We present a comparison of atmospheric transport models that simulate carbonyl sulfide (COS). This is part II of the ongoing Atmospheric Transport Model (ATM) Inter-comparison Project (TransCom–COS). Differently from part I, we focus on seven model intercomparison by transporting two recent COS inversions of NOAA surface data within TM5-4DVAR and LMDz models. The main goals of TransCom-COS part II are (a) to compare the COS simulations using the two sets of optimized fluxes with simulations that use a control scenario (part I) and (b) to evaluate the simulated tropospheric COS abundance with aircraft-based observations from various sources. The output of the seven transport models are grouped in terms of their vertical mixing strength: strong and weak mixing. The results indicate that all transport models capture the meridional distribution of COS at the surface well. Model simulations generally match the aircraft campaigns HIPPO and ATom. Comparisons to HIPPO and ATom demonstrate a gap between observed and modelled COS over the Pacific Ocean at 0–40N, indicating a potential missing source in the free troposphere. The effects of seasonal continental COS uptake by the biosphere, observed on HIPPO and ATom over oceans, is well reproduced by the simulations. We found that the strength of the vertical mixing within the column as represented in the various atmospheric transport models explains much of the model to model differences. We also found that weak-mixing models transporting the optimized flux derived from the strong-mixing TM5 model show a too strong seasonal cycle at high latitudes.

Chemistry transport models (CTMs) are essential tools for characterizing and predicting the role of atmospheric composition and chemistry in Earth’s climate system. This study demonstrates the use of airborne in situ observations to diagnose the representation of atmospheric composition by global CTMs. Process-based diagnostics are developed which minimize the spatial and temporal sampling differences between airborne in situ measurements and CTM grid points. The developed diagnostics make use of dynamical and chemical vertical coordinates as a means of highlighting areas where focused model improvement is needed. The chosen process is the chemical impact of the Asian summer monsoon (ASM), where deep convection serves a unique pathway for rapid transport of surface emissions and pollutants to the stratosphere. Two global CTM configurations are examined for their representation of the ASM upper troposphere and lower stratosphere (UTLS), using airborne observations collected over south Asia. Application of the developed diagnostics to the CTMs reveals the limitations of zonally-averaged surface boundary conditions for species with sufficiently short tropospheric lifetimes, and that species whose stratospheric loss rates are dominated by photolysis have excellent agreement compared to that observed. Overall, the diagnostics demonstrate the strength of airborne observations toward improving model predictions, and highlight the utility of highly-resolved CTMs to improve the understanding of reactive transport of anthropogenic pollutants to the stratosphere.

Tropospheric 18O18O is an emerging proxy for past tropospheric ozone and free-tropospheric temperatures. The basis of these applications is the idea that isotope-exchange reactions in the atmosphere drive 18O18O abundances toward isotopic equilibrium. However, previous work used an offline box-model framework to explain the 18O18O budget, approximating the interplay of atmospheric chemistry and transport. This approach, while convenient, has poorly characterized uncertainties. To investigate these uncertainties, and to broaden the applicability of the 18O18O proxy, we developed a scheme to simulate atmospheric 18O18O abundances (quantified as ∆36 values) online within the GEOS-Chem chemical transport model. These results are compared to both new and previously published atmospheric observations from the surface to 33 km. Simulations using a simplified O2 isotopic equilibration scheme within GEOS-Chem show quantitative agreement with measurements only in the middle stratosphere; modeled ∆36 values are too high elsewhere. Investigations using a comprehensive model of the O-O2-O3 isotopic photochemical system and proof-of-principle experiments suggest that the simple equilibration scheme omits an important pressure dependence to ∆36 values: the anomalously efficient titration of 18O18O to form ozone. Incorporating these effects into the online ∆36 calculation scheme in GEOS-Chem yields quantitative agreement for all available observations. While this previously unidentified bias affects the atmospheric budget of 18O18O in O2, the modeled change in the mean tropospheric ∆36 value since 1850 C.E. is only slightly altered; it is still quantitatively consistent with the ice-core ∆36 record, implying that the tropospheric ozone burden increased less than ~40% over the twentieth century.