Highly Efficient Photochemical Vapor Generation for Sensitive Determination of Iridium by Inductively Coupled Plasma...

Herein, we describe the highly efficient photochemical vapor generation (PVG) of a volatile species of Ir (presumably iridium tetracarbonyl hydride) for subsequent detection by inductively coupled plasma mass spectrometry (ICPMS). A thin-film flow-through photoreactor, operated in flow injection mode, provided high efficiency following optimization of identified key PVG parameters, notably, irradiation time, pH of the reaction medium, and the presence of metal sensitizers. For routine use and analytical application, PVG conditions comprising 4 M formic acid as the reaction medium, the presence of 10 mg L^-1 Co²⁺ and 25 mg L^-1 Cd²⁺ as added sensitizers, and an irradiation time of 29 s were chosen. An almost 90% overall PVG efficiency for both Ir³⁺ and Ir⁴⁺ oxidation states was accompanied by excellent repeatability of 1.0% (n = 15) of the peak area response from a 50 ng L^-1 Ir standard. Limits of detection ranged from 3 to 6 pg L^-1 (1.5-3 fg absolute), dependent on use of the ICPMS reaction/collision cell. Interferences from several transition metals and metalloids as well as inorganic acids and their anions were investigated, and outstanding tolerance toward chloride was found. Accuracy of the developed methodology was verified by analysis of NIST SRM 2556 (Used Auto Catalyst) following peroxide fusion for sample preparation. Practical application was further demonstrated by the direct analysis of spring water, river water, lake water, and two seawater samples with around 100% spike recovery and no sample preparation except the addition of formic acid and the sensitizers.