Organic Geochemistry of Earth's Upper Mantle Fluids

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Fresh, pseudotachylyte-bearing mantle peridotites from the lawsonite eclogite-facies san petrone unit, alpine corsica

Mantle peridotites exhumed in mountain belts provide important insights on the composition and evolution of the upper mantle, and additionally inform on metamorphic, geochemical, and tectonic processes-including seismic activity-at convergent margins. In this contribution, we present field, microstruc-tural, and mineralogical data of fresh, pseudotachylyte-bearing mantle peridotites from the lawsonite eclogite-facies San Petrone unit, Alpine Corsica, France. The present case study represents the first example of subducted fresh peridotite associated with fresh lawsonite eclogite-facies assemblages. Two bodies of fresh peridotite are embedded in fully serpentinized ultramafic rocks forming the substratum of a subducted ocean-continent transition of the Piemonte-Liguria Basin. Clinopyroxene and spinel mineral chemistry indicates that the investigated peridotite samples were part of a refertilized mantle and, therefore, the San Petrone unit likely belonged to the more distal part of the ocean-continent transition. Because small bodies of fresh peridotite embedded in fully serpentinized rocks can hardly be identified by means of geophysical investigations, this finding suggests that small, yet disseminated bodies of fresh mantle peridotite can potentially be more abundant than previously supposed at ocean-continent transition and, potentially, at mid-ocean ridges and in subduction zones. The preservation of fresh mantle peridotite bodies in subducting slabs is also discussed with respect to its potential implications on intermediate depth seismicity and geochemical cycling-including production of natural energy sources-from rifting to subduction

Electrophoretic deposition of Sr-containing mesoporous bioactive glass particles produced by spray-drying

Introduction Mesoporous bioactive glasses (MBGs) are gaining increasing interest in the biomedical field thanks to their exceptional textural characteristics (high surface area, high pore volume and highly ordered mesoporosity). These properties lead to an improved apatite kinetics formation, which allow these glasses to be successfully applied in bone tissue regeneration [1]. In this work we adopted an aerosol-based spray drying process in order to have high control and reproducibility over the morphology of particles. In order to increase their regenerative potential, the particles have been doped with strontium, element known for its osteogenic and bone antiresorptive properties [2]. Later the particles have been deposed by electrophoretic deposition (EPD) on glass-ceramic scaffolds fabricated by the polymer sponge replication method. EPD is a versatile technique which allows an easy control of the thickness of the deposited film through simple adjustment of the applied voltage and the deposition time. The scaffolds, based on a quaternary silicate glass (SCNA, SiO2–CaO–Na2O–Al2O3 oxide system), have good mechanical properties but low bioactivity [3]. Thanks to MBG particle deposition, they acquire a pronounced bioactive behaviour, thus becoming an excellent solution for bone tissue regeneration. Results and Discussion MBGs synthesized with the aerosol-based spray-drying process have a basic composition on the SiO2-CaO system and have been doped with the 1% molar of strontium (SD_Sr1). FESEM image of particles shows micro-sized spherical particles, with size mostly ranging between 500 nm and 5 µm. N2 adsorption analysis gives back a high specific surface area value, 160 m2/g, and a pore size distribution between 5 and 9 nm, which confirms the mesoporosity of the sample. Strontium incorporation inside the binary composition does not modify the bioactive behaviour of the glass: after 14 days in SBF nanoparticles are completely covered by a layer of hydroxyapatite.The EDS quantitative analysis shows that the amount of strontium effectively incorporated in the microparticles was 70% of the theoretical one, probably because of the high dimension of the ion which hinders its entrance into the glass network. Nevertheless, most of the Sr incorporated has been released after 14 days of immersion in SBF, as the coupled plasma-atomic emission spectrometry (ICP-AES) reveals. On the basis of literature data, the released concentrations are suitable for inducing osteogenesis [4]. EPD has been performed in ethanol, applying a voltage of 120 V for 5 minutes. The scaffolds, being not conductive, have been suspended between two stainless steel electrodes through a clamp. A dispersant (TEA, triethanolamine) has been used to keep the particles in suspension during the whole deposition time. The deposited layer was abundant but not uniform on the scaffold surface. After immersion for 7 days in SBF, hydroxyapatite formation has been observed on the surface of the microparticles deposited on the scaffold struts. This demonstrates that MBGs not only maintain their bioactivity after deposition but also transfer this property to scaffolds. Conclusions MBGs synthetized with aerosol-based spray-drying process and doped with strontium have excellent textural properties and a bioactive behaviour. After electrophoretic deposition, they maintain these properties and consequently they improve the bioactivity of SCNA scaffolds, which initially are almost biologically inert. In this way we demonstrate that it is possible to obtain a successful construct for bone tissue engineering with both excellent regenerative and mechanical properties

Feedback between high-pressure genesis of abiotic methane and strain localization in subducted carbonate rocks

AbstractFluid-rock interactions exert key control over rock rheology and strain localization. Redox may significantly affect the reaction pathways and, thereby, the mechanical properties of the rock. This effect may become critical in volatile-rich, redox sensitive rocks such as carbonate-rich lithologies, the breakdown of which can significantly modify the net volume change of fluid-mediated reactions. Subduction focus the largest recycling of crustal carbonates and the most intense seismic activity on Earth. Nevertheless, the feedbacks between deep carbon mobilization and deformation remain poorly investigated. We present quantitative microstructural results from natural samples and thermodynamic modeling indicating that percolation of reducing fluids exerts strong control on the mobilization of carbon and on strain localization in subducted carbonate rocks. Fluid-mediated carbonate reduction progressed from discrete domains unaffected by ductile deformation into localized shear zones deforming via diffusion creep, dissolution-precipitation creep and grain boundary sliding. Grain-size reduction and creep cavitation along localized shear zones enhanced fluid-carbonate interactions and fluid channelization. These results indicate that reduction of carbonate rocks can exert an important positive feedback on strain localization and fluid channelization, with potential implications on seismic activity and transport of deep hydrocarbon-bearing fluids.</jats:p

I Contratti di Fiume e la Strategia Nazionale per le Aree Interne: un banco di prova per l'approccio place-based in Italia

In the majority of European regions, territorial inequalities between main urban nodes and marginal territories are raising concerns and pose serious development challenges. Phenomena such as ageing, depopulation and impoverishment of inner areas, and the polarization of social, economic and cultural opportunities in urban areas are often the result of place-neutral, spatially-blind approaches and hinder the European objective of social, economic and territorial cohesion. Since a decade, the European Union is pushing towards more place-based approaches to development in order to face these challenges. The experiences of the River Agreements and the National Strategy for Inner Areas are relevant examples of the Italian take on the EU place-based logics, combining bottom-up and top-down logic within multilevel, multiactor and multifund context-sensitive processes. This contribution discusses the main features, potentials and limitations of the two approaches, aiming to contribute to the debate and policies for the sustainable reactivation of marginal areas and rebalance of territorial inequalities

An Experimental Study on Kinetics-Controlled Ca-Carbonate Aqueous Reduction into CH4 (1 and 2 GPa, 550 degrees C): Implications for C Mobility in Subduction Zones

Abiotic methane (CH4) generation under subduction zone conditions has been experimentally investigated through aqueous reduction of pure C-bearing materials (e.g. carbonate minerals and organic matter). However, quantitative assessments of CH(4 )production in these experiments, as well as the potential effects of other components such as SiO2 on the reduction processes, have not yet been well established. Here, we performed experiments to quantitatively evaluate the time-resolved Ca-carbonate aqueous reduction into CH4 at P = 1 and 2 GPa and T = 550 degrees C in the CaO + COH, CaO + SiO2 COH, and CaO + SiO2 + MgO + COH systems, employing calcite + water +/- quartz +/- serpentine (synthetic chlorine (Cl)-bearing chrysotile and natural Fe-Al-bearing antigorite) as starting materials. Redox conditions of the experiments were buffered by iron-wilstite (IW) using a double capsule setting, corresponding to oxygen fugacity (fO(2)) values (expressed as log units relative to the fayalite-magnetite-quartz buffer, Delta FMQ) in the inner capsule of Delta FMQ approximate to -5.5 at 1 GPa and Delta FMQ approximate to -6.0 at 2 GPa. The solid products are mainly composed of portlandite +/- larnite +/- wollastonite +/- brucite, while Ca-carbonate and/or silicate reactants commonly occur as relicts. Quadrupole mass spectrometric analysis shows that CH4 and H2O are the major COH molecular species in the fluid products, with molar ratios between CH4 and starting calcite representing the reaction progress ranging from similar to 0.13 to similar to 1.00. Comparisons of experimental run products with thermodynamically predicted phase assemblages, together with time-series experiments, indicate that the reduction processes are primarily controlled by reaction kinetics. At 1 GPa and 550 degrees C, rate constants of 4.0 x 10(-6) s(-1), 7.4 x 10(-6) s(-1) , and 2.6 x 10(-6 )s(-1) were retrieved for reactions starting with calcite + quartz + water, calcite + synthetic Cl-bearing chrysotile + water, and calcite + natural Fe-Al-bearing antigorite + water, respectively, significantly higher than the constant of 0.8 x 10(-6) s(-1 )for the silicate-absent reaction. Besides, an increase in pressures can also enhance the reduction efficiency of Ca-carbonates until reaching equilibrium with the fluids. Our data provide experimental evidence for kinetics-controlled Ca-carbonate aqueous reduction into CH4 in subduction zones, indicating that silicate involvement and/or pressure increase can accelerate the reaction rates through short-lived fluid-rock interactions, which may have important implications for deep C mobility

Abiotic methane generation through reduction of serpentinite-hosted dolomite: Implications for carbon mobility in subduction zones

Abiotic methane has been increasingly detected at the surface of Earth and other terrestrial planets, exerting a strong effect on the study of chemolithoautotrophic life and thus astrobiology. In contrast, abiotic methane generation in subduction zones, which is intimately linked to questions such as the mechanisms of deep carbon mobility, has received scarce attention. Experiments elucidated the significant production of abiotic methane through reduction of carbonate minerals under subduction zone conditions, whereas detailed geological conditions and processes for the reduction in natural rocks are hitherto poorly understood. Here, we report carbonate reduction and genesis of abiotic methane in dolomitized serpentinites (referred to as ophidolomites) from a fossil subduction zone (SW Tianshan, China). Detailed petrological, Raman spectroscopic, strontium and carbon isotopic, and thermodynamic results provide evidence for dolomite reduction into the phase assemblage of calcite + brucite + methane, likely associated with retrograde serpentinization starting at 7–9 kbar and 410–430 °C in the subduction zone. Microthermometric data for dolomite-hosted fluid inclusions are consistent with petrographic observations, indicative of fluid entrapment postdating the onset of dolomite reduction during exhumation. Model calculations suggest that water-rich fluids characterized by relatively high hydrogen fugacities can create favorable conditions for the reduction process, which, however, do not exclude the possibility of carbonate methanation by hydrogen-rich fluids as reported in previous studies. The widespread occurrence of methane in these rocks gives credence to the intricate redox transformations of subducted carbon, implying that the elevated hydrogen fugacities may facilitate abiotic synthesis of methane through dolomite reduction at convergent plate boundaries. Our work shows that alteration of dolomite-bearing lithologies represents a potential source for abiotic methane in subduction zones, which may have implications for the transfer of subducted carbon