bluuebunny/crossref_metadata_2025 huggingface dataset:
Variability and trends in total and vertically resolved stratospheric ozone based on the CATO ozone data set
Authors: Brunner D. , Staehelin J. , Maeder J. A. , Wohltmann I. , Bodeker G. E.
Published: April 2010

Abstract. Trends in ozone columns and vertical distributions were calculated for the period 1979–2004 based on the ozone data set CATO (Candidoz Assimilated Three-dimensional Ozone) using a multiple linear regression model. CATO has been reconstructed from TOMS, GOME and SBUV total column ozone observations in an equivalent latitude and potential temperature framework and offers a pole to pole coverage of the stratosphere on 15 potential temperature levels. The regression model includes explanatory variables describing the influence of the quasi-biennial oscillation (QBO), volcanic eruptions, the solar cycle, the Brewer-Dobson circulation, Arctic ozone depletion, and the increase in stratospheric chlorine. The effects of displacements of the polar vortex and jet streams due to planetary waves, which may significantly affect trends at a given geographical latitude, are eliminated in the equivalent latitude framework. The QBO shows a strong signal throughout most of the lower stratosphere with peak amplitudes in the tropics of the order of 10–20% (peak to valley). The eruption of Pinatubo led to annual mean ozone reductions of 15–25% between the tropopause and 23 km in northern mid-latitudes and to similar percentage changes in the southern hemisphere but concentrated at altitudes below 17 km. Stratospheric ozone is elevated over a broad latitude range by up to 5% during solar maximum compared to solar minimum, the largest increase being observed around 30 km. This is at a lower altitude than reported previously, and no negative signal is found in the tropical lower stratosphere. The Brewer-Dobson circulation shows a dominant contribution to interannual variability at both high and low latitudes and accounts for some of the ozone increase seen in the northern hemisphere since the mid-1990s. Arctic ozone depletion significantly affects the high northern latitudes between January and March and extends its influence to the mid-latitudes during later months. The vertical distribution of the ozone trend shows distinct negative trends at about 18 km in the lower stratosphere with largest declines over the poles, and above 35 km in the upper stratosphere. A narrow band of large negative trends extends into the tropical lower stratosphere. Assuming that the observed negative trend before 1995 continued to 2004 cannot explain the ozone changes since 1996. A model accounting for recent changes in equivalent effective stratospheric chlorine, aerosols and Eliassen-Palm flux, on the other hand, closely tracks ozone changes since 1995.
Formation of secondary organic aerosol and oligomers from the ozonolysis of enol ethers
Authors: Sadezky A. , Chaimbault P. , Mellouki A. , Römpp A. , Winterhalter R. , Le Bras G. , Moortgat G. K.
Published: April 2010

Abstract. Formation of secondary organic aerosol has been observed in the gas phase ozonolysis of a series of enol ethers, among them several alkyl vinyl ethers (AVE, ROCH=CH2), such as ethyl, propyl, n-butyl, iso-butyl, t-butyl vinyl ether, and ethyl propenyl ether (EPE, C2H5OCH=CHCH3). The ozonolysis has been studied in a 570 l spherical glass reactor at ambient pressure (730 Torr) and room temperature (296 K). Gas phase reaction products were investigated by in-situ FTIR spectroscopy, and secondary organic aerosol (SOA) formation was monitored by a scanning mobility particle sizer (SMPS). The chemical composition of the formed SOA was analysed by a hybrid mass spectrometer using electrospray ionization (ESI). The main stable gas phase reaction product is the respective alkyl formate ROC(O)H, formed with yields of 60 to 80%, implying that similar yields of the corresponding excited Criegee Intermediates (CI) CH2O2 for the AVE and CH3CHO2 for EPE are generated. Measured SOA yields are between 2 to 4% for all enol ethers. Furthermore, SOA formation is strongly reduced or suppressed by the presence of an excess of formic acid, which acts as an efficient CI scavenger. Chemical analysis of the formed SOA by ESI(+)/MS-TOF allows to identify oligomeric compounds in the mass range 200 to 800 u as its major constituents. Repetitive chain units are identified as CH2O2 (mass 46) for the AVE and C2H4O2 (mass 60) for EPE and thus have the same chemical compositions as the respective major Criegee Intermediates formed during ozonolysis of these ethers. The oligomeric structure and chain unit identity are confirmed by HPLC/ESI(+)/MS-TOF and ESI(+)/MS/MS-TOF experiments, whereby successive and systematic loss of a fragment with mass 46 for the AVE (and mass 60 for EPE) is observed. It is proposed that the oligomer has the following basic structure of an oligoperoxide, -[CH(R)-O-O]n-, where R=H for the AVE and R=CH3 for the EPE. Oligoperoxide formation is thus suggested to be another, so far unknown reaction of stabilized Criegee Intermediates in the gas phase ozonolysis of oxygen-containing alkenes leading to SOA formation.
Technical note: First spectral measurement of the Earth's upwelling emission using an uncooled wideband Fourier transform spectrometer
Authors: Palchetti L. , Belotti C. , Bianchini G. , Castagnoli F. , Carli B. , Cortesi U. , Pellegrini M. , Camy-Peyret C. , Jeseck P. , Té Y.
Published: April 2010

Abstract. The first spectral measurement of Earth's emitted radiation to space in the wideband range from 100 to 1400 cm−1 with 0.5 cm−1 spectral resolution is presented. The measurement was performed from a stratospheric balloon in tropical region using a Fourier transform spectrometer, during a field campaign held in Brazil in June 2005. The instrument, which has uncooled components including the detector module, is a prototype developed as part of the study for the REFIR (Radiation Explorer in the Far InfraRed) space mission. This paper shows the results of the field campaign with particular attention to the measurement capabilities of the prototype. The results are compared with measurements taken by IASI-balloon (Infrared Atmospheric Sounding Interferometer – Balloon version), aboard the same platform, and with forward model estimations. The infrared signature of clouds is observed in the measurements.
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 setup up to 0.01 hPa was used at spectral T42 resolution to simulate the lower and middle atmosphere. With the high vertical resolution the model simulates the Quasi-Biennial Oscillation. 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. In the simulations presented here 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. This allows an efficient and direct evaluation with satellite and in-situ data. It is shown that the tropospheric wave forcing of the stratosphere in the model suffices to reproduce 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 well, 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 inter-annual 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.
Can we explain the trends in European ozone levels?
Authors: Jonson J. E. , Simpson D. , Fagerli H. , Solberg S.
Published: April 2010

Abstract. Ozone levels in Europe are changing. Emissions of ozone precursors from Europe (NOx, CO and non-methane hydrocarbons) have been substantially reduced over the last 10–15 years, but changes in ozone levels cannot be explained by changes in European emissions alone. The observed ozone trends at many European sites are only partially reproduced by global or regional photochemistry models, and possible reasons for this are discussed. In order to further explain the European trends in ozone since 1990, the EMEP regional photochemistry model has been run for the years 1990 and 1995–2002. The EMEP model is a regional model centred over Europe but the model domain also includes most of the North Atlantic and the polar region. Climatological ozone data are used as initial and lateral boundary concentrations. Model results are compared to measurements over this timespan of 12 years. Possible causes for the measured trends in European surface ozone have been investigated using model sensitivity runs perturbing emissions and lateral boundary concentrations. The increase in winter ozone partially, and the decrease in the magnitude of high ozone episodes, is attributed to the decrease in ozone precursor emissions since 1990 by the model. Furthermore, the model calculations indicate that the emission reductions have resulted in a marked decrease in summer ozone in major parts of Europe, in particular in Germany. Such a trend in summer ozone is likely to be difficult to identify from the measurements alone because of large inter-annual variability.
Effects of methane outgassing on the Black Sea atmosphere
Authors: Kourtidis K. , Kioutsioukis I. , McGinnis D. F. , Rapsomanikis S.
Published: April 2010

Abstract. Methane in air and seawater was measured in the Eastern Black Sea during the 10–18 December 1999 BIGBLACK project cruise. The measurements allowed for the calculation of supersaturation ratios and methane fluxes across the air-sea interface. CH4 mixing ratios in air were generally in the 1.8–2.0 ppmv range, while surface (4 m depth) seawater concentrations varied from 4 to 93 ppmv. Above active seep areas, the water was supersaturated to around 500% with respect to the overlying atmosphere. Accordingly, flux densities varied greatly and were up to 3300 umol m−2 day−1. In the Sevastopol harbour, supersaturations up to around 3000%, similar to those at the Danube Delta, were observed, while in the Istanbul harbour supersaturations could not be determined because the very high values of water concentrations led to detector saturation. Simple modelling shows that the observed fluxes do not have any substantial impact on the methane content of the Black Sea atmosphere, as they would only raise its concentrations by less than 50 ppt. On the other hand, calculations performed as part of the CRIMEA project show that mud volcano eruptions could episodically raise the methane concentrations well above their regional background for several tens of kilometres downwind. These calculations, which also apply to mud volcano eruptions elsewhere on the globe, indicate that the spatial extend and the magnitude of the atmospheric perturbation is such that its observation might lie within the capabilities of existing satellite instrumentation such as SCIAMACHY on ENVISAT.
The total ozone field separated into meteorological regimes – Part II: Northern Hemisphere mid-latitude total ozone trends
Authors: Hudson R. D. , Andrade M. F. , Follette M. B. , Frolov A. D.
Published: April 2010

Abstract. Previous studies have presented clear evidence that the Northern Hemisphere total ozone field can be separated into distinct regimes (tropical, midlatitude, polar, and arctic) the boundaries of which are associated with the subtropical and polar upper troposphere fronts, and in the winter, the polar vortex. This paper presents a study of total ozone variability within these regimes, from 1979–2003, using data from the TOMS instruments. The change in ozone within each regime for the period January 1979–May 1991, a period of rapid total ozone change, was studied in detail. Previous studies had observed a zonal linear trend of −3.15% per decade for the latitude band 25°–60° N. When the ozone field is separated by regime, linear trends of −1.4%, 2.3%, and 3.0%, per decade for the tropical, midlatitude, and polar regimes, respectively, are observed. The changes in the relative areas of the regimes were also derived from the ozone data. The relative area of the polar regime decreased by about 20%; the tropical regime increased by about 10% over this period. No significant change was detected for the midlatitude regime. From the trends in the relative area and total ozone it is deduced that 35% of the trend between 25° and 60° N, from January 1979–May 1991 is due to movement of the upper troposphere fronts. The changes in the relative areas can be associated with a change in the mean latitude of the subtropical and polar fronts within the latitude interval 25° to 60° N. Over the period from January 1979 to May 1991, both fronts moved northward by 1.1±0.2 degrees per decade. Over the entire period of the study, 1979–2003, the subtropical front moved northward at a rate of 1.1±0.1 degrees per decade, while the polar front moved by 0.5±0.1 degrees per decade.
Modeling of biomass smoke injection into the lower stratosphere by a large forest fire (Part I): reference simulation
Authors: Trentmann J. , Luderer G. , Winterrath T. , Fromm M. D. , Servranckx R. , Textor C. , Herzog M. , Graf H.-F. , Andreae M. O.
Published: April 2010

Abstract. Wildland fires in boreal regions have the potential to initiate deep convection, so-called pyro-convection, due to their release of sensible heat. Under favorable atmospheric conditions, large fires can result in pyro-convection that transports the emissions into the upper troposphere and the lower stratosphere. Here, we present three-dimensional model simulations of the injection of fire emissions into the lower stratosphere by pyro-convection. These model simulations are constrained and evaluated with observations obtained from the Chisholm fire in Alberta, Canada, in 2001. The active tracer high resolution atmospheric model (ATHAM) is initialized with observations obtained by radiosonde. Information on the fire forcing is obtained from ground-based observations of the mass and moisture of the burned fuel. Based on radar observations, the pyro-convection reached an altitude of about 13 km, well above the tropopause, which was located at about 11.2 km. The model simulation yields a similarly strong convection with an overshoot of the convection above the tropopause. The main outflow from the pyro-convection occurs at about 10.6 km, but a significant fraction (about 8%) of the emitted mass of the smoke aerosol is transported above the tropopause. In contrast to regular convection, the region with maximum updraft velocity in the pyro-convection is located close to the surface above the fire. This results in high updraft velocities >10 m s−1 at cloud base. The temperature anomaly in the plume decreases rapidly with height from values above 50 K at the fire to about 5 K at about 3000 m above the fire. While the sensible heat released from the fire is responsible for the initiation of convection in the model, the release of latent heat from condensation and freezing dominates the overall energy budget. Emissions of water vapor from the fire do not significantly contribute to the energy budget of the convection.
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 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.
Methane emission from tropical savanna Trachypogon sp. grasses
Authors: Sanhueza E. , Donoso L.
Published: April 2010

Abstract. Methane flux measurements from the soil-grass system were made during the wet season in unperturbed plots and plots where standing dry and green Trachypogon sp. grasses were clipped to just above the soil surface. Results support the surprising discovery that vegetation emits methane. The results of this work allows to infer that the savanna dry/green mixture of grasses produce methane at a rate of ~10 ng m−2 s−1, which is in agreement with early published soil-grass system fluxes. An extrapolation of this flux to the global savanna produces an annual emission much lower than the CH4 production recently suggested in the literature. On the other hand, during the wet season savanna soil consume CH4 at a rate of ~4.7 ng m−2 s−1. Therefore, the tropical savanna soil-grass system would make a modest contribution to the global budget of methane.
Tecnical Note: Analysis of non-regulated vehicular emissions by extractive FTIR spectrometry: tests on a hybrid car in Mexico City
Authors: Reyes F. , Grutter M. , Jazcilevich A. , González-Oropeza R.
Published: April 2010

Abstract. A methodology to acquire valuable information on the chemical composition and evolution of vehicular emissions is presented. The analysis of the gases is performed by passing a constant flow of a sample gas from the tail-pipe into a 10 L multi-pass cell. The absorption spectra within the cell are obtained using an FTIR spectrometer at 0.5 cm−1 resolution along a 13.1 m optical path. Additionally, the total flow from the exhaust is continuously measured from a differential pressure sensor on a \\textit{Pitot} tube installed at the exit of the exhaust. This configuration aims to obtain a good speciation capability by coadding spectra during 30 s and reporting the emission (in g/km) of both criteria and non-regulated pollutants, such as CO2, CO, NO, SO2, NH3, HCHO and some NMHC, during predetermined driving cycles. The advantages and disadvantages of increasing the measurement frequency, as well as the effect of other parameters such as spectral resolution, cell volume and flow rate, are discussed. To test and evaluate the proposed technique, experiments were performed on a dynamometer running FTP-75 and typical driving cycles for the Mexico City Metropolitan Area (MCMA) on a Toyota Prius hybrid vehicle. This car is an example of recent marketed automotive technology dedicated to reduced emissions, increasing the need for sensitive detection techniques. This study shows the potential of the proposed technique to measure and report in real time the emissions of a large variety of pollutants, even from a super ultra-low emission vehicle (SULEV). The emissions of HC's, NOx, CO and CO2 obtained here were compared to experiments performed in other locations with the same model vehicle. The proposed technique provides a tool for future studies comparing in detail the emissions of vehicles using alternative fuels and emission control systems.
What can tracer observations in the continental boundary layer tell us about surface-atmosphere fluxes?
Authors: Gerbig C. , Lin J. C. , Munger J. W. , Wofsy S. C.
Published: April 2010

Abstract. We analyze the potential for inferring spatially resolved surface fluxes from atmospheric tracer observations within the mixed layer, such as from monitoring towers, using a receptor oriented transport model (Stochastic Time-Inverted Lagrangian Transport model - STILT) coupled to a simple biosphere in which CO2 fluxes are represented as functional responses to environmental drivers (radiation and temperature). Transport and biospheric fluxes are coupled on a dynamic grid using a polar projection with high horizontal resolution (~20 km) in near field, and low resolution far away (as coarse as 2000 km), reducing the number of surface pixels without significant loss of information. To test the system, and to evaluate the errors associated with the retrieval of fluxes from atmospheric observations, a pseudo data experiment was performed. A large number of realizations of measurements (pseudo data) and a priori fluxes were generated, and for each case spatially resolved fluxes were retrieved. Results indicate strong potential for high resolution retrievals based on a network of tall towers, subject to the requirement of correctly specifying the a priori uncertainty covariance, especially the off diagonal elements that control spatial correlations. False assumptions about the degree to which the uncertainties in the a priori fluxes are spatially correlated may lead to a strong underestimation of uncertainties in the retrieved fluxes, or, equivalently, to biased retrievals. The framework presented here, however, allows a conservative choice of the off diagonal elements that avoids biasing the retrievals.
Accuracy of analyzed temperatures, winds and trajectories in the Southern Hemisphere tropical and midlatitude stratosphere as compared to long-duration balloon flights
Authors: Knudsen B. M. , Christensen T. , Hertzog A. , Deme A. , Vial F. , Pommereau J.-P.
Published: April 2010

Abstract. Eight super-pressure balloons floating at constant level between 50 and 80 hPa and three Infra-Red Montgolfier balloons of variable altitude (15 hPa daytime, 40–80 hPa night time) have been launched at 22° S from Brazil in February–May 2004 in the frame of the HIBISCUS project. The flights lasted for 7 to 79 days residing mainly in the tropics, but some of them passed the tropical barrier and went to southern midlatitudes. Compared to the balloon measurements just above the tropical tropopause the ECMWF operational temperatures show a systematic cold bias of 0.9 K and the easterly zonal winds are too strong by 0.7 m/s. This bias in the zonal wind adds to the ECMWF trajectory errors, but they still are relatively small with e.g. about an error of 700 km after 5 days. The NCEP/NCAR reanalysis trajectory errors are substantially larger (1300 km after 5 days). In the southern midlatitudes the cold bias is the same, but the zonal wind bias is almost zero. The trajectories are generally more accurate than in the tropics, but for one balloon a lot of the calculated trajectories end up on the wrong side of the tropical barrier and this leads to large trajectory errors.
Seasonal dependence of peroxy radical concentrations at a Northern hemisphere marine boundary layer site during summer and winter: evidence for radical activity in winter
Authors: Fleming Z. L. , Monks P. S. , Rickard A. R. , Bandy B. J. , Brough N. , Green T. J. , Reeves C. E. , Penkett S. A.
Published: April 2010

Abstract. Peroxy radicals (HO2+Σ RO2) were measured at the Weybourne Atmospheric Observatory (52° N, 1° E), Norfolk using a PEroxy Radical Chemical Amplifier (PERCA) during the winter and summer of 2002. The peroxy radical diurnal cycles showed a marked difference between the winter and summer campaigns with maximum concentrations of 12 pptv at midday in the summer and maximum concentrations as high as 30 pptv (10 min averages) in winter at night. The corresponding nighttime peroxy radical concentrations were not as high in summer (3 pptv). The peroxy radical concentration shows a distinct anti-correlation with increasing NOx during the daylight hours. At night, peroxy radicals increase with increasing NOx indicative of the role of NO3 chemistry. The average diurnal cycles for net ozone production, N(O3) show a large variability in ozone production, P(O3), and a large ozone loss, L(O3) in summer relative to winter. For a daylight average, net ozone production in summer was higher than winter (1.51±0.5 ppbv h−1 and 1.11±0.47 ppbv h−1, respectively). The variability in NO concentration has a much larger effect on N(O3) than the peroxy radical concentrations. Photostationary state (PSS) calculations show an NO2 lifetime of 5 min in summer and 21 minutes in the winter, implying that steady-state NO-NO2 ratios are not always attained during the winter months. The results show an active peroxy radical chemistry at night and that significant oxidant levels are sustained in winter. The net effect of this with respect to production of ozone in winter is unclear owing to the breakdown in the photostationary state.
Simulating aerosol microphysics with the ECHAM4/MADE GCM – Part II: Results from a first multiannual simulation of the submicrometer aerosol
Authors: Lauer A. , Hendricks J.
Published: April 2010

Abstract. First results of a multiannual integration with the new global aerosol model system ECHAM4/MADE are presented. This model system enables simulations of the particle number concentration and size-distribution, which is a fundamental innovation compared to previous global model studies considering aerosol mass cycles only. The data calculated by the model provide detailed insights into the properties of the global submicrometer aerosol regarding global burden, chemical composition, atmospheric residence time, particle number concentration and size-distribution. The aerosol components considered by the model are sulfate (SO4), nitrate (NO3), ammonium (NH4), black carbon (BC), organic matter (OM), mineral dust, sea salt and aerosol water. The simulated climatological annual mean global atmospheric burdens (residence times) of the dominant submicrometer aerosol components are 2.25 Tg (4.5 d) for SO4, 0.46 Tg (4.5 d) for NH4, 0.26 Tg (6.6 d) for BC, and 1.77 Tg (6.5 d) for OM. The contributions of individual processes such as emission, nucleation, condensation or dry and wet deposition to the global sources and sinks of specific aerosol components and particle number concentration are quantified. Based on this analysis, the significance of aerosol microphysical processes (nucleation, condensation, coagulation) is evaluated by comparison to the importance of other processes relevant for the submicrometer aerosol on the global scale. The results reveal that aerosol microphysics are essential for the simulation of the particle number concentration and important but not vital for the simulation of particle mass concentration. Hence aerosol microphysics should be taken into account in simulations of atmospheric processes showing a significant dependence on aerosol particle number concentration. The analysis of the vertical variation of the microphysical net production and net depletion rates performed for particle number concentration, sulfate mass and black carbon mass concentration unveils the dominant source and sink regions. Prominent features can be attributed to dominant microphysical processes such as nucleation in the upper troposphere or wet deposition in the lower troposphere. Regions of efficient coagulation can be identified.
Processes controlling the concentration of hydroperoxides at Jungfraujoch Observatory, Switzerland
Authors: Walker S. J. , Evans M. J. , Jackson A. V. , Steinbacher M. , Zellweger C. , McQuaid J. B.
Published: April 2010

Abstract. An automated, ground-based instrument was used to measure gas-phase hydroperoxides at the Jungfraujoch High Altitude Research Station as part of the Free Tropospheric EXperiment (FREETEX) during February/March 2003. A nebulising reflux concentrator sampled ambient air twice hourly, prior to on-site analysis by HPLC speciation, coupled with post-column peroxidase derivatisation and fluorescence detection. Hydrogen peroxide (H2O2) concentrations reached up to 1330 pptv over the 13-day period with a mean of 183±233 pptv (± one standard deviation). Methyl hydroperoxide (CH3OOH) reached up to 379 pptv with a mean of 51±55 pptv. No other organic hydroperoxides were detected. The lack of an explicit diurnal cycle suggests that hydroperoxide concentrations are chiefly influenced by transport processes rather than local photochemistry at this mountainous site. There was some evidence that elevated concentrations of H2O2 existed in air-masses originating from the south-west, suggesting higher concentrations of HOx due to more active photochemistry. Air which had been recently polluted exhibited low H2O2 concentration due to a combination of suppression of HO2 by NOx and deposition. The concentrations of H2O2 sampled here are consistent with previous box modelling studies of hydroperoxides, except in periods influenced by the boundary layer, where agreement required a depositional sink.
The characterisation of pollution aerosol in a changing photochemical environment
Authors: Cubison M. J. , Alfarra M. R. , Allan J. , Bower K. N. , Coe H. , McFiggans G. B. , Whitehead J. D. , Williams P. I. , Zhang Q. , Jimenez J. L. , Hopkins J. , Lee J.
Published: April 2010

Abstract. Measurements are presented from a sampling location 50 km downwind of Greater London, UK, to investigate the timescales required for the atmospheric transformations of aerosol in urban emissions plumes in the context of photochemical age based on the benzene to toluene ratio. It is shown that particles at or around 100 nm in diameter exhibit the greatest systematic variability in chemical properties, and thus hygroscopic properties, on a timescale of 1–2 days. The smaller Aitken mode and larger accumulation mode particles exhibit less variability on these timescales, which we propose is as a result of their different residence times in the atmosphere. The larger accumulation particles have been in the atmosphere longer than the 100 nm particles and their chemistry and hygroscopic properties have been integrated over several days and potentially over several source regions. In contrast, the smaller Aitken mode particles show little systematic variability with photochemical age because their atmospheric lifetimes are short, thus chemical changes and hence changes in water affinity have not had time to occur. Increases in the particle diameter of up to 40% are observed at 90% relative humidity in the accumulation mode from the uptake of water as the particles become increasingly soluble in nature.
Cluster Analysis of the Organic Peaks in Bulk Mass Spectra Obtained During the 2002 New England Air Quality Study with an Aerodyne Aerosol Mass Spectrometer
Authors: Marcolli C. , Canagaratna M. R. , Worsnop D. R. , Bahreini R. , de Gouw J. A. , Warneke C. , Goldan P. D. , Kuster W. C. , Williams E. J. , Lerner B. M. , Roberts J. M. , Meagher J. F. , Fehsenfeld F. C. , Marchewka M. , Bertman S. B. , Middlebrook A. M.
Published: April 2010

Abstract. We applied hierarchical cluster analysis to an Aerodyne aerosol mass spectrometer (AMS) bulk mass spectral dataset collected aboard the NOAA research vessel R. H. Brown during the 2002 New England Air Quality Study off the east coast of the United States. Emphasizing the organic peaks, the cluster analysis yielded a series of categories that are distinguishable with respect to their mass spectra and their occurrence as a function of time. The differences between the categories mainly arise from relative intensity changes rather than from the presence or absence of specific peaks. The most frequent category exhibits a strong signal at m/z 44 and represents oxidized organic matter probably originating from both anthropogenic as well as biogenic sources. On the basis of spectral and trace gas correlations, the second most common category with strong signals at m/z 29, 43, and 44 contains contributions from isoprene oxidation products. The third through the fifth most common categories have peak patterns characteristic of monoterpene oxidation products and were most frequently observed when air masses from monoterpene rich regions were sampled. Taken together, the second through the fifth most common categories represent on average 17% of the total organic mass that stems likely from biogenic sources during the ship's cruise. These numbers have to be viewed as lower limits since the most common category was attributed to anthropogenic sources for this calculation. The cluster analysis was also very effective in identifying a few contaminated mass spectra that were not removed during pre-processing. This study demonstrates that hierarchical clustering is a useful tool to analyze the complex patterns of the organic peaks in bulk aerosol mass spectra from a field study.
Radiative forcing since preindustrial times due to ozone change in the troposphere and the lower stratosphere
Authors: Gauss M. , Myhre G. , Isaksen I. S. A. , Grewe V. , Pitari G. , Wild O. , Collins W. J. , Dentener F. J. , Ellingsen K. , Gohar L. K. , Hauglustaine D. A. , Iachetti D. , Lamarque F. , Mancini E. , Mickley L. J. , Prather M. J. , Pyle J. A. , Sanderson M. G. , Shine K. P. , Stevenson D. S. , Sudo K. , Szopa S. , Zeng G.
Published: April 2010

Abstract. Changes in atmospheric ozone have occurred since the preindustrial era as a result of increasing anthropogenic emissions. Within ACCENT, a European Network of Excellence, ozone changes between 1850 and 2000 are assessed for the troposphere and the lower stratosphere (up to 30 km) by a variety of seven chemistry-climate models and three chemical transport models. The modeled ozone changes are taken as input for detailed calculations of radiative forcing. When only changes in chemistry are considered (constant climate) the modeled global-mean tropospheric ozone column increase since preindustrial times ranges from 7.9 DU to 13.8 DU among the ten participating models, while the stratospheric column reduction lies between 14.1 DU and 28.6 DU in the models considering stratospheric chemistry. The resulting radiative forcing is strongly dependent on the location and altitude of the modeled ozone change and varies between 0.25 Wm−2 and 0.45 Wm−2 due to ozone change in the troposphere and −0.123 Wm−2 and +0.066 Wm−2 due to the stratospheric ozone change. Changes in ozone and other greenhouse gases since preindustrial times have altered climate. Six out of the ten participating models have performed an additional calculation taking into account both chemical and climate change. In most models the isolated effect of climate change is an enhancement of the tropospheric ozone column increase, while the stratospheric reduction becomes slightly less severe. In the three climate-chemistry models with detailed tropospheric and stratospheric chemistry the inclusion of climate change increases the resulting radiative forcing due to tropospheric ozone change by up to 0.10 Wm−2, while the radiative forcing due to stratospheric ozone change is reduced by up to 0.034 Wm−2. Considering tropospheric and stratospheric change combined, the total ozone column change is negative while the resulting net radiative forcing is positive.
The transport history of two Saharan dust events archived in an Alpine ice core
Authors: Sodemann H. , Palmer A. S. , Schwierz C. , Schwikowski M. , Wernli H.
Published: April 2010

Abstract. Mineral dust from the Saharan desert can be transported across the Mediterranean towards the Alpine region several times a year. When coinciding with snowfall, the dust can be deposited on Alpine glaciers and then appears as yellow or red layers in ice cores. Two such significant dust events were identified in an ice core drilled at the high-accumulation site Piz Zupó in the Swiss Alps (46°22' N, 9°55' E, 3850 m a.s.l.). From stable oxygen isotopes and major ion concentrations, the events were approximately dated as October and March 2000. In order to link the dust record in the ice core to the meteorological situation that led to the dust events, a novel methodology based on back-trajectory analysis was developed. It allowed the detailed analysis of the specific meteorologic flow evolution that was associated with Saharan dust transport into the Alps, and the identification of dust sources, atmospheric transport paths, and wet deposition periods for both dust events. Differences in the chemical signature of the two dust events were interpreted with respect to contributions from the dust sources and aerosol scavenging during the transport. For the October event, the trajectory analysis indicated that dust deposition took place during 13–15 October 2000. Mobilisation areas of dust were mainly identified in the Algerian and Libyan deserts. A combination of an upper-level potential vorticity streamer and a midlevel jet across Algeria first brought moist Atlantic air and later mixed air from the tropics and Saharan desert across the Mediterranean towards the Alps. The March event consisted of two different deposition phases which took place during 17–19 and 23–25 March 2000. The first phase was associated with an exceptional transport pathway past Iceland and towards the Alps from northerly directions. The second phase was similar to the October event. A significant peak of methanesulphonic acid associated with the March dust event was most likely caused by incorporation of biogenic aerosol while passing through the marine boundary layer of the western Mediterranean during a local phytoplankton bloom. From this study, we conclude that for a detailed understanding of the chemical signal recorded in dust events at Piz Zupó, it is essential to consider the whole transport sequence of mineral aerosol, consisting of dust mobilisation, transport, and deposition at the glacier.
Aerosol optical properties at Lampedusa (Central Mediterranean). 2. Determination of single scattering albedo at two wavelengths for different aerosol types
Authors: Meloni D. , di Sarra A. , Pace G. , Monteleone F.
Published: April 2010

Abstract. Aerosol optical properties were retrieved from direct and diffuse spectral irradiance measurements made by a multi-filter rotating shadowband radiometer (MFRSR) at the island of Lampedusa (35.5° N, 12.6° E), in the Central Mediterranean, in the period July 2001–September 2003. In a companion paper (Pace et al., 2006) the aerosol optical depth (AOD) and Ångström exponent were used together with airmass backward trajectories to identify and classify different aerosol types. The MFRSR diffuse-to-direct ratio (DDR) at 415.6 nm and 868.7 nm for aerosol classified as "biomass burning-urban/industrial", originating primarily from the European continent, and desert dust, originating from the Sahara, is used in this study to estimate the aerosol single scattering albedo (SSA). A detailed radiative transfer model is initialised with the measured aerosol optical depth; calculations are performed at the two wavelengths varying the SSA values until the modelled DDR matches the MFRSR observations. Sensitivity studies are performed to estimate how uncertainties on AOD, DDR, asymmetry factor (g), and surface albedo influence the retrieved SSA values. The results show that a 3% variation of AOD or DDR produce a change of about 0.02 in the retrieved SSA value at 415.6 and 868.7 nm; a ±0.06 variation of the asymmetry factor g produces a change of the estimated SSA of <0.04 at 415.6 nm, and <0.06 at 868.7 nm; finally, an increase of the assumed surface albedo of 0.05 causes very small changes (0.01–0.02) in the retrieved SSA. The calculations show that the SSA of desert dust (DD) increases with wavelength, from 0.81±0.05 at 415.6 nm to 0.94±0.05 at 868.7 nm; on the contrary, the SSA of urban/industrial (UN) aerosols decreases from 0.96±0.02 at 415.6 nm to 0.87±0.07 at 868.7 nm; the SSA of biomass burning (BB) particles is 0.82±0.04 at 415.6 nm and 0.80±0.05 at 868.7 nm. Episodes of UN aerosols occur usually in June and July; long lasting BB aerosol episodes with large AOD are observed mainly in July and August, the driest months of the year, when the development of fires is frequent.
Cluster activation theory as an explanation of the linear dependence between formation rate of 3nm particles and sulphuric acid concentration
Authors: Kulmala M. , Lehtinen K. E. J. , Laaksonen A.
Published: April 2010

Abstract. According to atmospheric observations new particle formation seems to be a function of sulphuric acid concentration to the power from one to two. The nucleation theorem then predicts that the critical cluster contains one to two sulphuric acid molecules. However, existing nucleation theories predicts that the power is more (or equal) than 2. Here we present an activation theory, which can explain the observed slope. In cluster activation the clusters containing one sulphuric acid molecule will activate for further growth due to heterogeneous nucleation, heterogeneous chemical reactions including polymerization or activation of soluble clusters. In the activation process organic vapours are typically needed as condensing agents.
Water activity and activation diameters from hygroscopicity data - Part II: Application to organic species
Authors: Koehler K. A. , Kreidenweis S. M. , DeMott P. J. , Prenni A. J. , Carrico C. M. , Ervens B. , Feingold G.
Published: April 2010

Abstract. A method has been developed for using particle hygroscopicity measurements made with a humidified tandem differential mobility analyzer (HTDMA) to determine water activity as a function of solute weight percent. In Part I, the method was tested for particles composed of sodium chloride and ammonium sulfate. Here, we report results for several atmospherically-relevant organic species: glutaric acid, malonic acid, oxalic acid and levoglucosan. Predicted water activities for aqueous dicarboxylic acid solutions are quite similar in some cases to published estimates and the simplified predictions of Köhler theory, while in other cases substantial differences are found, which we attribute primarily to the semivolatile nature of these compounds that makes them difficult to study with the HTDMA. In contrast, estimates of water activity for levoglucosan solutions compare very well with recently-reported measurements and with published data for aqueous glucose and fructose solutions. For all studied species, the critical dry diameters active at supersaturations between 0.2 and 1% that are computed with the HTDMA-derived water activities are generally within the experimental error (~20%) estimated in previously-published direct measurements using cloud condensation nuclei counters. For individual compounds, the variations in reported solution water activity lead to uncertainties in critical dry diameters of 5-25%, not significantly larger than the uncertainty in the direct measurements. To explore the impact of these uncertainties on modeled aerosol-cloud interactions, we incorporate the variations in estimates of solution water activities into the description of hygroscopic growth of aerosol particles in an adiabatic parcel model and examine the impact on the predicted drop number concentrations. For the limited set of initial conditions examined here, we find that the uncertainties in critical dry diameters for individual species lead to 0-21% changes in drop number concentration, with the largest effects at high aerosol number concentrations and slow updraft velocities. Ammonium sulfate, malonic acid and glutaric acid have similar activation behavior, while glutaric acid and levoglucosan are somewhat less hygroscopic and lead to lower drop number concentrations; sodium chloride is the most easily activated compound. We explain these behaviors in terms of a parameter that represents compound hygroscopicity, and conclude that this parameter must vary by more than a factor of 2 to induce more than a 15% change in activated drop number concentrations. In agreement with earlier studies, our results suggest that the number concentration of activated drops is more sensitive to changes in the input aerosol size and number concentrations and the applied updraft velocity than to modest changes in the aerosol composition and hygroscopic properties.
Volatile organic emissions from the distillation and pyrolysis of vegetation
Authors: Greenberg J. P. , Friedli H. , Guenther A. B. , Hanson D. , Harley P. , Karl T.
Published: April 2010

Abstract. Leaf and woody plant tissue (Pinus ponderosa, Eucalyptus saligna, Quercus gambelli, Saccharum officinarum and Oriza sativa) were heated from 30 to 300°C and volatile organic compound (VOC) emissions were identified and quantified. Major VOC emissions were mostly oxygenated and included acetic acid, furylaldehyde, acetol, pyrazine, terpenes, 2,3-butadione, phenol and methanol, as well as smaller emissions of furan, acetone, acetaldehyde, acetonitrile and benzaldehyde. Total VOC emissions from distillation and pyrolysis were on the order of 10 gC/kgC dry weight of vegetation, as much as 33% and 44% of CO2 emissions (gC(VOC)/gC(CO2)) measured during the same experiments, in air and nitrogen atmospheres, respectively. The emissions are similar in identity and quantity to those from smoldering combustion of woody tissue and of different character than those evolved during flaming combustion. VOC emissions from the distillation of pools and endothermic pyrolysis under low turbulence conditions may produce flammable concentrations near leaves and may facilitate the propagation of wildfires. VOC emissions from charcoal production are also related to distillation and pyrolysis; the emissions of the highly reactive VOCs from production are as large as the carbon monoxide emissions.