电子探针分析技术进展及面临的挑战

电子探针是研究地球与行星物质组成最基础的微束分析技术。近年来,固体地球科学和行星科学的不断发展,促使电子探针分析技术取得了一系列进展:矿物微量元素分析、稀土矿物测试方法完善、副矿物定年、富Fe矿物/熔体Fe~(3+)含量测定、场发射电子探针及软X射线分析谱仪的开发及应用等。同时,电子探针分析技术也面临着诸多挑战:微量元素测试在降低检测限的同时,还需要提高分析的准确度和精确度;降低二次荧光效应的影响;场发射电子探针在低电压下需要建立全新的分析条件和校正方式。基于这些挑战,电子探针未来在微量元素监测标样开发、二次荧光效应校正、场发射电子探针及软X射线分析谱仪应用、波谱仪完善和微区多种分析技术集成等方面具有发展潜力,以便为地学样品的研究提供更丰富、更准确的微米尺度成分信息。     

Homogeneity testing of microanalytical reference materials by electron probe microanalysis (EPMA)

Homogeneity testing of candidate reference materials requires distinguishing the effects of measurement uncertainty of the analytical method from true compositional variations within the material. Many in situ microanalytical techniques do not allow classical ANOVA homogeneity testing due to the infeasibility of truly replicated analyses on the same analysis volume. This also applies to the analysis of beam-sensitive and light element-bearing materials by electron probe microanalysis (EPMA). This reality has led me to reconsider the homogeneity index approach used in the testing of microanalytical reference materials by EPMA. Based on statistical considerations, I show that the homogeneity index is suitable for statistical significance testing using F and chi-squared statistics and allows estimating the contribution of compositional heterogeneity to the total uncertainty budget of the referenced values. However, there are problems of bias and masking of small compositional variations by measurement uncertainty. This contribution shows the strong impact of the total number of measurements on the resolution of a microanalytical homogeneity study and discusses how to quantify the relative contribution of heterogeneity to the total uncertainty budget. I present an example of EPMA to illustrate this approach and show some pitfalls and limitations in its application.     

皖南花山锑金矿床硫化物电子探针分析及其指示意义

花山锑金矿床位于皖南东至县境内, 是皖南地区代表性金-多金属矿床之一。 本次工作对花山锑金矿床开展了野外地质、岩相学特征观察以及金属硫化物电子探针分析, 得到以下结论：1） 花山锑金矿床主要成矿阶段可分为毒砂-黄铁矿（PyⅠ）阶段、黄铜矿-黄铁矿 （PyⅡ）阶段和方解石-辉锑矿阶段。 2） 金在不同阶段硫化物中均有赋存, 其矿化伴随整个热液成矿过程, 且以毒砂-PyⅠ阶段和黄铜矿-PyⅡ阶段为主。 毒砂-PyⅠ阶段和黄铜矿-PyⅡ阶段发育金矿化, 无锑矿化, 方解石-辉锑矿阶段发育锑、金共生矿化。 3） 早阶段即毒砂 -PyⅠ阶段和黄铜矿-PyⅡ阶段载金矿物为黄铁矿、毒砂及黄铜矿, 成矿物质来源以地层为 主;晚阶段即方解石-辉锑矿阶段载金矿物为辉锑矿, 成矿物质来源以燕山期岩浆岩为主。 本次工作对东至及皖南地区金矿床的寻找勘探具有重要的指示意义。     

电子探针和X射线衍射仪测定新疆祖母绿宝石

新疆首次发现了质量上佳的祖母绿宝石(绿柱石),受到了国内外学者的高度关注。文章对新疆祖母绿矿物晶体进行电子探针显微分析(EPMA)和X射线衍射(XRD)测试,获得EPMA成分分析结果及XRD测试晶胞参数、衍射图谱。结果表明,新疆祖母绿化学成分中Cr2O3含量较高,一般在0.21%~0.54%;典型样品晶胞参数测定结果为a0=0.923 3 nm,c0=0.920 6 nm,Z=2,主要粉晶谱线为2.871(100)、3.257(100)、7.996(100)。     

Electron probe microanalysis of rock-forming minerals with a JXA-8100 electron probe microanalyzer

The protocol for analysis of rock-forming mineral compositions by X-ray electron probe microanalysis used at the Institute of Geology and Mineralogy, Novosibirsk, Russia, is described. The analysis is conducted with a JXA-8100 electron probe microanalyzer capable to support a highly stable beam at relatively high probe currents for a long time. Elements that can be assayed range from sodium (atomic number Z = 11) to zinc (Z = 30). The operation conditions for routine analyses are substantiated: accelerating voltage 20 kV, probe current 50–100 nA, and signal accumulation time 10 s at both the peak and the background. The method of analytical problem formulation for measurements is presented. It is proven that the proprietary software is insufficient with the presence of the binary matrix effect and better correction methods are required. Metrological characteristics of the protocol have been studied. The variation coefficient, describing the reproducibility of results, averages 0.9% for major components (C > 10%), 2.5% for minor components (1 < C < 10%), and 6.8% for accessory components (0.3 < C < 1%). With still lower contents (0.05 < C < 0.3 %), the standard deviation of reproducibility is 0.02%. The values of the variation coefficient and standard deviation for measurement repeatability are approximately two times lower. The relative trueness of the method is within 1%. The detection limit (3o criterion) is generally within 0.01-0.03%. It can be improved by an order of magnitude by increasing the accumulation time and probe current.     

上扬子西南缘早三叠世嘉陵江组物源分析和构造环境:沉积学、重矿物电子探针和U- Pb年龄的限定

上扬子西南缘地区广泛分布峨眉山玄武岩,受其影响在中带金阳和外带荥经地区嘉陵江组发育滨岸和潮坪环境沉积物。本文在交错层理恢复的物源方向基础上,根据重矿物组成、重矿物电子探针和碎屑锆石测年结果,综合分析不同区域嘉陵江组物源区,进而探讨嘉陵江组形成的构造环境。嘉陵江组砂岩碎屑重矿物锆石、磷灰石、铬尖晶石等指示物源主要来自于岩浆岩,且自中带至外带基性岩浆岩所占比重逐渐减少。电气石电子探针分析显示,二者物源主要来自于贫锂花岗岩和变质砂岩、板岩。铬尖晶石显示,金阳地区物源来自峨眉山玄武岩和洋岛岩浆岩类岩石,荥经物源主要来自洋岛岩浆岩类岩石,个别为峨眉山玄武岩。碎屑锆石表明,嘉陵江组物源主要来自于新元古代岩浆岩和晚二叠世峨眉山玄武岩,前者经历再搬运。综合物源分析表明,嘉陵江组物源主要来自康滇古陆,岩石类型主要为峨眉山玄武岩和砂岩等。沉积序列和物源分析表明,嘉陵江组反映了沉积物蚀顶过程。结合地震资料、大火成岩省的分析成果表明,嘉陵江组形成于火山型裂谷边缘。     

某矿床铂钯等贵金属元素的电子探针分析

某矿床为一大型的铜镍铂钯矿床,原矿石化学分析有用元素为：Ｐｔ１－３８ｇｔＰｄ２－３６ｇｔ、Ｃｕ０－１４％、Ｎｉ０－２２％。显微镜观察发现,矿石主要金属矿物为黄铜矿、紫硫镍矿、黄铁矿、磁铁矿、铬铁矿,脉石矿物为蛇纹石、辉石等。经显微镜观察以及电子探针扫描分析,铂钯矿物在矿石中嵌布颗粒粒度细小,与不同矿物连生,根据电子探针分析,仍有许多超显微状态的铂钯矿物赋存在硫化矿物中。１　样品制备与仪器设备及实验条件从原矿石中挑选部分有代表性矿石,切割抛光制成矿石光片,经显微镜镜下鉴定后,留待进行电子探针分…     

Disproportionation of Fe<Superscript>2+</Superscript> in Al-free silicate perovskite in the laser heated diamond anvil cell as recorded by electron probe microanalysis of oxygen

Experimental evidence is reported for Fe²⁺ disproportionation in Al-free perovskite (Pv), when submitted to large temperature gradients (i.e., under off-equilibrium conditions) in a laser heated diamond anvil cell (LHDAC). To enable this effect, the experimental procedure was designed to produce large radial and axial temperature gradients. In the Pv and ferropericlase (Fp) assemblage synthesized after dissociation of natural olivine, the three chemical states of iron (i.e., Fe⁰, Fe²⁺ and Fe³⁺) could be evidenced by electron probe microanalysis (EPMA), through variations of oxygen contents attached to the Fe cations. Despite inherent difficulties for determination of O-contents and Fe³⁺/ΣFe ratios using EPMA, we recorded significant changes in iron oxidation state across the laser-heated strip. These changes are correlated with variations in composition for the major elements (Fe, Mg, and Si), which evidences that the Pv/Fp assemblage experienced large segregation under the strong temperature gradients. Grains of metallic iron were detected in parts of the laser-heated strip coexisting with a Pv phase with Fe/(Mg + Fe) = 6 at% and most of its iron as Fe³⁺. This Fe²⁺-disproportionation reaction involves insertion of Fe³⁺-defects in the Pv lattice. This Fe³⁺-bearing Pv phase is presumably unstable and decomposes into a mineral assemblage including magnesioferrite, which is detected at the border of the laser-heated strip.     

含超轻元素Be矿物的电子探针定量分析——测试条件的约束

铍（Be）是战略性资源,属于关键金属。Be在电子探针（EMPA）可分析的元素范围内属于最难测准的一个元素。难测准的原因在于Be属于超轻元素,其特征X-射线不但信号弱、能量低,而且易受其他元素强烈吸收效应的影响,因此硬件上需要EMPA配置大面网间距的特殊分光晶体。而不同厂家不同大面网间距分光晶体配置的EMPA在铍矿物的测试条件存在明显差异,即使同一EMPA测试不同Be矿物分析条件也不一致。尤其是占据国内市场主流的JEOL电子探针目前也只尝试分析过绿柱石一种Be的矿物。本文利用配置LDE3H分光晶体的JXA-8100（JEOL）电子探针,对除绿柱石之外的金绿宝石、硅铍石、硼铍石和锌日光榴石四种Be矿物开展了Be等元素最佳定量分析方法的研发。通过不同铍矿物的全元素扫描,发现与CAMECA电子探针不同,JEOL电子探针不存在Be_Kα峰被Si_L2,3,M1峰干扰问题。同时发现每种含Be矿物Be_Kα峰位存在不同程度的漂移现象,并结合原子轨道杂化及吸收效应等理论对该现象进行了合理的解释。在此基础上,建立起配置LDE3H分光晶体的JEOL电子探针定量分析金绿宝石、硅铍石、硼铍石和锌日光榴石不同Be矿物中Be等元素含量的有效方法。该Be矿物原位分析方法的探索,不仅为JEOL EMPA用户提供Be矿物分析的成熟经验,也必将为铍资源的相关研究和找矿勘查提供有力的技术支撑。

     

电子探针技术研究粤北龙华山岩体中独居石蚀变晕圈的结构与成分特征

淡钡钛石为含硼硅酸盐矿物,晶体结构属二轴晶单斜晶系,是典型的热液成因矿物。产于中国准噶尔盆地风城组页岩中的淡钡钛石尚未开展矿物学研究,其成因尚不明确。本文选取了该地玛页1钻井岩心中的淡钡钛石,采用电子探针(EPMA)、X射线能谱(EDS)和X射线衍射(XRD)分析其矿物成分和晶体结构特征。结果表明：风城组淡钡钛石晶体大小为微米级,形态呈板状或短柱状,与硅硼钠石共生。矿物主要元素组成为：BaO 12.64%,TiO₂ 13.47%,Na₂O 10.69%,SiO₂ 53.46%,B₂O₃ 10.11%;d=4.22(-220)、d=8.45(-110)、d=3.37(-112)对应的三个晶面最发育。风城组淡钡钛石元素组成及晶体衍射特征与国外发现的淡钡钛石相吻合,但更富硼元素。由于热液流体中硼含量与盐度呈明显正相关,因此风城组淡钡钛石形成于更高盐度热液流体中,深部热液流体侵入到风城组页岩中依次形成硅硼钠石、淡钡钛石。该研究结果为准噶尔盆地风城组淡钡钛石矿物学的进一步研究提供了基础资料。

     

水体悬浮颗粒物的扫描电镜与X射线能谱显微分析

通过对湖州地区74个土壤样品多环芳烃含量的测定,分析了湖州市不同土地利用类型土壤中多环芳烃(PAHs)的含量特征及污染水平。结果表明,湖州地区PAHs各组分的含量均有检出,各种土地利用类型表层土壤均受到一定程度的PAHs污染,但均小于荷兰土壤修复标准;湖州市区耕地中PAHs的含量最高;从PAHs低环/高环比值小于1以及芘/苯并(a)芘比值小于2,反映了湖州地区土壤中PAHs主要是由燃煤和生活污染产生的。     

Tephrological implications of beam size—sample‐size effects in electron microprobe analysis of glass shards

This paper concerns the potential consequences of varying procedures for the determination of tephra geochemistry by electron microprobe. Application of electron probe microanalysis to tephrostratigraphical methods has increasingly facilitated the resolution and refinement of Quaternary chronology associated with records of proxy‐environmental or proxy‐climatic change. The geographical range over which tephras are recovered has expanded significantly with the identification and analysis of crypto (or hidden) tephras in areas far removed from tephra sources. These tephras are dominated by glass shards, which, in many distal environments, may be either small in size (μm) or may be highly pumiceous with low glass:void ratios and thin (<10 μm) shard walls. We demonstrate that reducing the size of the electron beam used to analyse shard geochemistry cannot be used reliably to permit analysis of thin glass walls. This approach distorts the geochemical data, creating analytical differences that may generate inappropriate tephrogeochemical fingerprints. Additional distortion of the geochemical fingerprint in the form of hybrid analyses may be encountered in glass fragments containing micron‐sized crystalline phases such as feldspar. Copyright © 2001 John Wiley & Sons, Ltd.     

碎屑重矿物分析对内蒙古西乌旗早二叠世寿山沟组的物源指示及构造意义

碎屑重矿物由于相对比较稳定,蕴含重要的成因信息,对其进行电子探针成分分析,能够还原岩石形成的物源区和盆地构造背景。内蒙古西乌旗早二叠世寿山沟组一段主要由砂岩夹砾岩等组成,二段主要由粉砂岩、泥岩等组成。重矿物分析表明,寿山沟组一段和二段砂岩重矿物主要有锆石、尖晶石和石榴子石等,指示其物源区为岩浆岩和变质岩。重矿物电子探针成分分析结果显示,电气石成分指示其具贫锂花岗岩和变沉积岩物源,尖晶石成分指示其具岛弧和洋中脊玄武岩类物源,石榴子石成分指示其具高级变质基性岩源区。综合物源分析显示,寿山沟组主要来源于迪彦庙蛇绿岩、锡林浩特杂岩和本巴图组玄武岩等。结合区域地质对比,认为寿山沟组形成于弧后盆地,古亚洲洋在早二叠世时期尚未闭合。     

太原市灰霾期间黑碳气溶胶形貌与成分分析

为掌握太原市冬季灰霾发生期间黑碳气溶胶形貌特征和化学成分变化特点,分别于2011-12-30T08:00至2012-01-01 T 04:00和2018-11-25 T 08:00至2018-11-27 T 04:00灰霾发生期间在山西大学环境与资源学院楼顶使用MAY七级冲击式颗粒采样器每隔4h采集空气动力学直径分别为0.25～0.5μm、0.5～1.0μm以及1～2μm的大气单颗粒分析样品,运用带超薄窗口能谱仪的扫描电镜(JEOL JSM-6390)测定了样品中4330个颗粒的二次电子像及X射线能谱,通过基于蒙特卡罗模拟程序的定量电子探针微区分析技术对每个颗粒的元素原子浓度进行了计算,并对颗粒进行了分类与计数。共检测到6类颗粒,分别是矿物尘、碳质颗粒、钠盐颗粒、二次颗粒、富铁颗粒和其他,其中黑碳气溶胶数量相对丰度在2011和2018年样品中平均为26.8%和34.2%。按照伸长率(E)、纵横比(R)、是否与其他物质结合等将其分为伸展型、支链型、嵌入或粘附型和团聚型4种,反映了黑碳颗粒不同的老化过程。2011年样品中团聚型和支链型数量较多,而2018年样品中伸展型和嵌入型多于团聚型和支...     

Electron Microprobe/SIMS Determinations of Al in Olivine: Applications to Solar Wind,Pallasites and Trace Element Measurements

Electron probe microanalyser measurements of trace elements with high accuracy are challenging. Accurate Al measurements in olivine are required to calibrate SIMS implant reference materials for measurement of Al in the solar wind. We adopt a combined EPMA/SIMS approach that is useful for producing SIMS reference materials as well as for EPMA at the ~ 100 µg g^?1 level. Even for mounts not polished with alumina photoelectron spectroscopy shows high levels of Al surface contamination. In order to minimise electron beam current density, a rastered 50 × 100 µm electron beam was adequate and minimised sensitivity to small Al‐rich contaminants. Reproducible analyses of eleven SIMS‐cleaned spots on San Carlos olivine agreed at 69.3 ± 1.0 µg g^?1. The known Al mass fraction was used to calibrate an Al implant into San Carlos. Accurate measurements of Al were made for olivines in the pallasites: Imilac, Eagle Station and Springwater. Our focus was on Al in olivine, but our technique could be refined to give accurate electron probe measurements for other contamination‐sensitive trace elements. For solar wind, it is projected that the Al/Mg abundance ratio can be determined to 6%, a factor of 2 more precise than the solar spectroscopic ratio.     

Flotation of oxidized minerals of copper using a new synthetic chelating reagent as collector

A new synthetic reagent containing a mixed aliphatic-aromatic structure, with a hydrocarbon chain and an aminothiophenol chelating group, has proven to be an effective collector for the flotation of chrysocolla minerals. The flotation is optimum in the narrow pH range of 5.5 to 6, falls sharply at pH 5, and is moderate in the pH range 7 to 11. Infrared spectra indicate that copper aminothiophenolate chelates are formed on the surface of the chrysocolla under the conditions of maximum flotation.     

The Study Internal Structure of the Annual Layers in Lake Sediments Using Synchrotron Radiation with X-ray Focusing Optics

正1 Introduction Annually laminated(varve)sedimentary deposits are considered as one of the most important archives,since they offer precise temporal information(years)in combination with high time resolutions.Bottom sediments of the lakes contain detailed geochemical information on     

黔东施秉下翁哨地区金刚石指示矿物地球化学特征及其地质意义

对黔东施秉下翁哨地区金刚石指示矿物镁铝榴石、铬尖晶石分别进行了电子探针（EMPA）主量元素和LA- ICP- MS微区原位微量元素测试,结果表明：镁铝榴石主要属于G9型（约占87%）,次为G12型（约占11%）和G3型（约占2%）,源区为二辉橄榄岩和异剥橄榄岩,当其与橄榄石共生,获得平衡温度（tNi）为686~1225℃,压力（PCr）为1.9~4.0 GPa,少数落在形成金刚石的主要温压范围内（压力约4.0~6.5 GPa,温度约950~1300℃）;铬尖晶石主要来源于橄榄岩尖晶石捕虏晶（Xen）（约占90%）,少量为铬铁矿（Chr）（约占10%）,个别落在全球原生金刚石中铬铁矿包裹体的范围内。研究认为,恢复区域加里东期造山运动以来的古地貌,寻找金刚石指示矿物的母岩体/新岩体及开展其矿物间的对比研究工作,特别是对加里东期以来区域的地幔物质组成、岩石圈厚度和热状态等进行深入研究,将对扬子克拉通的演化、深部地幔结构剖析和金刚石成矿事件等具有重要的科学研究意义。