Existing forms of tungsten in hydrothermal solutions and forming conditions of scheelite

Experiments on the solubility of WO₃ in HCl and KCl solutions at 200°C show that tungsten cannot migrate in the form of chloride in solutions. In Cl-rich hydrothermal solutions of moderate salinity, tungsten migrates mainly as alkali salts of HWO ₄ ^? and WO ₄ ^2? . Determination of the solubility of WO₃ in HF and KHF₂ solutions at 100–300°C shows that tungsten migrates steadily as WO₃F^? and WO₂F ₃ ^? in F-rich hydrothermal solutions. Experiments and thermodynamic calculations also indicate that silico-wolframic acid, polymeric wolframic acid and sulfoxy wolframic acid cannot extensively occur in hydrothermal solutions. In addition, the physicochemical conditions of formation of scheelite are also discussed in the present paper.     

Experimental modeling of Au and Pt coupled transport by chloride hydrothermal fluids at 350–450°C and 500–1000 bar

The coupled solubility of Au_(cr) and Pt_(cr) has been measured in acidic chloride solutions at 350–450°С and 0.5 and 1 kb using the autoclave technique with determination of dissolved metal contents after quenching. The constants of the reaction combining the dominant species of Au and Pt in high-temperature hydrothermal fluids (K_(Au–Pt)) have been determined: 2 Au_(cr) + PtCl₄^2- = Pt_(cr) + 2AuCl₂^-; log K_(Au–Pt) =–1.02 ± 0.25 (450°С, 1 kb), 0.09 ± 0.15 (450°С, 0.5 kb), and –1.31 ± 0.20 (350°С, 1 kb). It has been established that the factors affecting the Au/Pt concentration ratio in hydrothermal fluids and precipitated ores are temperature, pressure, redox potential, and sulfur fugacity. An increase in temperature results in an increase in the Au/Pt concentration ratio (up to ~550°С at P = 1 kb). A decrease in pressure and redox potential leads to enrichment of fluid in Au. An increase in sulfur fugacity in the stability field of Pt sulfides results in increase in the Au/Pt concentration ratio. Native platinum is replaced by sulfide mineral in low-temperature systems enriched in Pt (relative to Au).     

Hydrothermal alterations in the Echassières granitic cupola (Massif central,france)

Detailed petrographic and mineralogic investigations of an albite-lepidolite granite at Echassières (Massif Central, France; scientific deep drill program) shows the existence of hydrothermal stages which are closely related to the magmatic and structural history. According to fluid inclusion data, K-Ar datations and ¹⁸O/¹⁶O-D/H compositions of secondary minerals, two successive hydrothermal periods have been recognized. The early one (273–268 million years) produced a series of aluminous phyllosilicates: muscovite, pyrophyllite, donbassite, tosudite, kaolinite which are observed as vein deposits (<10 mm wide) and alteration products of primary minerals in wall-rocks. The vein system was sealed by monomineralic assemblages during a cooling period (400–150°C). This early hydrothermal alteration stage was controlled by interactions of rock with low salinity (1–10 wt% NaCl equivalent) fluids expelled from the granitic body during the cooling processes. The chemical properties of these fluids were the following: low pH, very low Mg and Fe and high Li, Na and K contents. Thermodynamic calculations show that the sequence pyrophyllite, Li-bearing donbassite, tosudite is mostly temperature dependent. From the chemical composition of secondary minerals and isotopic data it can be deduced that these fluids, which have a meteoric origin, have been expelled from the granite body during its cooling period and after interaction with it at high temperature. The late hydrothermal stage corresponds to deposits of fluorite and Fe-Mg rich illite (151 million years) in subvertical fractures. Temperature conditions did not exceed 250° C and fluids came through the surrounding metamorphic rocks into the granitic body. IIlite/smectite mixed-layer minerals have been identified in subvertical fractures which were opened during Tertiary periods. In the host micaschists, successive hydrothermal alterations took place during the cooling of the Beauvoir granite. Early magmatic fluids interacted with these micaschists. Locally, the metamorphic assemblage is replaced by a metasomatic one. Secondary topaz and (F, Li)-rich mica crystals were formed over a range of 450 of 150°C. Later hydrothermal fluids reacted with the country rocks to form phengite-biotite, chlorite-illite and kaolinite over a range of 300 to 150°C. Illite/smectite mixed-layer minerals crystallized in the roof micaschists and within the Beauvoir granite during the Tertiary alteration period. Meteoric water invaded open fractures producing supergene alteration mineral assemblages.     

Solubility of tin,tungsten and molybdenum oxides in felsic magmas

Saturation versus undersaturation of granitic melts in tin, tungsten and molybdenum oxides is discussed on the basis of experimental data. Results of dry and hydrothermal experiments are evaluated under the assumption of ideal solubility of Sn, W and Mo oxides in granitic melts. A conservative interpretation arrives at concentration levels of 1000 ppm SnO₂, WO₃ and MoO₃ respectively, considered as the maximum solubility of these components in granitic melts at 750°C-800 °C. Such values are never reached in natural granites unaffected by hydrothermal alteration and therefore even highly evolved granites are expected to be undersaturated in these metals. Consequently cassiterite and scheelite are neither common liquidus minerals of ore-bearing granites nor restite minerals from partial melting events.     

赣中聚源大型石英脉型白钨矿床含铀富钨矿物初步研究

聚源钨矿是华南地区为数不多的大型石英脉型白钨矿矿床之一.在详细的野外地质调查基础上,本文利用α径迹蚀刻、电子显微镜、扫描电镜以及电子探针等实验手段,对该矿床含钨和含铀矿物开展了精细矿物学的研究工作,探讨了成矿过程中钨和铀的富集规律.研究显示,该矿床钨铀矿物的形成可分为四个阶段:第一阶段,钨铀主要进入富含Nb、Ti的氧化...     

Skarn mineralogy and trace elements of scheelite in Xianglushan tungsten deposit,Jiangxi Province,South China and their implications for mineralization processSCIEI北大核心CSCD

江西省香炉山钨矿是江南古陆斑岩-矽卡岩钨多金属成矿带内具有代表性的早白垩世矽卡岩型钨矿床。矿床的WO3储量约为22万t,平均品位约为0.641%。矿床的矿体以似层状和透镜状产出于燕山期黑云母花岗岩和寒武系杨柳岗组泥灰岩的接触带。本文在详细厘定成矿阶段矿物组合的基础上,对不同阶段产出的不同世代的白钨矿开展了原位LA-ICP-MS微量元素的系统测试。香炉山钨矿床可以划分为四个成矿阶段:矽卡岩阶段、退化蚀变阶段、石英-硫化物-白钨矿阶段和方解石-萤石阶段。根据各阶段矿物组合及与白钨矿共生关系,本次研究划分出四个阶段六个世代的白钨矿,分别为阶段Ⅰ白钨矿(产于云英岩中)、阶段Ⅱa和阶段Ⅱb白钨矿(产于退化蚀变岩)、阶段Ⅲa和阶段Ⅲb白钨矿(产于硫化物条带,Ⅲa为白钨矿核部,Ⅲb为白钨矿边部)和阶段Ⅳ白钨矿(产于石英-硫化物-白钨矿脉)。白钨矿的球粒陨石标准化稀土元素配分图有下凹型(阶段Ⅰ、阶段Ⅱa、阶段Ⅲb)、右倾型(阶段Ⅳ)和下凹右倾型(阶段Ⅲa)。各阶段白钨矿的微量元素特征表明,香炉山钨矿床白钨矿的∑REE含量高于世界上绝大部分脉状金和钨矿床,也高于我国华南地区钨多金属矿床。白钨矿中REE3+与Ca2+主要的替代机制为3Ca2+=2REE3++Ca(为一个Ca空位)。白钨矿的REE和Eu异常由流体决定,可以用来示踪流体的演化过程,Eu的活动主要以Eu2+为主。香炉山钨矿床为还原性矿床,不同阶段白钨矿中Mo等元素含量的变化指示流体演化各阶段的还原性强弱有波动。不同阶段白钨矿的稀土和微量元素特征有较大变化。香炉山白钨矿稀土元素的超常富集原因和机制仍有待进一步研究和探讨。     

碳酸岩型稀土矿床成矿流体演化机制研究现状及展望

与碱性岩有关的碳酸岩型内生稀土矿床在中国乃至世界上轻稀土资源储量中占有极为重要的地位,诸如我国内蒙古的白云鄂博稀土矿床、川西冕宁—德昌稀土成矿带中的牦牛坪、大陆槽等稀土矿床、山东微山县郗山稀土矿床以及美国的Mountain Pass稀土矿床等都属于这种类型的稀土矿床.当前,对于这类稀土矿床的成矿流体演化机制,学界主要存...     

Geology and Genesis of the Ta'ergou Skarn - Quartz Vein Tungsten Deposit in the North Qilian Caledonian Orogenic Belt, Northwest China

Abstract. The Ta'ergou tungsten deposit in Gansu province, northwestern China, is located in the western part of the North Qilian Caledonian orogen, and consists of scheelite skarn bodies and wolframite quartz veins. The tungsten‐bearing skarn developed by the replacement of carbonate layers intercalated in the Precambrian schist and amphibolite whereas wolframite‐quartz ore veins developed along a group of fractures that cut through horizontal skarns. The Ta'ergou tungsten deposit is genetically related to the Caledonian Yeniutan granodiorite intrusion and occurs ca. 500 m wide in the exo‐contact zone 300 ～ 500 m apart from the intrusion. The granodiorite displays a lower grade of differentiation, low content of SiO₂ and high contents of mafic components. There are three types of fluid inclusions in the wolframite‐quartz vein systems, i. e. aqueous, CO₂‐H₂O and CO₂‐rich. The homogenization temperature of aqueous inclusion ranges from 140 to 380d?C and their salinities from 6.4 to 17.4 equivalent wt% NaCl. Laser Raman spectroscopy shows that the inclusions contain a relatively high content of CO₂. The δ³⁴S values of skarn type sulfides range from +8.1 to +12.7 per mil and those of quartz vein sulfides from +9.3 to +14.9 per mil, similar to sulfides of the granodiorite with from +6.0 to +11.7 per mil. The δ¹⁸O values of quartz are between +10.5 and +13.3 per mil and those of wolframite between +3.4 and +5.1 per mil. The δ¹⁸O water values of ore forming fluids range from +0.6 to +6.4 per mil and suggest the mixture of magmatic fluids with meteoric water formed the ore‐forming fluids. It has been proved that Precambrian strata in the west sector of North Qilian region are enriched in tungsten. We propose the strata were remelted to be tungsten‐granitoid during subduction. The polymetallic tungsten was gradually accumulated into the roof pendants of the granite intrusion by fractional crystallization and then was deposited by hydrothermal fluids during metasomatism and infilling along fractures. On the other hand, the granite intrusion also acted as “heating machine” to make hydrothermal fluids leach out the metals from Precambrian strata and these metals joined the ore‐forming hydrothermal system.     

Geology,mineralization, and fluid inclusion characteristics of the Lermontovskoe reduced-type tungsten (±Cu,Au, Bi) skarn deposit,Sikhote-Alin,Russia

The Lermontovskoe deposit (∼48 Kt WO₃; average 2.6% WO₃, 0.24% Cu, 0.23 g/t Au) is situated in a W-Sn-Au metallogenic belt that formed in a collisional tectonic environment. This tungsten skarn deposit has a W-Au-As-Bi-Te-Sb signature that suggests an affinity with reduced intrusion-related Au deposits. The deposit is associated with an intrusion that is part of the ilmenite-series, high-K peraluminous granitoid (granodiorite to granite) suite. These rocks formed via mantle magma-induced melting of crustal sources.The deposit comprises reduced-type, pyroxene-dominated prograde and retrograde skarns followed by hydrosilicate (amphibole-chlorite-pyrrhotite-scheelite-quartz) and phyllic (muscovite/sericite-carbonate-albite-quartz-scheelite-sulfide, with abundant apatite) alteration assemblages. Fluid inclusions from the skarn assemblages indicate high-temperature (>500 °C), high-pressure (1400–1500 bars) and high-salinity (53–60 wt% NaCl-equiv.) magmatic-hydrothermal fluids. They were post-dated by high-carbonic, methane-dominate, low-salinity fluid at the hydrosilicate alteration stage. These fluids boiled at 360–380 °C and 1300–1400 bars. The subsequent phyllic alteration started again with a high-temperature (>450 °C), high-pressure (1000–1100 bars) and high-salinity (42–47 wt% NaCl-equiv.) fluid, with further incursion of high-carbonic, methane-dominated, low-salinity fluid that boiled at 390–420 °C and 1150–1200 bars. The latest phyllic alteration included the lower-temperature (340–360 °C), lower pressure (370–400 bars) high-carbonic, methane-dominated (but with higher CO₂ fraction), low-salinity fluid, and then the low-temperature (250–300 °C) H₂O-CO₂-CH₄-NaCl fluid, with both fluids boiled at the deposit level. The high-salinity aqueous fluids are interpreted to have come from crystallizing granitoid magma, whereas the reduced high-carbonic fluids probably came from a deeper mafic magma source. Both of these fluids potentially contributed to the W-Au-As-Bi-Te-Sb metal budget. Decreasing temperatures coupled with high aCa²⁺ and fluid boiling promoted scheelite deposition at all post-skarn hydrothermal stages.The deposit is characterized by limited downdip extent of mineralized zones and abundant coarse-grained muscovite-quartz (+apatite, scheelite) aggregates that formed at the phyllic alteration stage. Together with presence of high-temperature, high-pressure and high-salinity fluids directly exsolving from crystallizing magma, this suggests a root level of the mineralized magmatic-hydrothermal system of reduced W skarn deposits.     

Origins of Nd–Sr–Pb isotopic variations in single scheelite grains from Archaean gold deposits,Western Australia

Accessory gangue scheelite (CaWO₄) from the Archaean Mt. Charlotte lode Au deposit can be divided into two types with different rare earth element (REE) signatures. In some scheelite grains, specific REE signatures are reflected by different cathodoluminescence colours, which can be used to map their often complex oscillatory intergrowths. Domains with specific REE contents from two grains were sampled for Sm/Nd, Rb/Sr and Pb isotopic analyses using a micro-drilling technique.Type I scheelite is strongly enriched in middle REE (MREE) and Eu anomalies are either absent or slightly positive. Four fragments collected from Type I regions of two crystals have initial ⁸⁷Sr/⁸⁶Sr and ε_Nd values ranging from 0.70141 to 0.70163 and +2.5 to +3.5, respectively, and Pb isotope ratios reflecting the composition of greenstone sequence. This may indicate that Nd and Pb have their source, either locally or regionally, in the greenstones. Basic greenstone lithologies have ⁸⁷Sr/⁸⁶Sr<0.7015, and the radiogenic Sr signatures indicate that part of the Sr originated from felsic lithologies located either within or beneath the host greenstone pile. Alternatively, the Sr signature may have evolved from preferential leaching of a Rb-rich mineral during hydrothermal alteration of the greenstone.The REE patterns of Type II scheelite are either flat or MREE-depleted and have strong positive Eu anomalies. Three fragments collected from Type II regions of the same two crystals have initial ⁸⁷Sr/⁸⁶Sr ratios and ε_Nd values between 0.70130 and 0.70146, and +1.1 to +2.6, respectively, and Pb isotope signatures that are once again similar to that of the greenstone. This implies that ⁸⁷Sr/⁸⁶Sr ratios in Type II fluids were closer to those of the host dolerite (0.7008–0.7013), due to more extensive fluid interaction with the dolerite.A positive correlation between Na and REE suggests that REE³⁺ are accommodated by the coupled substitution REE³⁺+Na⁺=2 Ca²⁺ into both Type I and Type II scheelite. This is consistent with a fractional crystallisation model to explain the change in REE patterns from Type I to Type II, but not with a model involving different coupled substitutions and fluids from different origins. We propose that the complex REE and isotopic signatures of scheelite at Mt. Charlotte are related to small (<m) to medium (<km) scale processes involving mixing between “fresh” batches of hydrothermal fluid with fluids that had already been involved in extensive wall-rock alteration.The very high-ε_Nd values measured in some scheelites have been previously used to link gold mineralisation with komatiites containing unusually high Sm/Nd ratios. However, tiny (<20 μm) grains of secondary hydroxyl-bastnäsite were found within micro-fractures of one scheelite grain containing an extremely high-ε_Nd signature. The hydroxyl-bastnäsite probably formed during recent REE redistribution within the scheelite as a result of meteoric fluid circulation. The scale of this cryptic low-temperature alteration is sufficient to explain the anomalously high-ε_Ndi values observed in scheelite from Western Australia.     

Physicochemical parameters of the formation of hydrothermal deposits: A fluid inclusion study. I. Tin and tungsten deposits

The author’s database, which presently includes data from more than 18500 publications on fluid and melt inclusions in minerals and is continuing to be appended, was used to generalize results on physicochemical parameters of the formation of hydrothermal deposits and occurrences of tin and tungsten. The database includes data on 320 tin and tin-tungsten deposits and occurrences and 253 tungsten and tungstentin deposits around the world. For most typical minerals of these deposits (quartz, cassiterite, tungsten, scheelite, topaz, beryl, tourmaline, fluorite, and calcite), histograms of homogenization temperatures of fluid inclusions were plotted. Most of 463 determinations made for cassiterite are in the range of 300–500°C with maximum at 300–400°C, while those for wolframite and scheelite (453 determinations) fall in the range of 200–400°C with maximum at 200–300°C. Representative material on pressures of hydrothermal fluids included 330 determinations for tin and 430 determinations for tungsten objects. It was found that premineral, ore, and postmineral stages spanned a wide pressure range from 70–110 bar to 6000–6400 bar. High pressures of the premineral stages at these deposits are caused by their genetic relation with felsic magmatism. Around 50% of pressure determinations lie in the range of 500–1500 bar. The wide variations in total salinity and temperatures (from 0.1 to 80 wt % NaCl equiv and 20–800°C) were obtained for mineral-forming fluids at the tin (1800 determinations) and tungsten (2070 determinations) objects. Most of all determinations define a salinity less than 10 wt % NaCl equiv. (∼60%) and temperature range of 200–400°C (∼70%). The average composition of volatile components of fluids determined by different methods is reported. Data on gas composition of the fluids determined by Raman spectroscopy are examined. Based on 180 determinations, the fluids from tin objects have the following composition (in mol %): 41.2 CO₂, 39.5 CH₄, 19.15 N₂, and 0.15 H₂S. The volatile components of tungsten deposits (190 determinations) are represented by 56.1 CO₂, 30.7 CH₄, 13.2 N₂, and 0.01 H₂S. Thus, the inclusions of tungsten deposits are characterized by higher CO₂ content and lower (but sufficiently high) contents of CH₄ and N₂. The concentrations of tin and tungsten in magmatic melts and mineral-forming fluids were estimated from analysis of individual inclusions. The geometric mean Sn contents are 87 ppm (+ 610 ppm/−76 ppm) in the melts (569 determinations) and 132 ppm (+ 630 ppm/−109 ppm) in the fluids (253 determinations). The geometric mean W values are 6.8 ppm (+ 81/−6.2 ppm) in the magmatic melts (430 determinations) and 30 ppm (+ 144 ppm/−25 ppm) in the mineral-forming fluids (391 determinations).     

Geochemistry of stratabound scheelite mineralisation and associated calc-silicate rocks from Chitral,NE Hindu Kush,Pakistan

Tungsten mineralisation in the NE Hindu Kush terrain occurs 8 km NW of the Tirich Boundary Zone suture between Karakoram and Eastern Hindu Kush. Scheelite occurs mainly in calc-silicate rocks and subordinately in tourmalinites associated with metasediments at Miniki Gol, Chitral. The investigated area underwent two phases of deformation and was metamorphosed up to sillimanite grade, followed by the emplacement of leucogranite and hydrothermal activity. The mineral assemblages of the calc-silicate rocks, comprising clinozoisite, quartz, calcic-amphibole, plagioclase, chlorite, biotite, calcite, sphene, garnet and scheelite, clearly express a skarn type environment. The coexistence of the scheelite grains with clinozoisite and the occurrence of anomalous values of ZrO₂ and Ta₂O₅ in the scheelite grains imply a genetic link between the scheelite mineralisation and post-magmatic hydrothermal fluids. The enrichment of Zr, Hf, Be, Sn, W, Th, U, Ga, Nb, F and Y along with total REE in the scheelite-bearing calc-silicate rocks compared with the associated metasediments assigns that the rocks at Miniki Gol have undergone a pronounced hydrothermal activity. Strong positive correlations between Zr, Hf, Nb, Y, Ta, F and REE, and the mobility of REE are consistent with this consideration. Aqueous fluid inclusions in the scheelite-bearing calc-silicate rocks display very low salinity, suggesting a mixing of magmatic fluids with meteoric water. The formation of intergrown scheelite and clinozoisite indicates a high pH and CO₂-deficient fluid. The tungsten mineralization may be related to the Miniki Gol leucogranite which occurs at a distance of only 400 m.     

Fluid Inclusions and Hydrogen,Oxygen, Sulfur Isotopes of Nuri Cu‐W‐Mo Deposit in the Southern Gangdese,Tibet

The Nuri Cu‐W‐Mo deposit is located in the southern subzone of the Cenozoic Gangdese Cu‐Mo metallogenic belt. The intrusive rocks exposed in the Nuri ore district consist of quartz diorite, granodiorite, monzogranite, granite porphyry, quartz diorite porphyrite and granodiorite porphyry, all of which intrude in the Cretaceous strata of the Bima Group. Owing to the intense metasomatism and hydrothermal alteration, carbonate rocks of the Bima Group form stratiform skarn and hornfels. The mineralization at the Nuri deposit is dominated by skarn, quartz vein and porphyry type. Ore minerals are chalcopyrite, pyrite, molybdenite, scheelite, bornite and tetrahedrite, etc. The oxidized orebodies contain malachite and covellite on the surface. The mineralization of the Nuri deposit is divided into skarn stage, retrograde stage, oxide stage, quartz‐polymetallic sulfide stage and quartz‐carbonate stage. Detailed petrographic observation on the fluid inclusions in garnet, scheelite and quartz from the different stages shows that there are four types of primary fluid inclusions: two‐phase aqueous inclusions, daughter mineral‐bearing multiphase inclusions, CO₂‐rich inclusions and single‐phase inclusions. The homogenization temperature of the fluid inclusions are 280°C–386°C (skarn stage), 200°C–340°C (oxide stage), 140°C–375°C (quartz‐polymetallic sulfide stage) and 160°C–280°C (quartz‐carbonate stage), showing a temperature decreasing trend from the skarn stage to the quartz‐carbonate stage. The salinity of the corresponding stages are 2.9%–49.7 wt% (NaCl) equiv., 2.1%–7.2 wt% (NaCl) equiv._, 2.6%–55.8 wt% (NaCl) equiv. and 1.2%–15.3 wt% (NaCl) equiv., respectively. The analyses of CO₂‐rich inclusions suggest that the ore‐forming pressures are 22.1 M Pa–50.4 M Pa, corresponding to the depth of 0.9 km–2.2 km. The Laser Raman spectrum of the inclusions shows the fluid compositions are dominated in H₂O, with some CO₂ and very little CH₄, N₂, etc. δD values of garnet are between ?114.4‰ and ?108.7‰ and δ¹⁸O_H2O between 5.9‰ and 6.7‰; δD of scheelite range from ?103.2‰ to ?101.29‰ and δ¹⁸O_H2O values between 2.17‰ and 4.09‰; δD of quartz between ?110.2‰ and ?92.5‰ and δ¹⁸O_H2O between ?3.5‰ and 4.3‰. The results indicate that the fluid came from a deep magmatic hydrothermal system, and the proportion of meteoric water increased during the migration of original fluid. The δ³⁴S values of sulfides, concentrated in a rage between ?0.32‰ to 2.5‰, show that the sulfur has a homogeneous source with characteristics of magmatic sulfur. The characters of fluid inclusions, combined with hydrogen‐oxygen and sulfur isotopes data, show that the ore‐forming fluids of the Nuri deposit formed by a relatively high temperature, high salinity fluid originated from magma, which mixed with low temperature, low salinity meteoric water during the evolution. The fluid flow through wall carbonate rocks resulted in the formation of layered skarn and generated CO₂ or other gases. During the reaction, the ore‐forming fluid boiled and produced fractures when the pressure exceeded the overburden pressure. Themeteoric water mixed with the ore‐forming fluid along the fractures. The boiling changed the pressure and temperature, oxygen fugacity, physical and chemical conditions of the whole mineralization system. The escape of CO₂ from the fluid by boiling resulted in scheelite precipitation. The fluid mixing and boiling reduced the solubility of metal sulfides and led the precipitation of chalcopyrite, molybdenite, pyrite and other sulfide.     

Multiple sources for mineralizing fluids in the Charmitan gold(-tungsten) mineralization (Uzbekistan)

Mineral assemblages present within the Charmitan gold(-tungsten) quartz-vein mineralization have been investigated for their cathodoluminescence behaviour, chemical composition and noble gas isotope systematics. This inventory of methods allows for the first time a systematic reconstruction of the paragenetic relationships of quartz, scheelite, sulphides and native gold within the gold mineralization at Charmitan and provides the basis to utilise noble gas data in the discussion of sources and evolution of ore-forming fluids. The vein quartz is classified into four generations based on microscopic and cathodoluminescence investigations. Quartz I shows intense brittle deformation as associated scheelite I. Undeformed scheelite II overgrows scheelite I and has lower light rare earth element and higher intermediate rare earth element contents as well as higher strontium concentrations. Scheelite II is associated with the economic gold mineralization and formed during re-crystallisation and re-precipitation of material which was partly re-mobilised from early scheelite I during infiltration of gold-bearing fluids. Early stage native gold inclusions are often associated with stage 2 sulphides, scheelite II and bismuth tellurides and contain Ag (3.6–24.4 wt.%), Hg (≤1.0 wt.%) and Bi (≤0.2 wt.%). Later stage electrum grains occur in association with stage 3 sulphides and sulphosalts and contain Hg (<0.8 wt.%) and elevated Sb concentrations (up to 3.0 wt.%). Noble gas isotope data (³He/⁴He: 0.2-0.4 Ra) for hydrothermal ore fluids trapped in the gold-related sulphides and sulphosalts (stage 2 pyrite and arsenopyrite; stage 3 pyrite, sphalerite, galena and lead sulphosalts) suggest that diverse fluid sources were involved in the formation of the Charmitan gold deposit. These data are indicative of a small, but significant input of fluids from external, deep-seated (mantle and possibly lower crust) sources. A decrease in the input of mantle helium and an increasing role of crustal helium from early to later stages of the mineralization is suggested by the measured ³He/⁴He and ⁴⁰Ar*/⁴He ratios. Sulphides from ore veins in meta-sedimentary rocks contain higher portions of meteoric fluids than those in intrusive rock types as indicated by their lower ³He/³⁶Ar ratios. The ³He/³⁶Ar ratios in the meta-sedimentary rocks agree well with ratios typical of gold mineralizations in the Tien Shan gold province completely hosted by meta-sedimentary sequences, indicating intense fluid-wall rock interaction.     

浆液过渡态流体在矽卡岩型钨矿成矿过程中的作用——以湖南柿竹园钨锡多金属矿为例

湖南杮竹园是世界著名的大型矽卡岩型锡钨多金属矿床,产于千里山碱长花岗岩岩体南部接触带。矽卡岩中广泛发育网脉状碱交代脉和少量花岗岩脉、云英岩脉等各类脉体。碱交代脉主体由钾长石、萤石、少量石英、磁铁矿、黑钨矿、白钨矿及花岗岩构成,以往被统称为"云英岩脉"。其中早阶段碱交代脉中央发育花岗岩,边部为钾长石-萤石-黑钨矿,脉体两侧发育石榴子石透辉石矽卡岩化,对应矽卡岩阶段。晚阶段碱交代脉主要成分为钾长石、萤石,脉体及两侧出现大量阳起石、绿帘石、磁铁矿、白钨矿及辉钼矿、辉铋矿、自然铋等,对应退变质氧化物阶段。空间上,碱交代脉分布于矽卡岩和矽卡岩化大理岩中,不进入岩体。自花岗岩体→岩脉→碱交代脉→矽卡岩,Ca O、Ti O2、成矿元素W、Bi、Mo、Cu、Pb、Zn以及Sr、Ba等元素含量增高,显示出成矿元素向热液中富集,且岩浆和矽卡岩受到碳酸盐岩围岩的影响。碱交代脉的组构显示出其形成于富含成矿物质和挥发份流体的岩浆,其中广泛发育熔融包裹体和熔流包裹体,显示其浆液过渡态流体的成因性质。从岩浆晚期分异演化→热液阶段是连续演化的过程,块状云英岩和矽卡岩阶段,岩浆并未完全固结,成矿作用自岩浆固结之前已经开始。总结了杮竹园矿床成矿模型:碱长花岗岩岩浆演化晚期分异出的高度富含挥发份的熔浆,在岩体顶部聚集,部分形成似伟晶岩(壳)和块状云英岩以及条带状硅灰石符山石矽卡岩。进一步聚集以及矽卡岩化产生大量CO2引起大规模隐爆,富含挥发份的岩浆或浆液过渡态流体沿隐爆形成的碎裂裂隙进入碳酸盐岩围岩,与碳酸盐岩不断发生反应,在脉体边部形成钾长石化以及大范围的石榴子石透辉石矽卡岩化。至退变质氧化物阶段,随着岩浆冷凝和温度、压力的降低,地下水大范围参与,成矿流体逐渐转变为热液性质,形成大量阳起石、磁铁矿、白钨矿及钼、铋硫化物。硫化物阶段,大量的大气降水参与成矿,温度、盐度进一步降低,在矽卡岩及其外侧的碳酸盐岩中形成铅锌硫化物矿石。     

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.     

Experimental Studies of the Solubility of Cassiterite and the Extraction of Tin from Granitic Melts

Experiments indicate that the solubility of cassiterite can be enhanced by increasing either acidity or alkalinity in hydrothermal solutions as a consequence of the duality of tin.The minimum solubility of cassiterite is found in neutral solutions.F-and CL-coordination compounds of Sn can alternate with hydroxyl coordination compounds with changing pH in the solutions.In this case,F^- and Cl^- and OH^- can be substituted with each other.The dissolution reaction of cassiterite is of reducing nature.High temperature and acidic reducing environment are favorable for the dissolution of cassiterite and the trans-port of Sn^2 compounds in fluids or solutions.High-temperature fluoride and chloride fluids can all dissolve,extract and enrich Sn to form F^- and /or Cl-coordination compounds,However,Fplays a more important role than Cl.F-coordination compounds are more stable and efficient than Cl-coordination compounds during the transport an enrichment of Sn in melts or solutions.The solubili-ty of cassiterite and the amount of Sn extracted from granitic melt depend not only on T,P,pH and Eh in the fluids or solutions,but also on the amounts of dissociated F^- and Cl^- in the fluids.     

Geochronology and Ore‐Forming Fluids of the Baizhangyan W–Mo Deposit in the Chizhou Area,Middle‐Lower Yangtze Valley,SE‐China

The Baizhangyan skarn‐porphyry type W–Mo deposit is located in a newly defined Mo–W–Pb–Zn metallogenic belt, which is in the south of Middle‐Lower Yangtze Valley Cu–Fe–Au polymetallic metallogenic belt in SE China. The W–Mo orebodies occur mainly within the contact zone between fine‐grained granite and Sinian limestone strata. There are two types of W–Mo mineralization: major skarn W–Mo mineralization and minor granite‐hosted disseminated Mo mineralization which was traced by drilling at depth. Eight molybdenite samples from Mo‐bearing ores yield Re–Os dates that overlap within analytical error, with a weighted average age of 134.1 ± 2.2 Ma. These dates are in close agreement with SIMS U–Pb concordant zircon age for fine‐grained granite at 133.3 ± 1.3 Ma, indicating that crystallization of the granite and hydrothermal molybdenite formation were coeval and likely cogenetic. The Baizhangyan W–Mo deposit formed in the Early Cretaceous extensional tectonic setting at the Middle‐Lower Yangtze Valley metallogenic belt and the Jaingnan Ancient Continent. Based on mineral compositions and crosscutting relationships of veinlets, hydrothermal alteration and mineralization, the ore mineral paragenesis of the Baizhangyan deposit is divided into four stages: skarn stage (I), oxide stage (II), sulfide stage (III), and carbonate stage (IV). Fluid inclusions in garnet, scheelite, quartz and calcite from W–Mo ores are mainly aqueous‐rich (L + V) type inclusions. Following garnet deposition at stage I, the high‐temperature fluids gave way to progressively cooler, more dilute fluids associated with tungsten–molybdenite–base metal sulfide deposition (stage II and stage III) (162–360°C, 2.7–13.2 wt % NaCl equivalent) and carbonate deposition (stage IV) (137–190°C, 0.9–5 wt % NaCl equiv.). Hydrogen‐oxygen isotope data from minerals of different stages suggest that the ore‐forming fluids consisted of magmatic water, mixed in various proportions with meteoric water. From stage I to stage IV, there is a systematic decrease in the homogenization temperature of the fluid‐inclusion fluids and calculated δ¹⁸O values of the fluids. These suggest that increasing involvement of formation water or meteoric water during the fluid ascent resulted in successive deposition of scheelite and molybdenite at Baizhangyan.     

Ore Genesis of the Lunwei Granite‐Related Scheelite Deposit in the Wuyi Metallogenic Belt,Southeast China: Constraints from Geochronology,Fluid Inclusions,and H–O–S Isotopes

A granite‐related scheelite deposit has been recently discovered in the Wuyi metallogenic belt of southeast China. The veinlet–disseminated scheelite occurs mainly in the inner and outer contact zones of the porphyritic biotite granite, spatially associated with potassic feldspathization and silicification. Re–Os dating of molybdenite intergrowths with scheelite yield a well‐constrained isochron age of 170.4 ± 1.2 Ma, coeval with the LA–MC–ICP–MS concordant zircon age of porphyritic biotite granite (167.6 ± 2.2 Ma), indicating that the Lunwei W deposit was formed in the Middle Jurassic (~170 Ma). We identify three stages of ore formation (from early to late): (I) the quartz–K‐feldspar–scheelite stage; (II) the quartz–polymetallic sulfide stage; and (III) the quartz–carbonate stage. Based on petrographic observations and microthermometric criteria, the fluid inclusions in the scheelite and quartz are determined to be mainly aqueous two‐phase (liquid‐rich and gas‐rich) fluid inclusions, with minor gas‐pure and CO₂‐bearing fluid inclusions. Ore‐forming fluids in the Lunwei W deposit show a successive decrease in temperature and salinity from Stage I to Stage III. The homogenization temperature decreases from an average of 299 °C in Stage I, through 251 °C in Stage II, to 212 °C in Stage III, with a corresponding change in salinity from an average of 5.8 wt.%, through 5.2 wt.%, to 3.4 wt.%. The ore‐forming fluids have intermediate to low temperatures and low salinities, belonging to the H₂O–NaCl ± CO₂ system. The δ¹⁸O_H2O values vary from 1.8‰ to 3.3‰, and the δD_V‐SMOW values vary from –66‰ to –76‰, suggesting that the ore‐forming fluid was primarily of magmatic water mixed with various amounts of meteoric water. Sulfur isotope compositions of sulfides (δ³⁴S ranging from –1.1‰ to +2.4‰) and Re contents in molybdenite (1.45–19.25 µg/g, mean of 8.97 µg/g) indicate that the ore‐forming materials originated mainly in the crust. The primary mechanism for mineral deposition in the Lunwei W deposit was a decrease in temperature and the mixing of magmatic and meteoric water. The Lunwei deposit can be classified as a porphyry‐type scheelite deposit and is a product of widespread tungsten mineralization in South China. We summarize the geological characteristics of typical W deposits (the Xingluokeng, Shangfang, and Lunwei deposits) in the Wuyi metallogenic belt and suggest that porphyry and skarn scheelite deposits should be considered the principal exploration targets in this area.     

湘南黄沙坪多金属矿床花岗斑岩的矿物化学及其对矽卡岩白钨矿成矿的指示意义

黄沙坪多金属矿床是湖南最大的铅锌生产基地,并且在与矿床内花岗斑岩接触的矽卡岩带产有隐伏的大型矽卡岩型白钨矿和中型规模的辉钼矿。钨-钼矿化的时代为晚侏罗世,与矿床内花岗斑岩侵入时代一致。然而,已有研究认为,由于该花岗斑岩规模很小,矽卡岩型白钨矿的成矿热液应来自深部岩浆房而非此花岗斑岩。为此,我们对花岗斑岩进行了仔细的镜下观测,并且对其中的副矿物和黑云母以及矽卡岩中的白钨矿进行了电子探针成分分析,应用原位LA-ICP-MS方法测定了矽卡岩中白钨矿的稀土元素含量,试图对白钨矿矿化的物质和流体来源提供确切的证据。通过研究,首次在矿床内花岗斑岩中发现了与未蚀变黑云母伴生的黑钨矿和铌铁矿,表明花岗斑岩至少在岩浆结晶作用晚期或岩浆-热液过渡阶段早期就已发生钨的矿物富集,为确定花岗斑岩是控制钨矿化的成矿岩体提供了依据。此外,发现花岗斑岩中的黑云母(属铁叶云母)含有极高的氟含量(3%),指示其应形成于富含氟的高分异岩浆。研究进一步揭示,矽卡岩中白钨矿的轻稀土元素配分模式与花岗斑岩十分一致,而重稀土元素则显著亏损,而且Eu的含量较花岗斑岩更为富集。这暗示形成白钨矿的成矿流体应直接来自花岗斑岩,即:在早期无水矽卡岩阶段,石榴子石的沉淀导致流体中的重稀土亏损而Eu相对富集;白钨矿随后再从这种流体中沉淀。此外,白钨矿的Eu含量与Sm、Gd含量具有负相关关系,表明Eu的分配是相对独立的行为,主要以Eu2+存在,从而指示沉淀白钨矿的流体具有还原的性质。结合前人的研究成果及本文所提供的新证据,我们认为,形成矽卡岩型白钨矿的钨和成矿热液应来自高分异且富F的花岗斑岩,而所需的钙则可能来自于碳酸盐围岩,即矿床内花岗斑岩应是形成钨钼矿床的物质来源,驱动热液活动的能量来源,和寻找隐伏钨矿床的重要找矿标志。