A novel nanocomposite of MGO-NGC, composed of magnetic Fe3O4 nanoparticles (M), graphene oxide (GO), and N-methyl-d-glucamine functionalized calix[4]arene (NGC), was synthesized and applied as an effective adsorbent for the removal of two selected pesticides, namely hexaconazole and chlorpyrifos from water samples. The adsorbent was characterized by FTIR, SEM, EDX, TEM, and XRD. The main parameters affecting the adsorption process such as adsorbent dosage, pH of sample solution, salt effect, pesticide concentration, and adsorption time were investigated. The data from kinetic studies fitted well to the pseudo-second order kinetic model with R2 > 0.99. Among the isotherm models of Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich, the Langmuir isotherm fitted well to the adsorption process and demonstrated the monolayer adsorption pattern of the pesticides. Moreover, high adsorption capacities of 78.74 and 93.46 mg g-1 were obtained for chlorpyrifos and hexaconazole, respectively. Thermodynamic and free energy data indicated the physisorption mechanism for the adsorption process. The new adsorbent can be employed as an efficient, environment friendly, and highly reusable alternative for the removal of chlorinated pesticides from aqueous media.
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.
A new solid phase micro extraction (SPME) fiber coating composed of electrospun polyethylene terephthalate (PET) nanofibrous mat doped with superhydrophobic nanosilica (SiO2) was coated on a stainless-steel wire without the need of a binder. The coating was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectrometer (FTIR) techniques and it was used in headspace-SPME of 16 organochlorine pesticides in water samples prior to gass chromatography micro electron capture detector (GC-µECD) analysis. The effects of main factors such as adsorption composition, electrospinning flow rate, salt concentration, extraction temperature, extraction time, and desorption conditions were investigated. Under the optimum conditions, the linear dynamic range (8−1000 ng L−1, R2 > 0.9907), limits of detection (3−80 ng L−1), limits of quantification (8−200 ng L−1), intra-day and inter-day precisions (at 400 and 1000 ng L−1, 1.7−13.8%), and fiber-to-fiber reproducibility (2.4−13.4%) were evaluated. The analysis of spiked tap, sewage, industrial, and mineral water samples for the determination of the analytes resulted in satisfactory relative recoveries (78−120%).