Doppler-free flame spectrometry based on resonant degenerate four-wave mixing (D4WM) is shown to be an effective analytical tool for the determination of barium at high spectral resolution. Optical phase conjugation is produced in an air/acetylene flame, resulting in an optical signal that is a coherent time-reversed replica of the probe beam. The degenerate four-wave mixing spectrum of barium for the 6<i>s</i><sup>2</sup> <sup>1</sup><i>S</i><sub>0</sub>-6<i>s</i>6<i>p</i> <sup>1</sup><i>P</i><sub>1</sub> transition at 18,060.19 cm<sup>−1</sup> is collected with a linewidth of 0.08 cm<sup>−1</sup> (FWHM) with the use of a convenient continuously flowing atmospheric-pressure flame atomizer. A preliminary detection limit of 5 μg/mL barium, while a Doppler-free linewidth is maintained at 0.08 cm<sup>−1</sup>, is reported.

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