An amide-based covalent organic framework chemically anchored on silica nanoparticles for headspace microextraction sampling of halogenated hydrocarbons in air.

A needle trap device (NTD) was developed using an amide-based covalent-organic framework (COF), chemically bonded to silica nanoparticles. The NTD was coupled with gas chromatography-flame ionization detection (GC-FID) and employed for the headspace microextraction analysis of halogenated hydrocarbons (HHCs) in the air. The adsorbent was characterized using Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), and field-emission scanning electron microscopy (FE-SEM) techniques. Optimal values for the experimental variables were assessed using response surface methodology (RSM) with a central composite design (CCD), thereby reducing the number of experiments, material consumption, costs, and time. The optimal values for desorption time and temperature were obtained 5 min and 260 °C, respectively. Breakthrough volume (BtV) was studied over the range of 0.5 - 3 times the occupational exposure limit (OEL) and its optimal value was found to be 1200 mL. The optimal sampling temperature and relative humidity (RH) were obtained 20 °C, and 15 %, respectively. The limits of detection (LODs) and limits of quantification (LOQs) were ranged from 0.013 to 0.077 μg l and 0.041 to 0.21 μg l, respectively, with a linear dynamic range (LDR) of 0.04 to 100 μg l. The method's repeatability and reproducibility (RSD %) were observed over the ranges of 5.3 - 6.4 % and 4.7 -6.9 %, respectively. A statistically validated agreement was observed between the NTD-GC-FID method and the NIOSH 1003 standard procedure for the sampling and determination of HHCs in real workplace air samples, demonstrating the reliability and accuracy of the developed approach.