电感耦合等离子体质谱分析方法的重要进展（2005~2016年）

2005~2016这十几年中,电感耦合等离子体质谱（ICP-MS）仪器的性能得到了大幅改善,其灵敏度最高可达10⁶ cps/(1 μg/L, In),稳定性为1%～2%。多接收ICP-MS精密度的提高尤其显著,同位素测量精密度优于0.01%。各类ICP-MS普遍采用高速数据采集技术与数据库技术,使数据处理能力进一步加强。以三重四极杆和高分辨为代表的ICP-MS对基体干扰和多原子离子干扰消除能力进一步加强,绿色节能环保型和智能型ICP-MS也得到了关注。一些电离能较高的贵金属、类金属和非金属元素分析技术得到重视。以激光烧蚀（LA）、高效液相色谱（HPLC）、气相色谱（GC）、离子色谱（IC）、毛细管电泳（CE）、电热蒸发（ETV）和化学气体发生（CVG）为代表的联用技术及形态分析发展快速。单颗粒（SP）和单细胞（SC）等技术与ICP-MS的联用产生了以功能定义的专用ICP-MS,大大扩展了ICP-MS的应用领域。ICP-MS分析技术从传统的无机元素分析发展到有机生物及形态分析,从传统的样品消解后溶液进样分析发展到固体样品在线进样分析,从传统的元素含量分析发展到2D-3D成像分析和高精度同位素分析。ICP-MS在能源、地质、材料、环保、生物医学、食品、国土安全等诸多领域的应用进一步扩展,成熟的ICP-MS分析方法实现了标准化并得到推广和普及。本工作从6个方面总结回顾了2005~2016年间ICP-MS的重要进展,并对其发展前景进行了展望。     

电感耦合等离子体质谱法在临床样品分析中的应用

本文对近年来电感耦合等离子体质谱法（ICP-MS）在临床样品微量元素及形态分析中的应用进行了综述，讨论了应用ICP-MS技术测定临床样品微量元素的三种处理和分析方法（直接稀释法，湿法消解法和微波消解法），列举了部分含量测定的实例。介绍了联用技术高效液相色谱（HPLC）、气相色谱（GC）、超临界流体色谱（SFC）和毛细管电泳（CE）在形态分析中的应用，指出了现存的问题，探讨了可能的解决方案。     

电感耦合等离子体质谱联用技术应用进展

本文介绍电感耦合等离子体质谱联用技术（ICP-MS）特点和发展趋势,归纳近年来电感耦合等离子体质谱法联用技术在不同领域应用进展,并对ICP-MS联用技术的发展前景进行展望。     

碘的质谱测量方法研究进展

近年来,电感耦合等离子体质谱（ICP-MS）技术的发展着力于应对基质更加复杂的样品和解决测量过程中的干扰问题,同时与进样、分离系统的联用技术也在快速发展,而加速器质谱（AMS）则朝着更加小型化和更高灵敏度的方向发展。ICP-MS测量前需要对样品进行前处理以消解和提取碘,而AMS测量前则还需对样品进一步分离富集和纯化。本文总结了ICP-MS和AMS的发展概况及其在碘测量方面的应用,归纳了ICP-MS和AMS测量含碘样品的前处理方法,综述了国内外总碘、碘同位素及碘形态的质谱测量方法新进展。     

电感耦合等离子体质谱技术在核地质分析中的应用实践

电感耦合等离子体质谱（ICP-MS）技术已有40年发展历史,到目前为止,该方法仍然是无机元素分析领域最具影响力的高灵敏度分析技术。在核地质研究领域,ICP-MS已经成为铀矿地质勘查和高放废物地质处置的核心分析技术,每年为核地质科研生产提供大量的分析测试数据。应用ICP-MS分析的对象涉及水、土壤、沉积物、岩石、矿物、气体和天然类似物等,分析的元素达到70多种。本文总结了本实验室在核地质研究中应用ICP-MS的实践。     

HPLC/ICP-MS在环境样品的痕量元素形态分析中的应用

综述了高效液相色谱-电感耦合等离子体质谱联用技术（HPLC/ICP-MS）的最新进展和工作特点，介绍了该技术在环境样品分析中的应用概况、接口类型和应用同位素稀释技术进行元素形态分析等。     

电感耦合等离子体质谱在环境放射化学研究中的应用

电感耦合等离子体质谱（ICP-MS）在非放射性金属元素分析中已经成为首选技术。近年来,随着检测灵敏度和分辨率的提高,该技术在放射性核素含量和同位素比值测定中的应用日益突出。在探讨环境放射性核素含量以及同位素比值分析意义的基础上,列举了50余篇监测实例,并展望了ICP-MS技术的发展前景。     

电感耦合等离子体质谱在细菌多组分分析中的应用

对细菌特征蛋白和核酸进行高通量定量分析,有助于快速鉴定细菌种群及其功能研究。近年来,结合元素标记策略的电感耦合等离子体质谱（ICP-MS）在细菌蛋白和核酸检测中的应用受到关注。ICP-MS检测蛋白质、核酸等生物分子时,具有灵敏度高、线性范围宽、生物基体干扰小等优点,适用于细菌多组分定量分析。本文综述了细菌不同特征物质作为目标待测物的ICP-MS分析方法,并对其发展方向进行了展望,希望为细菌分析方法的研究提供参考。     

ICP-MS分析国际比对样品中无机元素含量

本试验应用电感耦合等离子体质谱法（ICP-MS）参加了英国食品分析水平评估计划（FAPAS）组织的国际测试活动，即FAPAS0758和FAPAS0761样品中的无机元素分析。反馈的统计结果显示两份样品共7个元素含量的 Z 值在0.0~1.3之间，结果均令人满意。     

激光溅射电离飞行时间质谱用于矿样分析的研究及技术比较

将自行研制的激光溅射电离飞行时间质谱仪（LAI-TOFMS）用于辉绿岩（GBW07123）、石榴石和硅化木3种矿物样品的直接分析,初步讨论了元素含量和元素相对含量的计算方法,计算过程中选Mn作参考元素,并将LAI-TOFMS与电感耦合等离子体质谱（ICP-MS）、X射线荧光光谱（XRF）在样品分析过程和分析结果方面进行比较。LAI-TOFMS中,元素含量是通过相对灵敏系数（RSC）和Mn的含量计算得到,元素的相对含量与元素的相对原子质量及其质谱峰的强度有关;对于ICP-MS和XRF,元素的相对含量是待测元素和Mn含量的比值。初步研究表明：LAI-TOFMS, ICP-MS和XRF 3种分析方法测得的元素含量和元素相对含量结果相对符合较好。此外,由于具有样品前处理简单、几乎不污染样品、样品消耗量少等优点,LAI-TOFMS能够提高矿物样品的分析检测效率。     

Bioimaging of metals by laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS)

The distribution analysis of (essential, beneficial, or toxic) metals (e.g., Cu, Fe, Zn, Pb, and others), metalloids, and non‐metals in biological tissues is of key interest in life science. Over the past few years, the development and application of several imaging mass spectrometric techniques has been rapidly growing in biology and medicine. Especially, in brain research metalloproteins are in the focus of targeted therapy approaches of neurodegenerative diseases such as Alzheimer's and Parkinson's disease, or stroke, or tumor growth. Laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) using double‐focusing sector field (LA‐ICP‐SFMS) or quadrupole‐based mass spectrometers (LA‐ICP‐QMS) has been successfully applied as a powerful imaging (mapping) technique to produce quantitative images of detailed regionally specific element distributions in thin tissue sections of human or rodent brain. Imaging LA‐ICP‐QMS was also applied to investigate metal distributions in plant and animal sections to study, for example, the uptake and transport of nutrient and toxic elements or environmental contamination. The combination of imaging LA‐ICP‐MS of metals with proteomic studies using biomolecular mass spectrometry identifies metal‐containing proteins and also phosphoproteins. Metal‐containing proteins were imaged in a two‐dimensional gel after electrophoretic separation of proteins (SDS or Blue Native PAGE). Recent progress in LA‐ICP‐MS imaging as a stand‐alone technique and in combination with MALDI/ESI‐MS for selected life science applications is summarized. © 2009 Wiley Periodicals, Inc., Mass Spec Rev 29:156–175, 2010     

Mass spectrometry in bioinorganic analytical chemistry

A considerable momentum has recently been gained by in vitro and in vivo studies of interactions of trace elements in biomolecules due to advances in inductively coupled plasma mass spectrometry (ICP MS) used as a detector in chromatography and capillary and planar electrophoresis. The multi-isotopic (including non-metals such as S, P, or Se) detection capability, high sensitivity, tolerance to matrix, and large linearity range regardless of the chemical environment of an analyte make ICP MS a valuable complementary technique to electrospray MS and MALDI MS. This review covers different facets of the recent progress in metal speciation in biochemistry, including probing in vitro interactions between metals and biomolecules, detection, determination, and structural characterization of heteroatom-containing molecules in biological tissues, and protein monitoring and quantification via a heteroelement (S, Se, or P) signal. The application areas include environmental chemistry, plant and animal biochemistry, nutrition, and medicine.     

同位素稀释电感耦合等离子体质谱法测定高纯石英中痕量硼

应用同位素稀释电感耦合等离子体质谱法 ( ID-ICP-MS)测定地质标样 ( GSD-4和 GSD-8)和高纯石英中的痕量硼。样品处理采用低温密封焖罐酸溶样技术 ,将样品与稀释剂充分混匀 ,硼损失较小。硼元素在碱性条件下主要以 B( OH) 4 -形式存在于溶液中 ,可被硼特效离子交换树脂所交换吸附 ,故能很好地与大部分基体元素分离 ,从而减少基体效应。测定结果表明 :该方法测定痕量硼具有较高的准确度和精密度 ,且方法的检出限低 ,可达 5 1 .7ng/g,是准确定量测定痕量硼的理想方法     

萃取色层分离ICP／MS测定U3O8中痕量杂质元素

本文叙述了结合CL－TBP萃取色层分离,运用ICP／MS测定U3O8中痕量杂质元素B、Ti、Cd、V、Cr、Zn、Mo、Sb、W、Bi的方法。U3O8经硝酸溶解后,采用CL－TBP草林树脂作固定相,5．5mol／L,硝酸作流动相的萃取色层法使杂质元素与铀基体分离,杂质元素淋洗液用ICP／MS测定。取样量为O．5g时,各杂质元素的测定下限为1×10（-8）g／g。方法的重加回收率在88％－116％之间,相对标准偏差小于14％。     

DRCⅡ型ICP-MS分析技术及其应用

本文简要介绍了动态反应池(Dynamic Reaction Cell)的电感耦合等离子体质谱(Inductively Coupled Plasma Mass Spectrometry)技术及其在环境、生物医学等领域中应用。     

微型ICP激发源及其应用

介绍一种新的原子发射光谱微型电感耦合等离子体(ICP)激发源,阐述这种激发源的结构、性能及其在光谱仪中的应用,它与平面结构的微型Fabry-Perot光谱仪联用可以作为微型气体分析仪使用。并简要介绍作者研制的在较低的13.56MHz下工作的微型ICP激发源。展望随着MEMS技术的发展,微型光谱仪的应用前景。     

Accurate and precise determination of isotopic ratios by MC‐ICP‐MS: A review

For many decades the accurate and precise determination of isotope ratios has remained a very strong interest to many researchers due to its important applications in earth, environmental, biological, archeological, and medical sciences. Traditionally, thermal ionization mass spectrometry (TIMS) has been the technique of choice for achieving the highest accuracy and precision. However, recent developments in multi‐collector inductively coupled plasma mass spectrometry (MC‐ICP‐MS) have brought a new dimension to this field. In addition to its simple and robust sample introduction, high sample throughput, and high mass resolution, the flat‐topped peaks generated by this technique provide for accurate and precise determination of isotope ratios with precision reaching 0.001%, comparable to that achieved with TIMS. These features, in combination with the ability of the ICP source to ionize nearly all elements in the periodic table, have resulted in an increased use of MC‐ICP‐MS for such measurements in various sample matrices. To determine accurate and precise isotope ratios with MC‐ICP‐MS, utmost care must be exercised during sample preparation, optimization of the instrument, and mass bias corrections. Unfortunately, there are inconsistencies and errors evident in many MC‐ICP‐MS publications, including errors in mass bias correction models. This review examines “state‐of‐the‐art” methodologies presented in the literature for achievement of precise and accurate determinations of isotope ratios by MC‐ICP‐MS. Some general rules for such accurate and precise measurements are suggested, and calculations of combined uncertainty of the data using a few common mass bias correction models are outlined. © 2009 Crown in the right of Canada. Published by Wiley Periodicals, Inc., Mass Spec Rev 28:990–1011, 2009     

Application of mass spectrometry in the analysis of polybrominated diphenyl ethers

This review summarized the applications of mass spectrometric techniques for the analysis of the important flame retardants polybrominated diphenyl ethers (PBDEs) to understand the environmental sources, fate and toxicity of PBDEs that were briefly discussed to give a general idea for the need of analytical methodologies. Specific performance of various mass spectrometers hyphenated with, for example, gas chromatograph, liquid chromatograph, and inductively coupled plasma (GC/MS, LC/MS, and ICP/MS, respectively) for the analysis of PBDEs was compared with an objective to present the information on the evolution of MS techniques for determining PBDEs in environmental and human samples. GC/electron capture negative ionization quadrupole MS (GC/NCI qMS), GC/high resolution MS (GC/HRMS) and GC ion trap MS (GC/ITMS) are most commonly used MS techniques for the determination of PBDEs. New analytical technologies such as fast tandem GC/MS and LC/MS become available to improve analyses of higher PBDEs. The development and application of the tandem MS techniques have helped to understand environmental fate and transformations of PBDEs of which abiotic and biotic degradation of decaBDE is thought to be one major source of Br_1‐9BDEs present in the environment in addition to direct loading from commercial mixtures. MS‐based proteomics will offer an insight into the molecular mechanisms of toxicity and potential developmental and neurotoxicity of PBDEs. © 2009 Wiley Periodicals, Inc., Mass Spec Rev 29:737–775, 2010     

基于ZYNQ的ICP-MS数据采集处理系统设计与实现

数据采集系统是电感耦合等离子体质谱仪(ICP-MS)的重要组成部分。本研究针对ICP-MS需要同步采集脉冲和模拟信号,且信号信噪比低的问题,提出了一种基于ZYNQ芯片的数据采集处理解决方案。利用ZYNQ集处理器和可编程逻辑于一体的特性,在ARM端搭载了用于流程控制及以太网通讯的FreeRTOS实时操作系统,在FPGA端基于FIR compiler和MCDMA IP核实现了数据的采集、缓存、动态滤波及传输。脱机测试结果表明,脉冲计数误差率小于0.000 5%,模拟计数线性度高达0.999 98,数字滤波幅频特性曲线与理论基本一致。在本团队自行研制的ICP-MS仪器中,利用本系统测试标准调谐液TUNE D,数据采集满足仪器需求,配置64阶低通滤波后,模拟计数中¹¹⁵In谱峰信噪比提高了49.59%。该系统FPGA端各资源占用率均小于50%,片上总功耗仅为2.28 W,有利于推动质谱仪小型化、智能化发展。     

Form-truing error compensation of diamond grinding wheel in CNC envelope grinding of free-form surface

In computer numerical control (CNC) grinding of free-form surface, an ideal arc profile of trued diamond grinding wheel is generally employed to plan 3D tool paths, whereas its form-truing errors greatly influence the ground form accuracy. A form-truing error compensation approach is proposed by using an approached wheel arc profile to replace the previously designed ideal one. The objective is to directly compensate the trued wheel arc-profile errors. It may avoid the time consumption of traditional approach that compensates the measured coordinate point errors of workpiece to an iterative grinding operation. First, the 3D tool path surface was constructed to plan the 3D tool paths. Second, the CNC arc truing of grinding wheel was conducted to analyze the form-truing error distribution relative to the applied wheel arc profile. Then, the form-truing error compensation was carried out in CNC envelope grinding. Finally, the iterative closest point (ICP) algorithm was used to match the measured coordinate points of workpiece to ideal free-form surface. It is shown that the 3D tool path surface constructed is practicable to plan arbitrary 3D tool paths for the form-truing error compensation. The ICP matching may be used to investigate 3D ground form error distribution. It is confirmed that the form-truing error compensation can directly improve the 3D ground form accuracy. It may decrease the 3D ground form error by about 20% when the 2D form-truing error is reduced by about 58% using the same truing conditions for CNC grinding.