bluuebunny/crossref_metadata_2025 huggingface dataset:
Haze in the Klang Valley of Malaysia
Authors: Keywood M. D. , Ayers G. P. , Gras J. L. , Boers R. , Leong C. P.
Published: April 2010

Abstract. Continuous measurements of dry aerosol light scattering (Bsp) were made at two sites in the Klang Valley of Malaysia between December 1998 and December 2000. In addition 24-h PM2.5 samples were collected on a one-day-in-six cycle and the chemical composition of the aerosol was determined. Periods of excessive haze were defined as 24-h average Bsp values greater than 150 Mm-1 and these occurred on a number of occasions, between May and September 1999, during May 2000, and between July and September 2000. The evidence for smoke being a significant contributor to aerosol during periods of excessive haze is discussed and includes features of the aerosol chemistry, the diurnal cycle of Bsp, and the coincidence of forest fires on Sumatra during the southwest (SW) monsoon period, as well as transport modelling for one week of the southwest Monsoon of 2000. The study highlights that whilst transboundary smoke is a major contributor to poor visibility in the Klang Valley, smoke from fires on Peninsular Malaysia is also a contributor, and at all times, the domestic source of secondary particle production is present.
Evaluated kinetic and photochemical data for atmospheric chemistry: Part 1 – gas phase reactions of Ox, HOx, NOx and SOx species
Authors: Atkinson R. , Baulch D. L. , Cox R. A. , Crowley J. N. , Hampson R. F. , Hynes R. G. , Jenkin M. E. , Rossi M. J. , Troe J.
Published: April 2010

Abstract. This article, the first in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Ox, HOx, NOx and SOx species, which were last published in 1997, and were updated on the IUPAC website in late 2001. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and five appendices containing the data sheets, which provide information upon which the recommendations are made.
Accounting for local meteorological effects in the ozone time-series of Lovozero (Kola Peninsula)
Authors: Tarasova O. A. , Karpetchko A. Y.
Published: April 2010

Abstract. The impact of local meteorological conditions on surface ozone was studied by means of regression models creation. Ozone and meteorological parameters measured at Lovozero site (250 m a.s.l., 68.5° N, 35.0° E, Kola Peninsula) for the period of 1999–2000 were used. The regression model of daily mean ozone concentrations on the meteorological parameters like temperature, relative humidity, and wind speed can explain up to 70% of the ozone variability, if the seasonal cycle is also considered. A regression model was created for separated time scales of the variables. The separation of short-term, synoptical and seasonal components was done by means of Kolmogorov-Zurbenko filtering. The synoptical scale variations were chosen as the most informative from the point of their relation with meteorological parameters. About 40% of synoptical scale variations of surface ozone can be explained by regression model on separated meteo parameters that is 30% more efficient than ozone residuals usage.
Evaporation of high speed sporadic meteors
Authors: Murad E. , Roth C.
Published: April 2010

Abstract. Recent measurements conducted at the Arecibo Observatory report high-speed sporadic meteors having velocities near 50 km/s. The results seem to indicate a bimodal velocity distribution in the sporadic meteors (maxima at ~20 km/s and ~50 km/s). The particles have a maximum mass of ~1 μg. This paper will present an analysis of the ablation of 1 μg meteoroids having velocities of 20, 30, 50, and 70 km/s. The calculations show that there is fractionation even for the fast meteoroids, the effect being particularly noticeable for the 1 μg sporadic particles, and less so for the heavier particles. The relevance of the calculations to the radar observations of the sporadic meteors will be discussed.
Commentary on "Homogeneous nucleation of NAD and NAT in liquid stratospheric aerosols: insufficient to explain denitrification" by Knopf et al.
Authors: Tabazadeh A.
Published: April 2010

Abstract. Abstract not available.
Nonlinear relationships between atmospheric aerosol and its gaseous precursors: Analysis of long-term air quality monitoring data by means of neural networks
Authors: Konovalov I. B.
Published: April 2010

Abstract. The nonlinear features of the relationships between concentrations of aerosol and volatile organic compounds (VOC) and nitrogen oxides (NOx) in urban environments are revealed directly from data of long-term routine measurements of NOx, VOC, and total suspended particulate matter (PM). The main idea of the method is development of special empirical models based on artificial neural networks. These models, that are basically, the nonlinear extension of the commonly used linear statistical models provide the best fit for the real (nonlinear) PM-NOx-VOC relationships under different atmospheric conditions. Such models may be useful in the context of various scientific and practical problems related to atmospheric aerosols. The method is demonstrated on an example of two empirical models based on independent data-sets collected at two air quality monitoring stations at South Coast Air Basin, California. It is shown that in spite of a rather large distance between the monitoring stations (more than 50 km) and thus substantially different environmental conditions, the empirical models demonstrate several common qualitative features. Specifically, under definite conditions, a decrease in the level of NOx or VOC may lead to an increase in mass concentration of aerosol. It is argued that these features are due to the nonlinear dependence of hydroxyl radical on VOC and NOx.
Ice condensation on sulfuric acid tetrahydrate: implications for polar stratospheric ice clouds
Authors: Fortin T. J. , Drdla K. , Iraci L. T. , Tolbert M. A.
Published: April 2010

Abstract. The mechanism of ice nucleation to form Type 2 PSCs is important for controlling the ice particle size and hence the possible dehydration in the polar winter stratosphere. This paper probes heterogeneous ice nucleation on sulfuric acid tetrahydrate (SAT). Laboratory experiments were performed using a thin-film, high-vacuum apparatus in which the condensed phase is monitored via Fourier transform infrared spectroscopy and water pressure is monitored with the combination of an MKS baratron and an ionization gauge. Results show that SAT is an efficient ice nucleus with a critical ice saturation ratio of Sice= 1.3 to 1.02 over the temperature range 169.8–194.5 K. This corresponds to a necessary supercooling of 0.1–1.3 K below the ice frost point. The laboratory data is used as input for a microphysical/photochemical model to probe the effect that this heterogeneous nucleation mechanism could have on Type 2 PSC formation and stratospheric dehydration. In the model simulations, even a very small number of SAT particles (e.g. 10−4 cm−3) result in ice nucleation on SAT as the dominant mechanism for Type 2 PSC formation. As a result, Type 2 PSC formation is more widespread, leading to larger-scale dehydration. The characteristics of the clouds are controlled by the assumed number of SAT particles present, demonstrating that a proper treatment of SAT is critical for correctly modeling Type 2 PSC formation and stratospheric dehydration.
Ground-based PTR-MS measurements of reactive organic compounds during the MINOS campaign in Crete, July–August 2001
Authors: Salisbury G. , Williams J. , Holzinger R. , Gros V. , Mihalopoulos N. , Vrekoussis M. , Sarda-Estève R. , Berresheim H. , von Kuhlmann R. , Lawrence M. , Lelieveld J.
Published: April 2010

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

Abstract. We measured the mixing ratios of ammonia (NH3), nitric acid (HNO3), nitrous acid (HONO), hydrochloric acid (HCl), sulfur dioxide (SO2) and the corresponding water-soluble inorganic aerosol species, ammonium (NH4+), nitrate (NO3−), nitrite (NO2−), chloride (Cl−) and sulfate (SO42−), and their diel and seasonal variations at a pasture site in the Amazon Basin (Rondônia, Brazil). This study was conducted within the framework of LBA-SMOCC (Large Scale Biosphere Atmosphere Experiment in Amazonia Smoke Aerosols, Clouds, Rainfall and Climate). Sampling was performed from 12 September to 14 November 2002, extending from the dry season (extensive biomass burning activity), through the transition period to the wet season (background conditions). Measurements were made continuously using a wet-annular denuder in combination with a Steam-Jet Aerosol Collector (SJAC) followed by suitable on-line analysis. A detailed description and verification of the inlet system for simultaneous sampling of soluble gases and aerosol compounds is presented. Overall measurement uncertainties of the ambient mixing ratios usually remained below 15%. The limit of detection (LOD) was determined for each single data point measured during the field experiment. Median LOD values (3σ-definition) were ≤0.015 ppb for acidic trace gases and aerosol anions and ≤0.118 ppb for NH3 and aerosol NH4+. Mixing ratios of acidic trace gases remained below 1ppb throughout the measurement period, while NH3 levels were an order of magnitude higher. Accordingly, mixing ratios of NH4+ exceeded those of other inorganic aerosol contributors by a factor of 4 to 10. During the wet season, mixing ratios decreased by nearly a factor of 3 for all compounds compared to those observed when intensive biomass burning took place. Additionally, N-containing gas and aerosol species featured pronounced diel variations. This is attributed to strong relative humidity and temperature variations between day and night as well as to changing photochemistry and stability conditions of the planetary boundary layer. HONO exhibited a characteristic diel cycle with high mixing ratios at nighttime and was not completely depleted by photolysis during daylight hours.
Seasonal cycles of isoprene concentrations in the Amazonian rainforest
Authors: Trostdorf C. R. , Gatti L. V. , Yamazaki A. , Potosnak M. J. , Guenther A. , Martins W. C. , Munger J. W.
Published: April 2010

Abstract. Tropical forests are an important global source of volatile organic compounds (VOCs) and other atmospheric trace gases. The high biodiversity in tropical rainforests complicates the extrapolation of biogenic volatile organic compound (BVOC) emissions from leaf-level measurements to landscape and regional or global scales. In Amazônia, a significant fraction of the carbon emitted from the biosphere to the atmosphere is emitted in the form of BVOCs, and the knowledge of these emissions is important to our understanding of tropical and global atmospheric chemistry and carbon cycling. As part of the Large scale Biosphere-atmosphere experiment in Amazônia (LBA). VOC concentrations were measured at two sites near Santarém, Para State, Brazil. The two sites are located in the National Forest of Tapajós, the first corresponding to primary forest and the second to a forest, that was selectively logged. The samples were collected simultaneously at heights of 65 and 55 m (20 and 10 m above forest canopy, respectively). The average isoprene mixing ratio was 2.2–2.5 ppb at the two sites and the standard deviations within a site ranged from 1 to 1.2 ppb. A strong seasonality of isoprene mixing ratio was observed and associated with the wet and dry seasons. The lowest mixing ratios were found during the transition between the wet to dry season, while at the start of the biomass burning season the mixing ratios increase. A qualitative analysis of a one dimensional model demonstrates that the seasonal cycle in concentrations reflects changes in isoprene production by the ecosystem, not changes in boundary layer dynamics or chemistry. The magnitude of the cycle indicates that the physiological capacity of the ecosystem to emit isoprene may depend on water availability although phenological changes could also contribute to the observed variations. A simple 1-D model that assumes mean daytime isoprene fluxes of 1.5 mg m−2h−1 and 0.9 mg m−2h−1 scaled by an algorithm depending on precipitation at the primary forest and selectively logged sites, respectively, is able to reproduce the observed vertical gradients.
Investigation of Arctic ozone depletion sampled over midlatitudes during the Egrett Campaign of spring/summer 2000
Authors: Ross D. E. M. , Pyle J. A. , Harris N. R. P. , McIntyre J. D. , Millard G. A. , Robinson A. D. , Busen R.
Published: April 2010

Abstract. A unique halocarbon dataset has been obtained using the Australian high altitude research aircraft, the Grob G520T Egrett, during May–June 2000 with GC instrument (DIRAC), which has been previously deployed on balloon platforms. The halocarbon data generally shows a good anticorrelation with ozone data obtained simultaneously from commercial sensors. On 5 June 2000, at 380 K, the Egrett entered a high latitude tongue of air over the UK CFC-11 and O3 data obtained on the flight show evidence of this feature. The dataset has been used, in conjunction with a 3D chemical transport model, to infer ozone depletion encountered in the midlatitude lower stratosphere during the flight. We calculate that ozone is depleted by 20% relative to its winter value in the higher latitude airmass. A suite of ozone loss tracers in the model have been used to track ozone depletion according to location relative to the vortex and chemical cycle responsible. The model, initialised on 9 December, indicates that 50% of the total chemical ozone destruction encountered in June in the middle latitudes occurred between the 90–70° N equivalent latitude band and that 70% was due to halogen chemistry.
Aerosol particle size distributions in the lower Fraser Valley: evidence for particle nucleation and growth
Authors: Mozurkewich M. , Chan T.-W. , Aklilu Y.-A. , Verheggen B.
Published: April 2010

Abstract. Particle size distributions from 9 to 640 nm diameter were measured at Eagle Ridge in the lower Fraser Valley from 13 August to 1 September 2001 as part of the Pacific 2001 Air Quality Study. The site was on top of a ridge, about 300 m above the valley floor, in a predominantly agricultural area about 70 km ESE of Vancouver. To further characterize the particles, their hygroscopic properties (affinity for water) were measured. The maximum of the number distributions was generally between 40 and 100 nm diameter, but the number distribution was sometimes dominated by ultrafine particles with diameters below 20 nm. These ultrafine particles, which appeared to some extent on all days, were frequently associated with elevated levels of CO and NOx, as expected for fresh vehicular emissions. The appearance of these fresh emissions was most pronounced when the growing mixed layer reached the altitude of the site. In contrast, pronounced nucleation events occurred on the five cleanest days; these resulted in particle number concentrations as high as 5×104 particles cm−3 and growth rates of 5 to 10 nm hr−1. These events appear to have been driven by the photochemical oxidation of biogenic organic compounds and to have been triggered when the UV flux reached about 25 W m−2. Dramatic growth events were also observed on the afternoons of the more polluted days; these produced an extremely narrow mode (σ<0.3) at a diameter of about 40 nm. Rainy days showed low number concentrations with the size distributions shifted to small sizes. On one of these days there was evidence of nucleation not far from the site; this may have been occurring in the vicinity of the clouds.
Seasonality and extent of extratropical TST derived from in-situ CO measurements during SPURT
Authors: Hoor P. , Gurk C. , Brunner D. , Hegglin M. I. , Wernli H. , Fischer H.
Published: April 2010

Abstract. We present airborne in-situ trace gas measurements which were performed on eight campaigns between November 2001 and July 2003 during the SPURT-project (SPURenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region). The measurements on a quasi regular basis allowed an overview on the seasonal variations of the trace gas distribution in the tropopause region over Europe from 35°–75° N to investigate the influence of transport and mixing across the extratropical tropopause on the lowermost stratosphere. From the correlation of CO and O3 irreversible mixing of tropospheric air into the lowermost stratosphere is identified. The CO distribution indicates that transport and subsequent mixing of tropospheric air across the extratropical tropopause predominantely affects a layer, which closely follows the shape of the local tropopause. In addition the seasonal cycle of CO2 illustrates the strong coupling of that layer to the extratropical troposphere. Both, horizontal gradients of CO on isentropes as well as the CO-O3-distribution in the lowermost stratosphere reveal that the influence of quasi-horizontal transport and subsequent mixing weakens with distance from the local tropopause. However, at large distances from the tropopause a significant influence of tropospheric air is still evident. The relation between N2O and CO2 indicates that a significant contribution of air originating from the tropical tropopause contributes to the background air in the extratropical lowermost stratosphere.
The annual cycle of hydrogen peroxide: is it an indicator of chemical instability?
Authors: Stewart R. W.
Published: April 2010

Abstract. A box model has been used to study the annual cycle in hydrogen peroxide concentrations with the objective of determining whether the observed difference in summer and winter values reflects instability in the underlying photochemistry. The model is run in both steady-state and time-dependent modes. The steady-state calculations show that, for some range of NOx background levels, two stable solutions to the continuity equations exist for a period of days in spring and fall. The corresponding time-dependent model indicates that, for sufficiently high background NOx concentrations, the spring and fall changes in H2O2 concentration may be interpreted as a forced transition between the two underlying stable regimes. The spring transition is more rapid than that in fall, an asymmetry that becomes more marked as background NOx increases. This asymmetry is related to the different time scales involved in chemical production and loss of H2O2. Observations of the spring increase in H2O2 concentration may therefore provide a better measure of the change in the underlying chemical regime than does the fall decrease.
Assessment of the NO-NO2-O3 photostationary state applicability on long-term measurements at the GAW global station Hohenpeissenberg, Germany
Authors: Mannschreck K. , Gilge S. , Plass-Duelmer C. , Fricke W. , Berresheim H.
Published: April 2010

Abstract. Continuous measurements of reactive gases, radiation, and meteorological parameters are carried out at the Meteorological Observatory Hohenpeissenberg (MOHp) as part of the Global Atmosphere Watch (GAW) Program. NO, NO2, O3 and JNO2 data from a four year period (March 1999–December 2002) are evaluated for consistency with photochemical steady state (PSS, Φ=1) conditions. In average PSS was reached in 17%, 13%, 22% and 32% of all cases for the year 1999, 2000, 2001 and 2002, respectively. The extent of deviation from PSS reveals a strong dependence on wind direction at the station. Median values of Φ in the south sector are in the range of 2.5–5.7 and show a high variability. In contrast, values for the other directions show a relatively low variability around a median level of 2. These differences can be explained by local effects. It is shown that the height of the sample inlet line, its distance to the forest and the surrounding topography has a strong impact on both the absolute and relative deviations from PSS. Global irradiance and thus, photolysis of NO2 is reduced within the dense forest. Since the reaction of NO with O3 is still proceeding under these conditions, increased NO2/NO ratios are produced locally in air which is transported through the forest and advected to the MOHp site. Estimates of the peroxy radical concentration (RO2) inferred from PSS are compared with peroxy radical measurements made at the site in June 2000 in a three week campaign. The PSS derived RO2 levels were higher than corresponding measured levels by at least a factor of 2–3. This analysis was made for a wind sector with minimal local effects on PSS. Thus the corresponding Φ median of 2 can be regarded as an upper limit for a deviation from PSS due to chemical reactions, i.e. by peroxy radicals and possible other oxidants converting additional NO to NO2.
Comment on “Improving the seasonal cycle and interannual variations of biomass burning aerosol sources" by Generoso et al.
Authors: Ji Y. , Stocker E.
Published: April 2010

Abstract. Generoso et al. (2003) suggest a method for improving current inventories of aerosol emission from biomass burning based on the Along Track Scanning Radiometer (ATSR) nighttime hot spot product. In order to show the validity and representative of the nighttime burning product for such applications, Genoroso et al. (2003) compared the ATSR nighttime products to the daily fire products from TRMM, AVHRR etc. in nine selected regions. Their analyses demonstrate that in most cases, the nighttime products show a seasonal cycle that is consistent with the daily observations. However, they noticed significant discrepancies in biomass seasonality between ATSR nighttime product and TRMM daily product in Sahel region. In a commentary paper, Giglio and Kendall (2003) clarify that the origin of TRMM fire data used in Generoso et al. (2003) is from TRMM Science Data and Information System (Ji and Stocker, 2002). We thank Giglio and Kendall for such clarifications that provide an opportunity for us to clarify several issues on the applications of TSDIS fire data.
Sudden increases in the NO2 column caused by thunderstorms: a case study in the northern subtropical region
Authors: Gil M. , Yela M. , Cuevas E. , Carreño V.
Published: April 2010

Abstract. A long-term program for NO2 column measurements started in 1993 at the subtropical Izaña Observatory (28° N, 16° W). Seasonal evolution shows a small day-to-day variability as compared with higher latitudes. Sharp increases in the column appear occasionally superimposed on the annual cycle. The origin of these spikes is explored by considering the possibility of tropospheric transport from polluted areas, stratospheric intrusions, meridional transport in the stratosphere and production by lightning, in a case study. From radiative transfer calculations and meteorological information available, it is shown that the NO2 increase takes place in the upper troposphere with values of 300–400 pptv. Back-trajectories reveal that, for the case studied, the air masses came from an area of thunderstorms located upwind. After the analysis of the various possibilities, the NO2 increase by lightning production appears to be the most feasible cause. Annual distribution of spikes displays a maximum in late winter and spring during the shift from midlatitude winter tropopause to summer tropopause.
Ultra-violet absorption cross sections of isotopically substituted nitrous oxide species: 14N14NO, 15N14NO, 14N15NO and 15N15NO
Authors: von Hessberg P. , Kaiser J. , Enghoff M. B. , McLinden C. A. , Sorensen S. L. , Röckmann T. , Johnson M. S.
Published: April 2010

Abstract. The isotopically substituted nitrous oxide species 14N14NO, 15N14NO, 14N15NO and 15N15NO were investigated by ultra-violet (UV) absorption spectroscopy. High precision cross sections were obtained for the wavelength range 181 to 218 nm at temperatures of 233 and 283 K. These data are used to calculate photolytic isotopic fractionation constants as a function of wavelength. The fractionation constants were used in a three-dimensional chemical transport model in order to simulate the actual fractionation of N2O in the stratosphere, and the results were found to be in good agreement with field studies.
Emergence of a linear tracer source from air concentration measurements
Authors: Issartel J.-P.
Published: April 2010

Abstract. The measurement of atmospheric concentrations by a monitoring network is potentially a useful tool investigated for the identification of the widespread sources of trace species. The paper addresses inversion strategies using base functions multiplicatively deduced from the concentrations adjoint to the measurements. This follows the concept of illumination: the various regions are well, poorly or not seen at all. With ordinary adjoint functions the illumination becomes excessive close to the detectors. This may be corrected by attributing each point of the space time domain a geometric weight. After stating the statistical implications, the choice of this renormalising function is shown to be constrained by an unambiguous formal criterion. The expectable values of the measurements are distinguished from the measurement errors. The entropic nature of the criterion is explained; it amounts to evenly distribute the information between the points organised with their weights as a "known domain" describing the influence of the measurements. Finally the criterion is shown to coincide with the definition of the pure states of quantum statistics, and this interpretation is investigated to describe the influence of the measurement uncertainties on the quality of a source estimate. The theory is illustrated by calculations performed with the experimental source ETEX1.
Long-term global distribution of earth’s shortwave radiation budget at the top of atmosphere
Authors: Hatzianastassiou N. , Fotiadi A. , Matsoukas Ch. , Pavlakis K. , Drakakis E. , Hatzidimitriou D. , Vardavas I.
Published: April 2010

Abstract. The mean monthly shortwave (SW) radiation budget at the top of atmosphere (TOA) was computed on 2.5° longitude-latitude resolution for the 14-year period from 1984 to 1997, using a radiative transfer model with long-term climatological data from the International Satellite Cloud Climatology Project (ISCCP-D2) supplemented by data from the National Centers for Environmental Prediction - National Center for Atmospheric Research (NCEP-NCAR) Global Reanalysis project, and other global data bases such as TIROS Operational Vertical Sounder (TOVS) and Global Aerosol Data Set (GADS). The model radiative fluxes at TOA were validated against Earth Radiation Budget Experiment (ERBE) S4 scanner satellite data (1985–1989). The model is able to predict the seasonal and geographical variation of SW TOA fluxes. On a mean annual and global basis, the model is in very good agreement with ERBE, overestimating the outgoing SW radiation at TOA (OSR) by 0.93 Wm−2 (or by 0.92%), within the ERBE uncertainties. At pixel level, the OSR differences between model and ERBE are mostly within ±10 Wm−2, with ±5 Wm−2 over extended regions, while there exist some geographic areas with differences of up to 40 Wm−2, associated with uncertainties in cloud properties and surface albedo. The 14-year average model results give a planetary albedo equal to 29.6% and a TOA OSR flux of 101.2 Wm-2. A significant linearly decreasing trend in OSR and planetary albedo was found, equal to 2.3 Wm−2 and 0.6% over the 14-year period (from January 1984 to December 1997), indicating an increasing solar planetary warming. This planetary SW radiative heating occurs in the tropical and sub-tropical areas (20° S–20° N), with clouds being the most likely cause. The computed global mean OSR anomaly ranges within ±4 Wm−2, with signals from El Niño and La Niña events or Pinatubo eruption, whereas significant negative OSR anomalies, starting from year 1992, are also detected.
The role of surfactants in Köhler theory reconsidered
Authors: Sorjamaa R. , Raatikainen T. , Laaksonen A.
Published: April 2010

Abstract. Atmospheric aerosol particles typically consist of inorganic salts and organic material. The inorganic compounds as well as their hygroscopic properties are well defined, but the effect of organic compounds on cloud droplet activation is still poorly characterized. The focus of the present study is in the organic compounds that are surface active i.e. they concentrate on droplet surface and decrease droplet surface tension. Gibbsian surface thermodynamics were used to find out how partitioning in binary and ternary aqueous solutions affects the droplet surface tension and the droplet bulk concentration in droplets large enough to act as cloud condensation nuclei. Sodium dodecyl sulfate was used as a model compound together with sodium chloride to find out the effect the correct evaluation of surfactant partitioning has on the solute effect (Raoult effect). While the partitioning is known to lead to higher surface tension compared to a case in which partitioning is neglected, the present results show that the partitioning also alters the solute effect, and that the change is large enough to further increase the critical supersaturation and hence decrease the droplet activation. The fraction of surfactant partitioned to droplet surface increases with decreasing droplet size, which suggests that surfactants might enhance the activation of larger particles relatively more thus leading to less dense clouds. Cis-pinonic acid-ammonium sulfate aqueous solution was studied in order to relate the partitioning to more realistic atmospheric situation and to find out the combined effects of dissolution and partitioning behaviour. The results show that correct partitioning consideration alters the shape of the Köhler curve when compared to a situation in which the partitioning is neglected either completely or in the Raoult effect.
A study of the phase transition behavior of mixed ammonium sulfate – malonic acid aerosols
Authors: Braban C. F. , Abbatt J. P. D.
Published: April 2010

Abstract. This is a study into the phase transitions of aerosol composed of the ternary system ammonium sulfate (AS) – malonic acid (MA) – water using infrared extinction spectroscopy. Twelve compositions were studied in both deliquescence and efflorescence mode experiments. The presence of a MA fraction, by dry mass, (fMA) of 0.1 in an AS aerosol altered the relative humidity at which the phase transitions occur in an atmospherically significant manner. For compositions with 0.25<fMA<0.90, no distinct "deliquescence" was observed, contrary to the observed behavior in the binary systems. The crystallization of both the MA and AS components is suppressed by the presence of the other component in the aerosol. At fMA=0.9, the crystallization relative humidity of MA was lowered from RH=6% to less than 1%. Similarly, at fMA=0.4, the AS component did not crystallize. The atmospheric implications of the results are discussed.
Rayleigh lidar observation of a warm stratopause over a tropical site, Gadanki (13.5° N; 79.2° E)
Authors: Sivakumar V. , Morel B. , Bencherif H. , Baray J. L. , Baldy S. , Hauchecorne A. , Rao P. B.
Published: April 2010

Abstract. The first Rayleigh lidar observation of a stratopause warming over a tropical site, Gadanki (13.5° N; 79.2° E) is presented in this paper. The warming event has been observed on 22–23 February 2001, and has been found to occur in the stratopause height region (~45–55 km). The magnitude of the warming is found to be ~18 K with respect to the winter-mean temperature profile derived from the lidar data collected over March 1998 to July 2001. The event observed by the lidar has also been seen in the data from Halogen Occultation Experiment (HALOE) on board the UARS satellite. The zonal-mean temperature at 80° N and the zonal-mean zonal wind at 60° N from National Centre for Environmental Prediction (NCEP) and European Centre for Medium-Range Weather Forecasts (ECMWF) reanalysis indicate that a major warming episode also took place in the northern polar hemisphere, a week before to the day of the observation over Gadanki. Eliassen-Palm (E-P) flux calculations from ECMWF reanalysis show evidence of propagation of planetary-wave activity from high and mid to low latitudes consecutive to the major warming episode over the pole. Our results support the view that the most likely source mechanism for the observed stratopause warming is the increase in planetary-wave activity.
Carbonyl compounds in boreal coniferous forest air in Hyytiälä, Southern Finland
Authors: Hellén H. , Hakola H. , Reissell A. , Ruuskanen T. M.
Published: April 2010

Abstract. A variety of C1-C12 carbonyl compounds were measured in the air of a boreal coniferous forest located in Hyytiälä, Southern Finland. 24-h samples were collected during March and April in 2003 using DNPH (2,4-dinitrophenyl hydrazine) coated C18-cartridges and analyzed by liquid chromatography-mass spectrometry (LC-MS). Altogether 22 carbonyl compounds were quantified. The most abundant carbonyls were acetone (24-h average 1340 ng/m3), formaldehyde (480 ng/m3) and acetaldehyde (360 ng/m3). In contrast, scaling of concentrations against reactivity with the hydroxyl (OH) radical significantly increased the contribution of larger aldehydes and ketones (e.g. decanal, octanal and 6-methyl-5-hepten-2-one). Concentrations of monoterpene reaction products nopinone (9 ng/m3) and limona ketone (5 ng/m3) were low compared to the most abundant low molecular weight carbonyls. The total concentration of carbonyl compounds in Hyytiälä in April/March 2003 was much higher than the concentration of aromatic hydrocarbons and monoterpenes in April 2002. Lifetimes of the measured carbonyls with respect to reactions with OH radicals, ozone (O3), and nitrate (NO3) radicals as well as photolysis were estimated. The main sinks for most of the carbonyl compounds in Hyytiälä in springtime are expected to be reactions with the OH radical and photolysis. For 6-methyl-5-hepten-2-one and limona ketone also reactions with ozone are important. The sources of carbonyl compounds are presently highly uncertain. Due to the relatively short lifetimes of aldehydes and ketones, secondary biogenic and anthropogenic sources, that is oxidation of volatile organic compounds, and primary biogenic sources are expected to dominate in Hyytiälä.
Laboratory evidence for volume-dominated nucleation of ice in supercooled water microdroplets
Authors: Duft D. , Leisner T.
Published: April 2010

Abstract. We report on measurements of the rate of homogeneous ice nucleation in supercooled water microdroplets levitated in an electrodynamic balance. By comparison of the freezing probability for droplets of radius 49 µm and 19 µm, we are able to conclude that homogeneous freezing is a volume-proportional process and that surface nucleation might only be important, if at all, for much smaller droplets.
Extrapolating future Arctic ozone losses
Authors: Knudsen B. M. , Andersen S. B. , Christiansen B. , Larsen N. , Rex M. , Harris N. R. P. , Naujokat B.
Published: April 2010

Abstract. Future increases in the concentration of greenhouse gases and water vapour are likely to cool the stratosphere further and to increase the amount of polar stratospheric clouds (PSCs). Future Arctic PSC areas have been extrapolated using the highly significant trends in the temperature record from 1958–2001. Using a tight correlation between PSC area and the total vortex ozone depletion and taking the decreasing amounts of ozone depleting substances into account we make empirical estimates of future ozone. The result is that Arctic ozone losses increase until 2010–2020 and only decrease slightly up to 2030. This approach is an alternative method of prediction to that based on the complex coupled chemistry-climate models (CCMs).
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 put on inter-comparing these methods. However, large uncertainties remain on the sensitivities to methods intrinsic parameters, and on the best measure for STE with regard to end effects on chemistry. The goal of the present study is to address these two fundamental issues in the context of the application of a trajectory-based Lagrangian method, which has been applied in the past to climatological studies and has also been involved in inter-comparison studies, to a typical baroclinic wave breaking event. The analysis sheds light on (i) the fine mesoscale temporal and spatial structures that are associated with episodic, rapid inflows of stratospheric air into the troposphere; (ii) the spatial resolution of 1°×1° required to reasonably capture STE fluxes in such a wave breaking event; (iii) the effective removal of spurious exchange events using a threshold residence time; (iv) the relevance of residence time distributions for capturing the effective chemical forcing of STE; (v) the large differences in the temporal evolution and geographical distribution of STE fluxes across the 2 and the 4 potential vorticity unit iso-surface definitions of the tropopause.
Measuring atmospheric naphthalene with laser-induced fluorescence
Authors: Martinez M. , Harder H. , Ren X. , Lesher R. L. , Brune W. H.
Published: April 2010

Abstract. A new method for measuring gas-phase naphthalene in the atmosphere is based on laser-induced fluorescence at low pressure. The fluorescence spectrum of naphthalene near 308 nm was identified. Naphthalene fluorescence quenching by N2, O2 and H2O was investigated in the laboratory. No significant quenching was found for H2O with mixing ratio up to 2.5%. The quenching rate of naphthalene fluorescence is (1.98±0.18)×10−11 cm3 molecule−1 s−1 for N2, and (2.48±0.08)×10−10 cm3 molecule−1 s−1 for O2 at 297 K. Instrument calibrations were performed with a range of naphthalene mixing ratios between 5 and 80 parts per billion by volume (ppbv, 10−9. In the current instrument configuration, the detection limit is estimated to be about 20 parts per trillion by volume (pptv, 10−12) with 2σ confidence and a 1-min integration time. Measurement of atmospheric naphthalene in three cities, Nashville, TN, Houston, TX, and New York City, NY, are presented. Good correlation between naphthalene and major anthropogenic pollutants is found.
Atmospheric particle formation events at Värriö measurement station in Finnish Lapland 1998–2002
Authors: Vehkamäki H. , Dal Maso M. , Hussein T. , Flanagan R. , Hyvärinen A. , Lauros J. , Merikanto J. , Mönkkönen P. , Pihlatie M. , Salminen K. , Sogacheva L. , Thum T. , Ruuskanen T. , Keronen P. , Aalto P. P. , Hari P. , Lehtinen K. E. J. , Rannik Ü. , Kulmala M.
Published: April 2010

Abstract. We have identified 147 clear 8 nm diameter particle formation events at the SMEAR I station in Värriö, northern Finland during calendar years 1998–2002. The events have been classified in detail according to the particle formation rate, growth rate, event starting time, different gas phase species concentrations and pre-existing particle concentrations as well as various meteorological conditions. Most of the events occurred during the spring months between March and May, suggesting that increasing biological activity might produce the precursor gases for particle formation. The apparent 8 nm particle formation rates were around 0.1/cm3s, and they were uncorrelated with growth rates that vary between 0.5 and 10 nm/h. The air masses, which had clearly elevated sulphur dioxide concentrations above 1.6 ppb came, as expected, from the direction of Nikel and Monschegorsk smelteries. Only 15 formation events can be explained by the pollution plume from these sources.
Using an extended Kalman filter learning algorithm for feed-forward neural networks to describe tracer correlations
Authors: Lary D. J. , Mussa H. Y.
Published: April 2010

Abstract. In this study a new extended Kalman filter (EKF) learning algorithm for feed-forward neural networks (FFN) is used. With the EKF approach, the training of the FFN can be seen as state estimation for a non-linear stationary process. The EKF method gives excellent convergence performances provided that there is enough computer core memory and that the machine precision is high. Neural networks are ideally suited to describe the spatial and temporal dependence of tracer-tracer correlations. The neural network performs well even in regions where the correlations are less compact and normally a family of correlation curves would be required. For example, the CH4-N2O correlation can be well described using a neural network trained with the latitude, pressure, time of year, and CH4 volume mixing ratio (v.m.r.). The neural network was able to reproduce the CH4-N2O correlation with a correlation coefficient between simulated and training values of 0.9997. The neural network Fortran code used is available for download.
Hydroxyl radicals maintain the self-cleansing capacity of the troposphere
Authors: Lelieveld J. , Dentener F. J. , Peters W. , Krol M. C.
Published: April 2010

Abstract. Billions of tons natural and anthropogenic gases are released and subsequently removed from the troposphere each year. Photochemical reactions, initiated by hydroxyl (OH) radicals, oxidise most gases to products which are more easily removed by precipitation and dry deposition at the Earth's surface. Since human-induced pollution emissions strongly affect OH formation and loss, large global changes in OH concentrations are possible. The available evidence as reviewed here, however, indicates that global mean OH has changed relatively little in the past century. Depletion of OH by reactive carbon gases has been compensated by increased OH formation by nitrogen oxides, an act of "inadvertent geo-engineering". Analyses of global mean OH for the past 2.5 decades, however, partly based on methyl chloroform measurements, are ambiguous. Especially the OH trend in the 1990s based on these analyses is at odds with present understanding. Since the discrepancy is dominated by the uncertainty in methyl chloroform emission estimates, improvements of source inventories and model analyses, combined with continued high precision methyl chloroform measurements, will help resolve this problem.
Systematic reduction of complex tropospheric chemical mechanisms using sensitivity and time-scale analyses
Authors: Whitehouse L. E. , Tomlin A. S. , Pilling M. J.
Published: April 2010

Abstract. Explicit mechanisms describing the complex degradation pathways of atmospheric volatile organic compounds (VOCs) are important, since they allow the study of the contribution of individual VOCS to secondary pollutant formation. They are computationally expensive to solve however, since they contain large numbers of species and a wide range of time-scales causing stiffness in the resulting equation systems. This paper and the following companion paper describe the application of systematic and automated methods for reducing such complex mechanisms, whilst maintaining the accuracy of the model with respect to important species and features. The methods are demonstrated via application to version 2 of the Leeds Master Chemical Mechanism. The methods of local concentration sensitivity analysis and overall rate sensitivity analysis proved to be efficient and capable of removing the majority of redundant reactions and species in the scheme across a wide range of conditions relevant to the polluted troposphere. The application of principal component analysis of the rate sensitivity matrix was computationally expensive due to its use of the decomposition of very large matrices, and did not produce significant reduction over and above the other sensitivity methods. The use of the quasi-steady state approximation (QSSA) proved to be an extremely successful method of removing the fast time-scales within the system, as demonstrated by a local perturbation analysis at each stage of reduction. QSSA species were automatically selected via the calculation of instantaneous QSSA errors based on user-selected tolerances. The application of the QSSA led to the removal of a large number of alkoxy radicals and excited Criegee bi-radicals via reaction lumping. The resulting reduced mechanism was shown to reproduce the concentration profiles of the important species selected from the full mechanism over a wide range of conditions, including those outside of which the reduced mechanism was generated. As a result of a reduction in the number of species in the scheme of a factor of 2, and a reduction in stiffness, the computational time required for simulations was reduced by a factor of 4 when compared to the full scheme.