Efficient photochemical vapor generation (PVG) of tungsten has been achieved for the first time using a 19 W thin film flow-through photoreactor. The volatile product (most probably tungsten hexacarbonyl) was generated using a flow injection mode and 40% (v/v) formic acid as the reaction medium. An inductively coupled plasma mass spectrometer was utilized for ultrasensitive detection. The addition of Cd2+ as a sensitizer was critical, enhancing the overall PVG efficiency some 30 000-fold. At an optimal irradiation time of 19 s, a 6.1-fold enhancement factor and an overall PVG efficiency of 43% were determined from a comparison of the response to direct solution nebulization when using a sample flow rate of 2 mL min–1 and 500 mg L–1 Cd2+ as a sensitizer. A limit of detection of 0.9 ng L–1 and repeatability (RSD) of 2% at 100 ng L–1 were achieved. Interference from inorganic acids (HNO3, HCl, H2SO4, and HF) was investigated with respect to analytical application to real samples. The accuracy and practical feasibility of this ultrasensitive methodology was successfully verified by analysis of Certified Reference Material CTA-FFA-1 (Fine Fly Ash) and six natural water samples with low W concentrations.

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 Co 2+ and 25 mg L −1 Cd 2+ . 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 Co 2+ and Cd 2+ sensitizers enhanced PVG efficiency by 3,200-fold, permitting a 31 s irradiation time. Although enhanced efficiency (≈40%) could be obtained with increased Co 2+ 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 Ru 3+ . 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).

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.

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