Kaolinite and dickite formation during shale diagenesis: isotopic data

Abstract

X-ray diffraction, scanning electron microscopy and O-isotope geochemistry have been used to investigate the origin and possible controls on polymorphic transformation of kaolin minerals filling veins in Cretaceous shales from the Gibraltar Strait area (southern Spain). The mineralogy of the enclosing shales indicates that kaolin minerals formed from smectite dissolution, a process that silmultaneously originated I/S mixed-layers and quartz. Kaolinite and dickite δ 18O values suggest that an increase in the water isotopic composition, from Cretaceous sea water values (−1%) to values of about 3%, occurred parallel to smectite dissolution, the intensity of this process being the main factor controlling the isotopic composition of kaolin minerals. The minimum formation temperature ranges from 62°C for kaolinite to 86–96°C for dickite, indicating that the depth of burial was the main control on polymorph formation. This temperature range agrees with that deduced for illite/smectite ordering. The passage from kaolinite- to dickite-rich veins was accompanied, as deduced from SEM examination, by a morphologic evolution characterized by the division of large vermiculae, dominant in kaolinite samples, and the formation of short stacks and platy crystals, which are predominant in dickite. The mechanism of dickite formation, however, remains uncertain.