Progress on the sample techniques and analytical methods for typical perfluorinated organic acids

doi:10.3724/SP.J.1123.2019.06016

Abstract

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

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.

Figures/Tables 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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