bluuebunny/crossref_metadata_2025 huggingface dataset:
Atmospheric transport and deposition of Indonesian volcanic emissions
Authors: Pfeffer M. A. , Langmann B. , Graf H.-F.
Published: April 2010

Abstract. A regional climate model has been used to study the transport and deposition of sulfur (SO2 and SO42-) and PbCl2 emissions from Indonesian volcanoes. The sensitivity of the atmospheric loss of these trace species to meteorological conditions and their solubility was examined. Two experiments were conducted: 1) volcanic sulfur released as primarily SO2 and subject to transport, deposition, and oxidation to SO42-; and 2) PbCl2 released as an infinitely soluble passive tracer subject to only transport and deposition. The first experiment was used to calculate SO2 loss rates from each active Indonesian volcano producing an annual mean loss rate for all volcanoes of 1.1×10-5 s-1, or an e-folding rate of approximately 1 day. SO2 loss rate was found to vary seasonally, be poorly correlated with wind speed, and uncorrelated with temperature or relative humidity. The variability of SO2 loss rates is found to be correlated with the variability of wind speeds, suggesting that it is much more difficult to establish a "typical'' SO2 loss rate for volcanoes that are exposed to changeable winds. Within an average distance of 70 km away from the active Indonesian volcanoes, 53% of SO2 loss is due to conversion to SO42-, 42% due to dry deposition, and 5% due to lateral transport away from the dominant direction of plume travel. The solubility of volcanic emissions in water is shown to influence their atmospheric transport and deposition. High concentrations of PbCl2 are predicted to be deposited near to the volcanoes while volcanic S travels further away until removal from the atmosphere primarily via the wet deposition of H2SO4. The ratio of the concentration of PbCl2 to SO2 is found to exponentially decay at increasing distance from the volcanoes. The more rapid removal of highly soluble species should be considered when observing SO2 in an aged plume and relating this concentration to other volcanic species. An assumption that the ratio between the concentrations of highly soluble volcanic compounds and SO2 within a plume is equal to that observed in fumarolic gases is reasonable at small distances from the volcanic vent, but will result in an underestimation of the emission flux of highly soluble species.
Importance of mineral cations and organics in gas-aerosol partitioning of reactive nitrogen compounds: case study based on MINOS results
Authors: Metzger S. , Mihalopoulos N. , Lelieveld J.
Published: April 2010

Abstract. The partitioning of reactive nitrogen compounds between the gas and the aerosol phase, as observed during the MINOS (Mediterranean INtensive Oxidant Study) campaign in Crete, Greece, in July and August 2001, has been studied with three thermodynamic gas-aerosol equilibrium models (EQMs) of different chemical complexity: ISORROPIA, which is limited to the ammonium-sulfate-nitrate-sodium-chloride-water-system; SCAPE2, which also includes mineral elements (calcium, magnesium and potassium); and EQSAM2, which additionally accounts for organic acids. The different EQMs are constrained by measured gas (g) and aerosol (a) concentrations: Total ammonia (NH3(g) and NH4(a)+), total nitrate (HNO3(g) and NO3(a)-), total sulfate (H2SO4(g) and SO4(a)2-), total chloride (HCl(g) and Cl-(a)), sodium (Na+(a)), calcium (Ca2+(a)), magnesium (Mg2+(a)), potassium (K+(a)) and organic acids (a). Although the three EQMs differ considerably in particular aspects, their application at the same level of complexity yields comparable results for the equilibrium composition and phase partitioning of ammonia and nitric acid, i.e. within the range of measurement uncertainties (~10%). Their application at different levels of complexity, however, gives rise to substantial differences for the gas-aerosol partitioning of reactive nitrogen compounds. Our results show that only if (soluble) mineral components and (lumped) organic acids are accounted for, the observed gas-aerosol partitioning of ammonia and nitric acid can be accurately reproduced for air pollution episodes characterized by a complex chemical mixture, typical for the Mediterranean lower atmosphere.
A TGA/FT-IR study for measuring OC and EC in aerosol samples
Authors: Fermo P. , Piazzalunga A. , Vecchi R. , Valli G. , Ceriani M.
Published: April 2010

Abstract. Carbon analysis consists in the evaluation of the carbonaceous content of the aerosol (TC) but, more importantly, of its distribution between the two components EC (Elemental Carbon) and OC (Organic Carbon) that are characterized by different physical-chemical properties. In spite of the numerous studies focused on this topic, nowadays a universal methodology for the determination of the two components EC and OC is not available. In fact OC and EC (also known as black carbon or soot) are operationally defined by the method of analysis and, as a consequence, different methods can produce different results. In this paper we present results on the application of TGA/FT-IR (Thermo-gravimetric Analysis/Fourier Transformed Infrared Spectroscopy) to the characterization of carbonaceous aerosols. The analytical methodology was applied to PM10 (particulate matter with aerodynamic diameter smaller than 10 μm) four-hour time resolution samples collected in Milan urban area. The method is a two-steps thermal one and it is based on the different thermal behaviour of OC and EC. It has been set up analyzing suitable standards containing both organic and elemental carbon. Carbon quantification is achieved by on-line, continuous monitoring of CO2 infrared absorption at 2361 cm−1. A good separation between OC and EC on particulate matter (PM) samples has been obtained. Ranges and average values were 12–70 μg/m3 and 20 μg/m3 for OC and 0.2–6 μg/m3 and 2 μg/m3 for EC. On average OC and EC made up 29 (±13)% and 2.5 (±1.8)% of the PM10 fraction, respectively. The method reliability has been verified by a preliminary comparison with TOT (Thermal Optical Transmission) technique. OC and EC values determined for ambient samples of PM10 were correlated with meteorological parameters as well as with Radon concentrations.
Stratosphere-troposphere exchange from the Lagrangian perspective: a case study and method sensitivities
Authors: Bourqui M. S.
Published: April 2010

Abstract. An important part of extra-tropical stratosphere-to-troposphere transport occurs in association with baroclinic wave breaking and cut-off decay at the tropopause. In the last decade many studies have attempted to estimate stratosphere-troposphere exchange (STE) in such synoptic events with various methods, and more recently efforts have been made to inter-compare these methods. These inter-comparisons show large variations between estimates from different methods. This large uncertainty points to a need to thoroughly evaluate such methods, assess the realism of the resulting STE estimates and determine the sensitivities to intrinsic parameters of the methods. The present study focuses on a trajectory-based Lagrangian method which has been applied in the past to climatological studies. This method is applied here to the quantification of STE in the context of a typical baroclinic wave breaking event. The analysis sheds light on (i) the complex three-dimensional temporal and spatial structures that are associated with the rapid inflow of stratospheric air into the troposphere, (ii) the variation of STE mass flux with the choice of the dynamical tropopause definition within 1.5 to 5 PVU, (iii) the sensitivity of the results to resolution, and in particular the minimum spatial resolution of 1°×1° required to reasonably capture STE fluxes in this wave breaking event, (iv) the effective removal of spurious exchange events using a threshold residence time larger than 8 h.
Atmospheric oxidation in the Mexico City Metropolitan Area (MCMA) during April 2003
Authors: Shirley T. R. , Brune W. H. , Ren X. , Mao J. , Lesher R. , Cardenas B. , Volkamer R. , Molina L. T. , Molina M. J. , Lamb B. , Velasco E. , Jobson T. , Alexander M.
Published: April 2010

Abstract. The Mexico City Metropolitan Area (MCMA) study in April 2003 had measurements of many atmospheric constituents, including OH and HO2. It provided the first opportunity to examine atmospheric oxidation in a megacity in a developing country that has more pollution than typical U.S. and European cities. At midday, OH typically reached 0.35 pptv (~7×106 cm−3), comparable to amounts observed in U.S. cities, but HO2 reached 40 pptv, more than observed in most U.S. cities. The OH reactivity was also measured, even during the highly polluted morning rush hour. MCMA's OH reactivity was 25 s−1 during most of the day and 120 s−1 at morning rush hour, which was several times greater than has been measured in any U.S. city. Median measured and modeled OH and HO2 agreed to within combined uncertainties, although for OH, the model exceeded the measurement by more than 30% during midday. OH production and loss, which were calculated from measurements, were in balance to within uncertainties, although production exceeded loss during morning rush hour. This imbalance has been observed in other cities. The HO2/OH ratio from measurements and steady-state analyses have essentially the same dependence on NO, except when NO was near 100 ppbv. This agreement is unlike other urban studies, in which HO2/OH ratio decreased much less than expected as NO increased. As a result of the active photochemistry in MCMA 2003, the median calculated ozone production from measured HO2 reached 50 ppb h−1, a much higher rate than observed in U.S. cities.
Chemical ozone loss in the Arctic winter 2002/2003 determined with Match
Authors: Streibel M. , Rex M. , von der Gathen P. , Lehmann R. , Harris N. R. P. , Braathen G. O. , Reimer E. , Deckelmann H. , Chipperfield M. , Millard G. , Allaart M. , Andersen S. B. , Claude H. , Davies J. , De Backer H. , Dier H. , Dorokov V. , Fast H. , Gerding M. , Kyrö E. , Litynska Z. , Moore D. , Moran E. , Nagai T. , Nakane H. , Parrondo C. , Skrivankova P. , Stübi R. , Vaughan G. , Viatte P. , Yushkov V.
Published: April 2010

Abstract. The Match technique was used to determine chemically induced ozone loss inside the stratospheric vortex during the Arctic winter 2002/2003. From end of November 2002, which is the earliest start of a Match campaign ever, until end of March 2003 approximately 800 ozonesondes were launched from 34 stations in the Arctic and mid latitudes. Ozone loss rates were quantified from the beginning of December until mid-March in the vertical region of 400–550 K potential temperature. In accordance with the occurrence of a large area of conditions favourable for the formation of polar stratospheric clouds in December ozone destruction rates varied between 10–15 ppbv/day depending on height. Maximum loss rates around 35 ppbv/day were reached during late January. Afterwards ozone loss rates decreased until mid-March when the final warming of the vortex began. In the period from 2 December 2002 to 16 March 2003 the accumulated ozone loss reduced the partial ozone column of 400–500 K potential temperature by 56±4 DU. This value is in good agreement with that inferred from the empirical relation of ozone loss against the volume of potential polar stratospheric clouds within the northern hemisphere. The sensitivity of the results on recent improvements of the approach has been tested.
Development of a cloud microphysical model and parameterizations to describe the effect of CCN on warm cloud
Authors: Kuba N. , Fujiyoshi Y.
Published: April 2010

Abstract. First, a hybrid cloud microphysical model was developed that incorporates both Lagrangian and Eulerian frameworks to study quantitatively the effect of cloud condensation nuclei (CCN) on the precipitation of warm clouds. A parcel model and a grid model comprise the cloud model. The condensation growth of CCN in each parcel is estimated in a Lagrangian framework. Changes in cloud droplet size distribution arising from condensation and coalescence are calculated on grid points using a two-moment bin method in a semi-Lagrangian framework. Sedimentation and advection are estimated in the Eulerian framework between grid points. Results from the cloud model show that an increase in the number of CCN affects both the amount and the area of precipitation. Additionally, results from the hybrid microphysical model and Kessler's parameterization were compared. Second, new parameterizations were developed that estimate the number and size distribution of cloud droplets given the updraft velocity and the number of CCN. The parameterizations were derived from the results of numerous numerical experiments that used the cloud microphysical parcel model. The input information of CCN for these parameterizations is only several values of CCN spectrum (they are given by CCN counter for example). It is more convenient than conventional parameterizations those need values concerned with CCN spectrum, C and k in the equation of N=CSk, or, breadth, total number and median radius, for example. The new parameterizations' predictions of initial cloud droplet size distribution for the bin method were verified by using the aforesaid hybrid microphysical model. The newly developed parameterizations will save computing time, and can effectively approximate components of cloud microphysics in a non-hydrostatic cloud model. The parameterizations are useful not only in the bin method in the regional cloud-resolving model but also both for a two-moment bulk microphysical model and for a global model. The effects of sea salt, sulfate, and organic carbon particles were also studied with these parameterizations and global model.
New particle formation in air mass transported between two measurement sites in Northern Finland
Authors: Komppula M. , Sihto S.-L. , Korhonen H. , Lihavainen H. , Kerminen V.-M. , Kulmala M. , Viisanen Y.
Published: April 2010

Abstract. This study covers four years of aerosol number size distribution data from Pallas and Värriö sites 250 km apart from each other in Northern Finland and compares new particle formation events between these sites. In air masses of eastern origin almost all events were observed to start earlier at the eastern station Värriö, whereas in air masses of western origin most of the events were observed to start earlier at the western station Pallas. This demonstrates that particle formation in a certain air mass type depends not only on the diurnal variation of the parameters causing the phenomenon (such as photochemistry) but also on some properties carried by the air mass itself. The correlation in growth rates between the two sites was relatively good, which suggests that the amount of condensable vapour causing the growth must have been at about the same level in both sites. The condensation sink was frequently much higher at the downwind station. It seems that secondary particle formation related to biogenic sources dominate in many cases over the particle sinks during the air mass transport between the sites. Two cases of transport from Pallas to Värriö were further analysed with an aerosol dynamics model. The model was able to reproduce the observed nucleation events 250 km down-wind at Värriö but revealed some differences between the two cases. The simulated nucleation rates were in both cases similar but the organic concentration profiles that best reproduced the observations were different in the two cases indicating that divergent formation reactions may dominate under different conditions. The simulations also suggested that organic compounds were the main contributor to new particle growth, which offers a tentative hypothesis to the distinct features of new particles at the two sites: Air masses arriving from the Atlantic Ocean typically spent approximately only ten hours over land before arriving at Pallas, and thus the time for the organic vapours to accumulate in the air and to interact with the particles is relatively short. This can lead to low nucleation mode growth rates and even to suppression of detectable particle formation event due to efficient scavenging of newly formed clusters, as was observed in the case studies.
Optical and physical properties of aerosols in the boundary layer and free troposphere over the Amazon Basin during the biomass burning season
Authors: Chand D. , Guyon P. , Artaxo P. , Schmid O. , Frank G. P. , Rizzo L. V. , Mayol-Bracero O. L. , Gatti L. V. , Andreae M. O.
Published: April 2010

Abstract. As part of the Large Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC) campaign, detailed surface and airborne aerosol measurements were performed over the Amazon Basin during the dry to wet season from 16 September to 14 November 2002. Optical and physical properties of aerosols at the surface, and in the boundary layer (BL) and free troposphere (FT) during the dry season are discussed in this article. Carbon monoxide (CO) is used as a tracer for biomass burning emissions. At the surface, good correlation among the light scattering coefficient (σs at 545 nm), PM2.5, and CO indicates that biomass burning is the main source of aerosols. Accumulation of haze during some of the large-scale biomass burning events led to high PM2.5 (225 μg m−3), σs (1435 Mm−1), aerosol optical depth at 500 nm (3.0), and CO (3000 ppb). A few rainy episodes reduced the PM2.5, number concentration (CN) and CO concentration by two orders of magnitude. The correlation analysis between σs and aerosol optical thickness shows that most of the optically active aerosols are confined to a layer with a scale height of 1617 m during the burning season. This is confirmed by aircraft profiles. The average mass scattering and absorption efficiencies (545 nm) for small particles (diameter Dp<1.5 μm) at surface level are found to be 5.0 and 0.33 m2 g−1, respectively, when relating the aerosol optical properties to PM2.5 aerosols. The observed mean single scattering albedo (ωo at 545 nm) for submicron aerosols at the surface is 0.92±0.02. The light scattering by particles (Δσs/Δ CN) increase 2–10 times from the surface to the FT, most probably due to the combined affects of coagulation and condensation.
Some ice nucleation characteristics of Asian and Saharan desert dust
Authors: Field P. R. , Möhler O. , Connolly P. , Krämer M. , Cotton R. , Heymsfield A. J. , Saathoff H. , Schnaiter M.
Published: April 2010

Abstract. The large (7 m×4 m cylinder, 84 m3) AIDA (Aerosol Interactions and Dynamics in the Atmosphere) cloud chamber facility at Forschungszentrum, Karlsruhe, Germany was used to test the ice nucleating ability of two desert dust samples from the Sahara and Asia. Aerosol samples were lognormally distributed with a mode diameter of 0.4(±0.1) μm and geometric standard deviation of ~1.7(±0.2). At temperatures warmer than −40°C droplets were formed before ice crystals formed and there was generally no deposition nucleation observed. At temperatures colder than −40°C both dust samples exhibited dual nucleation events that were observed during the same expansion experiment. The primary nucleation event occurred at ice saturation ratios of 1.1 to 1.3 and is likely to be a deposition nucleation mode. The secondary nucleation event occurred at ice saturation ratios between 1.35 and 1.5. We cannot categorically determine whether this ice nucleation event is via a further deposition mode or a condensation mode, but the presence of some soluble material in the dust samples leads us to favour the latter process. The activated fractions of desert dust ranged from ~5–10% at −20°C to 20–40% at temperatures colder than −40°C. There was no obvious difference between the nucleation behaviour of the two dust samples.
Efficiency of the deposition mode ice nucleation on mineral dust particles
Authors: Möhler O. , Field P. R. , Connolly P. , Benz S. , Saathoff H. , Schnaiter M. , Wagner R. , Cotton R. , Krämer M. , Mangold A. , Heymsfield A. J.
Published: April 2010

Abstract. The deposition mode ice nucleation efficiency of various dust aerosols was investigated at cirrus cloud temperatures between 196 and 223 K using the aerosol and cloud chamber facility AIDA (Aerosol Interaction and Dynamics in the Atmosphere). Arizona test dust (ATD) as a reference material and two dust samples from the Takla Makan desert in Asia (AD1) and the Sahara (SD2) were used for the experiments at simulated cloud conditions. The dust particle sizes were almost lognormally distributed with mode diameters between 0.3 and 0.5 μm and geometric standard deviations between 1.6 and 1.9. Deposition ice nucleation was most efficient on ATD particles with ice-active particle fractions of about 0.6 and 0.8 at an ice saturation ratio Si<1.15 and temperatures of 223 and 209 K, respectively. No significant change of the ice nucleation efficiency was found in up to three subsequent cycles of ice activation and evaporation with the same ATD aerosol. This indicates that the phenomenon of preactivation does not apply to ATD particles. The desert dust samples SD2 and AD1 showed a significantly lower fraction of active deposition nuclei, about 0.25 at 223 K and Si<1.35. For all samples the ice activated aerosol fraction could be approximated by an exponential equation as function of Si. This indicates that deposition ice nucleation on mineral particles may not be treated in the same stochastic sense as homogeneous freezing. The suggested formulation of ice activation spectra may be used to calculate the formation rate of ice crystals in models, if the number concentration of dust particles is known. More experimental work is needed to quantify the variability of the ice activation spectra as function of the temperature and dust particle properties.
Modeling atmospheric CO2 concentration profiles and fluxes above sloping terrain at a boreal site
Authors: Aalto T. , Hatakka J. , Karstens U. , Aurela M. , Thum T. , Lohila A.
Published: April 2010

Abstract. CO2 fluxes and concentrations were simulated in the planetary boundary layer above subarctic hilly terrain using a three dimensional model. The model solves the transport equations in the local scale and includes a vegetation sub-model. A WMO/GAW background concentration measurement site and an ecosystem flux measurement site are located inside the modeled region at a hilltop and above a mixed boreal forest, respectively. According to model results, the concentration measurement at the hill site was representative for continental background. However, this was not the case for the whole model domain. Concentration at few meters above active vegetation represented mainly local variation. Local variation became inseparable from the regional signal at about 60-100 m above ground. Flow over hills changed profiles of environmental variables and height of inversion layer, however CO2 profiles were more affected by upwind land use than topography. The hill site was above boundary layer during night and inside boundary layer during daytime. The CO2 input from model lateral boundaries dominated in both cases. Daily variation in the CO2 assimilation rate was clearly seen in the CO2 profiles. Concentration difference between the hill site and the forest site was about 5ppm during afternoon according to both model and measurements. The average modeled flux to the whole model region was about 40% of measured and modeled local flux at the forest site.
NO2 Profile retrieval using airborne multi axis UV-visible skylight absorption measurements over central Europe
Authors: Bruns M. , Buehler S. A. , Burrows J. P. , Richter A. , Rozanov A. , Wang P. , Heue K. P. , Platt U. , Pundt I. , Wagner T.
Published: April 2010

Abstract. A recent development in ground-based remote sensing of atmospheric constituents by UV/visible absorption measurements of scattered light is the simultaneous use of several directions with small elevation angles in addition to the traditional zenith-sky pointing. The different light paths through the atmosphere enable the vertical distribution of some atmospheric absorbers such as NO2, BrO or O3 to be retrieved. In this study, the amount of profile information that can be retrieved from such measurements on aircraft is investigated for the trace gas NO2. A Sensitivity study on synthetic data is performed for a combination of four lines of sight (LOS) (0°(nadir), 88°, 92°, and 180° (zenith)) and three wavelength regions [center wavelengths: 362.5 nm, 437.5 nm, and 485.0 nm]. The method used in this work is a combination of two previously established methods described in Petritoli et al. (2002) and Wang et al. (2004). The investigation presented here demonstrates the potential of this LOS/wavelengths setup to retrieve a significant amount of profile information from airborne multiax is differential optical absorption spectrometer (AMAXDOAS) measurements with a vertical resolution of 3.0 to 4.5 km in the lower troposphere and 2.0 to 3.5 km near flight altitude. Above 13 km the profile information content of AMAXDOAS measurements is sparse. The retrieval algorithm used in this work is the AMAXDOAS profile retrievalalgorithm (APROVAL). Further, retrieved profiles with a significant amount (up to 3.2 ppbv) of NO2 in the boundary layer over the Po-valley (Italy) are presented. Airborne multiaxis measurements are thus a promising tool for atmospheric studies in the troposphere.
The evolution of the global aerosol system in a transient climate simulation from 1860 to 2100
Authors: Stier P. , Feichter J. , Roeckner E. , Kloster S. , Esch M.
Published: April 2010

Abstract. The evolution of the global aerosol system from 1860 to 2100 is investigated through a transient atmosphere-ocean General Circulation Model climate simulation with interactively coupled atmospheric aerosol and oceanic biogeochemistry modules. The microphysical aerosol module HAM incorporates the major global aerosol cycles with prognostic treatment of their composition, size distribution, and mixing state. Based on an SRES A1B emission scenario, the global mean sulfate burden is projected to peak in 2020 while black carbon and particulate organic matter show a lagged peak around 2070. From present day to future conditions the anthropogenic aerosol burden shifts generally from the northern high-latitudes to the developing low-latitude source regions with impacts on regional climate. Atmospheric residence- and aging-times show significant alterations under varying climatic and pollution conditions. Concurrently, the aerosol mixing state changes with an increasing aerosol mass fraction residing in the internally mixed accumulation mode. The associated increase in black carbon causes a more than threefold increase of its co-single scattering albedo from 1860 to 2100. Mid-visible aerosol optical depth increases from pre-industrial times, predominantly from the aerosol fine fraction, peaks at 0.26 around the sulfate peak in 2020 and maintains a high level thereafter, due to the continuing increase in carbonaceous aerosols. The global mean anthropogenic top of the atmosphere clear-sky short-wave direct aerosol radiative perturbation intensifies to −1.1 W m−2 around 2020 and weakens after 2050 to −0.6 W m−2, owing to an increase in atmospheric absorption. The demonstrated modifications in the aerosol residence- and aging-times, the microphysical state, and radiative properties challenge simplistic approaches to estimate the aerosol radiative effects from emission projections.
Inverse modelling for mercury over Europe
Authors: Roustan Y. , Bocquet M.
Published: April 2010

Abstract. The fate and transport of mercury over Europe is studied using a regional Eulerian transport model. Because gaseous elemental mercury is a long-lived species in the atmosphere, boundary conditions must be properly taken into account. Ground measurements of gaseous mercury are very sensitive to the uncertainties attached to those forcing conditions. Inverse modelling can help to constrain the forcing fields and help to improve the predicted mercury concentrations. More generally, it allows to reduce the weaknesses of a regional model against a global or hemispherical model for such diffuse trace constituent. Adjoint techniques are employed to relate rigorously and explicitly the measurements to the forcing fields. This way, the inverse problem is clearly defined. Using EMEP measurements of gaseous mercury and performing the inversions, it is shown that boundary conditions can be improved significantly as well as the forecast concentrations. Using inverse modelling to improve the emission inventory is however much more difficult. Indeed, there are currently not enough mercury monitoring stations, and they are located far away from the center of Europe.
Oxalic acid as a heterogeneous ice nucleus in the upper troposphere and its indirect aerosol effect
Authors: Zobrist B. , Marcolli C. , Koop T. , Luo B. P. , Murphy D. M. , Lohmann U. , Zardini A. A. , Krieger U. K. , Corti T. , Cziczo D. J. , Fueglistaler S. , Hudson P. K. , Thomson D. S. , Peter T.
Published: April 2010

Abstract. Heterogeneous ice freezing points of aqueous solutions containing various immersed solid dicarboxylic acids (oxalic, adipic, succinic, phthalic and fumaric) have been measured with a differential scanning calorimeter. The results show that only the dihydrate of oxalic acid (OAD) acts as a heterogeneous ice nucleus, with an increase in freezing temperature between 2 and 5 K depending on solution composition. In several field campaigns, oxalic acid enriched particles have been detected in the upper troposphere with single particle aerosol mass spectrometry. Simulations with a microphysical box model indicate that the presence of OAD may reduce the ice particle number density in cirrus clouds by up to ~50% when compared to exclusively homogeneous cirrus formation without OAD. Using the ECHAM4 climate model we estimate the global net radiative effect caused by this heterogeneous freezing to result in a cooling as high as −0.3 Wm−2.
Black carbon or brown carbon? The nature of light-absorbing carbonaceous aerosols
Authors: Andreae M. O. , Gelencsér A.
Published: April 2010

Abstract. Although the definition and measurement techniques for atmospheric "black carbon" ("BC") or "elemental carbon'' ("EC") have long been subjects of scientific controversy, the recent discovery of light-absorbing carbon that is not black ("brown carbon, Cbrown") makes it imperative to reassess and redefine the components that make up light-absorbing carbonaceous matter (LAC) in the atmosphere. Evidence for the atmospheric presence of Cbrown comes from (1) spectral aerosol light absorption measurements near specific combustion sources, (2) observations of spectral properties of water extracts of continental aerosol, (3) laboratory studies indicating the formation of light-absorbing organic matter in the atmosphere, and (4) indirectly from the chemical analogy of aerosol species to colored natural humic substances. We show that brown carbon may severely bias measurements of "BC" and "EC" over vast parts of the troposphere, especially those strongly polluted by biomass burning, where the mass concentration of Cbrown is high relative to that of soot carbon. Chemical measurements to determine "EC" are biased by the refractory nature of Cbrown as well as by complex matrix interferences. Optical measurements of "BC" suffer from a number of problems: (1) many of the presently used instruments introduce a substantial bias into the determination of aerosol light absorption, (2) there is no unique conversion factor between light absorption and "EC" or "BC" concentration in ambient aerosols, and (3) the difference in spectral properties between the different types of LAC, as well as the chemical complexity of Cbrown, lead to several conceptual as well as practical complications. We also suggest that due to the sharply increasing absorption of Cbrown towards the UV, single-wavelength light absorption measurements may not be adequate for the assessment of absorption of solar radiation in the troposphere. We discuss the possible consequences of these effects for our understanding of tropospheric processes, including their influence on UV-irradiance, atmospheric photochemistry and radiative transfer in clouds.
Technical note: Evaluation of standard ultraviolet absorption ozone monitors in a polluted urban environment
Authors: Dunlea E. J. , Herndon S. C. , Nelson D. D. , Volkamer R. M. , Lamb B. K. , Allwine E. J. , Grutter M. , Ramos Villegas C. R. , Marquez C. , Blanco S. , Cardenas B. , Kolb C. E. , Molina L. T. , Molina M. J.
Published: April 2010

Abstract. The performance of the EPA Federal Equivalent Method (FEM) technique for monitoring ambient concentrations of O3 via ultraviolet absorption (UV) has been evaluated using data from the Mexico City Metropolitan Area field campaign (MCMA-2003). Comparisons of UV O3 monitors with open path Differential Optical Absorption Spectroscopy (DOAS) and open path Fourier Transform Infrared (FTIR) spectroscopy instruments in two locations revealed average discrepancies in the measured concentrations between +13% to −18%. Good agreement of two separate open path DOAS measurements at one location indicated that spatial and temporal inhomogeneities were not substantially influencing comparisons of the point sampling and open path instruments. The poor agreement between the UV O3 monitors and the open path instruments was attributed to incorrect calibration factors for the UV monitors, although interferences could not be completely ruled out. Applying a linear correction to these calibration factors results in excellent agreement of the UV O3 monitors with the co-located open path measurements; regression slopes of 0.94 to 1.04 and associated R2 values of >0.89. A third UV O3 monitor suffered from large spurious interferences, which were attributed to extinction of UV radiation within the monitor by fine particles (<0.2 µm). The overall performance of this particular monitor was poor owing to a combination of interferences from a contaminated particle filter and/or ozone scrubber. Suggestions for improved operation practices of these UV O3 monitors and recommendations for future testing are made.
A study on the aerosol extinction-to-backscatter ratio with combination of micro-pulse LIDAR and MODIS over Hong Kong
Authors: He Q. S. , Li C. C. , Mao J. T. , Lau A. K. H. , Li P. R.
Published: April 2010

Abstract. The aerosol extinction-to-backscatter ratio is an important parameter for inverting LIDAR signals in the LIDAR equation. It is a complicated function of the aerosol microphysical characteristics. In this paper, a method to retrieve the column-averaged aerosol extinction-to-backscatter ratio by constraining the aerosol optical depths (AOD) from a Micro-pulse LIDAR (MPL) by the AOD measurements from the Moderate Resolution Imaging Spectroradiometer (MODIS) is presented. Both measurements were taken on cloud free days between 1 May 2003 and 30 June 2004 over Hong Kong, a coastal city in south China. Simultaneous measurements of aerosol scattering coefficients with a forward scattering visibility sensor are compared with the LIDAR retrieval of aerosol extinction coefficients. The data are then analyzed to determine seasonal trends of the aetrosol extinction-to-backscatter ratio. In addition, the relationships between the extinction-to-backscatter ratio and wind conditions as well as other aerosol microphysical parameters are presented. The mean aerosol extinction-to-backscatter ratio for the whole period was found to be 29.1±5.8 sr, with a minimum of 18 sr in July 2003 and a maximum of 44 sr in March 2004. The ratio is lower in summer because of the dominance of oceanic aerosols in association with the prevailing southwesterly monsoon. In contrast, relatively larger ratios are noted in spring and winter because of the increased impact of local and regional industrial pollutants associated with the northerly monsoon. The extended LIDAR measurements over Hong Kong provide not only a more accurate retrieval of aerosol extinction coefficient profiles, but also significant substantial information for air pollution and climate studies in the region.
Vehicular fuel composition and atmospheric emissions in South China: Hong Kong, Macau, Guangzhou, and Zhuhai
Authors: Tsai W. Y. , Chan L. Y. , Blake D. R. , Chu K. W.
Published: April 2010

Abstract. Vehicular emission is an important source of air pollutants in urban cities in the Pearl River Delta (PRD) region of South China. In order to study the impact of evaporative loss of vehicular fuel on air quality, several commonly used fuel samples were collected in four main cities in the PRD region – Hong Kong, Guangzhou, Macau and Zhuhai, and analyzed for their volatile organic compounds (VOCs) composition. Source profiles of vapors of the vehicular fuels used in these cities were constructed and are believed to be the first reported for the PRD region. The C8-C10 hydrocarbons were the main constituents of diesel. Different from diesel, gasoline used in the PRD region was mainly comprised of lighter C4-C7 hydrocarbons, with toluene and i-pentane being the two most abundant species. The toluene content in the Hong Kong and Macau gasoline samples were higher than that in Guangzhou and Zhuhai, while the reverse was true for the benzene content. The benzene levels in Guangzhou and Zhuhai exceeded the maximum allowable benzene levels for Mainland China unleaded gasoline. Liquefied Petroleum Gas (LPG) samples were collected only in Hong Kong and were comprised mainly of n-butane, propane and i-butane. Traffic samples indicated that evaporative loss and vehicular combustion were the primary contributors to elevated VOC levels in roadside atmospheres. Significant i-pentane and toluene concentrations were observed in roadside atmospheres in all four cities. Ratio of i-pentane in gasoline vapors to that in roadside samples were calculated and this showed that the degree of evaporative loss were higher in Guangzhou and Zhuhai than that in Hong Kong and Macau. We suggest the difference is due to the better maintenance and more new cars in Hong Kong and Macau. From tunnel samples collected in Hong Kong in two different years, we found that the relative amount of propane, i-butane, and n-butane increased between 2001 to 2003, consistent with the 40% increase in LPG fueled vehicles. Propane to butanes ratios were calculated for LPG samples and tunnels samples, and the comparable ratios illustrated the LPG leakages from LPG fueled vehicles crossing the tunnel.
Airborne multi-axis DOAS measurements of tropospheric SO2 plumes in the Po-valley, Italy
Authors: Wang P. , Richter A. , Bruns M. , Burrows J. P. , Scheele R. , Junkermann W. , Heue K.-P. , Wagner T. , Platt U. , Pundt I.
Published: April 2010

Abstract. During the second FORMAT (FORMaldehyde as A Tracer of oxidation in the troposphere) campaign in 2003 the airborne multi-axis DOAS instrument (AMAXDOAS) performed scattered-light spectroscopic measurements of SO2 over the city of Mantova and the power plant Porto Tolle, both situated in the Po-valley, Northern Italy. The SO2 vertical columns and emission flux were derived from two days of measurements, 26 and 27 September 2003. The SO2 emission flux from the power plant Porto Tolle was calculated to 1.93×1025 molec s-1 on 26 September and in good agreement with official emission data, which quote 2.25×1025 molec s-1. On 27 September the measured flux was much lower (3.77×1024 molec s-1) if ECMWF wind data are used, but of comparable magnitude (2.4×1025 molec s-1) if the aircraft on-board wind measurements are utilised. Official emission data was 2.07×1025 molec s-1 indicating only a small change from the previous day. Over the city of Mantova, the observed SO2 vertical columns were 1.1×1016 molec cm-2 and 1.9×1016 molec cm-2 on 26 and 27 September, respectively. This is in good agreement with ground-based measurements of 5.9 ppbv and 10.0 ppbv which correspond to 1.2×1016 molec cm-2 and 2.2×1016 molec cm-2 if a well mixed boundary layer of 500m altitude is assumed.
Imaging gravity waves in lower stratospheric AMSU-A radiances, Part 1: Simple forward model
Authors: Eckermann S. D. , Wu D. L.
Published: April 2010

Abstract. Using a simplified model of in-orbit radiance acquisition by the Advanced Microwave Sounding Unit (AMSU-A), we derive three-dimensional temperature weighting functions for Channel 9 measurements (peaking at ~60–90 hPa) at all 30 cross-track beam positions and use them to investigate the sensitivity of these radiances to gravity waves. The vertical widths of the weighting functions limit detection to waves with vertical wavelengths of ≳10 km, with slightly better vertical wavelength sensitivity at the outermost scan angles due to the limb effect. Fourier Transforms of two-dimensional cross-track weighting functions reveal optimal sensitivity to cross-track wavelengths at the near-nadir scan angles, where horizontal measurement footprints are smallest. This sensitivity is greater for the AMSU-A on the Aqua satellite than for the identical instruments on the NOAA meteorological satellites, due to a lower orbit altitude and thus smaller horizontal footprints from antenna spreading. Small cross-track asymmetries in the radiance response to gravity waves are found that peak at the mid-range scan angles, with more symmetric responses at near-nadir and far off-nadir scan angles. Three-dimensional simulations show gravity wave oscillations imaged in horizontal AMSU-A radiance maps swept out by the scan pattern and satellite motion. A distorting curvature is added to imaged wave phase lines due to vertical variations in weighting function peaks with cross-track scan angle. This wave distortion is analogous to the well-known "limb darkening" and "limb brightening" of microwave radiances acquired from purely vertical background temperature profiles by cross-track scanners. Waves propagating along track are more visible in these images at the outermost scan angles than those propagating cross track, due to oversampling and narrower widths of the horizontal measurement footprints in the along track direction. Based on nominal noise floors and representative lower stratospheric wave temperature amplitudes, our modeling indicates that Channel 9 AMSU-A radiances can resolve and horizontally image gravity waves with horizontal wavelengths of ≳150 km and vertical wavelengths of ≳10 km.
A parameterization of size resolved below cloud scavenging of aerosols by rain
Authors: Henzing J. S. , Olivié D. J. L. , van Velthoven P. F. J.
Published: April 2010

Abstract. A size dependent parameterization for the removal of aerosol particles by falling rain droplets is developed. Scavenging coefficients are calculated explicitly as a function of aerosol particle size and precipitation intensity including the full interaction of rain droplet size distribution and aerosol particles. The actual parameterization is a simple and accurate three-parameter fit through these pre-calculated scavenging coefficients. The parameterization is applied in the global chemistry transport model TM4 and the importance of below-cloud scavenging relative to other removal mechanisms is investigated for sea salt aerosol. For a full year run (year 2000), we find that below-cloud scavenging accounts for 12% of the total removal of super-micron aerosol. At mid-latitudes of both hemispheres the fractional contribution of below-cloud scavenging to the total removal of super-micron sea salt is about 30% with regional maxima exceeding 50%. Below-cloud scavenging reduces the global average super-micron aerosol lifetime from 2.47 to 2.16 days in our simulations. Despite large uncertainties in precipitation, relative humidity, and water uptake by aerosol particles, we conclude that below cloud scavenging is likely an important sink for super-micron sized sea salt aerosol particles that needs to be included in size-resolved aerosol models.
Factors of air ion balance in a coniferous forest according to measurements in Hyytiälä, Finland
Authors: Tammet H. , Hõrrak U. , Laakso L. , Kulmala M.
Published: April 2010

Abstract. A new mathematical model describing air ion balance was developed and tested. It has improved approximations and includes dry deposition of ions onto the forest canopy. The model leads to an explicit algebraic solution of the balance equations. This allows simple calculation of both the ionization rate and the average charge of aerosol particles from measurements of air ions and aerosol particles, with some parameters of the forest. Charged aerosol particles are distinguished from cluster ions by their size, which exceeds 1.6 nm diameter. The relative uncertainty of the ionization rate is about the same or less than the relative uncertainties of the measurements. The model was tested with specific air ion measurements carried out simultaneously at two heights at the Hyytiälä forest station, Finland. Earlier studies have shown a difference in the predictions of the ionization rate in the Hyytiälä forest when calculated in two different ways: based on the measurements of the environmental radioactivity and based on the air ion and aerosol measurements. The new model explains the difference as a consequence of neglecting dry deposition of ions in the earlier models. The ionization rate during the 16 h campaign was 5.6±0.8 cm−3 s−1 at the height of 2 m and 3.9±0.2 cm−3 s−1 at the height of 14 m, between the tops of the trees. The difference points out the necessity to consider the height variation when the ionization rate is used as a parameter in studies of ion-induced nucleation. Additional results are some estimates of the parameters of air ion balance. The recombination sink of cluster ions on the ions of opposite polarity made up 9–13%, the sink on aerosol particles 65–69%, and the sink on forest canopy 18–26% of the total sink of cluster ions. The average lifetime of cluster ions was about 130 s for positive and about 110 s for negative ions. At the height of 2 m, about 70% of the space charge of air was carried by aerosol particles, and at the height of 14 m, about 84%.
Model simulations and aircraft measurements of vertical, seasonal and latitudinal O3 and CO distributions over Europe
Authors: Fischer H. , Lawrence M. , Gurk Ch. , Hoor P. , Lelieveld J. , Hegglin M. I. , Brunner D. , Schiller C.
Published: April 2010

Abstract. During a series of 8 measurement campaigns within the SPURT project (2001-2003), vertical profiles of CO and O3 have been obtained at subtropical, middle and high latitudes over western Europe, covering the troposphere and lowermost stratosphere up to ~14 km altitude during all seasons. The seasonal and latitudinal variation of the measured trace gas profiles are compared to simulations with the chemical transport model MATCH. In the troposphere reasonable agreement between observations and model predictions is achieved for CO and O3, in particular at subtropical and mid-latitudes, while the model overestimates (underestimates) CO (O3 in the lowermost stratosphere particularly at high latitudes, indicating too strong simulated bi-directional exchange across the tropopause. By the use of tagged tracers in the model, long-range transport of Asian air masses is identified as the dominant source of CO pollution over Europe in the free troposphere.