色谱 ›› 2021, Vol. 39 ›› Issue (8): 855-869.DOI: 10.3724/SP.J.1123.2020.12016

• 专论与综述 • 上一篇    下一篇

无固定相分离-电感耦合等离子体质谱法在环境中痕量金属纳米颗粒分析中的应用

姜皓文1,2, 李健3, 谭志强1,2,4,*(), 郭瑛瑛1,2, 刘艳伟1,2, 胡立刚1,2, 阴永光1,2,4,*(), 蔡勇1,5, 江桂斌1   

  1. 1.中国科学院生态环境研究中心, 北京 100085
    2.中国科学院大学, 北京 100049
    3.浙江环境监测工程有限公司, 浙江 杭州 310012
    4.国科大杭州高等研究院环境学院,浙江 杭州 310024
    5.佛罗里达国际大学化学与生物化学系, 美国佛罗里达州 迈阿密 33199
  • 收稿日期:2020-12-15 出版日期:2021-08-08 发布日期:2021-06-29
  • 通讯作者: 谭志强,阴永光
  • 作者简介:Tel:(010)62841180,E-mail: ygyin@rcees.ac.cn(阴永光).
    *Tel:(010)62844175,E-mail: zqtan@rcees.ac.cn(谭志强);
  • 基金资助:
    国家重点研发计划(2020YFA0907400);国家自然科学基金项目(21777178);中国科学院前沿科学重点项目(QYZDB-SSWDQC018);中国科学院交叉创新团队(JCTD-2018-04)

Application of non-stationary phase separation hyphenated with inductively coupled plasma mass spectrometry in the analysis of trace metal-containing nanoparticles in the environment

JIANG Haowen1,2, LI Jian3, TAN Zhiqiang1,2,4,*(), GUO Yingying1,2, LIU Yanwei1,2, HU Ligang1,2, YIN Yongguang1,2,4,*(), CAI Yong1,5, JIANG Guibin1   

  1. 1. Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
    2. University of Chinese Academy of Sciences, Beijing 100049, China
    3. Zhejiang Environmental Monitoring Engineering Limited Company, Hangzhou 310012, China
    4. School of Environment, Hangzhou Institute for Advanced Study, UCAS, Hangzhou 310024, China
    5. Department of Chemistry and Biochemistry, Florida International University, Miami 33199, United States
  • Received:2020-12-15 Online:2021-08-08 Published:2021-06-29
  • Contact: TAN Zhiqiang,YIN Yongguang
  • Supported by:
    National Key Research and Development Project(2020YFA0907400);National Natural Science Foundation of China(21777178);Key Projects for Frontier Sciences of the Chinese Academy of Sciences(CAS)(QYZDB-SSWDQC018);CAS Interdisciplinary Innovation Team(JCTD-2018-04)

摘要:

环境中金属纳米颗粒的分析检测不仅需要关注其浓度和化学组成,还需要对其形状、粒径和表面电荷等进行表征。此外,环境中金属纳米颗粒的分析需要解决其低赋存浓度以及复杂基质干扰的难题。无固定相分离技术与电感耦合等离子体质谱(ICP-MS)的在线联用,具有较强的颗粒分离能力和较低的元素检出限,能够快速准确地提供金属纳米颗粒的粒径分布、化学组成等信息,在金属纳米颗粒的分离检测方面表现出极大的潜能。但这一联用技术尚无法获得金属纳米颗粒物的颗粒数浓度和单个颗粒的元素信息,难以判断金属纳米颗粒涂层厚度、纯度以及颗粒的均相/异相团聚行为等。新兴的单颗粒-电感耦合等离子体质谱(SP-ICP-MS)与无固定相分离技术的在线联用,可以获得金属纳米颗粒的流体动力学粒径、元素质量计算粒径和颗粒数浓度等信息,进而弥补无固定相分离与ICP-MS在线联用技术的不足。该文介绍了流体动力色谱、毛细管电泳和场流分离3种常用无固定相分离技术的分离机制和适用检测器,着重综述了无固定相分离技术与ICP-MS/SP-ICP-MS在线联用技术的特点及其在环境金属纳米颗粒分析中的应用。关于场流分离,主要介绍了可以与ICP-MS联用的沉降场流分离和流场流分离。该文还对流体动力色谱、毛细管电泳和流场流分离与ICP-MS在线联用技术的特点进行了比较。最后,该文对无固定相分离技术与ICP-MS/SP-ICP-MS在线联用技术的发展提出了展望。

关键词: 金属纳米颗粒, 流体动力色谱, 毛细管电泳, 场流分离, 电感耦合等离子体质谱, 单颗粒-电感耦合等离子体质谱, 综述

Abstract:

Engineered metal-containing nanoparticles (MCNs), which have unique physical and chemical properties, are widely used in various fields such as medicine, pharmaceuticals, and microelectronics as well as in daily supplies. These MCNs are inevitably released into the environment during production and use, thus posing a threat to bacterial communities, animals, plants, and human health. There are also abundant natural MCNs in the environment, which play an important role in the environmental cycle of metals. The shape, size, and surface properties of MCNs have a significant impact on their migration, chemical and physical transformation, and biological intake in the environment. Therefore, the analysis and detection of MCNs in the environment should be aimed not only at quantifying their concentration and chemical composition, but also at determining their shape, particle size, and surface charge. In addition, for the detection of MCNs in the environment, challenges due to their low concentrations and the interference from complex environmental matrices must be overcome. A single detection technique is often insufficient for the analysis and detection of MCNs in a complex environment matrix. Therefore, the development of an effective and reliable online hyphenated technique is urgently needed for the separation and detection of MCNs in the environment. Such online hyphenated techniques should be able to eliminate the interference by complex matrices, improve the particle size detection range, and reduce the element detection limit. The online hyphenation of stationary phase-based separation techniques such as liquid chromatography and gel electrophoresis with inductively coupled plasma-mass spectrometry (ICP-MS) can effectively separate MCNs according to their particle size, with low element detection limits. However, these stationary phase-based separation techniques have a shortcoming of the adsorption of nanoparticles on the stationary phase, which leads to blockage of separation channels and low recoveries of nanoparticles. The online hyphenation of a non-stationary phase separation technique with ICP-MS also shows strong nanoparticle separation ability and low element detection limits, so that the problem of colloid blockage in stationary phase-based separation can be resolved. This method is very promising for the rapid and accurate characterization of the particle size distribution and chemical composition of MCNs. However, it cannot provide information about the nanoparticle number concentration of MCNs and the elemental content of a single MCN. In complex environmental samples, pure MCNs cannot be effectively distinguished from MCNs with environmental corona having different thicknesses or pure MCNs adsorbed on/hetero-agglomerated with inorganic/organic colloids. Online coupling single-particle ICP-MS (SP-ICP-MS), an emerging particle detection technique with non-stationary phase separation, can effectively help overcome the above shortcomings. This method can provide information on the hydrodynamic diameter, metal mass-derived diameter, total number concentration, size-dependent number, and size-dependent mass concentration of MCNs. Therefore, it enables comprehensive characterization of MCNs based on a variety of three-dimensional contour plot chromatograms. This review summarizes the separation mechanisms and applicable detectors for three commonly used non-stationary phase separation techniques: hydrodynamic chromatography (HDC), capillary electrophoresis (CE), and field-flow fractionation (FFF). In addition, it focuses on the characteristics and applications of online-coupling non-stationary phase separation with ICP-MS and SP-ICP-MS. Regarding FFF, this review focuses on the separation techniques that are suitable for online coupling with ICP-MS, such as sedimentation FFF and flow FFF (symmetrical flow FFF, asymmetrical flow FFF, and hollow fiber flow FFF). In addition, the characteristics of the online hyphenation of three non-stationary phase separations, HDC, CE, and flow FFF, with ICP-MS are compared, including the separation mechanism, sample volume, analytical time, detection sensitivity, size range, size resolution, recovery, reproducibility, and capability for ion analysis. Finally, this review proposes the prospects for future development of the online hyphenation of non-stationary phase separation techniques with ICP-MS and SP-ICP-MS.

Key words: metal-containing nanoparticles (MCNs), hydrodynamic chromatography (HDC), capillary electrophoresis (CE), field-flow fractionation (FFF), inductively coupled plasma mass spectrometry (ICP-MS), single particle-inductively coupled plasma mass spectrometry (SP-ICP-MS), review

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