New dating confirms that people occupied the Australian continent before the earliest time inferred from conventional radiocarbon analysis. Many of the new ages were obtained by accelerator mass spectrometry 14C dating after an acid–base–acid pretreatment with bulk combustion (ABA-BC) or after a newly developed acid–base–wet oxidation pretreatment with stepped combustion (ABOX-SC). The samples (charcoal) came from the earliest occupation levels of the Devil's Lair site in southwestern Western Australia. Initial occupation of this site was previously dated 35,000 14C yr B.P. Whereas the ABA-BC ages are indistinguishable from background beyond 42,000 14C yr B.P., the ABOX-SC ages are in stratigraphic order to ∼55,000 14C yr B.P. The ABOX-SC chronology suggests that people were in the area by 48,000 cal yr B.P. Optically stimulated luminescence (OSL), electron spin resonance (ESR) ages, U-series dating of flowstones, and 14C dating of emu eggshell carbonate are in agreement with the ABOX-SC 14C chronology. These results, based on four independent techniques, reinforce arguments for early colonization of the Australian continent.

The presence of an independently dated marker in an archaeological site offers rare opportunities for assessing the reliability of radiocarbon dates, especially when these are close to the age limit of the technique. Two different pretreatment protocols (routine ABA and more rigorous ABOx-SC) were employed in the chemical preparation of the same charcoal sample from a layer closely associated to the Campanian Ignimbrite tephra at the Russian Palaeolithic site of Kostenki 14 (Markina Gora). The ABA-treated fraction gave an age of ∽33 14C ka BP, comparable to a previous determination from the same layer, whereas the ABOx-SC produced an older age of ∽35 14C ka BP. This is the first radiocarbon determination of an archaeological sample to provide an age consistent with the "calendar" age for the CI tephra marker.

Charcoal is widely used for radiocarbon dating in archaeological and paleoenvironmental studies. Reliable 14C dating requires appropriate chemical treatment to remove postdeposition contamination from the charcoal samples. This study assesses two pretreatments: acid-base-acid (ABA) and acid-base-oxidation with stepped combustion (ABOx-SC). In addition to 14C, the effects of the treatments on the chemical structure and composition of charcoal were studied using Fourier transform infrared spectroscopy (FTIR) and C/H/O elemental analysis. Samples of pine wood charred in the laboratory at 270, 300, 400, 500, and 600°C, and environmental samples of charred pine wood from pyroclastic flow deposits in southern Kyushu, Japan, were tested. The laboratory-charred samples showed that NaOH treatment removed highly hydrophilic organic components derived from endogenous and exogenous organic materials in the samples and that oxidation treatment caused the oxidative degradation of molecules in samples starting from its edges. The ABA-treated environmental charcoal yielded younger 14C dates than the ABOx-treated samples, probably owing to the effects of remaining organic contaminants bound to the edges of the aromatic molecular structures produced by the original pyrolysis. Meanwhile, it was found that ABA-SC treatment can reduce contaminants as effectively as ABOx-SC treatment. This implies that the stepped combustion (SC), not the chemical oxidation, is the key to reduce contaminant residue left after ABA and ABOx treatments. The results in this study indicate that the investigation of the structural and compositional changes of charcoal during its pretreatment is useful for assessment of the reliability of the 14C ages.