bluuebunny/crossref_metadata_2025 huggingface dataset:
Impact of the new HNO3-forming channel of the HO2+NO reaction on tropospheric HNO3, NOx, HOx and ozone
Authors: Cariolle D. , Evans M. J. , Chipperfield M. P. , Butkovskaya N. , Kukui A. , Le Bras G.
Published: April 2010

Abstract. We have studied the impact of the recently observed reaction NO+HO2→HNO3 on atmospheric chemistry. A pressure and temperature-dependent parameterisation of this minor channel of the NO+HO2→NO2+OH reaction has been included in both a 2-D stratosphere-troposphere model and a 3-D tropospheric chemical transport model (CTM). Significant effects on the nitrogen species and hydroxyl radical concentrations are found throughout the troposphere, with the largest percentage changes occurring in the tropical upper troposphere (UT). Including the reaction leads to a reduction in NOx everywhere in the troposphere, with the largest decrease of 25% in the tropical and Southern Hemisphere UT. The tropical UT also has a corresponding large increase in HNO3 of 25%. OH decreases throughout the troposphere with the largest reduction of over 20% in the tropical UT. The mean global decrease in OH is around 13%, which is very large compared to the impact that typical photochemical revisions have on this modelled quantity. This OH decrease leads to an increase in CH4 lifetime of 5%. Due to the impact of decreased NOx on the OH:HO2 partitioning, modelled HO2 actually increases in the tropical UT on including the new reaction. The impact on tropospheric ozone is a decrease in the range 5 to 12%, with the largest impact in the tropics and Southern Hemisphere. Comparison with observations shows that in the region of largest changes, i.e. the tropical UT, the inclusion of the new reaction tends to degrade the model agreement. Elsewhere the model comparisons are not able to critically assess the impact of including this reaction. Only small changes are calculated in the minor species distributions in the stratosphere.
Radiative forcing from particle emissions by future supersonic aircraft
Authors: Pitari G. , Iachetti D. , Mancini E. , Montanaro V. , De Luca N. , Marizy C. , Dessens O. , Rogers H. , Pyle J. , Grewe V. , Stenke A. , Søvde O. A.
Published: April 2010

Abstract. In this work we focus on the direct radiative forcing (RF) of black carbon (BC) and sulphuric acid particles emitted by future supersonic aircraft, as well as on the ozone RF due to changes produced by emissions of both gas species (NOx, H2O) and aerosol particles capable of affecting stratospheric ozone chemistry. Heterogeneous chemical reactions on the surface of sulphuric acid stratospheric particles (SSA-SAD) are the main link between ozone chemistry and supersonic aircraft emissions of sulphur precursors (SO2) and particles (H2O–H2SO4). Photochemical O3 changes are compared from four independent 3-D atmosphere-chemistry models (ACMs), using as input the perturbation of SSA-SAD calculated in the University of L'Aquila model, which includes on-line a microphysics code for aerosol formation and growth. The ACMs in this study use aircraft emission scenarios for the year 2050 developed by AIRBUS as a part of the EU project SCENIC, assessing options for fleet size, engine technology (NOx emission index), Mach number, range and cruising altitude. From our baseline modeling simulation, the impact of supersonic aircraft on sulphuric acid aerosol and BC mass burdens is 53 and 1.5 μg/m2, respectively, with a direct RF of −11.4 and 4.6 mW/m2 (net RF=−6.8 mW/m2). This paper discusses the similarities and differences amongst the participating models in terms of changes to O3 precursors due to aircraft emissions (NOx, HOx,Clx,Brx) and the stratospheric ozone sensitivity to them. In the baseline case, the calculated global ozone change is −0.4 ±0.3 DU, with a net radiative forcing (IR+UV) of −2.5± 2 mW/m2. The fraction of this O3-RF attributable to SSA-SAD changes is, however, highly variable among the models, depending on the NOx removal efficiency from the aircraft emission regions by large scale transport.
Chemical composition of free tropospheric aerosol for PM1 and coarse mode at the high alpine site Jungfraujoch
Authors: Cozic J. , Verheggen B. , Weingartner E. , Crosier J. , Bower K. N. , Flynn M. , Coe H. , Henning S. , Steinbacher M. , Henne S. , Collaud Coen M. , Petzold A. , Baltensperger U.
Published: April 2010

Abstract. The chemical composition of submicron (fine mode) and supermicron (coarse mode) aerosol particles has been investigated at the Jungfraujoch high alpine research station (3580 m a.s.l., Switzerland) as part of the GAW aerosol monitoring program since 1999. A clear seasonality was observed for all major components throughout the period with low concentrations in winter (predominantly free tropospheric aerosol) and higher concentrations in summer (enhanced vertical transport of boundary layer pollutants). In addition, mass closure was attempted during intensive campaigns in March 2004, February–March 2005 and August 2005. Ionic, carbonaceous and non-refractory components of the aerosol were quantified as well as the PM1 and coarse mode total aerosol mass concentrations. A relatively low conversion factor of 1.8 for organic carbon (OC) to particulate organic matter (OM) was found in winter (February–March 2005). Organics, sulfate, ammonium, and nitrate were the major components of the fine aerosol fraction that were identified, while calcium and nitrate were the only two measured components contributing to the coarse mode. The aerosol mass concentrations for fine and coarse mode aerosol measured during the intensive campaigns were not typical of the long-term seasonality due largely to dynamical differences. Average fine and coarse mode concentrations during the intensive field campaigns were 1.7 μg m−3 and 2.4 μg m−3 in winter and 2.5 μg m−3 and 2.0 μg m−3 in summer, respectively. The mass balance of aerosols showed higher contributions of calcium and nitrate in the coarse mode during Saharan dust events (SDE) than without SDE.
Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO3)
Authors: Ng N. L. , Kwan A. J. , Surratt J. D. , Chan A. W. H. , Chhabra P. S. , Sorooshian A. , Pye H. O. T. , Crounse J. D. , Wennberg P. O. , Flagan R.  C. , Seinfeld J. H.
Published: April 2010

Abstract. Secondary organic aerosol (SOA) formation from the reaction of isoprene with nitrate radicals (NO3) is investigated in the Caltech indoor chambers. Experiments are performed in the dark and under dry conditions (RH<10%) using N2O5 as a source of NO3 radicals. For an initial isoprene concentration of 18.4 to 101.6 ppb, the SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) ranges from 4.3% to 23.8%. By examining the time evolutions of gas-phase intermediate products and aerosol volume in real time, we are able to constrain the chemistry that leads to the formation of low-volatility products. Although the formation of ROOR from the reaction of two peroxy radicals (RO2) has generally been considered as a minor channel, based on the gas-phase and aerosol-phase data it appears that RO2+RO2 reaction (self reaction or cross-reaction) in the gas phase yielding ROOR products is a dominant SOA formation pathway. A wide array of organic nitrates and peroxides are identified in the aerosol formed and mechanisms for SOA formation are proposed. Using a uniform SOA yield of 10% (corresponding to Mo≅10 μg m−3), it is estimated that ~2 to 3 Tg yr−1 of SOA results from isoprene+NO3. The extent to which the results from this study can be applied to conditions in the atmosphere depends on the fate of peroxy radicals in the nighttime troposphere.
A compact and stable eddy covariance set-up for methane measurements using off-axis integrated cavity output spectroscopy
Authors: Hendriks D. M. D. , Dolman A. J. , van der Molen M. K. , van Huissteden J.
Published: April 2010

Abstract. A Fast Methane Analyzer (FMA) is assessed for its applicability in a closed path eddy covariance field set-up in a peat meadow. The FMA uses off-axis integrated cavity output spectroscopy combined with a highly specific narrow band laser for the detection of CH4 and strongly reflective mirrors to obtain a laser path length of 2–20×103 m. Statistical testing and a calibration experiment showed high precision (7.8×10−3 ppb) and accuracy (<0.30%) of the instrument, while no drift was observed. The instrument response time was determined to be 0.10 s. In the field set-up, the FMA is attached to a scroll pump and combined with a 3-axis ultrasonic anemometer and an open path infrared gas analyzer for measurements of carbon dioxide and water vapour. The power-spectra and co-spectra of the instruments were satisfactory for 10 Hz sampling rates. Due to erroneous measurements, spikes and periods of low turbulence the data series consisted for 26% of gaps. Observed CH4 fluxes consisted mainly of emission, showed a diurnal cycle, but were rather variable over. The average CH4 emission was 29.7 nmol m−2 s−1, while the typical maximum CH4 emission was approximately 80.0 nmol m−2 s−1 and the typical minimum flux was approximately 0.0 nmol m−2 s−1. The correspondence of the measurements with flux chamber measurements in the footprint was good and the observed CH4 emission rates were comparable with eddy covariance CH4 measurements in other peat areas. Additionally, three measurement techniques with lower sampling frequencies were simulated, which might give the possibility to measure CH4 fluxes without an external pump and save energy. Disjunct eddy covariance appeared to be the most reliable substitute for 10 Hz eddy covariance, while relaxed eddy accumulation gave reliable estimates of the fluxes over periods in the order of days or weeks.
Measurement of ambient aerosols in northern Mexico City by single particle mass spectrometry
Authors: Moffet R. C. , de Foy B. , Molina L. T. , Molina M. J. , Prather K. A.
Published: April 2010

Abstract. Continuous ambient measurements with aerosol time-of-flight mass spectrometry (ATOFMS) were made in an industrial/residential section in the northern part of Mexico City as part of the Mexico City Metropolitan Area-2006 campaign (MCMA-2006). Results are presented for the period of 15–27 March 2006. The submicron size mode contained both fresh and aged biomass burning, aged organic carbon (OC) mixed with nitrate and sulfate, elemental carbon (EC), nitrogen-organic carbon, industrial metal, and inorganic NaK inorganic particles. Overall, biomass burning and aged OC particle types comprised 40% and 31%, respectively, of the submicron mode. In contrast, the supermicron mode was dominated by inorganic NaK particle types (42%) which represented a mixture of dry lake bed dust and industrial NaK emissions mixed with soot. Additionally, aluminosilicate dust, transition metals, OC, and biomass burning contributed to the supermicron particles. Early morning periods (2–6 a.m.) showed high fractions of inorganic particles from industrial sources in the northeast, composed of internal mixtures of Pb, Zn, EC and Cl, representing up to 73% of the particles in the 0.2–3μm size range. A unique nitrogen-containing organic carbon (NOC) particle type, peaking in the early morning hours, was hypothesized to be amines from local industrial emissions based on the time series profile and back trajectory analysis. A strong dependence on wind speed and direction was observed in the single particle types that were present during different times of the day. The early morning (3:30–10 a.m.) showed the greatest contributions from industrial emissions. During mid to late mornings (7–11 a.m.), weak northerly winds were observed along with the most highly aged particles. Stronger winds from the south picked up in the late morning (after 11 a.m.), resulting in a decrease in the concentrations of the major aged particle types and an increase in the number fraction of fresh biomass particles. The highest wind speeds were correlated with the highest number fraction of fresh biomass particles (up to 76% of the submicron number fraction) when winds were coming directly from fires that were located south and southeast of the city based on MODIS fire count data. This study provides a unique clock of hourly changes in single particle mixing state and sources as a function of meteorology in Mexico City. These new findings indicate that biomass burning and industrial emissions can make significant contributions to primary particle loadings in Mexico City that are strongly coupled with local meteorology.
Comparison of OMI ozone and UV irradiance data with ground-based measurements at two French sites
Authors: Buchard V. , Brogniez C. , Auriol F. , Bonnel B. , Lenoble J. , Tanskanen A. , Bojkov B. , Veefkind P.
Published: April 2010

Abstract. Ozone Monitoring Instrument (OMI), launched in July 2004, is dedicated to the monitoring of the Earth's ozone, air quality and climate. OMI is the successor of the Total Ozone Mapping Spectrometer (TOMS) instruments and provides among other atmospheric and radiometric quantities the total column of ozone (TOC), the surface ultraviolet (UV) irradiance at several wavelengths, the erythemal dose rates and the erythemal daily doses. The main objective of this work is to compare OMI data with data from ground-based instruments in order to use OMI products (collection 2) for scientific studies. The Laboratoire d'Optique Atmosphérique (LOA) located in Villeneuve d'Ascq (VdA) in the north of France performs solar UV measurements using a spectroradiometer. The site of Briançon in the French Southern Alps is also equipped with a spectroradiometer operated by Interaction Rayonnement Solaire Atmosphère (IRSA). The OMI total ozone column data is obtained from the OMI-TOMS and OMI-DOAS algorithms. The comparison between the TOC retrieved with ground-based measurements and OMI-TOMS data shows good agreement at both sites for all sky conditions with a relative difference for most of points better than 5%. For OMI-DOAS data, the agreement is generally better than 7% and these data show a significant dependence on solar zenith angle. Comparisons of spectral UV on clear sky conditions are also satisfying with relative differences smaller than 10% except at solar zenith angles larger than 65°. On the contrary, results of comparisons of the erythemal dose rates and erythemal daily doses for clear sky show that OMI overestimates surface UV doses at VdA by about 15% and that on cloudy skies, the bias increases. At Briançon, such a bias is observed if data corresponding to snow-covered surface are excluded.
Variability of cirrus clouds in a convective outflow during the Hibiscus campaign
Authors: Fierli F. , Di Donfrancesco G. , Cairo F. , Marécal V. , Zampieri M. , Orlandi E. , Durry G.
Published: April 2010

Abstract. Light-weight microlidar and water vapour measurements were taken on-board a stratospheric balloon during the HIBISCUS 2004 campaign, held in Bauru, Brazil (49° W, 22° S). Cirrus clouds were observed throughout the flight between 12 and 15 km height with a high mesoscale variability in optical and microphysical properties. It was found that the cirrus clouds were composed of different layers characterized by marked differences in height, thickness and optical properties. Simultaneous water vapour observations show that the different layers are characterized by different values of the saturation with respect to ice. A mesoscale simulation and a trajectory analysis clearly revealed that the clouds had formed in the outflow of a large and persistent convective region and that the observed variability of the optical properties and of the cloud structure is likely linked to the different residence times of the convectively-processed air in the upper troposphere.
A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients
Authors: Zuend A. , Marcolli C. , Luo B. P. , Peter T.
Published: April 2010

Abstract. Tropospheric aerosols contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. Interactions between these substances in liquid mixtures lead to discrepancies from ideal thermodynamic behaviour. By means of activity coefficients, non-ideal behaviour can be taken into account. We present here a thermodynamic model named AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) that is able to calculate activity coefficients covering inorganic, organic, and organic-inorganic interactions in aqueous solutions over a wide concentration range. This model is based on the activity coefficient model LIFAC by Yan et al. (1999) that we modified and reparametrised to better describe atmospherically relevant conditions and mixture compositions. Focusing on atmospheric applications we considered H+, Li+, Na+, K+, NH+4, Mg2+, Ca2+, Cl−, Br−, NO−3, HSO−4, and SO2−4 as cations and anions and a wide range of alcohols/polyols composed of the functional groups CHn and OH as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are well represented up to high ionic strength. Most notably, a semi-empirical middle-range parametrisation of direct organic-inorganic interactions in alcohol+water+salt solutions strongly improves the agreement between experimental and modelled activity coefficients. At room temperature, this novel thermodynamic model offers the possibility to compute equilibrium relative humidities, gas/particle partitioning and liquid-liquid phase separations with high accuracy. In further studies, other organic functional groups will be introduced. The model framework is not restricted to specific ions or organic compounds and is therefore also applicable for other research topics.
Why are estimates of global terrestrial isoprene emissions so similar (and why is this not so for monoterpenes)?
Authors: Arneth A. , Monson R. K. , Schurgers G. , Niinemets Ü. , Palmer P. I.
Published: April 2010

Abstract. Emissions of biogenic volatile organic compounds (BVOC) are a chief uncertainty in calculating the burdens of important atmospheric compounds like tropospheric ozone or secondary organic aerosol, reflecting either imperfect chemical oxidation mechanisms or unreliable emission estimates, or both. To provide a starting point for a more systematic discussion we review here global isoprene and monoterpene emission estimates to-date. We note a surprisingly small variation in the predictions of global isoprene emission rate that is in stark contrast with our lack of process understanding and the small number of observations for model parameterisation and evaluation. Most of the models are based on similar emission algorithms, using fixed values for the emission capacity of various plant functional types. In some cases, these values are very similar but differ substantially in other models. The similarities with regard to the global isoprene emission rate would suggest that the dominant parameters driving the ultimate global estimate, and thus the dominant determinant of model sensitivity, are the specific emission algorithm and isoprene emission capacity. But the models also differ broadly with regard to their representation of net primary productivity, method of biome coverage determination and climate data. Contrary to isoprene, monoterpene estimates show significantly larger model-to-model variation although variation in terms of leaf algorithm, emission capacities, the way of model upscaling, vegetation cover or climatology used in terpene models are comparable to those used for isoprene. From our summary of published studies there appears to be no evidence that the terrestrial modelling community has been any more successful in "resolving unknowns" in the mechanisms that control global isoprene emissions, compared to global monoterpene emissions. Rather, the proliferation of common parameterization schemes within a large variety of model platforms lends the illusion of convergence towards a common estimate of global isoprene emissions. This convergence might be used to provide optimism that the community has reached the "relief phase", the phase when sufficient process understanding and data for evaluation allows models' projections to converge, when applying a recently proposed concept. We argue that there is no basis for this apparent relief phase. Rather, we urge modellers to be bolder in their analysis, and to draw attention to the fact that terrestrial emissions, particularly in the area of biome-specific emission capacities, are unknown rather than uncertain.
AirClim: an efficient tool for climate evaluation of aircraft technology
Authors: Grewe V. , Stenke A.
Published: April 2010

Abstract. Climate change is a challenge to society and to cope with requires assessment tools which are suitable to evaluate new technology options with respect to their impact on global climate. Here we present AirClim, a model which comprises a linearisation of atmospheric processes from the emission to radiative forcing, resulting in an estimate in near surface temperature change, which is presumed to be a reasonable indicator for climate change. The model is designed to be applicable to aircraft technology, i.e. the climate agents CO2, H2O, CH4 and O3 (latter two resulting from NOx-emissions) and contrails are taken into account. AirClim combines a number of precalculated atmospheric data with aircraft emission data to obtain the temporal evolution of atmospheric concentration changes, radiative forcing and temperature changes. These precalculated data are derived from 25 steady-state simulations for the year 2050 with the climate-chemistry model E39/C, prescribing normalised emissions of nitrogen oxides and water vapour at various atmospheric regions. The results show that strongest climate impacts (year 2100) from ozone changes occur for emissions in the tropical upper troposphere (60 mW/m2; 80 mK for 1 TgN/year emitted) and from methane changes from emissions in the middle tropical troposphere (−2.7% change in methane lifetime; –30 mK per TgN/year). For short-lived species (e.g. ozone, water vapour, methane) individual perturbation lifetimes are derived depending on the region of emission. A comparison of this linearisation approach with results from a comprehensive climate-chemistry model shows reasonable agreement with respect to concentration changes, radiative forcing, and temperature changes. For example, the total impact of a supersonic fleet on radiative forcing (mainly water vapour) is reproduced within 10%. A wide range of application is demonstrated.
Retrieval of global upper tropospheric and stratospheric formaldehyde (H2CO) distributions from high-resolution MIPAS-Envisat spectra
Authors: Steck T. , Glatthor N. , von Clarmann T. , Fischer H. , Flaud J. M. , Funke B. , Grabowski U. , Höpfner M. , Kellmann S. , Linden A. , Perrin A. , Stiller G. P.
Published: April 2010

Abstract. The Fourier transform spectrometer MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) on Envisat measures infrared emission of the Earth's atmosphere in a limb viewing mode. High spectral resolution measurements of MIPAS are sensitive to formaldehyde from the upper troposphere to the stratopause. Single profile retrievals of formaldehyde are dominated by a 60% noise error; however zonal mean values for 30 days of data during 8 September 2003 and 1 December 2003 reduces this error by a factor of 20 or more. The number of degrees of freedom for single profile retrieval ranges from 2 to 4.5 depending on latitude and number of cloud-free tangent altitudes. In the upper tropical troposphere zonal mean values of about 70 parts per trillion by volume (pptv) were found, which have been attributed to biomass burning emissions. In the stratosphere, formaldehyde values are determined by photochemical reactions. In the upper tropical stratosphere, formaldehyde zonal mean maximum values can reach 130 pptv. Diurnal variations in this region can be up to 50 pptv. Comparisons with other satellite instruments show generally good agreement in the region of upper troposphere and lower stratosphere as well as in the upper stratosphere.
Relationship between drizzle rate, liquid water path and droplet concentration at the scale of a stratocumulus cloud system
Authors: Geoffroy O. , Brenguier J.-L. , Sandu I.
Published: April 2010

Abstract. The recent ACE-2, EPIC and DYCOMS-II field experiments showed that the drizzle precipitation rate of marine stratocumulus scales with the cloud geometrical thickness or liquid water path, and the droplet concentration, when averaged over a domain typical of a GCM grid. This feature is replicated here with large-eddy-simulations using state-of-the-art bulk parameterizations of precipitation formation in stratocumulus clouds. The set of numerical simulations shows scaling relationships similar to the ones derived from the field experiments, especially the one derived from the DYCOMS-II data set. This result suggests that the empirical relationships were not fortuitous and that they reflect the mean effect of cloud physical processes. Such relationships might be more suited to GCM parameterizations of precipitation from shallow clouds than bulk parameterizations of autoconversion, that were initially developed for cloud resolving models.
The relationship between tropospheric wave forcing and tropical lower stratospheric water vapor
Authors: Dhomse S. , Weber M. , Burrows J.
Published: April 2010

Abstract. Using water vapor data from HALOE and SAGE II, an anti-correlation between planetary wave driving (here expressed by the mid-latitude eddy heat flux at 50 hPa added from both hemispheres) and tropical lower stratospheric (TLS) water vapor has been obtained. This appears to be a manifestation of the inter-annual variability of the Brewer-Dobson (BD) circulation strength (the driving of which is generally measured in terms of the mid-latitude eddy heat flux), and hence amount of water vapor entering the stratosphere. Some years such as 1991 and 1997 show, however, a clear departure from the anti-correlation which suggests that the water vapor changes in TLS can not be attributed solely to changes in extratropical planetary wave activity (and its effect on the BD circulation). After 2000 a sudden decrease in lower stratospheric water vapor has been reported in earlier studies based upon satellite data from HALOE, SAGE II and POAM III indicating that the lower stratosphere has become drier since then. This is consistent with a sudden rise in the combined mid-latitude eddy heat flux with nearly equal contribution from both hemispheres as shown here and with the increase in tropical upwelling and decrease in cold point temperatures found by Randel et al. (2006). The low water vapor and enhanced planetary wave activity (in turn strength of the BD circulation) has persisted until the end of the satellite data records. From a multi-variate regression analysis applied to 27 years of NCEP and HadAT2 (radiosonde) temperatures (up to 2005) with contributions from solar cycle, stratospheric aerosols and QBO removed, the enhancement wave driving after 2000 is estimated to contribute up to 0.7 K cooling to the overall TLS temperature change during the period 2001–2005 when compared to the period 1996–2000. NCEP cold point temperature show an average decrease of nearly 0.4 K from changes in the wave driving, which is consistent with observed mean TLS water vapor changes of about −0.2 ppm after 2000.
Characterization of the South Atlantic marine boundary layer aerosol using an aerodyne aerosol mass spectrometer
Authors: Zorn S. R. , Drewnick F. , Schott M. , Hoffmann T. , Borrmann S.
Published: April 2010

Abstract. Measurements of the submicron fraction of the atmospheric aerosol in the marine boundary layer were performed from January to March 2007 (Southern Hemisphere summer) onboard the French research vessel Marion Dufresne in the Southern Atlantic and Indian Ocean (20° S–60° S, 70° W–60° E). We used an Aerodyne High-Resolution-Time-of-Flight AMS to characterize the chemical composition and to measure species-resolved size distributions of non-refractory aerosol components in the submicron range. Within the "standard" AMS compounds (ammonium, chloride, nitrate, sulfate, organics) "sulfate" is the dominant species in the marine boundary layer with concentrations ranging between 50 ng m−3 and 3 μg m−3. Furthermore, what is seen as "sulfate" by the AMS is likely comprised mostly of sulfuric acid. Another sulfur containing species that is produced in marine environments is methanesulfonic acid (MSA). There have been previously measurements of MSA using an Aerodyne AMS. However, due to the use of an instrument equipped with a quadrupole detector with unit mass resolution it was not possible to physically separate MSA from other contributions to the same m/z. In order to identify MSA within the HR-ToF-AMS raw data and to extract mass concentrations for MSA from the field measurements the standard high-resolution MSA fragmentation patterns for the measurement conditions during the ship campaign (e.g. vaporizer temperature) needed to be determined. To identify characteristic air masses and their source regions backwards trajectories were used and averaged concentrations for AMS standard compounds were calculated for each air mass type. Sulfate mass size distributions were measured for these periods showing a distinct difference between oceanic air masses and those from African outflow. While the peak in the mass distribution was roughly at 250 nm (vacuum aerodynamic diameter) in marine air masses, it was shifted to 470 nm in African outflow air. Correlations between the mass concentrations of sulfate, organics and MSA show a narrow correlation for MSA with sulfate/sulfuric acid coming from the ocean, but not with continental sulfate.
Nanoparticle formation in the exhaust of vehicles running on ultra-low sulfur fuel
Authors: Du H. , Yu F.
Published: April 2010

Abstract. The concern of adverse health impacts from exposure to vehicle-emitted nanoparticles has been escalating over the past few years. In order to meet more stringent EPA emission standards for particle mass emissions, advanced exhaust after-treatment systems such as continuously regenerating diesel particle filters (CRDPFs) have to be employed on vehicles and fuel with ultra-low sulfur is to be used. Although CRDPFs were found to be effective in reducing particle mass emissions, they were revealed to increase the potential of volatile nanoparticle formation. Significant nanoparticle concentrations have also been detected for vehicles running on ultra-low sulfur fuel but without CRDPFs. The main focus of this paper is the formation and evolution of nanoparticles in an exhaust plume under ultra-low sulfur conditions. Such a study is necessary to project future nanoparticle emissions as fuel compositions and after-treatment systems change. We have carried out a comprehensive quantitative assessment of the effects of enhanced sulfur conversion efficiency, sulfur storage/release, and presence of non-volatile cores on nanoparticle formation using a detailed composition resolved aerosol microphysical model with a recently improved H2SO4-H2O homogeneous nucleation (BHN) module. Two well-controlled case studies show good agreement between model predictions and measurements in terms of particle size distribution and temperature dependence of particle formation rate, which leads us to conclude that BHN is the main source of nanoparticles for vehicles equipped with CRDPFs. We found that the employment of CRDPFs may lead to the higher number concentration of nanoparticles (but smaller size) in the exhaust of vehicles running on ultra-low sulfur fuel compared to those emitted from vehicles running on high sulfur fuel. We have also shown that the sulfate storage and release effect can lead to significant enhancement in nanoparticle production under favorable conditions. For vehicles running on ultra-low sulfur fuel but without CRDPFs, the BHN is negligible; however, the condensation of low volatile organic compounds on nanometer-sized non-volatile cores may explain the observed nucleation mode particles.
Validation of ACE-FTS N2O measurements
Authors: Strong K. , Wolff M. A. , Kerzenmacher T. E. , Walker K. A. , Bernath P. F. , Blumenstock T. , Boone C. , Catoire V. , Coffey M. , De Mazière M. , Demoulin P. , Duchatelet P. , Dupuy E. , Hannigan J. , Höpfner M. , Glatthor N. , Griffith D. W. T. , Jin J. J. , Jones N. , Jucks K. , Kuellmann H. , Kuttippurath J. , Lambert A. , Mahieu E. , McConnell J. C. , Mellqvist J. , Mikuteit S. , Murtagh D. P. , Notholt J. , Piccolo C. , Raspollini P. , Ridolfi M. , Robert C. , Schneider M. , Schrems O. , Semeniuk K. , Senten C. , Stiller G. P. , Strandberg A. , Taylor J. , Tétard C. , Toohey M. , Urban J. , Warneke T. , Wood S.
Published: April 2010

Abstract. The Atmospheric Chemistry Experiment (ACE), also known as SCISAT, was launched on 12 August 2003, carrying two instruments that measure vertical profiles of atmospheric constituents using the solar occultation technique. One of these instruments, the ACE Fourier Transform Spectrometer (ACE-FTS), is measuring volume mixing ratio (VMR) profiles of nitrous oxide (N2O) from the upper troposphere to the lower mesosphere at a vertical resolution of about 3–4 km. In this study, the quality of the ACE-FTS version 2.2 N2O data is assessed through comparisons with coincident measurements made by other satellite, balloon-borne, aircraft, and ground-based instruments. These consist of vertical profile comparisons with the SMR, MLS, and MIPAS satellite instruments, multiple aircraft flights of ASUR, and single balloon flights of SPIRALE and FIRS-2, and partial column comparisons with a network of ground-based Fourier Transform InfraRed spectrometers (FTIRs). Between 6 and 30 km, the mean absolute differences for the satellite comparisons lie between −42 ppbv and +17 ppbv, with most within ±20 ppbv. This corresponds to relative deviations from the mean that are within ±15%, except for comparisons with MIPAS near 30 km, for which they are as large as 22.5%. Between 18 and 30 km, the mean absolute differences for the satellite comparisons are generally within ±10 ppbv. From 30 to 60 km, the mean absolute differences are within ±4 ppbv, and are mostly between −2 and +1 ppbv. Given the small N2O VMR in this region, the relative deviations from the mean are therefore large at these altitudes, with most suggesting a negative bias in the ACE-FTS data between 30 and 50 km. In the comparisons with the FTIRs, the mean relative differences between the ACE-FTS and FTIR partial columns (which cover a mean altitude range of 14 to 27 km) are within ±5.6% for eleven of the twelve contributing stations. This mean relative difference is negative at ten stations, suggesting a small negative bias in the ACE-FTS partial columns over the altitude regions compared. Excellent correlation (R=0.964) is observed between the ACE-FTS and FTIR partial columns, with a slope of 1.01 and an intercept of −0.20 on the line fitted to the data.
Parameterization of sea-salt optical properties and physics of the associated radiative forcing
Authors: Li J. , Ma X. , von Salzen K. , Dobbie S.
Published: April 2010

Abstract. The optical properties of sea-salt aerosol have been parameterized at shortwave and longwave wavelengths. The optical properties were parameterized in a simple functional form in terms of the ambient relative humidity based on Mie optical property calculations. The proposed parameterization is tested relative to Mie calculations and is found to be accurate to within a few percent. In the parameterization, the effects of the size distribution on the optical properties are accounted for in terms of effective radius of the sea-salt size distribution. This parameterization differs from previous works by being formulated directly with the wet sea-salt size distribution and, to our knowledge, this is the first published sea-salt parameterization to provide a parameterization for both shortwave and longwave wavelengths. We have used this parameterization in a set of idealized 1-D radiative transfer calculations to investigate the sensitivity of various attributes of sea-salt forcing, including the dependency on sea-salt column loading, effective variance, solar angle, and surface albedo. From these sensitivity tests, it is found that sea-salt forcings for both shortwave and longwave spectra are linearly related to the sea-salt loading for realistic values of loadings. The radiative forcing results illustrate that the shortwave forcing is an order of magnitude greater than the longwave forcing results and opposite in sign, for various loadings. Forcing sensitivity studies show that the influence of effective variance for sea-salt is minor; therefore, only one value of effective variance is used in the parameterization. The dependence of sea-salt forcing with solar zenith angle illustrates an interesting result that sea-salt can generate a positive top-of-the-atmosphere result (i.e. warming) when the solar zenith angle is relatively small (i.e. <30°). Finally, it is found that the surface albedo significantly affects the shortwave radiative forcing, with the forcing diminishing to zero as the surface albedo tends to unity.
Some considerations about Ångström exponent distributions
Authors: Wagner F. , Silva A. M.
Published: April 2010

Abstract. A simulation study has been performed in order to show the influence of the aerosol optical depth (AOD) distribution together with the corresponding error distribution on the resulting Ångström exponent (AE) distribution. It will be shown that the Ångström exponent frequency of occurrence distribution is only normal distributed when the relative error at the two wavelengths used for estimation of the Ångström exponent is the same. In all other cases a shift of the maximum of the AE-distribution will occur. It will be demonstrated that the Ångström exponent (or the maximum of an AE distribution) will be systematically over- or underestimated depending on whether the relative error of the shorter wavelength is larger or smaller compared with the relative error of the longer wavelength. In such cases the AE distribution are also skewed.
Intercomparison of erythemal broadband radiometers calibrated by seven UV calibration facilities in Europe and the USA
Authors: Hülsen G. , Gröbner J. , Bais A. , Blumthaler M. , Disterhoft P. , Johnsen B. , Lantz K. O. , Meleti C. , Schreder J. , Vilaplana Guerrero J. M. , Ylianttila L.
Published: April 2010

Abstract. A bi-lateral intercomparison of erythemal broadband radiometers was performed between seven UV calibration facilities. The calibrations provided by the instruments owners were compared relative to the characterisation and calibration performed at PMOD/WRC in Davos, Switzerland. The calibration consisted in the determination of the spectral and angular response of the radiometer, followed by an absolute calibration performed outdoors relative to a spectroradiometer which provided the absolute reference. The characterization of the detectors in the respective laboratories are in good agreement: The determinations of the angular responses have deviations below ±4% and the spectral responses agree within ±20%. A "blind" intercomparison of the erythemally weighted irradiances derived by the respective institutes and PMOD/WRC showed consistent measurements to within ±2% for the majority of institutes. One institute showed slightly larger deviation of 10%. The differences found between the different instrument calibrations are all within the combined uncertainty of the calibration.
Direct detection of OH formation in the reactions of HO2 with CH3C(O)O2 and other substituted peroxy radicals
Authors: Dillon T. J. , Crowley J. N.
Published: April 2010

Abstract. This work details the first direct observation of OH as a product from (R1): HO2+CH3C(O)O2→(products), which has generally been considered an atmospheric radical termination process. The technique of pulsed laser photolysis radical generation, coupled to calibrated laser induced fluorescence detection was used to measure an OH product yield for (R1) of α1(298 K)=(0.5±0.2). This study of (R1) included the measurement of a rate coefficient k1(298 K)=(1.4±0.5)×10−11cm3 molecule−1 s−1, substantially reducing the uncertainties in modelling this important atmospheric reaction. OH was also detected as a product from the reactions of HO2 with three other carbonyl-containing peroxy radicals, albeit at smaller yield, e.g. (R2): HO2+CH3C(O)CH2O2→(products), α2≈0.15. By contrast, OH was not observed (α<0.06) as a major product from reactions where carbonyl functionality was absent, e.g. HO2+HOCH2CH2O2 (R8), and HO2+CH3CH(OH)CH2O2 (R9).
Vertical profile of peroxyacetyl nitrate (PAN) from MIPAS-STR measurements over Brazil in February 2005 and its contribution to tropical UT NOy partitioning
Authors: Keim C. , Liu G. Y. , Blom C. E. , Fischer H. , Gulde T. , Höpfner M. , Piesch C. , Ravegnani F. , Roiger A. , Schlager H. , Sitnikov N.
Published: April 2010

Abstract. We report on the retrieval of PAN (CH3C(O)OONO2) in the upper tropical troposphere from limb measurements by the remote-sensor MIPAS-STR on board the Russian high altitude research aircraft M55-Geophysica. The measurements were performed close to Araçatuba, Brazil, on 17 February 2005. The retrieval was made in the spectral range 775–820 cm−1 where PAN exhibits its strongest feature but also more than 10 species interfere. Especially trace gases such as CH3CCl3, CFC-113, CFC-11, and CFC-22, emitting also in spectrally broad not-resolved branches, make the processing of PAN prone to errors. Therefore, the selection of appropriate spectral windows, the separate retrieval of several interfering species and the careful handling of the water vapour profile are part of the study presented. The retrieved profile of PAN has a maximum of about 0.14 ppbv at 10 km altitude, slightly larger than the lowest reported values (<0.1 ppbv) and much lower than the highest reported in the literature (0.65 ppbv). Besides the NOy constituents measured by MIPAS-STR (HNO3, ClONO2, HO2NO2, PAN), the in situ instruments aboard the Geophysica provide simultaneous measurements of NO, NO2, and the sum NOy. Comparing the sum of in-situ and remotely derived NO+NO2+HNO3+ClONO2+HO2NO2+PAN with total NOy a deficit of 30–40% (0.2–0.3 ppbv) in the troposphere remains unexplained whereas the values fit well in the stratosphere.
Effects of dust storms on microwave radiation based on satellite observation and model simulation over the Taklamakan desert
Authors: Ge J. , Huang J. , Weng F. , Sun W.
Published: April 2010

Abstract. Effects of dust particles on microwave radiation over the Taklamakan desert are studied with use of measurements from the Advanced Microwave Scanning Radiometer (AMSR-E) on the EOS Aqua satellite and a microwave radiation transfer model. Eight observed cases show that the signal from atmospheric dust can be separated from the surface radiation by the fact that the dust particles produce stronger scattering at high frequencies and depolarize the background desert signature. This result of satellite data is consistent with the model simulation.
Aerosol direct radiative effect in the Po Valley region derived from AERONET measurements
Authors: Clerici M. , Mélin F.
Published: April 2010

Abstract. The aerosol direct radiative effect (ADRE) affecting the Po Valley and the adjacent North Adriatic Sea is studied using 10-year series of measurements collected at two AERONET sites located in the western part of the Valley (Ispra), and on a platform (AAOT) offshore Venice. This region is characterized by a high, mostly continental, aerosol load with comparable average aerosol optical thickness τa at both locations (0.21 at 500 nm) and more absorbing aerosols at Ispra. A dynamic aerosol model accounting for the changes in scattering phase function with τa is used for radiative transfer calculations, together with boundary conditions representative of terrestrial and marine surfaces. A sensitivity analysis allows the construction of an error budget for the daily ADRE estimates, found to be of the order of 20% and mostly due to uncertainties on aerosol single scattering albedo and τa. The daily radiative efficiencies, normalized by τa at 500 nm, increase from December to June, from −17 to −24 W m−2 τa−1 at top-of-atmosphere (TOA) and −33 to −72 W m−2 τa−1 at surface for the Po Valley, and from −15 to −32 (TOA) and −35 to −65 W m−2 τa−1 (surface) for the AAOT site. The average of log-transformed ADRE for TOA, surface and atmosphere are −5.2, −12.2 and +6.8 W m−2 for the Po Valley case, and −6.5, −13.0 and +6.5 W m−2 for the AAOT site but these values can be much higher for individual days. Concurrent clear-sky days give indications on the regional atmospheric heating spatial gradients. Differences between the atmospheric ADRE at the two locations average 6.3 W m−2 with a gradient positive towards the inner valley in 65% of the cases. This study confirms the importance of duly considering the radiative impact of aerosols on the regional climate.
Source characteristics of volatile organic compounds during high ozone episodes in Hong Kong, Southern China
Authors: Zhang J. , Wang T. , Chameides W. L. , Cardelino C. , Blake D. R. , Streets D. G.
Published: April 2010

Abstract. Measurements of Volatile Organic Compounds (VOC) are analyzed to characterize the sources impacting the Hong Kong area. The ratios of different VOC species, m,p-xylenes-to-ethylbenzene, C6H14-to-toluene and p-xylene-to-total xylenes are used for diagnostic analyses. Photochemical age analysis shows that the sources of reactive aromatics, the most important contributor to the photochemical reactivity, do not appear to be preferentially located in downtown Hong Kong. In addition, they do not appear to be dominated by mobile emissions based on the analyses of speciated VOC data from an earlier study, but related to industrial, waterfront, and fuel-storage activities. The ratios, p-xylene-to-total xylenes and dSO2/dNOy, suggest that the anomalously high pollutant concentrations in western Hong Kong in the early morning hours of two episode days appear to have come from transport of urban-type emissions. Comparison of observed ambient ratios of selected VOC and their ratios in the speciated VOC emission inventories for Hong Kong and adjacent Pearl River Delta (PRD) Region gives mixed results. The observed ratio C6H14-to-toluene is consistent with the speciated version of the VOC emission inventory. The ratios of selected alkanes are not. This may be caused by the inaccuracies in the inventory and/or the speciation method.