The combination of isotopic measurements and micrometeorological flux measurements is a powerful new approach that will likely lead to new insight into the dynamics of CO2 exchange between terrestrial ecosystems and the atmosphere. Since the biological processes of photosynthesis and respiration modify the stable isotopic signature of atmospheric CO2 in different ways, measurements of the net fluxes of CO2, 13CO2, and C18OO can be used to investigate the relative contribution of each process to net ecosystem CO2 exchange. We used two independent approaches to measure isotopic fluxes of CO2 over a Tennessee oak-maple-hickory forest in summer 1998. These approaches involved (1) a combination of standard eddy covariance with intensive flask sampling, and (2) a modification to the relaxed eddy accumulation technique. Strong isotopic signals associated with photosynthesis and respiration were observed and persisted in forest air despite the potential for mixing due to atmospheric turbulence. Calm nights allowed a buildup of respiratory CO2 below the canopy and were associated with isotopically depleted forest air in the morning. Windy nights were followed by a relatively more enriched early-morning isotopic signal. Entrainment of air from above the decaying nocturnal boundary layer during daytime mixed layer growth exerted strong control on isotopic composition of forest air, resulting in similar isotope ratios in the late afternoon despite different isotopic starting points following calm or windy nights. The influences of the convective boundary layer and turbulent mixing within the forest cannot be ignored when using isotopes of CO2 investigate biological processes.