Search Results (305)

A diverse range of granitoids in the North Qilian Orogenic Belt (NQOB) offers valuable insights into the region’s tectonomagmatic evolution. In this study, we undertook a geochronological, mineralogical, geochemical, and zircon Hf isotopic analysis of granodiorites from the Yaogou area of the NQOB. Zircon U-Pb dating reveals that the Yaogou granodiorites formed during the Early–Middle Ordovician (473–460 Ma). The Yaogou granodiorites have high SiO₂ (63.3–71.1 wt.%), high Al₂O₃ (13.9–15.8 wt.%) contents, and low Zr (96–244 ppm), Nb (2.9–18 ppm), as well as low Ga/Al ratios (10,000 × Ga/Al ratios of 1.7–2.9) and FeO^T/MgO ratios (1.9–3.2), and are characterized by elevated concentrations of light rare earth elements and large-ion lithophile elements such as Rb, Th, and U, coupled with significant depletion in heavy rare earth elements and high-field-strength elements including Nb, Ta, and Ti. Additionally, the presence of negative europium anomalies further reflects geochemical signatures typical of I-type granitic rocks. The zircon grains from these rocks display negative ε_Hf(t) values (−14.6 to −10.7), with two-stage Hf model ages (T_DM2) from 2129 to 1907 Ma. These characteristics suggest that the magmatic source of the Yaogou granodiorites likely originated from the partial melting of Paleoproterozoic basement-derived crustal materials within a tectonic environment associated with subduction in the North Qilian Ocean. Integrating regional geological data, we suggest that during the Early Paleozoic, the North Qilian Oceanic slab underwent double subduction: initially southward, followed by a northward shift. Due to the deep northward subduction of the Qaidam continental crust and oceanic crust along the southern margin of the Qilian Orogenic Belt, the southward subduction of the North Qilian ocean was obstructed, triggering a reversal in subduction polarity. This reversal likely decelerated the southward subduction and initiated northward subduction, ultimately leading to the formation of the Yaogou granodiorites. These findings enhance our understanding of the complex tectonic processes that shaped the North Qilian Orogenic Belt during the Early Paleozoic, emphasizing the role of subduction dynamics and continental interactions in the region’s geological evolution. Full article

Ion-adsorption rare earth deposits are mainly formed by the weathering and leaching of granite ore-forming parent rocks, and heavy rare earth elements (HREEs) are predominantly hosted in this type of deposit. In this study, we focused on the Late Jurassic REE mineralization parent rock, specifically the Shuitou pluton. We employed chronology, petrogeochemistry, and isotope geochemistry to elucidate the REE enrichment process in the granite. The results show that the zircon U–Pb age of the Shuitou pluton is ~150 Ma, and the monazite U–Pb age is ~145 Ma, suggesting that the pluton was formed in the Yanshan Stage. The rocks have high SiO₂ (72.85–75.55 wt%), Al₂O₃ (12.85–14.63 wt%), and K₂O (4.46–5.27 wt%) content, with A/CNK values of 1.05–1.19, differentiation index (DI) values of 87.48–95.59, zircon saturation temperature values of 689–746 °C, Nb/Ta ratios of 2.72–9.54, and Zr/Hf ratios of 7.12–26.11. In addition, the rocks also contain peraluminous minerals such as muscovite and garnet. These characteristics indicate that these rocks belong to highly fractionated S-type granite. The ε_Hf(t) values of zircon and monazite range from −10.04 to −6.78 and from −9.3 to −8.2, respectively, indicating that the magma was primarily derived from Proterozoic metamorphosed sedimentary rocks of crustal origin. In the extensional tectonic setting of South China, a high temperature promotes the melting of REE-enriched accessory minerals, and a higher content of F increases the solubility of REEs in the molten mass. The presence of heavy rare earth minerals, such as garnet, in these rocks contributes to a high content of heavy rare earth elements (HREEs). Additionally, REE-enriched minerals like titanite, bastnaesite, and allanite create the necessary material conditions for the formation of ion-adsorption REE deposits. Full article

Along with the principal rare earth (REE) minerals such as monazite, xenotime, and bastnasite, Y-and REE-bearing zircon and associated minerals survive the combustion process and are found in coal-combustion fly ash. Beneficiated fly ash from a power plant burning an eastern-Kentucky-sourced coal blend was found to have zircon (ZrSiO₄), baddeleyite (ZrO₂), fergusonite (YNbO₄), yttriaite (Y₂O₃), and xenotime (YPO₄). Previous studies of the same fly had also identified monazite with a broad REE suite. Scanning electron microscopy–electron dispersive spectroscopy (EDS) and transmission electron microscopy (TEM)–EDS as well as other TEM-based techniques revealed a variety of zircon associations, including heavy-REE suites with Y, Nb, and Hf. Hafnium is a common accessory element in zircons and the Y and Nb may be present as fergusonite (YNbO₄) intermixed with zircon. Full article

In this study, we investigated and compared the influence of alumina nanoparticles (Al-NPs) and silicon nitride (SiN_x) layers individually deposited on multi-crystalline silicon (mc-Si) on mc-Si’s structural, optical, and optoelectronic characteristics to improve surface quality. Alumina nanoparticle-covered multi-crystalline silicon, immersion in HF/H₂O₂/HNO₃, and porous silicon (PS) covered with a silicon nitride structure are key components in achieving high electronic quality in multi-crystalline silicon. Surface reflectivity decreased from 27% to a minimum value of 2% for alumina nanoparticles/PS and a minimum value of 5% for silicon nitride/PS at a wavelength of 930 nm. Meanwhile, the minority carrier diffusion length increased from 2 µm to 300 µm for porous silicon combined with silicon nitride and to 100 µm for alumina nanoparticles/porous silicon. Two-dimensional current mapping further demonstrated a considerable enhancement in the generated current, rising from 2.8 nA for untreated mc-Si to 34 nA for Al-NPs/PS and 66 nA for PS/SiN_x. These results confirm that the surface passivation of mc-Si using Al-NPs or PS combined with SiN_x is a promising and efficient method to improve the electrical quality of mc-Si wafers, contributing to the development of high-performance mc-Si-based solar cells. Full article

As a candidate material for turbine blades in aerospace engines, Nb-Si-based alloys have attracted significant research attention due to their high melting point and low density. However, their poor high-temperature oxidation resistance limits practical applications. Different alloying elements, including Ti, Mo, and Hf, were added to Nb-Si-based alloys to study the microstructural evolution of alloys. Additionally, the oxidation behavior and the oxidation kinetics of different alloys, as well as the morphology and microstructure of oxide scale and interior alloys at 1523 K from 1 h to 20 h were analyzed systematically. The current findings indicated that the Mo element is more conducive to promoting the formation of high-temperature precipitates of β-Nb₅Si₃ than the Ti and Hf elements. Inversely, the Ti element tends to cause the transition from high-temperature-phase β-Nb₅Si₃ to low-temperature-phase α-Nb₅Si₃, while the Hf element improves the appearance of the γ-Nb₅Si₃ phase but inhibits the other phases and refines the primary Nbss effectively. Noteworthily, compared with the oxidation weight gain of different alloys, Nb-16Si-20Ti-5Mo-3Hf-2Al-2Cr alloy has excellent high-temperature oxidation resistance, in which the oxidation products are TiNb₂O₇, Nb₂O₅, SiO₂, TiO₂, and HfO₂. It can be determined that in the oxidation process, the Ti element will preferentially form an oxide film of TiO₂, thereby wrapping around the matrix phases, protecting the matrix, and improving the antioxidant capacity, while the Hf element can form an infinite solid solution with the matrix and consume the small number of oxygen atoms entering the matrix, so as to achieve the effect of improving the oxidation resistance. Full article

This paper presents an advanced dielectric engineering approach utilizing a composition-dependent hafnium zirconium oxide (Hf_1-xZr_xO₂) superlattice (SL) structure for Si nanosheet gate-all-around field-effect transistors (Si NSGAAFETs). The dielectric (DE) properties of solid solution (SS) and SL Hf_1-xZr_xO₂ capacitors were systematically characterized through capacitance-voltage (C-V) and polarization-voltage (P-V) measurements under varying annealing conditions. A high dielectric constant (k-value) of 59 was achieved in SL-Hf_0.3Zr_0.7O₂, leading to a substantial reduction in equivalent oxide thickness (EOT). Furthermore, the SL-Hf_0.3Zr_0.7O₂ dielectric was integrated into Si NSGAAFETs, with the interfacial layer (IL) further optimized via NH₃ plasma treatment. The resulting devices exhibited superior electrical performance, including an enhanced ON-OFF current ratio (I_ON/I_OFF) reaching 10⁷, an increased drive current, and significantly reduced gate leakage. These results highlight the potential of SL-Hf_0.3Zr_0.7O₂ as a high-k dielectric solution for overcoming EOT scaling challenges in advanced CMOS technology and enabling further innovation in next-generation logic applications. Full article

The Youjiang Basin is situated at the junction between the Tethyan and Pacific tectonic domains, and its Permian–Triassic volcanic rocks provide important geological archives recording the tectonic evolution and collisional interactions between the South China and Indochina blocks. This study employed LA-ICP-MS zircon U-Pb geochronology and whole-rock geochemistry to investigate interbedded Triassic felsic volcanics. Felsic volcanic rocks in Youjiang Basin were erupted during the Early–Middle Triassic period (ca. 241~251 Ma) and are situated within the strata of the Beisi, Baifeng, and Banba Formations. These rocks in the Daqingshan area are rich in SiO₂ (66.8~72.7 wt%), K₂O (1.4~5.1 wt%), U (5.2~6.7 ppm), and Th (26~32.1 ppm). Conversely, they are depleted in MgO (0.6~1.4 wt%), TiO₂ (0.5~0.9 wt%), Cr (13.1~19.7 ppm), Ni (7.3~10.1 ppm), and negative Eu anomalies (Eu/Eu* = 0.41~0.52), and they also exhibit negative zircon ε_Hf(t) values. It is inferred that these Triassic felsic volcanics originated from the partial melting of crustal rocks in high-pressure environments such as the garnet stability zone within the deep mantle. These felsic volcanic rocks were likely generated during the transitional stage from island arc subduction to syn-collisional settings. Notably, the syn-collisional interaction between South China and Indochina blocks exerted significantly greater tectonic control on the Youjiang Basin than oceanic subduction. Full article

Magma mixing or mingling is not just a geological phenomenon that widely occurs in granitoid magmatism, but a complex dynamic process that influences the formation of mafic microgranular enclaves (MMEs) and the diversity of granitic rocks. Herein, we carried out a comprehensive study that encompassed the petrology, mineral chemistry, zircon U-Pb ages, Lu-Hf isotopes, whole-rock elements, and Sr-Nd isotope compositions of the Menyuan Granodioritic Pluton in the northern margin of the Qilian Block, to elucidate the petrogenesis and physical and chemical processes occurring during magma mixing. The Menyuan Granodioritic Pluton is mainly composed of granodiorites accompanied by numerous mafic microgranular enclaves (MMEs) and is intruded by minor gabbro dikes. LA-ICP-MS zircon U-Pb dating reveals that these rocks possess a similar crystallization age of ca. 456 Ma. The Menyuan host granodiorites, characterized as metaluminous to weakly peraluminous, belong to subduction-related I-type calc-alkaline granites. The MMEs and gabbroic dikes have relatively low SiO₂ contents and high Mg^# values, probably reflecting a mantle-derived origin. They are enriched in large ion lithophile elements (LILEs) and light, rare earth elements (LREEs) but are depleted in high field strength elements (HFSEs), indicating continental arc-like geochemical affinities. The host granodiorites yield relatively enriched whole-rock Sr-Nd and zircon Hf isotopic compositions (⁸⁷Sr/⁸⁶Sr_i = 0.7072–0.7158; ε_Nd(t) = −9.21 to −4.23; ε_Hf(t) = −8.8 to −1.2), implying a derivation from the anatexis of the ancient mafic lower continental crust beneath the Qilian Block. The MMEs have similar initial Sr isotopes but distinct whole-rock Nd and zircon Hf isotopic compositions compared with the host granodiorites (⁸⁷Sr/⁸⁶Sr_i = 0.7078–0.7089; ε_Nd(t) = −3.88 to −1.68; ε_Hf(t) = −0.1 to +4.1). Field observation, microtextural and mineral chemical evidence, geochemical characteristics, and whole-rock Nd and zircon Hf isotopic differences between the host granodiorites and MMEs suggest insufficient magma mixing of lithospheric mantle mafic magma and lower continental crust felsic melt. In combination with evidence from regional geology, we propose that the anatexis of the ancient mafic lower continental crust and subsequent magma mixing formed in an active continental arc setting, which was triggered by the subducted slab rollback and mantle upwelling during the southward subduction of the Qilian Proto-Tethys Ocean during the Middle-Late Ordovician. Full article

Permian magmatic rocks are extensively distributed in the East Kunlun Orogenic Belt (EKOB), yet controversies persist regarding the petrogenesis of granitoid rocks and the tectonic evolution of the Buqingshan-A’nyemaqing Ocean (BAO), which is a part of the Paleo-Tethys. This study addresses these debates through petrological analyses, whole-rock geochemistry and zircon U-Pb-Lu-Hf isotopic investigations of newly identified granitoids in the EKOB. Monzogranite (MG) and quartz porphyry (QP) yield weighted mean ages of 254.7 ± 1.1 Ma and 254.3 ± 1.1 Ma, respectively. Geochemically, the MG shows metaluminous to weakly peraluminous low-K calc-alkaline I-type affinity, characterized by high SiO₂ and low K₂O, MgO and FeO^T contents, as well as marked enrichment in light rare earth elements (LREEs), but depletion in Eu, Ba, Sr, P and Ti anomalies. In contrast, the QP exhibits a peraluminous high-K calc-alkaline I-type affinity, displaying high SiO₂ but low Na₂O and P₂O₅ contents. It is enriched in LREEs and Rb but displays negative Nb, Sr, P and Ti anomalies. Zircon ε_Hf(t) values range from −1.6 to 2.6 for MG and −4.4 to 1.5 for QP. We suggest that both MG and QP were derived from the partial melting of juvenile mafic lower crust, and that MG underwent a high degree of fractional crystallization. A synthesis of multiscale geological evidence allows us to propose a five-stage tectonic evolution for the BAO in the EKOB: (1) oceanic basin initiation before ca. 345 Ma; (2) incipient northward subduction commencing at ca. 278 Ma; (3) slab rollback stage (263–240 Ma); (4) syn-collisional compression (240–230 Ma); (5) post-collisional extension (230–195 Ma). Full article

This study examines the origin, tectonic setting, and Cu–Pb–Zn polymetallic mineralization of the Yangjiayu Complex, situated on the southwestern margin of the Jiaolai Basin. We present detailed geochemical, zircon U–Pb geochronological, and Hf isotopic data for rhyolite porphyry and monzodiorite samples. Zircon U–Pb dating reveals that the emplacement of both intrusions occurred in the Early Cretaceous. While the monzodiorite (122.5 ± 0.7 Ma) is numerically slightly older than the rhyolite porphyry (121.2 ± 0.6 Ma), considering the error ranges, their ages are essentially similar. The rhyolite porphyry displays higher SiO₂ and Na₂O + K₂O contents and a lower Al₂O₃ content relative to the monzodiorite. Geochemically, both intrusions are classified as high-K calc-alkaline and peraluminous, characterized by enrichment in large-ion lithophile elements (LILEs; e.g., Ba, Rb, Pb) and light rare earth elements (LREEs), along with depletion in high-field-strength elements (HFSEs; e.g., Nb, P, Ta) and heavy rare earth elements (HREEs). The rhyolite porphyry further exhibits middle rare earth elements (MREEs; e.g., Eu, Gd, Tb, Dy) depletion. Similar zircon εHf(t) values (monzodiorite: −23.0 to −26.1; rhyolite porphyry: −23.2 to −25.0) suggest a shared source derived from partial melting of the thickened lower crustal rocks. In comparison to the monzodiorite, the rhyolite porphyry shows lower total REE contents, a more pronounced negative Eu anomaly and stronger MREE depletion, higher Rb, Th, and U concentrations, and more significant P depletion, features indicative of more extensive assimilation-fractional crystallization (AFC). These geochemical and geochronological data indicate that the Yangjiayu Complex originated within an extensional tectonic setting associated with the Early Cretaceous subduction of the Paleo-Pacific Plate underneath the Eurasian Plate. Cu–Pb–Zn mineralization, primarily localized within the monzodiorite, is interpreted to be generated by magmatic-hydrothermal fluids. Therefore, ~120 Ma dioritic intrusions within the Jiaolai Basin constitute prospective targets for (Cu)–Pb–Zn polymetallic exploration. Full article

The emergence of GaN-based micro-LEDs has revolutionized display technologies due to their superior brightness, energy efficiency, and thermal stability compared to traditional counterparts. However, the development of red-emitting micro-LEDs on silicon substrates (GaN-on-Si) faces significant challenges, among them including hydrogen-induced deactivation of p-GaN caused by hydrogen species generated from SiH₄ decomposition during SiO₂ passivation layer growth, which degrades device performance. This study systematically investigates the use of high-density metal-oxide dielectric passivation layers deposited by atomic layer deposition (ALD), specifically Al₂O₃ and HfO₂, to mitigate these effects and enhance device reliability. The passivation layers effectively suppress hydrogen diffusion and preserve p-GaN activation, ensuring improved ohmic contact formation and reduced forward voltage, which is measured by the probe station. The properties of the epitaxial layer and the cross-section morphology of the dielectric layer were characterized by photoluminescence (PL) and scanning electron microscopy (SEM), respectively. Experimental results reveal that Al₂O₃ exhibits superior thermal stability and lower current leakage under high-temperature annealing, while HfO₂ achieves higher light-output power (LOP) and efficiency under increased current densities. Electroluminescence (EL) measurements confirm that the passivation strategy maintains the intrinsic optical properties of the epitaxial wafer with minimal impact on Wp and FWHM across varying process conditions. The findings demonstrate the efficacy of metal-oxide dielectric passivation in addressing critical challenges in InGaN red micro-LED on silicon substrate fabrication, contributing to accelerating scalable and efficient next-generation display technologies. Full article

The tectonic evolution of Hainan Island during the Late Permian–Early Triassic period is still unclear. This study identified two types of basalts on the island and presented detailed geochronology, whole-rock geochemistry, and Hf isotope data of the Late Permian–Early Triassic basalts. U-Pb dating results indicated that baddeleyites and zircons of one sample from Group 1 basalts had formation ages of 256 ± 3 Ma and 255 ± 3 Ma, respectively, and two samples from Group 2 gave formation ages of 241 ± 2 Ma and 240 ± 3 Ma, respectively. Both groups are characterized by negative anomalies of Nb, Ta, and Ti, and enrichment in Ba, Th, U, and K. Group 1 belongs to sub-alkaline basalt and exhibited SiO₂ contents ranging from 50.50% to 51.05%, with ΣREE concentration of 136–148 ppm. Hf isotope analysis showed that the ε_Hf(t) values of baddeleyites and zircons were −10.56 to −4.70 and −14.94 to −6.95, respectively. Group 2 belongs to alkaline basalt and had a higher SiO₂ content of 52.48%–55.49% and ΣREE concentration of 168–298 ppm. They showed more depleted Hf isotopic composition with ε_Hf(t) values ranging from −2.82 to +4.74. These data indicate that the source area of Group 1 was an enriched mantle, likely derived from partial melting of spinel lherzolite mantle, and was modified by subduction-derived fluids. Group 2 was derived from depleted mantle, most likely originating from partial melting of garnet + spinel lherzolite mantle. They were contaminated by crustal materials and metasomatized by subduction-derived fluids with a certain degree of fractional crystallization. Comprehensive analysis suggests that Group 1 samples likely formed in an island arc tectonic setting, while Group 2 formed in a continental intraplate extensional (or initial rift) tectonic setting. Their formation was mainly controlled by the Paleo-Tethys tectonic domain. Group 1 basalts implied that subduction of the Paleo-Tethys oceanic crust lasted at least in the late Permian (ca. 255 Ma). Group 2 basalts revealed that the intra-plate extensional (or initial rift) stage occurred in the middle Triassic (ca. 240 Ma). Full article

The Kongco area of Nima in the northern part of the Lhasa terrane has a suite of alkaline granitic porphyry dykes associated with Early Cretaceous granites and accompanied by Cu/Mo mineralization. LA-ICP-MS ²⁰⁶Pb/²³⁸U zircon geochronology performed on the dykes produced an age of 104.15 ± 0.94 Ma (MSWD = 0.98), indicating the Early Cretaceous emplacement of the dykes. The dykes exhibit high silica (SiO₂ = 76.22~77.90 wt.%), high potassium (K₂O = 4.97~6.21 wt.%), high alkalinity (K₂O + Na₂O = 8.07~8.98 wt.%), low calcium (CaO = 0.24~0.83 wt.%), low magnesium (MgO = 0.06~0.20 wt.%), and moderate aluminum content (Al₂O₃ = 11.93~12.45 wt.%). The Rieterman index (σ) ranges from 1.93 to 2.34. A/NK (molar ratio Al₂O₃/(Na₂O + K₂O)) and A/CNK (molar ratio Al₂O₃/(CaO + Na₂O + K₂O)) values of the dykes range from 1.06 to 1.18 and 0.98 to 1.09, respectively. The dykes are relatively enriched in Rb, Th, U, K, Ta, Ce, Nd, Zr, Hf, Sm, Y, Yb, and Lu, and they show a noticeable relative depletion in Ba, Nb, Sr, P, Eu, and Ti, as well as an average differentiation index (DI) of 96.42. The dykes also exhibit high FeO_T/MgO ratios (3.60~10.41), Ga/Al ratios (2.22 × 10⁻⁴~3.01 × 10⁻⁴), Y/Nb ratios (1.75~2.40), and Rb/Nb ratios (8.36~20.76). Additionally, they have high whole-rock Zr saturation temperatures (884~914 °C), a pronounced Eu negative anomaly (δEu = 0.04~0.23), and a rightward-sloping “V-shaped” rare earth element pattern. These characteristics suggest that the granitic porphyry dykes can be classified as A2-type granites formed in a post-collisional tectonic environment and that they are weakly peraluminous, high-potassium, and Calc-alkaline basaltic rocks. Positive ε_Hf(t) values = 0.43~3.63 and a relatively young Hf crustal model age (T_DM2 = 826~1005 Ma, ⁸⁷Sr/⁸⁶Sr ratios = 0.7043~0.7064, and ε_Nd(t) = −8.60~−2.95 all indicate lower crust and mantle mixing. The lower crust and mantle mixing model is also supported by (²⁰⁶Pb/²⁰⁴Pb)t = 18.627~18.788, (²⁰⁷Pb/²⁰⁴Pb)t = 15.707~15.719, (²⁰⁸Pb/²⁰⁴Pb)t = 39.038~39.110). Together, the Hf, Sr and Pb isotopic ratios indicate that the Kongco granitic porphyry dykes where derived from juvenile crust formed by the addition of mantle material to the lower crust. From this, we infer that the Kongco granitic porphyry dykes are related to a partial melting of the lower crust induced by subduction slab break-off and asthenospheric upwelling during the collision between the Qiangtang and Lhasa terranes and that they experienced significant fractional crystallization dominated by potassium feldspar and amphibole. These dykes are also accompanied by significant copper mineralization (five samples, copper content 0.2%), suggesting a close relationship between the magmatism associated with these dykes and regional metallogenesis, indicating a high potential for mineral exploration. Full article

The Yidun island arc was formed in response to the Late Triassic westward subduction of the Ganzi–Litang oceanic plate, a branch of the Paleo-Tethys Ocean. The Zhongdian arc, located in the south of the Yidun island arc, has relatively large number of porphyry (skarn) type Cu–Mo ± Au polymetallic deposits, the largest of which is the Pulang Cu (–Mo–Au) deposit with proven Cu reserves of 5.11 Mt, Au reserves of 113 t, and 0.17 Mt of molybdenum. However, the relationship between mineralization and the potassic alteration zone, phyllic zone, and propylitic zone of the Pulang porphyry deposit is still controversial and needs further study. Titanite (CaTiSiO₅) is a common accessory mineral in acidic, intermediate, and alkaline igneous rocks. It is widely developed in various types of metamorphic rocks, hydrothermally altered rocks, and a few sedimentary rocks. It is a dominant Mo-bearing phase in igneous rocks and contains abundant rare earth elements and high-field-strength elements. As an effective geochronometer, thermobarometer, oxybarometer, and metallogenic potential indicator mineral, titanite is ideal to reveal the magmatic–hydrothermal evolution and the mechanism of metal enrichment and precipitation. In this paper, major and trace element contents of the titanite grains from different alteration zones were obtained using electron probe microanalysis (EPMA) and laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to define the changes in physicochemical conditions and the behavior of these elements during the process of hydrothermal alteration at Pulang. Titanite in the potassic alteration zone is usually shaped like an envelope. It occurs discretely or is enclosed by feldspar, with lower contents of CaO, Al, Sr, Zr and Hf; a low Nb/Ta ratio; high ∑REE + Y, U, Th, Ta, Nb, and Ga content; and high FeO/Al₂O₃ and LREE/HREE ratios. This is consistent with the characteristics of magmatic titanite from fresh quartz monzonite porphyry in Pulang and other porphyry Cu deposits. Titanite in the potassium silicate alteration zone has more negative Eu anomaly and a higher U content and Th/U ratio, indicating that the oxygen fugacity decreased during the transformation to phyllic alteration and propylitic alteration in Pulang. High oxygen fugacity is favorable for the enrichment of copper, gold, and other metallogenic elements. Therefore, the enrichment of copper is more closely related to the potassium silicate alteration. The molybdenum content of titanite in the potassium silicate alteration zone is 10²–10⁴ times that of the phyllic alteration zone and propylitic alteration zone, while the copper content is indistinctive, indicating that molybdenum was dissolved into the fluid or deposited in the form of sulfide before the medium- to low-temperature hydrothermal alteration, which may lead to the further separation and deposition of copper and molybdenum. Full article

The Ordovician/Silurian boundary (Wufeng/Longmaxi formations) in the Shizhu region, eastern Sichuan Basin, China hosts organic-rich black shales which are frequently interbedded with bentonite and hydrothermal minerals (e.g., pyrite). This study investigated the mineralogical, total organic carbon (TOC), total sulfur (TS), and major and trace element compositions of organic-rich samples. Non-visible volcanic input is identified to influence organic matter accumulation, as shown by the correlations between TOC and proxies, including Zr and Hf contents and the Cr/Al₂O₃, V/Al₂O₃, Ni/Al₂O₃, and SiO₂/Al₂O₃ ratios. Redox indicators (V/Cr, v/v + Ni, degree of pyritization (DOP), U/Th, and Mo contents) display positive correlations with TOC values, suggesting that an oxygen-depleted environment is necessary for organic matter (OM) preservation. The TOC values exhibit better regression coefficients (R²) against redox indicators, including DOP (0.43), U/Th (0.70), and Mo contents (0.62), than V/Cr (0.16) and v/v + Ni (0.21). This may because some V, Cr, and Ni is hosted in non-volcanic ashes within shales but not inherited from contemporaneous water columns. The greater scatter in TOC-DOP and TOC-Mo relative to TOC-U/Th relations may result from hydrothermal venting in shales, evidenced by the coexistence of framboid and euhedral pyrite and the previous finding of hydrothermally altered dolomites in the studied sections. There is no systematic relation between TOC and Ni/Co ratios, and this means that portions of Ni are contributed by non-visible volcanic ashes and Ni and Co are redistributed during the precipitation of hydrothermal pyrites due to their strong chalcophile affinities. Such a feature may further suggest that most pyrites are precipitated during hydrothermal venting. The DOP displays broad correlations with non-visible volcanic indicators, supporting that hydrothermal venting may be triggered by volcanic activities. The outcomes of this study highlight that caution is necessary when evaluating the sedimentary facies features of volcanism-affected organic-rich black shales with the used metallic proxies. Full article