Immiscible phases of magmatic fluid and their relation to Be and Mo mineralization at the Yermakovka F–Be deposit, Transbaikalia, Russia

Melt and fluid inclusions in minerals from the peralkaline granite intrusion and associated mineralized country rocks from the Yermakovka F–Be deposit were studied to characterize the behaviour of trace elements and exsolved fluids in the transition from magmatic to hydrothermal processes. Ore mineralization was mostly due to volatile release from a deep-seated pluton for which crystallization history and fluid exsolution can be tracked by three batches of magma (Gr1→Gr3) intruded at the level of the ore deposition to form the Yermakovka stock. Each batch of the sequential granite group is found to intrude at decreasing temperature (from 840 to 730 °C) and progressively increasing extent of crystallization of magma in the parental pluton. This resulted in the enrichment of the ascending melts in H₂O (3.9 to 6.1 wt.%), F (2.6 to 4.1 wt.%) and some incompatible elements (Zr, Nb, Th, Rb, Pb). Although the earliest evidence for the exsolution of homogeneous fluoride–sulphate brine correlates with the final stage of the Gr2 ascent, the most intensive volatile(s) release from the emplaced magmas is shown to occur during their in situ crystallization, which was associated with the separation of exsolved fluid into immiscible phases, brine and low-salinity solution. Compositions of these fluid phases are determined using atomic emission spectroscopy of the appropriate fluid inclusions opened by a laser microprobe and EMPA and SEM–EDS analyses of daughter crystals. The brine phase is enriched in Mo, Mn, Be (up to 17, 8, and 0.3 g/kg, respectively) and contains perceptible abundances of Ce, La, Pb, Zn, whereas the low-salinity phase is enriched only in Be (up to 0.6 g/kg). The selective mobilization of the metals from the melt into fluids is considered to result from the oxidized state of the melt and fluids, peralkalinity of the melt during crystallization, and high F content of the melt. The immiscible fluid phases are shown to migrate together through the solidifying stock giving rise to the albitized granite that is enriched in molybdenite but devoid of Be minerals. In the country rocks, solutions similar to the brine and low-salinity phases of the magmatic fluid made up separate fluid flows, which produced Be and Mo mineralization and were issued predominantly from the parental pluton. Both types of mineralization are nearly monometallic which suggests that of the metals, jointly transported by the brine, only Mo and, in part, Ce and La precipitated separately at the level where the low-salinity solutions deposited Be ores.     

Platinum mineralization of the Svetly Bor and Nizhny Tagil intrusions,Ural Platinum Belt

This paper presents the results of a detailed mineralogical and micro analytical study of two Ural-Alaskan type intrusions in the Ural Platinum Belt: (1) the dunite-hosted mineralization of the Svetly Bor intrusion, and (2) the chromitite mineralization of the Nizhny Tagil intrusion. Two generations of platinum minerals are typical of both intrusions: magmatic Pt–Fe(Ni) alloys, and post-magmatic Pt(Fe,Ni,Cu) alloys. A trend from ferroan platinum to isoferroplatinum (Pt,Fe → Pt₃Fe) is shown for magmatic alloys of the Svetly Bor intrusion. Magmatic alloys of the Nizhny Tagil intrusion are represented by ferroan platinum (with Ni) only, varying in Fe. The magmatic Pt–Fe alloys of both intrusions were depleted in Fe during the evolution of ore-forming systems and crystallized during the entire magmatic process, generally as fine cubic crystals and anhedral grains hosted by dunite at the magmatic stage during and after the crystallization of dunite (platinum–dunite type of the Svetly Bor intrusion). The evolution of mineral paragenesis was accompanied by a temperature drop, as well as increases in fO₂ and fS₂.Most of the platinum was concentrated in the residual melts together with chromium, and crystallized in the final stage of the magmatic process (platinum–chromite ore of the Nizhny Tagil intrusion). Post-magmatic Pt(Fe,Cu,Ni) alloys formed during the serpentinization of dunite evolved according to a general compositional trend from tetraferroplatinum and ferronickelplatinum to tulameenite and later to Pt–Cu alloy and Pt-oxide (PtFe) → Pt(Fe,Cu,Ni) → Cu₃Pt → Pt–O. Platinum-rich mineralization of both intrusions was formed in the late magmatic stage from a melt rich in volatiles, regardless of their location in dunite or chromitites. Most probably, the rock structure (fracture systems) was the determining factor in the migration of PGE-rich residual melts and ore accumulation.     

新疆阿尔泰巴斯铁列克钨多金属矿区花岗岩黑云母特征及成岩成矿意义

黑云母是花岗质岩石中常见的造岩矿物,其成分可以有效指示花岗岩形成的物理化学条件和岩石成因。巴斯铁列克矿床是近年来在新疆阿尔泰造山带南缘发现的首例二叠纪矽卡岩型钨多金属矿床。矿区出露多种类型二叠纪含钨花岗岩。为理清花岗质岩体之间、岩体与钨多金属矿化之间的关系,文章采用电子探针测定了黑云母花岗岩、二长花岗岩、二云母花岗岩和钾长花岗岩中的黑云母成分。结果表明,所有黑云母具有富铁、高铝、贫镁特征,含铁指数(Fe²⁺/(Mg+Fe²⁺))为0.66~0.80,二云母花岗岩属铁质黑云母而黑云母花岗岩、二长花岗岩和钾长花岗岩属铁叶黑云母。所有岩石是具有A型特征的I型花岗岩。不同类型岩石中黑云母的成分差异与岩浆来源、分异演化程度有关。二云母花岗岩中黑云母的w(MgO)与结晶温度最高,与黑云母平衡流体的log(fHF/fHCl)值（-1.13~-1.25）最低,log(fH₂O/fHF)值（4.64~4.96）最高,母岩浆相对富Cl;黑云母花岗岩中log(fHF/fHCl)值最高,log(fH₂O/fHF)最低,与二长花岗岩是同一岩浆房不同演化阶段的产物,与二云母花岗岩和钾长花岗岩属不同的岩浆体系,母岩浆相对富F元素。黑云母花岗岩与W矿化关系更密切。     

Partitioning of F between H2O and CO2 fluids and topaz rhyolite melt

Fluid/melt distribution coefficients for F have been determined in experiments conducted with peraluminous topaz rhyolite melts and fluids consisting of H₂O and H₂O+CO₂ at pressures of 0.5 to 5 kbar, temperatures of 775°–1000°C, and concentrations of F in the melt ranging from 0.5 to 6.9 wt%. The major element, F, and Cl concentrations of the starting material and run product glasses were determined by electron microprobe, and the concentration of F in the fluid was calculated by mass balance. The H₂O concentrations of some run product glasses were determined by ion microprobe (SIMS). The solubility of melt in the fluid phase increases with increasing F in the system; the solubility of H₂O in the melt is independent of the F concentration of the system with up to 6.3 wt% F in the melt. No evidence of immiscible silica- and fluoriderich liquids was detected in the hydrous but water-undersaturated starting material glasses (8.5 wt% F in melt) or in the water-saturated run product glasses. F concentrates in topaz rhyolite melts relative to coexisting fluids at most conditions studied; however, D_F (wt% F in fluid/wt% F in melt) increases strongly with increasing F in the system. Maximum values of D_F in this study are significantly larger than those previously reported in the literature. Linear extrapolation of the data suggests that D_F is greater than one for water-saturated, peraluminous granitic melts containing 8 wt% F at 800° C and 2 kbar. D_F increases as temperature and as (H₂O/H₂O+CO₂) of the fluid increase. For topaz rhyolite melts containing 1 wt% F and with H₂O-rich fluids, D_F is independent of changes in pressure from 2 to 5 kbar at 800° C; for melts containing 1 wt% F and in equilibrium with CO₂-bearing fluids the concentrations of F in fluid increases with increasing pressure. F-and lithophile element-enriched granites may evolve to compositions containing extreme concentrations of F during the final stages of crystallization. If F in the melt exceeds 8 wt%, D_F is greater than one and the associated magmatic-hydrothermal fluid contains >4 molal F. Such F-enriched fluids may be important in the mass transport of ore constituents, i.e., F, Mo, W, Sn, Li, Be, Rb, Cs, U, Th, Nb, Ta, and B, from the magma.     

白杨河超大型铍(铀)矿床中蓝柱石(BeAlSiO4(OH))的矿物特征与地质意义

蓝柱石作为一种较为罕见的含铍矿物,通常产在过铝-准铝性的岩浆-热液演化系统中,或发育于富铝质岩石的低级变质过程中。本文通过偏光显微镜、电子探针、X射线粉晶衍射、激光拉曼光谱和红外光谱等多种手段方法,在白杨河超大型铍(铀)矿床首次发现了除羟硅铍石以外的另一种含铍矿物-蓝柱石。系统的矿物学研究表明蓝柱石应由花岗斑岩岩浆分异的岩浆热液直接沉淀而成,且形成于富F环境中。结合前人关于矿床地质特征、成矿年代学和地球化学等方面的研究,认为白杨河矿床中的铍矿化应是花岗斑岩深部岩浆房分异的岩浆热液,在不断演化过程中形成的,而与后期流体(包括幔源流体和大气降水)的淋滤作用无关或关系很小。     

Pyroxenites of the Krestovskaya alkaline-ultramafic intrusion: Composition of parental magmas and their sources

The main rock-forming minerals of pyroxenites in the Krestovskaya intrusion in the Maimecha-Kotui alkaline-ultramafic province are Al- and Ti-fassaite and low-Al high-Mg diopside. Both clinopyroxene varieties bear primary inclusions of alkaline-ultramafic melts enriched in incompatible elements, F (up to 0.3–0.4 wt %), and probably also CO₂. The homogenization temperatures of the inclusions are approximately equal and lie within the range of 1200–1300° C. However, the melts preserved in the diopside are undersaturated in Si and Al and richer in Fe, Ba, Sr, Na, and incompatible elements than melt inclusions in the fassaite; they are free in H₂O (no more than 0.003 wt %); and are close in composition to katungite-mafurite. Melt inclusions in the fassaite are richer in Si, Mg, and Al; contain up to 0.435 wt % H₂O; and compositionally approach alkaline picritoids. Melts of such composition cannot be produced by the differentiation of a single parental magma and were most probably derived from different mantle sources. Judging from the high concentrations of incompatible elements and their distribution in the melt inclusions, these sources were localized in the undepleted mantle at various depths (the picritoid melts were derived from a deeper source) and underwent different degrees of partial melting, with garnet and plagioclase remaining in the residue. The coexistence of diopside and fassaite in a single rock can be explained by the concurrent development of magmatic chambers at different depths during rifting, when this process was repeatedly reactivated and it facilitated the arrival of primitive melts derived from different mantle sources into the same magmatic chambers, in which these melts mixed and evolved. These processes probably predetermined the origin of the alkaline-ultramafic carbonatite intrusions and perhaps also the potassic series in the East African Rift.     

Magmatic petrogenesis and the evolution of (F:Cl:OH) fluid composition in barren and tungsten skarn-associated plutons using apatite and biotite compositions: Case studies from the northern Canadian Cordillera

A detailed study of apatite and biotite compositions in multiple intrusive phases from five composite plutons in the northern Canadian Cordillera was undertaken with the aim of determining the composition of magmatic fluids relative to F:Cl:OH for several plutons―both barren and mineralizing―and for specific intrusive phases from each pluton that may be related to nearby tungsten skarns. Magmatic apatite and biotite compositions are consistent with a crustal source of magma, either derived from predominantly supracrustal rocks, and (or) derived from predominantly infracrustal rocks and fractionated to felsic compositions. Increasing MnO (± FeO and XF:XCl) with decreasing CaO in apatite broadly correlates with an increasing degree of magmatic differentiation, although Fe# vs. total aluminum in biotite is a better indicator of inter- and intra-plutonic differentiation. Anomalously iron-rich biotites occur in highly fractionated and (or) wallrock-contaminated phases of plutons associated with tungsten skarns.Estimates of magmatic fluid composition―calculated as the activity ratios log[aHCl / a_HF] and log[a_HOH / a_HF] from apatite and biotite compositions―show several trends with respect to magmatic differentiation. Two barren plutons demonstrate that fluids in silicic magmas become HF enriched relative to HCl with increasing differentiation, although re-equilibration with late-stage sub-solidus or hydrothermal fluids may obscure this trend. The three intrusions with associated tungsten skarn mineralization, including the world-class Cantung deposit, also become HF-enriched with magmatic evolution. However, magmatic apatite and biotite in individual intrusive phases that are the most closely associated with mineralization have equilibrated with compositionally distinct fluids. In these particular intrusive phases, apatite appears to have equilibrated with an earlier HCl- and H₂O-rich magmatic fluid, and biotite appears to have equilibrated with a later HCl- and (a particularly) H₂O-rich magmatic fluid. The fluid in these magmas apparently evolved to a H₂O-rich (or less saline) composition as the temperature of the magma decreased. None of the other intrusive phases, from either the barren or tungsten-associated plutons, have apatite and biotite activity ratios that are suggestive of equilibration with such an HCl/HF- and H₂O/HF-rich fluid. Instead, the activity ratios calculated from apatite and biotite in intrusive phases that are not as closely associated with mineralization are well-coupled and unremarkable (although small variations are common), which would suggest that both minerals equilibrated with similar fluids. These intrusive phases do not appear to have produced a large quantity of saline hydrous fluid capable of seggregating and transporting tungsten. The identification of intrusive phases that did produce magmatic fluids that were anomalously enriched in HCl and H₂O could, therefore, be a predictor of nearby tungsten skarn mineralization.     

Compositions of magmatic melts and evolution of mineral-forming fluids in the banska Stiavnica epithermal Au-Ag-Pb-Zn deposit, Slovakia: A study of inclusions in minerals

Melt and fluid inclusions were investigated in minerals from igneous rocks and ore (Au-Ag-Pb-Zn) veins of the Stiavnica ore field in Central Slovakia. High H₂O (7.1–12.0 wt %) and Cl (0.32–0.46 wt %) contents were found in silicate melt inclusions (65–69 wt % SiO₂ and 5.2–5.6 wt % K₂O) in plagioclase phenocrysts (An 68–36) from biotite-homblende andesites of the eastern part of the caldera. Similar high water contents are characteristic of magmatic melts (71–76 wt % SiO₂ and 3.7–5.1 wt % K₂O) forming the sanidine rhyolites of the Vyhne extrusive dome in the northwestern part of the Stiavnica caldera (up to 7.1 wt %) and the rhyolites of the Klotilda dike in the eastern part of the ore field (up to 11.5 wt %). The examination of primary inclusions in quartz and sanidine from the Vyhne rhyolites revealed high concentrations of N₂ and CO₂ in magmatic fluid (8.6 g/kg H₂O and 59 g/kg H₂O, respectively). Fluid pressure was estimated as 5.0 kbar on the basis of primary CO₂ fluid inclusions in plagioclase phenocrysts from the Kalvari basanites. This value corresponds to a depth of 18 km and may be indicative of a deep CO₂ source. Quartz from the granodiorites of the central part of the Stiavnica-Hodrusa complex crystallized from a melt with 4.2–6.1 wt % H₂O and 0.24–0.80 wt % Cl. Magmatic fluid cogenetic with this silicate melt was represented by a chloride brine with a salinity of no less than 77–80 wt % NaCl equiv. Secondary inclusions in quartz of the igneous rocks recorded a continuous trend of temperature, pressure, and solution salinity, from the parameters of magmatic fluids to the conditions of formation of ore veins. The gold mineralization of the Svyatozar vein system was formed from boiling low-salinity fluids (0.3–8.0 wt % NaCl equv.) at temperatures of 365–160°C and pressures of 160–60 bar. The Terezia, Bieber, Viliam, Spitaler, and Rozalia epithermal gold-silver-base metal veins were also formed from heterogeneous low-salinity fluids (0.3–12.1 wt %) at temperatures of 380–58°C and pressures of 240–10 bar. It was found that the salt components of the solutions were dominated by chlorides (high content of fluorine, up to 0.45 mol/kg H₂O, was also detected), and sulfate solutions appeared in the upper levels. The dissolved gas of ore-forming solutions was dominated by CO₂ (0.1–8.4 mol %, averaging 1.3 wt %) and contained minor nitrogen (0.00–0.85 mol %, averaging 0.05 mol %) and negligible methane admixtures (0.00–0.05 mol %, averaging 0.004 mol %). These data allowed us to conclude that the magmatic melts could be sources of H₂O, Cl, CO₂, and N₂. The formation of the epithermal mineralization of the Stiavnica ore field was associated with the mixing of magmatic fluid with low-concentration meteoric waters, and the fluid was in a heterogeneous state.     

东天山镁铁质_超镁铁质岩带岩石特征及铜镍成矿作用

东天山地区分布有众多镁铁质-超镁铁质岩体,岩体成群成带状分布,从北向南可划分为7个区带,受区域性韧性剪切带和断裂构造控制。从岩相学来看,本区含矿岩体可分为多期次侵入的复式杂岩体和单期次侵入的超镁铁质单式杂岩体,显示出深源岩浆充分分异的特征。含矿岩体具有高镁、低碱、低钙、低铝、低钛特征,具有较高的Mg#、m/f和m/s比值,兼具岩浆硫化物熔离作用与岩浆结晶分异作用。根据TiO2-10P2O5-10MnO图判别出本区岩浆具有拉斑玄武岩到钙碱玄武岩过渡的性质,岩浆源具有钙碱性玄武岩浆特征,富含含水矿物,预示了早期俯冲洋壳对幔源岩浆的交代作用。岩体矿化分为3种成矿作用和5期成矿步骤,且岩浆成矿作用与热液作用几乎同时进行,岩浆分异作用提供热液来源,而热液作用促进硫化物的饱和与熔离,造成岩石的热液蚀变结构并对岩浆期成矿进行改造。晚期岩体隆升后,矿体出露地表遭受氧化淋滤作用,形成特有的地表氧化带找矿标志。     

攀西地区镁铁质岩浆成矿系统的流体动力学模型

尽管镁铁质侵入体及其与成矿作用的关系得到了特别关注,但有许多科学问题迄今仍模糊不清。基于新的野外观察和理论分析,文中提出一个复杂性流体动力学模型,试图整合解释矿床地质学、矿相学和矿物学特征。假定岩浆成矿系统的行为取决于熔体和流体两个子系统的强相互作用,系统演化过程中子系统物理性质的连续改变可以导致多种非线性变化:(1)熔体子系统未发生明显结晶作用之前,含矿流体弥漫式透过熔体向上迁移,产生具有隐性火成层理的致矿侵入体和浸染状整合矿体。在这种条件下,高速运动的含矿流体可以导致岩浆侵入体全岩矿化;较低速上升的含矿流体也可以导致强烈的岩浆分异作用,但岩浆侵入体的边缘部分将没有成矿金属的富集。(2)岩浆侵入体部分固结(如半固结)时,含矿流体只能大规模输入到岩体中心尚未固结的部分,并导致强烈的双扩散对流,产生明显的韵律性层理和整合型块状矿体。(3)岩浆侵入体接近完全固结时,巨大的流体超压或远场应力场可导致板状侵入体沿补给通道方向破裂,含矿流体上升导致了不整合矿体的产生。(4)岩浆侵入体完全固结之后,后续含矿流体只能沿着层状侵入体与底板围岩的接触带迁移,形成新型板状矿体或巢状矿体,甚至夕卡岩型矿体。(5)富氧化物流体之后还可以有富硫化物流体上升,有利于产生硫化物矿体。这种分析大致符合攀西地区的客观实际,因而可以得出结论：(1)岩浆侵入体是否成为致矿侵入体取决于含矿流体的输入,而不是岩浆分异作用;(2)致矿侵入体的分异特征是含矿流体输入的结果,而不是相反;(3)镁铁质岩浆成矿系统是一种复杂性动力系统,含矿流体的输入是其行为发生非线性变化的根本原因;(4)攀西地区的镁铁质岩浆成矿系统包括整合型(包括块状和浸染状两种亚型)、不整合型和夕卡岩型铁矿子系统以及浸染状和块状硫化物型成矿子系统;(5)攀西地区的铁矿体不仅仅位于层状岩体之内,下伏围岩中也有找矿潜力,甚至发现块状硫化物的潜力。     

东天山图拉尔根铜镍钴硫化物矿床岩相、岩石地球化学特征及其形成的构造背景

新疆图拉尔根铜镍钴矿产于康古儿塔格—黄山韧性剪切带的北东段,是由硫化物深部熔离成矿为主兼就地熔离、热液叠加成矿多重作用形成的半隐伏矿床。1号岩体以全岩矿化为特征,可分为4个岩相:角闪橄榄岩、辉石橄榄岩、角闪辉石岩、辉长岩。岩性具有单期岩浆多次脉动上涌成矿特征。岩体m/f值为3.1～4.8,属于铁质超镁铁岩类,且具有低钛、低碱、低Al2O3特征,与黄山—镜儿泉镁铁质-超镁铁质杂岩带岩石化学特征相似。由稀土元素配分曲线和微量元素、过渡族元素蛛网图可知1号和2号岩体具有同源性,并具有互补性,预示2号岩体深部成矿潜力很大,虽然其地表辉长岩矿化微弱。根据横穿1号和2号岩体的大地电磁测深剖面图可以看出两个岩体在深部具有同一个岩浆通道,也验证了两岩体属于同一岩浆来源。较低的La/Sm(<2)和Th/Ta值(4.6)表明成矿岩浆为地幔来源,岩体就位时很少受到地壳的混染。     

长江中下游成矿带玢岩铁矿研究新进展及对矿床成因的启示

长江中下游成矿带的宁芜和庐枞火山岩盆地中发育了大量与早白垩世(约130 Ma)陆相火山-侵入岩有关的玢岩铁矿。这类矿床的特征为具有磁铁矿-磷灰石-阳起石(透辉石)矿物组合,在国际上一般被称为铁氧化物-磷灰石型(Iron Oxide-Apatite, IOA)或基鲁纳型(Kiruna-type)矿床。玢岩铁矿的概念自20世纪70年代提出以来,其成因就一直存在争议,主要有矿浆、岩浆热液及矿浆-热液过渡的观点。近年来的高精度年代学揭示出宁芜和庐枞盆地内玢岩铁矿在约130 Ma集中爆发成矿。矿物学、岩石学及地球化学的综合研究表明成矿物质主要来源于次火山岩体,且成矿早期流体具有高温(550~780 ℃)和超高盐度(可达90% NaCl_eq)的特点。这些特点与成矿岩体及周围火山岩在成矿早阶段发育大规模钠质蚀变相吻合;但同时S-Sr等同位素和流体包裹体成分分析表明在铁成矿过程中还有外来壳源(如膏盐层物质)流体的加入。一些研究工作还表明玢岩铁矿与夕卡岩型铁矿具有相似的热液蚀变演化过程,暗示两者或许存在某些成因联系,很可能是相似流体与不同性质围岩及在不同温度下水岩交代产物。这些新的证据为探讨玢岩铁矿的成矿作用过程和成因机制提供了新的制约,也带来了新问题。本文从成岩成矿年代学、成矿物质来源、成矿早期流体性质、玢岩铁矿与夕卡岩铁矿及其外围新发现的金铜矿化的成因联系等角度,对近年来长江中下游成矿带玢岩铁矿研究的主要新进展进行初步总结。当前IOA型矿床的成因研究成为国际上矿床学研究的一个热点,除了长期争论的矿浆成因和岩浆热液成因,最近提出多个了岩浆-热液复合成矿模型,如岩浆磁铁矿-气泡悬浮模型及富水铁熔体的上升、脱气和侵位成因模型。将IOA型矿床成因争论的焦点逐渐聚焦在岩浆到岩浆后(岩浆热液)阶段,铁质究竟是以含铁岩浆热液、铁矿浆 (Fe-O或P-Ca-Fe-O),还是岩浆磁铁矿微晶或其他未知的形式来富集成矿的,还有待进一步研究,文章对以上的新模型进行简要介绍和评述,并与长江中下游的矿床进行对比。     

Interaction of magma with sedimentary wall rock and magnetite ore genesis in the Panzhihua mafic intrusion,SW China

In southwestern China, several large magmatic Fe–Ti–V oxide ore deposits are hosted by gabbroic intrusions associated with the Emeishan flood basalts. The Panzhihua gabbroic intrusion, a little deformed sill that contains a large titanomagnetite deposit at its base, concordantly intrudes late-Proterozoic dolostones. Mineralogical and chemical studies of the contact aureole in the footwall dolostones demonstrate that the metamorphism was largely isochemical but released large quantities of CO₂ as the rocks were converted to marble and skarns during intrusion of the gabbroic magma. Petrological modelling of the crystallization of the intrusion, using H₂O-poor Emeishan basalt as parent magma, shows that under normal conditions, Fe–Ti oxides crystallize at a late stage, after the crystallization of abundant olivine, clinopyroxene and plagioclase. In order for titanomagnetite to separate efficiently to form the ore deposit, this mineral must have crystallized earlier and close to the liquidus. We propose that CO₂-rich fluids released during decarbonatization of sedimentary floor rocks passed up through the magma. Redox equilibria calculations show that when magma with the composition of Emeishan basalt is fluxed by a CO₂-rich gas phase, its equilibrium oxygen fugacity (fO₂) increases from the fayalite–magnetite–quartz buffer (FMQ) to FMQ + 1.5. From experimental constraints on magnetite saturation in basaltic magma under controlled fO₂, such an oxidizing event would allow magnetite to crystallize near to the liquidus, leading to the formation of the deposit.     

Ore Genesis of the Kalatongke Cu–Ni Sulfide Deposits, Western China: Constraints from Volatile Chemical and Carbon Isotopic Compositions

The Kalatongke Cu–Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt (CAOB). The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200–400°C, 400–900°C and 900–1200°C. The released volatiles from silicate mineral separates at 400–900°C and 900–1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O (av. ~92 mol%) with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values (from ?20.86‰ to ?12.85‰) of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantle-derived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200–400°C are dominated by H2O with minor CO2, N2+CO and SO2, with δ13CCO2 values (?25.66‰ to ?22.98‰) within the crustal ranges, and are considered to be related to secondary tectonic– hydrothermal activities.     

Formation of PGM-Cu-Ni deposits in the process of evolution of flood-basalt magmatism in the Noril’sk region

The timing of the emplacement of ore-bearing melts in the process of evolution of flood-basalt magmatism in the Noril’sk District is discussed. The current models of ore formation consider the emplacement of ore-bearing intrusions either under the conditions of a closed magmatic system as a product of a self-dependent magmatic event, or under the conditions of an open magmatic system, where intrusions are parts of the conduits feeding lava flows. In both cases, the composition of the initial magma, the content of volatile components therein, and the contribution of country rock assimilation are important for the development of a genetic model. The relationships between lavas and intrusions are exemplified in the South Maslov intrusion, which cuts through the rocks of the Nadezhdinsky Formation. No geological evidence for links of lavas to intrusions has been established. Substantial difference in geochemistry (Ti contents, Gd/Yb and La/Sm ratios, etc.) of the tuff and lava sequence on the northern shore of Lake Lama and the Maslov intrusions are demonstrated. It is concluded that the Noril’sk deposits were formed as products of emplacement of self-dependent portion of magma in the post-lower Nadezhdinsky time. The melt composition determined from melt inclusions in olivine corresponds to high-Mg tholeiitic basalt (up to 7–8 wt % MgO) containing up to 1 wt % H₂O and 0.3 wt % Cl and undersaturated with sulfur. The fluid regime of flood-basalt volcanism had no anomalous features—the fluid was aqueous-carbon dioxide. The melts of ore-bearing and barren intrusions had similar concentrations of volatile components. The distribution of major and trace elements in intrusive rocks of the contact zone with the lower part of the Nadezhdinsky Formation characterized by high (La/Sm)_N ratio in comparison with gabbroic rocks (2.8–2.3 and 1.3–1.6, respectively), indicates that contamination of the initial melt only took place in a narrow (1 m) contact zone or did not develop at all. New data on isotopic compositions of Sr (⁸⁷Sr/⁸⁶Sr)₂₅₁ = 0.7089 and Pb (²⁰⁶Pb/²⁰⁴Pb = 20.877–24.528 in anhydrite confirm that local assimilation did not play a substantial role in the formation of rock and ores. On the basis of chemical composition of ore-forming intrusions, their isotopic characteristics, and the composition of melt inclusions in olivine, it is suggested that the lower crustal rocks were a major source of ore-bearing magmas.     

Formation of extremely F-rich hydrous melt fractions and hydrothermal fluids during differentiation of highly evolved tin-granite magmas: a melt/fluid-inclusion study

Quartz crystals from topaz–zinnwaldite–albite granites from Zinnwald (Erzgebirge, Germany) contain, in addition to primary and secondary fluid inclusions (FIs), abundant crystalline silicate-melt inclusions (MIs) with diameters up to 200 m. These MIs represent various stages of evolution of a highly evolved melt system that finally gave rise to granite-related Sn–W mineralization. The combination of special experimental techniques with confocal laser Raman-microprobe spectroscopy and EMPA permits precise measurement of elevated contents of H₂O, F, and B in re-homogenized MIs. The contents of H₂O and F were observed to increase from 3 to 30 and 1.9 to 6.4 wt%, respectively, during magma differentiation. However, there is a second MI group, very rich in H₂O, with values up to 55 wt% H₂O and an F concentration of approximately 3 wt%. Ongoing enrichment of volatiles H₂O, F, B, and Cl and of Cs and Rb can be explained in terms of magma differentiation triggered by fractional crystallization and thus, is suggested to reflect elemental abundances in natural magmas, and not boundary-layer melts. Partitioning between melt and cogenetic fluids has further modified the magmatic concentrations of some elements, particularly Sn. The coexistence of two types of MIs with primary FIs indicates fluid saturation early in the history of magma crystallization, connected with a continuous sequestration of Sn, F, and B. The results of this study provide additional evidence for the extraordinary importance of the interplay of H₂O, F, and B in the enrichment of Sn during magma differentiation by decreasing the viscosity of and increasing the diffusivity in the melts as well as by the formation of various stable fluoride complexes in the melt and coexisting fluid.

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小岩浆大流体成大矿与透岩浆流体成矿作用——以东秦岭-大别山成矿带钼矿床为例

岩浆活动与内生金属成矿作用关系密切,备受国内外矿床学家的关注。表现为它们在时空上具有广泛的一致性,成矿与岩浆岩有关,成矿物质由同源岩浆分异演化而来。这便是著名的岩浆热液成矿理论,也称岩浆期后热液成矿理论,该理论把内生金属成矿系统看作是一个理想系统。东秦岭-大别山地区的钼矿-花岗岩关系研究表明,钼成矿与小岩体(小岩浆)关系密切,而大岩体/基与钼矿没有成生联系;地质事实表明,大型-超大型矿床往往广泛发育了大规模的热液(流体)蚀变(大流体),具有大的流体/岩浆比,其矿化蚀变范围是小岩体的几十甚至几百倍,表明成矿过程中必有外来流体的广泛参与。由于小岩体往往没有经过强烈的分异结晶作用,质量平衡计算表明,小岩浆体不可能产生足够数量的含矿流体和成矿物质;因此,成岩与成矿有本质的区别,成矿系统应是一个非线性的复杂性动力学系统。研究表明,东秦岭-大别山小斑岩体来源较深(下地壳),成矿流体来源于地幔,二者呈双层结构;岩浆实际上是沟通深部和浅部的通道,这种非岩浆分异的外来成矿流体我们称之为透岩浆流体。小岩体不是成矿的必备的条件,只有出现大流体时才能成大矿。东秦岭-大别山地区有200多个小岩体,但大型、超大型钼矿矿床仅有10余个,只有小岩浆(小岩体)大流体(强蚀变)成大矿,其余众多小岩体由于没有流体(蚀变)或流体少(弱蚀变)而不成矿或成小矿。由此可见,岩浆成矿系统实际上是一种流体(挥发分)过饱和系统或熔体-流体流及流体对熔体的强相互作用。当岩浆系统被加入大量源自地幔的高温高压含矿流体之后,系统将具有极大的活动能力,从而深部含矿流体沿裂隙快速上升到地壳浅部卸载成矿。为解释上述成矿特征,作者引入并厘定了透岩浆流体的概念。透岩浆流体被重新定义为透过岩浆活动并导致岩浆系统行为发生非线性变化的外来流体。据此,输入了含矿流体的岩浆可成矿,未输入含矿流体的岩浆不成矿。这种认识可以解释东秦岭-大别山地区大多数小岩体不成矿或只形成小矿的现象。     

Tin partition behavior and implications for the Furong tin ore formation associated with peralkaline intrusive granite in Hunan Province,China

Tin deposits are often closely associated with granitic intrusions. In this study, we analyzed tin partition coefficients between different fluids and melts (\({\text{D}}_{Sn}^{aq.fl./melt}\)) as well as various crystals and melts \({\text{D}}_{Sn}^{aq.fl./melt}\)(\({\text{D}}_{Sn}^{crystal/melt}\)) from the Furong tin deposit associated with the Qitianling A-type granite. Our experimental results indicate that tin partition behavior is affected by the chemical compositions of fluids, melts, and minerals. Tin is prone to partitioning into the residual magma in fractional crystallization or other differential magmatic processes if the magma originated from crustal sources with high alkali content, high volatile content, and low oxygen fugacity. Highly evolved residual peralkaline granitic magma enriched in tin can lead to tin mineralization in a later stage. Furthermore, the volatiles F and Cl in the magma play important roles in tin partitioning behavior. Low F contents in the melt phase and high Cl content in the aqueous fluid phase are favorable factors for tin partitioning in the aqueous fluid phase. High Cl content in the aqueous fluid catalyzes water–rock interaction and leads to the extraction of tin from tin-bearing minerals. All these findings support a hydrothermal origin for the tin deposits. In light of the geotectonic setting, petrochemical characteristics, and mineralizing physicochemical conditions of the Furong tin deposit, it is inferred that the ore-forming fluid of the Furong tin ore deposit could have derived from the Qitianling peralkaline intrusion.     

A Study of Ore-forming Fluids in the Shimensi Tungsten Deposit, Dahutang Tungsten Polymetallic Ore Field, Jiangxi Province, China

The Dahutang tungsten polymetallic ore field is located north of the Nanling W-Sn polymetallic metallogenic belt and south of the Middle—Lower Yangtze River Valley Cu-Mo-Au-Fe porphyry-skarn belt.It is a newly discovered ore field,and probably represents the largest tungsten mineralization district in the world.The Shimensi deposit is one of the mineral deposits in the Dahutang ore field,and is associated with Yanshanian granites intruding into a Neoproterozoic granodiorite batholith.On the basis of geologic studies,this paper presents new petrographic,microthermometric,laser Raman spectroscopic and hydrogen and oxygen isotopic studies of fluid inclusions from the Shimensi deposit.The results show that there are three types of fluid inclusions in quartz from various mineralization stages:liquid-rich two-phase fluid inclusions,vapor-rich two-phase fluid inclusions,and three-phase fluid inclusions containing a solid crystal,with the vast majority being liquid-rich two-phase fluid inclusions.In addition,melt and melt-fluid inclusions were also found in quartz from pegmatoid bodies in the margin of the Yanshanian intrusion.The homogenization temperatures of liquid-rich two-phase fluid inclusions in quartz range from 162 to 363℃ and salinities are 0.5wt%-9.5wt%NaCI equivalent.From the early to late mineralization stages,with the decreasing of the homogenization temperature,the salinity also shows a decreasing trend.The ore-forming fluids can be approximated by a NaCl-H_2O fluid system,with small amounts of volatile components including CO_2,CH_4 and N_2,as suggested by Laser Raman spectroscopic analyses.The hydrogen and oxygen isotope data show that δ5D_(V-smow) values of bulk fluid inclusions in quartz from various mineralization stages vary from-63.8‰ to-108.4‰,and the δ~(18)O_(H2O) values calculated from the δ~(18)O_(V-)smow values of quartz vary from-2.28‰ to 7.21‰.These H-O isotopic data are interpreted to indicate that the ore-forming fluids are mainly composed of magmatic water in the early stage,and meteoric water was added and participated in mineralization in the late stage.Integrating the geological characteristics and analytical data,we propose that the ore-forming fluids of the Shimensi deposit were mainly derived from Yanshanian granitic magma,the evolution of which resulted in highly differentiated melt,as recorded by melt and melt-fluid inclusions in pegmatoid quartz,and high concentrations of metals in the fluids.Cooling of the ore-forming fluids and mixing with meteoric water may be the key factors that led to mineralization in the Dahutang tungsten polymetallic ore field.     

Magma evolution and the formation of porphyry Cu–Au ore fluids: evidence from silicate and sulfide melt inclusions

Silicate and sulfide melt inclusions from the andesitic Farallón Negro Volcanic Complex in NW Argentina were analyzed by laser ablation ICPMS to track the behavior of Cu and Au during magma evolution, and to identify the processes in the source of fluids responsible for porphyry-Cu-Au mineralization at the 600 Mt Bajo de la Alumbrera deposit. The combination of silicate and sulfide melt inclusion data with previously published geological and geochemical information indicates that the source of ore metals and water was a mantle-derived mafic magma that contained approximately 6 wt.% H₂O and 200 ppm Cu. This magma and a rhyodacitic magma mixed in an upper-crustal magma chamber, feeding the volcanic systems and associated subvolcanic intrusions over 2.6 million years. Generation of the ore fluid from this magma occurred towards the end of this protracted evolution and probably involved six important steps: (1) Generation of a sulfide melt upon magma mixing in some parts of the magma chamber. (2) Partitioning of Cu and Au into the sulfide melt (enrichment factor of 10,000 for Cu) leading to Cu and Au concentrations of several wt.% or ppm, respectively. (3) A change in the tectonic regime from local extension to compression at the end of protracted volcanism. (4) Intrusion of a dacitic magma stock from the upper part of the layered magma chamber. (5) Volatile exsolution and resorption of the sulfide melt from the lower and more mafic parts of the magma chamber, generating a fluid with a Cu/Au ratio equal to that of the precursor sulfide. (6) Focused fluid transport and precipitation of the two metals in the porphyry, yielding an ore body containing Au and Cu in the proportions dictated by the magmatic fluid source. The Cu/S ratio in the sulfide melt inclusions requires that approximately 4,000 ppm sulfur is extracted from the andesitic magma upon mixing. This exceeds the solubility of sulfide or sulfate in either of the silicate melts and implies an additional source for S. The extra sulfur could be added in the form of anhydrite phenocrysts present in the rhyodacitic magma. It appears, thus, that unusually sulfur-rich, not Cu-rich magmas are the key to the formation of porphyry-type ore deposits. Our observations imply that dacitic intrusions hosting the porphyry–Cu–Au mineralization are not representative of the magma from which the ore-fluid exsolved. The source of the ore fluid is the underlying more mafic magma, and unaltered andesitic dikes emplaced immediately after ore formation are more likely to represent the magma from which the fluids were generated. At Alumbrera, these andesitic dikes carry relicts of the sulfide melt as inclusions in amphibole. Sulfide inclusions in similar dykes of other, less explored magmatic complexes may be used to predict the Au/Cu ratio of potential ore-forming fluids and the expected metal ratio in any undiscovered porphyry deposit.Editorial handling: B. Lehmann