Hydrothermal alteration and the remobilization of rare earth elements during reprecipitation of nano-scale apatite in phosphorites

Sedimentary phosphorites enriched in rare earth elements (i.e., REE) are an important reservoir of these critical metals and may have the potential to resolve the global REE supply risk in the future, which is widely distributed around world. However, the occurrence and utilizability of REE in phosphorites remain contentious. In this study, multiple-scale analysis techniques were used to investigate the mineralogical and geochemical charac-teristics of typical REE-enriched phosphorites from Zhijin, SW China. The mineralization was divided into two stages: early fluorapatite (Fap1) that formed during the sedimentary-diagenetic stage, and late fluorapatite (Fap2) that formed during the hydrothermal alteration stage. The in situ REE geochemical data (i.e., quantitative data and mapping analysis) and scanning electron microscopy images show that Fap1 is the main REE host phase, because it is abundant and high REE concentration. Data obtained by both laser-ablation-inductively coupled plasma-mass spectrometry and high-resolution transmission electron microscopy reveal that most REE are resident in the lattice of nano-scale fluorapatite, which could be remobilized by hydrothermal fluids during the process of dissolution of nano-scale Fap1 and reprecipitation of micro-scale Fap2. In addition, the formation of synchysite-(Y) in the altered phosphorites involved reprecipitation of the mobilized REE. We suggest that F -and SO42- in fluids play a major role in the mobilization of REE in fluorapatite and that CO32- sourced from dolomite alteration contributes to the precipitation of REE. Our results indicate that REE in fluorapatite can be remobilized and further enriched by hydrothermal alteration to REE fluorocarbonates (the current predominant economic source of REE minerals). Overall, our results reveal that REE occur mainly in the lattices of fluorapatite and synchysite-(Y) in phosphorites, and provide new insights into the mineralization mechanism and industrial availability of REE-enriched phosphorites.