The volcanic succession of Baoligaomiao,central Inner Mongolia: Evidence for Carboniferous continental arc in the central Asian orogenic belt

The Baoligaomiao Formation, within the Hegenshan ophiolite-arc-accretion complex is an important segment to understand the tectonic evolution of the Central Asian Orogenic Belt (CAOB), world's largest Phanerozoic orogenic belt. In this study, we present an integrated study of zircon U-Pb isotopic ages, whole rock major-trace elements, and Sr-Nd-Pb isotopic data from the volcanic succession in the Baoligaomiao Formation. The volcanic succession can be divided into the lower sequence with zircon U-Pb ages in the range of 326.3 Ma–307.4 Ma and the upper sequence of 305.3 Ma. The succession belongs to two suites: calc-alkaline volcanics and high-Si rhyolites. The calc-alkaline volcanic rocks include basaltic andesite through andesite and dacite to rhyolite and their pyroclastic equivalents. These rocks exhibit a well-defined compositional trend from basaltic to rhyolitic magma, reflecting continuous fractional crystallization. These rocks show obvious enrichment in LILEs and LREEs and relative depletion of HFSEs, typical of subduction-related magma. The calc-alkaline rocks have low initial ⁸⁷Sr/⁸⁶Sr (0.7023–0.7052), positive ɛNd(t) values (2.75–4.80), and their initial Pb isotopic compositions are 17.875–18.485 of ²⁰⁶Pb/²⁰⁴Pb, 15.481–15.520 of ²⁰⁷Pb/²⁰⁴Pb and 37.467–37.764 of ²⁰⁸Pb/²⁰⁴Pb, respectively. Geochemical and isotopic results suggest that the volcanic succession represents Carboniferous subduction-related, mature, continental arc volcanism. The outcrops of high-Si rhyolites are restricted to the northern edge of the continental arc, marking a transition zone between volcanic arc and back-arc basin, where they are interbedded with the calc-alkaline rocks in the lower sequence, and the upper sequence is composed only of high-Si rhyolites. The high-Si rhyolites have high SiO₂ (71.12–81.76 wt%) and varied total alkali contents (K₂O + Na₂O = 5.46–10.58 wt%), low TiO₂ (0.06–0.27 wt%), MgO (0.09–0.89 wt%) and CaO (0.08–0.72 wt%). Based on the presence of mafic alkali phenocrysts, such as arfvedsonite and siderophyllite, high Zr/Nb ratios (> 10) and peralkalinity index (PI) near unity, the high-Si rhyolites can be classified as peralkaline comendites. The high-Si rhyolites are characterized by unusually low Sr and Ba, and high abundance of Zr, Th, Nb, HREEs and Y. They show geochemical characteristics similar to those of typical A₂-type granites including their high K₂O + Na₂O, Nb, Zr and Y, and high ratios of FeO^T/MgO, Ga/Al and Y/Nb. Our study suggests that the high-Si rhyolites were derived from discrete trachytic parent magma with fractional crystallization within shallow magma reservoirs. Their Nd-Pb isotopic characteristics are similar to those of the calc-alkaline arc rocks and are compatible with partial melting of pre-existing juvenile continental arc crust. We observe that the widespread eruptions of A₂-rhyolitic magmas (305.3 Ma–303.4 Ma) following a short period of magmatic quiescence was temporally and spatially associated with voluminous intrusion of the bimodal magmas (304.3 Ma–299.3 Ma) in the pre-existing arc volcanic-plutonic belt (329 Ma–307 Ma). We envisage northward subduction and slab breakoff process resulting in an obvious change of the regional stress field to extensional setting within the Carboniferous continental arc running E-W for thousands of kilometers. Therefore, we propose the existence of an east-west-trending Carboniferous continental arc in the Hegenshan ophiolite-arc-accretion complex, with the slab breakoff event suggesting that the age of the upper sequence (305.3 ± 5.5 Ma) likely indicates the maximum age for the cessation of the northward subduction of the Hegenshan oceanic lithosphere.     

Fluorite solubility in hydrous haplogranitic melts at 100 MPa

Fluorite is the most common fluoride mineral in magmatic silicic systems and its crystallization can moderate or buffer fluorine concentrations in these settings. We have experimentally determined fluorite solubility and speciation mechanisms in haplogranitic melts at 800–950 °C, 100 MPa and aqueous-fluid saturation. The starting haplogranite compositions: peraluminous (alumina saturation index, ASI = 1.2), subaluminous (ASI = 1.0) and peralkaline (ASI = 0.8) were variably doped with CaO or F₂O₋₁ in the form of stoichiometric mineral or glass mixtures. The solubility of fluorite along the fluorite–hydrous haplogranite binaries is low: 1.054 ± 0.085 wt.% CaF₂ (peralkaline), 0.822 ± 0.076 wt.% (subaluminous) and 1.92 ± 0.15 wt.% (peraluminous) at 800 °C, 100 MPa and 10 wt.% H₂O, and exhibits a minimum at ASI ∼ 1. Fluorite saturation isotherms are strongly hyperbolic in the CaO–F₂O₋₁ space, suggesting that fluorite saturation is controlled by the activity product of CaO and F₂O₋₁, i.e., these components are partially decoupled in the melt structure. The form of fluorite liquidus isotherms implies distinct roles of fluorite crystallization: in Ca-dominant systems, fluorite crystallization is controlled by the fluorine concentration in the melt only and remains nearly independent of calcium contents; in F-rich systems, the crystallization of fluorite is determined by CaO contents and it does not buffer fluorine concentration in the melt. The apparent equilibrium constant, K, for the equilibrium CaO + cF₂O₋₁ = CaF₂ (+ associates) is log K= − (2.449 ± 0.085)·Al₂O₃^exc + (4.902 ± 0.066); the reaction-stoichiometry parameter varies as follows: c= − (0.92 ± 0.11)·Al₂O₃^exc + (1.042 ± 0.084) at 800 °C, 100 MPa and fluid saturation where Al₂O₃^exc are molar percent alumina in excess over alkali oxides. The reaction stoichiometry, c, changes at subaluminous composition: in peralkaline melts, competition of other network modifiers for excess fluorine anions leads to the preferential alkali–F short-range order, whereas in peraluminous compositions, excess alumina associates with calcium cations to form calcioaluminate tetrahedra. The temperature dependence of fluorite solubility is described by the binary symmetric Margules parameter, W = 36.0 ± 1.4 kJ (peralkaline), 39.7 ± 0.5 kJ (subaluminous) and 32.8 ± 0.7 kJ (peraluminous). The strong positive deviations from ideal mixing imply the occurrence of CaF₂–granite liquid–liquid immiscibility at temperatures above 1258 °C, which is consistent with previous experimental data. These experimental results suggest very low solubilities of fluorite in Ca-rich melts, consistent with the lack of fluorine enrichment in peralkaline rhyolites and calc-alkaline batholiths. On the other hand, high CaO concentrations necessary to crystallize fluorite in F-rich peraluminous melts are not observed in nature and thus magmatic crystallization of fluorite in topaz-bearing silicic suites is suppressed. A procedure for calculating fluorite solubility and the liquidus isotherms for a whole-rock composition and temperature of interest is provided.     

Rapid development of the great Millennium eruption of Changbaishan (Tianchi) Volcano,China/North Korea: Evidence from U–Th zircon dating

The Changbaishan (Tianchi) volcano extending across the border of northeast China and North Korea erupted ~ 100 km³ peralkaline rhyolites around 1000 AD. This Millennium eruption of the Changbaishan volcano is one of the two largest explosive eruptions in the past 2000 years. Here we report the results of uranium–thorium dating of zircons from the Changbaishan volcanic rocks. Our data indicate that the rhyolitic magmas were stored in the crust for only 8.2 ± 1.2 ka prior to eruption. Based on titanium-in-zircon geothermometer and alkali feldspar-glass geothermometer, the rhyolitic magmas were formed at a relatively low temperature (~ 740 ± 40 °C). This storage time is very short compared with other large volume catastrophic silicic eruptions. This work demonstrates that peralkaline rhyolitic magmas from the Changbaishan volcano can develop into a catastrophic eruptive phase quite quickly.     

Petrology,geochemistry, and geochronology of Paleoproterozoic volcanic and granitic rocks (1.89–1.88 Ga) of the Pitinga Province,Amazonian Craton,Brazil

This paper presents geochemical, petrographic, and geochronological data on the Uatumã magmatism in the Pitinga Province, where it is represented by volcanic rocks from the Iricoumé Group and granitic rocks from the Mapuera Suite. The Iricoumé Group (1.89–1.88 Ga) is constituted of the Divisor Formation (intermediate volcanic rocks), Ouro Preto Formation (acid effusive rocks), and Paraiso Formation (acid crystal-rich ignimbrites, surge deposits, and basic rocks). The volcanic sequence is intruded by granitoids from the Mapuera Suite (1.88 Ga), mainly represented by monzogranites and syenogranites. Structural and field relations suggest that caldera complex collapse controlled the emplacement of volcanics and granitoids of the Mapuera Suite. Subsequent structure reactivations allowed the younger Madeira Suite (1.82–1.81 Ga) to be emplaced in the central portion of the caldera complex. The felsic Iricoumé magmatism is mainly composed of rhyolites, trachydacites and latites, with SiO₂ contents between 64 wt% and 80 wt%. The plutonic rocks from the Mapuera Suite present SiO₂ between 65 wt% and 77 wt%. Volcanic and granitic rocks present identical geochemical characteristics and that is attributed to their co-magmatic character. The felsic volcanic rocks and granites are metaluminous to slightly peraluminous and show affinity with silica-saturated alkaline series or with A-type magmas. They have Na₂O + K₂O between 6.6% and 10.4%, FeO^t/(FeO^t + MgO) varying between 0.76 and 0.99, Ga/Al ratios between 1.5 and 4.9, like typical A-type rocks; and plot in the within-plate or post-collisional fields in the (Nb + Y) vs. Rb diagram. The Nb/Y ratios indicate that these rocks are comparable to A2-type granites. This magmatism can be related to the (i) potassic alkaline series, with low Sr content in the felsic rocks explained by plagioclase fractionation at low pressure and high temperature or, alternatively, (ii) a bimodal association where magma had high crustal influence. The similarity of the Iricoumé felsic magmatism with A2-type granitoids and their high ETRL/Nb ratios suggest its relation with mantle sources previously modified by subduction, probably in a post-collision environment. Alternatively, this can be interpreted as bimodal within-plate magmatism with contamination by crustal melts. In this context, the extreme F, Nb and Zr enrichment of Madeira Suite could be explained by the presence of a thin crust which favored the presence and continuity of convective systems in the upper mantle.     

Mineral chemistry and zircon geochronology of xenocrysts and altered mantle and crustal xenoliths from the Aries micaceous kimberlite: Constraints on the composition and age of the central Kimberley Craton,Western Australia

The Neoproterozoic (∼ 820 Ma) Aries micaceous kimberlite intrudes the central Kimberley Basin, northern Western Australia, and has yielded a suite of 27 serpentinised ultramafic xenoliths, including spinel-bearing and rare, metasomatised, phlogopite–biotite and rutile-bearing types, along with minor granite xenoliths. Proton-microprobe trace-element analysis of pyrope and chromian spinel grains derived from heavy mineral concentrates from the kimberlite has been used to define a ∼ 35–40 mW/m² Proterozoic geotherm for the central Kimberley Craton. Lherzolitic chromian pyrope highly depleted in Zr and Y, and Cr-rich magnesiochromite xenocrysts (class 1), probably were derived from depleted garnet peridotite mantle at ∼ 150 km depth. Sampling of shallower levels of the lithospheric mantle by kimberlite magmas in the north and north-extension lobes entrained high-Fe chromite xenocrysts (class 2), and aluminous spinel-bearing xenoliths, where both spinel compositions are anomalously Fe-rich for spinels from mantle xenoliths. This Fe-enrichment may have resulted from Fe–Mg exchange with olivine during slow cooling of the peridotite host rocks. Fine exsolution rods of aluminous spinel in diopside and zircon in rutile grains in spinel- and rutile-bearing serpentinised ultramafic xenoliths, respectively, suggest nearly isobaric cooling of host rocks in the lithospheric mantle, and indicate that at least some aluminous spinel in spinel-facies peridotites formed through exsolution from chromian diopside. Fe–Ti-rich metasomatism in the spinel-facies Kimberley mantle probably produced high-Ti phlogopite–biotite + rutile and Ti, V, Zn, Ni-enriched aluminous spinel ± ilmenite associations in several ultramafic xenoliths. U–Pb SHRIMP ²⁰⁷Pb/²⁰⁶Pb zircon ages for one granite (1851 ± 10 Ma) and two serpentinised ultramafic xenoliths (1845 ± 30 Ma; 1861 ± 31 Ma) indicate that the granitic basement and lower crust beneath the central Kimberley Basin are at least Palaeoproterozoic in age. However, Hf-isotope analyses of the zircons in the ultramafic xenoliths suggest that the underlying lithospheric mantle is at least late Archean in age.     

Mineralogy and petrogenesis of a Ba–Ti–Zr-rich peralkaline dyke from Šebkovice (Czech Republic): Recognition of the most lamproitic Variscan intrusion

A peralkaline, ultrapotassic dyke found at ?ebkovice (T?ebí? district, western Moravia) is a mineralogically extreme member of a dyke swarm occurring along the south-eastern border of the Moldanubian Region of the Bohemian Massif. The dyke shows a simple zoning, with a very fine-grained marginal zone grading into a medium-grained central zone. It has a primary mineral assemblage of microcline and potassic amphiboles, with accessory apatite and altered phlogopite. The microcline exhibits an unusual red luminescence colour and pronounced substitution of Fe³⁺ for Al, with measured contents of Fe₂O₃ up to 8.5 wt.% (0.31 apfu Fe³⁺). Amphiboles have very high K (up to 0.99 apfu) and Si contents; their compositions follow an alkaline fractionation trend from potassic-richterite to potassic-magnesio-arfvedsonite, characterized by an increase of Na/K and a decrease of Ca, Mg, Fe²⁺ and Ti via heterovalent substitutions ^[B]Ca + ^[C](Mg,Fe²⁺) → ^[B]Na + ^[C]Fe³⁺ and Ti + Mg → 2Fe³⁺. The most evolved apatite is significantly enriched in SrO (up to 9.7 wt.%; 0.49 apfu Sr). The core of the dyke and late veinlets contain unique late- to post-magmatic Ba–Ti–Zr-bearing mineral assemblages of baotite, henrymeyerite, titanite, rutile, benitoite and bazirite. Anhedral baotite fills interstices distributed inhomogeneously in the dyke centre; it is locally replaced by a Ba-bearing titanite + henrymeyerite + rutile + quartz assemblage. Henrymeyerite (the second record in a lamproite) shows variable Fe/Ti ratios and represents a solid solution of the hepta- and hexatitanate components. Euhedral crystals of benitoite and bazirite are enclosed in the late-stage quartz–titanite–apatite veinlets in the fine-grained margin of the intrusion. In terms of a mineralogical–genetic classification, the ?ebkovice dyke can be considered as a new high-silica (~ 57 wt.% SiO₂) variety of lamproite (variety ?ebkovice), and represents a unique expression of post-collisional potassic magmatism on the south-eastern border of the Bohemian Massif. The peralkaline dykes from this area show mineralogical and geochemical features similar to those of silica-rich orogenic lamproites emplaced at destructive plate margins. In terms of the modern classification of lamproites, the ?ebkovice dyke is the first lamproite recognised in the Variscan orogenic belt.     

Mafic and silica-rich glasses in mantle xenoliths from Wau-en-Namus,Libya: Textural and geochemical evidence for peridotite–melt reactions

Anhydrous spinel peridotite xenoliths in Quaternary nepheline-basanite and melilite- or sodalite-bearing lavas of the Wau-en-Namus volcano in S Libya range from lherzolites to harzburgites recording melt extraction in a shallow setting (≤ 2 GPa). Primary clinopyroxenes have distinct trace element characteristics documenting LILE (large ion lithophile element) depletion or enrichment events predating the formation of glass pockets and veins in the xenoliths. These glasses are aluminous and alkali-rich, range in composition from ultrabasic to silicic (43–67 wt.% SiO₂) and may contain empty vugs and micro-phenocrysts of olivine, clinopyroxene, spinel, plagioclase, sodalite, apatite that are similar in composition to phenocrysts in the host lavas. Reactions of infiltrating melt and xenolith minerals are documented by diffuse Fe–Ca-rich rims of olivine in contact with glass, and by spongy-textured reaction domains caused by incongruent dissolution of primary pyroxenes and spinel. Some glasses have trace element characteristics similar to that of the host Ne-basanite, suggesting they were derived from the same source during entrainment and transport to the surface. Incompatible element enrichment and Sr–Nd isotopic compositions of the analyzed host lava are similar to HIMU (high μ; μ = ²³⁸Pb/²⁰⁴Pb)-type magmas, but the Pb isotopic composition is less radiogenic compared to other intra-plate Neogene magmatic rocks from N Africa.     

Hydrothermal alteration and Cu–Ni–PGE mobilization in the charnockitic rocks of the footwall of the South Kawishiwi intrusion,Duluth Complex,USA

In the Neoarchean (~ 2.7 Ga) contact metamorphosed charnockitic footwall of the Mesoproterosoic (1.1 Ga) South Kawishiwi intrusion of the Duluth Complex, the primary metamorphic mineral assemblage and Cu–Ni–PGE sulfide mineralization is overprinted by an actinolite + chlorite + cummingtonite + prehnite + pumpellyite + quartz + calcite hydrothermal mineral assemblage along 2–3 cm thick veins. In calcite, hosted by the hydrothermal alteration zones and in a single recrystallized quartz porphyroblast, four different fluid inclusion assemblages are documented; the composition of these fluid inclusions provide p–T conditions of the fluid flow, and helps to define the origin of the fluids and evaluate their role in the remobilization and reprecipitation of the primary metamorphic sulfide assemblage.Pure CO₂ fluid inclusions were found as early inclusions in recrystallized quartz porphyroblast. These inclusions may have been trapped during the recrystallization of the quartz during the contact metamorphism of the footwall charnockite in the footwall of the SKI. The estimated trapping pressure (1.6–2.0 kbar) and temperature (810–920 °C) conditions correspond to estimates based on felsic veins in the basal zones of the South Kawishiwi intrusion.Fluid inclusion assemblages with CO₂–H₂O–NaCl and CH₄–N₂–H₂O–NaCl compositions found in this study along healed microfractures in the recrystallized quartz porphyroblast establish the heterogeneous state of the fluids during entrapment. The estimated trapping pressure and temperature conditions (240–650 bar and 120–150 °C for CO₂–H₂O–NaCl inclusions and 315–360 bar and 145–165 °C for CH₄–N₂–H₂O–NaCl inclusions) are significantly lower than the p–T conditions (> 700 °C and 1.6–2 kbar) during the contact metamorphism, indicating that this fluid flow might not be related to the cooling of the Duluth Complex and its contact aureole. The presence of chalcopyrite inclusions in these fluid inclusions and in the trails of these fluid inclusion assemblages confirms that at least on local scale these fluids played a role in base metal remobilization. No evidences have been observed for PGE remobilization and transport in the samples. The source of the carbonic phase in the carbonic assemblages (CO₂; CH₄) could be the graphite, present in the metasedimentary hornfelsed inclusions in the basal zones of the South Kawishiwi intrusion.The hydrothermal veins in the charnockite can be characterized by an actinolite + cummingtonite + chlorite + prehnite + pumpellyite + calcite (I–II) + quartz mineral assemblage. Chlorite thermometry yields temperatures around 276–308 °C during the earliest phase of the fluid flow. In the late calcite (II) phase, high salinity (21.6–28.8 NaCl + CaCl₂ equiv. wt.%), low temperature (90–160 °C), primary aqueous inclusions were found. Chalcopyrite (± sphalerite ± millerite), replacing and intersecting the early hydrothermal phases, are associated to the late calcite (II) phase. The composition of the formational fluids in the Canadian Shield is comparable with the composition of the studied fluid inclusions. This suggests that the composition of the fluids did not change in the past 2 Ga and base metal remobilization by formational fluids could have taken place any time after the formation of the South Kawishiwi intrusion.Sulfur isotope studies carried out on the primary metamorphic (δ³⁴S = 7.4–8.9‰) and the hydrothermal sulfide mineral assemblage (δ³⁴S = 5.5–5.7‰) proves, that during the hydrothermal fluid flow the primary metamorphic ores were remobilized.     

Fluid origin of fluorite-rich carbonate-hosted Pb–Zn mineralization of the Himalayan–Zagros collisional orogenic system: A case study of the Mohailaheng deposit,Tibetan Plateau,China

A significant belt of carbonate-hosted Pb–Zn mineralization occurs in the Himalayan–Zagros collisional orogenic system. Three differing types of these Pb–Zn deposits within this belt have been identified based on variations in gangue mineral assemblages, leading to the classification of carbonate-, quartz- and fluorite-rich classes of Pb–Zn deposits. The third Pb–Zn mineralization (fluorite-rich) type is common in this orogenic system, but little research has been undertaken on it. Here, we focus on the Mohailaheng deposit, a large-sized fluorite-rich carbonate-hosted Pb–Zn deposit (> 100 Mt Pb + Zn ores with average grade of 2.18%–4.23%); the deposit is located in the Sanjiang Cenozoic thrust-fold belt, an important part of the Himalayan–Zagros collisional orogenic system and an area that formed during the early Tertiary India–Eurasia collision. The main orebodies in this deposit are stratabound and are hosted by Carboniferous limestones that are located along secondary faults associated with a regional thrust fault. The main assemblage is a sphalerite + galena + pyrite sulfide assemblage associated with a calcite + fluorite + barite + quartz + dolomite gangue assemblage. Detailed field and experimental work indicates that the deposit formed during three distinct phases of hydrothermal activity. Studies on fluid inclusion and stable isotopes of gangue minerals indicate that two dominant distinct fluids involving the deposit formation. They include (1) a low-temperature (130–140 °C), high-salinity (23–24 wt.% NaCl equivalent) basinal brine containing Na⁺–K⁺–Mg^2 +–Ca^2 +–Cl⁻ ions and abnormally high SO₄^2 − concentrations, which probably derived from Tertiary basins in the regional district, and (2) a low- to moderate-temperature (170–180 °C) and moderate- to high-salinity (19–20 wt.% NaCl equivalent) metamorphic fluid containing Na⁺–K⁺–Mg^2 +–Cl^––SO₄^2 − ions and abnormally high F⁻ and organic matter concentrations, that probably formed during regional metamorphism. Some evaporated seawaters and meteoric fluids were also identified in mixtures with these two dominant fluids. The Pb–Zn mineralization at Mohailaheng formed during three distinct stages, consistent with the regional tectonic history. The first stage involved the formation of favorable lithological and structural traps at Mohailaheng during regional thrusting, leading to the migration of compressed metamorphic waters at depth along a detachment zone, sequestering metals from sediments within the region. Basinal brines at the surface also began to infiltrate down along the secondary faults, dissolving gypsum from the underlying sediments. The second stage was associated with the cessation of thrusting and the onset of strike-slip movements along these thrust faults. Metamorphic fluids containing high concentrations of halogen ions, organic gases, and metals ascended into the structural traps at Mohailaheng along the reactivated thrust faults, causing fluorite, calcite, and some sulfide precipitation. Then, basinal brines rich in SO₄^2 − quickly descended into the structural traps along the reactivated faults, causing reduction of SO₄^2 − by organic matter, and producing significant amounts of H₂S. The reduced sulfur then reacted with the metals in the fluids, causing significant sulfide precipitation. The third stage was associated with metal-depleted fluids, which only resulted in the precipitation of calcite from the diluted basinal brines. Combining these findings with research results on other fluorite-rich carbonate-hosted Pb–Zn deposits in the Himalayan–Zagros orogenic system suggests that this type of carbonate-hosted Pb–Zn deposits can also be classified as Mississippi Valley-type (MVT) deposits, and that the origin of the fluorite in these deposits may be related to multiple hydrothermal fluids involved in the mineralization evolution.     

Fault controlled Carboniferous A-type magmatism in the proto-Andean foreland (Sierras Pampeanas,Argentina): Geochemical constraints and petrogenesis

The intrusion of granitoids into the Eastern Sierras Pampeanas in the Early Carboniferous took place after a long period of mainly compressional deformation that included the Famatinian (Ordovician) and Achalian (Devonian) orogenies. These granitoids occur as small scattered plutons emplaced in a dominant extensional setting, within older metamorphic and igneous rocks, and many of them are arranged along a reactivated large shear zone. A set of 46 samples from different granitic rocks: Huaco granitic complex, San Blas pluton, and the La Chinchilla stock from the Sierra de Velasco, Zapata granitic complex from Sierra de Zapata, and the Los Árboles pluton from Sierra de Fiambalá, display high and restricted SiO₂ contents between 69.2 and 76.4 wt.%. On both FeO/(FeO + MgO) vs. SiO₂ and [(Na₂O + K₂O) ? CaO] vs. SiO₂ plots the samples plot in the ferroan and alkaline-calcic to calco-alkaline fields (FeO/(FeO + MgO) = 0.88–1.0%;[(Na₂O + K₂O) ? CaO] = 6.3–8.3%), thus showing an A-type granitoid signature. The high concentrations for the High Field Strength Elements (HSFE), such as Y, Nb, Ga, Ta, U, Th, etc. and flat REE patterns showing significant negative Eu anomalies are also typical features of A-type granites. Our petrogenetic model supports progressive fractional crystallization with dominant fractionation of feldspar and a source mineral assemblage enriched in plagioclase. Biotites have distinctive compositions with high FeO/MgO ratios (7.8–61.5), F (360–5610 ppm), and Cl (120–1050 ppm). The FeO/MgO ratios together with the F and Cl content of igneous biotites seem to reflect the nature of their parental host magmas and may be useful in identifying A-type granitoids. The isotopic data (Rb–Sr and Sm–Nd) confirm that the A-type granites represent variable mixtures of asthenospheric mantle and continental crust and different mixtures lead to different subtypes of A-type granite (illustrating the lack of consensus about A-type magma origin). We conclude that prominent shear zones play an important role in providing suitable conduits for ascending asthenospheric material and heat influx in the crust, a hypothesis that is in accord with other recent work on A-type granites.     

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.     

Boron isotopic constraints on the Nb and Ta mineralization of the syenitic dikes in the ~ 260 Ma Emeishan large igneous province (SW China)

Both Nb–Ta-mineralized and Nb–Ta-poor syenitic dikes in the Panxi region (SW China) are spatially and temporally associated with syenitic plutons, which are part of the ~ 260 Ma Emeishan large igneous province. These syenitic dikes are NW-striking, and have width varying from 1 to 5 m and length from 50 to 300 m. The dikes are mainly composed of K-feldspar, albite, aegirine and arfvedsonite, however, mineral modes are different in the Nb–Ta-mineralized and Nb–Ta-poor syenitic dikes. The major Nb–Ta-bearing mineral in the dikes is pyrochlore, which is closely associated with albite and occurs in places with intensive albitization. Rocks of the Nb–Ta-mineralized syenitic dikes contain more albite and less K-feldspar than the Nb–Ta-poor dikes, and have compositions more evolved than the Nb–Ta-poor dikes, indicating that the Nb–Ta-mineralized syenitic dikes formed from a highly evolved magma. We analyzed the B concentrations and B isotopic compositions of the samples of both Nb–Ta-mineralized and Nb–Ta-poor syenitic dikes and associated syenitic pluton using a single column purification method and ICP-AES and MC-ICP-MS techniques. The samples of the Nb–Ta-mineralized syenitic dikes have whole-rock B concentrations ranging from 11.4 to 23.9 ppm and δ¹¹B values from − 17.95 to − 14.54‰, whereas the samples of the Nb–Ta-poor dikes and syenitic plutons have B concentrations varying from 3.32 to 16.5 ppm and δ¹¹B values from − 13.45 to − 10.02‰. The high B concentration of the Nb–Ta-mineralized dikes relative to the Nb–Ta-poor dikes is consistent with that B is incompatible and tends to be rich in more evolved magma. The relatively low δ¹¹B values of the Nb–Ta-mineralized dikes indicate that the B isotopes may have fractionated between fluids and rocks in a transitional, magmatic–hydrothermal stage. We propose that the highly evolved magmas in a transitional, magmatic–hydrothermal stage may have Nb– and Ta–fluorine complexes dissolved in the hydrothermal fluids in the presence of Na⁺. Albite crystallization due to intensive albitization in this stage resulted in the decrease of Na⁺ in the fluids, decomposing the Nb– and Ta–fluorine complexes. The released Nb and Ta from the complexes were then dissolved in the fluids and finally entered the lattice of pyrochlore crystals in the stage of albitization.     

Reduction of buried oxidized oceanic crust during subduction

The relationship among subducted oxidized oceanic crust and oxidation state of the subarc mantle, and arc magmas is one of the important aspects to evaluate convergent margin tectonics. However details of the oxidized mass transferred from buried oceanic crust to the overlying subarc mantle wedge remain obscure. Here we investigate the Songduo eclogites from south Tibet formed by the subduction of the paleo-Tethyan oceanic crust, and identify an abrupt decrease in pyrope and increase in almandine contents from the mantle to rim of garnet grains. This is coupled with a decrease in the Fe^3 + content of epidote and Fe^3 +/(Fe^2 ++ Fe^3 +) ratios from garnet core to rim domains, as well as speciation of calcite, a new mineral phase, in the rock matrix. Minor sulfates occur only as inclusions in garnet core domains, whereas sulfides are confined to the matrix as an accessory mineral phase. Aegirine augite occurs as relics or inclusions in garnet and omphacite. These features clearly suggest that oxidized components, Fe^3 + and S^6 +, were reduced as Fe^2 + and S^2 −, respectively, at the subduction zone. Thermodynamic modeling in the P–T-log₁₀f_O2 space using updated Perplex_X programs further revealed that the Songduo eclogites experienced oxygen fugacity variation of up to 8 log₁₀ units, with decreasing pressure. Petrological observations further suggest that the strong redox processes took place, after breaking of garnet, during the initial exhumation of the eclogites. CO₂ and minor sulfur are subsequently transferred from the cold oceanic subduction zone to the overlying mantle wedge, partially released by arc volcanoes to atmosphere. Our study presents a case of C and S recycling between the Earth's exterior and interior.     

Metamorphic P–T path of mafic granulites from Eastern Hebei: Implications for the Neoarchean tectonics of the Eastern Block,North China Craton

This study documents the metamorphic evolution of mafic granulites from the Eastern Hebei Complex in the Eastern Block of the North China Craton. Mafic granulites from Eastern Hebei occur as boudins or enclaves within Neoarchean high-grade TTG gneisses. Petrographic observations reveal three characteristic metamorphic mineral assemblages in the mafic granulites: the pre-peak hornblende + plagioclase + ilmenite + quartz + sphene assemblage (M₁) existing as mineral inclusions within coarse-grained peak assemblage (M₂) represented by garnet + clinopyroxene + orthopyroxene + plagioclase + hornblende + ilmenite + quartz, and post-peak assemblage (M₃) marked by garnet + quartz ± ilmenite symplectites surrounding the peak pyroxene and plagioclase. Based on pseudosection modeling calculated in the NCFMASHTO model system using the program THERMOCALC, P–T conditions of the pre-peak (M₁), peak (M₂) and post-peak (M₃) assemblages are constrained at 600–715 °C/6.0 kbar or below, 860–900 °C/9.6–10.3 kbar, and 790–810 °C/9.6–10.4 kbar, respectively. These P–T estimates, combined with their mineral compositions and reaction relations, define an anticlockwise P–T path incorporating isobaric cooling subsequent to the peak medium-pressure granulite-facies metamorphism for the mafic granulites from Eastern Hebei. Such an anticlockwise P–T path suggests that the end-Neoarchean metamorphism of the Eastern Hebei Complex correlated closely with underplating and intrusion of voluminous mantle-derived magmas. In conjunction with other geological considerations, a mantle-plume model is favored to interpret the Neoarchean tectonothermal evolution of the Eastern Hebei Complex and other metamorphic complexes in the Eastern Block. The prograde amphibolite-facies metamorphism (M₁) was initiated due to the upwelling of the relatively cooler mantle plume head, followed by the peak medium-pressure granulite-facies metamorphism (M₂) as triggered by the uprising hotter plume “tail”, and finally when plume activity ceased, the heated metamorphic crust experienced nearly isobaric cooling (M₃).     

Petrology of Karoo volcanic rocks in the southern Lebombo monocline,Mozambique

The Karoo volcanic sequence in the southern Lebombo monocline in Mozambique contains different silicic units in the form of pyroclastic rocks, and two different basalt types. The silicic units in the lower part of the Lebombo sequence are formed by a lower unit of dacites and rhyolites (67–80 wt.% SiO₂) with high Ba (990–2500 ppm), Zr (800–1100 ppm) and Y (130–240 ppm), which are part of the Jozini–Mbuluzi Formation, followed by a second unit, interlayered with the Movene basalts, of high-SiO₂ rhyolites (76–78 wt.%; the Sica Beds Formation), with low Sr (19–54 ppm), Zr (340–480 ppm) and Ba (330–850 ppm) plus rare quartz-trachytes (64–66 wt.% SiO₂), with high Nb and Rb contents (240–250 and 370–381 ppm, respectively), and relatively low Zr (450–460 ppm). The mafic rocks found at the top of the sequence are basalts and ferrobasalts belonging to the Movene Formation. The basalts have roughly flat mantle-normalized incompatible element patterns, with abundances of the most incompatible elements not higher than 25 times primitive mantle. The ferrobasalt has TiO₂ ∼ 4.7 wt.%, Fe₂O_3t = 16 wt.%, and high Y (100 ppm), Zr (420 ppm) and Ba (1000 ppm). The Movene basalts have initial (at 180 Ma) ⁸⁷Sr/⁸⁶Sr = 0.7052–0.7054 and ¹⁴³Nd/¹⁴⁴Nd = 0.51232, and the Movene ferrobasalt has even lower ⁸⁷Sr/⁸⁶Sr (0.70377) and higher ¹⁴³Nd/¹⁴⁴Nd (0.51259). The silicic rocks show a modest range of initial Sr-(⁸⁷Sr/⁸⁶Sr = 0.70470–0.70648) and Nd-(¹⁴³Nd/¹⁴⁴Nd = 0.51223–0.51243) isotope ratios. The less evolved dacites could have been formed after crystal fractionation of oxide-rich gabbroic cumulates from mafic parental magmas, whereas the most silica-rich rhyolites could have been formed after fractional crystallization of feldspars, pyroxenes, oxides, zircon and apatite from a parental dacite magma. The composition of the Movene basalts imply different feeding systems from those of the underlying Sabie River basalts.     

Carbonatite and highly peralkaline nephelinite melts from Oldoinyo Lengai Volcano,Tanzania: The role of natrite-normative fluid degassing

Oldoinyo Lengai, located in the Gregory Rift in Tanzania, is a world-famous volcano owing to its uniqueness in producing natrocarbonatite melts and because of its extremely high CO₂ flux. The volcano is constructed of highly peralkaline [PI = molar (Na₂O + K₂O)/Al₂O₃ > 2–3] nephelinite and phonolites, both of which likely coexisted with carbonate melt and a CO₂-rich fluid before eruption. Results of a detailed melt inclusion study of the Oldoinyo Lengai nephelinite provide insights into the important role of degassing of CO₂-rich vapor in the formation of natrocarbonatite and highly peralkaline nephelinites. Nepheline phenocrysts trapped primary melt inclusions at 750–800 °C, representing an evolved state of the magmas beneath Oldoinyo Lengai. Raman spectroscopy, heating-quenching experiments, low current EDS and EPMA analyses of quenched melt inclusions suggest that at this temperature, a dominantly natrite_ss-normative, F-rich (7–14 wt%) carbonate melt and an extremely peralkaline (PI = 3.2–7.9), iron-rich nephelinite melt coexisted following degassing of a CO₂ + H₂O-vapor. We furthermore hypothesize that the degassing led to re-equilibration between the melt and liquid phases that remained and involved 1/ mixing between the residual (after degassing) alkali carbonate liquid and an F-rich carbonate melt and 2/ enrichment of the coexisting nephelinite melt in alkalis. We suggest that in the geological past similar processes were responsible for generating highly peralkaline silicate melts in continental rift tectonic settings worldwide.     

Magma mixing origin for the Aolunhua porphyry related to Mo–Cu mineralization,eastern Central Asian Orogenic Belt

Many Cu–Mo–Au deposits are considered to be related to adakitic porphyries formed in non-arc settings, e.g., in collisional orogenic zones and intra-plate environments, but their genesis is still under discussion. The Aolunhua porphyry complex and its related Mo–Cu deposit from the eastern Central Asian Orogenic Belt (CAOB) provide important insights into this issue. The porphyries are characterized by high Sr (496–705 ppm) and Sr/Y and La/Yb ratios similar to those of typical adakitic rocks, and low I_Sr ratios (0.7049–0.7052) and positive ε_Nd(t) (+ 0.5 to + 1.4) and ε_Hf(t) (+ 3.5 to + 9.8) values. These features, along with the occurrence of mafic microgranular enclaves (MMEs), compositional and textural disequilibrium of plagioclase phenocrysts and relatively high Mg# values (45–52), indicate that they were derived from mixing of felsic magma from partial melting of a juvenile arc-type lower crust and mafic magma from a lithospheric mantle previously metasomatized by subduction zone fluids/melts. High Sr/Y and La/Yb ratios are indicative of contribution from enriched mantle-derived materials (with high LILEs; e.g., Sr, La), which were strengthened by subsequent fractionation of ferromagnesian phases such as pyroxene and hornblende. MMEs hosted by the ore-bearing porphyry have zircon U–Pb ages of ca. 132 Ma, similar to those of the host rocks. The enclaves have elevated Mg^# (56–63), LILEs (e.g., Sr = 660–891 ppm), LREE (La_N = 68–150, (La/Sm)_N = 3.0–4.0, (La/Yb)_N = 12.0–19.6) and ratios of radiogenic isotopes of Nd- and Hf (ε_Nd = + 0.7 to + 1.6; ε_Hf = + 3.3 to + 10.9), suggesting that their parental magmas were derived from the metasomatized mantle source. The Mo–Cu mineralization was probably related to the high water content, high oxygen and sulfur fugacity of hybrid magma. Formation of the adakitic porphyries and related Mo–Cu deposits of the eastern CAOB could be related to the Early Cretaceous lithospheric extension, caused by the subduction of the Paleo-Pacific plate and its induced reactivation of juvenile arc-type lower crust.     

Metallogenic age and hydrothermal evolution of the Jidetun Mo deposit in central Jilin Province,northeast China: Evidence from fluid inclusions,isotope systematics,and geochronology

The Jidetun deposit is a large porphyry Mo deposit that is located in central Jilin Province, northeast China. The Mo mineralization occurs mainly at the edge of porphyritic granodiorite, as well as the adjacent monzogranite. Field investigations, cross-cutting relationships, and mineral paragenetic associations indicate four stages of hydrothermal activity. To determine the relationships between mineralization and associated magmatism, and better understand the metallogenic processes in ore district, we have undertaken a series of studies incluiding molybdenite Re–Os and zircon U–Pb geochronology, fluid inclusions microthermometry, and C–H–O–S–Pb isotope compositions. The molybdenite Re–Os dating yielded a well-defined isochron age of 168.9 ± 1.9 Ma (MSWD = 0.34) that is similar to the weighted mean ²⁰⁶Pb/²³⁸U age of 173.5 ± 1.5 Ma (MSWD = 1.8) obtained from zircons from the porphyritic granodiorite. The results lead to the conclusion that Mo mineralization, occurred in the Middle Jurassic (168.9 ± 1.9 Ma), was spatially, temporally, and genetically related to the porphyritic granodiorite (173.5 ± 1.5 Ma) rather than the older monzogranite (180.1 ± 0.6 Ma). Fluid inclusion and stable (C–H–O) isotope data indicate that the initial H₂O–NaCl fluids of mineralization stage I were of high-temperature and high-salinity affinity and exsolved from the granodiorite magma as a result of cooling and fractional crystallization. The fluids then evolved during mineralization stage II into immiscible H₂O–CO₂–NaCl fluids that facilitated the transport of metals (Mo, Cu, and Fe) and their separation from the ore-bearing magmas due to the influx of abundant external CO₂ and heated meteoric water. Subsequently, during mineralization stage III and IV, increase of pH in residual ore-forming fluids on account of CO₂ escape, and continuous decrease of ore-forming temperatures caused by the large accession of the meteoric water into the fluid system, reduced solubility and stability of metal clathrates, thus facilitating the deposition of polymetallic sulfides.     

Ore-forming process of the Huijiabao gold district,southwestern Guizhou Province,China: Evidence from fluid inclusions and stable isotopes

The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO₂ inclusions, CO₂–H₂O inclusions, hydrocarbon inclusions, and hydrocarbon–H₂O inclusions. The ore-forming fluids are characterized by a H₂O + CO₂ + CH₄ ± N₂ system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H₂O + NaCl → H₂O + NaCl + CO₂ + CH₄ ± N₂ → H₂O + NaCl ± CH₄ ± CO₂ with a slight decrease in homogenization temperature and salinity. The δ¹⁸O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δD_H2O and calculated δ¹⁸O_H2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H₂O–NaCl–CO₂ fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold.     

Geology,mineralization, stable isotope,and fluid inclusion characteristics of the Vostok-2 reduced W-Cu skarn and Au-W-Bi-As stockwork deposit,Sikhote-Alin,Russia

The large (>180 Kt WO₃ and at least 10–15 t Au) Vostok-2 deposit is situated in a metallogenic belt of W, Sn-W, Au, and Au-W deposits formed in late to post-collisional tectonic environment after cessation of active subduction. The deposit is related to an ilmenite-series high-K calc-alkaline plutonic suite that, by its petrologic signatures, is transitional between those at W-dominant and Au-dominant reduced intrusion-related deposits. Consistently, besides large W-Cu skarns of the reduced type, the deposit incorporates quartz stockworks with significant Au-W-Bi mineralization also formed in a reduced environment. The hydrothermal stages include prograde and retrograde, essentially pyroxene skarns, hydrosilicate (amphibole, chlorite, quartz) alteration, and phyllic (quartz, sericite, albite, apatite, and carbonate) alteration assemblages. These assemblages contain abundant scheelite associated with pyrrhotite, chalcopyrite and, at the phyllic stage, also with Bi minerals, As-Bi-Sb-Te-Pb-Zn sulfides and sulfosalts, as well as Au mineralization. The fluid evolution included hot, high-pressure (420–460 °C, 1.1–1.2 kbar), low-salinity (5.4–6.0 wt% NaCl-equiv.) aqueous fluids at the retrograde skarn stage, followed by lower temperature cyclic releases of high-carbonic, low salinity to non-carbonic moderate-salinity aqueous fluids. At the hydrosilicate stage, a high-carbonic, CH₄-dominated, hot (350–380 °C) low salinity fluid was followed by cooler (300–350 °C) non-carbonic moderate-salinity (5.7–14.9 wt% NaCl-equiv.) fluid. At the phyllic stage, a high-carbonic, CO₂-dominated, moderately-hot (330–355 °C, 0.9 kbar) low salinity fluid was followed by cooler (230–265 °C) non-carbonic moderate-salinity (6.6–12.0 wt% NaCl-equiv.) fluid. A homogenized magmatic source of water (δ¹⁸O_H2O = +8.3 to +8.7‰), and a sedimentary source of sulfur (δ³⁴S = −6.9 to −6.2‰) and carbon (δ¹³C_fluid = −20.1 to −14.9‰) at the hydrosilicate stage are suggested. A magmatic source of water (δ¹⁸O = +8.6 to +9.2‰) and a sedimentary source of sulfur (δ³⁴S = −9.3 to −4.1‰) but a magmatic (mantle- to crustal-derived) source of carbon (δ¹³C_fluid = −6.9 to −5.2‰) are envisaged for fluids that formed the early mineral assemblage of the phyllic stage. Then, the role of sedimentary carbon again increased toward the intermediate (δ¹³C_fluid = −16.4 to −14.5‰) and late (δ¹³C_fluid = −16.3 to −14.7‰) phyllic mineral assemblages. The magmatic differentiation was responsible for the fluid enrichment in W, whereas Au and Bi could also have been sourced from mafic magma. The decreasing temperatures, together with elevated Ca content in non-boiling fluids, promoted scheelite deposition at the early hydrothermal stages. The most intense scheelite deposition at the phyllic stage was caused by CO₂ removal due to boiling of CO₂-rich fluids; further cooling of non-boiling fluids favoured joint deposition of scheelite, Bi and Au.