Determination of residues of 9 herbicides of international concern in dairy products by high performance liquid chromatography-tandem mass spectrometry

Authors

YAN Wanying, Guangzhou Inspection and Testing Certification Group Company Limited, Guangzhou, Guangdong 511447, China; South China Agricultural University, Guangzhou, Guangdong 510642, China; Guangdong Bureau of the National Food and Strategic Reserves Administration, Guangzhou, Guangdong 510050, China
HE Minheng, Guangzhou Inspection and Testing Certification Group Company Limited, Guangzhou, Guangdong 511447, China
LI Mingming, Guangzhou Inspection and Testing Certification Group Company Limited, Guangzhou, Guangdong 511447, China
HUANG Shiying, Guangzhou Inspection and Testing Certification Group Company Limited, Guangzhou, Guangdong 511447, China
CHEN Wenjing, South China Agricultural University, Guangzhou, Guangdong 510642, China
SHEN Yingtao, Guangzhou Inspection and Testing Certification Group Company Limited, Guangzhou, Guangdong 511447, China
HUANG Jiale, Guangzhou Inspection and Testing Certification Group Company Limited, Guangzhou, Guangdong 511447, ChinaFollow

Corresponding Author(s)

黄嘉乐（1988—），女，广州检验检测认证集团有限公司质量高级工程师，硕士。E-mail：673510691@qq.com

Abstract

[Objective] To establish a rapid and precise determination method for 9 herbicides (asulam, hexazinone, indaziflam, norflurazon, pyrasulfotole, pyroxasulfone, sulfosulfuron, tebuthiuron, and tepraloxydim) in dairy products that are of international concern but without established maximum residue limits (MRLs) in China. [Methods] The samples are ultrasonically extracted with acetonitrile-acetone mixed reagent (v∶v=8∶2), and the extract is purified by the dispersed solid-phase extraction adsorbents Florisil, N-propylethylenediamine (PSA), and anhydrous MgSO4. A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method is established for determination. [Results] The nine herbicides are completely separated within 7 min. Their linear relationships are good within the range of 2.00~100 μg/L (r≥0.997). Their detection limits are 0.02~0.30 μg/kg, spiked recoveries are 71.6%~104.1%, and relative standard deviations are 0.4%~10.3%. [Conclusion] This method is simple to operate, has high sensitivity and good reproducibility, and can be used for rapid determination of residues of the 9 herbicides in dairy products.

Publication Date

1-23-2026

First Page

50

Last Page

57

DOI

10.13652/j.spjx.1003.5788.2025.80483

Recommended Citation

Wanying, YAN; Minheng, HE; Mingming, LI; Shiying, HUANG; Wenjing, CHEN; Yingtao, SHEN; and Jiale, HUANG (2026) "Determination of residues of 9 herbicides of international concern in dairy products by high performance liquid chromatography-tandem mass spectrometry," Food and Machinery: Vol. 42: Iss. 1, Article 7.
DOI: 10.13652/j.spjx.1003.5788.2025.80483
Available at: https://www.ifoodmm.cn/journal/vol42/iss1/7

References

[1] BUERGE I J,KASTEEL R,KRAUSS J,et al.Detection of the herbicide asulam in groundwater:translocation to roots of treated docks (rumex ) and exudation to subsoil as a potential input pathway [J].Pest Management Science,2025,81(7):4 135-4 142.
[2] KAUFMANN A,KAENZIG A.Contamination of honey by the herbicide asulam and its antibacterial active metabolite sulfanilamide [J].Food Additives & Contaminants,2004,21(6):564-571.
[3] OERLEMANS A,FIGUEIREDO D M,MOL J G J,et al.Personal exposure assessment of pesticides in residents:the association between hand wipes and urinary biomarkers [J].Environmental Research,2021,199:111282.
[4] MACHADO C S,FREGONESI B M,ALVES R I S,et al.Health risks of environmental exposure to metals and herbicidesin the Pardo River,Brazil [J].Environmental Science and Pollution Research International,2017,24(25):20 160-20 172.
[5] KÖNEN ADIGÜZEL S.The possible cytotoxicity and genotoxicity assessment of indaziflam on HepG 2 cells [J].Human & Experimental Toxicology,2023,42:9603271231183145.
[6] HONG T,PARK S,AN G,et al.Norflurazon causes cell death and inhibits implantation-related genes in porcine trophectoderm and uterine luminal epithelial cells [J].Food and Chemical Toxicology,2024,186:114559.
[7] 秦博,英君伍,崔东亮,等.磺酰草吡唑的合成与生物活性研究[J].现代农药,2020,19(4):19-22.QIN B,YING J W,CUI D L,et al.Synthesis and bioactivity of pyrasulfotole [J].Modern Agrochemicals,2020,19(4):19-22.
[8] ARYA R,SHARMA R,MALHOTRA M,et al.Biodegradation aspects of carbendazim and sulfosulfuron:trends,scope and relevance [J].Current Medicinal Chemistry,2015,22(9):1 147-1 155.
[9] FRANCO-BERNARDES M F,ROCHA O P,PEREIRA L C,et al.The herbicides trifluralin and tebuthiuron have no genotoxic or mutagenic potential as evidenced by genetic tests [J].Environmental Science and Pollution Research International,2017,24(30):24 029-24 037.
[10] DE OLIVEIRA B,PEREIRA L C,PAZIN M,et al.Do trifluralin and tebuthiuron impair isolated rat liver mitochondria ? [J].Pesticide Biochemistry and Physiology,2020,163:175-184.
[11] HUYNH D,WU C W.High-throughput identification of oxidative stress-inducing environmental chemicals in the C.elegans system [J].Free Radical Biology and Medicine,2022,191:59-65.
[12] SCHOLZ-AHRENS K E,AHRENS F,BARTH C A.Nutritional and health attributes of milk and milk imitations [J].European Journal of Nutrition,2020,59(1):19-34.
[13] 张敏,彭小雨,高宇,等.双峰驼乳的营养特性和生物活性研究进展 [J].食品与机械,2022,38(10):230-234.ZHANG M,PENG X Y,GAO Y,et al.Research progress on nutritional characteristics and biological activity of Bactrian camel milk [J].Food & Machinery,2022,38(10):230-234.
[14] TUDI M,DANIEL RUAN H,WANG L,et al.Agriculture development,pesticide application and its impact on the environment [J].International Journal of Environmental Research and Public Health,2021,18(3):1 112.
[15] 胡利锋,刘小安,孙兰,等.除草剂安全剂作用机理研究进展[J].农药学学报,2017,19(2):152-161.HU L F,LIU X,SUN L,et al.Progresses in the action mechanism of herbicide safeners [J].Chinese Journal of Pesticide Science,2017,19(2):152-161.
[16] SCHLEIFFER M,SPEISER B.Presence of pesticides in the environment,transition into organic food,and implications for quality assurance along the European organic food chain-A review [J].Environmental Pollution,2022,313:120116.
[17] SUH J H.Critical review:metabolomics in dairy science-evaluation of milk and milk product quality [J].Food Research International,2022,154:110984.
[18] 李子豪,王昌钊,赵铁营,等.超高效液相色谱—串联质谱法测 定 乳 及 乳 制 品 中 苯 菌 酮 的 残 留 量 [J].食 品 安 全 质 量 检 测学报,2022,13(20):6 684-6 691.LI Z H,WANG C Z,ZHAO T Y,et al.Determination of metrafenone residues in milk and milk products by ultra performance liquid chromatography-tandem mass spectrometry[J].Journal of Food Safety & Quality,2022,13(20):6 684-6 691.
[19] 高猛峰,童金蓉,梅博,等.超高效液相色谱—串联质谱法测定 生 牛 乳 中 10种 新 烟 碱 类 农 药 残 留 [J].食 品 与 机 械,2025,41(1):74-79.GAO M F,TONG J R,MEI B,et al.Simultaneous determination of 10 neonicotinoid pesticides in raw milk by ultra-high performance liquid chromatography tandem mass spectrometry [J].Food & Machinery,2025,41(1):74-79.
[20] 赵妍,杨军,辛少鲲,等.超高效液相色谱—高分辨质谱法测定 牛 奶 中 新 烟 碱 类 农 药 残 留 [J].中 国 食 品 卫 生 杂 志,2020,32(2):139-145.ZHAO Y,YANG J,XIN S K,et al.Determination of neonicotinoid residues in milk by ultra-high performance liquid chromatography-high resolution mass spectrometry [J].Chinese Journal of Food Hygiene,2020,32(2):139-145.
[21] FEDRIZZI G,ALTAFINI A,ARMORINI S,et al.LC-MS/MS analysis of five neonicotinoid pesticides in sheep and cow milk samples collected in Jordan valley [J].Bulletin of Environmental Contamination and Toxicology,2019,102(3):347-352.
[22] 邓龙,周思,黄佳佳,等.固相支撑液液萃取结合 LC-MS/MS快速测定生乳中 32种农药残留 [J].食品工业科技,2023,44(17):360-366.DENG L,ZHOU S,HUANG J J,et al.Determination of 32 kinds of pesticide residues in raw milk by supported liquid extraction with LC-MS/MS [J].Science and Technology of Food Industry,2023,44(17):360-366.
[23] YAO Y H,BAI L L,TIAN H F,et al.A fluorinated chitosan-based QuEChERS method for simultaneous determination of 20 organophosphorus pesticide residues in ginseng using GC-MS/MS [J].Biomedical Chromatography,2021,35(12):e5209.
[24] 吴敏莲,黄伟乾,吴俊发,等.UPLC-MS/MS 测定啤酒中茚嗪氟 草 胺 及 其 代 谢 物 残 留 量 [J].中 国 酿 造,2022,41(11):228-232.WU M L,HUANG W Q,WU J F,et al.Determination of indaziflam and its metabolites residues in beer by UPLC-MS/MS[J].China Brewing,2022,41(11):228-232.
[25] 国 家 卫 生 健 康 委 员 会,农 业 农 村 部,国 家 市 场 监 督 管 理 总|局.植 物 源 性 食 品 中 331种 农 药 及 其 代 谢 物 残 留 量 的 测 定 液 相 色 谱 — 质 谱 联 用 法:GB 23200.121—2021 [S].北 京:中国标准出版社,2021:1-5.National Health Commission,Ministry of Agriculture and Rural Affairs,State Administration for Market Regulation.Determination of 331 pesticides and metabolites residues in foods of plant origin.Liquid chromatography-tandem mass spectrometry method:GB 23200.121—2021 [S].Beijing:Standards Press of China,2021:1-5.
[26] 国 家 卫 生 健 康 委 员 会,农 业 农 村 部,国 家 市 场 监 督 管 理 总局.鸡蛋中氟虫腈及其代谢物残留量的测定 液相色谱—质谱 联 用 法:GB 23200.115—2018 [S].北 京:中 国 标 准 出 版 社,2018:1-5.National Health Commission,Ministry of Agriculture and Rural Affairs,State Administration for Market Regulation.Determination of fipronil and metabolites residues in eggs Liquid chromatography-tandem mass spectrometry method:GB 23200.115—2018 [S].Beijing:Standards Press of China,2018:1-5.
[27] 严 婉 盈,何 敏 恒,温 恒,等.分 散 固 相 萃 取 — 超 高 效 液 相 色谱 — 串 联 质 谱 法 测 定 乳 制 品 中 8种 杀 虫 剂 [J].食 品 与 机 械,2022,38(12):44-49.YAN W Y,HE M H,WEN H,et al.Determination of eight kinds of insecticides in dairy products by dispersed solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry [J].Food & Machinery,2022,38(12):44-49.
[28] KOBAYASHI M,SAKAI N,OHMACHI Y,et al.Determination of asulam in livestock products by LC-MS/MS[J].Shokuhin Eiseigaku Zasshi Journal of the Food Hygienic Society of Japan,2021,62(1):1-7.
[29] 王敬,艾连峰,马育松,等.气相色谱 /三重四极杆串联质谱法测定牛奶及奶粉中 213种农药多残留 [J].色谱,2015,33(11):1 175-1 185.WANG J,AI L F,MA Y S,et al.Determination of 213 pesticide residues in milk and milk power by gas chromatography-triple quadrupole tandem mass spectrometry[J].Chinese Journal of Chromatography,2015,33(11):1 175-1 185.
[30] PRATELLI G,TAMBURINI B,BADAMI G D,et al.Cow's milk:a benefit for human health ? omics tools and precision nutrition for lactose intolerance management [J].Nutrients,2024,16(2):320.
[31] 张磊,许秀丽,沈正超,等.基于气相色谱—静电场轨道阱高分辨质谱快速筛查和确证牛奶中 30种香豆素、香兰素及其衍生物 [J].中国乳品工业,2025,53(4):67-73,80.ZHANG L,XU X L,SHEN Z C,et al.Rapid screening and quantitative of thirty coumarins and vanillins and their derivatives in milk by gas chromatography-orbitrap mass spectrometry [J].China Dairy Industry,2025,53(4):67-73,80.
[32] 欧阳位麒.UPLC-MS/MS 法测定 10种果蔬中 19种农药残留的基质效应研究 [J].现代农业科技,2025 (9):138-143.OUYANG W Q.Study on the matrix effects of 19 pesticide residues in 10 kinds of fruits and vegetables determined by UPLC-MS/MS method [J].Modern Agricultural Science and Technology,2025 (9):138-143.
[33] 吴滋灵,姚晓庆,沈应涛,等.液态乳中 8种阴离子残留量的同时检测 [J].食品与机械,2023,39(10):56-61,68.WU Z L,YAO X Q,SHEN Y T,et al.Determination of eight anions in liquid milk [J].Food & Machinery,2023,39(10):56-61,68.
[34] 杜昕昕,王寅鹏,肖伟,等.基质固相分散萃取—高效液相色谱法同时测定五味子中 5种木脂素类化合物 [J].色谱,2023,41(3):257-264.DU X X,WANG Y P,XIAO W,et al.Simultaneous determination of five lignans from Schisandra chinensis by matrix solid-phase dispersion extraction-high performance liquid chromatography [J].Chinese Journal of Chromatography,2023,41(3):257-264.
[35] 黄曼谷,罗永浩,严婉盈,等.分散固相萃取—超高效液相色谱—串联质谱法测定液态奶中 11种农药残留量 [J].食品与机械,2023,39(12):48-54,87.HUANG M G,LUO Y H,YAN W Y,et al.Determination of 11 kinds of pesticide residues in liquid milk by dispersive solid phase extraction coupled with ultra performance liquid chromatography-tandem mass spectrometry [J].Food & Machinery,2023,39(12):48-54,87.