Apatite fingerprints on the magmatic-hydrothermal evolution of the Daheishan giant porphyry Mo deposit, NE China

Porphyry deposits are the main source for global Cu and Mo production. The generation of hydrous silicate magmas and subsequent separation of volatile-rich magmatic fluids with hydrothermal alteration are significant processes leading to the formation of porphyry deposits. However, a specific understanding of these processes has been limited by a lack of direct mineralogical records in the evolving magmatic-hydrothermal system. In this paper, we present an integrated textural and geochemical investigation on apatite from the giant Daheishan porphyry Mo deposit in NE China, illustrating that apatite can be a potential recorder of the magmatic-hydrothermal evolution of porphyry systems. Apatite from the ore-forming porphyry displays distinctive core-rim textures, with melt inclusions in the resorption cores (Type-A1) and co-existing of melt and fluid inclusions in the euhedral rims (Type-A2), indicating a magmatic-hydrothermal origin of apatite. This is also supported by both chemical and isotopic compositions obtained by in situ analyses using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and LA-multi collector-ICP-MS. The late Type-A2 apatite is relatively enriched in incompatible elements, such as rare earth elements (REE) and Th, but slightly depleted in fluid-mobile elements such as Na and S, compared to the early Type-A1 apatite. Relatively homogeneous (Sr-87/Sr-86)(i) ratios (0.70436-0.70504) of the Type-A1 and Type-A2 apatites indicate that they were formed in a relatively closed system without detectable contamination. Meanwhile, some apatite in the wall rock (biotite granodiorite) shows characteristics of secondary altered textures, resulting from the intensive alteration by hydrothermal fluids exsolved from the porphyry system. Apatite trapped in mineral phenocrysts of the wall rock is usually unaltered (Type-B1 apatite), with clear oscillatory growth zones in cathodoluminescence (CL) images. In contrast, the intergranular apatite is commonly altered (Type-B2 apatite), with chaotic zoning in CL images, abundant micro-fractures and secondary fluid inclusions. Compositionally, the Type-B2 apatite shows notable tetrad REE patterns, relatively lower light-REE and S contents, and elevated Sm-147/Nd-144 ratios compared to the Type-B1 apatite. LA-ICP-MS U-Pb dating yields a lower intercept age of 171.4 +/- 2.3 Ma for Type-B2, which is consistent with the age of 171.5 +/- 2.4 Ma for Type-A2, but is notably younger than the Type-B1 apatite (175.5 +/- 1.3 Ma). It is suggested that the Type-B2 apatite has been significantly reset by hydrothermal fluids exsolved from the porphyry system. Therefore, we conclude that the textures and geochemistry of apatite in porphyry systems can be used as a potential proxy for recording fluid exsolution and hydrothermal alteration processes.