Abstract

In the present work we propose, for the first time, bar adsorptive microextraction coated with carbon-based phase mixtures, followed by microliquid desorption and high performance liquid chromatography-diode array detection (BAμE-μLD/HPLC-DAD) analysis, to enhance the performance of the determination of traces of benzotriazoles (BTRs), benzothiazoles (BTs), and benzenesulfonamide derivatives (BSDs) in environmental water matrices. Assessing six carbon-based sorbents (CA1, CN1, B test EUR, SX PLUS, SX 1, and R) with different selectivity properties allowed us to tailor the best phase mixture (R, 12.5%/CN1, 87.5%) that has convenient porosity, texture, and surface chemistry (pHPZC,mix ~6.5) for trace analysis of benzenesulfonamide, 1-hydroxybenzotriazole, 1H-benzotriazole, 5-methyl-1H-benzotriazole, benzothiazole, and 1,3-benzothiazol-2-ol chemicals in aqueous media. Optimized experimental conditions provided average recoveries ranging from 37.9% to 59.2%, appropriate linear dynamic ranges (5.0 to 120.0 µg L−1; r2 ≥ 0.9964), limits of detection between 1.0 and 1.4 μg L−1, and good precisions (relative standard deviation (RSD) ≤ 9.3%). The proposed methodology (BAμE(R, 12.5%/CN1, 87.5%)-μLD/HPLC-DAD) also proved to be a suitable sorption-based static microextraction alternative to monitor traces of BTRs, BTs, and BSDs in rain, waste, tap, and estuarine water samples. From the data obtained, the proposed approach showed that the BAμE technique with the addition of lab-made devices allows users to adapt the technique to use sorbents or mixtures of sorbents with the best selectivity characteristics whenever distinct classes of target analytes occur simultaneously in the same application.

Highlights

  • Benzotriazoles (BTRs), benzothiazoles (BTs), and benzenesulfonamide derivatives (BSDs) are high production chemicals with varied applications both in industry and at home [1]

  • Several analytical methods have been proposed for the determination of these compounds in environmental water matrices [1,5,6,7], including microextraction-based techniques such as dispersive liquid-liquid microextraction (DLLME) [8], air assisted liquid-liquid microextraction (AALLME) [9], stir bar sorptive extraction (SBSE) [10], and solid phase microextraction (SPME) [11]

  • The HPLC-DAD conditions were evaluated by considering the UV/vis spectral data for the detection of each analyte (BSA, OHBT, BT, MeBT, BTh, and OHBTh) as well as the characteristics of the retention time and resolution

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Summary

Introduction

Benzotriazoles (BTRs), benzothiazoles (BTs), and benzenesulfonamide derivatives (BSDs) are high production chemicals with varied applications both in industry and at home [1]. Several analytical methods have been proposed for the determination of these compounds in environmental water matrices [1,5,6,7], including microextraction-based techniques such as dispersive liquid-liquid microextraction (DLLME) [8], air assisted liquid-liquid microextraction (AALLME) [9], stir bar sorptive extraction (SBSE) [10], and solid phase microextraction (SPME) [11] These technologies present recovery and reproducibility limitations, since the most commonly used sorbents/solvents are devoted to the enrichment of semi-polar to non-polar compounds, of which BTRs, BTs, and BSDs are not (−1.74 ≤ log D ≤ 2.49; 2.0 ≤ matrix pH ≤ 11.0 [12]; Table S1). The comparison with other microextraction-based methodologies reported in the literature is addressed

Instrumental Operating Conditions
Optimization of the BAμE-μLD Efficiency
Selection of the Carbon-Based Phase
Back-Extraction
Microextraction Stage Conditions
Validation Assessment
Comparison with Other Microextraction-Based Methodologies
Application to Environmental Water Matrices
Standards and and Materials
BAμE-μLD Assays
Assays on Real Water Matrices
Instrumental Set-Up
Conclusions
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