Comparing mass balance and adjoint methods for inverse modeling of nitrogen dioxide columns for global nitrogen oxide emissions

Satellite observations offer information applicable to top-down constraints on emission inventories through inverse modeling. Here we compare two methods of inverse modeling for emissions of nitrogen oxides (NOx) from nitrogen dioxide (NO2) columns using the GEOS-Chem chemical transport model and its adjoint. We treat the adjoint-based 4D-Var modeling approach for estimating top-down emissions as a benchmark against which to evaluate variations on the mass balance method. We use synthetic NO2 columns generated from known NOx emissions to serve as truth. We find that error in mass balance inversions can be reduced by up to a factor of 2 with an iterative process that uses finite difference calculations of the local sensitivity of NO2 columns to a change in emissions. In a simplified experiment to recover local emission perturbations, horizontal smearing effects due to NOx transport are better resolved by the adjoint approach than by mass balance. For more complex emission changes, or at finer resolution, the iterative finite difference mass balance and adjoint methods produce similar global top-down inventories when inverting hourly synthetic observations, both reducing the a priori error by factors of 3-4. Inversions of simulated satellite observations from low Earth and geostationary orbits also indicate that both the mass balance and adjoint inversions produce similar results, reducing a priori error by a factor of 3. As the iterative finite difference mass balance method provides similar accuracy as the adjoint method, it offers the prospect of accurately estimating top-down NOx emissions using models that do not have an adjoint.