利用扫描电镜和能谱技术研究四川会理铂钯矿床中的铂族矿物特征及铂族元素赋存状态

四川会理铂钯矿床是独立的铂族元素矿床,局部地段的铂钯含量已达工业品位,当前迫切需要详细掌握铂族矿物和铂族元素赋存状态。由于原矿铂族元素品位总体较低,采用化学分析方法分析测试只能间接研究铂族元素的赋存状态,所得结论并不全面。本文结合化学分析方法的测试结果,利用扫描电镜及能谱获得了会理铂钯矿床铂族矿物的精细特征。结果表明:该矿床中铂族元素主要是铂和钯;铑、铱、钌、锇含量很低,且未发现这四种元素的独立矿物。铂和钯有单质和与砷、碲、锑、铋形成的化合物;独立铂族矿物有17种,主要是自然铂、砷铂矿、砷钯铂矿或砷铂钯矿、钯铂铜矿或铂钯铜矿,其次可见少量承铂矿及其他铂族矿物。铂族矿物嵌布状态有两种——被包裹和粒间,被包裹占52.39%,粒间占47.62%。绝大多数铂族矿物呈他形粒状,只有少量砷铂矿晶形较好。铂族矿物粒径范围为1.36~32.7μm,大小差异大。有的铂族矿物表面具微孔结构,有的呈葡萄状,有的可见环边现象。接触方式以曲线接触为主,直线接触次之。这些信息为该矿床矿石选冶和铂族资源评价提供了科学依据。     

Mineralogical,geochemical, and age characteristics of the rocks of the Inagli dunite-clinopyroxenite-shonkinite massif with platinum-chromite and Cr-diopside mineralization (Aldan Shield)

We consider the mineralogical and geochemical features of the rocks of the Inagli dunite-clinopyroxenite-shonkinite massif with platinum-chromite and unique jewelry Cr-diopside mineralization, which is a reference object of concentric zonal complexes. The massif rocks, from dunites to pulaskites, including peridotites, clinopyroxenites, shonkinites, and melanocratic alkali syenites, form a single continuous comagmatic series. This is confirmed by a clear dependence of the compositions of olivine, pyroxene, phlogopites, and Cr-spinels on the MgO content of the rocks and on the behavior of trace elements in them. The similar compositions of pyroxenes and trace-element patterns of clinopyroxenite rocks and Cr-diopsidite veins indicate a genetic similarity of these rocks. The age and mineralogical and geochemical compositions of the rocks and the geologic and morphological features of the intrusion prove that the Inagli massif formed from high-K picritoid melts, which underwent gradual decompression solidification during the ascent and formed a cylindrical diapir-like body at the subsurface level in the Early Cretaceous. The new portions of differentiates supplied from the lower horizons of the magma column determined the complex composition of the massif: It has a concentric zonal structure cut by numerous radial-circular vein bodies of pegmatites and pure anchimonomineral rocks (Cr-diopsidites), in places, of jewelry quality.     

中国西部典型岩浆铂族元素矿床超常富集成矿机制

中国西部探明了一系列与新元古代以来幔源岩浆有关的镍铜铂族元素(platinum group elements, PGE)岩浆矿床,华北克拉通新元古代金川镍铜铂族硫化物矿床、峨眉山二叠纪大火成岩省金宝山铂族元素矿床等记录了不同构造环境幔源岩浆PGE超常富集成矿过程。亲铁性的铂族元素高度富集于地核,深部地幔起源、高程度部分熔融形成的镁铁质岩浆中PGE含量较高,地幔岩浆系统不同条件下铂族元素以纳米态元素簇、合金、硫化物熔体或超临界流体运移-聚集成矿,在阶段性岩浆房多阶段、多途径富集,成矿作用类型丰富。华北-华南克拉通岩石圈地幔PGE含量均略高于原始地幔值;华北克拉通岩石圈地幔PGE含量从古生代到中新生代略有降低,表明存在PGE抽取岩浆事件。中国西部新元古代以来的幔源岩浆源区PGE不亏损、岩浆活动时间长、岩浆-硫化物相互作用PGE多阶段富集及地幔柱岩浆动力学背景是PGE超常富集成矿的有利地质条件,其控制因素及动力学背景的认识对查明PGE成矿潜力和拓展资源储量具有重要意义。     

铂族元素的地球化学行为及全球主要铂族金属矿床类型

全球铂族金属矿床主要有6种类型,分别为：（1）镁铁质-超镁铁质层状岩体铂族金属矿床;（2）镁铁质-超镁铁质Cu-Ni硫化物矿床伴生的铂族金属矿床;（3）Urals杂岩体型铂族金属矿床;（4）蛇绿岩型铂族金属矿床;（5）与热液相关的铂族金属矿床;(6）外生型铂族金属矿床。除第4类型外其他类型的铂族矿床都具有经济意义。铂族金属矿床的形成主要与幔源岩浆性质及岩浆演化过程密切相关。大规模的幔源岩浆活动及在岩浆演化过程中具有产生硫饱和的条件是形成铂族金属矿床的有利条件,同时岩浆期后的热液作用能使铂族元素迁移并在特定条件下富集,对铂族金属矿床的形成有利。镁铁质-超镁铁质层状侵入体形成铂族金属矿床的有利条件是岩浆分异作用强,并且具有能产生高R因子的环境;镁铁质-超镁铁质Cu-Ni硫化物矿床中形成铂族金属矿床的有利条件是硫化物熔体的结晶分异作用;Urals型杂岩体中,由于岩浆在早期演化过程中硫的不饱和,形成的主要铂族矿物为Pt-Fe、Pt-Ir合金,且主要与铬铁矿共生,在岩浆演化硫饱和阶段可形成富Pd的铂族矿物,且与Cu-Fe-V-Ti-P金属共生;蛇绿岩型杂岩体中,主要形成的铂族矿物为含Ir- 、Os- 、Pt- 的合金或少量硫化物矿物,且主要赋存于铬铁矿中。     

Geochemistry of Platinum Group Elements in Mafic—Ultramafic Rocks of Xinjie Intrusion

The platinum group elements(PGE)in the mafic-ultramafic suite in the Xinjie layered intrusion and associated basalts and syenites were analyzed using neutron activation techniques after fire-assay preconcentration.On this basis,the geochemistry of the platinum group during the magmatic stage is discussed.With respect to PGE distribution,the Xijie layered intrusion is similar to the Bushveld ferruginous ultramafic series and is distinct from komatiite and Alpine-type peridotite.It is also similar to the Emeishan basalt in PGE characteristics,implying that the original magmas of them may be of the same type.     

"旧地重游",再次认识与评价:开拓铂族元素新资源的重要途径

简略介绍了几种在90年代报导或发现的工业铂族金属矿床,它们之中有一些是已知矿床重新认识和评价的新成果。     

Some Observations on the Determination of Gold and the Platinum-Group Elements in Black Shales

This research compares various ways of applying oxidative chemical decomposition to the analysis of gold-bearing black shale ores from the Russian Natalka and Sukhoj Log deposits. This study was conducted as part of the certification program for the Russian candidate black shale reference materials SLG-1 and SCHS-1 and also because of the paucity of data available on the determination of the platinum group elements (PGE) in analogous sample types. We report direct evidence of PGE volatilisation from black shale materials when processed in the presence of oxygen. We also developed a comprehensive analytical scheme for the quantitative determination of PGE in all phases (gaseous and ash) produced during slow combustion of carbonaceous materials in oxygen.
This study has shown that during combustion in oxygen at 600 °C, PGE contained in the Natalka black shale ores are lost as gaseous reaction products. Thus, the volatilized PGE (recovered in traps) account for up to 14% Pt, 40% Pd, 40% Ru and 10 % Ir relative to their total concentrations in a carbonaceous concentrate. It was also established that in the process of combustion, Au quantitatively remains in the ash cake.
In order to avoid the deleterious effects of oxygen on the volatility of the PGE, we propose a new comprehensive sample decomposition method based on the application of fluoroxidants such as BrF₃ and KBrF₄. This method was validated using samples of black shale ores and their processing products by comparing our results with those obtained independently using sealed autoclave processing of the same materials. It was shown that PGE in black shale ores and their processing products not only exist in commercially exploitable quantities but that a small proportion of PGE compounds are soluble in alcohol. We propose that in gold-bearing black shale ores, PGE are present as organometallic compounds.     

ICP-MS法测定化探样品中痕量金铂钯的富集分离方法研究

本方法用HCl和H_2O_2分解试样,以泡沫塑料富集Au、Pt和Pd,在酸性介质中解脱,用电感耦合等离子体质谱法测定化探样品中痕量金铂钯,研究了富集解脱介质及浓度。结果表明,在0.5%NaI+0.5%KBr+20%HCl介质中泡沫塑料对Au、Pt、Pd的吸附率大于95%;在1%硫脲+2%KSCN+2%HCl解脱介质中Au、Pt、Pd的回收率高于90%。方法检出限为Au 0.072 ng/g,Pt 0.17 ng/g,Pd 0.096 ng/g,标准物质的测定值与标准值基本一致,准确度和精密度满足相关规范要求,因此该方法对化探样品中痕量金铂钯的测定有一定实用性。     

铂电阻温度传感器现场检定和实验室检定不确定度评定对比分析

目前我国自动气象站铂电阻温度传感器的检定方式有现场检定和实验室检定两种。根据《JJG(气象)002-2015自动气象站铂电阻温度传感器检定规程》的指导方法,分别对相同的铂电阻温度传感器开展现场检定和实验室检定,并通过GUM法对两种检定方式的检定结果进行测量不确定度评定,对比两种检定方式的测量不确定度,结果表明现场检定中测量重复性引入的不确定度和测量设备引入的不确定度较实验室检定更高。分析两种检定方式的测量不确定度产生差异的原因,建议国家级自动气象站的铂电阻传感器采用实验室检定的方式开展计量检定工作。     

华北与黔西地区晚古生代煤层中铂族元素赋存状态及来源

运用电离耦合等离子体质谱仪(ICP-MS)对中国华北和黔西地区晚古生代煤系中54个样品的铂族元素(PGEs)进行了分析。分析结果表明,煤中铂族元素主要是通过岩浆热液活动、低温热液流体、同沉积火山灰、陆源碎屑输入和海水等诸种地质作用形成的,前3种作用是造成煤中铂族元素异常的主要原因。低含量的铂族元素(正常背景值)主要来源于硅质陆源区,煤中铂族元素的背景值为:Ru=0.005μg/g,Rh=0.014μg/g,Pd=0.181μg/g,Ir=0.001μg/g,Pt=0.037μg/g。煤中铂族元素以Pt-Pd分配模式为特征,并且Pd>Pt,Pd>>Ru、Rh、Ir,其中Pd在煤中的背景值约为地壳平均值的18倍。Pd、Pt与煤灰分呈正相关,表现出它与无机矿物的亲和性。