The Laal-Kan fluorite deposit,Zanjan Province,NW Iran: constraints on REE geochemistry and fluid inclusions

The Laal-Kan fluorite deposit (west of Zanjan city, NW Iran) mainly occurred as some open-space filling and vein/veinlet in the schist of the Paleozoic age. Mineralogically, calcite, fluorite types (white, smoky, and violet), and quartz are the principal constituents accompanied by a number of minor accessory minerals such as hemimorphite, hematite, barite, and clays. Based on chemical analyses, fluorites of various colors were found to have low rare earth element (REE) concentrations (4.16–25.67 ppm). The chondrite-normalized REE patterns indicated that early fluorites were enriched in LREE, relative to HREE, whereas late fluorites were enriched in HREE relative to LREE. This study, therefore, indicated that fugacity of oxygen likely played a significant role in the occurrence of positive Ce and negative anomaly in the late fluorite. Furthermore, the Gd behavior of the fluorite samples could be attributed to the Gd-F complex in ore-forming fluids. On the other hand, low pH hydrothermal fluids under alkaline conditions were probably the main mechanism responsible for the deposition of the early fluorites in this district. Fluorite-hosted fluid inclusion analyses also indicated that fluorite-forming fluids consisted of NaCl, MgCl₂, CaCl₂, and LiCl with a narrow T_H (118–151 °C) and high salinities (18.96–23.47 wt.% NaCl equiv.). Further, the diagram of Tb/La-Tb/Ca ratios revealed that fluorites were predominantly deposited in the hydrothermal environment and the late stage fluorites could be considered as the product of the secondary mineralization of the early fluorites due to the interaction of the fluid with the early fluorites.