Isotope Fractionation Research Articles

Extremely large Cl isotopic fractionation in Chang'e-5 impact glass beads

Lunar materials have recorded a very large δ37Cl variation, and the mechanism causing this variation has yet to be determined. We measured the F and Cl contents and the δ37Cl in Chang'e-5 impact glass beads using a nanoscale secondary ion mass spectrometry. These glass beads exhibit the largest δ37Cl variation observed to date, ranging from –0.7 ‰ to 119 ‰. Furthermore, the δ37Cl values are roughly negatively correlated with the Cl concentration. The correlations between F and Cl concentrations differ for homogeneous and heterogeneous glass beads. Our calculations indicate that NaCl (g) and HCl (g) degassing may have been the pivotal mechanism that elevated the δ37Cl value, with >50 % of Cl in the melt evaporating during glass formation. The glass beads may have incorporated the chlorine species condensed from early evaporation. Our results provide direct evidence to constrain the impact-induced degassing process of Cl on airless celestial bodies.

Carbon-13-isotopomics and metabolomics of fatty acids from triacylglycerols: overcoming the limitations of GC-C-IRMS for short- and medium-acyl chains.

Carbon-13 isotopomics of triacylglycerol (TAG) fatty acids or free fatty acids in biological matrices holds considerable potential in food authentication, forensic investigations, metabolic studies, and medical research. However, challenges arise in the isotopic analysis of short- and medium-chain (C4 to C10) fatty acid methyl esters (SMCFAMEs) through gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). The high volatility of these esters results in losses during their preparation, leading to isotopic fractionation. Moreover, the methoxy group added to acyl chains requires the correction of δ13C values, thereby increasing the uncertainty of the final results. Analyzing free fatty acids (FFAs) addresses both issues encountered with SMCFAMEs. To achieve this objective, we have developed a new protocol enabling the isotopomics of individual fatty acids (FAs) by GC-C-IRMS. The same experiment also provides the FA profile, i.e., the relative percentage of each FA in the TAG hydrolysate or its concentration in the studied matrix. The method exhibited high precision, as evidenced by the repeatability and within-lab reproducibility of results when tested on TAGs from both animal and vegetal origins. Compared to the analysis of FAMEs by GC-C-IRMS, the current procedure also brings several improvements in alignment with the principles of green analytical chemistry and green sample preparation. Thus, we present a two-in-one method for 13C-isotopomic and metabolomic biomarker quantitation within quasi-universal TAG compounds, encompassing the short- and medium-acyl chains.

The Differences in the Li Enrichment Mechanism between the No. 6 Li-Rich Coals and Parting in Haerwusu Mine, Ordos Basin: Evidenced Using In Situ Li Microscale Characteristics and Li Isotopes

As a potential strategic mineral resource, lithium (Li) in coal measures (including coal and parting) has attracted increasing attention from scholars globally. For a long time, Li in coal measures has been studied mainly on the macro-scale (whole rock); however, the microscopic characteristics of Li and Li isotope variations in coal measures are less well known. In this study, the No. 6 coal measures in the Haerwusu Mine were studied using ICP-MS, XRD, SEM-EDS, MC-ICP-MS, and LA-ICP-MS. The geochemical and mineralogical characteristics, the microscale distribution of Li in minerals, and the Li isotopes of Li-rich coal and parting in the No. 6 coal measure were investigated. The results show that the Li content in the No. 6 coal seam ranges from 3.8 to 190 μg/g (average 83 μg/g), which is lower than the parting (290 μg/g) and higher than the comprehensive evaluation index of Li in Chinese coal (80 μg/g). LA-ICP-MS imaging showed that Li in the coal is mainly contained within cryptocrystalline or amorphous lamellae aluminosilicate materials, and the Li content in lenticular aggregate kaolinite is low. The Li in parting is mainly found in illite/chlorite. The δ7Li of the coals was 3.86‰, which may be influenced by the input of the source rock. The δ7Li of the parting (7.86‰), which was higher than that of the coal, in addition to being inherited from the source rock, was also attributed to the preferential adsorption of 7Li by the secondary clay minerals entrapped in the parting from water during diagenetic compaction. Finally, by integrating the peat bog sediment source composition, sedimentary environment evolution, and Li isotope fractionation mechanism of No. 6 coal, a Li metallogenic model in the Li-rich coal measure was initially established. In theory, the research results should enrich the overall understanding of the Li mineralization mechanism in coal measures from the micro-scale in situ and provide a scientific basis for the comprehensive utilization of coal measure resources.

Vanadium isotope records of the transformation from carbonated melt to alkali basalt

Volcanic clasts from the International Ocean Discovery Program Site U1431 in the South China Sea (SCS) were analyzed for V isotopic compositions in this study. These volcanic clasts represent mantle-derived carbonated melts and record the transition from carbonated melts to alkali basalts. Based on the formation sequence, these clast samples were divided into early-stage (> 8.3 Ma) and late-stage (< 8.3 Ma) clasts. The early-stage volcanic clasts have δ51V values of −0.76‰ to −0.67‰, which provide an estimate for the V isotopic composition of primary carbonated melts. Their V isotopic compositions are slightly heavier than those of mid-ocean ridge basalts (−0.84‰ ± 0.10‰) and bulk silicate Earth (−0.86‰ to −0.91‰), reflecting the control of low-degree partial melting under conditions of high oxygen fugacity. The late-stage volcanic clasts have δ51V values ranging from −0.62‰ to 0.29‰, which are systematically heavier than those of early-stage volcanic clasts. The carbonated melts rose through and reacted with the lithospheric mantle and were transformed into alkali basalts by dissolving orthopyroxene and precipitating olivine and/or clinopyroxene. Because the reactants and reaction products do not lead to significant V isotope fractionation, the V isotopes show limited variations during transformation from carbonated melts to alkali basalts. The alkali basalts were emplaced into shallow crust by multiple pulses, in which the magma experienced variable degrees of magma differentiation, with δ51V values close to those of the initial alkali basalts or increasing due to fractional crystallization of FeTi oxides. The change in V isotopic compositions from early-stage volcanic clasts to late-stage volcanic clasts was driven by the varying magnitude of influence exerted by different magmatic processes en route from the deep mantle to the shallow crust.

Tracing sulfate sources in a tropical agricultural catchment with a stable isotope Bayesian mixing model

Sulfate (SO42−) is an essential anion in drinking water and a vital macronutrient for plant growth. However, elevated sulfate levels can impact ecosystem or human health and could be an important indicator of acid rock drainage or pollution. Therefore, monitoring SO42− sources and transport is important for water quality assessments. This study focused on exploring the sources and transformations of SO42− as well as estimating the proportional contribution of the potential SO42− pollutant sources to groundwater and surface water in a tropical river basin, the Densu River Basin. The study used major ions combined with stable sulfur and oxygen isotope compositions and a Bayesian isotope mixing model, MixSIAR. The major ion characteristics indicate that SO42− concentrations remain stable throughout the rainy and dry seasons but originate from diverse sources. The multi-isotope model (δ34SSO4, δ18OSO4) identified four potential SO42− sources: detergent, precipitation, sewage, and sulfate fertilizer. However, the δ34SSO4 and δ18OSO4 values of the fertilizer source signatures overlapped with those of precipitation and sewage. Nevertheless, the contributions from each source were disentangled using the MixSIAR model, which revealed sewage as the most dominant SO42− pollutant in the Densu Basin, accounting for ~47 % of sulfate in groundwater and ~ 56 % of sulfate in surface water. Sulfate fertilizer (~33 %) was the second most important source after sewage for groundwater, while detergent (~23 %) was the second most important source for surface water. The redox processes of bacterial sulfate reduction and sulfide oxidation were determined to have a minimal impact on the sulfur isotope fractionation within the basin. This study highlights the benefits of combining major ions, sulfur isotopes and the MixSIAR model for identifying sources of sulfate. This approach accounts for uncertainties in source contributions which allows for more robust and reliable apportionment of sulfate sources. The study emphasizes the need for effective waste management and pollution control measures to protect water quality and provides vital guidelines on how to partition sulfate sources on a large catchment scale and evidence for making pollution management decisions on water resources.

Technical note: Optimizing the in situ cosmogenic 36Cl extraction and measurement workflow for geologic applications

Abstract. In situ cosmogenic 36Cl analysis by accelerator mass spectrometry (AMS) is routinely employed to date Quaternary surfaces and assess rates of landscape evolution. However, standard laboratory preparation procedures for 36Cl dating require the addition of large amounts of isotopically enriched chlorine spike solution; these solutions are expensive and increasingly difficult to acquire from commercial sources. In addition, the typical workflow for 36Cl dating involves measuring both 35Cl/37Cl and 36Cl/Cl concurrently on the high-energy (post-accelerator) end of the AMS system, but 35Cl/37Cl determinations using this technique can be complicated by isotope fractionation and system memory during measurement. The traditional workflow also does not provide 36Cl extraction laboratories with the data needed to calculate native Cl concentrations in advance of 36Cl/Cl measurements. In light of these concerns, we present an improved workflow for extracting and measuring chlorine in geologic materials. Our initial step is to characterize 35Cl/37Cl on sample aliquots of up to ∼1 g prepared in Ag(Cl, Br) matrices, which greatly reduces the amount of isotopically enriched spike solution required to measure native Cl content in each sample. To avoid potential issues with isotope fractionation through the accelerator, 35Cl/37Cl is measured on the low-energy, pre-accelerator end of the AMS line. Then, for 36Cl/Cl measurements, we extract Cl as AgCl or Ag(Cl, Br) in analytical batches with a consistent total Cl load across all samples; this step is intended to minimize source memory effects during 36Cl/Cl measurements and allows the preparation of AMS standards that are customized to match known Cl contents in the samples. To assess the efficacy of this extraction and measurement workflow, we compare chlorine isotope ratio measurements on seven geologic samples prepared using standard procedures and the updated workflow. Measurements of 35Cl/37Cl and 36Cl/Cl are consistent between the two workflows, and 35Cl/37Cl values measured using our methods have considerably higher precision than those measured following standard protocols. The chemical preparation and measurement workflow presented here (1) reduces the amount of isotopically enriched chlorine spike used per rock sample by up to 95 %; (2) identifies rocks with high native Cl concentrations, which may be lower priority for 36Cl surface exposure dating, at an early stage of analysis; and (3) allows laboratory users to maintain control over the total chlorine content within and across analytical batches. These methods can be incorporated into existing laboratory and AMS protocols for 36Cl analyses and will increase the accessibility of 36Cl dating for geologic applications.

Unexpected increase of the deuterium to hydrogen ratio in the Venus mesosphere

This study analyzes H2O and HDO vertical profiles in the Venus mesosphere using Venus Express/Solar Occultation in the InfraRed data. The findings show increasing H2O and HDO volume mixing ratios with altitude, with the D/H ratio rising significantly from 0.025 at ~70 km to 0.24 at ~108 km. This indicates an increase from 162 to 1,519 times the Earth's ratio within 40 km. The study explores two hypotheses for these results: isotopic fractionation from photolysis of H2O over HDO or from phase change processes. The latter, involving condensation and evaporation of sulfuric acid aerosols, as suggested by previous authors [X. Zhang et al., Nat. Geosci. 3, 834-837 (2010)], aligns more closely with the rapid changes observed. Vertical transport computations for H2O, HDO, and aerosols show water vapor downwelling and aerosols upwelling. We propose a mechanism where aerosols form in the lower mesosphere due to temperatures below the water condensation threshold, leading to deuterium-enriched aerosols. These aerosols ascend, evaporate at higher temperatures, and release more HDO than H2O, which are then transported downward. Moreover, this cycle may explain the SO2 increase in the upper mesosphere observed above 80 km. The study highlights two crucial implications. First, altitude variation is critical to determining the Venus deuterium and hydrogen reservoirs. Second, the altitude-dependent increase of the D/H ratio affects H and D escape rates. The photolysis of H2O and HDO at higher altitudes releases more D, influencing long-term D/H evolution. These findings suggest that evolutionary models should incorporate altitude-dependent processes for accurate D/H fractionation predictions.

Carbon isotope fractionation during methane transport through tight sedimentary rocks: Phenomena, mechanisms, characterization, and implications

The phenomenon of carbon isotopic fractionation, induced by the transport of methane in tight sedimentary rocks through processes primarily involving diffusion and adsorption/desorption, is ubiquitous in nature and plays a significant role in numerous geological and geochemical systems. Consequently, understanding the mechanisms of transport-induced carbon isotopic fractionation both theoretically and experimentally is of considerable scientific importance. However, previous experimental studies have observed carbon isotope fractionation phenomena that are entirely distinct, and even exhibit opposing characteristics. At present, there is a lack of a convincing mechanistic explanation and valid numerical model for this discrepancy. Here, we performed gas transport experiments under different gas pressures (1–5 MPa) and confining pressures (10–20 MPa). The results show that methane carbon isotope fractionation during natural gas transport through shale is controlled by its pore structure and evolves regularly with increasing effective stress. Compared with the carbon isotopic composition of the source gas, the initial effluent methane is predominantly depleted in 13C, but occasionally exhibits 13C enrichment. The carbon isotopic composition of effluent methane converges to that of the source gas as mass transport reaches a steady state. The evolution patterns of the isotope fractionation curve, transitioning from the initial non-steady state to the final steady state, can be categorized into five distinct types. The combined effect of multi-level transport channels offers the most compelling mechanistic explanation for the observed evolution patterns and their interconversion. Numerical simulation studies demonstrate that existing models, including the Rayleigh model, the diffusion model, and the coupled diffusion-adsorption/desorption model, are unable to describe the observed complex isotope fractionation behavior. In contrast, the multi-scale multi-mechanism coupled model developed herein, incorporating diffusion and adsorption/desorption across multi-level transport channels, effectively reproduces all the observed fractionation patterns and supports the mechanistic rationale for the combined effect. Finally, the potential carbon isotopic fractionation resulting from natural gas transport in/through porous media and its geological implications are discussed in several hypothetical scenarios combining numerical simulations. These findings highlight the limitations of carbon isotopic parameters for determining the origin and maturity of natural gas, and underscore their potential in identifying greenhouse gas leaks and tracing sources.

Evaluating evaporites as potential archives of lake and seawater lithium isotopic ratios: An experimental study using various natural saline fluids

Reconstructing the lithium isotope composition (δ7Li) of ancient seawater and lacustrine environment is crucial for tracing silicate weathering processes that regulate Earth's carbon cycle and climate. This study examines the reliability of evaporite minerals in preserving the Li isotope signature of the original brines from which they precipitate. We conducted evaporation experiments on modern natural waters from Qinghai Lake, the Yellow Sea, and Chaka Salt Lake, each with unique salinity and chemical composition, to examine the behavior of lithium isotope ratios in the evolving brine and precipitated evaporite minerals.Our results show that initial hydrochemical conditions of the lake and ocean are the primary control on the evolution of major and trace elements and the mineral precipitation sequences during evaporative concentration. Aragonite, calcite, gypsum, and/or nesquehonite precipitated prior to halite. Li isotope fractionation of these non-halite precipitates varied significantly between 4‰ and 17‰. However, the δ7Li values of halite closely mirror those of the initial lake and seawater, indicating negligible Li isotope fractionation (<1‰) during halite precipitation. The δ7Li values of the evolving brines remain unchanged throughout the evaporation experiment. Solid phases precipitating before halite constitute <1–2% of the total moles of salt precipitated from the complete evaporation of the initial waters, thus, having little to no influence on the δ7Li values of evolving brines. Although halite comprises >77% of the total moles of salt, it does not fractionate Li isotopes. Therefore, halite more accurately reflects the δ7Li values of the co-evolving brine as well as those of the initial, unevaporated lake and seawater. These results underscore the potential of late stage evaporites, particularly halite, to serve as high-fidelity archives of ancient lacustrine and seawater δ7Li values. Such records are instrumental in reconstructing past silicate weathering and climatic conditions.

Dynamics of Cu isotope fractionation during the reactions of pyrite with Cu(I)-bearing hydrothermal fluids

Experimental investigation of the fractionation behavior of Cu isotopes during the replacement of pyrite by Cu-bearing sulfides (chalcopyrite, bornite, and chalcocite) was conducted under hydrothermal conditions. At the initial stages of the replacement reaction, small mounds of product formed on the pyrite surface; these mounds then grew and coalesced, progressively covering the pyrite grains as the reaction proceeded. Chalcopyrite, bornite, and chalcocite formed sequential monomineralic zones from the pyrite reaction front towards the solution. During the early stage of the reaction, Cu isotope fractionation between the solids and the aqueous solution (Δ65Cusolid-aqueous, Δ65Cusolid-aqueous = δ65Cusolid – δ65Cuaqueous) was approximately –0.6 ‰, similar to the calculated equilibrium Cu isotope fractionation factors between Cu-bearing sulfides (chalcopyrite, bornite, and chalcocite) and CuCl2–. However, the Δ65Cusolid-aqueous moved progressively further from equilibrium with prolonged reaction time, with fractionation factors ranging from approximately –0.6 ‰ to –1.2 ‰. We found that significant fractionation of Cu isotopes between the solid products and aqueous solution was mainly controlled by the amount of chalcopyrite that formed in the product layers. We interpret that the Δ65Cusolid-aqueous was controlled by the diffusion of aqueous Cu(I) species among the product layers and the changes in Cu redox state during the precipitation of chalcopyrite. These results imply that the δ65Cu values measured in sulfides from low-temperature hydrothermal deposits may be controlled by the local chemistry of the fluids in product layers that precipitate sulfides. This study highlights the importance of local fluid characteristics, such as redox conditions, metal speciation, and diffusion, in controlling isotope fractionation pathways during non-equilibrium mineral replacement.

Iron cycling and isotopic fractionation in a ferruginous, seasonally ice-covered lake

Ferruginous conditions, defined by anoxia and abundant dissolved ferrous iron (Fe2+aq), dominated the Precambrian oceans but are essentially non-existent in a modern, oxygenated world. Ferruginous meromictic lakes represent natural laboratories to ground truth our understanding of the stable Fe isotope proxy, which has been used extensively in interpreting the origins of Fe-rich sedimentary rocks like iron formations (IFs) and the interactions of early life with high-Fe2+aq conditions. Here we report comprehensive geochemical and Fe isotopic analyses of samples collected in May and August 2022, and March 2023, from Deming Lake, Minnesota, a ferruginous meromictic lake that undergoes surface freezing in winter and never becomes euxinic. Through chemical and Fe isotopic analyses of different putative Fe sources to Deming Lake; including eolian input trapped in winter ice cover, nearby bogs, and regional groundwaters sampled at surface springs; we find that a groundwater source provides the best chemical and Fe isotopic match for Deming Lake and can support Fe2+aq-rich waters at depth that maintain a permanent chemocline at ∼12 m. The ice-free Deming Lake water column can be split into three layers dominated by distinct Fe cycling regimes. Layer (I) extends from the lake surface to the base of the oxycline at ∼6 m, and its Fe cycling is dominated by isotopically light Fe uptake into biomass, likely from stabilized dissolved Fe3+, with variable eolian lithogenic influences. Layer (II) extends between the oxycline and the chemocline at ∼12 m and is dominated by partial Fe2+aq oxidation on approach to the oxycline, with the formation of variably isotopically heavy Fe3+-bearing particles. Layer (III) underlies the chemocline and is defined by Fe2+ phosphate (vivianite) and carbonate saturation and precipitation under anoxic, Fe2+aq-rich conditions with little Fe isotopic fractionation. The ice-covered winter water column features more homogenous Fe chemistry above the chemocline, which we attribute to seasonal homogenization of Layers (I) and (II), with suppressed ferric particle formation. Authigenic Fe minerals with non-crustal (light) Fe isotopic compositions only appreciably accumulate in sediments in Deming Lake underlying the chemocline. All sediments deposited above 12 m appear crustal in their Fe isotopic, Mn/Fe, and Fe/Al ratios, likely revealing efficient reductive dissolution of Fe3+-bearing lake precipitates and remineralization of Fe-bearing biomass. We find limited fractionation of Fe isotopes in the ice-covered water column and suggest this provides evidence that substantial delivery of oxidants is required to generate highly fractionated Fe isotopic compositions in Sturtian Snowball era IFs. By comparing Fe isotopic and Mn/Fe fractionation trends in the different Deming Lake layers, we also suggest that correlations between these two parameters in giant early Paleoproterozoic IFs requires the simultaneous deposition of multiple authigenic phases on the ancient seafloor. Finally, high-precision triple Fe isotopic analyses of dissolved Fe impacted by extensive oxidation near the Deming Lake oxycline reveal that the slope of the mass fractionation law for natural, O2-mediated Fe2+aq oxidation is identical to those previously defined for both UV photo-oxidation, and for an array of highly fractionated Paleoproterozoic IFs.

Potassium isotope compositions of Mariana arc lavas and their sedimentary input

We apply the stable potassium isotope system (41K/39K) to well-studied Mariana arc lavas, in which inter-island geochemical variability has been interpreted to reflect near constant addition of an aqueous fluid flux, that dominantly samples the subducting mafic oceanic crust and variable amounts of sediment melt addition to the sub-arc mantle wedge. The nature of the sediment component in the Mariana arc lavas remains enigmatic, with a mixture of melts from all subducted sediment lithologies and the altered-mafic oceanic crust seeming likely, but some interpretations point towards a component from melting of the volcaniclastic sediment alone. We present K isotopic data on a set of well-characterised Mariana arc lavas and sediment samples (from Ocean Drilling Program site 801). Our data show that the majority of Mariana arc lavas are isotopically heavy (ẟ41K), by up to ∼0.2 ‰, relative to mid-ocean ridge basalt (MORB), but most of the subducting sediment samples are slightly isotopically lighter than, or indistinguishable from MORB. The volumetrically important volcaniclastic sedimentary unit however is significantly isotopically lighter than MORB, by ∼0.8 ‰, which reflects marine diagenetic processes. Thus, volcaniclastic material significantly influences the bulk sediment K isotope composition. We show that ẟ41K compositions of the Mariana arc lavas can be reproduced by the addition of an aqueous fluid with isotopically heavy K (relative to MORB) and an additional fraction of an incompatible-element-enriched isotopically light melt component. Modelling of K isotopes together with K/La and radiogenic Nd indicate that the melt component is best explained by a mix of melts from bulk sediment and altered-mafic oceanic crust. Our results show that distinctive K isotopic variations in subduction zone inputs and K isotopic fractionation during dehydration reactions makes K a useful tracer of subduction zone processes.

On accurate calculations of equilibrium H/D fractionations at super-cold conditions (≤200 K) I: Full Partition Function Ratio (FPFR) vs. Path Integral Monte Carlo (PIMC)

Accurate estimations of Hydrogen/Deuterium (H/D) isotope effects have been a long-standing problem since the beginning of stable isotope geochemistry, primarily due to their strong nuclear quantum effects (NQEs). Currently, the D/H ratio plays a key role in deciphering the origin and evolution of water ice and organics in the solar system. Additionally, the Big-bang origin of Deuterium necessitates that the observed D/H variations be linked to isotope exchange reactions, such as HD + H2O ↔ H2 + HDO. Therefore, an accurate benchmark dataset describing the equilibrium H/D isotope fractionations at low temperatures (≤ 200 K) is essential for interpreting rapidly accumulating astrochemical observation data. In this study, we implemented and compared two methods developed for evaluating the NQEs of H/D isotopes: 1) the Full Partition Function Ratio (FPFR) method and 2) the Path Integral Monte Carlo (PIMC) method. Both were assessed for their accuracy and efficiency in estimating equilibrium isotope effects (EIEs) using 10 common interstellar small molecules (H2, HF, HCl, HCN, HNC, H2O, H2S, NH3, HCHO, and CH4) as examples. Most of them are calculated at high precision for the first time. For the FPFR method, several higher-order corrections to the Urey-Bigeleisen-Mayer model were considered, including anharmonicity, quantum mechanical rotation with nuclear-spin statistics, and corrections to the Born-Oppenheimer approximation. For the PIMC method, four different actions related to the thermal density matrix are used. These include the primitive and three fourth-order actions (Takahashi and Imada, Suzuki-Chin and Chin approximations), based on the direct scaled-coordinates transformation. Three main conclusions are obtained: 1) Under the framework of Born-Oppenheimer approximation, the PIMC method holds the same and even slightly better accuracy (more comprehensive descriptions of quantum anharmonicities) in estimating EIEs for H/D isotopes as the FPFR method. However, both methods suffer from the neglection of the DBOC when using the Born-Oppenheimer potential energy surfaces. For the PIMC method, additional corrections for particle distinguishability must be considered when nuclear spin statistics exhibit its effects at low temperatures (e.g., < 160 K for H2). 2) Among the four actions, three fourth-order actions show better convergence and efficiency (2.2 to 26.5 times speedups at 50 K) than the primitive action, making them superior candidates for PIMC simulations at super-cold (≤ 200 K) conditions. 3) A combination of accurate potential energy surface with the PIMC method serves as an alternative way for theoretical estimations of H/D isotope effects.

Adsorption pathways of boron on clay and their implications for boron cycling on land and in the ocean

Reversible adsorption and isotope fractionation of boron on the surface of clay minerals is a key process that impacts boron isotope cycling in porewater, rivers and the ocean. However, the differences in boron isotope fractionation factors between various clay minerals and their dependence on fluid chemistry are not well known. We performed two sets of experiments, using solutions of pure water with added boron and seawater, to explore the isotope behavior during adsorption of boron onto kaolinite, smectite and illite. We found that the amount of sorbed boron increases with ionic strength of solutions and is proportional to the cation exchange capacity of a given clay mineral. Maximum adsorption is observed in alkaline seawater, which we attribute to the efficient fixation of magnesium-borate ion pairs onto negatively charged surface sites. Isotopic fractionation is modestly different between clays and demonstrates that clay surfaces preferentially sorb borate, even when the concentration of borate in solution is low. In both pure water and seawater, adsorbed complexes retain the isotopic composition of their dissolved precursors (borate or boric acid) with minimal isotopic fractionation. In other words, isotopic composition of adsorbed boron is set by the ability of clays to adsorb boron from an already fractionated boron pool rather than specific fractionation associated with the complexation reaction. Our experimental results allow us to provide revised constraints on the adsorbed boron being transported in terrestrial fluids and the ocean.

Experimental constraints on barium isotope fractionation during adsorption–desorption reactions: Implications for weathering and erosion tracer applications

Constraining the processes that fractionate barium isotopes is essential for utilising barium isotope ratios as environmental tracers. Barium concentration measurements from soils, rivers, and estuaries demonstrate that adsorption–desorption reactions significantly influence the distribution of fluid–mobile barium at the Earth’s surface, potentially driving isotopic fractionation. To quantify the direction and magnitude of isotopic fractionation resulting from these reactions, a riverine and an estuarine series of batch experiments were conducted using environmentally important adsorbent minerals and surface waters. Himalayan river sediment and water samples were used to validate the experimental results.Adsorption–desorption reactions were found to be rapid, relative to the average transit time of sediment and water in catchments, and largely reversible. The direction and magnitude of isotopic fractionation in the riverine experiment series were consistent with the riverine field samples (preferential adsorption of the lighter isotopes). The reaction rate, reversibility, and magnitude of isotopic fractionation were found to depend primarily on the mineral. Experiments performed with iron oxyhydroxides (goethite and ferrihydrite) resulted in a greater degree of fractionation compared to clay minerals (kaolinite and montmorillonite). Estuarine experiments, designed to simulate sediment passage through a salinity gradient, demonstrated a high degree of reversibility, with 77% to 94% of adsorbed barium desorbed upon the addition of seawater to freshwater-equilibrated clay minerals.The results of the estuarine experiments suggest that barium isotope ratios measured in marine paleo-archives (e.g., corals) will reflect both the adsorbed and dissolved freshwater barium inputs to the ocean. The combined findings of this study indicate that the chemical and isotopic behaviour of barium differs from more conventional group 1 and 2 metal isotope systems due to a significant proportion of barium released from bedrock dissolution partitioning to mineral surfaces, rapid reaction rates between fluid–mobile phases, and a high degree of reaction reversibility. Consequently, riverine barium isotope ratios are likely to provide unique insights into the complex array of terrestrial weathering and erosion processes that sustain life on Earth.

Theoretical and experimental constraints on hydrogen isotope equilibrium in C1-C5 alkanes

Stable isotope ratios of C1–C5 alkanes, the major constituents of subsurface gaseous hydrocarbons, can provide valuable insights on their origins, transport, and fates. Equilibrium isotope effects are fundamental to interpreting stable isotope signatures, as recognition of them in natural materials indicates reversible processes and constrains the temperatures of equilibrated systems. Hydrogen isotope equilibrium of C1–C5 alkanes is of particular interest because evidence shows that alkyl H can undergo isotopic exchange with coexisting compounds under subsurface conditions. We present the results of a combined experimental and theoretical effort to determine equilibrium hydrogen isotope distributions in mixtures of these hydrocarbon compounds. We created two mixtures: one with C1, C2 and C3 (where C1 indicates methane, C2 ethane, etc., hereinafter called ‘C1–C3 mixture’) and another one with C2, C3, iC4, nC4, iC5 and nC5 (hereinafter called ‘C2–C5 mixture’); in both cases, the mixtures were created to start out of hydrogen isotope equilibrium. We tested the performance of several metal catalysts as aids to H isotopic exchange by exposing these mixtures to different metal catalysts at 100 or 200 °C and analyzing the compound-specific hydrogen isotope ratios of the product gases. The C1–C3 mixture exchanged hydrogen isotopes among the starting gas components rapidly in the presence of Ru/Al2O3 at 200 °C. The isotope ratios reach a steady-state (presumably equilibrium) after 72 h of heating (up to 120 h). The hydrogen isotopic ratios of alkanes in the C2–C5 mixture shifted significantly in the presence of Rh/Al2O3 at 100 °C and C3-C5 compounds approached steady state after 70 h, whereas C2 had not yet reached a steady state D/H ratio after 216 h of heating. We evaluated the reaction progress of isotope exchange for each compound as a function of time with a reaction-network model informed by constraints on chemical kinetics. The model indicates that C3, iC4, nC4, iC5 and nC5 in the C2-C5 mixture reached internal isotope equilibrium after 70 h, hence we used their values to calculate experimental equilibrium results. We also calculated equilibrium isotope fractionations with the Bigeleisen-Mayer theorem using vibrational frequencies computed from the density functional theory (B3LYP/aug-cc-pVTZ). We included torsional conformers and explicit H positions in the calculations. We found that the experimental results from both the 200 ˚C C1–C3 experiment and 100 ˚C C2–C5 experiment are consistent with theoretical equilibrium results within experimental uncertainty. Additionally, our reaction-network model for catalyzed hydrogen isotope exchange between alkanes succeeded in fitting our experimental results. This modeling framework can be adjusted to simulate exchange in natural settings for constraining temperature histories and sources of natural gases.

Vitamin B12 as a source of variability in isotope effects for chloroform biotransformation by Dehalobacter.

Carbon and chlorine isotope effects for biotransformation of chloroform by different microbes show significant variability. Reductive dehalogenases (RDase) enzymes contain different cobamides, affecting substrate preferences, growth yields, and dechlorination rates and extent. We investigate the role of cobamide type on carbon and chlorine isotopic signals observed during reductive dechlorination of chloroform by the RDase CfrA. Microcosm experiments with two subcultures of a Dehalobacter-containing culture expressing CfrA-one with exogenous cobamide (Vitamin B12, B12+) and one without (to drive native cobamide production)-resulted in a markedly smaller carbon isotope enrichment factor (εC, bulk) for B12- (-22.1 ± 1.9‰) compared to B12+ (-26.8 ± 3.2‰). Both cultures exhibited significant chlorine isotope fractionation, and although a lower εCl, bulk was observed for B12- (-6.17 ± 0.72‰) compared to B12+ (-6.86 ± 0.77‰) cultures, these values are not statistically different. Importantly, dual-isotope plots produced identical slopes of ΛCl/C (ΛCl/C, B12+ = 3.41 ± 0.15, ΛCl/C, B12- = 3.39 ± 0.15), suggesting the same reaction mechanism is involved in both experiments, independent of the lower cobamide bases. A nonisotopically fractionating masking effect may explain the smaller fractionations observed for the B12- containing culture.

Large Isotopic Shift in Volcanic Plume CO2 Prior to a Basaltic Paroxysmal Explosion

AbstractCarbon dioxide is a key gas to monitor at volcanoes because its concentration and isotopic signature can indicate changes to magma supply and degassing behavior prior to eruptions, yet carbon isotopic fluctuations at volcanic summits are not well constrained. Here we present δ13C results measured from plume samples collected at Stromboli volcano, Italy, by Uncrewed Aerial Systems (UAS). We found contrasting volcanic δ13C signatures in 2018 during quiescence (−0.36 ± 0.59‰) versus 10 days before the 3 July 2019 paroxysm (−5.01 ± 0.56‰). Prior to the eruption, an influx of CO2‐rich magma began degassing at deep levels (∼100 MPa) in an open‐system fashion, causing strong isotopic fractionation and maintaining high CO2/St ratios in the gas. This influx occurred between 10 days and several months prior to the event, meaning that isotopic changes in the gas could be detected weeks to months before unrest.

Testing triple oxygen isotope preservation in the new OPEnS totalizer against conventional monthly rainfall collectors

Understanding the mechanisms that drive spatial and temporal triple oxygen isotope (Δ′17O) variations in modern precipitation is the first step to expanding the utility of these measurements as an environmental tracer jointly with traditional stable isotope parameters δD, δ18O, and d-excess. However, “totalizers” designed to collect a single precipitation sample pooled over a calendar month and minimize evaporation and associated isotopic fractionation of the sample during that time have not been tested for Δ′17O. We conducted a 30-day laboratory experiment comparing mass losses and isotopic shifts in four totalizers: 1) the OPEnS (Openly Published Environmental Sensing) totalizer, 2) the classic oil-based totalizer, 3) the commercial tube dip-in/pressure equilibration totalizer (Palmex Ltd. RS1), and 4) a reference totalizer (the control, lacking any evaporation reduction mechanism). The OPEnS totalizer was designed as being readily user built with parts costs of about $10, oil-free to facilitate quick and easy sample preparation and risk-free sample analysis, and its collection device expands as it fills to maintain a small gas/water ratio and minimize internal evaporative losses. All totalizers were filled to 12 % of their 3-L volume and placed in a modified laboratory oven with a diurnal temperature change of 23 to 40 °C and an average relative humidity of 9.1 % to simulate extreme evaporative conditions. The OPEnS totalizer experienced the smallest mass loss of water (0.21 %) and smallest isotopic shifts (p < 0.05 for δ18O and d-excess), which were all within measurement error. The oil, tube, and reference totalizers showed larger mass losses (0.41, 1.37, and 1.61 %, respectively) and evaporative enrichment with respect to δD (+0.3, +0.8, and + 2.1 ‰), δ18O (+0.16, +0.23, and + 0.83 ‰), and d-excess (−0.9, −1.0, and − 4.5 ‰). The Δ′17O variations for all totalizers were within measurement error, so we suggest that in less harsh climates their triple oxygen isotope changes during secondary evaporation would be more acceptable. To test the OPEnS totalizer in field settings, we installed it alongside oil totalizers to collect monthly precipitation over three years in the towns of Jolly and San Antonio, Texas, with mean annual precipitation, temperature, and windspeed values of 556 and 563 mm, 18.7 and 21.9 °C, and 5.0 and 3.5 m/s, respectively. Results indicate that the OPEnS and oil totalizers can produce similar isotopic data in the field, but modifications to OPEnS have been implemented to minimize under-catch and stabilize the collection component where high winds are present and additional testing under a variety of environmental conditions is ongoing. OPEnS is scalable according to expected monthly precipitation amounts, providing a cost-effective, high-performance device for quantification of total rainfall and its isotopic composition without oil contamination risks.

HIDALGO: A FUN object from the earliest epoch of the solar system’s history

Chemical and isotopic measurements of HIDALGO, a stoichiometrically pure hibonite inclusion found in the matrix of the Dar al Gani 027 meteorite, were conducted by secondary ion mass spectrometry to investigate its origin and evolution. HIDALGO is characterized by large mass-dependent isotope fractionations in O, Ca, and Ti, as well as large negative anomalies in neutron-rich 48Ca and 50Ti, making it the newest member of the HAL-type FUN inclusions. The highly fractionated Ca and Ti isotopes but unfractionated Mg isotopes are consistent with HIDALGO being a residue from an extensive evaporation event, during which large fractions of initial Ca and Ti, and essentially all the initial Mg, in the precursor material were lost. HIDALGO appears to have incorporated live 26Al at a higher level than other HAL-type inclusions, but still at a lower amount compared to the Solar System’s initial 26Al abundance typically found in non-FUN CAIs. Interestingly, the inferred 10Be abundance in HIDALGO is comparable to the values observed in the majority of CV3 CAIs but ∼ 2.5 times higher than those in HAL-type samples. HIDALGO’s unusual 26Al/27Al and 10Be/9Be ratios, together with the 48Ca-50Ti anomalies, can be best explained by the formation of its precursor material in the isotopically heterogeneous solar nebula. Finally, large 7Li excesses correlating with Be/Li were found in HIDALGO, a behavior that can be interpreted as due to in-situ decay of live 7Be. Charged particle spallation of initially Li-free HIDALGO can simultaneously account for the inferred 7Be abundance and the measured Li elemental concentration. The consistency between the measurement and spallation calculation results provides support for the prior existence of 7Be in HIDALGO, possibly produced by irradiation close to the Sun