改进QuEChERS-浓H_2SO_4净化-气相色谱/质谱联用检测贝类中多溴联苯醚

Determination of Polybrominated Diphenyl Ethers in Shellfish by Improved QuEChERS-Concentrated Sulfuric Acid Cleaned Up-Gas Chromatography-Mass Spectrometry

本研究建立了贝类中8种指示性多溴联苯醚BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183和BDE-209的气相色谱/质谱联用检测方法。样品经正己烷-丙酮(1∶1,V/V)提取,采用改进的QuEChERS技术EMR-Lipid净化粉及浓H_2SO_4氧化净化。色谱选用短柱长、薄液膜的DB-5MS毛细管柱(15m×0.25mm×0.10μm),质谱以选择离子模式(SIM)监测,内标法定量,实现了贝类样品中低溴代及高溴代联苯醚的同时快速定性和定量分析。结果表明,8种目标多溴联苯醚类的检出限(LOD,S/N>3)除BDE-209为1.0μg/kg,其余为0.1μg/kg,定量限(LOQ,S/N>10)除BDE-209为3.0μg/kg,其余为0.3μg/kg;三个不同浓度的加标回收率在90.0%~120%之间,相对标准偏差皆小于10%。该方法的准确度和灵敏度较高,重现性好,且操作简便、高效,适合于贝类样品中多溴联苯醚类残留的同时检测。

A method for determination of residues of polybrominated biphenyl ethers（PBDEs）in shellfish was developed by gas chromatography-mass spectrometry（GC-MS）.Eight kinds of PBDEs（BDE-28,BDE-47,BDE-99,BDE-100,BDE-153,BDE-154,BDE-183 and BDE-209）were selected as target analytes.The efficient pretreatment method was applied,consisting of extraction with blended solution of hexane and acetone,cleaned-up by improved QuEChERS with EMR-Lipid,followed by purification with concentrated sulfuric acid.Qualitative and quantitative GC-MS analysis of eight PBDEs in shellfish were carried out by internal standard method.Moreover,the DB-5 MS coloum（15 m×0.25 mm×0.10μm）with thin liquid film was selected for fast analysis of PBDEs at the same time.The results showed that the limits of detection for eight kinds of PBDEs in shellfish were 0.1μg/kg（S/N〉3,1.0μg/kg for BDE-209）,and the limits of quantification were 0.3μg/kg（S/N〉10,3.0μg/kg for BDE-209）.The average spiked recoveries of eight kinds of PBDEs at three concentrations were between 90%and 120%,with relative standard deviations less than 10%.The method was accurate,sensitive,reproducible and efficient for analysis of PBDEs residues in shellfish samples.