Geochemical characteristics of Triassic and Cretaceous phosphorite horizons from the Transdanubian mountain range (western Hungary); genetic implications

The carbonate-dominated Mesozoic sequence of the Transdanubian Mountain Range contains Triassic, uranium-enriched phosphorite layers and Cretaceous, REE-enriched nodular phosphorite. Detailed investigation of these deposits may have an economic benefit because of their large U and REE contents. The dominant minerals in the Triassic phosphorite are carbonate-bearing fluorapatite (CFA) and calcite. According to the electron-probe microanalysis (EPMA) the U is mainly associated with the CFA crystals. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) measurement shows that CFA contains 137-612 ppm U and 113-261 ppm total REE + Y. The LA-ICP-MS U-Pb age of the uppermost phosphorite horizon is 237 ± 11 Ma, which conforms with the stratigraphic age of the host limestone. The Cretaceous nodular phosphorite occurs on the base of an Aptian crinoid-bearing limestone mostly in the form of encrustations around bio- and silicic-clasts, but the clasts also contain phosphorite. The main minerals in these crusts are CFA, calcite, quartz, glauconite and Fe-oxide-hydroxides. Based on EPMA the REE enrichment is related to CFA and LA-ICP-MS measurements show that it contains 748-2953 ppm total REE + Y. The redox-sensitive proxies and the shape of NASC normalized REE patterns indicate that both phosphorites formed in anoxic environments. There are significant differences between these deposits such as appearance, rock-forming minerals, and U and REE contents which indicate differences in their sedimentary environments. The present results suggest that the Triassic phosphorite was formed by inorganic precipitation in a reducing environment close to sea-mounts. The Cretaceous occurrence resulted from a concentric growth mechanism in cold, ascending seawater at the continental margin environment during the anoxic Selli Event (OAE 1a) and/or Paquier Episode (OAE 1b). The critical raw material contents were derived from other sources.