bluuebunny/crossref_metadata_2025 huggingface dataset:
Mass concentration and ion composition of coarse and fine particles in an urban area in Beirut: effect of calcium carbonate on the absorption of nitric and sulfuric acids and the depletion of chloride
Authors: Kouyoumdjian H. , Saliba N. A.
Published: April 2010

Abstract. Levels of coarse (PM10-2.5) and fine (PM2.5) particles were determined between February 2004 and January 2005 in the city of Beirut, Lebanon. While low PM mass concentrations were measured in the rainy season, elevated levels were detected during sand storms originating from Arabian desert and/or Africa. Using ATR-FTIR and IC, it was shown that nitrate, sulfate, carbonate and chloride were the main anionic constituents of the coarse particles, whereas sulfate was mostly predominant in the fine particles in the form of (NH4)2SO4. Ammonium nitrate was not expected to be important because the medium was defined as ammonium poor. In parallel, the cations Ca2+ and Na+ dominated in the coarse, and NH4+, Ca2+ and Na+ in the fine particles. Coarse nitrate and sulfate ions resulted from the respective reactions of nitric and sulfuric acid with a relatively high amount of calcium carbonate. Both CaCO3 and Ca(NO3)2 crystals identified by ATR-FTIR in the coarse particles were found to be resistant to soaking in water for 24 h but became water soluble when they were formed in the fine particles suggesting, thereby, different growth and adsorption phenomena. The seasonal variational study showed that nitrate and sulfate ion concentrations increased in the summer due to the enhancement of photochemical reactions which facilitated the conversion of NO2 and SO2 gases into NO3- and SO42-, respectively. While nitrate was mainly due to local heavy traffic, sulfates were due to local and long-range transport phenomena. Using the air mass trajectory HYSPLIT model, it was found that the increase in the sulfate concentration correlated with wind vectors coming from Eastern and Central Europe. Chloride levels, on the other hand, were high when wind originated from the sea and low during sand storms. In addition to sea salt, elevated levels of chloride were also attributed to waste mass burning in proximity to the site. In comparison to other neighboring Mediterranean countries, relatively higher concentrations of calcium in Beirut were good indication of calcitic crustal abundance. Considering the importance of the health and climate impacts of aerosols locally and regionally, this study constitutes a point of reference for eastern Mediterranean transport modeling studies and local regulatory and policy makers.
Aerosol light absorption in the North Atlantic: trends and seasonal characteristics during the period 1989 to 2003
Authors: Junker C. , Jennings S. G. , Cachier H.
Published: April 2010

Abstract. Aerosol light attenuation on quartz fibre filters has been measured since February 1989 at the Mace Head Atmospheric Research station near Carna, Co. Galway, Ireland, using an Aethalometer. The frequency of occurrence of the hourly averaged aerosol absorption data is found to be bimodally distributed. The two modes result from clean marine air and anthropogenically polluted continental air both being advected to the station dependent on the prevailing wind direction. The hourly averages of the marine portion of the aerosol light absorption are found to follow closely a lognormal distribution with a geometric mean of 0.310 Mm-1. The hourly averages of continental sector aerosol absorption are neither normally nor lognormally distributed and have an arithmetic mean of 6.36 Mm-1, indicating the presence of anthropogenic sources for BC east of the Mace Head station. The time series of the monthly averaged attenuation coefficient σatt of both marine and continental sector aerosol shows an increase from 1989 to 1997 and a levelling off thereafter. The monthly maximum of marine sector σatt is found in May. Trend and seasonal characteristics of the clean marine aerosol attenuation coefficients observed at Mace Head appear to be driven by meteorological factors, as indicated by rainfall data and by trends in the North Atlantic Oscillation (NAO) indices. The observed increasing trends of the continental sector σatt from 1989 up to 1997 are possibly related to changes in BC emissions over Ireland, calculated from UNSTAT (2002) fuel consumption data.
Modelling the budget of middle atmospheric water vapour isotopes
Authors: Zahn A. , Franz P. , Bechtel C. , Grooß J.-U. , Röckmann T.
Published: April 2010

Abstract. A one-dimensional chemistry model is applied to study the stable hydrogen (D) and stable oxygen isotope (17O, 18O) composition of water vapour in stratosphere and mesosphere. In the troposphere, this isotope composition is determined by "physical'' fractionation effects, that are phase changes (e.g. during cloud formation), diffusion processes (e.g. during evaporation from the ocean), and mixing of air masses. Due to these processes water vapour entering the stratosphere first shows isotope depletions in D/H relative to ocean water, which are ~5 times of those in 18O/16O, and secondly is mass-dependently fractionated (MDF), i.e. changes in the isotope ratio 17O/16O are ~0.52 times of those of 18O/16O. In contrast, in the stratosphere and mesosphere "chemical'' fractionation mechanisms, that are the production of HO due to the oxidation of methane, re-cycling of H2O via the HOx family, and isotope exchange reactions considerably enhance the isotope ratios in the water vapour imported from the troposphere. The model reasonably predicts overall enhancements of the stable isotope ratios in H2O by up to ~25% for D/H, ~8.5% for 17O/16O, and ~14% for 18O/16O in the mesosphere relative to the tropopause values. The 17O/16O and 18O/16O ratios in H2O are shown to be a measure of the relative fractions of HOx that receive the O atom either from the reservoirs O2 or O3. Throughout the middle atmosphere, MDF O2 is the major donator of oxygen atoms incorporated in OH and HO2 and thus in H2O. In the stratosphere the known mass-independent fractionation (MIF) signal in O3 is in a first step transferred to the NOx family and only in a second step to HOx and H2O. In contrast to CO2, O(1D) only plays a minor role in this MIF transfer. The major uncertainty in our calculation arises from poorly quantified isotope exchange reaction rate coefficients and kinetic isotope fractionation factors.
Sensitivity analysis by the adjoint chemistry transport model DRAISfor an episode in the Berlin Ozone (BERLIOZ) experiment
Authors: Nester K. , Panitz H.-J.
Published: April 2010

Abstract. The Berlin Ozone Experiment (BERLIOZ) was carried out in summer 1998. One of its purposes was the evaluation of Chemistry Transport Models (CTM). CTM KAMM/DRAIS was one of the models considered. The data of 20 July were selected for evaluation. On that day, a pronounced ozone plume developed downwind of the city. Evaluation showed that the KAMM/DRAIS model is able to reproduce the meteorological and ozone data observed, except at farther distances (60–80 km) downwind of the city. In that region, the DRAIS model underestimates the measured ozone concentrations by 10–15 ppb, approximately. Therefore, this study was conducted to detect possible reasons for this deviation. A comprehensive sensitivity analysis was carried out to determine the most relevant model parameters. The adjoint DRAIS model was developed for this purpose, because for this study the application of this model is the most effective method of calculating the sensitivities. The least squares of the measured and simulated ozone concentrations between 08:00 UTC and 16:00 UTC at two stations 30 km and 70 km downwind of the city centre were chosen as distance function. The model parameters considered in this study are the complete set of initial and boundary species concentrations, emissions, and reaction rates, respectively. A sensitivity ranking showing the relevance of the individual parameters in the set is determined for each parameter set. In order to find out which modification in the parameter sets most reduces the cost function, simplified 4-D data assimilation was carried out. The result of this data assimilation shows that modifications of the reaction rates provide the best agreement between the measured and the simulated ozone concentrations at both stations. However, the modified reaction rates seem to be unrealistic for the whole simulation period. Therefore, the good agreement should not be overestimated. The agreement is still acceptable when the parameters in the other sets are modified together. The investigation demonstrates that an analysis of this type can help to explain inconsistencies between observations and simulations. But in the case considered here the inconsistencies cannot be explained by an error in only one parameter set.
Size-resolved source apportionment of ambient particles by positive matrix factorization at Gosan background site in East Asia
Authors: Han J. S. , Moon K. J. , Lee S. J. , Kim Y. J. , Ryu S. Y. , Cliff S. S. , Yi S. M.
Published: April 2010

Abstract. Size- and time-resolved aerosol samples were collected using an eight-stage Davis rotating unit for monitoring (DRUM) sampler from 29 March to 29 May in 2002 at Gosan, Jeju Island, Korea, which is one of the representative background sites in East Asia. These samples were analyzed using synchrotron X-ray fluorescence for 3-h average concentrations of 19 elements consisting of S, Si, Al, Fe, Ca, Cl, Cu, Zn, Ti, K, Mn, Pb, Ni, V, Se, As, Rb, Cr, Br. The size-resolved data sets were then analyzed using the positive matrix factorization (PMF) technique in order to identify possible sources and estimate their contribution to particulate matter mass. PMF analysis uses the uncertainty of the measured data to provide an optimal weighting. Fifteen sources were resolved in eight size ranges (0.07~12 μm) and included continental soil, local soil, sea salt, biomass/biofuel burning, coal combustion, oil heating furnace, residual oil fired boiler, municipal incineration, nonferrous metal source, ferrous metal source, gasoline vehicle, diesel vehicle, copper smelter and volcanic emission. PMF analysis of size-resolved source contributions showed that natural sources represented by local soil, sea salt and continental soil contributed about 79% to the predicted primary particulate matter (PM) mass in the coarse size range (1.15~12 μm). On the other hand, anthropogenic sources such as coal combustion and biomass/biofuel burning contributed about 60% in the fine size range (0.56~2.5 μm). The diesel vehicle source contributed the most in the ultra-fine size range (0.07~0.56 μm) and was responsible for about 52% of the primary PM mass.
Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002
Authors: Fleming Z. L. , Monks P. S. , Rickard A. R. , Heard D. E. , Bloss W. J. , Seakins P. W. , Still T. J. , Sommariva R. , Pilling M. J. , Morgan R. , Green T. J. , Brough N. , Mills G. P. , Penkett S. A. , Lewis A. C. , Lee J. D. , Saiz-Lopez A. , Plane J. M. C.
Published: April 2010

Abstract. Peroxy radical (HO2+ΣRO2) measurements, using the PEroxy Radical Chemical Amplification (PERCA) technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX) at Mace Head in summer 2002, are presented and put into the context of marine, boundary-layer chemistry. A suite of other chemical parameters (NO, NO2, NO3, CO, CH4, O3, VOCs, peroxides), photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HOx. A good correlation exists between j(HCHO).[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HOx source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NO2] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO2/(HO2+ΣRO2) ratios are dependent on [NOx] ranging between 0.2 and 0.6, with the ratio increasing linearly with NOx. Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO3-alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv h-1. The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O3))/dln(NO)=1.0). The results imply that the N(O3) (the in-situ net photochemical rate of ozone production/destruction) will be strongly sensitive in the marine boundary layer to small changes in [NO] which has ramifications for changing NOx loadings in the European continental boundary layer.
The impact of ice uptake of nitric acid on atmospheric chemistry
Authors: von Kuhlmann R. , Lawrence M. G.
Published: April 2010

Abstract. The potential impact of the uptake of HNO3 on ice on the distribution of NOy species, ozone and OH has been assessed using the global scale chemistry-transport model MATCH-MPIC. Assuming equilibrium uptake according to dissociative Langmuir theory results in significant reductions of gas phase HNO3. Comparison to a large set of observations provides support that significant uptake of HNO3 on ice is occurring, but the degree of the uptake cannot be inferred from this comparison alone. Sensitivity simulations show that the uncertainties in the total amount of ice formation in the atmosphere and the actual expression of the settling velocity of ice particles only result in small changes in our results. The largest uncertainty is likely to be linked to the actual theory describing the uptake process and the value of the initial uptake coefficient. The inclusion of non-methane hydrocarbon chemistry partially compensates for the absence of HNO3 uptake on ice when this is neglected in the model. The calculated overall effect on upper tropospheric ozone concentrations and the tropospheric methane lifetime are moderate to low. These results support a shift in the motivation for future experimental and theoretical studies of HNO3-ice interaction towards the role of HNO3 in hydrometeor surface physics.
Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, sesquiterpenes, and related compounds
Authors: Varutbangkul V. , Brechtel F. J. , Bahreini R. , Ng N. L. , Keywood M. D. , Kroll J. H. , Flagan R. C. , Seinfeld J. H. , Lee A. , Goldstein A. H.
Published: April 2010

Abstract. A series of experiments has been conducted in the Caltech indoor smog chamber facility to investigate the water uptake properties of aerosol formed by oxidation of various organic precursors. Secondary organic aerosol (SOA) from simple and substituted cycloalkenes (C5-C8) is produced in dark ozonolysis experiments in a dry chamber (RH~5%). Biogenic SOA from monoterpenes, sesquiterpenes, and oxygenated terpenes is formed by photooxidation in a humid chamber (~50% RH). Using the hygroscopicity tandem differential mobility analyzer (HTDMA), we measure the diameter-based hygroscopic growth factor (GF) of the SOA as a function of time and relative humidity. All SOA studied is found to be slightly hygroscopic, with smaller water uptake than that of typical inorganic aerosol substances. The aerosol water uptake increases with time early in the experiments for the cycloalkene SOA, but decreases with time for the sesquiterpene SOA. This behavior could indicate competing effects between the formation of more highly oxidized polar compounds (more hygroscopic), and formation of longer-chained oligomers (less hygroscopic). All SOA also exhibit a smooth water uptake with RH with no deliquescence or efflorescence. The water uptake curves are found to be fitted well with an empirical three-parameter functional form. The measured pure organic GF values at 85% RH are between 1.09–1.16 for SOA from ozonolysis of cycloalkenes, 1.01–1.04 for sesquiterpene photooxidation SOA, and 1.06–1.10 for the monoterpene and oxygenated terpene SOA. The GF of pure SOA (GForg) in experiments in which inorganic seed aerosol is used is determined by assuming volume-weighted water uptake (Zdanovskii-Stokes-Robinson or "ZSR" approach) and using the size-resolved organic mass fraction measured by the Aerodyne Aerosol Mass Spectrometer. Knowing the water content associated with the inorganic fraction yields GForg values. However, for each precursor, the GForg values computed from different HTDMA-classified diameters agree with each other to varying degrees. Comparing growth factors from different precursors, we find that GForg is inversely proportional to the precursor molecular weight and SOA yield, which is likely a result of the fact that higher-molecular weight precursors tend to produce larger and less hygroscopic oxidation products.
A chemical probe technique for the determination of reactive halogen species in aqueous solution: Part 1 – bromide solutions
Authors: Matthew B. M. , Anastasio C.
Published: April 2010

Abstract. Reactive halogen species (X*=X•, •X2-, X2 and HOX, where X=Br, Cl, or I) in seawater, sea-salt particles, and snowpacks play important roles in the chemistry of the marine boundary layer. Despite this, relatively little is known about the steady-state concentrations or kinetics of reactive halogens in these environmental samples. In part this is because there are few instruments or techniques that can be used to characterize aqueous reactive halogens. To better understand this chemistry, we have developed a chemical probe technique that can detect and quantify aqueous reactive bromine and chlorine species (Br*(aq) and Cl*(aq)). This technique is based on the reactions of short-lived X*(aq) species with allyl alcohol (CH2=CHCH2OH) to form stable 3-halo-1,2-propanediols that are analyzed by gas chromatography. Using this technique in conjunction with competition kinetics allows determination of the steady state concentrations of the aqueous reactive halogens and, in some cases, the rates of formation and lifetimes of X* in aqueous solutions. We report here the results of the method development for aqueous solutions containing only bromide (Br-).
Kinetics and mechanism of heterogeneous oxidation of sulfur dioxide by ozone on surface of calcium carbonate
Authors: Li L. , Chen Z. M. , Zhang Y. H. , Zhu T. , Li J. L. , Ding J.
Published: April 2010

Abstract. Sulfate particles play a key role in the air quality and the global climate, but the heterogeneous formation mechanism of sulfates on surfaces of atmospheric particles is not well established. Carbonates, which act as a reactive component in mineral dust due to their special chemical properties, may contribute significantly to the sulfate formation by heterogeneous processes. This paper presents a study on the oxidation of SO2 by O3 on CaCO3 particles. Using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), the formation of sulfite and sulfate on the surface was identified, and the roles of O3 and water in oxidation processes were determined. The results showed that in the presence of O3, SO2can be oxidized to sulfate on the surface of CaCO3 particles. The reaction is first order in SO2 and zero order in O3. The reactive uptake coefficient for SO2 [(0.6–9.8)×1014 molecule cm-3] oxidation by O3 [(1.2–12)×1014 molecule cm-3] was determined to be (1.4±0.3)×10-7 using the BET area as the reactive area and (7.7±1.6)×10-4 using the geometric area. A two-stage mechanism that involves adsorption of SO2 followed by O3 oxidation is proposed and the adsorption of SO2 on the CaCO3 surface is the rate-determining step. The proposed mechanism can well explain the experiment results. The atmospheric implications were explored based on a box model calculation. It was found that the heterogeneous reaction might be an important pathway for sulfate formation in the atmosphere.
Application of positive matrix factorization in estimating aerosol secondary organic carbon in Hong Kong and its relationship with secondary sulfate
Authors: Yuan Z. B. , Yu J. Z. , Lau A. K. H. , Louie P. K. K. , Fung J. C. H.
Published: April 2010

Abstract. Secondary organic carbon (SOC) is often a significant portion of organic carbon (OC) in ambient particulate matter (PM). The levels and seasonal patterns of SOC in Hong Kong were examined using more than 2000 PM10 measurements made over a 4.5-year period (1998–2002) in a network of ten air quality monitoring stations. The positive matrix factorization (PMF) model was used to analyze this large data set for source identification and apportioning. SOC was subsequently estimated to be the sum of OC present in the secondary sources, i.e., secondary sulfate, secondary nitrate, and secondary organic aerosol. The annual average SOC as estimated by the PMF method was 4.25 μg C/m3 while the summer average was 1.66 μg C/m3 and the winter average was 7.05 μg C/m3. In comparison, the method that uses EC as a tracer for primary carbonaceous aerosol sources to derive SOC overestimated SOC by 70–212% for the summer samples and by 4–43% for the winter samples. The overestimation by the EC tracer method resulted from the inability of obtaining a single OC/EC ratio that represented a mixture of primary sources varying in time and space. We found that SOC and secondary sulfate had synchronous seasonal variation and were correlated in individual seasons, suggesting common factors that control their formation. Additionally, the presence of SOC was found to be enhanced more than that of secondary sulfate in the winter. We postulate this to be a combined result of favorable partitioning of semivolatile SOC species in the particle phase and more abundant SOC precursors in the winter.
The effect of physical and chemical aerosol properties on warm cloud droplet activation
Authors: McFiggans G. , Artaxo P. , Baltensperger U. , Coe H. , Facchini M. C. , Feingold G. , Fuzzi S. , Gysel M. , Laaksonen A. , Lohmann U. , Mentel T. F. , Murphy D. M. , O'Dowd C. D. , Snider J. R. , Weingartner E.
Published: April 2010

Abstract. The effects of atmospheric aerosol on climate forcing may be very substantial but are quantified poorly at present; in particular, the effects of aerosols on cloud radiative properties, or the "indirect effects" are credited with the greatest range of uncertainty amongst the known causes of radiative forcing. This manuscript explores the effects that the composition and properties of atmospheric aerosol can have on the activation of droplets in warm clouds, so potentially influencing the magnitude of the indirect effect. The effects of size, composition, mixing state and various derived properties are assessed and a range of these properties provided by atmospheric measurements in a variety of locations is briefly reviewed. The suitability of a range of process-level descriptions to capture these aerosol effects is investigated by assessment of their sensitivities to uncertainties in aerosol properties and by their performance in closure studies. The treatment of these effects within global models is reviewed and suggestions for future investigations are made.
Observation of mesospheric air inside the arctic stratospheric polar vortex in early 2003
Authors: Engel A. , Möbius T. , Haase H.-P. , Bönisch H. , Wetter T. , Schmidt U. , Levin I. , Reddmann T. , Oelhaf H. , Wetzel G. , Grunow K. , Huret N. , Pirre M.
Published: April 2010

Abstract. During several balloon flights inside the Arctic polar vortex in early 2003, unusual trace gas distributions were observed, which indicate a strong influence of mesospheric air in the stratosphere. The tuneable diode laser (TDL) instrument SPIRALE (Spectroscopie Infra-Rouge par Absorption de Lasers Embarqués) measured unusually high CO values (up to 600 ppb) on 27 January at about 30 km altitude. The cryosampler BONBON sampled air masses with very high molecular Hydrogen, extremely low SF6 and enhanced CO values on 6 March at about 25 km altitude. Finally, the MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) Fourier Transform Infra-Red (FTIR) spectrometer showed NOy values which are significantly higher than NOy* (the NOy derived from a correlation between N2O and NOy under undisturbed conditions), on 21 and 22 March in a layer centred at 22 km altitude. Thus, the mesospheric air seems to have been present in a layer descending from about 30 km in late January to 25 km altitude in early March and about 22 km altitude on 20 March. We present corroborating evidence from a model study using the KASIMA (KArlsruhe SImulation model of the Middle Atmosphere) model that also shows a layer of mesospheric air, which descended into the stratosphere in November and early December 2002, before the minor warming which occurred in late December 2002 lead to a descent of upper stratospheric air, cutting off a layer in which mesospheric air is present. This layer then descended inside the vortex over the course of the winter. The same feature is found in trajectory calculations, based on a large number of trajectories started in the vicinity of the observations on 6 March. Based on the difference between the mean age derived from SF6 (which has an irreversible mesospheric loss) and from CO2 (whose mesospheric loss is much smaller and reversible) we estimate that the fraction of mesospheric air in the layer observed on 6 March, must have been somewhere between 35% and 100%.
Vertical profiles of O3and NOxchemistry in the polluted nocturnal boundary layer in Phoenix, AZ: I. Field observations by long-path DOAS
Authors: Wang S. , Ackermann R. , Stutz J.
Published: April 2010

Abstract. Nocturnal chemistry in the atmospheric boundary layer plays a key role in determining the initial chemical conditions for photochemistry during the following morning as well as influencing the budgets of O3 and NO2. Despite its importance, chemistry in the nocturnal boundary layer (NBL), especially in heavily polluted urban areas, has received little attention so far, which greatly limits the current understanding of the processes involved. In particular, the influence of vertical mixing on chemical processes gives rise to complex vertical profiles of various reactive trace gases and makes nocturnal chemistry altitude-dependent. The processing of pollutants is thus driven by a complicated, and not well quantified, interplay between chemistry and vertical mixing. In order to gain a better understanding of the altitude-dependent nocturnal chemistry in the polluted urban environment, a field study was carried out in the downtown area of Phoenix, AZ, in summer 2001. Vertical profiles of reactive species, such as O3, NO2, and NO3, were observed in the lowest 140 m of the troposphere throughout the night. The disappearance of these trace gas vertical gradients during the morning coincided with the morning transition from a stable NBL to a well-mixed convective layer. The vertical gradients of trace gas levels were found to be dependent on both surface NOx emission strength and the vertical stability of the NBL. The vertical gradients of Ox, the sum of O3 and NO2, were found to be much smaller than those of O3 and NO2, revealing the dominant role of NO emissions followed by the O3+NO reaction for the altitude-dependence of nocturnal chemistry in urban areas. Dry deposition, direct emissions, and other chemical production pathways of NO2 also play a role for the Ox distribution. Strong positive vertical gradients of NO3, that are predominantly determined by NO3 loss near the ground, were observed. The vertical profiles of NO3 and the calculated vertical profiles of its reservoir species (N2O5) confirm earlier model results suggesting complex vertical distributions of atmospheric denoxification processes during the night.
Retrieval of stratospheric ozone profiles from MIPAS/ENVISAT limb emission spectra: a sensitivity study
Authors: Glatthor N. , von Clarmann T. , Fischer H. , Funke B. , Gil-López S. , Grabowski U. , Höpfner M. , Kellmann S. , Linden A. , López-Puertas M. , Mengistu Tsidu G. , Milz M. , Steck T. , Stiller G. P. , Wang D.-Y.
Published: April 2010

Abstract. We report on the dependence of ozone volume mixing ratio profiles, retrieved from limb emission infrared spectra of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), on different retrieval setups such as the treatment of the background continuum, cloud filtering, spectral regions used for analysis and a series of further more technical parameter choices. The purpose of this investigation is to better understand the error sources of the ozone retrieval, to optimize the current retrieval setup and to document changes in the data versions. It was shown that the cloud clearing technique used so far (cloud index 1.8) does not reliably exclude all cloud-contaminated spectra from analysis. Through analysis of spectra calculated for cloudy atmospheres we found that the cloud index should be increased to a value of 3.0 or higher. Further, it was found that assignment of a common background continuum to adjacent microwindows within 5 cm−1 is advantageous, because it sufficiently represents the continuum emission by aerosols, clouds and gases as reported in the literature, and is computationally more efficient. For ozone retrieval we use ozone lines from MIPAS band A (685–970 cm−1) and band AB (1020–1170 cm−1) as well. Therefore we checked ozone retrievals with lines from bands A or AB only for a systematic difference. Such a difference was indeed found and could, to a major part, be attributed to the spectroscopic data used in these two bands, and to a minor part to neglection of modelling of non-local thermodynamic (non-LTE) emissions. Another potential explanation, a bias in the radiance calibration of level-1B spectra of bands A and AB, could largely be ruled out by correlation analysis and inspection of broadband spectra. Further upgrades in the ozone retrieval consist of application of an all-zero a-priori profile and a weaker regularization. Finally, the ozone distribution obtained with the new retrieval setup (data versions V3o_O3_7) was compared to the data version used before (V2_O3_2). Differences are smaller than ±0.4 ppmv in the altitude region 15–50 km. Further, differences to ozone measured by the HALogen Occultation Experiment (HALOE) on the Upper Atmospheric Research Satellite (UARS) are partly reduced with the new MIPAS data version.
Highly resolved observations of trace gases in the lowermost stratosphere and upper troposphere from the Spurt project: an overview
Authors: Engel A. , Bönisch H. , Brunner D. , Fischer H. , Franke H. , Günther G. , Gurk C. , Hegglin M. , Hoor P. , Königstedt R. , Krebsbach M. , Maser R. , Parchatka U. , Peter T. , Schell D. , Schiller C. , Schmidt U. , Spelten N. , Szabo T. , Weers U. , Wernli H. , Wetter T. , Wirth V.
Published: April 2010

Abstract. During SPURT (Spurenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region) we performed measurements of a wide range of trace gases with different lifetimes and sink/source characteristics in the northern hemispheric upper troposphere (UT) and lowermost stratosphere (LMS). A large number of in-situ instruments were deployed on board a Learjet 35A, flying at altitudes up to 13.7 km, at times reaching to nearly 380 K potential temperature. Eight measurement campaigns (consisting of a total of 36 flights), distributed over all seasons and typically covering latitudes between 35° N and 75° N in the European longitude sector (10° W–20° E), were performed. Here we present an overview of the project, describing the instrumentation, the encountered meteorological situations during the campaigns and the data set available from SPURT. Measurements were obtained for N2O, CH4, CO, CO2, CFC12, H2, SF6, NO, NOy, O3 and H2O. We illustrate the strength of this new data set by showing mean distributions of the mixing ratios of selected trace gases, using a potential temperature-equivalent latitude coordinate system. The observations reveal that the LMS is most stratospheric in character during spring, with the highest mixing ratios of O3 and NOy and the lowest mixing ratios of N2O and SF6. The lowest mixing ratios of NOy and O3 are observed during autumn, together with the highest mixing ratios of N2O and SF6 indicating a strong tropospheric influence. For H2O, however, the maximum concentrations in the LMS are found during summer, suggesting unique (temperature- and convection-controlled) conditions for this molecule during transport across the tropopause. The SPURT data set is presently the most accurate and complete data set for many trace species in the LMS, and its main value is the simultaneous measurement of a suite of trace gases having different lifetimes and physical-chemical histories. It is thus very well suited for studies of atmospheric transport, for model validation, and for investigations of seasonal changes in the UT/LMS, as demonstrated in accompanying and elsewhere published studies.
Meteorological implementation issues in chemistry and transport models
Authors: Strahan S. E. , Polansky B. C.
Published: April 2010

Abstract. Offline chemistry and transport models (CTMs) are versatile tools for studying composition and climate issues requiring multi-decadal simulations. They are computationally fast compared to coupled chemistry climate models, making them well-suited for integrating sensitivity experiments necessary for understanding model performance and interpreting results. The archived meteorological fields used by CTMs can be implemented with lower horizontal or vertical resolution than the original meteorological fields in order to shorten integration time, but the effects of these shortcuts on transport processes must be understood if the CTM is to have credibility. In this paper we present a series of sensitivity experiments on a CTM using the Lin and Rood advection scheme, each differing from another by a single feature of the wind field implementation. Transport effects arising from changes in resolution and model lid height are evaluated using process-oriented diagnostics that intercompare CH4, O3, and age tracer carried in the simulations. Some of the diagnostics used are derived from observations and are shown as a reality check for the model. Processes evaluated include tropical ascent, tropical-midlatitude exchange, poleward circulation in the upper stratosphere, and the development of the Antarctic vortex. We find that faithful representation of stratospheric transport in this CTM is possible with a full mesosphere, ~1 km resolution in the lower stratosphere, and relatively low vertical resolution (>4 km spacing) in the middle stratosphere and above, but lowering the lid from the upper to lower mesosphere leads to less realistic constituent distributions in the upper stratosphere. Ultimately, this affects the polar lower stratosphere, but the effects are greater for the Antarctic than the Arctic. The fidelity of lower stratospheric transport requires realistic tropical and high latitude mixing barriers which are produced at 2°×2.5°, but not lower resolution. At 2°×2.5° resolution, the CTM produces a vortex capable of isolating perturbed chemistry (e.g. high Cly and low NOy) required for simulating polar ozone loss.
An inverse modeling procedure to determine particle growth and nucleation rates from measured aerosol size distributions
Authors: Verheggen B. , Mozurkewich M.
Published: April 2010

Abstract. Classical nucleation theory is unable to explain the ubiquity of nucleation events observed in the atmosphere. This shows a need for an empirical determination of the nucleation rate. Here we present a novel inverse modeling procedure to determine particle nucleation and growth rates based on consecutive measurements of the aerosol size distribution. The particle growth rate is determined by regression analysis of the measured change in the aerosol size distribution over time, taking into account the effects of processes such as coagulation, deposition and/or dilution. This allows the growth rate to be determined with a higher time-resolution than can be deduced from inspecting contour plots ("banana-plots''). Knowing the growth rate as a function of time enables the evaluation of the time of nucleation of measured particles of a certain size. The nucleation rate is then obtained by integrating the particle losses from time of measurement to time of nucleation. The regression analysis can also be used to determine or verify the optimum value of other parameters of interest, such as the wall loss or coagulation rate constants. As an example, the method is applied to smog chamber measurements. This program offers a powerful interpretive tool to study empirical aerosol population dynamics in general, and nucleation and growth in particular.
Strong spectral dependence of light absorption by organic carbon particles formed by propane combustion
Authors: Schnaiter M. , Gimmler M. , Llamas I. , Linke C. , Jäger C. , Mutschke H.
Published: April 2010

Abstract. We have measured the extinction and absorption cross sections of carbon particles emitted by a propane diffusion flame both in an aerosol chamber and on size-segregated samples deposited on optical windows. The absorption cross section, the single scattering albedo, and the Ångström exponent show drastic dependencies both on the C/O ratio and on the particle size. This is interpretated as being due to the appearance of nucleation modes of smaller organic particles at higher C/O ratios, which were detected by SMPS measurements and partially by TEM analysis. The spectral range of the validity of the absorption power-law (Ångström exponent) model is investigated by vacuum ultraviolet extinction measurements. These measurements give also indications for a preferentially aromatic nature of the OC component of the flame products.
Homogeneous nucleation rates of nitric acid dihydrate (NAD) at simulated stratospheric conditions – Part I: Experimental results
Authors: Stetzer O. , Möhler O. , Wagner R. , Benz S. , Saathoff H. , Bunz H. , Indris O.
Published: April 2010

Abstract. The low temperature aerosol chamber AIDA was used to study the nucleation of nitric acid dihydrate (NAD) in super-cooled nitric acid aerosols under simulated stratospheric conditions in the temperature range 192 K–197 K. The nucleating solution droplets had median diameters between 225 and 290 nm and molar fractions of nitric acid between 0.26 and 0.28. Nucleation of solid particles was unambiguously observed in two out of three experiments during time periods of up to five hours. The newly formed crystals could be clearly distinguished from the remaining liquid droplets by their increasing size with an optical particle spectrometer. The solid particles could be unequivocally identified as strongly aspherical nitric acid dihydrate crystals (α-NAD) by in-situ FTIR-spectroscopy. From our experimental data set there is no indication of direct nucleation of NAT or a conversion of NAD into NAT while having saturation ratios with respect to NAT of about 20–26. The temporal evolutions of the NAD particle concentrations were used to derive individual nucleation rates for NAD. The measured volume nucleation rates ranged from 3.9×105 cm−3 s−1 at 195.8 K and XNA=0.27 to 1.9×107 cm−3 s−1 at 192.1 K and XNA=0.28. The corresponding hypothetical surface nucleation rates of 2×100 to 1×102 cm−2 s−1 are smaller than the parameterization of Tabazadeh et al. (2002) by factors between 25 and >103.
The potential impact of ClOx radical complexes on polar stratospheric ozone loss processes
Authors: Vogel B. , Feng W. , Streibel M. , Müller R.
Published: April 2010

Abstract. The importance of radical-molecule complexes for atmospheric chemistry has been discussed in recent years. In particular, the existence of a ClO·O2 and ClOx water radical complexes like ClO·H2O, OClO·H2O, OClO·(H2O)2, and ClOO·H2O could play a role in enhancing the ClO dimer (Cl2O2) formation and therefore may constitute an important intermediate in polar stratospheric ozone loss cycles. Model simulations performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS) will be presented to study the role of radical complexes on polar stratospheric ozone loss processes. The model simulations are performed for the Arctic winter 2002/2003 at a level of 500 K potential temperature and the results are compared to observed ozone loss rates determined by the Match technique. Moreover, recently reported values for the equilibrium constant of the ClO dimer formation are used to restrict the number of possible model results caused by large uncertainties about radical complex chemistry. Our model simulations show that the potential impact of ClO·O2 on polar ozone loss processes is small (dO3/dt≪0.5 ppb/sunlight h) provided that the ClO·O2 complex is only weakly stable. Assuming that the binding energies of the ClOx water complexes are much higher than theoretically predicted an enhancement of the ozone loss rate by up to ≈0.5 ppb/sunlight h is simulated. Because it is unlikely that the ClOx water complexes are much more stable than predicted we conclude that these complexes have no impact on polar stratospheric ozone loss processes. Although large uncertainties about radical complex chemistry exist, our findings show that the potential impact of ClOx radical molecule complexes on polar stratospheric ozone loss processes is very small considering pure gas-phase chemistry. However the existence of ClOx radical-molecule complexes could possibly explain discrepancies for the equilibrium constant of the ClO dimer formation found between recent laboratory and stratospheric measurements.
Testing our understanding of Arctic denitrification using MIPAS-E satellite measurements in winter 2002/2003
Authors: Davies S. , Mann G. W. , Carslaw K. S. , Chipperfield M. P. , Remedios J. J. , Allen G. , Waterfall A. M. , Spang R. , Toon G. C.
Published: April 2010

Abstract. Observations of gas-phase HNO3 and N2O in the polar stratosphere from the Michelson Interferometer for Passive Atmospheric Sounding aboard the ENVISAT satellite (MIPAS-E) were made during the cold Arctic winter of 2002/2003. Vortex temperatures were unusually low in early winter and remained favourable for polar stratospheric cloud formation and denitrification until mid-January. MIPAS-E observations provide the first dataset with sufficient coverage of the polar vortex in mid-winter which enables a reasonable estimate of the timing of onset and spatial distribution of denitrification of the Arctic lower stratosphere to be performed. We use the observations from MIPAS-E to test the evolution of denitrification in the DLAPSE (Denitrification by Lagrangian Particle Sedimentation) microphysical denitrification model coupled to the SLIMCAT chemical transport model. In addition, the predicted denitrification from a simple equilibrium nitric acid trihydrate-based scheme is also compared with MIPAS-E. Modelled denitrification is compared with in-vortex NOy and N2O observations from the balloon-borne MarkIV interferometer in mid-December. Denitrification was clearly observed by MIPAS-E in mid-December 2002 and reached 80% in the core of the vortex by early January 2003. The DLAPSE model is broadly able to capture both the timing of onset and the spatial distribution of the observed denitrification. A simple thermodynamic equilibrium scheme is able to reproduce the observed denitrification in the core of the vortex but overestimates denitrification closer to the vortex edge. This study also suggests that the onset of denitrification in simple thermodynamic schemes may be earlier than in the MIPAS-E observations.
Polar tropospheric ozone depletion events observed in the International Geophysical Year of 1958
Authors: Roscoe H. K. , Roscoe J.
Published: April 2010

Abstract. The Royal Society expedition to Antarctica established a base at Halley Bay, in support of the International Geophysical Year of 1957–1958. Surface ozone was measured during 1958 only, using a prototype Brewer-Mast sonde. The envelope of maximum ozone was an annual cycle from 10 ppbv in January to 22 ppbv in August. These values are 35% less at the start of the year and 15% less at the end than modern values from Neumayer, also a coastal site. This may reflect a general increase in surface ozone since 1958 and differences in summer at the less windy site of Halley, or it may reflect ozone loss on the inlet together with long-term conditioning. There were short periods in September when ozone values decreased rapidly to near-zero, and some in August when ozone values were rapidly halved. Such ozone-loss episodes, catalysed by bromine compounds, became well-known in the Artic in the 1980s, and were observed more recently in the Antarctic. In 1958, very small ozone values were recorded for a week in midwinter during clear weather with light winds. The absence of similar midwinter reductions at Neumayer, or at Halley in the few measurements during 1987, means we must remain suspicious of these small values, but we can find no obvious reason to discount them. The dark reaction of ozone and seawater ice observed in the laboratory may be fast enough to explain them if the salinity and surface area of the ice is sufficiently amplified by frost flowers.
Imaging gravity waves in lower stratospheric AMSU-A radiances, Part 2: Validation case study
Authors: Eckermann S. D. , Wu D. L. , Doyle J. D. , Burris J. F. , McGee T. J. , Hostetler C. A. , Coy L. , Lawrence B. N. , Stephens A. , McCormack J. P. , Hogan T. F.
Published: April 2010

Abstract. Two-dimensional radiance maps from Channel 9 (~60–90 hPa) of the Advanced Microwave Sounding Unit (AMSU-A), acquired over southern Scandinavia on 14 January 2003, show plane-wave-like oscillations with a wavelength λh of ~400–500 km and peak brightness temperature amplitudes of up to 0.9 K. The wave-like pattern is observed in AMSU-A radiances from 8 overpasses of this region by 4 different satellites, revealing a growth in the disturbance amplitude from 00:00 UTC to 12:00 UTC and a change in its horizontal structure between 12:00 UTC and 20:00 UTC. Forecast and hindcast runs for 14 January 2003 using high-resolution global and regional numerical weather prediction (NWP) models generate a lower stratospheric mountain wave over southern Scandinavia with peak 90 hPa temperature amplitudes of ~5–7 K at 12:00 UTC and a similar horizontal wavelength, packet width, phase structure and time evolution to the disturbance observed in AMSU-A radiances. The wave's vertical wavelength is ~12 km. These NWP fields are validated against radiosonde wind and temperature profiles and airborne lidar profiles of temperature and aerosol backscatter ratios acquired from the NASA DC-8 during the second SAGE III Ozone Loss and Validation Experiment (SOLVE II). Both the amplitude and phase of the stratospheric mountain wave in the various NWP fields agree well with localized perturbation features in these suborbital measurements. In particular, we show that this wave formed the type II polar stratospheric clouds measured by the DC-8 lidar. To compare directly with the AMSU-A data, we convert these validated NWP temperature fields into swath-scanned brightness temperatures using three-dimensional Channel 9 weighting functions and the actual AMSU-A scan patterns from each of the 8 overpasses of this region. These NWP-based brightness temperatures contain two-dimensional oscillations due to this resolved stratospheric mountain wave that have an amplitude, wavelength, horizontal structure and time evolution that closely match those observed in the AMSU-A data. These comparisons not only verify gravity wave detection and horizontal imaging capabilities for AMSU-A Channel 9, but provide an absolute validation of the anticipated radiance signals for a given three-dimensional gravity wave, based on the modeling of Eckermann and Wu (2006).