Magnetic halloysite nanotube/polyaniline/copper composite coupled with gas chromatography-mass spectrometry: A rapid approach for determination of nitro-phenanthrenes in water and soil samples

A fast, sensitive and reliable ultrasound-assisted magnetic dispersive solid-phase microextraction (UAMDSPME) setup was developed and evaluated for the enrichment of nitro- phenanthrenes compound in environmental samples prior to GC-MS determination. A new type of nanocomposite sorbent was made based on halloysite nanotubes (HNTs). HNTs is a type of natural material, have attracted great interest because of their large surface area and high chemical and thermal stability. The hybrid nanocomposite (magnetic HNT@PANI@Cu) was obtained by coating the magnetic HNTs by polyaniline (PANI) and afterwards decorating with metalic copper. Its morphology and surface properties were characterized using Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, energy dispersive spectroscopy and vibrating sample magnetometry. In this work several factors that may affect the extraction efficiencies such as desorption solvent type and its volume, sonication times for extraction and desorption, sorbent amount, organic modifier content, salt concentration and matrix effect were investigated in detail. Under the optimal conditions, the limit of detection (S/N = 3) was 0.25 ng L−1 and the linearity was in the range of 0.01-100 μg L−1. The method precision expressed as relative standard deviations (RSDs%) were 4.6-6.1% (intra-day), and 7.2-9.6% (inter-day). Finally, the presented method was successfully applied to the rapid determination of trace levels of nitro-phenanthrenes in spiked water and soil samples.