bluuebunny/crossref_metadata_2025 huggingface dataset:
Characterization of African dust over southern Italy
Authors: Blanco A. , Dee Tomasi F. , Filippo E. , Manno D. , Perrone M. R. , Serra A. , Tafuro A. M. , Tepore A.
Published: April 2010

Abstract. Dust samples from rainfall residues have been collected in southeast Italy (40º 20' N, 18º 6' E) during dust outbreaks occurred from April to June 2002 to characterize morphological and elemental particle composition by different techniques, and investigate the dependence of particle properties on source regions. Four-day analytical back trajectories and satellite images have been used to infer source regions of the investigated dust samples. It has been found that the TOMS absorbing aerosol index was in the range 0.7-2.2 over Southern Italy when samples have been collected. The particle-size and -shape analysis by a scanning electron microscope (SEM) has revealed either that the particle-diameter distribution was between 0.3 and 30 mm with median-diameter values between 1.7-2.4 mm, and that the particles were characterized by a roundness factor varying from 0.8 to 2.5. The infrared transmission spectra have allowed recognizing that all dust samples contained a significant amount of illite. The X-ray energy dispersive (EDX) measurements have revealed that the Al/Si ratio of the transported dust varies from 0.41 to 0.50, and that the Al/Si, Ca/Al, K/Ca, and Fe/Ca ratios differ according to source regions and therefore can be used as indicators of dust source regions. Indeed, it has been found that dust samples with larger Ca/Al and Si/Al ratios and lower Fe/Ca and K/Ca ratios, have been collected along dust events with a source region in northwestern Sahara. On the contrary, the samples collected along dust events with the origin mainly in Chad, Niger, Algeria and Lybia were characterized by larger Fe/Ca and K/Ca ratios.
One year boundary layer aerosol size distribution data from five nordic background stations
Authors: Tunved P. , Hansson H.-C. , Kulmala M. , Aalto P. , Viisanen Y. , Karlsson H. , Kristensson A. , Swietlicki E. , Dal Maso M. , Ström J. , Komppula M.
Published: April 2010

Abstract. Size distribution measurements performed at five different stations have been investigated during a one-year period between 01 June 2000 and 31 May 2001 with focus on diurnal, seasonal and geographical differences of size distribution properties. The stations involved cover a large geographical area ranging from the Finnish Lapland (67º N) down to southern Sweden (56º N) in the order Värriö, Pallas, Hyytiälä, Aspvreten and Vavihill. The shape of the size distribution is typically bimodal during winter with a larger fraction of accumulation mode particles compared to the other seasons. Highest Aitken mode concentration is found during summer and spring during the year of study. The maximum of nucleation events occur during the spring months at all stations. Nucleation events occur during other months as well, although not as frequently. Large differences were found between different categories of stations. Northerly located stations such as Pallas and Värriö presented well-separated Aitken and accumulation modes, while the two modes often overlap significantly at the two southernmost stations Vavihill and Aspvreten. A method to cluster trajectories was used to analyse the impact of long-range transport on the observed aerosol properties. Clusters of trajectories arriving from the continent were clearly associated with size distributions shifted towards the accumulation mode. This feature was more pronounced the further south the station was located. Marine- or Arctic-type clusters were associated with large variability in the nuclei size ranges. A quasi-lagrangian approach was used to investigate transport related changes in the aerosol properties. Typically, an increase in especially Aitken mode concentrations was observed when advection from the north occurs, i.e. allowing more continental influence on the aerosol when comparing the different measurement sites. When trajectory clusters arrive to the stations from SW, a gradual decrease in number concentration is experienced in all modes as latitude of measurement site increases.
Ground-based FTIR measurements of CO from the Jungfraujoch: characterisation and comparison with in situ surface and MOPITT data
Authors: Barret B. , De Mazière M. , Mahieu E.
Published: April 2010

Abstract. CO vertical profiles have been retrieved from solar absorption FTIR spectra recorded at the NDSC station of the Jungfraujoch (46.5º N, 8º E and 3580 m a.s.l.) for the period from January 1997 to May 2001. The characterisation of these profiles has been established by an information content analysis and an estimation of the error budgets. A partial validation of the profiles has been performed through comparisons with correlative measurements. The average volume mixing ratios (vmr) in the 3 km layer above the station have been compared with coincident surface measurements. The agreement between monthly means from both measurement techniques is very good, with a correlation coefficient of 0.87, and no significant bias observed. The FTIR total columns have also been compared to CO partial columns above 3580 m a.s.l. derived from the MOPITT (Measurement Of Pollution In The Troposphere) instrument for the period March 2000 to May 2001. Relative to the FTIR columns, the MOPITT partial columns exhibit a positive bias of 8±8% for daytime and of 4±7% for nighttime measurements.
Weekly cycle of NO2 by GOME measurements: a signature of anthropogenic sources
Authors: Beirle S. , Platt U. , Wenig M. , Wagner T.
Published: April 2010

Abstract. Nitrogen oxides (NO+NO2=NOx and reservoir species) are important trace gases in the troposphere with impact on human health, atmospheric chemistry and climate. Besides natural sources (lightning, soil emissions) and biomass burning, fossil fuel combustion is estimated to be responsible for about 50% of the total production of NOx. Since human activity in industrialized countries largely follows a seven-day cycle, fossil fuel combustion is expected to be reduced during weekends. This "weekend effect" is well known from local, ground based measurements, but has never been analysed on a global scale before. The Global Ozone Monitoring Experiment (GOME) on board the ESA-satellite ERS-2 allows measurements of NO2 column densities. By estimating and subtracting the stratospheric column, and considering radiative transfer, vertical column densities (VCD) of tropospheric NO2 can be determined (e.g. Leue et al., 2001). We demonstrate the statistical analysis of weekly cycles of tropospheric NO2 VCDs for different regions of the world. In the cycles of the industrialized regions and cities in the US, Europe and Japan a clear Sunday minimum of tropospheric NO2 VCD can be seen. Sunday NO2 VCDs are about 25-50% lower than working day levels. Metropolitan areas with other religious and cultural backgrounds (Jerusalem, Mecca) show different weekly patterns corresponding to different days of rest. In China, no weekly pattern can be found. The presence of a weekly cycle in the measured tropospheric NO2 VCD may help to identify the different anthropogenic source categories. Furthermore, we estimated the lifetime of tropospheric NO2 by analysing the mean weekly cycle exemplarily over Germany, obtaining a value of about 6 h in summer and 18-24 h in winter.
Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes
Authors: Atkinson R.
Published: April 2010

Abstract. The available database concerning rate constants for gas-phase reactions of the hydroxyl (OH) radical with alkanes through early 2003 is presented over the entire temperature range for which measurements have been made (~180-2000 K). Measurements made using relative rate methods are re-evaluated using recent rate data for the reference compound (generally recommendations from this review). In general, whenever more than one study has been carried out over an overlapping temperature range, recommended rate constants or temperature-dependent rate expressions are presented. The recommended 298 K rate constants, temperature-dependent parameters, and temperature ranges over which these recommendations are applicable are listed in Table 1.
Modeling the chemical effects of ship exhaust in the cloud-free marine boundary layer
Authors: von Glasow R. , Lawrence M. G. , Sander R. , Crutzen P. J.
Published: April 2010

Abstract. The chemical evolution of the exhaust plumes of ocean-going ships in the cloud-free marine boundary layer is examined with a box model. Dilution of the ship plume via entrainment of background air was treated as in studies of aircraft emissions and was found to be a very important process that significantly alters model results. We estimated the chemical lifetime (defined as the time when differences between plume and background air are reduced to 5% or less) of the exhaust plume of a single ship to be 2 days. Increased concentrations of NOx (= NO + NO2) in the plume air lead to higher catalytical photochemical production rates of O3 and also of OH. Due to increased OH concentrations in the plume, the lifetime of many species (especially NOx) is significantly reduced in plume air. The chemistry on background aerosols has a significant effect on gas phase chemistry in the ship plume, while partly soluble ship-produced aerosols are computed to only have a very small effect. Soot particles emitted by ships showed no effect on gas phase chemistry. Halogen species that are released from sea salt aerosols are slightly increased in plume air. In the early plume stages, however, the mixing ratio of BrO is decreased because it reacts rapidly with NO. To study the global effects of ship emissions we used a simple upscaling approach which suggested that the parameterization of ship emissions in global chemistry models as a constant source at the sea surface leads to an overestimation of the effects of ship emissions on O3 of about 50% and on OH of roughly a factor of 2. The differences are mainly caused by a strongly reduced lifetime (compared to background air) of NOxin the early stages of a ship plume.
Wavelength dependence of isotope fractionation in N2O photolysis
Authors: Kaiser J. , Röckmann T. , Brenninkmeijer C. A. M. , Crutzen P. J.
Published: April 2010

Abstract. In previous reports on isotopic fractionation in the ultraviolet photolysis of nitrous oxide (N2O) only enrichments of heavy isotopes in the remaining N2O fraction have been found. However, most direct photolysis experiments have been performed at wavelengths far from the absorption maximum at 182 nm. Here we present high-precision measurements of the 15N and 18O fractionation constants (ε) in photolysis at 185 nm. Small, but statistically robust depletions of heavy isotopes for the terminal atoms in the linear N2O molecule are found. This means that the absorption cross sections σ(15N 14N 16O) and σ(14N218O) are larger than σ(14N216O) at this specific wavelength. In contrast, the central N atom becomes enriched in 15N. The corresponding fractionation constants (±1 standard deviation) are 15ε1 = σ(15N 14N 16O)/σ(14N2 16O) - 1 = (3.7±0.2) %o 18ε = σ(14N218O)/σ(14N216O) - 1 = (4.5±0.2) %o  and 15ε2 = σ(14N 15N 16O)/σ(14N216O) - 1 = (-18.6±0.5) %o To our knowledge, this is the first documented case of such a heavy isotope depletion in the photolysis of N2O which supports theoretical models and pioneering vacuum ultraviolet spectroscopic measurements of 15N substituted N2O species that predict fluctuations of ε around zero in this spectral region (Selwyn and Johnston, 1981). Such a variability in isotopic fractionation could have consequences for atmospheric models of N2O isotopes since actinic flux varies also strongly over narrow wavelength regions between 175 and 200 nm due to the Schumann-Runge bands of oxygen. However, the spacing between maxima and minima of the fractionation constants and of the actinic flux differ by two orders of magnitude in the wavelength domain. The wavelength dependence of fractionation constants in N2O photolysis can thus be approximated by a linear fit with negligible consequences on the actual value of the spectrally averaged fractionation constant. In order to establish this linear fit, additional measurements at wavelengths other than 185 nm were made using broadband light sources, namely D2, Hg/Xe and Sb lamps. The latter lamp was used in conjunction with various interference filters to shift the peak photolysis rate to longer wavelengths. From these experiments and existing data in the literature, a comprehensive picture of the wavelength dependence of N2O photolysis near room-temperature is created.
Intercontinental transport of nitrogen oxide pollution plumes
Authors: Wenig M. , Spichtinger N. , Stohl A. , Held G. , Beirle S. , Wagner T. , Jähne B. , Platt U.
Published: April 2010

Abstract. We describe the first satellite observation of intercontinental transport of nitrogen oxides emitted by power plants, verified by simulations with a particle tracer model. The analysis of such episodes shows that anthropogenic NOx plumes may influence the atmospheric chemistry thousands of kilometers away from its origin, as well as the ocean they traverse due to nitrogen fertilization. This kind of monitoring became possible by applying an improved algorithm to extract the tropospheric fraction of NO2 from the spectral data coming from the GOME instrument. As an example we show the observation of NO2 in the time period 4--14 May, 1998, from the South African Plateau to Australia which was possible due to favourable weather conditions during that time period which availed the satellite measurement. This episode was also simulated with the Lagrangian particle dispersion model FLEXPART which uses NOx emissions taken from an inventory for industrial emissions in South Africa and is driven with analyses from the European Centre for Medium-Range Weather Forecasts. Additionally lightning emissions were taken into account by utilizing Lightning Imaging Sensor data. Lightning was found to contribute probably not more than 25% of the resulting concentrations. Both, the measured and simulated emission plume show matching patterns while traversing the Indian Ocean to Australia and show great resemblance to the aerosol and CO2 transport observed by Piketh et al. (2000).
Atmospheric measurements of gas-phase HNO3 and SO2 using chemical ionization mass spectrometry during the MINATROC field campaign 2000 on Monte Cimone
Authors: Hanke M. , Umann B. , Uecker J. , Arnold F. , Bunz H.
Published: April 2010

Abstract. The EU-project MINATROC (MINeral dust And TROpospheric Chemistry) aims at enabling an estimation of the influence of mineral dust, a major, but to date largely ignored component of tropospheric aerosol, on tropospheric oxidant cycles. Within the scope of this project continuous atmospheric measurements of gas-phase HNO3 and SO2 were conducted in June and July 2000 at the CNR WMO station, situated on Monte Cimone (MTC) (44°11' N --10°42' E, 2165 m asl), Italy. African air transporting dust is occasionally advected over the Mediterranean Sea to the site, thus mineral aerosol emitted from Africa will encounter polluted air masses and provide ideal conditions to study their interactions. HNO3 and SO2 were measured with an improved CIMS (chemical ionization mass spectrometry) system for ground-based measurements that was developed and built at MPI-K Heidelberg. Since HNO3  is a very sticky compound special care was paid for the air-sampling and background-measurement system. Complete data sets could be obtained before, during and after major dust intrusions. For the first time these measurements might provide a strong observational indication of efficient uptake of gas-phase HNO3 by atmospheric mineral-dust aerosol particles.
On the transition between heterogeneous and homogeneous freezing
Authors: Gierens K.
Published: April 2010

Abstract. Box model simulations of an uplifting and adiabatically cooling cloud of aerosol have been performed in order to study the transition between cirrus formation dominated by homogeneous nucleation of ice to that dominated by heterogeneous nucleation. The aerosol was assumed to consist of an internal mixture of sulfuric acid solution droplets with inclusions of soot. The parametrisation of De Mott et al. (1997) was used to simulate the heterogeneous nucleation of ice in such droplets with soot inclusions. The simulations show that the transition from heterogeneous to homogeneous nucleation occurs over a narrow range of soot concentration. Thus it seems to be possible to fix critical concentrations of heterogeneous ice nuclei which must be exceeded if heterogeneous freezing dominates cirrus formation. A formula has been derived that allows to compute the critical concentrations of heterogeneous ice nuclei as a function of temperature, updraft speed, ambient pressure, and supersaturation at which heterogeneous freezing occurs. Generally, homogeneous nucleation dominates in regions with updrafts stronger than 20 cm s -1, with the exception of heavily polluted areas which could be common in the northern hemisphere due to air traffic, where updrafts of the order 1 m s-1 may be necessary to render heterogeneous nucleation unimportant. According to the present results it cannot be excluded that heterogeneous nucleation plays a more important role for cirrus formation in the northern midlatitudes than anywhere else. A possible consequence of these results is that air pollution may lead to a higher coverage of cirrus clouds, but then these clouds will be optically thinner than clouds formed by homogeneous freezing, with the exception of regions where condensation trails are frequent.
Chemical characteristics assigned to trajectory clusters during the MINOS campaign
Authors: Traub M. , Fischer H. , de Reus M. , Kormann R. , Heland H. , Ziereis H. , Schlager H. , Holzinger R. , Williams J. , Warneke C. , de Gouw J. , Lelieveld J.
Published: April 2010

Abstract. During the Mediterranean Intensive Oxidant Study (MINOS) in August 2001 a total of 14 measurement flights were performed with the DLR Falcon jet aircraft from Heraklion, Crete. One objective of this campaign was to investigate the role of long-range transport of pollutants into the Mediterranean area. An analysis of 5-day back trajectories indicates that in the lower troposphere (0-4 km) air masses originated from eastern and western Europe, in the mid-troposphere (4-8 km) from the North Atlantic Ocean region and in the upper troposphere (8-14 km) from North Atlantic Ocean/North America (NANA) as well as South Asia. We allocated all back trajectories to clusters based on their ending height and source region. The mixing ratios of ozone, nitrogen oxide, total reactive oxidized nitrogen (NOy), formaldehyde, methanol, acetonitrile, acetone, peroxyacetyl nitrate (PAN), carbon dioxide, carbon monoxide and methane measured along the flight tracks are examined in relation to the different cluster trajectories. In the lower troposphere the mean trace gas mixing ratios of the eastern Europe cluster trajectories were significantly higher than those from western Europe. In the upper troposphere air from the NANA region seems to be influenced by the stratosphere, in addition, air masses were transported from South Asia, being influenced by strong convection in the Indian monsoon.
DMS atmospheric concentrations and sulphate aerosol indirect radiative forcing: a sensitivity study to the DMS source representation and oxidation
Authors: Boucher O. , Moulin C. , Belviso S. , Aumont O. , Bopp L. , Cosme E. , von Kuhlmann R. , Lawrence M. G. , Pham M. , Reddy M. S. , Sciare J. , Venkataraman C.
Published: April 2010

Abstract. The global sulphur cycle has been simulated using a general circulation model with a focus on the source and oxidation of atmospheric dimethylsulphide (DMS). The sensitivity of atmospheric DMS to the oceanic DMS climatology, the parameterisation of the sea-air transfer and to the oxidant fields have been studied. The importance of additional oxidation pathways (by O3 in the gas- and aqueous-phases and by BrO in the gas phase) not incorporated in global models has also been evaluated. While three different climatologies of the oceanic DMS concentration produce rather similar global DMS fluxes to the atmosphere at 24-27 Tg S yr -1, there are large differences in the spatial and seasonal distribution. The relative contributions of OH and NO3 radicals to DMS oxidation depends critically on which oxidant fields are prescribed in the model. Oxidation by O3 appears to be significant at high latitudes in both hemispheres. Oxidation by BrO could be significant even for BrO concentrations at sub-pptv levels in the marine boundary layer. The impact of such refinements on the DMS chemistry onto the indirect radiative forcing by anthropogenic sulphate aerosols is also discussed.
Organic acids as cloud condensation nuclei: Laboratory studies of highly soluble and insoluble species
Authors: Pradeep Kumar P. , Broekhuizen K. , Abbatt J. P. D.
Published: April 2010

Abstract. The ability of sub-micron-sized organic acid particles to act as cloud condensation nuclei (CCN) has been examined at room temperature using a newly constructed continuous-flow, thermal-gradient diffusion chamber (TGDC). The organic acids studied were: oxalic, malonic, glutaric, oleic and stearic. The CCN properties of the highly soluble acids - oxalic, malonic and glutaric - match very closely Köhler theory predictions which assume full dissolution of the dry particle and a surface tension of the growing droplet equal to that of water. In particular, for supersaturations between 0.3 and 0.6, agreement between the dry particle diameter which gives 50% activation and that calculated from Köhler theory is to within 3nm on average. In the course of the experiments, considerable instability of glutaric acid particles was observed as a function of time and there is evidence that they fragment to some degree to smaller particles. Stearic acid and oleic acid, which are both highly insoluble in water, did not activate at supersaturations of 0.6% with dry diameters up to 140nm. Finally, to validate the performance of the TGDC, we present results for the activation of ammonium sulfate particles that demonstrate good agreement with Köhler theory if solution non-ideality is considered. Our findings support earlier studies in the literature that showed highly soluble organics to be CCN active but insoluble species to be largely inactive.
A numerical modelling study on regional mercury budget for eastern North America
Authors: Lin X. , Tao Y.
Published: April 2010

Abstract. In this study, we have integrated an up-to-date physio-chemical transformation mechanism of Hg into the framework of US EPA's CMAQ model system. In addition, the model adapted detailed calculations of the air-surface exchange for Hg to properly describe Hg re-emissions and dry deposition from and to natural surfaces. The mechanism covers Hg in three categories, elemental Hg (Hg0), reactive gaseous Hg (RGM) and particulate Hg (HgP). With interfacing to MM5 (meteorology processor) and SMOKE (emission processor), we applied the model to a 4-week period in June/July 1995 on a domain covering most of eastern North America. Results indicate that the model simulates reasonably well the levels of total gaseous Hg (TGM) and the specific Hg wet deposition measurements made by the Hg deposition network (MDN). Moreover, results from various scenario runs reveal that the Hg system behaves in a closely linear way in terms of contributions from different source categories, i.e. anthropogenic emissions, natural re-emissions and background. Analyses of the scenario results suggest that 37% of anthropogenically emitted Hg was deposited back in the model domain with 5155 kg of anthropogenic Hg moving out of the domain during the simulation period. Overall, the domain served as a net source, which supplied ~a half ton of Hg to the global background pool over the period. Our model validation and a sensitivity test further rationalized the rate constant for gaseous oxidation of Hg0 by hydroxyl radical OH used in the global scale modelling study by Bergan and Rodhe (2001). A further laboratory determination of the reaction rate constant, including its temperature dependence, stands as one of the important issues critical to improving our knowledge on the budget and cycling of Hg.
Haze in the Klang Valley of Malaysia
Authors: Keywood M. D. , Ayers G. P. , Gras J. L. , Boers C. P. ,   Leong
Published: April 2010

Abstract. Continuous measurements of dry aerosol light scattering (Bsp) were made at two sites in the Klang Valley of Malaysia between December 1998 and December 2000. In addition 24-hour PM2.5 samples were collected on a one-day-in-six cycle and the chemical composition of the aerosol was determined. Periods of excessive haze were defined as 24-hour average Bsp values greater than 150 Mm-1 and these occurred on a number of occasions, between May and September 1999, during May 2000, and between July and September 2000. The evidence for smoke from biomass burning being a significant contributor to aerosol during periods of excessive haze is discussed. For example, during periods of excessive haze, the chemical composition of the aerosol showed enhanced concentrations of elemental carbon, organic carbon and non-seasalt potassium. The diurnal cycle of Bsp and PM10 was disturbed from its usual pattern of maxima overnight and minuma during the day with morning and afternoon traffic peaks, and instead showed a maximum peak during the middle of the day. Periods of excessive haze were coincident with the presence of forest fires on Sumatra during the southwest (SW) monsoon period, the influence of which are demonstrated by transport modelling for one week of the SW monsoon of 2000. The study highlights that whilst transboundary smoke is a major contributor to poor visibility in the Klang Valley, smoke from fires on Peninsular Malaysia is also a contributor. In addition the uniform concentration of non-seasalt sulfate in PM2.5 at both sites over the entire sampling period suggests the presence of a domestic source of secondary aerosol production in the Klang Valley.
Comprehensive two-dimensional gas chromatography (GC × GC) measurements of volatile organic compounds in the atmosphere
Authors: Xu X. , Stee L. L. P. , Williams J , Beens J. , Adahchour M. , Vreuls R. J. J. , Brinkman U. A. , Lelieveld J.
Published: April 2010

Abstract. During the MINOS campaign in August 2001 comprehensive two-dimensional gas chromatography (GC x GC) was applied to the in situ measurements of atmospheric volatile organic compounds (VOCs) at the Finokalia ground station, Crete. The measurement system employs a thermal desorption unit for on-line sampling and injection, and a GC x GC separation system equipped with a flame ionization detector (FID) for detection. The system was optimized to resolve C7-C14 organic components. Two-dimensional chromatograms from measurements of Finokalia air samples show several hundred well-separated peaks. To facilitate peak identification, cartridge samples collected at Finokalia were analyzed using the same GC x GC system coupled with a time-of-flight mass spectrometer (TOF-MS). The resulting mass spectra were deconvoluted and compared to spectra from a database for tentative peak identification. About 650 peaks have been identified in the two-dimensional plane, with significant signal/noise ratios (>100) and high spectra similarities (>800). By comparing observed retention indices with those found in the literature, 235 of the identifications have been confirmed. 150 of the confirmed compounds show up in the C7-C14 range of the chromatogram from the in situ measurement. However, at least as many peaks remain unidentified. For quantification of the GC x GC measurements, peak volumes of measured compounds have been integrated and externally calibrated using a standard gas mixture.
Tropical tropospheric ozone derived using Clear-Cloudy Pairs (CCP) of TOMS measurements
Authors: Newchurch M. J. , Sun D. , Kim J. H. , Liu X.
Published: April 2010

Abstract. Using TOMS total-ozone measurements over high-altitude cloud locations and nearby paired clear locations, we describe the Clear-Cloudy Pairs (CCP) method for deriving tropical tropospheric ozone. The high-altitude clouds are identified by measured 380 nm reflectivities greater than 80% and Temperature Humidity InfraRed (THIR) measured cloud-top pressures less than 200 hPa. To account for locations without high-altitude clouds, we apply a zonal sine fitting to the stratospheric ozone derived from available cloudy points, resulting in a wave-one amplitude of about 4 DU. THIR data is unavailable after November 1984, so we extend the CCP method by using a reflectivity threshold of 90% to identify high-altitude clouds and remove the influence of high-reflectivity-but-low-altitude clouds with a lowpass frequency filter. We correct ozone retrieval errors associated with clouds, and ozone retrieval errors due to sun glint and aerosols. Comparing CCP results with Southern Hemisphere ADditional OZonesondes (SHADOZ) tropospheric ozone indicates that CCP tropospheric ozone and ozonesonde measurements agree, on average, to within 3 ± 1 DU standard error of the mean. The most significant difference between CCP and ozonesonde tropospheric ozone can be explained by the low Total Ozone Mapping Spectrometer (TOMS) version-7 retrieval efficiency of ozone in the lower troposphere.
Classification of tropospheric ozone profiles over Johannesburg based on mozaic aircraft data
Authors: Diab R. D. , Raghunandan A. , Thompson A. M. , Thouret V.
Published: April 2010

Abstract. Each ozone profile is a unique response to the photochemical and dynamic processes operating in the troposphere and hence is critical to our understanding of processes and their relative contributions to the tropospheric ozone budget. Traditionally, mean profiles, together with some measure of variability, averaged by season or year at a particular location have been presented as a climatology. However, the mean profile is difficult to interpret because of the counteracting influences present in the micro-structure. On the other hand, case study analysis, whilst revealing, only applies to isolated conditions. In a search for pattern and order within ozone profiles, a classification based on a cluster analysis technique has been applied in this study. Ozone profiles are grouped according to the magnitude and altitude of ozone concentration. This technique has been tested with 56 ozone profiles at Johannesburg, South Africa, recorded by aircraft as part of the MOZAIC (Measurement of Ozone and Water Vapor aboard Airbus In-service Aircraft) program. Six distinct groups of ozone profiles have been identified and their characteristics described. The widely recognized spring maximum in tropospheric ozone is identified through the classification, but a new summertime mid-tropospheric enhancement due to the penetration of tropical air masses from continental regions in central Africa has been identified. Back trajectory modeling is used to provide evidence of the different origins of ozone enhancements in each of the classes. Continental areas over central Africa are shown to be responsible for the low to mid-tropospheric enhancement in spring and the mid-tropospheric peak in summer, whereas the winter low-tropospheric enhancement is attributed to local sources. The dominance of westerly winds through the troposphere associated with the passage of a mid-latitude cyclone gives rise to reduced ozone values.
Methodology for prediction and estimation of consequences of possible atmospheric releases of hazardous matter: "Kursk" submarine study
Authors: Baklanov A. , Mahura A. , Sørensen J. H.
Published: April 2010

Abstract. There are objects with some periods of higher than normal levels of risk of accidental atmospheric releases (nuclear, chemical, biological, etc.). Such accidents or events may occur due to natural hazards, human errors, terror acts, and during transportation of waste or various operations at high risk. A methodology for risk assessment is suggested and it includes two approaches: 1) probabilistic analysis of possible atmospheric transport patterns using long-term trajectory and dispersion modelling, and 2) forecast and evaluation of possible contamination and consequences for the environment and population using operational dispersion modelling. The first approach could be applied during the preparation stage, and the second - during the operation stage. The suggested methodology is applied on an example of the most important phases (lifting, transportation, and decommissioning) of the ``Kursk" nuclear submarine operation. It is found that the temporal variability of several probabilistic indicators (fast transport probability fields, maximum reaching distance, maximum possible impact zone, and average integral concentration of 137Cs) showed that the fall of 2001 was the most appropriate time for the beginning of the operation. These indicators allowed to identify the hypothetically impacted geographical regions and territories. In cases of atmospheric transport toward the most populated areas, the forecasts of possible consequences during phases of the high and medium potential risk levels based on a unit hypothetical release (e.g. 1 Bq) are performed. The analysis showed that the possible deposition fractions of 10-11 (Bq/m2) over the Kola Peninsula, and 10-12 - 10-13 (Bq/m2) for the remote areas of the Scandinavia and Northwest Russia could be observed. The suggested methodology may be used successfully for any potentially dangerous object involving risk of atmospheric release of hazardous materials of nuclear, chemical or biological nature.
Forecast, observation and modelling of a deep stratospheric intrusion event over Europe
Authors: Zanis P. , Trickl T. , Stohl A. , Wernli H. , Cooper O. , Zerefos C. , Gaeggeler H. , Schnabel C. , Tobler L. , Kubik P. W. , Priller A. , Scheel H. E. , Kanter H. J. , Cristofanelli P. , Forster C. , James P. , Gerasopoulos E. , Delcloo A. , Papayannis A. , Claude H.
Published: April 2010

Abstract. A wide range of measurements was carried out in central and southeastern Europe within the framework of the EU project STACCATO (Influence of Stratosphere-Troposphere Exchange in a Changing Climate on Atmospheric Transport and Oxidation Capacity) with the principle goal to create a comprehensive data set on stratospheric air intrusions into the troposphere along a rather frequently observed pathway over central Europe from the North Sea to the Mediterranean Sea. The measurements were based on predictions by suitable quasi-operational trajectory calculations using ECMWF forecast data. A predicted deep Stratosphere to Troposphere Transport (STT) event, encountered during the STACCATO period on 20-21 June 2001, was followed by the measurements network almost from its inception. Observations provide evidence that the intrusion affected large parts of central and southeastern Europe. Especially, the ozone lidar observations on 20-21 June 2001 at Garmisch-Partenkirchen, Germany captured the evolution of two marked tongues of high ozone with the first one descending to nearly 2 km, thus providing an excellent data set for model intercomparisons and validation. In addition, for the first time to our knowledge concurrent surface measurements of the cosmogenic radionuclides 10Be and 7Be and their ratio 10Be/7Be are presented together as stratospheric tracers in a case study of a stratospheric intrusion. The ozone tracer columns calculated with the FLEXPART model were found to be in good agreement with water vapour satellite images, capturing the evolution of the observed dry streamers of stratospheric origin. Furthermore, the time-height cross section of ozone tracer simulated with FLEXPART over Garmisch-Partenkirchen captures many details of the evolution of the two observed high-ozone filaments measured with the IFU lidar, thus demonstrating the considerable progress in model simulations. Finally, the modelled ozone (operationally available since October 1999) from the ECMWF (European Centre for Medium-Range Weather Forecasts) atmospheric model is shown to be in very good agreement with the observations during this case study, which provides the first successful validation of a chemical tracer that is derived operationally from a weather forecast model. This suggests that coupling chemistry and weather forecast models may significantly improve both weather and chemical forecasts in the future.
Dependence of solar radiative forcing of forest fire aerosol on ageing and state of mixture
Authors: Fiebig M. , Stohl A. , Wendisch M. , Eckhardt S. , Petzold A.
Published: April 2010

Abstract. During airborne in situ measurements of particle size distributions in a forest fire plume originating in Northern Canada, an accumulation mode number mean diameter of 0.34 mm was observed over Lindenberg, Germany on 9 August 1998. Realizing that this is possibly the largest value observed for this property in a forest fire plume, scenarios of plume ageing by coagulation are considered to explain the observed size distribution, concluding that the plume dilution was inhibited in parts of the plume. The uncertainties in coagulation rate and transition from external to internal mixture of absorbing forest fire and non-absorbing background particles cause uncertainties in the plume's solar instantaneous radiative forcing of 20-40% and of a factor of 5-6, respectively. Including information compiled from other studies on this plume, it is concluded that the plume's characteristics are qualitatively consistent with a radiative-convective mixed layer.
A novel model to predict the physical state of atmospheric H2SO4/NH3/H2O aerosol particles
Authors: Colberg C. A. , Luo B. P. , Wernli H. , Koop T. , Peter Th.
Published: April 2010

Abstract. The physical state of the tropospheric aerosol is largely unknown despite its importance for cloud formation and for the aerosol's radiative properties. Here we use detailed microphysical laboratory measurements to perform a systematic global modelling study of the physical state of the H2SO4/NH3/H2O aerosol, which constitutes an important class of aerosols in the free troposphere. The Aerosol Physical State Model (APSM) developed here is based on Lagrangian trajectories computed from ECMWF (European Centre for Medium Range Weather Forecasts) analyses, taking full account of the deliquescence/efflorescence hysteresis. As input APSM requires three data sets: (i) deliquescence and efflorescence relative humidities from laboratory measurements, (ii) ammonia-to-sulfate ratios (ASR) calculated by a global circulation model, and (iii) relative humidities determined from the ECMWF analyses. APSM results indicate that globally averaged a significant fraction (17-57%) of the ammoniated sulfate aerosol particles contain solids with the ratio of solid-containing to purely liquid particles increasing with altitude (between 2 and 10 km). In our calculations the most abundant solid is letovicite, (NH4)3H(SO4)2, while there is only little ammonium sulfate, (NH4)2SO4. Since ammonium bisulfate, NH4HSO4, does not nucleate homogeneously, it can only form via heterogeneous crystallization. As the ammonia-to-sulfate ratios of the atmospheric H2SO4/NH3/H2O aerosol usually do not correspond to the stoichiometries of known crystalline substances, all solids are expected to occur in mixed-phase aerosol particles. This work highlights the potential importance of letovicite, whose role as cloud condensation nucleus (CCN) and as scatterer of solar radiation remains to be scrutinized.
Ground-based PTR-MS measurements of reactive organic compounds during the MINOS campaign in Crete, July–August 2001
Authors: Salisbury G. , Williams J. , Holzinger R. , Gros V. , Mihalopoulos N. , Vrekoussis M. , Sarda-Estève R. , Berresheim H. , von Kuhlmann R. , Lawrence M. , Lelieveld J.
Published: April 2010

Abstract. This study presents measurements of acetonitrile, benzene, toluene, methanol and acetone made using the proton-transfer-reaction mass spectrometry (PTR-MS) technique at the Finokalia ground station in Crete during the Mediterranean INtensive Oxidant Study (MINOS) in July-August 2001. Three periods during the campaign with broadly consistent back trajectories are examined in detail. In the first, air was advected from Eastern Europe without significant biomass burning influence (mean acetonitrile mixing ratio 154 pmol/mol). In the second period, the sampled air masses originated in Western Europe, and were advected approximately east-south-east, before turning south-west over the Black Sea and north-western Turkey. The third well-defined period included air masses advected from Eastern Europe passing east and south of/over the Sea of Azov, and showed significant influence by biomass burning (mean acetonitrile mixing ratio 436 pmol/mol), confirmed by satellite pictures. The mean toluene:benzene ratios observed in the three campaign periods described were 0.35, 0.37 and 0.22, respectively; the use of this quantity to determine air mass age is discussed. Methanol and acetone were generally well-correlated both with each other and with carbon monoxide throughout the campaign. Comparison of the acetone and methanol measurements with the MATCH-MPIC model showed that the model underestimated both species by a factor of 4, on average. The correlations between acetone, methanol and CO implied that the relatively high levels of methanol observed during MINOS were largely due to direct biogenic emissions, and also that biogenic sources of acetone were highly significant during MINOS (~35%). This in turn suggests that the model deficit in both species may be due, at least in part, to missing biogenic emissions.
Accounting for local meteorological effects in the ozone time-series of Lovozero (Kola Peninsula)
Authors: Tarasova O. A. , Karpetchko A. Yu.
Published: April 2010

Abstract. The relationship between local meteorological conditions and the surface ozone variability was studied by means of statistical modeling, using ozone and meteorological parameters measured at Lovozero (250 m a.s.l., 68.5°N, 35.0°E, Kola Peninsula) for the period of 1999-2000. The regression model of daily mean ozone concentrations on such meteorological parameters as temperature, relative humidity and wind speed explains up to 70% of day-to-day ozone variability in terms of meteorological condition changes, if the seasonal cycle is also considered. A regression model was created for separated time scales of the variables. Short-term, synoptical and seasonal components are separated by means of Kolmogorov-Zurbenko filtering. The synoptical scale variations were chosen as the most informative from the point of their mutual relation with meteorological parameters. Almost 40% of surface ozone variations in time periods of 11-60 days can be explained by the regression model on separated scales that is 30% more efficient than ozone residuals usage. Quantitative and qualitative estimations of the relations between surface ozone and meteorological predictors let us preliminarily conclude that at the Lovozero site surface ozone variability is governed mainly by dynamical processes of various time scale rather than photochemistry, especially during the cold season.
Rapid intercontinental air pollution transport associated with a meteorological bomb
Authors: Stohl A. , Huntrieser H. , Richter A. , Beirle S. , Cooper O. R. , Eckhardt S. , Forster C. , James P. , Spichtinger N. , Wenig M. , Wagner T. , Burrows J. P. , Platt U.
Published: April 2010

Abstract. Intercontinental transport (ICT) of trace substances normally occurs on timescales ranging from a few days to several weeks. In this paper an extraordinary episode in November 2001 is presented, where pollution transport across the North Atlantic took only about one day. The transport mechanism, termed here an intercontinental pollution express highway because of the high wind speeds, was exceptional, as it involved an explosively generated cyclone, a so-called meteorological "bomb''. To the authors' knowledge, this is the first study describing pollution transport in a bomb. The discovery of this event was based on tracer transport model calculations and satellite measurements of NO2, a species with a relatively short lifetime in the atmosphere, which could be transported that far only because of the high wind speeds produced by the bomb. A 15-year transport climatology shows that intercontinental express highways are about four times more frequent in winter than in summer, in agreement with bomb climatologies. The climatology furthermore suggests that intercontinental express highways may be important for the budget of short-lived substances in the remote troposphere. For instance, for a substance with a lifetime of 1 day, express highways may be responsible for about two thirds of the total ICT. We roughly estimate that express highways connecting North America with Europe enhance the average NOx mixing ratios over Europe, due to North American emissions, by about 2-3 pptv in winter.
Aerosol particle size distributions in the lower Fraser Valley: evidence for particle nucleation and growth
Authors: Mozurkewich M. , Chan T.-W. , Aklilu Y.-A. , Verheggen B.
Published: April 2010

Abstract. Particle size distributions from 9 to 640nm diameter were measured at Eagle Ridge in the lower Fraser Valley from 13 August to 1 September 2001 as part of the Pacific 2001 Air Quality Study. The site was on top of a ridge, about 300m above the valley floor, in a predominantly agricultural area about 70km ESE of Vancouver. To further characterize the particles, their hygroscopic properties (affinity for water) were measured. The maximum of the number distributions was generally between 40 and 100nm diameter, but the number distribution was sometimes dominated by ultrafine particles with diameters below 40nm. These ultrafine particles, which appeared to some extent on all days, were frequently associated with elevated levels of CO and NOx, as expected for fresh vehicular emissions. The appearance of these fresh emissions was most pronounced when the growing mixed layer reached the altitude of the site. In contrast, pronounced nucleation events occurred on the five cleanest days; these resulted in particle number concentrations as high as 5x104 particles cm-3 and growth rates of 5 to 10nmhr-1. Nucleation appears to have been triggered when the UV flux reached about 25Wm-2. The growth of these newly formed particles was probably driven by the photochemical oxidation of biogenic organic compounds. Dramatic growth events were also observed on the afternoons of the more polluted days; these produced an extremely narrow mode σ<0.3) at a diameter of about 40nm. Rainy days showed low number concentrations with the size distributions shifted to small sizes. On one of these days there was evidence of nucleation not far from the site; this may have been occurring in the vicinity of the clouds.
Modelling the formation of organic particles in the atmosphere
Authors: Anttila T. , Kerminen V.-M. , Kulmala M. , Laaksonen A. , O'Dowd C. D.
Published: April 2010

Abstract. Particle formation resulting from activation of inorganic stable clusters by a supersaturated organic vapour was investigated using a numerical model. The applied aerosol dynamic model included a detailed description of the activation process along with a treatment of the appropriate aerosol and gas-phase processes. The obtained results suggest that both gaseous sulphuric acid and organic vapours contribute to organic particle formation in continental background areas. The initial growth of freshly-nucleated clusters is driven mainly by condensation of gaseous sulphuric acid and by a lesser extent self-coagulation. After the clusters have reached sizes of around 2 nm in diameter, low-volatile organic vapours start to condense spontaneously into the clusters, thereby accelerating their growth to detectable sizes. A shortage of gaseous sulphuric acid or organic vapours limit, or suppress altogether, the particle formation, since freshly-nucleated clusters are rapidly coagulated away by pre-existing particles. The obtained modelling results were applied to explaining the observed seasonal cycle in the number of aerosol formation events in a continental forest site.