bluuebunny/crossref_metadata_2025 huggingface dataset:
Source apportionment of fine organic aerosols in Beijing
Authors: Wang Q. , Shao M. , Zhang Y. , Wei Y. , Hu M. , Guo S.
Published: April 2010

Abstract. Fine particles (PM2.5, i.e., particles with an aerodynamic diameter of ≤2.5 μm) were collected from the air in August 2005, August–September 2006, and January–February 2007, in Beijing, China. The chemical compositions of particulate organic matter in the ambient samples were quantified by gas chromatography/mass spectrometry. The dominant compounds identified in summertime were n-alkanoic acids, followed by dicarboxylic acids and sugars, while sugars became the most abundant species in winter, followed by polycyclic aromatic hydrocarbons, n-alkanes, and n-alkanoic acids. The contributions of seven emission sources (i.e., gasoline/diesel vehicles, coal burning, wood/straw burning, cooking, and vegetative detritus) to particulate organic matter in PM2.5 were estimated using a chemical mass balance receptor model. The model results present the seasonal trends of source contributions to organic aerosols. Biomass burning (straw and wood) had the highest contribution in winter, followed by coal burning, vehicle exhaust, and cooking. The contribution of cooking was the highest in summer, followed by vehicle exhaust and biomass burning, while coal smoke showed only a minor contribution to ambient organic carbon.
Sensitivity of polar stratospheric ozone loss to uncertainties in chemical reaction kinetics
Authors: Kawa S. R. , Stolarski R. S. , Newman P. A. , Douglass A. R. , Rex M. , Hofmann D. J. , Santee M. L. , Frieler K.
Published: April 2010

Abstract. The impact and significance of uncertainties in model calculations of stratospheric ozone loss resulting from known uncertainty in chemical kinetics parameters is evaluated in trajectory chemistry simulations for the Antarctic and Arctic polar vortices. The uncertainty in modeled ozone loss is derived from Monte Carlo scenario simulations varying the kinetic (reaction and photolysis rate) parameters within their estimated uncertainty bounds. Simulations of a typical winter/spring Antarctic vortex scenario and Match scenarios in the Arctic produce large uncertainty in ozone loss rates and integrated seasonal loss. The simulations clearly indicate that the dominant source of model uncertainty in polar ozone loss is uncertainty in the Cl2O2 photolysis reaction, which arises from uncertainty in laboratory-measured molecular cross sections at atmospherically important wavelengths. This estimated uncertainty in JCl2O2 from laboratory measurements seriously hinders our ability to model polar ozone loss within useful quantitative error limits. Atmospheric observations, however, suggest that the Cl2O2 photolysis uncertainty may be less than that derived from the lab data. Comparisons to Match, South Pole ozonesonde, and Aura Microwave Limb Sounder (MLS) data all show that the nominal recommended rate simulations agree with data within uncertainties when the Cl2O2 photolysis error is reduced by a factor of two, in line with previous in situ ClOx measurements. Comparisons to simulations using recent cross sections from Pope et al. (2007) are outside the constrained error bounds in each case. Other reactions producing significant sensitivity in polar ozone loss include BrO + ClO and its branching ratios. These uncertainties challenge our confidence in modeling polar ozone depletion and projecting future changes in response to changing halogen emissions and climate. Further laboratory, theoretical, and possibly atmospheric studies are needed.
Photolysis imprint in the nitrate stable isotope signal in snow and atmosphere of East Antarctica and implications for reactive nitrogen cycling
Authors: Frey M. M. , Savarino J. , Morin S. , Erbland J. , Martins J. M. F.
Published: April 2010

Abstract. The nitrogen (δ15N) and triple oxygen (δ17O and δ18O) isotopic composition of nitrate (NO3−) was measured year-round in the atmosphere and snow pits at Dome C, Antarctica (DC, 75.1° S, 123.3° E), and in surface snow on a transect between DC and the coast. Comparison to the isotopic signal in atmospheric NO3− shows that snow NO3− is significantly enriched in δ15N by >200‰ and depleted in δ18O by <40‰. Post-depositional fractionation in Δ17O(NO3−) is small, potentially allowing reconstruction of past shifts in tropospheric oxidation pathways from ice cores. Assuming a Rayleigh-type process we find fractionation constants ε of −60±15‰, 8±2‰ and 1±1‰, for δ15N, δ18O and Δ17O, respectively. A photolysis model yields an upper limit for the photolytic fractionation constant 15ε of δ15N, consistent with lab and field measurements, and demonstrates a high sensitivity of 15ε to the incident actinic flux spectrum. The photolytic 15ε is process-specific and therefore applies to any snow covered location. Previously published 15ε values are not representative for conditions at the Earth surface, but apply only to the UV lamp used in the reported experiment (Blunier et al., 2005; Jacobi et al., 2006). Depletion of oxygen stable isotopes is attributed to photolysis followed by isotopic exchange with water and hydroxyl radicals. Conversely, 15N enrichment of the NO3− fraction in the snow implies 15N depletion of emissions. Indeed, δ15N in atmospheric NO3− shows a strong decrease from background levels (4±7‰) to −35‰ in spring followed by recovery during summer, consistent with significant snowpack emissions of reactive nitrogen. Field and lab evidence therefore suggest that photolysis is an important process driving fractionation and associated NO3− loss from snow. The Δ17O signature confirms previous coastal measurements that the peak of atmospheric NO3− in spring is of stratospheric origin. After sunrise photolysis drives then redistribution of NO3− from the snowpack photic zone to the atmosphere and a snow surface skin layer, thereby concentrating NO3− at the surface. Little NO3− appears to be exported off the EAIS plateau, still snow emissions from as far as 600 km inland can contribute to the coastal NO3− budget.
On the capability of IASI measurements to inform about CO surface emissions
Authors: Fortems-Cheiney A. , Chevallier F. , Pison I. , Bousquet P. , Carouge C. , Clerbaux C. , Coheur P.-F. , George M. , Hurtmans D. , Szopa S.
Published: April 2010

Abstract. Between July and November 2008, simultaneous observations were conducted by several orbiting instruments that monitor carbon monoxide in the atmosphere, among them the Infrared Atmospheric Sounding Instrument (IASI) and Measurements Of Pollution In The Troposphere (MOPITT). In this paper, the concentration retrievals at about 700 hPa from these two instruments are successively used in a variational Bayesian system to infer the global distribution of CO emissions. Starting from a global emission budget of 479 Tg for the considered period, the posterior estimate of CO emissions using IASI retrievals gives a total of 643 Tg, which is in close agreement with the budget calculated with version 3 of the MOPITT data (649 Tg). The regional totals are also broadly consistent between the two inversions. Even though our theoretical error budget indicates that IASI constrains the emissions slightly less than MOPITT, because of lesser sensitivity in the lower troposphere, these first results indicate that IASI may play a major role in the quantification of the emissions of CO.
UV Raman lidar measurements of relative humidity for the characterization of cirrus cloud microphysical properties
Authors: Di Girolamo P. , Summa D. , Lin R.-F. , Maestri T. , Rizzi R. , Masiello G.
Published: April 2010

Abstract. Raman lidar measurements performed in Potenza by the Raman lidar system BASIL in the presence of cirrus clouds are discussed. Measurements were performed on 6 September 2004 in the frame of the Italian phase of the EAQUATE Experiment. The major feature of BASIL is represented by its capability to perform high-resolution and accurate measurements of atmospheric temperature and water vapour, and consequently relative humidity, both in daytime and night-time, based on the application of the rotational and vibrational Raman lidar techniques in the UV. BASIL is also capable to provide measurements of the particle backscatter and extinction coefficient, and consequently lidar ratio (at the time of these measurements, only at one wavelength), which are fundamental to infer geometrical and microphysical properties of clouds. A case study is discussed in order to assess the capability of Raman lidars to measure humidity in presence of cirrus clouds, both below and inside the cloud. While air inside the cloud layers is observed to be always under-saturated with respect to water, both ice super-saturation and under-saturation conditions are found inside these clouds. Upper tropospheric moistening is observed below the lower cloud layer. The synergic use of the data derived from the ground based Raman Lidar and of spectral radiances measured by the NAST-I Airborne Spectrometer allows the determination of the temporal evolution of the atmospheric cooling/heating rates due to the presence of the cirrus cloud. Lidar measurements beneath the cirrus cloud layer have been interpreted using a 1-D cirrus cloud model with explicit microphysics. The 1-D simulations indicate that sedimentation-moistening has contributed significantly to the moist anomaly, but other mechanisms are also contributing. This result supports the hypothesis that the observed mid-tropospheric humidification is a real feature which is strongly influenced by the sublimation of precipitating ice crystals. Results illustrated in this study demonstrate that Raman lidars, like the one used in this study, can resolve the spatial and temporal scales required for the study of cirrus cloud microphysical processes and appear sensitive enough to reveal and quantify upper tropospheric humidification associated with cirrus cloud sublimation.
Effect of biomass burning on marine stratocumulus clouds off the California coast
Authors: Brioude J. , Cooper O. R. , Feingold G. , Trainer M. , Freitas S. R. , Kowal D. , Ayers J.K. , Prins E. , Minnis P. , McKeen S. A. , Frost G. J. , Hsie E.-Y.
Published: April 2010

Abstract. Aerosol-cloud interactions are considered to be one of the most important and least known forcings in the climate system. Biomass burning aerosols are of special interest due to their radiative impact (direct and indirect effect) and their potential to increase in the future due to climate change. Combining data from Geostationary Operational Environmental Satellite (GOES) and MODerate-resolution Imaging Spectroradiometer (MODIS) with passive tracers from the FLEXPART Lagrangian Particle Dispersion Model, the impact of biomass burning aerosols on marine stratocumulus clouds has been examined in June and July of 2006–2008 off the California coast. Using a continental tracer, the indirect effect of biomass burning aerosols has been isolated by comparing the average cloud fraction and cloud albedo for different meteorological situations, and for clean versus polluted (in terms of biomass burning) continental air masses at 14:00 local time. Within a 500 km-wide band along the coast of California, biomass burning aerosols, which tend to reside above the marine boundary layer, increased the cloud fraction by 0.143, and the cloud albedo by 0.038. Absorbing aerosols located above the marine boundary layer lead to an increase of the lower tropospheric stability and a reduction in the vertical entrainment of dry air from above, leading to increased cloud formation. The combined effect was an indirect radiative forcing of −7.5% ±1.7% (cooling effect) of the outgoing radiative flux at the top of the atmosphere on average, with a bias due to meteorology of +0.9%. Further away from the coast, the biomass burning aerosols, which were located within the boundary layer, reduced the cloud fraction by 0.023 and the cloud albedo by 0.006, resulting in an indirect radiative forcing of +1.3% ±0.3% (warming effect) with a bias of +0.5%. These results underscore the dual role that absorbing aerosols play in cloud radiative forcing.
Estimating trajectory uncertainties due to flow dependent errors in the atmospheric analysis
Authors: Engström A. , Magnusson L.
Published: April 2010

Abstract. The uncertainty of a calculated trajectory is dependent on the uncertainty in the atmospheric analysis. Using the Ensemble Transform method (originally adapted for ensemble forecasting) we sample the analysis uncertainty in order to create an ensemble of analyses where a trajectory is started from each perturbed analysis. This method, called the Ensemble analysis method (EA), is compared to the Initial spread method (IS), where the trajectory receptor point is perturbed in the horizontal and vertical direction to create a set of trajectories used to estimate the trajectory uncertainty. The deviation growth is examined for one summer and one winter month and for 15 different geographical locations. We find up to a 40% increase in trajectory deviation in the mid-latitudes using the EA method. A simple model for trajectory deviation growth speed is set up and validated. It is shown that the EA method result in a faster error growth compared to the IS method. In addition, two case studies are examined to qualitatively illustrate how the flow dependent analysis uncertainty can impact the trajectory calculations. We find a more irregular behavior for the EA trajectories compared to the IS trajectories and a significantly increased uncertainty in the trajectory origin. We conclude that by perturbing the analysis in agreement with the analysis uncertainties the error in backward trajectory calculations can be more consistently estimated.
On the relationship of polar mesospheric cloud ice water content, particle radius and mesospheric temperature and its use in multi-dimensional models
Authors: Merkel A. W. , Marsh D. R. , Gettelman A. , Jensen E. J.
Published: April 2010

Abstract. The distribution of ice layers in the polar summer mesosphere (called polar mesospheric clouds or PMCs) is sensitive to background atmospheric conditions and therefore affected by global-scale dynamics. To investigate this coupling it is necessary to simulate the global distribution of PMCs within a 3-dimensional (3-D) model that couples large-scale dynamics with cloud microphysics. However, modeling PMC microphysics within 3-D global chemistry climate models (GCCM) is a challenge due to the high computational cost associated with particle following (Lagrangian) or sectional microphysical calculations. By characterizing the relationship between the PMC effective radius, ice water content (iwc), and local temperature (T) from an ensemble of simulations from the sectional microphysical model, the Community Aerosol and Radiation Model for Atmospheres (CARMA), we determined that these variables can be described by a robust empirical formula. The characterized relationship allows an estimate of an altitude distribution of PMC effective radius in terms of local temperature and iwc. For our purposes we use this formula to predict an effective radius as part of a bulk parameterization of PMC microphysics in a 3-D GCCM to simulate growth, sublimation and sedimentation of ice particles without keeping track of the time history of each ice particle size or particle size bin. This allows cost effective decadal scale PMC simulations in a 3-D GCCM to be performed. This approach produces realistic PMC simulations including estimates of the optical properties of PMCs. We validate the relationship with PMC data from the Solar Occultation for Ice Experiment (SOFIE).
Technical Note: Harmonized retrieval of column-integrated atmospheric water vapor from the FTIR network – first examples for long-term records and station trends
Authors: Sussmann R. , Borsdorff T. , Rettinger M. , Camy-Peyret C. , Demoulin P. , Duchatelet P. , Mahieu E. , Servais C.
Published: April 2010

Abstract. We present a method for harmonized retrieval of integrated water vapor (IWV) from existing, long-term, measurement records at the ground-based mid-infrared solar FTIR spectrometry stations of the Network for the Detection of Atmospheric Composition Change (NDACC). Correlation of IWV from FTIR with radiosondes shows an ideal slope of 1.00(3). This optimum matching is achieved via tuning one FTIR retrieval parameter, i.e., the strength of a Tikhonov regularization constraining the derivative (with respect to height) of retrieved water profiles given in per cent difference relative to an a priori profile. All other FTIR-sonde correlation parameters (intercept=0.02(12) mm, bias=0.02(5) mm, standard deviation of coincident IWV differences (stdv)=0.27 mm, R=0.99) are comparable to or better than results for all other ground-based IWV sounding techniques given in the literature. An FTIR-FTIR side-by-side intercomparison reveals a strong exponential increase in stdv as a function of increasing temporal mismatch starting at Δt≈1 min. This is due to atmospheric water vapor variability. Based on this result we derive an upper limit for the precision of the FTIR IWV retrieval for the smallest Δt(=3.75 min) still giving a statistically sufficient sample (32 coincidences), i.e., precision(IWVFTIR)<0.05 mm (or 2.2% of the mean IWV). The bias of the IWV retrievals from the two different FTIR instruments is nearly negligible (0.02(1) mm). The optimized FTIR IWV retrieval is set up in the standard NDACC algorithm SFIT 2 without changes to the code. A concept for harmonized transfer of the retrieval between different stations deals with all relevant control parameters; it includes correction for differing spectral point spacings (via regularization strength), and final quality selection of the retrievals (excluding the highest residuals (measurement minus model), 5% of the total). As first application examples long-term IWV data sets are retrieved from the FTIR records of the Zugspitze (47.4° N, 11.0° E, 2964 m a.s.l.) and Jungfraujoch (46.5° N, 8.0° E, 3580 m a.s.l.) NDACC sites. Station-trend analysis comprises a linear fit after subtracting an intra-annual model (3 Fourier components) and constructing an uncertainty interval [95% confidence] via bootstrap resampling. For the Zugspitze a significant trend of 0.79 [0.65, 0.92] mm/decade is found for the time interval [1996–2008], whereas for the Jungfraujoch no significant trend is found. This confirms recent findings that strong variations of IWV trends do occur above land on the local to regional scale (≈250 km) in spite of homogeneous surface temperature trends. This paper provides a basis for future exploitation of more than a dozen existing, multi-decadal FTIR measurement records around the globe for climate studies.
An approach to retrieve information on the carbonyl fluoride (COF2) vertical distributions above Jungfraujoch by FTIR multi-spectrum multi-window fitting
Authors: Duchatelet P. , Mahieu E. , Ruhnke R. , Feng W. , Chipperfield M. , Demoulin P. , Bernath P. , Boone C. D. , Walker K. A. , Servais C. , Flock O.
Published: April 2010

Abstract. We present an original multi-spectrum fitting procedure to retrieve volume mixing ratio (VMR) profiles of carbonyl fluoride (COF2) from ground-based high resolution Fourier transform infrared (FTIR) solar spectra. The multi-spectrum approach consists of simultaneously combining, during the retrievals, all spectra recorded consecutively during the same day and with the same resolution. Solar observations analyzed in this study with the SFIT-2 v3.91 fitting algorithm correspond to more than 2900 spectra recorded between January 2000 and December 2007 at high zenith angles, with a Fourier Transform Spectrometer operated at the high-altitude International Scientific Station of the Jungfraujoch (ISSJ, 46.5° N latitude, 8.0° E longitude, 3580 m altitude), Switzerland. The goal of the retrieval strategy described here is to provide information about the vertical distribution of carbonyl fluoride. The microwindows used are located in the ν4 or in the ν4 COF2 infrared (IR) absorption bands. Averaging kernel and eigenvector analysis indicates that our FTIR retrieval is sensitive to COF2 inversion between 17 and 30 km, with the major contribution to the retrieved information always coming from the measurement. Moreover, there was no significant bias between COF2 partial columns, total columns or VMR profiles retrieved from the two bands. For each wavenumber region, a complete error budget including all identified sources has been carefully established. In addition, comparisons of FTIR COF2 17–30 km partial columns with KASIMA and SLIMCAT 3-D CTMs are also presented. If we do not notice any significant bias between FTIR and SLIMCAT time series, KASIMA COF2 17–30 km partial columns are lower of around 25%, probably due to incorrect lower boundary conditions. For each times series, linear trend estimation for the 2000–2007 time period as well as a seasonal variation study are also performed and critically discussed. For FTIR and KASIMA time series, very low COF2 growth rates (0.4±0.2%/year and 0.3±0.2%/year, respectively) have been derived. However, the SLIMCAT data set gives a slight negative trend (−0.5±0.2%/year), probably ascribable to discontinuities in the meteorological data used by this model. We further demonstrate that all time series are able to reproduce the COF2 seasonal cycle, which main seasonal characteristics deduced from each data set agree quite well.
Aerosol vertical distribution and optical properties over M'Bour (16.96° W; 14.39° N), Senegal from 2006 to 2008
Authors: Léon J.-F. , Derimian Y. , Chiapello I. , Tanré D. , Podvin T. , Chatenet B. , Diallo A. , Deroo C.
Published: April 2010

Abstract. We present ground-based measurements of aerosol mass, optical properties and vertical extinction profiles acquired in M'Bour, Senegal (16.96° W; 14.39° N) from January 2006 to September 2008. This place of the world is all year long affected by the export of mineral dust as it moves westward to the north Atlantic ocean. The maximum in the dust activity is observed in summer (June–July), corresponding to a maximum in the aerosol optical thickness (above 0.5) and single scattering albedo (above 0.95). It also corresponds to a maximum in the top altitude of the transported aerosol layer (up to 6 km) and aerosol optical thickness scale height (up to 3.5 km) due to the presence of the Saharan Air Layer located between 2 and 6 km. The late summer shows an additional low level aerosol layer that increases in thickness in autumn. Severe dust storms are also systematically observed in spring (March) but with a lower vertical development and a stronger impact (factor 2 to 3) on the ground-level mass compared to summer. Sporadic events of biomass burning aerosols are observed in winter (January) and particularly in January 2006 when the biomass burning aerosol are advected between 1.5 and 3.5 km high. On average, the seasonal signal in the aerosol optical properties and vertical distribution is very similar from year to year over our 3 year monitoring.
Bacteria in the global atmosphere – Part 1: Review and synthesis of literature data for different ecosystems
Authors: Burrows S. M. , Elbert W. , Lawrence M. G. , Pöschl U.
Published: April 2010

Abstract. Bacteria are ubiquitous in the atmosphere, with concentrations of bacterial cells typically exceeding 1×104 m−3 over land. Numerous studies have suggested that the presence of bacteria in the atmosphere may impact cloud development, atmospheric chemistry, and microbial biogeography. A sound knowledge of bacterial concentrations and distributions in the atmosphere is needed to evaluate these claims. This review focusses on published measurements of total and culturable bacteria concentrations in the atmospheric aerosol. We discuss emission mechanisms and the impacts of meteorological conditions and measurement techniques on measured bacteria concentrations. Based on the literature reviewed, we suggest representative values and ranges for the mean concentration in the near-surface air of nine natural ecosystems and three human-influenced land types. We discuss the gaps in current knowledge of bacterial concentrations in air, including the lack of reliable, long-term measurements of the total microbial concentrations in many regions and the scarcity of emission flux measurements.
Characteristics of trace gaseous pollutants at a regional background station in Northern China
Authors: Meng Z. Y. , Xu X. B. , Yan P. , Ding G. A. , Tang J. , Lin W. L. , Xu X. D. , Wang S. F.
Published: April 2010

Abstract. Measurements of trace gaseous pollutants were taken at the Shangdianzi site, a WMO Global Atmosphere Watch (GAW) background station in Northern China. The results are presented for the period from September 2003 to December 2006. Seasonal and diurnal variations of the O3, NOx, SO2, and CO concentration are characterized and possible causes for them are discussed. The observed levels of the trace gases are comparable to those at some other background sites in polluted regions inside and outside of China. It was shown that the seasonal variation of O3 can change slightly from year to year due to the year-to-year alternation in the meteorological conditions. Higher CO concentrations were observed in some warmer months, particularly in June and July, 2006. Intensive biomass burning in the North China Plain region, in combination with the transport of regional pollution by more frequent southwesterly winds, is believed to be responsible for the elevated CO concentrations. The diurnal variation of O3, with delayed peaking times, suggests that the transport of photochemical aged plume is an important source for O3 at Shangdianzi. The diurnal variations of SO2 in all seasons show higher values during daytime, contradicting the common view. An explanation for this unusual phenomenon is hypothesized. To gain an insight into the impact of transport on the trace gases levels at Shangdianzi, air mass backward trajectories were calculated and analyzed in combination with corresponding pollutant concentrations. The results indicate that the transport of air masses from the North China Plain region and from the major coal mining regions west of Shangdianzi is responsible for the high concentrations of the gaseous pollutants.
The SCOUT-O3 Darwin Aircraft Campaign: rationale and meteorology
Authors: Brunner D. , Siegmund P. , May P. T. , Chappel L. , Schiller C. , Müller R. , Peter T. , Fueglistaler S. , MacKenzie A. R. , Fix A. , Schlager H. , Allen G. , Fjaeraa A. M. , Streibel M. , Harris N. R. P.
Published: April 2010

Abstract. An aircraft measurement campaign involving the Russian high-altitude aircraft M55 Geophysica and the German DLR Falcon was conducted in Darwin, Australia in November and December 2005 as part of the European integrated project SCOUT-O3. The overall objectives of the campaign were to study the transport of trace gases through the tropical tropopause layer (TTL), mechanisms of dehydration close to the tropopause, and the role of deep convection in these processes. In this paper a detailed roadmap of the campaign is presented, including rationales for each flight, and an analysis of the local and large-scale meteorological context in which they were embedded. The campaign took place during the pre-monsoon season which is characterized by a pronounced diurnal evolution of deep convection including a mesoscale system over the Tiwi Islands north of Darwin known as "Hector". This allowed studying in detail the role of deep convection in structuring the tropical tropopause region, in situ sampling convective overshoots above storm anvils, and probing the structure of anvils and cirrus clouds by Lidar and a suite of in situ instruments onboard the two aircraft. The large-scale flow during the first half of the campaign was such that local flights, away from convection, sampled air masses downstream of the "cold trap" region over Indonesia. Abundant cirrus clouds enabled the study of active dehydration, in particular during two TTL survey flights. The campaign period also encompassed a Rossby wave breaking event transporting stratospheric air to the tropical middle troposphere and an equatorial Kelvin wave modulating tropopause temperatures and hence the conditions for dehydration.
Diagnostics of the Tropical Tropopause Layer from in-situ observations and CCM data
Authors: Palazzi E. , Fierli F. , Cairo F. , Cagnazzo C. , Di Donfrancesco G. , Manzini E. , Ravegnani F. , Schiller C. , D'Amato F. , Volk C. M.
Published: April 2010

Abstract. A suite of diagnostics is applied to in-situ aircraft measurements and one Chemistry-Climate Model (CCM) data to characterize the vertical structure of the Tropical Tropopause Layer (TTL). The diagnostics are based on vertical tracer profiles and relative vertical tracer gradients, using tropopause-referenced coordinates, and tracer-tracer relationships in the tropical Upper Troposphere/Lower Stratosphere (UT/LS). Observations were obtained during four tropical campaigns performed from 1999 to 2006 with the research aircraft Geophysica and have been compared to the output of the ECHAM5/MESSy CCM. The model vertical resolution in the TTL (~500 m) allows for appropriate comparison with high-resolution aircraft observations and the diagnostics used highlight common TTL features between the model and the observational data. The analysis of the vertical profiles of water vapour, ozone, and nitrous oxide, in both the observations and the model, shows that concentration mixing ratios exhibit a strong gradient change across the tropical tropopause, due to the role of this latter as a transport barrier and that transition between the tropospheric and stratospheric regimes occurs within a finite layer. The use of relative vertical ozone and carbon monoxide gradients, in addition to the vertical profiles, helps to highlight the region where this transition occurs and allows to give an estimate of its thickness. The analysis of the CO-O3 and H2O-O3 scatter plots and of the Probability Distribution Function (PDF) of the H2O-O3 pair completes this picture as it allows to better distinguish tropospheric and stratospheric regimes that can be identified by their different chemical composition. The joint analysis and comparison of observed and modelled data allows to state that the model can represent the background TTL structure and its seasonal variability rather accurately. The model estimate of the thickness of the interface region between tropospheric and stratospheric regimes agrees well with average values inferred from observations. On the other hand, the measurements can be influenced by regional scale variability, local transport processes as well as deep convection, that can not be captured by the model.
Methane and nitrous oxide emissions in The Netherlands: ambient measurements support the national inventories
Authors: van der Laan S. , Neubert R. E. M. , Meijer H. A. J.
Published: April 2010

Abstract. We present net emission estimates of CH4 and N2O of The Netherlands based on measurements conducted during the period of May 2006 to April 2009 at station Lutjewad, The Netherlands (6°21' E, 53°24' N, 1 m a.s.l.). 222Radon mixing ratios were applied as an indicator for vertical mixing and long-range air mass transport and used to calculate the net surface fluxes from atmospheric mixing ratios of CH4 and N2O. Our study shows that our measurement site Lutjewad is well-suited to measure emissions from The Netherlands and validation of the national inventories using the 222Radon flux method. Since this study is purely observation-based it is independent from inventories or atmospheric models. Our results are compared to the national inventories as reported to the UNFCCC. We found net emissions of: (15.2±5.3) t km−2 a−1 for CH4 and (0.9±0.3) t km−2 a−1 for N2O. These values are lower than the inventory-based emissions (2006-2008 averages) of (18.3±3.3) t km−2 a−1 for CH4, and (1.3±0.6) t km−2 a−1 for N2O, but the differences are insignificant.
Aerosol number fluxes over the Amazon rain forest during the wet season
Authors: Ahlm L. , Nilsson E. D. , Krejci R. , Mårtensson E. M. , Vogt M. , Artaxo P.
Published: April 2010

Abstract. Number fluxes of particles with diameter larger than 10 nm were measured with the eddy covariance method over the Amazon rain forest during the wet season as part of the LBA (The Large Scale Biosphere Atmosphere Experiment in Amazonia) campaign 2008. The primary goal was to investigate whether sources or sinks dominate the aerosol number flux in the tropical rain forest-atmosphere system. During the measurement campaign, from 12 March to 18 May, 60% of the particle fluxes pointed downward, which is a similar fraction to what has been observed over boreal forests. The net deposition flux prevailed even in the absolute cleanest atmospheric conditions during the campaign and therefore cannot be explained only by deposition of anthropogenic particles. The particle transfer velocity vt increased with increasing friction velocity and the relation is described by the equation vt = 2.4×10−3×u* where u* is the friction velocity. Upward particle fluxes often appeared in the morning hours and seem to a large extent to be an effect of entrainment fluxes into a growing mixed layer rather than primary aerosol emission. In general, the number source of primary aerosol particles within the footprint area of the measurements was small, possibly because the measured particle number fluxes reflect mostly particles less than approximately 200 nm. This is an indication that the contribution of primary biogenic aerosol particles to the aerosol population in the Amazon boundary layer may be low in terms of number concentrations. However, the possibility of horizontal variations in primary aerosol emission over the Amazon rain forest cannot be ruled out.
The influence of the vertical distribution of emissions on tropospheric chemistry
Authors: Pozzer A. , Jöckel P. , Van Aardenne J.
Published: April 2010

Abstract. The atmospheric chemistry general circulation model EMAC (ECHAM5/MESSy atmospheric chemistry) is used to investigate the effect of height dependent emissions on tropospheric chemistry. In a sensitivity simulation, anthropogenic and biomass burning emissions are released in the lowest model layer. The resulting tracer distributions are compared to those of a former simulation applying height dependent emissions. Although the differences between the two simulations in the free troposphere are small (less than 5%), large differences are present in polluted regions at the surface, in particular for NOx (more than 100%), CO (up to 30%) and non-methane hydrocarbons (up to 30%), whereas for OH the differences at the same locations are somewhat lower (15%). Global ozone formation is virtually unaffected by the choice of the vertical distribution of emissions. Nevertheless, local ozone changes can be up to 30%. Model results of both simulations are further compared to observations from field campaigns and to data from measurement stations.
A three-dimensional model study of methanesulphonic acid to non sea salt sulphate ratio at mid and high-southern latitudes
Authors: Castebrunet H. , Martinerie P. , Genthon C. , Cosme E.
Published: April 2010

Abstract. The Antarctic and sub-Antarctic methanesulphonic acid (MSA) to non sea salt sulphate (nssSO4) ratio is simulated with the Laboratoire de Météorologie Dynamique Atmospheric General Circulation Model including an atmospheric sulphur chemistry module. Spatial variations of the MSA/nssSO4 ratio in different regions have been suggested to be mostly dependent on temperature or sulphur source contributions. Its past variations in ice cores have been interpreted as related to the DMS precursor source location. Our model results are compared with available field measurements in the Antarctic and sub-Antarctic regions. This suggests that the MSA/nssSO4 ratio in the extra-tropical south hemisphere is mostly dependent on the relative importance of various DMS oxidation pathways. In order to evaluate the effect of a rapid conversion of dimethyl sulphoxide (DMSO) into MSA, not implemented in the model, the MSA+DMSO to nssSO4 ratio is also discussed. Using this modified ratio, the model mostly captures the seasonal variations of MSA/nssSO4 at mid and high-southern latitudes. In addition, the model qualitatively reproduces the bell shaped meridional variations of the ratio, which is highly dependent on the adopted relative reaction rates for the DMS+OH addition and abstraction pathways, and on the assumed reaction products of the MSIA+OH reaction. MSA/nssSO4 ratio in Antarctic snow is fairly well reproduced except at the most inland sites characterized with very low snow accumulation rates. Our results also suggest that atmospheric chemistry plays an important role in the observed decrease of the ratio in snow between coastal regions and central Antarctica. The still insufficient understanding of the DMS oxidation scheme limits our ability to model the MSA/nssSO4 ratio. Specifically, reaction products of the MSIA+OH reaction should be better quantified, and the impact of a fast DMSO conversion to MSA in spring to fall over Antarctica should be evaluated. A better understanding of BrO source processes is needed in order to include DMS + BrO chemistry in global models. Completing the observations of DMS, BrO and MSA at Halley Bay with DMSO measurements would better constrain the role of BrO in DMS oxidation. Direct measurements of MSA and nssSO4 dry deposition velocities on Antarctic snow would improve our ability to model MSA and nssSO4 in ice cores.
The use of disjunct eddy sampling methods for the determination of ecosystem level fluxes of trace gases
Authors: Turnipseed A. A. , Pressley S. N. , Karl T. , Lamb B. , Nemitz E. , Allwine E. , Cooper W. A. , Shertz S. , Guenther A. B.
Published: April 2010

Abstract. The concept of disjunct eddy sampling (DES) for use in measuring ecosystem-level micrometeorological fluxes is re-examined. The governing equations are discussed as well as other practical considerations and guidelines concerning this sampling method as it is applied to either the disjunct eddy covariance (DEC) or disjunct eddy accumulation (DEA) techniques. A disjunct eddy sampling system was constructed that could either be combined with relatively slow sensors (response time of 2 to 40 s) to measure fluxes using DEC, or could also be used to accumulate samples in stable reservoirs for later laboratory analysis (DEA technique). Both the DEC and DEA modes of this sampler were tested against conventional eddy covariance (EC) for fluxes of either CO2 (DEC) or isoprene (DEA). Good agreement in both modes was observed relative to the EC systems. However, the uncertainty in a single DEA flux measurement was considerable (~40%) due to both the reduced statistical sampling and the analytical precision of the concentration difference measurements. We have also re-investigated the effects of nonzero mean vertical wind velocity on accumulation techniques as it relates to our DEA measurements. Despite the higher uncertainty, disjunct eddy sampling can provide an alternative technique to eddy covariance for determining ecosystem-level fluxes for species where fast sensors do not currently exist.
Simulation of trace gas redistribution by convective clouds – Liquid phase processes
Authors: Yin Y. , Parker D. J. , Carslaw K. S.
Published: April 2010

Abstract. A two-dimensional dynamic cloud model with detailed microphysics and a spectral treatment of gas scavenging was used to simulate trace gas vertical redistribution in precipitating continental and maritime clouds. A general picture of gas transport in such clouds has been developed by examining the sensitivity to a range of parameters, including cloud dynamic and microphysical structure, gas solubility, and the method of calculating gas uptake by droplets. Gases with effective Henry’s law constants (H*) ranging from zero to greater than 109 mol dm-3 atm-1 were simulated. The abundance of highly soluble gases in the uppermost parts (top 1 km or so) of continental precipitating clouds was found to be as much as 20–50% of that of the insoluble tracer under conditions where the mixing ratio of the tracer was approximately 5% of its boundary layer value. The abundance of highly soluble gases was approximately 6 times higher in the uppermost parts of the continental cloud than in the maritime cloud, due to differences in wet removal efficiency in the two cloud types. A fully kinetic calculation of gas uptake, as opposed to assuming Henry’s law equilibrium, was found to have a significant effect on gas transport, with the abundance of highly soluble gases in the uppermost parts of the cloud being a factor of 5 lower in the equilibrium simulations. The temperature dependence of the Henry’s law constant was also found to be an important parameter in determining the abundance of soluble gases at cloud top, with the abundance of moderately soluble gases being as much as 70% lower when the temperature dependence of H* was included. This reduction in abundance was found to be equivalent to increasing the temperature-independent solubility by a factor of 7. The vertical transport of soluble gases could be parameterized in large-scale models by normalizing against the transport of tracers. However, our results suggest that there is no straightforward scaling factor, particularly if small concentrations of highly soluble gases in the upper troposphere need to be defined.
Coastal zone production of IO precursors: A 2-dimensional study
Authors: Carpenter L. J. , Hebestreit K. , Platt U , Liss P. S.
Published: April 2010

Abstract. At Mace Head, Eire, in the coastal East Atlantic, diiodomethane has been identified as an important precursor of iodine oxide radicals. Peak concentrations of both CH2I2 and IO at low water indicate that the intertidal region is a strong source of organoiodines. Atmospheric measurements of CH2I2 made in marine air are used in conjunction with a 2-dimensional model incorporating horizontal and vertical dispersion to provide estimates of the intertidal and offshore fluxes of CH2I2 upwind of Mace Head. The strong signature of photolysis in the CH2I2 observations indicates that the emissions are not entirely local/coastal, but must include an additional offshore source. Good agreement between model and measured CH2I2 concentrations is achieved with an offshore flux of 2 × 104 molecules cm-2 s-1 and an intertidal flux ranging from 1.3 × 109 molecules cm-2 s-1 (low water) to 6.5 × 108 molecules cm-2 s-1 (high water), the latter over a 100 m wide coastal belt. The coastal emissions at low water are in good agreement with independent estimates made from seaweed emission data. We estimate that, although intertidal emissions are ~4 orders of magnitude higher than those offshore, their contribution to the measured CH2I2 concentrations at 10 m height is only ~50%.
298 K rate coefficients for the reaction of OH with i-C3H7I, n-C3H7I and C3H8
Authors: Carl S. A. , Crowley J. N.
Published: April 2010

Abstract. The kinetics of the title reactions were investigated using the laser photolysis - resonance fluorescence method, employing the sequential two-photon dissociation of NO2 in the presence of H2 as the OH source. The 298 K rate constant for OH + C3H8 was found to be (1.15±0.1) × 10-12 cm3 s-1, in excellent agreement with the literature recommendation, and with a separate determination using HNO3 photolysis at 248 nm as the OH source. The 298 K rate constants for OH + n-C3H7I and i-C3H7I were measured for the first time and found to be (1.47±0.08) and (1.22±0.06) × 10-12 cm3 s-1, respectively. The errors include an assessment of systematic error due to concentration measurement, which, for the propyl-iodides was minimised by on-line UV-absorption spectroscopy. The implications of these results for the reactive iodine budget of the marine boundary layer are discussed.
The influence of cloud chemistry on HOx and NOx in the Marine Boundary Layer: a 1-D modelling study
Authors: Williams J. E. , Dentener F. J. , van den Berg A. R.
Published: April 2010

Abstract. A 1-D marine stratocumulus cloud model has been supplemented with a comprehensive and up-to-date aqueous phase chemical mechanism for the purpose of assessing the impact that the presence of clouds and aerosols has on gas phase HOx, NOx and O3 budgets in the marine boundary layer. The simulations presented here indicate that cloud may act as a heterogeneous source of HONOg via the conversion of HNO4(g) at moderate pH (~4.5). The photolysis of nitrate (NO3-) has also been found to contribute to this simulated increase in HONOg by ~5% and also acts as a minor source of NO2(g). The effect of introducing deliquescent aerosol on the simulated increase of HONOg is negligible. The most important consequences of this elevation in HONOg are that, in the presence of cloud, gas phase concentrations of NOx species increase by a factor of 2, which minimises the simulated decrease in O3(g), and results in a regeneration of OHg. This partly compensates for the removal of OHg by direct phase transfer into the cloud and has important implications regarding the oxidising capacity of the marine boundary layer. The findings presented here also suggest that previous modelling studies, which neglect the heterogeneous HNO4(g) reaction cycle, may have over-estimated the role of clouds as a sink for OHg and O3(g)in unpolluted oceanic regions, by ~10% and ~2%, respectively.
Chemistry-transport modeling of the satellite observed distribution of tropical tropospheric ozone
Authors: Peters W. , Krol M. , Dentener F. , Thompson A. , Lelieveld J.
Published: April 2010

Abstract. We have compared the 14-year record of satellite derived tropical tropospheric ozone columns (TTOC) from the NIMBUS-7 Total Ozone Mapping Spectrometer (TOMS) to TTOC calculated by a chemistry-transport model (CTM). An objective measure of error, based on the zonal distribution of TTOC in the tropics, is applied to perform this comparison systematically. In addition, the sensitivity of the model to several key processes in the tropics is quantified to select directions for future improvements. The comparison indicates a widespread, systematic (~20%) underestimate of TTOC over the tropical Atlantic Ocean, which maximizes during austral spring. This 'Atlantic mismatch' is largely due to a misrepresentation of seasonally recurring processes in the model, while minor differences between model and observations over the tropical Pacific Ocean are mostly due to uncaptured interannual variability. Although chemical processes determine the TTOC extent, dynamical processes dominate the TTOC distribution, as the use of actual meteorology pertaining to the year of observations always leads to a better agreement with TTOC observations than using a random year or a climatology. The modeled TTOC is remarkably insensitive to many model parameters due to efficient feedbacks in the ozone budget. Nevertheless, the simulations would profit from an improved biomass burning calendar, as well as from an increase in NOx abundances in free tropospheric biomass burning plumes. The use of multi-year satellite derived tropospheric data to systematically test and improve a CTM is a promising new addition to existing methods of model validation, and is a first step to integrate tropospheric satellite observations into global ozone modeling studies.