Versatile Thin-Film Reactor for Photochemical Vapor Generation

A novel thin-film reactor is described and evaluated for its analytical performance with photochemical vapor generation (TF-PVG). The device, comprising both the generator and a gas-liquid separator, utilizes a vertical central quartz rod onto which the sample is pumped to yield a thin liquid film conducive to the rapid escape of generated hydrophobic species. The rod is housed within a concentric quartz tube through which a flow of argon carrier/stripping gas is passed to remove and transport the generated species to a detector, which in this study is an inductively coupled argon plasma optical emission spectrometer (ICP-OES). The concentric quartz tube is itself surrounded by a 78-turn 0.5 m long quartz coil low-pressure mercury discharge lamp operating at 20 W. The performance of this thin-film photoreactor was evaluated through comparison of analytical figures of merit for detection of a number of elements undergoing PVG in the presence of formic or acetic acid with those arising from conventional solution nebulization under optimized conditions. The TF-PVG reactor provided sensitivity enhancements, of 110-, 120-, 130-, 250-, 120-, 230-, 78-, 1.3-, 16-, and 32-fold for As, Sb, Bi, Sc, Te, Hg, Ni, Co, Fe, and I, respectively, and detection limit enhancements of 110-, 140-, 170-, 270-, 200-, 300-, 160-, 2.7-, 50-, and 44-fold for these same elements. Vapor generation efficiencies ranged from 20-100% for this suite of analytes. The utility of this technique was demonstrated by the determination of Fe and Ni in Certified Reference Materials DORM-3 (fish protein) and DOLT-4 (dogfish liver tissue).