Analysis of heavy metals in soils using laser-induced breakdown spectrometry combined with laser-induced fluorescence

The investigation of a hyphenated technique combining laser-induced breakdown spectrometry (LIBS) with laser-induced fluorescence (LIF) for the analysis of heavy metals in soils is described. In order to evaluate the applicability of the technique for fast in-situ analytical purposes, measurements were performed at atmospheric pressure. The plasma radiation was detected using a Paschen–Runge spectrometer equipped with photomultipliers for the simultaneous analysis of 22 different elements. The photomultiplier signals were processed by a fast gateable multichannel integrator. Calibration curves were recorded using a set of spiked soil samples. Limits of detection were derived from these curves for As (3.3 μg/g), Cd (6 μg/g), Cr (2.5 μg/g), Cu (3.3 μg/g), Hg (84 μg/g), Ni (6.8 μg/g), Pb (17 μg/g), Tl (48 μg/g) and Zn (98 μg/g) using the LIBS signals. LIBS-LIF measurements were performed for Cd and Tl. The excitation wavelength as well as the detected fluorescence wavelength for Cd was 228.8 nm. Alternatively, Tl was excited at 276.8 nm, where the observed fluorescence wavelength was 351.9 nm. The calibration curves based on the LIF signals showed significantly improved limits of detection of 0.3 and 0.5 μg/g for Cd and Tl, respectively.