bluuebunny/crossref_metadata_2025 huggingface dataset:
Synoptic influences on springtime tropospheric O3 and CO over the North American export region observed by TES
Authors: Hegarty J. , Mao H. , Talbot R.
Published: April 2010

Abstract. The relationship between synoptic circulation patterns over the western North Atlantic Ocean in spring (March, April, and May) and tropospheric O3 and CO was investigated using retrievals from the Tropospheric Emission Spectrometer (TES) for 2005 and 2006. Seasonal composites of TES retrievals reprocessed to remove the artificial geographic structure added from the a priori revealed a channel of slightly elevated O3 (>55 ppbv) and CO (>115 ppbv) at the 681 hPa retrieval level between 30° N and 45° N extending from North America out over the Atlantic Ocean. Ozone and CO in this region were correlated at r=0.22 with a slope value of 0.13 mol mol−1 indicative of the overall impact of photochemical chemical processes in North American continental export. Composites of TES retrievals for the six predominant circulation patterns identified as map types from sea level pressure fields of the NCEP FNL analyses showed large variability in the distribution of tropospheric O3. Map types MAM2 and MAM3 featuring cyclones near the US east coast produced the greatest export to the lower free troposphere with O3>65 ppbv and a relatively well-defined O3-CO correlation (slope values near 0.20 mol mol−1). The ensembles of HYSPLIT backward trajectories indicated that the high O3 levels were possibly a result of pollutants lofted to the free troposphere by the warm conveyor belt (WCB) of a cyclone. An important finding was that pollutant export occurred in the main WCB branch to the east of the cyclone and in a secondary branch circling to the back of the cyclone center. Conversely, a map type featuring a large anticyclone dominating the flow over the US east coast (MAM6) restricted export with O3 levels generally <55 ppbv and CO levels generally <110 ppbv. There was also evidence of stratospheric intrusions particularly to the north of 45° N in the 316 hPa composites predominately for MAM1 which featured a large cyclone near Newfoundland. However, the concurrence of these intrusions with pollutant export, specifically in the southwestern North Atlantic Ocean, made it difficult to delineate their respective contributions to the 681 hPa O3 composites.
Effects of regional-scale and convective transports on tropospheric ozone chemistry revealed by aircraft observations during the wet season of the AMMA campaign
Authors: Ancellet G. , Leclair de Bellevue J. , Mari C. , Nedelec P. , Kukui A. , Borbon A. , Perros P.
Published: April 2010

Abstract. The African Monsoon Multidisciplinary Analyses (AMMA) fourth airborne campaign was conducted in July–August 2006 to study the chemical composition of the middle and upper troposphere in West Africa with the major objective to better understand the processing of chemical emissions by the West African Monsoon (WAM) and its associated regional-scale and vertical transports. In particular, the french airborne experiment was organized around two goals. The first was to characterize the impact of Mesoscale Convective Systems (MCSs) on the ozone budget in the upper troposphere and the evolution of the chemical composition of these convective plumes as they move westward toward the Atlantic Ocean. The second objective was to discriminate the impact of remote sources of pollution over West Africa, including transport from the middle east, Europe, Asia and from southern hemispheric fires. Observations of O3, CO, NOx, H2O and hydroperoxide above West Africa along repeated meridional transects were coupled with transport analysis based on the FLEXPART lagrangian model. The cross analysis of trace gas concentrations and transport pathways revealed 5 types of air masses: convective uplift of industrial and urban emissions, convective uplift of biogenic emissions, slow advection from Cotonou polluted plumes near the coast, meridional transport of upper tropospheric air from the subtropical barrier region, and meridional transport of Southern Hemisphere (SH) biomass burning emissions. O3/CO correlation plots and the correlation plots of H2O2 with a OH proxy revealed not only a control of the trace gas variability by transport processes but also significant photochemical reactivity in the mid- and upper troposphere. The study of four MCSs outflow showed contrasted chemical composition and air mass origins depending on the MCSs lifetime and latitudinal position. Favorables conditions for ozone production were found for MCSs with increased MCS lifetime (>1.5 days), which allowed for more H2O2 formation, and with trajectories crossing the 10° N latitude, which increased CO transport to the upper troposphere. The upper tropospheric concentrations sampled in the MCS outflow regions showed mixed origins including local vertical convective transport, and uplifting of air from the low troposphere over the middle-east related to the summer Asian low pressure system or from the southern hemispheric fires.
Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol: Part 1 – Evidence from measurements
Authors: Wex H. , Petters M. D. , Carrico C. M. , Hallbauer E. , Massling A. , McMeeking G. R. , Poulain L. , Wu Z. , Kreidenweis S. M. , Stratmann F.
Published: April 2010

Abstract. Secondary Organic Aerosols (SOA) studied in previous laboratory experiments generally showed only slight hygroscopic growth, but a much better activity as a CCN (Cloud Condensation Nucleus) than indicated by the hygroscopic growth. This discrepancy was examined at LACIS (Leipzig Aerosol Cloud Interaction Simulator), using a portable generator that produced SOA particles from the ozonolysis of α-pinene, and adding butanol or butanol and water vapor during some of the experiments. The light scattering signal of dry SOA-particles was measured by the LACIS optical particle spectrometer and was used to derive a refractive index for SOA of 1.45. LACIS also measured the hygroscopic growth of SOA particles up to 99.6% relative humidity (RH), and a CCN counter was used to measure the particle activation. SOA-particles were CCN active with critical diameters of e.g. 100 nm and 55 nm at super-saturations of 0.4% and 1.1%, respectively. But only slight hygroscopic growth with hygroscopic growth factors ≤1.05 was observed at RH<98% RH. At RH>98%, the hygroscopic growth increased stronger than would be expected if a constant hygroscopicity parameter for the particle/droplet solution was assumed. An increase of the hygroscopicity parameter by a factor of 4–6 was observed in the RH-range from below 90% to 99.6%, and this increase continued for increasingly diluted particle solutions for activating particles. This explains an observation already made in the past: that the relation between critical super-saturation and dry diameter for activation is steeper than what would be expected for a constant value of the hygroscopicity. Combining measurements of hygroscopic growth and activation, it was found that the surface tension that has to be assumed to interpret the measurements consistently is greater than 55 mN/m, possibly close to that of pure water, depending on the different SOA-types produced, and therefore only in part accounts for the discrepancy between hygroscopic growth and CCN activity observed for SOA particles in the past.
Process based inventory of isoprenoid emissions from European forests: model comparisons, current knowledge and uncertainties
Authors: Keenan T. , Niinemets Ü. , Sabate S. , Gracia C. , Peñuelas J.
Published: April 2010

Abstract. Large uncertainties exist in our knowledge of regional emissions of non-methane biogenic volatile organic compounds (BVOC). We address these uncertainties through a two-pronged approach by compiling a state of the art database of the emissions potentials for 80 European forest species, and by a model assessment and inter-comparison, both at the local and regional scale, under present and projected future climatic conditions. We coupled three contrasting isoprenoid models with the ecophysiological forest model GOTILWA+ to evaluate leaf and ecosystem isoprenoid emissions, build an emissions inventory for European forests, and to consider model behaviour in present climate and under projected future climate change conditions. Hourly, daily and annual isoprene emissions as simulated by the models were evaluated against flux measurements. The validation highlighted a general model capacity to capture gross fluxes but inefficiencies in capturing short term variability. A regional inventory of isoprenoid emissions for European forests was created using each of the three modelling approaches. The models agreed on an average European emissions budget of 1.03 TgC a−1 for isoprene and 0.97 TgC a−1 for monoterpenes for the period 1960–1990, which was dominated by a few species with largest aerial coverage. Species contribution to total emissions depended both on species emission potential and geographical distribution. For projected future climate conditions, however, emissions budgets proved highly model dependent, illustrating the current uncertainty associated with isoprenoid emissions responses to potential future conditions. These results suggest that current model estimates of isoprenoid emissions concur well, but future estimates are highly uncertain. We conclude that development of reliable models is highly urgent, but for the time being, future BVOC emission scenario estimates should consider results from an ensemble of available emission models.
Validation of version-4.61 methane and nitrous oxide observed by MIPAS
Authors: Payan S. , Camy-Peyret C. , Oelhaf H. , Wetzel G. , Maucher G. , Keim C. , Pirre M. , Huret N. , Engel A. , Volk M. C. , Kuellmann H. , Kuttippurath J. , Cortesi U. , Bianchini G. , Mencaraglia F. , Raspollini P. , Redaelli G. , Vigouroux C. , De Mazière M. , Mikuteit S. , Blumenstock T. , Velazco V. , Notholt J. , Mahieu E. , Duchatelet P. , Smale D. , Wood S. , Jones N. , Piccolo C. , Payne V. , Bracher A. , Glatthor N. , Stiller G. , Grunow K. , Jeseck P. , Te Y. , Butz A.
Published: April 2010

Abstract. The ENVISAT validation programme for the atmospheric instruments MIPAS, SCIAMACHY and GOMOS is based on a number of balloon-borne, aircraft, satellite and ground-based correlative measurements. In particular the activities of validation scientists were coordinated by ESA within the ENVISAT Stratospheric Aircraft and Balloon Campaign or ESABC. As part of a series of similar papers on other species [this issue] and in parallel to the contribution of the individual validation teams, the present paper provides a synthesis of comparisons performed between MIPAS CH4 and N2O profiles produced by the current ESA operational software (Instrument Processing Facility version 4.61 or IPF v4.61, full resolution MIPAS data covering the period 9 July 2002 to 26 March 2004) and correlative measurements obtained from balloon and aircraft experiments as well as from satellite sensors or from ground-based instruments. In the middle stratosphere, no significant bias is observed between MIPAS and correlative measurements, and MIPAS is providing a very consistent and global picture of the distribution of CH4 and N2O in this region. In average, the MIPAS CH4 values show a small positive bias in the lower stratosphere of about 5%. A similar situation is observed for N2O with a positive bias of 4%. In the lower stratosphere/upper troposphere (UT/LS) the individual used MIPAS data version 4.61 still exhibits some unphysical oscillations in individual CH4 and N2O profiles caused by the processing algorithm (with almost no regularization). Taking these problems into account, the MIPAS CH4 and N2O profiles are behaving as expected from the internal error estimation of IPF v4.61 and the estimated errors of the correlative measurements.
Analysis of atmospheric neutral and charged molecular clusters in boreal forest using pulse-height CPC
Authors: Lehtipalo K. , Sipilä M. , Riipinen I. , Nieminen T. , Kulmala M.
Published: April 2010

Abstract. We measured the size distribution of atmospheric neutral and charged clusters and particles down to mobility diameter around 1.5 nm by applying pulse-height CPC technique at SMEAR II station in Hyytiälä, southern Finland during spring 2007 and May 2008. The concentration of molecular clusters smaller than 3 nm seems to be highly variable in boreal forest environment, the concentration varied typically between 500–50 000 cm−3. By comparing to concentrations measured with ion spectrometers, we conclude that ion clusters and neutral clusters produced by ion-ion recombination are usually not sufficient to explain all of the observed clusters; the median fraction of recombination products from all neutral clusters was 4.9%. Before and during most new particle formation events the cluster formation rate rose only slightly, or remained close to stable. Nocturnal formation of clusters was also frequently observed.
Flux estimates of isoprene, methanol and acetone from airborne PTR-MS measurements over the tropical rainforest during the GABRIEL 2005 campaign
Authors: Eerdekens G. , Ganzeveld L. , Vilà-Guerau de Arellano J. , Klüpfel T. , Sinha V. , Yassaa N. , Williams J. , Harder H. , Kubistin D. , Martinez M. , Lelieveld J.
Published: April 2010

Abstract. Tropical forests are a strong source of biogenic volatile organic compounds (BVOCs) to the atmosphere which can potentially impact the atmospheric oxidation capacity. Here we present airborne and ground-based BVOC measurements representative for the long dry season covering a large area of the northern Amazonian rainforest (6–3° N, 50–59° W). The measurements were conducted during the October 2005 GABRIEL (Guyanas Atmosphere-Biosphere exchange and Radicals Intensive Experiment with the Learjet) campaign. The vertical (35 m to 10 km) and diurnal (09:00–16:00) profiles of isoprene, its oxidation products methacrolein and methyl vinyl ketone and methanol and acetone, measured by PTR-MS (Proton Transfer Reaction Mass Spectrometry), have been used to empirically estimate their emission fluxes from the forest canopy on a regional scale. The mixed layer isoprene emission flux, inferred from the airborne measurements above 300 m, is 5.7 mg isoprene m−2 h−1 after compensating for chemistry and ~6.9 mg isoprene m−2 h−1 taking detrainment into account. This surface flux is in general agreement with previous tropical forest studies. Inferred methanol and acetone emission fluxes are 0.5 mg methanol m−2 h−1 and 0.35 mg acetone m−2 h−1, respectively. The BVOC measurements were compared with fluxes and mixing ratios simulated with a single-column chemistry and climate model (SCM). The inferred isoprene flux is substantially smaller than that simulated with an implementation of a commonly applied BVOC emission algorithm in the SCM.
Accurate satellite-derived estimates of the tropospheric ozone impact on the global radiation budget
Authors: Joiner J. , Schoeberl M. R. , Vasilkov A. P. , Oreopoulos L. , Platnick S. , Livesey N. J. , Levelt P. F.
Published: April 2010

Abstract. Estimates of the radiative forcing due to anthropogenically-produced tropospheric O3 are derived primarily from models. Here, we use tropospheric ozone and cloud data from several instruments in the A-train constellation of satellites as well as information from the GEOS-5 Data Assimilation System to accurately estimate the radiative effect of tropospheric O3 for January and July 2005. Since we cannot distinguish between natural and anthropogenic sources with the satellite data, our derived radiative effect reflects the unadjusted (instantaneous) effect of the total tropospheric O3 rather than the anthropogenic component. We improve upon previous estimates of tropospheric ozone mixing ratios from a residual approach using the NASA Earth Observing System (EOS) Aura Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS) by incorporating cloud pressure information from OMI. We focus specifically on the magnitude and spatial structure of the cloud effect on both the short- and long-wave radiative budget. The estimates presented here can be used to evaluate the various aspects of model-generated radiative forcing. For example, our derived cloud impact is to reduce the radiative effect of tropospheric ozone by ~16%. This is centered within the published range of model-produced cloud effect on unadjusted ozone radiative forcing.
Temporal and spatial variability of glyoxal as observed from space
Authors: Vrekoussis M. , Wittrock F. , Richter A. , Burrows J. P.
Published: April 2010

Abstract. Glyoxal, CHO.CHO, is produced during the oxidation of volatile organic compounds, VOC, released by anthropogenic activities, biogenic processes and biomass burning. It has a short chemical lifetime of a few hours in the boundary layer and lower troposphere and therefore serves as an indicator and a marker of photochemical hot-spots and their response to changing atmospheric conditions around the globe. For this reason more than five years of CHO.CHO observations (2002–2007), retrieved from the radiances measured by the satellite instrument SCIAMACHY, were obtained and analyzed both temporally and spatially. The largest columns of CHO.CHO (>6.1014 molec cm−2) are found in the tropical and sub-tropical regions, associated with high biological activity and the plumes from vegetation fires. The majority of the identified hot spots are characterized by a well-defined seasonality: the highest values being observed during the warm and dry periods as a result of the enhanced biogenic, primarily isoprene, emissions and/or biomass burning from natural or man-made fires. The regions influenced by anthropogenic pollution also encounter enhanced amounts of glyoxal. The ratio "CHO.CHO to HCHO, RGF" over the biogenically influenced photochemical hot-spots is approximately 0.045. For the studied regions, the presence of pyrogenic and anthropogenic emissions increases and decreases this number respectively. Although the 2002–2007 period of observation is limited, over the northeastern Asia a significant annual increase in CHO.CHO in addition to a seasonal cycle is reported.
Variability in regional background aerosols within the Mediterranean
Authors: Querol X. , Alastuey A. , Pey J. , Cusack M. , Pérez N. , Mihalopoulos N. , Theodosi C. , Gerasopoulos E. , Kubilay N. , Koçak M.
Published: April 2010

Abstract. The main objective of this study is the identification of major factors controlling levels and chemical composition of aerosols in the regional background (RB) along the Mediterranean Basin (MB). To this end, data on PM levels and speciation from Montseny (MSY, NE Spain), Finokalia (FKL, Southern Greece) and Erdemli (ERL, Southern Turkey) for the period 2001 to 2008 are evaluated. Important differences on PM levels and composition are evident when comparing the Western and Eastern MBs. The results manifest W-E and N-S PM10 and PM2.5 gradients along the MB, attributed to the higher frequency and intensity of African dust outbreaks in the EMB, while for PM1 very similar levels are encountered. PM in the EMB is characterized by higher levels of crustal material and sulphate as compared to WMB (and central European sites), however, RB nitrate and OC + EC levels are relatively constant across the Mediterranean and lower than other European sites. Marked seasonal trends are evidenced for PM levels, nitrate (WMB), ammonium and sulphate. Also relatively higher levels of V and Ni (WMB) are measured in the Mediterranean basin, probably as a consequence of high emissions from fuel-oil combustion (power generation, industrial and shipping emissions). Enhanced sulphate levels in EMB compared to WMB were measured. The high levels of sulphate in the EMB may deplete the available gas-phase NH3 so that little ammonium nitrate can form due to the low NH3 levels. This study illustrates the existence of three very important features within the Mediterranean that need to be accounted for when modeling climate effects of aerosols in the area, namely: a) the increasing gradient of dust from WMB to EMB; b) the change of hygroscopic behavior of mineral aerosols (dust) via nitration and sulfation; and c) the abundance of highly hygroscopic aerosols during high insolation (low cloud formation) periods.
Aerosol size-dependent below-cloud scavenging by rain and snow in the ECHAM5-HAM
Authors: Croft B. , Lohmann U. , Martin R. V. , Stier P. , Wurzler S. , Feichter J. , Posselt R. , Ferrachat S.
Published: April 2010

Abstract. Wet deposition processes are highly efficient in the removal of aerosols from the atmosphere, and thus strongly influence global aerosol concentrations, and clouds, and their respective radiative forcings. In this study, physically detailed size-dependent below-cloud scavenging parameterizations for rain and snow are implemented in the ECHAM5-HAM global aerosol-climate model. Previously, below-cloud scavenging by rain in the ECHAM5-HAM was simply a function of the aerosol mode, and then scaled by the rainfall rate. The below-cloud scavenging by snow was a function of the snowfall rate alone. The global mean aerosol optical depth, and sea salt burden are sensitive to the below-cloud scavenging coefficients, with reductions near to 15% when the more vigorous size-dependent below-cloud scavenging by rain and snow is implemented. The inclusion of a prognostic rain scheme significantly reduces the fractional importance of below-cloud scavenging since there is higher evaporation in the lower troposphere, increasing the global mean sea salt burden by almost 15%. Thermophoretic effects are shown to produce increases in the global and annual mean number removal of Aitken size particles of near to 10%, but very small increases (near 1%) in the global mean below-cloud mass scavenging of carbonaceous and sulfate aerosols. Changes in the assumptions about the below-cloud scavenging by rain of particles with radius smaller than 10 nm do not cause any significant changes to the global and annual mean aerosol mass or number burdens, despite a change in the below-cloud number removal rate for nucleation mode particles by near to five-fold. Annual and zonal mean nucleation mode number concentrations are enhanced by up to 30% in the lower troposphere with the more vigourous size-dependent below-cloud scavenging. Closer agreement with different observations is found when the more physically detailed below-cloud scavenging parameterization is employed in the ECHAM5-HAM model.
East Asian SO2 pollution plume over Europe – Part 1: Airborne trace gas measurements and source identification by particle dispersion model simulations
Authors: Fiedler V. , Nau R. , Ludmann S. , Arnold F. , Schlager H. , Stohl A.
Published: April 2010

Abstract. A large SO2-rich pollution plume of East Asian origin was detected by aircraft based CIMS (Chemical Ionization Mass Spectrometry) measurements at 3–7.5 km altitude over the North Atlantic. The measurements, which took place on 3 May 2006 aboard of the German research aircraft Falcon, were part of the INTEX-B (Intercontinental Chemical Transport Experiment-B) campaign. Additional trace gases (NO, NOy, CO, H2O) were measured and used for comparison and source identification. The atmospheric SO2 mole fraction was markedly increased inside the plume and reached up to 900 pmol/mol. Accompanying lagrangian FLEXPART particle dispersion model simulations indicate that the probed pollution plume originated at low altitudes from densely populated and industrialized regions of East Asia, primarily China, about 8–12 days prior to the measurements.
Simulating mixed-phase Arctic stratus clouds: sensitivity to ice initiation mechanisms
Authors: Sednev I. , Menon S. , McFarquhar G.
Published: April 2010

Abstract. The importance of Arctic mixed-phase clouds on radiation and the Arctic climate is well known. However, the development of mixed-phase cloud parameterization for use in large scale models is limited by lack of both related observations and numerical studies using multidimensional models with advanced microphysics that provide the basis for understanding the relative importance of different microphysical processes that take place in mixed-phase clouds. To improve the representation of mixed-phase cloud processes in the GISS GCM we use the GISS single-column model coupled to a bin resolved microphysics (BRM) scheme that was specially designed to simulate mixed-phase clouds and aerosol-cloud interactions. Using this model with the microphysical measurements obtained from the DOE ARM Mixed-Phase Arctic Cloud Experiment (MPACE) campaign in October 2004 at the North Slope of Alaska, we investigate the effect of ice initiation processes and Bergeron-Findeisen process (BFP) on glaciation time and longevity of single-layer stratiform mixed-phase clouds. We focus on observations taken during 9–10 October, which indicated the presence of a single-layer mixed-phase clouds. We performed several sets of 12-h simulations to examine model sensitivity to different ice initiation mechanisms and evaluate model output (hydrometeors' concentrations, contents, effective radii, precipitation fluxes, and radar reflectivity) against measurements from the MPACE Intensive Observing Period. Overall, the model qualitatively simulates ice crystal concentration and hydrometeors content, but it fails to predict quantitatively the effective radii of ice particles and their vertical profiles. In particular, the ice effective radii are overestimated by at least 50%. However, using the same definition as used for observations, the effective radii simulated and that observed were more comparable. We find that for the single-layer stratiform mixed-phase clouds simulated, process of ice phase initiation due to freezing of supercooled water in both saturated and subsaturated (w.r.t. water) environments is as important as primary ice crystal origination from water vapor. We also find that the BFP is a process mainly responsible for the rates of glaciation of simulated clouds. These glaciation rates cannot be adequately represented by a water-ice saturation adjustment scheme that only depends on temperature and liquid and solid hydrometeors' contents as is widely used in bulk microphysics schemes and are better represented by processes that also account for supersaturation changes as the hydrometeors grow.
Satellite observations and modeling of transport in the upper troposphere through the lower mesosphere during the 2006 major stratospheric sudden warming
Authors: Manney G. L. , Harwood R. S. , MacKenzie I. A. , Minschwaner K. , Allen D. R. , Santee M. L. , Walker K. A. , Hegglin M. I. , Lambert A. , Pumphrey H. C. , Bernath P. F. , Boone C. D. , Schwartz M. J. , Livesey N. J. , Daffer W. H. , Fuller R. A.
Published: April 2010

Abstract. An unusually strong and prolonged stratospheric sudden warming (SSW) in January 2006 was the first major SSW for which globally distributed long-lived trace gas data are available covering the upper troposphere through the lower mesosphere. We use Aura Microwave Limb Sounder (MLS), Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) data, the SLIMCAT Chemistry Transport Model (CTM), and assimilated meteorological analyses to provide a comprehensive picture of transport during this event. The upper tropospheric ridge that triggered the SSW was associated with an elevated tropopause and layering in trace gas profiles in conjunction with stratospheric and tropospheric intrusions. Anomalous poleward transport (with corresponding quasi-isentropic troposphere-to-stratosphere exchange at the lowest levels studied) in the region over the ridge extended well into the lower stratosphere. In the middle and upper stratosphere, the breakdown of the polar vortex transport barrier was seen in a signature of rapid, widespread mixing in trace gases, including CO, H2O, CH4 and N2O. The vortex broke down slightly later and more slowly in the lower than in the middle stratosphere. In the middle and lower stratosphere, small remnants with trace gas values characteristic of the pre-SSW vortex lingered through the weak and slow recovery of the vortex. The upper stratospheric vortex quickly reformed, and, as enhanced diabatic descent set in, CO descended into this strong vortex, echoing the fall vortex development. Trace gas evolution in the SLIMCAT CTM agrees well with that in the satellite trace gas data from the upper troposphere through the middle stratosphere. In the upper stratosphere and lower mesosphere, the SLIMCAT simulation does not capture the strong descent of mesospheric CO and H2O values into the reformed vortex; this poor CTM performance in the upper stratosphere and lower mesosphere results primarily from biases in the diabatic descent in assimilated analyses.
Detection of pollution transport events southeast of Mexico City using ground-based visible spectroscopy measurements of nitrogen dioxide
Authors: Melamed M. L. , Basaldud R. , Steinbrecher R. , Emeis S. , Ruíz-Suárez L. G. , Grutter M.
Published: April 2010

Abstract. This work presents ground based differential optical absorption spectroscopy (DOAS) measurements of nitrogen dioxide (NO2) during the MILAGRO field campaign in March 2006 at the Tenango del Aire research site located to the southeast of Mexico City. The DOAS NO2 column density measurements are used in conjunction with ceilometer, meteorological and surface nitric oxide (NO), nitrogen oxides (NOx) and total reactive nitrogen (NOy) measurements to analyze pollution transport events to the southeast of Mexico City during the MILARGO field campaign. The study divides the data set into three case study pollution transport events that occurred at the Tenango del Aire research site. The unique data set is then used to provide an in depth analysis of example days of each of the pollution transport events. An in depth analysis of 13 March 2006, a Case One day, shows the transport of several air pollution plumes during the morning through the Tenango del Aire research site when southerly winds are present and demonstrates how DOAS tropospheric NO2 vertical column densities (VCD), surface NO2 mixing ratios and ceilometer data are used to determine the vertical homogeneity of the pollution layer. The analysis of 18 March 2006, a Case Two day, shows that when northerly winds are present for the entire day, the air at the Tenango del Aire research site is relatively clean and no major pollution plumes are detected. Case 3 days are characterized by relatively clean air throughout the morning with large DOAS NO2 enhancements detected in the afternoon. The analysis of 28 March 2006 show the DOAS NO2 enhancements are likely due to lightning activity and demonstrate how suitable ground-based DOAS measruements are for monitoring anthropogenic and natural pollution sources that reside above the mixing layer.
Assessing positive matrix factorization model fit: a new method to estimate uncertainty and bias in factor contributions at the measurement time scale
Authors: Hemann J. G. , Brinkman G. L. , Dutton S. J. , Hannigan M. P. , Milford J. B. , Miller S. L.
Published: April 2010

Abstract. A Positive Matrix Factorization receptor model for aerosol pollution source apportionment was fit to a synthetic dataset simulating one year of daily measurements of ambient PM2.5 concentrations, comprised of 39 chemical species from nine pollutant sources. A novel method was developed to estimate model fit uncertainty and bias at the daily time scale, as related to factor contributions. A circular block bootstrap is used to create replicate datasets, with the same receptor model then fit to the data. Neural networks are trained to classify factors based upon chemical profiles, as opposed to correlating contribution time series, and this classification is used to align factor orderings across the model results associated with the replicate datasets. Factor contribution uncertainty is assessed from the distribution of results associated with each factor. Comparing modeled factors with input factors used to create the synthetic data assesses bias. The results indicate that variability in factor contribution estimates does not necessarily encompass model error: contribution estimates can have small associated variability across results yet also be very biased. These findings are likely dependent on characteristics of the data.
Modelling chemistry over the Dead Sea: bromine and ozone chemistry
Authors: Smoydzin L. , von Glasow R.
Published: April 2010

Abstract. Measurements of O3 and BrO concentrations over the Dead Sea indicate that Ozone Depletion Events (ODEs), widely known to happen in polar regions, are also occuring over the Dead Sea due to the very high bromine content of the Dead Sea water. However, we show that BrO and O3 levels as they are detected cannot solely be explained by high Br− levels in the Dead Sea water and the release of gas phase halogen species out of sea borne aerosol particles and their conversion to reactive halogen species. It is likely that other sources for reactive halogen compounds are needed to explain the observed concentrations for BrO and O3. To explain the chemical mechanism taking place over the Dead Sea leading to BrO levels of several pmol/mol we used the one-dimensional model MISTRA which calculates microphysics, meteorology, gas and aerosol phase chemistry. We performed pseudo Lagrangian studies by letting the model column first move over the desert which surrounds the Dead Sea region and then let it move over the Dead Sea itself. To include an additional source for gas phase halogen compounds, gas exchange between the Dead Sea water and the atmosphere is treated explicitly. Model calculations indicate that this process has to be included to explain the measurements.
In-cloud processes of methacrolein under simulated conditions – Part 1: Aqueous phase photooxidation
Authors:   Yao Liu, El Haddad I. , Scarfogliero M. , Nieto-Gligorovski L. , Temime-Roussel B. , Quivet E. , Marchand N. , Picquet-Varrault B. , Monod A.
Published: April 2010

Abstract. The photooxidation of methacrolein was studied in the aqueous phase under simulated cloud droplet conditions. The obtained rate constant of OH-oxidation of methacrolein at 6°C in unbuffered solutions was 5.8(±0.9)×109 M−1 s−1. The measured rate coefficient is consistent with OH-addition on the C=C bond. This was confirmed by the mechanism established on the study of the reaction products (at 25°C in unbuffered solutions) where methylglyoxal, formaldehyde, hydroxyacetone and acetic acid/acetate were the main reaction products. An upper limit for the total carbon yield was estimated to range from 53 to 85%, indicating that some reaction products remain unidentified. A possible source of this mismatch is the formation of higher molecular weight compounds as primary reaction products which are presented in El Haddad et al. (2009) and Michaud et al. (2009).
A two-step scheme for high-resolution regional atmospheric trace gas inversions based on independent models
Authors: Rödenbeck C. , Gerbig C. , Trusilova K. , Heimann M.
Published: April 2010

Abstract. Mixing ratio measurements of atmospheric tracers like CO2 can be used to estimate regional surface-air tracer fluxes using inverse methods, involving a numerical transport model. Currently available transport models are either global but rather coarse, or more accurate but only over a limited spatial and temporal domain. To obtain higher-resolution flux estimates within a region of interest, existing studies use zoomed or coupled models. The two-step scheme developed here uses global and regional models sequentially in separate inversion steps, coupled only via the data vector. This provides a nested atmospheric inversion scheme without the necessity of a direct coupled model implementation. For example, the scheme allows an easy nesting of Lagrangian models with their potential of very high resolution into global inversions based on Eulerian models.
Dynamical modes associated with the Antarctic ozone hole
Authors: Weare B. C.
Published: April 2010

Abstract. Generalized Maximum Covariance Analysis (GMCA) has been developed and applied to diagnosing the dynamical modes associated with variations in the Antarctic spring ozone hole. GMCA is used to identify the most important patterns of co-variability between interannual ozone mixing ratio variations in the Antarctic region and temperature, zonal, meridional and vertical velocities between 100 and 10 hPa in the same region. The most important two pairs of GMCA time coefficients show large year-to-year variations and trends, which are connected with the growth of the Antarctic Ozone Hole and the increase of ozone depleting substances. The associated spatial patterns of ozone variations may be characterized as being quasi-symmetric and asymmetric about the pole. These patterns of ozone variations are associated with comparable patterns of variations of temperature and winds through most of the vertical domain. The year 2000 is shown to be dominated by the asymmetric mode, whereas the adjacent year 2001 is dominated by the quasi-symmetric mode. A case study, focusing on the asymmetric differences between these two years, shows the magnitude of the ozone mixing ratio, temperature and zonal wind differences to be in the range of 2 e–6 kg/kg, 10°C and 10 m/s, respectively. Budget calculations show that transport processes contribute substantially to the ozone and temperature changes in the middle stratosphere over the Antarctic continent. However, both radiative and chemical processes also play important roles in the changes.
Implications of Lagrangian transport for simulations with a coupled chemistry-climate model
Authors: Stenke A. , Dameris M. , Grewe V. , Garny H.
Published: April 2010

Abstract. For the first time a purely Lagrangian transport algorithm is applied in a fully coupled chemistry-climate model (CCM). We use the numerically non-diffusive Lagrangian scheme ATTILA instead of the operational semi-Lagrangian scheme for the transport of water vapour, cloud water and chemical trace species in the CCM E39C. The new model version including the Lagrangian scheme is referred to as E39C-A. The implications of the Lagrangian transport scheme for stratospheric model dynamics and tracer distributions in E39C-A are evaluated by comparison with observations and results of the previous model version E39C. We found in a previous paper that several deficiencies in stratospheric dynamics in E39C originate from a pronounced modelled wet bias and an associated cold bias in the extra-tropical lowermost stratosphere. Contrary to the semi-Lagrangian scheme ATTILA shows a largely reduced meridional transport of water vapour from the tropical upper troposphere into the extratropical lowermost stratosphere. The reduction of the moisture and temperature bias in E39C-A leads to a significant advancement of stratospheric dynamics in terms of the mean state as well as annual and interannual variability. In this study we show that as a consequence of both, the favourable numerical characteristics of the Lagrangian transport scheme and the improved model dynamics, E39C-A generally shows more realistic distributions of chemical trace species: Compared to E39C high stratospheric chlorine (Cly) concentrations extend further downward. Therefore E39C-A realistically covers the altitude of maximum ozone depletion in the stratosphere. The location of the ozonopause, i.e. the transition from low tropospheric to high stratospheric ozone values, is also clearly improved in E39C-A. Not only the spatial distribution but also the temporal evolution of stratospheric Cly in the past is realistically reproduced in E39C-A which is an important step towards a more reliable projection of future changes, especially of stratospheric ozone. Despite a large number of improvements there are still remaining model deficiencies like a general overestimation of total column ozone.
The radiative forcing potential of different climate geoengineering options
Authors: Lenton T. M. , Vaughan N. E.
Published: April 2010

Abstract. Climate geoengineering proposals seek to rectify the Earth's current and potential future radiative imbalance, either by reducing the absorption of incoming solar (shortwave) radiation, or by removing CO2 from the atmosphere and transferring it to long-lived reservoirs, thus increasing outgoing longwave radiation. A fundamental criterion for evaluating geoengineering options is their climate cooling effectiveness, which we quantify here in terms of radiative forcing potential. We use a simple analytical approach, based on energy balance considerations and pulse response functions for the decay of CO2 perturbations. This aids transparency compared to calculations with complex numerical models, but is not intended to be definitive. It allows us to compare the relative effectiveness of a range of proposals. We consider geoengineering options as additional to large reductions in CO2 emissions. By 2050, some land carbon cycle geoengineering options could be of comparable magnitude to mitigation "wedges", but only stratospheric aerosol injections, albedo enhancement of marine stratocumulus clouds, or sunshades in space have the potential to cool the climate back toward its pre-industrial state. Strong mitigation, combined with global-scale air capture and storage, afforestation, and bio-char production, i.e. enhanced CO2 sinks, might be able to bring CO2 back to its pre-industrial level by 2100, thus removing the need for other geoengineering. Alternatively, strong mitigation stabilising CO2 at 500 ppm, combined with geoengineered increases in the albedo of marine stratiform clouds, grasslands, croplands and human settlements might achieve a patchy cancellation of radiative forcing. Ocean fertilisation options are only worthwhile if sustained on a millennial timescale and phosphorus addition may have greater long-term potential than iron or nitrogen fertilisation. Enhancing ocean upwelling or downwelling have trivial effects on any meaningful timescale. Our approach provides a common framework for the evaluation of climate geoengineering proposals, and our results should help inform the prioritisation of further research into them.
Mobile mini-DOAS measurement of the outflow of NO2 and HCHO from Mexico City
Authors: Johansson M. , Rivera C. , de Foy B. , Lei W. , Song J. , Zhang Y. , Galle B. , Molina L.
Published: April 2010

Abstract. We here present the results from mobile measurements using two ground-based zenith viewing Differential Optical Absorption Spectroscopy (DOAS) instruments. The measurement was performed in a cross-section of the plume from the Mexico City Metropolitan Area (MCMA) on 10 March 2006 as part of the MILAGRO field campaign. The two instruments operated in the UV and the visible wavelength region respectively and have been used to derive the differential vertical columns of HCHO and NO2 above the measurement route. This is the first time the mobile mini-DOAS instrument has been able to measure HCHO, one of the chemically most important and interesting gases in the polluted urban atmosphere. Using a mass-averaged wind speed and wind direction from the WRF model the instantaneous flux of HCHO and NO2 has been calculated from the measurements and the results are compared to the CAMx chemical model. The calculated flux through the measured cross-section was 1.9 (1.5–2.2) kg/s of HCHO and 4.4 (4.0–5.0) kg/s of NO2 using the UV instrument and 3.66 (3.63–3.73) kg/s of NO2 using the visible light instrument. The modeled values from CAMx for the outflow of both NO2 and HCHO, 1.1 and 3.6 kg/s, respectively, show a reasonable agreement with the measurement derived fluxes.
IASI measurements of reactive trace species in biomass burning plumes
Authors: Coheur P.-F. , Clarisse L. , Turquety S. , Hurtmans D. , Clerbaux C.
Published: April 2010

Abstract. This work presents observations of a series of short-lived species in biomass burning plumes from the Infrared Atmospheric Sounding Interferometer (IASI), launched onboard the MetOp-A platform in October 2006. The strong fires that have occurred in the Mediterranean Basin – and particularly Greece – in August 2007, and those in Southern Siberia and Eastern Mongolia in the early spring of 2008 are selected to support the analyses. We show that the IASI infrared spectra in these fire plumes contain distinctive signatures of ammonia (NH3), ethene (C2H4), methanol (CH3OH) and formic acid (HCOOH) in the atmospheric window between 800 and 1200 cm−1, with some noticeable differences between the plumes. Peroxyacetyl nitrate (CH3COOONO2, abbreviated as PAN) was also observed with good confidence in some plumes and a tentative assignment of a broadband absorption spectral feature to acetic acid (CH3COOH) is made. For several of these species these are the first reported measurements made from space in nadir geometry. The IASI measurements are analyzed for plume height and concentration distributions of NH3, C2H4 and CH3OH. The Greek fires are studied in greater detail for the days associated with the largest emissions. In addition to providing information on the spatial extent of the plume, the IASI retrievals allow an estimate of the total mass emissions for NH3, C2H4 and CH3OH. Enhancement ratios are calculated for the latter relative to carbon monoxide (CO), giving insight in the chemical processes occurring during the transport, the first day after the emission.
The influence of biogenic emissions from Africa on tropical tropospheric ozone during 2006: a global modeling study
Authors: Williams J. E. , Scheele M. P. , van Velthoven P. F. J. , Cammas J.-P. , Thouret V. , Galy-Lacaux C. , Volz-Thomas A.
Published: April 2010

Abstract. We have performed simulations using a 3-D global chemistry-transport model to investigate the influence that biogenic emissions from the African continent exert on the composition of the troposphere in the tropical region. For this purpose we have applied two recently developed biogenic emission inventories provided for use in large-scale global models (Granier et al., 2005; Lathière et al., 2006) whose seasonality and temporal distribution for biogenic emissions of isoprene, other volatile organic compounds and NO is markedly different. The use of the 12 year average values for biogenic emissions provided by Lathière et al. (2006) results in an increase in the amount of nitrogen sequestrated into longer lived reservoir compounds which contributes to the reduction in the tropospheric ozone burden in the tropics. The associated re-partitioning of nitrogen between PAN, HNO3 and organic nitrates also results in a ~5% increase in the loss of nitrogen by wet deposition. At a global scale there is a reduction in the oxidizing capacity of the model atmosphere which increases the atmospheric lifetimes of CH4 and CO by ~1.5% and ~4%, respectively. Comparisons against a range of different measurements indicate that applying the 12 year average of Lathière et al. (2006) improves the performance of TM4_AMMA for 2006 in the tropics. By the use of sensitivity studies we show that the release of NO from soils in Africa accounts for between ~2–45% of tropospheric ozone in the African troposphere, ~10% in the upper troposphere and between ~5–20% of the tropical tropospheric ozone column over the tropical Atlantic Ocean. The subsequent reduction in OH over the source regions allows enhanced transport of CO out of the region. For biogenic volatile organic C1 to C3 species released from Africa, the effects on tropical tropospheric ozone are rather limited, although this source contributes to the global burden of VOC by between ~2–4% and has a large influence on the organic composition of the troposphere over the tropical Atlantic Ocean.