离子交换色谱-串联质谱法快速测定茶叶中氯酸盐和高氯酸盐

doi:10.3724/SP.J.1123.2023.10026

色谱 ›› 2024, Vol. 42 ›› Issue (9): 875-880.DOI: 10.3724/SP.J.1123.2023.10026

离子交换色谱-串联质谱法快速测定茶叶中氯酸盐和高氯酸盐

叶明立¹, 赵国花², 王勇³^,⁴, 林季润¹, 刘文鑫¹, 卢捷¹, 赵永纲¹, 曹攽⁵^,^*()

1.浙江树人学院生物与环境工程学院,浙江杭州 310015
2.实朴检测技术(上海)股份有限公司, 上海 201203
3.东南大学化学化工学院,江苏南京 211189
4.南京市公安局刑事科学技术研究所,江苏南京 210001
5.浙江省地质院,浙江杭州 310015

收稿日期:2023-12-05 出版日期:2024-09-08 发布日期:2024-08-29
通讯作者: *E-mail:caob1981@163.com.
作者简介:第一联系人：
本文为“离子色谱及其相关技术专辑”稿件.
基金资助:
国家重点研发计划(2023YFF0713900);浙江省基础公益研究计划项目(LTGC24B050009)

Rapid determination of chlorate and perchlorate in tea by ion exchange chromatography-tandem mass spectrometry

YE Mingli¹, ZHAO Guohua², WANG Yong³^,⁴, LIN Jirun¹, LIU Wenxin¹, LU Jie¹, ZHAO Yonggang¹, CAO Ban⁵^,^*()

1. College of Biological and Environmental Engineering, Zhejiang Shuren University, Hangzhou 310015, China
2. SEP Analytical Services (Shanghai) Co., Ltd., Shanghai 201203, China
3. School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China
4. Institute of Forensic Science and Technology of Nanjing Public Security Bureau, Nanjing 210001, China
5. Zhejiang Institute of Geosciences, Hangzhou 310015, China

Received:2023-12-05 Online:2024-09-08 Published:2024-08-29
Supported by:
National Key Research and Development Program of China(2023YFF0713900);Zhejiang Provincial Program for Public Welfare of Technology Application Research Plan(LTGC24B050009)

摘要/Abstract

摘要：

目前,氯酸盐和高氯酸盐作为新型持久性环境污染物受到了广泛关注。茶树在我国有大面积种植,而在受高氯酸盐污染的土壤中,其含有的氯酸盐和高氯酸盐可在茶树中富集,鉴于氯酸盐和高氯酸盐对人体具有的潜在健康风险,因此亟需建立一种茶叶中氯酸盐和高氯酸盐残留量的快速检测方法。本文建立了茶叶中氯酸盐和高氯酸盐残留量的离子交换色谱-串联质谱检测方法。本研究优选Oasis PRiME HLB SPE柱对样品提取液进行净化,使用AceChrom Hybri-A (150 mm×2.1 mm, 5.0 μm)作为离子交换色谱柱,以100 mmol/L乙酸铵-乙腈(40∶60, v/v)作为流动相,在电喷雾负离子和MRM模式下,对目标物实现快速、准确的定性分析,并采用内标法定量。研究结果表明:当氯酸盐与高氯酸盐分别在2.00~200 μg/L和1.00~100 μg/L范围内时,方法的线性关系良好(r²>0.9990);在低、中、高3个加标水平下,氯酸盐和高氯酸盐平均回收率为88.54%~97.25%,方法的检出限分别为12.0 μg/kg和8.0 μg/kg,方法的定量限分别为40.0 μg/kg和26.6 μg/kg。该方法简单、快速、灵敏、准确,能够满足大批量茶叶样品中氯酸盐和高氯酸盐的快速筛查与定量分析。

关键词: 离子交换色谱-串联质谱, 氯酸盐, 高氯酸盐, 茶叶

Abstract:

Ion exchange chromatography-tandem mass spectrometry (IEC-MS/MS) has recently become the preferred method for detecting ionic substances in tea. In this study, an IEC-MS/MS method was developed for the rapid determination of chlorate and perchlorate residues in tea samples. The optimal sample extraction process, pretreatment column, and chromatographic and mass spectrometric conditions were systematically investigated. In the optimal process, the tea samples were ultrasonically extracted with methanol-water (13∶7, v/v), and a PRiME HLB SPE column was used to purify the sample extract. An AceChrom Hybri-A IEC column (150 mm×2.1 mm, 5.0 μm) was used for separation, and 100 mmol/L ammonium acetate-acetonitrile (40∶60, v/v) was used as the mobile phase for isocratic elution. The flow rate was 0.3 mL/min, the column temperature was 40 ℃, and the injection volume was 5.0 μL. The mass spectrometric data were collected in negative electrospray ionization mode combined with multiple reaction monitoring (MRM) mode to achieve the rapid and accurate separation and qualitative analysis of the desired chemical components. Quantification was performed using the internal standard (IS) method. The measurement results showed a good linear relationship when the mass concentrations of chlorate and perchlorate were between 2.00-200 and 1.00-100 μg/L, respectively, with correlation coefficients (r²) greater than 0.9990. The average recoveries of chlorate and perchlorate at three spiked levels of low, medium, and high ranged from 88.54% to 97.25% with relative standard deviations (RSDs, n=7) of 3.2%-5.2%. The limits of detection for chlorate and perchlorate were 12.0 and 8.0 μg/kg, respectively, while the limits of quantification were 40.0 and 26.6 μg/kg, respectively. The results of tests conducted to assess the linearity, specificity, accuracy, precision, and applicability of the method to the analysis of chlorate and perchlorate in 15 tea samples collected from a local market demonstrated its validity for the routine analysis of tea samples. The proposed method is simple, rapid, sensitive, and accurate, and can meet requirements for the rapid screening and quantitative analysis of residual trace chlorate and perchlorate in large quantities of tea samples.

Key words: ion exchange chromatography-tandem mass spectrometry (IEC-MS/MS), chlorate, perchlorate, tea

中图分类号:

O658

叶明立, 赵国花, 王勇, 林季润, 刘文鑫, 卢捷, 赵永纲, 曹攽. 离子交换色谱-串联质谱法快速测定茶叶中氯酸盐和高氯酸盐[J]. 色谱, 2024, 42(9): 875-880.

YE Mingli, ZHAO Guohua, WANG Yong, LIN Jirun, LIU Wenxin, LU Jie, ZHAO Yonggang, CAO Ban. Rapid determination of chlorate and perchlorate in tea by ion exchange chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2024, 42(9): 875-880.

图/表 6

表1 氯酸盐和高氯酸盐的质谱参数

Table 1 MS parameters of ClO3- and Cl O4-

Analyte	Precursor ion (m/z)	Product ion (m/z)	Declustering potential/V	Collision energy/eV
Cl $O 3 -$	82.97	67.01^*	74	12
	84.97	68.95	74	14
Cl $O 4 -$	98.90	82.99^*	74	18
	100.90	84.98	74	20
Cl $O 3 -$ -¹⁸O₃	88.97	71.01^*	76	14
Cl $O 4 -$ -¹⁸O₄	106.97	88.98^*	72	22
		71.01	72	28

表1 氯酸盐和高氯酸盐的质谱参数

Table 1 MS parameters of ClO3- and Cl O4-

Analyte	Precursor ion (m/z)	Product ion (m/z)	Declustering potential/V	Collision energy/eV
Cl $O 3 -$	82.97	67.01^*	74	12
	84.97	68.95	74	14
Cl $O 4 -$	98.90	82.99^*	74	18
	100.90	84.98	74	20
Cl $O 3 -$ -¹⁸O₃	88.97	71.01^*	76	14
Cl $O 4 -$ -¹⁸O₄	106.97	88.98^*	72	22
		71.01	72	28

表2 不同种类SPE柱对目标分析物的萃取效率

Table 2 Extraction efficiencies of different solid phase extraction columns on the target analytes

Analyte	Spiked level/ (μg/kg)	Recoveries/%
Analyte	Spiked level/ (μg/kg)	PRiME HLB SPE	Al₂O₃ SPE	C18 SPE
Cl $O 3 -$	80	92.36	78.58	51.86
	800	86.21	82.54	62.85
	3200	90.17	88.85	57.25
Cl $O 4 -$	40	89.12	86.85	89.57
	400	93.17	92.68	91.85
	1600	96.72	89.78	93.51

表2 不同种类SPE柱对目标分析物的萃取效率

Table 2 Extraction efficiencies of different solid phase extraction columns on the target analytes

Analyte	Spiked level/ (μg/kg)	Recoveries/%
Analyte	Spiked level/ (μg/kg)	PRiME HLB SPE	Al₂O₃ SPE	C18 SPE
Cl $O 3 -$	80	92.36	78.58	51.86
	800	86.21	82.54	62.85
	3200	90.17	88.85	57.25
Cl $O 4 -$	40	89.12	86.85	89.57
	400	93.17	92.68	91.85
	1600	96.72	89.78	93.51

图1 氯酸盐和高氯酸盐(100 μg/L)的提取离子色谱图

Fig. 1 Extracted ion chromatograms of the chlorate and perchlorate (100 μg/L) Volume ratio of 0.1 mol/L ammonium acetate aqueous solution to acetonitrile: (a) 90∶10; (b) 70∶30; (c) 40∶60.

表3 目标分析物的线性方程、相关系数、线性范围、检出限与定量限(n=6)

Table 3 Linear equations, correlation coefficients (r2), linear ranges, limits of detection (LODs) and limits of quantification (LOQs) of the target analytes (n=6)

Analyte	Linear equation	r²	Linear range/(μg/L)	LOD/(μg/kg)	LOQ/(μg/kg)
Cl $O 3 -$	Y=0.8199X+0.00623	0.9996	2.00-200	12.0	40.0
Cl $O 4 -$	Y=1.162X+0.00359	0.9998	1.00-100	8.0	26.6

表3 目标分析物的线性方程、相关系数、线性范围、检出限与定量限(n=6)

Table 3 Linear equations, correlation coefficients (r2), linear ranges, limits of detection (LODs) and limits of quantification (LOQs) of the target analytes (n=6)

Analyte	Linear equation	r²	Linear range/(μg/L)	LOD/(μg/kg)	LOQ/(μg/kg)
Cl $O 3 -$	Y=0.8199X+0.00623	0.9996	2.00-200	12.0	40.0
Cl $O 4 -$	Y=1.162X+0.00359	0.9998	1.00-100	8.0	26.6

表4 目标分析物的加标回收率和精密度(n=7)

Table 4 Recoveries and RSDs of the target analytes (n=7)

Analyte	Spiked level/(μg/kg)	Recovery/%	RSD/%
Cl $O 3 -$	80	89.56	4.2
	800	95.58	3.5
	3200	92.68	5.2
Cl $O 4 -$	40	88.54	4.9
	400	97.25	3.2
	1600	95.61	3.9

表4 目标分析物的加标回收率和精密度(n=7)

Table 4 Recoveries and RSDs of the target analytes (n=7)

Analyte	Spiked level/(μg/kg)	Recovery/%	RSD/%
Cl $O 3 -$	80	89.56	4.2
	800	95.58	3.5
	3200	92.68	5.2
Cl $O 4 -$	40	88.54	4.9
	400	97.25	3.2
	1600	95.61	3.9

图2 (a)实际样品和(b)加标样品中氯酸盐和高氯酸盐的提取离子色谱图

Fig. 2 Extracted ion chromatograms of chlorate and perchlorate in (a) a tea sample and (b) a spiked sample

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离子交换色谱-串联质谱法快速测定茶叶中氯酸盐和高氯酸盐

Rapid determination of chlorate and perchlorate in tea by ion exchange chromatography-tandem mass spectrometry

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