Trace and Rare Earth Elements, and Sr Isotopic Compositions of Fluorite from the Shihuiyao Rare Metal Deposit, Inner Mongolia: Implication for Its Origin

Abundant fluorites occur in the Shihuiyao rare metal (Nb-Ta-Rb) deposit in Inner Mongolia of NE China, and they can be classified by their occurrence into three types. Type I occurs disseminated in greisen pockets of albitized granite. Type II occurs in the skarn zone between granite and carbonate host rocks, and it can be subdivided into different subtypes according to color, namely dark purple (II-D), magenta (II-M), green (II-G), light purple (II-P), and white (II-W). Type III are the fluorite-bearing veins in the silty mudstones. On the basis of petrography of the fluorites and their high contents of HFSEs (high field strength elements) and LILEs (large ion lithophile elements), strong negative Eu anomalies, and tetrad effects, we suggest that Type I fluorites crystallized in a late-magmatic stage with all the components derived from the granite. The high Y/Ho ratios suggest that the Type II fluorites crystallized in the early- or late-hydrothermal stage. The rare earth elements (REEs) characterized by various Eu anomalies of the Type II fluorites indicate a mixed origin for ore-forming metals from granite-related fluids and limestones, and the oxygen fugacity increased during fluid migration and cooling. Compared to the Type II fluorites, the similar trace element contents of the Type III suggest a similar origin, and remarkable positive Eu anomalies represent a more oxidizing environment. The Sr isotopic composition (Sr-87/Sr-86)(i) = 0.710861) of the Type I fluorites may represent that of the granite-derived fluids, whereas the (Sr-87/Sr-86)(i) ratios of the Type II (0.710168-0.710380) and Type III (0.709018) fluorites are lower than that of the Type I fluorites but higher than those of the Late Permian-Early Triassic seawater, suggesting a binary mixed Sr source, i.e., granite-derived fluids and marine limestones. Nevertheless, the proportion of limestone-derived Sr in the mixture forming the Type III fluorites is much higher than that of Type II. The rare metal Nb and Ta get into the granite-derived F-rich fluids by complexing with F and precipitate in the form of columbite-group minerals after the Type I fluorites crystallize. Most of Nb and Ta may have deposited as columbite-group minerals during the magmatic stage, resulting in no Nb-Ta mineralization in the hydrothermal stage when the Type II and III fluorites formed. Hence, the Type I fluorites in the Shihuiyao mining area can be used as an important exploration tool for the Nb-Ta mineralization.