原位高分辨微区元素分布特征检测技术的应用进展

林梵宇; 尹希杰; 刘建鑫; 孙延鑫

doi:10.16495/j.1006-3757.2023.03.002

原位高分辨微区元素分布特征检测技术的应用进展

doi: 10.16495/j.1006-3757.2023.03.002

林梵宇^1,,
尹希杰^{1, 2, ,},
刘建鑫¹,
孙延鑫¹

1.
自然资源部第三海洋研究所，福建厦门　361005
2.
中国地质调查局舟山海洋地质灾害野外科学观测研究站，山东青岛　266237

基金项目: 中国地质调查局舟山海洋地质灾害野外科学观测研究站开放基金（编号：ZSORS-22-10）；国家自然科学基金项目（42176057），海洋甲烷拦截带对冷泉流体的消耗研究：来自南海东沙海域的观测与研究；国家自然科学基金项目(41976050)，台风对泉州湾入海污染物“从源到汇”过程的影响研究

详细信息

作者简介:
林梵宇（1984−），男，工程师，主要从事元素分布和定量检测研究，E-mail：linfanyu@tio.org.cn

通讯作者:
尹希杰（1977−），男，研究员，主要从事同位素研究，E-mail：yinxijie@tio.org.cn

中图分类号: O657
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- 文章访问数: 96
- HTML全文浏览量: 14
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- 被引次数: 0
出版历程
- 收稿日期: 2023-04-06
- 录用日期: 2023-07-03
- 修回日期: 2023-07-03
- 刊出日期: 2023-09-25

Application Progress of In Situ High Resolution Detection Technology of Element Distribution Characteristics in Micro-areas

LIN Fanyu^1
,,
YIN Xijie^{1, 2
, ,},
LIU Jianxin¹,
SUN Yanxin¹

1.
Third Institute of Oceanography, MNR, Xiamen 361005, Fujian China
2.
Zhoushan Field Scientific Observation and Research Station for Marine Geo-hazards, China Geological Survey, Qingdao 266237, China

Funds: Open Research Fund Program of Zhoushan Field Scientific Observation and Research Station for Marine Geo-hazards, China Geological Survey (No. ZSORS-22-10), National Natural Science Foundation of China (NSFC, No. 42176057) , Consumption of Cold Seeping Fluids by a Double "Methane Filter": It Observation and Numerical Simulation in the Dongsha Area, South China Sea; National Natural Science Foundation of China (NSFC, No. 41976050), Impact of Typhoons on the "Source to Sink" Processes of Pollutants in the Quanzhou Bay

摘要

摘要: 样品中各元素原位、微区、高分辨率的空间分布特征具有现实而重要的研究意义. 在生物样品中，元素原位空间分布特征可以作为生理过程的指示指标，揭示代谢途径，并可反映周围环境特征对生物体的影响方式. 在地质样品中，元素原位空间分布特征可以作为矿产评估依据，也可作为研究环境地球化学变化过程的重要指标. 目前常用的几种微区元素原位分布特征测试技术包括：微区XRF技术（μXRF）、同步辐射技术（SR）、能谱电子显微镜联用技术（EM-EDS）、电子探针技术（EP）、激光剥蚀联用电感耦合等离子体质谱技术（LA-ICP-MS）、激光诱导击穿等离子发射光谱技术（LIBS）等. 根据其测试原理，这些技术在是否无损、是否定量检测、适合样品类型和大小、前处理方式复杂程度、检出限高低、分辨率大小等方面存在差异. 介绍和总结了当前主流的微区原位元素分布检测技术，分析比较了各种技术的优缺点及其适用的样品类型和应用范围，对标准样品的选择、数据校准处理及可视化成图等方案进行初步探讨，为相关的科研分析工作提供技术参考.
- 微区 /
- 元素分布 /
- 生物样品 /
- 地质样品
Abstract: The in situ, micro-area and high-resolution spatial distribution characteristics of elements in the samples are of practical and important research significance. In biological samples, the in situ spatial distribution characteristics of elements can be used as indicators of physiological processes, reveal metabolic pathways, and reflect the ways in which environmental characteristics affect organisms. In geological samples, the in situ spatial distribution characteristics of elements can be used as a basis for mineral evaluation and an important indicator for studying the process of environmental geochemical changes. At present, several commonly used techniques for measuring the in situ distribution characteristics of elements in micro-areas include: micro X-ray fluorescence spectrometry (μXRF), synchrotron radiation technology (SR), electron microscopy-energy dispersive spectrometry (EM-EDS), electron probe technology (EP), laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), laser induced breakdown plasma emission spectroscopy (LIBS), etc. Based on the principle of testing samples, these technologies differ in many aspects such as non-destructive testing, quantitative testing, suitable sample type and size, complexity of pre-treatment methods, detection limits and resolution, and so on. The current mainstream of the micro-area in situ element distribution detection techniques were introduced and summarized, the advantages and disadvantages of various techniques and their applicable sample types and application ranges were analyzed and compared. The selection of standard samples, data calibration and processing and visualization into maps were discussed for the first time, which provides a technical reference for related scientific research and analysis work.
- micro-area /
- element distribution /
- biological sample /
- geological sample

HTML全文

图 1 微区XRF设备原理及示意图

Figure 1. Principle and schematic diagram of micro XRF equipment

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图 2 同步辐射设备硬件构造

Figure 2. Hardware structure of synchrotron radiation equipment

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图 3 SEM-EDS设备硬件构造

Figure 3. Hardware structure of SEM-EDS

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图 4 电子探针设备硬件构造

Figure 4. Hardware structure of electron probe equipment

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图 5 LA-ICP-MS设备硬件构造

Figure 5. Hardware structure of LA-ICP-MS

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图 6 LA-ICP-MS技术研究深海结核样品中微量及稀土元素分布特征

（a）扫描结核样品全貌及选取的扫描区域，（b）结核样品中微量元素分布特征（单位：g/kg），（c）结核样品中稀土元素分布特征（单位：mg/kg）

Figure 6. Distribution characteristics of trace and rare earth elements in deep-sea nodule samples by LA-ICP-MS

(a) nodule sample and selected scanning area, (b) distribution characteristics of trace elements in nodule samples (unit: g/kg), (c) distribution characteristics of rare earth elements in nodule samples (unit: mg/kg)

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图 7 LIBS设备硬件构造

Figure 7. Hardware structure of LIBS

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表 1 微区检测技术特点对比

Table 1. Comparison of micro-area detection technology

检测方法	样品前处理	样品大小	空间分辨率	适合元素种类	检出限	是否定量检测	是否损伤样品
微区XRF	简单，对高含水量的样品进行脱水处理即可	毫米到厘米级最大可达数十厘米	一般在5~10微米以上	通常Na~U，无法检测轻原子序数的元素	一般在几十到几百mg/kg以上量级，仅适合检测高含量元素	定性检测及半定量检测	无损
同步辐射	简单，对高含水量的样品进行脱水处理即可	微米至厘米级	通常在微米级，搭载光学组件后可达纳米级	原子序数Na以上	mg/kg级至亚mg/kg级	定性检测及半定量检测	无损
能谱电镜联用	需喷金膜或碳膜，样品平整度要求高	亚微米级别	纳米级别至亚微米级别	通常Na~U，无法准确检测轻原子序数的元素	一般在几十到几百mg/kg以上量级	定性检测及半定量检测	有损
电子探针	需喷金膜或碳膜，样品平整度要求高	毫米级别	1~2微米或更小	当含量处于亚百分比级别时，可测C、O等轻原子序数元素	一般在几十到几百mg/kg以上量级	相对准确的半定量检测	有损
LA-ICP-MS	主要采用以环氧树脂为载体的样品制备方式，样品平整度要求高	微米到厘米级	理论可达1~2微米，由于分馏效应等因素通常取30~50微米	质谱检测器可以检测几乎全部的金属元素，包括低原子序数的金属元素，但检测卤族元素时存在困难	mg/kg级	准确的定量检测	有损
LIBS	简单，对高含水量的样品进行脱水处理即可	毫米到厘米级	数十微米级至毫米级	检测范围广，除常规元素外还可检测C、N等轻原子序数元素	一般在几十到几百mg/kg以上量级	定性检测及半定量检测	有损

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