Search

The chemical weathering of continental silicate rocks removes CO2 from the atmosphere and exerts a fundamental control on the Earth’s climate over geological timescales. Characterizing silicate weathering in the past is therefore crucial for understanding the climate system. The lithium isotopic composition (δ7Li) of carbonates is considered to be a reliable archive of past seawater δ7Li values, which are useful as a tracer of silicate weathering. However, the Li isotopic fractionation during biogenic carbonate formation is complex, and local conditions such as carbonate system parameters could impact δ7Li values in marine calcifiers. For example, δ7Li values have been shown to be dependent on either pH or DIC in two studies using large benthic foraminifera. Those results are enigmatic, since both studies used similar species of the genus Amphistegina but reported differing controls on δ7Li values.The aim of this study was to address the earlier contradictory results on the Li isotope behaviour in the hyaline species Amphistegina lessonii. We performed culture experiments under decoupled pH/DIC conditions, and analysed the δ7Li values and Li/Ca ratios in the foraminifera tests. Two different light treatments (light/dark and dark) were also implemented to investigate the potential role of the symbionts.Contrary to the two previous studies, no links between either pH or DIC and δ7Li or Li/Ca values were observed for any of the treatments in our experiments. Additionally, growth rates also did not seem to influence the Li incorporation or isotopic fractionation. However, an effect of different light treatments was observed, probably due to different physiological processes of the symbionts occurring in dark conditions. Overall, these findings appear to support the use of Li isotopes in large benthic foraminifera to reconstruct past seawater chemistry and to infer changes in chemical weathering during carbon cycle perturbations over the last several hundred million years of Earth history.

The lithium (Li) isotopic composition of carbonates is considered to be a reliable archive of past seawater Li isotopic compositions, which are useful as a tracer of silicate weathering. However, δ7Li values have been shown to be dependent on either pH or DIC in two studies using similar species of large, benthic foraminifera from the genus Amphistegina. To resolve this issue, we conducted culture experiments on Amphistegina lessonii in decoupled pH–DIC conditions, under two different light treatments, and with normal or Li-enriched seawater. The δ7Li values and Li/Ca ratios in the foraminifera tests were analysed by ion microprobe and LA-ICP-MS, respectively. No links between either the pH or DIC and δ7Li or Li/Ca values were observed for any of the treatments, and growth rates also did not seem to influence the Li incorporation or isotopic fractionation, contrary to observations from inorganic carbonate-precipitation experiments. Overall, these findings appear to support the use of Li isotopes in large benthic foraminifera to reconstruct past seawater chemistry and to infer changes in chemical weathering during carbon-cycle perturbations. Keywords: δ7Li; Li/Ca; lithium; large benthic foraminifera; culture experiments; pH; DIC; geochemical proxies

The boron isotopic ratio (δ11B) of marine biogenic carbonates is a proxy for ocean pH through the geological times, provided that δ11B measurements reach precisions better than 0.8‰ (2 SD), corresponding to 0.1 pH-unit (magnitude of the Anthropocene ocean acidification). This level of precision is however challenging to achieve for samples with a small size and low B content used in paleoceanographic reconstructions. We developed a protocol combining (i) the fast-handling and very low blank (9 ± 7 pg, 1 SD, n = 7) microsublimation technique to purify boron from the carbonate matrix and (ii) the direct injection of the samples into the MC-ICP-MS plasma with the new μ-dDIHEN device, allowing for small sample volumes and low uptake rates. We further used Jet sampler and X skimmer cones and implemented two 1013 Ω amplifiers to respectively increase the sensitivity and enhance the signal/noise ratio, enabling the precise measurement of small B signals. Our protocol, that consumes only 240 μL for one triplicate sample-standard bracketing (SSB) measurement, was validated through repeated B extractions and measurements of the carbonate reference material MVS-1 at different B concentrations. It yielded 15.93 ± 0.24‰ (2 SD, n = 10) with only 1.2 ng consumed for one triplicate SSB measurement, with individual external repeatabilities (n = 5, 2 SD) of 0.19 ± 0.14‰. We further measured δ11B of modern biogenic carbonates (arthropods, brachiopods, molluscs, red algae and reef carbonate mixes) down to 0.5–0.7 ng of B and successfully compared these δ11B values with those obtained after B extraction of the same samples through ion exchange chromatography.

The Toba volcano super-eruption on the island of Sumatra occurred about 74,000 years ago[1], close to the transition between interglacial Marine Isotope Stage (MIS) 5 and glacial MIS 4. This eruption, called Youngest Toba Tuff (YTT), is currently described as the largest cataclysmic eruption of the Quaternary. However, the impact of this super-eruption on climate is widely debated and its effects on the ocean remains poorly understood.The aim of this work is to estimate its impact on oceanic pH at a site near the eruption center. To do so, we measured δ11B values (pH proxy) on monospecific samples of planktonic foraminifera Globigerinoides ruber and Pulleniatina obliquiloculata from sediment core BAR94-25 (Andaman Sea) using a recently developed method at the Institut de Physique du Globe de Paris (IPGP)[2]. G. ruber is a species that thrives preferentially in surface waters, while P. obliquiloculata lives at the thermocline. Therefore, δ11B measurements on their shells can reconstruct pH variations in surface and thermocline waters, respectively.We selected the interval from 258 to 355 cm, corresponding to an age between 57 and 82 ka. This interval contains two clearly visible tephra layers corresponding to the YTT, at the transition from MIS 5 to MIS 4, and to a post-YTT explosive activity during MIS 4. These layers are correlated with a significant decrease in carbonate content (CaCO3). Our results indicate a complex pH response during the two concerned volcanic episodes. Thermocline seawater doesn’t show significant pH decrease during the volcanic episodes compared to the overall signal recorded throughout the studied interval. Conversely, surface seawater shows a much more important pH decrease during part of the volcanic episodes than during the all studied interval. Such decrease in pH during the transition to a glacial state is particularly surprising because an increase in pH, due to the global reduction in atmospheric CO2, is rather expected, as shown by previous foraminifera δ11B records[3].The coupling of CaCO3 and pH decrease during tephra levels suggests acidification in the Andaman Sea as a consequence of the Toba volcanic eruptive activity. The seawater surface seems much more sensitive to pH changes than the thermocline zone. However, the reduction of carbonate in the two tephra layers may also be due to dilution from ash falling into the sediment. Other analyses, such as measuring the variation of calcification intensity in planktonic foraminifera, are therefore necessary to better interpret these paleo-pH data.[1] Storey et al., 2012, PNAS, 109 (46), 18684-18688[2] Buisson et al., 2021, JAAS, 36, 2116-2131[3] Foster et al., 2008, EPSL, 271, 254-266

Biogenic carbonate minerals are widely used as archives in paleoenvironmental research, providing substantial information for past depositional and diagenetic regimes. However, nearly all biogenic carbonates undergo post-mortem diagenetic alteration to variable degrees. Diagenetic features are essentially caused by complex fluid-solid interaction including recrystallization and neomorphosis of shell architecture and related geochemical resetting. A common conception is that a given primary shell texture is replaced by a secondary fabric via micro-scale dissolution-reprecipitation reactions that may reach geochemical and/or isotopic equilibrium with the diagenetic fluid. Here we document that the process of petrographic and geochemical alteration of a biogenic carbonate archive progresses stepwise, and the re-equilibration processes can be separated in space and time. More specifically, attached and bound aqueous fluids within the shell organic matter and fluid inclusions likely play a crucial role in the early stages of alteration within a relatively rock-buffered system. Degradation of organics was observed via decreased sulfur concentration and decreased fluorescence. In this early stage of alteration, the conversion of micro-scale aragonite biominerals to metastable diagenetic calcite (meso)crystals is documented by RAMAN spectroscopy, electron backscatter diffraction (EBSD), and a decrease in strontium concentrations. Further stabilization to larger, neomorphosed calcite crystals resulted from re-equilibration with external fluids and was evidenced by EBSD, oxygen isotope data, and further reduction of strontium. Spatial chemical and isotope data were used to decipher the impact of fluid availability and transfer behavior, i.e. carbonate-buffered versus diagenetic-fluid buffered, and isotope and element exchange behavior, and analyzed in context to textural alteration features. These data suggest that during diagenesis, the evolution to more sustainable (diagenetically induced) fabrics is accompanied by individual reaction steps traced by elemental and isotopic signatures. Kinetics, and thus degree of diagenetic alteration of biominerals at a given exposure to physicochemical alteration conditions is initially strongly controlled by the micro- to nano-scale internal architecture governing the availability and transfer of aqueous fluids. Results shown here have significance for those concerned with biogenic carbonate archives and have wider implications for a mechanistic understanding of carbonate diagenesis.

Cross-sections of calcitic prismatic layers in mollusk shells, cut perpendicular to growth direction, reveal well-defined polygonal shapes of individual “grains” clearly visible by light and electron microscopy. For several kinds of shells, it was shown that the average number of edges in an individual prism approaches six during the growth process. Taking into account the rhombohedral symmetry of calcite, often presented in hexagonal axes, all this led to the long-standing opinion that calcitic prisms grow along the c-axis of calcite. In this paper, using X-ray diffraction and electron backscatter diffraction (EBSD), we unambiguously show that calcitic prisms in pearl oyster Pinctada margaritifera predominantly grow perpendicular to the c-axis. The obtained results imply that the hexagon-like habitus of growing crystallites may be not necessarily connected to calcite crystallography and, therefore, other factors should be taken into consideration. We analyze this phenomenon by comparing the organic contents in Pinctada margaritifera and Pinna nobilis shells, the later revealing regular growth of calcitic prisms along the c-axis.

International audience; Diagenesis of carbonate minerals is ubiquitous throughout the geologic record. Alteration is initiated immediately after deposition, or takes place in the endo- and exoskeletons as early as during the lifetime of a given carbonate-secreting biota, and can continue throughout the burial history of carbonate sediments and rocks. Variations in the diagenetic response of carbonate archives pose challenges for the reconstruction of past environmental conditions based on proxy data. This paper comparatively assesses alteration features of different aragonitic materials by experimentally-induced diagenesis. A multitude of factors lead to different reactivity and responses of a given aragonite archive, and provide insight to the interpretation of diagenetically altered material in the rock record. Chosen materials used in this study include relatively organic-rich samples such as coral skeletons and bivalve shells, and organic-lean abiotic carbonates such as speleothems and aragonite single crystals. Obtained datasets include distributions of elements, organics, carbon and oxygen isotope ratios, and crystallographic features. Observed variations in diagenetic responses include mineralogy of the diagenetic phases, rate and extent of mineral transformation, distribution of foreign ions in the crystal lattice (primarily Sr, Mg, and S), and the number of specific processes and products along diagenetic pathways. Alteration is shown to be primarily controlled by the initial diagenetic susceptibility of the sample (including porosimetry and structural characteristics, concentrations of organic material, and primary amounts of trace elements in the carbonate, such as Mg). Structural characteristics lead to initial internally “fluid-” or “rock-buffered” conditions, with low porosity and permeability resulting in a greater effect of internal fluids and organics. Differences in the amount of organic content and internal fluids affect transformation rates, secondary mineralogy, and isotope equilibria. Samples with relatively high porosity, high mineral transformation rates, and high primary Mg/Ca, may preferentially form secondary aragonite during fast equilibration with the diagenetic environment. Our results suggest that the degree and nature of diagenetic alteration of aragonite materials are strongly controlled by the micro- to nano-scale internal architecture governing the availability and transfer of aqueous fluids. Results of this study provide significant implications for the interpretation of diagenetic signals in carbonate archives, and have direct significance for the mechanistic understanding of carbonate diagenesis and (paleo)environmental conditions.

The boron isotopic composition (δ11B) of benthic foraminifera provides a valuable tool to reconstruct past deep-water pH. As the abundance of monospecific species might be limited in sediments, microanalytical techniques can help to overcome this problem, but such studies on benthic foraminiferal δ11B are sparse. In addition, microanalytics provide information on the distribution of δ11B at high spatial resolution to increase the knowledge of e.g. biomineralization processes. For this study, we investigated the intra- and inter-shell δ11B variability of the epibenthic species Cibicidoides wuellerstorfi, which is widely used in paleoceanography, by secondary ion mass spectrometry (SIMS) and femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICPMS). While the average δ11B values obtained from these different techniques agree remarkably well with bulk solution values to within ± 0.1 ‰, a relatively large intra-shell variability was observed. Based on multiple measurements within single shells, the SIMS and LA data suggest median variations of 4.8 ‰ and 1.3 ‰ (2σ), respectively, where the larger spread for SIMS is attributed to the smaller volume of calcite being analyzed in each run. When analytical uncertainties and volume-dependent differences in δ11B variations are taken into account for these methods, the intra-shell variability is presumably in the order of ~ 3 ‰ and ~ 0.4 ‰ (2σ) on a ~ 20 µm and 100 µm scale, respectively. In comparison, the δ11B variability between shells exhibits a total range of ~ 3 ‰ for both techniques, suggesting that several shells need to be analyzed for accurate mean δ11B values. Based on a simple resampling method, we conclude that ~ 7 shells of C. wuellerstorfi must be analyzed using LA-MC-ICPMS to obtain an accurate average value within ± 0.5 ‰ (2σ) to resolve pH variations of ~ 0.1. Based on our findings, we suggest to prefer the conventional bulk solution MC-ICPMS over the in-situ methods for e.g. paleo-pH studies. However, SIMS and LA provide powerful tools for high-resolution paleoreconstructions, or for investigating ontogenetic trends in δ11B, possibly due to vital effects during chamber formation.

Understanding the atmosphere-continent-ocean carbon cycle and its associated oceanic carbon system is one of the keystones to face the Anthropocene’s climate change. Since the 1990s the isotopic ratio of boron (δ11B) in calcitic shells of planktonic foraminifera has proven to be a powerful geochemical proxy to determine the oceanic paleo-pH and its link to atmospheric CO2 level over geological times1, whereas the ratio B/Ca as proxy of the seawater carbonate chemistry is still questionable2,3.However, the use of planktonic foraminifera in paleoclimatic reconstructions requires calibrations of the pH – δ11B relationships to correct what is known as « vital effect »4: each species controls differently its calcification process and consequently slightly modifies the seawater chemistry during biomineralization5,6. Moreover, shell size effect on δ11B has been reported for some symbiont-bearing species due to photosynthetic increase of pH7,8.Calibrations for the symbiont-barren Globigerina bulloides have been already determined9,10 but sparse data have been reported so far for the test size effect on δ11B 11.Here we measured the δ11B of three different fractions (250-315, 315-400 and >400 μm) of G. bulloides sampled along the coretop PS97-122 from the Chilean margin (54.10°S, 74.91°W), by using a new protocol developed at IPGP and dedicated to small samples which couple a microsublimation technique and a micro-direct injection device (μ-dDIHEN12). Our preliminary results show significantly higher δ11B values for the large fractions compared to the small ones, as found for symbiont-bearing planktonic species such as Globigerinoides sacculifer7 and Globigerinoides ruber8. (1) Pearson & Palmer, 2000, Nature 406, 695-699 (2) Yu et al., 2007, Paleoceanography 22, PA2202 (3) Allen et al., 2012, EPSL 351-352, 270-280 (4) Urey et al., 1951, Soc. Am. Bull. 62, 399-416 (5) Erez, 2003, Rev. in Min. and Geochem. 54 (1), 115-149 (6) de Nooijer et al., 2014, Earth-Science Reviews 135, 48-58 (7) Hönisch & Hemming, 2004, Paleoceanography 19, PA4010 (8) Henehan et al., 2013, EPSL 364, 111-122 (9) Martínez-Botíet al., 2015, Nature 518, 219-222 (10) Raitzsch et al., 2018, EPSL 487, 138-150 (11) Henehan et al., 2016, EPSL 454, 282-292 (12) Louvat et al., 2019, JAAS 8, 1553-1563

This contribution explores the petrogenetic relationships between silicate and carbonatitic rocks in the Crevier Alkaline Intrusion (CAI, Québec, Canada). The CAI is located in the Proterozoic Grenville Province and is composed of a suite of undersaturated peralkaline rocks from ijolite to nepheline syenite and carbonatites. Petrogenetic relationships between different undersaturated alkaline igneous rocks, carbonate-bearing and carbonate-free nepheline syenite and carbonatites observed in the CAI suggest that (1) carbonate-bearing and carbonate-free silicate rocks are comagmatic with carbonatite, and that (2) both silicate and carbonatitic liquids are fractionated from an ijolitic parental magma that has undergone liquid immiscibility. One of the observed facies is characterized by spectacular ocelli of carbonate-bearing nepheline syenite in a matrix of carbonatite. The younger nepheline syenite facies can be divided into two groups based on the presence or absence of magmatic carbonates. Both groups are characterized by the presence of pyrochlore-group minerals that carry the Nb–Ta mineralization. We specifically use accessory minerals such as zircon, pyrochlore and apatite to constrain the temporal and physicochemical parameters of the immiscibility process. By coupling (1) mineral textures, (2) trace elements, (3) Ti-in-zircon thermometry, and (4) oxygen isotope compositions, we have traced the crystallization of zircon before, during and after the immiscibility process. The results allowed us to constrain the minimum temperature of this process at ∼815–865°C. In addition, two magmatic populations of pyrochlore are identified through their petrographic and geochemical characteristics within the younger nepheline syenite facies. Pyrochlore from the earlier ocelli facies of carbonate-bearing nepheline syenite follow a Nb–Ta differentiation trend, whereas pyrochlore from the younger carbonate-free nepheline syenite follow a more classical Nb–Ti trend. Following the complete immiscibility between the silicate and carbonatitic liquids, the fractionation between Nb and Ta stopped while a new generation of Nb-rich pyrochlore grew, displaying a more classical Nb–Ti fractionation trend and a higher Nb/Ta ratio in the nepheline syenite.

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio analyses by both solution-nebulisation MC-ICP-MS and laser ablation-ICP-MS, as well as of radioactive isotope geochronology by LA-ICP-MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis, however it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro-XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.

International audience; The sulfur isotope budget of Martian regolith breccia (NWA 7533) has been addressed from conventional fluorination bulk rock analyses and ion microprobe in situ analyses. The bulk rock analyses yield 865 ± 50 ppm S in agreement with LA‐ICP‐MS analyses. These new data support previous estimates of 80% S loss resulting from terrestrial weathering of NWA 7533 pyrite. Pyrite is by far the major S host. Apatite and Fe oxyhydroxides are negligible S carriers, as are the few tiny igneous pyrrhotite–pentlandite sulfide grains included in lithic clasts so far identified. A small nonzero Δ33S (−0.029 ± 0.010‰) signal is clearly resolved at the 2σ level in the bulk rock analyses, coupled with negative CDT‐normalized δ34S (−2.54 ± 0.10‰), and near‐zero Δ36S (0.002 ± 0.09‰). In situ analyses also yield negative Δ33S values (−0.05 to −0.30‰) with only a few positive Δ33S up to +0.38‰. The slight discrepancy compared to the bulk rock results is attributed to a possible sampling bias. The occurrence of mass‐independent fractionation (MIF) supports a model of NWA 7533 pyrite formation from surface sulfur that experienced photochemical reaction(s). The driving force that recycled crustal S in NWA 7533 lithologies—magmatic intrusions or impact‐induced heat—is presently unclear. However, in situ analyses also gave negative δ34S values (+1 to −5.8‰). Such negative values in the hydrothermal setting of NWA 7533 are reflective of hydrothermal sulfides precipitated from H2S/HS‐ aqueous fluid produced via open‐system thermochemical reduction of sulfates at high temperatures (>300 °C).

Fossil brachiopod shells are often used as valuable archives to reconstruct paleoenvironmental conditions in deep time. However, biomineralization processes can impact their fidelity as geochemical proxies. Brachiopod shells comprise an outer primary layer, a secondary fibrous layer and sometimes, a tertiary columnar layer. Therefore, it is essential to assess the potential effects of the biomineralization processes in each of the different shell microstructures of modern brachiopods. This study analyses the oxygen isotopic composition together with Li/Ca, Na/Ca Mg/Ca and Sr/Ca data at high spatial (20-50 μm) resolution in seven modern brachiopod species, focusing on differences between the primary, secondary and tertiary layers. In all studied species, δ18O values of the outer primary layer are consistently out of equilibrium with seawater. Also, this shell layer is enriched in Li, Na, Mg and Sr. Contrary to the primary layer, the innermost secondary layer is near or at oxygen isotopic and elemental equilibrium with ambient seawater. The columnar tertiary shell layer, if present, has the least variable and the heaviest oxygen isotopic composition, within the range of equilibrium values with seawater. This tertiary layer, however, is depleted in minor and trace elements relative to the other shell layers. Thus, the tertiary layer is more suitable for oxygen isotopic studies, whereas the innermost secondary layer of the most mature parts of the shell is the best target in two-layered shells. While we do not observe any clear interspecific relationships between Mg/Ca and Sr/Ca ratios, on one hand, and environmental parameters such as temperature, salinity and pH, on the other hand, there is a positive interspecific relationship between Na/Ca and salinity and a negative interspecific relationship between Li/Ca and temperature, suggesting their potential use as proxies of physicochemical parameters of seawater.

International audience; The mu-dDIHEN allows direct nebulization of small samples into the plasma at a flow rate down to 5 mu L min(-1). It is composed of a demountable direct injection high efficiency nebulizer (d-DIHEN), a flow injection analysis (FIA) valve and a gas displacement pump (GDP) connected to a mu-mass-flow meter delivering very stable liquid flow. The system was successfully tested with sample loops of 10 and 50 mu L and for liquid flow rates between 5 and 50 mu L min(-1) on two different inductively coupled plasma mass spectrometry (ICP-MS) instruments, a sector-field-ICP-MS (SF-ICP-MS) and a multi-collector-ICP-MS (MC-ICP-MS), and for three different applications: boron isotopic ratio measurement of geological samples, multi-element analyses of natural water samples and gold nanoparticle characterization by single particle ICPMS (spICP-MS). Signal sensitivity was increasing with the liquid uptake rate of the mu-dDIHEN (and the GDP gas flow rate), but stopped increasing above 30 mu L min(-1), due to bad spray quality and poor ionization under extra-wet conditions. We successfully measured boron isotopic ratios (delta B-11) for reference material solutions with B concentrations between 10 and 200 mu g L-1; the reproducibility of the measurements depending on both the B concentration of the sample and the uptake rate: B-10 signals below 20-30 mV (with 10(11) ohms amplifiers) gave 2SD reproducibility >= 0.5 parts per thousand (n = 5). The best measurement conditions were not necessarily with the lowest uptake rate but rather at 25 mu L min(-1), allowing for higher signals. We also tested transient versus continuous measurement modes for a series of natural samples (with 10 and 50 mu L sample loops). The two modes gave fully comparable results but the transient mode allows triplicate delta B-11 measurements and is recommended for very small samples (

The fluid history of “diamond” quartz crystals from Caravia-Berbes Fluorite district is intimately related with episodes of maturation and migration of hydrocarbons within the Asturian basin, probably linked to the structural activation of a Mesozoic rift system. These “diamond” quartz record the migration of hydrothermal silica-rich brines and associated hydrocarbons that recorded a temperature increase (outlined by fluid inclusion studies) from ∼90 to ∼140 °C. This gradient is also recorded by a change in the organic matter species trapped in quartz, from bitumen located in the inner quartz growth zones to liquid hydrocarbons trapped within the outer quartz overgrowths. Secondary ion mass spectrometer (SIMS) oxygen isotope microanalyses allowed to differentiate two δ18OH2O values corresponding to the oil-dominated zone (core) and the water-dominated zone (outer growth zone). The heavier δ18OH2O values in the water-dominated zone do not only record a higher temperature of formation, but also an increase in the δ18OH2O of the parental fluid. Isotopic compositions of diamond quartz suggest a heterogeneous source of surficial fluids and formation-waters expelled from claystones. Within the basin history, the diamond quartz precipitation took place during early Jurassic to Eocene subsidence periods. Pressure Temperature and composition (PTX) and δ18OH2O characteristics point out a probable relationship with Albian diagenetic events reported in Cantabrian and north Pyrenean basins.

The 2.1 billion-year-old sedimentary strata contain exquisitely preserved fossils that provide an ecologic snapshot of the biota inhabiting an oxygenated shallow-marine environment. Most striking are the pyritized string-shaped structures, which suggest that the producer have been a multicellular or syncytial organism able to migrate laterally and vertically to reach for food resources. A modern analogue is the aggregation of amoeboid cells into a migratory slug phase in modern cellular slime molds during time of food starvation. While it remains uncertain whether the amoeboidlike organisms represent a failed experiment or a prelude to subsequent evolutionary innovations, they add to the growing record of comparatively complex life forms that existed more than a billion years before animals emerged in the late Neoproterozoic.Evidence for macroscopic life in the Paleoproterozoic Era comes from 1.8 billion-year-old (Ga) compression fossils [Han TM, Runnegar B (1992) Science 257:232–235; Knoll et al. (2006) Philos Trans R Soc Lond B 361:1023–1038], Stirling biota [Bengtson S et al. (2007) Paleobiology 33:351–381], and large colonial organisms exhibiting signs of coordinated growth from the 2.1-Ga Francevillian series, Gabon. Here we report on pyritized string-shaped structures from the Francevillian Basin. Combined microscopic, microtomographic, geochemical, and sedimentologic analyses provide evidence for biogenicity, and syngenicity and suggest that the structures underwent fossilization during early diagenesis close to the sediment–water interface. The string-shaped structures are up to 6 mm across and extend up to 170 mm through the strata. Morphological and 3D tomographic reconstructions suggest that the producer may have been a multicellular or syncytial organism able to migrate laterally and vertically to reach food resources. A possible modern analog is the aggregation of amoeboid cells into a migratory slug phase in cellular slime molds at times of starvation. This unique ecologic window established in an oxygenated, shallow-marine environment represents an exceptional record of the biosphere following the crucial changes that occurred in the atmosphere and ocean in the aftermath of the great oxidation event (GOE).

RATIONALE In situ secondary ion mass spectrometry (SIMS) analysis requires the use of standards to unravel the instrumental mass fractionation (IMF) induced by the analytical procedures. Part of this IMF might be caused by the nature of the sample and the differences in composition and structure between the sample and the standards. This "matrix effect" has been tentatively corrected for by using standards with chemical compositions equivalent to the samples, or by the empirical use of chemical parameters. However, these corrections can only be applied to a narrow compositional range and fail to take proper account of the matrix effect when a wider chemical field is tested. METHODS We synthesized a series of glasses whose compositions span a very large part of the NCMAS (Na2 O-CaO-MgO-Al2 O3 -SiO2 ) system. Si and Ca isotopic analyses were performed on two ion microprobes (Cameca IMS-1270 and IMS-1280). RESULTS The matrix effect observed may reach 20‰ between extreme compositions and cannot be accounted for by the previously used "chemical" parameters (e.g. SiO2 , SiO2 /(SiO2 + Al2 O3 )) nor by the NBO/T parameter. It therefore appears necessary to consider not only the structure of the glasses, but also the nature of the different atoms. Consequently, we assessed the use of another concept, the optical basicity, based on the electronegativities of the constitutive elements of glass. CONCLUSIONS We show that this parameter significantly improves the efficiency of the matrix-effect correction and that it can be applied across the entire NCMAS compositional range studied here. Furthermore, the use of optical basicity reduces the number of glass standards required for a reliable isotopic study, and it can also be used to probe the structure of the glass. Copyright © 2016 John Wiley & Sons, Ltd.

We present ion probe measurements of Li/Ca, Na/Ca and Mg/Ca ratios of three scleractinian corals (Lophelia pertusa, Desmophyllum cristagalli, Porites lutea). These ratios are systematically enriched in Rapid Accretion Deposits (RADs) compared to surrounding fibres, or Thickening Deposits (TDs), and present huge variations that cannot be ascribed to any environmental parameter change. Moreover, these elemental ratios are positively correlated in the three coral species. We explore different mechanisms to explain these observations: (1) mixing between different carrier phases, (2) influence of specific ion pumps, (3) precipitation rate effects, (4) Rayleigh fractionation, and (5) pH change in the calcifying fluid. Of these possibilities, the most likely proposal seems to be kinetic effects that have influence on the number of defects (i.e., modification of the crystallographic structure), which are linked to the precipitation rate of the skeleton, and the partition coefficients are the cause of the positive correlation between Li, Na, and Mg in the coral skeleton. Temperature has an indirect influence on the skeletal concentration of these elements through its effect on the skeletal growth rate.

The powder infrared spectra of a sulfate-bearing calcitic coral sample are recorded at room temperature in attenuated total reflectance (ATR) geometry and at low temperature in transmission geometry. The comparison of ATR spectra recorded with diamond or Ge crystal confirms that the width and the shape of the prominent absorption bands, related to CO 3 groups, are dominantly affected by macroscopic electrostatic interactions. In contrast, the temperature-dependence of the position and width of weak and narrow absorption bands, related to CO 3 or SO 4 groups, can be interpreted in terms of thermal expansion, anharmonic coupling, and local strain fluctuations. The three SO 4 stretching bands display a contrasted thermal behavior, the frequency of one of them increasing with temperature. Based on first-principles calculation, this unusual temperature dependence is traced back to the anisotropy of calcite thermal expansion. These results sustain the previously proposed atomic-scale model of sulfate in calcite and attest to a dominantly structural nature of sulfate in the investigated sample. Accordingly, structurally substituted sulfur in deep-sea calcitic bamboo coral could be used as proxy of seawater sulfate.

We report in situ and bulk S-isotope analyses of the 3.2 Ga old barite deposit of the Sargur Group, Dharwar Craton, India. Compared with the two other coeval barite deposits in Western Australia (Pilbara Craton, Warrawoona and Sulfur Springs Group) and South Africa (Kaapvaal Craton, Onverwacht and Fig Tree Group), the rocks of the Sargur Group have experienced pervasive ductile deformation and equilibrated under high-grade metamorphic conditions, which could have caused partial S-isotope re-equilibration. However, in situ techniques revealed high spatial heterogeneities in δ 34 S of up to ∼18‰ in barite-bearing pyrites, as well as similar Δ 33 S anomalies compared to the associated sulfate indicating bacterial sulfate reduction isotope effects and a minor impact of the pervasive ductile deformation and metamorphism on the primary/diagenetic signatures. Our data in associated silicate rocks define consistent trends in Δ 33 S/δ 34 S and Δ 36 S/Δ 33 S reflecting metamorphic reworking of primary photolytic signatures with sulfide deriving from thermal reduction of the barite sulfate at >400 °C. Our results match the previous data obtained on other Early Archean barite deposits. This strongly suggests that similar sulfur sources were at play over the three continents during the production and preservation of atmospheric sulfate and elemental sulfur aerosols. This also confirms that the different Early Archean barite deposits known on Earth formed during periods of intense subaerial volcanism and record volcanic photolytic signatures different from those common in the Archean.

International audience; The boron isotopic and chemical content of carbonates (expressed as δ11B and B/Ca ratios) have been proposed as proxies for seawater carbonate system parameters. Thermodynamic and kinetic effects on δ11B and B partitioning are not yet fully constrained, underscoring the importance of exploring possible effects of growth rate on boron incorporation in synthetic calcium carbonate minerals, which is the focus of this study. Secondary Ion Mass Spectrometry (SIMS) measurements of B/Ca and δ11B were performed on single crystal of calcite synthesized by diffusion of CO2 under controlled conditions from a solution of NH4Cl–CaCl2 doped with boron. Growth rates of calcite (V, nm/s) within crystals grown isothermally at 24.6 °C were monitored by sequentially spiking calcite-precipitating fluids with rare earth element (REE) dopants. The REE were analyzed with SIMS at spots that match those locations where B/Ca and δ11B ratios were measured. Values for the boron Nernst partition coefficient, defined as DB = B(calcite)/B(fluid), increase from 0.5 (pHNBS = 8.15) to 0.9 (pH = 8.00) with values of V increasing from 0.04 to 0.13 nm/s. For δ11B behavior, it was not possible to draw conclusive results due to the analytical error (2.2‰; 2σ). pH effects on DB during calcite precipitation, associated with an increase in pH from 8.00 to 8.15, appear to be masked by the competing effects of changing V. We conclude that over the range of growth rates and other conditions investigated in this study, growth rate effects on B partitioning need to be accounted for when using B/Ca ratios in biogenic calcite as a proxy for seawater carbonate system parameters.

International audience

International audience; The occurrence of Early Archean barite deposits is intriguing since this type of sediment requires high availability of dissolved sulfate (SO42-), the oxidized form of sulfur, although most authors argued that the Archean eon was dominated by reducing conditions, with low oceanic sulfate concentration (56Fe values varying between -2.04‰ in Fe sulfide-dominated barite beds, to +2.14‰ in Fe oxide-bearing cherts. δ34S values of sulfides vary between -10.84 and +3.56‰, with Δ33S in a range comprised between -0.35 and +2.55‰, thus supporting an O2-depleted atmosphere (-5 PAL). Iron isotope variations together with major element correlations show that, although the sediments experienced a pervasive stage of hydrothermal alteration, the rocks preserved a primary/authigenic signature predating subsequent hydrothermal stage. Highly positive δ56Fe values recorded in primary Fe-oxides from ferruginous cherts support partial Fe oxidation in a reducing oceanic environment (O2 < 10-4 μM), but are incompatible with a model of complete oxidation at the redox boundary of a stratified water column. Iron oxide precipitation under low O2 levels was likely mediated by anoxygenic photosynthesis, and/or abiotic photo-oxidation processes. Our results are consistent with global anoxic conditions in the 3.2 Ga-old sediments, implying that the barite deposits were most likely sourced by atmospheric photolysis of S gases produced by large subaerial volcanic events, and possibly SO42- produced by magmatic SO2 disproportionation in hydrothermal systems.

In situ secondary ion mass spectrometry (SIMS) analysis requires the use of standards to unravel the instrumental mass fractionation (IMF) induced by the analytical procedures. Part of this IMF might be caused by the nature of the sample and the differences in composition and structure between the sample and the standards. This "matrix effect" has been tentatively corrected for by using standards with chemical compositions equivalent to the samples, or by the empirical use of chemical parameters. However, these corrections can only be applied to a narrow compositional range and fail to take proper account of the matrix effect when a wider chemical field is tested.We synthesized a series of glasses whose compositions span a very large part of the NCMAS (NaThe matrix effect observed may reach 20‰ between extreme compositions and cannot be accounted for by the previously used "chemical" parameters (e.g. SiOWe show that this parameter significantly improves the efficiency of the matrix-effect correction and that it can be applied across the entire NCMAS compositional range studied here. Furthermore, the use of optical basicity reduces the number of glass standards required for a reliable isotopic study, and it can also be used to probe the structure of the glass. Copyright © 2016 John WileySons, Ltd.

International audience; Sulfur isotopic anomalies (∆33S and ∆36S) have been used to trace the redox evolution of the Precambrian atmosphere and to document the photochemistry and transport properties of the modern atmosphere. Recently, it was shown that modern sulfate aerosols formed in an oxidizing atmosphere can display important isotopic anomalies, thus questioning the significance of Archean sulfate deposits. Here, we performed in situ 4S-isotope measurements of 3.2- and 3.5-billion-year (Ga)-old sulfates. This in situ approach allows us to investigate the diversity of Archean sulfate texture and mineralogy with unprecedented resolution and from then on to deconvolute the ocean and atmosphere Archean sulfur cycle. A striking feature of our data is a bimodal distribution of δ34S values at ∼+5‰ and +9‰, which is matched by modern sulfate aerosols. The peak at +5‰ represents barite of different ages and host-rock lithology showing a wide range of ∆33S between −1.77‰ and +0.24‰. These barites are interpreted as primary volcanic emissions formed by SO2 photochemical processes with variable contribution of carbonyl sulfide (OCS) shielding in an evolving volcanic plume. The δ34S peak at +9‰ is associated with non–33S-anomalous barites displaying negative ∆36S values, which are best interpreted as volcanic sulfate aerosols formed from OCS photolysis. Our findings confirm the occurrence of a volcanic photochemical pathway specific to the early reduced atmosphere but identify variability within the Archean sulfate isotope record that suggests persistence throughout Earth history of photochemical reactions characteristic of the present-day stratosphere.

Marine and freshwater ooids were historically thought to form by purely physicochemical processes in turbulent environments. Recently, organomineralization has been identified as a key process for the initiation of freshwater ooid cortex formation, but the exact biochemical mechanism(s) involved and subsequent contribution to the development of the growing cortex remain unknown. Here, we show that photosynthetic microbes not only enhance early carbonate precipitation around the ooid nucleus but also control the formation of the entire cortex in freshwater ooids from Lake Geneva, Switzerland. Microbial extracellular polymeric substances are first permineralized as amorphous magnesium silicates ( am Mg-Si) before being calcified. An ∼5‰–6‰ depletion of 13 C in ooid cortices compared to both bulk values and carbonate nuclei supports this photosynthetic microbial mechanism and argues against contributions from sulfate-reducing bacteria or methanogens. These data have significant implications for paleoenvironmental studies since photosynthetic microbes now provide an alternative to turbulent hydrodynamic conditions in the formation of freshwater ooids.

The Namalulu tsavorite (vanadian grossular up to 0.80 wt.% V 2 O 3 ) deposit in northeastern Tanzania occurs in metasomatized graphitic gneiss overlain by a dolomitic marble unit. These rocks belong to the Neoproterozoic metamorphic Mozambique Belt. The graphitic gneiss is composed of quartz, V-bearing kyanite (up to 0.4 wt.% V 2 O 3 ), V-bearing muscovite (up to 1.0 wt.% V 2 O 3 ), V-bearing rutile (up to 1.9 wt.% V 2 O 3 ), and graphite. This rock is affected by calcic metasomatism precipitating calcite and mobilizing the elements for tsavorite crystallization in quartz-calcite veins. The dolomitic marble unit hosts an anhydrite-gypsum-dolomite lens (lens I) and a calcite-scapolite-diopside-sulfides-graphite lens (lens II). This last unit is characterized by the presence of F-bearing minerals (tremolite, phlogopite, tainiolite, titanite), with up to 9.4 wt.% F for tainiolite, and Ba-bearing minerals (feldspar, phlogopite), with up to 7.5 wt.% BaO for feldspar. Lithium (up to 2.0 wt.% Li 2 O) and boron (up to 110 ppm) are also present in tainiolite, as well as in F-bearing tremolite. This is the first description of metamorphic tainiolite. The protoliths of the Namalulu rocks correspond to organic-rich black shales, pure and magnesian carbonates, and evaporites. They were presumably deposited in a marine coastal sabkha located at the eastern margin of the Congo-Kalahari cratons bounded by the Mozambique Ocean during early Neoproterozoic. Tsavorite formed in the Ca-metasomatized gneiss during amphibolite facies retrograde metamorphism at 5.6–6.7 kbar and 630 ± 30 °C.

– We report Si concentrations in the metal phases of iron meteorites. Analyses were performed by secondary ion mass spectrometry using a CAMECA 1270 ion probe. The Si concentrations are low (0.09–0.46 μg g−1), with no apparent difference in concentration between magmatic and nonmagmatic iron meteorites. Coexisting kamacite and Ni-rich metal phases have similar Si contents. Thermodynamic calculations show that Fe,Ni-metal in equilibrium with silicate melts at temperatures where metal crystallizes should contain approximately 100 times more Si than found in iron meteorites in this work. The missing Si may either occur as tiny silicate inclusions in metal or it may have diffused as Si-metal into surrounding silicates at low temperatures. In both cases, extensive low-temperature diffusion of Si in metal is required. It is therefore concluded that low Si in iron meteorites is a result of subsolidus reactions during slow cooling.

An analytical procedure is described for in situ measurements of iron isotope compositions of different sulfides and oxides with a spatial resolution of 15–20 μm using a Cameca IMS 1270 ion microprobe (SIMS). The 54 Fe and 56 Fe isotopes were measured on two Faraday cups. The isobaric 54 Cr interference on 54 Fe was corrected by measuring 53 Cr and 52 Cr intensities. For magnetite crystals, which contain some chromium, this correction is consistent at 0.11 ± 0.06‰. A SIMS instrumental mass fractionation was observed between oxides and sulfides, and this instrumental mass fractionation decreases with the oxidation state. The iron isotope composition of various reference materials, including hematite, pyrite, siderite and magnetite, were intercalibrated with those obtained by MC-ICP-MS. The SIMS δ 56 Fe reproducibility obtained on these various reference materials is typically 0.2–0.3‰ at 2σ; the MC-ICP-MS δ 56 Fe reproducibility is about 0.1‰ (2σ). This analytical procedure was applied to a Precambrian magnetite grain from the Gunflint Iron formation (1.88 Ga, Canada). This magnetite shows a large range of iron isotope compositions of about 4‰ between the rim and the core. We have also measured the oxygen isotope composition of this magnetite with the new IMS 1280 HR2 (CRPG–CNRS, Nancy), and observed no relation between δ 56 Fe and δ 18 O. The magnetite rim exhibits some extreme δ 56 Fe values of + 5.2‰ never reported before. This result emphasizes the crucial interest of in situ-measurements for studying the processes of Fe isotopic fractionation in depositional environments.

Elemental ratios and isotopic compositions of scleractinian corals are often used as proxies for the pH and the temperature of seawater from which they calcified. Nevertheless, these ratios recorded in the coral skeleton are offset from the ratios expected for equilibrium, due to vital effects. Ion microprobe δ11B measurements were performed in a modern tropical coral, Porites lutea, and in a Mediterranean coral, Cladocora caespitosa, grown under two different pCO2. We show that the δ11B variations measured at micrometer scale are principally controlled by biology via modification of the pH near the calcification sites. The range of calculated pH allows to reproduce the range of δ18O measured in corals via a kinetic model of oxygen isotopic equilibrium between water and DIC. Thus we show that temperature does not seem to be the primary control of the δ18O variations in coral, though the constants of reaction and the isotopic fractionation values obviously depend on temperature.

Dissolved boron in modern seawater occurs in the form of two species, trigonal boric acid B(OH)3 and tetrahedral borate ion B ( OH ) 4 − . One of the key assumption in the use of boron isotopic compositions of carbonates as pH proxy is that only borate ions, B ( OH ) 4 − , are incorporated into the carbonate. Here, we investigate the speciation of boron in deep-sea coral microstructures (Lophelia pertusa specimen) by using high field magic angle spinning nuclear magnetic resonance (11B MAS NMR) and electron energy-loss spectroscopy (EELS). We observe both boron coordination species, but in different proportions depending on the coral microstructure, i.e. centres of calcification versus fibres. These results suggest that careful sampling is necessary before performing boron isotopic measurements in deep-sea corals. By combining the proportions of B(OH)3 and B ( OH ) 4 − determined by NMR and our previous ion microprobe boron isotope measurements, we propose a new equation for the relation between seawater pH and boron isotopic composition in deep-sea corals.

The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ11B has some limitations such as the knowledge of the fractionation factor (α4-3) between boric acid and the borate ion and the amplitude of “vital effects” on this proxy that are not well constrained. Using secondary ion mass spectrometry (SIMS) we have examined the internal variability of the boron isotope ratio in the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24 ± 0.1 °C) in seawater with pH ranging between 7.90 and 8.45. Intra-shell boron isotopes showed large variability with an upper limit value of ≈30‰. Our results suggest that the fractionation factor α4-3 of 0.97352 ( Klochko et al., 2006 ) is in better agreement with our experiments and with direct pH measurements in seawater vacuoles associated with the biomineralization process in these foraminifera. Despite the large variability of the skeletal pH values in each cultured specimen, it is possible to link the lowest calculated pH values to the experimental culture pH values while the upper pH limit is slightly below 9. This variability can be interpreted as follows: foraminifera variably increase the pH at the biomineralization site to about 9. This increase above ambient seawater pH leads to a range in δ11B (Δ11B) for each seawater pH. This Δ11B is linearly correlated with the culture seawater pH with a slope of −13.1 per pH unit, and is independent of the fractionation factor α4-3, or the δ11Bsw through time. It may also be independent of the pKB (the dissociation constant of boric acid) value. Therefore, Δ11B in foraminifera can potentially reconstruct paleo-pH of seawater.

We present ion microprobe measurements of oxygen isotopic compositions in the deep-sea coral Lophelia pertusa . Compared to bulk skeletal aragonite fibres, the EMZ (early mineralization zone), near the inside of the calyx, was systematically depleted in 18 O. Rayleigh fractionation from a semi-closed fluid reservoir does not explain this and other geochemical differences. Furthermore, pH values estimated from skeletal δ 11 B data are inconsistent with the idea that EMZ (or centres of calcification) 18 O depletion reflects a more alkaline calcification environment. Our data, combined with microstructural and geochemical observations, indicate that the aragonitic fibres and EMZ are formed by a compartmentalized mineralization calicoblastic ectoderm, which exerts strong biological control on the composition of the skeleton. Hence, we propose a new model whereby amorphous calcium carbonates (ACC) are precursors to the EMZ, whereas the fibre precipitation is probably governed by kinetic processes.

The formation of diamond through metasomatic events, from volatiles-enriched fluids/melts brought into pre-existing mantle rocks, has been suggested from a series of independent studies. However, the link between these hypothetical volatile-rich fluids and deep-seated mineral inclusions (mostly silicate and sulphides) entrapped in diamonds remains unclear, yet the relationship between these two species may provide the key to our understanding of diamond crystallization. In order to address the relationship between the origin and formation of diamonds and their mineral inclusions, we carried out the first coupled stable isotopic study ( δ 13 C, δ 15 N and multiple S-isotopes as δ 34 S, δ 33 S, Δ 33 S) of diamonds containing sulphide inclusions, using samples from the Jwaneng kimberlite as our model system. Sulphides extracted from the present collection of 55 diamonds belong to either eclogitic (E-type, 52 diamonds) or peridotitic (P-type, 3 diamonds) paragenetic suites, as attested by their Cr and Ni content (Cr 0.18 wt.% and Ni > 14 wt.% for P-types). Sulphur isotopic compositions have been measured in-situ by multicollector secondary ion mass spectrometry and reveal that peridotitic sulphide inclusions in diamonds ( n = 4) lie on the terrestrial fractionation line whereas Mass Independent sulphur isotope Fractionations (MIF) are preserved inside eclogitic sulphides inclusions (− 0.5‰ 33 S n = 33). Such large MIF values, extended here to the negative values recorded in Archean sediments, are thought to be produced through photochemical reactions in the Archean atmosphere, which implies that sulphides inclusions contain an Archean sedimentary sulphur component that was transferred to the Earth's mantle. In contrast to this isotopic dichotomy between E-type and P-type sulphides, the geochemical characteristics of their host diamonds ( δ 13 C, δ 15 N, N-content, N-speciation) are largely homogeneous throughout the population, and differ from silicate-bearing diamonds previously studied in the same locality. Sulphide-bearing diamonds appear to define a distinct population, which might reflect a different crystallization process characterized by carbon and nitrogen isotopic compositions falling within the range of unfractionated mantle values. The lack of a distinct isotopic signature of recycled sedimentary nitrogen and carbon in sulphide-bearing diamonds leads us to infer that sulphide-bearing Jwaneng diamonds were not derived from the same chemical reservoir as their inclusions. One possible formation mechanism that is compatible with our observations is diamond crystallization from a mantle-derived carbon-bearing fluid associated with pre-existing sedimentary sulphide minerals. This model has important implications for the interpretation of diamond ages obtained from sulphide inclusions using Re–Os systematics. Here we suggest that the incorporation of a significant amount of mantle-related sulphur during a diamond growth event into the original sulphide could lead to a re-equilibration of the Re–Os isotope composition in any inclusion, and accordingly, account for some scatter on Re–Os isochrons.

Using secondary ion mass spectrometry (SIMS) we looked at the natural variability in the oxygen isotope ratio of the shallow water, symbionts-bearing foraminiferan Amphistegina lobifera . Live foraminifera were collected in February 2005 in the Gulf of Eilat, Israel. Vertical section exposing the knob area of this species represents the growth history of this species from August 2004 to February 2005. SIMS profile at a resolution of ∼15 μm (representing about 2 weeks considering the size of the knob area and the life span of ≈6 months of this foraminifera species) yielded δ 18 O changes of ∼1.5‰ that are compatible with the known temperature changes for the Gulf of Eilat for this period (21–27 °C). Natural variability between primary and secondary calcite at the knob area were obtained on horizontal section of the upper knob area. This section is semi-tangential to the growth lines and exposes relatively wide belts of the primary calcite which could be analysed using the SIMS (beam size of 10 × 20 μm). The primary calcite δ 18 O value is on average more than 3‰ lower than the secondary calcite that represents the bulk of the skeleton (more than 95% by weight). A vertical profile at the knob was obtained by rastering an area of 50 × 50 μm at vertical steps of roughly 1 μm. The profile revealed a narrow zone of lower δ 18 O compared to the higher values above and below it. The difference between the lowest δ 18 O and the highest one was also close to 2‰. The δ 18 O in the margin – keel area of A. lobifera is also lower compared to the bulk secondary calcite. Specimens that were cultured in the laboratory at a constant temperature and inorganic carbon but at different pH have increased their CaCO 3 weight by roughly a factor of 8. Single specimen from each pH (ranging between 7.90 and 8.45) were investigated with the SIMS at the knob area. While there is some variability within each specimen (perhaps related to the primary calcite), the general trend was a decrease in δ 18 O with increasing pH (or CO 3 2− concentration), in agreement with previous studies on planktonic foraminifera. Some other specimens grown at different temperatures (between 21 and 33 °C) were also measured with the SIMS at the knob area. For each temperature, we observed also some variability, nevertheless the trend of −0.2‰/°C in δ 18 O is observed.

This study presents the carbon, oxygen, and magnesium isotope compositions of two modern brachiopods, Terebratalia transversa and Frieleia halli, and one fossil specimen (2.3 Ma), 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 delta Mg-26 values. The two investigated brachiopod shells present the same range of delta(26)Mgvariation (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 delta Mg-26 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 delta Mg-26 values of seawater. (C) 2016 Elsevier B.V. All rights reserved.

The analytical capabilities of the ims 1270 ion microprobe (SIMS) in determining O and C isotope compositions in biogenic carbonate samples have been tested. Results indicated that, with a spot size of ≊ 30 μm, the average reproducibility at the 1s level was 0.3‰ for oxygen isotopes and 0.6‰ for carbon isotopes. Nevertheless, this reproducibility can reach 0.2‰ for oxygen isotope determinations during some sessions. These reproducibilities allowed us to perform analyses on biogenic carbonate samples for environmental studies. In this paper, examples of oxygen and carbon isotope measurements are presented for a modern coral and the Holocene scleractinian coral, Porites lutea. Les performances analytiques de la sonde ionique ims 1270 (SIMS) pour la determination des compositions isotopiques de O et C dans des echantillons de carbonates biogeniques ont ete testees. Les resultats indiquent que, avec une taille de faisceau d'environ 30 μm, la reproductibilite moyenne (1s) etait 0.3‰ pour les isotopes d'oxygene et 0.6‰ pour les isotopes du carbone. Neanmoins, cette reproductibilite peut atteindre 0.2‰ pour les analyses des isotopes de l'oxygene lors de certaines sessions. Ces reproductibilites nous permettent d'analyser des echantillons de carbonates biogeniques dans le cadre d'etudes environnementales. Des exemples de mesures isotopiques d'oxygene et de carbone sont presentes dans cet article pour un corail scleractiniaire moderne et de l'Holocene, Porites lutea.

Carbonaceous matter occurring in chert deposits of the 3.4–3.2 Ga old Barberton Greenstone Belt (BGB), South Africa, has experienced low grade regional metamorphism and variable degrees of local hydrothermal alteration. Here a detailed study is presented of in situ analysis of carbonaceous particles by LRS (laser Raman spectroscopy) and SIMS (secondary ion mass spectrometry), reporting degree of structural disorder, carbon isotope ratio and nitrogen-to-carbon ratio. This combination of in situ analytical tools is used to interpret the δ 13 C values of only the best preserved carbonaceous remains, enabling the rejection of non-indigenous (unmetamorphosed) material as well as the exclusion of strongly hydrothermally altered carbonaceous particles. Raman spectroscopy confirmed that all carbonaceous cherts studied here have experienced a regional sub- to lower-greenschist facies metamorphic event. Although this identifies these organics as indigenous to the cherts, it is inferred from petrographic observations that hydrothermal alteration has caused small scale migration and re-deposition of organics. This suggest that morphological interpretation of these carbonaceous particles, and in general of putative microfossils or microlaminae in hydrothermally altered early Archean cherts, should be made with caution. A chert in the Hooggenoeg Formation, which is older than and has been hydrothermally altered by a volcanic event 3445 Ma ago, contains strongly altered carbonaceous particles with a uniform N/C-ratio of 0.001 and a range of δ 13 C that is shifted from its original value. Cherts of the Kromberg Formation post-date this volcanic event, and contain carbonaceous particles with a N/C-ratio between 0.002 and 0.006. Both the Buck Reef Chert and the Footbridge Chert of the Kromberg Formation have retained fairly well-preserved δ 13 C values, with ranges from −34‰ to −24‰ and −40‰ to −32 ‰, respectively. Abiologic reactions associated with hydrothermal serpentinization of ultramafic crust (such as Fischer–Tropsch synthesis) were an unlikely source for carbonaceous material in these cherts. The carbonaceous matter in these cherts has all the characteristics of metamorphosed biologic material.

We have determined the δ18O and δ13C values of azooxanthellate (Lophelia pertusa) and zooxanthellate (Porites lutea) corals at a micrometer scale using an ion microprobe (SIMS—secondary ion mass spectrometry). In P. lutea, centers of calcification are small (10 to 15 μm) and difficult to locate during measurements. In L. pertusa, they are large (50 μm) and arranged in lines of centers of calcification. Our results show that centers of calcification in L. pertusa have a restricted range of variation in δ18O [-2.8±0.3‰ (PDB)], and a larger range in δ13C [14.3 to 10.9‰ (PDB)]. Surrounding skeletal fibers exhibit large isotopic variation both for C and O (up to 12‰), and δ13C and δ18O are positively correlated. The C and O isotopic compositions of the center of calcification deviate from this linear trend at the lightest δ18O values of the surrounding fibers. Ion microprobe results on P. lutea demonstrate also a large range of variation for the δ18O values (up to 10‰). No correlation is found with C isotopes that exhibit, in comparison with L. pertusa, a small range of variation (2‰). This variation of δ18O at a micrometer scale is probably the result of two processes: (1) an isotopic equilibrium calcification with 1 pH unit variation in the calcification fluid as indicated by direct measurements of coelenteron pH in the coral Galaxea fascicularis (Al-Horani et al. 2003) and (2) a kinetic fractionation. The δ13C apparent disequilibrium in P. lutea may be the result of mixing between metabolic CO2 (respiration) and dissolved inorganic carbon (DIC) coming directly from seawater.

Boron, carbon and oxygen isotopic compositions were determined at the micrometre scale by high-resolution ion microprobe in a sample of modern coral (massive hermatypic coral, Porites lutea). The ion probe data show for B and O much larger isotopic variations at the micrometre scale than those measured at the millimetre scale by conventional techniques: δ18OPDB values range from −10.6±0.9‰ to −0.2±0.5‰ and δ11B values range from +18.6±1.5‰ to +30.6±1.6‰. By contrast, δ13C values show the same range of variations, from −4.6±0.65‰ to −2.2±0.67‰ at the micrometre and millimetre scales. The range of δ11B values indicates that significant pH variations, from ≈7.1 to ≈9.0, are present at the sites of calcification. The largest δ18O variations correspond to the highest δ11B values, i.e. to the highest pHs. This measurement of pH allows modelling the oxygen isotopic fractionation occurring during aragonite precipitation. Taking into account the rate of O isotopic equilibrium between dissolved carbonate species (H2CO3, HCO3− and CO32−) and water via the two reactions of hydration and hydroxylation, the full range of δ18O values measured at the micrometre scale can be modelled for residence times of dissolved carbonates in the calcifying fluid ranging between ≈1 h and at maximum ≈12 h. The pH controls the δ18O of the growing carbonate through the relative fractions of dissolved carbonate species and through the kinetics of their isotopic equilibration with water via hydration and hydroxylation. The so-called ‘vital effect’ systematically observed for δ18O in corals can thus be understood as representing an average of rapid pH variations due to coral biology during coral growth. Selectively measuring δ18O values in the zones of coral skeletons that have low δ11B values (i.e. formed at low pH) should significantly improve the quality of palaeoclimatic reconstructions based on δ18O values.

International audience; Past ocean pH and pCO2 are critical parameters for establishing relationships between Earth's climate and the carbon cycle. Previous pCO2 estimates are associated with large uncertainties and are debated. In this study, laboratory cultures of the foraminiferan genus Amphistegina were performed in order to examine the possible factors that control the Li isotope composition (δ7Li) of their shells. δ7Li is insensitive to temperature and pH variations but correlates positively with the Dissolved Inorganic Carbon (DIC) of seawater. Li/Ca ratio in the shells shows negative correlation with δ7Li, consistent with published data for planktonic foraminifera from core tops and from short periods during the Cenozoic. We propose that the sensitivity of δ7Li and Li/Ca ratio to DIC is a biological phenomenon and is related to biomineralization mechanisms in foraminifera. We used the published foraminiferal δ7Li records, and our experimental results, to determine the paleo-ocean DIC and pH for the last glacial–interglacial cycle. The results are consistent with published estimates of pH and pCO2 based on boron isotopes and ice cores. We suggest Li and its isotopes may serve as a new complementary proxy for the paleo-ocean carbonate chemistry.

When using the boron isotopic composition (δ11B) of marine carbonates as a seawater pH proxy, it is assumed that only the tetrahedral borate ion is incorporated into the growing carbonate crystals and that no boron isotope fractionation occurs during uptake. However, the δ11B of the calcium carbonate from most modern foraminifera shells or corals skeletons is not the same as the δ11B of seawater borate, which depends on pH, an observation commonly attributed to vital effects. In this study, we combined previously published high-field 11B MAS NMR and new δ11B measurements on the same synthetic calcite and aragonite samples precipitated inorganically under controlled environments to avoid vital effects. Our results indicate that the main controlling factors of δ11B are the solution pH and the mineralogy of the precipitated carbonate mineral, whereas the aqueous boron concentration of the solution, CaCO3 precipitation rate and the presence or absence of growth seeds all appear to have negligible influence. In aragonite, the NMR data show that boron coordination is tetrahedral (BO4), in addition, its δ11B is equal to that of aqueous borate, thus confirming the paleo-pH hypothesis. In contrast, both trigonal BO3 and tetrahedral BO4 are present in calcite, and its δ11B values are higher than that of aqueous borate and are less sensitive to solution pH variations compared to δ11B in aragonite. These observations are interpreted in calcite as a reflection of the incorporation of decreasing amounts of boric acid with increasing pH. Moreover, the fraction of BO3 measured by NMR in calcite is higher than that inferred from δ11B which indicates a coordination change from BO4 to BO3 upon boron incorporation in the solid. Overall, this study shows that although the observed differences in δ11B between inorganic and biological aragonite are compatible with a pH increase at calcification sites, the B speciation and isotope composition of biological calcites call for a more complex mechanism of boron incorporation.