Radiocarbon analysis is an important tool in quantifying soil organic matter (SOM) dynamics within the terrestrial carbon cycle. However, there is increasing appreciation that representing SOM as a single, homogeneous pool with a single, mean 14C concentration is inadequate. We investigate whether the differing patterns in CO2 release during ramped-temperature oxidation reflect organic matter of different ages, and hypothesize that thermally labile SOM (combusting at low temperatures) consists of younger carbon than thermally resistant organic matter. Topsoil samples under contrasting land uses (native vegetation and long-term cultivation) were selected for 14C analysis before and after acid fumigation for the removal of carbonates. Results of bulk 14C analyses showed a significant shift in 14C age from 0.944 Fm under native vegetation to 0.790 Fm under cultivation. Four to 5 “fractions” associated with different CO2-evolution regions were identified by thermal analysis and analyzed for 14C via modifications to NOSAMS' established “programmed temperature pyrolysis system,” in which discrete CO2 fractions evolved during ramped-temperature oxidation were isotopically characterized by a microwave gas ion source (GIS) continuous-flow AMS (CFAMS) system. Results showed that while acid fumigation removed soil carbonates, the treatment also significantly altered the thermograms and inferred SOM composition. While direct attribution of 14C values to individual peaks is somewhat confounded by overlapping temperature ranges for oxidation of unique populations of carbon, in general, thermally stable fractions of SOM appear to be 14C-depleted compared to thermally reactive (low temperature) fractions regardless of pretreatment.