Penetration of surface-evaporated brines into the Proterozoic basement and deposition of Co and Ag at Bou Azzer (Morocco): Evidence from fluid inclusions

Ag-ores occur in a specific zone of the Bou Azzer Co–As deposit in the Precambrian basement of the Anti-Atlas belt (Morocco), especially in highly microfractured quartz-depleted diorite. They formed after the main Co–As stage of mineralization, but both ore stages (Co–As and Ag-ore) appear linked to similar immiscible fluids: an hyper-saline Na–Ca brine (5.5–22 wt.%. eq. NaCl and 13.5–18.5 wt.% eq. CaCl₂, with Na/Ca ranging from 0.4 to 1.2 during Ag-mineralization) occurring as L + V ± halite fluid inclusions and CH₄–(N₂) gas dominated fluids. Pressure–temperature estimates for the Ag-stage range from 40 to 80 MPa and 150 to 200 °C e.g. at a temperature slightly lower than that of the preceding Co–As stage (200–220 °C).Chlorinity, cation (Na/Ca ca. 2.2) and halogen ratios (Cl/Br from 300 to 360) are typical of deep basinal brines, especially of surface-evaporated brines that have exceeded halite saturation. The primary brines were modified by fluid–rock interaction during burial and migration through the basement. Ag-deposition was probably favoured by dilution and cooling due to the mixing of brines with less saline fluids. Similarities between the Ag-brines from Bou Azzer, Zgounder and Imiter suggest a regional scale circulation of basinal brines during extension probably later than the Triassic, during the early stages of rifting of the Atlantic.     

Melt impregnation phases in the mantle section of the Ślęża ophiolite (SW Poland)

The ultramafic member of the Variscan Ślęża Ophiolite (SW Poland) consists of heavily serpentinised, refractory harzburgites. Those located down to 1.5 km below paleo-Moho contain scarce grains or aggregates of olivine, clinopyroxene and spinel. Non-serpentine phases occur in various assemblages: M1—olivine (Fo 90.2–91.0%, NiO 0.38–0.47 wt.%) and rounded or amaeboidal aluminous chromite, rimmed by Al poor chromite and magnetite; M2—olivine (Fo 90.5–91.5, NiO 0.32–0.44 wt.%), olivine with magnetite inclusions (Fo 87.1–92.5, NiO 0.01–0.68 wt.%), rounded, cleavaged clinopyroxene I (Mg# 91.1–93.2, Al₂O₃ 3.00–4.00 wt.%, Cr₂O₃ 1.00–1.40 wt.%) and elongated clinopyroxene II and clinopyroxene from symplectites with magnetite (Mg# = 92.2–94.1, Al₂O₃ 2.20–3.20 wt.% and Cr₂O₃ 0.80–1.20 wt.%). Clinopyroxene is depleted in REEs relative to chondrite. The M3 assemblage consists of intergrown olivine (Fo 90.8–92.7, NiO 0.20–0.38 wt.%) and clinopyroxene (Mg# = 96.0–98.1, Al₂O₃ 0.00–1.00 wt.% and Cr₂O₃ 0.20–0.60 wt.%).The M1 assemblage contains chromite which records greenschist-facies metamorphism. Textural relationships and chemical composition of clinopyroxene occurring in the M2 assemblage are similar to those formed in oceanic spreading centres by LREE depleted basaltic melt percolation. Olivine occurring in M1 assemblage and part of that from M2 have composition typical of residual olivine from the abyssal harzburgites and of olivine formed in those rocks by melt percolation. The olivine with magnetite inclusions (M2 assemblage) and that from M3 record later deserpentinization event, which supposedly produced also M3 clinopyroxene. The non-serpentine phases from the Ślęża ophiolite mantle member, albeit very poorly preserved, document depleted basaltic melt percolation in the Variscan oceanic spreading centre.     

Geochronology and geochemistry of submarine volcanic rocks in the Yamansu iron deposit,Eastern Tianshan Mountains,NW China: Constraints on the metallogenesis

The Yamansu skarn iron deposit is hosted in Early Carboniferous submarine lava flow and volcaniclastic rocks of the Yamansu Formation in Eastern Tianshan Mountains, NW China. The lava flows are predominantly basaltic, with minor andesites. Laser ablation inductively coupled plasma mass spectrometry (LAICP-MS) U–Pb zircon dating of the basalts and skarns yields almost coeval ages of 324.4 ± 0.94 and 323.47 ± 0.95 Ma, respectively. The basalts contain clinopyroxene and plagioclase phenocrysts with a considerable amount of Fe–Ti oxide minerals in the groundmass as interstitial phases, probably suggesting that olivine–, clinopyroxene- and plagioclase fractionated within the magma chamber. Geochemically, the basalts are characterized by slight variations in SiO₂ (42.90–46.61 wt.%), P₂O₅ (0.08–0.12 wt.%), MnO (0.35–0.97 wt.%) and TiO₂ (0.74–0.82 wt.%), and relatively large variations in CaO (6.93–15.13 wt.%), Al₂O₃ (14.71–19.93 wt.%), total Fe₂O₃ (8.14–12.66 wt.%) and MgO (4.96–8.52 wt.%). They possess flat to light rare earth element (REE)-depleted patterns and display variable degrees of depletions in high field-strength elements (HFSE), suggesting a transitional feature between MORB and arc volcanic rocks, and indicating a back-arc tectonic setting. Furthermore, the geochemical signature also suggests that the volcanic rocks of Yamansu Formation were produced by partial melting of the spinel-facies, asthenospheric mantle peridotite which had been metasomatized by slab-derived fluids. The broadly overlapping ages of the basalts and skarn mineralization suggests that the skarn formation in the Yamansu deposit is related to subaqueous volcanism. In combination with the available information including fluid inclusions and stable isotope data, we infer that the hydrothermal fluids that generated the skarns could be a mixture of evolved magma-derived fluids and convecting sea water driven by the heat from the shallow active magma chamber. The Yamansu basalts provided the source of iron for the skarn mineralization. We envisage the submarine volcanism, skarn alteration and iron mineralization in the Yamansu iron deposit as a continuous process, different from either conventional intrusion-related skarn type or submarine volcanic exhalation sedimentation type.     

Decarbonation of subducting slabs: Insight from petrological–thermomechanical modeling

Subduction of heterogeneous lithologies (sediments and altered basalts) carries a mixture of volatile components (H₂O ± CO₂) into the mantle, which are later mobilized during episodes of devolatilization and flux melting. Several petrologic and thermodynamic studies investigated CO₂ decarbonation to better understand carbon cycling at convergent margins. A paradox arose when investigations showed little to no decarbonation along present day subduction geotherms at subarc depths despite field based observations. Sediment diapirism is invoked as one of several methods for carbon transfer from the subducting slab. We employ high-resolution 2D petrological–thermomechanical modeling to elucidate the role subduction dynamics has with respect to slab decarbonation and the sediment diapirism hypothesis. Our thermodynamic database is modified to account for H₂O–CO₂ binary fluids via the following lithologies: GLOSS average sediments (H₂O: 7.29 wt.% & CO₂: 3.01 wt.%), carbonated altered basalts (H₂O: 2.63 wt.% & CO₂: 2.90 wt.%), and carbonated peridotites (H₂O: 1.98 wt.% & CO₂: 1.50 wt.%). We include a CO₂ solubility P–x[H₂O wt.%] parameterization for sediment melts. We parameterize our model by varying two components: slab age (20, 40, 60, 80 Ma) and convergence velocity (1, 2, 3, 4, 5, 6 cm year^− 1). 59 numerical models were run and show excellent agreement with the original code base. Three geodynamic regimes showed significant decarbonation. 1) Sedimentary diapirism acts as an efficient physical mechanism for CO₂ removal from the slab as it advects into the hotter mantle wedge. 2) If subduction rates are slow, frictional coupling between the subducting and overriding plate occurs. Mafic crust is mechanically incorporated into a section of the lower crust and undergoes decarbonation. 3) During extension and slab rollback, interaction between hot asthenosphere and sediments at shallow depths result in a small window (~ 12.5 Ma) of high integrated CO₂ fluxes (205 kg m^− 3 Ma^− 1).     

New <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar age constraints on the Late Palaeozoic tectonic evolution of the western Tianshan (Xinjiang,northwestern China), with emphasis on Permian fluid ingress

Laser-probe dating of mylonite whole-rock samples from the North Tianshan—Main Tianshan fault zone that cross-cuts the North Tianshan domain’s southern margin yielded ⁴⁰Ar/³⁹Ar spectra with 255–285 Ma ages. Biotite from an undeformed, Early Carboniferous granite, which cuts the steep mylonitic foliation in the Proterozoic basement of the Yili arcs’s southern margin, gave a 263.4 ± 0.6 Ma plateau age (1σ). Pre-Carboniferous metasediments overlying this basement yielded plateau ages (1σ) of 253.3 ± 0.3 (muscovite) and 252.3 ± 0.3 (biotite) Ma. The Permian ages of mylonites date movement on these ductile, dextral strike-slip shear zones, whereas the mica ages are interpreted by recrystallisation as a result of fluid flow around such transcurrent faults. We propose that the Tianshan’s Permian syn-tectonic bimodal magmatism was created in a non-plume-related Yellowstone-like extensional–transtensional tectonic regime. Gold mineralisation, tracing aqueous flow in the crust, peaked in Permian time and continued locally into the Triassic. The picture is emerging that a convective fluid system partly driven by magmatic heat, existed in a strongly fractured and weakened crust with an elevated heat flow, leading to regional-scale isotope resetting. We suggest that surprisingly young isotopic ages in the literature for early orogenic (ultra)high-pressure metamorphism are similarly due to fluid-mediated recrystallisation.     

The Cretaceous sediment-hosted copper deposits of San Marcos (Coahuila,Northeastern Mexico): An approach to ore-forming processes

In the San Marcos ranges of Cuatrociénegas, NE Mexico, several sediment-hosted copper deposits occur within the boundary between the Coahuila Block, a basement high mostly granitic in composition and Late Paleozoic to Triassic in age, and the Mesozoic Sabinas rift basin. This boundary is outlined by the regional-scale synsedimentary San Marcos Fault. At the basin scale, the copper mineralization occurs at the top of a ～1000 m thick red-bed succession (San Marcos Formation, Berrisian), a few meters below a conformable, transitional contact with micritic limestones (Cupido Formation, Hauterivian to Aptian). It consists of successive decimeter-thick roughly stratiform copper-rich horizons placed just above the red-beds, in a transitional unit of carbonaceous grey-beds grading to micritic limestones. The host rocks are fine- to medium-grained arkoses, with poorly sorted and subangular to subrounded grains. The detrital grains are cemented by quartz and minor calcite; besides, late iron oxide grain-coating cement occurs at the footwall unmineralized red-beds. The source area of the sediments, indicated by their modal composition, is an uplifted basement. The contents of SiO₂ (40.70–87.50 wt.%), Al₂O₃ (5.91–22.00 wt.%), K₂O (3.68–12.50 wt.%), Na₂O (0.03–2.03 wt.%) and CaO (0.09–3.78 wt.%) are within the ranges expected for arkoses. Major oxide ratios indicate that the sedimentary-tectonic setting was a passive margin.The outcropping copper mineralization essentially consists in a supergene assemblage of chrysocolla, malachite and azurite. All that remains of the primary mineralization are micron-sized chalcocite grains shielded by quartz cement. In addition, pyrite subhedral grains occur scattered throughout the copper-mineralized horizons. In these weathered orebodies copper contents range between 4.24 and 7.72 wt.%, silver between 5 and 92 ppm, and cobalt from 8 to 91 ppm. Microthermometric measurements of fluid inclusions in quartz and calcite crystals from footwall barren veinlets gave temperatures of homogenization between 98 °C and 165 °C, and ice-melting temperatures between ?42.5 °C and ?26.1 °C.The primary copper mineralization formed during the early diagenesis, contemporary with the active life of the Sabinas Basin. The mineralizing fluids were dense, near neutral, moderately oxidized brines that originally formed from seawater that, driven by gravity, infiltrated to the deepest parts of the basin and dissolved evaporites. As a result, they became hydrothermal fluids of moderate temperature capable of leaching high amounts of copper. The source of this metal could be mafic detrital grains and iron oxides of the underlying Jurassic and Lower Cretaceous red-beds. Copper precipitation took place when the brines passed through the redox boundary marked by the transition from red- to grey-beds. The upward movement of the brines was promoted by a high heat flow that allowed their convective circulation and their ascent along the synsedimentary San Marcos Fault.     

Kimberlitic sources of super-deep diamonds in the Juina area,Mato Grosso State,Brazil

The Juina diamond field, in the 1970–80s, was producing up to 5–6 million carats per year from rich placer deposits, but no economic primary deposits had been found in the area. In 2006–2007, Diagem Inc. discovered a group of diamondiferous kimberlitic pipes within the Chapadão Plateau (Chapadão, or Pandrea cluster), at the head of a drainage system which has produced most of the alluvial diamonds mined in the Juina area. Diamonds from placer deposits and newly discovered kimberlites are identical; they have super-deep origins from the upper-mantle and transition zone. Field observations and petrographic studies have identified crater-facies kimberlitic material at seven separate localities. Kimberlitic material is represented by tuffs, tuffisites and various epiclastic sediments containing chrome spinel, picroilmenite, manganoan ilmenite, zircon and diamond. The diamond grade varies from 0.2–1.8 ct/m³. Chrome spinel has 30–61 wt.% Cr₂O₃. Picroilmenite contains 6–14 wt.% MgO and 0.2–4 wt.% Cr₂O₃. Manganoan ilmenite has less than 3 wt.% MgO and 0.38–1.41 wt.% MnO. The ¹⁷⁶Hf/¹⁷⁷Hf ratio in kimberlitic zircons is 0.028288–0.28295 with ε_Hf = 5.9–8.3, and lies on the average kimberlite trend between depleted mantle and CHUR. The previously known barren and weakly diamondiferous kimberlites in the Juina area have ages of 79–80 Ma. In contrast, zircons from the newly discovered Chapadão kimberlites have a mean ²⁰⁶Pb/²³⁸U age of 93.6 ± 0.4 Ma, corresponding to a time of magmatic activity related to the opening of the southern part of the Atlantic Ocean. The most likely mechanism of the origin of kimberlitic magma is super-deep subduction process that initiated partial melting of zones in lower mantle with subsequent ascent of proto-kimberlitic magma.     

The Cihai diabase in the Beishan region,NW China: Isotope geochronology,geochemistry and implications for Cornwall-style iron mineralization

Diabase dykes in Cihai, Beishan region, NW China are spatially and temporally associated with ‘Cornwall-type’ iron deposits. U–Pb dating of zircons from a diabase dyke using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) yields an age of 128.5 ± 0.3 Ma, indicating an Early Cretaceous crystallization age. Most of the diabases show low Mg-numbers, suggesting evolved magmas. The diabase dykes show typical ophitic or sub-ophitic textures, and are dominantly composed of phenocrysts of plagioclase (40–50%) and clinopyroxene (30–45%), with minor and varying amounts of biotite and hornblende (1–5%), and minor disseminated magnetite (∼5%). Their mineralogy reflects magma differentiation under relatively low oxygen fugacity conditions. The diabase dykes are characterized by minor variation in SiO₂ (44.67–49.76 wt.%) and MnO (0.14–0.26 wt.%), but show a marked range of Al₂O₃ (10.66–14.21 wt.%), total Fe₂O₃ (9.52–13.88 wt.%), TiO₂ (0.66–2.82 wt.%) and relatively high MgO (4.87–9.29 wt.%) with an Mg# value [atomic Mg/(Mg + Fe²⁺)] of up to 66. The Cihai diabases possibly experienced fractional crystallization of olivine + clinopyroxene and minor crustal contamination during the differentiation process. Prominent negative Nb, Ta and Ti anomalies suggest derivation from subduction-modified mantle. Furthermore, the rocks have relatively unradiogenic Sr- and Nd-isotopic ratios. These characteristics probably reflect partial melting of a subduction component in the source mantle lithosphere through heat input from an upwelling asthenospheric mantle. Such processes probably occurred within an extensional setting during the Early Cretaceous in the Beishan area. The iron-rich fluids were derived from deep sources, and the iron ores were concentrated through a convection cell driven by temperature gradients established by the intrusion of the diabase sills. The combined processes of subduction-related enrichment in the source, shallow depth of emplacement, and the involvement of large-scale circulation of basinal brines from an evaporitic source are inferred to have contributed to the formation of the ‘Cornwall-type’ mineralization in Cihai.     

Effects of fluorine on the solubilities of Nb,Ta, Zr and Hf minerals in highly fluxed water-saturated haplogranitic melts

The effect of fluorine on the solubilities of Mn-columbite (MnNb₂O₆), Mn-tantalite (MnTa₂O₆), zircon (ZrSiO₄) and hafnon (HfSiO₄) were determined in highly fluxed, water-saturated haplogranitic melts at 800 to 1000 °C and 2 kbar. The melt composition corresponds to the intersection of the granite minimum with the albite–orthoclase tieline (Ab₇₂Or₂₈) in the quartz–albite–orthoclase system (Q–Ab–Or), which is representative of a highly fluxed melt, from which high field strength element minerals may crystallize. The melt contains 1.7 wt.% P₂O₅, 1.05 wt.% Li₂O and 1.83 wt.% B₂O₃. The main purpose of this study is to examine the effect of F on columbite, tantalite, zircon and hafnon solubility for a melt with this composition. Up to 6 wt.% fluorine was added as AgF in order to keep the aluminum saturation index (ASI, molar Al/[Na + K]) of the melt constant. In an additional experiment F was added as AlF₃ to make a glass peraluminous. The nominal ASI of the melts are close to 1 for the minimum composition and approximately 1.32 in peraluminous glasses, but if Li is considered as an alkali, the molar ratio Al/[Na + K + Li] of the melts are alkaline (0.87) and subaluminous (1.09), respectively.The molar solubility products [MnO] 1 [Nb₂O₅] and [MnO] 1 [Ta₂O₅] are nearly independent of the F content of the melt, at approximately 18.19 ± 1.2 and 43.65 ± 2.5 × 10^− 4 (mol²/kg²), respectively for the minimum composition. By contrast, there is a positive dependence of zircon and hafnon solubilities on the fluorine content in the minimum composition, which increases from 2.03 ± 0.03 × 10^− 4 (mol/kg) ZrO₂ and 4.04 ± 0.2 × 10^− 4 (mol/kg) HfO₂ for melts with 0 wt.% F to 3.81 ± 0.3 × 10^− 4 (mol/kg) ZrO₂ and 6.18 ± 0.04 × 10^− 4 (mol/kg) HfO₂ for melts with 8 wt.% F. Comparison of the data from this work and previous studies indicates that ASI of the melt seems to have a stronger effect than the contents of fluxing elements in the melt and the overall conclusion is that fluorine is less important (relative to melt compositions) than previously thought for the control on the behavior of high field strength elements in highly evolved granitic melts. Moreover, this study confirms that although Nb, Ta, Zr and Hf are all high field strength elements, Nb–Ta and Zr–Hf are complexed differently in the melt.     

SHRIMP U-Pb zircon geochronology and Hf isotope analyses of Middle Permian–early triassic intrusions in southern Manzhouli area,Northeast China: implications for the subduction of Mongol-Okhotsk plate beneath the Erguna massif

ABSTRACT

The results of SHRIMP U-Pb ages and in situ Hf isotope of zircons from three granites in the southern Manzhouli region of northeast China, provide new data to understand the subduction process of Mongol-Okhotsk Plate beneath the Erguna massif. SHRIMP U-Pb zircon geochronology results yield an age of 265.5 Ma (middle Permian) for fine-grained monzogranite. Rocks from the Early–Middle Triassic are mainly granodiorite (247.4 ± 4.6 and 249.3 ± 4.9 Ma), the granites are with SiO₂ = 60.0–77.4 wt.%, Al₂O₃ = 12.3–16.8wt.% and Na₂O/K₂O = 0.7–1.9. Chemically, they are metaluminous to peraluminous and belong to the high-K calc-alkaline series. Enrichments in the large ion lithophile elements (e.g., Rb, Ba, and K) and depletions in the high field strength elements (e.g., Nb, Ta, and Ti) are typical for these rock types. The monzogranite (~265 Ma) and granodiorite (~247 Ma) contain zircons with εHf(t) values of 6.3–8.5 and 5.1–7.9, yielding T_DM2 model ages of 888–752 and 958–774 Ma, respectively. These geochemical and zircon Hf isotopic data indicate that primary magmas for Middle Permian–Early Triassic granites crystallized from primary magmas generated by Neoproterozoic crustal materials, formed in an active continental margin setting. The andesite of the Gegenaobao formation is similar with the Izu–Bonin–Mariana arc, relating to subduction initiation. Based on the characteristics of exposed rocks and zircon U-Pb ages of andesite and granitoid rocks in the study area, we conclude the onset subduction of Mongol-Okhotsk Plate beneath the Erguna massif may occur at early-middle Permian.     

Silver-base metal epithermal vein and listwanite hosted deposit Crnac,Rogozna Mts., Kosovo,part II: A link between magmatic rocks and epithermal mineralization

Crnac is an intermediate sulfidation Pb–Zn–Ag epithermal deposit located within the Vardar suture zone of the Central Balkan Peninsula. The epithermal Pb–Zn–Ag mineralization consists of (i) a series of steeply-dipping veins hosted within the Jurassic amphibolites, and (ii) overlying hydrothermal-explosive breccia with angular (level IV) or rounded fragments of listwanite (surface) cemented by epithermal mineralization. The mineralization is related to the Oligocene quartz latite dykes that crosscut the Crnac antiform. Quartz latite rocks predominantly display a shoshonitic character. The obtained ⁴⁰Ar/³⁹Ar age of fresh quartz latite is 28.9 ± 0.3 Ma. Fine-grained sericite from altered quartz latite is dated at 28.6 ± 0.5 Ma. Early, alteration related fluid inclusions within quartz latite show coexistence of high-density brine and a low-density vapor-saturated phase that homogenized at 280–405 °C. Phase separation occurs at a paleodepth of 0.6 to 0.9 km.Epithermal mineralization developed in three stages: (i) early pyrite–arsenopyrite–pyrrhotite–quartz–kaolinite; (ii) main sphalerite–galena–tetrahedrite–chalcopyrite and (iii) late carbonate–pyrite–arsenopyrite assemblage. The onset of mineral deposition within epithermal veins was initiated by boiling of Na–Cl ± K ± Ca ± Mg fluid at a paleodepth of 0.6 to 0.9 km. Coexisting vapor and liquid-rich inclusions display salinities and trapping temperatures of 4 wt.% NaCl equiv., 280–370 °C and 2–27 wt.% NaCl equiv., 230–375 °C, respectively. Boiling continued throughout the deposition of the sphalerite-galena-tetrahedrite-chalcopyrite assemblage. Late stage carbonate was deposited from diluted, non-boiling, low-temperature Na–Ca–Mg–Cl ± CO₂ fluid (0.2 to 4.8 wt.% NaCl equiv., 115–280 °C).About 100–150 m higher in the system, precipitation of listwanite breccia cement began as a result of boiling Na–Cl ± Ca ± Mg ± K fluid of medium salinities (2.6 to 12.1 wt.% NaCl equiv.) at temperatures of 245–370 °C. Boiling and dilution of fluids continue throughout the precipitation of the main sphalerite-galena-tetrahedrite and late, mainly carbonate assemblage. Surface listwanite breccia contain quartz phenocrysts deposited from a homogeneous fluid with a medium salinity (8–10 wt.% NaCl equiv.) and high temperatures (T_h = 295–315 °C), whereas the early and main stage of a surface listwanite breccia cement precipitated from a boiling fluid of decreasing salinity and temperature. Aqueous ± CO₂, high salinity (16 to 18 wt.% NaCl equiv.), low temperature (120 °C), homogeneously trapped fluid that precipitated late stage carbonates, is most likely a remnant of boiled off fluid. The epithermal assemblage of the surface listwanites precipitated at a paleodepth of 0.4 to 0.6 km.The δ¹³C values of the late stage ankerite range from − 4.2 to 4.1‰, whereas δ¹⁸O range from 9.6 to 17.5‰. The calculated δ¹⁸O of fluid that precipitated carbonates within epithermal veins, and listwanite breccia cement range from 6.3 to 11.3‰, indicating a contribution of magmatic water.Deposition of all mineralization types was initiated by neutralization of primary acidic magmatic fluid by water-rock reactions that caused widespread propylitization and sericitization. Extensive and long-lasting boiling combined with dilution by meteoric water increased the pH towards the final stage of hydrothermal activity.     

Evidence of fluid inclusions for two stages of fluid boiling in the formation of the giant Shapinggou porphyry Mo deposit,Dabie Orogen,Central China

The Shapinggou porphyry Mo deposit, one of the largest Mo deposits in Asia, is located in the Dabie Orogen, Central China. Hydrothermal alteration and mineralization at Shapinggou can be divided into four stages, i.e., stage 1 ore-barren quartz veins with intense silicification, followed by stage 2 quartz-molybdenite veins associated with potassic alteration, stage 3 quartz-polymetallic sulfide veins related to phyllic alteration, and stage 4 ore-barren quartz ± calcite ± pyrite veins with weak propylitization. Hydrothermal quartz mainly contains three types of fluid inclusions, namely, two-phase liquid-rich (type I), two- or three-phase gas-rich CO₂-bearing (type II) and halite-bearing (type III) inclusions. The last two types of fluid inclusions are absent in stages 1 and 4. Type I inclusions in the silicic zone (stage 1) display homogenization temperatures of 340 to 550 °C, with salinities of 7.9–16.9 wt.% NaCl equivalent. Type II and coexisting type III inclusions in the potassic zone (stage 2), which hosts the main Mo orebodies, have homogenization temperatures of 240–440 °C and 240–450 °C, with salinities of 34.1–50.9 and 0.1–7.4 wt.% NaCl equivalent, respectively. Type II and coexisting type III inclusions in the phyllic zone (stage 3) display homogenization temperatures of 250–345 °C and 220–315 °C, with salinities of 0.2–6.5 and 32.9–39.3 wt.% NaCl equivalent, respectively. Type I inclusions in the propylitization zone (stage 4) display homogenization temperatures of 170 to 330 °C, with salinities lower than 6.5 wt.% NaCl equivalent. The abundant CO₂-rich and coexisting halite-bearing fluid inclusion assemblages in the potassic and phyllic zones highlight the significance of intensive fluid boiling of a NaCl–CO₂–H₂O system in deep environments (up to 2.3 kbar) for giant porphyry Mo mineralization. Hydrogen and oxygen isotopic compositions indicate that ore-fluids were gradually evolved from magmatic to meteoric in origin. Sulfur and lead isotopes suggest that the ore-forming materials at Shapinggou are magmatic in origin. Re–Os dating of molybdenite gives a well-defined ¹⁸⁷Re/¹⁸⁷Os isochron with an age of 112.7 ± 1.8 Ma, suggesting a post-collisional setting.     

Crystallization conditions of peraluminous charnockites: constraints from mineral thermometry and thermodynamic modelling

Most igneous charnockites are interpreted to have crystallized at hot and dry conditions, i.e. at >800?°C and <3 wt.% H₂O and with an important CO₂ component in the system. These charnockites are metaluminous to weakly peraluminous and their formation involves a significant mantle-derived component. This study, in contrast, investigates the crystallization conditions of strongly peraluminous, metasediment-sourced charnockites from the Qinzhou Bay Granitic Complex, South China. To constrain the temperature-melt H₂O crystallization paths for the studied peraluminous charnockites, petrographic characterization was combined with fluid inclusion compositional data, mineral thermometry, and thermodynamic modelling. The uncertainties of the thermodynamic modelling in reconstructing the crystallization conditions of the granitic magmas have been evaluated by comparison between modelled and experimental phase relations for a moderately evolved, peraluminous granite (~70 wt.% SiO₂). The comparison suggests that the modelling reproduces the experimentally derived phase saturation boundaries with uncertainties of 20–60?°C and 0.5–1 wt.% H₂O for systems with ≤1–2 wt.% initial melt H₂O at ~0.2 GPa. For the investigated natural systems, the thermometric estimates and modelling indicate that orthopyroxene crystallized at relatively low temperature (750–790?±?30?°C) and moderately high to high melt H₂O content (3.5–5.6?±?0.5 wt.%). The charnockites finally solidified at relatively “cold” and “wet” conditions. This suggests that thermodynamic modelling affords a possible approach to constrain charnockite crystallization as tested here for peraluminous, moderately low pressure (≤0.3 GPa), and overall H₂O-poor systems (≤1–2 wt.% H₂O total), but yields results with increasing uncertainty for high-pressure or H₂O-rich granitic systems.     

Metamorphosed Pb–Zn–(Ag) ores of the Keketale VMS deposit,NW China: Evidence from ore textures,fluid inclusions,geochronology and pyrite compositions

The Keketale Pb–Zn deposit is located in the Devonian volcanic-sedimentary Maizi basin of the Altay orogenic belt. The mineralization at Keketale is hosted in marbles and deformed volcanic tuffs and biotite–garnet–chlorite schists, folded into a series of overturned synclines formed in multiple deformation events. Keketale contains economic amounts of Pb (0.89 Mt @ 1.51 wt.%), Zn (1.94 Mt @ 3.16 wt.%) and Ag (650 t @ 40 g/t).Detailed petrographic studies have defined two main generations of sulfide development. The banded pyrite of the early Stage A is commonly stratiform, with minor galena, sphalerite and chalcopyrite. Stage B is characterized by a large amount of polymetallic sulfides including pyrrhotite, chalcopyrite, sphalerite and galena, with minor pyrite hosted in quartz veins.Three types of fluid inclusions (FIs), including mixed carbonic-aqueous (C-type), pure carbonic (PC-type) and aqueous (W-type), have been recognized in quartz of stage B. The C-type FIs have homogenization temperatures of 150–326 °C and salinities of 0.2–16.6 wt.% NaCl equivalent. The PC-type FIs are dominated by CO₂ with minor CH₄ and N₂ and have initial ice-melting temperatures of − 57.5 to − 56.7 °C, CO₂ homogenization temperatures of 11–14.1 °C. The W-type primary FIs were completely homogenized at temperatures of 124–359 °C with salinities of 5.0–14.6 wt.% NaCl equivalent. Such CO₂-rich fluid inclusions are consistent with those discovered in orogenic-type deposits in the Altay area and elsewhere.Muscovite separates from the polymetallic quartz veinlets of stage B yield a well-defined ⁴⁰Ar/³⁹Ar isotopic plateau age of 259.33 ± 2.56 Ma, with an isochron age of 259.62 ± 2.65 Ma. This age is coeval with the closure of the Paleo-Asia Ocean and reactivation of the Ertix Fault system.LA-ICP-MS analyses of two generations of pyrite indicate that the banded pyrite of stage A is relatively depleted in metallic elements and contains low contents of Cu (0.39 ppm), Ag (0.20 ppm), Au (below the detection limits), Pb (17.43 ppm) and Zn (14.38 ppm); whereas the pyrite in quartz–polymetallic sulfide veinlets of the stage B is relatively rich in metallic elements, e.g., Cu (2.56 ppm), Ag (3.07 ppm), Au (0.01 ppm), Pb (1047 ppm) and Zn (1136 ppm). The trace amounts of Cu, Pb, Zn, Au and Ag are interpreted to have been initially locked in the lattice of type-A pyrite, and then liberated and precipitated as micromineral inclusions with type-B pyrite during subsequent metamorphism and deformation.Two key factors are considered vital to the formation of economic ores of the Keketale Pb–Zn deposit, namely the original Devonian banded pyrite formed in a VMS system and subsequent Permian deformation and metamorphic processes that liberated Cu, Pb, Zn, Au and Ag from the lattice of type-A pyrite to form galena, sphalerite and chalcopyrite with minor muscovite in quartz veinlets. The model provides a new interpretation of VMS Pb–Zn deposit occurring in back-arc basin environments followed by collision, and new insights into the unique regional Fe–Cu–Pb–Zn–Au mineralization in the Altay orogenic belt.     

Field geology,geochronology and geochemistry of mafic–ultramafic rocks from Alxa,China: Implications for Late Permian accretionary tectonics in the southern Altaids

The time of termination of orogenesis for the southern Altaids has been controversial. Systematic investigations of field geology, geochronology and geochemistry on newly discriminated mafic–ultramafic rocks from northern Alxa in the southern Altaids were conducted to address the termination problem. The mafic–ultramafic rocks are located in the Bijiertai, Honggueryulin, and Qinggele areas, stretching from west to east for about 100 km. All rocks occur high-grade gneisses as tectonic lenses that are composed of peridotite, pyroxenite, gabbro, and serpentinite, most of which have undergone pronounced alteration, i.e., serpentinization and chloritization. Geochemically, the rocks are characterized by uniform compositional trends, i.e., with low SiO₂-contents (42.51–52.21 wt.%) and alkalinity (Na₂O + K₂O) (0.01–5.45 wt.%, mostly less than 0.8 wt.%), and enrichments in MgO (7.37–43.36 wt.%), with Mg# = 52.75–91.87. As the rocks have been strongly altered and have a wide range of loss-on-ignition (LOI: 0.44–14.07 wt.%) values, they may have been subjected to considerable alteration by either seawater or metamorphic fluids. The REE and trace element patterns show a relatively fractionated trend with LILE enrichment and HFSE depletion, similar to that of T-MORB between N-MORB and E-MORB, indicating that the parental melt resulted from the partial melting of oceanic lithospheric mantle overprinted by fluid alteration of island-arc origin. The ultramafic rocks are relics derived from the magma after a large degree of partial melting of oceanic lithospheric mantle with superposed island arc processes under the influence of mid-ocean-ridge magmatism. LA-ICP MS U–Pb zircon ages of gabbros from three spots are 274 ± 3 Ma (MSWD = 0.35), 306 ± 3 Ma (MSWD = 0.49), 262 ± 5 Ma (MSWD = 1.2), respectively, representing the formation ages of the mafic–ultramafic rocks. Therefore, considering other previously published data, we suggest that the mafic–ultramafic rocks were products of south-dipping subduction, most probably with a slab window caused by ridge subduction, of the Paleo-Asian Ocean plate beneath the Alxa block in the Late Carboniferous to Late Permian before the Ocean completely closed. This sheds light on the controversial tectonic history of the southern Altaids and supports the concept that the termination of orogenesis was in the end-Permian to Triassic.     

Geochemistry,and zircon U–Pb and molybdenite Re–Os geochronology of Jilongshan Cu–Au deposit,southeastern Hubei Province,China

The Jilongshan skarn Cu–Au deposit is located at the Jiurui ore cluster region in the southwestern part of the Middle–Lower Yangtze River valley metallogenic belt. The region is characterized by NW‐, NNW‐ and EW‐trending faults and the mineralization occurs at the contact of lower Triassic carbonate rocks and Jurassic granodiorite porphyry intrusions. The intrusives are characterized by SiO₂, K₂O, and Na₂O concentrations ranging from 61.66 to 67.8 wt.%, 3.29 to 5.65 wt.%, and 2.83 to 3.9 wt.%, respectively. Their A/CNK (A/CNK = n(Al₂O₃)/[n(CaO) + n(Na₂O) + n(K₂O)]) ratio, δEu, and δCe vary from 0.77 to 1.17, 0.86 to 1, and 0.88 to 0.96, respectively. The rocks show enrichment in light rare earth elements ((La/Yb)_N = 7.61–12.94) and large ion lithophile elements (LILE), and depletion in high field strength elements (HFSE), such as Zr, Ti. They also display a peraluminous, high‐K calc‐alkaline signature typical of intrusives associated with skarn and porphyry Cu–Au–Mo polymetallic deposits. Laser ablation inductively coupled plasma spectrometry (LA‐ICP‐MS) zircon U–Pb age indicates that the granodiorite porphyry formed at 151.75 ± 0.70 Ma. A few inherited zircons with older ages (677 ± 10 Ma, 848 ± 11 Ma, 2645 ± 38 Ma, and 3411 ± 36 Ma) suggest the existence of an Archaean basement beneath the Middle–Lower Yangtze River region. The temperature of crystallization of the porphyry estimated from zircon thermometer ranges from 744.3 °C to 751.5 °C, and 634.04 °C to 823.8 °C. Molybdenite Re–Os dating shows that the Jilongshan deposit formed at 150.79 ± 0.82 Ma. The metallogeny and magmatism are correlated to mantle–crust interaction, associated with the subduction of the Pacific Plate from the east. Copyright © 2013 John Wiley & Sons, Ltd.     

Geochemical,Sr–Nd–Pb isotope,and zircon U–Pb geochronological constraints on the origin of Early Permian mafic dikes,northern North China Craton

Dolerite dike swarms are widespread across the North China Craton (NCC) of Hebei Province (China) and Inner Mongolia. Here, we report new geochemical, Sr–Nd–Pb isotope, and U–Pb zircon ages for representative samples of these dikes. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U–Pb analysis yielded consistent Permian ages of 274.8 ± 2.9 and 275.0 ± 4.5 Ma for zircons extracted from two dikes. The dolerites have highly variable compositions (SiO₂ = 46.99–56.18 wt.%, TiO₂ = 1.27–2.39 wt.%, Al₂O₃ = 14.42–16.20 wt.%, MgO = 5.18–7.75 wt.%, Fe₂O₃ = 8.03–13.52 wt.%, CaO = 5.18–9.75 wt.%, Na₂O = 2.46–3.79 wt.%, K₂O = 0.26–2.35 wt.%, and P₂O₅ = 0.18–0.37 wt.%) and are light rare earth element (LREE) and large ion lithophile element (LILE, e.g. Rb, Ba, and K, and Pb in sample SXG1-9) enriched, and Th and high field strength element (HFSE, e.g. Nb and Ta in sample SXG1-9, and Ti) depleted. The mafic dikes have relatively uniform (⁸⁷Sr/⁸⁶Sr)_i values from 0.7031 to 0.7048, (²⁰⁶Pb/²⁰⁴Pb)_i from 17.77 to 17.976, (²⁰⁷Pb/²⁰⁴Pb)_i from 15.50 to 15.52, (²⁰⁸Pb/²⁰⁴Pb)_i from 37.95 to 38.03, and positive ?_Nd(t) (3.6–7.3), and variable neodymium model ages (T_DM1 = 0.75–0.99 Ga, T_DM2 = 0.34–0.74 Ga). These data suggest that the dike magmas were derived from partial melting of a depleted region of the asthenospheric mantle, and that they fractionated olivine, pyroxene, plagioclase, K-feldspar, and Ti-bearing phases without undergoing significant crustal contamination. These mafic dikes within the NCC formed during a period of crustal thinning in response to extension after Permian collision between the NCC and the Siberian Block.     

Geology and genesis of the post-collisional porphyry–skarn deposit at Bangpu,Tibet

Bangpu deposit in Tibet is a large but poorly studied Mo-rich (~ 0.089 wt.%), and Cu-poor (~ 0.32 wt.%) porphyry deposit that formed in a post-collisional tectonic setting. The deposit is located in the Gangdese porphyry copper belt (GPCB), and formed at the same time (~ 15.32 Ma) as other deposits within the belt (12 ~ 18 Ma), although it is located further to the north and has a different ore assemblage (Mo–Pb–Zn–Cu) compared to other porphyry deposits (Cu–Mo) in this belt. Two distinct mineralization events have been identified in the Bangpu deposit which are porphyry Mo–(Cu) and skarn Pb–Zn mineralization. Porphyry Mo–(Cu) mineralization in the deposit is generally associated with a mid-Miocene porphyritic monzogranite rock, whereas skarn Pb–Zn mineralization is hosted by lower Permian limestone–clastic sequences. Coprecipitated pyrite and sphalerite from the Bangpu skarn yield a Rb–Sr isochron age of 13.9 ± 0.9 Ma. In addition, the account of garnet decreases and the account of both calcite and other carbonate minerals increases with distance from the porphyritic monzogranite, suggesting that the two distinct phases of mineralization in this deposit are part of the same metallogenic event.Four main magmatic units are associated with the Bangpu deposit, namely a Paleogene biotite monzogranite, and Miocene porphyritic monzogranite, diabase, and fine-grained diorite units. These units have zircon U–Pb ages of 62.24 ± 0.32, 14.63 ± 0.25, 14.46 ± 0.38, and 13.24 ± 0.04 Ma, respectively. Zircons from porphyritic monzogranite yield ε_Hf(t) values of 2.2–8.7, with an average of 5.4, whereas the associated diabase has a similar ε_Hf(t) value averaging at 4.7. The geochemistry of the Miocene intrusions at Bangpu suggests that they were derived from different sources. The porphyritic monzogranite has relatively higher heavy rare earth element (HREE) concentrations than do other ore-bearing porphyries in the GPCB and plots closer to the amphibolite lithofacies field in Y–Zr/Sm and Y–Sm/Yb diagrams. The Bangpu diabase contains high contents of MgO (> 7.92 wt.%), FeOt (> 8.03 wt.%) but low K₂O (< 0.22 wt.%) contents and with little fractionation of the rare earth elements (REEs), yielding shallow slopes on chondrite-normalized variation diagrams. These data indicate that the mineralized porphyritic monzogranite was generated by partial melting of a thickened ancient lower crust with some mantle components, whereas the diabase intrusion was directly derived from melting of upwelling asthenospheric mantle. An ancient lower crustal source for ore-forming porphyritic monzogranite explains why the Bangpu deposit is Mo-rich and Cu-poor rather than the Cu–Mo association in other porphyry deposits in the GPCB because Mo is dominantly from the ancient crust.The Bangpu deposit has alteration zonation, ranging from an inner zone of biotite alteration through silicified and phyllic alteration zones to an outer propylitic alteration zone, similar to typical porphyry deposits. Some distinct differences are also present, for example, K-feldspar alteration at Bangpu is so dispersed that a distinct zone of K-feldspar alteration has not been identified. Hypogene mineralization at Bangpu is characterized by the early-stage precipitation of chalcopyrite during biotite alteration and the late-stage deposition of molybdenite during silicification. Fluid inclusion microthermometry indicates a change in ore-forming fluids from high-temperature (320 °C–550 °C) and high-salinity (17 wt.%–67.2 wt.%) fluids to low-temperature (213 °C–450 °C) and low-salinity (7.3 wt.%–11.6 wt.%) fluids. The deposit has lower δD_V-SMOW (− 107.1‰ to − 185.8‰) values compared with other porphyry deposits in the GPCB, suggesting that the Bangpu deposit formed in a shallower setting and is associated with a more open system than is the case for other deposits in this belt. Sulfides at Bangpu yield δ³⁴S_V-CDT values of − 2.3‰ to 0.3‰, indicative of mantle-derived S implying that coeval mantle-derived mafic magma (e.g., diabase) simultaneously supplied S and Cu to the porphyry system at Bangpu. In comparison, the Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.79–19.28, ²⁰⁷Pb/²⁰⁴Pb = 15.64–15.93, ²⁰⁸Pb/²⁰⁴Pb = 39.16–40.45) of sulfides show that other metals (e.g., Mo, Pb, Zn) were likely derived mainly from an ancient crustal source. Therefore, the formation of the Bangpu deposit can be explained by a two-stage model involving (1) the partial melting of an ancient lower crust triggered by invasion of asthenospheric mantle-derived mafic melts that provide heat and metal Cu and (2) the formation of the Bangpu porphyry Mo–Cu system, formed by magmatic differentiation in the overriding crust in a post-collisional setting.     

Origin of siderite mineralisation in Petrova and Trgovska Gora Mts., NW Dinarides

The Petrova and Trgovska Gora Mts. (Gora=Mountain) are Variscan basement units incorporated into the northwestern Dinarides during the Alpine orogeny. They host numerous siderite-quartz-polysulphide, siderite-chalcopyrite, siderite-galena and barite veins, as well as stratabound hydrothermal-replacement ankerite bodies within carbonates in non-metamorphosed, flysch-like Permo-Carboniferous sequences. The deposits have been mined for Cu, Pb, Ag and Fe ores since Medieval times. Fluid inclusion studies of quartz from siderite-polysulphide-quartz and barite veins of both regions have shown the presence of primary aqueous NaCl?CaCl₂±MgCl₂?H₂O±CO₂ inclusions. The quartz-sulphide stage of both regions show variable salinities; 2.7–26.2 wt% NaCl eq. for the Trgovska Gora region and 3.4–23.4 wt% NaCl eq. for the Petrova gora region, and similar homogenisation temperatures (100–230°C). Finally, barite is precipitated from low salinity-low temperature solutions (3.7–15.8 wt % NaCl equ. and 115–145°C). P-t conditions estimated via isochore construction yield formation temperatures between 180–250°C for the quartz-sulphide stage and 160–180°C for the barite stage, using a maximum lithostatic pressure of 1 kbar (cc. 3 km of overburden). The sulphur isotope composition of barite from both deposits indicates the involvement of Permian seawater in ore fluids. This is supported by the elevated bromium content of the fluid inclusion leachates (120–660 ppm in quartz, 420–960 ppm in barite) with respect to the seawater, indicating evaporated seawater as the major portion of the ore-forming fluids. Variable sulphur isotope compositions of galena, pyrite and chalcopyrite, between ?3.2 and +2.7‰, are interpreted as a product of incomplete thermal reduction of the Permian marine sulphate mixed with organically- and pyrite-bound sulphur from the host sedimentary rocks. Ore-forming fluids are interpreted as deep-circulating fluids derived primarily from evaporated Permian seawater and later modified by interaction with the Variscan basement rocks. ⁴⁰Ar/³⁹Ar data of the detrital mica from the host rocks yielded the Variscan age overprinted by an Early Permian tectonothermal event dated at 266–274 Ma. These ages are interpreted as those reflecting hydrothermal activity correlated with an incipient intracontinental rifting in the Tethyan domain. Nevertheless, 75 Ma recorded at a fine-grained sericite sample from the alteration zone is interpreted as a result of later resetting of white mica during Campanian opening/closure of the Sava back arc in the neighbouring Sava suture zone (Ustaszewski et al. 2008).     

Sediment recycling and crustal growth in the Central Asian Orogenic Belt: Evidence from Sr–Nd–Hf isotopes and trace elements in granitoids of the Chinese Altay

Felsic igneous rocks are common constituents of volcanic arcs, and contain valuable information about subduction-related magmatism. In this study we investigate nine granitoids with S-type volcanic arc affinity from the Chinese Altay, emplaced from 507 to 391 Ma in an active subduction zone during the early–middle Paleozoic. These granitoids are characterized by moderate to high SiO₂ contents (61.01–75.30 wt.%), moderate total alkalis (Na₂O + K₂O, 3.43–7.64 wt.%), and high Al₂O₃ contents (13.29–17.18 wt.%). Negative εNd(t) values (− 6.1 to − 1.0), the wide range of εHf(t) values (− 7.0 to + 9.0), and enrichment of LILEs such as Pb, Th and U, all suggest that the granitoids were probably derived from the partial melting of subducting oceanic sediments and the associated mantle wedge. This inference is further supported by the Nd-isotope data. The high initial ⁸⁷Sr/⁸⁶Sr ratios (0.703963–0.719428), low Ba/Th ratios (7.00–118.93), and uniformly negative εNd(t) values (− 6.1 to − 1.0) indicate that slab-derived aqueous fluids were vital in generating the initial magma of these granitoids, and assimilation played only a minor role. Our data demonstrate that residual zircon retains a substantial amount of Hf during the partial melting of oceanic sediments, therefore, Hf may not be an effective tracer for the input of recycled sediments. We conclude that sediment recycling played an important role in the generation of arc magmatism and the growth of the Central Asian Orogenic Belt (CAOB).