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Primary quantum yields of NO2 photodissociation

The quantum yields of formation of NO, O2, and NO2 loss are measured for NO2 vapor at low pressures (0.13-0.30 torr) irradiated at 334-405 nm wavelengths and temperature in the range 273-370 K in order to study the primary quantum efficiencies of NO2 photodecomposition. The temperature and wavelength dependences of the primary quantum efficiencies are examined. It is observed that the primary quantum efficiencies increase rapidly from near zero at 424 nm to near unity for excitation at wavelengths less than 394 nm. The theory of Pitts et al. (1964) that the energy deficiency for photodissociation of NO2 excited at wavelengths greater than 397.9 nm is due to the rotational and vibrational energy of the NO2 molecules is confirmed by the data. Values for the primary quantum yields of NO2 photodecomposition as a function of wavelength are presented.

Gardner, Edward P.↗

Simultaneous in situ measurements and diurnal variations of NO, NO2, O3, jNO2, CH4, H2O, and CO2 in the 40- to 26-km region using an open path tunable diode laser spectrometer

Simultaneous in situ measurements of temperature, pressure, and the NO, NO2, O3, jNO2, CH4, H2O, and CO2 concentrations were conducted in the 40- to 26-km region of the stratosphere using the JPL Balloon-borne Laser In Situ Sensor, a tunable diode laser absorption spectrometer. The NO, NO2, CH4, H2O, and CO2 concentration measurements generally show good agreement with previous observations, with a tendency for somewhat lower NO2 amounts. Measured O3 concentrations at 38 km agree well with comparable measurements from in situ UV photometers, but at 28 km they are lower by about 10 percent and agree more closely with the solar backscattered UV data. A decline was found in NO2 during the night over a 5-km altitude range, which implies either lower NO2 postsunset profiles, or an NO2 decay rate that is significantly higher than current model predictions that use N2O5 chemistry.

Webster, Christopher R.↗

Variation of stratospheric NO2 during the solar eclipse

The numerical modeling of the changes of the concentration of trace gases in the atmosphere during the eclipse shows that the NO2 total content in the vertical column increases approximately by 80 percent. The first observations of the NO2 total content during the eclipse of 1981 have given 60 plus or minus 20 percent. In the observations of 1990 the more precise methods and instruments for stratospheric NO2 measurements were used. The surface ozone, NO, and NO2 concentrations were under control. The results of the observations give the increasing of the stratospheric NO2 during the eclipse by 55 plus or minus 6 percent. The maximum increasing of the NO2 content is observed at the moment of the maximum phase.

Elansky, Nikolay F.↗

Investigation of catalytic reduction and filter techniques for simultaneous measurements of NO, NO2, and HNO3 in the stratosphere

A concept for measuring stratospheric NOy-species is presented which utilizes the catalytic reduction of NO2 and HNO3 over heated metal catalysts and the chemisorption of HNO3 on Nylon. Using the Max Planck Institute for Aeronomy (MPAE) chemiluminescent balloon-borne sonde, stratospheric NO and NO2 profiles have been measured since 1983. NO is detected by chemiluminescence produced in reaction with O3 while NO2 needs first to be converted to NO over a heated stainless steel catalyst. To improve this technique for simultaneously measuring HNO3, the catalytic reduction of NO2 and HNO3 over several metal catalysts and the chemisorption of NO2 and HNO3 on Nylon have been investigated in laboratory tests. The results of these tests under simulated stratospheric conditions are presented in detail in this paper. They demonstrate that the simultaneous measurement of NO, NO2 and HNO3 is indeed possible with the combination of stainless steel or Au as a catalyst and a nylon filter.

Wendt, J.↗

First Global Maps of Stratospheric and Tropospheric NO2 from OMI

The Ozone Monitoring Instrument (OMI) was launched successfully in July 2004, as one of four instruments on the EOS Aura satellite. OMI makes hyperspectral measurements that are used to retrieve column densities of critical trace gases, including formaldehyde, BrO, SO2 and NO2 . We present the first results from the OM1 operational NO2 algorithm and demonstrate its ability to retrieve the tropospheric and stratospheric components of NO2. The DOAS method is used to determine slant column densities, and initial air mass factors (AMFs) are used. to give initial estimates of the vertical column densities (VCDs). VCDs from up to 15 consecutive orbits are collected, and a spatial filtering technique is applied to extract the synoptic-scale features characteristic of the stratospheric, field. features to be evidence of tropospheric excess NO2 , and apply an AMF appropriate to polluted conditions, to obtain an improved retrieval of the NO2 total VCD. We describe the assumptions underlying the algorithm in detail, and show global maps of NO2 VCDs, based on the first operational data from OMI.

Bucsela, Eric J.↗

NO2 Total and Tropospheric Vertical Column Densities from OMI on EOS Aura: Update

The Ozone Monitoring Instrument (OMI), which is on the EOS AURA satellite, retrieves vertical column densities (VCDs) of NO2, along with those of several other trace gases. The relatively high spatial resolution and daily global coverage of the instrument make it particularly well-suited to monitoring tropospheric pollution at scales on the order of 20 km. The OMI NO2 algorithm distinguishes polluted regions from background stratospheric NO2 using a separation algorithm that relies on the smoothly varying stratospheric NO2 and estimations of both stratospheric and tropospheric air mass factors (AMFs). Version 1 of OMI NO2 data has been released for public use. An overview of OMI NO2 data, some recent results and a description of the improvements for version 2 of the algorithm will be presented.

Gleason, J.F.↗

A New Retrieval Algorithm for OMI NO2: Tropospheric Results and Comparisons with Measurements and Models

Nitrogen oxides (NOx =NO+NO2) are important atmospheric trace constituents that impact tropospheric air pollution chemistry and air quality. We have developed a new NASA algorithm for the retrieval of stratospheric and tropospheric NO2 vertical column densities using measurements from the nadir-viewing Ozone Monitoring Instrument (OMI) on NASA's Aura satellite. The new products rely on an improved approach to stratospheric NO2 column estimation and stratosphere-troposphere separation and a new monthly NO2 climatology based on the NASA Global Modeling Initiative chemistry-transport model. The retrieval does not rely on daily model profiles, minimizing the influence of a priori information. We evaluate the retrieved tropospheric NO2 columns using surface in situ (e.g., AQS/EPA), ground-based (e.g., DOAS), and airborne measurements (e.g., DISCOVER-AQ). The new, improved OMI tropospheric NO2 product is available at high spatial resolution for the years 200S-present. We believe that this product is valuable for the evaluation of chemistry-transport models, examining the spatial and temporal patterns of NOx emissions, constraining top-down NOx inventories, and for the estimation of NOx lifetimes.

Swartz, W. H.↗

Inverse Modeling of Texas NOx Emissions Using Space-Based and Ground-Based NO2 Observations

Inverse modeling of nitrogen oxide (NOx) emissions using satellite-based NO2 observations has become more prevalent in recent years, but has rarely been applied to regulatory modeling at regional scales. In this study, OMI satellite observations of NO2 column densities are used to conduct inverse modeling of NOx emission inventories for two Texas State Implementation Plan (SIP) modeling episodes. Addition of lightning, aircraft, and soil NOx emissions to the regulatory inventory narrowed but did not close the gap between modeled and satellite observed NO2 over rural regions. Satellitebased top-down emission inventories are created with the regional Comprehensive Air Quality Model with extensions (CAMx) using two techniques: the direct scaling method and discrete Kalman filter (DKF) with Decoupled Direct Method (DDM) sensitivity analysis. The simulations with satellite-inverted inventories are compared to the modeling results using the a priori inventory as well as an inventory created by a ground-level NO2 based DKF inversion. The DKF inversions yield conflicting results: the satellite based inversion scales up the a priori NOx emissions in most regions by factors of 1.02 to 1.84, leading to 3-55% increase in modeled NO2 column densities and 1-7 ppb increase in ground 8 h ozone concentrations, while the ground-based inversion indicates the a priori NOx emissions should be scaled by factors of 0.34 to 0.57 in each region. However, none of the inversions improve the model performance in simulating aircraft-observed NO2 or ground-level ozone (O3) concentrations.

Nitrogen dioxide↗

Comparison of OMI NO2 Observations and Their Seasonal and Weekly Cycles with Ground-Based Measurements in Helsinki

We present the comparison of satellite-based OMI (Ozone Monitoring Instrument) NO2 products with ground-based observations in Helsinki. OMI NO2 total columns, available from standard product (SP) and DOMINO algorithm, are compared with the measurements performed by the Pandora spectrometer in Helsinki in 2012. The relative difference between Pandora 21 and OMI SP retrievals is 4 and 6 for clear sky and all sky conditions, respectively. DOMINO NO2 retrievals showed slightly lower total columns with median differences about 5 and 14 for clear sky and all sky conditions, respectively. Large differences often correspond to cloudy autumn-winter days with solar zenith angles above 65. Nevertheless, the differences remain within the retrieval uncertainties. Furthermore, the weekly and seasonal cycles from OMI, Pandora and NO2 surface concentrations are compared. Both satellite- and ground-based data show a similar weekly cycle, with lower NO2 levels during the weekend compared to the weekdays as result of reduced emissions from traffic and industrial activities. Also the seasonal cycle shows a similar behavior, even though the results are affected by the fact that most of the data are available during spring-summer because of cloud cover in other seasons. This is one of few works in which OMI NO2 retrievals are evaluated in an urban site at high latitudes (60N). Despite the city of Helsinki having relatively small pollution sources, OMI retrievals have proved to be able to describe air quality features and variability similar to surface observations. This adds confidence in using satellite observations for air quality monitoring also at high latitudes.

Validation↗

Spatial and Temporal Variability of Ground and Satellite Column Measurements of NO2 and O3 over the Atlantic Ocean During the Deposition of Atmospheric Nitrogen to Coastal Ecosystems Experiment

In situ measurements of O3 and nitrogen oxides (NO + NO2=NOx) and remote sensing measurements of total column NO2 and O3 were collected on a ship in the North Atlantic Ocean as part of the Deposition of Atmospheric Nitrogen to Coastal Ecosystems (DANCE) campaign in July August 2014,100 km east of the mid-Atlantic United States. Relatively clean conditions for both surface in situ mixing ratio and total column O3 and NO2 measurements were observed throughout the campaign. Increased surface and column NO2 and O3 amounts were observed when a terrestrial air mass was advected over the study region. Relative to ship-based total column measurements using a Pandora over the entire study, satellite measurements overestimated total column NO2 under these relatively clean atmospheric conditions over offshore waters by an average of 16. Differences are most likely due to proximity, or lack thereof, to surface emissions; spatial averaging due to the field of view of the satellite instrument; and the lack of sensitivity of satellite measurements to the surface concentrations of pollutants. Total column O3 measurements from the shipboard Pandora showed good correlation with the satellite measurements(r 0.96), but satellite measurements were 3 systematically higher than the ship measurements, in agreement with previous studies. Derived values of boundary layer height using the surface in situ and total column measurements of NO2 are much lower than modeled and satellite-retrieved boundary layer heights, which highlight the differences in the vertical distribution between terrestrial and marine environments.

Martins, Douglas K.↗

Aura OMI Observations of Regional SO2 and NO2 Pollution Changes from 2005 to 2015

The Ozone Monitoring Instrument (OMI) onboard NASA's Aura satellite has been providing global observations of the ozone layer and key atmospheric pollutant gases, such as nitrogen dioxide (NO2) and sulfur dioxide (SO2), since October 2004. The data products from the same instrument provide consistent spatial and temporal coverage and permit the study of anthropogenic and natural emissions on local-to-global scales. In this paper, we examine changes in SO2 and NO2 over some of the world's most polluted industrialized regions during the first decade of OMI observations. In terms of regional pollution changes, we see both upward and downward trends, sometimes in opposite directions for NO2 and SO2, for different study areas. The trends are, for the most part, associated with economic and/or technological changes in energy use, as well as regional regulatory policies. Over the eastern US, both NO2 and SO2 levels decreased dramatically from 2005 to 2015, by more than 40 and 80 percent, respectively, as a result of both technological improvements and stricter regulations of emissions. OMI confirmed large reductions in SO2 over eastern Europe's largest coal-fired power plants after installation of flue gas desulfurization devices. The North China Plain has the world's most severe SO2 pollution, but a decreasing trend has been observed since 2011, with about a 50 percent reduction in 2012-2015, due to an economic slowdown and government efforts to restrain emissions from the power and industrial sectors. In contrast, India's SO2 and NO2 levels from coal power plants and smelters are growing at a fast pace, increasing by more than 100 and 50 percent, respectively, from 2005 to 2015. Several SO2 hot spots observed over the Persian Gulf are probably related to oil and gas operations and indicate a possible underestimation of emissions from these sources in bottom-up emission inventories. Overall, OMI observations have proved valuable in documenting rapid changes in air quality over different parts of the world during last decade. The baseline established during the first 11 years of OMI is indispensable for the interpretation of air quality measurements from current and future satellite atmospheric composition missions.

SO2 and NO2↗

Aura OMI observations of regional SO2 and NO2 pollution changes from 2005 to 2015

The Ozone Monitoring Instrument (OMI) onboard NASA's Aura satellite has been providing global observations of the ozone layer and key atmospheric pollutant gases, such as nitrogen dioxide (NO2/ and sulfur dioxide (SO2/, since October 2004. The data products from the same instrument provide consistent spatial and temporal coverage and permit the study of anthropogenic and natural emissions on local-to-global scales. In this paper, we examine changes in SO2 and NO2 over some of the world's most polluted industrialized regions during the first decade of OMI observations. In terms of regional pollution changes, we see both upward and downward trends, sometimes in opposite directions for NO2 and SO2, for different study areas. The trends are, for the most part, associated with economic and/or technological changes in energy use, as well as regional regulatory policies. Over the eastern US, both NO2 and SO2 levels decreased dramatically from 2005 to 2015, by more than 40 and 80 %, respectively, as a result of both technological improvements and stricter regulations of emissions. OMI confirmed large reductions in SO2 over eastern Europe's largest coal-fired power plants after installation of flue gas desulfurization devices. The North China Plain has the world's most severe SO2 pollution, but a decreasing trend has been observed since 2011, with about a 50% reduction in 2012- 2015, due to an economic slowdown and government efforts to restrain emissions from the power and industrial sectors. In contrast, India's SO2 and NO2 levels from coal power plants and smelters are growing at a fast pace, increasing by more than 100 and 50 %, respectively, from 2005 to 2015. Several SO2 hot spots observed over the Persian Gulf are probably related to oil and gas operations and indicate a possible underestimation of emissions from these sources in bottom-up emission inventories. Overall, OMI observations have proved valuable in documenting rapid changes in air quality over different parts of the world during last decade. The baseline established during the first 11 years of OMI is indispensable for the interpretation of air quality measurements from current and future satellite atmospheric composition missions.

Pollution trends↗

Effects of Surface BRDF on the OMI Cloud and NO2 Retrievals: A New Approach Based on Geometry-Dependent Lambertian Equivalent Reflectivity (GLER) Derived from MODIS

The Ozone Monitoring Instrument (OMI) cloud and NO2 algorithms use a monthly gridded surface reflectivity climatology that does not depend upon the observation geometry. In reality, reflection of incoming direct and diffuse solar light from land or ocean surfaces is sensitive to the sun sensor geometry. This dependence is described by the bidirectional reflectance distribution function (BRDF). To account for the BRDF, we propose to use a new concept of geometry-dependent Lambertian equivalent reflectivity (GLER). Implementation within the existing OMI cloud and NO2 retrieval infrastructure requires changes only to the input surface reflectivity database. GLER is calculated using a vector radiative transfer model with high spatial resolution BRDF information from MODIS over land and the Cox Munk slope distribution over ocean with a contribution from water-leaving radiance. We compare GLER and climatological LER at 466 nm, which is used in the OMI O2-O2cloud algorithm to derive effective cloud fractions. A detailed comparison of the cloud fractions and pressures derived with climatological and GLERs is carried out. GLER and corresponding retrieved cloud products are then used as input to the OMI NO2 algorithm. We find that replacing the climatological OMI-based LERs with GLERs can increase NO2 vertical columns by up to 50 % in highly polluted areas; the differences include both BRDF effects and biases between the MODIS and OMI-based surface reflectance data sets. Only minor changes to NO2 columns (within 5 %) are found over unpolluted and overcast areas.

MODIS BRDF OMI clouds NO2 GLER↗

A photoionization study of the formation of NO2/+/ by reaction of excited O2/+/ ions with NO

Photoionization mass spectrometer results are presented for the first observation of the ion-molecule reaction in which O2(+) + NO yields NO2(+) + O. The reaction is energetically possible for ground state O2(+) ions in the lowest vibrational level. Photoionization efficiency curves for NO(+), O2(+), and NO2(+) are presented and compared, with special emphasis on autoionization features. In addition to the production of NO2(+) by the cited reaction, there is also a possibility for NO2(+) formation by the process O2 + NO(+) yielding NO2(+) + O. This reaction is calculated to be exothermic for incident photon energies of 11.73 eV.

Ajello, J. M.↗

A two-dimensional model study of the QBO signal in SAGE II NO2 and O3

Calculations of the quasi biennial oscillation (QBO) signal in Stratospheric Aerosol and Gas Experiment (SAGE) II O3 and NO2 data between 1984 and 1991 are presented and have been investigated by using a two-dimensional model. The isentropic 2D model is a fully interactive radiative-dynamical-chemical model in which the eddy fluxes of chemical species are calculated in a consistent manner. The QBO in the model has been forced by relaxing the equatorial zonal wind toward the observations at Singapore allowing the comparison of the model with observations from specific years. The model reproduces the observed vertical structure of the equatorial ozone anomaly with the well-known transition from dynamical to photochemical control at around 28km. The model also reproduces the observed vertical structure of the SAGE II observed NO2 anomaly. The model studies have shown that it is the QBO modulation of NO2 which the main cause of QBO signal in O3 above 30 km. The model also reproduces the observed latitudinal structure of the QBO signals in O3 and NO2. Due to the differing horizontal distribution of O3 and NO(y) the ozone signal shows a distinct phase change in the subtropics whereas the NO2 anomaly gives a broader signal.

Chipperfield, M. P.↗

Stratospheric NO and NO2 Abundances from ATMOS Solar-Occultation Measurements

Using results from a time-dependent photochemical model to calculate the diurnal variation of NO and NO2, we have corrected Atmospheric Trace MOlecule Spectroscopy (ATMOS) solar-occultation retrievals of the NO and NO2 abundances at 90' solar zenith angle. Neglecting to adjust for the rapid variation of these gases across the terminator results in potential errors in retrieved profiles of approximately 20% for NO2 and greater than 100% for NC at altitudes below 25 km. Sensitivity analysis indicates that knowledge of the local 03 and temperature profiles, rather than zonal mean or climatological conditions of these quantities, is required to obtain reliable retrievals of NO and NO2 in the lower stratosphere. Extremely inaccurate 03 or temperature values at 20 km can result in 50% errors in retrieved NO or NO2. Mixing ratios of NO in the mid-latitude, lower stratosphere measured by ATMOS during the November 1994 ATLAS-3 mission compare favorably with in situ ER-2 observations, providing strong corroboration of the reliability of the adjusted space-borne measurements.

Newchurch, M. J.↗

Planetary Aeronomy: NO2 In the Martian Atmosphere - 2

The transmission curve of the Martian atmosphere derived by Opik is compared with transmission curves of an atmosphere containing various amounts of nitrogen dioxide. It is found that the amount of 6 x l0(exp 18) sq cm column NO2 (or even less) given by Sinton as an upper limit for the Martian NO2 content could adequately explain the phenomenon of the blue haze. This finding made it worthwhile to investigate the effect of the temperature and pressure sensitive equilibrium 2 NO2 reversibly yields N204 upon the total NO2 content and the altitude-number density distributions of NO2 and N204. Computations were carried out for surface temperatures of 273 K, 243 K, 213 K, and 183 K and for three different temperature distributions. The discussion of the results leads to the suggestion of several important new experiments.

Warneck, P.↗

Algorithm for NO2 Vertical Column Retrieval from the Ozone Monitoring Instrument

We describe the operational algorithm for the retrieval of stratospheric, tropospheric, and total column densities of nitrogen dioxide NO2 from earthshine radiances measured by the Ozone Monitoring Instrument (OMI), aboard the EOS-Aura satellite. The algorithm uses the DOAS method for the retrieval of slant column NO densities. Air mass factors (AMFs) calculated from a stratospheric NO2 profile are used to make initial estimates of the vertical column density. Using data collected over a 24-h period, a smooth estimate of the global stratospheric field is constructed. Where the initial vertical column densities exceed the estimated stratospheric field, we infer the presence of tropospheric NO2, and recalculate the vertical column density (VCD) using an AMF calculated from an assumed tropospheric NO2 profile. The parameters that control the operational algorithm were selected with the aid of a set of data assembled from stratospheric and tropospheric chemical transport models. We apply the optimized algorithm to OMI data and present global maps of NO2 VCDs for the first time.

Bucsela, Eric J.↗