Optimization of a Natural-Deep-Eutectic-Solvent-Based Dispersive Liquid–Liquid Microextraction Method for the Multi-Target Determination of Emerging Contaminants in Wastewater

The widespread discharge of industrial and urban waste has led to significant increases in the environmental concentrations of numerous chemical substances. This work presents the development of a simple and environmentally friendly dispersive liquid–liquid microextraction (DLLME) method based on a...

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Main Authors: Beatriz Gómez-Nieto, Antigoni Konomi, Georgios Gkotsis, Maria-Christina Nika, Nikolaos S. Thomaidis
Format: Article
Language:English
Published: MDPI AG 2025-07-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/14/2988
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author Beatriz Gómez-Nieto
Antigoni Konomi
Georgios Gkotsis
Maria-Christina Nika
Nikolaos S. Thomaidis
author_facet Beatriz Gómez-Nieto
Antigoni Konomi
Georgios Gkotsis
Maria-Christina Nika
Nikolaos S. Thomaidis
author_sort Beatriz Gómez-Nieto
collection DOAJ
description The widespread discharge of industrial and urban waste has led to significant increases in the environmental concentrations of numerous chemical substances. This work presents the development of a simple and environmentally friendly dispersive liquid–liquid microextraction (DLLME) method based on a hydrophobic natural deep eutectic solvent (NADES) for the determination of selected compounds from benzotriazole, benzothiazole, paraben, and UV filter families in wastewater samples. Of the twelve NADES formulations evaluated, those composed of a 4:1 molar ratio of thymol and menthol presented the highest extraction efficiencies. The influence of key experimental variables such as the pH of the aqueous sample, the ratio of NADES phase to sample volume, and the extraction time on the extraction efficiency was investigated using a multivariate optimization. Under optimal conditions, relative standard deviations below 15% and recoveries for spiked wastewater samples ranged between 82 and 108%, demonstrating the suitability of the method for routine water-quality monitoring. The sustainability and practicality of the developed method was evaluated using the assessment tools ChlorTox, AGREEprep, AGRRE, and BAGI, obtaining scores of 0.005 g in the NADES-DLLME method, 0.70, 0.52, and 72.5, respectively, demonstrating that the method is green and reliable.
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spelling doaj-art-892b8a2eea2546edb2a623713aed97522025-08-20T03:56:46ZengMDPI AGMolecules1420-30492025-07-013014298810.3390/molecules30142988Optimization of a Natural-Deep-Eutectic-Solvent-Based Dispersive Liquid–Liquid Microextraction Method for the Multi-Target Determination of Emerging Contaminants in WastewaterBeatriz Gómez-Nieto0Antigoni Konomi1Georgios Gkotsis2Maria-Christina Nika3Nikolaos S. Thomaidis4Departamento de Química Analítica y Análisis Instrumental, Facultad de Ciencias, Universidad Autónoma de Madrid, Avda. Francisco Tomás y Valiente, 7, 28049 Madrid, SpainLaboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zografou, 15771 Athens, GreeceLaboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zografou, 15771 Athens, GreeceLaboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zografou, 15771 Athens, GreeceLaboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zografou, 15771 Athens, GreeceThe widespread discharge of industrial and urban waste has led to significant increases in the environmental concentrations of numerous chemical substances. This work presents the development of a simple and environmentally friendly dispersive liquid–liquid microextraction (DLLME) method based on a hydrophobic natural deep eutectic solvent (NADES) for the determination of selected compounds from benzotriazole, benzothiazole, paraben, and UV filter families in wastewater samples. Of the twelve NADES formulations evaluated, those composed of a 4:1 molar ratio of thymol and menthol presented the highest extraction efficiencies. The influence of key experimental variables such as the pH of the aqueous sample, the ratio of NADES phase to sample volume, and the extraction time on the extraction efficiency was investigated using a multivariate optimization. Under optimal conditions, relative standard deviations below 15% and recoveries for spiked wastewater samples ranged between 82 and 108%, demonstrating the suitability of the method for routine water-quality monitoring. The sustainability and practicality of the developed method was evaluated using the assessment tools ChlorTox, AGREEprep, AGRRE, and BAGI, obtaining scores of 0.005 g in the NADES-DLLME method, 0.70, 0.52, and 72.5, respectively, demonstrating that the method is green and reliable.https://www.mdpi.com/1420-3049/30/14/2988hydrophobic NADESmicroextractionemerging contaminantswastewatergreen analytical chemistryUHPLC-QTOF-MS
spellingShingle Beatriz Gómez-Nieto
Antigoni Konomi
Georgios Gkotsis
Maria-Christina Nika
Nikolaos S. Thomaidis
Optimization of a Natural-Deep-Eutectic-Solvent-Based Dispersive Liquid–Liquid Microextraction Method for the Multi-Target Determination of Emerging Contaminants in Wastewater
Molecules
hydrophobic NADES
microextraction
emerging contaminants
wastewater
green analytical chemistry
UHPLC-QTOF-MS
title Optimization of a Natural-Deep-Eutectic-Solvent-Based Dispersive Liquid–Liquid Microextraction Method for the Multi-Target Determination of Emerging Contaminants in Wastewater
title_full Optimization of a Natural-Deep-Eutectic-Solvent-Based Dispersive Liquid–Liquid Microextraction Method for the Multi-Target Determination of Emerging Contaminants in Wastewater
title_fullStr Optimization of a Natural-Deep-Eutectic-Solvent-Based Dispersive Liquid–Liquid Microextraction Method for the Multi-Target Determination of Emerging Contaminants in Wastewater
title_full_unstemmed Optimization of a Natural-Deep-Eutectic-Solvent-Based Dispersive Liquid–Liquid Microextraction Method for the Multi-Target Determination of Emerging Contaminants in Wastewater
title_short Optimization of a Natural-Deep-Eutectic-Solvent-Based Dispersive Liquid–Liquid Microextraction Method for the Multi-Target Determination of Emerging Contaminants in Wastewater
title_sort optimization of a natural deep eutectic solvent based dispersive liquid liquid microextraction method for the multi target determination of emerging contaminants in wastewater
topic hydrophobic NADES
microextraction
emerging contaminants
wastewater
green analytical chemistry
UHPLC-QTOF-MS
url https://www.mdpi.com/1420-3049/30/14/2988
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