Late Cretaceous black shales from the tuscan sedimentary succession (northern Tuscany, Italy): Geochemistry and ore mineralogy

We report on the first geochemical and mineralogical study of the Late Cretaceous black shales and black phyllites occurring within the basal portion of the “Scaglia toscana” and “Scisti sericitici” formations, respectively (Northern Apennines, northern Tuscany, Italy). The black shales occurring within the “Scaglia toscana” Formation are interbedded with red and greenish shales and form cm-thick layers; in some localities they are characterized by the occurrence of cm-sized pyrite nodules. Black phyllites and meta-cherts in the “Scisti sericitici” Formation are associated with Cu ores and with a small pyrite-molybdenite mineralization. These rocks are made of variable amounts of quartz, “chlorite”, illite/muscovite, pyrite ± calcite ± albite plus accessory amounts of baryte, apatite, sulfides and sulfosalts. In addition, they contain abundant carbonaceous matter (2-12 wt% total organic carbon). Whole-rock analyses by ICP-MS reveal a marked enrichment of Cd, Ag, Zn, Sb, Cu, Mo, V, Pb, and Tl with respect to the average marine shale and to the more typical shales of the “Scaglia toscana” Fm. The distribution of these elements in the studied samples is compatible with a strongly anoxic and euxinic depositional environment. The hyper-enrichment of Cd, Ag, Zn, Sb and Cu strongly suggests that besides from seawater these elements were extracted from additional sources, most likely hydrothermal vents