Isotope diffusion and re-equilibration of copper and evaporation of mercury during weathering of tetrahedrite in an oxidation zone

To understand the mobility of heavy metals during oxidative weathering of sulfides, we investigated weathering processes of tetrahedrite [(Cu,Fe,Zn,Hg)12(Sb,As)4S13] in an oxidation zone with abundant siderite (FeCO3) and baryte (BaSO4) at Rudňany (Slovakia). The focus of this work lied in the isotopic (δ65Cu, δ202Hg, δ34S) variations of the minerals during weathering and the interpretation of such changes. In the studied oxidation zone, Hg-rich tetrahedrite converts in situ to pockets of powdery cinnabar (HgS) and an X-ray amorphous mixture rich in Sb, Fe, and Cu that slowly re-crystallizes to Cu-rich tripuhyite (FeSbO4). Copper is mobile and precipitates as malachite [Cu2(OH)2(CO3)], azurite [Cu3(OH)2(CO3)2], or less abundant clinoclase [Cu3(AsO4)(OH)3]. The isotopic composition (δ65Cu) of tetrahedrite correlates well with the degree of weathering and varies between 0.0 ‰ and −4.0 ‰. This correlation is caused by isotopic changes during dissolution and subsequent rapid equilibration of δ65Cu values in the tetrahedrite relics. Simple diffusion models showed that equilibration of Cu isotopic values in the tetrahedrite relics proceeds rapidly, on the order of hundreds or thousands of years. Abundant secondary iron oxides draw light Cu isotopes from the aqueous solutions and shift the isotopic composition of malachite and azurite to higher δ65Cu values as the distance to the primary tetrahedrite increases. Clinoclase and tripuhyite have lower δ65Cu values and are spatially restricted near to the weathering tetrahedrite. The Hg and S isotopic composition of tetrahedrite is δ202Hg = −1.27 ‰, δ34S = −1.89 ‰, that of the powdery secondary cinnabar is δ202Hg = +0.07 ‰, δ34S = −5.50 ‰. The Hg isotopic difference can be explained by partial reduction of Hg(II) to Hg(0) by siderite and the following evaporation of Hg(0). The S isotopic changes indicate no involvement of biotic reactions in the oxidation zone, probably because of its hostility owing to high concentrations of toxic elements. This work shows that the Cu isotopic composition of the primary sulfides minerals changes during weathering through self-diffusion of Cu in those minerals. This finding is important for the use of Cu isotopes as tracers of geochemical cycling of metals in the environment. Another important finding is the Hg in the oxidation zones evaporates and contributes to the global cycling of this element through atmospheric emission

Solution speciation controls mercury isotope fractionation of Hg(II) sorption to goethite

The application of Hg isotope signatures as tracers for environmental Hg cycling requires the determination of isotope fractionation factors and mechanisms for individual processes. Here, we investigated Hg isotope fractionation of Hg(II) sorption to goethite in batch systems under different experimental conditions. We observed a mass-dependent enrichment of light Hg isotopes on the goethite surface relative to dissolved Hg (ε(202)Hg of -0.30‰ to -0.44‰) which was independent of the pH, chloride and sulfate concentration, type of surface complex, and equilibration time. Based on previous theoretical equilibrium fractionation factors, we propose that Hg isotope fractionation of Hg(II) sorption to goethite is controlled by an equilibrium isotope effect between Hg(II) solution species, expressed on the mineral surface by the adsorption of the cationic solution species. In contrast, the formation of outer-sphere complexes and subsequent conformation changes to different inner-sphere complexes appeared to have insignificant effects on the observed isotope fractionation. Our findings emphasize the importance of solution speciation in metal isotope sorption studies and suggest that the dissolved Hg(II) pool in soils and sediments, which is the most mobile and bioavailable, should be isotopically heavy, as light Hg isotopes are preferentially sequestered during binding to both mineral phases and natural organic matter

Source tracing of natural organic matter bound mercury in boreal forest runoff with mercury stable isotopes

Terrestrial runoff represents a major source of mercury (Hg) to aquatic ecosystems. In boreal forest catchments, such as the one in northern Sweden studied here, mercury bound to natural organic matter (NOM) represents a large fraction of mercury in the runoff. We present a method to measure Hg stable isotope signatures of colloidal Hg, mainly complexed by high molecular weight or colloidal natural organic matter (NOM) in natural waters based on pre-enrichment by ultrafiltration, followed by freeze-drying and combustion. We report that Hg associated with high molecular weight NOM in the boreal forest runoff has very similar Hg isotope signatures as compared to the organic soil horizons of the catchment area. The mass-independent fractionation (MIF) signatures (Δ; 199; Hg and Δ; 200; Hg) measured in soils and runoff were in agreement with typical values reported for atmospheric gaseous elemental mercury (Hg; 0; ) and distinctly different from reported Hg isotope signatures in precipitation. We therefore suggest that most Hg in the boreal terrestrial ecosystem originated from the deposition of Hg; 0; through foliar uptake rather than precipitation. Using a mixing model we calculated the contribution of soil horizons to the Hg in the runoff. At moderate to high flow runoff conditions, that prevailed during sampling, the uppermost part of the organic horizon (Oe/He) contributed 50-70% of the Hg in the runoff, while the underlying more humified organic Oa/Ha and the mineral soil horizons displayed a lower mobility of Hg. The good agreement of the Hg isotope results with other source tracing approaches using radiocarbon signatures and Hg : C ratios provides additional support for the strong coupling between Hg and NOM. The exploratory results from this study illustrate the potential of Hg stable isotopes to trace the source of Hg from atmospheric deposition through the terrestrial ecosystem to soil runoff, and provide a basis for more in-depth studies investigating the mobility of Hg in terrestrial ecosystems using Hg isotope signatures

Kinetics of Hg(II) exchange between organic ligands, goethite, and natural organic matter studied with an enriched stable isotope approach

The mobility and bioavailability of toxic Hg(II) in the environment strongly depends on its interactions with natural organic matter (NOM) and mineral surfaces. Using an enriched stable isotope approach, we investigated the exchange of Hg(II) between dissolved species (inorganically complexed or cysteine-, EDTA-, or NOM-bound) and solid-bound Hg(II) (carboxyl-/thiol-resin or goethite) over 30 days under constant conditions (pH, Hg and ligand concentrations). The Hg(II)-exchange was initially fast, followed by a slower phase, and depended on the properties of the dissolved ligands and sorbents. The results were described by a kinetic model allowing the simultaneous determination of adsorption and desorption rate coefficients. The time scales required to reach equilibrium with the carboxyl-resin varied greatly from 1.2 days for Hg(OH)2 to 16 days for Hg(II)-cysteine complexes and approximately 250 days for EDTA-bound Hg(II). Other experiments could not be described by an equilibrium model, suggesting that a significant fraction of total-bound Hg was present in a non-exchangeable form (thiol-resin and NOM: 53-58%; goethite: 22-29%). Based on the slow and incomplete exchange of Hg(II) described in this study, we suggest that kinetic effects must be considered to a greater extent in the assessment of the fate of Hg in the environment and the design of experimental studies, for example, for stability constant determination or metal isotope fractionation during sorption

Metal Stable Isotope Signatures as Tracers in Environmental Geochemistry

The biogeochemical cycling of metals in natural systems is often accompanied by stable isotope fractionation which can now be measured due to recent analytical advances. In consequence, a new research field has emerged over the last two decades, complementing the traditional stable isotope systems (H, C, O, N, S) with many more elements across the periodic table (Li, B, Mg, Si, Cl, Ca, Ti, V, Cr, Fe, Ni, Cu, Zn, Ge, Se, Br, Sr, Mo, Ag, Cd, Sn, Sb, Te, Ba, W, Pt, Hg, Tl, U) which are being explored and potentially applicable as novel geochemical tracers. This review presents the application of metal stable isotopes as source and process tracers in environmental studies, in particular by using mixing and Rayleigh model approaches. The most important concepts of mass-dependent and mass-independent metal stable isotope fractionation are introduced, and the extent of natural isotopic variations for different elements is compared. A particular focus lies on a discussion of processes (redox transformations, complexation, sorption, precipitation, dissolution, evaporation, diffusion, biological cycling) which are able to induce metal stable isotope fractionation in environmental systems. Additionally, the usefulness and limitations of metal stable isotope signatures as tracers in environmental geochemistry are discussed and future perspectives presented.ISSN:0013-936XISSN:1520-585

Metal Stable Isotope Signatures as Tracers in Environmental Geochemistry

The biogeochemical cycling of metals in natural systems is often accompanied by stable isotope fractionation which can now be measured due to recent analytical advances. In consequence, a new research field has emerged over the last two decades, complementing the traditional stable isotope systems (H, C, O, N, S) with many more elements across the periodic table (Li, B, Mg, Si, Cl, Ca, Ti, V, Cr, Fe, Ni, Cu, Zn, Ge, Se, Br, Sr, Mo, Ag, Cd, Sn, Sb, Te, Ba, W, Pt, Hg, Tl, U) which are being explored and potentially applicable as novel geochemical tracers. This review presents the application of metal stable isotopes as source and process tracers in environmental studies, in particular by using mixing and Rayleigh model approaches. The most important concepts of mass-dependent and mass-independent metal stable isotope fractionation are introduced, and the extent of natural isotopic variations for different elements is compared. A particular focus lies on a discussion of processes (redox transformations, complexation, sorption, precipitation, dissolution, evaporation, diffusion, biological cycling) which are able to induce metal stable isotope fractionation in environmental systems. Additionally, the usefulness and limitations of metal stable isotope signatures as tracers in environmental geochemistry are discussed and future perspectives presented

Organic matters, but inorganic matters too: column examination of elevated mercury sorption on low organic matter aquifer material using concentrations and stable isotope ratios

Sorption of mercury (Hg) in soils is suggested to be predominantly associated with organic matter (OM). However, there is a growing collection of research that suggests that clay minerals and Fe/Mn oxides are also important solid phases for the sorption of soluble Hg in soil–groundwater systems. We use a series of (60 mL syringe based) column experiments to examine sorption and subsequent desorption of HgCl2 solutions (experiment 1 (EXP1): 46.1 ± 1.1 mg L−1; experiment 2 (EXP2): 144 ± 6 mg L−1) in low-OM (0.16 ± 0.02 %) solid-phase aquifer materials. Analyses of total Hg concentrations, Hg speciation (i.e. pyrolytic thermal desorption (PTD)), and Hg stable isotopes are performed on both solid- and liquid-phase samples across sorption and desorption phases of the experiments. The sorption breakthrough curve best fitted a Freundlich model. Despite the very low-OM content, the Hg equilibrium sorptive capacity in these columns is very high: 1510 ± 100 and 2320 ± 60 mg kg−1 for EXP1 and EXP2, respectively, and it is similar to those determined for high-OM soils. Data from the experiments on mass-dependent Hg stable isotope fractionation data from these experiments (described by δ202Hg) support preferential sorption of lighter isotopes to the solid-phase materials with results indicating an isotopically heavier liquid phase and an isotopically lighter solid phase. Desorption fits exponential decay models, and 46 ± 6 % and 58 ± 10 % of the sorbed Hg is removed from the solid-phase materials at the termination of desorption in EXP1 and EXP2, respectively. The divergence of δ202Hg values between liquid and solid phases also continues into desorption. This desorption profile is linked to the initial release of easily exchangeable Hg(II) species physically sorbed to Fe/Mn oxides and clay mineral surfaces (liquid phase enriched in heavy isotopes) and then slower release of Hg(II) species that have undergone secondary reaction to more stable/less-soluble Hg(II) species and/or diffusion/transport into the mineral matrices (processes favouring lighter isotopes; solid phase enriched in lighter isotopes). The secondary production of Hg(0) within the columns is confirmed by PTD analyses that indicate distinct Hg(0) release peaks in solid-phase samples at <175 ∘C, which again agrees with field observations. Retardation (RD) and distribution (KD) coefficients are 77.9 ± 5.5 and 26.1 ± 3.0 mL g−1 in EXP1, respectively, and 38.4 ± 2.7 and 12.4 ± 0.6 mL g−1 in EXP2, respectively. These values are similar to values derived from column experiments on high-OM soil and provide the basis for future Hg fate and transport modelling in soil–groundwater systems

Mercury Isotope Fractionation during Precipitation of Metacinnabar (β-HgS) and Montroydite (HgO)

To utilize stable Hg isotopes as a tracer for Hg cycling and pollution sources in the environment, it is imperative that fractionation factors for important biogeochemical processes involving Hg are determined. Here, we report experimental results on Hg isotope fractionation during precipitation of metacinnabar (β-HgS) and montroydite (HgO). In both systems, we observed mass-dependent enrichments of light Hg isotopes in the precipitates relative to the dissolved Hg. Precipitation of β-HgS appeared to follow equilibrium isotope fractionation with an enrichment factor ε²⁰²Hg_{precipitate–supernatant} of −0.63‰. Precipitation of HgO resulted in kinetic isotope fractionation, which was described by a Rayleigh model with an enrichment factor of −0.32‰. Small mass-independent fractionation was observed in the HgS system, presumably related to nuclear volume fractionation. We propose that Hg isotope fractionation in the HgS system occurred in solution during the transition of O- to S-coordination of Hg­(II), consistent with theoretical predictions. In the HgO system, fractionation was presumably caused by the faster precipitation of light Hg isotopes, and no isotopic exchange between solid and solution was observed on the timescale investigated. The results of this work emphasize the importance of Hg solution speciation and suggest that bonding partners of Hg in solution complexes may control the overall isotope fractionation. The determined fractionation factor and mechanistic insights will have implications for the interpretation of Hg isotope signatures and their use as an environmental tracer

Equilibrium mercury isotope fractionation between dissolved Hg(II) species and thiol-bound Hg

Stable Hg isotope ratios provide a new tool to trace environmental Hg cycling. Thiols (-SH) are the dominant Hg-binding groups in natural organic matter. Here, we report experimental and computational results on equilibrium Hg isotope fractionation between dissolved Hg(II) species and thiol-bound Hg. Hg(II) chloride and nitrate solutions were equilibrated in parallel batches with varying amounts of thiol resin resulting in different fractions of thiol-bound and free Hg. Mercury isotope ratios in both fractions were analyzed by multiple collector inductively coupled plasma mass spectrometry (MC-ICPMS). Theoretical equilibrium Hg isotope effects by mass-dependent fractionation (MDF) and nuclear volume fractionation (NVF) were calculated for 14 relevant Hg(II) species. The experimental data revealed that thiol-bound Hg was enriched in light Hg isotopes by 0.53 per thousand and 0.62 per thousand (delta(202)Hg) relative to HgCl(2) and Hg(OH)(2), respectively. The computational results were in excellent agreement with the experimental data indicating that a combination of MDF and NVF was responsible for the observed Hg isotope fractionation. Small mass-independent fractionation (MIF) effects