Determination of ten hexabromocyclododecane diastereoisomers using two coupled reversed-phase columns and liquid chromatography/tandem mass spectrometry.
Determination of ten hexabromocyclododecane diastereoisomers using two coupled reversed-phase columns and liquid chromatography/tandem mass spectrometry.
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DOI：
10.1002/rcm.6922
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发表时间：
2014-07
期刊：
影响因子：
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通讯作者：
Qian Han;Han Song;Shutao Gao;Xiangying Zeng;Zhiqiang Yu;Yunjiang Yu;G. Sheng;Jia-mo Fu
中科院分区：
文献类型：
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作者：
Qian Han;Han Song;Shutao Gao;Xiangying Zeng;Zhiqiang Yu;Yunjiang Yu;G. Sheng;Jia-mo Fu
六溴环十二烷（HBCD）由于其潜在的持久性、生物累积性和毒性而引起关注。除了广泛报道的α-、β-、γ-六溴环十二烷异构体外，最近还在环境介质和生物群中发现了δ-六溴环十二烷等其他六溴环十二烷非对映异构体。这些新报告的非对映异构体可能会让我们更深入地了解六溴环十二烷的降解和生物转化。方法采用反相C18柱与C8柱联用，提高色谱分离度。优化了甲醇、乙腈和水组成的梯度移动的流动相以及串联质谱参数。采用液相色谱/串联质谱法，在多反应监测模式下，采用负电喷雾电离，最终确定了10种六溴环十二烷非对映异构体。结果10种六溴环十二烷中有8种可在反相色谱柱上分离。方法验证结果表明，重现性高，灵敏度好。方法的检出限为0.4 ~ 0.8 pg，日内和日间进样的相对标准偏差分别为1.8 ~ 5.1%和2.7 ~ 9.5%。所开发的方法进一步应用于六溴环十二烷商业产品和土壤样品中六溴环十二烷的分析。在商业产品和土壤样本中检测到δ-、η-、θ-和ε-六溴环十二烷。结论：本研究表明，δ-、η-、θ-和ε-六溴环十二烷可能普遍存在于环境介质和生物群中。这些新报告的非对映异构体可能有助于我们更好地了解六溴环十二烷在环境中的归宿和转化。
RATIONALE Hexabromocyclododecanes (HBCDs) are raising concern due to their potential persistence, bioaccumulation and toxicity. Apart from the widely reported isomers α-, β-, γ-HBCD, other HBCD diastereoisomers such as δ-HBCD have been also recently found in environmental media and biota. These newly reported diastereoisomers might give more insight into the degradation and biotransformation of HBCDs. METHODS A reversed-phase C18 column coupled to a C8 column was used to improve the chromatographic resolution. A gradient mobile phase consisting of methanol, acetonitrile, and water, as well as tandem mass spectrometry parameters, were optimized. Ten HBCD diastereoisomers were finally determined by liquid chromatography/tandem mass spectrometry in multiple reaction monitoring mode with negative electrospray ionization. RESULTS Eight of the ten HBCDs could be chromatographically separated by using the coupled reversed-phase columns. Results of the method validation indicate high reproducibility and good sensitivity. The limit of detection ranged from 0.4 to 0.8 pg, and the relative standard deviations of intra- and inter-day injections ranged from 1.8 to 5.1% and from 2.7 to 9.5%, respectively. The developed method was further applied to the analysis of HBCDs in HBCD commercial products and soil samples. δ-, η-, θ-, and ε-HBCD were detected in commercial products and soil samples. CONCLUSIONS The present study revealed that δ-, η-, θ-, and ε-HBCD might occur ubiquitously in environmental media and biota. These newly reported diastereoisomers may help us to better understand the fate and transformation of HBCDs in the environment.