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Geoscientists quickly recognized the broad applicability of Raman micro-probe spectroscopy to the Earth and planetary sciences, especially after commercially built microprobe instruments became available in the early 1980s. Raman spectra are sensitive to even minor (chemical or structural) perturbations within chemical bonds in (even amorphous) solids, liquids, and gases and can, thus, help identify, characterize, and differentiate between individual minerals, fluid inclusions, glasses, carbonaceous materials, solid solution phases, strain in minerals, and dissolved species in multi-component solutions. The articles in this issue explore how Raman spectroscopy has deepened and broadened our understanding of geological and extraterrestrial materials and processes.

International audience; Using continuous and time-resolved spectroscopy, we investigate Raman and luminescence signals from synthetic hydroxylapatites doped with trivalent REE including Dy 3+ , Eu 3+ , Nd 3+ , and Sm 3+ , as well as REE in natural apatites, with laser excitations at 532 nm and 785 nm. We demonstrate that time-resolved spectroscopy is an extremely efficient method to tone down the luminescence from Raman spectra or, alternatively, to investigate the luminescence signal without the interference from the Raman contribution. Time-resolved luminescence spectroscopy is found to be a powerful technique for generating specific high-quality luminescence spectra for the REE emission activators in apatites by using appropriate combinations of delay and gate width for the time synchronization of the laser pulse and ICCD detector. This allows for the unambiguous detection and identification of the activators by avoiding the overlapping of various emission signals in the luminescence spectra. This is particularly useful in the case of natural samples, which often have several activators for luminescence. In the case of synthetic REE-doped apatites, a quenching process for luminescence due to activator concentration is seen for Eu 3+ and Sm 3+ , i.e. the higher the concentration, the shorter the luminescence decay time. The interpretation of luminescence decay time in natural apatites is promising but more complex because of energy transfers between the various luminescence activators present in the crystal lattice. Luminescence is a powerful technique for detecting the presence of REE in apatites down to ppm levels, though quantifying the concentration is still a challenge.

International audience; Interpreting the environmental conditions under which ancient microbialites formed relies upon comparisons with modern analogues. This is why we need a detailed reference framework relating the chemical and mineralogical compositions of modern microbialites to the physical and chemical parameters prevailing in the environments where they form. Here, we measured the chemical, including major and trace elements, and mineralogical composition of microbialites from ten Mexican lakes as well as the chemical composition of the surrounding waters. Saturation states of lakes with different mineral phases were systematically determined and correlations between solution and solid chemical analyses were assessed using multivariate analyses. A large diversity of microbialites was observed in terms of mineralogical composition, with occurrence of diverse carbonate phases such as (Mg-)calcite, monohydrocalcite, aragonite, hydromagnesite, and dolomite as well as authigenic Mg-silicate phases (kerolite and/or stevensite). All lakes harbouring microbialites were saturated or supersaturated with monohydrocalcite, suggesting that such a saturation state might be required for the onset of microbialite formation and that precursor soluble phases such as amorphous calcium carbonate and monohydrocalcite play a pivotal role in these lakes. Subsequently, monohydrocalcite transforms partly or completely to aragonite or Mg-calcite, depending on the lake (Mg/Ca)aq. Moreover, lakes harbouring hydromagnesite-containing microbialites were saturated with an amorphous magnesium carbonate phase, supporting again the involvement of precursor carbonate phases. Last, authigenic Mg-silicates formed by homogenous or heterogenous nucleation in lakes saturated or supersaturated with a phase reported in the literature as “amorphous sepiolite” and with a H4SiO4 concentration superior to 0.2 mM. A strong correlation between the alkalinity and the salinity of all the lakes was observed. The observed large variations of alkalinity between the lakes relate to varying concentration stages of an initial alkaline dilute water, due to a varying hydrochemical functioning. In all cases, the size of microbialites in the lakes correlated positively with salinity, (Mg/Ca)aq ratio and alkalinity. The trace element compositions of the microbialites also varied significantly between the lakes. Detrital contamination of the studied microbialites was the major factor affecting their rare earth elements (REE) + Y patterns. In particular, the microbialites highly affected by detrital contamination showed a high (REE + Y) content and flat (REE + Y) patterns. In contrast, some microbialites poorly affected by detrital contamination showed (REE + Y) patterns with features commonly reported for marine microbialites, such as a superchondritic Y/Ho ratio, enrichment in heavy REE and a negative Ce anomaly. This last observation questions the possibility to infer the marine versus lacustrine origin of a microbialite based on (REE + Y) patterns only. Overall, while microorganisms can impact nucleation processes and textural arrangements in microbialites, we observe that the hydrogeochemical evolution of lakes exerts a primary control over the onset of microbialite formation and the evolution of their chemical and mineralogical composition. Moreover, while changes of all these chemical and mineralogical features upon diagenesis and metamorphism will need to be assessed, the present study, together with recent meta-analyses of modern microbialites, broadens the set of modern references available for comparisons with geological archives.

This article reviews nonconventional Raman spectroscopy techniques and discusses present and future applications of these techniques in the Earth and planetary sciences. Time-resolved spectroscopy opens new ways to limit or exploit luminescence effects, whereas techniques based on coherent anti-Stokes Raman scattering (CARS) or surface-enhanced Raman spectroscopy (SERS) allow the Raman signal to be considerably enhanced even down to very high spatial resolutions. In addition, compact portable Raman spectrometers are now routinely used out of the laboratory and are even integrated to two rovers going to Mars in the near future.

The Pulo do Lobo domain is one of the units exposed within the orogenic suture zone between the Ossa-Morena and the South Portuguese zones in the SW Iberian Variscides. This metasedimentary unit has been classically interpreted as a Rheic subduction-related accretionary prism formed during pre-Carboniferous convergence and eventual collision between the South Portuguese Zone (part of Avalonia) and the Ossa-Morena Zone (peri-Gondwanan terrane). Discrete mafic intrusions also occur within the dominant Pulo do Lobo metapelites, related to an intra-orogenic Mississippian transtensional and magmatic event that had a significant thermal input. Three different approaches have been applied to the Devonian-Carboniferous phyllites and slates of the Pulo do Lobo domain in order to study their poorly known low-grade metamorphic evolution. X-ray diffraction (XRD) was used to identify the mineralogy and measure crystallographic parameters (illite "crystallinity" and K-white mica b-cell dimension). Compositional maps of selected samples were obtained from electron probe micro-analysis, which allowed for processing with XMapTools software, and chlorite semiempirical and thermodynamic geothermometry was performed. Thermometry based on Raman spectroscopy of carbonaceous material (RSCM) was used to obtain peak temperatures. The microstructural study shows the existence of two phyllosilicate growth events in the chlorite zone, the main one (M-1) related to the development of a Devonian foliation S-1 and a minor one (M-2) associated with a crenulation cleavage (S-2) developed in middle-upper Carboniferous times. M-1 entered well into epizone (greenschist facies) conditions. M-2 conditions were at lower temperature, reaching the anchizone-epizone boundary. These data accord well with the angular unconformity that separates the Devonian and Carboniferous formations of the Pulo do Lobo domain. The varied results obtained by the different approaches followed, combined with microstructural analysis, provide different snapshots of the metamorphic history. Thus, RSCM temperatures are higher in comparison with the other methods applied, which is interpreted to reflect a faster re-equilibration during the short-lived thermal Mississippian event. Regarding the metamorphic pressure, the data are very homogeneous: very low celadonite content (0 %-10 %) in muscovite (and low values of K-white mica b-cell dimension; 8.995 angstrom mean value), indicating a low pressure-temperature gradient, which is unexpected in a subduction-related accretionary prism., This research has been supported by the Spanish Ministry of Science and Innovation (grant no. CGL2011-24101), the Spanish Ministry of Economy and Competitiveness (grant nos. CGL2015-71692-P, CGL2016-75679-P), the Andalusian Government (grant nos. RNM-148, RNM-179), and the doctoral scholarship to Irene Perez-Caceres from the Spanish Ministry of Science and Innovation (grant no. BES-2012-055754). The Raman facility in Paris has been funded by the city of Paris (Emergence program).

Achromatium is a long known uncultured giant gammaproteobacterium forming intracellular CaCO3 that impacts C and S geochemical cycles functioning in some anoxic sediments and at oxic-anoxic boundaries. While intracellular CaCO3 granules have first been described as Ca oxalate then colloidal CaCO3 more than one century ago, they have often been referred to as crystalline solids and more specifically calcite over the last 25 years. Such a crystallographic distinction is important since the respective chemical reactivities of amorphous calcium carbonate (ACC) and calcite, hence their potential physiological role and conditions of formation, are significantly different. Here, we analyzed the intracellular CaCO3 granules of Achromatium cells from Lake Pavin using a combination of Raman microspectroscopy and scanning electron microscopy. Granules in intact Achromatium cells were unequivocally composed of ACC. Moreover, ACC spontaneously transformed into calcite when irradiated at high laser irradiance during Raman analyses. Few ACC granules also transformed spontaneously into calcite in lysed cells upon cell death and/or sample preparation. Overall, the present study supports the original claims that intracellular Ca-carbonates in Achromatium are amorphous and not crystalline. In that sense, Achromatium is similar to a diverse group of Cyanobacteria and a recently discovered magnetotactic alphaproteobacterium, which all form intracellular ACC. The implications for the physiology and ecology of Achromatium are discussed. Whether the mechanisms responsible for the preservation of such unstable compounds in these bacteria are similar to those involved in numerous ACC-forming eukaryotes remains to be discovered. Last, we recommend to future studies addressing the crystallinity of CaCO3 granules in Achromatium cells recovered from diverse environments all over the world to take care of the potential pitfalls evidenced by the present study.

Subduction of crustal C governs the long-term global C cycling. The role of carbonates recycling in subduction zones and the related dissolution of C at various depths have been the subject of a large body of literature over the last decades. Much less is known about the contribution of carbonaceous material (CM) to the deep C cycling in subduction zones. This paper presents natural evidence for intense fluid-mediated leaching of CM in pelitic schists at high-pressure/low-temperature conditions relevant to the forearc region of subducting slabs. Manifestations of such process were identified along fluid pathways at various scales in the blueschist-facies subduction complexes of both Alpine Corsica and the Western Alps. Microstructural, whole-rock and Raman analyses across a selected metasomatic aureole were used to quantify the amount and mechanisms of C loss during fluid-rock interaction. In samples affected by intense fluid infiltration, >90% of the initial CM was removed from the rock. Microstructural and micro-Raman data indicate selective leaching of disordered CM relative to nearly crystalline graphite. The collected data allowed constraining the magnitude of fluid fluxes required to bleach the studied CM-bearing lithologies at different P-T-fO2 conditions, which corresponds to rather high time-integrated fluid fluxes in the order of ~106 m3/m2. In settings of large-scale fluid channelization, such as along regional-scale, lithological/tectonic boundaries or at the top of the subducted sedimentary pile, intense dissolution of subducted CM is expected. This process may thus exert a negative feedback on the sink of C phases into the deep mantle over the geological timescales and contribute to the release of isotopically light C from subducting slabs in forearc regions.

Graphitization in fault zones is associated both with fault weakening and orogenic gold mineralization. We examine processes of graphitic carbon emplacement and deformation in the active Alpine Fault Zone, New Zealand by analysing samples obtained from Deep Fault Drilling Project (DFDP) boreholes. Optical and scanning electron microscopy reveal a microtextural record of graphite mobilization as a function of temperature and ductile then brittle shear strain. Raman spectroscopy allowed interpretation of the degree of graphite crystallinity, which reflects both thermal and mechanical processes. In the amphibolite-facies Alpine Schist, highly crystalline graphite, indicating peak metamorphic temperatures up to 640°C, occurs mainly on grain boundaries within quartzo-feldspathic domains. The subsequent mylonitization process resulted in the reworking of graphite under lower temperature conditions (500–600°C), resulting in clustered (in protomylonites) and foliation-aligned graphite (in mylonites). In cataclasites, derived from the mylonitized schists, graphite is most abundant (

International audience; The chemical and isotopic compositions of biogenic apatite are important geochemical markers, which can suffer modifications during fossilisation. Compared with modern ones, fossil apatites generally exhibit variations in carbonate content, enrichment in fluorine, incorporation of trace elements and an increase in crystallinity parameters. Detailed understanding of these transformations induced by fossilisation should help assess the preservation of geochemical records in apatites. In this contribution, we investigate the transformation of modern bone altered under controlled conditions. Modern bone samples were soaked in aqueous solutions of neutral to alkaline pH (9–10) for one and three weeks at various temperatures (20 and 70 °C) and experiments were duplicated in fluorine-free and in 10−2 M NaF solutions. Bone transformation was monitored through the modifications of chemical (F, Ca, P) and isotopic (δ13C, δ18Oc, δ18Op) composition as well as using vibrational (ATR-FTIR, Raman) and solid-state (1H, 13C, 19F) NMR spectroscopies. The observed modifications sustain a transformation mechanism through partial dissolution of biogenic apatite and precipitation of secondary apatite. This transformation occurs irrespective of the presence or absence of fluorine and leads to the formation of carbonate-bearing fluorapatite or carbonate-bearing hydroxylapatite, respectively. The fraction of secondary apatite seems to be limited to ~60%, suggesting that its formation has a protecting role against further dissolution of the primary apatite. The observation of clumped (CO32−, F−) defects in the structural B-site of some samples as well as perturbation of the isotopic compositions attest to carbonate incorporation in the secondary apatite. Although the incorporation of fluoride ions can serve as a probe revealing dissolution-recrystallization of bone, the present study also underlines the difficulty to systematically relate mineralogical transformations to an open-system behaviour in bioapatite.

International audience

During the Quaternary, periodic glaciations transformed mountain landscapes. However, characterizing the way in which mountain erosion changes between glacier- and river-dominated conditions has been elusive. Here, using samples from an offshore sedimentary core, we estimated the spatial distribution of erosion in the southern part of the Southern Alps of New Zealand during a full transition from the Last Glacial Maximum (LGM), ca. 20 ka, to the last millennium. Raman spectroscopy analyses of carbonaceous material revealed a marked change in the sediment provenance, which we interpreted to reflect the evolving erosion pattern of the mountain range. Over the Holocene, since at least ca. 9 ka, erosion was focused on the chlorite zone schist within the upper reaches of the valleys (>15–20 km distance from the mountain front), possibly dominated by large-magnitude landslides. During the last glaciation, the proportion of sediments from the biotite schist and higher-grade metamorphic rocks in the lower-lying areas closer to the mountain front (

International audience; The South Tien Shan (STS) belt results from the last collision event in the western Central Asian Orogenic Belt (CAOB). Understanding its formation is of prime importance in the general framework of the CAOB. The Atbashi Range preserves high‐P (HP) rocks along the STS suture, but still, its global metamorphic evolution remains poorly constrained. Several HP units have been identified: (a) a HP tectonic mélange including boudins of mafic eclogites in a sedimentary matrix, (b) a large (>100 km long) high‐P metasedimentary unit (HPMU) and (c) a lower blueschist facies accretionary prism. Raman Spectroscopy on carbonaceous material combined with phengite and chlorite multiequilibria and isochemical phase diagram modelling indicates that the HPMU recorded homogeneous P–T conditions of 23–25 kbar and 560–570°C along the whole unit. 40Ar/39Ar dating on phengite from the HPMU ranges between 328 and 319 Ma at regional scale. These ages are interpreted as (re‐) crystallization ages of phengite during Tmax conditions at a pressure range of 20–25 kbar. Thermobarometry on samples from the HP tectonic mélange provides similar metamorphic peak conditions. Thermobarometry on the blueschist to lower greenschist facies accretionary prism indicates that it underwent P–T conditions of 5–6 kbar and 290–340°C, highlighting a 17–20 kbar pressure gap between the HPMU‐tectonic mélange units and the accretionary prism. Comparison with available geochronological data suggests a very short time span between the prograde path (340 Ma), HP metamorphic peak (330 Ma), the Tmax (328–319 Ma) and the final exhumation of the HPMU (303–295 Ma). Extrusion of the HPMU, accommodated by a basal thrust and an upper detachment, was driven by buoyant forces from 70–75 km up to 60 km depth, which directly followed continental subduction and detachment of the HPMU. At crustal depths, extrusion was controlled by collisional tectonics up to shallow levels. Lithological homogeneity of the HPMU and its continental‐derived character from the North Tien Shan suggest this unit corresponds to the hyper‐extended continental margin of the Kazakh continent, subducted southward below the north continental active margin of the Tarim craton. Integration of the available geological data allows us to propose a general geodynamic scenario for Tien Shan during the Carboniferous with a combination of (a) N‐dipping subduction below the Kazakh margin of Middle Tien Shan until 390–340 Ma and (b) S‐dipping subduction of remaining Turkestan marginal basins between 340 and 320 Ma.

International audience; The biogenicity of putative traces of life found in early-Archean rocks is strongly debated. To date, only equivocal lines of evidence have been reported, which has prevented a full consensus from emerging. Here we report elemental and molecular data from individual organic microfossils preserved within the 3.4 billion-year-old cherts of the Strelley Pool Formation, Western Australia. The present results support the growing body of evidence advocating their biogenicity, promoting them as the oldest known authentic organic microfossils. These microfossils consist of nitrogen- and oxygen- rich organic molecules that have been only slightly degraded despite experiencing temperatures of ~300 °C. Such molecular preservation emphasises the palaeobiological potential of the Earth’s oldest geological record, whilst providing a promising window into the early biosphere.

International audience; A combination of adapted chlorite thermometry and high-spatial-resolution analytical techniques (TEM-EDX/FIB) shows that the low-grade metamorphic chlorites of the Glarus Alps, Central Alps (Switzerland), do not record the peak metamorphic conditions as commonly assumed in previous studies of this reference area for low-grade metamorphism. Chlorites have rather recorded several stages of the retrograde path, through an intracrystalline nanometric-scale compositional zoning. The consistency of the nanoscale zoning patterns observed both within sample and along the transect suggests that local equilibrium was achieved at this spatial scale and maintained during growth or re-equilibration. Applying recent thermobarometers, we highlight that chlorites recorded a distinct behaviour between the northern and southern part of the studied transect: the south of the Glarus area displays a regular P-T exhumation path, from 3.0 ± 0.2 kbar and 310 ± 20 °C for maximum P-T (estimated with conventional thermometers), to ~0.8 kbar and ~220 °C according to chlorite crystal-core analysis, and to ~0.3 kbar and ~190 °C according to chlorite crystal-rim analysis. On the contrary, the north of the Glarus area shows an apparent break in the exhumation, with P estimates from chlorite crystal rims (~1.3 kbar) higher than from chlorite crystal cores (~0.8 kbar). Even if the absolute pressure values are fraught with large uncertainty, their contrasting core/rim pattern is not model dependent. We try to correlate these new thermobarometric results with independent data to refine the exhumation scenario of the North-Helvetic flyschs, confirming differential uplift along the transect. This reappraisal of Glarus chlorite thermometry demonstrates that an adapted thermometry/analysis protocol opens new prospects for investigating the evolution of low-grade metamorphic terranes.

Hybrid rocks formed by fluid–rock interactions at high-pressure (HP) metamorphic conditions are active players in the recycling of volatiles in subduction zones. Such rocks include chlorite–talc–amphibole-rich (± carbonate) rocks formed by chemical and mechanical mixing of mafic, ultramafic and sedimentary protoliths. Recent discovery of widespread formation of lawsonite-rich hybrid rocks extends the composition range of these rocks and their significance for volatile transfer to the deep Earth. In this study we quantify the drastic water enrichment across a metasomatic aureole characterized by intense chemical resetting and massive lawsonite precipitation in Alpine Corsica (France). The chemical composition of the metasomatic product, which in many cases approaches the CASH system, favors (i) the precipitation of lawsonite and the unexpected reincorporation of free water at HP conditions, and (ii) the stability of lawsonite at higher temperature and at greater depth compared to the MORB + H 2 O system. We conclude that these hybrid rocks may contribute to transfer water to great depth in subduction, with implications for water cycling to the mantle.

International audience; High-pressure metamorphic rocks exhumed in mountain belts provide a unique window on deep processes at subduction zones, such as the progressive transformation of blueschist into eclogite, which has important geochemical and geophysical implications, along with information on their exhumation mechanism. We provide a detailed characterization of the field and metamorphic relationships between blueschist- and eclogite-facies terranes of Alpine Corsica (France), where both primary, pre-subduction structures and Alpine high-pressure assemblages are very well preserved. We then compare our data with available observations from the Western Alps. Altogether, these data show systematic metamorphic patterns across the blueschist–eclogite boundary: temperature increases progressively without any gap across the contact, whereas a significant pressure jump (ca. 0.4 GPa) is observed. Lithostratigraphy in the two units suggests that they belong to two different types of oceanic (or transitional) crust, structures of which may have controlled their different mechanisms of decollement, accretion and exhumation. Lastly, the comparison of the exhumed terranes in Alpine belts with structures of modern analogues in present-day oceans, such as large detachment faults and oceanic core-complexes, stresses the importance of inherited extensional structures for subduction, exhumation and orogenic processes.

International audience; Fossil biominerals and fossils of microorganisms in ancient rocks contain important biogeochemical signals. Decoding this record may reveal crucial information about the evolution of life on Earth and terrestrial paleoenvironments. However, the identification of traces of life especially in very old rocks is extremely challenging because the morphological and chemical signatures of biominerals and microfossils are subtle, of microscopic size and inevitably alteredwith aging. In this review,we stress on the fact that biomineralization is often the first step of fossilization and produces particular chemical, structural and morphological features that can be preserved in fossil biominerals ormicrofossils, with a special focus on Fe-biomineralization. The taphonomic processes affecting biominerals andmicrofossils and altering theirmorphology and/or chemical composition over time are then discussed in light of experimental fossilization simulations and field sample analyses. Wesuggest that taxonomic biases observed in the fossil record may be related to differential abilities of species to trigger biomineralization. This calls for studies of the effective biomineralizing activity and fossilization potential of each species present in highly diverse natural microbial communities. Finally, recent analytical developments leave little doubt that very substantial progress in the study of biomineralization processes and ancient biostructures will be achieved in the near future.

International audience; Estimation of Fe3+/ΣFe ratios in materials at the submicrometre scale has been a long-standing challenge in the Earth and environmental sciences because of the usefulness of this ratio in estimating redox conditions as well as for geothermometry. To date, few quantitative methods with submicrometric resolution have been developed for this purpose, and most of them have used electron energy-loss spectroscopy carried out in the ultra-high vacuum environment of a transmission electron microscope (TEM). Scanning transmission X-ray microscopy (STXM) is a relatively new technique complementary to TEM and is increasingly being used in the Earth sciences. Here, we detail an analytical procedure to quantify the Fe3+/ΣFe ratio in silicates using Fe L2,3-edge X-ray absorption near edge structure (XANES) spectra obtained by STXM, and we discuss its advantages and limitations. Two different methods for retrieving Fe3+/ΣFe ratios from XANES spectra are calibrated using reference samples with known Fe3+ content by independent approaches. The first method uses the intensity ratio of the two major peaks at the L3-edge. This method allows mapping of Fe3+/ΣFe ratios at a spatial scale better than 50 nm by the acquisition of 5 images only. The second method employs a 2-eV-wide integration window centred on the L2 maximum for Fe3+, which is compared to the total integral intensity of the Fe L2-edge. These two approaches are applied to metapelites from the Glarus massif (Switzerland), containing micrometre-sized chlorite and illite grains and prepared as ultrathin foils by focused ion beam milling. Nanometre-scale mapping of iron redox in these samples is presented and shows evidence of compositional zonation. The existence of such zonation has crucial implications for geothermometry and illustrates the importance of being able to measure Fe3+/ΣFe ratios at the submicrometre scale in geological samples.

International audience

International audience; Carbonate-bearing lithologies are the main carbon carrier into subduction zones. Their evolution during metamorphism largely controls the fate of carbon, regulating its fluxes between shallow and deep reservoirs. Recent estimates predict that almost all subducted carbon is transferred into the crust and lithospheric mantle during subduction metamorphism via decarbonation and dissolution reactions at high-pressure conditions. Here we report the occurrence of eclogite-facies marbles associated with metasomatic systems in Alpine Corsica (France). The occurrence of these marbles along major fluid-conduits as well as textural, geochemical and isotopic data indicating fluid–mineral reactions are compelling evidence for the precipitation of these carbonate-rich assemblages from carbonic fluids during metamorphism. The discovery of metasomatic marbles brings new insights into the fate of carbonic fluids formed in subducting slabs. We infer that rock carbonation can occur at high-pressure conditions by either vein-injection or chemical replacement mechanisms. This indicates that carbonic fluids produced by decarbonation reactions and carbonate dissolution may not be directly transferred to the mantle wedge, but can interact with slab and mantle-forming rocks. Rock-carbonation by fluid–rock interactions may have an important impact on the residence time of carbon and oxygen in subduction zones and lithospheric mantle reservoirs as well as carbonate isotopic signatures in subduction zones. Furthermore, carbonation may modulate the emission of CO2 at volcanic arcs over geological time scales.

International audience; Orogenic wedges locally present chaotic tectonostratigraphic units that contain exotic blocks of various size, origin, age and lithology, embedded in a sedimentary matrix. The occurrence of ophiolitic blocks, sometimes huge, in such “mélanges” raises questions on (i) the mechanisms responsible for the incorporation of oceanic basement rocks into an accretionary wedge and (ii) the mechanisms allowing exhumation and redeposition of these exotic elements in “mélanges” during wedge growth.To address these questions, we present the results of a series of analogue experiments performed to characterize the processes and parameters responsible for accretion, exhumation and tectonosedimentary reworking of oceanic basement lithospheric fragments in an accretionary wedge.The experimental setup is designed to simulate the interaction between tectonics, erosion and sedimentation. Different configurations are applied to study the impact of various parameters, such as irregular oceanic floor due to structural inheritance, or the presence of layers with contrasted rheology that can affect deformation partitioning in the wedge (frontal accretion vs basal accretion) influencing its growth. Image correlation technique allows extracting instantaneous velocity field, and tracking of passive particles. By retrieving the particle paths determined from models, the pressure-temperature path of mélange units or elementary blocks can be discussed. The experimental results are then compared with observations from ophiolite-bearing mélanges in Taiwan (Lichi and Kenting mélanges) and Raman spectroscopy of carbonaceous material (RSCM) Thermometry data on rocks from the northern Apennines (Casanova mélange). A geological scenario is proposed following basic observations. The tectonic evolution of the retroside of doubly vergent accretionary wedges is mainly controlled by backthrusting and backfolding. The retro wedge is characterized by steep slopes that are prone to gravitational instabilities. It triggers submarine landslides inducing huge mass transfers. This erosion combined with backthrusting could favour exhumation of the ophiolitic fragments formerly accreted at the base of the wedge along the rough seafloor-sediments interface. Such an exhumed material can be reworked and deposited as debris- flows in proximal basins located at the foot of the retrowedge slope forming a tectono-sedimentary mélange. These syntectonic basins are continuously deformed and involved in prograding backthrusting-induced deformation.

The orogenic wedge of Taiwan results from the late Miocene collision of the Chinese passive margin and the Luzon volcanic arc. Because of the southward propagation of the collision over time, and because of its extreme rates of deformation and erosion, it has appeared as an ideal place to investigate mountain building processes. Here, we review existing metamorphic and thermochronological data on late Cenozoic burial and exhumation. Most of the island has been extensively investigated, in particular in terms of zircon or apatite fission-track and (U–Th)/He thermochronology. Peak metamorphic temperatures have also been quantified from the Raman spectroscopy of carbonaceous material along three transects in central Taiwan. The different datasets appear consistent, and indicate that cooling rates and exhumation are more intense within the Hsueshan Range and within the Tananao Complex. Lateral variations, from south to north are also observed, and they can be interpreted in terms of different stages of exhumation and mountain building. Existing models provide a framework to analyze the data and discuss the limits of some previous interpretations, in particular in terms of exhumational steady state or of recent acceleration of uplift and exhumation. These models are also discussed in light of available data. It appears that all of them fit thermochronological data within the Tananao Complex, whatever the kinematics, the depth of the wedge, or the mechanism responsible for exhumation, and that exhumation of the Hsueshan Range has been ignored in most models. Future models need therefore to consider the Taiwan wedge as a whole. Additional constraints on peak metamorphic conditions, on kinematics of shortening and exhumation, or on the geometry of the wedge at depth need to be gathered to further unravel mountain building processes at the scale of the whole orogen.

Morphological and chemical evidence of ancient life is widespread in sedimentary rocks retrieved from shallow depths in the Earth's crust. Metamorphism is highly detrimental to the preservation of biological information in rocks, thus limiting the geological record in which traces of life might be found. Deformation and increasing pressure/temperature during deep burial may alter the morphology as well as the composition and structure of both the organic and mineral constituents of fossils. However, microspore fossils have been previously observed in intensely metamorphosed rocks. It has been suggested that their small size, and/or the nature of the polymer composing their wall, and/or the mineralogy of their surrounding matrix were key parameters explaining their exceptional preservation. Here, we describe the remarkable morphological preservation of plant macrofossils in blueschist metamorphic rocks from New Zealand containing lawsonite. Leaves and stems can be easily identified at the macroscale. At the microscale, polygonal structures with walls mineralized by micas within the leaf midribs and blades may derive from the original cellular ultrastructure or, alternatively, from the shrinkage during burial of the gelified remnants of the leaves in an abiotic process. Processes and important parameters involved in the remarkable preservation of these fossils during metamorphism are discussed. Despite the excellent morphological preservation, the initial biological polymers have been completely transformed to graphitic carbonaceous matter down to the nanometer scale. This occurrence demonstrates that plant macrofossils may experience major geodynamic processes such as metamorphism and exhumation involving deep changes and homogenization of their carbon chemistry and structure but still retain their morphology with remarkable integrity even if they are not shielded by any hard-mineralized concretion.

The insoluble organic matter (IOM) of an unequilibrated enstatite chondrite Sahara (SAH) 97096 has been investigated using a battery of analytical techniques. As the enstatite chondrites are thought to have formed in a reduced environment at higher temperatures than carbonaceous chondrites, they constitute an interesting comparative material to test the heterogeneities of the IOM in the solar system and to constrain the processes that could affect IOM during solar system evolution. The SAH 97096 IOM is found in situ: as submicrometer grains in the network of fine-grained matrix occurring mostly around chondrules and as inclusions in metallic nodules, where the carbonaceous matter appears to be more graphitized. IOM in these two settings has very similar $\delta^{15}N$ and $\delta^{13}C$; this supports the idea that graphitized inclusions in metal could be formed by metal catalytic graphitization of matrix IOM. A detailed comparison between the IOM extracted from a fresh part and a terrestrially weathered part of SAH 97096 shows the similarity between both IOM samples in spite of the high degree of mineral alteration in the latter. The isolated IOM exhibits a heterogeneous polyaromatic macromolecular structure, sometimes highly graphitized, without any detectable free radicals and deuterium-heterogeneity and having mean H- and N-isotopic compositions in the range of values observed for carbonaceous chondrites. It contains some submicrometer-sized areas highly enriched in $^{15}N$ ($\delta^{15}N$ up to 1600 permil). These observations reinforce the idea that the IOM found in carbonaceous chondrites is a common component widespread in the solar system. Most of the features of SAH 97096 IOM could be explained by the thermal modification of this main component.

International audience; Abstract Pyritized plant tissues with well-preserved morphology were studied in rocks from Vanoise (western Alps, France) that experienced high-pressure, low-temperature metamorphic conditions in the blueschist facies during the Alpine orogeny. Organic and inorganic phases composing these fossils were characterized down to the nanometer scale by Raman microspectroscopy, scanning transmission X-ray microscopy and transmission electron microscopy. The graphitic but disordered organic matter composing these fossils is chemically and structurally homogeneous and mostly contains aromatic functional groups. Its original chemistry remains undefined likely because it was significantly transformed by diagenetic processes and/or thermal degradation during metamorphism. Various mineral phases are closely associated with this organic matter, including sulphides such as pyrite and pyrrhotite, carbonates such as ankerite and calcite, and iron oxides. A tentative time sequence of formation of these diverse mineral phases relative to organic matter decay is proposed. The absence of traces of organic matter sulphurization, the pervasive pyritization of the vascular tissues and the presence of ankerite suggest that the depositional/diagenetic environment of these metasediments was likely rich in reactive iron. Fe-sulphides and ankerite likely precipitated early and might have promoted the preservation of the fossilized biological soft tissues by providing mechanical resistance to compaction during diagenesis and subsequent metamorphism. In contrast, iron oxides which form rims of 100-nm in thickness at the interface between organic matter and Fe-sulphides may result from metamorphic processes. This study illustrates that it may be possible in some instances to deconvolve metamorphic from diagenetic imprints and opens new avenues to better constrain processes that may allow the preservation of organic fossils during diagenesis and metamorphism.

The occurrence and preservation of aragonite in eclogite-facies rocks of north-eastern Corsica is linked to an uncommon microtexture. Aragonite exclusively occurs as oriented fibres in garnet crystals of a graphitic, more or less siliceous marble that immediately overlies a serpentinite body of the meta-ophiolitic unit. The arrangement of the fibres is grossly radial, but more clearly sectoral in subhedral garnet, the fibres growing perpendicular to the garnet/matrix interface. Raman mapping reveals that the carbonate is calcite in the matrix and in poikiloblastic garnet cores, and that the fibres in the garnet mantle are aragonite alone in the case of a carbonate matrix, and both aragonite and quartz (in distinct fibres) in a quartz–carbonate matrix. These features are interpreted as prograde intergrowths, the result of garnet nucleation and growth in a calcite and then aragonite matrix (±quartz). Upon further heating and/or decompression, the aragonite matrix transformed back to calcite while the carbonates included in garnet retained their original structure, in spite of the relatively high temperature attained ( ca. 500 °C). These aragonite relics are one more example of the preservation of a high-pressure polymorph through mechanical shielding of inclusions in a rigid host. The aragonite–garnet intergrowths are similar to quartz–garnet intergrowths described in amphibolite-facies graphitic schists. They are evidence that oriented inclusions in garnet are not necessarily precipitates (‘exsolutions’). Unlike precipitates, their orientation is controlled more by the shape of the garnet growth front than by symmetry constraints.

The glacial way of wearing away The rate at which glaciers erode landscapes is an important but poorly constrained relationship. Herman et al. tackle this issue by considering the Franz Josef alpine glacier in New Zealand. The amount of sediment piling up at the edge of the glacier provided erosion rates, whereas remote sensing allowed for simultaneous tracking of glacial motion. The result was a nonlinear relationship, suggesting that fast glaciers are much more effective at gouging landscapes. This could explain the paradox of why long-term erosion rates are so much lower in polar regions with more permanent glaciers. Science , this issue p. 193

International audience; Carbon is transported from Earth's surface into its interior at subduction zones. Carbonates in sediments overlying hydrothermally altered rocks (including serpentinites) within the subducted slab are the main carriers of this carbon1. Part of the carbon is recycled back to the surface by volcanism, but some is transferred to the deep Earth1, 2. Redox transformations during shallow subduction control the transfer and long-term fate of carbon, but are poorly explored1, 3. Here we use carbon stable isotopes and Raman spectroscopy to analyse the reduction of carbonate in an exhumed serpentinite-sediment contact in Alpine Corsica, France. We find that highly crystalline graphite was formed during subduction metamorphism and was concentrated in the sediment, within a reaction zone in direct contact with the serpentinite. The graphite in this reaction zone has a carbon isotopic signature (δ13C) of up to 0.8±0.1‰, similar to that of the original calcite that composed the sediments, and is texturally associated with the calcium-bearing mineral wollastonite that is also formed in the process. We use mass-balance calculations to show that about 9% of the total carbonaceous matter in the sedimentary unit results from complete calcite reduction in the reaction zone. We conclude that graphite formation, under reducing and low-temperature conditions, provides a mechanism to retain carbon in a subducting slab, aiding transport of carbon into the deeper Earth.

International audience; Phyllosilicates are among the most important stable minerals within the Earth’s crust. Their use as geo-thermometer bears great potential for application to the thermal history of rocks within the stability range of layered silicates and was tested here.A high-resolution analytical technique combining focused ion beam (FIB) milling and analytical electron microscopy (AEM) analysis has been applied to a series of sandstone core samples from the Gulf Coast (Texas, U.S.A.). The nanoscale compositional variations of K-deficient mica and chlorite flakes show that rim compositions are the most likely to approach equilibrium compositions, whereas core compositions may be relict, especially for illite-like phases. These rim analyses were used to test existing empirical or thermodynamically formulated thermo(baro)meters against maximum temperatures, which are perfectly constrained for the selected samples as they were measured in situ during drilling (100–230 °C and 300–1200 bars). The results show that most of the empirical models overestimate the temperature, while thermodynamic models yields reasonable estimates for diagenetic to anchizonal conditions, especially if the Fe3+ content is taken into account. This study clearly shows that phyllosilicates thermometry is reliable when combined with an analytical technique giving access to the fine-scale compositional variations that may represent local equilibration, whereas using micrometric compositional analysis precludes trustworthy application of such thermometers.

International audience; Multiple pieces of geologic evidence suggest that interfaces between contrasted lithologies exert a strong control on the fate of volatiles in subduction zones. Here we present results from a contact between serpentinites and sediments, located in Corsica and metamorphosed in the blueschist facies during the alpine orogeny. It was shown previously that carbonates in the sediments have been reduced to graphitic carbonaceous material within a 5-10-cm-thick reaction zone at the contact with serpentinites. In an effort to investigate the mechanisms governing this unusual process, bulk rock geochemical analyses incorporating a statistical analysis of compositional data are presented. Observations show that the fate of C was decoupled from that of other elements such as O, H, and large-ion lithophile elements--e.g. K, Sr, Ba...,As--that were extensively leached from the reaction zone. Notably, Na is strongly enriched in the reaction zone and structurally linked to pectolite. Reducing conditions, manifested by the depletion of O in the reaction zone compared to the bulk metasediment, were likely maintained by the presence of Fe(II) in the serpentinite. Moreover, thermodynamic calculations show that the low solubility of carbon in COH fluids at high-pressure and low-temperature conditions was the main driver for graphite precipitation synchronously with carbonate destabilization. This may have been kinetically favored by the presence of already existing graphitized carbonaceous material and phengite in the metasediment. Limited lateral flow might have contributed as well to the geochemical and petrological patterns observed in these rocks.

Alpine Corsica consists of a stack of variably metamorphosed units of continental and Tethys-derived rocks. It represents an excellent example of high-pressure (H. P) orogenic belt, such as the Western Alps, exposed over a small and accessible area. Compared to the Western Alps, the geology of Alpine Corsica is poorly unraveled. During the 1970s-80s, based on either lithostratigraphic or metamorphic field observations, various classifications of the belt have been proposed, but these classifications have been rarely matched together. Furthermore, through time, the internal complexity of large domains has been progressively left aside in the frame of large-scale geodynamic reconstructions. As a consequence, major open questions on the internal structure of the belt have remained unsolved. Apart from a few local studies, Alpine Corsica has not benefited of modern developments in petrology and basin research. This feature results in several uncertainties when combining lithostratigraphic and metamorphic patterns and, consequently, in the definition of an exhaustive architecture of the belt. In this paper we provide a review on the geology of Alpine Corsica, paying particular attention to the available lithostratigraphic and metamorphic classifications of the metamorphic terranes. These data are completed by a new and exhaustive metamorphic dataset obtained by means of thermometry based on Raman Spectroscopy of Carbonaceous Material (RSCM). This technique provides reliable insights on the peak temperature of the metamorphic history for CM-bearing metasediments. A detailed metamorphic characterization of metasediments, which have been previously largely ignored due to retrogression or to the lack of diagnostic mineralogy, is thus obtained and fruitfully coupled with the available lithostratigraphic data. Nine main tectono-metamorphic units are defined, from subgreenschist (ca. 280-300 °C) to the lawsonite-eclogite-facies (ca. 500-550 °C) condition. These units are homogeneous in metamorphism, laterally continuous and have characteristic lithostratigraphic features. This study also suggests a direct link between the pre-orogenic extensional setting and the present-day compressional structure of Alpine Corsica, indicating that large sections of subducted lithosphere were subducted and exhumed as coherent domains. These features provide important insight on the mechanism of stacking and exhumation of H. P rocks, and make Alpine Corsica a unique reference for mountain-building processes in Tethyan-type orogens. © 2012 Elsevier B.V.

International audience; The evolution of chlorite composition with temperature (and pressure) serves as basis to a number of chlorite chemical thermometers, for which the oxidation state of iron has been recognised as a recurrent issue, especially at low temperature (T). A new chlorite geothermometer that does not require prior Fe3+ knowledge is formulated, calibrated on 161 analyses with well-constrained T data covering a wide range of geological contexts and tested here for low-T chlorites (T < 350 °C and pressures below 4 kbar). The new solid-solution model used involves six end-member components (the Mg and Fe end-members of ‘Al-free chlorite S’, sudoite and amesite) and so accounts for all low-T chlorite compositions; ideal mixing on site is assumed, with an ordered cationic distribution in tetrahedral and octahedral sites. Applied to chlorite analyses from three distinct low-T environments for which independent T data are available (Gulf Coast, Texas; Saint Martin, Lesser Antilles; Toyoha, Hokkaido), the new pure-Fe2+ thermometer performs at least as well as the recent models, which require an estimate of Fe3+ content. This relief from the ferric iron issue, combined with the simple formulation of the semi-empirical approach, makes the present thermometer a very practical tool, well suited for, for example, the handling of large analytical datasets—provided it is used in the calibration range (T < 350 °C, P < 4 kbar).

The Southern Alps orogen of New Zealand results from late Cenozoic convergence between the Indo-Australian and Pacific plates and is one of the most active mountain belts in the world. Metamorphic rocks carrying a polymetamorphic legacy, ranging from low-greenschist to high-grade amphibolites, are exhumed in the hanging wall of the Alpine Fault. On a regional scale, the metamorphic grade has previously been described in terms of metamorphic zones and mineral isograds; application of quantitative petrology being severely limited owing to unfavorable quartzofeldspathic lithologies. This study quantifies peak metamorphic temperatures (T) in a 300 × 20 km area, based on samples forming 13 transects along-strike from Haast in the south to Hokitika in the north, using thermometry based on Raman spectroscopy of carbonaceous material (RSCM). Peak metamorphic T decreases across each transect from ≥ 640 °C locally in the direct vicinity of the Alpine Fault to less than 330 °C at the drainage divide 15–20 km southeast of the fault. Thermal field gradients exhibit a degree of similarity from the southernmost to the northernmost transects, are greater in low-grade semischist than high-grade schist, are affected by folding or discontinuous juxtaposition of metamorphic zones, and contain limited information on crustal-scale geothermal gradients. Temperatures derived by RSCM thermometry are slightly (≤ 50 °C) higher than those derived by traditional quantitative petrology using garnet–biotite thermometry and THERMOCALC modeling. The age of RSCM T appears to be mostly pre-Cenozoic over most of the area except in central Southern Alps (Franz Josef–Fox area), where the amphibolite facies schists have T of likely Cenozoic age. The RSCM T data place some constraints on the mode of exhumation along the Alpine Fault and have implications for models of Southern Alps tectonics.

The study of continental subduction processes requires detailed Pressure Temperature ( P – T ) paths to understand the kinematic of burial and exhumation of continental units. In the French Western Alps, the Brianconnais zone is a remnant of the continental subduction wedge. P – T conditions have been estimated in its most internal parts, but there is a lack of data in the western part, known as the “Zone houillere”. This Brianconnais Zone houillere is classically divided into two sub-units: the upper and lower Houiller units. This study focuses on both of these in the Claree valley, north of Briancon. In this low-grade metamorphic terrain, estimation of P – T history is complicated because there are few adapted methods and these rocks have a poor metamorphic mineralogical content, including detrital metamorphic minerals inherited from their hercynian history. Therefore, to acquire accurate P – T estimates a multi-method approach is required, involving qualitative and quantitative Raman Study of Carbonaceous Material (RSCM), chemical analysis from quantified X-ray maps and thermodynamic modelling of chlorites and K-white micas. Such multi-approach P – T estimates on a sandstone sample allow distinguishing hercynian peak metamorphic conditions of 371 ± 26 °C and 3.5 ± 1.4 kbar and alpine peak metamorphic conditions of 275 ± 23 °C and 5.9 ± 1.7 kbar. These results are consistent with our RSCM and T max estimates. Raman study conducted on organic-rich schist samples shows an eastward increase of the alpine T max in the upper Houiller unit, from 280 to 300 °C across the Brianconnais Zone houillere. In contrast, carbonaceous material included in detrital grains of muscovite in the sandstone exhibits higher temperatures. This hercynian T max is estimated using thermodynamic modelling at 376 ± 50 °C. According to these results and previous work in more internal parts of the Brianconnais zone, a geodynamic reconstruction is proposed, which is characterized by a diachronous evolution of the Brianconnais zone involved in alpine continental subduction at different times. The geothermal gradient in the Brianconnais zone changes from 8 °C/km during early continental subduction, to 40 °C/km during the collisional event at about 35–30 Ma. The intermediate gradient of 15 °C/km estimated in the Brianconnais Zone houillere suggests that this unit was buried later, than the more internal Brianconnais units, after 40 Ma.

International audience; The composition of the phyllosilicates mica and chlorite is commonly used in thermobarometry to decipher the geological history of rocks. The thermobarometers that have been proposed during the last thirty years rely on the use of electron microprobe (EMP) analyses, with a spatial resolution limited to the micrometer scale. Such a resolution may not be appropriate for the size of clay particles or chemical zoning in very low grade rocks. In this respect, the transmission electron microscope coupled to an X-ray Energy Dispersive spectrometer (TEM-EDX) provides the proper spatial resolution in analysis. It is combined here with Focused Ion Beam (FIB) milling which makes possible in situ preparation of TEM samples with high spatial control and preservation of mineral microtextures. We test the suitability of FIB-milling for TEM-analysis of clay minerals, considering the effects of intrinsic preparation artefacts like amorphization, beam damage, Ga ions implantation and material redeposition. In addition, we evaluate a TEM-EDX analytical protocol adapted to clay minerals and yielding the FIB-section thickness at each analysis point in a non destructive way. The TEM k factors were calibrated on clay powders. A comparison between TEM-EDX and EMP analyses obtained on the same phyllosilicates in FIB and polished sections, respectively, shows excellent agreement, thereby validating the analytical protocol and the use of FIB-sections for the study of clay minerals. The combination of these preparation and analytical procedures opens new avenues for the petrologic study of clay-mineral-bearing assemblages at an unprecedented spatial resolution.

Terra Nova, 23, 85–91, 2011 Abstract Vitrinite reflectance and Raman spectroscopy of carbonaceous material data are used to better resolve the thermal history of the Hsuehshan Range, which is accreted between the foreland fold–thrust belt and bulldozer hinterland units in the Taiwan mountain belt. The observed thermal data indicate that the strata in the northern Hsuehshan Range underwent dynamic metamorphism during the Neogene orogeny, while the strata in the southern Hsuehshan Range may have predominantly experienced burial metamorphism during Palaeogene sedimentation. Based on the thermal constraints, the Hsuehshan Range is interpreted to consist of nappe stacks, originating from the rifted Eurasian continental margin. This interpretation is consistent with well-documented cases in the European Alps and the Himalayas and is also shown in physical modelling and thermo-kinematic studies invoking underplating and erosion processes.

International audience; In the Schistes Lustres of Alpine Corsica (France) serpentinized mantle rocks are associated with continental basement and meta-volcanic/-seclimentary cover rocks. The relationships among these different lithologies are especially well exposed in the Monte San Petrone unit, where Alpine metamorphism reached lawsonite-eclogite conditions. The contact between serpentinites and slivers of continental basement, relatively flat-lying over several kilometers, is characterized by evidence of cataclastic deformation pre-dating Alpine High-Pressure ductile fabrics. The serpentinite/continental basement pair is stratigraphically overlain by metasediments with a typical Jurassic-Cretaceous supra-ophiolitic lithostratigraphy, with metaradiolarites passing upward to marbles and cal cschists. Noticeably, no evidence of cataclastic deformation is found in metasediments. These observations indicate that the lithostratigraphy of the Monte San Petrone unit was established during a pre-Alpine polyphase evolution, which culminated in extensive brittle deformation along a flat-lying detachment fault prior to the deposition of Jurassic sediments. We suggest that the inferred Mesozoic extensional tectonics were related to the opening of the Westem Tethys. The Mesozoic architecture of the Monte San Petrone area, which is typical of an Ocean-Continent Transition (OCT) zone, was preserved despite Alpine deformation and metamorphism, when the different lithologies (i.e. meta-ophiolites, continent-derived rocks and metasediments) underwent a common metamorphic evolution, culminating at T=490-550 degrees C and P= 2.2-2.6 GPa. Similar tectonostratigraphic associations are observed in other high-pressure terranes of Alpine Corsica, suggesting that inherited OCT-type domains may be common in Alpine-type orogens.

International audience; Abstract Graphitizing anthracene-based cokes and non-graphitizing saccharose-based chars were processed at temperatures from 450 °C to 2900 °C at ambient pressure. This offers a whole set of samples that greatly differ in structure. Here, their structural evolution was monitored by combining XRD and visible (green) Raman spectroscopy as well as, for the first time, near-infrared Raman and synchrotron-based C-XANES spectroscopies. These different techniques provide complementary information especially regarding the spatial resolution they achieved. However, despite its importance, the quantitative comparison between the structural parameters extracted from these techniques is difficult. Based on a new signal deconvolution procedure to extract quantitative structural information from C-XANES data and the achievement of a new dataset on a complete series of graphitization, the reliability and the precision of the information which can be retrieved from each technique are discussed. C-XANES spectroscopy appears to provide reliable proxies for the extent of aromatic layers of graphitic compounds and an empirical calibration is proposed.

International audience; New peak metamorphic temperatures are obtained by Raman spectroscopy of Carbonaceous Material to document the thermal structure of the central Western Alps with high sampling resolution. We show that peak metamorphic T gradually increases eastward from

International audience; The Western Alps are a classic subduction-related collisional orogen with well-preserved, deeply subducted ophiolitic remnants of oceanic lithosphere. Some (e.g. Monviso, Voltri) were recognized as a palaeo-subduction channel, with tectonic blocks showing a wide range of pressure-temperature conditions. We herein evaluate for the first time the metamorphic homogeneity of the extensive Zermatt-Saas ophiolite. Zermatt-Saas peak eclogitic assemblages are represented by omphacite-garnet ± phengite ± epidote ± lawsonite ± glaucophane in MORB-derived metabasalts and garnet-chloritoid-talc ± lawsonite ± phengite in hydrothermalized metabasalts. Thermobarometric estimates with thermocalc and Raman Spectroscopy of carbonaceous material reveal homogeneous peak burial conditions at around 540 ± 20 °C and 23 ± 1 kbar. P-T paths indicate that the whole of the ophiolite, at least 60 km across, strikingly underwent similar burial and exhumation patterns and detached from the slab at depths around 80 km. The Zermatt-Saas ophiolite thus appears to be the world's largest oceanic lithosphere fragment exhumed from such depths, which provides important constraints on interplate coupling mechanisms.

International audience; The Taiwan mountain belt is classically viewed as a case example of a critical wedge growing essentially by frontal accretion and therefore submitted to distributed shortening. However, a number of observations call for a significant contribution of underplating to the growth of the orogenic wedge. We propose here a new thermokinematic model of the Taiwan mountain belt reconciling existing kinematic, thermometric and thermochronological constraints. In this model, shortening across the orogen is absorbed by slip on the most frontal faults of the foothills. Crustal thickening and exhumation are sustained by underplating beneath the easternmost portion of the wedge (Tananao Complex, TC), where the uplift rate is estimated to 6.3 mm a1, and beneath the westernmost internal region of the orogen (Hsueshan Range units, HR), where the uplift rate is estimated to 4.2 mm a1. Our model suggests that the TC units experienced a synchronous evolution along strike despite the southward propagation of the collision. It also indicates that they have reached a steady state in terms of cooling ages but not in terms of peak metamorphic temperatures. Exhumation of the HR units increases northward but has not yet reached an exhumational steady state. Presently, frontal accretion accounts for less than 10% of the incoming flux of material into the orogen, although there is indication that it was contributing substantially more (80%) before 4 Ma. The incoming flux of material accreted beneath the TC significantly increased 1.5 Ma ago. Our results also suggest that the flux of material accreted to the orogen corresponds to the top 7 km of the upper crust of the underthrust Chinese margin. This indicates that a significant amount (76%) of the underthrust material has been subducted into the mantle, probably because of the increase in density associated with metamorphism. We also show that the density distribution resulting from metamorphism within the orogenic wedge explains well the topography and the gravity field. By combining available geological data on the thermal and kinematic evolution of the wedge, our study sheds new light onto mountain building processes in Taiwan and allows for reappraising the initial structural architecture of the passive margin.

Continental erosion controls atmospheric carbon dioxide levels on geological timescales through silicate weathering, riverine transport and subsequent burial of organic carbon in oceanic sediments. The efficiency of organic carbon deposition in sedimentary basins is however limited by the organic carbon load capacity of the sediments and organic carbon oxidation in continental margins. At the global scale, previous studies have suggested that about 70 per cent of riverine organic carbon is returned to the atmosphere, such as in the Amazon basin. Here we present a comprehensive organic carbon budget for the Himalayan erosional system, including source rocks, river sediments and marine sediments buried in the Bengal fan. We show that organic carbon export is controlled by sediment properties, and that oxidative loss is negligible during transport and deposition to the ocean. Our results indicate that 70 to 85 per cent of the organic carbon is recent organic matter captured during transport, which serves as a net sink for atmospheric carbon dioxide. The amount of organic carbon deposited in the Bengal basin represents about 10 to 20 per cent of the total terrestrial organic carbon buried in oceanic sediments. High erosion rates in the Himalayas generate high sedimentation rates and low oxygen availability in the Bay of Bengal that sustain the observed extreme organic carbon burial efficiency. Active orogenic systems generate enhanced physical erosion and the resulting organic carbon burial buffers atmospheric carbon dioxide levels, thereby exerting a negative feedback on climate over geological timescales.

International audience; It is commonly believed that high-grade metamorphism erases all traces of fossils and, more generally, of biogenicity in rocks. To address this issue, we report in this study X-ray spectromicroscopy, Raman microspectroscopy, and electron microscopy observations at the nm-scale of fossil lycophytes megaspores found in Triassic metasedimentary rocks from the French Alps. These rocks have undergone high-pressure metamorphic conditions (not, vert, similar 14 kbar, not, vert, similar 360 °C) during the Alpine orogeny corresponding to a burial of not, vert, similar 35 km during subduction. Despite such metamorphism, the fossil megaspores are remarkably well-preserved texturally. An unusual mineralogical zonation consisting of magnetite, ankerite and calcite is superposed on the structures of the spore walls. In parallel, chemical heterogeneities of the organic matter (OM) composing the spore walls were detected. We discuss different interpretations for our observations, in particular a scenario in which these features are remnants of the original structural heterogeneities in the spores, and provide insights on the fossilization processes under high-grade metamorphic conditions. Whatever the processes leading to such heterogeneities, our observations oppose the usual assumption that high-grade metamorphism erases all indications of biogenicity in rocks and open new avenues for investigation at the nm-scale of the evolution of organic matter during diagenesis and metamorphism.