锡在流体和花岗质硅酸盐熔体间分配行为的实验研究

锡的成矿与花岗岩有着密切关系。为深入了解不同的岩浆组成及流体变化对锡分配行为的影响,以不同化学组成的凝胶和不同的流体分别作为初始固液相,进行了锡在流体与花岗质熔体间的分配行为实验研究。实验温度为850℃,压力为100 MPa。结果显示,当液相为0.1 mol/L的HCl时,熔体组成的变化对锡的分配行为有着明显的影响,锡在流熔体间的分配系数DSn随熔体中碱质(Na2O K2O)含量、钠钾(Na/K)和碱铝(AlK/Al)摩尔比的增加而减小;在固相(富钾过碱质熔体)不变的前提下,DSn随流体相中HCl浓度的增加而增大,而流体相中HF及K 、Na 浓度的改变对DSn影响不大;流体Cl-浓度和酸度升高有利于锡分配进入流体相。     

骑田岭岩体黑云母中挥发性组分的演化特征及对锡成矿的指示

挥发性组分F、Cl等是花岗质岩浆的重要组成部分,它可以直接或者间接影响到岩浆的性质和岩浆作用的种种过程,同时制约着Sn、Cu等成矿元素在熔体/流体间的分配、流体体系的地球化学特征以及成矿效应.本文以骑田岭花岗岩体中的黑云母为研究对象,对骑田岭花岗岩体中挥发性组分的演化特征以及与锡成矿关系进行探讨.     

硅酸盐熔体和流体中金的性质及行为研究进展

岩浆演化过程中岩浆—流体阶段发生的相转变过程控制了元素在两相之间的分配行为。作为与岩浆热液活动有密切成因联系的金矿床,其在硅酸盐熔体和流体中的性状及两相间的分配行为是控制该类矿床成矿的重要物理化学因素。介绍了金在流体、熔体中的性状,论述了其在流体/硅酸盐熔体间的分配行为不仅受温度、压力、氧逸度等物理化学条件的影响,还受流体组分(阴离子、阳离子)、熔体组成(Na2O+K2O/Al2O3,Na/K,SiO2,NBO/T)的制约;最后对目前实验研究存在的问题、改进方法以及今后的研究方向进行了探讨。     

与花岗岩有关锡矿成岩成矿作用研究若干问题讨论

文章基于近年来大量典型锡矿床和成矿区带成岩成矿作用及高温高压实验研究成果,对锡矿成矿年代学、成矿花岗岩类型、物质来源、源区物质的熔融条件及锡在岩浆中的存在形式、熔体-流体相间分配行为及热液流体中的存在形式等方面的研究进展及存在问题进行了系统综述,指出:①锡石原位U-Pb测年已成为直接测定锡成矿年龄的有效手段,近年来发展起来的多种矿石矿物U-Pb测年方法与传统蚀变矿物测年方法的结合,将为研究锡多金属矿床多期次成矿作用叠加、矿集区内不同类型矿床成因联系及区域矿床组合模型的建立提供关键的年代学依据;②锡的富集成矿不仅与花岗质岩浆的高程度的结晶分异密切相关,而且受源区组成及部分熔融条件的制约;③全球锡多金属矿床的不均匀分布、与准铝质花岗岩有关锡矿的富集成矿机制以及各类复杂的锡-钨-铜-钼-铅-锌银多金属矿种组合差异及其金属元素富集机制亟待查明;④已有的关于锡在花岗质熔体、热液流体相中的存在形式及两相间的分配行为的高温高压实验结果受锡与贵金属容器间合金效应的影响,人工合成流体包裹体等新的实验方法的开发及XAS同步辐射和激光拉曼等原位分析技术的应用,将为研究花岗岩浆-热液过程锡的迁移、富集及沉淀成矿机制提供更为直接、可靠的实验依据。     

钨、锡流-熔分配实验结果及其矿床成因意义

本文用实验确定了钨、锡在成分不同的花岗质熔体相与共存水热流体相的流-熔分配系数(D_(Me)~(V/L))及其与介质溶液(NaF,KF,HF,NaCl等水溶液)摩尔浓度间的函数关系。实验结果表明,钨、锡的分配行为明显不同。在相同条件下,随体系的不同,D_W~(V/L)比D_(Sn)~(V/L)大几倍至二十倍。钠和钾对钨、锡的流-熔分配行为的影响基本相同,而氟和氯对钨、锡的分配行为的影响相差甚远,花岗质熔体的主成分对D_W~(V/L)和D_(Sn)~(V/L)有复杂的影响。利用这些结果探讨与花岗岩有关的钨、锡矿床的成矿机理,得出了一些与前人不同的新认识。     

湘南地区钨锡多金属矿床浆液过渡态熔体类型成因联系及其成矿意义

岩浆液态不混溶形成的浆液过渡态熔体是与高度分异花岗岩有关的钨锡多金属成矿流体的重要形式。湘南地区与钨锡多金属成矿有关的浆液过渡态熔体有两种类型,一种富钠富挥发分,以芙蓉矿田矿化蚀变碱长花岗岩中的钠长石电气石石英囊为代表;另一种富钾富挥发分,以界牌岭矿床矿化蚀变花岗斑岩中的锂白云母萤石囊(团块)为代表。两种浆液过渡态熔体可形成于同一矿床,为同期岩浆活动产物,成分上K₂O与Na₂O负相关,表明它们具有密切的时空和成因联系,熔体-流体包裹体发育,为高度分异的花岗质岩浆液态不混溶产物。两种浆液过渡态熔体富含成矿物质,与成矿关系密切,湘南地区多数钨锡多金属矿床的云英岩型、构造蚀变带型、钾化花岗岩型钨锡多金属成矿可能与富钾富挥发分的浆液过渡态熔体有关,钠化花岗岩型铌钽矿化与富钠富挥发分的浆液过渡态熔体有关。     

花岗质岩浆挥发性组分演化对铜和铀成矿机制的制约

近二十年来,对岩浆中挥发性组分(H2O、CO2、F、Cl、B、S等)及其性状的研究,已成为花岗岩成岩、成矿研究领域十分重要的一环.一系列证据显示,挥发性组分是花岗质岩浆的重要组成部分,它们可直接或间接地影响到岩浆的性质和岩浆作用的种种过程,包括岩浆的产生和运移、岩浆的对流和扩散、岩浆的结晶分异和液相不混溶等,同时也制约着元素在熔体/流体相中的分配以及流体体系的地球化学行为及其成矿效应.     

伟晶岩结晶动力学和热力学及稀有金属超常富集成矿机制

本文综述了伟晶岩结晶动力学、热力学和伟晶岩熔体稀有金属元素实现超常富集成矿的机制。结晶动力学涉及成核动力学和晶体生长动力学两个方面。低成核速率和高晶体生长速率是伟晶岩结晶动力学的重要特征,在结晶过程受到水、助溶剂以及过冷条件三个因素共同制约。伟晶岩熔体的相态（超临界态）可能在伟晶岩形成和稀有金属元素超常富集中扮演重要角色。花岗伟晶岩稀有金属超常富集程度受到岩浆源区成分、岩浆结晶分异过程与熔体化学成分等因素的控制。花岗质岩浆高度分异结晶或者变质沉积岩部分熔融直接形成的成矿伟晶岩熔体均需要源岩中稀有金属元素预富集。深熔作用产生的低程度、小体积的伟晶岩熔体具有更高的稀有金属元素成矿潜力。在岩浆分异演化过程中,稀有金属元素的超常富集主要通过超临界熔体/流体、岩浆熔体作用、过冷作用实现。超临界熔体/流体发生熔体- 流体不混溶作用使稀有金属元素在熔体相和流体相间再分配和富集;岩浆熔离作用使稀有金属元素选择性分配到富挥发分的熔体中,导致稀有金属元素再次富集;过冷作用降低稀有金属矿物结晶的饱和浓度,促进稀有金属矿物结晶。熔体的化学成分（如挥发分）直接影响熔体的物理、化学性质。例如,挥发分的富集能够降低熔体黏度,促进岩浆分异结晶过程。挥发分和稀有金属元素的亲和性也控制稀有金属元素在不同相熔体中的分配和富集,显著增加稀有金属元素的溶解度和迁移富集能力,有助于伟晶岩中稀有金属超常富集和成矿。     

铜在熔体流体间分配实验的研究进展

与花岗岩有关的铜矿床主要为斑岩型铜矿,斑岩型铜矿是铜的主要类型。研究铜在岩浆/流体相转变过程中的分配行为,对深入认识斑岩型铜矿的形成机制有重要意义。本文总结了目前铜在熔体/流体间分配实验的研究进展并分述了流体、熔体对铜分配行为的影响以及目前实验研究存在的问题。     

金在流体/花岗质熔体间分配的实验研究

<正>斑岩型矿床是一种重要的金属矿床类型,为世界上提供了57%的铜资源和9%的金资源(Singer et al.,2005)。从全球范围来看,浅成热液型和斑岩型金铜矿床在时空上与侵入岩浆作用有关(Jégo Stébastien et al.,2012),岩浆和热液过程的共同作用形成了此类矿床。元素在流体和熔体间交换、分配过程是岩浆热液矿床形成的重要环节。研究金在硅酸盐熔体和流体中的分配行为及其影响因素对认识中酸性岩浆演化与成矿的关系具有重要意义。关于金在花岗质流体/     

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.     

Helium Isotope Geochemistry of Ore-forming Fluids from Furong Tin Orefield in Hunan Province, China

Abstract. The Furong tin orefield, located in southern Hunan, China, is a newly-discovered super-large tin orefield. In contrast to most other tin deposits associated with S-type granites, the Furong tin deposit is closely associated with the Qitianling A-type granite. The ³He/⁴He ratios of fluid inclusions in pyrite and arsenopyrite from this orefield range from 0.13 to 2.95 Ra. The influence of various post-mineralization processes on the helium isotopic composition of ore-forming fluid inclusions are estimated negligible. Thus, the analytical values of helium isotopic composition basically represent the original values of ore-forming fluids at the time they were trapped.
The ³He/⁴He ratios of ore-forming fluids from the Furong orefield indicate the existence of mantle-source components. It supports the idea that both the Furong tin orefield and Qitianling granite formed under the geodynamic background of mantle upwelling and crustal extension.     

Characteristics of rare-earth elements （REE）, strontium and neodymium isotopes in hydrothermal fluorites from the Bailashui tin deposit in the Furong ore field,southern Hunan Province,China

In this paper the authors present the REE concentrations and Sr and Nd isotopic compositions of fluorites from the Bailashui tin deposit of the Furong ore field, southern Hunan Province. The results showed that the total amount of REE in fluorites is usually low, ranging from 0.705 to 8.785 μg/g with the chondrite-normalized REE distribution patterns similar to those of the Qitianling granites in the study area, characterized by LREE-enrichment patterns with pronounced negative Eu anomalies. The fluorites vary in Sr isotopic composition within the range of 0.7083-0.7091, the values are lower than those of the granites and higher than those of the host carbonate rocks in this area. The εNd（t） values of fluorites vary between -9.4 and ＋10.3, revealing that both the crust- and mantle-source materials were involved in the ore-forming hydrothermal fluids. Combined with previous studies on this ore deposit, the Bailashui tin deposit is temporally and spatially closely related with granitic magmatism in this area. The hydrothermal fluorites are the product of fluid/rock interactions between granitic magmatic hydrothermal fluid and marine carbonate rocks. The REE and F in the ore-forming fluid were derived from the granites, whereas Sr in the ore-forming fluid came mainly from the granitic magmatic hydrothermal fluid and marine carbonate rocks, although variations in Sr isotopic composition cannot be explained by a simple mixture of these two end-members. Evidence demonstrated that the ore-forming fluids are of crustal-mantle mixing origin, but that the fluids were probably incompletely homogenized and this may be caused by inhomogeneous mixing of the fluids of different sources.     

富F熔体-溶液体系流体地球化学及其成矿效应--研究现状及存在问题

高度演化花岗岩类多为富F的熔体溶液体系 ,具有鲜明的、不同于其他体系的地球化学行为。富F岩浆固相线和液相线的降低和岩浆寿命的延长 ,使残余熔体与热水热液的性状差异减小 ,模糊了岩浆与热液之间的界线。最近对于富F、B和P伟晶岩中熔融包裹体的研究获得了新的进展。在约 70 0～ 5 0 0℃的温度和 1 0 0 0× 1 0 5Pa的压力下 ,在伟晶岩石英中发现两种不同类型的熔体包裹体 ,一种是富硅酸盐、贫水的熔体包裹体 ,另一种是贫硅酸盐、富水的熔体包裹体。两种熔体在硅酸盐 (+F +B +P) 水体系的溶离线边界上同时被圈闭。这表明 ,在地壳浅部侵位的侵入体 ,当温度≥ 70 0℃时 ,水在富F、B和P的熔体中可以无限混溶 ;而一旦温度降低 ,就会分离为两种共存的熔体并伴随强烈的元素分异作用。在溶离线的富水一侧形成与正常硅酸盐熔体有很大不同的高度富挥发份的熔体 ,这种致密、高粘度、高扩散性以及高活动性的超富水 (hyper aqueousmelt)熔体 ,可以与水溶液流体相类比。这为岩浆热液过渡性流体的假说提供了新的有利的证据。此外 ,在这种具有超富水和熔体特征的过渡性流体中 ,微迹元素可能具有特殊的地球化学行为 ,如在许多晚期花岗岩包括淡色花岗岩和伟晶岩中稀土元素配分模式所显示的四分组效应等。富F熔体溶液体?     

REE, Mn, Fe, Mg and C, O Isotopic Geochemistry of Calcites from Furong Tin Deposit, South China: Evidence for the Genesis of the Hydrothermal Ore-forming Fluids

The Furong tin deposit in the central Nanling region, South China, consists of three main types of mineralization ores, i.e. skarn-, altered granite- and greisen-type ores, hosted in Carboniferous and Permian strata and Mesozoic granitic intrusions. Calcite is the dominant gangue mineral intergrown with ore bodies in the orefield. We have carried out REE, Mn, Fe, and Mg geochemical and C, and O isotopic studies on calcites to constrain the source and evolution of the ore-forming fluids. The calcites from the Furong deposit exhibit middle negative Eu anomaly (Eu/Eu*= 0.311–0.921), except for one which has an Eu/Eu* of 1.10, with the total REE content of 5.49–133 ppm. The results show that the calcites are characterized by two types of REE distribution patterns: a LREE-enriched pattern and a flat REE pattern. The LREE-enriched pattern of calcites accompanying greisen-type ore and skarn-type ore are similar to those of Qitianling granite. The REE, Mn, Fe, and Mg abundances of calcites exhibit a decreasing tendency from granite rock mass to wall rock, i.e. these abundances of calcites associated with altered granite-type and greisen-type ores are higher than those associated with skarn-type ores. The calcites from primary ores in the Furong deposit show large variation in carbon and oxygen isotopic compositions. The δ¹³C and δ¹⁸O of calcites are −0.4 to −12.7‰ and 2.8 to 16.4‰, respectively, and mainly fall within the range between mantle or magmatic carbon and marine carbonate. The calcites from greisen and altered granite ores in the Furong deposit display a negative correlation in the diagram of δ¹³C versus δ¹⁸O, probably owing to the CO₂-degassing of the ore-forming fluids. From the intrusion to wall-rock, the calcites display an increasing tendency with respect to δ¹³C values. This implies that the carbon isotopic compositions of the ore-bearing fluids have progressively changed from domination by magmatic carbon to sedimentary carbonate carbon. In combination with other geological and geochemical data, we suggest that the ore-forming fluids represent magmatic origin. We believe that the fluids exsolved from fractionation of the granitic magma, accompanying magmatism of the Qitianling granite complex, were involved in the mineralization of the Furong tin polymetallic deposit.     

Geology,Geochemistry and Genesis of Yinyan Porphyry Tin Deposit

The Yinyan porphyry tin deposit is a blind deposit associated with a small granite porphyry stock.The petrology and geochemistry of the Yinyan granite porphyry suggest that it is genetically of the transfor-mation type,emplaced at the late stage of fractional crystallization within a high-level magma chamber.Ore-forming fluids are derived predominantly from the granitic magma and they interact with the wall rocks intensely when finding their way upwards through the granite porphyry.From the lower part of the porphyry upwards the following alteration zones can be distinguished(a)slightly altered granite porphyry (with weak potash feldspathization),(b)protolithionite-quartz greisenization zone,(c)to-paz-quartz greisenization zone,(d)senicite-quartz sericitization zone,and （e）silicification zone (quartz core at the surface).Tin mineralization is related to greisenization,especially to topaz-quartz greisenization.Rock and ore-forming temperatures and oxygen fugacities are estimated,respectively.There are significant differences in many aspects between the Yinyan porphyry tin deposit and volcan-ic-subvolcanic porphyry tin deposits.     

Experimental Study of Partial Melting of Mantle Peridotite--A Discussion about the Genesis of Silica-rich Fluids (Melts)

Experiments on partial melting of mantle lherzolite have been realized at 0.6 and 1.0 GPa and the chemical compositional variations of melts during different melting stages have been first discussed. The results show that the trends of variations in SiO2, CaO, Al2O3, Na2O and TiO2 are different at different melting stages. The melts produced at lower pressure are richer in SiO2 than those at higher pressure. The mantle-derived silica-rich fluids (silicate melts) are polygenetic, but the basic and intermediate-acid silicate melts in mantle peridotite xenoliths from the same host rocks, which have equivalent contents of volatile and alkali components and different contents of other components, should result from in-situ (low-degree) partial melting of mantle peridotite under different conditions (e.g. at different depths, with introduction of C-O-H fluids or in the presence of metasomatic minerals). The intermediate-acid melts may be the result of partial melting (at lower pressure) Opx + Sp + K-Na-rich fluid±(Amphi)±(Phlog)= Ol+melt.But the intermediate-acid magmas cannot be produced from the partial melting of normal mantle peridotite unless the crustal materials are introduced to some extent.     

湖南骑田岭芙蓉锡多金属矿田锡的赋存状态及迁移形式

芙蓉矿田锡矿床按成因可分为构造蚀变带-矽卡岩复合型、构造蚀变带型、蚀变岩体型、矽卡岩型、脉状云英岩型等五种类型。各类型矿体中锡主要以锡石锡的形式出现,其分布率由92.17~97.77%,硫化锡、胶态锡、硅酸锡的分布率<8%。锡元素在钠长石化成矿作用阶段,很可能是以氧的络阴离子SnO33-、氢氧络阴离子〔Sn(OH)6〕2-的形式迁移;在云英岩化成矿作用阶段,主要以氟的络合物,如Na2SnF6,Na2〔Sn(OH、F)6,〕SnF4,K2SnF6等形式搬运;到了绿泥石化锡石硫化物阶段,锡又以硫化锡酸盐、硫化物(Na2SnS3,SnS2,SnS)和氯的络合物(Na2SnC l6)、氟的络合物等形式进行迁移和搬运。     

Tetrad effects in the rare earth element patterns of granitoid rocks as an indicator of fluoride-silicate liquid immiscibility in magmatic systems

This paper focuses on reasons for the appearance of tetrad effects in chondrite-normalized REE distribution patterns of granitoids (Li-F granites, peralklaine granites, ongonites, fluorine-rich rhyolites, and granitic pegmatites). The analysis of published data showed that the alteration of such rocks by high- and/or low-temperature metasomatic processes does not result in most cases in the appearance or enhancement of M-type tetrad effects in REE patterns. These processes are accompanied by the removal or addition of lanthanides, a W-type sag appears between Gd and Ho, and negative or positive Ce anomalies develop sometimes in REE patterns. The formation conditions of peculiar rocks enriched in Ca and F from the Ary Bulak ongonite massif (eastern Transbaikalia) and the character of REE distribution in these rocks and melt inclusion glasses were discussed. Based on the obtained data and the analysis of numerous publications, it was concluded that REE tetrad effects in rare-metal granitoids are caused by fluoride-silicate liquid immiscibility and extensive melt differentiation in the accumulation chambers of fluorine-rich magmas. A considerable increase in fluorine content in a homogeneous granitoid melt can cause its heterogenization (liquation) and formation of fluoride melts of various compositions. The redistribution of lanthanides between the immiscible liquid phases of granitoid magma will result in the formation of M-type tetrad effects in the silicate melts, because the REE patterns of fluoride melts exhibit pronounced W-type tetrad effects. The maximum M-type tetrad effect between La and Nd, which is observed in many rare-metal granitoids, is related to the character of REE partitioning between fluoride and silicate melts and F- and Cl-rich magmatic fluids. The low non-chondritic Y/Ho ratio (<15) of many rare-metal granitoids may be indicative of a contribution of fluoride melts to the differentiation of F-rich silicic magmas, from which these rocks were formed. The influence of high-temperature F-Cl-bearing fluids on melts and/or granitoid rocks results in an increase in Y/Ho ratio owing to the elevated solubility of Ho in such fluids.