Abstract

Photochemical vapor generation (PVG) of bismuth was accomplished in a simple flow–injection system with a standard Hg low-pressure tube lamp and a coiled Teflon reactor. The influence of a reaction medium flow rate (irradiation time) and composition was investigated using a miniature diffusion flame atomizer and high-resolution continuum source atomic absorption spectrometry. Combination of 40% (v/v) acetic acid, 1.25% (v/v) formic acid and a metal sensitizer at a flow rate of 3 mL min−1 (irradiation time of 90 s) was found optimal. The use of various metals as sensitizers was studied to initiate and enhance PVG substantially. The evident positive effect was found for four metal cations and the enhancement effect was in the following order: Cu2+<Cd2+<Fe2+ ≪ Co2+. At 50 mg L−1 Co2+ as the sensitizer, the overall PVG efficiency of 54 ± 2% was determined from relative comparison of sensitivities obtained with PVG and liquid nebulization coupled simultaneously to inductively coupled plasma mass spectrometry. In order to reach low limits of detection (LOD) at low operation cost, a coupling of PVG to atomic fluorescence spectrometry was tested and conditions of atomization in two flame atomizers were optimized. A blank-limited LOD of 12 ng L−1 was obtained with an advanced flame-in-gas-shield atomizer, which competes with PVG coupled to inductively coupled plasma mass spectrometry (5 ng L−1). Interferences from commonly used inorganic acids (HNO3, HCl and H2SO4) and other elements (As3+, Pb2+, Sb3+, Se4+ and Te4+) were also investigated and the accuracy was verified by analysis of water Standard Reference Material NIST 1643f.

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