Investigation of hydroxyl-mediated spectral interference from easily ionized elements in laser-enhanced ionization spectrometry in the 281–285 nm range

The spectral background from 281 to 285 nm in the laser-enhanced ionization (LEI) spectrum of aqueous samples containing easily ionized elements (EIE) at concentrations similar to those found in blood was investigated. A complex, structured spectral background was observed, which appears in the presence of Na or K, but does not match the spectral signature of either element. The same behavior was also observed for Li. It was established that this background originates from an energy transfer between laser-excited hydroxyl (OH) molecules and ground-state EIEs. The intensity of this spectral feature was found to increase with EIE concentration and applied electrode voltage. This unexpected source of spectral interference may complicate the determination of trace metals by LEI in the presence of EIEs, since it can not be prevented by simply avoiding interference from atomic lines.