复杂环境基质中全氟化合物检测方法的优化及应用

doi:10.3969/j.issn.1000-5641.2024.06.004

摘要/Abstract

摘要：

利用固相萃取联合超高效液相色谱串联质谱仪技术优化了全氟化合物 (perfluoroalkyl substances, PFASs) 仪器检测方法和复杂环境样品前处理方法, 得到了一套环境多介质中41种全氟化合物的同步提取及检测方法. 在仪器优化方面, 通过单个标准品手动调谐确定了目标物最优化的离子对质荷比和质谱参数, 确定了2 mmol/L乙酸铵溶液和甲醇组合作为最优色谱流动相. 在样品萃取和净化方面, 发现固体样品在30℃水浴下超声萃取10 min比加速溶剂萃取的回收率更高且用时更短; 使用平行定量浓缩仪进行氮吹浓缩目标物平均回收率高达104.3%, 且比传统水浴氮吹仪节省约50%的时间; 分别使用2 mmol/L乙酸铵溶液(pH = 3)和1 mL 0.5%氨水甲醇溶液进行固相萃取柱淋洗和洗脱时, 样品平均回收率可达108.2%和105.5%. 利用优化后的方法对实际样品 (土壤、沉积物和水体) 进行检测, 方法检出限为0.01 ~ 0.34 ng, 基质加标回收率为67.9% ~ 174.9%, 平行样相对标准偏差为0.03% ~ 28.10%. 总体来讲, 优化后的样品前处理方法比以往方法更省时省溶剂, 且灵敏度和回收率都较好, 为环境样品的大批量检测提供了技术依据.

关键词: 全氟化合物, 环境多介质, 检测方法, 方法应用

Abstract:

The detection method for perfluorinated compounds (PFASs) and the sample pretreatment process for complex environments were optimized using solid-phase extraction in conjunction with ultra-high performance liquid chromatography–tandem mass spectrometry. This optimized method allowed concurrent extraction and identification of 41 PFASs in diverse environmental matrices. Optimal ion pairs and mass spectrometry parameters for the targets were determined through manual tuning of single standards for instrument optimization. The optimal chromatographic mobile phase was identified as a combination of 2 mmol/L ammonium acetate solution and methanol. Higher recovery rates and shorter extraction times compared to accelerated solvent extraction in the context of sample extraction and purification were found for ultrasonic extraction of solid samples at 30°C for 10 minutes. The use of a parallel quantitative concentrator for nitrogen evaporation resulted in an average recovery rate of 104.3%, with a process time half as long as the time required for the traditional water bath method. The average recovery rates were 108.2% and 105.5% when using 2 mmol/L ammonium acetate solution (pH = 3) and 1 mL of 0.5% ammonia methanol solution for solid-phase extraction column elution and washing, respectively. The optimized method was applied to actual samples (soil, sediment, and water), achieving detection limits of 0.01 ~ 0.34 ng, matrix spiking recovery rates of 67.9% ~ 174.9%, and relative standard deviations for parallel samples of 0.03% ~ 28.10%. Overall, the optimized sample preparation method is more time- and solvent-efficient than previous methods, offers better sensitivity and recovery rates, and thus provides a solid technical foundation for large-scale environmental sample detection.

Key words: perfluoroalkyl substances, environmental multi-media, detection methods, method application

中图分类号:

X830.2

李雨珊, 杨静, 李晔, 杨丁业, 丁方方, 王余意, 刘敏. 复杂环境基质中全氟化合物检测方法的优化及应用[J]. 华东师范大学学报（自然科学版）, 2024, 2024(6): 39-51.

Yushan LI, Jing YANG, Ye LI, Dingye YANG, Fangfang DING, Yuyi WANG, Min LIU. Optimization and application of detection methods for perfluorinated compounds in complex environmental matrices[J]. Journal of East China Normal University(Natural Science), 2024, 2024(6): 39-51.

图/表 9

表1

主要 PFASs 的名称、缩写、分子式、母离子及子离子"

化合物	缩写名称	分子式	质荷比(m/z)
化合物	缩写名称	分子式	母离子	子离子
¹H,¹H,²H,²H-全氟十二烷磺酸	10:2FTS	C₁₂H₄F₂₁SO₃Na	626.9	81.0/606.8
¹H,¹H,²H,²H-全氟己烷磺酸	4:2FTS	C₆H₄F₉SO₃Na	326.8	81.0/307.2
9-氯全氟-3-壬氧基磺酸钾	6:2Cl-PFESA	C₈F₁₆ClSO₄K	530.9	83.0/350.9
双(¹H,¹H,²H,²H-全氟辛基)磷酸	6:2diPAP	C₁₆H₈F₂₆O₄PNa	788.9	97.0/442.9
¹H,¹H,²H,²H-全氟辛烷磺酸	6:2FTS	C₈H₄F₁₃SO₃Na	426.9	81.1/406.7
双(全氟己基)次膦酸钠	6:6PFPi	C₁₂F₂₆O₂PNa	701.0	62.8/100.8
全氟己基(全氟辛基)次磷酸钠	6:8PFPi	C₁₄F₃₀O₂PNa	801.0	400.6/500.7
11-氯二十碳氟-3-氧十一烷-1-磺酸钾	8:2Cl-PFESA	C₁₀F₂₀ClSO₄K	630.9	83.0/450.9
双(¹H,¹H,²H,²H-全氟癸基)磷酸钠	8:2diPAP	C₂₀H₈F₃₄O₄PNa	988.8	96.9/542.8
¹H,¹H,²H,²H-全氟癸磺酸	8:2FTS	C₁₀H₄F₁₇SO₃Na	526.9	80.9/506.9
双(全氟辛基)次膦酸钠	8:8PFPi	C₁₆F₃₄O₂PNa	900.9	63.1/500.9
4.8-二氧杂-3H-全氟壬酸钠	NaDONA	C₇HF₁₂O₄Na	376.8	85.0/251.0
8-氯全氟辛烷磺酸钠	Cl-PFOS	C₈ClF₁₆SO₃Na	514.8	80.1/98.8
全氟辛烷磺酰胺	FOSA	C₈H₂F₁₇NO₂S	497.9	78.0/169.0
2,3,3,3-四氟-2-(1,1,2,2,3,3,3-七氟丙氧基)-丙酸	HFPO-DA(GenX)	C₆HF₁₁O₃	285.0	169.0
N-乙基全氟-1-辛烷磺酰胺乙酸	N-EtFOSAA	C₁₂H₈F₁₇NO₄S	584.0	418.9/525.7
全氟-3,6-二氧杂庚酸	NFDHA(3,6-OPFHpA)	C₅HF₉O₄	201.0	85.0
2-(N-甲基全氟辛烷磺酰氨基)乙酸	N-MeFOSAA	C₁₁H₆F₁₇NO₄S	569.9	219.0/419.0
全氟丁酸	PFBA	C₄HF₇O₂	212.9	168.8
全氟丁烷磺酸	PFBS	C₄HF₉O₃S	299.1	79.9/98.8
全氟癸酸	PFDA	C₁₀HF₁₉₀₂	512.9	218.8/469.0
全氟十二酸	PFDoA	C₁₂HF₂₃O₂	612.8	168.8/569.0
全氟癸烷磺酸	PFDS	C₁₀HF₂₁O₃S	598.8	80.0/99.0
全氟-4-乙基环己烷磺酸盐	PFECHS	C₈F₁₅SO₃K	460.9	99.1/380.9
全氟磺酸钾	PFEESA	C₄F₉SO₄K	314.9	83.0/135.0
全氟庚酸	PFHpA	C₇HF₁₃O₂	362.9	168.9/318.9
全氟庚烷磺酸	PFHpS	C₇HF₁₅O₃S	448.9	80.0/99.0
全氟己酸	PFHxA	C₆HF₁₁O₂	312.9	119.0/268.9
全氟十六酸	PFHxDA	C₁₆HF₃₁O₂	812.9	168.9/769.0
全氟己基磺酸	PFHxS	C₆HF₁₃O₃S	398.9	80.0/99.0
全氟-5-氧杂己酸	PFMBA	C₅HF₉O₃	278.9	85.0/235.0
全氟壬酸	PFNA	C₉HF₁₇O₂	462.9	219.0/418.9
全氟壬烷磺酸	PFNS	C₉HF₁₉O₃S	548.9	80.0/99.0
全氟辛酸	PFOA	C₈HF₁₅O₂	412.9	168.8/368.9
全氟十八酸	PFODA	C₁₈HF₃₅O₂	912.9	168.9/869.0
全氟辛基磺酸	PFOS	C₈HF₁₇O₃S	498.9	79.8/99.1
全氟戊酸	PFPeA	C₅HF₉O₂	262.9	218.8
全氟戊烷磺酸	PFPeS	C₅HF₁₁O₃S	348.9	80.1/99.0
全氟十四酸	PFTeDA	C₁₄HF₂₇O₂	712.9	168.9/669.1
全氟十三酸	PFTrDA	C₁₃HF₂₅O₂	662.9	168.9/619.0
全氟十一酸	PFUdA	C₁₁HF₂₁O₂	562.9	269.0/518.9
全氟丁酸-¹³C₄	PFBA-¹³C₄	¹³C₄HF₇O₂	217.0	172.0
全氟戊酸-¹³C₅	PFPeA-¹³C₅	¹³C₅HF₉O₂	267.9	223.0
2,3,3,3-四氟-2-(1,1,2,2,3,3,3-七氟丙氧基)-丙酸-¹³C₃	HFPO-DA-¹³C₃	¹³C₃¹²C₃HF₁₁O₃	287.0	169.0
全氟丁烷磺酸钠-¹³C₃	PFBS-¹³C₃	¹³C₃¹²CF₉SO₃Na	301.9	80.0/99.0
全氟己酸-¹³C₅	PFHxA-¹³C₅	¹³C₅¹²C₁HF₁₁O₂	317.9	119.9/272.9
全氟庚酸-¹³C₄	PFHpA-¹³C₄	¹³C₄¹²C₃HF₁₃O₂	366.9	169.0/321.9
全氟己烷磺酸钠-¹³C₃	PFHxS-¹³C₃	¹³C₃¹²C₃F₁₃SO₃Na	401.9	80.1/99.1
全氟辛酸-¹³C₈	PFOA-¹³C₈	¹³C₈HF₁₅O₂	421.0	172.0/376.0
¹H,¹H,²H,²H-全氟辛烷磺酸钠-¹³C₂	6:2FTS-¹³C₂	¹³C₂¹²C₆HF₁₃SO₃Na	428.9	408.8/81.0
全氟壬酸-¹³C₉	PFNA-¹³C₉	¹³C₉HF₁₇O₂	471.9	223.0/426.9
全氟辛烷磺酰胺-¹³C₈	FOSA-¹³C₈	¹³C₈H₂F₁₇NO₂S	506.0	78.0
全氟辛烷磺酸钠-¹³C₈	PFOS-¹³C₈	¹³C₈F₁₇SO₃Na	506.9	80.1/99.1
全氟癸酸-¹³C₆	PFDA-¹³C₆	¹³C₆¹²C₄HF₁₉O₂	518.9	223.0/473.9
全氟十一酸-¹³C₇	PFUdA-¹³C₇	¹³C₇¹²C₄HF₂₁O₂	569.9	274.0/524.9
全氟十二酸-¹³C₂	PFDoA-¹³C₂	¹³C₂¹²C₁₀HF₂₃O₂	614.9	169.0/569.9
全氟十四酸-¹³C₂	PFTeDA-¹³C₂	¹³C₂¹²C₁₂HF₂₇O₂	714.9	169.0/669.9
全氟十六酸-¹³C₂	PFHxDA-¹³C₂	¹³C₂¹²C₁₄HF₃₁O₂	815.0	169.3/769.9

表1

图1

图2

图3

图4

图5

图6

图7

表2

不同基质中全氟化合物的方法检出限、基质加标回收率和平行样相对标准偏差"

化合物	MDL/ng			基质加标回收率/%			平行样RSD/%
化合物	土壤	沉积物	水体	土壤	沉积物	水体	土壤	沉积物	水体
8:2diPAP	0.13	0.15	0.09	127.9	105.8	110.3	19.42	7.14	15.10
PFODA	0.06	0.07	0.08	93.9	100.3	97.3	11.84	9.70	6.40
8:8PFPi	0.02	0.03	0.04	120.5	108.4	105.5	0.37	3.49	8.81
PFHxDA	0.09	0.08	0.12	104.4	92.1	108.1	9.15	2.86	9.55
6:8PFPi	0.02	0.04	0.04	133.1	111.3	92.3	16.19	7.45	13.40
6:2diPAP	0.08	0.09	0.11	160.4	122.9	118.9	15.15	6.14	6.67
PFTeDA	0.10	0.11	0.16	121.4	105.9	109.7	5.56	8.27	1.93
6:6PFPi	0.04	0.05	0.05	165.6	132.1	107.6	10.14	9.18	4.89
PFTrDA	0.06	0.09	0.08	103.9	91.5	100.1	7.38	11.50	1.27
8:2Cl-PFESA	0.01	0.05	0.03	95.5	101.9	92.3	5.26	1.58	7.50
10:2FTS	0.02	0.07	0.05	112.0	138.2	122.7	0.34	13.50	0.83
PFDoA	0.05	0.04	0.06	107.1	100.3	97.1	25.16	2.45	1.75
PFDS	0.14	0.16	0.10	98.8	94.1	122.9	7.18	0.35	0.19
N-EtFOSAA	0.05	0.09	0.06	162.9	145.7	149.5	17.99	8.53	6.68
N-MeFOSAA	0.13	0.18	0.11	147.1	143.1	136.4	9.62	11.70	7.82
PFUdA	0.31	0.25	0.28	98.7	103.3	99.3	13.70	3.97	4.49
PFNS	0.02	0.05	0.03	106.5	112.5	97.5	5.82	0.82	4.44
6:2CL-PFESA	0.03	0.12	0.07	95.3	117.0	105.8	5.32	9.74	6.46
8:2FTS	0.03	0.07	0.05	109.2	103.8	111.8	0.45	6.15	6.15
NFDHA	0.12	0.15	0.11	129.1	114.3	112.1	6.47	3.66	1.21
PFBA	0.03	0.14	0.04	92.1	103.8	103.8	1.55	2.13	2.13
Cl-PFOS	0.01	0.09	0.06	94.0	115.3	108.9	5.19	5.36	10.30
PFDA	0.28	0.21	0.18	120.4	95.4	95.6	17.60	0.23	16.00
PFOS	0.1	0.17	0.12	110.7	114.2	92.5	18.40	2.52	11.80
FOSA	0.05	0.15	0.06	97.1	94.5	111.8	5.85	9.42	0.03
PFNA	0.14	0.18	0.12	110.6	109.3	100.3	13.50	7.33	5.66
PFECHS	0.15	0.12	0.10	110.8	100.5	111.4	0.52	2.14	7.84
PFHpS	0.21	0.15	0.11	97.9	93.2	103.0	8.58	10.10	2.70
6:2FTS	0.04	0.07	0.06	174.9	125.4	101.6	23.80	11.90	4.07
PFOA	0.23	0.20	0.20	102.6	105.6	107.1	23.30	1.87	1.20
PFHxS	0.02	0.04	0.03	100.1	103.8	102.7	4.67	3.43	1.91
NaDONA	0.01	0.06	0.05	83.6	106.2	102.1	0.22	5.62	2.95
PFHpA	0.34	0.31	0.24	104.2	102.9	99.4	8.38	0.37	0.04
PFPeS	0.03	0.08	0.04	112.7	97.9	97.8	5.13	4.89	0.23
4:2FTS	0.03	0.05	0.05	78.8	95.2	79.5	0.75	5.16	0.06
PFEESA	0.03	0.09	0.07	85.3	100.9	89.3	0.77	3.09	0.05
PFHxA	0.04	0.06	0.06	109.8	90.1	100.1	13.70	3.57	3.82
PFBS	0.06	0.10	0.05	75.4	96.6	96.6	20.30	1.86	0.95
HFPO-DA	0.09	0.13	0.10	96.8	105.7	116.3	2.23	2.15	2.04
PFMBA	0.13	0.17	0.12	96.6	110.9	114.1	1.46	2.74	3.16
PFPeA	0.18	0.24	0.16	67.9	97.1	99.4	28.10	6.35	6.80

表2

参考文献 24

1	PAUL A G, JONES K C, SWEETMAN A J.. A first global production, emission, and environmental inventory for perfluorooctane sulfonate. Environmental Science & Technology, 2009, 43 (2): 386- 392.
2	BUCK R C, FRANKLIN, J, BERGER, U, et al.. Perfluoroalkyl and polyfluoroalkyl substances in the environment: Terminology, classification, and origins. Integrated Environmental Assessment and Management, 2011, 7 (4): 513- 541.
3	GIESY J P, KANNAN K.. Peer reviewed: Perfluorochemical surfactants in the environment. Environmental Science & Technology, 2002, 36 (7): 146A- 152A.
4	ARVANITI O S, STASINAKIS A S.. Review on the occurrence, fate and removal of perfluorinated compounds during wastewater treatment. Science of the Total Environment, 2015, 524/525, 81- 92.
5	LIANG M, XIAN Y, WANG B, et al.. High throughput analysis of 21 perfluorinated compounds in drinking water, tap water, river water and plant effluent from southern China by supramolecular solvents-based microextraction coupled with HPLC-Orbitrap HRMS. Environmental Pollution, 2020, 263, 114389.
6	朱鹏安, 刘静, 马雪娟, 等.. 全氟/多氟烷基化合物的光学传感检测研究进展. 分析试验室, 2024, 43 (2): 208- 219.
7	MAO T, SHI X, LIN L, et al.. Research progress on up-conversion fluorescence probe for detection of perfluorooctanoic acid in water treatment. Polymers, 2023, 15 (3): 605.
8	ZHANG Q, LIAO M, XIAO K, et al.. A water-soluble fluorescence probe based on perylene diimide for rapid and selective detection of perfluorooctane sulfonate in 100% aqueous media. Sensors and Actuators B: Chemical, 2022, 350, 130851.
9	FANG C, ZHANG X, DONG Z, et al.. Smartphone app-based/portable sensor for the detection of fluoro-surfactant PFOA. Chemosphere, 2018, 191, 381.
10	谢琳娜, 张海婧, 侯沙沙, 等.. 人血清中18种全氟烷烃化合物UPLC-MS/MS的测定. 环境卫生学杂志, 2019, 9 (5): 494- 501.
11	DENG J W, YANG Y Y, FANG L, et al.. Coupling solid-phase microextraction with ambient mass spectrometry using surface coated wooden-tip probe for rapid analysis of ultra trace perfluorinated compounds in complex samples. Analytical Chemistry, 2014, 86 (22): 11159- 11166.
12	宋小飞, 施召才, 马伟文, 等.. 液相色谱-质谱联用法测定血液中全氟化合物. 分析试验室, 2020, 39 (1): 53- 56.
13	CASTIGLIONI, S, VALSECCHI, S, POLESELLO, S, et al.. Sources and fate of perfluorinated compounds in the aqueous environment and in drinking water of a highly urbanized and industrialized area in Italy. Journal of Hazardous Materials, 2015, 282, 51- 60.
14	LI X Q, HUA Z L, ZHANG J Y, et al.. Interactions between dissolved organic matter and perfluoroalkyl acids in natural rivers and lakes: A case study of the northwest of Taihu Lake Basin, China. Water Research, 2022, 216, 118324.
15	ISO. Water quality−Determination of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA)−Method for unfiltered samples using solid phase extraction and liquid chromatography/mass spectrometry [EB/OL]. (2009-03-01) [2024-06-26]. https://www.iso.org/standard/42742.htmL.
16	USEPA. EPA Method 533: Determination of per- and polyfluoroalkyl substances in drinking water byisotope dilution anion exchange solid phaseextraction and liquid chromatography/tandemmass spectrometry [EB/OL]. (2019-12-18) [2024-06-26]. https://www.epa.gov/dwanalyticalmethods/method-533-determination-and-polyfluoroalkyl-substances-drinking-water-isotope#: ~ :text=Method%20533%20is%20a%20solid%20phase%20extraction%20%28SPE%29,per-%20and%20polyfluoroalkyl%20substances%>20%28PFAS%29%20in%20drinking%20water.
17	USEPA. 3rd Draft method 1633 analysis of per- and polyfluoroalkyl substances (PFAS) in aqueous, solid, biosolids, and tissue samples by LC-MS/MS [EB/OL]. (2021-12-06) [2024-06-26]. https://nepis.epa.gov/Exe/ZyPURL.cgi?Dockey=P101687F.txt.
18	江苏省生态环境厅. 水质 17种全氟化合物的测定高效液相色谱串联质谱法: DB32/T4004—2021 [S/OL]. (2021-07-05) [2024-06-26]. https://sthjt.jiangsu.gov.cn/art/2021/7/5/art_83739_10098516.html.
19	中华人民共和国生态环境部. 水质全氟辛基磺酸和全氟辛酸及其盐类的测定同位素稀释/液相色谱-三重四极杆质谱法: HJ 1333—2023 [S/OL]. (2023-12-05) [2024-06-26]. https://www.mee.gov.cn/ywgz/fgbz/bz/bzwb/jcffbz/202312/t20231229_1060273.shtml.
20	中华人民共和国生态环境部. 土壤和沉积物全氟辛基磺酸和全氟辛酸及其盐类的测定同位素稀释/液相色谱-三重四极杆质谱法: HJ 1334—2023 [S/OL]. (2023-12-05) [2024-06-26]. https://www.mee.gov.cn/ywgz/fgbz/bz/bzwb/jcffbz/202312/t20231229_1060275.shtml.
21	NAVARRO I, DE LA TORRE A, SANZ P, et al.. Perfluoroalkyl acids (PFAAs): Distribution, trends and aquatic ecological risk assessment in surface water from Tagus River Basin (Spain). Environmental Pollution, 2020, 256, 113511.
22	HAN T, GAO L, CHEN J, et al.. Spatiotemporal variations, sources and health risk assessment of perfluoroalkyl substances in a temperate bay adjacent to metropolis, North China. Environmental Pollution, 2020, 265, 115011.
23	WANG Q W, YANG G P, ZHANG Z M, et al.. Optimization of sample preparation and chromatography for the determination of perfluoroalkyl acids in sediments from the Yangtze Estuary and East China Sea. Chemosphere, 2018, 205, 524- 530.
24	LU Y, HUA Z, CHU K, et al.. Distribution behavior and risk assessment of emerging perfluoroalkyl acids in multiple environmental media at Luoma Lake, East China. Environmental Research, 2021, 194, 110733.