Evaluation of the operating parameters of the liquid sampling-atmospheric pressure glow discharge (LS-APGD) ionization source for elemental mass spectrometry

Abstract

The liquid sampling-atmospheric pressure glow discharge (LS-APGD) has been assessed as an ionization source for elemental analysis with an interdependent, parametric evaluation regarding sheath/cooling gas flow rate, discharge current, liquid flow rate, and the distance between the plasma and the sampling cone of the mass spectrometer. In order to better understand plasma processes (and different from previous reports), no form of collision/reaction processing was performed to remove molecular interferents. The evaluation was performed employing five test elements: cesium, silver, lead, lanthanum and nickel (10⁻⁴ mol L⁻¹ in 1 mol L⁻¹ HNO₃). The intensity of the atomic ions, levels of spectral background, the signal-to-background ratios, and the atomic-to-oxide/hydroxide adduct ratios were monitored in order to obtain fundamental understanding with regards to not only how each parameter effects the performance of this LS-APGD source, but also the inter-parametric effects. The results indicate that the discharge current and the liquid sampling flow rates are the key aspects that control the spectral composition. A compromise set of operating conditions was determined: sheath gas flow rate = 0.9 L min⁻¹, discharge current = 10 mA, solution flow rate = 10 μL min⁻¹, and sampling distance = 1 cm. Limits of detection (LODs) were calculated using the SBR-RSDB (signal-to-background ratio/relative standard deviation of the background) approach under the optimized condition. The LODs for the test elementals ranged from 15 to 400 ng mL⁻¹ for 10 μL injections, with absolute mass values from 0.2 to 4 ng.