bluuebunny/crossref_metadata_2025 huggingface dataset:
Satellite-derived land surface parameters for mesoscale modelling of the Mexico City basin
Authors: de Foy B. , Molina L. T. , Molina M. J.
Published: April 2010

Abstract. Mesoscale meteorological modelling is an important tool to help understand air pollution and heat island effects in urban areas. Accurate wind simulations are difficult to obtain in areas of weak synoptic forcing. Local factors have a dominant role in the circulation and include land surface parameters and their interaction with the atmosphere. This paper examines an episode during the MCMA-2003 field campaign held in the Mexico City Metropolitan Area (MCMA) in April of 2003. Because the episode has weak synoptic forcing, there is the potential for the surface heat budget to influence the local meteorology. High resolution satellite observations are used to specify the land use, vegetation fraction, albedo and surface temperature in the MM5 model. Making use of these readily available data leads to improved meteorological simulations in the MCMA, both for the wind circulation patterns and the urban heat island. Replacing values previously obtained from land-use tables with actual measurements removes the number of unknowns in the model and increases the accuracy of the energy budget. In addition to improving the understanding of local meteorology, this sets the stage for the use of advanced urban modules.
Piecewise log-normal approximation of size distributions for aerosol modelling
Authors: von Salzen K.
Published: April 2010

Abstract. An efficient and accurate method for the representation of particle size distributions in atmospheric models is proposed. The method can be applied, but is not necessarily restricted, to aerosol mass and number size distributions. A piecewise log-normal approximation of the number size distribution within sections of the particle size spectrum is used. Two of the free parameters of the log-normal approximation are obtained from the integrated number and mass concentration in each section. The remaining free parameter is prescribed. The method is efficient in a sense that only relatively few calculations are required for applications of the method in atmospheric models. Applications of the method in simulations of particle growth by condensation and simulations with a single column model for nucleation, condensation, gravitational settling, wet deposition, and mixing are described. The results are compared to results from simulations employing single- and double-moment bin methods that are frequently used in aerosol modelling. According to these comparisons, the accuracy of the method is noticeably higher than the accuracy of the other methods.
The heterogeneous chemical kinetics of N2O5 on CaCO3 and other atmospheric mineral dust surrogates
Authors: Karagulian F. , Santschi C. , Rossi M. J.
Published: April 2010

Abstract. Uptake experiments of N2O5 on several mineral dust powder samples were carried out under continuous molecular flow conditions at 298±2 K. At [N2O5]0=(4.0±1.0)×1011 cm−3 we have found γss values ranging from (3.5±1.1)×10−2 for CaCO3 to (0.20±0.05) for Saharan Dust with γss decreasing as [N2O5]0 increased. The uptake coefficients reported in this work are to be regarded as upper limiting values owing to the fact that they are based on the geometric (projected) surface area of the mineral dust sample. We have observed delayed production of HNO3 upon uptake of N2O5 for every investigated sample owing to hydrolysis of N2O5 with surface-adsorbed H2O. Arizona Test Dust and Kaolinite turned out to be the samples that generated the largest amount of gas phase HNO3 with respect to N2O5 taken up. In contrast, the yield of HNO3 for Saharan Dust and CaCO3 is lower. On CaCO3 the disappearance of N2O5 was also accompanied by the formation of CO2. For CaCO3 sample masses ranging from 0.33 to 2.0 g, the yield of CO2 was approximately 42–50% with respect to the total number of N2O5 molecules taken up. The reaction of N2O5 with mineral dust and the subsequent production of gas phase HNO3 lead to a decrease in [NOx] which may have a significant effect on global ozone.
The origin of ozone
Authors: Grewe V.
Published: April 2010

Abstract. Highest atmospheric ozone production rates can be found at around 30 km in the tropical stratosphere, leading to ozone mixing ratios of about 10 ppmv. Those stratospheric air masses are then transported to extra-tropical latitudes via the Brewer-Dobson circulation. This is considered the main mechanism to generate mid- and high latitude ozone. By applying the climate-chemistry models E39/C and MAECHAM4/CHEM, this view is investigated in more detail. The origin of ozone in the troposphere and stratosphere is analysed, by incorporating a diagnostics ("marked ozone origin tracers") into the models, which allows to identify the origin of ozone. In most regions the simulated local ozone concentration is dominated by local ozone production, i.e. less than 50% of the ozone at higher latitudes of the stratosphere is produced in the tropics, which conflicts with the idea that the tropics are the global source for stratospheric ozone. Although episodic stratospheric intrusions occur basically everywhere, the main ozone stratosphere-to-troposphere exchange is connected to exchange processes at the sub-tropical jet-stream. The simulated tropospheric influx of ozone amounts to 420 Tg per year, and originates in the Northern Hemisphere from the extra-tropical stratosphere, whereas in the Southern Hemisphere a re-circulation of tropical tropospheric ozone contributes most to the influx of ozone into the troposphere. In the model E39/C, the upper troposphere of both hemispheres is clearly dominated by tropical tropospheric ozone (40%–50%) except for northern summer hemisphere, where the tropospheric contribution (from the tropics as well as from the Northern Hemisphere) does not exceed 20%.
Modelling study of the impact of deep convection on the UTLS air composition – Part 2: Ozone budget in the TTL
Authors: Rivière E. D. , Marécal V. , Larsen N. , Cautenet S.
Published: April 2010

Abstract. In this second part of a series of two papers which aim to study the local impact of deep convection on the chemical composition of the Upper Troposphere and Lower Stratosphere (UTLS), we focus on ozone simulation results using a mesoscale model that includes on-line chemistry. A severe convective system observed on 8 February 2001 at Bauru, Brazil, is studied. This unorganised convective system is composed of several convective cells that interact with each other. We show that there is an increase in the ozone concentration in the tropical transitional layer (TTL) in the model during this event, which is compatible with ozone sonde observations from Bauru during the 2004 convective season. The model horizontal variability of ozone in this layer is comparable with the variability of the ozone sonde observations in the same area. The calculation of the ozone budget in the TTL during a 24 h period in the area of the convective system shows that the ozone behaviour in this layer is mainly driven by dynamics. The horizontal flux at a specific time is the main contribution in the budget, since it drives the sign and the magnitude of the total ozone flux. However, when averaged over the 24 h period, the horizontal flux is smaller than the vertical fluxes, and leads to a net decrease of ozone molecule number of 23%. The upward motions at the bottom of the TTL, related to the convection activity is the main contributor to the budget over the 24h period since it can explain 70% of the total ozone increase in the TTL, while the chemical ozone production inside the TTL is estimated to be 29% of the ozone increase, if NOx production by lightning (LNOx) is taken into account. It is shown that downward motion at the tropopause induced by gravity waves generated by deep convection is non negligible in the TTL ozone budget, since it represents 24% of the ozone increase. The flux analysis shows the importance of the vertical contributions during the life time of the convective event (about 8 h). The TTL ozone is driven out of the domain horizontally by the convective outflow during this period, limiting the ozone increase in this layer.
Sources and transformations of particle-bound polycyclic aromatic hydrocarbons in Mexico City
Authors: Marr L. C. , Dzepina K. , Jimenez J. L. , Reisen F. , Bethel H. L. , Arey J. , Gaffney J. S. , Marley N. A. , Molina L. T. , Molina M. J.
Published: April 2010

Abstract. Understanding sources, concentrations, and transformations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere is important because of their potent mutagenicity and carcinogenicity. The measurement of particle-bound PAHs by three different methods during the Mexico City Metropolitan Area field campaign in April 2003 presents a unique opportunity for characterization of these compounds and intercomparison of the methods. The three methods are (1) collection and analysis of bulk samples for time-integrated gas- and particle-phase speciation by gas chromatography/mass spectrometry; (2) aerosol photoionization for fast detection of PAHs on particles' surfaces; and (3) aerosol mass spectrometry for fast analysis of size and chemical composition. This research represents the first time aerosol mass spectrometry has been used to measure ambient PAH concentrations and the first time that fast, real-time methods have been used to quantify PAHs alongside traditional filter-based measurements in an extended field campaign. Speciated PAH measurements suggest that motor vehicles and garbage and wood burning are important sources in Mexico City. The diurnal concentration patterns captured by aerosol photoionization and aerosol mass spectrometry are generally consistent. Ambient concentrations of particle-phase PAHs typically peak at ~110 ng m-3 during the morning rush hour and rapidly decay due to changes in source activity patterns and dilution as the boundary layer rises, although surface-bound PAH concentrations decay faster. The more rapid decrease in surface versus bulk PAH concentrations during the late morning suggests that freshly emitted combustion-related particles are quickly coated by secondary aerosol material in Mexico City's atmosphere and may also be transformed by heterogeneous reactions.
Large decadal scale changes of polar ozone suggest solar influence
Authors: Sinnhuber B.-M. , von der Gathen P. , Sinnhuber M. , Rex M. , König-Langlo G. , Oltmans S. J.
Published: April 2010

Abstract. Long-term measurements of polar ozone show an unexpectedly large decadal scale variability in the mid-stratosphere during winter. Negative ozone anomalies are strongly correlated with the flux of energetic electrons in the radiation belt, which is modulated by the 11-year solar cycle. The magnitude of the observed decadal ozone changes (≈20%) is much larger than any previously reported solar cycle effect in the atmosphere up to this altitude. The early-winter ozone anomalies subsequently propagate downward into the lower stratosphere and may even influence total ozone and meteorological conditions during spring. These findings suggest a previously unrecognized mechanism by which solar variability impacts on climate through changes in polar ozone.
Evolution of aerosol optical thickness over Europe during the August 2003 heat wave as seen from CHIMERE model simulations and POLDER data
Authors: Hodzic A. , Vautard R. , Chepfer H. , Goloub P. , Menut L. , Chazette P. , Deuzé J. L. , Apituley A. , Couvert P.
Published: April 2010

Abstract. This study describes the atmospheric aerosol load encountered during the large-scale pollution episode that occurred in August 2003, by means of the aerosol optical thicknesses (AOTs) measured at 865 nm by the Polarization and Directionality of the Earth's Reflectances (POLDER) sensor and the simulation by the CHIMERE chemistry-transport model. During this period many processes (stagnation, photochemistry, forest fires) led to unusually high particle concentrations and optical thicknesses. The observed/simulated AOT comparison helps understanding the ability of the model to reproduce most of the gross AOT features observed in satellite data, with a general agreement within a factor 2 and correlations in the 0.4–0.6 range. However some important aerosol features are missed when using regular anthropogenic sources. Additional simulations including emissions and high-altitude transport of smoke from wildfires that occurred in Portugal indicate that these processes could dominate the AOT signal in some areas. Our results also highlight the difficulties of comparing simulated and POLDER-derived AOTs due to large uncertainties in both cases. Observed AOT values are significantly lower than the simulated ones (30–50%). Their comparison with the ground-based Sun photometer Aerosol Robotic Network (AERONET) measurements suggests, for the European sites considered here, an underestimation of POLDER-derived aerosol levels with a factor between 1 and 2. AERONET AOTs compare better with simulations (no particular bias) than POLDER AOTs.
Retrieving the vertical distribution of stratospheric OClO from Odin/OSIRIS limb-scattered sunlight measurements
Authors: Krecl P. , Haley C. S. , Stegman J. , Brohede S. M. , Berthet G.
Published: April 2010

Abstract. The first vertical profiles of stratospheric OClO retrieved from Odin/OSIRIS limb-scattered sunlight radiances are presented. The retrieval method is based on a two-step approach, using differential optical absorption spectroscopy combined with the maximum a posteriori estimator. The details of the spectral window selection, spectral corrections and inversion technique are discussed. The results show that OClO can be detected inside the South polar vortex region between about 14 and 22 km altitude with a 2–5 km height resolution and an estimated retrieval error better than 50% at the peak. OClO concentrations show the expected relation to the atmospheric conditions in the lower stratosphere in the austral spring 2002. This unique data set of OClO profiles is very promising to study the stratospheric chlorine activation in both polar regions.
The semianalytical cloud retrieval algorithm for SCIAMACHY I. The validation
Authors: Kokhanovsky A. A. , Rozanov V. V. , Nauss T. , Reudenbach C. , Daniel J. S. , Miller H. L. , Burrows J. P.
Published: April 2010

Abstract. A recently developed cloud retrieval algorithm for the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) is briefly presented and validated using independent and well tested cloud retrieval techniques based on the look-up-table approach for MODeration resolutIon Spectrometer (MODIS) data. The results of the cloud top height retrievals using measurements in the oxygen A-band by an airborne crossed Czerny-Turner spectrograph and the Global Ozone Monitoring Experiment (GOME) instrument are compared with those obtained from airborne dual photography and retrievals using data from Along Track Scanning Radiometer (ATSR-2), respectively.
An unusual stratospheric ozone decrease in the Southern Hemisphere subtropics linked to isentropic air-mass transport as observed over Irene (25.5° S, 28.1° E) in mid-May 2002
Authors: Semane N. , Bencherif H. , Morel B. , Hauchecorne A. , Diab R. D.
Published: April 2010

Abstract. A prominent ozone minimum of less than 240 Dobson Units (DU) was observed over Irene (25.5° S, 28.1° E), a subtropical site in the Southern Hemisphere, by the Total Ozone Mapping Spectrometer (TOMS) during May 2002 with an extremely low ozone value of less than 219 DU recorded on 12 May, as compared to the climatological mean value of 249 DU for May between 1999 and 2005. In this study, the vertical structure of this ozone minimum is examined using ozonesonde measurements performed over Irene on 15 May 2002, when the total ozone (as given by TOMS) was about 226 DU. It is shown that this ozone minimum is of Antarctic polar origin with a low-ozone layer in the middle stratosphere above 625 K (where the climatological ozone gradient points equatorward), and is of tropical origin with a low-ozone layer in the lower stratosphere between the 400-K and 450-K isentropic levels (where the climatological ozone gradient is reversed). The upper and lower depleted parts of the ozonesonde profile for 15 May are then respectively attributed to equatorward and poleward transport of low-ozone air toward the subtropics in the Southern Hemisphere. The tropical air moving over Irene and the polar one passing over the same area associated with enhanced planetary-wave activity are successfully simulated using the high-resolution advection contour model of Ertel's potential vorticity MIMOSA. The unusual distribution of ozone over Irene during May 2002 in the middle stratosphere is connected to the anomalously pre-conditioned structure of the polar vortex at that time of the year. The winter stratospheric wave driving leading to the ozone minimum is investigated by means of the Eliassen-Palm flux computed from the European Center for Medium-range Weather Forecasts (ECMWF) ERA40 re-analyses.
Hygroscopic growth and critical supersaturations for mixed aerosol particles of inorganic and organic compounds of atmospheric relevance
Authors: Svenningsson B. , Rissler J. , Swietlicki E. , Mircea M. , Bilde M. , Facchini M. C. , Decesari S. , Fuzzi S. , Zhou J. , Mønster J. , Rosenørn T.
Published: April 2010

Abstract. The organic fraction of atmospheric aerosols contains a multitude of compounds and usually only a small fraction can be identified and quantified. However, a limited number of representative organic compounds can be used to describe the water-soluble organic fraction. In this work, initiated within the EU 5FP project SMOCC, four mixtures containing various amounts of inorganic salts (ammonium sulfate, ammonium nitrate, and sodium chloride) and three model organic compounds (levoglucosan, succinic acid and fulvic acid) were studied. The interaction between water vapor and aerosol particles was studied at different relative humidities: at subsaturation using a hygroscopic tandem differential mobility analyzer (H-TDMA) and at supersaturation using a cloud condensation nuclei spectrometer (CCN spectrometer). Surface tensions as a function of carbon concentrations were measured using a bubble tensiometer. Parameterizations of water activity as a function of molality, based on hygroscopic growth, are given for the pure organic compounds and for the mixtures, indicating van't Hoff factors around 1 for the organics. The Zdanovskii-Stokes-Robinson (ZSR) mixing rule was tested on the hygroscopic growth of the mixtures and it was found to adequately explain the hygroscopic growth for 3 out of 4 mixtures, when the limited solubility of succinic acid is taken into account. One mixture containing sodium chloride was studied and showed a pronounced deviation from the ZSR mixing rule. Critical supersaturations calculated using the parameterizations of water activity and the measured surface tensions were compared with those determined experimentally.
Geophysical validation of SCIAMACHY Limb Ozone Profiles
Authors: Brinksma E. J. , Bracher A. , Lolkema D. E. , Segers A. J. , Boyd I. S. , Bramstedt K. , Claude H. , Godin-Beekmann S. , Hansen G. , Kopp G. , Leblanc T. , McDermid I. S. , Meijer Y. J. , Nakane H. , Parrish A. , von Savigny C. , Stebel K. , Swart D. P. J. , Taha G. , Piters A. J. M.
Published: April 2010

Abstract. We discuss the quality of the two available SCIAMACHY limb ozone profile products. They were retrieved with the University of Bremen IFE's algorithm version 1.61 (hereafter IFE), and the official ESA offline algorithm (hereafter OL) versions 2.4 and 2.5. The ozone profiles were compared to a suite of correlative measurements from ground-based lidar and microwave, sondes, SAGE II and SAGE III (Stratospheric Aerosol and Gas Experiment). To correct for the expected Envisat pointing errors, which have not been corrected implicitly in either of the algorithms, we applied a constant altitude shift of -1.5 km to the SCIAMACHY ozone profiles. The IFE ozone profile data between 16 and 40 km are biased low by 3-6%. The average difference profiles have a typical standard deviation of 10% between 20 and 35 km. We show that more than 20% of the SCIAMACHY official ESA offline (OL) ozone profiles version 2.4 and 2.5 have unrealistic ozone values, most of these are north of 15° S. The remaining OL profiles compare well to correlative instruments above 24 km. Between 20 and 24 km, they underestimate ozone by 15±5%.
Single particle analysis of ice crystal residuals observed in orographic wave clouds over Scandinavia during INTACC experiment
Authors: Targino A. C. , Krejci R. , Noone K. J. , Glantz P.
Published: April 2010

Abstract. Individual ice crystal residual particles collected over Scandinavia during the INTACC (INTeraction of Aerosol and Cold Clouds) experiment in October 1999 were analyzed by Scanning Electron Microscopy (SEM) equipped with Energy-Dispersive X-ray Analysis (EDX). Samples were collected onboard the British Met Office Hercules C-130 aircraft using a Counterflow Virtual Impactor (CVI). This study is based on six samples collected in orographic clouds. The main aim of this study is to characterize cloud residual elemental composition in conditions affected by different airmasses. In total 609 particles larger than 0.1 μm diameter were analyzed and their elemental composition and morphology were determined. Thereafter a hierarchical cluster analysis was performed on the signal detected with SEM-EDX in order to identify the major particle classes and their abundance. A cluster containing mineral dust, represented by aluminosilicates, Fe-rich and Si-rich particles, was the dominating class of particles, accounting for about 57.5% of the particles analyzed, followed by low-Z particles, 23.3% (presumably organic material) and sea salt (6.7%). Sulfur was detected often across all groups, indicating ageing and in-cloud processing of particles. A detailed inspection of samples individually unveiled a relationship between ice crystal residual composition and airmass origin. Cloud residual samples from clean airmasses (that is, trajectories confined to the Atlantic and Arctic Oceans and/or with source altitude in the free troposphere) were dominated primarily by low-Z and sea salt particles, while continentally-influenced airmasses (with trajectories that originated or traveled over continental areas and with source altitude in the continental boundary layer) contained mainly mineral dust residuals. Comparison of residual composition for similar cloud ambient temperatures around –27°C revealed that supercooled clouds are more likely to persist in conditions where low-Z particles represent significant part of the analyzed cloud residual particles. This indicates that organic material may be poor ice nuclei, in contrast to polluted cases when ice crystal formation was observed at the same environmental conditions and when the cloud residual composition was dominated by mineral dust. The presented results suggest that the chemical composition of cloud nuclei and airmass origin have a strong impact on the ice formation through heterogeneous nucleation in supercooled clouds.
Measurements of CO2, its stable isotopes, O2/N2, and 222Rn at Bern, Switzerland
Authors: Sturm P. , Leuenberger M. , Valentino F. L. , Lehmann B. , Ihly B.
Published: April 2010

Abstract. A one-year time series of atmospheric CO2 measurements from Bern, Switzerland, is presented. O2/N2 and Ar/N2 ratios as well as stable carbon and oxygen isotopes of CO2 and δ29N2, δ34O2 and δ36Ar were measured periodically during a one year period. Additionally, the 222Rn activity was measured during three months in the winter 2004. Using the correlation from short-term fluctuations of CO2 and 222Rn we estimated a mean CO2 flux density between February 2004 and April 2004 in the region of Bern of 95±39 tC km–2month–1. The continuous observations of carbon dioxide and associated tracers shed light on diurnal and seasonal patterns of the carbon cycle in an urban atmosphere. There is considerable variance in nighttime δ13C and δ18O of source CO2 throughout the year, however, with generally lower values in winter compared to summertime. The O2:CO2 oxidation ratio during the nighttime build-up of CO2 varies between –0.96 and –1.69 mol O2/mol CO2. Furthermore, Ar/N2 measurements showed that artifacts like thermal fractionation at the air intake are relevant for high precision measurements of atmospheric O2.
Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change
Authors: Fuzzi S. , Andreae M. O. , Huebert B. J. , Kulmala M. , Bond T. C. , Boy M. , Doherty S. J. , Guenther A. , Kanakidou M. , Kawamura K. , Kerminen V.-M. , Lohmann U. , Russell L. M. , Pöschl U.
Published: April 2010

Abstract. In spite of impressive advances in recent years, our present understanding of organic aerosol (OA) composition, physical and chemical properties, sources and transformation characteristics is still rather limited, and their environmental effects remain highly uncertain. This paper discusses and prioritizes issues related to organic aerosols and their effects on atmospheric processes and climate, providing a basis for future activities in the field. Four main topical areas are addressed: i) sources of OA; ii) formation transformation and removal of OA; iii) physical, chemical and mixing state of OA; iv) atmospheric modelling of OA. Key questions and research priorities regarding these four areas are synthesized in this paper, and outstanding issues for future research are presented for each topical area. In addition, an effort is made to formulate a basic set of consistent and universally applicable terms and definitions for coherent description of atmospheric OA across different scales and disciplines.
Impact of transatlantic transport episodes on summertime ozone in Europe
Authors: Guerova G. , Bey I. , Attié J.-L. , Martin R. V. , Cui J. , Sprenger M.
Published: April 2010

Abstract. This paper reports on the transport of ozone (O3) and related species over the North Atlantic ocean and its impact on Europe. Measurements of nitrogen dioxide (NO2) and carbon monoxide (CO) columns from the GOME and MOPITT satellite instruments, respectively, are used in conjunction with the GEOS-CHEM global model of transport and tropospheric chemistry to identify the major events of long range transport that reach Europe over the course of summer 2000. Sensitivity model simulations are used to analyse observed O3 distributions with respect to the impact of long range transport events. For that purpose, we used in-situ O3 observations taken at the mountain site of Jungfraujoch as well as O3 vertical profiles taken in the vicinity of central European cities. Over the course of summer 2000, we identified 9 major episodes of transatlantic pollution transport; 7 events are associated with transient cyclones while 2 events occur through zonal transport (e.g. by advection in the strong low-level westerly winds established in summer between the Azores anticyclone and transient cyclones). We find that on average three episodes occur per month with the strongest ones being in June. The number and frequency of long range transport events that reach Europe are driven by the position and strength of the Azores anticyclone. Model sensitivity simulations indicate that the summer mean North American O3 contribution ranges from 3 to 5 ppb (7–11%) in the planetary boundary layer and 10 to 13 ppb (18–23%) in the middle and upper troposphere. During particular episodes, North American sources can result in O3 enhancements up to 25–28 ppb in the layer between 800–600 hPa and 10–12 ppb in the boundary layer. The impact of the zonal transport events on O3 distribution over Europe is more clearly seen below 700 hPa as they tend to transport pollution at lower levels while the events associated with transient cyclones are more likely to have an impact on the middle and upper troposphere (i.e. above 600 hPa). The air mass origins found in the GEOS-CHEM model are clearly confirmed by back trajectory analyses. During most of the 9 events, a strong contribution in North American O3 is in general associated with only little European O3 and vice-versa (in particular at the Jungfraujoch). A substantial North American contribution (e.g., 30% or higher) to O3 over Europe does not always result in pronounced O3 enhancements in the observations during our period of study.
Impact of climate variability and land use changes on global biogenic volatile organic compound emissions
Authors: Lathière J. , Hauglustaine D. A. , Friend A. D. , De Noblet-Ducoudré N. , Viovy N. , Folberth G. A.
Published: April 2010

Abstract. A biogenic emissions scheme has been incorporated in the global dynamic vegetation model ORCHIDEE (Organizing Carbon and Hydrology in Dynamic EcosystEms) in order to calculate global biogenic emissions of isoprene, monoterpenes, methanol, acetone, acetaldehyde, formaldehyde and formic and acetic acids. Important parameters such as the leaf area index are fully determined by the global vegetation model and the influences of light extinction (for isoprene emissions) and leaf age (for isoprene and methanol emissions) are also taken into account. We study the interannual variability of biogenic emissions using the satellite-based climate forcing ISLSCP-II as well as relevant CO2 atmospheric levels, for the 1983–1995 period. Mean global emissions of 460 TgC/yr for isoprene, 117 TgC/yr for monoterpenes, 106 TgC/yr for methanol and 42 TgC/yr for acetone are predicted. The mean global emission of all biogenic compounds is 752±16 TgC/yr with extremes ranging from 717 TgC/yr in 1986 to 778 TgC/yr in 1995, that is a 8.5% increase between both. This variability differs significantly from one region to another and among the regions studied, biogenic emissions anomalies were the most variable in Europe and the least variable in Indonesia (isoprene and monoterpenes) and North America (methanol). Two scenarios of land use changes are considered using the 1983 climate and atmospheric CO2 conditions, to study the sensitivity of biogenic emissions to vegetation alteration, namely tropical deforestation and European afforestation. Global biogenic emissions are highly affected by tropical deforestation, with a 29% decrease in isoprene emission and a 22% increase in methanol emission. Global emissions are not significantly affected by European afforestation, but on a European scale, total biogenic VOCs emissions increase by 54%.
Effect of humidity on nitric acid uptake to mineral dust aerosol particles
Authors: Vlasenko A. , Sjogren S. , Weingartner E. , Stemmler K. , Gäggeler H. W. , Ammann M.
Published: April 2010

Abstract. This study presents the first laboratory observation of HNO3 uptake by airborne mineral dust particles. The model aerosols were generated by dry dispersion of Arizona Test Dust (ATD), SiO2, and by nebulizing a saturated solution of calcium carbonate. The uptake of 13N-labeled gaseous nitric acid was observed in a flow reactor on the 0.2–2 s reaction time scale at room temperature and atmospheric pressure. The amount of nitric acid appearing in the aerosol phase at the end of the flow tube was found to be a linear function of the aerosol surface area. SiO2 particles did not show any significant uptake, while the CaCO3 aerosol was found to be more reactive than ATD. Due to the smaller uncertainty associated with the reactive surface area in the case of suspended particles as compared to bulk powder samples, we believe that we provide an improved estimate of the rate of uptake of HNO3 to mineral dust. The fact that the rate of uptake was smaller at a concentration of 1012 than at 1011 was indicative of a complex uptake mechanism. The uptake coefficient averaged over the first 2 s of reaction time at a concentration of 1012 molecules cm-3 was found to increase with increasing relative humidity, from 0.022±0.007 at 12% RH to 0.113±0.017 at 73% RH , which was attributed to an increasing degree of solvation of the more basic minerals. The extended processing of the dust by higher concentrations of HNO3 at 85% RH led to a water soluble coating on the particles and enhanced their hygroscopicity.
Aerosol and NOx emission factors and submicron particle number size distributions in two road tunnels with different traffic regimes
Authors: Imhof D. , Weingartner E. , Prévôt A. S. H. , Ordóñez C. , Kurtenbach R. , Wiesen P. , Rodler J. , Sturm P. , McCrae I. , Ekström M. , Baltensperger U.
Published: April 2010

Abstract. Measurements of aerosol particle number size distributions (18–700 nm), mass concentrations (PM2.5 and PM10) and NOx were performed in the Plabutsch tunnel, Austria, and in the Kingsway tunnel, United Kingdom. These two tunnels show different characteristics regarding the roadway gradient, the composition of the vehicle fleet and the traffic frequency. The submicron particle size distributions contained a soot mode in the diameter range D=80–100 nm and a nucleation mode in the range of D=20–40 nm. In the Kingsway tunnel with a significantly lower particle number and volume concentration level than in the Plabutsch tunnel, a clear diurnal variation of nucleation and soot mode particles correlated to the traffic density was observed. In the Plabutsch tunnel, soot mode particles also revealed a diurnal variation, whereas no substantial variation was found for the nucleation mode particles. During the night a higher number concentration of nucleation mode particles were measured than soot mode particles and vice versa during the day. In this tunnel with very high soot emissions during daytime due to the heavy-duty vehicle (HDV) share of 18% and another 40% of diesel driven light-duty vehicles (LDV) semivolatile species condense on the pre-existing soot surface area rather than forming new particles by homogeneous nucleation. With the low concentration of soot mode particles in the Kingsway tunnel, also the nucleation mode particles exhibit a diurnal variation. From the measured parameters real-world traffic emission factors were estimated for the whole vehicle fleet as well as differentiated into the two categories LDV and HDV. In the particle size range D=18–700 nm, each vehicle of the mixed fleet emits (1.50±0.08)×1014 particles km-1 (Plabutsch) and (1.26±0.10)×1014 particles km-1 (Kingsway), while particle volume emission factors of 0.209±0.008 cm3 km-1 and 0.036±0.004 cm3 km-1, respectively, were obtained. PM1 emission factors of 104±4 mg km-1 (Plabutsch) and 41±4 mg km-1 (Kingsway) were calculated. Emission factors determined in this work were in good agreement with results from other studies.
Detection and measurement of total ozone from stellar spectra: Paper 2. Historic data from 1935–1942
Authors: Griffin R. E. M.
Published: April 2010

Abstract. Atmospheric ozone columns are derived from historic stellar spectra observed between 1935 and 1942 at Mount Wilson Observatory, California. Comparisons with contemporary measurements in the Arosa database show a generally close correspondence, while a similar comparison with more sparse data from Table Mountain reveals a difference of ~15–20%, as has also been found by other researches of the latter data. The results of the analysis indicate that astronomy's archives command considerable potential for investigating the natural levels of ozone and its variability during the decades prior to anthropogenic interference.
Stratosphere-troposphere exchange in a summertime extratropical low: analysis
Authors: Brioude J. , Cammas J.-P. , Cooper O. R.
Published: April 2010

Abstract. Ozone and carbon monoxide measurements sampled during two commercial flights in airstreams of a summertime midlatitude cyclone are analysed with a Lagrangian-based study (backward trajectories and a Reverse Domain Filling technique) to gain a comprehensive understanding of transport effects on trace gas distributions. The study demonstrates that summertime cyclones can be associated with deep stratosphere-troposphere transport. A tropopause fold is sampled twice in its life cycle, once in the lower troposphere (O3≃100 ppbv; CO≃90 ppbv) in the dry airstream of the cyclone, and again in the upper troposphere (O3≃200 ppbv; CO≃90 ppbv) on the northern side of the large scale potential vorticity feature associated with baroclinic development. In agreement with the maritime development of the cyclone, the chemical composition of the anticyclonic portion of the warm conveyor belt outflow (O3≃40 ppbv; CO≃85 ppbv) corresponds to the lowest mixing ratios of both ozone and carbon monoxide in the upper tropospheric airborne observations. The uncertain degree of confidence of the Lagrangian-based technique applied to a 100 km segment of upper level airborne observations with high ozone (200 ppbv) and relatively low CO (80 ppbv) observed northwest of the cyclone prevents identification of the ozone enrichment process of air parcels embedded in the cyclonic part of the upper level outflow of the warm conveyor belt. Different hypotheses of stratosphere-troposphere exchange are discussed.
Aerosol direct radiative effect at the top of the atmosphere over cloud free ocean derived from four years of MODIS data
Authors: Remer L. A. , Kaufman Y. J.
Published: April 2010

Abstract. A four year record of MODIS spaceborne data provides a new measurement tool to assess the aerosol direct radiative effect at the top of the atmosphere. MODIS derives the aerosol optical thickness and microphysical properties from the scattered sunlight at 0.55–2.1 μm. The monthly MODIS data used here are accumulated measurements across a wide range of view and scattering angles and represent the aerosol's spectrally resolved angular properties. We use these data consistently to compute with estimated accuracy of ±0.6 Wm−2 the reflected sunlight by the aerosol over global oceans in cloud free conditions. The MODIS high spatial resolution (0.5 km) allows observation of the aerosol impact between clouds that can be missed by other sensors with larger footprints. We found that over the clear-sky global ocean the aerosol reflected 5.3±0.6 Wm−2 with an average radiative efficiency of −49±2 Wm−2 per unit optical thickness. The seasonal and regional distribution of the aerosol radiative effects are discussed. The analysis adds a new measurement perspective to a climate change problem dominated so far by models.
Aerosol activation and cloud processing in the global aerosol-climate model ECHAM5-HAM
Authors: Roelofs G. J. , Stier P. , Feichter J. , Vignati E. , Wilson J.
Published: April 2010

Abstract. A parameterization for cloud processing is presented that calculates activation of aerosol particles to cloud drops, cloud drop size, and pH-dependent aqueous phase sulfur chemistry. The parameterization is implemented in the global aerosol-climate model ECHAM5-HAM. The cloud processing parameterization uses updraft speed, temperature, and aerosol size and chemical parameters simulated by ECHAM5-HAM to estimate the maximum supersaturation at the cloud base, and subsequently the cloud drop number concentration (CDNC) due to activation. In-cloud sulfate production occurs through oxidation of dissolved SO2 by ozone and hydrogen peroxide. The model simulates realistic distributions for annually averaged CDNC although it is underestimated especially in remote marine regions. On average, CDNC is dominated by cloud droplets growing on particles from the accumulation mode, with smaller contributions from the Aitken and coarse modes. The simulations indicate that in-cloud sulfate production is a potentially important source of accumulation mode sized cloud condensation nuclei, due to chemical growth of activated Aitken particles and to enhanced coalescence of processed particles. The strength of this source depends on the distribution of produced sulfate over the activated modes. This distribution is affected by uncertainties in many parameters that play a direct role in particle activation, such as the updraft velocity, the aerosol chemical composition and the organic solubility, and the simulated CDNC is found to be relatively sensitive to these uncertainties.
In-situ comparison of the NOy instruments flown in MOZAIC and SPURT
Authors: Pätz H.-W. , Volz-Thomas A. , Hegglin M. I. , Brunner D. , Fischer H. , Schmidt U.
Published: April 2010

Abstract. Two aircraft instruments for the measurement of total odd nitrogen (NOy) were compared side by side aboard a Learjet A35 in April 2003 during a campaign of the AFO2000 project SPURT (Spurengastransport in der Tropopausenregion). The instruments albeit employing the same measurement principle (gold converter and chemiluminescence) had different inlet configurations. The ECO-Physics instrument operated by ETH-Zürich in SPURT had the gold converter mounted outside the aircraft, whereas the instrument operated by FZ-Jülich in the European project MOZAIC III (Measurements of ozone, water vapour, carbon monoxide and nitrogen oxides aboard Airbus A340 in-service aircraft) employed a Rosemount probe with 80 cm of FEP-tubing connecting the inlet to the gold converter. The NOy concentrations during the flight ranged between 0.3 and 3 ppb. The two data sets were compared in a blind fashion and each team followed its normal operating procedures. On average, the measurements agreed within 7%, i.e. within the combined uncertainty of the two instruments. This puts an upper limit on potential losses of HNO3 in the Rosemount inlet of the MOZAIC instrument. Larger transient deviations were observed during periods after calibrations and when the aircraft entered the stratosphere. The time lag of the MOZAIC instrument observed in these instances is in accordance with the time constant of the MOZAIC inlet line determined in the laboratory for HNO3.
A chemical probe technique for the determination of reactive halogen species in aqueous solution: Part 2 – chloride solutions and mixed bromide/chloride solutions
Authors: Anastasio C. , Matthew B. M.
Published: April 2010

Abstract. Although reactive halogen species (X*=X•, •X2-, X2 and HOX, where X=Br, Cl, or I) are important environmental oxidants, relatively little is known about their kinetics in condensed phases such as seawater and sea-salt particles. Here we describe a new technique to determine reactive chlorine and bromine species in aqueous solutions by using allyl alcohol (CH2=CHCH2OH) as a chemical probe. This probe is combined with competition kinetics in order to determine steady state concentrations of X*(aq). In some cases the technique also can be used to determine the rates of formation and lifetimes of X* in aqueous solution. In a companion paper we reported the results of our method development for aqueous solutions containing only bromide (Br-). In this paper, we discuss method development for solutions containing chloride (Cl-) alone, and for solutions containing both bromide and chloride.
Cloud Condensation Nuclei properties of model and atmospheric HULIS
Authors: Dinar E. , Taraniuk I. , Graber E. R. , Katsman S. , Moise T. , Anttila T. , Mentel T. F. , Rudich Y.
Published: April 2010

Abstract. Humic like substances (HULIS) have been identified as a major fraction of the organic component of atmospheric aerosols. These large multifunctional compounds of both primary and secondary sources are surface active and water soluble. Hence, it is expected that they could affect activation of organic aerosols into cloud droplets. We have compared the activation of aerosols containing atmospheric HULIS extracted from fresh, aged and pollution particles to activation of size fractionated fulvic acid from an aquatic source (Suwannee River Fulvic Acid), and correlated it to the estimated molecular weight and measured surface tension. A correlation was found between CCN-activation diameter of SRFA fractions and number average molecular weight of the fraction. The lower molecular weight fractions activated at lower critical diameters, which is explained by the greater number of solute species in the droplet with decreasing molecular weight. The three aerosol-extracted HULIS samples activated at lower diameters than any of the size-fractionated or bulk SRFA. The Köhler model was found to account for activation diameters, provided that accurate physico-chemical parameters are known.
Switching cloud cover and dynamical regimes from open to closed Benard cells in response to the suppression of precipitation by aerosols
Authors: Rosenfeld D. , Kaufman Y. J. , Koren I.
Published: April 2010

Abstract. The dynamic structure of the weakly sheared atmospheric marine boundary layer (MBL) supports three distinct states of cloud cover, which are associated with the concentrations of cloud condensation nuclei (CCN) aerosols in the MBL: (i) CCN rich MBL with closed Benard cellular convection that forms nearly full cloud cover; (ii) CCN depleted MBL with open cellular convection that forms <40% cloud cover; and, (iii) CCN starved MBL where clouds cannot form due to insufficient CCN, with near zero cloud cover. Here we propose a mechanism for the transition between these three states that involves the aerosol impacts on precipitation and the feedbacks on the dynamics of the clouds and on the aerosols deposition. By suppressing precipitation aerosols can reverse the direction of the airflow, converting the cloud structure from open to closed cells and more than doubling the cloud cover. The three states possess positive feedbacks for self maintenance, so that small changes of the conditions can lead to bifurcation of the MBL cloud regime. The transition between the closed and open cells occur at near pristine background level of aerosols, creating a large sensitivity of cloud radiative forcing to very small changes in aerosols at the MBL. The third state of super clean air can occur as the more efficient precipitation in cleaner air deposits the aerosols ever faster in a runaway positive feedback process. The proposed mechanism suggests that very small changes in the aerosols input to the MBL can have large impacts on the oceanic cloud cover and likely in turn on the global temperature, in ways that are not yet accounted for in the climate models.
Closure between measured and modeled cloud condensation nuclei (CCN) using size-resolved aerosol compositions in downtown Toronto
Authors: Broekhuizen K. , Chang R.Y.-W. , Leaitch W. R. , Li S.-M. , Abbatt J. P. D.
Published: April 2010

Abstract. Measurements of cloud condensation nuclei (CCN) were made in downtown Toronto during August and September, 2003. CCN measurements were performed at 0.58% supersaturation using a thermal-gradient diffusion chamber, whereas the aerosol size distribution and composition were simultaneously measured with a TSI SMPS and APS system and an Aerodyne Aerosol Mass Spectrometer (AMS), respectively. Aerosol composition data shows that the particles were predominately organic in nature, in particular for those with a vacuum aerodynamic diameter of <0.25 µm. In this study, the largest contribution to CCN concentrations came from this size range, suggesting that the CCN are also organic-rich. Using the size and composition information, detailed CCN closure analyses were performed. In the first analysis, the particles were assumed to be internally mixed, the organic fraction was assumed to be insoluble, and the inorganic fraction was assumed to be ammonium sulfate. The AMS time-of-flight data were used for Köhler theory predictions for each particle size and composition to obtain the dry diameter required for activation. By so doing, this closure analysis yielded an average value of CCNpredicted/CCNobserved=1.12±0.05. However, several sample days showed distinct bimodal distributions, and a closure analysis was performed after decoupling the two particle modes. This analysis yielded an average value of CCNpredicted/CCNobserved=1.03±0.05. A sensitivity analysis was also performed to determine the aerosol/CCN closure if the organic solubility, droplet surface tension, or chamber supersaturation were varied.