A review of the occurrence, form and origin of C-bearing species in the Khibiny Alkaline Igneous Complex, Kola Peninsula, NW Russia

The Khibiny Complex hosts a wide variety of carbon-bearing species that include both oxidized and reduced varieties. Oxidised varieties include carbonate minerals, especially in the carbonatite complex at the eastern end of the pluton, and Na-carbonate phases. Reduced varieties include abiogenic hydrocarbon gases, particularly methane and ethane, dispersed bitumens, solid organic substances and graphite. The majority of the carbon in the Khibiny Complex is hosted in either the carbonatite complex or within the so-called “Central Arch”. The Central Arch is a ring-shaped structure which separates khibinites (coarse-grained eudialite-bearing nepheline-syenites) in the outer part of the complex from lyavochorrites (medium-grained nepheline-syenites) and foyaites in the inner part. The Central Arch is petrologically diverse and hosts the major REE-enriched apatite–nepheline deposits for which the complex is best known. It also hosts zones with elevated hydrocarbon (dominantly methane) gas content and zones of hydrothermally deposited Na-carbonate mineralisation. The hydrocarbon gases are most likely the product of a series of post-magmatic abiogenic reactions. It is likely that the concentration of apatite-nepheline deposits, hydrocarbon gases and Na-carbonate mineralisation, is a function of long lived fluid percolation through the Central Arch. Fluid migration was facilitated by stress release during cooling and uplift of the Khibiny Complex. As a result, carbon with a mantle signature was concentrated into a narrow ring-shaped zone.     

Alteration, HFSE mineralisation and hydrocarbon formation in peralkaline igneous systems: Insights from the Strange Lake Pluton, Canada

Two characteristics of peralkaline igneous rocks that are poorly understood are the extreme enrichment in HFSE, notably Zr, Nb, Y and REE, and the occurrence of fluid inclusions dominated by methane and higher hydrocarbons. Although much of the HFSE enrichment can be explained by magmatic processes, the common intense alteration of the parts of the peralkaline intrusions most enriched in these elements suggests that hydrothermal processes also play an important role in HFSE enrichment. Likewise, although the origin of the higher order hydrocarbons that occur as inclusions in these rocks is still debated, there is strong evidence that at least in some cases their formation involved hydrothermal processes. The issues of HFSE enrichment and hydrocarbon formation in peralkaline intrusions are examined using data from the Strange Lake pluton, a small, middle-Proterozoic intrusion of peralkaline granite in northeast Canada. This pluton contains some of the highest concentrations of Zr, REE and Y ever reported in an igneous body, and is characterised by abundant hydrocarbon-dominated fluid inclusions in rocks that have been hydrothermally altered, including those that form a potential HFSE ore zone. We show that HFSE at Strange Lake were partly concentrated to near exploitable levels as a result of their transport in a high salinity magmatic aqueous liquid, and that this fluid coexisted immiscibly with a carbonic phase which reacted with hydrogen and iron oxides generated during the associated hydrothermal alteration to produce hydrocarbons via a Fischer–Tropsch synthesis. As a result, hydrocarbons and HFSE mineralization are intimately associated. We then go on to show that hydrothermal alteration, HFSE mineralisation and hydrocarbons are also spatially associated in other peralkaline complexes, and present a model to explain this association, which we believe may be applicable to any peralkaline intrusion where HFSE enrichment was accompanied by calcium metasomatism, hematisation and hydrothermal fluorite. We also suggest that, even where these criteria are not satisfied, hydrothermally enriched HFSE and hydrocarbons will be intimately associated simply because they are products of the same initial magmatic fluid. Finally, we speculate that the association of HFSE and hydrocarbons may in some cases actually be genetic, if, as seems possible, unmixing or effervescence of a reduced carbonic fluid from the original magmatic fluid caused changes in temperature, pH, fO₂ or the activity of volatile ligands sufficient to induce the deposition of HFSE minerals.     

A reassessment of models for hydrocarbon generation in the Khibiny nepheline syenite complex, Kola Peninsula, Russia

Although hydrocarbon-bearing fluids have been known from the alkaline igneous rocks of the Khibiny intrusion for many years, their origin remains enigmatic. A recently proposed model of post-magmatic hydrocarbon (HC) generation through Fischer-Tropsch (FT) type reactions suggests the hydration of Fe-bearing phases and release of H₂ which reacts with magmatically derived CO₂ to form CH₄ and higher HCs. However, new petrographic, microthermometric, laser Raman, bulk gas and isotope data are presented and discussed in the context of previously published work in order to reassess models of HC generation. The gas phase is dominated by CH₄ with only minor proportions of higher hydrocarbons. No remnants of the proposed primary CO₂-rich fluid are found in the complex. The majority of the fluid inclusions are of secondary nature and trapped in healed microfractures. This indicates a high fluid flux after magma crystallisation. Entrapment conditions for fluid inclusions are 450–550 °C at 2.8–4.5 kbar. These temperatures are too high for hydrocarbon gas generation through the FT reaction. Chemical analyses of rims of Fe-rich phases suggest that they are not the result of alteration but instead represent changes in magma composition during crystallisation. Furthermore, there is no clear relationship between the presence of Fe-rich minerals and the abundance of fluid inclusion planes (FIPs) as reported elsewhere. δ¹³C values for methane range from − 22.4‰ to − 5.4‰, confirming a largely abiogenic origin for the gas. The presence of primary CH₄-dominated fluid inclusions and melt inclusions, which contain a methane-rich gas phase, indicates a magmatic origin of the HCs. An increase in methane content, together with a decrease in δ¹³C isotope values towards the intrusion margin suggests that magmatically derived abiogenic hydrocarbons may have mixed with biogenic hydrocarbons derived from the surrounding country rocks.     

Sr–Nd–Pb isotopic compositions of the Kovdor phoscorite–carbonatite complex, Kola Peninsula, NW Russia

The Sr, Nd and Pb isotopic compositions for the Kovdor phoscorite–carbonatite complex (PCC), Kola Peninsula, NW Russia, have been determined to characterize the mantle sources involved and to evaluate the relative contributions of a plume and subcontinental lithospheric mantle in the formation of the complex. The Kovdor PCC is a part of the Kovdor ultramafic–alkaline–carbonatite massif, and consists of six intrusions. The initial isotopic ratios of the analyzed samples, calculated at 380 Ma, display limited variations: ε_Nd, + 2.0 to + 4.7; ⁸⁷Sr/⁸⁶Sr, 0.70319 to 0.70361 (ε_Sr, − 12.2 to − 6.2); ²⁰⁶Pb/²⁰⁴Pb, 18.38 to 18.74; ²⁰⁷Pb/²⁰⁴Pb, 15.45 to 15.50; ²⁰⁸Pb/²⁰⁴Pb, 37.98 to 39.28. The Nd and Sr isotope data of the Kovdor PCC generally fit the patterns of the other phoscorites and carbonatites from the Kola Alkaline Province (KAP), but some data are slightly shifted from the mixing line defined as the Kola Carbonatite Line, having more radiogenic ⁸⁷Sr/⁸⁶Sr ratios. However, the less radiogenic Nd isotopic compositions and negative Δ7/4 values of Pb isotopes of the analyzed samples exclude crustal contamination, but imply the involvement of a metasomatized lithospheric mantle source. Isotopic variations indicate mixing of at least three distinct mantle components: FOZO-like primitive plume component, EMI-like enriched component and DMM-like depleted component. The isotopic nature of the EMI- and DMM-like mantle component observed in the Kovdor samples is considered to be inherited from metasomatized subcontinental lithospheric mantle. This supports the previous models invoking plume–lithosphere interaction to explain the origin of the Devonian alkaline carbonatite magmatism in the KAP.     

Compositions of magmas and carbonate–silicate liquid immiscibility in the Vulture alkaline igneous complex, Italy

This paper presents a study of melt and fluid inclusions in minerals of an olivine-leucite phonolitic nephelinite bomb from the Monticchio Lake Formation, Vulture. The rock contains 50 vol.% clinopyroxene, 12% leucite, 10% alkali feldspars, 8% hauyne/sodalite, 7.5% nepheline, 4.5% apatite, 3.2% olivine, 2% opaques, 2.6% plagioclase, and < 1% amphibole. We distinguished three generations of clinopyroxene differing in composition and morphology. All the phenocrysts bear primary and secondary melt and fluid inclusions, which recorded successive stages of melt evolution. The most primitive melts were found in the most magnesian olivine and the earliest clinopyroxene phenocrysts. The melts are near primary mantle liquids and are rich in Ca, Mg and incompatible and volatile elements. Thermometric experiments with the melt inclusions suggested that melt crystallization began at temperatures of about 1200 °C. Because of the partial leakage of all primary fluid inclusions, the pressure of crystallization is constrained only to minimum of 3.5 kbar. Combined silicate–carbonate melt inclusions were found in apatite phenocrysts. They are indicative of carbonate–silicate liquid immiscibility, which occurred during magma evolution. Large hydrous secondary melt inclusions were found in olivine and clinopyroxene. The inclusions in the phenocrysts recorded an open-system magma evolution during its rise towards the surface including crystallization, degassing, oxidation, and liquid immiscibility processes.     

Geochemisty and tectonic setting of igneous rocks in the Glenrock Station area,N.S.W.

In the Upper Murray Valley, Victoria, Late Silurian, high‐Si igneous rocks, which are closely associated with alkalic, basaltic dykes, were emplaced at high crustal levels following the peak of the Benambran Orogeny, which deformed and metamorphosed the Wagga Zone in Late Ordovician‐Early Silurian times. These rocks, which are informally termed ‘the Upper Murray high‐Si magmatic suite’, include leucogranites, rhyolite dykes and flows, and ash‐flow tuffs characterised by the following features. They are transitional from mildly peraluminous to mildly metaluminous; they represent relatively anhydrous magmas, in which halides were important volatile constituents; they have high Si, total alkalies, Rb, Th, U, Nb, Sn and heavy rare earth elements; and they are relatively repleted in Mg, Ca, Sr, Eu, V, Cr and Ni. In these respects and in their post‐orogenic setting and close association with alkalic basalts, they resemble many post‐orogenic granitoids from elsewhere. Such granitoids appear to have formed as partial melts during crustal extension following major episodes of deformation and high‐Si magmatism. A residual granulitic crust, from which an earlier generation of granitoid magmas had been extracted, is argued to be the source rock‐type for these post‐orogenic magmas. Tectonic extension, affecting such a crust, was accompanied by deep fracturing and basaltic vol‐canism. Mantle‐derived, CO₂‐ and halide‐rich fluids moved into the residual crust, causing widespread metasomatism, and emplacement of basaltic magma caused temperatures to rise until melting took place and a second group of magmas was produced. This model explains most aspects of the trace and major element chemistry of post‐orogenic, high‐Si igneous rocks and, for the Upper Murray high‐Si suite it also provides an explanation for variations in trace elements and isotopic characteristics. Other processes, such as crystal fractionation, magma mixing, thermogravi‐tational diffusion, and separation and loss of a volatile phase, provide explanations for variations within individual units of the suite, but they do not explain overall variations or the highly fractionated nature of the suite.     

Geologic, fluid inclusion and isotopic characteristics of the Jinding Zn–Pb deposit, western Yunnan, South China: A review

With a reserve of  200 Mt ore grading 6.08% Zn and 1.29% Pb (i.e., a metal reserve of  15 Mt) hosted in Cretaceous and Tertiary terrestrial rocks, the Jinding deposit is the largest Zn–Pb deposit in China, and also the youngest sediment-hosted super giant Zn–Pb deposit in the world. The deposit mainly occurs in the Jinding dome structure as tabular orebodies within breccia-bearing sandstones of the Palaeocene Yunlong Formation (autochthonous) and in the overlying sandstones of the Early Cretaceous Jingxing Formation (allochthonous). The deposit is not stratiform and no exhalative sedimentary rocks have been observed. The occurrence of the orebodies, presence of hangingwall alteration, and replacement and open-space filling textures all indicate an epigenetic origin. Formation of the Jinding Zn–Pb deposit is related to a period of major continental crust movement during the collision of the Indian and Eurasian Plates. The westward thrusts and dome structure were successively developed in the Palaeocene sedimentary rocks in the ore district, and Zn–Pb mineralisation appears to have taken place in the early stage of the doming processes.The study of fluid inclusions in sphalerite and associated gangue minerals (quartz, celestine, calcite and gypsum) shows that homogenisation temperatures ranged from 54 to 309 °C and cluster around 110 to 150 °C, with salinities of 1.6 to 18.0 wt.% NaCl equiv. Inert gas isotope studies from inclusions in ore- and gangue-minerals reveal 2.0 to 15.6% mantle He, 53% mantle Ne and a considerable amount of mantle Xe in the ore-forming fluids. The Pb-isotope composition of ores shows that the metal is mainly of mantle origin, mixed with a lesser amount of crustal lead. The widely variable and negative δ³⁴S values of Jinding sulphides suggest that thermo-chemical or bacterial sulphate reduction produced reduced sulphur for deposition of the Zn–Pb sulphides. The mixing of a mantle-sourced fluid enriched in metals and CO₂ with reduced sulphide-bearing saline formation water in a structural–lithologic trap may have been the key mechanism for the formation of the Jinding deposit.The Jinding deposit differs from known major types of sediment-hosted Zn–Pb deposits in the world, including sandstone-type (SST), Mississippi Valley type (MVT) and sedimentary-exhalative (SEDEX). Although the fine-grained ore texture and high Zn/Pb ratios are similar to those in SEDEX deposits, the Jinding deposit lacks any exhalative sedimentary rocks. Like MVT deposits, Jinding is characterised by simple mineralogy, epigenetic features and involvement of basinal brines in mineralisation, but its host rocks are mainly sandstones and breccia-bearing sandstones. The Jinding deposit is also different from SST deposits with its high Zn/Pb ratios, among other characteristics. Most importantly, the Jinding deposit was formed in an intracontinental terrestrial basin with an active tectonic history in relation to plate collision, and mantle-sourced fluids and metals played a major role in ore formation, which is not the case for SEDEX, MVT, and SST. We propose that Jinding represents a new type of sediment-hosted Zn–Pb deposit, named the ‘Jinding type’.     

Crustal contamination of mafic magmas: evidence from a petrological, geochemical and Sr–Nd–Os–O isotopic study of the Proterozoic Isortoq dike swarm, South Greenland

The mid-Proterozoic Isortoq dike swarm in the Gardar Province, South Greenland, comprises a variety of alkaline rocks ranging from gabbroic to syenitic in composition. Major magmatic mineral phases are olivine, clinopyroxene, Fe–Ti oxides, amphibole, plagioclase and alkali feldspar. Quartz occurs in some samples as a late magmatic phase. Liquidus temperatures of olivine-bearing samples range between 1120 and 1145 °C and solidus temperatures are 850–930 °C. Calculated silica activities are highly variable between 0.53 and unity. Oxygen fugacities vary from −3 to +1 log units relative to the fayalite–magnetite–quartz buffer.

The rocks have MgO contents <6 wt.% with Mg# between 53 and 17. Primitive mantle-normalized trace element patterns show a relative enrichment of LIL elements with Ba peaks and Nb troughs. Clinopyroxenes show a general enrichment in REE relative to chondritic values with variable slightly positive to prominent negative Eu anomalies. Two of the dikes were dated with Sm–Nd three-point isochrons at 1190±44 and 1187±87 Ma, respectively. Initial ⁸⁷Sr/⁸⁶Sr ratios of mafic mineral separates range from 0.70289 to 0.70432 and initial _Nd values vary from +0.3 to −10.7. Whole-rock initial ¹⁸⁷Os/¹⁸⁸Os ratios are highly variable including very radiogenic values of up to 7.967. δ¹⁸O_v-smow values of separated clinopyroxene and amphibole range from +5.2‰ to +6.2‰ and fall within the range of typical mantle-derived rocks, although mixing with a lower crustal component is permitted by the data. Using energy-constrained assimilation-fractional crystallization (EC-AFC) modeling equations, the Sr–Nd isotope data of the more radiogenic samples can successfully be modeled by addition of up to 10% lower crustal granulite-facies Archean gneisses as contaminants. The Os isotopic data also suggest the involvement of old radiogenic crust. In accordance with seismic data, we conclude that a wedge of Archean crust extends from West Greenland further to the south below the present erosion level.     

Distinct zircon U–Pb and O–Hf–Nd–Sr isotopic behaviour during fluid flow in UHP metamorphic rocks: evidence from metamorphic veins and their host eclogite in the Sulu Orogen,China

Fluid plays a key role in metamorphism and magmatism in subduction zones. Veins in high‐pressure (HP) to ultrahigh‐pressure (UHP) rocks are the products of fluid‐rock interaction, and can thus provide important constraints on fluid processes in subduction zones. This contribution is an integrated study of zircon U–Pb and O–Hf, as well as whole‐rock Nd–Sr isotopic compositions for a quartz vein, a complex vein, and their host eclogite in the Sulu UHP terrane to decipher the timing and source of fluid flow under HP‐UHP metamorphic conditions. The inherited magmatic zircon cores from the host eclogite constrain the protolith age at c. 750 Ma. Their variable ε_Hf(t) values from ?1.11 to 2.54 and low δ¹⁸O values of 0.32–3.40‰ reflect a protolith that formed in a rift setting due to the breakup of the supercontinent Rodinia. The hydrothermal zircon from the quartz and the complex veins shows euhedral shapes, relatively flat HREE pattern, slight or no negative Eu anomaly, low ¹⁷⁶Lu/¹⁷⁷Hf ratios, and low formation temperatures of 660–690 °C, indicating they precipitated from fluids under HP eclogite facies conditions. This zircon yielded similar U–Pb ages of 217 ± 2 and 213 ± 3 Ma within analytical uncertainty, recording the timing of fluid flow during the exhumation of the UHP rock. It is inferred that the fluids might be of internal origin based on the homogeneity of δ¹⁸O values of the hydrothermal zircon from the quartz (?2.41 ± 0.13‰) and complex veins (?2.35 ± 0.12‰), and the metamorphic grown zircon of the host eclogite (?2.23 ± 0.16‰). The similar ε_Nd(t) values of the whole rocks also support such a point. Zircon O and whole‐rock Nd isotopic compositions are therefore useful to identify the source of fluid, for they are major and trace components in minerals involved in metamorphic reactions during HP‐UHP conditions. On the other hand, the hydrothermal zircon from the veins and the metamorphic zircon from the host eclogite exhibit variable ε_Hf(t) values. Model calculation suggests that the Hf was derived from the breakdown of major rock‐forming minerals and recycling of the inherited magmatic zircon. The variable whole‐rock initial ⁸⁷Sr/⁸⁶Sr ratios might be caused by subsequent retrograde metamorphism after the formation of the veins.     

Petrogenesis of Cretaceous igneous rocks from the Duolong porphyry Cu–Au deposit,central Tibet: evidence from zircon U–Pb geochronology,petrochemistry and Sr–Nd–Pb–Hf isotope characteristics

The Duolong porphyry Cu–Au deposit (5.4 Mt at 0.72% Cu, 41 t at 0.23 g/t Au) was recently discovered in the southern Qiangtang terrane, central Tibet. Here, new whole‐rock elemental and Sr–Nd–Pb isotope and zircon Hf isotopic data of syn‐ and post‐ore volcanic rocks and barren and ore‐bearing granodiorite porphyries are presented for a reconstruction of magmas associated with Cu–Au mineralization. LA–ICP–MS zircon U–Pb dating yields mean ages of 117.0 ± 2.0 and 120.9 ± 1.7 Ma for ore‐bearing granodiorite porphyry and 105.2 ± 1.3 Ma for post‐ore basaltic andesite. All the samples show high‐K calc‐alkaline compositions, with enrichment of light rare earth elements (LREE) and large ion lithophile elements (LILE: Cs and Rb) and depletion of high field strength elements (HFSE: Nb and Ti), consistent with the geochemical characteristics of arc‐type magmas. Syn‐ and post‐ore volcanic rocks show initial Sr ratios of 0.7045–0.7055, ε_Nd(t) values of −0.8 to 3.6, (²⁰⁶Pb/²⁰⁴Pb)_t ratios of 18.408–18.642, (²⁰⁷Pb/²⁰⁴Pb)_t of 15.584–15.672 and positive zircon ε_Hf(t) values of 1.3–10.5, likely suggesting they dominantly were derived from metasomatized mantle wedge and contaminated by southern Qiangtang crust. Compared to mafic volcanic rocks, barren and ore‐bearing granodiorite porphyries have relatively high initial Sr isotopic ratios (0.7054–0.7072), low ε_Nd(t) values (−1.7 to −4.0), similar Pb and enriched zircon Hf isotopic compositions [ε_Hf(t) of 1.5–9.7], possibly suggesting more contribution from southern Qiangtang crust. Duolong volcanic rocks and granodiorite porphyries likely formed in a continental arc setting during northward subduction of the Bangong–Nujiang ocean and evolved at the base of the lower crust by MASH (melting, assimilation, storage and homogenization) processes. Copyright © 2014 John Wiley & Sons, Ltd.     

Age and provenance of early Precambrian metasedimentary rocks in the Lapland–Kola Belt, Russia: evidence from Pb and Nd isotopic data

²⁰⁷Pb/²⁰⁶Pb ages are presented for detrital zircons (Laser Ablation Microprobe ICP‐MS) and whole‐rock Nd isotopic determinations (TIMS) from samples of Neoarchean and Palaeoproterozoic metasedimentary rocks from the Umba granulite terrane and the Keivy domain of the Central Kola composite terrane, Kola Peninsula, north‐western Russia. Three are samples of rocks from the Umba granulite terrane that were deposited ≈ 2.20–1.90 Ga; they contain Archaean detritus, much of it older than 3.0 Gyr, as well as abundant 2.20–1.95‐Gyr‐old material. Deposition may have occurred on the margin of an Archaean craton with an exposed Palaeoproterozoic magmatic arc source, possibly during orogenesis. Two samples from the Keivy domain have remarkably similar, dominantly Archaean detrital zircon age spectra. One was deposited pre‐2.4 Ga, whereas the other was probably deposited post‐2.01 Ga. Both had similar sources, compatible with the proximal country rocks, and possible shallow‐water (?) cratonic margin depositional settings.     

The evolution of the lithospheric mantle along the N. African Plate: geochemical and isotopic evidence from the tholeiitic and alkaline volcanic rocks of the Hyblean plateau, Italy

The geochemical characteristics of primitive tholeiitic and alkaline volcanic rocks that erupted in the Plio-Pleistocene along fissures on the Hyblean plateau in Sicily (Italy) were used to constrain the mantle sources involved in the volcanic activity of this area of the Mediterranean. It is shown that some of the Hyblean plateau magmas with the most extreme isotopic compositions have combined radiogenic Nd, Sr and Pb, a feature that is distinct from the mixing end-members of the oceanic array. In addition, alkalinity in the basalts is found to be positively correlated with an increase in some HFSE ratios (e.g. Nb/Ta, Zr/Hf) and negatively correlated with ratios between HFSE and MREE (e.g. Ti/Eu), a characteristic that is attributed to a mantle source that has been modified by a carbonatitic metasomatic agent. This metasomatic enrichment had the effect of increasing the U/Pb of portions of the lower lithosphere, possibly by adding phases such as sodic pyroxene and apatite to the basalt-depleted lithosphere. It is suggested that rock types that formed by melting metasomatized portions of lithosphere-asthenosphere boundary affected by this recent enrichment in U/Pb fall along a trend with a shallow slope in a plot of ²⁰⁶Pb/²⁰⁴Pb versus ²⁰⁷Pb/²⁰⁴Pb, and have Nd isotopic compositions that are as radiogenic as present day MORB. The isotopic compositions and trace-element concentrations of the Hyblean plateau basalts are, therefore, mostly consistent with the interaction of a MORB-type mantle source with a young lithosphere that was probably formed in the Phanerozoic and metasomatized by CO₂-rich fluids, possibly during the Jurassic. The absence of a geochemical component indicative of involvement of older Proterozoic lithosphere and continental crust in the evolution of these magmas distinguishes them from those erupted along the margins of the Tyrrhenian sea, and supports the suggestion that at least portions of the lithosphere underneath Sicily have oceanic affinity and may be genetically related to the adjacent Ionian abyssal plain. Received 4 June 1997 / Accepted 25 November 1997     

Fluid evolution in the W–Cu–Zn–Pb San Cristobal vein, Peru: fluid inclusion and stable isotope evidence

The Zn–Pb±Ag±Cu San Cristobal district is located 100 km east of Lima in the western cordillera of Peru. It is centred around the Chumpe intrusion and is composed of vein and carbonate replacement ore types. The main San Cristobal vein presents a paragenesis that can be divided into three stages: (a) an early wolframite–quartz–pyrite stage, (b) a quartz–base metal stage, and (c) a late quartz–carbonate–barite stage.

Fluid inclusions in quartz from the tungsten stage are biphase (LV) at room temperature and homogenise to the liquid phase between 146 and 257 °C. Their salinities range between 2.1 and 5.1 wt.% NaCl equiv. Rare inclusions contain an additional crystal of halite and have salinities of 46–54 wt.% NaCl equiv. Data of the first two stages show a decrease in homogenisation temperatures concomitant with a salinity decline. Fluid inclusions in quartz from the late stage homogenise at higher temperatures, between 252 and 323 °C, with salinities ranging between 4.6 and 6.7 wt.% NaCl equiv.

Hydrogen and oxygen isotope data indicate a two-stage evolution. Isotopic compositions of the fluid associated with the first two stages define a trend with constant δ¹⁸O values and decreasing δD values (δ¹⁸O=3.2‰ to 5.0‰ V-SMOW and δD=−60‰ to −112‰ V-SMOW), which is interpreted as mixing of a dominantly magmatic component with minor meteoric water that had equilibrated with the host rocks. This interpretation is supported by sulphur and lead isotopic data from previous studies. By contrast, the quartz–carbonate–barite stage bears isotopic characteristics defining a trend with a coupled decrease of δ¹⁸O and δD (δ¹⁸O=−8.1‰ to 2.5‰ V-SMOW and δD=−57‰ to −91‰ V-SMOW) and is explained by addition of meteoric water to the system and subsequent mixing with a less important magmatic component.

Different fluid origins are confirmed by laser ablation ICP-MS analyses of the triphase (LVH) and biphase (LV) primary inclusions. The concentrations of the major ore elements, i.e., W, Cu, Zn and Pb, decrease throughout the paragenesis; W, and to a lesser extent Cu, show significant variations, associated with a steep decrease in their concentration. The decreasing concentrations can be explained by mineral deposition and dilution by the meteoric fluid; differences in the rate of decrease indicate selective precipitation of W. Fluid inclusions of the quartz–carbonate stages show an abrupt increase in Ba and Sr concentrations. This is interpreted to reflect a higher volume of host rock silicate alteration, probably due to the increasing size of the fluid flow cell and is explained by the input of a third fluid of unknown origin. LA-ICP-MS analyses show that the fluids were already depleted in W and Cu before reaching the emplacement of carbonate replacement ore type, whereas Zn and Pb were still present in considerable amounts. This is again due to selective precipitation and is consistent with the interpretation that the economically interesting metals were dominantly introduced by magmatic fluids.     

Paleoproterozoic subduction-related metasomatic signatures in the lithospheric mantle beneath NE Brazil: inferences from trace element and Sr–Nd–Pb isotopic compositions of Neoproterozoic high-K igneous rocks

Late Neoproterozoic (ca. 580 Ma), high-K, mafic-intermediate rocks represent voluminous bimodal magmatism in the Borborema Province, northeast Brazil. These rocks show the following chemical signatures that reflect derivation from a subduction-modified lithospheric mantle source: (1) enrichment in large ion lithophile elements (Rb, Ba, K, Th) and light rare-earth elements (REE) (La/Yb_CN=11–70), (2) pronounced negative Nb anomalies, and (3) radiogenic Sr (0.71202–0.7059) and unradiogenic Nd (_Nd from −9.3–−20.1) isotopic compositions. T_DM model ages suggest that modification of the lithospheric mantle source (metasomatised garnet lherzolite) may have occurred in the Paleoproterozoic during the Transamazonian/Eburnean tectonics that affected the region. Interaction with asthenospheric fluids is believed to have partially melted this enriched source in the Neoproterozoic, probably as a result of asthenosphere-derived fluid percolation in the Brasiliano/Pan-African shear zones that controlled the emplacement of these mafic-intermediate magmas. The involvement of this asthenospheric component is supported by the nonradiogenic Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb=16–17.3, ²⁰⁷Pb/²⁰⁴Pb=15.1–15.6, ²⁰⁸Pb/²⁰⁴Pb=36–37.5), which contrast with the enriched Sr and Nd compositions and thereby suggest the decoupling of Rb–Sr, Sm–Nd, and U–Pb systems at the time of intrusion of the mafic-intermediate magmas in the crust.     

A study of igneous rocks related to Zn–Pb mineralization in the Shinyemi and Gagok deposits of the Taebaeksan Basin,South Korea

The Shinyemi and Gagok deposits, located in the Taebaeksan Basin, South Korea, display Zn–Pb mineralization along a contact between Cretaceous granitoids and Cambrian–Ordovician carbonates of the Joseon Supergroup. The Shinyemi mine is one of the largest polymetallic skarn‐type magnetite deposits in South Korea and comprises Fe and Fe–Mo–Zn skarns, and Zn–Cu–Pb replacement deposits. Both deposits yield similar Cretaceous mineralization ages, and granitoids associated with the two deposits displaying similar mineral textures and compositions, are highly evolved, and were emplaced at a shallow depth. They are classified as calc‐alkaline, I‐type granites (magnetite series) and were formed in a volcanic arc. Compositional variation is less in the Shinyemi granites and aplites (e.g., SiO₂ = 74.4–76.6 wt% and 74.4–75.1 wt%, respectively) than in the Gagok granites and aplites (e.g., SiO₂ = 65.6–68.0 wt% and 74.9–76.5 wt%, respectively). Furthermore, SiO₂ vs K/Rb and SiO₂ vs Rb/Sr diagrams indicate that the Shinyemi granitoids are more evolved than the Gagok granitoids. Shinyemi granitoids had been already differentiated highly in deep depth and then intruded into shallow depth, so both granite and aplite show the highly evolved similar chemical compositions. Whereas, less differentiated Gagok granitoids were separated into two phases in the last stage at shallow depth, so granite and aplite show different compositions. The amounts of granites and aplite are similar in the Shinyemi deposit, whereas the aplite appears in an amount less than the granite in the Gagok deposit. For this reason, the Shinyemi granitoids caused not only Fe enrichment during formation of the dolomite‐hosted magnesian skarn but also was associated with Mo mineralization in the Shinyemi deposit. Zn mineralization of the Gagok deposit was mainly caused by granite rather than aplite. Our data suggest that the variation in mineralization displayed by the two deposits resulted from differences in the compositions of their associated igneous intrusions.     

He–Ar and Nd–Sr isotopic compositions of late Pleistocene felsic plutonic back arc basin rocks from Ulleungdo volcanic island, South Korea: Implications for the genesis of young plutonic rocks in a back arc basin

We report analyses of noble gases and Nd–Sr isotopes in mineral separates and whole rocks of late Pleistocene (< 0.2 Ma) monzonites from Ulleungdo, South Korea, a volcanic island within the back arc basin of the Japan island arc. A Rb–Sr mineral isochron age for the monzonites is 0.12 ± 0.01 Ma. K–Ar biotite ages from the same samples gave relatively concordant ages of 0.19 ± 0.01and 0.22 ± 0.01 Ma. ⁴⁰Ar/³⁹Ar yields a similar age of 0.29 ± 0.09 Ma. Geochemical characteristics of the felsic plutonic rocks, which are silica oversaturated alkali felsic rocks (av., 12.5 wt% in K₂O + Na₂O), are similar to those of 30 alkali volcanics from Ulleungdo in terms of concentrations of major, trace and REE elements. The initial Nd–Sr isotopic ratios of the monzonites (⁸⁷Sr/⁸⁶Sr = 0.70454–0.71264, ¹⁴³Nd/¹⁴⁴Nd = 0.512528–0.512577) are comparable with those of the alkali volcanics (⁸⁷Sr/⁸⁶Sr = 0.70466–0.70892, ¹⁴³Nd/¹⁴⁴Nd = 0.512521–0.512615) erupted in Stage 3 of Ulleungdo volcanism (0.24–0.47 Ma). The high initial ⁸⁷Sr/⁸⁶Sr values of the monzonites imply that seawater and crustally contaminated pre-existing trachytes may have been melted or assimilated during differentiation of the alkali basaltic magma.A mantle helium component (³He/⁴He ratio of up to 6.5 RA) associated with excess argon was found in the monzonites. Feldspar and biotite have preferentially lost helium during slow cooling at depth and/or during their transportation to the surface in a hot host magma. The source magma noble gas isotopic features are well preserved in fluid inclusions in hornblende, and indicate that the magma may be directly derived from subcontinental lithospheric mantle metasomatized by an ancient subduction process, or may have formed as a mixture of MORB-like mantle and crustal components. The radiometric ages, geochemical and Nd–Sr isotopic signatures of the Ulleungdo monzonites as well as the presence of mantle-derived helium and argon, suggests that these felsic plutonic rocks evolved from alkali basaltic magma that formed by partial melting of subcontinental lithospheric mantle beneath the back arc basin located along the active continental margin of the southeastern part of the Eurasian plate.     

Crystal fractionation in the petrogenesis of an alkali monzodiorite–syenite series: the Oshurkovo plutonic sheeted complex, Transbaikalia, Russia

The Oshurkovo Complex is a plutonic sheeted complex which represents numerous successive magmatic injections into an expanding system of subparallel and subvertical fractures. It comprises a wide range of rock types including alkali monzodiorite, monzonite, plagioclase-bearing and alkali-feldspar syenites, in the proportion of about 70% mafic rocks to 30% syenite. We suggest that the variation within the complex originated mainly by fractional crystallization of a tephrite magma.

The mafic rocks are considered as plutonic equivalents of lamprophyres. They exhibit a high abundance of ternary feldspar and apatite, the latter may attain 7–8 vol.% in monzodiorite. Ternary feldspar is also abundant in the syenites. The entire rock series is characterized by high Ba and Sr concentrations in the bulk rock samples (3000–7000 ppm) and in feldspars (up to 1 wt.%). The mafic magma had amphibole at the liquidus at 1010–1030 °C based on amphibole geothermometer. Temperatures as low as this were due to high H₂O and P₂O₅ contents in the melt (up to 4–6 and 2 wt.%, respectively). Crystallization of the syenitic magmas began at about 850 °C (based on ternary feldspar thermometry). The series was formed at an oxygen fugacity from the NNO to HM buffer, or even higher.

The evolution of the alkali monzodiorite–syenite series by fractional crystallization of a tephritic magma is established on the basis of geological, mineralogical, geochemical and Sm–Nd and Rb–Sr isotope data. The geochemical modeling suggests that fractionation of amphibole with subordinate apatite from the tephrite magma leaves about 73 wt.% of the residual monzonite melt. Further extraction of amphibole and plagioclase with minor apatite and Fe–Ti oxides could bring to formation of a syenite residuum. Rb–Sr isotopic analyses of biotite, apatite and whole-rock samples constrain the minimum age of basic intrusions at ca. 130 Ma and that of cross-cutting granite pegmatites at ca. 120 Ma. Hence the entire evolution took place in an interval of ≤10 My. Initial ⁸⁷Sr/⁸⁶Sr ratios for the mafic rocks range from 0.70511 to 0.70514, and for syenites from 0.70525 to 0.70542. Initial _Nd (130 Ma) values for mafic rocks vary from −1.9 to −2.4, and for syenites from −2.9 to −3.5. In a _Nd(T) vs. (⁸⁷Sr/⁸⁶Sr)_i diagram, all rock types of the complex fall in the enriched portion of the Mantle Array, suggesting their derivation from a metasomatized mantle source. However, the small but distinguishable difference in Sr and Nd isotopic compositions between mafic rocks and syenites probably resulted from mild (10–20%) crustal contamination during differentiation. Large negative Nb anomalies are interpreted as a characteristic feature of the source region produced by Precambrian fluid metasomatism above a subduction zone rather than by crustal contamination.     

Cretaceous isochron ages from K–Ar and Ar / Ar dating of eclogitic rocks in the Tso Morari Complex, western Himalaya, India

The Tso Morari Complex, which is thought to be originally the margin of the Indian continent, is composed of pelitic gneisses and schists including mafic rock lenses (eclogites and basic schists). Eclogites studied here have the mineral assemblage Grt + Omp + Ca-Amp + Zo + Phn + Pg + Qtz + Rt. They also have coesite pseudomorph in garnet and quartz rods in omphacite, suggesting a record of ultrahigh-pressure metamorphism. They occur only in the cores of meter-scale mafic rock lenses intercalated with the pelitic schists. Small mafic lenses and the rim parts of large lenses have been strongly deformed to form the foliation parallel to that of the pelitic schists and show the mineral assemblages of upper greenschist to amphibolite facies metamorphism. The garnet–omphacite thermometry and the univariant reaction relations for jadeite formation give 13–21 kbar at 600 °C and 16–18 kbar at 750 °C for the eclogite formation using the jadeite content of clinopyroxene (X_Jd = 0.48).

Phengites in pelitic schists show variable Si / Al and Na / K ratios among grains as well as within single grains, and give K–Ar ages of 50–87 Ma. The pelitic schist with paragonite and phengite yielded K–Ar ages of 83.5 Ma (K = 4.9 wt.%) for paragonite–phengite mixture and 85.3 Ma (K = 7.8 wt.%) for phengite and an isochron age of 91 ± 13 Ma from the two dataset. The eclogite gives a plateau age of 132 Ma in Ar/Ar step-heating analyses using single phengite grain and an inverse isochron age of 130 ± 39 Ma with an initial ⁴⁰Ar / ³⁶Ar ratio of 434 ± 90 in Ar/Ar spot analyses of phengites and paragonites. The Cretaceous isochron ages are interpreted to represent the timing of early stage of exhumation of the eclogitic rocks assuming revised high closure temperature (500 °C) for phengite K–Ar system. The phengites in pelitic schists have experienced retrograde reaction which modified their chemistry during intense deformation associated with the exhumation of these rocks with the release of significant radiogenic ⁴⁰Ar from the crystals. The argon release took place in the schists that experienced the retrogression to upper greenschist facies metamorphisms from the eclogite facies conditions.     

Petrogenesis of Cretaceous adakitic and shoshonitic igneous rocks in the Luzong area, Anhui Province (eastern China): Implications for geodynamics and Cu–Au mineralization

Both adakitic and shoshonitic igneous rocks in the Luzong area, Anhui Province, eastern China are associated with Cretaceous Cu–Au mineralization. The Shaxi quartz diorite porphyrites exhibit adakite-like geochemical features, such as light rare earth element (LREE) enrichment, heavy REE (HREE) depletion, high Al₂O₃, MgO, Sr, Sr / Y and La / Yb values, and low Y and Yb contents. They have low ε_Nd(t) values (− 3.46 to − 6.28) and high (⁸⁷Sr / ⁸⁶Sr)_i ratios (0.7051–0.7057). Sensitive High-Resolution Ion Microprobe (SHRIMP) zircon analyses indicate a crystallization age of 136 ± 3 Ma for the adakitic rocks. Most volcanic rocks and the majority of monzonites and syenites in the Luzong area are K-rich (or shoshonitic) and were also produced during the Cretaceous (140–125 Ma). They are enriched in LREE and large-ion lithophile elements, and depleted in Ti, and Nb and Ba and exhibit relatively lower ε_Nd(t) values ranging from − 4.65 to − 7.03 and relatively higher (⁸⁷Sr / ⁸⁶Sr)_i ratios varying between 0.7057 and 0.7062. The shoshonitic and adakitic rocks in the Luzong area have similar Pb isotopic compositions (²⁰⁶Pb / ²⁰⁴Pb = 17.90–18.83, ²⁰⁷Pb / ²⁰⁴Pb = 15.45–15.62 and ²⁰⁸Pb / ²⁰⁴Pb = 38.07–38.80). Geological data from the Luzong area suggest that the Cretaceous igneous rocks are distributed along NE fault zones (e.g., Tanlu and Yangtze River fault zones) in eastern China and were likely formed in an extensional setting within the Yangtze Block. The Shaxi adakitic rocks were probably derived by the partial melting of delaminated lower crust at pressures equivalent to crustal thickness of > 50 km (i.e., 1.5 GPa), possibly leaving rutile-bearing eclogitic residue. The shoshonitic magmas, in contrast, originated mainly from an enriched mantle metasomatized by subducted oceanic sediments. They underwent early high-pressure (> 1.5 GPa) fractional crystallization at the boundary between thickened (> 50 km) lower crust and lithospheric mantle and late low-pressure (< 1.5 GPa) fractional crystallization in the shallow (< 50 km) crust. The adakitic and shoshonitic rocks appear to be linked to an intra-continental extensional setting where partial melting of enriched mantle and delaminated lower crust was probably controlled by lithospheric thinning and upwelling of hot asthenosphere along NE fault zones (e.g., Tanlu and Yangtze River fault zones) in eastern China. Both the shoshonitic and adakitic magmas were fertile with respect to Cu–Au mineralization.