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  • 1
    Publication Date: 2011-08-23
    Description: The photolysis of chlorine nitrate was studied using broadband flash photolysis coupled with long-path ultraviolet-visible absorption spectroscopy. Branching ratios for the Cl + NO3 and ClO + NO2 product channels were determined from time-dependent measurements of ClO and NO3 concentrations. Yields of the ClO and NO3 products displayed a dependence on the bath gas density and the spectral distribution of the photolysis pulse. Product yields decreased with increasing bath gas density regardless of the spectral distribution of the photolysis pulse; however, the decrease in product yield was much more pronounced when photolysis was limited to longer wavelengths. For photolysis in a quartz cell (lambda 〉 200 nm) the yield decreased by a factor of 2 over the pressure 10-100 Torr. In a Pyrex cell (lambda 〉 300 nm), the yield decreased by a factor of 50 over the same pressure range. When photolysis was limited to lambda 〉 350 nm, the yield decreased by a factor of 250. Branching ratios for the photolysis channels [ClONO2 + h.nu yields ClO + NO2 (1a) and ClONO2 + h.nu yields Cl + NO3 (lb)] were determined from the relative ClO and NO3 product yields at various pressures. Although the absolute product yield displayed a pressure dependence, the branching between the two channels was independent of pressure. The relative branching ratios (assuming negligible contributions from other channels) are 0.61 +/- 0.20 for channel 1a and 0.39 +/- 0.20 for channel lb for photolysis with lambda 〉 200 nm and 0.44 +/- 0.08 for channel 1a and 0.56 +/- 0.08 for channel 1b for photolysis with lambda 〉 300 nm. The implications of these results for the chemistry of the lower stratosphere are discussed.
    Keywords: Inorganic and Physical Chemistry
    Type: Journal of Physical Chemistry (ISSN 0022-3654); Volume 100; No. 20; 10165-10178
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  • 2
    Publication Date: 2018-06-11
    Description: The Tropospheric Emission Spectrometer (TES) on the EOS Aura satellite makes global measurements of infrared radiances which are used to derive profiles of species such as O3, CO, H2O, HDO and CH4 as routine standard products. In addition, TES has a variety of special modes that provide denser spatial mapping over a limited geographical area. A continuous-coverage mode (called ''transect'', about 460 km long) has now been used to detect additional molecules indicative of regional air pollution. On 10 July 2007 at about 05:37 UTC (13:24 LMST) TES conducted such a transect observation over the Beijing area in northeast China. Examination of the residual spectral radiances following the retrieval of the TES standard products revealed surprisingly strong features attributable to enhanced concentrations of ammonia (NH3) and methanol (CH3OH), well above the normal background levels. This is the first time that these molecules have been detected in space-based nadir viewing measurements that penetrate into the lower atmosphere.
    Keywords: Meteorology and Climatology
    Type: Geophysical Research Letters; Volume 35
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  • 3
    Publication Date: 2019-07-13
    Description: Geostationary Carbon Process Mapper (GCPM) is an earth science mission to measure key atmospheric trace gases related to climate change and human activity.Understanding of sources and sinks of CO2 is currently limited by frequency of observations and uncertainty in vertical transport. GCPM improves this situation by making simultaneous high resolution measurements of CO2, CH4, CF, and CO in near-IR, many times per day. GCPM is able to investigate processes with time scales of minutes to hours. CO2, CH4, CF, Co selected because their combination provides information needed to disentangle natural and anthropogenic sources/sinks. Quasi-continuous monitoring effectively eliminates atmospheric transport uncertainties from source/sink inversion modeling. will have one instrument (GeoFTS), hosted on a commercial communications satellite, planned for two years operation. GCPM will affordably advance the understanding of observed cycle variability improving future climate projections.
    Keywords: Meteorology and Climatology
    Type: 2012 IEEE Aerospace Conference; Mar 03, 2012 - Mar 10, 2012; Big Sky, MT; United States
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  • 4
    Publication Date: 2019-07-13
    Description: The uptake of peroxynitric acid (PNA), HO2NO2 or HNO4, on solid H2O ice at 193 K (-80 C) was studied using a fast flow-mass spectrometric technique. An uptake coefficient of 0.15 +/- 0.10 was measured, where the quoted uncertainty denotes 2 standard deviations. The uptake process did not result in the production of gas phase products. The composition of the condensed phase was investigated using programmed heating (3 K/min) of the substrate coupled with mass spectrometric detection of desorbed species. Significant quantities of HNO, and HNO3 desorbed from the substrates at temperatures above 225 K and 246 K, respectively. The desorbed HNO3, which was less than 9% of the desorbed HNO, and remained unchanged upon incubation of the substrate, was likely due to impurities in the HNO4 samples rather than reaction of HNO, on the substrate. The onset temperatures for HNO4 desorption increased with increasing H2O to HNO4 ratios, indicating that HNO4, like HNO3, tends to be hydrated in the presence of water. These observations suggest possible mechanisms for removal of HNO4 or repartitioning of total odd nitrogen species in the Earth's upper troposphere and stratosphere.
    Keywords: Inorganic and Physical Chemistry
    Type: Paper-96JD00065 , Journal of Geophysical Research (ISSN 0148-0227); 101; D3; 6795-6802
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  • 5
    Publication Date: 2019-08-17
    Description: Peroxyacetyl nitrate (PAN) vapor was photolyzed at 248 nm, and the NO2 photoproduct was detected by laser-induced fluorescence. The quantum yield for the production of NO2 from PAN photolysis was determined by comparison to HNO3 photolysis data taken under identical experimental conditions. The average of data collected over a range of total pressures, precursor concentrations, and buffer gases was 0.83 +/- 0.09 for the NO2 quantum yield, where the statistical uncertainty is 2 standard deviations.
    Keywords: Inorganic and Physical Chemistry
    Type: NASA-CR-203214 , NAS 1.26:203214 , The Journal of Physical Chemistry (ISSN 0022-3654); 99; 8162-8169
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  • 6
    Publication Date: 2019-08-14
    Description: Atmospheric moisture cycling is an important aspect of the Earth's climate system, yet the processes determining atmospheric humidity are poorly understood. For example, direct evaporation of rain contributes significantly to the heat and moisture budgets of clouds, but few observations of these processes are available. Similarly, the relative contributions to atmospheric moisture over land from local evaporation and humidity from oceanic sources are uncertain. Lighter isotopes of water vapour preferentially evaporate whereas heavier isotopes preferentially condense and the isotopic composition of ocean water is known. Here we use this information combined with global measurements of the isotopic composition of tropospheric water vapour from the Tropospheric Emission Spectrometer (TES) aboard the Aura spacecraft, to investigate aspects of the atmospheric hydrological cycle that are not well constrained by observations of precipitation or atmospheric vapour content. Our measurements of the isotopic composition of water vapour near tropical clouds suggest that rainfall evaporation contributes significantly to lower troposphere humidity, with typically 20% and up to 50% of rainfall evaporating near convective clouds. Over the tropical continents the isotopic signature of tropospheric water vapour differs significantly from that of precipitation, suggesting that convection of vapour from both oceanic sources and evapotranspiration are the dominant moisture sources. Our measurements allow an assessment of the intensity of the present hydrological cycle and will help identify any future changes as they occur.
    Keywords: Meteorology and Climatology
    Type: Nature; 445; 528-532
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