Characterization and quantification of methyl-benzotriazoles and chloromethyl-benzotriazoles produced from disinfection processes in wastewater treatment

Abstract

Wastewater treatment plants (WWTPs) are one of the major sources of contaminants of emerging concern (CECs) in the environment. Benzotriazole corrosion inhibitors are a class of CECs that are resistant to biodegradation and have been reported in waters varying from WWTP effluent to groundwater and drinking water. This study examined wastewater influent and effluent grab samples over three years using Comprehensive Two-Dimensional Gas Chromatography (GC × GC) to discover six target benzotriazoles, four of which have never been properly characterized in water prior to this work. The six benzotriazoles were two methyl isomers (4-methyl-1H-benzotriazole and 5-methyl-1H-benzotriazole) as well as four chloromethyl isomers (previously unidentified). Using targeted analysis, the benzotriazoles were quantified and semi-quantified in the wastewater. In all seasons sampled but one, the concentration of three of the four chloromethyl-benzotriazoles increased from the influent to effluent waters. For the first time, it was observed that the 4 and 5-methyl-benzotriazoles interact with the sodium hypochlorite in the tertiary treatment step of the WWTP leading to the formation of the four chloromethyl-benzotriazoles. This was confirmed with lab scale synthesis of the reaction where the products were chromatographically analyzed and matched mass spectral and retention time data of the water samples. Assisted by the mass spectral fragmentation information, the four chloromethyl-benzotriazole isomers were tentatively identified as 4-chloromethyl-2H-benzotriazole, 5-chloromethyl-1H-benzotriazole, 4-chloromethyl-1H-benzotriazole, and 5-chloromethyl-2H-benzotriazole, in order of elution. No analytical standards are available for the chloromethyl-benzotriazole compounds and this is the first attempted identification of them in waters. The yearly mass loadings of total benzotriazoles were estimated to average between 148.86 and 394.64 kg/year at this particular facility. The WWTP studied reuses all effluent water for irrigation of crop and forested land so this high value of benzotriazoles entering the environment is concerning and the impacts need to be further studied.