Formation of Chlorinated Organic Compounds from Cl Atom-Initiated Reactions of Aromatics and Their Detection in Suburban Shanghai

Chlorine (Cl) atoms generated from the photolysis of atmospheric reactive chlorine species can rapidly react with various volatile organic compounds (VOCs), forming chlorine- and non-chlorine-containing low-volatile oxygenated organic molecules. Yet, the formation mechanisms of chlorine-containing oxygenated organic molecules (Cl-OOMs) from reactions of Cl atoms with aromatics in the presence and absence of NOx are not fully understood. Here, we investigated Cl-OOMs formation from Cl-initiated reactions of three typical aromatics (i.e., toluene, m-xylene, and 1,2,4-trimethylbenzene (1,2,4-TMB)) in the laboratory and searched for ambient gaseous Cl-OOMs in suburban Shanghai. From our laboratory experiments, 19 Cl-containing peroxyl radicals and a series of Cl-OOMs originating from the Cl-addition-initiated reaction were detected, which provides direct evidence that the Cl-addition-initiated reaction is a non-negligible pathway. In addition, a total of 51 gaseous Cl-OOMs were identified during the winter in suburban Shanghai, 38 of which were also observed in laboratory experiments, hinting that Cl-initiated reaction of aromatics could serve as a source of Cl-OOMs in an anthropogenically influenced atmosphere. Toxicity evaluation of these Cl-OOMs shows potential adverse health effects. These findings demonstrate that Cl-OOMs can be efficiently formed via the Cl-addition pathway in the reactions between aromatics and Cl atoms and some of these Cl-OOMs could be toxic.