Differentiating between anthropogenic calcite in plaster, ash and natural calcite using infrared spectroscopy: implications in archaeology

Infrared spectroscopy provides information not only on the type of calcium carbonate polymorph, but also on the extent of atomic order. In calcite, three major infrared absorption peaks are identified: ν₃, ν₂, and ν₄. It was shown that the ratio between ν₂ and ν₄ bands reflects the order of the calcite crystal structure. In this paper we analyse this ratio in geologically formed calcites, archaeological plasters, modern plasters and experimentally prepared plasters. For the geological calcite, the values of the ν₂/ν₄ ratio are around 3, whereas for the experimentally prepared plasters, the values are around 6.5. The ν₂/ν₄ ratio for archaeological plasters varies from 3 to 6. This shows that a high ratio is indicative of disorder in the crystal, and implies that the calcite was formed from calcium oxide at high temperatures. It also implies that this disorder can be preserved for at least 14,000 years. The ν₂/ν₄ ratio of calcite from archaeological sites can thus be used to differentiate between anthropogenic calcite, such as in plaster, mortar and wood ash, from geogenic calcite, such as in limestone. The ratio may also be used to identify plaster or ash that still retains its original crystals and therefore carbon-14 content.