Background correction by wavelength modulation for pulsed-laser-excited atomic fluorescence spectrometry.

Instrumentation was constructed to modulate the dye laser wavelength for background correction in laser-excited atomic fluorescence spectrometry (LEAFS). To achieve wavelength modulation a piezoelectric pusher was used to drive the wavelength tuning mirror in a laboratory-constructed grazing incidence dye laser. The laser pulses were synchronized with the piezoelectric pusher movement so that alternate laser pulses measured the atomic fluorescence signal at the analytical atomic spectral line (on-line) and the background signal at a wavelength displaced to one side of the atomic line (off-line). The background-corrected signal was obtained by subtracting the off-line "background" from the on-line "signal plus background". The spectral line width (fwhm) of the dye laser was 0.003 nm, while the wavelength modulation interval was controllable over the range from 0 to 0.2 nm with a spectral resolution limited only by the spectral line width of the laser. This type of background correction could, in principle, be applied to other types of tunable lasers such as pulsed Ti: sapphire lasers. The performance of background correction by wavelength modulation (WM) was demonstrated by measurement of sodium resonance fluorescence in an air-acetylene flame and by thallium nonresonance fluorescence in a graphite furnace. The experimental data indicated that the wavelength modulation corrected, effectively and quantitatively, for flame background, blackbody emission from a graphite furnace, and scatter of laser radiation off aluminum chloride (1 mg/mL as AI) matrix particles in both the furnace and the flame. Analytical results were in good agreement with certified values for the determination of sodium in standard reference materials by the use of modulated LEAFS.