Combined statistical and petrological analysis of provenance and diagenetic history of mudrocks: Application to Alpine Tethydes shales (Sicily, Italy)

Abstract

Mineralogical (X-ray diffraction) and geochemical (X-ray fluorescence) compositional data of Alpine Tethyde mudrocks from Sicily were used to unravel the interplay of provenance and diagenesis by means of multivariate statistical methods (PCA, discriminant function analysis) designed for non-negative constant-sum data. The Sicilian Alpine Tethydes comprise Cretaceous–Eocene scaly shales (Mt. Soro and Upper Scagliose Shales Units), Eocene–Oligocene variegated shales (Troina and Nicosia Units), and Miocene Numidian shales (Nicosia Unit). The use of biplots of clr-transformed variables allows discrimination of two different groups of shales. High CIA values reveal a strongly weathered source area especially for the Numidian shales. The analyses of mixed-layered clay minerals indicate that the behaviour of K2O and geochemical affine elements is controlled by the diagenetic grade, which increases from south-west to north-east in response to tectonic loading. Ratios of selected elements (Zr, Y, La, Nb, Ti, Co, Cr, Ni), considered essentially unchanged with respect to the source rocks, are similar in the scaly and variegated shales, and resemble the Variscan Peloritani metamorphic basement. In contrast, the distinct geochemical signature of the Numidian shales reveals a source similar to the average cratonic sandstone, suggesting derivation from external sources located in the foreland. Multivariate discriminant analysis performed on selected trace elements confirms the previous suggestions.