Evaluation of hydrodynamic chromatography coupled to inductively coupled plasma mass spectrometry for speciation of dissolved and nanoparticulate gold and silver

In this study, hydrodynamic chromatography coupled to inductively coupled plasma mass spectrometry has been evaluated for the simultaneous determination of dissolved and nanoparticulate species of gold and silver. Optimization of mobile phase was carried out with special attention to the column recovery of the different species and the resolution between them. Addition of 0.05 mM penicillamine to the mobile phase allowed the quantitative recovery of ionic gold and gold nanoparticles up to 50 nm, whereas 1 mM penicillamine was necessary for quantitative recovery of ionic silver and silver nanoparticles up to 40 nm. The resolution achieved between ionic gold and 10-nm gold nanoparticles was 0.7, whereas it ranged between 0.31 and 0.93 for ionic silver and 10-nm silver nanoparticles, depending on the composition of mobile phase. Best-case mass concentration detection limits for gold and silver species were 0.05 and 0.75 μg L −1 , respectively. The developed methods allowed the simultaneous detection of nanoparticulate and dissolved species of gold and silver in less than 10 min. Size determination and quantification of gold and silver species were carried out in different dietary supplements, showing good agreement with the results obtained by electron microscopy and total and ultrafiltrable contents, respectively. Due to the attainable resolution, the quality of the quantitative results is affected by the relative abundance of nanoparticulate and dissolved species of the element and the size of the nanoparticles if present. Graphical abstract