Isotopic fractionation corrections for the radiocarbon composition ofCO 2 in the soil gas environment must include diffusion and mixing

Abstract. Earth systemscientists working with radiocarbon in organic samples use a stable carbon isotope (δ 13 C) correction to account for mass-dependent fractionation caused primarily by photosynthesis. Although researchers apply this correction routinely, it has not been evaluated for the soil gasenvironment, where both diffusive gas transport and diffusive mixing are important. Towards this end we applied an analytical soil gastransport model across a range of soil diffusivities and biological CO 2 production rates, allowing us to control the radiocarbon (Δ 14 C) and stable isotope (δ 13 C) compositions of modeled soil CO 2 production and atmospheric CO 2 . This approach allowed us to assess the bias that results from using the conventional correction method for estimating Δ 14 C of soil production. We found that the conventional correction is inappropriate for interpreting the radio-isotopic composition of CO 2 from biological production, because it does not account for diffusion and diffusive mixing. The resultant Δ 14 C bias associated with the traditional correction is highest (up to 150 ‰) in soils with low biological production and/or high soil diffusion rates. We propose a new solution for radiocarbon applications in the soil gasenvironment that fully accounts for diffusion and diffusive mixing.