bluuebunny/crossref_metadata_2025 huggingface dataset:
On the use of mass-conserving wind fields in chemistry-transport models
Authors: Bregman B. , Segers A. , Krol M. , Meijer E. , van Velthoven P.
Published: April 2010

Abstract. A new method has been developed that provides mass-conserving wind fields for global chemistry-transport models. In previous global Eulerian modeling studies a mass-imbalance was found between the model mass transport and the surface pressure tendencies. Several methods have been suggested to correct for this imbalance, but so far no satisfactory solution has been found. Our new method solves these problems by using the wind fields in a spherical harmonical form (divergence and vorticity) by mimicing the physics of the weather forecast model as closely as possible. A 3-D chemistry-transport model was used to show that the calculated ozone fields with the new processing method agree remarkably better with ozone observations in the upper troposphere and lower stratosphere. In addition, the calculated age of air in the lower stratosphere show better agreement with observations, although the air remains still too young in the extra tropical stratosphere.
Ozone decomposition on Saharan dust: an experimental investigation
Authors: Hanisch F. , Crowley J. N.
Published: April 2010

Abstract. The heterogeneous reaction between O3 and authentic Saharan dust surfaces was investigated in a Knudsen reactor at approx 296 K. O3 was destroyed on the dust surface and O2 was formed with conversion efficiencies of 1.0 and 1.3 molecules O2 per O3 molecule destroyed for unheated and heated samples, respectively. No O3 desorbed from exposed dust samples, showing that the uptake was irreversible. The uptake coefficients for the irreversible destruction of O3 on (unheated) Saharan dust surfaces depended on the O3 concentration and varied between 3.5 x10-4 and 5.5 x10-6 for the initial uptake coefficient (g0 approx 3 x10-5 at 30 ppbv O3 STP) and between 4.8 x10-5 and 2.2 x10-6 for the steady-state uptake coefficient (gss approx 7 x10-6 at 30 ppbv O3 STP). At very high O3 concentrations the surface was deactivated, and O3 uptake ceased after a certain exposure period. Sample re-activation (i.e. de-passivation) was found to occur over periods of hours, after exposure to O3 had ceased, suggesting that re-activation processes play a role both in the laboratory and in the atmosphere.
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 mmol -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.
Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds
Authors: Saunders S. M. , Jenkin M. E. , Derwent R. G. , Pilling M. J.
Published: April 2010

Abstract. Kinetic and mechanistic data relevant to the tropospheric degradation of volatile organic compounds (VOC), and the production of secondary pollutants, have previously been used to define a protocol which underpinned the construction of a near-explicit Master Chemical Mechanism. In this paper, an update to the previous protocol is presented, which has been used to define degradation schemes for 107 non-aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). The treatment of 18 aromatic VOC is described in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the reactions of the radical intermediates and the further degradation of first and subsequent generation products. Emphasis is placed on updating the previous information, and outlining the methodology which is specifically applicable to VOC not considered previously (e.g. a- and b-pinene). The present protocol aims to take into consideration work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Application of MCM v3 in appropriate box models indicates that the representation of isoprene degradation provides a good description of the speciated distribution of oxygenated organic products observed in reported field studies where isoprene was the dominant emitted hydrocarbon, and that the a-pinene degradation chemistry provides a good description of the time dependence of key gas phase species in a-pinene/NOX photo-oxidation experiments carried out in the European Photoreactor (EUPHORE). Photochemical Ozone Creation Potentials (POCP) have been calculated for the 106 non-aromatic non-methane VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. Where applicable, the values are compared with those calculated with previous versions of the MCM.
Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds
Authors: Jenkin M. E. , Saunders S. M. , Wagner V. , Pilling M. J.
Published: April 2010

Abstract. Kinetic and mechanistic data relevant to the tropospheric degradation of aromatic volatile organic compounds (VOC) have been used to define a mechanism development protocol, which has been used to construct degradation schemes for 18 aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). This is complementary to the treatment of 107 non-aromatic VOC, presented in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the degradation chemistry to first generation products via a number of competitive routes, and the further degradation of first and subsequent generation products. Emphasis is placed on describing where the treatment differs from that applied to the non-aromatic VOC. The protocol is based on work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Photochemical Ozone Creation Potentials (POCP) have been calculated for the 18 aromatic VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. These show distinct differences from POCP values calculated previously for the aromatics, using earlier versions of the MCM, and reasons for these differences are discussed.
Deep convective injection of boundary layer air into the lowermost stratosphere at midlatitudes
Authors: Fischer H. , de Reus M. , Traub M. , Williams J. , Lelieveld J. , de Gouw J. , Warneke C. , Schlager H. , Minikin A. , Scheele R. , Siegmund P.
Published: April 2010

Abstract. On 22 August 2001 a measurement flight was performed with the German research aircraft FALCON from Sardinia to Crete as part of the Mediterranean Oxidant Study (MINOS). Cruising at 8.2 km, the aircraft was forced to climb to 11.2 km over the southern tip of Italy to stay clear of the anvil of a large cumulonimbus tower. During ascent into the lowermost stratosphere in-situ measurements onboard the FALCON indicated several sharp increases in the concentrations of tropospheric trace gases, e.g. CO, acetone, methanol, benzene and acetonitrile, above the anvil. During one particular event deep in the stratosphere, at O3 concentrations exceeding 200 ppv, CO increased from about 60 to 90 ppv, while the concentration of acetone and methanol increased by more than a factor of 2 (0.7 to 1.8 ppv for acetone; 0.4 to 1.4 ppv for methanol). Enhancements for the short lived species benzene are even higher, increasing from 20 pptv in the stratosphere to approx. 130 pptv. The concentrations during the event were higher than background concentrations in the upper troposphere, indicating that polluted boundary layer air was directly mixed deep into the lowermost stratosphere.
Emission of ions and charged soot particles by aircraft engines
Authors: Sorokin A. , Vancassel X. , Mirabel P.
Published: April 2010

Abstract. In this article, a model which examines the formation and evolution of chemiions in an aircraft engine is proposed. This model which includes chemiionisation, electron thermo-emission, electron attachment to soot particles and to neutral molecules, electron-ion and ion-ion recombination, ion-soot interaction, allows the determination of the ion concentration at the exit of the combustor and at the nozzle exit of the engine. It also allows the determination of the charge of the soot particles. A comparison of the model results with the available ground-based experimental data obtained on the ATTAS research aircraft engines during the SULFUR experiments (Schumann, 2002) shows an excellent agreement.
Estimated variability of below-cloud aerosol removal by rainfall for observed aerosol size distributions
Authors: Andronache C.
Published: April 2010

Abstract. Below-cloud scavenging (BCS) coefficients of aerosols by rainfall are estimated for reported aerosol size distributions measured during field experiments in various environments. The method employed is based on explicit calculations of the efficiency of collision between a raindrop and aerosol particles. Results show that BCS coefficient increases with rainfall rate and has a significant dependence on aerosol size distribution parameters. Thus, BCS is important for very small particles (with diameters less than 0.01 µm) and for coarse particles (with diameters larger than 2 µm). For rainfall rate R ~ 1 mm hr -1, the 0.5-folding time of these particles is of the order of one hour. It is shown that BCS is negligible for aerosol particles in the range [0.1-1] µm if compared with in-cloud scavenging rates for low and moderate rainfall rates (R ~ 0.1-10 mm hr -1). The results indicate that a boundary layer aerosol size distribution with coarse mode is drastically affected very shortly after rain starts (in a fraction of one hour) and consequently, the below-cloud aerosol size distribution becomes dominated by particles in the accumulation mode.
Using 14C, 13C, 18O and 17O isotopic variations to provide insights into the high northern latitude surface CO inventory
Authors: Röckmann T. , Jöckel P. , Gros V. , Bräunlich M. , Possnert G. , Brenninkmeijer C. A. M.
Published: April 2010

Abstract. Measurements of the complete isotopic composition of atmospheric CO (13CO, 14CO, C17O, C18O) have been carried out at the high northern latitude stations Spitsbergen, Norway, and Alert, Canada. The annual changes of the isotope signatures reflect the seasonally varying contributions from the individual CO sources and the OH sink. Short-term variability is small at the remote sampling locations. Nevertheless, the interannual variability is considerable, in particular for the summer minimum. The most prominent event was a strong increase in CO in 1998 that persisted for several months. Using the isotope signatures it is possible to clearly identify extraordinarily strong biomass burning during that season as the cause for this large-scale CO anomaly. In 1997, on the other hand, biomass burning emissions were very low, leading to an unusually low summer minimum and corresponding isotope signatures. The results underscore that monitoring of CO and its isotopic composition at remote high latitude stations is a valuable tool to better understand long-term variations of CO that are representative for the whole high northern latitude region.
Intercontinental transport of nitrogen oxide pollution plumes
Authors: Wenig M. , Spichtinger N. , Stohl A. , Held G. , Beirle S. , Wagner T. , Jähne B. , Platt U.
Published: April 2010

Abstract. We describe the first satellite observation of intercontinental transport of nitrogen oxides emitted by power plants, verified by simulations with a particle tracer model. The analysis of such episodes shows that anthropogenic NOx plumes may influence the atmospheric chemistry thousands of kilometers away from its origin, as well as the ocean they traverse due to nitrogen fertilization. This kind of monitoring became possible by applying an improved algorithm to extract the tropospheric fraction of NO2 from the spectral data coming from the GOME instrument. As an example we show the observation of NO2 in the time period 4--14 May, 1998, from the South African Plateau to Australia which was possible due to favourable weather conditions during that time period which availed the satellite measurement. This episode was also simulated with the Lagrangian particle dispersion model FLEXPART which uses NOx emissions taken from an inventory for industrial emissions in South Africa and is driven with analyses from the European Centre for Medium-Range Weather Forecasts. Additionally lightning emissions were added by utilizing Lightning Imaging Sensor data. Lightning NOx  was found to amount to around 10% of the resulting concentrations. Both, the measured and simulated emission plume show matching patterns while traversing the Indian Ocean to Australia and show great resemblance to the aerosol and CO2 transport observed by Piketh et al. (2000)
Chemical mass balance of size-segregated atmospheric aerosol in an urban area of the Po Valley, Italy
Authors: Matta E. , Facchini M. C. , Decesari S. , Mircea M. , Cavalli F. , Fuzzi S. , Putaud J.-P. , Dell’Acqua A.
Published: April 2010

Abstract. A complete size segregated chemical characterisation was carried out for aerosol samples collected in the urban area of Bologna over a period of one year, using five-stage low pressure Berner impactors. An original dual-substrate technique was adopted to obtain samples suitable for a complete chemical characterisation. Total mass, inorganic, and organic components were analysed as a function of size, and a detailed characterisation of the water soluble organic compounds was also performed by means of a previously developed methodology, based on HPLC separation of organic compounds according to their acid character and functional group analysis by Proton Nuclear Magnetic Resonance. Chemical mass closure of the collected samples was reached to within a few percent on average in the submicron aerosol range, while a higher unknown fraction in the coarse aerosol range was attributed to soil-derived species not analysed in this experiment. Comparison of the functional group analysis results with model results simulating water soluble organic compound production by gas-to-particle conversion of anthropogenic VOCs showed that this pathway provides a minor contribution to the organic composition of the aerosol samples in the urban area of Bologna.
Partitioning of reactive nitrogen (NOy) and dependence on meteorological conditions in the lower free troposphere
Authors: Zellweger C. , Forrer J. , Hofer P. , Nyeki S. , Schwarzenbach B. , Weingartner E. , Ammann M. , Baltensperger U.
Published: April 2010

Abstract. Results of continuous nitrogen oxide (NO), nitrogen dioxide (NO2), peroxyacetyl nitrate (PAN) and total reactive nitrogen (NOy) measurements along with seasonal field campaigns of nitric acid (HNO3) and particulate nitrate (NO3-) measurements are presented for a two-year period at the high-alpine research station Jungfraujoch (JFJ), 3580 m asl. The NOy mixing ratio and partitioning is shown to strongly depend on meteorological conditions. Knowledge of these meteorological transport processes allows discrimination between undisturbed (i.e. clean) and disturbed (i.e. influenced by regional pollution sources) free tropospheric (FT) conditions at the JFJ. Median NOy concentrations during undisturbed FT periods ranged from 350 pptv (winter, December to February) to 581 pptv (spring, March to April). PAN was found to be the dominant NOy species during spring and summer, whereas NO2 was most abundant during autumn and winter. Particulate nitrate was found to contribute significantly to total NOy during thermally induced vertical transport. Föhn events, synoptical lifting (e.g. fronts) and thermally induced vertical transport resulted in mixing ratios up to 10 times higher at the JFJ compared to undisturbed FT conditions. Furthermore this meteorological variability of the NOy concentration and partitioning often dominated the seasonal variability. As a consequence the use of filters at the JFJ (and other mountainous sites) is crucial for the interpretation of data from such measurement sites. This study presents a further development of meteorological filters for the high-alpine site Jungfraujoch, which could be adapted to other mountainous measurement sites.
Interhemispheric differences in the chemical characteristics of the Indian Ocean aerosol during INDOEX
Authors: Norman M. , Leck C. , Rodhe H.
Published: April 2010

Abstract. The water soluble inorganic part of the sub-micrometer aerosol was measured from two research vessels over the Indian Ocean during the winter monsoon season (February and March) as part of the INDOEX project in 1998 and 1999. Additional measurements were made of gas phase SO2 from one of the vessels in 1999. All samples collected north of the ITCZ were clearly affected by continental, anthropogenic sources. A sharp transition occurred across the ITCZ with concentrations of nss-SO42, NH4+ and nss-K+ being lower by a factor of 7--15, >20 and >40, respectively, on the southern side of the ITCZ. The contribution from DMS to the sub-micrometer nss-SO42 was estimated to be up to 40% in clean air north of the ITCZ but less than 10% in polluted air originating from India. South of the ITCZ virtually all nss-SO42 was likely to be derived from oxidation of DMS. The concentration of \\chem{SO_2} decreased rapidly with distance from the Indian coast, the ratio \\SO2nss-SO42 reaching values below 5% after 35 h travel time over the ocean. Surprisingly, MSA, which is derived from DMS, also showed higher concentrations in the sub-micrometer aerosol north of the ITCZ than south of it. This could be explained by the larger sub-micrometer surface area available north of the ITCZ for the condensation of MSA. South of the ITCZ a major part of the MSA was found on the super-micrometer particles. The total amount of MSA, on both sub-micrometer and super-micrometer particles, varied little across the ITCZ. An analysis based on the air trajectories showed that systematic variation in the observed concentrations was associated with variations in the transport from source regions. For example, differences in time since air parcels left the Arabian or Indian coasts was shown to be an important factor for explaining the substantial differences in absolute concentrations.
The impact of mid-latitude intrusions into the polar vortex on ozone loss estimates
Authors: Grooß J.-U. , Müller R.
Published: April 2010

Abstract. Current stratospheric chemical model simulations underestimate substantially the large ozone loss rates that are derived for the Arctic from ozone sondes for January of some years. Until now, no explanation for this discrepancy has been found. Here, we examine the influence of intrusions of mid-latitude air into the polar vortex on these ozone loss estimates. This study focuses on the winter 1991/92. It is based on simulations performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS). The simulations for January 1992 show that the intrusions induce a reduction of vortex average ozone mixing ratio corresponding to a systematic offset of the ozone loss rate of about 12 ppb per day. Further, the results of the Match method are influenced by the intrusions, since the intruded air masses are deformed and reach dimensions below the Match radius. From our calculations we deduce a systematic offset of the Match ozone loss rate by about 10 ppb/day, which may explain about 28% of the published discrepancy between Match and box model simulations for the winter 1991/92.
Hohenpeissenberg Photochemical Experiment (HOPE 2000): Measurements and photostationary state calculations of OH and peroxy radicals
Authors: Handisides G. M. , Plass-Dülmer C. , Gilge S. , Bingemer H. , Berresheim H.
Published: April 2010

Abstract. Measurements of OH, the sum of peroxy radicals (ROx), non-methane hydrocarbons (NMHCs) and various other trace gases were made at the Meteorological Observatory Hohenpeissenberg in June 2000. The data from an intensive measurement period characterised by high solar insolation (18-21 June) are analysed. The maximum midday OH concentration ranged between 4.5 x 106 molecules cm-3 and 7.4 x 106 molecules cm-3. The maximum total ROx mixing ratio increased from about 55 pptv on 18 June to nearly 70 pptv on 20 and 21 June. A total of 64 NMHCs, including isoprene and monoterpenes, were measured every 1 to 6 hours. The oxidation rate of the NMHCs by OH was calculated and reached a total of over 14 x 106 molecules cm-3  s-1  on two days. A simple photostationary state balance model was used to simulate the ambient OH and ROx concentrations with the measured data as input. The model was able to reproduce the main features of the diurnal profiles of both OH and ROx. The model results proved to be most sensitive to assumptions about the mixing ratio of formaldehyde (HCHO), which was included as a proxy for carbonyl compounds, and about the partitioning between HO2 and RO2. The measured OH concentration and ROx mixing ratios were reproduced well by assuming the presence of 3 ppbv HCHO and a  ratio HO2/RO2 between 1:1 and 1:2. The most important source of OH, and conversely the greatest sink for ROx, was the recycling of  HO2 radicals to OH. This reaction was responsible for the recycling of more than 45 x 106 molecules cm-3  s-1 on two days. The most important sink for OH, and the largest source of  ROx, was the oxidation of NMHCs, in particular, of isoprene and the monoterpenes.
Factors controlling Arctic denitrification in cold winters of the 1990s
Authors: Mann G. W. , Davies S. , Carslaw K. S. , Chipperfield M. P.
Published: April 2010

Abstract. Denitrification of the Arctic winter stratosphere has been calculated using a 3-D microphysical model for the winters 1994/95, 1995/96, 1996/97 and 1999/2000. Denitrification is assumed to occur through the sedimentation of low number concentrations of large nitric acid trihydrate (NAT) particles, as observed extensively in 1999/2000. We examine whether the meteorological conditions that allowed NAT particles to grow to the very large sizes observed in 1999/2000 also occurred in the other cold winters. The results show that winter 1999/2000 had conditions that were optimum for denitrification by large NAT particles, which are a deep concentric cold pool and vortex. Under these conditions, NAT particles can circulate in the cold pool for several days, reaching several micrometres in radius and leading to a high downward flux of nitric acid. The other winters had shorter periods with optimum conditions for denitrification. However, we find that NAT particles could have grown to large sizes in all of these winters and could have caused significant denitrification. We define the quantity "closed flow area'' (the fraction of the cold pool in which air parcel trajectories can form closed loops) and show that it is a very useful indicator of possible denitrification. We find that even with a constant NAT nucleation rate throughout the cold pool, the average NAT number concentration and size can vary by up to a factor of 10 in response to this meteorological quantity. These changes in particle properties account for a high degree of variability in denitrification between the different winters. This large meteorologically induced variability in denitrification rate needs to be compared with that which could arise from a variable nucleation rate of NAT particles, which remains an uncertain quantity in models.
Surface ozone depletion episodes in the Arctic and Antarctic from historical ozonesonde records
Authors: Tarasick D. W. , Bottenheim J. W.
Published: April 2010

Abstract. Episodes of ozone depletion in the lowermost Arctic atmosphere (0--2 km) at polar sunrise have been intensively studied at Alert, Canada, and are thought to result from catalytic reactions involving bromine. Recent observations of high concentrations of tropospheric BrO over large areas of the Arctic and Antarctic suggest that such depletion events should also be seen by ozonesondes at other polar stations. An examination of historical ozonesonde records shows that such events occur frequently at Alert, Eureka and Resolute, but much less frequently at Churchill and at other stations. The differences appear to be attributable to differences in surface meteorology. The long record at Resolute shows depletions since 1966, but with an apparent increase in their frequency since about 1985. This is surprising, since the Br involved in the depletion mechanism is believed to be entirely of natural origin.
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 (>10 min) clouds, capable of exerting a measurable radiative or chemical impact, are generated within a narrow range of updraft speeds below 1 - 2 cm s -1 at temperatures below about 215K, with concentrations of ice crystals not exceeding 0.1 cm-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. Given these results, it seems likely that a limited number (<0.1 cm-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.
New particle formation during α- and β-pinene oxidation by O3, OH and NO3, and the influence of water vapour: particle size distribution studies
Authors: Bonn B. , Moortgat G. K.
Published: April 2010

Abstract. New particle formation during the oxidation of a- and b-pinene (C10H16) by ozone, OH and NO3 was studied by measuring the particle size distributions with a scanning mobility particle sizer (TSI 3936). The results indicate a drastically higher nucleation potential of the ozonolysis than in the reaction with either OH or NO3. On the contrary, the contribution of the individual oxidation reactions to form new aerosol volume was found to depend on the location of the carbon double bond to be oxidized: for the endocyclic a-pinene reactions the ozonolysis contributed mostly to the aerosol volume yield, whereas for the exocyclic b-pinene reactions the oxidation by O3, OH and NO3 yielded a similar aerosol volume. In a second part of this study the influence of water vapour on the nucleation in all three possible oxidation routes was examined. The observations revealed only an effect of water vapour during the ozonolysis reactions.
Uptake of HNO3 to deliquescent sea-salt particles
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 mm diameter). This implies that diffusion in the gas-phase is the limiting step to HNO3 uptake until the sea-salt has been completely processed.
Three years of routine Raman lidar measurements of tropospheric aerosols: Planetary boundary layer heights, extinction and backscatter coefficients
Authors: Schneider J. , Eixmann R.
Published: April 2010

Abstract. We have performed a three-year series of routine lidar measurements on a climatological base. To obtain an unbiased data set, the measurements were taken 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 in and above the planetary boundary layer. The aerosol extinction coefficient has been determined at 532 nm, but here the majority of the measurements has been restricted to heights above the boundary layer. Only after-sunset measurements are included in this data set since the Raman measurements were restricted to darkness. For the climatological analysis, we selected the cloud-free days out of a fixed measurement schedule. The annual cycle of the boundary layer height has been found to have a phase shift of about 25 days with respect to the summer/winter solstices. The mean values of the extinction and backscatter coefficients do not show significant annual differences. The backscatter coefficients in the planetary boundary layer were found to be about 10 times higher than above. The mean aerosol optical depth above the boundary layer and below 5 km is 0.26 (±1.0)  x 10-2 in summer, and 1.5 (±0.95)  x 10-2 in winter, which almost negligible compared to values measured in the boundary layer. A cluster analysis of the backward trajectories yielded two major directions of air mass origin above the planetary boundary layer and 4 major directions inside. A marked difference between the total aerosol load 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 draws due to the high variability of the measured backscatter coefficients.
The UV-visible absorption cross-sections of IONO2
Authors: Mössinger J. C. , Rowley D. M. , Cox R. A.
Published: April 2010

Abstract. The UV-visible absorption spectrum of gaseous IONO2 has been measured over the wavelength range 245--415 nm using the technique of laser photolysis with time-resolved UV-visible absorption spectroscopy. IONO2 was produced in situ in the gas phase by laser flash photolysis of NO2/CF3I/N2 mixtures. Post-flash spectra were deconvolved to remove contributions to the observed absorption from other reactant and product species. The resulting spectrum attributed to IONO2 consists of several overlapping broad absorption bands. Assuming a quantum yield of unity for IONO2 photolysis, model calculations show that during sunlit hours at noon, 53° N, the first order solar photolysis rate coefficient (J value) for IONO2 is 4.6 x 10-2 s-1.
Ground-based intercomparison of two isoprene measurement techniques
Authors: Leibrock E. , Huey L. G. , Goldan P. D. , Kuster W. C. , Williams E. , Fehsenfeld F. C.
Published: April 2010

Abstract. An informal intercomparison of two isoprene (C5H8) measurement techniques was carried out during Fall of 1998 at a field site located approximately 3 km west of Boulder, Colorado, USA. A new chemical ionization mass spectrometric technique (CIMS) was compared to a well-established gas chromatographic technique (GC). The CIMS technique utilized benzene cation chemistry to ionize isoprene. The isoprene levels measured by the CIMS were often larger than those obtained with the GC. The results indicate that the CIMS technique suffered from an interference associated with air masses from the Denver, CO metropolitan area. However, the CIMS technique is also demonstrated to be sensitive and fast and is a candidate for isoprene measurements in remote environments near isoprene sources.
On the origin of tropospheric O3 over the Indian Ocean during the winter monsoon: African biomass burning vs. stratosphere-troposphere exchange
Authors: de Laat A. T. J.
Published: April 2010

Abstract. A comparison and analysis of modeled and measured O3 profiles from the INDOEX campaign is presented. European Centre for Medium-Range Weather Forecast  (ECMWF) meteorological analyses have been assimilated into the model to represent actual meteorology. The focus of this study is on two commonly observed features in the O3 profiles: mid tropospheric O3 maxima (300--500 hPa) over the tropical Indian Ocean, and the upper-tropospheric O3  laminae that occur above approximately 14 km (>150 hPa) altitude. A comparison of model simulated O3 profiles with measured O3 profiles indicates that the model realistically simulates the observed mid-tropospheric O3 maxima. An analysis of the model simulations shows that the major source of the mid-tropospheric O3 maxima is advection of polluted air masses from continental biomass burning areas over Africa, with generally only a small contribution of stratospheric O3. Previous studies hinted at Stratosphere-Troposphere exchange (STE) along the subtropical jet (STJ) as the primary source of the mid-tropospheric O3 maxima over the Indian Ocean. Analysis of the model simulations shows that the mechanism causing the mid-tropospheric transport of African biomass burning pollution and stratospheric air masses are frontal zones or waves passing along the subtropical jets, causing advection of tropical air masses in the prefrontal zone. Furthermore, these frontal zones or waves also cause STE at the mid-latitudinal side of the STJ. The model simulations also indicate that the contribution of STE in general is minor compared to advection and in situ tropospheric production of O3 for the mid-tropospheric O3 budget over the Indian Ocean region. An analysis of the model simulations shows that the model cannot exactly reproduce the measured upper-tropospheric O3 maxima. However, modeled O3 mixing ratios at 14 and 16 km altitude are significantly higher than at 8 to 12 km altitude, indicating that the model does simulate an upper-tropospheric layer. According to the model simulations, the sources of O3 at 14 and 16 km altitude are advection of both tropospheric and stratospheric O3 as well as in situ O3 formation.
On the relationship between acetone and carbon monoxide in air masses of different origin
Authors: de Reus M. , Fischer H. , Arnold F. , de Gouw J. , Holzinger R. , Warneke C. , Williams J.
Published: April 2010

Abstract. Carbon monoxide and acetone measurements are presented for five aircraft measurement campaigns at mid-latitudes, polar and tropical regions in the northern hemisphere. Throughout all campaigns, free tropospheric air masses, which were influenced by anthropogenic emissions, showed a similar linear relation between CO and acetone, with a slope of 21–25 pptv acetone/ppbv CO. Measurements in the anthropogenically influenced marine boundary layer revealed a slope of 13–16 pptv acetone/ppbv CO. The different slopes observed in the marine boundary layer and the free troposphere indicate that acetone is emitted by the ocean in relatively clean air masses and taken up by the ocean in polluted air masses. In the lowermost stratosphere, a good correlation between CO and acetone was observed as well, however, with a much smaller slope (~5 pptv acetone/ppbv CO) compared to the troposphere. This is caused by the longer photochemical lifetime of CO compared to acetone in the lower stratosphere, due to the increasing photolytic loss of acetone and the decreasing OH concentration with altitude. No significant correlation between CO and acetone was observed over the tropical rain forest due to the large direct and indirect biogenic emissions of acetone. The common slopes of the linear acetone-CO relation in various layers of the atmosphere, during five field experiments, makes them useful for model calculations. Often a single observation of the CO-acetone correlation, determined from stratospheric measurements, has been used in box model applications. This study shows that different slopes have to be considered for marine boundary layer, free tropospheric and stratospheric air masses, and that the CO-acetone relation cannot be used for air masses which are strongly influenced by biogenic emissions.
A three-dimensional model study of long-term mid-high latitude lower stratosphere ozone changes
Authors: Chipperfield M. P.
Published: April 2010

Abstract. We have used a 3D off-line chemical transport model (CTM) to study the causes of the observed changes in ozone in the mid-high latitude lower stratosphere from 1979–1998. The model was forced by European Centre for Medium Range Weather Forecasts (ECMWF) analyses and contains a detailed chemistry scheme. A series of model runs were performed at a horizontal resolution of 7.5°×7.5° and covered the domain from about 12 km to 30 km. The basic model performs well in reproducing the decadal evolution of the springtime depletion in the northern hemisphere (NH) and southern hemisphere (SH) high latitudes in the 1980s and early 1990s. After about 1994 the modelled interannual variability does not match the observations as well, which is probably due in part to changes in the operational ECMWF analyses – which places limits on using this dataset to diagnose dynamical trends. For mid-latitudes (35°–60°) the basic model reproduces the observed column ozone decreases from 1980 until the early 1990s. Model experiments show that the halogen trends appear to dominate this modelled decrease and of this around 30–50% is due to high-latitude processing on polar stratospheric clouds (PSCs). Dynamically induced ozone variations in the model correlate with observations over the timescale of a few years. Large discrepancies between the modelled and observed variations in the mid 1980s and mid 1990s can be largely resolved by assuming that the 11-year solar cycle (not explicitly included in the 3D model) causes a 2% (min-max) change in mid-latitude column ozone.
Comprehensive two-dimensional gas chromatography (GC×GC) measurements of volatile organic compounds in the atmosphere
Authors: Xu X. , van Stee L. L. P. , Williams J. , Beens J. , Adahchour M. , Vreuls R. J. J. , Brinkman U. A. T. , Lelieveld J.
Published: April 2010

Abstract. During the MINOS campaign in August 2001 comprehensive two-dimensional gas chromatography (GC×GC) was applied to the in situ measurements of atmospheric volatile organic compounds (VOCs) at the Finokalia ground station, Crete. The measurement system employs a thermal desorption unit for on-line sampling and injection, and a GCxGC separation system equipped with a flame ionization detector (FID) for detection. The system was optimized to resolve C7−C14 organic components. Two-dimensional chromatograms from measurements of Finokalia air samples show several hundred well-separated peaks. To facilitate peak identification, cartridge samples collected at Finokalia were analyzed using the same GC×GC system coupled with a time-of-flight mass spectrometer (TOF-MS). The resulting mass spectra were deconvoluted and compared to spectra from a database for tentative peak identification. About 650 peaks have been identified in the two-dimensional plane, with significant signal/noise ratios (>100) and high spectra similarities (>800). By comparing observed retention indices with those found in the literature, 235 of the identifications have been confirmed. 150 of the confirmed compounds show up in the C7−C14 range of the chromatogram from the in situ measurement. However, at least as many peaks remain unidentified. For quantification of the GCxGC measurements, peak volumes of measured compounds have been integrated and externally calibrated using a standard gas mixture.
OH in the coastal boundary layer of Crete during MINOS: Measurements and relationship with ozone photolysis
Authors: Berresheim H. , Plass-Dülmer C. , Elste T. , Mihalopoulos N. , Rohrer F.
Published: April 2010

Abstract. Hydroxyl radical (OH) concentrations were measured in August 2001 at Finokalia Station on the northeastern coast of Crete during the Mediterranean Intensive Oxidant Study (MINOS). OH was measured based on selected ion chemical ionization mass spectrometry (SI/CIMS) with a time resolution of 30 s and signal integration of 5 min. The corresponding accuracy, precision, and detection limit were 20% (1s), 11% (1s), and 2.4×105 molecules cm−3 (2 s), respectively. OH levels showed a strong diurnal variability with high maxima (approximately 2×107 molecules cm−3) occurring around 13:30 LT (10:30 UTC) and nighttime values below the detection limit. Daily 24-hour average concentrations varied between 3.6–6.7×1016 cm−3. For the total measurement period (6–21 August) the mean and standard deviation were 4.5±1.1×106 cm−3. The OH data set is analyzed based on a classification into three periods: I: 6–8 August, II: 9–11 August, III: 13–18 August. For each of the three periods the measured OH concentrations are described by the empirical function [OH] = a J(O1D)0.68, with J(O1D) being the ozone photolysis frequency and a = 1.4×1010 s cm−3, 1.7×1010 s cm−3, and 2.2×1010 s cm−3, respectively. It is shown that this relationship is consistent with a CH4-CO box model yielding a corresponding exponent of 0.70. Taking into account the estimated precision of the OH measurements this empirical function explains 99% of the observed variance of OH.
Constraining tropospheric mixing timescales using airborne observations and numerical models
Authors: Good P. , Giannakopoulos C. , O’Connor F. M. , Arnold S. R. , de Reus M. , Schlager H.
Published: April 2010

Abstract. A technique is demonstrated for estimating atmospheric mixing time-scales from in-situ data, using a Lagrangian model initialised from an Eulerian chemical transport model (CTM). This method is applied to airborne tropospheric CO observations taken during seven flights of the Mediterranean Intensive Oxidant Study (MINOS) campaign, of August 2001. The time-scales derived, correspond to mixing applied at the spatial scale of the CTM grid. Specifically, they are upper bound estimates of the mix-down lifetime that should be imposed for a Lagrangian model to reproduce the observed small-scale tracer structure. They are relevant to the family of hybrid Lagrangian-Eulerian models, which impose Eulerian grid mixing to an underlying Lagrangian model. The method uses the fact that in Lagrangian tracer transport modelling, the mixing spatial and temporal scales are decoupled: the spatial scale is determined by the resolution of the initial tracer field, and the time scale by the trajectory length. The chaotic nature of lower-atmospheric advection results in the continuous generation of smaller spatial scales, a process terminated in the real atmosphere by mixing. Thus, a mix-down lifetime can be estimated by varying trajectory length so that the model reproduces the observed amount of small-scale tracer structure. Selecting a trajectory length is equivalent to choosing a mixing timescale. For the cases studied, the results are very insensitive to CO photochemical change calculated along the trajectories. The method is most appropriate for relatively homogeneous regions, i.e. it is not too important to account for changes in aircraft altitude or the positioning of stratospheric intrusions, so that small scale structure is easily distinguished. The chosen flights showed a range of mix-down time upper limits: 1 and 3 days for 8 August and 3 August, due to recent convective and boundary layer mixing respectively, and 7–9 days for 16, 17, 22a, 22c and 24 August. For the flight of 3 August, the observed concentrations result from a complex set of transport histories, and the models are used to interpret the observed structure, while illustrating where more caution is required with this method of estimating mix-down lifetimes.
Distribution and origin of ozone in the eastern Mediterranean free troposphere during MINOS (August 2001)
Authors: Roelofs G.-J. , Scheeren B. , Heland J. , Ziereis H. , Lelieveld J.
Published: April 2010

Abstract. A coupled tropospheric chemistry – climate model is used to reproduce and analyze tropospheric ozone distributions observed during the MINOS campaign in the eastern Mediterranean region (August, 2001). Generally, regional atmospheric dynamics in summer are strongly influenced by the occurrence of an upper tropospheric anti-cyclone, associated with the Asian summer monsoon and centered over the Tibetan Plateau. The anti-cyclone affects the chemical composition of the upper troposphere, where ozone concentrations of about 50 ppbv were measured, through advection of boundary layer air from South-East Asia. A layer between 4–6 km thickness and containing up to 120 ppbv of ozone was present beneath. Ozone from stratospheric origin and from lightning NOx contributed to this layer. Additionally, pollutant ozone from North America was mixed in. Ozone in the lower troposphere originated mainly from the European continent. Modeled ozone profiles are in reasonable agreement with the observations. The stratospheric influence is sometimes overestimated by the model due to too strong vertical diffusion associated with the relatively coarse vertical resolution of the model, and specific convective events are not reproduced realistically. The modeled tropospheric ozone column over the eastern Mediterranean is ~50 DU in summer, to which ozone from recent stratospheric origin contributes about 30%, ozone from lightning 13%, and from South-East Asia, North America and Europe about 7%, 8% and 14%, respectively, adding to a long-term hemispheric background of 25% of the column.