Ultrasensitive Detection of Ruthenium by Coupling Cobalt and Cadmium Ion-Assisted Photochemical Vapor Generation to...

An extremely sensitive methodology for the determination of Ru was developed by coupling photochemical vapor generation (PVG) analyte introduction with inductively coupled plasma mass spectrometry (ICPMS). PVG was undertaken with a thin-film flow-through photoreactor in a medium comprising 8 M formic acid in the presence of 10 mg L^-1 Co²⁺ and 25 mg L^-1 Cd²⁺. The volatile product (presumably ruthenium pentacarbonyl) was generated in a flow injection mode, yielding an overall efficiency of 29% at a sample flow rate of 1.4 mL min^-1. The presence of both Co²⁺ and Cd²⁺ sensitizers enhanced PVG efficiency by 3,200-fold, permitting a 31 s irradiation time. Although enhanced efficiency (≈40%) could be obtained with increased Co²⁺ concentration, this was not suitable for routine use due to co-generation of cobalt carbonyl. Excellent repeatability (<2.5%) and reproducibility (4%) were achieved for 200 ng L^-1 Ru³⁺. Limits of detection ranged from 20 to 42 pg L^-1 (10-21 fg absolute) depending on the measured isotope and operational mode of the ICPMS reaction/collision cell. Interferences from inorganic acids and their anions, several transition metals, and metalloids were investigated. Practical application of the methodology was demonstrated by the analysis of seven water samples of various matrix complexities (well water, spring water, contaminated water, and seawater).