Miniaturized matrix solid-phase dispersion based on deep eutectic solvent and carbon nitride associated with high-performance liquid chromatography: A new feasibility for extraction and determination of trace nitrotoluene pollutants in soil samples.

In this research, a miniaturized version of matrix solid phase dispersion (MSPD) method was developed for successful extraction of five nitrotoluenes from soil samples. The terpene based deep eutectic solvent (DES) composed of borneol and DL-menthol was used simultaneously as extraction solvent and dispersing liquid. Graphitic-carbon nitride (g-C3N4) as sorbent was prepared by pyrolysis of melamine at a muffle furnace. The MSPD mixture was obtained by grinding soil, DES, and g-C3N4. Minimum amount of acetonitrile was used in the elution step. Some experimental variables including type and volume of DES, type of dispersant, mass ratio of dispersant to sample, volume of elution solvent, grinding time, and ultrasonication time were evaluated. Analysis of extracted samples was performed by high performance liquid chromatography-ultra violet detection. Under the optimized conditions; the limits of detection were achieved in the range of 0.12-0.33 µg g-1, and the relative standard deviations were equal to or lower than 9.3%. The extraction recoveries were ranged from 78 to 96%. This straightforward and fast method is effective for environmentally friendly extraction of nitrotoluenes from soil samples.

Ferrofluid of magnetic clay and menthol based deep eutectic solvent: Application in directly suspended droplet microextraction for enrichment of some emerging contaminant explosives in water and soil samples.

In this work, for the first time, ferrofluid of magnetic montmorillonite nanoclay and deep eutectic solvent was prepared and coupled with directly suspended droplet microextraction. Incorporation of ferrofluid in a miniaturized sample preparation technique resulted in achieving high extraction efficiency while developing a green analytical method. The prepared ferrofluid has strong sorbing properties and hydrophobic characteristics. In this method, a micro-droplet of ferrofluid was suspended into the vortex of a stirring aqueous solution and after completing the extraction process, was easily separated from the solution by a magnetic rod without any operational problems. The predominant experimental variables affecting the extraction efficiency of explosives were evaluated. Under optimal conditions, the limits of detection were in the range 0.22-0.91 µg L-1. The enrichment factors were between 23 and 93 and the relative standard deviations were <10%. The relative recoveries were ranged from 88 to 104%. This method was successfully applied for the extraction and preconcentration of explosives in water and soil samples, followed their determination by high performance liquid chromatography with ultraviolet detection (HPLC-UV).

Deep eutectic solvent based magnetic nanofluid in the development of stir bar sorptive dispersive microextraction: An efficient hyphenated sample preparation for ultra-trace nitroaromatic explosives extraction in wastewater.

A deep eutectic solvent based magnetic nanofluid was coupled with stir bar sorptive dispersive microextraction as a hyphenated sample preparation technique. The neodymium core magnetic stir bar was coated physically with nanofluid of magnetic carbon nanotube nanocomposites and deep eutectic solvents. The prepared nanofluid has magnetic and strong sorbing properties and is compatible with gas chromatography. In this nanofluid, the deep eutectic solvent acts simultaneously as both carrier and stabilizer for magnetic nanotubes. The predominant experimental variables affecting the extraction efficiency of nitroaromatic compounds were evaluated. Under the optimized conditions, the limit of detection and enrichment factor were in the range of 0.2-4.9 ng/L and 852-1480, respectively. The relative standard deviations were between 5.6 and 10.2% (n = 6). Method validation was performed by both spiking-recovery method and comparison of results with other methods. Finally, the proposed method was successfully applied for the extraction and pre-concentration of nitroaromatic explosives in water samples, followed by determination by gas chromatography with micro-electron capture detection.

Determination of organophosphorus pesticides by gas chromatography with mass spectrometry using a large-volume injection technique after magnetic extraction.

A fast and efficient method was developed for the extraction and determination of organophosphorus pesticides in water samples. Organophosphorus pesticides were extracted by solid-phase extraction using magnetic multi-walled carbon nanotubes and determined by gas chromatography with ion-trap mass spectrometry. Parameters affecting the extraction were investigated. Under optimum conditions of the method, 10 mg magnetic multi-walled carbon nanotubes were added into 10 mL sample. After 2 min, adsorbent particles settled at the bottom of test tube with a magnet. After removing aqueous supernatant, the analytes were desorbed with acetonitrile. Then, 70 µL of acetonitrile phase was injected into the gas chromatography and mass spectrometry system that had an ion-trap analyzer. To achieve high sensitivity, the large-volume-injection technique was used with a programmed temperature vaporization inlet, and the ion-trap mass spectrometer was operated in single ion storage mode. Under the best conditions, the enrichment factors and extraction recoveries were in the range of 113-124 and 74-103%, respectively. The limits of detection were between 3 and 15 ng/L, and the relative standard deviations were < 10%. This method was successfully used for the determination of organophosphorus pesticides in dam water, lagoon water, and river water samples with good reproducibility and recovery.