High pressure melting of eclogite and metasomatism of garnet peridotites from Monte Duria Area (Central Alps, N Italy): A proxy for melt-rock reaction during subduction

In the Monte Duria area (Adula-Cima Lunga unit, Central Alps, N Italy) garnet peridotites occur in direct contact with migmatised orthogneiss (Mt. Duria) and eclogites (Borgo). Both eclogites and ultramafic rocks share a common high pressure (HP) peak at 2.8\u202fGPa and 750\u202f\ub0C and post-peak static equilibration at 0.8\u20131.0\u202fGPa and 850\u202f\ub0C. Garnet peridotites show abundant amphibole, dolomite, phlogopite and orthopyroxene after olivine, suggesting that they experienced metasomatism by crust-derived agents enriched in SiO2, K2O, CO2 and H2O. Peridotites also display LREE fractionation (La/Nd\u202f=\u202f2.4) related to LREE-rich amphibole and clinopyroxene grown in equilibrium with garnet, indicating that metasomatism occurred at HP conditions. At Borgo, retrogressed garnet peridotites show low strain domains characterised by garnet compositional layering, cut by a subsequent low-pressure (LP) chlorite foliation, in direct contact with migmatised eclogites. Kfs\u202f+\u202fPl\u202f+\u202fQz\u202f+\u202fCpx interstitial pocket aggregates and Cpx\u202f+\u202fKfs thin films around symplectites after omphacite parallel to the Zo\u202f+\u202fOmp\u202f+\u202fGrt foliation in the eclogites suggest that they underwent partial melting at HP. The contact between garnet peridotites and eclogites is marked by a tremolitite layer. The same rock also occurs as layers within the peridotite lens, showing a boudinage parallel to the garnet layering of peridotites, flowing in the boudin necks. This clearly indicates that the tremolitite boudins formed when peridotites were in the garnet stability field. Tremolitites also show Phl\u202f+\u202fTc\u202f+\u202fChl\u202f+\u202fTr pseudomorphs after garnet, both crystallised in a static regime postdating the boudins formation, suggesting that they derive from a garnet-bearing precursor. Tremolitites have Mg#\u202f>\u202f0.90 and Al2O3\u202f=\u202f2.75\u202fwt% pointing to ultramafic compositions but also show enrichments in SiO2, CaO, and LREE suggesting that they formed after the reaction between the eclogite-derived melt and the garnet peridotite at HP. To test this hypothesis, we performed a thermodynamic modelling at fixed P\u202f=\u202f3\u202fGPa and T\u202f=\u202f750\u202f\ub0C to model the chemical interaction between the garnet peridotite and the eclogite-derived melt. Our results show that this interaction produces an Opx\u202f+\u202fCpx\u202f+\u202fGrt assemblage plus Amp\u202f+\u202fPhl, depending on the water activity in the melt, suggesting that tremolitites likely derive from a previous garnet websterite with amphibole and phlogopite. Both peridotites and tremolitites also show a selective enrichment in LILE recorded by amphiboles in the spinel stability field, indicating that a fluid-assisted metasomatic event occurred at LP conditions, leading to the formation of a chlorite foliation post-dating the garnet layering in peridotites, and the retrogression of Grt-websterites in tremolitites. The Monte Duria area is a unique terrane where we can observe syn-deformation eclogite-derived melt interacting with garnet peridotite at HP, proxy of subduction environments

Redox processes and the role of carbon-bearing volatiles from the slab-mantle interface to the mantle wedge

The valence of carbon is governed by the oxidation state of the host system. The subducted oceanic lithosphere contains considerable amounts of iron so that Fe3+/Fe2+ equilibria in mineral assemblages are able to buffer the (intensive) fO2 and the valence of carbon. Alternatively, carbon itself can be a carrier of (extensive) \u2018excess oxygen\u2019 when transferred from the slab to the mantle, prompting the oxidation of the sub-arc mantle. Therefore, the correct use of intensive and extensive variables to define the slab-to-mantle oxidation by C-bearing fluids is of primary importance when considering different fluid/rock ratios. Fluid-mediated processes at the slab\u2013mantle interface can also be investigated experimentally. The presence of CO2 (or CH4 at highly reduced conditions) in aqueous COH fluids in peridotitic systems affects the positions of carbonation or decarbonation reactions and of the solidus. Some methods to produce and analyse COH fluid-saturated experiments in model systems are introduced, together with the measurement of experimental COH fluids composition in terms of volatiles and dissolved solutes. The role of COH fluids in the stability of hydrous and carbonate minerals is discussed comparing experimental results with thermodynamic models and the message of nature

Experimental determination of magnesia and silica solubilities in graphite-saturated and redox-buffered high-pressure COH fluids in equilibrium with forsterite + enstatite and magnesite + enstatite

We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 \ub0C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni\u2013NiO\u2013H2O (\u394FMQ = 12\u20090.21 to 12\u20091.01), employing a double-capsule setting. Fluids, binary H2O\u2013CO2 mixtures at the P, T, and fO2 conditions investigated, were generated from graphite, oxalic acid anhydrous (H2C2O4) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO2-bearing fluids. The experimental data show that forsterite\u2009+\u2009enstatite solubility in H2O\u2013CO2 fluids is higher compared to pure water, both in terms of dissolved silica (mSiO2\u2009=\u20091.24 mol/kgH2O versus mSiO2\u2009=\u20090.22 mol/kgH2O at P\u2009=\u20091 GPa, T\u2009=\u2009800 \ub0C) and magnesia (mMgO\u2009=\u20091.08 mol/kgH2O versus mMgO\u2009=\u20090.28 mol/kgH2O) probably due to the formation of organic C\u2013Mg\u2013Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H2O\u2013CO2 fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO2 ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO2 ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P\u2013T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest level of the upper mantle

Primary spinel + chlorite inclusions in mantle garnet formed at ultrahigh-pressure

Multiphase inclusions represent microenvironments where the interaction between fluid and host mineral is preserved during the rock geological path. Under its peculiar chemical-physical constraints, the entrapped solute-rich fluid might follow a crystallisation mechanism which is not predictable through simple equilibrium arguments. In this letter, by the modelling of solid-solution equilibrium and the application of principles of mass conservation, we demonstrate that cavities in mantle garnet filled with slab-derived fluids can re-equilibrate to a pyrope + spinel + chlorite assemblage at the same high P-T of their formation. The basis of this occurrence is a dissolution-reprecipitation mechanism, triggered by a dilute, non-equilibrated slab fluid

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

Dissolution susceptibility of glass-like carbon versus crystalline graphite in high-pressure aqueous fluids and implications for the behavior of organic matter in subduction zones

Organic matter, showing variable degrees of crystallinity and thus of graphitization, is an important source of carbon in subducted sediments, as demonstrated by the isotopic signatures of deep and ultra-deep diamonds and volcanic emissions in arc settings. In this experimental study, we investigated the dissolution of sp2 hybridized carbon in aqueous fluids at 1 and 3 GPa, and 800\ub0C, taking as end-members i) crystalline synthetic graphite and ii) X-ray amorphous glass-like carbon. We chose glass-like carbon as an analogue of natural \u201cdisordered\u201d graphitic carbon derived from organic matter, because unlike other forms of poorly ordered carbon it does not undergo any structural modification at the investigated experimental conditions, allowing approach to thermodynamic equilibrium. Textural observations, Raman spectroscopy, synchrotron X-ray diffraction and dissolution susceptibility of char produced by thermal decomposition of glucose (representative of non-transformed organic matter) at the same experimental conditions support this assumption. The redox state of the experiments was buffered at \u394FMQ 48 \u20130.5 using double capsules and either fayalite-magnetite-quartz (FMQ) or nickel-nickel oxide (NNO) buffers. At the investigated P\u2013T\u2013fO2 conditions, the dominant aqueous dissolution product is carbon dioxide, formed by oxidation of solid carbon. At 1 GPa and 800\ub0C, oxidative dissolution of glass-like carbon produces 16\u201319 mol% more carbon dioxide than crystalline graphite. In contrast, fluids interacting with glass-like carbon at the higher pressure of 3 GPa show only a limited increase in CO2 (fH2NNO) or even a lower CO2 content (fH2FMQ) with respect to fluids interacting with crystalline graphite. The measured fluid compositions allowed retrieving the difference in Gibbs free energy (\u394G) between glass-like carbon and graphite, which is +1.7(1) kJ/mol at 1 GPa\u2013800\ub0C and +0.51(1) kJ/mol (fH2NNO) at 3 GPa\u2013800\ub0C. Thermodynamic modeling suggests that the decline in dissolution susceptibility at high pressure is related to the higher compressibility of glass-like carbon with respect to crystalline graphite, resulting in G\u2013P curves crossing at about 3.4 GPa at 800\ub0C, close to the graphite\u2013diamond transition. The new experimental data suggest that, in the presence of aqueous fluids that flush subducted sediments, the removal of poorly crystalline \u201cdisordered\u201d graphitic carbon is more efficient than that of crystalline graphite especially at shallow levels of subduction zones, where the difference in free energy is higher and the availability of poorly organized metastable carbonaceous matter and of aqueous fluids produced by devolatilization of the downgoing slab is maximized. At depths greater than 110 km, the small differences in \u394G imply that there is minimal energetic drive for transforming \u201cdisordered\u201d graphitic carbon to ordered graphite; \u201cdisordered\u201d graphitic carbon could even be energetically slightly favored in a narrow P interval

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

Abiotic and biotic processes that drive carboxylation and decarboxylation reactions

© 2020 Walter de Gruyter GmbH, Berlin/Boston 2020. Carboxylation and decarboxylation are two fundamental classes of reactions that impact the cycling of carbon in and on Earth's crust. These reactions play important roles in both long-term (primarily abiotic) and short-term (primarily biotic) carbon cycling. Long-term cycling is important in the subsurface and at subduction zones where organic carbon is decomposed and outgassed or recycled back to the mantle. Short-term reactions are driven by biology and have the ability to rapidly convert CO2 to biomass and vice versa. For instance, carboxylation is a critical reaction in primary production and metabolic pathways like photosynthesis in which sunlight provides energy to drive carbon fixation, whereas decarboxylation is a critical reaction in metabolic pathways like respiration and the tricarboxylic acid cycle. Early life and prebiotic chemistry on Earth likely relied heavily upon the abiotic synthesis of carboxylic acids. Over time, life has diversified (de)carboxylation reactions and incorporated them into many facets of cellular metabolism. Here we present a broad overview of the importance of carboxylation and decarboxylation reactions from both abiotic and biotic perspectives to highlight the importance of these reactions and compounds to planetary evolution

Subducted organic matter buffered by marine carbonate rules the carbon isotopic signature of arc emissions

Ocean sediments consist mainly of calcium carbonate and organic matter (phytoplankton debris). Once subducted, some carbon is removed from the slab and returns to the atmo- sphere as CO2 in arc magmas. Its isotopic signature is thought to reflect the bulk fraction of inorganic (carbonate) and organic (graphitic) carbon in the sedimentary source. Here we challenge this assumption by experimentally investigating model sediments composed of 13C-CaCO3 + 12C-graphite interacting with water at pressure, temperature and redox con- ditions of an average slab–mantle interface beneath arcs. We show that oxidative dissolution of graphite is the main process controlling the production of CO2, and its isotopic compo- sition reflects the CO2/CaCO3 rather than the bulk graphite/CaCO3 (i.e., organic/inorganic carbon) fraction. We provide a mathematical model to relate the arc CO2 isotopic signature with the fluid–rock ratios and the redox state in force in its subarc source