Oxidation State Of Magma Research Articles

Processes controlling magma fertility at buenavista del cobre porphyry copper deposit (cananea, méxico): A new petrogenetic model based on zircon u-pb dating and apatite geochemistry

The Buenavista del Cobre is a world-class porphyry Cu-Mo deposit located in the Cananea Mining District, northern Sonora, México. Using zircon U-Pb dating, we show that the Proterozoic Cananea Granite, unconformably overlain regionally by Paleozoic limestones hosting skarn deposits underlies the present-day pit. We also present new crystallization ages for host rocks of copper mineralization in the District, dating for the first time a volcanic rock of the Henrietta Formation at 186.8 ± 1.1/3.0 Ma and the El Torre Syenite at 176.3 ± 1.1/2.9 Ma. Zircon U-Pb dating of the different porphyritic bodies reveals that the magmatic activity at Buenavista del Cobre lasted at least 4 Myr, from 59.7 ± 0.5/1.1 Ma to 56.1 ± 0.2/0.9 Ma. The deposit is composed by several porphyry intrusions referred to as “ore-rich” and “ore-poor” based on their individual metal contributions, which provides the opportunity to study the origin and processes enhancing magma fertility in an individual deposit. Combining our new geochronological dataset with geochemistry of apatite from the different porphyries allows us to propose a new petrogenetic model for the Buenavista del Cobre deposit. As the apatite Eu and Ce anomalies overlap with no clear difference between the ore-rich and ore-poor intrusions, we propose that the magmatic oxidation states of the magmas were similar. However, differences in apatite REE signatures, as well as variations in apatite Sr compositions between the two groups suggest that fractional crystallization processes in the parental magma influence the fertility of the porphyries. Additionally, apatite Cl contents of ore-rich porphyry intrusions are higher (>0.4 wt%) than the ore-poor intrusions (<0.2 wt%), suggesting an important role of the initial Cl content of the magmas in the mineralization process. These observations give new insights on the petrogenetic processes at origin of porphyry magma fertility. We propose that the evolution of the parental melt by fractional crystallization of hydrous minerals (hornblende) at upper crustal levels induced low H2O content of the residual magma, resulting in the formation of ore-poor porphyries. In contrast, we suggest that fractionation of anhydrous minerals (plagioclase) increased the H2O content in the residual melt, leading to the formation of ore-rich porphyries. Our new data allow us to propose an original genetic model for the Buenavista del Cobre deposit, which involves two cycles of supply, cooling and partial crystallization. This contribution shows that petrogenetic processes controlling porphyry copper magmas fertility are recorded in the composition of apatite at the deposit scale and highlights the importance of considering apatite geochemistry as an exploration tool.

Crustal magma oxidation state and endowments in porphyry copper deposits

Crustal magma oxidation state and endowments in porphyry copper deposits

Iron valence systematics in clinopyroxene crystals from ocean island basalts

The valence state of Fe plays a vital role in setting and recording the oxidation state of magmas, commonly expressed in terms of oxygen fugacity (fO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$f_{\ extrm{O}_{2}}$$\\end{document}). However, our knowledge of how and why fO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$f_{\ extrm{O}_{2}}$$\\end{document} varies within and between magmatic systems remains patchy because of diverse challenges associated with estimating the valence state of Fe in glasses and minerals routinely. Here we investigate Fe valence systematics in magmatic clinopyroxene crystals from ocean island basalts (OIBs) erupted in Iceland and the Azores to explore whether they record information about magma Fe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document} contents and magmatic fO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$f_{\ extrm{O}_{2}}$$\\end{document} conditions. Although many studies assume that all Fe in augitic clinopyroxene crystals from OIBs occurs as Fe2+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{2+}$$\\end{document}, we find that up to half of the total Fe present can occur as Fe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document}, with crystals from alkali systems typically containing more Fe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document} than those from tholeiitic systems. Thus, Fe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document} is a major if under-appreciated constituent of augitic clinopyroxene crystals erupted from ocean island volcanoes. Most Fe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document} in these crystals is hosted within esseneite component (CaFe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document}AlSiO6\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{6}$$\\end{document}), though some may be hosted in aegirine component (NaFe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document}Si2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document}O6\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{6}$$\\end{document}) in crystals from alkali systems. Observations from samples containing quenched matrix glasses suggest that the incorporation of Fe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document} is related to the abundance of tetrahedrally coordinated Al (IV\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mathrm {^{IV}}$$\\end{document}Al), implying some steric constraints over Fe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document} partitioning between clinopyroxene and liquid (i.e., DFe2O3cpx-liq\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$D\\mathrm {^{{cpx-liq}}_{{Fe_{2}O_{3}}}}$$\\end{document} values), though this may not be an equilibrium relationship. For example, IV\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mathrm {^{IV}}$$\\end{document}Al-rich {hk0}\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\{hk0\\}$$\\end{document} prism sectors of sector-zoned crystals contain more Fe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document} than IV\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mathrm {^{IV}}$$\\end{document}Al-poor {1¯11}\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\{\\bar{1}11\\}$$\\end{document} hourglass sectors. Moreover, IV\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mathrm {^{IV}}$$\\end{document}Al-rich compositions formed during disequilibrium crystallisation are enriched in Fe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document}. Apparent clinopyroxene-liquid Fe2+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{2+}$$\\end{document}–Mg exchange equilibria (i.e., KD,Fe2+-Mgcpx-liq\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$K\\mathrm{{_{D, {Fe^{2+}-Mg}}^{cpx-liq}}}$$\\end{document} values) are similarly affected by disequilibrium crystallisation in our samples. Nonetheless, it is possible to reconcile our observed clinopyroxene compositions with glass Fe valence systematics estimated from olivine-liquid equilibria if we assume that KD,Fe2+-Mgcpx-liq\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$K\\mathrm{{_{D, {Fe^{2+}-Mg}}^{cpx-liq}}}$$\\end{document} values lies closer to experimentally reported values of 0.24-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$-$$\\end{document}0.26 than values of ∼\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sim$$\\end{document}0.28 returned from a general model. In this case, olivine-liquid and clinopyroxene-liquid equilibria record equivalent narratives, with one of our glassy samples from Iceland recording evolution under fO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$f_{\ extrm{O}_{2}}$$\\end{document} conditions about one log unit above fayalite-magnetite-quartz (FMQ) equilibrium (i.e., ∼\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sim$$\\end{document}FMQ+1) and our glassy Azorean sample recording evolution under significantly more oxidising conditions (≥\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\ge$$\\end{document}FMQ+2.5) before experiencing syn-eruptive reduction, likely as a result of SO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document} degassing; our other glassy sample from Iceland was also affected by reductive SO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document} degassing. Overall, our findings demonstrate that the Fe valence systematics of clinopyroxene crystals can record information about the conditions under which OIBs evolve, but that further experimental work is required to properly disentangle the effects of magma composition, disequilibrium and fO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$f_{\ extrm{O}_{2}}$$\\end{document} conditions on clinopyroxene-liquid equilibria involving Fe2+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{2+}$$\\end{document} and Fe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document}.

Magmatic evolution and metallogenic diversity of the late Cretaceous granites in the Yidun terrane: Constraints from zircon and apatite geochemistry

Porphyry-hydrothermal type Cu-Mo(−W) deposits in the southern Yidun terrane (SYT) and hydrothermal-skarn type Sn-Pb-Zn-Ag deposits in the northern Yidun terrane (NYT) are closely related to late Cretaceous granitic intrusions in time and space. However, the genetic mechanisms and controlling factors responsible for the metallogenic diversity remain unclear. We investigated zircon and apatite compositions of the Sn-Pb-Zn-Ag-associated granites in northern Yidun terrane and the Mo-W-Cu and Mo-Cu-associated granites in southern Yidun terrane. The Cretaceous granites are distributed along a N–S-trending belt having ages ranging from 106 to 73 Ma, with a transition from predominant plagioclase crystallization to amphibole-dominated crystallization. Our data show that the granites from the NYT have lower zircon Eu/Eu* (0.06 ± 0.04), Ce4+/Ce3+, and ΔFMQ (FMQ is fayalite-magnetite-quartz) values compared to the granites in the SYT, indicating that the granites from the NYT are relatively reduced (ΔFMQ = -1.03 ± 1.02) in contrast to the oxidized granites in the SYT (ΔFMQ = 1.10 ± 1.05). Furthermore, apatite can record the volatile compositions of magma before fluid exsolution. Apatites in granites from the NYT with low XF/XCl ratios (≤120) are interpreted to have crystallized from volatile-undersaturated magma. These apatites are characterized by low Cl contents ranging from 0.04 to 0.12 wt% (0.07 ± 0.02 wt%; n = 21) and low SO3 contents of 0.01–0.06 wt%. In contrast, apatites in granite from the SYT with low XF/XCl ratios (≤80) have high Cl contents of 0.05 to 0.34 wt% (0.16 ± 0.07 wt%; n = 52) and SO3 contents of 0.01–0.46 wt%. The chemical compositions of zircon and apatite indicate that the Mo-W-Cu and Mo-Cu-associated granites in the SYT have higher fO2 and melt S contents before fluid exsolution than the Sn-Pb-Zn-Ag-associated granites in the NYT. Therefore, the contrasting magmatic oxidation states and S contents are critical in controlling the metallogenic diversity of the Cretaceous granites in the Yidun terrane. The Xingguolongba and Cuopu granites, first reported in this article, have U-Pb ages consistent with the Rongyicuo and Cuomolong granites. Furthermore, they exhibit similar geochemical properties, such as oxygen fugacity and volatiles, suggesting the possibility of forming Sn-Pb-Zn-Ag deposits.

Zircon fertility indicators compromised by mineral inclusion contamination: A case study from the Taoxikeng W deposit, South China

Zircon trace element compositions have been widely used as a tool to assess the ore-forming potential of magmatic-hydrothermal systems. However, many zircons contain accessory mineral inclusions which, if accidentally analyzed, could compromise reported zircon trace element signatures, especially when the mineral inclusions are sub-micrometer and thus hard to monitor using conventional microscopes. However, how mineral inclusion contamination influences the robustness of zircon fertility indicators (e.g., Ce and Eu anomalies) is still not well illustrated. In this study, we report U-Pb ages and trace element compositions of zircons from ore-forming muscovite granite plutons of the Taoxikeng W deposit, South China. The studied zircons are characterized by abundant small apatite inclusions. Although these had little influence on zircon Eu/Eu* (and thus probably the interpreted level of magmatic fractionation and melt water concentration), they could have resulted in a misestimation of the magmatic oxidation state either via the zircon Ce/Ce* or Loucks et al. (2020) methods. This is especially important for granite-related W-Sn systems since their magmatic zircons generally contain abundant mineral inclusions, which may be accidentally sampled during zircon trace element analysis. In practice, we can use La as a monitor of REE-enriched mineral (i.e., apatite, titanite) inclusions, although the criterion for identifying pure zircon trace element data is still controversial and awaits further work.

Geochronology, petrogenesis, and magmatic oxidation state of the Mangling intrusive complex, Northern Qinling Belt, Central China: Implications for magma fertility and tectonic setting

The Mangling intrusive complex has different dioritic to granitic phases and is spatially and temporally related to molybdenum deposits in the Qinling Orogen. Zircon U-Pb dating of the Mangling intrusive complex indicates that dioritic rocks (biotite diorite and biotite diorite enclave; ca. 150−147 Ma) formed earlier than granitic rocks (medium- to fine-grained and fine-grained monzogranite and K-feldspar granite; ca. 145−141 Ma). The Mangling dioritic rocks exhibit large ion lithosphere element (e.g., Rb) and light rare earth element enrichment and high field strength element (e.g., Nb, Ta, and Ti) depletion. They have low to moderate SiO2 (51.33−58.16 wt%), high MgO (3.10−4.75 wt%) and Mg# (48−60), and negative zircon εHf(t) values (−11.6 to −6.8), suggesting origination from the continental lithospheric mantle that may have been metasomatized by previous sediment-derived melts and slab-derived fluids constrained by high Nb/Y, Th/Yb, and Rb/Y ratios. The Mangling granitic rocks are I-type granites and have high SiO2 (67.90−81.88 wt%) and low MgO (0.16−0.74 wt%). They have low and negative zircon εHf(t) values (−18.7 to −1.9) and old zircon Hf two-stage model ages (2334−1287 Ma), as well as similar mineral fractionation (e.g., hornblende, biotite, sphene, and apatite) with the Mangling dioritic rocks, indicating that they were derived from the remelting of old crustal rocks (e.g., Xiong’er and Kuanping groups) by the evolved underplated mafic magma. Compared with the Taoguanping mineralized monzogranite in the Northern Qinling Belt, zircon geochemistry (e.g., Ce4+/Ce3+, Eu/Eu*, and ΔFMQ [relative fayalite-magnetite-quartz buffer]) indicates that magma of the Mangling intrusive complex (except the biotite diorite) has high oxygen fugacity and small fractionated granitic intrusions, which are coeval with the biotite diorite enclave or younger than the Mangling granitic rocks, may have potential for generating porphyry molybdenum mineralization. The combination of this study and previous studies corroborates that the Qinling Orogen underwent an intracontinental orogenic evolution in a post-collisional compression to extension transitional setting during the Late Jurassic to Early Cretaceous, affected by far-field Paleo-Pacific slab subduction.

Apatite geochemistry as a proxy for porphyry-skarn Cu genesis: a case study from the Sanjiang region of SW China

In view of the importance of the magmatic oxidation state and volatile composition (H2O-S-Cl) in porphyry Cu mineralization, identification of magmatic information has become the basis for the evaluation of the Cu-mineralization potential of porphyries. Apatite, as a common accessory mineral in porphyry, is recognized as an effective petrogenetic and metallogenic indicator. In this study, we analyze the in situ major and trace elements and Nd isotope content of apatite from four granitic plutons in the Yidun Terrane, SW China, in order to provide new insights into the identification of the magmatic features of Cu-mineralized plutons. The plutons investigated in this study are a Cu-mineralized pluton (Hongshan) and three non-mineralized plutons (Cilincuo, Rongyicuo, and Hagela). Chemical composition and textural analysis indicate that the apatites are all of magmatic origin and have not been altered. Our results show that apatite δCe values rather than δEu and Ga values are more valid indicators of the magma oxidation state of the four plutons. Based on apatite δCe values and zircon compositions, the parental magma of the Hongshan pluton is identified as having been more oxidized than those of the other three plutons. Moreover, the higher Cl content (0.06–0.23 wt%) in the Hongshan apatite compared to that in apatite from the other three plutons (0.01–0.09 wt%), indicates that the parental magma of the former pluton was more enriched in Cl. Apatite from the Hongshan pluton contains more SO3 (average 0.05 wt%) than that from the other three plutons (SO3 content mostly lower than the detection limit of electron probe micro-analysis), which may be related to higher magmatic oxygen fugacity of the Hongshan pluton. In addition, the Nd isotopic composition of apatite [εNd(t): −13.6−5.9] demonstrates that the Cu-mineralized and non-mineralized plutons were derived from the melting of ancient lower crust. Furthermore, based on the geochemical signature of adakite revealed by apatite Sr/Y and δEu values, the Hongshan pluton can be considered to have been produced as the result of partial melting of the thickened lower crust. Finally, an index system consisting of apatite δCe, Sr/Y, and F/Cl values is established to distinguish between the Cu-mineralized and non-mineralized plutons.

The Genetic Link between Iron-Oxide–Apatite and Porphyry Cu–Au Mineralization: Insight from the Biotite–Pyroxene–Zircon Study of the Nihe Fe Deposit and the Shaxi Cu–Au Deposit in the Lower Yangtze Valley, SE China

Different ore deposit types may evolve from a common magmatic-hydrothermal system. Establishing a genetic link between different deposit types in an ore cluster can not only deepen the understanding of the magmatic-hydrothermal mineralization process but can also guide exploration. Both the Nihe iron-oxide–apatite (IOA) deposit and the Shaxi porphyry Cu–Au deposit in the Lower Yangtze Valley, Anhui, Southeast China, formed in the Luzong Cretaceous volcanic basin at ~130 Ma. We examined a temporal–spatial and potential genetic link between these deposits based on stratigraphic lithofacies sections, biotite and clinopyroxene mineralogical chemistry, zircon chronology, Hf isotopes, and trace elements. Stratigraphy, petrology, mineralogical chemistry, and available fluid inclusion results support that the emplacement depth of the Nihe ore-related porphyry is shallower than that of the Shaxi porphyry. The magmatic zircon and hydrothermal zircon from Nihe provided U–Pb ages of 130.6 ± 0.7 Ma and 130.7 ± 0.7 Ma, respectively. The magmatic zircon U–Pb age (130.0 ± 0.8 Ma) of Shaxi overlaps with its molybdenite Re–Os age (130.0 ± 1.0 Ma). The agreement between the mineralization and porphyry emplacement ages of Nihe and Shaxi indicates a temporal coincidence and supports a possible genetic link between the two deposits, considering their close spatial relationship (in the same ore district, 15 km). The zircon Hf isotopes and trace elements support the evolution of both deposits from an enriched lithospheric mantle, although the Shaxi deposit may have experienced contamination of the Jiangnan-type basement. Both deposits lie above the fayalite-magnetite-quartz buffer, but the Nihe magmatic zircons are of lower temperature and less oxidized than that of Shaxi. The much higher Eu/Eu* and Yb/Dy values of zircons from Shaxi are likely caused by the suppression of early plagioclase crystallization and the prevalence of amphibole fractionation, thus indicating more hydrous content of the Shaxi ore-related magma. Additionally, the Shaxi ore-related porphyry has higher zircon Hf concentrations, suggesting that the porphyry Cu–Au deposit has experienced a greater degree of magma fractionation. Our study highlights that the Nihe IOA deposit and the Shaxi porphyry Cu–Au deposit have a common magma source, while different extent of crust contamination, magma oxidation state, hydrous content, and degree of magma fractionation collectively result in the two distinct ore deposits. This possible genetic link suggests a great potential of porphyry Cu–Au-PGE mineralization in the Middle–Lower Yangtze River metallogenetic belt, especially in the deep part of the IOA district in the Luzong Cretaceous volcanic basin.

Two stages of porphyry Cu mineralization at Jiru in the Tibetan collisional orogen: Insights from zircon, apatite, and magmatic sulfides

Continental collision−related porphyry copper (Cu) deposits provide significant global copper resources, but their genesis remains controversial because it is not clear whether remelting of remnant arc-derived lower-crustal Cu-rich cumulates is critical to their formation. We investigated zircon and apatite compositions of the Jiru porphyry Cu deposit in the Gangdese belt of southern Tibet, which is characterized by weaker early Eocene mineralization and more pronounced Miocene mineralization. Our data demonstrate that apatite hosted in zircon can record the volatile compositions of magma before fluid exsolution. Zircon-hosted apatites from the early Eocene granite that have low XF/XCl ratios (≤3) and are interpreted to have crystallized from volatile-undersaturated magma have Cl contents of 0.96−2.14 wt% (1.86 ± 0.38 wt%; n = 15) and SO3 contents of 0.01−0.14 wt% (0.08 ± 0.04 wt%; n = 15). In contrast, zircon-hosted apatites from the Miocene porphyry that have low XF/XCl ratios (≤10) and are interpreted to have crystallized from volatile-undersaturated magma have Cl contents of 0.40−0.56 wt% (0.47 ± 0.06 wt%; n = 11) and SO3 contents of 0.20−0.92 wt% (0.59 ± 0.29 wt%; n = 11). In addition, the early Eocene magma was relatively reduced (ΔFMQ = 0.86 ± 0.55, where FMQ is fayalite-magnetite-quartz) compared with the oxidized Miocene magma (ΔFMQ = 2.04 ± 0.43). The contrasting magmatic oxidation states and apatite/melt S contents were likely critical in controlling the different scales of Cu mineralization during the early Eocene and Miocene, as more highly oxidized magma can dissolve much larger amounts of sulfur and metals (e.g., Cu). Melt Cl content may not play a critical role in magma fertility, since the Jiru early Eocene granite had higher melt Cl contents than the Miocene porphyry. Magmatic sulfides (pyrrhotite, chalcopyrite, and pyrite) were not recognized in the Miocene zircons but did occur in the early Eocene zircons, and these sulfides were demonstrated to have crystallized before fluid exsolution in the shallow magma reservoir. The Jiru early Eocene magmatic sulfide saturation might not have enhanced the amount of copper available to hydrothermal fluids during the early Eocene. Late-stage sulfide saturation in the previous arc magmas might reduce the potential for collision-related porphyry Cu mineralization that is associated with remelting of the previous arc lower crust.

Progress and prospect of the oxidation state of magmas in convergent tectonic settings

Progress and prospect of the oxidation state of magmas in convergent tectonic settings

Possible source of Au in the Jiaodong area from lower crustal sulfide cumulates: Evidence from oxygen states and chalcophile elements contents of Mesozoic magmatic suites

The genesis of giant Jiaodong gold province remains perplexing although many ore-forming models have been proposed in the past decades. The key issues are what caused the burst of gold around 120 Ma and possible sources of gold. Here we report gold and platinum group elements (PGE) data and magmatic oxidation states of the pre-mineralization Mesozoic plutonic rocks and some mafic dykes to discuss their potential effects on gold mineralization. Gold concentrations of the Late Jurassic Linglong granite are 0.015–0.278 ppb. The Early Cretaceous plutonic rocks (129–127 Ma) have the same levels of Au concentrations (Au = 0.031–0.047 ppb). Both of the Jurassic and Cretaceous magmatic rocks are depleted in Au compared to normal granitic rocks worldwide (∼1 ppb). Palladium and platinum concentrations in the Linglong granite are 0.160–0.385 ppb and 0.046–0.116 ppb, respectively. Meanwhile, Pd and Pt contents of Cretaceous magmatic rocks are 0.069–0.363 ppb and 0.063–0.465 ppb, respectively.Oxygen fugacities of the Late Jurassic Linglong granite calculated by biotite oxybarometer are FMQ + 0.5 to FMQ + 1.2 (where FMQ refers to fayalite-magnetite-quartz buffer). Oxidation states of the Early Cretaceous magmatic rocks estimated via amphibole oxybarometer are from FMQ + 0.3 to FMQ + 1.1 for Guojialing granodiorite. Zircon trace element data yield overall higher fO2 values than those estimated with biotite and amphibole compositions. Oxygen fugacities are from FMQ – 0.6 to FMQ + 1.9 (sample CJ-3) and FMQ – 0.7 to FMQ + 1.1 (sample LL-1) for the two Linglong granite samples. Zircons from the Early Cretaceous Guojialing pluton yield oxidation states between FMQ – 0.8 and FMQ + 1.9 (DCW-1), which are about one log unit higher than those of the Beijie pluton (BJ-1: FMQ – 1.0 to FMQ + 0.7). However, oxidation states from nearly syn-mineralization mafic dyke reach FMQ + 2.0 to + 3.0 when estimated via zircon oxybarometer. Oxidation states given by whole rock Fe3+/Fe2+ ratios also support the results calculated by mineral compositions.There is no fractionation crystallization of redox-sensitive minerals, like magnetite or garnet, as indicated by geochemical data, which implies that the oxidation states of magmas may reflect their source regions. However, the depleted nature of Au and PGE must imply that these elements are missing. We propose that sulfide saturation at the deep crust can be invoked to explain the extremely low gold and PGE contents of these magmatic rocks. The sulfide cumulates act as sinks for sulfide-loving elements (e.g., Au), which are pre-enriched source for later large-scale gold mineralization in Jiaodong area. The underplated water-rich mafic magma from enriched mantle source ponded at the lower crust, continuously crystallized anhydrous minerals (e.g., olivine and clinopyroxene) and reached volatile saturation at the very moment. This volatile, probably carrying gold, resorbed the sulfide cumulate and escaped to shallow levels to form the giant Jiaodong gold deposits.

Using apatite to differentiate metallogenic potential and environment of granitic rocks: A case study from the Tongshanling W-Sn-Cu-Pb-Zn ore field, Nanling Range (South China)

The Tongshanling ore field is one of the most representative W–Sn–Cu–Pb–Zn polymetallic deposits in the central-western Nanling Ore Belt, which developed multiple mineralization types, including Cu–Pb–Zn (Tongshanling), W–Sn (Weijia), Pb–Zn (Jiangyong), and Mo (Yulong) deposits. Here, we analyzed apatite from the Tongshanling granodiorite and the Weijia granite porphyry, integrating major and trace elements, U–Pb dating, and Nd isotopic analyses to compare the difference in geochronology, magma source, redox environment, and evolution between the Tongshanling and Weijia deposit. The U–Pb dating of the Tongshanling and Weijia apatite samples yield a lower intercept age of 166.2 ± 11.3 Ma (1σ, MSWD = 0.22) and 160.87 ± 8.92 Ma (1σ, MSWD = 0.44) on Tera-Wasserburg diagrams, respectively. The 147Sm/144Nd and 143Nd/144Nd ratios of the Tongshanling apatite samples are 0.136769–0.182878 and 0.512159–0.512246, respectively, with corresponding εNd (t = 166 Ma) ranging from −8.32 to −6.60, suggesting that the Tongshanling granodiorite was produced by partial melting of metaigneous rocks in the deep crust. The Tongshanling apatite shows a right-inclined REE pattern, while the Weijia apatite displays a “V” type REE pattern. The Tongshanling apatite shows higher Eu/Eu* values, and lower Mn and Ce/Ce* values than the Weijia apatite, indicating that the former formed in higher magmatic oxidation state while the latter formed in more reduced conditions. The granodiorite in the Tongshanling deposit is characterized by a lower degree of fractionation than the granite porphyry in the Weijia deposit, of which the Weijia apatite has lower Sr, Mg contents, and higher Y contents. Furthermore, apatite from Cu-bearing granites exhibits lower F/Cl ratios compared to those from W-bearing granites in the South China Block. In the Tongshanling area, apatite from the Tongshanling granodiorite has higher Cl contents than the Weijia apatite, indicating that the crustal basement of the Tongshanling area was affected by the high Cl fluid derived from the Proterozoic oceanic subduction and remelted to form granite in the Mesozoic, while the Weijia granite porphyry formed from remelting of a sedimentary source. The Tongshanling granodiorite and Weijia granite porphyry with different degrees of fractionation, magma source, and halogens contents can be effectively distinguished by the geochemistry of apatite. The difference in trace elements (Sr, Y, Mg, and REE) and isotopes of apatite can be applied to the identification of different types of ore-bearing granites in the Nanling Range.

Titanite geochemistry and its indicators for Cu-mineralized magmas: Insight from three dioritic intrusions in the Tongling area of the Lower Yangtze River metallogenic belt

Titanite has been regarded as a potential petrogenetic and metallogenic indicator owing to its stability and enrichment of trace elements. To verify the availability of geochemical titanite proxies in the Cu-mineralized magma system and to reveal magmatic constraints on Cu mineralization related to magmatic hydrothermal fluid, in situ major and trace element abundances and Nd isotopes of igneous titanite were determined for three Mesozoic diorite intrusions in the Tongling ore district of eastern China. The investigated intrusions were the Tongguanshan, Fenghuangshan, and Hucun intrusions, all of which host porphyry-skarn Cu deposits. Our study shows that the titanite δEu value and Fe/Al ratio, rather than the δCe and Ga content, are more effective indicators of the magma oxidation state in all three intrusions. Based on the titanite δEu value and Fe/Al ratio, the causative magma of the Fenghuangshan intrusion (titanite δEu = 0.50 ± 0.08; Fe/Al = 0.21 ± 0.07) was identified as being less oxidized than those of the Tongguanshan (titanite δEu = 0.64 ± 0.09; Fe/Al = 0.93 ± 0.15) and Hucun (titanite δEu = 0.80 ± 0.03; Fe/Al = 0.91 ± 0.04) intrusions. This result was consistent with the zircon Ce4+/Ce3+ ratio. Moreover, owing to the limited effect of fluid exsolution and fractional crystallization on the F content of the investigated titanite, the higher titanite F content of the Fenghuangshan intrusion (titanite F = 0.40 ± 0.09 wt%) implies that the parental magma of this intrusion is more F-enriched than those of the Hucun (titanite F = 0.17 ± 0.09 wt%) and Tongguanshan (titanite F = 0.10 ± 0.07 wt%) intrusions; however, titanites from all three Cu-mineralized intrusions had similar or lower F content than those from intrusions without Cu mineralization. The above findings indicate that magmas with high oxygen fugacity have relatively high potential for porphyry-skarn Cu mineralization, while the high enrichment of F is not necessary for Cu mineralization. Additionally, we found that titanite εNd(t) values can inherit whole-rock εNd(t) values and thus can be used to investigate petrogenesis. This study confirms that titanite geochemistry is an efficient petrogenetic and metallogenic indicator for Cu-mineralized magma systems when the prerequisites are met.

Geochronology and Geochemistry of the Mamupu Cu‐Au Polymetallic Deposit, Eastern Tibet: Implications for Eocene Cu Metallogenesis in the Yulong Porphyry Copper Belt

AbstractThe Mamupu skarn‐type Cu‐Au polymetallic deposit represents the first discovery of a medium deposit in the southern Yulong porphyry copper belt (YPCB), eastern Tibet. The Cu‐Au mineralization mainly occurs as chalcopyrite in breccia, within the plate‐like carbonate interlayer, being closely related to chloritization (e.g., chlorite, magnetite and epidote) and skarnization (e.g., diopside, tremolite and garnet). The ore‐related quartz syenite porphyry (QSP) and granodiorite porphyry (GP) were emplaced at 40.1 ± 0.2 Ma and 39.9 ± 0.3 Ma, respectively. The QSP of Mamupu is an alkaline‐rich intrusion, relatively enriched in LREE, LILE, depleted in HFSE, with no significant negative Eu and Ce anomalies, slightly high (87Sr/86Sr)i, low ∊Nd(t), uniform (206Pb/204Pb)i and ∊Hf(t) values, which indicates that the porphyry magma may be caused by both the mixing of metasomatized EM II enriched mantle and thickened juvenile lower crust. The QSP in the Mamupu deposit shares a similar genesis of petrology to other ore‐related porphyries within the YPCB. High oxygen fugacity and water content of the magmas are essential for the formation of porphyry and skarn Cu deposits. The QSP has similar high magmatic oxidation states and water content to the Yulong deposit, which indicates that the Mamupu has a high prospecting potential. Differences in the geological characteristics and scale of mineralization between the Mamupu and other YPCB deposits may be due to the different emplacement depths of ore‐related intrusions, as well as differences in the surrounding rocks.

Rapid transition to fertile magma and promotion of porphyry mineralization: A case study from the Don Javier deposit

The Don Javier porphyry Cu–Mo deposit formed contemporaneously with the Incaic I orogeny (∼60 Ma) in southern Peru. The causative dacite porphyry is hosted by the Yarabamba Superunit, which is the youngest batholithic unit in the Toquepala arc. In this study, we conducted elemental and isotopic analyses on samples from the dacite porphyry and Yarabamba Superunit in an effort to clarify the origins and formation mechanism of the deposit. Zircon U–Pb dating shows that the young part of the Yarabamba Superunit was emplaced at 65.4 ± 0.7 to 63.5 ± 0.8 Ma, and the causative dacite porphyry was emplaced at Don Javier between 59.9 ± 0.4 and 59.2 ± 1.1 Ma. The Yarabamba Superunit and dacite porphyry have similar εHf(t) and δ18O isotope values, ranging from –4.6 to +1.9 and 5.1‰ to 6.4‰, respectively. The Yarabamba Superunit has initial Sr and Nd isotope values of 0.70533–0.70579 and 0.51242–0.51244, respectively. Isotopic data suggest that the Yarabamba Superunit and dacite porphyry evolved from an isotopically homogeneous magma reservoir with minor crustal assimilation. However, the dacite porphyry has whole-rock and zircon Eu/Eu* values of 0.9 and 0.34, respectively, higher than those of the Yarabamba Superunit (0.6 and 0.13).Additionally, the dacite porphyry has significantly higher apatite S content (0.07 wt%) and XCl values (0.21) than those of the Yarabamba Superunit (apatite S: 0.01 wt%; XCl values: 0.15). The calculated magmatic oxidation state shows that the dacite porphyry has a significantly higher magmatic oxygen fugacity (ΔFMQ +1.1) than the Yarabamba Superunit (ΔFMQ –0.5).Together, the data suggest that the magmas formed the Yarabamba Superunit and causative dacite porphyry are characteristics of distinct tectonic regimes. The magma of the Yarabamba Superunit was generated during normal subduction and underwent low-pressure, H2O-poor, plagioclase-dominated fractionation while the magma of the dacite porphyry was generated during arc compression and underwent high-pressure, H2O-rich, amphibole-(garnet) dominated fractionation, which led to a high oxidation state and volatile-rich magma that promoted porphyry mineralization at Don Javier. This rapid elevation of the magmatic oxidation state and volatile content occurred synchronously with the Incaic I orogeny (∼60 Ma), which indicates that this orogeny had a significant impact on the formation of the very large–super-giant porphyry ore systems in southern Peru.

Geology and factors controlling the formation of the newly discovered Beimulang porphyry Cu deposit in the western Gangdese, southern Tibet

The porphyry Cu deposits in the Gangdese metallogenic belt were mainly formed in the eastern portion. The Beimulang is a newly discovered deposit formed in post-collisional setting in the western part of the belt and adjacent to the super-large Zhunuo porphyry Cu deposit. There are three epochs of magmatism at Beimulang, including pre-mineralization quartz porphyry (PQP; 49.7 ± 0.4 Ma), inter-mineralization monzogranite porphyry (IMGP; 14.8 ± 0.2 Ma), monzogranite (IMG; 14.1 ± 0.2 Ma), and late-mineralization granite porphyry (LGP; 11.7 ± 0.1 Ma). The various degrees of alteration and sulfide occurred at the IMG(P) and LGP indicate that there are at least two episodes of fluid exsolution events associated with different intrusions spanning ∼ 3 m.y. at Beimulang, which are unlike other Gangdese porphyry Cu deposits showing single fluid exsolution around only one porphyry at Miocene (e.g., Qulong, Zhunuo, Dabu). The PQP is characterized by high SiO2 (75.6–81.4 wt%) and K2O (2.1–4.3 wt%) concentrations, high Nb/Ta (8.4–11.3) ratios, and low Mg# (22–43), Ni (1.5–2.7 ppm) contents. They have high (87Sr/86Sr)i (0.705098–0.707767) ratios and low εNd(t) (-4.9 to −1.9) values. These geochemical characteristics indicate that they were probably derived from a juvenile basaltic lower crust during the ongoing Indian-Asian collision. The IMGP and IMG show similar petrography and geochemical characteristics, such as high SiO2 (65.0–69.8 wt%), K2O (3.6–4.3 wt%), Sr (550–809 ppm) contents, high Sr/Y (79–89) ratios, and low Mg# (43–48), Th/Yb, and Nb/Yb values, combined with high (87Sr/86Sr)i (0.707254–0.708017) and low εNd(t) (-7.9 to −6.0), implying a similar source probably originated in the subduction-modified lower crust metasomatized by Neo-Tethyan oceanic slab-derived fluids. The LGP displays trends produced by fractionation of magma with a composition similar to the IMG(P), but wall rock assimilation plays a significant role during magmatic evolution. Zircons from the IMG(P) show higher Eu/Eu* (>0.3), 10000*(Eu/Eu*)/Y (>4), and (Ce/Nd)/Y (>0.04) ratios than those of the PQP, indicating the fertile magmas were more oxidized and hydrous. The high magmatic oxidation state for the IMG(P) is also supported by using the zircon (ΔFMQ = +4.1 to + 6.1), and amphibole (ΔFMQ =+2.6 to + 3.4) oxybarometers. Their high magmatic water contents are supported by evaluations using amphibole (∼3.5 wt%) and plagioclase (∼6.7 wt%) compositions, respectively. However, the LGP has higher magmatic oxygen fugacity (Eu/Eu* >0.3, ΔFMQ = +4.2 to + 7.3) caused probably by auto-oxidation of the magmas, but lower magmatic water contents (Sr/Y = 31 ± 15; V/Sc = 6 ± 4) caused presumably by previous fluid exsolution and/or fractionation of hydrous silicate minerals during magma ascent than those of the IMG(P). Therefore, the highly hydrous and oxidized magmas with juvenile material are favorable to form porphyry Cu deposits in Tibetan orogen. On the contrary, magmatic evolution can probably reduce the water content of magma chamber, which is not beneficial to porphyry Cu mineralization.

Geochronology and geochemistry of mineralized and barren intrusive rocks in the Yemaquan polymetallic skarn deposit, northern Qinghai-Tibet Plateau: A zircon perspective

The Yemaquan polymetallic skarn deposit is located in the Qimantagh metallogenic belt (QMB), northern Qinghai-Tibet Plateau, China, with total ore resources of 82.7 million metric tons at 29.46 percent Fe, 0.40% Cu, 2.08% Pb and 1.77% Zn. In this study, new trace element composition of zircon in tandem with LA-ICP-MS U-Pb geochronology are provided for mineralized and barren intrusive rocks occurring within two magnetic anomaly areas (M1 and M13) at the Yemaquan deposit. These data, combined with whole rock major and trace element compositions, allow to constrain the geochronological framework and magmatic processes for different types of intrusive rocks within the district.The zircon U-Pb ages reveal that the polymetallic mineralization in the M1 and M13 anomaly areas results from two temporally distinct intrusive centers. Different to the M13 area where only the mineralized Devonian intrusions are recorded, both mineralized and barren intrusive rocks in the M1 area were emplaced in the Late Triassic. Whole rock major and trace elements indicate that both Triassic mineralized and barren rocks underwent significant fractional crystallization, with the Triassic barren rocks displaying much stronger plagioclase fractionation. In contrast, the limited whole rock silica range and high Eu/Eu* of Devonian mineralized intrusions indicate that they did not experience evident fractionation. Zircon trace elements show that the two mineralized groups at Yemaquan display similar, high zircon Ce/Ce* but distinguishable Eu/Eu* ratios, which suggest a consistent, high magmatic oxidation state but different water content. The magmatic water content of Devonian mineralized rocks higher than that of their Triassic counterparts probably suggests that the former are more Cu-fertile. This study confirms that both Devonian and Triassic intrusive activities are responsible for skarn Fe-Cu-Pb-Zn mineralization at the Yemaquan deposit. Meanwhile, in view of the general feature of Yemaquan in the context of skarn deposits from the QMB, we thus suggest that in future mineral exploration great attention should be paid to both the Triassic and Devonian intrusive rocks.

Apatite and zircon compositions for Miocene mineralizing and barren intrusions in the Gangdese porphyry copper belt of southern Tibet: Implication for ore control

Gangdese porphyry copper belt in southern Tibet of China contains many Miocene fertile and barren adakite-like intrusions. Their magmatic oxidation state and volatile concentrations were poorly constrained. Here, we present apatite and zircon composition data for the Miocene fertile intrusions in the Qulong, Jiru, and Zhunuo porphyry copper deposits, and the coeval barren porphyries at Yare, Mayum, and Lasa in the Gangdese belt. Magmatic zircons of intrusions from the six locations share similar ΔFMQ (FMQ represents the reference buffer fayalite + magnetite + quartz) values, indicating both fertile and barren rocks have similar magmatic oxidation state. Variations of apatite Cl concentrations and characteristics of S- and Cl-rich core to abruptly S- and Cl-poor rim at Qulong, Jiru, Zhunuo, Yare, and Mayum are indicative of fluid exsolution from vapor-saturated magma. In contrast, fluid exsolution was not recognized from the available apatite composition data at Lasa which are characterized by constant or increasing apatite Cl concentrations with decreasing F/Cl ratios from core to rim. Some apatites at Lasa have high SO3 concentrations at the core compared with the rim, which would be attributed to early crystallization from S-rich magma followed by crystallization of sulfate minerals in a vapor-undersaturated magma. Some apatites from the fertile intrusions at Qulong, Jiru, and Zhunuo have lower Cl concentrations than those from the barren rocks at Yare, Mayum, and Lasa, which is consistent with the observation from the calculated melt Cl concentration. In addition, the SO3 concentrations at the core of apatites from all the fertile rocks are overlapping with those from all the barren rocks. Therefore, enrichment of Cl and S alone in melts may not be critical to forming economic porphyry copper mineralization in the Gangdese belt. Cautions must be taken when using compositions of detrital zircon and apatite grains to evaluate metallogenic potential during regional geochemical surveys.

Geochronology, geochemistry and Sr-Nd-Hf isotopes of the Heihuashan granite porphyry, NE China, and implications for Cu-Mo mineralization

Heihuashan is a newly discovered porphyry Cu-Mo prospect in Heilongjiang Province, northeastern China, with considerable Cu and Mo mineralization. Until now the ages of the Cu-Mo ores and the causative granite porphyry, the magma origin and characteristics, as well as the mineralization potential at depth are still unclear. In this contribution, whole rock geochemical and Sr-Nd isotopic compositions, zircon U-Pb ages and Hf isotopes, and molybdenite Re-Os dating, are presented to constrain the timing of the magmatism and mineralization, and the petrogenesis of the causative intrusion. The results also provide an opportunity for evaluating the potential of the deep Cu-Mo mineralization.Zircon U-Pb dating using LA-ICP-MS yields a crystallization age of 146.4 ± 1.8 Ma for the Heihuashan granite porphyry, which is consistent with the molybdenite Re-Os isochron age of 143.7 ± 3.1 Ma. These results indicate that the porphyry Cu-Mo mineralization at Heihuashan occurred at late Jurassic to early Cretaceous. The whole rockgeochemicaldatasuggest that the ore-related intrusion is mildly peraluminous and belongs to the high-Kcalc-alkalineseries, I-type granitoids. The granite porphyry samples are enriched in Rb, Ba, Th, U, and Sr, but depleted in Nb and Ta, showing typical arc magma affinities. They also have initial 87Sr/86Sr ratios of 0.70546–0.70550 and εNd(t) values between +0.4 and +0.7. The zircon εHf(t) values for the granitic intrusion range from +3.5 to +9.2, with two-stage Hf model ages of 977–614 Ma. The geochemical and Sr-Nd-Hf isotopic compositions suggest that the parental magma was dominantly derived from the slab-metasomatized mantle, which could have mixed with some lower crust components.The Fe2O3/FeO ratios of the Heihuashan granite porphyry are relatively high, ranging from 0.52 to 1.17, indicating a high magmatic oxidation state. This is also supported by the high zircon Ce/Ce*, Eu/Eu* and Ce/Nd ratios (33–2433, 0.22–0.70 and 2.4–44.0, respectively) and the high magmatic ΔFMQ values (+0.1 to +3.5 with an average of +2.1) calculated using the zircon trace elements. The intrusion has relatively high Sr/Y ratios (40–94) and displays negligible Eu anomalies (Eu/Eu* = 0.68–1.07); the zircons from the intrusion have high (Eu/Eu*)/Y (mostly > 0.0001) and (Ce/Nd)/Y ratios (mostly > 0.01), but low Dy/Yb ratios (generally < 0.4). These suggest that the fractionation of hornblende rather than plagioclase is dominant during the magma crystallization, which reveals a high magmatic water content. The above results indicate that the ore-related magma at Heihuashan is oxidized and hydrous, both of which are critical for porphyry Cu-Mo mineralization. The Heihuashan granite porphyry is geochemically similar to other Cu-related intrusions in NE China and also comparable to many porphyry Cu (-Mo) systems worldwide, implying a high Cu-Mo mineralization potential. Considering the surface and shallow levels at Heihuashan are characterized dominantly by sericite alteration, we suggest exploration and drilling focusing on the deeper levels beneath the currently mineralized domains, where major potassic alteration zones, likely associated with more extensive Cu-Mo mineralization, could be discovered.

Paleozoic Magmatism and Mineralization Potential of the Sanchakou Copper Deposit, Eastern Tianshan, Northwest China: Insights from Geochronology, Mineral Chemistry, and Isotopes

Abstract The Sanchakou Cu deposit is located in the eastern section of the Dananhu magmatic arc in the Eastern Tianshan orogenic belt, northwest China. Sanchakou is hosted by quartz diorite and granodiorite intrusions. Chalcopyrite and bornite are the dominant ore minerals and occur as disseminations, patches, veins, and veinlets. Secondary ion mass spectrometry (SIMS) U-Pb dating of zircons shows that the ore-bearing intrusions were emplaced at ca. 435–432 Ma, recording the early subduction of the Paleo-Tianshan oceanic plate. The enrichment in large ion lithophile elements (LILEs), depletion in high field strength elements (HFSEs), and moderate Mg# values, together with mantle-like bulk Sr-Nd and zircon Hf-O isotope signatures (δ18O = 4.0–5.3‰), suggest that they were generated from partial melting of metasomatized mantle materials by subducted slab fluids. In situ S and whole-rock Pb isotope results imply that the Sanchakou diorite magmas provided ore-forming components (S and metals), with additional minor metals (e.g., Cu and Pb) sourced from crustal components beneath the Dananhu arc. The redox state of diorite magmas ranges from initial high fO2 (&amp;gt;FMQ + 2, where FMQ is the fayalite-magnetite-quartz buffer) to relatively low fO2 (&amp;lt;FMQ + 2) upon magma ascent and cooling. The late-stage less oxidized magma compositions are consistent with the presence of magmatic sulfides in primary plagioclase and magnetite. Estimates of water-sulfur-chlorine contents in magma using plagioclase, amphibole, and apatite compositions reveal that the diorite magmas had high water (&amp;gt;7 wt %), normal S (8–393 ppm), and systematically low Cl (38–1,100 ppm) contents. A constant and favorable elevated magma oxidation state appears critical for generating an economic porphyry Cu deposit. Additionally, Cl melt concentrations may be a key factor that controlled metal fertility of the deposits in the Eastern Tianshan, although the mineralization potential may also relate to depth of emplacement of the hydrothermal system. The anomalous presence of stellerite with chalcopyrite in late-stage veins indicates that original porphyry-style mineralization at Sanchakou underwent deformation-related modification after its formation.