Changes in depositional paleoenvironment of black shales in the Permian Irati Formation (Paraná Basin, Brazil): Geochemical evidence and aromatic biomarkers

Abstract

Physicochemical changes that occurred during deposition of Irati black shales were investigated via outcrop samples collected in the northeastern and central-eastern Paraná Basin. Various traditional geochemical indicators were used, in addition to newly detected biomarkers: C32 lanostane, simonellite, sempervirane, and C32–C35 benzohopanes. Bulk geochemistry parameters, mineralogy, and conventional saturated biomarkers, such as tetracyclic polyprenoids (TPPs), reflect restricted and hypersaline marine deposition with freshwater input and increased terrigenous contribution toward the top of the studied outcrops. This led to stratification of the water column, establishing euxinic conditions in the photic zone and reducing conditions at the bottom of the water column, which enhanced preservation of organic matter. Principal component and hierarchical cluster analyses were performed to group the samples according to their similar geochemical characteristics: prevailing marine environment (basal outcrop samples) and higher freshwater inflow with greater terrigenous contribution (top outcrop samples). These geochemical observations were corroborated by aromatic biomarkers such as triaromatic steroids, trimethylnaphthalenes, simonellite, and sempervirane. The aryl isoprenoid ratio (AIR) indicates persistence of photic zone euxinia (PZE) during Irati black shale deposition. The presence of C32 lanostane and C32–C35 benzohopanes is directly related to the hypersaline depositional environment of the analyzed samples. Finally, the C32-33/C32-35 benzohopane ratio is proposed as a thermal maturity proxy because variations in the ratio can be linked to the presence of a diabase sill and temperature catalyst minerals near one of the outcrops.