Enrichment of rare earth elements in the early Cambrian Zhijin phosphorite deposit, SW China: Evidence from francolite micro-petrography and geochemistry

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The Zhijin phosphorite deposit is a giant early Cambrian rare earth element (REE) deposit, with particular enrichment in heavy REEs, and is of high economic significance. The REEs of the deposit occur almost entirely in apatite, which, on the basis of petrographic characteristics, can be divided into francolite grains (90%), amorphous apatite, and phosphate fossils. In this paper, we report an investigation into francolite grains in different types of phosphorite from ore sections of the Zhijin deposit. Detailed petrographic and transmission electron microscopy observations reveal that the francolite grains are composed of nano-apatite crystals measuring 120–160 nm long. Trace-element contents of pyrite and whole-rock geochemical indicators (such as Cr/Zr and V/Ni ratios and Th/U–Co/Ni plots) suggest that the Zhijin phosphorite formed in an anoxic hydrothermal sedimentary environment. However, the negative Ce/Ce* and Eu/Eu* anomalies indicate that the diagenetic environment of the francolite grains was oxidic. Different diagenetic redox environments and the presence of transportation fractures in francolite grains identified under back-scattered electron imaging reveal that the francolite grains underwent prolonged abrasion and transportation in seawater before sedimentation. Petrographic observations and laser ablation–mass spectrometry element surface scanning analyses indicate that the REEs are uniformly distributed in nano-apatite in isomorphic form, and no nano-inclusions or REE minerals were found, implying that late mineralization was not the cause of REE enrichment. The higher (La/Yb)N ratios of francolite grains relative to seawater indicate that the francolite grains captured abundant REEs during the early diagenetic stage. We infer that prolonged exposure to seawater and the high specific surface area of francolite grains are the key factors that led to the enrichment in REEs. Combining the timing of the metallogenic epoch (543 Ma), Sr–Nd isotopic data, and the Y/Ho ratio, which is close to those of modern seawater, indicates that the REEs were sourced from paleo-seawater. Paleogeographic information suggests that during the early Cambrian, extensive continental collisions caused great amounts of continental weathering products to enter the paleo-ocean, leading to the production of abundant amounts of hydrothermal–sedimentary phosphorus and REEs in shallow seas, thus forming an ideal sedimentary environment for generating the REE resources of the Zhijin phosphorite deposit.