Shales and claystones in the Permian Irati Formation consist of Al-rich or Fe-Mg clay minerals in its southern/central and northern parts, respectively. The constrasting compositions indicate particular geological and paleo-environmental conditions. The purpose of this study was to determine the conditions of formation by characterizing the black shales and claystones from different sections of the northern edge of the basin, some of which reveal the presence of intruded diabase sills.
Black shales consist of saponite or saponite-talc mixed layers, talc, lizardite, nontronite, and quartz. Green claystones are nontronite-rich but also contain lizardite, talc, and quartz. The chemical compositions of the black shale and claystones, except for one sample (POR-56), exhibit a positive correlation of the TiO2, Cr, and P2O5 contents with Al2O3, which typically results from weathering processes. The presence of saponite, nontronite, and some accessory minerals (spinel, pyroxene, native silver) suggests altered basic-ultrabasic rocks as sediment sources, consistent with the rare earth element (REE) composition being less than the Post-Archean Average Shale (PAAS) or North American Shale Composite (NASC) levels and with negative Ce and Eu anomalies. Sample POR-56 consists largely of nontronite and is anomalously rich in zircon, monazite, and apatite. Chemically, sample POR-56 is different from the black shales and claystones, being richer in Al2O3-Fe2O3, MgO-poor, and having greater REE contents than the PAAS or NASC standards. The POR-56 bed is probably a bentonite resulting from the alteration of volcanic ash in sea water (strong, negative Ce anomaly). The Zr/TiO2vs. Nb/Y relation indicates that the magmatism was andesitic. During the Upper Permian, intermediate to basic volcanic activity was recorded in the Mitu Group of the Central Andes.
Close to the diabase sill, the black shales and claystones contain saponite, talc, and lizardite but nontronite is absent. Saponite and talc crystals, however, exhibit a larger coherent scattering domain size (CSDS) and are randomly oriented with respect to the sedimentary bedding. The thermal metamorphism effect is confirmed by the presence of secondary enstatite-augite and albite crystals.