High-resolution Mass Spectrometry Recognized Tetrabromobisphenol A bis (2,3-dibromo-2-methylpropyl ether) (TBBPA-DBMPE) as a Contaminant in Sediment from a Flame Retardant Manufacturing Factory

IF 11.4 1区环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL

Water Research Pub Date : 2025-05-04 DOI:10.1016/j.watres.2025.123783

Hao Sun, Langjie Ye, Mengkai Yang, Guanyong Su

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Abstract

Information on contamination status of tetrabromobisphenol, and triazine-based novel brominated flame retardants (NBFRs) in sediment environment is very rare. Here, by use of high performance liquid chromatography coupled with quadrupole orbitrap mass spectrometry (HPLC-Q-Orbitrap/MS), we developed an analytical method for determination of three tetrabromobisphenol, and two triazine-based FRs in sediment samples. By applying this method for analysis of n=6 sediment samples from a flame retardant manufacturing factory, we observed that total concentrations of 6 NBFRs (∑₆NBFRs) ranged from 7.46 to 1020 ng/g dry weight (dw), which were comparable to those (3.83-820 ng/g dw) of n=11 sediment samples from e-waste recycling area. Both of them were statistically significantly (p < 0.001, one-way ANOVA) higher than those in n=10 sediment samples from Taihu Lake (1.22-8.22 ng/g dw). With an aim to find novel tetrabromobisphenol, and triazine-based compounds, we further investigated the ionization characteristics and the fragmentation patterns in ionization source of six target NBFRs. We observed that debromination, ether bond breakage, and the breakage of inter-benzene ring C-C and C-S bonds were the main in-source fragmentation pathways for TBBPA/S derivatives. On the basis of the observed ionization characteristics and an in-house suspect screening list, we tentatively identified 71 NBFR formulas, of which ten TBBPA/S derivatives and one triazine-based BFRs were found for the first time in sediments. Among these NBFR formulas, tetrabromobisphenol A bis (2,3-dibromo-2-methylpropyl ether) (TBBPA-DBMPE) is high of concern due to its male reproductive toxicity according to a recent study, and fully confirmed by comparing unique LC and HRMS characteristics of sediment sample with authentic standard. The work probably provides an opportunity for the structural identification of unknown TBBPA/S derivatives in environmental samples, and reports the occurrence of TBBPA-DBMPE in real environment.

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高分辨率质谱法鉴定出四溴双酚A双（2,3-二溴-2-甲基丙基醚）（TBBPA-DBMPE）是阻燃剂制造厂沉积物中的污染物

关于四溴双酚和三嗪基新型溴化阻燃剂在沉积物环境中的污染状况的资料非常少。本文采用高效液相色谱-四极杆轨道阱质谱联用技术（HPLC-Q-Orbitrap/MS），建立了沉积物样品中3种四溴双酚和2种三嗪类FRs的分析方法。将该方法应用于某阻燃剂制造厂n=6个沉积物样品的分析，发现6个NBFRs（∑6NBFRs）的总浓度为7.46 ~ 1020 ng/g干重（dw），与电子垃圾回收区n=11个沉积物样品的浓度（3.83 ~ 820 ng/g dw）相当。两组差异均有统计学意义(p <；0.001（单因素方差分析），高于太湖n=10个沉积物样品（1.22 ~ 8.22 ng/g dw）。为了寻找新的四溴双酚和三嗪基化合物，我们进一步研究了六种靶NBFRs的电离特性和电离源的碎片化模式。我们发现脱溴、醚键断裂、苯环间C-C和C-S键断裂是TBBPA/S衍生物的主要源内断裂途径。根据观察到的电离特性和内部可疑筛选列表，初步确定了71种NBFR配方，其中10种TBBPA/S衍生物和1种三嗪基bbfr为首次在沉积物中发现。在这些NBFR配方中，四溴双酚A双（2,3-二溴-2-甲基丙基醚）（TBBPA-DBMPE）因其男性生殖毒性而受到高度关注，并通过将沉积物样品的独特LC和HRMS特征与真实标准进行比较得到充分证实。该工作可能为环境样品中未知TBBPA/S衍生物的结构鉴定提供了机会，并报道了TBBPA- dbmpe在真实环境中的发生。

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来源期刊

Water Research 环境科学-工程：环境

CiteScore

20.80

自引率

9.40%

发文量

1307

审稿时长

38 days

期刊介绍： Water Research, along with its open access companion journal Water Research X, serves as a platform for publishing original research papers covering various aspects of the science and technology related to the anthropogenic water cycle, water quality, and its management worldwide. The audience targeted by the journal comprises biologists, chemical engineers, chemists, civil engineers, environmental engineers, limnologists, and microbiologists. The scope of the journal include: •Treatment processes for water and wastewaters (municipal, agricultural, industrial, and on-site treatment), including resource recovery and residuals management; •Urban hydrology including sewer systems, stormwater management, and green infrastructure; •Drinking water treatment and distribution; •Potable and non-potable water reuse; •Sanitation, public health, and risk assessment; •Anaerobic digestion, solid and hazardous waste management, including source characterization and the effects and control of leachates and gaseous emissions; •Contaminants (chemical, microbial, anthropogenic particles such as nanoparticles or microplastics) and related water quality sensing, monitoring, fate, and assessment; •Anthropogenic impacts on inland, tidal, coastal and urban waters, focusing on surface and ground waters, and point and non-point sources of pollution; •Environmental restoration, linked to surface water, groundwater and groundwater remediation; •Analysis of the interfaces between sediments and water, and between water and atmosphere, focusing specifically on anthropogenic impacts; •Mathematical modelling, systems analysis, machine learning, and beneficial use of big data related to the anthropogenic water cycle; •Socio-economic, policy, and regulations studies.