bluuebunny/crossref_metadata_2025 huggingface dataset:
What can we learn from European continuous atmospheric CO2 measurements to quantify regional fluxes – Part 1: Potential of the 2001 network
Authors: Carouge C. , Bousquet P. , Peylin P. , Rayner P. J. , Ciais P.
Published: April 2010

Abstract. An inverse model using atmospheric CO2 observations from a European network of stations to reconstruct daily CO2 fluxes and their uncertainties over Europe at 40 km resolution has been developed within a Bayesian framework. In this first part, a pseudo-data experiment is performed to assess the potential of continuous measurements over Europe using a network of 10 stations of the AEROCARB project such as in 2001 (http://www.aerocarb.cnrs-gif.fr/). Under the assumptions of a small observation noise and a perfect atmospheric transport model, the reconstruction of daily CO2 fluxes and in particular of their synoptic variability is best over Western Europe where the network is the densest. At least a 10 days temporal and a 1000 km spatial averaging of the inverted daily/40 km fluxes is required in order to obtain a good agreement between the estimated and the "true" fluxes in terms of correlation and variability. The performance of the inversion system rapidly degrades when fluxes are sought for a smaller temporal or spatial averaging.
Technical Note: Ensuring consistent, global measurements of very short-lived halocarbon gases in the ocean and atmosphere
Authors: Butler J. H. , Bell T. G. , Hall B. D. , Quack B. , Carpenter L. J. , Williams J.
Published: April 2010

Abstract. Very short-lived halocarbons are significant sources of reactive halogen in the marine boundary layer, and likely in the upper troposphere and lower stratosphere. Quantifying ambient concentrations in the surface ocean and atmosphere is essential for understanding the atmospheric impact of these trace gas fluxes. Despite the body of literature increasing substantially over recent years, calibration issues complicate the comparison of results and limit the utility of building larger-scale databases that would enable further development of the science (e.g. sea-air flux quantification, model validation, etc.). With this in mind, thirty-one scientists from both atmospheric and oceanic halocarbon communities in eight nations gathered in London in February 2008 to discuss the scientific issues and plan an international effort toward developing common calibration scales (http://tinyurl.com/c9cg58). Here, we discuss the outputs from this meeting, suggest the compounds that should be targeted initially, identify opportunities for beginning calibration and comparison efforts, and make recommendations for ways to improve the comparability of previous and future measurements.
Overview of mercury measurements in the Antarctic troposphere
Authors: Dommergue A. , Sprovieri F. , Pirrone N. , Ebinghaus R. , Brooks S. , Courteaud J. , Ferrari C. P.
Published: April 2010

Abstract. Polar ecosystems are considered to be the last pristine environments of the earth relatively uninfluenced by human activities. Antarctica in particular, compared to the Arctic is considered to be even less affected by any kind of anthropogenic influences. Once contaminants reach the Polar Regions, their lifetime in the troposphere depends on local removal processes. Atmospheric mercury, in particular, has unique characteristics that include long-range transport to Polar Regions and the transformation to more toxic and water-soluble compounds that may potentially become bioavailable. These chemical-physical properties have placed mercury on the priority list of an increasing number of International, European and National conventions, and agreements, aimed at the protection of the ecosystems including human health (i.e. GEO, UNEP, AMAP, UN-ECE, HELCOM, OSPAR). This interest, in turn, stimulates a significant amount of research including measurements of gaseous elemental mercury reaction rate constant with atmospheric oxidants, experimental and modelling studies in order to understand the cycling of mercury in Polar Regions, and its impact to these ecosystems. Special attention in terms of contamination of Polar Regions is paid to the consequences of the springtime phenomena, referred to as "Atmospheric Mercury Depletion Events" (AMDEs), during which elemental mercury through a series of photochemically-initiated reactions involving halogens, may be converted to a reactive form that may accumulate in polar coastal, or sea ice, ecosystems. The discovery of the AMDEs, first noted in the Arctic, has also been observed at both poles and was initially considered to result in an important net input of atmospheric mercury into the polar surfaces. However, recent studies point out that complex processes take place after deposition that may result in less significant net-inputs from the atmosphere since a fraction, sometimes significant, of deposited mercury may be recycled. Therefore, the contribution of this unique reactivity occurring in polar atmospheres to the global budget of atmospheric mercury, and the role played by snow and ice surfaces of these regions, are important issues. This paper presents a review of atmospheric mercury studies conducted in the Antarctic troposphere, both at coastal locations and on the Antarctic Plateau since 1985. Our current understanding of atmospheric reactivity in this region is also presented.
Synergetic use of millimeter- and centimeter-wavelength radars for retrievals of cloud and rainfall parameters
Authors: Matrosov S. Y.
Published: April 2010

Abstract. A remote sensing approach for simultaneous retrievals of cloud and rainfall parameters in the vertical column above the US Department of Energy's (DOE) Climate Research Facility at the Tropical Western Pacific (TWP) Darwin site in Australia is described. This approach uses vertically pointing measurements from a DOE Ka-band radar and scanning measurements from a nearby C-band radar pointing toward the TWP Darwin site. Rainfall retrieval constraints are provided by data from a surface impact disdrometer. The approach is applicable to stratiform precipitating cloud systems when a separation between the liquid hydrometeor layer, which contains rainfall and liquid water clouds, and the ice hydrometeor layer is provided by the radar bright band. Absolute C-band reflectivities and Ka-band vertical reflectivity gradients in the liquid layer are used for retrievals of the mean layer rain rate and cloud liquid water path (CLWP). C-band radar reflectivities are also used to estimate ice water path (IWP) in regions above the melting layer. The retrieval uncertainties of CLWP and IWP for typical stratiform precipitation systems are about 500–800 g m−2 (for CLWP) and a factor of 2 (for IWP). The CLWP retrieval uncertainties increase with rain rate, so retrievals for higher rain rates may be impractical. The expected uncertainties of layer mean rain rate retrievals are around 20%, which, in part, is due to constraints available from the disdrometer data. The applicability of the suggested approach is illustrated for two characteristic events observed at the TWP Darwin site during the wet season of 2007. A future deployment of W-band radars at the DOE tropical Climate Research Facilities can improve CLWP estimation accuracies and provide retrievals for a wider range of stratiform precipitating cloud events.
Global atmospheric budget of acetaldehyde: 3-D model analysis and constraints from in-situ and satellite observations
Authors: Millet D. B. , Guenther A. , Siegel D. A. , Nelson N. B. , Singh H. B. , de Gouw J. A. , Warneke C. , Williams J. , Eerdekens G. , Sinha V. , Karl T. , Flocke F. , Apel E. , Riemer D. D. , Palmer P. I. , Barkley M.
Published: April 2010

Abstract. We construct a global atmospheric budget for acetaldehyde using a 3-D model of atmospheric chemistry (GEOS-Chem), and use an ensemble of observations to evaluate present understanding of its sources and sinks. Hydrocarbon oxidation provides the largest acetaldehyde source in the model (128 Tg a−1, a factor of 4 greater than the previous estimate), with alkanes, alkenes, and ethanol the main precursors. There is also a minor source from isoprene oxidation. We use an updated chemical mechanism for GEOS-Chem, and photochemical acetaldehyde yields are consistent with the Master Chemical Mechanism. We present a new approach to quantifying the acetaldehyde air-sea flux based on the global distribution of light absorption due to colored dissolved organic matter (CDOM) derived from satellite ocean color observations. The resulting net ocean emission is 57 Tg a−1, the second largest global source of acetaldehyde. A key uncertainty is the acetaldehyde turnover time in the ocean mixed layer, with quantitative model evaluation over the ocean complicated by known measurement artifacts in clean air. Simulated concentrations in surface air over the ocean generally agree well with aircraft measurements, though the model tends to overestimate the vertical gradient. PAN:NOx ratios are well-simulated in the marine boundary layer, providing some support for the modeled ocean source. We introduce the Model of Emissions of Gases and Aerosols from Nature (MEGANv2.1) for acetaldehyde and ethanol and use it to quantify their net flux from living terrestrial plants. Including emissions from decaying plants the total direct acetaldehyde source from the land biosphere is 23 Tg a−1. Other terrestrial acetaldehyde sources include biomass burning (3 Tg a−1) and anthropogenic emissions (2 Tg a−1). Simulated concentrations in the continental boundary layer are generally unbiased and capture the spatial gradients seen in observations over North America, Europe, and tropical South America. However, the model underestimates acetaldehyde levels in urban outflow, suggesting a missing source in polluted air. Ubiquitous high measured concentrations in the free troposphere are not captured by the model, and based on present understanding are not consistent with concurrent measurements of PAN and NOx: we find no compelling evidence for a widespread missing acetaldehyde source in the free troposphere. We estimate the current US source of ethanol and acetaldehyde (primary + secondary) at 1.3 Tg a−1 and 7.8 Tg a−1, approximately 60{%} and 480% of the corresponding increases expected for a national transition from gasoline to ethanol fuel.
A review of the theoretical basis for bulk mass flux convective parameterization
Authors: Plant R. S.
Published: April 2010

Abstract. Most parameterizations for precipitating convection in use today are bulk schemes, in which an ensemble of cumulus elements with different properties is modelled as a single, representative entraining-detraining plume. We review the underpinning mathematical model for such parameterizations, in particular by comparing it with spectral models in which elements are not combined into the representative plume. The chief merit of a bulk model is that the representative plume can be described by an equation set with the same structure as that which describes each element in a spectral model. The equivalence relies on an ansatz for detrained condensate introduced by Yanai et al. (1973) and on a simplified microphysics. There are also conceptual differences in the closure of bulk and spectral parameterizations. In particular, we show that the convective quasi-equilibrium closure of Arakawa and Schubert (1974) for spectral parameterizations cannot be carried over to a bulk parameterization in a straightforward way. Quasi-equilibrium of the cloud work function assumes a timescale separation between a slow forcing process and a rapid convective response. But, for the natural bulk analogue to the cloud-work function, the relevant forcing is characterised by a different timescale, and so its quasi-equilibrium entails a different physical constraint. Closures of bulk parameterizations that use a parcel value of CAPE do not suffer from this timescale issue. However, the Yanai et al. (1973) ansatz must be invoked as a necessary ingredient of those closures.
Assessment of parameters describing representativeness of air quality in-situ measurement sites
Authors: Henne S. , Brunner D. , Folini D. , Solberg S. , Klausen J. , Buchmann B.
Published: April 2010

Abstract. The atmospheric layer closest to the ground is strongly influenced by variable surface fluxes (emissions, surface deposition) and can therefore be very heterogeneous. In order to perform air quality measurements that are representative of a larger domain or a certain degree of pollution, observatories are placed away from population centres or within areas of specific population density. Sites are often categorised based on subjective criteria that are not uniformly applied by the atmospheric community within different administrative domains yielding an inconsistent global air quality picture. A novel approach for the assessment of parameters reflecting site representativeness is presented here, taking emissions, deposition and transport towards 34 sites covering Western and Central Europe into account. These parameters are directly inter-comparable among the sites and can be used to select sites that are, on average, more or less suitable for data assimilation and comparison with satellite and model data. Advection towards these sites was simulated by backward Lagrangian Particle Dispersion Modelling (LPDM) to determine the sites' average catchment areas for the year 2005 and advection times of 12, 24 and 48 h. Only variations caused by emissions and transport during these periods were considered assuming that these dominate the short-term variability of most but especially short lived trace gases. The derived parameters describing representativeness were compared between sites and a novel, uniform and observation-independent categorisation of the sites based on a clustering approach was established. Six groups of European background sites were identified ranging from generally remote to more polluted agglomeration sites. These six categories explained 50 to 80% of the inter-site variability of median mixing ratios and their standard deviation for NO2 and O3, while differences between group means of the longer-lived trace gas CO were insignificant. The derived annual catchment areas strongly depended on the applied LPDM and input wind fields, the catchment settings and the year of analysis. Nevertheless, the parameters describing representativeness showed considerably less variability than the catchment geometry, supporting the applicability of the derived station categorisation.
Tracer measurements in the tropical tropopause layer during the AMMA/SCOUT-O3 aircraft campaign
Authors: Homan C. D. , Volk C. M. , Kuhn A. C. , Werner A. , Baehr J. , Viciani S. , Ulanovski A. , Ravegnani F.
Published: April 2010

Abstract. We present airborne in situ measurements made during the AMMA (African Monsoon Multidisciplinary Analysis)/SCOUT-O3 campaign between 31 July and 17 August 2006 on board the M55 Geophysica aircraft, based in Ouagadougou, Burkina Faso. CO2 and N2O were measured with the High Altitude Gas Analyzer (HAGAR), CO was measured with the Cryogenically Operated Laser Diode (COLD) instrument, and O3 with the Fast Ozone ANalyzer (FOZAN). We analyse the data obtained during five local flights to study the dominant transport processes controlling the tropical tropopause layer (TTL, here ~350–375 K) and lower stratosphere above West-Africa: deep convection up to the level of main convective outflow, overshooting of deep convection, and horizontal inmixing across the subtropical tropopause. Besides, we examine the morphology of the stratospheric subtropical barrier. Except for the flight of 13 August, distinct minima in CO2 mixing ratios indicate convective outflow of boundary layer air in the TTL. The CO2 profiles show that the level of main convective outflow was mostly located at potential temperatures between 350 and 360 K, and for 11 August reached up to 370 K. While the CO2 minima indicate quite significant convective influence, the O3 profiles suggest that the observed convective signatures were mostly not fresh, but of older origin (several days or more). When compared with the mean O3 profile measured during a previous campaign over Darwin in November 2005, the O3 minimum at the main convective outflow level was less pronounced over Ouagadougou. Furthermore O3 mixing ratios were much higher throughout the whole TTL and, unlike over Darwin, rarely showed low values observed in the regional boundary layer. Signatures of irreversible mixing following overshooting of convective air were scarce in the tracer data. Some small signatures indicative of this process were found in CO2 profiles between 390 and 410 K during the flights of 4 and 8 August, and in CO data at 410 K on 7 August. However, the absence of expected corresponding signatures in other tracer data makes this evidence inconclusive, and overall there is little indication from the observations that overshooting convection has a profound impact on gas-phase tracer TTL composition during AMMA. We find the amount of photochemically aged air isentropically mixed into the TTL across the subtropical tropopause to be not significant. Using the N2O observations we estimate the fraction of aged extratropical stratospheric air in the TTL to be 0.0±0.1 up to 370 K during the local flights. Above the TTL this fraction increases to 0.3±0.1 at 390 K. The subtropical barrier, as indicated by the slope of the correlation between N2O and O3 between 415 and 490 K, does not appear as a sharp border between the tropics and extratropics, but rather as a gradual transition region between 10° N and 25° N where isentropic mixing between these two regions may occur.
Application of positive matrix factorization to on-road measurements for source apportionment of diesel- and gasoline-powered vehicle emissions in Mexico City
Authors: Thornhill D. A. , Williams A. E. , Onasch T. B. , Wood E. , Herndon S. C. , Kolb C. E. , Knighton W. B. , Zavala M. , Molina L. T. , Marr L. C.
Published: April 2010

Abstract. The goal of this research is to quantify diesel- and gasoline-powered motor vehicle emissions within the Mexico City Metropolitan Area (MCMA) using on-road measurements captured by a mobile laboratory combined with positive matrix factorization (PMF) receptor modeling. During the MCMA-2006 ground-based component of the MILAGRO field campaign, the Aerodyne Mobile Laboratory (AML) measured many gaseous and particulate pollutants, including carbon dioxide, carbon monoxide (CO), nitrogen oxides (NOx), benzene, toluene, alkylated aromatics, formaldehyde, acetaldehyde, acetone, ammonia, particle number, fine particulate mass (PM2.5), and black carbon (BC). These serve as inputs to the receptor model, which is able to resolve three factors corresponding to gasoline engine exhaust, diesel engine exhaust, and the urban background. Using the source profiles, we calculate fuel-based emission factors for each type of exhaust. The MCMA's gasoline-powered vehicles are considerably dirtier, on average, than those in the US with respect to CO and aldehydes. Its diesel-powered vehicles have similar emission factors of NOx and higher emission factors of aldehydes, particle number, and BC. In the fleet sampled during AML driving, gasoline-powered vehicles are found to be responsible for 97% of total vehicular emissions of CO, 22% of NOx, 95–97% of each aromatic species, 72–85% of each carbonyl species, 74% of ammonia, negligible amounts of particle number, 26% of PM2.5, and 2% of BC; diesel-powered vehicles account for the balance. Because the mobile lab spent 17% of its time waiting at stoplights, the results may overemphasize idling conditions, possibly resulting in an underestimate of NOx and overestimate of CO emissions. On the other hand, estimates of the inventory that do not correctly account for emissions during idling are likely to produce bias in the opposite direction.The resulting fuel-based estimates of emissions are lower than in the official inventory for CO and NOx and higher for VOCs. For NOx, the fuel-based estimates are lower for gasoline-powered vehicles but higher for diesel-powered ones compared to the official inventory. While conclusions regarding the inventory should be interpreted with care because of the small sample size, 3.5 h of driving, the discrepancies with the official inventory agree with those reported in other studies.
Measurements of iodine monoxide at a semi polluted coastal location
Authors: Furneaux K. L. , Whalley L. K. , Heard D. E. , Atkinson H. M. , Bloss W. J. , Flynn M. J. , Gallagher M. W. , Ingham T. , Kramer L. , Lee J. D. , Leigh R. , McFiggans G. B. , Mahajan A. S. , Monks P. S. , Oetjen H. , Plane J. M. C. , Whitehead J. D.
Published: April 2010

Abstract. Point source measurements of IO by laser induced fluorescence spectroscopy were made at a semi-polluted coastal location during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) campaign in September 2006. The site, on the NW French coast in Roscoff, was characterised by extensive intertidal macroalgae beds which were exposed at low tide. The closest known iodine active macroalgae beds were at least 300 m from the measurement point. From 20 days of measurements, IO was observed above the instrument limit of detection on 14 days, of which a clear diurnal profile was observed on 11 days. The maximum IO mixing ratio was 30.0 pptv (10 s integration period) during the day, amongst the highest concentrations ever observed in the atmosphere, and 1–2 pptv during the night. IO concentrations were strongly dependent on tidal height, the intensity of solar irradiation and meteorological conditions. An intercomparison of IO measurements made using point source and spatially averaged DOAS instruments confirms the presence of hot-spots of IO caused by an inhomogeneous distribution of macroalgae. The co-incident, point source measurement of IO and ultra fine particles (2.5 nm≥d≥10 nm) displayed a strong correlation, providing evidence that IO is involved in the production pathway of ultra fine particles at coastal locations. Finally, a modelling study shows that high IO concentrations which are likely to be produced in a macrolagae rich environment can significantly perturb the concentrations of OH and HO2 radicals. The effect of IO on HOx is reduced as NOx concentrations increase.
IASI observations of seasonal and day-to-day variations of tropospheric ozone over three highly populated areas of China: Beijing, Shanghai, and Hong Kong
Authors: Dufour G. , Eremenko M. , Orphal J. , Flaud J.-M.
Published: April 2010

Abstract. IASI observations of tropospheric ozone over the Beijing, Shanghai and Hong Kong areas during one year (2008) have been analysed, demonstrating the capability of space-borne infrared nadir measurements to probe seasonal and even day-to-day variations of lower tropospheric ozone (0–6 km partial columns) on the regional scale of highly populated areas. The monthly variations of lower tropospheric ozone retrieved from IASI clearly show the influence of the Asian summer monsoon that brings clean air masses from the Pacific during summer. They exhibit indeed a sharp ozone maximum in late spring and early summer (May–June) followed by a summer minimum. The time periods and the intensities of the maxima and of the decreases are latitude-dependent: they are more pronounced in Hong Kong and Shanghai than in Beijing. Moreover, IASI provides the opportunity to follow the spatial variations of ozone over the surroundings of each megacity as well as its daily variability. We show here that the large lower tropospheric ozone amounts (0–6 km partial columns) observed with IASI are mainly downwind the highest populated areas in each region, thus possibly suggesting the anthropogenic origin of the large ozone amounts observed. Finally, an analysis of the mean ozone profiles over each region – for selected days with high ozone events – in association with the analysis of the meteorological situation shows that the high ozone amounts observed during winter are likely related to descents of ozone-rich air from the stratosphere, whereas in spring and summer the tropospheric ozone is likely enhanced by photochemical production in polluted areas and/or in air masses from fire plumes.
Characterization of oligomers from methylglyoxal under dark conditions: a pathway to produce secondary organic aerosol through cloud processing during nighttime
Authors: Yasmeen F. , Sauret N. , Gal J.-F. , Maria P.-C. , Massi L. , Maenhaut W. , Claeys M.
Published: April 2010

Abstract. Aqueous-phase oligomer formation from methylglyoxal, a major atmospheric photooxidation product, has been investigated in a simulated cloud matrix under dark conditions. The aim of this study was to explore an additional pathway producing secondary organic aerosol (SOA) through cloud processes without participation of photochemistry during nighttime. Indeed, atmospheric models still underestimate SOA formation, as field measurements have revealed more SOA than predicted. Soluble oligomers (n = 1–8) formed in the course of acid-catalyzed aldol condensation and acid-catalyzed hydration followed by acetal formation have been detected and characterized by positive and negative ion electrospray ionization mass spectrometry. Aldol condensation proved to be a favorable mechanism under simulated cloud conditions, while hydration/acetal formation was found to strongly depend on the pH of the system and only occurred at a pH<3.5. No evidence was found for formation of organosulfates. The aldol oligomer series starts with a β-hydroxy ketone via aldol condensation, where oligomers are formed by multiple additions of C3H4O2 units (72 Da) to the parent β-hydroxy ketone. Ion trap mass spectrometry experiments were performed to structurally characterize the major oligomer species. A mechanistic pathway for the growth of oligomers under cloud conditions and in the absence of UV-light and OH radicals, which could substantially enhance in-cloud SOA yields, is proposed here for the first time.
More evidence for very short-lived substance contribution to stratospheric chlorine inferred from HCl balloon-borne in situ measurements in the tropics
Authors: Mébarki Y. , Catoire V. , Huret N. , Berthet G. , Robert C. , Poulet G.
Published: April 2010

Abstract. Volume mixing ratio (vmr) vertical profiles of hydrogen chloride (HCl) are retrieved from in situ measurements performed by a balloon-borne infrared tunable diode laser absorption spectrometer (SPIRALE) during two balloon flights in the tropics (Teresina, Brazil, 5.1° S–42.9° W) in June 2005 and June 2008. HCl vertical profiles obtained from 15 to 31 km are presented and analysed to estimate the contribution of very short-lived substances (VSLS) to total stratospheric chlorine. Both retrieved vertical profiles of HCl from these flights agree very well with each other, with estimated overall uncertainties of 6% on vmr between 23 and 31 km. Upper limits of HCl vmr as low as 20 pptv in June 2008 and 30 pptv in June 2005 are inferred in the upper part of the tropical tropopause layer (TTL). Backward trajectory calculations and such low amounts suggest that the air masses sampled correspond to typical background conditions, i.e. neither influenced by recent tropospheric nor stratospheric air. Taking into account the recently reported VSL source gas measurements obtained in similar conditions (Laube et al., 2008) and the main intermediate degradation product gas COCl2 (Fu et al., 2007), a total VSLS contribution of 85±40 pptv to stratospheric chlorine is inferred. This refines the WMO (2007) estimation of 50 to 100 pptv, which was not taking into account any HCl contribution. In addition, comparisons of HCl measurements between SPIRALE and the Aura MLS satellite instrument in the tropical lower and middle stratosphere lead to a very good agreement. The previous agreement between MLS-deduced upper stratospheric total chlorine content and modelled values including 100 pptv of VSLS (Froidevaux et al., 2006) is thus supported by our present result about the VSLS contribution.
Impact of mineral dust on nitrate, sulfate, and ozone in transpacific Asian pollution plumes
Authors: Fairlie T. D. , Jacob D. J. , Dibb J. E. , Alexander B. , Avery M. A. , van Donkelaar A. , Zhang L.
Published: April 2010

Abstract. We use a 3-D global chemical transport model (GEOS-Chem) to interpret aircraft observations of nitrate and sulfate partitioning in transpacific dust plumes during the INTEX-B campaign of April–May 2006. The model includes explicit transport of size-resolved mineral dust and its alkalinity, nitrate, and sulfate content. The observations show that particulate nitrate is primarily associated with dust, sulfate is primarily associated with ammonium, and Asian dust remains alkaline across the Pacific. This can be reproduced in the model by using a reactive uptake coefficient for HNO3 on dust (γ(HNO3) ~10−3) much lower than commonly assumed in models and possibly reflecting limitation of uptake by dust dissolution. The model overestimates gas-phase HNO3 by a factor of 2–3, typical of previous model studies; we show that this cannot be corrected by uptake on dust. We find that the fraction of aerosol nitrate on dust in the model increases from ~30% in fresh Asian outflow to 80–90% over the Northeast Pacific, reflecting in part the volatilization of ammonium nitrate and the resulting transfer of nitrate to the dust. Consumption of dust alkalinity by uptake of acid gases in the model is slow relative to the lifetime of dust against deposition, so that dust does not acidify (at least not in the bulk). This limits the potential for dust iron released by acidification to become bio-available upon dust deposition. Observations in INTEX-B show no detectable ozone depletion in Asian dust plumes, consistent with the model. Uptake of HNO3 by dust, suppressing its recycling to NOx, reduces Asian pollution influence on US surface ozone in the model by 10–15% or up to 1 ppb.
Atmospheric sub-3 nm particles at high altitudes
Authors: Mirme S. , Mirme A. , Minikin A. , Petzold A. , Hõrrak U. , Kerminen V. -M. , Kulmala M.
Published: April 2010

Abstract. Formation of new atmospheric aerosol particles is known to occur almost all over the world and the importance of these particles to climate and air quality has been recognized. Recently, it was found that atmospheric aerosol particle formation begins at the diameter of around 1.5–2.0 nm and a pool of sub-3 nm atmospheric particles – consisting of both charged and uncharged ones – was observed at the ground level. Here, we report on the first airborne observations of the pool of sub-3 nm neutral atmospheric particles. Between 2 and 3 nm, their concentration is roughly two orders of magnitude larger than that of the ion clusters, depending slightly on the altitude. Our findings indicate that new particle formation takes place throughout the tropospheric column up to the tropopause. Particles were found to be formed via neutral pathways in the boundary layer, and there was no sign of an increasing role by ion-induced nucleation toward the upper troposphere. Clouds, while acting as a source of sub-10 nm ions, did not perturb the overall budget of atmospheric clusters or particles.
Constraint of anthropogenic NOx emissions in China from different sectors: a new methodology using multiple satellite retrievals
Authors: Lin J.-T. , McElroy M. B. , Boersma K. F.
Published: April 2010

Abstract. A new methodology is developed to constrain Chinese anthropogenic emissions of nitrogen oxides (NOx) from four major sectors (industry, power plants, mobile and residential) in July 2008. It combines tropospheric NO2 column retrievals from GOME-2 and OMI, taking advantage of their different passing time over China (~10:00 a.m. LT (local time) versus ~02:00 p.m.) and consistent retrieval algorithms. The approach is based on the difference of NOx columns at the overpass times of the two instruments; it thus is less susceptible to the likely systematic errors embedded in individual retrievals that are consistent with each other. Also, it explicitly accounts for diurnal variations and uncertainties of NOx emissions for individual sources. Our best top-down estimate suggests a national budget of 6.8 TgN/yr (5.5 TgN/yr for East China), close to the a priori bottom-up emission estimate from the INTEX-B mission for the year of 2006. The top-down emissions are lower than the a priori near Beijing, in the northeastern provinces and along the east coast; yet they exceed the a priori over many inland regions. Systematic errors in satellite retrievals are estimated to lead to underestimation of top-down emissions by at most 17% (most likely 10%). Effects of other factors on the top-down estimate are typically less than 15% each, including lightning, soil emissions, mixing in planetary boundary layer, anthropogenic emissions of carbon monoxide and volatile organic compounds, magnitude of a priori emissions, assumptions on emission diurnal variations, and uncertainties in the four sectors. The a posteriori emission budget is 5.7 TgN/yr for East China.
Effects of boundary layer particle formation on cloud droplet number and changes in cloud albedo from 1850 to 2000
Authors: Merikanto J. , Spracklen D. V. , Pringle K. J. , Carslaw K. S.
Published: April 2010

Abstract. We use a global aerosol microphysics model to estimate the effect of particle formation through activation nucleation in the boundary layer (BL) on cloud droplet number concentration (CDNC) on global and regional scales. The calculations are carried out for years 1850 and 2000 using historical emissions inventories for primary particles and aerosol precursor gases. Predicted CDNC in 2000 are in good agreement with in-situ observations when activation nucleation is included. We find that BL particle formation increases global annual mean CDNC by approximately the same relative amount in both years (16.0% in 1850 and 13.5% in 2000). As a result, global mean changes in cloud albedo are similar with and without BL particle formation. However, there are substantial regional effects of up to 50% enhancement or suppression of the 1850–2000 albedo change. Over most modern-day polluted northern hemisphere regions, including BL particle formation scheme suppresses the 1850–2000 increase in CDNC and cloud albedo because BL particle formation is already large in 1850. Over the Arctic the albedo change is suppressed by 23% in the annual mean and by 43% in summer when BL particle formation is taken into account. The albedo change of the persistent stratocumulus cloud deck west of Chile is enhanced by 49%.
Bromoform and dibromomethane in the tropics: a 3-D model study of chemistry and transport
Authors: Hossaini R. , Chipperfield M. P. , Monge-Sanz B. M. , Richards N. A. D. , Atlas E. , Blake D. R.
Published: April 2010

Abstract. We have developed a detailed chemical scheme for the degradation of the short-lived source gases bromoform (CHBr3) and dibromomethane (CH2Br2) and implemented it in the TOMCAT/SLIMCAT three-dimensional (3-D) chemical transport model (CTM). The CTM has been used to predict the distribution of the two source gases (SGs) and 11 of their organic product gases (PGs). These first global calculations of the organic PGs show that their abundance is small. The longest lived organic PGs are CBr2O and CHBrO, but their peak tropospheric abundance relative to the surface volume mixing ratio (vmr) of the SGs is less than 5%. We calculate their mean local tropospheric lifetimes in the tropics to be ~7 and ~2 days (due to photolysis), respectively. Therefore, the assumption in previous modelling studies that SG degradation leads immediately to inorganic bromine seems reasonable. We have compared observed tropical SG profiles from a number of aircraft campaigns with various model experiments. In the tropical tropopause layer (TTL) we find that the CTM run using p levels (TOMCAT) and vertical winds from analysed divergence overestimates the abundance of CH2Br2, and to a lesser extent CHBr3, although the data is sparse and comparisons are not conclusive. Better agreement in the TTL is obtained in the sensitivity run using θ levels (SLIMCAT) and vertical motion from diabatic heating rates. Trajectory estimates of residence times in the two model versions show slower vertical transport in the SLIMCAT θ-level version. In the p-level model even when we switch off convection we still find significant amounts of the SGs considered may reach the cold point tropopause; the stratospheric source gas injection (SGI) is only reduced by ~16% for CHBr3 and ~2% for CH2Br2 without convection. Overall, the relative importance of the SG pathway and the PG pathway for transport of bromine to the stratospheric overworld (θ>380 K) has been assessed. Assuming a 10-day washout lifetime of Bry in TOMCAT, we find the delivery of total Br from CHBr3 to be 0.72 pptv with ~53% of this coming from SGI. Similary, for CH2Br2 we find a total Br value of 1.69 pptv with ~94% coming from SGI. We infer that these species contribute ~2.4 pptv of inorganic bromine to the lower stratosphere with SGI being the dominant pathway. Slower transport to and through the TTL would decrease this estimate.
A meteorological overview of the ARCTAS 2008 mission
Authors: Fuelberg H. E. , Harrigan D. L. , Sessions W.
Published: April 2010

Abstract. The Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was a multi-aircraft project whose major objective was to investigate the factors driving changes in the Arctic's atmospheric composition and climate. It was conducted during April and June–July 2008. The summer ARCTAS deployment was preceded by a week of flights over and around California to address state issues of air quality and climate forcing. This paper focuses on meteorological conditions during the ARCTAS Spring and Summer campaigns. We examine mission averaged large-scale flow patterns at the surface, 500 hPa, and 300 hPa and determine their departures from climatology. Results from runs of the Weather Research and Forecasting (WRF) model are used to describe meteorological conditions on individual days. Our WRF configuration included a nested grid approach that provided horizontal spacing as small as 5 km. Trajectories calculated from the WRF output are used to determine transport pathways to the Arctic, including their origins and the altitudes at which they reach 70° N. We also present backward trajectories from selected legs of individual ARCTAS flights. Finally, the FLEXPART Lagrangian particle dispersion model, with the high resolution WRF data as input, is used to determine the paths of anthropogenic and biomass burning-derived CO. Results show that there was frequent and widespread transport to the Arctic during both phases of ARCTAS and that the three ARCTAS aircraft sampled air having a multitude of origins, following a myriad of paths, and experiencing many types of meteorological conditions.
New particle formation during a- and b-pinene oxidation by O3, OH and NO3, and the influence of water vapour: particle size distribution studies
Authors: Bonn B. , Moorgat G. K.
Published: April 2010

Abstract. New particle formation during the oxidation of a- and b-pinene (C10H16) by ozone, OH and NO3 was studied by measuring the particle size distributions with a scanning mobility particle sizer (TSI 3936). The results indicate a drastically higher nucleation potential of the ozonolysis than in the reaction with either OH or NO3. On the contrary, the contribution of the individual oxidation reactions to form new aerosol volume was found to depend on the location of the carbon double bond to be oxidised: for the endocyclic a-pinene reactions the ozonolysis contributed mostly to the aerosol volume yield, whereas for the exocyclic  b-pinene reactions the oxidation by O3, OH and NO3 yielded a similar aerosol volume. In a second part of this study the influence of water vapour on the nucleation in all three possible oxidation routes was examined. The observations revealed only an effect of water vapour during the ozonolysis reactions.
The impact of multiphase reactions of NO2 with aromatics: a modelling approach
Authors: Lahoutifard N. , Ammann M. , Gutzwiller L. , Ervens B. , George Ch.
Published: April 2010

Abstract. The impact of multiphase reactions involving nitrogen dioxide (NO2) and aromatic compounds was simulated in this study. A mechanism (CAPRAM 2.4, MODAC Mechanism) was applied for the aqueous phase reactions, whereas RACM was applied for the gas phase chemistry. Liquid droplets were considered as monodispersed with a mean radius of 0.1 µm and a liquid content (LC) of 50 µg m-3. The multiphase mechanism has been further extended to the chemistry of aromatics, i.e. reactions involving benzene, toluene, xylene, phenol and cresol have been added. In addition, reaction of NO2 with dissociated hydroxyl substituted aromatic compounds has also been implemented. These reactions proceed through charge exchange leading to nitrite ions and therefore to nitrous acid formation. The strength of this source was explored under urban polluted conditions. It was shown that it may increase gas phase HONO levels under some conditions and that the extent of this effect is strongly pH dependent. Especially under moderate acidic conditions (i.e. pH above 4) this source may represent more than 75% of the total HONO/NO2 - production rate, but this contribution drops down close to zero in acidic droplets (as those often encountered in urban environments).
Suppression of chlorine activation on aviation-produced volatile particles
Authors: Meilinger S. K. , Kärcher B. , Peter Th.
Published: April 2010

Abstract. We examine the effect of nanometer-sized aircraft-induced aqueous sulfuric acid (H2SO4/H2O) particles on atmospheric ozone as a function of temperature. Our calculations are based on a previously derived parameterization for the regional-scale perturbations of the sulfate surface area density due to air traffic in the North Atlantic Flight Corridor (NAFC) and a chemical box model. We confirm large scale model results that at temperatures T>210 K additional ozone loss -- mainly caused by hydrolysis of BrONO2 and N2O5 -- scales in proportion with the aviation-produced increase of the background aerosol surface area. However, at lower temperatures (< 210 K) we isolate two effects which efficiently reduce the aircraft-induced perturbation: (1) background particles growth due to H2O and HNO3 uptake enhance scavenging losses of aviation-produced liquid particles and (2) the Kelvin effect efficiently limits chlorine activation on the small aircraft-induced droplets by reducing the solubility of chemically reacting species. These two effects lead to a substantial reduction of heterogeneous chemistry on aircraft-induced volatile aerosols under cold conditions. In contrast we find contrail ice particles to be potentially important for heterogeneous chlorine activation and reductions in ozone levels. These features have not been taken into consideration in previous global studies of the atmospheric impact of aviation. Therefore, to parameterize them in global chemistry and transport models, we propose the following parameterisation: scale the hydrolysis reactions by the aircraft-induced surface area increase, and neglect heterogeneous chlorine reactions on liquid plume particles but not on ice contrails and aircraft induced ice clouds.
The part of the solar spectrum with the highest influence on the formation of SOA in the continental boundary layer
Authors: Boy M. , Kulmala M.
Published: April 2010

Abstract. The relationship between nucleation events and spectral solar irradiance was analysed using two years of data collected at the Station for Measuring Forest Ecosystem-Atmosphere Relations (SMEAR II) in Hyytiälä, Finland. We analysed the data in two different ways. In the first step we calculated ten nanometer average values from the irradiance measurements between 280 and 580 nm and explored if any special wavelengths groups showed higher values on event days compared to a spectral reference curve for all the days for 2 years or to reference curves for every month. The results indicated that short wavelength irradiance between 300 and 340 nm is higher on event days in winter (February and March) compared to the monthly reference graph but quantitative much smaller than in spring or summer. By building the ratio between the average values of different event classes and the yearly reference graph we obtained peaks between 1.17 and 1.6 in the short wavelength range (300--340 nm). In the next step we included number concentrations of particles between 3 and 10 nm and calculated correlation coefficients between the different wavelengths groups and the particles. The results were quite similar to those obtained previously; the highest correlation coefficients were reached for the spectral irradiance groups 3--5 (300--330 nm) with average values for the single event classes around 0.6 and a nearly linear decrease towards higher wavelengths groups by 30%. Both analyses indicate quite clearly that short wavelength irradiance between 300 and 330 or 340 nm is the most important solar spectral radiation for the formation of newly formed aerosols. In the end we introduce a photochemical mechanism as one possible pathway how short wavelength irradiance can influence the formation of SOA by calculating the production rate of excited oxygen. This mechanism shows in which way short wavelength irradiance can influence the formation of new particles even though the absolute values are one to two magnitudes smaller compared to irradiance between 400 and 500 nm.
On the use of ATSR fire count data to estimate the seasonal and interannual variability of vegetation fire emissions
Authors: Schultz M. G.
Published: April 2010

Abstract. Biomass burning has long been recognised as an important source of trace gases and aerosols in the atmosphere. The burning of vegetation has a repeating seasonal pattern, but the intensity of burning and the exact localisation of fires vary considerably from year to year. Recent studies have demonstrated the high interannual variability of the emissions that are associated with biomass burning. In this paper I present a methodology using active fire counts from the Along-Track Scanning Radiometer (ATSR) sensor on board the ERS-2 satellite to estimate the seasonal and interannual variability of global biomass burning emissions in the time period 1996--2000. From the ATSR data, I compute relative scaling factors of burning intensity for each month, which are then applied to a standard inventory for carbon monoxide emissions from biomass burning. The new, time-resolved inventory is evaluated using the few existing multi-year burned area observations on continental scales.