UPLC-MS/MS固相萃取法检测鸡肝、鸡胗中11种喹诺酮、4种四环素、氯霉素残留

摘要/Abstract

摘要： 目的建立检测鸡肝、鸡胗中11种喹诺酮、4种四环素、氯霉素残留的高效、便捷的检测方法。方法鸡胗、鸡肝经提取、净化、固相萃取等步骤处理后,利用超高压液相色谱-质谱/质谱仪（ultra-high performance liquidchromatography-tandem mass spectrometer,UPLC-MS/MS）对兽药残留进行分离,定量测定。结果 16种兽药残留线性范围为1.0~40 ng/mL（氯霉素0.1~4.0 mg/mL）,相关系数除诺氟沙星其他均>0.999 0,在不同浓度情况下测定平均回收率在61.6%~107.1%,诺氟沙星、环丙沙星、达氟沙星、四环素、强力霉素、土霉素、金霉素方法检出限为0.6 μg/kg,定量限为1.8 μg/kg;二氟沙星、培氟沙星、氧氟沙星、恩诺沙星、洛美沙星、沙拉沙星、恶喹酸、氟甲喹方法检出限为0.2 μg/kg,定量限为0.6 μg/kg;氯霉素方法检出限为0.02 μg/kg,定量限为0.06 μg/kg。结论用本方法对2022年采集的鸡胗、鸡肝样本进行检测,线性范围、检出限、精密度、准确度均达到检测要求。本方法提高了检测效率,适合市场上鸡肝、鸡胗的大量样品的兽药筛查检测,适合作为食品安全风险监测快速筛查的方法。

关键词: 超高压液相色谱-质谱/质谱仪, 固相萃取, 喹诺酮, 四环素, 氯霉素, 鸡胗, 鸡肝

Abstract: Objective To establish efficient and convenient detection methods for detecting 11 kinds of quinolones,4 kinds of tetracycline and chloramphenicol residues in chicken liver and gizzard. Methods After processing chicken gizzards and liver through extraction,purification and solid phase extraction,UPLC-MS/MS was used to separate and quantitatively determine the residues of veterinary drugs. Results The linear range of residues of 16 veterinary drugs was 1.0-40 ng/mL（chloramphenicol 0.1-4.0 ng/mL）,the correlation coefficient was greater than 0.999 0 except norfloxacin,and the average recovery rate was 61.6%-107.1% determined at different concentrations,and the detection limit of norfloxacin, ciprofloxacin, dafloxacin, tetracycline, doxycycline, oxytetracycline, chlortetracycline, doxycycline, and chlortetracycline was 0.6 μg/kg, and the limit of quantification was 1.8 μg/kg. The detection limit of difloxacin, pefloxacin, ofloxacin, enrofloxacin, lomefloxacin, salafloxacin, oxaquinic acid, and flumequine was 0.2 μg/kg, and the limit of quantification was 0.6 μg/kg. The detection limit of chloramphenicol was 0.02 μg/kg, and the limit of quantification was 0.06 μg/kg. Conclusion Using this method to detect the chicken gizzards and liver samples collected in 2022,the liner range, detection limit, precision and accuracy all meet the detection requirements. This method improves the detection efficiency,is suitable for veterinary drug screening and detection of a large number of samples of chicken liver and gizzard on the market,and is suitable as a rapid screening method for food safety risk monitoring.

Key words: Ultra-high performance liquidchromatography-tandem mass spectrometer, Solid phase extraction, Quinolones, Tetracycline, Chloramphenicol, Chicken gizzard, Chicken liver

中图分类号:

R115

李堃, 赵丹莹, 李晔, 郭爱华, 温雅. UPLC-MS/MS固相萃取法检测鸡肝、鸡胗中11种喹诺酮、4种四环素、氯霉素残留. [J]职业与健康, 2024, 40(6): 761-766.

LI Kun, ZHAO Danying, LI Ye, GUO Aihua, WEN Ya. UPLC-MS/MS and solid phase extraction determination of 11 quinolones,4 tetracyclines and chloramphenicol residues in chicken liver and gizzard. [J]OCCUPATION AND HEALTH, 2024, 40(6): 761-766.

参考文献

[1] 郎朗,张莹,杨昂瑾,等.哈尔滨蔬菜基地土壤中喹诺酮类抗生素的污染现状[J].生态毒理学报,2022,17(5):435-442.
[2] 谭蓉. 使用喹诺酮类抗生素人畜的排泄物对环境的污染[J].环境与健康杂志,2009,26(12):1125-1127.
[3] AMORIM C L,MAIA A S,MESQUITA R B,et al.Performance of aerobic granular sludge in a sequencing batch bioreactor exposed to ofloxacin,norfloxacin and ciprofloxacin[J].Water Res,2014(50):101-113.
[4] 马静静. 内蒙古牧区土壤中兽药青霉素的残留及吸附研究[D].呼和浩特:内蒙古大学,2010.
[5] 徐向月,马文瑾,安博宇,等.四环素类抗生素在环境中的风险评估研究进展[J].中国畜牧兽医,2020,47(3):948-957.
[6] 李晓琍. 动物性食品中抗生素类药物的残留污染[J].实用预防医学,2004,11(6):1304-1306.
[7] 王美娟,谢群,王华雨.2019—2021年某院325例血培养细菌分布及耐药性分析[J].实用预防医学,2023,30(1):108-111.
[8] 陈旭,王琳,李享宸,等.2018—2020年凉山彝族地区某医院细菌耐药性监测分析[J].实用预防医学,2022,29(12):1443-1447.
[9] ADESIYUN A A,FASINA F O,ABAFE O A,et al.Occurrence and concentrations of residues of tetracyclines,polyether ionophores,and anthelmintics in livers of chickens sold in the informal market in Gauteng province,South Africa[J].J Food Prot,2020,84(4):655-663.
[10] 方兰云,潘胜东,陆蓓蓓,等.2018—2020年宁波市动物源性食品中喹诺酮和四环素类兽药残留污染状况及暴露评估[J].卫生研究,2022,51(1):113-117.
[11] 彭文绣,李璇,成昕.鸡蛋中喹诺酮类兽药残留现状及对策建议[J].中国兽药杂志,2020,54(10):76-81.
[12] 石春力. 水中喹诺酮类抗生素的来源、现状及处理方法[J].科技展望,2015,25(20):69-71.
[13] 乔勤勤,文芳,郑楠,等.我国市场上UHT灭菌乳和巴氏杀菌乳中四种兽药残留风险评估[J].中国农业大学学报,2020,25(1):105-112.
[14] 中华人民共和国农业农村部,中华人民共和国国家卫生健康委员会,国家市场监督管理总局.食品安全国家标准食品中兽药最大残留限量:GB 31650—2019[S].北京:中国农业出版社,2019:1-55.
[15] 农业部.中华人民共和国农业部公告第235号[EB/OL].(2002-12-24)[2023-03-24].http://www.moa.gov.cn/govpublic/SYJ/201006/t20100606_1535491.htm?keywords=.
[16] 张莹,谷圣臣,潘俊池,等.基于ARIMA型的中国家禽出栏量预测[J].黑龙江八一农垦大学学报,2020,32(3):20-26.
[17] 解迎双,张欢,王新潮,等.动物源性食品中多种兽药残留UPLC-MS/MS分析方法的构建[J].中国口岸科学技术,2023,5(3):88-96.
[18] 吴春霞,张秋萍,王春民,等.超高效液相色谱-串联三重四级质谱法测定动物源性食品中的喹诺酮类和四环素类残留[J].中国卫生检验杂志,2022,32(19):2310-2314.
[19] 周瑞铮,林秋凤,易华娟,等.QuEChERS-dSPE-UPLC-MS/MS法筛查动物源性食品中9种兽药残留[J].现代食品,2021(21):170-175.
[20] GUO X J,TIAN H,YANG F,et al.Rapid determination of 103 common veterinary drug residues in milk and dairy products by ultra performance liquid chromatography tandem mass spectrometry[J].Front Nutr,2022,9:879518.
[21] WANG J Q,ZHAO W T,GUO W P,et al.Simultaneous screening and analysis of 155 veterinary drugs in livestock foods using ultra-high performance liquid chromatography tandem quadrupole linear-ion-trap mass spectrometry[J].Food Chem,2022,393:133260.
[20] 郭添荣,万渝平,孙利,等.通过式固相萃取结合超高效液相色谱-四极杆/静电场轨道阱高分辨质谱快速筛查畜禽肉中108种兽药残留[J].分析化学,2022,50(2):271-289.
[23] AL-AMRI I,KADIM I T,ALKINDI A,et al.Determination of residues of pesticides,anabolic steroids,antibiotics,and antibacterial compounds in meat products in Oman by liquid chromatography/mass spectrometry and enzyme-linked immunosorbent assay[J].Vet World,2021,14(3):709-720.
[24] 李宁,肖琎,王雪松,等.高效液相色谱-串联质谱法同时测定动物源性食品中15种禁限兽药残留[J].中国饲料,2023(2):97-100.
[25] 王志昱,张桂芳,张晓瑜,等.QuEChERS-高效液相色谱-质谱联用法同时检测鸡胗和鸡肝中15种喹诺酮类和四环素类抗生素[J].肉类研究,2020,34(3):51-57.
[26] DUBREIL E,GAUTIER S,FOURMOND M P,et al.Validation approach for a fast and simple targeted screening method for 75 antibiotics in meat and aquaculture products using LC-MS/MS[J].Food Addit Contam Part A Chem Anal Control Expo Risk Assess,2017,34(4):453-468.
[27] FREITAS A.Development and validation of analytical methodologies for the determination of antibiotics in food of animal origin for human consumption[D].Coimbra:Universidade de Coimbra,2015.
[28] 李娜,张玉婷,刘磊,等.QuEChERS-超高效液相色谱-串联质谱法测定动物源食品中4类29种禁限用兽药残留[J].色谱,2014,32(12):1313-1319.
[29] 刘柏林,谢继安,赵紫微,等.固相萃取-超高效液相色谱-串联质谱法同时测定动物源性食品中11种禁限兽药及代谢物[J].色谱,2021,39(4):406-414.
[30] MORETTI S,DUSI G,GIUSEPPONI D,et al.Screening and confirmatory method for multiclass determination of 62 antibiotics in meat[J].J Chromatogr A,2016,1429:175-188.