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Exposures of low-grade metabasalts and ophicarbonates in the Northern Apennines, and their high- and ultrahigh-pressure metamorphic equivalents in the Western and Ligurian Alps and Tianshan (representing an overall peak P- T range of ~ 0.2-3.0. GPa, 200-610. °C), allow investigation of the effects of prograde metamorphic devolatilization, and other fluid-rock interactions, on degrees of retention and isotopic evolution of C in subducting oceanic crust and associated mantle rocks. Such work can inform models of C cycling at convergent margins, helping to constrain the efficiency of return of initially subducted C via arc volcanism and the fraction of this subducted C entering the deeper mantle beyond arcs. In the metabasaltic rocks, the preservation of finely disseminated carbonate with δ13C overlapping that of seafloor-altered protoliths, and the minimal mineralogical evidence of decarbonation, indicates large degrees of carbonate retention in this suite extending to UHP conditions similar to those beneath modern volcanic fronts. For many of the metabasalts, the δ18O of this carbonate can be explained by closed-system equilibration with silicate phases (e.g., garnet, clinopyroxene) during HP/UHP metamorphism. Larger volumes of carbonate preserved in interpillow regions and as breccia-filling largely escaped decarbonation, showing little or no evidence for reaction with adjacent metabasalt. Calculated devolatilization histories demonstrate that, in a closed-system model, carbonate in metabasaltic rocks can largely be preserved to depths approaching those beneath volcanic fronts (80-90km). Modeling of open-system behavior indicates that episodic infiltration of such rocks by H2O-rich fluids would have greatly enhanced decarbonation. Trends in O-C isotope composition of carbonate in some metabasaltic suites likely reflect effects of infiltration by externally-derived fluid with or without resulting decarbonation. Most carbonated ultramafic rocks similarly show little mineralogical evidence for decarbonation, consistent with calculated reaction histories, and have δ13C largely overlapping that of seafloor equivalents. However, the high-grade ophicarbonates show more restricted ranges in δ18O consistent with some control by infiltrating fluids, likely during subduction. This combination of field, petrographic, and isotopic evidence, together with calculated decarbonation histories, is consistent with minimal loss of CO2 from these rocks via decarbonation during forearc metamorphism. Combining our results with those of Cook-Kollars et al. (2014; Chemical Geology) for associated W. Alps metasedimentary rocks, we suggest that the majority of the CO2 (perhaps 80-90%, considering the full range of rock types) could be retained through forearcs in more intact volumes of subducting sediment, basalt, and ophicarbonate experiencing closed- or limited open-system conditions. Deep in forearcs and beneath arcs, decarbonation (and also carbonate dissolution) could be enhanced in shear zones and highly fractured volumes experiencin...

Much of the long-term carbon cycle in solid earth occurs in subduction zones, where processes of devolatilization, partial melting of carbonated rocks, and dissolution of carbonate minerals lead to the return of CO2 to the atmosphere via volcanic degassing. Release of COH fluids from hydrous and carbonate minerals influences C recycling and magmatism at subduction zones. Contradictory interpretations exist regarding the retention/storage of C in subducting plates and in the forearc to subarc mantle. Several lines of evidence indicate mobility of C, of uncertain magnitude, in forearcs. A poorly constrained fraction of the 40-115 Mt/yr of C initially subducted is released into fluids (by decarbonation and/or carbonate dissolution) and 18-43 Mt/yr is returned at arc volcanoes. Current estimates suggest the amount of C released into subduction fluids is greater than that degassed at arc volcanoes: the imbalance could reflect C subduction into the deeper mantle, beyond subarc regions, or storage of C in forearc/subarc reservoirs.We examine the fate of C in plate-interface ultramafic rocks, and by analogy serpentinized mantle wedge, via study of fluid-rock evolution of marble and variably carbonated serpentinite in the Ligurian Alps. Based on petrography, major and trace element concentrations, and carbonate C and O isotope compositions, we demonstrate that serpentinite dehydration at 2-2.5 GPa, 550 °C released aqueous fluids triggering breakdown of dolomite in nearby marbles, thus releasing C into fluids. Carbonate + olivine veins document flow of COH fluids and that the interaction of these COH fluids with serpentinite led to the formation of high-P carbonated ultramafic-rock domains (high-P ophicarbonates). We estimate that this could result in the retention of ~0.5-2.0 Mt C/yr in such rocks along subduction interfaces. As another means of C storage, 1 to 3 km-thick layers of serpentinized forearc mantle wedge containing 50 modal % dolomite could sequester 1.62 to 4.85 Mt C/yr.We stress that lithologically complex interfaces could contain sites of both C release and C addition, further confounding estimates of net C loss at forearc and subarc depths. Sites of C retention, also including carbonate veins and graphite as reduced carbonate, could influence the transfer of slab C to at least the depths beneath volcanic fronts

O] based on single-crystal X-ray diffraction, electron microprobe, stable isotope analyses, and scanning electron microscope imaging. This is the first reported occurrence of kröhnkite in a cave environment. Atacamite represents the weathering product (in the presence of Lower-Cretaceous limestone-derived chlorine) of copper minerals washed into the cave from nearby ore bodies. Atacamite and kröhnkite have similar sources for copper and chlorine, whereas sodium probably originates from weathered Precambrian and Permian detrital rocks. Collinsite is believed to have precipitated from bat guano in a damp, nearneutral pH environment. The results show the following sequence of precipitation: ardealite-brushite-(gypsum)-atacamite-kröhnkite. This suggests that the observed mineral paragenesis is controlled by the neutralization potential of the host-rock mineralogy and the concentrations of Ca, Cl, Cu, and Na.Keywords: cave minerals, sulfates, phosphates, guano, stable isotopes, Cioclovina Cave, Romania Abstract: