Chemical vapor generation of tungsten for atomic spectrometric determination: Homogeneous sensitizer and mechanism study.

BACKGROUND:Inductively coupled plasma-mass spectrometry (ICP-MS) is one of the most powerful instrumental techniques for the determination of tungsten for its low detection limit and wide linear range, while it remains challenging since the analytical performance can be affected by complicated sample matrix. Chemical vapor generation (CVG) harbors the potential to be an alternative to conventional solution nebulization for sample introduction to reduce matrix effect. However, the CVG of tungsten was low in efficiency. It is clear that green and homogeneous enhancement for CVG of tungsten is desired and the mechanism is worth in-depth investigation. RESULTS:Two green and homogeneous enhancement systems for CVG of tungsten were studied, including photochemical vapor generation (PVG) and hydride generation (HG) with sensitizers, Fe3+ and DDTC, respectively. Under optimal conditions, the limits of detection (LODs) were 0.02 μg L-1 for the PVG and 0.003 μg L-1 for the HG, respectively. For PVG, the Fe3+/Fe2+ cycling, free radical species, gaseous product, and the chemical speciation evolution of W in the PVG process were studied in detail. Photo-Fenton effect, generated reductive radical ·CO2-, gaseous product Fe(CO)5, and the mixed valence of W5+/W6+ in the PVG process were found to be crucial for the enhancement. As for HG, the complexation between W(VI) and DDTC might be conducive to the enhanced HG efficiency. SIGNIFICANCE:This work not only in-depth expands the element scope of CVG, but also investigates the enhancement mechanisms experimentally, which might render a deep insight into the CVG processes and foreshadow new guidelines for screening green and efficient homogeneous sensitizers for CVGs of more elements in the future.