bluuebunny/crossref_metadata_2025 huggingface dataset:
Lagrangian analysis of low altitude anthropogenic plume processing across the North Atlantic
Authors: Real E. , Law K. S. , Schlager H. , Roiger A. , Huntrieser H. , Methven J. , Cain M. , Holloway J. , Neuman J. A. , Ryerson T. , Flocke F. , de Gouw J. , Atlas E. , Donnelly S. , Parrish D.
Published: April 2010

Abstract. The photochemical evolution of an anthropogenic plume from the New-York/Boston region during its transport at low altitudes over the North Atlantic to the European west coast has been studied using a Lagrangian framework. This plume, originally strongly polluted, was sampled by research aircraft just off the North American east coast on 3 successive days, and then 3 days downwind off the west coast of Ireland where another aircraft re-sampled a weakly polluted plume. Changes in trace gas concentrations during transport are reproduced using a photochemical trajectory model including deposition and mixing effects. Chemical and wet deposition processing dominated the evolution of all pollutants in the plume. The mean net photochemical O3 production is estimated to be −5 ppbv/day leading to low O3 by the time the plume reached Europe. Model runs with no wet deposition of HNO3 predicted much lower average net destruction of −1 ppbv/day O3, arising from increased levels of NOx via photolysis of HNO3. This indicates that wet deposition of HNO3 is indirectly responsible for 80% of the net destruction of ozone during plume transport. If the plume had not encountered precipitation, it would have reached Europe with O3 concentrations of up to 80 to 90 ppbv and CO between 120 and 140 ppbv. Photochemical destruction also played a more important role than mixing in the evolution of plume CO due to high levels of O3 and water vapour showing that CO cannot always be used as a tracer for polluted air masses, especially in plumes transported at low altitudes. The results also show that, in this case, an increase in O3/CO slopes can be attributed to photochemical destruction of CO and not to photochemical O3 production as is often assumed.
Interannual-to-decadal variability of the stratosphere during the 20th century: ensemble simulations with a chemistry-climate model
Authors: Fischer A. M. , Schraner M. , Rozanov E. , Kenzelmann P. , Schnadt Poberaj C. , Brunner D. , Lustenberger A. , Luo B. P. , Bodeker G. E. , Egorova T. , Schmutz W. , Peter T. , Brönnimann S.
Published: April 2010

Abstract. Interannual-to-decadal variability in stratospheric ozone and climate have a number of common sources, such as variations in solar irradiance, stratospheric aerosol loading due to volcanic eruptions, El Niño Southern Oscillation variability and the quasi-biennial oscillation (QBO). Currently available data records as well as model simulations addressing stratospheric chemical climate variability mostly cover only the past few decades, which is often insufficient to address natural interannual-to-decadal variability. Here we make use of recently reconstructed and re-evaluated data products to force and validate transient ensemble model simulations (nine members) across the twentieth century computed by means of the chemistry-climate model SOCOL (SOlar Climate Ozone Links). The forcings include sea surface temperatures, sea ice, solar irradiance, stratospheric aerosols, QBO, changes in land properties, greenhouse gases, ozone depleting substances, and emissions of carbon monoxides, and nitrogen oxides. The transient simulations are in good agreement with observations, reconstructions and reanalyses and allow quantification of interannual-to-decadal variability during the 20th century. All ensemble members are able to capture the low-frequency variability in tropical and mid-latitude total ozone as well as in the strength of the subtropical jet, suggesting a realistic response to external forcings in this area. The region of the northern polar vortex exhibits a large internal variability that is found in the frequency, seasonality, and strength of major warmings as well as in the strength of the modeled polar vortex. Results from process-oriented analysis, such as correlation between the vertical Eliassen Palm flux (EP flux) component and polar variables as well as stratospheric ozone trends, are of comparable magnitude to those observed and are consistent in all analysed ensemble members. Yet, trend estimates of the vertical EP flux component vary greatly among ensemble members precluding any robust conclusions. This suggests that internal variability in models must be accounted for in order to quantify the atmospheric model response in wave energy upon external forcings.
Equatorial wave analysis from SABER and ECMWF temperatures
Authors: Ern M. , Preusse P. , Krebsbach M. , Mlynczak M. G. , Russell J. M.
Published: April 2010

Abstract. Equatorial planetary scale wave modes such as Kelvin waves or Rossby-gravity waves are excited by convective processes in the troposphere. In this paper an analysis for these and other equatorial wave modes is carried out with special focus on the stratosphere using temperature data from the SABER satellite instrument as well as ECMWF temperatures. Space-time spectra of symmetric and antisymmetric spectral power are derived to separate the different equatorial wave types and the contribution of gravity waves is determined from the spectral background of the space-time spectra. Both gravity waves and equatorial planetary scale wave modes are main drivers of the quasi-biennial oscillation (QBO) in the stratosphere. Temperature variances attributed to the different wave types are calculated for the period from February 2002 until March 2006 and compared to previous findings. A comparison between SABER and ECMWF wave analyses shows that in the lower stratosphere SABER and ECMWF spectra and temperature variances agree remarkably well while in the upper stratosphere ECMWF tends to overestimate Kelvin wave components. Gravity wave variances are partly reproduced by ECMWF but have a significant low-bias. For the examples of a QBO westerly phase (October–December 2004) and a QBO easterly phase (November/December 2005, period of the SCOUT-O3 tropical aircraft campaign in Darwin/Australia) in the lower stratosphere we find qualitatively good agreement between SABER and ECMWF in the longitude-time distribution of Kelvin, Rossby (n=1), and Rossby-gravity waves.
The validity of the kinetic collection equation revisited
Authors: Alfonso L. , Raga G. B. , Baumgardner D.
Published: April 2010

Abstract. The kinetic collection equation (KCE) describes the evolution of the average droplet spectrum due to successive events of collision and coalescence. Fluctuations and non-zero correlations present in the stochastic coalescence process would imply that the size distributions may not be correctly modeled by the KCE. In this study we expand the known analytical studies of the coalescence equation with some numerical tools such as Monte Carlo simulations of the coalescence process. The validity time of the KCE was estimated by calculating the maximum of the ratio of the standard deviation for the largest droplet mass over all the realizations to the averaged value. A good correspondence between the analytical and the numerical approaches was found for all the kernels. The expected values from analytical solutions of the KCE, were compared with true expected values of the stochastic collection equation (SCE) estimated with Gillespie's Monte Carlo algorithm and analytical solutions of the SCE, after and before the breakdown time. The possible implications for cloud physics are discussed, in particular the possibility of application of these results to kernels modified by turbulence and electrical processes.
SAGE II measurements of stratospheric aerosol properties at non-volcanic levels
Authors: Thomason L. W. , Burton S. P. , Luo B.-P. , Peter T.
Published: April 2010

Abstract. Since 2000, stratospheric aerosol levels have been relatively stable and at the lowest levels observed in the historical record. Given the challenges of making satellite measurements of aerosol properties at these levels, we have performed a study of the sensitivity of the product to the major components of the processing algorithm used in the production of SAGE II aerosol extinction measurements and the retrieval process that produces the operational surface area density (SAD) product. We find that the aerosol extinction measurements, particularly at 1020 nm, remain robust and reliable at the observed aerosol levels. On the other hand, during background periods, the SAD operational product has an uncertainty of at least a factor of 2 due to the lack of sensitivity to particles with radii less than 100 nm.
Spatio-temporal variations of NOy species in the northern latitudes stratosphere measured with the balloon-borne MIPAS instrument
Authors: Wiegele A. , Kleinert A. , Oelhaf H. , Ruhnke R. , Wetzel G. , Friedl-Vallon F. , Lengel A. , Maucher G. , Nordmeyer H. , Fischer H.
Published: April 2010

Abstract. This paper presents the spatio-temporal distribution of NOy species at altitudes between 14 and 31 km as measured with the MIPAS-B instrument on the morning of 21 March 2003 in northern Scandinavia. At lower altitudes (below about 22 km), temperature variations, the distribution of ClONO2, and the tracer N2O reveal the dynamics through the edge of the late arctic polar vortex. At higher altitudes, continuous measurement before, during, and after sunrise provides information about photochemistry illustrating the evolution of the photochemically active gases NO2 and N2O5 around sunrise. The measured temporal evolution of NO2 and N2O5 is compared to box modelling that is run along backward calculated trajectories. While the comparison of measured and modelled N2O5 reveals significant differences, there is a good agreement between the model and observations for NO2 in terms of volume mixing ratios but the simulated decrease shortly after sunrise is underestimated compared to the measurements. The differences are attributed to the photolysis rates used in the box model calculations.
Asian dust outflow in the PBL and free atmosphere retrieved by NASA CALIPSO and an assimilated dust transport model
Authors: Hara Y. , Yumimoto K. , Uno I. , Shimizu A. , Sugimoto N. , Liu Z. , Winker D. M.
Published: April 2010

Abstract. Three-dimensional structures of Asian dust transport in the planetary boundary layer (PBL) and free atmosphere occurring successively during the end of May 2007 were clarified using results of space-borne backscatter lidar, Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP), and results obtained using a data-assimilated version of a dust transport model (RC4) based on a ground-based NIES lidar network. The dust layer depths and the vertical and horizontal structure simulated by RC4 agreed with those of CALIOP observations from the dust source region to the far-downstream region. Two important transport mechanisms of Asian dust in the PBL and free atmosphere were clarified: a low-level dust outbreak within the dry slot region of a well-developed low-pressure system, and formation of an elevated dust layer within the warm sector of a low-pressure system. We also represent the aging of pure dust particles using the particle depolarization ratio (PDR) at 532 nm and the color ratio (CR) at 1064 nm and 532 nm. Aerosols with high PDR were observed uniformly over the dust source region. While the dust cloud was transported to the eastern downwind regions, aerosols with low PDR and high CR occur in the layer of less than 1 km height, suggesting a mixing state of spherical aerosols and dust in the surface layer.
Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 1: measurement and simulation of organic aerosol evolution
Authors: Grieshop A. P. , Logue J. M. , Donahue N. M. , Robinson A. L.
Published: April 2010

Abstract. Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) emissions from flaming and smoldering hard- and soft-wood fires under plume-like conditions. This was done by exposing the dilute emissions from a small wood stove to UV light in a smog chamber and measuring the gas- and particle-phase pollutant concentrations with a suite of instruments including a Proton Transfer Reaction Mass Spectrometer (PTR-MS), an Aerosol Mass Spectrometer (AMS) and a thermodenuder. The measurements highlight how atmospheric processing can lead to considerable evolution of the mass and volatility of biomass-burning OA. Photochemical oxidation produced substantial new OA, increasing concentrations by a factor of 1.5 to 2.8 after several hours of exposure to typical summertime hydroxyl radical (OH) concentrations. Less than 20% of this new OA could be explained using a state-of-the-art secondary organic aerosol model and the measured decay of traditional SOA precursors. The thermodenuder data indicate that the primary OA is semivolatile; at 50°C between 50 and 80% of the fresh primary OA evaporated. Aging reduced the volatility of the OA; at 50°C only 20 to 40% of aged OA evaporated. The predictions of a volatility basis-set model that explicitly tracks the partitioning and aging of low-volatility organics was compared to the chamber data. The OA production can be explained by the oxidation of low-volatility organic vapors; the model can also reproduce observed changes in OA volatility and composition. The model was used to investigate the competition between photochemical processing and dilution on OA concentrations in plumes.
Cloud and surface classification using SCIAMACHY polarization measurement devices
Authors: Lotz W. A. , Vountas M. , Dinter T. , Burrows J. P.
Published: April 2010

Abstract. A simple scheme has been developed to discriminate surface, sun glint and cloud properties in satellite based spectrometer data utilizing visible and near infrared information. It has been designed for the use with data measured by SCIAMACHY's (SCanning Imaging Absorption SpectroMeter for Atmospheric CHartographY) Polarization Measurement Devices (PMD) but the applicability is not strictly limited to this instrument. The scheme is governed by a set of constraints and thresholds developed by using satellite imagery and meteorological data. Classification targets are ice, water and generic clouds, sun glint and surface parameters, such as water, land, snow/ice, desert and vegetation. The validation has been done using MERIS (MEdium Resolution Imaging Spectrometer) and meteorological data from METAR (MÉTéorologique Aviation Régulière – a network for the provision of meteorological data for aviation). Qualitative validation using MERIS satellite imagery shows good agreement. However, the quantitative agreement is hampered by the heterogeneity of MERIS classifications within each SCIAMACHY PMD ground pixel. The comparison with METAR data shows good agreement. The comparison for sun glint classifications and MERIS results exhibits excellent agreement.
Influence of non-ideality on condensation to aerosol
Authors: Compernolle S. , Ceulemans K. , Müller J.-F.
Published: April 2010

Abstract. Secondary organic aerosol (SOA) is a complex mixture of water and organic molecules. Its composition is determined by the presence of semi-volatile or non-volatile compounds, their saturation vapor pressure and activity coefficient. The activity coefficient is a non-ideality effect and is a complex function of SOA composition. In a previous publication, the detailed chemical mechanism (DCM) for α-pinene oxidation and subsequent aerosol formation BOREAM was presented. In this work, we investigate with this DCM the impact of non-ideality by simulating smog chamber experiments for α-pinene degradation and aerosol formation and taking the activity coefficient into account of all molecules in the aerosol phase. Several versions of the UNIFAC method are tested for this purpose, and missing parameters for e.g. hydroperoxides and nitrates are inferred from fittings to activity coefficient data generated using the SPARC model. Alternative approaches to deal with these missing parameters are also tested, as well as an activity coefficient calculation method based on Hansen solubility parameters (HSP). It turns out that for most experiments, non-ideality has only a limited impact on the interaction between the organic molecules, and therefore on SOA yields and composition, when water uptake is ignored. The reason is that often, the activity coefficient is on average close to 1 and, specifically for high-VOC experiments, partitioning is not very sensitive on the activity coefficient because the equilibrium is shifted strongly towards condensation. Still, for ozonolysis experiments with low amounts of volatile organic carbon (low-VOC), the UNIFAC parameterization of Raatikainen et al. leads to significantly higher SOA yields (by up to a factor 1.6) compared to the ideal case and to other parameterizations. Water uptake is model dependent, in the order: ideal > UNIFAC-Raatikainen > UNIFAC-Peng > UNIFAC-Hansen ≈ UNIFAC-Magnussen ≈ UNIFAC-Ming. In the absence of salt dissolution, phase splitting from pure SOA is unlikely.
Relating observations of contrail persistence to numerical weather analysis output
Authors: Duda D. P. , Palikonda R. , Minnis P.
Published: April 2010

Abstract. The potential for using high-resolution meteorological data from two operational numerical weather analyses (NWA) to diagnose and predict persistent contrail formation is evaluated using two independent contrail observation databases. Contrail occurrence statistics derived from surface and satellite observations between April 2004 and June 2005 are matched to the humidity, vertical velocity, wind shear and atmospheric stability derived from analyses from the Rapid Update Cycle (RUC) and the Advanced Regional Prediction System (ARPS) models. The relationships between contrail occurrence and the NWA-derived statistics are analyzed to determine under which atmospheric conditions persistent contrail formation is favored within NWAs. Humidity is the most important factor determining whether contrails are short-lived or persistent, and persistent contrails are more likely to appear when vertical velocities are positive. The model-derived atmospheric stability and wind shear do not appear to have a significant effect on contrail occurrence.
Severe ozone air pollution in the Persian Gulf region
Authors: Lelieveld J. , Hoor P. , Jöckel P. , Pozzer A. , Hadjinicolaou P. , Cammas J.-P. , Beirle S.
Published: April 2010

Abstract. Recently it was discovered that over the Middle East during summer ozone mixing ratios can reach a pronounced maximum in the middle troposphere. Here we extend the analysis to the surface and show that especially in the Persian Gulf region conditions are highly favorable for ozone air pollution. We apply the EMAC atmospheric chemistry-climate model to investigate long-distance transport and the regional formation of ozone. Further, we make use of available in situ and satellite measurements and compare these with model output. The results indicate that the region is a hot spot of photochemical smog where European Union air quality standards are violated throughout the year. Long-distance transports of air pollution from Europe and the Middle East, natural emissions and stratospheric ozone conspire to bring about relatively high background ozone mixing ratios. This provides a hotbed to strong and growing indigenous air pollution in the dry local climate, and these conditions are likely to get worse in the future.
Results of the first air ion spectrometer calibration and intercomparison workshop
Authors: Asmi E. , Sipilä M. , Manninen H. E. , Vanhanen J. , Lehtipalo K. , Gagné S. , Neitola K. , Mirme A. , Mirme S. , Tamm E. , Uin J. , Komsaare K. , Attoui M. , Kulmala M.
Published: April 2010

Abstract. The Air Ion Spectrometer (AIS) measures mobility and size distributions of atmospheric ions. The Neutral cluster and Air Ion Spectrometer (NAIS) can additionally measure neutral particles. The number of the (N)AIS instruments in the world is only 11. Nevertheless, they are already widely used in atmospheric ion studies, particularly related to the initial steps of new particle formation. There is no standard method applicable for calibrating the ion spectrometers in the sub-3 nm ion range. However, recent development of high resolution DMAs has enabled the size separation of small ions with good mobility resolution. For the first time, the ion spectrometers were intercompared and calibrated in a workshop, held in January–February 2008 in Helsinki, Finland. The overall goal was to experimentally determine the (N)AIS transfer functions. Monomobile mobility standards, 241-Am charger ions and silver particles were generated and used as calibration aerosols. High resolution DMAs were used to size-separate the smaller (1–10 nm) ions, while at bigger diameters (4–40 nm) the size was selected with a HAUKE-type DMA. Negative ion mobilities were detected by (N)AISs with slightly better accuracy than positive, nonetheless, both were somewhat overestimated. A linear fit of slope of one to the whole dataset of mobilities suggested that (N)AISs measured the negative mobilities 1.36±0.16 times larger compared with the reference instruments. Similarly, positive mobilities were measured 1.39±0.15 times larger compared with the reference instruments. The completely monomobile mobility standards were measured with the best accuracy. The (N)AIS concentrations were compared with an aerosol electrometer (AE) and a condensation particle counter (CPC). At sizes below 1.5 nm (positive) and 3 nm (negative) the ion spectrometers detected higher concentrations while at bigger sizes they showed similar concentrations as the reference instruments. The total particle concentrations measured by the NAISs were within ±50% of the reference CPC concentration at 4–40 nm sizes. The lowest cut-off size of the NAIS in neutral particle measurements was determined to be between 1.5 and 3 nm, depending on the measurement conditions and the polarity.
Evolution of NOx emissions in Europe with focus on road transport control measures
Authors: Vestreng V. , Ntziachristos L. , Semb A. , Reis S. , Isaksen I. S. A. , Tarrasón L.
Published: April 2010

Abstract. European emission trends of nitrogen oxides since 1880 and up to present are presented here and are linked to the evolution of road transport emissions. Road transport has been the dominating source of NOx emissions since 1970, and contributes with 40% to the total emissions in 2005. Five trend regimes have been identified between 1880 and 2005. The first regime (1880–1950) is determined by a slow increase in fuel consumption all over Europe. The second regime (1950–1980) is characterized by a continued steep upward trend in liquid fuel use and by the introduction of the first regulations on road traffic emissions. Reduction in fuel consumption determines the emission trends in the third regime (1980–1990) that is also characterized by important differences between Eastern and Western Europe. Emissions from road traffic continue to grow in Western Europe in this period, and it is argued here that the reason for this continued NOx emission increase is related to early inefficient regulations for NOx in the transport sector. The fourth regime (1990–2000) involves a turning point for road traffic emissions, with a general decrease of emissions in Europe during that decade. It is in this period that we can identify the first emission reductions due to technological abatement in Western Europe. In the fifth regime (2000–2005), the economic recovery in Eastern Europe imposes increased emission from road traffic in this area. Western European emissions are on the other hand decoupled from the fuel consumption, and continue to decrease. The implementation of strict measures to control NOx emissions is demonstrated here to be a main reason for the continued Western European emission reductions. The results indicate that even though the effectiveness of European standards is hampered by a slow vehicle turnover, loopholes in the type-approval testing, and an increase in diesel consumption, the effect of such technical abatement measures is traceable in the evolution of European road traffic emissions over the last 15 years.
Fossil and non-fossil sources of organic carbon (OC) and elemental carbon (EC) in Göteborg, Sweden
Authors: Szidat S. , Ruff M. , Perron N. , Wacker L. , Synal H.-A. , Hallquist M. , Shannigrahi A. S. , Yttri K. E. , Dye C. , Simpson D.
Published: April 2010

Abstract. Particulate matter was collected at an urban site in Göteborg (Sweden) in February/March 2005 and in June/July 2006. Additional samples were collected at a rural site for the winter period. Total carbon (TC) concentrations were 2.1–3.6 μg m−3, 1.8–1.9 μg m−3, and 2.2–3.0 μg m−3 for urban/winter, rural/winter, and urban/summer conditions, respectively. Elemental carbon (EC), organic carbon (OC), water-insoluble OC (WINSOC), and water-soluble OC (WSOC) were analyzed for 14C in order to distinguish fossil from non-fossil emissions. As wood burning is the single major source of non-fossil EC, its contribution can be quantified directly. For non-fossil OC, the wood-burning fraction was determined independently by levoglucosan and 14C analysis and combined using Latin-hypercube sampling (LHS). For the winter period, the relative contribution of EC from wood burning to the total EC was >3 times higher at the rural site compared to the urban site, whereas the absolute concentrations of EC from wood burning were elevated only moderately at the rural compared to the urban site. Thus, the urban site is substantially more influenced by fossil EC emissions. For summer, biogenic emissions dominated OC concentrations most likely due to secondary organic aerosol (SOA) formation. During both seasons, a more pronounced fossil signal was observed for Göteborg than has previously been reported for Zurich, Switzerland. Analysis of air mass origin using back trajectories suggests that the fossil impact was larger when local sources dominated, whereas long-range transport caused an enhanced non-fossil signal. In comparison to other European locations, concentrations of levoglucosan and other monosaccharide anhydrides were low for the urban and the rural site in the area of Göteborg during winter.
Cloud's Center of Gravity – a compact approach to analyze convective cloud development
Authors: Koren I. , Altaratz O. , Feingold G. , Levin Z. , Reisin T.
Published: April 2010

Abstract. As cloud resolving models become more detailed, with higher resolution outputs, it is often complicated to isolate the physical processes that control the cloud attributes. Moreover, due to the high dimensionality and complexity of the model output, the analysis and interpretation of the results can be very complicated. Here we suggest a novel approach to convective cloud analysis that yields more insight into the physical and temporal evolution of clouds, and is compact and efficient. The different (3-D) cloud attributes are weighted and projected onto a single point in space and in time, that has properties of, or similar to, the Center Of Gravity (COG). The location, magnitude and spread of this variable are followed in time. The implications of the COG approach are demonstrated for a study of aerosol effects on a warm convective cloud. We show that in addition to reducing dramatically the dimensionality of the output, such an approach often enhances the signal, adds more information, and makes the physical description of cloud evolution clearer, allowing unambiguous comparison of clouds evolving in different environmental conditions. This approach may also be useful for analysis of cloud data retrieved from surface or space-based cloud radars.
Temperature dependence of yields of secondary organic aerosols from the ozonolysis of α-pinene and limonene
Authors: Saathoff H. , Naumann K.-H. , Möhler O. , Jonsson Å. M. , Hallquist M. , Kiendler-Scharr A. , Mentel Th. F. , Tillmann R. , Schurath U.
Published: April 2010

Abstract. Secondary organic aerosol (SOA) formation has been investigated as a function of temperature and humidity for the ozone-initiated reaction of the two monoterpenes α-pinene (243–313 K) and limonene (253–313 K) using the 84.5 m3 aerosol chamber AIDA. This paper gives an overview of the measurements done and presents parameters specifically useful for aerosol yield calculations. The ozonolysis reaction, selected oxidation products and subsequent aerosol formation were followed using several analytical techniques for both gas and condensed phase characterisation. The effective densities of the SOA were determined by comparing mass and volume size distributions to (1.25±0.10) g cm−3 for α-pinene and (1.3±0.2) g cm−3 for limonene. The detailed aerosol dynamics code COSIMA-SOA proved to be essential for a comprehensive evaluation of the experimental results and for providing parameterisations directly applicable within atmospheric models. The COSIMA-assisted analysis succeeded to reproduce the observed time evolutions of SOA total mass, number and size distributions by adjusting the following properties of two oxidation product proxies: individual yield parameters (αi), partitioning coefficients (Ki), vapour pressures (pi) and effective accommodation coefficients (γi). For these properties temperature dependences were derived and parameterised. Vapour pressures and partitioning coefficients followed classical Clausius – Clapeyron temperature dependences. From this relationship enthalpies of vaporisation were derived for the two more and less volatile product proxies of α-pinene: (59±8) kJ mol−1 and (24±9) kJ mol−1, and limonene: (55±14) kJ mol−1 and (25±12) kJ mol−1. The more volatile proxy components had a notably low enthalpy of vaporisation while the less volatile proxy components gave enthalpies of vaporisation comparable with those of typical products from α-pinene oxidation, e.g. pinonaldehyde and pinonic acid.
Long term precipitation chemistry and wet deposition in a remote dry savanna site in Africa (Niger)
Authors: Galy-Lacaux C. , Laouali D. , Descroix L. , Gobron N. , Liousse C.
Published: April 2010

Abstract. Long-term precipitation chemistry have been recorded in the rural area of Banizoumbou (Niger), representative of a semi-arid savanna ecosystem. A total of 305 rainfall samples ~90% of the total annual rainfall) were collected from June 1994 to September 2005. From ionic chromatography, pH major inorganic and organic ions were detected. Rainwater chemistry is controlled by soil/dust emissions associated with terrigeneous elements represented by SO42−, Ca2+, Carbonates, K+ and Mg2+. It is found that calcium and carbonates represent ~40% of the total ionic charge. The second highest contribution is nitrogenous, with annual Volume Weighed Mean (VWM) for NO3− and NH4+ concentrations of 11.6 and 18.1 μeq.l−1, respectively. This is the signature of ammonia sources from animals and NOx emissions from savannas soil-particles rain-induced. The mean annual NH3 and NO2 air concentration are of 6 ppbv and 2.6 ppbv, respectively. The annual VWM precipitation concentration of sodium and chloride are both of 8.7 μeq.l−1 which reflects the marine signature of monsoonal and humid air masses. The median pH value is of 6.05. Acidity is neutralized by mineral dust, mainly carbonates, and/or dissolved gases such NH3. High level of organic acidity with 8μeq.l−1 and 5.2 μeq.l−1 of formate and acetate were also found. The analysis of monthly Black Carbon emissions and Fraction of Absorbed Photosynthetically Active Radiation (FAPAR) values show that both biogenic emission from vegetation and biomass burning could explain the rainfall organic acidity content. The interannual variability of the VWM concentrations around the mean (1994–2005) is between ±5% and ±30% and mainly due to variations of sources strength and rainfall spatio-temporal distribution. From 1994 to 2005, the total mean wet deposition flux in the Sahelian region is of 60.1 mmol.m−2.yr−1 ±25%. Finally, Banizoumbou measurements are compared to other long-term measurements of precipitation chemistry in the wet savanna of Lamto (Côte d'Ivoire) and in the forested zone of Zoétélé (Cameroon). The total chemical loading presents a maximum in the dry savanna and a minimum in the forest (from 143.7, 100.2 to 86.6 μeq.l−1), associated with the gradient of terrigeneous sources. The wet deposition fluxes present an opposite trend, with 60.0 mmol.m−2.yr−1 in Banizoumbou, 108.6 mmol.m−2.yr−1 in Lamto and 162.9 mmol.m−2.yr−1 in Zoétélé, controlled by rainfall gradient along the ecosystems transect.
Airborne measurement of OH reactivity during INTEX-B
Authors: Mao J. , Ren X. , Brune W. H. , Olson J. R. , Crawford J. H. , Fried A. , Huey L. G. , Cohen R. C. , Heikes B. , Singh H. B. , Blake D. R. , Sachse G. W. , Diskin G. S. , Hall S. R. , Shetter R. E.
Published: April 2010

Abstract. The measurement of OH reactivity, the inverse of the OH lifetime, provides a powerful tool to investigate atmospheric photochemistry. A new airborne OH reactivity instrument was designed and deployed for the first time on the NASA DC-8 aircraft during the second phase of Intercontinental Chemical Transport Experiment-B (INTEX-B) campaign, which was focused on the Asian pollution outflow over Pacific Ocean and was based in Hawaii and Alaska. The OH reactivity was measured by adding OH, generated by photolyzing water vapor with 185 nm UV light in a moveable wand, to the flow of ambient air in a flow tube and measuring the OH signal with laser induced fluorescence. As the wand was pulled back away from the OH detector, the OH signal decay was recorded; the slope of −Δln(signal)/Δ time was the OH reactivity. The overall absolute uncertainty at the 2σ confidence levels is about 1 s−1 at low altitudes (for decay about 6 s−1), and 0.7 s−1 at high altitudes (for decay about 2 s−1). From the median vertical profile obtained in the second phase of INTEX-B, the measured OH reactivity (4.0±1.0 s−1) is higher than the OH reactivity calculated from assuming that OH was in steady state (3.3±0.8 s−1), and even higher than the OH reactivity that was calculated from the total measurements of all OH reactants (1.6±0.4 s−1). Model calculations show that the missing OH reactivity is consistent with the over-predicted OH and under-predicted HCHO in the boundary layer and lower troposphere. The over-predicted OH and under-predicted HCHO suggest that the missing OH sinks are most likely related to some highly reactive VOCs that have HCHO as an oxidation product.
Measurements of OH and HO2 concentrations during the MCMA-2006 field campaign – Part 1: Deployment of the Indiana University laser-induced fluorescence instrument
Authors: Dusanter S. , Vimal D. , Stevens P. S. , Volkamer R. , Molina L. T.
Published: April 2010

Abstract. Measurements of tropospheric hydroxyl (OH) and hydroperoxy (HO2) radicals were made during the MCMA (Mexico City Metropolitan Area) field campaign as part of the MILAGRO (Megacity Initiative: Local and Global Research Observations) project during March 2006. These radicals were measured using a laser-induced fluorescence instrument developed at Indiana University. This new instrument takes advantage of the Fluorescence Assay by Gas Expansion technique (FAGE) together with direct excitation and detection of OH at 308 nm. HO2 is indirectly measured as OH by titration with NO inside the fluorescence cell. At this stage of development, IU-FAGE is capable of detecting 3.9×105 molecule/cm3 of both OH and HO2, with a signal to noise ratio of 1, an averaged laser power of 10-mW and an averaging time of 5-min. The calibration accuracies (1σ) are ±17% for OH and ±18% for HO2 using the water-vapor photolysis/O2 actinometry calibration technique. OH and HO2 concentrations were successfully measured at an urban site in Mexico City, with observed concentrations comparable to those measured in other polluted environments. Enhanced levels of OH and HO2 radicals were observed on several days between 09:30–11:00 a.m. and suggest an intense photochemistry during morning hours that may be due to elevated sources of HOx (OH+HO2) and a fast cycling between the radicals under the high NOx (NO+NO2) conditions of the MCMA.
Summertime PM2.5 ionic species in four major cities of China: nitrate formation in an ammonia-deficient atmosphere
Authors: Pathak R. K. , Wu W. S. , Wang T.
Published: April 2010

Abstract. Strong atmospheric photochemistry in summer can produce a significant amount of secondary aerosols, which may have a large impact on regional air quality and visibility. In the study reported herein, we analyzed sulfate, nitrate, and ammonium in PM2.5 samples collected using a 24-h filter system at suburban and rural sites near four major cities in China (Beijing, Shanghai, Guangzhou, and Lanzhou). Overall, the PM2.5 mass concentrations were high (with a mean value of 55–68 gμgm−3), which reflects the long-known particulate pollution in China's large urban centers. We observed very high concentrations of sulfate and nitrate at the Beijing and Shanghai sites, and, in particular, abnormally high levels of nitrate (24-h average concentration up to 42 gμgm−3 and contributing up to 25% of the PM2.5 mass) in the ammonium-poor samples. The Beijing and Shanghai aerosols were characterized by high levels of aerosol acidity (~220–390 nmol m−3) and low levels of in-situ pH (−0.77 to −0.52). In these samples, the formation of the observed high concentrations of particulate nitrate cannot be explained by homogeneous gas-phase reaction between ammonia and nitric acid. Examination of the relation of nitrate to relative humidity and aerosol loading suggests that the nitrate was most probably formed via the heterogeneous hydrolysis of N2O5 on the surface of the moist and acidic aerosols in Beijing and Shanghai. In comparison, the samples collected in Lanzhou and Guangzhou were ammonium-rich with low levels of aerosol acidity (~65–70 nmol m−3), and the formation of ammonium nitrate via the homogeneous gas-phase reaction was favored, which is similar to many previous studies. An empirical fit has been derived to relate fine nitrate to aerosol acidity, aerosol water content, aerosol surface area, and the precursor of nitrate for the data from Beijing and Shanghai.
Tropospheric ozone climatology at two Southern Hemisphere tropical/subtropical sites, (Reunion Island and Irene, South Africa) from ozonesondes, LIDAR, and in situ aircraft measurements
Authors: Clain G. , Baray J. L. , Delmas R. , Diab R. , Leclair de Bellevue J. , Keckhut P. , Posny F. , Metzger J. M. , Cammas J. P.
Published: April 2010

Abstract. This paper presents a climatology and trends of tropospheric ozone in the Southwestern Indian Ocean (Reunion Island) and South Africa (Irene and Johannesburg). This study is based on a multi-instrumental dataset: PTU-O3 ozonesondes, DIAL LIDAR and MOZAIC airborne instrumentation. The seasonal profiles of tropospheric ozone at Reunion Island have been calculated from two different data sets: ozonesondes and LIDAR. The two climatological profiles are similar, except in austral summer when the LIDAR profiles show greater values in the free troposphere, and in the upper troposphere when the LIDAR profiles show lower values during all seasons. These results show that the climatological value of LIDAR profiles must be discussed with care since LIDAR measurements can be performed only under clear sky conditions, and the upper limit of the profile depends on the signal strength. In addition, linear trends have been calculated from ozonesonde data at Reunion and Irene. Considering the whole tropospheric column, the trend is slightly positive for Reunion, and more clearly positive for Irene. Trend calculations have also been made separating the troposphere into three layers, and separating the dataset into seasons. Results show that the positive trend for Irene is governed by the lower layer that is affected by industrial pollution and biomass burning. On the contrary, for Reunion Island, the strongest trends are observed in the upper troposphere, and in winter when stratosphere-troposphere exchange is more frequently expected.
Stratospheric BrONO2 observed by MIPAS
Authors: Höpfner M. , Orphal J. , von Clarmann T. , Stiller G. , Fischer H.
Published: April 2010

Abstract. The first measurements of stratospheric bromine nitrate (BrONO2) are reported. Bromine nitrate has been clearly identified in atmospheric infrared emission spectra recorded with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the European Envisat satellite, and stratospheric concentration profiles have been determined for different conditions (day and night, different latitudes). The BrONO2 concentrations show strong day/night variations, with much lower concentrations during the day. Maximum volume mixing ratios observed during night are 20 to 25 pptv. The observed concentration profiles are in agreement with estimations from photochemical models and show that the current understanding of stratospheric bromine chemistry is generally correct.
Spatial distribution of Δ14CO2 across Eurasia: measurements from the TROICA-8 expedition
Authors: Turnbull J. C. , Miller J. B. , Lehman S. J. , Hurst D. , Peters W. , Tans P. P. , Southon J. , Montzka S. A. , Elkins J. W. , Mondeel D. J. , Romashkin P. A. , Elansky N. , Skorokhod A.
Published: April 2010

Abstract. Because fossil fuel derived CO2 is the only source of atmospheric CO2 that is devoid of 14C, atmospheric measurements of Δ14CO2 can be used to constrain fossil fuel emission estimates at local and regional scales. However, at the continental scale, uncertainties in atmospheric transport and other sources of variability in Δ14CO2 may influence the fossil fuel detection capability. We present a set of Δ14CO2 observations from the train-based TROICA-8 expedition across Eurasia in March–April 2004. Local perturbations in Δ14CO2 are caused by easily identifiable sources from nuclear reactors and localized pollution events. The remaining data show an increase in Δ14CO2 from Western Russia (40° E) to Eastern Siberia (120° E), consistent with depletion in 14CO2 caused by fossil fuel CO2 emissions in heavily populated Europe, and gradual dispersion of the fossil fuel plume across Northern Asia. Other trace gas species which may be correlated with fossil fuel CO2 emissions, including carbon monoxide, sulphur hexafluoride, and perchloroethylene, were also measured and the results compared with the Δ14CO2 measurements. The sulphur hexafluoride longitudinal gradient is not significant relative to the measurement uncertainty. Carbon monoxide and perchloroethylene show large-scale trends of enriched values in Western Russia and decreasing values in Eastern Siberia, consistent with fossil fuel emissions, but exhibit significant spatial variability, especially near their primary sources in Western Russia. The clean air Δ14CO2 observations are compared with simulated spatial gradients from the TM5 atmospheric transport model. We show that the change in Δ14CO2 across the TROICA transect is due almost entirely to emissions of fossil fuel CO2, but that the magnitude of this Δ14CO2 gradient is relatively insensitive to modest uncertainties in the fossil fuel flux. In contrast, the Δ14CO2 gradient is more sensitive to the modeled representation of vertical mixing, suggesting that Δ14CO2 may be a useful tracer for training mixing in atmospheric transport models.
Automatic detection of ship tracks in ATSR-2 satellite imagery
Authors: Campmany E. , Grainger R. G. , Dean S. M. , Sayer A. M.
Published: April 2010

Abstract. Ships modify cloud microphysics by adding cloud condensation nuclei (CCN) to a developing or existing cloud. These create lines of larger reflectance in cloud fields that are observed in satellite imagery. An algorithm has been developed to automate the detection of ship tracks in Along Track Scanning Radiometer 2 (ATSR-2) imagery. The scheme has been integrated into the Global Retrieval of ATSR Cloud Parameters and Evaluation (GRAPE) processing chain. The algorithm firstly identifies intensity ridgelets in clouds which have the potential to be part of a ship track. This identification is done by comparing each pixel with its surrounding ones. If the intensity of three adjacent pixels is greater than the intensity of their neighbours, then it is classified as a ridgelet. These ridgelets are then connected together, according to a set of connectivity rules, to form tracks which are classed as ship tracks if they are long enough. The algorithm has been applied to two years of ATSR-2 data. Ship tracks are most frequently seen off the west coast of California, and the Atlantic coast of both West Africa and South-Western Europe. The global distribution of ship tracks shows strong seasonality, little inter-annual variability and a similar spatial pattern to the distribution of ship emissions.
Gaseous elemental and reactive mercury in Southern New Hampshire
Authors: Sigler J. M. , Mao H. , Talbot R.
Published: April 2010

Abstract. We conducted measurements of Hg0 and RGM at two inland sites, Thompson Farm (TF) and Pac Monadnock (PM), and a marine site (Appledore Island (AI)) from the UNH AIRMAP observing network in New Hampshire in 2007. Measurements of other important trace gases and meteorological variables were used to help understand influences on the atmospheric Hg budget in New England. Seasonal variation in both species observed at TF and PM is attributable to such factors as seasonal variation in deposition strength, meteorological conditions and biogenic emissions. Hg0 and RGM varied diurnally at TF, particularly in spring, following the trend in air temperature and jNO2 and suggesting photochemical production of RGM. The diurnal patterns of Hg0 and RGM at AI during summer were nearly opposite in phase, with Hg0 decreasing through late afternoon, suggesting more significant photochemical oxidation of Hg0 to RGM in the marine environment, likely due to the presence of marine halogen compounds. A significant relationship of RGM with SO2 at TF suggests a strong contribution of RGM from anthropogenic sources. Significant levels of halogen compounds measured at TF in previous studies, as well as similar Hg0 levels and Hg0-CO ratios at TF and AI may suggest that similar air masses are prevalent at these sites.
Characterisation of episodic aerosol types over the Australian continent
Authors: Qin Y. , Mitchell R. M.
Published: April 2010

Abstract. Classification of Australian continental aerosol types resulting from episodes of enhanced source activity, such as smoke plumes and dust outbreaks, is carried out via cluster analysis of optical properties obtained from inversion of sky radiance distributions at Australian aerosol ground stations using data obtained over the last decade. The cluster analysis distinguishes four significant classes, which are identified on the basis of their optical properties and provenance as determined by satellite imagery and back-trajectory analysis. The four classes are identified respectively as aged smoke, fresh smoke, coarse dust and a super-absorptive aerosol. While the first three classes show similarities with comparable aerosol types identified elsewhere, the super-absorptive aerosol has no obvious foreign prototype. The class identified as coarse dust shows a prominent depression in single scattering albedo in the blue spectral region due to absorption by hematite, which is shown to be more abundant in central Australian dust relative to the "dust belt"of the Northern Hemisphere. The super-absorptive class is distinctive in view of its very low single scattering albedo (~0.7 at 500 nm) and variable enhanced absorption at 440 nm. The strong absorption by this aerosol requires a high black carbon content while the enhanced blue-band absorption may derive from organic compounds emitted during the burning of specific vegetation types. This aerosol exerts a positive radiative forcing at the top of atmosphere (TOA), with a large deposition of energy in the atmosphere per unit aerosol optical depth. This contrasts to the other three classes where the TOA forcing is negative. Optical properties of the four types will be used to improve the representation of Australian continental aerosol in climate models, and to enhance the accuracy of satellite-based aerosol retrievals over Australia.