The metasomatism affecting karstic bauxites from the south-central Pyrenees, Catalonia (NE Spain) and its implications on the REE geochemistry in similar geological settings.

Karstic bauxite deposits are the main resource of aluminum in Europe and are formed through a combination of weathering, leaching, and deposition processes known as bauxitization. Bauxites have recently been proposed as unconventional resources of rare-earth elements (REE) as well. The studied karstic bauxite deposits are located on the salt-detached Serres Marginals thrust sheet, at the external most unit of the south-central Pyrenees (Catalonia, NE Spain). The Pyrenean bauxites are found overlaying and filling karstic surfaces forming aligned pockets up to several meters thick. These deposits have been mined for more than 20 years and present high variability in SiO₂, Al₂O₃ and Fe₂O₃ contents. Here, we characterize these deposits for the first time by a combination of field geology, XRD, FTIR and XRF to determine their formation, mineralogy, and geochemistry and to understand the causes affecting their compositional variations. Field data indicate that the bauxite deposits fill a paleokarst system affecting Dogger dolostones and/or Tithonian-Berriasian limestones. XRD data indicate that the studied karstic bauxites are mainly composed of Al-rich minerals kaolinite and boehmite, in addition to the Fe-oxide hematite, and lesser amounts of the Ti-oxides rutile and anatase. The detailed study of the FTIR spectra also confirmed the presence of diaspore and dickite. XRF data confirm the presence of varying amounts of Al, Fe and Si in addition to varying low contents of REE. These results suggest that boehmite was formed first during bauxitization and later transformed to diaspore, kaolinite and finally to dickite upon metasomatism. The presence of dickite in faults and fractures provides a direct proof for such fluid circulation. Our results suggest that the mechanisms responsible of the compositional variations in karstic bauxites are rather complex and fall beyond the standard bauxitization processes. The observed metasomatism should be further assessed, since the inferred fluid-rock interactions are susceptible to affect and mobilize REE not only in the south-central Pyrenees karstic bauxites but elsewhere in similar geological settings.