bluuebunny/crossref_metadata_2025 huggingface dataset:
Aerosol-cloud interaction inferred from MODIS satellite data and global aerosol models
Authors: Myhre G. , Stordal F. , Johnsrud M. , Kaufman Y. J. , Rosenfeld D. , Storelvmo T. , Kristjansson J. E. , Berntsen T. K. , Myhre A. , Isaksen I. S. A.
Published: April 2010

Abstract. We have used the MODIS satellite data and two global aerosol models to investigate the relationships between aerosol optical depth (AOD) and cloud parameters that may be affected by the aerosol concentration. The relationships that are studied are mainly between AOD, on the one hand, and cloud cover, cloud liquid water path, and water vapour, on the other. Additionally, cloud droplet effective radius, cloud optical depth, cloud top pressure and aerosol Ångström exponent, have been analysed in a few cases. In the MODIS data we found, as in earlier studies, an enhancement in the cloud cover with increasing AOD. We find it likely that most of the strong increase in cloud cover with AOD, at least for AOD<0.2, is a result of aerosol-cloud interactions and a prolonged cloud lifetime. Large and mesoscale weather systems seem not to be a cause for the increase in cloud cover with AOD in this range. Sensitivity simulations show that when water uptake of the aerosols is not taken into account in the models the modelled cloud cover mostly decreases with AOD. Part of the relationship found in the MODIS data for AOD>0.2 can be explained by larger water uptake close to the clouds since relative humidity is higher in regions with higher cloud cover. The efficiency of the hygroscopic growth depends on aerosol type, the hygroscopic nature of the aerosol, the relative humidity, and to some extent the cloud screening. By analysing the Ångström exponent we find that the hygroscopic growth of the aerosol is not likely to be a main contributor to the cloud cover increase with AOD. Since the largest increase in cloud cover with AOD is for low AOD (~0.2) and thus also for low cloud cover, we argue that cloud contamination is not likely to play a large role. However, interpretation of the complex relationships between AOD and cloud parameters should be made with great care and further work is clearly needed.
Simulation study of the aerosol information content in OMI spectral reflectance measurements
Authors: Veihelmann B. , Levelt P. F. , Stammes P. , Veefkind J. P.
Published: April 2010

Abstract. The Ozone Monitoring Instrument (OMI) is an imaging UV-VIS solar backscatter spectrometer and is designed and used primarily to retrieve trace gases like O3 and NO2 from the measured Earth reflectance spectrum in the UV-visible (270–500 nm). However, also aerosols are an important science target of OMI. The multi-wavelength algorithm is used to retrieve aerosol parameters from OMI spectral reflectance measurements in up to 20 wavelength bands. A Principal Component Analysis (PCA) is performed to quantify the information content of OMI reflectance measurements on aerosols and to assess the capability of the multi-wavelength algorithm to discern various aerosol types. This analysis is applied to synthetic reflectance measurements for desert dust, biomass burning aerosols, and weakly absorbing anthropogenic aerosol with a variety of aerosol optical thicknesses, aerosol layer altitudes, refractive indices and size distributions. The range of aerosol parameters considered covers the natural variability of tropospheric aerosols. This theoretical analysis is performed for a large number of scenarios with various geometries and surface albedo spectra for ocean, soil and vegetation. When the surface albedo spectrum is accurately known and clouds are absent, OMI reflectance measurements have 2 to 4 degrees of freedom that can be attributed to aerosol parameters. This information content depends on the observation geometry and the surface albedo spectrum. An additional wavelength band is evaluated, that comprises the O2-O2 absorption band at a wavelength of 477 nm. It is found that this wavelength band adds significantly more information than any other individual band.
Asymmetricity of ground-based GPS slant delay data
Authors: Eresmaa R. , Järvinen H. , Niemelä S. , Salonen K.
Published: April 2010

Abstract. The ground-based measurements of the Global Positioning System (GPS) allow estimation of the tropospheric delay along the slanted signal paths through the atmosphere. The meteorological exploitation of such slant delay (SD) observations relies on the hypothesis of azimuthal asymmetry of the information content. This article addresses the validity of the hypothesis. A new concept of asymmetricity is introduced for studying the SD observations and their model counterparts. The asymmetricity is defined as the ratio of the absolute asymmetric delay component to total SD. The model counterparts are determined from 3-h forecasts of a numerical weather prediction (NWP) model, run with four different horizontal resolutions. The SD observations are compared with their model counterparts with emphasis on cases of high asymmetricity in order to see whether the observed asymmetry is a real atmospheric signature. The asymmetricity is found to be of the order of a few parts per thousand. Thus, the asymmetric delay component barely exceeds the assumed standard deviation of the SD observation error. However, the observed asymmetric delay components show a statistically significant meteorological signal. Benefit of the asymmetric SD observations is therefore expected to be taken in future, when NWP systems will explicitly represent the small-scale atmospheric features revealed by the SD observations.
Modelling the direct effect of aerosols in the solar near-infrared on a planetary scale
Authors: Hatzianastassiou N. , Matsoukas C. , Fotiadi A. ,   P. W. Stackhouse Jr., Koepke P. , Pavlakis K. G. , Vardavas I.
Published: April 2010

Abstract. We used a spectral radiative transfer model to compute the direct radiative effect (DRE) of natural plus anthropogenic aerosols in the solar near-infrared (IR), between 0.85–10 μm, namely, their effect on the outgoing near-IR radiation at the top of atmosphere (TOA, ΔFTOA), on the atmospheric absorption of near-IR radiation (ΔFatmab) and on the surface downward and absorbed near-IR radiation (ΔFsurf, and ΔFsurfnet, respectively). The computations were performed on a global scale (over land and ocean) under all-sky conditions, using detailed spectral aerosol optical properties taken from the Global Aerosol Data Set (GADS) supplemented by realistic data for the rest of surface and atmospheric parameters. The computed aerosol DRE, averaged over the 12-year period 1984–1995 for January and July, shows that on a global mean basis aerosols produce a planetary cooling by increasing the scattered near-IR radiation back to space by 0.48 W m−2, they warm the atmosphere by 0.37 W m−2 and cool the surface by decreasing the downward and absorbed near-IR radiation at surface by 1.03 and 0.85 W m−2, respectively. The magnitude of the near-IR aerosol DRE is smaller than that of the combined ultraviolet (UV) and visible DRE, but it is still energetically important, since it contributes to the total shortwave (SW) DRE by 22–31%. The aerosol-produced near-IR surface cooling combined with the atmospheric warming, may affect the thermal dynamics of the Earth-atmosphere system, by increasing the atmospheric stability, decreasing thus cloud formation, and precipitation, especially over desertification threatened regions such as the Mediterranean basin. This, together with the fact that the sign of near-IR aerosol DRE is sometimes opposite to that of UV-visible DRE, demonstrates the importance of performing detailed spectral computations to provide estimates of the climatic role of aerosols for the Earth-atmosphere system. This was demonstrated by sensitivity tests revealing very large differences (up to 300%) between aerosol DREs computed using detailed spectral and spectrally-averaged aerosol optical properties. Our model results indicate thus that the aerosol direct radiative effect on the near-IR radiation is very sensitive to the treatment of the spectral dependence of aerosol optical properties and solar radiation.
Fine aerosol bulk composition measured on WP-3D research aircraft in vicinity of the Northeastern United States – results from NEAQS
Authors: Peltier R. E. , Sullivan A. P. , Weber R. J. , Brock C. A. , Wollny A. G. , Holloway J. S. , de Gouw J. A. , Warneke C.
Published: April 2010

Abstract. During the New England Air Quality Study (NEAQS) in the summer of 2004, airborne measurements were made of the major inorganic ions and the water-soluble organic carbon (WSOC) of the submicron (PM1.0) aerosol. These and ancillary data are used to describe the overall aerosol chemical characteristics encountered during the study. Fine particle mass was estimated from particle volume and a calculated density based on measured particle composition. Fine particle organic matter (OM) was estimated from WSOC and a mass balance analysis. The aerosol over the northeastern United States (U.S.) and Canada was predominantly sulfate and associated ammonium, and organic components, although in unique plumes additional ionic components were also periodically above detection limits. In power generation regions, and especially in the Ohio River Valley region, the aerosol tended to be predominantly sulfate (~60% μg μg−1) and apparently acidic, based on an excess of measured anions compared to cations. In all other regions where sulfate concentrations were lower and a smaller fraction of overall mass, the cations and anions were balanced suggesting a more neutral aerosol. In contrast, the WSOC and estimated OM were more spatially uniform and the fraction of OM relative to PM mass was largely influenced by sources of sulfate. The study median OM mass fraction was 40%. Throughout the study region, sulfate and organic aerosol mass were highest near the surface and decreased rapidly with increasing altitude. The relative fraction of organic mass to sulfate was similar throughout all altitudes within the boundary layer (altitude less than 2.5 km), but was significantly higher at altitude layers in the free troposphere (above 2.5 km). A number of distinct biomass burning plumes from fires in Alaska and the Yukon were periodically intercepted, mostly at altitudes between 3 and 4 km. These plumes were associated with highest aerosol concentrations of the study and were largely comprised of organic aerosol components (~60%).
Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 & 2003 field campaigns
Authors: Velasco E. , Lamb B. , Westberg H. , Allwine E. , Sosa G. , Arriaga-Colina J. L. , Jobson B. T. , Alexander M. L. , Prazeller P. , Knighton W. B. , Rogers T. M. , Grutter M. , Herndon S. C. , Kolb C. E. , Zavala M. , de Foy B. , Volkamer R. , Molina L. T. , Molina M. J.
Published: April 2010

Abstract. A wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Four distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes, were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic in addition to meteorological processes. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air quality modeling studies suggests that some alkanes are underestimated in the emissions inventory, while some olefins and aromatics are overestimated.
Including the sub-grid scale plume rise of vegetation fires in low resolution atmospheric transport models
Authors: Freitas S. R. , Longo K. M. , Chatfield R. , Latham D. , Silva Dias M. A. F. , Andreae M. O. , Prins E. , Santos J. C. , Gielow R. , Carvalho J. A.
Published: April 2010

Abstract. We describe and begin to evaluate a parameterization to include the vertical transport of hot gases and particles emitted from biomass burning in low resolution atmospheric-chemistry transport models. This sub-grid transport mechanism is simulated by embedding a 1-D cloud-resolving model with appropriate lower boundary conditions in each column of the 3-D host model. Through assimilation of remote sensing fire products, we recognize which columns have fires. Using a land use dataset appropriate fire properties are selected. The host model provides the environmental conditions, allowing the plume rise to be simulated explicitly. The derived height of the plume is then used in the source emission field of the host model to determine the effective injection height, releasing the material emitted during the flaming phase at this height. Model results are compared with CO aircraft profiles from an Amazon basin field campaign and with satellite data, showing the huge impact that this mechanism has on model performance. We also show the relative role of each main vertical transport mechanisms, shallow and deep moist convection and the pyro-convection (dry or moist) induced by vegetation fires, on the distribution of biomass burning CO emissions in the troposphere.
Evaluation of ECMWF ERA-40 temperature and wind in the lower tropical stratosphere since 1988 from past long-duration balloon measurements
Authors: Christensen T. , Knudsen B. M. , Pommereau J.-P. , Letrenne G. , Hertzog A. , Vial F. , Ovarlez J. , Piot M.
Published: April 2010

Abstract. The temperature and wind of the ECMWF ERA-40 reanalysis in the tropical lower stratosphere during the period 1988–2001 has been evaluated by comparison with independent in situ measurements of 21 IR Montgolfier and superpressure long-duration balloon flights performed by CNES from Pretoria (26° S) in South Africa in 1988–1989, Latacunga (1° S) in Ecuador in 1991–1998 and Bauru (22° S) in Brazil in 2000–2001. The ERA-40 temperature displays a bias varying progressively from +1.16 K in 1988–1989, to +0.26 K in 1994–1996 and −0.46 K after 1998, the latter being fully consistent with recent evaluations of ECMWF operational analysis from radio occultation and in situ long-duration balloon observations. The amplitude of the bias and its evolution are very similar to the results of a previous evaluation from radiosondes in 1991–2003, suggesting that the origin of the drift of ERA-40 might be mainly due to errors in the series of satellite measurements of MSU, replaced by AMSU in 1998, assimilated in the model. The ERA-40 zonal wind speed in the lower stratosphere appears slightly overestimated by 0.7–1.0 m/s on average in both the tropics and equatorial region, that is by 5–10% compared to the average 10–20 m/s wind speed. This bias, fully consistent with a recent evaluation of ECMWF operational analysis in 2004, is found constant during the whole 1988–2001 period, suggesting a shortfall in the variabililty of ERA-40 horizontal winds in the lower stratosphere in the tropics and the equatorial region. Finally calculated trajectories using ERA-40, frequently used for analysing field observations, are found in error compared to that of the balloons by ±500 km after 5 days and ±1000 km after 10 days.
Cloud microphysics and aerosol indirect effects in the global climate model ECHAM5-HAM
Authors: Lohmann U. , Stier P. , Hoose C. , Ferrachat S. , Kloster S. , Roeckner E. , Zhang J.
Published: April 2010

Abstract. The double-moment cloud microphysics scheme from ECHAM4 that predicts both the mass mixing ratios and number concentrations of cloud droplets and ice crystals has been coupled to the size-resolved aerosol scheme ECHAM5-HAM. ECHAM5-HAM predicts the aerosol mass, number concentrations and mixing state. The simulated liquid, ice and total water content and the cloud droplet and ice crystal number concentrations as a function of temperature in stratiform mixed-phase clouds between 0 and −35° C agree much better with aircraft observations in the ECHAM5 simulations. ECHAM5 performs better because more realistic aerosol concentrations are available for cloud droplet nucleation and because the Bergeron-Findeisen process is parameterized as being more efficient. The total anthropogenic aerosol effect includes the direct, semi-direct and indirect effects and is defined as the difference in the top-of-the-atmosphere net radiation between present-day and pre-industrial times. It amounts to −1.9 W m−2 in ECHAM5, when a relative humidity dependent cloud cover scheme and aerosol emissions representative for the years 1750 and 2000 from the AeroCom emission inventory are used. The contribution of the cloud albedo effect amounts to −0.7 W m−2. The total anthropogenic aerosol effect is larger when either a statistical cloud cover scheme or a different aerosol emission inventory are employed because the cloud lifetime effect increases.
Physical and optical aerosol properties at the Dutch North Sea coast based on AERONET observations
Authors: Kusmierczyk-Michulec J. , De Leeuw G. , Moerman M. M.
Published: April 2010

Abstract. Sun photometer measurements at the AERONET station at the North Sea coast in The Hague (The Netherlands) provide a climatology of optical and physical aerosol properties for the area. Results are presented from the period January 2002 to July 2003. For the analysis and interpretation these data are coupled to chemical aerosol data from a nearby station of the Dutch National Air Quality Network. This network provides PM10 and black carbon concentrations. Meteorological conditions and air mass trajectories are also used. Due to the location close to the coast, the results are strongly dependent on wind direction, i.e. air mass trajectory. In general the aerosol optical properties are governed by industrial aerosol emitted form various industrial, agricultural and urban areas surrounding the site in almost all directions over land. For maritime air masses industrial aerosols are transported from over the North Sea, whereas very clean air is transported from the NW in clean polar air masses from the North Atlantic. In the winter the effect of the production of sea salt aerosol at high wind speeds is visible in the optical and physical aerosol data. In these cases fine and coarse mode radii are similar to those reported in the literature for marine aerosol. Relations are derived between the Ångström coefficients with both the fine/coarse mode fraction and the ratio of black carbon and PM10.
The effects of heating by transported dust layers on cloud and precipitation: a numerical study
Authors: Yin Y. , Chen L.
Published: April 2010

Abstract. There have been numerous recent publications showing that mineral dust might be a good absorber for solar radiation in addition to its capability to act as cloud condensation nuclei (CCN) and ice forming nuclei (IFN), and could lead to reduced cloud cover and precipitation in the region where it is present. This effect is investigated using a dynamic cloud model with detailed microphysics of both warm and ice phase processes. The model is initialized using measured size distributions and concentrations of mineral dust particles. Our results show that when dust appears at the cloud-base height and below 3 km, where the temperature is warmer than −5°C, the heating induced by the presence of dust layers can inhibit the formation of cloud droplets and suppresses the development of precipitation, leading to lower cloud optical depth and albedo. On the other hand, when the dust layers are located at altitudes with temperature colder than −5°C, or above the −5°C level, mineral aerosols can act as effective ice nuclei, intensify the ice-forming processes, and may enhance the development of cloud and precipitation. It is also found that the heating effect is more pronounced in continental clouds than in maritime clouds.
Retrieval of temperature profiles from CHAMP for climate monitoring: intercomparison with Envisat MIPAS and GOMOS and different atmospheric analyses
Authors: Gobiet A. , Kirchengast G. , Manney G. L. , Borsche M. , Retscher C. , Stiller G.
Published: April 2010

Abstract. This study describes and evaluates a Global Navigation Satellite System (GNSS) radio occultation (RO) retrieval scheme particularly aimed at delivering bias-free atmospheric parameters for climate monitoring and research. The focus of the retrieval is on the sensible use of a priori information for careful high-altitude initialisation in order to maximise the usable altitude range. The RO retrieval scheme has been meanwhile applied to more than five years of data (September 2001 to present) from the German CHAllenging Minisatellite Payload for geoscientific research (CHAMP) satellite. In this study it was validated against various correlative datasets including the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) and the Global Ozone Monitoring for Occultation of Stars (GOMOS) sensors on Envisat, five different atmospheric analyses, and the operational CHAMP retrieval product from GeoForschungsZentrum (GFZ) Potsdam. In the global mean within 10 to 30 km altitude we find that the present validation observationally constrains the potential RO temperature bias to be <0.2 K. Latitudinally resolved analyses show biases to be observationally constrained to <0.2–0.5 K up to 35 km in most cases, and up to 30 km in any case, even if severely biased (about 10 K or more) a priori information is used in the high altitude initialisation of the retrieval. No evidence is found for the 10–35 km altitude range of residual RO bias sources other than those potentially propagated downward from initialisation, indicating that the widely quoted RO promise of "unbiasedness and long-term stability due to intrinsic self-calibration" can indeed be realised given care in the data processing to strictly limit structural uncertainty. The results thus reinforce that adequate high-altitude initialisation is crucial for accurate stratospheric RO retrievals. The common method of initialising, at some altitude in the upper stratosphere, the hydrostatic integral with an upper boundary temperature or pressure value derived from meteorological analyses is prone to introduce biases from the upper boundary down to below 25 km. Also above 30 to 35 km, GNSS RO delivers a considerable amount of observed information up to around 40 km, which is particularly interesting for numerical weather prediction (NWP) systems, where direct assimilation of non-initialised observed RO bending angles (free of a priori) is thus the method of choice. The results underline the value of RO for climate applications.
Nucleation and growth of new particles in Po Valley, Italy
Authors: Hamed A. , Joutsensaari J. , Mikkonen S. , Sogacheva L. , Dal Maso M. , Kulmala M. , Cavalli F. , Fuzzi S. , Facchini M. C. , Decesari S. , Mircea M. , Lehtinen K. E. J. , Laaksonen A.
Published: April 2010

Abstract. Aerosol number distribution measurements are reported at San Pietro Capofiume (SPC) station (44°39' N, 11°37' E) for the time period 2002–2005. The station is located in Po Valley, the largest industrial, trading and agricultural area in Italy with a high population density. New particle formation was studied based on observations of the particle size distribution, meteorological and gas phase parameters. The nucleation events were classified according to the event clarity based on the particle number concentrations, and the particle formation and growth rates. Out of a total of 769 operational days from 2002 to 2005 clear events were detected on 36% of the days whilst 33% are clearly non-event days. The event frequency was high during spring and summer months with maximum values in May and July, whereas lower frequency was observed in winter and autumn months. The average particle formation and growth rates were estimated as ~6 cm−3 s−1 and ~7 nm h−1, respectively. Such high growth and formation rates are typical for polluted areas. Temperature, wind speed, solar radiation, SO2 and O3 concentrations were on average higher on nucleation days than on non-event days, whereas relative and absolute humidity and NO2 concentration were lower; however, seasonal differences were observed. Backtrajectory analysis suggests that during majority of nucleation event days, the air masses originate from northern to eastern directions. We also study previously developed nucleation event correlations with environmental variables and show that they predict Po Valley nucleation events with variable success.
Predicting arene rate coefficients with respect to hydroxyl and other free radicals in the gas-phase: a simple and effective method using a single topological descriptor
Authors: McGillen M. R. , Percival C. J. , Pieterse G. , Watson L. A. , Shallcross D. E.
Published: April 2010

Abstract. The reactivity of aromatic compounds is of great relevance to pure and applied chemical disciplines, yet existing methods for estimating gas-phase rate coefficients for their reactions with free radicals lack accuracy and universality. Here a novel approach is taken, whereby strong relationships between rate coefficients of aromatic hydrocarbons and a Randić-type topological index are investigated, optimized and developed into a method which requires no specialist software or computing power. Measured gas-phase rate coefficients for the reaction of aromatic hydrocarbons with OH radicals were correlated with a calculated Randić-type index, and optimized by including a term for side chain length. Although this method is exclusively for use with hydrocarbons, it is more diverse than any single existing methodology since it incorporates alkenylbenzenes into correlations, and can be extended towards other radical species such as O(3P) (and tentatively NO3, H and Cl). A comparison (with species common to both techniques) is made between the topological approach advocated here and a popular approach based on electrophilic subsituent constants, where it compares favourably. A modelling study was carried out to assess the impact of using estimated rate coefficients as opposed to measured data in an atmospheric model. The difference in model output was negligible for a range of NOx concentrations, which implies that this method has utility in complex chemical models. Strong relationships (e.g. for OH, R2=0.96) between seemingly diverse compounds including benzene, multisubstituted benzenes with saturated, unsaturated, aliphatic and cyclic substitutions and the nonbenzenoid aromatic, azulene suggests that the Randić-type index presented here represents a new and effective way of describing aromatic reactivity, based on a quantitative structure-activity relationship (QSAR).
Investigation of the formaldehyde differential absorption cross section at high and low spectral resolution in the simulation chamber SAPHIR
Authors: Brauers T. , Bossmeyer J. , Dorn H.-P. , Schlosser E. , Tillmann R. , Wegener R. , Wahner A.
Published: April 2010

Abstract. The results from a simulation chamber study on the formaldehyde (HCHO) absorption cross section in the UV spectral region are presented. We performed 4 experiments at ambient HCHO concentrations with simultaneous measurements of two DOAS instruments in the atmosphere simulation chamber SAPHIR in Jülich. The two instruments differ in their spectral resolution, one working at 0.2 nm (broad-band, BB-DOAS), the other at 2.7 pm (high-resolution, HR-DOAS). Both instruments use dedicated multi reflection cells to achieve long light path lengths of 960 m and 2240 m, respectively, inside the chamber. During two experiments HCHO was injected into the clean chamber by thermolysis of well defined amounts of para-formaldehyde reaching mixing rations of 30 ppbV at maximum. The HCHO concentration calculated from the injection and the chamber volume agrees with the BB-DOAS measured value when the absorption cross section of Meller and Moortgat (2000) and the temperature coefficient of Cantrell (1990) were used for data evaluation. In two further experiments we produced HCHO in-situ from the ozone + ethene reaction which was intended to provide an independent way of HCHO calibration through the measurements of ozone and ethene. However, we found an unexpected deviation from the current understanding of the ozone + ethene reaction when CO was added to suppress possible oxidation of ethene by OH radicals. The reaction of the Criegee intermediate with CO could be 240 times slower than currently assumed. Based on the BB-DOAS measurements we could deduce a high-resolution cross section for HCHO which was not measured directly so far.
Assessing the near surface sensitivity of SCIAMACHY atmospheric CO2 retrieved using (FSI) WFM-DOAS
Authors: Barkley M. P. , Monks P. S. , Hewitt A. J. , Machida T. , Desai A. , Vinnichenko N. , Nakazawa T. , Yu Arshinov M. , Fedoseev N. , Watai T.
Published: April 2010

Abstract. Satellite observations of atmospheric CO2 offer the potential to identify regional carbon surface sources and sinks and to investigate carbon cycle processes. The extent to which satellite measurements are useful however, depends on the near surface sensitivity of the chosen sensor. In this paper, the capability of the SCIAMACHY instrument on board ENVISAT, to observe lower tropospheric and surface CO2 variability is examined. To achieve this, atmospheric CO2 retrieved from SCIAMACHY near infrared (NIR) spectral measurements, using the Full Spectral Initiation (FSI) WFM-DOAS algorithm, is compared to in-situ aircraft observations over Siberia and additionally to tower and surface CO2 data over Mongolia, Europe and North America. Preliminary validation of daily averaged SCIAMACHY/FSI CO2 against ground based Fourier Transform Spectrometer (FTS) column measurements made at Park Falls, reveal a negative bias of about −2.0% for collocated measurements within ±1.0° of the site. However, at this spatial threshold SCIAMACHY can only capture the variability of the FTS observations at monthly timescales. To observe day to day variability of the FTS observations, the collocation limits must be increased. Furthermore, comparisons to in-situ CO2 observations demonstrate that SCIAMACHY is capable of observing a seasonal signal that is representative of lower tropospheric variability on (at least) monthly timescales. Out of seventeen time series comparisons, eleven have correlation coefficients of 0.7 or more, and have similar seasonal cycle amplitudes. Additional evidence of the near surface sensitivity of SCIAMACHY, is provided through the significant correlation of FSI derived CO2 with MODIS vegetation indices at over twenty selected locations in the United States. The SCIAMACHY/MODIS comparison reveals that at many of the sites, the amount of CO2 variability is coincident with the amount of vegetation activity. The presented analysis suggests that SCIAMACHY has the potential to detect CO2 variability within the lowermost troposphere arising from the activity of the terrestrial biosphere.
Aircraft pollution – a futuristic view
Authors: Søvde O. A. , Gauss M. , Isaksen I. S. A. , Pitari G. , Marizy C.
Published: April 2010

Abstract. Impacts of NOx, H2O and aerosol emissions from a projected 2050 aircraft fleet are investigated using the Oslo CTM2, with emissions provided through the EU project SCENIC. The aircraft emission scenarios consist of emissions from subsonic and supersonic aircraft. In particular it is shown that aerosol emissions from such an aircraft fleet can have a relatively large impact on ozone, and possibly reduce the total atmospheric NOx by more than what is emitted by aircraft. Without aerosol emissions this aircraft fleet leads to similar NOx increases for subsonic (at 11–12 km) and supersonic (at 18–20 km) emissions, 1.35 ppbv and 0.83 ppbv as annual zonal means, respectively. H2O increases are also comparable at these altitudes: 630 and 599 ppbv, respectively. Tropospheric ozone increases are about 10 ppbv in the Northern Hemisphere due to emissions from subsonic aircraft. Increased ozone loss from supersonic aircraft at higher altitudes leads to ozone reductions of about 39 ppbv in the Northern Hemisphere and 22 ppbv in the Southern Hemisphere. The latter reduction is a result of transport of ozone depleted air from northern latitudes. When including aircraft aerosol emissions, NOx is reduced due to heterogeneous chemistry. The reduced NOx seems to counterweight the reduction of ozone from emissions of NOx and H2O above 20 km. At these altitudes the NOx (and thus ozone loss) reduction is large enough to give an aircraft emissions induced increase in ozone. In the height range 11–20 km altitude, however, ozone production is reduced. Heterogeneous reactions and reduced NOx enhances ClO, further enhancing ozone loss in the lower stratosphere. This results in a 14 ppbv additional reduction of ozone. Although supersonic aircraft have opposite effects on ozone in the upper and lower stratosphere, the change in ozone columns is clearly dominated by the upper stratospheric loss, thus supersonic aircraft aerosol emissions lead to enhanced ozone columns. The largest increase in the ozone column due to aerosol emissions is therefore seen in the Northern Hemispheric autumn and winter, giving a column increase of 4.5 DU. It is further found that at high northern latitudes during spring the heterogeneous chemistry on PSCs is particularly efficient, thereby increasing the ozone loss.
Retrieval of cloud spherical albedo from top-of-atmosphere reflectance measurements performed at a single observation angle
Authors: Kokhanovsky A. , Mayer B. , von Hoyningen-Huene W. , Schmidt S. , Pilewskie P.
Published: April 2010

Abstract. The paper is aimed to the derivation of the simple analytical relationship between the cloud spherical albedo and the cloud reflection function in the visible. The relationship obtained can be used for the retrieval of the spherical albedo from backscattered solar light measurements performed by radiometers on geostationary and polar orbiting satellites. The example of the application of the technique to MODIS data is shown.
Emission rate and chemical state estimation by 4-dimensional variational inversion
Authors: Elbern H. , Strunk A. , Schmidt H. , Talagrand O.
Published: April 2010

Abstract. This study aims to assess the potential and limits of an advanced inversion method to estimate pollutant precursor sources mainly from observations. Ozone, sulphur dioxide, and partly nitrogen oxides observations are taken to infer source strength estimates. As methodology, the four-dimensional variational data assimilation technique has been generalised and employed to include emission rate optimisation, in addition to chemical state estimates as usual objective of data assimilation. To this end, the optimisation space of the variational assimilation system has been complemented by emission rate correction factors of 19 emitted species at each emitting grid point, involving the University of Cologne mesoscale EURAD model. For validation, predictive skills were assessed for an August 1997 ozone episode, comparing forecast performances of pure initial value optimisation, pure emission rate optimisation, and joint emission rate/initial value optimisation. Validation procedures rest on both measurements withheld from data assimilation and prediction skill evaluation of forecasts after the inversion procedures. Results show that excellent improvements can be claimed for sulphur dioxide forecasts, after emission rate optimisation. Significant improvements can be claimed for ozone forecasts after initial value and joint emission rate/initial value optimisation of precursor constituents. The additional benefits applying joint emission rate/initial value optimisation are moderate, and very useful in typical cases, where upwind emission rate optimisation is essential. In consequence of the coarse horizontal model grid resolution of 54 km, applied in this study, comparisons indicate that the inversion improvements can rest on assimilating ozone observations only, as the inclusion of NOx observations does not provide additional forecast skill. Emission estimates were found to be largely independent from initial guesses from emission inventories, demonstrating the potential of the 4D-var method to infer emission rate improvements. The study also points to the need for improved horizontal model resolution to more efficient use of NOx observations.
Physical controls on orographic cirrus inhomogeneity
Authors: Kay J. E. , Baker M. , Hegg D.
Published: April 2010

Abstract. Optical depth distributions (P(σ)) are a useful measure of radiatively important cirrus (Ci) inhomogeneity. Yet, the relationship between P(σ) and underlying cloud physical processes remains unclear. In this study, we investigate the influence of homogeneous and heterogeneous freezing processes, ice particle growth and fallout, and mesoscale vertical velocity fluctuations on P(σ) shape during an orographic Ci event. We evaluate Lagrangian Ci evolution along kinematic trajectories from a mesoscale weather model (MM5) using an adiabatic parcel model with binned ice microphysics. Although the presence of ice nuclei increased model cloud cover, our results highlight the importance of homogeneous freezing and mesoscale vertical velocity variability in controlling Ci P(σ) shape along realistic upper tropospheric trajectories.
Regional pollution potentials of megacities and other major population centers
Authors: Lawrence M. G. , Butler T. M. , Steinkamp J. , Gurjar B. R. , Lelieveld J.
Published: April 2010

Abstract. Megacities and other major population centers represent large, concentrated sources of anthropogenic pollutants to the atmosphere, with consequences for both local air quality and for regional and global atmospheric chemistry. The tradeoffs between the regional buildup of pollutants near their sources versus long-range export depend on meteorological characteristics which vary as a function of geographical location and season. Both horizontal and vertical transport contribute to pollutant export, and the overall degree of export is strongly governed by the lifetimes of pollutants. We provide a first quantification of these tradeoffs and the main factors influencing them in terms of "regional pollution potentials", metrics based on simulations of representative tracers using the 3-D global model MATCH (Model of Atmospheric Transport and Chemistry). The tracers have three different lifetimes (1, 10, and 100 days) and are emitted from 36 continental large point sources. Several key features of the export characteristics emerge. For instance, long-range near-surface pollutant export is generally strongest in the middle and high latitudes, especially for source locations in Eurasia, for which 17–34% of a tracer with a 10-day lifetime is exported beyond 1000 km and still remains below 1 km altitude. On the other hand, pollutant export to the upper troposphere is greatest in the tropics, due to transport by deep convection, and for six source locations, more than 50% of the total mass of the 10-day lifetime tracer is found above 5 km altitude. Furthermore, not only are there order of magnitude interregional differences, such as between low and high latitudes, but also often substantial intraregional differences, which we discuss in light of the regional meteorological characteristics. We also contrast the roles of horizontal dilution and vertical mixing in reducing the pollution buildup in the regions including and surrounding the sources. For some regions such as Eurasia, dilution due to long-range horizontal transport governs the local and regional pollution buildup; however, on a global basis, differences in vertical mixing are dominant in determining the pollution buildup both around and further downwind of the source locations.
Elimination of hidden a priori information from remotely sensed profile data
Authors: von Clarmann T. , Grabowski U.
Published: April 2010

Abstract. Profiles of atmospheric state variables retrieved from remote measurements often contain a priori information which causes complication in the statistical use of data and in the comparison with other measured or modeled data. For such applications it often is desirable to remove the a priori information from the data product. If the retrieval involves an ill-posed inversion problem, formal removal of the a priori information requires resampling of the data on a coarser grid, which in some sense, however, is a prior constraint in itself. The fact that the trace of the averaging kernel matrix of a retrieval is equivalent to the number of degrees of freedom of the retrieval is used to define an appropriate information-centered representation of the data where each data point represents one degree of freedom. Since regridding implies further degradation of the data and thus causes additional loss of information, a re-regularization scheme has been developed which allows resampling without additional loss of information. For a typical ClONO2 profile retrieved from spectra as measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), the constrained retrieval has 9.7 degrees of freedom. After application of the proposed transformation to a coarser information-centered altitude grid, there are exactly 9 degrees of freedom left, and the averaging kernel on the coarse grid is unity. Pure resampling on the information-centered grid without re-regularization would reduce the degrees of freedom to 7.1 (6.7) for a staircase (triangular) representation scheme.
The CO2 tracer clock for the Tropical Tropopause Layer
Authors: Park S. , Jiménez R. , Daube B. C. , Pfister L. , Conway T. J. , Gottlieb E. W. , Chow V. Y. , Curran D. J. , Matross D. M. , Bright A. , Atlas E. L. , Bui T. P. , Gao R.-S. , Twohy C. H. , Wofsy S. C.
Published: April 2010

Abstract. Observations of CO2 were made in the upper troposphere and lower stratosphere in the deep tropics in order to determine the patterns of large-scale vertical transport and age of air in the Tropical Tropopause Layer (TTL). Flights aboard the NASA WB-57F aircraft over Central America and adjacent ocean areas took place in January and February, 2004 (Pre-AURA Validation Experiment, Pre-AVE) and 2006 (Costa Rice AVE, CR-AVE), and for the same flight dates of 2006, aboard the Proteus aircraft from the surface to 15 km over Darwin, Australia (Tropical Warm Pool International Cloud Experiment, TWP-ICE). The data demonstrate that the TTL is composed of two layers with distinctive features: (1) the lower TTL, 350–360 K (potential temperature(θ); approximately 12–14 km), is subject to inputs of convective outflows, as indicated by layers of variable CO2 concentrations, with air parcels of zero age distributed throughout the layer; (2) the upper TTL, from θ=~360 K to ~390 K (14–18 km), ascends slowly and ages uniformly, as shown by a linear decline in CO2 mixing ratio tightly correlated with altitude, associated with increasing age. This division is confirmed by ensemble trajectory analysis. The CO2 concentration at the level of 360 K was 380.0(±0.2) ppmv, indistinguishable from surface site values in the Intertropical Convergence Zone (ITCZ) for the flight dates. Values declined with altitude to 379.2(±0.2) ppmv at 390 K, implying that air in the upper TTL monotonically ages while ascending. In combination with the winter slope of the CO2 seasonal cycle (+10.8±0.4 ppmv/yr), the vertical gradient of –0.78 (±0.09) ppmv gives a mean age of 26(±3) days for the air at 390 K and a mean ascent rate of 1.5(±0.3) mm s−1. The TTL near 360 K in the Southern Hemisphere over Australia is very close in CO2 composition to the TTL in the Northern Hemisphere over Costa Rica, with strong contrasts emerging at lower altitudes (<360 K). Both Pre-AVE and CR-AVE CO2 observed unexpected input from deep convection over Amazônia deep into the TTL. The CO2 data confirm the operation of a highly accurate tracer clock in the TTL that provides a direct measure of the ascent rate of the TTL and of the age of air entering the stratosphere.
GEM/POPs: a global 3-D dynamic model for semi-volatile persistent organic pollutants – Part 1: Model description and evaluations of air concentrations
Authors: Gong S. L. , Huang P. , Zhao T. L. , Sahsuvar L. , Barrie L. A. , Kaminski J. W. , Li Y. F. , Niu T.
Published: April 2010

Abstract. GEM/POPs was developed to simulate the transport, deposition and partitioning of semi-volatile persistent organic pollutants (POPs) in the atmosphere within the framework of Canadian weather forecasting model GEM. In addition to the general processes such as anthropogenic emissions, atmosphere/water and atmosphere/soil exchanges, GEM/POPs incorporates a dynamic aerosol module to provide the aerosol surface areas for the semi-volatile POPs to partition between gaseous and particle phases and a mechanism for particle-bound POPs to be removed. Simulation results of three PCBs (28, 153 and 180) for the year 2000 indicate that the model captured the main features of global atmospheric PCBs when compared with observations from EMEP, IADN and Alert stations. The annual averaged concentrations and the fractionation of the three PCBs as a function of latitudes agreed reasonably well with observations. The impacts of atmospheric aerosols on the transports and partitioning of the three PCBs are reasonably simulated. The ratio of particulate to gaseous PCBs in the atmospheric column ranges from less than 0.1 for PCB28 to as high as 100 for PCB180, increasing from the warm lower latitudes to the cold high latitudes. Application of GEM/POPs in a study of the global transports and budgets of various PCBs accompanies this paper.