超高效液相色谱-串联质谱法测定茶叶中毒死蜱及其主要代谢物残留
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摘要
建立了超高效液相色谱-串联质谱(UPLC-MS/MS)法同时测定茶叶中毒死蜱(CPF)及其代谢产物3,5,6-三氯-2-羟基吡啶(TCP)残留量的分析检测方法。茶叶样品经4 mL水润湿后,用5%(V/V)乙酸酸化的乙腈提取,100 mg石墨化炭黑(GCB)和200 mg十八烷基硅烷(C_(18))净化,在仪器分析前用去离子水等体积稀释净化。CPF和TCP分别采用电喷雾正离子(ESI~+)和负离子(ESI~-)电离,可编程多反应监测(sM RM)模式监测,基质标准溶液内标法定量。结果表明,CPF和TCP分别在0.4～400.0μg/L和0.4～80.0μg/L浓度范围内线性关系良好(R~2> 0.99),方法的检出限(LOD,S/N=3)分别为0.06μg/kg和0.04～0.08μg/kg,定量限(LOQ,S/N=10)分别为0.20μg/kg和0.14～0.26μg/kg。在2.0、10.0和20.0μg/kg添加水平下,CPF和TCP的回收率分别为93.9%～111.4%和92.4%～118.4%,相对标准偏差(RSD,n=6)在3.2%～11.1%之间。本方法简便、快速、灵敏度高、重现性好,适用于茶叶中CPF和TCP的快速测定。
A sensitive method was developed for simultaneous determination of chlorpyrifos (CPF) and its main metabolite 3,5,6-trichloro-2-pyridinol (TCP) in tea samples by Qu EChERS and ultra-high performance liquid chromatography coupled with tandem mass spectrometry. Tea samples were extracted with acidic acetonitrile (containing 5% acetic acid),and cleaned up by the mixture of adsorbents containing 100 mg of graphitized carbon black (GCB) and 200 mg of C_(18). The extracts were diluted with deionized water equally in volume prior to instrumental analysis. Scheduled multiple reaction monitoring in positive ion mode was applied to detection of chlorpyrifos and selected ion recording in negative mode was applied to detection of TCP. The matrix-matched internal standard method was used for quantification. The results showed that the method provided linear ranges from 0. 4 to 400 μg/kg and 0. 4 to 80 μg/kg for CPF and TCP respectively with the correlation coefficients of larger than 0.99. The limits of detection (S/N = 3) were 0.06 μg/kg for CPF and 0.04-0. 08 μg/kg for TCP,while the limits of quantification (S/N = 10) were 0. 20 μg/kg for CPF and0.14-0.26 μg/kg for TCP. The recoveries were ranged from 93.9% to 111.4% for CPF and 92.4% to 118.4%for TCP respectively with the relative standard deviations (RSD,n = 6) of 3. 2%-11. 1%. This method was sensitive,rapid, simple and had good reproducibility, indicating that it was suitable for simultaneous determination of CPF and TCP in tea samples.
A sensitive method was developed for simultaneous determination of chlorpyrifos (CPF) and its main metabolite 3,5,6-trichloro-2-pyridinol (TCP) in tea samples by Qu EChERS and ultra-high performance liquid chromatography coupled with tandem mass spectrometry. Tea samples were extracted with acidic acetonitrile (containing 5% acetic acid),and cleaned up by the mixture of adsorbents containing 100 mg of graphitized carbon black (GCB) and 200 mg of C_(18). The extracts were diluted with deionized water equally in volume prior to instrumental analysis. Scheduled multiple reaction monitoring in positive ion mode was applied to detection of chlorpyrifos and selected ion recording in negative mode was applied to detection of TCP. The matrix-matched internal standard method was used for quantification. The results showed that the method provided linear ranges from 0. 4 to 400 μg/kg and 0. 4 to 80 μg/kg for CPF and TCP respectively with the correlation coefficients of larger than 0.99. The limits of detection (S/N = 3) were 0.06 μg/kg for CPF and 0.04-0. 08 μg/kg for TCP,while the limits of quantification (S/N = 10) were 0. 20 μg/kg for CPF and0.14-0.26 μg/kg for TCP. The recoveries were ranged from 93.9% to 111.4% for CPF and 92.4% to 118.4%for TCP respectively with the relative standard deviations (RSD,n = 6) of 3. 2%-11. 1%. This method was sensitive,rapid, simple and had good reproducibility, indicating that it was suitable for simultaneous determination of CPF and TCP in tea samples.
引文
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21 WANG Na,SUN Juan,SHI Li-Li,JI Gui-Xiang,CHEN Guo-Song.Chinese Journal of Chromatography,2013,31(9):903-907王娜,孙娟,石利利,吉贵祥,陈国松.色谱,2013,31(9):903-907
22 KONG Zhi-Qiang,DONG Feng-Shou,LIU Xin-Gang,XU Jun,GONG Yong,SHAN Wei-Li,ZHENG Yong-Quan.Chinese J.Anal.Chem.,2012,40(3):474-477孔志强,董丰收,刘新刚,徐军,龚勇,单炜力,郑永权.分析化学,2012,40(3):474-477
23 CHEN Wu-Ying,DONG Feng-Shou,LIU Xin-Gang,QIN Dong-Mei,LIAO Xiao-Lan,CHENG Li,WANG Chen-Rui,ZHENG Yong-Quan.Chinese J.Anal.Chem.,2010,38(4):508-512陈武瑛,董丰收,刘新刚,秦冬梅,廖晓兰,程莉,王晨蕊,郑永权.分析化学,2010,38(4):508-512
24 DONG Ya-Lei,LIU Wen-Jing,CAO Jin,WANG Gang-Li.Chinese J.Anal.Chem.,2017,45(9):1397-1404董亚蕾,刘文婧,曹进,王钢力.分析化学,2017,45(9):1397-1404
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27 Anastassiades M,Lehotay S J,Stajnbaher D,Schenck F J.J.AOAC Int.,2003,86(2):412-431
28 YIN Peng,CHEN Hong-Ping,LIU Xin,ZHOU Su-Juan,WANG Chuan-Pi,Yu Liang-Zi.Chinese Journal of Analysis Laboratory,2013,32(6):54-58尹鹏,陈红平,刘新,周苏娟,王川丕,于良子.分析试验室,2013,32(6):54-58
29 Chen H P,Marín-Sáez J,Remero-González R,Frenich A G.Food Chem.,2017,218:173-180
30 Baeza A N,Urraca J L,Chamorro R,Orellana G,Castellari M,Moreno-Bondi M C.J.Chromatogr.A,2016,1474:121-129
31 Jiao W T,Xiao Y,Qian X S,Tong MM,Hu Y Z,Hou R Y,Hua R M.Food Chem.,2016,210:26-34
32 Liu X,Guan W B,Hao X H,Wu X L,Ma Y Q,Pan C P.Chromatographia,2014,77:31-37
2 Thrasher J D,Heuser G,Broughton A.Arch.Environ.Health,2002,57(3):181-187
3 GB2763-2016,Maximum Residue Limits for Pesticides in Food.National Food Safety Standard of the People’s Republic of China食品安全国家标准-食品中农药最大残留限量.中华人民共和国国家标准.GB 2763-2016
4 Codex Alimentarius Commission.Pesticide Residues in Food and Feed.[2018-11-20].http://www.fao.org/fao-whocodexalimentarius/codex-texts/dbs/pestres/zh/
5 European Commission.Products to which MRLs apply(Part A of Annex Ito Reg.396/2005).[2018-11-20].http://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/public/?event=pesticide.residue.CurrentMRL&language=EN
6 Maximum Residue Limits(MRLs)List of Agricultural Chemicals in Foods.[2018-11-20].http://db.foodmate.net/kending/agrdtl.php?a_inq=21800
7 Chen H P,Hao Z X,Wang Q H,Jiang Y,Pan R,Wang C,Liu X,Lu C.Hum.Ecol.Risk Assess.,2016,22(1):28-38
8 Shemer H,Sharpless C M,Linden K G.Water Air Soil Poll.,2005,168(1):145-155
9 Muscarella D E,Keown J F,Bloom S E.Environ.Mol.Mutagen.,1984,6(1):13-23
10 Cáceres T,He W X,Naidu R,Mallavarapu M.Water Res.,2007,41(19):4497-4503
11 GUO Xiang,HE Jun-Tao,LIU Fen,HE Jian,LIN Hui,GUO Mei-Qiong,LI Shuang-Feng.China Occupational Medicine,2016,43(5):590-593,596郭翔,何俊涛,刘奋,何坚,林辉,郭美琼,李双凤.中国职业医学,2016,43(5):590-593,596
12 HANG Chang,ZHU Lu-Sheng,WANG Jun,WANG Jin-Hua,XIE Hui,SU Jun.Journal of Agro-Environment Science,2009,28(7):1552-1556韩畅,朱鲁生,王军,王金花,谢慧,苏郡.农业环境科学学报,2009,28(7):1552-1556
13 XU Dun-Ming,CHEN An-Liang,YU Xiang-Yang,WANG Qing-Xia,HE Jun,ZHANG Xing.Chinese J.Anal.Chem.,2005,33(4):451-455徐敦明,陈安良,余向阳,王箐霞,何军,张兴.分析化学,2005,33(4):451-455
14 Ling Y,Wang H,Yong W,Zhang F,Sun L,Yang M L,Wu Y N,Chu X G.Food Control,2011,22(1):54-58
15 SONG Ning-Hui,XU Huai-Zhou,JI Gui-Xiang,ZHANG Sheng-Hu,ZHANG Qin,GUO Min,SHI Li-Li.Chinese J.Anal.Chem.,2018,46(5):796-802宋宁慧,徐怀洲,吉贵祥,张圣虎,张芹,郭敏,石利利.分析化学,2018,46(5):796-802
16 HAO Li-Li,LI Rui,HE Liang.Physical Testing and Chemical Analysis Part B:Chemical Analysis,2015,51(9):1247-1251郝力力,李锐,贺亮.理化检验(化学分册),2015,51(9):1247-1251
17 Li R,He L,Zhou T,Ji X F,Qian M R,Zhou Y,Wang Q.Anal.Bioanal.Chem.,2014,406(12):2899-2907
18 LING Yun,WANG Han,YONG Wei,CHU Xiao-Gang.Chinese Journal of Chromatography,2009,27(1):78-81凌云,王菡,雍炜,储晓刚.色谱,2009,27(1):78-81
19 LI Wen-Ming,HAN Yong-Tao,DONG Feng-Shou,XU Jun,LIU Xin-Gang,LI Yuan-Bo,KONG Zhi-Qiang,ZHENGYong-Quan.Chinese Journal of Pesticide Science,2013,15(2):223-227李文明,韩永涛,董丰收,徐军,刘新刚,李远播,孔志强,郑永权.农药学学报,2013,15(2):223-227
20 Han Y T,Li W M,Dong F S,Xu J,Liu X G,Li Y B,Kong Z Q,Liang X Y,Zheng Y Q.Food Control,2013,31(2):560-565
21 WANG Na,SUN Juan,SHI Li-Li,JI Gui-Xiang,CHEN Guo-Song.Chinese Journal of Chromatography,2013,31(9):903-907王娜,孙娟,石利利,吉贵祥,陈国松.色谱,2013,31(9):903-907
22 KONG Zhi-Qiang,DONG Feng-Shou,LIU Xin-Gang,XU Jun,GONG Yong,SHAN Wei-Li,ZHENG Yong-Quan.Chinese J.Anal.Chem.,2012,40(3):474-477孔志强,董丰收,刘新刚,徐军,龚勇,单炜力,郑永权.分析化学,2012,40(3):474-477
23 CHEN Wu-Ying,DONG Feng-Shou,LIU Xin-Gang,QIN Dong-Mei,LIAO Xiao-Lan,CHENG Li,WANG Chen-Rui,ZHENG Yong-Quan.Chinese J.Anal.Chem.,2010,38(4):508-512陈武瑛,董丰收,刘新刚,秦冬梅,廖晓兰,程莉,王晨蕊,郑永权.分析化学,2010,38(4):508-512
24 DONG Ya-Lei,LIU Wen-Jing,CAO Jin,WANG Gang-Li.Chinese J.Anal.Chem.,2017,45(9):1397-1404董亚蕾,刘文婧,曹进,王钢力.分析化学,2017,45(9):1397-1404
25 Duirk S E,Collette T W.Environ.Sci.Technol.,2006,40(2):546-551
26 PAN Rong,CHEN Hong-Ping,YIN Peng,WANG Qing-Hua,JIANG Ying,LIU Xin.Journal of Instrumental Analysis,2014,33(7):766-772潘蓉,陈红平,尹鹏,汪庆华,蒋迎,刘新.分析测试学报,2014,33(7):766-772
27 Anastassiades M,Lehotay S J,Stajnbaher D,Schenck F J.J.AOAC Int.,2003,86(2):412-431
28 YIN Peng,CHEN Hong-Ping,LIU Xin,ZHOU Su-Juan,WANG Chuan-Pi,Yu Liang-Zi.Chinese Journal of Analysis Laboratory,2013,32(6):54-58尹鹏,陈红平,刘新,周苏娟,王川丕,于良子.分析试验室,2013,32(6):54-58
29 Chen H P,Marín-Sáez J,Remero-González R,Frenich A G.Food Chem.,2017,218:173-180
30 Baeza A N,Urraca J L,Chamorro R,Orellana G,Castellari M,Moreno-Bondi M C.J.Chromatogr.A,2016,1474:121-129
31 Jiao W T,Xiao Y,Qian X S,Tong MM,Hu Y Z,Hou R Y,Hua R M.Food Chem.,2016,210:26-34
32 Liu X,Guan W B,Hao X H,Wu X L,Ma Y Q,Pan C P.Chromatographia,2014,77:31-37