Evaluation of solution-cathode glow discharge atomic emission spectrometry for the analysis of nanoparticle containing solutions

Abstract The Solution Cathode Glow Discharge (SCGD) is a novel atmospheric-pressure glow discharge plasma sustained in the ambient atmosphere that is an appealing alternative to the inductively-coupled plasma as a source for atomic emission spectrometry. Simple, low power, and inexpensive, the SCGD is an attractive source for continuous environmental monitoring applications such as the quantitation of metallic nanoparticle solutions by atomic emission spectrometry. Metallic nanoparticles (NP) with diameters from 5 nm-150 nm were directly analyzed by SCGD-AES and found to exhibit lower, and size-dependent, elemental sensitivity when compared to dissolved free-ion standard solutions. Acid digestion with matrix-matching was shown to be an effective approach to achieve accurate quantitation. The origin of these morphological matrix effects was studied by investigating experimental parameters such as discharge power, solution flow rate, and influence of added surfactants. Examination of the spatial distribution of atomic emission between cathode and anode showed a shift in peak atomic emission towards the anode of the SCGD for some NPs as compared to free-ion solutions. A novel nested capillary design was used to introduce NP into the SCGD without dissolution within the acidic solvent and showed difference in sensitivity from free-ion solutions to be a NP morphological effect. Correlation of NP boiling point with difference in sensitivity between free-ion and NP solutions supports the conclusion that delayed vaporization of nanoparticles is the source of the morphological matrix effect, due primarily to lower rate of vaporization within the SCGD by lower gas temperatures and short residence time. Analysis of NP of different chemical form, and alloyed nanoparticles composed of more than one element, showed correlation with boiling point. Implications of these results on the possible mechanisms by which material is transferred from the liquid cathode into the plasma are considered.