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All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Ab Initio Calculations of Singlet and Triplet Excited States of Chlorine Nitrate and Nitric Acid

Ab initio calculations of vertical excitations to singlet and triplet excited states of chlorine nitrate and nitric acid are reported. The nature of the electronic transitions are examined by decomposing the difference density into the sum of detachment and attachment densities. Counterparts for the three lowest singlet excited states of nitric acid survive relatively unperturbed in chlorine nitrate, while other low-lying singlet states of chlorine nitrate appear to be directly dissociative in the ClO chromophore. These results suggest an assignment of the two main peaks in the experimental chlorine nitrate absorption spectrum. In addition, triplet vertical excitations and the lowest optimized triplet geometries of both molecules are studied.

Grana, Ana M.↗
NASA NTRS1996

Balloon observations of organic and inorganic chlorine in the stratosphere: the role of HClO4 production on sulfate aerosols

Simultaneous observations of stratospheric organic and inorganic chlorine were made in September 1993 out of Fort Sumner, New Mexico, using JPL balloon-borne MkIV interferometer. Between 15 and 20 km, a significant fraction (20-60%) of the inorganic chlorine could not be accounted for by the sum of measured HCl, ClONO2, and HOCl. Laboratory measurements of the reaction of ClO radicals on sulfuric acid solutions have indicated that, along with HCl, small amounts of perchloric acid, HClO4, were formed. Very little is known about the fate of HClO4 in the stratosphere and we use a photochemical box model to determine the impact of this new species on the partitioning of inorganic chlorine in the stratosphere. Assuming that HClO4 is photochemically stable, it is shown that in the enhanced aerosol loading conditions resulting from Mt. Pinatubo's eruption, HClO4 could represent a significant reservoir of chlorine in the lower stratosphere, sequestering up to 0.2 ppbv (or 50%) of the total inorganic chlorine at 16 km. The occurrence of this new species could bring to closure the inorganic chlorine budget deficiency made apparent by recent ER-2 aircraft in situ measurements of HCl.

unmanned↗
NASA NTRS1994

UARS Microwave Limb Sounder Observations of Upper Atmosphere Ozone and Chlorine Monoxide

UARS MLS observations of stratospheric ozone and chlorine monoxide are described. Enhanced concentrations of ClO, the predominant form of reactive chlorine responsible for ozone depletion, are seen within both the northern and southern winter polar vortices. In the southern hemisphere, this leads directly to the development of the annual Antarctic ozone hole. While ozone depletion is also observed in the north, it is less severe and there is considerable interannual variability.

stratosphere ozone chlorine monoxide Microwave Lim↗
NASA NTRS2005

Polar processing and development of the 2004 Antarctic ozone hole : first results from MLS on Aura

The Microwave Limb Sounder (MLS) on Aura is providing an extensive data set on stratospheric winter polar processing, including the first daily global observations of HCl, together with simultaneous measurements of ClO, HNO3, H2O, O3, N2O, and temperature (among others). We present first results charting the evolution of these quantities during the 2004 Antarctic late winter. MLS observations of chlorine deactivation and ozone loss during this period are shown to be consistent with results from the SLIMCAT chemical transport model.

Microwave Limb Sounder (MLS)↗
NASA NTRS2006

Toward a Better Quantitative Understanding of Polar Stratospheric Ozone Loss

Previous studies have shown that observed large O3 loss rates in cold Arctic Januaries cannot be explained with current understanding of the loss processes, recommended reaction kinetics, and standard assumptions about total stratospheric chlorine and bromine. Studies based on data collected during recent field campaigns suggest faster rates of photolysis and thermal decomposition of ClOOCl and higher stratospheric bromine concentrations than previously assumed. We show that a model accounting for these kinetic changes and higher levels of BrO can largely resolve the January Arctic O3 loss problem and closely reproduces observed Arctic O3 loss while being consistent with observed levels of ClO and ClOOCl. The model also suggests that bromine catalyzed O3 loss is more important relative to chlorine catalyzed loss than previously thought.

Frieler, K.↗
NASA NTRS2007

3D Aerosol-Cloud Radiative Interaction Observed in Collocated MODIS and ASTER Images of Cumulus Cloud Fields

3D aerosol-cloud interaction is examined by analyzing two images containing cumulus clouds in biomass burning regions in Brazil. The research consists of two parts. The first part focuses on identifying 3D clo ud impacts on the reflectance of pixel selected for the MODIS aerosol retrieval based purely on observations. The second part of the resea rch combines the observations with radiative transfer computations to identify key parameters in 3D aerosol-cloud interaction. We found that 3D cloud-induced enhancement depends on optical properties of nearb y clouds as well as wavelength. The enhancement is too large to be ig nored. Associated biased error in 1D aerosol optical thickness retrie val ranges from 50% to 140% depending on wavelength and optical prope rties of nearby clouds as well as aerosol optical thickness. We caution the community to be prudent when applying 1D approximations in comp uting solar radiation in dear regions adjacent to clouds or when usin g traditional retrieved aerosol optical thickness in aerosol indirect effect research.

Wen, Guoyong↗
NASA NTRS2005

Sensitivity of Ozone to Bromine in the Lower Stratosphere

Measurements of BrO suggest that inorganic bromine (Br(sub y)) at and above the tropopause is 4 to 8 ppt greater than assumed in models used in past ozone trend assessment studies. This additional bromine is likely carried to the stratosphere by short-lived biogenic compounds and their decomposition products, including tropospheric BrO. Including this additional bromine in an ozone trend simulation increases the computed ozone depletion over the past approx.25 years, leading to better agreement between measured and modeled ozone trends. This additional Br(sub y) (assumed constant over time) causes more ozone depletion because associated BrO provides a reaction partner for ClO, which increases due to anthropogenic sources. Enhanced Br(sub y) causes photochemical loss of ozone below approx.14 km to change from being controlled by HO(sub x) catalytic cycles (primarily HO2+O3) to a situation where loss by the BrO+HO2 cycle is also important.

ozone trends↗
NASA NTRS2005

A Kinetic and Product Study of the Cl + HO2 Reaction

Absolute rate data and product branching ratios for the reactions Cl + HO2 to HCl + O2 (k1a) and Cl + HO2 to OH + ClO (k1b) have been measured from 226 to 336 K at a total pressure of 1 Torr of helium using the discharge flow resonance fluorescence technique coupled with infrared diode laser spectroscopy. For kinetic measurements, pseudo-first-order conditions were used with both reagents in excess in separate experiments. HO2 was produced by two methods: through the termolecular reaction of H atoms with O2 and also by the reaction of F atoms with H2O2. Cl atoms were produced by a microwave discharge of Cl2 in He. HO2 radicals were converted to OH radicals prior to detection by resonance fluorescence at 308 nm. Cl atoms were detected directly at 138 nm also by resonance fluorescence. Measurement of the consumption of HO2 in excess Cl yielded k1a and measurement of the consumption of Cl in excess HO2 yielded the total rate coefficient, k1. Values of k1a and k1 derived from kinetic experiments expressed in Arrhenius form are (1.6 +/- 0.2) x 10-11 exp[(249 +/- 34)/T] and (2.8 +/- 0.1) x 10-11 exp[(123 +/- 15)/T] cm3 molecule-1 s-1, respectively. As the expression for k1 is only weakly temperature dependent, we report a temperature-independent value of k1 = (4.5 +/- 0.4) x 10-11 cm3 molecule-1 s-1. Additionally, an Arrhenius expression for k1b can also be derived: k1b = (7.7 +/- 0.8) x 10-11 exp[-(708 +/- 29)/T] cm3 molecule-1 s-1. These expressions for k1a and k1b are valid for 226 K T 336 and 256 K T 296 K, respectively. The cited errors are at the level of a single standard deviation. For the product measurements, an excess of Cl was added to known concentrations of HO2 and the reaction was allowed to reach completion. HCl product concentrations were determined by IR absorption yielding the ratio k1a/k1 over the temperature range 236 K T 296 K. OH product concentrations were determined by resonance fluorescence giving rise to the ratio k1b/k1 over the temperature range 226 K T 336 K. Both of these ratios were subsequently converted to absolute numbers. Values of k1a and k1b from the product experiments expressed in Arrhenius form are (1.5 +/- 0.1) x 10-11 exp[(222 +/- 17)/T] and (10.6 +/- 1.5) x 10-11 exp[-(733 +/- 41)/T] cm3 molecule-1 s-1, respectively. These expressions for k1a and k1b are valid for 256 K T 296 and 226 K T 336 K, respectively. A combination of the kinetic and product data results in the following Arrhenius expressions for k1a and k1b of (1.4 +/- 0.3) x 10-11 exp[(269 +/- 58)/T] and (12.7 +/- 4.1) x 10-11 exp[-(801 +/- 94)/T] cm3 molecule-1 s-1, respectively. Numerical simulations were used to check for interferences from secondary chemistry in both the kinetic and product experiments and also to quantify the losses incurred during the conversion process HO2 to OH for detection purposes.

rate constants↗
NASA NTRS2006

Long-term Evolution of Upper Stratospheric Ozone at Selected Stations of the Network for the Detection of Stratospheric Change (NDSC)

The long-term evolution of upper stratospheric ozone has been recorded by lidars and microwave radiometers within the ground-based Network for the Detection of Stratospheric Change (NDSC), and by the space-borne Solar Backscatter Ultra-Violet instruments (SBUV), Stratospheric Aerosol and Gas Experiment (SAGE), and Halogen Occultation Experiment (HALOE). Climatological mean differences between these instruments are typically smaller than 5% between 25 and 50 km. Ozone anomaly time series from all instruments, averaged from 35 to 45 km altitude, track each other very well and typically agree within 3 to 5%. SBUV seems to have a slight positive drift against the other instruments. The corresponding 1979 to 1999 period from a transient simulation by the fully coupled MAECHAM4-CHEM chemistry climate model reproduces many features of the observed anomalies. However, in the upper stratosphere the model shows too low ozone values and too negative ozone trends, probably due to an underestimation of methane and a consequent overestimation of ClO. The combination of all observational data sets provides a very consistent picture, with a long-term stability of 2% or better. Upper stratospheric ozone shows three main features: (1) a decline by 10 to 15% since 1980, due to chemical destruction by chlorine; (2) two to three year fluctuations by 5 to 10%, due to the Quasi-Biennial Oscillation (QBO); (3) an 11-year oscillation by about 5%, due to the 11-year solar cycle. The 1979 to 1997 ozone trends are larger at the southern mid-latitude station Lauder (45 S), reaching 8%/decade, compared to only about 6%/decade at Table Mountain (35 N), Haute Provence/Bordeaux (approximately equal to 45 N), and Hohenpeissenberg/Bern(approximately equal to 47 N). At Lauder, Hawaii (20 N), Table Mountain, and Haute Provence, ozone residuals after subtraction of QBO- and solar cycle effects have levelled off in recent years, or are even increasing. Assuming a turning point in January 1997, the change of trend is largest at southern mid-latitude Lauder, +11%/decade, compared to +7%/decade at northern mid-latitudes. This points to a beginning recovery of upper stratospheric ozone. However, chlorine levels are still very high and ozone will remain vulnerable. At this point the most northerly mid-latitude station, Hohenpeissenberg/Bern differs from the other stations, and shows much less clear evidence for a beginning recovery, with a change of trend in 1997 by only +3%/decade. In fact, record low upper stratospheric ozone values were observed at Hohenpeissenberg/Bern, and to a lesser degree at Table Mountain and Haute Provence, in the winters 2003/2004 and 2004/2005.

Steinbrecht, W.↗
NASA NTRS2008

Gamma-Ray Emision from the Broad-Line Radio Galaxy 3C 111

The broad-line radio galaxy 3C 111 has been suggested as the counterpart of the Gamma-ray source 3EGJ0416+3650. While 3C 111 meets most of the criteria for a high-probability identification, like a bright fla t-spectrum radio core and a blazarlike broadband SED, in the Third EG RET Catalog, the large positional offset of about 1.5 degrees put 3C1 11 outside the 99% probability region for 3EG J0416+3650, making this association questionable. We present a re-analysis of all available data for 3C111 from the EGRET archives, resulting in probable detection of high-energy Gamma-ray emission above 1000MeV from a position clo se to the nominal position of 3C 111, in two separate viewing periods (VPs), at a 3sigma level in each. A new source, GROJ0426+3747, appea rs to be present nearby, seen only in the >1000MeV data. For >100MeV, the data are in agreement with only one source (at the original cata log position) accounting for most of the EGRET-detected emission of 3 EGJ0416+3650. A follow-up Swift UVOT/XRT observation reveals one mode rately bright X-ray source in the error box of 3EGJ0416+3650, but bec ause of the large EGRET position uncertainty, it is not certain that the X-ray and Gamma-ray sources are associated. A Swift observation of GROJ0426+3747 detected no X.ray source nearby.

Hartman, Robert C.↗
NASA NTRS2006

The Earth Observing System Microwave Limb Sounder (EOS MLS) on the Aura Satellite

The Earth Observing System Microwave Limb Sounder measures several atmospheric chemical species (OH, HO2, H2O, O3, HCl, ClO, HOCl, BrO, HNO3, N2O, CO, HCN, CH3CN, volcanic SO2), cloud ice, temperature, and geopotential height to improve our understanding of stratospheric ozone chemistry, the interaction of composition and climate, and pollution in the upper troposphere. All measurements are made simultaneously and continuously, during both day and night. The instrument uses heterodyne radiometers that observe thermal emission from the atmospheric limb in broad spectral regions centered near 118, 190, 240, and 640 GHz, and 2.5 THz. It was launched July 15, 2004 on the National Aeronautics and Space Administration's Aura satellite and started full-up science operations on August 13, 2004. An atmospheric limb scan and radiometric calibration for all bands are performed routinely every 25 s. Vertical profiles are retrieved every 165 km along the suborbital track, covering 82 S to 82 N latitudes on each orbit. Instrument performance to date has been excellent; data have been made publicly available; and initial science results have been obtained.

submillimeter wave↗
NASA NTRS2007

Observed and Modeled HOCl Profiles in the Midlatitude Stratosphere: Implication for Ozone Loss

Vertical profiles of stratospheric HOCl calculated with a diurnal steady-state photochemical model that uses currently recommended reaction rates and photolysis cross sections underestimate observed profiles of HOCl obtained by two balloon-borne instruments, FIRS-2 (a far-infrared emission spectrometer) and MkIV (a mid-infrared, solar absorption spectrometer). Considerable uncertainty (a factor of two) persists in laboratory measurements of the rate constant (k(sub 1)) for the reaction ClO + HO2 yields HOCl + O2. Agreement between modeled and measured HOCl can be attained using a value of k(sub 1) from Stimpfle et al. (1979) that is about a factor-of-two faster than the currently recommended rate constant. Comparison of modeled and measured HOCl suggests that models using the currently recommended value for k(sub 1) may underestimate the role of the HOCl catalytic cycle for ozone depletion, important in the midlatitude lower stratosphere.

temperature dependence↗
NASA NTRS2011

Direct EPP Affects on the Middle Atmosphere

Energetic precipitating particles (EPPs) can cause significant direct constituent changes in the mesosphere and stratosphere (middle atmosphere) during certain periods. Both protons and electrons can influence the polar middle atmosphere through ionization and dissociation processes. EPPs can enhance HOx (H, OH, HO2) through the formation of positive ions followed by complex ion chemistry and NOx (N, NO, NO2) through the dissociation of molecular nitrogen. The HOx increases result in direct ozone destruction in the mesosphere and upper stratosphere via several catalytic loss cycles. Such middle atmospheric HOx-caused ozone loss is rather short-lived due to the relatively short lifetime (hours) of the HOx constituents. The NOx family has a considerably longer lifetime than the HOx family and can also lead to catalytic ozone destruction. EPP-caused enhancements of the NOx family can affect ozone directly, if produced in the stratosphere. Ozone decreases from the EPPs lead to a reduction in atmospheric heating and, subsequent atmospheric cooling. Conversely, EPPs can cause direct atmospheric heating through Joule heating. Measured HOx constituents OH and HO2 showed increases due to solar protons. Observed NOx constituents NO and NO2 were enhanced due to both solar protons and precipitating electrons. Other hydrogen- and nitrogen-ocntaining constituents were also measured to be directly influenced by EPPs, including N2O, HNO3, HO2NO2, N2OS, H2O2, ClONO2, HCl, and HOCl. Observed constituents ClO and CO were directly affected by EPPs as well. Many measurements indicated significant direct ozone decreases. A significant number of satellites housed instruments, which observed direct EPP-caused atmospheric effects, including Nimbus 4 (BUV), Nimbus 7 (SBUV), several NOAA platforms (SBUV/2), SME, UARS (HALOE, CLAES), SCISAT-1 (ACE-FTS), Odin (OSIRIS), Envisat-l (GOMOS, MIPAS, SCIAMACHY), and Aura (MLS). Measurements by rockets and ground-based radar also indicated EPP direct impacts. Atmospheric models have been used with some success in predicting the direct EPP impacts on the mesosphere and stratosphere. A review of the observed direct effects of EPP on the middle atmosphere will be given in this presentation.

Jackman, Charles H.↗
NASA NTRS2014

10 meter Sub-Orbital Large Balloon Reflector (LBR)

The realization of a large, space-based 10 meter class telescope for far-infrared/THz studies has long been a goal of NASA. Such a telescope could study the origins of stars, planets, molecular clouds, and galaxies; providing a much needed means of following-up on tantalizing results from recent successful missions such as Spitzer, Herschel, and SOFIA. Indeed, Herschel began its life in the US space program as the Large Deployable Reflector (LDR) to be assembled in low Earth orbit by shuttle astronauts. Escalating costs and smaller federal budget allocations resulted in a downsizing of the mission. However, by combining successful suborbital balloon and ground-based telescope technologies, the dream of a 10 meter class telescope free of ~99% of the Earth's atmospheric absorption in the far-infrared can be realized. The same telescope can also be used to perform sensitive, high spectral and spatial resolution limb sounding studies of the Earth's atmosphere in greenhouse gases such as CO, ClO, O3, and water, as well as serve as a high flying hub for any number of telecommunications and surveillance activities. Flight times of 100+ days will be possible, with instruments having mass and power requirements in excess of ~500 kg and ~1 kW.Here we present the results of our NIAC Step 1, Phase B design study where each key aspect of the LBR concept is discussed and recommendations made for further study in Phase II.These aspects include realization of a large spherical reflecting surface, spherical corrector, pointing system, instrument module, and service module/gondola. Once each hardware component is introduced, a typical LBR Mission profile is described that enables the realization of a stratospheric 10 meter THz observatory and limb sounder. Verification of the design approach was achieved by using a combination of analytical modelling, lab testing of materials and techniques, and building a 3 meter rooftop LBR prototype.

Telescope↗
NASA NTRSDate not supplied

Evaluation of the GEOS-Chem UCX Stratosphere in the GEOS Composition Forecast System

The NASA GEOS Composition Forecast (GEOS-CF) system provides 3-dimensional atmospheric composition analyses and forecasts to the public in near-real time at the high spatial resolution of 25 km. While the main focus of this new product is on tropospheric air quality information, the GEOS-Chem chemistry model (v12) used in this system includes the UCX stratospheric chemistry mechanism. Here, we describe the GEOS-CF system and provide comparisons against remote-sensed observations for stratospheric composition, including measurements of HCl, ClO, NO2, and O3. The GEOS-CF nudges the stratospheric ozone towards the GEOS Forward Processing (GEOS FP) assimilated ozone product; as a result the stratospheric ozone analysis in theGEOS-CF agrees well with observations. Additionally, with the inclusion of the GEOS-Chem UCX stratospheric chemistry mechanism in GEOS-CF, 5-day forecasts, especially during the abnormal 2020 NH polar spring, capture the chemical and dynamical changes missed by the GEOS FP system, which tends towards climatology. The GEOS-CF is a new tool for the research community providing near-real time 3-dimensional gridded information on atmospheric composition throughout the troposphere and stratosphere.

Stratosphere↗