bluuebunny/crossref_metadata_2025 huggingface dataset:
Aerosol absorption and radiative forcing
Authors: Stier P. , Seinfeld J. H. , Kinne S. , Boucher O.
Published: April 2010

Abstract. We present a comprehensive examination of aerosol absorption with a focus on evaluating the sensitivity of the global distribution of aerosol absorption to key uncertainties in the process representation. For this purpose we extended the comprehensive aerosol-climate model ECHAM5-HAM by effective medium approximations for the calculation of aerosol effective refractive indices, updated black carbon refractive indices, new cloud radiative properties considering the effect of aerosol inclusions, as well as by modules for the calculation of long-wave aerosol radiative properties and instantaneous aerosol forcing. The evaluation of the simulated aerosol absorption optical depth with the AERONET sun-photometer network shows a good agreement in the large scale global patterns. On a regional basis it becomes evident that the update of the BC refractive indices to Bond and Bergstrom (2006) significantly improves the previous underestimation of the aerosol absorption optical depth. In the global annual-mean, absorption acts to reduce the short-wave anthropogenic aerosol top-of-atmosphere (TOA) radiative forcing clear-sky from −0.79 to −0.53 W m−2 (33%) and all-sky from −0.47 to −0.13 W m−2 (72%). Our results confirm that basic assumptions about the BC refractive index play a key role for aerosol absorption and radiative forcing. The effect of the usage of more accurate effective medium approximations is comparably small. We demonstrate that the diversity in the AeroCom land-surface albedo fields contributes to the uncertainty in the simulated anthropogenic aerosol radiative forcings: the usage of an upper versus lower bound of the AeroCom land albedos introduces a global annual-mean TOA forcing range of 0.19 W m−2 (36%) clear-sky and of 0.12 W m−2 (92%) all-sky. The consideration of black carbon inclusions on cloud radiative properties results in a small global annual-mean all-sky absorption of 0.05 W m−2 and a positive TOA forcing perturbation of 0.02 W m−2. The long-wave aerosol radiative effects are small for anthropogenic aerosols but become of relevance for the larger natural dust and sea-salt aerosols.
Middle atmosphere water vapour and dynamical features in aircraft measurements and ECMWF analyses
Authors: Feist D. G. , Geer A. J. , Müller S. , Kämpfer N.
Published: April 2010

Abstract. The European Centre for Medium-Range Weather Forecasts (ECMWF) provides global analyses of atmospheric humidity from the ground to the lower mesosphere. Unlike in the troposphere, in the stratosphere no humidity observations are assimilated. Humidity analyses here are essentially the results of a free-running model constrained by the ECMWF's analysed wind fields. So far only the broad-scale features of the resulting stratospheric water vapour distribution have been validated. This study provides the first in-depth comparison of stratospheric humidity from ECMWF with observations from an airborne microwave radiometer that has measured the distribution of stratospheric water vapour over an altitude range of roughly 15–60 km on several flight campaigns since 1998. The aircraft measurements provide a horizontal resolution that cannot be achieved by current satellite instruments. This study examines dynamical features in the moisture fields such as filamentation and the vortex edge, finding that features in the ERA-40 humidity analyses often do correspond to real atmospheric events that are seen in the aircraft measurements. However, the comparisons also show that in general the ECMWF model produces an unrealistically moist mesosphere. As a result it cannot replicate the descent of relatively dry mesospheric air into the polar vortex in winter and spring.
Influence of trans-Pacific pollution transport on acyl peroxy nitrate abundances and speciation at Mount Bachelor Observatory during INTEX-B
Authors: Wolfe G. M. , Thornton J. A. , McNeill V. F. , Jaffe D. A. , Reidmiller D. , Chand D. , Smith J. , Swartzendruber P. , Flocke F. , Zheng W.
Published: April 2010

Abstract. We present month-long observations of speciated acyl peroxy nitrates (APNs), including PAN, PPN, MPAN, APAN, and the sum of PiBN and PnBN, measured at the Mount Bachelor Observatory (MBO) as part of the INTEX-B collaborative field campaign during spring 2006. APN abundances, measured by thermal dissociation-chemical ionization mass spectrometry (TD-CIMS), are discussed in terms of differing contributions from the boundary layer (BL) and the free troposphere (FT) and in the context of previous APN measurements in the NE Pacific region. PAN mixing ratios range from 11 to 3955 pptv, with a mean value of 334 pptv for the full measurement period. PPN is linearly correlated with PAN (r2=0.96), with an average abundance of 6.5% relative to PAN; other APNs are generally <1% of PAN. Diurnal cycles and relationships of APNs with ozone reveal a gradient in hydrocarbon chemistry between the BL and the FT. On average, levels of APNs, ozone and PPN/PAN are substantially higher in FT air relative to BL air, suggesting that this site is strongly influenced by distant pollution sources. To estimate the impact of long-range transport of Asian pollution on atmospheric composition at MBO, we perform a detailed analysis utilizing HYSPLIT back trajectories. This analysis suggests that trans-Pacific transport of Asian pollution leads to substantial increases in APN and ozone mixing ratios at MBO, especially when transport occurs via the free troposphere. The ensemble of trajectories indicate that Asian-influenced free tropospheric air was sampled in ~16% of our data and contained a median PAN mixing ratio double that of the full dataset.
Seasonal variation of ozone deposition to a tropical rain forest in southwest Amazonia
Authors: Rummel U. , Ammann C. , Kirkman G. A. , Moura M. A. L. , Foken T. , Andreae M. O. , Meixner F. X.
Published: April 2010

Abstract. Within the project EUropean Studies on Trace gases and Atmospheric CHemistry as a contribution to Large-scale Biosphere-atmosphere experiment in Amazonia (LBA-EUSTACH), we performed tower-based eddy covariance measurements of O3 flux above an Amazonian primary rain forest at the end of the wet and dry season. Ozone deposition revealed distinct seasonal differences in the magnitude and diel variation. In the wet season, the rain forest was an effective O3 sink with a mean daytime (midday) maximum deposition velocity of 2.3 cm s−1, and a corresponding O3 flux of −11 nmol m−2 s−1. At the end of the dry season, the ozone mixing ratio was about four times higher (up to maximum values of 80 ppb) than in the wet season, as a consequence of strong regional biomass burning activity. However, the typical maximum daytime deposition flux was very similar to the wet season. This results from a strong limitation of daytime O3 deposition due to reduced plant stomatal aperture as a response to large values of the specific humidity deficit. As a result, the average midday deposition velocity in the dry burning season was only 0.5 cm s−1. The large diel ozone variation caused large canopy storage effects that masked the true diel variation of ozone deposition mechanisms in the measured eddy covariance flux, and for which corrections had to be made. In general, stomatal aperture was sufficient to explain the largest part of daytime ozone deposition. However, during nighttime, chemical reaction with nitrogen monoxide (NO) was found to contribute substantially to the O3 sink in the rain forest canopy. Further contributions were from non-stomatal plant uptake and other processes that could not be clearly identified. Measurements, made simultaneously on a 22 years old cattle pasture enabled the spatially and temporally direct comparison of O3 dry deposition values from this site with typical vegetation cover of deforested land in southwest Amazonia to the results from the primary rain forest. The mean ozone deposition to the pasture was found to be systematically lower than that to the forest by 30% in the wet and 18% in the dry season.
ACE-FTS observation of a young biomass burning plume: first reported measurements of C2H4, C3H6O, H2CO and PAN by infrared occultation from space
Authors: Coheur P.-F. , Herbin H. , Clerbaux C. , Hurtmans D. , Wespes C. , Carleer M. , Turquety S. , Rinsland C. P. , Remedios J. , Hauglustaine D. , Boone C. D. , Bernath P. F.
Published: April 2010

Abstract. In the course of our study of the upper tropospheric composition with the infrared Atmospheric Chemistry Experiment – Fourier Transform Spectrometer (ACE–FTS), we found an occultation sequence that on 8 October 2005, sampled a remarkable plume near the east coast of Tanzania. Model simulations of the CO distribution in the Southern hemisphere are performed for this period and they suggest that the emissions for this event likely originated from a nearby forest fire, after which the plume was transported from the source region to the upper troposphere. Taking advantage of the very high signal-to-noise ratio of the ACE–FTS spectra over a wide wavenumber range (750–4400 cm−1), we present in-depth analyses of the chemical composition of this plume in the middle and upper troposphere, focusing on the measurements of weakly absorbing pollutants. For this specific biomass burning event, we report simultaneous observations of an unprecedented number of organic species. Measurements of C2H4 (ethene), C3H4 (propyne), H2CO (formaldehyde), C3H6O (acetone) and CH3COO2NO2 (peroxyacetylnitrate, abbreviated as PAN) are the first reported detections using infrared occultation spectroscopy from satellites. Based on the lifetime of the emitted species, we discuss the photochemical age of the plume and also report, whenever possible, the enhancement ratios relative to CO.
Contribution of primary carbonaceous aerosol to cloud condensation nuclei: processes and uncertainties evaluated with a global aerosol microphysics model
Authors: Pierce J. R. , Chen K. , Adams P. J.
Published: April 2010

Abstract. This paper explores the impacts of primary carbonaceous aerosol on cloud condensation nuclei (CCN) concentrations in a global climate model with size-resolved aerosol microphysics. Organic matter (OM) and elemental carbon (EC) from two emissions inventories were incorporated into a preexisting model with sulfate and sea-salt aerosol. The addition of primary carbonaceous aerosol increased CCN(0.2%) concentrations by 65–90% in the globally averaged surface layer depending on the carbonaceous emissions inventory used. Sensitivity studies were performed to determine the relative importance of organic solubility/hygroscopicity in predicting CCN. In a sensitivity study where carbonaceous aerosol was assumed to be completely insoluble, concentrations of CCN(0.2%) still increased by 40–50% globally over the no carbonaceous simulation because primary carbonaceous emissions were able to become CCN via condensation of sulfuric acid. This shows that approximately half of the contribution of primary carbonaceous particles to CCN in our model comes from the addition of new particles (seeding effect) and half from the contribution of organic solute (solute effect). The solute effect tends to dominate more in areas where there is less inorganic aerosol than organic aerosol and the seeding effect tends to dominate in areas where there is more inorganic aerosol than organic aerosol. It was found that an accurate simulation of the number size distribution is necessary to predict the CCN concentration but assuming an average chemical composition will generally give a CCN concentration within a factor of 2. If a "typical" size distribution is assumed for each species when calculating CCN, such as is done in bulk aerosol models, the mean error relative to a simulation with size resolved microphysics is on the order of 35%. Predicted values of carbonaceous aerosol mass and aerosol number were compared to observations and the model showed average errors of a factor of 3 for carbonaceous mass and a factor of 4 for total aerosol number; however, errors in the accumulation mode concentrations were found to be lower in comparisons with European and marine observations.. The errors in CN and carbonaceous mass may be reduced by improving the emission size distributions of both primary sulfate and primary carbonaceous aerosol.
Technical Note: The air quality modeling system Polyphemus
Authors: Mallet V. , Quélo D. , Sportisse B. , Ahmed de Biasi M. , Debry É. , Korsakissok I. , Wu L. , Roustan Y. , Sartelet K. , Tombette M. , Foudhil H.
Published: April 2010

Abstract. Polyphemus is an air quality modeling platform which aims at covering the scope and the abilities of modern air quality systems. It deals with applications from local scale to continental scale, using two Gaussian models and two Eulerian models. It manages passive tracers, radioactive decay, photochemistry and aerosol dynamics. The structure of the system includes four independent levels with data management, physical parameterizations, numerical solvers and high-level methods such as data assimilation. This enables sensitivity and uncertainty analysis, primarily through multimodel approaches. On top of the models, drivers implement advanced methods such as model coupling or data assimilation.
Technical Note: Use of a beam width probe in an Aerosol Mass Spectrometer to monitor particle collection efficiency in the field
Authors: Salcedo D. , Onasch T. B. , Canagaratna M. R. , Dzepina K. , Huffman J. A. , Jayne J. T. , Worsnop D. R. , Kolb C. E. , Weimer S. , Drewnick F. , Allan J. D. , Delia A. E. , Jimenez J. L.
Published: April 2010

Abstract. Two Aerodyne Aerosol Mass Spectrometers (Q-AMS) were deployed in Mexico City, during the Mexico City Metropolitan Area field study (MCMA-2003) from 29 March–4 May 2003 to investigate particle concentrations, sources, and processes. We report the use of a particle beam width probe (BWP) in the field to quantify potential losses of particles due to beam broadening inside the AMS caused by particle shape (nonsphericity) and particle size. Data from this probe show that no significant mass of particles was lost due to excessive beam broadening; i.e. the shape- and size-related collection efficiency (Es) of the AMS during this campaign was approximately one. Comparison of the BWP data from MCMA-2003 with other campaigns shows that the same conclusion holds for several other urban, rural and remotes sites. This means that the aerodynamic lens in the AMS is capable of efficiently focusing ambient particles into a well defined beam and onto the AMS vaporizer for particles sampled in a wide variety of environments. All the species measured by the AMS during MCMA-2003 have similar attenuation profiles which suggests that the particles that dominate the mass concentration were internally mixed most of the time. Only for the smaller particles (especially below 300 nm), organic and inorganic species show different attenuation versus particle size which is likely due to partial external mixing of these components. Changes observed in the focusing of the particle beam in time can be attributed, in part, to changes in particle shape (i.e. due to relative humidity) and size of the particles sampled. However, the relationships between composition, atmospheric conditions, and particle shape and size appear to be very complex and are not yet completely understood.
A cloud filtering method for microwave upper tropospheric humidity measurements
Authors: Buehler S. A. , Kuvatov M. , Sreerekha T. R. , John V. O. , Rydberg B. , Eriksson P. , Notholt J.
Published: April 2010

Abstract. The paper presents a cloud filtering method for upper tropospheric humidity (UTH) measurements at 183.31±1.00 GHz. The method uses two criteria: a viewing angle dependent threshold on the brightness temperature at 183.31±1.00 GHz, and a threshold on the brightness temperature difference between another channel and 183.31±1.00 GHz. Two different alternatives, using 183.31±3.00 GHz or 183.31±7.00 GHz as the other channel, are studied. The robustness of this cloud filtering method is demonstrated by a mid-latitudes winter case study. The paper then studies different biases on UTH climatologies. Clouds are associated with high humidity, therefore the possible dry bias introduced by cloud filtering is discussed and compared to the wet biases introduced by the clouds radiative effect if no filtering is done. This is done by means of a case study, and by means of a stochastic cloud database with representative statistics for midlatitude conditions. Both studied filter alternatives perform nearly equally well, but the alternative using 183.31±3.00 GHz as other channel is preferable, because that channel is less likely to see the Earth's surface than the one at 183.31±7.00 GHz. The consistent result of all case studies and for both filter alternatives is that both cloud wet bias and cloud filtering dry bias are modest for microwave data. The recommended strategy is to use the cloud filtered data as an estimate for the true all-sky UTH value, but retain the unfiltered data to have an estimate of the cloud induced uncertainty. The focus of the paper is on midlatitude data, since atmospheric data to test the filter for that case were readily available. The filter is expected to be applicable also to subtropical and tropical data, but should be further validated with case studies similar to the one presented here for those cases.
Ozone production and hydrocarbon reactivity in Hong Kong, Southern China
Authors: Zhang J. , Wang T. , Chameides W. L. , Cardelino C. , Kwok J. , Blake D. R. , Ding A. , So K. L.
Published: April 2010

Abstract. Data obtained in Hong Kong during the Hong Kong and the Pearl River Delta (PRD) Pilot Air Monitoring Study in autumn 2002 are analyzed to unravel the relationship between ground-level ozone (O3), pollution precursors, and cross-border transport. Ten ozone episodes, during which the hourly O3 concentration exceeded 100 ppbv in 9 cases and 90 ppbv in one case, are subject to detailed analysis, including one case with hourly O3 of 203 ppbv, which is the highest concentration on record to date in Hong Kong. Combined with high-resolution back trajectories, dCO/dNOy (the ratio of enhancement of CO concentration above background to that of NOy) is used to define whether O3 is locally or regionally produced. Five out of the ten Hong Kong O3-episodes studied show a "pollution signature" that is indicative of impact from Guangdong Province. Examination of speciated volatile organic compounds (VOCs) shows that the reactivity of VOCs is dominated by anthropogenic VOCs, of which the reactive aromatics dominate, in particular xylenes and toluene. Calculations using a photochemical box model indicate that between 50–100% of the O3 increase observed in Hong Kong during the O3 episodes can be explained by photochemical generation within the Hong Kong area, provided that nitrous acid (HONO) is present at the concentrations derived from this study. An Observation-Based Model (OBM) is used to calculate the sensitivity of the O3 production to changes in the concentrations of the precursor compounds. Generally the production of O3 throughout much of the Hong Kong area is limited by VOCs, while high nitric oxide (NO) concentrations suppress O3 concentration.
The 1985 Southern Hemisphere mid-latitude total column ozone anomaly
Authors: Bodeker G. E. , Garny H. , Smale D. , Dameris M. , Deckert R.
Published: April 2010

Abstract. One of the most significant events in the evolution of the ozone layer over southern mid-latitudes since the late 1970s was the large decrease observed in 1985. This event remains unexplained and a detailed investigation of the mechanisms responsible for the event has not previously been undertaken. In this study, the 1985 Southern Hemisphere mid-latitude total column ozone anomaly is analyzed in detail based on observed daily total column ozone fields, stratospheric dynamical fields, and calculated diagnostics of stratospheric mixing. The 1985 anomaly appears to result from a combination of (i) an anomaly in the meridional circulation resulting from the westerly phase of the equatorial quasi-biennial oscillation (QBO), (ii) weaker transport of ozone from its tropical mid-stratosphere source across the sub-tropical barrier to mid-latitudes related to the particular phasing of the QBO with respect to the annual cycle, and (iii) a solar cycle induced reduction in ozone. Similar QBO and solar cycle influences prevailed in 1997 and 2006 when again total column ozone was found to be suppressed over southern mid-latitudes. The results based on observations are compared and contrasted with analyses of ozone and dynamical fields from the ECHAM4.L39(DLR)/CHEM coupled chemistry-climate model (hereafter referred to as E39C). Equatorial winds in the E39C model are nudged towards observed winds between 10° S and 10° N and the ability of this model to produce an ozone anomaly in 1985, similar to that observed, confirms the role of the QBO in effecting the anomaly.
Two adaptive radiative transfer schemes for numerical weather prediction models
Authors: Venema V. , Schomburg A. , Ament F. , Simmer C.
Published: April 2010

Abstract. Radiative transfer calculations in atmospheric models are computationally expensive, even if based on simplifications such as the δ-two-stream approximation. In most weather prediction models these parameterisation schemes are therefore called infrequently, accepting additional model error due to the persistence assumption between calls. This paper presents two so-called adaptive parameterisation schemes for radiative transfer in a limited area model: A perturbation scheme that exploits temporal correlations and a local-search scheme that mainly takes advantage of spatial correlations. Utilising these correlations and with similar computational resources, the schemes are able to predict the surface net radiative fluxes more accurately than a scheme based on the persistence assumption. An important property of these adaptive schemes is that their accuracy does not decrease much in case of strong reductions in the number of calls to the δ-two-stream scheme. It is hypothesised that the core idea can also be employed in parameterisation schemes for other processes and in other dynamical models.
Size distributions of non-volatile particle residuals (Dp<800 nm) at a rural site in Germany and relation to air mass origin
Authors: Engler C. , Rose D. , Wehner B. , Wiedensohler A. , Brüggemann E. , Gnauk T. , Spindler G. , Tuch T. , Birmili W.
Published: April 2010

Abstract. Atmospheric aerosol particle size distributions at a continental background site in Eastern Germany were examined for a one-year period. Particles were classified using a twin differential mobility particle sizer in a size range between 3 and 800 nm. As a novelty, every second measurement of this experiment involved the removal of volatile chemical compounds in a thermodenuder at 300°C. This concept allowed to quantify the number size distribution of non-volatile particle cores – primarily associated with elemental carbon, and to compare this to the original non-conditioned size distribution. As a byproduct of the volatility analysis, new particles originating from nucleation inside the thermodenuder can be observed, however, overwhelmingly at diameters below 6 nm. Within the measurement uncertainty, every particle down to particle sizes of 15 nm is concluded to contain a non-volatile core. The volume fraction of non-volatile particulate matter (non-conditioned diameter < 800 nm) varied between 10 and 30% and was largely consistent with the experimentally determined mass fraction of elemental carbon. The average size of the non-volatile particle cores was estimated as a function of original non-conditioned size using a summation method, which showed that larger particles (>200 nm) contained more non-volatile compounds than smaller particles (<50 nm), thus indicating a significantly different chemical composition. Two alternative air mass classification schemes based on either, synoptic chart analysis (Berliner Wetterkarte) or back trajectories showed that the volume and number fraction of non-volatile cores depended less on air mass than the total particle number concentration. In all air masses, the non-volatile size distributions showed a more and a less volatile ("soot") mode, the latter being located at about 50 nm. During unstable conditions and in maritime air masses, smaller values were observed compared to stable or continental conditions. This reflects the significant emission of non-volatile material over the continent and, depending on atmospheric stratification, increased concentrations at ground level.
Application of a diode array spectroradiometer to measuring the spectral scattering properties of cloud types in a laboratory
Authors: Smedley A. R. D. , Webb A. R. , Saunders C. P. R.
Published: April 2010

Abstract. In the last few years diode array spectroradiometers have become useful complements to traditional scanning instruments when measuring visible and ultraviolet solar radiation incident on the ground. This study describes the application of such an instrument to the problem of measuring the radiation scattered by different cloud-types in a laboratory environment. Details of how the instrument is incorporated into the experimental set-up are given together with the development of the system as a whole. The capability to measure a full spectrum for each scattering angle is an undoubted advantage, although the limited sensitivity impacts on the usefulness for optically thin clouds. Nevertheless example results are presented: (1) scattering phase functions at a range of wavelengths recorded simultaneously for water clouds, showing spectral deviation at the rainbow angle and verification of Mie theory; (2) likewise for mixed phase clouds, with evidence of both halo and rainbow features in a single scattering function; and, (3) detail of the forward scattering region in a glaciated cloud showing a barely perceptible halo feature, with implications for the small-scale structure of the ice crystals produced.
A new tropospheric and stratospheric Chemistry and Transport Model MOCAGE-Climat for multi-year studies: evaluation of the present-day climatology and sensitivity to surface processes
Authors: Teyssèdre H. , Michou M. , Clark H. L. , Josse B. , Karcher F. , Olivié D. , Peuch V.-H. , Saint-Martin D. , Cariolle D. , Attié J.-L. , Nédélec P. , Ricaud P. , Thouret V. , van der A R. J. , Volz-Thomas A. , Chéroux F.
Published: April 2010

Abstract. We present the configuration of the Météo-France Chemistry and Transport Model (CTM) MOCAGE-Climat that will be dedicated to the study of chemistry and climate interactions. MOCAGE-Climat is a state-of-the-art CTM that simulates the global distribution of ozone and its precursors (82 chemical species) both in the troposphere and the stratosphere, up to the mid-mesosphere (~70 km). Surface processes (emissions, dry deposition), convection, and scavenging are explicitly described in the model that has been driven by the ECMWF operational analyses of the period 2000–2005, on T21 and T42 horizontal grids and 60 hybrid vertical levels, with and without a procedure that reduces calculations in the boundary layer, and with on-line or climatological deposition velocities. Model outputs have been compared to available observations, both from satellites (TOMS, HALOE, SMR, SCIAMACHY, MOPITT) and in-situ instrument measurements (ozone sondes, MOZAIC and aircraft campaigns) at climatological timescales. The distribution of long-lived species is in fair agreement with observations in the stratosphere putting aside the shortcomings associated with the large-scale circulation. The variability of the ozone column, both spatially and temporarily, is satisfactory. However, because the Brewer-Dobson circulation is too fast, too much ozone is accumulated in the lower to mid-stratosphere at the end of winter. Ozone in the UTLS region does not show any systematic bias. In the troposphere better agreement with ozone sonde measurements is obtained at mid and high latitudes than in the tropics and differences with observations are the lowest in summer. Simulations using a simplified boundary layer lead to larger ozone differences between the model and the observations up to the mid-troposphere. NOx in the lowest troposphere is in general overestimated, especially in the winter months over the Northern Hemisphere, which may result from a positive bias in OH. Dry deposition fluxes of O3 and nitrogen species are within the range of values reported by recent inter-comparison model exercises. The use of climatological deposition velocities versus deposition velocities calculated on-line had greatest impact on HNO3 and NO2 in the troposphere.
Atmospheric deuterium fractionation: HCHO and HCDO yields in the CH2DO + O2reaction
Authors: Nilsson E. J. K. , Johnson M. S. , Taketani F. , Matsumi Y. , Hurley M. D. , Wallington T. J.
Published: April 2010

Abstract. The formation of formaldehyde via hydrogen atom transfer from the methoxy radical to molecular oxygen is a key step in the atmospheric photochemical oxidation of methane, and in the propagation of deuterium from methane to molecular hydrogen. We report the results of the first investigation of the branching ratio for HCHO and HCDO formation in the CH2DO + O2 reaction. Labeled methoxy radicals (CH2DO) were generated in a photochemical reactor by photolysis of CH2DONO. HCHO and HCDO concentrations were measured using FTIR spectroscopy. Significant deuterium enrichment was seen in the formaldehyde product, from which we derive a branching ratio of 88.2±1.1% for HCDO and 11.8±1.1% for HCHO. The implications of this fractionation on the propagation of deuterium in the atmosphere are discussed.
Regional aerosol optical properties and radiative impact of the extreme smoke event in the European Arctic in spring 2006
Authors: Lund Myhre C. , Toledano C. , Myhre G. , Stebel K. , Yttri K. E. , Aaltonen V. , Johnsrud M. , Frioud M. , Cachorro V. , de Frutos A. , Lihavainen H. , Campbell J. R. , Chaikovsky A. P. , Shiobara M. , Welton E. J. , Tørseth K.
Published: April 2010

Abstract. In spring 2006 a special meteorological situation occurred in the European Arctic region giving record high levels of air pollution. The synoptic situation resulted in extensive transport of pollution predominantly from agricultural fires in Eastern Europe into the Arctic region and record high air-pollution levels were measured at the Zeppelin observatory at Ny-Ålesund (78°54' N, 11°53' E) in the period from 25 April to 12 May. In the present study we investigate the optical properties of the aerosols from this extreme event and we estimate the radiative forcing of this episode. We examine the aerosol optical properties from the source region and into the European Arctic and explore the evolution of the episode and the changes in the optical properties. A number of sites in Eastern Europe, Northern Scandinavia and Svalbard are included in the study. The observations show that the maximum AOD was from 2–3 May at all sites and varies from 0.52 to 0.87, and the corresponding Ångstrøm exponent was relatively large. Lidar measurements from Minsk, ALOMAR (Arctic Lidar Observatory for Middle Atmosphere Research at Andenes) and Ny-Ålesund show that the aerosol layer was below 3 km at all sites the height is decreasing from the source region and into the Arctic. For the AERONET sites included (Minsk, Toravere, Hornsund) we have further studied the evolution of the aerosol size. The single scattering albedo at Svalbard is provided for two sites; Ny-Ålesund and Hornsund. Importantly the calculated single scattering albedo based on the aerosol chemical composition and size distribution from Ny-Ålesund and the AERONET measurements at Hornsund are consistent. We have found strong agreement between the satellite daily MODIS AOD and the ground-based AOD observations. This agreement is crucial for accurate radiative forcing calculations. We calculate a strong negative radiative forcing for the most polluted days employing the analysed ground based data, MODIS AOD and a multi-stream model for radiative transfer of solar radiation. During this specific pollution event the forcing reached values as low as −35 W m−2 in the region. For comparison, the direct forcing of a corresponding aerosol layer with a typical AOD of 0.05 for the season is around −5 W m−2.
Spectral absorption properties of atmospheric aerosols
Authors: Bergstrom R. W. , Pilewskie P. , Russell P. B. , Redemann J. , Bond T. C. , Quinn P. K. , Sierau B.
Published: April 2010

Abstract. We have determined the solar spectral absorption optical depth of atmospheric aerosols for specific case studies during several field programs (three cases have been reported previously; two are new results). We combined airborne measurements of the solar net radiant flux density and the aerosol optical depth with a detailed radiative transfer model for all but one of the cases. The field programs (SAFARI 2000, ACE Asia, PRIDE, TARFOX, INTEX-A) contained aerosols representing the major absorbing aerosol types: pollution, biomass burning, desert dust and mixtures. In all cases the spectral absorption optical depth decreases with wavelength and can be approximated with a power-law wavelength dependence (Absorption Angstrom Exponent or AAE). We compare our results with other recent spectral absorption measurements and attempt to briefly summarize the state of knowledge of aerosol absorption spectra in the atmosphere. We discuss the limitations in using the AAE for calculating the solar absorption. We also discuss the resulting spectral single scattering albedo for these cases.
Small-scale mixing processes enhancing troposphere-to-stratosphere transport by pyro-cumulonimbus storms
Authors: Luderer G. , Trentmann J. , Hungershöfer K. , Herzog M. , Fromm M. , Andreae M. O.
Published: April 2010

Abstract. Deep convection induced by large forest fires is an efficient mechanism for transport of aerosol particles and trace gases into the upper troposphere and lower stratosphere (UT/LS). For many pyro-cumulonimbus clouds (pyroCbs) as well as other cases of severe convection without fire forcing, radiometric observations of cloud tops in the thermal infrared (IR) reveal characteristic structures, featuring a region of relatively high brightness temperatures (warm center) surrounded by a U-shaped region of low brightness temperatures. We performed a numerical simulation of a specific case study of pyroCb using a non-hydrostatic cloud resolving model with a two-moment cloud microphysics parameterization and a prognostic turbulence scheme. The model is able to reproduce the thermal IR structure as observed from satellite radiometry. Our findings establish a close link between the observed temperature pattern and small-scale mixing processes atop and downwind of the overshooting dome of the pyroCb. Such small-scale mixing processes are strongly enhanced by the formation and breaking of a stationary gravity wave induced by the overshoot. They are found to increase the stratospheric penetration of the smoke by up to almost 30 K and thus are of major significance for irreversible transport of forest fire smoke into the lower stratosphere.
Attenuation of global ultraviolet and visible irradiance over Greece during the total solar eclipse of 29 March 2006
Authors: Kazantzidis A. , Bais A. F. , Emde C. , Kazadzis S. , Zerefos C. S.
Published: April 2010

Abstract. The variability of ultraviolet and photosynthetically active radiation (PAR) during the total solar eclipse of 29 March 2006 was examined in this study. The measurements from NILU-UV multichannel radiometers at 7 stations of the Greek UV Network were used, where the maximum eclipse percentage ranged from 73.1% to 94.8%. In addition, an extra instrument was established at a remote Greek island, Kastelorizo, which was within the Moon's umbral shadow. The reduction of irradiance at 305 and 312 nm relative to non-eclipse conditions at all sites was almost 1.5 times more than the corresponding decrease in the UVA and visible part of the spectrum and reached 98% for eclipse percentage equal to 94%. The availability of several instruments in close proximity to the path of the umbral shadow provided a challenging test for the models. The measured changes in UV and visible irradiance were compared with 1-D model calculations accounting for the limb darkening effect. The agreement between measurements and modeled values at all sites is within 3% for eclipse percentages of less than 30% and becomes worse as the eclipse progresses. The 1-D model reproduced the spectral effect of the eclipse in UVA and PAR wavelength regions within 3% for eclipse percentages up to 50%, but only the half of the observed change was captured as the eclipse progressed. At three sites, where the eclipse maximum was more than 94%, the measured irradiance at 305 nm for eclipse percentages of more than 85% decreased with slower rates than for longer wavelengths. As a result, the total ozone values, derived from the 305/320 nm ratios, apparently decreased significantly for high eclipse percentages. The effect is similar at all three sites, but the interpretation of this observation remains a challenge. Comparison results with 3-D model calculations shortly before, during and shortly after totality were performed for the first time and revealed an agreement with measurements within 20% in the UV-A region. However, the modeled estimates of irradiance at 312 nm are three times lower than measured values.
Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions – Part 2: Exemplary practical applications and numerical simulations
Authors: Ammann M. , Pöschl U.
Published: April 2010

Abstract. A kinetic model framework with consistent and unambiguous terminology and universally applicable rate equations and parameters for aerosol and cloud surface chemistry and gas-particle interactions has been presented in the preceding companion paper by Pöschl, Rudich and Ammann (Pöschl et al., 2007), abbreviated PRA. It allows to describe mass transport and chemical reaction at the gas-particle interface and to link aerosol and cloud surface processes with gas phase and particle bulk processes. Here we present multiple exemplary model systems and calculations illustrating how the general mass balance and rate equations of the PRA framework can be easily reduced to compact sets of equations which enable a mechanistic description of time and concentration dependencies of trace gas uptake and particle composition in systems with one or more chemical components and physicochemical processes. Time-dependent model scenarios show the effects of reversible adsorption, surface-bulk transport, and chemical aging on the temporal evolution of trace gas uptake by solid particles and solubility saturation of liquid particles. They demonstrate how the transformation of particles and the variation of trace gas accommodation and uptake coefficients by orders of magnitude over time scales of microseconds to days can be explained and predicted from the initial composition and basic kinetic parameters of model systems by iterative calculations using standard spreadsheet programs. Moreover, they show how apparently inconsistent experimental data sets obtained with different techniques and on different time scales can be efficiently linked and mechanistically explained by application of consistent model formalisms and terminologies within the PRA framework. Steady-state model scenarios illustrate characteristic effects of gas phase composition and basic kinetic parameters on the rates of mass transport and chemical reactions. They demonstrate how adsorption and surface saturation effects can explain non-linear gas phase concentration dependencies of surface and bulk accommodation coefficients, uptake coefficients, and bulk solubilities (deviations from Henry's law). Such effects are expected to play an important role in many real atmospheric aerosol and cloud systems involving a wide range of organic and inorganic components of concentrated aqueous and organic solution droplets, ice crystals, and other crystalline or amorphous solid particles.
Balloon-borne radiometer measurements of Northern Hemisphere mid-latitude stratospheric HNO3 profiles spanning 12 years
Authors: Toohey M. , Quine B. M. , Strong K. , Bernath P. F. , Boone C. D. , Jonsson A. I. , McElroy C. T. , Walker K. A. , Wunch D.
Published: April 2010

Abstract. Low-resolution atmospheric thermal emission spectra collected by balloon-borne radiometers over the time span of 1990–2002 are used to retrieve vertical profiles of HNO3, CFC-11 and CFC-12 volume mixing ratios between approximately 10 and 35 km altitude. All of the data analyzed have been collected from launches from a Northern Hemisphere mid-latitude site, during late summer, when stratospheric dynamic variability is at a minimum. The retrieval technique incorporates detailed forward modeling of the instrument and the radiative properties of the atmosphere, and obtains a best fit between modeled and measured spectra through a combination of onion-peeling and optimization steps. The retrieved HNO3 profiles are consistent over the 12-year period, and are consistent with recent measurements by the Atmospheric Chemistry Experiment-Fourier transform spectrometer satellite instrument. We therefore find no evidence of long-term changes in the HNO3 summer mid-latitude profile, although the uncertainty of our measurements precludes a conclusive trend analysis.
Seeking for the rational basis of the Median Model: the optimal combination of multi-model ensemble results
Authors: Riccio A. , Giunta G. , Galmarini S.
Published: April 2010

Abstract. In this paper we present an approach for the statistical analysis of multi-model ensemble results. The models considered here are operational long-range transport and dispersion models, also used for the real-time simulation of pollutant dispersion or the accidental release of radioactive nuclides. We first introduce the theoretical basis (with its roots sinking into the Bayes theorem) and then apply this approach to the analysis of model results obtained during the ETEX-1 exercise. We recover some interesting results, supporting the heuristic approach called "median model", originally introduced in Galmarini et al. (2004a, b). This approach also provides a way to systematically reduce (and quantify) model uncertainties, thus supporting the decision-making process and/or regulatory-purpose activities in a very effective manner.
A climatology of surface ozone in the extra tropics: cluster analysis of observations and model results
Authors: Tarasova O. A. , Brenninkmeijer C. A. M. , Jöckel P. , Zvyagintsev A. M. , Kuznetsov G. I.
Published: April 2010

Abstract. Important aspects of the seasonal variations of surface ozone are discussed. The underlying analysis is based on the long-term (1990–2004) ozone records of the Co-operative Programme for Monitoring and Evaluation of the Long-range Transmission of Air Pollutants in Europe (EMEP) and the World Data Centre of Greenhouse Gases, which provide data mostly for the Northern Hemisphere. Seasonal variations are pronounced at most of the 114 locations at all times of the day. A seasonal-diurnal variations classification using hierarchical agglomeration clustering reveals 6 distinct clusters: clean background, rural, semi-polluted non-elevated, semi-polluted semi-elevated, elevated and polar/remote marine. For the "clean background" cluster the seasonal maximum is observed in March-April, both for night and day. For those sites with a double maximum or a wide spring-summer maximum, the spring maximum appears both for day and night, while the summer maximum is more pronounced for daytime and hence can be attributed to photochemical processes. The spring maximum is more likely caused by dynamical/transport processes than by photochemistry as it is observed in spring for all times of the day. We compare the identified clusters with corresponding data from the 3-D atmospheric chemistry general circulation model ECHAM5/MESSy1 covering the period of 1998–2005. For the model output as for the measurements 6 clusters are considered. The simulation shows at most of the sites a spring seasonal maximum or a broad spring-summer maximum (with higher summer mixing ratios). For southern hemispheric and polar remote locations the seasonal maximum in the simulation is shifted to spring, while the absolute mixing ratios are in good agreement with the measurements. The seasonality in the model cluster covering background locations is characterized by a pronounced spring (April–May) maximum. For the model clusters which cover rural and semi-polluted sites the role of the photochemical production/destruction seems to be overestimated. Taking into consideration the differences in the data sampling procedure, the comparison demonstrates the ability of the model to reproduce the main regimes of surface ozone variations quite well.
The influence of biogenic emissions on upper-tropospheric methanol as revealed from space
Authors: Dufour G. , Szopa S. , Hauglustaine D. A. , Boone C. D. , Rinsland C. P. , Bernath P. F.
Published: April 2010

Abstract. The distribution and budget of oxygenated organic compounds in the atmosphere and their impact on tropospheric chemistry are still poorly constrained. Near-global space-borne measurements of seasonally resolved upper tropospheric profiles of methanol (CH3OH) by the ACE Fourier transform spectrometer provide a unique opportunity to evaluate our understanding of this important oxygenated organic species. ACE-FTS observations from March 2004 to August 2005 period are presented. These observations reveal the pervasive imprint of surface sources on upper tropospheric methanol: mixing ratios observed in the mid and high latitudes of the Northern Hemisphere reflect the seasonal cycle of the biogenic emissions whereas the methanol cycle observed in the southern tropics is highly influenced by biomass burning emissions. The comparison with distributions simulated by the state-of-the-art global chemistry transport model, LMDz-INCA, suggests that: (i) the background methanol (high southern latitudes) is correctly represented by the model considering the measurement uncertainties; (ii) the current emissions from the continental biosphere are underestimated during spring and summer in the Northern Hemisphere leading to an underestimation of modelled upper tropospheric methanol; (iii) the seasonal variation of upper tropospheric methanol is shifted to the fall in the model suggesting either an insufficient destruction of CH3OH (due to too weak chemistry and/or deposition) in fall and winter months or an unfaithful representation of transport; (iv) the impact of tropical biomass burning emissions on upper tropospheric methanol is rather well reproduced by the model. This study illustrates the potential of these first global profile observations of oxygenated compounds in the upper troposphere to improve our understanding of their global distribution, fate and budget.
The effect of H2O adsorption on cloud drop activation of insoluble particles: a theoretical framework
Authors: Sorjamaa R. , Laaksonen A.
Published: April 2010

Abstract. Cloud droplet activation of wettable insoluble compounds has been studied theoretically by assuming that droplet growth happens through multilayer adsorption. The idea is to include an adsorption isotherm in Köhler theory instead of the solute term. This makes it possible to describe the equilibrium growth of insoluble particles and to find out their critical saturation ratios. The critical saturation ratios calculated in this way are comparable to those of completely soluble particles at certain ranges of adsorption isotherm parameter values. The results indicate that adsorption could cause wettable insoluble compounds to activate in atmospheric conditions. However, more data on the adsorption parameters for wettable organic substances is needed to confirm this conclusion.