Search

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower stratosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 on sulfate aerosols agree with measured concentrations of NO, NO2, and ClO throughout the day, but fail to account for high concentrations of OH and HO2 observed near sunrise and sunset. The morning burst of [OH] and [HO2] coincides with the rise of [NO] from photolysis of NO2, suggesting a new source of HOxthat photolyzes in the near UV (350 to 400 nm) spectral region. A model that allows for the heterogeneous production of HNO2 results in an excellent simulation of the diurnal variations of [OH] and [HO2].

We describe a new 4D-Var inversion framework for N2O based on the GEOS-Chem chemical transport model and its adjoint, and apply this framework in a series of observing system simulation experiments to assess how well N2O sources and sinks can be constrained by the current global observing network. The employed measurement ensemble includes approximately weekly and quasi-continuous N2O measurements (hourly averages used) from several long-term monitoring networks, N2O measurements collected from discrete air samples aboard a commercial aircraft (CARIBIC), and quasi-continuous measurements from an airborne pole-to-pole sampling campaign (HIPPO). For a two-year inversion, we find that the surface and HIPPO observations can accurately resolve a uniform bias in emissions during the first year; CARIBIC data provide a somewhat weaker constraint. Variable emission errors are much more difficult to resolve given the long lifetime of N2O, and major parts of the world lack significant constraints on the seasonal cycle of fluxes. Current observations can largely correct a global bias in the stratospheric sink of N2O if emissions are known, but do not provide information on the temporal and spatial distribution of the sink. However, for the more realistic scenario where source and sink are both uncertain, we find that simultaneously optimizing both would require unrealistically small errors in model transport. Regardless, a bias in the magnitude of the N2O sink would not affect the a posteriori N2O emissions for the two-year timescale used here, given realistic initial conditions, due to the timescale required for stratosphere-troposphere exchange (STE). The same does not apply to model errors in the rate of STE itself, which we show exerts a larger influence on the tropospheric burden of N2O than does the chemical loss rate over short (< 3 year) timescales. We use a stochastic estimate of the inverse Hessian for the inversion to evaluate the spatial resolution of emission constraints provided by the observations, and find that significant, spatially explicit constraints can be achieved in locations near and immediately upwind of surface measurements and the HIPPO flight tracks; however, these are mostly confined to North America, Europe, and Australia. None of the current observing networks are able to provide significant spatial information on tropical N2O emissions. There, averaging kernels are highly smeared spatially and extend even to the midlatitudes, so that tropical emissions risk being conflated with those elsewhere. For global inversions, therefore, the current lack of constraints on the tropics also places an important limit on our ability to understand extratropical emissions. Based on the error reduction statistics from the inverse Hessian, we characterize the atmospheric distribution of unconstrained N2O, and identify regions in and downwind of South America, Central Africa, and Southeast Asia where new surface or profile measurements would have the most value for reducing present uncertainty in the global N2O budget. [ABSTRACT FROM AUTHOR]