The carbonation of serpentinites in the forearc region of the mantle wedge in subduction zones and of serpentinites within the subducting slab by fluids derived from prograde dehydration and decarbonation have important implications for the deep Earth carbon cycle. This study shows that the carbonation of serpentinites under the forearc can establish, over time, a significant reservoir for carbon within a partially hydrated mantle wedge and that carbonation of (ultra-) mafic rocks within the subducting slab contributes to C-transfer to greater depths and might supply carbon for arc volcanism or the deep mantle. We report a new high pressure experimental investigation of the interactions between oxidised CO -H fluids and serpentinite and model the reaction progress with time series experiments. The CO 2 , H 2 O and alkane (C n H 2n+2 , n=1-6; e.g. methane, ethane) contents in the fluid phase from quenched experimental run products have been analysed by gas chromatography and the results are compared with thermodynamic calculations. With progressive carbonation, the formation of magnesite + chlorite together with quartz, quartz + talc or talc at 1-2 GPa and 500-650 °C was observed. At temperatures above antigorite stability (T≳700 ºC and 2 GPa) magnesite + chlorite is stable together with talc, talc + enstatite, enstatite or enstatite + forsterite for decreasing CO 2-content in the fluid. Highlights Quantitative CO -H analyses of fluids after piston cylinder experiments Carbonation of serpentinites in the forearc region of the mantle wedge Carbonation is rapid and occurs within the first hour of the experiments Magnesite is a good monitor for Ca, Ba, Sr and Pb in subduction zone fluids

We have conducted high pressure far-infrared absorbance and Raman spectroscopic investigations on a natural iron-free dolomite sample up to 40 GPa. Comparison between the present observations and literature results unraveled the effect of hydrostatic conditions on the high pressure dolomite polymorph adopted close to 40 GPa, i.e. the triclinic Dol-IIIc modification. In particular, non-hydrostatic conditions impose structural disorder at these pressures, whereas hydrostatic conditions allow the detection of an ordered Dol-IIIc vibrational response. Hence, hydrostatic conditions appear to be a key ingredient for modeling carbon subduction at lower mantle conditions. Our complementary first-principles calculations verified the far-infrared vibrational response of the ambient-and high-pressure dolomite phases.

The presence of Ca-Mg-carbonates affects the melting and phase relations of peridotites and eclogites in the mantle, and (partial) melting of carbonates liberates carbon from the mantle to shallower depths. The onset and composition of incipient melting of carbonated peridotites and carbonated eclogites are influenced by the pure CaCO3-MgCO3-system making the understanding of the phase relations of Ca-Mg-carbonates fundamental in assessing carbon fluxes in the mantle. By performing high-pressure and high-temperature experiments, this study clarifies the suprasolidus phase relations of the nominally anhydrous CaCO3-MgCO3-system at 6 GPa showing that Ca-Mg-carbonates will (partially) melt for temperatures above ~1300 °C. A comparison with data from thermodynamic modeling confirms the experimental results. Furthermore, partition coefficients for Li, Na, K, Sr, Ba, Nb, Y, and rare earth elements between calcite and dolomitic melt, Ca-magnesite and dolomitic melt, and magnesite and dolomitic melt are established. Experiments were performed at 6 GPa and between 1350 to 1600 °C utilizing a rotating multi-anvil press. Rotation of the multi-anvil press is indispensable to establish equilibrium between solids and carbonate liquid. Major and trace elements were quantified with EPMA and LA-ICP-MS, respectively. The melting temperature and phase relations of Ca-Mg-carbonates depend on the Mg/Ca-ratio. For instance, Ca-rich carbonates with a molar Mg/(Mg+Ca)-ratio (XMg) of 0.2 will transform into a dolomitic melt (XMg = 0.33–0.31) and calcite crystals (XMg = 0.19–0.14) at 1350–1440 °C. Partial melting of Mg-rich carbonates (XMg = 0.85) will produce a dolomitic melt (XMg = 0.5–0.8) and Ca-bearing magnesite (XMg = 0.89–0.96) at 1400–1600 °C. Trace element distribution into calcite and magnesite seems to follow lattice constraints for divalent cations. For instance, the compatibility of calcite (XMg = 0.14–0.19) for Sr and Ba decreases as the cation radii increases. Ca-Mg-carbonates are incompatible for rare earth elements (REEs), whereby the distribution between carbonates and dolomitic melt depends on the Mg/Ca ratio and temperature. For instance, at 1600 °C, partition coefficients between magnesite (XMg = 0.96) and dolomitic melt (XMg = 0.8) vary by two orders of magnitudes from 0.001 to 0.1 for light-REEs to heavy-REEs. In contrast, partition coefficients of REEs (and Sr, Ba, Nb, and Y) between magnesite (XMg = 0.89) and dolomitic melt (XMg = 0.5) are more uniform scattering marginal between ~0.1–0.2 at 1400 °C.

High-pressure experiments were performed to investigate the effectiveness, rate and mechanism of carbonation of serpentinites by a carbon-saturated COH fluid at 1·5–2·5 GPa and 375–700 °C. This allows a better understanding of the fate and redistribution of slab-derived carbonic fluids when they react with the partially hydrated mantle within and above the subducting slab under pressure and temperature conditions corresponding to the forearc mantle. Interactions between carbon-saturated CO2–H2O–CH4 fluids and serpentinite were investigated using natural serpentinite cylinders with natural grain sizes and shapes in piston-cylinder experiments. The volatile composition of post-run fluids was quantified by gas chromatography. Solid phases were examined by Raman spectroscopy, electron microscopy and laser ablation inductively coupled plasma mass spectrometry. Textures, porosity and phase abundances of recovered rock cores were visualized and quantified by three-dimensional, high-resolution computed tomography. We find that carbonation of serpentinites is efficient at sequestering CO2 from the interacting fluid into newly formed magnesite. Time-series experiments demonstrate that carbonation is completed within ∼96 h at 2 GPa and 600 °C. With decreasing CO2,aq antigorite is replaced first by magnesite + quartz followed by magnesite + talc + chlorite in distinct, metasomatic fronts. Above antigorite stability magnesite + enstatite + talc + chlorite occur additionally. The formation of fluid-permeable reaction zones enhances the reaction rate and efficiency of carbonation. Carbonation probably occurs via an interface-coupled replacement process, whereby interconnected porosity is present within reaction zones after the experiment. Consequently, carbonation of serpentinites is self-promoting and efficient even if fluid flow is channelized into veins. We conclude that significant amounts of carbonates may accumulate, over time, in the hydrated forearc mantle.

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