bluuebunny/crossref_metadata_2025 huggingface dataset:
Temperature dependence of yields of secondary organic aerosols from the ozonolysis of α-pinene and limonene
Authors: Saathoff H. , Naumann K.-H. , Möhler O. , Jonsson Å. M. , Hallquist M. , Kiendler-Scharr A. , Mentel Th. F. , Tillmann R. , Schurath U.
Published: April 2010

Abstract. Secondary organic aerosol (SOA) formation has been investigated as a function of temperature and humidity for the ozone-initiated reaction of the two monoterpenes α-pinene (243–313 K) and limonene (253–313 K) using the 84.5 m3 aerosol chamber AIDA. This paper gives an overview of the measurements done and presents parameters specifically useful for aerosol yield calculations. The ozonolysis reaction, selected oxidation products and subsequent aerosol formation were followed using several analytical techniques for both gas and condensed phase characterisation. The effective densities of the SOA were determined by comparing mass and volume size distributions to (1.25±0.10) g cm−3 for α-pinene and (1.3±0.2) g cm−3 for limonene. The detailed aerosol dynamics code COSIMA-SOA proved to be essential for a comprehensive evaluation of the experimental results and for providing parameterisations directly applicable within atmospheric models. The COSIMA-assisted analysis succeeded to reproduce the observed time evolutions of SOA total mass, number and size distributions by adjusting the following properties of two oxidation product proxies: individual yield parameters (αi), partitioning coefficients (Ki), vapour pressures (pi) and effective accommodation coefficients (γi). For these properties temperature dependences were derived and parameterised. Vapour pressures and partitioning coefficients followed classical Clausius-Clapeyron temperature dependences. From this relationship enthalpies of vaporisation were derived for the two more and less volatile product proxies of α-pinene: (59±8) kJ mol−1 and (24±9) kJ mol−1, and limonene: (55±14) kJ mol−1 and (25±12) kJ mol−1. The more volatile proxy components had a notably low enthalpy of vaporisation while the less volatile proxy components gave enthalpies of vaporisation comparable with those of typical products from α-pinene oxidation, e.g. pinonaldehyde and pinonic acid.
Seasonal variation of aerosol size distribution at Puy de Dôme (1465 m a.s.l., central France)
Authors: Venzac H. , Sellegri K. , Villani P. , Picard D. , Laj P.
Published: April 2010

Abstract. Particle number concentration and size distribution are amongst the most important variables needed to constrain the role of the atmospheric particles in the Earth radiative budget. They are also linked to regulated variables such as particle mass (PM) and therefore of interest to air quality studies. However, data on their long-term variability are scarce, in particular at high altitudes where the occurrence of aerosol in elevated layers cannot be resolved from most instruments in space. Therefore it is crucial to provide ground based measurements of suited aerosol variables to obtain closure between all independent information sources. In this paper, we investigate diurnal and seasonal variability of aerosol number concentration and size distribution at the Puy de Dôme research station (France, 1465 m a.s.l.). We report variability of aerosol particle total number concentration measured over a five years (2003–2007) period and aerosol size distributions over a one year period (January to December 2006). Concentrations show a strong seasonality with maxima during summer and minima during winter. A diurnal variation is also observed with maxima between 12:00 and 18:00 UTC. At night (00:00–06:00 UTC), the median hourly total concentration varies from 600 to 800 cm−3 during winter and from 1700 to 2200 cm−3 during summer. During the day (08:00–18:00 UTC), the concentration is in the range of 700 to 1400 cm−3 during winter and from 2500 to 3500 cm−3 during summer. An averaged size distribution of particles (10–500 nm) was calculated for each season. A variability in the size of aerosols sampled at the Puy de Dôme is also observed on the seasonal and diurnal basis. Because the site lies in the free troposphere only a fraction of the time, in particular at night and during the winter season, we have subsequently analyzed the variability for free tropospheric conditions only. We show that the variability is due to both seasonal changes in air mass origin from winter to summer and enhanced concentration of the free troposphere in summer. The later observation can be explained by higher emission intensity in the boundary layer, stronger exchange between the boundary layer and the free troposphere as well as enhanced photochemical processes. Finally, aerosol mean size distributions are calculated for a given air mass type (marine/continental/regional) according to the season, for the specific conditions of the free troposphere. These results are of regional relevance and can be used to constrain chemical-transport models over Western Europe.
Fossil and non-fossil sources of organic carbon (OC) and elemental carbon (EC) in Göteborg, Sweden
Authors: Szidat S. , Ruff M. , Wacker L. , Synal H.-A. , Hallquist M. , Shannigrahi A. S. , Yttri K. E. , Dye C. , Simpson D.
Published: April 2010

Abstract. Particulate matter was collected at an urban site in Göteborg (Sweden) in February/March 2005 and in June/July 2006. Additional samples were collected at a rural site for the winter period. Elemental carbon (EC), organic carbon (OC), water-insoluble OC (WINSOC), and water-soluble OC (WSOC) were analyzed for 14C in order to distinguish fossil from non-fossil emissions. As wood burning is the single major source of non-fossil EC, its contribution can be quantified directly. For non-fossil OC, the wood burning fraction was determined independently by levoglucosan and 14C analysis and combined using Latin-hypercube sampling (LHS). For the winter period, the relative contribution of EC from wood burning to the total EC was >3 times higher at the rural site compared to the urban site, whereas the absolute concentrations of EC from wood burning were comparable at both sites. Thus, the urban site is substantially more influenced by fossil EC emissions. For summer, biogenic emissions dominated OC concentrations most likely due to secondary organic aerosol (SOA) formation. During both seasons, a more pronounced fossil signal was observed for Göteborg than has previously been reported for Zurich, Switzerland. Analysis of air mass origin using back trajectories suggests that the fossil impact was larger when local sources dominated, whereas long-range transport caused an enhanced non-fossil signal. In comparison to other European locations, concentrations of levoglucosan and other monosaccharide anhydrides were low for the urban and the rural site in the area of Göteborg during winter. The comparison of summer and winter results provides insight into the annual cycle of anthropogenic vs. biogenic contributions to the atmospheric aerosol.
Interannual variability of long-range transport as seen at the Mt. Bachelor Observatory
Authors: Reidmiller D. R. , Jaffe D. A. , Chand D. , Strode S. , Swartzendruber P. , Wolfe G. M. , Thornton J. A.
Published: April 2010

Abstract. Interannual variations in background tropospheric trace gases (such as carbon monoxide, CO) are largely driven by variations in emissions (especially wildfires), transport pathways and tropospheric oxidizing capacity. Understanding this variability is essential to quantify the intercontinental contribution to US air quality. We investigate the interannual variability of long-range transport of Asian pollutants to the Northeast Pacific via measurements from the Mt. Bachelor Observatory (MBO: 43.98° N, 121.69° W; 2.7 km above sea level) and GEOS-Chem chemical transport model simulations in spring 2005 vs. the INTEX-B campaign during spring 2006. Measurements of CO at MBO were significantly enhanced during spring 2005 relative to the same time in 2006 (the INTEX-B study period); a monthly mean decline in CO of 41 ppbv was observed between April 2005 and April 2006. Meteorological indices show that long-range transport of CO from the heavily industrialized region of East Asia was significantly greater in 2005 than in 2006. In addition, spring 2005 was an anomalously strong biomass burning season in Southeast Asia. Data presented by Yurganov et al. (2008) using MOPITT satellite retrievals from this area reveal an average CO burden anomaly (referenced to March 2000–February 2002 mean values) between October 2004 through April 2005 of 2.6 Tg CO vs. 0.6 Tg CO for the same period a year later. The Naval Research Laboratory's global aerosol transport model shows that emissions from these fires were efficiently transported to MBO throughout April 2005. Asian dust transport, however, was substantially greater in 2006 than 2005, particularly in May. Monthly mean aerosol light scattering coefficient at 532 nm (σsp) at MBO more than doubled from 2.7 Mm−1 in May 2005 to 6.2 Mm−1 in May 2006. We also evaluate CO interannual variability throughout the western US via Earth System Research Laboratory ground site data and throughout the Northern Hemisphere via MOPITT and TES satellite observations. Both in the Northeast Pacific and on larger scales, we reveal a significant decrease (from 2–21%) in springtime maximum CO between 2005 and 2006, evident in all platforms and the GEOS-Chem model. We attribute this to (a) anomalously strong biomass burning in Southeast Asia during winter 2004 through spring 2005, and (b) the transport pattern in 2006 which limited the inflow of Asian pollution to the lower free troposphere over western North America.
On the extraction of wind information from the assimilation of ozone profiles in Météo–France 4D-Var operational NWP suite
Authors: Semane N. , Peuch V.-H. , Pradier S. , Desroziers G. , El Amraoui L. , Brousseau P. , Massart S. , Chapnik B. , Peuch A.
Published: April 2010

Abstract. By applying four-dimensional variational data-assimilation (4D-Var) to a combined ozone and dynamics Numerical Weather Prediction model (NWP), ozone observations generate wind increments through the ozone-dynamics coupling. The dynamical impact of Aura/MLS satellite ozone profiles is investigated using Météo–France operational ARPEGE NWP 4D-Var assimilation system for a period of 3 months. A data-assimilation procedure has been designed and run on 6-h windows. The procedure includes: (1) 4D-Var assimilating both ozone and operational NWP standard observations, (2) ARPEGE transporting ozone as a passive-tracer, (3) MOCAGE, the Météo–France chemistry and transport model re-initializing the ARPEGE ozone background at the beginning time of the assimilation window. The Degrees of Freedom for Signal diagnostics show that the MLS data covering the 68.1–31.6 hPa vertical pressure range are the most informative and their information content is nearly of the same order as tropospheric humidity-sensitive radiances. Furthermore, with the help of error variance reduction diagnostics, the ozone contribution to the reduction of the horizontal divergence background-error variance is shown to be better than tropospheric humidity-sensitive radiances. Moreover, by using observation minus forecast statistics, it is found that the ozone assimilation reduces the wind bias in the lower stratosphere.
Past and future conditions for polar stratospheric cloud formation simulated by the Canadian Middle Atmosphere Model
Authors: Hitchcock P. , Shepherd T. G. , McLandress C.
Published: April 2010

Abstract. Observations of the Arctic winter lower stratosphere over the past four decades suggest that the thermodynamic conditions required for the formation of polar stratospheric clouds (PSCs) have become increasingly widespread in the Northern Hemisphere. The trend is apparent only in the coldest winters during which the Arctic stratosphere is minimally disturbed by upwelling wave activity from the troposphere. The mechanism responsible for this increase remains unclear. In an effort to evaluate possible mechanisms, we analyze here the polar stratospheric temperatures in an ensemble of three 150-year integrations of the Canadian Middle Atmosphere Model (CMAM), an interactive chemistry-climate model which simulates ozone depletion and recovery, as well as climate change. We find that in the Antarctic winter lower stratosphere, the low temperature extremes required for PSC formation increase in the model as ozone is depleted, but remain steady through the twenty-first century as the warming from ozone recovery roughly balances the cooling from climate change. Thus, ozone depletion itself plays a major role in the Antarctic response. The model trend in low temperature extremes in the Arctic through the latter half of the twentieth century is weaker and less statistically robust than the observed trend. It is not projected to continue into the future. Ozone depletion in the Arctic is weaker in the CMAM than in observations, which may account for the weak past trend in low temperature extremes. In the future, radiative cooling in the Arctic winter due to climate change is more than compensated by an increase in dynamically driven downwelling over the pole.
Aerosol hygroscopicity in the marine atmosphere: a closure study using high-resolution, size-resolved AMS and multiple-RH DASH-SP data
Authors: Hersey S. P. , Sorooshian A. , Murphy S. M. , Flagan R. C. , Seinfeld J. H.
Published: April 2010

Abstract. We have conducted the first closure study to couple high-resolution aerosol mass spectrometer (AMS) composition data with size-resolved, multiple-RH, high-time-resolution hygroscopic growth factor (GF) measurements from the differential aerosol sizing and hygroscopicity spectrometer probe (DASH-SP). These data were collected off the coast of Central California during seven of the 16 flights carried out during the MASE-II field campaign in July 2007. Two of the seven flights were conducted in airmasses that originated over the continental United States. These flights exhibited elevated organic volume fractions (VForganic=0.46±0.22, as opposed to 0.24±0.18 for all other flights), corresponding to significantly suppressed GFs at high RH (1.61±0.14 at 92% RH, as compared with 1.91±0.07 for all other flights), more moderate GF suppression at intermediate RH (1.53±0.10 at 85%, compared with 1.58±0.08 for all other flights, and no measurable GF suppression at low RH (1.31±0.06 at 74%, compared with 1.31±0.07 for all other flights). Organic loadings were slightly elevated in above-cloud aerosols, as compared with below-cloud aerosols, and corresponded to a similar trend of significantly suppressed GF at high RH, but more moderate impacts at lower values of RH. A hygroscopic closure based on a volume-weighted mixing rule provided excellent agreement with DASH-SP measurements (R2=0.79). Minimization of root mean square error between observations and predictions indicated mission-averaged organic GFs of 1.20, 1.43, and 1.46 at 74, 85, and 92% RH, respectively. These values agree with previously reported values for water-soluble organics such as dicarboxylic and multifunctional acids, and correspond to a highly oxidized, presumably water-soluble, organic fraction (O:C=0.92±0.33). Finally, a backward stepwise linear regression revealed that, other than RH, the most important predictor for GF is VForganic, indicating that a simple emperical model relating GF, RH, and the relative abundance of organic material can provide accurate predictions of hygroscopic growth in the marine atmosphere.
Influence of non-ideality on aerosol growth
Authors: Compernolle S. , Ceulemans K. , Müller J.-F.
Published: April 2010

Abstract. Secondary organic aerosol (SOA) is a complex mixture of water and organic molecules. Its composition is determined by the presence of semi-volatile or non-volatile compounds, their vapor pressure and activity coefficient. The activity coefficient is a non-ideality effect and is a complex function of SOA composition. In a previous publication, the detailed chemical mechanism (DCM) for α-pinene oxidation and subsequent aerosol formation BOREAM was presented. In this work, we investigate with this DCM the impact of non-ideality by simulating smog chamber experiments for α-pinene degradation and aerosol formation. Several versions of the UNIFAC method are tested for this purpose, and missing parameters for e.g. hydroperoxides and nitrates are inferred from fittings to activity coefficient data generated using the SPARC model. It turns out that for most experiments, non-ideality has only a limited impact on the interaction between the organic molecules, and therefore on SOA yields and composition, when water uptake is ignored. Still, for ozonolysis experiments with low amounts of volatile organic carbon (low-VOC), the UNIFAC parameterization of Raatikainen et al. leads to significantly higher SOA yields (by up to a factor 1.6) compared to the ideal case and to other parameterizations. Water uptake is model dependent, in the order: ideal>UNIFAC-Raatikainen>UNIFAC-Peng>UNIFAC-Hansen≈UNIFAC-Magnussen≈UNIFAC-Ming. In the absence of salt dissolution, phase splitting from pure SOA is unlikely.
Laboratory investigation of photochemical oxidation of organic aerosol from wood fires – Part 2: Analysis of aerosol mass spectrometer data
Authors: Grieshop A. P. , Donahue N. M. , Robinson A. L.
Published: April 2010

Abstract. Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) in dilute wood smoke by exposing emissions from soft- and hard-wood fires to UV light in a smog chamber. This paper focuses on changes in OA composition measured using a unit mass resolution quadrupole Aerosol Mass Spectrometer (AMS). The results highlight how photochemical processing can lead to considerable evolution of the mass, the volatility and the level of oxygenation of biomass-burning OA. Photochemical oxidation produced substantial new OA, more than doubling the primary contribution after a few hours of aging under typical summertime conditions. Aging decreased the OA volatility of the total OA as measured with a thermodenuder; it also made the OA progressively more oxygenated in every experiment. With explicit knowledge of the condensed-phase mass spectrum (MS) of the primary emissions from each fire, each MS can be decomposed into primary and residual spectra throughout the experiment. The residual spectra provide an estimate of the composition of the photochemically produced OA. These spectra are also very similar to those of the oxygenated OA that dominates ambient AMS datasets. In addition, aged wood smoke spectra are shown to be similar to those from OA created by photo-oxidized dilute diesel exhaust and aged biomass-burning OA measured in urban and remote locations. This demonstrates that the oxygenated OA observed in the atmosphere can be produced by photochemical aging of dilute emissions from combustion of fuels containing both modern and fossil carbon.
Results of the first air ion spectrometer calibration and intercomparison workshop
Authors: Asmi E. , Sipilä M. , Manninen H. E. , Vanhanen J. , Lehtipalo K. , Gagné S. , Neitola K. , Mirme A. , Mirme S. , Tamm E. , Uin J. , Komsaare K. , Attoui M. , Kulmala M.
Published: April 2010

Abstract. The air ion spectrometer (AIS) measures mobility and size distributions of atmospheric ions. The neutral air ion spectrometer (NAIS) can additionally measure neutral particles. The number of the (N)AIS instruments in the world is only 11. Nevertheless, they are already widely used in atmospheric ion studies, particularly related to the initial steps of new particle formation. There is no standard method applicable for calibrating the ion spectrometers in the sub-3 nm ion range. However, recent development of high resolution DMAs has enabled the size separation of small ions with good mobility resolution. For the first time, the ion spectrometers were intercompared and calibrated in a workshop, held in January–February 2008 in Helsinki, Finland. The overall goal was to experimentally determine the (N)AIS transfer functions. Monomobile mobility standards, 241-Am charger ions and silver particles were generated and used as calibration aerosols. High resolution DMAs were used to size-separate the smaller (1–10 nm) ions, while at bigger diameters (4–40 nm) the size was selected with a HAUKE-type DMA. Differences between the (N)AISs were small. Positive ion mobilities were detected by (N)AISs with better accuracy than negative, nonetheless, both were somewhat overestimated. The completely monomobile mobility standards were measured with the best accuracy. The (N)AIS concentrations were compared with an aerosol electrometer (AE) and a condensation particle counter (CPC). At sizes below 1.5 nm (positive) and 3 nm (negative) the ion spectrometers detected higher concentrations while at bigger sizes they showed similar concentrations as the reference instruments. The total particle concentrations measured by NAISs were ±50% of the reference CPC concentration at 4–40 nm sizes. The lowest cut-off size of the NAIS in neutral particle measurements was determined to be between 1.5 and 3 nm, depending on the measurement conditions and the polarity.
A global stratospheric bromine monoxide climatology based on the BASCOE chemical transport model
Authors: Theys N. , Van Roozendael M. , Errera Q. , Hendrick F. , Daerden F. , Chabrillat S. , Dorf M. , Pfeilsticker K. , Rozanov A. , Lotz W. , Burrows J. P. , Lambert J.-C. , Goutail F. , Roscoe H. K. , De Mazière M.
Published: April 2010

Abstract. A new climatology of stratospheric BrO profiles based on dynamical and chemical indicators has been developed, with the aim to apply it to the retrieval of tropospheric BrO columns from space nadir measurements. The suitability of the adopted parameterization is evaluated based on three years of output data from the 3-D chemistry transport model BASCOE. The impact of the atmospheric dynamics on the stratospheric BrO distribution is treated by means of Bry/ozone correlations build from 3-D-CTM model results, while photochemical effects are taken into account using stratospheric NO2 columns as an indicator of the BrO/Bry ratio. The model simulations have been optimized for bromine chemistry and budget, and validated through comparisons using an extensive data set of ground-based, balloon-borne and satellite limb (SCIAMACHY) stratospheric BrO observations.
Evaluation of upper tropospheric humidity forecasts from ECMWF using AIRS and CALIPSO data
Authors: Lamquin N. , Gierens K. , Stubenrauch C. J. , Chatterjee R.
Published: April 2010

Abstract. An evaluation of the upper tropospheric humidity from the European Centre of Medium-Range Weather Forecasts (ECMWF) Integrated Forecast System (IFS) is presented. We first make an analysis of the spinup behaviour of ice supersaturation in weather forecasts. It shows that a spinup period of at least 12 h is necessary before using forecast humidity data from the upper troposphere. We compare the forecasted upper tropospheric humidity with coincident relative humidity fields retrieved from the Atmospheric InfraRed Sounder (AIRS) and with cloud vertical profiles from the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO). The analysis is made over one year, from October 2006 to September 2007, and we discuss how relative humidity and cloud features appear both in the IFS and in the observations. In a last part, we investigate the presence of ice supersaturation within low vertical resolution pressure layers by comparing the IFS outputs for high-resolution and low-resolution humidity profiles and by simulating the interpolation of humidity over radiosonde data. A new correction method is proposed and tested with these data.
Exploring the relation between aerosol optical depth and PM2.5 at Cabauw, the Netherlands
Authors: Schaap M. , Apituley A. , Timmermans R. M. A. , Koelemeijer R. B. A. , de Leeuw G.
Published: April 2010

Abstract. To acquire daily estimates of PM2.5 distributions based on satellite data one depends critically on an established relation between AOD and ground level PM2.5. In this study we aimed to experimentally establish the AOD-PM2.5 relationship for the Netherlands. For that purpose an experiment was set-up at the AERONET site Cabauw. The average PM2.5 concentration during this ten month study was 18 μg/m3, which confirms that the Netherlands are characterised by a high PM burden. A first inspection of the AERONET level 1.5 (L1.5) AOD and PM2.5 data at Cabauw showed a low correlation between the two properties. However, after screening for cloud contamination in the AERONET L1.5 data, the correlation improved substantially. When also constraining the dataset to data points acquired around noon, the correlation between AOD and PM2.5 amounted to R2=0.6 for situations with fair weather. This indicates that AOD data contain information about the temporal evolution of PM2.5. We had used LIDAR observations to detect residual cloud contamination in the AERONET L1.5 data. Comparison of our cloud-screed L1.5 with AERONET L2 data that became available near the end of the study showed favorable agreement. The final relation found for Cabauw is PM2.5=124.5*AOD–0.34 (with PM2.5 in μg/m3) and is valid for fair weather conditions. The relationship determined between MODIS AOD and ground level PM2.5 at Cabauw is very similar to that based on the much larger dataset from the sun photometer data, after correcting for a systematic overestimation of the MODIS data of 0.05. We applied the relationship to a MODIS composite map to assess the PM2.5 distribution over the Netherlands. Spatial dependent systematic errors in the MODIS AOD, probably related to variability in surface reflectance, hamper a meaningful analysis of the spatial distribution of PM2.5 using AOD data at the scale of the Netherlands.
Measurements of Pollution In The Troposphere (MOPITT) validation through 2006
Authors: Emmons L. K. , Edwards D. P. , Deeter M. N. , Gille J. C. , Campos T. , Nédélec P. , Novelli P. , Sachse G.
Published: April 2010

Abstract. Comparisons of aircraft measurements of carbon monoxide (CO) to the retrievals of CO using observations from the Measurements of Pollution in The Troposphere (MOPITT) instrument onboard the Terra satellite are presented. Observations made as part of the NASA INTEX-B and NSF MIRAGE field campaigns during March–May 2006 are used to validate the MOPITT CO retrievals, along with routine samples from 2001 through 2006 from NOAA and the MOZAIC measurements from commercial aircraft. A significant positive bias, around 20% for total column CO, in MOPITT CO was found in the comparison to in situ measurements during 2006. Comparisons to the long-term records of measurements from NOAA and MOZAIC revealed an increasing bias in the V3 MOPITT CO retrievals over time. Possible causes for the drift have been investigated and should be significantly reduced in the next version (V4) of MOPITT retrievals.
The impact of traffic emissions on atmospheric ozone and OH: results from QUANTIFY
Authors: Hoor P. , Borken-Kleefeld J. , Caro D. , Dessens O. , Endresen O. , Gauss M. , Grewe V. , Hauglustaine D. , Isaksen I. S. A. , Jöckel P. , Lelieveld J. , Meijer E. , Olivie D. , Prather M. , Schnadt Poberaj C. , Staehelin J. , Tang Q. , van Aardenne J. , van Velthoven P. , Sausen R.
Published: April 2010

Abstract. To estimate the impact of emissions by road, aircraft and ship traffic on ozone and OH of the present-day atmosphere seven different atmospheric chemistry models simulated the atmospheric composition of the year 2003. Based on newly developed global emission inventories for road, maritime and aircraft emission data sets each model performed a series of five simulations: A base scenario using the full set of emissions, three sensitivity studies with each individual sector of transport reduced by 5% and one simulation with all traffic related emissions reduced by 5%. The approach minimizes non-linearities in atmospheric chemical effects and are later scaled to 100%. The global annual mean impact of ship emissions on ozone in the boundary layer leads to an increase of ozone of 1.2%, followed by road (0.87%) and aircraft emissions (0.3%). In the upper troposphere between 200–300 hPa both road and ship traffic affect ozone by 1.1%, whereas aircraft emissions contribute 0.9%. However, the sensitivity of ozone formation per NOx molecule emitted is highest for aircraft exhausts. The local maximum effect of the summed traffic emissions on the ozone column predicted by the models is 4.0 DU and occurs over the northern subtropical Atlantic. The impact of traffic emissions on total ozone in the Southern Hemisphere is approximately half of the northern hemispheric perturbation. Below 800 hPa both ozone and OH respond most sensitively to ship emissions in the marine boundary layer over the Atlantic, where the effect can exceed 10% (zonal mean) which is 80% of the total traffic induced ozone perturbation. In the Southern Hemisphere ship emissions contribute relatively strongly to the total ozone perturbation by 60%–80% throughout the year (equivalent to 1–1.5 ppbv). Road emissions have the strongest impact on ozone in the continental boundary layer and the free troposphere in summer. They also affect the upper troposphere particularly during northern summer associated with strong convection in mid latitudes. Ozone perturbations due to road traffic show the strongest seasonal cycle in the northern troposphere, and can even change sign in the continental boundary layer during winter. The OH concentration in the boundary layer is most strongly affected by ship emissions, which has a significant influence on the lifetime of many trace gases including methane. Methane lifetime changes due to ship emissions amount to 4.1%, followed by road (1.6%) and air traffic (1.0%).
Optical characteristics of biomass burning aerosols over Southeastern Europe determined from UV-Raman lidar measurements
Authors: Amiridis V. , Balis D. S. , Giannakaki E. , Stohl A. , Kazadzis S. , Koukouli M. E. , Zanis P.
Published: April 2010

Abstract. The influence of smoke on the aerosol loading in the free troposphere over Thessaloniki, Greece is examined in this paper. Ten cases during 2001–2005 were identified when very high aerosol optical depth values in the free troposphere were observed with a UV-Raman lidar. Particle dispersion modeling (FLEXPART) and satellite hot spot fire detection (ATSR) showed that these high free tropospheric aerosol optical depths are mainly attributed to the advection of smoke plumes from biomass burning regions over Thessaloniki. The biomass burning regions were found to extend across Russia in the latitudinal belt between 45° N–55° N, as well as in Eastern Europe (Baltic countries, Western Russia, Belarus, and the Ukraine). The highest frequency of agricultural fires occurred during the summer season (mainly in August). The data collected allowed the optical characterization of the smoke aerosols that arrived over Greece, where limited information has so far been available. Two-wavelength backscatter lidar measurements showed that the backscatter-related Ångström exponent ranged between 0.5 and 2.4 indicating a variety of particle sizes. UV-Raman lidar measurements showed that for smoke particles the extinction to backscatter ratios varied between 40 sr for small particles to 100 sr for large particles. Dispersion model estimations of the carbon monoxide tracer concentration profiles for smoke particles indicate that the variability of the optical parameters is a function of the age of the smoke plumes.
What can we learn from European continuous atmospheric CO2 measurements to quantify regional fluxes – Part 1: Potential of the network
Authors: Carouge C. , Bousquet P. , Peylin P. , Rayner P. J. , Ciais P.
Published: April 2010

Abstract. An inverse model using atmospheric CO2 observations from a European network of stations to reconstruct daily CO2 fluxes and their uncertainties over Europe at 50 km resolution has been developed within a Bayesian framework. In this first part, a pseudo-data experiment is performed to assess the potential of continuous measurements over Europe using a network of 10 stations such as in 2001. Under the assumptions of a small observation noise and a perfect atmospheric transport model, the reconstruction of daily CO2 fluxes and in particular of their synoptic variability is best over Western Europe where the network is the densest. At least a 10 days temporal and a 1000 km spatial averaging of the inverted daily/50 km fluxes is required in order to obtain a good agreement between the estimated and the "true" fluxes in terms of correlation and variability. The performances of the inversion system rapidly degrade when fluxes are sought for a smaller temporal or spatial averaging.
Characterisation of episodic aerosol types over the Australian continent
Authors: Qin Y. , Mitchell R. M.
Published: April 2010

Abstract. Classification of Australian continental aerosol types resulting from episodes of enhanced source activity, such as smoke plumes and dust outbreaks, is carried out via cluster analysis of microphysical properties obtained from inversion of sky radiance distributions at Australian aerosol ground stations using data obtained over the last decade. The cluster analysis distinguishes four significant classes, which are identified on the basis of their optical properties and provenance as determined by satellite imagery and back-trajectory analysis. The four classes are identified respectively as aged smoke, fresh smoke, coarse dust and a super-absorptive aerosol. While the first three classes show similarities with comparable aerosol types identified elsewhere, the super-absorptive aerosol has no obvious foreign prototype. The class identified as coarse dust shows a prominent depression in single scattering albedo in the blue spectral region due to absorption by hematite, which is shown to be more abundant in central Australian dust relative to the "dust belt" of the Northern Hemisphere. The super-absorptive class is distinctive in view of its very low single scattering albedo (~0.7 at 500 nm) and variable enhanced absorption at 440 nm. The strong absorption by this aerosol requires a high black carbon content while the enhanced blue-band absorption may derive from organic compounds emitted during the burning of specific vegetation types. This aerosol exerts a positive radiative forcing at the top of atmosphere (TOA), with a large deposition of energy in the atmosphere per unit aerosol optical depth. This contrasts to the other three classes where the TOA forcing is negative. Optical properties of the four types will be used to improve the representation of Australian continental aerosol in climate models, and to enhance the accuracy of satellite-based aerosol retrievals over Australia.
Oxygen isotopic signature of CO2 from combustion processes
Authors: Schumacher M. , Neubert R. E. M. , Meijer H. A. J. , Jansen H. G. , Brand W. A. , Geilmann H. , Werner R. A.
Published: April 2010

Abstract. For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (13C and 18O) abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the δ18O signature of CO2 from combustion processes, which are widely present both naturally (wild fires), and human induced (fossil fuel combustion, biomass burning) in the carbon cycle. All these combustion processes use atmospheric oxygen, of which the isotopic signature is assumed to be constant with time throughout the whole atmosphere. The combustion is generally presumed to take place at high temperatures, thus minimizing isotopic fractionation. Therefore it is generally supposed that the 18O signature of the produced CO2 is equal to that of the atmospheric oxygen. This study, however, reveals that the situation is much more complicated and that important fractionation effects do occur. From laboratory studies fractionation effects in the order of about 26‰ became obvious, a clear differentiation of about 7‰ was also found in car exhausts which were sampled directly under ambient atmospheric conditions. We investigated a wide range of materials (both different raw materials and similar materials with different inherent 18O signature), sample geometries (e.g. texture and surface-volume ratios) and combustion circumstances. We found that the main factor influencing the specific isotopic signatures of the combustion-derived CO2 and of the concomitantly released oxygen-containing side products, is the case-specific rate of combustion. This points firmly into the direction of (diffusive) transport of oxygen to the reaction zone as the cause of the isotope fractionation. The original 18O signature of the material appeared to have little or no influence.
A new analytical inversion method for determining regional and global emissions of greenhouse gases: sensitivity studies and application to halocarbons
Authors: Stohl A. , Seibert P. , Arduini J. , Eckhardt S. , Fraser P. , Greally B. R. , Maione M. , O'Doherty S. , Prinn R. G. , Reimann S. , Saito T. , Schmidbauer N. , Simmonds P. G. , Vollmer M. K. , Weiss R. F. , Yokouchi Y.
Published: April 2010

Abstract. A new analytical inversion method has been developed to determine the regional and global emissions of long-lived atmospheric trace gases. It exploits in situ measurement data from a global network and builds on backward simulations with a Lagrangian particle dispersion model. The emission information is extracted from the observed concentration increases over a baseline that is itself objectively determined by the inversion algorithm. The method was applied to two hydrofluorocarbons (HFC-134a, HFC-152a) and a hydrochlorofluorocarbon (HCFC-22) for the period January 2005 until March 2007. Detailed sensitivity studies with synthetic as well as with real measurement data were done to quantify the influence on the results of the a priori emissions and their uncertainties as well as of the observation and model errors. It was found that the global a posteriori emissions of HFC-134a, HFC-152a and HCFC-22 all increased from 2005 to 2006. Large increases (21%, 16%, 18%, respectively) from 2005 to 2006 were found for China, whereas the emission changes in North America and Europe were modest. For Europe, the a posteriori emissions of HFC-134a and HFC-152a were slightly higher than the a priori emissions reported to the United Nations Framework Convention on Climate Change (UNFCCC). For HCFC-22, the a posteriori emissions for Europe were substantially (by almost a factor 2) higher than the a priori emissions used, which were based on HCFC consumption data reported to the United Nations Environment Programme (UNEP). Combined with the reported strongly decreasing HCFC consumption in Europe, this suggests a substantial time lag between the reported timing of the HCFC-22 consumption and the actual timing of the HCFC-22 emission. Conversely, in China where HCFC consumption is increasing rapidly according to the UNEP data, the a posteriori emissions are only about 40% of the a priori emissions. This reveals a substantial storage of HCFC-22 and potential for future emissions in China. Deficiencies in the station locations of the current global network measuring halocarbons in relation to estimating regional emissions are also discussed in the paper. Applications of the inversion algorithm to other greenhouse gases such as methane, nitrous oxide or carbon dioxide are foreseen for the future.
Validation of an experimental setup to study atmospheric heterogeneous ozonolysis of semi-volatile organic compounds
Authors: Pflieger M. , Goriaux M. , Temime-Roussel B. , Gligorovski S. , Monod A. , Wortham H.
Published: April 2010

Abstract. There is currently a need of reliable experimental procedure to follow the heterogeneous processing simulating the atmospheric conditions. This work offers a new experimental approach to study the reactivity and the behaviour of SVOC associated with atmospheric particles. The heterogeneous ozonolysis of naphthalene adsorbed on silica and XAD-4 particles is investigated in specially designed flow tube reactors. The experimental procedure consists in adsorbing gaseous naphthalene on particles before exposing it to ozone. By this novel approach the kinetics is determined following the consumption of naphthalene. Using this procedure, the rate constant kO3 of naphthalene is equal to (2.26±0.09)×10−17cm3.molec−1.s−1 and (4.31±1.07)×10−19cm3.molec−1.s−1 at 25°C for silica and XAD-4, respectively. The results show both that nature of the particles significantly affects the kinetics and that heterogeneous ozonolysis of naphthalene is faster than in the gaseous phase.
Identifying convective transport of carbon monoxide by comparing remotely sensed observations from TES with cloud modeling simulations
Authors: Halland J. J. , Fuelberg H. E. , Pickering K. E. , Luo M.
Published: April 2010

Abstract. Understanding the mechanisms that transport pollutants from the surface to the free atmosphere is important for determining the atmosphere's chemical composition. This study quantifies the vertical transport of tropospheric carbon monoxide (CO) by deep mesoscale convective systems and assesses the ability of the satellite-borne Tropospheric Emission Spectrometer (TES) to detect the resulting enhanced CO in the upper atmosphere. A squall line that is similar to one occurring during NASA's INTEX-B mission is simulated using a typical environmental wind shear profile and the 2-D Goddard Cumulus Ensemble model. The simulation provides post-convection CO profiles. The structure of the simulated squall line is examined, and its vertical transport of CO is quantified. Then, TES' ability to resolve the convectively modified CO distribution is documented using a "clear-sky" retrieval scheme. Results show that the simulated squall line transports the greatest mass of CO in the upper levels, with a value of 96 t upward and 67 t downward at 300 hPa. Maximum updraft speed is found to be unimportant in determining the net CO flux transported by a storm, but is important in determining the altitude to which the storm transports the boundary layer CO. Results indicate that TES has sufficient sensitivity to resolve convectively lofted CO, as long as the retrieval scene is cloud-free. TES swaths located immediately downwind of squall lines have the greatest chance of sensing convective transport because the impact of clouds on retrieval quality becomes less. A note of caution is to always analyze TES-derived CO data (or data from any satellite sensor) together with the retrieval averaging kernel diagonals or other parameters describing the information content of the retrieval.
Observation of nitrate coatings on atmospheric mineral dust particles
Authors: Li W. J. , Shao L. Y.
Published: April 2010

Abstract. Nitrate compounds have recently received much attention because of their ability to alter the hygroscopic properties and cloud condensation nuclei (CCN) activity of mineral dust particles in the atmosphere. However, very little is known about specific characteristics of nitrate-coated mineral particles in an individual particle scale in field study. The sample collection was conducted during brown haze and dust episodes occurred between 24 May and 21 June 2007 in Beijing, northern China. The sizes, morphologies, and compositions of mineral dust particles together with their coatings were analyzed using transmission electron microscopy (TEM). 92% of the internally mixed mineral particles analyzed are covered with Ca-, Mg-, and Na-rich coatings, and 8% are associated with K- and S-rich coatings. The major coatings contain Ca, Mg, O, and N with minor amounts of S and Cl, suggesting that they are possibly nitrates mixed with less sulfates and chlorides. These nitrate coatings strongly relate with the presence of alkaline mineral components (e.g., calcite and dolomite) within individual mineral particles. Calcium sulfate particles with the diameter from 10 to 500 nm were also detected within Ca(NO3)2 and Mg(NO3)2 coatings. Our results indicate that mineral particles in brown haze episodes were involved in atmospheric heterogeneous reactions with two or more acidic gases (e.g., SO2, NO2, HCl, and HNO3). Mineral particles that acquire hygroscopic coatings tend to be more spherical and larger. Such changes enhance their light scattering and CCN activity, both of which have cooling effects on the climate.
SCIAMACHY formaldehyde observations: constraint for isoprene emissions over Europe?
Authors: Dufour G. , Wittrock F. , Camredon M. , Beekmann M. , Richter A. , Burrows J.
Published: April 2010

Abstract. Formaldehyde (HCHO) is an important intermediate compound in the degradation of volatile organic compounds (VOCs) in the troposphere. Sources of HCHO are largely dominated by its secondary production from VOC oxidation, methane and isoprene being the main precursors in unpolluted areas. As a result of the moderate lifetime of HCHO, its spatial distribution is determined by reactive hydrocarbon emissions. We focus here on Europe, never studied before, and investigate the influence of the different emissions on HCHO tropospheric columns with the CHIMERE chemical transport model in order to interpret the comparisons between SCIAMACHY and simulated HCHO columns. Observed columns present a bias less than 20% on average. The differences are discussed according to the errors on the model and the observations and the remaining discrepancies are attributed to a misrepresentation of biogenic emissions. This study requires the characterisation of: (1) the model errors and performances concerning formaldehyde. The errors on the HCHO columns, mainly related to chemistry and mixed emission types, are evaluated to 2×1015 molecule/cm2 and the model performances evaluated using surface measurements are satisfactory (~13%); (2) the observation errors that define the needs in spatial and temporal averaging for meaningful comparisons. Perspectives of using SCIAMACHY observations as constraint for biogenic isoprene emissions with an adapted averaging are approached: this new constraint should help to reduce their uncertainties more than 50% in region of intense emissions.
Dual-wavelength aerosol vertical profile measurements by MAX-DOAS at Tsukuba, Japan
Authors: Irie H. , Kanaya Y. , Akimoto H. , Iwabuchi H. , Shimizu A. , Aoki K.
Published: April 2010

Abstract. We present vertical profiles of the aerosol extinction coefficient retrieved from ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements at Tsukuba, Japan (36.1° N, 140.1° E), from November 2006 to March 2007. Retrievals utilizing absorption by the oxygen collision complex O4 are first made at two wavelengths, 354 and 476 nm. A robust assessment of the MAX-DOAS aerosol data is made using coincident lidar measurements throughout the period. Agreement between aerosol extinction coefficients measured by MAX-DOAS and the lidar tends to be better at the longer wavelength and at lower altitudes. At 476 nm, the best agreement, to within 30%, is found at altitudes of 0–1 km, confirming results from a literature assessment for a two-month measurement period. These findings are supported by comparisons of the aerosol optical depth by MAX-DOAS and sky radiometer measurements and are further explained by differences in the O4 absorption and the air mass factor profile between 354 and 476 nm. Thus, uncertainty in MAX-DOAS aerosol measurements is well quantified and characterized, providing a basis for quantitative studies using MAX-DOAS measurements.