GC-MS/MS法测定茶鲜叶中20种邻苯二甲酸酯类化合物

孙渝; 周利; 张新富; 孙荷芝

doi:10.13305/j.cnki.jts.2025.04.007

PDF(1394 KB)

茶叶科学 ›› 2025, Vol. 45 ›› Issue (4) : 625-636. DOI: 10.13305/j.cnki.jts.2025.04.007

研究报告

GC-MS/MS法测定茶鲜叶中20种邻苯二甲酸酯类化合物

孙渝^1,2, 周利², 张新富^1,*, 孙荷芝^2,*

作者信息 +

Determination of 20 Phthalate Acid Esters in Tea Leaves by GC-MS/MS

SUN Yu^1,2, ZHOU Li², ZHANG Xinfu^1,*, SUN Hezhi^2,*

Author information +

文章历史 +

摘要

建立了气相色谱-串联质谱（Gas chromatography-tandem mass spectrometry,GC-MS/MS）同时测定茶鲜叶中20种邻苯二甲酸酯类化合物的分析方法。茶鲜叶中的邻苯二甲酸酯类化合物经0.1%乙酸乙腈提取、氯化钠盐析、Florisil固相萃取柱净化、乙腈定容,色谱程序升温分离,多反应监测模式扫描（Multiple reaction monitoring,MRM）,外标法定量。通过优化样品提取、净化以及色谱条件,目标化合物在0.010~2.0 mg·kg^-1范围内线性良好,决定系数（R²）>0.995 5;在0.010、0.10 mg·kg^-1和1.0 mg·kg^-1 3个添加水平下,平均回收率在70%~118%,相对标准偏差（RSD）<17.8%;方法的定量限为0.010~0.10 mg·kg^-1。该方法稳定、可靠,可满足茶树鲜叶中邻苯二甲酸酯类化合物的检测需要。

Abstract

In this paper, an analytical method for the simultaneous determination of 20 phthalate esters in tea fresh leaves was developed by gas chromatography-tandem mass spectrometry (GC-MS/MS). The phthalate esters in tea fresh leaves were extracted by 0.1% acetonitrile acetate, salted out with sodium chloride, cleaned up with a florisil solid phase extraction column, resolved with acetonitrile, separated by temperature programmed chromatography, monitored with multiple reaction monitoring (MRM) mode, and quantified by the external standard method. Through the optimization of sample extraction, purification and chromatographic conditions, good linearity of the target compounds was obtained in the concentration range of 0.010-2.0 mg·kg^-1 with the corresponding coefficient of determination R²>0.995 5. The average recoveries ranged from 70% to 118% at the three spiked levels of 0.010 mg·kg^-1, 0.10 mg·kg^-1 and 1.0 mg·kg^-1, with the relative standard deviations (RSDs) of <17.8%. The limits of quantification were 0.010~0.050 mg·kg^-1. The method is stable and reliable, and it can meet the needs of the determination of phthalate acid esters in tea fresh leaves.

导出引用

孙渝, 周利, 张新富, 孙荷芝. GC-MS/MS法测定茶鲜叶中20种邻苯二甲酸酯类化合物[J]. 茶叶科学. 2025, 45(4): 625-636 https://doi.org/10.13305/j.cnki.jts.2025.04.007

SUN Yu, ZHOU Li, ZHANG Xinfu, SUN Hezhi. Determination of 20 Phthalate Acid Esters in Tea Leaves by GC-MS/MS[J]. Journal of Tea Science. 2025, 45(4): 625-636 https://doi.org/10.13305/j.cnki.jts.2025.04.007

中图分类号： S571.1 O657.7+2

参考文献

[1] Lin S, Chen Z, Chen T, et al.Theanine metabolism and transport in tea plants (Camellia sinensis L.): advances and perspectives[J]. Critical Reviews Biotechnology, 2023, 43(3): 327-341.
[2] 张文驹, 戎俊, 韦朝领, 等. 栽培茶树的驯化起源与传播[J]. 生物多样性, 2018, 26(4): 357-372.
Zhang W J, Rong J, Wei C L, et al.Domestication origin and spread of cultivated tea plants[J]. Biodiversity Science, 2018, 26(4): 357-372.
[3] 鲁钰婷, 柴云峰, 郝振霞, 等. 2023年茶叶质量安全检测技术研究进展[J]. 中国茶叶, 2024, 46(5): 1-9.
Lu Y T, Chai Y F, Hao Z X, et al.Research progress on tea quality and safety testing technology in 2023[J]. China Tea, 2024, 46(5): 1-9.
[4] 贺诗意, 张蕊, 周明慧, 等. 植物油中邻苯二甲酸酯类塑化剂检测技术研究现状[J/OL]. 中国油脂, 2024: 1-12[2024-12-24]. https://doi.org/10.19902/j.cnki.zgyz.1003-7969.230534.
He S Y, Zhang R, Zhou M H, et al. Current status of research on detection techniques for phthalate esters (PAEs) plasticizer in vegetable oil [J/OL]. China Oils and Fats, 2024: 1-12[2024-12-24]. https://doi.org/10.19902/j.cnki.zgyz.1003-7969.230534.
[5] Katsikantami I, Sifakis S, Tzatzarakis M N, et al.A global assessment of phthalates burden and related links to health effects[J]. Environment International, 2016, 97: 212-236.
[6] 刘平香, 陈红平, 张明露, 等. 茶叶中邻苯二甲酸酯污染水平及检测技术研究进展[J]. 浙江农业科学, 2015, 56(11): 1796-1804.
Liu P X, Chen H P, Zhang M L, et al.Research progress on phthalate contamination levels and detection techniques in tea leaves[J]. Journal of Zhejiang Agricultural Sciences, 2015, 56(11): 1796-1804.
[7] Zheng X C, Jing Z, Hong Y, et al.Study on the mechanism of interaction between phthalate acid esters and bovine hemoglobin[J]. Journal of Agricultural and Food Chemistry, 2016, 64(30): 6035-6041.
[8] Bui T T, Giovanoulis G, Cousins A P, et al.Human exposure, hazard and risk of alternative plasticizers to phthalate esters[J]. Science of the Total Environment, 2016, 541: 451-467. doi.org/10.1016/j.scitotenv.2015.09.036.
[9] 张依, 范金旭, 李秋雨, 等. 食品中邻苯二甲酸酯类塑化剂的毒性危害及检测方法的研究进展[J]. 食品安全导刊, 2022(26): 190-192.
Zhang Y, Fan J X, Li Q Y, et al.Research progress on toxicity and detection methods of phthalic acid esters in food[J]. China Food Safety Magazine, 2022(26): 190-192.
[10] 赖莺, 黄宗平, 葛秀秀, 等. 仿真饰品中邻苯二甲酸酯类增塑剂的含量测定和迁移风险考察[J]. 色谱, 2012, 30(7): 647-653.
Lai Y, Huang Z P, Ge X X, et al.Determination of phthalic acid esters in imitation jewellery and investigation of their migration risk[J]. Chinese Journal of Chromatography, 2012, 30(7): 647-653.
[11] 王笑妍, 薛燕波, 者东梅, 等. 邻苯二甲酸酯类增塑剂概况及法规标准现状[J]. 中国塑料, 2019, 33(6): 95-105.
Wang X Y, Xue Y B, Zhe D M, et al.Overview of phthalate plasticizers, current regulations and standards[J]. China Plastics, 2019, 33(6): 95-105.
[12] 周利, 王新茹, 张新忠, 等. 茶叶质量安全研究“十三五”进展及“十四五”发展方向[J]. 中国茶叶, 2021, 43(10): 34-40.
Zhou L, Wang X R, Zhang X Z, et al.Research progress on tea quality safety during the research progress on tea quality safety during the 13th five-year plan period and development direction in the 14th five-year plan period[J]. China Tea, 2021, 43(10): 34-40.
[13] 尹鹏. 邻苯二甲酸酯类化合物在茶叶上的污染水平及其迁移规律的研究[D]. 杭州: 中国农业科学院茶叶研究所, 2014.
Yin P.Occurrence of phthalate esters in tea and migration from plastic packages to tea [D]. Hangzhou: Tea Research Institute, Chinese Academy of Agricultural Sciences, 2014.
[14] Wang M, Tang Y, Mi S, et al.Difference in accumulation of five phthalate esters in different elite tea cultivars and their correlation with environment factors[J]. Agriculture, 2022, 12(10): 1516. doi:10.3390/agriculture 12101516.
[15] Wang M, Han S, Wu Y, et al.Spatiotemporal dynamics of phthalate esters in tea plants growing different geographical environments and an attempt on their risk assessment[J]. Journal of Agricultural and Food Chemistry, 2023, 71(16): 6434-6444.
[16] 林柏纬. 气相色谱-三重四极杆串联质谱法(GC-MS/MS)测定茶叶中19种邻苯二甲酸酯[J]. 福建轻纺, 2024(2): 20-26.
Lin B W.Determination of 19 phthalates in tea by gas chromatography-triple quadrupole culm tandem mass spectrometry (GC-MS/MS)[J]. The Light & Textile Industries of Fujian, 2024(2): 20-26.
[17] 刘平香. 茶叶中邻苯二甲酸酯污染来源与风险评估[D]. 杭州: 中国农业科学院茶叶研究所, 2017.
Liu P X.Pollution source and risk assessment of phthalate esters in tea [D]. Hangzhou: Tea Research Institute, Chinese Academy of Agricultural Sciences, 2017.
[18] Seenivasan S, Anderson T A, Narayanannair M.Heavy metal content in tea soils and their distribution in different parts of tea plants, Camellia sinensis (L). O. Kuntze[J]. Environmental Monitoring and Assessment, 2016, 188(7): 428. doi:10.1007/s10661-016-5440-y.
[19] Liu P X, Chen H P, Gao G W, et al.Occurrence and residue pattern of phthalate esters in fresh tea leaves and during tea manufacturing and brewing[J]. Journal of Agricultural and Food Chemistry, 2016, 64(46): 8909-8917.
[20] 严煌倩, 李勇, 翟丽菲, 等. 气相色谱-质谱法结合QuEChERS法快速检测青椒中15种邻苯二甲酸酯[J]. 江苏农业学报, 2018, 34(2): 459-465.
Yan H Q, Li Y, Zhai L F, et al.Determination of 15 phthalate acid esters in pepper by gas chromatography-mass spectrometry with QuEChERS method[J]. Jiangsu Journal of Agricultural Sciences, 2018, 34(2): 459-465.
[21] 钱传范. 农药残留分析原理与方法[M]. 北京: 化学工业出版社, 2021.
Qian C F.Principle and method of pesticide residue analysis [M]. Beijing: Chemical Industry Press, 2021.
[22] 姚键梅, 龙家寰, 张娟, 等. QuEChERS/GC-MS法快速检测干茶中11种塑化剂[J]. 贵茶, 2023(3): 24-30.
Yao J M, Long J H, Zhang J, et al.Rapid detection of 11 plasticizers in dry tea by QuEChERS/GC-MS[J]. Journal of Guizhou Tea, 2023(3): 24-30.
[23] 甘凝岚, 朱晓军, 李洁莉, 等. QuEChERS-超高效液相色谱-三重四极杆串联质谱法检测保健茶中18种违禁添加药物[J]. 茶叶科学, 2021, 41(2): 237-250.
Gan N L,Zhu X J,Li J L, et al.Detection of 18 prohibited additives in health-protecting tea by quechers method and ultra high performance liquid chromatography triple quadrupole tandem mass spectrometry[J]. Journal of Tea Science, 2021, 41(2): 237-250.
[24] Chen G, Cao P, Liu R.A multi-residue method for fast determination of pesticides in tea by ultra performance liquid chromatography-electrospray tandem mass spectrometry combined with modified QuEChERS sample preparation procedure[J]. Food Chemistry, 2011, 125(4): 1406-1411.
[25] 冯驰, 赖政, 查燕, 等. 城市绿化树种叶片多环芳烃含量水平与叶片特征的关系[J]. 江苏农业科学, 2018, 46(23): 366-370.
Feng C, Lai Z, Zha Y, et al.Relationship between polycyclic aromatic hydrocarbon content and leaf characteristics of urban greening tree species[J]. Jiangsu Agricultural Sciences, 2018, 46(23): 366-370.