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Hypogene dissolution-precipitation processes strongly affect the petrophysical properties of carbonate rocks and fluid migration pathways in sedimentary basins. In many deep carbonate reservoirs, hypogene cavernous voids are often associated with silicified horizons. The diagenesis of silica in carbonate sequences is still a poorly-investigated research topic. Studies exploring the complexity of silica dissolution-precipitation patterns in hypogene cave analogues are therefore fundamental to unravel the diagenetic and speleogenetic processes that may affect this kind of reservoir. In this work, we investigated an exhumed and silicified Neoproterozoic carbonate sequence in Brazil hosting a 1.4 km-long cave. Quartz mineralization and silicified textures were analyzed with a multidisciplinary approach combining petrography, fluid inclusion microthermometry, silicon-oxygen stable isotope analyses and U-Th-Pb dating of monazite crystals. We found that an early silicification event caused the replacement of the dolostone layers with micro-crystalline quartz forming chert nodules. This event was likely associated with mixing fluids (ancient Neoproterozoic seawater and hydrothermal solutions sourced from the underlying Mesoproterozoic basement) at relatively low temperatures (ca. 50-100 degrees C) and shallow depth. After the tectonic deformation produced by the Brasiliano orogeny, silica dissolution was promoted by high temperature and alkaline hydrothermal solutions rising from the quartzite basement along deep-rooted structures. Hypogene hydrothermal alteration promoted the dissolution of the cherty layers and the precipitation of chalcedony and megaquartz. Homogenization temperatures from primary fluid inclusions in megaquartz cement indicate minimum formation temperatures of 165-210 degrees C. Similar temperature estimates (110-200 degrees C) were obtained from the delta Si-30 and delta O-18 isotope systematics of quartz precipitated from hydrothermal solutions. The dissolved salts in the fluid inclusions were evaluated as NaCl + CaCl2 from microthermometric data combined with cryogenic Raman spectroscopy, corresponding to salinity ranging between 17 and 25 wt.%. No reliable age constraints for hydrothermal silica dissolution-precipitation phases were obtained from monazite U-Th-Pb dating. However, our results, interpreted in the regional context of the Sao Francisco Craton, suggest that the Cambrian tectono-thermal events could have been amongst the possible drivers for this hypogene process in the basin.

Although quantitative isotope data from speleothems has been used to evaluate isotope-enabled model simulations, currently no consensus exists regarding the most appropriate methodology through which to achieve this. A number of modelling groups will be running isotope-enabled palaeoclimate simulations in the framework of the Coupled Model Intercomparison Project Phase 6, so it is timely to evaluate different approaches to using the speleothem data for data-model comparisons. Here, we illustrate this using 456 globally distributed speleothem delta O-18 records from an updated version of the Speleothem Isotopes Synthesis and Analysis (SISAL) database and palaeoclimate simulations generated using the ECHAM5-wiso isotope-enabled atmospheric circulation model. We show that the SISAL records reproduce the first-order spatial patterns of isotopic variability in the modern day, strongly supporting the application of this dataset for evaluating model-derived isotope variability into the past. However, the discontinuous nature of many speleothem records complicates the process of procuring large numbers of records if data-model comparisons are made using the traditional approach of comparing anomalies between a control period and a given palaeoclimate experiment. To circumvent this issue, we illustrate techniques through which the absolute isotope values during any time period could be used for model evaluation. Specifically, we show that speleothem isotope records allow an assessment of a model's ability to simulate spatial isotopic trends. Our analyses provide a protocol for using speleothem isotope data for model evaluation, including screening the observations to take into account the impact of speleothem mineralogy on delta O-18 values, the optimum period for the modern observational baseline and the selection of an appropriate time window for creating means of the isotope data for palaeo-time-slices. European Geosciences Union - W2017/413; Irish Centre for Research in Applied Geosciences (iCRAG); European Association of Geochemistry (Early Career Ambassadors program 2017); Quaternary Research Association UK; Navarino Environmental Observatory, Stockholm University; University College Dublin, Savillex (UK) - SF1428; Ibn Zohr University, Morocco; University of Reading; European Research Council - 694481; Natural Environment Research Council (JPI-Belmont project "PAleao-Constraints on Monsoon Evolution and Dynamics (PACMEDY)"); Geological Survey Ireland - 2017-SC-056; Royal Irish Academy; Deutsche Forschungsgemeinschaft - RE3994/2-1; Past Global Changes (PAGES) programme; info:eu-repo/semantics/publishedVersion