title: Determination of benzotriazoles and benzothiazoles in human urine by liquid chromatography-tandem mass spectrometry.
abstract: Benzotriazole (BTR) and benzothiazole (BTH) derivatives are used in a wide variety of industrial and consumer products and have been reported to occur in the environment. Owing to a lack of analytical methods, human exposure to BTR and BTH is still unknown. In this study, a liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI(+)MS/MS) method was developed for simultaneous determination of five 1,2,3-benzotriazoles and five 1,3-benzothiazoles in human urine. The target benzotriazoles were 1H-benzotriazole, 1-hydroxy-benzotriazole, tolyltriazole, xylyltriazole (or 5,6-dimethyl-1H-benzotriazole), and 5-chloro-benzotriazole, and the target benzothiazoles were benzothiazole, 2-hydroxy-benzothiazole, 2-methylthio-benzothiazole, 2-amino-benzothiazole, and 2-thiocyanomethylthio-benzothiazole. Urine specimens were enzymatically deconjugated with β-glucuronidase and extracted by a solid-phase extraction (SPE) procedure for the measurement of total concentrations (i.e., free + conjugated forms) of BTRs and BTHs. Additionally, a liquid-liquid extraction (LLE) method was developed for comparison of extraction efficiencies between SPE and LLE. The limits of detection (LODs) ranged from 0.07 (2-amino-benzothiazole) to 4.0 ng/mL (benzothiazole) for the SPE method and from 0.04 (tolyltriazole) to 6.4 ng/mL (benzothiazole) for the LLE method. A total of 100 urine specimens, collected from Athens, Greece, were analyzed by enzymatic deconjugation and SPE. Benzothiazole and tolyltriazole were found frequently, and their concentrations were on the order of a few ng/mL. To our knowledge, this is the first study on the occurrence of 10 BTR and BTH compounds in human urine.
authors.affiliation: Wadsworth Center, New York State Department of Health, School of Public Health, State University of New York at Albany, United States.
authors.forename: Alexandros G
authors.initials: AG
authors.lastname: Asimakopoulos
authors.forename: Anna A
authors.initials: AA
authors.lastname: Bletsou
authors.forename: Qian
authors.initials: Q
authors.lastname: Wu
authors.forename: Nikolaos S
authors.initials: NS
authors.lastname: Thomaidis
authors.forename: Kurunthachalam
authors.initials: K
authors.lastname: Kannan
mesh_terms: D052160:Benzothiazoles / Q000302:isolation & purification / Q000378:metabolism / Q000652:urine*; D002851:Chromatography, High Pressure Liquid; D005966:Glucuronidase / Q000378:metabolism; D006801:Humans; D059625:Liquid-Liquid Extraction; D052616:Solid Phase Extraction; D021241:Spectrometry, Mass, Electrospray Ionization; D014230:Triazoles / Q000302:isolation & purification / Q000378:metabolism / Q000652:urine*
chemical_list: D052160:Benzothiazoles; D014230:Triazoles; C012771:benzotriazole; D005966:Glucuronidase