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  • 1
    Publication Date: 2018-02-12
    Description: Nitrous acid (HONO) photolysis is an important source of hydroxyl radicals (OH) in the lower atmosphere, in particular in winter when other OH sources are less efficient. The nighttime formation of HONO and its photolysis in the early morning have long been recognized as an important contributor to the OH budget in polluted environments. Over the past few decades it has become clear that the formation of HONO during the day is an even larger contributor to the OH budget and additionally provides a pathway to recycle NOx. Despite the recognition of this unidentified HONO daytime source, the precise chemical mechanism remains elusive. A number of mechanisms have been proposed, including gas-phase, aerosol, and ground surface processes, to explain the elevated levels of daytime HONO. To identify the likely HONO formation mechanisms in a wintertime polluted rural environment we present LP-DOAS observations of HONO, NO2, and O3 on three absorption paths that cover altitude intervals from 2 to 31, 45, and 68m above ground level (a.g.l.) during the UBWOS 2012 experiment in the Uintah Basin, Utah, USA. Daytime HONO mixing ratios in the 2–31m height interval were, on average, 78ppt, which is lower than HONO levels measured in most polluted urban environments with similar NO2 mixing ratios of 1–2ppb. HONO surface fluxes at 19ma.g.l., calculated using the HONO gradients from the LP-DOAS and measured eddy diffusivity coefficient, show clear upward fluxes. The hourly average vertical HONO flux during sunny days followed solar irradiance, with a maximum of (4.9±0.2) × 1010molec.cm−2s−1 at noontime. A photostationary state analysis of the HONO budget shows that the surface flux closes the HONO budget, accounting for 63±32% of the unidentified HONO daytime source throughout the day and 90±30% near noontime. This is also supported by 1-D chemistry and transport model calculations that include the measured surface flux, thus clearly identifying chemistry at the ground as the missing daytime HONO source in this environment. Comparison between HONO surface flux, solar radiation, NO2 and HNO3 mixing ratios, and results from 1-D model runs suggest that, under high NOx conditions, HONO formation mechanisms related to solar radiation and NO2 mixing ratios, such as photo-enhanced conversion of NO2 on the ground, are most likely the source of daytime HONO. Under moderate to low NO2 conditions, photolysis of HNO3 on the ground seems to be the main source of HONO.
    Print ISSN: 1680-7316
    Electronic ISSN: 1680-7324
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union (EGU).
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  • 2
    Publication Date: 2017-01-25
    Description: We report measurements of CH4 (measured in situ by the Harvard University Picarro Cavity Ringdown Spectrometer (HUPCRS) and NOAA Unmanned Aircraft System Chromatograph for Atmospheric Trace Species (UCATS) instruments), O3 (measured in situ by the NOAA dual-beam ultraviolet (UV) photometer), NO2, BrO (remotely detected by spectroscopic UV–visible (UV–vis) limb observations; see the companion paper of Stutz et al., 2016), and of some key brominated source gases in whole-air samples of the Global Hawk Whole Air Sampler (GWAS) instrument within the subtropical lowermost stratosphere (LS) and the tropical upper troposphere (UT) and tropopause layer (TTL). The measurements were performed within the framework of the NASA-ATTREX (National Aeronautics and Space Administration – Airborne Tropical Tropopause Experiment) project from aboard the Global Hawk (GH) during six deployments over the eastern Pacific in early 2013. These measurements are compared with TOMCAT/SLIMCAT (Toulouse Off-line Model of Chemistry And Transport/Single Layer Isentropic Model of Chemistry And Transport) 3-D model simulations, aiming at improvements of our understanding of the bromine budget and photochemistry in the LS, UT, and TTL.Changes in local O3 (and NO2 and BrO) due to transport processes are separated from photochemical processes in intercomparisons of measured and modeled CH4 and O3. After excellent agreement is achieved among measured and simulated CH4 and O3, measured and modeled [NO2] are found to closely agree with  ≤ 15ppt in the TTL (which is the detection limit) and within a typical range of 70 to 170ppt in the subtropical LS during the daytime. Measured [BrO] ranges between 3 and 9ppt in the subtropical LS. In the TTL, [BrO] reaches 0.5±0.5ppt at the bottom (150hPa∕355K∕14km) and up to about 5ppt at the top (70hPa∕425K∕18.5km; see Fueglistaler et al., 2009 for the definition of the TTL used), in overall good agreement with the model simulations. Depending on the photochemical regime, the TOMCAT∕SLIMCAT simulations tend to slightly underpredict measured BrO for large BrO concentrations, i.e., in the upper TTL and LS. The measured BrO and modeled BrO∕Bryinorg ratio is further used to calculate inorganic bromine, Bryinorg. For the TTL (i.e., when [CH4]  ≥ 1790ppb), [Bryinorg] is found to increase from a mean of 2.63±1.04ppt for potential temperatures (θ) in the range of 350–360K to 5.11±1.57ppt for θ = 390 − 400 K, whereas in the subtropical LS (i.e., when [CH4] ≤ 1790ppb), it reaches 7.66±2.95ppt for θ in the range of 390–400K. Finally, for the eastern Pacific (170–90°W), the TOMCAT/SLIMCAT simulations indicate a net loss of ozone of −0.3ppbvday−1 at the base of the TTL (θ = 355K) and a net production of +1.8ppbvday−1 in the upper part (θ = 383K).
    Print ISSN: 1680-7316
    Electronic ISSN: 1680-7324
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union (EGU).
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  • 3
    Publication Date: 2016-04-29
    Description: Atmospheric absorption in the O2 A-band (12950–13200cm−1) offers a unique opportunity to retrieve aerosol extinction profiles from space-borne measurements due to the large dynamic range of optical thickness in that spectral region. Absorptions in strong O2 lines are saturated; therefore, any radiance measured in these lines originates from scattering in the upper part of the atmosphere. Outside of O2 lines, or in weak lines, the atmospheric column absorption is small, and light penetrates to lower atmospheric layers, allowing for the quantification of aerosols and other scatterers near the surface. While the principle of aerosol profile retrieval using O2 A-band absorption from space is well-known, a thorough quantification of the information content, i.e., the amount of vertical profile information that can be obtained, and the dependence of the information content on the spectral resolution of the measurements, has not been thoroughly conducted. Here, we use the linearized vector radiative transfer model VLIDORT to perform spectrally resolved simulations of atmospheric radiation in the O2 A-band for four different aerosol extinction profile scenarios: urban (urban–rural areas), highly polluted (megacity areas with large aerosol extinction), elevated layer (identifying elevated plumes, for example for biomass burning) and low extinction (representative of small aerosol extinction, such as vegetated, marine and arctic areas). The high-resolution radiances emerging from the top of the atmosphere measurements are degraded to different spectral resolutions, simulating spectrometers with different resolving powers. We use optimal estimation theory to quantify the information content in the aerosol profile retrieval with respect to different aerosol parameters and instrument spectral resolutions. The simulations show that better spectral resolution generally leads to an increase in the total amount of information that can be retrieved, with the number of degrees of freedom (DoF) varying between 0.34–2.01 at low resolution (5cm−1) to 3.43–5.38 at high resolution (0.05cm−1) among all the different cases. A particularly strong improvement was found in the retrieval of tropospheric aerosol extinction profiles in the lowest 5km of the atmosphere. At high spectral resolutions (0.05cm−1), 1.18–1.48 and 1.31–1.96DoF can be obtained in the lower (0–2km) and middle (2–5km) troposphere, respectively, for the different cases. Consequently, a separation of lower and mid tropospheric aerosols is possible, implying the feasibility of identification of elevated biomass burning aerosol plumes (elevated layer scenario). We find that a higher single scattering albedo (SSA) allows for the retrieval of more aerosol information. However, the dependence on SSA is weaker at higher spectral resolutions. The vegetation (surface albedo 0.3), marine (surface albedo 0.05) and arctic (surface albedo 0.9) cases show that the dependence of DoF on the surface albedo decreases with higher resolution. At low resolution (5cm−1), the DoF are 1.19 for the marine case, 0.73 for the vegetation case and 0.34 for the arctic case, but increase considerably at 0.05cm−1 resolution to 3.84 (marine) and 3.43 (both vegetation and arctic), showing an improvement of a factor of 10 for the arctic case. Vegetation and arctic case also show the same DoF at higher resolution, showing that an increase of albedo beyond a certain value, i.e., 0.3 in our case, does not lead to a larger information content. The simulations also reveal a moderate dependence of information content on the integration time of the measurements, i.e., the noise of the spectra. However, our results indicate that a larger increase in DoF is obtained by an increase in spectral resolution despite lower signal-to-noise ratios.
    Print ISSN: 1867-1381
    Electronic ISSN: 1867-8548
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union (EGU).
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  • 4
    Publication Date: 2017-08-04
    Description: Nitrous acid (HONO) photolysis is an important source of hydroxyl radicals (OH) in the lower atmosphere, in particular in winter when other OH sources are less efficient. The nighttime formation of HONO and its photolysis in the early morning have long been recognized as an important contributor to the OH budget in polluted environments. Over the past few decades it has become clear that the formation of HONO during the day is an even larger contributor to the OH budget, and additionally provides a pathway to recycle NOx. Despite the recognition of this unidentified HONO daytime source, the precise chemical mechanism remains elusive. A number of mechanisms have been proposed, including gas-phase, aerosol, and ground surface processes, to explain the elevated levels of daytime HONO. To identify the likely HONO formation mechanisms in a wintertime polluted rural environment we present LP-DOAS observations of HONO, NO2, and O3 on three absorption paths that cover altitude intervals from 2 m to 31 m, 45 m, and 68 m agl during the UBWOS 2012 experiment in the Uintah Basin, Utah, USA. Daytime HONO mixing ratios in the 2–31 m height interval were, on average, 78 ppt, which is lower than HONO levels measured in most polluted urban environments with similar NO2 mixing ratios of 1–2 ppb. HONO surface fluxes at 16 m agl, calculated using the HONO gradients from the LP-DOAS and measured eddy diffusivity coefficient, show clear upward fluxes. The hourly average vertical HONO flux during sunny days followed solar irradiance, with a maximum of (4.9 ± 0.2) x 1010 molec. cm−2 s−1 at noontime. A photo-stationary state analysis of the HONO budget shows that the surface flux closes the HONO budget, accounting for 63 ± 32 % of the unidentified HONO daytime source throughout the day and 90 ± 30 % near noontime. This is also supported by 1D chemistry and transport model calculations that include the measured surface flux, thus clearly identifying chemistry at the ground as the missing daytime HONO source in this environment. Comparison between HONO surface flux, solar radiation, NO2 and HNO3 mixing ratios and results from 1D model runs suggest that, under high NOx conditions, HONO formation mechanisms related to solar radiation and NO2 mixing ratios, such as photo-enhanced conversion of NO2 on the ground, are most likely the source of daytime HONO. Under moderate to low NO2 conditions, photolysis of HNO3 on the ground seems to be the main source of HONO.
    Electronic ISSN: 1680-7375
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union (EGU).
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