福州盆地第四纪钻孔XRF连续扫描的元素特征及沉积相指示意义

对福州盆地河口地区一个39 m钻孔岩芯进行X-Ray Fluorescence(XRF)扫描,通过XRF元素连续扫描结果探讨福州盆地海陆交互地层在不同沉积单元中各元素的变化特征及其沉积相指示意义。钻孔岩芯从晚更新世晚期至全新世共经历了5个沉积阶段：湖泊相—河流冲积相—淤泥质滨海潮滩相—河口潮滩相—河流冲积相。XRF扫描结果表明：元素Co, Fe, Ti, Si及其与Rb的比值受到沉积物粒度影响较大,对陆相(河流相)和海相(潮滩相)中粒度特征相近的层位进行了元素均值统计显示,近岸河口湾海相沉积物中的Ca, Ti, Mn, Fe, Co等元素是陆相地层中的3～10倍,Si元素则在陆相层中相对富集。说明除了粒度因素,海-陆沉积环境的变化对元素的富集也起到了重要作用。Ca,Ti,Mn,Fe,Co等元素是较好的海相沉积指示元素,而Si则是较好的陆相沉积指示元素,K,Rb,Sr对陆相沉积具有一定的指示意义。研究结果表明XRF元素连续扫描可以识别沉积物的元素变化细节,并根据元素的强度变化进一步判断沉积相,可以作为沉积相划分的重要辅助手段。该研究为XRF连续扫描方法在海陆交互带的应用提供了实例。     

中国原子光谱技术及应用发展近况

原子光谱（atomic spectrometry,AS）技术作为分析领域一个重要的组成部分,是尖端科学快速发展的助推器。随着国家对高新技术的愈加重视,国内的分析检测技术也在飞速发展,原子光谱技术作的发展则成为了极其重要的推动力。对中国原子光谱近4年（2015年-2018年）的研究成果与应用进展做了一个综述,内容主要分为六大部分：原子发射光谱（atomic emission spectrometry, AES）包括电感耦合等离子体发射光谱（inductively coupled plasma optical emission spectrometry, ICP-OES）,辉光放电发射光谱（glow discharge optical emission spectrometry, GD-OES）,介质阻挡放电发射光谱（dielectric barrier discharge optical emission spectrometry, DBD-OES）和激光诱导击穿光谱（laser induced breakdown spectrometry, LIBS）;原子吸收光谱（atomic absorption spectrometry, AAS）包括火焰原子化吸收光谱（flame atomic absorption spectrometry, FAAS）,石墨炉原子化吸收光谱（graphite furnace atomic absorption spectrometry, GFAAS）和氢化物发生原子吸收光谱（hydride generation atomic absorption spectrometry, HGAAS）;原子荧光光谱（atomic fluorescence spectrometry, AFS）;X射线荧光光谱（X-ray fluorescence spectrometry, XRF）;元素质谱（elemental mass spectrometry, EMS）包括电感耦合等离子体质谱（inductively coupled plasma mass spectrometry, ICP-MS）,辉光放电质谱（glow discharge mass spectrometry, GDMS）,激光电离源质谱（laser ionization mass spectrometry, LIMS）和原子探针层析成像（atom probe tomography, APT）;原子光谱分析的联用技术。主要关注了各个技术及各种联用技术在仪器设备、检测方法、检测性能上的突破和创新,并简要介绍它们在电子、冶金、地质、环境、制药、食品、生命科学等多种领域中的应用。     

原子光谱/元素质谱在生命分析中的应用进展

原子光谱/元素质谱是元素分析的强有力手段,其在生命分析领域的应用也越来越广泛。在单细胞元素分析方面,相关研究工作主要关注元素在单细胞中的分布和形态变化;在元素标记策略分析领域,利用原子光谱（atomic spectrometry, AS）和电感耦合等离子体质谱（inductively coupled plasma mass spectrometry, ICP-MS）实现对小分子、核酸、蛋白质等目标分析物的高灵敏检测是研究热点;在金属药物分析领域,ICP-MS为研究金属药物在生物体中的摄入、分布、代谢和排泄等过程提供了便利,也为进一步阐明药物作用机理以及金属药物的设计和改进提供了数据支持;在生物元素成像领域,ICP-MS与激光剥蚀技术（laser ablation, LA）联用,可以对生物样品进行原位分析和微区分析,结合有机质谱实现元素相关生物过程的分子机制研究;与相关分离方法联用,原子光谱和元素质谱还可以对生物组织中元素进行形态分析,研究其在相关过程中的生物转化过程。本文从单细胞元素分析、元素标签标记策略、金属药物转运与代谢以及生物组织中元素分布分析等方面,评述了原子光谱和ICP-MS在生命分析中的应用实例,并对该领域的发展前景进行了展望。     

ICP-OES研究罗布泊“大耳朵”湖相沉积物常量元素地球化学特征及环境意义

光谱分析技术应用于地球化学元素分析研究,为湖泊沉积物反演环境变化提供了更多的环境信息。以罗布泊“大耳朵”区域L07-10剖面沉积物为研究对象,利用ICP-OES对常量地球化学元素进行了测定分析,结合AMS进行14C年代学测定,初步探讨了该地区16.34 ka BP以来的气候环境变化。结果表明：常量元素地球化学特征可以灵敏的指示环境变化,元素环境代用指标很好的反映了该地区的气候变化过程。总体来看, 常量元素分布特征指示16.34 ka BP以来,罗布泊区域气候经历了暖湿-暖干-凉湿-暖干的变化,在8.09～6.34 ka BP期间发生了一次较明显的短期升温阶段,这一时期气候温暖干燥,降水减少,与全球及区域气候变化相关记录相吻合。近2 000 a以来气候总体温暖,降水量减少,源区水热条件变差,水运的搬运能力降低。     

藏药珠西的化学成分与结构分析

采用X射线荧光(XRF)、电感耦合等离子体发射光谱(ICP-OES)和X射线衍射(XRD)对不同来源藏药珠西中的元素成分和结构组成进行测定,以期揭示其药理作用的物质基础。XRF和ICP-OES分析结果表明,藏药珠西中主要元素为Fe,S和O,及少量的Si,Na,Mg,Al,K,Ni,Ca,Ti等元素。XRD分析表明,藏药珠西中主要存在立方晶系FeS2,此外还含有少量的斜方晶系Fe+3O(OH)等。通过XRF,ICP-OES和XRD分析,获得了藏药珠西的化学成分和结构组成基本数据,为其药理作用物质基础的揭示和质量标准的制定提供了科学依据。     

安徽茶园茶叶中四种大量元素和七种微量元素的含量分析及生物富集研究

主要采用电感耦合等离子体质谱技术(inductively coupled plasma mass spectrometry,ICP-MS)测定了安徽茶园茶叶中四种大量元素(Ca,K,Mg,P)和七种微量元素(Al,Mn,Fe,Cu,Zn,Cd 和Pb)含量,并进行了生物富集分析。结果表明,嫩叶中Ca,K,Mg 和 P的含量最高(Ⅰ, >3.0 mg·g-1),Al,Mn,Zn 和 Fe的含量次之(Ⅱ, 0.2～3.0 mg·g-1),Cu,Pb 和 Cd的含量最低(Ⅲ, <0.05 mg·g-1);而老叶中含量最高的是Ca,K,Mg 和Al(Ⅰ, >3.0 mg·g-1),P,Mn,Zn 和 Fe的含量次之(Ⅱ, 0.2～3.0 mg·g-1),Cu,Pb 和 Cd的含量最低(Ⅲ, <0.05 mg·g-1)。其中,P和Mn是茶叶中富集能力最强的;此外,Cu, Pb和Cd的含量低于相关的限量标准。聚类分析结果表明舒茶早和龙井43两个品种之间矿质元素的组成没有显著性的差异。     

应用电感耦合等离子质谱测定饲料中的微量元素的研究

应用电感耦合等离子体质谱(inductively coupled plasma-mass spectrometry,ICP-MS)测定饲料中铜、锌、铁、锰、铬、镉、铅、砷和硒等微量元素的方法。考察了谱干扰、基体效应和记忆效应等因素对测量的影响。在优化的条件下,方法检出限达到10-9级,线性范围达到3个数量级,线性相关系数高于0.999。将该方法用于实际样品的测定,小麦粉标准品中各元素的测定值与标示量能很好的吻合,配合饲料中微量元素的回收率在86％～115％,相对标准偏差(RSD)≤8.2%(n=6)。预混合饲料中微量元素的含量与国家标准方法测得值能够较好的吻合。该方法与传统方法相比,具有简单快速,灵敏度高,能够同时测定多种元素的优点。     

Ar介质感应耦合等离子加热器能量转化与流动特性

对感应耦合等离子(inductively coupled plasma,ICP)加热器内能量转化过程与分布规律、 流动特性的研究和认识能够为高频等离子加热器的设计提供理论指导,同时能够为加热器向大功率、多介质、广适用方向的发展提供支撑.基于二维轴对称、层流流动和局部热力学平衡等假设条件,利用COMSOL对百千瓦级Ar介...     

湖泊沉积物微量元素ICP-AES与XRF分析方法和相关性研究

首次以托素湖沉积物为研究对象, ICP-AES法测定沉积物微量元素Cd,Cr,Cu,Zn和Pb的含量, 不同的消解法研究和优化结果确定了一个最适合托素湖沉积物前处理的体系为： 5∶5∶5∶1∶1的HCl-HNO₃-HF-HClO₄-H₂O₂体系。同时与定性的XRF岩芯扫描法对托素湖沉积物微量元素进行分析,以及用含水量校正的方法,讨论了含水量对扫描方法的影响。数据比较表明,与背景值相对比,托素湖沉积物中的微量元素Cd和Zn含量偏高,Cr,Cu和Pb的含量均在背景值范围内,而XRF岩芯扫描主要受沉积物元素的控制,在一定程度上也受到沉积物中含水量的影响,两种方法测量结果有显著的正相关关系(r为0.673～0.925),具有很好的可比性。     

藏药矾石化学成分与结构分析

采用X射线荧光(XRF)、等离子体发射光谱(ICP-OES)和X射线衍射(XRD)等方法对不同来源藏药矾石的化学成分和结构组成进行分析。XRF和ICP-OES分析表明,藏药矾石主要元素为Ca,O和C,还含有少量Mg,Al,Na,Si,K,Ag,Ba,Fe,Mn,S,Sr,Zn等元素。XRD结构分析表明,其体系中主要存在三方晶系(MgxCa1-x)CO3(空间群为R-3c)或三方晶系CaCO3(空间群为R-3c),此外还含有少量的斜方晶系CaCO3(空间群为Pmcn)和六方晶系SiO2(空间群为P3221)等物相。通过X射线荧光、等离子体发射光谱和X射线衍射等分析,获得了藏药矾石元素成分和结构组成数据,为其物质基础的揭示和质量标准的制定提供了科学依据。     

ICP-OES/ICP-MS测定葵花子中28种无机元素

建立了葵花子中微量元素组成的分析方法。采用HNO₃+H₂O₂混合酸为消解体系经微波消解葵花子样品,电感耦合等离子体发射光谱(ICP-OES)法测定葵花子中Al,B,Ca,Fe,K,Mg,Na,Si,P和S,电感耦合等离子体质谱(ICP-MS)法测定葵花子As,Ba,Cd,Co,Cr,Cu,Li,Mn,Mo,Ni,Pb,Rb,Sr,Sn,Sb,Ti,V和Zn。采用国家一级标准物质大米(GBW10045)验证了方法的准确性,结果表明,标准物质的测定结果与参考值基本一致,葵花子中Ca,K,Mg,P,S的含量较高。该方法具有良好的准确性和精密度。     

X射线荧光光谱法测定硅酸盐中硫等20个主、次、痕量元素

本文使用新研制的偏硼酸锂和四硼酸锂混合熔剂，在１０００℃熔融制样，以Ｘ射线荧光光谱法测定硅酸盐等样品中的Ｓ，Ｎａ，Ｍｇ，Ａｌ，Ｓｉ，Ｐ，Ｋ，Ｃａ，Ｔｉ，Ｍｎ，Ｆｅ，Ｂａ，Ｃｒ，Ｖ，Ｓｒ，Ｚｒ，Ｒｂ，Ｃｕ，Ｎｉ和Ｎｂ等２０种元素，采用理论α系数和康普顿散射线作内标校正元素间的吸收－增强效应。其分析结果的精密度和准确度可与化学法相比     

Studying variations in the elemental composition of annual layers in microsections of lake teletskoye sediments by means of scanning X-ray fluorescent microanalysis using synchrotron radiation

SR scanning XRF is used to analyze the annual elemental layers of bottom sediments from Lake Teletskoye. Scanning is conducted with a pitch of 0.1 mm at energies of 16, 24, and 38 keV. The content of more than 15 elements are determined: K, Ca, Ti, Mn, Fe, V, Cr, Ni, Cu, Zn, As, Rb, Sr, Y, Zr, Cd, Sn, I, and Ba (range of concentrations, 0.005–10%). A cross section containing (1) the upper part of an underlying layer, (2) the total annual layer, (3) one more complete layer, and (4) the lower part of an overlapping layer is measured. Geochemical indicators reflecting the rhythm of annual precipitation are found.     

XRF与ICP-MS法在福建省安溪县和华安县的铁观音茶中元素含量测定的应用研究

安溪是铁观音茶的源产地,茶叶总产值每年数亿元,但不同品质的铁观音茶价格参差不齐,市场上存在以次充好的现象。福建省安溪县和华安县为铁观音主要的茶产地,两县市的茶叶产量市场占有率较高,地理位置毗邻,但茶叶品质和风味各有不同,造成茶叶市场的困扰。铁观音中微量元素种类和含量的检测,对产地的溯源具有重要的意义。采用X射线荧光光谱无标样半定量分析法（XRF）和微波消解/电感耦合等离子体质谱法（ICP-MS）对福建省主要茶产区安溪县（感德、西坪、祥华）和华安县（良村、华丰、仙都）的30份铁观音进行元素含量对比分析。XRF法检测出两县茶样中存在的元素种类有K,Ca,S,P,Mg,Al,Si,Cl,Fe,Mn,Rb,Zn,Na和Sr,但含量上存在一定的差异。根据XRF法检测结果进行快速、准确稀释茶样用于ICP-MS法对比测定金属元素,优化样品前处理方法以满足痕量检测要求。对比发现当测定Ca,Mg,Al,Fe,Mn和Zn金属元素时,相关性系数R2在0.824 8~0.892 8,趋势线斜率在0.806 0~0.944 9,XRF法和ICP-MS法的可比性较好,说明检测这六种元素采用这两种方法皆适合。同1份安溪铁观音茶样采用XRF法的相对标准偏差皆＜6.0%,ICP-MS法的相对标准偏差皆＜3.0%。相对于ICP-MS法,XRF法前处理更简单,耗时少,因此需低成本、快速、简便检测茶样中的Ca,Mg,Al,Fe,Mn和Zn元素含量时,可选择XRF检测法。采用ICP-MS检测出的K,Ca,Mg,Al,Fe,Mn,Rb,Zn,Na和Sr金属元素进行逐步判别分析,通过建立Fisher判别模型对安溪县和华安县铁观音茶样实现有效区分,模型建立的判别函数的产地检验判别率为96.7%,交叉检验判别率为96.7%,对测试样品的识别正确率为100%。ICP-MS法检测金属元素结合逐步判别-Fisher判别分析,对安溪县和华安县铁观音茶样产地溯源具有较强的可行性。     

Application of the background standard method for the determination of Rb,Sr, Y,Zr, and Nb contents in phosphorites by x‐ray fluorescence

The aim of the present work is to demonstrate the application of the x‐ray fluorescence (XRF) technique to the determination of Rb, Sr, Y, Zr, and Nb contents in phosphorites. The effect of a chemical sample composition on fluorescence intensities of analytical lines has been taken into account using the background standard method. A novelty of the work is the detailed study of a background to choose the background position, free from the spectral line overlaps of the elements presented in the sample. The most suitable background position is the position at the angle 2θ = 29° when using the analyzing crystal LiF(200). During our investigation we faced a problem of choice of Certified Reference Materials (CRMs) for the calibration of the phosphorites. To estimate interelement effects and to choose CRMs for the calibration the intensities were theoretically calculated. The statistical processing of analytical results of the technique is carried out. This technique may be applied to the determination of Rb, Sr, Y, Zr, and Nb contents in the phosphorites. Also, the possibility has been demonstrated to use the XRF technique for geochemical investigations of rocks. Phosphorites of Bokson‐Khubsugul Basin were selected as an example. As a result of the investigation the genetic type of phosphorites was established, which corresponded to the present geodynamical depositional environment. The character of the distribution of Rb, Sr, Y, Zr, and Nb contents in the phosphorites was also studied. Copyright © 2008 John Wiley & Sons, Ltd.     

Quantitative non‐destructive determination of trace elements in archaeological pottery using a portable beam stability‐controlled XRF spectrometer

A portable beam stability‐controlled XRF spectrometer developed at the LNS/INFN laboratories at Catania (Italy) was used for the non‐destructive determination of some trace elements (Rb, Sr, Y, Zr and Nb) in fine pottery artefacts. The XRF system and the method developed to control the energy and intensity stability of the excitation beam are briefly discussed. Concentrations of Rb, Sr, Y, Zr and Nb were determined in 50 fine potsherds from the votive deposit of San Francesco in Catania by using a multi‐linear regression method. Additionally, in order to test the homogeneity of the material composing the fine pottery samples, a small portion of a few potsherds was powdered and analysed using the XRF system and the multilinear regression method. A comparison between non‐destructive and destructive approaches is presented and discussed. Finally, quantitative XRF data were compared with those obtained by chemical analysis of the powdered samples. The results allowed the testing of a non‐destructive methodology to be used for the identification and grouping of the different typological classes of fine pottery mainly represented in the San Francesco sanctuary. Copyright © 2005 John Wiley & Sons, Ltd.     

X‐ray spectrometry applied for characterization of bricks of Brazilian historical sites

This paper presents the results of X‐ray fluorescence (XRF) analysis of bricks sampled from historical places in Pernambuco, a state in the northeastern region of Brazil. In this study, twenty bricks found in historical sites were analyzed. Two bricks made in the 17th century, presumably used as ballast in ships coming from Holland, five locally manufactured bricks: one from 18th century, three from 19th century, and one from 20th century, and thirteen bricks collected from a recent Archeological investigation of Alto da Sé, in the town of Olinda. Qualitative determination of the chemical elements present in the samples was undertaken using a self‐assembled portable XRF system based on a compact X‐ray tube and a thermoelectrically cooled Si‐PIN photodiode system, both commercially available. X‐ray diffraction analysis was also carried out to assess the crystalline mineral phases present in the bricks. The results showed that quartz (SiO₂) is the major mineral content in all bricks. Although less expressive in the XRD patterns, mineral phases of illite, kaolinite, anorthite, and rutile are also identified. The trace element distribution patterns of the bricks, determined by the XRF technique, is dominated by Fe and, in decreasing order, by K, Ti, Ca, Mn, Zr, Rb, Sr, Cr, and Y with slight differences among them. Analyses of the chemical compositional features of the bricks, evaluated by principal component analysis of the XRF datasets, allowed the samples to be grouped into five clusters with similar chemical composition. These cluster groups were able to identify both age and manufacturing sites. Dutch bricks prepared with different geological clays compositions were defined.