中国农业科学 ›› 2019, Vol. 52 ›› Issue (24): 4555-4566.doi: 10.3864/j.issn.0578-1752.2019.24.010

• 土壤肥料·节水灌溉·农业生态环境 • 上一篇    下一篇

土壤重金属快速检测技术研究进展

毛雪飞,刘霁欣(),钱永忠()   

  1. 中国农业科学院农业质量标准与检测技术研究所/农业农村部农产品质量安全重点实验室,北京 100081
  • 收稿日期:2019-04-28 接受日期:2019-08-22 出版日期:2019-12-16 发布日期:2020-01-15
  • 通讯作者: 刘霁欣,钱永忠
  • 作者简介:毛雪飞,E-mail:mxf08@163.com&maoxuefei@caas.cn。
  • 基金资助:
    国家重点研发计划(2017YFD0801203);国家重点研发计划(2017YFF0108203);国家自然科学基金面上项目(31571924);中国农业科学院基本科研业务费专项(Y2019XK05)

Technical Review of Fast Detection of Heavy Metals in Soil

XueFei MAO,JiXin LIU(),YongZhong QIAN()   

  1. Institute of Quality Standard and Testing Technology for Agri-Products, Chinese Academy of Agricultural Sciences / Key Laboratory of Agri-Food Safety and Quality, Ministry of Agriculture and Rural Affairs, Beijing 100081
  • Received:2019-04-28 Accepted:2019-08-22 Online:2019-12-16 Published:2020-01-15
  • Contact: JiXin LIU,YongZhong QIAN

摘要:

近年来,随着我国工农业的高速发展,尤其是无节制的矿藏开采、“三废”排放、汽车尾气以及农业化学投入品的滥用,重金属污染已成为我国当前最严重的环境污染问题之一,因此土壤重金属监测工作显得尤为重要。但是,目前的土壤重金属检测标准方法仍以实验室确证性分析为主,无法用于土壤重金属的现场、快速分析,从而难以从源头上及时、有效地对土壤重金属污染进行监测和预防,开发重金属快速检测设备和技术势在必行。从土壤样品的基质特点来看,固体进样分析是最可行的技术方案,主要包括电热蒸发(ETV)原子光谱、X射线荧光光谱(XRF)、激光烧蚀(LA)、激光诱导击穿光谱(LIBS)、X射线吸收光谱(XAS)、中子活化(INAA)等。上述固体进样分析技术均无需样品消解处理,高效、快捷,但是部分技术的检出能力和稳定性尚难以满足土壤质量标准的全部要求,如XRF、LA、LIBS,还有部分技术难以实现现场化,如LA、XAS、INAA等。因此,基于电热蒸发(ETV)固体进样的原子光谱分析技术在分析灵敏度、稳定性和小型化方面具有特殊的优势。ETV是利用电加热将样品中的待测元素以气溶胶的形式导入原子化器或激发源的技术,可实现土壤中常见重金属元素的快速、高效导入,技术简单、通用性强,适用于原子吸收、原子荧光、原子发射、无机质谱等多种检测系统。ETV常采用碳、金属、石英等材料,如石墨管、多孔碳管、钨丝、铼丝、石英管,其中利用高熔点金属的电磁感应电热蒸发技术具有无冷点、升/降温速度快、易于小型化的优势。但是,土壤样品基质复杂,基体干扰一直是困扰ETV技术应用的核心瓶颈问题。新型的气相富集(GPE)、介质阻挡放电(DBD)、基体改进及背景校正等技术,有望实现土壤基体干扰的有效消除。特别是GPE技术,在特异性捕获消除基体干扰的同时,还可以通过预富集提高仪器的分析灵敏度。通过上述技术的集成与创新,可以有效解决固体进样的分析灵敏度和基体干扰问题,这将为土壤重金属速测技术的研发提供新的思路,从而为土壤环境监测与治理工作提供有效的技术支撑。

关键词: 土壤, 重金属, 快速检测, 电热蒸发, 固体进样, 基体干扰

Abstract:

Recently, with the high-speed development of industry and agriculture in China, the contamination of heavy metal has become a severe environmental problem caused by immoderate mining operation, "three wastes" emissions, vehicle exhaust, and misuse of agricultural chemical inputs. So, it is very important to monitor the contamination of heavy metals in soil. However, the national and industrial standards of detecting heavy metals in soil mainly focus on the traditional analytical approaches employed in laboratory at present. So, it is still difficult to achieve the on-site and fast detection of heavy metals in soil, which gives rise to such difficulty of monitoring and preventing the source contamination effectively and timely. In view of the matrix of soil sample, solid sampling analysis should be feasible to the fast detection of heavy metals, including electrothermal vaporization (ETV), X-ray fluorescence spectrometry (XRF), laser ablation (LA), laser induced breakthrough spectrometry (LIBS), X-ray photoelectron spectroscopy (XPS), and instrumental neutron activation analysis (INAA). The solid sampling techniques do not require digestion treatment and is thereby fast and efficient. However, among them, the detection limit and stability of XRF, LA, and LIBS cannot satisfy the all demands in standards of soil quality; on the other hand, it is too difficult to reach the miniaturization and on-site testing for LA, XAS, and INAA. By comparison, ETV is a kind of solid sampling tool with excellent advantages such as high analytical sensitivity, favorable stability, and being easy to be miniaturized, using electric heating to introduce analyses via aerosol from the sample into the atomizer or exciter for measurement. ETV is able to introduce heavy metals fast and efficiently, which is versatile to atomic absorption spectrometry (AAS), atomic fluorescence spectrometry (AFS), atomic emission spectrometry (AES), and induced coupled plasma mass spectrometry (ICP-MS). As usual, many materials such as carbon, metals, and quartz can be utilized for ETV, which are frequently processed into graphite furnace, porous carbon tube, tungsten coil, rhenium coil, quartz tube and so on. Among various ETV approaches, electromagnetic induction ETV is characterized with no cold zone, fast heating or cooling and miniaturization. Considering the complicated soil matrices, however, ETV has been always confronted with the bottleneck problem, namely matrix interference. Through integrating these advanced techniques including gas phase enrichment (GPE), dielectric barrier discharge, matrix modifier, background correction and so on, the matrix interference will be eliminated completely for the detection of heavy metals in soil when solid sampling by using ETV atomic spectrometers. Especially for GPE, it can realize both two aims at one time: eliminating matrix interference and improving analytical sensitivity. This review is about to bring some valuable suggestions for innovating the fast detection of heavy metals in soil, to play parts in the environmental monitoring and protection in the future.

Key words: soil, heavy metals, fast detection, electrothermal vaporization, solid sampling, matrix interference