利用激光气流分割技术同时测定斜长石的微量元素与Sr同位素

斜长石是火成岩中的主要造岩矿物之一。其微量元素和Sr同位素组成可以用来示踪多种地质过程。传统的斜长石研究需要进行2次独立的激光剥蚀电感耦合等离子体质谱分析,来分别测试微量元素和Sr同位素组成。然而对于具有复杂环带结构的斜长石, 2次激光剥蚀分析获得的微量元素和Sr同位素可能是解耦的。本研究采用近几年兴起的激光气流分割技术建立了通过1次激光剥蚀同时测试斜长石微量元素和Sr同位素的方法。该方法将1台激光剥蚀系统(LA)同时与1台高分辨率扇形磁场等离子体质谱(SF-ICP-MS)和1台多接收等离子体质谱(MC-ICP-MS)联机。在1次激光剥蚀过程中,通过Y形接头将激光剥蚀产生的气溶胶分为两路,一路气溶胶进入MC-ICP-MS进行同位素组成分析,另一路气溶胶进入SF-ICP-MS进行微量元素含量分析。使用本方法分析USGS玄武玻璃标样BHVO-2G和NKT-1G的Sr同位素组成和微量元素含量,分析结果在误差范围内均与推荐值或前人报道值一致。此外,本研究利用建立的方法对满洲里巴杨山塔木兰沟组火山岩中的斜长石斑晶进行了微量元素和Sr同位素的同时测试,并利用斜长石成分计算了平衡熔体的微量元素组成。...     

微区原位普通铅同位素分析技术及其地质应用进展

应用激光剥蚀-多接收器电感耦合等离子体质谱(LA-MC-ICP-MS)和二次离子质谱(SIMS)等分析技术进行微区原位普通Pb同位素分析是微区地球化学研究的重要内容之一.综述了矿物、熔体包裹体和沉积结核的微区原位普通Pb同位素分析技术及其地质应用的新进展.这些研究资料表明该分析技术在岩浆岩成因、沉积物物源示踪、地幔地球化学、古海洋学以及矿床学等的研究中提供了常规的全岩Pb同位素分析方法难以获得的重要信息,充分展示了该分析技术在地球科学研究中的应用前景.     

激光剥蚀等离子质谱微区分析在固体地球科学中的应用进展

当前分析化学技术正向着痕量微区方向发展。这使得我们能够用更小更少的样品直接得到更多的地球化学信息。在诸多微区测试技术中,激光剥蚀等离子质谱（LA-ICPMS）技术发展最快。其地质应用较广,激光探针等离子体质谱能够进行固体样品的微区微量元素和同位素的分析,具有灵敏度高、简便、快速的特点,同样具有在同位素定年上的潜力。近年来又研制出激光剥蚀多道接收等离子质谱（LA-MC-ICPMS）仪,使得微区同位素分析开始了新的革命。而多种微区技术综合应用为近几年分析地球化学新的趋势。     

同位素质谱分析测试技术进展

同位素质谱分析测试技术是同位素研究的基础。本文评述了同位素质谱分析测试技术中常用的多接收器等离子体质谱法、激光探针质谱、离子探针、热电离质谱法和高精度质谱计分析同位素的原理、应用范围、存在问题和研究进展,建议选择分析同住素方法时,需考虑每种方法各自的特点和优势、仪器的性能等。     

湖南铜山岭花岗闪长岩中榍石微区原位Nd同位素和微量元素组成及其岩石成因的指示意义

与热液矿床形成有关的花岗质岩石普遍遭受热液蚀变,且全岩成分仅代表均一化某一时间点的信息,采用全岩成分分析难以有效地揭示花岗质岩石的形成与演化。花岗质岩石中副矿物稳定不容易蚀变,近年原位测试技术的快速发展和日趋成熟,可以准确获取副矿物原位元素和同位素组成,通过副矿物元素和同位素组成可以有效地揭示岩浆来源和演化信息,显著提高了岩浆作用过程的空间分辨率,成为探讨岩石成因的新手段。本文以湘南与铜铅锌多金属成矿密切相关的铜山岭岩体为研究对象,利用电子探针(EPMA)、激光剥蚀等离子体质谱(LA-ICP-MS)和激光剥蚀多接收等离子体质谱(LA-MC-ICP-MS)等原位测试技术,对花岗闪长岩和暗色包体两类岩石样品中的副矿物榍石开展了原位元素和Nd同位素分析。结果表明：所有榍石中Al+Fe与Ti具有明显的负相关关系且稀土元素含量较高,稀土元素与Al和Fe一起主要通过(Al, Fe³⁺)+REE=Ti⁴⁺+O^2-方式替换榍石的Ti位和Ca位而进入晶格。球粒陨石标准化稀土配分模式上,大部分榍石显示Eu正异常。榍石中微量元素对Zr/Hf、...     

激光剥蚀-等离子体质谱技术及其在地球化学宇宙化学和环境研究中的应用

激光剥蚀-等离子体质谱(LA-ICPMS)已成为地球化学、宇宙化学和环境研究领域元素和同位素原位分析最重要的技术之一。文章介绍了多种类型的质谱仪及其使用的激光器。用途最广的LA-ICPMS仪器之一是单接收器扇形磁场质谱仪,配有Nd:YAG激光剥蚀系统(激光波长分为193 nm和213 nm两种),MPI Mainz实验室使用的就是这套系统,文章对此作一详细介绍。文中阐述了数据优化技术及其多种校正过程;介绍LA-ICPMS在痕量元素和同位素分析领域的一些应用,包括参考物质的研制,Hawaiian玄武岩、Martian陨石、生物骨针和珊瑚虫中痕量元素分析及熔融包裹体和富钙-铝碳质球粒陨石中的铅和锶同位素测量。     

地幔流体及其成矿作用

高灵敏度、高精密度、低检出限、多元素同时检测并可提供同位素组成比值信息的等离子体质谱与高空间分辨率的紫外激光采样技术结合 ,可定量地测定单个流体包裹体中常、微量元素含量 ,为成矿流体的研究提供了一个新的研究手段。文中简要地介绍了激光剥蚀电感耦合等离子体质谱 (LA ICP MS)分析仪器的发展 ,结合实验室的研究工作 ,就激光剥蚀池的设计、单个流体包裹体的剥蚀方法、元素的分馏效率、定量校正技术及其在成矿成因物理化学机制研究中的应用等进行评述 ,并阐述单个流体包裹体元素组成的LA ICP MS分析技术存在的局限和发展趋势。     

激光剥蚀电感耦合等离子体质谱微区分析 进展评述

激光剥蚀电感耦合(LA-ICP-MS)等离子体以其高空间分辨率、高灵敏度、多元素同时测定并可提供同位素比值信息的检测能力在原位微区分析中已得到广泛应用。现从仪器的发展、基础研究等方面评述了近年来LA-ICP-MS微区分析的进展,重点介绍了与等离子体质谱(ICP-MS)联用的激光器(纳秒和飞秒激光器)的发展、校正方法、分馏效应及其在地球科学微量元素、同位素、包裹体分析中的应用。并简要地阐述了LA-ICP-MS分析技术存在的局限和发展趋势。     

流体包裹体中Sr同位素的激光剥蚀多接收等离子体质谱原位微区分析

本文研究了用激光剥蚀多接收等离子体质谱（LA-MC-ICPMS）技术原位微区分析包裹体中Sr同位素的分析方法。5、10、16和30μm剥蚀序列进行包裹体的Sr同位素组成分析结果表明,包裹体中Sr同位素比值和Rb含量明显高于与包裹体接触的方解石矿物,从大个体包裹体（大于2μm）可获得较准确的Sr同位素组成（精密度为0.08%）。由于87Rb的含量只能通过85Rb计算而来,有限包裹体分析信号而导致的Sr同位素分析精度较传统的化学方法略差,因此本方法不能得到包裹体中的Rb-Sr年龄。     

铁同位素分析测试技术研究进展

铁是地球上丰度最高的变价元素,在自然界大量分布于各类矿物、岩石、流体和生物体中,并广泛参与成岩作用、成矿作用、热液活动和生命活动过程。铁同位素组成对地球化学、天体化学和生物化学方面提供重要的信息,是同位素地球化学研究领域的热点。铁同位素的精确测量是开展相关研究的重要基础。本文评述了铁同位素测试技术的研究进展,主要包括:①溶液法测试铁同位素样品纯化过程中阴离子树脂的改进;②质谱分析从传统的热电离质谱法发展为多接收电感耦合等离子体质谱法;③激光微区原位测试技术的研发等。在此基础上,对测试过程中会导致产生铁同位素分馏的步骤和校正方法进行了总结,并对各种测试方法的优缺点进行了评述。本文认为:溶液法分析流程长且复杂,但分析精度高(0.03‰,2SD)、方法稳定;微区原位分析方法从纳秒激光剥蚀发展为飞秒激光剥蚀,脉冲持续时间更短、脉冲峰值强度更高(可达10~(12)W),聚焦强度超过10~(20)W/cm~2,使其具有分析速度快、空间分辨率高的优势。微区原位法可以从微观角度去讨论铁同位素变化的地球化学过程,但基体效应的存在限制了微区原位铁同位素的广泛应用。因此,缩短溶液法分析流程,开发系列基体匹配的标准样品,是铁同位素分析方法研发的方向。     

A Preliminary Appraisal of Seven Natural Zircon Reference Materials for In Situ Hf Isotope Determination

There is a growing need for new zircon reference materials for in situ Hf-isotope analysis by laser ablation-multicollector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS). In this contribution we document the results of a preliminary investigation of seven natural zircons, conducted in order to test their suitability in this regard. Solution MC-ICP-MS data on separated Lu and Hf fractions provided reference compositional data while the results of ca. 750 in situ LA-MC-ICP-MS analyses allowed assessment of potential micrometre-scale heterogeneity. On the basis of these analyses and additional relevant considerations such as availability, size and (Lu)Yb/Hf ratio, we suggest that, of the currently available zircons, Temora-2 and Mud Tank are most likely to provide robust reference materials for Hf isotope determinations both at the present time and into the future. The former has the advantage of also being well-characterised for U-Th-Pb systematics and suitable for in situ age determination, while the latter is the most readily available and is of very large grain size. Additional materials such as BR266, and 91500, although limited in supply, show more consistent Lu/Hf ratios and are thus of use in monitoring elemental fractionation during ICP-MS analysis.     

Accurate U-Pb Age and Trace Element Determinations of Zircon by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry

Various zircons of Proterozoic to Oligocene ages (1060-31 Ma) were analysed by laser ablation-inductively coupled plasma-mass spectrometry. Calibration was performed using Harvard reference zircon 91500 or Australian National University reference zircon TEMORA 1 as external calibrant. The results agree with those obtained by SIMS within 2s error. Twenty-four trace and rare earth elements (P, Ti, Cr, Y, Nb, fourteen REE, Hf, Ta, Pb, Th and U) were analysed on four fragments of zircon 91500. NIST SRM 610 was used as the reference material and ²⁹Si was used as internal calibrant. Based on determinations of four fragments, this zircon shows significant intra-and inter-fragment variations in the range from 10% to 85% on a scale of 120 μm, with the variation of REE concentrations up to 38.7%, although the chondrite-normalised REE distributions are very similar. In contrast, the determined age values for zircon 91500 agree with TIMS data and are homogeneous within 8.7 Ma (2 s ). A two-stage ablation strategy was developed for optimising U-Pb age determinations with satisfactory trace element and REE results. The first cycle of ablation was used to collect data for age determination only, which was followed by continuous ablation on the same spot to determine REE and trace element concentrations. Based on this procedure, it was possible to measure zircon ages as low as 30.37 0.39 Ma (MSWD = 1.4; 2 s ). Other examples for older zircons are also given.     

The Role of Isotopic Reference Materials for the Analysis of "Non-Traditional" Stable Isotopes

The advent of multiple collector-inductively coupled plasma-mass spectrometry has provided an impetus to the study of isotope abundance variations in natural materials. In particular, the study of "non-traditional" stable isotopes has revealed isotope fractionation variations caused by a range of physiochemical and biological mechanisms. The magnitude of these variations may be < 1 per mil per mass unit, but are significant in terms of the experimental uncertainties involved, provided rigorous mass spectrometric protocols are followed. The double spike technique can be used effectively to evaluate isotope fractionation effects for both multiple collector-inductively coupled plasma-mass spectrometry and thermal ionisation mass spectrometry. The demanding nature of this research implies the need for internationally-accepted reference materials so that interlaboratory comparisons can be made with confidence. At present, isotopically certified reference materials are unavailable for many elements, including Cu, Zn, Mo and Cd, and it is important that this situation be rectified as soon as practicable. Until such time as isotopically certified reference materials become available for every element, stable isotope geochemists should adopt a common reference material as the standard for each element so that rigorous interlaboratory comparisons can be made.     

铀矿地质钻探岩心样品系统分析法

铀矿地质钻探岩心样品系统分析法包括：岩心样品的γ辐射测量、切片观测测量、样品粉碎、矿物微粒分选、激光拉曼光谱分析、傅立叶红外光谱分析、包体流体观测与测量、X射线荧光光谱分析、X射线衍射分析、电子探针分析、高纯锗γ能谱分析、湿法化学分析、ICP～MS微量元素分析、铀矿物和其它矿物同位素组成分析等步骤,通过这些步骤的系统分析,得到铀矿地质钻探岩心样品的全息资料,为铀矿地质勘探提供支持和服务。     

煤中痕量溴的分析测试方法研究进展

综述了近年来国内外煤中痕量溴测定方法的研究进展,介绍了间接分析法和直接分析法的基本特点和原理。间接分析法是先用高温热水解法、碱熔法或微波处理法等消解煤样品,使煤中溴进入溶液中,再用离子色谱法、电感耦合等离子体质谱法等技术测定煤消解液中溴的含量。直接分析法是用X射线荧光光谱法或中子活化法直接测定固体煤中溴的含量。对各种测试方法的适用性、存在问题及发展方向进行了比较和评述。     

电感耦合等离子体质谱法测定地质样品中锗和镉的干扰及校正

采用HF-HClO₄-HNO₃分解样品,8 mol/L HNO₃提取剂,外标法校准,电感耦合等离子体质谱法同时测定地球化学样品中锗和镉。选择¹⁰³Rh为内标,确定了最佳仪器参数,研究了Zn、Zr、Sn、Ce、Nd、Sm对Ge和Cd的干扰,试验选择质量数⁷⁴Ge和¹¹⁴Cd作为测定同位素,采用数学公式校正法校正了来自Nd和Sm的二次电离离子对Ge的干扰、Sn对Cd的同质异位素干扰。方法检出限（10s）分别为Ge 30 ng/L、Cd 15 ng/L,精密度（RSD,n=15）为Ge 1.35%、Cd 1.47%。对多种国家一级标准物质进行分析验证,结果与标准值相符。方法适用于地质样品中微量锗和镉的测定。     

The origin of variable-δ18O zircons in Jurassic and Cretaceous Mo-bearing granitoids in the eastern Xing–Meng Orogenic Belt,Northeast China

This study reports new zircon U–Pb ages, Lu–Hf isotope data, and oxygen isotope data for Mesozoic Mo-bearing granitoids in the eastern Xing–Meng Orogenic Belt (XMOB) of Northeast China, within the eastern Central Asian Orogenic Belt. Combining these new laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) zircon U–Pb ages with the results of previous research indicates that two stages of Mo-bearing granitoid magmatism occurred in the eastern XMOB, during the Early–Middle Jurassic (200–165 Ma) and the Early Cretaceous (ca. 111 Ma). The eastern XMOB also contains Mo-bearing granitoids with variable δ¹⁸O compositions that record variations in source oxygen isotopic compositions. Combining δ¹⁸O data with zircon U–Pb and Hf isotopic data provides evidence of the origin of these granitoids. Three types of zircon have been identified within these granitoids. Type 1 zircons formed during the Mesozoic and having high δ¹⁸O values (5.71–7.05‰) that are consistent with the compositions of magmatic zircons from the Luming, Jiapigou, and Kanchuangou areas. These zircons suggest that the Mo-bearing granitoids were derived from a source containing supracrustal materials. The type 2 zircons have extremely low and heterogeneous δ¹⁸O values (4.64–4.89‰) that are consistent with the compositions of magmatic zircons from the Jidetun and Fuanpu areas. These magmas were generated by the remelting of juvenile crustal material that was previously significantly modified by interaction with fluids. Type 3 zircons generally have mantle-like δ¹⁸O values (5.42–5.57‰), with several zircons yielding higher δ¹⁸O values, suggesting that these intrusions formed from mantle-derived magmas that assimilated and were metasomatized by crustal material. Combining these geochemical data with the geology of this region indicates that the Mo-bearing granitoids were generated as a result of subduction of the Palaeo-Pacific Plate beneath the Eurasian continent.     

碎屑锆石U-Pb年龄有效性初探

碎屑锆石U-Pb 年代学是限定沉积地层年龄、追踪沉积物源、揭示区域构造演化历史等重要的手段,在地质学和地理学领域应用广泛。近年来,单颗粒碎屑锆石数据获取技术日渐成熟,数据量激增,然而,部分邻近甚至相同地区不同研究组获得的原始数据存在差异甚至相互矛盾。如何高效严谨地获取及处理数据,并挖掘其中所蕴涵的丰富的地质信息,越来越受到研究者的重视,但目前相关方面的研究较少。以青藏高原东北缘酒西盆地新生代疏勒河组砂岩碎屑锆石为例,采用标准实验流程,通过试验数据之间的横向和纵向对比,确定合理的碎屑锆石颗粒测试数量,利用碎屑锆石颗粒外部形态与内部结构特征相结合的方法,选择有效的测试点,发现单颗粒锆石阴极发光（CL）图像在数据测试、分析和应用方面极具前景。具体取得如下认识:1）碎屑锆石U-Pb测年前处理时需采用标准的重矿物分选流程,以保持所采集的碎屑样品中单颗粒锆石分布的全貌,避免引起年龄组分丢失或偏差;制作样品靶及选择测年颗粒时,需将全部锆石单颗粒在体视显微镜及扫描电镜下的特征紧密结合,得到最优有效数量的单颗粒年龄,提高效率及数据的准确性、完整性;2）数据处理、分析及应用中,必须结合单颗粒锆石CL图像,修正或剔除异常数据,避免由于激光剥蚀点或离子束跨越特征不同的生长环带产生无意义的“混合年龄”。该研究为碎屑锆石U-Pb年代学大数据处理及应用提供了基础技术支撑,且为有效甄别U-Pb测年数据质量进而合理、准确地应用于地学研究提供了新的视角。     

Determination of Trace Elements in BCS CRM 313/1 (BAS) and NIST SRM 1830 by Inductively Coupled Plasma-Mass Spectrometry and Instrumental Neutron Activation Analysis

In the past, there has been little interest in the trace element characteristics of quartz, and in consequence little activity in the trace element characteristics of reference materials with high silicon content. The main purpose of this paper is to contribute to the characterisation of two international certified reference materials, BCS 313/1 from the Bureau of Analysed Samples, (BAS), UK and SRM 1830 from the National Institute of Standards and Technology (NIST), USA. BCS 313/1 was analysed by laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS), solution ICP-MS and instrumental neutron activation analysis (INAA). NIST SRM 1830 was analysed by LA-ICP-MS and INAA. Analytical results are reported for more than forty elements, most of them for the first time. For most elements, the results obtained by the different methods agree within 15 % relative. The recent, heightened interest in quartz and in particular the precise determination of trace0element contents in natural quartz samples requires the use of well characterised reference materials such as BCS 313/1 and SRM 1830, to which this study is designed to contribute.     

MAJOR AND TRACE ELEMENT DETERMINATIONS ON NIST GLASS STANDARD REFERENCE MATERIALS 611, 612, 614 AND 1834 BY INDUCTIVELY COUPLED PLASMA-MASS SPECTROMETRY

We report on the major and trace element composition and homogeneity of NIST (National Institute of Standards and Technology) glass standard reference materials 611, 612, 614, and 1834 for use as microanalytical trace element standards in laser ablation-inductively coupled plasma-mass spectrometry. The four analyzed NIST glasses were not designed as microanalytical standards, but their availability and careful preparation made them obvious candidates. Our data indicate that NIST 1834 is inhomogeneous on a scale of 100 mg with respect to several trace elements. Within analytical uncertainty, NIST 611, 612, and 614 are apparently homogeneous.