Huifan Chen, Huimin Zhou, Zhenguo Wang, Xialin Hu, Daqiang Yin
Key Laboratory of Yangtze River Environment, Ministry of Education, College of Environmental Science and Engineering, Tongji University, Shanghai, P. R. China.
J Sep Sci. 2025 Jul;48(7):e70200. doi: 10.1002/jssc.70200.
Benzotriazole ultraviolet stabilizers (BUVSs) are emerging persistent pollutants, due to the weak polarity and wide log K values, there is no general optimal analytical method for BUVSs. In this study, a solid-phase extraction-ultra performance liquid chromatography tandem mass spectrometry (SPE-UHPLC/MS/MS) method was developed for the simultaneous determination of seven BUVSs in the aqueous environment, based on the generalized electrospray ionization (ESI+) mode. The conditions of ESI-UHPLC-MS/MS detection and SPE were systematically optimized. A 50 mm UHPLC column at a column temperature of 40°C gave the highest response for the target BUVSs using methanol-0.1% (v/v) formic acid solution as the mobile phase. The effects of the four packed SPE cartridges (HLB, HC-C, LC-C and phenyl columns) and sample pH (3.0-9.0) on the SPE enrichment were comparatively analyzed, and the optimum condition was HLB cartridges at sample pH 3.0. The SPE elution solvent was optimized as 5 mL methanol + 5 mL dichloromethane (V:V = 1:1). The seven target BUVSs were quantified by isotope internal standard method, and the linear range of the standard curve was wide (0.1-50 ng∙L) with the correlation coefficient R > 0.998. The recoveries of the spiked standards for the purified water as well as the sample of Huangpu River were 80.6%-105.2% and 53.9%-103.7% (except UV-P: 141.6%-148.7%), respectively. The relative standard deviations (RSDs) of the intra-day were 4.1%-18.0%; and the RSDs of the inter-day were 3.4%-18.8%, respectively. The limits of detection of the method were in the range of 0.050-0.406 ng∙L. Compared with the reported studies, this method is more sensitive and stable, and the UHPLC-MS/MS instrument based on the ESI ionization source is more generalizable.
苯并三唑类紫外线稳定剂(BUVSs)是新兴的持久性污染物,由于其极性较弱且log K值范围较宽,目前尚无适用于BUVSs的通用最佳分析方法。本研究基于广义电喷雾电离(ESI+)模式,建立了一种固相萃取-超高效液相色谱串联质谱(SPE-UHPLC/MS/MS)法,用于同时测定水环境中的七种BUVSs。对ESI-UHPLC-MS/MS检测条件和SPE条件进行了系统优化。使用甲醇-0.1%(v/v)甲酸溶液作为流动相,在柱温40°C的50 mm UHPLC柱上,目标BUVSs的响应最高。比较分析了四种填充固相萃取柱(HLB柱、HC-C柱、LC-C柱和苯基柱)以及样品pH值(3.0 - 9.0)对SPE富集效果的影响,最佳条件为pH 3.0的HLB柱。将SPE洗脱溶剂优化为5 mL甲醇 + 5 mL二氯甲烷(V:V = 1:1)。采用同位素内标法对七种目标BUVSs进行定量,标准曲线线性范围宽(0.1 - 50 ng∙L),相关系数R > 0.998。纯化水以及黄浦江样品中加标标准物的回收率分别为80.6% - 105.2%和53.9% - 103.7%(UV-P除外:141.6% - 148.7%)。日内相对标准偏差(RSDs)为4.1% - 18.0%;日间RSDs分别为3.4% - 18.8%。该方法的检测限在0.050 - 0.406 ng∙L范围内。与已报道的研究相比,该方法更灵敏、稳定,基于ESI电离源的UHPLC-MS/MS仪器通用性更强。