The object of this study is magnesian clay minerals present in carbonate rocks of the post-rift phase of the pre-salt in the Santos Basin. These rocks developed in an Aptian-age alkaline lacustrine environment. This study summarizes the formation of clay minerals associated with different lithotypes in a range of 19 m and a depth of more than 5100 m. They were characterized from petrographic analysis by optical microscopy, X-ray diffraction (total sample and clay fraction), and modeling by Newmod^®; and examined and analyzed by scanning electron microscopy. An approach based on identifying lithotypes and characterization of microsites allowed us to understand the occurrence of different clay minerals. Kerolite was the most abundant mineral in the sampled range. It occurs in lamellar aggregates under greater preservation of the original rock lamination and in association with spherulites and shrubs. The Stv/Ker mixed layers occurs in the same association, and formed finer unlaminated aggregates associated with the more intense dolomitization and silicification processes. Saponite occurs associated with detrital minerals forming clayey levels intercalated with microcrystalline carbonates. Fluids with a high Mg/Si and pH < 9 favor the precipitation of kerolite. The increase in pH during diagenesis may be responsible for the formation of Stv/Ker mixed layers.

The characterization of Mg-clays in rock samples (well P1) from the Barra Velha Formation (Early Cretaceous) allowed the establishment of mineral assemblages on the basis of their kerolite and Mg-smectite (stevensite and saponite) content. Kerolite-rich assemblages (A and B) rarely contain saponite. Assemblage B is composed of kerolite-stevensite mixed layers, while assemblage A consists of more than 95% kerolite. Mg-smectite-rich assemblages (C and CB) are made up of both Mg-smectites. The predominance of stevensite in the lower interval of the stratigraphic succession suggests evaporative conditions, higher salinity and pH, which would favor its authigenesis by neoformation. In the upper portion, the occurrence of thick kerolite-rich intervals suggests regular water inputs, contributing with a decreasing in salinity and pH, favoring the neoformation of kerolite and later kerolite-stevensite mixed layering. The saponite would be the result of the transformation from Al-smectite into Mg-smectite in a Mg²⁺ rich medium. The results indicate that lake hydrochemical processes would have allowed the establishment of a basic depositional sequence, from base to top, as follows: (i) initial lake expansion stage marked by the occurrence of saponite, (ii) later kerolite neoformation, (iii) formation of kerolite-stevensite mixed layer with increasing salinity, and (iv) neoformation of stevensite, marking a final stage of maximum salinity (evaporation) and alkalinity of the lake.

This study investigates the mineralogy and chemical characteristics of pre-salt clay minerals, classifies them, and defines assemblages in reactive microsites. Using Electron Probe Micro-Analysis (EPMA), the chemical formulas of Mg-rich clays were determined. Stevensite exhibited low interlayer charge and aluminum content, while kerolite was characterized by a minimal charge. K/S (kerolite/stevensite) mixed layer showed intermediate compositions and charges between these endmembers. Saponite was distinguished by higher levels of Al, K, and Fe, along with a higher interlayer charge. The proposed assemblages are as follows: saponite in mudstone facies (without spherulites/shrubs), with a hybrid matrix; pure kerolite in spherulstone and shrubstone facies, marked by the absence of significant reactions and high preservation of matrix and textures; stevensite in facies with extensive matrix replacement by dolomitization/silicification; and K/S and kerolite in similar facies with intermediate matrix replacement levels and the coexistence of two intimately related clay mineral compositions. This study enables reliable differentiation of these species based on point mineral chemistry and mapping, combined with a microsite approach and conventional techniques. Additionally, it discusses the formation of pre-salt clays, influenced by significant kinetic and chemical interactions during their genesis and burial to depths of approximately 5 km.