Effect of Water Activity on Reaction Kinetics and Intergranular Transport: Insights from the Ca(OH) 2 + MgCO 3 → CaCO 3 + Mg(OH) 2 Reaction at 1·8 GPa

The kinetics of the irreversible reaction Ca(OH)2 + MgCO3 → CaCO3 + Mg(OH)2 were investigated at high pressures and temperatures relevant to metamorphic petrology, using both in situ synchrotron X-ray diffraction and post-mortem analysis of reaction rim growth on recovered samples. Reaction kinetics are found to strongly depend on water content; comparable bulk-reaction kinetics are obtained under water-saturated (excess water, c. 10 wt %) and under intermediate (0·1–1 wt % water) conditions when temperature is increased by c. 300 K. In contrast, similar reaction kinetics were observed at ∼673 K and 823 K between intermediate and dry experiments, respectively, where dry refers to a set of experiments with water activity below 1·0 (no free water), as buffered by the CaO–Ca(OH)2 assemblage. Given the activation energies at play, this gap—corresponding to the loss of no more than 1 wt % of water by the assemblage—leads to a difference of several orders of magnitude in reaction kinetics at a given temperature. Further analysis, at the microscopic scale, of the intermediate and dry condition samples, shows that intergranular transport of calcium controls the reaction progress. Grain boundary diffusivities could be retrieved from the classic treatment of reaction rim growth rate. In turn, once modeled, this rate was used to fit the bulk kinetic data derived from X-ray powder diffraction, offering an alternative means to derive calcium diffusivity data. Based on a comparison with effective grain boundary data for Ca and Mg from the literature, it is inferred that both dry and intermediate datasets are consistent with a water-saturated intergranular medium with different levels of connectivity. The very high diffusivity of Ca in the CaCO3 + Mg(OH)2 rims, in comparison with that of Mg in enstatite rims found by earlier workers, emphasizes the prominent role of the interactions between diffusing species and mineral surfaces in diffusion kinetics. Furthermore, we show that the addition of water is likely to change the relative diffusivity of Mg and Ca in carbonate aggregates. From a qualitative point of view, we confirm, in a carbonate-bearing system, that small water content variations within the 0–1 wt % range have tremendous effects on both intergranular transport mechanisms and kinetics. We also propose that the water content dependent diffusivity of major species (Mg, Ca) in low-porosity metamorphic rocks is strongly dependent on the interaction between diffusing species and mineral surfaces. This parameter, which will vary from one rock-type to another, needs also to considered when extrapolating (P, T, t, xH2O) laboratory diffusion data to metamorphic processes

Intermediate-depth brecciation along the subduction plate interface (Monviso eclogite, W. Alps)

International audienceThe Monviso meta-ophiolite complex (Northern Italy, Western Alps) represents an almost intact fragment of Tethyan oceanic lithosphere metamorphosed at 80 km depth ( 2.6GPa-550 °C) during the Alpine subduction. We focus our study on a major shear zone cutting across this slab fragment at low angle (the Lower Shear Zone; LSZ). Here, in its talc and tremolite-rich serpentinite matrix, are embedded (together with metasedimentary lenses) variously brecciated Fe-Ti and Mg-Al metagabbro blocks. The latter were either interpreted as eclogitic breccias resulting from intermediate-depth rupture or as inherited, overprinted oceanic core complex features. Our new field, structural and petrographic data testify the genesis of this metagabbro breccia blocks at eclogite-facies conditions. Three types of eclogitic blocks can be distinguished, with non-random distribution (and decreasing size from top to base) throughout the 200-m-thick and 15 km-long LSZ: (1) Fe-Ti-metagabbros, brecciated and scattered in the upper to intermediate levels of the LSZ; (2) meter-size blocks and decameter-scale slivers of intact Mg-Al metagabbros, locally brecciated; (3) dm- to m-scale blocks of intact Fe-Ti metagabbros without breccia fabrics. Brecciation at eclogite facies conditions (at 80 km depth) is documented by: i) the eclogitic foliation of intact Mg-Al-rich metagabbros (composed of omphacite + clinozoisite ± rutile and locally garnet) cut by breccia planes (cemented by omphacite + garnet ± lawsonite) and ii) the occurrence in breccia clasts of minerals that are fractured and offset along peak P-T omphacite-bearing planes. Rupture preferentially affected the Fe-Ti metagabbros, suggesting that rheological contrasts controlled the locus of brecciation. The occurrence of a first omphacite-rich matrix (M1, 2.7GPa - 580 °C) crosscut by omphacite + garnet-bearing matrix M2 ( 2.4GPa - 560 °C), witnesses multiple brittle rupture events, prior to a stage of eclogite facies fluid ingression marked by massive lawsonite recrystallization (matrix M3)

Fluid Pulses During Stepwise Brecciation at Intermediate Subduction Depths (Monviso Eclogites, W. Alps): First Internally Then Externally Sourced

Eclogite‐facies breccias from the Monviso metaophiolite complex (N‐Italy and W‐Alps) represent a unique opportunity to study the triggering mechanisms for transient brittle deformation at eclogite‐facies conditions in ductilely deforming subducted oceanic lithosphere. Here the intact foliation of Fe‐Ti‐rich and Mg‐Al‐rich metagabbro clasts, cemented by unfoliated eclogitic matrices (paragenesis: omphacite ± garnet ± lawsonite), demonstrates pristine brecciation at eclogite‐facies conditions. Successive generations of high‐pressure veins and eclogitic matrices reveal multiple brittle rupture events. Pseudosection modeling, textural observations, and geochemical data suggest that minerals of both prograde veins and first brecciation event (M1 matrix) crystallized in presence of fluids buffered by the surrounding metagabbro minerals, while M2 matrix composition suggests an incipient infiltration of external fluids. Trace element composition of the third M3 matrix, associated to its impressive lawsonite pseudomorphs, clearly points to the massive ingression of external, serpentinite‐derived fluids. Therefore, these rocks record the progressive increase in the scale of fluid circulation along multiple, stepwise eclogitic brecciation events, from locally released fluids (closed system) to kilometer‐scale fluid infiltration. The successive brecciation steps promoted permeability creation (at least transiently), which resulted in progressive opening of the system to large‐scale sustained fluid circulation. Eclogite‐facies brecciation also controlled the initial stages of strain localization, which highlights the importance, in ductilely deforming low‐permeability eclogite‐facies rocks, of brittle deformation events for both strain localization initiation and creation of large‐scale fluid circulation pathways. Thus, Monviso breccia blocks record the complete, stepwise development of a major shear zone, via progressive strain localization, permeability creation, and increasing scale of fluid circulation

The 3-D Thermal Structure of the Helvetic Nappes of the European Alps: Implications for Collisional Processes

International audienceUnderstanding the rheology of orogenic wedges requires the knowledge of the structural and thermal evolution of collisional units. In this study, we document the maximum temperature reached by the sedimentary cover nappes of the External Crystalline Massif (Western and central Alps) by Raman spectroscopy of carbonaceous material, between the Belledonne (France) and the Aar (Switzerland) Massifs. These cover units form the Helvetic/Dauphinois nappe complex. Maximum temperatures reached by the Upper Helvetic nappes lie in a range spanning from below 220 and 350 °C ± 50 °C. For the Lower Helvetic nappes, the temperatures spread between 226 and 358 °C ± 50 °C. These temperatures were projected on two structural cross sections in order to constrain the 3-D thermal structure. From these data, we propose that the Helvetic nappes were deformed and emplaced before and/or during the thermal peak, which supports recent findings that shortening in the External Crystalline Massif was mainly accommodated during a 5- to 10-Myr-long thermal peak before deformation localized along crustal thrusts, which exhumed and cooled down the wedge. During this late exhumation, the isotherms corresponding to the thermal peak were passively folded

Enhanced Olivine Carbonation within a Basalt as compared to single-phase experiments: reevaluating the Potential of CO2 Mineral Sequestration

International audienceBatch experiments were conducted in water at 150 °C and PCO2 = 280 bar on a Mg-rich tholeiitic basalt (9.3 wt % MgO and 12.2 wt % CaO) composed of olivine, Ti-magnetite, plagioclase, and clinopyroxene. After 45 days of reaction, 56 wt % of the initial MgO had reacted with CO2 to form Fe-bearing magnesite, (Mg0.8Fe0.2)CO3, along with minor calcium carbonates. The substantial decrease in olivine content upon carbonation supports the idea that ferroan magnesite formation mainly follows from olivine dissolution. In contrast, in experiments performed under similar run durations and P/T conditions with a San Carlos olivine separate (47.8 wt % MgO) of similar grain size, only 5 wt % of the initial MgO content reacted to form Fe-bearing magnesite. The overall carbonation kinetics of the basalt was enhanced by a factor of ca. 40. This could be explained by differences in the chemical and textural properties of the secondary silica layer that covers reacted olivine grains in both types of sample. Consequently, laboratory data obtained on olivine separates might yield a conservative estimate of the true carbonation potential of olivine-bearing basaltic rock

Pervasive silicification and hanging wall overplating along the 13°20'N oceanic detachment fault (Mid-Atlantic Ridge)

International audienceThe corrugated detachment fault zone of the active 13820 0 N oceanic core complex (Mid-Atlantic Ridge) was investigated with a deep-sea vehicle to assess the links between deformation, alteration, and magmatism at detachment fault zones. We present a study of 18 in situ fault rock samples from striated fault outcrops on the flanks of microbathymetric corrugations. All the samples are mafic breccias that are mostly derived from a diabase protolith, with two of them also showing mixing with ultramafic clasts. Brec-cias are cataclastic and display variable deformation textures, recording numerous slip events, and showing pervasive silicification throughout the fault zone. Deformation-silicification relationships are also complex, showing both static and syntectonic quartz precipitation; undeformed quartz overprints the fault breccia textures, and reflective and striated fault surfaces cross-cut silicified rocks. In situ detachment fault rocks are mainly fault breccias with almost exclusively basaltic clasts, with rare ultramafic ones, a lithology and texture never observed previously at other oceanic detachment fault zones. We propose the lower dyke complex in the hanging wall crust at the volcanic rift valley floor is the most plausible diabase source. Mechanical mixing of predominantly mafic and rare ultramafic clasts suggests an underlying ultramafic footwall and that mafic accretion operates in the shallowest crust (1-2 km), at the base of the dyke complex at temperatures >4008C. Silicification is produced by silica-rich fluids syntectonically channeled along the fault zone, and likely derived from hydrothermal alteration of basaltic rocks, likely mixed with serpentinization-derived fluids. Plain Language Summary This paper presents a textural, mineralogical, and microstructural study of the fault rocks recovered in situ on the 13820 0 N detachment fault zone (Mid-Atlantic ridge) during the ODEMAR cruise in 2013. This detachment is unique for the presence of mafic material integrated within the fault zone as breccias and the pervasive silicification observed throughout all the detachment surface. Our paper discusses the origin of the mafic breccias and proposes that they were captured from the base of the dyke complex within the hanging wall during the fault exhumation. Our study reveals furthermore that quartz mineralization occurred in depth during the exhumation and is likely linked with the presence of mafic material within the fault zone. Our study indicates a complex relationship between silicification and deformation during which quartz (re)crystallized under quasi-static conditions between periods of deformation. This work also demonstrates that extreme strain localization can be achieved in the absence of weak alteration phases (talc, serpentine) but with instead high-friction material (quartz), suggesting that elevated pore fluid pressures play an important role