Porphyry copper deposits are commonly associated with porphyries generated in arc environments. Assessing the contemporaneous arc volcanic rocks provides crucial insights into the potential for porphyry copper mineralization. The Triassic Yidun arc in the northern part of the Sanjiang orogen in southwest China, which formed in association with the subduction of the Paleo-Tethys Oceanic slab, hosts several porphyry copper deposits. However, the potential for porphyry copper mineralization in the Yunxian-Jinggu volcanic arc in the southern part of the Sanjiang orogen, which was also linked to the subduction of the Paleo-Tethys Oceanic slab, remains unclear. This study reports zircon U–Pb ages, trace element compositions and Hf isotopes, and whole-rock element compositions and Sr–Nd–Pb isotopes of the basaltic-andesitic-dacitic rocks in the Yunxian-Jinggu volcanic arc. Zircon SHRIMP U–Pb dating of the Wenyu basalts and andesites yielded ages of 244.3 ± 1.9 Ma and 242.5 ± 2.5 Ma, respectively. The basalts have arc geochemical affinities with εHf (t) values of 2.3 to 9.3, εNd(t) values of –0.6 to 0.2, and (87Sr/86Sr)i values of 0.7065 to 0.7068. They have high Ba concentrations (∼550 ppm), highly variable Ba/La ratios (0.01 to 0.10), and a narrow range of Th/Yb ratios (1.2 to 1.9). These characteristics suggest that the basalts were derived from mantle metasomatized by fluids likely released from the subducted Paleo-Tethys slab. The Wenyu andesites, with εHf (t) values range from 1.6 to 7.0, εNd (t) value of –0.4, and (87Sr/86Sr)i value of 0.7031, along with distinct Pb isotopes, were probably produced through basaltic magmas undergoing crustal fractional crystallization. The Minle dacites, sharing similar εHf (t) value (–1.6 to 10.7) but lower εNd (t) values (–3.1 to –4.9) compared to Wenyu volcanics, are interpreted as derived from partial melting of basaltic magmas with contamination from ancient crustal components. The zircon Eu/Eu* ratios (mostly < 0.4), zircon ΔFMQ value (–0.6 ± 1.1), and bulk-rock Sr/Y ratios (<10.3) for the Yunxian-Jinggu volcanic rocks indicate that co-genetic intrusions, if present, would likely be less hydrous and less oxidized, making them less favorable for porphyry copper mineralization.
Abstract Carbonatite intrusions host the world’s most important light rare earth element (LREE) deposits, and their formation generally requires extraordinary fertile sources, magmatic evolution, and hydrothermal events. However, carbonatitic magma evolution, particularly the role of fractional crystallization and contamination from silicate rocks in REE enrichment, remains enigmatic. The Maoniuping world-class REE deposit in southwestern China, is an ideal target to decipher magmatic evolution and related REE enrichment as it shows continuous textual evolution from medium- to coarse-grained calcite carbonatite (carbonatite I) at depth, to progressively pegmatoidal calcite carbonatite (carbonatite II) at shallow levels. In both types of calcite carbonatites, four generations of calcite can be classified according to petrographic and geochemical characteristics. Early-crystalizing calcite (Cal-I and Cal-II) are found in carbonatite I and exhibit equigranular and a polygonal mosaic textures, while late calcites (Cal-III and Cal-IV) in carbonatite II are large-size oikocrysts (>0.5 mm in length) with strain-induced undulatory extinction and bent twinning lamellae. All these generations of calcite yield similar, near-chondritic, Y/Ho ratios (26.6–28.1) and are inferred to be of magmatic origin. Remarkably, gradual enrichment of MgO, FeO and MnO from Cal-I to Cal-IV is coupled with a significant increase in REE contents (~800 to 2000 ppm), with LREE-rich and gentle-to-steep chondrite-normalized REE patterns ((La/Yb)N = 3.1–26.8 and (La/Sm)N = 0.9–3.9, respectively). Such significant REE enrichment is ascribed to protracted magma fractional crystallization with initial low degree of fractional crystallization (fraction of melt remining (F) = ~0.95) evolving to late stage (F = 0.5–0.6) by formation of abundant calcite cumulates. Differential LREE and HREE behavior during magma evolution largely depend on separation of phlogopite, amphibole, and clinopyroxene from the carbonatitic melt, which is indicated by progressively elevated (La/Yb)N ratios ranging from 3.1 to 26.8. The four generations of calcite have significantly different C and Sr isotopic compositions with δ13CV-PDB decreasing from −3.28 to −9.97‰ and 87Sr/86Sr increasing from 0.70613 to 0.70670. According to spatial relations and petrographic observations, the relative enrichment of δ13C and depletion in 87Sr/86Sr ratios of Cal-I and Cal-II show primary isotopic characteristics inherited from initial carbonatitic magma. By contrast, the variable Sr and C isotopic compositions of Cal-III and Cal-IV are interpreted as the results of contamination by components derived from silicate wall rocks and loss of CO2 by decarbonation reactions. To model such contamination processes, Raleigh volatilization and Monte Carlo simulation have been invoked and the model results reveal that carbonatitic melt-wall rock interaction requires 40% radiogenic Sr contamination from silicate rocks and 35% CO2 degassing from carbonatitic melt. Moreover, positive correlations between decreasing δ13C values and increasing REE contents, together with bastnäsite-(Ce) precipitation, indicate further REE accumulation during the contamination processes. In summary, alongside REE-rich magma sources, the extent of fractional crystallization and contamination during carbonatitic magma evolution are inferred to be important mechanisms in terms of REE enrichment and mineralization in carbonatite-related REE deposits worldwide.
Abstract Carbonatite complexes are globally significant sources of rare earth elements (REEs); however, mechanisms governing REE deposition in various tectono-lithologic settings, encompassing host rocks, wall rocks, ore-controlling structures, and metasomatism, remain inadequately understood. The Zhengjialiangzi mining camp, situated within the extensive Muluozhai deposit (containing 0.45 million metric tons [Mt] at 4.0 wt % REE2O3) in the northern segment of the Mianning-Dechang belt, Sichuan (southwestern China), is characterized by a complex vein system that evolved within metamorphosed supracrustal rocks of the Yangxin and Mount Emei Formations. The mineralization is coeval with Oligocene intrusions of carbonatite and nordmarkite at ~27 Ma. The major gangue minerals include fluorite, barite (transitional to celestine), and calcite, with bastnäsite serving as the primary host for REEs in all analyzed orebodies. Several other accessory to minor minerals were identified in the ore veins, including some that had not previously been known to occur in the Muluozhai deposits (e.g., thorite and pyrochlore). The stable isotopic (C-O-Ca) and trace element compositions of calcite, along with whole-rock data, suggest that carbonate material was derived from the mantle and subsequently reequilibrated with the Yangxin marbles. The radiogenic isotope (Sr-Nd-Pb) compositions of vein material remained unaffected by wall-rock contamination and suggest a mantle source influenced by crustal recycling, consistent with other REE deposits hosted by carbonatite and nordmarkite in the region. The combined petrographic and geochemical evidence suggests derivation of Muluozhai mineralization from a carbonatitic source and interaction of carbonatite-derived fluids with wall rocks, xenoliths, and early-crystallizing mineral phases, particularly barite.
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.
Copper deposits hosted by volcanic rocks can have different genetic types. Many copper vein deposits at the margin of the Cenozoic Lanping-Simao foreland fold-thrust belt in southwest China are controlled by thrust faults and hosted by Triassic volcanic rocks formed in association with the evolution of the Paleo-Tethys Ocean. The genesis of these copper deposits is poorly understood. Wenyu is a typical Cu deposit hosted in the Middle−Late Triassic basaltic-andesitic rocks and experienced three major hydrothermal stages characterized by mineral assemblages of calcite, anhydrite, and barite (Stage I); early quartz, chlorite, and epidote (Stage II); and Cu sulfides, galena, pyrite, hematite, and late quartz (Stage III). Consistency of the boiling temperature from fluid inclusions in the calcite and the temperature inferred from the C-O isotopes of the calcite, and the oxygen isotopes of the anhydrite and barite indicate that the stage I fluids probably have a δ13C value of ∼−4.5‰ and δ18O values in the range of ∼−3‰ to +4‰. Oxygen isotopes of the early quartz (δ18O = 15.1‰ to 17.4‰), D-O isotopes of chlorite and epidote, and the fluid inclusion data indicate that the stage II fluids have δ18O values of ∼2.4‰ to 5.0‰ and δ18D values of −68‰ to −53‰. Thus, the stage I and II fluids were inferred to be deep-seated brines with temperatures predominantly between 180 °C and 240 °C and salinities of 16−18 wt% NaCl eq. More significant meteoric water was involved during stage III based on the oxygen isotopes of the late quartz (δ18O = 6.2‰ to 9.5‰). The large variation in δ34S values (−21.3‰ to 1.6‰) in the sulfides, the sample- and grain-scale sulfur isotope fractionation, combined with the ore textural evidence that the sulfates and chlorite were replaced by Cu sulfides accompanied by hematite, indicate that the reduced sulfur responsible for sulfide precipitation was generated by inorganic reduction of the previously formed anhydrite and barite (δ34S = 6.3‰ to 8.6‰) or sulfates in the brines by oxidation of chlorite to hematite. Lead isotopes of galena (206Pb/204Pb = 18.67−18.87; 207Pb/204Pb = 15.68−15.72) and copper isotopes of Cu sulfides (δ65Cu = −0.34‰ to 0.51‰) indicate that the ore-forming metals (e.g., Cu and Pb) were derived from the ore-hosting Triassic volcanic rocks. The Wenyu copper deposit cannot be classified as a porphyry, epithermal, or volcanogenic massive sulfide deposit. It is believed that the deep-seated brines, such as the saline formation water in the Permian marine strata, migrated upward along the thrust faults into the Triassic basaltic-andesitic volcanic rocks, and leached metals from the volcanic rocks and precipitated Cu sulfides via inorganic sulfate reduction at Wenyu during the Cenozoic. Such mineralization processes may explain the genesis of the volcanic-hosted copper vein deposits in the Lanping-Simao foreland fold-thrust belt and other similar belts in the world.
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