Biofilm Medium Chemistry and Calcium Oxalate Morphogenesis

The present study is focused on the effect of biofilm medium chemistry on oxalate crystallization and contributes to the study of the patterns of microbial biomineralization and the development of nature-like technologies, using the metabolism of microscopic fungi. Calcium oxalates (weddellite and whewellite in different ratios) were synthesized by chemical precipitation in a weakly acidic environment (pH = 4–6), as is typical for the stationary phase of micromycetes growth, with a ratio of Ca²⁺/C₂O₄²⁻ = 4.0–5.5, at room temperature. Additives, which are common for biofilms on the surface of stone in an urban environment (citric, malic, succinic and fumaric acids; and K⁺, Mg²⁺, Fe³⁺, Sr²⁺, SO₄²⁺, PO₄³⁺ and CO₃²⁺ ions), were added to the solutions. The resulting precipitates were studied via X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDXS). It was revealed that organic acids, excreted by micromicetes, and some environmental ions, as well as their combinations, significantly affect the weddellite/whewellite ratio and the morphology of their phases (including the appearance of tetragonal prism faces of weddellite). The strongest unique effect leading to intensive crystallization of weddellite was only caused by the presence of citric acid additive in the medium. Minor changes in the composition of the additive components can lead to significant changes in the weddellite/whewellite ratio. The effect of the combination of additives on this ratio does not obey the law of additivity. The content of weddellite in the systems containing a representative set of both organic acids and environmental ions is ~20 wt%, which is in good agreement with natural systems.     

The first Raman spectroscopic study of San rock art in the Ukhahlamba Drakensberg Park,South Africa

San rock art sites are found throughout southern Africa; unfortunately this unique heritage is rapidly being lost through natural weathering processes, which have been the focus of various studies conducted in the uKhahlamba Drakensberg Park since 1992. It has recently been shown that the ability of Raman spectroscopy to identify salts on rock faces on a micro, as well as nano scale, can make a contribution to these projects. In order to test the feasibility of undertaking on‐site analyses, a small rock fragment with red and white pigments still attached, which had weathered off the rock face, was analysed with Raman spectroscopy under laboratory conditions, using a Dilor XY Raman instrument and a DeltaNu Inspector Raman portable instrument. A small sample of black pigment (<1 mm²), collected from a badly deteriorated painting and a few relevant samples collected on site, were analysed as well. It was possible to identify most of the inorganic pigments and minerals detected with previous XRD and EDX measurements including whewellite and weddellite coatings, which could be a tool for carbon dating purposes. Two carotenoid pigments were detected for the first time in San rock art pigments. Animal fat was also observed for the first time on both red and white pigments, on the rock face adjacent to the paintings and in highest concentrations on the back of the rock fragment. The spectra quality makes successful on‐site measurements a good prospect. Copyright © 2008 John Wiley & Sons, Ltd.