贵重和有色金属矿床钨氧化钐-钕同位素定年研究及其地质意义

本文结合国内外典型研究事例分析 ,介绍了钨氧化物钐 钕同位素直接定年技术在贵重和有色金属矿床研究中的适用性和局限性 ,探讨了利用钕同位素数据示踪成矿物质来源与流体运移轨迹的可能性 ,指出对同一金属矿床开展多种同位素分析的重要性和必要性。     

High Precision Hf-W Isotopic Measurements in Meteoritic Material Using Negative Thermal Ionisation Mass Spectrometry (NTIMS)

This paper presents a two-stage anion-exchange procedure for tungsten extraction, an improved mass spectrometric procedure for tungsten analysis and a simplified chemical separation and TIMS procedure for the determination of Hf concentrations. The chemical separation of tungsten is based on its complexing properties with HF and H₂O₂. The blank level for a sample size of 300 mg is about 80 pg for tungsten. The procedure is designed for the high sensitivity of negative thermal ionisation mass spectrometry (NTIMS) provided by the use of Mg oxide as an emitter on Ir filaments. Tungsten can be readily measured with a high precision in various meteoritical material and especially in small W-poor silicate fractions. Samples containing as little as a few ng g^-1 tungsten can be analysed reliably with this method.     

溴邻苯三酚红光度法测定含铬矿石中的钨

本文在资料邻苯三酚红(十六烷基三甲基氯化铵)三元络合物在硝酸介质中测定钨的基础上,研究了钨与溴邻苯三酚红(溴代十六烷基三甲基胺)三元络合物的测定条件,提出在硫酸介质中,用溴邻苯三酚红(溴代十六烷基三甲基胺)三元络合物不经分离测定含铬高的矿石中的钨。在盐酸羟胺、EDTA存在下,二十余种阴,阳离子不干扰测     

中国钨矿成矿地质特征与资源潜力分析

钨矿是中国传统优势矿种,前人在钨矿成矿理论方面积累了非常丰富的研究成果。然而,随着近年来在江西、云南和新疆等地取得的多项钨矿重大找矿突破,对原有的钨成矿带地质认识提出了挑战,急需进一步分析和总结其地质特征、成矿规律和资源潜力,为今后地质找矿工作提供理论指导。文中采用矿床模型综合地质信息预测方法,在各省区钨矿资源潜力预测成果的基础上,以MapGIS为平台,进行数据库汇总与综合分析研究。首先,基于全国1 538处钨矿产地数据的统计分析,初步总结了中国钨矿时空分布特征,以及岩浆岩、构造和地层等控矿因素。其次,根据钨矿床及预测区的空间分布和大地构造单元,划分了56个钨矿成矿区带。再次,将钨矿的预测类型划分为石英脉型、夕卡岩型、斑岩型、云英岩型、陆相火山岩型、沉积变质型、层控夕卡岩型和砂矿型,并建立了主要钨矿类型的预测模型。最后,在全国范围累计圈定的1 357个最小预测,累计预测资源量(WO3)2 973×104 t。根据钨矿区域成矿特征,将最小预测区归并为461个二级预测区,并进一步合并为118个钨矿三级预测区,其中,找矿潜力大的河南卢氏-栾川、新疆白干湖、湖南香花岭-瑶岗仙、甘肃野马滩-干巴河脑、江西坪背山-八仙脑和大湖塘等6个三级预测区可优先部署钨矿勘查工作。     

赣中聚源大型石英脉型白钨矿床含铀富钨矿物初步研究

聚源钨矿是华南地区为数不多的大型石英脉型白钨矿矿床之一.在详细的野外地质调查基础上,本文利用α径迹蚀刻、电子显微镜、扫描电镜以及电子探针等实验手段,对该矿床含钨和含铀矿物开展了精细矿物学的研究工作,探讨了成矿过程中钨和铀的富集规律.研究显示,该矿床钨铀矿物的形成可分为四个阶段:第一阶段,钨铀主要进入富含Nb、Ti的氧化...     

Review on carbon-based electrode materials for application in capacitive deionization process

Most of the electrochemical studies related to porous carbon electrodes are those which can be used for either electrostatic energy storage or for energy conversion [using electrical double layer capacitor (EDLC)]. The techniques, such as electrodialysis, membrane filtration, advanced oxidation process, thermal evaporation, can be used now-a-days to treat salty water. Among which, capacitive deionization (CDI) has emerged as a novel cost effective and environment friendly desalination technology. CDI process involves the removal of inorganic ions from the salty water by applying an electrical potential between two porous carbon electrodes. Because of the passage of electrical potentials in the system, the unwanted ions present in the water sample will be adsorbed on the electrode surfaces. Hence, the electrodes which are having high surface area can exhibit higher desalination capacity. In this article, the application of various carbon-based composite electrode materials such as activated carbon and PVDF composite, carbon–metal oxide composite, carbon–CNT composite, carbon–polymer composite and carbon sheet (carbon aerogel, activated carbon cloth) in CDI process is systematically reviewed and presented. CDI process is being developed now-a-days especially toward commercialization in treating the brackish water.     

云南北衙地区钨矿化特征与找矿方向

云南北衙矿床是中国21世纪初新发现的超大型矽卡岩-斑岩型金多金属矿床之一,除已经勘查评价的Au、Fe、Cu、Pb、Zn等元素外,还伴生有一定量的W元素等有益组分。文章对北衙金多金属矿床万硐山矿段及外围马头湾和南大坪矿区中的钨矿化开展系统的岩石学和矿物学研究,初步查明了万硐山矿段和其外围矿床中的钨矿化特征。研究发现,这些矿区(段)的含钨矿物主要为白钨矿,在万硐山矿段和马头湾矿区还有少量的黑钨矿产出;钨矿化主要产于岩体与围岩地层接触部位的矽卡岩或其退化蚀变岩中,白钨矿多充填在石榴子石等矿物的晶体间隙,个别被石榴子石包裹(南大坪矿区);万硐山矿段和马头湾矿区中的白钨矿具有较高的w(Mo)。这些特征表明,北衙地区的钨矿化作用与典型矽卡岩型白钨矿矿床基本一致。万硐山矿段中白钨矿交代黑钨矿的过程与磁铁矿的结晶过程密切相关,暗示钨矿化与铁、金矿化作用是同一成矿作用的产物。北衙地区的区域土壤W元素地球化学异常具有良好的浓度分级,且部分异常中心与已知的矿床/点明显对应,说明北衙地区具有良好的钨矿找矿潜力,白钨矿和黑钨矿均可以作为找矿标志性矿物,而Mo元素地球化学异常则可以作为间接找矿标志。     

湖南千里山岩体中金红石化学成分标型特征研究

金红石是湖南千里山岩体黑云母花岗岩中一种常见的副矿物。本文通过分析千里山黑云母花岗岩中金红石的化学成分,探讨了金红石对岩浆热液演化与钨锡成矿的指示作用。结果表明,金红石主要受热液蚀变作用的影响呈3种形态产出。第1种为形成于黑云母裂隙的他形金红石;第2种是颗粒较大的单晶金红石;第3种是呈集合体产出且粒度不等的条带状金红石。随着黑云母花岗岩的蚀变与成矿作用的不断增强,黑云母花岗岩金红石中的元素钨不断富集,表明金红石中的钨含量可以作为花岗岩成矿能力的判别标志,含钨高的金红石对钨矿的形成富集有一定的指示意义,可作为钨矿找矿的标志之一。     

发射光谱法测定地球化学样品中的锡

采用发射光谱法测定样品中锡元素,以焦硫酸钾、氟化钠、三氧化二铝和碳粉混合物作缓冲剂,锗作内标,于平面一米光栅摄谱仪上用垂直对电极进行两次重叠摄谱（截取曝光）,根据谱板中样品的含量选择相应分析线对在测光仪上测量谱线黑度,采用内标法计算得到样品中锡的含量.利用该方法可不用稀释直接在同一谱板上测定地球化学样品中的高含量锡,且在样品存在干扰谱线时,能通过不同分析线对进行干扰排除,有效地提高了测试准确度和工作效率.     

矽卡岩型钨矿床成矿作用研究进展

钨具有极高的熔点和硬度,是现代生活、工业、国防和高科技领域中不可或缺的基础材料。研究显示,矽卡岩型钨矿是世界钨矿床中最主要的类型,广泛分布于受俯冲影响的环太平洋大陆边缘和与碰撞有关的欧亚大陆内部古大陆边缘,形成时代集中在中生代和古生代。钨在岩浆演化过程中呈现不相容的特征,因此与钨矿化相关的岩浆岩演化程度较高,包括S型、A型以及高分异I型花岗岩。钨具有较高的流体亲和性,使其在熔-流体分异过程中倾向于富集在共存的流体相。钨在热液流体中以氯化物、氟化物和碳酸盐络合物,以及同多钨酸盐和杂多钨酸盐等形式迁移,主要受源岩、围岩成分和流体物化条件等因素影响。矽卡岩型钨矿的成矿作用存在多期次、多阶段演化特征,不同阶段的成矿流体的温度和盐度存在差异。白钨矿是矽卡岩型钨矿中主要的矿石矿物,其沉淀可能受到多种机制的影响,如降温、流体混合、流体沸腾及流体-围岩反应等。文章简要综述了世界矽卡岩型钨矿的时空分布、地质特征和相关成因矿物学研究,并重点总结了钨的成矿岩浆-热液体系特征,钨在岩浆-热液演化过程中的地球化学行为及其迁移和沉淀机制等方面的研究成果。文章指出,为了完善矽卡岩型钨矿的成矿和找矿勘查模型,应当加强矽卡岩型钨矿的成矿时代、成矿物质和流体来源以及成矿环境的精细研究。     

The geochemistry of tungsten in Bulgarian coals

This paper discusses the tungsten geochemistry in coal, based on the behavior of this element in 14 Bulgarian deposits. The W contents range from 0.5–4335 ppm in the ash and from 0.01–784 ppm in the coals. In four of the deposits the tungsten content proved to be 16 to 100 times higher than the Clarke value for sedimentary rocks. No correlation has been found between the W concentration and either the age of the coal-bearing strata or the coal rank. The deposits were divided in three groups on the basis of the relationship between tungsten and ash content. The role of sorption ash and terrigenous ash in tungsten binding was evaluated for each group. The correlation between tungsten and organic matter is demonstrated by the increased contents of tungsten in the ash of the low-ash coals, its concentration in the lighter coal fractions, its extraction from the coals by HF and NaOH only, and by model experiments. Sorption ash concentrates tungsten; terrigenous ash is a carrier of tungsten.Of the petrographic constituents of coal, vitrain was found to concentrate the largest amounts of tungsten.In two of the deposits richest in tungsten, there is a very distinct zonality in its vertical distribution — tungsten concentration decreases from the bottom to the top of the coal bed. This zonality might be explained by the diffusion (syngenetic or diagenetic with respect to the coal-forming process) through the coal bed of aqueous solutions enriched in tungsten.The wide range of variation of the tungsten concentrations, the considerable differences in the mean contents and the dispersions between the individual deposits show that tungsten is very sensitive to the differences of the source area.Coal deposits enriched in tungsten may be expected in the following favourable environments: (1) in areas with nitrogen-bearing thermal waters containing increased amounts of tungsten; (2) source areas with tungsten mineralizations; and (3) country rocks consisting of acid granitoids whose Clarke values of tungsten are the highest as compared to the other types of rocks.     

中国钨矿形成的大地构造背景

世界钨矿的主要分布在受俯冲作影响的环太平洋广义的大陆边缘,以及欧亚大陆内部广义古大陆边缘碰撞带.中国钨矿床从时间和空间分布,形成的大地构造背景皆与世界钨矿相似,是世界钨矿成矿带的重要组成部分.     

http://www.sciencedirect.com/science/article/pii/S167498711000037X

The tried and tested multianvil apparatus has been widely used for high-pressure and high-temperature experimental studies in Earth science. As a result, many important results have been obtained for a better understanding of the components, structure and evolution of the Earth. Due to the strength limitation of materials, the attainable multianvil pressure is generally limited to about 30 GPa (corresponding to about 900 km of the depth in the Earth) when tungsten carbide cubes are adopted as second-stage anvils. Compared with tungsten carbide, the sintered diamond is a much harder material. The sintered diamond cubes were introduced as second-stage anvils in a 6–8 type multianvil apparatus in the 1980s, which largely enhanced the capacity of pressure generation in a large volume press. With the development of material synthesis and processing techniques, a large sintered diamond cube (14 mm) is now available. Recently, maximum attainable pressures reaching higher than 90 GPa (corresponding to about 2700 km of the depth in the Earth) have been generated at room temperature by adopting 14-mm sintered diamond anvils. Using this technique, a few researches have been carried out by the quenched method or combined with synchrotron radiation in situ observation. In this paper we review the properties of sintered diamond and the evolution of pressure generation using sintered diamond anvils. As-yet unsolved problems and perspectives for uses in Earth Science are also discussed.     

西藏甲玛铜多金属矿床中白钨矿的产出特征及其找矿意义

西藏甲玛铜多金属矿床位于冈底斯成矿带中段,矿区内显示钨元素异常,局部矿化富集,但前人尚未对钨元素及钨矿物进行研究.为弥补该空缺,文章通过分析钨含量随孔深变化的关系、钨矿物显微镜下鉴定和电子探针分析,发现甲玛矿床矽卡岩型矿体的深部易于富集钨,且出现波峰,钨含量明显高于中浅部矿体;甲玛矿床中的钨矿物为白钨矿,主要赋存于矽卡...     

白钨矿精矿中黑钨矿的物相分析

白钨矿精矿中黑钨矿的物相分析,与黑钨矿中少量白钨矿的物相分析一样,都是由于两者的含量相差过于悬殊,很艰找到合适的选择性溶剂和条件,得到较为满意的分析结果,所以至今仍为国内外尚未过关的课题.本文应用新的选择性溶剂-结晶氯化铝,它比以往使用的那一种选择性溶剂对白钨矿的溶出率要大,采取适当措施后黑钨矿的溶出率可以降低得很小,并且对钨矿中的一些常见共生的含钙矿物能同时全部除去,在此基础上测定残渣中的钨(黑钨矿和残剩少量白钨矿的和)和钙(白钨矿的钙),钙的含量按CaWO_4固定组成换算成白钨矿的钨,差减即得黑钨矿的钨.     

福建行洛坑大型钨矿的地质特征、成矿时代及其找矿意义

行洛坑钨矿是目前福建最大也是武夷山成矿带最大的钨矿,已知储量主要分布于岩体内部,宜归属于斑岩型钨矿范畴。本文通过Re-Os法和Rb-Sr等时线法测定花岗岩体中辉钼矿的Re-Os等时线年龄为156.3±4.8Ma,石英脉中流体包裹体的Rb-Sr等时线年龄为147.5±2.9Ma,表明成矿作用与岩浆岩的形成基本同步,并延续了大约10Ma。因此,行洛坑钨矿虽然属于斑岩型钨钼矿但岩体以外的空间也可能找到石英脉钨矿,而整个武夷山成矿带中生代持续而复杂的成矿历史预示了其良好的找矿前景。     

Physicochemical parameters of the formation of hydrothermal deposits: A fluid inclusion study. I. Tin and tungsten deposits

The author’s database, which presently includes data from more than 18500 publications on fluid and melt inclusions in minerals and is continuing to be appended, was used to generalize results on physicochemical parameters of the formation of hydrothermal deposits and occurrences of tin and tungsten. The database includes data on 320 tin and tin-tungsten deposits and occurrences and 253 tungsten and tungstentin deposits around the world. For most typical minerals of these deposits (quartz, cassiterite, tungsten, scheelite, topaz, beryl, tourmaline, fluorite, and calcite), histograms of homogenization temperatures of fluid inclusions were plotted. Most of 463 determinations made for cassiterite are in the range of 300–500°C with maximum at 300–400°C, while those for wolframite and scheelite (453 determinations) fall in the range of 200–400°C with maximum at 200–300°C. Representative material on pressures of hydrothermal fluids included 330 determinations for tin and 430 determinations for tungsten objects. It was found that premineral, ore, and postmineral stages spanned a wide pressure range from 70–110 bar to 6000–6400 bar. High pressures of the premineral stages at these deposits are caused by their genetic relation with felsic magmatism. Around 50% of pressure determinations lie in the range of 500–1500 bar. The wide variations in total salinity and temperatures (from 0.1 to 80 wt % NaCl equiv and 20–800°C) were obtained for mineral-forming fluids at the tin (1800 determinations) and tungsten (2070 determinations) objects. Most of all determinations define a salinity less than 10 wt % NaCl equiv. (∼60%) and temperature range of 200–400°C (∼70%). The average composition of volatile components of fluids determined by different methods is reported. Data on gas composition of the fluids determined by Raman spectroscopy are examined. Based on 180 determinations, the fluids from tin objects have the following composition (in mol %): 41.2 CO₂, 39.5 CH₄, 19.15 N₂, and 0.15 H₂S. The volatile components of tungsten deposits (190 determinations) are represented by 56.1 CO₂, 30.7 CH₄, 13.2 N₂, and 0.01 H₂S. Thus, the inclusions of tungsten deposits are characterized by higher CO₂ content and lower (but sufficiently high) contents of CH₄ and N₂. The concentrations of tin and tungsten in magmatic melts and mineral-forming fluids were estimated from analysis of individual inclusions. The geometric mean Sn contents are 87 ppm (+ 610 ppm/−76 ppm) in the melts (569 determinations) and 132 ppm (+ 630 ppm/−109 ppm) in the fluids (253 determinations). The geometric mean W values are 6.8 ppm (+ 81/−6.2 ppm) in the magmatic melts (430 determinations) and 30 ppm (+ 144 ppm/−25 ppm) in the mineral-forming fluids (391 determinations).     

甘肃岷县寨上金钨矿床中钨矿特征及找矿标志

寨上矿床属于以金为主、伴生钨的多金属矿床。目前已发现15条钨矿化体,其中主要的6条钨矿体均与金矿体相重合。寨上矿区9处异常中有7处Au、W异常相重合。Au、W元素相伴生存在,局部地区形成金、钨矿化体共生的局面。钨矿物主要为白钨矿,极少量黑钨矿。白钨矿也是重要的载金矿物,金与钨关系密切。矿体主要产于碳质板岩、泥质板岩、钙质板岩等较软弱岩性地层。矿脉受控于层间或顺层断裂破碎带。矿区的主要蚀变类型有硅化、黄铁矿化,其次为碳酸盐化、绢云母化。低阻高极化异常能较准确的反映矿化带和矿脉的延伸位置。钨的水系沉积物异常和土壤异常均呈带状低值异常特征,与已知矿带吻合较好。研究成果及勘查实践证明,在该金矿化(带)体中寻找钨矿化体是最简捷的方法。     

A Preliminary Review of Metallogenic Regularity of Tungsten Deposits in China

Tungsten ore resources are abundant in China with relatively complete types of deposits. Skarn type and quartz vein type deposits are dominated in the tungsten resources, whereas quartz vein type wolframite deposits are most important in terms of exploitation and utilization. Skarn type tungsten deposits are concentratedly distributed in the central Nanling region, such as South Hunan, South Anhui and the eastern Qinling region, while quartz vein type tungsten deposits occur mainly in South China, such as West Fujian, South Jiangxi, North Guangdong and South Hunan. The most important metallogenic epoch of tungsten is the Mesozoic, while the metallogenic tectonic setting is featured by an intracontinental environment after orogeny with sever tectonic movements, deep-seated faults and frequent magmatic activities, especially Mesozoic granitoids closely related to tungsten-tin mineralization. 22 metallogenic series of ore deposits characterized by or significantly related to tungsten were defined based on precise statistic information of 1199 tungsten mining areas and thorough the summary of metallogenic regularities. Based on studies of the metallogenic regularity of tungsten deposits, skarn type (or greisen type), quartz vein type and massif-type of tungsten deposits are thought to be the key prediction types. 65 tungsten-forming belts and 22 key ore concentration areas were ascertained and a distribution map of tungsten-forming belts of China was compiled, which provided a theoretical basis for evaluation and prediction of potential tungsten resources.     

硫氰酸盐比色法测定钨的改进

硫氰酸盐比色法测定钨是基于W5+与硫氰酸盐形成黄色络合物。为使钨完全还原为5价,通常单独使用三氯化钛或氯化亚锡作还原剂。此方法在应用过程中,由于Ti3+本身呈紫色,加多会掩盖络合物的黄色,加少则出现硫氰酸铁之红色丝状物影响比色的情况。通过大量的试验,采用氯化亚锡-三氯化钛作双还原剂,控制最佳酸度、温度和时间,从而获得稳定的络合物,提高了分析结果的稳定性。通过对国家一级标准物质进行分析验证,从而证实方法可行,能够保证样品的测试精密度和准确度。本方法尤其适用于低含量、大批量钨矿样品的测定。