The rate of gaseous diffusion in soils affects the exchange of gases between the soil and the atmosphere, thereby affecting rates of soil respiration and other soil microbial processes. Understanding the causes of spatial and temporal variation in soil diffusivity will help explain controls of soil sources and sinks of atmospheric gases. In a study of sources of CO2 in deep soils of forests and pastures of the eastern Amazon, we estimated gaseous diffusivity from bulk density and volumetric water content using published equations that assume the soil to be either an aggregated or nonaggregated medium. The aggregated model requires differentiation of interand intra-aggregate pore space; we estimated intra-aggregate pore space from volumetric water content at field capacity. Steady state 222Rn profiles were predicted from a 1-D model using the diffusivities generated by both aggregated and nonaggregated models. Predicted values were compared with 222Rn activities measured to 5 m depth. While the models predict similar radon activities below about 1 m, large differences are predicted for the top 1 m of soil. The nonaggregated model underestimated diffusivity and overestimated 222Rn activities at 1 m and above, which is not surprising given that surface soils are usually well aggregated. Having validated the aggregated media model using the 222Rn profiles, estimates of diffusivity were combined with measured profiles of CO2 concentrations to estimate CO2 production by depth. About 70-80% of the measured CO2 flux from the soil surface was produced in the top 1 m of soil (including litter in the forest). The 20-30% produced below 1 m results from root respiration and microbial decay of root inputs at depth, indicating that deep soil processes are a non-trivial component of carbon cycling in these deep-rooting ecosystems. About 1% of the 20 kg C m−2 stock of soil C found between 1 m and 8 m depths turns over annually, indicating that land-use changes that affect rooting depth could significantly affect deep soil C stocks over decades to centuries. Fully understanding the role of land-use change on the global carbon cycle will require consideration of these deep soil processes.