典型全氟有机酸类化合物的样品前处理与分析方法研究进展

doi:10.3724/SP.J.1123.2019.06016

摘要/Abstract

摘要：

全氟辛烷磺酸（PFOS）和全氟辛烷羧酸（PFOA）是两种典型的全氟有机酸类化合物，也是全氟化合物（PFCs）前体物的最终降解产物，具有肝毒性、胚胎毒性、生殖毒性、神经毒性，检出率最高。在各种被污染的介质中，PFOS和PFOA含量往往很低，基体复杂多样，快速高效的样品前处理技术成为测定的关键环节。目前，国际上对PFOS和PFOA的测定无统一标准，而我国关于PFCs的分析研究落后于国际发展水平。该文介绍了PFOS和PFOA的特性，系统总结和评述了前处理技术（液液萃取、固相萃取、固相微萃取、超声萃取和QuEChERS法）及分析方法（色谱-质谱方法、光谱法、酶联免疫法和电化学法），以期为PFOS和PFOA的分析监测及标准制定提供参考。

关键词: 全氟化合物, 全氟辛烷磺酸, 全氟辛烷羧酸, 样品前处理, 分析方法, 综述

Abstract:

Perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) are typical perfluorinated organic acids with hepatotoxicity, embryonic toxicity, reproductive toxicity, and neurotoxicity. As the final degradation products of perfluorochemicals (PFCs) precursors, PFOS and PFOA are detected frequently. Presently, there are no unified standards for the detection of PFOS and PFOA. The analytical techniques used for PFCs in China are much less sophisticated than those in the developed countries. In this paper, the characteristics of PFOS and PFOA are introduced. Sample preparation technologies (liquid-liquid extraction, solid-phase extraction, solid-phase microextraction, ultrasonic extraction, and QuEChERS), and analytical methods (chromatography-mass spectrometry, spectrometry, ELISA, and electrochemical methods) are summarized and reviewed, so as to provide reference for monitoring and setting standards.

Key words: perfluorochemicals (PFCs), perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA), sample preparation, analytical methods, review

贺锦灿, 张诗韵, 苏榆媛, 宋嘉怡, 毋福海. 典型全氟有机酸类化合物的样品前处理与分析方法研究进展[J]. 色谱, 2020, 38(1): 86-94.

HE Jincan, ZHANG Shiyun, SU Yuyuan, SONG Jiayi, WU Fuhai. Progress on the sample techniques and analytical methods for typical perfluorinated organic acids[J]. Chinese Journal of Chromatography, 2020, 38(1): 86-94.

图/表 2

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Analytical methods	Sample preparation	LOD/ (ng/L)	Analytes	Advantages	Disadvantages
RRS: resonance Rayleigh scattering; ELISA: enzyme-linked immunosorbent assay; VALLME: vortex-assisted liquid-liquid microextraction; μ SPE: micro-solid-phase extraction; SPME: solid-phase microextraction; PFCs: perfluorochemicals.
GC-MS	magnetic SPE, derivation^[49]	86	PFOA and other PFCs in lake water	chromatographic peak with high resolution	derivation reaction using toxic reagent, complex operation and time-consuming
HPLC-MS	VALLME^[54]	0.22, 3.0	PFOS, PFOA, and other PFCs in seawater	without derivation, sensitive	incomplete analysis, consumption of large amounts of organic reagents, possible background pollution by fluorochemicals
HPLC-MS/MS	μSPE^[55]	0.06	PFOA and other PFCs in river and rain water	short extraction time, sensitive, mature and	possible background pollution by fluorochemicals, incomplete analysis
	magnetic SPE^[56]	0.05, 0.05	PFOS, PFOA, and other PFCs in river water	reliable
	online SPE^[58]	0.5, 1	PFOS, PFOA, and other PFCs in surface and underground water	automatic, rapid, accurate, sensitive	maintenance operations by professional personnel
MS	SPME^{[31, 32]}	0.06, 0.1^[31], 20, 30^[32]	PFOS, PFOA, and other PFCs in lake water, river water, whole blood, milk^[31], and body fluid in daphnia magna^[32]	without chromatogra- phic separation, rapid, sensitive	less choice for commercial SPME, high cost of use and maintenance of the instrument
	SPE^[51]	640	PFOS and other PFCs river water and tap water	without chromatogra- phic separation, rapid, direct analysis	less sensitive without preconcentration, high cost for use and maintenance of the instrument
Colorimetry	SPE^[59]	1000, 1000	PFOS and PFOA in tap water and river water	low cost, rapid, easy operation,	less sensitive than chromatography or MS
Fluore-scence	cation exchange resin^[70]	1100	PFOS in tap water and river water	low cost, rapid	less sensitive than chromatography or MS, analysis of one analyte at a time
	dilution^[71]	0.066, 0.085	PFOS in human urine and serum	rapid, selective, sensitive	analysis of one analyte at a time
RRS	cation exchange resin^[76]	4500	PFOA in tap water and river water	low cost, rapid, selective	less sensitive than chromatography or MS, analysis of one analyte at a time
ELISA		2.5^[77]	PFOS in river water, lake water, water in waterworks, and bottled purified water	rapid, convenient, high-throughput	less sensitive than chromatography or MS
Electrochemistry	SPE^[74]	10	PFOA in tap water, river water, and lake water	low cost, sensitive	complex modification of electrode, analysis of one analyte at a time

Analytical methods	Sample preparation	LOD/ (ng/L)	Analytes	Advantages	Disadvantages
RRS: resonance Rayleigh scattering; ELISA: enzyme-linked immunosorbent assay; VALLME: vortex-assisted liquid-liquid microextraction; μ SPE: micro-solid-phase extraction; SPME: solid-phase microextraction; PFCs: perfluorochemicals.
GC-MS	magnetic SPE, derivation^[49]	86	PFOA and other PFCs in lake water	chromatographic peak with high resolution	derivation reaction using toxic reagent, complex operation and time-consuming
HPLC-MS	VALLME^[54]	0.22, 3.0	PFOS, PFOA, and other PFCs in seawater	without derivation, sensitive	incomplete analysis, consumption of large amounts of organic reagents, possible background pollution by fluorochemicals
HPLC-MS/MS	μSPE^[55]	0.06	PFOA and other PFCs in river and rain water	short extraction time, sensitive, mature and	possible background pollution by fluorochemicals, incomplete analysis
	magnetic SPE^[56]	0.05, 0.05	PFOS, PFOA, and other PFCs in river water	reliable
	online SPE^[58]	0.5, 1	PFOS, PFOA, and other PFCs in surface and underground water	automatic, rapid, accurate, sensitive	maintenance operations by professional personnel
MS	SPME^{[31, 32]}	0.06, 0.1^[31], 20, 30^[32]	PFOS, PFOA, and other PFCs in lake water, river water, whole blood, milk^[31], and body fluid in daphnia magna^[32]	without chromatogra- phic separation, rapid, sensitive	less choice for commercial SPME, high cost of use and maintenance of the instrument
	SPE^[51]	640	PFOS and other PFCs river water and tap water	without chromatogra- phic separation, rapid, direct analysis	less sensitive without preconcentration, high cost for use and maintenance of the instrument
Colorimetry	SPE^[59]	1000, 1000	PFOS and PFOA in tap water and river water	low cost, rapid, easy operation,	less sensitive than chromatography or MS
Fluore-scence	cation exchange resin^[70]	1100	PFOS in tap water and river water	low cost, rapid	less sensitive than chromatography or MS, analysis of one analyte at a time
	dilution^[71]	0.066, 0.085	PFOS in human urine and serum	rapid, selective, sensitive	analysis of one analyte at a time
RRS	cation exchange resin^[76]	4500	PFOA in tap water and river water	low cost, rapid, selective	less sensitive than chromatography or MS, analysis of one analyte at a time
ELISA		2.5^[77]	PFOS in river water, lake water, water in waterworks, and bottled purified water	rapid, convenient, high-throughput	less sensitive than chromatography or MS
Electrochemistry	SPE^[74]	10	PFOA in tap water, river water, and lake water	low cost, sensitive	complex modification of electrode, analysis of one analyte at a time

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