Isotope Fractionation Factors Research Articles

Magmatic differentiation of peralkaline granites: Constraints from iron isotope fractionation between Fe-bearing minerals

Iron isotopes have been found useful in tracing magmatic processes of calc-alkaline granitic magmas, but its application in peralkaline granitic systems is hampered by the lack of information regarding the Fe isotope fractionation factors between alkali-rich ferromagnesian silicate minerals and FeTi oxides. To better understand the behavior of Fe isotopes during peralkaline magma differentiation, we carried out high-precision Fe isotope analyses on peralkaline and associated metaluminous high-silica granite rocks and Fe-bearing minerals separated from the rocks in Zhoushan archipelago, southeast China. The Fe-bearing mineral show a large dispersion in Fe isotope compositions, with δ56Fe ranging from 0.03 ‰ to 0.70 ‰, following the sequence of K-feldspar ≥ magnetite > aegirine > arfvedsonite > ilmenite. The δ56Fe differences between the mineral pairs are relatively consistent. Based on the magmatic temperatures defined by quartz-zircon oxygen isotopic geothermometer, the temperature-dependent equilibrium Fe isotope fractionation functions between following mineral pairs are obtained: Δ56Feaegirine-arfvedsonite = 0.20 (± 0.07) × 106/T2, Δ56Femagnetite-arfvedsonite = 0.38 (± 0.06) × 106/T2, and Δ56Femagnetite-aegirine = 0.16 (± 0.04) × 106/T2. The bulk peralkaline granites have variable but generally high δ56Fe values ranging from 0.28 ± 0.03 ‰ to 0.62 ± 0.04 ‰, with a mean of 0.42 ± 0.09 ‰ (1SD), which are higher than those of the associated metaluminous granitic samples (δ56Fe = 0.22 ± 0.05 ‰, 1SD). Furthermore, δ56Fe values of the peralkaline granites are negatively correlated with Sm/Yb and MnO, consistent with removal of isotopically light Fe-enriched arfvedsonite, implying that peralkaline granites experienced extensive magma differentiation regardless whether they were derived from differentiation of mantle-derived basaltic melts or partial melting of curst sources. Our results highlight a large Fe isotope fractionation between alkali ferromagnesian silicates and oxides, confirming Fe isotopes as a potential tool in tracking the differentiation processes of peralkaline magmas.

The soil-air interfacial migration process of volatile PFAS at the contaminated sites: Evidence from stable carbon isotopes with CSIA

Volatile per- and polyfluoroalkyl substances (PFAS) are prone to transport among various environmental media, with the soil-air interfacial migration process being an important pathway that significantly influences their environmental fate. To assess the migration and transformations of target volatile PFAS at contaminated site using compound-specific stable isotope analysis (CSIA), it is necessary to understand the isotopic fractionation that occurs during their transfer from soil to air. We have established methods for pre-treatment and GC/CSIA analysis methods of target volatile PFAS in soil and air samples and ensured the accuracy of carbon isotope analysis. GC/IRMS δ13C measurements showed optimal precision at instrumental response above 1.35–2.75 Vs, with recommended minimum on-column C levels of 1.67–5.00 nmol for target volatile PFAS. Stable carbon isotope fractionation factors related to the soil-air interfacial migration process for target volatile PFAS were determined by performing laboratory simulations. The observed εsoil-air values are all negative, suggesting that the soil-air interfacial migration process for target volatile PFAS is kinetic fractionation, the removal of molecules containing lighter isotopes. By comparing the simulated and experimentally observed δ13C (‰) values of target volatile PFAS, we found consistent trends in the soil and inverse trends in the air. These δ13C (‰) values and the related isotope fractionation model provide valuable insights into the isotopic behavior of target volatile PFAS during soil-air interfacial migration process, aiding in the assessment of their environmental fate.

Rhenium Isotopes Record Oxidative Weathering Intensity in Sedimentary Rocks

AbstractOxidative weathering of organic carbon in sedimentary rocks is a major source of CO2 to the atmosphere over geological timescales, but the size of this emission pathway in Earth's past has not been directly quantified due to a lack of available proxy approaches. We have measured the rhenium isotope composition of organic‐rich rocks sampled from unweathered drill cores and weathered outcrops in south Texas, whose stratigraphic successions can be tightly correlated. Oxidative weathering of more than 90% of the organic carbon and ∼85% of the rhenium is accompanied by a shift to lower rhenium isotope compositions in the weathered outcrops. The calculated isotope composition of rhenium weathered from the initial bedrock for individual samples varies systematically by ∼0.7‰ with different fractions of rhenium loss. This variation can be empirically modeled with isotope fractionation factors of α = 1.0002–1.0008. Our results indicate that the isotope composition of rhenium delivered to the oceans can be altered by weathering intensity of rock organic matter and that the rhenium isotope composition of seawater is sensitive to past oxidative weathering and associated CO2 emissions.

Monitoring of stable isotope composition of precipitation reveals thunderstorm dynamics

ABSTRACT The summer of 2019 is particularly well known for the famous heatwaves that swept across the European continent, with its associated drought and record-breaking air temperatures. This was followed by powerful thunderstorms, characterised by hail and heavy rain that damaged the crops on a regional scale. Here, we investigated one of the largest storm cells, lasting more than 6 h, which struck southwestern Romania. High-temporal resolution sampling of storm precipitation was performed for stable isotope measurements, rainfall and air temperature, to follow the storm dynamics. Hydrogen and oxygen isotope measurements show an abrupt decreasing temporal trend followed by superimposed V-shaped patterns interpreted as reflecting moisture replenishment by successive rain bands. To model the stable isotope values of precipitation in relation to the general trend of decreasing air temperatures, we applied a numerical Rayleigh condensation model for a non-constant α isotopic fractionation factor between liquid water and water vapour. The storm is powered by four consecutive moisture fronts, each following a Rayleigh distribution. About 40 % of the water vapour condenses during the sampled storm due to adiabatic expansion and cooling, which lowers saturation. Condensation ceases when cooling and absolute humidity can no longer sustain the dew point, stopping the rain. The timing of the event, occurring late at night and early in the morning, its duration of over 6 h as well as its synoptic scale may indicate a mesoscale convective complex.

Diatom silicon isotope ratios in Quaternary research: Where do we stand?

Silicon stable isotope ratios (expressed as δ30Si) in biogenic silica have been widely used as a proxy for past and present biogeochemical cycling in both marine and lacustrine settings, in particular for nutrient utilization reconstructions. Yet an analysis of publication trends suggests a significant decline in the application of δ30Si to Quaternary science questions in the last five years. At the same time as δ30Si proxy applications have decreased, we are learning more about its complexities: an expanding body of work is highlighting biases, caveats or complications involved in the application of δ30Si-based approaches to the sediment record. These include the demonstration of species-specific silicon isotope fractionation factors (i.e. ‘vital effects’) or the potential for Fe or other trace metals to influence silicon isotope fractionation. Others have inferred the potential of biogenic silica dissolution to alter an initial δ30Si value, or questioned the preservation of the initial δ30Si through early diagenetic processes more generally. Another challenge receiving more attention is centered around deconvolving a δ30Si-value into a signal reflecting biological productivity and a signal reflecting changes in the δ30Si of dissolved silicon driven by whole-system and/or circulation changes. Finally, a number of studies focus on analytical difficulties, especially during sample preparation related to achieving and demonstrating a contaminant free biogenic silica. These challenges lead us to posit that the Quaternary science community is moving away from silicon isotope proxies because they are losing confidence in their reliability and usefulness. Here, focusing on the diatoms – the dominant biosilicifiers in both lakes and the ocean – we synthesize progress in understanding nuances and caveats of δ30Si-based proxies in order to answer whether the fall-off in δ30Si-based Quaternary research is warranted. We suggest that with some simple steps that can be readily implemented, and with the closing of key knowledge gaps, there is no reason to believe silicon isotopes do not have a promising future in the Quaternary sciences.

Oxygen isotope fractionation during amorphous to crystalline calcium carbonate transformation at varying relative humidity and temperature

Crystalline calcium carbonate isotope compositions have been widely used to reconstruct past environments. However, if their isotopic compositions are modified because of crystallization from an amorphous precursor, their reliability as paleo-geochemical proxies can be compromised. This study explored the changes in the oxygen isotope compositions during the transformation of amorphous calcium carbonate (ACC) into crystalline carbonate under different conditions of relative humidity (RH of 33–95 %), temperature (T of 5 °C and 20 °C) and in the presence/absence of atmospheric CO2. The data showed that at low RH and T (e.g., RH ≤ 45 % and 5 °C) when a complete ACC-crystalline carbonate transformation did not take place then the original ACC δ18O values (δ18OCaCO3 = −15.9 ± 1.0 ‰, VPDB) were preserved throughout the experimental runtime (up to 144 days). In contrast, in fully crystallized CaCO3 (e.g., at RH ≥ 60 %) the δ18OCaCO3 values increased rapidly over the first few days, followed by a slower and gradual increase. By the end of the experiments (i.e., after 103–144 days) the crystalline δ18OCaCO3 values ranged from −10.4 ‰ to −8.1 ‰ in the presence of atmospheric CO2 and from −12.6 ‰ to −9.5 ‰ in the CO2-free experiments. These changes in oxygen isotope compositions of the CaCO3 reaction products (calcite and/or vaterite) were mainly driven by exchange with H2O from the hydrated ACC i.e. the synthesis fluid. In CO2-present experiments, oxygen isotope fractionation factors between the CaCO3 reaction products and the synthesis fluid (18αc–w) approached or exceeded oxygen isotope equilibrium values. This could be explained by a decrease in the initially high pH of the aqueous fluid released from ACC dissolution during CO2 hydration/hydroxylation, which would have increased the oxygen isotope exchange kinetics between H2O and dissolved inorganic carbon (DIC). In some experiments, the hydration/hydroxylation of 18O-enriched CO2, due to isotopic salt-effects, might have also resulted in 18O-enriched calcium carbonates and calculated fractionation factors that exceeded equilibrium values. In the CO2-free experiments, isotopic equilibrium between the crystalline phase and the synthesis fluid was not reached. This oxygen isotope disequilibrium suggests that without the pH lowering effect of the hydroxylation/hydration of CO2, the CO32− released during ACC/calcite dissolution-reprecipitation may have not isotopically equilibrated with the high pH synthesis fluid due to the long equilibration times required to reach isotope equilibrium at high pH values, leading to the self-buffering of δ18OCaCO3 values. The results suggest that the oxygen isotopic compositions of natural carbonates formed from ACC transformation in air and at low water/solid ratio (e.g., biominerals or carbonates formed in caves) are complex and cannot be used as simple proxies if the reaction kinetics (RH/CO2/T) and H2O sources are not known and quantified.

Deep regolith weathering controls δ30Si composition of groundwater under contrasting landuse in tropical watersheds

Land use changes are known to alter terrestrial silicon cycling and the export of dissolved silicon from soil to fluvial systems, but the impact of such changes on groundwater systems remain unclear. In order to identify the processes responsible for groundwater geochemistry and to assess the impact of agricultural processes, we examined multiple isotopic tracers (δ30Si, oxygen (δ18O) and hydrogen (δ2H) isotopes) in groundwater, soil porewater and surface water from two contrasted watersheds having the same gneissic lithology, one forested (Mule Hole) and one intensely cultivated (Berambadi) in the Kabini basin in South India. In the cultivated watershed, groundwater exhibits high Cl− and NO3− concentrations indicative of fertilizer inputs and solute enrichment from evapotranspiration due to multiple groundwater pumping/recharge cycles. The DSi concentration in groundwater is significantly higher in the cultivated watershed (980 ± 313 μM) than in the forested one (711 ± 154 μM), indicating more intense evapotranspiration due to irrigation cycles. The groundwater δ30Si values ranged from 0.6 ‰ to 3.4 ‰ and exhibit no significant differences between cultivated (1.2 ± 0.5 ‰) and forested (1.0 ± 0.2 ‰) watersheds, indicating limited impact of land use and land cover. Groundwater also shows no significant seasonal differences in DSi and δ30Si within watersheds, indicating a buffer to seasonal recharge during wet season. The δ30Si of a majority of groundwater samples fits a steady-state open flow through system, with an isotopic fractionation factor (30ε) between precipitating phase and groundwater ranging from −1.0 ‰ and − 2.0 ‰, consistent with precipitation of kaolinite-type clays, dominant in the study area. The steady-state flow through system in groundwater can be interpreted as a continuous DSi input from mineral weathering reactions with a dynamic equilibrium between Si supply and precipitation of secondary phases. We also observe, in both watersheds, similar DSi and δ30Si values in local surface water that includes small streams and a river (406 ± 194 μM, 1.6 ± 0.3 ‰) and in soil porewater (514 ± 119 μM, 1.6 ± 0.2 ‰). Compared to soil porewater, groundwater exhibits significantly lower δ30Si signatures and higher DSi, reflecting the contribution of an isotopically light silicon source, resulting from water-rock interaction during percolation through the unsaturated zone. We assign this steady input of DSi to the weathering of primary silicate minerals in the regolith, such as Na-plagioclase, biotite and chlorite, with formation of kaolinite and smectites type clays. A simple isotopic mass balance suggests that deep regolith weathering can contribute to almost half of the DSi in groundwater. We conclude that silicon cycling in soil porewaters, and surface waters are directly impacted by land use, while the isotopic composition of groundwater remains unaffected. Our results indicate that Si isotopic signatures of weathering, adsorption, and plant uptake occurring in the shallow soil and saprolite horizons are partly overprinted and homogenized by the regolith weathering in the deep critical zone, irrespective of land use and seasonality.

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.

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.

Applications of zinc stable isotope analysis in environmental and biological systems: a review

Zinc (Zn) is an essential trace element that is involved in both biotic and abiotic processes in Earth's surface environments. Over the last 20 years, advances in mass spectrometry instrumentation have enabled unprecedented high-precision Zn isotope abundance ratio determinations in natural and anthropogenic samples. Supported by a solid theoretical background inherited from the traditional non-metal stable isotopes (C, N, H, O, S), the understanding of the controlling factors of Zn isotope fractionation has rapidly evolved. In this article, we review the main applications and findings of Zn isotopes in a variety of scientific domains, including metal contamination, magmatic differentiation, plant uptake, weathering, global climate change, dietary and trophic chains, and biomedicine. The analytical aspects of Zn isotope determination in solid and water samples and the principles and mechanisms of Zn isotope fractionation are also reviewed. This work aims to provide a general yet in-depth panorama of Zn isotope chemistry and to demonstrate the versatility and potential of this isotope system for studying the biological, geological and chemical cycling of Zn.

Composition effects on equilibrium oxygen isotope fractionation factors between garnets and quartz/calcite/olivine: Implication from vibration frequencies of garnets at high temperatures and high pressures

Garnet-group minerals, with their wide range of compositions, play a significant role in Earth's crust and upper mantle, participating in various petrological and geochemical processes. Oxygen isotope fractionation factors between garnets and other minerals hold crucial implications in these contexts. In this work, vibration frequencies were measured via Raman spectra on five garnet mineral samples in the pyrope-almandine-spessartine ternary system and four synthetic pyrope-grossular solid solutions at temperatures up to 1000 °C and pressures up to 17 GPa. Isobaric (γiP) and isothermal (γiT) mode Grüneisen, as well as anharmonic (ai) parameters, were determined for the observed modes. Our study shows that the vibration bands tend to shift to lower frequencies with increasing temperature and to higher frequencies with increasing pressure. Moreover, the anharmonic correction has been found to contribute positively to equilibrium oxygen isotope fractionation β factors in garnets, typically within 0.5 ‰ above 1000 K. The 103∙lnβ(T) factors calculated from vibration spectra (considering Г points only) align closely with those from theoretical calculations (including all frequencies in the Brillouin zone). Contributions from phonon dispersion (including none-Г points) are typically smaller than the uncertainties propagated from frequency measurements. Additionally, the pressure effect on the oxygen isotope fractionation in garnet, evaluated from the isothermal Grüneisen parameters, is found to be insignificant under crustal and upper mantle conditions, consistent with thermodynamic expectations. Using published oxygen isotope fractionation β factors for quartz and calcite, the equilibrium oxygen isotope fractionation factors (103∙lnα) are calculated between garnets of diverse compositions and any of these phases as functions of temperature, pressure and fraction of garnet endmembers. Considering composition effects helps to reduce the discrepancies among experimental and empirical calibrations of oxygen isotope fractionation factors between garnet and quartz. As an example application, oxygen isotope fractionation factors 103∙lnα(P, T) between garnets and forsterite were calculated under upper mantle conditions. Our findings suggest that these fractionation factors are predominantly dependent on temperature and garnet compositions, with minor influence from pressure. Compared with our calculated fractionation factors between garnet and olivine, the oxygen isotope exchange equilibrium may have been reached in some in kimberlite and mantle xenolith samples between garnet and olivine. However, in other samples, the fractionation factors cannot be explained solely by the composition effect, likely due to metasomatism. Our results underscore the importance of considering garnet compositions when interpreting their oxygen isotope compositions.

Experimental determination of Si, Mg, and Ca isotope fractionation during enstatite melt evaporation

Abstract Evaporation of silicate materials from Earth or its precursors may be important in shaping their primordial compositions represented by undifferentiated meteorites, e.g., enstatite chondrites; however, the conditions under which evaporation occurs and the extent of evaporation-induced elemental and isotope fractionation remain uncertain. Here, we experimentally determine the volatility and isotope fractionation of Si, Mg, Ca, Nb, and Ta during enstatite melt evaporation at 2423–2623 K using a high-temperature conical nozzle levitator. Homogenous glasses are recovered after experiments; then we use EPMA and LA-ICP-MS to measure the elemental compositions, MC-ICP-MS to measure the Si and Mg isotopes, and TIMS to measure the Ca isotopes. Our results show that the evaporation rates of Si are larger than Mg, and the mean vapor/melt isotope fractionation factors (α = Rvapor/Rmelt; R = isotope ratio) are 0.99585 ± 0.00002 for 29Si/28Si and 0.98942 ± 0.00130 for 25Mg/24Mg. However, neither evaporative loss of Ca, Nb, and Ta nor Ca isotope fractionation was observed within analytical uncertainty. In conjunction with previous studies, we find that in an evaporation experiment the saturation degree (partial vapor pressure/equilibrium vapor pressure) of Si (SSi) is larger than SMg when Si is more volatile than Mg, and vice versa. If the Mg/Ca and Si/Ca ratios and isotopes in the bulk silicate Earth are attributed to the evaporation of enstatite chondrite-like precursors, evaporation temperatures >5000 K and SSi < SMg are required.

Heavy magnesium isotopic signatures in arc lavas may be attributed to dehydration of subducting hydrated mantle

Fluids released from subducting slabs profoundly affect mantle composition, rock melting points, and arc magma generation. However, identifying fluid sources (sediments, crust, or mantle) and their ascent paths remains challenging. Magnesium isotopes are potential tracers for subduction-related fluids, though their behavior during hydrous peridotite dehydration remains unclear. Here we determined the equilibrium magnesium isotope fractionation factors between aqueous fluids and hydrous peridotitic minerals using first-principles calculations. Aqueous fluids prefer heavy magnesium isotopes relative to mantle silicate minerals, indicating that fluids released during hydrous peridotite dehydration are enriched in heavy magnesium isotopes relative to the residual minerals. Our simulations proposed that magnesium isotope variations in arc lavas from different subduction zones could be attributed to different dehydration reactions influenced by subduction zone thermal structures. This study highlights the potential of magnesium isotopes for tracing fluids originating from subducting hydrated mantle, providing insights into the thermal structure of various subduction zones.

The Theoretical Calculation of the Cu Isotope Fractionation Effect in Solution/Hydrothermal Solution Systems.

Copper (Cu) is an important transition metal, and its isotopes have important applications in geology, environmental science, soil science, and other fields. Cu isotope fractionation can occur in many natural processes. However, the mechanism of Cu isotope fractionation in solution/hydrothermal solution systems is not very clear. In this study, the fractionation effects of complexes of Cu(I) and Cu(II) in solution/hydrothermal solution systems were systematically studied by means of an ab initio method based on first principles. In the simulation of an aqueous solution system, the theoretical treatment method used is the "water-droplet" method. The results show that the heavy Cu isotope (65Cu) enrichment capacity of the Cu-bearing complex solutions is greatly affected by the ligand types both for Cu(I) and Cu(II). For Cu(I) complex solutions, the heavy Cu isotope enrichment sequence is [Cu(HS)2]-·(H2O)42 > [Cu(HS)(H2O)]·(H2O)42 ≈ [Cu(HS)(H2S)]·(H2O)42 > [CuCl]·(H2O)42 > [CuCl2]-·(H2O)42 > [CuCl3]2-·(H2O)42. For the aqueous solutions of Cu(II) with an inorganic ligand (such as H2O, OH-, NO3-, SO42- and CN-), the order of heavy Cu isotope enrichment is as follows: [Cu(H2O)6]2+·(H2O)42 > [Cu(NO3)2]·(H2O)42 > [Cu(OH)2]·(H2O)42 > [CuSO4(H2O)3]·(H2O)42 > [CuNO3(H2O)4]+·(H2O)42 > [CuCN]+·(H2O)42. For the Cu(II) complex solutions with a halogen as ligands, the change order of 1000lnβ is [CuCl]+·(H2O)42 > [CuCl2]·(H2O)42 > [CuBr2]·(H2O)42 > [CuCl3]-·(H2O)42. The sequence of 1000lnβ for Cu(II) organic complex aqueous solutions is [Cu(HOC6H4COO)]+·(H2O)42 > [Cu(CH3CH2COO)]+·(H2O)42 > [Cu(COOHCOO)]+·(H2O)42. The calculation also found that for Cu(I) complex aqueous solutions, the difference in Cu isotope fractionation parameters (1000lnβ) between [CuCl2]-·(H2O)42 and [Cu(HS)2]-·(H2O)42 is relatively large. At 100 °C, the 1000lnβ of the two species are 1.14 and 1.55 (‱), respectively. The difference between the two could be reached up to 0.41 (‱). The Cu isotope fractionation parameter obtained with the "water droplet" method is also very different from the results of previous studies, which indicate that the Cu isotope fractionation behavior of the two is similar. At the same time, the exciting discovery is that the enrichment capacity of heavy Cu isotopes is significantly different between Cu(I) complex aqueous solutions and Cu(II) complex aqueous solutions. At 100 °C, the 1000lnβ of 6 Cu(I) complex aqueous solutions and 13 Cu(II) complex aqueous solutions ranged from 0.90 to 1.55 and 2.24 to 3.25(‱), respectively. It also shows that the REDOX reaction has a significant effect on the Cu isotope fractionation, especially in ore-forming fluids. Therefore, the ligand type is a factor that cannot be ignored when considering the mechanism of Cu isotope fractionation in solution/hydrothermal solution systems. Whether the solvation effect of an aqueous solution is considered or not has a great influence on the numerical values of the final Cu isotope fractionation factors. Hence, the solvation effect of an aqueous solution is an essential determinant in the theoretical calculation of the Cu isotope fractionation factors for Cu-bearing complex solutions.

Calcium isotopic composition of the bulk silicate Earth: A komatiite perspective

Calcium (Ca) isotopic composition of the mantle has been previously estimated as δ44/40Ca. However, δ44/40Ca of the mantle records both its stable isotopic composition and excess/deficit in radiogenic 40Ca that can be produced by the decay of 40K. Here, we present the high-precision Ca isotopic compositions of 16 Archean komatiites from five representative localities (Barberton, Munro, Abitibi, Yilgarn, and Taishan). Due to the high degrees of partial melting that led to their formation, these komatiites are used here to simultaneously estimate ε40/44Ca, δ44/40Ca, and δ44/42Ca of the bulk silicate Earth. The komatiites exhibit a resolvable negative ε40/44Ca relative to SRM915a, with an average of −0.6 ± 0.1 (2SE, 95 c.i.% if not specified). Given the lack of significant differences among the samples and the non-zero value of ε40/44Ca, we suggest using δ44/42Ca to report the stable Ca isotopic composition in this study. Excluding one sample (SD6/400), which may have been affected by alteration, the remaining komatiites display relatively homogeneous δ44/42Ca, ranging from 0.39 ± 0.02‰ (2SE, N = 16) to 0.49 ± 0.02‰ (2SE, N = 10), defining a mean of 0.44 ± 0.02‰ (2SE, N = 15). The absence of correlations between δ44/42Ca and LOI, Sr/Nd, (Dy/Yb)N, and (La/Sm)N among the komatiites indicates that post-eruption alteration, the influence of residual garnet, as well as prior melt extraction from the mantle source have had a negligible influence on their stable Ca isotopic compositions. Based on available experimental petrological data and isotope fractionation factors, it is demonstrated that komatiites were insignificantly fractionated from their mantle sources (i.e., <0.02% in δ44/42Ca). Their δ44/42Ca represents the ambient mantle at the time of segregation. Accordingly, we suggest that the average δ44/42Ca and ε40/44Ca of the komatiites measured here are representative of the bulk silicate Earth. Our new estimate can serve as a reference point for Ca isotopes as a two-dimensional tracer for sources and geological processes.

Synthesis of 13C-depleted organic matter from CO in a reducing early Martian atmosphere

Organic matter found in early Martian sediment may yield clues to the planet’s environmental conditions, prebiotic chemistry and habitability, but its origin remains unclear. Strong 13C depletion in sedimentary organic matter at Gale crater was recently detected by the Curiosity rover. Although this enigmatic depletion remains debated, if correct, a mechanism to cause such strong 13C depletion is required. Here we show from CO2 photolysis experiments and theoretical considerations that solar ultraviolet photolysis of CO2 in a reducing atmosphere can yield strongly 13C-depleted CO. We suggest that atmospheric synthesis of organic compounds from photolysis-produced CO is a plausible mechanism to explain the source of isotopically depleted organic matter in early Martian sediments. Furthermore, this mechanism could explain 13C enrichment of early Martian CO2 without requiring long-term carbon escape into space. A mass balance model calculation using our estimated isotopic fractionation factor indicates the conversion of approximately 20% of volcanic CO2 emissions on early Mars into organics via CO, consistent with the available data for carbon isotopes of carbonate. Although alternative pathways for organic compound production have been proposed, our findings suggest that considerable amounts of organic matter may have been synthesized from CO in a reducing early Martian atmosphere and deposited in sediments.

Ca isotopic gradients in epeiric marine carbonates: Diagenetic origins of and significance for Ca cycle reconstructions

Marine carbonates record geochemical information on the state of Earth’s surface environment in the geological past, but recrystallization during burial can make the records difficult to interpret. Here, we report shore to basin gradients in δ44Ca values in matrix limestone and burrow dolomite across a sequence of Late Ordovician (Katian Stage) burrow-mottled carbonates in the Williston Basin, an intracratonic epeiric marine basin in North America. Both gradients are interpreted to have diagenetic origins. The gradient in limestone δ44Ca values developed in a bathymetrically controlled sediment- to fluid-buffered diagenetic system operating between the center and the edges of the basin. Two dolomitizing events formed the gradient in dolomite δ44Ca values. The sediment-buffered end of the limestone gradient preserves the δ44Ca value of the original carbonate mud (∼–1.28 ± 0.10 ‰). The fluid-buffered end of the gradient conserves the δ44Ca value of contemporaneous seawater (–0.47 ± 0.10 ‰), because: (1) pore water exchange drivers operated with greater variety and intensity in shallow water settings, (2) shallow nearshore deposits exchanged more Ca with seawater during recrystallization to diagenetic calcite than deeper offshore deposits, and (3) diagenetic calcite formed with negligible fractionation under equilibrium conditions. The gradient conserves the local value of Δsed (–0.81 ± 0.20 ‰) despite its diagenetic origin, and the magnitude of Δsed is consistent with primary calcite precipitation in a ‘calcite sea’. Field assessment of the equilibrium Ca isotope fractionation factor between calcite and dolomite of –0.41 ± 0.17 ‰ at ambient temperature is applied to correct basin-centered dolomite for fractionation, yielding –1.62 ± 0.27 ‰, which is very different from the –0.25 ± 0.07 ‰ value of Ca in evaporatively concentrated seawater from which the dolomite originally formed. Applying the same fractionation factor to correct literature data on early diagenetic dolomite in the Great Basin, North America, yields –0.69 ± 0.22 ‰ for the δ44Ca value of seawater, which is ∼0.2 ‰ lower than ‘normal marine’ waters in stratigraphically equivalent deposits in the Willison Basin, and 0.44 ‰ lower than evaporatively concentrated seawater during a brief period of basin restriction and anhydrite deposition. The nearly 0.5 ‰ variation in the δ44Ca value of Katian seawater falls within the range of scatter in the brachiopod reconstruction of seawater Ca isotopes. Here, we propose that the true ocean record of secular change lies towards the bottom of the range of scatter, and that the higher values in the record reflect local Ca cycling and circulation restriction in epeiric seas. Epeiric seas cultivate the fluid-buffered diagenetic conditions required to promote Ca isotope exchange between reactive carbonate sediments and seawater through carbonate mineral dissolution/recrystallization, crystal coarsening by way of Ostwald ripening, and replacive dolomitization. It is not the apportioning of kinetically fractionated aragonite and calcite in the carbonate deposition flux that drove secular changes in global value of Δsed between ‘calcite’ and ‘aragonite’ seas, but rather the replacement of kinetic fractionations with equilibrium fractionations during fluid-buffered diagenesis with seawater.

Experimental and theoretical constraints on lithium isotope fractionation during brine evaporation and halite precipitation

Marine evaporitic halite, precipitating from the advanced stage of extremely evaporated seawater, is the most common and abundant evaporitic mineral. The extent to which lithium (Li) is incorporated into evaporite halite during geological periods of massive halite deposition, and the mechanisms of incorporation, are both unknown. These are each important, however, for the quantification of the isotope effect of the evaporitic sink on δ7Liseawater, and for the potential use of halite as a recorder of seawater δ7Li. Here, new experimental data are presented for the Li fractionation factor for halite from an isothermal evaporation experiment (25∘C for 100 days) using marine-derived brine. The resultant solids were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) to confirm the mineralogy and crystallinity of the product. Our results show that Li isotopes are not constant during the evaporation process implying that there must be a process that fractionates Li isotopes during halite precipitation. We suggest that this results from Li ionic substitution for sodium (Na) in crystalline halite, a scenario supported by ab-initio calculations, but we also show that Li within halite is predominantly present within fluid inclusions. Thus, the Li isotopic composition of halite is controlled by a mixture of Li within the fluid inclusions and Li that is incorporated into the halite crystalline structure. Overall, the brine becomes enriched in Li7 during evaporation due to the preferential incorporation of Li6 into chloride precipitates, and the evolution of δ7Librine is controlled by the precipitated mineral assemblage. The theoretical equilibrium fractionation factor 1000lnαmineral−fluid is -7.8▪ for Li-halite (LiNa26Cl27) at 25 C∘ at equilibrium, which is at the lower limit of Li isotope fractionation factors. Rayleigh fractionation models were fitted to the experimental data yielding a fractionation factor of -25▪3▪. The difference in Li isotope fractionation factor between brine and structurally bound Li may result from kinetic fractionation effects. This study presents a scenario highlighting that extensive halite deposits, formed over geological time in environments with relatively high Li concentration, could potentially impact the δ7Li values of seawater during that period, and place constraints on their utility as an archive for δ7Liseawater.

Calcium isotope fractionation by intracellular amorphous calcium carbonate (ACC) forming cyanobacteria.

The formation of intracellular amorphous calcium carbonate (ACC) by various cyanobacteria is a widespread biomineralization process, yet its mechanism and importance in past and modern environments remain to be fully comprehended. This study explores whether calcium (Ca) isotope fractionation, linked to ACC-forming cyanobacteria, can serve as a reliable tracer for detecting these microorganisms in modern and ancient settings. Accordingly, we measured stable Ca isotope fractionation during Ca uptake by the intracellular ACC-forming cyanobacterium Cyanothece sp. PCC 7425. Our results show that Cyanothece sp. PCC 7425 cells are enriched in lighter Ca isotopes relative to the solution. This finding is consistent with the kinetic isotope effects observed in the Ca isotope fractionation during biogenic carbonate formation by marine calcifying organisms. The Ca isotope composition of Cyanothece sp. PCC 7425 was accurately modeled using a Rayleigh fractionation model, resulting in a Ca isotope fractionation factor (Δ44Ca) equal to -0.72 ± 0.05‰. Numerical modeling suggests that Ca uptake by these cyanobacteria is primarily unidirectional, with minimal back reaction observed over the duration of the experiment. Finally, we compared our Δ44Ca values with those of other biotic and abiotic carbonates, revealing similarities with organisms that form biogenic calcite. These similarities raise questions about the effectiveness of using the Ca isotope fractionation factor as a univocal tracer of ACC-forming cyanobacteria in the environment. We propose that the use of Δ44Ca in combination with other proposed tracers of ACC-forming cyanobacteria such as Ba and Sr isotope fractionation factors and/or elevated Ba/Ca and Sr/Ca ratios may provide a more reliable approach.

Isotope fractionation of alkaline and alkaline-earth elements (Li, K, Rb, Mg, Ca, Sr, Ba) during diffusion in aqueous solutions

In this study, we used an improved “diffusion cell” method to precisely determine the diffusion-driven kinetic isotope fractionation factors of the Li, K, Rb, Mg, Ca, Sr, and Ba cations in aqueous solutions under room temperature. The obtained isotope fractionation factors (±2σ errors) are, α7/6Li = 0.996139 ± 0.000140, α41/39K = 0.998572 ± 0.000072, α87/85Rb = 0.999333 ± 0.000020, α26/24Mg = 0.999877 ± 0.000010, α44/42Ca = 0.999704 ± 0.000010, α88/86Sr = 0.999781 ± 0.000014, α138/135Ba = 0.999716 ± 0.000018. The results show that the charge of the cation and the ion-water bond length for the aquo ions are the two predominant factors affecting the mass dependence of isotope fractionation (β factor) during cation diffusion in aqueous solutions. Cations with higher charge numbers and shorter ion-water bond lengths exhibit less kinetic isotope fractionation during diffusion. Therefore, the isotope separation effect during diffusion (or β factor) in fluids is fundamentally controlled by the intensity of ion-water interaction. Weaker ion-water interaction (e.g., lower charge number, longer ion-water bond length) leads to less prominent hydrodynamic behavior for diffusing ions at the molecular level, thus more significant isotope fractionation in bulk solutions, and vice versa. Ions of larger radius would show stronger mass dependence of isotope fractionation (β factor), which can cancel the effect of decreasing relative isotope mass difference for heavier elements, thus kinetic isotope fractionation during diffusion in aqueous solutions remains prominent even for heavy elements such as Rb, Sr, and Ba. The diffusion-driven kinetic isotope fractionation factors measured in this study could provide a useful basis for interpreting specific natural isotopic variability of alkaline and alkaline-earth elements in supergene environments where chemical diffusion takes place.