Acid-based deep eutectic solvents followed by GFAAS for the speciation of As(III), As(V), total inorganic arsenic and total arsenic in rice samples.

In the present study, an efficacious, safe, inexpensive and eco-friendly microextraction was provided by deep eutectic solvents based on dispersive liquid-liquid microextraction (DLLME - DES) followed by GFAAS. A series of DESs were synthesised using l-menthol as hydrogen bond acceptor (HBA) and carboxylic acids with 4, 6, 8 and 10 carbon atoms as hydrogen bond donors (HBD). The synthesised DESs were used as extractants of arsenic ions. Under optimised conditions, good linearity with coefficient of determination (r2) 0.992 and an acceptable linear range of 0.3-100 µg kg-1 was obtained. The limit of detection was 0.1 µg kg-1 (S/N = 3) for arsenite (As(III)) ions, and a high enrichment factor (EF = 200) was obtained. The enhancement factor and extraction recovery (ER%) of the method were 340 and 60%, respectively. RSDs including inter- and intra-day ranged from 3.2% to 5.8% in three examined concentrations. After a specific digestion, the capability of the synthesised DES in the extraction of As(III) from rice was tested. Total inorganic arsenic was separated similarly after reduction of arsenate (As(V)) to As(III), and As(V) concentration was calculated by difference. Using a second digestion method, total arsenic concentration (sum of organic and inorganic arsenic) in the samples was determined.

Trace determination of triazine herbicides in fruit and vegetables using novel hydrophobic deep eutectic solvent-based dispersive liquid-liquid microextraction followed by high-performance liquid chromatography-ultraviolet.

In the present research, a novel hydrophobic deep eutectic solvent-based dispersive liquid-liquid microextraction technique was established and combined with high-performance liquid chromatography-ultraviolet for the determination of triazine herbicides in fruit and vegetable samples. A deep eutectic solvent was synthesized using l-menthol as a hydrogen bond acceptor and ethylene glycol as a hydrogen bond donor and used as a green extractant. The characterization of deep eutectic solvent was investigated by Fourier-transform infrared, nuclear magnetic resonance, and thermogravimetric analysis. Under the optimum conditions, relative standard deviation values for intra-day and inter-day of the method based on seven replicate measurements of 50.0 µg/kg of triazines were in the range of 2.8%-5.5% and 3.7%-7.2%, respectively. The calibration graphs were linear in the range of 3.0-500 µg/kg and the limits of detection were in the range of 1.0-2.0 µg/kg. The relative recoveries of different fruit and vegetable samples that have been spiked with two levels of target compounds were 91.5%-109.8%. The method has good linearity, sensitivity, accuracy, and precision. It is also environmentally friendly and was successfully used to determine the concentrations of triazines in fruit and vegetable samples.

Novel deep eutectic solvent-based liquid phase microextraction for the extraction of estrogenic compounds from environmental samples.

Steroid hormones, such as estrone (E1), 17ß-estradiol (E2), 17ß-ethinylestradiol (EE2) and estriol (E3) are a group of lipophilic active substances, synthesized biologically from cholesterol or chemically. A pH-switchable hydrophobic deep eutectic solvent-based liquid phase microextraction (DES-LPME) technique was established and combined with gas chromatography-mass spectroscopy for the determination of estrogenic compounds in environmental water and wastewater samples. A DES was synthesized using l-menthol as HBA and (1S)-(+)-camphor-10-sulfonic acid (CSA) as HBD, and used as a green extraction solvent. By adjusting the pH of the solution, the unique behavior of the DES in the phase transition and extraction of the desired analytes was investigated. The homogenization process of the mixture is done only by manual shaking in less than 30 seconds and the phase separation is done only by changing the pH and without centrifugation. Some effective parameters on the extraction and derivatization, such as molar ratio of DES components, DES volume, KOH concentration, HCl volume, salt addition, extraction and derivatization time and derivatization prior or after extraction were studied and optimized. Under the optimum conditions, relative standard deviation (RSD) values for intra-day and inter-day of the method based on 7 replicate measurements of 20 ng L-1 of estrogenic compounds and 10 ng L-1 for internal standard in different samples were in the range of 2.2-4.6% and 3.9-5.7%, respectively. The calibration graphs were linear in the range of 0.5-100 ng L-1 and the limits of detection (LODs) were in the range of 0.2-1.0 ng L-1. The relative recoveries of environmental water and wastewater samples which have been spiked with different levels of target compounds were 91.0-108.8%.