The Pliocene Punta Piccola series, deposited on the Sicily sill at 100–400 m depths, consists of alternating whitish hemipelagic marl and carbonate-poor, organic-carbon-richer, brownish dark marl. The rhythmic bedding is interpreted to result from the precession driven alternation of more or less humid periods. In the present study, we compare the mineralogical and geochemical composition (isotope ratios of oxygen and carbon; Ca, Mn, Mg, Sr, and Fe concentrations) of the carbonate fractions of the whitish marl to those of the dark layers to evaluate the environmental changes that likely produced these alternations.
High Mn concentrations in the dark layers, and the occurrence of pseudo-kutnahorite (Mn-Ca mixed carbonate), bioturbation, ostracodes, and benthic foraminifera favour the hypothesis of the dark-layer deposition taking place under oxygen-bearing bottom waters. The original value of the concentration of the organic carbon in the dark layers of Punta Piccola, estimated from the δ13C measured in the carbonate fraction, was higher than the post-diagenetic one. It may have reached 7% in the dark layer 107, which was therefore a true sapropel at the time of deposition. This result indicates that anoxic conditions are not a prerequisite for sapropelic sediment formation. However, the pristine concentration of the organic carbon in the dark layers at Punta Piccola is lower than those of coeval sapropels cored in the nearby deep settings, which were deposited under an anoxic water column. This difference may result from the effect of water column anoxia on the organic carbon content.
Diagenetic reactions took place in the dark layers through the oxidation of large amounts of organic matter. The dissolution of primary calcium carbonates (biogenic in origin) and the reduction of Fe and Mn oxyhydroxides led the interstitial solutions to be supersaturated towards Mn-rich calcite and/or pseudo-kutnahorite. The secondary carbonates are Mg-enriched and Sr and Fe-depleted. The negative shifts of the δ18O signal in the carbonates of the dark layers of Punta Piccola are consistent with an increased river discharge in the Mediterranean at the time of deposition.