Magma mixing and magmatic-to-hydrothermal fluid evolution revealed by chemical and boron isotopic signatures in tourmaline from the Zhunuo–Beimulang porphyry Cu-Mo deposits

We present coupled textural, elemental, and boron isotopic data of tourmaline from the large Zhunuo–Beimulang collision-related porphyry copper deposits (PCDs) located within the western Gangdese, Tibet. Based on morphology and high-resolution mapping, the tourmaline is classified into three paragenetic generations. The first generation of schorlitic Tur-1 occurs in the monzogranite porphyry as disseminations intergrown with porphyritic K-feldspar and plagioclase. It shows decreasing Fe and Ca and increasing Mg and Al contents from core to rim and has relatively homogeneous δ¹¹B values (− 9.9 to − 8.6‰); low Fe³⁺/(Fe²⁺ + Fe³⁺), Cu, F, H₂O, and Sr/Y ratios; and high rare earth elements. These features indicate Tur-1 formed in a low fO₂ and metal-poor granitic magma during the pre-mineralization stage. The second generation of porphyritic euhedral Tur-2 is hosted in diorite porphyry enclaves and dikes, where it is intergrown with plagioclase and biotite. It forms part of the schorl-dravite solid solution, with high Fe³⁺/(Fe²⁺ + Fe³⁺), Cu, F, H₂O, Sr/Y, and δ¹¹B (− 9.7 to − 5.1‰) values. These features indicate it crystallized from a hydrous, oxidized, metal-, and volatile-rich diorite magma. The third generation of Tur-3 is the most volumetrically important and occurs as veinlets and disseminations in the porphyry, or around Tur-1 and Tur-2. It shows radial and oscillatory zoning and is locally intergrown with chalcopyrite and pyrite within the main mineralization assemblage. It has δ¹¹B values (− 10.5 to − 6.0‰) that overlap with Tur-1 and Tur-2 values. Tur-3 also has variable Fe³⁺/(Fe²⁺ + Fe³⁺), Cu, and volatiles (F and H₂O), indicating it crystallized from oxidized to relatively reducing metal- and volatile-rich hydrothermal fluids. Overall, the three generations of tourmaline show a narrow range of δ¹¹B values between − 10.5 and − 5.1‰ that are indicative of a single magmatic source. The high Cu, ferric iron, volatiles, and δ¹¹B values in Tur-2 are interpreted to reflect injection of diorite magma into an open crustal magma storage system that led to the formation of an oxidizing and metal-volatile-rich porphyry system. The three stages of tourmaline formation reflect evolution of the magmatic–hydrothermal system from low fO₂ conditions towards more oxidizing, volatile-rich conditions and then a return to more reducing conditions that accompanied Cu precipitation. Overall, the injection of oxidized metal-rich magma into a long-lived magma reservoir is a critical driving force for the development of collision-related PCDs.