Mercury Isotope Fractionation Research Articles

Mercury isotope fractionation and mercury source analysis in coal

Understanding the sources of mercury (Hg) in coal is crucial for understanding the natural Hg cycle in the Earth's system, as coal is a natural Hg reservoir. We conducted analyses on the mass-dependent fractionation (MDF), reported as δ202Hg, and mass-independent fractionation (MIF), reported as Δ199Hg, of Hg isotopes among individual Hg species and total Hg (THg) in Chinese coal samples. This data, supplemented by a review of prior research, allowed us to discern the varying trend of THg isotope fractionation with coal THg content. The Hg isotopic composition among identified Hg species in coal manifests notable disparities, with species exhibiting higher thermal stability tending to have heavier δ202Hg values, whereas HgS species typically display the most negative Δ199Hg values. The sources of Hg in coal are predominantly attributed to Hg accumulation from the original plant material and subsequent input from hydrothermal activity. Hg infiltrates peat swamps via vegetation debris, thus acquiring a negative Δ199Hg isotopic signature. Large-scale lithospheric Hg recycling via plate tectonics facilitates the transfer of Hg with a positive Δ199Hg from marine reservoirs to the deep crust. The later-stage hydrothermal input of Hg with a positive Δ199Hg enhances coal Hg content. This process has resulted in an upward trend of Δ199Hg values corresponding with the increase in coal THg content, ultimately leading to near-zero Δ199Hg in high-Hg coals. Coal Hg reservoirs are affected by large-scale natural Hg cycling, which involves the exchange of Hg between continents and seas.

Mercury Isotope Fractionation during Dark Abiotic Reduction of Hg(II) by Dissolved, Surface-Bound, and Structural Fe(II).

Stable mercury (Hg) isotope ratios are an emerging tracer for biogeochemical transformations in environmental systems, but their application requires knowledge of isotopic enrichment factors for individual processes. We investigated Hg isotope fractionation during dark, abiotic reduction of Hg(II) by dissolved iron(Fe)(II), magnetite, and Fe(II) sorbed to boehmite or goethite by analyzing both the reactants and products of laboratory experiments. For homogeneous reduction of Hg(II) by dissolved Fe(II) in continuously purged reactors, the results followed a Rayleigh distillation model with enrichment factors of -2.20 ± 0.16‰ (ε202Hg) and 0.21 ± 0.02‰ (E199Hg). In closed system experiments, allowing reequilibration, the initial kinetic fractionation was overprinted by isotope exchange and followed a linear equilibrium model with -2.44 ± 0.17‰ (ε202Hg) and 0.34 ± 0.02‰ (E199Hg). Heterogeneous Hg(II) reduction by magnetite caused a smaller isotopic fractionation (-1.38 ± 0.07 and 0.13 ± 0.01‰), whereas the extent of isotopic fractionation of the sorbed Fe(II) experiments was similar to the kinetic homogeneous case. Small mass-independent fractionation of even-mass Hg isotopes with 0.02 ± 0.003‰ (E200Hg) and ≈ -0.02 ± 0.01‰ (E204Hg) was consistent with theoretical predictions for the nuclear volume effect. This study contributes significantly to the database of Hg isotope enrichment factors for specific processes. Our findings show that Hg(II) reduction by dissolved Fe(II) in open systems results in a kinetic MDF with a larger ε compared to other abiotic reduction pathways, and combining MDF with the observed MIF allows the distinction from photochemical or microbial Hg(II) reduction pathways.

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.

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.

Mercury loss and isotope fractionation during thermal maturation of organic-rich mudrocks

Mercury (Hg) concentration and isotopic composition of organic-rich sedimentary rocks have been widely used as proxies to track ancient volcanism and associated environmental perturbations. However, interpretation of the Hg data is based on the assumption that the thermal maturity of the sedimentary rocks has limited effects on Hg abundance and isotopic composition, which is yet to be evaluated. Here we conduct closed-system anhydrous pyrolysis experiments to investigate the changes of Hg concentration and isotope composition during the thermal mature process, using both marine and lacustrine mudrocks. A siliceous shale section (Luocun, China) with heterogeneous thermal maturity caused by dike intrusion was also analyzed for Hg. Significant Hg loss (over 80%), with variations of δ202Hg (by 0.3 to 0.7‰) but small variations of Δ199Hg (by <0.1 to 0.36‰), were observed during the experiment. The Hg isotopic variation may be caused by the release of isotopically distinct Hg in different mineral phases at different temperatures. Samples from the Luocun section have anomalously low Hg and Hg/TOC values, due to thermal maturity. These findings suggest that (1) thermal maturation of organic-rich shales may be an important factor in distribution of Hg in sediments, and (2) the use of Hg, Hg/TOC and Hg isotopes proxies for paleoclimate and paleoceanography reconstruction should be applied in caution in substrates that may have experienced significant thermal alteration, especially if sill/dike intrusions were present that may cause large varieties of thermal maturity within sedimentary sections.

Mercury loss and isotope fractionation during high-pressure and high-temperature processing of sediments: Implication for the behaviors of mercury during metamorphism

Metamorphic rocks show much lower mercury (Hg) levels than sedimentary rocks, which may be due to the loss of Hg during high-pressure and high-temperature conditions during metamorphism. To test this hypothesis, we conduct high-pressure and high-temperature experiments on ancient and modern sediments (WH black shale and GSS-4 soil). Under 0.3 GPa, the Hg concentrations decrease while the δ202Hg values increase with rising temperatures (WH black shale: 333–89 ppb, −1.34 to −0.79‰, 250–700 °C; GSS-4: 545–265 ppb, −1.39 to −1.01‰, 400–700 °C), suggesting the loss of isotopically light Hg isotopes under high-temperature conditions. Under constant temperatures of both 200 °C and 500 °C, with increasing pressure (0.5–1.4 GPa), GSS-4 shows only a slight decrease in Hg concentration with no variation in δ202Hg, suggesting that high-pressure conditions restrain the loss of isotopically lighter isotopes. Consistent Δ199Hg and Δ200Hg values were observed in both samples during our experiment, implying no Hg isotope mass-independent fractionation (Hg-MIF) under high-temperature and high-pressure conditions. While results of this imply that metamorphism may lead to the emission of isotopically lighter Hg from sedimentary rocks to the surface environment, the lack of Hg-MIF during metamorphism provides important support for the use of Hg isotopes for paleoenvironment reconstruction.

Mantle Hg isotopic heterogeneity and evidence of oceanic Hg recycling into the mantle

The geochemical cycle of mercury in Earth’s surface environment (atmosphere, hydrosphere, biosphere) has been extensively studied; however, the deep geological cycling of this element is less well known. Here we document distinct mass-independent mercury isotope fractionation (expressed as Δ199Hg) in island arc basalts and mid-ocean ridge basalts. Both rock groups show positive Δ199Hg values up to 0.34‰ and 0.22‰, respectively, which deviate from recent estimates of the primitive mantle (Δ199Hg: 0.00 ± 0.10‰, 2 SD)1. The positive Δ199Hg values indicate recycling of marine Hg into the asthenospheric mantle. Such a crustal Hg isotope signature was not observed in our samples of ocean island basalts and continental flood basalts, but has recently been identified in canonical end-member samples of the deep mantle1, therefore demonstrating that recycling of mercury can affect both the upper and lower mantle. Our study reveals large-scale translithospheric Hg recycling via plate tectonics.

Mercury Isotope Fractionation during the Exchange of Hg(0) between the Atmosphere and Land Surfaces: Implications for Hg(0) Exchange Processes and Controls.

Atmosphere-surface exchange of elemental mercury (Hg(0)) is a vital component in global Hg cycling; however, Hg isotope fractionation remains largely unknown. Here, we report Hg isotope fractionation during air-surface exchange from terrestrial surfaces at sites of background (two) and urban (two) character and at five sites contaminated by Hg mining. Atmospheric Hg(0) deposition to soils followed kinetic isotope fractionation with a mass-dependent (MDF) enrichment factor of -4.32‰, and negligible mass-independent fractionation (MIF). Net Hg(0) emission generated average MDF enrichment factors (ε202Hg) of -0.91, -0.59, 1.64, and -0.42‰ and average MIF enrichment factors (E199Hg) of 0.07, -0.20, -0.14, and 0.21‰ for urban, background, and Hg mining soils and cinnabar tailing, respectively. Positive correlations between ε202Hg and ambient Hg(0) concentration indicate that the co-occurring Hg(0) deposition (accounting for 10-39%) in a regime of net soil emission grows with ambient Hg(0). The MIF of Hg(0) emission from soils (E199Hg range -0.27 to 0.14‰, n = 8) appears to be overall controlled by the photochemical reduction of kinetically constrained Hg(II) bonded to O ligands in background soils, while S ligands may have been more important in Hg mining area soils. In contrast, the small positive MIF of Hg(0) emission from cinnabar ore tailing (mean E199Hg = 0.21‰) was likely controlled by abiotic nonphotochemical reduction and liquid Hg(0) evaporation. This research provides critical observational constraints on understanding the Hg(0) isotope signatures released from and deposited to terrestrial surfaces and highlight stable Hg isotopes as a powerful tool for resolving atmosphere-surface exchange processes.

Mass-Independent Fractionation of Mercury Isotopes during Photoreduction of Soot Particle Bound Hg(II).

Soot and mercury (Hg) are two notorious air pollutants, and the fate and transport of Hg may be affected by soot at various scales in the environment as soot may be both a carrier and a reactant for active Hg species. This study was designed to quantify photoreduction of Hg(II) in the presence of soot and the associated Hg isotope fractionation under both atmospheric aerosol and aqueous conditions (water-saturated). Photoreduction experiments were conducted with diesel soot particulate matter under controlled temperature and relative humidity (RH) conditions using a flow-through semibatch reactor system. Mass-dependent fractionation resulted in the enrichment of heavier Hg isotopes in the remaining Hg(II) with enrichment factors (ε202Hg) of 1.48 ± 0.02‰ (±2 standard deviation) to 1.75 ± 0.05‰ for aerosol-phase reactions (RH 28-68%) and from 1.26 ± 0.11 to 1.50 ± 0.04‰ for aqueous-phase reactions. Positive odd mass-independent fractionation (MIF) was observed in aqueous-phase reactions, resulting in Δ199Hg values for reactant Hg(II) as high as 5.29‰, but negative odd-MIF occurred in aerosol-phase reactions, in which Δ199Hg values of reactant Hg(II) varied from -1.02 to 0‰. The average ratio of Δ199Hg/Δ201Hg (1.1) indicated that under all conditions, MIF was dominated by magnetic isotope effects during photoreduction of Hg(II). Increasing RH resulted in higher reduction rates but lower extents of negative MIF in the aerosol-phase experiments, suggesting that the reduction of soot particle-bound Hg(II) was responsible for the observed negative odd-MIF. Our results suggest that mass-independent Hg isotope fractionation during Hg(II) photoreduction varies with soot aerosol water content and that Hg-stable isotope ratios may be used to understand the transformational histories of aerosol-bound Hg(II) in the environment.

Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science.

A prerequisite for environmental and toxicological applications of mercury (Hg) stable isotopes in wildlife and humans is quantifying the isotopic fractionation of biological reactions. Here, we measured stable Hg isotope values of relevant tissues of giant petrels (Macronectes spp.). Isotopic data were interpreted with published HR-XANES spectroscopic data that document a stepwise transformation of methylmercury (MeHg) to Hg-tetraselenolate (Hg(Sec)4) and mercury selenide (HgSe) (Sec = selenocysteine). By mathematical inversion of isotopic and spectroscopic data, identical δ202Hg values for MeHg (2.69 ± 0.04‰), Hg(Sec)4 (-1.37 ± 0.06‰), and HgSe (0.18 ± 0.02‰) were determined in 23 tissues of eight birds from the Kerguelen Islands and Adélie Land (Antarctica). Isotopic differences in δ202Hg between MeHg and Hg(Sec)4 (-4.1 ± 0.1‰) reflect mass-dependent fractionation from a kinetic isotope effect due to the MeHg → Hg(Sec)4 demethylation reaction. Surprisingly, Hg(Sec)4 and HgSe differed isotopically in δ202Hg (+1.6 ± 0.1‰) and mass-independent anomalies (i.e., changes in Δ199Hg of ≤0.3‰), consistent with equilibrium isotope effects of mass-dependent and nuclear volume fractionation from Hg(Sec)4 → HgSe biomineralization. The invariance of species-specific δ202Hg values across tissues and individual birds reflects the kinetic lability of Hg-ligand bonds and tissue-specific redistribution of MeHg and inorganic Hg, likely as Hg(Sec)4. These observations provide fundamental information necessary to improve the interpretation of stable Hg isotope data and provoke a revisitation of processes governing isotopic fractionation in biota and toxicological risk assessment in wildlife.

Chemistry and Isotope Fractionation of Divalent Mercury during Aqueous Reduction Mediated by Selected Oxygenated Organic Ligands.

We have investigated the chemistry and Hg isotope fractionation during the aqueous reduction of HgII by oxalic acid, p-quinone, quinol, and anthraquinone-2,6-disulfonate (AQDS), a derivate of anthraquinone (AQ) that is found in secondary organic aerosols (SOA) and building blocks of natural organic matter (NOM). Each reaction was examined for the effects of light, pH, and dissolved O2. Using an excess of ligand, UVB photolysis of HgII was seen to follow pseudo-first-order kinetics, with the highest rate of ∼10-3 s-1 observed for AQDS and oxalic acid. Mass-dependent fractionation (MDF) occurs by the normal kinetic isotope effect (KIE). Only the oxalate ion, rather than oxalic acid, is photoreactive when present in HgC2O4, which decomposes via two separate pathways distinguishable by isotope anomalies. Upon UVB photolysis, only the reduction mediated by AQDS results in a large odd number mass-independent fractionation (odd-MIF) signified by enrichment of odd isotopes in the reactant. Consistent with the rate, MDF, and odd-MIF reported for fulvic acid, our AQDS result confirms previous assumptions that quinones control HgII reduction in NOM-rich waters. Given the magnitude of odd-MIF triggered via a radical pair mechanism and the significant rate in the presence of air, reduction of HgII by photoproducts of AQDS may help explain the positive odd-MIF observed in ambient aerosols depleted of HgII.

Equilibrium mercury and lead isotope fractionation caused by nuclear volume effects in crystals

To investigate equilibrium mercury (Hg) and lead (Pb) isotope fractionation caused by the nuclear volume effect (NVE) in crystals, the electron densities at nuclei (i.e., |Ψ(0)|2) for Hg- or Pb-bearing crystalline compounds were investigated by using the relativistic spin orbit zeroth-order regular approximation (ZORA) method with a three-dimensional periodic boundary condition based on the density functional theory (DFT). Many isotope fractionation factors of crystalline compounds are provided for the first time. Our results show, even at 1000 °C, NVE-driven Hg and Pb isotope fractionation are meaningfully large, i.e., range from 0.12‰ to 0.49‰ (202Hg/198Hg), from − 0.20‰ to 0.17‰ (208Pb/206Pb) and from − 0.08‰ to 0.06‰ (207Pb/206Pb) relative to Hg0 vapor and Pb0 vapor, respectively. Specifically, the fractionations range from − 0.06‰ to − 0.20‰ (208Pb/206Pb) and from − 0.02‰ to − 0.08‰ (207Pb/206Pb) for Pb2+-bearing species, from 0.10‰ to 0.17‰ (208Pb/206Pb) and from 0.04‰ to 0.06‰ (207Pb/206Pb) for Pb4+-bearing species in crystals. All calculated Hg-bearing species in crystals will enrich heavier isotope (202Hg) relative to Hg0 vapor. Meanwhile, Pb4+-bearing species enrich heavier Pb isotopes (208Pb and 207Pb) than Pb2+-bearing species in crystals, which the enrichment can be up to 0.37‰ (208Pb/206Pb) and 0.14‰ (207Pb/206Pb) at 1000 °C, due to their NVEs are in opposite directions. The NVE-driven MIFs of Hg isotopes, which are compared to the Hg202- Hg198 baseline, are up to − 0.158‰ ( $$\Delta {}_{{{\text{NV}}}}^{199} {\text{Hg}}$$ ), − 0.024‰ ( $$\Delta {}_{{{\text{NV}}}}^{200} {\text{Hg}}$$ ) and − 0.094‰ ( $$\Delta {}_{{{\text{NV}}}}^{201} {\text{Hg}}$$ ) relative to Hg0 vapor at 500 °C. For all studied Hg-bearing species in crystals, the MIFs of two odd-mass isotopes (i.e., $$\Delta {}_{{{\text{NV}}}}^{199} {\text{Hg}}$$ and $$\Delta {}_{{{\text{NV}}}}^{201} {\text{Hg}}$$ ) will be changed proportionally and their ratio (i.e., $$\Delta {}_{{{\text{NV}}}}^{199} {\text{Hg}}$$ / $$\Delta {}_{{{\text{NV}}}}^{201} {\text{Hg}}$$ ) will be a constant 1.67. The NVE can also cause mass-independent fractionations for 207Pb and 204Pb compared to the baseline of 208Pb and 206Pb. The largest NVE-driven MIFs are 0.043‰ ( $$\Delta {}_{{{\text{NV}}}}^{207} {\text{Pb}}$$ ) and − 0.040‰ ( $$\Delta {}_{{{\text{NV}}}}^{204} {\text{Pb}}$$ ) among all the studied species relative to Pb0 vapor at 500 °C. The magnitudes of odd-mass isotope MIF ( $$\Delta {}_{{{\text{NV}}}}^{207} {\text{Pb}}$$ ) and even-mass isotope MIF ( $$\Delta {}_{{{\text{NV}}}}^{204} {\text{Pb}}$$ ) are almost the same but with opposite signs, leading to the MIF ratio of them (i.e., $$\Delta {}_{{{\text{NV}}}}^{207} {\text{Pb}}$$ / $$\Delta {}_{{{\text{NV}}}}^{204} {\text{Pb}}$$ ) is − 1.08.

Recycling of mercury from the atmosphere-ocean system into volcanic-arc–associated epithermal gold systems

Abstract Photochemical processes generate mass-independent fractionation (MIF) of mercury (Hg) isotopes in the atmosphere-ocean system, and the subduction of marine sediments or hydrated oceanic crust may recycle the resultant Hg isotope signature into the volcanic-arc environment. This environment typically hosts epithermal gold deposits, which are characterized by a specific Hg-Sb-As metal association. We investigated the Hg isotopic composition of seven volcanic-arc–related epithermal gold deposits in northeast China and revisited the isotopic composition of Hg in hydrothermal ore deposits in circum-Pacific and Mediterranean volcanic arcs. The gold ore samples in northeast China mostly display positive Δ199Hg values (0.11‰ ± 0.07‰, 1σ, n = 48) similar to those observed in the Pacific Rim (0.07‰ ± 0.09‰, 1σ, n = 182) and the Mediterranean Cenozoic volcanic belt (0.09‰ ± 0.08‰, 1σ, n = 9). Because Hg in marine sediments and seawater has positive Δ199Hg, we infer that Hg-bearing epithermal deposits in active continental margin settings receive most Hg from recycled seawater in marine sediments, through the release of Hg by dehydration from the subducting oceanic slab. However, negative to near-zero Δ199Hg values were observed in Hg-bearing deposits in the South China craton (−0.09‰ ± 0.05‰, 1σ, n = 105) and in the intraplate magmatic-hydrothermal Almadén Hg deposit in Spain (−0.02‰ ± 0.06‰, 1σ, n = 26), which are considered to relate to basement and mantle sources, respectively. Hg isotopes have the potential to trace lithospheric Hg cycling.

Denitrification devices in urban boilers change mercury isotope fractionation signatures of coal combustion products.

The installation rate of denitrification devices is accelerating in Chinese urban boilers. Previous studies on pulverized coal-fired boilers without denitrification devices showed that combustion products containing mainly oxidized mercury (Hg) preferably enriched lighter Hg isotopes than feed coals. However, the magnitude of this enrichment becomes less pronounced if denitrification devices are installed. The underlying Hg isotope fractionation mechanisms are still unclear. In this study, three types of urban boilers (two pulverized coal-fired boilers, one circulating fluidized bed boiler and one municipal waste incinerator boiler) all installed with denitrification devices were measured for Hg isotope compositions of their feed fuels and corresponding combustion products. We observed little mass independent fractionation but very significant mass dependent fractionation (MDF) between feed fuels and combustion products. The fly ash and desulfurization products both enriched heavier Hg isotopes than feed coals in three coal-fired boilers, and the enrichment of heavy Hg isotopes increased with sequential removal of combustion products in all boilers. Different from previously suggested kinetic MDF for gaseous Hg0(g)→HgII(g) and gaseous HgII(g)→particulate HgII(p) in coal combustion flue gases, we propose an equilibrium MDF for Hg0(g)↔HgII(g) followed by a kinetic MDF for HgII(g)→HgII(p). This equilibrium MDF most likely occurs during Hg0(g) oxidation in denitrification devices, which enriches heavy Hg isotopes in oxidized products (HgII(g) and HgII(p)) that are then sequestrated in fly ash and desulfurization products. The paradigm shift of MDF in boilers with denitrification devices was further verified by parallel Hg isotope measurement in urban atmosphere particulates. Our study clearly demonstrates that modern coal-fired boilers with denitrification devices have a quite different MDF compared to traditional boilers without denitrification devices. This has important implications for estimating isotope signatures of urban boiler Hg emissions, and for isotope tracing of anthropogenic Hg emissions.

Mercury Isotope Fractionation during the Photochemical Reduction of Hg(II) Coordinated with Organic Ligands.

The photochemical reduction of Hg(II) is an important pathway in the environmental Hg cycle because it competes with Hg methylation and potentially limits the formation of bioaccumulative methylmercury. Hg stable isotope systematics have proven to be an effective tool for investigating the transport, transformation, and bioaccumulation of Hg. The dominant cause of mass independent isotope fractionation (MIF) of Hg in nature is the photochemical reduction of various species of Hg(II). However, it is difficult to fully interpret Hg stable isotope signatures due to the lack of mechanistic information about which Hg compounds are susceptible to MIF and why. This study investigates Hg isotope fractionation during the photochemical reduction of Hg(II) complexed to organic ligands, which are representative of the available binding sites in natural dissolved organic matter. The photochemical reduction of Hg(II) in the presence of cysteine resulted in both negative and positive MIF in residual Hg(II), where the sign depended on pH and dissolved oxygen level. In the presence of serine, either nuclear volume or magnetic isotope effects were observed depending on the wavelength of light and the extent of Hg(II) complexation by serine. In the presence of ethylenediamine, MIF was negative. Our Hg stable isotope results suggest that MDF and MIF are induced at different steps in the overall photochemical reduction reaction and that MIF does not depend on the rate-determining step but instead depends on photophysical aspects of the reaction such as intersystem crossing and hyperfine coupling. The behavior of Hg isotopes reported here will allow for a better understanding of the underlying reaction mechanisms controlling the Hg isotope signatures recorded in natural samples.

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.

In vivo fractionation of mercury isotopes in tissues of a mammalian carnivore (Neovison vison)

The use of isotope ratios to trace Hg contamination sources in environmental compartments is now generally accepted. However, for biota and especially for mammals, it is still unknown if and/or how Hg isotopes fractionate in vivo and which tissue is most representative of the source(s) of contamination. We measured fractionation of Hg in mink (Neovison vison) tissues (fur, brain, blood, liver, kidney) collected during a controlled feeding experiment where captive mink were fed differing amounts of methylmercury. There was no significant effect of dietary MeHg concentrations on Hg fractionation in most tissues. Net fractionation of Hg, i.e., fractionation corrected for diet (δ202Hgtissue−δ202Hgdiet) was observed in all tissues with the greatest net fractionation occurring in the mink liver (−1.39‰) and kidney (−0.95‰). Less net fractionation, occurred in the brain (−0.12‰), blood (0.38‰) and fur (0.30‰). In the absence of brain tissue, fur is a suitable proxy which is readily obtainable and can be non-lethally collected. In these mink, it appears that biochemical processes such as demethylation, contribute to significant fractionation of Hg in the liver and kidney, but not as much in the brain and fur, where transport of Hg via thiol-containing complexes may be more important.

Isotopic and chemical characteristics of mercury in organs and tissues of fish in a mercury-polluted lake: Evidence for fractionation of mercury isotopes by physiological processes.

Organs and tissues of whitefish and trout from mercury (Hg)-polluted Lake Ontario were analyzed for Hg isotopes, methylmercury (CH3 Hg+ ), and inorganic Hg to investigate possible mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes by physiological processes of the fish. Isotope signatures of different body parts were defined by δ-values of 198 Hg/202 Hg, 199 Hg/202 Hg, 200 Hg/202 Hg, and 201 Hg/202 Hg ratios and by Δ-values representing effects of MIF on 199 Hg/202 Hg and 201 Hg/202 Hg ratios. The research yielded the following evidence for MDF and MIF, including MIF of isotopes with even as well as odd mass numbers, by metabolic activities: 1) anomalously low δ-values for whitefish kidneys but not for trout kidneys; 2) widely varying differences between the δ-values of different body parts of whitefish but practically uniform differences for those of trout; 3) different relationships between Δ199 Hg and Δ201 Hg for whitefish than for trout; 4) nonlinear correlation between δ198 Hg and δ200 Hg for whitefish but linear correlation for trout; 5) an inverse correlation between the δ199 Hg values and CH3 Hg+ concentrations of whitefish and trout; 6) an inverse correlation between the δ201 Hg/δ199 Hg and CH3 Hg+ /inorganic Hg ratios of trout kidneys and gills (and lipids of trout near the sources of pollution) but a positive correlation for muscle, liver, and gut; and 7) inverse correlations between Δ199 Hg and the CH3 Hg+ /inorganic Hg ratio for trout liver, kidneys, and gut. Environ Toxicol Chem 2018;37:515-529. © 2017 SETAC.

Recent Developments in Mercury Stable Isotope Analysis

The first Reviews in Mineralogy volume on the Geochemistry of Non-Traditional Stable Isotopes was compiled before it was appropriate to include a chapter on mercury (Hg) stable isotope geochemistry. At that time there were only a few papers on this new topic (Jackson 2001; Lauretta et al. 2001; Hintelmann and Lu 2003), and there were still some important analytical issues that needed to be resolved. But the field has come a long way in a decade. Now we have a different problem; at our last count there were well over 100 publications utilizing mercury stable isotopes and it is becoming very difficult to synthesize this vast amount of exciting and rapidly developing research. Experimental studies have expanded our knowledge of the mechanisms of mercury isotope fractionation and applications of mercury isotope measurements have touched virtually every area of research in mercury biogeochemistry. There have been a number of previous reviews of the mercury stable isotope literature as it has developed (Ridley and Stetson 2006; Bergquist and Blum 2009; Yin et al. 2010; Blum 2011; Hintelmann 2012; Blum et al. 2014). It is our view that the field has become too large to comprehensively review the entire literature on mercury stable isotopes. Ten years ago Hg isotope researchers were just beginning to explore the boundaries of natural Hg isotope variation and the mechanisms that cause this variation in the environment. At that time large and relatively easily measured isotope signals were of great interest and mercury isotope researchers were beginning to develop theories to explain mass dependent isotope fractionation (MDF) and mass independent isotope fractionation of the odd mass-numbered isotopes of mercury (odd-MIF). More recently researchers have discovered a wider range of types of isotopic variability (even-MIF), some of which are subtle and …

Fractionation of mercury stable isotopes during coal combustion and seawater flue gas desulfurization

In the current study, fractionation of mercury isotopes during coal combustion and seawater flue gas desulfurization (SFGD) in a coal-fired power plant using a SFGD system was investigated. Fourteen samples were collected from the power plant. The samples were pretreated with a combustion-trapping method and were analyzed with a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). Compared with the raw coal, the bottom ash was enriched with lighter mercury isotopes with δ202Hg values ranging from −0.45 to −0.03‰. The fly ash was enriched with lighter mercury isotopes with δ202Hg values ranging from −1.49 to −0.73‰ for Chinese coal and from −1.47 to −0.62‰ for Indonesian coal. The δ202Hg of fresh seawater and desulfurized seawater was found to be −1.32 and −0.32‰ respectively. These δ202Hg values indicated that the desulfurized seawater was enriched with heavier mercury isotopes. Based upon the calculated results obtained from the mass balance equation, it was suggested that the stack emissions were enriched with lighter mercury isotopes. Mass independent fractionation was observed in most of the samples with a Δ199Hg/Δ201Hg ratio of approximately 0.96. The results help in improving the understanding of mercury isotope fractionation during coal combustion and SFGD, and are also useful in tracing the mercury emissions from coal fired power plants.