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Visible-ultraviolet absorption cross sections for NO2 as a function of temperature

A redetermination of the temperature dependence of the absorption cross-section (sigma) of NO2 in the visible-ultraviolet region was made in order to provide a more reliable data base for the calculation of NO2 photolysis rates in the atmosphere. Experiments over a wide range of temperatures and NO2 concentrations were conducted. The integral of a plot of sigma versus the inverse of the wavelength was essentially independent of temperature. Increasing temperature produced a shift of the spectrum toward longer wavelengths, resulting in a small negative temperature dependence of sigma over the 264-400 nm range and a small positive dependence over the 450-649 nm range. Increasing temperature produced broadening of individual spectral features, resulting in a systematic lowering of peaks and filling of valleys. Recommended cross sections are presented for use in tropospheric NO2 photolysis rate calculations.

Davidson, J. A.↗

Stratospheric column NO2 measurements from three Antarctic sites

The significance of stratospheric odd-nitrogen compounds in Antarctic ozone depletion studies has prompted an increase in Antarctic activities. Although several species are being studied, work has concentrated on the acquisition of NO2 data. Ground-based measurements of stratospheric column NO2 have been made at Arrival Heights, Antarctica, since spring 1982, with some gaps in the data base. Additional data has been acquired since February 1986 at Pole Station and Halley Bay, thus providing a chain of stations across the continent. The technique used is that of absorption spectroscopy in several wavelength regions, although here only those measurements are reported in the 430 to 450 nm region where strongly structured absorption been determined experimentally. However, theory features due to NO2 are identified in scattered sunlight in the zenith sky. Operation of a moon-tracking system at Arrival Heights has provided some additional data during the polar night. Previous analyses have shown that the NO2 column observed from the ground is strongly influenced by the season, and by the location of the site with respect to that of the polar vortex. The column amount correlates strongly with stratospheric temperature at about 70 mbar. The present data set further illustrates these features, and demonstrates both the strengths and qualifications apparent in the technique.

Keys, J. G.↗

Stratospheric NO2 over Antarctica as measured by the Solar Mesosphere Explorer during austral spring, 1986

This paper presents the results of polar NO2 measurements carried out by the SME satellite during the fall and spring of 1985 and 1986 and compares the results with observations at the north pole and the results of model calculations. During the austral spring, a polar low was observed in stratospheric NO2 densities measured between 24 and 40 km, consistent with the predictions of standard photochemical theory. The geographic extent of the area of low NO2 densities was found to decrease as the hours of sunlight increased, in marked contrast to the behavior of the Antarctic ozone hole during the same period. A comparison of measurements with model calculations for NO2 imply that much of the odd nitrogen is converted to HNO3 during the polar night. Data also suggest no evidence that changes in high-altitude odd nitrogen are influencing the ozone below, or that the 'ozone hole' penetrates above 24 km to affect odd nitrogen there.

Thomas, Ronald J.↗

An airborne compatible photofragmentation two-photon laser-induced fluorescence instrument for measuring background tropospheric levels of NO, NO(x), and NO2

The operating principle, design, and performance of a two-photon LIF (TP-LIF) sensor for simultaneous measurements of NO, NO(x) (NO + NO2), and NO2 are described. In this instrument, NO is first measured by direct spectroscopic TP-LIF detection; NO2 is converted to NO by photofragmentation using an XeF excimer laser operating at 353 nm; and the resulting NO is then detected quantitatively by TP-LIF. The detection limits of the instrument are found to be 3.5 parts per trillion by volume (pptv) of NO and 10 pptv for NO2, with integration times of 2 and 6 min, respectively. The in-flight performance of the instrument was evaluated during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 program in summer 1986, as reported by Gregory et al. (1990).

Sandholm, S. T.↗

Ground based NO2 and O3 measurements by visible spectrometer at Syowa Base (69 deg S), Antarctica

The column amounts of NO2 and ozone have been measured using visible spectroscopy at Syowa Base (69 deg S) since March 1990. Ozone was also measured at the same location with a Dobson spectrometer as well as ozonesondes being flown regularly. The characteristic features of the seasonal and diurnal variations of NO2 are presented. The column ozone values from the visible spectrometers are compared with the Dobson data. The very low values of NO2 in midwinter and early spring are consistent with the conditions predicted to be needed for heterogeneous ozone destruction in early spring. In late spring and summer of 1991, NO2 amounts were considerably smaller than in 1990, presumably due to the effect of Mt. Pinatubo eruption.

Kondo, Y.↗

NO2 column changes induced by volcanic eruptions

Nitrogen dioxide slant column amounts measured by ground-based remote sensing from Lauder, New Zealand (45 deg S) and Campbell Island (53 deg S) during the second half of 1991 and early 1992 show anomalously low values that are attributed to the effects of volcanic eruptions. It is believed that the eruptions of Mount Pinatubo in the Philippines in June 1991 and possibly Mount Hudson in Chile in August 1991 are responsible for the stratospheric changes, which first became apparent in July 1991. The effects in the spring of 1991 are manifested as a reduction in the retrieved NO2 column amounts from normal levels by 35 to 45 percent, and an accompanying increase in the overnight decay of NO2. The existence of an accurate long-term record of column NO2 from the Lauder site enables us to quantify departures from the normal seasonal behavior with some confidence. Simultaneous retrievals of column ozone agree well with Dobson measurements, confirming that only part of the NO2 changes can be attributed to a modification of the scattering geometry by volcanic aerosols. Other reasons for the observed behavior are explored, including the effects of stratospheric temperature increases resulting from the aerosol loading and the possible involvement of heterogeneous chemical processes.

Johnston, Paul V.↗

Total ozone and total NO2 latitudinal distribution derived from measurements in the Atlantic Ocean in May 1988

Total ozone and NO2 were measured aboard a ship in the 40S - 40N latitude band in the Atlantic Ocean in the second half of May 1988. The main features of the latitudinal distributions of total NO2 and ozone are similar. There is seen an increase of total ozone and NO2 from the tropical to subtropical latitudes, strongest in the region of the subtropical jet stream. The fine structure has been revealed in the total ozone and NO2 latitudinal distributions, connected most likely with stratosphere-troposphere exchange processes in the tropopause folding zone.

Elokhov, Alexander S.↗

An examination of global variations of sunset NO2 as measured by SAGE II

Global variations of sunset NO2 are examined for the period October 24, 1984 through May 28, 1991 using Stratospheric Aerosol and Gas Experiment (SAGE) II data. Between 60 deg S and 60 deg N declining trends are observed at all latitudes and at all altitudes above 25 km. For the column NO2 above 25 km, the area-weighted integrated trend between these latitudes is -2.5%/year. The largest rates of decline (5%/year) are at mid to high latitudes in each hemisphere. Different temporal behavior is observed with latitude and in the two hemispheres. The largest percentage changes of NO2 from year to year are observed near 40 km at high latitudes and can be as large as 160%. These results and previously reported simulations suggest that a modulating polar source of NO(y) and variations in atmospheric temperature and advective transport both contribute to the observed NO2 variations.

Callis, L. B.↗

The response of C1O radical concentrations to variations in NO2 radical concentrations in the lower stratosphere

The respose of ClO concentrations to changes in NO2 concentrations has been inferred from simultaneous observations of (ClO), (NO), (NO2) and (O3) in the midlatitude lower stratosphere. This analysis demonstrates that (ClO) is inversely correlated with (NO2), consistent with formation and photolysis of (ClONO2). A factor of ten range in the concentration if NO2 was sampled (0.1 to 1 x 10(exp 9) mol/cu cm), with a comparable range in the ratio of (ClO) to total available inorganic chlorine (1% less than or equal to (ClO)/(Cl(sub y)) less than or equal to 5%. This analysis leads to an estimate of (ClONO2)/(Cl(sub y)) = 0.12 (x/2), in the mid-latitude, lower-stratospheric air masses sampled.

Stimfle, R. M.↗

Observations of the loss of stratospheric NO2 following volcanic eruptions

Observations of stratospheric column amounts of nitrogen dioxide (NO2), nitric oxide (NO) and nitric acid (HNO3) have been made following major eruptions of the El Chichon and Mt. Pintatubo volcanoes. Midlatitude abundances of NO2 and NO were reduced by as much as 70% in the months following the appearance of the volcanic aerosols as compared to volcanically quite periods. There are heterogeneous reactions which could occur on the volcanic aerosols to convert NO2 into HNO3 but no commensurate increase in HNO3 column amounts was observed at the times of NO2 decrease.

Coffey, M. T.↗

The Response of ClO Radical Concentrations to Variations in NO2 Radical Concentrations in the Lower Stratosphere

The response of ClO concentrations to changes in NO2 concentrations has been inferred from simultaneous observations of [ClO], [NO], [NO2] and [O3] in the mid-latitude lower stratosphere. This analysis demonstrates that [ClO] is inversely correlated with [NO2], consistent with formation and photolysis of [ClONO2]. A factor of ten range in the concentration of NO2 was sampled (0.1 to 1 x 10(exp 9) mol/cc), with a comparable range in the ratio of [ClO] to total available inorganic chlorine (1% <= [ClO]/[Cl(sub y)] <= 5%). This analysis leads to an estimate of [ClONO2]/[Cl(sub y)] = 0.12 (x/divided by 2), in the mid-latitude, lower-stratospheric air masses sampled.

Stimpfle, R. M.↗

The uptake of NO3-, NO2-, and NH4+ by intact wheat (Triticum aestivum) seedlings. I. Induction and kinetics of transport systems

The inducibility and kinetics of the NO3-, NO2-, and NH4+ transporters in roots of wheat seedlings (Triticum aestivum cv Yercora Rojo) were characterized using precise methods approaching constant analysis of the substrate solutions. A microcomputer-controlled automated high performance liquid chromatography system was used to determine the depletion of each N species (initially at 1 millimolar) from complete nutrient solutions. Uptake rate analyses were performed using computerized curve-fitting techniques. More precise estimates were obtained for the time required for the extent of the induction of each transporter. Up to 10 and 6 hours, respectively, were required to achieve apparent full induction of the NO3- and NO2- transporters. Evidence for substrate inducibility of the NH4+ transporters requiring 5 hours is presented. The transport of NO3- was mediated by a dual system (or dual phasic), whereas only single systems were found for transport of NO2- and NH4+. The Km values for NO3-, NO2-, and NH4+ were, respectively, 0.027, 0.054, and 0.05 millimolar. The Km for mechanism II of NO3- transport could not be defined in this study as it exhibited only apparent first order kinetics up to 1 millimolar.

NASA Program CELSS↗

Intercomparison of SCIAMACHY and OMI Tropospheric NO2 Columns: Observing the Diurnal Evolution of Chemistry and Emissions from Space

Concurrent (August 2006) measurements of tropospheric NO2 columns from OMI aboard Aura (1330 local overpass time) and SCIAMACHY aboard Envisat (1000 local overpass time) offer an opportunity to examine the consistency between the two instruments under tropospheric background conditions and the effect of different observing times. For scenes with tropospheric NO 2 columns <5.0 x 10(exp 15) molecules cm 2, SCIAMACHY and OMI agree within 1.0-2.0 x 10(exp 15) molecules cm 2, consistent with the detection limits of both instruments. We find evidence for a low bias of 0.2 x 10(exp 15) molecules cm 2 in OMI observations over remote oceans. Over the fossil fuel source regions at northern midlatitudes, we find that SCIAMACHY observes up to 40% higher NO2 at 1000 local time (LT) than OMI at 1330 LT. Over biomass burning regions in the tropics, SCIAMACHY observes up to 40% lower NO 2 columns than OMI. These differences are present in the spectral fitting of the data (slant column) and are augmented in the fossil fuel regions and dampened in the tropical biomass burning regions by the expected increase in air mass factor as the mixing depth rises from 1000 to 1330 LT. Using a global 3-D chemical transport model (GEOS-Chem), we show that the 1000-1330 LT decrease in tropospheric NO2 column over fossil fuel source regions can be explained by photochemical loss, dampened by the diurnal cycle of anthropogenic emissions that has a broad daytime maximum. The observed 1000-1330 LT NO2 column increase over tropical biomass burning regions points to a sharp midday peak in emissions and is consistent with a diurnal cycle of emissions derived from geostationary satellite fire counts.

Boersma, K. Folkert↗

Airborne MAX-DOAS Measurements Over California: Testing the NASA OMI Tropospheric NO2 Product

Airborne Multi-AXis Differential Optical Absorption Spectroscopy (AMAX-DOAS) measurements of NO2 tropospheric vertical columns were performed over California for two months in summer 2010. The observations are compared to the NASA Ozone Monitoring Instrument (OMI) tropospheric vertical columns (data product v2.1) in two ways: (1) Median data were compared for the whole time period for selected boxes, and the agreement was found to be fair (R = 0.97, slope = 1.4 +/- 0.1, N= 10). (2) A comparison was performed on the mean of coincident AMAX-DOAS measurements within the area of the corresponding OMI pixels with the tropospheric NASA OMI NO2 assigned to that pixel. The effects of different data filters were assessed. Excellent agreement and a strong correlation (R = 0.85, slope = 1.05 +/- 0.09, N= 56) was found for (2) when the data were filtered to eliminate large pixels near the edge of the OMI orbit, the cloud radiance fraction was<50%, the OMI overpass occurred within 2 h of the AMAX-DOAS measurements, the flight altitude was>2 km, and a representative sample of the footprint was taken by the AMAX-DOAS instrument. The AMAX-DOAS and OMI data sets both show a reduction of NO2 tropospheric columns on weekends by 38 +/- 24% and 33 +/- 11%, respectively. The assumptions in the tropospheric satellite air mass factor simulations were tested using independent measurements of surface albedo, aerosol extinction, and NO2 profiles for Los Angeles for July 2010 indicating an uncertainty of 12%.

remote sensing↗

Top-Down NOx Emissions of European Cities Based on the Downwind Plume of Modelled and Space-Borne Tropospheric NO2 Columns

Top-down estimates of surface NOX emissions were derived for 23 European cities based on the downwind plume decay of tropospheric nitrogen dioxide (NO2) columns from the LOTOS-EUROS (Long Term Ozone Simulation-European Ozone Simulation) chemistry transport model (CTM) and from Ozone Monitoring Instrument (OMI) satellite retrievals, averaged for the summertime period (April-September) during 2013. Here we show that the top-down NOX emissions derived from LOTOS-EUROS for European urban areas agree well with the bottom-up NOX emissions from the MACC-III inventory data (R(exp 2) = 0.88) driving the CTM demonstrating the potential of this method. OMI top-down NOX emissions over the 23 European cities are generally lower compared with the MACC-III emissions and their correlation is slightly lower (R(exp 2) = 0.79). The uncertainty on the derived NO2 lifetimes and NOX emissions are on average ~55% for OMI and ~63% for LOTOS-EUROS data. The downwind NO2 plume method applied on both LOTOS-EUROS and OMI tropospheric NO2 columns allows to estimate NOX emissions from urban areas, demonstrating that this is a useful method for real-time updates of urban NOX emissions with reasonable accuracy.

NOx emissions↗

The Version 3 OMI NO2 Standard Product

We describe the new version 3.0 NASA Ozone Monitoring Instrument (OMI) standard nitrogen dioxide (NO2) products (SPv3). The products and documentation are publicly available from the NASA Goddard Earth Sciences Data and Information Services Center (https://disc.gsfc.nasa.gov/datasets/OMNO2_V003/summary/). The major improvements include (1) a new spectral fitting algorithm for NO2 slant column density (SCD) retrieval and (2) higher-resolution (1° latitude and 1.25° longitude) a priori NO2 and temperature profiles from the Global Modeling Initiative (GMI) chemistry–transport model with yearly varying emissions to calculate air mass factors (AMFs) required to convert SCDs into vertical column densities (VCDs). The new SCDs are systematically lower (by ∼10-40%) than previous, version 2, estimates. Most of this reduction in SCDs is propagated into stratospheric VCDs. Tropospheric NO2 VCDs are also reduced over polluted areas, especially over western Europe, the eastern US, and eastern China. Initial evaluation over unpolluted areas shows that the new SPv3 products agree better with independent satellite- and ground-based Fourier transform infrared (FTIR) measurements. However, further evaluation of tropospheric VCDs is needed over polluted areas, where the increased spatial resolution and more refined AMF estimates may lead to better characterization of pollution hot spots.

Ozone Monitoring Instrument (OMI)↗

Nitrogen Oxides in the Global Upper Troposphere: Interpreting Cloud-Sliced NO2 Observations from the OMI Satellite Instrument

Nitrogen oxides (NOx≡NO+NO2) in the upper troposphere (UT) have a large impact on global tropospheric ozone and OH (the main atmospheric oxidant). New cloud-sliced observations of UT NO2 at 450–280 hPa (∼6–9 km) from the Ozone Monitoring Instrument (OMI) produced by NASA and the Royal Netherlands Meteorological Institute (KNMI) provide global coverage to test our understanding of the factors controlling UT NOx. We find that these products offer useful information when averaged over coarse scales (20°×32°, seasonal), and that the NASA product is more consistent with aircraft observations of UT NO2. Correlation with Lightning Imaging Sensor (LIS) and Optical Transient Detector (OTD) satellite observations of lightning flash frequencies suggests that lightning is the dominant source of NOx to the upper troposphere except for extratropical latitudes in winter. The NO2 background in the absence of lightning is 10–20 pptv. We infer a global mean NOx yield of 280±80 moles per lightning flash, with no significant difference between the tropics and midlatitudes, and a global lightning NOx source of 5.9±1.7 Tg N a(exp −1). There is indication that the NOx yield per flash increases with lightning flash footprint and with flash energy.

Marais, Eloise A.↗

Joint Assimilation of Surface, GEO, and LEO CO, NO2, and O3 In Situ and Partial Column/Profile Retrievals with WRF-Chem/DART

Low earth orbiting (LEO) satellites like OMI or TROPOMI and geostationary satellites like TEMPO (to be launched January 2023) provide ozone (O3) retrieval profiles that extend into the stratosphere. Regional models like WRF-Chem generally do not include the stratosphere and have vertical grids that end near the tropopause. This causes difficulties when assimilating O3 retrievals (both column and profile retrievals) because the respective observation forward operators require model O3 profiles that extend into the stratosphere. In this presentation, we look at results from assimilating O3 observation from surface (in situ measurements), multiple LEO (profile retrievals), and GEO (proxy profile retrievals) platforms in as regional model where we use a global chemical transport model (GCTM) to provide O3 upper boundary conditions (BCs) to enable application of the O3 observation forward operators. We will also present results from assimilating O3 retrievals together with carbon monoxide (CO) observations from surface (in situ measurements) and multiple LEO platforms (column and profile retrievals), and nitrogen dioxide (NO2) observations from surface (in situ measurements), multiple LEO (column retrievals), and GEO (proxy column retrievals) platforms. Our joint assimilation experiments show that sometimes the observations complement each, e.g., when assimilating surface and satellite CO or NO2 observations, and sometimes the observations conflict with each other, e.g., when assimilating observations that are biased with respect to other observations (e.g., CO retrievals), or when the assimilation increments conflict due to their chemical interaction (e.g., surface O3 and NO2 retrievals). Results from assimilation of O3 retrieval profiles in regional model are preliminary and will also be discussed in our presentation. Our expectation is that using GCTM O3 as upper BCs in the regional model for evaluation of the O3 forward operator will improve our O3 forecasts. In summary, we will present results from jointly assimilating surface, LEO, and GEO CO, NO2, and O3 in situ and satellite observations in a regional model with dynamic emissions estimation. This study uses proxy GEO observations as a prelude to actual observations because the GEO platform will not be launched until after our presentation.

WRF-Chem/DART↗