Molybdenite Re–Os and albite 40Ar/39Ar dating of Cu–Au–Mo and magnetite porphyry systems in the Yangtze River valley and metallogenic implications

The area of the Middle–Lower Yangtze River valley, Eastern China, extending from Wuhan (Hubei province) to western Zhenjiang (Jiangsu province), hosts an important belt of Cu–Au–Mo and Fe deposits. There are two styles of mineralization, i.e., skarn/porphyry/stratabound Cu–Au–Mo–(Fe) deposits and magnetite porphyry deposits in several NNE-trending Cretaceous fault-bound volcanic basins. The origin of both deposit systems is much debated. We dated 11 molybdenite samples from five skarn/porphyry Cu–Au–Mo deposits and 5 molybdenite samples from the Datuanshan stratabound Cu–Au–Mo deposit by ICP-MS Re–Os isotope analysis. Nine samples from the same set were additionally analyzed by NTIMS on Re–Os. Results from the two methods are almost identical. The Re–Os model ages of 16 molybdenite samples range from 134.7 ± 2.3 to 143.7 ± 1.6 Ma (2σ). The model ages of the five samples from the Datuanshan stratabound deposit vary from 138.0 ± 3.2 to 140.8 ± 2.0 Ma, with a mean of 139.3 ± 2.6 Ma; their isochron age is 139.1 ± 2.7 Ma with an initial Os ratio of 0.7 ± 8.1 (MSWD = 0.29). These data indicate that the porphyry/skarn systems and the stratabound deposits have the same age and suggest an origin within the same metallogenic system. Albite ⁴⁰Ar/³⁹Ar dating of the magnetite porphyry deposits indicates that they formed at 123 to 125 Ma, i.e., 10–20 Ma later. Both mineralization styles characterize transitional geodynamic regimes, i.e., the period around 140 Ma when the main NS-trending compressional regime changed to an EW-trending lithospheric extensional regime, and the period of 125–115 Ma of dramatic EW-trending lithospheric extension.     

Late Cretaceous metallogeny in the Zhongdian area: Constraints from Re–Os dating of molybdenite and pyrrhotite from the Hongshan Cu deposit,Yunnan, China

The Zhongdian area in Yunnan, southwestern China, located at the southern end of the Yidun volcano-magmatic arc that was formed during the Triassic westward subduction of the Gaze-Litang Ocean, hosts numerous Triassic large porphyry and skarn deposits. The arc suffered Jurassic to Cretaceous arc-continental orogenic collision and Cenozoic intracontinental strike-slip shearing. The Hongshan Cu (–Mo–Pb–Zn) deposit is potentially a large deposit and contains two ore types: 1) predominant layered skarn Cu–(Pb–Zn) ores along marble-hornfels contacts; and 2) minor crosscutting vein-type Cu–Mo mineralization. Previous research forwards a two-stage genetic model without sufficient dating evidence, supposing the skarn mineralization is related to the Triassic calc-alkalic intrusions and the vein-type mineralization related to Cretaceous quartz monzonite porphyries. Re–Os dating of molybdenite from vein-type ores and quartz monzonite porphyries and that of pyrrhotite from skarn ores are presented here to constrain the mineralization age and rebuild the genetic model. Analyses of eight molybdenite samples yield an isochron age of 79.7 ± 3.1 Ma (MSWD = 9.2) for the vein-type mineralization and a model age of 81.9 ± 1.1 Ma for the quartz monzonite porphyries. Isotope data on seven pyrrhotite samples from the skarn ores yield an isochron age of 79 ± 16 Ma z(MSWD = 8.4). The Re–Os ages for the two ore types are concordant within analytical errors, indicating that the Hongshan deposit was formed in the Late Cretaceous. Elevated Re contents in molybdenite (13.65 to 63.91 μg/g) and extremely radiogenic initial ¹⁸⁷Os/¹⁸⁸Os ratios in pyrrhotite (0.7673 to 0.8184; weighted average 0.796 ± 0.038), together with elevated γ_Os values in pyrrhotite (507 to 547; average 528) imply a significant crustal component in the ore-forming materials that was likely derived from a lower crustal reservoir. Combined with the tectonic evolution of the Zhongdian area and geochemical characteristics of corresponding intrusions, the ages of mineralization obtained in this study indicate that the Hongshan deposit was formed in a post-collision setting with a genetic relationship to the emplacement of the quartz monzonite porphyry. These results provide significant new information for the study and exploration of the Late Cretaceous metallogeny in the Zhongdian area.     

The post-collisional Cihai iron skarn deposit,eastern Tianshan,Xinjiang, China

The Cihai iron skarn deposit is located in the southern part of the eastern Tianshan, Xinjiang, northwestern China. The major iron orebodies are banded and nearly parallel to each other. The iron ores are hosted in an early diabase dike and in skarn. Post-ore diabase dikes cut the iron ores and their hosting diabase. Hydrothermal activity can be divided into four stages based on geological and petrographic observations: initial K–Na alteration (stage I), skarn-minor magnetite event (II), retrograde skarn-magnetite main ore event (III), and quartz–calcite–sulfide veining (IV). Zircon U–Pb dating yields ages of 286.5 ± 1.8 Ma for early diabase and 275.8 ± 2.2 Ma for post-ore diabase dikes. Amphibole separated from massive magnetite ore gives a ⁴⁰Ar–³⁹Ar plateau age of 281.9 ± 2.2 Ma and is the time of ore formation. Formation of the Cihai iron deposit is closely related to post-collisional magmatism and associated Cu–Ni–Au polymetallic mineralization in the eastern Tianshan.     

In-situ LA-ICPMS trace elements and U–Pb analysis of titanite from the Mesozoic Ruanjiawan W–Cu–Mo skarn deposit,Daye district,China

In this paper, we present U–Pb ages and trace element compositions of titanite from the Ruanjiawan W–Cu–Mo skarn deposit in the Daye district, eastern China to constrain the magmatic and hydrothermal history in this deposit and provide a better understanding of the U–Pb geochronology and trace element geochemistry of titanite that have been subjected to post-crystallization hydrothermal alteration. Titanite from the mineralized skarn, the ore-related quartz diorite stock, and a diabase dike intruding this stock were analyzed using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Titanite grains from the quartz diorite and diabase dike typically coexist with hydrothermal minerals such as epidote, sericite, chlorite, pyrite, and calcite, and display irregular or patchy zoning. These grains have low LREE/HREE and high Th/U and Lu/Hf ratios, coupled with negative Eu and positive Ce anomalies. The textural and compositional data indicate that titanite from the quartz diorite has been overprinted by hydrothermal fluids after being crystallized from magmas. Titanite grains from the mineralized skarn are texturally equilibrated with retrograde skarn minerals including actinolite, quartz, calcite, and epidote, demonstrating that these grains were formed directly from hydrothermal fluids responsible for the mineralization. Compared to the varieties from the quartz diorite stock and diabase dike, titanite grains from the mineralized skarn have much lower REE contents and LREE/HREE, Th/U, and Lu/Hf ratios. They have a weighted mean ²⁰⁶Pb/²³⁸U age of 142 ± 2 Ma (MSWD = 0.7, 2σ), in agreement with a zircon U–Pb age of 144 ± 1 Ma (MSWD = 0.3, 2σ) of the quartz diorite and thus interpreted as formation age of the Ruanjiawan W–Cu–Mo deposit. Titanite grains from the ore-related quartz diorite have a concordant U–Pb age of 132 ± 2 Ma (MSWD = 0.5, 2σ), which is 10–12 Ma younger than the zircon U–Pb age of the same sample and thus interpreted as the time of a hydrothermal overprint after their crystallization. This hydrothermal overprint was most likely related to the emplacement of the diabase dike that has a zircon U–Pb age of 133 ± 1 Ma and a titanite U–Pb age of 131 ± 2 Ma. The geochronological results thus reveal two hydrothermal events in the Ruanjiawan deposit: an early one forming the Wu–Cu–Mo ores related to the emplacement of the quartz diorite stock and a later one causing alteration of the quartz diorite and its titanite due to emplacement of diabase dike. It is suggested that titanite is much more susceptible to hydrothermal alteration than zircon. Results from this study also highlight the utilization of trace element compositions in discriminating titanite of magmatic and hydrothermal origins, facilitating a more reasonable interpretation of the titanite U–Pb ages.     

Geochronology,geochemistry, and mineralization of the granodiorite porphyry hosting the Matou Cu–Mo (±W) deposit,Lower Yangtze River metallogenic belt,eastern China

Porphyry and skarn Cu–Fe–Au–Mo deposits are widespread in the Middle and Lower Yangtze River metallogenic belt (MLYMB), eastern China. The Matou deposit has long been regarded as a typical Cu–Mo porphyry deposit within Lower Yangtze part of the belt. Recently, we identified scheelite and wolframite in quartz veins in the Matou deposit, which is uncommon in other porphyry and skarn deposits in the MLYMB. We carried out detailed zircon U–Pb dating and geochemical and Sr–Nd–Hf isotopic studies of the granodiorite porphyry at Matou to define any differences from other ore-related granitoids. The porphyry shows a SiO₂ content ranging from 61.85 wt.% to 65.74 wt.%, K₂O from 1.99 wt.% to 3.74 wt.%, and MgO from 1.74 wt.% to 2.19 wt.% (Mg^# value ranging from 45 to 55). It is enriched in light rare earth elements and large ion lithophile elements, but relatively depleted in Nb, Ta, Y, Yb and compatible trace elements (such as Cr, Ni, and V), with slight negative Eu anomalies (Eu/Eu^* = 0.88–0.98) and almost no negative Sr anomalies. Results of electron microprobe analysis of rock-forming silicate minerals indicate that the Matou porphyry has been altered by an oxidized fluid that is rich in Mg, Cl, and K. The samples show relatively low ε_Nd(t) values from −7.4 to −7.1, slightly high initial ⁸⁷Sr/⁸⁶Sr values from 0.708223 to 0.709088, and low ε_Hf(t) values of zircon from −9.0 to −6.5, when compared with the other Cu–Mo porphyry deposits in the MLYMB. Zircon U–Pb dating suggests the Matou granodiorite porphyry was emplaced at 139.5 ± 1.5 Ma (MSWD = 1.8, n = 15), which is within the age range of the other porphyries in the MLYMB. Although geochemical characteristics of the Matou and other porphyries in the MLYMB are similar and all adakitic, the detrital zircons in the samples from Matou suggest that Archean lower crust (2543 ± 29 Ma, MSWD = 0.25, n = 5) was involved with the generation of Matou magma, which is different from the other porphyries in the belt. Our study suggests that the Matou granodiorite porphyry originated from partial melting of thickened lower crust that was delaminated into the mantle, similar to the other porphyries in the MLYMB, but it has a higher proportion of lower crustal material, including Archean rocks, which contributed to the formation of the porphyry and related W-rich magmatic-hydrothermal system.     

Origin of the inconsistent apparent Re–Os ages of the Jinchuan Ni–Cu sulfide ore deposit,China: Post-segregation diffusion of Os

Apparent Re–Os ages of some magmatic sulfide ore deposits are older than the zircon and baddeleyite U–Pb ages which are interpreted as the formation age of the host intrusions. The Jinchuan Ni–Cu–PGE deposit of China, the world's third largest, is such a case. We report apparent Re–Os isochron ages of 1117 ± 67 Ma, 1074 ± 120 Ma and 867 ± 75 Ma with initial ¹⁸⁷Os/¹⁸⁸Os ratios of 0.120 ± 0.012, 0.162 ±0.017 and 0.235 ± 0.027 for disseminated ores, sulfides from the disseminated ores and massive ores from Jinchuan, respectively. Using these data and Re–Os ages from the literature, we find that the oldest apparent Re–Os age and lowest initial Os isotope ratio are from disseminated ores which contain small amounts of sulfide minerals, the highest initial Os isotope ratios and youngest apparent Re–Os ages, consistent with the zircon and baddeleyite U–Pb ages, are from massive ores containing 90–100 modal% sulfide, and net-textured ores with about 25 modal% sulfides yield apparent Re–Os ages and initial Os ratios intermediate between those of the disseminated and massive ores.Because Os diffusion between sulfides is inhibited by the intervening silicates even at high temperatures, re-equilibration did not occur in the disseminated ore and the samples retained the Os ratios of the contaminated magma, leading to geologically meaningless ages that are older than the formation age of the rocks. While Os-bearing sulfide minerals and magnetite show low closure temperatures of Os diffusion and the sulfide minerals in the massive ore are closely connected with each other, facilitating fast diffusion of Os, re-equilibration of Os was achieved during cooling of the ore from about 850 °C after the segregation to about 400 °C. Thus, an age corresponding to the formation time and an elevated initial Os ratio were yielded by the massive ore. Os isotopes in the net-textured ore behave in the way intermediate between the disseminated and massive ores. Pb isotope data support the Os results. Disseminated ores have heterogeneous Pb isotope ratios whereas Pb in the massive ores is more uniform, consistent with Pb isotopic equilibration in the massive ores, but not in the disseminated ores.     

Re-Os systematics and geochemistry of cobaltite (CoAsS) in the Idaho cobalt belt,Belt-Purcell Basin,USA: Evidence for middle Mesoproterozoic sediment-hosted Co-Cu sulfide mineralization with Grenvillian and Cretaceous remobilization

We report the first study of the Re-Os systematics of cobaltite (CoAsS) using disseminated grains and massive sulfides from samples of two breccia-type and two stratabound deposits in the Co-Cu-Au Idaho cobalt belt (ICB), Lemhi subbasin to the Belt-Purcell Basin, Idaho, USA. Using a ¹⁸⁵Re + ¹⁹⁰Os spike solution, magnetic and non-magnetic fractions of cobaltite mineral separates give reproducible Re-Os analytical data for aliquot sizes of 150 to 200 mg. Cobaltite from the ICB has highly radiogenic ¹⁸⁷Os/¹⁸⁸Os ratios (17–45) and high ¹⁸⁷Re/¹⁸⁸Os ratios (600–1800) but low Re and total Os contents (ca. 0.4–4 ppb and 14–64 ppt, respectively). Containing 30 to 74% radiogenic ¹⁸⁷Os, cobaltite from the ICB is amenable to Re-Os age determination using the isochron regression approach.Re-Os data for disseminated cobaltite mineralization in a quartz-tourmaline breccia from the Haynes-Stellite deposit yield a Model 1 isochron age of 1349 ± 76 Ma (2σ, n = 4, mean squared weighted deviation MSWD = 2.1, initial ¹⁸⁷Os/¹⁸⁸Os ratio = 4.7 ± 2.2). This middle Mesoproterozoic age is preserved despite a possible metamorphic overprint or a pulse of metamorphic-hydrothermal remobilization of pre-existing cobaltite that formed along fold cleavages during the ca. 1190–1006 Ma Grenvillian orogeny. This phase of remobilization is tentatively identified by a Model 3 isochron age of 1132 ± 240 Ma (2σ, n = 7, MSWD = 9.3, initial ¹⁸⁷Os/¹⁸⁸Os ratio of 9.0 ± 2.9) for cobaltite in the quartz-tourmaline breccia from the Idaho zone in the Blackbird mine.All Mesoproterozoic cobaltite mineralization in the district was affected by greenschist- to lower amphibolite-facies (garnet zone) metamorphism during the Late Jurassic to Late Cretaceous Cordilleran orogeny. However, the fine- to coarse-grained massive cobaltite mineralization from the shear zone-hosted Chicago zone, Blackbird mine, is the only studied deposit that has severely disturbed Re-Os systematics with evidence for a linear trend of mixing with (metamorphic?) fluids.The new Re-Os ages and extremely high initial ¹⁸⁷Os/¹⁸⁸Os ratios of cobaltite reported here favor a magmatic-hydrothermal genetic model for a multi-stage REE-Y-Co-Cu-Au mineralization occurring at ca. 1370 to 1349 Ma, and related to the emplacement of the Big Deer Creek granite pluton at ca. 1377 Ma. In our model, deposition of paragenetically early xenotime and gadolinite was followed by an influx of Mesoproterozoic evaporitic brines and magmatic-hydrothermal fluids containing metals and reduced sulfur derived from mafic and oceanic island-arc Archean to Paleoproterozoic rocks in the Laurentian basement. Cobaltite mineralization occurred upon cooling of these fluids at an inferred temperature of 300 °C or below.     

Geology and molybdenite Re–Os age of the Dahutang granite-related veinlets-disseminated tungsten ore field in the Jiangxin Province,China

This is a brief research report about the recently-discovered and currently being explored Dahutang tungsten deposit (or ore field) in northwestern Jiangxi, south-central China. The deposit is located south of the Middle–Lower Yangtze River valley Cu–Au–Mo–Fe porphyry–skarn belt (YRB). The mineralization is genetically associated with Cretaceous porphyritic biotite granite and fine-grained biotite granite and is mainly hosted within a Neoproterozoic biotite granodiorite batholith. The Dahutang ore field comprises veinlets-disseminated (~ 95% of the total reserve), breccia (~ 4%) and wolframite–scheelite quartz vein (~ 1%) ore styles. The mineralization and alteration are close to the pegmatite shell between the Cretaceous porphyritic biotite granite and Neoproterozoic biotite granodiorite and the three styles of ore bodies mentioned above are related to zoned hydrothermal alteration that includes greisenization, K-feldspar alteration, silicification, carbonatization, chloritization and fluoritization arranged in time (early to late) and space (bottom to top).Five samples of molybdenite from the three types of ores have been collected for Re/Os dating. The results show Re/Os model ages ranging from 138.4 Ma to 143.8 Ma, with an isochron age of 139.18 ± 0.97 Ma (MSWD = 2.9). The quite low Re content in molybdenite falls between 0.5 ppm and 7.8 ppm that is indicative of the upper crustal source. This is quite different from molybdenites in the YRB Cu–Au–Mo–Fe porphyry–skarn deposits that contain between 53 ppm and 1169 ppm Re, indicating a mantle source.The Dahutang tungsten system is sub-parallel with the YRB porphyry–skarn Cu–Au–Mo–Fe system. Both are situated in the north margin of the Yangtze Craton and have a close spatial–temporal relationship. This possibly indicates a comparable tectonic setting but different metal sources. Both systems are related to subduction of the Paleo-Pacific plate beneath the Eurasian continent in Early Cretaceous. The Cu–Au–Mo–Fe porphyry–skarn ores are believed genetically related to granitoids derived from the subducting slab, whereas the porphyry W deposits are associated with S-type granitoids produced by remelting of the upper crust by heat from upwelling asthenoshere.     

A hydrothermal origin for the large Xinqiao Cu-S-Fe deposit,Eastern China: Evidence from sulfide geochemistry and sulfur isotopes

The Xinqiao Cu-S-Fe deposit in the Tongling ore district, Middle-Lower Yangtze River Valley Metallogenic Belt (MLYB; Eastern China), is located along the northern margin of the Yangtze Craton. The stratiform- and skarn-type Xinqiao mineralization comprises five stages, namely the early skarn (Stage I, garnet and diopside), late skarn (Stage II, epidote-dominated), iron oxides (Stage III, hematite and magnetite), colloform pyrite (Stage IV) and quartz-sulfides (Stage V). There are three pyrite types at Xinqiao, i.e., colloform (Py1; Stage IV), fine-grained (Py2, from Py1 recrystallization; Stage V) and coarse-grained (Py3; Stage V) pyrites.Scanning Electron Microscope (SEM) imagery for Py1 reveals that they are cubic microcrystalline pyrite aggregates, and the EDS and XRD data indicate that some Py1 contain minor siderite impurities. Electron Microprobe Analysis (EMPA) and LA-ICP-MS geochemical data demonstrate that the three pyrite types have relatively high Fe/S ratios and distinctly high Mn, Cu and As concentrations. Compared to Py2 and Py3, Py1 has higher Pb, Bi and Ag, but lower Co, Ni, Se, Cd, Te and Au. Ratios of Fe/S (0.837 to 0.906), Se/Te (2.39 to 14.50) and Co/Ni (0.67 to 4.67) of the Xinqiao pyrites resemble typical hydrothermal pyrites. δ³⁴S_CDT of Py1 (− 0.6‰ to 2.7‰, average 0.58‰), Py2 (1.8‰ to 2.5‰, average 2.1‰) and Py3 (1.9‰ to 4.4‰, average 3.5‰) are close to those of the Xinqiao skarn-type orebodies (1.3‰ to 4.1‰), but distinct from those of the Upper Carboniferous Huanglong Formation limestone (− 9.5‰ to − 15.4‰), suggesting that the three pyrite types (especially Py1) were genetically linked to the Yanshanian (Jurassic-Cretaceous) magmatic-hydrothermal events, with Py1 probably reflecting rapid crystallization during fluid mixing. We interpret that the Xinqiao stratiform mineralization may have been associated with the Jitou quartz diorite stock, as may be the case also for the skarn-type mineralization hosted in the contact between the Yanshanian Jitou stock and the Lower Permian Qixia Formation limestone. Overall, the Xinqiao Cu-S-Fe mineralization may have been generated by the Jurassic-Cretaceous tectono-thermal event in Eastern China.     

New Lu–Hf and Sm–Nd geochronology constrains the subduction of oceanic crust during the Carboniferous–Permian in the Dabie orogen

Eclogites from the Huwan shear zone in the western Dabie were investigated in terms of their P–T evolution, geochemistry, and combined Lu–Hf and Sm–Nd geochronology. Trace element and isotope data suggest a normal mid-ocean ridge rather than an intraplate or ocean island setting for the protoliths of the eclogites. Electron microprobe analyses of representative garnets show typical prograde zoning profiles. Estimated peak metamorphic temperatures of 540–590 °C most likely did not exceed the closure temperature of the Lu–Hf and Sm–Nd systems. The consistent Lu–Hf and Sm–Nd ages, therefore, most likely reflect garnet growth and are interpreted to reflect high-pressure eclogite-facies metamorphism due to the occurrence of omphacite inclusions from core to rim in garnets and the spherical geometry effect despite the well-preserved prograde zoning in the garnets. The high-pressure mineral assemblage of the eclogite yielded a statistically robust Lu–Hf age of 260.0 ± 1.0 Ma (2σ, 10 points, MSWD = 1.0) and a Sm–Nd age of 260.4 ± 2.0 Ma (2σ, 9 points, MSWD = 1.4), which are younger than the Carboniferous zircon U–Pb ages of ca. 310 Ma. The new Lu–Hf and Sm–Nd data, in combination with published geochronological data, define two distinct Carboniferous and Permian population ages for the oceanic-type eclogites from the Huwan shear zone, which may require that these rocks experienced two episodes of high-pressure metamorphism within less than 50 Myr.     

In situ zircon U–Pb dating and O isotopes of the Neoarchean Hongtoushan VMS Cu–Zn deposit in the North China Craton: Implication for the ore genesis

The Hongtoushan volcanogenic massive sulfide (VMS) deposit is the largest Archean Cu–Zn deposit in China, located in the Qingyuan greenstone belt on the northern margin of the North China Craton. The Cu–Zn mineralization was stratigraphically controlled by the interbeds (~ 100 m in thickness) of mafic–felsic volcanic sets and overlain by banded iron layers. However, the relationship between VMS deposits and associated volcanics has not been examined. This study ultimately clarifies the times and sources of the volcanics and mineralization. Based on in situ zircon U–Pb and O isotope on VMS-hosting mafic, felsic volcanic rocks, banded and massive sulfide ores and postmineralization pegmatite vein, we considered that there were two main formation stages for the Qingyuan Cu–Zn deposits; one was exhalative-hydrothermal sedimentation and another was further Cu–Zn enriched by later hydrothermal processes. The timing of the first stage occurred at 2571 ± 6 Ma based on the magmatic zircons in the VMS-hosting mafic volcanic rocks, from which the inherited zircons also indicate the existence of 2.65–3.12 Ga ancient supercrustal rocks in the Qingyuan district. A modern mantle-like δ¹⁸Ozircon value of 5.5 ± 0.1‰ (2SD) for this volcanism was well preserved in the inherited core domains of ore samples. It suggests that the mafic volcanics was most likely sourced from partial melting of juvenile crust, e.g., TTG granites. A large-scale metamorphic or hydrothermal event is documented by the recrystallized zircons in sulfide ores. The timing is tightly constrained by the hydrothermal zircon U–Pb ages. They are 2508 ± 4 Ma for the banded ore, 2507 ± 4 Ma for the massive ore and 2508 ± 2 Ma for the postmineralization pegmatite vein. These indistinguishable ages indicate that the 2507 Ma hydrothermal systems played a significant role in the upgrading of the VMS Cu–Zn orebodies. The weighted δ¹⁸O values of hydrothermal zircons show a successively increasing trend from 6.0 ± 0.1‰ (2σ) for the banded ore, 6.6 ± 0.2‰ (2σ) for the massive ore to 7.3 ± 0.2‰ (2σ) for the later pegmatite vein. This variation might be induced by gradual inputting of the δ¹⁸O-rich oceanic crust and/or oceanic sediment during the hydrothermal cycling system. Considering its modern mantle-like oxygen isotope composition of 2571 Ma volcanism, a submarine volcanic hydrothermal system involving mantle plumes is a preferred setting for the Neoarchean VMS Cu–Zn deposits in the Qingyuan greenstone belt.     

Zircon and titanite U-Pb dating of the Zhangjiawa iron skarn deposit,Luxi district,North China Craton: Implications for a craton-wide iron skarn mineralization

The North China craton hosts numerous iron skarn deposits containing more than 2600 Mt of iron ores, mostly with an average grade of >45 wt% Fe, which have been among the most important source of high-grade iron ores for the last three decades in China. These deposits typically form clusters and can be roughly divided into the western and eastern belts, which are located in the middle of Trans-North China orogen and to the west of the Tan-Lu fault zone in the eastern part of North China craton, respectively. The western belt mainly consists of the southern Taihang district, as well as the Linfen and Taiyuan ore fields, whereas the eastern belt comprises the Luxi and Xu-Huai districts. The Zhangjiawa deposit in the Luxi district has proven reserves of 290 Mt at an average of 46% Fe (up to >65%). The iron mineralization occurs mainly along contact zones between the Kuangshan dioritic intrusion and middle Ordovician marine carbonate rocks that host numerous evaporite intercalations. Titanite grains from the mineralized skarn are closely intergrown with magnetite and retrograde skarn minerals including chlorite, phlogopite and minor epidote, indicating a hydrothermal origin. The titanite grains have extremely low REE contents and low Th/U ratios, consistent with their precipitation directly from hydrothermal fluids responsible for the iron mineralization. Ten hydrothermal titanite grains yield a weighted mean ²⁰⁶Pb/²³⁸U age of 131.0 ± 3.9 Ma (MSWD = 0.1, 1σ), which is in excellent agreement with a zircon U-Pb age (130 ± 1 Ma) of the ore-related diorite. This age consistency confirms that the iron skarn mineralization is temporally and likely genetically related to the Kuangshan intrusion. Results from this study, when combined with existing isotopic age data, suggest that iron skarn mineralization and associated magmatism throughout both the eastern and western belts took place coevally between 135 and 125 Ma, with a peak at ca. 130 Ma. As such, those deposits may represent the world's only major Phanerozoic iron skarn concentration hosted in Precambrian cratons. The magmatism and associated iron skarn mineralization coincide temporally with the culmination of lithospheric thinning and destruction of the North China craton, implying a causal link between the two.     

Geology and genesis of Kafang Cu–Sn deposit,Gejiu district,SW China

Kafang is one of the main ore deposits in the world-class Gejiu polymetallic tin district, SW China. There are three main mineralization types in the Kafang deposit, i.e., skarn Cu–Sn ores, stratiform Cu ores hosted by basalt and stratiform Cu–Sn ores hosted by carbonate. The skarn mainly consists of garnet and pyroxene, and retrograde altered rocks. These retrograde altered rocks are superimposed on the skarn and are composed of actinolite, chlorite, epidote and phlogopite. Major ore minerals are chalcopyrite, pyrrhotite, cassiterite, pyrite and scheelite. Sulfur and Pb isotopic components hint that the sources of different types of mineralization are distinctive, and indicate that the skarn ore mainly originated from granitic magma, whereas the basalt-hosted Cu ores mainly derived from basalt. Microthermometry results of fluid inclusions display a gradual change during the ore-forming process. The homogenization temperature of different types of inclusions continuously decreases from early to late mineralization stages. The salinities and freezing temperatures exhibit similar evolutionary tendencies with the T _{homogenization}, while the densities of the different types keep constant, the majority being less than 1. Oxygen and hydrogen isotopic values (δ¹⁸O and δD) of the hydrothermal fluids fall within ranges of 3.1 to 7.7‰ with an average of 6.15‰, calculated at the corresponding homogenization temperature, and − 73 and − 98‰ with an average of − 86.5‰, respectively. Microthermometry data and H–O isotopes indicate that the ore-forming fluid of the Kafang deposit is mainly derived from magma in the early stage and a mixture of meteoric and magmatic water in late stage. Molybdenite Re–Os age of the skarn type mineralization is 83.4 ± 2.1 Ma, and the stratiform ores hosted by basalt is 84.2 ± 7.3 Ma, which are consistent with the LA-ICP-MS zircon age of the Xinshan granite intrusion (83.1 ± 0.4 Ma). The evidence listed above reflects the fact that different ore styles in the Kafang deposit belong to the same mineralization system.     

Re–Os pseudo-isochron of disseminated ore from the Kalatongke Cu–Ni sulfide deposit,Xinjiang, Northwest China: Implications for Re–Os dating of magmatic Cu–Ni sulfide deposits

Re–Os dating of disseminated ore from the Kalatongke Cu–Ni sulfide mineral deposit, Xinjiang, Northwest (NW) China, yields an apparent isochron age of 433 ± 31 Ma with an apparent initial ¹⁸⁷Os/¹⁸⁸Os (433 Ma) ratio of 0.197 ± 0.027. This apparent age is older than not only the zircon U–Pb age of the host intrusion (287 ± 5 Ma, Han et al., 2004) but also the stratigraphic age of the intruded country rock. Thus, the regression line is a pseudo-isochron. However, previous Re–Os dating of massive ores of the same deposit yielded an age that is consistent, within analytical uncertainty, with the zircon U–Pb age (Zhang et al., 2008). This relationship is similar to that observed in the Jinchuan deposit, NW China. Therefore, we suggested that the same mechanism, post-segregation diffusion of Os (Yang et al., 2008), is applicable to the Kalatongke deposit.Re–Os isotopic studies of Kalatongke, Jinchuan and representative magmatic Cu–Ni sulfide deposits suggest that the massive ores of mafic–ultramafic-rock-associated Cu–Ni sulfide deposits would yield geologically meaningful Re–Os age, whereas a pseudo-isochron would be obtained for the disseminated ores. Therefore, to obtain a geologically meaningful Re–Os age, the type of the deposit, the type of the ore and the ore-forming process should be taken into account.     

The genesis of the ores and granitic rocks at the Hongshi Au deposit in Eastern Tianshan,China: Constraints from zircon U–Pb geochronology,geochemistry and isotope systematics

The Hongshi gold deposit is located in the southwestern margin of the Kanggur–Huangshan ductile shear zone in Eastern Tianshan, Northwest China. The gold ore bodies are predominantly hosted in the volcanogenic metasedimentary rocks of the Lower Carboniferous Gandun Formation and the Carboniferous syenogranite and alkali-feldspar granite. The syenogranite and the alkali-feldspar granite yield SHRIMP zircon U–Pb ages of 337.6 ± 4.5 Ma (2σ, MSWD = 1.3) and 334.0 ± 3.7 Ma (2σ, MSWD = 1.1), respectively, indicating that the Hongshi gold deposit is younger than 334 Ma. The granitoids belong to shoshonitic series and are relatively enriched in large ion lithophile elements (Rb, K, Ba, and Pb) and depleted in high field-strength elements (Nb, Ta, P, and Ti). Moreover, these granitoids have high SiO₂, Al₂O₃, and K₂O contents, low Na₂O, MgO, and TiO₂ contents, low Nb/Ta ratios, and slightly positive Eu anomalies. The ε_Hf(t) values of the zircons from a syenogranite sample vary from + 1.5 to + 8.8 with an average of + 5.6; the ε_Hf(t) values of the zircons from an alkali-feldspar granite sample vary from + 5.0 and + 10.1 with an average of + 7.9. The δ³⁴S values of 10 sulfide samples ranged from − 11.5‰ to + 4.2‰, with peaks in the range of + 1‰ to + 4‰. The above-mentioned data suggest that the Hongshi granitoids were derived from the melting of juvenile lower crust mixed with mantle components formed by the southward subduction of the paleo-Tianshan ocean plate beneath the Aqishan–Yamansu island arc during the Early Carboniferous. The Hongshi gold deposit was formed by post-collisional tectonism during the Permian. The granitoids most likely acted as impermeable barriers that prevented the leakage and runoff of ore-bearing fluids. Thus, the granitoids probably played an important role in controlling gold mineralization.     

The origin of the world class tin-polymetallic deposits in the Gejiu district,SW China: Constraints from metal zoning characteristics and 40Ar–39Ar geochronology

The Gejiu tin-polymetallic deposits in the Western Cathaysia Block of South China comprise the world's largest primary tin district, with a total resource of approximately 300 million metric ton ores, at an average grade of 1 wt percent Sn. Tin polymetallic mineralization occurs in five deposits and has four ore types, i.e., greisen, skarn, stratabound cassiterite-sulfide (mostly oxidized) and vein type ore. In each deposit the orebodies typically occur in an extensive hydrothermal system centered on a shallow Late Cretaceous granitoid cupola. Metal zoning is well developed both vertically and horizontally over the entire district, from W + Be + Bi ± Mo ± Sn ores inside granite intrusions, to Sn + Cu-dominated ores at intrusion margins and farther out to Pb + Zn deposits in the surrounding host carbonate. This zoning pattern is similar to that of other hydrothermal deposits in other parts of the world, indicating a close genetic relationship between magmatism and mineralization. In this paper, we dated thirteen mica samples from all types of mineralization and from the five deposits in the Gejiu district. The ages range from 77.4 ± 0.6 Ma to 95.3 ± 0.7 Ma and are similar to the existing zircon U–Pb age of the granitic intrusions (77.4 ± 2.5–85.8 ± 0.6), indicating a genetic relationship between the mineralization and the intrusions. Geological characteristics, metal zoning patterns and new geochronological data all indicate that the tin-polymetallic ores in the Gejiu district are hydrothermal in origin and are genetically related to the nearby granitic intrusions. It is unlikely that the deposits are syngenetic, as has been proposed in recent years.     

铜陵新桥层状菱铁矿成因的矿物学证据及成矿意义

安徽铜陵新桥矿区二叠系栖霞组底部和石炭系黄龙组—船山组之间产出层状、似层状菱铁矿矿层。开展菱铁矿矿层成因研究对于深入剖析区域层控矽卡岩型铜铁矿床成矿机制具有重要意义。本文利用粉晶X射线衍射（XRD）、扫描电镜（SEM）对菱铁矿矿石进行矿物学研究,结果发现菱铁矿矿石主要由菱铁矿、石英、伊利石和有机质等组成,菱铁矿颗粒粒径较小,表面具有成岩自生的自形石英硬模的微结构,SEM原位微区成分分析显示菱铁矿中除了主量元素铁,还含有大量的锰、锌和钙。矿石中存在两种微结构和不同成因的石英：表面具菱铁矿硬模和次生加大结构的碎屑石英;具六方双锥、单锥以及生物成因球形的自生石英。菱铁矿矿石的组成和矿物表面微结构表明其为沉积成因,非岩浆热液起源。富有机质和亚铁的沉积菱铁矿层和沉积胶状黄铁矿层协同作用,可能是铜陵地区乃至长江中下游成矿带层状铜铁矿床层控性重要制约因素,以及可能作为燕山期中酸岩浆演化的氧化性含铜成矿流体卸载成矿的地球化学还原障。

     

Timing of skarn deposit formation of the Tonglushan ore district,southeastern Hubei Province,Middle–Lower Yangtze River Valley metallogenic belt and its implications

The Tonglushan ore district in the Middle–Lower Yangtze River Valley metallogenic belt includes the Tonglushan Cu–Fe, the Jiguanzui Au–Cu, and the Taohuazui Au–Cu skarn deposits. They are characterized by NE-striking ore bodies and hosted at the contact of Triassic carbonate rocks and Late Mesozoic granitoid deposits. New Sensitive High-Resolution Ion Microprobe (SHRIMP) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA–ICP-MS) zircon U–Pb, molybdenite Re–Os, and phlogopite ⁴⁰Ar–³⁹Ar ages indicate that these skarn deposits formed between 140.3 ± 1.1 and 137.3 ± 2.4 Ma. These dates are identical to the zircon U–Pb ages for host quartz diorites ranging from 140 ± 2 to 139 ± 1 Ma. These results confirm that both skarn mineralization and related intrusions were initiated during the Early Cretaceous. The high rhenium contents (261.4–1152 μg/g) of molybdenites indicate that a metasomatic mantle fluid was involved in the ore-forming process of these skarn ore systems. This conclusion is consistent with previously published constraints from sulfur, deuterium, and oxygen isotope compositions, and the geochemical signatures, and Sr–Nd isotopic data of the mineralization-hosting intrusions. Geological and geochronological evidence demonstrates that there were two igneous events in the Tonglushan ore district. The first resulted in the emplacement of quartz diorite during the Early Cretaceous (140 ± 2 to 139 ± 1 Ma), and the second is characterized by the eruption of volcanic rocks during the mid-Early Cretaceous (130 ± 2 to 124 ± 2 Ma). The former is spatially, temporally and genetically associated with skarn gold-bearing mineralization (140.3 ± 1.1 to 137.3 ± 2.4 Ma). The recognition of these two igneous events invalidates previous models that proposed continuous magmatism and associated mineral deposits in the Middle–Lower Yangtze River Valley metallogenic belt.     

Mineralogy,fluid inclusions,and isotopes of the Cihai iron deposit,eastern Tianshan,NW China: Implication for hydrothermal evolution and genesis of subvolcanic rocks-hosted skarn-type deposits

Most skarn deposits are closely related to granitoids that intruded into carbonate rocks. The Cihai (>100 Mt at 45% Fe) is a deposit with mineral assemblages and hydrothermal features similar to many other typical skarn deposits of the world. However, the iron orebodies of Cihai are mainly hosted within the diabase and not in contact with carbonate rocks. In addition, some magnetite grains exhibit unusual relatively high TiO₂ content. These features are not consistent with the typical skarn iron deposit. Different hydrothermal and/or magmatic processes are being actively investigated for its origin. Because of a lack of systematic studies of geology, mineral compositions, fluid inclusions, and isotopes, the genetic type, ore genesis, and hydrothermal evolution of this deposit are still poorly understood and remain controversial.The skarn mineral assemblages are the alteration products of diabase. Three main paragenetic stages of skarn formation and ore deposition have been recognized based on petrographic observations, which show a prograde skarn stage (garnet-clinopyroxene-disseminated magnetite), a retrograde skarn stage (main iron ore stage, massive magnetite-amphibole-epidote ± ilvaite), and a quartz-sulfide stage (quartz-calcite-pyrite-pyrrhotite-cobaltite).Overall, the compositions of garnet, clinpyroxene, and amphibole are consistent with those of typical skarn Fe deposits worldwide. In the disseminated ores, some magnetite grains exhibit relatively high TiO₂ content (>1 wt.%), which may be inherited from the diabase protoliths. Some distinct chemical zoning in magnetite grains were observed in this study, wherein cores are enriched in Ti, and magnetite rims show a pronounced depletion in Ti. The textural and compositional data of magnetite confirm that the Cihai Fe deposit is of hydrothermal origin, rather than associated with iron rich melts as previously suggested.Fluid inclusions study reveal that, the prograde skarn (garnet and pyroxene) formed from high temperature (520–600 °C), moderate- to high-salinity (8.1–23.1 wt.% NaCl equiv, and >46 wt.% NaCl equiv) fluids. Massive iron ore and retrograde skarn assemblages (amphibole-epidote ± ilvaite) formed under hydrostatic condition after the fracturing of early skarn. Fluids in this stage had lower temperature (220°–456 °C) and salinity (8.4–16.3 wt.% NaCl equiv). Fluid inclusions in quartz-sulfide stage quartz and calcite also record similar conditions, with temperature range from 128° to 367 °C and salinity range from 0.2 to 22.9 wt.% NaCl equiv. Oxygen and hydrogen isotopic data of garnet and quartz suggest that mixing and dilution of early magmatic fluids with external fluids (e.g., meteoric waters) caused a decrease in fluid temperature and salinity in the later stages of the skarn formation and massive iron precipitation. The δ¹⁸O values of magnetite from iron ores vary between 4.1 and 8.5‰, which are similar to values reported in other skarn Fe deposits. Such values are distinct from those of other iron ore deposits such as Kiruna-type and magmatic Fe-Ti-V deposits worldwide. Taken together, these geologic, geochemical, and isotopic data confirm that Cihai is a diabase-hosted skarn deposit related to the granitoids at depth.     

Combined zircon and cassiterite U–Pb dating of the Piaotang granite-related tungsten–tin deposit,southern Jiangxi tungsten district,China

The large low-grade Piaotang W–Sn deposit in the southern Jiangxi tungsten district of the eastern Nanling Range, South China, is related to a hidden granite pluton of Jurassic age. The magmatic-hydrothermal system displays a zonation from an inner greisen zone to quartz veins and to peripheral veinlets/stringers (Five-floor zonation model). Most mineralization is in quartz veins with wolframite > cassiterite. The hidden granite pluton in underground exposures comprises three intrusive units, i.e. biotite granite, two-mica granite and muscovite granite. The latter unit is spatially associated with the W–Sn deposit.Combined LA-MC-ICP-MS U–Pb dating of igneous zircon and LA-ICP-MS U–Pb dating of hydrothermal cassiterite are used to constrain the timing of granitic magmatism and hydrothermal mineralization. Zircon from the three granite units has a weighted average ²⁰⁶Pb/²³⁸U age of 159.8 ± 0.3 Ma (2 σ, MSWD = 0.3). The cathodoluminescence (CL) textures indicate that some of the cassiterite crystals from the wolframite-cassiterite quartz vein system have growth zonations, i.e. zone I in the core and zone II in the rim. Dating on cassiterite (zone II) yields a weighted average ²⁰⁶Pb/²³⁸U age of 159.5 ± 1.5 Ma (2 σ, MSWD = 0.4), i.e. the magmatic and hydrothermal systems are synchronous. This confirms the classical model of granite-related tin–tungsten mineralization, and is against the view of a broader time gap of >6 Myr between granite magmatism and W–Sn mineralization which has been previously proposed for the southern Jiangxi tungsten district. The elevated trace element concentrations of Zr, U, Nb, Ta, W and Ti suggest that cassiterite (zone II) formed in a high-temperature quartz vein system related to the Piaotang granite pluton.