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At least 667 records · Page 37

High Resolution Chemical Study of ALH84001

We have studied the chemistry of a sample of the SNC meteorite ALH84001 using an environmental scanning electron microscope (ESEM) with an energy dispersive chemical analytical detector and a focused ion beam secondary ion mass spectrometer (FIB-SIMS). Here we present the chemical data, both spectra and images, from two techniques that do not require sample preparation with a conductive coating, thus eliminating the possibility of preparation-induced textural artifacts. The FIB-SIMS instrument includes a column optimized for SEM with a quadrupole type mass spectrometer. Its spatial and spectral resolution are 20 nm and 0.4 AMU, respectively. The spatial resolution of the ESEM for chemical analysis is about 100 nm. Limits of detection for both instruments are mass dependent. Both the ESEM and the FIB-SIMS instrument revealed contrasting surficial features; crumbled, weathered appearance of the matrix in some regions as well as a rather ubiquitous presence of euhedral halite crystals, often associated with cracks or holes in the surface of the rock. Other halogen elements present in the vicinity of the NaCl crystals include K and Br. In this report, elemental inventories are shown as mass spectra and as X-ray maps.

Conrad, Pamela G.↗

HALOE Algorithm Improvements for Upper Tropospheric Sounding

This report details the ongoing efforts by GATS, Inc., in conjunction with Hampton University and University of Wyoming, in NASA's Mission to Planet Earth Upper Atmospheric Research Satellite (UARS) Science Investigator Program entitled 'HALOE Algorithm Improvements for Upper Tropospheric Sounding.' The goal of this effort is to develop and implement major inversion and processing improvements that will extend Halogen Occultation Experiment (HALOE) measurements further into the troposphere. In particular, O3, H2O, and CH4 retrievals may be extended into the middle troposphere, and NO, HCl and possibly HF into the upper troposphere. Key areas of research being carried out to accomplish this include: pointing/tracking analysis; cloud identification and modeling; simultaneous multichannel retrieval capability; forward model improvements; high vertical-resolution gas filter channel retrievals; a refined temperature retrieval; robust error analyses; long-term trend reliability studies; and data validation. The current (first year) effort concentrates on the pointer/tracker correction algorithms, cloud filtering and validation, and multichannel retrieval development. However, these areas are all highly coupled, so progress in one area benefits from and sometimes depends on work in others.

Thompson, Robert Earl↗

Two-Step Calibration of a Multiwavelength Pyrometer for High Temperature Measurement Using a Quartz Lamp

There is no theoretical upper temperature limit for pyrometer application in temperature measurements. NASA Glenn's multiwavelength pyrometer can make measurements over wide temperature ranges. However, the radiation spectral response of the pyrometer's detector must be calibrated before any temperature measurement is attempted, and it is recommended that calibration be done at temperatures close to those for which measurements will be made. Calibration is a determination of the constants of proportionality at all wavelengths between the detector's output (voltage) and its input signals (usually from a blackbody radiation source) in order to convert detector output into radiation intensity. To measure high temperatures, the detectors are chosen to be sensitive in the spectral range from 0.4 to 2.5 micrometers. A blackbody furnace equilibrated at around 1000 C is often used for this calibration. Though the detector may respond sensitively to short wavelengths radiation, a blackbody furnace at 1000 C emits only feebly at very short wavelengths. As a consequence, the calibration constants that result may not be the most accurate. For pyrometry calibration, a radiation source emitting strongly at the short wavelengths is preferred. We have chosen a quartz halogen lamp for this purpose.

Ng, Daniel↗

Sources of Variability in the Stratospheric Column of Nitrogen Dioxide

Instruments such as the Global Ozone Monitoring Experiment (GOME, on the European Remote Sensing Satellite (ERS-2), launched 1995), the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY, on ENVISAT, to be launched July 2001) and the Ozone Monitoring Instrument (OMI on EOS Aura, to be launched 2003) make measurements of the total column of NO2. There is interest in separating the stratospheric and tropospheric contributions to the column, as the tropospheric column provides a measure of pollution. We are using a 3D chemistry and transport model driven by winds from the Goddard Space Flight Center Data Assimilation System to examine variability in the stratospheric NO2 column. Model results for NOx = NO + NO2 + 2N2O5 will be shown to compare well with sunset observations from the Halogen Occultation Experiment on the Upper Atmosphere Research Satellite, and to exhibit similar temporal and spatial dependence. Partitioning between NO, NO2, and N2O5 is also shown to compare well with observations. This good agreement supports the use of simulated fields in the stratosphere to derive the tropospheric column from the total column. Preliminary comparisons of the tropospheric column with model simulations for the troposphere will also be shown.

Douglass, Anne↗

Data Comparison: Satellite and Falling Sphere Temperatures

Small meteorological rocketsondes providing temperature data have beam used for comparison with, and validation of measurements from satellite-borne instruments. A significant number of rocket-borne falling spheres were launched in conjunction with the Upper Atmosphere Research Satellite (UARS) for validation of the Halogen Occultation Experiment (HALOE), High Resolution Doppler Interferometer (HRDI), and the Microwave Limb Sounder (MLS) instruments. Upper stratosphere and mesosphere temperatures measured with these instruments on UARS are compared with inflatable spheres launched from Wallops Island (1992-1999), Brazil (1994), Hawaii (1992), Norway (1992), and Sweden (1993 and 1996). Time and space differences varied between the satellite measurement and the rocketsonde launch, for example HALOE overpasses occurred within 5 days and in some cases there were spatial differences of up to 30 degrees longitude. Validation measurements of the HRDI instrument occurred at Wallops Island when it passed within 20 minutes and 330 kilometers of the launch site. Because of discontinuity in the falling sphere drag coefficients when fall speed neared MACH 1 falling sphere temperatures near 70 kilometers attitude are biased toward lower temperatures. Availability of improved software and a new atmospheric model have helped to reduce this bias. The validated remote instrument measurements permit a new perspective of atmospheric structure to be formed, not always possible with the limited number of falling sphere measurements. Features of the remote measurement temperature profiles and their possible use to extend the climatological data base at the rocketsonde sites will be discussed.

Schmidlin, Francis J.↗

Ab Initio Studies of Stratospheric Ozone Depletion Chemistry

An overview of the current understanding of ozone depletion chemistry, particularly with regards the formation of the so-called Antarctic ozone hole, will be presented together with an outline as to how ab initio quantum chemistry can be used to further our understanding of stratospheric chemistry. The ability of modern state-of-the art ab initio quantum chemical techniques to characterize reliably the gas-phase molecular structure, vibrational spectrum, electronic spectrum, and thermal stability of fluorine, chlorine, bromine and nitrogen oxide species will be demonstrated by presentation of some example studies. The ab initio results will be shown to be in excellent agreement with the available experimental data, and where the experimental data are either not known or are inconclusive, the theoretical results are shown to fill in the gaps and to resolve experimental controversies. In addition, ab initio studies in which the electronic spectra and the characterization of excited electronic states of halogen oxide species will also be presented. Again where available, the ab initio results are compared to experimental observations, and are used to aid in the interpretation of experimental studies.

Lee, Timothy J.↗

Evaluation of SAGE II and Balloon-Borne Stratospheric Aerosol Measurements: Evaluation of Aerosol Measurements from SAGE II, HALOE, and Balloonborne Optical Particle Counters

Stratospheric aerosol measurements from the University of Wyoming balloonborne optical particle counters (OPCs), the Stratospheric Aerosol and Gas Experiment (SAGE) II, and the Halogen Occultation Experiment (HALOE) were compared in the period 1982-2000, when measurements were available. The OPCs measure aerosol size distributions, and HALOE multiwavelength (2.45-5.26 micrometers) extinction measurements can be used to retrieve aerosol size distributions. Aerosol extinctions at the SAGE II wavelengths (0.386-1.02 micrometers) were computed from these size distributions and compared to SAGE II measurements. In addition, surface areas derived from all three experiments were compared. While the overall impression from these results is encouraging, the agreement can change with latitude, altitude, time, and parameter. In the broadest sense, these comparisons fall into two categories: high aerosol loading (volcanic periods) and low aerosol loading (background periods and altitudes above 25 km). When the aerosol amount was low, SAGE II and HALOE extinctions were higher than the OPC estimates, while the SAGE II surface areas were lower than HALOE and the OPCS. Under high loading conditions all three instruments mutually agree to within 50%.

Hervig, Mark↗

Evaluation of SAGE II and Balloon-Borne Stratospheric Aerosol Measurements

Under funding from this proposal we evaluated measurements of stratospheric sulfate aerosols from three platforms. Two were satellite platforms providing solar extinction measurements, the Stratospheric Aerosol and Gas Experiment (SAGE) II using wavelengths from 0.386 - 1.02 microns, and the Halogen Occultation Experiment (HALOE) using wavelengths from 2.45 to 5.26 microns. The third set of measurements was from in situ sampling by balloonborne optical particle counters (OPCs). The goal was to determine the consistency among these data sets. This was accomplished through analysis of the existing measurement records, and through additional balloonborne OPC flights coinciding with new SAGE II observations over Laramie, Wyoming. All analyses used the SAGE II v 6.0 data. This project supported two balloon flights per year over Laramie dedicated to SAGE II coincidence. Because logistical factors, such as poor surface weather or unfavorable payload impact location, can make it difficult to routinely obtain close coincidences with SAGE II, we attempt to conduct nearly every Laramie flight (roughly one per month) in conjunction with a SAGE II overpass. The Laramie flight frequency has varied over the years depending on field commitments and funding sources. Current support for the Laramie measurements is from the National Science Foundation in addition to support from this NASA grant. We have also completed a variety of comparisons using aerosol measurements from SAGE II, OPCs, and HALOE. The instruments were compared for their various estimates of aerosol extinction at the SAGE II wavelengths and for aerosol surface area. Additional results, such as illustrated here, can be found in a recently accepted manuscript describing comparisons between SAGE II, HALOE, and OPCs for the period 1982 - 2000. While overall, the impression from these results is encouraging, the agreement of the measurements changes with latitude, altitude, time, and parameter. In the broadest sense, these comparisons fall into two categories: high aerosol loading (volcanic periods) and low aerosol loading (background periods and altitudes above 25 km). When the aerosol amount is low SAGE II and HALOE extinctions are higher than the OPC estimates, while the SAGE II surface areas are lower than HALOE and the OPCS. Under high loading conditions, all three instruments mutually agree to within 50%.

Source record↗

Heterogeneous Uptake and Conversion of HOBr on H2SO4 at Upper Tropospheric and Stratospheric Temperatures (255 - 210 K)

Halogen species are known to catalytically destroy ozone in several different regions of the atmosphere. In addition to directly destroying ozone, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr), a key species in the linkage of BrOx to ClOx and HOx, is produced by the hydrolysis of BrONO2 on sulfate aerosols, and thus the heterogeneous behavior of HOBr must be understood. We have measured the solubility of HOBr in 45 to 70 percent by weight sulfuric acid solutions. Over the temperature range 208 to 255 K, HOBr is very soluble in sulfuric acid, H(*) = 10(exp 4) to 10(exp 8) M/atm. The solubility is temperature dependent, and our results agree well with those of Waschewsky and Abbott for 60 percent by weight H2SO4. HOBr is nearly as soluble as HBr, indicating that equilibrium concentrations of HOBr could approach those of HBr in sulfuric acid aerosols. Despite the high solubility of HOBr, stratospheric aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Uptake of HOBr was nearly always accompanied by reaction, producing Br2O and possibly Br2. The effect of this bromine conversion pathway on the HOx and ClOx families, particularly at temperatures as warm as 255 K, will be considered.

Iraci, Laura T.↗

A Miniature Mineralogical Instrument for In-Situ Characterization of Ices and Hydrous Minerals at the Lunar Poles

Lunar missions over the past few years have provided new evidence that water may be present at the lunar poles in the form of cold-trapped ice deposits, thereby rekindling interest in sampling the polar regions. Robotic landers fitted with mineralogical instrumentation for in-situ analyses could provide unequivocal answers on the presence of crystalline water ice and/or hydrous minerals at the lunar poles. Data from Lunar Prospector suggest that any surface exploration of the lunar poles should include the capability to drill to depths of more than 40 cm. Limited data on the lunar geotherm indicate temperatures of approximately 245-255 K at regolith depths of 40 cm, within a range where water may exist in the liquid state as brine. A relevant terrestrial analog occurs in Antarctica, where the zeolite mineral chabazite has been found at the boundary between ice-free and ice-cemented regolith horizons, and precipitation from a regolith brine is indicated. Soluble halogens and sulfur in the lunar regolith could provide comparable brine chemistry in an analogous setting. Regolith samples collected by a drilling device could be readily analyzed by CheMin, a mineralogical instrument that combines X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques to simultaneously characterize the chemical and mineralogical compositions of granular or powdered samples. CheMin can unambiguously determine not only the presence of hydrous alteration phases such as clays or zeolites, but it can also identify the structural variants or types of clay or zeolite present (e.g., well-ordered versus poorly ordered smectite; chabazite versus phillipsite). In addition, CheMin can readily measure the abundances of key elements that may occur in lunar minerals (Na, Mg, Al, Si, K, Ca, Fe) as well as the likely constituents of lunar brines (F, Cl, S). Finally, if coring and analysis are done during the lunar night or in permanent shadow, CheMin can provide information on the chemistry and structure of any crystalline ices that might occur in the regolith samples.

Sarrazin, P.↗

Characterization of Polar Mesospheric Clouds Using Infrared Measurements from HALOE

Measurements from the Halogen Occultation Experiment (HALOE) revealed the infrared signature of polar mesospheric clouds (PMCs), for the first time, HALOE PMC observations at eight wavelengths (2.45 - 10 microns) show remarkable agreement with model PMC spectra based on ice particle extinction, and thus provide the first confirmation that water ice is the primary component of PMCs. Because PMCs respond to changes in temperature and water vapor, they are considered an indicator of global climate change. We propose to further the understanding of PMCs using a decade of infrared measurements form HALOE. This effort will characterize PMC spectral properties, extinction profiles, and size distributions. Using this information, HALOE measurements will be used to make simultaneous retrievals of H2O3, and temperature, in the presence of PMCs. The simultaneous retrievals of particle properties, H2O3, and temperature will be used with HALOE NO data to provide a significant step forward in the knowledge of PMC characteristics and formation conditions. We will challenge fundamental theories of PMC formation, and investigate changes in PMC properties and related conditions over the length of the HALOE measurement record. HALOE has been operating without flaw since it was launched on October 11, 1991. Consequently, ten southern and ten northern PMC seasons have been observed thus far, providing a wealth of data for the study of PMC and related parameters.

Hervig, Mark E.↗

SAGE (version 5.96) Ozone Trends in the Lower Stratosphere

Ozone retrievals from Stratospheric Aerosol and Gas Experiment (SAGE) II version 5.96 (v5.96) below approx. 25 km altitude are discussed. This version of the algorithm includes improved constraints on the wavelength dependence of aerosol extinctions based on the ensemble of aerosol size distribution measurements. This results in a reduction of SAGE ozone errors in the 2 years after the Mount Pinatubo eruption. However, SAGE ozone concentrations are still approx. 10% larger than ozonesonde and Halogen Occultation Experiment (HALOE) measurements below 20 km altitude under nonvolcanic conditions (and by more than this in the tropics). The analysis by Steele and Turco suggests that the SAGE ozone overpredictions are in the wrong direction to be explained by aerosol extinction extrapolation errors. Moreover, preliminary SAGE 11 v6.0a retrievals suggest that they are partially accounted for by geometric difficulties at low altitudes in v5.96 and prior retrievals. SAGE ozone trends for the 1979-1996 and 1984-1996 periods are calculated and compared, and the sources of trend errors are discussed. These calculations are made after filtering out ozone data during periods of high, local aerosol extinctions. In the lower stratosphere, below approx. 28 km altitude, there is shown to be excellent agreement in the altitudinal structure of ozone decreases at 45 deg N between SAGE and ozonesondes with the largest decrease in both between 1979 and 1996 having occurred below 20 km altitude, amounting to 0.9 +/- 0.7% yr (2sigma) at 16 km altitude. However, in contrast to the fairly steady decreases at 45 deg N, both SAGE measurements and Lauder ozonesondes show ozone increases at 45 deg S over the period from the mid-1980s to 1996 of 0.2 +/- 0.5%/yr (2sigma) from 15 to 20 km altitude. The SAGE data suggest that this increase is a wintertime phenomenon which occurs in the 15-20 km height range. Changes in dynamics are suggested as the most likely cause of this increase. These hemispheric differences in ozone trends are supported by ozone column measurements by the Total Ozone Mapping Spectrometer (TOMS).

Cunnold, D. M.↗

A Reference Model for Middle Atmosphere Ozone in 1992-1993

An ozone climatology for the period April 1992 to March 1993 and covering pressures from 0.1 to 100 hPa and from 80 deg N to 80 deg S is derived from satellite-based measurements by the Stratospheric Aerosol and Gas Experiment (SAGE), the Halogen Occultation Experiment (HALOE), and the Microwave Limb Sounder (MLS). At pressures less than 1 hPa, separate distributions are given for daytime and nighttime conditions. From 0.46 to 32 hPa the accuracy of the distribution is estimated to be 5%, and the precision is also approx. 5%. Estimates of atmospheric variability are provided on the basis of standard deviations of the measurements within months. Distributions of ozone monthly means and standard deviations are also given in a potential temperature, equivalent latitude coordinate system. This data set is included in the UARS reference atmosphere, and it is accessible through that web site.

Wang, H. J.↗

A Reference Model for Middle Atmosphere Ozone in 1992/1993: Differences from That of Keating et al (1996)

Ozone distributions have been derived from recent satellite-based measurements by the Stratospheric Aerosol and Gas Experiment (SAGE), the Halogen Occultation Experiment (HALOE) and the Microwave Limb Sounder (MLS). An ozone distribution for the period April 1992 to March 1993 and covering pressures from 0.1 to 100 mb and from 80 deg N to 80 deg S is summarized. At pressures less than 1 mb, separate distributions are given for daytime and nighttime conditions. The resulting distributions extend to somewhat higher latitudes and lower altitudes than previous COSPAR reference atmosphere distributions for ozone. Differences versus the most recent COSPAR distribution by Keating et al are illustrated.

Wang, H. J.↗

Characterization of Polar Mesospheric Clouds Using Infrared Measurements From HALOE

Measurements from the Halogen Occultation Experiment (HALOE) revealed the infrared signature of polar mesospheric clouds (PMCs), for the first time, HALOE PMC observations at eight wavelengths (2.45 - 10 microns) show remarkable agreement with model PMC spectra based on ice particle extinction, and thus provide the first confirmation that water ice is the primary component of PMCs. Because PMCs respond to changes in temperature and water vapor, they are considered an indicator of global climate change. We propose to further the understanding of PMCs using a decade of infrared measurements form HALOE. This effort will characterize PMC spectral properties, extinction profiles, and size distributions. Using this information, HALOE measurements will be used to make simultaneous retrievals of H2O, O3, and temperature, in the presence of PMCs. The simultaneous retrievals of particle properties, H2O, O3, and temperature will be used with HALOE NO data to provide a significant step forward in the knowledge of PMC characteristics and formation conditions. We will challenge fundamental theories of PMC formation, and investigate changes in PMC properties and related conditions over the length of the HALOE measurement record. HALOE has been operating without flaw since it was launched on October 11, 1991. Consequently, ten southern and ten northern PMC seasons have been observed thus far, providing a wealth of data for the study of PMCs and related parameters.

Hervig, Mark E.↗

Laser Systems

Tunable diode lasers are employed as radiation sources in high resolution infrared spectroscopy to determine spectral characteristics of gaseous compounds. With other laser systems, they are produced by Spectra-Physics, and used to monitor chemical processes, monitor production of quantity halogen lamps, etc. The Laser Analytics Division of Spectra-Physics credits the system's reliability to a program funded by Langley in the 1970s. Company no longer U.S.-owned. 5/22/97

Source record↗

Using Kalman Filter Chemical Data Assimilation to Study Ozone Catalytic Loss Cycles in January 1992

This paper presents for the first time a global study of the ozone catalytic destruction cycles operating in the stratosphere using a stratospheric analyses for January 1992. The chemical analyses were produced using a Kalman filter data assimilation system. Because a major component of the variability of trace gases is due to the atmospheric motions the analyses have been cast in a flow-tracking coordinate system that moves with the large scale flow pattern. Particular attention is paid to the kinetic aspects of these cycles such as the rate limiting step and chain length. Although it is an important kinetic parameter, the chain length of the various cycles is seldom considered when the various catalytic cycles are discussed. This survey highlights that in the low stratosphere the cycles involving HO2 and halogens (notably bromine) are particularly important. In approximate order of effectiveness the most important ozone loss cycles in the polar lower stratosphere are the BrO/ClO, HO2/BrO, and OH/HO2 cycles. The ClO/ClO cycle clearly delineates the regions of chlorine activation. The chain length of the HO2/ClO, OH/HO2, Br/BrO, and ClO/NO2, clearly delineate the vortex edge region. The chain length of the BrO/NO2 and Cl/NO2 cycles highlight the regions of chemical processing outside the vortex where streamers of chemically processed air are stripped-off and transported away from the vortex. This is also true in the very low stratosphere for the Cl/ClO and BrO/ClO cycles.

Lary, David J.↗