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.

Faculty of Science Department of Analytical Chemistry Charles University Hlavova 8 128 43 Prague Czech Republic

Institute of Analytical Chemistry of the Czech Academy of Sciences Veveří 97 602 00 Brno Czech Republic

National Research Council of Canada 1200 Montreal Road Ottawa Ontario K1A 0R6 Canada

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NIST Chemistry WebBook

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Identification of Photochemically Generated Volatile Species of Ruthenium and Osmium Using Direct Analysis in Real Time Mass Spectrometry

Sensitive and Spectral Interference-Free Determination of Rhodium by Photochemical Vapor Generation Inductively Coupled Plasma Mass Spectrometry

Efficient Photochemical Vapor Generation from Low Concentration Formic Acid Media