Authigenic titanite in weathered basalts: Implications for paleoatmospheric reconstructions

The stability of titanite is sensitive to temperature and partial pressure of CO2. The finding of authigenic titanite grains in weathering regolith formed on Paraná basalts, Brazil, under tropical climatic conditions, reveals the thermodynamically-driven conversion from calcite to titanite at elevated ambient temperatures. Being unusual nowadays, this phase transition provides important implications for the understanding of silicate weathering in earlier geological epochs. Two types of secondary titanites were identified in the weathering profile of the study area. The tiny grains of 10 ​μm are forming in the microscopic voids in the rock. Also, large fractures filled with Fe-rich clay minerals contain bigger specimens of up to 170 ​μm. The titanites of second type often coexist with chalcedony and barite. No carbonate minerals were found in the weathering profile. Weathering sphene can be discriminated from other titanite types by its strong positive Eu anomaly, increased Al2O3 content and low content of trace elements. Its specific chemical composition and reactive transport modeling link this secondary mineral with dissolution of plagioclase. The titanite precipitation is controlled by slow diffusion in poorly-aerated, highly-alkaline pore fluids. The subaerial weathering of basaltic rocks provides a significant reservoir for atmospheric CO2. However, the deposition of carbonate minerals is thermodynamically avoided at the stability field of titanite. We demonstrate a complex feedback between CO2 and soil carbonates. The rise in pCO2 triggers the precipitation of calcite in the weathering regolith, but the greenhouse effect increasing the temperature can cease carbonate deposition. Secondary titanites were found in several paleosols and at least a part of them can be of weathering origin. [Display omitted] •Authigenic titanite forms in weathered basalts under tropical climatic conditions.•Weathering titanite has a specific chemical composition.•The diffusion in O2-free alkaline pore fluids controls titanite precipitation.•Calcite does not precipitate in regolith at the stability field of titanite.•Titanite in paleosols indicates elevated temperatures or low pCO2 in the atmosphere.