摘要
建立了高效液相色谱-四极杆/静电场轨道阱高分辨质谱对水产品中污染物的非定向快速筛查与测定的方法。筛查时样品用乙腈提取、氮气浓缩吹干、甲醇-水溶液定容,采用全扫描数据依赖二级扫描模式进样分析。利用Trace Finder软件对水产样品中未知污染物的精确质量数、同位素丰度比、二级碎片离子进行数据库检索匹配。定量时样品采用优化的QuEChERS方法净化,对筛查过程确认的三环唑、咖啡因和乙氧基喹啉3种污染物进行目标离子二级扫描模式定量分析。鱼和虾中3种化合物在5～1 000μg/L范围内线性关系良好,相关系数均大于0. 99;方法检出限(LOD)为1μg/kg,定量限(LOQ)为5μg/kg,平均回收率为70. 5～90. 9%,相对标准偏差为5. 4%～12. 8%。筛查方法具有快速、准确、高通量等优点,结合定量方法能够用于实际水产品中未知污染物的筛查与测定。
A method has been developed for rapid untargeted screening and determination of unknown contaminants in aquatic products by high performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry. The samples were extracted by acetonitrile,dried under nitrogen,dissolved in methanol-water( 3 ∶ 7,v/v),and analyzed via the full MS scan/data dependent MS2 mode during the screening process. The Trace Finder software was used to match the precise mass,the isotope abundance ratio,the fragment ion to search for unknown contaminants in aquatic samples. The optimized QuEChERS method is used to purify the samples when quantifying. The quantitative analyses of triazole,caffeine,and ethoxyquinoline were performed via the target-MS2 mode. The correlation coefficients of the three compounds in fish and shrimp samples were higher than 0. 99 in the linear range of 5-1 000 μg/L. The limit of detection was 1 μg/kg,and the limit of quantitation was 5 μg/kg. The average recoveries were between 70. 5% and 90. 9% with the relative standard deviations ranging from 5. 4% to 12. 8%. The screening method has the advantages of fast,accurate,and high throughput; when combined with the quantitative method,it can be used to screen and determine unknown contaminants in the actual aquatic products.
引文
[1] Zhang H,Sun C. Research of Agricultural Modernization,2009,30(4):430张欢,孙琛.农业现代化研究,2009,30(4):430
[2] Zhao L,Geng R,Ouyang H Y. World Agriculture,2015(5):121赵蕾,耿瑞,欧阳海鹰.世界农业,2015(5):121
[3] Yang X L,Guo W W,Sun Q. Chinese Fishery Quality and Standards,2013,3(4):1杨先乐,郭微微,孙琪.中国渔业质量与标准,2013,3(4):1
[4] China Food and Drug Administration. Notice of the General Administratio n o n Special Inspectio n Results o f Key Aquatic Pro ducts in Operatio n(No. 34 o f 2017).(2017-02-24)[2017-02-25]. http://new s.fo o dmate.net/2017/02/418886.html国家食药监总局.总局关于经营环节重点水产品专项检查结果的通告(2017年第34号).(2017-02-24)[2017-02-25]. http://new s.fo o dmate.net/2017/02/418886.html
[5] China Food and Drug Administration. Notice of the General Administratio n o n Mo nito ring Results o f fresh Aquatic Pro ducts in Operatio n(No. 176 o f 2017).(2017-11-02)[2017-11-09]. http://new s.fo o dmate.net/2017/11/449104.html国家食品药品监督管理总局.总局关于经营环节鲜活水产品抽检监测结果的通告(2017年第176号).(2017-11-02)[2017-11-09]. http://new s.fo o dmate.net/2017/11/449104.html
[6] Chen S J,Li L H,Yang X Q,et al. Journal of Food Science,2015,36(17):300陈胜军,李来好,杨贤庆,等.食品科学,2015,36(17):300
[7] Song C,Hu G D,Meng S L,et al. Journal of Agriculture,2017,7(9):58宋超,胡庚东,孟顺龙,等.农学学报,2017,7(9):58
[8] LüX M. Environmental Monitoring in China,2012,28(4):118吕小明.中国环境监测,2012,28(4):118
[9] Zhou X J,Chen Y,Yang S J,et al. Chinese Journal of Chromato graphy,2017,35(8):787周秀锦,陈宇,杨赛军,等.色谱,2017,35(8):787
[10] Xu Y Y,Zhang D,Qiu J,et al. Journal of Quality and Safety o f Agro-Pro ducts,2016(5):13许彦阳,张丹,邱静,等.农产品质量与安全,2016(5):13
[11] Wu B,Ding T,Liu H,et al. Chinese Journal of Chromatography,2012,30(12):1246吴斌,丁涛,柳菡,等.色谱,2012,30(12):1246
[12] Krauss M,Singer H,Hollender J. Anal Bioanal Chem,2010,397(3):943
[13] Ondarza P M,Gonzalez M,Fillmann G,et al. Chemosphere,2014,94(1):135
[14] Chiesa L M,Labella G F,Panseri S,et al. Chemosphere,2016,153:162
[15] Nacher-Mestre J,Serrano R,Portoles T,et al. J Agric Food Chem,2014,62(10):2165
[16] Tengstrand E,Rosén J,Hellenas K E,et al. Anal Bioanal Chem,2013,405(4):1237
[17] Shi Y F,Cai Y Q,Yu H J,et al. Chinese Journal of Analytical Chemistry,2014,42(11):1640史永富,蔡友琼,于慧娟,等.分析化学,2014,42(11):1640
[18] Mao T,Lu Y,Jiang J,et al. Journal of Food Science,2016,37(5):245毛婷,路勇,姜洁,等.食品科学,2016,37(5):245
[19] Meng D,Tan Z J,Liu Y T,et al. Chinese Agricultural Science Bulletin,2015,31(14):56孟娣,谭志军,刘永涛,等.中国农学通报,2015,31(14):56
[20] Zhang P W,Zhou H D,Zhao G F,et al. Environmental Science,2016,37(9):3348张盼伟,周怀东,赵高峰,等.环境科学,2016,37(9):3348
[21] Zhang P W,Zhou H D,Zhao G F,et al. Environmental Science,2017,38(5):1852张盼伟,周怀东,赵高峰,等.环境科学,2017,38(5):1852
[22] GB 2763-2016
