Depositional redox conditions of the Grybów Succession (Oligocene, Polish Carpathians) in the light of petrological and geochemical indices

This study details the petrology and chemistry of the Oligocene succession of the Grybów Nappe in its stratotype-locality in the Grybów tectonic window (Polish Carpathians). The section studied is composed of the Sub-Grybów Beds, the Grybów Marl Formation (GMF), and the Cergowa Beds, representing the middle to upper part of the Oligocene succession. The rocks studied consist of quartz, calcite, Na-plagioclase, muscovite and clay minerals (illite-smectite with 25–30% of smectite and kaolinite). Additionally, hematite occurs in the GMF and chlorite in the Cergowa Beds, respectively. The macerals assemblage of the GMF is dominated by landplant-derived compounds of liptinite, associated with minor amounts of vitrinite representing type II kerogen. The total organic carbon (TOC) content is between 0.45 and 6.16 wt.%. The δ13Corg values of the GMF vary between –27.1 and –27.9‰. The values of both carbon and oxygen isotopic ratios of carbonates range for δ13C from –1.1 to –4.3‰ VPDB, and for O from –1.5 to –4.8‰ VPDB. The concentrations of Co, U, Ni, As, and Mo are higher in the GMF than in the adjacent strata and positively correlate with TOC and S. Values of the TOC/S and V/V+Ni ratios are 0.7 to 3.5 and 0.67 to 0.78, respectively, and indicate anoxic conditions. The ratios of U/Th and V/Cr (0.3–2.2, 1.18–3.18, respectively) suggest the change of oxic conditions to reducing conditions occurred during the GMF deposition. This change could have been preceded by a plankton bloom, initiated by a nutrient-rich freshwater inflow that is inferred from the decrease of the δ13Ccarb values and the terrestrial detritus supply. Thermal alteration of the Grybów Succession is concluded on the basis of smectite illitisation and low δ18O values.