同位素稀释-气相色谱串联质谱法测定饲料中指示性多氯联苯
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摘要
建立了气相色谱-串联质谱法(GC-MS/MS)测定动物饲料中6种指示性多氯联苯的痕量分析方法。样品中的多氯联苯经溶剂加速萃取,用44%酸性硅胶柱脱脂和复合硅胶柱净化,气相色谱-串联质谱法分析。采用DB-5MS毛细管柱分离,电子轰击电离源(EI)电离,多反应监测模式下(MRM)检测,同位素稀释法进行定量分析。结果表明,方法的线性范围为0.1～500.0 ng/m L,相关系数(R~2)均大于0.999,平均相对响应因子(RRF)为1.08～1.21;定量限为5.5～9.2 pg/g,样品添加回收率为92.8%～109.7%,RSD为1.6%～14.8%;定量内标的回收率为32.6%～90.2%。应用此方法对北京市周边地区采集的10个配合饲料样品进行检测,6种指示性PCBs均有检出,其中PCB28和PCB52为优势单体,总浓度范围为54.7～191.7 pg/g,远低于我国国标饲料限量标准(10μg/kg)。
A method was developed for determination of 6 kinds of indictor polychlorinated biphenyls in animal feed by chromatography-tandem mass spectrometry (GC-MS/MS). Analytical procedure consisted of accelerate solvent extraction (ASE),lipid removal with 44% acidic silica and clean-up using a column packed with multilayer silica. The analytes were separated on a DB-5 MS capillary column,detected with electron ionization (EI) and multiple reaction monitor mode (MRM),and quantified using isotope dilution technique. The result showed that the calibration curves with good correlation coefficients (R~2> 0.999) were obtained in the concentration range of 0. 1-500. 0 ng/m L. The average relative response factors of PCBs in calibration solvent were 1.08-1.21,and the limit of quantification were 5.5-9.2 pg/g. The average recoveries of PCBs in animal feed at two spiked concentration levels ranged from 92.8% to 109.7% with relative standard deviations (RSDs) of 1. 6%-14. 8% (n = 5),and the average recoveries of quantitative internal standards were 32.6%-90.2%. Then the proposed method was successfully applied to detect the compound feed samples from the surrounding area of Beijing,and it was found that the 6 kinds of indictor PCBs were detected in all samples (n = 10) with the total concentration ranges of 54. 7-191. 7 pg/g,which were far below the limit standard (10 μg/kg) of Chinese National Standards.
A method was developed for determination of 6 kinds of indictor polychlorinated biphenyls in animal feed by chromatography-tandem mass spectrometry (GC-MS/MS). Analytical procedure consisted of accelerate solvent extraction (ASE),lipid removal with 44% acidic silica and clean-up using a column packed with multilayer silica. The analytes were separated on a DB-5 MS capillary column,detected with electron ionization (EI) and multiple reaction monitor mode (MRM),and quantified using isotope dilution technique. The result showed that the calibration curves with good correlation coefficients (R~2> 0.999) were obtained in the concentration range of 0. 1-500. 0 ng/m L. The average relative response factors of PCBs in calibration solvent were 1.08-1.21,and the limit of quantification were 5.5-9.2 pg/g. The average recoveries of PCBs in animal feed at two spiked concentration levels ranged from 92.8% to 109.7% with relative standard deviations (RSDs) of 1. 6%-14. 8% (n = 5),and the average recoveries of quantitative internal standards were 32.6%-90.2%. Then the proposed method was successfully applied to detect the compound feed samples from the surrounding area of Beijing,and it was found that the 6 kinds of indictor PCBs were detected in all samples (n = 10) with the total concentration ranges of 54. 7-191. 7 pg/g,which were far below the limit standard (10 μg/kg) of Chinese National Standards.
引文
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15 SONG Zi-Liang,LI Fu-Er,WANG Yong,RILEY William,TANG Shu-Ze.Guangdong Agricultural Sciences,2012,39(21):122-125宋梓亮,李福儿,汪勇,Riley William,唐书泽.广东农业科学,2012,39(21):122-125
16 Sun H Z,Wang P,Li H H,Li Y M,Zheng S C,Matsiko J,Hao Y F,Zhang W W,Wang D,Zhang Q H.Sci.China Chem.,2017,60(5):670-677
17 HU Hong-Mei,GUO Yuan-Ming,HAO Qing,SUN Xiu-Mei,JIN Yan-Jian,ZHONG Zhi,LI Tie-Jun.Chinese J.Anal.Chem.,2016,44(1):88-94胡红美,郭远明,郝青,孙秀梅,金衍健,钟志,李铁军.分析化学,2016,44(1):88-94
18 SHAO Yang,YANG Guo-Sheng,HAN Shen,MA Ling-Ling,LUO Min,LIU Wei-Hua,XU Dian-Dou.Chinese J.Anal.Chem.,2016,44(5):698-706邵阳,杨国胜,韩深,马玲玲,罗敏,刘韦华,徐殿斗.分析化学,2016,44(5):698-706
19 GB 2762-2017.National Food Safety Standard.Determination of Indicator Polychlorinated Biphenyls in Foods.National Standard of the People's Republic of China GB 2762-2017,食品安全国家标准:食品中指示性多氯联苯含量的测定,中华人民共和国国家标准
20 LI Jing-Guang,ZHAO Yun-Feng,WU Yong-Ning.Chinese J.Anal.Chem.,2005,33(9):1223-1226李敬光,赵云峰,吴永宁.分析化学,2005,33(9):1223-1226
2 Nieminen P,Lehtiniemi H,Huusko A,Vhkangas K,Rautio A.Chemosphere,2013,91(2):131-138
3 Afful S,Awudza J A,Twumasi S K,Osae S.Chemosphere,2013,93(8):1556-1560
4 GB 13078-2001.Hygienical Standard for Feeds.National Standard of the People's Republic of China GB 13078-2001.饲料卫生标准.中华人民共和国国家标准
5 Kim M,Kim S,Yun S,Lee M,Cho B,Park J,Son S,Kim O.Chemosphere,2004,54(10):1533-1538
6 Zhu Q,Zheng M,Liu G,Zhang X,Dong S,Gao L,Liang Y.Environ.Sci.Pollut.Res.,2016,24(2):1-8
7 Yang J S,Lee D W,Lim H.J.Liquid Chromatogr.Related Technol.,2003,26(5):803-818
8 Kim L,Jeon J W,Son J Y,Park M K,Kim C S,Jeon H J,Nam T H,Kim K,Park B J,Choi S D,Lee S E.Environ.Geochem.Health,2017,39(2):1-13
9 Baqar M,Sadef Y,Ahmad SR,Mahmood A,Qadir A,Aslam I,Li J,Zhang G.Environ.Sci.Pollut.Res.Inter.,2017,24(1-3):1-18
10 Olanca B,Cakirogullari G C,Ucar Y,Kirisik D,Kilic D.Chemosphere,2014,94(1):13-19
11 Ahmadkhaniha R,Nodehi R N,Rastkari N,Aghamirloo H M.J.Environ.Health Sci.Engineer.,2017,15(1):15-21
12 Stancheva M,Georgieva S,Makedonski L.Food Control,2016,72:205-210
13 Sporring S,Bj9rklund E.J.Chromatogr.A,2004,1040(2):155-161
14 Fernández-González R,Yebra-Pimentel I,Martínez-Carballo E,Regueiro J,Simal-Gándara J.Food Chem.,2013,140(1-2):296-304
15 SONG Zi-Liang,LI Fu-Er,WANG Yong,RILEY William,TANG Shu-Ze.Guangdong Agricultural Sciences,2012,39(21):122-125宋梓亮,李福儿,汪勇,Riley William,唐书泽.广东农业科学,2012,39(21):122-125
16 Sun H Z,Wang P,Li H H,Li Y M,Zheng S C,Matsiko J,Hao Y F,Zhang W W,Wang D,Zhang Q H.Sci.China Chem.,2017,60(5):670-677
17 HU Hong-Mei,GUO Yuan-Ming,HAO Qing,SUN Xiu-Mei,JIN Yan-Jian,ZHONG Zhi,LI Tie-Jun.Chinese J.Anal.Chem.,2016,44(1):88-94胡红美,郭远明,郝青,孙秀梅,金衍健,钟志,李铁军.分析化学,2016,44(1):88-94
18 SHAO Yang,YANG Guo-Sheng,HAN Shen,MA Ling-Ling,LUO Min,LIU Wei-Hua,XU Dian-Dou.Chinese J.Anal.Chem.,2016,44(5):698-706邵阳,杨国胜,韩深,马玲玲,罗敏,刘韦华,徐殿斗.分析化学,2016,44(5):698-706
19 GB 2762-2017.National Food Safety Standard.Determination of Indicator Polychlorinated Biphenyls in Foods.National Standard of the People's Republic of China GB 2762-2017,食品安全国家标准:食品中指示性多氯联苯含量的测定,中华人民共和国国家标准
20 LI Jing-Guang,ZHAO Yun-Feng,WU Yong-Ning.Chinese J.Anal.Chem.,2005,33(9):1223-1226李敬光,赵云峰,吴永宁.分析化学,2005,33(9):1223-1226