Browsing by Subject "AEROSOLS"

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  • Belis, C. A.; Karagulian, F.; Amato, F.; Almeida, M.; Artaxo, P.; Beddows, D. C. S.; Bernardoni, V.; Bove, M. C.; Carbone, S.; Cesari, D.; Contini, D.; Cuccia, E.; Diapouli, E.; Eleftheriadis, K.; Favez, O.; El Haddad, I.; Harrison, R. M.; Hellebust, S.; Hovorka, J.; Jang, E.; Jorquera, H.; Kammermeier, T.; Karl, M.; Lucarelli, F.; Mooibroek, D.; Nava, S.; Nojgaard, J. K.; Paatero, P.; Pandolfi, M.; Perrone, M. G.; Petit, J. E.; Pietrodangelo, A.; Pokorna, P.; Prati, P.; Prevot, A. S. H.; Quass, U.; Querol, X.; Saraga, D.; Sciare, J.; Sfetsos, A.; Valli, G.; Vecchi, R.; Vestenius, M.; Yubero, E.; Hopke, P. K. (2015)
    The performance and the uncertainty of receptor models (RMs) were assessed in intercomparison exercises employing real-world and synthetic input datasets. To that end, the results obtained by different practitioners using ten different RMs were compared with a reference. In order to explain the differences in the performances and uncertainties of the different approaches, the apportioned mass, the number of sources, the chemical profiles, the contribution-to-species and the time trends of the sources were all evaluated using the methodology described in Bells et al. (2015). In this study, 87% of the 344 source contribution estimates (SCEs) reported by participants in 47 different source apportionment model results met the 50% standard uncertainty quality objective established for the performance test. In addition, 68% of the SCE uncertainties reported in the results were coherent with the analytical uncertainties in the input data. The most used models, EPA-PMF v.3, PMF2 and EPA-CMB 8.2, presented quite satisfactory performances in the estimation of SCEs while unconstrained models, that do not account for the uncertainty in the input data (e.g. APCS and FA-MLRA), showed below average performance. Sources with well-defined chemical profiles and seasonal time trends, that make appreciable contributions (>10%), were those better quantified by the models while those with contributions to the PM mass close to 1% represented a challenge. The results of the assessment indicate that RMs are capable of estimating the contribution of the major pollution source categories over a given time window with a level of accuracy that is in line with the needs of air quality management. (C) 2015 The Authors. Published by Elsevier Ltd.
  • Ylivinkka, Ilona; Kaupinmäki, Santeri; Virman, Meri; Peltola, Maija; Taipale, Ditte; Petäjä, Tuukka; Kerminen, Veli-Matti; Kulmala, Markku; Ezhova, Ekaterina (2020)
    We developed a simple algorithm to classify clouds based on global radiation and cloud base height measured by pyranometer and ceilometer, respectively. We separated clouds into seven different classes (stratus, stratocumulus, cumulus, nimbostratus, altocumulus + altostratus, cirrus + cirrocumulus + cirrostratus and clear sky + cirrus). We also included classes for cumulus and cirrus clouds causing global radiation enhancement, and we classified multilayered clouds, when captured by the ceilometer, based on their height and characteristics (transmittance, patchiness and uniformity). The overall performance of the algorithm was nearly 70% when compared with classification by an observer using total-sky images. The performance was best for clouds having well-distinguishable effects on solar radiation: nimbostratus clouds were classified correctly in 100% of the cases. The worst performance corresponds to cirriform clouds (50 %). Although the overall performance of the algorithm was good, it is likely to miss the occurrences of high and multilayered clouds. This is due to the technical limits of the instrumentation: the vertical detection range of the ceilometer and occultation of the laser pulse by the lowest cloud layer. We examined the use of clearness index, which is defined as a ratio between measured global radiation and modeled radiation at the top of the atmosphere, as an indicator of clear-sky conditions. Our results show that cumulus, altocumulus, altostratus and cirriform clouds can be present when the index indicates clear-sky conditions. Those conditions have previously been associated with enhanced aerosol formation under clear skies. This is an important finding especially in the case of low clouds coupled to the surface, which can influence aerosol population via aerosol-cloud interactions. Overall, caution is required when the clearness index is used in the analysis of processes affected by partitioning of radiation by clouds.
  • Hasan, Galib; Salo, Vili-Taneli; Valiev, Rashid; Kubecka, Jakub; Kurten, Theo (2020)
    Organic peroxy radicals (RO2) are key intermediates in the chemistry of the atmosphere. One of the main sink reactions of RO2 is the recombination reaction RO2 + R'O-2, which has three main channels (all with O-2 as a coproduct): (1) R-H=O + R'OH, (2) RO + R'O, and (3) ROOR'. The RO + R'O "alkoxy" channel promotes radical and oxidant recycling, while the ROOR' "dimer" channel leads to low-volatility products relevant to aerosol processes. The ROOR' channel has only recently been discovered to play a role in the gas phase. Recent computational studies indicate that all of these channels first go through an intermediate complex( 1)(RO center dot center dot center dot O-3(2)center dot center dot center dot OR'). Here, O-3(2) is very weakly bound and will likely evaporate from the system, giving a triplet cluster of two alkoxy radicals: (3)(RO center dot center dot center dot OR'). In this study, we systematically investigate the three reaction channels for an atmospherically representative set of RO + R'O radicals formed in the corresponding RO2+ R'O-2 reaction. First, we systematically sample the possible conformations of the RO center dot center dot center dot OR' clusters on the triplet potential energy surface. Next, we compute energetic parameters and attempt to estimate reaction rate coefficients for the three channels: evaporation/dissociation to RO + R'O, a hydrogen shift leading to the formation of R'(-H)=O + ROH, and "spin-flip" (intersystem crossing) leading to, or at least allowing, the formation of ROOR' dimers. While large uncertainties in the computed energetics prevent a quantitative comparison of reaction rates, all three channels were found to be very fast (with typical rates greater than 10 6 s(-1)). This qualitatively demonstrates that the computationally proposed novel RO2 + R'O-2 reaction mechanism is compatible with experimental data showing non-negligible branching ratios for all three channels, at least for sufficiently complex RO2.
  • Hari, Pertti Kaarlo Juhani; Petäjä, Tuukka Taneli; Bäck, Jaana Kaarina; Kerminen, Veli-Matti; Lappalainen, Hanna K; Vihma, Timo; Laurila, Tuomas; Viisanen, Yrjö; Vesala, Timo Veikko; Kulmala, Markku Tapio (2016)
    The global environment is changing rapidly due to anthropogenic emissions and actions. Such activities modify aerosol and greenhouse gas concentrations in the atmosphere, leading to regional and global climate change and affecting, e.g., food and fresh-water security, sustainable use of natural resources and even demography. Here we present a conceptual design of a global, hierarchical observation network that can provide tools and increased understanding to tackle the inter-connected environmental and societal challenges that we will face in the coming decades. The philosophy behind the conceptual design relies on physical conservation laws of mass, energy and momentum, as well as on concentration gradients that act as driving forces for the atmosphere-biosphere exchange. The network is composed of standard, flux and/or advanced and flagship stations, each of which having specific and identified tasks. Each ecosystem type on the globe has its own characteristic features that have to be taken into consideration. The hierarchical network as a whole is able to tackle problems related to large spatial scales, heterogeneity of ecosystems and their complexity. The most comprehensive observations are envisioned to occur in flagship stations, with which the process-level understanding can be expanded to continental and global scales together with advanced data analysis, Earth system modelling and satellite remote sensing. The denser network of the flux and standard stations allows application and up-scaling of the results obtained from flagship stations to the global level.
  • Ding, A. J.; Huang, X.; Nie, W.; Sun, J. N.; Kerminen, V. -M.; Petäjä, T.; Su, H.; Cheng, Y. F.; Yang, X. -Q.; Wang, M. H.; Chi, X. G.; Wang, J. P.; Virkkula, A.; Guo, W. D.; Yuan, J.; Wang, S. Y.; Zhang, R. J.; Wu, Y. F.; Song, Y.; Zhu, T.; Zilitinkevich, S.; Kulmala, M.; Fu, C. B. (2016)
    Aerosol-planetary boundary layer (PBL) interactions have been found to enhance air pollution in megacities in China. We show that black carbon (BC) aerosols play the key role in modifying the PBL meteorology and hence enhancing the haze pollution. With model simulations and data analysis from various field observations in December 2013, we demonstrate that BC induces heating in the PBL, particularly in the upper PBL, and the resulting decreased surface heat flux substantially depresses the development of PBL and consequently enhances the occurrences of extreme haze pollution episodes. We define this process as the dome effect of BC and suggest an urgent need for reducing BC emissions as an efficient way to mitigate the extreme haze pollution in megacities of China.
  • Kurten, Theo; Hyttinen, Noora; D'Ambro, Emma Louise; Thornton, Joel; Prisle, Nonne Lyng (2018)
    We have used COSMO-RS (the conductor-like screening model for real solvents), as implemented in the COSMOtherm program, to compute the saturation vapor pressures at 298 K of two photo-oxidation products of isoprene: the dihydroxy dihydroperoxide C5H12O6, and the dihydroperoxy hydroxy aldehyde, C5H10O6. The predicted saturation vapor pressures were significantly higher (by up to a factor of 1000) than recent experimental results, very likely due to the overestimation of the effects of intramolecular hydrogen bonds, which tend to increase saturation vapor pressures by stabilizing molecules in the gas phase relative to the liquid. Modifying the hydrogen bond enthalpy parameter used by COSMOtherm can improve the agreement with experimental results - however the optimal parameter value is likely to be system-specific. Alternatively, vapor pressure predictions can be substantially improved (to within a factor of 5 of the experimental values for the two systems studied here) by selecting only conformers with a minimum number of intramolecular hydrogen bonds. The computed saturation vapor pressures were very sensitive to the details of the conformational sampling approach, with the default scheme implemented in the COSMOconf program proving insufficient for the task, for example by predicting significant differences between enantiomers, which should have identical physical properties. Even after exhaustive conformational sampling, COSMOtherm predicts significant differences in saturation vapor pressures between both structural isomers and diastereomers. For C5H12O6, predicted differences in p(sat) between structural isomers are up to 2 orders of magnitude, and differences between stereoisomers are up to a factor of 20 - though these differences are very likely exaggerated by the overestimation of the effect of intramolecular H-bonds. For C5H10O6, the maximum predicted differences between the three studied structural isomers and their diastereomer pairs are around a factor of 8 and a factor of 2, respectively, when only conformers lacking intramolecular hydrogen bonds are included in the calculations. In future studies of saturation vapor pressures of polyfunctional atmospheric oxidation products using COSMOtherm, we recommend first performing thorough conformational sampling and subsequently selecting conformers with a minimal number of intramolecular H-bonds.
  • Fung, Pak Lun; Zaidan, Martha Arbayani; Niemi, Jarkko V.; Saukko, Erkka; Timonen, Hilkka; Kousa, Anu; Kuula, Joel; Rönkkö, Topi; Karppinen, Ari; Tarkoma, Sasu; Kulmala, Markku; Petäjä, Tuukka; Hussein, Tareq (2022)
    Lung-deposited surface area (LDSA) has been considered to be a better metric to explain nanoparticle toxicity instead of the commonly used particulate mass concentration. LDSA concentrations can be obtained either by direct measurements or by calculation based on the empirical lung deposition model and measurements of particle size distribution. However, the LDSA or size distribution measurements are neither compulsory nor regulated by the government. As a result, LDSA data are often scarce spatially and temporally. In light of this, we developed a novel statistical model, named the input-adaptive mixed-effects (IAME) model, to estimate LDSA based on other already existing measurements of air pollutant variables and meteorological conditions. During the measurement period in 2017–2018, we retrieved LDSA data measured by Pegasor AQ Urban and other variables at a street canyon (SC, average LDSA = 19.7 ± 11.3 µm2 cm−3) site and an urban background (UB, average LDSA = 11.2 ± 7.1 µm2 cm−3) site in Helsinki, Finland. For the continuous estimation of LDSA, the IAME model was automatised to select the best combination of input variables, including a maximum of three fixed effect variables and three time indictors as random effect variables. Altogether, 696 submodels were generated and ranked by the coefficient of determination (R2), mean absolute error (MAE) and centred root-mean-square difference (cRMSD) in order. At the SC site, the LDSA concentrations were best estimated by mass concentration of particle of diameters smaller than 2.5 µm (PM2.5), total particle number concentration (PNC) and black carbon (BC), all of which are closely connected with the vehicular emissions. At the UB site, the LDSA concentrations were found to be correlated with PM2.5, BC and carbon monoxide (CO). The accuracy of the overall model was better at the SC site (R2=0.80, MAE = 3.7 µm2 cm−3) than at the UB site (R2=0.77, MAE = 2.3 µm2 cm−3), plausibly because the LDSA source was more tightly controlled by the close-by vehicular emission source. The results also demonstrated that the additional adjustment by taking random effects into account improved the sensitivity and the accuracy of the fixed effect model. Due to its adaptive input selection and inclusion of random effects, IAME could fill up missing data or even serve as a network of virtual sensors to complement the measurements at reference stations.
  • Enroth, Joonas; Kangasluoma, Juha; Korhonen, Frans; Hering, Susanne; Picard, David; Lewis, Greg; Attoui, Michel; Petäjä, Tuukka (2018)
    Condensation particle counter (CPC) technology has continued to evolve, with the introduction of several new instruments over the last several years. An important aspect in the characterization of these instruments is the measurement of their time response. Yet there is no standardly accepted approach for this measurement. Here we evaluate different classically used methods for determining CPC time response, and present the potential pitfalls associated with these approaches. Further, we introduce a new simple definition for the term response time, E, which is based on the first-order systems response, while providing a practical definition by corresponding to approximate to 95% change in concentration. We also present results for various commonly used CPCs, and for the Airmodus A11 nano Condensation Nucleus Counter (nCNC) system, the TSI 3777+3772 Nano Enhancer system, and Aerosol Dynamics Inc.'s (ADI) new versatile water condensation particle counter.Copyright (c) 2018 American Association for Aerosol Research
  • Hakola, H; Tarvainen, V; Bäck, Jaana; Ranta, H; Bonn, Boris; Rinne, Janne; Kulmala, Markku (2006)
  • Svensson, Jonas; Virkkula, Aki; Meinander, Outi; Kivekäs, Niku; Hannula, Henna-Reetta; Järvinen, Onni; Peltoniemi, Jouni I.; Gritsevich, Maria; Heikkila, Anu; Kontu, Anna; Neitola, Kimmo; Brus, David; Dagsson-Waldhauserova, Pavla; Anttila, Kati; Vehkamäki, Marko; Hienola, Anca; De Leeuw, Gerrit; Lihavainen, Heikki (2016)
    Soot has a pronounced effect on the cryosphere and experiments are still needed to reduce the associated uncertainties. This work presents a series of experiments to address this issue, with soot being deposited onto a natural snow surface after which the albedo changes were monitored. The albedo reduction was the most pronounced for the snow with higher soot content, and it was observed immediately following soot deposition. Compared with a previous laboratory study the effects of soot on the snow were not as prominent in outdoor conditions. During snowmelt, about 50% of the originally deposited soot particles were observed to remain at the snow surface. More detailed experiments are however needed to better explain soot's effect on snow and to better quantify this effect. Our albedo versus soot parameterization agreed relatively well with previously published relationships.
  • Elm, Jonas; Hyttinen, Noora; Lin, Jack J.; Kurten, Theo; Prisle, Nonne L. (2019)
    The physical properties of small straight-chain dicarboxylic acids are well known to exhibit even/odd alternations with respect to the carbon chain length. For example, odd numbered diacids have lower melting points and higher saturation vapor pressures than adjacent even numbered diacids. This alternation has previously been explained in terms of solid-state properties, such as higher torsional strain of odd number diacids. Using quantum chemical methods, we demonstrate an additional contribution to this alternation in properties resulting from gas-phase dimer formation. Due to a combination of hydrogen bond strength and torsional strain, dimer formation in the gas phase occurs efficiently for glutaric acid (CS) and pimelic acid (C7) but is unfavorable for succinic acid (C4) and adipic acid (C6). Our results indicate that a significant fraction of the total atmospheric gas-phase concentration of glutaric and pimelic acid may consist of dimers.
  • Hyttinen, Noora; Heshmatnezhad, Reyhaneh; Elm, Jonas; Kurten, Theo; Prisle, Nonne L. (2020)
    We have used the COSMOtherm program to estimate activity coefficients and solubilities of mono- and alpha, omega-dicarboxylic acids and water in binary acid-water systems. The deviation from ideality was found to be larger in the systems containing larger acids than in the systems containing smaller acids. COnductor-like Screening MOdel for Real Solvents (COSMO-RS) underestimates experimental monocarboxylic acid activity coefficients by less than a factor of 2, but experimental water activity coefficients are underestimated more especially at high acid mole fractions. We found a better agreement between COSMOtherm-estimated and experimental activity coefficients of monocarboxylic acids when the water clustering with a carboxylic acid and itself was taken into account using the dimerization, aggregation, and reaction extension (COSMO-RS-DARE) of COSMOtherm. COSMO-RS-DARE is not fully predictive, but fit parameters found here for water-water and acid-water clustering interactions can be used to estimate thermodynamic properties of monocarboxylic acids in other aqueous solvents, such as salt solutions. For the dicarboxylic acids, COSMO-RS is sufficient for predicting aqueous solubility and activity coefficients, and no fitting to experimental values is needed. This is highly beneficial for applications to atmospheric systems, as these data are typically not available for a wide range of mixing states realized in the atmosphere, due to a lack of either feasibility of the experiments or sample availability. Based on effective equilibrium constants of different clustering reactions in the binary solutions, acid dimer formation is more dominant in systems containing larger dicarboxylic acids (C-5-C-8), while for monocarboxylic acids (C-1-C-6) and smaller dicarboxylic acids (C-2-C-4), hydrate formation is more favorable, especially in dilute solutions.