bluuebunny/crossref_metadata_2025 huggingface dataset:
Application of a diode array spectroradiometer to measuring the spectral scattering properties of cloud types in a laboratory
Authors: Smedley A. R. D. , Webb A. R. , Saunders C. P. R.
Published: April 2010

Abstract. In the last few years diode array spectroradiometers have become useful complements to traditional scanning instruments when measuring visible and ultraviolet solar radiation incident on the ground. This study describes the application of such an instrument to the problem of measuring the radiation scattered by different cloud types in a laboratory environment. Details of how the instrument is incorporated into the experimental set-up are given together with the development of the system as a whole. The capability to measure a full spectrum for each scattering angle is an undoubted advantage, although the limited dynamic range impacts on the usefulness for optically thin clouds. Nevertheless example results are presented: (1) scattering phase functions at a range of wavelengths recorded simultaneously for water clouds, showing spectral deviation at the rainbow angle and verification of Mie theory; (2) likewise for mixed phase clouds, with evidence of both halo and rainbow features in a single scattering function; and, (3) detail of the forward scattering region in a glaciated cloud showing a barely perceptible halo feature, with implications for the small-scale structure of the ice crystals produced.
Vertical profiles of urban aerosol complex refractive index in the frame of ESQUIF airborne measurements
Authors: Raut J.-C. , Chazette P.
Published: April 2010

Abstract. A synergy between lidar, sunphotometer and in situ measurements has been applied to airborne observations performed during the Etude et Simulation de la QUalité de l'air en Ile-de-France (ESQUIF), enabling the retrieval of vertical profiles for the aerosol complex refractive index (ACRI) and single-scattering albedo with a vertical resolution of 200 m over Paris area. The averaged value over the entire planetary boundary layer (PBL) for the ACRI is close to 1.51(±0.02)–i0.017(±0.003) at 532 nm. The single-scattering albedo of the corresponding aerosols is found to be ~0.9 at the same wavelength. A good agreement is found with previous studies for urban aerosols. A comparison of vertical profiles of ACRI with simulations combining in situ measurements and relative humidity (RH) profiles has highlighted a modification in aerosol optical properties linked to their history and the origin of the air mass. The determination of ACRI in the atmospheric column enabled to retrieve vertical profiles of extinction coefficient in accordance with lidar profiles measurements.
Effects of uncertainties in the thermodynamic properties of aerosol components in an air quality model – Part I: Treatment of inorganic electrolytes and organic compounds in the condensed phase
Authors: Clegg S. L. , Kleeman M. J. , Griffin R. J. , Seinfeld J. H.
Published: April 2010

Abstract. Air quality models that generate the concentrations of semi-volatile and other condensable organic compounds using an explicit reaction mechanism require estimates of the physical and thermodynamic properties of the compounds that affect gas/aerosol partitioning: vapour pressure (as a subcooled liquid), and activity coefficients in the aerosol phase. The model of Griffin, Kleeman and co-workers (e.g., Griffin et al., 1999; Kleeman et al., 1999) assumes that aerosol particles consist of an aqueous phase, containing inorganic electrolytes and soluble organic compounds, and a hydrophobic phase containing mainly primary hydrocarbon material. Thirty eight semi-volatile reaction products are grouped into ten surrogate species which partition between the gas phase and both phases in the aerosol. Activity coefficients of the organic compounds are calculated using UNIFAC. In a companion paper (Clegg et al., 2007) we examine the likely uncertainties in the vapour pressures of the semi-volatile compounds and their effects on partitioning over a range of atmospheric relative humidities. In this work a simulation for the South Coast Air Basin surrounding Los Angeles, using lower vapour pressures of the semi-volatile surrogate compounds consistent with estimated uncertainties in the boiling points on which they are based, yields a doubling of the predicted 24-h average secondary organic aerosol concentrations. The dependency of organic compound partitioning on the treatment of inorganic electrolytes in the air quality model, and the performance of this component of the model, are determined by analysing the results of a trajectory calculation using an extended version of the Aerosol Inorganics Model of Wexler and Clegg (2002). Simplifications are identified where substantial efficiency gains can be made, principally: the omission of dissociation of the organic acid surrogates; restriction of aerosol organic compounds to one of the two phases (aqueous or hydrophobic) where equilibrium calculations suggest partitioning strongly in either direction; a single calculation of activity coefficients of the organic compounds for simulations where they are determined by the presence of one component at high concentration in either phase (i.e., water in the aqueous phase, or a hydrocarbon surrogate compound P8 in the hydrophobic phase) and are therefore almost invariant. The implications of the results for the development of aerosol models are discussed.
Effects of uncertainties in the thermodynamic properties of aerosol components in an air quality model – Part II: Predictions of the vapour pressures of organic compounds
Authors: Clegg S. L. , Kleeman M. J. , Griffin R. J. , Seinfeld J. H.
Published: April 2010

Abstract. Air quality models that generate the concentrations of semi-volatile and other condensable organic compounds using an explicit reaction mechanism require estimates of the vapour pressures of the organic compounds that partition between the aerosol and gas phases. The model of Griffin, Kleeman and co-workers (e.g., Griffin et al., 2005) assumes that aerosol particles consist of an aqueous phase, containing inorganic electrolytes and soluble organic compounds, and a hydrophobic phase containing mainly primary hydrocarbon material. Thirty eight semi-volatile reaction products are grouped into ten surrogate species. In Part I of this work (Clegg et al., 2007) the thermodynamic elements of the gas/aerosol partitioning calculation are examined, and the effects of uncertainties and approximations assessed, using a simulation for the South Coast Air Basin around Los Angeles as an example. Here we compare several different methods of predicting vapour pressures of organic compounds, and use the results to determine the likely uncertainties in the vapour pressures of the semi-volatile surrogate species in the model. These are typically an order of magnitude or greater, and are further increased when the fact that each compound represents a range of reaction products (for which vapour pressures can be independently estimated) is taken into account. The effects of the vapour pressure uncertainties associated with the water-soluble semi-volatile species are determined over a wide range of atmospheric liquid water contents. The vapour pressures of the eight primary hydrocarbon surrogate species present in the model, which are normally assumed to be involatile, are also predicted. The results suggest that they have vapour pressures high enough to exist in both the aerosol and gas phases under typical atmospheric conditions.
Water dimer absorption of visible light
Authors: Hargrove J.
Published: April 2010

Abstract. Laboratory measurements of water vapor absorption using cavity ring-down spectroscopy revealed a broad absorption at 405 nm with a quadratic dependence on water monomer concentration, a similar absorption with a linear component at 532 nm, and only linear absorption at 570 nm in the vicinity of water monomer peaks. D2O absorption is weaker and linear at 405 nm. Van't Hoff plots constructed at 405.26 nm suggest that for dimerization, Keq=0.056±0.02 atm−1, ΔH°301 K=−16.6±2 kJ mol−1 and ΔS°301 K=−80±10 J mol−1 K−1. This transition peaks at 409.5 nm, could be attributed to the 8th overtone of water dimer and the 532 nm absorption to the 6th overtone. It is possible that some lower overtones previously searched for are less enhanced. These absorptions could increase water vapor feed back calculations leading to higher global temperature projections with currently projected greenhouse gas levels or greater cooling from greenhouse gas reductions.
N2O release from agro-biofuel production negates global warming reduction by replacing fossil fuels
Authors: Crutzen P. J. , Mosier A. R. , Smith K. A. , Winiwarter W.
Published: April 2010

Abstract. The relationship, on a global basis, between the amount of N fixed by chemical, biological or atmospheric processes entering the terrestrial biosphere, and the total emission of nitrous oxide (N2O), has been re-examined, using known global atmospheric removal rates and concentration growth of N2O as a proxy for overall emissions. The relationship, in both the pre-industrial period and in recent times, after taking into account the large-scale changes in synthetic N fertiliser production and deforestation, is consistent, showing an overall conversion factor of 3–5%. This factor is covered only in part by the ~1% of "direct" emissions from agricultural crop lands estimated by IPCC (2006), or the "indirect" emissions cited therein. This means that the extra N2O entering the atmosphere as a result of using N to produce crops for biofuels will also be correspondingly greater than that estimated just on the basis of IPCC (2006). When the extra N2O emission from biofuel production is calculated in "CO2-equivalent" global warming terms, and compared with the quasi-cooling effect of "saving" emissions of fossil fuel derived CO2, the outcome is that the production of commonly used biofuels, such as biodiesel from rapeseed and bioethanol from corn (maize), can contribute as much or more to global warming by N2O emissions than cooling by fossil fuel savings. Crops with less N demand, such as grasses and woody coppice species have more favourable climate impacts. This analysis only considers the conversion of biomass to biofuel. It does not take into account the use of fossil fuel on the farms and for fertilizer and pesticide production, but it also neglects the production of useful co-products. Both factors partially compensate each other. This needs to be analyzed in a full life cycle assessment.
Validation of aerosol and cloud layer structures from the space-borne lidar CALIOP using Seoul National University ground-based lidar
Authors: Kim S.-W. , Berthier S. , Chazette P. , Raut J.-C. , Dulac F. , Yoon S.-C.
Published: April 2010

Abstract. We present first observationally based validations of the space-borne lidar CALIOP onboard CALIPSO satellite using coincidental observations from a ground-based SNU lidar for 3 different types of atmospheric scenes. Both lidar measurements were taken in nearly same airmass in space and time. Total attenuated backscatters at 532 nm from the two instruments show similar aerosol and cloud layer structures (the top and bottom heights) both under cloud-free conditions and in case of multi-aerosol layers underlying semi-transparent cirrus clouds. This result confirms that the CALIPSO science team algorithms of the discrimination of cloud and aerosol as well as of their layer top and base altitudes are sound. Under thick clouds conditions, only information on the cloud top (bottom) height is reliable from CALIOP (ground-based lidar) observations due to strong signal attenuations. However, simultaneous space-borne CALIOP and ground-based SNU lidar measurements complement each other and provide full information on the vertical distribution of aerosols and clouds. Discrepancies between space-borne and ground-based lidar signals are partly explained by the strong spatial and vertical inhomogeneous distributions of clouds at few kilometer horizontal scales.
The SOA/VOC/NOx system: an explicit model of secondary organic aerosol formation
Authors: Camredon M. , Aumont B. , Lee-Taylor J. , Madronich S.
Published: April 2010

Abstract. Our current understanding of secondary organic aerosol (SOA) formation is limited by our knowledge of gaseous secondary organics involved in gas/particle partitioning. The objective of this study is to explore (i) the potential for products of multiple oxidation steps contributing to SOA, and (ii) the evolution of the SOA/VOC/NOx system. We developed an explicit model based on the coupling of detailed gas-phase oxidation schemes with a thermodynamic condensation module. Such a model allows prediction of SOA mass and speciation on the basis of first principles. The SOA/VOC/NOx system is studied for the oxidation of 1-octene under atmospherically relevant concentrations. In this study, gaseous oxidation of octene is simulated to lead to SOA formation. Contributors to SOA formation are shown to be formed via multiple oxidation steps of the parent hydrocarbon. The behaviour of the SOA/VOC/NOx system simulated using the explicit model agrees with general tendencies observed during laboratory chamber experiments. This explicit modelling of SOA formation appears as a useful exploratory tool to (i) support interpretations of SOA formation observed in laboratory chamber experiments, (ii) give some insights on SOA formation under atmospherically relevant conditions and (iii) investigate implications for the regional/global lifetimes of the SOA.
A new chemistry-climate tropospheric and stratospheric model MOCAGE-Climat: evaluation of the present-day climatology and sensitivity to surface processes
Authors: Teyssèdre H. , Michou M. , Clark H. L. , Josse B. , Karcher F. , Olivié D. , Peuch V.-H. , Saint-Martin D. , Cariolle D. , Attié J.-L. , Ricaud P. , van der A R. J. , Chéroux F.
Published: April 2010

Abstract. We present the chemistry-climate configuration of the Météo-France Chemistry and Transport Model, MOCAGE-Climat. MOCAGE-Climat is a state-of-the-art model that simulates the global distribution of ozone and its precursors (82 chemical species) both in the troposphere and the stratosphere, up to the mid-mesosphere (~70 km). Surface processes (emissions, dry deposition), convection, and scavenging are explicitly described in the model that has been driven by the ECMWF operational analyses of the period 2000–2005, on T21 and T42 horizontal grids and 60 hybrid vertical levels, with and without a procedure that reduces calculations in the boundary layer, and with on-line or climatological deposition velocities. Model outputs have been compared to available observations, both from satellites (TOMS, HALOE, SMR, SCIAMACHY, MOPITT) and in-situ instrument measurements (ozone sondes, MOZAIC and aircraft campaigns) at climatological timescales. The distribution of long-lived species is in fair agreement with observations in the stratosphere putting apart shortcomings linked to the large-scale circulation. The variability of the ozone column, both spatially and temporarily, is satisfactory. However, the too fast Brewer-Dobson circulation accumulates too much ozone in the lower to mid-stratosphere at the end of winter. Ozone in the UTLS region does not show any systematic bias. In the troposphere better agreement with ozone sonde measurements is obtained at mid and high latitudes than in the tropics and differences with observations are the lowest in summer. Simulations using a simplified boundary layer lead to ozone differences between the model and the observations up to the mid-troposphere. NOx in the lowest troposphere is in general overestimated, especially in the winter months over the northern hemisphere, which might result from a positive bias in OH. Dry deposition fluxes of O3 and nitrogen species are within the range of values reported by recent inter-comparison model exercises. The use of climatological deposition velocities versus deposition velocities calculated on-line had greatest impact on HNO3 and NO2 in the troposphere.
Effects on surface atmospheric photo-oxidants over Greece during the total solar eclipse event of 29 March 2006
Authors: Zanis P. , Katragkou E. , Kanakidou M. , Psiloglou B. , Karathanasis S. , Vrekoussis M. , Gerasopoulos E. , Lysaridis I. , Markakis K. , Poupkou A. , Amiridis V. , Melas D. , Mihalopoulos N. , Zerefos C.
Published: April 2010

Abstract. This study investigates the effects of the total solar eclipse of 29 March 2006 on surface air-quality levels over Greece based on observations at a number of sites in conjunction with chemical box modelling and 3-D air-quality modelling. Emphasis is given on surface ozone and other photooxidants at four Greek sites Kastelorizo, Finokalia (Crete), Pallini (Athens) and Thessaloniki, which are located at gradually increasing distances from the path of the eclipse totality and are characterized by different air pollution levels. The eclipse offered the opportunity to test our understanding of air pollution build-up and the response of the gas-phase chemistry of photo-oxidants during a photolytical perturbation using both a photochemical box model and a regional air-quality offline model based on the modeling system WRF/CAMx. At the relatively unpolluted sites of Kastelorizo and Finokalia no clear impact of the solar eclipse on surface O3, NO2 and NO concentrations can be deduced from the observations and model simulations as the calculated changes in net ozone production rates between eclipse and non eclipse conditions are rather small compared to the ozone variability and hence the solar eclipse effects on ozone can be easily masked by transport. At the polluted sites of Thessaloniki and Pallini, the solar eclipse effects on O3, NO2 and NO concentrations are clearly revealed from both the measurements and 3-D air-quality modeling with the net effect being a decrease in O3 and NO and an increase in NO2 as NO2 formed from the reaction of O3 with NO while at the same time NO2 is not efficiently photolysed. It is evident from the 3-D air quality modeling over Greece that the maximum effects of the eclipse on O3, NO2 and NO are reflected at the large urban agglomerations of Athens, and Thessaloniki where the maximum of the emissions occur.
Capturing vertical profiles of aerosols and black carbon over the Indian Ocean using autonomous unmanned aerial vehicles
Authors: Corrigan C. E. , Roberts G. C. , Ramana M. V. , Kim D. , Ramanathan V.
Published: April 2010

Abstract. Measurements of the vertical distribution of aerosol properties provide essential information for generating more accurate model estimates of radiative forcing and atmospheric heating rates compared with employing remotely sensed column averaged properties. A month long campaign over the Indian Ocean during March 2006 investigated the interaction of aerosol, clouds, and radiative effects. Routine vertical profiles of aerosol and water vapor were determined using autonomous unmanned aerial vehicles equipped with miniaturized instruments. Comparisons of these airborne instruments with established ground-based instruments and in aircraft-to-aircraft comparisons demonstrated an agreement within 10%. Aerosol absorption optical depths measured directly using the unmanned aircraft differed from columnar AERONET sun-photometer results by only 20%. Measurements of total particle concentration, particle size distributions, aerosol absorption and black carbon concentrations are presented along with the trade wind thermodynamic structure from the surface to 3000 m above sea level. Early March revealed a well-mixed layer up to the cloud base at 500 m above mean seal level (m a.s.l.), followed by a decrease of aerosol concentrations with altitude. The second half of March saw the arrival of a high altitude plume existing above the mixed layer that originated from a continental source and increased aerosol concentrations by more than tenfold, yet the surface air mass showed little change in aerosol concentrations and was still predominantly influenced by marine sources. Black carbon concentrations at 1500 m above sea level increased from 70 ng/m³ to more than 800 ng/m³ with the arrival of this polluted plume. The absorption aerosol optical depth increased from as low as 0.005 to as much as 0.035 over the same period. The spectral dependence of the aerosol absorption revealed an absorption Angstrom exponent of 1.0, which is typical of an aerosol with most of its absorption attributed to black carbon and generally indicates the absorbing component originated from fossil fuel sources and other high-temperature combustion sources. The results indicate that surface measurements do not represent the aerosol properties within the elevated layers, especially if these layers are influenced by long range transport.
Aerosol and precipitation chemistry in a remote site in Central Amazonia: the role of biogenic contribution
Authors: Pauliquevis T. , Lara L. L. , Antunes M. L. , Artaxo P.
Published: April 2010

Abstract. A long-term (2–3 years) measurement of aerosol and precipitation chemistry was carried out in a remote site in Central Amazonia, Balbina, (1°55' S, 59°29' W, 174 m above sea level), about 200 km north of Manaus city. Aerosols were sampled using stacked filter units (SFU), which separate fine (d<2.5 μm) and coarse mode (2.5 μm<d<10.0 μm). Filters were analyzed for particulate mass (PM), black carbon (BC) and elemental composition by Particle Induced X-Ray Emission (PIXE). Rainwater samples were collected using a wet-only sampler and samples were analyzed for pH and ionic composition, which was determined using ionic chromatography (IC). Aerosol mass was predominantly of biogenic origin and concentrated in coarse mode, comprising up to 81% of PM10 concentration during the wet season. Natural biogenic aerosol also dominates the fine mode in the wet season, with very low concentrations (average 2.2 μg/m3). Large-scale transport of smoke from biomass burning was the second most important contribution, reaching 77% of fine mode particulate mass during the dry season. Soil dust was responsible by a minor fraction of the aerosol mass (less than 17%). Rainwater chemistry was controlled by biogenic emissions. The volume-weighted mean (VWM) pH was 4.90. The most important contribution to acidity was weak organic acids. The organic acidity was predominantly associated with the presence of acetic acid, instead of formic acid which is more often observed in pristine tropical areas. Deposition rates for major species did not differ significantly between dry and wet season, except for NH4+ and acetate, which had smaller deposition rates during dry season. While biomass burning emissions were clearly identified in the aerosol component, it was not possible to discern any presence of biomass burning emissions in rainwater chemistry. The long-range transport of sea salt and biogenic particles was observed both in aerosols and rainwater composition. The results showed here indicate that in Amazonia it is still possible to observe pristine atmospheric conditions, relatively free of anthropogenic influences.
LACIS-measurements and parameterization of sea-salt particle hygroscopic growth and activation
Authors: Niedermeier D. , Stratmann F. , Wex H. , Brüggemann E. , Kiselev A. , Henk H. , Heintzenberg J.
Published: April 2010

Abstract. The Leipzig Aerosol Cloud Interaction Simulator (LACIS) was used to investigate the hygroscopic growth and activation of sea-salt particles which were generated from three different sea-water samples. Köhler theory was utilized to model the hygroscopic growth of these particles. Some parameters used in this model are unknown for sea-salt. These parameters are combined in an "ionic density" ρion. For each sea-salt sample an average ρion was determined by fitting the Köhler equation to the data from the hygroscopic growth measurements. LACIS was also used to measure the activation of the sea-salt particles at three different supersaturations: 0.10%, 0.16% and 0.30%. A CCN-closure was tested by calculating the critical diameters Dcrit for the sea-salt particles at these supersaturations, using the Köhler model and the corresponding ρion as derived from the hygroscopic growth data. These calculated critical diameters were compared to the measured ones. Measured and calculated values of Dcrit agree within the level of uncertainty. Based on this successful closure, a new parameterization to describe sea-salt-particle hygroscopic growth (at RH>95%) and activation has been developed.
A compact and stable eddy covariance set-up for methane measurements using off-axis integrated cavity output spectroscopy
Authors: Hendriks D. M. D. , Dolman A. J. , van de Molen M. K. , van Huissteden J.
Published: April 2010

Abstract. A DLT-100 Fast Methane Analyser (FMA) from Los Gatos Research (LGR) Ltd. is assessed for its applicability in a closed path eddy covariance field set-up. The FMA uses off-axis integrated cavity output spectroscopy (ICOS) combined with a highly specific narrow band laser for the detection of CH4 and strongly reflective mirrors to obtain a laser path length of 2×10³ to 20×10³ m. Statistical testing, a calibration experiment and comparison with high tower data showed high precision and very good stability of the instrument. The measurement cell response time was tested to be 0.10 s. In the field set-up, the FMA is attached to a scroll pump and combined with a Gill Windmaster Pro 3 axis Ultrasonic Anemometer and a Licor 7500 open path infrared gas analyzer. The power-spectra and co-spectra of the instrument are satisfactory for 10 Hz sampling rates. The correspondence with CH4 flux chamber measurements is good and the observed CH4 emissions are comparable with (eddy covariance) CH4 measurements in other peat areas. CH4 emissions are rather variable over time and show a diurnal pattern. The average CH4 emission is 50±12.5 nmol m−2 s−1, while the typical maximum CH4 emission is 120±30 nmol m−2 s−1 (during daytime) and the typical minimum flux is –20±2.5 nmol m−2 s−1 (uptake, during night time). Additionally, the set-up was tested for three measurement techniques with slower measurement rates, which could be used in the future to make the scroll pump superfluous and save energy. Both disjunct eddy covariance as well as slow 1 Hz eddy covariance showed results very similar to normal 10 Hz eddy covariance. Relaxed eddy accumulation (REA) only matched with normal 10 Hz eddy covariance over an averaging period of at least several weeks.
Summertime stratospheric processes at northern mid-latitudes: comparisons between MANTRA balloon measurements and the Canadian Middle Atmosphere Model
Authors: Melo S. M. L. , Blatherwick R. , Davies J. , Fogal P. , de Grandpré J. , McConnell J. , McElroy C. T. , McLandress C. , Murcray F. J. , Olson J. R. , Semeniuk K. , Shepherd T. G. , Strong K. , Tarasick D. , Williams-Rioux B. J.
Published: April 2010

Abstract. In this paper we report on a study conducted using the Middle Atmospheric Nitrogen TRend Assessment (MANTRA) balloon measurements of stratospheric constituents and temperature and the Canadian Middle Atmosphere Model (CMAM) in order to evaluate the ability of the model to reproduce the measured fields and to thereby test our ability to describe mid-latitude summertime stratospheric processes. The MANTRA measurements used here are vertical profiles of ozone, temperature, N2O, CH4, HNO3, and HCl obtained during four campaigns, involving the launch of both ozonesondes and large balloons from Vanscoy, Saskatchewan, Canada (52° N, 107° W). The campaigns were conducted in August and September 1998, 2000, 2002 and 2004. During late summer at mid-latitudes, the stratosphere is close to photochemical control, providing an ideal scenario for the study reported here. From this analysis we found that: (1) reducing the value for the vertical diffusion coefficient in CMAM to a more physically reasonable value results in the model better reproducing the measured profiles of long-lived species; (2) the existence of compact correlations among the constituents, as expected from independent measurements in the literature and from models, confirms the self-consistency of the MANTRA measurements; and (3) the 1998 ozone measurements show a narrow layer of low ozone centered near 25 km that is consistent with fossil debris from the polar vortex, suggesting that localized springtime ozone anomalies can persist through summer, affecting ozone levels at mid-latitudes.
The impact of mixing across the polar vortex edge on Match ozone loss estimates
Authors: Grooß J.-U. , Müller R. , Konopka P. , Steinhorst H.-M. , Engel A. , Möbius T. , Volk C. M.
Published: April 2010

Abstract. The Match method for quantification of polar chemical ozone loss is investigated mainly with respect to the impact of mixing across the vortex edge onto this estimate. We show for the winter 2002/03 that significant mixing across the vortex edge occurred and was accurately modeled by the Chemical Lagrangian Model of the Stratosphere. Observations of inert tracers and ozone in-situ from HAGAR on the Geophysica aircraft and sondes and also remote from MIPAS on ENVISAT were reproduced well. The model even reproduced a small vortex remnant that was isolated until June 2003 and was observed in-situ by a balloon-borne whole air sampler. We use this CLaMS simulation to quantify the impact of cross vortex edge mixing on the results of the Match method. It is shown that a time integration of the determined vortex average ozone loss rates as performed in Match results in larger ozone loss than the polar vortex average ozone loss in CLaMS. Also, the determination of the Match ozone loss rates can be influenced by mixing. This is especially important below 430 K, where ozone outside the vortex is lower than inside and the vortex boundary is not a strong transport barrier. This effect and further sampling effects cause an offset between vortex average ozone loss rates derived from Match and deduced from CLaMS with an even sampling for the entire vortex. Both, the time-integration of ozone loss and the determination of ozone loss rates for Match are evaluated using the winter 2002/03 CLaMS simulation. These impacts can explain the differences between CLaMS and Match column ozone loss. While the investigated effects somewhat reduce the apparent discrepancy in January ozone loss rates, a discrepancy between simulations and Match remains. However, its contribution to the accumulated ozone loss over the winter is not large.
SIMPOL.1: A simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds
Authors: Pankow J. F. , Asher W. E.
Published: April 2010

Abstract. The SIMPOL.1 group contribution method is developed for predicting the liquid vapor pressure pLo (atm) and enthalpy of vaporization ΔHvap (kJ mol-1) of organic compounds as functions of temperature (T). For each compound i, the method assumes log10pL,io(T)=Σkνk,ibk(T) where νk,i is the number of groups of type k, and bk(T) is the contribution to log10 pL,io(T) by each group of type k. A zeroeth group is included that uses b0(T) with ν0,i=1 for all i. A total of 30 structural groups are considered: molecular carbon, alkyl hydroxyl, aromatic hydroxyl, alkyl ether, alkyl ring ether, aromatic ether, aldehyde, ketone, carboxylic acid, ester, nitrate, nitro, alkyl amine (primary, secondary, and tertiary), aromatic amine, amide (primary, secondary, and tertiary), peroxide, hydroperoxide, peroxy acid, C=C, carbonylperoxynitrate, nitro-phenol, nitro-ester, aromatic rings, non-aromatic rings, C=C–C=O in a non-aromatic ring, and carbon on the acid-side of an amide. The T dependence in each of the bk(T) is assumed to follow b(T)=B1/T+B2+B3T+B4lnT. Values of the B coefficients are fit using an initial basis set of 272 compounds for which experimentally based functions pL,io=fi(T) are available. The range of vapor pressure considered spans fourteen orders of magnitude. The ability of the initially fitted B coefficients to predict pLo values is examined using a test set of 161 compounds and a T range that is as wide as 273.15 to 393.15 K for some compounds. σFIT is defined as the average over all points of the absolute value of the difference between experimental and predicted values of log10pL,io(T). After consideration of σFIT for the test set, the initial basis set and test set compounds are combined, and the B coefficients re-optimized. For all compounds and temperatures, σFIT=0.34: on average, pL,io(T) values are predicted to within a factor of 2. Because d(log10pL,io(T))/d(1/T) is related to the enthalpy of vaporization ΔHvap,i, the fitted B provide predictions of ΔHvap,i based on structure.
A comprehensive modelling way for assessing real-time mixings of mineral and anthropogenic pollutants in East Asia
Authors: Lasserre F. , Cautenet G. , Bouet C. , Dong X. , Kim Y. J. , Sugimoto N. , Matsui I. , Shimizu A.
Published: April 2010

Abstract. In order to assess the complex mixing of atmospheric anthropogenic and natural pollutants over the East Asian region, we propose to take into account the main aerosols simultaneously present over China, Korea and Japan during the spring season. With the mesoscale RAMS (Regional Atmospheric Modeling System) tool, we present a simulation of natural (desert) dust events along with some of the most critical anthropogenic pollutants over East Asia: sulphur elements (SO2 and SO42−) and Black Carbon (BC). During a 2-week case study of dust events which occurred in April 2005 over an area extending from the Gobi deserts to the Japan surroundings, we retrieve the behaviours of the different aerosols plumes. We focus on possible dust mixing with the anthropogenic pollutants from megalopolis. For both natural and anthropogenic pollution, the model results are in general agreement with the horizontal and vertical distributions of concentrations as measured by remote data, in situ LIDAR, PM10 data and literature. In particular, we show that a simplified chemistry approach of this complex issue can be efficient enough to model this event, with a real-time step of 3 h. The model provides the good shapes and orders of magnitude for the Aerosol Optical Thickness (AOT) and species contributions (via the Angström Exponent) when compared with the AERONET data.
Reversible and irreversible processing of biogenic olefins on acidic aerosols
Authors: Liggio J. , Li S.-M.
Published: April 2010

Abstract. Recent evidence has suggested that heterogeneous chemistry of oxygenated hydrocarbons, primarily carbonyls, plays a role in the formation of secondary organic aerosol (SOA); however, evidence is emerging that direct uptake of alkenes on acidic aerosols does occur and can contribute to SOA formation. In the present study, significant uptake of monoterpenes, oxygenated monoterpenes and sesquiterpenes to acidic sulfate aerosols is found under various conditions in a reaction chamber. Proton transfer mass spectrometry is used to quantify the organic gases, while an aerosol mass spectrometer is used to quantify the organic mass uptake and obtain structural information for heterogeneous products. Aerosol mass spectra are consistent with several mechanisms including acid catalyzed olefin hydration, cationic polymerization and organic ester formation, while measurable decreases in the sulfate mass on a per particle basis suggest that the formation of organosulfate compounds is also likely. A portion of the heterogeneous reactions appears to be reversible, consistent with reversible olefin hydration reactions. A slow increase in the organic mass after a fast initial uptake is attributed to irreversible reactions, consistent with polymerization and organosulfate formation. Uptake coefficients (γ) were estimated for a fast initial uptake governed by the mass accommodation coefficient (α) and ranged from 1×10-6–2.5×10−2. Uptake coefficients for a subsequent slower reactive uptake ranged from 1×10-7–1×10-4. These processes are estimated to potentially produce greater than 2.5 μg m−3 of SOA from the various biogenic hydrocarbons under atmospheric conditions, which can be highly significant given the large array of atmospheric olefins.
Comparison between the first Odin-SMR, Aura MLS and CloudSat retrievals of cloud ice mass in the upper tropical troposphere
Authors: Eriksson P. , Ekström M. , Rydberg B. , Wu D. L. , Austin R. T. , Murtagh D. P.
Published: April 2010

Abstract. Emerging microwave satellite techniques are expected to provide improved global measurements of cloud ice mass. CloudSat, Aura MLS and Odin-SMR fall into this category and first cloud ice retrievals from these instruments are compared. The comparison is made for partial ice water columns above 12 km, following the SMR retrieval product. None of the instruments shows significant false cloud detections and a consistent view of the geographical distribution of cloud ice is obtained, but differences on the absolute levels exist. CloudSat gives the lowest values, with an overall mean of 2.12 g/m2. A comparable mean for MLS is 4.30 g/m2. This relatively high mean can be an indication of overestimation of the vertical altitude of cloud ice by the MLS retrievals. The vertical response of SMR has also some uncertainty, but this does not affect the comparison between MLS and CloudSat. SMR observations are sensitive to cloud inhomogeneities inside the footprint and some compensation is required. Results in good agreement with CloudSat, both in regard of the mean and probability density functions, are obtained for a weak compensation, while a simple characterisation of the effect indicates the need for stronger compensation. The SMR mean was found to be 1.89/2.62/4.10 g/m2 for no/selected/strongest compensation, respectively. Assumptions about the particle size distribution are a consideration for all three instruments, and constitute the dominating retrieval uncertainty for CloudSat. The comparison indicates a retrieval accuracy of about 40% (3.1±1.2 g/m2). This number is already very small compared to uncertainties of cloud ice parametrisation in atmospheric models, but can be decreased further through a better understanding of main retrieval error sources.
Ozone profile retrieval from limb scatter measurements in the HARTLEY bands: methodology, algorithm description, sensitivity studies, and validation
Authors: Rohen G. J. , Savigny C. v. , Kaiser J. W. , Llewellyn E. J. , Froidevaux L. , López-Puertas M. , Steck T. , Palm M. , Winkler H. , Burrows J. P. , Sinnhuber M. , Bovensmann H.
Published: April 2010

Abstract. SCIAMACHY limb scatter spectra have been used to retrieve atmospheric ozone profiles in the upper stratosphere and lower mesosphere. Through a selection of the wavelengths in the HARTLEY bands of ozone, profiles extending to 60 or 70 km altitude were retrieved. This constitutes the highest possible ozone profile information retrieval using the backscatter technique. Comparisons with profiles measured by a ground based radiometer in Norway, MIPAS on board ENVISAT, HALOE on UARS and MLS on AURA indicate a good agreement of the ozone profiles in the upper stratosphere within 10% but also an increasing overestimation above 50 to 55 km. Sensitivity studies show that solar zenith uncertainty and tangent height errors are the largest error sources. Although the tangent height is corrected through an own retrieval the correction seemed to be be worser with increasing altitude and remains therefore as the largest error source for this presented profile retrieval.
Chemical composition of free tropospheric aerosol for PM1 and coarse mode at the high alpine site Jungfraujoch
Authors: Cozic J. , Verheggen B. , Weingartner E. , Crosier J. , Bower K. , Flynn M. , Coe H. , Henning S. , Steinbacher M. , Collaud Coen M. , Petzold A. , Baltensperger U.
Published: April 2010

Abstract. The chemical composition of submicron (fine mode) and supermicron (coarse mode) aerosol particles has been investigated since 1999 within the GAW aerosol monitoring program at the high alpine research station Jungfraujoch (3580 m a.s.l., Switzerland). Clear seasonality was observed for all major components in the last 9 years with low concentrations in winter (predominantly free tropospheric aerosol) and higher concentrations in summer (enhanced vertical transport of boundary layer pollutants). In addition, mass closure was attempted during intensive experiments in March 2004, February–March 2005 and August 2005. Ionic, carbonaceous and refractory components of the aerosol were quantified as well as the PM1 and coarse mode total aerosol mass concentrations. A relatively low conversion factor of 1.8 for organic carbon (OC) to particulate organic matter (OM) in winter (February–March 2005) was found. Organics, sulfate, ammonium, and nitrate were the major identified components of the fine aerosol fraction, while calcium and nitrate were the two major measured components in the coarse mode. The aerosol mass concentrations for fine and coarse mode aerosol during the intensive campaigns were not typical of the long term seasonality due largely to dynamical differences. Average fine and coarse mode concentrations during the intensive field campaigns were 1.7 μg m−3 and 2.4 μg m−3 in winter and 2.5 μg m−3 and 2.0 μg m−3 in summer, respectively. The mass balance of aerosols showed higher contributions of calcium and nitrate in the coarse mode during Saharan dust events (SDE) than without SDE.
Changes in aerosol properties during spring-summer period in the Arctic troposphere
Authors: Engvall A.-C. , Krejci R. , Ström J. , Treffeisen R. , Scheele R. , Hermansen O. , Paatero J.
Published: April 2010

Abstract. The change in aerosol properties during the transition from the more polluted spring to the clean summer Arctic troposphere was studied. A six year data set of observations from Ny-Ålesund, Svalbard, covering the months April through June serve as the basis for the characterisation of this time period. In addition four-day-back trajectories were used to describe air mass histories. The observed transition in aerosol properties from an accumulation mode dominated to an Aitken mode dominated size distribution is discussed with respect to long-range transport and influences from natural and anthropogenic sources of aerosols and pertinent trace gases. Our study shows that the air-mass transport is an important factor modulating the physical and chemical properties observed. However, the air-mass transport cannot alone explain the yearly repeatable systematic and rather rapid change in aerosol properties, occurring within a limited time window of approximately 10 days. With a simplified phenomenological model, which delivers the nucleation potential for new particle formation, we suggest that the rapid shift in aerosol microphysical properties between the Arctic spring and summer is mainly driven by the incoming solar radiation in concert with transport of precursor gases and changes in condensational sink.
A strategy for climate evaluation of aircraft technology: an efficient climate impact assessment tool – AirClim
Authors: Grewe V. , Stenke A.
Published: April 2010

Abstract. Climate change is a challenge to society and to cope with requires assessment tools which are suitable to evaluate new technology options with respect to their impact on climate. Here we present AirClim, a model which comprises a linearisation of the processes occurring from the emission to an estimate in near surface temperature change, which is presumed to be a reasonable indicator for climate change. The model is designed to be applicable to aircraft technology, i.e.~the climate agents CO2, H2O, CH4 and O3 (latter two resulting from NOx-emissions) and contrails are taken into account. It employs a number of precalculated atmospheric data and combines them with aircraft emission data to obtain the temporal evolution of atmospheric concentration changes, radiative forcing and temperature changes. The linearisation is based on precalculated data derived from 25 steady-state simulations of the state-of-the-art climate-chemistry model E39/C, which include sustained normalised emissions at various atmospheric regions. The results show that strongest climate impacts from ozone changes occur for emissions in the tropical upper troposphere (60 mW/m²; 80 mK for 1 TgN emitted), whereas from methane in the middle tropical troposphere (–2.7% change in methane lifetime; –30 mK per TgN). The estimate of the temperature changes caused by the individual climate agents takes into account a perturbation lifetime, related to the region of emission. A comparison of this approach with results from the TRADEOFF and SCENIC projects shows reasonable agreement with respect to concentration changes, radiative forcing, and temperature changes. The total impact of a supersonic fleet on radiative forcing (mainly water vapour) is reproduced within 5%. For subsonic air traffic (sustained emissions after 2050) results show that although ozone-radiative forcing is much less important than that from CO2 for the year 2100. However the impact on temperature is of comparable size even when taking into account temperature decreases from CH4. That implies that all future measures for climate stabilisation should concentrate on both CO2 and NOx emissions. A direct comparison of super- with subsonic aircraft (250 passengers, 5400 nm) reveals a 5 times higher climate impact of supersonics.
Modelling the impact of sub-grid scale emission variability on upper-air concentration
Authors: Galmarini S. , Vinuesa J.-F. , Martilli A.
Published: April 2010

Abstract. The long standing issue of sub-grid emission heterogeneity and its influence to upper air concentration is addressed here and a subgrid model proposed. The founding concept of the approach is the assumption that average emission acts as source terms of average concentration, while emission fluctuations are source for the concentration variance. The model is based on the derivation of the sub-grid contribution of emission and the use of the concentration variance equation to transport it in the atmospheric boundary layer. The model has been implemented in an existing mesoscale model and the results compared with Large-Eddy Simulation data for ad-hoc simulation devised to test specifically the parametrization. The results show and excellent agreement of the models. For the first time a time evolving error bar reproducing the sub-grid scale heterogeneity of the emissions and the way in which it affects the concentration has been shown. The concentration variance is presented as an extra attribute to better define the mean concentrations in a Reynolds-average model. The model has applications from meso to global scale and that go beyond air quality.
On the attribution of stratospheric ozone and temperature changes to changes in ozone-depleting substances and well-mixed greenhouse gases
Authors: Shepherd T. G. , Jonsson A. I.
Published: April 2010

Abstract. The vertical profile of global-mean stratospheric temperature changes has traditionally represented an important diagnostic for the attribution of the cooling effects of stratospheric ozone depletion and CO2 increases. However, CO2-induced cooling alters ozone abundance by perturbing ozone chemistry, thereby coupling the stratospheric ozone-temperature response to changes in CO2 and ozone-depleting substances (ODSs). Here we untangle the ozone-temperature coupling and show that the attribution of global-mean stratospheric temperature changes to CO2 and ODS changes (which are the true anthropogenic forcing agents) can be quite different from the traditional attribution to CO2 and ozone changes. The significance of these effects is quantified empirically using simulations from a three-dimensional chemistry-climate model. The results confirm the essential validity of the traditional approach in attributing changes during the past period of rapid ODS increases, although we find that about 10% of the upper stratospheric ozone decrease from ODS increases over the period 1975–1995 was offset by the increase in CO2, and the CO2-induced cooling in the upper stratosphere has been somewhat overestimated. When considering ozone recovery, however, the ozone-temperature coupling is a first-order effect; fully 2/5 of the upper stratospheric ozone increase projected to occur from 2010–2040 is attributable to CO2 increases. Thus, it has now become necessary to base attribution of global-mean stratospheric temperature changes on CO2 and ODS changes rather than on CO2 and ozone changes.