Subsurface approaches for measuring soil CO2 isotopologue flux: Theory and application

Measurements of the stable isotope composition of soil flux have many uses, from separating autotrophic and heterotrophic components of respiration to teasing apart information about gas transport physics. While soil flux chambers are typically used for these measurements, subsurface approaches are becoming more accessible with the introduction of field-deployable isotope analyzers. These subsurface measurements have the unique benefit of offering depth-resolved isotopologue flux data, which can help to disentangle the many soil respiration processes that occur throughout the soil profile. These methods are likely to grow in popularity in the coming years and a solid methodological basis needs to be formed in order for data collected in these subsurface studies to be interpreted properly. Here we explore the range of possible techniques that could be used for subsurface isotopologue gas interpretation and rigorously test the assumptions and application of each approach using a combination of numerical modeling, laboratory experiments, and field studies. Our results suggest that methodological uncertainties arise due to poor assumptions and mathematical instabilities but certain methods, particularly those based on diffusion physics, are able to cope with these uncertainties well and produce excellent depth-resolved isotopologue flux data.