On-site quantitative elemental analysis of metal ions in aqueous solutions by underwater laser-induced breakdown spectroscopy combined with electrodeposition under controlled potential.

We propose a technique of on-site quantitative analysis of Zn(2+) in aqueous solution based on the combination of electrodeposition for preconcentration of Zn onto a Cu electrode and successive underwater laser-induced breakdown spectroscopy (underwater LIBS) of the electrode surface under electrochemically controlled potential. Zinc emission lines are observed with the present technique for a Zn(2+) concentration of 5 ppm. It is roughly estimated that the overall sensitivity over 10 000 times higher is achieved by the preconcentration. Although underwater LIBS suffers from the spectral deformation due to the dense plasma confined in water and also from serious shot-to-shot fluctuations, a linear calibration curve with a coefficient of determination R(2) of 0.974 is obtained in the range of 5-50 ppm.

Single-pulse underwater laser-induced breakdown spectroscopy with nongated detection scheme.

We investigated spatially resolved emission spectra of Al atoms in a very small (∼0.1 mm) laser ablation plasma produced by a single long-pulse (∼100 ns) irradiation of an Al target in water. The spectral feature varied considerably, depending on the position to be measured. The density of the plasma periphery was low enough to neglect the self-absorption effect, even when resonance lines were observed. By properly selecting the position, we successfully obtained well-resolved spectral lines even without time-gated detection. This suggests that time-gating is not necessary anymore in the practical applications of underwater laser-induced breakdown spectroscopy when employing spatially resolved detection system.

Synergetic effects of double laser pulses for the formation of mild plasma in water: toward non-gated underwater laser-induced breakdown spectroscopy.

We experimentally study the dynamics of the plasma induced by the double-laser-pulse irradiation of solid target in water, and find that an appropriate choice of the pulse energies and pulse interval results in the production of an unprecedentedly mild (low-density) plasma, the emission spectra of which are very narrow even without the time-gated detection. The optimum pulse interval and pulse energies are 15-30 µs and about ~1 mJ, respectively, where the latter values are much smaller than those typically employed for this kind of study. In order to clarify the mechanism for the formation of mild plasma we examine the role of the first and second laser pulses, and find that the first pulse produces the cavitation bubble without emission (and hence plasma), and the second pulse induces the mild plasma in the cavitation bubble. These findings may present a new phase of underwater laser-induced breakdown spectroscopy.