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孙书堂, 严倩, 黎宁, 黄理金, 帅琴. 铁丝原位自转化-固相微萃取新涂层应用于萃取环境水样中多环芳烃的性能研究[J]. 岩矿测试, 2020, 39(3): 408-416. DOI: 10.15898/j.cnki.11-2131/td.202002030014
引用本文: 孙书堂, 严倩, 黎宁, 黄理金, 帅琴. 铁丝原位自转化-固相微萃取新涂层应用于萃取环境水样中多环芳烃的性能研究[J]. 岩矿测试, 2020, 39(3): 408-416. DOI: 10.15898/j.cnki.11-2131/td.202002030014
SUN Shu-tang, YAN Qian, LI Ning, HUANG Li-jin, SHUAI Qin. In situ Self-transforming Membrane as Solid Phase Microextraction Coating Extraction of PAHs in Environmental Water Samples[J]. Rock and Mineral Analysis, 2020, 39(3): 408-416. DOI: 10.15898/j.cnki.11-2131/td.202002030014
Citation: SUN Shu-tang, YAN Qian, LI Ning, HUANG Li-jin, SHUAI Qin. In situ Self-transforming Membrane as Solid Phase Microextraction Coating Extraction of PAHs in Environmental Water Samples[J]. Rock and Mineral Analysis, 2020, 39(3): 408-416. DOI: 10.15898/j.cnki.11-2131/td.202002030014

铁丝原位自转化-固相微萃取新涂层应用于萃取环境水样中多环芳烃的性能研究

In situ Self-transforming Membrane as Solid Phase Microextraction Coating Extraction of PAHs in Environmental Water Samples

  • 摘要: 多环芳烃(PAHs)是一类具有致癌作用且难以降解的持久性有机污染物,广泛存在于环境中。环境中痕量PAHs的直接分析往往因检测手段的检出限达不到要求而存在困难,需要结合分离富集手段。常规的样品前处理技术如索氏提取、液液萃取等存在耗时长、使用大量有机溶剂等问题。因此为了提高效率、避免对自然环境的二次污染,有必要开发一种简便、环境友好的新型样品前处理技术。固相微萃取(SPME)是一种集采样、富集、进样于一体的无溶剂前处理技术,与气相色谱-质谱(GC-MS)等技术联用可实现复杂基质中痕量有机物的快速富集和检测。目前SPME技术的研究热点主要集中在改善涂层的萃取性能以及提高其机械强度方面。本文采用铁丝(IW)作为载体,同时又提供了铁离子来源,以原位自转化的方式在具有良好机械稳定性的铁丝上生长出一层多孔结构的金属有机骨架化合物多孔膜MIL-53(Fe);将其作为固相微萃取涂层IW@MIL-53(Fe),以7种难挥发的稠环PAHs作为目标分析物,以浸入式模式进行萃取,并结合GC-MS作为检测手段验证其萃取性能。结果表明:新涂层的萃取性能是商用100μm PDMS涂层的1~2倍,且涂层可稳定使用120次以上。该方法的检出限为0.03~2.25ng/L,线性范围为250~10000ng/L,相关系数为0.9903~0.9991。将建立的方法应用于自然水体中PAHs的检测,加标回收率为80.1%~108.5%。本研究不仅为高性能SPME涂层简单、快速制备提供了新思路,而且所建立的方法有望应用于水体中痕量有机污染物的准确和高灵敏检测。

     

    Abstract:
    BACKGROUNDPolycyclic aromatic hydrocarbons (PAHs) are one of the persistent organic pollutants which are carcinogenic and difficult to degrade, and are widespread in the environment. The direct analysis of trace PAHs in the environment is often difficult because of the low sensitivity of the detection methods. It is necessary to combine separation and enrichment methods. Conventional sample pretreatment techniques, such as Soxhlet extraction and liquid-liquid extraction, are time-consuming and use a large number of organic solvents.
    OBJECTIVESTo develop a new, simple, and environmentally-friendly method for sample pretreatment.
    METHODSSolid phase microextraction (SPME) is a solvent-free pretreatment technology which integrates sampling, enrichment and injection. Combined with gas chromatography-mass spectrometry (GC-MS), it can produce the rapid enrichment and detection of trace organic compounds in a complex matrix. At present, the research focus of improving SPME technology is to improve the mechanical strength and extraction performance of the coating. Using iron wire (IW) as the carrier, which also provided the iron ion source, a porous MOFs filmMIL-53(Fe) was grown on iron wire with good mechanical stability by in-situ self-transformation. It was used as the solid phase microextraction coatingIW@MIL-53(Fe). Seven kinds of non-volatile condensed ring PAHs were used as the target analyte, and immersion extraction mode combined with GC-MS as detection means were used to verify its extraction performance.
    RESULTSResults showed that the extraction performance of the new coating was 1-2 times higher than that of the commercial 100μm PDMS coating, and the coating can be used stably for more than 120 times. The detection limits of the methods were 0.03-2.25ng/L, the linear ranges were 250-10000ng/L, and the correlation coefficients were in the range of 0.9903-0.9991. The coating was applied successfully to the detection of PAHs in natural water, where the recoveries were from 80.1% to 108.5%.
    CONCLUSIONSThis study not only provides an idea for the simple and rapid preparation of high-efficiency SPME coatings, but also has great potential to be applied to determinate trace volatile organic pollutants in water with high accurateness and efficiency.

     

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