Geochemical, and stable and radiogenic isotope records in Devonian and Early Carboniferous carbonates from Valle de Tena, central Pyrenees (Spain): evidence for their diagenetic environments

Abstract

Mineralogical, textural and geochemical investigations were made to determine the post-depositional evolution of Devonian and Early Carboniferous carbonates from Valle de Tena. The carbonate association is made up of low-Mg calcite, which occurs as micrite, spar cements, neomorphic patches and spar filling veinlets. Non-stoichiometric dolomite and ankerite occur as cements (dolomite also as replacements) in the Middle Devonian, post-dating calcite types. All these phases pre-date tectonic stylolites, indicating compaction after stabilization of the carbonate minerals. Strontium concentrations indicate that Early Devonian and Early Carboniferous micrites initially precipitated as aragonite; Middle and Late Devonian micrites precipitated as high-Mg calcites. Both precursors were diagenetically stabilized to low-Mg calcites through interaction with meteoric waters in phreatic environments. Trace elements in dolomite and ankerite indicate precipitation from Sr-enriched meteoric water. All studied carbonates, except Middle Devonian limestones, precipitated in reducing environments, which favoured incorporation of Fe and Mn. Late calcite generations precipitated from more saline waters than micrites. Light δ18O values in micrites suggest alteration mainly in meteoric-phreatic environments. The dolomites and ankerites precipitated from more 18O-depleted fluids than the calcites, suggesting a greater contribution from meteoric waters. Variations in δ13C of micrites represent primary secular trends, according to published δ13C variations. The δ13C oscillations within each succession probably relate to sea-level oscillations. Strontium isotopes also point to a meteoric origin of diagenetic fluids. Model calculations suggest that O and Sr isotopes equilibrated between calcites and fluid at relatively low water/rock ratios, whereas C isotopic signatures are inherited from limestones.