ALBERT

Description: Measurements from actinic flux spectroradiometers on board the NASA DC-8 during the Atmospheric Tomography (ATom) mission provide an extensive set of statistics on how clouds alter photolysis rates (J values) throughout the remote Pacific and Atlantic Ocean basins. J values control tropospheric ozone and methane abundances, and thus clouds have been included for more than three decades in tropospheric chemistry modeling. ATom made four profiling circumnavigations of the troposphere capturing each of the seasons during 2016–2018. This work examines J values from the Pacific Ocean flights of the first deployment, but publishes the complete Atom-1 data set (29 July to 23 August 2016). We compare the observed J values (every 3 s along flight track) with those calculated by nine global chemistry–climate/transport models (globally gridded, hourly, for a mid-August day). To compare these disparate data sets, we build a commensurate statistical picture of the impact of clouds on J values using the ratio of J-cloudy (standard, sometimes cloudy conditions) to J-clear (artificially cleared of clouds). The range of modeled cloud effects is inconsistently large but they fall into two distinct classes: (1) models with large cloud effects showing mostly enhanced J values aloft and or diminished at the surface and (2) models with small effects having nearly clear-sky J values much of the time. The ATom-1 measurements generally favor large cloud effects but are not precise or robust enough to point out the best cloud-modeling approach. The models here have resolutions of 50–200 km and thus reduce the occurrence of clear sky when averaging over grid cells. In situ measurements also average scattered sunlight over a mixed cloud field, but only out to scales of tens of kilometers. A primary uncertainty remains in the role of clouds in chemistry, in particular, how models average over cloud fields, and how such averages can simulate measurements.

Description: An approach for analysis and modeling of global atmospheric chemistry is developed for application to measurements that provide a tropospheric climatology of those heterogeneously distributed, reactive species that control the loss of methane and the production and loss of ozone. We identify key species (e.g., O3, NOx, HNO3, HNO4, C2H3NO5, H2O, HOOH, CH3OOH, HCHO, CO, CH4, C2H6, acetaldehyde, acetone) and presume that they can be measured simultaneously in air parcels on the scale of a few km horizontally and a few tenths of a km vertically. As a first step, six global models have prepared such climatologies sampled at the modeled resolution for August with emphasis on the vast central Pacific Ocean basin. Objectives of this paper are to identify and characterize differences in model-generated reactivities as well as species covariances that could readily be discriminated with an unbiased climatology. A primary tool is comparison of multidimensional probability densities of key species weighted by the mass of such parcels or frequency of occurrence as well as by the reactivity of the parcels with respect to methane and ozone. The reactivity-weighted probabilities tell us which parcels matter in this case, and this method shows skill in differentiating among the models' chemistry. Testing 100 km scale models with 2 km measurements using these tools also addresses a core question about model resolution and whether fine-scale atmospheric structures matter to the overall ozone and methane budget. A new method enabling these six global chemistry–climate models to ingest an externally sourced climatology and then compute air parcel reactivity is demonstrated. Such an objective climatology containing these key species is anticipated from the NASA Atmospheric Tomography (ATom) aircraft mission (2015–2020), executing profiles over the Pacific and Atlantic Ocean basins. This modeling study addresses a core part of the design of ATom.

Description: We examine the relative contribution of processes controlling the interannual variability (IAV) of tropospheric ozone over four sub-regions of the southern hemispheric tropospheric ozone maximum (SHTOM) over a 20-year period. Our study is based on hindcast simulations from the National Aeronautics and Space Administration Global Modeling Initiative chemistry transport model (NASA GMI-CTM) of tropospheric and stratospheric chemistry, driven by assimilated Modern Era Retrospective Analysis for Research and Applications (MERRA) meteorological fields. Our analysis shows that over SHTOM region, the IAV of the stratospheric contribution is the most important factor driving the IAV of upper tropospheric ozone (270 hPa), where ozone has a strong radiative effect. Over the South Atlantic region, the contribution from surface emissions to the IAV of ozone exceeds that from stratospheric input at and below 430 hPa. Over the South Indian Ocean, the IAV of stratospheric ozone makes the largest contribution to the IAV of ozone with little or no influence from surface emissions at 270 and 430 hPa in austral winter. Over the tropical South Atlantic region, the contribution from IAV of stratospheric input dominates in austral winter at 270 hPa and drops to less than half but is still significant at 430 hPa. Emission contributions are not significant at these two levels. The IAV of lightning over this region also contributes to the IAV of ozone in September and December. Over the tropical southeastern Pacific, the contribution of the IAV of stratospheric input is significant at 270 and 430 hPa in austral winter, and emissions have little influence.

Description: We examine the capability of the Global Modeling Initiative (GMI) chemistry and transport model to reproduce global mid-tropospheric (618 hPa) ozone–carbon monoxide (O3–CO) correlations determined by the measurements from the Tropospheric Emission Spectrometer (TES) aboard NASA's Aura satellite during boreal summer (July–August). The model is driven by three meteorological data sets (finite-volume General Circulation Model (fvGCM) with sea surface temperature for 1995, Goddard Earth Observing System Data Assimilation System Version 4 (GEOS-4 DAS) for 2005, and Modern-Era Retrospective Analysis for Research and Applications (MERRA) for 2005), allowing us to examine the sensitivity of model O3–CO correlations to input meteorological data. Model simulations of radionuclide tracers (222Rn, 210Pb, and 7Be) are used to illustrate the differences in transport-related processes among the meteorological data sets. Simulated O3 values are evaluated with climatological profiles from ozonesonde measurements and satellite tropospheric O3 columns. Despite the fact that the three simulations show significantly different global and regional distributions of O3 and CO concentrations, they show similar patterns of O3–CO correlations on a global scale. All model simulations sampled along the TES orbit track capture the observed positive O3–CO correlations in the Northern Hemisphere midlatitude continental outflow and the Southern Hemisphere subtropics. While all simulations show strong negative correlations over the Tibetan Plateau, northern Africa, the subtropical eastern North Pacific, and the Caribbean, TES O3 and CO concentrations at 618 hPa only show weak negative correlations over much narrower areas (i.e., the Tibetan Plateau and northern Africa). Discrepancies in regional O3–CO correlation patterns in the three simulations may be attributed to differences in convective transport, stratospheric influence, and subsidence, among other processes. To understand how various emissions drive global O3–CO correlation patterns, we examine the sensitivity of GMI/MERRA model-calculated O3 and CO concentrations and their correlations to emission types (fossil fuel, biomass burning, biogenic, and lightning NOx emissions). Fossil fuel and biomass burning emissions are mainly responsible for the strong positive O3–CO correlations over continental outflow regions in both hemispheres. Biogenic emissions have a relatively smaller impact on O3–CO correlations than other emissions but are largely responsible for the negative correlations over the tropical eastern Pacific, reflecting the fact that O3 is consumed and CO generated during the atmospheric oxidation process of isoprene under low-NOx conditions. We find that lightning NOx emissions degrade both positive correlations at mid- and high latitudes and negative correlations in the tropics because ozone production downwind of lightning NOx emissions is not directly related to the emission and transport of CO. Our study concludes that O3–CO correlations may be used effectively to constrain the sources of regional tropospheric O3 in global 3-D models, especially for those regions where convective transport of pollution plays an important role.

Description: An assessment of global particulate nitrate and ammonium aerosol based on simulations from nine models participating in the Aerosol Comparisons between Observations and Models (AeroCom) phase III study is presented. A budget analysis was conducted to understand the typical magnitude, distribution, and diversity of the aerosols and their precursors among the models. To gain confidence regarding model performance, the model results were evaluated with various observations globally, including ground station measurements over North America, Europe, and east Asia for tracer concentrations and dry and wet depositions, as well as with aircraft measurements in the Northern Hemisphere mid-to-high latitudes for tracer vertical distributions. Given the unique chemical and physical features of the nitrate occurrence, we further investigated the similarity and differentiation among the models by examining (1) the pH-dependent NH3 wet deposition; (2) the nitrate formation via heterogeneous chemistry on the surface of dust and sea salt particles or thermodynamic equilibrium calculation including dust and sea salt ions; and (3) the nitrate coarse-mode fraction (i.e., coarse/total). It is found that HNO3, which is simulated explicitly based on full O3-HOx-NOx-aerosol chemistry by all models, differs by up to a factor of 9 among the models in its global tropospheric burden. This partially contributes to a large difference in NO3−, whose atmospheric burden differs by up to a factor of 13. The atmospheric burdens of NH3 and NH4+ differ by 17 and 4, respectively. Analyses at the process level show that the large diversity in atmospheric burdens of NO3−, NH3, and NH4+ is also related to deposition processes. Wet deposition seems to be the dominant process in determining the diversity in NH3 and NH4+ lifetimes. It is critical to correctly account for contributions of heterogeneous chemical production of nitrate on dust and sea salt, because this process overwhelmingly controls atmospheric nitrate production (typically 〉 80 %) and determines the coarse- and fine-mode distribution of nitrate aerosol.

Description: We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating these data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14 880 parcels along 180∘ W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10 % of parcels control 25–30 % of the total reactivities), but do not fully agree on which parcels comprise the top 10 %. Distinct differences in specific features occur, including the spatial regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the six models tested here, three are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify four, effectively distinct, chemical models. Based on this work, we suggest that water vapor differences in model simulations of past and future atmospheres may be a cause of the different evolution of tropospheric O3 and CH4, and lead to different chemistry-climate feedbacks across the models.

Description: We examine the relative contribution of processes controlling the interannual variability (IAV) of tropospheric ozone over four sub-regions of the southern hemispheric tropospheric ozone maximum (SHTOM) over a twenty-year period. Our study is based on hindcast simulations from the National Aeronautics and Space Administration Global Modeling Initiative – Chemistry transport model (NASA GMI-CTM) of tropospheric and stratospheric chemistry, driven by assimilated Modern Era Retrospective-Analysis for Research and Applications (MERRA) meteorological fields. Our analysis shows that over SHTOM region, the IAV of the stratospheric contribution is the most important factor driving the IAV of upper tropospheric ozone (270 hPa), where ozone has a strong radiative effect. Over the south Atlantic region, the contribution from surface emissions to the IAV of ozone exceeds that from stratospheric input at and below 430 hPa. Over the south Indian Ocean, the IAV of stratospheric ozone makes the largest contribution to the IAV of ozone with little or no influence from surface emissions at 270 hPa and 430 hPa in austral winter. Over the tropical south Atlantic region, the contribution from IAV of stratospheric input dominates in austral winter at 270 hPa and drops to less than half but is still significant at 430 hPa. Emission contributions are not significant at these two levels, even during September. The IAV of lightning over this region also contributes to the IAV of ozone in September and December. Over the tropical southeastern Pacific, the contribution of the IAV of stratospheric input is significant at 270 hPa and 430 hPa in austral winter, and emissions have little influence.

Description: An assessment of global nitrate and ammonium aerosol based on simulations from nine models participating in the AeroCom Phase III study is presented. A budget analyses was conducted to understand the typical magnitude, distribution, and diversity of the aerosols and their precursors among the models. To gain confidence on model performance, the model results were evaluated with various observations globally, including ground station measurements over North America, Europe, and East Asia for tracer concentrations and dry and wet depositions, as well as with aircraft measurements in the Northern Hemisphere mid-high latitudes for tracer vertical distributions. Given the unique chemical and physical features of the nitrate occurrence, we further investigated the similarity and differentiation among the models by examining: (1) the pH-dependent NH3 wet deposition; (2) the nitrate formation via heterogeneous chemistry on the surface of dust and sea-salt particles; and (3) the nitrate coarse mode fraction (i.e., coarse/total). It is found that HNO3, which is simulated explicitly based on full O3–HOx–NOx–aerosol chemistry by all models, differs by up to a factor of 9 among the models in its global tropospheric burden. This partially contributes to a large difference in NO3−, whose atmospheric burden differs by up to a factor of 13. Analyses at the process level show that the large diversity in atmospheric burdens of NO3−, NH3, and NH4+ is also related to deposition processes. Wet deposition seems to be the dominant process in determining the diversity in NH3 and NH4+ lifetimes. It is critical to correctly account for contributions of heterogeneous chemical production of nitrate on dust and sea-salt, because this process overwhelmingly controls atmospheric nitrate production (typically 〉 80 %) and determines the coarse and fine mode distribution of nitrate aerosol.

Description: An approach for analysis and modeling of global atmospheric chemistry is developed for application to measurements that provide a tropospheric climatology of those heterogeneously distributed, reactive species that control the loss of methane and the production and loss of ozone. We identify key species (e.g., O3, NOx, HNO3, HNO4, C2H3NO5, H2O, HOOH, CH3OOH, HCHO, CO, CH4, C2H6, acetaldehyde, acetone), and presume that they can be measured simultaneously in air parcels on the scale of a few km horizontally and a few tenths vertically. Six global models have prepared such climatologies (at model resolution) for August with emphasis on the vast central Pacific and Atlantic Ocean basins. We show clear differences in model generated reactivities as well as species covariances that could readily be discriminated with an unbiased climatology. A primary tool is comparison of multi-dimensional probability densities of key species weighted by frequency of occurrence as well as by the reactivity of the parcels with respect to methane and ozone. The reactivity-weighted probabilities tell us which parcels matter in this case. Testing 100-km scale models with 2-km measurements using these tools also addresses a core question about model resolution and whether fine-scale atmospheric structures matter to the overall ozone and methane budget. A new method enabling these six global chemistry-climate models to ingest an externally-sourced climatology and then compute air parcel reactivity is demonstrated. Such an observed climatology is anticipated from the NASA Atmospheric Tomography (ATom) aircraft mission (2015–2020), measuring the key species, executing profiles over the Pacific and Atlantic Ocean basins. This work is a core part of the design of ATom.

Description: We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating over the data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14,880 parcels along 180 W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10 % of parcels control 25–30 % of the total reactivities), but do not fully agree on which parcels comprise the top 10 %. Distinct differences in specific features occur, including the regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the 6 models tested here, 3 are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify 4, effectively distinct, chemical models. Based on this work, we suggest that water vapor differences in model simulations of past and future atmospheres may be a cause of the different evolution of tropospheric O3 and CH4, and lead to different chemistry-climate feedbacks across the models.