Raman spectroscopy of hot desert, high altitude epilithic lichens

Twenty-three highly-coloured lichen specimens belonging to the genera Candelariella, Aspicilia and Xanthoria from high altitude sites in the Atacama Desert, Chile, 2300-4500 metres, have been analysed non-destructively by Raman spectroscopy. The vibrational band assignments in the spectra of the specimens, which were still attached to their limestone or sandstone substrata, were accomplished by comparison with the chemical compositions obtained from wet chemical extraction methods. Carotenoids and chlorophyll were found in all specimens as major components and the characteristic spectral signatures of calcium oxalate monohydrate (whewellite) and dihydrate (weddellite) could be identified; chemical signatures were found for these materials even in lichen thalli growing on the non-calcareous substrata, indicating probably that the calcium was provided here from wind- or rain-borne sources. The Raman spectral biomarkers for a variety of protective biomolecules and accessory pigments such as usnic acid, calycin, pulvinic acid dilactone and rhizocarpic acid have been identified in the lichens, in broad agreement with the chemical extraction profiles. The present study indicates that some form of non-destructive taxonomic identification based on Raman spectroscopy was also possible.