A new headspace liquid-phase microextraction technique based on using a copper foam nanostructure substrate followed by gas chromatography-flame ionization detection was developed for the determination of volatile organic compounds in water and wastewater samples. The copper foam with highly porous nanostructured walls was fabricated on the surface of a copper wire by a rapid and facile electrochemical process and used as the extractant solvent holder. Propyl benzoate was immobilized in the pores of the copper foam coating and used for the microextraction of benzene, toluene, ethylbenzene and xylenes. The experimental parameters such as the type of organic solvent, desorption temperature, desorption time, salt concentration, sample temperature, equilibrium time and extraction time, were investigated and optimized. Under the optimum conditions, the method detection limit was between 0.06 and 0.25 μg L−1. The relative standard deviation of the method for the analytes at 4–8 μg L−1 concentration level ranged from 7.9 to 11%. The fiber-to-fiber reproducibility for three fibers prepared under the same condition was 9.3–12%. The enrichment factor was in the range of 615–744. Different water samples were analyzed for the evaluation of the method in real sample analysis. Relative recoveries for spiked tap, river and wastewater samples were in the range of 85–94%. Finally, the extraction efficiency of the method was compared with those of headspace single drop microextraction and headspace SPME with the commercial fibers.
