Significant Isotope Fractionation Research Articles

Equilibrium fractionation of REE isotopes in nature: Insights from NRIXS and DFT+U studies of Eu and Dy phonon density of states

Rare Earth Elements (REEs) are commonly utilized in Earth and environmental sciences to study a variety of geological processes due to their distinct patterns and radioactive-radiogenic decay systems (147Sm-143Nd, 146Sm-142Nd, 138La-138Ce). Advances in analytical techniques now enable the use of REE stable isotopic fractionations to clarify lingering ambiguities in REE systematics. In this study, we employed Nuclear Resonant Inelastic X-ray Scattering (NRIXS) to study the phonon density of states of 151Eu and 161Dy in several pure compounds, as well as in synthetic basalt and andesite glasses, and rhyolite glasses produced under various redox conditions, to determine equilibrium isotopic fractionation factors for the REEs. We additionally utilized Density Functional Theory with a Hubbard U correction (DFT+U) to calculate these factors. Our findings indicate that the directionally averaged mean force constant of Dy3+ is ∼270 N/m across various compounds, while those of Eu2+ and Eu3+ are ∼83 and 214 N/m, respectively, in geologically relevant glasses and other pure compounds. These force constants were then used to estimate those of all REEs using scaling arguments. The results suggest that equilibrium isotopic fractionation should be limited for REEs in igneous rocks, allowing for the interpretation of REE isotopic fractionation in these rocks and minerals as a result of kinetic effects. This could facilitate understanding the role of diffusion in igneous rocks and ore formation. Additionally, our results imply that significant Eu isotopic fractionation could exist in hydrothermal fluids, which could aid in understanding the formation of ore deposits and REE cycling in the oceans.

Extreme Copper Isotope Fractionation Driven by Redox Oscillation During Gleysols Weathering in Mun River Basin, Northeast Thailand

AbstractCopper (Cu) isotopes are utilized to track Cu geochemical cycling in weathered gleysols of tropical zones. A significant isotope fractionation of Cu in these soils is primarily redox‐controlled; however, it is rarely reported how the frequency of redox fluctuations affects the soil Cu isotope signature. This study investigated the variations of Cu content and isotope fractionation in two low‐humic gleysol profiles (S1 and S2) from a dry tropical savanna zone. Owing to redox oscillation during weathering, δ65Cu values in profile S2 showed a stronger positive correlation with the mafic index of alteration of reducing environment than S1, and isotopically light Cu is more retained in the Zone II of profile S2 than S1. As the frequency of redox fluctuation increased, the retained stable Cu(I) species and light Cu isotopes increased in the residual soils through re‐adsorption or re‐precipitation by iron oxyhydroxide (i.e., ferrihydrite). Importantly, an Mn‐enriched zone was formed after reduction events in profile S2, and found to be enriched in light Cu isotopes. The heavier Cu fraction might be lost by adsorption on Fe oxyhydroxides in the Mn‐rich zone, while the relatively light Cu might be retained through adsorption on Mn oxyhydroxides. Additionally, a significant Soil Organic Carbon (SOC) contribution to Cu was found due to the high δ65Cu‐SOC correlation (R2 = 0.80) in S1 (depth <1 m). Therefore, our study shows that the Cu isotope signature can respond to redox changes in the terrestrial ecosystem, and these Cu isotope signatures may have significant implications for assessing soil ecological vulnerability under future climate change scenarios.

Magnesium isotopic composition of modern human teeth enamel and its implications for dietary reconstructions

Metal stable isotopic composition of dental enamel is a novel proxy for reconstructing human dietary structure. Magnesium is the second most prevalent element in teeth only after calcium. Significant isotopic fractionation of Mg isotopes during biological processes implies its great advantages in reconstructing human recipes. To evaluate the potential of the Mg isotopic composition of dental enamel in learning the human dietary structure, elemental and Mg isotopic analyses were performed on the modern human teeth from regions in northern and southern China with various dietary characteristics. Our findings reveal that southern Chinese teeth enamel has higher Mg contents and heavier Mg isotopic compositions (-0.69‰ for SN and -0.66‰ for Hangzhou) than those of their northern counterparts (−1.27‰ for Weinan and −1.33‰ for Puyang). Such discrepancy cannot be attributed to the provenance heterogeneity or individual metabolic processes. Instead, the correlations between cereal-based dietary patterns and the δ26Mg in dental enamel demonstrate that the structure of the staple diet is more responsible for the Mg isotopic signatures. Moreover, heavier Mg isotopic compositions have been observed in dental enamel of individuals with higher rice and lower wheat in the diet, indicating that Mg isotopes are a promising tracer for rebuilding individual or population plant-based dietary structures as well as distinguishing more specific species within C3 plants. These findings suggest that Mg isotopes in teeth enamel have the great potential to better identify the food composition and constrain the diet structure of ancient humans.

Cadmium isotope fractionation during adsorption onto calcite

Adsorption on mineral surfaces is a crucial process controlling (bio)geochemical cycling of Cd, and Cd isotopic behaviour during adsorption is an important but little investigated aspect of Cd isotope systematics. This work looked at the fractionation of Cd isotopes during Cd adsorption onto calcite, which is an important sink of Cd but isotopic behaviour has only previously been investigated in co-precipitation experiments. The Cd isotope composition of calcite adsorbed components was determined to be lighter and consistent with equilibrium fractionation in all experiments. And degree of fractionation observed in our experiments is not influenced by the Cd/CaCO3 ratio, pH value or Cd/PO43− ratio in the studied range. In MQ water, the observed fractionation value αsorbed-aqueous is 0.99934 but this α value is affected by the presence of other compounds. Notably, αsorbed-aqueous = 0.99984, a reduced but resolvably lower value fractionation, was observed in the presence of PO43− which may be an important factor to be considered when interpreting Cd isotope signatures in nature. The enrichment of lighter Cd isotopes may result from highly distorted octahedral CdO6 sites of inner-sphere Cd complexes on calcite, indicated by extended X-ray absorption fine structure (EXAFS). However, near identical coordination environments of the aqueous and sorbed Cd species in the presence of PO43− likely led to the reduced Cd isotope fractionation. This work suggests adsorption of Cd onto carbonates minerals may produce significant Cd isotope fractionation between fluids and solid phase. Our observations offer an alternative process apart from co-precipitation when interpreting Cd isotope ratios in the presence of calcite in paleo-geological studies and could be helpful to better understand Cd (bio)geochemical cycling.

Cadmium isotope fractionation during metal-silicate partitioning – Results and implications for Earth's volatile accretion

Metal-silicate partitioning experiments were carried out at 1.5 GPa and 1508 to 1843 K to constrain Cd partitioning and isotope fractionation during core formation. At the studied conditions, there was no significant stable isotope fractionation during Cd partitioning between metal and silicate phases with a mean ∆114Cdmet-sil = −0.02 ± 0.09‰ (2SD, n = 7). Two experiments that investigated sulphide-silicate partitioning of Cd yielded fractionation factors of −0.04 ± 0.06‰ and − 0.23 ± 0.07‰ (2SE), whereby the latter result was obtained for a short run that may not represent full equilibrium. In summary, the findings suggest that Cd isotope fractionation during segregation of Earth's core was either absent or very minor. The Cd partitioning data of this and previous investigations were combined in multiple linear regression analyses to better constrain Cd metal-silicate partitioning during core formation. In accord with earlier work, the analyses reveal that Cd metal-silicate partitioning is not significantly impacted by temperature and pressure but affected by the S content of the metal phase. In addition, it is shown that the presence of C and Si in the metal reduce the siderophile character of Cd. Based on estimates for the composition of Earth's core, the data suggest a metal-silicate partition coefficient DCd of about 0.4 for a single-stage core formation event. However, given uncertainties about the light element composition of Earth's core, DCd values larger than 1 cannot be ruled out at present for core formation. The results of this study and data on the composition of the bulk silicate Earth and chondritic meteorites were applied in mass balance calculations to constrain the Cd signature of Earth's main stage accretion material prior to delivery of the late veneer. The modelling indicates Earth's main stage of accretion involved material with an average Cd isotope composition that was lighter than that of known carbonaceous and enstatite chondrites. Most likely, this reflects either poor characterisation of these meteorites by the few precise data currently available or that a significant fraction of the terrestrial volatile inventory was acquired from material not directly related to carbonaceous and enstatite chondrites. Furthermore, terrestrial accretion most likely did not encompass the addition of a volatile-rich late veneer exceeding 2% of Earth's mass, in accord with accretion models, which invoke that volatile delivery occurred primarily during main stage accretion, alongside core formation.

Carbon and hydrogen stable isotope fractionation of sulfamethoxazole during anaerobic transformation catalyzed by Desulfovibrio vulgaris Hildenborough

The fate of antibiotics in aquatic environments is of high concern and approaches are needed to assess the transformation of antibiotics in wastewater treatment plants. Here we used the model organism Desulfovibrio vulgaris Hildenborough to analyze compound specific isotope fractionation associated with anaerobic transformation of the antibiotic sulfamethoxazole (SMX). The results show that the rearrangement of the isoxazole ring in SMX is leading to significant carbon and hydrogen isotopic fractionation (εC = −5.8 ± 0.7‰, εH = −34 ± 9‰) during anaerobic transformation. The observed carbon isotopic fractionation is significantly higher than the values reported for aerobic degradation (εC = −0.6 ± 0.1‰) or abiotic reactions (εC = −0.8 to −4.8‰ for photolysis, εC = −0.8 to −2.2‰ for advanced oxidation). This indicates that carbon isotope fractionation can be used as a parameter to differentiate reaction mechanisms of SMX transformation. The corresponding apparent kinetic isotope effect (AKIEC) for anaerobic transformation of SMX was 1.029 ± 0.003, suggesting that the mechanism for anaerobic transformation is distinct from the mechanism reported for microbial aerobic degradation (AKIEC = 1.006 ± 0.001). In addition, dual-element (C–H) isotope analysis of SMX was performed in the present study, which was achieved by utilizing gas chromatography (GC) as the separation method instead of routine liquid chromatography. This dual-element isotope analysis resulted in a Λ value of 4.5 ± 2.2. Overall, compound specific isotope analysis can be a feasible tool to monitor the mitigation of SMX in wastewater treatment plants.

Reactive transport of micropollutants in laboratory aquifers undergoing transient exposure periods

Groundwater quality is of increasing concern due to the ubiquitous occurrence of micropollutant mixtures. Stream-groundwater interactions near agricultural and urban areas represent an important entry pathway of micropollutants into shallow aquifers. Here, we evaluated the biotransformation of a micropollutant mixture (i.e., caffeine, metformin, atrazine, terbutryn, S-metolachlor and metalaxyl) during lateral stream water flow to adjacent groundwater. We used an integrative approach combining concentrations and transformation products (TPs) of the micropollutants, compound-specific isotope analysis (δ13C and δ15N), sequencing of 16S rRNA gene amplicons and reactive transport modeling. Duplicate laboratory aquifers (160 cm × 80 cm × 7 cm) were fed with stream water and subjected over 140 d to three successive periods of micropollutant exposures as pulse-like (6000 μg L−1) and constant (600 μg L−1) injections under steady-state conditions. Atrazine, terbutryn, S-metolachlor and metalaxyl persisted in both aquifers during all periods (<10 % attenuation). Metformin attenuation (up to 14 %) was only observed from 90 d onwards, suggesting enhanced degradation over time. In contrast, caffeine dissipated during all injection periods (>90 %), agreeing with fast degradation rates (t1/2 < 3 d) in parallel microcosm experiments and detection of TPs (theobromine and xanthine). Significant stable carbon isotope fractionation (Δδ13C ≥ 6.6 ‰) was observed for caffeine in both aquifers, whereas no enrichment in 15N occurred. A concentration dependence of caffeine biotransformation in the aquifers was further suggested by model simulations following Michaelis-Menten kinetics. Changes in bacterial community composition reflected long-term bacterial adaptation to micropollutant exposures. Altogether, the use of an integrative approach can help to understand the interplay of subsurface hydrochemistry, bacterial adaptations and micropollutants biotransformation during stream-groundwater interactions.

Research progress on isotopic fractionation in the process of shale gas/coalbed methane migration

The research progress of isotopic fractionation in the process of shale gas/coalbed methane migration has been reviewed from three aspects: characteristics and influencing factors, mechanism and quantitative characterization model, and geological application. It is found that the isotopic fractionation during the complete production of shale gas/coalbed methane shows a four-stage characteristic of “stable-lighter-heavier-lighter again”, which is related to the complex gas migration modes in the pores of shale/coal. The gas migration mechanisms in shale/coal include seepage, diffusion, and adsorption/desorption. Among them, seepage driven by pressure difference does not induce isotopic fractionation, while diffusion and adsorption/desorption lead to significant isotope fractionation. The existing characterization models of isotopic fractionation include diffusion fractionation model, diffusion-adsorption/desorption coupled model, and multi-scale and multi-mechanism coupled model. Results of model calculations show that the isotopic fractionation during natural gas migration is mainly controlled by pore structure, adsorption capacity, and initial/boundary conditions of the reservoir rock. So far, the isotope fractionation model has been successfully used to evaluate critical parameters, such as gas-in-place content and ratio of adsorbed/free gas in shale/coal etc. Furthermore, it has shown promising application potential in production status identification and decline trend prediction of gas well. Future research should focus on: (1) the co-evolution of carbon and hydrogen isotopes of different components during natural gas migration, (2) the characterization of isotopic fractionation during the whole process of gas generation-expulsion-migration-accumulation-dispersion, and (3) quantitative characterization of isotopic fractionation during natural gas migration in complex pore-fracture systems and its application.

Coupling Molecular-Scale Spectroscopy with Stable Isotope Analyses to Investigate the Effect of Si on the Mechanisms of Zn-Al LDH Formation on Al Oxide.

While silicate has been known to affect metal sorption on mineral surfaces, the mechanisms remain poorly understood. We investigated the effects of silicate on Zn sorption onto Al oxide at pH 7.5 and elucidated the mechanisms using a combination of X-ray absorption fine structure (XAFS) spectroscopy, Zn stable isotope analysis, and scanning transmission electron microscopy (STEM). XAFS analysis revealed that Zn-Al layered double hydroxide (LDH) precipitates were formed in the absence of silicate or at low Si concentrations (≤0.4 mM), whereas the formation of Zn-Al LDH was inhibited at high silicate concentrations (≥0.64 mM) due to surface-induced Si oligomerization. Significant Zn isotope fractionation (Δ66Znsorbed-aqueous = 0.63 ± 0.03‰) was determined at silicate concentrations ≥0.64 mM, larger than that induced by sorption of Zn on Al oxide (0.47 ± 0.03‰) but closer to that caused by Zn bonding to the surface of Si oxides (0.60-0.94‰), suggesting a presence of Zn-Si bonding environment. STEM showed that the sorbed silicates had a close spatial coupling with γ-Al2O3, indicating that >Si-Zn inner-sphere complexes (">" denotes surface) likely bond to the γ-Al2O3 surface to form >Al-Si-Zn ternary inner-sphere complexes. This study not only demonstrates that dissolved silicate in the natural environment plays an important role in the fate and bioavailability of Zn but also highlights the potential of coupled spectroscopic and isotopic methods in probing complex environmental processes.

Stable carbon and hydrogen isotope fractionation of volatile organic compounds caused by vapor-liquid equilibrium

Several types of laboratory experiments were conducted to evaluate isotope fractionation caused by phase transfer process for a selection of common environmental contaminants. Carbon and hydrogen isotope fractionation caused by vaporization of non-aqueous phase liquid (NAPL), by volatilization from water and by dissolution into an organic solvent (tetraethylene glycol dimethylether or TGDE) under equilibrium conditions was investigated with closed system experimental setups to isolate the air-liquid partitioning process. A selection of aromatic, aliphatic and chlorinated compounds along with one fuel oxygenate (methyl tert-butyl ether or MTBE) were evaluated to determine isotope enrichment factor related to respective phase transfer process. During NAPL vaporization, the residual mass of aromatic compounds, aliphatic compounds and MTBE became progressively depleted in heavy carbon and hydrogen isotopes. In contrast, during volatilization from water, the residual mass of aromatic compounds and MTBE dissolved in the water became progressively enriched in heavy hydrogen isotopes, whereas no significant change in carbon isotope was observed, except for MTBE showing a significant depletion. For the air-TGDE partitioning process, most of the aromatic compounds tested led to no significant carbon (except ethylbenzene) or hydrogen (except toluene and o-xylene) isotope fractionation. In contrast, significant carbon isotope fractionation was observed for aliphatic and chlorinated compounds and hydrogen isotope fractionation for aliphatic compounds, and are comparable to progressive NAPL vaporization in direction and magnitude. The isotope fractionation factors determined in this study are key for interpreting the change in isotope ratios when assessing the fate of gas-phase VOCs present in the soil air or when gas-phase VOCs are sampled using TGDE as the sink matrix. The results of this study contribute to expand the list of common environmental contaminants that can be assessed by the compound-specific isotope analysis (CSIA) method deployed in the frame of gas-phase studies.

The factors controlling equilibrium inter-mineral Ca isotope fractionation: Insights from first-principles calculations

Equilibrium isotope fractionation factors are crucial to quantitatively interpreting Ca isotope data of natural samples. Recent studies have revealed significant equilibrium Ca isotope fractionation between minerals, but the controlling factors remain poorly understood. Using density functional theory, this study calculates the reduced partition function ratios (RPFRs) among amphiboles (richterite and tremolite), sorosilicates (akermanite and gehlenite), K-bearing carbonates (butschliite), Na-bearing diopside (jadeite), and other Ca-bearing minerals (fluorapatite, anhydrite, CaTiO3 perovskite, and fluorite) at 0 GPa. The RPFRs of diopside and anorthite over a pressure range from 0 to 5 GPa are calculated to investigate the pressure effect. The effect of force constant, bond length, coordination number, anion type, solid solution composition, and pressure on RPFRs are discussed by compiling the literature data. The RPFRs show good correlations with the force constant and bond length but have no clear correlation with the coordination number. This suggests that the bond length is more reliable than the coordination number for roughly predicting the signs and magnitudes of inter-mineral isotope fractionation. Na-bearing clinopyroxene (e.g., jadeite) has similar RPFR with Na-free clinopyroxene, suggesting that the jadeite effect should be insignificant in natural samples. The RPFR of anorthite is lower than that of diopside at low pressure, and the two minerals both show a positive correlation between RPFR and pressure. Notably, the heavy Ca isotope enrichment between these two minerals can be reversed at high pressure (>3 GPa at 1000 K) because anorthite’s RPFR changes more sharply with increasing pressure than that of diopside. However, such a reverse may not occur in Earth's modern crust due to the stability of anorthite at lower pressures. Combining the theoretical predictions of amphibole and plagioclase and natural sample observation on granitoids, we infer that the RPFR of granitic magma may be lower than that of basaltic magma.

Lithium Isotope Geochemistry in the Barton Peninsula, King George Island, Antarctica

Lithium (Li) has two stable isotopes, 6Li and 7Li, whose large relative mass difference is responsible for significant isotopic fractionation during physico-chemical processes, allowing Li isotopes to be a good tracer of continental chemical weathering. Although physical erosion is dominant in the Polar regions due to glaciers, increasing global surface temperature may enhance chemical weathering, with possible consequences on carbon biogeochemical cycle and nutriment flux to the ocean. Here, we examined elemental and Li isotope geochemistry of meltwaters, suspended sediments, soils, and bedrocks in the Barton Peninsula, King George Island, Antarctica. Li concentrations range from 8.7 nM to 23.3 μM in waters, from 0.01 to 1.43 ppm in suspended sediments, from 9.56 to 36.9 ppm in soils, and from 0.42 to 28.3 ppm in bedrocks. δ7Li values are also variable, ranging from +16.4 to +41.1‰ in waters, from −0.4 to +13.4‰ in suspended sediments, from −2.5 to +6.9‰ in soils, and from −1.8 to +11.7‰ in bedrocks. Elemental and Li isotope geochemistry reveals that secondary phase formation during chemical weathering mainly control dissolved δ7Li values, rather than a mixing with sea salt inputs from atmosphere or ice melting. Likewise, δ7Li values of suspended sediments and soils lower than those of bedrocks indicate modern chemical weathering with mineral neoformation. This study suggests that increasing global surface temperature enhances modern chemical weathering in Antarctica, continuing to lower δ7Li values in meltwater with intense water-rock interactions.

CleanEx: A Versatile Automated Methane Preconcentration Device for High-Precision Analysis of 13CH4, 12CH3D, and 13CH3D.

The relative abundance of methane isotopologues offers key insights into the global methane (CH4) cycle. Advances in laser spectroscopy enable routine high-precision measurements even for rare deuterated methane isotopologues, 12CH3D and 13CH3D, provided there are sufficiently high methane amount fractions and reproducible measurement conditions, which can be achieved by CH4 adsorption-desorption techniques. We present a new cryogen-free automated preconcentration device─CleanEx─designed for quantitative extraction of CH4 from large volumes of sample gas and for cleaning by stepwise temperature-controlled desorption to separate interferant gases. We show that CleanEx has the capability to preconcentrate methane by almost 2000-fold from ∼18 L of air. The performance is demonstrated in a range of methane amount fractions between 2 ppm (μmol mol-1), which corresponds to the present-day ambient air, up to 1000 ppm, representative for close to source or process conditions. Advantages over existing devices are a significantly larger primary adsorption trap and a secondary cryo-focusing step, which ensures separation of methane from major atmospheric compounds, i.e., O2, Ar, and CO2. We have demonstrated quantitative extraction of methane, with no significant isotopic fractionation and high repeatability of 0.2‰, 0.6‰, and 0.8‰ (n = 42) for the studied isotopologue ratios, 13CH4/12CH4, 12CH3D/12CH4, and 13CH3D/12CH4, during cryogenic adsorption-desorption on HayeSep D material. The developed device in combination with a suitable laser spectrometer offers a robust and autonomous method for precise continuous monitoring of δ13C-CH4 and δD-CH4 in ambient air and optionally Δ13CH3D in process-derived methane.

Pesticide degradation in an integrated constructed wetland: Insights from compound-specific isotope analysis and 16S rDNA sequencing

Carbon isotope analysis and the 16S rDNA sequencing were adopted to investigate the degradation process of chlorpyrifos during its transport in the integrated constructed wetland (ICW). Firstly, the extent of concentration decrease of chlorpyrifos was examined, and the removal efficiency in the first 36 h was found to be the highest. The removal rate reached 96.83 % after 96 h, and this process fit to the first-order kinetic model, with a kinetic constant (k) of 0.066 h−1. A significant carbon isotope fractionation was observed, with a change of the δ13C values from −26.54 ± 0.07 ‰ to −25.41 ± 0.08 ‰. The average chlorpyrifos biodegradation proportion reached 71.23 % (60.42 %–85.04 %), and it was predicted that about 11.79 %–36.41 % of chlorpyrifos removal in the ICW was attributed to abiotic factors. The outlet of the subsurface flow constructed wetland saw the highest D∗/B∗ value (1.38–3.88), indicating that the remaining fraction of dilution was much more significant than that of degradation in this period. The top 20 phyla of microbial community were identified in the ICW. Proteobacteria was the most dominant phylum, accounting for >40 % of the bacterial communities in all sampling locations. Acidobacteria and Bacteroidetes were the second and third dominant phyla. At the genus level, the microbial community composition differed more greatly in every stage of the ICW, and the spatial distribution difference was quite significant in the ICW. This study is important to figure out the migration and transformation of chlorpyrifos when the ICW was adopted as a removal tool for organic micro-pollutants, and more similar studies could be carried out in the future to promote the evaluation of pollutant removal capacity of the ICWs, and to further develop the application of stable isotope analysis of compounds in the natural environment.

Stable potassium (K) isotope characteristics at mid-ocean ridge hydrothermal vents and its implications for the global K cycle

Recent discoveries of significant variations in stable K isotope ratios (41K/39K or δ41K) among various terrestrial samples indicate that K isotopes can be a novel tracer for the global K cycle, but a key observation that seawater δ41K is ∼0.6‰ higher than the bulk silicate Earth remains unexplained. An unconstrained component critical to this puzzle is hydrothermal systems that represent both a major K source and sink in the ocean. Here we report δ41K results on mid-ocean ridge (MOR) hydrothermal fluids from the Gorda Ridge and ∼9°N East Pacific Rise (EPR), including time-series samples that recorded major perturbations in fluid chemistry induced by a local volcanic eruption. Fluid δ41K values range from -0.46‰ to -0.15‰, falling between those of fresh basalts and seawater. δ41K values of “time-zero” fluids collected shortly after the volcanic eruption are shifted towards the seawater value, followed by a return to pre-eruption values within ∼2 years. Fluid δ41K variations are largely influenced by water–rock interactions, but they cannot be solely explained by simple mixing of seawater and K leached from basalts at high temperatures. Instead, these data imply small but significant isotope fractionation that enriches heavy K isotopes in basalts, likely caused by low-temperature alteration during the recharge stage of hydrothermal circulation. Our results preclude MOR hydrothermal systems as the cause for the heavy δ41K value of seawater. Using fluid δ41K data and K isotope fractionation constrained here for hydrothermal systems, a K mass-balance model implies a critical role for a marine sedimentary sink, possibly authigenic clay formation, in the global K cycle. Also, applying the K isotope fractionation constrained here to the published δ41K data from ophiolites shows the possibility for significantly lower seawater δ41K during the Ordovician, which can be explained by enhanced reverse weathering in response to distinct climate and tectonics at that time.

Stable isotope fingerprinting traces essential amino acid assimilation and multichannel feeding in a vertebrate consumer

Abstract Animals often consume resources from multiple energy channels, thereby connecting food webs and driving trophic structure. Such ‘multichannel feeding’ can dictate ecosystem function and stability, but tools to quantify this process are lacking. Stable isotope ‘fingerprints’ are unique patterns in essential amino acid (EAA) δ13C values that vary consistently between energy channels like primary production and detritus, and they have emerged as a tool to trace energy flow in wild systems. Because animals cannot synthesize EAAs de novo and must acquire them from dietary proteins, ecologists often assume δ13C fingerprints travel through food webs unaltered. Numerous studies have used this approach to quantify energy flow and multichannel feeding in animals, but δ13C fingerprinting has never been experimentally tested in a vertebrate consumer. We tested the efficacy of δ13C fingerprinting using captive deer mice Peromyscus maniculatus raised on diets containing bacterial, fungal and plant protein, as well as a combination of all three sources. We measured the transfer of δ13C fingerprints from diet to consumer liver, muscle and bone collagen, and we used linear discriminant analysis (LDA) and isotopic mixing models to estimate dietary proportions compared to known contributions. Lastly, we tested the use of published δ13C source fingerprints previously used to estimate energy flow and multichannel feeding by consumers. We found that EAA δ13C values exhibit significant isotopic (i.e. trophic) fractionation between consumer tissues and diets. Nevertheless, LDA revealed that δ13C fingerprints are consistently routed and assimilated into consumer tissues, regardless of isotopic incorporation rate. Isotopic mixing models accurately estimated the proportional diets of consumers, but all models overestimated plant‐based protein contributions, likely due to the digestive efficiencies of protein sources. Lastly, we found that δ13C source fingerprints from published literature can lead to erroneous diet reconstruction. We show that δ13C fingerprints accurately measure energy flow to vertebrate consumers across tissues with different isotopic incorporation rates, thereby enabling the estimation of multichannel feeding at various temporal scales. Our findings illustrate the power of δ13C fingerprinting for quantifying food web dynamics, but also reveal that careful selection of dietary source data is critical to the accuracy of this emerging technique.

Magnesium isotope fractionation during carbonate precipitation associated with bacteria and extracellular polymeric substances

Magnesium (Mg) is abundant on Earth's surface aquatic environments and plays an important role during the precipitation of biogenic CaCO3 minerals. Moreover, Mg isotopes are increasingly used to study a number of bio-induced mineralization processes of calcite. In this study, Mg isotope signatures during calcite and aragonite precipitation in the presence of Curvibacter sp. HJ-1 and of their extracellular polymeric substances (EPS) were investigated and the evolution of mineralogical and liquid composition were tracked over time. The results showed that light Mg isotopes were preferentially incorporated into the precipitated solids in all the experiments with and without bacteria. Significant Mg isotope fractionation was associated with the transformation of amorphous calcium carbonate (ACC) to crystal carbonate (Δ26Mgcrystals-ACC = −0.9‰ and −0.7‰ in biotic and EPS experiments, respectively), and obvious Mg isotope fractionation was noted between solids and liquid (Δ26Mgsolid-liquid achieved −2.2‰ and −2.0‰ in biotic and EPS experiments, respectively). Besides, δ26Mg values were significantly correlated with pH, Mg content in liquid and solid, bacterial density and presence of EPS in biotic experiments. These findings indicated that strain HJ-1 had an effect on Mg isotope fractionation during calcite and aragonite precipitation. The difference in Mg isotope fractionation may be a new tool for understanding the biologically mediated effects on Mg-bearing carbonate precipitation, and serves as a useful alternative for aqueous Mg isotope, which is vital for reconstructing past environmental changes.

Fractionation of Dissolved Selenium Isotopic composition during a Phytoplankton Bloom in an Estuary

Selenium (Se) isotopes have been widely used to track the Earth's redox evolution based on the assumption that terrestrial Se is faithfully transported at the land-ocean interface without nonconservative behavior or biological fractionation affecting its isotope composition. However, dissolved Se isotope behavior in estuaries is poorly constrained, which calls this assumption into question. In this study, we present the first dissolved inorganic Se (DISe) isotope dataset along a salinity gradient during transport of the Changjiang river. Water and phytoplankton samples from a bloom event were collected. The δ82/76DISe values increased from 0.96‰ to 1.74‰ along the salinity gradient (from 0.1 to 34.5). The nonconservative behavior of DISe was revealed by large offsets of δ82/76DISe from theoretical mixing of the bloom waters. The dynamics of δ82/76DISe in the Changjiang Estuary (CJE) were controlled by the combination of physical mixing and biological utilization. In those bloom waters, the heavy δ82/76DISe values (1.66‰ ± 0.07‰) in the waters corresponded to the light Se isotopes for phytoplankton (−0.35‰ ± 0.18‰). The significantly increased δ82/76DISe signatures in the bloom waters due to the utilization of DISe by phytoplankton led to an Se isotope fractionation factor (reported as ε82/76Se = 1000 × (α82/76Se − 1) in) of −1.92‰ ± 0.16‰ (Rayleigh model) or −2.14‰ ± 0.18‰ (steady-state model). We propose that biological activities modify the nonconservative activity of Se and induce significant Se isotope fractionation with a factor of approximately −2‰ during transport. Our findings highlight that interpreting Se isotopes in the sedimentary record requires the consideration of nonconservative behavior and biological fractionation of Se.

Flooding-drainage alternations impact mobilization and isotope fractionation of cadmium in soil-rice systems

Sequential flooding and draining substantially alter Cd mobilization in paddy fields, primarily due to redox-driven changes in Fe-Mn (hydro)oxides and Cd-sulfides. However, the impacts of carbonates on Cd mobilization during flooding-drainage alternations remain poorly understood. In this study, Cd isotope compositions were analyzed in soils and plants at three growth stages, and the results show a pH-dependent Cd mobilization and isotope fractionation. Sequential extraction shows the Cd mainly binds to the exchangeable fraction and carbonates, and their amounts vary with pH. Exchangeable Cd with light isotopes coprecipitates into carbonates due to increased pH during flooding (tillering and panicle initiation). Whereas in drained soils (maturity), the carbonate-bound Cd releases with decreased pH. Light isotopes are enriched in rice compared with exchangeable Cd, but this enrichment is insignificant at maturity. This difference is mainly caused by the change in Cd isotope composition of exchangeable Cd pool due to carbonate coprecipitation during flooding. Limited isotope fractionation between roots and aboveground tissues is found at tillering, whereas significant isotope fractionation is observed at two other stages, suggesting the nodes might work during Cd translocation between tissues. These findings demonstrate alternating flooding-drainage impacts the mobilization of carbonate-bound Cd and, consequently, isotope fractionation in soil-rice systems.

Selective Diffusive Gradients in Thin Films (DGT) for the Simultaneous Assessment of Labile Sr and Pb Concentrations and Isotope Ratios in Soils.

A method using diffusive gradients in thin films (DGT) for the accurate quantification of trace-level (μg L–1) Sr and Pb concentrations and isotope ratios [δSRM 987(87Sr/86Sr) and δSRM 981(207Pb/206Pb)] in labile, bioavailable element fractions in soils is reported. The method is based on a novel poly(tetrafluoroethylene) (PTFE) membrane binding layer with combined di(2-ethyl-hexyl)phosphoric acid (HDEHP) and 4,4′(5′)-bis-t-butylcyclohexano-18-crown-6 (crown-ether) functionality with high selectivity for Sr and Pb (TK100 membrane). Laboratory evaluation of the TK100 DGT showed linear uptake of Sr over time (2–24 h) up to very high Sr mass loadings on TK100 membranes (288 μg cm–2) and effective performance in the range of pH (3.9–8.2), ionic strength (0.001–0.1 mol L–1), and cation competition (50–160 mg L–1 Ca in a synthetic soil solution matrix) of environmental interest. Selective three-step elution of TK100 membranes using hydrochloric acid allowed us to obtain purified Sr and Pb fractions with adequate (≥75%) recovery and quantitative (≥96%) matrix reduction. Neither DGT-based sampling itself nor selective elution or mass loading effects caused significant isotopic fractionation. Application of TK100 DGT in natural soils and comparison with conventional approaches of bioavailability assessment demonstrated the method’s unique capability to obtain information on Sr and Pb resupply dynamics and isotopic variations with low combined uncertainty within a single sampling step.