Abiotic Methylation of Tetrabromobisphenol A (TBBPA) with the Occurrence of Methyl Iodide in Aqueous Environments.

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant in the world. Its biotic methylation products, tetrabromobisphenol A mono- and dimethyl ether (TBBPA MME and TBBPA DME, respectively), are frequently detected in the environment, but the importance of abiotic methylation reactions of TBBPA in the environment is not known. In this study, the methylation of TBBPA mediated by methyl iodide (CHI), a ubiquitous compound in aqueous environments, was investigated in simulated waters in the laboratory. It was found that abiotic methylation occurred under both light and dark conditions and was strongly affected by the pH, temperature, and natural organic matter concentration of the water. Abiotic methylation was further verified in natural river water, and the yield of TBBPA MME mediated abiotically by CHI was much greater than that of biotic methylation. According to our calculations and by comparison of the activation energies ( ) for the abiotic methylation of TBBPA and the other four typical phenolic contaminants and/or metabolites (bisphenol A, triclosan, 5-OH-BDE-47, and 4'-OH-CB-61) mediated by CHI, those phenolic compounds all show great methylation potentials. The results indicate a new abiotic pathway for generating TBBPA MME and TBBPA DME from TBBPA, and they also confirm the potentials for abiotic methylation of other phenolic contaminants in aqueous environments.