Laser-induced breakdown spectroscopy (LIBS) is a powerful analytical technique for detecting and identifying trace elemental contaminants by monitoring the visible atomic emission from small plasmas. However, mid-infrared (MIR), generally referring to the wavelength range between 2.5 to 25 μm, molecular vibrational and rotational emissions generated by a sample during a LIBS event has not been reported. The LIBS investigations reported in the literature largely involve spectral analysis in the ultraviolet–visible–near-infrared (UV-VIS-NIR) region (less than 1 μm) to probe elemental composition and profiles. Measurements were made to probe the MIR emission from a LIBS event between 3 and 5.75 μm. Oxidation of the sputtered carbon atoms and/or carbon-containing fragments from the sample and atmospheric oxygen produced CO<sub>2</sub> and CO vibrational emission features from 4.2 to 4.8 μm. The LIBS MIR emission has the potential to augment the conventional UV-VIS electronic emission information with that in the MIR region.

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