Formation of the emerging disinfection byproducts halocyclopentadienes from phenolic compounds after chlorination

Halocyclopentadienes (HCPDs) are an emerging class of alicyclic disinfection by-products (DBPs) with high toxicity in disinfected drinking water. However, their potential precursors remain unclear, which hinders the understanding of their formation and further development of control strategies. In this study, two HCPDs, 1,2,3,4-tetrachloro-1,3-cyclopentadiene (TCC) and 1,2,3,4,5,5-hexachloro-1,3-cyclopentadiene (HCC), were identified in chlorinated lignin and tannic acid samples for the first time. The chlorination of four lignin-like and two tannic-like phenolic model compounds confirmed that guaiacol and digallic acid can produce HCPDs. According to their structures, ortho-substituents of phenolic compounds were speculated to be crucial for HCPDs formation. The simulated disinfection of catechol, 2-ethoxyphenol (2-EOP), 2-propoxyphenol (2-POP) and 3,4-dihydroxy-5-methoxybenzoic acid (DH-5-MBA) with different ortho-substituents demonstrated that three of these compounds can generate HCPDs, except catechol, which further indicates that ortho-substituents, such as the methoxy, ethoxy and propoxy groups, contribute to HCPDs generation. Guaiacol was the simplest compound for generating HCPDs, and possible formation pathways during chlorination were proposed. Seven hydroxy-chlorocyclopentadienes were tentatively identified and are likely important intermediates of HCPDs formation. Additionally, TCC and HCC were confirmed in tap water and chlorinated SRNOM samples with total concentrations up to 11.07 ng/L and 65.66 ng/L, respectively, further demonstrating the wide existence of HCPDs and their precursors. This study reports the clear precursors of HCPDs and provides a theoretical foundation for controlling HCPDs formation in disinfected drinking water.