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Ozone Budgets from a Global Chemistry/ Transport Model and Comparison to Observations from POLARIS

The objective of the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) field mission was to obtain data to better characterize the summertime seasonal decrease of ozone at mid to high latitudes. The decrease in ozone occurs mainly in the lower stratosphere and is expected to result from in situ chemical destruction. Instrumented balloons and aircraft were used in POLARIS, along with satellites, to measure ozone and chemical species which are involved with stratospheric ozone chemistry. In order to close the seasonal ozone budget, however, ozone transport must also be estimated. Comparison to a global chemistry and transport model (CTM) of the stratosphere indicates how well the summertime ozone loss processes are simulated and thus how well we can predict the ozone response to changing amounts of chemical source gases. Moreover, the model gives insight into the possible relative magnitude of transport contributions to the seasonal ozone decline. Initial comparison to the Goddard CTM, which uses transport winds and temperatures from meteorological data assimilation, shows a high ozone bias in the model and an attenuated summertime ozone loss cycle. Comparison of the model chemical partitioning, and ozone catalytic loss rates to those derived from measurements shows fairly close agreement both at ER-2 altitudes (20 km) and higher. This suggests that the model transport is too active in resupplying ozone to the high latitude region, although chemistry failings cannot be completely ruled out. Comparison of ozone and related species will be shown along with a full diagnosis of the model ozone budget and its possible sources of error.

Kawa, S. Randy↗

Ozone Budgets from a Global Chemistry/Transport Model and Comparison to Observations from POLARIS

The objective of the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) field mission was to obtain data to better characterize the summertime seasonal decrease of ozone at mid to high latitudes. The decrease in ozone occurs mainly in the lower stratosphere and is expected to result from in situ chemical destruction. Instrumented balloons and aircraft were used in POLARIS, along with satellites, to measure ozone and chemical species which are involved with stratospheric ozone chemistry. In order to close the seasonal ozone budget, however, ozone transport must also be estimated. Comparison to a global chemistry and transport model (CTM) of the stratosphere indicates how well the summertime ozone loss processes are simulated and thus how well we can predict the ozone response to changing amounts of chemical source gases. Moreover, the model gives insight into the possible relative magnitude of transport contributions to the seasonal ozone decline. Initial comparison to the Goddard CTM, which uses transport winds and temperatures from meteorological data assimilation, shows a high ozone bias in the model and an attenuated summertime ozone loss cycle. Comparison of the model chemical partitioning and ozone catalytic loss rates to those derived from measurements shows fairly close agreement both at ER-2 altitudes (20 km) and higher. This suggests that the model transport is too active in resupplying ozone to the high latitude region, although chemistry failings cannot be completely ruled out. Comparison of ozone and related species will be shown along with a full diagnosis of the model ozone budget and its possible sources of error.

Kawa, S. Randolph↗

Aura OMI Observations of Global SO2 and NO2 Pollution from 2005 to 2013

The Ozone Monitoring Instrument (OMI), a NASA partnership with the Netherlands and Finland, flies on the NASA Aura satellite and uses reflected sunlight to measure the two critical atmospheric trace gases: nitrogen dioxide (NO2) and sulfur dioxide (SO2) characterizing daily air quality. Both gases and the secondary pollutants they produce (particulate matter, PM2.5, and tropospheric ozone) are USEPA designated criteria pollutants, posing serious threats to human health and the environment (e.g., acid rain, plant damage and reduced visibility). Our group at NASA GSFC has developed and maintained OMI standard SO2 and NO2 data products. We have recently released an updated version of the standard NO2 L2 and L3 products (SP v2.1) and continue improving the algorithm. We are currently in the process of releasing next generation pollution SO2 product, based on an innovative Principal Component Analysis (PCA) algorithm, which greatly reduces the noise and biases. These new standard products provide valuable datasets for studying anthropogenic pollution on local to global scales. Here we highlight some of the OMI observed changes in air quality over several regions. Over the US average NO2 and SO2 pollution levels had decreased dramatically as a result of both technological improvements (e.g., catalytic converters on cars) and stricter regulations of emissions. We see continued decline in pollution over Europe. Over China OMI observed an increase of about 60 percent in NO2 pollution between 2005 and 2013, despite a temporal reversal of the growing trend due to both 2008 Olympic Games and the economic recession in 2009. Chinese SO2 pollution seems to have stabilized since peaking in 2007, probably due to government efforts to curb SO2 emissions from the power sector. We have also observed large increases in both SO2 and NO2 pollution particularly in Eastern India where a number of large new coal power plants had been built in recent years. We expect that further improvements in the OMI NO2 and SO2 products will allow more robust quantification of long-term trends in global air quality.

SO2↗

Status of Middle Atmosphere-Climate Models: Results SPARC-GRIPS

The middle atmosphere is an important component of the climate system, primarily because of the radiative forcing of ozone. Middle atmospheric ozone can change, over long times, because of changes in the abundance of anthropogenic pollutants which catalytically destroy it, and because of the temperature sensitivity of kinetic reaction rates. There is thus a complex interaction between ozone, involving chemical and climatic mechanisms. One question of interest is how ozone will change over the next decades , as the "greenhouse-gas cooling" of the middle atmosphere increases but the concentrations of chlorine species decreases (because of policy changes). concerns the climate biases in current middle atmosphere-climate models, especially their ability to simulate the correct seasonal cycle at high latitudes, and the existence of temperature biases in the global mean. A major obstacle when addressing this question This paper will present a summary of recent results from the "GCM-Reality Intercomparison Project for SPARC" (GRIPS) initiative. A set of middle atmosphere-climate models has been compared, identifying common biases. Mechanisms for these biases are being studied in some detail, including off-line assessments of the radiation transfer codes and coordinated studies of the impacts of gravity wave drag due to sub-grid-scale processes. ensemble of models will be presented, along with numerical experiments undertaken with one or more models, designed to investigate the mechanisms at work in the atmosphere. The discussion will focus on dynamical and radiative mechanisms in the current climate, but implications for coupled ozone chemistry and the future climate will be assessed.

Pawson, Steven↗

Active and Widespread Halogen Chemistry in the Tropical and Subtropical Free Troposphere

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10degN to 40degS), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (approx.3.4 pptv at 13.5 km), and are 2-4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5-6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.

Wang, Siyuan↗

Exploring Connectivity in Sequence Space of Functional RNA

Emergence of replicable genetic molecules was one of the marking points in the origin of life, evolution of which can be conceptualized as a walk through the space of all possible sequences. A theoretical concept of fitness landscape helps to understand evolutionary processes through assigning a value of fitness to each genotype. Then, evolution of a phenotype is viewed as a series of consecutive, single-point mutations. Natural selection biases evolution toward peaks of high fitness and away from valleys of low fitness. whereas neutral drift occurs in the sequence space without direction as mutations are introduced at random. Large networks of neutral or near-neutral mutations on a fitness landscape, especially for sufficiently long genomes, are possible or even inevitable. Their detection in experiments, however, has been elusive. Although a few near-neutral evolutionary pathways have been found, recent experimental evidence indicates landscapes consist of largely isolated islands. The generality of these results, however, is not clear, as the genome length or the fraction of functional molecules in the genotypic space might have been insufficient for the emergence of large, neutral networks. Thorough investigation on the structure of the fitness landscape is essential to understand the mechanisms of evolution of early genomes. RNA molecules are commonly assumed to play the pivotal role in the origin of genetic systems. They are widely believed to be early, if not the earliest, genetic and catalytic molecules, with abundant biochemical activities as aptamers and ribozymes, i.e. RNA molecules capable, respectively, to bind small molecules or catalyze chemical reactions. Here, we present results of our recent studies on the structure of the sequence space of RNA ligase ribozymes selected through in vitro evolution. Several hundred thousands of sequences active to a different degree were obtained by way of deep sequencing. Analysis of these sequences revealed several large clusters defined such that every sequence in a cluster can be reached from any other sequence in the same cluster through a series of single point mutations. Sequences in a single cluster appear to adopt more than one secondary structure. The mechanism of refolding within a single cluster was examined. To shed light on possible evolutionary paths in the space of ribozymes, the connectivity between clusters was investigated. The effect of length of RNA molecules on the structure of the fitness landscape and possible evolutionary paths was examined by way of comparing functional sequences of 20 and 80 nucleobases in length. It was found that sequences of different lengths shared secondary structure motifs that were presumed responsible for catalytic activity, with increasing complexity and global structural rearrangements emerging in longer molecules.

Wei, Chenyu↗

Determining Latitudinal Extent of Energetic Electron Precipitation Using MEPED On-Board NOAA/POES

Energetic Electron Precipitation (EEP) from the plasma sheet and the radiation belts ionizes the polar lower thermosphere and mesosphere. EEP increases the production of NO x and HO x , which will catalytically destroy ozone, an important element of atmospheric dynamics. Therefore, measurement of the latitudinal extent of the precipitation boundaries is important in quantifying the atmospheric effects of the Sun-Earth interaction. This study uses measurements by the Medium Energy Proton Electron Detector (MEPED) of six NOAA/POES and EUMETSAT/METOP satellites from 2004 to 2014 to determine the latitudinal boundaries of EEP and their variability with geomagnetic activity and solar wind drivers. Variation of the boundaries for different electron energies and Magnetic Local Time (MLT) is studied. Regression analyses are applied to determine the best predictor variable based on solar wind parameters and geomagnetic indices. The highest correlation was found for the pressure-corrected Dst index when applying a linear regression model. A model of the equatorward EEP boundary is developed separately for three different energy channels, >43, >114, and >292 keV, and for 3 hour MLT sectors. For >43 keV EEP, 80% of the equatorward boundaries predicted by the model are within ±2.2° cgmlat. The model exhibits a solar cycle bias where it systematically exaggerates the equatorward movement of the EEP region during solar minimum. The highest accuracy of the model is found in periods dominated by corotating interaction regions/high speed solar wind streams. The result will be a key element for constructing a model of EEP variability to be applied in atmosphere climate models.

E. M. Babu↗

Catalytic-Metal/PdO(sub x)/SiC Schottky-Diode Gas Sensors

Miniaturized hydrogen- and hydrocarbon-gas sensors, heretofore often consisting of Schottky diodes based on catalytic metal in contact with SiC, can be improved by incorporating palladium oxide (PdOx, where 0 less than or equal to x less than or equal to 1) between the catalytic metal and the SiC. In prior such sensors in which the catalytic metal was the alloy PdCr, diffusion and the consequent formation of oxides and silicides of Pd and Cr during operation at high temperature were observed to cause loss of sensitivity. However, it was also observed that any PdOx layers that formed and remained at PdCr/SiC interfaces acted as barriers to diffusion, preventing further deterioration by preventing the subsequent formation of metal silicides. In the present improvement, the lesson learned from these observations is applied by placing PdOx at the catalytic metal/SiC interfaces in a controlled and uniform manner to form stable diffusion barriers that prevent formation of metal silicides. A major advantage of PdOx over other candidate diffusion-barrier materials is that PdOx is a highly stable oxide that can be incorporated into gas sensor structures by use of deposition techniques that are standard in the semiconductor industry. The PdOx layer can be used in a gas sensor structure for improved sensor stability, while maintaining sensitivity. For example, in proof-of-concept experiments, Pt/PdOx/SiC Schottky-diode gas sensors were fabricated and tested. The fabrication process included controlled sputter deposition of PdOx to a thickness of 50 Angstroms on a 400-m-thick SiC substrate, followed by deposition of Pt to a thickness of 450 Angstroms on the PdOx. The SiC substrate (400 microns in thickness) was patterned with photoresist and a Schottky-diode photomask. A lift-off process completed the definition of the Schottky-diode pattern. The sensors were tested by measuring changes in forward currents at a bias potential of 1 V during exposure to H2 in N2 at temperatures ranging from 450 to 600 C for more than 750 hours. The sensors were found to be stable after a break-in time of nearly 200 hours. The sensors exhibited high sensitivity: sensor currents changed by factors ranging from 300 to 800 when the gas was changed from pure N2 to 0.5 percent H2 in N2.

Hunter, Gary W.↗

On the Quality of the Nimbus 7 LIMS Version 6 Ozone for Studies of the Middle Atmosphere

The Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) radiance profile dataset of 1978/79 was reconditioned and reprocessed to Version 6 (V6) profiles of temperature and species that are improved significantly over those from Version 5 (V5). The LIMS V6 dataset was archived for public use in 2002. Improvements for its ozone include: (1) a more accurate accounting for instrument and spacecraft motion effects in the radiances, (2) the use of better spectroscopic line parameters for its ozone forward model, (3) retrievals of all its scans, (4) more accurate and compatible temperature versus pressure profiles (or T(p)), which are needed for the registration of the ozone radiances and for the removal of temperature effects from them, and (5) a better accounting for interfering species in the lower stratosphere. The retrieved V6 ozone profiles extend from near cloud top altitudes to about 80 km and from 64S to 84N latitude with better sampling along the orbit than for the V5 dataset. Calculated estimates of the single-profile precision and accuracy are provided for the V6 ozone from this study. Precision estimates based on the data themselves are of order 3% or better from 1 to 30 hPa. Estimates of total systematic error for a single profile are hard to generalize because the separate sources of error may not all be of the same sign and they depend somewhat on the atmospheric state. It is estimated that the V6 zonal mean ozone distributions are accurate to within 9% to 7% from 50 hPa to 3 hPa, respectively. Effects of a temperature bias can be significant and may be present at 1 to 2 hPa though. There may be ozone biases of order 10% at those levels due to possible biases of up to +2 K, but there is no indication of a similar problem elsewhere in the stratosphere. Simulation studies show that the LIMS retrievals are also underestimating slightly the small amplitudes of the atmospheric temperature tides, which affect its retrieved day/night ozone differences. There are small biases in the middle to lower stratosphere for the ascending versus descending node LIMS ozone, due principally to not accounting for the asymmetric weighting of its radiances across the tangent layer. The estimates of total accuracy were assessed by comparing the daily zonal mean LIMS ozone distributions against those from the Nimbus 7 SBUV Version 8 (V8) dataset for the same period. Generally, the LIMS V6 ozone agrees well with SBUV, except perhaps in the tropical lower stratosphere where the LIMS ozone is less. Still, the accuracy for LIMS V6 ozone in the lower stratosphere is improved over that found for LIMS V5, as indicated by several LIMS comparisons with ECC ozonesonde profiles. The LIMS V6 ozone is considered especially suitable for detailed studies of large-scale stratospheric processes above the 100-hPa level. Comparison of diurnal, photochemical model calculations with the monthly-averaged, upper stratospheric ozone observed from LIMS V6 indicates only a slight ozone deficit for the model at about 2 hPa. However, that deficit exhibits little to no seasonal variation and is in good agreement with similar model comparisons for a seasonal time series of ozone obtained with ground-based microwave instruments. Because the LIMS V6 ozone in the lower stratosphere has improved accuracy and sampling versus that of V5, it should now be possible to conduct quantitative studies of ozone transport and chemistry for the northern hemisphere, polar stratospheric winter of 1978/79 a time period when the catalytic loss of ozone due to reactive chlorine should not have been a major factor for the Arctic region.

Remsberg, Ellis↗