheric mercury deposition: Evidence from mercury isotopes in an alpine peat core

Abstract Mercury is a global pollutant that can undergo long-range transport in the atmosphere. While anthropogenic activities have largely increased atmospheric Hg emission and deposition since global industrialization, mechanisms governing the atmospheric Hg cycle in preindustrial periods remain unclear. Alpine peatlands receive Hg mainly from atmospheric Hg deposition and are sensitive to climatic changes, therefore alpine peat cores can be a useful archive for understanding the relationship between atmospheric Hg deposition and climate change. Here we reconstruct a 1200-year Hg deposition record based on a core drilled from an ombrotrophic peat bog in Yunnan-Guizhou Plateau, SW China. This core shows a dramatic change of Hg deposition fluxes (30.3–515 μg/m2/yr) associated with variable Hg isotopic composition (δ202Hg: –1.02‰ to –2.01‰; Δ199Hg: –0.16‰ to –0.50‰; Δ200Hg: –0.08‰ to 0.07‰). Using a Δ200Hg-based model, deposition fluxes of atmospheric Hg(0) and Hg(II) were estimated, which vary coherently with climatic indices (e.g., temperature, precipitation, and monsoon intensity). Results of this study imply that atmospheric Hg deposition in SW China is governed by two climate scenarios. In warm-house climates, low precipitation intensity and vegetation growth rates in SW China caused low atmospheric Hg(II) and Hg(0) deposition fluxes, respectively. In cold-house climates, high precipitation intensity and vegetation growth rates caused high atmospheric Hg(II) and Hg(0) deposition fluxes. This study highlights that climate changes can have a strong control on atmospheric Hg deposition.

A 1500-year record of mercury isotopes in seal feces documents sea ice changes in the Antarctic

Temporal and spatial variations in sea ice coverage at high Northern Hemisphere latitudes have been shown to affect the photodegradation of methylmercury in seawater and the mercury isotope signatures in biological samples, suggesting the potential of mercury isotopes to reconstruct sea ice variability. Here we study the mercury isotopic composition of a 1500-year sediment profile strongly affected by seal activities on the Fildes Peninsula, King George Island, Antarctic Peninsula. The mass independent isotope fractionation of mercury (represented by Δ199Hg) in sediments dominated by seal feces input reflects the Δ199Hg of marine methylmercury before entering the food web, documenting the changes in the degree of photodemethylation. We found much higher Δ199Hg in sediments deposited during a warm period (~700-1000 years ago), suggesting that reduced sea ice promoted greater photodemethylation. Thus, this study demonstrates the modulation of methylmercury photodegradation by sea ice in the Antarctic, and that mercury isotopes can record historical sea ice changes.

Mercury accumulation, biomagnification, and relationships to δ13C, δ15N and δ34S of fishes and marine mammals in a coastal Arctic marine food web

Combining mercury and stable isotope data sets of consumers facilitates the quantification of whether contaminant variation in predators is due to diet, habitat use and/or environmental factors. We investigated inter-species variation in total Hg (THg) concentrations, trophic magnification slope between δ15N and THg, and relationships of THg with δ13C and δ34S in 15 fish and four marine mammal species (249 individuals in total) in coastal Arctic waters. Median THg concentration in muscle varied between species ranging from 0.08 ± 0.04 μg g−1 dw in capelin to 3.10 ± 0.80 μg g−1 dw in beluga whales. Both δ15N (r2 = 0.26) and δ34S (r2 = 0.19) best explained variation in log-THg across consumers. Higher THg concentrations occurred in higher trophic level species that consumed more pelagic-associated prey than consumers that rely on the benthic microbial-based food web. Our study illustrates the importance of using a multi-isotopic approach that includes δ34S when investigating trophic Hg dynamics in coastal marine systems.

Recurrent photic zone euxinia limited ocean oxygenation and animal evolution during the Ediacaran

The Ediacaran Period (~635–539 Ma) is marked by the emergence and diversification of complex metazoans linked to ocean redox changes, but the processes and mechanism of the redox evolution in the Ediacaran ocean are intensely debated. Here we use mercury isotope compositions from multiple black shale sections of the Doushantuo Formation in South China to reconstruct Ediacaran oceanic redox conditions. Mercury isotopes show compelling evidence for recurrent and spatially dynamic photic zone euxinia (PZE) on the continental margin of South China during time intervals coincident with previously identified ocean oxygenation events. We suggest that PZE was driven by increased availability of sulfate and nutrients from a transiently oxygenated ocean, but PZE may have also initiated negative feedbacks that inhibited oxygen production by promoting anoxygenic photosynthesis and limiting the habitable space for eukaryotes, hence abating the long-term rise of oxygen and restricting the Ediacaran expansion of macroscopic oxygen-demanding animals.

Mercury isotopes trace historical mercury pollution from Pb[sbnd]Zn smelter in China

Lead–zinc (PbZn) smelting is one of the largest anthropogenic emission sources of mercury (Hg) in China and the world. In the last few decades, Hg emission control devices have been employed in PbZn smelters to reduce Hg emissions. To evaluate the effectiveness of Hg emission control, this study uses Hg isotopes to trace the sources of Hg in soils and reservoir sediments near the Zhuzhou smelter, the largest Zn production facility in China. The results showed that Hg concentrations in reservoir sediments were higher than those in soils at the three study sites, suggesting that reservoir sediments accumulate more Hg than soils do under the same conditions. Hg concentrations and deposition fluxes in reservoir sediments have dramatically decreased since the year 2000, suggesting the effectiveness of Hg emission control in the Zhuzhou smelter. Mercury isotope compositions in soil suggest binary mixing of Hg from the Zhuzhou smelter and the local background, and the contribution of Hg from the Zhuzhou smelter to soils and sediment is mainly a function of location and distance from the source. The model output suggested that approximately 61–75% of Hg in reservoir sediments was sourced from the Zhuzhou smelter. This study demonstrates that legacy Hg will continue to be a source to local ecosystems, even after Hg emission control has been implemented for decades.

Paleo‐Pacific Plate Subduction and Basement Mobilization Triggered Large‐Scale Formation of Mesozoic Gold Deposits in the Northern Margin of the North China Craton

AbstractThe northern margin of the North China Craton (NNCC) hosts Mesozoic gold deposits of significant economic importance. The metal sources of these gold systems have long been debated with mainly magmatic‐hydrothermal versus metamorphic fluid models. Mercury (Hg) isotopes, which undergo unique mass‐independent fractionation, can provide important insights into the source of metals in gold deposits due to the close association between Hg and Au in such systems. Here, we investigated the Hg isotopic composition of six gold deposits of the Middle Jurassic to Early Cretaceous age and potential source rocks in the NNCC. Variable ∆199Hg values were observed in bulk ore and pyrite samples (−0.28‰ to 0.34‰, n = 51) and coeval granites (−0.21‰ to 0.13‰; n = 25). The negative ∆199Hg values of bulk ore and pyrite samples mostly agree with that observed for metamorphic basement rocks (−0.37‰ to 0.11‰; n = 32). The positive ∆199Hg values of bulk ore and pyrite samples agree with those reported in marine sediments (0‰–0.3‰). So the data suggest binary mixing of ocean‐recycled Hg originated from the subducted oceanic slab, and terrestrial‐recycled Hg from the Precambrian basement in Mesozoic gold deposits. The contribution of Hg (and Au, by analogy) from both reservoirs varies depending on active continental arc versus intracontinental setting and is ultimately controlled by translithospheric heat flow driven by paleo‐Pacific plate subduction.

Volcanism intensity and associated climate-ocean-land dynamics during the Cryogenian interglaciation: Insights from mercury isotopes

The Cryogenian interglaciation (ca. 660 Ma to 650 Ma) was an interlude between the Sturtian glaciation (ca. 717 Ma to 660 Ma) and Marinoan glaciation (ca. 650 Ma to 635 Ma). Recent observations of anomalously high mercury (Hg) concentrations in Cryogenian interglacial sediments at basinal settings in the Nanhua Rift Basin, South China, imply that large volcanism can be a possible driving force of the Cryogenian interglaciation. To test this hypothesis and understand the potential linkage between large volcanism and climate-ocean-land dynamics during the Cryogenian interglaciation, we investigate mercury (Hg) concentrations and isotopic composition of Cryogenian interglacial sediments at shallow water (shelf/slope) settings in the Nanhua Rift Basin, South China. The basal Mn-bearing black shales show an increased pattern in Hg concentrations (318 to 4400 ppb) and Hg/TOC ratios (243 to 1730 ppb/wt%), and overall positive Δ199Hg values (0.00 to 0.10‰), suggesting increasing volcanic Hg input into the ocean via atmospheric Hg(II) deposition in the early Cryogenian interglaciation. The upper siltstone samples show a dramatic decrease in Hg concentrations (from 5110 to 459 ppb) and a drop of Δ199Hg values (from 0.04 to −0.05‰), suggesting weakened volcanism during the middle-late Cryogenian interglaciation. Combined with the analyses of major and trace elements proxies, we demonstrate that (1) greenhouse climate in the early Cryogenian interglaciation induced high oceanic productivity, high organic burial on the seafloor and high terrestrial sulfate input into the ocean, which favors the deposition of Mn-bearing black shales in the ocean; and (2) weakened volcanism and continued continental weathering exhausted atmospheric CO2 and drove the global climate to the Marinoan glaciation. This study, therefore, provides important insights into the climate-ocean-land dynamics during the Cryogenian interglaciation.

Atmospheric Mercury Isotope Shifts in Response to Mercury Emissions from Underground Coal Fires.

Pollutant emissions from coal fires have caused serious concerns in major coal-producing countries. Great efforts have been devoted to suppressing them in China, notably at the notorious Wuda Coalfield in Inner Mongolia. Recent surveys revealed that while fires in this coalfield have been nearly extinguished near the surface, they persist underground. However, the impacts of Hg volatilized from underground coal fires remain unclear. Here, we measured concentrations and isotope compositions of atmospheric Hg in both gaseous and particulate phases at an urban site near the Wuda Coalfield. The atmospheric Hg displayed strong seasonality in terms of both Hg concentrations (5-7-fold higher in fall than in winter) and isotope compositions. Combining characteristic isotope compositions of potential Hg sources and air mass trajectories, we conclude that underground coal fires were still emitting large amounts of Hg into the atmosphere that have been transported to the adjacent urban area in the prevailing downwind direction. The other local anthropogenic Hg emissions were only evident in the urban atmosphere when the arriving air masses did not pass directly through the coalfield. Our study demonstrates that atmospheric Hg isotope measurement is a useful tool for detecting concealed underground coal fires.

Mercury isotope evidence for recurrent photic-zone euxinia triggered by enhanced terrestrial nutrient inputs during the Late Devonian mass extinction

Widespread oceanic anoxia marked by globally extensive deposition of organic-rich black shale during the Late Devonian was a major factor in the mass extinctions at the Frasnian-Famennian (FFB, ∼372 million years ago) and Devonian-Carboniferous boundaries (DCB, ∼359 million years ago), although the triggers for these deoxygenation events are still under debate. Here, we apply a novel paleoredox proxy, Hg isotopes, to investigate Late Devonian ocean redox variation and its causes. We found no Hg enrichments in North America across either the FFB or DCB, thus arguing against the hypothesis of global-scale volcanism as the trigger for Late Devonian environmental and biotic crises. Gradual negative shifts of both mass-independent fractionation (Δ199Hg) and mass-dependent fractionation (δ202Hg) occurred between the FFB and DCB, suggesting a progressive increase of Hg inputs associated with terrestrial organic matter. Moreover, multiple abrupt negative excursions of Δ199Hg (down to −0.19‰) along with concurrent positive shifts of δ202Hg occurred just above the FFB and across the DCB, providing strong evidence for recurrent photic-zone euxinia (PZE) that was preceded by increasing terrestrial inputs in the epicontinental seas of North America. We suggest that the increase of terrestrial inputs of nutrients, probably via expansion of vascular land plants, stimulated marine primary productivity and eventually PZE, which may have been a key kill mechanism for the Late Devonian mass extinction.

Mercury isotope evidence for marine photic zone euxinia across the end-Permian mass extinction

The driving forces, kill and recovery mechanisms for the end-Permian mass extinction (EPME), the largest Phanerozoic biological crisis, are under debate. Sedimentary records of mercury enrichment and mercury isotopes have suggested the impact of volcanism on the EPME, yet the causes of mercury enrichment and isotope variations remain controversial. Here, we model mercury isotope variations across the EPME to quantitatively assess the effects of volcanism, terrestrial erosion and photic zone euxinia (PZE, toxic, sulfide-rich conditions). Our numerical model shows that while large-scale volcanism remains the main driver of widespread mercury enrichment, the negative shifts of Δ199Hg isotope signature across the EPME cannot be fully explained by volcanism or terrestrial erosion as proposed before, but require additional fractionation by marine mercury photoreduction under enhanced PZE conditions. Thus our model provides further evidence for widespread and prolonged PZE as a key kill mechanism for both the EPME and the impeded recovery afterward.

Mercury isotopes show vascular plants had colonized land extensively by the early Silurian

The colonization and expansion of plants on land is considered one of the most profound ecological revolutions, yet the precise timing remains controversial. Because land vegetation can enhance weathering intensity and affect terrigenous input to the ocean, changes in terrestrial plant biomass with distinct negative Δ199Hg and Δ200Hg signatures may overwrite the positive Hg isotope signatures commonly found in marine sediments. By investigating secular Hg isotopic variations in the Paleozoic marine sediments from South China and peripheral paleocontinents, we highlight distinct negative excursions in both Δ199Hg and Δ200Hg at Stage level starting in the early Silurian and again in the Carboniferous. These geochemical signatures were driven by increased terrestrial contribution of Hg due to the rapid expansion of vascular plants. These excursions broadly coincide with rising atmospheric oxygen concentrations and global cooling. Therefore, vascular plants were widely distributed on land during the Ordovician-Silurian transition (~444 million years), long before the earliest reported vascular plant fossil, Cooksonia (~430 million years).

Mercury biomagnification at higher rates than the global average in aquatic ecosystems of the Qinghai-Tibet Plateau

Mercury biomagnification in aquatic ecosystems is a global issue. Biomagnification patterns and drivers in alpine regions remain poorly understood. Hg biomagnification in the aquatic food web of the Qinghai-Tibetan Plateau (Q-T Plateau) was investigated. A total of 302 fish and macroinvertebrate tissue samples were analysed for total mercury (THg) and nitrogen (δ15N) stable isotope ratios. Overall, 26.75% of fish individuals exceeded the USFWS consumption guidelines. A total of 52.17% of the sampling sites covering different habitats exhibited a significantly positive THg–δ15N relationship, which confirmed the Hg biomagnification potential of Q-T Plateau aquatic ecosystems. The Q-T Plateau Hg biomagnification rates were generally far higher than global averages regardless of the habitat type. Hg in sediments, elevation and population density were positively related to the Hg biomagnification magnitude on the Q-T Plateau, which could be attributed to the disproportionate response of Hg concentrations in macroinvertebrates and fishes along environmental gradients. Our findings offer empirical evidence that fish consumption on the Q-T Plateau poses a substantial Hg exposure risk to people living along river and lake shores. Higher biomagnification rates could further disproportionately accelerate Hg pollution in Q-T Plateau aquatic ecosystems under future anthropogenic activities and climate warming trajectories.

Mercury Isotopes in Deep-Sea Epibenthic Biota Suggest Limited Hg Transfer from Photosynthetic to Chemosynthetic Food Webs.

Deep oceans receive mercury (Hg) from upper oceans, sediment diagenesis, and submarine volcanism; meanwhile, sinking particles shuttle Hg to marine sediments. Recent studies showed that Hg in the trench fauna mostly originated from monomethylmercury (MMHg) of the upper marine photosynthetic food webs. Yet, Hg sources in the deep-sea chemosynthetic food webs are still uncertain. Here, we report Hg concentrations and stable isotopic compositions of indigenous biota living at hydrothermal fields of the Indian Ocean Ridge and a cold seep of the South China Sea along with hydrothermal sulfide deposits. We find that Hg is highly enriched in hydrothermal sulfides, which correlated with varying Hg concentrations in inhabited biota. Both the hydrothermal and cold seep biota have small fractions (<10%) of Hg as MMHg and slightly positive Δ199Hg values. These Δ199Hg values are slightly higher than those in near-field sulfides but are 1 order of magnitude lower than the trench counterparts. We suggest that deep-sea chemosynthetic food webs mainly assimilate Hg from ambient seawater/sediments and hydrothermal fluids formed by percolated seawater through magmatic/mantle rocks. The MMHg transfer from photosynthetic to chemosynthetic food webs is likely limited. The contrasting Hg sources between chemosynthetic and trench food webs highlight Hg isotopes as promising tools to trace the deep-sea Hg biogeochemical cycle.

Aquatic methylmercury is a significant subsidy for terrestrial songbirds: Evidence from the odd mass-independent fractionation of mercury isotopes

In contrast to aquatic food chains, knowledge of the origins and transfer of mercury (Hg) and methylmercury (MeHg) in terrestrial food chains is relatively limited, especially in songbirds. We collected soil, rice plants, aquatic and terrestrial invertebrates, small wild fish, and resident songbird feathers from an Hg-contaminated rice paddy ecosystem for an analysis of stable Hg isotopes to clarify the sources of Hg and its transfer in songbirds and their prey. Significant mass-dependent fractionation (MDF, δ202Hg), but no mass-independent fractionation (MIF, ∆199Hg) occurred in the trophic transfers in terrestrial food chains. Piscivorous, granivorous, and frugivorous songbirds and aquatic invertebrates were all characterized by elevated Δ199Hg values. The estimated MeHg isotopic compositions obtained using linear fitting and a binary mixing model explained both the terrestrial and aquatic origins of MeHg in the terrestrial food chains. We found that MeHg from aquatic habitats is an important subsidy for terrestrial songbirds, even those that feed mainly on seeds, fruits, or cereals. The results show that MIF of the MeHg isotope is a reliable tool to reveal MeHg sources in songbirds. Because the MeHg isotopic compositions was calculated with a binary mixing model or directly estimated from the high proportions of MeHg, compound-specific isotope analysis of Hg would be more useful for the interpretation of the Hg sources, and is highly recommended for future studies.

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

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