在线固相萃取-超高效液相色谱-串联质谱法测定水源水和饮用水中51种全氟和多氟烷基物质

doi:10.3724/SP.J.1123.2024.12020

摘要/Abstract

摘要：

本研究建立了在线固相萃取-超高效液相色谱-串联质谱法快速筛查和检测水源水及饮用水中51种全氟和多氟烷基物质（PFASs）的分析方法。样品中加入甲酸铵及24种PFASs内标物质，混匀后使样品中甲酸铵浓度为2 mmol/L，PFASs内标物质质量浓度为2.5~50 ng/L，样品经0.22 μm孔径醋酸纤维素滤膜过滤后5 mL进样，经HLB在线固相萃取柱吸附后用2 mmol/L甲酸铵淋洗，以乙腈和2 mmol/L甲酸铵水溶液为流动相在线固相萃取后经BEH C₁₈色谱柱进行分离，采用电喷雾离子源负离子模式电离、多反应监测模式检测，内标法定量。以水源水及饮用水作为基质，对其准确度和精密度进行方法学验证，结果表明：51种PFASs在其相应范围内线性关系良好（相关系数r²>0.995），方法的检出限和定量限分别为0.03~1.5 ng/L和0.1~5.0 ng/L。将目标分析物在1、10、50 ng/L水平下加标，水源水和饮用水的加标回收率分别为60.2%~126.9%和60.4%~122.6%，相对标准偏差分别为0.3%~17.9%（n=6）和0.4%~17.7%（n=6）。用该方法测定水源水和饮用水中PFASs残留，结果显示，全氟烷基羧酸、全氟烷基磺酸、全氟烷基醚酸有较高水平的检出，其中水源水中检出质量浓度为0.1~209.7 ng/L，饮用水中检出质量浓度为0.1~63.6 ng/L。与离线固相萃取方法相比，本方法样品用量少，提高了样品采集便捷性的同时减少了内标物质用量。分析速度快且灵敏度高，重复性好，样品从在线富集至检测完成仅耗时20 min即可完成51种PFASs ng/L水平的同时测定。该方法适用于水源水和饮用水中全氟烷基羧酸、全氟烷基磺酸、全氟烷基醚酸、氟调聚物、氟烷基磺酰胺等多类PFASs的痕量测定，有效提高了水体中PFASs类物质的检测效率，实际应用价值较高。

关键词: 在线固相萃取, 超高效液相色谱-串联质谱法, 全氟和多氟烷基物质, 水源水, 饮用水

Abstract:

In this study， an online solid-phase extraction-ultra performance liquid chromatography-tandem mass spectrometry （online SPE-UPLC-MS/MS） method was established to rapidly screen and determine 51 per- and polyfluoroalkyl substances （PFASs） in raw and drinking water. Ammonium formate and 24 PFAS internal standards were added to each sample. The ammonium formate concentration in the sample was 2 mmol/L after mixing， and the contents of the PFAS internal standards ranged between 2.5 and 50 ng/L. Each sample was filtered through a 0.22-μm cellulose acetate filter， and a 5-mL aliquot was injected and adsorbed using an HLB online solid-phase extraction column and rinsed with 2 mmol/L ammonium formate. Acetonitrile and 2 mmol/L aqueous ammonium formate were used as mobile phases. Separation was performed on a BEH C₁₈ chromatographic column with gradient elution. Electrospray ionization source negative ion mode and multiple reaction monitoring mode were used for detection， with quantification performed using the internal standard method. The method was validated by determining accuracies and precisions for the 51 PFASs using raw water and drinking water as matrices. Excellent linear relationships within their respective ranges were observed， with correlation coefficients （r²）>0.995. The method exhibited limits of detection （LODs， S/N=3） and quantification （LOQs， S/N=10） of 0.03–1.5 and 0.1–5.0 ng/L， respectively. The PFASs were spiked at levels of 1， 10 and 50 ng/L， with spiked recoveries of 60.2%–126.9% and 60.4%–122.6% obtained for raw- and drinking-water samples， respectively， along with corresponding relative standard deviations （RSDs， n=6） of 0.3%-17.9% and 0.4%-17.7%， respectively. The developed method was used to determine PFAS residues in raw and drinking water， with perfluoroalkyl carboxylic acids， perfluoroalkyl sulfonic acids， and perfluoroalkyl ether acids detected at relatively high rates with contents of 0.1–209.7 and 0.1–63.6 ng/L in raw water and drinking water， respectively. Compared to offline solid-phase extraction methods， the developed method requires fewer samples， is more convenient from a sample-collection perspective， and uses lower quantities of internal standards. It also analyzes rapidly and is highly sensitive and reproducible. Only 20 min was required to determine the 51 PFASs at the ng/L level， from online enrichment to detection. The developed method is suitable for the trace determination of various types of PFAS， such as perfluoroalkyl carboxylic acids， perfluoroalkyl sulfonic acids， perfluoroalkyl ether acids， fluorotelomers， and fluoroalkyl sulfonamides， in raw and drinking water， thereby effectively boosting the detection efficiency for perfluoroalkyl substances in water in a manner that has substantial practical applications value.

Key words: online solid-phase extraction （online SPE）, ultra performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS）, per- and polyfluoroalkyl substances （PFASs）, raw water, drinking water

中图分类号:

O658

陈永艳, 吕佳, 叶必雄, 张岚, 王园媛, 金宁. 在线固相萃取-超高效液相色谱-串联质谱法测定水源水和饮用水中51种全氟和多氟烷基物质[J]. 色谱, 2025, 43(11): 1222-1234.

CHEN Yongyan, LYU Jia, YE Bixiong, ZHANG Lan, WANG Yuanyuan, JIN Ning. Determination of 51 per- and polyfluoroalkyl substances in raw water and drinking water by online solid-phase extraction coupled with ultra performance liquid chromatography- tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2025, 43(11): 1222-1234.

图/表 10

表 1 液相色谱和在线固相萃取梯度洗脱条件

Table 1 Gradient elution conditions of liquid chromatography and online solid-phase extraction （online-SPE）

Liquid chromatography					Online-SPE
Time/min	Flow rate/（mL/min）	φ（2 mmol/L ammonium formate）/%	φ（Acetonitrile）/%	Curve parameter	Time/min	Flow rate/（mL/min）	φ（2 mmol/L ammonium formate）/%	φ（Methanol）/%	Curve parameter
0	0.35	90	10	11^*	0	2.00	100	0	11
3.5	0.01	90	10	11	0.5	1.00	100	0	11
4.5	0.35	90	10	6^*	3.5	0.01	100	0	11
5.0	0.35	90	10	6	4.5	2.00	0	100	11
7.5	0.35	50	50	6	7.5	2.00	100	0	11
12.0	0.35	5	95	6	20.0	2.00	100	0	11
16.0	0.35	5	95	6
16.5	0.35	90	10	6
20.0	0.35	90	10	6

表 2 51种PFASs及24种内标的质谱参数

Table 2 MS parameters of the 51 per- and polyfluoroalkyl substances （PFASs） and 24 internal standards （ISs）

图1 51种PFASs（50 ng/L）混合标准溶液的总离子流图

Fig. 1 Total ion chromatogram of the 51 PFASs in mixed standard solition （50 ng/L）

图2 甲酸铵的浓度对回收率的影响

Fig. 2 Effects of concentrations of ammonium formate on the recoveriesRec.： recovery.

图3 样品的保存温度和时间对回收率的影响

Fig. 3 Effects of sample storage temperature and time on the recoveries

图4 不同材质滤膜对PFASs回收率的影响

Fig. 4 Effect of different materials of filter membranes on the recoveries of the PFASs

表3 51种PFASs的线性范围、线性方程、相关系数、检出限和定量限

Table 3 Linear ranges， linear equations， correlation coefficients （r2）， LODs， LOQs of the 51 PFASs

表4 51种PFASs的加标回收率和相对标准偏差（n=6）

Table 4 Recoveries and RSDs of the 51 PFASs （n=6）

表 5 水源水和饮用水中PFASs的检出情况

Table 5 Detection of PFASs in raw water and drinking water

表 6 本方法与其他方法的比较

Table 6 Comparison of this proposed method with other methods

Detection method	Samples	Number of detected PFASs	Type of detected PFASs	LOQs/（ng/L）	Sample volume/mL	Ref.
Online-SPE-LC-MS/MS	raw water， drinking water	51	PFCAs， PFSAs， PFECAs， FASAs， FTs， Cl-PFESAs， PFESAs	0.1-5	5	this study
SPE-LC-MS/MS	drinking water	18	PFCAs， PFSAs， PFECAs， FASAs， Cl-PFESAs	0.53-6.3	250	［14］
SPE-LC-MS/MS	drinking water	25	PFCAs， PFSAs， PFECAs， FTs， PFESAs	1.4-16	250	［15］
SPE-LC-MS/MS	drinking water	11	PFCAs， PFSAs	3-5	1000	［16］
SPE-LC-MS/MS	surface water， ground water， waste water， seawater	2	PFCAs， PFSAs	2.0-2.4	500	［17］

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