Geochemical characteristics of tin-bearing magnetite-skarns

Geological and geochemical characteristics of tin-bearing magnetite-skarns are reviewed in this paper, together with the author’s opinion with respect to the mechanism of transport of tin in this environment. In addition to cassiterite, the most common form of occurrence of tin in nature, three other forms of occurrence are also of interest in tin-bearing magnetite-skarns: (1) tin present in the form of fine exsolution colloidal grains of cassiterite; (2) tin found as independent tin-bearing minerals, such as malayaite, stokesite, nordenskiöldine, Sn-paigeite, Sn-ludwigite and hulsite in a variety of skarns; (3) tin occurring in the lattice of some skarn minerals, such as garnet, pyroxene, spinel, amphibole, epidote, wollastonite and axinite in the manner of ionic replacement. When Mg²⁺ and Fe²⁺ bearing minerals, in some cases even Sulfides or other mineralizer-containing minerals, replace tin-bearing Fe³⁺ and Ti⁴⁺ skarn minerals during the late stage of skarn alteration, tin in the pre-existing silicates maybe extracted and remobilized, thus contributing to the formation of associated tin deposits.     

Tin-carrier minerals in metaluminous granites of the western Nanling Range (southern China): Constraints on processes of tin mineralization in oxidized granites

Huashan, Guposhan and Qitianling are three similar and representative metaluminous A-type tin granites in the western Nanling Range, China. They all have a high oxidization state with magnetite as the dominant Fe–Ti oxide. This study presents an understanding of systematic mineralogy of Sn-bearing minerals (biotite, titanite, magnetite and cassiterite) in the three granites. Biotite has an annite composition and both electron-microprobe and LA-ICP-MS analyses indicate trace amounts of tin in biotite (approximately 100–20 ppm). Chloritization of biotite is accompanied by formation of Sn-rich rutile and cassiterite. Titanite has a long history of crystallization from the early-magmatic stage through the late-magmatic stage to the hydrothermal stage. Owing to its solid-solution relationship with malayaite (CaSnSiO₅), titanite always contains tin to various extents. Early-magmatic titanite contains about 0.5 wt.% SnO₂, while the late-magmatic titanite is markedly enriched in tin (on average 14.8 and 3.4 SnO₂ in titanite from the Qitianling and Huashan granites, respectively). Magnetite grains typically display a trellis structure with ilmenite lamellae, where microinclusions of cassiterite (<1 μm in size) are present. This is likely consistent with features of the “oxy-exsolution” process of Sn-bearing titanomagnetite precursor. Cassiterite may be observed as late-magmatic phase, but most commonly appears as an alteration product of other primary minerals. All tin-bearing minerals in the three granites record a complete process of tin mineralization in granite. The features of tin in primary biotite, titanite and magnetite reflect an initial enrichment during the early stage of magmatic crystallization of the Huashan, Guposhan and Qitianling granites. Association of interstitial Sn-titanite and cassiterite suggests further tin enrichment related to fractional crystallization of granitic magmas. Fluids and alteration of primary minerals play an important role in the leaching, concentration and transportation of Sn during hydrothermal processes, which favors vein-type Sn mineralization.     

Cassiterite exsolution with ilmenite lamellae in magnetite from the Huashan metaluminous tin granite in southern China

Sn⁴⁺ is generally the dominant form of tin in magnetite-series granites as shown by the presence of cassiterite or its incorporation into Ti-bearing minerals such as biotite and titanite. Little is known about the behavior of tin in magnetite. The Huashan granite is an oxidized tin granite in the Nanling Range, southern China, where it contains magnetite as the dominant Fe oxide mineral. It is included in biotite as an early phase and also as interstitial grains spatially associated with ilmenite, cassiterite, Sn-rich titanite (SnO₂ up to 5.9?wt.%), fluorite and apatite. This association indicates that tin enrichment occurred during the late stage of magma crystallization. Ilmenite lamellae display a trellis structure consistent with features of the “oxy-exsolution” process of Sn-bearing titanomagnetite precursor. Micro-inclusions of cassiterite (<1?μm in size) are found only within ilmenite lamellae. This suggests that magnetite with cassiterite inclusions is likely an indicator mineral of oxidized tin granites. Although rare in nature, Sn-bearing magnetite from weathered granites where concentrated in stream sediments, may serve as a strategic tracer for tin exploration in granite districts and in placer deposits, in general.     

Tin mineralization in the Dajing tin–polymetallic deposit, Inner Mongolia, China

Dajing is a large-scale tin–polymetallic deposit that hosts the largest tin mine in North China. It is a hydrothermal vein-type deposit containing Sn, Cu, Pb, Zn, Ag, and minor components Co and In. The deposit consists of more than 690 veins hosted within Upper Permian sedimentary rocks.Three mineralization stages and six ore types are recognized with cassiterite constituting the dominant tin mineral. The SnO₂ content of cassiterite increases in the sequence of mineralization stages shear-deformation→cassiterite–quartz→cassiterite–sulfide (or chalcopyrite–pyrite) stage, while the content of FeO, TiO₂, Nb₂O₅, Ta₂O₅, and In₂O₅ tends to decrease with increases in NiO and Ga₂O₅. It is considered that the negative correlation between SnO₂ and FeO, Nb₂O₅, Ta₂O₅, and In₂O₅ results from elemental substitutions. The early stage cassiterite is much richer in Ta and the later stage cassiterite is much poorer in Ti and Fe than is usual in hydrothermal vein type tin deposits. This is interpreted to indicate that the component of early stage cassiterite reflects a granitic magma source while the composition of later stage cassiterite has a more obvious strata source. The compositional variation of cassiterite corresponds to decreasing crystallization temperatures within each stage and between sequential stages with time. The characteristics of REE in cassiterite from two stages are in accord with that of subvolcanic rocks and the Linxi formation. It suggests that tin transported during the cassiterite–quartz stage may have originated from subvolcanic dikes (e.g., dacite porphyry), while in the cassiterite–sulfide stage, tin may have been derived from wallrock (e.g. siltstone) of the Upper Permian-age Linxi Formation.     

新疆东准噶尔老鸦泉富碱花岗岩型锡矿床地质及成矿流体

老鸦泉碱性花岗岩位于新疆北部东准噶尔地区。老鸦泉碱性花岗岩体及其内卡姆斯特、干梁子锡矿床的矿石和岩石的岩矿鉴定、稀土元素以及流体包裹体的系统研究表明,老鸦泉碱性花岗岩及其内的花岗斑岩及含矿石英岩、云英岩化锡矿体、石英脉锡矿体,实际上是富碱花岗质岩浆逐渐分异演化的同源和最终产物,锡成矿流体为中-高温、低盐度。碱性岩浆晚期分异的大量气水热液富锡、富硅、富碱、富含F、Cl、SO²₄离子及离子团,其氧逸度高、酸度高、温度高,这种热液引起花岗岩体的硅化、云英岩化等自变质作用,在该作用中随温度、压力的降低及CH₄等还原性气体及CO₂气体的逃逸,改变了成矿流体的氧化-还原环境,流体向相对还原及碱性条件转化,在新的氧化还原、酸碱度界面条件下,其携带的锡的络合物不稳定而分解,锡沉淀成矿。     

西藏列廷冈铁多金属矿床矽卡岩矿物学特征及其地质意义

西藏列廷冈铁多金属矿床位于冈底斯北缘弧背断隆带内,是近年来勘查评价的规模可达中型的接触交代矽卡岩型矿床。矿区矽卡岩主要呈层状、似层状,矽卡岩型铁多金属矿体赋存于下-中三叠统查曲浦组(T_(1-2)c)矽卡岩和大理岩中,矿体呈透镜状、囊状、似层状产出,矽卡岩矿物较发育。为进一步查明矿床矽卡岩矿物种属及矽卡岩类型,剖析矽卡岩形成环境及其与矿化类型之间的关系,基于对矽卡岩矿物系统的显微镜下观测,利用电子探针对矿床主要矽卡岩矿物化学成分进行了系统分析。矽卡岩矿物主要为石榴子石、透辉石、角闪石、绿帘石、绿泥石等,矿床矽卡岩具典型钙矽卡岩特征。根据矿物共生组合及交代关系推断成矿流体经历了5个阶段,分别为早期矽卡岩阶段、退化蚀变阶段、早期热液阶段、石英硫化物阶段和碳酸盐阶段。特征矿物的电子探针分析结果表明,石榴子石主要为钙铁榴石-钙铝榴石系列(And_(18.37~99.89)Gro_(0.24~79.05)Ura+Pyr+Spe_(0.98~6.63)),且发育环带结构;辉石主要为透辉石-钙铁辉石系列(Di_(53.56~99.91)Hd_(1.61~44.55)Jo_(0.08~5.11));角闪石主要为阳起石,次为铁、镁角闪石,均属钙质角闪石系列;绿泥石主要为富铁的铁镁绿泥石;绿帘石贫Fe、Mg。在矿床成矿演化过程中,其成矿环境是发生改变的,早期矽卡岩阶段到最晚期碳酸盐阶段,成矿环境至少经历了从高温、偏碱性的氧化环境到相对低温、偏酸性的还原环境的转变。     

略论个旧锡矿床地质找矿的新发现及其途径

个旧锡矿区是个矿产资源丰富,开采历史悠久的老矿区。据历史记载,矿床发现约在汉代(距今2100a左右)。元、明两代有少量开采,清康熙(1700a)以前多采冶银、铅,至清乾隆(1740a)以后采锡增加,清末产锡量已居世果第四位。解放后三十年来开展了大规模的地质勘探,探明了五大矿田几十处矿床,探获锡、铜、铅、钨等金属储量数百万吨。七十年代以来,随着勘探工作和矿山开采程度日益加深,地质找矿面临“深、新、隐”等问题。通过不断学习、探索和试验研究。我们在地质认识、找矿效果和方法手段等方面又取得了一些新进展。     

Geology and Metallogeny of the Shizhuyuan Skarn-Greisen Deposit,Hunan Province,China

The Shizhuyuan deposit is the largest among the economically important polymetallic tungsten deposits in China. The deposit occurs within the thermal aureole of Yanshanian felsic intrusions that were emplaced into Devonian carbonates and marls. The mineralization can be divided into three phases that are genetically associated with three episodes of granitic emplacement-pseudoporphyritic biotite granite, equigranular biotite granite, and granite porphyry. During the emplacement of pseudoporphyritic biotite granite, thermal metamorphism and subsequent skarnization developed around the stock. The pure limestone was transformed to marble, whereas marls and argillite interlayers were changed to a series of metamorphic rocks such as grossular-diopside hornfels, wollastonite hornfels, diopside hornfels, wollastonite-vesuvianite hornfels, muscovite-K-feldspar-anorthite hornfels, and prehnitevermiculite hornfels. Because of the subsequent strong skarn development, most hornfelses later were transformed into skarns. The skarns distributed around the granite stock are mainly calcic. They are massive in structure, and are composed mainly of garnet, pyroxene, vesuvianite, and wollastonite, with interstitial fluorite, scheelite, and bismuthinite. Although there is no cassiterite in the early skarns, their tin contents average 0.1%. The distribution and compositional and mineralogical relationships of skarn minerals suggest that they formed as a result of progressive reactions of a hydrothermal solution with a limestone of generally constant composition, and that the dominant process was progressive removal of Ca and addition of other constituents to the rocks.

Following the primary skarn formation, some of the assemblages were retrograded to new assemblages such as fluorite-magnetite-salite rock, magnetite-fluorite-amphibole rock, and magnetite-fluorite-chlorite rock. The retrograde alteration of the skarns is characterized by a progressive addition of fluorine, alkali components, silica, tin, tungsten, and bismuth. A zonation from garnet-pyroxene skarn or garnet skarn, through fluorite-magnetite-salite rock, to magnetite-fluorite-chlorite rock frequently can be recognized in the deposit. All retrograde-altered rocks contain scheelite, cassiterite, molybdenite, and bismuthinite.

During the emplacement of equigranular biotite granite, skarn veins several tens of centimeters wide were developed; they contain large crystals of garnet and vesuvianite, and interstitial scheelite, wolframite, cassiterite, and molybdenite. This second stage of mineralization occurs predominantly as coarse and fine stockwork greisens, which were superimposed on the massive skarns and surrounding marble. Such W-Sn-Mo-Bi-bearing greisens can be divided into topaz greisen, protolithionite greisen, muscovite greisen, and margarite greisen. Besides calcic skarn veins and greisens, manganese skarn veinlets also were developed; they consist of rhodonite, spessartine-almandine solid solution, spessartine, and helvite. The distribution of greisens is responsible for a metal zonation—i.e., W-Sn-Mo-Bi and Sn-Be-Cu-F zones from the contact boundary between the granite stock and skarns outward in the deposit. A third stage of mineralization is represented by lead-zinc veins, which also are accompanied by manganese skarns consisting of spessartine, rhodonite, manganese-rich pyroxene, helvite, tephroite, fluorite, tourmaline, and manganese-rich phlogopite.     

Chemical and thermodynamic constraints on the hydrothermal transport and deposition of tin: I. Calculation of the solubility of cassiterite at high pressures and temperatures

Estimation of equation of state parameters for Sn⁺⁺ and calculation of the thermodynamic properties of other aqueous species and dissociation constants for various stannous and stannic complexes as a function of temperature permit prediction of the high temperature solution chemistry of tin and calculation of the solubility of cassiterite in hydrothermal solutions. The results of these calculations indicate that in the absence of appreciable chloride and fluoride concentrations, Sn(OH)₂⁰ and Sn(OH)₄⁰ are the predominant tin species in H₂O up to 350°C at ~2 $\text{\$}\text{?}$pH $\text{\$}\text{?}$7.5. The calculations also indicate that chloride complexes of Sn⁺⁺ predominate by several orders of magnitude over their fluoride and hydroxide counterparts in 1–3 molal (m) NaCl solutions, except in the presence of geologically unrealistic concentrations of fluoride or a pH greater than ~3.5 at 250°C or ~5.0 at 350°C. At higher pH values, most of the tin in solution is present as hydroxide complexes, even at concentrations of NaCl as high as 3 m. Calculated values of the solubility of cassiterite at high temperatures compare favorably with experimental data reported in the literature. Depending on the fugacity of oxygen and solution composition, the solubility of cassiterite in hydrothermal solutions may exceed 100 ppm under geologically realistic conditions.     

滇东南老君山锡-钨-锌-铟多金属矿集区含矿矽卡岩成因研究

滇东南老君山矿集区广泛分布的矽卡岩是本区锡-钨-锌-铟多金属矿床的主要赋存围岩。长期以来,该区含矿矽卡岩的成因争议较大,由此也制约了对该区锡钨多金属成矿规律的认识。本文以区内代表性的都龙和南秧田矿区含矿矽卡岩为研究对象,在对其地质特征详细研究的基础上,运用电子探针和ICP-MS分别测定了上述两个矿区含矿矽卡岩的矿物成分、微量和稀土元素组成,探讨了它们和多金属矿床的成岩成矿机制的关系。结果表明,区内同时存在与地层产状一致的"层状"含矿矽卡岩和明显切割层理的穿层含矿矽卡岩。都龙矿区含矿矽卡岩富Fe、贫Al,主要矿物端元成分为钙铁榴石(And_(52-69)Gro_(28-45)Spe_(1-4))、钙铁辉石(Di_(11-41)Hd_(51-73)Jo_(0-28))和铁阳起石等,从干矽卡岩到退化蚀变阶段,形成环境由酸性的弱还原环境向偏碱性的相对氧化环境变化。南秧田矿区含矿矽卡岩富Mg、Al,贫Fe,主要矿物端元成分为钙铝榴石(Gro_(82-89)Alm_(7-13)And_(2-5))、透辉石(Di_(55-81)Hd_(18-42)Jo_(0-5))和透闪石(阳起石)等,形成于相对还原的环境。都龙和南秧田矿区含矿矽卡岩与花岗岩都显示出相似的、LREE相对富集的右倾型稀土配分模式,多具有中等-弱Eu负异常,与典型的热液交代成因矽卡岩特征相似。综合分析认为,该区含矿矽卡岩主要形成于燕山晚期花岗岩浆热液与围岩的交代作用,"层状"矽卡岩可能是热液沿层间构造、岩相突变带等有利位置进行交代的结果。     

Mineral Association and Mineralogical Criteria for the Formation Conditions of A B—F—Sn—Bi Skarn in Damoshan,Gejiu Tin Field,Sothwest China

The Damoshan deposit is a small B-F-Sn Bi exoskarn deposit and contains a distinctive mineral assemblage comprising andradite,vesuvianite,calcite,diopside,magnetite,hematite,nordenskioldine,cassiterite,varlamoffite,schenfliesite,native bismuth,eulytite,bismite and bismuthite,in which the occurrence of eulytite is the first reported in China.Textures of the mineral paragenses show that andradite,vesuvianite and diopside were the earliest phases formed during metasomatism,i.e.,the skarn forming stage.Then nordenskioldine,magnetite and native bismuth,perhaps together with eulytite,were precipitated at the stage of retrograde alteration.The minerals varlamoffite,schoenfliesite,hematite ,bismite and bismuthite were probably the product of supergene alteration.The minerals were analyzed by means of electron microprobe.The data on the ,coexisting phases and their compositons show that during the metasomatism reduced F-and Sn-rich primary mineralizing solutions reacted with highly oxidized carbonated of the Gejie Formation,producing a high Fe^2 /Fe^3 skarn(vesuvianite-fluorite skarn)near the contact of granite,and a low Fe^2 /Fe^3 skarn(vesuvianite-fluorite skarn)near the contact of granite,and a low Fe^2 /Fe^3 skarn(andradite skarn)in the outer zone of the skarn body in which andradite is extremely tin-bearing up to 5.14 wt% SnO2),In the retrograde alteration stage ,B-rich,but F-and Si-deficient mineralizing solutions replaced the tin-bearing andradite,forming an association of nordenskioldine and magnetite,No sulphides were deposited at this stage because of the oxidization ambient conditions in the andradite skarn.In the spergene oxidation zone,the nordenskioldine was dissolved into varlmoffite and calcite,the native bismuth was transformed into bismite or bismuthite ,and the magnetite was altered into hematite under the action of the CO2-rich supergene solutions.     

The effect of temperature of reaction on the extraction of tin from calc-silicate rocks by NH4I volatilisation

Extraction of lattice-bound tin from calc-silicate minerals in the determination of tin in skarn rocks by NH₄I volatilisation is reported. This analytical technique has previously been regarded as specific for cassiterite and stannite. Although the NH₄I volatilisation reaction does not decompose calc-silicate minerals there is an increase in the yield of NH₄I-volatilised tin when the volatilisation temperature is raised above 500°C. The temperature effect is only observed for whole-rock samples and the type of behaviour appears related to the mineralogy of the rock. For instance, magnetite-bearing rocks have a different temperature yield curve to pyrrhotite-bearing rocks. When concentrates of single minerals are reacted with NH₄I this temperature dependence is not observed, although there is an increase in tin yield with decreasing grainsize.     

Strong tin enrichment in a pegmatite-forming melt

To investigate processes of magmatic tin enrichment and cassiterite deposition, we studied the abundances of major, trace, and volatile elements in a large number of rehomogenized silicate melt inclusions in quartz and topaz from a pegmatite body at the Ehrenfriedersdorf Sn–W deposit. This deposit is associated with evolved Variscan granites of the central Erzgebirge, southeast Germany. The melt inclusions are peraluminous; the molar aluminum saturation index (ASI) ranges from 1.15 to 2.0, and many inclusions are characterized by a very high content of fluxing components and volatiles. Some inclusions contain more than 20 wt% of H₂O, F, Cl, and P₂O₅, plus Li as well as very high levels of Sn. Some rare, highly evolved fractions of late-stage pegmatite-forming liquid at Ehrenfriedersdorf contained up to 7000 ppm Sn. The presence of hydrogen and methane in addition to water and carbon dioxide in the vapor phase of the melt inclusions suggests a very low oxygen fugacity for some fractions of magma. The extreme levels of tin, volatiles, and fluxing components in this magma had an important influence on processes of melt movement and cassiterite precipitation. Melts, like these, that are high in volatiles and alkalis (sum of Li₂O, Na₂O, K₂O, Rb₂O, and Cs₂O is >8 wt%) have low densities (≤1.8 g/cm³), low viscosities (<10 Pa.s at 700 °C), facilitate relatively rapid diffusion of ions through melts, and hence are excellent solvents for extracting and transporting ore-forming elements. Received: 1 February 1999 / Accepted: 19 January 2000     

Cassiterite LA-MC-ICP-MS U/Pb and muscovite 40Ar/39Ar dating of tin deposits in the Tengchong-Lianghe tin district,NW Yunnan,China

The Tengchong-Lianghe tin district in northwestern Yunnan, China, is an important tin mineralization area in the Sanjiang Tethyan Metallogenic Domain. There are three N–S trending granite belts in the Tengchong-Lianghe area, with emplacement ages ranging from Early Cretaceous to Late Cretaceous and Early Cenozoic. Tin mineralization is spatially associated with these granitic rocks. However, the petrogenetic link between the tin deposits and the host granites is not clear because of the lack of age data for the tin mineralization. We investigate the possibility of direct dating of cassiterite from three typical tin deposits in the Tengchong-Lianghe tin district, using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). In situ LA-MC-ICP-MS dating of seven cassiterite samples from the Lailishan (LLS-1 and LLS-2), Xiaolonghe (XLH, WDS, DSP, and HJS), and Tieyaoshan (TYS) tin deposits yielded well-defined ²⁰⁶Pb/²⁰⁷Pb–²³⁸U/²⁰⁷Pb isochron ages. To assess the accuracy of the in situ U/Pb dating of cassiterite, ⁴⁰Ar/³⁹Ar dating of coexisting muscovite (in samples LLS-1, DSP, and TYS) was also performed. The cassiterite in situ U/Pb ages (47.4?±?2.0, 71.9?±?2.3, and 119.3?±?1.7 Ma, respectively) are in excellent agreement with the coexisting muscovite ⁴⁰Ar/³⁹Ar ages (48.4?±?0.3, 71.9?±?1.4, and 122.4?±?0.7 Ma, respectively). The U/Pb ages of cassiterite combined with the ⁴⁰Ar/³⁹Ar ages of muscovite indicate that there are three tin mineralization events in this district: the Lailishan tin deposit at 47.4?±?2.0 to 52?±?2.7 Ma, the Xiaolonghe tin deposit at 71.6?±?2.4 to 3.9?±?2.0 Ma, and the Tieyaoshan tin deposit at 119.3?±?1.7 to 122.5?±?0.7 Ma. These ages are highly consistent with the zircon U/Pb ages of the host granites. It is su.ggested that the Cretaceous tin mineralization might have taken place in a subduction environment, while the Early Tertiary tin metallogenesis was in a postcollisional geodynamic setting.     

The origin of the Tongkeng-Changpo tin deposit,Dachang metal district,Guangxi, China: clues from fluid inclusions and He isotope systematics

Tongkeng-Changpo is the largest tin deposit within the giant Dachang polymetallic tin ore field in Guangxi, southern China, which is part of a large skarn system associated with Cretaceous granitoids. The Tongkeng-Changpo mineralization consists of veins and stockworks in the upper levels and replacement stratiform orebodies (mantos) at lower levels. Based on textural relationships, three major mineralizing stages can be recognized: stage I with cassiterite, sulphides, stannite, tourmaline, and quartz; stage II with cassiterite, sulphides, sulphosalts, quartz, and calcite; and stage III with calcite as the main phase. The study of fluid inclusions has shown that there are two main fluid types: CO₂ and NaCl-H₂O. Homogenization temperatures are 270 to 365°C, 210 to 240°C, and 140 to 190°C for stages I, II, and III, respectively. Salinities range from 1 to 7 wt.% NaCl equiv. in the early ore stage and 3 to 10 wt.% NaCl equiv. in the late stages. Laser Raman Spectroscopy indicates that the inclusion fluids in stages I and II were of carbono-aqueous composition, with minor amounts of CH₄ and H₂S, whereas those in stage III were aqueous. Helium isotopic analyses of inclusion fluids indicate that the ³He/⁴He ratios in the ore veins are in between 1.2 to 2.9 Ra (Ra = 1.4 × 10⁻⁶, modern atmospheric ratio), and range from 1.6 to 2.5 Ra in the stratiform orebodies. This range of ³He/⁴He ratios is significantly higher than that of crustal fluids (0.01–0.05 Ra). The similar characteristics of fluid inclusions and their He isotopic composition, as well as age constraints, indicate that the ore veins and stratiform orebodies of the Tongkeng-Changpo deposit formed from the same hydrothermal system, likely related to granite intrusions of the Mesozoic Yanshanian tectono-thermal event. In addition, the high R/Ra ratios indicate a mantle contribution in the ore fluids.     

滇西松山锡矿锡石LA-SF-ICP-MS U-Pb年代学及其对区域锡成矿作用的指示

松山锡矿位于滇西临沧花岗岩基的西北侧。矿体主要赋存于临沧黑云母二长花岗岩与松山组绢云石英片岩接触带矽卡岩以及花岗岩和围岩的裂隙中。由于缺乏精确的成矿年代学数据,在一定程度上限制了对矿床成因的认识,并制约了进一步的找矿勘查工作。本文首次利用LA-SF-ICP-MS微区原位U-Pb同位素测年技术对松山锡矿床矽卡岩型和电气石石英脉型矿石中的锡石矿物开展了 U-Pb年代学研究获得2件锡石样品的~(207) Pb/~(206)Pb-~(238) U/~(206) Pb谐和年龄分别为76.6±1.5Ma和79.6±3.6Ma,说明松山锡矿锡的成矿作用主要发生在晚白垩世,与临沧花岗岩主体侵位时间(三叠纪)明显不同。结合地质特征和前人年代学研究成果本文认为该地区存在明显的晚白垩世锡的成矿事件,研究区下一步的找矿工作应围绕岩体与围岩接触带,以及岩体和围岩中的断裂展开。     

A combined EMPA and LA-ICP-MS study of Li-bearing mica and Sn–Ti oxide minerals from the Qiguling topaz rhyolite (Qitianling District,China): The role of fluorine in origin of tin mineralization

The Sn-rich Qiguling topaz rhyolite dike intrudes the Qitianling biotite granite of the Nanling Range in southern China; the granite hosts the large Furong Sn deposit. The rhyolite dike is typically peraluminous, volatile-enriched, and highly evolved. Whole-rock F and Sn concentrations attain 1.9 wt.% and 2700 ppm, respectively. The rhyolite consists of a fine-grained matrix formed by quartz, feldspar, mica and topaz, enclosing phenocrysts of quartz, feldspar and mica; it is locally crosscut by quartz veinlets. Lithium-bearing micas in both phenocrysts and the groundmass can be classified as primary zinnwaldite, “Mus-Ann” (intermediate member between annite and muscovite), and secondary Fe-rich muscovite. Topaz is present in the groundmass only; common fluorite occurs in the groundmass and also in a specific cassiterite, rutile and fluorite (Sn–Ti–F) assemblage. Cassiterite and rutile are the only Sn and Ti minerals; both cassiterite and Nb-rich rutile are commonly included in the phenocrysts. The Sn–Ti–F assemblage is pervasive, and contains spongy cassiterite in some cases; cassiterite also occurs in quartz veinlets which cut the groundmass. Electron microprobe and LA-ICP-MS compositions were used to study the magmatic and hydrothermal processes and the role of F in Sn mineralization. The presence of zinnwaldite and “Mus-Ann”, which are respectively representative of early and late mica crystallization during magma differentiation, also suggests a significant decrease in f(HF)/f(H₂O) of the system. Cassiterite included in the zinnwaldite phenocrysts is suggested to have crystallized from the primary magma at high temperature. Within the Sn–Ti–F aggregates, rutile crystallized as the earliest mineral, followed by fluorite and cassiterite. Spongy cassiterite containing inclusions of the groundmass minerals indicate a low viscosity of the late fluid. The cassiterite in the quartz veinlets crystallized from low-temperature hydrothermal fluids, which possibly mixed with meteoric water. In general, cassiterite precipitated during both magmatic and hydrothermal stages, and over a range of temperatures. The original fluorine and tin enrichments, f(HF)/f(H₂O) change in the residual magma, formation of Ca,Sn,F-rich immiscible fluid, decrease of the f(HF) during groundmass crystallization, and mixing of magma-derived fluids with low-saline meteoric water during the late hydrothermal stage, are all factors independently or together responsible for the Sn mineralization in the Qiguling rhyolite.     

Malayaite and tin‐bearing silicates from a skarn at Doradilla via Bourke,New South Wales

An extensive complex zoned skarn is developed at the contact of a leucoadamellite intrusive at Doradilla, NW New South Wales. The skarn is a disequilibrium assemblage resulting from a progressive sequence of replacement of a carbonate precursor. Early grossular‐clinopyroxene rocks are replaced by andradite with 0.5–3.5 wt.% SnO₂ clinopyroxene and quartz. Later alteration along fractures and bedding planes of the garnet‐clinopyroxene quartz assemblage has produced calcite‐malayaite (CaSn0.95Ti0.05SiO₅) veins. The final replacement stage was the overprinting of the silicate phases by assemblages containing sulphides, cassiterite, magnetite, titanite, fluorite, biotite and chlorite. The tin content of garent increases with increasing andradite component suggesting replacement of Fe³⁺ by Sn⁴⁺. Associated clinopyroxenes contain 0.1% SnO₂. The coexistence of titanite and its tin isomorph malayaite with extremely limited solid solution indicates late stage skarn temperatures of less than 400°C.     

西藏浦桑果铅锌多金属矿床矽卡岩矿物学特征及其地质意义

西藏浦桑果铅锌多金属矿床位于南冈底斯成矿带火山岩浆弧内,矿区矽卡岩型铅锌矿体主要呈似层状和透镜状近东西向赋存于白垩系塔克那组第4岩性段矽卡岩化大理岩中,矽卡岩矿物较发育。为进一步查明矽卡岩矿物种属及矽卡岩类型,剖析矽卡岩的形成环境及其与成矿的关系,在对矽卡岩矿物系统的显微镜下鉴定基础上,利用电子探针对矿区内主要矽卡岩矿物化学成分进行了系统分析。结果表明,石榴子石主要为非连续的钙铁榴石钙铝榴石类质同像系列(And47.39~98.17Gro0.59~50.22Ura+Pyr+Spe0~3.53),且早期主要形成钙铁榴石,部分钙铁榴石含锰质较高;单斜辉石主要为钙铁辉石-锰钙辉石-透辉石类质同像系列(Hd37.91~74.16Jo0.91~61.66Di0.43~46.07);似辉石主要为硅灰石,端员组分为Wo99.09~99.26En0.50~0.56Fs0.13~0.24;角闪石主要为镁角闪石,具钙质角闪石属性;绿帘石贫铁、镁而富铝、钙;绿泥石属于密绿泥石类。矿床矽卡岩矿物组合特征表明,浦桑果矿床矽卡岩兼具钙质矽卡岩和锰质矽卡岩的特征。早期矽卡岩形成于高温、偏碱性、强氧化的开放体系中,成矿流体具有较高氧逸度。锰质矽卡岩矿物特征及独立银矿物的存在综合表明矿区具有银矿找矿潜力,为下步找矿工作提供了思路和方向。     

Carbonates and sources of fluids in ores and metasomatites of the Ermakovka fluorite-bertrandite-phenacite deposit (western Transbaikalia)

We present results of isotope-geochemical study of the Ermakovka F-Be deposit, including data on the oxygen and carbon isotope compositions in dolomite and calcite marbles and in carbonates accompanying skarns, of early and late stages of ore formation and of post-ore parageneses. To elucidate the sources of fluids participated in the ore formation, we calculated the oxygen isotope composition in water and the hydrogen isotope composition in hydroxyl-containing minerals. Phlogopite in marbleized dolomites, vesuvianite and amphibole in skarns, eudidimite and bertrandite in ore parageneses, and bavenite formed during post-ore processes are analyzed. Most of the ore-stage minerals are depleted in heavy oxygen. Their 5¹⁸O values are lower than 5-6%c (SMOW). Oxygen in carbonate minerals of the initial stage (dolomite and bastnaesite) is heavier (1.3-4.9%c) than that in calcite (+ 2 to -3.7%c). The 5¹⁸O values of water in equilibrium both with carbonate and with silicate minerals (-4 to -14%c) suggest the contribution of meteoric water to the mineral formation. A magmatic fluid (5¹⁸O from + 6 to + 9%c) participated in the skarn formation at the initial stage, and a meteoric fluid, at the final stage (5¹⁸O from -1 to -9%c). A meteoric source is confirmed by the depleted hydrogen isotope composition in minerals (5D from -119 to -192%c).