Detection of 32 pesticide residues in vegetables by SinChERS purification ultra-high performance liquid chromatography-tandem mass spectrometry

Abstract

Abstract:

Objective To establish a single step，cheap，effective，rugged，safe（SinChERS） purification ultra-high performance liquid chromatography-tandem mass spectrometry method for simultaneous detection of 32 pesticides in vegetables，providing relevant technical support for monitoring chemical pollutants and harmful factors in local vegetables in Qiqihar City. Methods Local vegetables in Qiqihar City from February to September 2024 were collected.Vegetable samples were extracted with acetonitrile and subjected to salt precipitation treatment.After purification using a SinChERS column，32 pesticides were simultaneously detected using ultra-high performance liquid chromatography tandem-mass spectrometry.Qualitative analysis was performed based on retention time and relative ion abundance ratio，while quantitative analysis was performed using an external standard method. Results Totally 32 pesticides showed a good linear relationship within the range of 5-200 μg/L，with correlation coefficients all greater than 0.998.The detection limit was 0.003 mg/kg，the quantification limit was 0.01 mg/kg，and the average recovery rate was between 74.5%-109.3%，with relative standard deviations all less than 10%.Among 186 types of local vegetables，71 were found to contain pesticide residues，with a detection rate of 38.2%. Conclusion The established method is easy to operate，fast，has good reproducibility，high accuracy，and low cost，and is suitable for batch detection of vegetable pesticide residue content.

Key words: Vegetables, Pesticide residues, Ultra-high performance liquid chromatography-tandem mass spectrometry, Detection

CLC Number:

R115

ZHANG Jing, ZHANG Lei, SHE Tiejun, WANG Jiao, FAN Wensu, JIA Shoushi. Detection of 32 pesticide residues in vegetables by SinChERS purification ultra-high performance liquid chromatography-tandem mass spectrometry. [J]OCCUPATION AND HEALTH, 2026, 42(4): 465-469.

Figures/Tables 7

References 18

[1]	惠媛, 张丽. 蔬菜中农药残留的危害及预防措施[J]. 农业科技与信息, 2017(18):45-46.
[2]	王建博, 王宏梅. 农药残留对食品安全性的影响[J]. 农家参谋, 2020(16):39.
[3]	张珊珊, 吴远高. 农药残留对食品安全的影响及应对策略分析[J]. 现代食品, 2020(20):215-217.
[4]	吕学冲. 农药残留在水果蔬菜和地下水中的风险评估及其可视化研究[D]. 保定: 河北大学, 2022.
[5]	王涛, 张虹, 周寒琳, 等. 固相萃取/高效液相色谱-串联质谱法同时测定土壤中12种有机磷酸酯[J]. 分析测试学报, 2023, 42(7):825-832.
[6]	曾霞, 于雅汇, 王鸟, 等. QuEChERS前处理技术在农药多残留检测中的研究进展[J]. 当代化工研究, 2022(6):33-35.
[7]	陈玲, 刘霜霜, 王锡兰, 等. QuEChERS技术净化材料在果蔬农药残留检测中的应用进展[J]. 食品安全质量检测学报, 2023, 14(3):1-9.
[8]	陈文辉, 王华威, 李建勋, 等. 基于亲水型低共熔溶剂的分散液液微萃取技术测定茶叶中的农药多残留[J]. 核农学报, 2023, 37(9):1823-1834. DOI
[9]	郭春丽, 余晓峰, 韩芳, 等. 磁固相萃取结合超高效液相色谱串联质谱法检测绿茶中19种有机磷农药残留[J]. 食品工业科技, 2024, 45(3):253-261.
[10]	SNEH R, ARPNA K, SAROJ A, et al. Multi-residue pesticides analysis in water samples using reverse phase high performance liquid chromatography(RP-HPLC)[J]. Methods, 2018,5:744-751.
[11]	郭爱华, 李晔, 王玮, 等. 高效液相色谱法测定粮谷中13种农药残留[J]. 预防医学情报杂志, 2018, 34(5):631-636.
[12]	邢露智, 黄毅娜. 农产品中农药残留检测技术研究进展[J]. 绿色科技, 2020(18):180-181.
[13]	SHIDA S S, HAMASAKA T, NEMOTO S, et al. Multiresidue determination of pesticides in tea by liquid chromatogra phy-high-resolution mass spectrometry:Comparison between Orbitrap and time-of-flight mass analyzers[J]. Food Chem, 2018,256:140-148.
[14]	CASADO J, SANTILLO D, JOHNSTON P. Multi-residue analysis of pesticides in surface water by liquid chromatography quadrupole-Orbitrap high resolution tandem mass spectrometry[J]. Anal Chim Acta, 2018,1024:1-17.
[15]	SZARKA A, TURKOVA D, HROUZKOVA S. Dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry for the determination of pesticide residues in nutraceutical drops[J]. J Chromatogr A, 2018,1570:126-134.
[16]	CACHO J I, CAMOILLO N, VINAS P, et al. In situ ionic liquid dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry for the determination of organophosphorus pesticides[J]. J Chromatogr A, 2018,1559:95-101.
[17]	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会.实验室质量控制规范食品理化检测:GB/T 27404—2008[S]. 北京: 中国标准出版社,2008:27.
[18]	国家卫生健康委员会, 农业农村部和国家市场监督管理总局.食品安全国家标准食品中农药最大残留限量:GB 2763—2021[S]. 北京: 中国标准出版社,2021:10-342.

时间（min）	流速（mL/min）	流动相A	流动相B
0.0	0.4	100	0
4.0	0.4	80	20
5.5	0.4	60	40
10.5	0.4	0	100
12.9	0.4	0	100
15.0	0.4	100	0
20.0	0.4	100	0

时间（min）	流速（mL/min）	流动相A	流动相B
0.0	0.4	100	0
4.0	0.4	80	20
5.5	0.4	60	40
10.5	0.4	0	100
12.9	0.4	0	100
15.0	0.4	100	0
20.0	0.4	100	0

农药	保留时间（min）	母离子（m/z）	子离子（m/z）	锥孔电压（V）	碰撞能量（eV）	极性	农药	保留时间（min）	母离子（m/z）	子离子（m/z）	锥孔电压（V）	碰撞能量（eV）	极性
甲拌磷砜	8.65	293.0	171.0^a/143.0	24	10/17	ESI+	噻虫嗪	5.51	292.0	211.1^a/181.1	25	10/20	ESI+
甲霜灵	8.79	280.0	220.0^a/192.0	30	15/20	ESI+	环氧虫啶	5.74	323.2	126.0^a/277.0	48	36/12	ESI+
嘧霉胺	8.81	200.1	107.0^a/183.0	25	24/25	ESI+	吡虫啉	6.28	256.1	175.1^a/209.1	25	20/12	ESI+
烯酰吗啉1&2	9.27/9.48	388.1	301.1^a/165.1	30	20/30	ESI+	噻虫胺	6.29	250.0	169.1^a/132.0	30	8/12	ESI+
三唑酮	9.50	294.0	69.0^a/197.0	30	20/14	ESI+	氯噻啉	6.52	262.0	181.0^a/122.1	30	13/30	ESI+
腈菌唑	9.56	289.1	70.1^a/125.1	25	15/30	ESI+	乐果	6.57	230.0	125.0^a/199.0	20	22/10	ESI+
联苯肼酯	9.60	301.0	198.0^a/170.0	25	10/20	ESI+	3-羟基克百威	6.67	238.0	181.0^a/163.0	34	12/20	ESI+
戊唑醇	10.07	308.2	70.1^a/125.0	30	24/40	ESI+	啶虫脒	6.69	223.1	126.0^a/56.2	30	20/15	ESI+
吡唑醚菌酯	10.18	388.0	163.1^a/194.1	25	25/12	ESI+	氟吡呋喃酮	6.72	289.1	126.1^a/90.0	30	15/50	ESI+
甲拌磷	10.26	261.1	75.1^a/199.0	15	12/8	ESI+	氟啶虫胺腈1&2	6.83/6.92	278.0	173.9^a/153.9	10	10/30	ESI+
氟啶胺	10.75	462.9	415.9^a/397.9	32	16/18	ESI-	噻虫啉	7.07	253.0	126.0^a/90.1	30	20/40	ESI+
炔螨特	10.96	368.0	231.1^a/175.1	15	10/15	ESI+	涕灭威	7.39	208.1	116.2^a/89.1	10	7/16	ESI+
乙螨唑	10.96	360.0	141.1^a/304.3	30	25/15	ESI+	哌虫啶1&2	7.46/7.97	367.2	137.1^a/263.1	38	26/16	ESI+
螺螨酯	11.08	411.0	71.1^a/313.0	35	15/10	ESI+	残杀威	7.99	210.1	111.1^a/93.1	12	6/14	ESI+
哒螨灵	11.24	365.0	147.0^a/309.0	10	24/12	ESI+	克百威	8.05	222.1	123.1^a/165.1	5	20/10	ESI+
阿维菌素	11.32	895.5	751.3^a/449.2	20	15/25	ESI+	甲拌磷亚砜	8.56	277.0	143.0^a/199.0	24	20/15	ESI+

农药	保留时间（min）	母离子（m/z）	子离子（m/z）	锥孔电压（V）	碰撞能量（eV）	极性	农药	保留时间（min）	母离子（m/z）	子离子（m/z）	锥孔电压（V）	碰撞能量（eV）	极性
甲拌磷砜	8.65	293.0	171.0^a/143.0	24	10/17	ESI+	噻虫嗪	5.51	292.0	211.1^a/181.1	25	10/20	ESI+
甲霜灵	8.79	280.0	220.0^a/192.0	30	15/20	ESI+	环氧虫啶	5.74	323.2	126.0^a/277.0	48	36/12	ESI+
嘧霉胺	8.81	200.1	107.0^a/183.0	25	24/25	ESI+	吡虫啉	6.28	256.1	175.1^a/209.1	25	20/12	ESI+
烯酰吗啉1&2	9.27/9.48	388.1	301.1^a/165.1	30	20/30	ESI+	噻虫胺	6.29	250.0	169.1^a/132.0	30	8/12	ESI+
三唑酮	9.50	294.0	69.0^a/197.0	30	20/14	ESI+	氯噻啉	6.52	262.0	181.0^a/122.1	30	13/30	ESI+
腈菌唑	9.56	289.1	70.1^a/125.1	25	15/30	ESI+	乐果	6.57	230.0	125.0^a/199.0	20	22/10	ESI+
联苯肼酯	9.60	301.0	198.0^a/170.0	25	10/20	ESI+	3-羟基克百威	6.67	238.0	181.0^a/163.0	34	12/20	ESI+
戊唑醇	10.07	308.2	70.1^a/125.0	30	24/40	ESI+	啶虫脒	6.69	223.1	126.0^a/56.2	30	20/15	ESI+
吡唑醚菌酯	10.18	388.0	163.1^a/194.1	25	25/12	ESI+	氟吡呋喃酮	6.72	289.1	126.1^a/90.0	30	15/50	ESI+
甲拌磷	10.26	261.1	75.1^a/199.0	15	12/8	ESI+	氟啶虫胺腈1&2	6.83/6.92	278.0	173.9^a/153.9	10	10/30	ESI+
氟啶胺	10.75	462.9	415.9^a/397.9	32	16/18	ESI-	噻虫啉	7.07	253.0	126.0^a/90.1	30	20/40	ESI+
炔螨特	10.96	368.0	231.1^a/175.1	15	10/15	ESI+	涕灭威	7.39	208.1	116.2^a/89.1	10	7/16	ESI+
乙螨唑	10.96	360.0	141.1^a/304.3	30	25/15	ESI+	哌虫啶1&2	7.46/7.97	367.2	137.1^a/263.1	38	26/16	ESI+
螺螨酯	11.08	411.0	71.1^a/313.0	35	15/10	ESI+	残杀威	7.99	210.1	111.1^a/93.1	12	6/14	ESI+
哒螨灵	11.24	365.0	147.0^a/309.0	10	24/12	ESI+	克百威	8.05	222.1	123.1^a/165.1	5	20/10	ESI+
阿维菌素	11.32	895.5	751.3^a/449.2	20	15/25	ESI+	甲拌磷亚砜	8.56	277.0	143.0^a/199.0	24	20/15	ESI+

农药	豇豆	茄子	黄瓜	芹菜	辣椒	青花菜	油麦菜	大白菜
噻虫嗪	89.8±1.2	82.6±1.4	92.5±1.1	82.0±1.0	90.3±1.1	91.7±1.0	81.1±1.2	83.2±1.3
环氧虫啶	84.6±1.1	89.0±1.1	87.3±1.2	109.3±1.0	101.7±0.9	90.2±0.9	87.9±1.1	102.4±1.3
吡虫啉	92.3±1.4	91.5±0.9	92.6±1.2	99.4±0.9	98.2±1.0	90.7±0.8	91.9±1.0	88.5±1.2
噻虫胺	93.8±1.0	89.0±0.9	95.6±1.0	98.3±1.2	87.8±0.9	95.1±1.1	94.2±1.0	96.5±1.3
氯噻啉	95.1±1.0	99.8±1.0	102.5±0.9	103.7±0.9	96.7±1.1	101.3±1.0	93.7±1.0	99.5±1.1
乐果	88.1±1.2	87.4±0.9	90.6±0.8	91.2±0.9	92.1±0.9	87.9±0.9	86.2±1.0	93.4±1.0
3-羟基克百威	92.4±0.9	88.2±1.0	86.1±1.2	95.6±1.3	93.1±1.0	89.5±0.8	91.4±1.1	94.9±1.1
啶虫脒	97.0±1.1	90.1±1.1	93.9±0.9	96.1±0.9	95.6±1.0	92.3±0.9	94.1±1.1	93.0±1.2
氟吡呋喃酮	101.2±1.0	93.5±1.2	98.2±1.0	99.7±1.0	96.3±0.9	97.4±1.1	100.2±0.9	93.6±1.2
氟啶虫胺腈	103.8±1.1	107.3±0.9	102.9±0.9	106.4±0.9	101.4±0.9	105.4±1.0	102.6±0.8	104.3±1.2
噻虫啉	87.5±1.0	91.3±0.9	93.2±0.9	89.9±0.9	88.7±1.1	90.2±1.2	87.9±1.0	92.9±1.0
涕灭威	85.6±1.0	87.3±1.3	83.9±1.0	88.6±1.5	74.5±1.2	79.1±1.0	80.6±1.3	76.8±1.3
哌虫啶	101.4±0.8	99.3±1.3	102.4±1.0	105.2±1.2	103.4±1.1	98.9±0.8	100.9±0.9	104.2±1.2
残杀威	90.7±0.9	89.4±1.3	94.5±1.3	97.6±1.2	92.3±1.0	95.4±1.0	94.1±1.2	91.0±1.2
克百威	98.2±0.9	100.1±1.0	89.3±1.3	103.2±1.0	91.0±0.9	93.2±1.0	98.5±1.1	101.0±1.2
甲拌磷亚砜	99.4±1.0	98.2±1.0	100.3±1.1	102.7±1.0	99.8±1.3	100.3±1.0	101.2±1.2	98.7±1.1
甲拌磷砜	88.6±1.0	89.0±1.2	92.1±1.3	96.2±1.2	91.5±0.9	93.2±1.1	89.7±1.0	94.0±0.9
甲霜灵	86.2±1.1	94.6±1.3	100.2±1.3	89.3±1.2	88.2±1.0	91.2±1.3	97.6±1.0	90.3±1.2
嘧霉胺	85.5±1.2	83.6±1.3	82.7±0.9	86.2±1.0	84.8±1.2	86.2±1.2	81.3±1.4	87.0±1.1
烯酰吗啉	95.3±1.0	96.6±0.9	99.3±1.0	95.8±1.3	96.0±1.2	95.8±0.9	97.1±1.0	100.1±1.2
三唑酮	97.1±1.2	95.2±1.0	89.9±1.1	90.5±1.2	91.2±0.9	94.3±1.1	97.0±1.1	92.5±1.0
腈菌唑	100.8±1.2	98.2±1.0	102.4±1.2	99.8±1.2	97.9±1.1	100.1±0.9	99.2±1.2	98.0±1.3
联苯肼酯	103.2±1.0	88.7±0.9	92.4±1.3	89.5±0.9	90.5±1.0	91.8±1.0	100.2±1.2	93.1±1.2
戊唑醇	104.8±0.9	100.2±0.9	103.1±1.3	101.3±1.3	102.5±1.2	99.9±1.0	101.7±1.0	104.3±1.2
吡唑醚菌酯	103.2±1.0	99.6±1.3	101.7±1.2	104.3±1.2	100.2±1.0	98.9±1.0	101.3±1.2	103.2±1.2
甲拌磷	92.1±1.1	88.5±1.3	86.1±1.0	90.7±1.1	89.1±1.2	90.2±1.0	91.4±1.3	92.5±1.0
氟啶胺	89.7±1.2	90.3±1.0	92.4±1.2	97.9±1.2	91.5±0.9	91.0±1.0	93.4±1.2	96.7±1.3
炔螨特	93.6±1.2	96.1±1.3	89.9±1.3	93.8±1.3	90.8±1.2	91.2±1.0	94.0±1.2	96.2±1.2
乙螨唑	97.9±1.2	90.3±1.3	98.5±1.2	100.4±0.9	91.2±1.0	96.6±1.2	90.3±1.2	97.8±1.0
螺螨酯	104.5±1.1	101.7±0.9	106.2±0.9	109.3±1.2	105.3±1.2	103.4±1.0	101.8±1.1	104.5±1.1
哒螨灵	101.3±1.0	100.8±0.9	105.3±1.3	107.2±1.2	102.3±1.1	102.4±1.2	100.7±1.0	104.8±1.3
阿维菌素	97.2±0.9	94.7±1.3	99.4±1.1	102.3±0.9	96.1±0.9	94.9±1.2	95.7±1.2	101.2±1.0