LA-ICP-MS trace element analysis of pyrite from the Xiaoqinling gold district, China: Implications for ore genesis

The Xiaoqinling district, the second largest gold producing district in China, is located on the southern margin of the North China Craton. It consists of three ore belts, namely, the northern ore belt, the middle ore belt and the southern ore belt. Pyrite from the Dahu gold deposit in the northern ore belt and Wenyu and Yinxin gold deposits in the southern ore belt were investigated using a combination of ore microscopy and in-situ laser-ablation inductively-coupled plasma-mass spectrometry (LA-ICP-MS). A range of trace elements was analyzed, including Au, Te, Ag, Pb, Bi, Cu, Co, Ni, Zn, Mo, Hg, As and Si. The results show that there are no systematic differences between the trace element compositions of pyrite in the three deposits from different ore belts. In general, Au concentrations in pyrite are low (from < 0.01 ppm to 2.2 ppm) but Ni concentrations are rather high (up to 8425 ppm). A four-stage mineralization process is indicated by microscopic and field observations and this can be related to the systematic trace element differences between distinct generations of pyrite. Stage I precedes the main gold mineralization stage; pyrite of this stage has the lowest Au concentrations. Stages II and III contributed most of the gold to the ore-forming system. The corresponding pyrite yielded the highest concentrations of Au and Ni. Our microscopic observations suggest that pyrite in the main gold mineralization stage precipitated simultaneously with molybdenite that has been previously dated as Indosinian (~ 218 Ma by Re–Os molybdenite dating), indicating the Indosinian as the main gold mineralization stage. The Indosinian mineralization age and the geological and geochemical features of these gold deposits (e.g., low salinity, CO₂-rich ore fluids; spatial association with large-scale compressional structures of the Qinling orogen; δ¹⁸O and δD data suggestive of mixing between metamorphic and meteoric waters; δ³⁴S and Pb-isotopic data that point to a mixed crustal-mantle source) all point to typical orogenic-type gold deposits. High Ni concentrations (up to 8425 ppm) of pyrite possibly linked to deep-seated mafic/ultramafic metamorphic rocks provide further evidence on the orogenic gold deposit affinity, but against the model of a granitic derivation of the mineralizing fluid as previously suggested by some workers. Generally low Au concentration in pyrite is also consistent with those from worldwide orogenic gold deposits. Therefore, the gold mineralization in the Xiaoqinling district is described as orogenic type, and is probably related to Indosinian collision between the North China Craton and the Yangtze Craton.     

Trace elements in pyrite from the Petropavlovsk gold–porphyry deposit (Polar Urals): Results of LA-ICP-MS analysis

The first study of the pyrite composition from gold deposit in the Urals by the LA-ICP-MS method has been carried out. In the pyrite high contents of Au (up to 49 ppm), Ag (105 ppm), and other micronutrients (As (417 ppm), Ag (105 ppm), Co (2825 ppm), Ni (75 ppm), Cu (1442 ppm), and Zn (19 ppm)) were detected. Furthermore, an increase in the concentrations of trace elements from early to later generations of pyrite (from Py-1 to Py-3) Au, Ag, Te, Sn, Te, and Bi and depletion of Co, As, and Ni have been revealed. Gold is mainly concentrated in the pyrite of the second generation (Py-2) and occurs mostly as an “invisible” form with prevalence of nano-sized particles of native Au, similar in composition to electrum AuAg, as well as Au- and Au–Ag tellurides. The presence in the pyrite of admixtures of Cu, Co, Ni, Pb, As, and Te, possibly favors the entrance of Au into it (up to 5–50 ppm), while in common pyrite, poor in the mentioned impurities, the gold content is <1 ppm.     

LA-ICPMS原位微区面扫描分析技术及其矿床学应用实例

LA-ICPMS原位微区面扫描技术的发展对解析具有包裹体、环带结构的矿物或受多期岩浆/热液活动影响形成的溶蚀再结晶的矿物具有重要的地质意义。黄铁矿作为最普遍的硫化物种类之一,可形成于各种类型矿床中,其微量元素组份记录了矿床形成过程的重要信息。通过LA-ICPMS原位微区面扫描技术获得的黄铁矿晶体内部结构组份信息可用来限定成矿流体的性质、厘定成矿流体的演化规律、示踪成矿物质来源、约束变形变质作用过程中元素的活化和迁移行为,以及约束矿床成因等。本次研究选取了内蒙古二连盆地中巴彦乌拉大型铀矿床、辽宁青城子地区榛子沟铅锌矿、加拿大Pardo砂金矿中的黄铁矿作为研究对象,运用原位微区LA-ICPMS元素面扫描技术揭示其内部组份及结构信息,探索该技术在不同类型矿床中的应用价值。巴彦乌拉大型砂岩型铀矿床中的黄铁矿的内部组构信息显示成矿体系的p H和Eh对硫酸盐还原细菌活动均有影响,并控制与之相关的铀矿化;且成矿体系的p H和Eh受到外界不断供给的地下水的影响,呈振荡性变化。辽宁榛子沟铅锌矿中的黄铁矿的内部组构信息显示矿化过程受到了至少两期流体活动的叠加影响,包括早期同沉积时期的流体以及晚期与燕山期岩浆活动有关的热液流体。加拿大Pardo金矿中黄铁矿的内部组构信息显示矿床中半自形-自形的黄铁矿实际包含碎屑成因的磨圆状核部及后期热液活动形成的增生边;金主要呈浸染状分布在碎屑成因的黄铁矿核部,后期热液活动对金矿化影响微弱。     

Trace-element characteristics of different pyrite types in Mesoarchaean to Palaeoproterozoic placer deposits

A comparative in situ LA-ICP MS trace-element study on pyrite from three different, variably auriferous, Archaean to Palaeoproterozoic palaeoplacer deposits in the Ouro Fino Syncline (Quadrilátero Ferrífero; Brazil), the Elliot Lake area north of Lake Huron (SE Canada) and several deposits within the Witwatersrand Basin (South Africa) revealed systematic differences between morphologically different pyrite types and between the various palaeoplacer deposits. Especially the Ni and Au concentrations as well as Co/Ni and Mo/Ni ratios were found to be systematically different in detrital compact, detrital porous and post-sedimentary/hydrothermal pyrite grains from different source areas. High Co/Ni ratios and low Au concentrations are typical of post-sedimentary pyrite, which is hydrothermal in origin. In contrast, relatively low Co/Ni ratios and high Au contents characterise detrital porous banded and concentric pyrite grains (Au > 1 ppm), which are syn-sedimentary in origin. In the Elliot Lake area and the Witwatersrand Basin, detrital compact rounded pyrite is characterised by high Co/Ni ratios, which is in agreement with derivation from a hydrothermal source. Low Au concentrations in this pyrite type support the contention of the gold and the pyrite in these deposits coming from different source rocks. In contrast, derivation from an originally diagenetic pyrite is suggested for the detrital compact pyrite in the Ouro Fino Syncline because of low to intermediate Co/Ni ratios. High Au contents may indicate a genetic relationship between pyrite and gold there. Systematic differences exist between the three areas with respect to Au, Ni, Co, Mo and Cu distributions in detrital pyrite, which reflects differences in the provenance. A predominantly mafic/ultramafic source is indicated for the Ouro Fino, a felsic source for the Elliot Lake, and a mixed felsic–mafic provenance for the Witwatersrand pyrite populations. Independently of pyrite type, the higher Au endowment of the studied Witwatersrand and Ouro Fino conglomerates are also reflected by an overall higher Au concentration in the respective pyrite grains compared to the relatively Au-poor samples from Elliot Lake. In general, a strong positive correlation between Au and Pb levels in the various pyrite grains is noted. Analogous to Pb, which is well known for not being easily accommodated in the pyrite crystal lattice but occurring as discrete PbS phases, Au is considered to be present mainly in the form of discrete Au phases in minute pores and interstices of the pyrite grains rather than within the pyrite lattice.     

胶东焦家金成矿带2420~3206 m垂深金矿物和黄铁矿微量元素特征

在胶东莱州吴一村地区完成的3266.06 m深钻,是目前焦家金成矿带最深见矿钻孔,研究钻孔揭露的深部矿石中金矿物及黄铁矿微量元素特征,对探讨深部成矿作用演化具有重要意义。笔者采取深钻中2420~3206 m垂深的岩（矿）芯样品进行了详细的岩相学和矿相学研究,结合扫描电镜和电子探针微区分析,研究了矿石中金矿物的赋存状态和成分。对不同成矿阶段形成的黄铁矿进行了LA-ICPMS微量元素分析。研究结果表明,深部矿石中载金矿物主要为黄铁矿,其次为石英、黄铜矿、方铅矿,可见金主要以自然金和银金矿的形式存在,以晶隙金和裂隙金为主,其次为包体金。与浅部金矿床比较,深部金的成色较高。黄铁矿分为6种类型,第Ⅰ成矿阶段形成富Co型黄铁矿Py1,第Ⅱ成矿阶段形成富Ni型黄铁矿Py2a和Py2b,第Ⅲ成矿阶段形成富Au、As型黄铁矿Py3a和富Au、Ag、Pb、Bi型黄铁矿Py3b,第Ⅳ成矿阶段形成贫微量元素黄铁矿Py4。其中,Py1和Py2a发生强烈破碎,裂隙表面对热液中的Au络合物产生吸附作用,对金沉淀富集起重要作用。黄铁矿中Co、Ni、As等微量元素主要以类质同象形式赋存,而Au、Ag、Cu、Pb、Zn、Bi等主要以纳米级、微米级矿物包体形式赋存。Pb+Bi、Cu+Pb+Zn、Te+Bi与Au+Ag呈明显正相关,而Au与As相关性较差。黄铁矿中Co、Ni含量较低,而Au+Ag+As或Au+Ag+Pb+Bi+Cu含量较高指示成矿有利。另外,黄铁矿中Co、Ni含量较高,并且破碎强烈,成矿相关元素含量较高也指示成矿有利。     

Trace metal nanoparticles in pyrite

Hydrothermal pyrite contains significant amounts of minor and trace elements including As, Pb, Sb, Bi, Cu, Co, Ni, Zn, Au, Ag, Se and Te, which can be incorporated into nanoparticles (NPs). NP-bearing pyrite is most common in hydrothermal ore deposits that contain a wide range of trace elements, especially deposits that formed at low temperatures. In this study, we have characterized the chemical composition and structure of these NPs and their host pyrite with high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), analytical electron microscopy (AEM), and electron microprobe analysis (EMPA). Pyrite containing the NPs comes from two types of common low-temperature deposits, Carlin-type (Lone Tree, Screamer, Deep Star (Nevada, USA)), and epithermal (Pueblo Viejo (Dominican Republic) and Porgera (Papua New-Guinea)).EMPA analyses of the pyrite show maximum concentrations of As (11.2), Ni (3.04), Cu (2.99), Sb (2.24), Pb (0.99), Co (0.58), Se (0.2), Au (0.19), Hg (0.19), Ag (0.16), Zn (0.04), and Te (0.04) (in wt.%). Three types of pyrite have been investigated: “pure” or “barren” pyrite, Cu-rich pyrite and As-rich pyrite. Arsenic in pyrite from Carlin-type deposits and the Porgera epithermal deposit is negatively correlated with S, whereas some (colloform) pyrite from Pueblo Viejo shows a negative correlation between As + Cu and Fe. HRTEM observations and SAED patterns confirm that almost all NPs are crystalline and that their size varies from 5 to 100 nm (except for NPs of galena, which have diameters of up to 500 nm). NPs can be divided into three groups on the basis of their chemical composition: (i) native metals: Au, Ag, Ag–Au (electrum); (ii) sulfides and sulfosalts: PbS (galena), HgS (cinnabar), Pb–Sb–S, Ag–Pb–S, Pb–Ag–Sb–S, Pb–Sb–Bi–Ag–Te–S, Pb–Te–Sb–Au–Ag–Bi–S, Cu–Fe–S NPs, and Au–Ag–As–Ni–S; and (iii) Fe-bearing NPs: Fe–As–Ag–Ni–S, Fe–As–Sb–Pb–Ni–Au–S, all of which are in a matrix of distorted and polycrystalline pyrite. TEM-EDX spectra collected from the NPs and pyrite matrix document preferential partitioning of trace metals including Pb, Bi, Sb, Au, Ag, Ni, Te, and As into the NPs. The NPs formed due to exsolution from the pyrite matrix, most commonly for NPs less than 10 nm in size, and direct precipitation from the hydrothermal fluid and deposition into the growing pyrite, most commonly for those > 20 nm in size. NPs containing numerous heavy metals are likely to be found in pyrite and/or other sulfides in various hydrothermal, diagenetic and groundwater systems dominated by reducing conditions.     

Multi-stage growth and invisible gold distribution in pyrite from the Kundarkocha sediment-hosted gold deposit,eastern India

Gold mineralization at Kundarkocha, India, is hosted in sheared gray quartz veins that were emplaced in carbonaceous pyritic phyllite. Gold occurs as enclosed grains within sulfides and free grains in quartz. Based on characteristic textural and chemical features, documented by X-ray element imaging, electron probe microanalysis and laser-ablation inductively-coupled plasma mass spectrometry analyses, four pyrite types were identified in carbonaceous phyllites and auriferous veins. Rock-hosted fine-grained syn-sedimentary to early diagenetic pyrite framboids (PyI) have lower contents of Co and As but consistently high gold values. Pyrite of the next generation (PyII) has numerous silicate and rare sulfide inclusions; lower contents of Co and Ni, moderate As values; the highest mean value of invisible gold and maximum concentrations of trace elements such as Li, Ti, Zn, Rb, Sr, Y, Zr, Nb, La, Ce, Ta, Th, U and Cr. Pyrite of the third generation (PyIII) shows evidence of overgrowth over PyII, contains both silicate and sulfide inclusions, and are characterized by moderate contents of Co, high Ni and low Au values and higher concentrations of large ion lithophile elements, but lesser amount of high field strength elements. Pyrites of the latest type (PyIV) occur as polycrystalline aggregates that contain inclusions of gold, sulfides and rare silicates, show oscillatory zoning of Co and As and the lowest concentrations of all other trace elements. Successive decrease in contents of majority of trace elements from PyII to PyIV is attributed to fluid-assisted recrystallization during diagenesis and low grade metamorphism.Later generation pyrites (PyII through PyIV) exhibit higher Au contents regardless of their As values, indicating occurrence of invisible gold mostly as nanoparticles, at times reaching up to 500 ppm. Unlike the majority of trace elements that underwent large-scale remobilizations, gold was somehow locked up in pyrite resulting in a rather lean deposit at Kundarkocha.     

An evaluation of trace element release associated with acid mine drainage

The determination of trace element release from geologic materials, such as oil shale and coal overburden, is important for proper solid waste management planning. The objective of this study was to determine a correlation between trace element residency and concentration to trace element release using the following methods: (1) sequential selective dissolution for determining trace element residencies, (2) toxicity characteristic leaching procedure (TCLP), and (3) humidity cell weathering study simulating maximum trace element release. Two eastern oil shales were used, a New albany shale that contains 4.6 percent pyrite, and a Chattanooga shale that contains 1.5 percent pyrite. Each shale was analyzed for elemental concentrations by soluble, adsorbed, organic, carbonate, and sulfide phases. All leachates were analyzed to determine total trace element concentrations. The results of the selective dissolution studies show that each trace element has a unique distribution between the various phases. Thus, it is possible to predict trace element release based on trace element residency. The TCLP results show that this method is suitable for assessing soluble trace element release but does not realistically assess potential hazards. The results of the humidity cell studies do demonstrate a more reasonable method for predicting trace element release and potential water quality hazards. The humidity cell methods, however, require months to obtain the required data with a large number of analytical measurements. When the selective dissolution data are compared to the trace element concentrations in the TCLP and humidity cell leachates, it is shown that leachate concentrations are predicted by the selective dissolution data. Therefore, selective dissolution may represent a rapid method to assess trace element release associated with acid mine drainage.     

邦布造山型金矿床黄铁矿原位微量元素特征及其成矿意义数

邦布金矿床是目前在雅江缝合带研究程度最高且唯一正在开采的大型造山型金矿床.为理解邦布金矿床中金的来源及迁移沉淀机制,运用原位微区分析技术对邦布矿床中不同世代含金黄铁矿的微量元素组成进行测定.结果显示,亲铁元素Co、Ni主要以类质同象的形式进入到黄铁矿的晶格中替代Fe,As和Se呈类质同象形式替换S,Au是以纳米颗粒的形式均匀或不均匀的分布于不同产状的黄铁矿之中.邦布金矿床中的含金石英脉中三个不同世代的黄铁矿的Co/Ni比值均小于1,保存了围岩中黄铁矿的信息,显示出一种沉积或沉积改造成因.Au与As和Se具有明显的正相关关系,As和Se对Au的迁移及富集具有重要的作用.      

金矿床中环带状黄铁矿及其生长演化过程的研究

利用电子探针对黔南卡林型金矿床中环带状黄铁矿进行研究，把它划分成三种类型，并分别测定内外带中Ａｓ、Ｓｂ、Ａｕ、Ｈｇ和Ｔｌ等微量元素的含量，绘制了以步间距１μｍ，横穿环带的这五种元素的Ｘ射线强度变化曲线图，图中清楚显示出环带起因于微量元素含量的变化，这五种元素在微观尺度上呈正相关的振荡式变化，具有同源性。讨论黄铁矿经由胶体粒子的聚集、固结与结晶的生长演化过程，提供了低温热液可能是一种富含成矿质的多相     

胶东三山岛金矿床黄铁矿显微结构和微量元素特征:对金富集机制的指示

三山岛金矿床是位于胶东金矿集区西北部的超大型破碎带蚀变岩型金矿床.该矿床细致的矿相学及元素地球化学研究尚有不足,限制了对其金富集机制及过程的理解.基于野外地质调查和室内矿相学研究将该矿床划分为4个成矿阶段:石英?绢云母?黄铁矿阶段(I)、石英?金?黄铁矿阶段(I I)、石英?金?多金属硫化物阶段(I I I)和碳酸盐?...     

山东莱州曲家金矿黄铁矿微量元素对成矿过程的指示

曲家金矿位于我国重要的蚀变岩型金矿矿集区之焦家金矿带的中段，矿床赋存标高为-726～-1 334 m。为研究黄铁矿的演化及其对金成矿过程的指示，运用LA-ICP-MS分析黄铁矿原位微量元素含量，结合岩相学观察和点群分析对黄铁矿进行了分类。发现黄铁矿中Co、Ni、As等微量元素主要以类质同像形式赋存，而Au、Ag、Cu、Zn、Pb、Bi等元素主要以纳米级、微米级矿物包裹体形式赋存。黄铁矿主要分为5种类型：富Co型Py1,富Ni型Py2,富Au、As型Py3,富Au、Ag、Pb、Bi型Py4及“干净”型Py5。黄铁矿微量元素特征指示成矿物质可能主要来源于前寒武纪变质基底岩石和中生代岩浆岩，少量来源于地幔，成矿热液可能属变质热液、岩浆热液和浅部大气降水的混合成因。不同类型黄铁矿反映成矿热液由富Co、Ni经富As、Au向富Pb、Bi、Au、Ag演化。Py1和Py2形成后受构造活动影响发生强烈破碎，裂隙表面对热液中金络合物增强的吸附作用促使金在裂隙中沉淀，对金的富集成矿可能起重要作用。Co、Ni含量较低，同时Au、Ag、As、Pb、Bi等元素含量较高的黄铁矿与成矿作用有密切关系。另外，黄铁矿中C...     

Invisible gold in arsenian pyrite and arsenopyrite from a multistage Archaean gold deposit: Sunrise Dam,Eastern Goldfields Province,Western Australia

The Sunrise Dam gold mine (11.1 Moz Au) is the largest deposit in the Archaean Laverton Greenstone Belt (Eastern Goldfields Province, Yilgarn Craton, Western Australia). The deposit is characterized by multiple events of fluid flow leading to repeated alteration and mineralization next to a major crustal-scale structure. The Au content of arsenian pyrite and arsenopyrite from four mineralizing stages (D₁, D₃, D_4a, and D_4b) and from different structural and lithostratigraphic environments was measured using in situ laser ablation inductively coupled plasma mass spectrometry. Pyrite contains up to 3,067 ppm Au (n = 224), whereas arsenopyrite contains up to 5,767 ppm (n = 19). Gold in arsenopyrite (D_4a stage) was coprecipitated and remained as “invisible gold” (nanoparticles and/or lattice-bound) during subsequent deformation events. In contrast, gold in pyrite is present not only as “invisible gold” but also as micrometer-size inclusions of native gold, electrum, and Au(Ag)–tellurides. Pristine D₁ and D₃ arsenian pyrite contains relatively low Au concentrations (≤26 ppm). The highest Au concentrations occur in D_4a arsenian-rich pyrite that has recrystallized from D₃ pyrite. Textures show that this recrystallization proceeded via a coupled dissolution–reprecipitation process, and this process may have contributed to upgrading Au grades during D_4a. In contrast, Au in D_4b pyrite shows grain-scale redistribution of “invisible” gold resulting in the formation of micrometer-scale inclusions of Au minerals. The speciation of Au at Sunrise Dam and the exceptional size of the deposit at province scale result from multiple fluid flow and multiple Au-precipitating mechanisms within a single plumbing system.     

Paragenesis and geochemistry of ore minerals in the epizonal gold deposits of the Yangshan gold belt,West Qinling,China

Six epizonal gold deposits in the 30-km-long Yangshan gold belt, Gansu Province are estimated to contain more than 300 t of gold at an average grade of 4.76 g/t and thus define one of China's largest gold resources. Detailed paragenetic studies have recognized five stages of sulfide mineral precipitation in the deposits of the belt. Syngenetic/diagenetic pyrite (Py₀) has a framboidal or colloform texture and is disseminated in the metasedimentary host rocks. Early hydrothermal pyrite (Py₁) in quartz veins is disseminated in metasedimentary rocks and dikes and also occurs as semi-massive pyrite aggregates or bedding-parallel pyrite bands in phyllite. The main ore stage pyrite (Py₂) commonly overgrows Py₁ and is typically associated with main ore stage arsenopyrite (Apy₂). Late ore stage pyrite (Py₃), arsenopyrite (Apy₃), and stibnite occur in quartz ± calcite veins or are disseminated in country rocks. Post-ore stage pyrite (Py₄) occurs in quartz ± calcite veins that cut all earlier formed mineralization. Electron probe microanalyses and laser ablation-inductively coupled plasma mass spectrometry analyses reveal that different generations of sulfides have characteristic of major and trace element patterns, which can be used as a proxy for the distinct hydrothermal events. Syngenetic/diagenetic pyrite has high concentrations of As, Au, Bi, Co, Cu, Mn, Ni, Pb, Sb, and Zn. The Py₀ also retains a sedimentary Co/Ni ratio, which is distinct from hydrothermal ore-related pyrite. Early hydrothermal Py₁ has high contents of Ag, As, Au, Bi, Cu, Fe, Sb, and V, and it reflects elevated levels of these elements in the earliest mineralizing metamorphic fluids. The main ore stage Py₂ has a very high content of As (median value of 2.96 wt%) and Au (median value of 47.5 ppm) and slightly elevated Cu, but relatively low values for other trace elements. Arsenic in the main ore stage Py₂ occurs in solid solution. Late ore stage Py₃, formed coevally with stibnite, contains relatively high As (median value of 1.44 wt%), Au, Fe, Mn, Mo, Sb, and Zn and low Bi, Co, Ni, and Pb. The main ore stage Apy₂, compared to late ore stage arsenopyrite, is relatively enriched in As, whereas the later Apy₃ has high concentrations of S, Fe, and Sb, which is consistent with element patterns in associated main and late ore stage pyrite generations. Compared with pyrite from other stages, the post-ore stage Py₄ has relatively low concentrations of Fe and S, whereas As remains elevated (2.05～3.20 wt%), which could be interpreted by the substitution of As^? for S in the pyrite structure. These results suggest that syngenetic/diagenetic pyrite is the main metal source for the Yangshan gold deposits where such pyrite was metamorphosed at depth below presently exposed levels. The ore-forming elements were concentrated into the hydrothermal fluids during metamorphic devolatilization, and subsequently, during extensive fluid–rock interaction at shallower levels, these elements were precipitated via widespread sulfidation during the main ore stage.     

In Situ Determination of Au and Cu in Natural Pyrite by Near‐Infrared Femtosecond Laser Ablation‐Inductively Coupled Plasma‐Quadrupole Mass Spectrometry: No Evidence for Matrix Effects

Gold and copper concentrations were determined in natural pyrite by near‐infrared femtosecond LA‐ICP‐QMS, using both sulfide reference materials (pyrrhotite Po‐726 and in‐house natural chalcopyrite Cpy‐RM) and NIST SRM 610 as external calibrators. Firstly, using NIST SRM 610 as the external calibrator, we calculated the Au concentration in Po‐726 and the Cu concentration in Cpy‐RM. The calculated concentration averages for Au and Cu were similar to the values published for Po‐726 and Cpy‐RM, respectively. Secondly, we calculated Au and Cu concentrations taking NIST SRM 610 as an unknown sample and using Po‐726 and Cpy‐RM as external calibrators. Again, the average values obtained closely reflected the preferred concentrations for NIST SRM 610. Finally, we calculated Au and Cu concentrations in natural pyrite using sulfide and silicate reference materials as external calibrators. In both cases, calculated concentrations were very similar, independent of the external calibrator used. The aforementioned data, plus the fact that we obtained very small differences in relative sensitivity values (percentage differences are between 5% and 17% for ⁵⁷Fe, ⁶³Cu and ¹⁹⁷Au) on analyses of silicate and sulfide RMs, indicate that there were no matrix effects related to the differences in material composition. Thus, it is possible to determine Au and Cu in natural sulfides using NIST silicate glasses as an external calibrator.     

辽宁生金皋和赵家堡子金矿黄铁矿的找矿标志

在辽宁生金皋地区和赵家堡子地区的找金过程中,采用黄铁矿矿物学方法,对黄铁矿晶体的形态、主要成份和微量元素特征等进行分析。结果表明以五角十二面体晶形为特征的半自形细粒状黄铁矿含金性较高;黄铁矿主成份S、Fe含量相对低,而黄铁矿中Cu、Pb、Zn、Au、Ag等微量元素总量相对高的黄铁矿分布区域与金矿化关系密切;提出赵家堡子地区具备找到一处中型以上金矿的前景,而在生金皋地区找到大型金矿床的可能性很小,但有望找到伴生金矿床。     

胶东邓格庄金矿床矿物化学研究

本文研究了胶东邓格庄金矿床金银系列矿物、黄铁矿、石英和方解石的化学成分,金银系列矿物主要为银金矿和金银矿,含Pt等微量元素,与金矿化关系密切的黄铁矿以Fe亏损占优势,富Au、Te、As和Ag为特点;石英具高的Al、K、Cu、Pb和Zn,低的Li含量;黄铁矿、石英和方解石的稀土元素组成指示成矿热液可能有二种来源,方解石的稀土元素组成指示成矿热液为岩浆或深部来源。     

Specific composition of native silver from the Rogovik Au–Ag deposit,Northeastern Russia

The first data on native silver from the Rogovik Au–Ag deposit in northeastern Russia are presented. The deposit is situated in central part of the Okhotsk–Chukchi Volcanic Belt (OCVB) in the territory of the Omsukchan Trough, unique in its silver resources. Native silver in the studied ore makes up finely dispersed inclusions no larger than 50 μm in size, which are hosted in quartz; fills microfractures and interstices in association with küstelite, electrum, acanthite, silver sulfosalts and selenides, argyrodite, and pyrite. It has been shown that the chemical composition of native silver, along with its typomorphic features, is a stable indication of the various stages of deposit formation and types of mineralization: gold–silver (Au–Ag), silver–base metal (Ag–Pb), and gold–silver–base metal (Au–Ag–Pb). The specificity of native silver is expressed in the amount of trace elements and their concentrations. In Au–Ag ore, the following trace elements have been established in native silver (wt %): up to 2.72 S, up to 1.86 Au, up to 1.70 Hg, up to 1.75 Sb, and up to 1.01 Se. Native silver in Ag–Pb ore is characterized by the absence of Au, high Hg concentrations (up to 12.62 wt %), and an increase in Sb, Se, and S contents; the appearance of Te, Cu, Zn, and Fe is notable. All previously established trace elements—Hg, Au, Sb, Se, Te, Cu, Zn, Fe, and S—are contained in native silver of Au–Ag–Pb ore. In addition, Pb appears, and silver and gold amalgams are widespread, as well as up to 24.61 wt % Hg and 11.02 wt % Au. Comparison of trace element concentrations in native silver at the Rogovik deposit with the literature data, based on their solubility in solid silver, shows that the content of chalcogenides (S, Se, Te) exceeds saturated concentrations. Possible mechanisms by which elevated concentrations of these elements are achieved in native silver are discussed. It is suggested that the appearance of silver amalgams, which is unusual for Au–Ag mineralization not only in the Omsukchan Trough, but also in OCVB as a whole, is caused by superposition of the younger Dogda–Erikit Hg-bearing belt on the older Ag-bearing Omsukchan Trough. In practice, the results can be used to determine the general line of prospecting and geological exploration at objects of this type.     

The determination of minor and trace element associations in coal using a sequential microwave digestion procedure

A sequential extraction procedure, using acid digestion in a CEM MDS-81D® microwave system, is reported for the investigation of trace and minor element associations in coal in (1) mineral phases other than pyrite, (2) pyrite and (3) the organic matrix. The concentrations of sulphate, pyrite and organic sulphur can also be determined by this method. The extract solutions from each stage are rapidly analysed by ICP-AES. The association of major, minor and trace elements with mineral and organic phases is suggested for a suite of certified reference coal samples. In stage 1, a significant percentage of the total Ba, Co, Cr, Cu, Mn, Ni, Pb and Sr was extracted suggesting an association with silicate, carbonate, sulphate and phosphate minerals for these elements. In stage 2, a proportion of the Cu, Mn, Ni, Pb and Zn was dissolved implying the occurrence of these elements in pyrite. An association with the organic matrix is suggested for Cr and also for Ba and Sr in lower rank coals.     

湖南龙山金锑矿黄铁矿微量元素特征及其对成矿过程的指示

黄铁矿中的微量元素含量既可提供元素赋存状态的信息,又可示踪热液成矿过程。利用电子探针对龙山金锑矿赋矿地层新鲜板岩、蚀变围岩以及矿石中黄铁矿的多种微量元素进行了分析,研究结果表明:沉积黄铁矿中Au主要以纳米颗粒形式存在;热液黄铁矿中既有固溶体金,也有纳米金。沉积黄铁矿中Co、Ni、Sb、Mn、Te可能以固溶体形式存在,As、Pb、Zn、Cu、Ag以包裹体形式存在;热液黄铁矿中As、Sb、Mn、Te可能以固溶体的形式存在,Co、Ni、Pb、Zn、Cu、Ag以矿物包裹体形式存在。龙山金锑矿至少经历了两个成矿期:早期是由深部的富Ni岩浆流体引发的金、铅、铜、钨矿化,该期矿化强度不大;晚期是以大气降水循环引起的金、锑矿化,是龙山金锑矿的主要成矿期,并大致可分为显微金阶段、次显微金辉锑矿阶段、可见金辉锑矿阶段和辉锑矿阶段4个成矿阶段。