Isotopic fractionation corrections for the radiocarbon composition of CO₂ in the soil gas environment must include diffusion and mixing

Abstract. Earth system scientists working with radiocarbon in organic samples use a stable carbon isotope (δ13C) 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 gas environment, where both diffusive gas transport and diffusive mixing are important. Towards this end we applied an analytical soil gas transport model across a range of soil diffusivities and biological CO2 production rates, allowing us to control the radiocarbon (Δ14C) and stable isotope (δ13C) compositions of modeled soil CO2 production and atmospheric CO2. This approach allowed us to assess the bias that results from using the conventional correction method for estimating Δ14C of soil production. We found that the conventional correction is inappropriate for interpreting the radio-isotopic composition of CO2 from biological production, because it does not account for diffusion and diffusive mixing. The resultant Δ14C 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 gas environment that fully accounts for diffusion and diffusive mixing.