bluuebunny/crossref_metadata_2025 huggingface dataset:
Technical note: application of α-QSS to the numerical integration of kinetic equations in tropospheric chemistry
Authors: Liu F. , Schaller E. , Mott D. R.
Published: April 2010

Abstract. A major task in many applications of atmospheric chemistry transport problems is the numerical integration of stiff systems of Ordinary Differential Equations (ODEs) describing the chemical transformations. A faster solver that is easier to couple to the other physics in the problem is still needed. The integration method, α-QSS, corresponding to the solver CHEMEQ2 aims at meeting the demands of a process-split, reacting-flow simulation (Mott 2000; Mott and Oran, 2001). However, this integrator has yet to be applied to the numerical integration of kinetic equations in tropospheric chemistry. A zero-dimensional (box) model is developed to test how well CHEMEQ2 works on the tropospheric chemistry equations. This paper presents the testing results. The reference chemical mechanisms herein used are Regional Atmospheric Chemistry Mechanism (RACM) (Stockwell et al., 1997) and its secondary lumped successor Regional Lumped Atmospheric Chemical Scheme (ReLACS) (Crassier et al., 2000). The box model is forced and initialized by the DRY scenarios of Protocol Ver. 2 developed by EUROTRAC (Poppe et al., 2001). The accuracy of CHEMEQ2 is evaluated by comparing the results to solutions obtained with VODE. This comparison is made with parameters of the error tolerance, relative difference with respect to VODE scheme, trade off between accuracy and efficiency, global time step for integration etc. The study based on the comparison concludes that the single-point α-QSS approach is fast and moderately accurate as well as easy to couple to reacting flow simulation models, which makes CHEMEQ2 one of the best candidates for three-dimensional atmospheric Chemistry Transport Modelling (CTM) studies. In addition the RACM mechanism may be replaced by ReLACS mechanism for tropospheric chemistry transport modelling. The testing results also imply that the accuracy for chemistry numerical simulations is highly different from species to species. Therefore ozone is not the good choice for testing numerical ODE solvers or for evaluation of mechanisms because current tropospheric chemistry mechanisms are mainly designed for troposphere ozone prediction.
Optical properties of humic-like substances (HULIS) in biomass-burning aerosols
Authors: Hoffer A. , Gelencsér A. , Guyon P. , Kiss G. , Schmid O. , Frank G. , Artaxo P. , Andreae M. O.
Published: April 2010

Abstract. We present here the optical properties of humic-like substances (HULIS) isolated from the fine fraction of biomass burning aerosol collected in the Amazon basin during the LBA-SMOCC (Large scale Biosphere atmosphere experiment in Amazonia – SMOke aerosols, Clouds, rainfall and Climate) experiment in September 2002. From the isolated HULIS, aerosol particles were generated and their scattering and absorption coefficients measured. The size distribution and mass of the particles were also recorded. The value of the index of refraction was derived from "closure'' calculations based on particle size, scattering and absorption measurements. On average, the complex index of refraction at 532 nm of HULIS collected during day and nighttime was 1.65–0.00187i and 1.69–0.00163i, respectively. In addition, the imaginary part of the complex index of refraction was calculated using the measured absorption coefficient of the bulk HULIS. The mass absorption coefficient of the HULIS was found to be quite low at 532 nm (0.031 and 0.029 m2g−1 for the day and night samples, respectively). However, due to the high Ångström exponent of HULIS (6–7) the specific absorption increases substantially towards shorter wavelengths m2g−1 at 300 nm), causing a relatively high (up to 50%) contribution to the absorption at this wavelength. For the relative contribution of HULIS to light absorption in the entire solar spectrum, lower values (6.4–8.6%) are obtained, but those are still not negligible.
Mobile laboratory measurements of black carbon, polycyclic aromatic hydrocarbons and other vehicle emissions in Mexico City
Authors: Jiang M. , Marr L. C. , Dunlea E. J. , Herndon S. C. , Jayne J. T. , Kolb C. E. , Knighton W. B. , Rogers T. M. , Zavala M. , Molina L. T. , Molina M. J.
Published: April 2010

Abstract. Black carbon (BC) and polycyclic aromatic hydrocarbons (PAHs) are of concern due to their effects on climate and health. The main goal of this research is to provide the first estimate of emissions of BC and particle-phase PAHs (PPAHs) from motor vehicles in Mexico City. The emissions of other pollutants including carbon monoxide (CO), oxides of nitrogen (NOx), volatile organic compounds (VOCs), and particulate matter of diameter 2.5 µm and less (PM2.5) are also estimated. As a part of the Mexico City Metropolitan Area field campaign in April 2003 (MCMA-2003), a mobile laboratory was driven throughout the city. The laboratory was equipped with a comprehensive suite of gas and particle analyzers, including an aethalometer that measured BC and a photoionization aerosol sensor that measured PPAHs. While driving through traffic, the mobile lab is continuously sampling exhaust plumes from the vehicles around it. We have developed a method of automatically identifying exhaust plumes, which are then used as the basis for calculation of fleet-average emission factors. In the approximately 75 h of on-road sampling during the field campaign, we have identified ~30 000 exhaust measurement points that represent a variety of vehicle types and driving conditions. The large sample provides a basis for estimating fleet-average emission factors and thus the emission inventory. Motor vehicles in the Mexico City area are estimated to emit 1700±200 metric tons BC, 57±6 tons PPAHs, 1 190 000±40 000 tons CO, 120 000±3000 tons NOx, 202 000±4000 tons VOCs, and 4400±400 tons PM2.5 per year, not including cold start emissions. The estimates for CO, NOx, and PPAHs may be low by up to 10% due to the slower response time of analyzers used to measure these species. Compared to the government's official motor vehicle emission inventory for the year 2002, the estimates for CO, NOx, VOCs, and PM2.5 are 38% lower, 23% lower, 7% higher, and 26% higher, respectively. The distributions of emission factors of BC, PPAHs, and PM2.5 are highly skewed, i.e. asymmetric, while those for benzene, measured as a surrogate for total VOCs, and NOx are less skewed. As a result, the total emissions of BC, PPAHs, and PM2.5 could be reduced by approximately 50% if the highest 20% of data points were removed, but ''super polluters'' are less influential on overall NOx and VOC emissions.
Overview of SCIAMACHY validation: 2002–2004
Authors: Piters A. J. M. , Bramstedt K. , Lambert J.-C. , Kirchhoff B.
Published: April 2010

Abstract. SCIAMACHY, on board Envisat, is now in operation for almost three years. This UV/visible/NIR spectrometer measures the solar irradiance, the earthshine radiance scattered at nadir and from the limb, and the attenuation of solar radiation by the atmosphere during sunrise and sunset, from 240 to 2380 nm and at moderate spectral resolution. Vertical columns and profiles of a variety of atmospheric constituents are inferred from the SCIAMACHY radiometric measurements by dedicated retrieval algorithms. With the support of ESA and several international partners, a methodical SCIAMACHY validation programme has been developed jointly by Germany, the Netherlands and Belgium (the three instrument providing countries) to face complex requirements in terms of measured species, altitude range, spatial and temporal scales, geophysical states and intended scientific applications. This summary paper describes the approach adopted to address those requirements. The actual validation of the operational SCIAMACHY processors established at DLR on behalf of ESA has been hampered by data distribution and processor problems. Since first data releases in summer 2002, operational processors were upgraded regularly and some data products – level-1b spectra, level-2 O3, NO2, BrO and clouds data – have improved significantly. Validation results summarised in this paper conclude that for limited periods and geographical domains they can already be used for atmospheric research. Nevertheless, remaining processor problems cause major errors preventing from scientific usability in other periods and domains. Untied to the constraints of operational processing, seven scientific institutes (BIRA-IASB, IFE, IUP-Heidelberg, KNMI, MPI, SAO and SRON) have developed their own retrieval algorithms and generated SCIAMACHY data products, together addressing nearly all targeted constituents. Most of the UV-visible data products (both columns and profiles) already have acceptable, if not excellent, quality. Several near-infrared column products are still in development but they have already demonstrated their potential for a variety of applications. In any case, scientific users are advised to read carefully validation reports before using the data. It is required and anticipated that SCIAMACHY validation will continue throughout instrument lifetime and beyond. The actual amount of work will obviously depend on funding considerations.
Simulating regional scale secondary organic aerosol formation during the TORCH 2003 campaign in the southern UK
Authors: Johnson D. , Utembe S. R. , Jenkin M. E. , Derwent R. G. , Hayman G. D. , Alfarra M. R. , Coe H. , McFiggans G.
Published: April 2010

Abstract. A photochemical trajectory model has been used to simulate the chemical evolution of air masses arriving at the TORCH field campaign site in the southern UK during late July and August 2003, a period which included a widespread and prolonged photochemical pollution episode. The model incorporates speciated emissions of 124 non-methane anthropogenic VOC and three representative biogenic VOC, coupled with a comprehensive description of the chemistry of their degradation. A representation of the gas/aerosol absorptive partitioning of ca. 2000 oxygenated organic species generated in the Master Chemical Mechanism (MCM v3.1) has been developed and implemented, allowing simulation of the contribution to organic aerosol (OA) made by semi- and non-volatile products of VOC oxidation; emissions of primary organic aerosol (POA) and elemental carbon (EC) are also represented. Simulations of total OA mass concentrations in nine case study events (optimised by comparison with observed mass loadings derived from aerosol mass spectrometry measurements) imply that the OA can be ascribed to three general sources: (i) POA emissions; (ii) a ubiquitous background concentration of 0.7 µg m−3; and (iii) gas-to-aerosol transfer of lower volatility products of VOC oxidation generated by the regional scale processing of emitted VOC, but with all partitioning coefficients increased by a species-independent factor of 500. The requirement to scale the partitioning coefficients, and the implied background concentration, are both indicative of the occurrence of chemical processes within the aerosol which allow the oxidised organic species to react by association and/or accretion reactions which generate even lower volatility products, leading to a persistent, non-volatile secondary organic aerosol (SOA). The contribution of secondary organic material to the simulated OA results in significant elevations in the simulated ratio of organic carbon (OC) to EC, compared with the ratio of 1.1 assigned to the emitted components. For the selected case study events, [OC]/[EC] is calculated to lie in the range 2.7–9.8, values which are comparable with the high end of the range reported in the literature.
Intercomparison exercise between different radiative transfer models used for the interpretation of ground-based zenith-sky and multi-axis DOAS observations
Authors: Hendrick F. , Van Roozendael M. , Kylling A. , Petritoli A. , Rozanov A. , Sanghavi S. , Schofield R. , von Friedeburg C. , Wagner T. , Wittrock F. , Fonteyn D. , De Mazière M.
Published: April 2010

Abstract. We present the results of an intercomparison exercise between six different radiative transfer (RT) models carried out in the framework of QUILT, an EU funded project based on the exploitation of the Network for the Detection of Stratospheric Change (NDSC). RT modeling is an important step in the interpretation of Differential Optical Absorption Spectroscopy (DOAS) observations. It allows the conversion of the slant column densities (SCDs) into vertical column densities (VCDs) using calculated air mass factors (AMFs). The originality of our study resides in comparing SCD simulations in multi-axis (MAX) geometry (trace gases: NO2 and HCHO) and in taking into account the photochemical enhancement for calculating SCDs of rapidly photolysing species (BrO, NO2, and OClO) in zenith-sky geometry. Concerning the MAX simulations, good agreement is observed between the different models with the calculated NO2 and HCHO SCDs differing by no more than 5% in the elevation and solar zenith angles (SZA) ranges investigated (5°–20° and 35°–85°, respectively). The impacts of aerosol scattering, ground albedo, and relative azimuth on MAX simulations have also been tested. Large discrepancies appear for the aerosol effect, suggesting differences between models in the treatment of the aerosol scattering. A better agreement is obtained in the case of the ground albedo and relative azimuth effects. In zenith-sky geometry, the different models agree generally well, especially below 90° SZA. At higher SZA, larger discrepancies are observed with relative difference values between 2% and 14% in some cases. All the initialization data and results have been made publicly available through the QUILT project web site (http://nadir.nilu.no/quilt/), enabling the testing of other RT codes designed for the calculation of SCDs/AMFs.
Chemical transformations in organic aerosol from biomass burning
Authors: Hoffer A. , Gelencsér A. , Blazsó M. , Guyon P. , Artaxo P. , Andreae M. O.
Published: April 2010

Abstract. Fine aerosol particles were collected separately during daytime and nighttime at a tropical pasture site in Rondônia, Brazil, during the burning and dry-to-wet transition period in 2002. Total carbon (TC) and water-soluble organic carbon (WSOC) were measured by evolved gas analysis (EGA). Based on the thermochemical properties of the fine aerosol, the relative amounts of the low and higher molecular weight compounds were estimated. It was found that the thermally refractory (possibly higher molecular weight) compounds dominated the TC composition. Their contribution to TC was higher in the daytime samples than in the nighttime ones. The relative share of WSOC also showed a statistically significant diel variation and so did its refractory fraction. Anhydrosugars and phenolic acids were determined by GC-MS and their diel variation was studied. Based on the decrease of their relative concentrations between the biomass burning and transition periods and their distinctly different diel variations, we suggest that the phenolic acids may undergo chemical transformations in the aerosol phase, possibly towards more refractory compounds (humic-like substances, HULIS), as has been suggested previously. These conclusions are supported by the results of the thermally assisted hydrolysis and methylation gas chromatography-mass spectrometry of the same filter samples.
A 2003 stratospheric aerosol extinction and PSC climatology from GOMOS measurements on Envisat
Authors: Vanhellemont F. , Fussen D. , Bingen C. , Kyrölä E. , Tamminen J. , Sofieva V. , Hassinen S. , Verronen P. , Seppälä A. , Bertaux J. L. , Hauchecorne A. , Dalaudier F. , Fanton d’Andon O. , Barrot G. , Mangin A. , Theodore B. , Guirlet M. , Renard J. B. , Fraisse R. , Snoeij P. , Koopman R. , Saavedra L.
Published: April 2010

Abstract. Stratospheric aerosols play an important role in a number of atmospheric issues such as midlatitude ozone depletion, atmospheric dynamics and the Earth radiative budget. Polar stratospheric clouds on the other hand are a crucial factor in the yearly Arctic 5 and Antarctic ozone depletion. It is therefore important to quantify the stratospheric aerosol/PSC abundance. In orbit since March 2002, the GOMOS instrument onboard the European Envisat satellite has provided a vast aerosol extinction data set. In this paper we present an aerosol/PSC climatology that was constructed from this data set, together with a discussion of the results.
Size-segregated aerosol chemical composition at a boreal site in southern Finland, during the QUEST project
Authors: Cavalli F. , Facchini M. C. , Decesari S. , Emblico L. , Mircea M. , Jensen N. R. , Fuzzi S.
Published: April 2010

Abstract. Size-segregated aerosol samples were collected during the QUEST field campaign at Hyytiälä, a boreal forest site in Southern Finland, during spring 2003. Aerosol samples were selectively collected during both particle formation events and periods in which no particle formation occurred. A comprehensive characterisation of the aerosol chemical properties (water-soluble inorganic and organic fraction) and an analysis of the relevant meteorological parameters revealed how aerosol chemistry and meteorology combine to determine a favorable "environment" for new particle formation. The results indicated that all events, typically favored during northerly air mass advection, were background aerosols (total mass concentrations range between 1.97 and 4.31 μg m−3), with an increasingly pronounced marine character as the northerly air flow arrived progressively from the west and, in contrast, with a moderate SO2-pollution influence as the air arrived from more easterly directions. Conversely, the non-event aerosol, transported from the south, exhibited the chemical features of European continental sites, with a marked increase in the concentrations of all major anthropogenic aerosol constituents. The higher non-event mass concentration (total mass concentrations range between 6.88 and 16.30 μg m−3) and, thus, a larger surface area, tended to suppress new particle formation, more efficiently depleting potential gaseous precursors for nucleation. The analysis of water-soluble organic compounds showed that clean nucleation episodes were dominated by aliphatic biogenic species, while non-events were characterised by a large abundance of anthropogenic oxygenated species. Interestingly, a significant content of α-pinene photo-oxidation products was observed in the events aerosol, accounting for, on average, 72% of their WSOC; while only moderate amounts of these species were found in the non-event aerosol. If the organic vapors condensing onto accumulation mode particles are responsible also for the growth of newly formed thermodynamically stable clusters, our finding allows one to postulate that, at the site, α-pinene photo-oxidation products (and probably also photo-oxidation products from other terpenes) are the most likely species to contribute to the growth of nanometer-sized particles.
Intercomparison of O3 profiles observed by SCIAMACHY, ground based microwave and FTIR instruments
Authors: Palm M. , v. Savigny C. , Warneke T. , Velazco V. , Notholt J. , Künzi K. , Burrows J. , Schrems O.
Published: April 2010

Abstract. Ozone profiles retrieved from limb scattering measurements of the SCIAMACHY instrument based on the satellite ENVISAT are compared to ground based low altitude resolution remote sensors. All profiles are retrieved using optimal estimation. Following the work of 5 Rodgers and Connor (2003) the retrievals of the ground based instruments are simulated using the SCIAMACHY retrieval. The SCIAMACHY results and the results of the ground based microwave radiometer in Bremen and Ny Alesund agree within the expected covariance of the intercomparison. There are not enough coincident measurements of the FTIR instrument in order to allow for a conlusive statistical 10 treatment. However, preliminary intercomparison results are presented.
Interannual variation patterns of total ozone and temperature in observations and model simulations
Authors: Steinbrecht W. , Haßler B. , Brühl C. , Dameris M. , Giorgetta M. A. , Grewe V. , Manzini E. , Matthes S. , Schnadt C. , Steil B. , Winkler P.
Published: April 2010

Abstract. We report results from a multiple linear regression analysis of long-term total ozone observations (1979 to 2002, by TOMS/SBUV), of temperature reanalyses (1958 to 2002, NCEP), and of two chemistry-climate model simulations (1960 to 1999, by ECHAM4.L39(DLR)/CHEM (=E39/C), and MAECHAM4-CHEM). The model runs are transient experiments, where observed sea surface temperatures, increasing source gas concentrations (CO2, CFCs, CH4, N2O, NOx), 11-year solar cycle, volcanic aerosols and the quasi-biennial oscillation (QBO) are all accounted for. MAECHAM4-CHEM covers the atmosphere from the surface up to 0.01 hPa (≈80 km). For a proper representation of middle atmosphere (MA) dynamics, it includes a parametrization for momentum deposition by dissipating gravity wave spectra. E39/C, on the other hand, has its top layer centered at 10 hPa (≈30 km). It is targeted on processes near the tropopause, and has more levels in this region. Both models reproduce the observed amplitudes and much of the observed low-latitude patterns of the various modes of interannual variability, MAECHAM4-CHEM somewhat better than E39/C. Total ozone and lower stratospheric temperature show similar patterns. Main contributions to the interannual variations of total ozone and lower stratospheric temperature at 50 hPa come from a linear trend (up to −30 Dobson Units (DU) per decade, or −1.5 K/decade), the QBO (up to 25 DU, or 2.5 K peak to peak), the intensity of the polar vortices (up to 50 DU, or 5 K peak to peak), and from tropospheric weather (up to 30 DU, or 3 K peak to peak). Smaller variations are related to the 11-year solar cycle (generally less than 25 DU, or 2.5 K), and to ENSO (up to 15 DU, or 1.5 K). Volcanic eruptions have resulted in sporadic changes (up to −40 DU, or +3 K). Most stratospheric variations are connected to the troposphere, both in observations and simulations. At low latitudes, patterns are zonally symmetric. At higher latitudes, however, strong, zonally non-symmetric signals are found close to the Aleutian Islands or south of Australia. Such asymmetric features appear in the model runs as well, but often at different longitudes than in the observations. The results point to a key role of the zonally asymmetric Aleutian (or Australian) stratospheric anti-cyclones for interannual variations at high- latitudes, and for coupling between polar vortex strength, QBO, 11-year solar cycle and ENSO.
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.
Phase transitions and hygroscopic growth of aerosol particles containing humic acid and mixtures of humic acid and ammonium sulphate
Authors: Badger C. L. , George I. , Griffiths P. T. , Braban C. F. , Cox R. A. , Abbatt J. P. D.
Published: April 2010

Abstract. The phase transitions and hygroscopic growth of two humic acid aerosols (Aldrich sodium salt and Leonardite Standard (IHSS)) and their mixtures with ammonium sulphate have been investigated using a combination of two techniques, Fourier transform infra-red (FTIR) spectroscopy and tandem differential mobility analysis (TDMA). A growth factor of 1.16 at 85% relative humdity (RH) was found for the Aldrich humic acid which can be regarded as an upper limit for growth factors of humic-like substances (HULIS) found in atmospheric aerosol and is significantly smaller than that of typical atmospheric inorganics. We find that the humic acid aerosols exhibit water uptake over all relative humidites with no apparent phase changes, suggesting that these aerosols readily form supersaturated droplets. In the mixed particles, the humic acid component decreases the deliquescence relative humidity (DRH) and increases the efflorescence relative humidity (ERH) of the ammonium sulphate component, and there is some degree of water uptake prior to ammonium sulphate deliquescence. In addition, at low RH, the FTIR spectra show that the ammonium is present in a different chemical environment in the mixed aerosols than in crystalline ammonium sulphate, perhaps existing as a complex with the humic materials. The growth factors of the mixed aerosols are intermediate between those of the single component aerosols and can be predicted assuming that the inorganic and organic fractions take up water independently.
Satellite-derived land surface parameters for mesoscale modelling of the Mexico City basin
Authors: de Foy B. , Molina L. T. , Molina M. J.
Published: April 2010

Abstract. Mesoscale meteorological modelling is an important tool to help understand air pollution and heat island effects in urban areas. Accurate wind simulations are difficult to obtain in areas of weak synoptic forcing. Local factors have a dominant role in the circulation and include land surface parameters and their interaction with the atmosphere. This paper examines an episode during the MCMA-2003 field campaign held in the Mexico City Metropolitan Area (MCMA) in April of 2003. High resolution satellite observations are used to specify the land use, vegetation fraction, albedo and surface temperature in the MM5 model. Making use of these readily available data leads to improved meteorological simulations in the MCMA, both for the wind circulation patterns and the urban heat island. Replacing values previously obtained from land-use tables with actual measurements removes the number of unknowns in the model and increases the accuracy of the energy budget. In addition to improving the understanding of local meteorology, this sets the stage for the use of advanced urban modules.
Modeling the possible role of iodine oxides in atmospheric new particle formation
Authors: Pechtl S. , Lovejoy E. R. , Burkholder J. B. , von Glasow R.
Published: April 2010

Abstract. We studied the possible role of iodine oxides in atmospheric new particle formation with the one-dimensional marine boundary layer model MISTRA, which includes chemistry in the gas and aerosol phase as well as aerosol microphysics. The chemical reaction set focuses on halogen (Cl-Br-I) chemistry. We included a two-step nucleation parameterization, where in the first step, the ''real'' nucleation process is parameterized, i.e., the formation of cluster-sized nuclei via homogeneous condensation of gases. We considered both ternary sulfuric acid-ammonia-water nucleation and homomolecular homogeneous OIO nucleation. For the latter, we derived a parameterization based on combined laboratory-model studies. The second step of the nucleation parameterization treats the ''apparent'' nucleation rate, i.e., the growth of clusters into the model's lowest size bin by condensable vapors such as OIO. We compared different scenarios for a clean marine versus a polluted continental background atmosphere. In every scenario, we assumed the air to move, independent of its origin, first over a coastal region (where it is exposed to surface fluxes of different reactive iodine precursors) and later over the open ocean. According to these sensitivity studies, in the clean marine background atmosphere OIO can be responsible for both homogeneous nuclei formation and the subsequent growth of the clusters to detectable sizes. In contrast to this, in the continental case with its higher levels of pollutants, gas phase OIO mixing ratios, and hence related nucleation rates, are significantly lower. Compared to ternary H2SO4-NH3-H2O nucleation, homogeneous OIO nucleation can be neglected for new particle formation in this case, but OIO can contribute to early particle growth, i.e., to apparent nucleation rates. In general, we found OIO to be more important for the growth of newly formed particles than for the formation of new nuclei itself. According to our studies, observations of particle ''bursts'' can only be explained by hot spot-like, not by homogeneously distributed emissions.
Evaluation of organic markers for chemical mass balance source apportionment at the Fresno Supersite
Authors: Chow J. C. , Watson J. G. , Lowenthal D. H. , Chen L.-W. A. , Zielinska B. , Rinehart L. R. , Magliano K. L.
Published: April 2010

Abstract. Sources of PM2.5 at the Fresno Supersite during high PM2.5 episodes occurring from 15 December 2000–3 February 2001 were estimated with the Chemical Mass Balance (CMB) receptor model. The ability of source profiles with organic markers to distinguish motor vehicle, residential wood combustion (RWC), and cooking emissions was evaluated with simulated data. Organics improved the distinction between gasoline and diesel vehicle emissions and allowed a more precise estimate of the cooking source contribution. Sensitivity tests using average ambient concentrations showed that the gasoline vehicle contribution was not resolved without organics. Organics were not required to estimate hardwood combustion contributions. The most important RWC marker was the water-soluble potassium ion. The estimated cooking contribution did not depend on cholesterol because its concentrations were below the detection limit in most samples. Winter time source contributions were estimated by applying the CMB model to individual and average sample concentrations. RWC was the most significant source, contributing 29–31% of the measured PM2.5. Hardwood and softwood combustion accounted for 16–17% and 12–15%, respectively. Secondary ammonium nitrate and motor vehicle emissions accounted for 31–33% and 9–15%, respectively. The gasoline vehicle contribution (3–10%) was comparable to the diesel vehicle contribution (5–6%). The cooking contribution was 5–19% of PM2.5. Fresno source apportionment results were consistent with those estimated in previous studies.
Simplified representation of atmospheric aerosol size distributions using absolute principal component analysis
Authors: Chan T. W. , Mozurkewich M.
Published: April 2010

Abstract. Principal component analysis provides a fast and robust method to reduce the data dimensionality of an aerosol size distribution data set. Here we describe a methodology for applying principal component analysis to aerosol size distribution measurements. We illustrate the method by applying it to data obtained during five field studies. Most variations in the sub-micrometer aerosol size distribution over periods of weeks can be described using 5 components. Using 6 to 8 components preserves virtually all the information in the original data. A key aspect of our approach is the introduction of a new method to weight the data; this preserves the orthogonality of the components while taking the measurement uncertainties into account. We also describe a new method for identifying the approximate number of aerosol components needed to represent the measurement quantitatively. Applying Varimax rotation to the resultant components decomposes a distribution into independent monomodal distributions. Normalizing the components provides physical meaning to the component scores. The method is relatively simply, computationally fast, and numerically robust. The resulting data simplification provides an efficient method of representing complex data sets and should greatly assist in the analysis of size distribution data.
Boundary layer concentrations and landscape scale emissions of volatile organic compounds in early spring
Authors: Haapanala S. , Rinne J. , Hakola H. , Hellén H. , Laakso L. , Lihavainen H. , Janson R. , Kulmala M.
Published: April 2010

Abstract. Boundary layer concenrations of several volatile organic compounds (VOC) were measured during two campaigns in springs of 2003 and 2006. Measurements were conducted over boreal forests near SMEAR II measurement station in Hyytiälä, Southern Finland. In 2003 the measuremens were performed using light aircraft and in 2006 using hot air ballon. Isoprene concentrarions were low, usually below detection limit. This is explained by low biogenic production due to cold weather. Monoterpenes were observed frequently. Average total monoterpene concentration in the boundary layer was 33 pptv. Many anthropogenic compounds e.g. benzene, xylene and toluene, were observed in high amounts. Ecosystem scale surface emissions were estimated using simple mixed box budget methodology. Total monoterpene fluxes varied up to 80 μg m−2 h−1, α-pinene contributing typically more than two thirds of that. Highest fluxes of anthropogenic compounds were those of p/m xylene.
Connections between atmospheric sulphuric acid and new particle formation during QUEST III–IV campaigns in Heidelberg and Hyytiälä
Authors: Riipinen I. , Sihto S.-L. , Kulmala M. , Arnold F. , Dal Maso M. , Birmili W. , Saarnio K. , Teinilä K. , Kerminen V.-M. , Laaksonen A. , Lehtinen K. E. J.
Published: April 2010

Abstract. This study investigates the connections between atmospheric sulphuric acid and new particle formation during QUEST III and BACCI/QUEST IV campaigns. The campaigns have been conducted in Heidelberg (2004) and Hyytiälä (2005), the first representing a polluted site surrounded by deciduous forest, and the second a rural site in a boreal forest environment. We have studied the role of sulphuric acid in particle formation and growth by determining 1) the power-law dependencies between sulphuric acid ([H2SO4]), and particle concentrations (N3–6) or formation rates at 1 nm and 3 nm (J1 and J3; 2) the time delays between [H2SO4] and N3–6 or J3, and the growth rates for 1–3 nm particles; 3) the empirical nucleation coefficients A and K in relations J1=A[H2SO4] and J1=K[H2SO4]2, respectively; 4) theoretical predictions for J1 and J3 for the days when no significant particle formation is observed, based on the observed sulphuric acid concentrations and condensation sinks. In both environments, N3–6 or J3 and [H2SO4] were linked via a power-law relation with exponents typically ranging from 1 to 2. The result suggests that the cluster activation theory and kinetic nucleation have the potential to explain the observed particle formation. However, some differences between the sites existed: The 1–3 nm growth rates were slightly higher and the nucleation coefficients about an order of magnitude greater in Heidelberg than in Hyytiälä conditions. The time lags between J3 and [H2SO4] were consistently lower than the corresponding delays between N3–6 and [H2SO4]. The exponents in the J3∝[H2SO4]nJ3-connection were consistently higher than or equal to the exponents in the relation N3–6∝[H2SO4]nN36. In the J1 values, no significant differences were found between the observed rates on particle formation event days and the predictions on non-event days. The J3 values predicted by the cluster activation or kinetic nucleation hypotheses, on the other hand, were considerably lower on non-event days than the rates observed on particle formation event days. This study provides clear evidence implying that the main process limiting the observable particle formation is the competition between the growth of the freshly formed particles and their loss by scavenging, rather than the initial particle production by nucleation of sulphuric acid. In general, it can be concluded that the simple models based on sulphuric acid concentrations and particle formation by cluster activation or kinetic nucleation can predict the occurence of atmospheric particle formation and growth well, if the particle scavenging is accurately accounted for.
Relation of air mass history to nucleation events in Po Valley, Italy, using back trajectories analysis
Authors: Sogacheva L. , Hamed A. , Facchini M. C. , Kulmala M. , Laaksonen A.
Published: April 2010

Abstract. In this paper, we study the transport of air mass to San Pietro Capofiume (SPC) in Po Valley, Italy, by means of back trajectory analysis. Our main aim is to investigate whether air masses originate from different regions on nucleation event days and on nonevent days, during three years when nucleation events have been continuously recorded at SPC. The results indicate that nucleation events occur frequently in air masses arriving form Central Europe, whereas event frequency is much lower in air transported from southern directions and from the Atlantic Ocean. We also analyzed the behaviour of meteorological parameters during 96 h transport to SPC, and found that on average, event trajectories undergo stronger subsidence during the last 12 h before the arrival at SPC than nonevent trajectories. This causes a reversal in the temperature and relative humidity (RH) differences between event and nonevent trajectories: between 96 and 12 h back time, temperatures are lower and RH's higher for event than nonevent trajectories and between 12 and 0 h vice versa. Boundary layer mixing is stronger along the event trajectories compared to nonevent trajectories. The absolute humidity (AH) is similar for the event and nonevent trajectories between about 96 h and about 60 h back time, but after that, the event trajectories AH becomes lower due to stronger rain. We also studied transport of SO2 to SPC, and conclude that although sources in Po Valley most probably dominate the measured concentrations, certain Central and Eastern European sources can also have a non-negligible contribution.
Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, sesquiterpenes, and related compounds
Authors: Varutbangkul V. , Brechtel F. J. , Bahreini R. , Ng N. L. , Keywood M. D. , Kroll J. H. , Flagan R. C. , Seinfeld J. H. , Lee A. , Goldstein A. H.
Published: April 2010

Abstract. A series of experiments has been conducted in the Caltech indoor smog chamber facility to investigate the water uptake properties of aerosol formed by oxidation of various organic precursors. Secondary organic aerosol (SOA) from simple and substituted cycloalkenes (C5-C8) is produced in dark ozonolysis experiments in a dry chamber (RH~5%). Biogenic SOA from monoterpenes, sesquiterpenes, and oxygenated terpenes is formed by photooxidation in a humid chamber (~50% RH). Using the hygroscopicity tandem differential mobility analyzer (HTDMA), we measure the diameter-based hygroscopic growth factor (GF) of the SOA as a function of time and relative humidity. All SOA studied is found to be slightly hygroscopic, with smaller water uptake than that of typical inorganic aerosol substances. The aerosol water uptake increases with time early in the experiments for the cycloalkene SOA, but decreases with time for the biogenic SOA. This behavior could indicate competing effects between the formation of more highly oxidized polar compounds (more hygroscopic), and formation of longer-chained oligomers (less hygroscopic). All SOA also exhibit a smooth water uptake with RH with no deliquescence or efflorescence. The water uptake curves are found to be fitted well with an empirical three-parameter functional form. The measured pure organic GF values at 85% RH are between 1.09–1.16 for SOA from ozonolysis of cycloalkenes, 1.01–1.04 for sesquiterpene photooxidation SOA, and 1.06–1.11 for the monoterpene and oxygenated terpene SOA. The GF of pure SOA (GForg) in experiments in which inorganic seed aerosol is used is determined by assuming volume-weighted water uptake (Zdanovskii-Stokes-Robinson or ''ZSR'' approach) and using the size-resolved organic mass fraction measured by the Aerodyne Aerosol Mass Spectrometer. Knowing the water content associated with the inorganic fraction yields GForg values. However, for each precursor, the GForg values computed from different HTDMA-classified diameters agree with each other to varying degrees. Lack of complete agreement may be a result of the non-idealities of the solutions that are not captured by the ZSR method. Comparing growth factors from different precursors, we find that GForg is inversely proportional to the precursor molecular weight and SOA yield, which is likely a result of the fact that higher-molecular weight precursors tend to produce larger and less hygroscopic oxidation products.
Stratospheric dryness
Authors: Lelieveld J. , Brühl C. , Jöckel P. , Steil B. , Crutzen P. J. , Fischer H. , Giorgetta M. A. , Hoor P. , Lawrence M. G. , Milz M. , Sausen R. , Stiller G. P. , Tost H.
Published: April 2010

Abstract. The mechanisms responsible for the extreme dryness of the stratosphere have been debated for decades. A key difficulty has been the lack of models which are able to reproduce the observations. Here we examine results from a new atmospheric chemistry general circulation model (ECHAM5/MESSy1) together with satellite observations. Our model results match observed temperatures in the tropical lower stratosphere and realistically represent recurrent features such as the semi-annual oscillation (SAO) and the quasi-biennual oscillation (QBO), indicating that dynamical and radiation processes are simulated accurately. The model reproduces the very low water vapor mixing ratios (1–2 ppmv) periodically observed at the tropical tropopause near 100 hPa, as well as the characteristic tape recorder signal up to about 10 hPa, providing evidence that the dehydration mechanism is well-captured, albeit that the model underestimates convective overshooting and consequent moistening events. Our results show that the entry of tropospheric air into the stratosphere at low latitudes is forced by large-scale wave dynamics; however, radiative cooling can regionally limit the upwelling or even cause downwelling. In the cold air above cumulonimbus anvils thin cirrus desiccates the air through the sedimentation of ice particles, similar to polar stratospheric clouds. Transport deeper into the stratosphere occurs in regions where radiative heating becomes dominant, to a large extent in the subtropics. During summer the stratosphere is moistened by the monsoon, most strongly over Southeast Asia.
Remote sensed and in situ constraints on processes affecting tropical tropospheric ozone
Authors: Sauvage B. , Martin R. V. , van Donkelaar A. , Liu X. , Chance K. , Jaeglé L. , Palmer P. I. , Wu S. , Fu T.-M.
Published: April 2010

Abstract. We use a global chemical transport model (GEOS-Chem) to evaluate the consistency of satellite measurements of lightning flashes and ozone precursors with in situ measurements of tropical tropospheric ozone. The measurements are tropospheric O3, NO2, and HCHO columns from the GOME satellite instrument, lightning flashes from the OTD and LIS instruments, profiles of O3, CO, and relative humidity from the MOZAIC aircraft program, and profiles of O3 from the SHADOZ ozonesonde network. We interpret these multiple data sources with our model to better understand what controls tropical tropospheric ozone. Tropical tropospheric ozone is mainly affected by lightning and convection in the upper troposphere and by surface emissions in the lower troposphere. Scaling the spatial distribution of lightning in the model to the observed flash counts improves the simulation of O3 in the upper troposphere by 5–20 ppbv versus in situ observations and by 1–4 Dobson Units versus GOME retrievals of tropospheric O3 columns. A lightning source strength of 5±2 Tg N/yr best represents in situ observations from aircraft and ozonesonde. Tropospheric NO2 and HCHO columns from GOME are applied to provide top-down constraints on emission inventories of NOx (biomass burning and soils) and VOCs (biomass burning). The top-down biomass burning inventory is larger by a factor of 2 for HCHO and alkenes, and by 2.6 for NOx over northern equatorial Africa. These emissions increase lower tropospheric O3 by 5–20 ppbv, improving the simulation versus aircraft observations, and by 4 Dobson Units versus GOME observations of tropospheric O3 columns. Emission factors in the a posteriori inventory are more consistent with a recent compilation from in situ measurements. The ozone simulation using two different dynamical schemes (GEOS-3 and GEOS-4) is evaluated versus observations; GEOS-4 better represents O3 observations by 5–15 ppbv due to enhanced convective detrainment in the upper troposphere. Heterogeneous uptake of HNO3 on aerosols reduces simulated O3 by 5–7 ppbv, reducing a model bias versus in situ observations over and downwind of deserts. Exclusion of HO2 uptake on aerosols improves O3 by 5 ppbv in biomass burning regions.