Browsing by Subject "SULFURIC-ACID"

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  • Doulgeris, Konstantinos M.; Brus, David; Raatikainen, Tomi; Kerminen, Veli-Matti (2018)
    The Finnish Meteorological Institute-Aerosol Cloud Interaction Tube (FMI-ACIT) is a multi-purpose instrument for investigating atmospherically relevant interactions between aerosol particles and water vapor under defined laboratory conditions. This work introduces an experimental setup of FMI-ACIT for investigation of the aerosol activation and the droplet growth under supersaturated conditions. Several simulations and experimental tests were conducted to find out what the proper operational parameters are. To verify the ability of FMI-ACIT to perform as a cloud condensation nuclei (CCN) counter, activation experiments were executed using size selected ammonium sulfate [(NH4)(2)SO4] particles in the size range of 10-300 nm. Supersaturations from 0.18% to 1.25% were tested by experiments with different temperature gradients. Those showed that FMI-ACIT can effectively measure CCN in this range. Measured droplet size distributions at supersaturations 0.18% and 1.25% are in good agreement with those determined by a droplet growth model. Published by AIP Publishing.
  • Franchin, Alessandro; Downard, Andy; Kangasluoma, Juha; Nieminen, Tuomo; Lehtipalo, Katrianne; Steiner, Gerhard; Manninen, Hanna E.; Petäjä, Tuukka; Flagan, Richard C.; Kulmala, Markku (2016)
    Reliable and reproducible measurements of atmospheric aerosol particle number size distributions below 10 nm require optimized classification instruments with high particle transmission efficiency. Almost all differential mobility analyzers (DMAs) have an unfavorable potential gradient at the outlet (e.g., long column, Vienna type) or at the inlet (nano-radial DMA), preventing them from achieving a good transmission efficiency for the smallest nanoparticles. We developed a new high-transmission inlet for the Caltech nano-radial DMA (nRDMA) that increases the transmission efficiency to 12% for ions as small as 1.3 nm in Millikan-Fuchs mobility equivalent diameter, D-p (corresponding to 1.2 x 10(-4) m(2) V-1 s(-1) in electrical mobility). We successfully deployed the nRDMA, equipped with the new inlet, in chamber measurements, using a particle size magnifier (PSM) and as a booster a condensation particle counter (CPC). With this setup, we were able to measure size distributions of ions within a mobility range from 1.2 x 10(-4) to 5.8 x 10(-6) m(2) V-1 s(-1). The system was modeled, tested in the laboratory and used to measure negative ions at ambient concentrations in the CLOUD (Cosmics Leaving Outdoor Droplets) 7 measurement campaign at CERN. We achieved a higher size resolution (R = 5.5 at D-p = 1.47 nm) than techniques currently used in field measurements (e.g., Neutral cluster and Air Ion Spectrometer (NAIS), which has a R similar to 2 at largest sizes, and R similar to 1.8 at D-p = 1.5 nm) and maintained a good total transmission efficiency (6.3% at D-p = 1.5 nm) at moderate inlet and sheath airflows (2.5 and 30 L min(-1), respectively). In this paper, by measuring size distributions at high size resolution down to 1.3 nm, we extend the limit of the current technology. The current setup is limited to ion measurements. However, we envision that future research focused on the charging mechanisms could extend the technique to measure neutral aerosol particles as well, so that it will be possible to measure size distributions of ambient aerosols from 1 nm to 1 mu m.
  • Lappalainen, Hanna K.; Sevanto, Sanna; Dal Maso, Miikka; Taipale, Risto; Kajos, Maija; Kolari, Pasi; Back, Jaana (2013)
  • Xausa, Filippo; Paasonen, Pauli; Makkonen, Risto; Arshinov, Mikhail; Ding, Aijun; Van Der Gon, Hugo Denier; Kerminen, Veli-Matti; Kulmala, Markku (2018)
    Climate models are important tools that are used for generating climate change projections, in which aerosol-climate interactions are one of the main sources of uncertainties. In order to quantify aerosol-radiation and aerosolcloud interactions, detailed input of anthropogenic aerosol number emissions is necessary. However, the anthropogenic aerosol number emissions are usually converted from the corresponding mass emissions in pre-compiled emission inventories through a very simplistic method depending uniquely on chemical composition, particle size and density, which are defined for a few, very wide main source sectors. In this work, the anthropogenic particle number emissions converted from the AeroCom mass in the ECHAM-HAM climate model were replaced with the recently formulated number emissions from the Greenhouse Gas and Air Pollution Interactions and Synergies (GAINS) model. In the GAINS model the emission number size distributions vary, for example, with respect to the fuel and technology. Special attention was paid to accumulation mode particles (particle diameter d(p) > 100 nm) because of (i) their capability of acting as cloud condensation nuclei (CCN), thus forming cloud droplets and affecting Earth's radiation budget, and (ii) their dominant role in forming the coagulation sink and thus limiting the concentration of sub-100 nm particles. In addition, the estimates of anthropogenic CCN formation, and thus the forcing from aerosol-climate interactions, are expected to be affected. Analysis of global particle number concentrations and size distributions reveals that GAINS implementation increases CCN concentration compared with AeroCom, with regional enhancement factors reaching values as high as 10. A comparison between modeled and observed concentrations shows that the increase in number concentration for accumulation mode particles agrees well with measurements, but it leads to a consistent underestimation of both nucleation mode and Aitken mode (d(p) <100 nm) particle number concentrations. This suggests that revisions are needed in the new particle formation and growth schemes currently applied in global modeling frameworks.
  • Rannik, Ullar; Zhou, Luxi; Zhou, Putian; Gierens, Rosa; Mammarella, Ivan; Sogachev, Andrey; Boy, Michael (2016)
    A 1-D atmospheric boundary layer (ABL) model coupled with a detailed atmospheric chemistry and aerosol dynamical model, the model SOSAA, was used to predict the ABL and detailed aerosol population (characterized by the number size distribution) time evolution. The model was applied over a period of 10 days in May 2013 to a pine forest site in southern Finland. The period was characterized by frequent new particle formation events and simultaneous intensive aerosol transformation. The aim of the study was to analyze and quantify the role of aerosol and ABL dynamics in the vertical transport of aerosols. It was of particular interest to what extent the fluxes above the canopy deviate from the particle dry deposition on the canopy foliage due to the above-mentioned processes. The model simulations revealed that the particle concentration change due to aerosol dynamics frequently exceeded the effect of particle deposition by even an order of magnitude or more. The impact was, however, strongly dependent on particle size and time. In spite of the fact that the timescale of turbulent transfer inside the canopy is much smaller than the timescales of aerosol dynamics and dry deposition, leading us to assume well-mixed properties of air, the fluxes at the canopy top frequently deviated from deposition inside the forest. This was due to transformation of aerosol concentration throughout the ABL and resulting complicated pattern of vertical transport. Therefore we argue that the comparison of timescales of aerosol dynamics and deposition defined for the processes below the flux measurement level do not unambiguously describe the importance of aerosol dynamics for vertical transport above the canopy. We conclude that under dynamical conditions reported in the current study the micrometeorological particle flux measurements can significantly deviate from the dry deposition into the canopy. The deviation can be systematic for certain size ranges so that the time-averaged particle fluxes can be also biased with respect to deposition sink.
  • Massoli, Paola; Stark, Harald; Canagaratna, Manjula R.; Krechmer, Jordan E.; Xu, Lu; Ng, Nga L.; Mauldin, Roy L.; Yan, Chao; Kimmel, Joel; Misztal, Pawel K.; Jimenez, Jose L.; Jayne, John T.; Worsnop, Douglas R. (2018)
    We present measurements of highly oxidized multifunctional molecules (HOMs) detected in the gas phase using a high-resolution time-of flight chemical ionization mass spectrometer with nitrate reagent ion (NO3- CIMS). The measurements took place during the 2013 Southern Oxidant and Aerosol Study (SOAS 2013) at a forest site in Alabama, where emissions were dominated by biogenic volatile organic compounds (BVOCs). Primary BVOC emissions were represented by isoprene mixed with various terpenes, making it a unique sampling location compared to previous NO3- CIMS deployments in monoterpene-dominated environments. During SOAS 2013, the NO3- CIMS detected HOMs with oxygen-to-carbon (O:C) ratios between 0.5 and 1.4 originating from both isoprene (C-5) and monoterpenes (C-10) as well as hundreds of additional HOMs with carbon numbers between C-3 and C-20. We used positive matrix factorization (PMF) to deconvolve the complex data set and extract information about classes of HOMs with similar temporal trends. This analysis revealed three isoprene-dominated and three monoterpene-dominated PMF factors. We observed significant amounts of isoprene- and monoterpene-derived organic nitrates (ONs) in most factors. The abundant presence of ONs was consistent with previous studies that have highlighted the importance of NOx-driven chemistry at the site. One of the isoprene-dominated factors had a strong correlation with SO2 plumes likely advected from nearby coal-fired power plants and was dominated by an isoprene derived ON (C5H10N2O8). These results indicate that anthropogenic emissions played a significant role in the formation of low volatility compounds from BVOC emissions in the region.
  • Hemmilä, Marja; Hellén, Heidi; Virkkula, Aki; Makkonen, Ulla; Praplan, Arnaud P.; Kontkanen, Jenni; Ahonen, Lauri; Kulmala, Markku; Hakola, Hannele (2018)
    We measured amines in boreal forest air in Finland both in gas and particle phases with 1 h time resolution using an online ion chromatograph (instrument for Measuring AeRosols and Gases in Ambient Air - MARGA) connected to an electrospray ionization quadrupole mass spectrometer (MS). The developed MARGA-MS method was able to separate and detect seven different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA), and butylamine (BA). The detection limits of the method for amines were low (0.2-3.1 ng m(-3)), the accuracy of ICMS analysis was 11-37 %, and the precision 10-15 %. The proper measurements in the boreal forest covered about 8 weeks between March and December 2015. The amines were found to be an inhomogeneous group of compounds, showing different seasonal and diurnal variability. Total MMA (MMA(tot)) peaked together with the sum of ammonia and ammonium ions already in March. In March, monthly means for MMA were 90 %, gas-phase DMA correlated well with 1.1-2 nm particle number concentration (R-2 = 0.63) suggesting that it participates in atmospheric clustering. EA concentrations were low all the time. Its July means were <0.36 and 0.4 +/- 0.4 ng m(-3) in gas and aerosol phases, respectively, but individual concentration data correlated well with monoterpene concentrations in July. Monthly means of PA and BA were below detection limits at all times.
  • Groess, Johannes; Hamed, Amar; Sonntag, Andre; Spindler, Gerald; Manninen, Hanna Elina; Nieminen, Tuomo; Kulmala, Markku; Horrak, Urmas; Plass-Dülmer, Christian; Wiedensohler, Alfred; Birmili, Wolfram (2018)
    This paper revisits the atmospheric new particle formation (NPF) process in the polluted Central European troposphere, focusing on the connection with gas-phase precursors and meteorological parameters. Observations were made at the research station Melpitz (former East Germany) between 2008 and 2011 involving a neutral cluster and air ion spectrometer (NAIS). Particle formation events were classified by a new automated method based on the convolution integral of particle number concentration in the diameter interval 2-20 nm. To study the relevance of gaseous sulfuric acid as a precursor for nucleation, a proxy was derived on the basis of direct measurements during a 1-month campaign in May 2008. As a major result, the number concentration of freshly produced particles correlated significantly with the concentration of sulfur dioxide as the main precursor of sulfuric acid. The condensation sink, a factor potentially inhibiting NPF events, played a subordinate role only. The same held for experimentally determined ammonia concentrations. The analysis of meteorological parameters confirmed the absolute need for solar radiation to induce NPF events and demonstrated the presence of significant turbu-lence during those events. Due to its tight correlation with solar radiation, however, an independent effect of turbulence for NPF could not be established. Based on the diurnal evolution of aerosol, gas-phase, and meteorological parameters near the ground, we further conclude that the particle formation process is likely to start in elevated parts of the boundary layer rather than near ground level.
  • Chu, Biwu; Kerminen, Veli-Matti; Bianchi, Federico; Yan, Chao; Petäjä, Tuukka; Kulmala, Markku (2019)
    New particle formation (NPF) studies in China were summarized comprehensively in this paper. NPF frequency, formation rate, and particle growth rate were closely compared among the observations carried out at different types of sites in different regions of China in different seasons, with the aim of exploring the nucleation and particle growth mechanisms. The interactions between air pollution and NPF are discussed, emphasizing the properties of NPF under heavy pollution conditions. The current understanding of NPF cannot fully explain the frequent occurrence of NPF at high aerosol loadings in China, and possible reasons for this phenomenon are proposed. The effects of NPF and some aspects of NPF research requiring further investigation are also summarized in this paper.
  • Sipilä, M.; Sarnela, N.; Jokinen, T.; Junninen, H.; Hakala, J.; Rissanen, M. P.; Praplan, A.; Simon, M.; Kürten, A.; Bianchi, F.; Dommen, J.; Curtius, J.; Petäjä, T.; Worsnop, D.R. (2015)
    Atmospheric amines may play a crucial role in formation of new aerosol particles via nucleation with sulfuric acid. Recent studies have revealed that concentrations below 1 pptV can significantly promote nucleation of sulfuric acid particles. While sulfuric acid detection is relatively straightforward, no amine measurements to date have been able to reach the critical sub-pptV concentration range and atmospheric amine concentrations are in general poorly characterized. In this work we present a proof-of-concept of an instrument capable of detecting dimethyl amine (DMA) with concentrations even down to 70 ppqV (parts per quadrillion, 0.07 pptV) for a 15 min integration time. Detection of ammonia and amines other than dimethyl amine is discussed. We also report results from the first ambient measurements performed in spring 2013 at a boreal forest site. While minute signals above the signal-to-noise ratio that could be attributed to trimethyl or propyl amine were observed, DMA concentration never exceeded the detection threshold of ambient measurements (150 ppqV), thereby questioning, though not excluding, the role of DMA in nucleation at this location.
  • Zhou, Putian; Ganzeveld, Laurens; Taipale, Ditte; Rannik, Ullar; Rantala, Pekka; Rissanen, Matti Petteri; Chen, Dean; Boy, Michael (2017)
    A multilayer gas dry deposition model has been developed and implemented into a one-dimensional chemical transport model SOSAA (model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to calculate the dry deposition velocities for all the gas species included in the chemistry scheme. The new model was used to analyse in-canopy sources and sinks, including gas emissions, chemical production and loss, dry deposition, and turbulent transport of 12 featured biogenic volatile organic compounds (BVOCs) or groups of BVOCs (e.g. monoterpenes, isoprene+2-methyl-3-buten-2-ol (MBO), sesquiterpenes, and oxidation products of mono-and sesquiterpenes) in July 2010 at the boreal forest site SMEAR II (Station for Measuring Ecosystem-Atmosphere Relations). According to the significance of modelled monthly-averaged individual source and sink terms inside the canopy, the selected BVOCs were classified into five categories: 1. Most of emitted gases are transported out of the canopy (monoterpenes, isoprene + MBO). 2. Chemical reactions remove a significant portion of emitted gases (sesquiterpenes). 3. Bidirectional fluxes occur since both emission and dry deposition are crucial for the in-canopy concentration tendency (acetaldehyde, methanol, acetone, formaldehyde). 4. Gases removed by deposition inside the canopy are compensated for by the gases transported from above the canopy (acetol, pinic acid, beta-caryophyllene's oxidation product BCSOZOH). 5. The chemical production is comparable to the sink by deposition (isoprene's oxidation products ISOP34OOH and ISOP34NO3). Most of the simulated sources and sinks were located above about 0.2 h(c) (canopy height) for oxidation products and above about 0.4 h(c) for emitted species except formaldehyde. In addition, soil deposition (including deposition onto understorey vegetation) contributed 11-61% to the overall in-canopy deposition. The emission sources peaked at about 0.8-0.9 h(c), which was higher than 0.6 h(c) where the maximum of dry deposition onto overstorey vegetation was located. This study provided a method to enable the quantification of the exchange between atmosphere and biosphere for numerous BVOCs, which could be applied in large-scale models in future. With this more explicit canopy exchange modelling system, this study analysed both the temporal and spatial variations in individual in-canopy sources and sinks, as well as their combined effects on driving BVOC exchange. In this study 12 featured BVOCs or BVOC groups were analysed. Other compounds could also be investigated similarly by being classified into these five categories.
  • Sporre, Moa K.; Blichner, Sara M.; Karset, Inger H. H.; Makkonen, Risto; Berntsen, Terje K. (2019)
    Both higher temperatures and increased CO2 concentrations are (separately) expected to increase the emissions of biogenic volatile organic compounds (BVOCs). This has been proposed to initiate negative climate feedback mechanisms through increased formation of secondary organic aerosol (SOA). More SOA can make the clouds more reflective, which can provide a cooling. Furthermore, the increase in SOA formation has also been proposed to lead to increased aerosol scattering, resulting in an increase in diffuse radiation. This could boost gross primary production (GPP) and further increase BVOC emissions. In this study, we have used the Norwegian Earth System Model (NorESM) to investigate both these feedback mechanisms. Three sets of experiments were set up to quantify the feedback with respect to (1) doubling the CO2, (2) increasing temperatures corresponding to a doubling of CO2 and (3) the combined effect of both doubling CO2 and a warmer climate. For each of these experiments, we ran two simulations, with identical setups, except for the BVOC emissions. One simulation was run with interactive BVOC emissions, allowing the BVOC emissions to respond to changes in CO2 and/or climate. In the other simulation, the BVOC emissions were fixed at present-day conditions, essentially turning the feedback off. The comparison of these two simulations enables us to investigate each step along the feedback as well as estimate their overall relevance for the future climate. We find that the BVOC feedback can have a significant impact on the climate. The annual global BVOC emissions are up to 63 % higher when the feedback is turned on compared to when the feedback is turned off, with the largest response when both CO2 and climate are changed. The higher BVOC levels lead to the formation of more SOA mass (max 53 %) and result in more particles through increased new particle formation as well as larger particles through increased condensation. The corresponding changes in the cloud properties lead to a -0.43 W m(-2) stronger net cloud forcing. This effect becomes about 50 % stronger when the model is run with reduced anthropogenic aerosol emissions, indicating that the feedback will become even more important as we decrease aerosol and precursor emissions. We do not find a boost in GPP due to increased aerosol scattering on a global scale. Instead, the fate of the GPP seems to be controlled by the BVOC effects on the clouds. However, the higher aerosol scattering associated with the higher BVOC emissions is found to also contribute with a potentially important enhanced negative direct forcing (-0.06 W m(-2)). The global total aerosol forcing associated with the feedback is -0.49 W m(-2), indicating that it has the potential to offset about 13 % of the forcing associated with a doubling of CO2.
  • Gordon, Hamish; Kirkby, Jasper; Baltensperger, Urs; Bianchi, Federico; Breitenlechner, Martin; Curtius, Joachim; Dias, Antonio; Dommen, Josef; Donahue, Neil M.; Dunne, Eimear M.; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C.; Frege, Carla; Fuchs, Claudia; Hansel, Armin; Hoyle, Christopher R.; Kulmala, Markku; Kurten, Andreas; Lehtipalo, Katrianne; Makhmutov, Vladimir; Molteni, Ugo; Rissanen, Matti P.; Stozkhov, Yuri; Trostl, Jasmin; Tsagkogeorgas, Georgios; Wagner, Robert; Williamson, Christina; Wimmer, Daniela; Winkler, Paul M.; Yan, Chao; Carslaw, Ken S. (2017)
    New particle formation has been estimated to produce around half of cloud-forming particles in the present-day atmosphere, via gas-to-particle conversion. Here we assess the importance of new particle formation (NPF) for both the present-day and the preindustrial atmospheres. We use a global aerosol model with parametrizations of NPF from previously published CLOUD chamber experiments involving sulfuric acid, ammonia, organic molecules, and ions. We find that NPF produces around 67% of cloud condensation nuclei at 0.2% supersaturation (CCN0.2%) at the level of low clouds in the preindustrial atmosphere (estimated uncertainty range 45-84%) and 54% in the present day (estimated uncertainty range 38-66%). Concerning causes, we find that the importance of biogenic volatile organic compounds (BVOCs) in NPF and CCN formation is greater than previously thought. Removing BVOCs and hence all secondary organic aerosol from our model reduces low-cloud-level CCN concentrations at 0.2% supersaturation by 26% in the present-day atmosphere and 41% in the preindustrial. Around three quarters of this reduction is due to the tiny fraction of the oxidation products of BVOCs that have sufficiently low volatility to be involved in NPF and early growth. Furthermore, we estimate that 40% of preindustrial CCN0.2% are formed via ion-induced NPF, compared with 27% in the present day, although we caution that the ion-induced fraction of NPF involving BVOCs is poorly measured at present. Our model suggests that the effect of changes in cosmic ray intensity on CCN is small and unlikely to be comparable to the effect of large variations in natural primary aerosol emissions. Plain Language Summary New particle formation in the atmosphere is the process by which gas molecules collide and stick together to form atmospheric aerosol particles. Aerosols act as seeds for cloud droplets, so the concentration of aerosols in the atmosphere affects the properties of clouds. It is important to understand how aerosols affect clouds because they reflect a lot of incoming solar radiation away from Earth's surface, so changes in cloud properties can affect the climate. Before the Industrial Revolution, aerosol concentrations were significantly lower than they are today. In this article, we show using global model simulations that new particle formation was a more important mechanism for aerosol production than it is now. We also study the importance of gases emitted by vegetation, and of atmospheric ions made by radon gas or cosmic rays, in preindustrial aerosol formation. We find that the contribution of ions and vegetation to new particle formation was also greater in the preindustrial period than it is today. However, the effect on particle formation of variations in ion concentration due to changes in the intensity of cosmic rays reaching Earth was small.
  • Hirvonen, Viivi; Myllys, Nanna; Kurtén, Theo; Elm, Jonas (2018)
    The role of covalently bound dimer formation is studied using highlevel quantum chemical methods. Reaction free energy profiles for dimer formation between common oxygen-containing functional groups are calculated, and based on the Gibbs free energy differences between transition states and reactants, we show that none of the studied two-component gas-phase reactions are kinetically feasible at 298.15 K and 1 atm. Therefore, the catalyzing effect of water, base, or acid molecules is calculated, and sulfuric acid is identified to lower the activation free energies significantly. We find that the reactions yielding hemiacetal, peroxyhemiacetal, alpha-hydroxyester, and geminal diol products occur with activation free energies of less than 10 kcal/mol with sulfuric acid as a catalyst, indicating that these reactions could potentially take place on the surface of sulfuric acid clusters. Additionally, the formed dimer products bind stronger onto the pre-existing cluster than the corresponding reagent monomers do. This implies that covalent dimerization reactions stabilize the existing cluster thermodynamically and make it less likely to evaporate. However, the studied small organic compounds, which contain only one functional group, not able to form dimer are products that are stable against evaporation at atmospheric conditions. Calculations of dimer formation onto a cluster surface and the clustering ability of dimer products should be extended to large terpene oxidation products in order to estimate the real atmospheric significance.
  • Liu, Ling; Kupiainen-Maatta, Oona; Zhang, Haijie; Li, Hao; Zhong, Jie; Kurten, Theo; Vehkamaki, Hanna; Zhang, Shaowen; Zhang, Yunhong; Ge, Maofa; Zhang, Xiuhui; Li, Zesheng (2018)
    The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with di↵erent reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acids, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reaction using Density Functional Theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. In atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, andthe product can further participate in the clustering process. The di↵erences in cluster structures and properties induced by the hydration reaction lead to significant di↵erences in cluster formation rates and pathways at relatively low temperatures.
  • Valadbeigi, Younes; Kurten, Theo (2019)
    HClO4 is an important catalyst in organic chemistry, and also acts as a reservoir or sink species in atmospheric chlorine chemistry. In this study, we computationally investigate the interactions of Bronsted (H2SO4, HClO4, HNO3) and Lewis acids (BH3, BF3, BCl3, BBr3, B(OH)(3)) with HClO4 using the omega B97xD method and the aug-cc-pVDZ basis set. Different isomers of clusters with up to 4 molecules (tetramer) were optimized, and the most stable structures were determined. The enthalpies, Delta H, and Gibbs free energies, Delta G, of cluster formation were calculated in the gas phase at 298 K. Atoms in molecules (AIM) calculations find B-O bond critical points only in the (BH3)(n)HClO4 clusters, while formation of other clusters was based on hydrogen bonding interactions. (H2SO4)HClO4 and (B(OH)(3))HClO4, with formation enthalpies of -14.1 and -12.0 kcal mol(-1), were the most stable, and (BCl3)HClO4 with a formation enthalpy of -2.9 kcal mol(-1), was the least stable cluster among the dimers. Clustering of the Lewis and Bronsted acids with HClO4 enhanced its acidity, so that clustering of four HClO4 molecules and formation of (HClO4)(4) increases the acidity of HClO4 by about 35 kcal mol(-1). The most acidic dimer cluster found in the study was (BBr3)HClO4, with Delta H-acid of 275 kcal mol(-1); 26 kcal mol(-1) stronger than that of the HClO4 monomer.
  • Kulmala, Markku; Nieminen, Tuomo; Nikandrova, Anna; Lehtipalo, Katrianne; Manninen, Hanna E.; Kajos, Maija K.; Kolari, Pasi; Lauri, Antti; Petaja, Tuukka; Krejci, Radovan; Hansson, Hans-Christen; Swietlicki, Erik; Lindroth, Anders; Christensen, Torben R.; Arneth, Almut; Hari, Pertti; Back, Jaana; Vesala, Timo; Kerminen, Veli-Matti (2014)
  • Hao, Liqing; Garmash, Olga; Ehn, Mikael; Miettinen, Pasi; Massoli, Paola; Mikkonen, Santtu; Jokinen, Tuija; Roldin, Pontus; Aalto, Pasi; Yli-Juuti, Taina; Joutsensaari, Jorma; Petäjä, Tuukka; Kulmala, Markku; Lehtinen, Kari E. J.; Worsnop, Douglas R.; Virtanen, Annele (2018)
    Characterizing aerosol chemical composition in response to meteorological changes and atmospheric chemistry is important to gain insights into new particle formation mechanisms. A BAECC (Biogenic Aerosols - Effects on Clouds and Climate) campaign was conducted during the spring 2014 at the SMEAR II station (Station for Measuring Forest Ecosystem-Aerosol Relations) in Finland. The particles were characterized by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). A PBL (planetary boundary layer) dilution model was developed to assist interpreting the measurement results. Right before nucleation events, the mass concentrations of organic and sulfate aerosol species were both decreased rapidly along with the growth of PBL heights. However, the mass fraction of sulfate aerosol of the total aerosol mass was increased, in contrast to a decrease for the organic mass fraction. Meanwhile, an increase in LVOOA (low-volatility oxygenated organic aerosol) mass fraction of the total organic mass was observed, in distinct comparison to a reduction of SVOOA (semi-volatile OOA) mass fraction. Our results demonstrate that, at the beginning of nucleation events, the observed sulfate aerosol mass was mainly driven by vertical turbulent mixing of sulfate-rich aerosols between the residual layer and the newly formed boundary layer, while the condensation of sulfuric acid (SA) played a minor role in interpreting the measured sulfate mass concentration. For the measured organic aerosols, their temporal profiles were mainly driven by dilution from PBL development, organic aerosol mixing in different boundary layers and/or partitioning of organic vapors, but accurate measurements of organic vapor concentrations and characterization on the spatial aerosol chemical composition are required. In general, the observed aerosol particles by AMS are subjected to joint effects of PBL dilution, atmospheric chemistry and aerosol mixing in different boundary layers. During aerosol growth periods in the nighttime, the mass concentrations of organic aerosols and organic nitrate aerosols were both increased. The increase in SVOOA mass correlated well with the calculated increase in condensed HOMs' (highly oxygenated organic molecules) mass. To our knowledge, our results are the first atmospheric observations showing a connection between increase in SVOOA and condensed HOMs during the nighttime.
  • Zieger, P.; Weingartner, E.; Henzing, J.; Moerman, M.; de Leeuw, G.; Mikkilä, Jyri; Ehn, Mikael; Petäjä, Tuukka; Clemer, K.; van Roozendael, M.; Yilmaz, S.; Friess, U.; Irie, H.; Wagner, T.; Shaiganfar, R.; Beirle, S.; Apituley, A.; Wilson, K.; Baltensperger, U. (2011)
  • Paasonen, Pauli; Peltola, Maija; Kontkanen, Jenni; Junninen, Heikki; Kerminen, Veli-Matti; Kulmala, Markku (2018)
    Growth of aerosol particles to sizes at which they can act as cloud condensation nuclei (CCN) is a crucial factor in estimating the current and future impacts of aerosol-cloud-climate interactions. Growth rates (GRs) are typically determined for particles with diameters (d(P)) smaller than 40 nm immediately after a regional new particle formation (NPF) event. These growth rates are often taken as representatives for the particle growth to CCN sizes (d(P) > 50-100 nm). In modelling frameworks, the concentration of the condensable vapours causing the growth is typically calculated with steady state assumptions, where the condensation sink (CS) is the only loss term for the vapours. Additionally, the growth to CCN sizes is represented with the condensation of extremely low-volatility vapours and gas-particle partitioning of semi-volatile vapours. Here, we use a novel automatic method to determine growth rates from below 10 nm to hundreds of nanometres from a 20-year-long particle size distribution (PSD) data set in boreal forest. With this method, we are able to detect growth rates also at times other than immediately after a NPF event. We show that the GR increases with an increasing oxidation rate of monoterpenes, which is closely coupled with the ambient temperature. Based on our analysis, the oxidation reactions of monoterpenes with ozone, hydroxyl radical and nitrate radical all are capable of producing vapours that contribute to the particle growth in the studied size ranges. We find that GR increases with particle diameter, resulting in up to 3-fold increases in GRs for particles with d(P) similar to 100 nm in comparison to those with d(P) similar to 10 nm. We use a single particle model to show that this increase in GR can be explained with aerosol-phase reactions, in which semi-volatile vapours form non-volatile dimers. Finally, our analysis reveals that the GR of particles with d(P) <100 nm is not limited by the condensation sink, even though the GR of larger particles is. Our findings suggest that in the boreal continental environment, the formation of CCN from NPF or sub-100 nm emissions is more effective than previously thought and that the formation of CCN is not as strongly self-limiting a process as the previous estimates have suggested.