bluuebunny/crossref_metadata_2025 huggingface dataset:
Two-years of NO3radical observations in the boundary layer over the Eastern Mediterranean
Authors: Vrekoussis M. , Mihalopoulos N. , Gerasopoulos E. , Kanakidou M. , Crutzen P. J. , Lelieveld J.
Published: April 2010

Abstract. This is the first study that investigates the seasonal variability of nitrate (NO3) radicals in the marine boundary layer over the East Mediterranean Sea. An extensive data set of NO3 radical observations on the north coast of Crete for more than two years (June 2001–September 2003) is presented here. NO3 radicals follow a distinct seasonal dependency with the highest seasonally average mixing ratios in summer (5.6±1.2 pptv) and the lowest in winter (1.2±1.2 pptv). Episodes with high NO3 mixing ratios have been encountered mainly in polluted air masses originating from mainland Greece, Central and East Europe, and Turkey. Ancillary measurements of ozone, nitrogen dioxide (NO2) and meteorological parameters have been conducted and used to reveal possible relationship with the observed NO3 variability. The acquired NO2 nighttime observations provide the up-to-date most complete overview of NO2 temporal variability in the area. The data show correlations of the NO3 nighttime mixing ratios with temperature (positive), relative humidity (negative) and to a lesser extend with O3 (positive). As inferred from these observations, on average the major sink of NO3 radicals in the area is the heterogeneous reaction of dinitrogen pentoxide (N2O5) on aqueous particles whereas the homogeneous gas phase reactions of NO3 are most important during spring and summer. These observations support a significant contribution of NO3 nighttime chemistry to the oxidizing capacity of the troposphere.
Aerosol single-scattering albedo and asymmetry parameter from MFRSR observations during the ARM Aerosol IOP 2003
Authors: Kassianov E. I. , Flynn C. J. , Ackerman T. P. , Barnard J. C.
Published: April 2010

Abstract. Multi-filter Rotating Shadowband Radiometers (MFRSRs) provide routine measurements of the aerosol optical depth (τ) at six wavelengths (0.415, 0.5, 0.615, 0.673, 0.870 and 0.94 μm). The single-scattering albedo (π0) is typically estimated from the MFRSR measurements by assuming the asymmetry parameter (g). In most instances, however, it is not easy to set an appropriate value of g due to its strong temporal and spatial variability. Here, we introduce and validate an updated version of our retrieval technique that allows one to estimate simultaneously π0 and g for different types of aerosol. We use the aerosol and radiative properties obtained during the Atmospheric Radiation Measurement (ARM) Program's Aerosol Intensive Operational Period (IOP) to validate our retrieval in two ways. First, the MFRSR-retrieved optical properties are compared with those obtained from independent surface, Aerosol Robotic Network (AERONET), and aircraft measurements. The MFRSR-retrieved optical properties are in reasonable agreement with these independent measurements. Second, we perform radiative closure experiments using the MFRSR-retrieved optical properties. The calculated broadband values of the direct and diffuse fluxes are comparable (~5 W/m2) to those obtained from measurements.
Bias determination and precision validation of ozone profiles from MIPAS-Envisat retrieved with the IMK-IAA processor
Authors: Steck T. , von Clarmann T. , Fischer H. , Funke B. , Glatthor N. , Grabowski U. , Höpfner M. , Kellmann S. , Kiefer M. , Linden A. , Milz M. , Stiller G. P. , Wang D. Y. , Allaart M. , Blumenstock Th. , von der Gathen P. , Hansen G. , Hase F. , Hochschild G. , Kopp G. , Kyrö E. , Oelhaf H. , Raffalski U. , Redondas Marrero A. , Remsberg E. , Russell III J. , Stebel K. , Steinbrecht W. , Wetzel G. , Yela M. , Zhang G.
Published: April 2010

Abstract. This paper characterizes vertical ozone profiles retrieved with the IMK-IAA (Institute for Meteorology and Climate Research, Karlsruhe – Instituto de Astrofisica de Andalucia) science-oriented processor from high spectral resolution data (until March 2004) measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the environmental satellite Envisat. Bias determination and precision validation is performed on the basis of correlative measurements by ground-based lidars, Fourier transform infrared spectrometers, and microwave radiometers as well as balloon-borne ozonesondes, the balloon-borne version of MIPAS, and two satellite instruments (Halogen Occultation Experiment and Polar Ozone and Aerosol Measurement III). Percentage mean differences between MIPAS and the comparison instruments for stratospheric ozone are generally within ±10%. The precision in this altitude region is estimated at values between 5 and 10% which gives an accuracy of 15 to 20%. Below 18 km, the spread of the percentage mean differences is larger and the precision degrades to values of more than 20% depending on altitude and latitude. The main reason for the degraded precision at low altitudes is attributed to undetected thin clouds which affect MIPAS retrievals, and to the influence of uncertainties in the water vapor concentration.
Secondary organic aerosol formation fromm-xylene, toluene, and benzene
Authors: Ng N. L. , Kroll J. H. , Chan A. W. H. , Chhabra P. S. , Flagan R. C. , Seinfeld J. H.
Published: April 2010

Abstract. Secondary organic aerosol (SOA) formation from the photooxidation of m-xylene, toluene, and benzene is investigated in the Caltech environmental chambers. Experiments are performed under two limiting NOx conditions; under high-NOx conditions the peroxy radicals (RO2) react only with NO, while under low-NOx conditions they react only with HO2. For all three aromatics studied (m-xylene, toluene, and benzene), the SOA yields (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) under low-NOx conditions substantially exceed those under high-NOx conditions, suggesting the importance of peroxy radical chemistry in SOA formation. Under low-NOx conditions, the SOA yields for m-xylene, toluene, and benzene are constant (36%, 30%, and 37%, respectively), indicating that the SOA formed is effectively nonvolatile under the range of Mo(>10 μg m−3) studied. Under high-NOx conditions, aerosol growth occurs essentially immediately, even when NO concentration is high. The SOA yield curves exhibit behavior similar to that observed by Odum et al. (1996, 1997a, b), although the values are somewhat higher than in the earlier study. The yields measured under high-NOx conditions are higher than previous measurements, suggesting a "rate effect" in SOA formation, in which SOA yields are higher when the oxidation rate is faster. Experiments carried out in the presence of acidic seed aerosol reveal no change of SOA yields from the aromatics as compared with those using neutral seed aerosol.
Atmospheric effects of volcanic eruptions as seen by famous artists and depicted in their paintings
Authors: Zerefos C. S. , Gerogiannis V. T. , Balis D. , Zerefos S. C. , Kazantzidis A.
Published: April 2010

Abstract. Paintings created by famous artists, representing sunsets throughout the period 1500–1900, provide proxy information on the aerosol optical depth following major volcanic eruptions. This is supported by a statistically significant correlation coefficient (0.8) between the measured red-to-green ratios of a few hundred paintings and the dust veil index. A radiative transfer model was used to compile an independent time series of aerosol optical depth at 550 nm corresponding to Northern Hemisphere middle latitudes during the period 1500–1900. The estimated aerosol optical depths range from 0.05 for background aerosol conditions, to about 0.6 following the Tambora and Krakatau eruptions and cover a period practically outside of the instrumentation era.
Observations of OH and HO2 radicals in coastal Antarctica
Authors: Bloss W. J. , Lee J. D. , Heard D. E. , Salmon R. A. , Bauguitte S. J.-B. , Roscoe H. K. , Jones A. E.
Published: April 2010

Abstract. OH and HO2 radical concentrations have been measured in the boundary layer of coastal Antarctica for a six-week period during the austral summer of 2005. The measurements were performed at the British Antarctic Survey's Halley Research Station (75° 35' S, 26° 19' W), using the technique of on-resonance laser-induced fluorescence to detect OH, with HO2 measured following chemical conversion through addition of NO. The mean radical levels were 3.9×105 molecule cm−3 for OH, and 0.76 ppt for HO2 (ppt denotes parts per trillion, by volume). Typical maximum (local noontime) levels were 7.9×105 molecule cm−3 and 1.50 ppt for OH and HO2 respectively. The main sources of HOx were photolysis of O3 and HCHO, with potentially important but uncertain contributions from HONO and higher aldehydes. Of the measured OH sinks, reaction with CO and CH4 dominated, however comparison of the observed OH concentrations with those calculated via the steady state approximation indicated that additional co-reactants were likely to have been present. Elevated levels of NOx resulting from snowpack photochemistry contributed to HOx cycling and enhanced levels of OH, however the halogen oxides IO and BrO dominated the CH3O2 – HO2 – OH conversion in this environment, with associated ozone destruction.
Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: uptake kinetics, condensed-phase products, and particle size change
Authors: George I. J. , Vlasenko A. , Slowik J. G. , Broekhuizen K. , Abbatt J. P. D.
Published: April 2010

Abstract. The kinetics and reaction mechanism for the heterogeneous oxidation of saturated organic aerosols by gas-phase OH radicals were investigated under NOx-free conditions. The reaction of 150 nm diameter Bis(2-ethylhexyl) sebacate (BES) particles with OH was studied as a proxy for chemical aging of atmospheric aerosols containing saturated organic matter. An aerosol reactor flow tube combined with an Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS) and scanning mobility particle sizer (SMPS) was used to study this system. Hydroxyl radicals were produced by 254 nm photolysis of O3 in the presence of water vapour. The kinetics of the heterogeneous oxidation of the BES particles was studied by monitoring the loss of a mass fragment of BES with the ToF-AMS as a function of OH exposure. We measured an initial OH uptake coefficient of γ0=1.3 (±0.4), confirming that this reaction is highly efficient. The density of BES particles increased by up to 20% of the original BES particle density at the highest OH exposure studied, consistent with the particle becoming more oxidized. Electrospray ionization mass spectrometry analysis showed that the major particle-phase reaction products are multifunctional carbonyls and alcohols with higher molecular weights than the starting material. Volatilization of oxidation products accounted for a maximum of 17% decrease of the particle volume at the highest OH exposure studied. Tropospheric organic aerosols will become more oxidized from heterogeneous photochemical oxidation, which may affect not only their physical and chemical properties, but also their hygroscopicity and cloud nucleation activity.
Insights into the role of soot aerosols in cirrus cloud formation
Authors: Kärcher B. , Möhler O. , DeMott P. J. , Pechtl S. , Yu F.
Published: April 2010

Abstract. Cirrus cloud formation is believed to be dominated by homogeneous freezing of supercooled liquid aerosols in many instances. Heterogeneous ice nuclei such as mineral dust, metallic, and soot particles, and some crystalline solids within partially soluble aerosols are suspected to modulate cirrus properties. Among those, the role of ubiquitous soot particles is perhaps the least understood. Because aviation is a major source of upper tropospheric soot particles, we put emphasis on ice formation in dispersing aircraft plumes. The effect of aircraft soot on cirrus formation in the absence of contrails is highly complex and depends on a wide array of emission and environmental parameters. We use a microphysical-chemical model predicting the formation of internally mixed, soot-containing particles up to two days after emission, and suggest two principal scenarios: high concentrations of original soot emissions could slightly increase the number of ice crystals; low concentrations of particles originating from coagulation of emitted soot with background aerosols could lead to a significant reduction in ice crystal number. Both scenarios assume soot particles to be moderate ice nuclei relative to cirrus formation by homogeneous freezing in the presence of few efficient dust ice nuclei. A critical discussion of laboratory experiments reveals that the ice nucleation efficiency of soot particles depends strongly on their source, and, by inference, on atmospheric aging processes. Mass and chemistry of soluble surface coatings appear to be crucial factors. Immersed soot particles tend to be poor ice nuclei, some bare ones nucleate ice at low supersaturations. However, a fundamental understanding of these studies is lacking, rendering extrapolations to atmospheric conditions speculative. In particular, we cannot yet decide which indirect aircraft effect scenario is more plausible, and options suggested to mitigate the problem remain uncertain.
Light induced conversion of nitrogen dioxide into nitrous acid on submicron humic acid aerosol
Authors: Stemmler K. , Ndour M. , Elshorbany Y. , Kleffmann J. , D'Anna B. , George C. , Bohn B. , Ammann M.
Published: April 2010

Abstract. The interactions of aerosols consisting of humic acids with gaseous nitrogen dioxide (NO2) were investigated under different light conditions in aerosol flow tube experiments at ambient pressure and temperature. The results show that NO2 is converted on the humic acid aerosol into nitrous acid (HONO), which is released from the aerosol and can be detected in the gas phase at the reactor exit. The formation of HONO on the humic acid aerosol is strongly activated by light: In the dark, the HONO-formation was below the detection limit, but it was increasing with the intensity of the irradiation with visible light. Under simulated atmospheric conditions with respect to the actinic flux, relative humidity and NO2-concentration, reactive uptake coefficients γrxn for the NO2→HONO conversion on the aerosol between γrxn <10−7 (in the dark) and γrxn=6×10−6 were observed. The observed uptake coefficients decreased with increasing NO2-concentration in the range from 2.7 to 280 ppb and were dependent on the relative humidity (RH) with slightly reduced values at low humidity (<20% RH) and high humidity (>60% RH). The measured uptake coefficients for the NO2→HONO conversion are too low to explain the HONO-formation rates observed near the ground in rural and urban environments by the conversion of NO2→HONO on organic aerosol surfaces, even if one would assume that all aerosols consist of humic acid only. It is concluded that the processes leading to HONO formation on the Earth surface will have a much larger impact on the HONO-formation in the lowermost layer of the troposphere than humic materials potentially occurring in airborne particles.
A case study on biomass burning aerosols: effects on aerosol optical properties and surface radiation levels
Authors: Arola A. , Lindfors A. , Natunen A. , Lehtinen K. E. J.
Published: April 2010

Abstract. In spring 2006, biomass burning aerosols from eastern Europe were transported extensively to Finland, and to other parts of northern Europe. They were observed as far as in the European Arctic. In the first part of this paper, temporal and spatial evolution and transport of these biomass burning aerosols are monitored with MODIS retrieved aerosol optical depth (AOD) imagery at visible wavelengths (0.55 μm). Comparison of MODIS and AERONET AOD is conducted at Tõravere, Estonia. Then trajectory analyses, as well as MODIS Fire Mapper products are used to better understand the type and origin of the air masses. During the studied four-week period AOD values ranged from near zero up to 1.2 at 0.55 μm and the linear correlation between MODIS and AERONET was very high (~0.97). Temporal variability observed within this four-week period was also rather well explained by the trajectory analysis in conjunction with the fire detections produced by the MODIS Rapid Response System. In the second part of our study, the surface measurements of global and UV radiation at Jokioinen, Finland are used to study the effect of this haze episode on the levels of surface radiation. We found reductions up to 35% in noon-time surface UV irradiance (at 340 nm) as compared to typical aerosol conditions. For global (total solar) radiation, the reduction was always smaller, in line with the expected wavelength dependence of the aerosol effect.
Ambient aerosol concentrations of sugars and sugar-alcohols at four different sites in Norway
Authors: Yttri K. E. , Dye C. , Kiss G.
Published: April 2010

Abstract. Sugars and sugar-alcohols are demonstrated to be important constituents of the ambient aerosol water-soluble organic carbon fraction, and to be tracers for primary biological aerosol particles (PBAP). In the present study, levels of four sugars (fructose, glucose, sucrose, trehalose) and three sugar-alcohols (arabitol, inositol, mannitol) in ambient aerosols have been quantified using a novel HPLC/HRMS-TOF (High Performance Liquid Chromatography in combination with High Resolution Mass Spectrometry – Time of Flight) method to assess the contribution of PBAP to PM>sub>10 and PM2.5. Samples were collected at four sites in Norway at different times of the year in order to reflect the various contributing sources and the spatial and seasonal variation of the selected compounds. Sugars and sugar-alcohols were present at all sites investigated, underlining the ubiquity of these highly polar organic compounds. The highest concentrations were reported for sucrose, reaching a maximum concentration of 320 ng m−3 in PM10 and 55 ng m−3 in PM2.5. The mean concentration of sucrose was up to 10 times higher than fructose, glucose and the dimeric sugar trehalose. The mean concentrations of the sugar-alcohols were typically lower, or equal, to that of the monomeric sugars and trehalose. Peak concentrations of arabitol and mannitol did not exceed 30 ng m−3 in PM10, and for PM2.5 all concentrations were below 6 ng m−3. Sugars and sugar-alcohols were associated primarily with coarse aerosols except during wintertime at the suburban site in Elverum, where a shift towards sub micron aerosols was observed. It is proposed that this shift was due to the intensive use of wood burning for residential heating at this site during winter, confirmed by high concurrent concentrations of levoglucosan. Elevated concentrations of sugars in PM2.5 were observed during spring and early summer at the rural background site Birkenes. It is hypothesized that this was due to ruptured pollen.
Halogens and their role in polar boundary-layer ozone depletion
Authors: Simpson W. R. , von Glasow R. , Riedel K. , Anderson P. , Ariya P. , Bottenheim J. , Burrows J. , Carpenter L. J. , Frieß U. , Goodsite M. E. , Heard D. , Hutterli M. , Jacobi H.-W. , Kaleschke L. , Neff B. , Plane J. , Platt U. , Richter A. , Roscoe H. , Sander R. , Shepson P. , Sodeau J. , Steffen A. , Wagner T. , Wolff E.
Published: April 2010

Abstract. During springtime in the polar regions, unique photochemistry converts inert halide salt ions (e.g. Br−) into reactive halogen species (e.g. Br atoms and BrO) that deplete ozone in the boundary layer to near zero levels. Since their discovery in the late 1980s, research on ozone depletion events (ODEs) has made great advances; however many key processes remain poorly understood. In this article we review the history, chemistry, dependence on environmental conditions, and impacts of ODEs. This research has shown the central role of bromine photochemistry, but how salts are transported from the ocean and are oxidized to become reactive halogen species in the air is still not fully understood. Halogens other than bromine (chlorine and iodine) are also activated through incompletely understood mechanisms that are probably coupled to bromine chemistry. The main consequence of halogen activation is chemical destruction of ozone, which removes the primary precursor of atmospheric oxidation, and generation of reactive halogen atoms/oxides that become the primary oxidizing species. The different reactivity of halogens as compared to OH and ozone has broad impacts on atmospheric chemistry, including near complete removal and deposition of mercury, alteration of oxidation fates for organic gases, and export of bromine into the free troposphere. Recent changes in the climate of the Arctic and state of the Arctic sea ice cover are likely to have strong effects on halogen activation and ODEs; however, more research is needed to make meaningful predictions of these changes.
Modelling the cloud condensation nucleus activity of organic acids on the basis of surface tension and osmolality measurements
Authors: Varga Z. , Kiss G. , Hansson H.-C.
Published: April 2010

Abstract. In this study vapour pressure osmometry was used to determine water activity in the solutions of organic acids. The surface tension of the solutions was also monitored in parallel and then Köhler curves were calculated for nine organic acids (oxalic, malonic, succinic, glutaric, adipic, maleic, malic, citric and cis-pinonic). Surface tension depression is negligible for most of the organic acids in dilute (≤1 w/w%) solutions. Therefore, these compounds affect equilibrium vapour pressure only in the beginning phase of droplet formation when the droplet solution is more concentrated but not necessarily at the critical size. An exception is cis-pinonic acid which remarkably depress surface tension also in dilute (0.1 w/w%) solution and hence at the critical point. The surface tension of organic acid solutions is influenced by the solubility of the compound, the length of the carbon chain and also by the polar functional groups present in the molecule. Similarly to surface tension solubility plays an important role also in water activity: compounds with higher solubility (e.g. malonic, maleic and glutaric acid) reduce water activity significantly in the early phase of droplet formation while less soluble acids (e.g. succinic and adipic acid) are saturated in small droplets and the solution starts diluting only in bigger droplets. As a consequence, compounds with lower solubility have a minor effect on water activity in the early phase of droplet formation. To deduce the total effect Köhler curves were calculated and critical supersaturations (Sc) were determined for the organic acids using measured surface tension and water activity. It was found that critical supersaturation grew with growing carbon number. Oxalic acid had the lowest critical supersaturation in the size range studied and it was comparable to the activation of ammonium sulphate. The Sc values obtained in this study were compared to data from CCNC experiments. In most cases good agreement was found. For modelling purposes Sc vs. ddry plots are given and the dependence of water activity and surface tension on concentration are also formulated.
ISORROPIA II: a computationally efficient thermodynamic equilibrium model for K+–Ca2+–Mg2+–NH4+–Na+–SO42−–NO3−–Cl−–H2O aerosols
Authors: Fountoukis C. , Nenes A.
Published: April 2010

Abstract. This study presents ISORROPIA II, a thermodynamic equilibrium model for the K+–Ca2+–Mg2+–NH4+–Na+–SO42−–NO3−–Cl−–H2O aerosol system. A comprehensive evaluation of its performance is conducted against water uptake measurements for laboratory aerosol and predictions of the SCAPE2 thermodynamic module over a wide range of atmospherically relevant conditions. The two models agree well, to within 13% for aerosol water content and total PM mass, 16% for aerosol nitrate and 6% for aerosol chloride and ammonium. Largest discrepancies were found under conditions of low RH, primarily from differences in the treatment of water uptake and solid state composition. In terms of computational speed, ISORROPIA II was more than an order of magnitude faster than SCAPE2, with robust and rapid convergence under all conditions. The addition of crustal species does not slow down the thermodynamic calculations (compared to the older ISORROPIA code) because of optimizations in the activity coefficient calculation algorithm. Based on its computational rigor and performance, ISORROPIA II appears to be a highly attractive alternative for use in large scale air quality and atmospheric transport models.
Tropospheric OH and Cl levels deduced from non-methane hydrocarbon measurements in a marine site
Authors: Arsene C. , Bougiatioti A. , Kanakidou M. , Bonsang B. , Mihalopoulos N.
Published: April 2010

Abstract. In situ continuous hourly measurements of C2–C8 non-methane hydrocarbons (NMHCS) have been performed from March to October 2006 at two coastal locations (natural and rural) on the island of Crete, in the Eastern Mediterranean. Well defined diel variations were observed for several short lived NMHCS (including ethene, propene, n-butane, n-pentane, n-hexane, 2-methyl-pentane). The daytime concentration of hydroxyl (OH) radicals estimated from these experimental data varied from 1.3×106 to ~4.0×106 radical cm−3, in good agreement with box-model simulations. In addition the relative variability of various hydrocarbon pairs (at least 7) was used to derive the tropospheric levels of Cl atoms. The Cl atom concentration has been estimated to range between 0.6×104 and 4.7×104 atom cm−3, in good agreement with gaseous hydrochloric acid (HCl) observations in the area. Such levels of Cl atoms can be of considerable importance for the oxidation capacity of the troposphere on a regional scale.
Cloud-scale model intercomparison of chemical constituent transport in deep convection
Authors: Barth M. C. , Kim S.-W. , Wang C. , Pickering K. E. , Ott L. E. , Stenchikov G. , Leriche M. , Cautenet S. , Pinty J.-P. , Barthe Ch. , Mari C. , Helsdon J. H. , Farley R. D. , Fridlind A. M. , Ackerman A. S. , Spiridonov V. , Telenta B.
Published: April 2010

Abstract. Transport and scavenging of chemical constituents in deep convection is important to understanding the composition of the troposphere and therefore chemistry-climate and air quality issues. High resolution cloud chemistry models have been shown to represent convective processing of trace gases quite well. To improve the representation of sub-grid convective transport and wet deposition in large-scale models, general characteristics, such as species mass flux, from the high resolution cloud chemistry models can be used. However, it is important to understand how these models behave when simulating the same storm. The intercomparison described here examines transport of six species. CO and O3, which are primarily transported, show good agreement among models and compare well with observations. Models that included lightning production of NOx reasonably predict NOx mixing ratios in the anvil compared with observations, but the NOx variability is much larger than that seen for CO and O3. Predicted anvil mixing ratios of the soluble species, HNO3, H2O2, and CH2O, exhibit significant differences among models, attributed to different schemes in these models of cloud processing including the role of the ice phase, the impact of cloud-modified photolysis rates on the chemistry, and the representation of the species chemical reactivity. The lack of measurements of these species in the convective outflow region does not allow us to evaluate the model results with observations.
Using a moving measurement platform for determining the chemical composition of atmospheric aerosols between Moscow and Vladivostok
Authors: Kuokka S. , Teinilä K. , Saarnio K. , Aurela M. , Sillanpää M. , Hillamo R. , Kerminen V.-M. , Pyy K. , Vartiainen E. , Kulmala M. , Skorokhod A. I. , Elansky N. F. , Belikov I. B.
Published: April 2010

Abstract. The TROICA-9 expedition (Trans-Siberian Observations Into the Chemistry of the Atmosphere) was carried out at the Trans-Siberian railway between Moscow and Vladivostok in October 2005. Measurements of aerosol physical and chemical properties were made from an observatory carriage connected to a passenger train. Black carbon (BC) concentrations in fine particles (PM2.5, aerodynamic diameter <2.5 μm) were measured with an aethalometer using a five-minute time resolution. Concentrations of inorganic ions and some organic compounds (Cl−, NO3−, SO42−, Na+, NH4+, K+, Ca2+, Mg2+, oxalate and methane sulphonate) were measured continuously by using an on-line system with a 15-min time resolution. In addition, particle volume size distributions were determined for particles in the diameter range 3–850 nm using a 10-min time resolution. The continuous measurements were completed with 24-h PM2.5 filter samples stored in a refrigerator and analyzed later in a chemical laboratory. The analyses included the mass concentrations of PM2.5, ions, monosaccharide anhydrides (levoglucosan, galactosan and mannosan) and trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V and Zn). The mass concentrations of PM2.5 varied in the range of 4.3–34.8 μg m−3 with an average of 21.6 μg m−3. Fine particle mass consisted mainly of BC (average 27.6%), SO42− (13.0%), NH4+ (4.1%) and NO3− (1.4%). One of the major constituents was obviously organic carbon which was not determined. The contribution of BC was high compared with other studies made in Europe and Asia. High concentrations of ions, BC and particle volume were observed between Moscow and roughly 4000 km east of it, as well as close to Vladivostok, primarily due to local anthropogenic sources. In the natural background area between 4000 and 7200 km away from Moscow, observed concentrations were low, even though local particle sources, such as forest fires, occasionally increased concentrations. During the measured forest fire episodes, most of the aerosol mass appeared to consist of organic particulate matter. Concentrations of the biomass burning tracers levoglucosan, oxalate and potassium were elevated close to the forest fire areas observed by the MODIS satellite. The polluted air masses from Asia seem to have significant influences on the concentration levels of fine particles over south-eastern Russia.
Sensitivity of stratospheric inorganic chlorine to differences in transport
Authors: Waugh D. W. , Strahan S. E. , Newman P. A.
Published: April 2010

Abstract. Correctly modeling stratospheric inorganic chlorine (Cly) is crucial for modeling the past and future evolution of stratospheric ozone. However, comparisons of the chemistry climate models used in the latest international assessment of stratospheric ozone depletion have shown large differences in the modeled Cly, with these differences explaining many of the differences in the simulated evolution of ozone over the next century. Here in, we examine the role of transport in determining the simulated Cly using three simulations from the same off-line chemical transport model that have the same lower tropospheric boundary conditions and the same chemical solver, but differing resolution and/or meteorological fields. These simulations show that transport plays a key role in determining the Cly distribution, and that Cly depends on both the time scales and pathways of transport. The time air spends in the stratosphere (e.g., the mean age) is an important transport factor determining stratospheric Cly, but the relationship between mean age and Cly is not simple. Lower stratospheric Cly depends on the fraction of air that has been in the upper stratosphere, and transport differences between models having the same mean age can result in differences in the fraction of organic chlorine converted into Cly. Differences in transport pathways result in differences in vertical profiles of CFCs, and comparisons of observed and modeled CFC profiles provide a stringent test of transport pathways in models.
Civil Aircraft for the regular investigation of the atmosphere based on an instrumented container: The new CARIBIC system
Authors: Brenninkmeijer C. A. M. , Crutzen P. , Boumard F. , Dauer T. , Dix B. , Ebinghaus R. , Filippi D. , Fischer H. , Franke H. , Frieβ U. , Heintzenberg J. , Helleis F. , Hermann M. , Kock H. H. , Koeppel C. , Lelieveld J. , Leuenberger M. , Martinsson B. G. , Miemczyk S. , Moret H. P. , Nguyen H. N. , Nyfeler P. , Oram D. , O'Sullivan D. , Penkett S. , Platt U. , Pupek M. , Ramonet M. , Randa B. , Reichelt M. , Rhee T. S. , Rohwer J. , Rosenfeld K. , Scharffe D. , Schlager H. , Schumann U. , Slemr F. , Sprung D. , Stock P. , Thaler R. , Valentino F. , van Velthoven P. , Waibel A. , Wandel A. , Waschitschek K. , Wiedensohler A. , Xueref-Remy I. , Zahn A. , Zech U. , Ziereis H.
Published: April 2010

Abstract. An airfreight container with automated instruments for measurement of atmospheric gases and trace compounds was operated on a monthly basis onboard a Boeing 767-300 ER of LTU International Airways during long-distance flights from 1997 to 2002 (CARIBIC, Civil Aircraft for Regular Investigation of the Atmosphere Based on an Instrument Container, http://www.caribic-atmospheric.com). Subsequently a more advanced system has been developed, using a larger capacity container with additional equipment and an improved inlet system. CARIBIC phase #2 was implemented on a new long-range aircraft type Airbus A340-600 of the Lufthansa German Airlines (Star Alliance) in December 2004, creating a powerful flying observatory. The instrument package comprises detectors for the measurement of O3, total and gaseous H2O, NO and NOy, CO, CO2, O2, Hg, and number concentrations of sub-micrometer particles (>4 nm, >12 nm, and >18 nm diameter). Furthermore, an optical particle counter (OPC) and a proton transfer mass spectrometer (PTR-MS) are incorporated. Aerosol samples are collected for analysis of elemental composition and particle morphology after flight. Air samples are taken in glass containers for laboratory analyses of hydrocarbons, halocarbons and greenhouse gases (including isotopic composition of CO2) in several laboratories. Absorption tubes collect oxygenated volatile organic compounds. Three differential optical absorption spectrometers (DOAS) with their telescopes mounted in the inlet system measure atmospheric trace gases such as BrO, HONO, and NO2. A video camera mounted in the inlet provides information about clouds along the flight track. The flying observatory, its equipment and examples of measurement results are reported.
Arctic smoke – record high air pollution levels in the European Arctic due to agricultural fires in Eastern Europe in spring 2006
Authors: Stohl A. , Berg T. , Burkhart J. F. , Fjǽraa A. M. , Forster C. , Herber A. , Hov Ø. , Lunder C. , McMillan W. W. , Oltmans S. , Shiobara M. , Simpson D. , Solberg S. , Stebel K. , Ström J. , Tørseth K. , Treffeisen R. , Virkkunen K. , Yttri K. E.
Published: April 2010

Abstract. In spring 2006, the European Arctic was abnormally warm, setting new historical temperature records. During this warm period, smoke from agricultural fires in Eastern Europe intruded into the European Arctic and caused the most severe air pollution episodes ever recorded there. This paper confirms that biomass burning (BB) was indeed the source of the observed air pollution, studies the transport of the smoke into the Arctic, and presents an overview of the observations taken during the episode. Fire detections from the MODIS instruments aboard the Aqua and Terra satellites were used to estimate the BB emissions. The FLEXPART particle dispersion model was used to show that the smoke was transported to Spitsbergen and Iceland, which was confirmed by MODIS retrievals of the aerosol optical depth (AOD) and AIRS retrievals of carbon monoxide (CO) total columns. Concentrations of halocarbons, carbon dioxide and CO, as well as levoglucosan and potassium, measured at Zeppelin mountain near Ny Ålesund, were used to further corroborate the BB source of the smoke at Spitsbergen. The ozone (O3) and CO concentrations were the highest ever observed at the Zeppelin station, and gaseous elemental mercury was also elevated. A new O3 record was also set at a station on Iceland. The smoke was strongly absorbing – black carbon concentrations were the highest ever recorded at Zeppelin – and strongly perturbed the radiation transmission in the atmosphere: aerosol optical depths were the highest ever measured at Ny Ålesund. We furthermore discuss the aerosol chemical composition, obtained from filter samples, as well as the aerosol size distribution during the smoke event. Photographs show that the snow at a glacier on Spitsbergen became discolored during the episode and, thus, the snow albedo was reduced. Samples of this polluted snow contained strongly elevated levels of potassium, sulphate, nitrate and ammonium ions, thus relating the discoloration to the deposition of the smoke aerosols. This paper shows that, to date, BB has been underestimated as a source of aerosol and air pollution for the Arctic, relative to emissions from fossil fuel combustion. Given its significant impact on air quality over large spatial scales and on radiative processes, the practice of agricultural waste burning should be banned in the future.
Inferring thermodynamic properties from CCN activation experiments: single-component and binary aerosols
Authors: Padró L. T. , Asa-Awuku A. , Morrison R. , Nenes A.
Published: April 2010

Abstract. This study presents a new method, Köhler Theory Analysis (KTA), to infer the molar volume and solubility of organic aerosol constituents. The method is based on measurements of surface tension, chemical composition, and CCN activity coupled with Köhler theory. KTA is evaluated by inferring the molar volume of six known organics (four dicarboxylic acids, one amino acid, and one sugar) in pure form and in mixtures with ammonium sulfate ((NH4)2SO4). The average error in inferred molar volumes are to within 18% of their expected value for organic fractions between 50 and 90%. This suggests that KTA is a potentially powerful tool for determining the CCN characteristic of ambient water soluble organic carbon (WSOC), providing physically-based constraints for aerosol-cloud interaction parameterizations.
Observation of Polar Stratospheric Clouds down to the Mediterranean coast
Authors: Keckhut P. , David Ch. , Marchand M. , Bekki S. , Jumelet J. , Hauchecorne A. , Höpfner M.
Published: April 2010

Abstract. A Polar Stratospheric Cloud (PSC) was detected for the first time in January 2006 over Southern Europe after 25 years of systematic lidar observations. This cloud was observed while the polar vortex was highly distorted during the initial phase of a major stratospheric warming. Very cold stratospheric temperatures (<190 K) centred over the Northern-Western Europe were reported, extending down to the South of France where lidar observations were performed. CTM (Chemical Transport Model) investigations show that this event led to a significant direct ozone destruction (35 ppb/day), within and outside the vortex as chlorine activated air masses were moved to sunlight regions allowing ozone destruction. If such exceptional events of mid-latitudes PSCs were to become frequent in the future, they should not compromise the ozone recovery because their effect appears to be limited temporally and spatially. More importantly, these events might tend to be associated with the initial phase of a stratospheric warming that results into a weakening and warming of the polar vortex and hence into a reduced probability occurrence of PSC temperatures during the rest of the winter.
CALIPSO observations of stratospheric aerosols: a preliminary assessment
Authors: Thomason L. W. , Pitts M. C. , Winker D. M.
Published: April 2010

Abstract. We have examined the 532-nm aerosol backscatter coefficient measurements by the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) for their use in the monitoring of stratospheric aerosol. CALIPSO makes observations that span from 82° S to 82° N each day and, for each profile, backscatter coefficient values reported up to ~40 km. The possibility of using CALIPSO for stratospheric aerosol monitoring is demonstrated by the clear observation of the 20 May 2006 eruption of Montserrat in the earliest CALIPSO data in early June as well as by observations showing the 7 October 2006 eruption of Tavurvur (Rabaul). However, the very low aerosol loading within the stratosphere makes routine observations of the stratospheric aerosol far more difficult than relatively dense volcanic plumes. Nonetheless, we found that averaging a complete days worth of nighttime-only data into 5-deg latitude by 1-km vertical bins yields a stratospheric aerosol distribution that is fairly consistent with past measurements by spaceborne instruments. Based on comparisons with 2004 data from the Stratospheric Aerosol and Gas Experiment, the derived values are close to expectation except in the tropics where they are larger by about a factor of 2. The cause of the difference in the tropics is not readily apparent but is most likely related to difficulties in the lidar calibration process currently found in the CALIOP data at tropical latitudes.
The weekend effect within and downwind of Sacramento – Part 1: Observations of ozone, nitrogen oxides, and VOC reactivity
Authors: Murphy J. G. , Day D. A. , Cleary P. A. , Wooldridge P. J. , Millet D. B. , Goldstein A. H. , Cohen R. C.
Published: April 2010

Abstract. Day-of-week patterns in human activities can be used to examine the ways in which differences in primary emissions result in changes in the rates of photochemical reactions, and the production of secondary pollutants. Data from twelve California Air Resources Board monitoring sites in Sacramento, CA, and the downwind Mountain Counties air basin are analyzed to reveal day of week patterns in ozone and its precursors in the summers of 1998–2002. Measurements of non-methane hydrocarbons are available for the summers of 2001–2003 at three of these sites and NOx at six of these sites for the full time period. This routine monitoring data is complemented by data sets of ozone and nitrogen oxide concentrations obtained in the summers of 2001 and 2003 at three sites in the region and comprehensive measurements of VOC reactivity at two sites in 2001. Daytime concentrations of nitrogen oxides (NOx≡NO+NO2) are approximately 35% lower on weekends at all the sites, whereas the VOC reactivity changes by less than 10%. All six sites in the Sacramento Valley have higher 8-h maximum average ozone on the weekend and are more likely to exceed the national standard of 85 ppb on the weekend. In contrast, all the sites in the Mountain Counties are less likely to exceed the federal ozone standard on the weekend. Analysis of the day-of-week trends in odd oxygen show that the weekend effect of ozone within Sacramento is strongly influenced by NO sources close to the monitoring sites. This suggests that ozone measurements from monitoring sites close to highways, including two rural locations, may not be representative of the regional abundance, and lead to underestimates of long term exposure for humans and ecosystems.
PM measurement campaign HOVERT in the Greater Berlin area: model evaluation with chemically specified particulate matter observations for a one year period
Authors: Beekmann M. , Kerschbaumer A. , Reimer E. , Stern R. , Möller D.
Published: April 2010

Abstract. The HOVERT (HOrizontal and VERtical Transport of ozone and particulate matter) campaign held in the Berlin Brandenburg area in Eastern Germany from September 2001 to September 2002 allowed to collect a unique data set of the aerosol chemical speciation (daily averages) at traffic, urban and rural sites. These observations are used for a thorough evaluation of the aerosol part in the REM-CALGRID model (RCG) developed at the Free University of Berlin (FUB). For inorganic ions (sulphate, nitrate and ammonium), simulated annual averages agree to observations within ±30% at more than half of the sites and always within a factor of two. Correlation coefficients are larger than in previous studies for SO42− and NH4+ (>0.7). For nitrate, less elevated correlations, 0.4–0.7 in the cold season, 0.2–0.4 in the warm season, are encountered. To our knowledge, this is one of the first comparisons of air quality model simulated elemental and organic carbon (EC and OC) with daily observations for a whole year. It suggests an overestimation of EC and OC emissions in the Berlin area (through a scaling techniques between EC, OC and NOx and when assuming correct NOx emissions), and an underestimation of EC and OC at rural sites. Secondary organic aerosol (SOA) formation, recently introduced into the model (SORGAM module, Schell et al., 2001), is simulated as a very variable process, SOA levels varying from close to zero for most days to more than 5 μg/m3. Correlation between simulated SOA to observed OC is about 0.6, indicating that simulated variability partly corresponds to reality.
Intercontinental transport of pollution and dust aerosols: implications for regional air quality
Authors: Chin Mian , Diehl T. , Ginoux P. , Malm W.
Published: April 2010

Abstract. We use the global model GOCART to examine the impact of pollution and dust aerosols emitted from their major sources on surface fine particulate matter concentrations at regional and hemispheric scales. Focusing on the North America region in 2001, we use measurements from the IMPROVE network in the United States to evaluate the model-simulated surface concentrations of the "reconstructed fine mass" (RCFM) and its components of ammonium sulfate, black carbon (BC), organic matter (OM), and fine mode dust. We then quantify the RCFM budget in terms of the RCFM chemical composition, source type, and region of origin to find that in the eastern U.S., ammonium sulfate is the dominant RCFM component (~60%) whereas in the western U.S., dust and OM are just as important as sulfate but have considerable seasonal variations, especially in the NW. On an annual average, pollution aerosol (defined as aerosols from fuel combustion for industrial and transportation uses) from North America accounts for 65–70% of the surface RCFM in the eastern U.S. and for a lower proportion of 30–40% in the western U.S.; by contrast, pollution from outside of North America contributes to just 2–6% (~0.2 μg m−3) of the total RCFM over the U.S. In comparison, long-range transport of dust brings 3 to 4 times more fine particles than the transport of pollution to the U.S. (0.5–0.8 μg m−3 on an annual average) with a maximum influence in spring and over the NW. Of the major pollution regions, Europe has the largest potential to affect the surface aerosol concentrations in other continents due to its shorter distance from receptor continents and its larger fraction of sulfate-producing precursor gas in the outflow. With the IPCC emission scenario for the year 2000, we find that European emissions increase levels of ammonium sulfate by 1–5 μg m−3 over the surface of northern Africa and western Asia, and its contribution to eastern Asia (≥0.2 μg m−3) is twice as much as the Asian contribution to North America. Asia and North America pollution emissions exert strong impacts on their neighboring oceans, but their influences over other continents are relatively small (≤10%) due to long traveling distances across the oceans and efficient removal during transport. Among the major dust source regions, Asia displays a significant influence over large areas in the northern hemisphere except over the North Atlantic and the tropics, where African dust dominates. We also notice that the African dust and European pollution can travel eastward through a pathway spanning across Asia and North Pacific to western North America; such a pathway is difficult to detect because these aerosols usually merge and travel together with Asian dust and pollution labeled as "Asian outflow".