Determination of 32 Kinds of Pesticide Residues in Raw Milk by Supported Liquid Extraction with LC-MS/MS

DENG Long; ZHOU Si; HUANG Jiajia; ZENG Shangmin; ZHANG Jingwen

doi:10.13386/j.issn1002-0306.2022120075

Volume 44 Issue 17

Aug. 2023

Turn off MathJax

Article Contents

Abstract

References

Science and Technology of Food Industry > 2023 > 44(17): 360-366. > DOI: 10.13386/j.issn1002-0306.2022120075

DENG Long, ZHOU Si, HUANG Jiajia, 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. (in Chinese with English abstract). doi: 10.13386/j.issn1002-0306.2022120075.

Citation:

PDF (4890 KB)

Determination of 32 Kinds of Pesticide Residues in Raw Milk by Supported Liquid Extraction with LC-MS/MS

1.
Guangdong Food and Drug Vocational College, Guangzhou 510520, China
2.
Guangzhou Centre for Disease Control and Prevention, Guangzhou 510440, China

More Information

Received Date: December 07, 2022
Available Online: June 28, 2023

Graphical Abstract

Abstract

Abstract

To provide scientific support for guaranteeing food safety in raw milk, a rapid method for the determination of pesticide residues in raw milk was developed using supported liquid extraction technique and ultra-performance liquid chromatography tandem mass spectrometry. The sample was precipitated with acetonitrile and then separated by high speed centrifugation. The supernatant was purified by SLE column. Separation of pesticide residues was achieved by a CORTECS C₁₈ column. Pesticide residues were detected by ultra-performance liquid chromatography tandem mass spectrometry with electrospray ionization in the multiple reaction monitoring mode, and the quantification was accomplished by external standard method of matrix standard curve. Method validation revealed satisfactory linearities with correlation coefficients higher than 0.9962, and limits of detection and quantification for target compounds were 0.1~2.5 μg/kg and 0.3~7.5 μg/kg, the average recoveries at three spiked levels were in the range of 69.4%~113.6% with relative standard deviation (RSD, n=6) less than 8.2%. This method is simple, quickly and reliable, and shows great promise for detecting 32 different pesticide residues in raw milk.
- supported liquid extraction,
- LC-MS/MS,
- pesticide residues

FullText(HTML)

References (30)

References

[1]	SUH J H. Critical review: Metabolomics in dairy science-evaluation of milk and milk product quality[J]. Food Research International,2022,154:110984. doi: 10.1016/j.foodres.2022.110984
[2]	LI C, ZHU H, LI C, et al. The present situation of pesticide residues in China and their removal and transformation during food processing[J]. Food Chemistry,2021,354:129552. doi: 10.1016/j.foodchem.2021.129552
[3]	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):1112. doi: 10.3390/ijerph18031112
[4]	张峰祖, 朴秀英, 李富根. 国际食品法典委员会动物源性食品中农药最大残留限量制定现状[J]. 农药学学报,2021,23(1):22−30. [ZHANG F Z, PIAO X Y, LI F G. Current situation on setting of pesticide maximum residue limits in food commodities of animal origin in Codex Alimentarius Commission[J]. Chinese Journal of Pesticide Science,2021,23(1):22−30. doi: 10.16801/j.issn.1008-7303.2021.0019 [ZHANG F Z, PIAO X Y, LI F G. Current situation on setting of pesticide maximum residue limits in food commodities of animal origin in Codex Alimentarius Commission[J]. Chinese Journal of Pesticide Science, 2021, 23(1): 22-30. doi: 10.16801/j.issn.1008-7303.2021.0019
[5]	袁娜, 杨臻, 乔璐, 等. 中国与主要贸易国水产品中农药残留限量标准对比分析[J]. 食品安全质量检测学报,2021,12(10):4244−4256. [YUAN N, YANG Z, QIAO L, et al. Comparative analysis of pesticide residue limit standards in aquatic products between China and major trading countries[J]. Journal of Food Safety & Quality,2021,12(10):4244−4256. doi: 10.19812/j.cnki.jfsq11-5956/ts.2021.10.054 YUAN N, YANG Z, QIAO L, et al. Comparative analysis of pesticide residue limit standards in aquatic products between China and major trading countries[J]. Journal of Food Safety & Quality, 2021, 12(10): 4244-4256. doi: 10.19812/j.cnki.jfsq11-5956/ts.2021.10.054
[6]	中华人民共和国国家卫生健康委员会, 中华人民共和国农业农村部, 国家市场监督管理总局. GB 2763-2021食品安全国家标准食品中农药最大残留限量[S]. 北京: 中国农业出版社, 2021 The People’s Republic of China, National Health Commission, Ministry of Agriculture and Rural Affairs, State Administration for Market Regulation. GB 2763-2021 National food safety standard-Maximum residue limits for pesticides in food[S]. Beijing: China Agriculture Press, 2021.
[7]	中华人民共和国国家卫生和计划生育委员会, 中华人民共和国农业农村部, 国家市场监督管理总局. GB 23200.85-2016食品安全国家标准乳及乳制品中多种拟除虫菊酯农药残留量的测定气相色谱-质谱法[S]. 北京: 中国农业出版社, 2016: 2−3 The People’s Republic of China, National Health and Family Planning Commission, Ministry of Agriculture and Rural Affairs, State Administration for Market Regulation. GB 23200.85-2016 National food safety standards-Determination of multiple pyrethroid pesticide residues in dairy products gas chromatography-mass spectrometry[S]. Beijing: China Agriculture Press, 2016: 2−3.
[8]	中华人民共和国国家卫生和计划生育委员会, 中华人民共和国农业农村部, 国家市场监督管理总局. 23200.86-2016食品安全国家标准乳及乳制品中多种有机氯农药残留量的测定气相色谱-质谱/质谱法[S]. 北京: 中国农业出版社, 2016: 2−3 The People’s Republic of China, National Health and Family Planning Commission, Ministry of Agriculture and Rural Affairs, State Administration for Market Regulation. GB 23200.86-2016 National food safety standards-Determination of multiple residue of organochlorine pesticides in milk and dairy products gas chromatography-mass spectrometry[S]. Beijing: China Agriculture Press, 2016: 2−3.
[9]	WENG R, LOU S, PANG X, et al. Multi-residue analysis of 126 pesticides in chicken muscle by ultra-high-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry[J]. Food Chemistry,2020,309:125503. doi: 10.1016/j.foodchem.2019.125503
[10]	PARK J A, ABD EL-ATY A M, ZHENG W J, et al. Simultaneous determination of clanobutin, dichlorvos, and naftazone in pork, beef, chicken, milk, and egg using liquid chromatography tandem mass spectrometry[J]. Food Chemistry,2018,252:40−48. doi: 10.1016/j.foodchem.2018.01.085
[11]	HILDMANN F, GOTTERT C, FRENZEL T, et al. Pesticide residues in chicken eggs-A sample preparation methodology for analysis by gas and liquid chromatography/tandem mass spectrometry[J]. Journal of Chromatography A,2015,1403:1−20. doi: 10.1016/j.chroma.2015.05.024
[12]	文静, 莫楠, 张立佳, 等. 超高效液相色谱-串联质谱法测定牛乳中氯虫苯甲酰胺、氟苯虫酰胺和2甲4氯的残留[J]. 食品工业科技,2023,44(5):285−291. [WEN J, MO N, ZHANG L J, et al. Determination of chlorantraniliprole, flubendiamide and 2-methy 4-chlorophenoxyacetic acid residues in milk by ultra performance liquid chromatography-tandem mass spectrometry[J]. Science and Technology of Food Industry,2023,44(5):285−291. doi: 10.13386/j.issn1002-0306.2022050039 WEN J, MO N, ZHANG L J, et al. Determination of chlorantraniliprole, flubendiamide and 2-methy 4-chlorophenoxyacetic acid residues in milk by ultra performance liquid chromatography-tandem mass spectrometry[J]. Science and Technology of Food Industry, 2023, 44(5): 285-291. doi: 10.13386/j.issn1002-0306.2022050039
[13]	LEDOUX M. Analytical methods applied to the determination of pesticide residues in foods of animal origin: A review of the past two decades[J]. Journal of Chromatography A,2011,1218(8):1021−1036. doi: 10.1016/j.chroma.2010.12.097
[14]	BANERJEE K. Novel GC/MS, HPLC/MS, and HPLC-diode array detector-based methods for determination of pesticide residues in food, feed, water, and soil samples[J]. Journal of AOAC International,2010,93(2):353−354. doi: 10.1093/jaoac/93.2.353
[15]	LI Y, AN Q, ZHANG C, et al. Comparison of Sin-QuEChERS nano and d-SPE methods for pesticide multi-residues in lettuce and chinese chives[J]. Molecules,2020,25(15):3391. doi: 10.3390/molecules25153391
[16]	DUBEY J K, PATYAL S K, SHARMA A. Validation of QuEChERS analytical technique for organochlorines and synthetic pyrethroids in fruits and vegetables using GC-ECD[J]. Environmental Monitoring and Assessment,2018,190(4):231. doi: 10.1007/s10661-018-6584-8
[17]	张朋杰, 张宪臣, 李云松, 等. QuEChERS结合超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法快速测定禽畜肉中157种农药残留[J]. Journal of Food Safety & Quality,2022,13(16):5391−5400. [ZHANG P J, ZHANG X C, LI Y S, et al. Rapid determination of 157 kinds of pesticide residues in livestock and poultry meat by QuEChERS combined with ultra performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry[J]. Journal of Food Safety & Quality,2022,13(16):5391−5400. ZHANG P J, ZHANG X C, LI Y S, et al. Rapid determination of 157 kinds of pesticide residues in livestock and poultry meat by QuEChERS combined with ultra performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry[J]. Journal of Food Safety & Quality, 2022, 13(16): 5391-5400.
[18]	张蓉, 陈跃, 郑培, 等. 凝胶渗透色谱-气相色谱-离子阱质谱法测定桔梗原药和当归提取物中101种农药残留[J]. 色谱, 2023, 41(2): 178-186 ZHANG R, CHEN Y, ZHENG P, et al. Determination of 101 Pesticide Residues in platycodis radix and extracts of angelica sinensis by gel permeation chromatograpgy gas chromatograpgy-ion trap mass spectrometry[J]. Chinese Journal of Chromatography, 2023, 41(2): 178-186.
[19]	ZHOU S, ZHANG L, GUO C X, et al. Comparing liquid-liquid, solid-phase, and supported-liquid extraction for the determination of polycyclic aromatic hydrocarbons in serum samples and their application for human biomonitoring[J]. Microchemical Journal,2022,181:107182.
[20]	BREITENBUCHER J G, ARIENTI K L, MCCLURE K J. Scope and limitations of solid-supported liquid-liquid extraction for the high-throughput purification of compound libraries[J]. Journal of Combinatorial Chemistry,2001,3(6):528−533. doi: 10.1021/cc010039f
[21]	BYLDA C, THIELE R, KOBOLD U, et al. Recent advances in sample preparation techniques to overcome difficulties encountered during quantitative analysis of small molecules from biofluids using LC-MS/MS[J]. Analyst,2014,139(10):2265−2276. doi: 10.1039/c4an00094c
[22]	YAKIMAVETS V, QIU T, PANUWET P, et al. Simultaneous quantification of urinary tobacco and marijuana metabolites using solid-supported liquid-liquid extraction coupled with liquid chromatography tandem mass spectrometry[J]. Journal of Chromatography B,2022,1208:123378. doi: 10.1016/j.jchromb.2022.123378
[23]	MOON J Y, LEE H S, KIM J H, et al. Supported liquid extraction coupled to gas chromatography-selective mass spectrometric scan modes for serum steroid profiling[J]. Analytica Chimica Acta,2018,1037:281−292. doi: 10.1016/j.aca.2018.02.059
[24]	CHEN S, LI S, FANG K, et al. Rapid determination of 93 banned industrial dyes in beverage, fish, cookie using solid-supported liquid-liquid extraction and ultrahigh-performance liquid chromatography quadrupole orbitrap high-resolution mass spectrometry[J]. Food Chemistry,2022,388:132976. doi: 10.1016/j.foodchem.2022.132976
[25]	商婷, 赵灵娟, 李佩, 等. 固相支撑液液萃取-液相色谱-串联质谱法测定尿液中10种单羟基多环芳烃[J]. 分析化学,2019,47(6):876−882. [SHANG T, ZHAO L J, LI P, et al. Determination of 10 kinds of monohydroxylated polycyclic aromatic hydrocarbons in human urine by supported liquid extraction followed by liquid chromatographytandem mass spectrometry[J]. Chinese Journal of Analytical Chemistry,2019,47(6):876−882. doi: 10.19756/j.issn.0253-3820.191069 SHANG T, ZHAO L J, LI P, et al. Determination of 10 kinds of monohydroxylated polycyclic aromatic hydrocarbons in human urine by supported liquid extraction followed by liquid chromatographytandem mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2019, 47(6): 876-882. doi: 10.19756/j.issn.0253-3820.191069
[26]	陈雅莉, 扈洪志, 肖小华, 等. 乳制品样品前处理与分析检测技术研究进展[J]. 分析测试学报,2021,40(7):1098−1108. [CHEN Y L, HU H Z, XIAO X H, et al. Progress of sample preparation and analytical methods for dairy products[J]. Journal of Instrumental Analysis,2021,40(7):1098−1108. doi: 10.3969/j.issn.1004-4957.2021.07.019 CHEN Y L, HU H Z, XIAO X H, et al. Progress of sample preparation and analytical methods for dairy products[J]. Journal of Instrumental Analysis, 2021, 40(7): 1098-1108. doi: 10.3969/j.issn.1004-4957.2021.07.019
[27]	ISMAIEL O A, ZHANG T, JENKINS R G, et al. Investigation of endogenous blood plasma phospholipids, cholesterol and glycerides that contribute to matrix effects in bioanalysis by liquid chromatography/mass spectrometry[J]. Journal of Chromatography B,2010,878(31):3303−3316. doi: 10.1016/j.jchromb.2010.10.012
[28]	KAUFMANN A, BUTCHER P, MADEN K, et al. Multi-residue quantification of veterinary drugs in milk with a novel extraction and cleanup technique: salting out supported liquid extraction (SOSLE)[J]. Analytica Chimica Acta,2014,820:56−68. doi: 10.1016/j.aca.2014.02.038
[29]	RYSKA M. How to deal with the "matrix effect" as an unavoidable phenomenon[J]. European Journal of Mass Spectrometry,2015,21(3):423−432. doi: 10.1255/ejms.1355
[30]	中华人民共和国国家质量监督检验检疫总局. GB/T 27404-2008实验室质量控制规范食品理化检测[S]. 北京: 中国标准出版社, 2008: 26−27 General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China. GB/T 27404-2008 Criterion on quality control of laboratories-chemical testing of food[S]. Beijing: China Standards Press, 2008: 26−27.

Supplements (0)

Cited By

Cited by

Periodical cited type(7)

1.	冯薇，孟然，李赵嘉，吴哲，鲁雪林，陈悦，王秀萍. 甲基磺酸乙酯对蒲公英胚性细胞基因表达的影响. 中草药. 2025(06): 2111-2121 .
2.	冯薇，吴哲，孟然，李赵嘉，鲁雪林，张丽娜，王秀萍. 蒲公英白粉病病原菌鉴定及种质资源抗病性评价. 中国蔬菜. 2025(03): 104-110 .
3.	晋海军，杨灵丽，梁建东，龚荣英，邢益政，王国凯，陈美娟，田维毅. 蒲公英水提液的发酵工艺优化及其机制研究. 食品与发酵工业. 2024(21): 112-120 .
4.	刘红宁，姜佳恩，单雅慧，郑凯麒，周权，陈丽华. 茶剂产品的开发现状与创新发展趋势. 中成药. 2023(11): 3683-3688 .
5.	程丽英，沈纪健，胡西阳，王若男，高源，李印帮. 蒲公英的营养保健价值及其在食品中开发利用现状. 食品工业. 2022(08): 331-334 .
6.	李家磊，高扬，管立军，严松，徐娜，卢淑雯，李波，周野. 蒲公英超微粉馒头的研制及品质分析. 食品科技. 2022(12): 141-148 .
7.	伍建军. 国民营养计划背景下的中国营养保健食品行业创新发展趋势. 食品安全质量检测学报. 2021(08): 3164-3171 .