Hybrid porous material supported in a cellulose acetate polymeric membrane for the direct immersion thin-film microextraction of parabens in water

A simple and sensitive direct immersion thin-film microextraction (DI-TFME) method based on MIL-101(Cr) modified with carbon nanofibers supported in cellulose acetate (CA-MIL-101(Cr)@CNFs) polymeric membrane was developed for the extraction and preconcentration of parabens in environmental water samples. A high-performance liquid chromatography-diode array detector (HPLC-DAD) was used for the determination and quantification of methylparaben (MP) and propylparaben (PP). The factors affecting the DI-TFME performance were investigated using central composite design (CCD). The linearity of the DI-TFME/HPLC-DAD method obtained under optimal conditions was 0.04–0.04–500 µg/L with a correlation coefficient (R²) greater than 0.99, respectively. The limits of detection (LOD) and quantification (LOQ) for methylparaben were 11 ng/L and 37 ng/L; for propylparaben, they were 13 ng/L and 43 ng/L, respectively. The enrichment factors were 93.7 and 123 for methylparaben and propylparaben. The intraday (repeatability) and interday (reproducibility) precisions expressed as relative standard deviations (%RSD) were less than 5%. Furthermore, the DI-TFME/HPLC-DAD method was validated using real water samples spiked with known concentrations of the analytes. The recoveries ranged from 91.5 to 99.8%, and intraday and interday trueness values were less than ±15%. The DI-TFME/HPLC-DAD approach was effectively used for the preconcentration and quantification of parabens in river water and wastewater samples.