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

doi:10.3724/SP.J.1123.2023.10026

Abstract

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

CLC Number:

O658

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.

Figures/Tables 6

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

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

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

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

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.

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

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

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

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

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

References

[1]	Zhang Q, Mao W F, Guo W D, et al. Journal of Food Safety and Quality, 2021, 12(20): 7940
[1]	张卿, 毛伟峰, 郭卫东, 等. 食品安全质量检测学报, 2021, 12(20): 7940
[2]	Dong H T, Zhang Y F, Ai Y, et al. Journal of Food Safety and Quality, 2021, 12(16): 6522
[2]	董恒涛, 张亚锋, 艾芸, 等. 食品安全质量检测学报, 2021, 12(16): 6522
[3]	Lei K, Wang F, Wei Y X, et al. Modern Preventive Medicine, 2016, 43(18): 3391
[3]	雷凯, 王芳, 魏玉霞, 等. 现代预防医学, 2016, 43(18): 3391
[4]	Li D G, Wu F, Lü L L, et al. Food Industry, 2021, 42(4): 497
[4]	李冬桂, 吴凤, 吕丽兰, 等. 食品工业, 2021, 42(4): 497
[5]	Wei Y, Fang C R, Zhao Y F, et al. Journal of Instrumental Analysis, 2021, 40(4): 583
[5]	韦昱, 方从容, 赵云峰, 等. 分析测试学报, 2021, 40(4): 583
[6]	Tonacchera M, Pinchera A, Dimida A, et al. Thyroid, 2004, 14: 1012
[7]	Bellanger M, Demeneix B, Granjean P, et al. J Clin Endocr Metab, 2015, 100: 1256
[8]	Bellinger D C. Environ Health Persp, 2011, 120: 501
[9]	Tian Y M, Gong Z Y. Food Science, 2020, 41(5): 276
[9]	田一媚, 宫智勇. 食品科学, 2020, 41(5): 276
[10]	Rubin R, Pearl M, Kharrazi M, et al. Environ Res, 2017, 158(10): 72
[11]	Pleus R C, Corey L M. Toxicol Appl Pharm, 2018, 358: 102
[12]	Zhang S H, Ying L, Zhang S F, et al. Science and Technology of Food Industry, 2019, 40(7): 224
[12]	张少华, 应璐, 张书芬, 等. 食品工业科技, 2019, 40(7): 224
[13]	European Food Safety Authority. EFSA J, 2014, 12(10): 3869
[14]	European Food Safety Authority. EFSA J, 2015, 13(6): 4135
[15]	Liu Y, Sun H, Zhou L, et al. Food Chem, 2019, 274: 180
[16]	Zhang H, Feng X, Liu D, et al. Microchem J, 2022. 181: 107822
[17]	Huertas-Perez J F, Mottier P, Basle Q, et al. Microchem J, 2022, 177: 107281
[18]	Liu L J, Yang Y, Zhang W T, et al. Physical Testing and Chemical Analysis Part B: Chemical Analysis, 2021, 57(3): 247
[18]	刘丽菁, 杨艳, 张文婷, 等. 理化检验(化学分册), 2021, 57(3): 247
[19]	Jia N, Zhang C L, Liu B B, et al. Physical Testing and Chemical Analysis Part B: Chemical Analysis, 2019, 55(11): 1337
[19]	贾娜, 张辰凌, 刘冰冰, 等. 理化检验(化学分册), 2019, 55(11): 1337
[20]	Wang Z W, Sparling M, Tague B. Food Addit Contam A, 2018, 35(10): 2022
[21]	Zhu W, Ning X J, Qin Y. Journal of Food Safety and Quality, 2019, 10(11): 3474
[21]	朱伟, 宁啸骏, 秦宇. 食品安全质量检测学报, 2019, 10(11): 3474
[22]	Bauer A, Luetjohann J, Rohn S, et al. Food Control, 2018, 86: 71
[23]	Mari A, Koji K, Nobue Y. J Health Sci, 2009, 55(4): 549
[24]	Zhang H, Huo Z, Liu H, et al. Microchem J, 2021, 165: 106167
[25]	Zhang H, Jiang X H, Huo Z L. Food Science, 2021, 42(12): 315
[25]	张昊, 蒋晓宏, 霍宗利. 食品科学, 2021, 42(12): 315