Karst bauxite deposits are currently investigated as a new resource for rare earth elements (REE) in order to avoid present and future supply shortfalls of these critical metals. The present work focuses on the geochemistry and mineralogy of the REE in karst bauxite deposits of the Catalan Coastal Range (CCR), NE-Spain. It is revealed that the studied bauxitic ores have a dominant breccia and local ooido-pisoidic and pelitomorphic texture. The bauxitic ores are mostly composed of kaolinite and hematite, as well as of lesser amounts of boehmite, diaspore, rutile and calcite. The mineralogy and major element composition indicate incomplete bauxitization of an argillaceous precursor material possibly derived from the erosion of the Mesozoic Ebro massif paleo-high. The studied bauxites are characterized by ∑REE (including Sc, Y) between 286 and 820 ppm (av. 483 ppm) and light REE to heavy REE (LREE/HREE) ratios up to 10.6. REE are mainly concentrated in phosphate minerals, identified as monazite-(Ce) and xenotime-(Y) of detrital origin and unidentified REE-phosphates of a possible authigenic origin. REE remobilization presumably took place under acidic conditions, whereas REE entrapment in the form of precipitation of authigenic rare earth minerals from percolating solutions was related to neutral to slightly alkaline conditions. During the bauxitization process no significant REE fractionation took place and the REE distribution pattern of the bauxitic ores was governed by the REE budget of the precursor material. Finally, adsorption as a main REE scavenging mechanism in the studied CCR bauxite deposits should not be considered, since the presented data did not reveal significant REE contents in Fe-and Mn-oxyhydroxides and clay minerals.
The Virulundo carbonatite in Angola is one of the largest in the world and contains pyrochlore as an accessory mineral in all of the carbonatite units (calciocarbonatites, ferrocarbonatites, carbonatite breccias and trachytoids). The primary magmatic pyrochlore is fluorine dominant and typically contains about equal molar quantities of Ca and Na at the A site. High-temperature hydrothermal processes have resulted in the pseudomorphic replacement of the primary pyrochlore by a second generation of pyrochlore with less F and Na. Low-temperature hydrothermal replacement of the first and second generation pyrochlore, associated with quartz-carbonate-fluorite vein formation in the carbonatite, has produced a third generation of pyrochlore, with a high Sr content. The Sr appears to have been released by low-temperature hydrothermal replacement of the primary magmatic carbonates. Finally, supergene alteration processes have produced late-stage carbonates, goethite, hollandite and rare earth element (REE) minerals (mainly synchysite-(Ce), britholite-(Ce), britholite-(La), cerite-(Ce)). Cerium separated from the other REE s in oxidizing conditions and Ce4+ was incorporated into a late generation of supergene pyrochlore, which is strongly enriched in Ba and strongly depleted in Ca and Na.