Rock hyraces: a cause of San rock art deterioration?

San rock art sites are found throughout southern Africa, many showing signs of deterioration. In order to conserve this invaluable heritage, a long-term multidisciplinary project has been launched to monitor the rate of their deterioration and determine the various chemical processes that are possibly contributing to the decay. This study was initiated to establish if Raman spectroscopy could contribute to this project and since rock hyrax colonies live in close proximity to many of these archaeological sites, the possible influence of their metabolic products on the deterioration process was investigated. The precipitates from the urine of rock hyraces were analysed with Raman and Fourier-transform infrared (FTIR) spectroscopy. Where the urine was in contact with the faeces, the precipitates are a mixture of vaterite (a rare polymorph of CaCO3) and the hydrated salt calcium monohydrocalcite (also rarely found in nature). On areas where this contact is at a minimum the common and stable polymorph of CaCO3, calcite, is the main component. SEM micrographs and XRD analysis support the Raman and FTIR results. XRD, FTIR and preliminary GC-MS analyses of hyraceurn, the fossilised mixture of faeces and urine, identified an inorganic phase (potassium chloride, with small concentrations of other salts, e.g. vaterite and weddelite) and anorganic phase, which is a cocktail of various aromatic compounds, mainly amides, alcohols and acids. These compounds could contribute to the crystallisation of these rare carbonates, as well as other uncommon salts detected on the cave walls, such as syngenite. The presence of phosphates in the urine may further act as a stabilizing agent. Copyright (C) 2007 John Wiley & Sons, Ltd.