Apatite and Zircon Geochemistry in Yao’an Alkali-Rich Porphyry Gold Deposit, Southwest China: Implications for Petrogenesis and Mineralization

The Yao’an gold deposit is located in the middle of the Jinshajiang-Ailaoshan alkali-rich metallogenic belt, and this belt hosts many porphyry-type Cu-Au-Mo deposits formed at 46–33 Ma. Yao’an porphyry gold-mineralization is intimately associated with biotite syenite porphyry, whereas the contemporaneous quartz syenite porphyry is barren. In this study, we compared the major and trace elements of apatite and zircon and isotopic compositions of zircon from the biotite syenite porphyry and quartz syenite porphyry, to explore their geochemical differences that may affect their mineralization potential. The results show that both porphyries were derived from the partial melting of the thickened lower crust, which has been modified by slab-derived fluids, but has different mineral crystallization sequences, magma fluid activities, and magma oxidation states, respectively. REE contents in apatite and zircon can be used to reveal the crystallization sequence of minerals. A rapid decrease of (La/Yb)N ratio in apatite from both porphyries may be caused by the crystallization of allanite. Large variation of Cl contents and negative correlation between F/Cl and (La/Yb)N in apatite from fertile porphyry indicate that it has experienced the exsolution of Cl-bearing hydrothermal fluid. Higher Y/Ho and lower Zr/Hf in zircon from fertile porphyry indicate a stronger fluid activity than barren porphyry. The high S, V, As contents, δEu, low δCe in apatite, as well as high Ce4+/Ce3+ and log(fO2) estimated from zircon geochemistry from fertile porphyry, indicate high a oxidation state of fertile porphyry, similar to other fertile porphyries in this metallogenic belt. High fluid activity and fluid exsolution are conducive to the migration and enrichment of metal elements, which are very important for mineralization. High oxygen fugacity inhibits the precipitation of metal in the form of sulfide, thereby enhancing the mineralization potential of rock. Therefore, the exsolution of Cl-bearing hydrothermal fluid and high oxygen fugacity are the key factors promoting mineralization in Yao’an area.

Generation of Calc-Alkaline Magmas During Crystallization at High Oxygen Fugacity: An Experimental and Petrologic Study of Tephras from Buldir Volcano, Western Aleutian Arc, Alaska, USA

Despite agreement that calc-alkaline volcanism occurs at subduction zones and is responsible for the genesis of continental landmasses, there is no consensus on the source of the Fe-depleted signature hallmark to calc-alkaline volcanism. In this study, we utilize mafic tephras collected from Buldir Volcano to address the genesis of strongly calc-alkaline volcanic rocks (those with a low Tholeiitic Index; ≤0.7) in a segment of the western Aleutian Arc to determine if the eruptions are plausibly part of a liquid line of descent, if they are mixtures of crustal melts and parental magmas, or if they are mixtures of melts of the mantle and the subducting slab. We conducted a series of H2O-saturated phase equilibrium experiments (1175–1000 °C; 100 MPa) in a rapid-quench cold-seal (MHC) apparatus on the most primitive natural lava from Buldir (9.34 wt% MgO) at oxidizing conditions near the Re-ReO2 buffer. We confirmed that all experiments equilibrated 0.3 ± 0.23 log units above the Re-ReO2 buffer (ΔQFM ∼ +2.8) using X-ray Absorption Near Edge Structure (XANES) spectroscopy. Chromite is the liquidus phase, followed by olivine, then plagioclase, then clinopyroxene, and finally hornblende. Once clinopyroxene saturates, spinel composition shifts to magnetite. We compared our experimental results to the major element geochemistry and petrology of six tephras (51.9–54.8 wt% SiO2) from Buldir collected during the 2015 field season of the GeoPRISMS shared platform. Tephras contain olivine + plagioclase + clinopyroxene + spinel ± hornblende; plagioclase comprises most of the crystalline volume, followed by either olivine or hornblende. Spinel is ubiquitous; with Cr- rich spinel inclusions in olivine and hornblende, and magnetite in the groundmass. Variations in phenocryst assemblages and compositions between samples can be attributed to differences in pre-eruptive temperatures, where hotter samples are devoid of hornblende, and contain Fo-rich olivine and plagioclase with lower An-contents, owing to the position of the mineral-in curves at fluid-saturated conditions. Experimental glasses match the depletion in FeOT observed in the tephra whole rock compositions. The continuous depletion in FeOT is attributable to saturation of spinel as a liquidus phase (initially as chromite) and continuous crystallization through the experimental series (changing to magnetite at colder temperatures). In contrast to the natural samples, the experiments show enrichment in TiO2 with decreasing MgO, suggesting that differentiation did not occur at 100 MPa on Buldir. The TiO2 depletion in volcanic rocks from Buldir can be accounted for if hornblende crystallization occurs close to the liquidus of a parental magma; a condition that is met at higher pressures and hydrous conditions. The emerging picture for Buldir Island is that (1) oxidizing conditions are required to drive the observed depletions in FeOT via crystallization of spinel, and (2) elevated H2O contents and high pressures are required to saturate hornblende close to the liquidus to reproduce the entire suite of major elements. Our study provides a mechanism to generate the calc-alkaline trends observed at Buldir without requiring mixing of slab and mantle melts. We conclude that calc-alkaline volcanic rocks with extremely low Tholeiitic Indices (0.7), like those from Buldir, cannot be generated in absence of high oxygen fugacity, even at high pressure and/or elevated water pressures.

Genesis of Volcanic Rocks in the Zijinshan Ore District, SE China: Implications for Porphyry-Epithermal Mineralization

Volcanic rocks, as the extrusive counterparts of the mineralized intrusions, can provide important information on the magma source, petrogenesis, and metallogenic conditions of the coeval porphyry-epithermal system. Shanghang Basin volcanic rocks are spatially and temporally related to a series of adjacent porphyry-epithermal Cu–Au deposits, and they can be used as a window to study the related deposits. Two laser-ablation–inductively coupled plasma–mass spectrometry zircon U–Pb analyses of the volcanic rocks yield weighted mean ages of ~105 Ma, identical to the age of the coeval porphyry-epithermal mineralization. Rocks have SiO2 contents of 55.4 to 74.8 wt % and belong to the high-K to shoshonitic series, characterized by strong differentiation of light rare-earth elements (REEs) relative to heavy REEs (mean LaN/YbN = 16.88); enrichment in light REEs, Rb, Th, and U; and depletion in Nb, Ta, Zr, Hf, and Ti. The volcanic rocks display (87Sr/86Sr)i values of 0.709341 to 0.711610, εNd(t) values of −6.9 to −3.3 εHf(t) values of −3.95 to −0.30, and δ18O values of 6.07‰–6.79‰, suggesting that the parental magmas were derived from a mantle source enriched by subduction-related progress. SiO2 content shows a strong negative correlation with the contents of some major and trace elements, indicating that fractional crystallization played an important role in the generation of these rocks. A binary mixing model of Hf–O isotopes gives an estimated degree of crustal contamination of 30%. In addition, magnetite crystallized early, and the samples showed high zircon EuN/EuN* values (0.48–0.68), indicating that the parental magma had a high oxygen fugacity. The inferred suppression of plagioclase crystallization and increasing hornblende crystallization during magma evolution suggest that the magma was water rich. The high-water content and high oxygen fugacity of the magma promoted the dissolving of sulfides containing Cu and Au in the source area and contributed to the migration of ore-forming elements.