摘要
目的:建立同时测定地龙中25个多溴二苯醚(PBDEs)和5个新兴溴代阻燃剂(eBFRs)的方法,并对15批市售地龙进行溴代阻燃剂残留测定。方法:地龙样品粉末2.0 g用70 mL正己烷-二氯甲烷(1∶1,v/v)超声提取后,12 g的50%硫酸硅胶净化过夜,上清液浓缩至约1~2 mL,复合硅胶柱固相萃取,正己烷-二氯甲烷(1∶1,v/v)洗脱,浓缩近干,200μL内标溶液复溶后,采用脉冲不分流进样GC-NCI-MS内标法测定。使用安捷伦DB-5MS毛细管色谱柱(15 m×0.25 mm,0.1μm)程序升温分离,载气为高纯氦气,流速1.0 mL·min^-1,进样口、传输线、离子源温度分别设置为290、300、230℃;采用负离子选择离子检测模式,反应气为甲烷。结果:30个化合物的线性关系良好,相关系数r均大于0.9996,检测下限为0.1~13 ng·kg^-1,定量下限为0.3~42 ng·kg^-1,低中高加标水平下平均回收率在68.9%~119.1%之间,RSD为2.2%~11.3%,内标BDE-77和BDE-118的提取回收率分别为83.4%~102.0%和84.4%~97.0%。15批地龙样品均检出PBDEs和eBFRs,其中以十溴二苯醚(BDE-209)和十溴二苯乙烷(DBDPE)含量最高,分别为92.5~875.1 ng·kg^-1和84.3~2042.8 ng·kg^-1。结论:该方法准确、灵敏、可靠,可同时测定地龙中30个溴代阻燃剂,中药材的质量控制应关注持久性有机污染物的污染。
Objective:To develop a method for the simultaneous determination of 25 polybrominated flame retardants(PBDEs) and 5 new emerging brominated flame retardants(e BFRs) in Dilong,and to apply the established method in determination of flame retardants residues in 15 batches of Dilong from the markets. Methods:2.0 g of the powdered Dilong sample was extracted by ultrasonic method with 70 mL of n-hexane-dichloromethane mixture(1∶1,v/v)and digested by 12 g of 50% sulfuric acid silica gel overnight. Then the supernatant was concentrated to 1-2 mL and purified by solid-phase extraction with a composite silica gel column using n-hexanedichloromethane mixture(1∶1,v/v) as the elution. The eluent was concentrated nearly to dry,reconstituted with 200 μL of the internal reference standard solution,and then analyzed by GC-NCI-MS using pulsed split-less mode,and internal standard method. The separation was carried on an Agilent DB-5 MS capillary column(15 m×0.25 mm,0.1 μm) with a temperature program. The carrier gas was high-purity helium,the flow rate was 1.0 mL·min^-1,and the temperature of sample inlet,transmission lines and ion source was set at 290,300 and 230 ℃,respectively. The mass spectrometer was operated in negative selected ion monitoring(SIM) mode,and the reaction gas was methane. Results:Good linear calibration curves were obtained for the 30 compounds with the correlation coefficients all above 0.999 6. The detection limits of the method were between 0.1 and 13 ng·kg^-1,and the quantitative limits were between 0.3 and 42 ng·kg^-1. The average recoveries ranged from 68.9% to 119.1%,with RSD between 2.2% and 11.3% at low,medium and high standard addition levels. The recoveries of internal standard BDE-77 and BDE-118 were from 83.4% to 102.0% and from 84.4% to 97.0%,respectively. The determination results of 15 batches Dilong showed that PBDEs and eBFRs were detected in all the samples,among which BDE-209 and DBDPE were the predominant congeners with the contents of 92.5-875.1 ng·kg^-1 and 84.3-2 042.8 ng·kg^-1,respectively. Conclusion:The established method is accurate,sensitive and reliable. It can be used for the simultaneous determination of 30 brominated flame retardants in Dilong. Attentions should be paid to the persistent organic pollutants in Chinese medicinal materials.
作者
孙晶
杭太俊
谭力
冯有龙
胡浩彬
李珂瑜
王沁怡
曹玲
杨功俊
SUN Jing;HANG Tai-jun;TAN Li;FENG You-long;HU Hao-bin;LI Ke-yu;WANG Qing-yi;CAO Ling;YANG Gong-jun(School of Pharmacy,China Pharmaceutical University,Nanjing 211198,China;Jiangsu Institute for Food and Drug Control,Nanjing 210019,China)
出处
《药物分析杂志》
CAS
CSCD
北大核心
2020年第8期1425-1436,共12页
Chinese Journal of Pharmaceutical Analysis
基金
江苏省高层次卫生人才“六个一工程”拔尖人才项目(LGY2018101)。
关键词
持久性有机污染物
溴代阻燃剂
多溴二苯醚
十溴二苯乙烷
地龙
中药材
persistent organic pollutants
brominated flame retardants
polybrominated diphenyl ethers
decabromodiphenyl ethane
Dilong
Chinese medicinal materials
