Combining gold nanoparticle-based headspace single-drop microextraction and a paper-based colorimetric assay for selenium determination.

A novel method combining headspace single-drop microextraction with a paper-based colorimetric assay was developed. Headspace single-drop microextraction using a microdrop containing unmodified gold nanoparticles (AuNPs) as both the extractant and the colorimetric probe was used for the sensitive and selective determination of Se(IV). The method relies on the color change of the microdrop solution caused by the adsorption of in situ-generated hydrogen selenide on the surface of AuNPs. Following extraction, the microdrop was spotted onto cellulose paper, and scanometric-assisted digital image analysis was used for selenium quantification. The analytical variables affecting the method sensitivity, including the drop volume, the concentrations of KBH4, HCl, and AuNP solutions, and the extraction time, were studied. Under the optimal conditions, a linear correlation between the colorimetric signal and Se(IV) concentration in the range from 15-100 μg L-1 with a limit of quantification of 12 μg L-1 was achieved. The repeatability of the method was studied by the calculation of intraday and interday precision for the standard solutions at concentrations of 20 and 70 μg L-1. The batch-to-batch reproducibility of the AuNPs synthesized under the same conditions was also assessed. The relative standard deviations were less than 7%. The method provided satisfactory results for the determination of selenium in real samples.