IMDEA-Water (Madrid Institute for Advanced Studies-Water), Punto Net, Edificio ZYE 2º, Parque Científico Tecnológico, Madrid, Spain.
Rapid Commun Mass Spectrom. 2013 Jun 15;27(11):1237-50. doi: 10.1002/rcm.6575.
Polycyclic musks have become a concern due to their bioaccumulation potential and ecotoxicological effects. The HHCB transformation product (TP) (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta[γ]-2-benzopyran; HHCB-lactone) is the most stable intermediate generated and it is frequently detected in river waters. The aim of this work was the identification of relevant TPs generated from UV irradiation and ozone treatments.
Identification of HHCB TPs was carried out by liquid chromatography/hybrid quadrupole time-of-flight mass spectrometry (LC/ESI-QTOF-MS) and two-dimensional gas chromatography/electron impact time-of-flight mass spectrometry (GC×GC-EI-TOF-MS). With LC/ESI-QTOF-MS, TPs were characterized by means of mass accuracy in both full-scan and MS/MS modes through information-dependent acquisition (IDA) and direct injection on-column. With stir bar sorptive extraction (SBSE)-GC×GC-EI-TOF-MS, identification was based on the enhanced separation capacity and screening of unknowns through the acquisition of full-range mass spectra.
The effectiveness of these complementary techniques allowed a detailed evaluation of the main TPs. Eighteen TPs were elucidated based on mass accuracy, in both full-scan and MS/MS modes using LC/ESI-QTOF-MS with mass errors below 5 ppm and 10 ppm (mostly), respectively. Most of the TPs had not been analytically identified in previous studies. Separation of the enantiomeric species (R) and (S) of HHCB-lactone, and the identification of other relevant TPs, was performed using SBSE-GC×GC-EI-TOF-MS.
LC/ESI-QTOF-MS and GC×GC-EI-TOF-MS analysis provides the best alternative for TP identification of chemicals of concern, which have a wide range of polarities and isobaric compounds. A prediction of PBT (persistence, bioaccumulation and toxicity) using the PBT Profiler program suggested a classification of 'very persistent' and 'very toxic' for most of the TPs identified.
多环麝香由于其生物累积潜力和生态毒理学效应而受到关注。HHCB 的转化产物 (TP)（1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基-环戊[γ]-2-苯并吡喃；HHCB-内酯）是生成的最稳定的中间体，并且经常在河水中检测到。本工作的目的是鉴定由紫外线辐照和臭氧处理生成的相关 TP。
通过液相色谱/混合四极杆飞行时间质谱 (LC/ESI-QTOF-MS) 和二维气相色谱/电子轰击飞行时间质谱 (GC×GC-EI-TOF-MS) 对 HHCB TP 进行鉴定。使用 LC/ESI-QTOF-MS，通过信息依赖性采集 (IDA) 和直接在线进样，在全扫描和 MS/MS 模式下通过质量精度对 TP 进行了表征。使用搅拌棒吸附萃取 (SBSE)-GC×GC-EI-TOF-MS，通过全范围质谱的获取和未知物的筛选，基于增强的分离能力进行鉴定。
这些互补技术的有效性允许对主要 TP 进行详细评估。基于质量精度，通过 LC/ESI-QTOF-MS 在全扫描和 MS/MS 模式下鉴定了 18 个 TP，使用 LC/ESI-QTOF-MS 时的质量误差分别低于 5 ppm 和 10 ppm（大多数）。大多数 TP 在以前的研究中尚未进行分析鉴定。使用 SBSE-GC×GC-EI-TOF-MS 分离 HHCB-内酯的对映异构体 (R) 和 (S)，并鉴定其他相关 TP。
LC/ESI-QTOF-MS 和 GC×GC-EI-TOF-MS 分析为极性范围广泛和同系物化合物的关注化学物质 TP 鉴定提供了最佳选择。使用 PBT 分析器程序对持久性、生物累积性和毒性 (PBT) 进行预测，结果表明大多数鉴定的 TP 被归类为“极持久”和“极毒”。
