气质联用测定胶州湾北岸潮间带底泥中的新型溴代阻燃剂

Determination of new brominated flame retardants in the North shore of jiaozhou bay intertidal sediments by gas chromatography mass spectrometry

本文利用索式提取和复合硅胶层析柱净化技术对底泥样品进行前处理,以BDE30、PCB209L为回收率添加标,以BDE118为进样内标,采用气相色谱质谱联用仪(GC-MS)对胶州湾北岸潮间带底泥中的7种非多溴联苯醚(non-PBDE)类溴代阻燃剂(1,3,5-三溴苯(TBB)、2,3,5,6-四溴对二甲苯(p TBX)、五溴甲苯(PBT)、三溴苯乙烯(PBEB)、六溴苯(HBB)、六氯二溴辛烷(HCDBCO)、2,2',4,4',5,5'-六溴联苯(BB153))进行分析.结果表明:各化合物的仪器检出限在0.03—0.59 ng·g-1之间、定量限在0.09—1.96 ng·g-1之间;底泥中各化合物的加标回收率在80%—107%之间;回收率添加标BDE30和PCB209L的回收率分别为80%—95%和85%—105%.实验中实际检出5种non-PBDE类溴代阻燃剂(TBB、PBT、PBEB、HBB、HCDBCO),其含量在0.13—0.96 ng·g-1(干重)之间.Non-PBDE类溴代阻燃剂进行主成分分析和相关性分析表明:PBEB和HCDBCO是底泥中的两大主要成分,具有相似的源-水体-底泥转化效率.TBB与其他溴代阻燃剂呈现负相关,相关系数为-0.130—-0.461;PBEB与HBB的相关系数r为0.813(α=0.05),可能来源于同一种溴代阻燃剂的降解.

In this study, sediment samples from the north shore of Jiaozhou Bay were extracted by Soxhlet extraction and cleaned by composite silica gel column. BDE30 and PCB209L were added as surrogate compounds, and BDE118 was used as internal standard. Seven new brominated flame retardants （non-polybrominated diphenyls ethers, non-PBDE）, including TBB, pTBX, PBT, PBEB, HBB, HCDBCO and BB153, were analyzed by gas chromatography mass spectrometry （GC-MS）. The results showed that the detection limit varied from 0.03 to 0.59 ng·g^-1 and the quantitative limit ranged from 0.09 to 1.96 ng·g^-1. Moreover, the average recoveries of the spiked compounds in the sediments were in the range of 80% to 107%, and the recoveries of BDE30 and PCB209L were 80%-95%, 85%-105%, respectively. Five kinds of non-PBDE brominated flame retardants （TBB, PBT, PBEB, HBB, HCDBCO） were detected, and the concentration ranged from 0.13 to 0.96 ng·g^-1 （dry weight）. Principal component analysis and Pearson correlation analysis suggested that PBEB and HCDBCO were two main components, and have similar sources-water-sediment transformation efficiency. There were negative correlations between TBB and other non-PBDE BFRs correlation coefficients from-0.130 to-0.461. PBEB and HBB may have come the degradation of same brominated flame retardant, as the correlation coefficients was 0.813 （α=0.05）.