基于金属有机骨架多孔碳材料的分散固相萃取-超高效液相色谱-串联质谱法测定水中四种酚类内分泌干扰物
[Determination of four phenolic endocrine-disrupting chemicals in water by dispersive solid-phase extraction-ultra performance liquid chromatography-tandem mass spectrometry based on metal-organic skeleton porous carbon materials].
作者信息
Wang Pan, Ma Ji-Ping, Li Shuang, Cheng Jia-Wen, Huang Chao-Nan
机构信息
School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266525, China.
出版信息
Se Pu. 2024 Mar 8;42(3):264-274. doi: 10.3724/SP.J.1123.2023.05012.
Phenolic endocrine-disrupting chemicals (EDCs) are exogenous substances that interfere with the endocrine system and disrupt normal cell functions upon entering a living organism, leading to reproductive and developmental toxicity. Therefore, the development of a rapid and efficient analytical method for detecting phenolic EDCs in environmental waters is crucial. Owing to the low concentration of phenolic EDCs in environmental water, appropriate sample pretreatment methods are necessary to remove interferences caused by the sample matrix and enrich the target analytes before instrumental analysis. Dispersive solid-phase extraction (DSPE) has gained considerable attention as a simple and rapid sample pretreatment method for environmental-sample analysis. In this method, an adsorbent material is uniformly dispersed in a sample solution and the target analytes are extracted through processes such as vortexing. Compared with traditional solid-phase extraction (SPE), DSPE increases the contact area between the adsorbent and sample solution, reduces the required amounts of adsorbent and organic solvents, and improves the extraction efficiency. The adsorbent material plays a critical role in DSPE because it determines the extraction efficiency of the method. Metal-organic frameworks (MOFs) are porous framework materials composed of metal clusters and multifunctional organic ligands. They possess many excellent properties such as tunable pore sizes, large surface areas, and good thermal and chemical stability, rendering them ideal adsorbent materials for sample pretreatment. MOF-derived porous carbon materials obtained through high-temperature carbonization not only increase the density of MOF materials for better separation but also retain the advantages of a large surface area, highly ordered porous structure, and high porosity. In this study, a porous carbon material derived from an MOF, named as University of Oslo-66-carbon (UiO-66-C), was synthesized using a solvothermal method and applied as an adsorbent to enrich four phenolic EDCs (bisphenol A, 4--octylphenol, 4-nonylphenol, and nonylphenol) in water. A method combining DSPE with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to analyze these phenolic EDCs in water. The UiO-66-C dosage, pH of water sample, adsorption time, eluent type and volume, elution time, and ion strength were optimized. Gradient elution was performed using methanol-water as the mobile phase. The target analytes were separated on an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm), and multiple reaction monitoring (MRM) was conducted in negative electrospray ionization mode. The method exhibited a linear correlation within the range of 0.5-100 μg/L for the four phenolic EDCs. The limits of detection (LODs) and quantification (LOQs) of the four phenolic EDCs were 0.01-0.13 μg/L and 0.03-0.42 μg/L, respectively. The precision of the method was evaluated through intra- and inter-day relative standard deviations (RSDs), with values ranging from 1.5% to 10.6% and from 6.1% to 13.2%, respectively. When applied to the detection of phenolic EDCs in tap and surface water, the spiked recoveries of the four phenolic EDCs were 77.1%-116.6%. Trace levels of 4-nonylphenol and nonylphenol were detected in surface water at levels of 1.38 and 0.26 μg/L, respectively. The proposed method exhibits good accuracy and precision; thus, it provides a new rapid, efficient, and sensitive approach for the detection of phenolic EDCs in environmental water.
酚类内分泌干扰物(EDCs)是一类外源性物质,它们会干扰内分泌系统,并在进入生物体后破坏正常细胞功能,导致生殖和发育毒性。因此,开发一种快速高效的分析方法来检测环境水体中的酚类EDCs至关重要。由于环境水中酚类EDCs的浓度较低,在进行仪器分析之前,需要采用适当的样品预处理方法来去除样品基质引起的干扰并富集目标分析物。分散固相萃取(DSPE)作为一种用于环境样品分析的简单快速的样品预处理方法受到了广泛关注。在该方法中,吸附剂材料均匀分散在样品溶液中,目标分析物通过涡旋等过程被萃取出来。与传统固相萃取(SPE)相比,DSPE增加了吸附剂与样品溶液之间的接触面积,减少了吸附剂和有机溶剂的用量,并提高了萃取效率。吸附剂材料在DSPE中起着关键作用,因为它决定了该方法的萃取效率。金属有机框架(MOFs)是由金属簇和多功能有机配体组成的多孔框架材料。它们具有许多优异的性能,如孔径可调、比表面积大、热稳定性和化学稳定性好等,使其成为样品预处理的理想吸附剂材料。通过高温碳化获得的MOF衍生多孔碳材料不仅提高了MOF材料的密度以实现更好的分离,还保留了比表面积大、多孔结构高度有序和孔隙率高的优点。在本研究中,采用溶剂热法合成了一种由MOF衍生的多孔碳材料,命名为奥斯陆大学-66-碳(UiO-66-C),并将其用作吸附剂来富集水中的四种酚类EDCs(双酚A、4-辛基酚、4-壬基酚和壬基酚)。建立了一种将DSPE与超高效液相色谱-串联质谱(UPLC-MS/MS)相结合的方法来分析水中的这些酚类EDCs。对UiO-66-C用量、水样pH值、吸附时间、洗脱剂类型和体积、洗脱时间以及离子强度进行了优化。使用甲醇-水作为流动相进行梯度洗脱。目标分析物在ACQUITY UPLC BEH C18柱(100 mm×2.1 mm,1.7 μm)上分离,并在负电喷雾电离模式下进行多反应监测(MRM)。该方法对四种酚类EDCs在0.5 - 100 μg/L范围内呈现线性相关。四种酚类EDCs的检测限(LODs)和定量限(LOQs)分别为0.01 - 0.13 μg/L和0.03 - 0.42 μg/L。通过日内和日间相对标准偏差(RSDs)对该方法的精密度进行评估,其值分别在1.5%至10.6%和6.1%至13.2%之间。当应用于自来水和地表水的酚类EDCs检测时,四种酚类EDCs的加标回收率为77.1% - 116.6%。在地表水中检测到痕量的4-壬基酚和壬基酚,含量分别为1.38和0.26 μg/L。所提出的方法具有良好的准确度和精密度;因此,它为环境水体中酚类EDCs的检测提供了一种新的快速、高效且灵敏的方法。