超高效液相色谱-串联质谱法同时测定水、沉积物和生物样品中57种全/多氟化合物

引用本文: 杨愿愿, 李偲琳, 赵建亮, 应光国, 陈长二. 超高效液相色谱-串联质谱法同时测定水、沉积物和生物样品中57种全/多氟化合物[J]. 分析化学, 2022, 50(8): 1243-1251. doi: 10.19756/j.issn.0253-3820.210621 shu

Citation: YANG Yuan-Yuan, LI Cai-Lin, ZHAO Jian-Liang, YING Guang-Guo, CHEN Chang-Er. Determination of 57 Kinds of Per- and Polyfluoroalkyl Substances in Water, Sediments and Biological Samples by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry[J]. Chinese Journal of Analytical Chemistry, 2022, 50(8): 1243-1251. doi: 10.19756/j.issn.0253-3820.210621 shu

超高效液相色谱-串联质谱法同时测定水、沉积物和生物样品中57种全/多氟化合物

1.
华南师范大学环境研究院, 广东省化学污染与环境安全重点实验室, 环境理论化学教育部重点实验室, 广州 510006;
2.
华南师范大学环境学院, 广州 510006

通讯作者: 陈长二,E-mail:changer.chen@scnu.edu.cn

基金项目:
国家自然科学基金项目(No.42007380)、中科院海洋大科学中心重点部署项目(No.COMS2019J08)、广州市科技创新计划项目(No.201904010291)和广东省化学品污染与环境安全重点实验室项目(No.2019B030301008)资助。 # 共同第一作者

摘要: 本研究建立了一种适用于地表水、污水处理厂进水和出水、沉积物和生物基质样品中57种全/多氟化合物(PFAS)的样品前处理和仪器检测方法。水样利用WAX固相萃取柱进行富集和净化;沉积物样品采用离子对试剂萃取的方法进行提取净化;鱼肉样品采用碱消解方法去除其中的蛋白质和脂肪等杂质,再利用WAX固相萃取柱进行富集和净化。样品中的PFAS采用超高效液相色谱-串联质谱法在电喷雾负离子模式(ESI^-)下,采用内标法定量检测。所有目标化合物经反相色谱柱分离后可在10 min内得到有效分离,线性范围为0.5~100 μg/L (R²＞0.99)。地表水、污水处理厂进水和出水、沉积物和鱼肉中57种PFAS的回收率分别为61.2%~143.0%、60.1%~128.0%、60.5%~128.0%、60.3%~134.0%和60.9%~127.0%,相对标准偏差在0.2%~24.0%范围内,方法的定量限分别为0.04~6.90 ng/L、0.05~8.50 ng/L、0.04~9.30 ng/L、0.01~2.20 ng/g和0.21~7.90 ng/g。将本方法应用于深圳段茅洲河中水和沉积物样品、某污水处理厂进出水样品以及北江鱼样品中PFAS的测定,在茅洲河地表水和沉积物中分别检出19和20种PFAS,其中均为PFOS的浓度最高(50.5 ng/L和8.79 ng/g);在污水处理厂进水和出水中共检出11种PFAS,其中PFOA的浓度最高,所有检出的PFAS的去除率均小于25%;鱼样品中共检出8种长链PFAS,其中PFOS的浓度最高(最高达14.8 ng/g)。本方法灵敏度高、重现性好,适用于不同环境基质和生物样品中多种PFAS的同时检测,可为PFAS的环境行为研究提供重要的方法学基础。

关键词:

English

Determination of 57 Kinds of Per- and Polyfluoroalkyl Substances in Water, Sediments and Biological Samples by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry

1.
Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety & MOE Key Laboratory of Theoretical Chemistry of Environment, Environmental Research Institute, South China Normal University, Guangzhou 510006, China;
2.
School of Environment, South China Normal University, Guangzhou 510006, China

Corresponding author: CHEN Chang-Er, changer.chen@scnu.edu.cn

Received Date: 09 July 2021
Revised Date: 30 April 2022
Fund Project:
Supported by the National Natural Science Foundation of China (No.42007380), the Key Deployment Project of Centre for Ocean Mega-Research of Science, Chinese Academy of Sciences (No.COMS2019J08), the Guangzhou Municipal Science and Technology Project (No.201904010291) and the Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety (No.2019B030301008).

Abstract: A method including sample pretreatment and instrumental detection was developed for quantifying 57 kinds of per- and polyfluoroalkyl substances (PFAS) in surface water, influent and effluent water of wastewater treatment plants (WWTPs), sediment and biological samples. The water samples and sediment samples were concentrated and purified by WAX solid phase extraction (SPE) columns and ion-pairing liquid-extraction method, respectively; while the fish samples were firstly digested with alkaline to protein and fat, and then extracted by WAX SPE column. The target PFAS were detected by ultra-high liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) in negative electrospray ionization (ESI^-) mode and quantified with internal standard method and calibration curve (0.5-100 μg/L). All PFAS could be separated within 10 min and the determination coefficients for PFAS were all >0.99. The recoveries of 57 kinds of PFAS in surface water, influent and effluent waters, sediment and fish were 61.2%-143.0%, 60.1%-128.0%, 60.5%-128.0%, 60.3%-134.0% and 60.9%-127.0%, respectively, with relative standard deviations (RSDs) ranging from 0.18% to 24%. Besides, the method quantification limits (MQLs) were 0.04-6.90 ng/L, 0.05-8.50 ng/L, 0.04-9.30 ng/L, 0.01-2.20 ng/g and 0.21-7.90 ng/g, respectively. The method was applied to determination of PFAS in water samples from Maozhou River, influent and effluent waters from a WWTP and fish samples from the North River. Twenty kinds of PFAS were found in the water and sediment from the Maozhou river, dominated by PFOS (50.5 ng/L and 8.79 ng/g, respectively); 11 kinds of PFAS were detected in the WWTP with PFOA as the main compound, and the removal rates were less than 25%. Only 8 kinds of longer chain-length PFAS were observed in the fish samples, dominated by PFOS (up to 14.8 ng/g). The established method was sensitive and accurate, and suitable for simultaneous detection of 57 kinds of PFAS in various environmental matrix and biological samples.

Key words:

Perand polyfluoroalkyl substances
/ Surface water
/ Sediment
/ Liquid chromatography-tandem mass spectrometry
/ Biological sample

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

超高效液相色谱-串联质谱法同时测定水、沉积物和生物样品中57种全/多氟化合物

通讯作者: 陈长二,E-mail:changer.chen@scnu.edu.cn

English

Determination of 57 Kinds of Per- and Polyfluoroalkyl Substances in Water, Sediments and Biological Samples by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry

Corresponding author: CHEN Chang-Er, changer.chen@scnu.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

超高效液相色谱-串联质谱法同时测定水、沉积物和生物样品中57种全/多氟化合物

通讯作者: 陈长二,E-mail:changer.chen@scnu.edu.cn

English

Determination of 57 Kinds of Per- and Polyfluoroalkyl Substances in Water, Sediments and Biological Samples by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry

Corresponding author: CHEN Chang-Er, changer.chen@scnu.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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