Comparison of monochloramination and chlorination of 1,3-diphenylguandine (DPG): kinetics, transformation products, and cell-based in-vitro testing

Abstract

As a widely used secondary vulcanization accelerator in the rubber industry, 1,3-diphenylguanidine (DPG) poses risks to human health and the environment. To compare and comprehend the disinfection process of DPG, this work investigates the reaction kinetics, toxicity, and transformation products (TPs) of DPG during chlorination and monochloramination. It has been revealed that the reactivity of monochloramine is significantly slower compared to chlorination of DPG, with the maximum efficiency observed at pH 7 to pH 8. Cytotoxicity assessment using HepG2 and THP-1 cells reveals that cytotoxicity hierarchy is as follows: chlorine TPs > monochloramine TPs > DPG. Moreover, oxidant-to-DPG molar ratios 10 and 20 lead to higher cytotoxicity in both chlorination and monochloramination compared to ratio 5 and 100. Additionally, cell bioenergetics experiments demonstrate that chlorine and monochloramine TPs induce mitochondrial dysfunction and enhance glycolytic function in HepG2 cells. The genotoxic response from p53 signaling further suggested genotoxic effects of certain TPs. Furthermore, analysis of TPs using high-resolution mass spectrometry (HRMS) identifies ten TPs, with chlorination yielding more TPs than monochloramination. Generally, a chlorine or monochloramine molar ratio to DPG of 10-20 results in an increased formation of TPs and heightened cytotoxicity. Notably, higher oxidant molar ratios increased the formation of monoguanidine TPs and DPG hydroxylation during chlorination, whereas monochloramination lead to DPG substitution predominantly generating chlorinated DPG due to weaker oxidation effects. These findings provide valuable information for the appropriate treatment of DPG and disinfection processes in water facilities to mitigate potential risks to human health and the ecosystem.