Oxygen Isotope Disequilibrium Research Articles

The effect of cave ventilation on carbon and oxygen isotopic fractionation between calcite and drip water

Rapid CO2 degassing and calcite precipitation driven by cave ventilation influence the speleothem δ18O and δ13C. However, the drivers of cave ventilation are not completely understood due to the lack of monitoring of multiple environmental factors. Furthermore, the understanding of isotope fractionation caused by the dissolution of speleothem in undersaturated drip water is limited during the cave air stagnation. In this study, we displayed four years of cave microenvironment monitoring in Shawan Cave, Southwestern China, and analyzed the δ13CDIC and δ18O of drip water, and calcite precipitation δ18O and δ13C. The results show that the ventilation process is attributed to buoyancy airflow between external atmosphere, fissure air, and cave air. This causes that the higher (lower) cave air pCO2 in the summer (winter) is associated with upward airflow mode (downward airflow mode). Furthermore, cave ventilation could control the isotopic fractionation. Specifically, when cave air pCO2 is lower, the carbon isotopic disequilibrium between calcite and dissolved inorganic carbon (DIC) is controlled by the degassing of CO2 associated with calcite precipitation. The disequilibrium fractionation in carbon isotopes is less pronounced at slower drip-rate sites. The oxygen isotope fractionation between calcite and the drip water is found to be close to equilibrium. However, the high cave air pCO2 (exceeding 10,000 ppm) may result in drip water undersaturation to drive the dissolution of speleothem calcite. The δ18O values of drip water are pulled away from their original values to disequilibrate to the calcite because the exchange time of oxygen in the dissolved carbonates with the oxygen in the water is sufficiently long. Hence, the dissolution of speleothems may be a new mechanism to explain the oxygen isotopic disequilibrium between the calcite and drip water during the cave air stagnation. The carbon isotope fractionation between calcite and drip water is close to equilibrium.

Disequilibrium in historic volcanic rocks from Fogo, Cape Verde traces carbonatite metasomatism of recycled ocean crust

Fogo, Cape Verde, located upon thick oceanic lithosphere, provides a window into processes occurring in the mantle where recycled ocean crust in an upwelling mantle plume interacts with ambient mantle. Our objective is to investigate the nature of the lithologies of the mantle sources involved in the petrogenesis of historic volcanic rocks from Fogo. We observe enclaves and mingling textures in the lavas combined with oxygen isotope disequilibrium between olivine and clinopyroxene phenocrysts. Olivine δ18O values display positive correlations with Zr/Hf and Zr/Y and a negative correlation with U/Th, whereas clinopyroxene δ 18O values correlate positively with Ba/Nb. Heterogeneity between crystal populations and within the groundmass indicates that multiple magma batches are mixed beneath Fogo. In terms of mantle endmembers and source lithologies, a HIMU endmember was generated by melting of carbonated eclogite as indicated by low δ 18O values, Zr/Hf, Ba/Nb and high U/Th ratios. In contrast, we show the EM1 endmember has high δ 18O, Zr/Hf, Ba/Nb and low U/Th ratios, derived from melting of variably carbonated peridotite. Additionally, Ba/Th ratio are high, indicating that carbonatite melts have contributed to alkaline magma compositions at Fogo.

Dual clumped (Δ47-Δ48) isotope data for amorphous carbonates and transformation products reveal a novel mechanism for disequilibrium clumped isotope effects

Amorphous precursors to minerals have been observed in laboratory materials and in nature, including across diverse phyla. These metastable phases allow for the incorporation of cations at higher concentrations than classical crystallization pathways, thus, their chemistry and behavior have implications in an array of disciplines. Currently, little is known about the isotopic composition of the anion in amorphous carbonates and how isotopic values evolve during transformation into a mineral. Here, we examined the evolution of isotopic values in amorphous carbonates and mineral transformation products to identify the potential origins of disequilibrium isotopic compositions in carbonate minerals that form from an amorphous precursor. We measured dual carbonate clumped isotopes (13C18O16O - Δ47; 12C18O18O - Δ48), bulk stable isotope ratios (δ13C, δ18O), and chemical and structural data throughout the transformation of amorphous calcium magnesium carbonate (ACMC) into high Mg-calcite (HMC) over 1 year, with crystallization occurring in solutions from 10 to 60 °C. The Δ47, Δ48, and δ18O values evolved significantly during transformation, indicating dissolution of ACMC and reprecipitation of HMC. After crystallization, the Δ47 and Δ48 values achieved a disequilibrium steady state, while δ18O values continued to evolve. For the fully crystallized HMC samples, the low temperature samples formed at 10 °C had the greatest extent of oxygen isotope disequilibrium (measured value – equilibrium value = −39‰); conversely; the greatest clumped isotope disequilibrium was observed in high temperature samples formed at 40 and 60 °C (0.068‰ for Δ47, 0.072‰ for Δ48). These results are consistent with a new potential mechanism of disequilibrium clumped isotope values in carbonate minerals. Specifically, the dissolution of ACMC during transformation causes disequilibrium oxygen and clumped isotope values in the dissolved inorganic carbon (DIC) pool. The extent of isotopic disequilibrium in DIC during transformation is temperature dependent, and is recorded by the forming mineral. Isotopic results may also reflect mixing effects, as scanning electron microscopy (SEM) showed ACMC and HMC existing simultaneously during transformation, indicating that ACMC likely progressively dissolves and reprecipitates as the DIC pool isotopically evolves. This may result in heterogeneous isotopic values in HMC. In total, these data suggest a highly dynamic localized environment could exist in biomineralizing organisms and abiotic systems that utilize amorphous precursors to form carbonate minerals, potentially resulting in isotopic values that are not representative of formation temperature.

Stable isotopic study of carbonatites from the Pakkanadu Alkaline Complex, southern India: Constraints on carbonatite melt evolution and sub-solidus, high temperature fluid-rock interaction

Carbonatites of the Pakkanadu Alkaline Complex (PAC) of the Dharmapuri Rift Zone (DRZ), in the Northern Granulite Terrain (NGT) of southern India, were intruded as small concordant and discordant bodies into pyroxenites and syenites during the Neoproterozoic (∼759‐–750 Ma). Carbonatite samples from the PAC were grouped into three major groups for oxygen and carbon isotope analysis: (A) calcite-dominated (88–100%), (B) dolomite-dominated (83–97%) and (C) admixtures of calcite and dolomite. End-member isotopic compositions were ẟ 13 C = −5.7 ± 0.1‰ and ẟ 18 O = +8.4 ± 0.2‰ for calcite and ẟ 13 C = −6.0‰ and ẟ 18 O = +6.9‰ for dolomite. The carbonatite isotopic compositions lie within the range known for primary igneous carbonatites (PIC), indicating their origin from a mantle source. The higher ẟ 18 O of the calcite end-member than the dolomite end-member indicates oxygen isotopic disequilibrium in the carbonatites. This disequilibrium was the product of sub-solidus oxygen isotope exchange with fluids derived from carbonatite melt during the brine-melt stage (600–400 °C). The narrow range of ẟ 13 C of the carbonatites and its similarity to the ẟ 13 C of depleted upper mantle (−6 ± 2‰) suggests that very little CO 2 was associated with the carbonatite melt. We infer that this type of carbonatite melt evolved from the upper asthenosphere or the base of the lithosphere (> 3 GPa, i.e., >100 km). Similar observations were made based on compiled ẟ 13 C and ẟ 18 O data for carbonatites from Salem-Attur fault, Sevathur, and Hogenakkal regions of the NGT. The ẟ 13 C and ẟ 18 O compositions of carbonatites from Samalpatti, India, however, are distinctly different and suggest two sources for carbonatite melts, one containing a significant amount of CO 2 and possibly evolved from somewhere in the middle of the lithospheric mantle (∼ 2–3 GPa, i.e., 60–100 km) and the other associated with crustal sedimentary or metasedimentary carbonates, which were possibly incorporated during emplacement of carbonatite melts originating from the lithospheric mantle. This study shows that carbonatite melts in the NGT mostly evolved from different levels of the upper mantle and were emplaced to crustal levels, perhaps via a rifting-induced fracture network. • Carbonatites of the Pakkanadu Alkaline Complex from southern India were investigated. • ẟ 13 C and ẟ 18 O of the carbonatites indicate their origin from a mantle source. • O isotope exchange occurred between the carbonatite and carbonatite-derived fluids. • CO 2 production was insignificant during partial melting of the mantle source. • The carbonatite was emplaced to crustal levels via a rift-related fracture system.

Asynchronous infiltration-driven growth of forsterite and periclase during metamorphism in marbles of the inner Alta aureole, Utah: δ18O and textural records of oxygen isotope disequilibrium, rapid forsterite growth and reaction history

Asynchronous infiltration-driven growth of forsterite and periclase during metamorphism in marbles of the inner Alta aureole, Utah: δ18O and textural records of oxygen isotope disequilibrium, rapid forsterite growth and reaction history

Isotopic evidence for pallasite formation by impact mixing of olivine and metal during the first 10 million years of the Solar System.

Pallasites are mixtures of core and mantle material that may have originated from the core-mantle boundary of a differentiated body. However, recent studies have introduced the possibility that they record an impact mix, in which case an isotopic difference between metal and silicates in pallasites may be expected. We report a statistically significant oxygen isotope disequilibrium between olivine and chromite in main group pallasites that implies the silicate and metal portions of these meteorites stem from distinct isotopic reservoirs. This indicates that these meteorites were formed by impact mixing, during which a planetary core was injected into the mantle of another body. The impactor likely differentiated within ∼1-2Myr of the start of the Solar System based on Hf-W chronology of pallasite metal, and we infer the age of the impact based on Mn-Cr systematics and cooling rates at between ∼1.5 and 9.5Myr after Ca-Al-rich inclusions (CAIs). When combined with published slow subsolidus cooling rates for these meteorites and considering that several pallasite groups exist, our results indicate that such impacts may be an important stage in the evolution of planetary bodies.

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.

Are oxygen isotope fractionation factors between calcite and water derived from speleothems systematically biased due to prior calcite precipitation (PCP)?

The equilibrium oxygen isotope fractionation factor between calcite and water (18αcalcite/H2O) is an important quantity in stable isotope geochemistry and allows in principle to infer temperature variations from carbonate δ18O if carbonate formation occurred in thermodynamic equilibrium. For this reason, many studies intended to determine the value of the oxygen isotope fractionation factor between calcite and water (18αcalcite/H2O) for a wide range of temperatures using modern cave calcite and the corresponding cave drip water or ancient speleothem carbonate and fluid inclusion samples. However, the picture that emerges from all of these studies indicates that speleothem calcite is not formed in thermodynamic equilibrium but under kinetic conditions, provoking a large variability of determined 18αcalcite/H2O values. Here we present a conceptual framework that can explain the variability of 18αcalcite/H2O values obtained by cave studies. Prior calcite precipitation (PCP) is calcite precipitation before cave drip water is dripping from the cave ceiling and impinges on the surface of a stalagmite or watch glass. Prior to the karst water dripping from the cave ceiling, PCP can occur in the karst above the cave as well as on the cave ceiling, the cave walls and on the surface of stalactites. We argue that PCP leads to increasing the δ18O value of the dissolved HCO3− (δ18OHCO3-), resulting in an oxygen isotope disequilibrium of the δ18OHCO3- values with respect to the δ18O value of water (δ18OH2O). The oxygen isotope disequilibrium between HCO3− and H2O is re-equilibrated by oxygen isotope exchange between H2O and HCO3. Depending on the temperature, the re-equilibration time varies from hours to days and is usually much longer than the residence time of the drip water on stalactites, but much shorter than the time required to percolate through the karst. Therefore, while the oxygen isotope equilibrium between HCO3− and H2O is very likely re-established when PCP occurred in the karst, oxygen isotope disequilibrium conditions between HCO3− and H2O still prevail when PCP occurred inside a cave, e.g., on stalactites. If the oxygen isotope disequilibrium conditions between HCO3− and H2O is not re-established, the precipitated calcite will inherit the elevated δ18O value of the HCO3− and not be in oxygen isotope equilibrium with the corresponding drip water. Consequently, if the 18αcalcite/H2O value is calculated from cave calcite samples affected by PCP, the derived value will be systematically biased.

Constraining speleothem oxygen isotope disequilibrium driven by rapid CO2 degassing and calcite precipitation: Insights from monitoring and modeling

Oxygen isotopes are the most commonly applied speleothem proxy for reconstructing Quaternary changes in precipitation and/or temperature. These interpretations are either limited to qualitative wetting and drying trends or rely on theoretical, experimental and/or empirical equilibrium isotope fractionation factors for more quantitative constraints. These various fractionation factors have similar temperature sensitivities, but their absolute values differ, and cave calcite does not appear to generally precipitate in isotopic equilibrium with its drip water. Rapid CO2 degassing paired with calcite precipitation, both occurring under disequilibrium conditions, are a set of mechanisms commonly invoked to explain offsets between observed and equilibrium isotopic fractionation between cave calcites and drip waters. However, the relevance of these disequilibrium mechanisms to speleothem records remains unresolved. Here, we compare measured δ18O values of modern speleothem calcite from a tropical cave in Guam to calcite δ18O values predicted by a modified version of the ISOLUTION proxy system model. This extends the global comparison of cave drip water and modern calcite δ18O values to higher temperatures. We initialize the model using contemporaneous measurements of drip water (δ18O values, [Ca+], and pH), and cave air (CO2, and T) from four drip sites over 3.5 years of monitoring in the cave. Through this comparison, we show that for a slow drip-rate site, ventilation-driven CO2 degassing can explain seasonal variations in calcite oxygen isotope composition. At faster-dripping sites in this cave, the seasonal effect is limited. At these sites, the DIC reservoir is replenished by new drips faster than its isotopic composition can be modified by degassing CO2 and calcite precipitation, whether occurring each is occurring as an equilibrium or kinetic process. For the slow drip rate site, however, this is the first observation of cave air CO2 variations exerting a control on cave calcite oxygen isotope values. The confirmation of ventilation-driven processes controlling oxygen isotope values at a slow-drip site advances the process-based understanding of stalagmite formation that is required to move beyond the wetter-or-drier paradigm and make quantitative interpretations of speleothem oxygen isotope records.

Oxygen Isotope Fractionation between Phenocrysts and Melt: Equilibrium Estimation for the Alkaline Lavas of Changbaishan Volcano (Northeast China)

The mechanisms of the occurrence of nonequilibrium oxygen isotope fractionation between olivine and plagioclase phenocrysts and the groundmass of rocks (from alkaline basalts to alkaline rhyolites) of Changbaishan volcano are considered. The basaltic trachyandesite–trachyte–comendite–pantellerite rock series shows a systematic increase of the δ18O values of feldspar (from 5.4 to 7.8‰) and the rock groundmass (from 5.6 to 7.1‰). In contrast, the δ18О values of olivine decrease from 5.35‰ typical of mantle peridotites to significantly lower values (3.88–4.14‰). This is accompanied by changes in olivine composition from the Mg-rich (Fo = 74–79) to almost pure fayalite (Fo = 1), thus indicating a positive correlation between the Mg–number and δ18О of olivine. It is shown that feldspar and the rock groundmass are close to the oxygen isotopic equilibrium, whereas olivine–rock groundmass and olivine–feldspar pairs did not approach the oxygen isotopic equilibrium. The main mechanisms leading to the oxygen isotopic disequilibrium in the mineral–melt system are considered. An approach to the estimation of oxygen isotope equilibrium between the phenocrysts and melts is proposed. It takes into account the degree of melt polymerization (NBO/T ratio). This approach makes it possible to explain the positive correlation between δ18О values and olivine Mg-numbers in the Changbaishan lavas, as well as the occurrence of low δ18O values (down to +3‰) in ferrous olivine from alkaline–salic rocks. The δ18О values observed in the olivine and the rock groundmass reflect changes in the degree of melt polymerization during crystal fractionation. The proposed model does not require an additional geological process, in particular, the contribution of a low–δ18О material in the formation of the Changbaishan differentiated rock series.

Oxygen isotope disequilibrium in the juvenile portion of oyster shells biases seawater temperature reconstructions

For decades, bivalve shells have constituted one of the most common supports for paleoclimatic archives based on stable isotope approaches. In this work, we conducted chemical marking and recapture techniques to study the fluctuation of δ18O values of oyster shells of the species Magallana gigas reared in natural environment in Normandy (France) for two years. The results were compared to the continuous monitoring of temperature and salinity and monthly records of seawater δ18O. Isotopic measurements were performed on the hinge area that regroups the whole life of the oysters. Here we demonstrate that oysters mineralized their shells with no significant growth breaks during the two-years experiment, even at temperatures below 6 °C. The results confirm that adult oysters (i.e. > 1 yr) mineralized their shells at equilibrium. However, juvenile specimens exhibit a strong isotopic disequilibrium, with a maximum shift of the δ18O values of 3‰ in winter, likely due to kinetic isotope effects. This corresponds to a reconstructed temperature up to 13 °C warmer than expected. This work indicates that although these oyster shells can be used as an accurate archive of (paleo)environmental conditions, the shell portion mineralized during the juvenile stage (i.e. < 1 yr) should be avoided for paleotemperature reconstructions. Given the wide use of bivalve shells as environmental archives, similar studies on others species are required.

Oxygen isotope composition of waters recorded in carbonates in strong clumped and oxygen isotopic disequilibrium

Abstract. Paleoenvironmental reconstructions, which are mainly retrieved from oxygen isotope (δ18O) and clumped isotope (Δ47) compositions of carbonate minerals, are compromised when carbonate precipitation occurs in isotopic disequilibrium. To date, knowledge of these common isotopic disequilibria, known as vital effects in biogenic carbonates, remains limited, and the potential information recorded by δ18O and Δ47 offsets from isotopic equilibrium values is largely overlooked. Additionally, in carbonates formed in isotopic equilibrium, the use of the carbonate δ18O signature as a paleothermometer relies on our knowledge of the paleowaters' δ18O value, which is often assumed. Here, we report the largest Δ47 offsets observed to date (as much as −0.270 ‰), measured on microbial carbonates that are strongly linked to carbonate δ18O offsets (−25 ‰) from equilibrium. These offsets are likely both related to the microorganism metabolic activity and yield identical erroneous temperature reconstructions. Unexpectedly, we show that the δ18O value of the water in which carbonates precipitated, as well as the water–carbonate δ18O fractionation dependence on temperature at equilibrium, can be retrieved from these paired δ18O and Δ47 disequilibrium values measured in carbonates. The possibility to retrieve the δ18O value of paleowaters, sediments' interstitial waters or organisms' body water at the carbonate precipitation loci, even from carbonates formed in isotopic disequilibrium, opens long-awaited research avenues for both paleoenvironmental reconstructions and biomineralization studies.

Oxygen isotope systematics of chondrule olivine, pyroxene, and plagioclase in one of the most pristine CV3Red chondrites (Northwest Africa 8613).

We performed in situ oxygen three-isotope measurements of chondrule olivine, pyroxenes, and plagioclase from the newly described CVRed chondrite NWA 8613. Additionally, oxygen isotope ratios of plagioclase in chondrules from the Kaba CV3OxB chondrite were determined to enable comparisons of isotope ratios and degree of alteration of chondrules in both CV lithologies. NWA 8613 was affected by only mild thermal metamorphism. The majority of oxygen isotope ratios of olivine and pyroxenes plot along a slope-1 line in the oxygen three-isotope diagram, except for a type II and a remolten barred olivine chondrule. When isotopic relict olivine is excluded, olivine, low- and high-Ca pyroxenes are indistinguishable regarding Δ17O values. Conversely, plagioclase in chondrules from NWA 8613 and Kaba plot along mass-dependent fractionation lines. Oxygen isotopic disequilibrium between phenocrysts and plagioclase was caused probably by exchange of plagioclase with 16O-poor fluids on the CV parent body. Based on an existing oxygen isotope mass balance model, possible dust enrichment and ice enhancement factors were estimated. Type I chondrules from NWA 8613 possibly formed at moderately high dust enrichment factors (50× to 150× CI dust relative to Solar abundances); estimates for water ice in the chondrule precursors range from 0.2 to 0.6× the nominal amount of ice in dust of CI composition. Findings agree with results from an earlier study on oxygen isotopes in chondrules of the Kaba CV chondrite, providing further evidence for a relatively dry and only moderately high dust-enriched disk in the CV chondrule-forming region.

Nebular history of an ultrarefractory phase bearing CAI from a reduced type CV chondrite

Ultrarefractory (UR) phases in CAIs could have formed at higher T compared to common CAI minerals and thus they potentially provide constraints on very high-T processes in the solar nebula. We report a detailed characterization of an UR phase davisite bearing CAI from a reduced type CV chondrite. Absence of secondary iron- and/or alkali-rich phases and occurrence of LIME olivine indicate that primitive chemical and isotopic compositions are preserved in the CAI. Davisite occur only in one lithological unit that consists of three chemically and isotopically distinct parts: i) $^{16}$O-poor regions with reversely-zoned melilite and davisite; ii) $^{16}$O-rich regions consisting of unzoned, gehlenitic melilite, diopside and spinel; and iii) spinel framboids composed of $^{16}$O-rich spinel and $^{16}$O-poor melilite. Random distribution of chemical and isotopic heterogeneities with sharp boundaries in the CAI indicates its formation by an aggregation of mineral assemblages formed and processed separately at different time and/or space. Although isotope exchange prior to the final agglomeration of the CAI cannot be ruled out, we suggest that modification of chemical and isotopic composition of porous CAI precursors or aggregation of isotopically distinct mineral assemblages are alternative scenarios for the origin of O-isotopic heterogeneity in CAIs. In either case, coexistence of spatially and/or temporally distinct $^{16}$O-rich and -poor gaseous reservoirs at the earliest stage of the solar system formation is required. The grain-scale oxygen isotopic disequilibrium in the CAI indicate that post-formation heating of the CAI was short, which can be achieved by rapid outward transport of the CAI. High Ti$^{3+}$/Ti$^{\mathrm{tot}}$ ratios of pyroxene and presence of LIME olivine document that the entire CAI formation process took place under highly reducing conditions.

Oxygen isotope disequilibrium during serpentinite dehydration

AbstractTalc + olivine in metaperidotites result from the serpentinite breakdown due to increasing temperature in the Bergell contact aureole. Jack‐straw olivine textures are present in close proximity to the serpentine breakdown reaction. As the intrusion is approached, the number of olivine crystals increases while the size of the crystals decreases; this feature documents increased overstepping with increased heating rates. Talc veinlets are observed in the outer parts of the talc–olivine zone and are interpreted to be pathways of fluid produced during devolatilization of serpentine. None of the talc–olivine oxygen isotope pairs analysed are in isotopic equilibrium with respect to the peak contact temperature. This implies that escaping fluids cannot be in equilibrium with both phases. Hence, the fluid produced by serpentine reaction does not directly reflect the protolith composition, and attention must be given to the reaction mechanism before interpreting fluid isotope composition.

Oxygen and hydrogen isotopic composition of phlogopites and amphiboles in diamond-bearing kimberlite hosted MARID xenoliths: Constraints on fluid-rock interaction and recycled crustal material in the deep continental lithospheric mantle

Abstract MARID (Mica-Amphibole-Rutile-Ilmenite-Diopside) xenoliths are transported from the deep-cratonic lithosphere to the Earth's surface by Cretaceous kimberlites emplaced in the Kimberley area of the Kaapvaal Craton. MARID xenoliths have high modal abundances (70–80 vol%) of mica and amphibole, indicating their origin from a hydrous source. The δ18O values (4.7 ≤ δ18O ≤ 6.9‰) of phlogopite micas from 14 MARID samples indicate that these minerals are both 18O–enriched and 18O–depleted with respect to the average upper mantle δ18O value of 5.8 ± 0.6‰. The range of δ2H values of phlogopites (−83 ≤ δ2H ≤ −53‰, n = 14) of MARID xenoliths are slightly larger than the average mantle δ2H value (−70 ± 10‰). The oxygen (Δ18Ophlogopites-amphibole = −0.4 and 0.4‰) and hydrogen (Δ2Hphlogopite-amphibole = 14 and 36‰) isotopic disequilibrium recorded from two MARID xenoliths suggests the duration of the last isotopic exchange, possibly just before the kimberlite emplacement, between these minerals and metasomatic fluids was too short to reach isotopic equilibrium. Our model calculation indicates that the phlogopites of MARID xenoliths underwent isotopic exchange with fluids of δ18O = 5.5 to 10‰, δ2H = −62 to −90‰. The range of δ18O value of the calculated metasomatic fluids resembles the oxygen isotopic composition of the primary mantle carbonate (~ 6–9‰) suggesting interaction between carbonatic melt and MARID xenoliths in the continental lithospheric mantle. Furthermore, δ18O values of phlogopites together with previously published nitrogen isotope data (−11 ≤ δ15N ≤ 9‰; Banerjee et al., 2015) indicates incorporation of inhomogeneously distributed recycled crustal material from subducted crust within their source magma. Therefore, O-H-N isotope data for MARID xenoliths indicates their crystallization from geochemically heterogeneous magma in the upper continental mantle and subsequent metasomatism with mantle fluids.

Disequilibrium δ18O values in microbial carbonates as a tracer of metabolic production of dissolved inorganic carbon

Carbon and oxygen stable isotope compositions of carbonates are widely used to retrieve paleoenvironmental information. However, bias may exist in such reconstructions as carbonate precipitation is often associated with biological activity. Several skeleton-forming eukaryotes have been shown to precipitate carbonates with significant offsets from isotopic equilibrium with water. Although poorly understood, the origin of these biologically-induced isotopic shifts in biogenic carbonates, commonly referred to as “vital effects”, could be related to metabolic effects that may not be restricted to mineralizing eukaryotes. The aim of our study was to determine whether microbially-mediated carbonate precipitation can also produce offsets from equilibrium for oxygen isotopes. We present here δ18O values of calcium carbonates formed by the activity of Sporosarcina pasteurii, a carbonatogenic bacterium whose ureolytic activity produces ammonia (thus increasing pH) and dissolved inorganic carbon (DIC) that precipitates as solid carbonates in the presence of Ca2+. We show that the 1000lnαCaCO3-H2O values for these bacterially-precipitated carbonates are up to 24.7‰ smaller than those expected for precipitation at isotopic equilibrium. A similar experiment run in the presence of carbonic anhydrase (an enzyme able to accelerate oxygen isotope equilibration between DIC and water) resulted in δ18O values of microbial carbonates in line with values expected at isotopic equilibrium with water. These results demonstrate for the first time that bacteria can induce calcium carbonate precipitation in strong oxygen isotope disequilibrium with water, similarly to what is observed for eukaryotes. This disequilibrium effect can be unambiguously ascribed to oxygen isotope disequilibrium between DIC and water inherited from the oxygen isotope composition of the ureolytically produced CO2, probably combined with a kinetic isotope effect during CO2 hydration/hydroxylation. The fact that both disequilibrium effects are triggered by the metabolic production of CO2, which is common in many microbially-mediated carbonation processes, leads us to propose that metabolically-induced offsets from isotopic equilibrium in microbial carbonates may be more common than previously considered. Therefore, precaution should be taken when using the oxygen isotope signature of microbial carbonates for diagenetic and paleoenvironmental reconstructions.

Variability in magnesium, carbon and oxygen isotope compositions of brachiopod shells: Implications for paleoceanographic studies

This study presents the carbon, oxygen, and magnesium isotope compositions of two modern brachiopods, Terebratalia transversa and Frieleia halli, and one fossil specimen (2.3Ma), Terebratula scillae. The aim of this study is to investigate the variability of these isotopic compositions and to evaluate the potential of brachiopods as a proxy of past seawater δ26Mg values. The two investigated brachiopod shells present the same range of δ26Mg variation (up to 2‰). This variation cannot be ascribed to changes in environmental parameters (temperature or pH). As has been previously observed, the primary layer of calcite shows the largest degree of oxygen and carbon isotope disequilibrium relative to seawater. In contrast, the δ26Mg value of the primary layer is comparable to that of the secondary calcite layer value. In both T. scillae and T. transversa, negative trends are observable between magnesium isotopic compositions and oxygen and carbon isotopic compositions. These trends can be explained by kinetic effects linked to changes in growth rate during the brachiopod life. The innermost calcite layer of T. transversa is in isotopic equilibrium for both oxygen and magnesium and could therefore be the best target for reconstructing past δ26Mg values of seawater.

A systematic for oxygen isotopic variation in meteoritic chondrules

Primitive meteorites are characteristically formed from an aggregation of sub-millimeter silicate spherules called chondrules. Chondrules are known to present large three-isotope oxygen variations, much larger than shown by any planetary body. We show here that the systematic of these oxygen isotopic variations results from open-system gas–melt exchanges during the formation of chondrules, a conclusion that has not been fully assessed up to now. We have considered Mg-rich porphyritic chondrules and have modeled the oxygen isotopic effects that would result from high-temperature interactions in the disk between precursor silicate dust and a gas enriched in SiO during the partial melting and evaporation of this dust. This formation process predicts: (i) a range of oxygen isotopic composition for bulk chondrules in agreement with that observed in Mg-rich porphyritic chondrules, and (ii) variable oxygen isotopic disequilibrium between chondrule pyroxene and olivine, which can be used as a proxy of the dust enrichment in the chondrule-forming region(s). Such enrichments are expected during shock waves that produce transient evaporation of dust concentrated in the mid-plane of the accretion disk or in the impact plumes generated during collisions between planetesimals. According to the present model, gas–melt interactions under high PSiO(gas) left strong imprints on the major petrographic, chemical and isotopic characteristics of Mg-rich porphyritic chondrules.

Control of ambient pH on growth and stable isotopes in phytoplanktonic calcifying algae

The present work examines the relationship between pH-induced changes in growth and stable isotopic composition of coccolith calcite in two coccolithophore species with a geological perspective. These species (Gephyrocapsa oceanica and Coccolithus pelagicus) with differing physiologies and vital effects possess a growth optimum corresponding to average pH of surface seawater in the geological period during their first known occurrence. The “ancestral” C. pelagicus has much wider pH tolerance in terms of growth rates than the more recently evolved G. oceanica. Diminished growth rates are explained by the challenge of proton translocation into the extracellular environment at low pH and enhanced aqueous CO2 limitation at high pH. Reducing the cell dynamics in this way leads to a lower degree of oxygen isotopic disequilibrium in G. oceanica. In contrast, the slower growing species C. pelagicus, which typically precipitates near-equilibrium calcite, does not show any modulation of oxygen isotope signals with changing pH. Overall, carbon and oxygen isotope compositions are best explained by the degree of utilization of the internal dissolved inorganic carbon (DIC) pool and the dynamics of isotopic reequilibration inside the cell. Thus, the “carbonate ion effect” may not apply to coccolithophores. This difference with foraminifera can be traced to different modes of DIC incorporation into these two distinct biomineralizing organisms. From a geological perspective, these findings have implications for refining the use of oxygen isotopes to infer more reliable sea surface temperatures (SSTs) from fossil carbonates and contribute to a better understanding of how climate-relevant parameters are recorded in the sedimentary archive.