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The Lyngen Magmatic Complex (LMC) is the lowest unit of the Lyngsfjellet Nappe (Upper Allochthon, North Norwegian Caledonides). The fabrics of the LMC rocks range from undeformed to mylonitic. The undeformed rock is a gabbro-norite formed primarily by anorthite-rich (93%) plagioclase, enstatite, and augite. Two deformation events are distinguished in the LMC: (D1) an earlier shearing that has produced a N—S trending vertical foliation with sub-horizontal stretching lineation and dextral sense of shear, and (D2) a top-to-SE-directed thrust contact with the lower nappe series at the base of the meta-gabbro-norite. In the thrust contact region, the early vertical foliation is rotated into a flat-lying orientation and shows an ESE-trending stretching lineation. Deformed fabrics of D1 have developed successively from lower amphibolite, to epidote-amphibolite, and to greenschist metamorphic grades, i.e., on a retrograde temperature-path. The fabrics of the thrust contact have also developed from amphibolite to greenschist conditions.Rock fabrics associated to D1 are dominantly located in the northern portion of the LMC (from Lyngstuva to the north side of the Kjosen fjord). The amphibole compositions of these rocks vary from core to rim, showing a trend from pargasitic to actinolitic composition, consistent with the transition from high- to low-temperature (amphibolite to greenschist facies). U-Pb dating of titanite associated with the greenschist grade in meta-gabbro-norite assemblages indicates a date of 485±9 Ma. This date is interpreted as a deformation/metamorphic age, because the analysed titanite forms from pargasite breakdown and is aligned parallel to the deformed fabric. As this deformation event is synchronous with the crystallization age of the LMC (481±6 Ma, Augland et al., 2014), the deformation associated to the N—S oriented stretching lineation and vertical foliation is linked to sea floor strike slip movements during back-arc spreading of the LMC. D2-rock-fabrics are dominantly located in the southern portion of the LMC and represent typical structures of nappe stacking during the Scandian collisional stage of the Caledonian orogeny. Close to the lower boundary of the LMC, garnet-bearing amphibolites, allow refining the P and T conditions for this unit. Thermobarometric estimates result in conditions of 650°C and 10kbar. This temperature is in contrast with the Raman spectroscopy values averaging around 530°C for the graphite bearing sediments below the lower contact of the LMC, i.e. sediments between the meta-gabbro-norite and the underlying Reisa nappe. The temperature difference between the two deformation events indicates re-heating of the meta-gabbro-norite during the Scandian thrusting.The D1 structural relationships described in the LMC appears common for supra-subduction zone settings, and could potentially be observed at deeper mantle sections as reported in younger analogue tectonic settings as the Wadi al Wasit area of the Oman ophiolite. D2 appears linked to out-of-sequence thrusting at the base of the LMC with respect to the surrounding nappes, contributing to the north Norwegian Caledonides nappe transport sequence.

Alkaline magmatism is an important chemical end-member of magmatic activity that typically occurs in response to small volume melting of asthenospheric- and/or lithospheric mantle material in intra-continental settings. Understanding trace element partitioning and phase equilibria during alkaline magmatism can therefore provide constraints on intra-continental geodynamic settings. However, the partitioning of trace elements between alkaline melts and their dominant equilibrium mineral phases remains poorly constrained. Feldspathoids in particular have received limited attention with regards to their trace element contents, hampering our ability to interpret geochemical trends in alkaline magmatic systems. In this study, we performed a series of 1 atmosphere experiments in a gas-mixing furnace using a variety of highly alkaline (Na2O + K2O = 4.15–14.97 wt%) and silica-undersaturated (SiO2 = 36.73–45.96 wt%) lava compositions from Nyiragongo, Democratic Republic of Congo, in order to investigate the partitioning behaviour of trace elements in minerals from alkaline magmas. Experimental runs were performed with oxygen fugacity buffered at both QFM (quartz-fayalite-magnetite equilibrium) and QFM + 1 and cover a range of geologically-relevant temperatures (1025–1200 °C). The quenched products of these experiments contained leucite, nepheline, melilite, clinopyroxene, olivine, and rhönite crystals, of which glass-crystal pairs were analysed for rare earth elements, large-ion lithophile elements, and high-field-strength elements. Leucite and nepheline host considerable quantities of large-ion lithophile elements but take up negligible amounts of more highly charged cations. Åkermanitic melilite readily incorporates mono- to trivalent cations with a preference for light over heavy rare earth elements, but incorporates only select divalent cations. Rhönite and clinopyroxene have analogous partitioning behaviours, with a strong preference for heavy over light rare earth elements. Fractionation modelling using the reported partitioning behaviours reproduces the 2021 eruption products of Nyiragongo, with 48% fractionation from an olivine-melilitic parental melt composition. Crystallization of trace-element poor feldspathoid amplifies pre-existing high LREE/MREE ratios of the parental magma and progressively increase trace element abundances for all but monovalent cations.

International audience; The metamorphic sole of the Mt. Albert ophiolitic complex (Gaspé peninsula, Quebec, Canada) is a sliver of Ordovician oceanic crust accreted to the base of an incomplete ophiolitic sequence, along a suture zone throughout the north-eastern Appalachians linked to the Taconian orogeny. A detailed mineralogical study of the rocks in the metamorphic section of the sole is provided in this publication: these rocks record valuable information in terms of petrological processes and conditions of accretion, with limited retrogression. The petrology of the metamorphic sole shows that it originates from ocean floor and that it is the equivalent of the Shick-Shock volcanics group, metamorphosed to granulite/higher amphibolite facies. Presence of aluminosilicate bearing metapelites allows constraining pressure conditions in a more robust way than in the case of the famous Semail ophiolite (Oman). Thermobarometric estimates for peak metamorphic conditions for the metamorphic sole of the Mont Albert ophiolitic complex indicate temperatures above 800 °C close to the contact with the overlying peridotite, decreasing to ~650 °C within

International audience; The Queyras-Monviso traverse of the Schistes Lustrés complex, is a stack of underplated nappes of oceanic rocks subducted from blueschist- to eclogite-facies conditions.This study reports on salinities and gas contents of primary fluid inclusions trapped in high pressure veins from metasediments and metamafic rocks (445 fluid inclusions in 22 samples). These data provide snapshots of the compositions of fluids present at peak burial conditions, varying from ~30 to 80 km depth and illustrate the evolution of fluid composition with burial along a cold subduction zone.Fluid inclusions trapped in lawsonite- and carpholite-bearing veins in metasediments contain moderately saline aqueous fluids (average salinity of 4.6 wt% NaCl eq.) with subordinate amounts of CO2 and CH4 in the vapor phase. The observed salinity decrease with increasing grade is interpreted as reflecting progressive dilution of initial seawater-like pore fluid by low-salinity fluids released locally by dehydration reactions. Less-frequently measured higher salinities in the uppermost metasedimentary-dominated tectonic unit suggest brine infiltration from embedded blocks of margin units containing evaporites. CO2 and CH4 (and scarce potential hydrocarbons) appear to be locally released from fluid interaction with carbonates and carbonaceous matter-rich pelitic horizons, respectively.Fluid inclusions in high pressure omphacite veins in metagabbros record higher salinities (mean salinity about 17 wt% NaCl eq.) with small amounts of N2 in eclogitic veins only, and a variety of minerals (calcite, white mica, salts) indicative of complex chemical systems. These high salinities are interpreted as partly inherited from seafloor high-temperature hydrothermal alteration of gabbros, resulting in phase separation and brine formation. Progressive breakdown of hydrothermal Cl-rich amphibole to glaucophane (blueschist-facies) and then omphacite (eclogite-facies) and release of brines trapped in fluid inclusions could account for the high salinity fluids. Therefore, in metagabbros, fluid inclusions record progressive release of Cl in the fluid phase with increasing grade.Fluid signatures of metasediments and metamafics appear characteristic of each rock type. Local fluid signatures and redox conditions were preserved within units, possibly due to restricted and transient fluid circulation (at the hm-scale at most).Fluid inclusions in Alpine metasediments show salinities and gas contents comparable with other subducted fragments of oceanic lithosphere worldwide, whereas fluid salinities of Alpine metagabbros are higher than salinities recorded elsewhere, either due to (1) higher-temperature hydrothermal alteration and brine formation in Alpine metagabbros (compared to metavolcanics) or (2) more restricted infiltration by sediment-derived fluids compared to block-in-mélange subduction complexes.

Subduction zones are crucial features of Earth’s plate tectonics, yet subduction initiation remains enigmatic and controversial. Herein, we reappraise the timing of formation of the first fragments detached from the leading edge of the downgoing slab during subduction initiation (i.e., the Semail metamorphic sole; Oman–United Arab Emirates). Based on geochronology and phase equilibrium modeling, we demonstrate that subduction initiated prior to 105 Ma and at a slow pace (< cm/yr). Subduction stagnated at relatively warm conditions (15–20°C/km) for at least 10 Myr before evolving into a faster (≥ 2–5 cm/yr) and colder (~7°C/km) self-sustained regime. Subduction unlocking at 95-96 Ma, through the progressive change of the interplate thermo-mechanical structure, triggered the onset of slab retreat, large-scale corner flow and fast ocean spreading in the overriding plate. These results reconcile conflicting analogue and numerical subduction initiation models and reveal the thermal, mechanical and kinematic complexity of early subduction steps.

Strain accommodation in upper crustal rocks is often accompanied by fluid-mediated crystallization of phyllosilicates, which influence rock strength and shear zone formation. The composition of these phyllosilicates is commonly used for pressure-temperature-time constraints of deformation events, although it is often highly heterogeneous. This study investigates the reactions producing a phyllosilicate, chlorite, in and below greenschist-facies conditions and the variations in chlorite composition, along a strain gradient in the Bielsa granitoid (Axial Zone, Pyrenees). Compositional maps of chlorite (including iron speciation) are compared to nanostructures observed by transmission electron microscopy in increasingly-strained samples and related to mechanisms of fluid percolation and scales of compositional homogenisation. In the Bielsa granitoid, altered at the late Variscan, Alpine-age shear zones are found with high strain gradients. The undeformed granitoid exhibits local equilibria, pseudomorphic replacement and high compositional heterogeneities in chlorite. This is attributed to: (i) variable element supply and reaction mechanisms observed at nanoscale and (ii) little interconnected intra- and inter-grain nanoporosity causing isolation of fluid evolving in local reservoirs. In samples with discrete and mm-sized fractures, channelized fluid triggered the precipitation of homogeneous Alpine chlorite in fractures, preserving late-Variscan chlorite within the matrix. In low-grade mylonites, where brittle-ductile deformation is observed, micro-, nano-cracks and defects allows the fluid percolating into the matrix at the scale of hundreds of µm. This results in a more pervasive replacement of late-Variscan chlorite by Alpine chlorite. Local equilibria and high compositional heterogeneities in phyllosilicates as chlorite are therefore preserved according (i) matrix-fracture porosity contrasts at nanoscale and (ii) the location and interconnection of nanoporosity between crystallites of phyllosilicates that control reaction mechanisms and element mobility. In low grade mylonites, mineral and compositional replacement remains incomplete despite the high strain.

International audience; Understanding how halogens are distributed among usual hydrous silicates in the lithosphere is important to constrain their deep geochemical cycle and fluid-rock interactions in subduction zones. This article presents firstprinciples modelling of halogen (F-, Cl-, Br-) incorporation in hydrous silicates including mica, chlorite, serpentine, amphibole, epidote and carpholite. The approach allows studying the impact of crystal chemistry on halogen partitioning by quantification of the energetic cost of halogen incorporation in minerals. Calculations are carried out in large systems where halogens are in minor to trace concentrations. Estimations show that F-bearing defects must be separated at least 9 Å from one another to reproduce trace element behaviour, this value increasing to at least 10 Å for Cl and Br. Results highlight the competition between the effects of electrostatic interactions and steric hindrance for incorporation of halogens, where steric hindrance has greater importance for heavy halogens, in particular for Br. Interaction with alkalis is a major control for F incorporation, especially in mica. Other parameters such as octahedral site occupancy, Si/Al ratio of tetrahedral sites and the nature of alkalis in amphibole and mica (K or Na) appear to play subordinate roles. Partition coefficients have been estimated in mineral assemblages in an effort to be representative of subduction zone metamorphism. Results show that pargasite, biotite and lizardite are favoured hosts for all three halogens, followed by clinochlore, tremolite and carpholite. The energetic cost of incorporating halogens into dioctahedral phyllosilicates and epidote is comparatively higher, and partitioning is predicted as unfavourable to these minerals. Fractionation between halogens in subduction zones is predicted by the evolution of mineral assemblages and partition coefficients, a consequence of the influence of crystal chemistry over halogen incorporation in hydrous silicates.

International audience; Strain accommodation in upper crustal rocks is often accompanied by fluid-mediated crystallization of phyllosilicates, which influence rock strength and shear zone formation. The composition of these phyllosilicates is frequently used for pressure-temperature-time constraints of deformation events, although it is often highly heterogeneous, even in mylonites. This study investigates the reactions producing a phyllosilicate, chlorite, in and below grenschist-facies conditions and the variations in chlorite composition along a strain gradient in the Variscan Bielsa granitoid (Axial Zone, Pyrenees). Compositional maps of chlorite including iron speciation are compared to nanostructures observed by transmission electron microscopy in increasingly-strained samples and related to mechanisms of fluid percolation. In the Bielsa granitoid, altered at the late Variscan, Alpine-age shear zones are found with high strain gradients. The undeformed granitoid exhibits local equilibria, pseudomorphic replacement and high compositional heterogeneities in chlorite. This is attributed to variable reaction mechanisms at nanoscale and element supply, little interconnected intra-and inter-grain nanoporosity and isolation of fluid evolving in local reservoirs. In samples with discrete and mm-sized fractures, channelized fluid triggered the precipitation of homogeneous Alpine chlorite in fractures, preserving late-Variscan chlorite within the matrix. In low-grade mylonites, where brittle-ductile deformation is observed, micro and nanocracks and defects allows the fluid percolating into the matrix at the scale of hundreds of µm. This results in a more pervasive but incomplete replacement of late-Variscan chlorite by Alpine chlorite, despite the high strain. In studied granitoids deformed under greenschist-facies conditions, local equilibria and high compositional heterogeneities in phyllosilicates as chlorite are therefore preserved according reaction mechanisms and element mobility controlled by (i) matrix-fracture porosity contrasts at nanoscale and (ii) the location and interconnection of nanoporosity between crystallites of phyllosilicates. This preservation influences our ability to reconstruct the pre-and syn-kinematic metamorphic history of granitic rocks in low-grade units of orogens.

International audience; This study investigates the reactions allowing crystallization of large amounts of lawsonite (CaAl 2 Si 2 O 7 (OH) 2 • [H 2 O]) found in calcschists metamorphosed in a subduction zone setting. Previous studies of lawsonite-forming reactions in metasediments have highlighted its importance for the large-scale budget of CO 2 , as the calcium required to form lawsonite is thought to originate from decarbonation reactions. Yet, thermodynamic modelling as well as isotopic measurements have indicated that 80 to 90% of the carbon is retained in sediments, and there is no evidence of major decarbonation in the field. As lawsonite contains abundant H 2 O and has a large stability field, understanding its crystallization is also important to assess fluid migration and mass transfer in a critical part of the subduction system where slow earthquakes are nucleating (such as low frequency earthquakes or episodic tremor and slip). The upper units of the blueschist facies metasediments of the Schistes Lustrés complex (Western Alps), buried to depths of~30-40 km, have been selected as an ideal case study as they host up to 40 vol% of lawsonite. Lawsonite is found crystallized over several generations, in veins and in reactions fronts as well as in the rock matrix. Three types of lawsonite were identified. The most abundant type of lawsonite is associated with quartz and ankerite. This assemblage formed from phyllosilicates and calcite in a continuous reaction: chlorite + calcite + kaolinite = lawsonite + ankerite + quartz + H 2 O. According to thermodynamic modelling, this reaction is restricted to a narrow pressure-temperature domain and initiates around 180°C and 0.4 GPa. Lawsonite is also observed and predicted to grow from Fe-Mg-carpholite at higher metamorphic conditions. None of these reactions allow efficient net export of carbon, as one carbonate replaces another, and most observations are consistent with closed-system behaviour at outcrop-scale, in agreement with geochemical studies. At sample-scale and below, crystallization of lawsonite is linked to homogenization of carbonate and pelitic domains in geologically fast reactions. Dissolution of calcite produces reactive fluids prone to react with pelitic domains and crystallize lawsonite and another carbonate. Although metamorphic veins are ubiquitous to the upper units of the Schistes Lustrés Complex, most of them result from local reactions and do no indicate large-scale mass transfer.

Metamorphic soles are m to ~500 m thick tectonic slices welded beneath most large- scale ophiolites (usually ~20 km thick). They typically show a steep inverted metamorphic structure where the pressure and temperature (T) conditions of crystallization increase upward, from the base of the sole (500 ± 100°C at 0.5 ± 0.2 GPa) to the contact with the overlying peridotite (800 ± 100°C at 1.0 ± 0.2 GPa). The inverted T gradient was historically interpreted as a result of heat transfer from the incipient mantle wedge toward the nascent slab synchronously with the overlying ophiolite formation (within only 1-2 Myrs). Their mineralogical assemblage and deformation pattern provide major constraints on the nature and the timing of the processes controlling the dynamics of the plate interface during early subduction.Soret et al. (2017, 2019) recently reappraised the tectonic–petrological model for the formation of metamorphic soles below ophiolites, showing that the present-day structure of the sole results from the successive stacking of several homogeneous oceanic crustal slivers (without internal T gradient). This stacking marks the evolution of rheological properties of slab material and peridotites of the upper plate as the plate interface progressively cools (Agard et al., 2016). These findings outline the thermal and mechanical complexity of early subduction dynamics, and highlight the need for refined numerical modelling studies.Lu-Hf geochronology on garnet from the Oman metamorphic sole has recently shown that the earliest accreted subunit, found directly against the upper plate mantle, was initially buried ≥ 8 Ma earlier than previously estimated (Guilmette et al., 2017). These results imply initiation ≥ 8 Ma before the formation of the ophiolite, which underscores the common belief that ophiolite-sole couples record spontaneous subduction initiation and rather indicates far-field forcing long before upper plate extension and mantle upwelling.We herein present new U-Pb titanite and monazite petrochronology across the different sub-units of the Oman metamorphic sole. Our results confirm the time lag of several million years between subduction initiation and the ophiolite formation, therefore supporting the recently proposed model of far-field forced subduction initiation. They also reveal a significant time lag between the underplating and exhumation of each sub-unit of the sole.

Halogens are volatile elements of great interest for the study of fluid-rock interactions between minerals of metamorphic and mantle rocks. Constraining the partitioning of these elements between minerals is also key to understanding their deep geochemical cycle. Hydrous silicates such as micas, amphiboles, chlorites, epidotes or serpentines often contain minor to trace amounts of halogens incorporated by the OH- = X- (X- = F-, Cl-, Br- or I-) mechanism. Their abundance in metamorphic and mantle rocks grants them a major role in storing and transporting halogens through the subduction zone. However, low halogen concentrations hamper in situ analyses, and quantifying the partitioning of low-concentrated halogens remains then very challenging.The present study focusses on incorporation of halogens (F-, Cl-, Br-, I-) into hydroxyl sites in phyllosilicates and amphiboles, on both analytical and theoretical grounds.In situ measurements in minerals using electron probe microanalysis and LA-ICP-MS/MS have been carried out, allowing investigation of minor to ultra-trace halogen concentrations. Average detection limits with the electron probe are of 200 ppm for F and 35-40 ppm for Cl, Br and I. LA-ICP-MS/MS allowed simultaneous measurement of Cl, Br and I, reaching detection limits of about 50-100 ppm of Cl, 1-10 ppm of Br and well below 1 ppm for I. Calibrations have been carried out using international and house standards. Halogen ratios and partition coefficients between minerals have been measured.Ab-initio modelling of the OH- = X- exchange in phyllosilicate end-members of interest (e.g. phlogopite, muscovite, clinochlore) is underway (CRYSTAL17, Dovesi et al., 2014). Halogen-bearing defects are modelled as diluted as much as possible in crystals (≤ 1 wt. %) to mimic trace concentrations. Crystal strain and energetic cost of the substitution as well as theoretical partition coefficients have been computed and compared between optimised structures. Comparison of F and Cl partitioning between Mg-biotite and muscovite shows that the effect of dioctahedral vacancies over the position of hydroxyl groups strongly influences halogen partitioning, where F and Cl distribute in favour of biotite. Forthcoming modelling will quantify the strain and energetic impact of halogen incorporation in chlorite and amphibole end-members. ReferenceDovesi, R.; Orlando, R.; Erba, A.; Zicovich-Wilson, C. M.; Civalleri, B., … Kirtman, B. (2014). International Journal of Quantum Chemistry, 114(19), 1287–1317.

Using partition coefficients is extremely useful to model melting processes and fluid-rock interactions. However, partition coefficients values remain scarce in regard of their sensitivity to mineral composition and to the variability of mineral composition. In addition, the inferred equilibrium between phases is not necessarily reached, even in high-grade metamorphic conditions associated to melting. Disequilibrium may dramatically hamper the effective mobility of species and lead to element distribution far from the predicted values.This contribution aims at estimating partition coefficients for chromium (Cr) between garnet and clinopyroxene, and testing them in natural rocks of various metamorphic grades. As a poorly mobile trivalent element, Cr is chosen as a proxy to rare earth elements.Theoretical partition coefficients for Cr between garnet and clinopyroxene are calculated ab initio from structures where Cr3+ is modelled as a defect in Al3+ sites using CRYSTAL17 (Dovesi et al., 2014) and the thermodynamic description of Dubacq and Plunder (2018). Results are compared to electron microprobe measurements in mineral assemblages containing tens to thousands of ppm of Cr, where element mapping brings much information. Results of ab initio computations highlight the role of crystal-chemistry over the strain field around point defects, controlling the dynamics of the Cr3+ = Al3+ exchange between clinopyroxene and garnet. As expected, the partitioning of Cr between garnet and clinopyroxene depends strongly on the grossular and pyrope content: Cr incorporates grossular preferentially to jadeite, but jadeite incorporates Cr preferentially to pyrope.Comparison between predicted and measured partition coefficients allowed to estimate the deviation from equilibrium. Disequilibrium is evidenced even for samples metamorphosed around 850°C, as shown by the distribution of Cr-rich and Cr-depleted domains. Disequilibrium is attributed to slow diffusivity of Cr in fluid and at grain boundaries during crystal growth, leading to interface-coupled dissolution-precipitation.Dovesi, R., Orlando, R., Erba, A., Zicovich‐Wilson, C. M., Civalleri, B., Casassa, S., ... & Noël, Y. (2014). CRYSTAL14: A program for the ab initio investigation of crystalline solids. International Journal of Quantum Chemistry, 114(19), 1287-1317.Dubacq, B., & Plunder, A. (2018). Controls on trace element distribution in oxides and silicates. Journal of Petrology, 59(2), 233-256.

International audience; This contribution investigates mechanisms controlling subduction development and stabilization over time (coined as 'slabitization'), from a nascent slab to a mature slab viscously coupled to mantle convection, from grain scale to plate tectonics scale. Frozen-in, deep and warm portions of the subduction plate interface with both sides still preserved are found at the base of ophiolites in almost pristine state. Both sides record changes in the mineralogy, structure, fluid content and rheology due to devolatilization of subducting metamorphic rocks. They allow characterizing the evolution, shortly after subduction initiation (~1–10 Ma), of interplate coupling, mantle resistance to slab penetration or incipient mantle wedge metasomatism, as well as transformations occurring at depth in warm or cold subduction zones today.This study combines structural field work, mineralogical and crystallographic data, detailed petrology, thermodynamic modelling and geochemistry from/on both sides of the plate interface, i.e. the base of the mantle wedge (basal ophiolitic peridotites) and crustal fragments from the slab (metamorphic soles). Data collected across the entire Semail ophiolite (Oman, UAE territory) and other similar settings worldwide (e.g., Canada, Turkey, New Caledonia) show a continuous evolution of the subduction plate interface from 1.2–0.9 GPa 900–750 °C to 0.7–0.5 GPa 750–600 °C, with progressive localization of strain and fluid transfer. Crystallization of neo-formed minerals, enrichment in fluid-mobile elements and their isotopic signature (e.g., for boron) indicate that metasomatism of the mantle base results from interaction with subduction fluids derived from the dehydrating metamorphic sole and slab tip, migrating at velocities ~1–10 m/a. Coeval deformation and metamorphic reactions in metabasalts of the downgoing slab reveal the importance of mineral changes (e.g., amphibole content) and deformation modes in controlling fluid delivery, stepwise detachment and accretion of successive slices from the downgoing slab (HTa, HTb and then LT soles) to the mylonitized mantle.This study demonstrates how the interplay between metamorphic reactions, fluid/melt transfer and deformation mechanisms, in particular dissolution-precipitation creep (DPC), controls the mechanical coupling state of the plate interface: (i) suppression of fluid transfer and DPC at depth triggers the onset of viscous coupling. This occurs near ~ 30 km depth during subduction infancy and HTa sole formation; (ii) with increased cooling and fluid availability, strain localization progressively develops downwards and unzips the subduction interface. The downward migration of viscous coupling triggers localized mantle wedge upwelling, potentially leading to short-lived suprasubduction ophiolite or forearc lithosphere formation; (iii) the locus of viscous coupling stabilizes near ~80–100 km in mature (and cold) subduction zones, and sets mantle counterflow. This is where and when plates get reattached and slabs become part of the mantle convection system.Recent geochronological data suggest that the duration from subduction nucleation to ophiolite formation is probably slower than suspected (~5–10 Ma), and that another 5–10 Ma may be needed to reach mature subduction and profuse arc magmatism. These results refine our view of the subduction factory and have important implications for how, how much, and which sort of fluid is being fluxed into the mantle wedge at depths where serpentine is no longer stable.

International audience; Pre‐kinematic greenschist facies metamorphism is often observed in granites and basement units of mountain belts, but rarely dated and accounted for in orogenic cycle reconstructions. Studying pre‐kinematic alteration is challenging because of its usual obliteration by subsequent syn‐kinematic metamorphism often occurring at conditions typical of the brittle–ductile transition. It is, however, to be expected that pre‐kinematic alteration has major implications for the rheology of the upper crust. In the 305 Ma‐old Variscan basement of the Bielsa massif (located in the Axial Zone of the Pyrenees), successive fluid–rock interaction events are recorded in granites below 350°C. Combined microstructural and petrographic analysis, low‐T thermobarometry and in situ U–Th/Pb dating of anatase, titanite and monazite show extensive pre‐orogenic (pre‐Alpine) and pre‐kinematic alteration related to feldspar sericitization and chloritization of biotite and amphibole at temperatures of 270–350°C at 230–300 Ma. This event is followed by a second fluid–rock interaction stage marked by new crystallization of phyllosilicates at 200–280°C and is associated with the formation of mylonitic shear zones and fractures parallel to the shear planes. U–Pb anatase and monazite ages as well as the microtextural relationships of accessory minerals suggest an age for this event at 40–70 Ma, consistent with independent regional geology constraints. The Variscan basement was therefore softened at late to post‐Variscan time, at least 150–200 Ma before the main Alpine shortening while Alpine‐age compression (c. 35–50 Ma) leads to the formation of a dense net of mylonites. The associated deformation, both distributed at the scale of the Bielsa massif and localized at decametric scale in mylonitic corridors, precedes the strain localization along the major thrusts of the Axial Zone. The Bielsa massif is a good example where inherited, pre‐orogenic upper crustal softening controls the deformation patterns in granitic basement units through low‐grade metamorphic reactions.

The strength of the lithosphere may be constrained qualitatively by field observations on localized vs distributed modes of deformation and by the mineral assemblages formed during deformation. The internal deformation of the Bielsa basement unit of the Pyrenean Axial zone is investigated through structural, microstructural and thermometric data. In this area, shortening is widely distributed as attested by the folded attitude of the interface between the basement and its sedimentary Triassic cover. Shortening is estimated around 1.7 km (13%) from a regional balanced cross-section and should be considered in pre-Pyrenean reconstructions. Shortening probably occurred before strain localization on crustal ramps as suggested by zircon fission-track analysis. Distributed shortening is characterized at small-scale by low-temperature mylonites and cataclasites. In thin-section, feldspar originally present in the magmatic protolith is partially to totally sericitized. This transformation led to significant weakening of the rock and took place in the 250–350 °C temperature range. Sericitization is ubiquitous, even in un-deformed granodiorites. This shows that the weakening effect of sericitization not only occurs in ultra-mylonites, ultra-cataclasites and phyllonites but also more generally in the upper crust early during the shortening history, with implications for the shortening style. Estimates of the geothermal gradient suggest that inherited thermicity may also have influenced the style of shortening. We propose that the upper crust was very weak before or at the onset of its shortening due to high-thermal gradients and fluid circulation that induced large-scale sericitization in greenschist facies conditions. This has strong implications on the rheological evolution of the upper crust submitted to metamorphic alteration in the greenschist facies and below.

International audience; Chlorite is a ubiquitous product of metamorphism, alteration of magmatic rocks and hydrothermal processes owing to its large stability field and wide compositional range. Its composition is governed by several substitutions and has been used as a geothermometer, on the basis of empirical, semi-empirical, and thermodynamic models. As in some other phyllosilicates of petrological interest, the oxidation state of iron in chlorite may differ from the usually assumed divalent state. However, the crystal chemistry of trivalent iron in chlorite remains poorly known, and the thermodynamic properties of ferric chlorite are missing from databases used for petrological modeling. As part of an attempt to fill this gap, we present results from in situ, micrometer-scale measurements of the oxidation state of iron in various chlorite-bearing samples. X-ray absorption near-edge spectroscopy (XANES) was combined with electron probe microanalysis (EPMA) on the same crystals. Results show iron oxidation states varying from ferrous to ferric; iron is in octahedral coordination in all ferromagnesian chlorites but to ~25% tetrahedral in the lithian chlorite cookeite (1.0 wt% Fe2O3(total)). Absolute amounts of ferric iron cover an unprecedented range (0 to ~30 wt% Fe2O3). For highly magnesian, ferric chlorite, Fe concentrations are low and can be accounted for by Al = Fe3+ substitution. In Fe-rich samples, Fe3+ may exceed 2 atoms per formula unit (pfu, 18 oxygen basis). When structural formulas are normalized to 28 charges corresponding to the standard O10(OH)8 anionic basis, these measurements define the exchange vector of a di-trioctahedral-type substitution: 3 VI(Mg, Fe2+) = VI☐ + 2 VIFe3+, as described in earlier studies. However, structural formulas calculated on the basis of the oxygen contents actually measured by EPMA show that this trend is an artifact, due to the neglect of variations in the number of protons in the structure. Our measurements indicate increasing hydrogen deficiency with increasing Fe3+ content, up to ~ 2 H+ pfu in the Fe3+-rich chlorite samples, corresponding to a net exchange vector of the type R2+ + H+ = Fe3+. These results do not support substitutions toward di-trioctahedral ferric end-members, and highlight the need for considering substitution toward an “oxychlorite” (i.e., H-deficient) ferric component, close to tri-trioctahedral, with an O12(OH)6 anionic basis, even in green, pristine-looking chlorite. The effects of iron oxidation and H deficiency on chlorite geothermometers were explored. They are deterring if H deficiency is ignored but, given the sensitivity of most thermometers to octahedral vacancy, the assumption FeTotal = Fe2+ is still safer than using high measured Fe3+ contents and the standard 28 charge basis, which artificially increases vacancies. In such ferric chlorites, EPMA measurement of oxygen allows a fair estimate of H content if Fe3+/Fe2+ is known; it should be more systematically implemented. For the same reasons, literature data reporting Fe3+-rich chlorite with vacancy content along the possibly artificial di-trioctahedral-type substitution should be verified. With the help of constraints from thermodynamic models, charge balance, crystal symmetry, and proton loss, a new cation site distribution is proposed for di-tri- to tri-trioctahedral chlorites in the Fe2+-Fe3+-Mg-Al-Si-O-H system, allowing a more realistic thermodynamic handling of their solid solutions.

This study sheds light on the deformation mechanisms of subducted mafic rocks metamorphosed at amphibolite and granulite facies conditions and on their importance for strain accommodation and localization at the top of the slab during subduction infancy. These rocks, namely metamorphic soles, are oceanic slivers stripped from the downgoing slab and accreted below the upper plate mantle wedge during the first million years of intraoceanic subduction, when the subduction interface is still warm. Their formation and intense deformation (i.e., shear strain ≥5) attest to a systematic and transient coupling between the plates over a restricted time span of ∼1 Myr and specific rheological conditions. Combining microstructural analyses with mineral chemistry constrains grain-scale deformation mechanisms and the rheology of amphibole and amphibolites along the plate interface during early subduction dynamics, as well as the interplay between brittle and ductile deformation, water activity, mineral change, grain size reduction and phase mixing. Results indicate that increasing pressure and temperature conditions and slab dehydration (from amphibolite to granulite facies) lead to the nucleation of mechanically strong phases (garnet, clinopyroxene and amphibole) and rock hardening. Peak conditions (850 ∘C and 1 GPa) coincide with a pervasive stage of brittle deformation which enables strain localization in the top of the mafic slab, and therefore possibly the unit detachment from the slab. In contrast, during early exhumation and cooling (from ∼850 down to ∼700 ∘C and 0.7 GPa), the garnet–clinopyroxene-bearing amphibolite experiences extensive retrogression (and fluid ingression) and significant strain weakening essentially accommodated in the dissolution–precipitation creep regime including heterogeneous nucleation of fine-grained materials and the activation of grain boundary sliding processes. This deformation mechanism is closely assisted with continuous fluid-driven fracturing throughout the exhumed amphibolite, which contributes to fluid channelization within the amphibolites. These mechanical transitions, coeval with detachment and early exhumation of the high-temperature (HT) metamorphic soles, therefore controlled the viscosity contrast and mechanical coupling across the plate interface during subduction infancy, between the top of the slab and the overlying peridotites. Our findings may thus apply to other geodynamic environments where similar temperatures, lithologies, fluid circulation and mechanical coupling between mafic rocks and peridotites prevail, such as in mature warm subduction zones (e.g., Nankai, Cascadia), in lower continental crust shear zones and oceanic detachments.

International audience; The basal mantle of the Semail ophiolite directly overlying the metamorphic sole has been affected by a late and relatively low temperature ductile deformation event, ascribed to the deformation of the mantle just above the plate interface during subduction infancy (which ultimately led to ophiolite obduction). We show that this deformation results in the formation of proto-mylonitic (∼850–750°C) to ultra-mylonitic (∼750–650°C) shear zones wrapping lenses of porphyroclastic tectonites deformed at higher temperature (∼1200°C). In proto- to ultra-mylonites, syn-deformation hydrous fluid/peridotite interaction triggered the dissolution of coarser grains (olivine1, orthopyroxene1 and clinopyroxene1) and the crystallization of polymineralic mixtures of smaller grains (olivine2, orthopyroxene2, clinopyroxene2, spinel2 ± sulfide, together with magnesio-hornblende to pargasitic amphibole). This modal metasomatism is associated with cryptic metasomatism marked by striking mineral enrichment in some fluid-mobile-elements (especially B and Li). From the major and trace elements composition of the newly precipitated grains and estimated conditions of fluid/peridotite interaction (∼800°C), we interpret the metasomatic agent as a fluid derived from the dehydration of the amphibolitic to granulitic metamorphic sole (i.e. the metamorphosed crust from the downgoing plate) underlying the mantle during incipient subduction. We propose that this high temperature sole was accreted to the proto-mylonitic banded unit while dehydrating and that both units were exhumed together during peridotite ultra-mylonitic deformation, thereby preserving a fossilized warm subduction interface and evidence of an incipiently (de)forming mantle wedge.

International audience; Despite decades of petrological and geochemical studies, the nature and setting of obducted ophiolites remain controversial: the influence of supra-subduction zone environments on pre-existing oceanic lithosphere is yet to assess, and the processes leading to subduction/obduction initiation are still poorly constrained. Our study documents successive influx of slab-derived fluids and progressive strain localization within the upper mantle in a supra-subduction environment during the first few My of the subduction history. We focus on strongly sheared mafic amphibolites intruding peridotites near the mantle–crust transition of the New Caledonia obducted ophiolite and ~ 50 to 100 m above the basal thrust contact of the ophiolite. These m- to hm-long and several m-thick shear bands are interpreted as inherited small-scale intrusions of mafic melts, probably dikes or sills, which were derived from a moderately refractory mantle source refertilized by supra-subduction zone fluids. 40Ar/39Ar age constraints on pargasite at ca. 90 Ma suggest that they could be inherited from the former Pacific west-dipping subduction.Secondary deformation of these mafic intrusions is intimately associated to three major stages of fluid infiltration: (1) the first stage of deformation and metasomatism is marked by syn-kinematic growth of Ca-amphibole (at 700–800 °C and 3–5 kbar) with a distinctive supra-subduction zone signature, and controlled later channelization of aqueous fluids. 40Ar/39Ar dating on magnesio-hornblende indicates that this deformation episode occurred at ca. 55 Ma, coincident with east-dipping subduction initiation; (2) the main metasomatic stage, characterized by the development of a phlogopite-rich matrix wrapping peridotites and amphibolite boudins, points to the percolation of alkali-rich aqueous fluids at still high temperature (650–750 °C); (3) the last, low temperature (< 600 °C) metasomatic stage results in the formation of deformed veinlets containing talc, chlorite and serpentine.

Metamorphic soles are tectonic slices welded beneath most large-scale ophiolites. These slivers of oceanic crust metamorphosed up to granulite facies conditions are interpreted as forming during the first million years of intra-oceanic subduction following heat transfer from the incipient mantle wedge towards the top of the subducting plate. This study reappraises the formation of metamorphic soles through detailed field and petrological work on three key sections from the Semail ophiolite (Oman and United Arab Emirates). Based on thermobarometry and thermodynamic modelling, it is shown that metamorphic soles do not record a continuous temperature gradient, as expected from simple heating by the upper plate or by shear heating as proposed in previous studies. The upper, high-temperature metamorphic sole is subdivided in at least two units, testifying to the stepwise formation, detachment and accretion of successive slices from the down-going slab to the mylonitic base of the ophiolite. Estimated peak pressure-temperature conditions through the metamorphic sole, from top to bottom, are 850°C and 1 GPa, 725°C and 0.8 GPa and 530°C and 0.5 GPa. These estimates appear constant within each unit but differing between units by 100 to 200°C and ~0.2 GPa. Despite being separated by hundreds of kilometres below the Semail ophiolite and having contrasting locations with respect to the ridge axis position, metamorphic soles show no evidence for significant petrological variations along strike. These constraints allow us to refine the tectonic–petrological model for the genesis of metamorphic soles, formed via the stepwise stacking of several homogeneous slivers of oceanic crust and its sedimentary cover. Metamorphic soles result not so much from downward heat transfer (ironing effect) as from progressive metamorphism during strain localization and cooling of the plate interface. The successive thrusts originate from rheological contrasts between the sole, initially the top of the subducting slab, and the peridotite above as the plate interface progressively cools. These findings have implications for the thickness, the scale and the coupling state at the plate interface during the early history of subduction/obduction systems. This article is protected by copyright. All rights reserved.

International audience; The dissolution of CO 2 into formation brines and the subsequent reactions of the CO 2-charged brines with reservoir minerals are two key processes likely to increase the security of geological carbon-dioxide storage. These processes will be dependent on the permeability structure and mineral compositions of the reservoirs, but there is limited observational data on their rates. In this paper we report the cation and anion concentrations and Sr, oxygen and carbon isotopic compositions of formation waters from four extraction wells sampled at surface, over~6 months after commencement of CO 2 injection in a five spot pattern for enhanced oil recovery at the Salt Creek field, Wyoming. Sampled fluids, separated from the minor oil component, exhibit near-monotonic increases in alkalinity and concentrations of cations but little change in Cl and Br concentrations and oxygen and deuterium isotope ratios. The increases in alkalinity are modelled in terms of reaction with reservoir calcite and silicate minerals as the changes in fluid chemistry and Sr-isotopic compositions are inconsistent with simple addition of injected fluids sampled over the course of the experiment. The reservoir mineral chemical and isotopic compositions are characterised by sampling core as well as surface exposures of the Frontier Formation elsewhere in Wyoming. The evolution of the fluid chemistries reflects extensive dissolution of both carbonate and silicate minerals over the course of the six months sampling implying rapid dissolution of CO 2 in the formation waters and reaction of CO 2-bearing brines with formation minerals. Rates of CO 2 diffusion into the brines and advection of CO 2 charged brines in the reservoir are sufficiently slow that, if present, calcite should react to be close to equilibrium with the fluids. This allows estimation of the CO 2 partial pressures in the sampled fluids and comparison with the thermodynamic driving force for the relatively rapid average plagioclase dissolution rates of~10 − 12 mol•m − 2 •s − 1 .

Mobilization of contaminants by CO2-charged brines is one concern relating to injection of CO2 as part of carbon capture and storage projects. This study monitors the mobility of trace metals in an exhumed CO2-charged aquifer near the town of Green River, Utah (USA), where CO2-charged brines have bleached red sandstones, and concentrated trace metals at the bleaching reaction front. Mass balance calculations on the trace metal enrichments are used to calculate time-integrated fluid fluxes and show that a significant fraction of the metals mobilized by the CO2-rich brines are redeposited locally. A sequential extraction procedure on metal-enriched samples shows that these metals are incorporated into secondary carbonate and oxide phases which have been shown to grow at the CO2-promoted bleaching reaction front. We argue that while CO2-charged brines are capable of mobilizing trace metals, local metal redeposition implies that the potential for contamination of overlying freshwater aquifers is low.

CO2 sequestration is regarded as an important strategy for reducing anthropogenic CO2 emissions. Both the nature and rate of fluid–mineral reactions in CO2–water–rock systems are crucial, yet poorly constrained, parameters in understanding the fate of CO2 injected in geological formations. This study models reactions and reaction rates in an exhumed CO2-charged aquifer where CO2-rich brines have bleached red sandstones by dissolution of hematite grain coatings. We show that the vertical movement of the reaction front is dominated by diffusion and this allows calculation of reaction rates for the dissolution of hematite grain coatings and K-feldspar. Using mineral surface areas calculated from BET measurements, we estimate K-feldspar dissolution rates of 3.4 ± 2.0 × 10 − 13 mol m − 2 s − 1 ; and hematite reaction rates of 6.1 ± 5.0 × 10 − 16 mol m − 2 s − 1 . The rates for K-feldspar are lower than previous, experimentally derived, estimates of K-feldspar dissolution rates by 1–2 orders of magnitude, likely explained by the proximity of the natural system to equilibrium. The inferred hematite reaction rates are 5–6 orders of magnitude slower than laboratory experiments and appear to be controlled by the chemical gradients imposed by the more sluggish K-feldspar dissolution. As the majority of potentially mobile trace metals are hosted in iron-oxide grain coatings, we argue that the rate of contaminant mobilization by CO2-charged brines will be lower than suggested by laboratory experiments.

The arguments of Nieto et al. (2010) in favor of the incorporation of H3O+ rather than H2O in interlayer positions of illite are disputable. Stoichiometric arguments suggest that the excess water in the Silver Hill illite is in the form of H2O. Moreover, recent thermodynamic models assuming the incorporation of interlayer H2O in illite provide reasonable estimates of temperature and water content using the AEM/TEM analyses of Nieto et al. (2010).

International audience; Subduction infancy corresponds to the first few million years following subduction initiation, when slabs start their descent into the mantle. It coincides with the transient (yet systematic) transfer of material from the top of the slab to the upper plate, as witnessed by metamorphic soles welded beneath obducted ophiolites. Combining structure–lithology–pressure–temperature–time data from metamorphic soles with flow laws derived from experimental rock mechanics, this study highlights two main successive rheological switches across the subduction interface (mantle wedge vs. basalts, then mantle wedge vs. sediments; at ∼800 °C and ∼600 °C, respectively), during which interplate mechanical coupling is maximized by the existence of transiently similar rheologies across the plate contact. We propose that these rheological switches hinder slab penetration and are responsible for slicing the top of the slab and welding crustal pieces (high- then low-temperature metamorphic soles) to the base of the mantle wedge during subduction infancy. This mechanism has implications for the rheological properties of the crust and mantle (and for transient episodes of accretion/exhumation of HP-LT rocks in mature subduction systems) and highlights the role of fluids in enabling subduction to overcome the early resistance to slab penetration.

International audience; Modelling the progress of geochemical processes in CO₂storage sites is frustrated by uncertainties in the rates of CO₂ flow and dissolution, and in the rates and controlling mechanisms of fluid-mineral reactions that stabilise the CO₂ in geological reservoirs. Dissolution of CO₂ must be controlled by the complexities of 2-phase flow of CO₂ and formation brines and the smaller-scale heterogeneities in the permeability in the reservoirs which increase the fluid contact areas. The subsequent fluid mineral reactions may increase storage security by precipitating CO₂ in carbonate minerals but the consequences of fluid-mineral reactions on caprock rocks or potential leakage pathways up fault zones are less certain as the CO₂-charged brines may either corrode minerals or decrease permeabilities by precipitating carbonates. Observations from CO₂-injection experiments and natural analogues provide important constraints on the rates of CO₂ and brine flow and on the progress of CO₂ dissolution and mineral-fluid reactions. In these experiments brines in contact with the propagating plume appear to rapidly saturate with CO₂. Dissolution of the CO₂ drives the dissolution of oxide and carbonate minerals, on times scales of days to weeks. These reactions buffer fluid pH and produce alkalinity such that carbonate dissolution moves to carbonate precipitation over time-scales of weeks to months. The dissolution of Fe-oxide grain coatings and the release of Fe to solution is important in stabilising insoluble Fe-Mg-Ca carbonate minerals but the rate limiting step for carbonate mineral precipitation is the transport of CO₂-charged brines and silicate mineral dissolution rates. Observations from CO₂-EOR experiments and natural analogues suggest that the silicate mineral dissolution reactions are initially fast in the low pH fluids surrounding the CO₂ plume but that reaction progress over months to years drives minerals towards thermodynamic equilibrium and dissolution rates slow over 2-5 orders of magnitude as equilibrium is approached. The sluggish dissolution of silicate minerals is likely to preside over the long-term fate of the CO₂ in geological reservoirs. Observations from injection experiments and natural analogues suggest that the potentially harmful trace elements mobilised by the drop in pH are immobilised as adsorbed and precipitated phases as fluid pH is buffered across mineral reaction fronts. There are very few observations of caprock exposed to CO₂-rich brines. Preliminary examination of core recently recovered from scientific drilling of a natural CO₂ accumulation in Utah suggests that the diffusion of CO₂ into reservoir caprocks drives dissolution of Fe-oxides but subsequent precipitation of carbonate minerals likely retards the diffusion distance of the CO₂. At this site thin siltstone layers are shown to be effective seals to the CO₂-charged fluids, which has significant implications for the long term security of CO₂ in geological reservoirs.

International audience; XMapTools is a MATLAB©-based graphical user interface program for electron microprobe X-ray image processing, which can be used to estimate the pressure-temperature conditions of crystallization of minerals in metamorphic rocks. This program (available online at http://www.xmaptools.com) provides a method to standardize raw electron microprobe data and includes functions to calculate the oxide weight percent compositions for various minerals. A set of external functions is provided to calculate structural formulae from the standardized analyses as well as to estimate pressure-temperature conditions of crystallization, using empirical and semi-empirical thermobarometers from the literature. Two graphical user interface modules, Chem2D and Triplot3D, are used to plot mineral compositions into binary and ternary diagrams. As an example, the software is used to study a high-pressure Himalayan eclogite sample from the Stak massif in Pakistan. The high-pressure paragenesis consisting of omphacite and garnet has been retrogressed to a symplectitic assemblage of amphibole, plagioclase and clinopyroxene. Mineral compositions corresponding to $165,000 analyses yield estimates for the eclogitic pressure-temperature retrograde path from 25 kbar to 9 kbar. Corresponding pressure- temperature maps were plotted and used to interpret the link between the equilibrium conditions of crystallization and the symplectitic microstructures. This example illustrates the usefulness of XMapTools for studying variations of the chemical composition of minerals and for retrieving information on metamorphic conditions on a microscale, towards computation of continuous pressure-temperature-and relative time path in zoned metamorphic minerals not affected by post-crystallization diffusion.

International audience; We present a semi-empirical thermodynamic model with uncertainties that encompasses the full range of compositions in H2 O-CO2 -NaCl mixtures in the range of 10-380°C and 1-3500 bars. For binary H2O-CO2 mixtures, the activity-composition model is built from solubility experiments. The parameters describing interactions between H2O and CO2 are independent of the absolute thermodynamic properties of the end-members and vary strongly non-linearly with pressure and temperature. The activity of water remains higher than 0.88 in CO2-saturated solutions across the entire pressure-temperature range. In the H2O-NaCl system, it is shown that the speciation of aqueous components can be accounted for by a thermodynamic formalism where activities are described by interaction parameters varying with intensive properties such as pressure and temperature but not with concentration or ionic strength, ensuring consistency with the Gibbs-Duhem relation. The thermodynamic model reproduces solubility experiments of halite up to 650°C and 10 kbar, and accounts for ion pairing of aqueous sodium and chloride ions with the use of associated and dissociated aqueous sodium chloride end-members whose relative proportions vary with salinity. In the H2O-CO2-NaCl system, an activity-composition model reproduces the salting-out effect with interactions parameters between aqueous CO2 and the aqueous species created by halite dissolution. The proposed thermodynamic properties are compatible with the THERMOCALC database (Holland and Powell, J.M.G., 2011, 29, 333-383) and the equations used to retrieve the activity model in H2O-CO2 can be readily applied to other systems, including minerals.

International audience; The timing of onset of modern-style plate tectonics is debated. The apparent lack of blueschist metamorphism1--a key indicator of modern plate subduction2--in rocks aged more than about 1 billion years calls into question the existence of plate tectonics during the Archaean and Palaeoproterozoic eras3, 4. Instead, plate tectonics and subduction could have either not occurred at that time5, or could have proceeded differently6 owing to warmer conditions in the early Earth mantle7. Here we use thermodynamic models8, 9, 10 to investigate the formation conditions of metamorphic minerals in the 2.2-2.0 Gyr old West African metamorphic province. We find a record of blueschist metamorphism in these rocks. We show that minerals such as chlorite and phengite formed at high pressures of 10-12 kbar, low temperatures of 400-450 °C and under a geothermal gradient of 10-12 °C km−1. These conditions are typical of modern subduction zones. We therefore suggest that modern-style plate tectonics existed during the Palaeoproterozoic era. We conclude that ancient blueschist metamorphism may exist in other parts of the world, but the identification of these rocks has so far been hampered by methodological problems associated with deciphering their pressure and temperature evolution.

Red sandstones near Green River, Utah (United States), have been bleached by diagenetic fluids. Field relationships, modeling, fluid inclusion and isotopic data suggest that the causal fluid was a CO2-charged brine, distinguishing this site from hydrocarbon-related bleaching elsewhere on the Colorado Plateau. Mineralogical and chemical profiles from unbleached to bleached sandstone show that bleaching is related to hematite dissolution and precipitation of a 1–2 cm band of secondary oxide and carbonate at the reaction front. Trace metals are mobilized by the fluid and concentrated near the reaction front. High-flux fluid pathways are more heavily altered with large-scale secondary calcite and iron oxide precipitation. Changes may be modeled by a reaction with stoichiometry 20Fe2O3 + 5CH4 + 64CO2 + 19H2O + 11H+ = 30Fe2+ + 10FeHCO3+ + 59HCO3–. The Fe-rich, reduced fluid precipitates iron-oxides and carbonate at the reaction front between bleached and unbleached sandstone. These findings make the site an analogue for processes occurring over long time scales in geological carbon storage projects. Trace metals moblized by CO2-charged brines are likely to be rapidly re-precipitated at reaction fronts.

Secure storage of anthropogenic carbon dioxide (CO2) in geological reservoirs requires predicting gas–water–rock interactions over millennial timescales. Noble gases and carbon isotope measurements can be used to shed light on the nature of competing dissolution—precipitation processes over different timescales, from the fast dissolution of gaseous CO2 in groundwater to more sluggish reactions involving dissolution and precipitation of newly formed minerals in the reservoir. Here we study a compilation of gas analyses including noble gases and δ13C of CO2 from nine different natural CO2 reservoirs. Amongst these reservoirs, the Bravo Dome CO2 field (New Mexico, USA) shows distinct geochemical trends which are explained by degassing of noble gases from groundwater altering the composition of the gas phase. This groundwater degassing is synchronous with the dissolution of CO2 in groundwater. Progressive creation of alkalinity via CO2-promoted mineral dissolution is required to explain the observed positive correlation between CO2/3He and δ13C of the gas phase, a unique feature of Bravo Dome. The differences between Bravo Dome and other natural CO2 reservoirs are likely explained by the more recent filling of Bravo Dome, reflecting CO2–water–rock interactions over thousands of years rather than over millions of years in older reservoirs.

During chemical weathering, magnesium (Mg) is released by the dissolution of both carbonate and silicate sources. The degree to which solute concentrations and isotopic compositions of rivers reflect the relative proportions of these two inputs, or cycling by a series of processes associated with weathering is poorly constrained. In the river waters of the Mackenzie Basin (Canada), the Mg content is high and Mg isotope ratios (26Mg/24Mg expressed as δ Mg 26 ) show in excess of one per mil variability. Part of this variability is attributed to the 3‰ range in the carbonate and silicate rocks drained. Despite this inherent lithological control on river water δ Mg 26 values, there is also evidence for a fractionation control. A linear positive covariation between lithium (7Li/6Li, expressed as δ Li 7 ) and Mg isotope ratios in the river waters of the Mackenzie Basin is reported. This covariation is not expected because previously reported fractionation related to physicochemical processes associated with clays or oxides should induce a negative covariation with Mg isotope ratios. This continental-scale covariation can be resolved by either process-related fractionation or mixing. Evidence for fractionation associated with clays is provided firstly by comparing Mg and Li isotopes in both the waters and sediments carried in suspension. Secondly a linear covariation between the sediment concentrations of large ion lithophile elements caesium and rubidium (a proxy for clay content of the sediment) and δ Mg 26 values of the water suggests that processes linked to clay, such as neoformation of clay, cation exchange or adsorption may be important. Simple models illustrate that if the covariation is induced by fractionation, there is either more than one process acting, or a single process is kinetically limited. Alternatively, the data can be reconciled by mixtures between at least three different water bodies, two of which have similar isotopic compositions but differing Li/Mg ratios. This intriguing data set highlights the challenges associated with distinguishing mixing from process with stable isotope data. Despite the complexity, the data question to what extent and by what mechanism clays mediate river water chemistry, at least in terms of the stable isotope compositions of Mg and Li. These questions are fundamental to the quantification of carbon dioxide consumption by silicate weathering and its role in climatic feedback.

International audience; Predicting phase relations and reactions involving phyllosilicates is of critical importance when modeling geological reservoirs and making thermobarometric estimates at temperatures below 350 °C. However, it is difficult to perform experimental studies of phase relations of phyllosilicates because of very slow reaction rates. Simple methods of estimations of thermodynamic properties of minerals such as oxide summation techniques are insufficient to constrain activity models for minerals. In this study, we use a recent atomistic technique that allows constraining activity models in minerals independently from kinetics. Among the various solid solutions occurring in phyllosilicates, the magnitude and the thermodynamic significance of the pyrophyllitic substitution has strong implications on the stability of clay minerals at surface conditions. We have applied a lattice energy estimation method combined with Monte Carlo simulations to estimate the energy of mixing along the muscovite-pyrophyllite solid solution at 25 °C and 1 bar. The results suggest a strongly positive and asymmetric Gibbs free energy of mixing, concordant at first order with previous thermodynamic models issued from phase relations and with field observations. The calculated solvus implies that pyrophyllite-rich phyllosilicates are unstable, unless another phenomenon such as hydration stabilizes them. Calculated structures at low muscovite contents present large variations of interlayer occupancies due to short- and long-range ordering. The observed ordering suggests that sub-layers in illite/smectite mixed layers minerals are not independent as the alternation of K-rich and K-depleted sublayers minimizes the Gibbs free energy of the mineral.

[1] The northeastern continental margin of Oman in the Saih Hatat region is characterized by high-pressure (HP) chloritoid- or carpholite-bearing metasediments and highly deformed mafic eclogites and blueschists in a series of tectonic units bounded by high-strain ductile shear zones. New data on the upper cover units of this HP nappe stack indicate that all of them underwent similar P conditions to the underlying Hulw structural unit (with a cooler exhumation pressure-temperature path). Early SSW directed crustal thickening during ophiolite emplacement created recumbent folds and strong schistose fabrics in these Permian-Mesozoic shelf carbonates and was followed by later NNE dipping normal sense shear zones and normal faults. The Mayh unit shows high strain in a 15–25 km long sheath fold that likely formed at carpholite grade pressures of 8–10 kbar. We show that there are no significant P differences across the Hulw shear zone (upper plate–lower plate discontinuity) or between the overlying Mayh, Yenkit-Yiti, and Ruwi units. Postpeak metamorphic exhumation of the HP rocks was therefore accomplished by bottom-to-SSW (rather than top-to-NNE) active footwall extrusion beneath a fixed, static, passive hanging wall. Footwall uplift beneath these passive roof faults resulted in progressive expulsion of the HP rocks from depths of ∼80–90 km (eclogites) and mainly 30–35 km (blueschists and chloritoid-/carpholite-bearing units) during the Campanian–Early Maastrichtian. Oman thus provides a detailed record of how continental material (thick platform shelf carbonates) progressively jammed a subduction zone and emphasizes the contrasting behavior between cover units and their underlying basement.

International audience; We propose a thermodynamic approach to model the stepwise dehydration with increasing temperature or decreasing H2O activity of K, Na, Ca and Mg-smectite. The approach relies on the relative stability of the different solid-solutions that describe the hydration of di- or trioctahedral-smectites containing 0, 1, 2 or 3 interlayer water layers. The inclusion of anhydrous mica end-members makes it possible to cover, with the same solid-solution model, the entire range of composition from low-charge to high-charge smectite, through illite to mica. Non-ideal Margules parameters were used to describe the non-ideality of the solid solutions between the hydrated and dehydrated smectite end-members. Standard state properties of all smectite end-members as well as Ca- and Mg-muscovite and -phlogopite were initially estimated by oxide summation. These values were then refined and the other non-ideal interactions were estimated on the basis of different experimental data. The stepwise dehydration of smectite, and its stability and compatibility relations were calculated by Gibbs free energy minimizing. Our results account for the progressive evolution of smectite to interlayered illite/smectite and then to mica, as observed in nature and experiments, and our model provides an explanation for the thermodynamic stability of smectite and illite/smectite compared to mica + kaolinite or pyrophyllite assemblages. The results suggest that the enthalpic contribution of interlayer water is a function of the ionic potential of the interlayer cation and the number of interlayer water molecules. This evolution makes possible to estimate the standard-state thermodynamic parameters and hydration-temperature behaviour of smectite of virtually all possible compositions. For the four-interlayer cations considered in the study, our model reproduces the 3 → 2 → 1 water-layer transitions that accompany a reduction of water activity or an increase of temperature at ambient pressure. The range of water content and interlayer distance calculated for the 3w, 2w and 1w states are also in fair agreement with the experimental values at ambient pressure.

Journal of physics / Conference Series 499, 012012 (2014). doi:10.1088/1742-6596/499/1/012012, Rocks are commonly polycrystalline systems presenting multi-scale chemical and structural heterogeneities inherited from crystallization processes or successive metamorphic events. This work illustrates how spatially resolved analytical techniques coupled with thermodynamic approaches allow rock compositional variations to be related to large-scale geodynamic processes. Emphasis is placed on the contribution of quantitative chemical imaging to the study of 2.2-2.0 Gy old metamorphic rocks from the West African Craton. A thorough analysis of elemental chemical maps acquired on rock thin sections enabled high pressure relic minerals to be located and re-analyzed later with precise point analyses. The pressure-temperature conditions of crystallization calculated from these analyses are typical of modern subduction zones. These results push back the onset of modern-style plate tectonics to 2.15 Gy, i.e. more than one billion years earlier than was consensually accepted. The second part of the paper describes the imaging capabilities offered by the new ultra-bright diffraction limited synchrotron sources. Experimental data acquired with the Maia detector at beamline P06 at Petra III as well as simulations of μ-XRF spectra that will be generated at the SRX beamline at NSLS-II are presented. These results demonstrate that cm2 large chemical maps can be acquired with submicron spatial resolution and a precision suitable for thermobarometric estimates, with dwell time smaller than 1 millisecond. The last part of the paper discusses the relevance of utilizing recent X-ray fluorescence nanoprobes for diagenetic to low grade metamorphism applications., Published by IOP Publ., Bristol

Chorite is a phyllosilicate crystallizing in a wide range of pressure and temperature conditions, among a diversity of rocks : from diagenesis to metamorphic conditions, typically in greenschist facies but also in blueschist and amphibolite facies. Chlorite is useful for metamorphic petrology as a geothermometer, as its composition is sensitive to the temperature of crystallization and chlorite is commonly found within mineral assemblages. Chlorite shows many solid solutions, among which Fe may be incorporated in large proportions in divalent (Fe2+) and/or trivalent (Fe3+) state. Unfortunately current models for geothermometry on chlorite either neglect Fe3+ or require evaluating the thermodynamic properties of Fe3+-rich chlorite for increased accuracy. This study aims at providing new crystal-chemistry data on ferric chlorite from a wide range of composition and origin, and to answer the following questions : (1) how much Fe3+ may be incorporated in chlorite ? (2) what are the cationic substitutions and end-members for Fe3+ incorporation ? (3) how is Fe3+ distributed within the chlorite structure ? and (4) what are the dependencies between Fe3+ in chlorite and the pressure-temperature conditions, and oxygen fugacity, at crystal and mineral scales ? This work investigates the speciation of iron in chlorite with different techniques; X-ray absorption near-edge spectroscopy at the Fe-K edge (K XANES), and electron energy-loss spectroscopy (EELS) combined with electron microprobe major element analyzes. X-ray diffraction investigation brings structural information on the structure of ferric chlorite. This analytical strategy is focused on chlorite from natural rock samples and experimental syntheses made at fixed pressure and temperature, and under buffered oxygen fugacity.A new database on ferric chlorite crystal-chemistry is the major output of this work, which highlights substitutions involving Fe3+. A Fe3+ -rich, vacant endmember is required to account for the di-trioctahedral substitution, and a magnesian end-member with 1 Fe3+ replacing Al for the homovalent Al - Fe3+ substitution. These results are observed in natural specimens and confirmed by experimental synthsesis of ferric chlorite. In addition, chlorite with Fe3+ > 1.5 p.f.u. shows systematic deviation from the ideal O10(OH)8 anionic basis, where proton deficit has been inferred from indirect measurements of H+ content. These results are consistent with the existence of an "oxychlorite" group within the classification of phyllosilicates. At mineral scale, the variations of the oxidation state take place at nanoscale and are unrelated to variations in the amount of Fe. Chlorite crystallized via experimental synthesis shows similar features. These results explain the poor success of geothermometry on some iron-rich chlorite, and allow us to propose improved cation distribution algorithms for geo thermometry. Our study paves the way for future experimental synthesis focused on oxychlorite.; Les chlorites sont des phyllosilicates ayant la particularité de cristalliser sur une large gamme de conditions de pression et température, et dans une variété de roches et d’environnements géologiques pouvant aller du contexte diagénétique au contexte métamorphique de type schiste bleu à amphibolitique. La composition des chlorites est sensible à leur température de cristallisation, et avec leur présence récurrente au sein des paragénèses, celles-ci sont couramment utilisées pour l’estimation des conditions thermobarométriques par les pétrologues. Cependant la plupart des modèles thermobarométriques actuels ne permettent pas d’estimer de manière fiable des températures au sein de l’ensemble des compositions des chlorites. Les modèles thermodynamiques en particulier ne prennent pas en compte ou sous-estiment l’état d’oxydation du fer dans les chlorites qui peut être sous forme Fe2+ ou Fe3+. Ce travail de thèse a ainsi pour objectif d’apporter de nouvelles données cristallochimiques sur un large panel de chlorites ayant incorporé du fer trivalent de compositions et contextes variés, tout en répondant aux questions sur : (1) la quantité de Fe3+ qui peut être incorporée dans les chlorites, (2) les substitutions cationiques permettant l’incorporation du Fe3+ dans les chlorites et leurs pôles purs associés, (3) la localisation du Fe3+ et des autres cations dans les sites cristallographiques des chlorites et enfin, (4) sur le lien éventuel entre le Fe3+ dans les chlorites et les conditions thermodynamiques du milieu que sont la pression, température, et la fugacité en oxygène à l’échelle du cristal et du minéral.Ce travail de thèse utilise différentes méthodes de mesure du Fe3+/FeTOT ; la spectroscopie d’absorption du fer au seuil K (K XANES), et la spectroscopie par perte d’énergie des électrons (EELS) couplées à l’utilisation de la microsonde électronique. Ce volet analytique est complété par des analyses de diffraction des rayons X. L’approche utilisée repose sur l’étude de chlorites naturelles échantillonnées pour leur représentativité du domaine de composition, ainsi que sur des chlorites synthétisées expérimentalement sous pression, température, et fugacité en oxygène contrôlées.Une nouvelle base de données cristallochimiques sur les chlorites ferriques constitue l’apport principal de ce travail, et a permis en particulier de mettre en évidence les substitutions contrôlant l’incorporation du Fe3+ dans la structure. Ainsi la substitution di-trioctaédrique 3R2+ = 2Fe3+ + _ et l’échange Al = Fe3+ semblent expliquer le domaine de composition des chlorites ferriques jusqu’à Fe3+ ∼ 1.5 p.f.u., permettant de définir un ou plusieurs pôles purs de type ferri-sudoite en plus d’un pôle ferrique non lacunaire et magnésien, dans les chlorites naturelles et synthétiques. Mais l’analyse de l’oxygène dans les chlorites les plus ferriques montrent un déficit de protons interprété comme lié à l’oxydation du fer divalent, tel que : Fe2+ + H+ = Fe3+, mettant en évidence un composant "oxychlorite" à base anionique O12(OH)6. Une implication importante est que la présence de lacunes et la substitution di-trioctaédrique précédemment révélées sont largement un artefact de normalisation sur la base anionique O10(OH)8.A l’échelle du minéral la distribution du rapport Fe3+/FeTOT dans les chlorites montre des variations pouvant atteindre jusqu’à ∼ 30 %, sur une échelle de la centaine à dizaine de nanomètres. Cette hétérogénéité se retrouve également à l’échelle du micromètre mais n’est pas corrélée à la distribution du FeTOT et des autres éléments majeurs dans la lame. Enfin en plus de confirmer les substitutions des chlorites naturelles, les synthèses de chlorites ont permis d’identifier un probable contrôle de la fugacité en oxygène sur le rapport Fe3+/FeTOT mais pas sur la quantité de Fe3+ incorporée, indépendamment de la composition de départ.Ces résultats améliorent les connaissances cristallochimiques sur les chlorites ferriques et permettent de proposer un nouvel algorithme d’allocation des cations dans les sites, en vue de l’élaboration d’un modèle thermodynamique prenant en compte l’incorporation du Fe3+.

Chorite is a phyllosilicate crystallizing in a wide range of pressure and temperature conditions, among a diversity of rocks : from diagenesis to metamorphic conditions, typically in greenschist facies but also in blueschist and amphibolite facies. Chlorite is useful for metamorphic petrology as a geothermometer, as its composition is sensitive to the temperature of crystallization and chlorite is commonly found within mineral assemblages. Chlorite shows many solid solutions, among which Fe may be incorporated in large proportions in divalent (Fe2+) and/or trivalent (Fe3+) state. Unfortunately current models for geothermometry on chlorite either neglect Fe3+ or require evaluating the thermodynamic properties of Fe3+-rich chlorite for increased accuracy. This study aims at providing new crystal-chemistry data on ferric chlorite from a wide range of composition and origin, and to answer the following questions : (1) how much Fe3+ may be incorporated in chlorite ? (2) what are the cationic substitutions and end-members for Fe3+ incorporation ? (3) how is Fe3+ distributed within the chlorite structure ? and (4) what are the dependencies between Fe3+ in chlorite and the pressure-temperature conditions, and oxygen fugacity, at crystal and mineral scales ? This work investigates the speciation of iron in chlorite with different techniques; X-ray absorption near-edge spectroscopy at the Fe-K edge (K XANES), and electron energy-loss spectroscopy (EELS) combined with electron microprobe major element analyzes. X-ray diffraction investigation brings structural information on the structure of ferric chlorite. This analytical strategy is focused on chlorite from natural rock samples and experimental syntheses made at fixed pressure and temperature, and under buffered oxygen fugacity.A new database on ferric chlorite crystal-chemistry is the major output of this work, which highlights substitutions involving Fe3+. A Fe3+ -rich, vacant endmember is required to account for the di-trioctahedral substitution, and a magnesian end-member with 1 Fe3+ replacing Al for the homovalent Al - Fe3+ substitution. These results are observed in natural specimens and confirmed by experimental synthsesis of ferric chlorite. In addition, chlorite with Fe3+ > 1.5 p.f.u. shows systematic deviation from the ideal O10(OH)8 anionic basis, where proton deficit has been inferred from indirect measurements of H+ content. These results are consistent with the existence of an "oxychlorite" group within the classification of phyllosilicates. At mineral scale, the variations of the oxidation state take place at nanoscale and are unrelated to variations in the amount of Fe. Chlorite crystallized via experimental synthesis shows similar features. These results explain the poor success of geothermometry on some iron-rich chlorite, and allow us to propose improved cation distribution algorithms for geo thermometry. Our study paves the way for future experimental synthesis focused on oxychlorite.; Les chlorites sont des phyllosilicates ayant la particularité de cristalliser sur une large gamme de conditions de pression et température, et dans une variété de roches et d’environnements géologiques pouvant aller du contexte diagénétique au contexte métamorphique de type schiste bleu à amphibolitique. La composition des chlorites est sensible à leur température de cristallisation, et avec leur présence récurrente au sein des paragénèses, celles-ci sont couramment utilisées pour l’estimation des conditions thermobarométriques par les pétrologues. Cependant la plupart des modèles thermobarométriques actuels ne permettent pas d’estimer de manière fiable des températures au sein de l’ensemble des compositions des chlorites. Les modèles thermodynamiques en particulier ne prennent pas en compte ou sous-estiment l’état d’oxydation du fer dans les chlorites qui peut être sous forme Fe2+ ou Fe3+. Ce travail de thèse a ainsi pour objectif d’apporter de nouvelles données cristallochimiques sur un large panel de chlorites ayant incorporé du fer trivalent de compositions et contextes variés, tout en répondant aux questions sur : (1) la quantité de Fe3+ qui peut être incorporée dans les chlorites, (2) les substitutions cationiques permettant l’incorporation du Fe3+ dans les chlorites et leurs pôles purs associés, (3) la localisation du Fe3+ et des autres cations dans les sites cristallographiques des chlorites et enfin, (4) sur le lien éventuel entre le Fe3+ dans les chlorites et les conditions thermodynamiques du milieu que sont la pression, température, et la fugacité en oxygène à l’échelle du cristal et du minéral.Ce travail de thèse utilise différentes méthodes de mesure du Fe3+/FeTOT ; la spectroscopie d’absorption du fer au seuil K (K XANES), et la spectroscopie par perte d’énergie des électrons (EELS) couplées à l’utilisation de la microsonde électronique. Ce volet analytique est complété par des analyses de diffraction des rayons X. L’approche utilisée repose sur l’étude de chlorites naturelles échantillonnées pour leur représentativité du domaine de composition, ainsi que sur des chlorites synthétisées expérimentalement sous pression, température, et fugacité en oxygène contrôlées.Une nouvelle base de données cristallochimiques sur les chlorites ferriques constitue l’apport principal de ce travail, et a permis en particulier de mettre en évidence les substitutions contrôlant l’incorporation du Fe3+ dans la structure. Ainsi la substitution di-trioctaédrique 3R2+ = 2Fe3+ + _ et l’échange Al = Fe3+ semblent expliquer le domaine de composition des chlorites ferriques jusqu’à Fe3+ ∼ 1.5 p.f.u., permettant de définir un ou plusieurs pôles purs de type ferri-sudoite en plus d’un pôle ferrique non lacunaire et magnésien, dans les chlorites naturelles et synthétiques. Mais l’analyse de l’oxygène dans les chlorites les plus ferriques montrent un déficit de protons interprété comme lié à l’oxydation du fer divalent, tel que : Fe2+ + H+ = Fe3+, mettant en évidence un composant "oxychlorite" à base anionique O12(OH)6. Une implication importante est que la présence de lacunes et la substitution di-trioctaédrique précédemment révélées sont largement un artefact de normalisation sur la base anionique O10(OH)8.A l’échelle du minéral la distribution du rapport Fe3+/FeTOT dans les chlorites montre des variations pouvant atteindre jusqu’à ∼ 30 %, sur une échelle de la centaine à dizaine de nanomètres. Cette hétérogénéité se retrouve également à l’échelle du micromètre mais n’est pas corrélée à la distribution du FeTOT et des autres éléments majeurs dans la lame. Enfin en plus de confirmer les substitutions des chlorites naturelles, les synthèses de chlorites ont permis d’identifier un probable contrôle de la fugacité en oxygène sur le rapport Fe3+/FeTOT mais pas sur la quantité de Fe3+ incorporée, indépendamment de la composition de départ.Ces résultats améliorent les connaissances cristallochimiques sur les chlorites ferriques et permettent de proposer un nouvel algorithme d’allocation des cations dans les sites, en vue de l’élaboration d’un modèle thermodynamique prenant en compte l’incorporation du Fe3+.