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Zinc (Zn) is a bioessential element whose cycling in the marine environment is closely linked to the biological pump. As a vital micronutrient, Zn is depleted in marine surface waters and enriched in deep waters. This has given rise to the longstanding hope that Zn could serve as a robust paleoproductivity proxy. There has been a recent focus on how Zn isotope signatures can be used to track the evolution of the biological pump. However, the factors controlling variations in the sedimentary Zn isotope composition of core-top sediments are debated and these values are influenced by changes in the relative contributions of biological uptake and scavenging processes and by mineral fractionations. In order to provide a new perspective on the Zn isotopic signature of marine core-top sediments and their potential for tracing ocean biogeochemical processes, we developed a sample preparation procedure to extract organically bound Zn (excluding inorganic Zn) without a significant isotope fractionation. We tested five potential organic solvents and found that the isopropanol extraction procedure provided a reproducible and robust result that yielded the highest recovery rate of organically bound Zn without a significant associated isotopic fractionation and appeared to exclude common mineral bound forms of Zn. This extraction procedure was used to analyze the Zn concentrations and isotopic compositions (δ66Zn) of core-top sediment samples from Long Island Sound and the Peruvian continental margin. Our results suggest that the δ66Zn value of organic Zn increases with water depth, thus providing additional support for the finding that burial of isotopically light Zn occurs predominantly in shallow high-productivity sediments. However, we also found that the δ66Zn values of the estimated authigenic Zn component are consistently lighter than those of the organic Zn fraction, consistent with diagenetic (sediment pile) scavenging of organic derived Zn in sulfides imparting an isotope fractionation.

Oceans play a key role in the global mercury (Hg) cycle, but studies on Hg isotopes in seawater are rare due to the extremely low Hg concentration and the lack of a good preconcentration method. Here, we introduce a new coprecipitation method for separating and preconcentrating Hg from seawater for accurate isotope measurement. The coprecipitation was achieved by sequential addition of 0.5 mL of 0.5 M CuSO4, 1 mL of 0.5 M Na2S, and 1 mL of 0.5 M CuSO4 reagents, which allowed for quantitatively precipitating Hg from up to 10 L of seawater. The protocol was validated by testing synthetic solutions with varying Hg and iodide (I-) concentrations and by comparing the reaction times of various reagents added. The method resulted in a quantitative recovery of 98 ± 12% (n = 32, two standard deviations, 2 SD) and a relatively low procedure blank (103 pg of Hg, n = 8). The precipitates were filtrated and analyzed for Hg isotopes. Repeated measurements of synthetic seawaters spiked with certificated standard materials (NIST 3133 and 3177) using the entire method gave identical Hg isotope ratios with near-quantitative Hg recovery, indicating no isotope fractionation during preconcentration. A total of six nearshore seawater samples from the Yellow Sea and the Bohai Sea (China) were analyzed using the coprecipitation method. The data showed a large fractionation of Hg isotopes and revealed the possible impact of both atmospheric and anthropogenic inputs to the coastal seawater Hg budget, implying the potential application of this method in studying marine Hg systematics and global Hg cycling.

Ammonium nitrate (AN) is one of the most commonly used explosives in criminal cases. The comparison and source-tracing of AN is important for investigation of attribution and fingerprinting of an explosive used at different events. The stable isotope signature of AN is an important index for comparison and tracing. However, the characteristics of the stable nitrogen isotopic ratios of AN (δ15 NNH4NO3 ) alone are not sufficient to achieve a fine comparison between different AN samples. To increase the comparison index and further improve the discriminability between stable nitrogen isotopic ratios of different ANs, a method of isolation and analysis of nitrate ions in AN was established using stable-isotope-ratio mass spectrometry (IRMS). The method was based on the principle that strong alkali react with AN to produce ammonia and nitrate. After the isolation, stable nitrogen isotopes of nitrate ions (δ15 NNO3 ) were obtained using IRMS, and then the stable nitrogen isotopes of ammonium ions from AN (δ15 NNH4 ) was calculated according to the principle of mass balance. The results show that the method is effective for the isolation of nitrate ions without notable isotope fractionation. The developed method was applied to analyze and discriminate AN samples from eight different cities in China. Three samples out of the initial eight AN samples with similar δ15 NNH4NO3 values were further distinguished by their δ15 NNH4 and δ15 NNO3 values. The isolation and stable-nitrogen isotopic analysis method developed for nitrate ions in AN is simple and effective, thereby increasing the discriminability of the stable isotope ratios in AN.

Molybdenum (Mo) and tungsten (W) concentration patterns and isotope signatures are widely used to study changes in ocean redox conditions. This is in part due to the differential adsorption of Mo and W onto various types of minerals that are abundant under different redox regimes. The speciation of Mo and W, which also varies under different redox conditions, greatly controls their particle reactivities in the environment. Manganese (Mn) oxide minerals can not only provide surfaces for Mo and W adsorption, but also catalyze Mo and W speciation change. Thus, the Mn oxides that are often present at redox interfaces can play an important role in Mo and W speciation change. However, we lack knowledge of how rates for Mn oxide catalyzed Mo and W speciation transformation compare to rates for their adsorption and isotope fractionation processes, which creates uncertainty in our ability to interpret Mo and W concentration and isotope patterns in sediments and sedimentary rocks. Here, we present data that constrain rates, environmental controls, and mechanisms for tetrathiomolybdate (MoS42–) and tetrathiotungstate (WS42–) hydrolysis on Mn oxide surfaces, which transforms the thioanion species to oxyanion species. The experimental results show that hydrolysis rate constants for these Mo and W thioanions are first order with respect to Mn oxide surface areas. Hence, high abundance of Mn oxides in aquatic environments greatly catalyzes MoS42– and WS42– hydrolysis. In addition, experimental results indicate that crystal structure differences of Mn oxides contribute to differences in rates for Mo and W thioanion hydrolysis reactions. Solution pH and ionic strength have limited impacts on Mo and W thioanion hydrolysis rates catalyzed by Mn oxides, while sulfate has a moderate impact. Geochemical modeling results indicate that equilibrium times for MoS42– and WS42– hydrolysis reactions in the presence of Mn oxides at abundances found in the modern ocean are three orders of magnitude longer than those for adsorption and isotope fractionation of Mo and W on Mn oxide surfaces. This implies that Mn oxides play a larger role in affecting adsorption and isotope fractionation processes than Mo and W speciation transformation in the modern, well-oxygenated ocean. In contrast, the potentially high levels of dissolved Mn(II) in the Archean ocean would have shortened the equilibrium time for Mo or W speciation transformation such that this process could compete with their adsorption and isotope fractionation processes, and subsequently affect sedimentary Mo and W isotope records. The impact of dissolved Mn(II) catalyzed Mo and W speciation change should be considered in future studies of Archean Mo and W isotope records.

Oxygen stable isotopes in uranium oxides processed through the nuclear fuel cycle may have the potential to provide information about a material's origin and processing history. However, a more thorough understanding of the fractionating processes governing the formation of signatures in real-world samples is still needed. In this study, laboratory synthesis of uranium oxides modeled after industrial nuclear fuel fabrication was performed to follow the isotope fractionation during thermal decomposition and reduction of ammonium diuranate (ADU). Synthesis of ADU occurred using a gaseous NH3 route, followed by thermal decomposition in a dry nitrogen atmosphere at 400, 600, and 800 °C. The kinetic impact of heating ramp rates on isotope effects was explored by ramping to each decomposition temperature at 2, 20, and 200 °C min-1. In addition, ADU was reduced using direct (ramped to 600 °C in a hydrogen atmosphere) and indirect (thermally decomposed to U3O8 at 600 °C, then exposed to a hydrogen atmosphere) routes. The bulk oxygen isotope composition of ADU (δ18O = -16 ± 1‰) was very closely related to precipitation water (δ18O = -15.6‰). The solid products of thermal decomposition using ramp rates of 2 and 20 °C min-1 had statistically indistinguishable oxygen isotope compositions at each decomposition temperature, with increasing δ18O values in the transition from ADU to UO3 at 400 °C (δ18OUO3 - δ18OADU = 12.3‰) and the transition from UO3 to U3O8 at 600 °C (δ18OU3O8 - δ18OUO3 = 2.8‰). An enrichment of 18O attributable to water volatilization was observed in the low temperature (400 °C) product of thermal decomposition using a 200 °C min-1 ramp rate (δ18OUO3 - δ18OADU = 9.2‰). Above 400 °C, no additional fractionation was observed as UO3 decomposed to U3O8 with the rapid heating rate. Indirect reduction of ADU produced UO2 with a δ18O value 19.1‰ greater than the precipitate and 4.0‰ greater than the intermediate U3O8. Direct reduction of ADU at 600 °C in a hydrogen atmosphere resulted in the production of U4O9 with a δ18O value 17.1‰ greater than the precipitate. Except when a 200 °C min-1 ramp rate is employed, the results of both thermal decomposition and reduction show a consistent preferential enrichment of 18O as oxygen is removed from the original precipitate. Hence, the calcination and reduction reactions leading to the production of UO2 will yield unique oxygen isotope fractionations based on process parameters including heating rate and decomposition temperature.

Microbial and hydrothermal venting activities on the seafloor are important for the formation of sediment-hosted stratiform sulfide (SHSS) deposits. Fe isotopic compositions are sensitive to both microbial and hydrothermal activities and may be used to investigate the formation of these deposits. However, to the best of our knowledge, no Fe isotopic studies have been conducted on SHSS deposits. In the Devonian Dajiangping SHSS-type pyrite deposit (389 Ma), South China, laminated pyrite ores were precipitated from exhalative hydrothermal fluids, whereas black shales were deposited during intervals with no exhalation. Pyrite grains from black shales mostly display positive δ56Fe-py (0.01–0.73‰), higher than marine sediments (ca. 0‰), due to pyrite deriving Fe from basinal shuttled Fe(III) (hydr-)oxides and slowly crystallizing in pores of sediments with equilibrium fractionation, except for negative δ56Fe-py (−0.17‰ to −0.24‰) of two samples caused by mixing of Fe from underlain laminated ores. The positive δ34S-py (3.50–24.5‰) of black shales reflect that sulfur of pyrite originated from quantitative reduction of sulfate in closed pores of sediments. In contrast, pyrite grains of laminated ores have negative δ56Fe-py (−0.60‰ to −0.21‰), which were not only inherited from the negative δ56Fe of hydrothermal fluids but also caused by kinetic fractionation during rapid precipitation of a pyrite precursor (FeS) in hydrothermal plumes. These ores have negative δ34S-py (−28.7‰ to −1.82‰), because H2S for pyrite mineralization was produced by bacterial sulfate reduction (BSR) in a sulfate-rich seawater column or shallow sediments. The δ56Fe-py values of laminated ores co-vary positively with δ34S-py and δ13C-carbonate along the ore stratigraphy, with δ13C-carbonate values ranging from −12.0‰ to −2.50‰. However, they correlate negatively with aluminum-normalized total organic carbon (TOC/Al2O3). Organic carbon is thus considered to enhance the production of H2S by BSR activities, increase pyrite precipitation rates and promote the expression of kinetic fractionation of Fe isotopes. Intriguingly, in the ore units with vigorous hydrothermal venting activities, δ56Fe-py, δ34S-py and δ13C-carbonate values display a consistently increasing trend. Such results suggest that venting hydrothermal fluids significantly inhibited the H2S production of BSR, which then reduced the pyrite crystallization rate and decreased the kinetic fractionation of Fe isotopes. Our study reveals that the formation of SHSS deposits relies on H2S from microbial activities and metals from hydrothermal exhalation on the seafloor, but that vigorous exhalation can inhibit microbial activities and thus sulfide precipitation rates. The integrated use of Fe, S, and C isotopes can effectively elucidate these dynamic interactions between hydrothermal venting and microbial activities during the formation of SHSS deposits.

Sediment-hosted marine sulfur cycling has played a significant role in regulating Earth's surface chemistry over our planet's history. Microbially-mediated reactions involving sulfur are often accompanied by sulfur isotope fractionation that, in turn, is captured by sulfate and sulfide minerals, providing the opportunity to track changes in the microbial utilization of sulfur and thus the marine sulfur cycle. Studying sulfur diagenesis within the Bornholm Basin, Baltic Sea, we explore the interplay between carbon, sulfur and iron, focusing on the fate of sulfur and the dynamics of the sulfur and oxygen isotopic response as a function of the varying thickness of the organic carbon-rich Holocene Mud Layer (HML) across the basin. Using a one-dimensional reaction-transport model, porewater sulfate and sulfide profiles were used to calculate net sulfate reduction rates (SRR) and net sulfide production rates, respectively. These calculations suggest a positive relationship between the thickness of the HML and net rates of sulfate reduction and sulfide production. Given that ascending sulfide is enriched in 34S relative to that produced in-situ, a heightened sulfide flux promotes spatially variable precipitation of 34S-enriched pyrite (δ34S ≈ −10‰) close to the sediment–water interface. Modeling results indicate that this isotopically “heavy” sulfide is formed as a consequence of mixing between ascending sulfide (up to +6.3‰) and that produced in-situ (ca. −40‰). Further, we show that the sulfur and oxygen isotopic composition of porewater sulfate is controlled by the net SRR: when the net SRR is high (i.e., in sulfide-replete settings) the downcore increase in δ18OSO4 is dampened relative to increase in δ34SSO4, whereas when net SRR is low (i.e., in iron-rich parts of the basin) downcore δ18OSO4 values increase while δ34SSO4 values remain invariant. We conclude that sedimentation rates and open system diffusion strongly influence the distribution of sulfur species and their sulfur isotopic composition, as well as the oxygen isotopic composition of sulfate, through the interaction between iron, sulfur and methane. This work highlights the importance of considering diffusion to better understand open system diagenesis and the δ34S signatures of sulfate and sulfide in both modern settings and ancient rocks.

How and when Earth’s volatile content was established is controversial with several mechanisms postulated, including planetesimal evaporation, core formation and the late delivery of undifferentiated chondrite-like materials. The isotopes of volatile elements such as sulfur can be fractionated during planetary accretion and differentiation and thus are potential tracers of these processes. Using first-principles calculations, we examine sulfur isotope fractionation during core formation and planetesimal evaporation. We find no measurable sulfur isotope fractionation between silicate and metallic melts at core-forming conditions, indicating that the observed light sulfur isotope composition of the bulk silicate Earth relative to chondrites cannot be explained by metal–silicate fractionation. Our thermodynamic calculations show that sulfur evaporates mostly as H2S during planetesimal evaporation when nebular H2 is present. The observed bulk Earth sulfur isotope signature and abundance can be reproduced by evaporative loss of about 90% sulfur mainly as H2S from molten planetesimals before nebular H2 is dissipated. The heavy sulfur isotope composition of the Moon relative to the Earth is consistent with evaporative sulfur loss under 94–98% saturation condition during the Moon-forming giant impact. In summary, volatile evaporation from molten planetesimals before Earth’s formation probably played a key role in establishing Earth’s volatile element content. Earth’s volatile element content was established largely by volatile evaporation from molten planetesimals before Earth’s formation, according to first-principles calculations and examination of sulfur isotope fractionation.

Author(s): Eldridge, DL; Kamyshny, A; Farquhar, J | Abstract: Inorganic polysulfur compounds (polysulfides, Sx2-; polysulfur radical ions, Sx·-; thiosulfate, S2O32-; polythionate, SxO62-; elemental sulfur, e.g. S8) participate in numerous geochemical processes related to the sulfur cycle. These include authigenic pyrite formation in sediments undergoing early stages of diagenesis, reactions associated with magmatic-hydrothermal processes, and numerous other aquatic sulfur redox processes (e.g., pyrite and sulfide oxidation). Sulfur isotope fractionations among many of these and associated compounds (e.g., H2S, HSO4-) are either unknown or unconstrained over wide ranges of temperatures. We present theoretical estimates of equilibrium sulfur isotope fractionation factors among aqueous polysulfur compounds (including select polysulfides, polysulfur radical anions, and polythionates) and select aqueous sulfide and sulfate compounds that correspond to all three stable isotope ratios of sulfur (33S/32S, 34S/32S, 36S/32S). Our estimates are based on electronic structure calculations performed at the B3LYP/6–31+G(d,p) level of theory and basis set implemented in concert with an explicit solvation model whereby molecules are encapsulated in water clusters of varying size (30–52 H2O) to simulate the aqueous solvation environment. These calculations yield relatively small magnitude fractionation factors between aqueous polysulfides, polysulfur radicals, and reduced sulfur moieties in polythionates relative to the aqueous sulfide compounds but reveal numerous crossovers that result in non-intuitive temperature dependencies. Our predictions of 34S/32S-based fractionation factors among aqueous sulfur compounds generally agree with previous experimental constraints where available within estimated uncertainties (e.g., HSO4-/H2S(aq), H2S(aq)/HS-, HSO4-/S0, H2S(aq)/S0). We use our calculations to explore equilibrium isotope fractionations among polysulfur and sulfide compounds that are precursors to authigenic pyrite in the framework of established mechanisms (e.g., the polysulfide mechanism). We examine possible explanations for why pyrite formation may be associated with relatively small isotope fractionation with respect to precursor aqueous sulfur compounds. We additionally use our theoretical calculations to constrain multiple sulfur isotope (33S/32S, 34S/32S, 36S/32S) mass balance models associated with the abiotic hydrolytic disproportionation of intermediate sulfur compounds (SO2, S8, S3·-) relevant to hydrothermal-magmatic-volcanic systems in order to illustrate the potential for subtle but potentially resolvable effects expressed in values of Δ33S and Δ36S associated with these processes. We apply a SO2 disproportionation mass balance model based on previous work but newly constrained by our theoretical calculations to (hyper-) acid crater lakes associated with active volcanoes, and newly highlight the potential for the utility of multiple sulfur isotope analyses in volcanic gas monitoring and constraining sulfur cycling processes in such systems.

The elemental and isotopic fractionation of lithium between inorganic calcite and aqueous solutions has been measured as a function of solution chemistry in mixed CaCl2-NaHCO3 aqueous solutions spanning a range of pH from ~6 to ~9.5 at room temperature. Vaterite added to the solution recrystallized to calcite with limited change in solution chemistry. With this experimental design solution pH and Na/Ca strongly correlate. The ratio of the concentration of Li in the calcite to that of the solution (Kd,Li = [Li]calcite/[Li]solution), increased by about an order of magnitude with increasing pH. The Li exchange coefficient (Kd,Li/Ca=([Li]calcite/[Ca]calcite)/([Li]solution/[Ca]solution) decreased by about four orders of magnitude, from ~10−2 to ~10−6 with increasing pH due to the large decrease in solution Ca content with increasing experiment pH. The Li isotope fractionation also changed systematically as the pH of the solution increased from 6.5 to 9.5 with the calcite ranging from about −6‰ to +2‰ relative to the solution it grew from. No change in either the elemental or isotopic partitioning was observed with either a change in the Li concentration of the solution or with a change in the experimental duration (5–400 days). To better understand the role of diffusive Li isotope fractionation a series of experiments were performed to determine the relative diffusivity of 6Li and 7Li in solutions with different pH. The results suggest little or no difference in relative diffusivity (D6Li ~ 0.998D7Li) across the range of solution chemistry considered (pH 4 to ~7.5). The change in Li partitioning between calcite and solution with changing solution chemistry is consistent with Li incorporation into calcite as LiHCO3 and hence a dependence on solution H+/Ca2+. If this interpretation is correct, it means that the concentration of Li in inorganic calcite precipitated from seawater at fixed Ca and Li concentrations will increase with decreasing pH. The change in the Li isotope fractionation factor with changing solution chemistry may either reflect a kinetic isotope fractionation associated with changing calcite growth rates or a change in the equilibrium fractionation factor due to changing Li speciation in the solution. These results, while not directly applicable to pristine biogenic calcite, have important implications for interpreting the Li content of calcite that has undergone any diagenetic modification (e.g., all bulk carbonate Li isotope data). Diagenesis under variable conditions provides a plausible alternative explanation for Li isotope excursions in carbonate sediment sequences that have been interpreted as indicating changing seawater δ7Li that deserves further investigation.

At Earth's surface the stable isotope ratio of strontium (88Sr/86Sr) is predominantly set by biological uptake of Sr and its storage in plant litter. This conclusion was reached from a stable isotope mass balance that was independently validated by direct determination of elemental fluxes between the Critical Zone compartments (rock, soil, vegetation, and stream water) of three field sites located in the Swiss Alps, the US Sierra Nevada, and the tropical highlands of Sri Lanka. These sites cover a gradient in erosion rates, which is inversely related to the residence time of solids in the Critical Zone thereby constituting an “erodosequence”. For eroding landscapes, previous stable isotope models predicted that isotope ratios are set by the rate at which secondary solids form during the conversion of rock to regolith. Counter to this expectation we found that, after release from primary minerals, Sr is partitioned into one fraction taken up by plants and the remainder into dissolved Sr flux. The formation of secondary weathering products such as clays and oxides plays a subordinate role in determining the Sr budget. A Sr isotope fractionation factor for biological uptake was determined for each of the three ecosystems from the average Sr stable isotope composition in bulk plants and its dissolved counterpart in stream water. This fractionation factors range from ca. −0.3 ‰ for the Alps and Sierra Nevada to ∼0 ‰ for the tropical Sri Lanka site. That these isotope fingerprints caused by biologic uptake are preserved means that more Sr was physically removed in plant litter than recycled. Such Sr removal in plant litter appears to be strongest at the slowly-eroding site, whereas the dissolved Sr export by streams is highest at the site with the fastest erosion rate. There, all Sr taken up by plants is returned from litter back into solution. The site with short residence time of solids is the only one at which parent material and dissolved export differ in their Sr isotope composition. Our study shows that the behavior of Sr in the Critical Zone is in stark contrast to that of metals of which the isotope fractionation is not affected by biological uptake (for example lithium, mostly set by formation of secondary solids) or affected by both secondary solid formation and biological uptake (for example silicon). Strontium stable isotope signatures offer the new opportunity to quantify nutrient cycling in the Critical Zone as a function of environmental and ecological parameters.

International audience; Fluids in magmas play a key role in magma differentiation and transportation of economic metals for ore deposits. As a chalcophile and incompatible element, zinc and its isotopes have been increasingly applied to study the magmatic-hydrothermal processes. However, zinc isotopic fractionation between aqueous fluids and magmas has not been well constrained. Here we experimentally determined equilibrium fractionation factors of Zn isotopes between aqueous fluids and silicate magmas (Δ66Znfluid-magma= δ66Znfluid - δ66Znmagma). The results reveal that aqueous fluids are isotopically heavier than the coexisting silicate magmas. No correlation between Δ66Znfluid-magma and temperature or chlorine contents in fluids is observed under our experimental conditions. Instead, Δ66Znfluid-magma is negatively corresponded with NBO/T of the melt (the ratio of non-bridge oxygen and tetrahedron ions), and positively correlated with the molar ratio of Al/(0.5K+Ca+Fe) in the bulk magmas, suggesting the controlling of silicate composition on Zn isotope fractionation. Our data therefore indicate that the isotopically heavier Zn in the fluids exsolved from magmas may account for the higher δ66Zn of pegmatites and high-silica granitic rocks. Moreover, involvement of magmatic fluids can explain the highly variable and remarkably heavier Zn isotopic signatures of fumaroles, thermal spring waters, and seafloor hydrothermal fluids compared to the igneous rocks. This study provides information that can be used to guide research using Zn isotopes to trace fluid activity and magmatism.

In this study, alkali/acid treatment and ion exchange post-synthesis modification methods to modify the pore diameter and structure of molecular sieve 13X (MS13X) were applied to obtain products, which could then be implemented to improve the enrichment recovery of hopanoids in petroleum. The modification products were analyzed by SEM with EDS, XRD and nitrogen physisorption. The results indicated that the product which had been prepared in the oxalic acid ethanol solution formed some mesopores, and also retained the initial framework of crystal. It was revealed that this product was able to remarkably increase the recovery rate of hopanoids in petroleum without leading to a significant isotope fractionation phenomenon. It is thus shown that this modification method of non-aqueous oxalic acid solution for MS13X can be used as an effective pretreatment tool in the application of compound-specific isotope analysis of hopanes with low concentration.

In order to characterize antimony (Sb) isotope fractionation in hydrothermal systems, we present Sb isotope compositions of primary stibnite ores from a large Sb deposit in south China. A total number of 39 analyses reveals a large δ123Sb range of −0.27 to +0.86‰, representing an up to 1.13‰ variation in this hydrothermal system. A gradual increase of Sb isotope ratios from the proximal to the distal parts was observed in stibnite ores. Rayleigh distillation models the systematic variation trend of the Sb isotope values, demonstrating that ore fluids are preferentially enriched in heavier Sb isotopes during the precipitation of isotopically light stibnite. In this way, we consider that separation of stibnite from a Sb-bearing fluid related to reaction kinetics as a cause for Sb isotope fractionation. The modeled data constrain a Sb isotope fractionation factor (αfluid-stibnite) between hydrothermal fluid and stibnite at approximately 0.9994. The model also constrains an initial Sb isotope value of ~0.45‰, which indicates metal sources in the basement rocks of the study area. Given that distal stibnites possess higher Sb isotopic values, Sb isotopes could be used to fingerprint hydrothermal fluid flow and unravel different processes in natural systems.

Diffusional isotope fractionation has been widely used to explain lithium (Li) isotope variations in minerals and rocks. Isotopic mass dependence of Li diffusion can be empirically expressed as D 7 Li D 6 Li = 6 7 β , where D is the diffusivity of a Li isotope. The knowledge about temperature and compositional dependence of the β factor which is essential for understanding diffusion profiles and mechanisms remains unclear. Based on the potential energy and interatomic forces generated by deep neural networks trained with ab initio data, we performed deep potential molecular dynamics (DPMD) simulations of several Li pseudo-isotopes (with mass = 2, 7, 21, 42 g/mol) in albite, hydrous albite, and model basalt melts to evaluate the β factor. Our calculated diffusivities for 7Li in albite and model basalt melts at 1800 K compare well with experimental results. We found that β in albite melt decreases from 0.267 ± 0.006 at 4000 K to 0.225 ± 0.004 at 1800 K. The presence of water appears to slightly weaken the temperature dependence of β , with β decreasing from 0.250 ± 0.012 to 0.228 ± 0.031 in hydrous albite melt. The calculated β in model basalt melt takes much smaller values, decreasing from 0.215 ± 0.006 at 4000 K to 0.132 ± 0.015 at 1800 K. Our prediction of β in albite and hydrous albite melts is in good agreement with experimental data. More importantly, our results suggest that Li isotope diffusion in silicate melts is strongly dependent on melt composition. The temperature and compositional effects on β can be qualitatively explained in terms of ionic porosity and the coupled relationship between Li diffusion and the mobility of the silicate melt network. Two types of diffusion experiments are suggested to test our predicted temperature and compositional dependence of β . This study shows that DPMD is a promising tool to simulate the diffusion of elements and isotopes in silicate melts.

Knowledge of Sn(II) speciation in aqueous and gaseous phases and the corresponding isotope effects are critical for understanding the transport and deposition of Sn in various geological and cosmochemical processes. In this study, we use first principles method to investigate the speciation of stannous (Sn(II)) chloride in fluids under hydrothermal and supercritical conditions. The results show that SnCl3−, SnCl2(H2O) and SnCl(H2O)2+ are stable in hydrothermal solutions at temperatures of up to 300 °C, with SnCl3− being the dominant species, whereas SnCl2 and SnCl2(H2O) are the stable species in vapor phases. Notably, SnCl2 is found to be stable under supercritical conditions. The reduced partition function ratios (β factors) for the stable Sn(II) species and three major Sn minerals (cassiterite, megawite, and romarchite) are also calculated by first principles methods. The calculation results show that under equilibrium, heavy Sn isotopes are preferentially partitioned into stannic (Sn(IV)) species, and gaseous species enrich heavy Sn isotopes relative to aqueous species. Based on the equilibrium Sn isotope fractionation factors derived in this study, we use a transport-precipitation model to evaluate the Sn isotope response to cassiterite precipitation in hydrothermal fluids. The modeling results show that significant Sn isotope variability could be produced during cassiterite precipitation, with temperature and Sn speciation being the primary controlling factors. Furthermore, by comparing the Sn isotope variability in natural cassiterite and those derived from the model, we argue that Sn should occur predominantly as Sn(IV) species in hydrothermal fluids during cassiterite precipitation in tin mineralizing systems.

Cadmium (Cd) pollution in agricultural soils has become a severe threat to food security and human health in recent years. Stable Cd isotopes are a potentially powerful tool for identifying the sources of Cd in soils. However, many Earth surface processes, including adsorption, leaching, and biogeochemical cycles in plants, may generate Cd isotope fractionation, which can complicate the potential application of Cd isotopes in tracing the sources of Cd pollution in soils. In this work, the Cd isotope compositions of typical Fe-Mn nodules (FMNs) and surrounding soils in two different soil profiles are investigated. Our results show that the FMNs in lower layers (i.e., C and W horizons) are isotopically lighter than the surrounding soils by –0.114‰ to –0.156‰ (Δ114/110CdFMN-soil). We interpret this fractionation as the result of preferential adsorption of isotopically light Cd onto the surface of goethite. In the upper layers (i.e., P and A horizons), the Δ114/110CdFMN-soil values are more negative in the P horizon (–0.213‰ to –0.388‰) but more positive in the A horizon (0.061‰ to 0.204‰). We interpret these fractionations as the result of natural biogeochemical processes (i.e., leaching and biological cycling) during soil development. Soil leaching preferentially releases isotopically heavy Cd into the underlying soil (i.e., P horizon), shifting the topsoil towards lower δ114/110Cd values but the underlying soils towards higher δ114/110Cd values. Moreover, biological cycling contributes isotopically heavy Cd to the topsoil, probably shifting the topsoil towards higher δ114/110Cd values. Our study demonstrates that the formation of Fe oxyhydroxides, leaching, and biological cycling can considerably modify the soil Cd isotope signature, highlighting the need to consider natural biogeochemical processes when using Cd isotopes to trace heavy metal pollution in soils.

As a transition metal that is moderately volatile at high temperatures, copper shows limited isotopic fractionation in terrestrial mantle-derived rocks but significant enrichment in its heavier isotope (up to 12.5‰ for 65Cu/63Cu) in objects that experienced volatile loss during formation, such as tektites, trinitite glasses, and lunar rocks. Previous efforts to model the Cu isotope fractionation trend from measurements of δ65Cu in tektites found that the trend cannot be explained by the theoretical isotope fractionation factor (α) for free evaporation of Cu, making it necessary to experimentally study Cu isotope fractionation under conditions similar to tektite formation. Here we present new experimental data of elemental (Na, K, Cu) and isotopic (Cu) fractionation during evaporation. Our experiments, conducted by laser-heating an aerodynamically levitated glass sphere to 1750, 2000, and 2150 °C, show rapid loss of Na, K, and Cu from the molten glass. In particular, > 99.99% of Cu was lost within 60 seconds. The evaporation induced loss of Cu is accompanied by progressive enrichment in its heavier isotope in the residue glass, with a maximum fractionation in δ65Cu of ∼18‰ relative to the synthesized initial sample. The empirical fractionation factor (α) calculated from our laser levitation data is 0.9960 ± 0.0002. Compared to similar experiments conducted for Zn, Cu appears to be significantly more volatile and show higher degrees of Cu isotope fractionation, consistent with observations in natural tektites. Comparing isotopic fractionation in a range of moderately volatile elements among laser levitation experiments, tektites, trinitites, and the bulk silicate Moon suggest that they experienced evaporation under various degrees of effective vapor saturation (∼74%, 93%, ∼99%, ∼99%), which depart significantly from free-evaporation (0%).

The responses of δ15N–N2O isotopic signatures to nitrogen (N) fertilization in in situ soils are not yet clear in agricultural field settings. We therefore conducted a 1-year field experiment to assess how N fertilization (0 and 400 kg N ha−1 year−1, N0 and N400) affects the δ15N–N2O isotopic signatures both at soil surface and in soil profile (0–3 m) in a wheat–maize rotation in North China. N fertilization increased N2O concentrations by 18–79% in the soil profile. It increased N2O fluxes by 9 times and 1–7 times at the soil surface and 0–0.9 m soil depth, respectively. In comparison, N fertilization reduced δ15N–N2O values by 10–74% in the soil profile. It reduced δ15N–N2O isotopic signatures at the soil surface and in the soil profile by 18% and 33%, respectively. The δ15N–N2O isotopic signature was dominated by substrate δ15N signature and N isotope fractionation during cold and warm seasons, respectively. Our results indicate that denitrification steps of NO3− → N2O dominated N2O production (over 99%) in the N0 treatment and the N400 treatment during N-fertilizer-free period. Following N fertilization, the NO3− → N2O dominated N2O production (over 99%) in the soil profile, N2O flux from the soil surface was mostly derived from NO3− → N2O and less from NH4+ → N2O. Overall, denitrification was found to dominate soil N2O transformation metabolism in the wheat–maize rotation cropland in North China.

Significant bromine (Br) isotope composition variations are found in natural salts and brines, which are often even larger than those of co-existing chlorine isotope compositions. The cause of such large Br isotope variations remains elusive. In this study, equilibrium Br isotope fractionations among Br-bearing gaseous molecules, aqueous species and crystalline minerals are provided via the density functional theory (DFT) based first-principles calculations. These fractionation factors form the base for future Br isotope geochemistry studies. Specifically, the first-principles molecular dynamics (FPMD) method is used to evaluate the tricky solvation effects, i.e., dozens of snapshots of FPMD trajectories are selected and re-optimized to their lowest energy atomic coordinates, then the reduced partition function ratios (i.e., β factors) of aqueous Br-bearing species are obtained by computing the average values of those snapshots. In this way, the configurational effects of aqueous Br-bearing species are included. For crystalline compounds, the static first-principles periodic DFT methods are used. We find that the β factors generally increase as the oxidation states of Br increase, indicating that heavy Br isotopes tend to be enriched in substances with higher Br oxidation states. The aqueous Br-bearing species in brines have detectable but small Br isotope fractionations with each other. However, the fractionations between gaseous molecules and NaBr(aq) are significantly larger, e.g., Δ81BrCH3Br(gas)-NaBr(aq) is 0.95 ± 0.041‰ at 20 °C. As for minerals, the fractionation between Br-halite(p) (pure NaBr crystal) and NaBr(aq) is close to zero, but for Br-halite(1/124) (Na125Cl124Br1) and NaBr(aq), the fractionation is 0.206 ± 0.041‰. Similar results are found for the fractionations between Br-sylvite, Br-bischofite and Br-bearing solutions, indicating that Br isotope compositions are closely related to Br/Cl ratios in minerals. By using the calculated isotope fractionation factors, we have modeled the Br isotope composition variations during salt precipitation processes. At 20 °C, the total variations of Br isotopes of salts and brines are found to be −0.45‰ to +0.21‰ and −0.39‰ to 0‰, respectively. They are much smaller than the observed Br isotope variations in natural samples. There must be other ways to fractionate Br isotopes to the extent that observed in nature. Based on the predicted equilibrium Br isotope fractionations among substances with different Br oxidation states, the large Br isotope variations in nature can be explained by the change of Br oxidation state. The sudden change of Br isotope compositions hence can be used as a new indicator for the change of redox conditions.

In the northwestern margin of the Youjiang basin (NWYB) in SW China, many Carlin-like gold deposits are highly antimony (Sb)-rich, and many vein-type Sb deposits contain much Au. These deposits have similar ages, host rocks, ore-forming temperatures, ore-related alterations and ore mineral assemblages, but the Au and Sb metallogenic relations and their ore-forming process remain enigmatic. Here we investigate the large Qinglong Sb deposit in the NWYB, which has extensive sub-economic Au mineralization, and present a new metallogenic model based on in-situ trace elements (EPMA and LA-ICP-MS) and sulfur isotopes (NanoSIMS and fs-LA-MC-ICP-MS) of the ore sulfides. At Qinglong, economic Sb ores contain coarse-grained stibnite, jasperoid quartz and fluorite, whilst the sub-economic Au–Sb ores comprise dominantly veined quartz, arsenian pyrite and fine-grained stibnite. Three generations of ore-related pyrite (Py1, Py2 and Py3) and two generations of stibnite (Stb1 and Stb2) are identified based on their texture, chemistry, and sulfur isotopes. The pre-ore Py1 is characterized by the lower ore element (Au, As, Sb, Cu and Ag) contents (mostly below the LA-ICP-MS detection limit) and Co/Ni ratios (average 0.31) than the ore-stage pyrites (Py2 and Py3), implying a sedimentary/diagenetic origin. The Py2 and Py3 have elevated ore element abundance (maximum As ​= ​6500 ​ppm, Au ​= ​22 ​ppm, Sb ​= ​6300 ​ppm, Cu ​= ​951 ​ppm, Ag ​= ​77 ​ppm) and Co/Ni ratios (average 1.84), and have positive As vs. Au–Sb–Cu–Ag correlations. Early-ore Stb1 has lower As (0.12–0.30 ​wt.%) than late-ore Stb2 (0.91–1.20 ​wt.%). These features show that the progressive As enrichment in ore sulfides is accompanied by increasing Au, Sb, Cu and Ag with the hydrothermal evolution, thereby making As a good proxy for Au. As-rich, As-poor and As-free zones are identified via NanoSIMS mapping of the Au-bearing pyrite. The As-rich zones in the Qinglong Au-bearing pyrites (Py2 and Py3) and ore stibnites (Stb1 and Stb2) have narrow δ 34 S H 2 S ranges (−8.9‰ to +4.1‰, average −3.1‰) and −2.9‰ to +6.9‰, average ​+ ​1.3‰), respectively, indicating that the Au-rich and Sb-rich fluids may have had the same sulfur source. Published in-situ sulfur isotopic data of pyrite As-rich zones from other Carlin-like Au deposits (Shuiyindong, Taipingdong, Nayang, Getang and Lianhuashan) in the NWYB have similar ore-fluid δ S H 2 S 34 values (−4.5‰ to +6.7‰, average −0.6‰) to those of Qinglong. Therefore, we infer that the sulfur of both Au and Sb mineralization was derived from the same magmatic-related source (0 ​± ​5‰) in the NWYB. Moreover, the core of pyrites (Py1) has variable S isotope fractionation (−18.9‰ to +18.1‰, mostly +3‰ to +12‰), suggesting that the higher-34S H2S was produced by bacterial sulfate reduction (BSR). The hydrothermal pyrite (Py2 and Py3) δ34S values gradually decrease with increasing As concentrations, and ultimately, within the restricted range (−5‰ to +5‰) in As-rich zones. This variation implies that the As-rich pyrite was formed through ongoing interactions of the magmatic-hydrothermal fluid with pre-existing sedimentary pyrites, causing the progressive decreasing δ34S values with As content increase, Hence, the fluid/mineral interaction may have generated the observed variation in δ34S and As contents. Overall, comparing the Au and Sb deposits in the NWYB, we favor a magmatic-related source for the Au–Sb–As-rich fluids, but the Au- and Sb-ore fluids were likely evolved at separate stages in the ore-forming system.

The stable chromium (Cr) isotope system has been used extensively over the past decade as a paleoredox proxy. The prevailing view has been that Cr oxidation is essentially limited to terrestrial settings and that the Cr isotope system is thus ideally suited to track atmospheric oxygenation. Further, although manganese(III,IV) oxide minerals (MnOx) are generally accepted to be the primary naturally occurring oxidants for the oxidation of insoluble Cr(III) to Cr(VI) and may fractionate Cr isotopes, there are conflicting reports in the literature regarding the direction and magnitude of Cr isotope fractionation by MnOx. We investigated Cr isotope fractionation during coupled Mn(II) and Cr(III) oxidation by laboratory cultures of marine Mn(II)-oxidizing bacteria and by natural microbial communities in seawater samples collected from the seasonally low-oxygen zone of the Chesapeake Bay, Maryland, USA. We found evidence for rapid marine Cr(III) oxidation linked to microbial Mn(II) oxidation. We also show that the initial partial oxidation of Cr(III) to Cr(VI) can produce an isotope fractionation of 0.8 ± 0.1‰. Further, given that Cr(VI) reduction and sequestration into marine sediments can lead to large isotopic fractionations (>1‰), evidence for rapid Cr oxidation in marine environments contradicts the idea that Cr isotope variations in the sedimentary record must be linked to subaerial oxidative weathering. As oxygen can accumulate in the surface ocean even under an anoxic atmosphere, these results call for a reevaluation of how we can link Cr isotope values to atmospheric oxygenation.

This work examines the stable isotope fractionation of carbon and oxygen in gaseous, supercritical, and liquid carbon dioxide systems at temperatures from -27.1 to +43.5 °C. For pressurized single-, supercritical-, and dual-phase carbon dioxide, both carbon and oxygen isotope fractionations can be measured and are significant when subjected to variations within this temperature range. The δ 13C and δ 18O values ranged from -41.55 to -41.38 ‰ (VPDB) and -27.74 to -24.9 ‰ (VPDB), respectively, for gas-phase carbon dioxide from 9.3 to 39 °C. A pressure variation of 27.58 barg to 34.48 barg was measured throughout this temperature range. In order to evaluate the effect of supercritical formation and liquefaction on the stable isotope values, cylinders were filled to varying pressures. When stored at cold temperatures, the δ13C value as measured in the headspace of the liquid phase varied from -41.23 to -41.13 ‰ (VPDB) and -41.50 to -41.44 ‰ (VPDB) in the supercritical phase. The δ18O value was between -25.51 and -25.36 ‰ (VPDB) in the liquid phase and between -24.79 and -24.77 ‰ (VPDB) in the supercritical phase. Temperatures in these experiments were selected to mimic outdoor conditions (winter and summer) that stable isotope laboratory practitioners may encounter when storing compressed carbon dioxide cylinders containing stable isotope working reference gases. The carbon and oxygen isotope composition of carbon dioxide gas within these pressurized cylinders return to their precooled isotope values within ∼24 h when warmed to laboratory temperatures (∼24 °C). A headspace analysis performed immediately after the carbon dioxide cylinder was removed from the cold environment yielded δ13C values that were relatively enriched, while δ18O values were relatively depleted. This is likely an effect of 12C and 18O being preferentially partitioned in the liquid phase within the cylinder. As the cylinder warmed, both liquid and gas equilibrated, and carbon and oxygen homogenized isotopically. As the cylinder was heated into the supercritical phase, a slight opposite isotope effect at higher pressure and temperatures was noted. That is, a slight 13C depletion and 18O enrichment were observed in the gas phase. However, these isotope variations were just slightly outside of the analytical error. Additionally, a separate gas-phase carbon dioxide cylinder was kept at a constant laboratory temperature as a control. This carbon dioxide showed no measurable carbon or oxygen isotope variation throughout the duration of the experimental work. The measured isotope fractionation was significantly higher comparing the phase transition from the gaseous to liquid phase versus the gaseous phase to supercritical phase. The proper handling of pressurized carbon dioxide cylinders used as reference gases for an isotope ratio mass spectrometer includes using carbon dioxide at pressures of less than ∼34.88 barg to ensure that the gas is present as a single phase, storing the gas in a temperature-controlled environment, and allowing the gaseous carbon dioxide to equilibrate to ambient conditions for 24-48 h if storage in a controlled ambient environment is not feasible.

Ammonium (NH4+), ammonia (NH3) and N2 are key nitrogen species in geological nitrogen recycling. NH3 has also been proposed to play an important role in mobilizing base metals in the form of metal-ammine complexes in hydrothermal fluids. The nitrogen isotope fractionation factors among these nitrogen species in aqueous and gaseous phases are essential parameters to trace source signatures and geochemical properties in geological processes. However, the nitrogen isotope fractionation factors for metal-ammine complexes are largely absent, and the few existing nitrogen isotope fractionation factors for the aqueous NH4+ – aqueous NH3 pair show large discrepancy between experimental results and theoretical calculations. In this study, we employed the density functional theory to systematically calculate the nitrogen isotope fractionation factors among the nitrogen species that may occur in a hydrothermal system, i.e., gaseous N2, gaseous and aqueous NH4+ and NH3, and ammine complexes of Co, Zn, Cu, Cd, Ag, Au, and Pt. Based on these new results, the large nitrogen isotope fractionations for the aqueous NH4+ – aqueous NH3 pair observed in previous experimental studies can be well explained by a combined effect of an equilibrium isotope fractionation between aqueous NH4+ and aqueous NH3 and a kinetic isotope fractionation during NH3 degassing from the solution. This suggests that the nitrogen isotopic behavior during NH3 degassing in natural hydrothermal system can be more complicated than previous thought. A numeric model is thus established here to quantify the combined isotopic effect on partial NH3 degassing. Using the new results of metal-ammine complexes, we also tested the hypothesis that nitrogen mobilization could be controlled by copper-ammine complex based on the copper concentration-δ15N relationship previously observed in meta-gabbros.

To better understand the role and extent of inter-mineral diffusion during subsolidus processes, we investigated the iron and magnesium isotopic compositions of olivine, orthopyroxene, and chromite separates from the Peridotite Zone of the Stillwater Complex. Olivine and orthopyroxene show limited Mg isotopic variations, with δ26Mg values ranging from −0.40 to −0.26‰ and from −0.29 to −0.22‰, respectively. In contrast, chromite displays extremely large Mg isotopic variations, with δ26Mg values ranging from −0.05 to +0.84‰. The δ56Fe values of olivine and orthopyroxene range from 0.00 to +0.17‰ and −0.04 to +0.06‰, respectively, whereas those of chromite range from −0.09 to +0.13‰. Most olivine-orthopyroxene pairs in our samples show no clear Fe-Mg isotopic differences, whereas silicate and coexisting chromite pairs plot away from theoretically predicted equilibrium lines, indicating disequilibrium inter-mineral fractionation. Higher δ56Fe values in silicates than in chromite and significantly higher δ26Mg values in chromite than in silicates indicate that subsolidus re-equilibration is responsible for the observed disequilibrium Fe-Mg isotope fractionation. We develop a quantitative model based on the investigated olivine and chromite to reproduce the observed kinetic Fe-Mg isotope fractionations. Our model results indicate a systematic difference between the Fe and Mg isotope fractionation factors, β, of olivine (βFe ≈ 0.27 and βMg ≈ 0.16) and chromite (0.03

Target lithologies and post-impact hydrothermal mineral assemblages in a new 1.3 km deep core from the peak ring of the Chicxulub impact crater indicate sulfate reduction was a potential energy source for a microbial ecosystem (Kring et al., 2020). That sulfate was metabolized is confirmed here by microscopic pyrite framboids with δ34S values of -5 to -35 ‰ and ΔSsulfate-sulfide values between pyrite and source sulfate of 25 to 54 ‰, which are indicative of biologic fractionation rather than inorganic fractionation processes. These data indicate the Chicxulub impact crater and its hydrothermal system hosted a subsurface microbial community in porous permeable niches within the crater's peak ring.

Chromium stable isotope ratios are used to trace the reduction of Cr(VI) to Cr(III) in both ancient and modern systems. However, quantitative interpretation of Cr isotopic signatures has been stymied by the large variability in isotopic fractionation factors for Cr(VI) reduction by different reductants. Here we determine Cr isotope fractionation factors during Cr(VI) reduction by Fe(II/III)-bearing clay minerals, which are abundant in subsurface environments. Several variables were tested: pH, total Fe content of the clay, and the fraction of reduced Fe within the clay (Fe(II)/Fe(total)). The latter controls the standard reduction potential of the clay. Our results demonstrate that neither pH nor total Fe content of the clay have major effects on isotopic fractionation. In contrast, as the effective standard reduction potential of the clay and thus the standard free energy of Cr(VI) reduction become more negative, Cr isotope fractionation factors decrease in magnitude from −4.9 to −1.3‰ according to a linear free energy relationship. This linear free energy relationship can be predicted from Marcus electron transfer theory and allows first-order predictions of Cr isotope fractionation factors to be made from the standard reduction potential or Fe(II)/Fe(total) of a clay, potentially improving our ability to model Cr isotope signatures in geochemical systems. Chromium is the first isotope system to show such a linear free energy relationship over a diverse range of reductants, including both aqueous and solid-phase reductants, and may provide a model for determining other redox-driven kinetic isotope effects in environmentally important isotope systems.

Barium isotopes could be a novel tracer in low-temperature geochemical processes such as the Ba cycle in rivers and oceans. Equilibrium Ba isotope fractionation between Ba-hosting minerals and aqueous solution is of great importance for the applications of Ba isotopes in geochemistry, but it remains poorly constrained. In this study, we performed first-principles calculations based on the density functional theory (DFT) to determine the equilibrium Ba isotope fractionation between minerals and aqueous solution (103lnαmineral-Ba_aq of 137Ba/134Ba). The structural properties of aqueous Ba2+ are well predicted by the first-principles molecular dynamics (FPMD) simulation and 121 snapshots are extracted from FPMD trajectories to estimate the reduced partition function ratio (β factor or 103lnβ of 137Ba/134Ba) of aqueous Ba2+. The 103lnβ decreases in the sequence of aragonite > calcite > aqueous Ba2+ ∼ witherite > barite. The β factor is dominantly determined by the force constant, which is affected by both the average Ba O bond length and the coordination number. Our results show that 103lnαaragonite-Ba_aq and 103lnαwitherite-Ba_aq are 0.36‰ and −0.02‰ at 300 K, respectively, consistent with results of experimental studies at equilibrium. The depletion of heavy Ba isotopes observed in natural corals relative to seawater suggests that kinetic effects play an important role in Ba isotope fractionation during coral growth. The 103lnαbarite-Ba_aq is only −0.17‰ at 300 K, indicating limited Ba isotope fractionation caused by the Ba removal stemmed from inorganic barite precipitation. Overall, the equilibrium Ba isotope fractionation factors between minerals and aqueous Ba2+ calculated in this study provide a guideline for the applications of Ba isotopes in low-temperature geochemistry.

Funding: These field and related experimental studies were supported through US NSF grants: 0549547, 0751771, 0813861, 0961188 and 1736679 (WES). Mid-ocean ridge (MOR) hydrothermal vent fluids are enriched with dissolved barium, but due to barite (BaSO4) precipitation during mixing between Ba-bearing vent fluids and SO4-bearing seawater, the magnitude of hydrothermal Ba input to the ocean remains uncertain. Deep-ocean Ba isotopes show evidence for non-conservative behavior, which might be explained by input of isotopically heavy hydrothermal Ba. In this study we present the first Ba isotope data in mid-ocean ridge hydrothermal vent fluids and particles from systems on the Mid-Atlantic Ridge (Rainbow 36°N and TAG 26°N), the East Pacific Rise (EPR9–10°N and 13°N) and the Juan de Fuca Ridge (MEF and ASHES). The vent fluids display a wide range of dissolved Ba concentrations from 0.43 to 97.9 μmol/kg and δ138/134Ba values from −0.26 to +0.91‰, but are modified relative to initial composition due to precipitation of barite. Calculated endmember vent fluid δ138/134Ba values, prior to barite precipitation, are between −0.17 and +0.09‰, consistent with the values observed in oceanic basalts and pelagic sediments. Water-rock interaction at depth in the oceanic crust appears to occur without Ba isotope fractionation. During subsequent venting and mixing with seawater, barite precipitation preferentially removes isotopically light Ba from vent fluids with a fractionation factor of Δ138/134Bahyd-barite-fluid = −0.35 ± 0.10‰ (2SE, n = 2). Based on knowledge of barite saturation and isotope fractionation during precipitation, the effective hydrothermal Ba component that mixes with seawater after barite precipitation has completed can be calculated: δ138/134Bahyd = +1.7 ± 0.7‰ (2SD). This value is isotopically heavier than deep ocean waters and may explain the observed non-conservative of Ba isotopes in deep waters. These new constraints on hydrothermal Ba compositions enable the hydrothermal input of Ba to Atlantic deep waters to be assessed at ≈3–9% of the observed Ba. Barium isotopes might be used as a tracer to reconstruct the history of hydrothermal Ba inputs and seawater SO4 concentrations in the past. Postprint

In this study, a new purification procedure for high precision Sb isotopic analysis was developed by using a thiol silica gel column and is applied to determine Sb isotope composition in natural water samples affected by mining activities. In our proposed procedure, Sb(V) was firstly pre-reduced with 0.5% (w/v) KI–ascorbic acid mixed solution and then Sb(III) in the solution could be separated and purified simply by elution with hydrochloric acid. With the developed procedure, the recovery of antimony was greater than 95.2% and blank values were

That silicon is an important element in global biogeochemical cycles is widely recognised. Recently, its relevance for global crop production has gained increasing attention in light of possible deficits in plant-available Si in soil. Silicon is beneficial for plant growth and is taken up in considerable amounts by crops like rice or wheat. However, plants differ in the way they take up silicic acid from soil solution, with some species rejecting silicic acid while others actively incorporate it. Yet because the processes governing Si uptake and regulation are not fully understood, these classifications are subject to intense debate. To gain a new perspective on the processes involved, we investigated the dependence of silicon stable isotope fractionation on silicon uptake strategy, transpiration, water use, and Si transfer efficiency. Crop plants with rejective (tomato, Solanum lycopersicum, and mustard, Sinapis alba) and active (spring wheat, Triticum aestivum) Si uptake were hydroponically grown for 6 weeks. Using inductively coupled plasma mass spectrometry, the silicon concentration and isotopic composition of the nutrient solution, the roots, and the shoots were determined. We found that measured Si uptake does not correlate with the amount of transpired water and is thus distinct from Si incorporation expected for unspecific passive uptake. We interpret this lack of correlation to indicate a highly selective Si uptake mechanism. All three species preferentially incorporated light 28Si, with a fractionation factor 1000×ln (α) of −0.33 ‰ (tomato), −0.55 ‰ (mustard), and −0.43 ‰ (wheat) between growth medium and bulk plant. Thus, even though the rates of active and passive Si root uptake differ, the physico-chemical processes governing Si uptake and stable isotope fractionation do not. We suggest that isotope fractionation during root uptake is governed by a diffusion process. In contrast, the transport of silicic acid from the roots to the shoots depends on the amount of silicon previously precipitated in the roots and the presence of active transporters in the root endodermis, facilitating Si transport into the shoots. Plants with significant biogenic silica precipitation in roots (mustard and wheat) preferentially transport silicon depleted in 28Si into their shoots. If biogenic silica is not precipitated in the roots, Si transport is dominated by a diffusion process, and hence light silicon 28Si is preferentially transported into the tomato shoots. This stable Si isotope fingerprinting of the processes that transfer biogenic silica between the roots and shoots has the potential to track Si availability and recycling in soils and to provide a monitor for efficient use of plant-available Si in agricultural production.

Intramolecular isotope distributions, including isotope clumping and position specific fractionation, can provide proxies for the formation temperature and formation and destruction pathways of molecules. In this study, we explore the position-specific hydrogen isotope distribution in propane. We analyzed propane samples from 10 different petroleum systems with high-resolution molecular mass spectrometry. Our results show that the hydrogen isotope fractionation between central and terminal positions of natural propanes ranges from −102‰ to +205‰, a much larger range than that expected for thermodynamic equilibrium at their source and reservoir temperatures (36–63‰). Based on these findings, we propose that the hydrogen isotope structure of catagenic propane is largely controlled by irreversible processes, expressing kinetic isotope effects (KIEs). Kinetic control on hydrogen isotope composition of the products of thermal cracking is supported by a hydrous pyrolysis experiment using the Woodford Shale as substrate, in which we observed isotopic disequilibrium in the early stage of pyrolysis. We make a more general prediction of KIE signatures associated with kerogen cracking by simulating this chemistry in a kinetic Monte Carlo model for different types of kerogens. In contrast, unconventional shale fluids or hot conventional reservoirs contain propane with an isotopic structure close to equilibrium, presumably reflecting internal and/or heterogeneous exchange during high temperature storage (ca. 100–150 °C). In relatively cold (

A series of photochemical experiments with sulfur dioxide were carried out using a xenon lamp (λ > 200 nm), a low-pressure mercury lamp (λ = 184.9 and 253.7 nm), and an UP-213 laser system (λ = 213 nm) as light sources. Based on the isotope data obtained for elemental sulfur (the end product of SO2 photolysis), we revealed specifics in correlations between δ34S, ∆33S, and ∆36S values depending on the spectral characteristics of the incident radiation. Our studies showed that the Archean Δ33S/δ34S and Δ36S/Δ33S ratios could be reproduced in the SO2 photolysis experiments by combining spectral composition of the radiation, the intensity of the spectral components, and the partial pressure of SO2. The results of the experiments suggest that the UV radiation with wavelengths less than 200 nm was a determining factor in the production of sulfur isotopic anomalies in the Archean atmosphere.

Low maturity coal samples were taken from the Ordos Basin to conduct gold tube thermal simulation experiment in a closed system, and the characteristics of the products were analyzed to find out the fractionation mechanism of carbon isotopes and the causes of abnormal carbon isotopic compositions of natural gas. At the heating rates of 2 °C/h (slow) and 20 °C/h (rapid), the low maturity coal samples of the Ordos Basin had the maximum yields of alkane gas of 302.74 mL/g and 230.16 mL/g, the δ13C1 ranges of −34.8‰ to −23.6‰ and −35.5‰ to −24.0‰; δ13C2 ranges of −28.0‰ to −9.0‰ and −28.9‰ to −8.3‰; and δ13C3 ranges of −25.8‰ to −14.7‰ and −26.4‰ to −13.2‰, respectively. Alkane gas in the thermal simulation products of rapid temperature rise process showed obvious partial reversal of carbon isotope series at 550°C, and at other temperatures showed positive carbon isotope series. In the two heating processes, the δ13C1 turned lighter first and then heavier, and the non-monotonic variation of the δ13C1 values is because the early CH4 is from different parent materials resulted from heterogeneity of organic matter or the carbon isotope fractionation formed by activation energy difference of early enriched 12CH4 and late enriched 13CH4. The reversal of carbon isotope values of heavy hydrocarbon gas can occur not only in high to over mature shale gas (oil-type gas), but also in coal-derived gas. Through thermal simulation experiment of toluene, it is confirmed that the carbon isotope value of heavy hydrocarbon gas can be reversed and inversed at high to over mature stage. The isotope fractionation effect caused by demethylation and methyl linkage of aromatic hydrocarbons may be an important reason for carbon isotope inversion and reversal of alkane gas at the high to over mature stage.

The sulfur isotope composition of single sulfide grains has been studied taking into account their paragenetic sequence in the samples collected from three hydrothermal fields (Logatchev, Krasnov, and Rainbow), located in the northern part of the Mid-Atlantic Ridge. The δ34S values of sulfides are +3.9 to +6, +7.1 to +9.8, and +2.1 to +8.4 ‰ in the Logatchev, Krasnov, and Rainbow fields, respectively. Late-generation sulfides within the studied domains (1–10 mm) of the samples are enriched in 34S isotope relative to early generations, and the sulfur isotope composition shows no relationship with the composition of sulfide minerals. In single grains of hydrothermal barite, the δ34S values exceed the generally accepted range for modern seawater sulfates. A model of the sulfur isotope fractionation in the hydrothermal system is proposed, based on the assumption of thermogenic sulfate reduction during fluid–rock interaction in the system, which is closed with respect to fluid. The model also takes into account simultaneous sulfur leaching from host rocks, the proportion of released sulfur from which depends on the progress of thermogenic sulfate reduction. Application of this model explains some well-known contradictions found in studying the sulfur isotope composition of sulfides from other hydrothermal fields in the World Ocean.

The feedback between CO2 sources and sinks through chemical weathering is one of the important reasons why Earth has maintained a habitable climate for over four billion years. The lithium (Li) isotopic system is a promising tracer of silicate weathering, but the mechanisms causing its isotope fractionation during weathering remain ambiguous. Here, we performed batch experiments of Li adsorption to one of the common clay minerals -kaolinite in three sets, including the time-series, pH-dependent, and concentration-control sets. Our results demonstrate that the liquid-solid Li isotope fractionation reaches up to 36‰, with up to 99% initial Li being adsorbed on kaolinite. The magnitudes of Li adsorption and isotope fractionation increase with reaction time, and reach the steady-state after ∼1000 min. The magnitude of Li isotope fractionation increases with the adsorption ratio of Li, in positive relationships with solute pH and ionic strength. At constant solute pH = 8.5 and ionic strength of 0.001 M, the adsorption ratio and isotope fractionation of Li on kaolinite reach the maximum with the lowest initial Li concentration of 2 μM. In experiments, Li is removed by kaolinite as the inner-sphere and/or outer-sphere complexes, likely followed by structural occupation as supported by incomplete desorption. We model the Li isotope fractionation in all three sets, which can be best described by Rayleigh distillation models. In summary, significant Li isotope fractionation occurs following a kinetic law in closed-systems during adsorption on kaolinite. Adsorption-driven isotope fractionation conforms to a kinetic solid-liquid isotope fractionation factor α ∼ 0.992, consistent with theoretical ion-desolvation between complexed and dissolved ions (α = 0.9925, Hofmann et al., 2012). This study reveals a vital kinetic role of clay uptake in Li isotope fractionation during chemical weathering, suggesting rapid forward adsorption reaction versus relatively slow backward reaction. The dominance of the kinetic mechanism over the equilibrium mechanism further explains field observations from rivers worldwide. Given above, the outcome of this study calls for additional attention on low-temperature kinetic Li isotope fractionation at Earth’s surface and further refinement of quantitative models using geological Li records to trace weathering and reconstruct climate.

We investigate the effects that the spectral composition of radiation that plants are exposed to during their development has on the fractionation of carbon isotopes between atmospheric carbon dioxide and the primary products of photosynthesis in plant tissues. The difference in carbon isotope composition between carbon in air near the leaves and carbon in the leaves varies in the range of 7 to 19 depending on the spectral composition of incident light, with an increase in the red component resulting in enrichment of the leaves with the light isotope 12C. This differences are (i) the measure of isotope fractionation during the vital activity of plants and (ii) the rate of carbon assimilation due to photosynthetic reactions.

Mass-independent fractionation of sulfur isotopes (MIF-S)—as recorded primarily in pre-2.5 billion years ago (Ga) sedimentary rocks—has been interpreted as evidence of photolysis of volcanic SO2 in an anoxic troposphere. Here, I present thermodynamic and kinetic calculations, combined with data on the geology, mineralogy and chemical and isotopic compositions of modern and Archaean (3.8–2.5 Ga) aged volcanic samples from different tectonic settings, to examine early Earth’s sulfur cycle. Based partly on the similarities between submarine hydrothermal deposits and arc volcanic rocks in pyrite (FeS2) abundances and sulfur isotopic compositions (for example, the presence of both positive and negative δ34S values), I conclude that degassing of sulfur (mostly as SO2) into the atmosphere has been carried out primarily by subaerial eruptions of oxidized, arc-like magmas since at least 3.5 Ga. The generation of volcanic SO2 requires plate tectonics and the involvement of sulfate-rich seawater, which requires large exposed lands and an oxygenated atmosphere. I propose that the MIF-S signatures in sedimentary rocks were created by ultraviolet photochemical reactions between SO2 from explosive volcanic eruptions and O2 in the stratosphere, above an oxygen-rich troposphere, or by high-temperature reactions between organic compounds and sulfate in the oceans. Formation of mass-independent isotope fractionation of sulfur signatures recorded in Archaean sedimentary rocks could have occurred in an oxygen-rich atmosphere, according to thermodynamic and kinetic calculations and analysis of Earth’s early sulfur cycle.

Magnesium (Mg) isotopes in carbonate minerals are a useful proxy for paleoclimate studies, but interpretations are often limited by an inadequate understanding of the various factors controlling Mg isotopic fractionation during carbonate formation. Previous work has studied a number of parameters including aqueous chemistry, mineralogy, temperature, and precipitation rate. However, little is known about the impact of solid/solution ratio, calcite growth mechanism, and crystal morphology on isotope fractionation. In this work, two groups of seeded chemo-stat calcite precipitation experiments were conducted at 25 °C to explore the potential impact of crystal growth and morphology on the fractionation of Mg isotopes. Group-1 experiments (G1) contained nine individual runs that were performed under identical physicochemical conditions, except for solid/solution ratio and the length of an experiment. The isotope fractionation between precipitated calcite and aqueous solution is limited, with ΔMg ranging from −2.58 to −2.40‰ and an average of −2.49 ± 0.12‰ (2SD, n = 9). The Group-2 experiments (G2) contained 3 paired runs with solution Mg/Ca molar ratios of 0.5, 2.0, and 5.0, and yielded ΔMg values that ranged from −2.69 to −2.36‰ with an average of −2.62 ± 0.25‰ (2SD, n = 6). The average ΔMg value for both sets of experiments is −2.54 ± 0.22‰ (2SD, n = 15), and it is independent of precipitation rate, solution Mg/Ca molar ratio, solid/solution ratio, amount of overgrowth, and mol% Mg content in overgrowth. The form and texture of the calcite overgrowths in our experiments range from {104} rhombohedra with smooth crystal faces containing few macrosteps to {104} rhombohedra containing extensive evidence for 2-D nucleation on crystal faces, to more steeply sided rhombohedra {0kl}. While significant changes in crystal morphology are related to solid/solution ratio and solution composition in the G1 and G2 experiments, respectively, there was no difference in Mg isotope systematics, suggesting that crystal morphology does not affect the Mg isotopic composition of calcite within the range of features investigated and 2-D nucleation may be less affected by calcite growth kinetics than a spiral growth mechanism. Integrating our results with previous published values, an equilibrium isotopic fractionation factor of −2.47 ± 0.09‰ (weighted average ± weighted 2SD, n = 70) between calcite and aqueous solutions is derived at room temperature., We thank Sylvia Riechelmann and one anonymous reviewer for their insightful and critical comments, which significantly improved the manuscript. The careful and efficient editorial handing by AE Adrian Immenhauser is greatly appreciated. We would also like to thank Bing-Yu Lee for assistance on sample processing and column chemistry for Mg isotope analyses, Heng-Ci Tian, Yan Hu, and Mingzhu Liu for discussion and constructive comments, Jon Tonner for assistance on PHREEQC, and the Quantachrome’s Material Characterization Laboratory for providing surface area analyses of calcite seed material. This work was financially supported by National Science Foundation EAR-1747706, NASA Astrobiology Institute grant NNA13AA94A, the Summer Research Fellowship program through the Office of Undergraduate Research at Furman University, the Spanish Government FEDER projects CGL2016-75679-P and CGL2016-79458-P, and the Dutch Research Council (NWO) Origins Center project 190438131.

For many years after the discovery of the two stable isotopes of boron (10B,11B) in 1920 they were not used as tracers in the soil–plant system due to analytical constraints. However, with the adve...

Selenium (Se) isotope fractionation has been widely used for constraining redox conditions and microbial processes in both modern and ancient environments, but our knowledge of the controls on fractionation during microbial reduction of Se-oxyanions is based on a limited number of studies. Here we complement and expand the currently available pure culture data for Se isotope fractionation by investigating for the first time six phylogenetically diverse, mesophilic, and non-respiring bacterial strains that reduce Se-oxyanions to elemental Se [Se(0)]. Experiments were performed with either selenate [Se(VI)] or selenite [Se(IV)] at lower, more environmentally-relevant Se (9–47 μM) and carbon (500 μM) concentrations than previously investigated. Enterobacter cloacae SLD1a-1, Desulfitobacterium chlororespirans Co23 and Desulfitobacterium sp. Viet-1 were incubated with Se(VI) and Se(IV). Geobacter sulfurreducens PCA, Anaeromyxobacter dehalogenans FRC-W and Shewanella sp. (NR) were examined for their ability reducing Se(IV) to Se(0). Our data confirm that microbial reduction of both Se-oxyanions is accompanied by large kinetic isotopic fractionation (reported as 82/76e = 1000×(82/76α-1) in ‰). Under our experimental conditions, microbial reduction of Se(VI) shows consistently greater isotope fractionation (e = −9.2‰ to −11.8‰) than reduction of Se(IV) (e = −6.2 to −7.8‰) confirming the difference in metabolic pathways for the reduction of the two Se-oxyanions. For Se(VI), an inverse relationship between normalized cell specific reduction rate (cSRR) and Se isotope fractionation suggests that the kinetic isotope effect for Se(VI) reduction is governed by an enzymatically-specific pathway related to the bacterial strain-specific physiology. In contrast, the lack of correlation between normalized cSRR and isotope fractionation for Se(IV) reduction indicates a non-enzyme specific pathway which is dominantly extracellular. Our study highlights the importance to understand microbially-mediated Se isotope fractionation depending on Se species, and cell-specific reduction rates before Se isotope ratios can become a fully applicable tool to interpret Se isotopic changes in modern and ancient environments.

The selenium (Se) isotope system has been proposed as a redox proxy in environmental and paleoceanographic studies. However, Se isotope exchange among various Se species can potentially interfere with redox-related isotope signatures, and is still poorly understood. In this work, we investigated Se isotope exchange kinetics and equilibrium fractionations between aqueous Se(IV) and Se(VI) under various experimental conditions. At pH = 7, low-Se concentration experiments (0.026 mM Se(IV) and 0.026 mM Se(VI)) at 25 °C, 38 °C and 60 °C were conducted for 900 days, while high-Se concentrations (0.13 mM Se (IV) and 0.14 mM Se(VI); 1.3 mM Se(IV) and 1.4 mM Se(VI)) at 60 °C were conducted for 1547 days. All experiments did not reach isotopic equilibrium, with observed Se isotope fractionations The exchange kinetics between Se(IV) and Se(VI) were also investigated using a 82Se tracer. The exchange rates (R) at 0.13 mM Se(IV) and 0.13 mM Se(VI) at 25 °C, 38 °C and 60 °C were determined to be ≤6.34 × 10−10 M day−1, ≤1.12 × 10−09 M day−1 and ≤1.17 × 10−09 M day−1, respectively. Using the upper bound for the isotope exchange rate at 25 °C and theoretically calculated equilibrium fractionations, and assuming a first order isotope exchange reaction between Se(IV) and Se(VI) by analogy to the sulfur system, the timescale of isotope exchange between aqueous Se (IV) and Se (VI) in a natural lake (Sweitzer Lake, Colorado, USA) was estimated. The minimum half-time (t1/2, time to reach 50% isotopic equilibrium) and the minimum time for detectable isotope exchange (tmin) are ≥440,000 and ≥18,000 years, respectively. In the modern oceans, t1/2 and tmin are ≥51 million and ≥3.6 million years, respectively. These timescales are much longer than the residence time of Se in Sweizer Lake (2.4 years) and the modern ocean (26,000 years). Therefore, when using Se isotopes to trace the biogeochemical cycle of Se in lakes and oceans, the effect caused by isotope exchange between aqueous Se(IV) -Se(VI) systems is insignificant.

The oxygen and clumped isotope signatures of Mg calcites are routinely used as environmental proxies in a broad range of surroundings, where Mg calcite forms either by classical nucleation or via an amorphous calcium magnesium carbonate (ACMC) precursor. Although the (trans)formation of ACMC to Mg calcite has been identified for an increasing number of settings, the behavior of both isotope proxies throughout this stage is still unexplored. In the present study ACMC (trans)formation experiments were carried out at constant pH (8.30 ± 0.03) and temperature (25.00 ± 0.03 °C) to yield high Mg calcite (up to 20 mol% Mg). The experimental data indicate that the oxygen isotope values of the amorphous and/or crystalline precipitate (δ$^{18}$O$_{prec}$, analyzed as Mg calcite) are affected by the (trans)formation pathway, whereas clumped isotopes (Δ$_{47prec}$ = Δ$_{47Mg-calcite}$) are not. The oxygen isotope evolution of the solid phase can be explained by the instantaneous trapping of the isotopic composition of the aqueous (bi)carbonate complexes. This entrapment results in remarkably high 10$^{3}$ln(α$_{prec-H2O}$) values of ∼33‰ at the initial ACMC formation stage. During the ACMC transformation process the oxygen isotope equilibrium is approached rapidly between Mg calcite and water (Δ$^{18}$O$_{Mg calcite-water}$ = 30.3 ± 0.4‰) and no isotopic memory of the initial to the final Mg calcite at the end of the experiment occurs. The implications for oxygen and clumped isotope signatures of Mg calcite formed via ACMC are discussed in the aspects of various scenarios of (trans)formation conditions and their use as environmental proxies.

Large mass-independent fractionation signatures in Hg have been observed in the laboratory and the environment, prompting deep questions about the chemical reasons behind these signatures. Since the relative lack of mechanistic information about Hg chemistry in the environment has precluded explanations of these isotope effects, the present study uses high-level electronic structure methods to evaluate the possible photochemical mechanisms of mass-independent isotope effects (MIEs) in HgX2 and CH3HgX (X = Cl, Br, I, and SCH3). The results show that spin-orbit coupling wipes out the potential of MIEs for Hg bound to Br or I, but that complexes involving lighter elements, HgX2 and CH3HgX (X = Cl and SCH3), have relatively small spin-orbit couplings upon photolysis. This unexpected finding shows that magnetic isotope fractionation due to hyperfine coupling is possible, depending on the identity of the Hg complex. By examination of the photolysis potential energy profiles, this study shows that HgX2 complexes can have a positive or a negative MIE (depending on reaction conditions), while CH3HgX complexes exclusively result in a positive MIE. These findings agree with MIE recorded in natural samples, demonstrating a plausible mechanism for the surprising mass-independent fractionation of Hg in the environment.

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.

Adsorption plays an important role in the biogeochemical cycling of selenium (Se) in natural environments and Se isotope fractionation during adsorption is a significant but poorly studied part of Se isotope system. This paper examined Se(IV) and Se(VI) adsorption onto four naturally occurring metal oxides (hematite, manganese dioxide (β-MnO2), and α and γ-alumina oxides) and revealed Se isotope fractionation as a function of the absorbents used, Se species adsorbed, exposure time, and pH. The results show that Se(IV)/(VI) adsorption was initially rapid and was accompanied with kinetic isotope fractionations as large as 3‰, but slowed down as adsorption equilibrium was approached, eventually approaching isotopic equilibrium. The Se(IV) adsorption onto the studied metal oxides took at least 12 h to reach adsorption equilibrium, longer than Se(VI) adsorption (

Understanding the process of CO2 degassing during precipitation of calcite from a Ca2+–HCO3− solution is crucial for interpreting isotope compositions in the calcite precipitates. Unlike diffusion-controlled outgassing, i.e., dissolved CO2 escaping from the solution via diffusion, degassing caused by precipitation of calcite is accompanied by a large carbon isotope fractionation between CO2(g) and HCO3− due to breaking of C O bond, with an equilibrium fractionation of ca. −9‰ at ambient temperature. Such a magnitude of fractionation has a great influence on carbon isotope compositions (δ13C) of DIC (dissolved inorganic carbon) reservoir in the solution and thus on δ13C of calcite precipitated from it. However, knowledge on isotope fractionation is limited during precipitation-associated degassing of CO2 in a supersaturated solution where rapid calcite precipitation drives CO2 degassing out of isotopic equilibrium. Here we show the data of water chemistry and carbon isotope compositions of DIC and carbonate precipitates in a mountain stream at Baishuitai, China. Results from numerical models show there exist large degrees of carbon isotope disequilibrium during precipitation-associated degassing of CO2 via HCO3− dehydration and dehydroxylation. Average carbon isotope fractionation between CO2(g) and HCO3− ( e C O 2 (g) - HC O 3 - ) calculated from our dataset is about −20‰ which is much lower than the equilibrium value. Moreover, an inverse correlation between e C O 2 (g) - HC O 3 - and precipitation rate was observed, indicating higher precipitation rates cause e C O 2 (g) - HC O 3 - farther from equilibrium value. By compiling the data from this study and literatures, we infer that disequilibrium isotope fractionation of carbon between CO2(g) and HCO3− may be common during the growth of speleothem and travertine from a solution supersaturated with respect to calcite. The rate dependence of e C O 2 (g) - HC O 3 - has special implications for speleothem archives from ventilated caves. As partial pressure of CO2 in cave atmosphere evolves with ventilation, variable precipitation rates of calcite will cause inconstant degrees of disequilibrium isotope fractionation between CO2 and DIC and thus perturb the time-series of speleothem’s δ13C records for paleo-environmental reconstruction.

The chemical and isotopic signatures of moderately volatile elements are useful for understanding processes of volatile depletion in planetary formation and differentiation. However, the fractionation factors between gas and melt phases during evaporation that are required to model these planetary volatile depletion processes are still sparse. In this study, twenty heating experiments were conducted in 1 atm gas-mixing furnaces to constrain the behavior of K, Cu, and Zn evaporation and isotopic fractionation from basaltic melts at high temperatures. The temperatures range from 1300 °C to 1400 °C, and durations are from 2 to 8 days. Oxygen fugacities (fO2) range from one log unit below to ten log units above that of the iron-wustite buffer (IW–1 to IW + 10, corresponding to logfO2 of –10.7 to –0.68 at 1400 °C). The conditions were selected to achieve an evaporation-dominated regime (where timescales of diffusion ≪ evaporation for trace elements) in order to avoid diffusion-limited evaporation. Our results show during evaporation Zn behaved as the most volatile, followed by Cu and then K, regardless of temperature and oxygen fugacity. Partitioning of Zn into spinel layers within experimental capsules, however, has been observed, which has substantial effects on the Zn isotope fractionation factor. Therefore, Zn results are presented but further discussion is excluded. Element loss depends on both temperature and oxygen fugacity, where higher temperatures and lower oxygen fugacities promote evaporation. However, with varying temperature and oxygen fugacity, the kinetic isotopic fractionation factors, α (where, R R 0 = f α - 1 ), for K and Cu remain constant, thus these factors can be applied to a wider range of conditions than those in this study. The experimentally determined fractionation factors for K, and Cu during evaporation from basaltic melts are 0.9944, and 0.9961, respectively. The fractionation factors for these elements with varying volatilities are significantly larger than the “apparent observed fractionation factors,” which approach one and are inferred from lunar basalts relative to the Bulk Silicate Earth. This observation suggests near-equilibrium conditions during volatile-element loss from the Moon as the “apparent observed fractionation factors” of lunar basalts are similar for all three elements.

Highlights • Sr isotope composition in different minerals is an excellent proxy, that can be used to reconstruct the environmental conditions of their precipitation. In order to study Strontium (Sr) isotope fractionation during the precipitation of strontianite (SrCO3) as a function of the specific precipitation rate (R*) and temperature (T), strontianite was precipitated at 12.5, 25.0 and 37.5 °C by diffusing NH3 and CO2 gases into aqueous solutions. The specific precipitation rate R* (mol/cm2.h) for every sample was determined by applying the initial rate method. The mean isotope difference between bulk solution and precipitate (∆88/86Srstrontianite-solution) was found to be −0.279 ± 0.005‰ (2σmean) independent of both rate and temperature. Hence, Sr isotope fractionation in strontianite is completely different from that in calcite and aragonite, where a strong dependency from both rate and temperature can be observed. The latter is interpreted to reflect the competition between Sr2+ and Ca2+ ions for incorporation into the calcium carbonate crystal lattice, which is absent during the precipitation of pure strontianite. The isotope difference between strontianite and bulk solution then simply reflects the intermolecular forces in the aqueous solutions as well as the kinetic effect. The difference in the (∆88/86Srstrontianite-solution between experiments then reflects the dehydration energy of Sr ions in the adsorption layer of SrCO3.