Alkaline granites and Be (Phenakite-bertrandite) mineralization: An example of the Orot and Ermakovka deposits

The Orot (Or) and Ermakovka (Er) intrusions of aegirine granites with various resources of accompanying Be mineralization in Transbaikalia were studied to reproduce Be behavior during the crystallization and degassing of alkaline granite magma. Data on the petrography and geochemistry of the rocks and the microthermomety and microprobe analysis of fluid and melt inclusions in them indicate that the intrusions were formed by discrete magma portions derived from a single magmatic source during successive stages of its differentiation. The intrusions crystallized at temperatures higher than 1030–1070°C (Or) and 840–640°C (Er), and the melts contained elevated concentrations of H₂O and F: from 2.1 to 3.5% F and from <1 to 1% H₂O for the former intrusion and from 3.9 to 6.7% F and from <2.6 to 4.1% H₂O for the latter. Fluids were released from the magma during a late crystallization stage for the Orot intrusion and an intermediate stage for the Ermakovka intrusion. Early in the course of this process, the fluids were halide-sulfate brines with the Cl: F ratio higher for the Orot intrusion and lower for the Ermakovka intrusion. A temperature decrease resulted in the exsolution of the fluids into two immiscible phases, one of which contained low and the other high concentrations of salts. The magmatic brines and low-salinity solutions of both intrusions were enriched in Be (up to 1.1 g/kg), which is comparable with the concentration of this element in the emanations of Be-bearing pegmatites in the Pamirs and is manyfold higher than C _Be in magmatic fluids related to granite intrusions with W-Sn mineralization. The Be ore mineralization of the Orot and Ermakovka deposits was produced by solutions whose composition and Be concentrations were analogous to those in the low-salinity phase of the corresponding magmatic fluids. The brines of the Ermakovka intrusion were enriched in Mo (up to 17 g/kg) and, to a lesser extent, Mn, Ce, and La and produced uneconomic monazite-molybdenite ore mineralization. Based on available data and results of our calculations, we arrived at the conclusion that the very high alkali concentrations in the melts of both intrusions (ASI < 1), their high F concentrations (up to 4.1%), and the absence of magmatic Be-bearing minerals facilitated Be selective extraction by the separated fluids in the form of its most soluble F-complexes. The high oxidation of the melt predetermined the predominance of hexavalent S and Mo compounds, which could be efficiently extracted by the fluid phase in the form of sulfates and molybdates of alkali metals. The differences in the ore potentials of the Orot and Ermakovka intrusions were caused by the different H₂O, F, and perhaps, also Be concentrations in the parental melts, which was, in turn, caused by their different degrees of differentiation during the preintrusive stages of their magmatic evolution.     

Direct evolution of W-rich brines from crystallizing melt within the Mariktikan granite pluton, west Transbaikalia

Uneconomic tungsten mineralization associated with the Mariktikan granite pluton of the Transbaikalian igneous province, eastern Siberia, is confined to a marginal part of the pluton referred to as the Andreyevsky body. This is composed of rocks similar to those of the main pluton, but is likely to be an autonomous, although kindred, body. On the basis of cross-cutting relationships between rock varieties, and their textural features, the crystallization history is subdivided into three stages of unequal duration. Melt and fluid inclusions related to each of them have been studied using microthermometric and micro-analytical procedures, including a technique for atomic emission spectroscopy of individual fluid inclusions opened by a laser microprobe. During the main crystallization stage (1045–1012 °C) more than 70% of the parental magma is believed to have crystallized (at the level studied), resulting in the formation of a crystalline framework rigid enough for the appearance of fractures within which some portion of the intercrystalline melt accumulated, giving rise to thin aplite veins. Almost complete crystallization of intercrystalline and fracture-hosted melt occurred during the late stage (1012–990 °C), whereas during the final stage only small bunches of schlieric, sometimes miarolitic pegmatite were formed from a few pockets of residual melt (990–917 °C). In spite of the low water content of the melt (about 1 wt.%), fluid separation took place from the onset of crystallization. During the main crystallization stage, the exsolved fluid divided into two immiscible phases, CO₂-rich gas and salt-rich liquid (brine). However, it was homogeneous thereafter. Major ore components of the brine (Mn, Fe, W) displayed different behaviour as crystallization progressed. W concentration was below 0.1 wt.% at the main stage, attained 1 wt.% during the late stage and increased to 1.8 wt.% at the final stage. Comparison of these data with calculations carried out using estimated parameters for the parental magma enables us to infer that obtained concentration values are reasonable for the special case studied here. However, they are unlikely to be attainable if the magma is H₂O enriched and lacks an anomalously high W content. In the Andreyevsky body of the Mariktikan pluton, the following features of the parental magma made possible the generation of W-rich solutions: (1) high liquidus temperature (1045 °C) and elevated Cl content (c.0.15 wt.%) that resulted in enlargement of the fluid/melt distribution coefficient (c.10), (2) low water content (c.1%) and elevated W content (c.0.001 wt.%) that provided a relatively high W/H₂O ratio within the system. At the same time, because of the low water content of the magma, the total mass of W-bearing solutions has proved to be insufficient for the production of large-scale mineralization (a reduced W content of the great bulk of the exsolved brine may have had an unfavourable effect as well). Received: 2 May 1996 / Accepted: 29 January 1997     

内蒙古红彦镇地区山神府花岗岩熔融-流体包裹体特征及其成矿意义

通过内蒙古红彦镇地区山神府花岗岩的包裹体研究来探讨岩浆-热液过渡阶段的流体特征和成矿潜力.研究表明,山神府花岗岩包裹体类型可分为熔融包裹体、熔-流包裹体和流体包裹体3大类.熔-流包裹体的存在表明花岗岩经历岩浆-热液过渡阶段,而岩体中心相-边缘相流体包裹体均一温度从281 ℃变化到大于550 ℃,盐度从1.1% NaCl eqv变化到大于66.8% NaCl eqv同样指示了这一特征.根据不同温度、盐度包裹体等容线和水饱和花岗质岩浆固相线相交法可计算岩浆出溶流体温压范围,结合CO₂三相包裹体对岩体最小侵位压力有较好限制,估算出山神府花岗岩最小侵位深度为7.6~9.5 km,出溶温度为580~700 ℃,出溶深度集中在6.0~14.9 km.包裹体拉曼特征表明,熔-流包裹体固相成分含有重晶石、蓝铜矿和赤铁矿等强氧化性物质,说明岩浆-热液体系具有高氧逸度,而在高温高压高盐条件下非常有利于岩浆中Cu等金属向出溶流体中富集,结合野外矿化蚀变特征,分析得出山神府地区具有较好寻找岩浆热液型Cu矿床的成矿潜力.      

云南哈播斑岩铜(-钼-金)矿床流体包裹体研究

哈播斑岩Cu-(Mo-Au)矿床产于哀牢山富碱斑岩带的南段,形成于青藏高原后碰撞阶段构造转换环境,属于陆-陆碰撞型斑岩矿床.根据脉体的交切关系,确定哈播矿床各种脉的演化序列为早期石英脉→石英-黄铜矿脉→石英辉钼矿脉.脉中流体包裹体的岩相学、显微测温和激光拉曼光谱分析等研究结果显示,各期脉中均有富气相包裹体、富液相包裹体和含子矿物多相包裹体,各种包裹体的气相均含有CO2、SO2、H2O等气体.各期脉中多种包裹体并存并具有相似的均一温度范围,富液相包裹体均一温度149～427℃,盐度ω(NaCleq)6.0％～15.0％;富气相包裹体均一温度205～405℃,盐度ω(NaCleq) 3.4％～19.0％;含子矿物多相包裹体均一温度305～516℃,盐度w(NaCleq) 33.5％～61.0％.哈播矿床的初始成矿流体由稳定共存、不混溶的低盐度流体和高盐度流体组成,高盐度流体是哈播矿床成矿元素迁移的主要载体.成矿流体在400℃左右发生“二次沸腾”、分相,温度下降和挥发分持续逃逸可能是Cu-Au成矿的诱因.Mo元素在成矿流体多次沸腾、分相过程中,持续优先分配进入高盐度流体中而逐步富集;温度下降,使含钼硫化物在流体中溶解度降低、沉淀,形成石英-辉钼矿±黄铜矿脉.     

斑岩型铜、金、钼矿床成岩成矿特征差异的原因和意义

文中简要总结了斑岩型金矿、铜矿和钼矿在产出的构造环境,岩石地球化学特征和出溶流体的温度、压力、盐度、蚀变等方面的异同点,重点从元素的地球化学性质、岩浆的源区和过程(熔体和流体演化)3个方面解释了上述差异。Au、Cu和Mo在地球化学性质尤其是亲硫性上的差异决定了元素在不同的大地构造环境下的岩浆作用过程中的分布、迁移和富集特征,最终控制了矿床的分布。岩浆的源区及其温压条件、熔体上升过程中矿物的分离结晶和中上地壳岩浆房内的演化程度控制了成矿岩浆的地球化学特征,进而影响其就位时的压力和温度,从而导致出溶流体在p-T-X上的变化。结合岩浆岩中大离子亲石元素和SiO2的含量,可以评估斑岩型矿床的类型：高的Rb含量是斑岩型钼矿的特征,高的Ba含量是斑岩型钼+铜矿的特征,高的Sr含量是斑岩型铜+金矿的特征。相对于俯冲环境,后俯冲环境下的成矿岩体具有更高的大离子亲石元素含量。矿区中酸性岩石的结构(斑状、似斑状、不等粒和等粒结构)可以用来初步指示成矿的潜力。     

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.     

The behavior of trace elements during the chemical evolution of the H2O-, B-, and F-rich granite–pegmatite–hydrothermal system at Ehrenfriedersdorf, Germany: a SXRF study of melt and fluid inclusions

Detailed melt and fluid inclusion studies in quartz hosts from the Variscan Ehrenfriedersdorf complex revealed that ongoing fractional crystallization of the highly evolved H₂O-, B-, and F-rich granite magma produced a pegmatite melt, which started to separate into two immiscible phases at about 720°C, 100 MPa. With cooling and further chemical evolution, the immiscibilty field expanded. Two conjugate melts, a peraluminous one and a peralkaline one, coexisted down to temperatures of about 490°C. Additionally, high-salinity brine exsolved throughout the pegmatitic stage, along with low-density vapor. Towards lower temperatures, a hydrothermal system gradually developed. Boiling processes occurred between 450 and 400°C, increasing the salinities of hydrothermal fluids at this stage. Below, the late hydrothermal stage is dominated by low-salinity fluids. Using a combination of synchrotron radiation-induced X-ray fluorescence analysis and Raman spectroscopy, the concentration of trace elements (Mn, Fe, Zn, As, Sb, Rb, Cs, Sr, Zr, Nb, Ta, Ag, Sn, Ta, W, rare earth elements (REE), and Cu) was determined in 52 melt and 8 fluid inclusions that are representative of distinct stages from 720°C down to 380°C. Homogenization temperatures and water contents of both melt and fluid inclusions are used to estimate trapping temperatures, thus revealing the evolutionary stage during the process. Trace elements are partitioned in different proportions between the two pegmatite melts, high-salinity brines and exsolving vapors. Concentrations are strongly shifted by co ncomitant crystallization and precipitation of ore-forming minerals. For example, pegmatite melts at the initial stage (700°C) have about 1,600 ppm of Sn. Concentrations in both melts decrease towards lower temperatures due to the crystallization of cassiterite between 650 and 550°C. Tin is preferentially fractionated into the peralkaline melt by a factor of 2–3. While the last pegmatite melts are low in Sn (64 ppm at 500°C), early hydrothermal fluids become again enriched with about 800 ppm of Sn at the boiling stage. A sudden drop in late hydrothermal fluids (23 ppm of Sn at 370°C) results from precipitation of another cassiterite generation between 400 and 370°C. Zinc concentrations in peraluminous melts are low (some tens of parts per million) and are not correlated with temperature. In coexisting peralkaline melts and high-T brines, they are higher by a factor of 2–3. Zinc continuously increases in hydrothermal fluids (3,000 ppm at 400°C), where the precipitation of sphalerite starts. The main removal of Zn from the fluid system occurs at lower temperatures. Similarly, melt and fluid inclusion concentrations of many other trace elements directly reflect the crystallization and precipitation history of minerals at distinctive temperatures or temperature windows.     

Geochemical evolution of halogen-enriched granite magmas and mineralizing fluids of the Zinnwald tin-tungsten mining district,Erzgebirge, Germany

We remelted and analyzed crystallized silicate melt inclusions in quartz from a porphyritic albite-zinnwaldite microgranite dike to determine the composition of highly evolved, shallowly intruded, Li- and F-rich granitic magma and to investigate the role of crystal fractionation and aqueous fluid exsolution in causing the extreme extent of magma differentiation. This dike is intimately associated with tin- and tungsten-mineralized granites of Zinnwald, Erzgebirge, Germany. Prior research on Zinnwald granite geochemistry was limited by the effects of strong and pervasive greisenization and alkali-feldspar metasomatism of the rocks. These melt inclusions, however, provide important new constraints on magmatic and mineralizing processes in Zinnwald magmas.The mildly peraluminous granitic melt inclusions are strongly depleted in CAFEMIC constituents (e.g., CaO, FeO, MgO, TiO₂), highly enriched in lithophile trace elements, and highly but variably enriched in F and Cl. The melt inclusions contain up to several thousand ppm Cl and nearly 3 wt% F, on average; several inclusions contain more than 5 wt% F. The melt inclusions are geochemically similar to the corresponding whole-rock sample, except that the former contain much more F and less CaO, FeO, Zr, Nb, Sr, and Ba. The Sr and Ba abundances are very low implying the melt inclusions represent magma that was more evolved than that represented by the bulk rock. Relationships involving melt constituents reflect increasing lithophile-element and halogen abundances in residual melt with progressive magma differentiation. Modeling demonstrates that differentiation was dominated by crystal fractionation involving quartz and feldspar and significant quantities of topaz and F-rich zinnwaldite. The computed abundances of the latter phases greatly exceed their abundances in the rocks, suggesting that the residual melt was separated physically from phenocrysts during magma movement and evolution.Interactions of aqueous fluids with silicate melt were also critical to magma evolution. To better understand the role of halogen-charged, aqueous fluids in magmatic differentiation and in subsequent mineralization and metasomatism of the Zinnwald granites, Cl-partitioning experiments were conducted with a F-enriched silicate melt and aqueous fluids at 2,000 bar (200 MPa). The results of the experimentally determined partition coefficients for Cl and F, the compositions of fluid inclusions in quartz and other phenocrysts, and associated geochemical modeling point to an important role of magmatic-hydrothermal fluids in influencing magma geochemistry and evolution. The exsolution of halogen-charged fluids from the Li- and F-enriched Zinnwald granitic magma modified the Cl, alkali, and F contents of the residual melt, and may have also sequestered Li, Sn, and W from the melt. Many of these fluids contained strongly elevated F concentrations that were equivalent to or greater than their Cl abundances. The exsolution of F-, Cl-, Li-, ± W- and Sn-bearing hydrothermal fluids from Zinnwald granite magmas was important in effecting the greisenizing and alkali-feldspathizing metasomatism of the granites and the concomitant mineralization.Editorial Handling: B. Lehmann     

Fluid evolution in the nepheline syenites of the Ditrău Alkaline Massif, Transylvania, Romania

The Ditrău Alkaline Massif is an intrusion into the Bucovina nappe system that is part of the Mesozoic crystalline zone located in Transylvania, Romania, in the Eastern Carpathians. Nepheline syenites are the most abundant rocks in the central and eastern part of the Massif, and represent the last major intrusion of the complex. Fluid inclusions in nepheline, aegirine and albite were trapped at magmatic conditions on or below the H₂O-saturated nepheline syenite solidus at about 400–600 °C and 2.5–5 kbars. Early nepheline, and to a lesser extent albite, were altered by highly saline fluids to produce cancrinite, sodalite and analcime, during this process cancrinite also trapped fluid inclusions. The fluids, in most cases, can be modeled by the H₂O–NaCl system with varying salinity; however inclusions with more complex fluid composition (containing K, Ca, CO₃, etc., in addition to NaCl) are common. Raman spectroscopic analyses of daughter minerals confirm the presence of alkali-carbonate fluids in some of the earliest inclusions in nepheline, aegirine and albite.

During crystallization, the melts exsolved a high salinity, carbonate-rich magmatic fluid that evolved to lower salinity as crystallization progressed. Phases that occur early in the paragenesis contain high-salinity inclusions while late phases contain low-salinity inclusions. The salinity trend is consistent with experimental data for the partitioning of chlorine between silicic melt and exsolved aqueous fluid at about 2.0 kbars. The activity of water (a_H2O) in the melt increases during crystallization, resulting in the formation of hydrous phases during late-stage crystallization of the nepheline syenites.     

内蒙古赤峰维拉斯托大型锡多金属矿的地质地球化学特征

2014年发现的维拉斯托锡锌矿是继20世纪末该矿区铜锌矿之后的重要找矿进展,已控制Sn金属资源量10万t。成矿作用与隐伏花岗岩体有关,该岩体侵入于前寒武纪变质岩中。矿化类型包括岩体顶部的花岗岩型锡锌矿、岩体外侧的石英脉型锡锌矿以及外围的铜锌矿。针对花岗岩、各类矿体开展了岩石学、矿床学、主微量元素地球化学、年代学等研究,初步查明岩浆演化机制、矿床成因及三类矿化的关系。细粒斑状碱长花岗岩La-ICPMS锆石UPb年龄(139.5±1.2)Ma(MSWD=3.3)。岩石中发育多级斑晶,结晶(沉淀)顺序为钠长石→石英→钾长石→钠长石→石英、黄玉、锡石、闪锌矿。花岗岩富Si O2贫Al2O3、Ti O2、TFe2O3、Ca O等,高Rb、Cs、Nb、Ta及W、Mo、Bi、Cu、Zn、In等元素,低Sr、Ba等,钠长石An0.3,与锡钨多金属矿成矿花岗岩性质相似。岩浆晚期经历了岩浆-热液过渡阶段(浆液过渡态流体),自硅酸盐相中分离出富Si、富F和富S的流体相,分别形成花岗岩型矿石中的石英、黄玉、锡石-闪锌矿囊状体(珠滴),伴随熔融包裹体和熔流包裹体,晚期逐渐、连续地向热液阶段过渡。岩浆-热液过渡阶段在岩体顶部形成花岗岩型锡锌矿石,热液阶段在岩体外侧和外围形成石英脉型锡锌矿及铜锌矿、铅锌银矿。这些矿体连同成矿花岗岩共同构成岩浆-热液型锡多金属矿床成矿系统。锡林郭勒—赤峰地区,很多脉状铅锌银矿的成矿作用与酸性侵入岩有关,深部可能存在大规模岩浆-热液型锡(钨)多金属矿。     

Fluid inclusions,muscovite Ar–Ar age,and fluorite trace elements at the Baiyanghe volcanic Be–U–Mo deposit,Xinjiang, northwest China: Implication for its genesis

The Baiyanghe Be–U–Mo deposit is located in the Late Paleozoic Xuemisitan–Kulankazi island arc of the northwestern margin of the Junggar plate, Northwest China. It is the largest Be deposit (2.2 M tons of ore with grades ranging from 0.2% to 1.4%) in Asia. Orebodies in the deposit occur as fractures along contact zones between the Yangzhuang granite porphyry intrusion and Devonian pyroclastic country rocks and within the porphyry itself. Muscovite–fluorite veins are closely associated with the Be–U–Mo mineralization. A new Ar–Ar dating of the muscovite in this study yields a plateau age of 303.0 ± 1.6 Ma, which constrains the timing of the Be–U–Mo mineralization of the deposit. Three stages of fluorite of different colors have been identified at the deposit, with the earliest dark-purple fluorite more closely associated with the mineralization. Microthermometry of fluid inclusions obtained from the three stages of fluorite suggests that the fluorites were precipitated as veins from low temperature (120–150 °C) hydrothermal fluids with salinity ranging from 4.7 to 19.7 wt.% NaCl eqv. Based on the trace elemental concentrations and REE patterns of the fluorite, the style of veining, and the low salinity and low temperature characters of the fluid inclusions, it is suggested that Be and U were most likely transported as fluoride complexes and Mo as hydroxyl complexes. Pb isotopic compositions of the ores and country rocks, as well as O and H isotopic characters of the ore-related muscovite, indicate mixing between magmatic and meteoric waters; both contributed to formation of the ore-forming fluids. Metallic Be, U, and Mo were most likely leached out from the granite porphyry by the fluids. The fluid mixing led to the reduction of U, Mo, and Be and their precipitation at the deposit.     

江西德兴铜厂斑岩铜矿成矿物质来源的再认识——来自流体包裹体的证据

本文从江西德兴斑岩铜矿铜厂矿床的流体包裹体研究出发,讨论了矿床成矿物质来源与矿床成因。矿床中流体包裹体分为6类,即富液包裹体、富气包裹体、含石盐多相包裹体、含CO2多相包裹体以及熔体包裹体和熔体-流体包裹体。富气包裹体、含石盐多相包裹体和熔体与熔体-流体包裹体代表了成矿早期岩浆热液的特征。在这些包裹体中发现黄铜矿等金属矿物,表明成矿金属主要源自岩浆。含石盐多相包裹体和富气包裹体与矿体关系不甚密切,但其中所含有的金属矿物特别是黄铜矿,暗示早期来自岩浆的热液流体金属含量较高,形成于大气降水与岩浆热液混合之前。成矿中晚期大气降水流体在冷却和稀释岩浆流体方面对于矿床的形成作出了一定贡献,但是来自围岩的大气降水可能并没有向成矿体系提供大量金属。     

西藏曲水县达布斑岩型铜钼矿床金属沉淀机制探讨

西藏曲水县达布斑岩型铜钼矿床位于冈底斯成矿带中东段,其矿化体主要产于含矿斑岩体与围岩的内外接触带中。文章以矿石内Cu、Mo矿化石英脉中的流体包裹体为研究对象,探讨了成矿金属沉淀的机制。通过详细的显微镜下鉴定,发现Cu、Mo矿化阶段的流体包裹体类型均以L型为主,但Cu矿化阶段的V型包裹体明显较Mo矿化阶段多,而S型包裹体较少。Cu、Mo矿化石英脉中,常见L型、V型、S型流体包裹体共存的现象,且它们的均一温度范围非常接近,说明成矿流体经历了不混溶作用,使得高盐度流体与低密度气相流体发生分离。单个流体包裹体激光拉曼光谱测试显示,在Cu、Mo矿化阶段的气相包裹体中均检测到CO2的特征峰和H2O峰,而在Mo矿化阶段的气相包裹体仅检测到CH4特征峰,说明Mo矿化阶段的流体的相对还原性更强;同时,检测到硬石膏、赤铁矿、磁铁矿、黄铜矿、黄铁矿等子矿物,但硬石膏、赤铁矿、磁铁矿主要分布于Cu矿化阶段,说明Cu矿化阶段的流体氧化性相对较强。对单个流体包裹体进行同步辐射X射线荧光分析(SR-RXF)显示,Cu、Au等金属主要富集于流体包裹体气相中,表明Cu、Au元素可能是气相运移。对Cu、Mo硫化物沉淀的一系列化学反应研究表明,呈氧化态以及酸度低(HCl浓度低,即偏中性)的流体会促进黄铜矿饱和;活性较高的H2S和略呈还原性的流体有利于辉钼矿的沉淀。综合分析认为,铜矿化与偏中性、结晶分异程度相对较低的花岗闪长斑岩关系密切,而钼矿化与酸性、结晶分异程度相对较高的花岗斑岩关系密切。     

岩浆热液出溶和演化对斑岩成矿系统金属成矿的制约

岩浆热液过渡阶段对于与岩浆热液有关矿床的形成非常重要。以往的研究多侧重于岩浆结晶阶段和低于固相线的热液阶段过程和演化 ,但对于流体从熔体出溶到熔体最后固结过程的理解却很有限。基于流体包裹体冷热台研究、单个流体和熔体包裹体原位无损成分分析技术 ,并结合挥发份和成矿元素在共存相间分配的实验和质量平衡计算模拟 ,岩浆热液出溶和演化对金属成矿制约的研究取得了很大进展。文中从岩浆中挥发份的出溶和演化、成矿元素在岩浆热液过渡体系各相之间的分配、斑岩矿床成矿流体及与金属成矿的关系、浅成热液矿床成矿流体及与金属成矿的关系几个方面进行了阐述。研究表明 :( 1)岩浆熔体不仅含有足够的挥发性组分 ,而且出溶的挥发份能够被圈闭在流体包裹体中而成为岩浆出溶热液的实物证据。 ( 2 )挥发份和成矿元素不仅在岩浆熔体和出溶的溶液间分配 ,还将在熔体与盐水溶液、熔体与气相以及盐水溶液与气相间进行分配。Cu在岩浆蒸气中比在共存的熔体中要富集数百倍 ,而Cu ,As,Au(可能作为HS配合物 )则偏向于分配进入与液体相共存的蒸气相中。 ( 3 )成矿元素在熔体 /溶液间的分配系数受控于熔体中初始水含量与饱和水含量之比值和岩浆熔体与共存出溶水溶液的w(Cl) /w(H2 O)和w(F) /w(Cl)比值。 ( 4 )斑岩     

中酸性岩浆体系成矿流体及微量元素地球化学特征

从流体成矿作用角度出发，与酸性岩浆体系有关的成矿流体可以分为：酸性岩浆硅酸盐熔融体，岩浆一热液过渡阶段硅酸盐熔融体及其分异的流体，酸性岩浆熔体分异形成的热水成矿溶液。酸性岩浆体系主要提供热源和部分矿质，其提供的热源驱动地下水淋滤、萃取围岩中的成矿物质形成地下水热液成矿流体。变质岩混合岩化形成花岗质岩浆过程中所形成的混合岩化成矿流体。在此基础上，讨论了上述不同成矿流体的微量元素地球化学特征及其对成矿的控制作用。     

Fluid and source magma evolution of the Questa porphyry Mo deposit,New Mexico,USA

Combined fluid inclusion microthermometry and microanalysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) are used to constrain the hydrothermal processes forming a typical Climax-type porphyry Mo deposit. Molybdenum mineralisation at Questa occurred in two superimposed hydrothermal stages, a magmatic-hydrothermal breccia and later stockwork veining. In both stages, texturally earliest fluids were single-phase, of low salinity (~7 wt.% NaCl_equiv.) and intermediate-density. Upon decompression to ~300 bar, they boiled off a vapour phase, leaving behind a residual brine (up to 45 wt.% NaCl_equiv) at temperatures of ~420°C. The highest average Mo concentrations in this hot brine were ~500 μg/g, exceeding the Mo content of the intermediate-density input fluid by about an order of magnitude and reflecting pre-concentration of Mo by fluid phase separation prior to MoS₂ deposition from the brine. Molybdenum concentrations in brine inclusions, then, decrease down to 5 μg/g, recording Mo precipitation in response to cooling of the saline liquid to ~360°C. Molybdenite precipitation from a dense, residual and probably sulphide-depleted brine is proposed to explain the tabular shape of the ore body and the absence of Cu-Fe sulphides in contrast to the more common Cu-Mo deposits related to porphyry stocks. Cesium and Rb concentrations in the single-phase fluids of the breccia range from 2 to 8 and from 40 to 65 μg/g, respectively. In the stockwork veins, Cs and Rb concentrations are significantly higher (45–90 and 110–230 μg/g, respectively). Because Cs and Rb are incompatible and hydrothermally non-reactive elements, the systematic increase in their concentration requires two distinct pulses of fluid exsolution from a progressively more fractionated magma. By contrast, major element and ore metal concentrations of these two fluid pulses remain essentially constant. Mass balance calculations using fluid chemical data from LA-ICPMS suggest that at least 25 km³ of melt and 7 Gt of deep input fluid were necessary to provide the amount of Mo contained in the stockwork vein stage alone. While the absolute amounts of fluid and melt are uncertain, the well-constrained element ratios in the fluids together with empirical fluid/melt partition coefficients derived from the inclusion analyses suggest a high water content of the source melt of ~10%. In line with other circumstantial evidence, these results suggest that initial fluid exsolution may have occurred at a confining pressure exceeding 5 kbar. The source of the molybdenum-mineralising fluids probably was a particularly large magma chamber that crystallised and fractionated in the lower crust or at mid-crustal level, well below the shallow intrusions immediately underlying Questa and other porphyry molybdenum deposits. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Immiscibility between silicate magmas and aqueous fluids: a melt inclusion pursuit into the magmatic-hydrothermal transition in the Omsukchan Granite (NE Russia)

Exsolution (unmixing) of the volatile element-rich phases from cooling and crystallising silicate magmas is critical for element transport from the Earth’s interior into the atmosphere, hydrosphere, crustal hydrothermal systems, and the formation of orthomagmatic ore deposits. Unmixing is an inherently fugitive phenomenon and melt inclusions (droplets of melt trapped by minerals) provide robust evidence of this process. In this study, melt inclusions in phenocrystic and miarolitic quartz were studied to better understand immiscibility in the final stages of cooling of, and volatile exsolution from, granitic magmas, using the tin-bearing Omsukchan Granite (NE Russia) as an example.

Primary magmatic inclusions in quartz phenocrysts demonstrate the coexistence of silicate melt and magma-derived Cl-rich fluids (brine and vapour), and emulsions of these, during crystallisation of the granite magma. Microthermometric experiments, in conjunction with PIXE and other analytical techniques, disclose extreme heterogeneity in the composition of the non-silicate phases, even in fluid globules within the same silicate melt inclusion. We suggest that the observed variability is a consequence of strong chemical heterogeneity in the residual silicate-melt/brine/vapour system on a local scale, owing to crystallisation, immiscibility and failure of individual phases to re-equilibrate. The possible evolution of non-silicate volatile magmatic phases into more typical “hydrothermal” chloride solutions was examined using inclusions in quartz from associated miarolitic cavities.     

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.     

Crucial control on magmatic-hydrothermal Sn deposit in the Tengchong block,SW China: Evidence from magma differentiation and zircon geochemistry

Magmatic-hydrothermal Sn deposits are commonly associated with high silica magmas, but why most global high silica granites do not bear economic Sn ore grades remains unclear. Two crucial factors controlling magmatic-hydrothermal Sn mineralization, including advanced fractionation and depressurization-induced rapid cooling, were revealed in the case study of the Guyong granitic pluton linked with the Xiaolonghe Sn deposit, in the Tengchong block, SW China. The Guyong granitic pluton comprises three petrological facies: less evolved biotite syenogranite, evolved alkali granite and leucogranite, and highly evolved facies (the protolith of greisenized granite). Similar crystallization ages (～77 Ma) and gradual contact between different petrological facies indicate the Guyong granitic pluton records a continuous fractionation process. Monte Carlo-revised Rayleigh fractionation model suggests the fractionation degree of the Guyong pluton is markedly high (>87 wt.%) that can only be achieved by a high initial water (≥4 wt.%) content in the parent granitic magma revealed by rhyolite-MELTS calculation. Advanced degree fractionation causes the first Sn enrichment but it also significantly increases the viscosity of evolved magmas, suppressing the exsolution and transport of hydrothermal fluids. Hence, it must be compensated by the second critical factor: depressurization-induced rapid cooling, reflected by the occurrence of highly metamict zircons in the greisenized granite. The highly metamict feature, indicated by the large full width at half maximum (FWHM) values of zircon ν₃(SiO₄) peak (>19.5 cm^?1), suggests these zircons do not experience thermal annealing but rapidly ascend into a shallow cooling environment. Depressurization-induced rapid cooling facilitates exsolution and transport of hydrothermal fluids, interacting with wall rocks and resulting in Sn mineralization.     

Fluid inclusion evidence for hydrothermal fluid evolution in the Darreh-Zar porphyry copper deposit,Iran

The Darreh-Zar porphyry copper deposit is associated with a quartz monzonitic–granodioritic–porphyritic stock hosted by an Eocene volcanic sedimentary complex in which magmatic hydrothermal fluids were introduced and formed veins and alteration. Within the deepest quartz-rich and chalcopyrite-poor group A veins, LVHS2 inclusions trapped high salinity, high temperature aqueous fluids exsolved directly from a relatively shallow magma (0.5 kbar). These late fluids were enriched in NaCl and reached halite saturation as a result of the low pressure of magma crystallization and fluid exsolution. These fluids extracted Cu from the crystallizing melt and transported it to the hydrothermal system. As a result of ascent, the temperature and pressure of these fluids decreased from 600 to 415 °C, and approximately 500–315 bars. At these conditions, K-feldspar and biotite were stabilized. Type A veins were formed at a depth of ∼1.2 km under conditions of lithostatic pressure and abrupt cooling. Upon cooling and decompressing, the fluid intersected with the liquid–vapor field resulting in separation of immiscible liquid and vapor. This stage was recorded by formation of LVHS1, LVHS3 and VL inclusions. These immiscible fluids formed chalcopyrite–pyrite–quartz veins with sericitic alteration envelopes (B veins) under the lithostatic–hydrostatic pressure regime at temperatures between 415 and 355 °C at 1.3 km below the paleowater table. As the fluids ascended, copper contents decreased and these fluids were diluted by mixing with the low salinity-external fluid. Therefore, pyrite-dominated quartz veins were formed in purely hydrostatic conditions in which pressure decreased from 125 bars to 54 bars and temperature decreased from 355 to 298 °C. During the magmatic-hydrothermal evolution, the composition and P–T regime changed drastically and caused various types of veins and alterations. The abundance of chalcopyrite precipitation in group B veins suggests that boiling and cooling were important factors in copper mineralization in Darreh-Zar.