Simultaneous determination of benzotriazole and benzothiazole derivatives in aqueous matrices by mixed-mode solid-phase extraction followed by liquid chromatography–tandem mass spectrometry

Abstract

An improved selectivity method for the simultaneous determination of four benzotriazoles (benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, and 5,6-dimethyl-1H-benzotriazole) and six benzothiazoles (benzothiazole, 2-hydroxybenzothiazole, 2-benzothiazolamine, mercaptobenzothiazole, 2-methylbenzothiazole, and 2-methylthiobenzothiazole) in aqueous matrices has been developed. Under optimal conditions, analytes are concentrated using a MAX solid-phase extraction (SPE) cartridge, based on divinylbenzene-N-vinylpyrrolidone functionalized with quaternary amine groups, which allows reversed-phase interactions in combination with ionic exchange. Selected compounds are recovered with methanol–acetone 7:3 (v/v) whereas acidic interferences remained attached to the sorbent, and as determined by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS), LOQs for surface, urban and industrial wastewater are in the range of 0.002-0.29 ng/mL. Figures of merit of the method revealed good precision (RSD% <12%), linearity (R2 > 0.99) and accuracy (%R = 80-100%) for surface waters and effluents allowing direct external standard quantification. For more complex samples, such as urban and industrial raw wastewater, either the standard addition method or pseudo-external standard calibration using matrix matched standards are recommended. Analysis of different real samples, surface, urban wastewater and, for the first time, metal industry wastewater, reflected concentrations up to 310 ng/mL. The methylbenzotriazole isomers ratio was also determined.

The washout effect during laundry on benzothiazole, benzotriazole, quinoline, and their derivatives in clothing textiles

“…Deuterated benzotriazole (d 4 -BTri), a commonly used internal standard for benzothiazole and benzotriazole analysis, has been reported to elute in the beginning of the chromatogram and may not be the most appropriate internal standard for all of the compounds (Herrero et al 2013). In addition, methods have been developed for determination of MeBT, but it has not been detected in, e.g., water samples (Carpinteiro et al 2012;Reemtsma 2000), neither in the clothing textiles investigated in this study.…”

Presence of benzotriazoles, benzothiazoles and benzenesulfonamides in surface water samples by liquid chromatography coupled to high‐resolution mass spectrometry

“…Typically, BTRs, BTs and BSAs in water samples are determined by liquid chromatography mainly coupled to tandem mass spectrometry [11][12][13][14][15][16][17][18]24] even though highresolution mass spectrometry (HRMS) is also used in some studies [19,23]. In the past few years, the use of HRMS based on time-of flight or Orbitrap analysers for trace analysis has become more widely accepted and affordable.…”

Solid-Phase Extraction of Polar Benzotriazoles as Environmental Pollutants: A Review

“…In this review, we focus on the polar compounds listed in Table 1 . Due to a high aqueous mobility stemming from their polarity (observable as log K ow in Table 1 ) they are ubiquitously present in the hydrosphere, having been found in snow, groundwater, rivers, lakes, seas, treated and untreated wastewater, recycled water and also in drinking water [ 2 , 5 , 6 , 7 , 8 , 9 , 10 , 11 ]. Furthermore, they have been also determined in air, soil, sediments, house dust and textiles [ 12 , 13 , 14 , 15 , 16 ], in human urine, amniotic fluid and plants [ 11 , 17 , 18 ].…”

“…The main sources of these pollutants appear to be airport run-off and industrial and municipal wastewater [ 2 , 5 , 8 ], as benzotriazoles are not readily biodegradable. According to different sources, only 13–62% of BTZ and 11–72% of MBZ are removed in public wastewater treatment plants [ 2 , 5 , 19 ] due to their long half-lives [ 20 ], with 5MBZ being much more susceptible to degradation than 4MBZ.…”

“…In the majority of cases, separation has been performed on various C columns [ 4 , 10 , 11 , 21 , 37 , 38 , 39 ], although columns with phenyl stationary phase have also been used [ 2 , 8 , 22 ]. Usually, the mobile phase has initially a high water content and is then gradually adjusted to raise the ratio of organic solvent, this solvent being either methanol (MeOH) [ 10 , 40 ], acetonitrile (ACN) [ 22 , 32 ] or both [ 38 , 41 ].…”