Tourmaline in the Vetka porphyry copper-molybdenum deposit of the Chukchi Peninsula of Russia

Three generations of tourmaline have been identified in propylite in the Vetka porphyry copper-molybdenum deposit of the Chukchi Peninsula of Russia. Tourmaline-I is characterized by its Fe_tot/(Fe_tot + Mg) value, which ranges from 0.33 to 0.49. Tourmaline-II, which crystallizes at a lower temperature, overgrowing tourmaline-I or occurring as isolated crystals, is distinguished by a higher Fe_tot/(Fe_tot + Mg), which varies from 0.46 to 0.72. The Fe_tot/(Fe_tot + Mg) ratio in tourmaline-III, which overgrows tourmaline-II is lower (0.35–0.49), and is identical to that of the first tourmaline generation. This is probably caused by the beginning of sulfide deposition. Tourmalines in the deposit characterized by complex isomorphic substitutions can be attributed to the intermediate members of the dravite—“hydroxy-uvite”-“oxy-uvite” and schorl-“hydroxy-feruvite”-“oxy-feruvite” series. Tourmaline starts to crystallize at temperatures above 340°C. The fluid responsible for the tourmaline deposition was magmatic, with a significant admixture of meteoric water (δ¹⁸O_{H 2}O = −0.85 to −0.75‰). The high Fe³⁺/Fe_tot ratio (0.50) indicates high oxygen activity when the tourmaline precipitated. It has been established that the isomorphic substitution Fe_tot → Al is typomorphic of tourmalines from porphyry copper deposits worldwide.     

Tourmaline from deposits of the Birgil’da-Tomino ore cluster, South Urals

Tourmalines from the Kalinovka porphyry copper deposit with epithermal bismuth-gold-basemetal mineralization and the Michurino gold-silver-base-metal prospect have been studied in the South Urals. Tourmaline from the Kalinovka deposit occurs as pockets and veinlets in quartz-sericite metasomatic rock and propylite. The early schorl-“oxy-schorl” [Fe_tot/(Fe_tot + Mg) = 0.66?0.81] enriched in Fe³⁺ is characterized by the homovalent isomorphic substitution of Fe³⁺ for Al typical of propylites at porphyry copper deposits. The overgrowing tourmalines of the second and third generations from propylite and quartz-sericite metasomatic rock are intermediate members of the dravite-magnesio-foitite solid solution series [Fe_tot/(Fe_tot + Mg) = 0.05?0.46] with homovalent substitution of Mg for Fe²⁺ and coupled substitution of ^X _? + ^YAl for ^XNa + ^YMg. These substitutions differ from the coupled substitution of ^YAl + ^WO^2? for ^YFe²⁺ + ^WOH^? in tourmaline from quartz-sericite rocks at porphyry copper deposits. At the Michurino prospect, the tourmaline hosted in the chlorite-pyrite-quartz veins and veinlets with Ag-Au-Cu-Pb-Zn mineralization is an intermediate member of the dravite-magnesio-foitite solid solution series [Fe_tot/(Fe_tot + Mg) = 0.20?0.31] with homovalent substitution of Mg for Fe²⁺ and coupled substitutions of ^X _? + ^YAl for ^XNa + ^YMg identical to that of late tourmaline at the Kalinovka deposit. Thus, tourmalines of the porphyry and epithermal stages are different in isomorphic substitutions, which allow us to consider tourmaline as an indicator of super- or juxtaposed mineralization.     

Protomylonite evolution potentially revealed by the 3D depiction and fractal analysis of chemical data from a feldspar

Tourmalinization associated with peraluminous granitic intrusions in metapelitic host-rocks has been widely recorded in the Iberian Peninsula, given the importance of tourmaline as a tracer of granite magma evolution and potential indicator of Sn-W mineralizations. In the Penamacor-Monsanto granite pluton (Central Eastern Portugal, Central Iberian Zone), tourmaline occurs: (1) as accessory phase in two-mica granitic rocks, muscovite-granites and aplites, (2) in quartz (±mica)-tourmaline rocks (tourmalinites) in several exocontact locations, and (3) as a rare detrital phase in contact zone hornfels and metapelitic host-rocks. Electron microprobe and stable isotope (δ¹⁸O, δD, δ¹¹B) data provide clear distinctions between tourmaline populations from these different settings: (a) schorl–oxyschorl tourmalines from granitic rocks have variable foititic component (^X□ = 17–57 %) and Mg/(Mg + Fe) ratios (0.19–0.50 in two-mica granitic rocks, and 0.05–0.19 in the more differentiated muscovite-granite and aplites); granitic tourmalines have constant δ¹⁸O values (12.1 ± 0.1 ‰), with wider-ranging δD (?78.2 ± 4.7 ‰) and δ¹¹B (?10.7 to ?9.0 ‰) values; (b) vein/breccia oxyschorl [Mg/(Mg + Fe) = 0.31–0.44] results from late, B- and Fe-enriched magma-derived fluids and is characterized by δ¹⁸O = 12.4 ‰, δD = ?29.5 ‰, and δ¹¹B = ?9.3 ‰, while replacement tourmalines have more dravitic compositions [Mg/(Mg + Fe) = 0.26–0.64], close to that of detrital tourmaline in the surrounding metapelitic rocks, and yield relatively constant δ¹⁸O values (13.1–13.3 ‰), though wider-ranging δD (?58.5 to ?36.5 ‰) and δ¹¹B (?10.2 to ?8.8 ‰) values; and (c) detrital tourmaline in contact rocks and regional host metasediments is mainly dravite [Mg/(Mg + Fe) = 0.35–0.78] and oxydravite [Mg/(Mg + Fe) = 0.51–0.58], respectively. Boron contents of the granitic rocks are low (<650 ppm) compared to the minimum B contents normally required for tourmaline saturation in granitic melts, implying loss of B and other volatiles to the surrounding host-rocks during the late-magmatic stages. This process was responsible for tourmalinization at the exocontact of the Penamacor-Monsanto pluton, either as direct tourmaline precipitation in cavities and fractures crossing the pluton margin (vein/breccia tourmalinites), or as replacement of mafic minerals (chlorite or biotite) in the host-rocks (replacement tourmalinites) along the exocontact of the granite. Thermometry based on ¹⁸O equilibrium fractionation between tourmaline and fluid indicates that a late, B-enriched magmatic aqueous fluid (av. δ¹⁸O ~12.1 ‰, at ~600 °C) precipitated the vein/breccia tourmaline (δ¹⁸O ~12.4 ‰) at ~500–550 °C, and later interacted with the cooler surrounding host-rocks to produce tourmaline at lower temperatures (400–450 °C), and an average δ¹⁸O ~13.2 ‰, closer to the values for the host-rock. Although B-metasomatism associated with some granitic plutons in the Iberian Peninsula seems to be relatively confined in space, extending integrated studies such as this to a larger number of granitic plutons may afford us a better understanding of Variscan magmatism and related mineralizations.     

Boron,sulphur and copper isotope systematics in the orogenic gold deposits of the Archaean Hattu schist belt,eastern Finland

The Hattu schist belt is located in the western part of the Archaean Karelian domain of the Fennoscandian Shield. The orogenic gold deposits with Au–Bi–Te geochemical signatures are hosted by NE–SW, N–S and NW–SE oriented shear zones that deform 2.76–2.73 Ga volcanic and sedimentary sequences, as well as 2.75–2.72 Ga tonalite–granodiorite intrusions and diverse felsic porphyry dykes. Mo–W mineralization is also present in some tonalite intrusions, both separate from, and associated with Au mineralization. Somewhat younger, unmineralized leucogranite intrusions (2.70 Ga) also intrude the belt. Lower amphibolite facies peak metamorphism at 3–5 kbar pressures and at 500–600 °C temperatures affected the belt at around 2.70 Ga and post-date hydrothermal alteration and ore formation. In this study, we investigated the potential influence of magmatic-hydrothermal processes on the formation of orogenic gold deposits on the basis of multiple stable isotope (B, S, Cu) studies of tourmaline and sulphide minerals by application of in situ SIMS and LA ICP MS analytical techniques.Crystal chemistry of tourmaline from a Mo–W mineralization hosted by a tonalite intrusion in the Hattu schist belt is characterized by Fe^3 +–Al^3 +-substitution indicating relatively oxidizing conditions of hydrothermal processes. The range of δ¹¹B data for this kind of tourmaline is from − 17.2‰ to − 12.2‰. The hydrothermal tourmaline from felsic porphyry dyke swith gold mineralization has similar crystal chemistry (e.g. dravite–povondraite compositional trend with Fe^3 +–Al^3 + substitution) and δ¹¹B values between − 19.0‰ and − 9.6‰. The uvite–foitite compositional trend and δ¹¹B ‰ values between − 24.1% and − 13.6% characterize metasomatic–hydrothermal tourmaline from the metasediment-hosted gold deposits. Composition of hydrothermal vein-filling and disseminated tourmaline from the gold-bearing shear zones in metavolcanic rocks is transitional between the felsic intrusion and metasedimentary rock hosted hydrothermal tourmaline but the range of average boron isotope data is essentially identical with that of the metasediment-hosted tourmaline. Rock-forming (magmatic) tourmaline from leucogranite has δ¹¹B values between − 14.5‰ and − 10.8‰ and the major element composition is similar to that of the metasediment-hosted tourmaline.The range of δ³⁴S_VCDT values measured in pyrite, chalcopyrite and pyrrhotite is from − 9.1 to + 8.5‰, which falls within the typical range of sulphur isotope data for Archaean orogenic gold deposits. In the Hattu schist belt, positive δ³⁴S_VCDT values characterize metasediment-hosted gold ores with sulphide parageneses dominated by pyrrhotite and arsenopyrite. The δ³⁴S_VCDT values are both positive and negative in ore mineral parageneses within felsic intrusive rocks in which variable amounts of pyrrhotite are associated with pyrite. Purely negative values were only recorded from the pyrite-dominated gold mineralization within metavolcanic units. Therefore the shift of δ³⁴S_VCDT values to the negative values reflects precipitation of sulphide minerals from relatively oxidizing fluids. The range of measured δ⁶⁵Cu_NBS978 values from chalcopyrite is from − 1.11 to 1.19‰. Positive values are common for mineralization in felsic intrusive rocks and negative values are more typical for deposits confined to metasedimentary rocks. Positive and negative δ⁶⁵Cu_NBS978 values occur in the ores hosted by metavolcanic rocks. There is no correlation between sulphur and copper isotope data obtained in the same chalcopyrite grains.Evaluation of sulphur and boron isotope data together and comparisons with other Archaean orogenic gold provinces supports the hypothesis that the metasedimentary rocks were the major sources of sulphur and boron in the orogenic gold deposits in the Hattu schist belt. Variations in major element and boron isotope compositions in tourmaline, as well as in the δ³⁴S_VCDT values in sulphide minerals are attributed to localized involvement of magmatic fluids in the hydrothermal processes. The results of copper isotope studies indicate that local sources of copper in orogenic gold deposits may potentially be recognized if the original, distinct signatures of the sources have not been homogenized by widespread interaction of fluids with a large variety of rocks and provided that local chemical variations have been too small to trigger changes in the oxidation state of copper during hydrothermal processes.     

Oxygen,carbon and sulphur isotope studies in the Keban Pb–Zn deposits,eastern Turkey: An approach on the origin of hydrothermal fluids

Pb–Zn deposits are widespread and common in various parts of the Taurus Belt. Most of the deposits are of pyrometasomatic and hydrothermal origin. The Keban Pb–Zn deposits are located along the intrusive contact between the Paleozoic – Lower Triassic Keban Metamorphic Formation and the syenite porphyry of the Upper Cretaceous Keban igneous rocks. Various studies have already been carried out; using fluid inclusion studies on fluorite, calcite and quartz on the pyrite–chalcopyrite bearing Keban ore deposits. This study focuses on the interpretation of stable isotope compositions in connexion with fluid inclusion data. Sulphur isotope values (δ³⁴S) of pyrite are within the range of ?0.59 to +0.17‰_V-CDT (n = 10). Thus, the source of sulphur is considered to be magmatic, as evidenced by associated igneous rocks and δ³⁴S values around zero“0”. Oxygen isotope values δ¹⁸O of quartz vary between +10.5 and +19.9‰_(SMOW). However, δ¹⁸O and δ¹³C values of calcite related to re-crystallized limestone (Keban Metamorphic Formation) reach up to +27.3‰_(SMOW) and +1.6‰_(PDB), respectively. The δ³⁴S, δ¹³C and δ¹⁸O values demonstrate that skarn-type Pb–Zn deposits formed within syeno-monzonitic rocks and calc-schist contacts could have developed at low temperatures, by mixing metamorphic and meteoric waters in the final stages of magmatism.     

Tourmaline from quartz lenses of the Urtui granite pluton,Strel’tsovka orefield,Ttansbaikal krai

Quartz-tourmaline lenses, around which host granite is impregnated by uraninite, have been found among porphyritic granite with large phenocrysts of the Urtui pluton in the Ttansbaikal krai framing the Strel’tsovka volcano-tectonic structure. Two generations of tourmaline are distinguished. Most individual crystals belong to the first generation attributed to “fluor-schorl”; tourmaline-II attributed to schorl occurs as thin rims overgrowing tourmaline-I. The major type of cation isomorphic substitution in both tourmalines is Fe²⁺ → Mg. The Fe³⁺/Fe_tot value and Li content in the average sample are 2% and 80 ppm, respectively. The high F content, comparatively high Li, low Fe³⁺/Fe_tot value, and character of cation isomorphic substitution indicate that the tourmaline relates to greisens. The combination of these features allows one to distinguish greisen-type tourmaline-bearing rocks. The impregnated uranium mineralization in granite of the Urtui pluton, one of the probable sources of uranium in economic U ore of the Strel’tsovka deposit, is suggested to be caused by greisenization and the formation of quartz-tourmaline lenses.     

Development and Re‐Evaluation of Tourmaline Reference Materials for In Situ Measurement of Boron δ Values by Secondary Ion Mass Spectrometry

Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ¹¹B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ¹¹B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO₂ and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).     

Geology,Fluid Inclusion Characteristics and H–O–C Isotopes of Large Lijiagou Pegmatite Spodumene Deposit in Songpan–Garze Fold Belt,Eastern Tibet: Implications for ore Genesis

The large, newly discovered Lijiagou pegmatite spodumene deposit, is located southeast of the Ke'eryin pegmatite ore field, in the central Songpan–Garze Fold Belt (SGFB), Eastern Tibet. The Lijiagou albite spodumene pegmatites are unzoned, granite‐pegmatites of the subtype LCT (Lithium, Cesium, and Tantalum) and consist of medium‐ to coarse‐grained spodumene, lepidolite, microcline, albite, quartz, muscovite, and accessory amounts of beryl, cassiterite, columbite–tantalite and zircon. Secondary fluid inclusions in quartz and spodumene include two‐phase aqueous inclusions (V + L), mono‐phase vapor inclusions (V); three‐phase CO₂‐rich CO₂–H₂O inclusions (CO₂ + V + L) and less abundant liquid inclusions (L). The homogenization temperature of the fluid inclusions are low (257.3 to 204.3°C in early stage, 250.3 to 199.6°C in middle stage, 218.7 to 200.6°C in late stage). Fluid inclusions were formed during the long cooling period from the temperature of the pegmatite emplacement. Liquid–vapor–gas boiling was extensive during the middle and late stages. The salinity of the corresponding stages are 15.4 to 13.0 wt.% NaCl equiv., 12.5 to 9.1 wt.% NaCl equiv. and 9.8 to 7.8 wt.% NaCl equiv., respectively. δ¹⁸O values of fluid are 7.2 to 5.2‰, 5.6 to 3.9‰ and 2.7 to −0.2‰ from early to late stages; and δD range from −75.1 to −76.8‰, −59.0 to −73.5‰ and −61.6 to −85.5‰ respectively. The δ¹³C of CO₂ values are −5.6 to −6.6‰, −8.5 to −19.9‰, −11.8 to −18.7‰ from early to late stages, suggesting that CO₂ in the fluids were probably sourced from a magmatic system, possibly with some mixing of CO₂ dissolved in groundwater. δD and δ¹⁸O values of fluid indicate that the fluids were originally magmatic water and mixed with some meteoric water in late stage. The magma evolution sequence in the Ke'eryin orefield, from the central two‐mica granite through the Lijiagou deposit out to the distal pegmatites, with the ages gradually decreasing, indicates that the Ke'eryin complex rocks are the product of multistage magmatic activity. The large Lijiagou spodumene deposit is a typical magmatic, fractional crystallization related pegmatite deposit.     

The Laqiong Sb-Au deposit: Implications for polymetallic mineral systems in the Tethys-Himalayan zone of southern Tibet,China

The Himalayan mineral field includes over 50 quartz-vein type Sb-Au deposits, and placer Au deposits. The poorly documented Laqiong deposit is a typical example of quartz-vein type Sb-Au mineralisation in Tethys Himalayan sequence. The orebody are controlled by shallow north-dipping normal faults and north–south trending faults. Magmatic zircons extracted from muscovitic leucocratic granite from the southern part of the Laqiong mine area yield a Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry U-Pb age of 14 ± 1 Ma (n = 12, MSWD = 0.9) that is similar to the ⁴⁰Ar/³⁹Ar age of ca. 14 Ma from hydrothermal sericite in auriferous sulphide-quartz veins. The ε_Hf(t) values for the magmatic zircon rims range from −5.4 to −1.9, corresponding to two-stage Hf model ages of 1403–1214 Ma. Quartz from the mineralised veins has δ¹⁸O_H2O-SMOW values varying from +4.97 to +9.59‰ and δD_H2O-SMOW values ranging from −119.7 to −108.1‰. The δ¹³C_V-PDB values for calcite from the ore Stage III range from −6.9 to −5.3‰, and calcite from Stage IV are −3.5 to −1.7‰. The δ¹⁸O_V-SMOW values for calcite from Stage III are +20.3 to +20.6‰ and for Stage IV are −6.3 to −4.9‰. The stibnite and pyrite samples have ²⁰⁸Pb/²⁰⁴Pb ratios of 38.158 to 39.02, ²⁰⁷Pb/²⁰⁴Pb ratios of 15.554 to 15.698, and ²⁰⁶Pb/²⁰⁴Pb ratios of 17.819 to 18.681, and bulk and in-situ δ³⁴S_V-CDT values for stibnite, arsenopyrite and pyrite range from −1.1 to +2.3‰. The calcite from the orebodies are enriched in MREE and depleted in LREE and HREE. Fieldwork, petrological, and geochemical data collected during our study leads to the following salient findings: the mineralising fluid is a mix of magmatic and meteoric fluids; and the deposit is closely related to the emplacement of Miocene granites originating from a thickened continental crust.     

Geology and Isotope Geochemistry of the Dongzhongla Pb–Zn Deposit in Tibet: Implications for the Origin of the Ore‐Forming Fluids and Storage Condition of Certain Metals

As a newly discovered medium‐sized deposit (proven Pb + Zn resources of 0.23 Mt, 9.43% Pb and 8.73% Zn), the Dongzhongla skarn Pb–Zn deposit is located in the northern margin of the eastern Gangdese, central Lhasa block. Based on the geological conditions in this deposit of ore‐forming fluids, H, O, C, S, Pb, Sr, and noble gas isotopic compositions were analyzed. Results show that δ¹⁸O_SMOW of quartz and calcite ranged from −9.85 to 4.17‰, and δD_SMOW ranged from −124.7 to −99.6‰ (where SMOW is the standard mean ocean water), indicating magma fluids mixed with meteoric water in ore‐forming fluids. The δ¹³C_PDB and δ¹⁸O_SMOW values of calcite range from −1.4 to −1.1‰ and from 5.3 to 15.90‰, respectively, show compositions consistent with the carbonate limestone in the surrounding rocks, implying that the carbon was primarily sourced from the dissolution of carbonate strata in the Luobadui Formation. The ore δ³⁴S composition varied in a narrow range of 2.8 to 5.7‰, mostly between 4‰ and 5‰. The total sulfur isotopic value δ³⁴S was 4.7‰ with characteristics of magmatic sulfur. The ³He/⁴He values of pyrite and galena ranged from 0.101 to 5.7 Ra, lower than those of mantle‐derived fluids (6 ± 1 Ra), but higher than those of the crust (0.01–0.05 Ra), and therefore classified as a crust–mantle mixed source. The Pb isotopic composition for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb values of the ores were in the ranges of 18.628–18.746, 15.698–15.802, and 39.077–39.430, respectively, consistent with the Pb isotopic composition of magmatic rocks in the deposit, classified as upper‐crust lead. The ore lead was likely sourced partially from the crustal basement of the Lhasa Terrane. The initial (⁸⁷Sr/⁸⁶Sr)_i value from five sulfide samples ranged from 0.71732 to 0.72767, and associated ore‐forming fluids were mainly sourced from the partial melting of the upper‐crust materials. Pb isotopic compositions of ore sulfides from the Dongzhongla deposit are similar to that of the Yuiguila and Mengya'a deposit, indicating that they have similar sources of metal‐rich ore‐forming solution. According to basic skarn mineralogy, the economic metals, and the origin of the ore‐forming fluids, the Dongzhongla deposit was classified as a skarn‐type Pb–Zn deposit.     

Magmatic hydrothermal origin of the Hadamengou-Liubagou Au-Mo deposit,Inner Mongolia,China: Constrains on geology,stable and Re-Os isotopes

The Hadamengou-Liubagou Au-Mo deposit is the largest gold deposit in Inner Mongolia of North China. It is hosted by amphibolite to granulite facies metamorphic rocks of the Archean Wulashan Group. To the west and north of the deposit, there occur three alkaline intrusions, including the Devonian-Carboniferous Dahuabei granitoid batholith, the Triassic Shadegai granite and the Xishadegai porphyritic granite with molybdenum mineralization. Over one hundred subparallel, sheet-like ore veins are confined to the nearly EW-trending faults in the deposit. They typically dip 40° to 80° to the south, with strike lengths from hundreds to thousands of meters. Wall rock alterations include potassic, phyllic, and propylitic alteration. Four distinct mineralization stages were identified at the deposit, including K-feldspar-quartz-molybdenite stage (I), quartz-pyrite-epidote/chlorite stage (II), quartz-polymetallic sulfide-gold stage (III), and carbonate-sulfate-quartz stage (IV). Gold precipitated mainly during stage III, while Mo mineralization occurred predominantly in stage I. The δD_H2O and δ¹⁸O_H2O values of the ore-forming fluids range from −125‰ to −62‰ and from 1.4‰ to 7.5‰, respectively, indicating that the fluids were dominated by magmatic water with a minor contribution of meteoric water. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal carbonate minerals vary from −10.3‰ to −3.2‰ and from 3.7‰ to 15.3‰, respectively, suggesting a magmatic carbon origin. The δ³⁴S_CDT values of sulfides from the ores vary from −21.7‰ to 5.4‰ and are typically negative (mostly −20‰ to 0‰). The wide variation of the δ³⁴S_CDT values, the relatively uniform δ¹³C values of carbonates (typically −5.5‰ to −3.2‰), as well as the common association of barite with sulfides suggest that the minerals were precipitated under relatively high fo₂ conditions, probably in a magmatic fluid with δ³⁴S_ƩS ≈ 0‰. The Re-Os isotopic dating on molybdenite from Hadamengou yielded a weighted average age of 381.6 ± 4.3 Ma, indicating that the Mo mineralization occurred in Late Devonian. Collectively, previous ⁴⁰Ar-³⁹Ar and Re-Os isotopic dates roughly outlined two ranges of mineralizing events of 382–323 Ma and 240–218 Ma that correspond to the Variscan and the Indosinian epochs, respectively. The Variscan event is approximately consistent with the Mo mineralization at Hadamengou-Liubagou and the emplacement of the Dahuabei Batholith, whereas the Indosinian event roughly corresponds to the possible peak Au mineralization of the Hadamengou-Liubagou deposit, as well as the magmatic activity and associated Mo mineralization at Xishadegai and Shadegai. Geologic, petrographic and isotopic evidence presented in this study suggest that both gold and molybdenum mineralization at Hadamengou-Liubagou is of magmatic hydrothermal origin. The molybdenum mineralization is suggested to be associated with the magmatic activity during the southward subduction of the Paleo-Asian Ocean beneath the North China Craton (NCC) in Late Devonian. The gold mineralization is most probably related to the magma-derived hydrothermal fluids during the post-collisional extension in Triassic, after the final suturing between the Siberian and NCC in Late Permian.     

Geochemistry and genesis of the banded iron formations of the Cauê Formation,Quadrilátero Ferrífero,Minas Gerais,Brazil

The Cauê Formation of the Paleoproterozoic Minas Supergroup hosts banded iron formations (BIFs), locally called itabirites, deposited in shallow marine passive margin settings. Two major compositional types of itabirite, dolomitic and quartz itabirites, are found in the northwestern part of QF. The former consists of alternating dolomite-rich and hematite-rich bands, whereas the latter is formed with alternating quartz-rich and hematite-rich bands. Accessory minerals are chlorite, sericite, and apatite in both types.Dolomitic and quartz itabirites have a very simple chemical composition. In the dolomitic itabirite, Fe₂O₃ plus CaO, MgO, and LOI range from 95.8 to 97.8%, while in the quartz itabirite, Fe₂O₃ plus SiO₂ range from 94.4 to 99.6%. Both itabirites are highly oxidized and present Fe³⁺/(Fe²⁺ + Fe³⁺) ratios higher than 0.98, by far superior than the average ratios of Paleoproterozoic BIFs. Trace element concentrations in itabirites are very low, ranging from <10 to 55 ppm. Dolomite shows negative δ¹³C values varying from −2.5 to −0.8‰ versus PDB, while the oxygen isotope data display δ¹⁸O values varying from −12.4 to −8.5‰ versus PDB. The δ¹³C values of the dolomitic itabirite are in the same range of those of the overlying stromatolitic dolomites of the Gandarela Formation. C and O isotopes, REE signatures, and Y/Ho ratios suggest a marine origin for the sediments of the Cauê Formation. The HREE enrichment pattern exhibited by the itabirites shows a modern seawater REE signature overprinted by a hydrothermal pattern marked by positive Eu anomalies. Very low contents of Al₂O₃ and TiO₂ and a strong positive correlation between them indicate a minor terrigenous component in the chemically-precipitated marine sediments of the Cauê Formation. Differences in the HREE signatures of itabirites suggest that dolomitic itabirite precipitated in shallower waters receiving sediments from the continent, while quartz itabirite precipitated in deeper waters. Sea-level fluctuations caused by marine transgression–regressions possibly contributed to changes in the composition and varied input of the terrigenous sediments. These changes are expressed by the co-existence of dolomitic, quartz, and amphibolitic itabirites in the Cauê Formation, which represent lateral and vertical facies transitions of dolomitic, cherty, and shaly BIFs, respectively.     

Origin and migration of palaeofluids in the Upper Visean of the Campine Basin, northern Belgium

Upper Visean limestones in the Campine Basin of northern Belgium are intensively fractured. The largest and most common fractures are cemented by non-ferroan, dull brown-orange luminescent blocky calcite. First melting temperatures of fluid inclusions in these calcites are around -57°C, suggesting that precipitation of the cements occurred from NaCl-CaCl₂-MgCl₂ fluids. The final melting temperatures (T_m^ice) are between -5 and -33°C. The broad range in the T_m^ice data can be explained by the mixing of high salinity fluids with meteoric waters, but other hypotheses may also be valid. Homogenization temperatures from blocky calcite cements in the shelf limestones are interpreted to have formed between 45 and 75°C. In carbonates which were deposited close to and at the shelf margin, precipitation temperatures were possibly in the range 70-85°C and 72-93°C, respectively. On the shelf, the calcites have a δ¹⁸O around -9.3‰ PDB and they are interpreted to have grown in a fluid with a δ¹⁸O between −3.5 and +1.0‰ SMOW. At the shelf margin, blocky calcites (δ¹⁸O∼ - 13.5‰ PDB) could have precipitated from a fluid with a δ¹⁸O betweenn -4.0 and -1.1‰ SMOW. The highest oxygen isotopic compositions are comparable to those of Late Carboniferous marine fluids (δ¹⁸O= - 1‰ SMOW). The lowest values are more positive than a previously reported composition for Carboniferous meteoric waters (δ¹⁸O= -7‰ SMOW). Precipitation is likely to have occurred in marine-derived fluids, which mixed with meteoric waters sourced from near the Brabant Massif. Fluids with a similar negative oxygen isotopic composition and high salinity are actually present in Palaeozoic formations. The higher temperature range in the limestones near the shelf margin is explained by the upward migration of fluids from the ‘basinal’ area along fractures and faults into the shelf.     

Hydrothermal Alteration and Mineralization of Middle Jurassic Dexing Porphyry Cu-Mo Deposit, Southeast China

The Dexing deposit is located in a NE‐trending magmatic belt along the southeastern margin of the Yangtze Craton. It is the largest porphyry copper deposit in China, consisting of three porphyry copper orebodies of Zhushahong, Tongchang and Fujiawu from northwest to southeast. It contains 1168 Mt of ores with 0.5% Cu and 0.01% Mo. The Dexing deposit is hosted by Middle Jurassic granodiorite porphyries and pelitic schist of Proterozoic age. The Tongchang granodiorite porphyry has a medium K cal‐alkaline series, with medium K₂O content (1.94–2.07 wt%), and low K₂O/(Na₂O + K₂O) (0.33–0.84) ratios. They have high large‐ion lithophile elements, high light rare‐earth elements, and low high‐field‐strength elements. The hydrothermal alteration at Tongchang is divided into four alteration mineral assemblages and related vein systems. They are early K‐feldspar alteration and A vein; transitional (chlorite + illite) alteration and B vein; late phyllic (quartz + muscovite) alteration and D vein; and latest carbonate, sulfate and oxide alteration and hematite veins. Primary fluid inclusions in quartz from phyllic alteration assemblage include liquid‐rich (type 1), vapor‐rich (type 2) and halite‐bearing ones (type 3). These provide trapping pressures of 20–400 ´ 10⁵ Pa of fluids responsible for the formation of D veins. Igneous biotite from least altered granochiorite porphyry and hydrothermal muscovite in mineralized granodiorite porphyry possess δ¹⁸O and δD values of 4.6‰ and ?87‰ for biotite and 7.1–8.9‰, ?71 to ?73‰ for muscovite. Stable isotopic composition of the hydrothermal water suggests a magmatic origin. The carbon and oxygen isotope for hydrothermal calcite are ?4.8 to ?6.2‰ and 6.8–18.8‰, respectively. The δ³⁴S of pyrite in quartz vein ranges from ?0.1 to 3‰, whereas δ³⁴S for chalcopyrite in calcite veins ranges from 4 to 5‰. These are similar to the results of previous studies, and suggest a magmatic origin for sulfur. Results from alteration assemblages and vein system observation, as well as geochemical, fluid inclusion, stable isotope studies indicate that the involvement of hydrothermal fluids exsolved from a crystallizing melt are responsible for the formation of Tongchang porphyry Cu‐Mo orebodies in Dexing porphyry deposit.     

东秦岭花岗伟晶岩中电气石地球化学特征及成矿指示意义

东秦岭地区是我国重要的花岗伟晶岩区及稀有金属成矿区.电气石在东秦岭各类花岗伟晶岩中广泛发育,通常在无矿化伟晶岩、铍矿化及锂矿化伟晶岩中呈黑色-深蓝色.本文旨在通过各类伟晶岩中电气石的对比研究揭示电气石地球化学特征对东秦岭伟晶岩矿化类型的指示作用.本文所研究电气石为作为东秦岭各类伟晶岩贯通矿物的黑电气石系列.在双峰村、碾...     

Late Cretaceous magmatism and related metallogeny in the Tengchong area: Evidence from geochronological,isotopic and geochemical data from the Xiaolonghe Sn deposit,western Yunnan,China

Xiaolonghe is a poorly studied greisen-type tin deposit that is hosted by biotite granite in the western Yunnan tin belt. The mineralisation-related metaluminous and weak peraluminous granite is characterised by high Si, Al and K and low Mg, Fe and Ca, with an average A/CNK of 1.02. The granite is enriched in LILEs (K and Rb), LREEs and HFSEs (Zr, Hf, Th, U and Ce) and depleted in Ba, Nb, Sr, P, and Ti, with zircon εHf(t) = − 10.8 to − 7.5 (T_DM2 = 1.61–1.82 Ga). These characteristics indicate that the magma was generated by the partial melting of a thickened ancient crust. LA-ICP-MS U–Pb dating of igneous zircon and hydrothermal cassiterite yield ages of 71.4 ± 0.4 Ma and 71.6 ± 4.8 Ma, respectively. The igneous biotite and hydrothermal muscovite samples show Ar–Ar plateau ages of 72.3 ± 0.4 Ma and 70.6 ± 0.2 Ma, respectively. The close temporal relationship between the igneous emplacement and hydrothermal activity suggests that the tin mineralisation was closely linked to the igneous emplacement. The δ¹⁸O and δD values for the deposit range from + 3.11‰ to − 4.5‰ and from − 127.3‰ to − 94.7‰, respectively. The hydrothermal calcite C and O isotopic data show a wide range of δ¹³C_PDB values from − 5.7‰ to − 4.4‰, and the δ¹⁸O_SMOW values range from + 1.4‰ to + 11.2‰. The δ³⁴S_V-CDT data range from + 4.8‰ to + 8.9‰ for pyrite, and the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios range from 18.708 to 18.760, from 15.728 to 15.754 and from 39.237 to 39.341, respectively. The stable isotopic (C–H–O–S–Pb) compositions are all similar to those of magmatic and mantle-derived fluids, which indicate that the ore-forming fluids and materials were mainly derived from magmatic sources that were accompanied by meteoric water. The tin mineralisation in the Xiaolonghe district was closely associated with the Late Cretaceous crustal-melting S-type granites that formed during the subduction of the Neo-Tethys oceanic lithosphere. Combined with the tin deposits in the Southeast Asian tin belt, Tengchong block and Central Lhasa, we interpreted that a giant intermittent tin mineralisation belt should be present along the Asian Neo-Tethys margin.     

Genesis and Metallogenic Process of the Lujing Uranium Deposit,Southwest Jiangxi Province,China: Constraints of Micropetrography and S–C–O Isotopes

The Lujing uranium deposit, located in the southeastern part of the Nanling metallogenic province, is one of the representative granite‐related hydrothermal uranium deposits in South China. Basic geology, geochemistry, and geochronology of the deposit have been extensively studied. However, there is still a chronic lack of systematic research on the genesis and metallogenic process of the deposit. Thus, we recently carried out an electron microprobe and stable isotopic analysis. The main research results and progresses are as follows: Uranium minerals in this deposit include coffinite, pitchblende, and uranothorite, and small amounts of uranium exist in accessory minerals in the form of isomorphism. Coffinite, which occurs predominantly as the pseudomorphs after pitchblende, also occurs as a primary mineral and is locally formed from the remobilization of uranium from adjacent uranium‐bearing minerals. The mineralizing fluid was originally composed of a magmatic fluid generated by late Yanshanian magmatism. The high As content of pyrite in ores may reflect the addition of meteoric water, or the formation water (or both), to the magmatic hydrothermal system. The δ³⁴S values vary from −14.4‰ to 13.9‰ (mean δ³⁴S = −3.9‰), showing a range that is similar to nearby Cambrian metamorphic strata and Indosinian granites, indicating that these host rocks represent the source of sulfur; however, the possibility of a mantle source cannot be completely ruled out. According to our new isotopic data and recent Pb isotopic data, we conclude that the uranium in ores was derived by leaching dominantly from the uranium‐rich host rocks, especially the Cambrian metamorphic strata. The δ¹³C_PDB values (−8.75‰ to 1.40‰; mean δ¹³C_PDB = −5.41‰) and δ¹⁸O_SMOW values (5.45–18.62‰; mean δ¹⁸O = 13.02‰) of reddish calcite from the ore‐forming stage suggest that the CO₂ in the mineralizing fluids was derived predominantly from the mantle, with a small component contributed by marine carbonates. Based on these new data and previous research results, this paper proposes that uranium metallogenesis in the Lujing deposit is closely associated with mafic magmatism resulting from crustal extension during the Cretaceous to Paleogene in South China.     

The origin of the Dapingzhang volcanogenic Cu–Pb–Zn ore deposit,Yunnan province,SW China: Constraints from host rock geochemistry and ore Os–Pb–S–C–O–H isotopes

The Dapingzhang volcanogenic Cu–Pb–Zn sulfide deposit is located in the Lancangjiang tectonic zone within the Sanjiang region, Yunnan province of southwestern China. The deposit occurs within a felsic volcanic dome belonging to a mid-Silurian volcanic belt stretching for more than 100 km from Dapingzhang to Sandashan. The mineralized volcanic rocks are predominantly keratophyre and quartz keratophyre with subordinate spilite. The Dapingzhang deposit is characterized by well-developed vertical zonation with stockwork ores in the bottom, disseminated sulfide ores in the middle, and massive sulfide ores in the top, overlain by a thin layer of chemical sedimentary exhalative rocks (chert and barite). The Re–Os age of the pyrites from the deposit is 417 ± 23 Ma, indistinguishable from the age of the associated felsic volcanic rocks. The associated felsic volcanic rocks are characterized by negative Nb–Ta anomalies and positive ε_Nd(t) values (+ 4.4–+6.5), similar to the coeval calc-alkaline volcanic rocks in the region. This observation supports the interpretation that the felsic volcanic rocks associated with the Dapingzhang deposit are the derivatives of arc basaltic magma by extensive fractional crystallization. The δ³⁴S values of the sulfides from the deposit vary from − 1.24 to + 4.32‰, indicating a predominantly magmatic source for the sulfur. The sulfides are also characterized by homogeneous and relatively low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.310–18.656, ²⁰⁷Pb/²⁰⁴Pb = 15.489–15.643 and ²⁰⁸Pb/²⁰⁴Pb = 37.811–38.662), similar to the Pb isotopic compositions of the associated volcanic rocks. The Pb isotopic data indicate that mantle-derived Pb is more prevalent than crust-derived Pb in the deposit. The S–Pb isotopic data indicate that the important ore-forming materials were mainly derived from the associated volcanic rocks. The δ¹³C_PDB and δ¹⁸O_SMOW values of the associated hydrothermal calcite crystals vary from − 2.3‰ to + 0.27‰ and from + 14.6 to + 24.4‰, respectively. These values are between the mantle and marine carbonate values. The narrow range of the δ¹³C_PDB values for the calcite indicates that carbon-bearing species in the hydrothermal fluids were primarily derived from marine carbonates. The δ¹⁸O values for the hydrothermal fluids, calculated from the measured values for quartz, are between − 2.1‰ and + 3.5‰. The corresponding δD values for the fluids range from − 59‰ to − 84‰. The O–H isotopic data indicate mixing between magmatic fluids and seawater in the ore-forming hydrothermal system. Similar to a typical volcanogenic massive sulfide (VMS) deposit, the ore-forming fluids contained both magmatic fluids and heated seawater; the ore metals and regents were derived from the underlying magma as well as felsic country rocks.     

Chemical composition and species attribution of tourmalines from a rare-metal pegmatite vein with scapolite, Sangilen Upland, Tuva

A detailed study of the chemical composition and substitutions in calcium tourmalines from a scapolite-bearing rare-metal pegmatite vein from the Sol’bel’der River basin has shown that their species attribution is determined by occupancy of octahedral site Y. The composition of the yellow tourmaline most abundant in the central part of the pegmatite bodyis rather constant and characterized by the ideal formula Ca(Mg₂Li)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃F. Variations in the chemical composition of zonal tourmaline crystals from the contact part of the pegmatite are controlled by abrupt change in the chemical medium during their formation. The yellow cores of these crystals are close in composition to tourmaline from the central part of the pegmatite vein. The Mg content abruptly decreases toward the crystal margin: Mg²⁺ → Fe²⁺, 2Mg²⁺ → Li⁺ + Al³⁺, and Mg²⁺ + OH → Al³⁺ + O²⁻. The composition of dark green marginal zones in tourmaline is characterized by the ideal formula Ca(Al_1.5Li_1.5)Al₆(Si₆O₁₈)(BO₃)₃ (OH₂O)(F). The results indicate specific formation conditions of pegmatite. The crystallochemical formulas of the studied tourmalines allow us to regard them as new mineral species in the tourmaline group.     

Boron isotopes in tourmaline as a tracer of metasomatic processes in the Bamble sector of Southern Norway

The Bamble sector of southern Norway comprises metagabbros and metasediments that were metasomatically altered to various extents during a late stage of the Sveconorwegian orogeny (~1.06 Ga). The infiltration of highly saline brines along veins led to penetrative scapolitization and albitization on a regional scale and the local deposition of Fe–Ti oxides. Typical secondary mineral assemblages include either scapolite + apatite + amphibole + phlogopite + tourmaline, or albite + epidote + calcite + chlorite + white mica, indicating that the fluids introduced large amounts of Na, Cl, Mg, Ca, K, P, and B to the system. Metasomatic tourmalines associated with different alteration stages as identified by variations in major-element composition and initial ⁸⁷Sr/⁸⁶Sr were analyzed for B isotopic compositions to constrain possible sources and the evolution of the hydrothermal fluid(s). Measured δ¹¹B values range from ?5 to +27 ‰ relative to SRM-951, suggesting marine evaporites interlayered with various amounts of continental detritus and pelagic clay as a possible B source reservoir. The influence of a seawater-derived component is clearly indicated by the heavy B isotope signature of tourmaline related to Al–Mg-rich metapelites. In contrast, negative δ¹¹B values can be explained by the influence of pneumatolytic fluids associated with granitic pegmatites. On a regional scale (i.e., several km), δ¹¹B values in tourmaline vary widely, whereas variations within a single outcrop (tens of m) are typically small and can be ascribed to different generations of tourmaline related to several fluid pulses.