Fluorite REE-Y (REY) geochemistry of the ca. 850 Ma Tumen molybdenite–fluorite deposit, eastern Qinling, China: Constraints on ore genesis

• The ca. 850 Ma Tumen Mo-F deposit occurs in the southern margin of NCC.
• The ΣREE, Y/Y* and Y/Ho values in fluorite increase from early to late.
• The Eu/Eu*, Ce/Ce* and (La/Yb)N values in fluorite decrease from early to late.
• The fluid became less reducing and less acidic along with cooling.
• Fluorite was formed by interaction of magmatic fluids with carbonate wallrocks.

The Tumen molybdenite–fluorite vein system is hosted by carbonate rocks of the Neoproterozoic Luanchuan Group, located on the southern margin of the North China Craton (NCC) in central China. Previous studies divided the mineralization into four stages according to the crosscutting relationships between veinlets and their mineral assemblages. In this contribution, two distinctive types of fluorite mineralization are recognized: 1) the first type (Type 1) includes colourless, white or green fluorite grains present in Stage 1 veins; and 2) the second type includes Type 2a purple fluorite present in Stage 2 veins and does not coexist with sulfides, and Type 2b purple fluorite crystals associated with sulfides in Stage 2 veins. The rare earth element (REE) content in the fluorite ranges between 13.8 and 27.9 ppm in Type 1, 16.9 and 27.2 ppm in Type 2a, and 42.5 and 75.1 ppm in Type 2b, which suggests that the fluorite was precipitated from acidic fluids (given that REEs are mobile in saline HCl-bearing fluids at high temperature (~ 400 °C)). Comparing the REE chemistry of the Stage 1 against Stage 2 fluorite, the LREE/HREE ratios decrease from 9.8 to 4.0, La/Yb ratios decrease from 16.0 to 6.9 and La/Ho ratios decrease from 10.2 to 3.0, indicating that the hydrothermal process was at high-T and low-pH conditions. The Eu/Eu* ratios in the fluorite decrease from 1.11 ± 0.35 for Type 1 through 0.89 ± 0.19 for Type 2a to 0.75 ± 0.17 for Type 2b, suggesting a gradual increase in oxygen fugacity (fO2) and pH of the mineralising fluid. The Tb/Ca, Tb/La and Y/Ho ratios of the fluorite types indicate that they were formed from the interaction between magmatic fluids and carbonate wallrocks. The fluorite samples show similar REE + Y (REY) patterns to those of dolostone units in the Luanchuan Group and the nearby Neoproterozoic syenite, suggesting that the REY in the fluorite was mainly sourced from the host-rocks, although the syenite could be an additional minor source.