Investigation of spectrochemical matrix effects in the liquid sampling-atmospheric pressure glow discharge source

The liquid sampling-atmospheric pressure glow discharge (LS-APGD) microplasma was evaluated with regard to its spectrochemical robustness in its application as a miniaturized optical emission spectroscopy (OES) source for liquid samples. The susceptibility to perturbations in excitation/ionization conditions was probed across a wide range test species, including transition metals, easily ionized elements (group I), and elements with low second ionization potentials (group II). Spectrochemical metrics included the plasma excitation temperature (T_exc), ionization temperatures (T_ion), and magnesium (Mg) ionic:atomic (Mg II:Mg I) ratios. The introduction of the 11 different matrix elements into the LS-APGD at concentrations of 500 μg mL^{- 1} yielded no significant changes in the optically-determined plasma characteristics, indicating a relative immunity to spectrochemical matrix effects. T_exe values for the plasma, using He I as the spectrometric species averaged 2769 ± 79 K across the test matrix, with Mg-based ionization temperature values centered at 6665 ± 151 K. Typical Mg II:Mg I ratios (the so-called robustness parameter) were 0.95 ± 0.3. The lack of appreciable perturbation in excitation/ionization conditions observed here is also manifested in virtually no changes in the probe Mg II and I species' intensities, even at matrix loadings of up to 1000 μg mL^{- 1} of Ba. These observations indicate that the LS-APGD could serve as an OES source for the analysis of diverse aqueous samples without appreciable spectroscopic matrix effects, though potential physical matrix effects including vaporization effects must be evaluated.