Laser-induced breakdown spectroscopy for soil diagnostics

Summary Laser-optical measurements and fibre optics are potentially attractive tools for applications in soil science because of their great sensitivity and selectivity and their capabilities for on-line and in situ analysis. We have investigated laser-induced breakdown spectroscopy (LIBS) for the quantitative detection of metal ions on the surface of natural soil samples from two sites (Hohenschulen and Oderbruch, Germany). The LIBS technique allows the spatially resolved investigation of adsorption and desorption effects of ions in soil. A frequency doubled (532 nm) and Q-switched Nd:YAG laser with a pulse duration of 8 ns is focused on the soil surface and induces a plasma. Typical power densities are 150 mJ mm−2. The plasma emission is recorded in time and spectrally resolved by a gateable optical multichannel analyser (OMA). A delay time of about 500 ns between laser pulse and OMA gate was used to resolve single atomic and ionic spectral lines from the intense and spectrally broad light that is emitted by the plasma itself. The dependency of the LIBS signal of a single spectral line on the amount of water in the sample is investigated in detail. The results indicate that quenching of water in the plasma plume reduces the line intensities, while the interaction with aquatic colloids increases the intensity. The two processes compete with each other, and a non-linear correlation between measured line intensities and the amount of water in the sample is obtained. This is verified by a simple computer simulation and has to be taken into account for the quantitative interpretation of LIBS signals, e.g. when absolute concentrations are estimated. In the present investigation natural calcium concentrations < 2 μg kg−1 were measured with the LIBS technique in the samples for the two test sites. In addition, measurements were made with dry and water-saturated BaCl2 mixed soil samples, and no significant difference in the detection limit for barium was obtained.