Headspace Extraction of Chlorobenzenes from Water Using Electrospun Nanofibers Fabricated with Calix[4]arene-Doped Polyurethane-Polysulfone

Chlorobenzenes (CBs) are persistent and potentially have a carcinogenic effect on mammals. Thus, the determination of CBs is essential for human health. Hence, in this study, novel polyurethane−polysulfone/calix[4]arene (PU-PSU/calix[4]arene) nanofibers were synthesized using an electrospinning approach over in-situ coating on a stainless-steel wire. The nanosorbent was comprehensively characterized using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR) techniques. The SEM analysis depicted the nanofiber’s unique morphology and size distribution in the range of 50−200 nm. To determine the levels of 1,2,4-trichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,3,4-tetrachlorobenzene in water samples, freshly prepared nanosorbent was employed using headspace-solid phase microextraction (HS-SPME) in combination with gas chromatography micro electron capture detector (GC-µECD). Other calixarenes, such as sulfonated calix[4]arene, p-tert-calixarene, and calix[6]arene were also examined, and among the fabricated sorbents, the PU−PSU/calix[4]arene showed the highest efficiency. The key variables of the procedure, including ionic strength, extraction temperature, extraction duration, and desorption conditions were examined. Under optimal conditions, the LOD (0.1−1.0 pg mL−1), the LDR (0.4−1000 pg mL−1), and the R2 > 0.990 were determined. Additionally, the repeatability from fiber to fiber and the intra-day and inter-day reproducibility were determined to be 1.4−6.0, 4.7−10.1, and 0.9−9.7%, respectively. The nanofiber adsorption capacity was found to be 670−720 pg/g for CBs at an initial concentration of 400 pg mL−1. A satisfactory recovery of 80−106% was attained when the suggested method’s application for detecting chlorobenzenes (CBs) in tap water, river water, sewage water, and industrial water was assessed.