Coexistence of a Fluid Phase with Granitic Magma: Geochemical Characteristics of REE and Cu in Miyako Granite and in Scheelite-bearing Aplitic Veins at the Yamaguchi Cu-W Skarn Deposit, Iwate, Japan

Abstract: The North granitic body of the Miyako pluton is located in the Northern Kitakami belt, Northeast Japan. The formation of the scheelite–chalcopyrite–magnetite–bearing aplitic veins and scheelite–chalcopyrite–magnetite–bearing Yamaguchi skarn deposit was closely associated with the formation of the Miyako plutons. Petrographic facies of the North granitic body vary from quartz diorite in marginal zone (zone A), to tonalite and granodiorite (zone B), and to granite (zone C) in the central. The large numbers of aplitic veins distributed around the Yamaguchi mining area are divided into two groups: barren and scheelite–mag–netite–chalcopyrite–bearing aplitic veins. The latter cut massive clinopyroxene skarns of the Yamaguchi deposit, and are composed of plagioclase, K‐feldspar and titanite. Some plagioclase crystals have dusty cores with irregularly shaped K‐feldspar flakes, and clear rims of albite. Textures of plagioclase in the mineralized aplitic veins are different from the idiomorphic textures with sharp plagioclase crystal boundaries that occur in the North granitic body and barren aplitic veins. These textural data suggest that the mineralized aplitic veins were formed from hydrothermal fluid. Changes in the contents of major and minor (Rb, Sr, Sc, Co, Th, U) elements in the North Miyako granitic body are similar to those of zoned plutons formed by typical magmatic differentiation processes. On the other hand, concentrations of REE, especially middle to heavy REE, of granitic rocks in zone C and barren aplitic veins are significantly lower than those of granitic rocks in zones A and B. The hypothetical chondrite‐normalized REE patterns, calculated assuming fractional crystallization from zone B granitic melt, suggest that REE concentrations of the residual melt increased with the degree of fractional crystallization, and changed into a pattern with enriched LREE and strongly negative Eu anomaly. However, the REE patterns of granitic rocks in zone C are different from the hypothetical patterns. Moreover, the REE patterns of magnetite–scheelite–chalcopyrite aplitic veins are quite different from those of granitic rocks. The Cu contents of granitic rocks in the North Miyako body increase from zone A (5–26 ppm) to zone B (10–26 ppm), and then clearly decrease to zone C (5–7 ppm) and drastically increase to the barren aplitic veins (39–235 ppm). Concentrations of Cu in the mineralized aplitic veins are also higher than those of the granitic rocks in zone C. The decrease in REE and Cu contents of granitic rocks from zone B to zone C is not a result of simple magmatic fractional differentiation. Fluid inclusions in quartz from mineralized aplitic veins contain 3.3 wt% NaCl equivalent and 5.8 wt% CO₂. It was also demonstrated experimentally that the removal of MREE and HREE by fluid from melt enabled the formation of complexes of REE and ligands of OH^‐ and CO₃^2‐. Based on the possibility that the melt of the granitic rocks of zone C and the mineralized aplitic veins coexisted with CO₂‐bearing fluid, it is thought that REE were extracted from the melt to the CO₂‐bearing fluid, and that the REE in the mineralized aplitic veins were transported by the CO₂‐bearing fluid. It is likely that the low HREE and Cu contents of the granitic rocks in zone C could have been caused by the removal of those elements from the granitic melt by the fluid coexisting with the melt. The expelled materials could have been the sources of scheelite–magnetite–chalcopyrite–bearing aplitic veins and copper mineralization of the Yamaguchi Cu‐W skarn deposit.     

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.     

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.     

Hydrothermal alteration processes in the giant Dahutang tungsten deposit,South China: Implications from litho-geochemistry and mass balance calculation

The giant Dahutang tungsten (W) deposit has a total reserve of more than 1.31 Mt WO₃. Veinlet-disseminated scheelite and vein type wolframite mineralization are developed in this deposit, which are related to Late Mesozoic biotite granite. Four major types of alterations, which include albitization, potassic-alteration, and greisenization, and overprinted silicification developed in contact zone. The mass balance calculate of the four alteration types were used to further understanding of the mineralization process. The fresh porphyritic biotite granite has high Nb, Ta, and W, but low Ca and Sr while the Jiuling granodiorite has high Ca and Sr, but low Nb, Ta, and W concentrations. The altered porphyritic biotite granite indicated that the Nb, Ta, and W were leached out from the fresh porphyritic biotite granite, especially by sodic alteration. The low Ca and Sr contents of the altered Neoproterozoic Jiuling granodiorite indicate that Ca and Sr had been leached out from the fresh granodiorite by the fluid from Mesozoic porphyritic biotite granites. The metal W of the Dahutang deposit was mainly derived from the fluid exsolution from the melt and alteration of W-bearing granites. This study of alteration presents a new hydrothermal circulation model to understand tungsten mineralization in the Dahutang deposit.     

Genesis of the Xuebaoding W–Sn–Be Crystal Deposits in Southwest China: Evidence from Fluid Inclusions,Stable Isotopes and Ore Elements

The Xuebaoding crystal deposit, located in northern Longmenshan, Sichuan Province, China, is well known for producing coarse‐grained crystals of scheelite, beryl, cassiterite, fluorite and other minerals. The orebody occurs between the Pankou and Pukouling granites, and a typical ore vein is divided into three parts: muscovite and beryl within granite (Part I); beryl, cassiterite and muscovite in the host transition from granite to marble (Part II); and the main mineralization part, an assemblage of beryl, cassiterite, scheelite, fluorite, apatite and needle‐like tourmaline within marble (Part III). No evidence of crosscutting or overlapping of these ore veins by others suggests that the orebody was formed by single fluid activity. The contents of Be, W, Sn, Li, Cs, Rb, B, and F in the Pankou and Pukouling granites are similar to those of the granites that host Nanling W–Sn deposits. The calculated isotopic compositions of beryl, scheelite and cassiterite (δD, ?69.3‰ to ?107.2‰ and δ¹⁸O_H2O, 8.2‰ to 15.0‰) indicate that the ore‐forming fluids were mainly composed of magmatic water with minor meteoric water and CO₂ derived from decarbonation of marble. Primary fluid inclusions are CO₂? CH₄+ H₂O ± CO₂ (vapor), with or without clathrates and halites. We estimate the fluid trapping condition at T = 220 to 360°C and P > 0.9 kbar. Fluid inclusions are rich in H₂O, F^‐ and Cl^‐. Evidence for fluid‐phase immiscibility during mineralization includes variable L/V ratios in the inclusions and inclusions containing different phase proportions. Fluid immiscibility may have been induced by the pressure released by extension joints, thereby facilitating the mineralization found in Part III. Based on the geochemical data, geological occurrence, and fluid inclusion studies, we hypothesize that the coarse‐grained crystals were formed by: (i) the high content of ore elements and volatile elements such as F in ore‐forming fluids; (ii) occurrence of fluid immiscibility and Ca‐bearing minerals after wall rock transition from granite to marble making the ore elements deposit completely; (iii) pure host marble as host rock without impure elements such as Fe; and (iv) sufficient space in ore veins to allow growth.     

Vostok-2 gold-base-metal-tungsten skarn deposit,Central Sikhote-Alin,Russia

Vostok-2—East Russia’s largest skarn deposit of high-grade sulfide-scheelite ore with substantial base-metal and gold mineralization—was formed during the Mesozoic orogenic epoch of evolution of the Far East marginal continental system as an element of the gold-tin-tungsten metallogenic belt. The deposit is related to the multistage monzodiorite-granodiorite-granite complex pertaining to the ilmenite series and spatially associated with a minor granodiorite porphyry (?) stock, which bears petrological features transi- tional to those of intrusive rocks occurring at Au-W and Au deposits. The hydrothermal metasomatic alteration of host rocks evolved from pyroxene skarn via retrograde postskarn and propylitic (hydrosilicate) metasomatic rocks to the late, low-temperature quartz-sericite metasomatic rocks often with albite, chlorite, carbonate, and apatite. The mineral assemblages of skarn and postskarn metasomatic rocks correspond to those at the reduced-type tungsten skarn deposits. Zoning of the postskarn metasomatic rocks is controlled by granodiorite stock. The hydrothermal metasomatic alteration was accompanied by development of mineralization from scheelite via sulfide-scheelite with pyrrhotite and chalcopyrite to the gold-base-metal-scheelite assemblage with arsenopyrite, Bi-Sb-Te-Pb-Zn sulfides and sulfosalts. Several scheelite generations are recognized. Scheelite of the late generations is enriched in Eu, as is typical of gold deposits. The associated gold mineralization comprises both native gold varying in fineness and Au-bearing arsenopyrite. The significant gold mineralization emphasizes genetic links of this deposit with intrusion-related Au-W and Au deposits of the reduced type.     

THE COLANGUIL BATHOLITH (29-31° S), CORDILLERA FRONTAL,ARGENTINA: STRUCTURE AND TECTONIC ENVIRONMENT

This paper assesses chemical-mineralogical changes resulting from hydrothermal alteration associated with granite-hosted gold mineralization in southern Salamanca province, Spain. Within the mineralized veins, along planes of quartz growth, two types of fluid inclusions were observed. One type is rich in CH₄ with minor CO₂, the other is rich in H₂O with CO₂ (± CH₄). These are interpreted as reflecting the immiscibility of an initial fluid rich in H₂O-CH₄ and some CO₂. Inclusions with similar composition are seen at the silicification formed at the granite contact with host rocks. However, differences in P-T conditions and immiscibility of fluids are indicated by the microthermometric study and relation of the inclusions. These are consistent with the temperatures calculated from the arsenopyrite-pyrite geothermometer. Formation temperatures of 445 ± 15° C were deduced for the mineralization at the granite contact and temperatures not exceeding 386° C for the vein mineralization.

Metasomatically altered granites are depleted in Na and K in comparison to fresh granites. A gain in CO₂ has been measured in the altered rocks. No correlation was found between gold contents and any of the major or trace elements analyzed.

δ³⁴S arsenopyrite values suggest a variable source of sulfur. Calculated δD_fluid values show significant variability (?66 to ?37%₀ SMOW), whereas δ¹⁸O fluid values show small variation (from +7.6 to +8.4%_o SMOW). These values for the fluids are consistent with interaction between magmatic fluids and metamorphic rocks. Gold deposition in quartz veins could be explained by the loss of H₂S during fluid immiscibility.     

长岭凹陷深层天然气藏中CO_2及CH_4充注次序的流体包裹体证据

对长岭凹陷深层天然气藏储层——营城组火山岩中发育的流体包裹体进行了详细研究,结果表明在火山岩发育的石英、方解石细网脉中均存在较多的碳质流体包裹体,单个包裹体激光拉曼光谱分析结果表明其主要为CO2及CH4两种类型的碳质包裹体。其中方解石细网脉体中发育有原生及次生CH4包裹体,而含CO2包裹体多以原生包裹体产于石英细网脉中。很多含CO2包裹体的石英细脉中发现了含CH4包裹体的方解石脉体的角砾,这就表明石英细脉形成晚于方解石细脉。营城组火山岩储层中CO2及CH4包裹体的产状特征研究表明,松辽盆地深层天然气藏的形成系火山岩成岩后CO2及CH4等气体不同期次充注的结果,CH4气的充注时间早于CO2气,火山岩中发育的原生孔隙及次生裂隙为上述气体的充注和聚集提供了重要通道。     

Compositional characteristics of fluid inclusions as exploration tool for Au-mineralization at Larafella, Burkina Faso

The Larafella Au-prospect (Burkina Faso) lies within dacitic rocks of the Palaeoproterozoic Birimian greenstone belts. Gold mineralization is intimately associated with zones of cataclastic deformation. Whilst the lode-vein mineralization is closely associated with CO₂-rich fluid inclusions, the barren quartz veins are characterized by H₂O ± salt-bearing inclusions. Geochemical studies on the immediate wall-rock of the quartz veins have shown an increase of As in zones of gold enrichment, while alteration overprints such as carbonatization and chloritization cannot be correlated unequivocally with Au-mineralization. Consequently, fluid inclusion studies of quartz veins and As-anomalies constitute important exploration tools for mesothermal gold mineralization, since Au-rich zones can be distinguished from Au-depleted zones.     

The origin and significance of non-aqueous CO2 fluid inclusions in the auriferous veins of Bin Yauri,northwestern Nigeria

Non-aqueous CO₂ and CO₂-rich fluid inclusions are found in the vein quartz hosting mesothermal gold-sulphide mineralization at Bin Yauri, northwestern Nigeria. Although mineralizing fluids responsible for gold mineralization are thought to be CO₂-rich, the occurrence of predominantly pure to nearly pure CO₂ inclusions is nevertheless unusual for a hydrothermal fluid system. Many studies of similar CO₂-rich fluid inclusions, mainly in metamorphic rocks, proposed preferential loss (leakage) of H₂O from H₂O-CO₂ inclusions after entrapment. In this study however, it is proposed that phase separation (fluid immiscibility) of low salinity CO₂-rich hydrothermal fluids during deposition of the gold mineralization led to the loss of the H₂O phase and selective entrapment of the CO₂. The loss of H₂O to the wallrocks resulted in increasing oxidizing effects. There is evidence to suggest that the original CO₂-rich fluid was intrinsically oxidized, or perhaps in equilibrium with oxidizing conditions in the source rocks. The source of the implicated fluid is thought to be subducted metasediments, subjected to dehydration and devolatilization reactions along a transcurrent Anka fault/shear system, which has been described as a Pan-African (450–750 Ma) crustal suture.     

Geochemical Characteristics and Zonation of Primary Halos of Pulang Porphyry Copper Deposit,Northwestern Yunnan Province,Southwestern China

The Pulang (普朗) porphyry copper deposit, located in the southern segment of the Yidun-Zhongdian (义敦-为中甸) island arc ore-forming belt of the Tethys-Himalaya ore-forming domain, is a recently discovered large copper deposit. Compared with the composition of granodiorite in China, the porphyry rocks in this area are enriched in W, Mo, Cu, Au, As, Sb, F, V, and Na2O (K1≥1.2). Compared with the composition of fresh porphyry rocks in this district, the mineralized rocks are enriched in Cn, Au, Ag, Mo, Pb, Zn, W, As, Sb, and K2O (K≥1.2). Some elements show clear anomalies, such as Zn, Ag, Cu, Au, W, and Mo, and can be regarded as pathfinders for prospecting new ore bodies in depth. It has been inferred from factor analysis that the Pulang porphyry copper deposit may have undergone the multiple stages of alteration and mineralization: (a) Cu-Au mineralization; (b) W-Mo mineralization; and (c) silicification and potassic metasomatism in the whole ore-forming process. A detailed zonation sequence of indicator elements is obtained using the variability index of indicator elements as follows: Zn→Ag→Cu→Au→W→Mo. According to this zonation, an index such as (Ag×Zn) D/(Mo×W) D can be constructed and regarded as a significant criterion for predicting the Cu potential at a particular depth.     

Mineralisation at the Carrock Fell Tungsten Mine,N. England: Paragenetic,fluid inclusion and geochemical study

Tungsten ore at Carrock Fell Mine comprises wolframite and scheelite in polyminerallic quartz veins which traverse the Grainsgill Granite cupola and surrounding country rocks. In the veins, a wolframite-scheelite-apatite assemblage pre-dates a scheelite-arsenopyrite-pyrite (plus other sulphides) assemblages. Temperatures of mineralisation declined from a peak near 350°C to 170°C, and the hydrothermal fluid contained about 6 weight% NaCl and 3 wt% NaHCO₃. Contemporaneous greisenisation involved loss of Na, Cr, Ca and Ba from granite, but Si and K were retained while B, Be and Al increased slightly. Sn also increased but is always a trace constituent, and F appears to have decreased. Zones of intense alteration contain high concentrations of quartzhosted fluid inclusions resulting from penetration of the granite by fluid chemically similar to that in the vein quartz. The W-rich, Sn-poor nature of the mineralisation may relate to the weakly saline, F-deficient but CO₂-rich fluid chemistry. The alteration and mineralisation processes took place during late cooling of the Lower-Devonian Skiddaw Granite. Cross-cutting quartz-ankerite veins and argillitic zones which may be considerably younger than those producing the tungsten ore, have a distinct mineral suite lacking W and As and including major Pb and Zn. Temperatures at this late stage were below 150°C, and the fluid is estimated to have contained approximately 12 wt% NaCl and 15 wt% CaCl₂.     

The Cretaceous Ofuku Pluton and Its Relation to Mineralization in the Western Akiyoshi Plateau,Yamaguchi Prefecture,Japan

The relationship between the magmatism of the Cretaceous Ofuku pluton and mineralization in and around the Akiyoshi Plateau, Yamaguchi Prefecture, Japan was investigated using a combination of field observation, petrographic and geochemical analyses, K–Ar geochronology, and fluid inclusion data. The Ofuku pluton has a surface area of 1.5 × 1.0 km, and was intruded into the Paleozoic accretionary complexes of the Akiyoshi Limestone, Ota Group and Tsunemori Formation in the western part of the Akiyoshi Plateau. The pluton belongs to the ilmenite‐series and is zoned, consisting mainly of early tonalite and granodiorite that share a gradational contact, and later granite and aplite that intruded the tonalite and granodiorite. Harker diagrams show that the Ofuku pluton has intermediate to silicic compositions ranging from 60.4 to 77.9 wt.% SiO₂, but a compositional gap exists between 70.5 to 73.4 wt.% SiO₂ (anhydrous basis). Modal and chemical variations indicate that the assumed parental magma is tonalitic. Quantitative models of fractional crystallization based on mass balance calculations and the Rayleigh fractionation model using major and trace element data for all crystalline phases indicate that magmatic fractionation was controlled mainly by crystal fractionation of plagioclase, hornblende, clinopyroxene and orthopyroxene at the early stage, and quartz, plagioclase, biotite, hornblende, apatite, ilmenite and zircon at the later stage. The residual melt extracted from the granodiorite mush was subsequently intruded into the northern and western parts of the Ofuku pluton as melt lens to form the granite and aplite. The age of the pluton was estimated at 99–97 Ma and 101–98 Ma based on K–Ar dating of hornblende and biotite, respectively. Both ages are consistent within analytical error, indicating that the Ofuku pluton and the associated Yamato mine belong to the Tungsten Province of the San‐yo Belt, which is genetically related to the ilmenite‐series granitoids of the Kanmon to Shunan stages. The aplite contains Cl‐rich apatite and REE‐rich monazite‐(Ce), allanite‐(Ce), xenotime and bastnäsite‐(Ce), indicating that the residual melt was rich in halogens and REEs. The tonalite–granodiorite of the Ofuku pluton contains many three‐phase fluid inclusions, along with daughter minerals such as NaCl and KCl, and vapor/liquid (V/L) volume ratios range from 0.2 to 0.9, suggesting that the fluid was boiling. In contrast, the granite and aplite contain low salinity two‐phase inclusions with low V/L ratios. The granodiorite occupies a large part of the pluton, and the inclusions with various V/L ratios with chloride daughter minerals suggest the boiling fluids might be related to the mineralization. This fluid could have carried base metals such as Cu and Zn, forming Cu ore deposits in and around the Ofuku pluton. The occurrence and composition of fluid inclusions in the igneous rocks from the Akiyoshi Plateau are directly linked to Cu mineralization in the area, demonstrating that fluid inclusions are useful indicators of mineralization.     

江西大湖塘钨矿田平苗矿区含矿花岗岩矿物学特征及对成矿的指示意义

赣西北大湖塘钨矿田位于江南造山带东段,是世界级超大型W-Cu-Mo多金属矿田,矿化类型以细脉浸染型矿化为主,成矿作用与燕山期高分异花岗岩密切相关。本文通过对平苗矿区与成矿关系密切的燕山期花岗岩中黑云母和斜长石等矿物进行系统的原位主量元素和微量元素分析,探究岩浆的氧逸度、岩浆系统的深部动力学特征和详细结晶过程,并对成矿作用的指示意义进行探讨。研究表明,似斑状二云母花岗岩从岩浆结晶早期到晚期,一直保持较低的氧逸度（NNO-QFM）,可能与岩浆源区中更多的富泥质沉积岩有关,这种富钨的泥质岩源区和还原性岩浆环境更有利于钨矿的形成。燕山期花岗岩中斜长石的钙长石（An）和CaO含量均远低于晋宁期黑云母花岗闪长岩,很难为白钨矿化提供足够的钙,而黑云母花岗闪长岩由于体积巨大、钙含量高,很可能为区内大规模的白钨矿化贡献了大量的钙元素。斜长石原位分析显示,An和Al₂O₃含量之间存在显著的正相关性,而与FeO含量之间无明显的正相关性,FeO随着An含量的增加基本保持稳定,斜长石中Sr和Ba含量之间也无显著的负相关性,表明该区岩浆房为化学成分相对封闭的岩浆系统,岩浆演化过程中只有热量混合和/或减压作用,没有发生明显的镁铁质岩浆注入与混合。因此,钨、铜、硫等成矿元素应主要来自岩浆源区双桥山群的富泥质变质沉积岩和变质玄武岩的贡献,而非由外来基性岩浆的补给提供。该区岩浆岩形成于华南板块由挤压向伸展的转换期,挤压环境有利于在地壳浅部形成长期稳定的、规模较大的高分异岩浆房,促进成矿元素高度富集和大规模岩浆热液的形成,导致该区发生大规模的钨铜矿化。     

Gold Mineralization of the Gatsuurt Deposit in the North Khentei Gold Belt,Central Northern Mongolia

Mineral assemblages, chemical compositions of ore minerals, wall rock alteration and fluid inclusions of the Gatsuurt gold deposit in the North Khentei gold belt of Mongolia were investigated to characterize the gold mineralization, and to clarify the genetic processes of the ore minerals. The gold mineralization of the deposit occurs in separate Central and Main zones, and is characterized by three ore types: (i) low‐grade disseminated and stockwork ores; (ii) moderate‐grade quartz vein ores; and (iii) high‐grade silicified ores, with average Au contents of approximately 1, 3 and 5 g t^?1 Au, respectively. The Au‐rich quartz vein and silicified ore mineralization is surrounded by, or is included within, the disseminated and stockwork Au‐mineralization region. The main ore minerals are pyrite (pyrite‐I and pyrite‐II) and arsenopyrite (arsenopyrite‐I and arsenopyrite‐II). Moderate amounts of galena, tetrahedrite‐tennantite, sphalerite and chalcopyrite, and minor jamesonite, bournonite, boulangerite, geocronite, scheelite, geerite, native gold and zircon are associated. Abundances and grain sizes of the ore minerals are variable in ores with different host rocks. Small grains of native gold occur as fillings or at grain boundaries of pyrite, arsenopyrite, sphalerite, galena and tetrahedrite in the disseminated and stockwork ores and silicified ores, whereas visible native gold of variable size occurs in the quartz vein ores. The ore mineralization is associated with sericitic and siliceous alteration. The disseminated and stockwork mineralization is composed of four distinct stages characterized by crystallization of (i) pyrite‐I + arsenopyrite‐I, (ii) pyrite‐II + arsenopyrite‐II, (iii) galena + tetrahedrite + sphalerite + chalcopyrite + jamesonite + bournonite + scheelite, and iv) boulangerite + native gold, respectively. In the quartz vein ores, four crystallization stages are also recognized: (i) pyrite‐I, (ii) pyrite‐II + arsenopyrite + galena + Ag‐rich tetrahedrite‐tennantite + sphalerite + chalcopyrite + bournonite, (iii) geocronite + geerite + native gold, and (iv) native gold. Two mineralization stages in the silicified ores are characterized by (i) pyrite + arsenopyrite + tetrahedrite + chalcopyrite, and (ii) galena + sphalerite + native gold. Quartz in the disseminated and stockwork ores of the Main zone contains CO₂‐rich, halite‐bearing aqueous fluid inclusions with homogenization temperatures ranging from 194 to 327°C, whereas quartz in the disseminated and stockwork ores of the Central zone contains CO₂‐rich and aqueous fluid inclusions with homogenization temperatures ranging from 254 to 355°C. The textures of the ores, the mineral assemblages present, the mineralization sequences and the fluid inclusion data are consistent with orogenic classification for the Gatsuurt deposit.     

Mineralogy, fluid inclusion, and oxygen isotope constraints on the genesis of the Lalla Zahra W-(Cu) deposit, Alouana district, northeastern Morocco

The Lalla Zahra W-(Cu) prospect of northeastern Morocco is hosted in a Devonian volcaniclastic and metasedimentary sequence composed of graywacke, siltstone, pelite, and shale interlayered with minor tuff and mudstone. Intrusion of the 284?±?7 Ma Alouana concentrically zoned, two micas, calc-alkaline, and post-collisional Alouana granitoid pluton has contact metamorphosed the host rocks, giving rise to a metamorphic assemblage of quartz, plagioclase, biotite, muscovite, chlorite, and alusite, and cordierite. The mineralization occurs in and along subvertical, 20 to 40 cm thick, and structurally controlled tensional veins composed of quartz accompanied by molybdenite, wolframite, scheelite, base metal sulphides, carbonates, barite, and fluorite. Three main stages of mineralization (I, II, and III), each characterized by a specific mineral assemblage and/or texture, are recognized. Quartz dominates in all the veins and commonly displays multiple stages of vein filling and brecciation, and a variety of textures. The early tungsten-bearing stage consists of quartz-1, tourmaline, muscovite, wolframite, scheelite, and molybdenite. With advancing paragenetic sequence, the mineralogy of the veins shifted from stage I tungsten-bearing mineralization through stage II, dominated by base metal sulphides, to stage III with late barren carbonates and barite?±?fluorite mineral assemblages. Pervasive hydrothermal alteration affected, to varying degrees, the Alouana intrusion, resulting in microclinization, albitization, episyenitization, and greisenization of all the granitic units. Fluid inclusion data yield homogenization temperatures ranging from 124°C to 447°C for calculated salinity estimates in the range of 0.4 to ~60 wt% NaCl equiv. Similarly, the δ¹⁸O values for the three generations of quartz range from 11.7‰ to 13.9‰ V-SMOW. Calculated δ¹⁸O values of the parent fluid in the range between ?3‰ and +9‰ V-SMOW are consistent either with a mixture of water of different origins, including magmatic water, or an origin from seawater or meteoric water that probably exchanged oxygen with rocks at elevated temperatures. The coexistence of CO₂-rich and H₂O-rich fluid inclusions reflect the presence of a boiling fluid associated with the deposition of the early tungsten-bearing stage mineralization at relatively high temperature. The general temperature and salinity decrease with advancing paragenetic sequence suggest that the early high temperature, magmatic, highly saline, and boiling fluid mixed with meteoric non-boiling fluid results in the precipitation of base metal sulphide and carbonate–barite stage mineral assemblages, respectively.     

Halogen signatures of biotites from the Maher-Abad porphyry copper deposit,Iran: characterization of volatiles in syn- to post-magmatic hydrothermal fluids

Copper and gold mineralization in the Maher-Abad area, eastern Iran, is closely related to multiple episodes of emplacement of a late Eocene granodiorite into a quartz-monzonitic stock and andesitic volcaniclastic rocks. Hypogene and supergene porphyry Cu–Au mineralization occurred within the porphyritic granodiorite and quartz-monzonite host rocks extensively altered into dominantly potassic, propylitic, phyllic, and argillic assemblages. Temperature and pressure estimates using the plagioclase–hornblende thermometer and Al-in-hornblende barometer indicate that the granodiorite intruded at 758 ± 10°C and 1.4 ± 0.2 kbar.

Biotites from the alteration zones have more variable Al^IV than those in the fresh granodiorite, but nearly all are close to the ideal phlogopite composition. Biotite compositions display an increase in Al₂O₃, FeO, TiO₂, and Cl, but a decrease in SiO₂ and F, from the porphyritic granodiorite and potassic to the transitional phyllic alteration zones. Biotite from the potassic zone (X _phl?=?0.63–0.67) possesses a moderate F content (0.53 to 0.82 wt.%) that is significantly higher than that in the phyllic zone (0.22 to 0.38 wt.%), exhibiting a positive correlation with X _Mg and negative correlation with Cl.

With a decrease in the temperature, log (fH₂O/fHF) and log (fH₂O/fHCl) values calculated for fluids equilibrated with biotite increase progressively from the granodiorite through the potassic to the phyllic zones, whereas log (fHF/fHCl) shifts towards more negative values. Fugacity ratio trends in the Maher-Abad porphyry copper deposit are quite similar to those of other porphyry copper systems. The decrease in halogen content of hydrothermal fluids towards outer parts of the deposits reflects an increase in the degree of mixing between magmatic fluid and meteoric water.     

Origin of CO2-rich fluid inclusions in leucosomes from the Skagit migmatites, North Cascades, Washington, USA

CO₂–CH₄ fluid inclusions are present in anatectic layer-parallel leucosomes from graphite-bearing metasedimentary rocks in the Skagit migmatite complex, North Cascades, Washington. Petrological evidence and additional fluid inclusion observations indicate, however, that the Skagit Gneiss was infiltrated by a water-rich fluid during high-temperature metamorphism and migmatization. CO₂-rich fluid inclusions have not been observed in Skagit metasedimentary mesosomes or melanosomes, meta-igneous migmatites, or unmigmatized rocks, and are absent from subsolidus leucosomes in metasedimentary migmatites. The observation that CO₂-rich inclusions are present only in leucosomes interpreted to be anatectic based on independent mineralogical and chemical criteria suggests that their formation is related to migmatization by partial melting. Although some post-entrapment modification of fluid inclusion composition may have occurred during decompression and deformation, the generation of the CO₂-rich fluid is attributed to water-saturated partial melting of graphitic metasedimentary rocks by a reaction such as biotite + plagioclase + quartz + graphite ± Al₂SiO₅+ water-rich fluid = garnet + melt + CO₂–CH₄. The presence of CO₂-rich fluid inclusions in leucosomes may therefore be an indication that these leucosomes formed by anatexis. Based on the inferences that (1) an influx of fluid triggered partial melting, and (2) some episodes of fluid inclusion trapping are related to migmatization by anatexis, it is concluded that a free fluid was present at some time during high-temperature metamorphism. The infiltrating fluid was a water-rich fluid that may have been derived from nearby crystallizing plutons. Because partial melting took place at pressures of at least 5 kbar, abundant free fluid may have been present in the crust during orogenesis at depths of at least 15 km.     

Genesis of the Nanyangtian scheelite deposit in southeastern Yunnan Province,China: evidence from mineral chemistry,fluid inclusions,and C–O isotopes

The Nanyangtian skarn-type scheelite deposit is an important part of the Laojunshan W–Sn polymetallic metallogenic region in southeastern Yunnan Province, China. The deposit comprises multiple scheelite ore bodies; multilayer skarn-type scheelite ore bodies are dominant, with a small amount of quartz vein-type ore bodies. Skarn minerals include diopside, hedenbergite, grossular, and epidote. Three mineralization stages exist: skarn, quartz–scheelite, and calcite. The homogenization temperatures of fluid inclusions in hydrothermal minerals that formed in different paragenetic phases were measured as follows: 221–423 °C (early skarn stage), 177–260 °C (quartz–scheelite stage), and 173–227 °C (late calcite stage). The measured salinity of fluid inclusions ranged from 0.18% to 16.34% NaCleqv (skarn stage), 0.35%–7.17% NaCleqv (quartz–scheelite stage), and 0.35%–2.24% NaCleqv (late calcite vein stage). Laser Raman spectroscopic studies on fluid inclusions in the three stages showed H₂O as the main component, with N₂ present in minor amounts. Minor amounts of CH₄ were found in the quartz–scheelite stage. It was observed that the homogenization temperature gradually reduced from the early to the late mineralization stages; moreover, δ¹³C_PDB values for ore-bearing skarn in the mineralization period ranged from ? 5.7‰ to ? 6.9‰ and the corresponding δ¹⁸O_SMOW values ranged from 5.8‰ to 9.1‰, implying that the ore-forming fluid was mainly sourced from magmatic water with a minor amount of meteoric water. Collectively, the evidence indicates that the formation of the Nanyangtian deposit is related to Laojunshan granitic magmatism.     

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.