title: Biotransformation of benzotriazoles: insights from transformation product identification and compound-specific isotope analysis.
abstract: Benzotriazoles are widely used domestic and industrial corrosion inhibitors and have become omnipresent organic micropollutants in the aquatic environment. Here, the range of aerobic biological degradation mechanisms of benzotriazoles in activated sludge was investigated. Degradation pathways were elucidated by identifying transient and persistent transformation products in batch experiments using liquid chromatography-high-resolution tandem mass spectrometry (LC-HR-MS/MS). In addition, initial reactions were studied using compound-specific isotope analysis (CSIA). Biodegradation half-lives of 1.0 days for 1H-benzotriazole, 8.5 days for 4-methyl-1H-benzotriazole, and 0.9 days for 5-methyl-1H-benzotriazole with activated sludge confirmed their known partial persistence in conventional wastewater treatment. Major transformation products were identified as 4- and 5-hydroxy-1H-benzotriazole for the degradation of 1H-benzotriazole, and 1H-benzotriazole-5-carboxylic acid for the degradation of 5-methyl-1H-benzotriazole. These transformation products were found in wastewater effluents, showing their environmental relevance. Many other candidate transformation products, tentatively identified by interpretation of HR-MS/MS spectra, showed the broad range of possible reaction pathways including oxidation, alkylation, hydroxylation and indicate the significance of cometabolic processes for micropollutant degradation in biological wastewater treatment in general. The combination of evidence from product analysis with the significant carbon and nitrogen isotope fractionation suggests that aromatic monohydroxylation is the predominant step during the biotransformation of 1H-benzotriazole.
authors.affiliation: Eawag, Swiss Federal Institute of Aquatic Science and Technology, 8600 Dübendorf, Switzerland.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Huntscha
authors.forename: Thomas B
authors.initials: TB
authors.lastname: Hofstetter
authors.forename: Emma L
authors.initials: EL
authors.lastname: Schymanski
authors.forename: Stephanie
authors.initials: S
authors.lastname: Spahr
authors.forename: Juliane
authors.initials: J
authors.lastname: Hollender
mesh_terms: D061249:Batch Cell Culture Techniques; D001673:Biodegradation, Environmental; D019149:Bioreactors; D001711:Biotransformation; D002247:Carbon Isotopes; D005591:Chemical Fractionation; D007553:Isotope Labeling / Q000379:methods*; D009587:Nitrogen Isotopes; D012722:Sewage / Q000737:chemistry / Q000382:microbiology; D013997:Time Factors; D014230:Triazoles / Q000378:metabolism*
chemical_list: D002247:Carbon Isotopes; D009587:Nitrogen Isotopes; D012722:Sewage; D014230:Triazoles; C062152:1H-benzotriazole-5-carboxylic acid; C012771:benzotriazole