Graduation Year


Document Type




Degree Granting Department


Major Professor

Jonathan Wynn, Ph.D.


Stable isotopes, Carbon, Oxygen, Carbonates, Fractionation


Global carbon cycle dynamics and fluxes of CO2 between biosphere and atmosphere have been progressed through the use of Keeling Plots. Processes that control and effect the isotopic composition of soil-respired CO2, soil CO2, and equilibrated soil carbonate are specifically addressed in this study through the use of Keeling Plots. Replicate grassland soil profiles containing either C3 or C4 homogenized organic matter were constructed and maintained under controlled settings to encourage the production of soil-respired CO2 and the precipitation of pedogenic carbonate. Soil CO2 was sampled over five months and analyzed with IRMS. Keeling Plots illustrated source CO2 affected by mixing with atmospheric CO2 near the surface and equilibration with ¹³C-depleted CO2 at depth in the zone of likely carbonate precipitation. The d ¹³C Keeling Plot intercepts for the surface horizons (~ -24.7 per mil for C3 profiles and ~ -11.1 per mil for C4 profiles) follow the diffusion-production model when corrected with a constant 4.4 per mil diffusional fractionation, but the Keeling Plot intercepts for developing Bk horizons were curved towards depleted values (~ -36.2 per mil for C3 profiles and ~ -18.4 per mil for C4 profiles). This change in isotopic composition with depth deviates from the usual interpretations of Keeling Plots (steady-state, source to background diffusional mixing). d ¹³C Keeling Plot intercepts indicated evaporative enrichment in the surface horizons of C3 and C4 profiles). This study uses Keeling Plots as a measure of mixing to assess the efficacy of steady-state diffusion-production models of soil CO2 equilibration with soil carbonate.