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Porphyry Mo deposits have traditionally been classified into two major classes, arc-related and Climax-type, based on the tectonic setting and chemistry of associated intrusions. Although there is a consensus that porphyry Mo systems were formed by the optimal coincidence of geological processes operating at different scales, it is unclear what key parameter(s) render systems productive and whether the two classes of porphyry Mo deposits are unique in their mode of formation, or if they share fundamentally similar geological processes. These questions are important as a clearer understanding of the optimum conditions for the formation of porphyry Mo deposits is a prerequisite for more efficient exploration. This contribution presents a detailed assessment of the factors affecting the formation of porphyry Mo deposits through the investigation of barren and mineralized intrusions from the arc-related Songbei-Yangjiazhangzi-Lanjiagou (SYL) ore zone and the Climax-type Hashitu deposit of northeastern China. Our results show that the syn-mineralization intrusions from the SYL ore zone are quite evolved (SiO2 ~ 75 wt%; Na2O+K2O ~ 8.7 wt%) and are characterized by apparent light rare earth element (LREE) enrichments (LaN/YbN = 2.7–33.1) and moderate negative Eu anomalies (Eu/Eu* = 0.4–0.7). They show enriched zircon Hf isotopic compositions [εHf(t) = –11.9 to –4.8], indicating their parental magmas were likely derived from an ancient crustal source. Melt inclusions from the SYL syn-mineralization intrusions contain negligible F and Cl. In contrast, Hashitu syn-mineralization intrusions are characterized by weak LREE enrichments (LaN/YbN = 2.2–6.9) and strong negative Eu anomalies (Eu/Eu* = 0.02–0.10), with SiO2 and Na2O+K2O contents similar to the SYL syn-mineralization intrusions. They show depleted zircon Hf isotopic compositions [εHf(t) = 3.1–5.0], indicating their parental magmas were likely derived from a juvenile crustal source. Melt inclusions from the Hashitu syn-mineralization intrusions contain up to 0.4 wt% F and 0.03 to 0.09 wt% Cl. However, in both cases, the syn-mineralization intrusions are Mo-poor (1–7 ppm Mo), oxidized (above the quartz-fayalite-magnetite buffer), water-saturated (4.4–7.8 wt% H2O), and were emplaced at palaeodepths of 3.3 to 8.3 km. These data imply that magma source composition is not a key factor in the formation of porphyry Mo deposits. In contrast, magma oxygen fugacity, water content, and emplacement depth appear to play fundamental roles in the formation of porphyry Mo deposits of both arc-related and Climax-type. Within individual deposits, no systematic differences between pre- and syn-mineralization intrusions are observed in terms of magma source, fractionation degree, oxygen fugacity, emplacement depth, and volatile and Mo contents. Instead, a crucial apparent difference lies in the geometry of the intrusions, i.e., pre-mineralization intrusions generally occur as flat, ponded bodies, whereas syn-mineralization intrusions commonly develop as small stocks or dikes. Our results, in combination with an examination of other porphyry Mo systems, suggest that the sudden depressurization of magma chambers and subsequent venting of voluminous fluids along focusing structures (such as small stocks or dikes) most likely plays a critical role in the formation of porphyry Mo deposits of both arc-related and Climax-type. The findings of this study indicate that fluid processes in the shallow crust are pivotal for the formation of porphyry Mo deposits and that settings with ideal magmatic-hydrothermal architectures are most likely to develop into productive porphyry Mo systems.

The Mesozoic (160–130 Ma), fault-controlled Xikuangshan Sb deposit within Devonian limestone strata of Hunan Province, Southern China is the world’s largest Sb deposit containing a proven reserve of ~2.5 m Sb. Although mined for over a century, its genesis remains poorly understood. Here we use new He-Ar isotope data of hydrothermal stibnite and both new and existing C-O-Sr-Nd isotopes of hydrothermal calcite with known stages to decipher its genesis and the major constraints on mineralization intensity. The 3He/4He and 40Ar/36Ar ratios of fluid inclusions trapped in stibnite are from 0.01 to 0.04 Ra (Ra: atmospheric 3He/4He ratio) and 304–1077, respectively, indicating the ore-forming fluids at Xikuangshan were dominated by air-saturated meteoric groundwater after interaction with crustal rocks. Ore-stage calcite C and O isotopes indicated that most CO2 in the fluids was acquired from marine carbonate rocks by dissolution; whereas Sr and Nd isotopes differed from deposited Devonian country rocks but were similar to the underlying regional Proterozoic clastic rocks in the region. Calcite from early and late stages showed a strong positive correlation between δ18O and 87Sr/86Sr, consistent with the mixing between the circulating groundwater and compounds released from the Proterozoic rocks due to extensive fluid-rock interaction. The 3He/Q ratios of the fluid inclusions are low, varying from 4.3 to 18.5 × 10−15 cm3 standard temperature and pressure (STP) J−1, indicating deep-seated magma could have provided heat by conduction but no volatiles into the ore-forming fluids. Based on these new results, we suggest that deep-seated granitic magma heated the down-going meteoric groundwater along fault zones, after which the groundwater extensively interacted with and extracted Sb from the Proterozoic Sb-rich rocks to form Sb-rich fluids. The Sb-rich fluids then ascended through regional faults and deposited Sb as stibnites at favorable structural traps to form the Xikuangshan Sb deposit. This study highlights that extensive water-rock interaction is essential to form the deposit, and more intensive water-rock interaction at an early stage allowed for early-stage mineralization yielding higher Sb reserves (>80%) at Xikuangshan.

Identifying magma fertility is an important task in ore genesis research. In this paper, we use apatite chemistry and Sr-Nd isotopes for such a study. The apatite crystals are from four Cretaceous coeval granodiorite intrusions with different styles of hydrothermal mineralization in the Tongling ore district, South China. The selected intrusions are Hucun, Dongguashan, and Xinwuli, which host both porphyry and skarn Cu deposits, and the Chaoshan, which hosts a skarn Au deposit. The abundances of apatite major and trace elements, such as Mn, V, Ce, S, F, Cl, and Cu, together with the whole-rock compositions, are used to decipher the oxidation states, volatile compositions, and Cu fertility of the parental magmas. The apatite Sr-Nd isotope compositions are used as tracers for the magma sources. The results show that: (1) the parental magma of the Au-mineralized intrusion is less oxidized and has higher S-Cl contents than those of the Cu-mineralized intrusions, and (2) the proportion of mantle-derived melt is much higher in the former than in the latter. The results also reveal that the Cumineralized intrusions have highly variable apatite Cu-Cl-S compositions. Specifically, the Xinwuli intrusion has much higher Cu but lower Cl-S contents in apatite than the other two intrusions, indicating that a Cu-rich magma is not universally required for the formation of hydrothermal Cu deposits. This study demonstrates that apatite is a robust petrogenetic and metallogenic indicator for porphyry and skarn-type Cu-Au ore deposits.

Processes controlling the metal endowment of arc-related porphyry Mo deposits are not well understood. Located in northeastern China, the arc-related Luming porphyry Mo deposit has a proven reserve of 0.75 Mt Mo at an average grade of 0.092 wt % and is characterized by multiple pulses of alteration and mineralization. These features make this deposit an ideal location to investigate the role of multiple pulses of magmatism and fluid release in the evolution and formation of an arc-related porphyry Mo deposit. Molybdenum mineralization at Luming is typically observed as a series of molybdenite-bearing veins hosted within a composite intrusive complex, referred to as the Luming Intrusive Suite. Crosscutting relationships between intrusive units and offset veins indicate that the Luming Intrusive Suite is composed of five major, successive granitic intrusions: the premineralization plutonic biotite monzogranite and monzogranite units, and the synmineralization stock- and dike-like porphyritic monzogranite, granite porphyry, and syenogranite units. Each synmineralization unit is associated with similar vein sequences that comply with the general form of early EB-type biotite veins, through A-type quartz ± biotite and B-type quartz-molybdenite veins, to late D-type quartz-molybdenite ± pyrite ± chalcopyrite, molybdenite, quartz-pyrite ± calcite, and calcite ± clays veins. The intensity and volume of alteration and mineralization within a given synmineralization unit decrease from early- through inter- to late-mineralization units. Although minor Mo mineralization is associated with potassic alteration along B-type veins, the majority of the ore is associated with D-type quartz-molybdenite-pyrite and molybdenite veins rimmed by sericite-chlorite-pyrite alteration, which are primarily hosted in the two premineralization units.A combination of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) zircon U-Pb and hydrothermal biotite 40Ar/39Ar studies, together with available isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS) molybdenite Re-Os data, has resulted in a substantial reappraisal of the timing of magmatism and its association with molybdenite mineralization at Luming. The volumetrically dominant premineralization intrusive units have indistinguishable zircon U-Pb weighted mean 206Pb/238U ages ranging from 187.5 ± 2.8 to 186.5 ± 3.6 Ma (2σ), whereas the synmineralization units yield weighted mean 206Pb/238U ages from 178.6 ± 2.2 to 175.6 ± 3.0 Ma (2σ). The zircon U-Pb weighted mean 206Pb/238U ages of the synmineralization units are indistinguishable from the mean molybdenite Re-Os model (178.1 ± 2.7; 2σ) and hydrothermal biotite 40Ar/39Ar plateau (174.7 ± 1.1 Ma; 2σ) ages within uncertainty, confirming a genetic link with mineralization. Melt inclusion data show that the synmineralization intrusions were Mo poor, with Mo concentrations The data presented here suggest that molybdenite mineralization at Luming was most likely accomplished through three discrete magmatic-hydrothermal events during assembly of the Mo-poor synmineralization intrusive complex. The giant Luming deposit appears to be related to multiple pulses of magmatic-hydrothermal activities, resulting in the superposition of temporally distinct mineralization events. Our results suggest that pulsed release of ore-forming magmas and fluids, which are channeled along focusing structures like small porphyry fingers within a focused area, from a large magma chamber at depth may play a major role in the formation of large to giant porphyry Mo deposits of both the arc-related and Climax types. This conclusion is in line with field observations of a number of large to giant porphyry Mo deposits, which commonly show reversals in magmatic-hydrothermal evolutionary trend and are associated with multiple pulses of small stocks and dikes that are separate in time and space.

The Jinding deposit, located in the northern part of Lanping basin in southwest China, is the second largest Zn-Pb deposit in China and the third largest Mississippi Valley-type deposit identified globally. The deposit consists of several large tabular orebodies within the Jinding dome. Two stages of sulfide mineralization (sphalerite, galena, and pyrite) are identified, which are mainly hosted in the siliciclastic strata of Early Cretaceous and Paleocene age. The early sulfide minerals are mostly fine grained ( The δ34S values, ranging from –30 to –10‰ for the fine-grained and disseminated sulfide minerals and from –24.50 to –16.27‰ for the solid bitumen in the early (main) mineralization stage, suggest that H2S was generated by microbial sulfate reduction. We propose that this occurred in the Triassic strata prior to or during migration of hydrocarbons to the Jinding dome to form a H2S-enriched paleo-oil reservoir. This hypothesis is supported by the similarity of the δ34S values (–27.62 to –17.38‰) of solid bitumen in the Sanhedong Formation (the source rocks) to that of bitumen in the ores. The late-ore sulfide, however, displays significantly higher δ34S values, ranging from –8 to 0‰. We propose that the H2S of this stage was mainly generated by thermochemical sulfate reduction as a result of the interaction between hydrocarbons, sulfate, and hydrothermal fluid. The hydrocarbons were oxidized into bitumen that has δ34S values from –7.38 to –4.61‰.

The Youjiang basin on the southwestern margin of the Yangtze block in southwestern China is the world’s second largest Carlin-type gold province after Nevada, USA. The lack of precise age determinations on gold deposits in this province has hindered understanding of their genesis and relation to the geodynamic setting. Although most Carlin-type gold deposits in the basin are hosted in calcareous sedimentary rocks, ~70% of the ore in the Badu Carlin-type gold deposit is hosted by altered and sulfidized dolerite. Although in most respects Badu is similar to other Carlin-type gold deposits in the province, alteration of the unusual dolerite host produced hydrothermal rutile and monazite that can be dated. Field observations show that gold mineralization is spatially associated with, but temporally later than, dolerite. In situ secondary ion mass spectrometry (SIMS) U-Pb dating on magmatic zircon from the least altered dolerite yielded a robust emplacement age of 212.2 ± 1.9 Ma (2σ, mean square of weighted deviates [MSWD] = 0.55), providing a maximum age constraint on gold mineralization. The U-Th/He ages of detrital zircons from hydrothermally mineralized sedimentary host rocks at Badu and four other Carlin-type gold deposits yielded consistent weighted mean ages of 146 to 130 Ma that record cooling from a temperature over 180° to 200°C and place a lower limit on the age of gold mineralization in the basin. Hydrothermal rutile and monazite that are coeval with gold mineralization have been identified in the mineralized dolerite. Rutile is closely associated with hydrothermal ankerite, sericite, and gold-bearing pyrite. It has high concentrations of W, Fe, V, Cr, and Nb, as well as growth zones that are variably enriched in W, Fe, Nb, and U. Monazite contains primary two-phase fluid inclusions and is intergrown with gold-bearing pyrite and hydrothermal minerals. In situ SIMS U-Pb dating of rutile yielded a Tera-Wasserburg lower intercept age of 141.7 ± 5.8 Ma (2σ, MSWD = 1.04) that is within error of the in situ SIMS Th-Pb age of 143.5 ± 1.4 Ma (2σ, MSWD = 1.5) on monazite. These ages are ~70 m.y. younger than magmatic zircons in the host dolerite and are similar to the aforementioned U-Th/He cooling ages on detrital zircons from hydrothermally mineralized sedimentary host rocks. We, therefore, conclude that the Badu Carlin-type gold deposit formed at ca. 144 Ma. The agreement of the rutile and monazite ages with the U-Th-He cooling ages of Badu and four other Carlin-type gold deposits in the Youjiang basin suggests that ca. 144 Ma is representative of a regional Early Cretaceous Carlin-type hydrothermal event formed during back-arc extension.

The genesis of the giant Ag-Cu-Pb-Zn polymetallic mineralization in the northern Lanping basin, Southwest China, remains controversial. To address the sources of metals, a systematic study on Hg isotope compositions was conducted for the Cu-dominated deposit at Baiyangping and the Pb-Zn-dominated deposits at Fulongchang and Liziping. The Cu deposit shows positive Δ199Hg signatures (0.14 ± 0.13‰), in contrast to the Δ199Hg of the Pb-Zn deposits (− 0.09 ± 0.06‰). As positive Δ199Hg values are commonly observed in marine sediments and the Lanping Triassic marine sedimentary rocks show exclusively positive Δ199Hg signals (0.03 ± 0.07‰), the Hg in Cu ores was mainly sourced from the Triassic strata. The negative Δ199Hg signals observed in the Pb-Zn deposits, typical of terrestrial Hg, agree roughly with those of the Jurassic to Paleocene terrestrial sedimentary rocks (− 0.05 ± 0.08 ‰), indicating that the terrestrial strata provided the Hg in Pb-Zn ores. Compared to the source rocks, the Cu deposit shows isotopically lighter Hg enrichments (δ202Hg = − 2.30 ± 0.35‰), possibly resulting from fractionations induced by Hg2+ sorption, organic complexation, and precipitation of Hg-bearing sulfides. The Pb-Zn deposits show comparable or slightly heavier δ202Hg (− 0.56 ± 0.48‰); moreover, δ202Hg values of late-stage sulfides are higher than early-stage δ202Hg values, suggesting that the δ202Hg variation was primarily caused by sulfide precipitation. Thus, Hg isotope data indicate that separate hydrothermal events resulted in Cu and Pb-Zn mineralization. More importantly, this study reveals the great potential of Hg isotopes to discriminate sedimentary sources of metals for low-temperature hydrothermal deposits.

The Jinding deposit in the Lanping basin, southwest China, is the largest sandstone-hosted Zn deposit in the world and the second largest Zn-Pb deposit in China. However, questions related to the metal compositions and origin of the ore fluids remain. In this study, microthermometry and laser ablation-inductively coupled plasmamass spectrometry (LA-ICP-MS) were employed to determine the properties and compositions of individual fluid inclusions trapped in sphalerite and calcite. The results show that the fluid inclusions trapped in sphalerite and calcite have similar homogenization temperatures (79°–173°C with the majority 100°–130°C), salinities (10.3–29.1 wt % NaCl + CaCl2 equiv with the majority 24.5–27.4 wt % NaCl + CaCl2 equiv), and concentrations of alkali and alkali earth elements (e.g., Na, Ca, Mg, K, Sr, Ba, Li, Rb, and Cs). However, the concentrations of ore and associated metals (e.g., Pb, Sb, Ag, and Tl) in the fluid inclusions hosted by sphalerite are significantly higher than those hosted by calcite. Based on these observations, we propose that the sulfides including sphalerite were precipitated from a low-temperature, high-salinity, Ca-rich, metal-rich fluid, while the gangue minerals such as calcite crystallized subsequently from fluids depleted in metals due to prior precipitation of sulfides, and that the high salinities of the fluid inclusions are likely due to a combination of seawater evaporation and subsequent dissolution of evaporitic sequences during fluid percolation. The LA-ICP-MS analyses reveal that the fluid inclusions have K/Na, Rb/Na, and Cs/Na ratios within the range of modern basinal brines, and Li/Na, Ba/Na, and Ca/Na ratios share similar compositions with the ore fluids of basement interacted deposits in the world. The Jinding ore fluids contain ~200 to 650 ppm Pb, based on the data of fluid inclusions trapped in sphalerite. The estimated concentrations of Zn in the ore fluids are also very high at ~200 to 6,500 ppm. Our results reveal that anomalously metal rich fluids played a critical role in the formation of the giant Jinding sediment-hosted Pb-Zn deposit. We concur with the previous suggestion that sulfide precipitation at Jinding occurred when ascending metal-rich brines encountered an H2S-rich, Ca-rich fluid, which was produced by interaction of hydrocarbons with evaporites, in the cap of the Jinding dome.

Mineral resources are essential to prosperity and security of modern societies. How mineral resources can guarantee sustainable development of economy in countries, especially those developing countries, has long been a focus of attention of international communities. This paper provides a comprehensive summary for major advance of the research on mineral resources in past decades, and proposes some key issues regarding ore-forming mechanism, exploration and utilization of major and critical mineral resources. On the basis of these aspects, we also identify four priority science issues to be addressed in the future, including (1) mechanism of both metal circulation and extremely high concentration, (2) theories and technologies of prospecting deep-earth resources, (3) investigation of mineral resources in seafloor and polar regions, and (4) efficient, clean and recycling utilization of mineral resources. It can be expected that new advances in these four issues would tremendously promote the innovation of mineral resource science, and provide scientific and technologic support to meet the demand of mineral resources for human activities and the harmonious development of both mineral-resource exploration and ecological restoration.

Extremely thick Fe-Ti-V oxide layers are hosted in mafic-ultramafic intrusions of the Emeishan large igneous province (LIP) in the Pan-Xi district of southwest China, accounting for a quarter of the world’s Ti and V resource. It is unclear why these small intrusions contain such huge ore reserves that form world-class Fe-Ti-V oxide deposits. We find that the Hongge intrusion contains 35% Fe-Ti-V oxides, which is twice the typical content in mafic-ultramafic intrusions worldwide and the experimentally determined cotectic proportion in natural ferrobasaltic magma systems. The V content is almost constant in titanomagnetite across the entire Hongge intrusion in the Emeishan LIP, indicating a small (10–20%) proportion of cotectic Fe-Ti-V oxide during fractional crystallization. The bulk composition of the intrusion indicates an open magma system at the time of its formation. Clinopyroxene phenocrysts from overlying basalts contain Fe-Ti-V oxide inclusions, indicating that the phenocrysts crystallized at depth from magma saturated in Fe-Ti-V oxide and were then transported to the surface. We suggest that these intrusions were feeder conduits to the overlying basalts, where the silicates were cotectic with Fe-Ti-V oxides which were then extracted from the underlying intrusion as phenocrysts. Such a fundamental process is key to increase the proportion of oxide minerals in the residual assemblage, thereby upgrading the barren oxide-bearing rocks to world-class Fe-Ti-V oxide deposits in the small intrusions of the Emeishan LIP. A similar process might have occurred in LIPs elsewhere, meaning that intrusions formed as conduit-like open systems to the basalts in LIPs are good exploration targets for giant high-grade Fe-Ti-V oxide deposits.

The Luoboling Cu-Mo deposit, with 1.4 million tons (Mt) Cu and 0.11 Mt Mo, is the largest porphyry deposit in the Zijinshan district of southeast China. Mineralization at Luoboling is divided into premineralization, synmineralization, and late-mineralization stages. Consistent Cs/(Na + K) ratios in fluid inclusions suggest that the mineralizing fluids originated from a common source—the Luoboling granodiorite porphyry. The absence of initial supercritical fluid inclusions and abundant coexisting vapor and brine fluid inclusions imply that the fluids exsolved at low-pressure two-phase conditions, with temperatures of 250° to 600°C and salinities of 30 to 60 wt % NaCl equiv (brines) and

The Baiyangping Cu–Ag polymetallic ore district is located in the northern part of the Lanping-Simao foreland fold belt, between the Jinshajiang-Ailaoshan and Lancangjiang faults, and the deposit can be divided into eastern and western ore zones. Based upon microscope observation of ore minerals and analysis of zinc, copper, and strontium isotope composition, we conclude that: (1) the zinc isotopic compositions of sphalerite from the eastern and western ore belt of the Baiyangping polymetallic ore deposits are enriched in both the heavy (− 0.09‰ to + 0.15‰) and light (− 0.19‰ to − 0.01‰) zinc isotopes. Rayleigh fractionation is likely the additional factor controlling the observed temporal and spatial variations in zinc isotopes in the two studied ore zones. The zinc isotopic composition in the Baiyangping polymetallic Pb–Zn deposits may have the same fractionation as that of magmatic-hydrothermal, VHMS, SEDEX, and MVT deposits, as demonstrated by geological and other geochemical evidence; (2) the range of δ65Cu in massive tetrahedrite is from − 0.06‰ to + 0.12 ‰ that relates to the early stages of ore-formation, which are higher than that of venial chalcopyrite (from − 0.72‰ to − 0.07‰) formed at a late ore-forming stage in the western ore belt. Different ore-forming stages and alteration or leaching processes are likely the main factors controlling the observed variations in copper isotopes in the western ore zone; (3) the 87Sr/86Sr value of hydrothermal calcite in eastern (0.7080–0.7093) and western (0.7085–0.7113) ore belt suggested that mineralization of early calcite, with 87Sr/86Sr values much higher than in ancient Late Triassic seawater, may be related to recrystallization from a radiogenic Sr-rich or silicifying fluid, either from the strata that the ore-forming fluid flows through or from other fluids.

The reduced nature of the subducting slab has been used to explain the relatively poor endowment of economic porphyry copper deposits in Paleo-Tethyan arc systems. The presence of numerous porphyry Cu deposits in the southern Yidun terrane potentially challenges this model, because these deposits are thought to be the product of Paleo-Tethyan subduction. To investigate this, two representative deposits (i.e., Pulang and Songnuo porphyry Cu deposits) from the southern Yidun terrane have been studied. Zircon U-Pb ages of pre- and syn-mineral porphyries in Pulang are 221 ± 2 Ma (MSWD = 0.89) and 215 ± 2 Ma (MSWD = 1.50), respectively. Zircon and garnet U-Pb ages of the Songnuo syn-mineral porphyry are 217 ± 2 Ma (MSWD = 1.15) and 223 ± 5 Ma (MSWD = 0.97), respectively. The Pulang and Songnuo porphyries both have high whole-rock Sr/Y ratios with minor or no negative Eu anomalies, consistent with derivation from hydrous magmas that underwent minor early plagioclase crystallization but abundant amphibole fractionation. The two porphyry intrusions are characterized by high large-ion-lithophile elements (LILE: Th, U, Ba, Rb) abundances, and low concentrations of high-field-strength elements (HFSE: Nb, Ta, Ti, Zr, Hf). They have similar initial Sr isotope ratios from 0.7055 to 0.7073, ƐNd (t) values from − 4.3 to − 1.6 and zircon ƐHf (t) values of − 1.81 ± 1.34 (n = 47) that are distinct from published results for the Permian–Early Triassic Paleo-Tethyan arc granitoids in the Sanjiang region but similar to the Neoproterozoic arc intrusions in the nearby western Yangtze craton. The Pulang and Songnuo porphyries have relatively high zircon EuN/EuN* ratios (0.59 ± 0.04, n = 52) and calculated Δ log fO2 (FMQ) values (1.61 ± 0.23, n = 52), consistent with relatively oxidized magmas. This feature is similar to the published data for the Neoproterozoic arc intrusions (EuN/EuN* = 0.55 ± 0.08; Δ log fO2 (FMQ) = 2.14 ± 0.60), but distinct from the published data for the reduced normal Paleo-Tethyan arc magmas (EuN/EuN* = 0.29 ± 0.10; Δ log fO2 (FMQ) = − 0.68 ± 0.88). Given that the most recent tectonic reconstruction models suggest that the Paleo-Tethys Ocean closed before ~ 220 Ma, we propose that the Pulang and Songnuo porphyries Cu deposits were formed in a postsubduction setting from oxidized melts generated by reactivating the Neoproterozoic arc root, unrelated to Paleo-Tethyan subduction.

Most of the World’s large tungsten deposits are genetically related to fluorine-rich granitic magmas, their ores contain fluorine minerals, such as fluorite and topaz, and their host rocks have commonly undergone fluorine metasomatism to form greisens. In view of this evidence that tungsten ore fluids are enriched in fluorine, and the potential for fluoride to form stable complexes with hard acids (e.g., W6+), we investigated the solubility and speciation of tungsten in fluoride-bearing fluids at hydrothermal conditions. Experiments were conducted to measure the solubility of tungsten trioxide solid in fluoride-bearing aqueous fluids at temperatures between 100 and 250 °C and vapour-saturated water pressure. Based on the results of these experiments, tungsten is dissolved predominantly as H3WO4F2− in solutions containing 0.05–0.30 m HF at pH(T) values between 1.5 and 3.4. Significantly, the concentration of H3WO4F2− was up to two orders of magnitude higher than that of tungstate species in these experimental solutions. This species formed via the reaction WO3cryst + H2O + 2HF = H3WO4F2− + H+, logarithms of the equilibrium constants for which, vary from −4.39 ± 0.18 at 100 °C to −5.10 ± 0.17 at 250 °C. In solutions containing

A genetic link between Sb mineralization and magmatism has previously been proposed, yet little is known about the mobility of Sb during magma degassing. We have carried out a series of experiments to understand the effects of fluid composition, oxygen fugacity (fO2), pressure and temperature on the partitioning of Sb between magmatic fluids and a rhyolitic melt at crustal conditions (T = 850 °C, P = 200 MPa). The experiments were carried out in Molybdenum - Hafnium Carbide (MHC) pressure vessel assemblies at T = 850 to 1000 °C, P = 100 to 200 MPa and logfO2 from 1.64 log units below to 1.78 log units above the Ni-NiO buffer. Antimony partitions into aqueous chloride-bearing fluids weakly, with the fluid/silicate melt partition coefficient of Sb (DSbfluid/melt) increasing from 0.48 ± 0.11 (1σ) to only 0.85 ± 0.17 (1σ) as the total chlorine concentration in the fluid increases from 0.99 to 16.24 m, indicating the lack of significant Sb-chloride species in the fluid. In contrast, DSbfluid/melt increased from 0.89 ± 0.19 to 1.49 ± 0.19 as the aluminum saturation index (ASI) of the melt increased from 1.02 to 1.24. The moderate increase in DSbfluid/melt with increasing ASI of the melt (and HCl/metal chloride in the fluid) most likely relates to decreasing Sb solubility in the melt and further demonstrates the lack of significant chloride complexing of Sb. We also found that DSbfluid/melt is only slightly influenced by fO2 suggesting that Sb does not change oxidation state (Sb3+) at redox conditions typical of arc magmatism. Furthermore, the presence of reduced S species in the fluid phase caused only a minor increase in DSbfluid/melt indicating that Sb-sulfide complexes are not particularly stable in magmatic fluids. Our data also show that pressure and temperature, within the range of 100 to 200 MPa and 850 to 1000 °C, do not significantly influence DSbfluid/melt. Thus it is apparent that at most possible conditions at which rhyolitic melts degas in the upper crust, Sb will only weakly partition into the fluid phase and it is likely that the Sb budget of large epithermal Sb deposits is not directly derived from primary magmatic fluids.

The Yangtze Block is one of the major geological units in China. Numerous and diverse mineralization are extensively distributed in this block, making the Yangtze Block be one of the well-known providers of mineral-resources worldwide. In the southwestern Yangtze Block, since Proterozoic, the diverse mineralization involves magmatic, magmatic-hydrothermal, low-temperature hydrothermal and weathering-sedimentary processes were extensively developed, of which critical metal mineralization (e.g., In, Ge, Ga, Cd, Re, W, Sn, Li, Nb, REE, and PGE) is generally present as by-products in some basic or precious deposits or as independent deposits. Previous studies have revealed ten types of critical metal mineralization in the region, specifically including the REE-rich phosphorite, PGE-Re-rich black shales, carbonate clay-type Li-Ga-REE, basalt weathering-type Nb-Ga-Zr-REE, In-rich cassiterite sulfide, REE-rich IOCG, Tl-rich low-temperature hydrothermal, Ge-rich Pb-Zn, Cu-Ni-PGE sulfides and carbonatite-related REE deposits. In the past decade, numerous studies have advanced our understanding of the mineralization styles, timing and ore genesis of these types of critical-metal mineralization, and are summarized in this paper. It was indicated that the Cu-Ni-PGE sulfide deposits are genetically related to the late Permian E’meishan mantle plume, whereas the carbonatite-related REE deposits are Cenozoic in age and have formed during post-collision between the Indian and Asian continents. Moreover, the REE-rich IOCG deposits were newly identified, constituting a Proterozoic IOCG metallogenic province that was first documented in China, and enrichments of REEs were suggested to be related to the chemical attributes of the late Cu mineralizing fluids; the In-rich sulfide deposits, distributed in a small area of the SW Yangtze Block, were suggested to be genetically related to late Yanshanian granites; the low-temperature hydrothermal mineralization, characterized mainly by the Pb-Zn and Au-As-Sb-Hg-Tl deposits that define one of the two world-largest low-temperature metallogenic provinces, was mainly formed at the Indosinian and Yanshanian periods during which granitic activities are relatively weak; numerous marine-facies sedimentary rocks particularly including the black shales and carbonate rocks are associated with the development of multi-episodes of sedimentary and/or weathering-sedimentary deposits that are uniquely enriched in Li, Nb, Zr, Ga. Re, REE and PGE. We also proposed some issues that are important but currently poorly addressed, including aspects of the evaluation of REE resource potential and mechanisms of REE concentrations in IOCG deposits, and key factors controlling the extreme enrichment of Ge, Ga, Cd and Tl in the Mesozoic low-temperature metallogenic province, with focuses on the background values of these elements in the region. Moreover, available studies show that In is extremely enriched in four giant cassiterite-rich, granite-related sulfide deposits distributed in the border area of Yunnan and Guangxi, making this area a unique In metallogenic province in the world. However, it is currently not clear why In is enriched in cassiterite-rich sulfide deposits and why In is enriched in the sphalerite as a function of “indium window” effect, which should be constrained through a combined study involving crust-mantle circulation, crystallization fractionation of magma, geochemical behaviors of metals and mineralogy. We also proposed that the weathering-sedimentary deposits, such as the clay-type Li-Ga-REE and basalt weathering-type Nb-Ga-Zr-REE ones, are likely brand-new types with huge potential of critical metal resources, and emphasized that in addition to ore genesis studies, researches on the distributions of metals and potential utilization of resources should also be paid more attention. We also highlight that current prospecting techniques and methods that are mostly used for exploration of some common basic or precious deposits are likely not applicable for the exploration of critical metal deposits. As such, new techniques and methods involving the integration of prospecting information, predication and locating of ore bodies and evaluation of resources should also be developed for critical metal deposits.

The relationship between plate tectonics and the reworking of continental crust remains controversial. Multistage, hornblende-free, S-type granites across the Malay Peninsula Sn belt are ideal for investigating this research question. Here we present zircon U-Pb ages, in-situ apatite Nd and zircon Hf isotope data, and whole-rock major and trace element data for these S-type granites and spatially associated dykes. Four generations of Permian–Triassic (276–272, 262–260, 231–222, and 202 Ma) S-type granites were identified. The different S-type granites show distinct in-situ zircon Hf and apatite Nd isotopic compositions, implying generation from different sedimentary protoliths. Input of mantle-derived components for the formation of all these S-type granites, further indicating that both continental crustal reworking and growth occurred in the Malay Peninsula during the Permian–Triassic. A 250 Ma dolerite dyke in the Eastern Province was derived from an E-MORB-like mantle source. However, a 202 Ma monzonite dyke in the Western Province, was derived from mafic magmas produced by the melting of enriched mantle, followed by subsequent incorporation of crustal materials. All these S-type granitic magmas were reduced that inherited from sedimentary protoliths, which were favourable for Sn mineralization. Apatite F-Cl concentrations and F/Cl ratios in the S-type granites and related dykes changed systematically through time. We infer that the formation of these S-type granites and related dykes corresponds to the Palaeo-Tethyan evolution (i.e., early subduction of Palaeo-Tethyan oceanic lithosphere and subsequent collision between the Sibumasu and Indochina blocks). Our study also support that multistage S-type granites can be generated in distinct tectonic environments at different times in the same region.

It is widely considered that arc magmas are highly oxidized, and can thus dissolve a large amount of sulfur, thereby preventing significant sulfide saturation prior to fluid saturation. Therefore, chalcophile metals (e.g., Cu and Au) are retained in the magma and finally extracted by exsolved hydrothermal fluids. To test this hypothesis, we analyzed the abundances of platinum-group elements (PGEs) in a suite of arc volcanic rocks, which are the extrusive counterparts of magmas associated with the world-class Zijinshan porphyry–epithermal Cu–Au ore district in SE China. All of these volcanic rocks are depleted in PGEs (e.g., Pd = 0.02–0.40 ppb) in comparison with fertile arc magmas, and the PGE contents decrease with decreasing MgO from basalt to dacite. The results show that the parental magmas for these rocks reached sulfide saturation before they evolved to 7 wt.% MgO, which is earlier than the onset of magnetite crystallization. Sulfide liquid and monosulfide solid solution (MSS) were removed from the magma before it evolved into a dacitic composition. This process extracted most of the Au and Cu from the magma. Modeling results indicate that Au concentrations would not exceed 7–10 times the Pd concentrations in the residual silicate magma, irrespective of the partition coefficients between the sulfide and silicate melt. Given the low Pd contents in dacitic arc magmas worldwide, depletion of Au and Cu might be a common feature of highly evolved arc magmas. Thus, the hydrothermal ore fluids separated from such evolved arc magmas would not contain enough metals to form the giant Zijinshan porphyry–epithermal Cu–Au ore district. We propose a model in which the magmas parental to the arc volcanic rocks achieved S saturation, and thus large amounts of sulfides accumulated in the underlying magma chamber before the magmas were extruded from depth to the surface. During solidification of the magma chamber, these deposits formed from exsolved magmatic hydrothermal fluids that dissolved abundant pre-existing magmatic Cu–Au-rich sulfide assemblages. Release of large amounts of Au, Cu and S to the ore-forming aqueous fluids by dissolution of sulfides can account for the metal and S budgets of giant porphyry–epithermal Cu–Au deposits.

Permian-Triassic granites and associated tin deposits are widespread in the Eastern and Western belts of Peninsular Malaysia. The ages and key controlling factors of tin mineralization, however, are poorly constrained. Cassiterite separates from the Sintok and Rahman tin deposits in the Western belt, and Bandi, Setahum, Lembing, and Cherul tin deposits in the Eastern belt have U-Pb ages of 218.9 ± 3.4 and 226.8 ± 7.6 Ma, and 213.1 ± 3.9, 270.6 ± 4.6, 282.7 ± 4.6, and 281.3 ± 3.5 Ma, respectively. These ages directly constrain the tin mineralization in Peninsular Malaysia to two separate periods: 290 to 270 Ma and 230 to 210 Ma. Zircon crystals from tin-bearing granites in the Cherul and Sintok deposits have U-Pb ages of 276.0 ± 1.9 and 221.9 ± 0.6 Ma, respectively, consistent with the cassiterite U-Pb ages within uncertainties. Zircon crystals from barren granites of the Kuantan pluton in the Eastern belt have a U-Pb age of 260.5 ± 0.7 Ma, which is between the two tin mineralization periods. Zircon from these barren granites have εHf(t) values from −5.4 to 3.6, two-stage Hf model ages (TDM2) from 1.4 to 1.0 Ga, and Ce4+/Ce3+ ratios from 40 to 120. By comparison, zircon crystals from the tin-bearing granites have low εHf(t) values (−9.7 to −3.2) and Ce4+/Ce3+ ratios (4–67) and high TDM2 (1.8–1.4 Ga). Zircon ages, Hf isotopes, and trace elements indicate that the tin-bearing granitic magmas in Peninsular Malaysia had relatively low oxygen fugacity and were derived from reworking of Paleo- to Mesoproterozoic sedimentary rock-dominated crust in response to the Paleo-Tethyan subduction and continental collision. This study confirms that the nature of magma sources and redox states of magmas were key in the formation of the tin-rich granites and associated tin deposits and that the granite-related tin mineralization in Peninsular Malaysia was closely related to the evolution of the eastern Paleo-Tethys.

The solubility of molybdenum trioxide (MoO3(s)) in aqueous solutions has been investigated experimentally at 250°, 300°, and 350°C and saturated water vapor pressure, and total Na concentrations ranging from 0 to 3 molal (m). Results of these experiments show that the solubility of MoO3(s) increases with increasing temperature and at 350°C can reach several thousand parts per million at high salinity (>1 m NaCl). At low Na+ activity, MoO3(s) dissolves dominantly as HMoO4,− whereas at high Na+ activity, the dominant species is NaHMoO40. The two dissolution reactions are MoO3(s)+H2O=HMoO4−+H+(1) and MoO3(s)+H2O+Na+=NaHMoO40+H+.(2) The values of the logarithms of the equilibrium constants for reaction (1) are –5.20 ± 0.12, –5.31 ± 0.17, and –5.50 ± 0.09 at 250°, 300°, and 350°C, respectively, and for reaction (2) the values are –3.40 ± 0.11, –3.25 ± 0.19, and –2.97 ± 0.09 for the same temperatures. In combination, these equilibrium constants yield equilibrium constants for the reaction relating the two aqueous species: Na++HMoO4−=NaHMoO40.(3) The values of the logarithms of the equilibrium constants for reaction (3) are 1.80 ± 0.16, 2.06 ± 0.25, and 2.53 ± 0.13 at 250°, 300°, and 350°C, respectively. Calculations, based on the results of this study and thermodynamic data available for other species, suggest strongly that in ore-forming hydrothermal systems, molybdenum is transported mainly as NaHMoO40 and deposits as molybdenite in response to cooling and possibly a reduction in fO2.

To better understand processes leading to porphyry Mo deposit formation, the metal content, volatile content, and crystallization conditions of melt inclusions from pre- and synmineralization intrusions in six porphyry(-skarn) Mo deposits of northeastern China (Aolunhua, Hashitu, Lanjiagou, Songbei, Wanbaoyuan, and Yangjiazhangzi) were investigated by means of laser ablation-inductively coupled plasma-mass spectrometry and electron microprobe analysis. The ore-forming silicate melts were one to four times more evolved than average granite with 1 to 7 ppm Mo. The ore-related intrusions crystallized predominantly at 760° to 690°C and 3.7 to 1.0 kbar, except for the one at Hashitu, which crystallized at 770° to 740°C and lower pressures (2.0–1.0 kbar). Fertile silicate melts at Hashitu contain up to 0.4 wt % F, 0.03 to 0.09 wt % Cl, 5.0 to 7.0 wt % H2O, 10 to 24 ppm Cs, and 200 to 500 ppm Rb, whereas those at Yangjiazhangzi and Wanbaoyuan contain less Cs (3–6 ppm and 5–7 ppm, respectively), less Rb (180–220 ppm and 200–240 ppm, respectively), and negligible F (Comparison between syn- and premineralization intrusions in individual deposits reveals that the ore-related intrusions were similarly evolved and had similar Mo contents and crystallization conditions as the nonmineralizing intrusions. The only difference is that the premineralization intrusions tend to occur as batholiths. The key to porphyry Mo mineralization lies in the focusing of fluid into and through a small rock volume on the top of the intrusion.For the studied porphyry Mo deposits, the mineralizing magmas are all Mo poor, indicating Mo enrichment is not required to form porphyry Mo deposits. Metal endowments in porphyry Mo deposits have no direct relationship with the composition and crystallization condition of mineralizing melts but are linked with the fluid flux released from the underlying magma chamber through a cupola.

It has been well established that metal and sulfur sources in mineral deposits can be very difficult to identify, especially for ore deposits hosted in sedimentary rocks. Using the world’s largest Sb deposit at Xikuangshan in southern China as a case study, this study combined Hg isotopes and in situ sulfur isotope measurements to constrain the sources of Sb and sulfur. A variation of 1.1‰ in δ202Hg (0.04 to 1.15‰) was observed in stibnite ore samples, suggesting that mass-dependent fractionation of Hg isotopes occurred during the formation of the deposit. Significant mass-independent fractionation of Hg isotopes, with △199Hg ranging from − 0.03 to − 0.17‰, was also observed in the ore samples, suggesting that Hg transported by the ore fluids was inherited from Proterozoic basement metamorphic rocks as these rocks show similar △199Hg signatures (− 0.03 to 0.07‰). In situ sulfur isotope measurements yielded δ34S values that cluster in the range of + 6.8 to + 10.2‰, providing evidence that sulfur contained in ore fluids may also have been dominantly derived from underlying Proterozoic basement metamorphic rocks (δ34S = +5.6 to + 11.5‰). Using the new results from Hg and S isotopes, we proposed that deep-circulated meteoric water mobilized Sb, Hg, and S from the Proterozoic metamorphic basement, ascended along deep faults, and subsequently deposited Sb at favorable structural zones as a result of boiling of the hydrothermal fluids, generating the world-class Xikuangshan Sb deposit. This study also highlights the combined use of Hg-S isotopes as a novel method to provide new and additional insights into the source regions of ore materials for sedimentary-hosted Sb deposits.

The Shuiyindong Carlin-like gold deposit, the largest one of this type in China, is located in the Late Paleozoic–Early Mesozoic Youjiang basin. The pyrites in the studied ore bodies (No. I to V) can be divided into four main types plus several sub-types: (1) As-poor pyrites include Py1 (Py1a and Py1b), Py2, and Py3; and (2) As-rich pyrite Py4 (Py4a and Py4b). In situ LA-ICP-MS analyses show that the As-rich pyrite also contains higher Au, Cu, Sb, and Tl than the other pyrite types. In situ NanoSIMS analyses show the δ34S variation of Py1 (48.1~67.5‰), Py2 (2.4~7.6‰), Py3 (9.2~14.2‰), and Py4 (− 3.0~6.6‰), with the average values of 58.1‰, 5.1‰, 11.4‰, and 3.1‰, respectively. The large δ34S variations of As-poor pyrites may reflect a sedimentary source. However, the narrow ranges of δ34S values for the As-rich pyrite (Py4) may not reflect a sedimentary but a magmatic or metamorphic origin. A metamorphic sulfur source of Py4 is favored due to paucity of coeval magmatism in the region and decreasing variations of δ34S values from Py1 to Py4. Integrated transmission electron microscope (TEM) and NanoSIMS element mapping show that the distribution and concentration of Au are discordant with As and Cu at the submicron scale, also implied by the occurrence of some of Au as nano-submicron particles in Py4. Overall, our new data indicate that the ore fluids were not only enriched in Au but also in As, Cu, and S. Taking an alternative of fluid oxidation probably resulting in the decreasing δ34S values of Py4, our result of I to V orebodies indicates the mixing between the underlying metamorphic fluid and meteoric water. Integrated variations in δ34S and As-Au-Cu correlations across individual pyrite grains infer the physicochemical changes of aqueous and/or aqueous-carbonic fluids along migration paths.

The giant Yulong porphyry Cu Mo deposit was formed in postsubduction setting in eastern Tibet. Origin of the ore-related Yulong intrusion remains a matter of debate. This study presents new whole-rock major and trace element geochemistry, in-situ apatite Sr Nd and zircon Hf O isotopes, and mineralogical chemistry of the Yulong intrusion. Least-altered samples from the Yulong intrusion have high SiO2 (66.3–69.5 wt%) and Al2O3 (14.9–15.5 wt%) contents, high La/Yb (36.4–68.0) and Sr/Y (46.0–76.3) ratios, and low MgO (0.63–1.24 wt%) and Cr ( Nd isotopes show limited variations ((87Sr/86Sr)i = 0.7060–0.7068, eNd(t) = −4.8–0.2), which plot between Paleo-Tethys ocean-related arc magmas and the ancient crust in eastern Tibet. Zircon grains from this study and published studies have mostly positive yet variable eHf(t) values (−20.6 to +12.2) and young Hf model ages that overlap those of the Paleo-Tethys ocean-related arc magmas. The above Sr-Nd-Hf isotopes, together with the elevated zircon δ18O values (6.4 to 9.3‰) and arc-like trace element patterns, collectively suggest that the Yulong intrusion may have originated from partial melting of juvenile lower arc crust related to the subduction of the Paleo-Tethys ocean, with incorporation of a small amount of ancient crustal materials. Two generations of amphibole were recognized at Yulong. Their compositions are used to calculate crystallization depths, magmatic oxidation states, and water contents. The caculated results show that the early-stage euhedral high-Al (5.87–8.51 wt%) amphibole phenocrysts may have crystallized in the underlying magma chamber (7.1–12.5 km in depth), whereas the late-stage xenomorphic low-Al (3.47–4.87 wt%) amphibole grains may have crystallized in the porphyritic stock (4.0–5.6 km). Magmatic water contents decrease from early- (3.5–4.6 wt%) to late-stage (2.8–3.5 wt%) amphibole, which is interpreted to indicate fluid exsolution from the magma chamber during emplacement of the Yulong intrusion. Caculated oxidation states increase from early- (ΔNNO = 0.6–1.5) to late-stage (ΔNNO = 1.9–2.3) amphibole. Plagioclase phenocrysts show periodic or reverse core-to-rim zonation of An contents (range up to 25 mol%), which are coupled by FeO contents, probably suggesting magma recharge events. Collectively, we propose that the magma chamber beneath Yulong was recharged by a less evolved magma, and was saturated in fluids to produce intensive alteration and mineralization. The relatively high oxidation states allow the metals to be enriched in the evolving magma, and to be deposited in the hydrothermal alteration stage.

High-Mg andesitic rocks (HMAs) are commonly generated through slab-mantle interactions in arc settings. In this study, however, we report the high-Mg diorites in the Zibo and Laiwu areas of the eastern North China Craton (NCC), which were particularly produced during lithospheric thinning within an intracontinental setting. Some of the rocks generated large-scale Fe skarn deposits (e.g., the Zibo quartz monzonite and the Laiwu Kuangshan monzonite), whereas the others are ore-barren (e.g., the Zibo gabbroic diorite and the Laiwu Jinniushan and Jiaoyu monzodiorites), providing an excellent case to reveal how the non-arc HMAs were formed and the crucial factors controlling the Fe mineralization. All the rocks are characterized by high Mg# values (51–84) at andesitic compositions (52.5–65.0 wt%) and show arc-like geochemistry (e.g., enriched in LREEs and LILEs and depleted in HREEs and HFSEs), of which the strongly mineralized intrusions are more felsic with higher Mg# values (69–84) and stronger fractionation between LREEs and HREEs. Zircon U-Pb dating indicates that these rocks were emplaced at the early Cretaceous (130–132 Ma), coeval with the peak thinning of the lithosphere in the eastern NCC. All the rocks have transitional Sr-Nd-Pb isotopic compositions (0.704726

The Xikuangshan Sb deposit in central Hunan, South China is the largest Sb deposit in the world, which has supplied more than 50% of the world’s Sb and with total Sb metal reserves of about 2.5 Mt. However, the age of this deposit is still not well constrained due to a lack of suitable minerals for reliable radiometric dating, which hampered the generation of a generally accepted genetic model of mineralization. Since the fluid-inclusion data suggest that the temperature of ore-forming fluids in the Xikuangshan deposit is up to 360 °C, zircon (U-Th)/He thermochronometry with the closure temperature of 160–200 °C was chosen here to elucidate the age of Sb mineralization. Detrital zircons in the altered host rocks from the Xikuangshan deposit yielded two (U-Th)/He age populations of 156–117 and 97–86 Ma. The older age population (156–117 Ma), which is well in accordance with previous Sm-Nd dating on hydrothermal calcite (156–124 Ma), probably represents the timing of main-stage Sb mineralization in the Xikuangshan Sb deposit, while the younger zircon (U-Th)/He ages may result from partial loss of He in zircon caused by the distal effect of deep-seated intrusions beneath the deposit. This study demonstrates that the (U-Th)/He dating of zircon in altered host rocks can be viable for constraining the timing of low-temperature mineralization.

A common perception is that oxidized magma is critical for the formation of a porphyry Cu ± Mo ± Au ore deposit. We have used an ore-bearing pluton (Tongchang) and an ore-barren pluton (Shilicun) in the western rim of the South China block to test this idea and to determine other important controls on ore genesis. Zircon U Pb ages indicate that the Tongchang and Shilicun plutons were emplaced at 36.3 ± 0.2 Ma and 35.2 ± 0.4 Ma, respectively, broadly coinciding with strike-slip faulting in the region and continental collision that occurred ~300 km to the west. These two plutons are all characterized by significant light REE enrichments and pronounced negative Nb Ta anomalies, similar to the bulk crust. Apatite separates from these two plutons all have elevated initial 87Sr/86Sr (Tongchang, 0.70690 to 0.70796; Shilicun, 0.70703 to 0.70726) and negative eNd(t) (Tongchang, −6.2 to −7.3; Shilicun, −4.5 to −5.8). The mean eHf(t) and δ18O of zircon from these plutons are −1.4 and 6.8‰ for Tongchang, and −0.3 and 6.5‰ for Shilicun. The Sr-Nd-Hf isotope compositions are all within the ranges of the Neoproterozoic mafic arc lower crust in the region. Whole-rock U-Nb-Ta systematics indicate that the Tongchang and Shilicun plutons originated from an amphibole-bearing source and a garnet-bearing source, respectively, implying a shallower and more H2O-rich mafic source for the former than the latter. Quartz trace element data indicate that the Tongchang pluton was emplaced at a shallower depth than the Shilicun pluton. Zircon Ce4+/Ce3+ and whole-rock V/Sc ratios, and apatite SO3 and MnO contents indicate that the parental magmas of both plutons are as oxidized as those of some porphyry Cu deposits in northern Chile, but the parental magma of the Tongchang pluton is less oxidized than that of the Shilicun pluton. Apatite Cl-F-OH systematics and higher abundant hydrous silicate minerals such as amphibole and biotite in the Tongchang pluton than the Shilicun pluton indicate that the parental magma of the Tongchang pluton has higher Cl and H2O content than that of the Shilicun pluton. Our results show that oxidized magma is important but this alone cannot make a porphyry Cu ± Mo ± Au ore deposit. High contents of H2O-Cl in magma and shallow depth of emplacement are also important.

Carlin-style (sediment-hosted, “invisible” gold) and epithermal gold deposits are commonly enriched in mercury (Hg), but the source of this metal is not well-known. In the world, the association of...

The Yulong porphyry Cu-Mo ore district in eastern Tibet features a series of Eocene felsic porphyry intrusions, only one of which is intensively mineralized. In this study, zircon U-Pb ages, and major and trace element compositions of whole rock samples and in-situ accessory minerals (zircon, apatite and titanite) from these various intrusions were analyzed to determine the factors controlling Cu mineralization. New zircon U-Pb dating, together with published zircon U-Pb ages, suggest that these porphyry intrusions were emplaced over a relatively short period of time (43.9 ± 0.6 Ma to 40.9 ± 0.3 Ma), with the mineralized Yulong intrusion emplaced at a late stage of the magmatic activity (41.1 ± 0.3 Ma to 40.9 ± 0.3 Ma). These intrusions have indistinguishable whole-rock major and trace element compositions, but the mineralized Yulong intrusion has higher apatite and titanite La/Yb ratios (average apatite La/Yb = 115.1 ± 28.5, n = 52; average titanite La/Yb = 22.4 ± 4.9, n = 38) than the earlier subeconomic intrusions (average apatite La/Yb = 50.4 ± 12.3, n = 72; average titanite La/Yb = 12.4 ± 3.5, n = 58), suggesting more fractionation of amphibole from the magmas that sourced it. Additionally, a negative relationship between La/Yb and CeN/CeN* ratios in apatite and titanite are interpreted to reflect increasing oxidation states through magma evolution. Indistinguishable zircon EuN/EuN* values and apatite core SO3 contents from the mineralized (zircon EuN/EuN* = 0.69 ± 0.06, n = 25; apatite SO3 = 0.65 ± 0.24 wt%, n = 21) and subeconomic intrusions (zircon EuN/EuN* = 0.62 ± 0.05, n = 64; apatite SO3 = 0.61 ± 0.27 wt%, n = 15) suggest that the entire magmatic suite was relatively oxidized, hydrous and sulfur-rich, and was therefore fertile for ore-formation. However, apatite crystals from the mineralized Yulong intrusion have significantly lower Cl contents (0.08 ± 0.03 wt%, n = 72) and higher F/Cl ratios (47.80 ± 21.97, n = 72) than those from the subeconomic intrusions (Cl = 0.29 ± 0.29 wt%; F/Cl = 12.87 ± 5.16; n = 78). These data may reflect more extensive fluid exsolution from the parental magma chamber at the time of emplacement of the mineralizing Yulong magmas. Sudden and voluminous release of volatiles coeval with emplacement of the Yulong intrusion was triggered by an as yet unidentified process, but possibly including magmatic recharge.

The Sichuan–Yunnan–Guizhou metallogenic province of Southwest China contains more than 200 Mt of Pb–Zn ore in carbonate-hosted Pb–Zn deposits, representing ~ 27% of the total Pb and Zn resources of China. Sources of metals and pathways of ore-forming fluids were elucidated through a study of the Pb–Zn–S–Cd isotopic compositions of sphalerite from the Tianbaoshan, Fusheng, Maozu, Jinshachang, and Daliangzi carbonate-hosted Pb–Zn deposits. δ34S values indicate that S in the deposits is derived mainly from evaporites in Cambrian to Triassic sedimentary strata, sulfates coexisting with sulfides, and Meso–Neoproterozoic folded basement. δ66Zn values and Pb isotopic ratios indicate that these metals originate mainly from Sinian to lower Permian sedimentary rocks and Proterozoic basement. There is a trend towards isotopically heavier Cd and Zn compositions of sphalerite from Maozu to Daliangzi, Jinshachang, and Tianbaoshan, which are all hosted in the upper Sinian Dengying Formation. Previous studies showed that there would be a trend of enrichment in heavier Zn and Cd isotopes following the migration of fluids and precipitation of minerals. The above observations suggest that the ore-forming fluids of these deposits are probably derived from the same hydrothermal fluid system. The fluids most likely flowed through Maozu first, migrating along the Xiaojiang and Anninghe fault belts and their branch faults to Daliangzi, Jinshachang, and Tianbaoshan, respectively. Zn and Cd isotopes could be useful tools in tracing the pathways of ore-forming fluids in this district, and heavier Zn and Cd isotopic compositions could provide a geochemical fingerprint for detecting remote orebodies in large hydrothermal fluid systems.

Chemical weathering of silicate rocks controls the fluvial input of dissolved Ge and Si into the ocean, and has substantial influence on the global Ge and Si geochemical cycles. The heavier dissolved Ge isotope compositions in the rivers (relative to the bulk silicate earth) suggest preferential incorporation of light isotopes into secondary weathering products during rock weathering (Baronas et al., 2017a). In this paper, we present the Ge isotope and Ge/Si ratio variations in the solid weathering products (soil and saprolite) from a well-developed basalt weathering profile (>15 m thick, including soil, saprolite, semi-weathered rock and fresh basalt) on the tropical island of Hainan (South China). We discussed the elemental/isotopic fractionation mechanism and the possible influence of major oxide composition on Ge isotope fractionation during extreme weathering of basalts in tropical climate. The Ge content ([Ge] = 2.19–4.12 ppm, 2.93 ppm on average, n = 52) and Ge/Si ratios (5.55–13.7 μmol/mol, 7.42 μmol/mol on average, n = 52) of solid weathering products are distinctly higher than those of the fresh basalts (avg. [Ge] = 1.64 ppm, Ge/Si = 2.66 μmol/mol, n = 5). The δ74Ge values of solid weathering products range from −0.02 ± 0.10‰ (2σ) to 0.63 ± 0.10‰ (2σ), and exhibits complex stratigraphic variation across the weathering profile. There are no distinct correlations between the concentrations of Ge (or the Ge/Si ratio and δ74Ge values) and SiO2, Al2O3, Fe2O3 and MnO for most of the soil and saprolite samples. The distinct positive δ74Ge vs. Ge (or τGe value and Ge/Si ratio) correlations for most soil and saprolite samples indicate that the enrichment (or depletion) of Ge content, Ge isotopes and Ge/Si fractionation are controlled by a common sorption process of solid weathering products. The predicted opposite relationships between Ge/Si ratios and δ74Ge values for pore water and that for solid weathering products can be evidenced by the positive Ge/Si vs. δ74Ge correlation in the Wenchang basalt weathering profile and a negative one in the river water (Baronas et al., 2017a). Moreover, the estimated negative Δ74Gesolid-dissolved (1000 * Ln(α)) value (−1.38 ± 0.28‰ (2σ)) indicates that solid weathering products are a sink for light Ge isotopes, possibly balancing the isotopic budget with heavy Ge isotope compositions in global rivers and oceans.

The Huize Zn–Pb–Ag deposit in SW China has an ore reserve in excess of 5 Mt. with an ore grade of ≥25 wt% Zn + Pb and 46–100 g/t Ag. This deposit is hosted in Carboniferous dolostone and limestone. Sulfide mineralization is dominated by sphalerite, galena, and pyrite. Four types of pyrite (Py1 to Py4) are temporally and spatially related to mineralization distinguished on the basis of textural features and mineral associations. Pyrite 1 to 3 corresponds to the pyrite-sphalerite sub-stage, whereas Py4 corresponds to sphalerite-galena-pyrite sub-stage. Pyrite 1 shows zoned texture composed of an inclusion-rich core and an inclusion-free rim, whereas Py2, Py3, and Py4 show replacement relic or overgrowth textures. The zoned texture in Py1 was formed by multiple stages of ore fluids, whereas replacement relic texture in Py2 to Py4 was formed by replacement of pyrite by late Pb-Zn-rich fluids. Trace element variation in pyrite results from a combination of mineral inclusions, co-precipitating minerals, and various fluid compositions. Sphalerite, pyrite, and galena have δ34S values of 10.4–23.5‰, suggesting that sulfur was probably derived from the thermochemical reduction of marine sulfates. The Huize pyrite has Co and Ni concentrations (0.02–9.5 ppm and 0.08–143 ppm, respectively) and Co/Ni ratios (~0.01–2.63) similar to pyrite from sedimentary exhalative deposits, submarine hydrothermal vents, and sedimentary pyrite, which may be due to pyrite precipitation from low-temperature (

The Xihuashan tungsten ore deposit in the central Nanling region, South China is a vein-type hydrothermal deposit associated with the Late Jurassic granitoids that were previously thought to be the products of crustal anatexis alone. In this study, we use helium (He) and argon (Ar) isotopes of fluid inclusions entrapped in pyrite and arsenopyrite to determine the origin of the ore-forming fluids. The 3He/4He ratios of the crushed fluid inclusions vary from 0.15 to 1.16 Ra, with a mean of 0.72 Ra (Ra, the atmospheric 3He/4He ratio of 1.4 × 10−6), indicating the presence of mantle-derived noble gasses in the fluids. The amounts of the mantle-derived noble gasses are estimated to be between ∼2 and 17%. The 40Ar/36Ar ratios of the fluid inclusions vary from 306 to 1023, with an average of 440. These ratios are significantly higher than the average crustal value, indicating the presence of air-saturated water in the volatiles released from the mineral separates. The results from this study indicate that the associated, coeval granitoids, which is believed to provide the ore-forming fluids during magma evolution, are not the products of pure crustal melts. Mantle-derived volatiles and heat was also involved in the genesis of the host granite pluton.

The Laochang polymetallic deposit is located in the Sanjiang Tethyan metallogenic province of southwestern China. This deposit contains stratabound (and locally vein-type) Pb–Zn–Ag mineralization and underlying porphyry–skarn Mo mineralization. The stratabound Pb–Zn–Ag mineralization is characterized by massive sulfide ores composed mainly of pyrite, sphalerite, galena, and minor chalcopyrite, whereas the underlying porphyry–skarn Mo mineralization is characterized by quartz–sulfide veins comprising mainly pyrite, chalcopyrite, molybdenite, and minor sphalerite and galena. The age and origin of the stratabound Pb–Zn–Ag mineralization has long been debated, and its relationship to the porphyry–skarn Mo mineralization remains unknown. Integrated pyrite Re-Os isotope, sulfur isotope, and in situ trace element data are used here to constrain the age and origin of both types of mineralization and their genetic relationships. Pyrite related to porphyry–skarn Mo mineralization yields a Re-Os isochron age of 47.3 ± 4.8 Ma, which is consistent with a previous molybdenite Re-Os age of the quartz–sulfide ores and zircon U-Pb ages of the granite porphyry (~44–50 Ma). Pyrite from the stratabound Pb–Zn–Ag mineralization failed to yield a geologically meaningful age, but associated sphalerite and galena have a Re-Os isochron age of 308 ± 25 Ma (Liu et al., 2015), which is consistent with the Carboniferous age of the host basalts. Pyrite, sphalerite, galena, and chalcopyrite from the stratabound Pb–Zn–Ag mineralization have δ34S values (−2.1 to 0.5‰; average 0.48‰) indistinguishable from those of sulfides from the porphyry–skarn Mo mineralization (−4 to 1.9‰; average 0.52‰). Initial Os isotope ratios indicate a mainly crustal origin for both types of mineralization. The calculated (Se/S)fluid and Co/Ni values of pyrite from the stratabound Pb–Zn–Ag mineralization indicate a mixed sedimentary and hydrothermal origin, with a significant magmatic contribution. The identification of a magmatic component, Eocene sulfide mineralization, and phyllic and propylitization alteration in stratabound Pb–Zn–Ag ores indicates that the magmatic–hydrothermal component reflects the overprinting of Carboniferous volcanogenic massive sulfide mineralization by magmatic–hydrothermal fluids derived from an Eocene granite porphyry.

To characterize the integrated magmatic processes for magma plumbing systems from mantle sources to magma chambers, we present Mg–Sr–Nd isotopic data for a representative mafic–ultramafic intrusion in Xiarihamu, northern Tibetan Plateau, China. The intrusion hosts the largest magmatic Ni–Cu sulfide deposit in an orogenic setting in the world and is composed predominantly of harzburgite, orthopyroxenite, websterite, and gabbronorite. The cumulate harzburgites have relatively low δ26Mg of orthopyroxene (–0·49 to –0·34‰) and moderately high (87Sr/86Sr)i and positive εNd(t) values (0·7067–0·7080 and +0·4 to +1·8, respectively). Most of the orthopyroxenites, websterites, and gabbronorites have slightly higher δ26Mg of orthopyroxene (–0·34 to –0·21‰) and higher (87Sr/86Sr)i and lower εNd(t) values (0·7087–0·7118 and –4·0 to –1·4, respectively) than the harzburgites. On the other hand, marginal facies (i.e. a few centimeters to meters from the contact between the intrusion and country rocks of schist, gneiss, and marble) including websterite and gabbronorite are marked by low δ26Mg of orthopyroxene (–0·44 to –0·33‰) and extremely high (87Sr/86Sr)i and negative εNd(t) values (0·7127–0·7172 and –5·4 to –4·8, respectively). The relatively low δ26Mg, moderately high (87Sr/86Sr)i, and positive εNd(t) of the harzburgites are best interpreted by inheritance from the mantle source, which was previously metasomatized by subducted Mg-rich carbonates. Given the fact that the solidus of carbonated mantle is significantly lower than that of volatile-free mantle, mantle metasomatism by carbonates may be critical to generate voluminous mafic magmas and to form the giant Xiarihamu Ni–Cu deposit and other magmatic sulfide deposits in convergent settings worldwide. The relatively high δ26Mg, high (87Sr/86Sr)i, and low εNd(t) of most orthopyroxenites, websterites, and gabbronorites were produced by extensive contamination of isotopically heavy crustal rocks in a deep-seated magma chamber. The slightly low δ26Mg, extremely high (87Sr/86Sr)i and negative εNd(t) of the marginal facies, compared with other websterites and gabbronorites, were governed by assimilation of local low-δ26Mg country rocks (e.g. gneiss and marble) at the Xiarihamu magma chamber during emplacement. These observations indicate that mafic–ultramafic cumulates away from marginal facies can preserve their primitive Mg–Sr–Nd isotope signatures inherited from deep magma chambers, even from mantle sources, with negligible crustal contamination during magma ascent and emplacement. These findings for the first time, to our knowledge, provide observational evidence to characterize the integrated magmatic processes of a single magma plumbing system from deep mantle source to magma chambers, which sheds light on the petrogenesis and mineralization of mafic–ultramafic intrusions.