REEs and U distribution in P-rich nodules from Gelasian Apulian Tethyan carbonate: A genetic record

In the Tethyan realm the carbonate-dominated Meso-Cenozoic South Tethyan Phosphogenic Province is of considerable economic importance since it represents the greatest accumulation of sedimentary phosphorites. In southern Italy, in the Salentine peninsula (the southern part of the Apulian Carbonate Platform, ACP), is well documented the occurrence of Cenozoic P-rich levels consisting of nodules and pebbles and showing a large P2O5 fluctuation (4.07-22.07 wt%), due to variable calcite abundance. The mainly observed P-bearing minerals are hydroxyapatite and carbonate fluorapatite and U, together with Sr and Pb, preferentially acts as Ca substitutes in both lattices. Minor authigenic monazite (LREE-bearing phosphate) and xenotime (HREE+Y-bearing phosphate), likely formed during sediment burial compaction and diagenesis. The total REEs' abundances and the shape of the shale-normalized REE-patterns in the P-rich nodules are in the range of those typically observed in Paleocene-Eocene through Pleistocene-Recent P-rich sediments, supporting the idea of a broadly consistent ocean chemistry in this span of geological time. The (La/Yb)N proxy is within the modern seawater range, signifying early diagenetic adsorption played only a minor role in affecting the REEs' distribution. The Ce and Pr anomalies suggest some P-rich nodules experienced very localized hypoxic to anoxic conditions promoting Ce/Ce* spurious results in a generally oxic to hypoxic environment causing real negative Ce anomaly. This scenario is reinforced by the lack of the coupled uranium-vanadium enrichment typically observed in an anoxic environment. Since the Pliocene the eastern Mediterranean was variously affected by oxygenation and productivity and it is likely the ACP phosphate-rich sediments formed under low sedimentation rates and authigenesis in a bottom current-dominated regime, as also indicated by the glauconite occurrence. Transgressions and sea levels rising following major glaciations may have favored the deposition of phosphate sediments by creating new restricted basin configurations and increased nutrient input promoted by upwelling processes.