Deep eutectic solvent-based ferrofluid for vortex-assisted liquid-liquid microextraction of nonsteroidal anti-inflammatory drugs from environmental waters

A novel ferrofluid of Fe3O4 nanoparticles and a deep eutectic solvent (DES) composed of menthol and pentanoic acid was introduced as a green microextraction medium. The ferrofluid was successfully used as an extractant for vortex-assisted liquid-liquid microextraction (VALLME) of nonsteroidal anti-inflammatory drugs (NSAIDs) in environmental waters prior to their determination by HPLC-DAD. Once the ferrofluid was dispersed in the sample by vortex agitation, phase separation could be easily achieved by placing a neodymium magnet next to the tube, which eliminated the centrifugation step and simplified the operational procedure. As a result, the sample pretreatment took only ≈2 min. The experimental parameters, including pH, nanoparticle amount, ferrofluid volume, vortex time, salt amount, and disruptive solvent type and its volume, were optimized stepwise. The method showed linear behavior for all NSAIDs from 5 to 100 μg/L, with limit of detection values and enrichment factors in the ranges of 1.68–2.05 μg/L and 38.9–50.6, respectively. Intra- and Inter-day accuracies obtained from the analysis of spiked river, lake, and tap water samples at low and high-quality control levels (20 and 80 μg/L) ranged from 90.3% to 108.0%, with relative standard deviations less than <12.3%. The results of this study demonstrate that the use of DES-based ferrofluid in VALLME can be considered a simple, environmentally friendly, and reliable alternative for the determination of NSAIDs in environmental waters.