Rutile and Chlorite Geochemistry Constraints on the Formation of the Tuwu Porphyry Cu Deposit, Eastern Tianshan and Its Exploration Significance

The chemical composition of rutile has been used as an indicator in magmatic and metamorphic-related diagenetic systems, but rarely in porphyry-style ore systems. The Tuwu deposit (557 Mt at 0.58% Cu) is a large porphyry-style Cu mineralization in Eastern Tianshan, Xinjiang, with typical disseminated, stockwork mineralized veins hosted in tonalite and diorite porphyry, and to a lesser extent in volcanic rocks of the Qi’eshan Group. We first present determination of rutile minerals coupled with chlorite identified in mineralized porphyries from Tuwu to reveal their geochemical features, thus providing new insights into the ore-forming processes and metal exploration. Petrographic and BSE observations show that the rutile generally occurs as large crystals (30 to 80 µm), in association with hydrothermal quartz, chlorite, pyrite, and chalcopyrite. The rutile grains display V, Fe, and Sn enrichment and flat LREE-MREE patterns, indicating a hydrothermal origin. Titanium in rutile (TiO2) is suggested to be sourced from the breakdown and re-equilibration of primary magmatic biotite and Ti-magnetite, and substituted by Sn4+, high field strength elements (HFSE; e.g., Zr4+ and Hf4+), and minor Mo4+ under hydrothermal conditions. The extremely low Mo values (average 30 ppm) in rutile may be due to rutile formation postdating that of Mo sulfides (MoS2) formation in hydrothermal fluids. Chlorite analyses imply that the ore-forming fluids of the main stage were weakly oxidized (logfO2 = −28.5 to −22.1) and of intermediate temperatures (308 to 372 °C), consistent with previous fluid inclusion studies. In addition, Zr-in-rutile geothermometer yields overestimated temperatures (>430 °C) as excess Zr is incorporated into rutile, which is likely caused by fast crystal growth or post crystallization modification by F-Cl-bearing fluid. Thus, application of this geothermometer to magmatic-hydrothermal ore systems is questionable. Based on the comparison of rutile characteristics of porphyry Cu with other types of ore deposits and barren rocks, we suggest that porphyry Cu-related rutile typically has larger grain size, is enriched in V (average 3408 ppm, compared to <1500 ppm of barren rocks) and to a lesser extent in W and Sn (average 121 and 196 ppm, respectively), and has elevated Cr + V/Nb + Ta ratios. These distinctive signatures can be used as critical indicators of porphyry-style Cu mineralization and may serve as a valuable tool in mineral exploration.

Generation of the Giant Porphyry Cu-Au Deposit by Repeated Recharge of Mafic Magmas at Pulang in Eastern Tibet

The giant Pulang porphyry Cu-Au district (446.8 Mt at 0.52% Cu and 0.18 g/t Au) is located in the Yidun arc, eastern Tibet. The district is hosted in an intrusive complex comprising, in order of emplacement, premineralization fine-grained quartz diorite and coarse-grained quartz diorite, intermineralization quartz monzonite, and late-mineralization diorite porphyry, which were all emplaced at ca. 216 ± 2 Ma. Mafic magmatic enclaves are found in both the coarse-grained quartz diorite and quartz monzonite. The well-preserved primary mineral crystals in such a systematic magma series (including contemporaneous relatively mafic intrusions) with well-defined timing provide an excellent opportunity to investigate upper crustal magma reservoir processes, particularly to test the role of mafic magma recharge in porphyry Cu formation. Two groups of amphibole crystals, with different aluminum contents, are observed in these four rocks. Low-Al amphibole crystals (Аl2О3 = 6.2–7.6 wt %) with crystallization temperatures of ~780°C mainly occur in the coarse-grained quartz diorite and quartz monzonite, whereas high-Al amphibole crystals (Al2O3 = 8.0–13.3 wt %) with crystallization temperatures of ~900°C mainly occur in the fine-grained quartz diorite and diorite porphyry. These characteristics, together with detailed petrographic observations and mineral chemistry studies, indicate that the coarse-grained quartz diorite and quartz monzonite probably formed by crystal fractionation in the same felsic magma reservoir, whereas the fine-grained quartz diorite and diorite porphyry formed from relatively mafic magmas sourced from different magma reservoirs. The occurrence of mafic magmatic enclaves, disequilibrium phenocryst textures, and cumulate clots indicates that the coarse-grained quartz diorite and quartz monzonite evolved in an open crustal magma storage system through a combination of crystal fractionation and repeated mafic magma recharge. Mixing with incoming batches of hotter mafic magma is indicated by the appearance of abundant microtextures, such as reverse zoning (Na andesine core with Ca-rich andesine or labradorite rim overgrowth), sharp zoning (Ca-rich andesine or labradorite core with abrupt rimward anorthite decrease) and patchy core (Ca-rich andesine or labradorite and Na andesine patches) textured plagioclase, zoned amphibole, high-Al amphibole clots, skeletal biotite, and quartz ocelli (mantled quartz xenocrysts). Using available partitioning models for apatite crystals from the coarse-grained quartz diorite, quartz monzonite, and diorite porphyry, we estimated absolute magmatic S contents to be 20–100, 25–130, and &gt;650 ppm, respectively. Estimates of absolute magmatic Cl contents for these three rocks are 1,000 ± 600, 1,800 ± 1,100, and 1,300 ± 1,000 ppm, respectively. The slight increase in both magmatic S and Cl contents from the premineralization coarse-grained quartz diorite magma to intermineralization quartz monzonite magma was probably due to repeated recharge of the relatively mafic diorite porphyry magma with higher S but similar Cl contents. Mass balance constraints on Cu, S, and Cl were used to estimate the minimum volume of magma required to form the Pulang porphyry Cu-Au deposit. Magma volume calculated using Cu mass balance constraints implies that a minimum of 21–36 km3 (median of 27 km3) of magma was required to provide the total of 2.3 Mt of Cu at Pulang. This magma volume can explain the Cl endowment of the deposit but is unlikely to supply the sulfur required. Recharge of 5–11 km3 of diorite porphyry magma to the felsic magma reservoir is adequate to account for the additional 6.5–15 Mt of S required at Pulang. Repeated diorite porphyry magma recharge may have supplied significant amounts of S and some Cl and rejuvenated the porphyry system, thus aiding formation of the large, long-lived magma reservoir that produced the porphyry Cu-Au deposit at Pulang.

Geochemistry of Tourmaline from the Laodou Gold Deposit in the West Qinling Orogen, Central China: Implications for the Ore-Forming Process

The Laodou gold deposit, located in the West Qinling Orogen of central China, is a newly recognized intrusion-related gold deposit. It consists of auriferous quartz-sulfide-tourmaline and minor quartz-stibnite veins that are structurally controlled by fault zones transecting the host quartz diorite porphyry. Two types of tourmaline were identified in this study: Type 1 tourmaline occurs as quartz-tourmaline nodules within the quartz diorite porphyry, whereas type 2 tourmaline occurs as quartz-sulfide-tourmaline veins in auriferous lodes. Here, we present a major and trace element analysis by electron microprobe and laser ablation inductively coupled plasma mass spectrometry on these two types of tourmaline. Both tourmaline types fall into the alkali group, and are classified under the schorl-dravite solid solution series. The substitutions of FeMg–1, FeAl–1, AlO((Fe, Mg)(OH)) –1, and X-site vacancyCa–1 are inferred by the variations of their major element compositions. Field and mineralogy observations suggest that type 1 tourmaline is a product of the late crystallization process of the quartz diorite porphyry, whereas type 2 tourmaline coexists with Au-bearing arsenopyrite and is crystallized from the ore-forming fluids. Their rare earth element compositions record the related magmatic hydrothermal evolution. The Co and Ni concentrations of the coexisting type 2 tourmaline and arsenopyrite define a regression line (correlation coefficient = 0.93) with an angular coefficient of 0.66, which represents the Co/Ni ratio of the tourmaline and arsenopyrite-precipitating fluids. This value is close to the Co/Ni ratios of the host quartz diorite porphyry, indicating a magma origin of the ore-forming fluids. The substitution of Al3+ by Fe3+ in both tourmaline types shows that type 1 tourmaline approaches the end member of povondraite whereas type 2 tourmaline occurs in opposite plots near the end member of Oxy-dravite, reflecting a more oxidizing environment for type 2 tourmaline formation. Moreover, the redox-sensitive V and Cr values of type 2 tourmaline are commonly 1–2 orders of magnitude higher than those of type 1 tourmaline, which also suggests that type 2 tourmaline forms from more oxidizing fluids. Combined with gold occurrence and fluid properties, we propose that the increasing of oxygen fugacity in the ore-forming fluids is a trigger of gold precipitation.

Mineralization Age and Hydrothermal Evolution of the Fukeshan Cu (Mo) Deposit in the Northern Great Xing’an Range, Northeast China: Evidence from Fluid Inclusions, H–O–S–Pb Isotopes, and Re–Os Geochronology

The Fukeshan Cu (Mo) deposit is a newfound porphyry deposit in the northern Great Xing’an Range (GXR), northeast China. In this paper, we present results of chalcopyrite Re–Os geochronology, microthermometry of the fluid inclusions (FIs), and isotopic (H–O–S–Pb) compositions of the Fukeshan Cu (Mo) deposit. Its ore-forming process can be divided into sulfide-barren quartz veins (A vein; stage I), quartz + chalcopyrite + pyrite veins (B vein; stage II), quartz + polymetallic sulfide veins (D vein; stage III), and barren quartz + carbonate ± pyrite veins (E vein; stage IV), with Cu mineralization mainly occurred in stage II. Three types of FIs are identified in this deposit: liquid-rich two-phase (L-type) FIs, vapor-rich two-phase (V-type) FIs, daughter mineral-bearing three-phase (S-type) FIs. The homogenization temperatures of primary FIs hosted in quartz of stages I–IV are 381–494 °C, 282–398 °C, 233–340 °C, and 144–239 °C, with salinities of 7.2–58.6, 4.8–9.9, 1.4–7.9, and 0.9–3.9 wt. % NaCl equivalent, respectively. FIs microthermometry and H–O isotope data suggest that the ore-forming fluids were magmatic in origin and were gradually mixed with meteoric water from stages II to IV. Sulfur and lead isotope results indicate that the ore-forming materials of the Fukeshan Cu (Mo) deposit were likely to have originated from Late Jurassic intrusive rocks. The available data suggest that fluid cooling and incursions of meteoric water into the magmatic fluids were two important factors for Cu precipitation in the Fukeshan Cu (Mo) deposit. Chalcopyrite Re–Os dating yielded an isochron age of 144.7 ± 5.4 Ma, which is similar to the zircon U–Pb age of the quartz diorite porphyry, indicating that Late Jurassic quartz diorite porphyry and Cu mineralization occurred contemporaneously.

Geochronology, geochemistry, and Pb–Hf isotopes of mineralization-related magmatism in the Dongyang gold deposit, Fujian Province, southeastern China

The recently discovered Dongyang low-sulphidation epithermal Au deposit is located in Fujian Province. The Au mineralization hosted in rhyolite porphyry and the Lower Jurassic Nayuan Formation continental volcanic rocks is considered to be related to intermediate–acidic intrusions (rhyolite porphyry, quartz diorite porphyry, and dacite porphyry). The zircon U–Pb ages of these samples are 160.3 ± 0.8, 156.6 ± 0.8, and 154.1 ± 0.6 Ma, respectively, and the sulphide Rb–Sr isotope isochron age is 152.4 ± 1.7 Ma, indicating a temporal link between porphyry emplacement and Au mineralization. Porphyries are enriched in large-ion lithophile elements and light rare earth elements and slightly depleted in heavy rare earth elements and high field strength elements, belong to the high-potassium calc-alkaline or shoshonitic series, and show characteristics of volcanic arcs or active continental margins. Moreover, the εHf(t) values of the porphyries range from −11.6 to −7.6, −11.2 to −5.4, and −9.8 to −4.6, respectively. The 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb values of the ore minerals are from 38.417 to 38.406, 15.603, and from 18.179 to 18.175, respectively. Pb and Hf isotopes indicate that the intermediate–acidic magma related to mineralization originated from Mesoproterozoic lower crust. Consequently, these data favour an intermediate–acidic magma origin for Au mineralization in the Dongyang deposit. Integrating new and published data on the tectonic evolution, we suggest that the rhyolite porphyry, quartz diorite porphyry, dacite porphyry, and associated Au mineralization in the Dongyang deposit formed at 160–152 Ma in an extensional environment related to subduction of the Palaeo-Pacific Plate beneath the South China block.

A genetic link between iron oxide-apatite and iron skarn mineralization in the Jinniu volcanic basin, Daye district, eastern China: Evidence from magnetite geochemistry and multi-mineral U-Pb geochronology

Various styles of ore deposits may form from a single magmatic-hydrothermal system. Identification of a possible genetic link between different ore types in a region is not only of critical importance for a better understanding of the magmatic-hydrothermal processes, but can also help in successful mineral exploration. Both iron oxide-apatite (IOA) and iron skarn deposits are closely associated with intrusive rocks of intermediate to felsic in composition, but whether these two ore types can form from the same magmatic intrusion remains poorly understood. In this study, we present a comparative study between a newly identified subsurface IOA ore body located at the apex of a diorite porphyry and the iron skarn ore bodies located immediately above it in the Jinniu volcanic basin of the Daye district, Middle-Lower Yangtze River metallogenetic belt (MLYRMB), eastern China in order to highlight a genetic link between these two styles of mineralization. The IOA ores are dominated by Ti-rich magnetite with variable amounts of fluorapatite, diopside, and actinolite. This mineralogical assemblage is distinctly different from the iron skarn ores, which consist mainly of Ti-depleted magnetite and subordinate pre-ore garnet and diopside, and post-ore quartz, chlorite, calcite, and pyrite. In addition, magnetite from the IOA ores is characterized by well-developed ilmenite lamellae and has high concentrations of Ni, V, Co, and Ga, consistent with high temperature crystallization, whereas magnetite grains from the iron skarn ores usually exhibit oscillatory growth zones and contain much lower Ni, V, Co, and Ga, indicating their formation under relatively low temperatures. Titanite and fluorapatite from the IOA ores have U-Pb ages of 132.5 ± 2.4 Ma to 128.4 ± 3.0 Ma, which match a titanite U-Pb age for the associated iron skarn ores (132.3 ± 2.0 Ma), and are consistent with zircon U-Pb ages for the ore-hosting diorite porphyry (130.4 ± 0.7 Ma to 130.3 ± 0.5 Ma). This age consistency supports a possible genetic link among the diorite porphyry, IOA ores, and iron skarn ores. We propose that the IOA and skarn ores are the products of two consecutive mineralization stages of the same magmatic-hydrothermal system, involving a high-temperature, hypersaline fluid coexisting with the diorite porphyry magma during emplacement and a subsequent low temperature, diluted hydrothermal fluid. Other IOA and iron skarn deposits of similar ages (130 Ma) are found in a series of volcanic basins in the MLYRMB, which forms one of the world’s largest IOA metallogenic belts. The close association of the two ore styles identified at Daye provides a useful exploration guide for IOA and iron skarn deposits both on a local and regional scale.