Enantiomeric analysis of polycyclic musks AHTN and HHCB and HHCB-lactone in sewage sludge by gas chromatography/tandem mass spectrometry.
Enantiomeric analysis of polycyclic musks AHTN and HHCB and HHCB-lactone in sewage sludge by gas chromatography/tandem mass spectrometry.
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DOI：
10.1002/rcm.8390
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发表时间：
2019-03
期刊：
影响因子：
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通讯作者：
Shutao Gao;Boyang Tian;Xiangying Zeng;Zhiqiang Yu
中科院分区：
文献类型：
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作者：
Shutao Gao;Boyang Tian;Xiangying Zeng;Zhiqiang Yu
手性化合物的对映选择性分析是一种有趣且具有挑战性的技术，用于阐明这些化合物的降解/转化机制或了解其环境过程。在这项研究中，我们已经开发了一种有效的分离和检测方法的对映体分析的AHTN和HHCB，以及转化产物的HHCB（HHCB-内酯），在污泥样品。方法采用气相色谱-串联质谱（GC/MS/MS）联用技术，以环糊精为对映体，对映体选择性色谱柱进行分离。优化了GC烘箱温度梯度、氦气载气的线速度以及MS/MS参数，包括定量和定性离子对、停留时间和碰撞能量，以实现所有目标对映体的良好分离和高灵敏度。结果所有目标对映体均得到基线分离。所有对映异构体的定量限（LOQ）范围为0.010 - 0.045 μg/L，所有单一对映异构体的校准线性均高于0.99。AHTN、HHCB和HHCB-内酯的所有单一对映异构体的日内和日间精密度范围分别为0.8 - 3.8%和4.2 - 8.3%。结论：通过对17个污水处理厂污泥样品中AHTN、HHCB和HHCB-内酯的对映体选择性分析，完全验证了所开发的方法。污泥样品中HHCB和HHCB-内酯的对映体分数（EF）明显偏离0.50，表明HHCB具有显著的对映体选择性转化，优先降解4S对映体。污泥样品中cis-HHCB对映体和cis-HHCB-内酯对映体的EF值之间存在显著的正相关性，表明HHCB降解转化为HHCB-内酯的机理仍需进一步研究。
RATIONALE Enantioselective analysis of chiral compounds is an interesting and challenging technique used to elucidate the degradation/transformation mechanisms of these compounds or understand their environmental processes. In this study, we have developed an effective separation and detection approach for the enantiomeric analysis of AHTN and HHCB, as well as a transformation product of HHCB (HHCB-lactone), in sludge samples. METHODS The analytical method was developed using a cyclodextrin-based enantioselective gas chromatography column combined with tandem mass spectrometry (GC/MS/MS). The GC oven temperature gradients, the linear velocity of the helium carrier gas, as well as the MS/MS parameters, including quantitative and qualitative ion pairs, dwell times, and collision energies, were optimized to achieve good separation and high sensitivity for all target enantiomers. RESULTS Baseline separations of all target enantiomers were observed. Limits of quantification (LOQs) for all enantiomers ranged from 0.010 to 0.045 μg/L, and calibration linearity for all single enantiomers was higher than 0.99. The intra-day and inter-day precisions for all single enantiomers of AHTN, HHCB, and HHCB-lactone ranged from 0.8 to 3.8% and from 4.2 to 8.3%, respectively. CONCLUSIONS The developed method was fully validated through enantioselective analyses of AHTN, HHCB, and HHCB-lactone in sludge samples collected from 17 WWTPs. The enantiomeric fractions (EFs) of HHCB and HHCB-lactone in sludge samples distinctly deviated from 0.50, indicating a significant enantioselective transformation of HHCB with preferential degradation of the 4S enantiomers. Significant positive correlations were found between the EF values of cis-HHCB enantiomers and cis-HHCB-lactone enantiomers in the sludge samples, implying that further efforts are still needed to clarify the degradation/transformation mechanism from HHCB to HHCB-lactone.