Equilibrium Isotope Fractionation Research Articles

Position-specific and clumped isotope equilibria in propane: Ab initio calculations beyond the harmonic and Born-Oppenheimer approximations

Position-specific and clumped isotope compositions that reveal intramolecular isotope distributions can offer novel insights into the physical and chemical properties of substances. In particular, the intramolecular isotope effects observed in propane have demonstrated significant potential for constraining the formation and evolution of hydrocarbons. To calibrate measurements and interpret observations, a comprehensive understanding of equilibrium isotope fractionation within propane is required. However, previous studies yielded inconsistent calculations of position-specific isotope equilibria, and lacked any prediction of clumped isotope equilibria in the methyl group of propane. Here, we employ quantum chemical calculations beyond the harmonic approximation and the Born-Oppenheimer approximation to study the intramolecular isotope equilibria in propane. Benchmark coupled cluster calculations (CCSD(T)) were used to produce reliable frequencies of propane isotopologues. By integrating the CCSD(T) outcomes with effects beyond the harmonic and Born-Oppenheimer approximations, we present high-accuracy equilibrium carbon and hydrogen isotope fractionation between the methylene and methyl sites, and report for the first time the equilibrium Δ13CH2D and Δ12CHD2 signatures of the methyl group in propane. Our results of position-specific isotope equilibria can serve as a reference frame for calibrating both theoretical calculations and experimental measurements. The equilibrium Δ13CH2D and Δ12CHD2 values provide a theoretical framework for further studies of 13CD and DD clumping in methyl groups of alkanes, and are valuable for tracing the sources and sinks of methyl groups as well as processes related to methylation.

Equilibrium Fractionation of Stable Strontium Isotopes During Adsorption to Mn Oxides

AbstractUnderstanding the stable strontium isotope fractionation between seawater and ferromanganese crusts/nodules is crucial for reconstructing seawater Sr isotopic history. This study explores stable Sr isotope fractionation during adsorption to manganese oxides, as preliminary experiments indicated their higher Sr adsorption capacity compared to iron oxides. We observed that equilibrium in concentration and isotopic composition can be achieved within a day. The lighter isotope (86Sr) is preferentially adsorbed, with the fractionation extent showing no significant change with respect to reaction time, pH, or Sr concentration under low ionic strength conditions (−0.14‰). Equilibrium fractionation processes, rather than Rayleigh fractionation, more accurately represent the isotopic composition trends of dissolved and adsorbed Sr. Experiments in synthetic seawater demonstrated greater Sr isotope fractionation (−0.20‰) compared to low ionic‐strength solutions. This fractionation during adsorption by manganese oxides in synthetic seawater is consistent with the isotopic discrepancy between seawater and ferromanganese nodules, suggesting that Mn oxide adsorption is the primary mechanism for Sr accumulation in ferromanganese deposits. These results imply that ferromanganese deposit Sr isotopic compositions could be proxies for reconstructing seawater Sr isotopic history, which is influenced by carbonate burial and continental weathering, reflecting the global carbon cycle changes.

Antimony isotope fractionation during Sb(V) and Sb(III) adsorption on secondary Fe-minerals (schwertmannite, ferrihydrite) typical of mine waters

The application of antimony (Sb) isotopes as tracers for Sb environmental cycling is currently limited. Indeed, there is a lack of knowledge of isotope fractionation factors associated with key (bio-) geochemical processes controlling its behaviour in surface environments. This study investigated the equilibrium isotope fractionation generated by Sb(V) and Sb(III) sorption on two iron minerals typical of acid mine drainage (AMD) impacted streams, ferrihydrite and schwertmannite, under controlled conditions of pH and solid to liquid ratio. Sorption behaviour and Sb isotope fractionation were similar for the different mineral phases and Sb oxidation degrees, with fractionation factors Δ123Sbsolid-solution of −0.25 ± 0.08 ‰ for Sb(III) and −0.34 ± 0.08 ‰ for Sb(V) adsorbed on ferrihydrite and −0.36 ± 0.06 ‰ for Sb(III) and −0.27 ± 0.03 ‰ for Sb(V) adsorbed on schwertmannite. The pH and initial Fe:Sb ratio did not significantly affect the Δ123Sbsolid-solution value under the experimental conditions. The light 121Sb isotope was preferentially adsorbed on the mineral phases, following an equilibrium closed system between dissolved and adsorbed Sb species. This fractionation may be related to the apparition of iron as the second closest neighbour which distorts the Sb(OH)3 or Sb(OH)6- atomic polyhedron. This study confirms that Sb equilibrium isotope fractionation occurs during sorption of Sb(III) and Sb(V) onto secondary iron minerals and suggests that the pH and redox of Sb do not exert significant effect. pH and redox conditions are important parameters which control Sb mobility in AMD streams, therefore, the study provides data for interpreting Sb isotope signatures in mine waters.

Metal-binding amino acid ligands commonly found in metalloproteins differentially fractionate copper isotopes

Copper (Cu) is a cofactor in numerous key proteins and, thus, an essential element for life. In biological systems, Cu isotope abundances shift with metabolic and homeostatic state. However, the mechanisms underpinning these isotopic shifts remain poorly understood, hampering use of Cu isotopes as biomarkers. Computational predictions suggest that isotope fractionation occurs when proteins bind Cu, with the magnitude of this effect dependent on the identity and arrangement of the coordinating amino acids. This study sought to constrain equilibrium isotope fractionation values for Cu bound by common amino acids at protein metal-binding sites. Free and bound metal ions were separated via Donnan dialysis using a cation-permeable membrane. Isotope ratios of pre- and post-dialysis solutions were measured by MC-ICP-MS following purification. Sulfur ligands (cysteine) preferentially bound the light isotope (63Cu) relative to water (Δ65Cucomplex-free = − 0.48 ± 0.18‰) while oxygen ligands favored the heavy isotope (65Cu; + 0.26 ± 0.04‰ for glutamate and + 0.16 ± 0.10‰ for aspartate). Binding by nitrogen ligands (histidine) imparted no isotope effect (− 0.01 ± 0.04‰). This experimental work unequivocally demonstrates that amino acids differentially fractionate Cu isotopes and supports the hypothesis that metalloprotein biosynthesis affects the distribution of transition metal isotopes in biological systems.

Fractionation of iron and titanium isotopes by ilmenite and the isotopic compositions of lunar magma ocean cumulates

Basaltic volcanism on the Moon produced low- and high-Ti mare basalt suites that are also distinct with respect to their iron, titanium, and magnesium isotopic compositions. Here, the equilibrium fractionation of Fe and Ti isotopes between ilmenite and melt was experimentally investigated in order to evaluate the role of ilmenite in generating the isotopic compositional variability among the lunar mare basalts. Ilmenite crystallization experiments were conducted using two bulk compositions: an ilmenite-saturated basaltic andesite and an ilmenite-saturated Apollo 14 black glass, and the Fe and Ti isotopic compositions of the experimental ilmenites and glass (quenched melt) were analyzed using solution MC-ICPMS after hand-picking. Additionally, Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements on synthetic ilmenite were conducted and compared to previous NRIXS measurements on synthetic lunar glasses in order to derive temperature-dependent equilibrium ilmenite-melt Fe isotopic fractionations. Experimentally determined ilmenite-melt fractionations were then incorporated into a lunar magma ocean crystallization model that tracks the major element and isotopic compositional evolution of lunar magma ocean cumulates and residual liquid. There is good agreement between the Fe equilibrium isotopic fractionation measured by NRIXS and the laboratory equilibration experiments, and we find that the isotopic fractionation is sensitive to ilmenite compositional differences (0 vs. 10% Fe3+). Further, the light Ti isotopic composition of ilmenite relative to the melt (Δ49Ti=ilmenite-melt−0.09±0.03‰ at 1100∘C) is consistent with the higher coordination of Ti in ilmenite relative to melts and results of previous studies. The modeled Ti isotopic compositions for lunar magma ocean cumulates display Ti isotopic variability sufficient to explain the low- and high-Ti mare basalt sources. However, the difference in Fe isotopic composition between the low- and high-Ti mare basalts cannot be attributed solely to ilmenite fractionation. Instead, Fe isotopic fractionation by additional products of lunar magma ocean crystallization, such as clinopyroxene, is required to generate the inferred Fe and Mg isotopic variability in the lunar mantle. Alternatively, the Fe and Mg isotopic compositions of the lunar mare basalts may indicate Fe-Mg interdiffusion has occurred in the Ti-rich component of the mare basalt source regions via reaction between ilmenite cumulates and the olivine- and pyroxene-rich lunar mantle.

Calcium isotopic compositions of eclogite melts and negligible modification during reaction with lithospheric mantle

Subduction-driven recycling of crustal materials plays a substantial role in the generation of geochemical and lithological heterogeneities in the Earth’s mantle. Because the distinct compositions and/or mineral-specific equilibrium isotopic fractionation effects are present in eclogitized crustal materials, stable isotopes of major elements that exert significant impacts on geochemical and petrologic properties of the mantle may serve as powerful tracers for linking the geochemical anomaly to lithological heterogeneity within the Earth’s interior. Here we present high-precision Ca isotope data, combined with previously reported Mg-Fe isotopes, for a suite of intraplate basalts with a large contribution from recycled crustal material in their mantle sources. The δ44/40Ca in these potassic basalts are consistently lower (0.66–0.78 ‰) than those of mid-ocean ridge basalt (MORBs; 0.85 ± 0.09 ‰), with an average of 0.72 ± 0.09 ‰. The co-variations of major elements with radiogenic isotopes (e.g., MgO-ɛNd) reflect the mixing of two distinct endmembers, one of which is the low-MgO primitive melts and the other is the lithospheric mantle. The low-MgO, SiO2-rich primitive melts are characterized by low CaO/Al2O3 (<0.4) and high Dy/Yb (>5). Remarkably, the primitive melts exhibit low δ44/40Ca (ca. 0.70 ‰)-δ26Mg (ca. –0.60 ‰), and elevated δ57Fe (ca. 0.30 ‰) relative to MORBs. These features are consistent with their origin as partial melts of eclogitic crustal materials. During ascending to the surface, these melts reacted with the surrounding lithospheric peridotite. This process resulted in a noticeable shift of the Mg-Fe isotopes towards the typical mantle values but very limited δ44/40Ca modification. These results suggest that Ca isotopes largely hold the signature of primary melts and are a promising tracer of eclogite in the mantle source of basalts. We further show that the combined isotopes of Ca-Mg-Fe, which are stoichiometrically incorporated into mantle minerals, offer substantial potential to establish the links between lithological and geochemical heterogeneity in the mantle.

Complexation of Zr and Hf in fluoride-rich hydrothermal aqueous fluids and its significance for high field strength element fractionation

Zirconium and hafnium behave nearly identically in most geological processes due to their identical nominal ionic charge and similar radius. Some of the most pronounced exceptions from this rule are observed in fluoride-rich aqueous systems, suggesting that aqueous fluoride complexation may be involved in Zr/Hf fractionation. To understand the mechanisms causing this phenomenon, we investigated complexation of Zr4+ and Hf4+ in fluoride-rich (1.0 mol/kg HF) aqueous solutions at 40 MPa and 100–400 °C, using synchrotron X-ray absorption spectroscopy (X-ray absorption near edge structure and extended X-ray absorption fine structure) combined with classical and ab initio molecular dynamics simulations. The dominant experimentally observed complexes are [Zr(F,OH)4·2H2O]0 and [Hf(F,OH)4·2H2O]0, respectively. The first coordination shell comprises a distorted octahedron, with fluoride and hydroxide ligands at a similar mean radial distance (1.9–2.0 Å) from the central cation, and H2O ligands at a slightly greater distance (>2.1 Å). With increasing temperature, the H2O ligands move further out, causing first an increasing distortion of the octahedron and subsequently a partial transition to less hydrated complexes as a certain fraction of the H2O molecules move to the second shell at > 3 Å. As a consequence, the radial distance of the F- and OH– anions from the central cation, as well as the overall average radial distance of the first shell decreases due to decreased steric repulsion from the H2O ligands. Both experiments and simulations agree in that Hf forms slightly shorter bonds to its nearest neighbors than Zr. The results suggest two hypotheses for the mechanism of Zr/Hf fractionation during precipitation of minerals from fluoride-rich hydrothermal solutions: 1) The heavy twin (Hf) prefers the lower coordination (shorter bonds) and is thus less likely to enter into the higher coordination found in the solids. This mechanism would be analogous to equilibrium isotope fractionation. 2) The change of Hf into a higher coordination environment (e.g., from solution to solid) is slower because it forms stronger ligand-bonds than Zr. This would be analogous to reactive kinetic isotope fractionation. In either case mass dependent fractionation qualitatively matches the observations but mass independent effects on bond strength may also be significant. Quantitative investigations of these effects are needed and may also shed light on the currently still somewhat enigmatic fractionation behavior of Zr isotopes.

Copper isotope fractionation by diffusion in a basaltic melt

Copper shows limited isotopic variation in equilibrated mantle-derived silicate rocks, but large isotopic fractionation during kinetic processes. For example, lunar and terrestrial samples that have experienced evaporation were found to have an isotopic fractionation of up to 12.5‰ in their 65Cu/63Cu ratios, while komatiites, lherzolites, mid-ocean ridge and ocean island basalts show negligible Cu isotope fractionation as a result of equilibrium partial melting and crystal fractionation. The contrast between the observed magnitudes of equilibrium and kinetic isotope fractionation for Cu calls for a better understanding of kinetic Cu isotope fractionation. One of the mechanisms for creating large kinetic isotopic fractionation even at magmatic temperatures is diffusion. In this study, we performed Cu isotopic measurements on Cu diffusion couple experiments to constrain the beta factor for Cu isotopic fractionation by diffusion. We demonstrate a Monte Carlo approach for the regression and error estimation of the measured isotope profiles, which yielded beta values of 0.16 ± 0.03 and 0.18 ± 0.03 for the two experimental charges measured. Our results are subsequently applied to a quantitative model for the evaporation of a molten sphere to discuss the role of diffusion in affecting the bulk Cu isotopic fractionation between liquid and vapor during evaporation. We apply the model to Cu evaporation experiments and tektite data to show that convection primarily governs mass transport for evaporation during tektite formation. In addition, we show that Cu isotopes can be used as a tool to test the role of kinetics during various magmatic processes such as magmatic sulfide ore deposit formation, porphyry-type ore deposit formation, and fluid-rock interactions.

Variations in triple oxygen isotope of speleothems from the Asian monsoon region reveal moisture sources over the past 300 years

Characterization of moisture origins is crucial to understanding hydroclimatic processes. Nevertheless, documenting past atmospheric moisture contents and their sources remains challenging partially due to insufficient moisture-tracing proxies. Here, we present triple oxygen isotope compositions in 21 cave speleothems from monsoonal Asia to examine spatial moisture origin differences in eastern Asia over the past 300 years. Our data suggest an isotopic equilibrium fractionation during speleothem formation, and thus parent water 17O anomalies (Δ′17O) values reconstructed from speleothems preserve information on moisture origins and recycling across space. Notably, speleothem Δ′17O records exhibit a distinct geographical distribution, with low values in central-eastern and southern China, high values in northwestern and northern China, and relatively high values in the Yangtze River region. This spatial pattern underscores the diverse influence of different moisture sources regulated by regional hydrological circulation, and demonstrates the potential use of speleothem Δ′17O in reconstructing the moisture cycle at spatial scales.

High-temperature inter-mineral potassium isotope fractionation in ultrapotassic and granitic rocks: Implications for the potassium isotopic compositions of arc magmas

To constrain the mechanism and magnitude of inter-mineral K isotope fractionation during high-temperature magmatic processes, we conducted high-precision K isotope measurements on ultrapotassic and granitic rocks and mineral separates from the Qinling Orogenic Belt, China, as well as first-principles investigations of the corresponding K-bearing minerals. Our results show that the ultrapotassic rocks (−0.33 to −0.14‰) have considerably higher δ41K than the primitive mantle (−0.42 ± 0.08‰), confirming the previous conclusion that slab-derived fluids have contributed heavy K isotopic signatures to their mantle sources. Specifically, the K isotopic fractionation between biotite and microcline (Δ41Kbiotite-microcline = −0.11 to 0.05‰, with biotite and microcline ranging from −0.49 to −0.14‰ and − 0.48 to −0.12‰, respectively) agrees well with the calculated equilibrium isotopic fractionation scale. This evidence, together with the homogeneous mineral chemical compositions, suggests equilibrium K isotopic fractionation between biotite and microcline. Notably, amphiboles (δ41K ranging from −0.41 to 0.48‰) have heterogeneous K isotopic compositions and are generally heavier than coexisting microcline and biotite. In addition, the determined K isotopic fractionation between amphibole/plagioclase and microcline is inconsistent with the calculated results and is likely caused by the kinetic fractionation processes. To reveal the potential controls on the K isotopic compositions of arc magma, we utilized theoretical and measured K isotopic fractionation factors to model K isotopic fractionation behavior during amphibole crystallization. The results show that when Δ41Kamphibole-melt = 0.05‰, the fractional crystallization of amphibole shows negligible effect on the K isotopic composition of the residual melts. Even in the case of Δ41Kamphibole-melt = 0.24‰, fractional crystallization of amphibole exerts an insignificant control on the K isotopic composition of arc magma. Therefore, although amphibole may have heavier K isotopic compositions than the melts, its fractional crystallization may not distinctly decrease the K isotopic composition of residual melts.

Calcium isotopic fractionation during aragonite and high-Mg calcite precipitation at methane seeps

The formation of authigenic carbonate in marine environments represents a process that buffers ocean chemistry and atmospheric carbon dioxide levels. The isotopic composition of calcium (δ44/40Ca) in authigenic carbonate can be used to investigate the calcium (Ca) cycle, seawater chemistry, and diagenesis of carbonate rocks, archiving key information on the evolution of the Earth's surface environments. Laboratory experiments have shown that Ca isotopic fractionation during carbonate precipitation – the basis of the δ44/40Ca proxy – is mainly determined by both mineral phase and precipitation rate. However, the precipitation rate of submarine authigenic carbonate is much lower than rates in laboratory experiments. This study investigated the Ca isotopic composition of pore water and carbonate nodules collected from two gravity piston cores and one push core from the Haima seeps in the northern South China Sea. Methane fluxes calculated for the three cores range from 12 to 134 µmol cm−2 yr−1. The core with intermediate methane flux showed evidence of aragonite precipitation, while high-Mg calcite was the dominant mineral phase in the other two cores as indicated by Mg/Ca and Sr/Ca ratios of pore water. Numerical modeling of pore water geochemistry revealed that: (1) precipitation rates of carbonate per unit reactive surface area range from 0.05 to 21 µmol m−2 h−1, which is one to three orders of magnitude lower than rates in precipitation experiments; (2) Ca isotopic fractionation for aragonite precipitation is –1.8 ± 0.3 ‰, close to the reported equilibrium isotopic fractionation in precipitation experiments; and (3) Ca isotopic fractionation for high-Mg calcite precipitation is similar for the two cores (−0.9 ± 0.3 ‰ and −0.8 ± 0.3 ‰), although the modeled precipitation rates differed by two orders of magnitude. These results indicate that mineralogy rather than precipitation rate is the primary control on Ca isotopic fractionation during carbonate precipitation at seeps, resulting in lower δ44/40Ca values of aragonite (0.91±0.06 ‰, N = 4) than of high-Mg calcite (1.41±0.04 ‰, N = 9) reported relative to NIST SRM915a. This study documents distinguishable Ca isotopic fractionation during the formation of methane-derived high-Mg calcite and aragonite, providing fundamental parameters for further exploration of the calcium isotopic composition of marine authigenic carbonates in the geological record.

Bayesian inference on the isotopic building blocks of Mars and Earth

Elements with differing siderophile affinities provide insights into various stages of planetary accretion. The isotopic anomalies they exhibit offer a deeper understanding of the materials responsible for the formation of terrestrial planets. By analyzing new iron isotopic anomaly data from Martian meteorites and drawing insights from published data for O, Ca, Ti, Cr, Fe, Ni, Sr, Zr, Mo, Ru, and Si, we scrutinize potential changes in the isotopic composition of the material accreted by Mars and Earth during their formation. Our methodology employs a Bayesian inference method, executed using a Markov Chain Monte Carlo (MCMC) algorithm.The Bayesian method helps us balance the task of emulating the compositions of the terrestrial planets (reflected in the likelihood) with the flexibility to explore the isotopic compositions of mixing components within permissible intervals (indicated by the priors of the nuisance parameters). A Principal Component Analysis of isotopic anomalies in meteorites identifies three main clusters (forming the three parts of the isotopic trichotomy): CI, CC=CM + CO + CV + CR, and NC = EH + EL + H + L + LL. We adopt CI, COCV, O, and E as endmember compositions in the mixtures. We are concerned here with explaining isotopic anomalies in Mars and Earth, not their chemical compositions. Previous studies have shown that Earth's chemical composition could not be well explained by solely considering undifferentiated meteorites, as it requires incorporation of a refractory component enriched in forsterite. The endmember chondrite components considered here are assumed to be representative of isotopic reservoirs that were present in the solar nebula, but the actual building blocks could have had different chemical compositions, and we use cursive letters to denote those putative building blocks (CI for CI, COCV for COCV, O for O, and E for E).Because Earth's mantle composition is an endmember for some isotopic systems, it cannot be reproduced exactly by considering known chondrite groups only and requires involvement of a component that is missing from meteorite collections but is likely close to enstatite meteorites. With this caveat in mind, our results suggest that Earth is primarily an isotopic mixture of ~92% E, 6% CI, and < 2% COCV and O. Mars, on the other hand, appears to be a mixture of ~65% E, 33% O, and < 2% CI and COCV. We establish that Earth's CI contribution substantially increased during the latter half of its accretion. Mars began accreting a mix of O and E but predominantly accreted E later.Mars' changing isotopic makeup during accretion can be explained if it underwent gas-driven type I migration from its origin near the O - E boundary to a location well within the E region during the first few million years of solar system history. Earth's later increased CI contribution may be attributed to the stochastic impact of an interloper carbonaceous embryo that moved inside the inner solar system region while nebular gas was still present, and subsequently participated in the stage of chaotic growth.The discovery that a significant portion of Earth's building blocks closely resembles enstatite chondrites contrasts with recent findings of Si isotopic anomalies in enstatite chondrites when compared to terrestrial rocks. We suggest that this discrepancy likely stems from insufficient correction for high-temperature equilibrium isotopic fractionation, whether of nebular or planetary origin. With appropriate adjustments for this influence, both the silicate Earth and enstatite chondrites exhibit comparable Si isotopic anomalies, reaffirming a genetic link between them.

Lithium partition and isotopic fractionation for cation exchange in clay: Insights from molecular simulations

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 Kc (Li → Na) = 2.0, Kc (Li → K) = 10.0 for Arizona-type montmorillonite and Kc (Li → Na) = 1.0, Kc (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 (Δ7Limonolayer-aq = −2.0‰). While Li isotope fractionation between aqueous solution and mica structural sites is significant (Δ7Listructural-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.

No biological effect on magnesium isotope fractionation during stromatolite growth

The growth and morphology of stromatolites have been previously linked to diverse microbial activities. However, the role of microbial metabolisms on carbonate formation during stromatolite growth remains controversial. Magnesium isotopes have been proposed to serve as a tracer of microbial carbonate formation, implying a potential biological isotope fractionation. To further elucidate whether Mg isotope fractionation is modified during microbial carbonate formation, this study reports Mg isotope compositions of Holocene stromatolites and pore waters from Lagoa Salgada, a coastal ephemeral lake in Brazil. The stromatolitic carbonates are composed of high-Mg calcites characterized by extremely positive inorganic δ13C values, up to +20‰, and variable δ26Mg values, ranging from −2.98‰ to −0.68‰. Multiple pieces of evidence consistently demonstrate changes in microbial metabolism resulting from ecosystem fluid chemistry evolution. However, the direction of Mg isotope fractionation associated with carbonate precipitation remained invariable despite the changes in microbial activity. Mineralogical features indicate that the stromatolitic carbonates formed via 2-D nucleation. An isotopic mass balance calculation based on the observed variations in δ26Mg values and Mg concentrations of associated pore waters argues for an Mg isotopic equilibrium fractionation factor of −2.60‰ associating with the carbonate formation at Lagoa Salgada, well-matching experimental values for abiotic calcite precipitation. Thus, the observed δ26Mg variability of stromatolitic carbonates is primarily controlled by the changes of physicochemical conditions in the ambient fluid. We infer that during the formation of stromatolites, a consortium of different microbial communities produces extracellular polymeric substances, which serve as a substrate for carbonate nucleation from ambient fluid without significantly affecting the fractionation of Mg-isotopes. Our findings shed light on the effects of microbial processes on carbonate formation during stromatolite growth and improve the current understanding of the Mg isotope record in microbial carbonates.

Origin of carbonatites and associated silicate rocks revealed by Mg triple-isotope approach

Carbonatites are rare carbonate-rich igneous rocks derived from carbon and carbonate-rich regions of Earth's mantle. Although a number of igneous processes are recognized to have controlled their compositions, the origin of the carbonate-rich nature of these magmas remains debated and has been linked to various mantle-related processes, including subduction and plume–lithosphere interaction. High-precision isotope measurements can provide insights into carbonatite petrogenesis, including the identification of subducted crustal material in their source region. In particular, combining mass-dependent and kinetically corrected Mg isotope data, also known as the triple-isotope approach, provides insights into mass fractionation processes driving mass dependent fractionation, which in turn allows to distinguish between equilibrium and kinetic processes. In this work, we report high-precision Mg stable isotope data for 59 carbonatites and associated silicate rocks from different localities and ages ranging from 3000 Ma to present-day, as well as C and O isotopic analysis for 38 carbonatites and Sr isotopic analysis for 41 carbonatites and silicate rocks. In addition, we also report Mg isotope data for 17 Phanerozoic carbonate rocks, with the aim of identifying the isotopic signature of carbonate-rich material potentially recycled to the carbonatite mantle source regions. Collectively, the data reveal a range of stable Mg isotope compositions from δ25/24MgDTS-2 = −1.20 ± 0.01‰ to +0.08 ± 0.01‰. We observe positive residual deviations after kinetic mass fractionation correction of the Mg isotope data for our carbonatites; an isotope signal that is also present in Phanerozoic carbonates. This observation establishes that a component of the Mg present in these samples experienced mass-dependent equilibrium isotopic fractionation processes, which are significantly larger at low temperatures. Given that the Mg results do not covary with C and O isotopic signals, the magnitude of the fractionation following the equilibrium law observed in carbonatites provides strong evidence for recycled material from the Earth's surface in the mantle source of Ca- and Mg-rich carbonatites. Furthermore, associated silicate rocks present mantle-like Mg isotopic compositions in contrast with the genetically linked carbonatites - based on the Sr isotopes - for some complexes, which is best explained if the carbonatites and associated silicate rocks represent distinct generation of partial melts of a mantle source containing recycled carbonate.

Equilibrium partitioning and isotopic fractionation of nitrogen between biotite, plagioclase, and K-feldspar during magmatic differentiation

A significant portion of the continental crust is composed of plutonic igneous rocks. However, little is known about the geochemical behaviour of N between the different minerals during magmatic differentiation. To provide new constraints for the behaviour of N during crust formation, we have characterised the geochemistry of nitrogen (N) in the compositionally zoned calc-alkaline pluton at Loch Doon, SW Scotland. We present N concentration and N isotope values for whole-rock data alongside biotite, plagioclase and K-feldspar mineral separates and assess the degree to which these data preserve equilibrium partitioning during magmatic differentiation. We show that whole rock likely inherited its N contents and δ15N signatures from the initial source composition and that this signature is homogenous at a pluton scale. Whilst the whole-rock data are best explained as crust-derived N in the source, the degree of homogenisation across a pluton scale is inconsistent with empirical N diffusivities, ruling out syn-emplacement crustal assimilation as the source of N. Instead, our data suggest a crustal signature inherited from depth associated with the Iapetus subduction zone. At a mineral scale, we find that N preferentially partitions into the feldspars over mica in this system in the order K-feldspar > plagioclase ≈ biotite > quartz, with average mineral–mineral distribution coefficients of DN plagioclase-biotite = 1.3 ± 0.6 and DN Kspar-biotite = 2.8 ± 0.6. Partitioning is accompanied by a large and near constant equilibrium isotope fractionation factor between biotite and both feldspars (averages are Δ15NPlag-Biotite = +7.8 ± 1.2‰ and Δ15NKspar-Biotite = +7.9 ± 1.0‰). In contrast, Δ15NKspar-Plagioclase closely approximates 0‰, where both minerals show δ15N values overlapping with the bulk rock δ15N values. These results show that mica crystallisation generates a 15N-depleted reservoir within plutonic rocks. Moreover, our dataset suggests that feldspars might be a more significant host of N in the igneous portion of Earth’s continental and oceanic crust than previously thought.

Geological control on carbon isotope equilibrium and kinetic fractionation of CH4-CO2-HCO3− in microbial coalbed and shale gas systems

Microbial coalbed gas (CBG) and shale gas (SG), predominately composed of methane (CH4) and carbon dioxide (CO2), are important economic resources and potent greenhouse gases. Although isotopic equilibrium of CH4 and CO2 has been observed in microbial CBG and SG basins, it is difficult to judge under what geological conditions equilibrium is achieved. Moreover, the effects of CO2 dissolution on the isotopic fractionation process need to be considered. We use data from eight microbial CBG and SG basins to discuss the geological conditions in which equilibrium and kinetic isotopic fractionation in CH4-CO2-HCO3− system is achieved. Based on isotopic equilibrium temperatures calculated using computer codes developed in MatLab software, we show that, in deep and closed reservoirs, the CH4-CO2 and CH4-HCO3− are close to carbon isotope equilibrium. In contrast, in shallow and open reservoirs, they are in disequilibrium. The CO2-HCO3− is in disequilibrium in most reservoirs. We propose that both low free energy gradients and long coexisting time of CH4 and CO2/HCO3− are necessary to attain isotopic equilibrium. However, it is difficult to accurately estimate the timescale for attaining isotope equilibrium among them. In general, a closed and deep CBG/SG reservoir is likely to be geologically and geochemically stable over long timescales, favoring isotopic equilibrium of CH4-CO2 and CH4-HCO3−. However, a shallow and open reservoir is unfavourable for their isotopic equilibrium due to shorter timescales for the coexistence of CH4-CO2-HCO3−. Using data from systems close to equilibrium, we estimated the percentage of CO2 in total CH4 and CO2 in CBG reservoirs in various basins to be from 27% to 50%, where methanogenesis is mainly by CO2 reduction. This is significantly higher than the CO2 content (1% to 15%) in gaseous CH4 and CO2 in these basins but is consistent with those (36% to 48%) from culture experiments for coal conversion by methanogenesis. Further study shows that 53–99% of the CO2 formed during CBG generation has dissolved into groundwaters to form dissolved inorganic carbon (DIC) in CBG reservoirs. We propose that CO2 dissolution likely has significantly affect the abundance and isotopic compositions of gaseous CO2 in subsurface.

Formation pathways and source apportionments of inorganic nitrogen-containing aerosols in urban environment: Insights from nitrogen and oxygen isotopic compositions in Guangzhou, China

Air quality issues caused by PM2.5-induced persistent extreme haze episodes have become increasingly serious in urban environments in recent years. Secondary water-soluble inorganic sulfate (SO42−), nitrate (NO3−) and ammonium (NH4+) ions are the major components of PM2.5. However, the contributions of inorganic nitrogen species, especially nitrate, to PM2.5 have greatly increased during haze episodes in many cities in China. Therefore, better understanding of their emission sources and formation pathways holds the key to controlling urban PM2.5 pollution more efficiently and effectively. In this study, water-soluble ionic characteristics and isotopic compositions and sources of NH4+ and NO3−, as well as NO3− formation pathways were determined in PM2.5 aerosol samples collected in Guangzhou, China, during 2015–2018. The PM2.5 concentrations varied from 30.5 to 189.8 μg⋅m−3 and their mean values were highest in spring (111.1 μg⋅m−3) and lowest in summer (63.5 μg⋅m−3). The δ15N–NH4+ and δ15N–NO3- values ranged from +4.5 to +20.2‰ and from +4.8 to +14.8‰, respectively, with their mean values being highest in winter (14.0‰ and 9.5‰, respectively) and lowest in summer (10.4‰ and 7.1‰, respectively). The seasonal δ15N variability was mainly attributed to isotopic equilibrium fractionation, and partly due to the changes in NH3 and NOx sources. The average δ18O–NO3- value of 63.0‰, ranging seasonally from +58.6‰ in summer to +68.0‰ in spring, suggests that NO2 +⋅OH pathway played a vital role (70.3–85.9%) in NO3− formation. The Bayesian isotope mixing model results revealed fossil fuel combustion sources as dominant sources of atmospheric NH3 and NOx. This study suggests that more effort should be devoted to reduce NH3 and NOx from combustion-related processes and highlights the importance of δ18O–NO3- analysis for exploring variations of nitrate formation pathways in urban atmospheres.

Antimony Isotope Fractionation Revealed from EXAFS during Adsorption on Fe (Oxyhydr)oxides.

A lack of knowledge about antimony (Sb) isotope fractionation mechanisms in key geochemical processes has limited its environmental applications as a tracer. Naturally widespread iron (Fe) (oxyhydr)oxides play a key role in Sb migration due to strong adsorption, but the behavior and mechanisms of Sb isotopic fractionation on Fe (oxyhydr)oxides are still unclear. Here, we investigate the adsorption mechanisms of Sb on ferrihydrite (Fh), goethite (Goe), and hematite (Hem) using extended X-ray absorption fine structure (EXAFS) and show that inner-sphere complexation of Sb species with Fe (oxyhydr)oxides occurs independent of pH and surface coverage. Lighter Sb isotopes are preferentially enriched on Fe (oxyhydr)oxides due to isotopic equilibrium fractionation, with neither surface coverage nor pH influencing the degree of fractionation (Δ123Sbaqueous-adsorbed). Limited Fe atoms are present in the second shell of Hem and Goe, resulting in weaker surface complexes and leading to greater Sb isotopic fractionation than with Fh (Δ123Sbaqueous-adsorbed of 0.49 ± 0.004, 1.12 ± 0.006, and 1.14 ± 0.05‰ for Fh, Hem, and Goe, respectively). These results improve the understanding of the mechanism of Sb adsorption by Fe (oxyhydr)oxides and further clarify the Sb isotope fractionation mechanism, providing an essential basis for future application of Sb isotopes in source and process tracing.

Site-specific isotope effect: Insights from equilibrium magnesium isotope fractionation in mantle minerals

The equilibrium Mg isotope fractionation factors (lnα) derived from both theoretical calculation and experimental studies are not consistent with the values from natural sample observation. Different cation sites, which have identical coordinate numbers but different bond strengths, contribute equally to lnα in theoretical calculations. These non-equivalent sites might complicate the inter-mineral equilibrium isotope fractionations. Here, we investigate reduced partition function ratios (103lnβ) of non-equivalent Mg cation sites (e.g., M1, M2, and M3) in forsterite, orthoenstatite, clinoenstatite, tremolite, omphacite, pyrope and spinel to explore the site-specific effect on the intra- and inter-mineral equilibrium isotope fractionation. Based on all-electron first-principles calculations, 103lnβ in different cation sites decreases in the following sequence of spinelM1 > tremoliteM3 > orthoenstatiteM1 > forsteriteM1 > omphaciteM1 > tremoliteM1 > tremoliteM2 > clinoenstatiteM1 > forsteriteM2 > orthoenstatiteM2 > clinoenstatiteM2 > pyropeM1. These findings suggest that cation sites with larger polyhedron volumes prefer light Mg isotopes to those with smaller polyhedron volumes inside minerals, and the different contribution of intra-mineral cation sites could result in significant variations of equilibrium Mg isotope fractionation between minerals. The range of lnα between minerals induced by specific sites is defined as the equilibrium isotope fractionation domain. The site-corrected lnα can provide better evaluation of equilibrium fractionation factor of Mg isotopes between spinel and olivine and clarify the equilibrium state between mantle minerals. In addition, we establish spinel-olivine and omphacite-pyrope Mg isotope geothermometers based on the site-specific effect. This study suggests that the site-specific effect could be prevalent in solid materials and thus important for other isotope systems.