bluuebunny/crossref_metadata_2025 huggingface dataset:
Improving cloud information over deserts from SCIAMACHY Oxygen A-band measurements
Authors: Fournier N. , Stammes P. , de Graaf M. , van der A R. , Piters A. , Grzegorski M. , Kokhanovsky A.
Published: April 2010

Abstract. The retrieval of column densities and concentration profiles of atmospheric trace gas species from satellites is sensitive to light scattered by clouds. The SCanning Imaging Absorption SpectroMeter for Atmospheric CHartographY (SCIAMACHY) instrument on the Envisat satellite, principally designed to retrieve trace gases in the atmosphere, is also capable of detecting clouds. FRESCO (Fast Retrieval Scheme for Clouds from the Oxygen A-band) is a fast and robust algorithm providing cloud information from the O2 A-band for cloud correction of ozone. FRESCO provides a consistent set of cloud products by retrieving simultaneously effective cloud fraction and cloud top pressure. The FRESCO retrieved values are compared with the SCIAMACHY Level 2 operational cloud fraction of OCRA (Optical Cloud Recognition Algorithm) but, also, with cloud information from HICRU (Heidelberg Iterative Cloud Retrieval Utilities), SACURA (SemiAnalytical CloUd Retrieval Algorithm) and the MODIS (Moderate Resolution Imaging Spectroradiometer) instrument. The results correlate well, but FRESCO overestimates cloud fraction over deserts. Thus, to improve retrievals at these locations, the FRESCO surface albedo databases are decontaminated from the presence of desert dust aerosols. This is achieved by using the GOME Absorbing Aerosol Index. It is shown that this approach succeeds well in producing more accurate cloud information over the Sahara.
Technical note: Simulating chemical systems in Fortran90 and Matlab with the Kinetic PreProcessor KPP-2.1
Authors: Sandu A. , Sander R.
Published: April 2010

Abstract. This paper presents the new version 2.1 of the Kinetic PreProcessor (KPP). Taking a set of chemical reactions and their rate coefficients as input, KPP generates Fortran90, Fortran77, Matlab, or C code for the temporal integration of the kinetic system. Efficiency is obtained by carefully exploiting the sparsity structures of the Jacobian and of the Hessian. A comprehensive suite of stiff numerical integrators is also provided. Moreover, KPP can be used to generate the tangent linear model, as well as the continuous and discrete adjoint models of the chemical system.
Evaluation of high-resolution forecasts with the non-hydrostaticnumerical weather prediction model Lokalmodell for urban air pollutionepisodes in Helsinki, Oslo and Valencia
Authors: Fay B. , Neunhäuserer L.
Published: April 2010

Abstract. The operational numerical weather prediction model Lokalmodell LM with 7 km horizontal resolution was evaluated for forecasting meteorological conditions during observed urban air pollution episodes. The resolution was increased to experimental 2.8 km and 1.1 km resolution by one-way interactive nesting without introducing urbanisation of physiographic parameters or parameterisations. The episodes examined are two severe winter inversion-induced episodes in Helsinki in December 1995 and Oslo in January 2003, three suspended dust episodes in spring and autumn in Helsinki and Oslo, and a late-summer photochemical episode in the Valencia area. The evaluation was basically performed against observations and radiosoundings and focused on the LM skill at forecasting the key meteorological parameters characteristic for the specific episodes. These included temperature inversions, atmospheric stability and low wind speeds for the Scandinavian episodes and the development of mesoscale recirculations in the Valencia area. LM forecasts often improved due to higher model resolution especially in mountainous areas like Oslo and Valencia where features depending on topography like temperature, wind fields and mesoscale valley circulations were better described. At coastal stations especially in Helsinki, forecast gains were due to the improved physiographic parameters (land fraction, soil type, or roughness length). The Helsinki and Oslo winter inversions with extreme nocturnal inversion strengths of 18°C were not sufficiently predicted with all LM resolutions. In Helsinki, overprediction of surface temperatures and low-level wind speeds basically led to underpredicted inversion strength. In the Oslo episode, the situation was more complex involving erroneous temperature advection and mountain-induced effects for the higher resolutions. Possible explanations include the influence of the LM treatment of snow cover, sea ice and stability-dependence of transfer and diffusion coefficients. The LM simulations distinctly improved for winter daytime and nocturnal spring and autumn inversions and showed good skill at forecasting further episode-relevant meteorological parameters. The evaluation of the photochemical Valencia episode concentrated on the dominating mesoscale circulation patterns and showed that the LM succeeds well in describing all the qualitative features observed in the region. LM performance in forecasting the examined episodes thus depends on the key episode characteristics and also the season of the year with a need to improve model performance in very stable inversion conditions not only for urban simulations.
Impacts of using reformulated and oxygenated fuel blends on the regional air quality of the upper Rhine valley
Authors: Vinuesa J.-F. , Mirabel Ph. , Ponche J.-L.
Published: April 2010

Abstract. The effects of using three alternative gasoline fuel blends on regional air quality of the upper Rhine valley have been investigated. The first of the tested fuels is oxygenated by addition of ethyl-tertio-butyl ether (ETBE), the second is based on a reformulation of its composition and the third on is both oxygenated and reformulated. The upper Rhine valley is a very sensitive region for pollution episodes and several meteorological and air quality studies have already been performed. High temporal and spatial emission inventories are available allowing relevant and realistic modifications of the emission inventories. The calculation period, i.e., 11 May 1998, corresponds to a regional photochemical ozone pollution episode during which ozone concentrations exceeded several times the information threshold of the ozone directive of the European Union (180 μg m-3 as 1 hourly average). New emission inventories are set up using specific emission factors related to the alternative fuels by varying the fraction of gasoline passenger cars (from 50% to 100%) using the three fuel blends. Then air quality modeling simulations are performed using these emission inventories over the upper Rhine valley. The impact of alternative fuels on regional air quality is evaluated by comparing these simulations with the one using a reference emission inventory, e.g., where no modifications of the fuel composition are included. The results are analyzed by focusing on peak levels and daily averaged concentrations. The use of the alternative fuels leads to general reductions of ozone and volatile organic compounds (VOC) and increases of NOx levels. We found different behaviors related to the type of the area of concern i.e. rural or urban. The impacts on ozone are enhanced in urban areas where 15% reduction of the ozone peak and daily averaged concentrations can be reached. This behavior is similar for the NOx for which, in addition, an increase of the levels can be noted in urban plumes over rural areas. The most important decreases of the total VOC levels are mainly located over rural areas (more than 5% reduction of the levels except in urban plumes). By comparing these results with those from a local study related to the air quality of Strasbourg, we estimate that the regional contribution to the urban air quality of Strasbourg allows an enhancement of the results by using alternative fuel blends at the regional scale.
Effects of column density on I2spectroscopy and a determination of I2absorption cross section at 500 nm
Authors: Spietz P. , Gómez Martín J. , Burrows J. P.
Published: April 2010

Abstract. The use of ro-vibronic spectra of I2 in the region of 543 nm to 578 nm as reference spectra for atmospheric Differential Optical Absorption Spectroscopy is studied. It is shown that the retrieval of atmospheric column densities with Differential Optical Absorption Spectroscopy set-ups at FWHM at and above 1 nm depends critically on the column density, under which the used reference spectrum was recorded. Systematic overestimation of the comparatively low atmospheric column density of I2 of the order of 13% is possible. Under low pressure conditions relevant in laboratory studies, the systematic deviations may grow up to 45%. To avoid such effects with respect to field measurements, new reference spectra of I2 were determined under column density of the order of 1016 cm-2 close to that expected for an atmospheric measurement. Two typical configurations of Differential Optical Absorption Spectroscopy, which use grating spectrometers, were chosen for the spectroscopic set-up. One spectrum was recorded at similar resolution (0.25 nm FWHM) but finer binning (0.035 nm/pixel) than previously published data. For the other (0.59 nm FWHM, 0.154 nm/pixel) no previously published spectra exist. Wavelength calibration is accurate to ±0.04 nm and ±0.11 nm respectively. The absorption cross section for the recordings was determined under low column density with an accuracy of ±4% and ±3% respectively. The absolute absorption cross section of I2 at 500 nm (wavelength: in standard air) in the continuum absorption region was determined using a method independent of iodine vapour pressure. Obtained was σI2 (500 nm)=(2.186±0.021·10-18 cm2 in very good agreement with previously published results, but at 50% smaller uncertainty. From this and previously published results a weighted average of σI2(500 nm)=(2.191±0.02)·10-18 cm2 is determined.
The quantitative infrared and NIR spectrum of CH2I2 vapor: vibrational assignments and potential for atmospheric monitoring
Authors: Johnson T. J. , Masiello T. , Sharpe S. W.
Published: April 2010

Abstract. Diiodomethane (CH2I2) has recently become a molecule of significant atmospheric interest as it can contribute to coastal IO formation. As part of the PNNL database of gas-phase infrared spectra, the quantitative absorption spectrum of CH2I2 has been acquired at 0.1 cm-1 resolution. Two strong b2 symmetry A-type bands at 584 and 1114 cm-1 are observed, but are not resolved when broadened to 760 Torr with nitrogen and appear as B-type. In contrast, the b1 symmetry C-type bands near 5953, 4426 and 3073 cm-1 are resolved with rotational structure, including Q-branches with widths ≤1 cm-1. The quantitative infrared and near-infrared vapor-phase spectra (600–10 000 cm-1) are reported for the first time. Some bands are discussed in terms of their potential for atmospheric monitoring and theoretical detection limits on a selected basis. FT-Raman spectra and ab initio calculations are used to complete vibrational assignments in the C2v point group.
Ozone observations by the Gas and Aerosol Measurement Sensor during SOLVE II
Authors: Pitts M. C. , Thomason L. W. , Zawodny J. M. , Wenny B. N. , Livingston J. M. , Russell P. B. , Yee J.-H. , Swartz W. H. , Shetter R. E.
Published: April 2010

Abstract. The Gas and Aerosol Measurement Sensor (GAMS) was deployed aboard the NASA DC-8 aircraft during the second SAGE III Ozone Loss and Validation Experiment (SOLVE II). GAMS acquired line-of-sight (LOS) direct solar irradiance spectra during the sunlit portions of ten science flights of the DC-8 between 12 January and 4 February 2003. Differential line-of-sight (DLOS) optical depth spectra are produced from the GAMS raw solar irradiance spectra. Then, DLOS ozone number densities are retrieved from the GAMS spectra using a multiple linear regression spectral fitting technique. Both the DLOS optical depth spectra and retrieved ozone data are compared with coincident measurements from two other solar instruments aboard the DC-8 platform to demonstrate the robustness and stability of the GAMS data. The GAMS ozone measurements are then utilized to evaluate the quality of the Wulf band ozone cross sections, a critical component of the SAGE III aerosol, water vapor, and temperature/pressure retrievals. Results suggest the ozone cross section compilation of Shettle and Anderson currently used operationally in SAGE III data processing may be in error by as much as 10–20% in the Wulf bands, and their lack of reported temperature dependence is a significant deficiency. A second, more recent, cross section database compiled for the SCIAMACHY satellite mission appears to be of much better quality in the Wulf bands, but still may have errors as large as 5% near the Wulf band absorption peaks, which is slightly larger than their stated uncertainty. Additional laboratory measurements of the Wulf band cross sections should be pursued to further reduce their uncertainty and better quantify their temperature dependence.
Ambient formaldehyde measurements made at a remote marine boundary layer site during the NAMBLEX campaign – a comparison of data from chromatographic and modified Hantzsch techniques
Authors: Still T. J. , Al-Haider S. , Seakins P. W. , Sommariva R. , Stanton J. C. , Mills G. , Penkett S. A.
Published: April 2010

Abstract. Ambient formaldehyde concentrations are reported from the North Atlantic Marine Boundary Layer Experiment (NAMBLEX) campaign at Mace Head on the west coast of Eire during August 2002. The results from two techniques, using direct determination via gas chromatography and the Hantzsch technique, show similar trends but a significant off set in concentrations. For westerly air flows characteristic of the marine boundary layer, formaldehyde concentrations from the gas chromatographic and Hantzsch technique ranged from 0.78–1.15 ppb and 0.13–0.43 ppb, respectively. Possible reasons for the discrepancy have been investigated and are discussed, however, no satisfactory explanation has yet been found. In a subsequent laboratory intercomparison the two techniques were in good agreement. The observed concentrations have been compared with previous formaldehyde measurements in the North Atlantic marine boundary layer and with other measurements from the NAMBLEX campaign. The measurements from the Hantzsch technique and the GC results lie at the lower and upper ends respectively of previous measurements. In contrast to some previous measurements, both techniques show distinct diurnal profiles with day maxima and with an amplitude of approximately 0.15 ppb. Strong correlations were observed with ethanal concentrations measured during NAMBLEX and the ratio of ethanal to formaldehyde determined by the gas chromatographic technique is in good agreement with previous measurements. Some simple box modelling has been undertaken to investigate possible sources of formaldehyde. Such models are not able to predict absolute formaldehyde concentrations as they do not include transport processes, but the results show that oxygenated VOCs such as ethanal and methanol are very significant sources of formaldehyde in the air masses reaching Mace Head.
Atmospheric carbon gases retrieved from SCIAMACHY by WFM-DOAS: version 0.5 CO and CH4and impact of calibration improvements on CO2retrieval
Authors: Buchwitz M. , de Beek R. , Noël S. , Burrows J. P. , Bovensmann H. , Schneising O. , Khlystova I. , Bruns M. , Bremer H. , Bergamaschi P. , Körner S. , Heimann M.
Published: April 2010

Abstract. The three carbon gases carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4) are important atmospheric constituents affecting air quality and climate. The near-infrared nadir spectra measured by SCIAMACHY on ENVISAT contain information on the vertical columns of these gases which we retrieve using a modified DOAS algorithm (WFM-DOAS or WFMD). Our main data products are CO vertical columns and dry-air column averaged mixing ratios of methane (CH4) and CO2 (denoted XCH4 and XCO2). For CO and CH4 we present new results for the year 2003 obtained with an improved version of WFM-DOAS (WFMDv0.5) retrieved from Level 1 version 4 (Lv1v4) spectra. This data set has recently been compared with a network of ground based FTIR stations. Here we describe the WFMDv0.5 algorithm, present global and regional maps, and comparisons with global reference data. We show that major problems of the previous versions (v0.4 and v0.41) related to the varying ice-layer on the SCIAMACHY channel 8 detector have been solved. Compared to MOPITT the SCIAMACHY CO columns are on average higher by about 10–20%. Regionally, however, especially over central South America, differences can be much larger. For methane we present global and regional maps which are compared to TM5 model simulations performed using standard methane emission inventories. We show that methane source regions can be clearly detected with SCIAMACHY. We also show that the methane data product can be significantly further improved using Lv1v5 spectra with improved calibration. For CO2 we present three years of SCIAMACHY CO2 measurements over Park Falls, Wisconsin, USA, retrieved from Lv1v5. We show that the quality of CO2 retrieved from these spectra is significantly higher compared to WFMDv0.4 XCO2 retrieved from Lv1v4.
The influence of polar vortex ozone depletion on NH mid-latitude ozone trends in spring
Authors: Andersen S. B. , Knudsen B. M.
Published: April 2010

Abstract. Reverse domain-filling trajectory calculations have been performed for the years 1993, 1995, 1996, 1997, and 2000 to calculate the spreading of ozone depleted air from the polar vortex to midlatitudes in spring. We find that for these years with massive Arctic ozone depletion the zonal mean total ozone column at midlatitudes is reduced with between 7 and 12 DU in the April-May period. The polar vortex and remnants have preferred locations which leads to longitudinal differences in the midlatitude ozone trends. Together with decadal variations in circulation the dilution of ozone depleted air may explain the major fraction of longitudinal differences in midlatitude ozone trends. For the period 1979–1997 the dilution may explain 50% of the longitudinal differences in ozone trends and for the period 1979–2002 it may explain 45%. The dilution also has a significant impact on the zonal mean ozone trends in the April-May period. Although uncertainties are large due to uncertainties in the ozone depletion values and neglect of ozone depletion in other years than 1993, 1995, 1996, 1997, and 2000 we have tried to calculate the size of this effect. We estimate that dilution may explain 29% of the trend in the period 1979–1997 and 33% of the trend in the period 1979–2002 as a lower limit.
The time-space exchangeability of satellite retrieved relations between cloud top temperature and particle effective radius
Authors: Lensky I. M. , Rosenfeld D.
Published: April 2010

Abstract. A 3-minute 3-km rapid scan of the METEOSAT Second Generation geostationary satellite over southern Africa was applied to tracking the evolution of cloud top temperature (T) and particle effective radius (re) of convective elements. The evolution of T-re relations showed little dependence on time, leaving re to depend almost exclusively on T. Furthermore, cloud elements that fully grew to large cumulonimbus stature had the same T-re relations as other clouds in the same area with limited development that decayed without ever becoming a cumulonimbus. Therefore, a snap shot of T-re relations over a cloud field provides the same relations as composed from tracking the time evolution of T and re of individual clouds, and then compositing them. This is the essence of exchangeability of time and space scales, i.e., ergodicity, of the T-re relations for convective clouds. This property has allowed inference of the microphysical evolution of convective clouds with a snap shot from a polar orbiter. The fundamental causes for the ergodicity are suggested to be the observed stability of re for a given height above cloud base in a convective cloud, and the constant renewal of growing cloud tops with cloud bubbles that replace the cloud tops with fresh cloud matter from below.
Homogeneous nucleation rates of nitric acid dihydrate (NAD) at simulated stratospheric conditions – Part II: Modelling
Authors: Möhler O. , Bunz H. , Stetzer O.
Published: April 2010

Abstract. 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.
Development and validation of tools for the implementation of european air quality policy in Germany (Project VALIUM)
Authors: Schatzmann M. , Bächlin W. , Emeis S. , Kühlwein J. , Leitl B. , Müller W. J. , Schäfer K. , Schlünzen H.
Published: April 2010

Abstract. In the framework of the German Atmospheric Research Program AFO-2000 a system of consistent coupled numerical models has been developed. The purpose of the model system is to serve as a tool for the execution of European urban air quality regulations. A consortium with the acronym VALIUM was formed, which consisted of German research institutes, environmental consultancies and an environmental agency. A substantial part of the VALIUM program was devoted to the generation of a set of high quality data for the validation of the numerical model system. The validation data are based on a combination of field studies, tracer experiments and corresponding wind tunnel experiments. The field experiments were carried out inside and around a street canyon in a city district of Hanover/Germany. After a brief introduction to the VALIUM project a summary of the main results will be given.
Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature)
Authors: Guenther A. , Karl T. , Harley P. , Wiedinmyer C. , Palmer P. I. , Geron C.
Published: April 2010

Abstract. 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.
Aerosol chemical and optical properties over the Paris area within ESQUIF project
Authors: Hodzic A. , Vautard R. , Chazette P. , Menut L. , Bessagnet B.
Published: April 2010

Abstract. Aerosol chemical and optical properties are extensively investigated for the first time over the Paris Basin in July 2000 within the ESQUIF project. The measurement campaign offers an exceptional framework to evaluate the performances of the chemistry-transport model CHIMERE in simulating concentrations of gaseous and aerosol pollutants, as well as the aerosol-size distribution and composition in polluted urban environments against ground-based and airborne measurements. A detailed comparison of measured and simulated variables during the second half of July with particular focus on 19 and 31 pollution episodes reveals an overall good agreement for gas-species and aerosol components both at the ground level and along flight trajectories, and the absence of systematic biases in simulated meteorological variables such as wind speed, relative humidity and boundary layer height as computed by the MM5 model. A good consistency in ozone and NO concentrations demonstrates the ability of the model to reproduce the plume structure and location fairly well both on 19 and 31 July, despite an underestimation of the amplitude of ozone concentrations on 31 July. The spatial and vertical aerosol distributions are also examined by comparing simulated and observed lidar vertical profiles along flight trajectories on 31 July and confirm the model capacity to simulate the plume characteristics. The comparison of observed and modeled aerosol components in the southwest suburb of Paris during the second half of July indicates that the aerosol composition is rather correctly reproduced, although the total aerosol mass is underestimated by about 20%. The simulated Parisian aerosol is dominated by primary particulate matter that accounts for anthropogenic and biogenic primary particles (40%), and inorganic aerosol fraction (40%) including nitrate (8%), sulfate (22%) and ammonium (10%). The secondary organic aerosols (SOA) represent 12% of the total aerosol mass, while the mineral dust accounts for 8%. The comparison demonstrates the absence of systematic errors in the simulated sulfate, ammonium and nitrates total concentrations. However, for nitrates the observed partition between fine and coarse mode is not reproduced. In CHIMERE there is a clear lack of coarse-mode nitrates. This calls for additional parameterizations in order to account for the heterogeneous formation of nitrate onto dust particles. Larger discrepancies are obtained for the secondary organic aerosols due to both inconsistencies in the SOA formation processes in the model leading to an underestimation of their mass and large uncertainties in the determination of the measured aerosol organic fraction. The observed mass distribution of aerosols is not well reproduced, although no clear explanation can be given.
Application of thermal-dissociation laser induced fluorescence (TD-LIF) to measurement of HNO3, Σalkyl nitrates, Σperoxy nitrates, and NO2 fluxes using eddy covariance
Authors: Farmer D. K. , Wooldridge P. J. , Cohen R. C.
Published: April 2010

Abstract. Nitrogen exchange between the atmosphere and biosphere directly influences atmospheric composition. While much is known about mechanisms of NO and N2O emissions, instrumentation for the study of mechanisms contributing to exchange of other major nitrogen species is quite limited. Here we describe the application of a new technique, thermal dissociation-laser induced fluorescence (TD-LIF), to eddy covariance measurements of the fluxes of NO2, total peroxy acyl and peroxy nitrates, total alkyl and multifunctional alkyl nitrates, and nitric acid. The technique offers the potential for investigating mechanisms of exchange of these species at the canopy scale over timescales from days to years. Examples of flux measurements at a ponderosa pine plantation in the mid-elevation Sierra Nevada Mountains in California are reported and used to evaluate instrument performance.
Probing stratospheric transport and chemistry with new balloon and aircraft observations of the meridional and vertical N2O isotope distribution
Authors: Kaiser J. , Engel A. , Borchers R. , Röckmann T.
Published: April 2010

Abstract. A comprehensive set of stratospheric balloon and aircraft samples was analyzed for the position-dependent isotopic composition of nitrous oxide (N2O). Results for a total of 220 samples from between 1987 and 2003 are presented, nearly tripling the number of mass-spectrometric N2O isotope measurements in the stratosphere published to date. Cryogenic balloon samples were obtained at polar (Kiruna/Sweden, 68° N), mid-latitude (southern France, 44° N) and tropical sites (Hyderabad/India, 18° N). Aircraft samples were collected with a newly-developed whole air sampler on board of the high-altitude aircraft M55 Geophysica during the EUPLEX 2003 campaign. For mixing ratios above 200 nmol mol−1, relative isotope enrichments (δ values) and mixing ratios display a compact relationship, which is nearly independent of latitude and season and which can be explained equally well by Rayleigh fractionation or mixing. However, for mixing ratios below 200 nmol mol−1 this compact relationship gives way to meridional, seasonal and interannual variations. A comparison to a previously published mid-latitude balloon profile even shows large zonal variations, justifying the use of three-dimensional (3-D) models for further data interpretation. In general, the magnitude of the apparent fractionation constants (i.e., apparent isotope effects) increases continuously with altitude and decreases from the equator to the North Pole. Only the latter observation can be understood qualitatively by the interplay between the time-scales of N2O photochemistry and transport in a Rayleigh fractionation framework. Deviations from Rayleigh fractionation behavior also occur where polar vortex air mixes with nearly N2O-free upper stratospheric/mesospheric air (e.g., during the boreal winters of 2003 and possibly 1992). Aircraft observations in the polar vortex at mixing ratios below 200 nmol mol−1 deviate from isotope variations expected for both Rayleigh fractionation and two-end-member mixing, but could be explained by continuous weak mixing between intravortex and extravortex air (Plumb et al., 2000). However, it appears that none of the simple approaches described here can capture all features of the stratospheric N2O isotope distribution, again justifying the use of 3-D models. Finally, correlations between 18O/16O and average 15N/14N isotope ratios or between the position-dependent 15N/14N isotope ratios show that photo-oxidation makes a large contribution to the total N2O sink in the lower stratosphere (possibly up to 100% for N2O mixing ratios above 300 nmol mol−1). Towards higher altitudes, the temperature dependence of these isotope correlations becomes visible in the stratospheric observations.
Characterization of the organic composition of aerosols from Rondônia, Brazil, during the LBA-SMOCC 2002 experiment and its representation through model compounds
Authors: Decesari S. , Fuzzi S. , Facchini M. C. , Mircea M. , Emblico L. , Cavalli F. , Maenhaut W. , Chi X. , Schkolnik G. , Falkovich A. , Rudich Y. , Claeys M. , Pashynska V. , Vas G. , Kourtchev I. , Vermeylen R. , Hoffer A. , Andreae M. O. , Tagliavini E. , Moretti F. , Artaxo P.
Published: April 2010

Abstract. The chemical composition of carbonaceous aerosols collected during the LBA-SMOCC field experiment, conducted in Rondônia, Brazil, in 2002 during the transition from the dry to the wet season, was investigated by a suite of state-of-the-art analytical techniques. The period of most intense biomass burning was characterized by high concentrations of submicron particles rich in carbonaceous material and water-soluble organic compounds (WSOC). At the onset of the rainy period, submicron total carbon (TC) concentrations decreased by about 20 times. In contrast, the concentration of supermicron TC was fairly constant throughout the experiment, pointing to a constant emission of coarse particles from the natural background. About 6–8% of TC (9–11% of WSOC) was speciated at the molecular level by GC-MS and liquid chromatography. Polyhydroxylated compounds, aliphatic and aromatic acids were the main classes of compounds accounted for by individual compound analysis. Functional group analysis by proton NMR and chromatographic separation on ion-exchange columns allowed characterization of ca. 50–90% of WSOC into broad chemical classes (neutral species/light acids/humic-like substances). In spite of the significant change in the chemical composition of tracer compounds from the dry to the wet period, the functional groups and the general chemical classes of WSOC changed only to a small extent. Model compounds representing size-resolved WSOC chemical composition for the different periods of the campaign are then proposed in this paper, based on the chemical characterization by both individual compound analysis and functional group analysis deployed during the LBA-SMOCC experiment. Model compounds reproduce quantitatively the average chemical structure of WSOC and can be used as best-guess surrogates in microphysical models involving organic aerosol particles over tropical areas affected by biomass burning.
Some experimental constraints for spectral parameters used in the Warner and McIntyre gravity wave parameterization scheme
Authors: Ern M. , Preusse P. , Warner C. D.
Published: April 2010

Abstract. In order to incorporate the effect of gravity waves (GWs) on the atmospheric circulation most global circulation models (GCMs) employ gravity wave parameterization schemes. To date, GW parameterization schemes in GCMs are used without experimental validation of the set of global parameters assumed for the GW launch spectrum. This paper focuses on the Warner and McIntyre GW parameterization scheme. Ranges of parameters compatible with absolute values of gravity wave momentum flux (GW-MF) derived from CRISTA-1 and CRISTA-2 satellite measurements are deduced for several of the parameters and the limitations of both model and measurements are discussed. The findings presented in this paper show that the initial guess of spectral parameters provided by by Warner and McIntyre (2001) are some kind of compromise with respect to agreement of absolute values and agreement of the horizontal structures found in both measurements and model results. Better agreement can be achieved by using a vertical wavenumber launch spectrum with a wider saturated spectral range and reduced spectral power in the unsaturated part. However, even with this optimized set of global launch parameters not all features of the measurements are matched. This indicates that for further improvement spatial and seasonal variations of the launch parameters should be included in GW parameterization schemes.
Simulations of preindustrial, present-day, and 2100 conditions in the NASA GISS composition and climate model G-PUCCINI
Authors: Shindell D. T. , Faluvegi G. , Unger N. , Aguilar E. , Schmidt G. A. , Koch D. M. , Bauer S. E. , Miller R. L.
Published: April 2010

Abstract. A model of atmospheric composition and climate has been developed at the NASA Goddard Institute for Space Studies (GISS) that includes composition seamlessly from the surface to the lower mesosphere. The model is able to capture many features of the observed magnitude, distribution, and seasonal cycle of trace species. The simulation is especially realistic in the troposphere. In the stratosphere, high latitude regions show substantial biases during period when transport governs the distribution as meridional mixing is too rapid in this model version. In other regions, including the extrapolar tropopause region that dominates radiative forcing (RF) by ozone, stratospheric gases are generally well-simulated. The model's stratosphere-troposphere exchange (STE) agrees well with values inferred from observations for both the global mean flux and the ratio of Northern (NH) to Southern Hemisphere (SH) downward fluxes. Simulations of preindustrial (PI) to present-day (PD) changes show tropospheric ozone burden increases of 11% while the stratospheric burden decreases by 18%. The resulting tropopause RF values are −0.06 W/m2 from stratospheric ozone and 0.40 W/m2 from tropospheric ozone. Global mean mass-weighted OH decreases by 16% from the PI to the PD. STE of ozone also decreased substantially during this time, by 14%. Comparison of the PD with a simulation using 1979 pre-ozone hole conditions for the stratosphere shows a much larger downward flux of ozone into the troposphere in 1979, resulting in a substantially greater tropospheric ozone burden than that seen in the PD run. This implies that reduced STE due to stratospheric ozone depletion may have offset as much as 2/3 of the tropospheric ozone burden increase from PI to PD. However, the model overestimates the downward flux of ozone at high Southern latitudes, so this estimate is likely an upper limit. In the future, the tropospheric ozone burden increases by 101% in 2100 for the A2 scenario including both emissions and climate changes. The primary reason is enhanced STE, which increases by 124% (168% in the SH extratropics, and 114% in the NH extratropics). Climate plays a minimal role in the SH increases, but contributes 38% in the NH. Chemistry and dry deposition both change so as to reduce tropospheric ozone, partially in compensation for the enhanced STE, but the increased ozone influx dominates the burden changes. The net RF due to projected ozone changes is 0.8 W/m2 for A2. The influence of climate change alone is −0.2 W/m2, making it a substantial contributor to the net RF. The tropospheric oxidation capacity increases seven percent in the full A2 simulation, and 36% due to A2 climate change alone.
Aerosol composition and source apportionment in the Mexico City Metropolitan Area with PIXE/PESA/STIM and multivariate analysis
Authors: Johnson K. S. , de Foy B. , Zuberi B. , Molina L. T. , Molina M. J. , Xie Y. , Laskin A. , Shutthanandan V.
Published: April 2010

Abstract. Aerosols play an important role in the atmosphere but are poorly characterized, particularly in urban areas like the Mexico City Metropolitan Area (MCMA). The chemical composition of urban particles must be known to assess their effects on the environment, and specific particulate emissions sources should be identified to establish effective pollution control standards. For these reasons, samples of particulate matter ≤2.5 μm (PM2.5) were collected during the MCMA-2003 Field Campaign for elemental and multivariate analyses. Proton-Induced X-ray Emission (PIXE), Proton-Elastic Scattering Analysis (PESA) and Scanning Transmission Ion Microscopy (STIM) measurements were done to determine concentrations of 19 elements from Na to Pb, hydrogen, and total mass, respectively. The most abundant elements from PIXE analysis were S, Si, K, Fe, Ca, and Al, while the major emissions sources associated with these elements were industry, wind-blown soil, and biomass burning. Wind trajectories suggest that metals associated with industrial emissions came from northern areas of the city whereas soil aerosols came from the southwest and increased in concentration during dry conditions. Elemental markers for fuel oil combustion, V and Ni, correlated with a large SO2 plume to suggest an anthropogenic, rather than volcanic, emissions source. By subtracting major components of soil and sulfates determined by PIXE analysis from STIM total mass measurements, we estimate that approximately 50% of non-volatile PM2.5 consisted of carbonaceous material.
Implementation and testing of a desert dust module in a regional climate model
Authors: Zakey A. S. , Solmon F. , Giorgi F.
Published: April 2010

Abstract. In an effort to improve our understanding of aerosol impacts on climate, we implement a desert dust module within a regional climate model (RegCM). The dust module includes emission, transport, gravitational settling, wet and dry removal and calculations of dust optical properties. The coupled RegCM-dust model is used to simulate two dust episodes observed over the Sahara region (a northeastern Africa dust outbreak, and a west Africa-Atlantic dust outbreak observed during the SHADE "Saharan Dust Experiment"), as well as a three month simulation over an extended domain covering the Africa-Europe sector. Comparisons with satellite and local aerosol optical depth measurements shows that the model captures the main spatial (both horizontal and vertical) and temporal features of the dust distribution. The main model deficiency occurs in the representation of certain dynamical patterns observed during the SHADE case which is associated with an active easterly wave that contributed to the generation of the dust outbreak. The model appears suitable to conduct long term simulations of the effects of Saharan dust on African and European climate.
Aerosol nucleation over oceans and the role of galactic cosmic rays
Authors: Kazil J. , Lovejoy E. R. , Barth M. C. , O'Brien K.
Published: April 2010

Abstract. We investigate formation of sulfate aerosol in the marine troposphere from neutral and charged nucleation of H2SO4 and H2O. A box model of neutral and charged aerosol processes is run on a grid covering the oceans. Input data are taken from a model of galactic cosmic rays in the atmosphere, and from global chemistry and transport models. We find a weak aerosol production over the tropical oceans in the lower and middle troposphere, and a stronger production at higher latitudes, most notably downwind of industrial regions. The strongest aerosol production however occurs in the upper troposphere over areas with frequent convective activity, in particular in the tropics. This finding supports the proposition by which non-sea salt marine boundary layer aerosol in tropical regions does not form in situ, but nucleates in the upper troposphere from convectively lifted and cloud processed boundary layer air rich in aerosol precursor gases, from where it descends in subsiding air masses compensating convection. Convection of boundary layer air also appears to drive the formation of condensation nuclei in the tropical upper troposphere which maintains the stratospheric aerosol layer in the absence of volcanic activity. Neutral nucleation contributes only marginally to aerosol production in our simulations. This highlights the importance of other mechanisms, including charged binary and ternary, and neutral ternary nucleation for aerosol formation. Our analysis indicates that the variation of ionization by galactic cosmic rays over the decadal solar cycle does not entail a response in aerosol production and cloud cover via the second indirect aerosol effect that would explain observed variations in global cloud cover. We estimate that the variation in radiative forcing resulting from a response of clouds to the change in galactic cosmic ray ionization and subsequent aerosol production over the decadal solar cycle is smaller than the concurrent variation of total solar irradiance.
Constraints on N2O budget changes since pre-industrial time from new firn air and ice core isotope measurements
Authors: Bernard S. , Röckmann T. , Kaiser J. , Barnola J.-M. , Fischer H. , Blunier T. , Chappellaz J.
Published: April 2010

Abstract. A historical record of changes in the N2O isotope composition is important for a better understanding of the global N2O atmospheric budget. Here we have combined measurements of trapped gases in the firn and in ice cores of one Arctic site (North GReenland Ice core Project - NGRIP) and one Antarctic site (Berkner Island). We have performed measurements of the 18O and position dependent 15N isotopic composition of N2O. By comparing these data to simulations carried out with a firn air diffusion model, we have reconstructed the temporal evolution of the N2O isotope signatures since pre-industrial times. The decrease observed for all signatures is consistent from one pole to the other. Results obtained from the air occluded in the ice suggest a decrease of about -2.8, -2.4, -3.2 and -1.6 for δ15N, 1δ15N, 2δ15N and δ18O, respectively, since 1700 AD. Firn air data imply a decrease of about -1.1, -1.2, -1.0 and -0.6 for δ15N, 1δ15N, 2δ15N and δ18O, respectively, since 1970 AD. These results imply consistent trends from firn and ice measurements for δ15N and δ18O. The trends for the intramolecular distribution of 15N are less well constrained than the bulk 15N trends because of the larger experimental error for the position dependent 15N measurements. The decrease in the heavy isotope content of atmospheric N2O can be explained by the increasing importance of agriculture for the present atmospheric N2O budget.
Investigating the composition of organic aerosol resulting from cyclohexene ozonolysis: low molecular weight and heterogeneous reaction products
Authors: Hamilton J. F. , Lewis A. C. , Reynolds J. C. , Carpenter L. J. , Lubben A.
Published: April 2010

Abstract. The composition of organic aerosol formed from the gas phase ozonolysis of cyclohexene has been investigated in a smog chamber experiment. Comprehensive gas chromatography with time of flight mass spectrometric detection was used to determine that dicarboxylic acids and corresponding cyclic anhydrides dominated the small gas phase reaction products found in aerosol sampled during the first hour after initial aerosol formation. Structural analysis of larger more polar molecules was performed using liquid chromatography with ion trap tandem mass spectrometry. This indicated that the majority of identified organic mass was in dimer form, built up from combinations of the most abundant small acid molecules, with frequent indication of the inclusion of adipic acid. Trimers and tetramers potentially formed via similar acid combinations were also observed in lower abundances. Tandem mass spectral data indicated dimers with either acid anhydride or ester functionalities as the linkage between monomers. High-resolution mass spectrometry identified the molecular formulae of the most abundant dimer species to be C10H16O6, C11H18O6, C10H14O8 and C11H16O8 and could be used in some cases to reduce uncertainty in exact chemical structure determination by tandem MS.