bluuebunny/crossref_metadata_2025 huggingface dataset:
Secondary maxima in ozone profiles
Authors: Lemoine R.
Published: April 2010

Abstract. Ozone profiles from balloon soundings as well as SAGEII ozone profiles were used to detect anomalous large ozone concentrations of ozone in the lower stratosphere. These secondary ozone maxima are found to be the result of differential advection of ozone-poor and ozone-rich air associated with Rossby wave breaking events. The frequency and intensity of secondary ozone maxima and their geographical distribution is presented. The occurrence and amplitude of ozone secondary maxima is connected to ozone variability and trend at Uccle and account for a large part of the total ozone and lower stratospheric ozone variability.
The influence of organic compounds on the development of precipitation acidity in maritime clouds
Authors: Alfonso L. , Raga G. B.
Published: April 2010

Abstract. In order to estimate the anthropogenic influence of gas and aerosol emissions from the Petroleum Industry in maritime zones with clouds of small vertical extent, a numerical 1-D Eulerian cloud-chemical model with detailed microphysics (Alfonso and Raga, 2002) is used to simulate the influence of water soluble organic compounds (WSOC) and organic+inorganic gas emissions on cloud development. Following Mircea et al. (2002), we tested the sensitivity of the cloud and precipitation development in the classical inorganic case (CIC) and the inorganic+organic case (IOC) with respect to CCN compositions. The results indicate an increase in the droplet concentration for the IOC, and a delay in the development of precipitation. The pH spectral evolution was studied during both the development and precipitation stages. The influence of the diffusion of formic acid and its generation by oxidation of hydrated formaldehyde in the aqueous phase result in a reduction in the pH of precipitation in the range between 0.05 and 0.15 pH units (from 1 to 3%) for the high ambient SO2 concentration (20 ppb) and between 0.2-0.5 pH units (from 4 to 10%) for the low ambient SO2 concentration (1 ppb) case.
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 218nm at temperatures of 233 and 283K. 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.
Ten-year global distribution of downwelling longwave radiation
Authors: Pavlakis K. G. , Hatzidimitriou D. , Matsoukas C. , Drakakis E. , Hatzianastassiou N. , Vardavas I.
Published: April 2010

Abstract. Downwelling longwave fluxes, DLFs, have been derived for each month over a ten year period (1984-1993), on a global scale with a spatial resolution of 2.5x2.5 degrees and a monthly temporal resolution. The fluxes were computed using a deterministic model for atmospheric radiation transfer, along with satellite and reanalysis data for the key atmospheric input parameters, i.e. cloud properties, and specific humidity and temperature profiles. The cloud climatologies were taken from the latest released and improved International Satellite Climatology Project D2 series. Specific humidity and temperature vertical profiles were taken from three different reanalysis datasets; NCEP/NCAR, GEOS, and ECMWF (acronyms explained in main text). DLFs were computed for each reanalysis dataset, with differences reaching values as high as 30 Wm-2 in specific regions, particularly over high altitude areas and deserts. However, globally, the agreement is good, with the rms of the difference between the DLFs derived from the different reanalysis datasets ranging from 5 to 7 Wm-2. The results are presented as geographical distributions and as time series of hemispheric and global averages. The DLF time series based on the different reanalysis datasets show similar seasonal and inter-annual variations, and similar anomalies related to the 86/87 El Niño and 89/90 La Niña events. The global ten-year average of the DLF was found to be between 342.2 Wm-2 and 344.3 Wm-2, depending on the dataset. We also conducted a detailed sensitivity analysis of the calculated DLFs to the key input data. Plots are given that can be used to obtain a quick assessment of the sensitivity of the DLF to each of the three key climatic quantities, for specific climatic conditions corresponding to different regions of the globe. Our model downwelling fluxes are validated against available data from ground-based stations distributed over the globe, as given by the Baseline Surface Radiation Network. There is a negative bias of the model fluxes when compared against BSRN fluxes, ranging from -7 to -9 Wm-2, mostly caused by low cloud amount differences between the station and satellite measurements, particularly in cold climates. Finally, we compare our model results with those of other deterministic models and general circulation models.
Partially oxidised organic components in urban aerosol using GCXGC-TOF/MS
Authors: Hamilton J. F. , Webb P. J. , Lewis A. C. , Hopkins J. R. , Smith S. , Davy P.
Published: April 2010

Abstract. Partially oxidised organic compounds associated with PM2.5 aerosol collected in London, England, have been analysed using direct thermal desorption coupled to comprehensive gas chromatography-time of flight mass spectrometry (GCXGC-TOF/MS). Over 10000 individual organic components were isolated from around 10µg of aerosol material in a single procedure and with no sample pre-treatment. Chemical functionalities observed using this analytical technique ranged from alkanes to poly-oxygenated species. The chemical band structures commonly used in GCXGC for group type identifications overlap for this sample type, and have required mass spectrometry as an additional level of instrument dimensionality. An investigation of oxygenated volatile organic compounds (o-VOC) contained within urban aerosol has been performed and in a typical sample around 130 o-VOCs were identified based on retention behaviour and spectral match. In excess of 100 other oxygenated species were also observed but lack of mass spectral library or pure components prevents positive identification. Many of the carbonyl species observed could be mechanistically linked to gas phase aromatic hydrocarbon oxidation and there is good agreement in terms of speciation between the urban samples analysed here and those degradation products observed in smog chamber experiments of aromatic oxidation. The presence of partially oxidised species such as linear chain aldehydes and ketones and cyclic products such as furanones suggests that species generated early in the oxidative process may undergo gas to particle partitioning despite their relatively high volatility.
Ozone decomposition kinetics on alumina: effects of ozone partial pressure, relative humidity and repeated oxidation cycles
Authors: Sullivan R. C. , Thornberry T. , Abbatt J. P. D.
Published: April 2010

Abstract. The room temperature kinetics of gas-phase ozone loss via heterogeneous interactions with thin alumina films has been studied in real-time using 254nm absorption spectroscopy to monitor ozone concentrations. The films were prepared from dispersions of fine alumina powder in methanol and their surface areas were determined by an in situ procedure using adsorption of krypton at 77K. The alumina was found to lose reactivity with increasing ozone exposure. However, some of the lost reactivity could be recovered over timescales of days in an environment free of water, ozone and carbon dioxide. From multiple exposures of ozone to the same film, it was found that the number of active sites is large, greater than 1.4x1014 active sites per cm2 of surface area or comparable to the total number of surface sites. The films maintain some reactivity at this point, which is consistent with there being some degree of active site regeneration during the experiment and with ozone loss being catalytic to some degree. The initial uptake coefficients on fresh films were found to be inversely dependent on the ozone concentration, varying from roughly 10-6 for ozone concentrations of 1014 molecules/cm3 to 10-5 at 1013 molecules/cm3. The initial uptake coefficients were not dependent on the relative humidity, up to 75%, within the precision of the experiment. The reaction mechanism is discussed, as well as the implications these results have for assessing the effect of mineral dust on atmospheric oxidant levels.
Longpath DOAS tomography on a motorway exhaust gas plume: numerical studies and application to data from the BAB II campaign
Authors: Laepple T. , Knab V. , Mettendorf K.-U. , Pundt I.
Published: April 2010

Abstract. This paper presents a procedure for performing and optimizing inversions for DOAS tomography and its application to measurement data. DOAS tomography is a new technique to determine 2- and 3-dimensional concentration fields of air pollutants or other trace gases by combining differential optical absorption spectroscopy (DOAS) with tomographic inversion techniques. Due to the limited amount of measured data, the resulting concentration fields are sensitive to the inversion process. Therefore detailed error estimations are needed to determine the quality of the reconstruction. In this paper we compare different row acting methods for the inversion, present a procedure for optimizing the parameters of the reconstruction process and propose a way to estimate the error-fields by numerical studies. The procedure was applied to data from the motorway emission campaign BAB II. Two dimensional NO2 cross sections at right angles to the motorway could be reconstructed qualitatively well at different meteorological situations. Additionally we present error fields for the reconstructions which show the problems and skills of the used measurement setup. Numerical studies on an improved setup for future motorway campaigns show, that DOAS tomography is able to produce high quality concentration maps.
Thermal stability analysis of particles incorporated in cirrus crystals and of non-activated particles in between the cirrus crystals: comparing clean and polluted air masses
Authors: Seifert M. , Ström J. , Krejci R. , Minikin A. , Petzold A. , Gayet J.-F. , Schlager H. , Ziereis H. , Schumann U. , Ovarlez J.
Published: April 2010

Abstract. A thermal volatility technique is used to provide indirect information about the chemical composition of the aerosol involved in cirrus cloud formation. The fraction of particles that disappears after being heated to 125°C is termed volatile and the fraction that disappears between 125 and 250°C is termed semi-volatile. Particles that still remain after being heated to 250°C make up the non-volatile fraction. The thermal composition of residual particles remaining from evaporated cirrus crystals is presented and compared to interstitial aerosol particles (non-activated particles in between the cirrus crystals) for two temperature regimes (cold: T< -38°C, warm: -38≤T< -23°C), based on in-situ observations. The observations were conducted in cirrus clouds in the Southern Hemisphere (SH) and Northern Hemisphere (NH) midlatitudes during the INCA project. In the cold temperature regime, the non-volatile fraction of the residual particles was typically in the range 10 to 30% in the NH and 30 to 40% in the SH. In the warm temperature regime, the non-volatile residual fraction was typically 10 to 30% (NH) and 20 to 40% (SH). At high crystal number densities the non-volatile fraction in both temperature regimes was even higher: in the range of 30 to 40% (NH) and 40 to 50% (SH). The semi-volatile fraction was typically less than 10% in both hemispheres, causing the volatile fraction to essentially be a complement to the non-volatile fraction. In terms of the fractioning into the three types of particles, the SH cold case is clearly different compared to the other three cases (the two warm cases and the cold NH case), which share many features. In the NH data the distribution of different particle types does not seem to be temperature dependent. In all the cases, the non-volatile fraction is enriched in the residual particles compared to the fractions observed for the interstitial particles. This enrichment corresponds to about 15 (NH) and 30 (SH) percent units in the two cold cases and to 15-25 (NH) and 25-35 (SH) percent units in the two warm cases. In the NH cold case, there is a clear relation between the fractions observed in the interstitial particles and what is observed in the residual particles. The observed large fractions of non-volatile particles show that particles forming ice crystals are not entirely made up of water-soluble sulfate particles.
Diurnal and annual variations of meteor rates at the arctic circle
Authors: Singer W. , von Zahn U. , Weiß J.
Published: April 2010

Abstract. Meteors are an important source for (a) the metal atoms of the upper atmosphere metal layers and (b) for condensation nuclei, the existence of which are a prerequisite for the formation of noctilucent cloud particles in the polar mesopause region. For a better understanding of these phenomena, it would be helpful to know accurately the annual and diurnal variations of meteor rates. So far, these rates have been little studied at polar latitudes. Therefore we have used the 33 MHz meteor radar of the ALOMAR observatory at 69° N to measure the meteor rates at this location for two full annual cycles. This site, being within 3° of the Arctic circle, offers in addition an interesting capability: The axis of its antenna field points (almost) towards the North ecliptic pole once each day of the year. In this particular viewing direction, the radar monitors the meteoroid influx from (almost) the entire ecliptic Northern hemisphere. We report on the observed diurnal variations (averaged over one month) of meteor rates and their significant alterations throughout the year. The ratio of maximum over minimum meteor rates throughout one diurnal cycle is in January and February about 5, from April through December 2.3±0.3. If compared with similar measurements at mid-latitudes, our expectation, that the amplitude of the diurnal variation is to decrease towards the North pole, is not really borne out. Observations with the antenna axis pointing towards the North ecliptic pole showed that the rate of deposition of meteoric dust is substantially larger during the Arctic NLC season than the annual mean deposition rate. The daylight meteor showers of the Arietids, Zeta Perseids, and Beta Taurids supposedly contribute considerably to the June maximum of meteor rates. We note, though, that with the radar antenna pointing as described above, all three meteor radiants are close to the local horizon but all three radiants were detected.
Reactive uptake coefficients for heterogeneous reaction of N2O5 with submicron aerosols of NaCl and natural sea salt
Authors: Stewart D. J. , Griffiths P. T. , Cox R. A.
Published: April 2010

Abstract. The kinetics of uptake of gaseous N2O5 on submicron aerosols containing NaCl and natural sea salt have been investigated in a flow reactor as a function of relative humidity (RH) in the range 30-80% at 295±2K and a total pressure of 1bar. The measured uptake coefficients, γ, were larger on the aerosols containing sea salt compared to those of pure NaCl, and in both cases increased with increasing RH. These observations are explained in terms of the variation in the size of the salt droplets, which leads to a limitation in the uptake rate into small particles. After correction for this effect the uptake coefficients are independent of relative humidity, and agree with those measured previously on larger droplets. A value of γ=0.025 is recommended for the reactive uptake coefficient for N2O5 on deliquesced sea salt droplets at 298K and RH>40%.
Evaluation of two ozone air quality modelling systems
Authors: Ortega S. , Soler M. R. , Beneito J. , Pino D.
Published: April 2010

Abstract. The aim of this paper is to compare two different modelling systems and to evaluate their ability to simulate high values of ozone concentration in typical summer episodes which take place in the north of Spain near the metropolitan area of Barcelona. As the focus of the paper is the comparison of the two systems, we do not attempt to improve the agreement by adjusting the emission inventory or model parameters. The first model, or forecasting system, is made up of three modules. The first module is a mesoscale model (MASS). This provides the initial condition for the second module, which is a nonlocal boundary layer model based on the transilient turbulence scheme. The third module is a photochemical box model (OZIPR), which is applied in Eulerian and Lagrangian modes and receives suitable information from the two previous modules. The model forecast is evaluated against ground base stations during summer 2001. The second model is the MM5/UAM-V. This is a grid model designed to predict the hourly three-dimensional ozone concentration fields. The model is applied during an ozone episode that occurred between 21 and 23 June 2001. Our results reflect the good performance of the two modelling systems when they are used in a specific episode.
Divergence of sun-rays by atmospheric refraction at large solar zenith angles
Authors: Uhl R. , Reddmann T.
Published: April 2010

Abstract. For the determination of photolysis rates at large zenith angles it has been demonstrated that refraction by the earth's atmosphere must be taken into account. In fact, due to the modified optical path the optical transmittance is thereby increased in most instances. Here we show that in addition the divergence of sun-rays, which is also caused by refraction but which reduces the direct solar irradiance, should not be neglected. Our calculations are based on a spherically symmetric atmosphere and include extinction by Rayleigh scattering, ozone, and background aerosol. For rays with 10km tangent altitude the divergence yields a reduction of about 10% to 40% at solar zenith angles of 91° to 96°. Moreover, we find that the divergence effect can completely cancel the relative enhancement caused by the increase of transmittance.
Modelling the formation and composition of secondary organic aerosol from α- and β-pinene ozonolysis using MCM v3
Authors: Jenkin M. E.
Published: April 2010

Abstract. The formation and detailed composition of secondary organic aerosol (SOA) from the gas phase ozonolysis of α- and β-pinene has been simulated using the Master Chemical Mechanism version 3 (MCM v3), coupled with a representation of gas-to-aerosol transfer of semivolatile and involatile oxygenated products. A kinetics representation, based on equilibrium absorptive partitioning of ca. 200 semivolatile products, was found to provide an acceptable description of the final mass concentrations observed in a number of reported laboratory and chamber experiments, provided partitioning coefficients were increased by about two orders of magnitude over those defined on the basis of estimated vapour pressures. This adjustment is believed to be due, at least partially, to the effect of condensed phase association reactions of the partitioning products. Even with this adjustment, the simulated initial formation of SOA was delayed relative to that observed, implying the requirement for the formation of species of much lower volatility to initiate SOA formation. The inclusion of a simplified representation of the formation and gas-to-aerosol transfer of involatile dimers of 22 bi- and multifunctional carboxylic acids (in addition to the absorptive partitioning mechanism) allowed a much improved description of SOA formation for a wide range of conditions. The simulated SOA composition recreates certain features of the product distributions observed in a number of experimental studies, but implies an important role for multifunctional products containing hydroperoxy groups (i.e. hydroperoxides). This is particularly the case for experiments in which 2-butanol is used to scavenge OH radicals, because [HO2]/[RO2] ratios are elevated in such systems. The optimized mechanism is used to calculate SOA yields from α- and β-pinene ozonolysis in the presence and absence of OH scavengers, and as a function of temperature.
Optical properties in the UV and visible spectral region of organic acids relevant to tropospheric aerosols
Authors: Lund Myhre C. E. , Nielsen C. J.
Published: April 2010

Abstract. Refractive and absorption indices in the UV and visible region of selected aqueous organic acids relevant to tropospheric aerosols are reported. The acids investigated are the aliphatic dicarboxylic acids oxalic, malonic, tartronic, succinic and glutaric acid. In addition we report data for pyruvic, pinonic, benzoic and phthalic acid. To cover a wide range of conditions we have investigated the aqueous organic acids at different concentrations spanning from highly diluted samples to concentrations close to saturation. The density of the investigated samples is reported and a parameterisation of the absorption and refractive index that allows the calculation of the optical constants of mixed aqueous organic acids at different concentrations is presented. The single scattering albedo is calculated for two size distributions using measured and a synthetic set of optical constants. The results show that tropospheric aerosols consisting of only these organic acids and water have a pure scattering effect.
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-hour 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-hour average 1340ng/m3), formaldehyde (480ng/m3) and acetaldehyde (360ng/m3). Concentrations of monoterpene reaction products nopinone (9ng/m3) and limona ketone (5ng/m3) were low compared to the most abundant low molecular weight carbonyls. Trajectory analysis showed that highest concentrations of carbonyls were measured in the air masses coming from the East and the lowest in the air masses cycled long time over Scandinavia. The total concentration of carbonyl compounds in Hyytiälä in March/April 2003 was much higher than the concentration of aromatic hydrocarbons and monoterpenes in April 2002. Scaling the concentrations against reactivity with the OH-radical showed, that in spite of relatively low ambient concentrations higher molecular weight aldehydes contribute significantly to the total OH-reactive mass of carbonyls. The impact of carbonyl compounds on OH-radical chemistry is important. Contribution of carbonyls as an OH sink is comparable to that of NO2 and higher than monoterpenes and aromatic hydrocarbons. 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 sink reactions 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. Based on the comparisons with urban concentrations the direct anthropogenic emissions are not as important as secondary biogenic and anthropogenic sources or primary biogenic sources in Hyytiälä.
Refinements in the use of equivalent latitude for assimilating sporadic inhomogeneous stratospheric tracer observations, 1: Detecting transport of Pinatubo aerosol across a strong vortex edge
Authors: Good P. , Pyle J.
Published: April 2010

Abstract. The use of PV equivalent latitude for assimilating stratospheric tracer observations is discussed - with particular regard to the errors in the equivalent latitude coordinate, and to the assimilation of sparse data. Some example measurements are assimilated: they sample the stratosphere sporadically and inhomogeneously. The aim was to obtain precise information about the isentropic tracer distribution and evolution as a function of equivalent latitude. Precision is important, if transport across barriers like the vortex edge are to be detected directly. The main challenges addressed are the errors in modelled equivalent latitude, and the non-ideal observational sampling. The methods presented allow first some assessment of equivalent latitude errors and a picture of how good or poor the observational coverage is. This information determines choices in the approach for estimating as precisely as possible the true equivalent latitude distribution of the tracer, in periods of good and poor observational coverage. This is in practice an optimisation process, since better understanding of the equivalent latitude distribution of the tracer feeds back into a clearer picture of the errors in the modelled equivalent latitude coordinate. Error estimates constrain the reliability of using equivalent latitude to make statements like "this observation samples air poleward of the vortex edge" or that of more general model-measurement comparisons. The approach is demonstrated for ground-based lidar soundings of the Mount Pinatubo aerosol cloud, focusing on the 1991-92 arctic vortex edge between 475-520K. Equivalent latitude is estimated at the observation times and locations from Eulerian model tracers initialised with PV and forced by UK Meteorological Office analyses. With the model formulation chosen, it is shown that tracer transport of a few days resulted in an error distribution that was much closer to Gaussian form, although the mean error was not significantly affected. The analysis of the observations revealed a small amount of irreversible transport of aerosol across the vortex edge during late January 1992, coincident with a strongly disturbed vortex.
Implementing growth and sedimentation of NAT particles in a global Eulerian model
Authors: van den Broek M. M. P. , Williams J. E. , Bregman A.
Published: April 2010

Abstract. Here we present a concise and efficient algorithm to mimic the growth and sedimentation of Nitric Acid Trihydate (NAT) particles in the polar vortex in a state-of-the-art 3D chemistry transport model. The particle growth and sedimentation are calculated using the microphysical formulation of Carslaw et al. (2002). Once formed, NAT particles are transported in the model as tracers in the form of size-segregated quantities or size bins. Two different approaches were adopted for this purpose: one assuming a fixed particle number density ("FixedDens") and the other assuming a discrete set of particle diameter values ("FixedRad"). Simulations were performed for three separate 10-day periods during the 1999-2000 Arctic winter and compared to the results of an existing Lagrangian model study, which uses similar microphysics in a computationally more expensive method for the simulation of NAT particle growth. The resulting particle sizes for both our approaches compare favourably at 430K with those obtained from this previous model study, and also in-situ observations related to the size of large NAT particles. The particle growth is faster for "FixedDens" resulting in a difference in (de)nitrification by a factor of ~2 for all three simulation periods. Comparisons were made with a standard equilibrium approach and the differences in the redistribution of HNO3 were found to be substantial. For both approaches the performance of the algorithm is rather insensitive to both the number of size bins and the shape of the size distribution, and show a weak dependence on the prescribed total particle number density during the coldest period. This results in an increase of 7% for the "FixedRad" approach and 17% for the "FixedDens" approach when increasing the total particle number density by a factor of 2.5.
Using GOME NO2 satellite data to examine regional differences in TOMCAT model performance
Authors: Savage N. H. , Law K. S. , Pyle J. A. , Richter A. , Nüß H. , Burrows J. P.
Published: April 2010

Abstract. This paper compares column measurements of NO2 made by the GOME instrument on ERS-2 to model results from the TOMCAT global CTM. The overall correlation between the model and observations is good (0.79 for the whole world, and 0.89 for North America) but the modelled columns are larger than GOME over polluted areas (gradient of 1.4 for North America and 1.9 for Europe). NO2 columns in the region of outflow from North America into the Atlantic are higher in winter in the model compared to the GOME results, whereas the modelled columns are smaller off the coast of Africa where there appear to be biomass burning plumes in the satellite data. Several hypotheses are presented to explain these discrepancies. Weaknesses in the model treatment of vertical mixing and chemistry appear to be the most likely explanations.
Laboratory studies of the homogeneous nucleation of iodine oxides
Authors: Burkholder J. B. , Curtius J. , Ravishankara A. R. , Lovejoy E. R.
Published: April 2010

Abstract. Laboratory experimental results of iodine oxide nucleation are presented. Nucleation was induced following UV photolysis of CF3I or CH2I2 in the presence of excess ozone. Measurements were performed in a 70 L Teflon reactor with new particles detected using an Ultrafine Condensation Particle Counter, UCPC. The experimental results are interpreted using a coupled chemical - aerosol model to derive model parameters assuming single component homogeneous nucleation of OIO. The aerosol model results have been applied in an atmospheric box-model to interpret the possible implications of iodine oxide nucleation in the marine boundary layer. The model calculations demonstrate that IO and OIO concentrations reported in recent field measurements using long path absorption (Allan et al., 2000, 2001) are not sufficient to account for significant aerosol production either in the coastal or open ocean marine boundary layer using the mechanism presented. We demonstrate that inhomogeneous sources of iodine oxides, i.e. "hot" spots with elevated iodine species emissions, could account for the aerosol production bursts observed in the coastal region near Mace Head, Ireland.
A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer
Authors: Toyota K. , Kanaya Y. , Takahashi M. , Akimoto H.
Published: April 2010

Abstract. A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl sulfide, NOx, and O3 in the MBL.
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 was observed on 22-23 February 2001, and found to occur in the stratopause region (~45km). The magnitude of the warming was found to be ~18K 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 data from the 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 the National Centre for Environmental Prediction (NCEP) reanalysis and the European Centre for Medium-Range Weather Forecasts (ECMWF) analysis indicate that a major warming episode took place in the northern polar hemisphere a week before the day of the observation over Gadanki. Eliassen-Palm (E-P) flux calculations from ECMWF analysis show evidence of propagation of planetary-wave activity from high and mid- to low latitudes subsequent 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.
Systematic reduction of complex tropospheric chemical mechanisms, Part II: Lumping using a time-scale based approach
Authors: Whitehouse L. E. , Tomlin A. S. , Pilling M. J.
Published: April 2010

Abstract. This paper presents a formal method of species lumping that can be applied automatically to intermediate compounds within detailed and complex tropospheric chemical reaction schemes. The method is based on grouping species with reference to their chemical lifetimes and reactivity structures. A method for determining the forward and reverse transformations between individual and lumped compounds is developed. Preliminary application to the Leeds Master Chemical Mechanism (MCMv2.0) has led to the removal of 734 species and 1777 reactions from the scheme, with minimal degradation of accuracy across a wide range of test trajectories relevant to polluted tropospheric conditions. The lumped groups are seen to relate to groups of peroxy acyl nitrates, nitrates, carbonates, oxepins, substituted phenols, oxeacids and peracids with similar lifetimes and reaction rates with OH. In combination with other reduction techniques, such as sensitivity analysis and the application of the quasi-steady state approximation (QSSA), a reduced mechanism has been developed that contains 35% of the number of species and 40% of the number of reactions compared to the full mechanism. This has led to a speed up of a factor of 8 in terms of computer calculation time within box model simulations.
Retrieval of nitrogen dioxide stratospheric profiles from ground-based zenith-sky UV-visible observations: validation of the technique through correlative comparisons
Authors: Hendrick F. , Barret B. , Van Roozendael M. , Boesch H. , Butz A. , De Mazière M. , Goutail F. , Hermans C. , Lambert J.-C. , Pfeilsticker K. , Pommereau J.-P.
Published: April 2010

Abstract. A retrieval algorithm based on the Optimal Estimation Method (OEM) has been developed in order to provide vertical distributions of NO2 in the stratosphere from ground-based (GB) zenith-sky UV-visible observations. It has been applied to observational data sets from the NDSC (Network for Detection of Stratospheric Change) stations of Harestua (60° N, 10° E) and Andøya (69° N, 16° E) in Norway. The information content and retrieval errors have been analyzed following a formalism used for characterizing ozone profiles retrieved from solar infrared absorption spectra. In order to validate the technique, the retrieved NO2 vertical profiles and columns have been compared to correlative balloon and satellite observations. Such extensive validation of the profile and column retrievals was not reported in previously published work on the profiling from GB UV-visible measurements. A good agreement - generally better than 25% - has been found with the SAOZ (Système d'Analyse par Observations Zénithales) and DOAS (Differential Optical Absorption Spectroscopy) balloons. A similar agreement has been reached with correlative satellite data from the HALogen Occultation Experiment (HALOE) and Polar Ozone and Aerosol Measurement (POAM) III instruments above 25km of altitude. Below 25km, a systematic underestimation - by up to 40% in some cases - of both HALOE and POAM III profiles by our GB profile retrievals has been observed, pointing out more likely a limitation of both satellite instruments at these altitudes. We have concluded that our study strengthens our confidence in the reliability of the retrieval of vertical distribution information from GB UV-visible observations and offers new perspectives in the use of GB UV-visible network data for validation purposes.
The role of surfactants in Köhler theory reconsidered
Authors: Sorjamaa R. , Svenningsson B. , Raatikainen T. , Henning S. , Bilde M. , 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 the organic compounds that are surface active i.e. tend to concentrate on droplet surface and decrease the surface tension. Gibbsian surface thermodynamics was used to find out how partitioning between droplet surface and the bulk of the droplet affects the surface tension and the surfactant bulk concentration in droplets large enough to act as cloud condensation nuclei. Sodium dodecyl sulfate (SDS) was used together with sodium chloride to investigate the effect of surfactant partitioning on the Raoult effect (solute effect). While accounting for the surface to bulk partitioning is known to lead to lowered bulk surfactant concentration and thereby to increased surface tension compared to a case in which the partitioning is neglected, the present results show that the partitioning also alters the Raoult effect, and that the change is large enough to further increase the critical supersaturation and hence decrease cloud 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 solutions were studied in order to study the partitioning with compounds found in the atmosphere and to find out the combined effects of dissolution and partitioning behavior. The results show that the partitioning consideration presented in this paper alters the shape of the Köhler curve when compared to calculations in which the partitioning is neglected either completely or in the Raoult effect. In addition, critical supersaturation was measured for SDS particles with dry radii of 25-60nm using a static parallel plate Cloud Condensation Nucleus Counter. The experimentally determined critical supersaturations agree very well with theoretical calculations taking the surface to bulk partitioning fully into account and are much higher than those calculated neglecting the partitioning.
Ground-based water vapour soundings by microwave radiometry and Raman lidar on Jungfraujoch (Swiss Alps)
Authors: Gerber D. , Balin I. , Feist D. G. , Kämpfer N. , Simeonov V. , Calpini B. , van den Bergh H.
Published: April 2010

Abstract. Water vapour has been measured from the International Scientific Station Jungfraujoch (ISSJ, 47° N, 7° E, 3580m above sea level) during the winters of 1999/2000 and 2000/2001 by microwave radiometry and Raman lidar. The abundance of atmospheric water vapour between the planetary boundary layer and the upper stratosphere varies over more than three orders of magnitude. The currently used measurement techniques are only suited to determine the abundance of water vapour in different atmospheric regimes. None can resolve the vertical distribution profile from ground level to the top of the stratosphere by itself. We present such a water vapour profile where simultaneous measurements from a Raman lidar and a microwave radiometer were combined to cover both the troposphere and the stratosphere, respectively. We also present a study of the stratospheric and tropospheric water vapour variability for the two consecutive winters.
Actinic flux and O1D photolysis frequencies retrieved from spectral measurements of irradiance at Thessaloniki, Greece
Authors: Kazadzis S. , Topaloglou C. , Bais A. F. , Blumthaler M. , Balis D. , Kazantzidis A. , Schallhart B.
Published: April 2010

Abstract. The results of two methods retrieving actinic flux and ozone photolysis frequencies (JO1D), from measurements of irradiance with a Brewer MKIII spectroradiometer are investigated in this paper. The first method uses actinic flux retrieved from irradiance measurements by the use of known formulas while the second is an empirical method converting irradiance to JO1D through polynomials extracted from a study of synchronous actinic flux and irradiance measurements. When examining the actinic fluxes derived from the first method to those measured by an actinic flux spectrometer data agree within ±10% for solar zenith angles lower than 75° for the UV-B and the UV-A wavelength band. Also, the actinic to global irradiance ratio derived, deviates within ±6% for solar zenith angles lower than 70° compared with cloudless sky calculations of the TUV model. For both cases the deviations are in the order of the magnitude of the measurement or model uncertainties. Values of JO1D calculated by the second method show a mean ratio of 0.99±0.10 (1σ) and 0.98±0.06 for all data and for cloudless skies respectively when compared with values of JO1D derived by a Bentham actinic flux spectroradiometer. Finally, the agreement of the two methods is within ±5% comparing two years' data of JO1D retrieved from irradiance measurements at Thessaloniki, Greece. The use of such methods on extensive data sets of global irradiance can provide JO1D values with acceptable uncertainty, a parameter of particular importance for chemical process studies.
Past and future simulations of NO2 from a coupled chemistry-climate model in comparison with observations
Authors: Struthers H. , Kreher K. , Austin J. , Schofield R. , Bodeker G. , Johnston P. , Shiona H. , Thomas A.
Published: April 2010

Abstract. Trends in derived from a 45 year integration of a chemistry-climate model (CCM) run have been compared with ground-based measurements at Lauder (45° S) and Arrival Heights (78° S). Observed trends in at both sites exceed the modelled trends in N2O, the primary source gas for stratospheric NO2. This suggests that the processes driving the trend are not solely dictated by changes in but are coupled to global atmospheric change, either chemically or dynamically or both. If CCMs are to accurately estimate future changes in ozone, it is important that they comprehensively include all processes affecting NOx (NO+NO2) because NOx concentrations are an important factor affecting ozone concentrations. Comparison of measured and modelled NO2 trends is a sensitive test of the degree to which these processes are incorporated in the CCM used here. At Lauder the 1980-2000 CCM NO2 trends (4.2% per decade at sunrise, 3.8% per decade at sunset) are lower than the observed trends (6.5% per decade at sunrise, 6.0% per decade at sunset) but not significantly different at the 2σ level. Large variability in both the model and measurement data from Arrival Heights makes trend analysis of the data difficult. CCM predictions (2001-2019) of NO2 at Lauder and Arrival Heights show significant reductions in the rate of increase of NO2 compared with the previous 20 years (1980-2000). The model results indicate that the partitioning of oxides of nitrogen changes with time and is influenced by both chemical forcing and circulation changes.
On the role of hydroxyl radicals in the self-cleansing capacity of the troposphere
Authors: Lelieveld J. , Dentener F. J. , Peters W. , Krol M. C.
Published: April 2010

Abstract. Thousands of megatons 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. Global models and observations of trace gas distributions from global networks have been used to study geographical and temporal changes in tropospheric OH. Here we present a synopsis of recent studies, indicating that global mean OH has changed remarkably little in the past century, even though regional changes have probably been substantial. Globally, depletion of OH by reactive carbon gases has been compensated by increased OH formation by nitrogen oxides, an act of "inadvertent geo-engineering". However, OH analyses for the past 1-2 decades, partly based on methyl chloroform measurements, are inconclusive. Some work, assuming that methyl chloroform emissions have largely ceased, suggests a very strong downward global OH trend in the 1990s, inconsistent with modelling studies. The discrepancy could be much reduced by assuming continued small emissions of methyl chloroform. We recommend the continuation of high precision monitoring of this compound and improved analyses based on detailed meteorological-chemical models.
Impact of reactive bromine chemistry in the troposphere
Authors: von Glasow R. , von Kuhlmann R. , Lawrence M. G. , Platt U. , Crutzen P. J.
Published: April 2010

Abstract. Recently several field campaigns and satellite observations have found strong indications for the presence of bromine oxide (BrO) in the free troposphere. Using a global atmospheric chemistry transport model we show that BrO mixing ratios of a few tenths to 2 pmol mol-1 lead to a reduction in the zonal mean O3 mixing ratio of up to 18% in widespread areas and regionally up to 40% compared to a model run without bromine chemistry. A lower limit approach for the marine boundary layer, that does not explicitly include the release of halogens from sea salt aerosol, shows that for dimethyl sulfide (DMS) the effect is even larger, with up to 60% reduction of its tropospheric column. This is accompanied by dramatic changes in DMS oxidation pathways, reducing its cooling effect on climate. In addition there are changes in the HO2:OH ratio that also affect NOx and PAN. These results imply that potentially significant strong sinks for O3 and DMS have so far been ignored in many studies of the chemistry of the troposphere.