ALBERT

Description: This is the second 'reference' or 'archival' paper for the SHADOZ (Southern Hemisphere Additional Ozonesondes) network and is a follow-on to the recently accepted paper with similar first part of title. The latter paper compared SHADOZ total ozone with satellite and ground-based instruments and showed that the equatorial wave-one in total ozone is in the troposphere. The current paper presents details of the wave-one structure and the first overview of tropospheric ozone variability over the southern Atlantic, Pacific and Indian Ocean basins. The principal new result is that signals of climate effects, convection and offsets between biomass burning seasonality and tropospheric ozone maxima suggest that dynamical factors are perhaps more important than pollution in determining the tropical distribution of tropospheric ozone. The SHADOZ data at (〈http://code9l6.gsfc.nasa.gov/Data_services/shadoz〉) are setting records in website visits and are the first time that the zonal view of tropical ozone structure has been recorded - thanks to the distribution of the 10 sites that make up this validation network.

Description: Ozone vertical profile measurements obtained from ozonesondes flown at Fiji, Samoa, Tahiti and the Galapagos are used to characterize ozone in the troposphere over the tropical Pacific. There is a significant seasonal variation at each of these sites. At sites in both the eastern and western Pacific, ozone is highest at almost all levels in the troposphere during the September-November season and lowest during, March-May. There is a relative maximum at all of the sites in the mid-troposphere during all seasons of the year (the largest amounts are usually found near the tropopause). This maximum is particularly pronounced during, the September-November season. On average, throughout the troposphere at all seasons, the Galapagos has larger ozone amounts than the western Pacific sites. A trajectory climatology is used to identify the major flow regimes that are associated with the characteristic ozone behavior at various altitudes and seasons. The enhanced ozone seen in the mid-troposphere during September-November is associated with flow from the continents. In the western Pacific this flow is usually from southern Africa (although 10-day trajectories do not always reach the continent), but also may come from Australia and Indonesia. In the Galapagos the ozone peak in the mid-troposphere is seen in flow from the South American continent and particularly from northern Brazil. The time of year and flow characteristics associated with the ozone mixing ratio peaks seen in both the western and eastern Pacific suggest that these enhanced ozone values result from biomass burning. In the upper troposphere low ozone amounts are seen with flow that originates in the convective western Pacific.

Description: The chemical and dynamical processes governing the zonal variability of tropical tropospheric ozone and carbon monoxide are investigated for November 2004 using satellite observations, in-situ measurements, and chemical transport models in conjunction with inverse-estimated surface emissions. Vertical ozone profile estimates from the Tropospheric Emission Spectrometer (TES) and ozone sonde measurements from the Southern Hemisphere Additional Ozonesondes (SHADOZ) network show the so called zonal 'wave-one' pattern, which is characterized by peak ozone concentrations (70-80 ppb) centered over the Atlantic, as well as elevated concentrations of ozone over Indonesia and Australia (60-70 ppb) in the lower troposphere. Observational evidence from TES CO vertical profiles and Ozone Monitoring Instrument (OMI) NO2 columns point to regional surface emissions as an important contributor to the elevated ozone over Indonesia. This contribution is investigated with the GEOS-Chem chemistry and transport model using surface emission estimates derived from an optimal inverse model, which was constrained by TES and Measurements Of Pollution In The Troposphere (MOPITT) CO profiles (Jones et al., 2007). These a posteriori estimates, which were over a factor of 2 greater than climatological emissions, reduced differences between GEOS-Chem and TES ozone observations by 30-40% and led to changes in GEOS-Chem upper tropospheric ozone of up to 40% over Indonesia. The remaining residual differences can be explained in part by upper tropospheric ozone produced from lightning NOx in the South Atlantic. Furthermore, model simulations from GEOS-Chem indicate that ozone over Indonesian/Australian is more sensitive to changes in surface emissions of NOx than ozone over the tropical Atlantic.

Description: Our research was targeted at three issues: (1) the factors controlling ozone in the tropical troposphere, (2) the Asian outflow of ozone and its precursors, and (3) the causes of decadal trends observed in ozone and CO. We have also used support from this ACMAP grant to (1) work with Kelly Chance on the retrieval and interpretation of HCHO and NO2 observations from GOME, and (2) develop GEOS-CHEM into a versatile model supporting the work of a large number of users including outside Harvard. ACMAP has provided the core support for GEOS-CHEM development. Applications of the GEOS-CHEM model with primary support from ACMAP are discussed below. A list of publications resulting from this grant is given at the end of the report.

Description: We use a space-based plume height climatology derived from observations made by the Multi-angle Imaging SpectroRadiometer (MISR) instrument aboard the NASA Terra satellite to evaluate the ability of a plume-rise model currently embedded in several atmospheric chemical transport models (CTMs) to produce accurate smoke injection heights. We initialize the plume-rise model with assimilated meteorological fields from the NASA Goddard Earth Observing System and estimated fuel moisture content at the location and time of the MISR measurements. Fire properties that drive the plume-rise model are difficult to estimate and we test the model with four estimates for active fire area and four for total heat flux, obtained using empirical data and Moderate Resolution Imaging Spectroradiometer (MODIS) re radiative power (FRP) thermal anomalies available for each MISR plume. We show that the model is not able to reproduce the plume heights observed by MISR over the range of conditions studied (maximum r2 obtained in all configurations is 0.3). The model also fails to determine which plumes are in the free troposphere (according to MISR), key information needed for atmospheric models to simulate properly smoke dispersion. We conclude that embedding a plume-rise model using currently available re constraints in large-scale atmospheric studies remains a difficult proposition. However, we demonstrate the degree to which the fire dynamical heat flux (related to active fire area and sensible heat flux), and atmospheric stability structure influence plume rise, although other factors less well constrained (e.g., entrainment) may also be significant. Using atmospheric stability conditions, MODIS FRP, and MISR plume heights, we offer some constraints on the main physical factors that drive smoke plume rise. We find that smoke plumes reaching high altitudes are characterized by higher FRP and weaker atmospheric stability conditions than those at low altitude, which tend to remain confined below the BL, consistent with earlier results. We propose two simplified parameterizations for computing injection heights for fires in CTMs and discuss current challenges to representing plume injection heights in large scale atmospheric models.

Description: key challenge in assessing the habitability of martian environments is the detection of organic matter - a requirement of all life as we know it. The Curiosity rover, which landed on August 6, 2012 in Gale Crater of Mars, includes the Sample Analysis at Mars (SAM) instrument suite capable of in situ analysis of gaseous organic components thermally evolved from sediment samples collected, sieved, and delivered by the MSL rover. On Sol 94, SAM received its first solid sample: scooped sediment from Rocknest that was sieved to 〈150 m particle size. Multiple 10-40 mg portions of the scoop #5 sample were delivered to SAM for analyses. Prior to their introduction, a blank (empty cup) analysis was performed. This blank served 1) to clean the analytical instrument of SAMinternal materials that accumulated in the gas processing system since integration into the rover, and 2) to characterize the background signatures of SAM. Both the blank and the Rocknest samples showed the presence of hydrocarbon components.

Description: We analyze the Asian outflow of CO, ozone, and nitrogen oxides (NOx) to the Pacific in spring by using the GEOS-CHEM global three-dimensional model of tropospheric chemistry and simulating the Pacific Exploratory Mission-West (PEM-West B) aircraft mission in February-March 1994. The GEOS-CHEM model uses assimilated meteorological fields from the NASA Goddard Earth Observing System (GEOS). It reproduces relatively well the main features of tropospheric ozone, CO, and reactive nitrogen species observed in PEM-West B, including latitudinal and vertical gradients of the Asian pollution outflow over the western Pacific although simulated concentrations of CO tend to be too low (possibly because biogenic sources are underestimated). We use CO as a long-lived tracer to diagnose the processes contributing to the outflow. The highest concentrations in the outflow are in the boundary layer (0-2 km), but the strongest outflow fluxes are in the lower free troposphere (2-5 km) and reflect episodic lifting of pollution over central and eastern China ahead of eastward moving cold fronts. This frontal lifting, followed by westerly transport in the lower free troposphere, is the principal process responsible for export of both anthropogenic and biomass burning pollution from Asia. Anthropogenic emissions from Europe and biomass burning emissions from Africa make also major contributions to the Asian outflow over the western Pacific; European sources dominate in the lower troposphere north of 40 degrees N, while African sources are important in the upper troposphere at low latitudes. For the period of PEM-West B (February-March) we estimate that fossil fuel combustion and biomass burning make comparable contributions to the budgets of CO, ozone, and NO, in the Asian outflow. We find that 13% of NO, emitted in Asia is exported as NO, or PAN, a smaller fraction than for the United States because of higher aerosol concentrations that promote heterogeneous conversion of NOx to HNO3. Production and export of ozone from Asia in spring is much greater than from the United States because of the higher photochemical activity.

Description: Observations from long-term ozonesonde measurements show robust variations and trends in the evolution of ozone in the middle and upper troposphere over Reunion Island (21.1 degrees South Latitude, 55.5 degrees East Longitude) in June-August. Here we examine possible causes of the observed ozone variation at Reunion Island using hindcast simulations by the stratosphere-troposphere Global Modeling Initiative chemical transport model for 1992-2014, driven by assimilated Modern-Era Retrospective Analysis for Research and Applications (MERRA) meteorological fields. Reunion Island is at the edge of the subtropical jet, a region of strong stratospheric-tropospheric exchange. Our analysis implies that the large interannual variation (IAV) of upper tropospheric ozone over Reunion is driven by the large IAV of the stratospheric influence. The IAV of the large-scale, quasi-horizontal wind patterns also contributes to the IAV of ozone in the upper troposphere. Comparison to a simulation with constant emissions indicates that increasing emissions do not lead to the maximum trend in the middle and upper troposphere over Reunion during austral winter implied by the sonde data. The effects of increasing emission over southern Africa are limited tothe lower troposphere near the surface in August-September.

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 hectopascals), 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 hectopascals. 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 hectopascals in austral winter. Over the tropical South Atlantic region, the contribution from IAV of stratospheric input dominates in austral winter at 270 hectopascals and drops to less than half but is still significant at 430 hectopascals. 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 hectopascals in austral winter, and emissions have little influence.