加速溶剂萃取-同步净化/气相色谱-质谱法检测沉积物中4种新型溴代阻燃剂

Determination of Four Kinds of Novel Brominated Flame Retardants in Sediments by Gas Chromatography- Mass Spectrometry Combined with Accelerated Solvent Extraction- Synchronous Purification

摘要：建立了同时测定沉积物中2-乙基己基．四溴苯甲酸（TBB）、1，2-二（2，4，6-三溴苯氧基）乙烷（BTB-PE）、2，3，4，5-四溴．苯二羧酸双（2-乙基己基）酯（TBPH）及十溴二苯乙烷（DBDPE）4种新型溴代阻燃剂的加速溶剂萃取-同步净化／气相色谱-质谱分析方法。冷冻干燥后的环境沉积物样品经改进后的加速溶剂萃取（ASE）并净化后，浓缩液过Florisil固相萃取小柱，用4mL正已烷和二氯甲烷分步洗脱，氮吹定容后用气相色谱-质谱（Gc—Ms）检测。结果表明，4种溴代阻燃剂的线性范围为2～1000μg·L^-1（其中DBDPE为20～10000μg·L^-1），相关系数均大于0．995，定量下限（S／N≥10）为0．074～44．4斗g·kg^-1；在2，10μg·L^-1两个加标水平下的方法回收率为79．5％-119．7％，相对标准偏差为2．6％～15．3％。采用本方法对上海市主要水体中6个河流段采样点沉积物中的4种新型溴代阻燃剂进行检测，除1个采样点未检出TBB外，其余采样点均检出4种新型溴代阻燃剂。该方法简便、快速、灵敏度高、定性定量准确，满足沉积物中新型溴代阻燃剂的检测要求。

A simple method based on accelerated solvent extraction （ASE） /solid phase extraction （ SPE ） coupled with gas chromatography - mass spectrometry （ GC - MS） was developed for the simul- taneous determination of 2-ethylhexyl-2, 3, 4, 5-tetrabromobenzoate （TBB） , 1, 2-bis （2, 4, 6- tribromophenoxy） ethane （ BTBPE ）, bis （ 2-ethylhexyl ） 2, 3, 4, 5-tetrabromophthalate （ TBPH ） and decabromodiphenylethane（DBDPE） in sediments. Extraction and cleanup of four novel bromina- ted flame retardants in lyophilized sediments were performed by improved accelerated solvent extrac- tion （ASE）, and the concentrated solution was cleanup using Florisil solid phase extraction cartridges with 4 mL hexane, then eluted with 4 mL dichloromethane. The eluents was concentrated under a gentle N2 stream and analyzed by GC -MS. The calibration curves were linear in the range of 20 - 10 000 μg ·L^-1 for DBDPE, and 2 - 1 000 μg ·L^-1 for the rest of compounds, with correlation co- efficients more than 0. 995. The instrumental limits of quantitation（ S/N〉 10） for target compounds were in the range of 0. 074 - 44. 4 μg ·L^-1.The average recoveries of target compounds at two spiked levels（2, 10μg ·L^-1 ） were in the range of 79.5% - 119.7% , with relative standard devia- tions（RSDs） of 2. 6% - 15.3%. The proposed method was applied in the determination of four no- vel brominated flame retardants in sediments at six different sediments sampling sites from principalwatersheds of Shanghai. All samples were detected to be contain TBB, BTBPE, TBPH and DB- DPE, except one sampling site without TBB. The method was simple and sensitive, and could meet the requirements for rapid and accurate determination of four novel brominated flame retardants.