Analysis of rock samples collected from rock hewn churches of Lalibela, Ethiopia using laser-induced breakdown spectroscopy

With the aim to study alteration processes of the rock hewn churches from Lalibela (Ethiopia), we applied Laser Induced Breakdown Spectroscopy (LIBS) technique to measure the elemental composition both of the bulk rock materials and their external layers, exposed to the environmental factors. The analytical plasma was generated by nanosecond pulses of an Nd: YAG laser emitting at 1064 nm. Different major and minor sample constituents were detected, including Ca, Mg, Na, Fe, Ti, Al and K. The detected O emission originates both from air surrounding and the sample, while the intensity of N lines, coming exclusively from air, was used for the LIBS signal normalization. By depth profiling of the weathered basalt rock, we observed a lower presence of K in the external layers, corresponding to the first 5 laser shots. The emission from this element is anti-correlated with the line intensities from O, and this was attributed to the variations in relative abundances of clay minerals and K-feldspar. The analogue measurements were performed on the tuff rock, and compared to the spectra from powder samples containing only the external soft material, scratched from the rocks. These analyses show an abundance of H in the weathered, wetted layers and suggest that cations are lost from the constituent primary minerals and replaced by H+; this process disrupts the lattice structure and causes a marked loss of strength. The studies presented here demonstrate that LIBS is a useful technique for studying the alteration processes in the rocks, caused by environmental factors.

► Enrichment of hydrogen was shown for samples collected from the outer wall of the churches.
► R2 decreases as the similarity between two samples line intensities of elements shows different.
► Variation between K and oxygen with a strong inverse association were observed at depth.
►  LIBS line intensity of elements that constitute the samples allows classifying the type of mineral.