Underwater sediment analyses by laser induced breakdown spectroscopy and calibration procedure for fluctuating plasma parameters

Laser Induced Breakdown Spectroscopy (LIBS) was applied on sediments directly under water. The aim of the research was to develop a method for measuring the sediment elemental composition, including minor elements, which could be implemented in-situ. The plasma was generated by a double-pulse, Q-Switched Nd:YAG laser operated at 1064 nm. For signal detection, both ICCD and non-gated, compact detectors were used. The major difficulties in underwater sediment analyses are related to the natural and laser induced surface roughness, and to the sample softness. The latter is responsible for the formation of particle clouds above the surface, which scatter both the laser and plasma radiation, and often results in breakdown formation above the analyzed surface. In such cases, a broad sonoluminescence emission from water, formed during the gas bubble collapse was sometimes registered. Under optimized experimental conditions, even by using a non-gated detector and single shot acquisition, it was possible to detect several minor sediment constituents, such as titanium, barium, manganese and others. A crude estimation of the Limit of Detection (LODs) for these elements was performed by underwater measurements on certified soils/sediments. Due to strong shot-to-shot fluctuations in the plasma temperature, well correlated calibration curves, aimed for quantitative analyses, could only be obtained after applying an appropriate data processing procedure. The latter selects automatically only the spectra characterized by similar plasma parameters, which are related to their continuum spectral distribution. Application of such a procedure improves the measurement accuracy also in other surroundings and on samples different from the ones analyzed here.