bluuebunny/crossref_metadata_2025 huggingface dataset:
Microscopic characterization of carbonaceous aerosol particle aging in the outflow from Mexico City
Authors: Moffet R. C. , Henn T. R. , Tivanski A. V. , Hopkins R. J. , Desyaterik Y. , Kilcoyne A. L. D. , Tyliszczak T. , Fast J. , Barnard J. , Shutthanandan V. , Cliff S. S. , Perry K. D. , Laskin A. , Gilles M. K.
Published: April 2010

Abstract. This study was part of the Megacities Initiative: Local and Global Research Observations (MILAGRO) field campaign conducted in Mexico City metropolitan area during spring 2006. The physical and chemical transformations of particles aged in the outflow from Mexico City were investigated for the transport event of 22 March 2006. A detailed chemical analysis of individual particles was performed using a combination of complementary microscopy and micro-spectroscopy techniques. The applied techniques included scanning transmission X-ray microscopy (STXM) coupled with near edge X-ray absorption fine structure spectroscopy (NEXAFS) and computer controlled scanning electron microscopy with an energy dispersive X-ray analyzer (CCSEM/EDX). As the aerosol plume evolves from the city center, the organic mass per particle increases and the fraction of carbon-carbon double bonds (associated with elemental carbon) decreases. Organic functional groups enhanced with particle age include: carboxylic acids, alkyl groups, and oxygen bonded alkyl groups. At the city center (T0) the most prevalent aerosol type contained inorganic species (composed of sulfur, nitrogen, oxygen, and potassium) coated with organic material. At the T1 and T2 sites, located northeast of T0 (~29 km and ~65 km, respectively), the fraction of homogenously mixed organic particles increased in both size and number. These observations illustrate the evolution of the physical mixing state and organic bonding in individual particles in a photochemically active environment.
Application of the variability-size relationship to atmospheric aerosol studies: estimating aerosol lifetimes and ages
Authors: Williams J. , de Reus M. , Krejci R. , Fischer H. , Ström J.
Published: April 2010

Abstract. Aerosol variability is examined as function of particle size for data collected over the Northern Indian Ocean in February 1999 as part of the INDOEX experiment. It was found that for particles believed to be of terrestrial or oceanic origin, the variability correlated with the average number concentration. For particles that are thought to be formed and grow in the atmosphere through coagulation and condensation an anticorrelation was observed, the minimum in variability coinciding with the maximum in the number concentration. Three altitude ranges were examined (0--1, 4--8 and 8--13 km) and the minimum in variability was found to occur at lower particle sizes in the free troposphere (0.065 mm) than in the boundary layer (0.165 mm). The observed variability has been compared to that generated by a numerical model in order to determine the relative importance of the physical processes. Modelled variability of 0.02 mm particles caused by nucleation was not observed in the measurements. A previously derived empirical relationship for aerosol residence time was compared with the measured variability as a function of bin size. The aerosol variability / residence time relationship was characterised by a coefficient (b) at all altitudes and for both correlating and anticorrelating regimes. By combining the derived coefficient with the model predicted lifetime for 0.020 mm particles we estimated residence times and ages as a function of particle size and altitude. General agreement was found with previous estimates of aerosol residence time. In the upper atmosphere aerosols of 0.065 mm in size have residence times of approximately 1 month and can be transported on a hemispheric scale. The same size aerosol has a lifetime one order of magnitude less in the boundary layer and therefore will not be transported far from the source regions.
Properties of subvisible cirrus clouds formed by homogeneous freezing
Authors: Kärcher B.
Published: April 2010

Abstract. Number concentrations and mean sizes of ice crystals and derived microphysical and optical properties of subvisible cirrus clouds (SVCs) formed by homogeneous freezing of supercooled aerosols are investigated as a function of temperature and updraft speed of adiabatically ascending air parcels. The properties of such clouds are insensitive to variations of the aerosol number and size distribution. Based on criteria constraining the optical extinction, sedimentation time, and existence time of SVCs, longer-lived (>10min) clouds, capable of exerting a measurable radiative or chemical impact, are generated within a narrow range of updraft speeds below 1-2cm s-1 at temperatures below about 215K, with concentrations of ice crystals not exceeding 0.1cm-3. The clouds do not reach an equilibrium state because the ice crystals sediment out of the formation layer typically before the supersaturation is removed. Two important conclusions emerge from this work. First, the above characteristics of SVCs may provide an explanation for why SVCs are more common in the cold tropical than in the warmer midlatitude tropopause region. Second, it seems likely that a limited number (<0.1cm-3) of effective heterogeneous freezing nuclei that nucleate ice below the homogeneous freezing threshold can control the formation and properties of SVCs, although homogeneous freezing nuclei are far more abundant.
The flux of carbonyl sulfide and carbon disulfide between the atmosphere and a spruce forest
Authors: Xu X. , Bingemer H. G. , Schmidt U.
Published: April 2010

Abstract. Turbulent fluxes of carbonyl sulfide (COS) and carbon disulfide (CS2) were measured over a spruce forest in Central Germany using the relaxed eddy accumulation (REA) technique. A REA sampler was developed and validated using simultaneous measurements of CO2 fluxes by REA and by eddy correlation. REA measurements were conducted during six campaigns covering spring, summer, and fall between 1997 and 1999. Both uptake and emission of COS and CS2 by the forest were observed, with deposition occurring mainly during the sunlit period and emission mainly during the dark period. On the average, however, the forest acts as a sink for both gases. The average fluxes for COS and CS2 are  -93 ± 11.7 pmol m-2 s-1 and  -18 ± 7.6 pmol m-2 s-1, respectively. The fluxes of both gases appear to be correlated to photosynthetically active radiation and to the CO2 and H2O fluxes, supporting the idea that the air-vegetation exchange of both gases is controlled by stomata. An uptake ratio COS/CO2 of 10 ± 1.7 pmol μmol-1 has been derived from the regression line for the correlation between the COS and CO2 fluxes. This uptake ratio, if representative for the global terrestrial net primary production, would correspond to a sink of 2.3 ± 0.5 Tg COS yr-1.
The adsorption of nitrogen oxides on crystalline ice
Authors: Bartels T. , Eichler B. , Zimmermann P. , Gäggeler H. W. , Ammann M.
Published: April 2010

Abstract. The partitioning of nitrogen oxides between ice and air is of importance to the ozone budget in the upper troposphere. In the present study, adsorption of nitrogen oxides on ice was investigated at atmospheric pressure using a chromatographic technique with radioactively labelled nitrogen oxides at low concentrations. The measured retentions solely depended on molecular adsorption and were not influenced by dimerisation, formation of encapsulated hydrates on the ice surface, dissociation of the acids, nor by migration into a quasi-liquid layer or grain boundaries. Based on the chromatographic retention and the model of thermo-chromatography, the standard adsorption enthalpy of -20 kJ mol-1 for NO, -22kJ mol-1 for NO2, -30kJ mol-1 for peroxyacetyl nitrate, -32kJ mol-1 for HON} and -44 kJ mol-1 for HNO3 was calculated. To perform those calculations within the model of thermo-chromatography, the standard adsorption entropy was calculated based on statistical thermodynamics. In this work, two different choices of standard states were applied, and consequently different values of the standard adsorption entropy, of either between -39 kJ mol-1 and -45kJ mol-1, or -164 kJ mol-1 and -169 kJ mol-1 for each nitrogen oxide were derived. The standard adsorption enthalpy was identical for both standard adsorption entropies and thus shown to be independent of the choice of standard state. A brief outlook on environmental implications of our findings indicates that adsorption on ice might be an important removal process of HNO3. In addition, it might be of some importance for HONO and peroxyacetyl nitrate and irrelevant for NO and NO2.
Uptake of HNO3 to deliquescent sea-salt particles: a study using the short-lived radioactive isotope tracer 13N
Authors: Guimbaud C. , Arens F. , Gutzwiller L. , Gäggeler H. W. , Ammann M.
Published: April 2010

Abstract. The uptake of HNO3 to deliquescent airborne sea-salt particles (RH = 55%, P = 760 torr, T = 300 K) at concentrations from 2 to 575 ppbv is measured in an aerosol flow tube using 13N as a tracer. Small particles ( 70 nm diameter) are used in order to minimize the effect of diffusion in the gas phase on the mass transfer. Below 100 ppbv, an uptake coefficient (gupt) of 0.50 ± 0.20 is derived. At higher concentrations, the uptake coefficient decreases along with the consumption of aerosol chloride. Data interpretation is further supported by using the North American Aerosol Inorganics Model (AIM), which predicts the aqueous phase activities of ions and the gas-phase partial pressures of H2O, HNO3, and HCl at equilibrium for the NaCl/HNO3/H2O system. These simulations show that the low concentration data are obtained far from equilibrium, which implies that the uptake coefficient derived is equal to the mass accommodation coefficient under these conditions. The observed uptake coefficient can serve as input to modeling studies of atmospheric sea-salt aerosol chemistry. The main sea-salt aerosol burden in the marine atmosphere is represented by coarse mode particles (> 1 µm diameter). This implies that diffusion in the gas-phase is the limiting step to HNO3 uptake until the sea-salt has been completely processed.
Global ozone forecasting based on ERS-2 GOME observations
Authors: Eskes H. J. , van Velthoven P. F. J. , Kelder H. M.
Published: April 2010

Abstract. The availability of near-real time ozone observations from satellite instruments has recently initiated the development of ozone data assimilation systems. In this paper we present the results of an ozone assimilation and forecasting system, in use since Autumn 2000. The forecasts are produced by an ozone transport and chemistry model, driven by the operational medium range forecasts of ECMWF. The forecasts are initialised with realistic ozone distributions, obtained by the assimilation of near-real time total column observations of the GOME spectrometer on ERS-2. The forecast error diagnostics demonstrate that the system produces meaningful total ozone forecasts for up to 6 days in the extratropics. In the tropics meaningful forecasts of the small anomalies are restricted to shorter periods of about two days with the present model setup. It is demonstrated that important events, such as the breakup of the South Pole ozone hole and mini-hole events above Europe can be successfully predicted 4--5 days in advance.
Redistribution of trace gases by convective clouds - mixed-phase processes
Authors: Yin Y. , Carslaw K. S. , Parker D. J.
Published: April 2010

Abstract. The efficiency of gas transport to the free and upper troposphere in convective clouds is investigated in an axisymmetric dynamic cloud model with detailed microphysics. In particular, we examine the sensitivity of gas transport to the treatment of gas uptake by different ice hydrometeors. Two parameters are used to describe this uptake. The gas retention coefficient defines the fraction of dissolved gas that is retained in an ice particle upon freezing, which includes also the riming process. We also define a gas burial efficiency defining the amount of gas entrapped in ice crystals growing by vapour diffusion. Model calculations are performed for continental and maritime clouds using a complete range of gas solubilities, retention coefficients and burial efficiencies. The results show that the magnitude of the gas retention coefficient is much more important for gas transport in maritime clouds than in continental clouds. The cause of this difference lies in the different microphysical processes dominating the formation and evolution of hydrometeors in the two cloud types. For highly soluble gases, the amount of gas transported to the free troposphere in maritime clouds falls approximately linearly by a factor of 12 as the retention coefficient is varied between 0 and 1. Gas transport is relatively insensitive to the magnitude of the gas burial efficiency. However, the burial efficiency strongly controls the concentration of trace gases inside anvil ice crystals, which subsequently form cirrus clouds.
Three years of routine Raman lidar measurements of tropospheric aerosols: Backscattering, extinction, and residual layer height
Authors: Schneider J. , Eixmann R.
Published: April 2010

Abstract. We have performed a three-year series of routine lidar measurements at preselected times. The measurements were performed between 1 December 1997, and 30 November 2000, at Kühlungsborn, Germany (54°07' N, 11°46' E). Using a Rayleigh/Mie/Raman lidar system, we measured the aerosol backscatter coefficients at three wavelengths and the extinction coefficient at one wavelength. The present data analysis focuses on after-sunset Raman measurements obtained on cloud-free days. Aerosol backscatter profiles are available for altitudes above 100 m, while the majority of the extinction measurements has been restricted to heights above the residual layer. The residual layer shows an annual cycle with its maximum height in summer (2000 m) and minimum height in winter (850 m). The backscatter coefficients in the residual layer were found to be about 10 times higher than above. The mean aerosol optical depth above the residual layer and below 5 km is 0.3(±1.0) x10-2 in summer, and 1.5(±1.0) x10-2 in winter, which almost is negligible compared to values measured in during daytime in the planetary boundary layer. A cluster analysis of the backward trajectories yielded two major directions of air mass origin above the residual layer and 4 major directions inside. A marked difference between the aerosol properties dependent on the air mass origin could be found for air masses originating from the west and travelling at high wind speeds. Comparing the measured spectral dependence of the backscatter coefficients with data from the Global Aerosol Data Set, we found a general agreement, but only a few conclusions with respect to the aerosol type could be drawn due to the high variability of the measured backscatter coefficients.
Comparing forward and inverse models to estimate the seasonal variation of hemisphere-integrated fluxes of carbonyl sulfide
Authors: Kettle A. J. , Kuhn U. , von Hobe M. , Kesselmeier J. , Liss P. S. , Andreae M. O.
Published: April 2010

Abstract. A simple inverse model is proposed to deduce hemisphere-integrated COS flux based on published time series of total column COS. The global atmosphere is divided into two boxes representing the Northern and Southern Hemispheres, and the total column COS data from several stations are used to calculate hemispheric COS loadings. The integrated flux within each hemisphere is calculated as a linear combination of a steady-state solution and time-varying perturbation. The nature of the time-varying perturbation is deduced using two different approaches: an analytic solution based on a cosine function that was fitted to the original total column COS measurement time series and a Simplex optimization with no underlying assumption about the functional form of the total column time series. The results suggest that there is a steady-state COS flux from the Northern to the Southern Hemisphere. There is a seasonal variation superimposed on this flux that in the Southern Hemisphere has a maximum rate of COS input into the atmosphere around January and a maximum rate of COS removal from the atmosphere around August--September. In the Northern Hemisphere, the maximum rate of COS input into the atmosphere is around May--June, and the maximum rate of COS removal is either August or January, depending on which station in the Northern Hemisphere is considered. The results of the inverse model are compared with the outcome of a forward approach on the temporal and spatial variation of the dominant global sources and sinks published earlier. In general, the deduced hemisphere-integrated flux estimates showed good agreement with the database estimates, though it remains uncertain whether COS removal from the atmosphere in the Northern Hemisphere is dominated by plant and soil uptake in the boreal summer or by oceanic uptake in boreal winter.
Uptake and reaction of HOBr on frozen and dry NaCl/NaBr surfaces between 253 and 233 K
Authors: Adams J. W. , Holmes N. S. , Crowley J. N.
Published: April 2010

Abstract. The uptake and reaction of HOBr with frozen salt surfaces of variable NaCl / NaBr composition and temperature were investigated with a coated wall flow tube reactor coupled to a mass spectrometer for gas-phase analysis. HOBr is efficiently taken up onto the frozen surfaces at temperatures between 253 and 233 K where it reacts to form the di-halogens BrCl and Br2, which are subsequently released into the gas-phase. The uptake coefficient for HOBr reacting with a frozen, mixed salt surface of similar composition to sea-spray was  10-2. The relative concentration of BrCl and Br2 released to the gas-phase was found to be strongly dependent on the ratio of Cl- to Br - in the solution prior to freezing / drying. For a mixed salt surface of similar composition to sea-spray the major product at low conversion of surface reactants (i.e. Br - and Cl-) was Br2. Variation of the pH of the NaCl / NaBr solution used to prepare the frozen surfaces was found to have no significant influence on the results. The observations are explained in terms of initial formation of BrCl in a surface reaction of HOBr with Cl-, and conversion of BrCl to Br2 via reaction of surface Br -. Experiments on the uptake and reaction of BrCl with frozen NaCl / NaBr solutions served to confirm this hypothesis. The kinetics and products of the interactions of BrCl, Br2 and Cl2 with frozen salt surfaces were also investigated, and lower limits to the uptake coefficients of > 0.034, >0.025 and >0.028 respectively, were obtained. The uptake and reaction of HOBr on dry salt surfaces was also investigated and the results closely resemble those obtained for frozen surfaces. During the course of this study the gas diffusion coefficients of HOBr in He and H2O were also measured as (273 ± 1) Torr cm2 s-1 and (51 ± 1) Torr cm2 s-1, respectively, at 255 K. The implications of these results for modelling the chemistry of the Arctic boundary layer in springtime are discussed.
Reply to: "Tropical cirrus and water vapor: an effective Earth infrared iris feedback?"
Authors: Chou M.-D. , Lindzen R. S. , Hou A. Y.
Published: April 2010

Abstract. In assessing the iris effect suggested by Lindzen et al. (2001), Fu et al. (2002) found that the response of high-level clouds to the sea surface temperature had an effect of reducing the climate sensitivity to external radiative forcing, but the effect was not as strong as LCH found. The approach of FBH to specifying longwave emission and cloud albedos appears to be inappropriate, and the derived cloud optical properties may not have real physical meaning. The cloud albedo calculated by FBH is too large for cirrus clouds and too small for boundary layer clouds, which underestimates the iris effect.
Uncertainties and assessments of chemistry-climate models of the stratosphere
Authors: Austin J. , Shindell D. , Beagley S. R. , Brühl C. , Dameris M. , Manzini E. , Nagashima T. , Newman P. , Pawson S. , Pitari G. , Rozanov E. , Schnadt C. , Shepherd T. G.
Published: April 2010

Abstract. In recent years a number of chemistry-climate models have been developed with an emphasis on the stratosphere. Such models cover a wide range of time scales of integration and vary considerably in complexity. The results of specific diagnostics are here analysed to examine the differences amongst individual models and observations, to assess the consistency of model predictions, with a particular focus on polar ozone. For example, many models indicate a significant cold bias in high latitudes, the "cold pole problem", particularly in the southern hemisphere during winter and spring. This is related to wave propagation from the troposphere which can be improved by improving model horizontal resolution and with the use of non-orographic gravity wave drag. As a result of the widely differing modelled polar temperatures, different amounts of polar stratospheric clouds are simulated which in turn result in varying ozone values in the models. The results are also compared to determine the possible future behaviour of ozone, with an emphasis on the polar regions and mid-latitudes. All models predict eventual ozone recovery, but give a range of results concerning its timing and extent. Differences in the simulation of gravity waves and planetary waves as well as model resolution are likely major sources of uncertainty for this issue. In the Antarctic, the ozone hole has probably reached almost its deepest although the vertical and horizontal extent of depletion may increase slightly further over the next few years. According to the model results, Antarctic ozone recovery could begin any year within the range 2001 to 2008. The limited number of models which have been integrated sufficiently far indicate that full recovery of ozone to 1980 levels may not occur in the Antarctic until about the year 2050. For the Arctic, most models indicate that small ozone losses may continue for a few more years and that recovery could begin any year within the range 2004 to 2019. The start of ozone recovery in the Arctic is therefore expected to appear later than in the Antarctic. Further, interannual variability will tend to mask the signal for longer than in the Antarctic, delaying still further the date at which ozone recovery may be said to have started. Because of this inherent variability of the system, the decadal evolution of Arctic ozone will not necessarily be a direct response to external forcing.
Climatologies of subtropical mixing derived from 3D models
Authors: Eyring V. , Dameris M. , Grewe V. , Langbein I. , Kouker W.
Published: April 2010

Abstract. Fingerlike structures reaching from lower into extra-tropical latitudes significantly contribute to the tropical-extratropical exchange of air masses. This is also an exchange of upper tropospheric and stratospheric air. Those so called streamers can, on a horizontal plane, be detected in N2O or O3 since they are characterised by high N2O or low O3 values compared to undisturbed mid-latitude values. A climatology of streamer events has been established, employing the chemical-transport model KASIMA, which is driven by ECMWF re-analyses (ERA) and operational analyses. For the first time, the seasonal and geographical distribution of streamer frequencies has been determined on the basis of 9 years of meteorological analyses. For the current investigation, a meridional gradient criterion has been newly formulated and applied to the N2O distributions calculated with KASIMA. A climatology has been derived by counting all streamer events between 21 and 25 km for the years 1990 to 1998. The results have been compared with a streamer climatology which has been established in the same way employing data of a multi-year simulation with the coupled chemistry-climate model ECHAM4.L39(DLR)/CHEM (E39/C). Both climatologies are qualitatively in agreement, in particular in the northern hemisphere, where much higher streamer frequencies are found in winter than in summer. In the southern hemisphere, the KASIMA analyses indicate strongest streamer activity in September. E39/C streamer frequencies clearly displays an offset from June to October, pointing to model deficiencies with respect to tropospheric dynamics. KASIMA and E39/C results agree well from November to May. Some of the findings give strong indications that the streamer events found in the altitude region between 21 and 25 km are mainly forced from the troposphere and are not directly related to the dynamics of the stratosphere, in particular not to the dynamics of the polar vortex. Sensitivity simulations with E39/C, which represent recent and possible future atmospheric conditions, have been employed to answer the question how climate change would alter streamer frequencies. This shows that the seasonal cycle does not change but that significant changes occur in months of minimum and maximum streamer frequencies. This could have an impact on the mid-latitude distribution of chemical tracers and compounds.
Laboratory study on heterogeneous decomposition of methyl chloroform on various standard aluminosilica clay minerals as a potential tropospheric sink
Authors: Kutsuna S. , Chen L. , Ohno K. , Negishi N. , Takeuchi K. , Ibusuki T. , Tokuhashi K. , Sekiya A.
Published: April 2010

Abstract. Methyl chloroform (1,1,1-trichloroethane, CH3CCl3) was found to decompose heterogeneously on seven types of standard clay minerals (23 materials) in dry air at 313 K in the laboratory. All reactions proceeded through the elimination of HCl; CH3CCl3 was converted quantitatively to CH2=CCl2. The activities of the clay minerals were compared via their pseudo-first-order reaction rate constants (k1). A positive correlation was observed between the k1 value and the specific surface area (S) of clay minerals, where the S value was determined by means of the general Brunauer-Emmett-Teller (BET) equation. The k1 value was anti-correlated with the value of n, which was a parameter of the general BET equation and related to the average pore size of the clay minerals, and correlated with the water content that can be removed easily from the clay minerals. The reaction required no special pretreatment of clay minerals, such as heating at high temperatures; hence, the reaction can be expected to occur in the environment. Photoillumination by wavelengths present in the troposphere did not accelerate the decomposition of CH3CCl3, but it induced heterogeneous photodecomposition of CH2=CCl2. The temperature dependence of k1, the adsorption equilibrium coefficient of CH3CCl3 and CH2=CCl2, and the surface reaction rate constant of CH3CCl3 were determined for an illite sample. The k1 value increased with increasing temperature. The amount of CH3CCl3 adsorbed on the illite during the reaction was proportional to the partial pressure of CH3CCl3. The reaction was sensitive to relative humidity and the k1 value decreased with increasing relative humidity. However, the reaction was found to proceed at a relative humidity of 22% at 313 K, although the k1 value was about one-twentieth of the value in non-humidified air. The conditions required for the reaction may be present in major desert regions of the world. A simple estimation indicates that the possible heterogeneous decomposition of CH3CCl3 on the ground surface in arid regions is worth taking into consideration when inferring the tropospheric lifetime of CH3CCl3 and global OH concentration from the global budget concentration of CH3CCl3.
Ultrathin Tropical Tropopause Clouds (UTTCs): I. Cloud morphology and occurrence
Authors: Peter Th. , Luo B. P. , Wirth M. , Kiemle C. , Flentje H. , Yushkov V. A. , Khattatov V. , Rudakov V. , Thomas A. , Borrmann S. , Toci G. , Mazzinghi P. , Beuermann J. , Schiller C. , Cairo F. , Di Donfrancesco G. , Adriani A. , Volk C. M. , Strom J. , Noone K. , Mitev V. , MacKenzie R. A. , Carslaw K. S. , Trautmann T. , Santacesaria V. , Stefanutti L.
Published: April 2010

Abstract. Subvisible cirrus clouds (SVCs) may contribute to dehydration close to the tropical tropopause. The higher and colder SVCs and the larger their ice crystals, the more likely they represent the last efficient point of contact of the gas phase with the ice phase and, hence, the last dehydrating step, before the air enters the stratosphere. The first simultaneous in situ and remote sensing measurements of SVCs were taken during the APE-THESEO campaign in the western Indian ocean in February/March 1999. The observed clouds, termed Ultrathin Tropical Tropopause Clouds (UTTCs), belong to the geometrically and optically thinnest large-scale clouds in the Earth's atmosphere. Individual UTTCs may exist for many hours as an only 200--300 m thick cloud layer just a few hundred meters below the tropical cold point tropopause, covering up to 105 km2. With temperatures as low as 181 K these clouds are prime representatives for defining the water mixing ratio of air entering the lower stratosphere.
First observations of noctilucent clouds by lidar at Svalbard, 78°N
Authors: Höffner J. , Fricke-Begemann C. , Lübken F.-J.
Published: April 2010

Abstract. In summer 2001 a potassium lidar was installed near Longyearbyen (78° N) on the north polar island of Spitsbergen which is part of the archipelago Svalbard. At the same place a series of meteorological rockets ("falling spheres", FS) were launched which gave temperatures from the lower thermosphere to the stratosphere. The potassium lidar is capable of detecting noctilucent clouds (NLCs) and of measuring temperatures in the lower thermosphere, both under daylight conditions. In this paper we give an overview on the NLC measurements (the first at this latitude) and compare the results with temperatures from meteorological rockets which have been published recently (Lübken and Mülleman, 2003) NLCs were observed from 12 June (the first day of operation) until 12 August when a period of bad weather started. When the lidar was switched on again on 26 August, no NLC was observed. The mean occurrence frequency in the period 12 June -- 12 August ("lidar NLC period") is 77%. The mean of all individual NLC peak altitudes is 83.6 km (variability: 1.1 km). The mean peak NLC altitude does not show a significant variation with season. The average top and bottom altitude of the NLC layer is 85.1 and 82.5 km, respectively, with a variability of ~1.2 km. The mean of the maximum volume backscatter coefficient bmax at our wavelength of 770 nm is 3.9 x 10-10/m/sr with a large variability of ±3.8 x 10-10/m/sr. Comparison of NLC characteristics with measurements at ALOMAR (69° N) shows that the peak altitude and the maximum volume backscatter coefficient are similar at both locations but NLCs occur more frequently at higher latitudes. Simultaneous temperature and NLC measurements are available for 3 flights and show that the NLC layer occurs in the lower part of the height range with super-saturation. The NLC peak occurs over a large range of degree of saturation (S) whereas most models predict the peak at S = 1. This demonstrates that steady-state considerations may not be applicable when relating individual NLC properties to background conditions. On the other hand, the mean variation of the NLC appearance with height and season is in agreement with the climatological variation of super-saturation derived from the FS temperature measurements.
The role of volatile organic compounds in the polluted urban atmosphere of Bristol, England
Authors: Rivett A. C. , Martin D. , Gray D. J. , Price C. S. , Nickless G. , Simmonds P. G. , O’Doherty S. J. , Greally B. R. , Knights A. , Shallcross D. E.
Published: April 2010

Abstract. The results of a field campaign carried out from early spring through to the late summer of 2000, in Bristol, England, are presented. Continuous measurements of over 40 hydrocarbons have been made at an urban background site, located at Bristol University, for approximately nine months using a Gas Chromatography - Flame Ionisation Detection (GC-FID) system and for a selection of halocarbons for approximately one month using a Gas Chromatography - Electron Capture Detection (GC-ECD) system. In this paper we present the time-series of the nine halocarbons and selected hydrocarbons. Daytime and night-time hydroxyl radical concentrations have been estimated based on the diurnal variations of a selection of the measured hydrocarbons. The average summer daytime concentration of OH was found to be 2.5x106 molecules cm-3 and the night-time concentration to be in the range 104 to 105 molecules cm-3. In addition, the role played by certain VOCs in the formation of ozone is assessed using the POCP (Photochemical Ozone Creation Potential) concept.
Atmospheric impact of the 1783–1784 Laki Eruption: Part II Climatic effect of sulphate aerosol
Authors: Highwood E.-J. , Stevenson D. S.
Published: April 2010

Abstract. The long 1783-1784 eruption of Laki in southern Iceland, was one of the first eruptions to have been linked to an observed climate anomaly, having been held responsible for cold temperatures over much of the Northern Hemisphere in the period 1783-1785. Results from the first climate model simulation of the impact of a similar eruption to that of 1783-1784 are presented. Using sulphate aerosol fields produced in a companion chemical transport model simulation by Stevenson et al. (2003), the radiative forcing and climate response due to the aerosol are calculated here using the Reading Intermediate General Circulation Model (IGCM). The peak Northern Hemisphere mean direct radiative forcing is -5.5 Wm-2 in August 1783. The radiative forcing dies away quickly as the emissions from the volcano decrease; however, a small forcing remains over the Mediterranean until March 1784. There is little forcing in the Southern Hemisphere. There is shown to be an uncertainty of at least 50% in the direct radiative forcing due to assumptions concerning relative humidity and the sophistication of the radiative transfer code used. The indirect effects of the Laki aerosol are potentially large but essentially unquantifiable at the present time. In the IGCM at least, the aerosol from the eruption produces a climate response that is spatially very variable. The Northern Hemisphere mean temperature anomaly averaged over the whole of the calendar year containing most of the eruption is -0.21 K, statistically significant at the 95% level and in reasonable agreement with the available observations of the temperature during 1783.
Sensitivity studies of oxidative changes in the troposphere in 2100 using the GISS GCM
Authors: Grenfell J. L. , Shindell D. T. , Grewe V.
Published: April 2010

Abstract. We examine the relative importance of chemical precursor emissions affecting ozone (O3) and hydroxyl (OH) for the year 2100. Runs were developed from the Comparison of Tropospheric Oxidants (Ox_Comp) modeling workshop year 2100 A2p emissions scenario, part of the Intergovernmental Panel on Climate Change (IPCC) third assessment report (TAR). While TAR examined only cumulative change, we examine individual components (NOx, CH4, CO, etc.). Also, since there will be climate changes in 2100 (not accounted for by TAR), we investigate the effect of changing our fixed SSTs/ocean ice from present day to 2100 conditions, as projected by a coupled ocean-atmosphere model with doubled CO2. Unlike TAR we perform multiannual integrations and we include interactive lightning. Largest changes arose from the run with 2100 industrial NOx (O3=+16.9%, OH=+29.4% in July) and the run with 2100 methane (O3=+17.4%, OH= -19.1% in July). In the latter run, large ozone increases in the NH upper troposphere appeared to repartition HO2 into OH to such an extent that the lowering in OH associated with increased methane was overwhelmed in that region. Incorporating all changes collectively led to the July tropospheric ozone burden increasing from 426 to 601 Tg (+41.1%) and the July OH concentration increasing from 13.6 to 15.2x105 molecules/cm3 (+11.8%).
Averaging kernels for DOAS total-column satellite retrievals
Authors: Eskes H. J. , Boersma K. F.
Published: April 2010

Abstract. The Differential Optical Absorption Spectroscopy (DOAS) method is used extensively to retrieve total column amounts of trace gases based on UV-visible measurements of satellite spectrometers, such as ERS-2 GOME. In practice the sensitivity of the instrument to the tracer density is strongly height dependent, especially in the troposphere. The resulting tracer profile dependence may introduce large systematic errors in the retrieved columns that are difficult to quantify without proper additional information, as provided by the averaging kernel (AK). In this paper we discuss the DOAS retrieval method in the context of the general retrieval theory as developed by Rodgers. An expression is derived for the DOAS AK for optically thin absorbers. It is shown that the comparison with 3D chemistry-transport models and independent profile measurements, based on averaging kernels, is no longer influenced by errors resulting from a priori profile assumptions. The availability of averaging kernel information as part of the total column retrieval product is important for the interpretation of the observations, and for applications like chemical data assimilation and detailed satellite validation studies.
Comment on evidence for surface-initiated homogeneous nucleation
Authors: Kay J. E. , Tsemekhman V. , Larson B. , Baker M. , Swanson B.
Published: April 2010

Abstract. We investigate theoretical, laboratory, and atmospheric evidence for a recently proposed hypothesis: homogeneous ice nucleation initiates at the surface, not in the volume, of supercooled water drops. Using existing thermodynamic arguments, laboratory experiments, and atmospheric data, we conclude that ice embryo formation at the surface cannot be confirmed or disregarded. Ice nucleation rates measured as a function of drop size in an air ambient could help distinguish between volume and surface nucleation rates.
New-particle formation events in a continental boundary layer: first results from the SATURN experiment
Authors: Stratmann F. , Siebert H. , Spindler G. , Wehner B. , Althausen D. , Heintzenberg J. , Hellmuth O. , Rinke R. , Schmieder U. , Seidel C. , Tuch T. , Uhrner U. , Wiedensohler A. , Wandinger U. , Wendisch M. , Schell D. , Stohl A.
Published: April 2010

Abstract. During the SATURN experiment, which took place from 27 May to 14 June 2002, new particle formation in the continental boundary layer was investigated. Simultaneous ground-based and tethered-balloon-borne measurements were performed, including meteorological parameters, particle number concentrations and size distributions, gaseous precursor concentrations and SODAR and LIDAR observations. Newly formed particles were observed inside the residual layer, before the break-up process of the nocturnal inversion, and inside the mixing layer throughout the break-up of the nocturnal inversion and during the evolution of the planetary boundary layer.
Trace gas measurements from infrared satellite for chemistry and climate applications
Authors: Clerbaux C. , Hadji-Lazaro J. , Turquety S. , Mégie G. , Coheur P.-F.
Published: April 2010

Abstract. Space-borne thermal infrared instruments working in the nadir geometry are providing spectroscopic measurements of species that impact on the chemical composition of the atmosphere and on the climate forcing: H2O, CO2, N2O, CH4, CFCs, O3, and CO. The atmospheric abundances obtained from the analysis of IMG/ADEOS measurements are discussed in order to demonstrate the potential scientific return to be expected from future missions using advanced infrared nadir sounders. Some strengths and limitations of passive infrared remote sensing from space are illustrated.
Contribution of gaseous and particulate species to droplet solute composition at the Puy de Dôme, France
Authors: Sellegri K. , Laj P. , Marinoni A. , Dupuy R. , Legrand M. , Preunkert S.
Published: April 2010

Abstract. Chemical reactions of dissolved gases in the liquid phase play a key role in atmospheric processes both in the formation of secondary atmospheric compounds and their wet removal rate but also in the regulation of the oxidizing capacity of the troposphere. The behavior of gaseous species and their chemical transformation in clouds are difficult to observe experimentally given the complex nature of clouds. During a winter field campaign at the summit of the Puy de Dôme (central France, 1465 m a.s.l), we have deployed an experimental set-up to provide a quantification of phase partitioning of both organic (CH3COOH, HCOOH, H2C2O4) and inorganic (NH3, HNO3, SO2, HCl) species in clouds. We found that nitric and hydrochloric acids can be considered close to Henry's law equilibrium, within analytical uncertainty and instrumental errors. On another hand, for NH3 and carboxylic acids, dissolution of material from the gas phase is kinetically limited and never reaches the equilibrium predicted by thermodynamics, resulting in significant sub-saturation of the liquid phase. On the contrary, SIV is supersaturated in the liquid phase, in addition to the presence of significant aerosol-derived SVI transferred through nucleation scavenging. Upon droplet evaporation, a significant part of most species, including SIV, tends to efficiently return back into the gas phase. Overall, gas contribution to the droplet solute concentration ranges from at least 48.5 to 98% depending on the chemical species. This is particularly important considering that aerosol scavenging efficiencies are often calculated assuming a negligible gas-phase contribution to the solute concentration. Our study emphasizes the need to account for the in-cloud interaction between particles and gases to provide an adequate modeling of multiphase chemistry systems and its impact on the atmospheric aerosol and gas phases.
Global modelling of secondary organic aerosol in the troposphere: a sensitivity analysis
Authors: Tsigaridis K. , Kanakidou M.
Published: April 2010

Abstract. A global 3-dimensional chemistry/transport model able to describe O3, NOx, Volatile Organic Compounds (VOC), sulphur and NH3 chemistry has been extended to simulate the temporal and spatial distribution of primary and secondary carbonaceous aerosols in the troposphere focusing on Secondary Organic Aerosol (SOA) formation. A number of global simulations have been performed to determine a possible range of annual global SOA production and investigate uncertainties associated with the model results. The studied uncertainties in the SOA budget have been evaluated to be in decreasing importance: the potentially irreversible sticking of the semi-volatile compounds on aerosols, the enthalpy of vaporization of these compounds, the partitioning of SOA on non-carbonaceous aerosols, the conversion of aerosols from hydrophobic to hydrophilic, the emissions of primary carbonaceous aerosols, the chemical fate of the first generation products and finally the activity coefficient of the condensable species. The large uncertainties associated with the emissions of VOC and the adopted simplification of chemistry have not been investigated in this study. Although not all sources of uncertainties have been investigated, according to our calculations, the above factors within the experimental range of variations could result to an overall uncertainty of about a factor of 20 in the global SOA budget. The global annual SOA production from biogenic VOC might range from 2.5 to 44.5 Tg of organic matter per year, whereas that from anthropogenic VOC ranges from 0.05 to 2.62 Tg of organic matter per year. These estimates can be considered as a lower limit, since partitioning on coarse particles like nitrate, dust or sea-salt, together with the partitioning and the dissociation of the semi-volatile products in aerosol water has been neglected. Comparison of model results to observations, where available, shows a better agreement for the upper budget estimates than for the lower ones.
Transport and build-up of tropospheric trace gases during the MINOS campaign: comparision of GOME, in situ aircraft measurements and MATCH-MPIC-data
Authors: Ladstätter-Weißenmayer A. , Heland J. , Kormann R. , von Kuhlmann R. , Lawrence M. G. , Meyer-Arnek J. , Richter A. , Wittrock F. , Ziereis H. , Burrows J. P.
Published: April 2010

Abstract. The MINOS (Mediterranean INtensive Oxidant Study) campaign was an international, multi-platform field campaign to measure long-range transport of air-pollution and aerosols from South East Asia and Europe towards the Mediterranean basin during August 2001. High pollution events were observed during this campaign. For the Mediterranean region enhanced tropospheric nitrogen dioxide (NO2) and formaldehyde (HCHO), which are precursors of tropospheric ozone (O3), were detected by the satellite based GOME (Global Ozone Monitoring Experiment) instrument and compared with airborne in situ measurements as well as with the output from the global 3D photochemistry-transport model MATCH-MPIC (Model of Atmospheric Transport and CHemistry - Max Planck Institute for Chemistry). The increase of pollution in that region leads to severe air quality degradation with regional and global implications.
Characteristics and direct radiative effect of mid-latitude continental aerosols: the ARM case
Authors: Iziomon M. G. , Lohmann U.
Published: April 2010

Abstract. A multi-year field measurement analysis of the characteristics and direct radiative effect of aerosols at the Southern Great Plains (SGP) central facility of the Atmospheric Radiation Measurement (ARM) Program is presented. Inter-annual mean and standard deviation of submicrometer scattering fraction (at 550 nm) and Ångström exponent å (450 nm, 700 nm) at the mid-latitude continental site are indicative of the scattering dominance of fine mode aerosol particles, being 0.84±0.03 and 2.25±0.09, respectively. We attribute the diurnal variation of submicron aerosol concentration to coagulation, photochemistry and the evolution of the boundary layer. Precipitation does not seem to play a role in the observed afternoon maximum in aerosol concentration. Submicron aerosol mass at the site peaks in the summer (12.1±6.7mg m-3), with the summer value being twice that in the winter. Of the chemically analyzed ionic components (which exclude carbonaceous aerosols), SO4= and NH4+ constitute the dominant species at the SGP seasonally, contributing 23-30% and 9-12% of the submicron aerosol mass, respectively. Although a minor species, there is a notable rise in NO3- mass fraction in winter. We contrast the optical properties of dust and smoke haze. The single scattering albedo w0 shows the most remarkable distinction between the two aerosol constituents. We also present aircraft measurements of vertical profiles of aerosol optical properties at the site. Annually, the lowest 1.2 km contributes 70% to the column total light scattering coefficient. Column-averaged and surface annual mean values of hemispheric backscatter fraction (at 550 nm), w0 (at 550 nm) and å (450 nm, 700 nm) agree to within 5% in 2001. Aerosols produce a net cooling (most pronounced in the spring) at the ARM site