Multi-element analysis of unfiltered samples in river water monitoring-digestion and single-run analyses of 67 elements.

Routine analysis of inorganic analytes in whole water samples from rivers (unfiltered river water) is rarely reported in scientific publications. However, this sample type is valuable and often used in long-term monitoring, regulation, and catchment element budgets, as it includes the dissolved, colloidal, and particulate fraction in one sample type. Preservation measures are not needed and solid-liquid partitioning can be disregarded, which simplifies automated sampling and storage procedures. In this study, we provide several digestion protocols for whole water samples from rivers and the subsequent multi-element analysis of 67 major, minor, and trace elements: Li, Be, B, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ru, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Ir, Pt, Au, Hg, Tl, Pb, Bi, Th, U. In the absence of whole water reference materials for inorganic analytes, we introduce simulated whole water samples by suspending sediment reference materials as quality control measures. The applicability for improved routine water quality monitoring was successfully tested on samples from different rivers revealing variations of the element fingerprints over time.

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.

Quantification of 68 elements in river water monitoring samples in single-run measurements.

Triple-quadrupole inductively coupled plasma mass spectrometry (ICP-QQQ-MS) is a unique analytical technique which is, next to speciation analyses, applied for the determination of total element concentrations in several matrices. Due to its wide linear range, short analysis times, and the collision-reaction gas technology, it is capable of addressing a high number of analytes in a single run with sufficient low limits of quantification for river water monitoring. Over the last decades, the focus of the environmental monitoring changed from "traditional" and regulated analytes to elements of possibly rising concern from new applications such as the so-called technology-critical elements (TCE). By widening the analytical window of this method for applications in networks of future river water monitoring, a better understanding of natural transport processes and global biogeochemical element cycles will be established and the total number of methods can be reduced. During method development and validation, certified reference materials, calibration check solutions, and spiked river water samples from 12 major German rivers covering different catchment areas were measured and evaluated with the three cell gases He, H2 and O2. The method delivers a best as possible undisturbed simultaneous determination for 68 out of 71 target analytes with recoveries in an accepted range of 80-120% for river water samples (dissolved fraction; <0.45 µm). After comprehensive evaluation, we offer a novel best-practice multi-element method for river water monitoring with the goal of fostering the exchange and discussion between practitioners in long-term river monitoring. It enables the readers to create their own methods based on the scientific needs to monitor elemental "fingerprints" of rivers and their catchments.

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.

Mercury isotope signatures of digests and sequential extracts from industrially contaminated soils and sediments.

Environmental mercury (Hg) pollution is a matter of global concern. Mercury speciation controls its environmental behaviour, and stable isotope ratios can potentially trace Hg movement through environmental compartments. Here we investigated Hg in industrially contaminated soils and sediments (Visp, Valais, Switzerland) using concentration and stable isotope analysis (CV-MC-ICP-MS) of total digests, and a four-step sequential extraction procedure. The sequential extraction employed (1) water (labile Hg species), (2) NaOH or Na4P2O7 (organically-bound Hg), (3) hydroxylamine-HCl (Hg bound to Mn and Fe (oxyhydr)oxides), and (4) aqua regia (residual Hg pools). The majority of Hg was extracted in step 4 and up to 36% in step 2. Mercury bound to organic matter was the dominant source of Hg in water, NaOH and Na4P2O7 extracts. Sulfides and colloidal oxide minerals were possible additional sources of Hg in some samples. The inconsistent comparative performance of NaOH and Na4P2O7 extractions showed that these classical extractants may not extract Hg exclusively from the organically-bound pool. Samples taken at the industrial facility displayed the greatest isotopic variation (δ202Hg: -0.80‰â€¯±â€¯0.14‰ to 0.25‰â€¯±â€¯0.13‰, Δ199Hg: -0.10‰â€¯±â€¯0.03‰ to 0.02‰â€¯±â€¯0.03‰; all 2SD) whereas downstream of the facility there was much less variation around average values of δ202Hg = -0.47‰â€¯±â€¯0.11‰ and Δ199Hg = -0.05‰â€¯±â€¯0.03‰ (1SD, n = 19). We interpret the difference as the result of homogenisation by mixing of canal sediments containing Hg from the various sources at the industrial facility with preservation of the mixed industrial Hg signature downstream. In contrast to previous findings, Hg isotopes in the sequential extracts were largely similar to one another (2SD < 0.14‰), likely demonstrating that the Hg speciation was similar among the extracts. Our results reveal that Hg resides in relatively stable soil pools which record an averaged isotope signature of the industrial sources, potentially facilitating source tracing studies with Hg isotope signatures at larger spatial scales further downstream.

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 (Δ199Hg and Δ200Hg) measured in soils and runoff were in agreement with typical values reported for atmospheric gaseous elemental mercury (Hg0) 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 Hg0 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.

Methyl Mercury Formation in Hillslope Soils of Boreal Forests: The Role of Forest Harvest and Anaerobic Microbes.

Final harvest (clear-cutting) of coniferous boreal forests has been shown to increase streamwater concentrations and export of the neurotoxin methyl mercury (MeHg) to freshwater ecosystems. Here, the spatial distribution of inorganic Hg and MeHg in soil as a consequence of clear-cutting is reported. A comparison of soils at similar positions along hillslopes in four 80 years old Norway spruce (Picea abies) stands (REFs) with those in four similar stands subjected to clear-cutting (CCs) revealed significantly (p < 0.05) enhanced MeHg concentrations (ng g(-1)), MeHg areal masses (g ha(-1)), and percent MeHg of HgTOT in O horizons of CCs located between 1 and 41 m from streams. Inorganic Hg measures did not differ between REFs and CCs at any position. The O horizon thickness did not differ between CCs and REFs, but the groundwater table and soil water content were significantly higher at CCs than at REFs. The largest difference in percent MeHg of HgTOT (12 times higher at CCs compared to REFs, p = 0.003) was observed in concert with a significant enhancement in soil water content (p = 0.0003) at intermediate hillslope positions (20-38 m from stream), outside the stream riparian zone. Incubation experiments demonstrated that soils having significantly enhanced soil pools of MeHg after clear-cutting also showed significantly enhanced methylation potential as compared with similarly positioned soils in mature reference stands. The addition of inhibitors demonstrated that sulfate-reducing bacteria (SRB) and methanogens were key methylators. Rates of demethylation did not differ between CCs and REFs. Our results suggest that enhanced water saturation of organic soils providing readily available electron donors stimulate Hg-methylating microbes to net formation and buildup of MeHg in O horizons after forest harvest.

Mercury deposition and re-emission pathways in boreal forest soils investigated with Hg isotope signatures.

Soils comprise the largest terrestrial mercury (Hg) pool in exchange with the atmosphere. To predict how anthropogenic emissions affect global Hg cycling and eventually human Hg exposure, it is crucial to understand Hg deposition and re-emission of legacy Hg from soils. However, assessing Hg deposition and re-emission pathways remains difficult because of an insufficient understanding of the governing processes. We measured Hg stable isotope signatures of radiocarbon-dated boreal forest soils and modeled atmospheric Hg deposition and re-emission pathways and fluxes using a combined source and process tracing approach. Our results suggest that Hg in the soils was dominantly derived from deposition of litter (∼90% on average). The remaining fraction was attributed to precipitation-derived Hg, which showed increasing contributions in older, deeper soil horizons (up to 27%) indicative of an accumulation over decades. We provide evidence for significant Hg re-emission from organic soil horizons most likely caused by nonphotochemical abiotic reduction by natural organic matter, a process previously not observed unambiguously in nature. Our data suggest that Histosols (peat soils), which exhibit at least seasonally water-saturated conditions, have re-emitted up to one-third of previously deposited Hg back to the atmosphere. Re-emission of legacy Hg following reduction by natural organic matter may therefore be an important pathway to be considered in global models, further supporting the need for a process-based assessment of land/atmosphere Hg exchange.

Mercury isotope fractionation during precipitation of metacinnabar (ß-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 (ß-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 ß-HgS appeared to follow equilibrium isotope fractionation with an enrichment factor ε(202)Hg(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.

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.

Mercury isotope signatures in contaminated sediments as a tracer for local industrial pollution sources.

Mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) may cause characteristic isotope signatures of different mercury (Hg) sources and help understand transformation processes at contaminated sites. Here, we present Hg isotope data of sediments collected near industrial pollution sources in Sweden contaminated with elemental liquid Hg (mainly chlor-alkali industry) or phenyl-Hg (paper industry). The sediments exhibited a wide range of total Hg concentrations from 0.86 to 99 µg g(-1), consisting dominantly of organically-bound Hg and smaller amounts of sulfide-bound Hg. The three phenyl-Hg sites showed very similar Hg isotope signatures (MDF δ(202)Hg: -0.2‰ to -0.5‰; MIF Δ(199)Hg: -0.05‰ to -0.10‰). In contrast, the four sites contaminated with elemental Hg displayed much greater variations (δ(202)Hg: -2.1‰ to 0.6‰; Δ(199)Hg: -0.19‰ to 0.03‰) but with distinct ranges for the different sites. Sequential extractions revealed that sulfide-bound Hg was in some samples up to 1‰ heavier in δ(202)Hg than organically-bound Hg. The selectivity of the sequential extraction was tested on standard materials prepared with enriched Hg isotopes, which also allowed assessing isotope exchange between different Hg pools. Our results demonstrate that different industrial pollution sources can be distinguished on the basis of Hg isotope signatures, which may additionally record fractionation processes between different Hg pools in the sediments.

Stable Hg isotope signatures in creek sediments impacted by a former Hg mine.

The goal of this study was to investigate the Hg stable isotope signatures of sediments in San Carlos Creek downstream of the former Hg mine New Idria, CA, USA and to relate the results to previously studied Hg isotope signatures of unroasted ore waste and calcine materials in the mining area. New Idria unroasted ore waste was reported to have a narrow δ(202)Hg range (−0.09 to 0.16‰), while roasted calcine materials exhibited a very large variability in δ(202)Hg (−5.96 to 14.5‰). In this study, creek sediment samples were collected in the stream bed from two depths (0­10 and 10­20 cm) at 10 locations between the mine adit and 28 km downstream. The sediment samples were size-fractionated into sand, silt, and (if possible) clay fractions as well as hand-picked calcine pebbles. The sediment samples contained highly elevated Hg concentrations (8.2 to 647 µg g(­1)) and displayed relatively narrow mass-dependent fractionation (MDF, δ(202)Hg; ± 0.08‰, 2SD) ranges (−0.58 to 0.24‰) and little to no mass-independent fractionation (MIF, Δ(199)Hg; ± 0.04‰, 2SD) (0.00 to 0.10‰), similar to what was observed previously for the unroasted ore waste. However, due to the highly variable and overlapping δ(202)Hg signatures of the calcines, they could not be ruled out as source of Hg to the creek sediments. Overall, our results suggest that analyzing creek sediments downstream of former Hg mines can provide a more reliable Hg isotope source signature for tracing studies at larger spatial scales, than analyzing the isotopically highly heterogeneous tailing piles typically found at former mining sites. Creek sediments carry an integrated isotope signature of Hg transported away from the mine with runoff into the creek, eventually affecting ecosystems downstream.

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.

Mercury isotope signatures as tracers for Hg cycling at the New Idria Hg mine.

Mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes provides a new tool for tracing Hg in contaminated environments such as mining sites, which represent major point sources of Hg pollution into surrounding ecosystems. Here, we present Hg isotope ratios of unroasted ore waste, calcine (roasted ore), and poplar leaves collected at a closed Hg mine (New Idria, CA, U.S.A.). Unroasted ore waste was isotopically uniform with δ(202)Hg values from -0.09 to 0.16‰ (± 0.10‰, 2 SD), close to the estimated initial composition of the HgS ore (-0.26‰). In contrast, calcine samples exhibited variable δ(202)Hg values ranging from -1.91‰ to +2.10‰. Small MIF signatures in the calcine were consistent with nuclear volume fractionation of Hg isotopes during or after the roasting process. The poplar leaves exhibited negative MDF (-3.18 to -1.22‰) and small positive MIF values (Δ(199)Hg of 0.02 to 0.21‰). Sequential extractions combined with Hg isotope analysis revealed higher δ(202)Hg values for the more soluble Hg pools in calcines compared with residual HgS phases. Our data provide novel insights into possible in situ transformations of Hg phases and suggest that isotopically heavy secondary Hg phases were formed in the calcine, which will influence the isotope composition of Hg leached from the site.

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.

Iron isotope fractionation during Fe uptake and translocation in alpine plants.

The potential of stable Fe isotopes as a tracer for the biogeochemical Fe cycle depends on the understanding and quantification of the fractionation processes involved. Iron uptake and cycling by plants may influence Fe speciation in soils. Here, we determined the Fe isotopic composition of different plant parts including the complete root system of three alpine plant species (Oxyria digyna, Rumex scutatus, Agrostis gigantea) in a granitic glacier forefield, which allowed us, for the first time, to distinguish between uptake and in-plant fractionation processes. The overall range of fractionation was 4.5 per thousand in delta(56)Fe. Mass balance calculations demonstrated that fractionation toward lighter Fe isotopic composition occurred in two steps during uptake: (1) before active uptake, probably during mineral dissolution and (2) during selective uptake of Fe at the plasma membrane with an enrichment factor of -1.0 to -1.7 per thousand for all three species. Iron isotopes were further fractionated during remobilization from old into new plant tissue, which changed the isotopic composition of leaves and flowers over the season. This study demonstrates the potential of Fe isotopes as a new tool in plant nutrition studies but also reveals challenges for the future application of Fe isotope signatures in soil-plant environments.

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 (<0.1 per thousand) were observed representing one of the first experimental evidences for MIF of Hg isotopes by NVF. Our results indicate that significant equilibrium Hg isotope fractionation can occur without redox transition, and that NVF must be considered in addition to MDF to explain Hg isotope variations.

Iron isotope fractionation during proton-promoted, ligand-controlled, and reductive dissolution of Goethite.

Iron isotope fractionation during dissolution of goethite (alpha-FeOOH) was studied in laboratory batch experiments. Proton-promoted (HCl), ligand-controlled (oxalate dark), and reductive (oxalate light) dissolution mechanisms were compared in order to understand the behavior of iron isotopes during natural weathering reactions. Multicollector ICP-MS was used to measure iron isotope ratios of dissolved iron in solution. The influence of kinetic and equilibrium isotope fractionation during different time scales of dissolution was investigated. Proton-promoted dissolution did not cause iron isotope fractionation, concurrently demonstrating the isotopic homogeneity of the goethite substrate. In contrast, both ligand-controlled and reductive dissolution of goethite resulted in significant iron isotope fractionation. The kinetic isotope effect, which caused an enrichment of light isotopes in the early dissolved fractions, was modeled with an enrichment factor for the 57Fe/ 54Fe ratio of -2.6 per thousandth between reactive surface sites and solution. Later dissolved fractions of the ligand-controlled experiments exhibit a reverse trend with a depletion of light isotopes of approximately 0.5 per thousandth in solution. We interpret this as an equilibrium isotope effect between Fe(III)-oxalate complexes in solution and the goethite surface. In conclusion, different dissolution mechanisms cause diverse iron isotope fractionation effects and likely influence the iron isotope signature of natural soil and weathering environments.