Abstract. The carbon isotopic composition (δ13C) of CO2 efflux (δ13Cefflux) from soil is generally interpreted to represent the actual isotopic composition of the respiratory source (δ13CRs). However, soils contain a large CO2 pool in air-filled pores. This pool receives CO2 from belowground respiration and exchanges CO2 with the atmosphere (via diffusion and advection) and the soil liquid phase (via dissolution). Natural or artificial modification of δ13C of atmospheric CO2 (δ13Catm) or δ13CRs causes isotopic disequilibria in the soil-atmosphere system. Such disequilibria generate divergence of δ13Cefflux from δ13CRs (termed "disequilibrium effect"). Here, we use a soil CO2 transport model and data from a 13CO2/12CO2 tracer experiment to quantify the disequilibrium between δ13Cefflux and δ13CRs in ecosystem respiration. The model accounted for diffusion of CO2 in soil air, advection of soil air, dissolution of CO2 in soil water, and belowground and aboveground respiration of both 12CO2 and 13CO2 isotopologues. The tracer data were obtained in a grassland ecosystem exposed to a δ13Catm of −46.9 ‰ during daytime for 2 weeks. Nighttime δ13Cefflux from the ecosystem was estimated with three independent methods: a laboratory-based cuvette system, in-situ steady-state open chambers, and in-situ closed chambers. Earlier work has shown that the δ13Cefflux measurements of the laboratory-based and steady-state systems were consistent, and likely reflected δ13CRs. Conversely, the δ13Cefflux measured using the closed chamber technique differed from these by −11.2 ‰. Most of this disequilibrium effect (9.5 ‰) was predicted by the CO2 transport model. Isotopic disequilibria in the soil-chamber system were introduced by changing δ13Catm in the chamber headspace at the onset of the measurements. When dissolution was excluded, the simulated disequilibrium effect was only 3.6 ‰. Dissolution delayed the isotopic equilibration between soil CO2 and the atmosphere, as the storage capacity for labelled CO2 in water-filled soil pores was 18 times that of soil air. These mechanisms are potentially relevant for many studies of δ13CRs in soils and ecosystems, including FACE experiments and chamber studies in natural conditions. Isotopic disequilibria in the soil-atmosphere system may result from temporal variation in δ13CRs or diurnal changes in the mole fraction and δ13C of atmospheric CO2. Dissolution effects are most important under alkaline conditions.
Measuring and modelling the isotopic composition of soil respiration: insights from a grassland tracer experiment