bluuebunny/crossref_metadata_2025 huggingface dataset:
Laboratory studies of H2SO4/H2O binary homogeneous nucleation from the SO2+OH reaction: evaluation of the experimental setup and preliminary results
Authors: Young L. H. , Benson D. R. , Kameel F. R. , Pierce J. R. , Junninen H. , Kulmala M. , Lee S.-H.
Published: April 2010

Abstract. Binary homogeneous nucleation (BHN) of sulphuric acid and water (H2SO4/H2O) is one of the most important atmospheric nucleation processes, but laboratory observations of this nucleation process are very limited and there are also large discrepancies between different laboratory studies. The difficulties associated with these experiments include wall loss of H2SO4 and uncertainties in estimation of H2SO4 concentration ([H2SO4]) involved in nucleation. We have developed a new laboratory nucleation setup to study H2SO4/H2O BHN kinetics and provide relatively constrained [H2SO4] needed for nucleation. H2SO4 is produced from the SO2+OH→HSO3 reaction and OH radicals are produced from water vapor UV absorption. The residual [H2SO4] were measured at the end of the nucleation reactor with a chemical ionization mass spectrometer (CIMS). Wall loss factors (WLFs) of H2SO4 were estimated by assuming that wall loss is diffusion limited and these calculated WLFs were in good agreement with simultaneous measurements of the initial and residual [H2SO4] with two CIMSs. The nucleation zone was estimated from numerical simulations based on the measured aerosol sizes (particle diameter, Dp) and [H2SO4]. The measured BHN rates (J) ranged from 0.01–220 cm−3 s−1 at the initial and residual [H2SO4] from 108−1010 cm−3, a temperature of 288 K and relative humidity (RH) from 11–23%; J increased with increasing [H2SO4] and RH. J also showed a power dependence on [H2SO4] with the exponential power of 3–8. These power dependences are consistent with other laboratory studies under similar [H2SO4] and RH, but different from atmospheric field observations which showed that particle number concentrations are often linearly dependent on [H2SO4]. These results, together with a higher [H2SO4] threshold (108–109 cm−3) needed to produce the unit J measured from the laboratory studies compared to the atmospheric conditions (106–107 cm−3), imply that H2SO4/H2O BHN alone is insufficient to explain atmospheric aerosol formation and growth. Particle growth rates estimated from the measured aerosol size distributions, residence times (tr), and [H2SO4] were 100–500 nm h−1, much higher than those seen from atmospheric field observations, because of the higher [H2SO4] used in our study.
Repeatability and randomness in heterogeneous freezing nucleation
Authors: Vali G.
Published: April 2010

Abstract. This study is aimed at clarifying the relative importance of the specific character of the nuclei and of the duration of supercooling in heterogeneous freezing nucleation by immersed impurities. Laboratory experiments were carried out in which sets of water drops underwent multiple cycles of freezing and melting. The drops contained suspended particles of mixtures of materials; the resulting freezing temperatures ranged from −6°C to −24°C. Rank correlation coefficients between observed freezing temperatures of the drops in successive runs were >0.9 with very high statistical significance, and thus provide strong support for the modified singular model of heterogeneous immersion freezing nucleation. For given drops, changes in freezing temperatures between cycles were relatively small (<1°C) for the majority of the events. These frequent small fluctuations in freezing temperatures are interpreted as reflections of the random nature of embryo growth and are associated with a nucleation rate that is a function of a temperature difference from the characteristic temperatures of nuclei. About a sixth of the changes were larger, up to ±5°C, and exhibited some systematic patterns. These are thought to arise from alterations of the nuclei, some being permanent and some transitory. The results are used to suggest ways of describing ice initiation in cloud models that account for both the temperature and the time dependence of freezing nucleation.
What can 14CO measurements tell us about OH?
Authors: Krol M. C. , Meirink J. F. , Bergamaschi P. , Mak J. E. , Lowe D. , Jöckel P. , Houweling S. , Röckmann T.
Published: April 2010

Abstract. The possible use of 14CO measurements to constrain hydroxyl radical (OH) concentrations in the atmosphere is investigated. 14CO is mainly produced in the upper atmosphere from cosmic radiation. Measurements of 14CO at the surface show lower concentrations compared to the upper atmospheric source region, which is the result of oxidation by OH. In this paper, the sensitivity of 14CO mixing ratio surface measurements to the 3-D OH distribution is assessed with the TM5 model. Simulated 14CO mixing ratios agree within a few molecules 14CO cm−3 (STP) with existing measurements at five locations worldwide. The simulated cosmogenic 14CO distribution appears mainly sensitive to the assumed upper atmospheric 14C source function, and to a lesser extend to model resolution. As a next step, the sensitivity of 14CO measurements to OH is calculated with the adjoint TM5 model. The results indicate that 14CO measurements taken in the tropics are sensitive to OH in a spatially confined region that varies strongly over time due to meteorological variability. Given measurements with an accuracy of 0.5 molecules 14CO cm−3 STP, a good characterization of the cosmogenic 14CO fraction, and assuming perfect transport modeling, a single 14CO measurement may constrain OH to 0.2–0.3×106 molecules OH cm−3 on time scales of 6 months and spatial scales of 70×70 degrees (latitude×longitude) between the surface and 500 hPa. The sensitivity of 14CO measurements to high latitude OH is about a factor of five higher. This is in contrast with methyl chloroform (MCF) measurements, which show the highest sensitivity to tropical OH, mainly due to the temperature dependent rate constant of the MCF–OH reaction. A logical next step will be the analysis of existing 14CO measurements in an inverse modeling framework. This paper presents the required mathematical framework for such an analysis.
Technical Note: Molecular characterization of aerosol-derived water soluble organic carbon using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry
Authors: Wozniak A. S. , Bauer J. E. , Sleighter R. L. , Dickhut R. M. , Hatcher P. G.
Published: April 2010

Abstract. Despite the acknowledged relevance of aerosol-derived water-soluble organic carbon (WSOC) to climate and biogeochemical cycling, characterization of aerosol WSOC has been limited. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was utilized in this study to provide detailed molecular level characterization of the high molecular weight (HMW; m/z>223) component of aerosol-derived WSOC collected from rural sites in Virginia and New York, USA. More than 3000 peaks were detected by ESI FT-ICR MS within a m/z range of 223–600 for each sample. Approximately 86% (Virginia) and 78% (New York) of these peaks were assigned molecular formulas using only carbon (C), hydrogen (H), oxygen (O), nitrogen (N), and sulfur (S) as elemental constituents. H/C and O/C molar ratios were plotted on van Krevelen diagrams and indicated a strong contribution of lignin-like and lipid-like compounds to the aerosol-derived WSOC samples. Approximately 1–4% of the peaks in the aerosol-derived WSOC mass spectra were classified as black carbon (BC) on the basis of double bond equivalents calculated from the assigned molecular formulas. In addition, several high-magnitude peaks in the mass spectra of samples from both sites corresponded to molecular formulas proposed in previous secondary organic aerosol (SOA) laboratory investigations indicating that SOAs are important constituents of the WSOC. Overall, ESI FT-ICR MS provides a level of resolution adequate for detailed compositional and source information of the HMW constituents of aerosol-derived WSOC.
Towards improving the simulation of meteorological fields in urban areas through updated/advanced surface fluxes description
Authors: Baklanov A. , Mestayer P. G. , Clappier A. , Zilitinkevich S. , Joffre S. , Mahura A. , Nielsen N. W.
Published: April 2010

Abstract. The increased resolution of numerical weather prediction models allows nowadays addressing more realistically urban meteorology and air pollution processes. This has triggered new interest in modelling and describing experimentally the specific features and processes of urban areas. Recent developments and results performed within the EU-funded project FUMAPEX on integrated systems for forecasting urban meteorology and air pollution are reported here. Sensitivity studies with respect to optimum resolution, parametrisation of urban roughness and surface exchange fluxes and the role of urban soil layers are carried out with advanced meso- or sub-meso meteorological models. They show that sensible improvements can be achieved by higher model resolution that is accompanied with better description of urban surface features. Recommendations, especially with respect to advanced urban air quality forecasting and information systems, are given together with an assessment of the needed further research and data.
A multi-model assessment of pollution transport to the Arctic
Authors: Shindell D. T. , Chin M. , Dentener F. , Doherty R. M. , Faluvegi G. , Fiore A. M. , Hess P. , Koch D. M. , MacKenzie I. A. , Sanderson M. G. , Schultz M. G. , Schulz M. , Stevenson D. S. , Teich H. , Textor C. , Wild O. , Bergmann D. J. , Bey I. , Bian H. , Cuvelier C. , Duncan B. N. , Folberth G. , Horowitz L. W. , Jonson J. , Kaminski J. W. , Marmer E. , Park R. , Pringle K. J. , Schroeder S. , Szopa S. , Takemura T. , Zeng G. , Keating T. J. , Zuber A.
Published: April 2010

Abstract. We examine the response of Arctic gas and aerosol concentrations to perturbations in pollutant emissions from Europe, East and South Asia, and North America using results from a coordinated model intercomparison. These sensitivities to regional emissions (mixing ratio change per unit emission) vary widely across models and species. Intermodel differences are systematic, however, so that the relative importance of different regions is robust. North America contributes the most to Arctic ozone pollution. For aerosols and CO, European emissions dominate at the Arctic surface but East Asian emissions become progressively more important with altitude, and are dominant in the upper troposphere. Sensitivities show strong seasonality: surface sensitivities typically maximize during boreal winter for European and during spring for East Asian and North American emissions. Mid-tropospheric sensitivities, however, nearly always maximize during spring or summer for all regions. Deposition of black carbon (BC) onto Greenland is most sensitive to North American emissions. North America and Europe each contribute ~40% of total BC deposition to Greenland, with ~20% from East Asia. Elsewhere in the Arctic, both sensitivity and total BC deposition are dominated by European emissions. Model diversity for aerosols is especially large, resulting primarily from differences in aerosol physical and chemical processing (including removal). Comparison of modeled aerosol concentrations with observations indicates problems in the models, and perhaps, interpretation of the measurements. For gas phase pollutants such as CO and O3, which are relatively well-simulated, the processes contributing most to uncertainties depend on the source region and altitude examined. Uncertainties in the Arctic surface CO response to emissions perturbations are dominated by emissions for East Asian sources, while uncertainties in transport, emissions, and oxidation are comparable for European and North American sources. At higher levels, model-to-model variations in transport and oxidation are most important. Differences in photochemistry appear to play the largest role in the intermodel variations in Arctic ozone sensitivity, though transport also contributes substantially in the mid-troposphere.
Surface observation of sand and dust storm in East Asia and its application in CUACE/Dust
Authors: Wang Y. Q. , Zhang X. Y. , Gong S. L. , Zhou C. H. , Hu X. Q. , Liu H. L. , Niu T. , Yang Y. Q.
Published: April 2010

Abstract. The spatial-temporal distributions and sources of sand and dust storm (SDS) in East Asia from 2001 to 2006 were investigated on the basis of visibility and PM10 data from the routine SDS and weather monitoring networks run by CMA (China Meteorological Administration). A power functional relationships between PM10 and visibility was found among various regions generally with a good correlation (r2=0.90), especially in Asian SDS source regions. In addition, three SDS occurrence centers, i.e. western China, Mongolia and northern China, were identified with the Mongolia source contributing more dust to the downwind areas including Korea and Japan than other two sources. Generally, high PM10 concentrations were observed in most areas of northern China. The highest value was obtained in the center of western China with a spring daily mean value of 876 μgm−3, and the value in other source regions exceeds 200 μgm−3. These data sets together with the satellite observations in China form the main observation database for the evaluation and data assimilation of CUACE/Dust system – an operational SDS forecasting system for East Asia.
Comprehensive airborne characterization of aerosol from a major bovine source
Authors: Sorooshian A. , Murphy S. M. , Hersey S. , Gates H. , Padro L. T. , Nenes A. , Brechtel F. J. , Jonsson H. , Flagan R. C. , Seinfeld J. H.
Published: April 2010

Abstract. We report an extensive airborne characterization of aerosol downwind of a massive bovine source in the San Joaquin Valley (California) on two flights during July 2007. The Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter probed chemical composition, particle size distribution, mixing state, sub- and supersaturated water uptake behavior, light scattering properties, and the interrelationship between these parameters and meteorology. Total PM1.0 levels and concentrations of organics, nitrate, and ammonium were enhanced in the plume from the source as compared to the background aerosol. Organics dominated the plume aerosol mass (~56–64%), followed either by sulfate or nitrate, and then ammonium. Particulate amines were detected in the plume aerosol by a particle-into-liquid sampler (PILS) and via mass spectral markers in the Aerodyne C-ToF-AMS. Amines were found to be a significant atmospheric base even in the presence of ammonia; particulate amine concentrations are estimated as at least 14–23% of that of ammonium in the plume. Enhanced sub- and supersaturated water uptake and reduced refractive indices were coincident with lower organic mass fractions, higher nitrate mass fractions, and the detection of amines. The likelihood of suppressed droplet growth owing to kinetic limitations from hydrophobic organic material is explored. After removing effects associated with size distribution and mixing state, the normalized activated fraction of cloud condensation nuclei (CCN) increased as a function of the subsaturated hygroscopic growth factor, with the highest activated fractions being consistent with relatively lower organic mass fractions and higher nitrate mass fractions. Subsaturated hygroscopic growth factors for the organic fraction of the aerosol are estimated based on employing the Zdanovskii-Stokes Robinson (ZSR) mixing rule. Representative values for a parameterization treating particle water uptake in both the sub- and supersaturated regimes are reported for incorporation into atmospheric models.
Comparison of ground-based Brewer and FTIR total column O3 monitoring techniques
Authors: Schneider M. , Redondas A. , Hase F. , Guirado C. , Blumenstock T. , Cuevas E.
Published: April 2010

Abstract. We compare the currently most precise, ground-based total O3 measurement techniques: Brewer and FTIR. We give an overview of the similarities and the differences between the measurements and the retrieval approaches of both experiments. We compare coincident measurements performed at the Atmospheric Observatory of Izaña from 2005 to 2007 and demonstrate that, if the properties of the instruments are well characterised, the scatter between both experiments is as small as 0.5%. This is in agreement with the theoretical predictions and confirms empirically that both techniques are able to monitor total O3 amounts with a precision of better than 0.4%. However, we found systematic differences between both techniques of around 4.5%, which we think are mainly due to discrepancies between the applied UV and infrared spectroscopic parameters.
Quality assessment of O3 profiles measured by a state-of-the-art ground-based FTIR observing system
Authors: Schneider M. , Hase F. , Blumenstock T. , Redondas A. , Cuevas E.
Published: April 2010

Abstract. Ground-based Fourier Transform Infra-Red (FTIR) measurements are an important component of the global atmospheric monitoring system. Their essential role in validating satellite measurements requires a precise documentation of their quality. Here we present an extensive quality documentation of ground-based FTIR O3 profiles. This is done in the form of theoretical and empirical error estimations. The latter is achieved by an intercomparison with ECC-sonde O3 profiles. The FTIR O3 amounts are obtained by applying the most advanced instrumentation and retrieval strategies and consequently represent the current potential of this remote sensing technique.
Quantitative performance metrics for stratospheric-resolving chemistry-climate models
Authors: Waugh D. W. , Eyring V.
Published: April 2010

Abstract. A set of performance metrics is applied to stratospheric-resolving chemistry-climate models (CCMs) to quantify their ability to reproduce key processes relevant for stratospheric ozone. The same metrics are used to assign a quantitative measure of performance ("grade") to each model-observations comparison shown in Eyring et al. (2006). A wide range of grades is obtained, both for different diagnostics applied to a single model and for the same diagnostic applied to different models, highlighting the wide range in ability of the CCMs to simulate key processes in the stratosphere. No model scores high or low on all tests, but differences in the performance of models can be seen, especially for processes that are mainly determined by transport where several models get low grades on multiple tests. The grades are used to assign relative weights to the CCM projections of 21st century total ozone. For the diagnostics used here there are generally only small differences between weighted and unweighted multi-model mean and variances of total ozone projections. This study raises several issues with the grading and weighting of CCMs that need further examination. However, it does provide a framework and benchmarks that will enable quantification of model improvements and assignment of relative weights to the model projections.
Mesospheric N2O enhancements as observed by MIPAS on Envisat during the polar winters in 2002–2004
Authors: Funke B. , López-Puertas M. , Garcia-Comas M. , Stiller G. P. , von Clarmann T. , Glatthor N.
Published: April 2010

Abstract. N2O abundances ranging from 0.5 to 6 ppbv were observed in the polar upper stratosphere/lower mesosphere by the MIPAS instrument on the Envisat satellite during the Arctic and Antarctic winters in the period July 2002 to March 2004. A detailed study of the observed N2O-CH4 correlations shows that such enhancements cannot be explained by dynamics without invoking an upper atmospheric chemical source of N2O. The N2O enhancements observed at 58 km occurred in the presence of NOx intrusions from the upper atmosphere which were related to energetic particle precipitation. Further, the inter-annual variability of mesospheric N2O correlates well with observed precipitating electron fluxes. The analysis of possible chemical production mechanisms shows that the major part of the observed N2O enhancements is most likely generated under dark conditions by the reaction of NO2 with atomic nitrogen at altitudes around 70–75 km in the presence of energetic particle precipitation (EPP). A possible additional source of N2O in the middle and upper polar atmosphere is the reaction of N2(A3Σu+), generated by precipitating electrons, with O2, which would lead to N2O production peaking at altitudes around 90–100 km. N2O produced by the latter mechanism could then descend to the mesosphere and upper stratosphere during polar winter. The estimated fraction of EPP-generated N2O to the total stratospheric N2O inside the polar vortex above 20 km (30 km) never exceeds 1% (10%) during the 2002–2004 winters. Compared to the global amount of stratospheric N2O, the EPP-generated contribution is negligible.
LACIS-measurements and parameterization of sea-salt particle hygroscopic growth and activation
Authors: Niedermeier D. , Wex H. , Voigtländer J. , Stratmann F. , 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. The measurements showed that the sea-salt particles exhibit a slightly reduced hygroscopic growth compared to pure NaCl particles. 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: 0.11%, 0.17% and 0.32%. 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.
Validation of NO2 and NO from the Atmospheric Chemistry Experiment (ACE)
Authors: Kerzenmacher T. , Wolff M. A. , Strong K. , Dupuy E. , Walker K. A. , Amekudzi L. K. , Batchelor R. L. , Bernath P. F. , Berthet G. , Blumenstock T. , Boone C. D. , Bramstedt K. , Brogniez C. , Brohede S. , Burrows J. P. , Catoire V. , Dodion J. , Drummond J. R. , Dufour D. G. , Funke B. , Fussen D. , Goutail F. , Griffith D. W. T. , Haley C. S. , Hendrick F. , Höpfner M. , Huret N. , Jones N. , Kar J. , Kramer I. , Llewellyn E. J. , López-Puertas M. , Manney G. , McElroy C. T. , McLinden C. A. , Melo S. , Mikuteit S. , Murtagh D. , Nichitiu F. , Notholt J. , Nowlan C. , Piccolo C. , Pommereau J.-P. , Randall C. , Raspollini P. , Ridolfi M. , Richter A. , Schneider M. , Schrems O. , Silicani M. , Stiller G. P. , Taylor J. , Tétard C. , Toohey M. , Vanhellemont F. , Warneke T. , Zawodny J. M. , Zou J.
Published: April 2010

Abstract. Vertical profiles of NO2 and NO have been obtained from solar occultation measurements by the Atmospheric Chemistry Experiment (ACE), using an infrared Fourier Transform Spectrometer (ACE-FTS) and (for NO2) an ultraviolet-visible-near-infrared spectrometer, MAESTRO (Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation). In this paper, the quality of the ACE-FTS version 2.2 NO2 and NO and the MAESTRO version 1.2 NO2 data are assessed using other solar occultation measurements (HALOE, SAGE II, SAGE III, POAM III, SCIAMACHY), stellar occultation measurements (GOMOS), limb measurements (MIPAS, OSIRIS), nadir measurements (SCIAMACHY), balloon-borne measurements (SPIRALE, SAOZ) and ground-based measurements (UV-VIS, FTIR). Time differences between the comparison measurements were reduced using either a tight coincidence criterion, or where possible, chemical box models. ACE-FTS NO2 and NO and the MAESTRO NO2 are generally consistent with the correlative data. The ACE-FTS and MAESTRO NO2 volume mixing ratio (VMR) profiles agree with the profiles from other satellite data sets to within about 20% between 25 and 40 km, with the exception of MIPAS ESA (for ACE-FTS) and SAGE II (for ACE-FTS (sunrise) and MAESTRO) and suggest a negative bias between 23 and 40 km of about 10%. MAESTRO reports larger VMR values than the ACE-FTS. In comparisons with HALOE, ACE-FTS NO VMRs typically (on average) agree to ±8% from 22 to 64 km and to +10% from 93 to 105 km, with maxima of 21% and 36%, respectively. Partial column comparisons for NO2 show that there is quite good agreement between the ACE instruments and the FTIRs, with a mean difference of +7.3% for ACE-FTS and +12.8% for MAESTRO.
Vertical mixing in atmospheric tracer transport models: error characterization and propagation
Authors: Gerbig C. , Körner S. , Lin J. C.
Published: April 2010

Abstract. Imperfect representation of vertical mixing near the surface in atmospheric transport models leads to uncertainties in modelled tracer mixing ratios. When using the atmosphere as an integrator to derive surface-atmosphere exchange from mixing ratio observations made in the atmospheric boundary layer, this uncertainty has to be quantified and taken into account. A comparison between radiosonde-derived mixing heights and mixing heights derived from ECMWF meteorological data during May–June 2005 in Europe revealed random discrepancies of about 40% for the daytime with insignificant bias errors, and much larger values approaching 100% for nocturnal mixing layers with bias errors also exceeding 50%. The Stochastic Time Inverted Lagrangian Transport (STILT) model was used to propagate this uncertainty into CO2 mixing ratio uncertainties, accounting for spatial and temporal error covariance. Average values of 3 ppm were found for the 2 month period, indicating that this represents a large fraction of the overall uncertainty. A pseudo data experiment shows that the error propagation with STILT avoids biases in flux retrievals when applied in inversions. The results indicate that flux inversions employing transport models based on current generation meteorological products have misrepresented an important part of the model error structure likely leading to biases in the estimated mean and uncertainties. We strongly recommend including the solution presented in this work: better, higher resolution atmospheric models, a proper description of correlated random errors, and a modification of the overall sampling strategy.
Attenuation of concentration fluctuations of water vapor and other trace gases in turbulent tube flow
Authors: Massman W. J. , Ibrom A.
Published: April 2010

Abstract. Recent studies with closed-path eddy covariance (EC) systems have indicated that the attenuation of fluctuations of water vapor concentration is dependent upon ambient relative humidity, presumably due to sorption/desorption of water molecules at the interior surface of the tube. Previous studies of EC-related tube attenuation effects have either not considered this issue at all or have only examined it superficially. Nonetheless, the attenuation of water vapor fluctuations is clearly much greater than might be expected from a passive tracer in turbulent tube flow. This study reexamines the turbulent tube flow issue for both passive and sorbing tracers with the intent of developing a physically-based semi-empirical model that describes the attenuation associated with water vapor fluctuations. Toward this end, we develop a new model of tube flow dynamics (radial profiles of the turbulent diffusivity and tube airstream velocity). We compare our new passive-tracer formulation with previous formulations in a systematic and unified way in order to assess how sensitive the passive-tracer results depend on fundamental modeling assumptions. We extend the passive tracer model to the vapor sorption/desorption case by formulating the model's wall boundary condition in terms of a physically-based semi-empirical model of the sorption/desorption vapor fluxes. Finally we synthesize all modeling and observational results into a single analytical expression that captures the effects of the mean ambient humidity and tube flow (Reynolds number) on tube attenuation.
Observations of iodine monoxide columns from satellite
Authors: Schönhardt A. , Richter A. , Wittrock F. , Kirk H. , Oetjen H. , Roscoe H. K. , Burrows J. P.
Published: April 2010

Abstract. Iodine species in the troposphere are linked to ozone depletion and new particle formation. In this study, a full year of iodine monoxide (IO) columns retrieved from measurements of the SCIAMACHY satellite instrument is presented, coupled with a discussion of their uncertainties and the detection limits. The largest amounts of IO are found near springtime in the Antarctic. A seasonal variation of iodine monoxide in Antarctica is revealed with high values in springtime, slightly less IO in the summer period and again larger amounts in autumn. In winter, no elevated IO levels are found in the areas accessible to satellite measurements. This seasonal cycle is in good agreement with recent ground-based measurements in Antarctica. In the Arctic region, no elevated IO levels were found in the period analysed. This implies that different conditions with respect to iodine release exist in the two Polar Regions. To investigate possible release mechanisms, comparisons of IO columns with those of tropospheric BrO, and ice coverage are described and discussed. Some parallels and interesting differences between IO and BrO temporal and spatial distributions are identified. Overall, the large spatial coverage of satellite retrieved IO data and the availability of a long-term dataset provide new insight about the abundances and distributions of iodine compounds in the troposphere.
Airborne in-situ measurements of vertical, seasonal and latitudinal distributions of carbon dioxide over Europe
Authors: Gurk Ch. , Fischer H. , Hoor P. , Lawrence M. G. , Lelieveld J. , Wernli H.
Published: April 2010

Abstract. Airborne in-situ observations of carbon dioxide (CO2) were made during 7 intensive measurement campaigns between November 2001 and April 2003 as part of the SPURT project. Vertical profiles and latitudinal gradients in the upper troposphere/lowermost stratosphere were measured along the western shore of Europe from the subtropics to high northern latitudes during different seasons. In the boundary layer, CO2 exhibits a strong seasonal cycle with the maximum mixing ratios in winter and minimum values in summer, reflecting the strength of CO2 exchange with vegetation. Seasonal variations are strongest in high latitudes and propagate to the free troposphere and lowermost stratosphere, although with reduced amplitude. In the lowermost stratosphere, the CO2 seasonal cycle is phase-shifted relative to the free troposphere by approximately 3 months, with highest mixing ratios during the summer. Modelling studies support the interpretation that altitude gradients of CO2 are likely due to stratosphere-troposphere-transport.
Redox activity and chemical speciation of size fractioned PM in the communities of the Los Angeles-Long Beach harbor
Authors: Hu S. , Polidori A. , Arhami M. , Shafer M. M. , Schauer J. J. , Cho A. , Sioutas C.
Published: April 2010

Abstract. In this study, two different types of assays were used to quantitatively measure the redox activity of PM and to examine its intrinsic toxicity: 1) in vitro exposure to rat alveolar macrophage (AM) cells using dichlorofluorescin diacetate (DCFH-DA) as the fluorescent probe (macrophage ROS assay), and: 2) consumption of dithiothreitol (DTT) in a cell-free system (DTT assay). Coarse (PM10–2.5), accumulation (PM2.5–0.25), and quasi-ultrafine (quasi-UF, PM0.25) mode particles were collected weekly at five sampling sites in the Los Angeles-Long Beach harbor and at one site near the University of Southern California campus (urban site). All PM samples were analyzed for organic (total and water-soluble) and elemental carbon, organic species, inorganic ions, and total and water-soluble elements. Quasi-UF mode particles showed the highest redox activity at all Long Beach sites (on both a per-mass and per-air volume basis). A significant association (R2=0.61) was observed between the two assays, indicating that macrophage ROS and DTT levels are affected at least partially by similar PM species. Relatively small variation was observed for the DTT measurements across all size fractions and sites, whereas macrophage ROS levels showed more significant ranges across the three different particle size modes and throughout the sites (coefficients of variation, or CVs, were 0.35, 0.24 and 0.53 for quasi-UF, accumulation, and coarse mode particles, respectively). Association between the PM constituents and the redox activity was further investigated using multiple linear regression models. The results showed that OC was the most important component influencing the DTT activity of PM samples. The variability of macrophage ROS was explained by changes in OC concentrations and water-soluble vanadium (probably originating from ship emissions – bunker oil combustion). The multiple regression models were used to predict the average diurnal DTT levels as a function of the OC concentration at one of the sampling sites.
The travel-related carbon dioxide emissions of atmospheric researchers
Authors: Stohl A.
Published: April 2010

Abstract. Most atmospheric scientists agree that greenhouse gas emissions have already caused significant changes to the global climate system and that these changes will accelerate in the near future. At the same time, atmospheric scientists who – like other scientists – rely on international collaboration and information exchange travel a lot and, thereby, cause substantial emissions of CO2. In this paper, the CO2 emissions of the employees working at an atmospheric research institute (the Norwegian Institute for Air Research, NILU) caused by all types of business travel (conference visits, workshops, field campaigns, instrument maintainance, etc.) were calculated for the years 2005–2007. It is estimated that more than 90% of the emissions were caused by air travel, 3% by ground travel and 5% by hotel usage. The travel-related annual emissions were between 1.9 and 2.4 t CO2 per employee or between 3.9 and 5.5 t CO2 per scientist. For comparison, the total annual per capita CO2 emissions are 4.5 t worldwide, 1.2 t for India, 3.8 t for China, 5.9 t for Sweden and 19.1 t for Norway. The travel-related CO2 emissions of a NILU scientist, occurring in 24 days of a year on average, exceed the global average annual per capita emission. Norway's per-capita CO2 emissions are among the highest in the world, mostly because of the emissions from the oil industry. If the emissions per NILU scientist derived in this paper are taken as representative for the average Norwegian researcher, travel by Norwegian scientists would nevertheless account for a substantial 0.2% of Norway's total CO2 emissions. Since most of the travel-related emissions are due to air travel, water vapor emissions, ozone production and contrail formation further increase the relative importance of NILU's travel in terms of radiative forcing.
Variation and balance of positive air ion concentrations in a boreal forest
Authors: Hõrrak U. , Aalto P. P. , Salm J. , Komsaare K. , Tammet H. , Mäkelä J. M. , Laakso L. , Kulmala M.
Published: April 2010

Abstract. Air ions are characterized on the basis of measurements carried out in a boreal forest at the Hyytiälä SMEAR station, Finland, during the BIOFOR III campaign in spring 1999. The air ions were discriminated as small ions (charged molecular aggregates of the diameter of less than 2.5 nm), intermediate ions (charged aerosol particles of the diameter of 2.5–8 nm), and large ions (charged aerosol particles of the diameter of 8–20 nm). Statistical characteristics of the ion concentrations and the parameters of ion balance in the atmosphere are presented separately for the nucleation event days and non-event days. In the steady state, the ionization rate is balanced with the loss of small ions, which is expressed as the product of the small ion concentration and the ion sink rate. The widely known sinks of small ions are the recombination with small ions of opposite polarity and attachment to aerosol particles. The dependence of small ion concentration on the concentration of aerosol particles was investigated applying a model of the bipolar diffusion charging of particles by small ions. When the periods of relative humidity above 95% and wind speed less than 0.6 m s−1 were excluded, then the small ion concentration and the theoretically calculated small ion sink rate were closely negatively correlated (correlation coefficient −87%). However, an extra ion loss term of the same magnitude as the ion loss onto aerosol particles is needed for a quantitative explanation of the observations. This term is presumably due to the small ion deposition on coniferous forest. The hygroscopic growth correction of the measured aerosol particle size distributions was also found to be necessary for the proper estimation of the ion sink rate. In the case of nucleation burst events, the concentration of small positive ions followed the general balance equation, no extra ion loss in addition to the deposition on coniferous forest was detected, and the hypothesis of the conversion of ions into particles in the process of ion-induced nucleation was not proved. The estimated average ionization rate of the air at the Hyytiälä station in early spring, when the ground was partly covered with snow, was about 6 ion pairs cm−3 s−1. The study of the charging state of nanometer aerosol particles (diameter 2.5–8 nm) in the atmosphere revealed a strong correlation (correlation coefficient 88%) between the concentrations of particles neutralized in the aerosol spectrometer and naturally positively charged particles (air ions) during nucleation bursts. The charged fraction of particles varied from 3% to 6% in accordance with the hypothesis that the particles are quasi-steady state charged.
Diurnal variations in the UV albedo of arctic snow
Authors: Meinander O. , Kontu A. , Lakkala K. , Heikkilä A. , Ylianttila L. , Toikka M.
Published: April 2010

Abstract. The relevance of snow for climate studies is based on its physical properties, such as high surface reflectivity. Surface ultraviolet (UV) albedo is an essential parameter for various applications based on radiative transfer modeling. Here, new continuous measurements of the local UV albedo of natural Arctic snow were made at Sodankylä (67°22'N, 26°39'E, 179 m a.s.l.) during the spring of 2007. The data were logged at 1-min intervals. The accumulation of snow was up to 68 cm. The surface layer thickness varied from 0.5 to 35 cm with the snow grain size between 0.2 and 2.5 mm. The midday erythemally weighted UV albedo ranged from 0.6 to 0.8 in the accumulation period, and from 0.5 to 0.7 during melting. During the snow melt period, under cases of an almost clear sky and variable cloudiness, an unexpected diurnal decrease of 0.05 in albedo soon after midday, and recovery thereafter, was detected. This diurnal decrease in albedo was found to be asymmetric with respect to solar midday, thus indicating a change in the properties of the snow. Independent UV albedo results with two different types of instruments confirm these findings. The measured temperature of the snow surface was below 0°C on the following mornings. Hence, the reversible diurnal change, evident for ~1–2 h, could be explained by the daily metamorphosis of the surface of the snowpack, in which the temperature of the surface increases, melting some of the snow to liquid water, after which the surface freezes again.
FRESCO+: an improved O2 A-band cloud retrieval algorithm for tropospheric trace gas retrievals
Authors: Wang P. , Stammes P. , van der A R. , Pinardi G. , van Roozendael M.
Published: April 2010

Abstract. The FRESCO (Fast Retrieval Scheme for Clouds from the Oxygen A-band) algorithm has been used to retrieve cloud information from measurements of the O2 A-band around 760 nm by GOME, SCIAMACHY and GOME-2. The cloud parameters retrieved by FRESCO are the effective cloud fraction and cloud pressure, which are used for cloud correction in the retrieval of trace gases like O3 and NO2. To improve the cloud pressure retrieval for partly cloudy scenes, single Rayleigh scattering has been included in an improved version of the algorithm, called FRESCO+. We compared FRESCO+ and FRESCO effective cloud fractions and cloud pressures using simulated spectra and one month of GOME measured spectra. As expected, FRESCO+ gives more reliable cloud pressures over partly cloudy pixels. Simulations and comparisons with ground-based radar/lidar measurements of clouds show that the FRESCO+ cloud pressure is about the optical midlevel of the cloud. Globally averaged, the FRESCO+ cloud pressure is about 50 hPa higher than the FRESCO cloud pressure, while the FRESCO+ effective cloud fraction is about 0.01 larger. The effect of FRESCO+ cloud parameters on O3 and NO2 vertical column density (VCD) retrievals is studied using SCIAMACHY data and ground-based DOAS measurements. We find that the FRESCO+ algorithm has a significant effect on tropospheric NO2 retrievals but a minor effect on total O3 retrievals. The retrieved SCIAMACHY tropospheric NO2 VCDs using FRESCO+ cloud parameters (v1.1) are lower than the tropospheric NO2VCDs which used FRESCO cloud parameters (v1.04), in particular over heavily polluted areas with low clouds. The difference between SCIAMACHY tropospheric NO2 VCDs v1.1 and ground-based MAXDOAS measurements performed in Cabauw, The Netherlands, during the DANDELIONS campaign is about −2.12×1014molec cm−2.
Measurements of UV aerosol optical depth in the French Southern Alps
Authors: Lenoble J. , Brogniez C. , de La Casinière A. , Cabot T. , Buchard V. , Guirado F.
Published: April 2010

Abstract. Routine measurements of global and diffuse UV irradiances at Briançon station (1310 m a.s.l.) are used to retrieve the direct solar irradiance and the aerosol optical depth (AOD), for cloudless days. Data of three years (2003, 2004, 2005) are analyzed; the results confirm those of a preliminary analysis for 2001, 2002. The atmosphere is very clear in winter, with AODs between 0.05 and 0.1. The turbidity increases slowly in spring, starting end of February, with AODs around 0.2–0.3 in mid summer, some values reaching 0.4. A similar behaviour is observed for all years, with somewhat higher values in late summer for the year 2003.
Statistical analysis of water vapour and ozone in the UT/LS observed during SPURT and MOZAIC
Authors: Kunz A. , Schiller C. , Rohrer F. , Smit H. G. J. , Nedelec P. , Spelten N.
Published: April 2010

Abstract. A statistical analysis for the comparability of water (H2O) and ozone (O3) data sets sampled during the SPURT aircraft campaigns and the MOZAIC passenger aircraft flights is presented. The Kolmogoroff-Smirnoff test reveals that the distribution functions from SPURT and MOZAIC trace gases differ from each other with a confidence of 95%. A variance analysis shows a different variability character in both trace gas data sets. While the SPURT H2O data only contain atmospheric processes variable on a diurnal or synoptical timescale, MOZAIC H2O data also reveal processes, which vary on inter-seasonal and seasonal timescales. The SPURT H2O data set does not represent the full MOZAIC H2O variance in the UT/LS for climatological investigations, whereas the variance of O3 is much better represented. SPURT H2O data are better suited in the stratosphere, where the MOZAIC RH sensor looses its sensitivity.
Steady-state aerosol distributions in the extra-tropical, lower stratosphere and the processes that maintain them
Authors: Wilson J. C. , Lee S.-H. , Reeves J. M. , Brock C. A. , Jonsson H. H. , Lafleur B. G. , Loewenstein M. , Podolske J. , Atlas E. , Boering K. , Toon G. , Fahey D. , Bui T. P. , Diskin G. , Moore F.
Published: April 2010

Abstract. Measurements of aerosol, N2O and OCS made in the Northern Hemisphere below 21 km altitude following the eruption of Pinatubo are presented and analyzed. After September 1999, the oxidation of OCS and sedimentation of particles in the extra-tropical overworld north of 45 N are found to maintain the aerosol in a steady state. This analysis empirically links precursor gas to aerosol abundance throughout this region. These processes are tracked with age-of-air which offers advantages over tracking as a function of latitude and altitude. In the extra-tropical, lowermost stratosphere, normalized volume distributions appear constant in time after the fall of 1999. Exchange with the troposphere is important in understanding aerosol evolution there. Size distributions of volcanically perturbed aerosol are included to distinguish between volcanic and non-volcanic conditions. This analysis suggests that model failures to correctly predict OCS and aerosol properties below 20 km in the Northern Hemisphere extra tropics result from inadequate descriptions of atmospheric circulation.
Direct observation of two dimensional trace gas distributions with an airborne Imaging DOAS instrument
Authors: Heue K.-P. , Wagner T. , Broccardo S. P. , Walter D. , Piketh S. J. , Ross K. E. , Beirle S. , Platt U.
Published: April 2010

Abstract. In many investigations of tropospheric chemistry information about the two dimensional distribution of trace gases on a small scale (e.g. tens to hundreds of metres) is highly desirable. An airborne instrument based on imaging Differential Optical Absorption Spectroscopy has been built to map the two dimensional distribution of a series of relevant trace gases including NO2, HCHO, C2H2O2, H2O, O4, SO2, and BrO on a scale of 100 m. Here we report on the first tests of the novel aircraft instrument over the industrialised South African Highveld, where large variations in NO2 column densities in the immediate vicinity of several sources e.g. power plants or steel works, were measured. The observed patterns in the trace gas distribution are interpreted with respect to flux estimates, and it is seen that the fine resolution of the measurements allows separate sources in close proximity to one another to be distinguished.