bluuebunny/crossref_metadata_2025 huggingface dataset:
CHEM2D-OPP: A new linearized gas-phase ozone photochemistry parameterization for high-altitude NWP and climate models
Authors: McCormack J. P. , Eckermann S. D. , Siskind D. E. , McGee T. J.
Published: April 2010

Abstract. The new CHEM2D-Ozone Photochemistry Parameterization (CHEM2D-OPP) for high-altitude numerical weather prediction (NWP) systems and climate models specifies the net ozone photochemical tendency and its sensitivity to changes in ozone mixing ratio, temperature and overhead ozone column based on calculations from the CHEM2D interactive middle atmospheric photochemical transport model. We evaluate CHEM2D-OPP performance using both short-term (6-day) and long-term (1-year) stratospheric ozone simulations with the prototype high-altitude NOGAPS-ALPHA forecast model. An inter-comparison of NOGAPS-ALPHA 6-day ozone hindcasts for 7 February 2005 with ozone photochemistry parameterizations currently used in operational NWP systems shows that CHEM2D-OPP yields the best overall agreement with Aura Microwave Limb Sounder ozone profile measurements. A 1-year free-running NOGAPS-ALPHA simulation using CHEM2D-OPP produces a realistic seasonal cycle in zonal mean ozone throughout the stratosphere. We find that the combination of a model cold temperature bias at high latitudes in winter and a warm bias in the CHEM2D-OPP temperature climatology can degrade the performance of the linearized ozone photochemistry parameterization over seasonal time scales despite the fact that the parameterized temperature dependence is weak in these regions.
Elimination of hidden a priori information from remotely sensed profile data
Authors: von Clarmann T. , Grabowski U.
Published: April 2010

Abstract. Profiles of atmospheric state parameters retrieved from remote measurements often contain a priori information which causes complication in the use of data for validation, comparison with models, or data assimilation. For such applications it often is desirable to remove the a priori information from the data product. If the retrieval involves an ill-posed inversion problem, formal removal of the a priori information requires resampling of the data on a coarser grid, which, however, is a prior constraint in itself. The fact that the trace of the averaging kernel matrix of a retrieval is equivalent to the number of degrees of freedom of the retrieval is used to define an appropriate information-centered representation of the data where each data point represents one degree of freedom. Since regridding implies further degradation of the data and thus causes additional loss of information, a re-regularization scheme has been developed which allows resampling without additional loss of information. For a typical ClONO2 profile retrieved from spectra as measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), the constrained retrieval has 9.7 degrees of freedom. After application of the proposed transformation to a coarser information-centered altitude grid, there are exactly 9 degrees of freedom left, and the averaging kernel on the coarse grid is unity. Pure resampling on the information-centered grid without re-regularization would reduce the degrees of freedom to 7.1.
Comparison of CO2 fluxes estimated using atmospheric and oceanic inversions, and role of fluxes and their interannual variability in simulating atmospheric CO2 concentrations
Authors: Patra P. K. , Mikaloff Fletcher S. E. , Ishijima K. , Maksyutov S. , Nakazawa T.
Published: April 2010

Abstract. We use a time-dependent inverse (TDI) model to estimate regional sources and sinks of atmospheric CO2 from 64 and then 22 regions based on atmospheric CO2 observations at 87 stations. The air-sea fluxes from the 64-region atmospheric-CO2 inversion are compared with fluxes from an analogous ocean inversion that uses ocean interior observations of dissolved inorganic carbon (DIC) and other tracers and an ocean general circulation model (OGCM). We find that, unlike previous atmospheric inversions, our flux estimates in the southern hemisphere are generally in good agreement with the results from the ocean inversion, which gives us added confidence in our flux estimates. In addition, a forward tracer transport model (TTM) is used to simulate the observed CO2 concentrations using (1) estimates of fossil fuel emissions and a priori estimates of the terrestrial and oceanic fluxes of CO2, and (2) two sets of TDI model corrected fluxes. The TTM simulations of TDI model corrected fluxes show improvements in fitting the observed interannual variability in growth rates and seasonal cycles in atmospheric CO2. Our analysis suggests that the use of interannually varying (IAV) meteorology and a larger observational network have helped to capture the regional representation and interannual variabilities in CO2 fluxes realistically.
On the time-averaging of ultrafine particle number size spectra in vehicular plumes
Authors: Yao X. , Lau N. T. , Fang M. , Chan C. K.
Published: April 2010

Abstract. Ultrafine particle (<100 nm) number size distributions presented in the literature are mostly averages of long scan-time (~30 s or more) spectra mainly due to the non-availability of commercial instruments that can measure particle distributions in the <10 nm to 100 nm range faster than 30 s even though individual researchers have built faster (1–2.5 s) scanning instruments. With the introduction of the Engine Exhaust Particle Sizer (EEPS) in 2004, high time-resolution (1 full 32-channel spectrum per second) particle size distribution data become possible and allow atmospheric researchers to study the characteristics of ultrafine particles in rapidly and perhaps randomly varying high concentration environments such as roadside, on-road and tunnel. In this study, particle size distributions in these environments were found to vary as rapidly as one second frequently. This poses the question on the generality of using averages of long scan-time spectra for dynamic and/or mechanistic studies in rapidly and perhaps randomly varying high concentration environments. One-second EEPS data taken at roadside, on roads and in tunnels by a mobile platform are time-averaged to yield 5, 10, 30 and 120 s distributions to answer this question.
Rayleigh lidar observations of double stratopause structure over three different northern hemisphere stations
Authors: Sivakumar V. , Bencherif H. , Hauchecorne A. , Keckhut P. , Rao D. N. , Sharma S. , Chandra H. , Jayaraman A. , Rao P. B.
Published: April 2010

Abstract. Using four years of Rayleigh lidar data collected from three different northern hemisphere stations (Gadanki 13.5° N, 79.2° E ; Mt. Abu 24.5° N, 72.7° E and Observatoire de Haute Provence: OHP; 44° N, 6° E), the characteristics of double (separated) stratopause occurrence are presented here, for the first time. The characteristics are illustrated by a seasonal change during summer and winter and the variation in percentage of occurrence from place to place. It is found that the over-all mean normal stratopause (NS) positioned at the middle level of double stratopause (upper and lower level) with its location nearer to the lower level of double stratopause (LDS) than to the upper level of double stratopause (UDS). The frequency distribution of NS, LDS and UDS demonstrated variability with location, indicating role of dynamical activity. By making use of a quasi-continuous 40 days of lidar observations over Gadanki and OHP, the responsibility of Gravity Wave (GW) and Planetary Wave (PW) activity for the LDS and UDS occurrence are examined and presented.
The atmospheric chemistry general circulation model ECHAM5/MESSy1: consistent simulation of ozone from the surface to the mesosphere
Authors: Jöckel P. , Tost H. , Pozzer A. , Brühl C. , Buchholz J. , Ganzeveld L. , Hoor P. , Kerkweg A. , Lawrence M. G. , Sander R. , Steil B. , Stiller G. , Tanarhte M. , Taraborrelli D. , van Aardenne J. , Lelieveld J.
Published: April 2010

Abstract. The new Modular Earth Submodel System (MESSy) describes atmospheric chemistry and meteorological processes in a modular framework, following strict coding standards. It has been coupled to the ECHAM5 general circulation model, which has been slightly modified for this purpose. A 90-layer model version up to 0.01 hPa was used at T42 resolution (~2.8 latitude and longitude) to simulate the lower and middle atmosphere. The model meteorology has been tested to check the influence of the changes to ECHAM5 and the radiation interactions with the new representation of atmospheric composition. A Newtonian relaxation technique was applied in the tropospheric part of the domain to weakly nudge the model towards the analysed meteorology during the period 1998–2005. It is shown that the tropospheric wave forcing of the stratosphere in the model suffices to reproduce the Quasi-Biennial Oscillation and major stratospheric warming events leading e.g. to the vortex split over Antarctica in 2002. Characteristic features such as dehydration and denitrification caused by the sedimentation of polar stratospheric cloud particles and ozone depletion during winter and spring are simulated accurately, although ozone loss in the lower polar stratosphere is slightly underestimated. The model realistically simulates stratosphere-troposphere exchange processes as indicated by comparisons with satellite and in situ measurements. The evaluation of tropospheric chemistry presented here focuses on the distributions of ozone, hydroxyl radicals, carbon monoxide and reactive nitrogen compounds. In spite of minor shortcomings, mostly related to the relatively coarse T42 resolution and the neglect of interannual changes in biomass burning emissions, the main characteristics of the trace gas distributions are generally reproduced well. The MESSy submodels and the ECHAM5/MESSy1 model output are available through the internet on request.
Isolated lower mesospheric echoes seen by medium frequency radar at 70° N, 19° E
Authors: Hall C. M. , Manson A. H. , Meek C. E. , Nozawa S.
Published: April 2010

Abstract. We have noted sporadic instances of strong isolated reflections of medium frequency (MF) radar waves from the mesosphere from as low as 50 km altitude and have devised a set of criteria for isolating these apparently anomalous echoes from those normally occurring from progressive partial reflections in the D-region. The object of this study is therefore to map the occurrences of such echoes facilitating comparisons with other observations. For example, the similarity and simultaneity of the echo structure for the 20 January 2005 with VHF radar results presented by Lübken et al. (2006) are particularly striking. In presenting a number of such echo events since 2001 selected from the MF radar dataset (which spans 1997 to present), we find that virtually all echo occurrences coincide with enhanced solar proton fluxes suggesting that substantial ionisation of the mesosphere is a necessary condition. Strong partial reflections of the radio wave in the lower mesosphere combined with seasonally varying total absorption higher up, thus giving false impressions of lower mesospheric layers preferentially in winter, constitute a scenario consistent with our observations.
Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 and 2003 field campaigns
Authors: Velasco E. , Lamb B. , Westberg H. , Allwine E. , Sosa G. , Arriaga-Colina J. L. , Jobson B. T. , Alexander M. , Prazeller P. , Knighton W. B. , Rogers T. M. , Grutter M. , Herndon S. C. , Kolb C. E. , Zavala M. , de Foy B. , Volkamer R. , Molina L. T. , Molina M. J.
Published: April 2010

Abstract. A wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Five distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air quality modeling studies suggests that some, but not all, VOC classes are underestimated in the emissions inventory by factors of 1.1 to 3.
Mid-winter lower stratosphere temperatures in the Antarctic vortex: comparison between observations and ECMWF operational model.
Authors: Parrondo M. C. , Yela M. , Gil M. , von der Gathen P. , Ochoa H.
Published: April 2010

Abstract. Radiosonde temperature profiles from Belgrano (78° S) and other Antarctic stations have been compared with European Centre for Medium-Range Weather Forecasts (ECMWF) data during the winter of 2003. Results show a bias in the operational model which is height and temperature dependent, being too cold at layers peaking at 80 and 25–30 hPa, and hence resulting in an overestimation of the predicted potential PSC areas. Here we show the results of the comparison by considering the possibility of a bias in the sondes at extremely low temperatures and discuss the potential implications that this bias might have on the ozone depletion computed by Climate Transport Model based on ECMWF temperature fields.
Night-time radical chemistry during the NAMBLEX campaign
Authors: Sommariva R. , Pilling M. J. , Bloss W. J. , Heard D. E. , Lee J. D. , Fleming Z. L. , Monks P. S. , Plane J. M. C. , Saiz-Lopez A. , Ball S. M. , Bitter M. , Jones R. L. , Brough N. , Penkett S. A. , Hopkins J. R. , Lewis A. C. , Read K. A.
Published: April 2010

Abstract. Night-time chemistry in the Marine Boundary Layer has been modelled using a number of observationally constrained zero-dimensional box-models. The models were based upon the Master Chemical Mechanism (MCM) and the measurements were taken during the North Atlantic Marine Boundary Layer Experiment (NAMBLEX) campaign at Mace Head, Ireland in July–September 2002. The model could reproduce, within the combined uncertainties, the measured concentration of HO2 (within 30–40%) during the night 31 August–1 September and of HO2+RO2 (within 15–30%) during several nights of the campaign. The model always overestimated the NO3 measurements made by Differential Optical Absorption Spectroscopy (DOAS) by up to an order of magnitude or more, but agreed with the NO3 Cavity Ring-Down Spectroscopy (CRDS) measurements to within 30–50%. The most likely explanation of the discrepancy between the two instruments and the model is reaction of the nitrate radical with inhomogeneously distributed NO, which was measured at concentrations of up to 10 ppt, even though this is not enough to fully explain the difference between the DOAS measurements and the model. A rate of production and destruction analysis showed that radicals were generated during the night mainly by the reaction of ozone with light alkenes. The cycling between HO2/RO2 and OH was maintained during the night by the low concentrations of NO and the overall radical concentration was limited by slow loss of peroxy radicals to form peroxides. A strong peak in [NO2] during the night 31 August–1 September allowed an insight into the radical fluxes and the connections between the HOx and the NO3 cycles.
Understanding the kinetics of the ClO dimer cycle
Authors: von Hobe M. , Salawitch R. J. , Canty T. , Keller-Rudek H. , Moortgat G. K. , Grooß J.-U. , Müller R. , Stroh F.
Published: April 2010

Abstract. Among the major factors controlling ozone loss in the polar winter is the kinetics of the ClO dimer catalytic cycle. The most important issues are the thermal equilibrium between ClO and Cl2O2, the rate of Cl2O2 formation, and the Cl2O2 photolysis rate. All these issues have been addressed in a large number of laboratory, field and theoretical studies, but large discrepancies between individual results exist and a self-consistent set of parameters compatible with field observations of ClO and Cl2O2 has not been identified. Here, we use thermodynamic calculations and unimolecular rate theory to constrain the ClO/Cl2O2 equilibrium constant and the rate constants for Cl2O2 formation and dissociation. This information is used together with available atmospheric data to examine Cl2O2 photolysis rates based on different Cl2O2 absorption cross sections. Good overall consistency is achieved using a ClO/Cl2O2 equilibrium constant recently suggested by Plenge et al. (2005), the Cl2O2 recombination rate constant reported by Nickolaisen et al. (1994) and Cl2O2 photolysis rates based on averaged absorption cross sections that are roughly intermediate between the JPL 2002 assessment and a laboratory study by Burkholder et al. (1990).
Inverse modelling for mercury over Europe
Authors: Roustan Y. , Bocquet M.
Published: April 2010

Abstract. The fate and transport of mercury over Europe is studied using a regional Eulerian transport model. Because gaseous elemental mercury is a long-lived species in the atmosphere, boundary conditions must be properly taken into account. Ground measurements of gaseous mercury are very sensitive to the uncertainties attached to those forcing conditions. Inverse modelling can help to constrain the forcing fields and help to improve the predicted mercury concentrations. More generally, it allows to reduce the weaknesses of a regional model against a global or hemispherical model for such diffuse trace constituent. Adjoint techniques are employed to relate rigorously and explicitly the measurements to the forcing fields. This way, the inverse problem is clearly defined. Using EMEP measurements of gaseous mercury and performing the inversions, it is shown that boundary conditions can be improved significantly as well as the forecast concentrations. Using inverse modelling to improve the emission inventory is however much more difficult since there are currently not enough mercury monitoring stations, and their location far from Europe centre.
Characterizing ozone production in the Mexico City Metropolitan Area: a case study using a chemical transport model
Authors: Lei W. , de Foy B. , Zavala M. , Volkamer R. , Molina L. T.
Published: April 2010

Abstract. An episodic simulation is conducted to characterize ozone (O3) photochemical production and investigate its sensitivity to emission changes of ozone precursors in the Mexico City Metropolitan Area (MCMA) using the Comprehensive Air Quality Model with extensions (CAMx). High Ox (O3+NO2) photochemical production rates of 10–80 ppb/h are predicted due to the high reactivity of volatile organic compounds (VOCs) in which alkanes, alkenes, and aromatics exert comparable contributions. The predicted ozone production efficiency is between 4–10 O3 molecules per NOx molecule oxidized, and increases with VOC-to-NO2 reactivity ratio. Process apportionment analyses indicate significant outflow of pollutants such as O3 and peroxyacetyl nitrate (PAN) from the urban area to the surrounding regional environment. PAN is not in chemical-thermal equilibrium during the photochemically active periods. Sensitivity studies of O3 production suggest that O3 formation in the MCMA urban region with less chemical aging (NOz/NOy<0.3) is VOC-limited. Both the simulated behavior of O3 production and its sensitivities to precursors suggest that midday O3 formation during this episode is VOC sensitive in the urban region on the basis of the current emissions inventory. More episodic studies are needed to construct a comprehensive and representative picture of the O3 production characteristics and its response to emission controls.
Airborne measurements of nucleation mode particles I: coastal nucleation and growth rates
Authors: O’Dowd C. D. , Yoon Y. J. , Junkerman W. , Aalto P. , Kulmala M. , Lihavainen H. , Viisanen Y.
Published: April 2010

Abstract. A light aircraft was equipped with a bank of Condensation Particle Counters (CPCs) (50% cut from 3–5.4–9.6 nm) and a nano-Scanning Mobility Particle Sizer (nSMPS) and deployed along the west coast of Ireland, in the vicinity of Mace Head. The objective of the exercise was to provide high resolution micro-physical measurements of the coastal nucleation mode in order to map the spatial extent of new particle production regions and to evaluate the evolution, and associated growth rates of the coastal nucleation-mode aerosol plume. Results indicate that coastal new particle production is occurring over most areas along the land-sea interface with peak concentrations at the coastal plume-head in excess of 106 cm−3. Pseudo-Lagrangian studies of the coastal plume evolution illustrated significant growth of new particles to sizes in excess of 8 nm approximately 10 km downwind of the source region. Close to the plume head (<1 km) growth rates can be as high as 123–171 nm h−1, decreasing gradually to 53–72 nm h−1 at 3 km. Further along the plume, at distances up to 10 km, the growth rates are calculated to be 17–32 nm h−1. Growth rates of this magnitude suggest that after a couple of hours, coastal nucleation mode particles can reach significant sizes where they can contribution to the regional aerosol loading.
Evaluation of radar multiple scattering effects in Cloudsat configuration
Authors: Battaglia A. , Ajewole M. O. , Simmer C.
Published: April 2010

Abstract. MonteCarlo simulations have been performed to evaluate the importance of multiple scattering effects in co- and cross-polar radar returns for 94GHz radars in Cloudsat and airborne configurations. Thousands of vertically structured profiles derived from some different cloud resolving models are used as a test-bed. Mie theory is used to derive the single scattering properties of the atmospheric hydrometeors. Multiple scattering effects in the cross polar channel (reflectivity enhancement) are particularly elusive, especially in airborne configuration. They can be quite consistent in satellite configurations, like Cloudsat, especially in regions of high attenuation and in the presence of highly forward scattering layers associated with snow and graupel particles. When the cross polar returns are analysed, high LDR values appear both in space and in airborne configurations. The LDR signatures are footprints of multiple scattering effects since they cannot be explained by single scattering computations, even including non-spherical particles. We see these signatures confirmed by some experimental data collected during the Wakasa Bay experiment. Multiple scattering effects can be important for Clousat applications like rainfall and snowfall retrievals since single scattering based algorithms will be otherwise burdened by positive biases.
A modeling analysis of a heavy air pollution episode occurred in Beijing
Authors: An X. , Zhu T. , Wang Z. , Li C. , Wang Y.
Published: April 2010

Abstract. Because concentrations of fine particulate matter (PM) and ozone in Beijing often exceed healthful levels, China is to taking steps to improve Beijing's air quality for the 2008 Olympic Games. In this paper the Models-3 Community Multiscale Air Quality (CMAQ) Modeling System was used to investigate a heavy air pollution episode in Beijing during 3–7 April 2005. The modeling domain covered from East Asia with four nested grids with 81 to 3 km horizontal resolution focusing on urban Beijing. This was coupled with a regional emissions inventory with a 10 km resolution and a local 1km Beijing emissions database. The trend of predicted concentrations of various pollutants agreed reasonably well with the observations and captured the main features of this heavy pollution episode. The simulated column concentration distribution of PM was correlated reasonably with the MODIS remote sensing products. Control runs with and without Beijing emissions were conducted to quantify the contributions of non-Beijing sources (NBS) to the Beijing local air pollution. The contributions of NBS to each species differed spatially and temporally with the order of PM25>PM10>SO2>SOIL for this episode. The percentage contribution of NBS to fine particle (PM2.5) in Beijing was averaged about 40%, up to 80% at the northwest of urban Beijing and only 10–20% at southwest. The spatial distribution of NBS contributions for PM10 was similar to that for PM2.5, with a slightly less average percentage of about 30%. The NBS contributions for SO2 and SOIL (diameter between 2.5 μm and 10 μm) were only 10–20% and 5–10%. In addition, the pollutant transport flux was calculated and compared at different levels to investigate transport pathway and magnitude. It was found that the NBS contribution correlated with the transport flux, contributing 70% of PM10 concentration in Beijing at the time of transport flux peak during a strong episode with a transport path from southwest to northeast.
A single parameter representation of hygroscopic growth and cloud condensation nucleus activity
Authors: Petters M. D. , Kreidenweis S. M.
Published: April 2010

Abstract. We present a method to describe the relationship between dry particle diameter and cloud condensation nuclei (CCN) activity using a single hygroscopicity parameter. Values of the hygroscopicity parameter are between 0.5 and 2 for highly-CCN-active salts such as sodium chloride, between 0.01 and 0.5 for slightly to very hygroscopic organic species, and 0 for nonhygroscopic components. If compositional data are available and if the hygroscopicity parameter of each component is known, a multicomponent hygroscopicity parameter can be computed by weighting component hygroscopicity parameters by their volume fractions in the mixture. In the absence of information on chemical composition, experimental data for complex, multicomponent particles can be fitted to obtain the hygroscopicity parameter. The hygroscopicity parameter can thus also be used to conveniently model the CCN activity of atmospheric particles, including those containing insoluble components. We confirm the general applicability of the hygroscopicity parameter and its mixing rule by applying it to published hygroscopic diameter growth factor and CCN-activation data for single- and multi-component particles.
A 3D-CTM with detailed online PSC-microphysics: analysis of the Antarctic winter 2003 by comparison with satellite observations
Authors: Daerden F. , Larsen N. , Chabrillat S. , Errera Q. , Bonjean S. , Fonteyn D. , Hoppel K. , Fromm M.
Published: April 2010

Abstract. We present the first detailed microphysical simulations which are performed online within the framework of a global 3-D chemical transport model (CTM) with full chemistry. The model describes the formation and evolution of four types of polar stratospheric cloud (PSC) particles. Aerosol freezing and other relevant microphysical processes are treated in a full explicit way. Each particle type is described by a binned size distribution for the number density and chemical composition. This set-up allows for an accurate treatment of sedimentation and for detailed calculation of surface area densities and optical properties. Simulations are presented for the Antarctic winter of 2003 and comparisons are made to a diverse set of satellite observations (optical and chemical measurements of POAM III and MIPAS) to illustrate the capabilities of the model. This study shows that a combined resolution approach where microphysical processes are simulated in coarse-grained conditions gives good results for PSC formation and its large-scale effect on the chemical environment through processes such as denitrification, dehydration and ozone loss. It is also shown that the influence of microphysical parameters can be measured directly from these processes.
First Odin sub-mm retrievals in the tropical upper troposphere: ice cloud properties
Authors: Eriksson P. , Ekström M. , Rydberg B. , Murtagh D. P.
Published: April 2010

Abstract. There exists today no established satellite technique for measuring the amount of ice in thicker clouds. Sub-mm radiometry is a promising technique for the task, and a retrieval scheme for the first such instrument in space, Odin-SMR, is presented. Several advantages of sub-mm observations are confirmed, such as low influence of particle shape and orientation, and a high dynamic range of the retrievals. In the case of Odin-SMR, cloud ice amounts above ~12.5 km can be determined. The presented retrieval scheme gives a detection threshold of ~4 g/m2 without saturation even for thickest observed clouds. The main retrieval uncertainty is the assumed particle size distribution. Initial results are found to be consistent with similar Aura MLS retrievals. It is then shown that important differences compared to atmospheric models exist. This first retrieval algorithm is limited to lowermost Odin-SMR tangent altitudes, and further development should improve the detection threshold and the vertical resolution.
COMET: a Lagrangian transport model for greenhouse gas emission estimation – forward model technique and performance for methane
Authors: Vermeulen A. T. , Pieterse G. , Hensen A. , van den Bulk W. C. M. , Erisman J. W.
Published: April 2010

Abstract. The Lagrangian transport model COMET has been developed to evaluate emission estimates based on atmospheric concentration observations. This paper describes the model and its application in modelling the methane concentrations at the European stations Cabauw and Macehead. The COMET model captures in most cases both synoptic and diurnal variations of the concentrations as a function of time and in absolute size quite well. The explained variability by COMET of the mixed layer concentration for Cabauw varies from 50% to 84%; for all hourly observations in 2002 the explained variability is 71% with a RMSE of 112 ppb. The explained variability for Macehead is 48%. The most important model parameters were tested for their influence on model performance, but in general the model is not very sensitive to variations within acceptable limits. For a regionally and locally polluted continental site the COMET model shows only a small bias and a moderate random error, and therefore is considered to capture the influence of the sources on the concentration variations quite well. It is therefore concluded that inverse methods and more specifically the COMET model is suitable to be applied in deriving independent estimates of greenhouse gas emissions using Source-Receptor relationships.
Characterization of the 222Rn family turbulent transport in the convective atmospheric boundary layer
Authors: Vinuesa J.-F. , Galmarini S.
Published: April 2010

Abstract. The combined effect of turbulent transport and radioactive decay on the distribution of 222Rn and its progeny in convective atmospheric boundary layers (CBL) is investigated. Large eddy simulation is used to simulate their dispersion in steady state CBL and in unsteady conditions represented by the growth of a CBL within a pre-existing reservoir layer. The exact decomposition of the concentration and flux budget equations under steady state conditions allowed us to determine which processes are responsible for the vertical distribution of 222Rn and its progeny. Their mean concentrations are directly correlated with their half-life, e.g. 222Rn and 210Pb are the most abundant whereas 218Po show the lowest concentrations. 222Rn flux decreases linearly with height and its flux budget is similar to the one of inert emitted scalar, i.e., a balance between on the one hand the gradient and the buoyancy production terms, and on the other hand the pressure and dissipation at smaller scales which tends to destroy the fluxes. While 222Rn exhibits the typical bottom-up behavior, the maximum flux location of the daughters is moving upwards while their rank in the 222Rn progeny is increasing leading to a typical top-down behavior for 210Pb. We also found that 222Rn short-lived daughters, e.g. 218Po and 214Pb, have relevant radioactive decaying contributions acting as flux sources leading to deviations from the linear flux shape. In addition, while analyzing the vertical distribution of the radioactive decay contributions to the concentrations, e.g. the decaying zone, we found a discrepancy in height of 222Rn daughters' radioactive transformations. Under unsteady conditions, the same behaviors reported under steady state conditions are found: deviation of the fluxes from the linear shape for 218Po, enhanced discrepancy in height of the radioactive transformation contributions for all the daughters. In addition, 222Rn and its progeny concentrations collapse due to the rapid growth of the CBL. The analysis emphasizes the crucial role of turbulent transport in the behavior of 222Rn morning concentrations, in particular the ventilation at the top of the boundary layer that leads to the dilution of 222Rn by mixing with radon low concentration air.
Ozone production and hydrocarbon reactivity in Hong Kong, Southern China
Authors: Zhang J. , Wang T. , Chameides W. L. , Cardelino C. , Kwok J. , Blake D. R. , Ding A. , So K. L.
Published: April 2010

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

Abstract. The probability density on a height-meridional plane of negative refractive index squared f(nk2<0) is introduced as a new analysis tool to investigate the climatology of the propagation properties of stationary planetary waves based on NCEP/NCAR reanalysis data for 44 Northern Hemisphere boreal winters (1958–2002). This analysis shows the control of the atmospheric state on planetary wave propagation. It is found that not only the variability of atmospheric stability with altitudes, but also the variability with latitudes has significant influence on planetary wave propagation. Eliassen-Palm flux and divergence are also analyzed to investigate the eddy activities and forcing on zonal mean flow. Only the ultra-long planetary waves with zonal wave number 1, 2 and 3 are investigated. In Northern Hemisphere winter the atmosphere shows a large possibility for stationary planetary waves to propagate from the troposphere to the stratosphere. On the other hand, waves induce eddy momentum flux in the subtropical troposphere and eddy heat flux in the subpolar stratosphere. Waves also exert eddy momentum forcing on the mean flow in the troposphere and stratosphere at middle and high latitudes. A similar analysis is also performed for stratospheric strong and weak polar vortex regimes, respectively. Anomalies of stratospheric circulation affect planetary wave propagation and waves also play an important role in constructing and maintaining of interannual variations of stratospheric circulation.
Technical note: The heterogeneous Zeldovich factor
Authors: Vehkamäki, H. , Määttänen, A. , Lauri A. , Napari I. , Kulmala M.
Published: April 2010

Abstract. In this technical note we present the exact form of the Zeldovich factor for heterogeneous nucleation on spherical pre-existing particles. We study the error caused by planar pre-existing surface approximations, which have been used in our earlier heterogeneous nucleation model and elsewhere in the literature. We also test the significance of widely used approximations for cluster surface area and circumference. We conclude that the approximations do not affect the predicted onset saturation. Especially for small pre-existing particles the nucleation rates calculated with the exact and approximative models differ significantly.
Sensitivity of middle atmospheric temperature and circulation in the UIUC GCM to the treatment of subgrid-scale gravity-wave breaking
Authors: Yang F. , Schlesinger M. E. , Rozanov E. V. , Andronova N. , Zubov V. A. , Callis L. B.
Published: April 2010

Abstract. The sensitivity of the middle atmospheric temperature and circulation to the treatment of mean-flow forcing due to breaking gravity waves at the sub-grid scale was investigated using the University of Illinois at Urbana-Champaign 40-layer General Circulation Model (GCM). The gravity-wave forcing was represented either by Rayleigh friction or by a detailed parameterization scheme with different sets of parameters. The modeled middle atmospheric temperature and circulation exhibit large sensitivity to the parameterized sub-grid gravity-wave forcing. A large warm bias of up to 50°C was found in the model's summer upper mesosphere and lower thermosphere. This warm bias was caused by the inability of the GCM to simulate the reversal of the zonal winds from easterly to westerly crossing the mesopause in the summer hemisphere. Attempts were made to slow down the easterly winds near the mesopause and to reduce the warm bias. The GCM was able to realistically simulate the semi-annual oscillation in the upper stratosphere and lower mesosphere with observational constraints on certain parameter values, but failed to simulate the quasi-biennial oscillation in any of the experiments. Budget analysis indicates that in the middle atmosphere the forces that act to maintain a steady zonal-mean zonal wind are primarily those associated with the meridional transport circulation and breaking gravity waves. Contributions from the interaction of the model-resolved eddies with the mean flow are secondary.
Identification and classification of the formation of intermediate ions measured in boreal forest
Authors: Hirsikko A. , Bergman T. , Laakso L. , Dal Maso M. , Riipinen I. , Hõrrak U. , Kulmala M.
Published: April 2010

Abstract. We have measured the size distributions of air ions (0.42–7.5 nm in diameter) with the Balanced Scanning Mobility Analyzer in boreal forest, in Southern Finland since spring 2003. The size range covers the size range of cluster ions (approximately 0.42–1.6 nm) and naturally charged nanometre aerosol particles (1.6–7.5 nm) or intermediate air ions. Based on the measurements from April 2003 to March 2006 we studied the characteristics of charged aerosol particle formation by classifying each day either as a particle formation event, undefined or non-event day. The principal of the classification, as well as the statistical description of the charged aerosol particle formation events are given. We found in total 269 and 226 particle formation days for negative and positive intermediate ions, respectively. For negatively charged particles we classified 411 undefined and 349 non-event days whereas for positively charged particles 342 undefined and 461 non-event days. The results were compared with the ordinary classification based on Differential Mobility Particle Sizer (DMPS) measurements carried out at the same place. The above-presented values differed slightly from that found from the DMPS data, with a lower particle diameter of 3 nm. In addition, we have found the rain-induced intermediate ion bursts frequently. The rain effect was detected on 163 days by means of negative ions and on 104 days by positive ones. Another interesting phenomenon among the charged aerosol particles was the appearance and existence of intermediate ions during the snowfall. We observed this phenomenon 24 times with negatively charged particles and 21 times with positively charged ones during winter months (October–April). These intermediate air ions were seen during the snowfall and may be caused by ice crystals, although the origin of these intermediate ions is unclear at the moment.
Measurements of O3, NO2 and BrO at the Kaashidhoo Climate Observatory (KCO) during the INDOEX (INDian Ocean EXperiment) Campaign using ground based DOAS (Differential Optical Absorption Spectroscopy) and satellite based GOME (Global Ozone Monitoring Experiment) data
Authors: Ladstätter-Weißenmayer A. , Altmeyer H. , Bruns M. , Richter A. , Rozanov A. , Rozanov V. , Wittrock F. , Burrows J. P.
Published: April 2010

Abstract. The INDian Ocean EXperiment (INDOEX) was an international, multi-platform field campaign to measure long-range transport of air masses from South and South-East-(SE) Asia towards the Indian Ocean. During the dry monsoon season between January and March 1999, local measurements were carried out from ground based platforms and were compared with satellite based data. The objective of this study was to characterise stratospheric and tropospheric trace gas amounts in the equatorial region, and to investigate the impact of air pollution at this remote site. For the characterisation of the chemical composition of the outflow from the S-SE-Asian region, we performed ground based dual-axis-DOAS (Differential Optical Absorption Spectroscopy) measurements at the KCO (Kaashidhoo Climate Observatory) in the Maldives (5.0° N, 73.5° E). The ground based dual-axis-DOAS measurements were conducted using two different observation modes (off-axis and zenith-sky). This technique allows the separation of the tropospheric and stratospheric columns for different trace gases like O3 and NO2. These dual-axis DOAS data were compared with O3-sonde measurements performed at KCO and satellite based GOME (Global Ozone Measuring Experiment) data during the intensive measuring phase of the INDOEX campaign in February and March 1999. From GOME observations, tropospheric and stratospheric columns for O3 and NO2 were retrieved. In addition, the analysis of the O3-sonde measurements allowed the determination of the tropospheric O3 amount. The comparison shows that the results of all three measurement systems agree within their error limits. During the INDOEX campaign, background conditions were observed most of the time, but in a single case an increase of tropospheric NO2 during a short pollution event was observed and the impact on the vertical columns was calculated. In the GOME measurements, evidence was found for large tropospheric contributions to the BrO budget, probably located in the free troposphere and present throughout the year. The latter has been investigated by the comparison of satellite pixels influenced by high and low cloud conditions based on GOME data which allows the determination of the detection limit of tropospheric BrO columns.
An annual cycle of long lived stratospheric gases from MIPAS
Authors: Juckes M. N.
Published: April 2010

Abstract. MIPAS, on ENVISAT, has made high quality observations of ozone, methane and water vapour. Gridded fields, at 4 hourly intervals and approximately 2 degree resolution, have been calculated for all of 2003 using data assimilation with isentropic advection as a constraint. The gridded fields are validated against independent measurements (from 7 other instruments in the case of ozone, 3 for water vapour and one for methane). For ozone the results are in agreement with previously published results. For water vapour the bias relative to HALOE is below 10% between 20 and 48 km, and the standard error is below 12% in this range. Departures from SAGE II and POAM III are substantially larger. The methane analysis has a bias of less than 5% relative to HALOE between 23 and 40 km, with a standard error less than 10% in this height range. The water vapour field clearly reflects the upward motion in the lower tropical stratosphere, while both water vapour and methane show the signature of advection higher up. In the polar regions the descent in the vortex is clearly visible, with strong descent in autumn giving way to weaker descent through the winter. Descent rates of around 100 m/day are found during the formation of the polar vortices, slowing to around 30 m/day during the winter. Ascent of around 20 m/day in the tropics is revealed by the water vapour and total observed hydrogen fields (4 times the methane plus twice the water vapour concentration). The total observed hydrogen is depleted where air is advected down from the upper mesosphere.
A chemical probe technique for the determination of reactive halogen species in aqueous solution: Part 2 – chloride solutions and mixed bromide/chloride solutions
Authors: Anastasio C. , Matthew B. M.
Published: April 2010

Abstract. Although reactive halogen species (X*=X●, ●X2−, X2 and HOX, where X=Br, Cl, or I) are important environmental oxidants, relatively little is known about their kinetics in condensed phases such as seawater and sea-salt particles. Here we describe a new technique to determine reactive chlorine and bromine species in aqueous solutions by using allyl alcohol (CH2=CHCH2OH) as a chemical probe. This probe is combined with competition kinetics in order to determine steady state concentrations of X*(aq). In some cases the technique also can be used to determine the rates of formation and lifetimes of X* in aqueous solution. In a companion paper we reported the results of our method development for aqueous solutions containing only bromide (Br−). In this paper, we discuss method development for solutions containing chloride (Cl−) alone, and for solutions containing both bromide and chloride.