bluuebunny/crossref_metadata_2025 huggingface dataset:
Methane production from mixed tropical savanna and forest vegetation in Venezuela
Authors: Crutzen P. J. , Sanhueza E. , Brenninkmeijer C. A. M.
Published: April 2010

Abstract. Measurements of methane concentrations in the boundary layer in the northern part of the Guayana shield, Venezuela, during the wet season (October 1988), showed the presence of substantial methane surface emissions. The measuring site is within the savanna climate region, but is affected by emissions from savanna and forest vegetation. From day versus night concentration measurements, with higher concentrations during night, a methane source strength near the site of 3–7×1011 molecules/cm2/s can be estimated, which includes emissions from small tracts of flooded soils, termites and especially tropical vegetation. Extrapolated to the entire savanna, this may imply a methane source of ~30–60 Tg yr−1 similar to the one calculated for tropical vegetation on the basis of recently published in vitro plant emission experiments by Keppler et al. (2006), which indicate emissions of ~30 Tg yr−1 for tropical savannas and grasslands and ~78 Tg yr−1 for tropical forests.
A study on aerosol extinction-to-backscatter ratio with combination of micro-pulse lidar and MODIS over Hong Kong
Authors: He Q. S. , Li C. C. , Mao J. T. , Lau A. K. H.
Published: April 2010

Abstract. The aerosol extinction-to-backscatter ratio is an important parameter for inverting LIDAR signals in the LIDAR equation. It is also a complicated function of aerosol microphysical characteristics depending on geographical and meteorological conditions. In this paper, a method to retrieve the column-averaged aerosol extinction-to-backscatter ratio by constraining the aerosol optical depths (AOD) recorded by the Moderate Resolution Imaging Spectroradiometer (MODIS) to the ones measured by a Micro-pulse LIDAR (MPL) is presented. Both measurements were taken between 1 May 2003 and 30 June 2004 over Hong Kong, a coastal city in south China. Simultaneous scattering coefficients measured by a forward scattering visibility sensor are compared with the LIDAR retrieval. The data are then analyzed in terms of monthly and seasonal trends. In addition, the relationships between the extinction-to-backscatter ratio and wind conditions as well as other aerosol microphysical parameters are also presented. The mean aerosol extinction-to-backscatter ratio for the whole period is found to be 28.9±6.1 sr, with the minimum of 12 sr in August 2003 and the maximum of 44 sr in March 2004. The ratio is lower in the summer because of the dominance of oceanic aerosols in association with the prevailing southwesterly monsoon. In contrast, relatively larger ratios are noted in spring and winter because of the increased impact of local and regional industrial pollutants associated with the northerly monsoon. The extended LIDAR measurements over Hong Kong provide not only a more accurate retrieval of aerosol extinction coefficient profiles, but also significant information for air pollution and climate studies in the region.
Factors of air ion balance in a coniferous forest according to measurements in Hyytiälä, Finland
Authors: Tammet H. , Hõrrak U. , Laakso L. , Kulmala M.
Published: April 2010

Abstract. A new theoretical model includes dry deposition of ions onto the forest canopy and takes into account different parameters of positive and negative ions. Explicit algebraic solution of the air ion balance equations allows calculating the ionization rate and the average charge of aerosol particles according to air ion and aerosol measurements, and parameters of forest. The transformation of direct measurements to the values of the ionization rate does not bring along amplification of measurement errors. The model was used to estimate the ionization rate at the Hyytiälä forest station, Finland, and it solved the controversy of different estimates in the earlier study. The ionization rate during one-day measurements proved to be 5.6±0.8 cm−3 s−1 at the standard measuring height of 2 m and 3.9±0.2 cm−3 s−1 at the height of 14 m between the tops of the trees. The height variation should be considered when the ionization rate is used as a parameter in models of ion-induced nucleation. The recombination sink of cluster ions on the ions of opposite polarity made up 9–13%, the sink on aerosol particles 65–69%, and the sink on forest canopy 18–26% of the total sink of cluster ions. The average lifetime of cluster ions was about 130 s for positive ions and about 110 s for negative ions. About 70% of the space charge of the air was carried by aerosol particles at the height of 2 m and about 84% at the height of 14 m.
The composition of nucleation and Aitken modes particles during coastal nucleation events: evidence for marine secondary organic contribution
Authors: Vaattovaara P. , Huttunen P. E. , Yoon Y. J. , Joutsensaari J. , Lehtinen K. E. J. , O’Dowd C. D. , Laaksonen A.
Published: April 2010

Abstract. Newly-formed nanometer-sized particles have been observed at coastal and marine environments worldwide. Interestingly, organic species have so far not been detected in those newly-formed nucleation mode particles. In this study, we applied the UFO-TDMA (ultrafine organic tandem differential mobility analyzer) method to study the possible existence of an organic fraction in recently formed coastal nucleation mode particles (d<20 nm) at the Mace Head research station. Furthermore, effects of those nucleation events to potential CCN (cloud condensation nuclei) were studied. The coastal events were typical for the Mace Head region and they occurred at low tide conditions during efficient solar radiation and high biological activity (HBA, i.e. a high mass concentration of chlorophyll a of the ocean) in spring 2002. Additionally, a PHA-UCPC (pulse height analyzer ultrafine condensation particle counter) technique was used to study the composition of newly-formed particles formed in low tide conditions during a lower biological activity (LBA, i.e. a lower mass concentration of chlorophyll a of the ocean) in October 2002. The overall results of the UFO-TDMA and the PHA-UCPC measurements indicate that those coastally/marinely formed nucleation mode particles include a remarkable fraction of secondary organic products, beside iodine oxides, which are likely to be responsible for the nucleation. During clean marine air mass conditions, the origin of those secondary organic oxidation compounds can be related to marine/coastal biota and thus a major fraction of the organics may originate from biosynthetic production of alkenes such as isoprene and their oxidation by iodine, hydroxyl radical, and ozone. During modified marine conditions, also anthropogenic secondary organic compounds may contribute to the nucleation mode organic mass, in addition to biogenic secondary organic compounds. Thus, the UFO-TDMA results suggest that the secondary organic compounds may, in addition to being significant contributors to the nucleation mode processes, accelerate the growth of freshly nucleated particles and increase their survival probability to CCN and even larger radiatively active particle sizes. The results give new insights to the coastal/marine particle formation, growth, and properties. The marine biota driven secondary organic contributions to coastal/marine particle formation and composition can be anticipated in other species specific biologically active oceans and fresh-waters areas around the world and thus, they may be significant also to the global radiative bugdet, atmosphere-biosphere feedbacks, and climate change.
Black carbon or brown carbon? The nature of light-absorbing carbonaceous aerosols
Authors: Andreae M. O. , Gelencsér A.
Published: April 2010

Abstract. Although the definition and measurement methods of atmospheric ''black carbon'' (''BC'') have long been subjects of scientific controversy, the recent discovery of light-absorbing carbon that is not black (''brown carbon, Cbrown'') makes it imperative to reassess and redefine the components that make up light-absorbing carbonaceous matter (LAC) in the atmosphere. Evidence for the atmospheric presence of Cbrown comes directly from aerosol absorption measurements near specific combustion sources, from observations of spectral properties of water extracts of continental aerosol, from laboratory studies indicating the formation of light-absorbing organic matter in the atmosphere, and indirectly from the chemical analogy of aerosol species to colored natural humic substances. We show that these species may severely bias measurements of ''BC'' and ''EC'' over vast parts of the troposphere, where mass concentration of Cbrown is high relative to that of combustion soot. We also imply that due to the strongly skewed absorption of Cbrown towards the UV, single-wavelength light absorption measurements may not be adequate for the assessment of absorption of solar radiation in the troposphere. The possible consequences of these effects on our understanding of tropospheric processes are discussed.
Importance of the surface reaction OH+Cl- on sea salt aerosol for the chemistry of the marine boundary layer – a model study
Authors: von Glasow R.
Published: April 2010

Abstract. The reaction of the hydroxyl radical with chloride on the surface of sea salt aerosol producing gas phase Cl2 and particulate OH- and its implications for the chemistry of the marine boundary layer under coastal, remote, and very remote conditions have been investigated with a numerical model. This reaction had been suggested by Laskin et al. (2003) to play a major role in the sulfur cycle in the marine boundary layer by increasing the sulfate production in sea salt by O3 oxidation due to the additional production of alkalinity in the particle. Based on literature data a new "best estimate'' for the rate coefficient of the reaction was deduced and applied, showing that the additional initial sulfate production by this reaction is less than 1%, therefore having only a minor impact on sulfate production. Even though the gas phase concentration of Cl2 increased strongly in the model the concentration of Cl radicals increased by less than 5% for the "best guess'' case. Additional feedbacks between the cycles of chlorine and sulfur in the marine boundary layer are discussed as well as a two-stage acidification of large fresh sea salt aerosol.
First space-borne measurements of methanol inside aged tropical biomass burning plumes using the ACE-FTS instrument
Authors: Dufour G. , Boone C. D. , Rinsland C. P. , Bernath P. F.
Published: April 2010

Abstract. First measurements from space of upper tropospheric and lower stratospheric methanol profiles within aged fire plumes are reported. Elevated levels of methanol at 0–45° S from 30 September to 3 November 2004 have been measured by the high resolution infrared spectrometer ACE-FTS onboard the SCISAT satellite. Methanol volume mixing ratios higher than 4000 pptv are detected and are strongly correlated with other fire products such as CO, C2H6, and HCN. A sensitivity study of the methanol retrieval, accounting for random and systematic contributions, shows that the retrieved methanol profile is reliable from 8.5 to 16.5 km, with an accuracy of about 20% for measurements inside polluted air masses. The upper tropospheric enhancement ratio of methanol with respect to CO is estimated from the correlation plot between methanol and CO for aged tropical biomass burning plumes. This ratio is in good agreement with the ratio measured in the free troposphere (up to 12 km) by recent aircraft studies and does not suggest any secondary production of methanol by oxidation in aged biomass burning plumes.
Aerosol chemical and optical properties over the Paris area within ESQUIF project
Authors: Hodzic A. , Vautard R. , Chazette P. , Menut L. , Bessagnet B.
Published: April 2010

Abstract. Aerosol chemical and optical properties are extensively investigated for the first time over the Paris Basin in July 2000 within the ESQUIF project. The measurement campaign offers an exceptional framework to evaluate the performances of the chemistry-transport model CHIMERE in simulating concentrations of gaseous and aerosol pollutants, as well as the aerosol-size distribution and composition in polluted urban environment against ground-based and airborne measurements. A detailed comparison of measured and simulated variables during the second half of July with particular focus on 19 and 31 pollution episodes reveals an overall good agreement for gas-species and aerosol components both at the ground level and along flight trajectories, and the absence of systematic biases in simulated meteorological variables such as wind speed, relative humidity and boundary layer height as computed by the MM5 model. A good consistency in ozone and NO concentrations demonstrates the ability of the model to reproduce fairly well the plume structure and location both on 19 and 31 July, despite an underestimation of the amplitude of ozone concentrations on 31 July. The spatial and vertical aerosol distributions are also examined by comparing simulated and observed lidar vertical profiles along flight trajectories on 31 July and confirmed the model capacity to simulate the plume characteristics. The comparison of observed and modeled aerosol components in the southwest suburb of Paris during the second half of July indicated that the aerosol composition is rather correctly reproduced, although the total aerosol mass is underestimated of about 20%. The simulated Parisian aerosol is dominated by primary particulate matter that accounts for anthropogenic and biogenic primary particles (40%) and inorganic aerosol fraction (40%) including nitrate (8%), sulfate (22%) and ammonium (10%). The secondary organic aerosols (SOA) represent 12% of the total aerosol mass, while the mineral dust accounts for 8%. The comparison demonstrated the absence of systematic errors in the simulated sulfate, ammonium and nitrates total concentrations. However for nitrates the observed partition between fine and coarse mode is not reproduced. In CHIMERE there is a clear lack of coarse-mode nitrates. This calls for additional parameterizations in order to account for the heterogeneous formation of nitrate onto dust particles. Larger discrepancies are obtained for the secondary organic aerosols due to both inconsistencies in the SOA formation processes in the model leading to an underestimation of their mass and large uncertainties in the determination of the measured aerosol organic fraction. The observed mass distribution of aerosols is not well reproduced, although no clear explanation can be given.
Correlation between traffic density and particle size distribution in a street canyon and the dependence on wind direction
Authors: Voigtländer J. , Tuch T. , Birmili W. , Wiedensohler A.
Published: April 2010

Abstract. Combustion of fossil fuel in gasoline and diesel powered vehicles is a major source of aerosol particles in a city. In a street canyon, the number concentration of particles smaller than 300 nm in diameter, which can be inhaled and cause serious health effects, is dominated by particles originating from this source. In this study we measured both, particle number size distribution and traffic density continuously in a characteristic street canyon in Germany for a time period of 6 months. The street canyon with multistory buildings and 4 traffic lanes is very typical for larger cities. Thus, the measurements are also representative for many other street canyons. In contrast to previous studies, we measured and analyzed the particle number size distribution with high size resolution using a Twin Differential Mobility Analyzer (TDMPS). The measured size range was from 3 to 800 nm, separated into 40 size channels. Correlation coefficients between particle number concentration for integrated size ranges and traffic up to 0.5 counts were determined. Correlations were also calculated for each of the 40 size channels of the DMPS system, respectively. We found two maxima of the correlation coefficient for particles about 10 nm and in the size range 60–80 nm in diameter. Furthermore, correlations between traffic and particles in dependence of meteorological data were calculated. Relevant parameters were identified by a multiple regression method. In our experiment only wind parameters have influenced the particle number concentration significantly. Very high correlation coefficients (up to 0.85) could be observed in the lee side of the street canyon as well as particles in the range between 60 and 80 nm in diameter. These values are significantly higher than correlation coefficients for other wind directions and other particle sizes. A minimum was found in the luff side of the street. These findings are in good agreement with theory of fluid dynamics in street canyons.
MIPAS database: Validation of HNO3 line parameters using MIPAS satellite measurements
Authors: Flaud J.-M. , Brizzi G. , Carlotti M. , Perrin A. , Ridolfi M.
Published: April 2010

Abstract. Using new and accurate experimental results concerning the spectroscopic properties of the HNO3 molecule as well as improved theoretical methods it has been possible to generate an improved set of line parameters for this molecule in the spectral range covered by the MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) experiment. These line parameters, which have been validated using broadband atmospheric spectra recorded by MIPAS, have been included in the last version of the MIPAS spectroscopic database to be used for future processing of the MIPAS spectra.
Probing stratospheric transport and chemistry with new balloon and aircraft observations of the meridional and vertical N2O isotope distribution
Authors: Kaiser J. , Engel A. , Borchers R. , Röckmann T.
Published: April 2010

Abstract. A comprehensive set of stratospheric balloon and aircraft samples was analyzed for the position-dependent isotopic composition of nitrous oxide (N2O). Results for a total of 220 samples from between 1987 and 2003 are presented, nearly tripling the number of mass-spectrometric N2O isotope measurements in the stratosphere published to date. Cryogenic balloon samples were obtained at polar (Kiruna/Sweden, 68° N), mid-latitude (southern France, 44° N) and tropical sites (Hyderabad/India, 18° N). Aircraft samples were collected with a newly-developed whole air sampler on board of the high-altitude aircraft M55 Geophysica during the EUPLEX 2003 campaign. All samples were analyzed by laboratory mass spectrometry for their 18O/16O and position-dependent 15N/14N isotope ratios with very high precision (standard deviation about 0.15 per mil for 18O/16O and average 15N/14N ratios, about 0.5 per mil for 15NNO/14NNO and N15NO/N14NO ratios). For mixing ratios above 200 nmol mol−1, relative isotope enrichments (δ values) and mixing ratios display a compact relationship, which is nearly independent of latitude and season and which can be explained equally well by Rayleigh fractionation or mixing. However, for mixing ratios below 200 nmol mol−1 this compact relationship gives way to meridional, seasonal and interannual variations. A comparison to a previously published mid-latitude balloon profile even shows large zonal variations, justifying the use of three-dimensional models for further data interpretation. In general, the magnitude of the apparent fractionation constants (apparent isotope effects) increases continuously with altitude and decreases from the equator to the North pole, which can be qualitatively understood by the interplay between the time-scales of N2O photochemistry and transport. Deviations from this behavior occur where polar vortex air mixes with nearly N2O-free upper stratospheric/mesospheric air (e.g., during the boreal winter of 2003 and possibly 1992). Aircraft observations in the polar vortex at mixing ratios below 200 nmol mol−1 deviate from isotope variations expected for both Rayleigh fractionation and end-member mixing, but could be explained by continuous weak mixing between intravortex and extravortex air (Plumb et al., 2000). Finally, correlations between 18O/16O and average 15N/14N isotope ratios or between the position-dependent 15N/14N isotope ratios show that photo-oxidation makes a large contribution to the total N2O sink in the lower stratosphere (up to 100%). Towards higher altitudes, the temperature dependence of these isotope correlations becomes visible in the stratospheric observations.
Long-memory processes in global ozone and temperature variations
Authors: Varotsos C. , Kirk-Davidoff D.
Published: April 2010

Abstract. Global column ozone and tropospheric temperature observations made by ground-based (1964–2004) and satellite-borne (1978–2004) instrumentation are analyzed. Ozone and temperature fluctuations in small time-intervals are found to be positively correlated to those in larger time-intervals in a power-law fashion. For temperature, the exponent of this dependence is larger in the mid-latitudes than in the tropics at long time scales, while for ozone, the exponent is larger in tropics than in the mid-latitudes. The ability of the models to reproduce this scaling could be a good test for improved predictions of future variations in ozone layer and global warming.
Key aspects of stratospheric tracer modeling
Authors: Bregman B. , Meijer E. , Scheele R.
Published: April 2010

Abstract. This study describes key aspects of global chemistry-transport models and the impact on stratospheric tracer transport. We concentrate on global models that use assimilated winds from numerical weather predictions, but the results also apply to tracer transport in general circulation models. We examined grid resolution, numerical diffusion and dispersion of the winds fields, the meteorology update time intervals, update frequency, and time interpolation. For this study we applied the three-dimensional chemistry-transport Tracer Model version 5 (TM5) and a trajectory model and performed several diagnoses focusing on different transport regimes. Covering different time and spatial scales, we examined (1) polar vortex dynamics during the Arctic winter, (2) the large-scale stratospheric meridional circulation, and (3) air parcel dispersion in the tropical lower stratosphere. Tracer distributions inside the Arctic polar vortex show considerably worse agreement with observations when the model grid resolution in the polar region is reduced to avoid numerical instability. Using time interpolated winds improve the tracer distributions only marginally. Considerable improvement is found when the update frequency of the assimilated winds is increased from 6 to 3h, both in the large-scale tracer distribution and the polar regions. It further reduces in particular the vertical dispersion of air parcels in the tropical lower stratosphere. The results in this study demonstrates significant progress in the use of assimilated meteorology in chemistry-transport models, which is important for both short- and long-term integrations.
The ASSET intercomparison of ozone analyses: method and first results
Authors: Geer A. J. , Lahoz W. A. , Bekki S. , Bormann N. , Errera Q. , Eskes H. J. , Fonteyn D. , Jackson D. R. , Juckes M. N. , Massart S. , Peuch V.-H. , Rharmili S. , Segers A.
Published: April 2010

Abstract. This paper examines 11 sets of ozone analyses from 7 different data assimilation systems. Two are numerical weather prediction (NWP) systems based on general circulation models (GCMs); the other five use chemistry transport models (CTMs). These systems contain either linearised or detailed ozone chemistry, or no chemistry at all. In most analyses, MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) ozone data are assimilated. Two examples assimilate SCIAMACHY (Scanning Imaging Absorption Spectrometer for Atmospheric Chartography) observations. The analyses are compared to independent ozone observations covering the troposphere, stratosphere and lower mesosphere during the period July to November 2003. Through most of the stratosphere (50 hPa to 1 hPa), biases are usually within ±10% and standard deviations less than 10% compared to ozonesondes and HALOE (Halogen Occultation Experiment). Biases and standard deviations are larger in the upper-troposphere/lower-stratosphere, in the troposphere, the mesosphere, and the Antarctic ozone hole region. In these regions, some analyses do substantially better than others, and this is mostly due to differences in the models. At the tropical tropopause, many analyses show positive biases and excessive structure in the ozone fields, likely due to known deficiencies in assimilated tropical wind fields and a degradation in MIPAS data at these levels. In the southern hemisphere ozone hole, only the analyses which correctly model heterogeneous ozone depletion are able to reproduce the near-complete ozone destruction over the pole. In the upper-stratosphere and mesosphere (above 5 hPa), some ozone photochemistry schemes caused large but easily remedied biases. The diurnal cycle of ozone in the mesosphere is not captured, except by the one system that includes a detailed treatment of mesospheric chemistry. In general, similarly good results are obtained no matter what the assimilation method (Kalman filter, three or four dimensional variational methods, direct inversion), or system (CTM or NWP system) and this in part reflects the generally good quality of the MIPAS ozone observations. Analyses based on SCIAMACHY total column are almost as good as the MIPAS analyses; analyses based on SCIAMACHY limb profiles are worse in some areas, due to problems in the SCIAMACHY retrievals. Using the analyses as a transfer standard, and treating MIPAS observations as point retrievals, it is seen that MIPAS is ~5% higher than HALOE in the mid and upper stratosphere and mesosphere (above 30 hPa), and of order 10% higher than ozonesonde and HALOE in the lower stratosphere (100 hPa to 30 hPa).
Vertical profiles of NOx chemistry in the polluted nocturnal boundary layer in Phoenix, AZ: I. Field observations by long-path DOAS
Authors: Wang S. , Ackermann R. , Stutz J.
Published: April 2010

Abstract. Nocturnal chemistry in the atmospheric boundary layer plays a key role in determining the initial chemical conditions for photochemistry during the following morning as well as influencing the budgets of O3 and NO2. Despite its importance, chemistry in the nocturnal boundary layer (NBL), especially in heavily polluted urban areas, has received little attention so far, which greatly limits the current understanding of the processes involved. In particular, the influence of vertical mixing on chemical processes gives rise to complex vertical profiles of various reactive trace gases and makes nocturnal chemistry altitude-dependent. The processing of pollutants is thus driven by a complicated, and not well quantified, interplay between chemistry and vertical mixing. In order to gain a better understanding of the altitude-dependent nocturnal chemistry in the polluted urban environment, a field study was carried out in the downtown area of Phoenix, AZ, in summer 2001. Vertical profiles of reactive species, such as O3, NO2, and NO3, were observed in the lowest 140 m of the troposphere throughout the night. The disappearance of these trace gas vertical profiles during the morning coincided with the morning transition from a stable NBL to a well-mixed convective layer. The vertical gradients of trace gas levels were found to be dependent on both surface NOx emission strength and the vertical stability of the NBL. The vertical gradients of Ox, the sum of O3 and NO2, were found to be much smaller than those of O3 and NO2, revealing the dominant role of NO emissions followed by the O3+NO reaction for the altitude-dependence of nocturnal chemistry in urban areas. Dry deposition, direct emissions, and other chemical production pathways of NO2 also play a role for the Ox distribution. Strong positive vertical gradients of NO3, that are predominantly determined by NO3 loss near the ground, were observed. The vertical profiles of NO3 and its reservoir species (N2O5) confirm earlier model results suggesting complex vertical distributions of atmospheric denoxification processes during the night.
Observations of lunar tides in the mesosphere and lower thermosphere at Arctic and middle latitudes
Authors: Sandford D. J. , Muller H. G. , Mitchell N. J.
Published: April 2010

Abstract. Meteor radars have been used to measure the horizontal winds in the mesosphere and lower thermosphere over Castle Eaton (52° N) in the UK and over Esrange (68° N) in Arctic Sweden. We consider a 16-year data set covering the interval 1988–2004 for the UK and a 6-year data set covering the interval 1999–2005 for the Arctic. The signature of the 12.42-h (M2) lunar tide has been identified at both locations. The lunar tide is observed to reach amplitudes as large as 11 ms−1. The Arctic radar has an interferometer and so allows investigation of the vertical structure of the lunar tide. At both locations the tide has maximum amplitudes in winter with a second autumnal maximum. The amplitude is found to increase with height over the 80–100 km height range observed. Vertical wavelengths are very variable, ranging from about 15 km in summer to more than 60 km in winter. Comparisons with the Vial and Forbes, 1994 model reveals generally good agreement, except in the case of the summer vertical wavelengths which are observed to be significantly shorter than predicted.
Simulations of preindustrial, present-day, and 2100 conditions in the NASA GISS composition and climate model G-PUCCINI
Authors: Shindell D. T. , Faluvegi G. , Unger N. , Aguilar E. , Schmidt G. A. , Koch D. M. , Bauer S. E. , Miller R. L.
Published: April 2010

Abstract. A model of atmospheric composition and climate has been developed at the NASA Goddard Institute for Space Studies (GISS) that includes composition seamlessly from the surface to the lower mesosphere. The model is able to capture many features of the observed magnitude, distribution, and seasonal cycle of trace species. The simulation is especially realistic in the troposphere. In the stratosphere, high latitude regions show substantial biases during period when transport governs the distribution as meridional mixing is too rapid in this model version. In other regions, including the extrapolar tropopause region that dominates radiative forcing (RF) by ozone, stratospheric gases are generally well-simulated. The model's stratosphere-troposphere exchange (STE) agrees well with values inferred from observations for both the global mean flux and the ratio of Northern to Southern Hemisphere downward fluxes. Simulations of preindustrial (PI) to present-day (PD) changes show tropospheric ozone burden increases of 11% while the stratospheric burden decreases by 18%. The resulting tropopause RF values are −0.06 W/m2 from stratospheric ozone and 0.40 W/m2 from tropospheric ozone. Global mean mass-weighted OH decreases by 16% from the PI to the PD. STE of ozone also decreased substantially during this time, by 14%. Comparison of the PD with a simulation using 1979 pre-ozone hole conditions for the stratosphere shows a much larger downward flux of ozone into the troposphere in 1979, resulting in a substantially greater tropospheric ozone burden than that seen in the PD run. This implies that reduced STE due to Antarctic ozone depletion may have offset as much as 2/3 of the tropospheric ozone burden increase from PI to PD. However, the model overestimates the downward flux of ozone at high Southern latitudes, so this estimate is likely an upper limit. In the future, the tropospheric ozone burden increases sharply in 2100 for the A1B and A2 scenarios, by 41% and 101%, respectively. The primary reason is enhanced STE, which increases by 71% and 124% in the two scenarios. Chemistry and dry deposition both change so as to reduce ozone, partially in compensation for the enhanced STE. Thus even in the high-pollution A2 scenario, and certainly in A1B, the increased ozone influx dominates the burden changes. However, STE has the greatest influence on middle and high latitudes and towards the upper troposphere, so RF and surface air quality are dominated by emissions. Net RF values due to projected ozone changes depend strongly on the scenario, with 0.1 W/m2 for A1B and 0.8 W/m2 for A2. Changes in oxidation capacity are also scenario dependent, with values of plus and minus seven percent in the A2 and A1B scenarios, respectively.
Centennial evolution of the atmospheric methane budget: what do the carbon isotopes tell us?
Authors: Lassey K. R. , Etheridge D. M. , Lowe D. C. , Smith A. M. , Ferretti D. F.
Published: April 2010

Abstract. Little is known about how the methane source inventory and sinks have evolved over recent centuries. New and detailed records of methane mixing ratio and isotopic composition (12CH4, 13CH4 and 14CH4) from analyses of air trapped in polar ice and firn can enhance this knowledge. We use existing bottom-up constructions of the source history, including ''EDGAR''-based constructions, to assemble a model of the evolving global budget for methane and for its carbon isotope composition through the 20th century. By matching such budgets to atmospheric data, we examine the constraints imposed by isotope information on those budget evolutions. Balancing both 12CH4 and 13CH4 budgets requires participation by a highly-fractionating atmospheric sink such as active chlorine (removing at least 10 Tg yr-1), which has been proposed independently. Examining a companion budget evolution for 14CH4 exposes uncertainties in inferring the fossil-methane source from atmospheric 14CH4 data. Specifically, methane evolution during the nuclear era is sensitive to the cycling dynamics of ''bomb 14C'' (originating from atmospheric weapons tests) through the biosphere. In addition, since ca 1970, direct production and release of 14CH4 from nuclear-power facilities is influential but poorly quantified. Atmospheric 14CH4 determinations in the nuclear era have the potential to better characterize biospheric carbon cycling and to better quantify the ill-determined nuclear-power source.
Aerosol activation and cloud processing in the global aerosol-climate model ECHAM5-HAM
Authors: Roelofs G. J. , Stier P. , Feichter J. , Vignati E. , Wilson J.
Published: April 2010

Abstract. A parameterization for cloud processing is presented that calculates activation of aerosol particles to cloud drops, cloud drop size, and pH-dependent aqueous phase sulfur chemistry. The parameterization is implemented in the global aerosol-climate model ECHAM5-HAM. The cloud processing parameterization uses updraft speed, temperature, and aerosol size and chemical parameters simulated by ECHAM5-HAM to estimate the maximum supersaturation at the cloud base, and subsequently the cloud drop number concentration (CDNC) due to activation. In-cloud sulfate production occurs through oxidation of dissolved SO2 by ozone and hydrogen peroxide. The model simulates realistic distributions for annually averaged CDNC although it is underestimated especially in remote marine regions. On average, CDNC is dominated by particles from the accumulation mode, with smaller contributions from the Aitken and coarse modes. The simulations indicate that in-cloud sulfate production is a potentially important source of accumulation mode sized cloud condensation nuclei, due to chemical growth of activated Aitken particles and to enhanced coalescence of processed particles. The strength of this source depends on the distribution of produced sulfate over the activated modes. This distribution is affected by uncertainties in many parameters that play a direct role in particle activation, such as the updraft velocity, the aerosol chemical composition and the organic solubility, and the simulated CDNC is found to be relatively sensitive to these uncertainties.
Impact of H2SO4/H2O coating and ice crystal size on radiative properties of sub-visible cirrus
Authors: Räisänen P. , Bogdan A. , Sassen K. , Kulmala M. , Molina M. J.
Published: April 2010

Abstract. Recent laboratory experiments showed that at conditions resembling those near the tropopause region, small quasi-spherical ice particles can be coated by a liquid H2SO4/H2O over-layer formed after the freezing of diluted sulfuric acid/water aerosol drops. Here, idealized radiative transfer tests are conducted to evaluate the impact that such an over-layer would have on the radiative effects produced by sub-visible cirrus clouds (SVCs). The calculations show that the over-layer increases both the shortwave (SW) and longwave (LW) cloud radiative effects (CRE), but the impact is small: ~0.02 W m-2, or even less, for the total (LW+SW) CRE at the top of the atmosphere. For the smallest ice particles, for which the over-layer is thickest, the fractional change in CRE can, however, reach ~20% for the SW CRE and over 50% for the LW CRE. The dependence of LW and SW CRE on particle size is also considered in the paper. Calculations for spherical uncoated ice particles show that even for high, optically thin cirrus clouds, the total CRE can be negative, if the diameter of the particles is smaller than about 3–4 µm. Apart from the SVCs, this result could be relevant for contrail cirrus clouds, which are believed to consist of large numbers of very small ice particles.
Technical Note: Anthropogenic and natural offline emissions and the online EMissions and dry DEPosition submodel EMDEP of the Modular Earth Submodel system (MESSy)
Authors: Ganzeveld L. N. , van Aardenne J. A. , Butler T. M. , Lawrence M. G. , Metzger S. M. , Stier P. , Zimmermann P. , Lelieveld J.
Published: April 2010

Abstract. We present the online calculated Earth's surface trace gas and aerosol emissions and dry deposition in the Modular Earth Submodel System (MESSy) submodel EMDEP as well as the currently applied anthropogenic and natural emissions inventories. These inventories, being read-in by the MESSy submodel OFFLEM, include the industrial, fossil fuel, agricultural and biomass burning emissions considering emission height profiles as a function of the source category based on the EDGAR v3.2 fast track 2000 inventory. Terrestrial and marine emissions of a selection of trace gases and aerosols are calculated online in EMDEP using climate model parameters such as wind speed, temperature and land cover and land use parameters. The online dry deposition calculation includes gases and aerosols, where the default selection for the trace gases for the dry deposition scheme can be easily extended using a commonly applied method based on trace gas solubility and reactivity. In general, the simulated global annual emissions agree with previously reported inventories, although differences exist, partly dependent on the applied model resolution. A high sensitivity of the simulated dry deposition to the applied emission height profiles stresses the importance of a realistic and consistent representation of the spatial and temporal variability in surface exchange processes in Earth system models.
Technical Note: Implementation of prescribed (OFFLEM), calculated (ONLEM), and pseudo-emissions (TNUDGE) of chemical species in the Modular Earth Submodel System (MESSy)
Authors: Kerkweg A. , Sander R. , Tost H. , Jöckel P.
Published: April 2010

Abstract. We present the submodels OFFLEM, ONLEM, and TNUDGE for the Modular Earth Submodel System (MESSy). Prescribed emissions from input files are handled by OFFLEM. ONLEM deals with online-calculated emissions, i.e., emissions that are calculated during the simulation. The submodel TNUDGE uses the ''tracer nudging'' technique for pseudo-sources and -sinks. For species with highly uncertain emission fluxes and/or with sufficiently long lifetimes, e.g., CH4, it is common to create such pseudo-fluxes by prescribing the observed mixing ratio of the species at a given boundary (e.g., the mixing ratio of methane at the surface, or the ozone mixing ratio at the tropopause). All three submodels substantially simplify the inclusion of emissions into a model. Specific emissions can easily be switched on or off. New prescribed emissions can be included without rewriting any code. New online emissions only require one additional subroutine containing the new parameterization. A major advantage is that input fields at arbitrary resolution can be used. The problem of incompatible grids between emission data and model is overcome by utilizing the MESSy data import interface. To further simplify the creation of new offline emission data, the preprocessing program EDGAR2NC is provided. EDGAR2NC transforms files from the EDGAR format into the netCDF format which is required by OFFLEM. The presented routines are a part of the community modeling project MESSy and can be made available for use to the atmospheric modeling community.
Winter and summer time size distributions and densities of traffic-related aerosol particles at a busy highway in Helsinki
Authors: Virtanen A. , Rönkkö T. , Kannosto J. , Mäkelä J. M. , Keskinen J. , Pakkanen T. , Pirjola L. , Hämeri K.
Published: April 2010

Abstract. The number concentration and size distribution of traffic related particles were measured at road-side in Helsinki. Two winter campaigns took place in 10–26 February 2003 and 28 January–12 February 2004 and two summer campaigns in 12–27 August 2003 and 6–20 August 2004. The measurements were performed simultaneously at distances of 9 m and 65 m from the highway. This study concentrates on data that were measured when the wind direction was from the road to the measurement site. The total concentration in winter time was 2–3 times higher than in summer time and it was dominated by nucleation mode particles. The particles smaller than 63 nm (at aerodynamic size) constitute ~90% of all particles in winter time and ~80% of particles in summer time. The particle total concentration increases with increasing traffic rate. The dependence of particles smaller than 63 nm on traffic rate is stronger than for particles larger than 63 nm both during summer and winter. The particle distribution at the roadside consists of two distinguishable modes. The GMD of nucleation mode (Mode 1) was 20.3 nm at summer and 18.9 nm at winter. The GMD of the larger mode (Mode 2) was 72.0 nm at summer and 75.1 nm at winter. The GMD values of the modes do not depend on traffic rate. The average density value for Mode 1 particles was 1.0 g/cm3 both in summer and winter time, while the average density value for Mode 2 was 1.5±0.1 g/cm3 and 1.8±0.3 g/cm3 for summer and winter time, respectively.
Stable isotopes provide revised global limits of aerobic methane emissions from plants
Authors: Ferretti D. F. , Miller J. B. , White J. W. C. , Lassey K. R. , Lowe D. C. , Etheridge D. M.
Published: April 2010

Abstract. Recently Keppler et al. (2006) discovered a surprising new source of methane – terrestrial plants under aerobic conditions, with an estimated global production of 62–236 Tg yr−1 by an unknown mechanism. This is ~10–50% of the annual total of methane entering the modern atmosphere and ~30–100% of annual methane entering the pre-industrial (0 to 1700 AD) atmosphere. Here we test this reported global production of methane from plants against ice core records of atmospheric methane concentration (CH4) and stable carbon isotope ratios (δ13CH4) over the last 2000 years. Our top-down approach determines that global plant emissions must be much lower than proposed by Keppler et al. (2006) during the last 2000 years and are likely to lie in the range 0–46 Tg yr−1.
Small HONO emissions from snow surfaces at Browning Pass, Antarctica
Authors: Beine H. J. , Amoroso A. , Dominé F. , King M. D. , Nardino M. , Ianniello A. , France J. L.
Published: April 2010

Abstract. Measured Fluxes of nitrous acid at Browning Pass, Antarctica were very low, despite conditions that are generally understood as favorable for HONO emissions, including: acidic snow surfaces, an abundance of NO3− anions in the snow surface, and abundant UV light for NO3− photolysis. Photochemical modeling suggests noon time HONO fluxes of 5–10 nmol m−2 h−1; the measured fluxes, however, were close to zero throughout the campaign. The analysis of soluble mineral ions in snow reveals that the NO3− ion is probably present in aged snows as NaNO3. This is peculiar to our study site, and we suggest that this may affect the photochemical reactivity of NO3−, by preventing the release of products, or providing a reactive medium for newly formed HONO. In fresh snow, the NO3− ion is probably present as dissolved or adsorbed HNO3 and yet, no HONO emissions were observed. We speculate that HONO formation from NO3− photolysis may involve electron transfer reactions of NO2 from photosensitized organics and that fresh snows at our site had insufficient concentrations of adequate organic compounds to favor this reaction.
Seasonal variation of PM10 main constituents in two valleys of the French Alps. I: EC/OC fractions
Authors: Aymoz G. , Jaffrezo J.-L. , Chapuis D. , Cozic J. , Maenhaut W.
Published: April 2010

Abstract. Daily PM10 samples were collected at two urban sites within two valleys in the French Alps (Chamonix and St Jean de Maurienne) during a period of two and a half years. The carbonaceous species EC (elemental carbon) and OC (organic carbon) were analysed to investigate the possible sources of EC and OC, and their seasonal variations. Mean OC concentrations are in the very high range of concentrations measured for other European sites, and represent at least one third of the PM10 mass on each site. On the basis of the comparison between EC and OC concentrations with several tracers, we were able to show that their main sources are local primary combustion sources. Biomass burning emissions (residential heating) have a significant impact on OC concentrations while heavy duty traffic emissions have an impact only on EC concentrations. Finally, we estimated the contribution of SOA (secondary organic carbon) to OC, using the EC-to-OC primary ratio method (Castro et al., 1999) and demonstrated that the calculation of SOA mass with this method is highly uncertain, if the hypothesis of a constant primary EC-to-OC ratio is not very closely examined.
Towards a climatology of stratospheric bromine monoxide from SCIAMACHY limb observations
Authors: Sheode N. , Sinnhuber B.-M. , Rozanov A. , Burrows J. P.
Published: April 2010

Abstract. Retrievals of stratospheric bromine monoxide (BrO) profiles from two years of limb measurements from the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) instrument onboard ENVISAT are analysed and a global climatology of stratospheric BrO is prepared. A comparison of the SCIAMACHY BrO retrievals with a set of four balloon-borne BrO profiles shows mean relative differences in the altitude range from 18 to 30 km between −42%. The SCIAMACHY BrO observations provide for the first time a picture of the seasonal variation of stratospheric BrO on a global scale. At mid-latitudes of both hemispheres BrO shows a strong seasonal cycle with a maximum in winter and a minimum in summer. The seasonal variation of BrO is closely correlated with changes in nitrogen dioxide (NO2), confirming our present understanding of gas phase bromine chemistry. Using the SCIAMACHY BrO observations together with the calculated bromine partitioning from a photochemical model constrained by the SCIAMACHY NO2 observations, the total stratospheric bromine loading is estimated to be 18.5±4 pptv. This indicates a contribution of about 3.5±4 pptv from short lived bromine species in addition to methyl bromide and the halons.