Upper cretaceous clayey levels from western Portugal (Aveiro and Taveiro regions): Clay mineral and trace-element distribution

Abstract

Clay-rich deposits of Upper Cretaceous levels in the Taveiro (Reveles and S. Pedro) and Aveiro (Bustos) regions of west-central Portugal are economically and environmentally important, but detailed chemical and mineralogical characterization is lacking. The purpose of this study was to partially fill that gap by correlating the trace-element geochemistry (particularly the rare earth elements, REE) with the mineralogy of both the whole rock and of the <2 μm fraction along selected stratigraphic levels of the formations. The results will help the ceramics industry in the region and will be important in paleoreconstruction environmental studies. Mineralogical and chemical characterizations were carried out using X-ray diffraction (XRD), X-ray fluorescence (XRF), and instrumental neutron activation analysis (INAA). The following clay-mineral associations were identified: (1) at Reveles - smectite, illite, and kaolin minerals; (2) at S. Pedro - kaolin minerals and illite; and (3) at Bustos - illite, kaolin minerals, and mixed-layer illite-smectite. The distribution of trace elements in the <2 μm fraction depended on the clay mineralogy, suggesting that the trace elements were incorporated in, adsorbed to, or even replaced major elements in the clays, as follows: (1) first-row transition elements, particularly Zn and Ga, were enriched when smectite predominated; (2) As, Rb, and Cs were enriched in this fraction of the S. Pedro deposit, the only one with Fe (oxyhydr)oxides and a high proportion of illite; and (3) REE were more concentrated when kaolin minerals predominated. Eu was enriched in the <2 μm fraction, which was due to preferential incorporation in the Fe (oxyhydr)oxides and/or carbonates.