色谱 ›› 2022, Vol. 40 ›› Issue (10): 872-881.DOI: 10.3724/SP.J.1123.2022.03030

• 专论与综述 • 上一篇    下一篇

六溴环十二烷的样品前处理和检测方法研究进展

程嘉雯, 马继平(), 李爽, 田永   

  1. 青岛理工大学环境与市政工程学院, 山东 青岛 266525
  • 收稿日期:2021-12-23 出版日期:2022-10-08 发布日期:2022-10-12
  • 通讯作者: 马继平
  • 基金资助:
    国家自然科学基金(21976099);山东省自然科学基金(ZR2019MB046)

Progress in sample pretreatment and detection methods of hexabromocyclododecanes

CHENG Jiawen, MA Jiping(), LI Shuang, TIAN Yong   

  1. School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266525, China
  • Received:2021-12-23 Online:2022-10-08 Published:2022-10-12
  • Contact: MA Jiping
  • Supported by:
    National Natural Science Foundation of China(21976099);Natural Science Foundation of Shandong Province of China(ZR2019MB046)

摘要:

作为一种常见的溴代阻燃剂,六溴环十二烷(HBCDs)因具备持久性、长距离迁移性、生物蓄积性和高毒性,于2013年被列入《斯德哥尔摩公约》。因此,环境样品中HBCDs污染水平的准确分析和严格控制对完善环境监管长效机制至关重要。然而,实际样品中HBCDs的定性定量分析正面临着基质复杂、目标物含量低等问题。尤其,HBCDs在高温环境及特定有机溶剂中易降解,会产生异构体,提高了分析难度。该综述简述了HBCDs的理化性质、毒性危害和标准限制,重点围绕不同基质中HBCDs的样品前处理和仪器检测两方面进行了总结。论文内容引用2000~2022年的70余篇源于科学引文索引(SCI)与中文核心期刊中的相关论文。总结归纳了固体和液体样品中HBCDs分析的前处理技术,包括索式提取、超声辅助萃取、加速溶剂萃取、超临界流体萃取、液液萃取、分散液液微萃取、固相萃取、分散固相萃取和固相微萃取等,介绍了气相色谱、液相色谱和色谱-质谱联用技术等仪器检测方法在HBCDs分析中的应用。通过综述近期相关研究,侧面表明HBCDs的分析方法研究发展迅速,但也面临一些挑战,如样品前处理步骤繁琐、耗时长、样品量和有机溶剂用量大等问题。最后,对新型样品前处理技术在HBCDs分析中的应用进行了展望。

关键词: 样品前处理, 检测方法, 六溴环十二烷, 溴代阻燃剂, 综述

Abstract:

Hexabromocyclododecanes (HBCDs) are a group of brominated flame retardants that are extensively employed in the industrial production of plastics, furniture, and construction materials. Due to their regular use and massive emissions, HBCDs have been distributed in the environment (air, water, soil, and sediments). Due to their high toxicity, persistent and long-distance transport, and bioaccumulation, HBCDs were listed in the Stockholm Convention in 2013. Thus, the accurate analysis and strict control of the pollution levels of HBCDs in environmental samples are critical to the government’s long-term environmental supervision mechanism. However, the concentration levels of HBCDs in real samples are low, combined with complex matrices, which seriously limits the determination of HBCDs. The target isomers are particularly transformed or degraded, which makes analysis challenging due to the high temperatures and specific organic solvents. The physicochemical features, toxic and environmental dangers, usage, and standard limitations of HBCDs are briefly discussed herein. Sample pretreatment and instrument detection of HBCDs in various matrices are summarized (i. e., soil, sediment, food, electronics, atmosphere, animals, and water). More than 70 research papers (2000-2022) from the Science Citation Index (SCI) and Chinese core publications are cited herein. First, the entire process of extraction, purification, separation, and enrichment of HBCDs is compared, including soxhlet extraction (SE), ultrasonic-assisted extraction (UAE), accelerated solvent extraction(ASE), supercritical fluid extraction (SFE), solid phase extraction (SPE), dispersed solid phase extraction (DSPE), liquid-liquid extraction (LLE), dispersive liquid-liquid microextraction (DLLME), and solid phase microextraction (SPME). In the literature, UAE is the most commonly employed process, accounting for a quarter of all HBCDs sample pretreatments. Additionally, SPE sample pretreatment technology can completely separate the targets and impurities to reduce the effect of matrix; and enrich the targets to improve sensitivity of method. By using SPE technology, the enrichment factor can be increased due to the massive sample volume, thus enabling detect HBCDs concentrations (nanogram per liter level) in water. Second, the advantages and disadvantages of instrument approaches are examined and discussed, including gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS), liquid chromatography (LC), and liquid chromatography-tandem mass spectrometry (LC-MS/MS), which offer a reference for meeting the requirements in the determination of HBCDs in real samples, i. e., the total HBCDs can be detected by GC or GC-MS and three HBCD isomers (α-HBCD, β-HBCD, γ-HBCD) can be determined by LC or LC-MS. By using the triple quadrupole mass spectrometer, the sensitivity of the method can be improved. Till date, LC-MS/MS has been chosen as an instrument for the determination of HBCDs in various matrices (i. e., seawater, marine sediment, marine organisms, toys, and electronic products) in China. However, there are several challenges. The sample pretreatment is tedious; large sample volumes and organic solvent utilization. These challenges point to the development trends of analytical approaches for HBCDs. The development of green, automated, low-cost, fast, and efficient sample pretreatment approaches for new adsorption materials is the main development direction in the analysis of HBCDs in the future.

Key words: sample pretreatment, detection methods, hexabromocyclododecanes (HBCDs), brominated flame retardants, review

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