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NO2 Profile retrieval using airborne multi axis UV-visible skylight absorption measurements over central Europe

A recent development in ground-based remote sensing of atmospheric constituents by UV/visible absorption measurements of scattered light is the simultaneous use of several directions with small elevation angles in addition to the traditional zenith-sky pointing. The different light paths through the atmosphere enable the vertical distribution of some atmospheric absorbers such as NO2, BrO or O3 to be retrieved. In this study, the amount of profile information that can be retrieved from such measurements on aircraft is investigated for the trace gas NO2. A Sensitivity study on synthetic data is performed for a combination of four lines of sight (LOS) (0°(nadir), 88°, 92°, and 180° (zenith)) and three wavelength regions [center wavelengths: 362.5 nm, 437.5 nm, and 485.0 nm]. The method used in this work is a combination of two previously established methods described in Petritoli et al. (2002) and Wang et al. (2004). The investigation presented here demonstrates the potential of this LOS/wavelengths setup to retrieve a significant amount of profile information from airborne multiax is differential optical absorption spectrometer (AMAXDOAS) measurements with a vertical resolution of 3.0 to 4.5 km in the lower troposphere and 2.0 to 3.5 km near flight altitude. Above 13 km the profile information content of AMAXDOAS measurements is sparse. The retrieval algorithm used in this work is the AMAXDOAS profile retrievalalgorithm (APROVAL). Further, retrieved profiles with a significant amount (up to 3.2 ppbv) of NO2 in the boundary layer over the Po-valley (Italy) are presented. Airborne multiaxis measurements are thus a promising tool for atmospheric studies in the troposphere.
Homogeneous nucleation rates of nitric acid dihydrate (NAD) at simulated stratospheric conditions – Part II: Modelling

Activation energies ΔGact for the nucleation of nitric acid dihydrate (NAD) in supercooled binary HNO3/H2O solution droplets were calculated from volume-based nucleation rate measurements using the AIDA (Aerosol, Interactions, and Dynamics in the Atmosphere) aerosol chamber of Forschungszentrum Karlsruhe. The experimental conditions covered temperatures T between 192 and 197 K, NAD saturation ratios SNAD between 7 and 10, and nitric acid molar fractions of the nucleating sub-micron sized droplets between 0.26 and 0.28. Based on classical nucleation theory, a new parameterisation for ΔGact=A×(T ln SNAD)−2+B is fitted to the experimental data with A=2.5×106 kcal K2 mol−1 and B=11.2−0.1(T−192) kcal mol−1. A and B were chosen to also achieve good agreement with literature data of ΔGact. The parameter A implies, for the temperature and composition range of our analysis, a mean interface tension σsl=51 cal mol−1 cm−2 between the growing NAD germ and the supercooled solution. A slight temperature dependence of the diffusion activation energy is represented by the parameter B. Investigations with a detailed microphysical process model showed that literature formulations of volume-based (Salcedo et al., 2001) and surface-based (Tabazadeh et al., 2002) nucleation rates significantly overestimate NAD formation rates when applied to the conditions of our experiments.
The potential impact of ClOx radical complexes on polar stratospheric ozone loss processes

The importance of radical-molecule complexes for atmospheric chemistry has been discussed in recent years. In particular, the existence of a ClO·O2 and ClOx water radical complexes like ClO·H2O, OClO·H2O, OClO·(H2O)2, and ClOO·H2O could play a role in enhancing the ClO dimer (Cl2O2) formation and therefore may constitute an important intermediate in polar stratospheric ozone loss cycles. Model simulations performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS) will be presented to study the role of radical complexes on polar stratospheric ozone loss processes. The model simulations are performed for the Arctic winter 2002/2003 at a level of 500 K potential temperature and the results are compared to observed ozone loss rates determined by the Match technique. Moreover, recently reported values for the equilibrium constant of the ClO dimer formation are used to restrict the number of possible model results caused by large uncertainties about radical complex chemistry. Our model simulations show that the potential impact of ClO·O2 on polar ozone loss processes is small (dO3/dt≪0.5 ppb/sunlight h) provided that the ClO·O2 complex is only weakly stable. Assuming that the binding energies of the ClOx water complexes are much higher than theoretically predicted an enhancement of the ozone loss rate by up to ≈0.5 ppb/sunlight h is simulated. Because it is unlikely that the ClOx water complexes are much more stable than predicted we conclude that these complexes have no impact on polar stratospheric ozone loss processes. Although large uncertainties about radical complex chemistry exist, our findings show that the potential impact of ClOx radical molecule complexes on polar stratospheric ozone loss processes is very small considering pure gas-phase chemistry. However the existence of ClOx radical-molecule complexes could possibly explain discrepancies for the equilibrium constant of the ClO dimer formation found between recent laboratory and stratospheric measurements.
Rayleigh lidar observations of double stratopause structure over three different northern hemisphere stations

Using four years of Rayleigh lidar data collected from three different northern hemisphere stations (Gadanki 13.5° N, 79.2° E ; Mt. Abu 24.5° N, 72.7° E and Observatoire de Haute Provence: OHP; 44° N, 6° E), the characteristics of double (separated) stratopause occurrence are presented here, for the first time. The characteristics are illustrated by a seasonal change during summer and winter and the variation in percentage of occurrence from place to place. It is found that the over-all mean normal stratopause (NS) positioned at the middle level of double stratopause (upper and lower level) with its location nearer to the lower level of double stratopause (LDS) than to the upper level of double stratopause (UDS). The frequency distribution of NS, LDS and UDS demonstrated variability with location, indicating role of dynamical activity. By making use of a quasi-continuous 40 days of lidar observations over Gadanki and OHP, the responsibility of Gravity Wave (GW) and Planetary Wave (PW) activity for the LDS and UDS occurrence are examined and presented.
Oxalic acid as a heterogeneous ice nucleus in the upper troposphere and its indirect aerosol effect

Heterogeneous ice freezing points of aqueous solutions containing various immersed solid dicarboxylic acids (oxalic, adipic, succinic, phthalic and fumaric) have been measured with a differential scanning calorimeter. The results show that only the dihydrate of oxalic acid (OAD) acts as a heterogeneous ice nucleus, with an increase in freezing temperature between 2 and 5 K depending on solution composition. In several field campaigns, oxalic acid enriched particles have been detected in the upper troposphere with single particle aerosol mass spectrometry. Simulations with a microphysical box model indicate that the presence of OAD may reduce the ice particle number density in cirrus clouds by up to ~50% when compared to exclusively homogeneous cirrus formation without OAD. Using the ECHAM4 climate model we estimate the global net radiative effect caused by this heterogeneous freezing to result in a cooling as high as −0.3 Wm−2.
Black carbon or brown carbon? The nature of light-absorbing carbonaceous aerosols

Although the definition and measurement techniques for atmospheric "black carbon" ("BC") or "elemental carbon' ("EC") have long been subjects of scientific controversy, the recent discovery of light-absorbing carbon that is not black ("brown carbon, Cbrown") makes it imperative to reassess and redefine the components that make up light-absorbing carbonaceous matter (LAC) in the atmosphere. Evidence for the atmospheric presence of Cbrown comes from (1) spectral aerosol light absorption measurements near specific combustion sources, (2) observations of spectral properties of water extracts of continental aerosol, (3) laboratory studies indicating the formation of light-absorbing organic matter in the atmosphere, and (4) indirectly from the chemical analogy of aerosol species to colored natural humic substances. We show that brown carbon may severely bias measurements of "BC" and "EC" over vast parts of the troposphere, especially those strongly polluted by biomass burning, where the mass concentration of Cbrown is high relative to that of soot carbon. Chemical measurements to determine "EC" are biased by the refractory nature of Cbrown as well as by complex matrix interferences. Optical measurements of "BC" suffer from a number of problems: (1) many of the presently used instruments introduce a substantial bias into the determination of aerosol light absorption, (2) there is no unique conversion factor between light absorption and "EC" or "BC" concentration in ambient aerosols, and (3) the difference in spectral properties between the different types of LAC, as well as the chemical complexity of Cbrown, lead to several conceptual as well as practical complications. We also suggest that due to the sharply increasing absorption of Cbrown towards the UV, single-wavelength light absorption measurements may not be adequate for the assessment of absorption of solar radiation in the troposphere. We discuss the possible consequences of these effects for our understanding of tropospheric processes, including their influence on UV-irradiance, atmospheric photochemistry and radiative transfer in clouds.
Testing our understanding of Arctic denitrification using MIPAS-E satellite measurements in winter 2002/2003

Observations of gas-phase HNO3 and N2O in the polar stratosphere from the Michelson Interferometer for Passive Atmospheric Sounding aboard the ENVISAT satellite (MIPAS-E) were made during the cold Arctic winter of 2002/2003. Vortex temperatures were unusually low in early winter and remained favourable for polar stratospheric cloud formation and denitrification until mid-January. MIPAS-E observations provide the first dataset with sufficient coverage of the polar vortex in mid-winter which enables a reasonable estimate of the timing of onset and spatial distribution of denitrification of the Arctic lower stratosphere to be performed. We use the observations from MIPAS-E to test the evolution of denitrification in the DLAPSE (Denitrification by Lagrangian Particle Sedimentation) microphysical denitrification model coupled to the SLIMCAT chemical transport model. In addition, the predicted denitrification from a simple equilibrium nitric acid trihydrate-based scheme is also compared with MIPAS-E. Modelled denitrification is compared with in-vortex NOy and N2O observations from the balloon-borne MarkIV interferometer in mid-December. Denitrification was clearly observed by MIPAS-E in mid-December 2002 and reached 80% in the core of the vortex by early January 2003. The DLAPSE model is broadly able to capture both the timing of onset and the spatial distribution of the observed denitrification. A simple thermodynamic equilibrium scheme is able to reproduce the observed denitrification in the core of the vortex but overestimates denitrification closer to the vortex edge. This study also suggests that the onset of denitrification in simple thermodynamic schemes may be earlier than in the MIPAS-E observations.
Technical note: Evaluation of standard ultraviolet absorption ozone monitors in a polluted urban environment

The performance of the EPA Federal Equivalent Method (FEM) technique for monitoring ambient concentrations of O3 via ultraviolet absorption (UV) has been evaluated using data from the Mexico City Metropolitan Area field campaign (MCMA-2003). Comparisons of UV O3 monitors with open path Differential Optical Absorption Spectroscopy (DOAS) and open path Fourier Transform Infrared (FTIR) spectroscopy instruments in two locations revealed average discrepancies in the measured concentrations between +13% to −18%. Good agreement of two separate open path DOAS measurements at one location indicated that spatial and temporal inhomogeneities were not substantially influencing comparisons of the point sampling and open path instruments. The poor agreement between the UV O3 monitors and the open path instruments was attributed to incorrect calibration factors for the UV monitors, although interferences could not be completely ruled out. Applying a linear correction to these calibration factors results in excellent agreement of the UV O3 monitors with the co-located open path measurements; regression slopes of 0.94 to 1.04 and associated R2 values of >0.89. A third UV O3 monitor suffered from large spurious interferences, which were attributed to extinction of UV radiation within the monitor by fine particles (<0.2 µm). The overall performance of this particular monitor was poor owing to a combination of interferences from a contaminated particle filter and/or ozone scrubber. Suggestions for improved operation practices of these UV O3 monitors and recommendations for future testing are made.
Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature)

Reactive gases and aerosols are produced by terrestrial ecosystems, processed within plant canopies, and can then be emitted into the above-canopy atmosphere. Estimates of the above-canopy fluxes are needed for quantitative earth system studies and assessments of past, present and future air quality and climate. The Model of Emissions of Gases and Aerosols from Nature (MEGAN) is described and used to quantify net terrestrial biosphere emission of isoprene into the atmosphere. MEGAN is designed for both global and regional emission modeling and has global coverage with ~1 km2 spatial resolution. Field and laboratory investigations of the processes controlling isoprene emission are described and data available for model development and evaluation are summarized. The factors controlling isoprene emissions include biological, physical and chemical driving variables. MEGAN driving variables are derived from models and satellite and ground observations. Tropical broadleaf trees contribute almost half of the estimated global annual isoprene emission due to their relatively high emission factors and because they are often exposed to conditions that are conducive for isoprene emission. The remaining flux is primarily from shrubs which have a widespread distribution. The annual global isoprene emission estimated with MEGAN ranges from about 500 to 750 Tg isoprene (440 to 660 Tg carbon) depending on the driving variables which include temperature, solar radiation, Leaf Area Index, and plant functional type. The global annual isoprene emission estimated using the standard driving variables is ~600 Tg isoprene. Differences in driving variables result in emission estimates that differ by more than a factor of three for specific times and locations. It is difficult to evaluate isoprene emission estimates using the concentration distributions simulated using chemistry and transport models, due to the substantial uncertainties in other model components, but at least some global models produce reasonable results when using isoprene emission distributions similar to MEGAN estimates. In addition, comparison with isoprene emissions estimated from satellite formaldehyde observations indicates reasonable agreement. The sensitivity of isoprene emissions to earth system changes (e.g., climate and land-use) demonstrates the potential for large future changes in emissions. Using temperature distributions simulated by global climate models for year 2100, MEGAN estimates that isoprene emissions increase by more than a factor of two. This is considerably greater than previous estimates and additional observations are needed to evaluate and improve the methods used to predict future isoprene emissions.
Comparison of GOME tropospheric NO2 columns with NO2 profiles deduced from ground-based in situ measurements

Nitrogen dioxide (NO2) vertical tropospheric column densities (VTCs) retrieved from the Global Ozone Monitoring Experiment (GOME) are compared to coincident ground-based tropospheric NO2 columns. The ground-based columns are deduced from in situ measurements at different altitudes in the Alps for 1997 to June 2003, yielding a unique long-term comparison of GOME NO2 VTC data retrieved by a collaboration of KNMI (Royal Netherlands Meteorological Institute) and BIRA/IASB (Belgian Institute for Space Aeronomy) with independently derived tropospheric NO2 profiles. A first comparison relates the GOME retrieved tropospheric columns to the tropospheric columns obtained by integrating the ground-based NO2 measurements. For a second comparison, the tropospheric profiles constructed from the ground-based measurements are first multiplied with the averaging kernel (AK) of the GOME retrieval. The second approach makes the comparison independent from the a priori NO2 profile used in the GOME retrieval. This allows splitting the total difference between the column data sets into two contributions: one that is due to differences between the a priori and the ground-based NO2 profile shapes, and another that can be attributed to uncertainties in both the remaining retrieval parameters (such as, e.g., surface albedo or aerosol concentration) and the ground-based in situ NO2 profiles. For anticyclonic clear sky conditions the comparison indicates a good agreement between the columns (n=157, R=0.70/0.74 for the first/second comparison approach, respectively). The mean relative difference (with respect to the ground-based columns) is −7% with a standard deviation of 40% and GOME on average slightly underestimating the ground-based columns. Both data sets show a similar seasonal behaviour with a distinct maximum of spring NO2 VTCs. Further analysis indicates small GOME columns being systematically smaller than the ground-based ones. The influence of different shapes in the a priori and the ground-based NO2 profile is analysed by considering AK information. It is moderate and indicates similar shapes of the profiles for clear sky conditions. Only for large GOME columns, differences between the profile shapes explain the larger part of the relative difference. In contrast, the other error sources give rise to the larger relative differences found towards smaller columns. Further, for the clear sky cases, errors from different sources are found to compensate each other partially. The comparison for cloudy cases indicates a poorer agreement between the columns (n=60, R=0.61). The mean relative difference between the columns is 60% with a standard deviation of 118% and GOME on average overestimating the ground-based columns. The clear improvement after inclusion of AK information (n=60, R=0.87) suggests larger errors in the a priori NO2 profiles under cloudy conditions and demonstrates the importance of using accurate profile information for (partially) clouded scenes.