Tracing anthropogenic mercury in soils from Fe-Hg mining/smelting area: Isotopic and speciation insights.

Mercury (Hg) stable isotope ratios supplemented by Hg solid speciation data were determined in soils in a former Fe-Hg mining/smelting area (Jedová hora, Czech Republic, Central Europe). The dominant Hg phase in the studied soils was found to be cinnabar (HgS). A secondary form of soil Hg(II) was represented by Hg weakly and strongly bound to mineral (micro)particles, as revealed by thermo-desorption analysis. These Hg species probably play a key role in local soil Hg processes and biogeochemical cycling. The Hg isotopic data generally showed small differences between HgS (-1.1 to -0.8‰; δ202Hg) and the soil samples (-1.4 to -0.9‰; δ202Hg), as well as limited isotopic variability within the two studied soil profiles. On the other hand, the detected negative δ202Hg shift (∼0.4‰) in organic horizons compared to mineral soils in the highly contaminated profile suggests the presence of secondary post-depositional Hg processes, such as sorption or redox changes. For the less contaminated profile, the observed Hg isotopic variation (∼0.3‰; δ202Hg) in the subsurface mineral soil compared to both overlying and underlying horizons is likely due to cyclic redox reactions associated with Hg isotopic fractionation. We assume that the adsorption of Hg(II) to secondary Fe(III)/Mn(III,IV)-oxides could be of major importance in such cases.

Unveiling the Sources and Transfer of Mercury in Forest Bird Food Chains Using Techniques of Vivo-Nest Video Recording and Stable Isotopes.

Knowledge gaps in mercury (Hg) biomagnification in forest birds, especially in the most species-rich tropical and subtropical forests, limit our understanding of the ecological risks of Hg deposition to forest birds. This study aimed to quantify Hg bioaccumulation and transfer in the food chains of forest birds in a subtropical montane forest using a bird diet recorded by video and stable Hg isotope signals of biological and environmental samples. Results show that inorganic mercury (IHg) does not biomagnify along food chains, whereas methylmercury (MeHg) has trophic magnification factors of 7.4-8.1 for the basal resource-invertebrate-bird food chain. The video observations and MeHg mass balance model suggest that Niltava (Niltava sundara) nestlings ingest 78% of their MeHg from forest floor invertebrates, while Flycatcher (Eumyias thalassinus) nestlings ingest 59% from emergent aquatic invertebrates (which fly onto the canopy) and 40% from canopy invertebrates. The diet of Niltava nestlings contains 40% more MeHg than that of Flycatcher nestlings, resulting in a 60% higher MeHg concentration in their feather. Hg isotopic model shows that atmospheric Hg0 is the main Hg source in the forest bird food chains and contributes >68% in most organisms. However, three categories of canopy invertebrates receive ∼50% Hg from atmospheric Hg2+. Overall, we highlight the ecological risk of MeHg exposure for understory insectivorous birds caused by atmospheric Hg0 deposition and methylation on the forest floor.

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

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

Significant biomagnification of methylmercury in songbird nestlings through a rice-based food web: Insights from stable mercury isotopes.

To elucidate the sources and transfer of mercury (Hg) in terrestrial food chains, particularly in heavily Hg-contaminated rice paddy ecosystems, we collected rice leaves, invertebrates, and Russet Sparrow nestlings from a clear food chain and analyzed the dietary compositions and potential Hg sources using stable Hg isotopes coupled with a Bayesian isotope mixing model (BIMM). Our findings indicated that MeHg exposure is dominant through the dietary route, with caterpillars, grasshoppers, and katydids being the main prey items, while the less provisioned spiders, dragonflies, and mantises contributed the most of the Hg to nestlings. We found minimal MIF but certain MDF in this terrestrial food chain and identified two distinct MeHg sources of dietary exposure and maternal transfer. We firstly found that the dietary route contributed substantially (almost tenfold) more MeHg to the nestlings than maternal transfer. These findings offer new insights into the integration of Hg from the dietary route and maternal transfers, enhancing our understanding of fluctuating Hg exposure risk during the nestling stage. Our study suggested that Hg isotopes combined with BIMM is an effective approach for tracing Hg sources in birds and for gaining in-depth insight into the trophic transfers and biomagnification of MeHg in food chains.

Optimization of a pre-concentration method for the analysis of mercury isotopes in low-concentration foliar samples.

Hg isotope analysis in samples from background regions is constrained by the presence of low Hg concentration and therefore requires a pre-concentration method. Existing Hg pre-concentration methods are constrained by long sample processing time and limited sample loading capacity. Using foliar samples as a test case, an optimized Hg pre-concentration method is presented that involves the microwave-assisted digestion of samples for Hg isotope analysis with the addition of a pre-digestion step. Microwave-digested foliar samples and CRMs were transferred to an impinger, reduced with SnCl2, and collected in a 2.25 mL concentrated inverse aqua regia (3:1 HNO3:HCl, v/v). This resulted in an optimal acid concentration in the solution ideal for analysis on MC-ICP-MS. The time for purging with Hg-free N2 was optimized to 30 min and the efficiency of the pre-concentration method was tested using a combination of approaches. Tests performed on pure reagents and matrix of foliar samples spiked with 197Hg radiotracer showed recoveries averaging 99 ± 1.7% and 100 ± 3.0%, respectively. Mercury at concentrations as low as 1.83 ng g-1 was pre-concentrated by digesting aliquots of foliage samples in individual digestion vessels. Recoveries following their pre-concentration averaged 99 ± 6.0%, whereas recoveries of 95 ± 4.7% and 95 ± 2.5% were achieved for NIST SRM 1575a (pine needle) and reagents spiked with NIST SRM 3133, respectively. Analysis using multicollector-ICP-MS showed low fractionation of δ202Hg during sample pre-concentration with no significant mass-independent fractionation. The proposed method is a relatively simple and robust way to prepare Hg samples for Hg isotopic analysis and is suitable even for complex biological matrices.

Increased Contribution of Circumpolar Deep Water Upwelling to Methylmercury in the Upper Ocean around Antarctica: Evidence from Mercury Isotopes in the Ornithogenic Sediments.

Upwelling plays a pivotal role in supplying methylmercury (MeHg) to the upper oceans, contributing to the bioaccumulation of MeHg in the marine food web. However, the influence of the upwelling of Circumpolar Deep Water (CDW), the most voluminous water mass in the Southern Ocean, on the MeHg cycle in the surrounding oceans and marine biota of Antarctica remains unclear. Here, we study the mercury (Hg) isotopes in an ornithogenic sedimentary profile strongly influenced by penguin activity on Ross Island, Antarctica. Results indicate that penguin guano is the primary source of Hg in the sediments, and the mass-independent isotope fractionation of Hg (represented by Δ199Hg) can provide insights on the source of marine MeHg accumulated by penguin. The Δ199Hg in the sediments shows a significant decrease at ∼1550 CE, which is primarily attributed to the enhanced upwelling of CDW that brought more MeHg with lower Δ199Hg from the deeper seawater to the upper ocean. We estimate that the contribution of MeHg from the deeper seawater may reach more than 38% in order to explain the decline in Δ199Hg at ∼1550 CE. Moreover, we found that the intensified upwelling may have increased the MeHg exposure for marine organisms, highlighting the importance of CDW upwelling on the MeHg cycle in Antarctic coastal ecosystems.

Foraging behavior and sea ice-dependent factors affecting the bioaccumulation of mercury in Antarctic coastal waters.

To elucidate the potential risks of the toxic pollutant mercury (Hg) in polar waters, the study of accumulated Hg in fish is compelling for understanding the cycling and fate of Hg on a regional scale in Antarctica. Herein, the Hg isotopic compositions of Antarctic cod Notothenia coriiceps were assessed in skeletal muscle, liver, and heart tissues to distinguish the differences in Hg accumulation in isolated coastal environments of the eastern (Chinese Zhongshan Station, ZSS) and the antipode western Antarctica (Chinese Great Wall Station, GWS), which are separated by over 4000 km. Differences in odd mass-independent isotope fractionation (odd-MIF) and mass-dependent fractionation (MDF) across fish tissues were reflection of the specific accumulation of methylmercury (MeHg) and inorganic Hg (iHg) with different isotopic fingerprints. Internal metabolism including hepatic detoxification and processes related to heart may also contribute to MDF. Regional heterogeneity in iHg end-members further provided evidence that bioaccumulated Hg origins can be largely influenced by polar water circumstances and foraging behavior. Sea ice was hypothesized to play critical roles in both the release of Hg with negative odd-MIF derived from photoreduction of Hg2+ on its surface and the impediment of photochemical transformation of Hg in water layers. Overall, the multitissue isotopic compositions in local fish species and prime drivers of the heterogeneous Hg cycling and bioaccumulation patterns presented here enable a comprehensive understanding of Hg biogeochemical cycling in polar coastal waters.

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.

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.

Impact of forest fire on the mercury stable isotope composition in litter and soil in the Amazon.

Mercury (Hg) emissions from forest fires, especially tropical forests such as the Amazonian forest, were shown to contribute significantly to the atmospheric mercury budget, but new methods are still necessary to improve the traceability and to reduce the great uncertainties related to this emission source. Recent studies have shown that the combustion process can result in Hg stable isotope fractionation that allows tracking coal combustion Hg emissions, as influenced by different factors such as combustion temperature. The main goal of the present study was, therefore, to investigate for the first time the potential of Hg stable isotopes to trace forest fire Hg emissions and pathways. More specifically, small-scale and a large scale prescribed forest fire experiments were conducted in the Brazilian Amazonian forest to study the impact of fire severity on Hg isotopic composition of litter, soil, and ash samples and associated Hg isotope fractionation pathways. In the small-scale experiment, no difference was found in the mercury isotopic composition of the samples collected before and after burning. In contrast, the larger-scale experiment resulted in significant mass dependent fractionation (MDF δ202Hg) in soils and ash suggesting that higher combustion temperature influence Hg isotopic fractionation with the emission of lighter Hg isotopes to the atmosphere and enrichment with heavier Hg in ashes. As for coal combustion, mass independent fractionation was not observed. To our knowledge, these results are the first to highlight the potential of forest fires to cause Hg isotopic fractionation, depending on the fire severity. The results also allowed to establish an isotopic fingerprint for tropical forest fire Hg emissions that corresponds to a mixture of litter and soil Hg isotopic composition (resulting atmospheric δ202Hg, Δ200Hg and Δ199Hg were -1.79 ± 0.24‰, -0.05 ± 0.04‰ and -0.45 ± 0.12‰, respectively).

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.

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 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 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.

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.

Coupling of nitric acid digestion and anion-exchange resin separation for the determination of methylmercury isotopic composition within organisms.

Isotope ratios of methylmercury (MeHg) within organisms can be used to identify sources of MeHg that have accumulated in food webs, but these isotopic compositions are masked in organisms at lower trophic levels by the presence of inorganic mercury (iHg). To facilitate measurement of MeHg isotope ratios in organisms, we developed a method of extracting and isolating MeHg from fish and aquatic invertebrates for compound-specific isotopic analysis involving nitric acid digestion, batch anion-exchange resin separation, and pre-concentration by purge and trap. Recovery of MeHg was quantified after each step in the procedure, and the average cumulative recovery of MeHg was 93.4 ± 2.9% (1 SD, n = 28) for biological reference materials and natural biota samples and 96.9 ± 1.8% (1 SD, n = 5) for aqueous MeHgCl standards. The amount of iHg impurities was also quantified after each step, and the average MeHg purity was 97.8 ± 4.3% (1 SD, n = 28) across all reference materials and natural biota samples after the final separation step. Measured MeHg isotopic compositions of reference materials agreed with literature values obtained using other MeHg separation techniques, and MeHg isotope ratios of aqueous standards, reference materials, and natural biota samples were reproducible. On average, the reproducibility associated with reference material process replicates (2 SD) was 0.10‰ for δ202MeHg and 0.04‰ for Δ199MeHg. This new method provides a streamlined, reliable technique that utilizes a single sample aliquot for MeHg concentration and isotopic analysis. This promotes a tight coupling between MeHg concentration, %MeHg, and Hg isotopic composition, which may be especially beneficial for studying complex food webs with multiple isotopically distinct sources of iHg and/or MeHg.

Mercury isotopic evidence for the importance of particles as a source of mercury to marine organisms.

The origin of methylmercury in pelagic fish remains unclear, with many unanswered questions regarding the production and degradation of this neurotoxin in the water column. We used mercury (Hg) stable isotope ratios of marine particles and biota to elucidate the cycling of methylmercury prior to incorporation into the marine food web. The Hg isotopic composition of particles, zooplankton, and fish reveals preferential methylation of Hg within small (< 53 µm) marine particles in the upper 400 m of the North Pacific Ocean. Mass-dependent Hg isotope ratios (δ202Hg) recorded in small particles overlap with previously estimated δ202Hg values for methylmercury sources to Pacific and Atlantic Ocean food webs. Particulate compound specific isotope analysis of amino acids (CSIA-AA) yield δ15N values that indicate more-significant microbial decomposition in small particles compared to larger particles. CSIA-AA and Hg isotope data also suggest that large particles (> 53 µm) collected in the equatorial ocean are distinct from small particles and resemble fecal pellets. Additional evidence for Hg methylation within small particles is provided by a statistical mixing model of even mass-independent (Δ200Hg and Δ204Hg) isotope values, which demonstrates that Hg within near-surface marine organisms (0-150 m) originates from a combination of rainfall and marine particles. In contrast, in meso- and upper bathypelagic organisms (200-1,400 m), the majority of Hg originates from marine particles with little input from wet deposition. The occurrence of methylation within marine particles is supported further by a correlation between Δ200Hg and Δ199Hg values, demonstrating greater overlap in the Hg isotopic composition of marine organisms with marine particles than with total gaseous Hg or wet deposition.

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

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