Ultra-micro analysis of liquids and suspensions based on laser-induced plasma emissions

Spectrochemical analysis of liquids and suspensions using laser-induced plasma emissions was investigated. Nd:YAG pulsed-laser (532-nm) ablation of aqueous samples produced plasmas that were hot (few eV) and extensively ionized, with electron density in the 10 ¹⁸ cm ^-3 range. Analyte line signals were initially masked by intense plasma continuum emissions, and would only emerge briefly above the background when the plume temperature dropped below 1 eV during the course of its very rapid cooling. In contrast, 193-nm laser ablation at similar fluence generated plasmas of much lower (< 1 eV) temperature but comparable electron density. The plasma continuum emissions were relatively weak and the signal-to-back-ground ratio was a thousand times better. This 'cold' plasma was ideal for sampling trace amounts of biologically important elements such as sodium and potassium. By ablating hydrodynamically focused jets in a sheath-flow, and with acoustic normalization for improved precision, the single-shot detection limits of sodium and potassium were 8 and 50 fg, respectively. Using the sheath-flow arrangement, the amounts of sodium and potassium inside single human red blood cells were simultaneously determined for the first time. The intracellular contents for a given blood donor were found to vary significantly, with only very weak correlation between the amounts of sodium and potassium in individual cells.