Head space solid phase microextraction based on nano-structured lead dioxide: Application to the speciation of volatile organoselenium in environmental and biological samples

A novel and efficient speciation method based on the nano-structured lead dioxide as stationary phase of head space solid phase microextraction combined with gas chromatography mass spectrometry (GC–MS) was developed for the determination of volatile organoselenium compounds (dimethylselenide (DMSe) and dimethyldiselenide (DMDSe)) in different biological and environmental samples. PbO2 particles with a diameter in the range of 50–70 nm have been grown on platinum wire via elechtrochemical deposition. The effect of different variables on the extraction efficiency was studied simultaneously using an experimental design. The variables of interest in the HS-SPME were condition of coating preparation, desorption time, stirring rate, desorption temperature, ionic strength, time and temperature of extraction. A Plackett–Burman design was performed for screening in order to determine the significant variables affecting the extraction efficiency. Then, the significant factors were optimized by a Box–Behnken design (BBD) and the response surface equations were derived. The detection limit and relative standard deviation (RSD) (n = 5, c = 50 μg L−1) for DMSe were 16 ng L−1 and 4.3%, respectively. They were also obtained for DMDSe as 11 ng L−1 and 4.6%, respectively. The developed technique was found to be applicable to spiked environmental and biological samples.