Oxygen Isotope Exchange Research Articles

A possibility of 18O-depleted oceans in the Precambrian inferred from triple oxygen isotope of shales and oceanic crust

Oxygen-18/16 ratio recorded in geological media has been utilized to reconstruct surface temperature and discuss associated climatological forcing through Earth’s history. The accuracy of the estimated paleo-temperature through the application of the δ18O record, however, is limited by our understanding of the oceanic 18O/16O ratio in the past. As a longstanding issue, sedimentary rocks in the Precambrian, which are generally depleted in 18O relative to the modern sediments, can be interpreted either to have reflected higher surface temperature when assuming relatively constant oceanic δ18O values, or more 18O-depleted oceans relative to the present day with limited global temperature (climate) deviations. Additional use of a third isotope, 17O, can help constrain the isotopic composition of the porewater during the formation of a rock record as it provides an additional fractionation equation within the same isotopic system. This study utilizes reactive-transport models of triple oxygen isotope (16O, 17O, 18O) for continental weathering and hydrothermal alteration of oceanic crust, built upon the δ18O modeling framework developed by Kanzaki (2020a, b). Comprehensive oxygen isotope exchanges in dynamically moving media, both rocks and porewaters, are realized in these models, reflecting spatially-variable and process-dependent alteration conditions (e.g., spreading rate of midocean ridges, uplift rate of continents, porewater advection rate, and isotope exchange kinetics). The models were confirmed to be able to reproduce the signatures of triple oxygen isotope in Phanerozoic shales and oceanic crust. The validated models were then applied to Precambrian shales, which suggests that the Precambrian oceans could have been depleted in 18O, e.g., as low as −12‰ at >2.5 Ga and − 4‰ around 0.5 Ga, relative to the present-day seawater. General absence of positive and near-zero Δ′17O signatures in oceanic crust also suggests that the buffering of oceanic 18O through hydrothermal alteration of the oceanic crust could have been weak. The 18O flux from continental weathering thus could have played a significant role in controlling the 18O/16O ratio of ancient sea and together with climatic forcing could have enabled a secular transition of oceanic δ18O during the Precambrian.

Temperature dependence of isotopic fractionation in the CO2 -O2 isotope exchange reaction.

RationaleOxygen isotope exchange between O2 and CO2 in the presence of heated platinum (Pt) is an established technique for determining the δ 17O value of CO2. However, there is not yet a consensus on the associated fractionation factors at the steady state.MethodsWe determined experimentally the steady‐state α 17 and α 18 fractionation factors for Pt‐catalyzed CO2‐O2 oxygen isotope exchange at temperatures ranging from 500 to 1200°C. For comparison, the theoretical α 18 equilibrium exchange values reported by Richet et al. (1997) have been updated using the direct sum method for CO2 and the corresponding α 17 values were determined. Finally, we examined whether the steady‐state fractionation factors depend on the isotopic composition of the reactants, by using CO2 and O2 differing in δ18O value from −66 ‰ to +4 ‰.ResultsThe experimentally determined steady‐state fractionation factors α 17 and α 18 are lower than those obtained from the updated theoretical calculations (of CO2‐O2 isotope exchange under equilibrium conditions) by 0.0024 ± 0.0001 and 0.0048 ± 0.0002, respectively. The offset is not due to scale incompatibilities between isotope measurements of O2 and CO2 nor to the neglect of non‐Born‐Oppenheimer effects in the calculations. There is a crossover temperature at which enrichment in the minor isotopes switches from CO2 to O2. The direct sum evaluation yields a θ value of ~0.54, i.e. higher than the canonical range maximum for a mass‐dependent fractionation process.ConclusionsUpdated theoretical values of α 18 for equilibrium isotope exchange are lower than those derived from previous work by Richet et al. (1997). The direct sum evaluation for CO2 yields θ values higher than the canonical range maximum for mass‐dependent fractionation processes. This demonstrates the need to include anharmonic effects in the calculation and definition of mass‐dependent fractionation processes for poly‐atomic molecules. The discrepancy between the theory and the experimental α 17 and α 18 values may be due to thermal diffusion associated with the temperature gradient in the reactor.

Spectral dependence of UV light penetration into powder TiO2 anatase

The penetration depth of UV monochromatic light into deposited TiO2 anatase powder was investigated. The light penetration depth was considered in units of numbers of surface hole, Ns, and electron, NO2, centers activated during irradiation. The numbers of hole centers Ns were obtained from photostimulated oxygen isotope exchange reaction registered by means of mass spectrometry. The numbers of electron centers NO2 were obtained from subsequent thermo-programmed desorption spectroscopy of photoadsorbed oxygen O2-. It was shown that the depth D of UV light penetration into UV absorbing TiO2 powder coat depends on the wavelength and intensity I0 of incident UV light and obeys to the equation DI0=1kefflg(I0/Im) obtained from the Beer–Lambert–Bouguer law with effective extinction coefficient keff and minimal value of light intensity Im, below which the photoactivation is considered negligible. Commonly, the value Im has an order of a few microwatts/cm2 for activation of electron and hole type centers except for a case of 334 nm falling into the band of the first direct band-to-band transition of anatase, where relatively high threshold value Im=0.063 mW/cm2 for photoactivation of hole centers was revealed. Effective extinction coefficient keff may be considered proportional to the absorption coefficient of TiO2 in the region of fundamental absorption, whereas, in the non-fundamental absorption region, keff exceeds significantly that of TiO2 due to, probably, dominating scattering processes. At small intensities of the incident light, there is a strong sensitivity of the penetration depth (and activated surface) to the intensity.

Oxygen isotope evidence for progressively assimilating trans-crustal magma plumbing systems in Iceland

Abstract The oxygen isotope composition of mantle-derived melts can place important constraints on how magmas are processed as they traverse the crust. Assimilation of crustal material is a crucial aspect of basalt petrogenesis, as it affects the chemical and rheological characteristics of eruptive magmas at active volcanoes. We report oxygen isotope (δ18O) and trace element (TE) data from a suite of well-characterized basaltic melt inclusions and groundmass glasses from the Bárðarbunga volcanic system in Iceland to assess how and where in the plumbing system crustal rocks interact with ascending magmas. While both melt inclusions and groundmass glasses record a large range in δ18O values (+3.2‰ to +6.4‰ and +2.6‰ to +5.5‰, respectively) groundmass glasses record lower values on average. Relationships between incompatible trace element (e.g., Zr/Nb) and oxygen isotope ratios are best explained with three-component mixing, where primary melts derived from depleted and enriched mantle components with distinct δ18O values mix and acquire a low-δ18O character upon progressive contamination with altered Icelandic crust. The majority (60%) of melt inclusions require 10–30% exchange of oxygen with the Icelandic crust. In addition, for the first time, we link the extent of oxygen isotope exchange with melt equilibration depths, showing that most of the contamination occurs at 1–2 kbar (3–7 km depth). We propose that a progressively assimilating, multi-tiered plumbing system is a characteristic feature of the Bárðarbunga volcanic system, whereby chemical modifications resulting from interaction with the crust systematically increase as melts migrate through higher crustal levels. We show that similar processes may also occur across the active rift zone in Iceland.

Influence of the substitution with rare earth elements on the properties of layered lanthanum nickelate – Part 1: Structure, oxygen transport and electrochemistry evaluation

This study is aimed at studying the properties of La2NiO4+δ (LNO) substituted with rare earth elements to increase its oxygen over-stoichiometry and enhance oxygen transport thus improving electrochemical properties of the related electrodes. Materials of the La1.6Ln0.4NiO4+δ series (where Ln = Pr (LPNO), Nd (LNNO), Sm (LSNO), Eu (LENO), Gd (LGNO)) are synthesized by a nitrate combustion technique and their structural features, oxygen over-stoichiometry, and oxygen transport properties are investigated by different methods such as X-ray diffraction, TGA, temperature programmed isotopic oxygen exchange with C18O2 (TPIE) in a flow reactor. The unit cell volume in the La1.6Ln0.4NiO4+δ series decreases from Pr (V = 188.3 Å3) to Gd (V = 186.7 Å3). According to the TGA data, the LNO value of oxygen over-stoichiometry, δ, is equal to 0.15, while all substituted materials, except LGNO, show higher values: 0.16 for LENO, 0.17 for LSNO and LNNO, and the highest value equal to 0.18 has been revealed for LPNO. Oxygen mobility and surface reactivity are studied by the temperature-programmed isotope exchange of oxygen with C18O2 in a flow reactor. All samples can be characterized by a fast oxygen diffusivity provided by cooperative mechanism of oxygen migration involving both regular and highly mobile interstitial oxygen. Variation of oxygen tracer diffusion coefficient with dopant cation nature is probably associated with interstitial oxygen content. The best characteristics have been acquired for Ln = Eu (D⁎ = 2.4∙10−9 cm2/s at 700 °C). Electrochemical properties of the related La1.6Ln0.4NiO4+δ electrodes are investigated in a contact with a Ce0.8Sm0.2O1.9 solid-state electrolyte. The influence of the temperature of the electrode formation and the effect of the collector layer on the electrode electrochemical activity are considered. The LENO, LPNO and LSNO-based electrodes demonstrate low polarization resistance related to the enhanced oxygen diffusion properties. Substitution with Gd, contrarily, significantly deteriorates electrochemical properties of LNO.

Sampling Volcanic Plume Using a Drone-Borne SelPS for Remotely Determined Stable Isotopic Compositions of Fumarolic Carbon Dioxide

Both chemical and isotopic compositions of concentrated volcanic plumes are highly useful in evaluating the present status of active volcanoes. Monitoring their temporal changes is useful for forecasting volcanic eruptions as well. Recently, we developed a drone-borne automatic volcanic plume sampler, called SelPS, wherein an output signal from a sulfur dioxide (SO2) sensor triggered a pump to collect plume samples when the SO2 concentration exceeded a predefined threshold. In this study, we added a radio transmission function to the sampler, which enabled our operator to monitor real-time SO2 concentration during flights and thus obtain more concentrated volcanic plume samples through precise adjustment of the hovering position. We attached the improved SelPS to a drone at Nakadake crater, Aso volcano (Japan), and successfully obtained volcanic plume samples ejected from the crater more concentrated than those obtained by using previous version of SelPS in 2019. Additionally, we found a significant linear correlation between the reciprocal of the concentration and isotopic ratios for the 2H/1H ratios of H2, 18O/16O ratios of CO2, and 13C/12C ratios of CO2 within the plume samples. Based on the isotopic ratios of fumarolic H2 (δ2H = −239 ± 6‰) and fumarolic CO2 (δ13C = −3.58 ± 0.85‰ and δ18O = +22.01 ± 0.68‰) determined from the linear correlations, we estimated the apparent equilibrium temperatures (AETs) with magmatic H2O simultaneously and precisely for the first time in erupting volcanoes, assuming hydrogen isotope exchange equilibrium between H2 and H2O (AETD = 629 ± 32°C) and oxygen isotope exchange equilibrium between CO2 and H2O (AET18O = 266 ± 65°C). We found that the AET18O was significantly lower than the AETD in the crater. While the temperature of the magmatic gases was originally 600°C or more, most of the gases cooled just beneath the crater to temperatures around the boiling point of water. The improved SelPS enable us to determine both AETD and AET18O in eruptive volcanoes, wherein fumaroles are inaccessible. Simultaneous and precise determination of both the AET18O and AETD can provide novel information on each volcano, such as the physicochemical conditions of magma degassing and the development of fluid circulation systems beneath each volcano.

Oxygen Isotope Exchange between Carbon Dioxide and Iron Oxides on Mars' Surface.

An investigation of the fundamental processes leading to the incorporation of 18O isotopes in carbon dioxide and in iron oxides is critical to understanding the atmospheric evolution and geochemistry of Mars. Whereas signatures of 18O have been observed by the Phoenix Lander and the sample analysis at Mars for carbon dioxide, the underlying isotopic exchange pathways with minerals of the crust of Mars are still elusive. Here, we reveal that reactions of gaseous 18O-carbon dioxide over goethite (FeO(OH)) and hematite (Fe2O3) lead to an 18O transfer from the atmosphere that enriches the 18O content of the iron oxides in the absence of water and light. This proof-of-concept study shows that isotopic enrichment processes on Mars not only are limited to the atmosphere but also proceed via chemical interaction with dry iron oxides. These processes are decisive to comprehending the 18O cycle between the atmosphere and the surface on the planetary scale.

Increasing the reliability of compound identification in biological samples using 16O/18O-exchange mass spectrometry.

The task of multipurpose analysis of biological samples and identification of individual compounds in them is actual for many organizations in various fields; the results of such analyses can affect lives. The most frequently used, most accurate, and highly sensitive method used for this kind of analysis is the combination of gas/liquid chromatography and high-resolution mass spectrometry. However, in some areas, it is necessary to increase the reliability of compound identification. In this paper, we present a method that combines the reaction of oxygen isotope exchange with mass spectrometry; the method allows to increase the reliability of identification of individual compounds. Oxygen isotope exchange reaction is a "selective" one, which means that not all oxygen present in the molecule can exchange, but only in certain functional groups. Thus, by the number of isotope exchanges that have occurred in this molecule, the right structural formula might be more accurately chosen. The method was tested both on pure pharmaceutical substances and on real human urine samples. In both cases, the effectiveness of the method was shown: the number of expected exchanges in known substances coincided with the experimental one, and from several possible structures of unknown substances, the correct one was chosen based on the number of isotope exchanges.

Heterogeneous isotope effects decouple conifer leaf and branch sugar δ18O and δ13C.

Isotope ratios of tree-ring cellulose are a prominent tool to reconstruct paleoclimate and plant responses to environmental variation. Current models for cellulose isotope ratios assume a transfer of the environmental signals recorded in bulk leaf water to carbohydrates and ultimately into stem cellulose. However, the isotopic signal of carbohydrates exported from leaf to branch may deviate from mean leaf values if spatial heterogeneity in isotope ratios exists in the leaf. We tested whether the isotopic heterogeneity previously observed along the length of a ponderosa pine (Pinus ponderosa) leaf water was preserved in photosynthetic products. We observed an increase in both sugar and bulk tissue δ18O values along the needle, but the increase in carbohydrate δ18O values was dampened relative to the trend observed in leaf water. In contrast, δ13C values of both sugar and bulk organic matter were invariant along the needle. Phloem-exported sugar measured in the branch below the needles did not match whole-needle values of δ18O or δ13C. Instead, there was a near-constant offset observed between the branch and needle sugar δ13C values, while branch δ18O values were most similar to δ18O values observed for sugar at the base of the needle. The observed offset between the branch and needle sugar δ18O values likely arises from partial isotope oxygen exchange between sugars and water during phloem loading and transport. An improved understanding of the conditions producing differential δ13C and δ18O isotope effects between branch phloem and needle sugars could improve tree-ring-based climate reconstructions.

Geochemistry of Brines and Oil Occurrences in the Udachnaya Kimberlite Pipe (Siberian Platform)

Abstract —Results of a geochemical study of brines and oil occurrences in the Udachnaya kimberlite pipe are presented. Like other intrusions in the Daldyn–Alakit diamondiferous region, this diamond deposit is a unique cryohydrogeologic microstructure differing from the host sedimentary rocks and other diamond pipes of the Yakutian diamond-bearing province. Two waterlogged zones distinguished in the section of orebodies at the explored depths of the deposit correspond to the upper and middle Cambrian aquifers. Predominantly acidic (average pH = 5.5) Cl–Ca and Cl–Ca–Na brines with TDS from 94.3 to 391.3 g/dm3 are widespread within the orebodies and host rocks. The brine mineralization and contents of major salt-forming components increase with depth, to the horizon at the -365 m elevation, where TDS reaches 391 g/dm3, while below, at the –650 m level with noted hydrogeochemical-field inversion, TDS is 253 g/dm3. The mineralization of Cl–Ca, Cl–Ca–Na, Cl–Ca–Mg, and Cl–Ca–Mg–Na brines in the upper Cambrian rocks varies from 102.9 to 192.9 g/dm3, and the pH values, from 4.9 to 6.2, averaging 5.6. Among the microcomponents, the highest average concentrations (mg/dm3) are found for Br1292.8 > S875.7 > Sr453.7 > Fe79.7 > Li53.4 > B32.7 > I13.3 > Si10.8 > Mn6.4 > Se3.6 > Rb2.3. The values of genetic coefficients vary widely: The rNa/rCl coefficient ranges from 0.18 to 0.31; rCa/rMg, from 1.03 to 3.60; Ca/Cl, from 0.2 to 0.3; and the integrated metamorphism index S (according to S.L. Shvartsev) varies from 193 to 277. The middle Cambrian rock complex, containing more saline brines, has been examined in much more detail. It hosts Cl–Ca, Cl–Ca–Na, Cl–Ca–Mg, and Cl–Na–Mg brines with TDS from 94.3 to 391.3 g/dm3 and high average concentrations (mg/dm3) of microcomponents: Br2224.9 > Sr1024.9 >S500.1 > B202.9 > Li147.1 > Fe97.0 > I33.2 > Rb11.4 > Si9.6 > Se9.5 > Mn3.6 > Ni1.7. As compared with brines in the overlying rocks, the middle Cambrian brines show a wider variation in element ratios: rNa/rCl from 0.14 to 0.34, rCa/rMg from 0.66 to 9.71, and Ca/Cl from 0.03 to 0.45. These brines are also characterized by a significantly higher metamorphism grade, which is indicated not only by the rNa/rCl and rCa/rMg ratios but also by the S index varying from 278 to 316. The composition of stable isotopes δD and δ18O) and dissolved inorganic carbon δ13C) of the brines was investigated. The studied waters are assumed to be of sedimentary–metamorphic origin. Their isotopic composition reflects the climatic conditions existing at the time of their burial, which were probably aggravated by the contribution of the oxygen isotope exchange with water-bearing rocks. The δ13C values of carbon dioxide dissolved in water allow an inference about its biogenic origin. The biogenic carbon isotope exchange is governed by the relationship between methanogenic and SMT processes. Analysis of the 87Rb/86Sr and 87Sr/86Sr isotope ratios of the studied brines has revealed affinity between the isotopic compositions of waters in the Cambrian deposits and in ancient seawaters. The mass chromatograms of saturated-hydrocarbon (HC) fractions show at least two individual types of oils and malthas (naphthides). The third variety resulted from their mixing at different stages of migration. The fourth is from the contact zone; it changed during the explosion of kimberlites. The first, most common, type of naphthides (“postexplosive”) is similar in all geochemical parameters to oils from the Nepa–Botuobiya anteclise, in particular, to those from the Mirnyi arch. Oils of the second (pre-explosive) type are found only in the Udachnaya Formation, within the depth range 1130–1430 m.

Oxygen Isotope Exchange Reaction for Untargeted LC-MS Analysis.

LC-MS is a key technique for the identification of small molecules in complex samples. Accurate mass, retention time, and fragmentation spectra from LC-MS experiments are compared to reference values for pure chemical standards. However, this information is often unavailable or insufficient, leading to an assignment to a list of candidates instead of a single hit; therefore, additional features are desired to filter candidates. One such promising feature is the number of specific functional groups of a molecule that can be counted via derivatization or isotope-exchange techniques. Hydrogen/deuterium exchange (HDX) is the most widespread implementation of isotope exchange for mass spectrometry, while oxygen 16O/18O exchange is not applied as frequently as HDX. Nevertheless, it is known that some functional groups may be selectively exchanged in 18O enriched media. Here, we propose an implementation of 16O/18O isotope exchange to highlight various functional groups. We evaluated the possibility of using the number of exchanged oxygen atoms as a descriptor to filter database candidates in untargeted LC-MS-based workflows. It was shown that 16O/18O exchange provides 62% (median, n = 45) search space reduction for a panel of drug molecules. Additionally, it was demonstrated that studying the fragmentation spectra after 16O/18O can aid in eliminating false positives and, in some cases, help to annotate fragments formed with water traces in the collisional cell.

Understanding the oxygen reduction kinetics on Sr2-xFe1.5Mo0.5O6-δ: Influence of strontium deficiency and correlation with the oxygen isotopic exchange data

This paper presents, for the first time, the results of studies of the electrochemical reaction of oxygen reduction on Sr2Fe1.5Mo0.5O6-δ and Sr-deficient Sr1.95Fe1.5Mo0.5O6-δ, as promising electrodes for solid state electrochemical devices, by the electrochemical impedance method with the subsequent interpretation of the data using the concepts outlined in the Adler et al. model. It was established that the oxygen reduction reaction for both electrodes is determined by two relaxation processes associated with oxygen diffusion, oxygen surface exchange, and Knudsen diffusion in the pores of the electrode. Strontium deficiency was found to have a positive effect on the electrochemical activity of the electrodes, enhancing the stage related to oxygen diffusion and surface exchange. Also, for the first time, for Sr2Fe1.5Mo0.5O6-δ, a quantitative correlation for the surface oxygen exchange and diffusion coefficients obtained from the impedance data and by the isotopic exchange method is demonstrated.

Oxygen Isotope Exchange over Copper-Containing Mordenite: The Effect of Copper Loading and Si/Al Ratio

Oxygen Isotope Exchange over Copper-Containing Mordenite: The Effect of Copper Loading and Si/Al Ratio

ZSM-5 core–shell structured catalyst for enhancing low-temperature NH3-SCR efficiency and poisoning resistance

By constructing core–shell ZSM-5@CeO2 support rather than bulk phase for loading copper, the enhanced NH3-SCR performance as well as H2O and SO2 tolerance was achieved. Cu/(ZSM-5@CeO2) catalyst exhibited the superior activity with the lowest T90 at 215 °C, which is due to the interaction between CeO2 shell and copper ions that promotes the redox properties as evidenced by oxygen isotopic exchange technique. The ZSM-5 core provides more acid sites to improve the ammonia adsorption. Thus, the highest activity of Cu/(ZSM-5@CeO2) catalyst can be ascribed to the synergistic effect of redox ability and acidity. The CeO2 shell can react with SO2 preferentially and lead to a high sulfur tolerance. This study provides a strategy for design and the practical applications of NH3-SCR zeolite catalysts.

Clumped isotope acid fractionation factors for dolomite and calcite revisited: Should we care?

During the analysis of the Δ47 values of CO2 derived from carbonates, the acid fractionation factor not only allows Δ47 values produced from carbonates and reacted at different temperatures (usually 25 and 90 °C) to be compared to one another, but also provides an effective tool to better understand the mechanism and rate of isotopic exchange of oxygen with water during the phosphoric acid digestion of carbonate minerals. In this study, experiments have been conducted in which calcite (1 sample) and dolomite (4 samples), with varying Δ47 values, have been digested in phosphoric acid (H3PO4) at five different temperatures between 25 and 90 °C using both the common acid bath and sealed vessel methods. From these experiments, we show that calcite has an acid fractionation factor which is independent of the reaction method. In contrast, all four dolomites show significant differences between the two methods with the sealed vessel reactions showing much smaller acid fractionation factors than the common acid bath. The magnitude of the acid fractionation factor in the dolomites is also dependent upon the absolute Δ47 value of the sample, with samples possessing lower Δ47 values producing lower acid fractionation factors than those with higher Δ47 values. The explanation for the difference in the behavior of acid fractionation factors between calcite and dolomite, in regard to the technique used, is believed to be related to the rate of reaction of the two minerals and thus the time in which the CO2 is in contact with the acid and allowed to exchange with the H2O in the acid and produced during the reaction.

A density functional theory (DFT) study on reduced partition function ratios of oxygen species adsorbed on a Pt19 cluster and oxygen isotope effects

ABSTRACT A density functional theory (DFT) computation on oxygen species adsorbed on platinum (Pt) catalyst surfaces has been carried out to elucidate oxygen isotope fractionation observed at the cathode of a polymer electrolyte membrane fuel cell (PEMFC). The Pt(111) catalyst surface was modelled by a Pt19 cluster, and O, OH, OHH, OO, OOH, OHOH and HOHOH were assumed to be the oxygen species adsorbed on the Pt(111) surface. The oxygen isotope reduced partition function ratios (RPFRs) of the adsorbed species were calculated using the vibrational frequencies obtained by normal mode analyses performed on the optimized structures. Various oxygen isotope exchange equilibria among the adsorbed oxygen species and oxygen and water molecules in the gas phase were examined using their RPFRs. Experimental observation that the lighter 16O is enriched in water molecules exhausted from the cathode is explainable in a satisfactory manner by assuming oxygen isotope exchange equilibria of O2 molecule with O, OH, OO and OOH adsorbed on the Pt(111) surface that appear in the first half of the conversion reaction from O2 to H2O and those of H2O molecule with the adsorbed oxygen species, OHH, OHOH and HOHOH, formed in the latter half of the conversion reaction.

In situ oxidation of sulfide minerals supports widespread sulfate reducing bacteria in the deep subsurface of the Witwatersrand Basin (South Africa): Insights from multiple sulfur and oxygen isotopes

Dissolved sulfate is a crucial electron acceptor for the subsurface biosphere, particularly for the living microbial ecosystems in the long-isolated (on the order of millions to billions of years) deep subsurface fracture waters in Precambrian cratons, e.g., in the Witwatersrand Basin of the Kaapvaal Craton, South Africa. Aiming to understand the role of sulfate in the sustainability of the subsurface habitat and the spatial extent of the terrestrial subsurface biosphere, we carried out a basin-scale examination on the sources and producing mechanisms of dissolved sulfur (sulfate and sulfide) in the subsurface fracture waters in the Witwatersrand Basin using multiple sulfur isotopes (32,33,34,36S) and oxygen isotopes (16,18O). Dissolved sulfates in 14 fracture water samples collected from 900 to 3,413 meters below the surface at 6 sites show isotopic ranges from −5.3‰ to +19.4‰ for δ34S, −0.40‰ to +0.50‰ for Δ33S, and −1.1‰ to +10.9‰ for δ18O. These isotopic signatures are distinct to those of the sulfate minerals (e.g., the carbonate-associated sulfate in local Transvaal Supergroup dolomite sequences: δ34S = +31.4‰ to +39.2‰; Δ33S = −0.01‰ to +0.16‰), but identical to those of the sulfide minerals in the host rocks. This indicates that the dissolved sulfate in the fracture waters were dominantly generated by in situ oxidation of sulfide minerals at basin scale, although mixing of a small amount of surface sulfate at some sites cannot be completely ruled out. The dissolved sulfates in the less deep and less saline fracture waters are in oxygen isotope disequilibrium with their host waters, a surprising result given that the water residence times are orders of magnitude longer than the time required for oxygen isotope exchange to reach equilibrium. This implies that vigorous in situ sulfate production has occurred after the fracture waters were isolated. In contrast, the dissolved sulfate in the deeper, more saline waters are in apparent oxygen isotope equilibration or close to equilibration with their host waters. This might be attributed to a combined effect of faster oxygen isotope exchange between sulfate and water at higher temperatures, larger extent of sulfate reduction, and/or less efficient sulfate production. The dissolved sulfide in the fracture waters has similar Δ33S values but is 3.0‰ to 26.4‰ lower in δ34S than coexisting sulfate, suggesting that the dissolved sulfide is mostly generated from bacterial sulfate reduction, which is consistent with the widespread existence of sulfate-reducing bacteria down to >3.4 km below surface in the Witwatersrand Basin. Overall, these novel isotopic results demonstrate that geological processes can provide a steady long-term sulfate source in deep fracture fluids by in situ oxidation of sulfide minerals in their host rocks, and thereby a mechanism to sustain the terrestrial subsurface biosphere, even in deep, high-temperature, long-isolated water systems. Thus, sulfate as a terminal electron acceptor is not the limiting factor for the spatial expansion of terrestrial subsurface biosphere.

Isotopic exchange of oxygen, sulfur, hydrogen and copper between aqueous phase and the copper minerals brochantite, libethenite and olivenite

AbstractFractionation factors for the isotopes of O, H, S, or Cu (as appropriate) were determined for the minerals brochantite [Cu4(SO4)(OH)6], libethenite [Cu2(PO4)(OH)] and olivenite [Cu2(AsO4)(OH)] and corresponding aqueous solutions at temperatures between 30 and 70°C. All samples used for this determination were synthetic and the degree of fractionation was expressed as 1000 ln α = (A × 106/T2) + B, where A and B are empirical parameters. A few natural libethenite samples from its type locality Ľubietová-Podlipa were also analysed and compared to the prediction based on the isotopic composition of meteoric water and our fractionation factors. The hydrogen fractionation factors agreed with the prediction well, whereas those for oxygen did not. A possible explanation is the disequilibrium of aqueous phosphate (and also arsenate) species and the solution in our experiments or the interaction of meteoric fluids with the isotopically heavy (in terms of oxygen) country rocks. Because the effects of isotopic disequilibrium in our experiments cannot be ruled out, the oxygen fractionation factors should be used with caution. The determined fractionation factors can be used as an isotope geothermometer, given that it can be proven that the phases of interest precipitated from the same fluid in equilibrium. Libethenite is predicted to have slightly lower δ65Cu values than its parental solution, but brochantite slightly higher δ65Cu values than its parental solution. Simple forward models, simulating neutralisation or reduction of mine drainage, show that precipitation of these minerals and removal of the co-existing fluid, could cause isotopic variations (in δ65Cu) on the order of 1‰ or more.

Oxygen Isotopic Compositions in a Plagioclase‐Olivine Inclusion from Ningqiang Similar to Those in Al‐rich Chondrules

AbstractWe report the petrology and oxygen isotopic composition, using a Cameca NanoSIMS 50L ion microprobe, of a plagioclase–olivine inclusion, C#1, found in the Ningqiang carbonaceous chondrite. In addition to major phases (plagioclase, spinel and olivine), C#1 is also surrounded by a pyroxene rim (64 vol % Ca‐rich and 36 vol % Ca‐poor pyroxenes). On a three‐isotope oxygen diagram, δ17O vs. δ18O, the compositions of individual minerals analyzed in C#1 fall along the carbonaceous chondrite anhydrous mineral line (CCAM), and oxygen isotopic compositions in C#1 show significant variability in δ18O and δ17O. The oxygen isotopic compositions of the pyroxene rim minerals are similar to those of the other host minerals, which suggests that the rim likely formed from the same melting process as the host. The rim is considered to have formed as a result of interaction between an 16O‐poor gas and a melt. Some spinel grains are typically 16O‐rich and likely of relict origin, which is similar to 16O‐rich Ca‐, Al‐rich inclusions, which are probably a precursor of C#1. The inclusion then likely melted in an 16O‐poor region where chondrules form, accompanied by oxygen isotope exchange with an 16O‐poor gas. Some anorthite, pyroxene and spinel might have undergone fluid‐assisted thermal metamorphism on the Ningqiang chondrite parent body. The oxygen isotope data and evolution of the C#1 plagioclase–olivine inclusion are similar with those of Al‐chondrules in chondrites.

An experimental study on oxygen isotope exchange reaction between CAI melt and low-pressure water vapor under simulated Solar nebular conditions

Calcium-aluminum-rich inclusions (CAIs) are known as the oldest high-temperature mineral assemblages of the Solar System. The CAIs record thermal events that occurred during the earliest epochs of the Solar System formation in the form of heterogeneous oxygen isotopic distributions between and within their constituent minerals. Here, we explored the kinetics of oxygen isotope exchange during partial melting events of CAIs by conducting oxygen isotope exchange experiments between type B CAI-like silicate melt and 18O-enriched water vapor (PH2O = 5 × 10−2 Pa) at 1420 °C. We found that the oxygen isotope exchange between CAI melt and water vapor proceeds at competing rates with surface isotope exchange and self-diffusion of oxygen in the melt under the experimental conditions. The 18O concentration profiles were well fitted with the three-dimensional spherical diffusion model with a time-dependent surface concentration. We determined the self-diffusion coefficient of oxygen to be ∼1.62 × 10−11 m2 s−1, and the oxygen isotope exchange efficiency on the melt surface was found to be ∼0.28 in colliding water molecules. These kinetic parameters suggest that oxygen isotope exchange rate between cm-sized CAI melt droplets and water vapor is dominantly controlled by the supply of water molecules to the melt surface at PH2O < ∼10−2 Pa and by self-diffusion of oxygen in the melt at PH2O > ∼1 Pa at temperatures above the melilite liquidus (1420–1540 °C). To form type B CAIs containing 16O-poor melilite by oxygen isotope exchange between CAI melt and disk water vapor, the CAIs should have been heated for at least a few days at PH2O > 10−2 Pa above temperatures of the melilite liquidus in the protosolar disk. The larger timescale of oxygen isotopic equilibrium between CAI melt and H2O compared to that between H2O and CO in the gas phase suggests that the bulk oxygen isotopic compositions of ambient gas at ∼1400 °C in the type B CAI-forming region is preserved in the oxygen isotopic compositions of type B CAI melilite. Based on the observed oxygen isotopic composition, we suggest that a typical type B1 CAI (TS34) from Allende was cooled at a rate of ∼0.1–0.5 K h−1 during fassaite crystallization.