Constraints of stable isotopes on the origin of alunite from advanced argillic alteration systems in Bulgaria

Voluminous areas of advanced argillic alteration (AAA) constitute major exploration targets for surficial Cu–Au epithermal and potentially underlying porphyry-type deposits. In Bulgaria, more than 30 alunite occurrences are recognised, few of them being associated with a mineralised system. A mineralogical study combined with a stable isotopic (O, H, S) study has been carried out on nine alunite occurrences of advanced argillic zones hosted by volcanic rocks of Late Cretaceous age in the Srednogorie belt and of Oligocene age in the Rhodopes belt. This work was realised in order to constrain the origin of alunite and to define criteria to discriminate alunite from ore deposits and alunite from large barren alteration systems.Mineralogy of the nine occurrences consists of alunite + quartz + minor alumino-phospho-sulphates, associated with more or less kaolinite, dickite, pyrophyllite, diaspore and zunyite, depending on formation temperature. Alunite generally occurs as tabular crystals but is also present as fine-crystalline pseudocubic phases at Boukovo and Sarnitsa, in Eastern Rhodopes. In the advanced argillic alterations associated with economic ore, the presence of zunyite in the deeper parts indicates acid–fluorine–sulphate hydrothermal systems, whereas it is absent in uneconomic and barren advanced argillic alteration. All occurrences are formed at temperatures between 200 and 300 °C.(H, O, S) isotopic signatures of alunite combined with mineralogical features from all the studied occurrences, whatever their type, show characteristics of magmatic-hydrothermal systems. Sulphur data indicate essentially a magmatic origin for sulphur. Oxygen and hydrogen data suggest that hydrothermal fluids result from a mixing between magmatic fluids and an external component, which is identified as seawater-derived fluids or meteoric water in the vicinity of a sea. In most of the alunite occurrences, magmatic fluids are dominant and H₂S/SO₄ ratios are estimated to be higher than 2. Two exceptions exist in the Rhodopes. At Boukovo and Sarnitsa, where the estimated formation temperatures of alunite are the lowest, the external fluids are dominant and H₂S/SO₄ratios are estimated to be lower than or close to 1.At this stage of the work, the mineralogical and isotopic criteria do not enable a clear distinction between economic and uneconomic systems. However, some features are common in the economic ore deposits: the presence of zunyite in the deeper part of the system, the relatively high temperatures suggested by the zunyite + pyrophyllite + alunite + diaspore assemblages, the (O, H, S) signature of alunite, which is characteristic of dominant magmatic–hydrothermal acid–sulphate–fluorine systems.     

安徽庐枞盆地矾山酸性蚀变岩帽形成时代及其地质意义

酸性蚀变岩帽是岩浆热液流体和围岩在近地表相互作用的产物,是斑岩-浅成低温热液成矿系统的重要指标。发育在长江中下游成矿带庐枞盆地内的矾山酸性蚀变岩帽产出面积较大( 20km~2)。前人对该酸性蚀变岩帽中的明矾石矿床的地质和地化特征进行了相关研究,但详细的年代学研究工作尚未开展。为精确厘定矾山酸性蚀变岩帽的形成时代,本文开展了明矾石~(40)Ar-~(39)Ar法和金红石原位U-Pb法定年。矾山酸性蚀变岩帽中明矾石共有三种类型:ⅠA型明矾石主要呈交代蚀变发生在热液蚀变早阶段,与石英、粒状黄铁矿或赤铁矿、少量金红石共生;ⅠB型明矾石形成于热液蚀变晚阶段,主要呈叶片状集合体充填在开放空间中,与石英、星点状赤铁矿、粒状金红石集合体共生,少量金红石和赤铁矿沿明矾石解理裂隙分布;Ⅱ型明矾石是表生明矾石,主要呈细粒集合体沿裂隙分布,与赤铁矿、高岭石、地开石共生。三类明矾石形成于不同环境下:ⅠA和ⅠB型明矾石形成于岩浆热液环境下,是大矾山明矾石矿区的主要产物;Ⅱ型细粒明矾石分布在矾山酸性蚀变岩帽的非明矾石矿区,是表生环境下的产物。ⅠA型明矾石的~(40)Ar-~(39)Ar定年的坪年龄为131±6Ma,代表了矾山酸性蚀变岩帽的形成时代。与Ⅱ型明矾石密切共生的金红石U-Pb定年结果为32. 7±4Ma,在该期间,整个盆地内无岩浆活动发生,该年龄反映了矾山酸性蚀变岩帽经历表生氧化作用的时间。明矾石和金红石定年结果分别对应岩浆热液和表生明矾石的形成时代。在利用明矾石进行找矿工作时需先明确明矾石成因,矾山酸性蚀变岩帽中深成明矾石是下一阶段的找矿研究的基础。     

蚀变岩帽的特征、成因以及在华南的分布探讨

Sillitoe（1995）蚀变岩帽（Lithocap）的定义为大范围富黄铁矿的硅化、高级泥化和泥化蚀变,在地质环境上位于古地表和浅成中-酸性岩浆侵入体之间。蚀变岩帽往往显示为突出的正地形,有助于寻找隐伏的斑岩矿化体。但蚀变岩帽在地表的范围往往多达几十个平方千米,又常常掩盖下覆斑岩矿床的蚀变矿化特征及其地球化学印记,因此大型的蚀变岩帽又给勘探工作带来一定的挑战。蚀变岩帽相关矿床的勘探需以地质填图为基础,结合近红外光谱分析（SWIR）进行蚀变填图,以及全岩地球化学以及矿物地球化学表现的元素或元素组合异常,来帮助定位热源或深部斑岩体。遥感和地球物理中的激电响应,也可以辅助定位岩体。华南地区的蚀变岩帽主要分布于长江中下游成矿带和东南沿海火山岩带。前人对安徽庐枞盆地中的矾山蚀变岩帽进行了系统研究,确定了矾山蚀变岩帽形成于白垩纪,与围岩砖桥组火山岩年龄一致。同位素和流体包裹体工作证明了形成矾山蚀变岩帽的流体主要为深部岩浆热液中的酸性气体与浅部大气降水的混合,在浅部高渗透率的火山岩及其岩性界面反应,广泛发育了一套硅化和高级泥化蚀变,指示与矾山相关可能存在斑岩和高硫型浅成低温热液铜金矿床。福建紫金山地区有中国最大的高硫型浅成低温热液矿床,主要赋存于紫金山蚀变岩帽中。紫金山蚀变岩帽的地质特征和蚀变分带已经研究的较为详细,但目前深部的侵入体还没有发现。浙江的蚀变岩帽是中国非金属矿产的重要来源,包括明矾石矿、地开石矿和红柱石矿等,这些蚀变岩帽与金属矿化的关系尚未有相关研究。根据目前的资料总结,有较多的蚀变岩帽分布在中国华南,这些蚀变岩帽特征典型,但目前的研究程度尚浅。现有的研究结果表明,华南的蚀变岩帽的成矿潜力巨大,可能存在一条巨型的斑岩-浅成低温矿床成矿带,具有广阔的找矿勘查前景,建议加强蚀变岩帽及相关矿床的找矿与研究工作。     

Prediction of Gibbs free energies of formation of minerals of the alunite supergroup

A method for the prediction of Gibbs free energies of formation for minerals belonging to the alunite family is proposed, based on an empirical parameter Δ_GO⁼ M^z+(c) characterizing the oxygen affinity of the cation M^z+. The Gibbs free energy of formation from constituent oxides is considered as the sum of the products of the molar fraction of an oxygen atom bound to any two cations, multiplied by the difference of oxygen affinity Δ_GO⁼ M^z+(c) between any two consecutive cations. The Δ_GO⁼ M^z+(c) value, using a weighing scheme involving the electronegativity of a cation in a specific site (12-fold coordination site, octahedral and tetrahedral) is assumed to be constant. It can be calculated by minimizing the difference between experimental Gibbs free energies (determined from solubility measurements) and calculated Gibbs free energies of formation from constituent oxides. Results indicate that this prediction method gives values within 0.5% of the experimentally measured values. The relationships between Δ_GO⁼ M^z+(alunite) corresponding to the electronegativity of a cation in either dodecahedral sites, octahedral sites or tetrahedral sites and known as Δ_GO⁼ M^z+(aq) were determined, thereby allowing the prediction of the electronegativity of rare earth metal ions and trivalent ions in dodecahedral sites and highly charged ions in tetrahedral sites. This allows the prediction of Gibbs free energies of formation of any minerals of the alunite supergroup (bearing various ions located in the dodecahedral and tetrahedral sites). Examples are given for hydronium jarosite and hindsalite, and the results appear excellent when compared to experimental values.     

浙江省明矾石矿床地质特征及其成因类型

浙江非金属矿产资源丰富,其中明矾石等5种矿产的储量居全国首位,对明矾石资源的开发利用也居全国前列;但对其的控矿因素、成矿机理、成因类型的研究相对滞后。通过综合分析浙江省境内典型矿床的地质特征、成矿条件与环境,将其分成:火山喷发沉积-热液交代型、火山热液交代型两种类型。     

庐枞盆地高硫化型浅成低温热液成矿系统:来自矾山明矾石矿床地质特征和硫同位素地球化学的证据

庐枞中生代火山盆地位于长江中下游断陷带内,地处扬子板块的北缘。庐枞盆地内火山岩和侵入岩分布广泛,包括龙门院、砖桥、双庙和浮山四组火山岩以及34个侵入岩体。盆地内产出一系列铁、铜、铅、锌、铀等金属矿床,同时还大量产出以明矾石和硬石膏为代表的非金属矿床。庐枞盆地北部砖桥组火山岩内中酸性硫酸盐蚀变广泛发育,指示盆地内存在高硫化型浅成低温热液系统。本文以盆地北部矾山明矾石矿床为研究对象,查明了矾山明矾石矿体主要赋存在火山碎屑岩内,矿体呈似层状,产状基本上与围岩一致,矿石类型以黄铁矿-石英-明矾石矿石为主,明矾石主要为钾明矾石,主要蚀变类型包括明矾石化、硅化、高岭土化和绢云母化。明矾石的δ34S值范围为20.29‰~23.18‰,平均值为21.86‰,黄铁矿δ34S值范围为-7.06‰~-8.36‰,平均值为-7.49‰,明矾石和黄铁矿δ34S平均值计算Δ34SAlun-Py为29.35‰,指示矾山明矾石为岩浆热液与火山岩地层水岩作用的产物,硫同位素温度计计算得出明矾石形成温度为264℃。通过相关对比研究,本文认为庐枞盆地内存在高硫化型低温热液系统,系统中广泛发育的酸性蚀变很可能是玢岩铁矿成矿系统的组成部分,是玢岩铁矿系统成矿气液不断作用并演化到了最晚阶段的产物。     

紫金山铜金矿明矾石交代蚀变岩的岩石地球化学特征

在野外地质调查和岩(矿)相学的基础上,通过对比分析紫金山铜金矿各种交代蚀变岩的岩石地球化学特征,对本矿高硫化型浅成低温热液成矿体系有了进一步认识.相比其他种类的交代蚀变岩,明矾石交代蚀变岩的岩石地球化学特征主要表现为:①主量元素中Al2O3,K2O明显增加,而SiO2明显降低,其他造岩元素也都有降低的趋势;②成矿元素Cu与运矿元素S,F相关性密切;Cu与Au,Ag等成矿元素呈一定的正相关性,而与Pb,Zn,Sn等矿化相关性较差;③微量元素均显示出大离子亲石元素较高,明显富集Rb,Ba,Tb,U,Pb,而低P,Ti;④稀土元素普遍具有较高的轻稀土、较低的重稀土,负Eu异常较小或不明显.明矾石交代蚀变岩的这些岩石地球化学特征显示出紫金山铜金矿高硫化型浅成低温热液是富含Cu,Au,Ag等多种成矿元素和S,F等运矿元素的成矿流体,其形成是与燕山晚期中酸性的火山—侵入杂岩有关的岩浆热液与燕山早期的花岗岩类长期广泛水—岩反应的结果.     

Relative age of Cordilleran base metal lode and replacement deposits, and high sulfidation Au–(Ag) epithermal mineralization in the Colquijirca mining district, central Peru

At Colquijirca, central Peru, a predominantly dacitic Miocene diatreme-dome complex of 12.4 to 12.7 Ma (⁴⁰Ar/³⁹Ar biotite ages), is spatially related to two distinct mineralization types. Disseminated Au–(Ag) associated with advanced argillic alteration and local vuggy silica typical of high- sulfidation epithermal ores are hosted exclusively within the volcanic center at Marcapunta. A second economically more important mineralization type is characterized as "Cordilleran base metal lode and replacement deposits." These ores are hosted in Mesozoic and Cenozoic carbonate rocks surrounding the diatreme-dome complex and are zoned outward from pyrite–enargite–quartz–alunite to pyrite–chalcopyrite–dickite–kaolinite to pyrite–sphalerite–galena–kaolinite–siderite. Alunite samples related to the Au–(Ag) epithermal ores have been dated by the ⁴⁰Ar/³⁹Ar method at 11.3–11.6 Ma and those from the Cordilleran base metal ores in the northern part of the district (Smelter and Colquijirca) at 10.6–10.8 Ma. The significant time gap (~0.5 My) between the ages of the two mineralization types in the Colquijirca district indicates they were formed by different hydrothermal events within the same magmatic cycle. The estimated time interval between the younger mineralization event (base metal mineralization) at ~10.6 Ma and the ages of ~12.5 Ma obtained on biotites from unmineralized dacitic domes flanking the vicinity of the diatreme vent, suggest a minimum duration of the magmatic–hydrothermal cycle of around 2 Ma. This study on the Colquijirca district offers for the first time precise absolute ages indicating that the Cordilleran base metal lode and replacement deposits were formed by a late hydrothermal event in an intrusive-related district, in this case post Au–(Ag) high-sulfidation epithermal mineralization.Electronic Supplementary Material Supplementary material is available for this article if you access the article at . A link in the frame on the left on that page takes you directly to the supplementary material.Editorial handling: O. Christensen     

Equilibrium data and process design for adsorption of disperse dyes onto Alunite

Adsorption of disperse dyes from aqueous solutions onto calcined alunite has been investigated to assess the possibility of using alunite for removing disperse dyes from aqueous solutions. The effects of particle size, adsorbent mass, initial pH and temperature of the dye solution on the adsorption capacities have been evaluated. Acidic pH was favorable for the adsorption of all dyes: Disperse Blue 56 (DB56), Disperse Red 74 (DR74) and Disperse Yellow 119 (DY119). The experimental data were correlated reasonably well by the Langmuir isotherm and the isotherm parameters (K_L and a_L) have been calculated. The adsorption capacities were found to be 498, 525 and 500 mg of dye per g of calcined alunite for DB56, DR74 and DY119, respectively. The single-stage batch adsorber design of the adsorption of disperse dyes onto alunite has been studied based on the Langmuir isotherm equation.     

Single-crystal elastic properties of alunite, KAl3(SO4)2(OH)6

The single-crystal elastic constants of natural alunite (ideally KAl₃(SO₄)₂(OH)₆) were determined by Brillouin spectroscopy. Chemical analysis by electron microprobe gave a formula KAl₃(SO₄)₂(OH)₆. Single crystal X-ray diffraction refinement with R ₁ = 0.0299 for the unique observed reflections (|F _o| > 4σ _F) and wR ₂ = 0.0698 for all data gave a = 6.9741(3) Å, c = 17.190(2) Å, fractional positions and thermal factors for all atoms. The elastic constants (in GPa), obtained by fitting the spectroscopic data, are C ₁₁ = 181.9 ± 0.3, C ₃₃ = 66.8 ± 0.8, C ₄₄ = 42.8 ± 0.2, C ₁₂ = 48.2 ± 0.5, C ₁₃ = 27.1 ± 1.0, C ₁₄ = 5.4 ± 0.5, and C ₆₆ = ½(C ₁₁–C ₁₂) = 66.9 ± 0.3 GPa. The VRH averages of bulk and shear modulus are 63 and 49 GPa, respectively. The aggregate Poisson ratio is 0.19. The high value of the ratio C ₁₁/C ₃₃ = 2.7 and of the ratio C ₆₆/C ₄₄ = 1.6 are characteristic of an anisotropic structure with very weak interlayer interactions along the c-axis. The basal plane (001) is characterized by 0.1% longitudinal acoustic anisotropy and 0.9–1.1% shear acoustic anisotropy, which gives alunite a characteristic pseudo-hexagonal elastic behavior, and is related to the pseudo-hexagonal arrangement of the Al(O,OH)₆ octahedra in the basal layer. The elastic Debye temperature of alunite is 654 K. The large discrepancy between the elastic and heat capacity Debye temperature is also a consequence of the layered structure.