Manganese micro-nodules on ancient brick walls

Romans, Jews, Arabs and Christians built the ancient city of Toledo (Spain) with bricks as the main construction material. Manganese micro-nodules (circa 2 μm in diameter) have grown under the external bio-film surface of the bricks. Recent anthropogenic activities such as industrial emissions, foundries, or traffic and housing pollution have further altered these old bricks. The energy-dispersive X-ray microanalyses (XPS) of micro-nodules show Al, Si, Ca, K, Fe and Mn, with some carbon species. Manganese atoms are present only as Mn4+ and iron as Fe3+ (FeOOH–Fe2O3 mixtures). The large concentration of alga biomass of the River Tagus and the Torcón and Guajaraz reservoirs suggest manganese micro-nodules are formed either from water solutions rich in anthropogenic MnO4K in a reduction environment (from Mn7+ to Mn4+) or by oxidation mechanisms from dissolved Mn2+ (from Mn2+ to Mn4+) linked to algae biofilm onto the ancient brick surfaces. Ancient wall surfaces were also studied by scanning electron microscopy (SEM-EDS) and X-ray diffraction (XRD). Chemical and biological analyses of the waters around Toledo are also analysed for possible sources of manganese. Manganese micro-nodules on ancient brick walls are good indicators of manganese pollution.