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.

Endocrine disrupting effects of benzotriazole in rare minnow (Gobiocypris rarus) in a sex-dependent manner

“…Recently, BT was detected in drinking water in the UK with an average concentration of 30.9 ng L À1 (Janna et al, 2011). In addition, the occurrence of BT was also reported in air (Pervova et al, 2010), indoor dust (Wang et al, 2013a), and human urine (Asimakopoulos et al, 2012).…”

A false positive finding in liquid chromatography/triple quadrupole mass spectrometry analysis by a non‐isobaric matrix component: the case of benzotriazole in urine for human biomonitoring

“…Our results indicate the importance of sufficient quality criteria in LC/MS/MS (two SRM transitions, retention time and Q/q ratio) for confirmation of positive results. In HBM, especially for small molecules in complex matrices, this is not always practiced …”

“…[7,8] 1H-BT may be determined from human urine by gas chromatography/MS/MS with a limit of detection of 2.8 μg/L or by LC/MS/MS with a limit of detection for 1H-BT of 0.38 μg/L. [9,10] The latter method, when used to monitor over 300 urine samples, resulted in a detection frequency of 0 to 29% for 1H-BT for different countries. The median concentrations ranged from the limit of quantification to 6.4 μg/L for each country.…”

Brain quantitative proteomic responses reveal new insight of benzotriazole neurotoxicity in female Chinese rare minnow (Gobiocypris rarus)

“…(Asimakopoulos et al, 2012. Thus, BT can be a relatively ubiquitous chemical found in surface waters at levels that may elicit adverse effects on aquatic organisms and humans.…”