Archaeological age constraints from extrusion ages of obsidian: Examples from the Middle Awash, Ethiopia

Extrusion ages of archaeological obsidian, especially as determined by the 40Ar/39Ar method, can provide reliable maximum ages for tool manufacture. In at least one case in the Middle Awash of Ethiopia, freshly extruded obsidian was used for tool making, resulting in useful maximum ages for site occupation. Hydration resulting in mobility of K and/or Ar in glass, and recoil artifacts produced by neutron irradiation, fatally affect most glass shards from volcanic ashes. The much lower surface area to volume ratio of most archaeological obsidian, however, indicates that the affected areas can be manually removed prior to analysis and the recoil and hydration problems can be easily overcome. A more important issue in dating obsidian is that of possible mass-dependent kinetic isotope fractionation during or subsequent to quenching of volcanic glasses. This is evidenced in some cases by sub-atmospheric initial 40Ar/36Ar ratios, and more generally in sub-atmospheric 38Ar/36Ar. Resulting bias can be avoided through the use of isochron ages, which do not entail the assumption of an initial value of 40Ar/36Ar as is required for plateau ages. Since step heating of glasses often yields limited variability in 40Ar:39Ar:36Ar (and therefore little spread on isochrons), another approach is to use an average value for initial 40Ar/36Ar, with concomitantly larger uncertainty than is associated with atmospheric 40Ar/36Ar, when calculating a plateau age. The 38Ar/36Ar of an un-irradiated subset of our samples validates the inference of kinetic fractionation, and potentially provides a basis for determining initial 40Ar/36Ar in samples that fail to yield isochrons, but only in samples lacking magmatic excess 40Ar. These approaches allow us to reliably apply the 40Ar/39Ar method to volcanic glasses, which has resulted in maximum ages for archaeological sites that are not amenable to traditional geochronological methods. 40Ar/39Ar geochronology can also provide information on the geological provenance of the raw material used for tool making, especially when combined with geochemical data.