滤过型萃取柱-超高效液相色谱-串联质谱法同时测定水果中11种农药残留

王子剑; 赵劲松; 郭晓宇; 李倩; 郑天驰; 商爱媛; 范赛

doi:10.16495/j.1006-3757.2023.01.004

滤过型萃取柱-超高效液相色谱-串联质谱法同时测定水果中11种农药残留

doi: 10.16495/j.1006-3757.2023.01.004

1.
北京市大兴区疾病预防控制中心，北京　102600
2.
北京市疾病预防控制中心，北京　100013

详细信息

作者简介:
王子剑（1987−），男，主管检验师，研究方向为食品检测技术，E-mail：398127430@qq.com

通讯作者:
范赛（1982−），男，研究员，《分析测试技术与仪器》青年编委，研究方向为食品检测技术，E-mail：fansai@163.com

中图分类号: O657. 63
计量
- 文章访问数: 120
- HTML全文浏览量: 66
- PDF下载量: 93
- 被引次数: 0
出版历程
- 收稿日期: 2023-01-16
- 录用日期: 2023-02-24
- 修回日期: 2023-02-24
- 刊出日期: 2023-03-31

Simultaneous Determination of 11 Pesticide Residues in Fruits by Filtered Extraction Column-Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

1.
Daxing Center for Disease Control and Prevention, Beijing 102600, China
2.
Beijing Center for Disease Control and Prevention, Beijing 100013, China

摘要

摘要: 建立了超高效液相色谱-串联质谱测定水果中杀虫剂、杀菌剂、除草剂等11种常见农药的方法. 水果样品经乙腈提取，提取液经滤过型萃取柱（m-PFC）净化，正离子多反应模式（MRM）监测，外标法定量. 水果中11种农药的检出限为1~3 μg/kg，在1.0~100.0 ng/mL的范围内线性关系良好，相关系数r不低于0.996 9. 在样品基质中分别添加5、20、50 μg/kg的标准品进行加标回收试验，11种农药的平均回收率为88.9%~110.1%，相对标准偏差（RSD）为2.7%~8.5%（n=6）. 方法操作简单、灵敏度高，能够准确测定水果中11种农药残留.
- 农药残留 /
- 滤过型萃取柱 /
- 超高效液相色谱-串联质谱法 /
- 水果
Abstract: A method for the determination of 11 common pesticides in fruits, such as pesticides, fungicides and herbicides, was set up using the ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The fruit samples were extracted with acetonitrile, and the extracts were purified using a filtered extraction column (m-PFC), monitored by the positive ion multiple reaction mode (MRM), and quantified by the external standard method. The detection limits of 11 pesticides in fruits were 1~3 μg/kg, with good linearity in the range of 1.0~100.0 ng/mL, with the correlation coefficient r not less than 0.996 9. The standards of 5, 20 and 50 μg/kg were added to the sample matrix for spiked recovery tests. The average recoveries rate of 11 pesticides were 88.9%~110.1%, and the relative standard deviation (RSD) were 2.7%~8.5% (n=6). The method is simple and sensitive, and can accurately determine 11 pesticide residues in fruits.
- pesticide residues /
- m-PFC /
- UPLC-MS/MS /
- fruits

HTML全文

图 1 11种农药标准品的MRM色谱图（10 ng/mL）

Figure 1. MRM chromatograms of 11 pesticide standards (10 ng/mL)

下载: 全尺寸图片幻灯片

图 2 IC-QuE3150-CP与QuEChERS在加标质量分数为20 μg/kg下的加标回收率对比

Figure 2. Spiked recoveries of IC-QuE3150-CP and QuEChERS at adding mass fraction of 20 μg/kg

下载: 全尺寸图片幻灯片

图 3 不同溶剂在加标质量分数为20 μg/kg下的提取效率对比

Figure 3. Extraction efficiencies of different solvents at adding mass fraction of 20 μg/kg

下载: 全尺寸图片幻灯片

图 4 阳性样品谱图

（a）阳性京白梨样品，（b）阳性葡萄样品，（c）阳性草莓样品一，（d）阳性草莓样品二

Figure 4. Positive sample spectrogram

下载: 全尺寸图片幻灯片

表 1 梯度洗脱条件

Table 1. Gradient elution conditions

时间/min	纯乙腈/%	0.1%甲酸水溶液/%
0.01	10.0	90.0
7.0	95.0	5.0
8.0	95.0	5.0
8.1	10.0	90.0
20.0	10.0	90.0

下载: 导出CSV

表 2 目标化合物质谱参数

Table 2. MS parameters of target compounds

化合物	母离子/ （m/z）	子离子/ （m/z）	去簇电压（DP）/V	碰撞能量（CE）/V
萎锈灵	236.1	142.9*	70	21
		87.0	70	33
嘧菌环胺	226.1	93.0	100	50
		108.1*	100	35
腈菌唑	289.1	70.0*	120	35
		125.0	120	49
克百威	222.1	165.0*	70	17
		123.1	70	29
氟虫腈	454.0	368.1*	50	33
		290.1	50	42
硫环磷	256.2	168.0*	51	31
		139.0	51	22
噻虫啉	253.1	126.1*	81	29
		99.1	81	57
氰草津	241.1	214.2*	86	27
		104.1	86	47
氟噻草胺	364.0	194.0*	70	16
		152.0	70	27
特丁津	230.1	174.1*	40	23
		104.1	40	41
噻吩磺隆	388.0	167.0	36	21
		205.0*	36	33
*：定量离子对

下载: 导出CSV

表 3 11种农药的线性方程、线性范围、相关系数及检出限

Table 3. Linear equation, linear range, correlation coefficient and detection limit of 11 pesticides

化合物	线性方程	线性范围/（μg/L）	相关系数（r）	检出限/（μg/kg）
萎锈灵	y=2 290.53x+266.06	1.0~100.0	0.999 4	1
嘧菌环胺	y=2 876.76x+101.30	1.0~100.0	0.996 9	1
腈菌唑	y=3 278.41x+402.91	1.0~100. 0	0.999 5	1
克百威	y=2 926.46x+619.69	1.0~100.0	0.998 4	1
氟虫腈	y=1 785.38x+321.71	1.0~100.0	0.999 4	1
硫环磷	y=2 683.87x+353.99	1.0~100.0	0.998 3	1
噻虫啉	y=1 966.98x+329.43	1.0~100.0	0.998 9	1
氰草津	y=1 419.88x+235.12	1.0~100.0	0.998 6	1
氟噻草胺	y=1 962.42x+312.87	1.0~100.0	0.999 1	1
特丁津	y=5 098.76x-185.04	1.0~100.0	0.999 6	1
噻吩磺隆	y=1 061.23x-159.69	1.0~100.0	0.998 1	3

下载: 导出CSV

表 4 11种农药回收率及精密度（n=6）

Table 4. Recovery rate and precision of 11 pesticides (n=6)

化合物	5 μg/kg			20 μg/kg			50 μg/kg
化合物	测定质量分数/ (μg/kg)	回收率/%	RSD/%	测定质量分数/ (μg/kg)	回收率/%	RSD/%	测定质量分数/ (μg/kg)	回收率/%	RSD/%
萎锈灵	5.085	101.7	6.2	19.68	98.4	5.7	51.10	102.2	4.7
嘧菌环胺	4.855	97.1	5.8	20.56	102.8	4.3	55.05	110.1	2.7
腈菌唑	4.525	90.5	8.3	19.42	97.1	7.1	51.35	102.7	4.9
克百威	4.760	95.2	7.5	20.70	103.5	4.4	54.05	108.1	3.9
氟虫腈	4.445	88.9	5.7	19.66	98.3	5.5	51.35	102.7	3.2
硫环磷	4.915	98.3	8.2	19.10	95.5	7.2	47.70	95.4	5.7
噻虫啉	4.790	95.8	8.2	19.42	97.1	4.3	50.45	100.9	3.7
氰草津	4.785	95.7	7.5	20.00	100.0	6.3	47.85	95.7	4.5
氟噻草胺	4.830	96.6	7.2	18.46	92.3	4.6	53.75	107.5	3.5
特丁津	4.835	96.7	7.7	19.14	95.7	6.2	52.35	104.7	4.0
噻吩磺隆	4.930	98.6	8.5	20.54	102.7	6.3	53.70	107.4	3.8

下载: 导出CSV

参考文献(16)

[1]	中华人民共和国农业部. 蔬菜和水果中有机磷、有机氯、拟除虫菊酯和氨基甲酸酯类农药多残留的测定: NY/T 761—2008[S]. 北京: 农业出版社, 2008 Ministry of Agriculture of the People's Republic of China. Pesticide multiresidue sceen methods for determination of organophosphorus pesticides, organochlorine pesticides, pyrethroid pesticides and carbamate pesticedes in vegetables and fruits: NY/T 761—2008[S]. Beijing, Agricultural Press, 2008.
[2]	冯美艳. 常见蔬菜水果农药残留检测技术及质量安全管理[J]. 农业工程技术,2022,42(17):93-94 FENG Meiyan. Detection technology and quality safety management of pesticide residues in common vegetables and fruits[J]. Agricultural Engineering Technology,2022,42 (17):93-94.
[3]	李富根, 廖先骏, 朴秀英, 等. 2021版食品中农药最大残留限量国家标准(GB 2763)解析[J]. 现代农药,2021,20(3):7-12 LI Fugen, LIAO Xianjun, PIAO Xiuying, et al. Analysis on the national food safety standard-maximum residue limits for pesticides in food in 2021[J]. Modern Agrochemicals,2021,20 (3):7-12.
[4]	朱玉龙, 陈增龙, 张昭, 等. 我国农药残留监管与标准体系建设[J]. 植物保护,2017,43(2):1-5 doi: 10.3969/j.issn.0529-1542.2017.02.001 ZHU Yulong, CHEN Zenglong, ZHANG Zhao, et al. Pesticide residue supervision and standard system construction in China[J]. Plant Protection,2017,43 (2):1-5. doi: 10.3969/j.issn.0529-1542.2017.02.001
[5]	王维茜, 杜业刚, 陈玉浩. 水产品中农药残留国内外标准体系分析与检测方法研究进展[J]. 食品安全质量检测学报,2022,13(11):3690-3696 WANG Weiqian, DU Yegang, CHEN Yuhao. Analysis of domestic and foreign standard system and research progress of detection methods for pesticide residues in aquatic products[J]. Journal of Food Safety & Quality,2022,13 (11):3690-3696.
[6]	赵海玲, 邱宏萌, 雷琼, 等. Qu EChERS-气相色谱-质谱法测定水果中多种农药残留[J]. 中国卫生检验杂志,2022,32(13):1544-1548 ZHAO Hailing, QIU Hongmeng, LEI Qiong, et al. Determination of pesticide residues in fruits by QuEChERS-gas chromatography-mass spectrometry[J]. Chinese Journal of Health Laboratory Technology,2022,32 (13):1544-1548.
[7]	韩璐, 陈达炜, 吕冰, 等. 超高效液相色谱-串联质谱法快速筛查茶叶中的多种农药残留[J]. 中国食品卫生杂志,2015,27(4):386-393 HAN Lu, CHEN Dawei, LV Bing, et al. Rapid screening of multi-residue pesticides in tea by UPLC-MS/MS[J]. Chinese Journal of Food Hygiene,2015,27 (4):386-393.
[8]	廖华勇, 徐碧珠. 固相微萃取在农药残留分析中的应用[J]. 中国卫生检验杂志,2002,12(1):122-127 LIAO Huayong, XU Bizhu. Application of solid-phase microextraction in pesticide residue analysis[J]. Chinses Journal of Health Laboratory Technology,2002,12 (1):122-127.
[9]	赵祥梅, 董英, 王和生. QuEChERS法在农产品农药残留物检测中的应用研究进展[J]. 中国卫生检验杂志,2008,18(5):952-954 ZHAO Xiangmei, DONG Ying, WANG Hesheng. Research progress on application of QuEChERS method in detection of pesticide residues in agricultural products[J]. Chinese Journal of Health Laboratory Technology,2008,18 (5):952-954.
[10]	陈茹, 黄柳霞, 叶日金, 等. QuEChERS-高效液相色谱-质谱/质谱法测定茶叶中的10种农药残留[J]. 质量与市场,2022(S1):64-67 CHEN Ru, HUANG Liuxia, YE Rijin, et al. Determination of 10 pesticide residues in tea by QuEChERS- HPLC-MS/MS[J]. Quality & Market,2022 (S1):64-67.
[11]	韩瑨烜, 罗芸, 叶恩里克·金恩斯, 等. 改良QuEChERS/超高效液相色谱-质谱联用技术快速筛查5类常见水果蔬菜中15种典型农药残留[J]. 食品科技,2022,47(5):297-303 doi: 10.3969/j.issn.1005-9989.2022.5.spkj202205044 HAN Jinxuan, LUO Yun, YEENLIKE. Jinensi, et al Rapid determination of 15 typical pesticide residues in 5 common fruits and vegetables by improved QuEChERS/UPLC-MS/MS[J]. Food Science and Technology,2022,47 (5):297-303. doi: 10.3969/j.issn.1005-9989.2022.5.spkj202205044
[12]	胡翠, 唐婧苗, 谢柏艳. 超高效液相色谱-串联质谱法测定水果中42种农药残留[J]. 食品安全质量检测学报,2021,12(9):3635-3641 HU Cui, TANG Jingmiao, XIE Baiyan. Determination of 42 pesticides in fruits by ultra performance liquid chromatography-tandem mass spectrometry[J]. Journal of Food Safety & Quality,2021,12 (9):3635-3641.
[13]	李兴元, 高健, 邹广辉, 等. 关于果蔬农残检测前处理方法的探讨[J]. 食品安全导刊,2022(5):165-167 doi: 10.3969/j.issn.1674-0270.2022.5.spaqdk202205059 LI Xingyuan, GAO Jian, ZOU Guanghui, et al. Discussion on pretreatment method of pesticide residue detection in fruits and vegetables[J]. China Food Safety Magazine,2022 (5):165-167. doi: 10.3969/j.issn.1674-0270.2022.5.spaqdk202205059
[14]	李健潇, 李淑云, 周洋, 等. 滤过型萃取柱-超高效液相色谱-串联质谱法测定食用菌中15种农药[J]. 卫生研究,2021,50(4):633-640 LI Jianxiao, LI Shuyun, ZHOU Yang, et al. Detect 15 pesticides fungicide in edible fungi by multiplug filtration clean-up pretreatment technology with ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Journal of Hygiene Research,2021,50 (4):633-640.
[15]	任彩君, 梁馨文, 薛晓锋, 等. 滤过型净化柱结合HPLC-MS/MS测定蜂花粉中9种农药[J]. 农药,2021,60(11):821-824, 828 REN Caijun, LIANG Xinwen, XUE Xiaofeng, et al. Simultaneous determination of 9 pesticide residues in bee pollen using multiplug filtration cleanup coupled HPLC-MS/MS[J]. Agrochemicals,2021,60 (11):821-824, 828.
[16]	吴岩, 姜冰, 徐义刚, 等. QuEChERS-液相色谱-串联质谱法同时测定果蔬中16种农药残留[J]. 色谱,2015,33(3):228-234 doi: 10.3724/SP.J.1123.2014.10026 WU Yan, JIANG Bing, XU Yigang, et al. Determination of 16 pesticide residues in fruits and vegetables by QuEChERS-liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography,2015,33 (3):228-234. doi: 10.3724/SP.J.1123.2014.10026