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, spat 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.