Abstract

This work aimed to investigate, in detail, the elemental and molecular composition of soil samples collected from the various horizons of an Amazon spodosol profile by combining the atomic technique laser-induced breakdown spectroscopy (LIBS) with two molecular techniques, i.e., Raman and fluorescence spectroscopies. The emission lines of the elements Fe, C, Si, Mg, Al, Ti, Ca, and K with various relative intensities were detected by using LIBS. In particular, C appeared to accumulate in the transition horizon and was proven to be mostly humified by fluorescence analysis. The Raman peaks detected at 465 cm−1 and 800 cm−1 corresponded with the symmetric stretching and bending modes of O-Si-O and Si-OH, respectively. Small shifts toward higher frequencies and slight increases in the width and full width at half maximum (FWHM) of the quartz band at 465 cm−1 appeared in the Tr to K2 horizons, which could be ascribed to a local distortion caused by the high contents of Al of kaolinite mineral phases, as also shown by the LIBS data. Thus, a small amount of kaolinite mineral phase and K measured by LIBS would be present also in the A1 to E2 horizons. The lifetime fluorescence was almost constant in the surface and middle horizons, whereas it increased sharply in the transition horizon and then decreased slightly in the kaolin horizons, which confirmed the presence of more humified recalcitrant organic matter in deeper soil horizons. In conclusion, the combined use of the three spectroscopic techniques appeared to be a very promising approach for studying Amazon soils.

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