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At least 163 records · Page 9

Global Burden of Tropospheric Ozone: Effects of Particulate Nitrate Photolysis and Assimilation of NO2 Measurements

Tropospheric ozone is a major pollutant, a greenhouse gas, and the primary source of the hydroxyl radical. It is largely produced in situ from the oxidation of CO and volatile organic compounds in the presence of nitrogen oxides (NOx=NO+NO2). Global atmospheric chemistry models generally underestimate NOx and CO concentrations in the northern hemisphere away from source regions, which would lead to an underestimate in the tropospheric ozone burden. Here we evaluate the tropospheric ozone simulation in the GEOS-Chem model (version 14) using observations from satellite, aircraft, and ozonesondes. We include GEOS-Chem simulations conducted in the standard offline mode, as well as in the online mode within the NASA GEOS earth system model which forms the basis for the GEOS Composition Forecasts (GEOS-CF). In both configurations, GEOS-Chem underestimates ozone concentrations in the northern midlatitude free troposphere in spring and summer. We find that we can improve the ozone simulation by including an additional NOx source over the oceans from particulate nitrate photolysis on sea salt aerosols at rates inferred from field studies over the Atlantic Ocean. We investigate whether further improvements in the ozone simulation can be achieved by assimilating satellite measurements of NO2 from the Ozone Monitoring Instrument (OMI) and CO from the Measurement of Pollution in the Troposphere (MOPITT) instruments.

tropospheric ozone↗

Accurate Modeling of Lyα Profiles and their Impact on Photolysis of Terrestrial Planet Atmospheres

Accurately measuring and modeling the Lyα (Lyα; λ1215.67 Å) emission line from low-mass stars is vital for our ability to build predictive high energy stellar spectra, yet interstellar medium (ISM) absorption of this line typically prevents model-measurement comparisons. Lyα also controls the photodissociation of important molecules, like water and methane, in exoplanet atmospheres such that any photochemical models assessing potential biosignatures or atmospheric abundances require accurate Lyα host star flux estimates. Recent observations of three early M and K stars (K3, M0, M1) with exceptionally high radial velocities (>100 km s −1 ) reveal the intrinsic profiles of these types of stars as most of their Lyα flux is shifted away from the geocoronal line core and contamination from the ISM. These observations indicate that previous stellar spectra computed with the PHOENIX atmosphere code have underpredicted the core of Lyα in these types of stars. With these observations, we have been able to better understand the microphysics in the upper atmosphere and improve the predictive capabilities of the PHOENIX atmosphere code. Since these wavelengths drive the photolysis of key molecular species, we also present results analyzing the impact of the resulting changes to the synthetic stellar spectra on observable chemistry in terrestrial planet atmospheres.

Sarah Peacock↗

Formation of Insoluble Organic Material from the Ultraviolet Irradiation of Laboratory Ice Photolysis Residues

We present preliminary results from the study of ice photolysis residues which were exposed to ultraviolet (UV)/extreme UV (EUV) photon radiation. The residues were produced from the simultaneous deposition and UV irradiation of ice mixtures of astrophysical interest (H2O, CH3OH, CO, NH3, without/with N2 and/or O2, and without/with small quantities of aromatic compounds) at 15–20 K using an H2 lamp, which emits 10.2-eV (121.6 nm) Lyman-α photons and a continuum at 7.5–8 eV (155–165 nm). After warm-up to room temperature and subsequent sublimation of volatile compounds, the refractory materials (residues) recovered at room temperature were analyzed with infrared (IR) microscopy and then further irradiated with UV/EUV photons at a synchrotron facility, on a beamline providing a broad-band photon beam in the 4–45-eV range with a ~1016 photons s-1 flux.2 The residues were UV/EUV irradiated with increasing photon doses ranging from ~1018 to ~1021 photons, i.e., covering 4 orders of magnitude and relevant to those experienced by ice-coated grains in the protosolar nebula.1. After UV/EUV irradiation, residues were analyzed with IR microscopy and the data compared to those before irradiation to identify changes in chemical composition as a function of the photon dose. UV/EUV-irradiated residues were also analyzed with other techniques such as nanoscale secondary-ion mass spectrometry (nanoSIMS) to the study the changes in isotopic composition, and scanning transmission electron microscopy to look at variations in structure and C bonding distribution. Results will be compared with data from extraterrestrial materials, in particular, meteoritic insoluble organic material (IOM) and interplanetary dust particles (IDPs).

Ices↗

Mid- and far-infrared spectroscopic studies of the influence of temperature, ultraviolet photolysis and ion irradiation on cosmic-type ices

Infrared (IR) studies of laboratory ices can provide information on the evolution of cosmic-type ices as a function of different simulated space environments involving thermal, ultraviolet (UV), or ion processing. Laboratory radiation experiments can lead to the formation of complex organic molecules. However, because of our lack of knowledge about UV photon and ion fluxes, and exposure lifetimes, it is not certain how well our simulations represent space conditions. Appropriate laboratory experiments are also limited by the absence of knowledge about the composition, density, and temperature of ices in different regions of space. Our current understanding of expected doses due to UV photons and cosmic rays is summarized here, along with an inventory of condensed-phase molecules identified on outer solar system surfaces, comets and interstellar grains. Far-IR spectra of thermally cycled H2O are discussed since these results reflect the dramatic difference between the amorphous and crystalline phases of H2O ice, the most dominant condensed-phase molecule in cosmic ices. A comparison of mid-IR spectra of products in proton-irradiated and UV-photolyzed ices shows that few differences are observed for these two forms of processing for the simple binary mixtures studied to date. IR identification of radiation products and experiments to determine production rates of new molecules in ices during processing are discussed. A new technique for measuring intrinsic IR band strengths of several unstable molecules is presented. An example of our laboratory results applied to Europa observations is included.

Spectrophotometry, Infrared/methods↗

The Quantum Yield of NO3 from Peroxyacetyl Nitrate Photolysis

Peroxyacetyl nitrate (PAN) vapor was photolyzed at 248nm and the NO3 photoproduct was detected by laser induced fluorescence. The excited state flourescence contributions were investigated and a data analysis methodology was established to minimize their effects.

Peroxyacetyl Nitrate Photolysis↗