Genesis of the Kamioka Skarn Deposits: An Important Role of Clinopyroxene Skarn and Graphite-bearing Limestone in Precipitating Sulfide Ore

Abstract: A genetical relationship between skarn formation and mineralization is investigated for the Kamioka skarn deposits which are the largest Zn-Pb producer in Japan. In the Mozumi deposit, one of main deposits in the Kamioka mining area as well as Tochibora and Maruyama, clinopyroxene skarn was generally subjected to later replacement by garnet or magnetite–calcite–quartz during the Zn-Pb mineralization. The replacement of hedenbergitic clinopyroxene by andraditic garnet resulted in the formation of diopsidic clinopyroxene relicts. With the progress of replacement, the S/So value (So: an estimated area occupied by an original clinopyroxene grain in a thin section, S: a total area of relict clinopyroxene fragments) which is an index of the degree of replacement decreases from 0. 7 to 0. 1, and the hedenbergite mole percent of relict clinopyroxene decreases drastically from about 65 to less than 40. A close association of andraditic garnet and sphalerite suggests that heden-bergitic clinopyroxene skarn played an important role to reduce the relatively oxic ore-forming fluid enriched in Zn²⁺ and SO4^2– and to precipitate sphalerite from the fluid. Ferrous iron in the hedenbergitic clinopyroxene skarn was oxidized to form andraditic garnet. Besides this garnet formation, the mineral assemblage of magnetite–calcite–quartz replaced the clinopyroxene skarn at the time of mineralization. In both cases, the reduction of relatively oxic ore-forming fluid by hedenbergitic clinopy-roxene skarn at the later stage brought about the precipitation of sulfide minerals. In contrast, these types of later replacement are not found in the Tochibora deposit. Instead, graphite-bearing crystalline limestone and relatively fresh clinopyroxene skarn are common. Mineralized clinopyroxene skarn has high graphite carbon contents relative to barren one, suggesting that the amount of graphite in the skarn was an important controlling factor for mineralization. It is very likely that the graphite played a role of reducing agent during the mineralization in the Tochibora deposit.     

Metamorphic charnockite in contact aureoles around intrusive enderbite from Natal, South Africa

In the Port Edward area of southern Kwa-Zulu Natal, South Africa, charnockitic aureoles up to 10 m in width in the normally garnetiferous Nicholson's Point Granite, are developed adjacent to intrusive contacts with the Port Edward Enderbite and anhydrous pegmatitic veins. Mineralogical differences between the country rock and charnockitic aureole suggest that the dehydration reaction Bt + Qtz → Opx + Kfs + H₂O and the reaction of Grt + Qtz → Opx + Pl were responsible for the charnockitization. The compositions of fluid inclusions show systematic variation with: (1) the Port Edward Enderbite being dominated by CO₂ and N₂ fluid inclusions; (2) the non-charnockitized granite by saline aqueous inclusions with 18–23 EqWt% NaCl; (3) the charnockitic aureoles by low-salinity and pure water inclusions (<7 EqWt% NaCl); (4) the pegmatites by aqueous inclusions of various salinity with minor CO₂. As a result of the thermal event the homogenization temperatures of the inclusions in charnockite show a much larger range (up to 390 °C) compared to the fluid inclusions in granite (mostly <250 °C). Contrary to fluid-controlled charnockitization (brines, CO₂) which may have taken place along shear zones away from the intrusive body, the present “proximal” charnockitized granite formed directly at the contact with enderbite. The inclusions indicate contact metamorphism induced by the intrusion of “dry” enderbitic magma into “wet” granite resulting in local dehydration. This was confirmed by cathodoluminescence microscopy showing textures indicative for the local reduction of structural water in the charnockite quartz. Two-pyroxene thermometry on the Port Edward Enderbite suggests intrusion at temperatures of ∼1000–1050 °C into country rock with temperature of <700 °C. The temperature of aureole formation must have been between ∼700 °C (breakdown of pyrite to form pyrrhotite) and ∼1000 °C. Charnockitization was probably controlled largely by heat related to anhydrous intrusions causing dehydration reactions and resulting in the release and subsequent trapping of dehydration fluids. The salinity of the metamorphic fluid in the contact zones is supposed to have been higher at an early stage of contact metamorphism, but it has lost its salt content by K-metasomatic reactions and/or the preferential migration of the saline fluids out of the contact zones towards the enderbite. The low water activity inhibited the localized melting of the granite. Mineral thermobarometry suggests that after charnockite aureole genesis, an isobaric cooling path was followed during which reequilibration of most of the aqueous inclusions occurred. Received: 8 November 1998 / Accepted: 21 June 1999     

The clustered nucleation and growth processes of garnet in regional metamorphic rocks from north-west Connecticut,USA

Serial sectioning and imaging with a flatbed scanner yielded the three-dimensional size and spatial distribution of garnet porphyroblasts in two garnet schists and one staurolite-bearing schist from the Everett Formation, north-west Connecticut. The dominant garnet-producing reaction in all samples was chlorite+quartz=garnet+H₂O. The appearance of staurolite, and additional garnet growth in the staurolite-bearing sample, was due to the reaction chloritoid=garnet+staurolite+chlorite. Statistical measures of garnet spatial distributions, using the pair correlation function (PCF), indicate that garnet crystals are weakly to strongly clustered at length scales between 2 and 10 mm. Such clustered nucleation may reflect minor bulk compositional variations. Covariance measures between garnet size and nearest-neighbour distance, using the mark covariance function (MCF), suggest a very weak correlation between crystal size and nearest-neighbour distance for length scales of 2 mm or less. These statistical data suggest that if diffusional gradients were present around growing garnet crystals, they did not influence nucleation and growth patterns at length scales greater than c. 2 mm. Compositional maps, through the garnet centres, show that the smaller crystals have lower Mn core compositions relative to larger crystals, consistent with progressive nucleation during pro-grade metamorphism. Radius-rate plots calculated from compositional X-ray maps show similar growth rates for garnet crystals of different size, consistent with an interface-controlled growth model for garnet. The presence of minor diffusional gradients around growing garnet cannot be entirely dismissed, but the lack of observable reaction rims, the clustered spatial distribution and the radius-rate data are most consistent with an interface-controlled garnet growth model.     

Water in garnet of garnetite (metarodingite) and eclogite from the Erzgebirge and the Lepontine Alps

Little is known about water in nominally anhydrous minerals of orogenic garnet peridotite and enclosed metabasic rocks. This study is focused on peridotite-hosted eclogite and garnetite (metarodingite) from the Erzgebirge (EG), Germany, and the Lepontine Alps (LA), Switzerland. Newly discovered, peridotite-hosted eclogite in the Erzgebirge occurs in the same ultra-high pressure (UHP) unit as gneiss-hosted coesite eclogite, from which it is petrologically indistinguishable. Garnet is present in all mafic and ultramafic high pressure (HP) rocks providing for an ideal proxy to compare the H₂O content of the different rock types. Garnet composition is very similar in EG and LA samples and depends on the rock type. Garnet from garnetite, compared to eclogite, contains more CaO (garnetite: 10.5–16.5 wt%; eclogite: 5–11 wt%) and is also characterized by an anomalous REE distribution. In contrast, the infrared (IR) spectra of garnet from both rock types reveal the same OH absorption bands that are also identical to those of previously studied peridotitic garnet from the same locations. Two groups of IR bands, SW I (3,650 ± 10 cm⁻¹) and SW II (3,570–3,630 cm⁻¹) are ascribed to structural hydroxyl (colloquially ‘water’). A third, broad band is present in about half of the analysed garnet domains and related to molecular water (MW) in submicroscopic fluid inclusions. The primary content of structural H₂O, preserved in garnet domains without fluid inclusions (and MW bands), varies systematically—depending on both the location and the rock type. Garnet from EG rocks contains more water compared to LA samples, and garnet from garnetite (EG: 121–241 wt.ppm H₂O; LA: 23–46 wt.ppm) hosts more water than eclogitic garnet (EG: 84 wt.ppm; LA: 4–11 wt.ppm). Higher contents of structural water (SW) are observed in domains with molecular water, in which the SW II band (being not restricted to HP conditions) is simultaneously enhanced. This implies that fluid influx during decompression not only led to fluid inclusions but also favoured the uptake of secondary SW. The results signify that garnet from all EG and LA samples was originally H₂O-undersaturated. Combining the data from eclogite, garnetite and previously studied peridotite, H₂O and CaO are positively correlated, pointing to the same degree of H₂O-undersaturation at peak metamorphism in all rock types. This ubiquitous water-deficiency cannot be reconciled with the derivation of any of these rocks from the lowermost part of the mantle wedge that was in contact with the subducting plate. This agrees with the previously inferred abyssal origin for part of the rocks from the LA (Cima di Gagnone). A similar origin has to be invoked for the Erzgebirge UHP unit. We suggest that all mafic and ultramafic rocks of this unit not only shared the same metamorphic evolution but also a common protolith origin, most probably on the ocean floor. This inference is supported by the presence of peridotite-hosted garnetite, representing metamorphosed rodingite.     

新疆西天山查岗诺尔铁矿床环带石榴子石和绿帘石的发现及意义

查岗诺尔铁矿是新疆西天山阿吾拉勒铁矿带内的重要大型铁矿床之一。矿体赋存在下石炭统大哈拉军山组安山质火山岩中,与普遍发育的石榴子石化、阳起石化和绿帘石化时空关系密切。石榴子石和绿帘石分属不同热液成矿阶段,它们均发育丰富的环带结构,具体表现为明显地颜色、干涉色、背散射图像及成分（FeO、Al₂O₃、SiO₂、MnO、TiO₂）等差异性。石榴子石具有2个世代、3个类型。早世代石榴子石（Grt1和Grt2）产于块状石榴子石-磁铁矿蚀变岩,呈褐黄色,粒度较细,发育核-边结构,呈非均质性,显示异常干涉色,其核部（Grt1-c）均匀相对富钙铝榴石（Gro_51-53And_41-43Spr_4-8）,而边部（Grt1-r）发育振荡成分环带,总体相对富钙铁榴石（Gro_18-35And_60-77Spr_4-6）;Grt2核部（Grt2-c）呈均质性,为钙铁榴石（And_99-100Spr_0-1）,边部显异常干涉色,发育振荡成分环带,为钙铝铁榴石（Gro_34-54And_38-61Spr_6-9）。晚世代的石榴子石（Grt3）以细脉状或角砾胶结物形式分布,呈红褐色,自形粗粒结构,显非均质性,发育振荡成分环带,端员组分总体以钙铁榴石为主,次为钙铝榴石（Gro_27-43And_50-68Spr_3-8）。石榴子石结构和元素含量变化表明,早期石榴子石形成于弱氧化-氧化、中性-碱性流体体系,其中向边部生长过程,由于新注入流体以及周期性压力汇聚和释放,体系的氧逸度、pH值呈振荡变化;晚期石榴子石形成于弱氧化、弱碱性、动荡的开放流体环境。绿帘石发育3个世代（Ep1、Ep2和Ep3）。Ep1发育核-边结构,核部（Ep1-c）均匀无环带,X_Fe值（X_Fe=Fe³⁺/（Al+Fe³⁺）,原子比值）为0.19~0.21,w（MnO）为0.05%~0.18%,w（TiO₂）为0.10%~0.12%,生长边（Ep1-r）多发育振荡环带,X_Fe值为0.26~0.29,w（MnO）为0.01%~0.14%,w（TiO₂）为0.19%~0.26%。Ep2沿Ep1-r边缘生长,不均匀且经历了溶解-再沉淀过程,X_Fe值为0.15~0.20,w（MnO）为0.42%~1.19%,w（TiO₂）为0.02%~0.07%。Ep3呈柱状或不规则粒状交代Ep2、贴近或穿切Ep1-r生长,较均匀、无环带结构,X_Fe值为0.28~0.37,w（MnO）为0.12%~0.77%,w（TiO₂）为0.02%~0.10%。绿帘石成分变化表明,从Ep1-c到Ep1-r,到Ep2,再到Ep3,流体体系氧逸度经历了先增加,后降低,再升高的变化过程。同时,流体成分也在变化,先从相对贫Ti和Mn向相对富Ti贫Mn演化,而后又变为富Mn贫Ti。因此,在热液磁铁矿矿化阶段,查岗诺尔铁矿的成矿热液的物理-化学环境是不断变化的。研究显示,石榴子石和绿帘石结构和成分研究可以刻画热液成矿系统的流体演化历史。     

On the mechanism of resorption zoning in metamorphic garnet

Abstract An analytical electron microscope study of almandine garnet from a metamorphosed Al–Fe‐rich rock revealed detailed composition profiles and defect microstructures of resorption zoning along fluid‐infiltrated veins and even into the garnet/ilmenite (inclusion) interface. This indicates a limited volume diffusion for the cations in substitution (mainly Ca and Fe) and an interface‐controlled partition for the extension of a composition‐invariant margin. A corrugated interface between the Ca‐rich margin/zone and the almandine garnet core is characterized by dislocation arrays and recovery texture further suggesting a resorption process facilitated by diffusion‐induced recrystallization, diffusion‐induced dislocation migration and diffusion–induced grain boundary migration. Integrated microstructural and chemical studies are essential for understanding the underlying mechanisms of processes such as garnet zoning and its modification. Without this understanding, it will not be possible to reliably use garnet compositions for thermobarometry and other applications that rely on garnet chemical information.     

福建云霄石榴子石宝石矿物学特征

福建云霄是我国重要的宝石级石榴子石产地,然而该区石榴子石的致色机理不清,制约了对其形成机制的理解及后续开发利用。本文选取7件福建云霄橙黄-橙红色石榴子石样品,利用傅立叶红外光谱、紫外-可见光光谱和拉曼光谱分析其谱学特征,使用电子探针及激光剥蚀电感耦合等离子体质谱仪(LA-ICP-MS)分析限定其主量、微量元素组成。结果表明云霄石榴子石主要为锰铝榴石,其颜色主要与二价锰(Mn²⁺)和铁离子(Fe²⁺)对可见光的吸收有关,Mn²⁺导致其主体呈橙色,少量Fe²⁺控制其橙红色调,微量Ti⁴⁺使其呈褐色调。福建云霄石榴子石样品核部锰含量相对较低而铁、镁含量较高,锰元素含量由核部向边部逐渐升高,且具有重稀土元素富集、轻稀土元素亏损的左倾配分模式和Eu负异常,表明其形成于岩浆结晶作用晚期。     

大别—苏鲁超高压榴辉岩中高钛石榴子石的成分特征及其与金红石包裹体的成因联系

石榴子石是榴辉岩中的基本造岩矿物。本文对苏鲁地体中的毛北榴辉岩和大别地体中的双河榴辉岩中的石榴子石进行了研究。结果显示,石榴子石都表现出中心“富”钛特征,即石榴子石颗粒的中心部位的TiO₂含量（0.10%~0.50%）明显高于正常榴辉岩中石榴子石的钛含量(TiO₂ 一般<0.1%)。另外,在石榴子石中心部位含有大量金红石及其它钛矿物包裹体,其定向分布特征揭示其出溶成因模式。计算结果显示,出溶金红石的原始石榴子石大约含1.7% TiO₂,揭示其超深源特征。此外,在石榴子石中发现了一颗TiO₂含量达8%~9%的钙铝榴石,具超深源成因特征。因此,本文认为超钛钙铝榴石也是超高压变质作用的标志矿物。     

南天山基性麻粒岩中变形石英和石榴子石的TEM研究

基性麻粒岩产于大陆地壳深部,它的研究可以为大陆岩石圈的性质、组成、演化和深部动力学过程提供重要信息。南天山库米什榆树沟地区发育总厚达1000多米的基性麻粒岩构造岩片,走向南东,朝北东推覆。剖面上和石炭纪蛇绿混杂岩共存,并发生了石榴子石的旋转变形和强烈的石英-长石矿物相韧性变形。然而它们的变形条件至今尚未被研究。本文运用透射电镜(TEM)超微组构技术对榆树沟基性麻粒岩中石英和石榴子石进行了详细研究,结果表明,石英中存在着丰富的超显微变形构造,自由位错、亚颗粒和位错网非常发育,这表明研究区基性麻粒岩在折返抬升过程中曾遭受过较强的石英-长石相韧性变形作用;石榴子石中的超微变形构造则极为少见,只在其中发现几根自由位错,并在其颗粒边缘发现少量亚颗粒构造,说明该矿物主体属于脆性变形。这两种矿物变形性质的差异,反映了石榴子石的晶体结构在该条件下比石英更稳定,而且说明石榴子石的变质温度没有超过900℃,也就是说,本区麻粒岩的变质作用并非发生在极高温度的条件下。     

大别山黄土岭麻粒岩锆石和共生矿物的微量元素分析及其地质意义

对大别山黄土岭麻粒岩中的锆石进行了LA-ICPMS微区微量元素分析.结果表明,黄土岭麻粒岩中锆石的不同区域有不同的微量元素组成,麻粒岩相变质锆石的大多数微量元素含量明显低于岩浆锆石,表明麻粒岩相变质条件下形成的锆石具有较低的微量元素组成.锆石及其共生矿物的微量元素分析结果表明,该麻粒岩中变质锆石Eu负异常是变质锆石形成时长石稳定存在的结果.锆石与石榴子石之间微量元素分配特点表明,变质锆石与石榴子石之间到达了平衡.这些结果表明,该样品的变质锆石形成于麻粒岩相峰期变质阶段,这些变质锆石区域测定的年龄结果对应于麻粒岩相峰期变质作用时间.锆石和共生矿物的微量元素分析对锆石的成因及得到的年龄的解释具有重要的指示意义.锆石与石榴子石之间微量元素的分配特征,不但可以指示锆石与石榴子石之间是否达到平衡,而且可以通过石榴子石这一"桥梁",为锆石的U-Pb年龄提供合理的p-T条件限定.