基于ESI-TOF-MS的结合态铝团簇形态解析及转化机制研究

Owing to the lack of speciation analysis method for low concentration Al cluster, the existing speciation and the transformation mechanism of Al137+ and other hydrolyzed Al clusters in flocculants are not clear after they complex with inorganic or organic ligands in water treatment processes. As a newly introduced Al cluster speciation analytic method, Electrospray Ionization Time-of-Flight Mass Spectrometry (ESI-TOF-MS) has high potentiality but was not used to solve the problem, and the unclear technique mechanism is the primary bottle neck. Therefore, based on our previous researches-the ESI-TOF-MS analytic method of the hydrolyzed aluminum clusters, this study will investigate the analysis theory, principle, method and application mode of inorganically and organically bound Al clusters, and thus put forward the qualitative and quantitative analytic technology of ESI-TOF-MS. With the new technology, this research further explore the transformation processes and mechanism of the inorganically and organically bound Al clusters, and reveal the influence mechanism of coexisting inorganic or organic ligands and some other factors. This study can help understanding the residual aluminum speciation in tap water and revising the standards of residual aluminum in drinking water in future, and also will provide theoretical basis and technical support to ensure the drinking water safety of Beijing 2022 Olympic Winter Games.

受低浓度铝团簇形态解析技术不足的限制，Al137+等水解团簇随聚合铝絮凝剂投加入水后与无机、有机配体离子的结合形态及其转化机理尚不清楚。而电喷雾飞行时间质谱（ESI-TOF-MS）作为铝形态分析的新引入技术，有较高应用潜力但对此研究几近空白，相关铝谱解析技术原理不清是主要瓶颈。为此，本研究基于前期研究成果-水解态铝团簇形态ESI-TOF-MS解析方法，探讨无机、有机结合态铝团簇形态ESI-TOF-MS解析原理、原则、方法和应用模式，改进提出结合态铝团簇形态ESI-TOF-MS定性及定量解析技术；并以此新型技术为主要研究手段，探讨结合态铝团簇形态结构转化过程与机理，揭示共存无机、有机配体等因子影响机制，以期为认识自来水中铝形态残余特征，进一步修订饮用水铝残余标准，保障2022北京冬奥会饮用水安全提供理论依据和技术支撑。

本课题主要研究了无机和有机离子共存下铝团簇形态电喷雾质谱铝谱解析理论方法以及在ESI雾化、模拟配水和实际水处理过程中铝团簇形态的转化过程机理。取得以下代表性成果：（1）从方法学研究角度优化提出了无机、有机结合态铝团簇形态ESI-MS解析原理、原则、方法和定性和定量解析模式；（2）基于ESI-MS技术实现跟踪分析铝团簇在混凝过程中的形态转化过程（尤其是微界面促发下单体铝向Al13的转化）；（3）首次系统阐述多水源供水条件下水源-水厂-管网-水龙头水中溶解态、结合态铝团簇形态残留特征及主要影响因素；（4）基于铝团簇形态ESI-MS铝谱解析阐释典型铝团簇形态的河蚬毒性效应。研究成果为进一步开展无机和有机结合态铝团簇形态表征技术研究提供参考，同时为饮用水中铝团簇形态的残余控制提供理论支撑。相关研究成果发表SCI学术论文9篇，拟出版专著1部（题目：聚合氯化铝絮凝残余过程与毒性效应，合同已签），公示发明专利1项，发表中文核心期刊论文1篇（已接收，环境化学）。发表的9篇学术论文均为SCI top期刊文章，其中一篇发表在环境领域旗舰刊物Water Research上，一篇发表在Environmental Science：Nano（IF=7.701）并被选做期刊封面。同时，受该期刊邀请，该期刊对本课题研究成果也进行了特别介绍和报道。