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The Titanium (Ti) isotope compositions of felsic rocks are heavier than their mafic counterparts, and alkaline magmas develop heavier Ti isotope compositions compared to other magma series during magmatic differentiation. Both observations are interpreted to reflect the preferential sequestration of light Ti isotopes in Fe-Ti oxides, such as rutile, ilmenite and titanomagnetite. However, such interpretations so far rely on whole rock studies of cogenetic magmatic samples and the detailed mechanics of oxide-melt equilibrium on the Ti isotope composition of magmas is poorly constrained. To address this, we have measured the Ti isotope composition of co-existing Fe-Ti oxides and groundmass or silicate melt in both natural lavas from contrasting tectonic settings (Heard Island and Santorini), and experimental run products (rutile-melt). All Fe-Ti oxide phases are consistently isotopically lighter than their respective host groundmass or silicate melt, with the magnitude of Δ49/47Tioxide-melt increasing from rutile to ilmenite, and titanomagnetite. The observed difference in Ti isotope fractionation between rutile-melt experiments and ilmenite-groundmass pairs is primarily reflective of small differences in their Tisingle bondO bond length, with ilmenite being isotopically lighter (Δ49/47Tiilmenite-melt extrapolated to 1000 K = −0.600 ± 0.035‰) compared to rutile (Δ49/47Tirutile-melt at extrapolated to 1000 K = −0.404 ± 0.099‰) due to slightly longer Tisingle bondO bonds in ilmenite. In contrast, the variation in Δ49/47Ti observed between titanomagnetite-groundmass pairs increases as a function of increasing TiO2 content (increasing ulvöspinel component) in titanomagnetite, with Δ49/47Tititanomagnetite-melt values extrapolated to 1000 K ranging from −0.811 to −1.451‰ in Ti-rich titanomagnetite (21–23 wt.% TiO2; Usp66-73) from Heard Island compared to −0.673‰ to −0.863 in Santorini (14–15 wt.% TiO2; Usp45-49). We interpret this to result from a weaker and distorted crystal lattice due to changes in the local cationic environment resulting from exchange of smaller Fe3+ ions with larger Fe2+ ions during magnetite-ulvöspinel solid solution. Our results are consistent with fractionation factors inferred from Ti isotopic analyses of mineral separates and ab-initio calculations. We use these fractionation factors in combination with Ti isotope fractionation factors for silicate minerals recalculated from previous studies, along with petrologic information to model the behaviour of Ti isotopes during partial melting of Earth’s mantle as well as reproducing the observed variation in δ49/47Ti of differentiated magmas from distinct geodynamic settings.

The determination of fractionation factors associated with important biogeochemical processes controlling Ni availability in the environment is necessary to confidently use Ni isotope signatures as tracers in environmental studies. In this paper we present experimental results on Ni isotope fractionation during the precipitation of Ni secondary minerals (Ni hydroxide, Ni hydroxycarbonate and Ni sulfide minerals) that can control Ni fate and mobility in settings where high dissolved Ni(II) concentrations may pose a serious threat to the environment. Results show a preferential partition of lighter isotopes into the solid phase with associated fractionation factors e of −0.40‰ ± 0.04‰, −0.50‰ ± 0.02‰, and −0.73‰ ± 0.08‰ relative to the hydroxide, carbonate and sulfide systems, respectively. Early kinetically induced isotope fractionation, followed by possible re-equilibration with the reacting solutions was suggested for the three investigated systems. Distortions of Ni-O bonds in the octahedra constituting the structures of Ni hydroxide and hydroxycarbonate minerals could have also contributed to the isotopic fractionation measured in these systems. In contrast, for Ni sulfide system, the magnitude of Ni isotope fractionation seemed to be determined by water and sulfide ligands exchange in solution prior to mineral nucleation. Although there is insufficient evidence to determine whether complete equilibrium occurred in the three studied systems, the fractionation factors reported in this study can provide useful indicators of Ni isotope fractionation associated with fast precipitation of secondary minerals involved in the sequestration of Ni from contaminated environments. These findings also contribute to the characterization of Ni isotope systematics which is still in the early stages of development.

The short-lived 146Sm-142Nd isotope system traces key early planetary differentiation processes that occurred during the first 500 million-years of solar system history. The variations of 142Nd/144Nd in terrestrial samples, typically within a range of ±20 ppm, are determined using high-precision mass spectrometry that requires quantitative separation of Nd from all other elements in the sample, including the neighboring lanthanides. Recent improvements in mass spectrometry have pushed the analytical precision of 142Nd/144Nd measurements down to ~2ppm. Non-mass-dependent isotope fractionation produced during the Nd separation, however, is a major factor limiting the quality of the 142Nd data. Popular chemical separation methods using Ln resins have unpredictable nuclear field shift effects that generate anomalous Nd isotope ratios. In order to solve this problem and potentially for resolving small 142Nd/144Nd variations within ±5 ppm, in this study, we present a new two-step column separation method that effectively removes the isobaric interferences of Ce, Pr and Sm, with a recovery rate of Nd greater than 98%. JNdi-1 standard solutions doped with these interfering elements, and geological reference materials are tested to document the performance of this method. A set of titanite samples from the Pilbara craton in western Australia was also investigated to test the potential isotope fractionation effects. The same samples were processed using our method and the widely used Ln method. In contrast to the nuclear field shift effects observed from the samples using the Ln method, the results based on our new method show no detectable isotope fractionation, which further confirms the reliability of this new column chemistry scheme that is optimized for ppm-level precision Nd isotope ratio measurement, especially for resolving small variations in 142Nd/144Nd caused by the decay of 146Sm.

Geochemical proxies—such as the isotopic compositions and abundances of redox-sensitive metals, organic biomarkers, and sedimentological indicators—can be used qualitatively and quantitatively to reconstruct marine redox landscapes through Earth history. Isotopic proxies with residence times longer than ocean mixing times, including uranium (238U/235U, commonly denoted as δ238U), are a promising but still developing approach to constrain global changes in redox conditions. Our current understanding of the controls on δ238U variability and associated isotopic fractionations is limited, complicating the interpretation of δ238U records through Earth history. With these gaps in mind, we investigate the major controls on the expression of uranium (U) isotope fractionation within two basins of the Miocene Monterey Formation (ca. 18–6 Ma) that represent contemporaneous deposition under different environmental conditions. Our finding that the isotopic offset in the productive and anoxic Santa Barbara Basin is similar to that in modern euxinic settings suggests that highly productive settings without persistent euxinia can also exert significant leverage on seawater δ238U. Distinct patterns in U concentrations and δ238U between basins demonstrate that local depositional controls can impart a strong influence on the U isotope offset in reducing settings, as has been observed in modern sediment datasets. High productivity and low sedimentation rates are predicted to result in a diagnostic inverse relationship between U enrichment and δ238U, which can partially explain the overall weak negative correlation between [U] and δ238U in the distal Naples Beach section in the Santa Barbara Basin. In a core from a more restricted proximal setting in the San Joaquin Basin, we propose that changes in basin hydrography led to a potential relationship between [U] and δ238U. These interpretations are consistent with the characteristic depositional conditions interpreted independently for each basin (e.g., persistence of anoxia, productivity, sedimentation rates, phosphate content, and basin hydrography) and are supported by modeling results of U enrichment and isotope fractionation under these conditions. In particular, our results suggest that the isotope offset of U in reducing sinks varies and has done so over Earth history and in different paleogeographic locations as a result of local productivity and basin restriction. These variations indicate the need to consider these uncertainties in quantitative models of global redox conditions from δ238U records—and specifically in using δ238U to distinguish between euxinic and oxic redox states without considering other oxygen-depleted environments as part of a continuum of settings that can impact δ238U if spatially widespread. This study also highlights the utility of using different lithologies to evaluate global versus local controls on δ238U records as well as multi-proxy approaches to constrain ancient redox landscapes.

Zircon is often used to study granites (sensu lato) and continental crust because it is very resistant and can be analyzed for various isotope systems that provide time and source information about their parental melts. Granites with different petrological histories have distinct bulk-rock silicon isotope compositions but it is unclear if these differences are also detectable in zircon because of superimposed fractionation effects (e.g., related to temperature, silica content, magmatic processes). The present study explores the Si isotope signatures of zircon from various granite types to constrain their isotope fractionation behavior and uses them as igneous petrogenetic tools, and possibly as granite source discriminators when zircon is found in detrital sediments. Our results show that although Si isotope compositions in zircon can be modified by secondary (post-crystallization) processes such as alteration/weathering and metamorphism, they are primarily controlled by zircon-melt isotope fractionation, which depends on both zircon crystallization temperature and magma silica content. Once these fractionation effects are understood and filtered out, a pattern emerges between Si isotope signatures of zircons from different granite types that is consistent with theoretical and experimental results as well as with known Si isotope differences at the bulk-rock scale. Silicon isotope ratios in zircon can track magma evolution (e.g., temperature and SiO2 changes) and, hence, reveal complex processes that involved magma mingling, fractional crystallization, and/or multiple sources. This study, therefore, illustrates that Si isotopes in zircon can be used to investigate magma evolution and represents a useful complement to existing techniques in granite studies involving zircon (e.g., U-Th-Pb, Lu-Hf and O isotopes) provided that it is not used as a stand-alone technique.

Metal stable isotopes in marine carbonates have been widely used as novel proxies for metal cycling through the geological past. Amongst these metals, copper (Cu) and zinc (Zn) have received great attention owing to their vital roles in metabolic processes. However, whether modern marine biogenic carbonates record the seawater isotope signatures of Cu (δ65Cu) and Zn (δ66Zn) and mechanisms and factors controlling isotope fractionation of these metals remain unclear, hindering applications of both isotope systems in paleoceanography. Here we present annually-resolved records of δ65Cu and δ66Zn in seven coral (Porites) cores sampled from different marine settings in the South China Sea and the Luzon Strait, western Pacific. We find that the aragonitic skeletons of corals are enriched in light Cu but heavy Zn isotopes relative to surface seawaters, with δ65Cu and δ66Zn in the range of −0.16 ± 0.06‰ to 0.40 ± 0.05‰ and 0.06 ± 0.04‰ to 0.46 ± 0.08‰ (2SD), respectively. The coral δ65Cu exhibits significant inter- and intra-colony variations, which are most likely controlled by Rayleigh-type fractionation in the calcifying fluids of corals rather than by changes in environmental factors or seawater δ65Cu. We thus suggest that δ65Cu in ancient carbonates may not be a direct record of Cu isotope compositions in coeval seawaters. In contrast, coral δ66Zn shows insignificant temporal variation, and the Zn isotope fractionation between individual corals and seawaters are relatively small and constant (0.10 ± 0.05‰, n = 33, 2SD). This limited Zn isotope fractionation is much lower than that determined during inorganic precipitation of calcite, which is likely due to pH up-regulation by the coral that changes aqueous Zn speciation, and preferential organic complexation of the heavy Zn isotopes in the calcifying fluids. Therefore, Porites corals are promising archives for tracking historical changes of surface seawater δ66Zn. Our new datasets of reef carbonates, particularly the coral δ65Cu values which are measured for the first time, could provide a better constrain on marine Cu and Zn geochemistry and their modern oceanic mass and isotope budgets.

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.

The photosensitized transformation of organic chemicals is an important degradation mechanism in natural surface waters, aerosols, and water films on surfaces. Dissolved organic matter including humic-like substances (HS), acting as photosensitizers that participate in electron transfer reactions, can generate a variety of reactive species, such as OH radicals and excited triplet-state HS (3HS*), which promote the degradation of organic compounds. We use phthalate esters, which are important contaminants found in wastewaters, landfills, soils, rivers, lakes, groundwaters, and mine tailings. We use phthalate esters as probes to study the reactivity of HS irradiated with artificial sunlight. Phthalate esters with different side-chain lengths were used as probes for elucidation of reaction mechanisms using 2H and 13C isotope fractionation. Reference experiments with the artificial photosensitizers 4,5,6,7-tetrachloro-2′,4′,5′,7′-tetraiodofluorescein (Rose Bengal), 3-methoxy-acetophenone (3-MAP), and 4-methoxybenzaldehyde (4-MBA) yielded characteristic fractionation factors (−4 ± 1, −4 ± 2, and −4 ± 1‰ for 2H; 0.7 ± 0.2, 1.0 ± 0.4, and 0.8 ± 0.2‰ for 13C), allowing interpretation of reaction mechanisms of humic substances with phthalate esters. The correlation of 2H and 13C fractions can be used diagnostically to determine photosensitized reactions in the environment and to differentiate among biodegradation, hydrolysis, and photosensitized HS reaction.

International audience; Stable Ti isotopes have been applied in the detrital sediment record to reconstruct the bulk composition of Earth's continental crust due to the relationship between magmatic differentiation and Ti isotopic compositions. However, no study has systematically evaluated the influence of provenance, physical, and chemical weathering on the composition of sediments relative to the protolith they originated from. To test the influence of these processes on Ti isotopic compositions we investigate the Ti isotope composition of 82 surface samples including loess, volcaniclastic rocks, river sediment, and two separate weathering profiles through igneous rocks, collected from a broad geographical area and a range of environmental conditions. Limited but significant Ti isotope fractionation exists in samples subjected to extreme chemical weathering processes, potentially as a result of elemental mobilization. For example, the δ49Ti isotopic composition of bauxites developed on Columbia River basalt varies by up to 0.1‰, becoming isotopically heavier with increasing weathering intensity. However, negligible variation in δ49Ti was found in a second profile of saprolites developed on weathered diabase. Titanium isotope variations in loess do not correlate with chemical weathering intensity or size sorting, but may instead be related to the provenance of the sediment. We find that the δ49Ti of Amazon River sediments is correlated with the Al/Zr ratio, indicating that δ49Ti is impacted by sediment sorting. At our study sites, the river averaged offset between the isotopic composition of the bedload and the suspended sediment fraction is 0.051‰, with the largest offset being + 0.116‰. Our data suggest that during chemical weathering, heavy Ti isotopes are preferentially incorporated into secondary minerals producing higher δ49Ti in intensely weathered soils. During fluvial transport, the Ti isotopic composition of fine-grained sediment is heavier than that of its coarser counterpart. Crustal protolith composition and sorting during transport and sedimentation have a stronger effect on the Ti isotopic composition than chemical weathering. Our results have implications for studies that utilize the Ti elemental concentration to calculate relative enrichment or depletion during chemical weathering and physical transport processes in the Critical Zone and for studies using Ti isotopes in terrigenous sediments to infer the composition of their provenance.

Jezero Crater on Mars is a paleolacustrine environment where Mg-carbonates may host evidence of ancient life. To elucidate the environmental and mineralogical controls on biosignature preservation, we examined samples from five terrestrial analogs: Lake Salda (Turkey), Lake Alchichica (Mexico), Qinghai-Tibetan Plateau (China), Mg-carbonate playas (British Columbia, Canada), and a mine with fine-grained ultramafic tailings (Yukon, Canada). The mineralogical compositions of the samples varied, yet were often dominated by either aragonite (CaCO3) or hydromagnesite [Mg-5(CO3)(4)(OH)(2)center dot 4H(2)O]. Aragonite-rich samples from Alchichica, Mg-carbonate playas, and the ultramafic mine contained an abundance of entombed microbial biomass, including organic structures that resembled cells, whereas hydromagnesite-rich samples were devoid of microfossils. Aragonite often precipitates subaqueously where microbes thrive, thereby increasing the likelihood of biomass entombment, while hydrated Mg-carbonates typically form by evaporation in subaerial settings where biofilms are less prolific. Magnesite (MgCO3), the most stable Mg-carbonate, forms extremely slowly, which may limit the capture of biosignatures. Hydrated Mg-carbonates are prone to transformation via coupled dissolution-precipitation reactions that may expose biosignatures to degradation. Although less abundant, aragonite is commonly found in Mg-carbonate environments and is a better medium for biosignature preservation due to its fast precipitation rates and relative stability, as well as its tendency to form subaqueously and lithify. Consequently, we propose that aragonite be considered a valuable exploration target on Mars.

The potential transformation of hexachlorocyclohexane isomers (HCHs) within tree trunks could have a significant impact on the use of phytoscreening. However, the transformation mechanisms of HCH in trunks particularly in growth rings are not yet well understood. Therefore, a field study on an HCH-contaminated field site was conducted to investigate the fate of HCH, particularly α-HCH in tree trunks using multielement compound-specific isotope analysis (ME-CSIA) and enantiomer fractionation. The results indicate that α-HCH was transformed, as evidenced by higher δ13C and δ37Cl values detected across different growth ring sections and in the bark compared to those in muck and soil. Remarkably, in the middle growth ring section, δ13C values of HCH were only marginally higher or comparable to those in muck, whereas δ37Cl values were higher than those of the muck, indicating a different transformation mechanism. Moreover, the δ37Cl values of β-HCH also increased in the tree trunks compared to those in soil and muck, implying a transformation of β-HCH. Additionally, dual-element isotope analysis revealed that there are different transformation mechanisms between the middle growth rings and other sections. Our findings suggest that the transformation of HCHs in trunks could bias quantitative phytoscreening approaches; however, ME-CISA offers an option to estimate the degradation extent.

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.

International audience; The origin of volatile element depletion in terrestrial planets and meteorites relative to a solar composition represented by CI carbonaceous chondrites remains an unsolved problem. The isotope compositions of moderately volatile elements may offer the possibility to distinguish between the various processes that may have caused this depletion (e.g., partial condensation or partial evaporation). We report high precision Sn isotope measurements in carbonaceous chondrites and ordinary chondrites and the results are reported as δ124/116Sn. Four carbonaceous chondrites (Orgueil CI, Murchison CM2, NWA 5240 CV3 and Allende CV3) show a limited range in δ124/116Sn (-0.02‰ to 0.11‰) with an average value of 0.04 ± 0.11‰ (2 s.d.) for a wide range of Sn concentrations (0.63 ppm to 1.57 ppm). The absence of Sn isotope fractionation among carbonaceous chondrites suggests that volatile depletion may have taken place under thermodynamic equilibrium conditions between solid and vapor in the Solar Nebula. Alternatively, the mixing of two components, a volatile-free component containing no or little Sn and a volatile-rich component could explain this trend. This latter hypothesis is consistent with the overall trace element pattern found in carbonaceous chondrites, showing a constant relative abundance when normalized to CI chondrites for the most volatile elements. In contrast with carbonaceous chondrites, ordinary chondrites exhibit a larger range of Sn isotope compositions (δ124/116Sn from -2.02‰ to 0.64‰), but neither the degree of metamorphism (3-6) nor the group (H, L, LL) is correlated with Sn isotopic variations, or with the Sn contents (range 0.20 to 1.44 ppm). Nineteen out of twenty-one ordinary chondrites are enriched in light Sn isotopes compared with carbonaceous chondrites and the bulk silicate Earth. The trace element patterns of volatile elements in ordinary chondrites suggest that equilibrated ordinary chondrites have been disturbed by parent body processes related to metamorphic or shock overprinting but also inherited isotope fractionation found in unequilibrated ordinary chondrites. Last, the isotope composition of the bulk silicate Earth (BSE) indicates that the volatile element depletion observed in the Earth took place in conditions perhaps similar to those of carbonaceous chondrites, as a simple model describing the effect of Earth's core formation on Sn isotopes shows that the Sn isotope composition of the bulk Earth is identical to that of the BSE and of carbonaceous chondrites.

We report the first zinc isotope data (expressed as δ66Zn relative to the JMC-Lyon standard) for chromian spinels (Cr-spinels) and coexisting olivines in oceanic peridotites. All spinel-olivine pairs fall on the 1:1 fractionation line in the diagram of δ66Znspinel versus δ66Znolivine, suggesting equilibrium isotope fractionation. Cr-spinels are always isotopically lighter than coexisting olivines (Δ66Znspinel-olivine = δ66Znspinel − δ66Znolivine = −0.50‰ to −0.33‰; n = 13), which is opposite to the positive Zn isotope fractionation between Al-spinel and olivine observed in cratonic peridotites. The “inverse” Zn isotope fractionation between Cr-spinel and olivine is unlikely to have been caused by low-temperature alteration of the oceanic peridotites, given the lack of correlation between Δ66Znspinel-olivine values and chemical indices of serpentinization and weathering (e.g., LOIs, MgO/SiO2). Ionic model calculation indicates that even considering that Zn occurs at both tetrahedral and octahedral sites in the crystal lattice of spinel, the magnitude of equilibrium fractionation is still inconsistent with the observed Zn isotope fractionation between Cr-spinel and olivine. We suggest a “chemical effect” in which the Zn O bond length (tetrahedral site) in spinel increases when Cr substitutes Al in octahedral site, which is corroborated by the striking negative correlation of δ66Zn with Cr# [molar Cr3+/(Cr3+ + Al)] in natural spinels. Therefore, Zn isotopic compositions of natural spinels can be highly variable depending on their chemical compositions. During magma differentiation, zinc is moderately incompatible in silicate minerals (olivine and pyroxene) but highly compatible in Cr-spinels/chromites that have Zn contents tens of times higher than those of basaltic melts. Given its light Zn isotopic composition, chromite crystallization–if any–can evidently elevate δ66Zn and lower Zn contents of the residual melts. Lunar mare basalts are typically characterized by higher δ66Zn and lower Zn contents relative to terrestrial basalts, but modelling suggests that chromite crystallization during magmatic differentiation is unlikely to account for Zn isotopic and elemental data of lunar mare basalts. Global ocean island basalts (OIBs) and some intraplate alkali basalts have systematically higher δ66Zn and higher Zn contents than those of the normal mantle-derived melts (e.g., mid-ocean ridge basalts; MORBs), which contradicts with a chromite crystallization model. Instead, such signatures can reflect recycling of surface carbonates into the Earth’s deep mantle, reinforcing the application of zinc isotopes as a tracer of deep carbonate recycling.

Serpentinite is one of the most important sources of volatiles and fluid-mobile elements in subduction zones. Attempts have been made to discriminate serpentinite-derived fluid from other sources (e.g., sediments, altered oceanic crusts) using a variety of geochemical tools, but such differentiation has proven to be changeling because fluids from different lithologies are dynamically mixed in the subduction channel. Serpentinites are essentially distinguished by high Cr contents and variable degrees of 53Cr excess. Given high Cr mobility in Cl-rich metamorphic fluids based on experimental determination, Cr elemental and isotope compositions could be potential markers for fluid-mediated mass transfer from serpentinites. Here, we test this hypothesis by analyzing Cr concentrations and isotope compositions of meta-basalts, as well as country mica schists, marbles and serpentinites from the southwestern Tianshan Orogen. The meta-basalts have highly variable Cr concentrations (30.0–625 ppm) and resolvable δ53Cr variations (−0.25‰ to −0.05‰), while mica schists and marbles have similar isotope compositions and low Cr contents (δ53Cr of −0.15‰ to −0.14‰ with Cr contents of 89.5–110 ppm for mica schists, δ53Cr of −0.21‰ to −0.17‰ with Cr contents of 4.1–8.73 ppm for marbles, respectively). Most of the investigated meta-basalts were carbonated. The positive correlations of loss on ignition (LOI), CO2, Sb and Sb/Ce with Cr contents, as well as with δ53Cr for these carbonated meta-basalts indicate that the metamorphic fluids are at least partially sourced from serpentinites and sedimentary carbonates. High pressure serpentinites display similar δ53Cr variations from −0.19‰ to −0.02‰, but high Cr contents ranging from 934 to 4920 ppm. Chromium isotope variations of these serpentinites could not be generated by serpentinization, due to opposite trends of Cr isotopes and serpentinization indexes compared with previous observations. Instead, dehydration of serpentinites during subduction/exhumation accounts for Cr isotope variations, generating fluids with high Cr concentrations and relatively lighter isotope compositions. According to a Rayleigh dehydration model, the estimated Cr isotope fractionation factor (αfluid-residue) between fluids and residual serpentinites is approximately 0.99995 –0.99975, implying that Cr species in the subducted serpentine derived fluid is probably as complexes of Cr3+-Cl− H2O(OH–). The mixing model reveals that investigated carbonated meta-basalts were sourced from initial evolved oceanic basalts metamorphosed by fluids from serpentinite dehydrations, with contributions from sedimentary carbonates. This work emphasizes that coupled Cr element and isotope systems present the potential ability to discriminate the complex fluid sources in subduction zones, particularly serpentinites.

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.

Rubidium is an active element on Earth, but whether and how its isotopes fractionate during geological processes are not known yet. In this study, we present data showing large variations in δ87Rb in bulk samples and individual mineral species from a granite weathering profile in South China as well as in surrounding stream water. The bulk samples show that the mobility of Rb ( τ R b TiO 2 ) fluctuates dramatically from −42.0% to 259%, and δ87Rb values vary from −0.30 ± 0.13‰ in the unaltered bedrock to 0.04 ± 0.08‰ in the weathered saprolites. Significant isotopic variations exist among individual mineral species. In the parent rock, biotite, chlorite, K-feldspar and plagioclase have the δ87Rb values of −0.42‰, −0.30‰, −0.23‰ and +0.01‰, respectively. In weathered products, major Rb-bearing minerals are K-feldspar, illite and kaolinite. The δ87Rb values of K-feldspar range from −0.23‰ to 0.14‰, which are likely influenced by the secondary clay minerals adhered on the surface. Illite is the intermediate secondary mineral during biotite and K-feldspar decomposition into kaolinite. The δ87Rb values of illite vary from −0.28‰ to −0.10‰. As the final product of chemical weathering in this profile, kaolinite has the heaviest isotopic composition, with calculated δ87Rb values ranging from −0.07‰ to 0.20‰. Chemical weathering drives the δ87Rb values of saprolites to become heavier. Nearby stream water has the average δ87Rb value of −0.22‰, which is slightly heavier than the value of parent rock but lighter than the saprolites at the upper part of the profile. Our results demonstrate significant Rb isotope fractionation at the Earth’s surface and that adsorption and desorption of clay minerals play a crucial role in triggering Rb isotope fractionation.

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.

Potassium elemental and isotope systematics were investigated for a suite of central European tektites from three strewn sub-fields in Czech Republic and possible parent sedimentary materials from the vicinity of the Ries impact structure in SE Germany, supplemented by data for several other impact-related materials (bediasites, Ivory Coast tektites, Libyan Desert Glass). This is paralleled by computation of potential K loss and attendant isotope fractionation for physico–chemical conditions typical for formation of tektite precursor melts. These theoretical calculations indicate a

Selenium behaves as a chalcophile and moderately volatile element during planetary accretion and magmatic processes on Earth. Together with the geochemically similar S and Te, Se is more volatile than most other moderately volatile elements and thus potentially becomes a new tracer to constrain the mechanism of volatile depletion in the Earth's mantle and other planetary bodies. As previously observed for several volatile elements, stable isotopes of Se are expected to fractionate upon eruptive outgassing of magmas. To understand the degassing behavior of Se and associated isotope fractionation, we report on Se and Te contents and Se isotope compositions (δSe) of submarine glasses across a range of distant ridge depth intervals along the Reykjanes Ridge and subglacial/subaerial basalts on Iceland (51–65°N; N = 22). Selenium (150–399 ng/g) and Te (2.61–14.5 ng/g) contents of the submarine glasses display progressive enrichment along the Reykjanes Ridge towards Iceland. This can be explained either by enhanced mantle melting towards Iceland or by enrichment of Se–Te contents in the mantle source due to the Icelandic plume–Reykjanes Ridge interaction. Both scenarios are equally plausible. The δSe values of submarine Reykjanes Ridge glasses range between −0.20 ± 0.08‰ and −0.08 ± 0.08‰ (on average −0.15 ± 0.07‰; 2SD, N = 15), which are unaffected by the Icelandic plume contribution and remain strictly within the previously reported average for depleted MORBs. These new data combined with literature δSe for depleted MORBs define a highly homogeneous depleted mantle composition δSe = −0.15 ± 0.11‰ (2SD, N = 44). On the other hand, we observed degassing of Se and Te to a variable extent (~40–95%) in submarine Reykjanes glasses at depths shallower than ~250 m and in subaerial/subglacial basalts on Iceland. Degassing-induced Se isotope fractionation shifted δSe of subaerial lavas towards heavier values (by up to ~0.44‰) well outside the range of submarine MORBs. However, when Se outgassing is associated with subglacial eruption, the outer glass rim of basalt preserves the primary/undegassed Se isotopic signature; whereas the pillow interior experiencing further Se loss (~50%) is enriched in heavier isotopes (−0.01 ± 0.12‰) relative to the outer glass rim (−0.22 ± 0.08‰). These observations are complemented by measurements of BHVO-2G from high-temperature heating experiments of the natural Hawaiian basalt BHVO-2, which show evaporation of 40% Se and 85% Te and resulting shift in δSe by ~+0.74‰. Degassing-induced Se isotope fractionation during volcanic eruption may be well explained by a simple Rayleigh distillation model with an empirical fractionation factor α of ~0.9998 (between volcanic gas and silicate melt). The results presented here show that Se isotope and Se–Te systematics can potentially contribute further constraints on degassing of chalcophile and volatile elements during terrestrial volcanism and large-scale planetary processes., We are especially grateful to Jean-Guy Schilling for his initial support and encouragement of the project, and to Katherine A. Kelley for providing us with all the samples. We acknowledge fruitful discussions with Ronny Schoenberg, Jabrane Labidi, and Timon Kurzawa, and lab support from Elmar Reitter and Maria Isabel Varas-Reus. We also thank Frances Jenner, Alex McCoy-West, and an anonymous reviewer for their through reviews and constructive suggestions, and Julie Prytulak for the efficient editorial handling. S. K. acknowledges financial support by the ERC Starting Grant O2RIGIN (636808).

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.

The isotopic composition of the detrital sediment record harbours a valuable proxy for estimating the composition of the erodible upper crust since the Archaean. Refractory elements such as titanium (Ti) and zirconium (Zr) can display systematic variations in their isotopic composition as a result of magmatic differentiation. Hence, the isotopic composition of such elements in detrital sediments could potentially be used to infer the average composition (e.g., SiO2 content) of their source region, even when elemental systematics are obfuscated by weathering and diagenetic processes. A key premise of this approach is that the isotopic composition of sediments remains unbiased relative to their protolith. To what extent isotopic fractionation can occur during sedimentary processes, notably the hydrodynamic sorting of heavy mineral assemblages with contrasting isotopic compositions, remains poorly understood. We investigate the effects of such processes on the Ti and Zr isotope composition of a suite of detrital sediments from the Eastern Mediterranean Sea (EMS). These sediments are binary mixtures of two main provenance components, Saharan dust and Nile sediment, with strongly contrasting mineralogical and geochemical signatures. The EMS sediments display clear evidence for hydrodynamic sorting of zircon, expressed as a large variation in Zr/Al2O3 and deviation of εHf relative to the terrestrial εNd-εHf array. Our new data, however, do not show pronounced Zr isotope variation resulting from either hydrodynamic sorting of zircon or sediment provenance. Although this agrees with theoretical models that predict negligible equilibrium zircon-melt Zr isotope fractionation, it contrasts with recent observations suggesting that kinetic Zr isotope fractionation might be a common feature in igneous rocks. For the EMS sediments, the negligible shift in Zr isotope composition through hydrodynamic sorting means that fine-grained samples accurately reflect the composition of their source. The nearly overlapping Zr isotope compositions of Sahara- and Nile-derived sediment, however, mean that Zr isotopes, in this case, have insufficient resolution to be a useful provenance proxy. Titanium behaves differently. A small but resolvable, systematic difference in Ti isotope composition is observed between the Sahara and Nile provenance components. Samples with a strong Saharan dust signature show some Ti isotope evidence for hydrodynamic sorting of oxides in tandem with zircon, but a much stronger effect is inferred for Nile sediment. Regression of the EMS sediment samples shows that the Ti isotope composition of the Nile-derived component is strongly fractionated compared to its protolith, the Ethiopian flood basalts. Whereas Ti in Nile sediment is carried in essentially unmodified concentration, and by inference isotope composition, from its sources to the delta, large-scale hydrodynamic sorting of Fe-Ti oxides occurs in the littoral cell. This process causes a decrease in TiO2/Al2O3 of the residual fine-grained sediment fraction and shifts its Ti isotope composition to heavier compositions. The potential of such an “oxide effect” in detrital sediments has implications for crustal evolution models that use Ti isotopes as a proxy for the proportion of felsic crust and can account for the observed scatter in the shale record.

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.

Speleothem formations are one of the most important and informative objects in paleoclimatological research. However, in order to interpret the data that reflect environmental conditions, we have to know the operation of the given cave, and it should be determined how the composition of the carbonate formed at the given site is related to the changes in the environmental parameters. The study presents the results of stable isotope geochemical analysis of speleothem formations and carbonate precipitated on glass plates collected in the Vacska Cave (Pilis Hills). The youngest layer of carbonate formations, formed in the last 1-2 decades, shows an isotope fractionation sign indicating strong ventilation, with the exception of a single site farthest from the entrance to the cave. The isotope shift was also accompanied by a change in carbonate fabric. Preceding the fabric change, the carbonate of the speleothem formations did not show ventilation-related shifts in the isotope compositions, suggesting that the exploration and opening of the cave areas may have caused the change. Based on this, we recommend the installation of local closures in the Vacska Cave and in the entire Ariadne cave system. The study provides a good example of how the results of basic research can be utilized in practical environmental protection, in the preservation of a strictly protected cave environment.

This study investigated the isotope effects of δ13C and δ15N and microbial response during biodegradation of hydrocarbons by biostimulation with nitrate or compost in the petroleum-contaminated soil. Compost and KNO3 amendments promoted the total petroleum hydrocarbon (TPH) removal accompanied by a significant increase of Actinobacteria and Firmicutes phyla. Soil alpha diversity decreased after 90 days of biostimulation. An inverse significant carbon isotope effect (ec = 16.6 ± 0.8‰) and strong significant nitrogen isotope effect (eN = −24.20 ± 9.54‰) were shown by the KNO3 supplementation. For compost amendment, significant carbon and nitrogen isotope effect were ec = 38.8 ± 1.1‰ and eN = −79.49 ± 16.41‰, respectively. A clear difference of the carbon and nitrogen stable isotope fractionation was evident by KNO3 or compost amendment, which indicated that the mechanisms of petroleum degradation by adding compost or KNO3 may be different.

Sorption to mineral surfaces is a key process that protects amino acids from oxidation and aids their polymerization into complex biomolecules. Sorption of neutral amino acids is driven by a combination of intermolecular forces, commonly through hydrogen bonds with surface functional groups. Substitutions of heavy isotopes are known to influence the strength of intermolecular interactions, but global C isotope fractionation associated with sorption is small ( 2‰) was observed for specific positions within a molecule during chromatographic separation, indicating that fractionation during sorption is likely more significant at positions that interact with a surface. We used quantitative isotopic 13C NMR to measure the relative difference in position-specific C isotopic distributions within glycine, l -alanine, l -serine, l -leucine, and l -phenylalanine sorbed to an ice surface versus in an aqueous solution. Isotopic differences up to 8.5‰ at functional sites were observed between sorbed and free amino acids, suggesting that sorption can alter primary isotopic patterns associated with their synthesis. Further, postion-specific isotope patterns appear to reflect the orientation of amino acids on the ice surface. As a result, position-specific isotope analysis may provide further understanding of mineral-mediated polymerization reactions.

Ferromanganese (Fe-Mn) crusts are potential archives of the Cu and Zn isotope compositions of seawater through time. In this study, the Cu and Zn isotopes of the top surface of 28 Fe-Mn crusts and 2 Fe-Mn nodules were analysed by MC-ICP-MS using combined sample-standard bracketing for mass bias correction. The Zn isotope compositions of the top surface of Fe-Mn crusts are in the range of 0.71‰ to 1.08‰, with a mean δB66Zn value of 0.94‰±0.21‰ (2SD, n=28). The δ65Cu values of the top surface of Fe-Mn crusts range from 0.33‰ to 0.73‰, with a mean value of 0.58‰±0.20‰ (2SD, n=28). The Cu isotope compositions of Fe-Mn crusts are isotopically lighter than that of dissolved Cu in deep seawater (0.58‰ vs. 0.9‰). In contrast, the δ66Zn values of Fe-Mn crusts appear to be isotopically heavy compared to deep seawater (0.94‰±0.21‰ vs. 0.51‰±0.14‰). The isotope fractionation between Fe-Mn crusts and seawater is attributed to equilibrium partitioning between the sorption to crusts and the organic-ligand-bound Cu and Zn in seawater. The Cu and Zn isotopes in the top surface of Fe-Mn crusts are not a direct reflection of the Cu and Zn isotopes, but a function of Cu and Zn isotopes in modern seawater. This study proposes that Fe-Mn crusts have the potential to be archives for paleoceanography through Cu and Zn isotope analysis.

Recent analytical advances have provided means to measure potassium (K) isotopes in various terrestrial materials, but little is known about K distribution and stable isotope composition in the lithospheric mantle because of: (a) common low K abundances, (b) potential contamination and alteration, (c) diversity of mantle rocks and minerals hosting K in different tectonic settings. We report K abundances and δ(41)K values for well-studied whole-rock (WR) mantle xenoliths (spinel and garnet peridotites and pyroxenites) from mobile belts, a craton, a subduction zone, as well as for K-rich phases (mica, amphibole, silicate glass) and xenolith-bearing volcanic materials (67 samples). The xenolith materials show extremely broad ranges of K content (7 μg/g to 6.6 wt.%) and δ(41)K (−2.77‰ to 0.62‰). They contrast with the narrow δ(41)K range for host volcanic materials (−0.53‰ to −0.27‰) and literature data on oceanic basalts (melting products of upwelling asthenosphere: −0.43 ± 0.17‰, 2sd). Amphibole-bearing subduction zone peridotites show the highest WR δ(41)K values (0.40 to 0.62‰) likely inherited from fluids released into the mantle wedge from subducted oceanic crust. All other WR samples yield negative δ(41)K: −0.06‰ to −2.77‰ for peridotites and −0.17‰ to −0.52‰ for pyroxenites. The δ(41)K in K-rich mantle phases range from positive values (0.16 to 0.57‰) for phlogopite in strongly metasomatized peridotites to negative values (−0.27 to −0.94‰) for phlogopite, amphibole and glass pockets from other samples, which cannot be explained by equilibrium inter-mineral fractionation inferred from ab initio calculations. We attribute the broad δ(41)K variations to (a) isotope fractionation during fluid-rock interaction in the mantle, and (b) distinct sources of K-bearing fluids. Kinetic isotope fractionation during fluid percolation and diffusion is inferred for composite xenoliths (phlogopite and pyroxenite veins in peridotites) that have lower δ(41)K in the hosts than in the veins due to slower migration of (41)K than (39)K from the veins (former fluid channels) to host mantle. Overall, the K isotope fractionation in the lithospheric mantle appears to be greater than for magmatic fractionation in the crust. The average δ(41)K of normal off-craton continental lithospheric mantle calculated from the least altered fertile and lightly metasomatized lherzolites is −0.57 ± 0.28‰ (2sd). This value is within error (though a little lower) of estimates for both continental crust and MORB and OIB mantle sources indicating that these major silicate Earth reservoirs have similar bulk δ(41)K values, apparently due to low or negligible K isotopic fractionation during their formation by magmatic differentiation and melting. By contrast, K isotopes in modern and fossil subduction zones are fractionated via fluid-related equilibrium and kinetic processes.

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.

To constrain the mechanisms governing the extremely large variations of Mg and Fe isotopes in magmatic Fe–Ti oxides in layered mafic intrusions, we investigate Mg isotopic compositions of magnetite, coupled with its chemical data and whole-rock major element and Sr-Nd isotope compositions from the Baima layered mafic intrusion in the Emeishan large igneous province, SW China. The Baima intrusion is mainly composed of magnetite-wehrlite and magnetite-troctolite (i.e., oxide-rich rocks) in the Lower Zone, and troctolite and gabbro (i.e., oxide-barren rocks) in the Middle and Upper Zones. Magnetite separates display large Mg isotopic variation, with δ26Mg ranging from −0.17 ± 0.06 to +0.58 ± 0.04‰ in the oxide-rich rocks and from −0.18 ± 0.06 to +0.98 ± 0.04‰ in the oxide-barren ones. The lack of correlation of δ26Mg with trace elements in magnetite and whole-rock Sr-Nd isotopic compositions indicates that the large Mg isotopic variation in magnetite was not produced by fractional crystallization, magma mixing, crustal contamination, and/or trapped liquid shift. Instead, equilibrium isotope fractionation induced by Mg–Fe re-equilibration between magnetite and ilmenite at different subsolidus temperatures controlled the Mg isotopic variation in the oxide-rich rocks; and kinetic isotope fractionation driven by Mg–Fe inter-diffusion between magnetite and olivine and/or clinopyroxene dominated the oxide-barren rocks. Both processes were primarily controlled by the assemblage and modal abundance of coexisting minerals to which magnetite adjoins. Overall, fractional crystallization and subsequent subsolidus diffusion played crucial roles in the genesis of the Fe–Ti oxides in the Baima intrusion. Our results also reveal widespread isotope disequilibrium between coexisting minerals in mafic magma chambers and suggest that Mg isotope geochemistry has a great potential to characterize the formation of Fe–Ti oxides in layered mafic intrusions.

Hydrogen isotope ratios (D/H) measured on geological samples are used to trace the pathways of water in magmatic and hydrothermal systems. Interpreting respective isotope data relies thereby on the theoretical and empirical constraints on hydrogen isotope fractionation. This study revisits a recently discovered hydrogen isotope fractionation effect between alkali-rich and alkali-poor regions within hydrous alkali silicate melts (Wang et al., 2015). In a series of experiments conducted at variable P-T-XH2O, D2O conditions, we studied this intramolecular isotope effect by 1H and 2H solid-state nuclear magnetic resonance (NMR) spectroscopy on quenched hydrous sodium tetrasilicate melts (Na2O⋅4SiO2 with 1:1 H2O and D2O). The results indicate a marked difference in the reactivity of the protonated and deuterated hydrous species. It is observed that c. 70% of deuterium concentrates as deuterated silanols (Si-OD) in proximity to the sodium cations in the silicate melt structure, while the remaining 30% occupy the Na-poor regions in the silicate melt in the form of Si-OD and presumably molecular water (HDOm). This distribution remains nearly constant under all experimental conditions. In contrast, the concentration of protonated hydrous species (Si-OH, H2Om) in the Na-rich and -poor regions of the silicate melt varies as a response to changing experimental P-T-XH2O and cooling rate, which is linked to common water speciation reactions taking place within the melt (Si-O-Si + H2Om = 2Si-OH). Previously considered insignificant, 1H NMR indicates that the speciation equilibrium is sensitive to pressure and correlates positively with Si-OH concentration. The significantly different reactivity of the isotope substituted hydrous species results in large molecular variations in the D/H ratio inside the sodium silicate melt. Measured intramolecular hydrogen isotope fractionation yields a 2- to 9-fold (in average 3-fold) enrichment of deuterium in Na-rich depolymerized regions in the silicate network, which translates to intramolecular fractionations of 1000ln(α) = 400 to 2200. Generally, intramolecular fractionation tends to increase when the melt evolves towards fluid-saturated conditions. The pre-concentration of deuterium in the depolymerized Na-rich regions of the silicate melt results in a higher local D/H ratio that may carry over when these regions disintegrate into a silicate saturated aqueous fluid. In this way, intramolecular isotope fractionation poses a potent way of enriching silicate saturated aqueous fluids in deuterium, potentially explaining previous experimental in-situ observations of large hydrogen isotope fractionations in the hydrous-melt – silicate-saturated fluid system. The observed affinity of deuterium to combine with alkali-associated silanols could comprise an important molecular sieving mechanism for deuterium that enhances the D/H fractionation between silicate-rich fluids (and hydrous melts) and the surrounding host rock. Consequently, intramolecular hydrogen isotope fractionation in hydrous silicate melts and silicate-rich aqueous fluids may be a very effective deuterium filter acting in the deep geological water cycle.

The scavenging of dissolved trace metals such as chromium (Cr), molybdenum (Mo) and tungsten (W) and their authigenic enrichment in sedimentary archives mainly occur by particle shuttling that cause resolvable isotope fractionation. Because their scavenging is also dependent on the local marine redox potential and the overall marine chemical environment, the stable isotope composition of these elements in Archean sediments is widely used as paleoredox proxy. Tungsten, a new element in this tool box, is dissolved as the oxyanion tungstate (WO42−) at extremely low marine redox potentials and can thus help to reconstruct the earliest changes in the marine redox state. We tested the applicability of stable W isotopes as a new paleoredox proxy of the atmosphere–ocean system. We analyzed the δ186/184W of Precambrian igneous rocks to investigate the detrital background δ186/184W signature. This Precambrian igneous inventory (PII) shows δ186/184W values between −0.007 and +0.097‰, identical to the range of modern igneous crustal rocks, which indicates that the average Earth’s crust δ186/184W remained constant over billions of years. Furthermore, we present δ186/184W values of euxinic sediments from the Black Sea as a modern sedimentary analog, which we then compare with δ186/184W data of Archean and Proterozoic black shales (3.47–2.3 Ga). Modern Black Sea sapropels reveal crustal-like δ186/184W values between +0.050 and +0.071‰ suggesting limited authigenic enrichment of W in euxinic environments. Similarly, post-Great Oxidation Event shales (2.3 Ga) show crustal- or PII-like δ186/184W values indicating the deposition in euxinic or oxic environment. However, the Archean shale sample suites show elevated W concentrations and fractionated δ186/184W values up to +0.246‰, which we attribute to authigenic enrichment of heavy seawater W in a ferruginous setting. Thus, black shales δ186/184W values can help to distinguish between anoxic-ferruginous and euxinic depositional environments. Furthermore, we combine previously published Cr and Mo isotope data with new Cr and W isotope data to quantify the evolution of the marine redox state during the Archean. By combining the Eh-pH stability fields of W and Mo with the δ186/184W and δ98/95Mo values of Precambrian sediments, we suggest a 3-step evolution of the Precambrian ocean. (1) From 3.47 to 3.0 Ga, the Eh of a dominantly ferruginous ocean was between −0.4 V and −0.25 V, enabling the persistence of soluble WO42− but not MoO42− and thus only the authigenic enrichment of isotopically fractionated W. (2) Starting from 3.0 Ga, the Eh of some shallow-marine environments increased above −0.25 V, as indicated by δ98/95Mo values above the detrital background in shallow-marine sediments, while the Eh of the deep ocean still remained below −0.25 V indicated by the lack of authigenic Mo enrichment and fractionated δ98/95Mo values in deep-sea shales. (3) After 2.7 Ga elevated δ98/95Mo and δ186/184W values in deep-marine sediments suggest that the Eh of the ferruginous open-ocean now also increased above −0.25 V. We therefore suggest that the combination of δ98/95Mo and δ186/184W values of shales is a very promising tool to investigate earliest changes in marine redox conditions during the Archean.

Previous work has shown that about 10% of total clay-bound Fe(III) in unaltered nontronite NAu-1 is bioreducible, although it remains unclear how much of the bioreducible Fe pool persists after repeated oscillations between anoxic and oxic conditions. Here, we report on results from an experiment where we monitored the abundance of bioreducible Fe(III) in NAu-1 over three consecutive redox cycles using chemical extractions and Fe isotope analysis to document the changes in the nature and extent of Fe atom exchange. During each cycle, NAu-1 was reduced biotically by Shewanella oneidensis MR-1 and then re-oxidized abiotically by O2 via aeration. By the third reduction period (RP3), the bacteria were only able to reduce 5.7% of the total clay Fe, that is, 40% less than during the first reduction period (RP1). The decrease in bioreducible Fe(III) is attributed to preferential reductive dissolution of Fe(III) from the finest clay particles. Extrapolation of the observed trend implies that, once the reducible Fe of the finest clay particles is removed, around 4% of the total Fe of the clay remains permanently redox-active, presumably as Fe atoms within the octahedral mineral structure that are accessible to the bacteria. The proposed particle size-dependent evolution of bioreducible Fe(III) from RP1 to RP3 is supported by the observed increasing crystalline domain size, preferential Fe dissolution from the smallest aggregates, and decreasing Fe isotope fractionation factors between aqueous Fe(II) and structural Fe(III) and between solid-bound Fe(II) and structural Fe(III). Our results imply that, in redox dynamic environments, the fraction of insoluble clay-bound Fe that is potentially renewable for use by Fe-reducing bacteria is a function of the evolving size distribution of the clay particles.

The direct determination of silicate melts iron and silicon isotopes signature remains a major challenge of high-temperature isotope geochemistry. For this reason, melts are often approximated by silicate glasses. Calculation of precise equilibrium Si and Fe isotopes fractionation factors between minerals and melt would indeed allow us to distinguish equilibrium fractionation from diffusion-driven kinetic fractionation involved in the iron and silicon isotopes signatures of Earth and other planets. In this study, we use for the first time, first-principles molecular dynamics based on density functional theory to determine iron and silicon isotope compositions of different silicate melts, namely: iron-rich basalt, iron-depleted basalt, basanite, trachyte and phonolite. The 57Fe/ 54Fe reduced partition function ratios (β-factors) of the different melts span over a 1.1 ‰ range at 1000 Kelvin (K) while 30Si/ 28Si β-factors are much less influenced by the melt composition with a 0.5 ‰ fractionation range at the same temperature. The main parameter controlling iron isotope fractionation in silicate melts having similar iron oxidation state is, after temperature, the average Fe-O bond length. The chemical environment around iron (e.g. Fe-Fe distances) is suggested to contribute to Fe isotope fractionation as well. Silicon isotopes fractionation seems also affected, but to a lesser extent, by its local chemical composition with decreasing Si-Fe distances leading to slightly higher Si β-factor in the melt. From these melts Fe and Si β-factors, a new set of equilibrium fractionation factors between a variety of minerals and melts has been calculated. These new Δ 57Fe min-melt and Δ 30Si min-melt sets allow us to discuss whether processes such as fractional crystallization, partial melting and diffusion could be responsible for the documented Fe and Si isotopes variations in igneous rocks. Our results suggest that: 1) fractional crystallization may explain at least part of the Fe and Si isotopic evolution during magmatic differentiation, for values up to δ 57Fe = 0.65 ‰ and δ 30Si = -0.1 ‰, respectively, 2) partial melting of the upper mantle can produce the Mid-Ocean Ridge Basalts (MORB) iron isotopes signature. Finally, we calculated that olivine at equilibrium with a basaltic melt could display an iron isotope composition down to −0.1 ‰ for δ 57Fe. Hence, the lower isotopic compositions (δ 57Fe < -0.1 ‰) observed in natural olivines are most likely due to diffusion-driven kinetic fractionation.

The basis for the δ13C values of plant tissues used to infer past ecological environments is their relationships with modern ecological conditions. A total of 71 pairs of pollen and leaf samples were collected from Pinus yunnanensis, an endemic species of the Yunnan plateau, in northwestern Yunnan, China. Their carbon isotopic composition was examined to investigate the two tissues’ difference of stable carbon isotopes, possible factors affecting their δ13C values, and their distinctiveness within Pinus and Pinaceae. Our study showed that pollen δ13C values range from −32.92 to −26.34‰ with an average of −30.88‰, whereas leaf δ13C values vary between −33.79 and −28.96‰ with an average value of −31.2‰, suggesting an isotope fractionation between the two tissues. A statistically significant negative correlation between the pollen δ13C values and altitudes of the sampling sites as well as no significant correlation between the leaf δ13C values and altitudes suggested that pollen may be more sensitive to some climatic parameters than leaf. A comparison of the pollen and leaf δ13C values from Pinus yunnanensis with the available data from other Pinus species and other genus species of Pinaceae indicated that the pollen and leaf δ13C values of Pinus yunnanensis are the lowest, partially due to the effects of water availability.

Nitrogen oxides, classified as NOx (nitric oxide (NO) + nitrogen dioxide (NO2)) and NOy (NOx+ NO3, N2O5 HNO3, + HNO4+ HONO + Peroxyacetyl nitrate (PAN) + organic nitrates + any oxidized N compound), are important trace gases in the troposphere, which play an important role in the formation of ozone, particulate matter (PM), and secondary organic aerosols (SOA). There remain many uncertainties in the origin and fate of atmospheric N compounds including the understanding of NOy cycling, NOx emission budgets, unresolved issues within the heterogeneous uptake coefficients of N2O5, and the formation of organic nitrates in urban forests, to name a few. A potential tool to resolve some of these uncertainties are using natural abundance N isotopes in NOy compounds. Here we have developed a photochemical mechanism used to simulate tropospheric photochemistry to include 15N compounds and reactions as a means to simulate δ15N values in NOy compounds. The 16 N compounds and 96 reactions involving N used in the Regional Atmospheric Chemistry Mechanism (RACM) were replicated using 15N in a new mechanism called iNRACM. The 192 N reactions in iNRACM were tested to see if isotope effects were relevant with respect to significantly changing the δ15N values (±1 ‰) of NOx, HONO, and/or HNO3. The isotope fractionation factors (α) for relevant reactions were assigned based on recent experimental or calculated values. Each relevant reaction in the iNRACM mechanism was tested individually and in concert in order to assess the controlling reactions. The controlling reactions and their diurnal importance are discussed. A comparison between iNRACM predictions and observed δ15N NO3- in particulate matter from Tucson, Arizona, suggests the model, and isotope fractionation factors incorporated into it, are accurately capturing the isotope effects occurring during the photochemistry of NOy. The implication is that measurements of δ15N in NOy compounds may be a new way of tracing in situ N chemistry and a means of assessing NOx emission budgets.

Cadmium (Cd) isotopes have great potential for understanding Cd geochemical cycling in soil and aquatic systems. Iron (oxyhydr)oxides can sequester Cd via adsorption and isomorphous substitution, but how these interactions affect Cd isotope fractionation remains unknown. Here, we show that adsorption preferentially enriches lighter Cd isotopes on iron (oxyhydr)oxide surfaces through equilibrium fractionation, with a similar fractionation magnitude (Δ114/110Cdsolid-solution) for goethite (Goe) (−0.51 ± 0.04‰), hematite (Hem) (−0.54 ± 0.10‰), and ferrihydrite (Fh) (−0.55 ± 0.03‰). Neither the initial Cd2+ concentration or ionic strength nor the pH influence the fractionation magnitude. The enrichment of the light isotope is attributed to the adsorption of highly distorted [CdO6] on solids, as indicated by Cd K-edge extended X-ray absorption fine-structure analysis. In contrast, Cd incorporation into Goe by substitution for lattice Fe at a Cd/Fe molar ratio of 0.05 preferentially sequesters heavy Cd isotopes, with a Δ114/110Cdsolid-solution of 0.22 ± 0.01‰. The fractionation probably occurs during the transformation of Fh into Goe via dissolution and reprecipitation. These results improve the understanding of the Cd isotope fractionation behavior being affected by iron (oxyhydr)oxides in Earth’s critical zone and demonstrate that interactions with minerals can obscure anthropogenic and natural Cd isotope characteristics, which should be carefully considered when applying Cd isotopes as environmental tracers.

As an important volcanic geothermal region in China, Tengchong belongs to the Mediterranean-Himalayan geothermal belt and is characterized by a wide distribution of geothermal systems. The study area- Rehai- is the sole geothermal area in Tengchong in mainland China that discharges both acidic and alkaline hot springs with pH values ranging from 1.6 to 9.7 at temperatures between 50 and 97 °C. Natural geothermal environments with large variations in pH and temperature are ideal study sites to investigate silicon (Si) isotope fractionation mechanisms which are still insufficiently understood. In this study, we investigated 3 different geothermal systems, which have distinct fluid characteristics: (1) type I fluid from Diretiyan Spring (pH: 1.6–2.5, H SO4 water, saturated with respect to quartz), (2) type II fluid from Zhenzhuquan Spring (pH: 6.4, Na Cl SO4 water, saturated with respect to quartz), and (3) type III fluid from Dagunguo Spring (pH: 7.8–9.7, Na Cl water, oversaturated with respect to amorphous silica: SiO2am). The mechanisms controlling Si isotope fractionation during Si precipitation differ significantly between the three fluid types. In type I fluid, equilibrium fractionation controls Si isotope variability during silica precipitation, causing the highest natural Si isotope equilibrium fractionation (Δ30Si) detected to date, ranging in Δ30Siquartz-fluid from +1.09‰ to +2.78‰. The equilibrium isotope fractionation is essentially caused by balanced precipitation and dissolution rates and high ionic strength of the geothermal fluids. In type II fluid, amorphous silica formed during evaporation and/or cooling of the spring water during capillary rise and a kinetically controlled, uni-directional Si isotope fractionation is observed. In type III fluid, the Δ 30 S i S i O 2 a m - f l u i d ranges from −1.57‰ to +0.55‰ at the temperature range of 80–100 °C. The Δ 30 S i S i O 2 a m - f l u i d show a shift from kinetic to equilibrium controlled fractionation and demonstrate that isotopic re-equilibration can reset the original kinetic Si isotope values in dependence of the hydrochemical conditions like pH, temperature and ionic strength as well as reaction time. Here we show that isotopic re-equilibration after solid formation can shift the isotopic signatures originally inherited during precipitation, challenging the interpretation of Si isotope values in the ancient rock record.

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.

The number of studies using various stable isotope systems for tracing contamination sources and various biogeochemical processes is rapidly rising due to the increased availability of the techniqu...

To investigate isotope fractionation between biogenic carbonates and modern seawater, we measured K concentration, phase, and isotopic composition in calcified skeletons from a variety of calcifying species. Samples included deep-sea corals, hermatypic corals, bivalves, gastropods, brachiopods, and planktonic foraminifera recovered globally over the past ten years in habitats with temperatures varying from 2 to 29 °C. The δ41K values of the calcified organisms vary significantly, ranging from −0.72 ± 0.11 to 0.94 ± 0.04‰. Deep-sea corals exhibit the largest isotopic variability and the lowest δ41K, ranging from −0.72 ± 0.11 to 0.28 ± 0.09‰. Hermatypic corals display a moderate δ41K, ranging from −0.20 ± 0.07 to 0.37 ± 0.10‰. Bivalves display widely variable δ41K values from 0.04 ± 0.05 to 0.94 ± 0.04‰, including the highest δ41K observed. Gastropods exhibit δ41K values between −0.42 ± 0.06 and −0.12 ± 0.06‰, while brachiopods have δ41K values from −0.30 ± 0.05 to 0.24 ± 0.06‰. Limited foraminifera samples (n = 2) reveal δ41K values of 0.15 ± 0.06 to 0.21 ± 0.06‰. Synchrotron-based atomic analyses show that K in biogenic carbonates is dominantly hosted in amorphous K2CO3, calcite-like and aragonite-like K phases, and intracrystalline organic matrices of varying proportions. The K isotopic composition of marine biogenic carbonates is not strongly temperature-dependent, in general, but correlates with skeletal K phases. This phase-control may indicate a first-order biological control on skeletal K incorporation, partitioning, and associated K isotope fractionation. This appears to reflect a substantial “vital effect”; i.e., physiological modification of the environmental information recorded in calcifying organisms. Substantial variations in δ41K call for additional scrutiny before using marine biogenic carbonates to interpret ancient seawater δ41K composition as physiological modulation substantially complicates the interpretation of marine carbonate δ41K records through time. Future studies should include species-specific calibration with complementary synchrotron data to refine K isotope applications for paleoceanography.

Organic tracers (bulk δ13C and δ15N) are being increasingly used in sediment/particulate organic carbon source apportionment studies at the catchment scale to support sustainable land management decisions. Here, the use of these isotopic tracers in sediment fingerprinting depends on the critical assumption that δ13C and δ15N values remain conservative during the sediment delivery continuum. Such assumption, however, requires critical evaluation, especially since standard tracer conservation tests applied in conjunction with catchment scale studies are prone to masking potential issues at smaller spatial scales including the field scale. Against this background, our study evaluated the subtle isotopic shift associated with sediment redistribution to edge-of-field and assessed the impact on sediment source apportionment. In a C3-grass dominated study field, δ13C and δ15N values exhibited differences (i.e., Δ13C = 1.4 ± 0.7‰ and Δ15N = 0.4 ± 0.4‰) between soil depths of 0–5 cm and 5–10 cm. Sampled sediments at the edge-of-field flume had higher δ13C values than the 0–5 cm soil layer; i.e., Δ13C values were 0.3 ± 0.4‰ and 0.8 ± 0.4‰ for suspended and deposited (materials deposited in a basket downstream of a flume) sediment, respectively. In contrast, δ15N values increased in suspended (Δ15N = 0. 8 ± 0.6‰) but decreased (Δ15N = − 0.4 ± 0.5‰) in deposited sediment, compared to the 0–5 cm soil layer, suggesting that the N isotopes can respond differently in edge-of-field sediment types. Although current fingerprinting work tends to not take explicit account of organic tracer alteration during transport or after deposition, our results demonstrate that correcting sediment δ13C and δ 15N values for tracer alteration in a Bayesian un-mixing model generated robust and reliable estimates of source contributions to both target sediment types. We therefore recommend taking account of the subtle but consistently altered δ13C and δ 15N values along the sediment cascade in un-mixing modelling to help better discriminate sources and to improve un-mixing model estimates at the catchment scale.

Interpreting isotopic signatures documented in natural rocks requires knowledge of equilibrium isotopic fractionation factors. Here, we determine equilibrium Fe isotope fractionation factors between several common rock-forming minerals using a comparative approach involving three independent methods: (i) isotopic analyses of natural minerals from a metapelite from Mt. Moosilauke, New Hampshire, for which equilibration temperature and pressure are well constrained to be near the aluminosilicate triple point (T ≃ 500 °C, P ≃ 4 kbar), (ii) Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements of Fe force constants of minerals, and (iii) Density Functional Theory (DFT) ab initio calculations of Fe force constants of minerals. The minerals studied for Fe isotopes include, in increasing order of their β-factors: garnet We show how the newly determined equilibrium fractionation factors can be used to address diverse problems in Earth and planetary sciences, notably (i) Fe and Mg isotopic fractionation during anatexis, (ii) Fe isotopic fractionation in lunar ilmenite, and (iii) Ti isotopic fractionation during fluvial transport of minerals.