Hydrated amorphous silicon dioxide (SiO2.nH2O), or opal-A, is deposited naturally from seepage and runoff water as white or brown rock surface coatings, called ‘skins’, that often partly obscure rock paintings and engravings, but occasionally, a thin translucent silica skin can form a protective film over rock art. White lustrous silica skins, less than 1mm thick, occur where seepage water regularly flows from bedding and joint planes, whereas much thinner brown skins form on the sides of boulders and cliffs where runoff water periodically flows. To find the degree of silica skin variability and to determine how climate and rock type affect the properties of silica skins I collected samples at seven Australian and two Canadian rock painting sites that were located in temperate, tropical and sub-arctic regions. The skins had developed on sandstone, quartzite, schist, gneiss and migmatite. I studied the effects of the skins on rock art stability, documented their compositions, textures and structures to establish their common properties, and searched for a way to date the silica which would provide an indication of the minimum age of the underlying art. I also made replication experiments to determine factors that influence the properties of artificial silica skins and the rates of their precipitation so that I could propose a mechanism for natural silica skin formation, and ascertain whether an artificial silica skin could act as a protective rock art conservation measure. I was able to subdivide the analysed samples into silica skin Type’s I, II and III on the basis of their colour (translucent, white or brown), composition (SiO2, Al2O3 and absorbed water contents) and texture (smooth vitreous or vermiform). I propose that silica skins initially begin to form on stable rock surfaces by a process involving a combination of evaporation- and ionic-induced polymerisation of silicic acid in seepage and runoff water. Condensation reactions, random clustering of small silica spheres and deposition of the resulting aggregates eventually produce a thin surficial silica film. Deposition of silica often traps micro-organisms that live in the damp seepage and runoff water zones, and these fossils in finely laminated skins enable the radiocarbon dating of silica deposition, and therefore the dating of rock paintings enclosed by silica. Micro-excavation of silica layers associated with rock art combined with accelerator mass spectrometry gave preliminary radiocarbon determinations that were either consistent with, or contradicted, prevailing opinions about the antiquity of the rock art at selected sites. Experiments using a laser technique for combusting fossilised microorganisms in finely laminated skins were unable to generate sufficient carbon for dating. Catalysis of a mixture of equal proportions of methyl-trimethoxy silane and water produces a translucent stable film that may be suitable as a consolidant, whereas other artificial silica skins made from silica glass and tetra-ethoxy silane develop microfractures on drying, and these are unsuitable as rock art consolidants.
|Date of Award||1996|
|Supervisor||Colin Pearson (Supervisor) & Graham Taylor (Supervisor)|