Ce-anomalies in the textural components of Upper Cretaceous karst bauxites from the Apulian carbonate platform (southern Italy)

Abstract

The chemical and mineralogical composition of Upper Cretaceous Apulian karst bauxites (southern Italy) and their textural components, i.e. ooids and matrix, has been studied. The bulk samples are composed of boehmite, hematite, anatase and kaolinite. The samples collected along a vertical profile show a downward enrichment for the elements Rb, Sr, Ba, Ni and Cr. A similar distribution is observed in deposits bauxitized in situ at the expense of matrix-like material collected in the karst zone. The ooids consist mainly of hematite with minor boehmite and anatase, whereas in the matrix boehmite prevails on hematite, kaolinite and anatase. In the void fillings in the matrix there is a Ca-fluorocarbonate having a Ce/Ce * of 5.8. The ooids, with the exception of Ce, are enriched in REE and show a higher (La/Yb) ch ratio relative to the matrix. The matrix exhibits a large positive Ce-anomaly whereas the ooids have negative Ce-anomaly. The Ce fractionation between the textural components can be explained assuming: (1) Ce oxidation and cerianite precipitation in the uppermost part of the deposits; (2) scavenging of REE from Ce-depleted percolating solutions by the iron oxide, inducing both REE-enrichment and Ce-negative anomalies in ooids; (3) remobilization of cerium as fluoride complex, as a consequence of more acidic conditions in the uppermost part of the deposit, and precipitation of Ce 3+ as fluorocarbonate mineral toward the carbonate bedrock barrier, at alkaline pH. Alternatively, the cerium remobilization, possibly as a carbonate–fluoride complex, could be due to an Eh decrease, favoured by a rise of the groundwater level.