关键词: 六氯丁二烯, 持久性有机污染物, 样品前处理, 仪器检测, 综述

Abstract:

Hexachlorobutadiene (HCBD) is one of persistent organic pollutants (POPs) listed in Annex A and Annex C of the Stockholm Convention in 2015 and 2017, respectively. Research on the sources, environmental occurrences, and biological effects of HCBD has a great significance in controlling this newly added POPs. Sensitive and credible methods for the determination of HCBD are preconditions and form the basis for related research work. In recent years, many researchers have included HCBD as one of the analytes in monitoring or methodological studies. Based on the results of these studies, this paper reviews the research progress on analytical methods for the determination of HCBD and focuses on sample pretreatment methods for the analysis of HCBD in various matrices such as air, water, soil, sewage sludge, and biological tissues. The advantages and disadvantages of the methods are also compared to provide reference for further research in this field.
For air samples, HCBD was usually collected by passing air through sorbent cartridges. Materials such as Tenax-TA, Carbosieve, Carbopack, Carboxen 1000, or their mixtures were used as the sorbent. HCBD was thermally desorbed and re-concentrated in a trap and finally transferred for instrumental analysis. Limits of detection (LODs) for HCBD in these methods were at the ng/m³ scale. Compared to sampling using pumps, passive air samplers (PAS) such as polyurethane foam PAS (PUF-PAS) do not require external power supply and are more convenient for sampling POPs in air at a large scale. The LOD of the sorbent-impregnated PUF PAS (SIP-PAS) method was much lower (0.03 pg/m³) than that of the PUF-PAS method (20 pg/m³). However, the sampling volumes in the SIP-PAS and PUF-PAS methods (-6 m³) calculated from the log K_OA value of HCBD have significant uncertainty, and this must be confirmed in the future.
For water samples, HCl or copper sulfate was added to the sample immediately after sampling to prevent any biological activities. HCBD can be extracted from water using methods such as the purge and trap method, liquid-liquid extraction (LLE) method, and solid phase extraction (SPE) method. Among these methods, SPE enabled the simultaneous extraction, purification, and concentration of trace HCBD in a single step. Recoveries of HCBD on Strata-X and Envi-Carb SPE cartridges (63%-64%) were higher than those on Envi-disk, Oasis HLB, and Strata-C18 cartridges (31%-46%). Drying is another key step for obtaining high recoveries of HCBD. Disk SPE involving the combination of a high-vacuum pump and a low-humidity atmosphere is an effective way to eliminate the residual water. In addition, a micro SPE method using functionalized polysulfone membranes as sorbents and employing ultrasonic desorption was developed for extracting HCBD from drinking water. The recovery of HCBD reached 102%, with a relative standard deviation (RSD) of 3.5%.
For solid samples such as dust, soil, sediment, sewage sludge, fly ash, and biota tissue, multiple pretreatment methods were used in combination, owing to the more complex matrix. Freeze or air drying, grinding, and sieving of samples were commonly carried out before the extraction. Soxhlet extraction is a typical extraction method for HCBD; however, it requires many organic reagents and is time consuming. The accelerated solvent extraction (ASE) method requires a small amount of organic reagent, and the extraction can be performed rapidly. It was recently applied for the extraction of HCBD from solid samples under 10.34 MPa and at 100 ℃. Purification could be achieved simultaneously by mixing florisil materials with samples in the ASE pool. Nevertheless, employing the ASE methods widely is difficult because of their high costs. Ultrasonic-assisted extraction (UAE) has the same extraction efficiency for HCBD, with much lower costs compared to ASE, and is therefore adopted by most researchers. The type of extraction solvent, solid-to-liquid ratio, ultrasonic temperature, and power affect the extraction efficiency. Ultrasonic extraction at 30 ℃ and 200 W using 30 mL dichloromethane as the extraction solvent resulted in acceptable recoveries (64.0%-69.4%) of HCBD in 2 g fly ash. After extraction, a clean-up step is necessary for the extracts of solid samples. Column chromatography is frequently used for purification. The combined use of several columns or a multilayer column filled with florisil, silica gel, acid silica gel, or alumina can improve the elimination efficiency of interfering substances.
Instrumental analysis for HCBD is mainly performed with a gas chromatograph equipped with a mass spectrometer operating in selected ion monitoring mode. DB-5MS, HP-5MS, HP-1, ZB-5MS, and BP-5 can be used as the chromatographic columns. Qualification ions and quantification ions include m/z 225, 223, 260, 227, 190, and 188. GC-MS using an electron ionization (EI) source was more sensitive to HCBD than GC-MS using a positive chemical ionization source (PCI) and atmospheric pressure chemical ionization source (APCI). Gas chromatography-tandem mass spectrometry (GC-MS/MS), gas chromatography-high-resolution mass spectrometry (GC-HRMS), and high-resolution gas chromatography-high-resolution mass spectrometry (HRGC-HRMS) have recently been used for the separation and determination of HCBD and various other organic pollutants. Instrumental detection limits for HCBD in GC-MS/MS, GC-HRMS, and HRGC-HRMS were more than ten times lower than that in GC-MS, indicating the remarkable application potential of these high-performance instruments in HCBD analysis.

Key words: hexachlorobutadiene, persistent organic pollutants (POPs), sample pretreatment, instrumental detection, review