Determination of Residues of Carbofuran and 3-Hydroxycarbofuran in Bee Products by Liquid Chromatography Tandem Mass Spectrometry with QuEChERS
摘 要
提出了QuEChERS前处理结合液相色谱-串联质谱法(LC-MS/MS)测定蜂产品(蜂蜜,蜂胶和蜂王浆)中克百威及3-羟基克百威的残留量。蜂产品样品使用乙腈提取,用无水硫酸镁脱水,再用无水硫酸镁、乙二胺-N-丙基硅烷化硅胶(PSA)和十八烷基硅烷键合硅胶(C18)混合剂净化,采用Accucore aQ C18色谱柱(150 mm×2.1 mm,2.6 μm)进行分离,以不同体积比的甲醇和含5 mmol·L-1甲酸铵的0.1%(体积分数)甲酸溶液混合液为流动相进行梯度洗脱,多反应监测(MRM)模式下进行质谱检测,外标法定量。结果表明,克百威及3-羟基克百威的质量浓度在0.002~0.100 mg·L-1内与对应的峰面积呈线性关系,克百威和3-羟基克百威在蜂蜜、蜂王浆中的测定下限(10S/N)均为0.01 mg·kg-1,在蜂胶中的测定下限(10S/N)为0.05 mg·kg-1。按照标准加入法进行回收试验,回收率为84.5%~108%,测定值的相对标准偏差(n=6)小于7.0%。
Abstract
A method for determination of residues of carbofuran and 3-hydroxycarbofuran in bee products (honey, propolis and royal jelly) was proposed by QuEChERS pretreatment combined with liquid chromatography tandem mass spectrometry (LC-MS/MS). The bee product sample was extracted with acetonitrile, dehydrated by anhydrous magnesium sulfate, and purified with the mixed agent of anhydrous magnesium sulfate, PSA and C18. Accucore aQ C18 column (150 mm×2.1 mm, 2.6 μm) was used for the separation, and the mixtures of methanol and 0.1% (volume fraction) formic acid solution containing 5 mmol·L-1 ammonium formate at different volume ratios were used as the mobile phase for gradient elution. Multiple reaction monitoring (MRM) mode was adopted in MS detection, with external standard method for quantification. As shown by the results, linear relationships between values of the corresponding peak area and mass concentration of carbofuran and 3-hydroxycarbofuran were found in the range of 0.002-0.100 mg·L-1, with lower limits of determination (10S/N) of carbofuran and 3-hydroxycarbofuran in honey and royal jelly of 0.01 mg·kg-1, and those in propolis of 0.05 mg·kg-1. Test for recovery was made by the standard addition method, giving the results in the range of 84.5%-108%, with RSDs (n=6) of the determined values less than 7.0%.
中图分类号 O657.63 DOI 10.11973/lhjy-hx202312004
所属栏目 工作简报
基金项目 国家重点研发计划项目(2019YFC1605403)
收稿日期 2022/11/16
修改稿日期
网络出版日期
作者单位点击查看
备注黎天勇,工程师,主要从事食品质量安全检测研究工作
引用该论文: LI Tianyong,LI Ju,WU Shuyue,XI Jing,WANG Lan. Determination of Residues of Carbofuran and 3-Hydroxycarbofuran in Bee Products by Liquid Chromatography Tandem Mass Spectrometry with QuEChERS[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2023, 59(12): 1388~1394
黎天勇,李菊,吴舒悦,席静,王岚. QuEChERS-液相色谱-串联质谱法测定蜂产品中克百威和3-羟基克百威的残留量[J]. 理化检验-化学分册, 2023, 59(12): 1388~1394
共有人对该论文发表了看法,其中:
人认为该论文很差
人认为该论文较差
人认为该论文一般
人认为该论文较好
人认为该论文很好
参考文献
【1】钟水桥,梁美艳.EMR-Lipid-超高效液相色谱-串联质谱法快速测定猪肉中多种氨基甲酸酯类农药残留量[J].现代食品, 2020(6):170-172.
【2】冯晓青,汪怡,王芹,等.凝胶渗透色谱-高效液相色谱法测定食用菌中呋喃丹农药残留[J].分析仪器, 2016(5):6-9.
【3】张艳,陈国,吴银良.固相萃取-液相色谱串联质谱法测定鸡蛋中16种氨基甲酸酯类杀虫剂残留量[J].食品安全质量检测学报, 2020,11(6):1728-1735.
【4】DONOVAN S, TAGGART M, RICHARDS N. An overview of the chemistry, manufacture, environmental fate and detection of carbofuran[M]. Hoboken:Carbofuran and wildlife poisoning, 2011:1-18.
【5】李梦怡,彭博,李博,等.农用乙酰胆碱酯酶抑制剂研究进展[J].生物技术进展, 2017,7(2):127-134.
【6】隋海霞,刘兆平,张磊.毒理学关注阈值方法在农药活性成分转化产物慢性膳食风险评估中的应用[J].中华预防医学杂志, 2013,47(6):569-572.
【7】MISHRA S, ZHANG W P, LIN Z Q, et al. Carbofuran toxicity and its microbial degradation in contaminated environments[J]. Chemosphere, 2020,259:127419.
【8】MUNIR M A, ANJUM K M, JAVID A, et al. Sublethal toxicity of carbofuran in cattle egret (Bubulcus ibis coromandus):Hematological, biochemical, and histopathological alterations[J]. Brazilian Journal of Biology, 2024,84:255055.
【9】杨静,刘超,徐善智.气相色谱-质谱联用法快速检测食物中毒案例中的克百威农药[J].食品安全质量检测学报, 2018,9(6):1395-1399.
【10】燕娅娅,刘峰,徐飞.一起克百威致急性中毒事件的调查分析[J].中国卫生检验杂志, 2022,32(13):1623-1625.
【11】周佳,何丹,王炳志,等.胶体金免疫层析法同时检测果蔬中克百威、水胺硫磷、百菌清及虫酰肼的应用研究[J].食品安全质量检测学报, 2021,12(19):7606-7610.
【12】孟晓萌,潘少香,谭梦男,等.气相色谱-三重四极杆质谱法同时测定草莓中多种农残及其衍生物残留[J].食品科技, 2020,45(8):276-281.
【13】马宏,吴宇,陈晋莹,等.生物荧光酶抑制法快速定性测定粮食中有机磷类和氨基甲酸酯类农药残留[J].中国粮油学报, 2022,37(2):167-174.
【14】陈俊秀,马晓年,李文廷,等.超高效液相色谱-串联质谱法测定蔬菜中4种氨基甲酸酯类农药残留量[J].食品安全质量检测学报, 2021,12(5):1789-1797.
【15】杭学宇,吴珺玮,宋鑫,等.QuEChERS提取-超高效液相色谱-串联质谱法测定蔬菜中氨基甲酸酯类农药的残留量[J].理化检验-化学分册, 2020,56(1):60-65.
【16】褚乾梅,黄大明,朱梦洁,等.液质联用法测定果蔬中氨基甲酸酯类农药残留[J].湖北农业科学, 2019,58(21):163-166.
【17】董冰岩,沈璐璐,章海啸.超高效液相色谱法测定陈皮、蒲公英根中2种氨基甲酸酯类农药残留[J].农药, 2020,59(4):281-283.
【18】ZHAO Y J, TAN G Y, WANG M, et al. Application of immunoassays for rapid monitor of carbofuran residue in vegetables[J]. Journal of Food Science, 2019,84(11):3296-3302.
【19】WANG N, LI R Y, WANG Q S, et al. Boron-doped and serine and histidine-functionalized graphene quantum dots with strong yellow fluorescence emissions for highly sensitive detection of carbofuran in cucumber and cabbage[J]. New Journal of Chemistry, 2021,45(37):17258-17265.
【20】LAN J Q, WANG M F, DING S, et al. Simultaneous detection of carbofuran and 3-hydroxy-carbofuran in vegetables and fruits by broad-specific monoclonal antibody-based ELISA[J]. Food and Agricultural Immunology, 2019,30(1):1085-1096.
【21】ZHANG C P, HE H M, YU J Z, et al. Residues of carbosulfan and its metabolites carbofuran and 3-hydroxy carbofuran in rice field ecosystem in China[J]. Journal of Environmental Science and Health, Part B, 2016,51(6):351-357.
【22】周添,刘菲.小体积液液萃取气相色谱-质谱法测定地下水中的克百威与3-羟基克百威[J].岩矿测试, 2021,40(3):358-364.
【23】高翠玲,韩智峰,侯广月,等.超高效液相色谱-串联质谱法测定水中11种氨基甲酸酯类农药[J].分析试验室, 2021,40(11):1269-1274.
【24】LAN J Q, SUN W M, CHEN L J, et al. Simultaneous and rapid detection of carbofuran and 3-hydroxy-carbofuran in water samples and pesticide preparations using lateral-flow immunochromatographic assay[J]. Food and Agricultural Immunology, 2020,31(1):165-175.
【25】DIUZHEVA A, DEJMKOVÁ H, FISCHER J, et al. Simultaneous determination of three carbamate pesticides using vortex-assisted liquid-liquid microextraction combined with HPLC-amperometric detection[J]. Microchemical Journal, 2019,150:104071.
【26】CHEN S Y, YU Y, MA J S, et al. Simultaneous determination of carbofuran and 3-hydroxycarbofuran in duck liver by an UPLC-MS/MS[J]. Acta Chromatographica, 2021,33(4):354-360.
【27】GONÇALVES V, HAZARBASSANOV N Q, DE SIQUEIRA A, et al. Development and validation of carbofuran and 3-hydroxycarbofuran analysis by high-pressure liquid chromatography with diode array detector (HPLC-DAD) for forensic veterinary medicine[J]. Journal of Chromatography B, 2017,1065/1066:8-13.
【28】平文卉,杨娟,杨清华,等.磁固相萃取-高效液相色谱-串联质谱法测定蜂蜜中的克百威[J].食品科技, 2020,45(5):319-322.
【2】冯晓青,汪怡,王芹,等.凝胶渗透色谱-高效液相色谱法测定食用菌中呋喃丹农药残留[J].分析仪器, 2016(5):6-9.
【3】张艳,陈国,吴银良.固相萃取-液相色谱串联质谱法测定鸡蛋中16种氨基甲酸酯类杀虫剂残留量[J].食品安全质量检测学报, 2020,11(6):1728-1735.
【4】DONOVAN S, TAGGART M, RICHARDS N. An overview of the chemistry, manufacture, environmental fate and detection of carbofuran[M]. Hoboken:Carbofuran and wildlife poisoning, 2011:1-18.
【5】李梦怡,彭博,李博,等.农用乙酰胆碱酯酶抑制剂研究进展[J].生物技术进展, 2017,7(2):127-134.
【6】隋海霞,刘兆平,张磊.毒理学关注阈值方法在农药活性成分转化产物慢性膳食风险评估中的应用[J].中华预防医学杂志, 2013,47(6):569-572.
【7】MISHRA S, ZHANG W P, LIN Z Q, et al. Carbofuran toxicity and its microbial degradation in contaminated environments[J]. Chemosphere, 2020,259:127419.
【8】MUNIR M A, ANJUM K M, JAVID A, et al. Sublethal toxicity of carbofuran in cattle egret (Bubulcus ibis coromandus):Hematological, biochemical, and histopathological alterations[J]. Brazilian Journal of Biology, 2024,84:255055.
【9】杨静,刘超,徐善智.气相色谱-质谱联用法快速检测食物中毒案例中的克百威农药[J].食品安全质量检测学报, 2018,9(6):1395-1399.
【10】燕娅娅,刘峰,徐飞.一起克百威致急性中毒事件的调查分析[J].中国卫生检验杂志, 2022,32(13):1623-1625.
【11】周佳,何丹,王炳志,等.胶体金免疫层析法同时检测果蔬中克百威、水胺硫磷、百菌清及虫酰肼的应用研究[J].食品安全质量检测学报, 2021,12(19):7606-7610.
【12】孟晓萌,潘少香,谭梦男,等.气相色谱-三重四极杆质谱法同时测定草莓中多种农残及其衍生物残留[J].食品科技, 2020,45(8):276-281.
【13】马宏,吴宇,陈晋莹,等.生物荧光酶抑制法快速定性测定粮食中有机磷类和氨基甲酸酯类农药残留[J].中国粮油学报, 2022,37(2):167-174.
【14】陈俊秀,马晓年,李文廷,等.超高效液相色谱-串联质谱法测定蔬菜中4种氨基甲酸酯类农药残留量[J].食品安全质量检测学报, 2021,12(5):1789-1797.
【15】杭学宇,吴珺玮,宋鑫,等.QuEChERS提取-超高效液相色谱-串联质谱法测定蔬菜中氨基甲酸酯类农药的残留量[J].理化检验-化学分册, 2020,56(1):60-65.
【16】褚乾梅,黄大明,朱梦洁,等.液质联用法测定果蔬中氨基甲酸酯类农药残留[J].湖北农业科学, 2019,58(21):163-166.
【17】董冰岩,沈璐璐,章海啸.超高效液相色谱法测定陈皮、蒲公英根中2种氨基甲酸酯类农药残留[J].农药, 2020,59(4):281-283.
【18】ZHAO Y J, TAN G Y, WANG M, et al. Application of immunoassays for rapid monitor of carbofuran residue in vegetables[J]. Journal of Food Science, 2019,84(11):3296-3302.
【19】WANG N, LI R Y, WANG Q S, et al. Boron-doped and serine and histidine-functionalized graphene quantum dots with strong yellow fluorescence emissions for highly sensitive detection of carbofuran in cucumber and cabbage[J]. New Journal of Chemistry, 2021,45(37):17258-17265.
【20】LAN J Q, WANG M F, DING S, et al. Simultaneous detection of carbofuran and 3-hydroxy-carbofuran in vegetables and fruits by broad-specific monoclonal antibody-based ELISA[J]. Food and Agricultural Immunology, 2019,30(1):1085-1096.
【21】ZHANG C P, HE H M, YU J Z, et al. Residues of carbosulfan and its metabolites carbofuran and 3-hydroxy carbofuran in rice field ecosystem in China[J]. Journal of Environmental Science and Health, Part B, 2016,51(6):351-357.
【22】周添,刘菲.小体积液液萃取气相色谱-质谱法测定地下水中的克百威与3-羟基克百威[J].岩矿测试, 2021,40(3):358-364.
【23】高翠玲,韩智峰,侯广月,等.超高效液相色谱-串联质谱法测定水中11种氨基甲酸酯类农药[J].分析试验室, 2021,40(11):1269-1274.
【24】LAN J Q, SUN W M, CHEN L J, et al. Simultaneous and rapid detection of carbofuran and 3-hydroxy-carbofuran in water samples and pesticide preparations using lateral-flow immunochromatographic assay[J]. Food and Agricultural Immunology, 2020,31(1):165-175.
【25】DIUZHEVA A, DEJMKOVÁ H, FISCHER J, et al. Simultaneous determination of three carbamate pesticides using vortex-assisted liquid-liquid microextraction combined with HPLC-amperometric detection[J]. Microchemical Journal, 2019,150:104071.
【26】CHEN S Y, YU Y, MA J S, et al. Simultaneous determination of carbofuran and 3-hydroxycarbofuran in duck liver by an UPLC-MS/MS[J]. Acta Chromatographica, 2021,33(4):354-360.
【27】GONÇALVES V, HAZARBASSANOV N Q, DE SIQUEIRA A, et al. Development and validation of carbofuran and 3-hydroxycarbofuran analysis by high-pressure liquid chromatography with diode array detector (HPLC-DAD) for forensic veterinary medicine[J]. Journal of Chromatography B, 2017,1065/1066:8-13.
【28】平文卉,杨娟,杨清华,等.磁固相萃取-高效液相色谱-串联质谱法测定蜂蜜中的克百威[J].食品科技, 2020,45(5):319-322.
相关信息