电子探针能谱矿物定量分析

文章以不同类型矿物作为分析实例，说明电子探针能谱仪和谱仪在矿物分析中的作用。实验表明使用能谱各类矿物主元素进行定量分析，既满足精密要求又能缩短分析时间，提高工效约２０倍，对能谱用于定量分析过程中的若干技术问题进行了讨论，以期获得最佳精密度的分析结果。     

硫化物矿物的主微(痕)量元素分析进展

金属或半金属元素(Fe、Mo、As、Cu、Co、Ni、Zn、Pb等)、贵金属元素(Au、Ag)和铂族元素(PGE)、稀有分散元素(Re、Ga、In等)以高浓度富集或微量赋存于硫化物矿物中,常形成具有工业意义和经济价值的大型矿床,对研究矿床成因、经济地质、环境地球化学具有重要意义。因此,对硫化物组成的精确分析是了解上述方向的重要途径。硫化物矿物的主微(痕)量元素的快速、精确定量分析一直以来备受关注,本文就近几十年来对硫化物矿物的定量分析进展作了详细介绍,重点评述了电子探针(EPMA)、X射线荧光光谱(XRF)、电感耦合等离子体质谱(ICP-MS和LA-ICPMS)和电感耦合等离子体发射光谱(ICP-AES)在硫化物矿物主微(痕)量分析中的应用。     

扫描电镜-X射线能谱仪在丹巴地区铂族矿物物相特征分析中的应用

丹巴地区铜镍硫化物铂族矿床品位低、铂族矿物颗粒细、铂族元素间的类质同象普遍,此类铂族资源的赋存状态研究及矿石的选冶长期以来都是较为棘手的问题。本文采用扫描电镜-X射线能谱仪器组合,对丹巴铜镍硫化物铂族矿床中含量达到1‰的元素进行快速的定性/定量分析,研究了铂族矿物原位的赋存状态和形貌特征。通过扫描电镜观察到该矿床的铂族矿物主要为砷铂矿、锑钯矿、碲锑钯矿,其次以自然铂、硫砷铑矿、硫砷铱矿,呈椭圆状、纺锤状等形式赋存于黄铁矿、磁黄铁矿及蛇纹石中,部分以类质同象的形式存在,极少量的铂与钯元素呈固溶体形式存在。X射线能谱分析表明该矿床中主要的铂族元素为Pt、Pd,其次为Ru、Rh、Ir、Os; 点分析表明砷铂矿中Pt的含量为52.84%,锑钯矿中Pd的含量为45.15%; 线扫描和面扫描分析表明铂族元素主要分布在含铁的硫化物中,Pt、Pd等铂族元素的含量与铁、镍的含量成正相关关系,反映了丹巴地区铂族元素亲铁、亲镍、亲硫的地球化学特征。     

XRF半定量分析技术在矿石光片鉴定中的应用

偏光显微镜反光镜下鉴定金属矿物是最常用、最快捷有效的方法,然而鉴定结果容易受到鉴定者主观因素或磨片情况的影响。为了更快速、准确地在反光镜下鉴定矿物,利用XRF半定量分析技术快速、无损、前处理简单等特点,以及磨平抛光的矿石矿物在半定量分析过程中能较好地避免楔入效应和阴影效应的有利因素,采取了先用XRF半定量分析测得的结果去反推矿物,再在显微镜下鉴定矿物的方法。以多金属硫化物矿石、含铀多金属矿石及含微量铀的矿石样品为例进行鉴定,结果表明,在鉴定前知道光片上的元素及其质量分数,通过地球化学方法和经验法反推矿物,结合显微镜观察需要鉴定的矿物,可有效避免忽略掉透明/半透明矿物（锡石）、小粒径矿物（沥青铀矿）、易混淆矿物（铀黑）,提高光片鉴定工作的效率和准确性。     

X射线荧光光谱法半定量分析高烧失量矿物的准确度研究

应用X射线荧光光谱半定量分析软件（SQX）分析未知样品时,SQX软件可对样品中的⁹F～⁹²U元素进行半定量分析,而对H₂O、C这些参数不能直接测定。对于烧失量和结晶水含量较高的铝土矿、CO₂含量较高的碳酸盐矿物、硫碳含量较高的硫化物金属矿等样品,平衡归一化计算时,未测定参数对样品中的Al₂O₃、SiO₂、CaO、MgO、Fe等主要元素分析结果影响较大,半定量分析数据的准确度较低。本文通过试验研究,提出了一种校正模式。该校正模式根据XRF半定量分析初步结果,选择性地对未知样品中的烧失量、结晶水、二氧化碳、硫等参数进行化学定量分析,将化学定量分析结果输入SQX,二次平衡归一计算得出新的半定量分析结果。实验结果表明,使用该校正模式分析铝土矿、碳酸盐矿物、硫化物金属矿中的多元素,平均准确度提高了2.6～4.5倍。本方法可快速、较为准确地测定铝土矿、碳酸盐矿物、硫化物金属矿等高烧失量矿物中的多元素。     

一种成矿溶液活化硫化矿物中成矿组分的理论模拟方法

以成矿组分活化地质理论、金属离子浓度综合平衡方程和硫化物离解平衡方程为基础,提出了成矿深液活化矿物中成矿组分的理论模拟方法。从定量分析的角度,为硫化矿物中成矿组分的活化及成矿作用研究中一些不易直接观察到的环节提供了新认识,探讨了这一方法的影响因素精度问题。     

硫化物矿物的表面反应及其在矿山环境研究中的应用

硫化物矿物的表面反应机理决定了以硫化物矿物为主的尾矿的重金属释放、吸附、解吸机制，其反应动力学与矿山环境污染程度存在内在联系。本文系统介绍了硫化物矿物的表面反应研究现状，包括反应机理、表面结构、表面位、反应产物、反应速率等，并指出了有待进一步研究的几个问题。     

硫化物矿物对银的表面吸附作用及其成矿意义

通过硫化物矿物对银离子的吸附实验研究表明，在５０℃时，硫化物矿物对溶液中银离子的等温饱和吸附量大小顺序是：方铅矿＞黄铜矿＞辉锑矿＞闪锌矿；当温度超过７０℃时，这个顺序变为：辉锑矿＞方铅矿＞黄铜矿＞闪锌矿。这与天然多金属矿床中硫化物矿物银的含量顺序是一致的。实验证明，硫化物具有把溶液中的银富集到固体（矿物中）达１０６量级以上的能力。这些结果极好地解释了多金属矿床中银在普通硫化物中含量大小的顺序及锑和银在矿床和矿物上密切共生的关系。     

长株潭近地表大气尘矿物特征及环境指示意义

通过X射线粉末衍射(XRD)、扫描电镜/能谱(SEM/EDX)方法对长沙、株洲和湘潭(以下简称长株潭)地区近地表大气尘中矿物成份进行分析研究,结果显示大气尘中含有石英、石膏、方解石、白云石、硫酸镉等23种自然矿物,还含有SiS2、Cadmium Arsenide(Cd3As2)、RhZn、Cr2Nb、NiTi、HfMo2等14种非自然矿物;近地表大气尘矿物形貌特征显示Cd元素主要富集在有矿物颗粒的地方,且呈近浸染状分布,能谱半定量分析,Cd含量可达4%,表明Cd易被吸附在矿物表面。分析长株潭地区大气尘中矿物成份、空间分布特征及其来源,对长株潭城市一体化具有及其重要的环境指导意义。     

硫化物矿物中痕量元素的激光剥蚀-电感耦合等离子体质谱微区分析进展

第一行过渡金属元素及痕量贵金属元素高度富集在硫化物矿物中,常形成具有工业意义的矿床,使得硫化物具有重大的经济价值。对天然硫化物矿物中的这些痕量金属元素丰度及其分布的研究,在矿石成因学、经济地质学、环境地球化学等领域具有重要的应用价值。激光剥蚀-电感耦合等离子体质谱(LA-ICP-MS)微区分析技术是一种强大的痕量元素分析工具,非常适合直接分析硫化物矿物中痕量元素的浓度及其空间分布。由于硫化物的激光剥蚀特性与硅酸盐及氧化物不同,分析校准用的标准物质又极度缺乏,严重阻碍了这一技术在硫化物矿物微区分析中的应用。本文评述了硫化物简介、硫化物中痕量金属元素分析的意义、LA-ICP-MS微区分析技术在硫化物矿物痕量元素分析中的优势及近年来的应用进展、硫化物分析中的干扰与校准、包含铂族元素及金的硫化物标准物质的研制进展及合成硫化物标准物质最有应用前景的方法。     

硫化矿原电池效应研究现状

硫化矿原电池效应普遍存在于金属硫化物矿山、硫化矿的人工开采与利用过程中,在浮选、湿法冶金、生物冶金、地球化学过程、重金属离子污染和酸性矿山排水的污染治理方面有重要作用,已引起高度重视。本文综述了硫化矿原电池反应原理、电化学研究方法及其在浮选、湿法冶金、生物冶金、地球化学过程、重金属离子污染和酸性矿山排水的污染与治理上的影响和应用现状。指出建立天然硫化物矿物原电池地球化学,从源头上实现消除或减弱硫化矿原电池效应导致的重金属离子和酸性矿山排水环境污染,将成为今后原电池效应在地学的重要研究方向。     

一个干旱地区毛矾石矿氧化带的矿物组合

在陆相古火山角砾岩筒中由火山热液蚀变产生的含黄铁矿次生石英岩中的硫化物,在特别干旱的条件下生成了以毛矾石及黄钾铁钒为主的13种钒类矿物组成的硫化矿床氧化带,并在其中聚集了毛矾石矿体。毛钒石矿是由反复进行的氧化-渗透淋滤作用而富集形成的。     

Mineralogy of gold in the Elshitsa massive sulphide deposit, Sredna Gora zone, Bulgaria

The Elshitsa volcanic hosted massive sulphide deposit occurs in the central part of the Srena Gora metallogenic zone in Bulgaria. The gold-bearing massive sulphide mineralization is considered to be the product of an island arc volcano-plutonic process and hydrothermal activity that took place during the Late Cretaceous. In addition to the major gold-hosted opaque minerals such as pyrite, chalcopyrite, sphalerite and galena there are minor phases of tennantite, goldfieldite, Se-bearing aikinite, native silver and bornite in the massive sulphide lenses and stringer zones. Most of the sulphide minerals are Se-bearing. All of the six mineral assemblages that were deposited during the pyrite and copper-pyrite stages of mineralization are gold-bearing. The gold tenor as a rule is less than 1 g/t. Native gold and electrum occur as blebs or intergranular particles in the sulphide minerals. Gold in the early massive pyrite is of submicroscopic type (< 0,1 μm) and of colloidal ori-gin. Pyrite deformation and recrystallization in the temperature range 250°–160 °C has led to Au and Ag migration to cracks and grain boundaries of the sulphide minerals. As a result of these process the native gold and electrum grain size increases from submicroscopic (< 0,1 μm) in the early colloform pyrite to microscopic (0,1–100 μm) and macroscopic (> 100 μm) in the late gold-sulphide assemblages. The electrum fineness in 41 individually studied grains varies between 780 and 992‰ with a mean of 895‰. Native silver was found in association with bornite. Cu, Te, Sb and Bi are the most common trace-elements in gold and electrum. The Cu-Zn-Pb association is most important as a Au-Ag-carrier. A model for gold behaviour during sulphide deformation is proposed involving coarsening of gold grain size from the earlier to the later sulphide mineral assemblages. Received: 4 December 1995 / Accepted: 23 September 1996     

硫化物固—液界面电化学效应实验探讨

硫化物作为一类重要的常见矿物，目前国内外对其表面矿物学特征研究有限。具体到硫化物固－液界面处的行为机理，前人的研究程度就更低了。笔者自行设计了一个Fe1-xS-Cr^6 原电池，通过实测电动势（E），t-E关系曲线，溶液可见光吸收谱及其λ－A关系曲线，阐明硫化物与Cr^6＋溶液间的界面行为机理。认为其界面行为过程为；硫化物溶解→离子反应（氧化还原）→吸附Cr^3 。该原电池与一般原电池结构不同，其主要差别在于将反应电极和测量电极分开，从而解决电极反应过程中的浓度极化问题，提高了电化学实验的精度。该研究成果有助于揭示矿物－液体相互作用机理，完善和丰富表面矿物学研究内容，深化化界面成矿理论，并对环境治理，矿物材料应用等开发领域具有重要的参考价值。     

Oxidative pre-treatment in thiosulphate leaching of sulphide gold ores

A diagnostic leaching showed that partial oxidation of the sulphide minerals in a gold ore was beneficial for thiosulphate leaching of gold. A pre-treatment process with oxidative ammoniacal solution enhanced the thiosulphate leaching of the sulphide ore, while the thiosulphate consumption was substantially reduced. The sulphide minerals partially decomposed in the pre-treatment process, exposing gold to the leach solution. Oxygen input by air bubbling and a longer contact time enhanced the oxidative ammonia pre-treatment process and hence accelerated subsequent thiosulphate leaching of the sulphide ore. Gold extraction in 0.8 M ammonia and 0.1 M thiosulphate solution after 24 h increased from 69% without pre-treatment to 81%, 84%, 90% and 94% respectively after 1, 3, 7 and 22 h pre-treatment. The consumption of sodium thiosulphate was 2.37 kg/t after 24 h leaching without pre-treatment, but was negligible after over 1 h oxidative ammonia pre-treatment. A counter-current leaching process was conducted in the leaching of the sulphide ore. The fresh leachant still gave higher leaching rates in contact with the pre-leached ore, while the pre-used leachant had significantly lower leaching kinetics and overall gold extraction in contact with the fresh ore. This 2-step counter-current leaching process proved that the leachant, other than the passivation, was the determinant factor causing the gold leaching rates to decrease after a certain time of leaching. The findings enable the thiosulphate leaching of high sulphide containing gold ores to be more efficient at lower thiosulphate consumption following the oxidative ammoniacal pre-treatment.     

The effectiveness of the very low frequency electromagnetic method (VLF-EM) in the exploration of sulphide mineralization in arid environments,case study from South Sinai Peninsula,Egypt

Very low frequency electromagnetic (VLF-EM) measurements were carried out in Wadi Isbayia area, south Sinai Peninsula, to test the efficiency of the VLF-EM method in the exploration of sulphide mineralization in arid environments. The VLF-EM field measurements, including tilt angle, real and imaginary components of the received VLF field, were carried out along fifteen profiles covering a quartz monzonite bedrock. Interpretation of the VLF measurements, in the light of geological information, has showed that sulphide minerals in the Wadi Isbayia area extend from the ground surface to a depth of about 200 m. However, the structural lineaments, especially faults, have controlled the distribution of the sulphide mineralization. A few of polished sections for rock samples, collected from the sites of the VLF-EM anomalies in the study area, have been prepared and examined by ore microscopy which confirmed the presence of pyrite and chalcopyrite as well as iron oxides, disseminated in the quartz monzonite bedrock. These results showed that the VLF-EM method is an effective tool in the exploration of sulphide minerals in the arid environments.     

安徽铜陵马山层控金铜硫矿床成因

安徽铜陵马山金铜硫矿床产于中石炭统黄龙组白云岩与灰岩地层之间,主矿体呈层状。矿石结构构造、成矿元素地层学分带、硫化物矿物微量元素地球化学和硫、铅同位素等特征表明,该矿床是中石炭世海底喷流沉积的块状硫化物矿床,成矿后在燕山期又受到了石英闪长岩体的改造和叠加。在长江中、下游断裂拗陷带中有许多硫化物矿床在成因上与马山相似。研究表明,在晚古生代,有一片洋壳拖着扬子板块往北向华北板块俯冲,故这类矿床形成于扬子古陆北缘的被动大陆边缘环境。     

The use of a new modifier,Kr6D,in differential sulphide flotation

The suitability of a new reagent, Kr6D, as a depressant for galena and sphalerite in a differential sulphide flotation stage has been tested. Small-scale laboratory flotation tests on pure sulphide minerals indicated that the reagent is capable of depressing both galena and sphalerite when used in small doses. At higher concentrations, chalcopyrite is also depressed. Single-stage batch-scale flotation tests have been carried out on bulk sulphide concentrates containing the three sulphide minerals. Kr6D has been compared with starch as a depressant both in the presence and in the absence of sulphur dioxide. In each case the new modifier has been shown to be more effective. When using sodium dichromate as a differential depressant in similar tests, it has been shown that the quantity necessary to achieve selectivity between chalcopyrite and galena may be considerably reduced if small quantities of Kr6D are added.     

Mineralogy and geochemistry of platinum-group elements in the Aguablanca Ni-Cu deposit (SW Spain)

Summary The Aguablanca Ni-Cu-(PGE) magmatic sulphide deposit is associated with a magmatic breccia located in the northern part of the Aguablanca gabbro (SW, Iberia). Three types of ores are present: semi-massive, disseminated, and chalcopyrite-rich veined ore. The principal ore minerals are pyrrhotite, pentlandite and chalcopyrite. A relatively abundant platinum-group mineral (PGM) assemblage is present and includes merenskyite, melonite, michenerite, moncheite and sperrylite. Moreover, concentrations of base and precious metals and micro-PIXE analyses were obtained for the three ore-types. The mineralogy and the mantle-normalised chalcophile element profiles strongly suggest that semi-massive ore represents mss crystallisation, whereas the disseminated ore represents an unfractionated sulphide liquid and the chalcopyrite-rich veined ore a Cu-rich sulphide liquid. Palladium-bearing minerals occur commonly enclosed within sulphides, indicating a magmatic origin rather than hydrothermal. The occurrences and the composition of these minerals suggest that Pd was initially dissolved in the sulphides and subsequently exsolved at low temperatures to form bismutotellurides. Negative Pt and Au anomalies in the mantle-normalised chalcophile element profiles, a lack of Cu-S correlation and textural observations (such as sperrylite losing its euhedral shape when in contact with altered minerals) suggest partial remobilisation of Pt, Au and Cu by postmagmatic hydrothermal fluids after the sulphide crystallisation. Authors’ addresses: R. Pi?a, L. Ortega, R. Lunar, Departamento de Cristalografía y Mineralogía, Facultad de Geología, Universidad Complutense de Madrid, ES-28040 Madrid, Spain; F. Gervilla, Facultad de Ciencias, Instituto Andaluz de Ciencias de la Tierra, Universidad de Granada-CSIC, Avda. Fuentenueva, s/n, ES-18002 Granada, Spain     

安徽铜陵冬瓜山铜、金矿床两阶段成矿模式

冬瓜山铜金矿床包括层状硫化物矿体、矽卡岩型和斑岩型矿体。层状硫化物矿体具层状形态和层控特征，矿石具块状、层纹状和揉皱状构造。燕山期岩浆岩及其岩浆流体对层状矿体进行了叠加和改造，改变了其结构构造、矿物组合和矿石成分，并在其上叠加蚀变和矿化。层状矿体中的铜是由含铜流体交代块状硫化物矿石形成的。冬瓜山铜金矿床经历了两次成矿作用：第一成矿阶段．在石炭纪中期，海底喷流作用形成了块状硫化物矿床，矿石成分以硫、铁矿为主；第二成矿阶段。燕山期岩浆侵人，一方面岩浆热液与围岩相互作用发生矽卡岩化、硅化、钾长石化、石英绢云母化和青磐岩化，形成矽卡岩型和斑岩型矿体，另一方面岩浆流体对块状硫化物矿体进行叠加改造，致使块状硫化物矿体富集铜等成矿物质。