bluuebunny/crossref_metadata_2025 huggingface dataset:
Model intercomparison of indirect aerosol effects
Authors: Penner J. E. , Quaas J. , Storelvmo T. , Takemura T. , Boucher O. , Guo H. , Kirkevåg A. , Kristjánsson J. E. , Seland Ø.
Published: April 2010

Abstract. Modeled differences in predicted effects are increasingly used to help quantify the uncertainty of these effects. Here, we examine modeled differences in the aerosol indirect effect in a series of experiments that help to quantify how and why model-predicted aerosol indirect forcing varies between models. The experiments start with an experiment in which aerosol concentrations, the parameterization of droplet concentrations and the autoconversion scheme are all specified and end with an experiment that examines the predicted aerosol indirect forcing when only aerosol sources are specified. Although there are large differences in the predicted liquid water path among the models, the predicted aerosol first indirect effect for the first experiment is rather similar, about −0.6 Wm−2 to −0.7 Wm−2. Changes to the autoconversion scheme can lead to large changes in the liquid water path of the models and to the response of the liquid water path to changes in aerosols. Adding an autoconversion scheme that depends on the droplet concentration caused a larger (negative) change in net outgoing shortwave radiation compared to the 1st indirect effect, and the increase varied from only 22% to more than a factor of three. The change in net shortwave forcing in the models due to varying the autoconversion scheme depends on the liquid water content of the clouds as well as their predicted droplet concentrations, and both increases and decreases in the net shortwave forcing can occur when autoconversion schemes are changed. The parameterization of cloud fraction within models is not sensitive to the aerosol concentration, and, therefore, the response of the modeled cloud fraction within the present models appears to be smaller than that which would be associated with model "noise". The prediction of aerosol concentrations, given a fixed set of sources, leads to some of the largest differences in the predicted aerosol indirect radiative forcing among the models, with values of cloud forcing ranging from −0.3 Wm−2 to −1.4 Wm−2. Thus, this aspect of modeling requires significant improvement in order to improve the prediction of aerosol indirect effects.
Chemical composition of boundary layer aerosol over the Atlantic Ocean and at an Antarctic site
Authors: Virkkula A. , Teinilä K. , Hillamo R. , Kerminen V.-M. , Saarikoski S. , Aurela M. , Viidanoja J. , Paatero J. , Koponen I. K. , Kulmala M.
Published: April 2010

Abstract. Aerosol chemical composition was measured over the Atlantic Ocean in November–December 1999 and at the Finnish Antarctic research station Aboa in January 2000. The concentrations of all anthropogenic aerosol compounds decreased clearly from north to south. An anthropogenic influence was still evident in the middle of the tropical South Atlantic, background values were reached south of Cape Town. Chemical mass apportionment was calculated for high volume filter samples (Dp<3 μm). North of the equator 70–80% of the aerosol consisted of non-sea-salt species. The contribution of sea salt was ~25% in the polluted latitudes, >80% in the Southern Ocean, and <10% at Aboa. The contribution of organic carbon was >10% in most samples, also at Aboa. The correlation of biomass-burning-related aerosol components with 210Pb was very high compared with that between nss calcium and 210Pb which suggests that 210Pb is a better tracer for biomass burning than for Saharan dust. The ratio of the two clear tracers for biomass burning, nss potassium and oxalate, was different in European and in African samples, suggesting that this ratio could be used as an indicator of biomass burning type. The concentrations of continent-related particles decreased exponentially with the distance from Africa. The shortest half-value distance, ~100 km, was for nss calcium. The half-value distance of particles that are mainly in the submicron particles was ~700±200 km. The MSA to nss sulfate ratio, R, increased faster than MSA concentration with decreasing anthropogenic influence, indicating that the R increase could largely be explained by the decrease of anthropogenic sulfate.
Diel and seasonal variations in the chemical composition of biomass burning aerosol
Authors: Hoffer A. , Gelencsér A. , Blazsó M. , Guyon P. , Artaxo P. , Andreae M. O.
Published: April 2010

Abstract. Fine aerosol particles were collected separately during daytime and nighttime at a tropical pasture site in Rondônia, Brazil, during the burning and dry-to-wet transition period in 2002. Total carbon (TC) and water-soluble organic carbon (WSOC) were measured by evolved gas analysis (EGA). Based on the thermochemical properties of the fine aerosol, the relative amounts of the volatile and refractory compounds were estimated. It was found that the thermally refractory (possibly higher molecular weight) compounds dominated the TC composition. Their contribution to TC was higher in the daytime than in the nighttime samples. The relative share of WSOC also showed a statistically significant diel variation as did its refractory fraction. Anhydrosugars and phenolic acids were determined by GC-MS and their diel variation was studied. Based on the decrease of their relative concentrations between the biomass burning and transition periods and their distinctly different diel variations, we suggest that the phenolic acids may undergo chemical transformations in the aerosol phase, possibly towards more refractory compounds (humic-like substances, HULIS), as has been suggested previously. These conclusions are supported by the results of the thermally assisted hydrolysis and methylation gas chromatography-mass spectrometry of the same filter samples.
Measuring atmospheric CO2 from space using Full Spectral Initiation (FSI) WFM-DOAS
Authors: Barkley M. P. , Frieß U. , Monks P. S.
Published: April 2010

Abstract. Satellite measurements of atmospheric CO2 concentrations are a rapidly evolving area of scientific research which can help reduce the uncertainties in the global carbon cycle fluxes and provide insight into surface sources and sinks. One of the emerging CO2 measurement techniques is a relatively new retrieval algorithm called Weighting Function Modified Differential Optical Absorption Spectroscopy (WFM-DOAS) that has been developed by Buchwitz et al. (2000). This algorithm is designed to measure the total columns of CO2 (and other greenhouse gases) through the application to spectral measurements in the near infrared (NIR), made by the SCIAMACHY instrument on-board ENVISAT. The algorithm itself is based on fitting the logarithm of a model reference spectrum and its derivatives to the logarithm of the ratio of a measured nadir radiance and solar irradiance spectrum. In this work, a detailed error assessment of this technique has been conducted and it has been found necessary to include suitable a priori information within the retrieval in order to minimize the errors on the retrieved CO2 columns. Hence, a more flexible implementation of the retrieval technique, called Full Spectral Initiation (FSI) WFM-DOAS, has been developed which generates a reference spectrum for each individual SCIAMACHY observation using the estimated properties of the atmosphere and surface at the time of the measurement. Initial retrievals over Siberia during the summer of 2003 show that the measured CO2 columns are not biased from the input a priori data and that whilst the monthly averaged CO2 distributions contain a high degree of variability, they also contain interesting spatial features.
Technical note: Recursive rediscretisation of geo-scientific data in the Modular Earth Submodel System (MESSy)
Authors: Jöckel P.
Published: April 2010

Abstract. This technical note describes a method for the rediscretisation of "gridded" geo-scientific data. A recursive algorithm (NREGRID) is derived to solve the rediscretisation problem for orthogonal grids (including curvilinear) of arbitrary dimension. The algorithm is used within the program NCREGRID to handle geo-scientific data. These data are typically 2-dimensional (latitude-longitude grid), or 3-dimensional (latitude-longitude grid with a vertical pressure, or hybrid pressure coordinate, as used in atmospheric modelling). NCREGRID can be used as stand-alone program for the transformation ("regridding") of data from and to data files in netCDF format. Moreover, NCREGRID constitutes the core of the Modular Earth Submodel System (MESSy) data import interface, providing a powerful tool for accessing data independently of the applied grid resolution ("automatic regridding").
Importance of the surface reaction OH + Cl− on sea salt aerosol for the chemistry of the marine boundary layer – a model study
Authors: von Glasow R.
Published: April 2010

Abstract. The reaction of the hydroxyl radical with chloride on the surface of sea salt aerosol producing gas phase Cl2 and particulate OH− and its implications for the chemistry of the marine boundary layer under coastal, remote, and very remote conditions have been investigated with a numerical model. This reaction had been suggested by Laskin et al. (2003) to play a major role in the sulfur cycle in the marine boundary layer by increasing the sulfate production in sea salt by O3 oxidation due to the additional production of alkalinity in the particle. Based on literature data a new "best estimate" for the rate coefficient of the reaction was deduced and applied, showing that the additional initial sulfate production by this reaction is less than 1%, therefore having only a minor impact on sulfate production. Even though the gas phase concentration of Cl2 increased strongly in the model, the concentration of Cl radicals increased by less than 5% for the "best guess" case. Additional feedbacks between the cycles of chlorine and sulfur in the marine boundary layer are discussed as well as a two-stage acidification of large fresh sea salt aerosol.
Combined observational and modeling based study of the aerosol indirect effect
Authors: Storelvmo T. , Kristjánsson J. E. , Myhre G. , Johnsrud M. , Stordal F.
Published: April 2010

Abstract. The indirect effect of aerosols via liquid clouds is investigated by comparing aerosol and cloud characteristics from the Global Climate Model CAM-Oslo to those observed by the MODIS instrument onboard the TERRA and AQUA satellites http://modis.gsfc.nasa.gov). The comparison is carried out for 15 selected regions ranging from remote and clean to densely populated and polluted. For each region, the regression coefficient and correlation coefficient for the following parameters are calculated: Aerosol Optical Depth vs. Liquid Cloud Optical Thickness, Aerosol Optical Depth vs. Liquid Cloud Droplet Effective Radius and Aerosol Optical Depth vs. Cloud Liquid Water Path. Modeled and observed correlation coefficients and regression coefficients are then compared for a 3-year period starting in January 2001. Additionally, global maps for a number of aerosol and cloud parameters crucial for the understanding of the aerosol indirect effect are compared for the same period of time. Significant differences are found between MODIS and CAM-Oslo both in the regional and global comparison. However, both the model and the observations show a positive correlation between Aerosol Optical Depth and Cloud Optical Depth in practically all regions and for all seasons, in agreement with the current understanding of aerosol-cloud interactions. The correlation between Aerosol Optical Depth and Liquid Cloud Droplet Effective Radius is variable both in the model and the observations. However, the model reports the expected negative correlation more often than the MODIS data. Aerosol Optical Depth is overall positively correlated to Cloud Liquid Water Path both in the model and the observations, with a few regional exceptions.
Simulating regional scale secondary organic aerosol formation during the TORCH 2003 campaign in the southern UK
Authors: Johnson D. , Utembe S. R. , Jenkin M. E. , Derwent R. G. , Hayman G. D. , Alfarra M. R. , Coe H. , McFiggans G.
Published: April 2010

Abstract. A photochemical trajectory model has been used to simulate the chemical evolution of air masses arriving at the TORCH field campaign site in the southern UK during late July and August 2003, a period which included a widespread and prolonged photochemical pollution episode. The model incorporates speciated emissions of 124 non-methane anthropogenic VOC and three representative biogenic VOC, coupled with a comprehensive description of the chemistry of their degradation. A representation of the gas/aerosol absorptive partitioning of ca. 2000 oxygenated organic species generated in the Master Chemical Mechanism (MCM v3.1) has been implemented, allowing simulation of the contribution to organic aerosol (OA) made by semi- and non-volatile products of VOC oxidation; emissions of primary organic aerosol (POA) and elemental carbon (EC) are also represented. Simulations of total OA mass concentrations in nine case study events (optimised by comparison with observed hourly-mean mass loadings derived from aerosol mass spectrometry measurements) imply that the OA can be ascribed to three general sources: (i) POA emissions; (ii) a "ubiquitous" background concentration of 0.7 µg m-3; and (iii) gas-to-aerosol transfer of lower volatility products of VOC oxidation generated by the regional scale processing of emitted VOC, but with all partitioning coefficients increased by a species-independent factor of 500. The requirement to scale the partitioning coefficients, and the implied background concentration, are both indicative of the occurrence of chemical processes within the aerosol which allow the oxidised organic species to react by association and/or accretion reactions which generate even lower volatility products, leading to a persistent, non-volatile secondary organic aerosol (SOA). The contribution of secondary organic material to the simulated OA results in significant elevations in the simulated ratio of organic carbon (OC) to EC, compared with the ratio of 1.1 assigned to the emitted components. For the selected case study events, [OC]/[EC] is calculated to lie in the range 2.7-9.8, values which are comparable with the high end of the range reported in the literature.
A scaling analysis of ozone photochemistry
Authors: Ainslie B. , Steyn D. G.
Published: April 2010

Abstract. A scaling analysis has been used to capture the integrated behaviour of several photochemical mechanisms for a wide range of precursor concentrations and a variety of environmental conditions. The Buckingham Pi method of dimensional analysis was used to express the relevant variables in terms of dimensionless groups. These grouping show maximum ozone, initial NOx and initial VOC concentrations are made non-dimensional by the average NO2 photolysis rate (jav) and the rate constant for the NO–O3 titration reaction (kNO); temperature by the NO–O3 activation energy (ENO) and Boltzmann constant (k) and total irradiation time by the cumulative javΔt photolysis rate. The analysis shows dimensionless maximum ozone concentration can be described by a product of powers of dimensionless initial NOx concentration, dimensionless temperature, and a similarity curve directly dependent on the ratio of initial VOC to NOx concentration and implicitly dependent on the cumulative NO2 photolysis rate. When Weibull transformed, the similarity relationship shows a scaling break with dimensionless model output clustering onto two straight line segments, parameterized using four variables: two describing the slopes of the line segments and two giving the location of their intersection. A fifth parameter is used to normalize the model output. The scaling analysis, similarity curve and parameterization appear to be independent of the details of the chemical mechanism, hold for a variety of VOC species and mixtures and a wide range of temperatures and actinic fluxes.
Long-memory processes in ozone and temperature variations at the region 60° S–60° N
Authors: Varotsos C. , Kirk-Davidoff D.
Published: April 2010

Abstract. Global column ozone and tropospheric temperature observations made by ground-based (1964–2004) and satellite-borne (1978–2004) instrumentation are analyzed. Ozone and temperature fluctuations in small time-intervals are found to be positively correlated to those in larger time-intervals in a power-law fashion. For temperature, the exponent of this dependence is larger in the mid-latitudes than in the tropics at long time scales, while for ozone, the exponent is larger in tropics than in the mid-latitudes. In general, greater persistence could be a result of either stronger positive feedbacks or larger inertia. Therefore, the increased slope of the power distribution of temperature in mid-latitudes at long time scales compared to the slope in the tropics could be connected to the poleward increase in climate sensitivity predicted by the global climate models. The detrended fluctuation analysis of model and observed time series provides a helpful tool for visualizing errors in the treatment of long-range correlations, whose correct modeling would greatly enhance confidence in long-term climate and atmospheric chemistry modeling.
The semianalytical cloud retrieval algorithm for SCIAMACHY II. The application to MERIS and SCIAMACHY data
Authors: Kokhanovsky A. A. , von Hoyningen-Huene W. , Rozanov V. V. , Noël S. , Gerilowski K. , Bovensmann H. , Bramstedt K. , Buchwitz M. , Burrows J. P.
Published: April 2010

Abstract. The SemiAnalytical CloUd Retrieval Algorithm (SACURA) is applied to the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) data. In particular, we derive simultaneously cloud optical thickness (COT) and cloud top height (CTH), using SCIAMACHY measurements in the visible (442 nm, COT) and in the oxygen A-band (755–775 nm, CTH). Some of the results obtained are compared with those derived from the Medium Resolution Imaging Spectrometer (MERIS), which has better spatial resolution and observes almost the same scene as SCIAMACHY. The same cloud algorithm is applied to both MERIS and SCIAMACHY data. In addition, we perform the vicarious calibration of SCIAMACHY at the wavelength 442 nm, using MERIS measurements at the same wavelength. Differences in the retrieved COT for the same cloud field obtained using MERIS and SCIAMACHY measurements are discussed.
A modified band approach for the accurate calculation of online photolysis rates in stratospheric-tropospheric Chemical Transport Models
Authors: Williams J. E. , Landgraf J. , Bregman A. , Walter H. H.
Published: April 2010

Abstract. Here we present an efficient and accurate method for the online calculation of photolysis rates relevant to both the stratosphere and troposphere for use in global Chemistry Transport Models and General Circulation Models. The method is a modified version of the band model introduced by Landgraf and Crutzen (1998) which has been updated to improve the performance of the approach for solar zenith angles >72° without the use of any implicit parameterisations. For this purpose, additional sets of band parameters have been defined for instances where the incident angle of the light beam is between 72–93°, in conjunction with a scaling component for the far UV region of the spectrum (λ=178.6–202.0 nm). For incident angles between 85–93° we introduce a modification for pseudo-sphericity that improves the accuracy of the 2-stream approximation. We show that this modified version of the Practical Improved Flux Method (PIFM) is accurate for angles <93° by comparing the resulting height resolved actinic fluxes with a recently developed full spherical reference model. We also show that the modified band method is more accurate than the original, with errors generally being less than ±10% throughout the atmospheric column for a diverse range of chemical species. Moreover, we perform certain sensitivity studies that indicate it is robust and performs well over a wide range of conditions relevant to the atmosphere.
Impact of cloud-borne aerosol representation on aerosol direct and indirect effects
Authors: Ghan S. J. , Easter R. C.
Published: April 2010

Abstract. Aerosol particles attached to cloud droplets are much more likely to be removed from the atmosphere and are much less efficient at scattering sunlight than if unattached. Models used to estimate direct and indirect effects of aerosols employ a variety of representations of such cloud-borne particles. Here we use a global aerosol model with a relatively complete treatment of cloud-borne particles to estimate the sensitivity of simulated aerosol, cloud and radiation fields to various approximations to the representation of cloud-borne particles. We find that neglecting transport of cloud-borne particles introduces little error, but that diagnosing cloud-borne particles produces global mean biases of 20% and local errors of up to 40% for aerosol, droplet number, and direct and indirect radiative forcing. Aerosol number, aerosol optical depth and droplet number are significantly underestimated in regions and seasons where and when wet removal is primarily by stratiform rather than convective clouds (polar regions during winter), but direct and indirect effects are less biased because of the limited sunlight there and then. A treatment that predicts the total mass concentration of cloud-borne particles for each mode yields smaller errors and runs 20% faster than the complete treatment. The errors are much smaller than current estimates of uncertainty in direct and indirect effects of aerosols, which suggests that the treatment of cloud-borne aerosol is not a significant source of uncertainty in estimates of direct and indirect effects.
Simulating the detailed chemical composition of secondary organic aerosol formed on a regional scale during the TORCH 2003 campaign in the southern UK
Authors: Johnson D. , Utembe S. R. , Jenkin M. E.
Published: April 2010

Abstract. Following on from the companion study (Johnson et al., 2006), a photochemical trajectory model (PTM) has been used to simulate the chemical composition of organic aerosol for selected events during the 2003 TORCH (Tropospheric Organic Chemistry Experiment) field campaign. The PTM incorporates the speciated emissions of 124 non-methane anthropogenic volatile organic compounds (VOC) and three representative biogenic VOC, a highly-detailed representation of the atmospheric degradation of these VOC, the emission of primary organic aerosol (POA) material and the formation of secondary organic aerosol (SOA) material. SOA formation was represented by the transfer of semi- and non-volatile oxidation products from the gas-phase to a condensed organic aerosol-phase, according to estimated thermodynamic equilibrium phase-partitioning characteristics for around 2000 reaction products. After significantly scaling all phase-partitioning coefficients, and assuming a persistent background organic aerosol (both required in order to match the observed organic aerosol loadings), the detailed chemical composition of the simulated SOA has been investigated in terms of intermediate oxygenated species in the Master Chemical Mechanism, version 3.1 (MCM v3.1). For the various case studies considered, 90% of the simulated SOA mass comprises between ca. 70 and 100 multifunctional oxygenated species derived, in varying amounts, from the photooxidation of VOC of anthropogenic and biogenic origin. The anthropogenic contribution is dominated by aromatic hydrocarbons and the biogenic contribution by α- and β-pinene (which also constitute surrogates for other emitted monoterpene species). Sensitivity in the simulated mass of SOA to changes in the emission rates of anthropogenic and biogenic VOC has also been investigated for 11 case study events, and the results have been compared to the detailed chemical composition data. The role of accretion chemistry in SOA formation, and its implications for the results of the present investigation, is discussed.
Validation of remotely sensed profiles of atmospheric state variables: strategies and terminology
Authors: von Clarmann T.
Published: April 2010

Abstract. This paper summarizes and classifies the various approaches to validation of remote measurements of atmospheric state variables, and tries to recommend a clear and unambiguous terminology. The following approaches have been identified: Intercomparison of individual profiles for accuracy validation; statistical comparison of matched pairs of measurements with respect to bias determination and precision validation; statistical intercomparison of randomly sampled measurements by two instruments, and comparison of a single measurement to an ensemble of measurements. Applicable statistics are shortly reviewed, and recipes for evaluation of the co-incidence error due to less than perfect co-incidences are presented. An approach is suggested to quantitatively validate profile measurements when full covariance matrices are unavailable.
Some aspects of the energy balance closure problem
Authors: Foken T. , Wimmer F. , Mauder M. , Thomas C. , Liebethal C.
Published: April 2010

Abstract. After briefly discussing several reasons for the energy balance closure problem in the surface layer, the paper focuses on the influence of the low frequency part of the turbulence spectrum on the residual. Changes in the turbulent fluxes in this part of the turbulence spectrum were found to have a significant influence on the changes of the residual. Using the ogive method, it was found that the eddy-covariance method underestimates turbulent fluxes in the case of ogives converging for measuring times longer than the typical averaging interval of 30 min. Additionally, the eddy-covariance method underestimates turbulent fluxes for maximal ogive functions within the averaging interval, both mainly due to advection and non-steady state conditions. This has a considerable influence on the use of the eddy-covariance method.
Dry and wet deposition of inorganic nitrogen compounds to a tropical pasture site (Rondônia, Brazil)
Authors: Trebs I. , Lara L. L. , Zeri L. M. M. , Gatti L. V. , Artaxo P. , Dlugi R. , Slanina J. , Andreae M. O. , Meixner F. X.
Published: April 2010

Abstract. The input of nitrogen (N) to ecosystems has increased dramatically over the past decades. While total (wet + dry) N deposition has been extensively determined in temperate regions, only very few data sets of N wet deposition exist for tropical ecosystems, and moreover, reliable experimental information about N dry deposition in tropical environments is lacking. In this study we estimate dry and wet deposition of inorganic N for a remote pasture site in the Amazon Basin based on in-situ measurements. The measurements covered the late dry (biomass burning) season, a transition period and the onset of the wet season (clean conditions) (12 September to 14 November 2002) and were a part of the LBA-SMOCC (Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall, and Climate) 2002 campaign. Ammonia (NH3), nitric acid (HNO3), nitrous acid (HONO), nitrogen dioxide (NO2), nitric oxide (NO), ozone (O3), aerosol ammonium (NH4+) and aerosol nitrate (NO3-) were measured in real-time, accompanied by simultaneous meteorological measurements. Dry deposition fluxes of NO2 and HNO3 are inferred using the ''big leaf multiple resistance approach'' and particle deposition fluxes are derived using an established empirical parameterization. Bi-directional surface-atmosphere exchange fluxes of NH3 and HONO are estimated by applying a ''canopy compensation point model''. N dry and wet deposition is dominated by NH3 and NH4+, which is largely the consequence of biomass burning during the dry season. The grass surface appeared to have a strong potential for daytime NH3 emission, owing to high canopy compensation points, which are related to high surface temperatures and to direct NH3 emissions from cattle excreta. NO2 also significantly accounted for N dry deposition, whereas HNO3, HONO and N-containing aerosol species were only minor contributors. Ignoring NH3 emission from the vegetation surface, the annual net N deposition rate is estimated to be about −11 kgN ha-1 yr-1. If on the other hand, surface-atmosphere exchange of NH3 is considered to be bi-directional, the annual net N budget at the pasture site is estimated to range from −2.15 to −4.25 kgN ha-1 yr-1.
Analysis of the frequency-dependent response to wave forcing in the extratropics
Authors: Haklander A. J. , Siegmund P. C. , Kelder H. M.
Published: April 2010

Abstract. A quasigeostrophic model for the frequency-dependent response of the zonal-mean flow to planetary-wave forcing at Northern Hemisphere (NH) midlatitudes is applied to 4-D-Var ECMWF analysis data for six extended winter seasons. The theoretical response is a non-linear function of the frequency of the forcing, the thermal damping time α−1, and a scaling parameter µ which includes the aspect ratio of the meridional to the vertical length scale of the response. Regression of the calculated response from the analyses onto the theoretical response yields height-dependent estimates for both α−1 and µ. The thermal damping time estimated from this dynamical model is about 2 days in the troposphere, 7–10 days in the stratosphere, and 2–4 days in the lower mesosphere. For the stratosphere and lower mesosphere, the estimates lie within the range of existing radiative damping time estimates, but for the troposphere they are significantly smaller.
Comparisons between SCIAMACHY atmospheric CO2retrieved using (FSI) WFM-DOAS to ground based FTIR data and the TM3 chemistry transport model
Authors: Barkley M. P. , Monks P. S. , Frieß U. , Mittermeier R. L. , Fast H. , Körner S. , Heimann M.
Published: April 2010

Abstract. Atmospheric CO2 concentrations, retrieved from spectral measurements made in the near infrared (NIR) by the SCIAMACHY instrument, using Full Spectral Initiation Weighting Function Modified Differential Optical Absorption Spectroscopy (FSI WFM-DOAS), are compared to ground based Fourier Transform Infrared (FTIR) data and to the output from a global chemistry-transport model. Analysis of the FSI WFM-DOAS retrievals with respect to the ground based FTIR instrument, located at Egbert, Canada, show good agreement with an average negative bias of approximately −4.0% with a standard deviation of  3.0%. This bias which exhibits an apparent seasonal trend, is of unknown origin, though slight differences between the averaging kernels of the instruments and the limited temporal coverage of the FTIR data may be the cause. The relative scatter of the retrieved vertical column densities is larger than the spread of the FTIR measurements. Normalizing the CO2 columns using the surface pressure does not affect the magnitude of this bias although it slightly decreases the scatter of the FSI data. Comparisons of the FSI retrievals to the TM3 global chemistry-transport model, performed over four selected Northern Hemisphere scenes show reasonable agreement. The correlation, between the time series of the SCIAMACHY and model monthly scene averages, are  0.7 or greater, demonstrating the ability of SCIAMACHY to detect seasonal changes in the CO2 distribution. The amplitude of the seasonal cycle, peak to peak, observed by SCIAMACHY however, is larger by a factor of 2–3 with respect to the model, which cannot be explained. The yearly means detected by SCIAMACHY are within 2% of those of the model with the mean difference between the CO2 distributions also approximately 2.0%. Additionally, analysis of the retrieved CO2 distributions reveals structure not evident in the model fields which correlates well with land classification type. From these comparisons, it is estimated that the overall bias of the CO2 columns retrieved by the FSI algorithm is <4.0% with the precision of monthly 1°×1° gridded data close to 1.0%.
Calibration of LACIS as a CCN detector and its use in measuring activation and hygroscopic growth of atmospheric aerosol particles
Authors: Wex H. , Kiselev A. , Ziese M. , Stratmann F.
Published: April 2010

Abstract. A calibration for LACIS (Leipzig Aerosol Cloud Interaction Simulator) for its use as a CCN (cloud condensation nuclei) detector has been developed. For this purpose, sodium chloride and ammonium sulfate particles of known sizes were generated and their grown sizes were detected at the LACIS outlet. From these signals, the effective critical super-saturation was derived as a function of the LACIS wall temperature. With this, LACIS is calibrated for its use as a CCN detector. The applicability of LACIS for measurements of the droplet activation, and also of the hygroscopic growth of atmospheric aerosol particles was tested. The activation of the urban aerosol particles used in the measurements was found to occur at a critical super-saturation of 0.46% for particles with a dry diameter of 75 nm, and at 0.42% for 85 nm, respectively. Hygroscopic growth was measured for atmospheric aerosol particles with dry diameters of 150, 300 and 350 nm at relative humidities of 98 and 99%, and it was found that the larger dry particles contained a larger soluble volume fraction of about 0.85, compared to about 0.6 for the 150 nm particles.
Potential impacts of CF3I on ozone as a replacement for CF3Br in aircraft applications
Authors: Li Y. , Patten K. O. , Youn D. , Wuebbles D. J.
Published: April 2010

Abstract. Iodotrifluoromethane (CF3I) has been considered to be a candidate replacement for bromotrifluoromethane (CF3Br), which is used in aircraft for fuel inerting and for fire fighting. In this study, the chemical effects of aircraft-released CF3I on atmospheric ozone were examined with the University of Illinois at Urbana-Champaign two-dimensional chemical-radiative-transport (UIUC 2-D CRT) model. Using an earlier estimate of the aircraft emission profile for tank inerting in military aircraft, the resulting equivalent Ozone Depletion Potentials (ODPs) for CF3I were in the range of 0.07 to 0.25. As a sensitivity study, we also analyzed CF3I emissions associated with fuel inerting if it were to occur at lower altitudes using an alternative estimate. The model calculations of resulting effects on ozone for this case gave ODPs≤0.05. Furthermore, through interactions with the National Institute of Standards and Technology (NIST), we analyzed the potential effects on ozone resulting from using CF3I in fire fighting connected with engine nacelle and auxiliary power unit applications. The scenarios evaluated using the NIST estimate suggested that the ODPs obtained by assuming aircraft flights occurring in several different latitude regions of the Northern Hemisphere are extremely low. According to the model calculation, the altitude where CF3I is released from aircraft is a dominant factor in its ozone depletion effects. On the assumption that the CF3I emission profile is representative of actual release characteristics, aircraft-released CF3I has much lower impacts than CF3Br.
Prompt deliquescence and efflorescence of aerosol nanoparticles
Authors: Biskos G. , Paulsen D. , Russell L. M. , Buseck P. R. , Martin S. T.
Published: April 2010

Abstract. Literature reports have differed on the possibilities of discontinuous and continuous (i.e., prompt and nonprompt) deliquescence and efflorescence of aerosol particles in the nanosize regime. Experiments reported herein using a hygroscopic tandem nano-differential mobility analyzer demonstrate prompt deliquescence and efflorescence of ammonium sulfate particles having diameters from 6 to 60 nm. Apparent nonpromptness can be induced both by operation of the experimental apparatus and by interpretation of the measurements, even though the underlying phase transitions of individual particles remain prompt. No nanosize effect on the relative humidity values of deliquescence or efflorescence is observed for the studied size range. Smaller hygroscopic growth factors are, however, observed for the nanoparticles, in agreement with thermodynamic calculations that include the Kelvin effect. A slightly nonspherical shape for dry ammonium sulfate particles is inferred from their hygroscopically induced reconstruction between 5 and 30% relative humidity. Our results provide a further understanding of nanoparticle behavior, especially relevant to the growth rates of atmospheric nanoparticles.
Carbonate precipitation in brine – a potential trigger for tropospheric ozone depletion events
Authors: Sander R. , Burrows J. , Kaleschke L.
Published: April 2010

Abstract. Tropospheric ozone depletion events (ODEs) at high latitudes were discovered 20 years ago and are attributed to bromine explosions. However, an unresolved issue is the explanation of how the acid-catalyzed reaction cycle is triggered in atmospheric particles derived from alkaline sea water. By simulating the chemistry occuring in polar regions over recently formed sea ice, we can model successfully the transformation of inert sea-salt bromide to reactive bromine monoxide (BrO) and the subsequent ODE when precipitation of calcium carbonate from freezing sea water is taken into account. In addition, we found the temperature dependence of the equilibrium BrCl+Br−↔Br2Cl− to be important.
Scavenging of ultrafine particles by rainfall at a boreal site: observations and model estimations
Authors: Andronache C. , Grönholm T. , Laakso L. , Phillips V. , Venäläinen A.
Published: April 2010

Abstract. Values of the scavenging coefficient determined from observations of ultrafine particles (with diameters in the range 10–510 nm) during rain events at a boreal forest site in Southern Finland between 1996 and 2001 were reported by Laakso et al. (2003a). The estimated range of the median values of the scavenging coefficient was [7×10−6–4×10−5] s−1, which is generally higher than model calculations based only on below-cloud processes (Brownian diffusion, interception, and typical phoretic and charge effects). In the present study, in order to interpret these observed data on scavenging coefficients from Laakso et al. (2003a), we use a model that includes below-cloud scavenging processes, mixing of ultrafine particles from the boundary layer (BL) into cloud, followed by cloud condensation nuclei activation and in-cloud removal by rainfall. The range of effective scavenging coefficient predicted by the new model, corresponding to wide ranges of values of its input parameters, are compared with observations. Results show that ultrafine particle removal by rain depends on aerosol size, rainfall intensity, mixing processes between BL and cloud elements, in-cloud scavenged fraction, in-cloud collection efficiency, and in-cloud coagulation with cloud droplets. The scavenging coefficients predicted by the new model are found to be significantly sensitive to the choice of representation of: (1) mixing processes; (2) raindrop size distribution; (3) phoretic effects in aerosol-raindrop collisions; and (4) cloud droplet activation. Implications for future studies of BL ultrafine particles scavenging are discussed.
Re-evaluation of the 1950–1962 total ozone record from Longyearbyen, Svalbard
Authors: Vogler C. , Brönnimann S. , Hansen G.
Published: April 2010

Abstract. The historical total ozone measurements taken with Dobson Spectrophotometer #8 at Longyearbyen (78.2° N, 15.6° E), Svalbard, Norway, in the period 1950–1962 have been re-analyzed and homogenized based on the original measurement logs, using present-day procedures. In lack of sufficient calibration information, an empirical quality assessment was performed, based on a climatological comparison with ozone measurements in Tromsø, using TOMS data at both sites in the period 1979–2001, and ground-based Dobson data in the period 1950–1962. The assessment revealed that the C wavelength pair direct-sun (DS) measurements are most trustworthy (and most frequent), while the WMO standard reference mode AD direct-sun has a systematic bias. Zenith-blue (ZB) measurements at solar zenith angles (SZA) <78° were adjusted to DS data using different empirical functions before and after 1957 (the start of the International Geophysical Year). ZB measurements at larger SZAs were homogenized by means of a normalization function derived from days with measurements over a wide range of SZAs. Zenith-cloudy measurements, which are particularly frequent during the summer months, were homogenized by applying correction factors depending on the cloud type (high thin clouds and medium to low thick clouds). The combination of all measurements yields a total of 4685 single values, covering 1637 days from September 1950 to September 1962; moon measurements during the polar night add another 137 daily means. The re-evaluated data show a convincing consistence with measurements since 1979 (TOMS, SAOZ, Dobson) as well as with the 1957–1962 data stored at the World Ozone and UV Data Centre (WOUDC).
Modelling of nitrate and ammonium-containing aerosols in presence of sea salt
Authors: Myhre G. , Grini A. , Metzger S.
Published: April 2010

Abstract. A thermodynamical model for treatment of gas/aerosol partitioning of semi volatile inorganic aerosols has been implemented in a global chemistry and aerosol transport model (Oslo CTM2). The sulphur cycle and sea salt particles have been implemented earlier in the Oslo CTM2 and the focus of this study is on nitrate partitioning to the aerosol phase and if particulate nitrate is expected to form in fine or coarse mode aerosols. Modelling of the formation of fine mode nitrate particles is complicated since it depends on other aerosol components and aerosol precursors as well as meteorological condition. The surface concentrations from the model are compared to observed surface concentrations at around 20 sites around Europe for nitrate and ammonium. The agreement for nitrate is good but the modelled values are somewhat underestimated compared to observations at high concentrations, whereas for ammonium the agreement is very good. However, we underscore that such a comparison is not of large importance for the aerosol optical depth of particulate nitrate since the vertical profile of aerosol components and their precursors are so important. Fine mode nitrate formation depends on vertical profiles of both ammonia/ammonium and sulphate. The model results show that fine mode particulate nitrate play a non-negligible role in the total aerosol composition in certain industrialized regions and therefore have a significant local radiative forcing. On a global scale the aerosol optical depth of fine mode nitrate is relatively small due to limited availability of ammonia and loss to larger sea salt particles. Inclusion of sea salt in the calculations reduces the aerosol optical depth and burden of fine mode nitrate by 25% on a global scale but with large regional variations.
Characterization of aerosol pollution events in France using ground-based and POLDER-2 satellite data
Authors: Kacenelenbogen M. , Léon J.-F. , Chiapello I. , Tanré D.
Published: April 2010

Abstract. We analyze the relationship between daily fine particle mass concentration (PM2.5) and columnar aerosol optical thickness derived from the Polarization and Directionality of Earth's Reflectances (POLDER) satellite sensor. The study is focused over France during the POLDER-2 lifetime between April and October 2003. We have first compared the POLDER derived aerosol optical thickness (AOT) with integrated volume size distribution derived from ground-based Sun Photometer observations. The good correlation (R=0.72) with sub-micron volume fraction indicates that POLDER derived AOT is sensitive to the fine aerosol mass concentration. Considering 1974 match-up data points over 28 fine particle monitoring sites, the POLDER-2 derived AOT is fairly well correlated with collocated PM2.5 measurements, with a correlation coefficient of 0.55. The correlation coefficient reaches a maximum of 0.80 for particular sites. We have analyzed the probability to find an appropriate air quality category (AQC) as defined by U.S. Environmental Protection Agency (EPA) from POLDER-2 AOT measurements. The probability can be up to 88.8% (±3.7%) for the "Good" AQC and 89.1% (±3.6%) for the "Moderate" AQC.
The relative importance of competing pathways for the formation of high-molecular-weight peroxides in the ozonolysis of organic aerosol particles
Authors: Mochida M. , Katrib Y. , Jayne J. T. , Worsnop D. R. , Martin S. T.
Published: April 2010

Abstract. High-molecular-weight (HMW) organic compounds are an important component of atmospheric particles, although their origins, possibly including in situ formation pathways, remain incompletely understood. This study investigates the formation of HMW organic peroxides through reactions involving stabilized Criegee intermediates (SCI's). The model system is methyl oleate (MO) mixed with dioctyl adipate (DOA) and myristic acid (MA) in submicron aerosol particles, and Criegee intermediates are formed by the ozonolysis of the double bond in methyl oleate. An aerosol flow tube coupled to a quadrupole aerosol mass spectrometer (AMS) is employed to determine the relative importance of different HMW organic peroxides following the ozonolysis of different mixing mole fractions of MO in DOA and MA. Possible peroxide products include secondary ozonides (SOZ's), α-acyloxyalkyl hydroperoxides and α-acyloxyalkyl alkyl peroxides (αAAHP-type compounds), diperoxides, and monoperoxide oligomers. Of these, the AMS data identify two SOZ's as major HMW products in the ozonolysis of pure methyl oleate as well as in an inert matrix of DOA to as low as 0.04 mole fraction MO. In comparison, in mixed particles of MO and MA, αAAHP-type compounds form in high yields for MO mole fractions of 0.5 or less, suggesting that SCI's efficiently attack the carboxylic acid group of myristic acid. The reactions of SCI's with carboxylic acid groups to form αAAHP-type compounds therefore compete with those of SCI's with aldehydes to form SOZ's, provided that both types of functionalities are present at significant concentrations. The results therefore suggest that SCI's in atmospheric particles contribute to the transformation of carboxylic acids and other protic groups into HMW organic peroxides.
Implementation of a Markov Chain Monte Carlo method to inorganic aerosol modeling of observations from the MCMA-2003 campaign – Part I: Model description and application to the La Merced site
Authors: San Martini F. M. , Dunlea E. J. , Grutter M. , Onasch T. B. , Jayne J. T. , Canagaratna M. R. , Worsnop D. R. , Kolb C. E. , Shorter J. H. , Herndon S. C. , Zahniser M. S. , Ortega J. M. , McRae G. J. , Molina L. T. , Molina M. J.
Published: April 2010

Abstract. The equilibrium inorganic aerosol model ISORROPIA was embedded in a Markov Chain Monte Carlo algorithm to develop a powerful tool to analyze aerosol data and predict gas phase concentrations where these are unavailable. The method directly incorporates measurement uncertainty, prior knowledge, and provides a formal framework to combine measurements of different quality. The method was applied to particle- and gas-phase precursor observations taken at La Merced during the Mexico City Metropolitan Area (MCMA) 2003 Field Campaign and served to discriminate between diverging gas-phase observations of ammonia and predict gas-phase concentrations of hydrochloric acid. The model reproduced observations of particle-phase ammonium, nitrate, and sulfate well. The most likely concentrations of ammonia were found to vary between 4 and 26 ppbv, while the range for nitric acid was 0.1 to 55 ppbv. During periods where the aerosol chloride observations were consistently above the detection limit, the model was able to reproduce the aerosol chloride observations well and predicted the most likely gas-phase hydrochloric acid concentration varied between 0.4 and 5 ppbv. Despite the high ammonia concentrations observed and predicted by the model, when the aerosols were assumed to be in the efflorescence branch they are predicted to be acidic (pH~3).