激光显微光谱分析近似定量测定铌钽铁矿中铌、钽、铁、锰

一、概念 随着激光显微光谱分析的广泛应用,国内外许多人致力于分析方法的研究,已报道的有相对比值法,显线法、校正系数法,内标法等。几年来我们主要应用相对比值法分析了上千个岩矿样品,结合实践也对上述几种分析方法作了比较。前几种方法,使用同类标样,通过测量     

铌与钽的某些地球化学问题

针对地球圈层之间Nb、Ta质量不平衡的难题,较系统收集分析了我国基性岩墙(脉)群、太古宙基性火山岩、碱性岩、大火成岩省火山岩,俯冲带中富Nb玄武岩、高压变质岩、花岗岩类的Nb、Ta含量、比值、相关同位素组成以及Nb、Ta实验地球化学资料.这些资料表明,Nb、Ta在这些岩类中的分布呈现非常不均匀变化,除花岗岩外,上述岩石的Nb/Ta比值均高于或近于球粒陨石值17.5.花岗岩中的幔源斜长花岗岩及与裂谷、热点环境有关的碱性花岗岩Nb/Ta比值近于地球平均值,而普通S型及I型花岗岩,特别是高演化花岗岩,Nb/Ta比值均明显低于球粒陨石(<10),甚至呈现Nb/Ta≤1.这些资料表明,在不均匀的地幔中可能存在呈布丁状分布的Nb/Ta比值高于球粒陨石的储源.金红石的稳定性及Nb、Ta分配系数实验资料不支持地球深部存在高Nb/Ta比值的含金红石榴辉岩.     

白云鄂博铁、铌、稀土矿床:研究进展、存在问题和新认识

白云鄂博是世界第一大稀土元素矿床,其稀土元素资源量占世界目前已知稀土元素资源总量的三分之二以上,具有重要的经济和战略地位。白云鄂博自1927年发现至今已有92年,对其的开发和研究历史悠久,在赋矿碳酸岩的成因、成矿年代、稀土矿物学等方面取得了一系列重要进展,为碳酸岩型稀土元素成矿理论发展做出了突出贡献。由于矿床经历了成矿后复杂的构造变形和热液蚀变,致使其地质、地球化学特征复杂,学界对其成因和成矿过程一直存在不同认识,对成矿碳酸岩的岩浆演化、稀土元素迁移与富集机理等方面的研究也相对薄弱。笔者最新研究表明,矿区过去被认为是下白云鄂博群的H1、H2、H9岩石单元并非沉积变质岩或变质火山岩,而应为岩浆侵入成因,矿区其他岩石单元(H3～H7)的成因也值得商榷。H9岩石单元中的黑云母岩(前人称为黑云母板岩)和富含黑云母的碳酸岩(前人称为暗色板岩)为成矿碳酸岩的一部分,是碳酸岩不同岩相带的表现。黑云母岩和富黑云母碳酸岩相对于含矿碳酸岩具有相对低的稀土元素含量和轻、重稀土元素比值,表明岩浆演化可能对稀土元素的富集和分异具有重要贡献。矿区主要岩石单元成因的新认识不仅为矿床成因、成矿背景研究提供了新的依据,同时也为研究区域构造演化、正确厘定矿区构造式样和指导矿区深部和外围找矿提供了新的思路。     

元素地球化学特征在识别碳酸盐岩层序界面中的应用——以冀北坳陷中元古界高于庄组为例

元素是组成岩石矿物的基本单元,它们对环境的变化极为敏感。地层中元素的分配及比值变化、组合都在一定程度上纪录着古沉积环境的演化历程,这些对恢复古沉积环境,研究海相碳酸盐古盐度、海平面相对变化具有重要的指示意义。利用元素地球化学特征对冀北坳陷中元古界高于庄组层序地层单元进行研究,发现在古气候的影响下,古盐度、相对海平面变化与碳酸盐中的元素含量及有关元素比值呈现明显的旋回变化特征。其中Sr/Ba比值法与硼法判别精度相对较高,可以作为识别和划分碳酸盐岩层序界面的有效标志。     

碳酸钠-硼酸熔融酒石酸介质ICP-MS测定地质样品中铌、钽、锆、铪

本实验采用石墨粉垫底碳酸钠-硼酸混合熔剂熔融分解样品,1%酒石酸试液测定铌、钽、锆、铪,结果显示,熔融温度为900℃,熔融时间为10 min,碳酸钠:硼酸比值为1:2,样品与熔剂比值为1:5。采用GSS4,GSD14,GSR8,GSR1,GSR2标准物质3份平行测定,计算得到RSD%为:Zr:0.3~1.7%;Nb:1.1~3.9%;Hf:0.3~2.2%;Ta:2.5~21.4%,满足地质样品测试要求。采用1%酒石酸溶液测定,与传统稀硝酸溶液测定相比,分析结果的重现性显著提高。     

祁漫塔格成矿带磁铁矿Fe2+/Fe3+比值测定方法对比研究

为了厘清磁铁矿成分测试过程中Fe²⁺/Fe³⁺比值分析各种方法的准确性及适用范围;采用直接测氧法、Lβ/Lα强度比值法、电价差值法、剩余氧法和穆斯堡尔谱法,对祁漫塔格成矿带中典型矿床中磁铁矿的Fe²⁺/Fe³⁺比值进行了研究,结果表明电价差值法、剩余氧法和穆斯堡尔谱法是相对比较准确的测试方法,但穆斯堡尔谱法不是原位分析方法,存在适用范围的缺陷。     

南岭地区钨锡铌钽花岗岩及其成矿作用

在晚侏罗世时,南岭地区发生了与花岗岩有关的钨锡铌钽大规模成矿作用。依据花岗岩的岩石学、地球化学及其矿化特征,可将南岭地区含钨锡铌钽花岗岩划分为三个主要类型：含钨花岗岩、含锡钨花岗岩和含钽铌花岗岩。含钨花岗岩的地球化学特征可归纳为铝过饱和,低Ba+Sr 和TiO2,轻重稀土比值低,铕亏损强烈,富Y 和Rb,Rb/Sr 比值高,分异强烈。含锡钨花岗岩总体特征表现为TiO2 含量高,准铝质—弱过铝质,轻重稀土比值和CaO/(K2O+Na2O)比值高,富高场强元素、稀土、Ba+Sr 和Rb,低Rb/Sr 比值,分异演化程度较低。含钽铌花岗岩的地球化学特征主要为TiO2 含量和CaO/(K2O+Na2O)比值低,Al2O3/TiO2 和Rb/Sr 比值明显偏高,强过铝质,贫Ba+Sr、稀土和高场强元素,铕亏损强烈,明显富Rb 和Nb,高度分异演化。三类含矿花岗岩具有明显不同的演化特征,成矿作用与它们的演化密切相关。黑云母花岗岩主要与锡成矿作用有关,二云母花岗岩和白云母花岗岩主要产生钨矿化或锡钨共生矿化,钠长石花岗岩主要与钽铌或锡（钨）钽铌矿化有关。总结了南岭锡钨钽铌矿床的重要类型,提出了绿泥石化花岗岩型锡矿新类型,指出南岭地区要特别注意在含锡钨花岗岩中寻找此类锡矿和云英岩- 石英脉型锡钨矿。     

广西栗木锡铌钽矿田成矿物质来源的惰性气体同位素示踪

文章利用黄铁矿流体包裹体惰性气体同位素,探讨了广西栗木锡铌钽矿田成矿流体的来源.黄铁矿流体包裹体的3He/4He比值为0.14～0.97 Ra,远远低于地幔流体的比值,接近饱和大气水的比值,并与地壳流体的比值处在相同的数量级上;40 Ar/36 Ar比值为555.98～ 855.11,平均705.55,显然偏离大气氩的同位素组成;40Ar*/4He比值为0.08～0.27,平均值为0.153,接近地壳值;20Ne/22 Ne=9.671～9.748和21Ne/22 Ne=0.0306～ 0.0330,具有饱和大气水的Ne同位素比值特征.结果表明,广西栗木锡铌钽矿田老虎头、牛栏岭和金竹源3个矿床的成矿流体是大气水和地壳流体的混合流体;水溪庙矿床的成矿流体也主要是大气水和地壳流体的混合流体,但可能有少量地幔流体的加入.     

黄土中方解石、长石和石英的红外光谱定量测定

我们曾用黄土和其他沉积物样品红外光谱中方解石、长石与石英吸收带强度的相对比值,求这三种矿物的相对含量,并且根据这些比值,参照其他方法的研究结果,讨论黄土在形成时期及形成后所经受的气候变化。在实际工作中,往往不但要求知道研究对象中方解石、长石和石英彼此之间的相对含量,还要求确定它们的百分含量。此外,就方解石和石英这两种矿物而言,它们不但分布广,而且含量高,在红外光谱上的反映又特别灵敏。因此,它们经常干扰其他矿物的测定,需要对这些干扰矿物有量的认识。鉴于这些考虑,我们对这三种矿物进行了定量测定。     

迭代目标转换因子分析法同时测定钛、锆、铌的研究

本文利用迭代目标转换因子分析光度法,用高灵敏显色剂水扬基萤光酮(SAF).在CTMAB存在的强酸性介质中,对标准合成试样及合金标样中Ti、Zr、Nb的同时测定进行了研究.结果表明,相对误差一般都在10％以内,相对标准偏差<5％,获得满意结果.     

Wavelength-dispersive X-ray fluorescence spectrometric determination of Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites

Komatiites are mantle-derived ultramafic volcanic rocks. Komatiites have been discovered in several States of India, notably in Karnataka. Studies on the distribution of trace-elements in the komatiites of India are very few. This paper proposes a simple, accurate, precise, rapid, and non-destructive wavelength-dispersive x-ray fluorescence (WDXRF) spectrometric technique for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites, and discusses the accuracy, precision, limits of detection, x-ray spectral-line interferences, inter-element effects, speed, advantages, and limitations of the technique. The accuracy of the technique is excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Zr, Nb, Ba, Pb, and Th and very good (within 4%) for Y. The precision is also excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th. The limits of detection are: 1 ppm for Sc and V; 2 ppm for Cr, Co, and Ni; 3 ppm for Cu, Zn, Rb, and Sr; 4 ppm for Y and Zr; 6 ppm for Nb; 10 ppm for Ba; 13 ppm for Pb; and 14 ppm for Th. The time taken for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in a batch of 24 samples of komatiites, for a replication of four analyses per sample, by one operator, using a manual WDXRF spectrometer, is only 60 hours.     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案(1999/30/EC),对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提     

Isotopic systematics of He,Ar, S,Cu, Ni,Re, Os,Pb, U,Sm, Nd,Rb, Sr,Lu, and Hf in the rocks and ores of the Norilsk deposits

This paper reports the first results of a study of 11 isotope systems (³He/⁴He, ⁴⁰Ar/³⁶Ar, ³⁴S/³²S, ⁶⁵Cu/⁶³Cu, ⁶²Ni/⁶⁰Ni, ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ^206–208Pb/²⁰⁴Pb, Hf–Nd, U–Pb, and Re–Os) in the rocks and ores of the Cu–Ni–PGE deposits of the Norilsk ore district. Almost all the results were obtained at the Center of Isotopic Research of the Karpinskii All-Russia Research Institute of Geology. The use of a number of independent genetic isotopic signatures and comprehensive isotopic knowledge provided a methodic basis for the interpretation of approximately 5000 isotopic analyses of various elements. The presence of materials from two sources, crust and mantle, was detected in the composition of the rocks and ores. The contribution of the crustal source is especially significant in the paleofluids (gas–liquid microinclusions) of the ore-forming medium. Crustal solutions were probably a transport medium during ore formation. Air argon is dominant in the ores, which indicates a connection between the paleofluids and the atmosphere. This suggests intense groundwater circulation during the crystallization of ore minerals. The age of the rocks and ores of the Norilsk deposits was determined. The stage of orebody formation is restricted to a narrow age interval of 250 ± 10 Ma. An isotopic criterion was proposed for the ore-bearing potential of mafic intrusions in the Norilsk–Taimyr region. It includes several interrelated isotopic ratios of various elements: He, Ar, S, and others.     

硅酸盐中铁、锰、钛、钙、钾、磷、硅、铝、镁、钠、锶、铷、钡的X-射线荧光光谱定量测定

本文介绍样品经四硼酸锂熔融制成玻璃小饼。采用Lachance模式和理论a系数来校正元素间的效应,由3080E型X-射线荧光谱仪和DF-350B数据处理系统完成硅酸盐中十三个项目的测定。     

硅酸盐类样品中硅、铁、铝、钛、锰、钙、镁、钾、钠和磷的x射线荧光光谱测定

本文拟定了一种以熔融法制备样片,用X射线荧光光谱测定硅酸盐类样品中Si、Fe、Al、Tj、Mn、Ca、Mg、K、Na、P等元素的分析方法。在对不同靶材X光管和分光晶体实验对比的基础上,选择了最佳的测量条件。该法具有快速、准确,测量范围广,检测限低,价格便宜等优点。经过近百个各种类型标样或管理样品的分析对比表明,本法不仅适用于硅酸盐类岩石样品的分析,还适用于铁矿、铝土矿、碳酸盐类岩矿样品以及水泥、耐火材料等样品的分析。     

Viscous, cohesive, non-Newtonian, depositing, radial slurry flow

Mining induced subsidence can significantly affect mining costs where major surface facilities and natural environment need to be protected. Overburden grout injection is a technology used to control coal mine subsidence by injecting the mine waste material extracted from the coal back into the inter-burden rock during longwall mining. The flowing slurry is here categorised as a nonlinear viscous cohesive (Bingham plastic) fluid. During longwall mining the grout slurry is pumped into the separated beds of the rock mass through a central vertical borehole, which is drilled deep into the inter-burden rock strata above the coal seam. However, a blockage can occur in the injection system when the slurry velocity falls below a certain critical threshold velocity, indicating a material phase change from cohesive-viscous to cohesive-frictional. In situ field injection tests through boreholes have been simulated at a smaller scale at the CSIRO laboratory in Brisbane by pumping the slurry through a radial disk (gap = 4 mm) from its centre. Laboratory experiments indicate a general, nonlinear, cohesive, viscous, frictional model for shear behaviour of the slurry, in which the material shear parameters are functions of the disk radial distance. Complete dimensional and dimensionless analytical solutions have been developed based on an approach related to Bingham–Herschel–Bulkley fluid mechanics. The derived formulae include relations for minimum pump pressure, local pressure and pressure gradient, wall shear stress, volume rate, velocity and velocity gradient. The theoretical results match the experimental measurements. The experiments covered slurries with maximum particle sizes of 0.5 to 2 mm with about 50% being larger than 100 µm. The viscosities at the various solids concentrations were measured with a standard torsion viscometer. This study differs from the previous research in several distinct aspects, namely, consideration of the variable shear parameters rather than fixed values, inclusion of total nonlinear behaviour, and implementation of a friction function to mimic behaviour of the deposited and consolidating stiff slurry, which can cause a significant pressure rise as a result of the increased shear resistance.     

Mountains,nations, parks,and conservation

Between 1985 and 1991, two new mountain protected areas (MTNPA) covering more than 35,000 km² and based on participatory management models — the Makalu-Barun National Park and Conservation Area, Nepal, and Qomolangma Nature Preserve, Tibet Autonomous Region — were successfully established through the collaborative efforts of Woodlands Mountain Institute and conservationists in China and Nepal. Characteristics common to both projects include the importance of establishing (1) effective rationales, (2) local support constituencies, (3) a senior advisory group, (4) a task force, (5) linkages between conservation and development, and (6) fund raising mechanisms. The lessons derived from the experiences of Woodlands Mountain Institute are of significant value to others in preserving MTNPA. Increased collaboration and communication between all interested in conservation, however, will remain a critical component for expanding mountain protected area coverage to throughout the world.     

Regional distribution of Al,B, Ba,Ca, K,La, Mg,Mn, Na,P, Rb,Si, Sr,Th, U and Y in terrestrial moss within a 188,000 km2 area of the central Barents region: influence of geology,seaspray and human activity

Five hundred and ninety-eight samples of terrestrial moss (Hylocomium splendens and Pleurozium schreberi) collected from a 188,000 km² area of the central Barents region (NE Norway, N Finland, NW Russia) were analysed by ICP-AES and ICP-MS. Analytical results for Al, B, Ba, Ca, K, La, Mg, Mn, Na, P, Rb, Si, Sr, Th, U and Y concentrations are reported here. Graphical methods of data analysis, such as geochemical maps, cumulative frequency diagrams, boxplots and scatterplots, are used to interpret the origin of the patterns for these elements. None of the elements reported here are emitted in significant amounts from the smelting industry on the Kola Peninsula. Despite the conventional view that moss chemistry reflects atmospheric element input, the nature of the underlying mineral substrate (regolith or bedrock) is found to have a considerable influence on moss composition for several elements. This influence of the chemistry of the mineral substrate can take place in a variety of ways. (1) It can be completely natural, reflecting the ability of higher plants to take up elements from deep soil horizons and shed them with litterfall onto the surface. (2) It can result from naturally increased soil dust input where vegetation is scarce due to harsh climatic conditions for instance. Alternatively, substrate influence can be enhanced by human activity, such as open-cast mining, creation of ‘technogenic deserts’, or handling, transport and storage of ore and ore products, all of which magnify the natural elemental flux from bedrock to ground vegetation. Seaspray is another natural process affecting moss composition in the area (Mg, Na), and this is most visible in the Norwegian part of the study area. Presence or absence of some plant species, e.g., lichens, seems to influence moss chemistry. This is shown by the low concentrations of B or K in moss on the Finnish and Norwegian side of the (fenced) border with Russia, contrasting with high concentrations on the other side (intensive reindeer husbandry west of the border has selectively depleted the lichen population).     

NEW SET OF LOW CONCENTRATION STANDARDS FOR LA, CE, SM, YB, LU, Y, SC, V, NB AND TA IN SILICATES

We have developed a set of four synthetic standards for the rare earth and high field strength elements designed for use in the determination of those elements in silicates. The base material is a glass nominally at the eutectic of the MgO-Al₂O₃-SiO₂ ternary system. The nominal doping level was 2 wt% of the elements as oxides. To avoid problems associated with peak interference, the elements were doped in four separate glasses.