铜钴矿样品X荧光快速测定技术的初步研究

使用基于Si-PIN探测器和嵌入式计算机的便携式高能量分辨率X荧光(XRF)分析仪,对采自刚果(金)的铜钴矿样品进行测量。通过对实测数据的处理与分析,分含量段建立目标元素的工作曲线,同时求出相应的基体效应校正模型,并编制到仪器内置X荧光分析应用软件中。实现仪器根据实测多道微分谱线中相关元素的特征X射线计数率,自动切换工作曲线与基体效应修正模型,快速输出Cu和Co的含量的测定结果。通过与化学分析结果比较,快速测定结果精确度较高。     

熔融制样X射线荧光光谱法测定含硫量高的石膏矿物中主次量元素

X射线荧光光谱法(XRF)已经应用于石膏等非金属矿物的测定,但由于石膏标准物质匮乏、硫含量较高且在高温易挥发损失,给测定带来了一定困难。本文采用石膏标准物质、高纯硫酸钙和其他国家一级标准物质(土壤、水系沉积物、碳酸盐)配制人工标准物质拟合校准曲线,优化稀释比、熔矿温度等熔融制样条件,用理论α系数校正基体效应,建立了采用XRF同时测定石膏矿中10个主次量元素(硅铝铁钙镁钾钠钛硫锶)的分析方法。样品与四硼酸锂-偏硼酸锂熔剂的稀释比为1∶9,在1050℃温度下样品熔融完全。方法检出限为4~135μg/g,精密度(RSD,n=12)小于3.0%。本方法配制的人工校准样品加强了样品基体的适应性,使用的四硼酸锂-偏硼酸锂熔剂在样品熔融过程中可有效地结合硫,抑制了硫的挥发损失,适用于批量分析硫含量高达12.60%~51.91%的实际石膏矿物。     

X射线荧光光谱法测定高锶高钡的硅酸盐样品中主量元素

用百分总和检查硅酸盐岩石全分析数据的质量是分析工作者的传统做法,但对于微量元素含量较高的样品,采用X射线荧光光谱法(XRF)进行测定,如果不考虑微量元素的含量及其对主量元素基体效应的影响,往往会使主量元素含量更加偏离真实值。本文针对Sr、Ba含量较高的硅酸盐样品,通过人工配制标准样品,扩大了Sr、Ba校准曲线的定量范围,主量元素校准中加入Sr、Ba的基体校正系数,达到了主量元素定量更加准确可靠的实际效果。采用此方法分析国家标准物质,各主量元素的精密度(RSD)均小于2%;分析不参加回归的标准物质和人工配制的标准样品,主量元素的测量值与标准值(或参考值)基本一致。该方法可以满足硅酸盐的测定要求,主量元素各项结果的加和能够达到《地质矿产实验室测试质量管理规范》的一级标准(99.3%～100.7%)。     

X射线荧光光谱法同时测定钛精矿中主次量组分

采用铁矿标准样品和高纯二氧化钛混合配制钛精矿的校准样品,X射线荧光光谱法同时测定钛精矿中氧化镁、三氧化二铝、二氧化硅、磷、硫、氧化钙、二氧化钛、五氧化二钒、锰、铁等主次量成分,并对熔剂选择、熔融条件、钒Kα峰位确定及基体效应校正等进行了探讨。测定结果与标准样品标称值吻合,相对标准偏差(RSD,n=7)除低含量的磷、硫外均在5%以下,能满足钛精矿的检测需要。     

多仪器协同-X射线荧光光谱法在区域地球化学调查分析中的应用评价

在区域地球化学调查样品多元素分析测试中,通常将XRF、ICP-OES、ICP-MS、AFS等仪器相互配套使用,但由于XRF测定20多个元素,与其他仪器测定速度并不同步,影响了项目的整体进度。本方法对配套方案进行了优化,调整了XRF部分测量元素的分析方法,即将基体校正和谱线重叠校正涉及Na_2O、MgO、V的数据由ICP-OES法测量;Cu、Pb、Zn、Mn、Th的数据由ICP-MS法测量;As、Bi的数据由AFS法测量。优化后的XRF方法测量元素减少为16个:SiO_2、Al_2O_3、Ca O、TFe_2O_3、K_2O、Ti、P、Sr、Ba、Zr、Nb、Y、Rb、Br、Ga、Cl。通过设计的XRF数据处理程序,实现了这些不同方法的测量数据共享,利用ICP-OES、ICP-MS、AFS等测量数据对XRF数据进行基体效应和谱线重叠干扰校正。本方法精密度(RSD,n=12)为0.55%~8.22%,准确度(ΔlogC)为0.000~0.031,用国家标准物质及实际样品验证的结果满足区域地球化学调查样品分析测试质量规范要求。本方案减少了XRF直接测量元素的数量,提高了多种仪器协同的分析效率。     

全谱发射光谱仪应用于分析地质样品中的银锡硼钼铅

掌握地质样品中银锡硼钼铅的含量对于研究成矿规律和地球化学找矿极其重要,目前的分析方法很少能一次性准确高效检出银锡硼钼铅。本文在前人研究基础上建立了应用全谱发射光谱仪固体粉末进样,一次性高效、准确地分析检测地质样品中银锡硼钼铅的方法。采用国家一级标准物质(岩石、土壤和水系沉积物)对合成硅酸盐标准曲线进行第二次拟合以降低基体的干扰;设置元素分析谱线转换值实现元素分析谱线的简单切换,不同的样品含量使用不同的分析谱线,达到分析结果更加接近样品真值的效果,同时扩大了标准曲线线性范围。结果表明:银锡硼钼铅的检出限分别为0.0077μg/g、0.19μg/g、0.68μg/g、0.058μg/g、0.49μg/g,方法精密度在3.23%～9.39%之间。应用本方法分析土壤、水系沉积物、岩石国家一级标准物质的测定值与其认定值相符,△logC值的绝对值均小于0.10;实际样品和外控样的一次测试结果合格率分别为92%～98%、100%。本方法简单,分析速度快,避免了样品稀释带来的污染,使用多条分析谱线测定国家标准物质,相比传统发射光谱法使用单分析谱线的测定值更加接近认定值,检出限优于《地质矿产实验室测试质量管理规范》的规定值。     

核地球物理X辐射取样中克服基体效应的研究

克服基体效应的影响是Ｘ辐射取样技术中的关键问题。应用谱线分解技术,对样品的复合谱线进行分解,求得各元素的净Ｘ射线荧光计数率,在此基础上建立了“特散比法与吸收元素校正法联合应用”的数理方程,进行基体效应的校正。应用此技术对人工配制的样品和两个铜矿区实际样品进行了测量。     

熔融制样-X射线荧光光谱法测定稀土矿石中的主量元素和稀土元素

应用熔融制样-X射线荧光光谱法(XRF)分析矿石样品具有定量准确、试剂用量少、重现性好等优点,但由于目前稀土标准物质较少,不能满足复杂稀土矿石类样品的准确定量要求。本文采用配置人工标准样品,解决了现有稀土标准物质较少的问题,加入高纯稀土氧化物La2O3、Ce O2、Y2O3扩展了La、Ce、Y的线性范围,利用人工标准样品和现有稀土标准物质、碳酸盐标准物质制作工作曲线,建立了XRF测定稀土矿石、矿化样品中25种主量元素和稀土元素的分析方法。针对主量元素采用理论α系数法校准,稀土元素采用经验系数法校准,对有谱线重叠的元素进行干扰校正,使绝大多数主量元素的相对标准偏差(RSD,n=13)小于1.5%,稀土元素含量在300"g/g以上时RSD(n=13)在0.69%~6.94%之间。通过未知样品考核,主量元素、稀土元素和烧失量的加和结果为99.41%~100.63%,满足《地质矿产实验室测试质量管理规范》的一级标准。     

利用微区XRF技术测定地质样品中元素含量研究

微区XRF是新兴的固体样品表面元素半定量分析技术,由于缺少同类基质标样和仪器参数整体优化方案等问题,使得该技术在定量分析方面的研究较少.本研究利用微区XR F技术对黄铁矿地质标样硫、铁元素进行检测,探讨了真空度、驻留时间、检测器频率、X射线功率等仪器参数对非标定量准确度的影响,结果显示了真空度和X射线功率是影响检测准确度的重要指标,真空条件下,硫、铁元素检测结果与标样理论值的相对误差从非真空时的-52.25％和59.95％减少到0.51％和-0.21％;在20、30、40和50 keV的X射线功率下,硫元素的相对误差分别为-12.65％、-5.70％、-1.22％、0.51％,而铁元素分别为 14.79％、6.86％、1.76％、-0.21％.在优化的仪器参数下(检测器频率Tc设置为1 ps,驻留时间设置为100 s,X射线功率设置为50 keV,检测环境设置为真空),对土壤样品GSS-1进行非标定量,发现多数元素平行性良好,3次检测的相对标准偏差在3％以内;由于样品基质复杂,定量准确度较差,相对误差范围在-14.08％到905.98％之间.为优化准确度,采用GSS-2～GSS-10 土壤标样建立标准曲线,以标样GSS-1作为样品进行检测分析,结果显示通过线性校准曲线校正,GSS-1样品中多种元素检测值与理论值的相对误差减少到-13.07％到4.72％之间,而通过拟合标准曲线校正,相对误差在-13.64％到14.91％之间,两种标准曲线校正后全部元素的定量结果与理论值相对误差均在±15％之内.本研究结果表明,通过优化微区XRF测试参数,对黄铁矿简单基质样品可直接进行定量;对土壤基质复杂的样品,通过类似的基质标样建立相应标准曲线进行校准,也可获得准确度相对较好的定量结果.     

X射线荧光光谱仪同时测定红土型镍矿中主次量组份

以无水四硼酸锂作熔剂,硝酸铵为氧化剂,碘化钾为脱模剂,在高频熔样机上于1050℃熔融,制成玻璃片,使用标准曲线对谱线重叠干扰和基体效应进行校正,建立XRF测定红土型镍矿中TFe、SiO2、Al2O3、Cr2O3、MgO、Ni、Co的分析方法,经标准样品和检测样品外部比对结果验证,结果准确,可靠,方法快速、简便。     

A site-specific study on the measurement of sorption coefficients for radionuclides

A study on the potential of geological media from the vicinity of the mining site in Tummalapalle region of Andhra Pradesh in India for retardation of radionuclide migration in groundwater was conducted. The studies included the measurement of sorption coefficients for six radionuclides, uranium, thorium, lead, bismuth, radium and polonium, between two groundwater simulants and two site-specific samples of geological media. Initial parametric studies involving chemical composition, pH, calcium carbonate and organic carbon contents of both geological media and ground water simulants were carried out. Significant differences in sorption coefficients were observed as a result of varying pH, calcium carbonate and presence of trace quantities of organic contents in simulant solutions. For example, uranium has a hundred fold lower distribution coefficient in the case of simulant solution having higher carbonate content. Similarly, in the case of the geological media having higher calcium carbonate and organic carbon contents, higher distribution coefficients were obtained for all radionuclides. Among the six radionuclides studied thorium showed the largest and radium the smallest distribution coefficient values for the soil samples assessed. The site-specific sorption coefficients will be used for contaminant transport study.     

The magnesium and calcium contents of sediments,especially pelites,as a function of age and degree of metamorphism

The silicate and carbonate fraction of 98 non-metamorphic shale samples from the Australian platform and of different geological age were analysed for calcium, magnesium, ferrous iron and carbonate. Cainozoic and Mesozoic shales prove to be essentially calcitic, Cambrian and Proterozoic shales are essentially dolomitic and sideritic. A similar trend of high MgO values can be demonstrated for the silicate fraction of the old shales. Extensive literature study confirms these trends for shales and carbonate rocks from all over the world. Slates, hornfelses and schists are Mg rich and Ca poor, whether young or old.Ronov's model of the evolution of the earth's crust ocean and atmosphere, explaining these trends, is critically reviewed but rejected because of impossible storage problems of calcium in the Proterozoic. The increased magnesium content of the old sediments is explained by calcium carbonate sweating out of the sedimentary column, magnesium introduction from altering volcanic rocks within the sedimentary pile and magnesium introduction from connate brines in sandstones. The increasing calcium content of all kinds of sediments with decreasing age is claimed to be related to preferential weathering of extrusive volcanic rocks and sweating out of calcium carbonate from the sedimentary column.     

不同熔（溶）矿方法对硅酸盐岩石中氧化钛分析结果的影响

不同熔（溶）矿方法对硅酸盐岩石中氧化钛分析结果的影响苗升明江苏省东海县环境监测站，东海，２２２３００关键词：熔（溶）矿法，硅酸盐岩石，氧化钛，化学分析，江苏东海ＥｆｆｅｃｔｉｖｅｎｅｓｓｏｆＤｉｆｆｅｒｅｎｔＭｅｔｈｏｄｓｏｆＭｅｌｔｉｎｇｏｒＤｉｓ...     

Sr speciation in producing SrCO3 with celestite

Strontium speciation transferring in strontium residue and mixing strontium ore are investigated with extracting experiment, X-ray powder diffraction （XRD）, X-ray fluorescence spectrometer （XRF） and Atomic Absorption Spectroscopy （AAS）. The results show that there are strontium carbonate, strontium sulfate, strontium sulfide, and a little amount of strontium silicate and strontium ferrite in strontium residue. Impurities in strontium residue mainly contain carbonate and oxide of calcium, iron, magnesium and aluminum etc. The amount of strontium sulfide in strontium residue is larger than that in strontium ore. And a little strontium silicate and strontium ferrite are found in strontium ore. It is concluded that acid soluble method is used firstly in the process of producing strontium carbonate from mixing strontium ore. In addition, mechanical smash method and surface active treatment to strontium samples are beneficial to the ratio-leaching increase of strontium. The research achievement helps to save energy and decrease pollutants emission in strontium processing industry.     

电感耦合等离子体法测定灰岩中的钙镁钾钠铝钛铁锰

灰岩样品的主要成分为碳酸钙,而镁、钾、钠、铝、钛、铁、锰的含量非常低,测试的灵敏度要求很高。该文采用一次溶矿电感耦合等离子体法直接测试灰岩中的镁、钾、钠、铝、钛、铁、锰。实验表明：在5％的盐酸介质中测试镁、钾、钠、铝、钛、铁、锰能取得很好的效果。通过测试国家标准样品,与国家标准值相比较,分析结果基本一致,准确度和精密度均令人满意,镁、钾、钠、铝、钛、铁、锰元素的相对标准偏差≤0．07％。钙元素的标准偏差≤0．15％。     

Geochemistry of banded iron formation of Orissa,India

Major and trace element analyses of representative samples of various types of banded iron-formation and its various minerals, associated sediments, iron ores and volcanic tuff from different localities of Orissa, India, are presented in this paper. The Orissa banded iron-formation is classified as Precambrian banded iron formation and is similar to the oxide facies iron formation of Lake Superior type. The Orissa iron formation consists only of iron oxide and silica with total absence of iron silicate, sulfide and carbonate minerals, and is devoid of terrigenous material. The trace element content suggests the source of the underlying quartzite to be a continental igneous rock mass, while the interbedded tuff are of undoubted volcanic origin. The overlying iron formation were chemically precipitated as oxidate sediments in which the principal iron mineral — magnetite — was formed at low temperature in a shallow marine environment. From the overwhelming similarity of major and trace element contents of all the samples from the different localities, it is postulated that these detached outcrops originated in the same continous basin.     

Comparison of Two Background Correction Procedures for X-Ray Fluorescence Trace element Analysis of Some Standard Samples

Ten geochemical reference samples were analysed for Rb, Sr and Cr by X-ray fluorescence spectrometry. The results obtained by two different background correction procedures are compared. For Sr both the correction procedures yield almost similar results in carbonate matrix; however, for Rb and Sr in silicate samples some significant differences are often noticed.     

The automated photometric determination of vanadium in geological samples with 4-(2-pyridylazo) resorcinol

Vanadium is determined in geological samples utilising the red complex formed between V⁵⁺ and 4-(2-pyridylazo) resorcinol. The determination is performed with the Technicon Auto Analyzer. The method has been applied to the determination of the element in standard rock and mineral samples after fusion with sodium carbonate and magnesium oxide. Using this sensitive method, it is possible to determine as little as 1 p.p.m. vanadium in a 200-mg sample of silicate rock or mineral.     

Primary Mineral Information and Depositional Models of Relevant Mineral Facies of the Early Precambrian BIF—A Preliminary Review

The primary mineral compositions of BIF are regarded as ferric oxyhydroxide or iron silicate nanoparticles (mainly greenalite and stilpnomelane ) whichcan transform into minerals like hematite, magnetite and siderite. On the basis of predominant iron minerals, three distinctive sedimentary facies are recognized in BIF: oxide facies, silicate facies and carbonate facies. Marked by the Great Oxidation Event (GOE, 2.4~2.2 Ga), sedimentary facies can be divided into two models: “anoxic and reducing” model and “stratified ocean” model. The ancient ocean was anoxic and reducing before GOE, and under this circumstance, BIF was distributed from the distal to proximal zones transforming from hematite facies through magnetite facies to carbonate facies, such as West Rand Group BIF (2.96~2.78 Ga) and Kuruman BIF (~2.46 Ga) in south Africa. However, the ancient ocean was a stratified ocean during and after GOE, which means that shallow seawater was oxidizing while deeper seawater was reducing, leading to an opposite sedimentary facies distribution compared to the former one: BIF was distributed from the distal to proximal zones transforming from carbonate facies through magnetite facies to hematite facies, such as Yuanjiacun BIF in China (~2.3 Ga) and Sokoman iron formation in Canada (~1.88 Ga). Overall, BIF is an unrepeatable formation in geological history, which can only form in specific sedimentary environment. The key point to speculate the paleo-ocean environment, namely the problems to be solved at the moment, is to identify and derive the primary mineral compositions, to make sure the genetic mechanism of sedimentary facies especially silicate facies, to restrict the sedimentary conditions and to study microbial activities contacting with BIF.