In-situ molybdenite and rutile geochemistry of the Nannihu porphyry Mo-W deposit, East Qinling, China: A perspective on ore-forming processes

Abstract

As the important strategic mineral resource, molybdenum is widely utilised by various industries of national economy. Most of the Chinese Mo deposits are classified as porphyry deposits, such as the Nannihu porphyry Mo-W deposit that is one of the biggest Mo deposits in China. Previous studies mostly focused on the geochemistry, geochronology, and isotopic geochemistry of the Nannihu deposit, but its element immigration and occurrence as well as the ore-forming source remain unclear, which limits the development of ore prospecting. Here we document in-situ major and trace element geochemistry of different stages of molybdenite and rutile from the Nannihu deposit, with major aims to determine ore-forming element immigration and occurrence and to reveal ore-forming processes. Based on mineral assemblages and micro-texture, three types of rutile were identified in the Nannihu deposit. The type-1 rutile has stable Y/Ho ratios 16.74–20.82 and similar upper crust rare earth elements (REEs) patterns, which suggest magmatic and crustal origin. The type-2 and 3 rutiles show wide variation Y/Ho ratios (10.69–49.55 for type-2 and 17.85–43.64 for type-3) and belong to hydrothermal rutiles. In addition, two types of molybdenite are also presented, with the Mo1-type for the major ore-forming stage and the Mo2-type for the late ore-forming stage. The fluctuation of elements in the time resolved LA-ICP-MS spectra curve diagram of the Mo1- and Mo2-type molybdenites indicate that the Te, Bi, Pb, Fe and Mn elements are hosted as mineral inclusions in molybdenite lattices. However, the Re and Se elements in these molybdenites display flat signatures and have negative correlations with Mo and S elements, which imply that the Mo and S elements are substituted and occur as isomorphous constituents in molybdenite lattices. The low Re contents (1.60–12.90 ppm) of molybdenites also suggest crustal-mantle mixing metallic sources for the Nannihu deposit. The increasing Fe (4245 to 23943 ppm) and W (1631 to 5922 ppm) contents in hydrothermal type-2 and type-3 rutiles as well as the increasing W contents (113 to 243 ppm) in Mo1- and Mo2-type molybdenites both indicate that the Nannihu ore-forming fluids were under the temperature and oxygen fugacity (fO2) of reduction conditions. The Mo1-type molybdenite is enriched in light REEs and depleted in high field strength elements (HFSEs), and coupled with the late ore-forming stage of F-rich fluorite, which indicate the ore-forming fluid evolution from Cl- to F-rich. Integrating with previous studies, the mineralising fluids of the Nannihu deposit are suggested to be featured by high Cl−, CO2 and metallic contents. The Mo and W ions in mineralising fluids immigrate as Cl-complexes at the early stage of mineralisation, the Mo4+ is then replaced by W4+ in molybdenite lattices at the later stage, and the high temperature and fO2 of the early ore-forming fluids promote the migration of Mo and W elements during ore-forming processes. Eventually, the fluids boiling, and the reduction conditions in temperature and fO2 jointly result in the final precipitation of Mo and W to generate the giant Nannihu deposit under extensional tectonics.