Laboratory of Advanced Analytical Chemistry and Detection Technology, Research Center for Eco-Environmental Engineering, Dongguan University of Technology, Dongguan, 523808, China; State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China.
State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China.
Anal Chim Acta. 2022 Apr 29;1204:339618. doi: 10.1016/j.aca.2022.339618. Epub 2022 Feb 17.
Halogenated organic compounds (HOCs) are a huge group of pollutants, which have caused severe environmental pollution worldwide. This study developed a nontarget analysis method for characterization of known and unknown HOCs in tap water, fly ash, soil and sediment using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) with aid of scripting data-processing approaches. The FT-ICR-MS was equipped with an electrospray ionization source operated in negative ion mode, and full scan at a mass resolution around 200,000 was applied. Data screening scripts were developed based on exact mass differences and abundance ratios between neighboring chlorine/bromine isotopologues. Cosine similarity analysis was applied to evaluating similarity between measured and simulated isotopologue distributions which were constituted by abundance ratios between neighboring isotopologues for identification of polychlorinated and polybrominated compounds. From huge amount of peaks in raw mass spectra, thousands of MS features of HOCs were screened out. In total 824 HOC formulae were finally identified, including 702 organochlorines, 108 organobromines, and 14 mix-chlorine/bromine-containing organic compounds (OClBrs), mainly being monochlorinated/monobrominated compounds (∼90%) whose abundances were also the most prominent. Dozens of HOCs were tentatively structurally elucidated, including halogenated phenols, carboxylic acids, benzenesulfonic acids, etc. Three novel OClBrs were structurally identified, i.e., bromochlorobenzoic acid, bromodichlorophenol and bromotrichlorophenol. The data-processing scripts and strategies can facilitate accurate and high-throughput nontarget analysis of both common and novel/emerging halogenated organic pollutants in complex matrices. The research results provide informative insights into pollution profiles of HOCs in the environment, suggesting that halogenated organic pollutants remain to be seriously concerned.
卤代有机化合物（HOCs）是一大类污染物，已在全球范围内造成严重的环境污染。本研究开发了一种非靶向分析方法，用于使用傅里叶变换离子回旋共振质谱（FT-ICR-MS）结合脚本数据处理方法，对自来水中、飞灰中、土壤中和沉积物中的已知和未知 HOC 进行特征描述。FT-ICR-MS 配备了电喷雾电离源，以负离子模式运行，并在大约 200,000 的质量分辨率下进行全扫描。数据筛选脚本是基于精确质量差异和相邻氯/溴同位素之间的丰度比开发的。余弦相似性分析用于评估测量和模拟同位素分布之间的相似性，这些分布由相邻同位素之间的丰度比组成，用于识别多氯和多溴化合物。从原始质谱中大量的峰中，筛选出数千种 HOC 的 MS 特征。最终确定了 824 种 HOC 分子式，包括 702 种有机氯、108 种有机溴和 14 种混合氯/溴含碳有机化合物（OClBrs），主要是一氯/一溴化合物（约 90%），其丰度也最为显著。数十种 HOC 被暂定结构阐明，包括卤代酚类、羧酸类、苯磺酸类等。结构鉴定了三种新型 OClBrs，即溴氯苯甲酸、溴二氯苯酚和溴三氯苯酚。数据处理脚本和策略可以促进复杂基质中常见和新型/新兴卤代有机污染物的准确和高通量非靶向分析。研究结果提供了有关环境中 HOC 污染概况的信息性见解，表明卤代有机污染物仍然需要严重关注。
