Stable carbon and oxygen isotopic compositions of wood ash: an experimental study with archaeological implications

Wood ash, composed mainly of the mineral calcite, is an important component in many archaeological sites. Identification of wood ash in the archaeological record is often difficult due to mixing of ash with other calcitic components of geogenic origin and/or due to diagenetic changes. A recent empirical study using the stable isotope compositions of carbon (δ¹³C) and oxygen (δ¹⁸O) in wood ash enabled the identification of mixtures of wood ash with geogenic calcite and to follow diagenetic changes due to partial dissolution and re-precipitation of ash in two prehistoric cave sites in Israel. Little however is known about the processes responsible for the isotopic compositions of wood ash in relation to formation at various temperatures and the influence on isotopic composition of ash from a variety of plant species. Here we present an experimental study of wood ash formed by burning three C3 tree species and one C4 desert bush at different temperatures. The results indicate that there are significant differences in the isotopic compositions of carbon and oxygen between wood ash that forms by combustion at a relatively low temperature (500 °C) and at a higher temperature (900 °C). In addition, we show that the isotopic composition of carbon and oxygen in high temperature wood ash approaches equilibrium over a period of several months and that the carbon isotopic composition of low temperature wood ash may reflect the photosynthetic pathway of the burnt woody species. Lastly, we show that the isotopic compositions obtained from wood ash prepared at different temperatures do not reflect a temperature dependent fractionation process, but a mixing line between calcite that formed by low temperature combustion and calcite formed by high temperature combustion which later underwent re-carbonation with atmospheric CO₂. In addition, we suggest that exchange processes may possibly occur during combustion between decomposing calcium-oxalate and atmospheric O₂, CO₂ and CO. The archaeological implications of this study are discussed in relation to identification of wood ash in the archaeological record, identification of fuel sources and burning temperatures, and diagenetic changes expected in karstic cave environments. The method presented here can be applied at any archaeological site.