bluuebunny/crossref_metadata_2025 huggingface dataset:
Do organic surface films on sea salt aerosols influence atmospheric chemistry? – a model study
Authors: Smoydzin L. , von Glasow R.
Published: April 2010

Abstract. Organic material from the ocean's surface can be incorporated into sea salt aerosol particles often producing a surface film on the aerosol. Such an organic coating can reduce the mass transfer between the gas phase and the aerosol phase influencing sea salt chemistry in the marine atmosphere. To investigate these effects and their importance for the marine boundary layer (MBL) we used the one-dimensional numerical model MISTRA. We considered the uncertainties regarding the magnitude of uptake reduction, the concentrations of organic compounds in sea salt aerosols and the oxidation rate of the organics to analyse the possible influence of organic surfactants on gas and liquid phase chemistry with a special focus on halogen chemistry. By assuming destruction rates for the organic coating based on laboratory measurements we get a rapid destruction of the organic monolayer within the first meters of the MBL. Larger organic initial concentrations lead to a longer lifetime of the coating but lead also to an unrealistically strong decrease of O3 concentrations as the organic film is destroyed by reaction with O3. The lifetime of the film is increased by assuming smaller reactive uptake coefficients for O3 or by assuming that a part of the organic surfactants react with OH. With regard to tropospheric chemistry we found that gas phase concentrations for chlorine and bromine species decreased due to the decreased mass transfer between gas phase and aerosol phase. Aqueous phase chlorine concentrations also decreased but aqueous phase bromine concentrations increased. Differences for gas phase concentrations are in general smaller than for liquid phase concentrations. The effect on gas phase NO2 or NO is very small (reduction less than 5%) whereas liquid phase NO2 concentrations increased in some cases by nearly 100%. We list suggestions for further laboratory studies which are needed for improved model studies.
Emissions from forest fires near Mexico City
Authors: Yokelson R. J. , Urbanski S. P. , Atlas E. L. , Toohey D. W. , Alvarado E. C. , Crounse J. D. , Wennberg P. O. , Fisher M. E. , Wold C. E. , Campos T. L. , Adachi K. , Buseck P. R. , Hao W. M.
Published: April 2010

Abstract. The emissions of NOx (defined as NO (nitric oxide) + NO2 (nitrogen dioxide)) and hydrogen cyanide (HCN), per unit amount of fuel burned, from fires in the pine forests that dominate the mountains surrounding Mexico City (MC) are about 2 times higher than normally observed for forest burning. The ammonia (NH3) emissions are about average for forest burning. The upper limit for the mass ratio of NOx to volatile organic compounds (VOC) for these MC-area mountain fires was ~0.38, which is similar to the NOx/VOC ratio in the MC urban area emissions inventory of 0.34, but much larger than the NOx/VOC ratio for tropical forest fires in Brazil (~0.068). The nitrogen enrichment in the fire emissions may be due to deposition of nitrogen-containing pollutants in the outflow from the MC urban area. This effect may occur worldwide wherever biomass burning coexists with large urban areas (e.g. the tropics, southeastern US, Los Angeles Basin). The molar emission ratio of HCN to carbon monoxide (CO) for the mountain fires was 0.012±0.007, which is 2–9 times higher than widely used literature values for biomass burning. The ambient molar ratio HCN/CO in the MC-area outflow is about 0.003±0.0003. Thus, if only mountain fires emit significant amounts of HCN, these fires may be contributing about 25% of the CO production in the MC-area (~98–100 W and 19–20 N). Comparing the PM10/CO and PM2.5/CO mass ratios in the MC Metropolitan Area emission inventory (0.0115 and 0.0037) to the PM1/CO mass ratio for the mountain fires (0.133) then suggests that these fires could produce as much as ~79–92% of the primary fine particle mass generated in the MC-area. Considering both the uncertainty in the HCN/CO ratios and secondary aerosol formation in the urban and fire emissions implies that about 50±30% of the "aged" fine particle mass in the March 2006 MC-area outflow could be from these fires.
Trends and variability in stratospheric mixing: 1979–2005
Authors: Garny H. , Bodeker G. E. , Dameris M.
Published: April 2010

Abstract. Changes in climate are likely to drive changes in stratospheric mixing with associated implications for changes in transport of ozone from tropical source regions to higher latitudes, transport of water vapour and source gas degradation products from the tropical tropopause layer into the mid-latitude lower stratosphere, and changes in the meridional distribution of long-lived trace gases. To diagnose long-term changes in stratospheric mixing, global monthly fields of Lyapunov exponents were calculated on the 450 K, 550 K, and 650 K isentropic surfaces by applying a trajectory model to wind fields from NCEP/NCAR reanalyses over the period 1979 to 2005. Potential underlying geophysical drivers of trends and variability in these mixing fields were investigated by applying a least squares regression model, which included basis functions for a mean annual cycle, seasonally dependent linear trends, the quasi-biennial oscillation (QBO), the solar cycle, and the El Niño Southern Oscillation (ENSO), to zonal mean time series of the Lyapunov exponents. Long-term positive trends in mixing are apparent over southern middle to high latitudes at 450 K through most of the year, while negative trends over southern high latitudes are apparent at 650 K from May to August. Wintertime negative trends in mixing over northern mid-latitudes are apparent at 550 K and 650 K. Over low latitudes, within 40° of the equator, the QBO exerts a strong influence on mixing at all three analysis levels. This QBO influence is strongly modulated by the annual cycle and shows a phase shift across the subtropical mixing barrier. Solar cycle and ENSO influences on mixing are generally not significant. The diagnosed long-term changes in mixing should aid the interpretation of trends in stratospheric trace gases.
Evaluating model performance of an ensemble-based chemical data assimilation system during INTEX-B field mission
Authors:   A. F. Arellano Jr., Raeder K. , Anderson J. L. , Hess P. G. , Emmons L. K. , Edwards D. P. , Pfister G. G. , Campos T. L. , Sachse G. W.
Published: April 2010

Abstract. We present a global chemical data assimilation system using a global atmosphere model, the Community Atmosphere Model (CAM3) with simplified chemistry and the Data Assimilation Research Testbed (DART) assimilation package. DART is a community software facility for assimilation studies using the ensemble Kalman filter approach. Here, we apply the assimilation system to constrain global tropospheric carbon monoxide (CO) by assimilating meteorological observations of temperature and horizontal wind velocity and satellite CO retrievals from the Measurement of Pollution in the Troposphere (MOPITT) satellite instrument. We verify the system performance using independent CO observations taken on board the NSF/NCAR C-130 and NASA DC-8 aircrafts during the April 2006 part of the Intercontinental Chemical Transport Experiment (INTEX-B). Our evaluations show that MOPITT data assimilation provides significant improvements in terms of capturing the observed CO variability relative to no MOPITT assimilation (i.e. the correlation improves from 0.62 to 0.71, significant at 99% confidence). The assimilation provides evidence of median CO loading of about 150 ppbv at 700 hPa over the NE Pacific during April 2006. This is marginally higher than the modeled CO with no MOPITT assimilation (~140 ppbv). Our ensemble-based estimates of model uncertainty also show model overprediction over the source region (i.e. China) and underprediction over the NE Pacific, suggesting model errors that cannot be readily explained by emissions alone. These results have important implications for improving regional chemical forecasts and for inverse modeling of CO sources and further demonstrate the utility of the assimilation system in comparing non-coincident measurements, e.g. comparing satellite retrievals of CO with in-situ aircraft measurements.
Introducing the concept of Potential Aerosol Mass (PAM)
Authors: Kang E. , Root M. J. , Toohey D. W. , Brune W. H.
Published: April 2010

Abstract. Potential Aerosol Mass (PAM) can be defined as the maximum aerosol mass that the oxidation of precursor gases produces. In the measurement, all precursor gases are rapidly oxidized with extreme amounts of oxidants to low volatility compounds, resulting in the aerosol formation. Oxidation occurs in a small, simple, flow-through chamber that has a short residence time and is irradiated with ultraviolet light. The amount of the oxidants ozone (O3), hydroxyl (OH), and hydroperoxyl (HO2) were measured directly and can be controlled by varying the UV light and the relative humidity. Maximum values were 40 ppmv for O3 500 pptv for OH, and 4 ppbv for HO2. The oxidant amounts are 100 to 1000 times troposphere values, but the ratios OH/O3 and HO2/OH are similar to troposphere values. The aerosol production mechanism and the aerosol mass yield were studied for several controlling variables, such as temperature, relative humidity, oxidant concentration, presence of nitrogen oxides (NOx), precursor gas composition and amount, and the presence of acidic seed aerosol. The measured secondary organic aerosol (SOA) yield of several natural and anthropogenic volatile organic compounds and a mixture of hydrocarbons in the PAM chamber were similar to those obtained in large, batch-style environmental chambers. This PAM method is being developed for measuring potential aerosol mass in the atmosphere, but is also useful for examining SOA processes in the laboratory and in environmental chambers.
On the variability of the Ring effect in the near ultraviolet: understanding the role of aerosols and multiple scattering
Authors: Langford A. O. , Schofield R. , Daniel J. S. , Portmann R. W. , Melamed M. L. , Miller H. L. , Dutton E. G. , Solomon S.
Published: April 2010

Abstract. The "filling-in" (FI) of Fraunhofer lines, often referred to as the Ring effect, was examined using measurements of near ultraviolet sunlight scattered from the zenith sky above Boulder, Colorado during July and August 2005. The FI of the 344.1 nm Fe I line was directly determined by comparing direct sun and cloud-free zenith sky spectra recorded on the same day. The results, obtained over solar zenith angles (SZA) from 20° to 70°, are compared to the predictions of a simple rotational Raman Scattering (RRS) spectral model. The measured FI was found to be up to 70% greater than that predicted by first-order molecular scattering with a much stronger SZA dependence. Simultaneously measured aerosol optical depths and Monte Carlo calculations show that the combination of aerosol scattering and second-order molecular scattering can account for these differences, and potentially explain the contradictory SZA dependences in previously published measurements of FI. These two scattering processes also introduce a wavelength dependence to FI that complicates the fitting of diffuse sunlight observations in differential optical absorption spectroscopy (DOAS). A simple correction to improve DOAS retrievals by removing this wavelength dependence is described.
Effects on surface atmospheric photo-oxidants over Greece during the total solar eclipse event of 29 March 2006
Authors: Zanis P. , Katragkou E. , Kanakidou M. , Psiloglou B. E. , Karathanasis S. , Vrekoussis M. , Gerasopoulos E. , Lisaridis I. , Markakis K. , Poupkou A. , Amiridis V. , Melas D. , Mihalopoulos N. , Zerefos C.
Published: April 2010

Abstract. This study investigates the effects of the total solar eclipse of 29 March 2006 on surface air-quality levels over Greece based on observations at a number of sites in conjunction with chemical box modelling and 3-D air-quality modelling. Emphasis is given on surface ozone and other photooxidants at four Greek sites Kastelorizo, Finokalia (Crete), Pallini (Athens) and Thessaloniki, which are located at gradually increasing distances from the path of the eclipse totality and are characterized by different air pollution levels. The eclipse offered the opportunity to test our understanding of air pollution build-up and the response of the gas-phase chemistry of photo-oxidants during a photolytical perturbation using both a photochemical box model and a regional air-quality offline model based on the modeling system WRF/CAMx. At the relatively unpolluted sites of Kastelorizo and Finokalia no clear signal of the solar eclipse on surface O3, NO2 and NO concentrations can be deduced from the observations while there is no correlation of observed O3, NO2 and NO with observed global radiation. The box and regional model simulations for the two relatively unpolluted sites indicate that the calculated changes in net ozone production rates between eclipse and non eclipse conditions are rather small compared to the observed short-term ozone variability. Furthermore the simulated ozone lifetime is in the range of a few days at these sites and hence the solar eclipse effects on ozone can be easily masked by local and regional transport. At the polluted sites of Thessaloniki and Pallini, the solar eclipse effects on O3, NO2 and NO concentrations are revealed from both the measurements and modeling with the net effect being a decrease in O3 and NO and an increase in NO2 as NO2 formed from the reaction of O3 with NO while at the same time NO2 is not efficiently photolysed. This result is also supported by a positive correlation of observed global radiation with O3 and NO and a negative correlation with NO2. It is evident from the 3-D air quality modeling over Greece that the maximum effects of the eclipse on O3, NO2 and NO are reflected on the large urban agglomerations of Athens, and Thessaloniki where the maximum of the emissions occur.
Technical Note: Performance of Chemical Ionization Reaction Time-of-Flight Mass Spectrometry (CIR-TOF-MS) for the measurement of atmospherically significant oxygenated volatile organic compounds
Authors: Wyche K. P. , Blake R. S. , Ellis A. M. , Monks P. S. , Brauers T. , Koppmann R. , Apel E. C.
Published: April 2010

Abstract. The performance of a new chemical ionization reaction time-of-flight mass spectrometer (CIR-TOF-MS) utilising the environment chamber SAPHIR (Simulation of Atmospheric Photochemistry In a large Reaction Chamber- Forschungzentrum Jülich, Germany) is described. The work took place as part of the ACCENT (Atmospheric Composition and Change the European NeTwork for excellence) supported oxygenated volatile organic compound (OVOC) measurement intercomparison during January 2005. The experiment entailed the measurement of 14 different atmospherically significant OVOCs at various mixing ratios in the approximate range 10.0–0.6 ppbV. The CIR-TOF-MS operated throughout the exercise with the hydronium ion (H3O+) as the primary chemical ionization (CI) reagent in order to facilitate proton transfer to the analyte OVOCs. The results presented show that the CIR time-of-flight mass spectrometer is capable of detecting a wide range of atmospheric OVOCs at mixing ratios of around 10 ppbV in "real-time" (i.e. detection on the one-minute time scale), with sub-ppbV measurement also achieved following an increase in averaging time to tens of minutes. It is shown that in general OVOC measurement is made with high accuracy and precision, with integration time, mixing ratio and compound dependent values as good as 4–13% and 3–15% respectively. It is demonstrated that CIR-TOF-MS has rapid multi-channel response at the required sensitivity, accuracy and precision for atmospheric OVOC measurement.
Closure study between chemical composition and hygroscopic growth of aerosol particles during TORCH2
Authors: Gysel M. , Crosier J. , Topping D. O. , Whitehead J. D. , Bower K. N. , Cubison M. J. , Williams P. I. , Flynn M. J. , McFiggans G. B. , Coe H.
Published: April 2010

Abstract. Measurements of aerosol properties were made in aged polluted and clean background air masses encountered at the North Norfolk (UK) coastline as part of the TORCH2 field campaign in May 2004. Hygroscopic growth factors (GF) at 90% relative humidity (RH) for D0=27–217 nm particles and size-resolved chemical composition were simultaneously measured using a Hygroscopicity Tandem Differential Mobility Analyser (HTDMA) and an Aerodyne aerosol mass spectrometer (Q-AMS), respectively. Both hygroscopic properties and chemical composition showed pronounced variability in time and with particles size. With this data set we could demonstrate that the Zdanovskii-Stokes-Robinson (ZSR) mixing rule combined with chemical composition data from the AMS makes accurate quantitative predictions of the mean GF of mixed atmospheric aerosol particles possible. In doing so it is crucial that chemical composition data are acquired with high resolution in both particle size and time, at least matching the actual variability of particle properties. The closure results indicate an ensemble GF of the organic fraction of ~1.20±0.10 at 90% water activity. Thus the organics contribute somewhat to hygroscopic growth, particularly at small sizes, however the inorganic salts still dominate. Furthermore it has been found that most likely substantial evaporation losses of NH4NO3 occurred within the HTDMA instrument, exacerbated by a long residence time of ~1 min. Such an artefact is in agreement with our laboratory experiments and literature data for pure NH4NO3, both showing similar evaporation losses within HTDMAs with residence times of ~1 min. Short residence times and low temperatures are hence recommended for HTDMAs in order to minimise such evaporation artefacts.
On the parameterization of turbulent fluxes over the tropical Eastern Pacific
Authors: Raga G. B. , Abarca S.
Published: April 2010

Abstract. We present estimates of turbulent fluxes of heat and momentum derived from low level (~30 m) aircraft measurements over the tropical Eastern Pacific and provide empirical relationships that are valid under high wind speed conditions (up to 25 ms−1). The estimates of total momentum flux and turbulent kinetic energy can be represented very accurately (r2=0.99, when data are binned every 1 ms−1) by empirical fits with a linear and a cubic terms of the average horizontal wind speed. The latent heat flux shows a strong quadratic dependence on the horizontal wind speed and a linear relationship with the difference between the air specific humidity and the saturated specific humidity at the sea surface, explaining 96% of the variance. The estimated values were used to evaluate the performance of three currently used parameterizations of turbulence fluxes, varying in complexity and computational requirements. The comparisons with the two more complex parameterizations show good agreement between the observed and parameterized latent heat fluxes, with less agreement in the sensible heat fluxes, and one of them largely overestimating the momentum fluxes. A third, very simple parameterization shows a surprisingly good agreement of the sensible heat flux, while momentum fluxes are again overestimated and a poor agreement was observed for the latent heat flux (r2=0.62). The performance of all three parameterizations deteriorates significantly in the high wind speed regime (above 10–15 ms−1). The dataset obtained over the tropical Eastern Pacific allows us to derive empirical functions for the turbulent fluxes that are applicable from 1 to 25 ms−1, which can be introduced in meteorological models under high wind conditions.
The Chisholm firestorm: observed microstructure, precipitation and lightning activity of a pyro-cumulonimbus
Authors: Rosenfeld D. , Fromm M. , Trentmann J. , Luderer G. , Andreae M. O. , Servranckx R.
Published: April 2010

Abstract. A fire storm that occurred on 28 May 2001 and devastated the town of Chisholm, ~150 km north of Edmonton, Alberta, induced a violent fire-invigorated cumulonimbus cloud. This pyro-cumulonimbus (pyro-Cb) had overshooting tops of 2.5–3 km above the tropopause, and injected massive amounts of smoke into the lower stratosphere. Fortunately, this event occurred under good coverage of radar, rain gauge, lightning and satellite measurements, which allowed in-depth documentation of the event, and gave us an opportunity to study the cloud top morphology and microstructure, precipitation and cloud electrification of the pyro-Cb. The combination of heat and smoke created a cloud with extremely small drops, which ascended rapidly in violent updrafts. There appeared to be little freezing up to the homogeneous freezing isotherm level of −38°C. A cloud with such small and short-lived highly supercooled drops is incapable of producing precipitation except for few large graupel and hail, which produced the observed radar echoes and charged the cloud with positive lightning. The small cloud drops froze homogeneously to equally small ice particles, for which there is no mechanism to aggregate into precipitation particles, and which hence remain in the anvil. The lack of significant precipitation implies that only a small fraction of the smoke is scavenged, so that most of it is exhausted through the anvil to the upper troposphere and lower stratosphere. Comparisons with other cases suggest that a pyro-Cb does not have to be as violent as the Chisholm case for precipitation to be strongly suppressed. However, this level of convective vigor is necessary to create the overshooting updraft that injects the smoke into the lower stratosphere.
Air-sea fluxes of methanol, acetone, acetaldehyde, isoprene and DMS from a Norwegian fjord following a phytoplankton bloom in a mesocosm experiment
Authors: Sinha V. , Williams J. , Meyerhöfer M. , Riebesell U. , Paulino A. I. , Larsen A.
Published: April 2010

Abstract. The ocean's influence on volatile organic compounds (VOCs) in the atmosphere is poorly understood. This work characterises the oceanic emission and/or uptake of methanol, acetone, acetaldehyde, isoprene and dimethyl sulphide (DMS) as a function of photosynthetically active radiation (PAR) and a suite of biological parameters. The measurements were taken following a phytoplankton bloom, in May/June 2005 with a proton transfer reaction mass spectrometer (PTR-MS), from mesocosm enclosures anchored in the Raunefjord, Southern Norway. The net flux of methanol was always into the ocean, and was stronger at night. Isoprene and acetaldehyde were emitted from the ocean, correlating with light (ravcorr, isoprene=0.49; ravcorr, acetaldehyde=0.70) and phytoplankton abundance. DMS was also emitted to the air but did not correlate significantly with light (ravcorr, dms=0.01). Under conditions of high biological activity and a PAR of ~450 μmol photons m−2 s−1, acetone was emitted from the ocean, otherwise it was uptaken. The inter-VOC correlations were highest between the day time emission fluxes of acetone and acetaldehyde (rav=0.96), acetaldehyde and isoprene (rav=0.88) and acetone and isoprene (rav=0.85). The mean fluxes for methanol, acetone, acetaldehyde, isoprene and DMS were −0.26 ng m−2 s−1, 0.21 ng m−2 s−1, 0.23 ng m−2 s−1, 0.12 ng m−2 s−1 and 0.3 ng m−2 s−1, respectively. This work shows that compound specific PAR and biological dependency should be used for estimating the influence of the global ocean on atmospheric VOC budgets.
Integrated systems for forecasting urban meteorology, air pollution and population exposure
Authors: Baklanov A. , Hänninen O. , Slørdal L. H. , Kukkonen J. , Bjergene N. , Fay B. , Finardi S. , Hoe S. C. , Jantunen M. , Karppinen A. , Rasmussen A. , Skouloudis A. , Sokhi R. S. , Sørensen J. H. , Ødegaard V.
Published: April 2010

Abstract. Urban air pollution is associated with significant adverse health effects. Model-based abatement strategies are required and developed for the growing urban populations. In the initial development stage, these are focussed on exceedances of air quality standards caused by high short-term pollutant concentrations. Prediction of health effects and implementation of urban air quality information and abatement systems require accurate forecasting of air pollution episodes and population exposure, including modelling of emissions, meteorology, atmospheric dispersion and chemical reaction of pollutants, population mobility, and indoor-outdoor relationship of the pollutants. In the past, these different areas have been treated separately by different models and even institutions. Progress in computer resources and ensuing improvements in numerical weather prediction, air chemistry, and exposure modelling recently allow a unification and integration of the disjunctive models and approaches. The current work presents a novel approach that integrates the latest developments in meteorological, air quality, and population exposure modelling into Urban Air Quality Information and Forecasting Systems (UAQIFS) in the context of the European Union FUMAPEX project. The suggested integrated strategy is demonstrated for examples of the systems in three Nordic cities: Helsinki and Oslo for assessment and forecasting of urban air pollution and Copenhagen for urban emergency preparedness.
Tropospheric ozone climatology over Beijing: analysis of aircraft data from the MOZAIC program
Authors: Ding A. J. , Wang T. , Thouret V. , Cammas J.-P. , Nédélec P.
Published: April 2010

Abstract. Ozone (O3) profiles recorded over Beijing from 1995 to 2005 by the Measurement of Ozone and Water Vapor by Airbus In-Service Aircraft (MOZAIC) program were analyzed to provide a first climatology of tropospheric O3 over Beijing and the North China Plains (NCPs), one of the most populated and polluted regions in China. A pooled method was adopted in the data analysis to reduce the influence of irregular sampling frequency. The tropospheric O3 over Beijing shows a seasonal and vertical distribution typical of mid-latitude locations in the Northern Hemisphere, but has higher daytime concentrations in the lower troposphere, when compared to New York City, Tokyo, and Paris at similar latitude. The tropospheric O3 over Beijing exhibits a common summer maximum and a winter minimum, with a broad summer maximum in the middle troposphere and a narrower early summer (June) peak in the lower troposphere. Examination of meteorological and satellite data suggests that the lower tropospheric O3 maximum in June is a result of strong photochemical production, transport of regional pollution, and possibly also more intense burnings of biomass in Central-Eastern China. Trajectory analysis indicates that in summer the regional pollution from the NCPs, maybe mixed with urban plumes from Beijing, played important roles on the high O3 concentrations in the boundary layer, but had limited impact on the O3 concentrations in the middle troposphere. A comparison of the data recorded before and after 2000 reveals that O3 in the lower troposphere over Beijing had a strong positive trend (approximately 2% per year from 1995 to 2005) in contrast to a flat or a decreasing trend over Tokyo, New York City, and Paris, indicating worsening photochemical pollution in Beijing and the NCPs.
Temporal variations in black carbon concentrations with different time scales in Helsinki during 1996–2005
Authors: Järvi L. , Junninen H. , Karppinen A. , Hillamo R. , Virkkula A. , Mäkelä T. , Pakkanen T. , Kulmala M.
Published: April 2010

Abstract. Variations in black carbon (BC) concentrations over different timescales, including annual, weekly and diurnal changes, were studied during ten years in Helsinki, Finland. Measurements were made in three campaigns between 1996 and 2005 at an urban area locating two kilometres of the centre of Helsinki. The first campaign took place from November 1996 to June 1997, the second from September 2000 to May 2001 and the third from March 2004 to October 2005. A detailed comparison between the campaigns was only made for winter and spring months when data from all campaigns existed. The effect of traffic and meteorological variables on the measured BC concentrations was studied by means of a multiple regression analysis, where the meteorological data was obtained from a meteorological pre-processing model (MPP-FMI). The BC concentrations showed annual pattern with maxima in fall and late winter due to the weakened mixing and enhanced emissions. Between 1996 and 2005, the campaign median BC concentrations decreased slightly from 1.11 to 1.00 μg m−3. The lowest campaign median concentration (0.93 μg m−3) was measured during the second campaign in 2000–2001, when also the lowest traffic rates were measured. The strongest decrease between Campaigns 1 and 3 was observed on weekday daytimes, when also the traffic rates are highest. The variables affecting the measured BC concentrations most were traffic, wind speed and mixing height. On weekdays, traffic had clearly the most important influence before the wind speed and on weekends the effect of wind speed diluted the effect of traffic. The affecting variables and their influence on the BC concentrations were similar in winter and spring. The separate examination of the three campaigns showed that the effect of traffic on the BC concentrations had decreased during the studied years. This reduction was caused by lower emitting vehicles, since between years 1996 and 2005 the traffic rates had increased.
Effects of uncertainties in the thermodynamic properties of aerosol components in an air quality model – Part 1: Treatment of inorganic electrolytes and organic compounds in the condensed phase
Authors: Clegg S. L. , Kleeman M. J. , Griffin R. J. , Seinfeld J. H.
Published: April 2010

Abstract. Air quality models that generate the concentrations of semi-volatile and other condensable organic compounds using an explicit reaction mechanism require estimates of the physical and thermodynamic properties of the compounds that affect gas/aerosol partitioning: vapour pressure (as a subcooled liquid), and activity coefficients in the aerosol phase. The model of Griffin, Kleeman and co-workers (e.g., Griffin et al., 2003; Kleeman et al., 1999) assumes that aerosol particles consist of an aqueous phase, containing inorganic electrolytes and soluble organic compounds, and a hydrophobic phase containing mainly primary hydrocarbon material. Thirty eight semi-volatile reaction products are grouped into ten surrogate species which partition between the gas phase and both phases in the aerosol. Activity coefficients of the organic compounds are calculated using UNIFAC. In a companion paper (Clegg et al., 2008) we examine the likely uncertainties in the vapour pressures of the semi-volatile compounds and their effects on partitioning over a range of atmospheric relative humidities. In this work a simulation for the South Coast Air Basin surrounding Los Angeles, using lower vapour pressures of the semi-volatile surrogate compounds consistent with estimated uncertainties in the boiling points on which they are based, yields a doubling of the predicted 24-h average secondary organic aerosol concentrations. The dependency of organic compound partitioning on the treatment of inorganic electrolytes in the air quality model, and the performance of this component of the model, are determined by analysing the results of a trajectory calculation using an extended version of the Aerosol Inorganics Model of Wexler and Clegg (2002). Simplifications are identified where substantial efficiency gains can be made, principally: the omission of dissociation of the organic acid surrogates; restriction of aerosol organic compounds to one of the two phases (aqueous or hydrophobic) where equilibrium calculations suggest partitioning strongly in either direction; a single calculation of activity coefficients of the organic compounds for simulations where they are determined by the presence of one component at high concentration in either phase (i.e., water in the aqueous phase, or a hydrocarbon surrogate compound P8 in the hydrophobic phase) and are therefore almost invariant. The implications of the results for the development of aerosol models are discussed.
Effects of uncertainties in the thermodynamic properties of aerosol components in an air quality model – Part 2: Predictions of the vapour pressures of organic compounds
Authors: Clegg S. L. , Kleeman M. J. , Griffin R. J. , Seinfeld J. H.
Published: April 2010

Abstract. Air quality models that generate the concentrations of semi-volatile and other condensable organic compounds using an explicit reaction mechanism require estimates of the vapour pressures of the organic compounds that partition between the aerosol and gas phases. The model of Griffin, Kleeman and co-workers (e.g., Griffin et al., 2005) assumes that aerosol particles consist of an aqueous phase, containing inorganic electrolytes and soluble organic compounds, and a hydrophobic phase containing mainly primary hydrocarbon material. Thirty eight semi-volatile reaction products are grouped into ten surrogate species. In Part 1 of this work (Clegg et al., 2008) the thermodynamic elements of the gas/aerosol partitioning calculation are examined, and the effects of uncertainties and approximations assessed, using a simulation for the South Coast Air Basin around Los Angeles as an example. Here we compare several different methods of predicting vapour pressures of organic compounds, and use the results to determine the likely uncertainties in the vapour pressures of the semi-volatile surrogate species in the model. These are typically an order of magnitude or greater, and are further increased when the fact that each compound represents a range of reaction products (for which vapour pressures can be independently estimated) is taken into account. The effects of the vapour pressure uncertainties associated with the water-soluble semi-volatile species are determined over a wide range of atmospheric liquid water contents. The vapour pressures of the eight primary hydrocarbon surrogate species present in the model, which are normally assumed to be involatile, are also predicted. The results suggest that they have vapour pressures high enough to exist in both the aerosol and gas phases under typical atmospheric conditions.
An improvement on the dust emission scheme in the global aerosol-climate model ECHAM5-HAM
Authors: Cheng T. , Peng Y. , Feichter J. , Tegen I.
Published: April 2010

Abstract. Formulation of the dust emission scheme in the global aerosol-climate modeling system ECHAM5-HAM has been improved. Modifications on the surface aerodynamic roughness length, soil moisture and East-Asian soil properties are included in the parameterization, which result in a large impact on the threshold wind friction velocity for aeolian erosion and thus influence the simulated dust emission amount. The annual global mean of dust emission in the year 2000 is reduced by 76.5% and 2.2%, respectively, due to changes in the aerodynamic roughness length and the soil moisture. An inclusion of detailed East-Asian soil properties leads to an increase of 16.6% in the annual global mean of dust emission, which exhibits mainly in the arid and semi-arid areas of northern China and southern Mongolia. Measurements of the surface dust concentrations are collected in remote marine sites globally and in dust source regions of East Asia. The averaged relative differences between model results and measurements are reduced from 17% to 12% in global remote marine sites and from 69% to 30% in East Asia, by including the improvements. Comparisons between model results and available measurements verify a more realistic dust distribution with the improved emission scheme.
PM speciation and sources in Mexico during the MILAGRO-2006 Campaign
Authors: Querol X. , Pey J. , Minguillón M. C. , Pérez N. , Alastuey A. , Viana M. , Moreno T. , Bernabé R. M. , Blanco S. , Cárdenas B. , Vega E. , Sosa G. , Escalona S. , Ruiz H. , Artíñano B.
Published: April 2010

Abstract. Levels of PM10, PM2.5 and PM1 and chemical speciation of PM10 and PM2.5 were measured during the MILAGRO campaign (1st to 31st March 2006, but extended in some cases until 6th April) at four urban, one suburban, two rural background and two rural sites, with different degree of industrial influence, in the Mexico City Metropolitan Area (MCMA) and adjacent regions. PM10 and PM2.5 daily levels varied between 50–56μg/m3 and 24–46μg/m3 at the urban sites, 22–35μg/m3 and 13–25μg/m3 at the rural sites, and 75μg/m3 and 31μg/m3 at the industrial hotspot, lower than those recorded at some Asian mega-cities and similar to those recorded at other Latin American cities. At the urban sites, hourly PM2.5 and PM1 concentrations showed a marked impact of road traffic emissions (at rush hours), with levels of coarse PM remaining elevated during daytime. At the suburban and rural sites different PM daily patterns were registered according to the influence of the pollution plume from MCMA, and also of local soil resuspension. The speciation studies showed that mineral matter accounted for 25–27% of bulk PM10 at the urban sites and a higher proportion (up to 43%) at the suburban and rural sites. This pattern is repeated in PM2.5, with 15% at urban and 28% at suburban and rural sites. Carbonaceous compounds accounted for a significant proportion at the urban and industrial sites (32–46% in PM10, and 51–55% in PM2.5), markedly reduced at the suburban and rural sites (16–23% in PM10, and 30% in PM2.5). The secondary inorganic aerosols accounted for 10–20% of bulk PM10 at urban, suburban, rural and industrial sites, with a higher proportion (40%) at the industrial background site. A relatively high proportion of nitrate in rural sites was present in the coarse fraction. Typically anthropogenic elements (As, Cr, Zn, Cu, Pb, Sn, Sb, Ba, among others) showed considerably high levels at the urban sites; however levels of particulate Hg and crustal trace elements (Rb, Ti, La, Sc, Ga) were generally higher at the suburban site. Principal component analysis identified three major common factors: crustal, regional background and road traffic. Moreover, some specific factors were obtained for each site.
Spatial variation in particle number size distributions in a large metropolitan area
Authors: Mejía J. F. , Morawska L. , Mengersen K.
Published: April 2010

Abstract. Air quality studies have indicated that particle number size distribution (NSD) is unevenly spread in urban air. To date, these studies have focussed on differences in concentration levels between sampling locations rather than differences in the underlying geometries of the distributions. As a result, the existing information on the spatial variation of the NSD in urban areas remains incomplete. To investigate this variation in a large metropolitan area in the southern hemisphere, NSD data collected at nine different locations during different campaigns of varying duration were compared using statistical methods. The spectra were analysed in terms of their modal structures (the graphical representation of the number size distribution function), cumulative distribution and number median diameter (NMD). The study found that with the exception of one site all distributions were bimodal or suggestive of bimodality. In general, peak concentrations were below 30 nm and NMDs below 50 nm, except at a site dominated by diesel trucks, where it shifted to around 50 and 60 nm respectively. Ultrafine particles (UFPs (<100 nm)) contributed to 82–90% of the particle number, nanoparticles (<50 nm) to around 60–70%, except at the diesel traffic site, where their contribution dropped to 50%. Statistical analyses found that the modal structures heterogeneously distributed throughout Brisbane whereas it was not always the case for the NMD. The discussion led to the following site classification: (1) urban sites dominated by petrol traffic, (2) urban sites affected by the proximity to the road and (3) an isolated site dominated by diesel traffic. Comparisons of weekday and weekend data indicated that, the distributions were not statistically different. The only exception occurred at one site, where there is a significant drop in the number of diesel buses on the weekend. The differences in sampling period between sites did not affect the results. The statistics instead suggested variations in traffic composition. However, the relative contribution of petrol vehicle emissions at each site could not be assessed due to the limited traffic information available.
Modelling sea salt aerosol and its direct and indirect effects on climate
Authors: Ma X. , von Salzen K. , Li J.
Published: April 2010

Abstract. A size-dependent sea salt aerosol parameterization was developed based on the piecewise log-normal approximation (PLA) for aerosol size distributions. Results of this parameterization from simulations with a global climate model produce good agreement with observations at the surface and for vertically-integrated volume size distributions. The global and annual mean of the sea salt burden is 10.1 mg m−2. The direct radiative forcing is calculated to be −1.52 and −0.60 W m−2 for clear sky and all sky, respectively. The first indirect radiative forcing is about twice as large as the direct forcing for all-sky (−1.34 W m−2). The results also show that the total indirect forcing of sea salt is −2.9 W m−2 if climatic feedbacks are taken into account. The sensitivity of the forcings to changes in the burdens and sizes of sea salt particles was also investigated based on additional simulations with a different sea salt source function.
A long-term comparison of wind and tide measurements in the upper mesosphere recorded with an imaging Doppler interferometer and SuperDARN radar at Halley, Antarctica
Authors: Hibbins R. E. , Jarvis M. J.
Published: April 2010

Abstract. Data from a near co-located imaging Doppler interferometer (IDI) and SuperDARN radar recorded since 1996 have been analysed in a consistent manner to compare the derived mean winds and tides in the upper mesosphere. By comparing only days when both techniques were recording good quality meridional wind data it is shown that the SuperDARN radar winds and tides correlate best with the IDI height bin 90–95 km. On timescales of one hour the winds derived from the IDI have a much greater associated variance and correlate poorly with the SuperDARN winds. Regression analysis reveals that the observed SuperDARN daily mean meridional wind strength is approximately 65% that recorded by the IDI, in good quantitative agreement with previous studies which have shown contamination to SuperDARN derived winds due to the significant back lobe of the radar radiation pattern. Climatologically the two techniques observe similar monthly mean winds with the SuperDARN meridional winds suppressed compared to the IDI which tends to record winds more poleward than those derived by the SuperDARN radar during the summer months, and to be slightly more equatorward during the winter. The 12-h tidal amplitude and phase derived from both techniques are in good agreement, whereas the 24-h tides are seen much more strongly in the SuperDARN radar, especially in wintertime, with poor phase agreement. Long term comparison of the two techniques reveals a tendency for the IDI meridional winds to be more poleward during solar maximum especially during summer time; an effect which is not reproduced in the meridional winds derived from the SuperDARN radar. These results are discussed in the context of previous studies to independently determine the veracity of each technique, and to highlight the circumstances where data derived from these two techniques can be used to draw reliable conclusions from comparative studies based on geographically distributed pairs of instruments.
Modeling the impact of sub-grid scale emission variability on upper-air concentration
Authors: Galmarini S. , Vinuesa J.-F. , Martilli A.
Published: April 2010

Abstract. The long standing issue of sub-grid emission heterogeneity and its influence to upper air concentration is addressed here and a subgrid model proposed. The founding concept of the approach is the assumption that average emission act as source terms of average concentration, emission fluctuations are source for the concentration variance. The model is based on the derivation of the sub-grid contribution of emission and the use of the concentration variance equation to transport it in the atmospheric boundary layer. The model has been implemented in an existing mesoscale model and the results compared with Large-Eddy Simulation data for ad-hoc simulation devised to test specifically the parametrization. The results show an excellent agreement of the models. For the first time a time evolving error bar reproducing the sub-grid scale heterogeneity of the emissions and the way in which it affects the concentration has been shown. The concentration variance is presented as an extra attribute to better define the mean concentrations in a Reynolds-average model. The model has applications from meso to global scale and that go beyond air quality.
On the attribution of stratospheric ozone and temperature changes to changes in ozone-depleting substances and well-mixed greenhouse gases
Authors: Shepherd T. G. , Jonsson A. I.
Published: April 2010

Abstract. The vertical profile of global-mean stratospheric temperature changes has traditionally represented an important diagnostic for the attribution of the cooling effects of stratospheric ozone depletion and CO2 increases. However, CO2-induced cooling alters ozone abundance by perturbing ozone chemistry, thereby coupling the stratospheric ozone and temperature responses to changes in CO2 and ozone-depleting substances (ODSs). Here we untangle the ozone-temperature coupling and show that the attribution of global-mean stratospheric temperature changes to CO2 and ODS changes (which are the true anthropogenic forcing agents) can be quite different from the traditional attribution to CO2 and ozone changes. The significance of these effects is quantified empirically using simulations from a three-dimensional chemistry-climate model. The results confirm the essential validity of the traditional approach in attributing changes during the past period of rapid ODS increases, although we find that about 10% of the upper stratospheric ozone decrease from ODS increases over the period 1975–1995 was offset by the increase in CO2, and the CO2-induced cooling in the upper stratosphere has been somewhat overestimated. When considering ozone recovery, however, the ozone-temperature coupling is a first-order effect; fully 2/5 of the upper stratospheric ozone increase projected to occur from 2010–2040 is attributable to CO2 increases. Thus, it has now become necessary to base attribution of global-mean stratospheric temperature changes on CO2 and ODS changes rather than on CO2 and ozone changes.
Volatile Organic Compound (VOC) measurements in the Pearl River Delta (PRD) region, China
Authors: Liu Ying , Shao Min , Lu Sihua , Chang Chih-chung , Wang Jia-Lin , Chen Gao
Published: April 2010

Abstract. We measured levels of ambient volatile organic compounds (VOCs) at seven sites in the Pearl River Delta (PRD) region of China during the Air Quality Monitoring Campaign spanning 4 October to 3 November 2004. Two of the sites, Guangzhou (GZ) and Xinken (XK), were intensive sites at which we collected multiple daily canister samples. The observations reported here provide a look at the VOC distribution, speciation, and photochemical implications in the PRD region. Alkanes constituted the largest percentage (>40%) in mixing ratios of the quantified VOCs at six sites; the exception was one major industrial site that was dominated by aromatics (about 52%). Highly elevated VOC levels occurred at GZ during two pollution episodes; however, the chemical composition of VOCs did not exhibit noticeable changes during these episodes. We calculated the OH loss rate to estimate the chemical reactivity of all VOCs. Of the anthropogenic VOCs, alkenes played a predominant role in VOC reactivity at GZ, whereas the contributions of reactive aromatics were more important at XK. Our preliminary analysis of the VOC correlations suggests that the ambient VOCs at GZ came directly from local sources (i.e., automobiles); those at XK were influenced by both local emissions and transportation of air mass from upwind areas.