bluuebunny/crossref_metadata_2025 huggingface dataset:
Interpreting the variability of space-borne CO2 column-averaged volume mixing ratios over North America using a chemistry transport model
Authors: Palmer P. I. , Barkley M. P. , Monks P. S.
Published: April 2010

Abstract. We use the GEOS-Chem chemistry transport model to interpret the sources and sinks of CO2 that determine variability of column-averaged volume mixing ratios (CVMRs), as observed by the SCIAMACHY satellite instrument, during the 2003 North American growing season. GEOS-Chem generally reproduces the magnitude and seasonal cycle of observed CO2 surface VMRs across North America and is quantitatively consistent with column VMRs in later years. However, it cannot reproduce the magnitude or variability of FSI-WFM-DOAS SCIAMACHY CVMRs. We use model tagged tracers to show that local fluxes largely determine CVMR variability over North America, with the largest individual CVMR contributions (1.1%) from the land biosphere. Fuel sources are relatively constant while biomass burning makes a significant contribution only during midsummer. We also show that non-local sources contribute significantly to total CVMRs over North America, with the boreal Asian land biosphere contributing close to 1% in midsummer at high latitudes. We used the monthly-mean Jacobian matrix for North America to illustrate that:~1) North American CVMRs represent a superposition of many weak flux signatures, but differences in flux distributions should permit independent flux estimation; and 2) the atmospheric e-folding lifetimes for many of these flux signatures are 3–4 months, beyond which time they are too well-mixed to interpret. These long lifetimes will improve the efficacy of observed CVMRs as surface CO2 flux constraints.
The effect of organic compounds on the growth rate of cloud droplets in marine and forest settings
Authors: Shantz N. C. , Leaitch W. R. , Phinney L. , Mozurkewich M. , Toom-Sauntry D.
Published: April 2010

Abstract. Organic matter represents an important fraction of the fine particle aerosol, yet our knowledge of the roles of organics in the activation of aerosol particles into cloud droplets is poor. A cloud condensation nucleus (CCN) counter is used to examine the relative growth rates of cloud droplets for case studies from field measurements on the North Pacific Ocean and in a coniferous forest. A model of the condensational growth of water droplets, on particles dissolving according to their solubility in water, is used to simulate the initial scattering of the droplets as they grow in the CCN counter. Simulations of the growth rates of fine particles sampled in the marine boundary layer of the North Pacific Ocean shows no evidence of natural marine organic material contributing to the CCN water uptake but there is an indication of an influence from organics from diesel ship emissions on the size distribution of sulphate and the ability of these particles to act as CCN. Simulations of the observations of water uptake on biogenic organic aerosol particles sampled in a coniferous forest indicate an impact of the organic on the water uptake rates, but one that is still smaller than that of pure sulphate. The existence of organics becomes important in determining the water uptake as the organic mass increases relative to sulphate. The values of the organic component of the hygroscopicity parameter κ that describes the CCN activity were found to be negligible for the marine particles and 0.02–0.05 for the forest particles.
The impact of free convection on late morning ozone decreases on an Alpine foreland mountain summit
Authors: Mayer J.-C. , Staudt K. , Gilge S. , Meixner F. X. , Foken T.
Published: April 2010

Abstract. Exceptional patterns in the diurnal course of ozone mixing ratio at a mountain top site (998 m a.s.l.) were observed during a field experiment (September 2005). They manifested themselves as strong and sudden decreases of ozone mixing ratio with a subsequent return to previous levels. The evaluation of corresponding long-term time series (2000–2005) revealed that such events occur mainly during summer, and affect the mountain top site on about 18% of the summer days. Combining (a) surface layer measurements at mountain summit and at the foot of the mountain, (b) in-situ (tethered balloon) and remote sensing (SODAR-RASS) measurements within the atmospheric boundary layer, the origin of these events of sudden ozone decrease could be attributed to free convection. The free convection was triggered by a rather frequently occurring wind speed minimum around the location of the mountain.
Technical Note: Chemistry-climate model SOCOL: version 2.0 with improved transport and chemistry/microphysics schemes
Authors: Schraner M. , Rozanov E. , Schnadt Poberaj C. , Kenzelmann P. , Fischer A. M. , Zubov V. , Luo B. P. , Hoyle C. R. , Egorova T. , Fueglistaler S. , Brönnimann S. , Schmutz W. , Peter T.
Published: April 2010

Abstract. We describe version 2.0 of the chemistry-climate model (CCM) SOCOL. The new version includes fundamental changes of the transport scheme such as transporting all chemical species of the model individually and applying a family-based correction scheme for mass conservation for species of the nitrogen, chlorine and bromine groups, a revised transport scheme for ozone, furthermore more detailed halogen reaction and deposition schemes, and a new cirrus parameterisation in the tropical tropopause region. By means of these changes the model manages to overcome or considerably reduce deficiencies recently identified in SOCOL version 1.1 within the CCM Validation activity of SPARC (CCMVal). In particular, as a consequence of these changes, regional mass loss or accumulation artificially caused by the semi-Lagrangian transport scheme can be significantly reduced, leading to much more realistic distributions of the modelled chemical species, most notably of the halogens and ozone.
The roles of convection, extratropical mixing, and in-situ freeze-drying in the Tropical Tropopause Layer
Authors: Read W. G. , Schwartz M. J. , Lambert A. , Su H. , Livesey N. J. , Daffer W. H. , Boone C. D.
Published: April 2010

Abstract. Mechanisms for transporting and dehydrating air across the tropical tropopause layer (TTL) are investigated with a conceptual two dimensional (2-D) model. The 2-D TTL model combines the Holton and Gettelman cold trap dehydration mechanism (Holton and Gettelman, 2001) with the two column convection model of Folkins and Martin (2005). We investigate 3 possible transport scenarios through the TTL: 1) slow uniform ascent across the level of zero radiative heating without direct convective mixing, 2) convective mixing of H2O vapor at 100% relative humidity with respect to ice (RHi) with no ice retention, and 3) convective mixing of extremely subsaturated air (100% RHi following the moist adiabatic temperature above the level of neutral buoyancy) with sufficient ice retention such that total H2O is 100%RHi. The three mechanisms produce similar seasonal cycles for H2O that are in good quantitative agreement with the Aura Microwave Limb Sounder (MLS) measurements. We use Aura MLS measurement of CO and Atmospheric Chemistry Experiment-Fourier Transform Spectrometer measurement of HDO to distinguish among the transport mechanisms. Model comparisons with the observations support the view that H2O is predominantly controlled by regions having the lowest cold point tropopause temperature but the trace species CO and HDO support the convective mixing of dry air and lofted ice. The model provides some insight into the processes affecting the long term trends observed in stratospheric H2O.
Iodine speciation in rain, snow and aerosols
Authors: Gilfedder B. S. , Lai S. C. , Petri M. , Biester H. , Hoffmann T.
Published: April 2010

Abstract. Iodine oxides, such as iodate, should be the only thermodynamically stable sink species for iodine in the troposphere. However, field observations have increasingly found very little iodate and significant amounts of iodide and soluble organically bound iodine (SOI) in precipitation and aerosols. The aim of this study was to investigate iodine speciation, including the organic fraction, in rain, snow, and aerosols in an attempt to further clarify aqueous phase iodine chemistry. Diurnal aerosol samples were taken with a 5 stage cascade impactor and a virtual impactor (PM2.5) from the Mace Head research station, Ireland, during summer 2006. Rain was collected from Australia, New Zealand, Patagonia, Germany, Ireland, and Switzerland and snow was obtained from Greenland, Germany, Switzerland, and New Zealand. Aerosols were extracted from the filters with water and all samples were analysed for total soluble iodine (TSI) by inductively coupled plasma mass spectrometry (ICP-MS) and iodine speciation was determined by coupling an ion chromatography unit to the ICP-MS. The median concentration of TSI in aerosols from Mace Head was 222 pmol m−3 (summed over all impactor stages) of which the majority was associated with the SOI fraction (median day: 90±4%, night: 94±2% of total iodine). Iodide exhibited higher concentrations than iodate (median 6% vs. 1.2% of total iodine), and displayed significant enrichment during the day compared to the night. Interestingly, up to 5 additional, presumably anionic iodo-organic peaks were observed in all IC-ICP-MS chromatograms, composing up to 15% of the TSI. Soluble organically bound iodine was also the dominant fraction in all rain and snow samples, with lesser amounts of iodide and iodate (iodate was particularly low in snow). Two of the same unidentified peaks found in aerosols were also observed in precipitation from both Southern and Northern Hemispheres. This suggests that these species are transferred from the aerosols into precipitation and that they have either a relatively long lifetime or are rapidly recycled. It is thought that SOI is formed by reactions between HOI or I2 and organic matter derived from the ocean surface layer. SOI may then photolytically decompose to yield iodide and the unidentified species. The data in this study show that iodine oxides are the least abundant species in rain, snow, and aerosols and therefore considerably more effort is required on aqueous phase iodine chemistry for a holistic understanding of the iodine cycle.
Case studies of particle formation events observed in boreal forests: implications for nucleation mechanisms
Authors: Yu F. , Turco R.
Published: April 2010

Abstract. Aerosol nucleation events observed worldwide may have significant climatic and health implications. However, the specific nucleation mechanisms remain ambiguous. Here, we report case studies of eight nucleation events observed during an intensive field campaign at a boreal forest site (Hyytiälä, Finland) in spring 2005. The present analysis is based on comprehensive kinetic simulations using an ion-mediated nucleation (IMN) model in which the key physical and chemical parameters are constrained by a variety of recent measurements. Out of the 22 days of the campaign on which nucleation events were observed, eight major events were selected for detailed analysis on the basis of indications that the observed air masses were relatively homogeneous. In most of these cases, reasonable agreement is found between IMN predictions and field data for a range of variables, including critical nucleation sizes, size-dependent overcharging ratios, and the concentrations of 1.8–3 nm stable clusters and 3–6 nm particles, and their diurnal variations. The possible reasons leading to substantial differences between observation and theory in some cases are also explored. Statistically, roughly 80% of the nucleation events recorded during the Hyytiälä campaign exhibited mean size-dependent particle overcharging ratios within the range of, or exceeding, those predicted by the IMN model, suggesting that ion nucleation processes were significant during these events. The nucleation rates calculated using the IMN modeling approach are contrasted with those predicted by other theories/models, and key differences between the results are discussed. In particular, it is concluded that the ion nucleation model originally developed by Lovejoy et al. (2004) significantly under-predicts ion nucleation rates, and cannot explain the new observations from Hyytiälä regarding the electrical properties of nanoparticles. We also show that, for the well documented conditions of the Hyytiälä project, the binary and ternary homogeneous nucleation rates calculated using the most current theories would fall well below ~10−7 cm−3 s−1, and thus would be negligible.
Transpacific transport of ozone pollution and the effect of recent Asian emission increases on air quality in North America: an integrated analysis using satellite, aircraft, ozonesonde, and surface observations
Authors: Zhang L. , Jacob D. J. , Boersma K. F. , Jaffe D. A. , Olson J. R. , Bowman K. W. , Worden J. R. , Thompson A. M. , Avery M. A. , Cohen R. C. , Dibb J. E. , Flock F. M. , Fuelberg H. E. , Huey L. G. , McMillan W. W. , Singh H. B. , Weinheimer A. J.
Published: April 2010

Abstract. We use an ensemble of aircraft, satellite, sonde, and surface observations for April–May 2006 (NASA/INTEX-B aircraft campaign) to better understand the mechanisms for transpacific ozone pollution and its implications for North American air quality. The observations are interpreted with a global 3-D chemical transport model (GEOS-Chem). OMI NO2 satellite observations constrain Asian anthropogenic NOx emissions and indicate a factor of 2 increase from 2000 to 2006 in China. Satellite observations of CO from AIRS and TES indicate two major events of Asian transpacific pollution during INTEX-B. Correlation between TES CO and ozone observations shows evidence for transpacific ozone pollution. The semi-permanent Pacific High and Aleutian Low cause splitting of transpacific pollution plumes over the Northeast Pacific. The northern branch circulates around the Aleutian Low and has little impact on North America. The southern branch circulates around the Pacific High and some of that air impacts western North America. Both aircraft measurements and model results show sustained ozone production driven by peroxyacetylnitrate (PAN) decomposition in the southern branch, roughly doubling the transpacific influence from ozone produced in the Asian boundary layer. Model simulation of ozone observations at Mt. Bachelor Observatory in Oregon (2.7 km altitude) indicates a mean Asian ozone pollution contribution of 9±3 ppbv to the mean observed concentration of 54 ppbv, reflecting mostly an enhancement in background ozone rather than episodic Asian plumes. Asian pollution enhanced surface ozone concentrations by 5–7 ppbv over western North America in spring 2006. The 2000–2006 rise in Asian anthropogenic emissions increased this influence by 1–2 ppbv.
Water vapor release from biomass combustion
Authors: Parmar R. S. , Welling M. , Andreae M. O. , Helas G.
Published: April 2010

Abstract. We report on the emission of water vapor from biomass combustion. Concurrent measurements of carbon monoxide and carbon dioxide are used to scale the concentrations of water vapor found, and are referenced to carbon in the biomass. The investigated fuel types include hardwood (oak and African musasa), softwood (pine and spruce, partly with green needles), and African savanna grass. The session-averaged ratio of H2O to the sum of CO and CO2 in the emissions from 16 combustion experiments ranged from 1.2 to 3.7, indicating the presence of water that is not chemically bound. This non-bound biomass moisture content ranged from 33% in the dry African hardwood, musasa, to 220% in fresh pine branches with needles. The moisture content from fresh biomass contributes significantly to the water vapor in biomass burning emissions, and its influence on the behavior of fire plumes and pyro-cumulus clouds needs to be evaluated.
Relationships between submicrometer particulate air pollution and air mass history in Beijing, China, 2004–2006
Authors: Wehner B. , Birmili W. , Ditas F. , Wu Z. , Hu M. , Liu X. , Mao J. , Sugimoto N. , Wiedensohler A.
Published: April 2010

Abstract. The Chinese capital Beijing is one of the global megacities where the effects of rapid economic growth have led to complex air pollution problems that are not well understood. In this study, ambient particle number size distributions in Beijing between 2004 and 2006 are analysed as a function of regional meteorological transport. An essential result is that the particle size distribution in Beijing depends to large extent on the history of the synoptic scale air masses. A first approach based on manual back trajectory classification yielded differences in particulate matter mass concentration by a factor of two between four different air mass categories, including three main wind directions plus the case of stagnant air masses. A back trajectory cluster analysis refined these results, yielding a total of six trajectory clusters. Besides the large scale wind direction, the transportation speed of an air mass was found to play an essential role on the PM concentrations in Beijing. Slow-moving air masses were shown to be associated with an effective accumulation of surface-based anthropogenic emissions due to both, an increased residence time over densely populated land, and their higher degree of vertical stability. For the six back trajectory clusters, differences in PM1 mass concentrations by a factor of 3.5, in the mean air mass speed by a factor of 6, and in atmospheric visibility by a factor of 4 were found. The main conclusion is that the air quality in Beijing is not only degraded by anthropogenic aerosol sources from within the megacity, but also by sources across the entire Northwest China plain depending on the meteorological situation.
4D-Var assimilation of MIPAS chemical observations: ozone and nitrogen dioxide analyses
Authors: Errera Q. , Daerden F. , Chabrillat S. , Lambert J. C. , Lahoz W. A. , Viscardy S. , Bonjean S. , Fonteyn D.
Published: April 2010

Abstract. This paper discusses the global analyses of stratospheric ozone (O3) and nitrogen dioxide (NO2) obtained by the Belgian Assimilation System for Chemical Observations from Envisat (BASCOE). Based on a chemistry transport model (CTM) and the 4-dimensional variational (4D-Var) method, BASCOE has assimilated chemical observations of O3, NO2, HNO3, N2O, CH4 and H2O, made between July 2002 and March 2004 by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard the European Space Agency (ESA) Environment Satellite (ENVISAT). This corresponds to the entire period during which MIPAS was operating at its nominal resolution. Our analyses are evaluated against assimilated MIPAS data and independent HALOE (HALogen Occultation Experiment) and POAM-III (Polar Ozone and Aerosol Measurement) satellite data. A good agreement is generally found between the analyses and these datasets, in both cases within the estimated error bars of the observations. The benefit of data assimilation is also evaluated by comparing a BASCOE free model run with MIPAS observations. For O3, the gain from the assimilation is significant during ozone hole conditions, and in the lower stratosphere. Elsewhere, the assimilation does not provide significant improvement. For NO2, the gain from the assimilation is realized through most of the stratosphere. Using the BASCOE analyses, we estimate the differences between MIPAS data and independent data from HALOE and POAM-III, and find results close to those obtained by classical validation methods involving only direct measurement-to-measurement comparisons. Our results extend and reinforce previous MIPAS data validation efforts by taking into account a much larger variety of atmospheric states and measurement conditions. This study discusses possible further developments of the BASCOE data assimilation system; these concern the horizontal resolution, a better filtering of NO2 observations, and the photolysis calculation near the lid of the model. The ozone analyses are part of the PROMOTE project and are publicly available via the BASCOE website (http://www.bascoe.oma.be/promote/).
Long-term observation of mass-independent oxygen isotope anomaly in stratospheric CO2
Authors: Kawagucci S. , Tsunogai U. , Kudo S. , Nakagawa F. , Honda H. , Aoki S. , Nakazawa T. , Tsutsumi M. , Gamo T.
Published: April 2010

Abstract. Stratospheric and upper tropospheric air samples were collected during 1994–2004 over Sanriku, Japan and in 1997 over Kiruna, Sweden. Using these archived air samples, we determined the triple oxygen-isotope composition of stratospheric CO2 and the N2O mixing ratio. The maximum Δ17OCO2 value of +12.2‰, resembling that observed previously in the mesosphere at 60 km height, was found in the middle stratosphere over Kiruna at 25.6 km height, suggesting that upper stratospheric and mesospheric air descended to the middle stratosphere through strong downward advection. A least-squares regression analysis of our observations on a δ18OCO2−δ17OCO2 plot (r2>0.95) shows a slope of 1.63±pm0.10, which is similar to the reported value of 1.71±0.06, thereby confirming the linearity of three isotope correlation with the slope of 1.6–1.7 in the mid-latitude lower and middle stratosphere. The slope decrease with increasing altitude and a curvy trend in three-isotope correlation reported from previous studies were not statistically significant. Using negative linear correlations of Δ17OCO2 and δ18OCO2 with the N2O mixing ratio, we quantified triple oxygen-isotope fluxes of CO2 to the troposphere as +48‰ GtC/yr (Δ17OCO2) and +38‰ GtC/yr (δ18OCO2) with ~30% uncertainty. Comparing recent model results and observations, underestimation of the three isotope slope and the maximum Δ17OCO2 value in the model were clarified, suggesting a smaller O2 photolysis contribution than that of the model. Simultaneous observations of δ18OCO2, δ17OCO2, and N2O mixing ratios can elucidate triple oxygen isotopes in CO2 and clarify complex interactions among physical, chemical, and photochemical processes occurring in the middle atmosphere.
Absolute rate constant and O(3P) yield for the O(1D)+N2O reaction in the temperature range 227 K to 719 K
Authors: Vranckx S. , Peeters J. , Carl S. A.
Published: April 2010

Abstract. The absolute rate constant for the reaction that is the major source of stratospheric NOx, O(1D)+N2O → products, has been determined in the temperature range 227 K to 719 K, and, in the temperature range 248 K to 600 K, the fraction of the reaction that yields O(3P). Both the rate constants and product yields were determined using a recently-developed chemiluminescence technique for monitoring O(1D) that allows for higher precision determinations for both rate constants, and, particularly, O(3P) yields, than do other methods. We found the rate constant, kR1, to be essentially independent of temperature between 400 K and 227 K, having a value of (1.37±0.11)×10−10 cm3 s−1, and for temperatures greater than 450 K a marked decrease in rate constant was observed, with a rate constant of only (0.94±0.11)×10−10 cm3 s−1 at 719 K. The rate constants determined over the 227 K–400 K range show very low scatter and are significantly greater, by 20% at room temperature and 15% at 227 K, than the current recommended values. The fraction of O(3P) produced in this reaction was determined to be 0.002±0.002 at 250 K rising steadily to 0.010±0.004 at 600 K, thus the channel producing O(3P) can be entirely neglected in atmospheric kinetic modeling calculations. A further result of this study is an expression of the relative quantum yields as a function of temperature for the chemiluminescence reactions (kCL1)C2H + O(1D) → CH(A) + CO and (kCL2)C2H + O(3P) → CH(A) + CO, both followed by CH(A) → CH(X) + hν, as kCL1(T)/kCL2(T)=(32.8T−3050)/(6.29T+398).
A single parameter representation of hygroscopic growth and cloud condensation nucleus activity – Part 2: Including solubility
Authors: Petters M. D. , Kreidenweis S. M.
Published: April 2010

Abstract. The ability of a particle to serve as a cloud condensation nucleus in the atmosphere is determined by its size, hygroscopicity and its solubility in water. Usually size and hygroscopicity alone are sufficient to predict CCN activity. Single parameter representations for hygroscopicity have been shown to successfully model complex, multicomponent particles types. Under the assumption of either complete solubility, or complete insolubility of a component, it is not necessary to explicitly include that component's solubility into the single parameter framework. This is not the case if sparingly soluble materials are present. In this work we explicitly account for solubility by modifying the single parameter equations. We demonstrate that sensitivity to the actual value of solubility emerges only in the regime of 2×10−1–5×10−4, where the solubility values are expressed as volume of solute per unit volume of water present in a saturated solution. Compounds that do not fall inside this sparingly soluble envelope can be adequately modeled assuming they are either infinitely soluble in water or completely insoluble.
Four-dimensional variational data assimilation for inverse modelling of atmospheric methane emissions: method and comparison with synthesis inversion
Authors: Meirink J. F. , Bergamaschi P. , Krol M. C.
Published: April 2010

Abstract. A four-dimensional variational (4D-Var) data assimilation system for inverse modelling of atmospheric methane emissions is presented. The system is based on the TM5 atmospheric transport model. It can be used for assimilating large volumes of measurements, in particular satellite observations and quasi-continuous in-situ observations, and at the same time it enables the optimization of a large number of model parameters, specifically grid-scale emission rates. Furthermore, the variational method allows to estimate uncertainties in posterior emissions. Here, the system is applied to optimize monthly methane emissions over a 1-year time window on the basis of surface observations from the NOAA-ESRL network. The results are rigorously compared with an analogous inversion by Bergamaschi et al. (2007), which was based on the traditional synthesis approach. The posterior emissions as well as their uncertainties obtained in both inversions show a high degree of consistency. At the same time we illustrate the advantage of 4D-Var in reducing aggregation errors by optimizing emissions at the grid scale of the transport model. The full potential of the assimilation system is exploited in Meirink et al. (2008), who use satellite observations of column-averaged methane mixing ratios to optimize emissions at high spatial resolution, taking advantage of the zooming capability of the TM5 model.
Influence of future air pollution mitigation strategies on total aerosol radiative forcing
Authors: Kloster S. , Dentener F. , Feichter J. , Raes F. , van Aardenne J. , Roeckner E. , Lohmann U. , Stier P. , Swart R.
Published: April 2010

Abstract. We apply different aerosol and aerosol precursor emission scenarios reflecting possible future control strategies for air pollution in the ECHAM5-HAM model, and simulate the resulting effect on the Earth's radiation budget. We use two opposing future mitigation strategies for the year 2030: one in which emission reduction legislation decided in countries throughout the world are effectively implemented (current legislation; CLE 2030) and one in which all technical options for emission reductions are being implemented independent of their cost (maximum feasible reduction; MFR 2030). We consider the direct, semi-direct and indirect radiative effects of aerosols. The total anthropogenic aerosol radiative forcing defined as the difference in the top-of-the-atmosphere radiation between 2000 and pre-industrial times amounts to −2.00 W/m2. In the future this negative global annual mean aerosol radiative forcing will only slightly change (+0.02 W/m2) under the "current legislation" scenario. Regionally, the effects are much larger: e.g. over Eastern Europe radiative forcing would increase by +1.50 W/m2 because of successful aerosol reduction policies, whereas over South Asia it would decrease by −1.10 W/m2 because of further growth of emissions. A "maximum feasible reduction" of aerosols and their precursors would lead to an increase of the global annual mean aerosol radiative forcing by +1.13 W/m2. Hence, in the latter case, the present day negative anthropogenic aerosol forcing could be more than halved by 2030 because of aerosol reduction policies and climate change thereafter will be to a larger extent be controlled by greenhouse gas emissions. We combined these two opposing future mitigation strategies for a number of experiments focusing on different sectors and regions. In addition, we performed sensitivity studies to estimate the importance of future changes in oxidant concentrations and the importance of the aerosol microphysical coupling within the range of expected future changes. For changes in oxidant concentrations caused by future air pollution mitigation, we do not find a significant effect for the global annual mean radiative aerosol forcing. In the extreme case of only abating SO2 or carbonaceous emissions to a maximum feasible extent, we find deviations from additivity for the radiative forcing over anthropogenic source regions up to 10% compared to an experiment abating both at the same time.
Modelling representation errors of atmospheric CO2 mixing ratios at a regional scale
Authors: Tolk L. F. , Meesters A. G. C. A. , Dolman A. J. , Peters W.
Published: April 2010

Abstract. Inverse modelling of carbon sources and sinks requires an accurate quality estimate of the modelling framework to obtain a realistic estimate of the inferred fluxes and their uncertainties. So-called "representation errors" result from our inability to correctly represent point observations with simulated average values of model grid cells. They may add substantial uncertainty to the interpretation of atmospheric CO2 mixing ratio data. We simulated detailed variations in the CO2 mixing ratios with a high resolution (2 km) mesoscale model (RAMS) to estimate the representation errors introduced at larger model grid sizes of 10–100 km. We found that meteorology is the main driver of representation errors in our study causing spatial and temporal variations in the error estimate. Within the nocturnal boundary layer, the representation errors are relatively large and mainly caused by unresolved topography at lower model resolutions. During the day, convective structures, mesoscale circulations, and surface CO2 flux variability were found to be the main sources of representation errors. Interpreting observations near a mesoscale circulation as representative for air with the correct footprint relative to the front can reduce the representation error substantially. The remaining representation error is 0.5–1.5 ppm at 20–100 km resolution.
Trend analysis of greenhouse gases over Europe measured by a network of ground-based remote FTIR instruments
Authors: Gardiner T. , Forbes A. , de Mazière M. , Vigouroux C. , Mahieu E. , Demoulin P. , Velazco V. , Notholt J. , Blumenstock T. , Hase F. , Kramer I. , Sussmann R. , Stremme W. , Mellqvist J. , Strandberg A. , Ellingsen K. , Gauss M.
Published: April 2010

Abstract. This paper describes the statistical analysis of annual trends in long term datasets of greenhouse gas measurements taken over ten or more years. The analysis technique employs a bootstrap resampling method to determine both the long-term and intra-annual variability of the datasets, together with the uncertainties on the trend values. The method has been applied to data from a European network of ground-based solar FTIR instruments to determine the trends in the tropospheric, stratospheric and total columns of ozone, nitrous oxide, carbon monoxide, methane, ethane and HCFC-22. The suitability of the method has been demonstrated through statistical validation of the technique, and comparison with ground-based in-situ measurements and 3-D atmospheric models.
Modeling the effect of plume-rise on the transport of carbon monoxide over Africa with NCAR CAM
Authors: Guan H. , Chatfield R. B. , Freitas S. R. , Bergstrom R. W. , Longo K. M.
Published: April 2010

Abstract. We investigated the effects of fire-induced plume-rise on the simulation of carbon monoxide (CO) over Africa and its export during SAFARI 2000 using the NCAR Community Atmosphere Model (CAM) with a CO tracer and a plume-rise parameterization scheme. The plume-rise parameterization scheme simulates the consequences of strong buoyancy of hot gases emitted from biomass burning, including both dry and cloud-associated (pyro-cumulus) lofting. The current implementation of the plume-rise parameterization scheme into the global model provides an opportunity to examine the effect of plume-rise on long-range transport. The CAM simulation with the plume-rise parameterization scheme seems to show a substantial improvement of the agreements between the modeled and aircraft-measured vertical distribution of CO over Southern Africa biomass-burning area. The plume-rise mechanism plays a crucial role in lofting biomass-burning pollutants to the middle troposphere. In the presence of deep convection we found that the plume-rise mechanism results in a decrease of CO concentration in the upper troposphere. The plume-rise depletes the boundary layer, and thus leaves lower concentrations of CO to be lofted by the deep convection process. The effect of the plume-rise on free troposphere CO concentration is more important for the source area (short-distance transport) than for remote areas (long-distance transport). A budget analysis of CO burden over Southern Africa reveals the plume-rise process to have a similar impact as the chemical production of CO by OH and CH4. In addition, the plume-rise process has an minor impact on the regional export. These results further confirm and extend previous findings in a regional model study. Effective lofting of large concentration of CO by the plume-rise mechanism also has implications for local air quality forecasting in areas affected by other fire-related pollutants.
Evaluation of tropospheric and stratospheric ozone trends over Western Europe from ground-based FTIR network observations
Authors: Vigouroux C. , De Mazière M. , Demoulin P. , Servais C. , Hase F. , Blumenstock T. , Kramer I. , Schneider M. , Mellqvist J. , Strandberg A. , Velazco V. , Notholt J. , Sussmann R. , Stremme W. , Rockmann A. , Gardiner T. , Coleman M. , Woods P.
Published: April 2010

Abstract. Within the European project UFTIR (Time series of Upper Free Troposphere observations from an European ground-based FTIR network), six ground-based stations in Western Europe, from 79° N to 28° N, all equipped with Fourier Transform infrared (FTIR) instruments and part of the Network for the Detection of Atmospheric Composition Change (NDACC), have joined their efforts to evaluate the trends of several direct and indirect greenhouse gases over the period 1995–2004. The retrievals of CO, CH4, C2H6, N2O, CHClF2, and O3 have been optimized. Using the optimal estimation method, some vertical information can be obtained in addition to total column amounts. A bootstrap resampling method has been implemented to determine annual partial and total column trends for the target gases. The present work focuses on the ozone results. The retrieved time series of partial and total ozone columns are validated with ground-based correlative data (Brewer, Dobson, UV-Vis, ozonesondes, and Lidar). The observed total column ozone trends are in agreement with previous studies: 1) no total column ozone trend is seen at the lowest latitude station Izaña (28° N); 2) slightly positive total column trends are seen at the two mid-latitude stations Zugspitze and Jungfraujoch (47° N), only one of them being significant; 3) the highest latitude stations Harestua (60° N), Kiruna (68° N) and Ny-Ålesund (79° N) show significant positive total column trends. Following the vertical information contained in the ozone FTIR retrievals, we provide partial columns trends for the layers: ground-10 km, 10–18 km, 18–27 km, and 27–42 km, which helps to distinguish the contributions from dynamical and chemical changes on the total column ozone trends. We obtain no statistically significant trends in the ground-10 km layer for five out of the six ground-based stations. We find significant positive trends for the lowermost stratosphere at the two mid-latitude stations, and at Ny-Ålesund. We find smaller, but significant trends for the 18–27 km layer at Kiruna, Harestua, Jungfraujoch, and Izaña. The results for the upper layer are quite contrasted: we find significant positive trends at Kiruna, Harestua, and Jungfraujoch, and significant negative trends at Zugspitze and Izaña. These ozone partial columns trends are discussed and compared with previous studies.
Measurements of the relation between aerosol properties and microphysics and chemistry of low level liquid water clouds in Northern Finland
Authors: Lihavainen H. , Kerminen V.-M. , Komppula M. , Hyvärinen A.-P. , Laakia J. , Saarikoski S. , Makkonen U. , Kivekäs N. , Hillamo R. , Kulmala M. , Viisanen Y.
Published: April 2010

Abstract. Physical and chemical properties of boundary layer clouds, together with relevant aerosol properties, were investigated during the first Pallas Cloud Experiment (First Pace) conducted in northern Finland between 20 October and 9 November 2004. Two stations located 6 km apart from each other at different altitudes were employed in measurements. The low-altitude station was always below the cloud layer, whereas the high-altitude station was inside clouds about 75% of the time during the campaign. Direct measurements of cloud droplet populations showed that our earlier approach of determining cloud droplet residual particle size distributions and corresponding activated fractions using continuous aerosol number size distribution measurements at the two stations is valid, as long as the cloud events are carefully screened to exclude precipitating clouds and to make sure the same air mass has been measured at both stations. We observed that a non-negligible fraction of cloud droplets originated from Aitken mode particles even at moderately-polluted air masses. We found clear evidence on first indirect aerosol effect on clouds but demonstrated also that no simple relation between the cloud droplet number concentration and aerosol particle number concentration exists for this type of clouds. The chemical composition of aerosol particles was dominated by particulate organic matter (POM) and sulphate in continental air masses and POM, sodium and chlorine in marine air masses. The inorganic composition of cloud water behaved similarly to that of the aerosol phase and was not influenced by inorganic trace gases.
Monthly-averaged anthropogenic aerosol direct radiative forcing over the Mediterranean based on AERONET aerosol properties
Authors: Bergamo A. , Tafuro A. M. , Kinne S. , De Tomasi F. , Perrone M. R.
Published: April 2010

Abstract. The all-sky direct radiative effect by anthropogenic aerosol (DREa) is calculated in the solar (0.3–4 μm) and infrared (4–200 μm) spectral ranges for six Mediterranean sites. The sites are differently affected by pollution and together reflect typical aerosol impacts that are expected over land and coastal sites of the central Mediterranean basin. Central to the simulations are aerosol optical properties from AERONET sun-/sky-photometer statistics for the year 2003. A discussion on the variability of the overall (natural + anthropogenic) aerosol properties with site location is provided. Supplementary data include MODIS satellite sensor based solar surface albedos, ISCCP products for high- mid- and low cloud cover and estimates for the anthropogenic aerosol fraction from global aerosol models. Since anthropogenic aerosol particles are considered to be smaller than 1 μm in size, mainly the solar radiation transfer is affected with impacts only during sun-light hours. At all sites the (daily average) solar DREa is negative all year round at the top of the atmosphere (ToA). Hence, anthropogenic particles produce over coastal and land sites of the central Mediterranean a significant cooling effect. Monthly DREa values vary from site to site and are seasonally dependent as a consequence of the seasonal dependence of available sun-light and microphysical aerosol properties. At the ToA the monthly average DREa is −(4±1) W m−2 during spring-summer (SS, April–September) and −(2±1) W m−2 during autumn-winter (AW, October–March) at the polluted sites. In contrast, it varies between −(3±1) W m−2 and −(1±1) W m−2 on SS and AW, respectively at the less polluted site. Due to atmospheric absorption the DREa at the surface is larger than at the ToA. At the surface the monthly average DREa varies between the most and the least polluted site between −(7±1) W m−2 and −(4±1) W m−2 during SS, and between −(4±3) W m−2 and −(1±1) W m−2 during AW. The DREa at infrared wavelengths is positive but negligible, especially at the ToA (<0.3 W m−2). The average of DREa monthly-means referring to all sites has allowed getting a ToA- and sfc-DREa yearly-mean value of −(3±2) and −(5±3) W m−2, respectively at solar wavelengths. Last data, even if refer to a particular year, indicate that the radiative energy-balance of Central Mediterranean land and coastal sites is quite affected by anthropogenic particles.
A chemical model of meteoric ablation
Authors: Vondrak T. , Plane J. M. C. , Broadley S. , Janches D.
Published: April 2010

Abstract. Most of the extraterrestrial dust entering the Earth's atmosphere ablates to produce metal vapours, which have significant effects on the aeronomy of the upper mesosphere and lower thermosphere. A new Chemical Ablation Model (CAMOD) is described which treats the physics and chemistry of ablation, by including the following processes: sputtering by inelastic collisions with air molecules before the meteoroid melts; evaporation of atoms and oxides from the molten particle; diffusion-controlled migration of the volatile constituents (Na and K) through the molten particle; and impact ionization of the ablated fragments by hyperthermal collisions with air molecules. Evaporation is based on thermodynamic equilibrium in the molten meteoroid (treated as a melt of metal oxides), and between the particle and surrounding vapour phase. The loss rate of each element is then determined assuming Langmuir evaporation. CAMOD successfully predicts the meteor head echo appearance heights, observed from incoherent scatter radars, over a wide range of meteoroid velocities. The model also confirms that differential ablation explains common-volume lidar observations of K, Ca and Ca+ in fresh meteor trails. CAMOD is then used to calculate the injection rates into the atmosphere of a variety of elements as a function of altitude, integrated over the meteoroid mass and velocity distributions. The most abundant elements (Fe, Mg and Si) have peak injection rates around 85 km, with Na and K about 8 km higher. The more refractory element Ca ablates around 82 km with a Na:Ca ratio of 4:1, which does therefore not explain the depletion of atomic Ca to Na, by more than 2 orders of magnitude, in the upper mesosphere. Diffusion of the most volatile elements (Na and K) does not appear to be rate-limiting except in the fastest meteoroids. Non-thermal sputtering causes ~35% mass loss from the fastest (~60–70 km s−1) and smallest (10−17–10−13 g) meteoroids, but makes a minor contribution to the overall ablation rate.
Technical Note: The CCCma third generation AGCM and its extension into the middle atmosphere
Authors: Scinocca J. F. , McFarlane N. A. , Lazare M. , Li J. , Plummer D.
Published: April 2010

Abstract. The Canadian Centre for Climate Modelling and Analysis third generation atmospheric general circulation model (AGCM3) is described. The discussion summarizes the details of the complete physics package emphasizing the changes made relative to the second generation version of the model. AGCM3 is the underlying model for applications which include the IPCC fourth assessment, coupled atmosphere-ocean seasonal forecasting, the first generation of the CCCma earth system model (CanESM1), and middle-atmosphere chemistry-climate modelling (CCM). Here we shall focus on issues related to an upwardly extended version of AGCM3, the Canadian Middle-Atmosphere Model (CMAM). The CCM version of CMAM participated in the 2006 WMO/UNEP Scientific Assessment of Ozone Depletion and issues concerning its climate such as the impact of gravity-wave drag, the modelling of a spontaneous QBO, and the seasonality of the breakdown of the Southern Hemisphere polar vortex are discussed here.
Sensitivity of US air quality to mid-latitude cyclone frequency and implications of 1980–2006 climate change
Authors: Leibensperger E. M. , Mickley L. J. , Jacob D. J.
Published: April 2010

Abstract. We show that the frequency of summertime mid-latitude cyclones tracking across eastern North America at 40°–50° N (the southern climatological storm track) is a strong predictor of stagnation and ozone pollution days in the eastern US. The NCEP/NCAR Reanalysis, going back to 1948, shows a significant long-term decline in the number of summertime mid-latitude cyclones in that track starting in 1980 (−0.15 a−1). The more recent but shorter NCEP/DOE Reanalysis (1979–2006) shows similar interannual variability in cyclone frequency but no significant long-term trend. Analysis of NOAA daily weather maps for 1980–2006 supports the trend detected in the NCEP/NCAR Reanalysis 1. A GISS general circulation model (GCM) simulation including historical forcing by greenhouse gases reproduces this decreasing cyclone trend starting in 1980. Such a long-term decrease in mid-latitude cyclone frequency over the 1980–2006 period may have offset by half the ozone air quality gains in the northeastern US from reductions in anthropogenic emissions. We find that if mid-latitude cyclone frequency had not declined, the northeastern US would have been largely compliant with the ozone air quality standard by 2001. Mid-latitude cyclone frequency is expected to decrease further over the coming decades in response to greenhouse warming and this will necessitate deeper emission reductions to achieve a given air quality goal.
Measurement of glyoxal using an incoherent broadband cavity enhanced absorption spectrometer
Authors: Washenfelder R. A. , Langford A. O. , Fuchs H. , Brown S. S.
Published: April 2010

Abstract. We describe an instrument for simultaneous measurements of glyoxal (CHOCHO) and nitrogen dioxide (NO2) using cavity enhanced absorption spectroscopy with a broadband light source. The output of a Xenon arc lamp is coupled into a 1 m optical cavity, and the spectrum of light exiting the cavity is recorded by a grating spectrometer with a charge-coupled device (CCD) array detector. The mirror reflectivity and effective path lengths are determined from the known Rayleigh scattering of He and dry zero air (N2+O2). Least-squares fitting, using published reference spectra, allow the simultaneous retrieval of CHOCHO, NO2, O4, and H2O in the 441 to 469 nm spectral range. For a 1-min sampling time, the precision (±1σ) on signal for measurements of CHOCHO and NO2 is 29 pptv and 20 pptv, respectively. We directly compare measurements made with the incoherent broadband cavity enhanced absorption spectrometer with those from cavity ringdown instruments detecting CHOCHO and NO2 at 404 and 532 nm, respectively, and find linear agreement over a wide range of concentrations. The instrument has been tested in the laboratory with both synthetic and real air samples, and the demonstrated sensitivity and specificity suggest a strong potential for field measurements of both CHOCHO and NO2.