Sulfur K- and L-edge X-ray absorption spectroscopy of sphalerite,chalcopyrite and stannite

Sulfur K-edge x-ray absorption spectra (XANES and EXAFS) and L-edge XANES of sphalerite (ZnS), chalcopyrite (CuFeS₂) and stannite (Cu₂FeSnS₄) have been recorded using synchrotron radiation. The K- and L-edge XANES features are interpreted using a qualitative MO/energy band structure model. The densities of unoccupied states at the conduction bands of sphalerite, chalcopyrite and stannite are determined using S K- and L-edge XANES features (up to 15 eV above the edge), combined with published metal K-edge XANES. The SK- and L-edge XANES also indicate that, for sphalerite, the Fe²⁺ 3d band at the fundamental gap has little or no bonding hybridization with S 3p and S 3s orbitals; for chalcopyrite, the Cu⁺ 3d and Fe³⁺ 3d bands have strong mixing with S 3p and S 3s states, while for stannite the Cu⁺ 3d band strongly hybridizes with S 3p and S 3s orbitals, but the Fe²⁺ 3d band does not. The post-edge XANES features (15–50 eV above the edge) of sphalerite, chalcopyrite and stannite are similar. These features are related to the tetrahedral coordination of sulfur in all these structures, and interpreted by a multiple scattering model. The resonance energies from both the K-edge and L-edge XANES for these minerals are well correlated with reciprocal interatomic distances and lattice spaces. Sulfur K-edge EXAFS analyses using Fourier transform and curve fitting procedures are presented. Comparison of the structural parameters from EXAFS with x-ray structure data shows that the first shell bond distances (BD) from EXAFS are usually accurate to ±0.02 Å, and that coordination numbers (CN) are generally accurate to ±20 percent. For sphalerite, EXAFS analysis yields the structure parameters for the first three neighbour shells around a sulfur atom; the BD and CN even for the third shell are in close agreement with the x-ray structure, and the Debye-Waller term decreases from the first shell to the third shell. It is shown that sphalerite (ZnS) is a good model compound for EXAFS analysis of sulfur in chalcogenide glasses and metalloproteins.     

Bulk compositions of intimate intergrowths of chalcopyrite and sphalerite and their genetic implications

To determine the bulk chemical compositions of chalcopyrite containing starlike sphalerite and sphalerite including dotlike chalcopyrite, specimens from various types of ore deposits in Japan were used for modal and electron microprobe analyses. According to the analytical results, most of the measured zinc contents in chalcopyrite containing starlike sphalerite are less than 0.8 at%, corresponding to the maximum solubility of zinc in chalcopyrite as determined experimentally at 400°C. However, specimens from the Maruyama deposit in the Tsumo mine contain 1.2–1.4 at% Zn, which are within the solubility limit of an intermediate solid solution (ISS) above 400°C. It is therefore concluded that starlike sphalerite in chalcopyrite are exsolution products derived from primary chalcopyrite solid solution and/or zincic ISS. Measured copper contents in sphalerite including dotlike chalcopyrite yield considerably higher values, i.e., 1.5–6.0 at%, which exceed the solubility limits of copper in sphalerite solid solution as determined experimentally. This result suggests that not all the chalcopyrite dots were exsolved from sphalerite, but that most of them are the product of some other mechanisms.     

Chalcopyrite Intergrowths in sphalerite in the Meixian Lead—Zine Deposit,Fujian Province and their Metallogenic Significance

Ore textures and electron microprobe analyses show that in addition to highly scattered blebs in sphalerite grains,intergrown chalcopyrite also occurs as rods,myrmekites and lamellae aligned along cleavages and twin boundaries of the host sphalerite.The majority of the intergrowths could have been formed by replacement of sphalerite by chalcopyrite,albeit part of them may have resulted from exsolution,Not only copper,but also iron were introduced into the sphalerite by replacive fluids.While the front of the replacing fluid was moving forward through a sulphide orebody,Zn and Pb were dissolved and Cu was precipitated,resulting in zonal refining of the sulphide ores,The remobilized zinc and lead were precipitated at favourable sites with changed physico-chemical conditions .This is a possible mechanism for the formation of copper-poor zinc and lead ores above or lateral to the copper orebodies in some of the massive sulphide deposits reworked and overprinted by late-stage granites and their hydrothermal fluids.     

Collectorless flotation of chalcopyrite and sphalerite ores by using sodium sulfide

The flotation of chalcopyrite and sphalerite from copper and copper-zinc ores has been achieved without using thiol-type collectors. Typically, a sulfide ore sample is first treated with sodium sulfide either during grinding or during the preflotation conditioning period, and then the chalcopyrite is floated with frother alone. With a copper-zinc ore, sphalerite is subsequently floated from the chalcopyrite tailings by activating it with copper sulphate. Results of the collectorless flotation tests are comparable to those obtained by using thiol collectors. The mechanisms of selective collectorless flotation are discussed on the basis of differences in the solubilities of sulfide minerals.     

Iron and zinc partitioning between coexisting stannite and sphalerite: a possible indicator of temperature and sulfur fugacity

Stannite and sphalerite coexisting with iron sulfides (pyrite and/or pyrrhotite) from Japanese ore deposits associated with tin mineralization were analyzed. Based on the iron and zinc partitioning between stannite and sphalerite, the formation temperature and sulfur fugacity for this mineral assemblage were estimated. A good correlation between stannite-sphalerite temperatures and filling temperatures of fluid inclusions and sulfur isotope temperatures was obtained. This good correlation suggests that the stannite-sphalerite pair is a useful indicator of temperature and sulfur fugacity. It is deduced that the formation temperatures are not different for skarn-type, polymetallic vein-type and Sn-W vein-type deposits, whereas the sulfur fugacities are different; sulfur fugacities increase from the skarn-type through the Sn-W vein-type to the polymetallic vein-type deposits.     

Trace and minor elements in sphalerite from metamorphosed sulphide deposits

Sphalerite is a common sulphide and is the dominant ore mineral in Zn-Pb sulphide deposits. Precise determination of minor and trace element concentrations in sulphides, including sphalerite, by Laser-Ablation Inductively-Coupled-Plasma Mass-Spectrometry (LA-ICP-MS) is a potentially valuable petrogenetic tool. In this study, LA-ICP-MS is used to analyse 19 sphalerite samples from metamorphosed, sphalerite-bearing volcanic-associated and sedimentary exhalative massive sulphide deposits in Norway and Australia. The distributions of Mn, Fe, Co, Cu, Ga, Se, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb and Bi are addressed with emphasis on how concentrations of these elements vary with metamorphic grade of the deposit and the extent of sulphide recrystallization. Results show that the concentrations of a group of trace elements which are believed to be present in sphalerite as micro- to nano-scale inclusions (Pb, Bi, and to some degree Cu and Ag) diminish with increasing metamorphic grade. This is interpreted as due to release of these elements during sphalerite recrystallization and subsequent remobilization to form discrete minerals elsewhere. The concentrations of lattice-bound elements (Mn, Fe, Cd, In and Hg) show no correlation with metamorphic grade. Primary metal sources, physico-chemical conditions during initial deposition, and element partitioning between sphalerite and co-existing sulphides are dominant in defining the concentrations of these elements and they appear to be readily re-incorporated into recrystallized sphalerite, offering potential insights into ore genesis. Given that sphalerite accommodates a variety of trace elements that can be precisely determined by contemporary microanalytical techniques, the mineral has considerable potential as a geothermometer, providing that element partitioning between sphalerite and coexisting minerals (galena, chalcopyrite etc.) can be quantified in samples for which the crystallization temperature can be independently constrained.     

Zinc and sulfur isotope variation in sphalerite from carbonate-hosted zinc deposits,Cantabria, Spain

We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ⁶⁶Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from ?0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ³⁴S?=?+6.6 and stage 2 has δ³⁴S?=??0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light ⁶⁶Zn-depleted signatures with δ⁶⁶Zn values from ?0.80 to ?0.01 per mil (mostly between ?0.80 and ?0.24 per mil) and δ³⁴S values from +10.7 to +15.7 per mil without any relationship between the δ⁶⁶Zn and δ³⁴S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250–320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH₂S?>?mZn²⁺ as a result of change in pH, T, and Zn predominant species. The light δ⁶⁶Zn accompanied by heavy δ³⁴S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ⁶⁶Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.     

广东长埔—吉水门锡矿带某些成矿规律和矿床成因

广东长埔—吉水门锡矿带内的锡矿床(点)几乎毫无例外地赋存于下侏罗统金鸡群第二亚群中,锡矿带的展布格局和矿体的形态、产状等特征说明,锡矿受地层层位控制。锡矿带受莲花山断裂带的次一级断裂制约,矿床、矿体主要产于NE-NEE向层间滑动断裂及其派生裂隙中,锡矿具有构造定位的特征。矿床一般经历了早、晚两个成矿期,第一成矿期发生于晚侏罗世火山作用之前,第二成矿期形成于晚侏罗世末期至早白垩世。成矿物质是多来源的,但主要来自地层。金鸡群地层富含锡等成矿组分,是重要的矿源层。成矿溶液以变质水为主,并有大气降水混入。锡矿床属沉积-变成层控矿床。     

Formation of the strata-bound Kellhuani tin deposits,Bolivia

A magmatic-hydrothermal model of tin ore formation can best explain the geological, petrographical and geochemical data on the strata-bound Kellhuani tin district. The tin specialization of the magmatic system of the Chacaltaya porphyry stock, centered in the Kellhuani mining area, is the result of advanced fractional crystallization. The regional tin background of the least fractionated members of the Cordillera Real granite series and of their sedimentary country rocks corresponds to average crustal tin contents.Dedicated to Prof. H.-J. Schneider on the occasion of his 60th birthday     

Compositional characteristics of wolframite in tin deposits,Dupangling, Guangxi

Statistical data on major, trace and rare-earth elements in wolframite from the quartz vein-and greisen-type tin deposits in the Dupangling orefield reveal: (1) The components in wolframite can be divided into two relatively independent groups: the WO₃-Nb-Ta-Sc-REE group, in which WO₃ is negatively correlated with the others and the FeO-MnO-Sn group, in which MnO is negatively correlated with the other two; (2) In general, REE fractionation is not significant, reflected mainly by the separation of Eu from other REE’s. LREE and HREE increase or decrease simultaneously, with HREE being more variable; (3) Nb, Ta, Sc, REE substitute for W, and Sn may enter into wolframite lattice accompanied by Fe-Mn substitution; (4) In contrast to wolframite in quartz veins, which is poor in REE, Nb, Ta and Sc and has highδ Eu values and LREE / HREE and Nb/Ta ratios, wolframite in greisen is rich in REE, Nb, Ta, Sc and has lowδ Eu values and LREE/HREE and Nb/Ta ratios; and (5) The contents and ratios of trace elements and REE partitioning parameters of wolframite can be used as guide for prospecting.     

Indium in cassiterite and ores of tin deposits

The results obtained with LA-ICP-MS by less abundant lighter ¹¹³In isotope and EPMA show that in cassiterite of cassiterite–quartz veins the indium contents do not exceed 160 ppm, while cassiterite from Sn–sulfide veins is characterized by higher indium contents from 40 to 485 ppm; sulfides of Sn–sulfide veins unlike sulfides of cassiterite–quartz veins also have the highest indium contents: Fe-sphalerite (100–25,000 ppm), chalcopyrite (up to 1000 ppm), and stannite (up to 60,000 ppm). Indium contents in the Sn–sulfide ore of the Tigrinoe and Pravourmiiskoe deposits obtained using SR-XRF, ICP-MS and atomic absorption methods range from 10 to 433 ppm with average values of 56–65 ppm. Indium-rich Sn–sulfide mineralization in five large Sn–Ag ore districts of the Far East Russia (Khingansky, Badzhalsky, Komsomolsky, Arminsky, Kavalerovsky) provides the impetus for further exploration of deposits with Sn–sulfide mineralization as the most promising indium resources in Russia. Empirical observations from geology and geochronology of cassiterite–quartz and Sn–sulfide mineralization show that the combined contribution from granite and alkaline–subalkaline mafic sources and multistage ore-forming processes doubled indium resources of deposits being the main factors in the formation of high grade indium mineralization.     

湖南骑田岭地区锡矿床特征及找矿前景

骑田岭地区锡矿找矿的突破，是近两年国土资源重大调查取得的重大成果。区内锡矿产于骑田岭复式花岗岩体南部以及接触带，多呈脉状产出。锡矿类型以云英岩化花岗岩型、蚀变斑状花岗岩型、蚀变构造带型为主，具有矿体厚度碱、蚀变强、品位较高、矿石利用性能好的特点。现已估算锡资源量约60万吨，还有成矿条件类似的北部及同一构造岩浆岩带的其他地区，进一步开展该地区国土资源大调查将会扩大现有的找矿成果。     

西昆仑阿巴列克铜铅矿床黄铜矿Re-Os定年及地质意义

除了传统的测试Rb-Sr、Sm-Nd、U-Th-Pb、K-Ar或Ar-Ar等方法来讨论碳酸盐岩层控型铅锌矿的成矿年龄外,利用硫化物矿物Re-Os分析成矿过程,在矿床成矿系统上也是十分重要而有效的工具.从新疆西昆仑阿巴列克铜铅矿床的主矿体中,选取7个黄铜矿和1件黄铁矿样品,对其进行了Re-Os定年,结果表明它们分别含有626×10-9～14533×10-9 Re和0.026×10-9 ～0.36×10-9Os,给出海西期的331.3±5.2Ma等时线年龄.样品的高Re/Os比值、低含量普通Os和高放射成因Os的组成特性支持这组黄铜矿样品为表壳构造成因.构造演化历史表明,塔里木地块西南缘在晚古生代属于被动大陆边缘,赋矿地层霍什拉甫组属于台地相碳酸盐岩-碎屑岩建造,地层时代与上述等时年龄几乎相近.本次工作提供了一个新的证据,支持阿巴列克矿床在海西期经历了同生成矿作用,矿床类型主要为沉积层控型,成矿物质主要来源于地层,矿化发生在上泥盆统与下石炭统的结合部位,岩性以砂岩与碳酸盐岩组合为主,具有特定的层位控制特点.从中可以看出,碳酸盐岩层控型铅锌铜矿床成因具有一定的复杂性,具有深入研究的广阔空间.     

Features of tin mineralization in carbonate deposits,as in Eastern Siberia

The paper shows differences in character of tin mineralization in skarns which develop after dolomites (magnesial) and limestones (limy). Cassiterite is not deposited in the former, since because of the relatively high alkalinity and the high activity of boron (B₂0₃), tin preferentially enters the crystal structures of Sn-borates such as hulseite, ludwigite, and nordenskioldine rather than cassiterite. In limy skarns, tin is largely dissipated in garnets (up to 0.62%), axinites (up to 0.2%), and other minerals. It is only at the end of the appropriate stage, at relatively high acidity, that tin is deposited as cassiterite in magnetitic and amphibole-axinitic skarns. The latter are very favorable for development of economic ore bodies. Conclusions are made to the effect that a) tin is present in the postmagmatic solutions during each of the three stages, and also b) concerning optimum conditions for deposition of tin minerals in any stage (depending on magnitudes of Eh and pH environments and B₂O₃ and S^2- activities. -- Author.     

Partition of cadmium and manganese between coexisting sphalerite and galena from some Japanese epithermal deposits

Sphalerites from Japanese epithermal Pb-Zn vein-type deposits, namely, Yatani, Oizumi and Hosokura, contain 2900–3400 ppm cadmium and 760–2100 ppm manganese. And galenas from the same deposits contain cadmium and manganese 19.2–26.9 ppm and 7.8–218.3 ppm, respectively. The temperatures, evaluated from the partition of cadmium between coexisting sphalerite and galena, are consistent within a total range of 150°C at maximum within an individual deposit. No systematic change with depth can be observed at the Shoko-hi vein, Hosokura mine and Hompi vein, Yatani mine. In several samples, the temperatures obtained from the partition of cadmium have been compared with those obtained from sulfur isotope fractionations. Iron content in sphalerite coexisting with pyrite indicates that the deposition of ore minerals at these deposits may have taken place from ore-forming solutions in which H₂S or HS^– was the predominant dissolved sulfur species, and the solutions may have been free from in situ oxidation or reduction.     

粤东莲花山地区锡矿矿产类型

锡矿是粤东优势矿种之一。在收集分析粤东莲花山地区61个锡矿床（点）成矿特征的基础上,对该地区锡矿床（点）矿产类型进行划分归类,建立了粤东莲花山地区锡矿工业类型,主要有为锡石-硫化物型、锡石-硅酸盐型、锡石-石英脉型、斑岩型4类;对4种不同类型锡矿床所具有的矿物组合进行归纳,并开展各类型代表性矿床综合研究,初步构建了4个类型代表性矿区的成矿模式图,为粤东地区锡矿研究提供了基础资料。     

Fractional crystallization and the origin of tin deposits in granitoids

A comparison between tin-bearing granitoids in an anorogenic setting (Bushveld Complex) and an orogenic setting (Blue Tier Batholith, Tasmania) reveals a number of genetically important similarities. These include: in situ fractional crystallization characterised by marked decrease in Ba and Sr and increase in Rb; the accumulation of late melt in a sheet-like form near the roof zone; the association of barren pegmatites overlying the ore; and of aplites; and the occurrence of conformable tin-bearing sheets, often exhibiting greisenization. These features allow the formulation of the following genetic model. A crustally-derived granitoid magma is emplaced and undergoes fractional crystallization from the margins inwards, with bottom crystallization dominating. Disruption of earlier formed solids by rest liquid commonly occurs. Continued fractional crystallization causes enrichment in volatiles and incompatible elements in the late rest melts, which have a sheet-like habit. The efficiency of enrichment of incompatible elements is critically dependant on the degree of separation of melt from solids throughout crystallization. An early, tin-poor vapour may separate after initial water-saturation of the magma is achieved, and this collects under the roof, commonly forming an impermeable barrier to later tin-bearing fluids. Continued fractional crystallization on the floor further enriches incompatible elements, and at a very late stage a Sn-rich vapour separates within the intercumulus phase and becomes concentrated by progressive crystallization of the intercumulus melt. At a late stage of solidification, this vapour loses equilibrium with the earlier formed feldspars and greisenization ensues, accompanied by the crystallization of cassiterite and other ore minerals. The nature of the mineralization changes if through-going fractures tap the late fluids. This model predicts systematic changes in trace element geochemistry with crystallization which provide useful tools for assessing the tin potential of a granitoid, and for indicating the direction of crystallization of the magma, and hence the location of possible ore.     

The three geochemical series of tin deposits and their evolution

Three geochemical series, i.e., the siderophile, chalcophile and lithophile series, have been classified for tin deposits based on geological-geochemical data on tin mineralization in China. The three series are distinct from each other in geological settings, ore-forming elements, minor elements, REE, stable isotopes, ore-forming fluids and physicochemical conditions. The formation of tin deposits of the three series could be closely related to the evolution of the Earth’s crust.     

湘南粤北铅锌矿床闪锌矿的标型特征及指示意义

湘南粤北位于南岭成矿带中段,是我国最重要的铅锌矿集区之一。本文选取湘南粤北地区MVT和岩浆热液型两类铅锌矿床的闪锌矿样品,对闪锌矿的形态、结构、化学成分、硫同位素组成、流体包裹体成分等进行系统研究,分析其成矿温度、硫的来源和成矿流体特征,为揭示成矿作用提供可靠依据。研究结果表明:MVT铅锌矿床成矿作用发生在中低温、氧化-弱还原、较低压力环境,硫主要来源于容矿地层,成矿流体主要来自于热卤水和沉积物变质脱水;岩浆热液型铅锌矿床成矿作用发生在中高温、弱还原、较高压力条件下,硫源主要以岩浆硫为主,成矿流体早期以岩浆热液为主,晚期为混合流体。结合矿体与岩体的形成时间、空间分布、大地构造背景,认为岩浆热液型铅锌矿床由燕山早期(180~150 Ma)古太平洋向大陆俯冲、岩石圈加厚,爆发大规模花岗质岩浆岩侵位,导致铅锌成矿;MVT铅锌矿床由燕山晚期(130~90 Ma)欧亚大陆岩石圈伸展减薄产生的岩浆热液叠加改造泥盆系的原始矿源层形成。     

Trace elements of Indium-bearing sphalerite from tin-polymetallic deposits in Bolivia,China and Japan: A femto-second LA-ICPMS study

Indium-bearing tin-polymetallic base metal deposits in Japan (Toyoha, Ashio and Akenobe), China (Dulong and Dachang), and Bolivia (Potosi, Huari Huari, Bolivar and Porco), were studied using femto-second Laser Ablation ICPMS (fsLA-ICPMS) and EPMA analyses for major and minor elements in sphalerite, paying special attention to In concentrations.Sphalerite is a principal mineral in these tin-polymetallic deposits and a broad range of In concentration is measured in the ores. There are distinct differences in mode of occurrence of the sphalerite and the distribution of In. The highest In concentration (up to 18 wt.%) occur as a Zn–In mineral within black sphalerite zones in an oscillatory-zoned sphalerite from the Huari Huari deposits. Additionally, jamesonite from the Huari Huari deposit also contains anomalous In values, ranging from several hundreds to thousands μg/g. Sphalerite from the Toyoha and the other Bolivian deposits are characterized by oscillatory and chemical zoning, whereas those from Akenobe and the Chinese deposits are represented by homogeneous distribution of In. The 1000In/Zn values of sphalerite are in good agreement with those of the ore grade for each of the selected tin polymetallic deposits indicating that sphalerite is the principal host of In.The In-bearing sphalerite principally involves the combined coupled substitutions (2Zn^2 +) ↔ (Cu⁺, In^3 +), (3Zn^2 +) ↔ (Cu⁺, Ag⁺, Sn^4 +) and (3Zn^2 +) ↔ (2Cu⁺, Sn^4 +). The first of these is apparent in sphalerite from Huari Huari and Bolivar, whereas the second is prominent in sphalerite from Toyoha, Ashio, Potosi, Porco and Dachang. Akenobe and Dulong sphalerite features the dominant coupled substitution of (2Zn^2 +) ↔ (Cu⁺ or Ag⁺, In^3 +), owing to their poor Sn content. Occasionally, sub-micron inclusions of minerals such as stannite and Pb–Sb-bearing sulfides can occur in sphalerite, contributing to high Cu–Sn and high-Ag contents, respectively. The observed correlations of each element in the In–Cu–Ag–Sn-bearing sphalerite can be proposed as a fundamental reason for the indium enrichment related to sulfur-rich oxidized magmatism. In addition, the Ag content in sphalerite is considered a possible indicator of formation depth, which ranges from plutonic to subvolcanic environments.