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We estimated δ13C of the C–H–O fluid produced by the decomposition of stearic acid at high-pressure and high-temperature conditions (10 and 17 GPa, 800–1600°C) from δ13C of the solid carbon products and the initial stearic acid. The δ13C of the stearic acid and the recovered graphite/diamond were −28.0‰ and −27.08 to −29.35‰, respectively. Then, the δ13C of the coexisting C–H–O fluid was estimated to be −26.3 to −29.2‰ based on the stoichiometry of the decomposition reaction C18H36O2 → 10C + 8CH4 + 2H2O. In the studied P-T-t conditions, carbon isotope fractionation through the stearic acid decomposition is as small as < 3‰. This means that the δ13C of the C–H–O fluid is almost identical to that of the initial stearic acid and can be a useful tracer of carbon source for diamond forming reaction such as in fluid/carbonate systems. [ABSTRACT FROM AUTHOR]

Hydrothermal alteration is crucial in the formation of many ore deposits, with potassium (K) mobilization and cycling being prevalent. Potassic metasomatism of wall rocks generally forms K-bearing minerals, such as hydrothermal feldspar and mica. However, determining the source and redistribution of K (and other elements transported by the same fluid) in hydrothermal systems is challenging. K isotopes offer a potential solution to this problem. This study presents new K isotope data from two K-rich alteration assemblages — K-feldspar and sericite-quartz-pyrite — in the Jiaodong gold province of China. The data covers a compositional range from unaltered granites to syn -magmatic potassic alteration (formation of K-feldspar) and post-magmatic syn -mineralization phyllic alteration (formation of sericite). Potassic alteration in granite correlates with significant K addition, whereas phyllic alteration of earlier phases of magmatic and hydrothermal K-feldspar resulted in K loss. K-feldspar altered granites display similar δ41K values (–0.55 to –0.42 ‰ for whole-rocks and –0.56 to –0.48 ‰ for K-feldspar separates) as unaltered granite (–0.52 to –0.47 ‰). The narrow δ41K range suggests that magmatic fluid exsolution and magmatic-hydrothermal alteration have a minor effect on δ41K of the altered rock. Phyllic alteration of K-feldspar altered precursor rock leads to K loss and elevated δ41K values ranging from –0.36 to –0.19 ‰ for whole-rocks and –0.34 to –0.17 ‰ for sericite mineral separates. As sericite preferentially incorporates 41K, sericite will have higher δ41K values than the precursor K-feldspar, whereas the fluids will have lower δ41K values. Our study demonstrates that hydrothermal alteration may affect the K isotope composition of altered rocks in several ways, contingent on the nature of the involved phases, making K isotopes a promising tool for studying hydrothermal alteration and associated mineralization. [ABSTRACT FROM AUTHOR]

It is generally accepted that organic–inorganic interactions involving H-rich fluids (i.e., H2O and H2) contribute significantly to hydrocarbon (HC) generation in sedimentary basins. However, the effects of two hydrogenation processes involving H2O and H2 on the generation and C/H isotope fractionation of HC gases from organic matter (OM) remain unclear. In this study, two groups of hydrothermal experiments involving low-mature kerogen without (Group 1) and with FeS (Group 2) at 330–420 °C and 50 MPa were conducted to simulate the hydrogenation of OM by H2O and H2, respectively. The experimental results show that the redox reactions between H2O and FeS lead to the generation of considerable amounts of H2 in the Group 2 experiments. HC gas yield in the Group 2 experiments reaches 1.8–3.6 times that in the Group 1 experiments at Easy%Ro of 1.05–2.50%. In addition, indirect hydrogenation via H2O-derived H2 generates HC gases with smaller 13C fractionation and more negative δ2H compared with direct hydrogenation via H2O. On this basis, the mechanisms for HC gas generation from two hydrogenations were addressed. Additionally, it is demonstrated that the equilibrium isotope effect (EIE) is responsible for the 13C and 2H isotope fractionation in the hydrogenation of OM by H2. [ABSTRACT FROM AUTHOR]

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Abstract Nitrogen isotope analyses of amino acids (δ15N‐AA) are being increasingly used to decipher trophic dynamics. Interpretation of δ15N‐AA in consumers relies on the assumption that consumer physiological status and nutritional status of prey have negligible influences on the trophic discrimination factor (TDF), hence a constant TDF value is used in trophic position (TP) equations. Recent experiments have shown that this is not always the case and there is also a need to validate derived TP estimates in the field. We take advantage of the uniquely long time series of environmental monitoring data and archived (frozen) samples from the species‐poor Baltic Sea. We analyzed δ15N‐AA in similar sized individuals of cod and in its prey herring from four decades, 1980–2018; including time periods where dramatic reduction in condition status of cod has occurred. We expected that TDF in trophic AAs would increase during periods of poor cod condition, resulting in inflated TP estimates. We found that calculated TP and empirical estimates of TDF (difference in δ15N in trophic AAs between cod and herring) for cod increased in recent decades and that this was linked to condition status, herring (prey) lipid content and the hypoxic state of the ecosystem. Statistically adjusting TP for condition and prey lipid content as well as environmental stress (hypoxia) resulted in lower cod TP which better resembled the observed decrease in herring TP in recent decades. TP calculated from stomach analysis data in cod individuals over the same period showed no trend over time and confirmed that adjusted TP estimates mirror the real dietary TP better than unadjusted. By simultaneously measuring condition/nutritional status in both predator and prey it is possible to adjust for them as confounding variables and decipher actual consumer TP, partly overcoming the issues of unknown and variable TDF‐values. Our study also highlights the importance of including environmental stressors (here hypoxia) when interpreting TP and reconstructing food webs.

Carbonate-silicate rocks of unclear origin have been observed in granulites of the Porya Guba of the Lapland-Kolvitsa Belt within the Fennoscandinavian Shield. The present work aims to reconstruct possible protoliths and conditions of metamorphic transformation of these rocks based on oxygen and carbon isotopic ratios combined with phase equilibria modeling. Isotope analysis and lithochemical reconstructions suggest that carbonate-silicate rocks of the Porya Guba represent metamorphosed sediments (possibly marls) with the isotopic composition corresponding to the Precambrian diagenetically transformed carbonates (δ18O ≈ 17.9 ‰, SMOW and δ13C ≈ –3.4 ‰, PDB). The chemical composition varies depending on the balance among the carbonate, clay, and clastic components. Significant changes of the isotopic composition during metamorphism are caused by decomposition reactions of primary carbonates (dolomite, siderite, and ankerite) producing CO2 followed by degassing. These reactions are accompanied by δ18O and δ13C decrease of calcite in isotopic equilibrium with CO2 down to 15 ‰ (SMOW) and –6 ‰ (PDB), respectively. The isotopic composition is buffered by local reactions within individual rock varieties, thus excluding any pronounced influence of magmatic and/or metasomatic processes.

Chemical weathering of silicate minerals is an important source for Ca, Mg, Na and K. However, in comparison with other major elements (e.g., Ca, Mg and Na) in waters, how K behaves during water-rock interaction remains poorly understood. Recent studies have shown that large K isotopic fractionation could occur during various processes of low-temperature water-rock interaction such as chemical weathering and adsorption, making K isotopes gradually become a powerful tracer for the sources, migration and transformation of K cycling in the subsurface. This overview summarizes K isotopic compositions of major reservoirs at the Earth’s surface, including upper continental crust, hydrosphere and other reservoirs (plants and fertilizers). We conclude that 41K is enriched in hydrosphere than upper continental crust, providing an opportunity to identify the K source in groundwater.The magnitudes and mechanisms of K isotope fractionation during common water-rock interaction processes are also summarized (i.e., silicate dissolution, secondary mineral formation, adsorption, cation exchange), demonstrating that limited K isotope fractionation occurs during silicate dissolution, while clay formation results in enrichment of 41K in waters and adsorption and cation exchange leads to depletion of 41K occurring in waters. These different behaviors of K during these water-rock interactions provide an opportunity for tracing the migration and transformation process of K in groundwater. This paper presents the latest research that applied K isotopes to trace silicate weathering and water pollution. Since K isotopes are an excellent tracer for silicate weathering, they can be used to reveal the sources, migration and transformation of K cycling in aquifers with abundant CO2. Additionally, the distinguishable behavior of K isotopes during chemical weathering, clay adsorption and cation exchange can be used to identify various water-rock interactions. Future K isotopic studies in the field of hydrogeochemistry should focus on: (1) constraining the contribution of multi-endmember control on sources of potassium in groundwater; (2) quantifying K behavior during long-term groundwater circulation; and (3) using multiple isotopes to trace carbon cycle-related processes.

The hydrogen isotope ratios (δ2HAA values) of amino acids in all organisms are substantially fractionated relative to growth water. In addition, they exhibit large variations within microbial biomass, animals, and human tissues, hinting at rich biochemical information encoded in such signals. In lipids, such δ2H variations are thought to primarily reflect NADPH metabolism. Analogous biochemical controls for amino acids remain largely unknown, but must be elucidated to inform the interpretation of these measurements. Here, we measured the δ2H values of amino acids from five aerobic, heterotrophic microbes grown on different carbon substrates, as well as five Escherichia coli mutant organisms with perturbed NADPH metabolisms. We observed similar δ2HAA patterns across all organisms and growth conditions, which–consistent with previous hypotheses–suggests a first-order control by biosynthetic pathways. Moreover, δ2HAA values varied systematically with the catabolic pathways activated for substrate degradation, with variations explainable by the isotopic compositions of important cellular metabolites, including pyruvate and NADPH, during growth on each substrate. As such, amino acid δ2H values may be useful for interrogating organismal physiology and metabolism in the environment, provided we can further elucidate the mechanisms underpinning these signals.

Abstract The fluxes of metal cations and isotopes released by weathering of silicate rocks are crucial and a prerequisite for constraining geochemical fluxes to rivers and oceans. This study presents mineral and elemental compositions along with 87Sr/86Sr and δ88Sr data from a basaltic weathering regolith on Hainan Island, South China to elucidate Sr isotope fractionation and weathering fluxes. The 87Sr/86Sr ratios vary from 0.703936 to 0.706338 as a result of differential weathering of the minerals. δ88Sr values in the weathering regolith range from −0.29 to 0.37‰, with the majority of the weathering regolith having lower δ88Sr values than the parent rock. Sr is leached into the soil solution during plagioclase decomposition, while 86Sr is preferentially adsorbed on the surface of secondary minerals. As weathering progresses, smectite decomposes and kaolinite desorbs under weakly acidic conditions, releasing the previously adsorbed 86Sr into the soil solution. The differential weathering of kaolinite and smectite controls the δ88Sr values of the weathering regolith, with pH being an important determinant of isotope fractionation. Furthermore, Sr elemental fluxes (SrFlux) and Sr isotopic fluxes (δ88SrFlux) of this weathering regolith were calculated using a mass balance model, yielding mean values of 0.20 (mg cm−3 Myr−1) and 0.052 (‰ (mg cm−3 Myr−1)), respectively. The δ88SrFlux exhibits a nonlinear positive correlation with the Chemical Index of Alteration (CIA), indicating that enhanced weathering leads to significant stable Sr isotope fractionation at CIA values below 95%. Our research promotes the understanding of Sr recycling and the fractionation behavior of stable Sr isotopes during consecutive weathering.

As important metal sulfides in the geochemical cycle of sulfur, the characteristics and formation processes of pyrites can provide useful clues regarding their environment. Based on previous findings, shale pyrites were divided into three major classes (euhedral pyrites, framboidal pyrites (framboids) and metasomatic pyrites) and six sub-classes in this study. At the microscopic scale, each type of pyrite is associated with a different formation process. Framboids are formed by burst nucleation in environments with a homogeneous distribution of nutrients while euhedral pyrites are usually formed on pre-existing sites (such as =FeS on the minerals surface) in the heterogeneous system. Metasomatic pyrites formed by the replacement of other ions in accountable material by iron ions and hydrogen sulfide ions in hydrothermal events. The morphology and isotope value of pyrite provide information to track the origins of their nutrient and characteristics of sulfur and iron pools. In addition, the trace element content of pyrite can serve as a proxy for paleo-ocean trace element abundance, indicating changes in atmospheric oxygen content. Additionally, pyrite can also serves as an indicator of shale gas reservoirs. [ABSTRACT FROM AUTHOR]

The genesis of peralkaline granites has fundamental implications for understanding their source characters and tectonic settings, yet it remains highly controversial after decades of research. Two major challenges in studies of peralkaline granites are how the peralkaline magmas evolve and how to trace their magmatic evolution. Here we use K isotopes in granites from Zhoushan archipelago of southeast China to explore these two issues. The Zhoushan archipelago hosts two groups of Cretaceous high-silica granites, which are the peralkaline rocks (PAG) and the calc-alkaline rocks (CAG). The CAG rocks exhibit a small variation (δ41K = −0.54 ± 0.06 ‰ to −0.36 ± 0.06 ‰) in K isotopic compositions, in contrast to the larger variation for the PAG rocks (δ41K = −0.67 ± 0.07 ‰ to −0.27 ± 0.05 ‰). The PAG rocks show strong correlations between δ41K values and various whole-rock major elements (i.e., Al 2 O 3 , Na 2 O, and K 2 O contents), but these correlations are absent for the CAG rocks. We propose that the separation of Na-rich alkali-feldspar, rather than low-Na alkali-feldspar and/or plagioclase, controlled the K isotope variability in PAG. The alkali-feldspar in PAG is enriched in Na, among which the alkali-feldspar with Or (orthoclase; mol. %) <15 is characterized by high δ41K ranging from −0.34 ‰ to 0.36 ‰. Geochemical modeling demonstrates that 23–33 % fractional crystallization of such Na-rich alkali-feldspar is required to generate the geochemical trends observed in PAG. Those findings suggest that crystallization of Na-rich alkali-feldspars dominates the magma evolution for peralkaline magmatism, supporting strong fractional crystallization in high-silica peralkaline magma. K isotopes show promise to trace detailed magmatic processes and provide constraints on the generation of peralkaline granites. [ABSTRACT FROM AUTHOR]

To better understand the behavior of Ti isotope fractionation during alkaline magma differentiation, we studied well characterized alkaline lavas from St. Helena Island (South Atlantic), as well as their titanomagnetite separates. The lavas are classified into three groups according to petrographic observations and major element composition. Group 1 and Group 2 samples (5 to > 13 wt.% MgO) have a narrow δ49/47Ti range (− 0.02 to 0.05‰), suggesting that Ti isotopic fractionation is insignificant in less evolved basaltic lavas. Conversely, Group 3 samples (MgO < 5 wt.%) are saturated with titanomagnetite and display a wide range in δ49/47Ti (− 0.02 to 1.96‰). The δ49/47Ti values for Group 3 samples show significant correlation with TiO2 and SiO2 content, as well as with Mg and Fe isotopic values. Moreover, titanomagnetite phenocrysts from Group 3 rocks have remarkably lighter δ49/47Ti values (− 0.54 to 0.01‰) relative to the corresponding whole rock (− 0.02 to 0.21‰), indicating that titanomagnetite crystallization exerts significant control over the δ49/47Ti of Group 3 samples. These observations are further supported by modeling calculations. Together with published Ti isotope data, the results demonstrate that the range in Ti isotopic evolution in alkaline, calc-alkaline and tholeiitic magmatic systems is controlled by fractional crystallization of diverse Fe-Ti oxides with contrasting Ti isotopic compositions. This makes Ti stable isotopes an important geochemical tracer for magma evolution. [ABSTRACT FROM AUTHOR]

Marine mammals detoxify organic methylmercury (MeHg) as inorganic mercury selenide (HgSe), yet the nature of the reaction intermediate species and the tissue-specific redistribution of Hg species in the body are unknown. We report that the identity and proportion of the dominant Hg species in long-finned pilot whale (Globicephala melas) tissues can be obtained from the bulk variation of isotopic values of δ202Hg against the extent of demethylation (percentage of total Hg as MeHg, %MeHg) using an alternating regularized inversion method. Our analysis of isotope data from two previous studies supports that MeHg is demethylated as a tetraselenolate species (Hg(Sec)4), which further transforms into HgSe. Hg(Sec)4 occurs in the liver, kidneys, muscle, heart, and brain, whereas HgSe biomineralization occurs only in the liver and kidneys. This study provides a mathematical approach that facilitates probing the molecular-level chemistry of mercury in biological tissues using bulk isotopic data.

Purposes In China, the exploration and development of deep oil and gas resources have gained significant attention in recent years. In order to meet the demands of development, many scholars have conducted research on the process of deep natural gas diffusion and have made noteworthy advancements. Methods Aimg to evaluate the applicability of deep natural gas diffusion behavior and the carbon isotope fractionation effect, the study is based on an analysis of Fick diffusion, Knudsen diffusion, surface diffusion, and configuration diffusion. Establishing an accurate mathematical model is believed crucial in comprehensively understanding the mechanism of diffusion behavior. Conclusions The current models for coupling can analyze not only the behavior of natural gas diffusion in deep nanometer pores, but also how it affects the overall intensity of diffusion and the degree of carbon isotope fractionation in low-permeability conditions. Furthermore, these mathematical models allow for the calculation of gas loss intensity when combined with the history of strata evolution. The objective of this research is to provide a more precise and quantitative representation of deep gas diffusion behavior. This will aid in the exploration and development of deep oil and gas reserves, and also have significant implications for the evaluation of deep gas reservoirs in terms of preservation and destruction.

The trophic discrimination factor (TDF) is a key parameter for stable isotope analysis and due to a lack of species-specific TDFs, mean universal values have been used, resulting in uncertainties about the trophic position of species and a call for more experiments. In this study, we have addressed the lack of experimental species-specific TDFs conducting three experiments of 128 days each to determine the TDF (muscle and liver) of three species, the piscivore Pseudoplatystoma corruscans (Spix & Agassiz, 1829), and the omnivores Piaractus mesopotamicus (Holmberg, 1887) and Astyanax lacustris (Lütken, 1875), tropical fishes native to the La Plata River basin. Then, we calculated the trophic position (TP) using the mean universal TDF from literature and the species-specific TDF produced in this study for Pseudoplatystoma corruscans. We estimated the TDFs for the three species through experiment and the values found differed from the mean universal TDF in the literature. Moreover, the TP was lower when using the species-specific TDFs. The TP is important for several analyses, including its use in functional diversity. Therefore, we recommend using species-specific TDF values for calculating TP once it differs from the results calculated with mean universal TDF.

The oceans, serving as some of the most extensive reservoirs of mercury (Hg) on Earth, play an essential role in the global Hg biogeochemical circulation, as a sink for atmospheric deposits and surface runoff while simultaneously emitting Hg to the atmosphere. Clarifying the mechanisms during cycling of Hg in marine ecosystems is a crucial segment in elucidating global Hg behavior and assessing its risks to wildlife and humans. The stable Hg isotope technique has emerged as a powerful tool for identifying potential sources and certain processes of Hg. Herein, the research advances in marine Hg biogeochemical cycling were reviewed from an isotopic tracing perspective, including sources of marine Hg, isotopic fingerprints across various marine media, and applications of Hg isotopes in pathways, transport, and transformation mechanisms associated with marine environments. The knowledge gaps and challenges were further discussed in the development of ultratrace level and species-specific isotopic analytical methods, the isotope fractionation mechanisms in reactions and processes, and the integration of multiple approaches and cross disciplines. These future studies would advance our understanding of Hg behavior in oceanic environments, its authentic function, and interactions with other ecosystems in the global Hg cycle, and evaluate its response to environmental changes. [ABSTRACT FROM AUTHOR]

The stable calcium (Ca) isotopes offer a minimally invasive method for assessing Ca balance in the body, providing a new avenue for research and clinical applications. In this study, we measured the Ca isotopic composition of soft tissues (brain, muscle, liver, and kidney), mineralized tissue (bone), and blood (plasma) from 10 mice (5 females and 5 males) with three different genetic backgrounds and same age (3 months old). The results reveal a distinctive Ca isotopic composition in different body compartments of mice, primally controlled by each compartment's unique Ca metabolism and genetic background, independent of sex. The bones are enriched in the lighter Ca isotopes (δ44/40Cabone = − 0.10 ± 0.55 ‰) compared to blood and other soft tissues, reflecting the preferential incorporation of lighter Ca isotopes through bone formation, while heavier Ca isotopes remain preferentially in blood. The brain and muscle are enriched in lighter Ca isotopes (δ44/40Cabrain = − 0.10 ± 0.53 ‰; δ44/40Camuscle = 0.19 ± 0.41 ‰) relative to blood and other soft tissues, making the brain the isotopically lightest soft tissues of the mouse body. In contrast, the kidney is enriched in heavier isotopes (δ44/40Cakidney = 0.86 ± 0.31 ‰) reflecting filtration and reabsorption by the kidney. This study provides important insight into the Ca isotopic composition of various body compartments and fluids. [ABSTRACT FROM AUTHOR]

The geochemistry of Ba is commonly used to study igneous processes and fluid-melt interaction in subduction zone and granitic environments. Recent advances in analytical techniques have also indicated that Ba isotope geochemistry has the potential to significantly augment these studies. Understanding the Ba isotope fractionation mechanisms is thus critical if this potential is to be fully realized. Hence, we have used the first-principles calculations based on the density functional theory (DFT) and long-time ab initio molecular dynamics (AIMD) simulation to calculate Ba isotope fractionation during felsic magma evolution. In fluids, the reduced partition function ratio (β factor) of aqueous Ba2+ is highly variable, depending on the coordination number (n) of H 2 O in the first hydration shell. At ambient surface conditions on the Earth, n = 8 best represents the aqueous Ba2+ species in natural fluid, and the temperature-dependent equilibrium Ba isotope fractionation between barite/witherite and fluids can be described by the relationships: 103ln α witherite-fluid = −0.00009×(106/T2) 2 + 0.0603×(106/T2) + 0.0003 and 103ln α barite-fluid = −0.0001×(106/T2) 2 + 0.0648×(106/T2) + 0.0004, which is consistent with previous theoretical and experimental studies. In hydrothermal fluids, the hydration number of Ba2+ varies from 4 to 6 at high P-T, and the cumulative average of 103lnβ is derived to be 0.0798 ± 0.005‰ in 923.15 K and 0.2 GPa. In silicate minerals, the enrichment of heavy Ba isotopes decreases in the sequence of muscovite > microcline ≈ celsian ≈ sanbornite > barylite > phlogopite. Variations in Ba concentrations and the degree of Al-Si disordering only induce limited Ba isotope fractionation, which would be hard to distinguish analytically. At high temperatures (> 600 °C), the melt phase is enriched in heavy Ba isotopes relative to any coexisting aqueous fluid and crystallizing minerals. During the early stages of felsic magma differentiation involving plagioclase crystallization as the main mineral, the δ138/134Ba and concentration in the residual melt remain close to their initial values, but any fluid exsolved from the melt will have light δ138/134Ba values. The high Ba distribution coefficient of K-feldspar means that the resultant K-feldspar granite inherits > 90% of the Ba contained in the initial magma reservoir. Hence, the δ138/134Ba of K-feldspar is close to that of the initial melt. During the final stage of felsic magma evolution, mixing of exsolved fluids from deeper reservoirs may significantly reduce the δ138/134Ba of the now Ba-depleted melt, and can account for the low δ138/134Ba values measured in highly differentiated leucogranites and pegmatites. [ABSTRACT FROM AUTHOR]

Zinc, an essential trace element that serves as a cofactor for numerous cellular and viral proteins, plays a central role in the dynamics of HIV-1 infection. Among the viral proteins, the nucleocapsid NCp7, which contains two zinc finger motifs, is abundantly present viral particles and plays a crucial role in coating HIV-1 genomic RNA, thus concentrating zinc within virions. In this study, we investigated whether HIV-1 virus production impacts cellular zinc homeostasis and whether isotopic fractionation occurs between the growth medium, the producing cells, and the viral particles. We found that HIV-1 captures a significant proportion of cellular zinc in the neo-produced particles. Furthermore, as cells grow, they accumulate lighter zinc isotopes from the medium, resulting in a concentration of heavier isotopes in the media, and the viruses exhibit a similar isotopic fractionation to the producing cells. Moreover, we generated HIV-1 particles in HEK293T cells enriched with each of the five zinc isotopes to assess the potential effects on the structure and infectivity of the viruses. As no strong difference was observed between the HIV-1 particles produced in the various conditions, we have demonstrated that enriched isotopes can be accurately used in future studies to trace the fate of zinc in cells infected by HIV-1 particles. Comprehending the mechanisms underlying zinc absorption by HIV-1 viral particles offers the potential to provide insights for developing future treatments aimed at addressing this specific facet of the virus's life cycle. [ABSTRACT FROM AUTHOR]

Multi element compound-specific stable isotope analysis (ME-CSIA) is a tool to assess (bio)chemical reactions of molecules in the environment based on their isotopic fingerprints. To that effect, ME-CSIA concepts are initially developed with laboratory model experiments to determine the isotope fractionation factors specific for distinct (bio)chemical reactions. Here, we determined for the first time the carbon and hydrogen isotope fractionation factors for the monooxygenation of the short-chain alkanes ethane, propane, and butane. As model organism we used Thauera butanivorans strain Bu-B1211 which employs a non-haem iron monooxygenase (butane monooxygenase) to activate alkanes. Monooxygenation of alkanes was associated with strong carbon and hydrogen isotope effects: εbulkC = -2.95 ± 0.5 ‰ for ethane, -2.68 ± 0.1 ‰ for propane, -1.19 ± 0.18 ‰ for butane; εbulkH = -56.3 ± 15 ‰ for ethane, -40.5 ± 2.3 ‰ for propane, -14.6 ± 3.6 ‰ for butane. This resulted in lambda (Λ ≈ εHbulk/εCbulk) values of 16.2 ± 3.7 for ethane, 13.2 ± 0.7 for propane, and 11.4 ± 2.8 for butane. The results show that ME-CSIA can be used to track the occurrence and impact of monooxygenase-dependent aerobic processes converting short-chain alkanes in natural settings like marine and terrestrial seeps, gas reservoirs, and other geological formations impacted by natural gas. [ABSTRACT FROM AUTHOR]

Chemical weathering is one of the most important processes on the Earth's surface, and lithium isotopes have been used as a promising tracer of silicate weathering, as the secondary clay minerals precipitated during silicate weathering are thought to preferentially incorporate the lighter 6Li isotope. However, to utilize lithium isotopes as a geochemical tracer, it is essential to quantitatively understand the partitioning of Li in clay minerals, including structurally bound Li and exchangeable interlayer ions, as well as the associated isotope fractionation. With classical molecular dynamic simulations and thermodynamic calculations, the cation exchange between Na-/K-montmorillonite and solvated Li in environmental solution are disclosed under different aqueous activity conditions. The Li+ ion, whose hydration ability is stronger than Na+ and K+ ions, is easier to swell the montmorillonite and shows less affinity for the clay. And the calculated cationic selectivity coefficients between Na+/K+ and Li+ ions are K c (Li → Na) = 2.0, K c (Li → K) = 10.0 for Arizona-type montmorillonite and K c (Li → Na) = 1.0, K c (Li → K) = 4.0 for Wyoming-type montmorillonite, which are comparable to reported experiments. The cationic partition of Li in the clay interlayer decreases when the hydration states of montmorillonite transform from triple-layer to bilayer and then to monolayer. Based on the density functional theory, the Li isotope fractionations for Li in clay interlayer sites and structural octahedral sites are further derived by thermodynamic calculations with path integral molecular dynamic simulation, which deals with the quantum anharmonicity. The behaviors of Li isotope in the bilayer hydration state closely resembles that in the aqueous solution, and only a slight Li isotope fractionation is found between the monolayer hydrated octahedral-substituted clay and solution phase (Δ7Li monolayer-aq = −2.0‰). While Li isotope fractionation between aqueous solution and mica structural sites is significant (Δ7Li structural-aq = −10.4‰) and shows an obvious quantum anharmonicity, which indicates the importance of the anharmonic treatment for Li isotope fractionation calculations. The newly calculated Li equilibrium isotope fractionation between clay and aqueous solution deviates from the experimentally determined fractionation factor, which can be attributed to the kinetic effects. Moreover, on the basis of the surface kinetic reaction model, the Li isotope fractionation becomes more pronounced with higher clay growth rate. By integrating the cationic selectivity coefficient and Li isotope fractionation, it is possible to constrain the fluid composition during Li-clay deposit and diagenesis, and to evaluate the intensity of chemical weathering processes as well as the related carbon cycle. [ABSTRACT FROM AUTHOR]

Isotope fractionation of metals/metalloids in biological systems is an emerging research area that demands the application of state-of-the-art analytical chemistry tools and provides data of relevance to life sciences. In this work, Se uptake and Se isotope fractionation were measured during the biofortification of baker's yeast (Saccharomyces cerevisiae)—a product widely used in dietary Se supplementation and in cancer prevention. On the other hand, metabolic labeling with 15N is a valuable tool in mass spectrometry-based comparative proteomics. For Se-yeast, such labeling would facilitate the assessment of Se impact on yeast proteome; however, the question arises whether the presence of 15N in the microorganisms affects Se uptake and its isotope fractionation. To address the above-mentioned aspects, extracellularly reduced and cell-incorporated Se fractions were analyzed by hydride generation–multi-collector inductively coupled plasma–mass spectrometry (HG MC ICP–MS). It was found that extracellularly reduced Se was enriched in light isotopes; for cell-incorporated Se, the change was even more pronounced, which provides new evidence of mass fractionation during biological selenite reduction. In the presence of 15N, a weaker preference for light isotopes was observed in both, extracellular and cell-incorporated Se. Furthermore, a significant increase in Se uptake for 15N compared to 14N biomass was found, with good agreement between hydride generation microwave plasma–atomic emission spectrometry (HG MP–AES) and quadrupole ICP–MS results. Biological effects observed for heavy nitrogen suggest 15N-driven alteration at the proteome level, which facilitated Se access to cells with decreased preference for light isotopes. [ABSTRACT FROM AUTHOR]

We have conducted Mo isotope analyses of granites and related hydrothermal molybdenite from six Sn-W deposits in the western belt of the Southeast Asian Tin Province (Myanmar and Yunnan, China). Our data show that tin granites have notably heavier Mo isotope compositions (avg. δ98Mo = 0.44 ‰) than arc lavas (avg. δ98Mo = −0.12 ‰). The lack of systematic variation of Mo isotope composition with SiO2, Differentiation Index, Rb/Sr, and Zr/Hf values of the studied tin granites suggests there was no Mo isotope fractionation caused by fractional crystallization of the reduced magma. We infer that the elevated Mo isotope compositions in tin granites are mainly inherited from reduced sedimentary sources with black shales (avg. δ98Mo = 0.44 ‰). We also observed remarkable Mo isotope fractionation during the magmatic-hydrothermal transition. The preferential incorporation of Mo4+ and isotopically light Mo into magmatic sulfides and partitioning of Mo6+ and heavy Mo isotopes into hydrothermal fluids account for significant fluid-melt fractionation of Mo isotopes during fluid exsolution from the reduced melt. The elevated Mo isotope composition in hydrothermal molybdenite from granite-related Sn-W deposits compared to that of porphyry Cu–Mo deposits derives from both the notably heavy Mo isotope signature of the reduced sedimentary sources and fluid-melt fractionation of Mo isotopes during the magmatic-hydrothermal transition. The sequestration of Mo during crystallization of reduced melt and the low Mo precipitation efficiency in the hydrothermal evolution prevents the formation of economic Mo mineralization in reduced magmatic-hydrothermal systems. Combined with published data from different Mo sinks, we propose a Mo cycling and isotope fractionation model for arc and back-arc systems of Andean-type subduction settings. [ABSTRACT FROM AUTHOR]

Key message: Little vertical or circumferential variation in within-tree xylem water δ2H and δ18O within three tree species. Vertical and circumferential patterns of xylem water isotope signatures in large trees are rarely characterized but may influence interpretation of water source investigations and soil/xylem water isotope offsets. To examine vertical and circumferential variation in xylem water δ2H and δ18O, we collected xylem tissue at 5 heights (0, 1, 4, 7 and 10 m) from three replicate trees of three species with contrasting xylem anatomy, two angiosperms (Liquidambar styraciflua and Quercus nigra) and one gymnosperm (Pinus taeda). Concurrently, we also determined δ2H and δ18O of groundwater, soil water, and recent precipitation. On a different day, we collected circumferential samples at 1 m from the same trees to test for sectorality effects. Water from stem and soil samples were cryogenically extracted and analyzed for δ2H and δ18O. Mean xylem water δ2H and δ18O were significantly different between species, both vertically and circumferentially. We did not find significant (p = 0.05) systematic variation in δ2H or δ18O with height. We found no significant evidence for sectorality effects on δ2H, δ18O. Variances of vertical synoptic xylem water δ2H or δ18O were similar between species, 7.2–10.4‰ for δ2H and 0.58–0.81‰ for δ18O. Circumferential variances were also similar between species, 4.0–6.0 for δ2H and 0.37–0.44 for δ18O. A mixing model showed that sweetgum, water oak and loblolly pine, were drawing most of their water from deep soil from 45 to 190 cm (84.7, 68.4 and 53.2%, respectively) however, soil water-excess values indicate δ2H fractionation effects on these estimates. Dual isotope mixing model evaluation with single and multiple sample configurations showed that source water estimates were not affected by within tree variability of xylem water signatures. Xylem water δ2H and δ18O variability with height or circumference, was 3.2 and 2.7 times less than between tree variation because of transient temporal and spatial processes and is, therefore, not likely to affect interpretations of water sourcing in these three species. [ABSTRACT FROM AUTHOR]

Redox-driven copper (Cu) isotope fractionation has been widely observed in low-temperature weathering and hydrothermal processes. However, how Cu isotopes may fractionate during magmatic processes remain unknown. To address this issue, we studied MORB samples from the East Pacific Rise (EPR) at 10°30′N to explore the Cu isotope behavior during magma differentiation. These samples are globally ideal because they are generated from a uniformly depleted sub-ridge mantle source but have experienced varying extents of fractional crystallization and sulfide segregation with large variations of MgO (1.76–7.38 wt%) and Cu (16.0–75.2 μg/g). Lavas with MgO ≥ 4.9 wt% involving olivine, clinopyroxene and plagioclase as the major liquidus minerals show homogeneous δ65Cu of 0.05 ± 0.03‰, suggesting little Cu isotope fractionation at this stage of magma differentiation. However, after Fe-Ti oxides appear on the liquidus, melt δ65Cu values first decrease rapidly to –0.41‰ at MgO of 3.9 wt% and then increase with the most evolved sample having δ65Cu of 0.08‰. Such a significant Cu isotope fractionation during magma differentiation has never been reported before. We suggest the large Cu isotope variation at MgO < 4.9 wt% reflect a redox change of MORB melt resulting from fractional crystallization of Fe-Ti oxides. The crystallization of ilmenite (Fe2+TiO 3), which is the first Fe-Ti oxide phase during MORB differentiation, causes a sudden increase of Fe3+/∑Fe in the residual melt and drives the redox reaction Fe3+ + Cu1+ → Fe2+ + Cu2+. As a result, sulfides segregated from the MORB melts have high Cu2+ content and heavy Cu isotope compositions with Δ65Cu Sulfide-Silicate melt > 0 because of the preferential bonding of heavy Cu isotopes (65Cu vs. 63Cu) with Cu2+, whose fractionation rapidly decreases δ65Cu of the residual melts. The increase of Fe3+/∑Fe will quickly drive the melt to be saturated in titanomagnetite (magnetite-Ulvöspinel solid solutions), whose crystallization decreases melt Fe3+/∑Fe and drives the redox reaction Fe2+ + Cu2+ → Fe3+ + Cu1+. As a result, the segregated sulfides after titanomagnetite saturation have decreasing Cu2+ content. These sulfides are also predicted to have low Ni content and exhibit Δ65Cu Sulfide-Silicate melt < 0, whose segregation raises δ65Cu in the residual melts. Therefore, we suggest a significant influence of redox states of Cu and abundance of Ni in the segregated sulfides on the Cu isotope fractionation during MORB differentiation. During mantle melting for MORB at ΔFMQ < 0, Cu isotope fractionation between melt and mantle sulfide is inferred to be limited, and the upper mantle has primitive MORB-like δ65Cu of 0.06 ± 0.05‰. [ABSTRACT FROM AUTHOR]

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Due to the different sources of raw materials and manufacturing processes, different automotive paint samples have different isotopic signatures, which can be used as the basis for distinguishing similar paint samples. The varnish is the paint applied on the outermost layer of the car, which is easily affected by the storage conditions. Therefore, the isotope ratios of different varnish samples under different storage conditions were analyzed. Ten automotive varnish samples were collected and stored for 6 months at room temperature away from light, high temperature of 60 ℃, low temperature of -20 ℃ and strong ultraviolet light. After that, the samples were analyzed by elemental analyzer-isotope ratio mass spectrometry (EA-IRMS). The carbon, hydrogen and oxygen isotope values were determined. The results showed that the carbon, hydrogen and oxygen isotope ratios of different paint samples can be used to distinguish different samples, the potential of identification and differentiation of paint samples using stable isotopes of carbon, hydrogen and oxygen were demonstrated. The carbon, hydrogen and oxygen isotope fractionation of the paint samples occurred under different storage conditions. The δ13C value of the samples shifted to a negative value after storage at high temperature and low temperature, greater variation of samples occurred at high temperature, and the influence of strong ultraviolet radiation was weak, which meant that UV light had little effect on the δ13C value of the paint samples. The δ2H value shifted to a positive value under the three conditions, which was most affected by ultraviolet radiation, and minimal change in the condition of high temperature. The δ18O value shifted to more negative under the three conditions. But the shift amplitude of the δ18O value was different between samples of different resin types. Among the three resin types of samples, polymethyl methacrylate lipid resin samples had the smallest offset due to the least oxygen content in the molecules, the variation ranges of glyceryl elaidate and sorbitan monostearate paint samples had little difference under the three storage conditions. Stable isotope analysis method can provide high resolution three-dimensional fingerprints for paint samples, which has great potential in paint identification applications, and can be applied to traceability analysis of paint physical evidence.

The origin of dolomite in Shahejie Formation shale of Jiyang Depression in eastern China were studied by means of petrologic identification, compositional analysis by X-ray diffraction, stable carbon and oxygen isotopic composition, and trace element and rare earth element analyses. The results show that the development of dolomite is limited in the lacustrine organic rich shale of Shahejie Formation in the study area. Three kinds of dolomite minerals can be identified: primary dolomite (D1), penecontemporaneous dolomite (D2), and ankerite (Ak). D1 has the structure of primary spherical dolomite, high magnesium and high calcium, with order degree of 0.3-0.5, and is characterized by the intracrystalline corrosion and coexistence of secondary enlargement along the outer edge. D2 has the characteristics of secondary enlargement, order degree of 0.5-0.7, high magnesium, high calcium and containing a little iron and manganese elements. Ak is characterized by high order degree of 0.7-0.9, rhombic crystal, high magnesium, high calcium and high iron. The micritic calcite belongs to primary origin on the basis of the carbon and oxygen isotopic compositions and the fractionation characteristics of rare earth elements. According to the oxygen isotopic fractionation equation between paragenetic dolomite and calcite, it is calculated that the formation temperature of dolomite in the shale is between 36.76-45.83 °C, belonging to lacustrine low-temperature dolomite. Based on the maturation and growth mechanism of primary and penecontemporaneous dolomite crystals, a dolomite diagenetic sequence and the dolomitization process are proposed, which is corresponding to the diagenetic environment of Shahejie Formation shale in the study area.

After the atmosphere, the ocean is the most well-mixed and homogeneous global geochemical reservoir. Both physical and biological processes generate elemental and isotope variations in seawater. Contrasting geochemical behaviors cause elements to be susceptible to different fractionation mechanisms, with their isotopes providing unique insights into the composition and evolution of the ocean over the course of geological history. Supplementing the traditional stable isotopes (H, C, O, N, S) that provide information about ocean processes and past environmental conditions, radiogenic isotope (Sr, Nd, Os, Pb, U) systems can be used as time markers, indicators of terrestrial weathering, and ocean water mass mixing. Recent instrumentation advances have made possible the measurement of natural stable isotope variations produced by both mass-dependent and mass-independent fractionation for an ever-increasing number of metal elements (e.g. Li, B, Mg, Si, Ca, V, Cr, Fe, Ni, Cu, Zn, Se, Mo, Cd, Tl, U). The major emphasis in this review is on the isotopic composition of the light elements based on a comparatively large literature. Unlike O, H and S, the stable isotopes of C, N and Si do not have a constant isotopic composition in the modern ocean. The major cations Ca, Mg, and Sr fixed in carbonate shells provide the best proxies for reconstruction of the composition of the ocean in the past. Exhibiting large isotope enrichments in ocean water, B and Li are suitable for the investigation of water/rock interactions and can act as monitors of former oceanic pH. The bioessential elements Zn, Cd, and Ni are indicators of paleoproductivity in the ocean. Characteristic isotope enrichments or depletions of the multivalent elements V, Cr, Fe, Se, Mo, and U record the past redox state of the ocean/atmosphere system. Case studies describe how isotopes have been used to define the seawater composition in the geological past. [ABSTRACT FROM AUTHOR]

Lithium (Li) isotopes are widely used as a tracer of silicate weathering. However, Li isotopic compositions of non-silicate phases carried by sediments/suspended particulate matters (SPM) have not been systematically investigated, and their influences on the dissolved δ7Li variations remain poorly known. This study investigated Li geochemistry of different chemical fractions extracted by sequential leaching from SPM samples in the Changjiang (Yangtze River) Estuary. Our results demonstrate that Fe-Mn oxyhydroxide is the largest reservoir of non-silicate Li, accounting for ∼5% of Li in bulk SPM samples. The proportion of Li in exchangeable fraction is only 0.3 ± 0.1%, with δ7Li values ranging from 14.2‰ to 22.4‰. In response to seawater addition, the dissolved Na progressively replaces physically-adsorbed Li, and the chemically-adsorbed Li is isotopically fractionated with a factor of 0.9883. In the Changjiang Estuary, δ7Li of Fe-Mn oxyhydroxides responds rapidly to environmental variations. The isotope fractionation factors during Li uptake into authigenic Fe- and Mn-oxyhydroxides are 0.981 and 0.9735, respectively. Possibly due to short interaction time during SPM passing through the estuary, incorporation of Li into non-silicate phases cannot drive a detectable alteration of estuarine dissolved Li concentration. By contrast, this study highlights the possibility of oxyhydroxides affecting δ7Li values of river water. Further work may focus on determining Li isotopic behaviours of non-silicate phases and their applications on environment reconstruction. [ABSTRACT FROM AUTHOR]

Stishovite is a key mineral for understanding the deep Earth water cycle because of its potential as a main carrier for water into the transition zone and lower mantle. During subduction-related metamorphism of basaltic oceanic crust, stishovite stabilizes at 8–9 GPa and comprises 10–25 vol% of the bulk mineralogy, with some experimental studies indicating that stishovite can accommodate 3.5 wt% H2O or more in the transition zone and upper lower mantle. This large water solubility has been explained by a hydrogarnet substitution mechanism (1Si4+ ↔ 4H+) and/or the incorporation of interstitial molecular water. To investigate water speciation and hydrogen isotope behavior, we synthesized partially deuterated hydrous stishovite at 9 GPa and 450 °C in a multi-anvil press (MA). The hydrous stishovite contains on average 1.69 ± 0.05 wt% water, which is consistent with earlier MA studies but is significantly lower than the 3.5 wt% reported from in situ diamond anvil cell (DAC) studies made at higher pressures and temperatures. 1H MAS NMR spinning sideband characteristics suggest a high abundance of interstitial molecular water in hydrous stishovite, while the presence of a hydrogarnet defect cannot be ruled out. Unit-cell volumes and deuterium enrichment in the quenched hydrous stishovite indicate that ~ 45% of the water is lost from the stishovite upon quenching and decompression of the experiment, consistent with a higher solubility. This implies that the pristine water contents of a P–T–fO2 equilibrated hydrous stishovite cannot be quenched to 1 atm and room temperature from classical MA experiments. We further present a capillary-based recovery method for fluid from experimental capsules, allowing direct determination of the D/H ratio of the experimental fluid and indirect determination of the hydrous stishovite. Using Rayleigh modeling to account for the quench-related water loss, we find that, at 450 °C and 9 GPa, deuterium is 3.5–4.5 times enriched in hydrous stishovite relative to coexisting aqueous fluid. This is opposite of what is commonly observed for mineral–fluid pairs above 300 °C, rendering hydrous stishovite a potential sink for deuterium and decreasing the D/H ratio of coexisting aqueous fluids. Partial decomposition (30–60%) of hydrous stishovite during mantle upwelling and production of primary basaltic melts could be accompanied by high-temperature D/H fractionation, decreasing the hydrogen isotope composition of such melts towards "mantle-like" δD values between −75 and −220‰. [ABSTRACT FROM AUTHOR]

Uranium (U) contamination of the environment causes high risk to health, demanding for effective and sustainable remediation. Bioremediation via microbial reduction of soluble U(VI) is generating high fractions (>50%) of insoluble non-crystalline U(IV) which, however, might be remobilized by sulfuroxidizing bacteria. In this study, the efficacy of Acidithiobacillus (At.) ferrooxidans and Thiobacillus (T.) denitrificans to mobilize non-crystalline U(IV) and associated U isotope fractionation were investigated. At. ferrooxidans mobilized between 74 and 91% U after 1 week, and U mobilization was observed for both, living and inactive cells. Contrary to previous observations, no mobilization by T. denitrificans could be observed. Uranium mobilization by At. ferrooxidans did not cause U isotope fractionation suggesting that U isotope ratio determination is unsuitable as a direct proxy for bacterial U remobilization. The similar mobilization capability of active and inactive At. ferrooxidans cells suggests that the mobilization is based on the reaction with the cell biomass. This study raises doubts about the longterm sustainability of in-situ bioremediation measures at U-contaminated sites, especially with regard to non-crystalline U(IV) being the main component of U bioremediation. [ABSTRACT FROM AUTHOR]

Sulfide-silicate liquid immiscibility (i.e., the coexistence of two liquid phases in equilibrium) plays a significant role in the processes of planetary-scale differentiation, the formation of Earth's crust, and the genesis of magmatic sulfide ore deposits. The stable isotope geochemistry of nickel can potentially take advantage of fractionation signals produced in magmatic systems where immiscible sulfide and silicate liquid have equilibrated. Variations in Ni isotope ratio beyond those found in sulfide-undersaturated basaltic rocks can provide a hallmark of fractionation processes that control chalcophile and siderophile element abundances. We report high-precision Ni isotope ratio data for a stratigraphically-controlled sequence of Siberian Trap basalts in a volcanic edifice centered over the world's largest concentration of magmatic sulfide ore deposits at Noril'sk-Talnakh, Russia. Nickel isotope ratios (δ60Ni (‰) = [(60Ni/58Ni) sample /(60Ni/58Ni) SRM986 -1] × 1000) in the basaltic rocks range from +0.07 ± 0.02‰ to +1.00 ± 0.04‰ and correlate negatively with Ni and precious metal abundance levels, indicating extensive Ni isotope fractionation due to sulfide saturation of the silicate magma. A Rayleigh fractionation model fits the observed results and enables a precise estimate of the fractionation factor (α) between sulfide liquid and silicate melt to be 0.99965 (i.e., 103*lnα = −0.35). Our study illustrates the application of Ni isotope ratio data in understanding sulfide-silicate liquid immiscibility and the broader implications with respect to the formation of the largest known magmatic sulfide ore deposits in association with the Siberian Trap. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Multi element compound-specific stable isotope analysis (ME-CSIA) is a tool to assess (bio)chemical reactions of molecules in the environment based on their isotopic fingerprints. To that effect, ME-CSIA concepts are initially developed with laboratory model experiments to determine the isotope fractionation factors specific for distinct (bio)chemical reactions. Here, we determined for the first time the carbon and hydrogen isotope fractionation factors for the monooxygenation of the short-chain alkanes ethane, propane, and butane. As model organism we used Thauera butanivorans strain Bu-B1211 which employs a non-haem iron monooxygenase (butane monooxygenase) to activate alkanes. Monooxygenation of alkanes was associated with strong carbon and hydrogen isotope effects: εbulkC = −2.95 ± 0.5 ‰ for ethane, −2.68 ± 0.1 ‰ for propane, −1.19 ± 0.18 ‰ for butane; εbulkH = −56.3 ± 15 ‰ for ethane, −40.5 ± 2.3 ‰ for propane, −14.6 ± 3.6 ‰ for butane. This resulted in lambda (Λ ≈ εHbulk/εCbulk) values of 16.2 ± 3.7 for ethane, 13.2 ± 0.7 for propane, and 11.4 ± 2.8 for butane. The results show that ME-CSIA can be used to track the occurrence and impact of monooxygenase-dependent aerobic processes converting short-chain alkanes in natural settings like marine and terrestrial seeps, gas reservoirs, and other geological formations impacted by natural gas.

The oxygen-isotope fractionations between brucite and water, portlandite and water, and brucite and portlandite have been calculated over the temperature range of 0 to 450 °C using quantum-chemical methods and several basis sets and functionals. The calculations also employ embedded clusters that are chosen using the Pauling-bond-strength-conserving termination method that maintains a neutral cluster with fractional charges assigned to terminal atoms. These calculations improve upon the previous semiempirical methods for predicting mineral-mineral fractionations. These semiempirical methods fail to accurately predict the relative enrichment and depletion of oxygen isotopes for the brucite-portlandite pair. The quantum calculations presented here also fail to predict at the absolute values for enrichment of oxygen isotopes between minerals and water, and a simple correction must be employed to achieve agreement with experiments if water is in the reaction. No such correction is needed to predict fractionation between minerals. The trends derived from the calculations are robust to changes in basis sets and functionals.

Uranium (U) contamination of the environment causes high risk to health, demanding for effective and sustainable remediation. Bioremediation via microbial reduction of soluble U(VI) is generating high fractions (>50%) of insoluble non-crystalline U(IV) which, however, might be remobilized by sulfur-oxidizing bacteria. In this study, the efficacy of Acidithiobacillus (At.) ferrooxidans and Thiobacillus (T.) denitrificans to mobilize non-crystalline U(IV) and associated U isotope fractionation were investigated. At. ferrooxidans mobilized between 74 and 91% U after 1 week, and U mobilization was observed for both, living and inactive cells. Contrary to previous observations, no mobilization by T. denitrificans could be observed. Uranium mobilization by At. ferrooxidans did not cause U isotope fractionation suggesting that U isotope ratio determination is unsuitable as a direct proxy for bacterial U remobilization. The similar mobilization capability of active and inactive At. ferrooxidans cells suggests that the mobilization is based on the reaction with the cell biomass. This study raises doubts about the long-term sustainability of in-situ bioremediation measures at U-contaminated sites, especially with regard to non-crystalline U(IV) being the main component of U bioremediation.

In aqueous geological environments, the fate and transport of Zn are controlled by geochemical reactions (e.g., sorption) occurring at the mineral/water interface. However, many of the underlying Zn fixation mechanisms, especially the kinetics of surface-induced precipitation, are still unclear. Additionally, Zn stable isotope fractionation during sorption has recently been shown to be an important process, but the relationship between Zn isotope fractionation and sorption mechanisms (e.g., surface complexation, precipitation) is also not well understood. To address these issues, we employed X-ray absorption fine structure (XAFS) spectroscopy, high-resolution transmission electron microscopy (HRTEM), and in situ/operando quick-scanning XAS (QXAS) spectroscopy to elucidate the sorption/precipitation mechanisms of Zn at palygorskite/solution interfaces. We also measured Zn isotope ratios during some sorption experiments to illustrate how Zn isotope fractionation behavior is affected by the evolution of coordination environments at different pH values, initial concentrations, and reaction times. Our results demonstrate that Zn sorption mechanisms vary as a function of pH, ionic strength, initial concentration, and reaction time. At low pH (pH < 7.0) and low ionic strength (I ≤ 0.01 M), Zn(II) predominantly forms an outer-sphere surface complex in octahedral coordination. At low pH (pH < 7.0) and high ionic strength (I = 0.1 M), Zn(II) is predominantly sorbed as an inner-sphere octahedral surface complex with insignificant isotopic fractionation (Δ66Zn sorbed-aqueous = −0.02 ± 0.05‰). At high pH and high initial Zn concentration (pH 7.5, C 0 ≥ 0.2 mM), the formation of octahedral Zn phyllosilicate precipitates is observed, yielding a small fractionation with an average Δ66Zn sorbed-aqueous of 0.10 ± 0.07‰. In addition, in situ/operando QXAS of Zn sorption at pH 7.5 in a flow cell revealed that the predominant sorbed Zn species shifted from inner-sphere tetrahedral complexes during the initial stage (e.g., within minutes) to inner-sphere octahedral complexes during later stages (e.g., within hours), followed by the formation of Zn-phyllosilicate precipitates (e.g., within days). This molecular evidence coincides with the evolution of Zn isotope fractionation from a large Δ66Zn sorbed-aqueous value (0.53 ± 0.05‰) to a small value of 0.05 ± 0.04‰ during the sorption process. The combination of QXAS and isotope fractionation results reveals a change in the Zn local environment from tetrahedral coordination to octahedral coordination. The findings in this study not only provide new insight into surface adsorption/precipitation mechanisms but also demonstrate that stable isotope fractionation is linked with the local molecular/bonding environments at mineral–water interfaces. [ABSTRACT FROM AUTHOR]

Birnessite minerals help control the fate of Zn in surface environments and readily fractionate Zn isotopes through adsorption reactions, yet little is known about the role played by various reactive sites in stable isotopic fractionation. Here we present the Zn isotope fractionation data cause by adsorption on birnessite under different reaction times, pH values, and Zn concentrations. We observe that isotopic equilibrium of Zn is attained after ∼120 h of reaction time at pH 6. At pH 3–5 and Zn concentrations of 0.05–0.3 mM, the isotopic fractionation (Δ66Zn adsorbed-aqueous) is around −0.46 ± 0.04‰, and gradually increases to −0.09 ± 0.05‰ at pH 6–8 and Zn concentrations of 0.2 mM. The change in Zn isotopic compositions as a function of pH and Zn concentration is well described using the surface complexation model, where two binding sites are involved: external edge sites and interlayer vacancies. According to this model, two different isotopic fractionation factors of Zn are calculated: Δ66Zn adsorbed-aqueous = −0.46 ± 0.04‰ for adsorption on vacancy sites and Δ66Zn adsorbed-aqueous = 0.52 ± 0.04‰ for binding to edge sites. Extended X-ray absorption fine structure spectroscopy (EXAFS) demonstrates that Zn forms triple-corner-sharing (TCS) octahedral complex on birnessite vacancies at pH 3 and Zn concentrations of 0.05–0.2 mM, where Zn is coordinated on one side to three oxygen atoms of the Mn vacancy (∼2.03 Å) and to three water molecules on the other side (∼2.15 Å), suggesting the formation of distorted Zn O octahedra (average bond length: ∼2.09 Å). At pH 6 and 8, double-corner-sharing (DCS) complexes on layer edges formed in addition to the TCS octahedral complex on vacancies. Density functional theory (DFT) optimisations suggest that DCS Zn complex exist in tetrahedral coordination. Based on EXAFS spectroscopy, DFT optimisations and surface complexation modeling, the distinct isotopic fractionation of Zn is related to the differences in Zn local structure at different reactive sites of birnessite. Our results provide a molecular-scale understanding of Zn isotopic fractionation in natural birnessite-containing settings, as well as new insights into predicting the links between adsorption and fractionation of other similar metals. [ABSTRACT FROM AUTHOR]

Organophosphorus flame retardants (OPFRs) are widely used in consumer products and are frequently detected in water, thereby threatening public health. In the present study, we investigated the mechanism of degradation of two representative OPFRs, tri(2-chloroethyl) phosphate (TCEP) and tri-n-butyl phosphate (TnBP), by thermally activated persulphate (PS). First, the experimental data were in accordance with the modelling simulations. In the absence of Cl−, the instantaneous concentration of SO 4 –• was 3.12 × 10−15 M. When the concentration of Cl− increased from 7.5 mM to 450 mM, Cl 2 –• became the dominant radical, with its concentration increasing from 7.39 × 10−14 M to 7.91 × 10−13 M. Conversely, the concentration of SO 4 –• declined from 6.3 × 10−17 M to 2.6 × 10−19 M. Second, owing to the transition of dominant radicals from SO 4 –• to Cl 2 –•, the resultant pseudo-first-order decay rates (r obs) of TCEP and TnBP were reduced. Without Cl−, r obs of TCEP and TnBP were (1.8 ± 0.1)× 10−2 h−1 and (6.1 ± 0.4)× 10−2 h−1, respectively. When the Cl− concentration reached 450 mM, the r obs of TCEP and TnBP dropped to (2.2 ± 0.2)× 10−3 h−1 and (2.4 ± 0.2)× 10−2 h−1, respectively. Additionally, despite the presence of oxidised Cl 2 –• compounds, when Cl− participated in PS oxidation, no primary organic chlorinated byproducts were detected. These results indicated that Cl− did not affect the toxicity of TCEP and TnBP transformation intermediates. Finally, the apparent kinetic isotope effects for carbon (AKIE C) and hydrogen (AKIE H) were detected to be 1.01 and 1.370–3.049, respectively. The results implied that the C-H split occurred during the PS-activated transformation of TCEP and TnBP. The present study combines quantitative steady-state radical calculation, transformation product identification, and isotope fractionation to characterise the radical transformation of typical OPFRs, thereby laying the foundation for regulating PS oxidation to eliminate OPFRs in real-world systems. [ABSTRACT FROM AUTHOR]

Fractional crystallization of Fe–Ti oxides can induce detectable Mg isotopic changes during late-stage basalt differentiation. Because chromite and olivine are early crystallizing phases during basaltic melt differentiation, the effect of chromite crystallization on the fractionation of Mg isotopes during early-stage basalt differentiation is still poorly understood. Here, we examine the possibility of chromite induced Mg isotope fractionation with a Mg isotopic study of chromite–olivine pairs in dunites and chromitites collected from major types of basaltic intrusive rock suites formed by fractional crystallization in different tectonic settings. The chromite δ26Mg (= [(26Mg/24Mg)sample / (26Mg/24Mg)DSM3–1] × 1000) values range from −0.19‰ to 0.30‰ in the Luobusa ophiolite, −0.09‰ to 0.78‰ in the Kızıldağ ophiolite, −0.04 to 0.42‰ in the Gaositai Alaskan-type complex, similar to those previously reported from the Stillwater layered intrusion (−0.05 to 0.84‰; Bai et al., 2021). They are significantly higher than those of coexisting olivine (δ26Mg = −0.48 to −0.10‰). The Δ26MgChr-Ol (= δ26MgChr − δ26MgOl) values in the rock suites investigated here fall largely between equilibrium fractionation lines of spinel–olivine pairs and magnesioferrite–olivine pairs, indicating equilibrium Mg isotopic fractionation. Furthermore, the Δ26MgChr-Ol values increase with decreasing Cr content of chromite in the dunites and chromitites, showing that high 26Mg has a greater affinity to Al-rich chromite than Cr-rich chromite. Fractional crystallization of such isotopically high chromite is expected to progressively lower the Mg isotope values of the in the remaining magma. Furthermore, continental basaltic magmas typically experience early crystallization of olivine and Al-rich chromite. Their δ26Mg values correlate positively with MgO (FeO, Cr,) and CaO/Al2O3 ratios and negatively with total alkali contents (Na2O + K2O). This indicates that detectable Mg isotopic fractionation occurred in intra-continental basalt magmas, probably by fractional crystallization of olivine and chromite. The observed low-δ26Mg intra-continental basalts can be accurately modeled by olivine + chromite fractionation with fractionation factors (Δ26MgChr-Melt) of 0.20‰, 0.60‰, and 1.18‰ as observed in the chromitites investigated during this study. Therefore, the early-stage basaltic melt differentiation involving separation of olivine and chromite may induce resolvable Mg isotopic fractionation, and the δ26Mg values of continental basalts should be used with caution in petrogenetic studies. [ABSTRACT FROM AUTHOR]

The Xihuashan and Yaogangxian granitic plutons in South China comprise highly evolved multiphase Li‐rich granites and host quartz‐vein‐type tungsten deposits. The δ7Li values of Phase A (early stage), B (middle stage), and C (late stage) from the Xihuashan pluton are 1.0–1.2‰, 1.1–3.0‰, and 2.4–2.8‰ respectively, increasing through chemical evolution. The granites from the Yaogangxian pluton also display gradually enriched in heavy Li isotopes in a later stage, although systematically lighter than those of the Xihuashan pluton. In both plutons, the δ7Li shows good correlations with SiO2 and Li concentrations as well as Rb/Sr, Nb/Ta, and Zr/Hf ratios, indicating Li isotopic fractionation most likely caused by magmatic differentiation. In situ analyses show that the minerals of Xihuashan pluton record a continuous elemental spectrum, reflecting the results of progressive magmatic differentiation. The δ7Li values of quartz, feldspar, mica, and zircon all correlate well with the chemical evolutions of granitic magma, systematically elevated in Phases B and C relative to Phase A. The Li isotope data of the mineral separates further document that the enrichment of 7Li in the residual melt was most likely due to the equilibrium fractionation between the mineral and melts. The data are interpreted to reflect that intense magmatic differentiation was responsible for Li isotopic variations coupled with the enrichment in the Li, F, P, and rare metals in the late‐phase granites of the Xihuashan pluton. The lithium isotope behavior documented in this study provides new insights into magmatic differentiation and associated rare‐metal mineralization. Plain Language Summary: In the past, magmatic differentiation was thought not to produce resolvable Li isotopic fractionation based on studies of basaltic rocks. Overall, only sparse studies on Li isotopes of highly evolved granites have been reported, and thus possible isotope fractionation of Li isotopes during differentiation of felsic magma could have been neglected. In this study, we present evidence of Li isotope fractionation during the differentiation of granitic magma. The most evolved (late‐stage) rare‐metal‐rich granites are systematically enriched in heavier Li isotopes. The chemical and isotopic compositions of both bulk rocks and mineral separates (e.g., zircon and mica) indicate that equilibrium fractionation during fractional crystallization governs Li isotopic behavior and enriches heavier Li isotopes in the residual melts. Our quantitative modeling also supports the equilibrium fractionation between minerals and magma as the primary mechanism for the observed Li isotopic variations. Key Points: Large Li isotopic fractionations are observed in rare‐metal‐rich peraluminous granitesFractional crystallization governs Li isotopic behavior and enriches heavier Li isotopes in the highly evolved granitesLithium isotopes provide new insights into the granitic magmatic differentiation process and rare‐metal mineralization [ABSTRACT FROM AUTHOR]

The practice of using isotope analysis in archaeological research, which has been developed in recent years, requires knowledge of the features of isotope fractionation in cultural layers and buried soils. The structural properties of geoarchaeological sites are determined by the local relief, climate, vegetation, landscape hydrology, and physical and chemical properties of soil-forming and underlying rocks, and the existence of cultures, and, therefore, their isotopic signature has a complex cumulative character. The aim of this work was to study the variability of the carbon-isotope composition of soils, rocks, and cultural layers of various landscape parts of geoarchaeological mounds in different natural zones of the Russian Plain to identify general climatic trends and the contribution of the anthropogenic factor to carbon isotope fractionation. The defensive ramparts of the Dmitrov Kremlin (Moscow oblast), Davydovo ancient settlement (Tambov oblast), Vodyanskii ancient settlement (Volgograd oblast), and necropolises of the Zhereno and Kvetun' archaeological complexes (Bryansk oblast) were chosen as study objects. It is shown that a significant variability in the carbon-isotope composition is typical for soils and cultural layers of geoarchaeological locations of different natural zones and enables us to identify the stages of stable soil formation on the surface of embankments and the stages of backfill structures. The isotopic ratios decrease in the humus horizons of modern and buried soils. An increase in isotopic ratios is characteristic of the cultural layers of geoarchaeological objects in all natural zones and marks the epochs of the existence of cultures; however, the mechanisms of this process require further research. Despite the predominant distribution of herbaceous vegetation on the day surface of the sites, the isotope signature of buried soils reflects the type of dominant zonal vegetation and, using the features of the photosynthesis type, enables the reconstruction of climate features in the region at various chronostages of the object existence. [ABSTRACT FROM AUTHOR]