Browsing by Subject "PARTICLE FORMATION"

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  • Dal Maso, M.; Liao, L.; Wildt, J.; Kiendler-Scharr, A.; Kleist, E.; Tillmann, R.; Sipilä, M.; Hakala, J.; Lehtipalo, K.; Ehn, M.; Kerminen, V. -M.; Kulmala, M.; Worsnop, D.; Mentel, T. (2016)
    Aerosol formation from biogenic and anthropogenic precursor trace gases in continental background areas affects climate via altering the amount of available cloud condensation nuclei. Significant uncertainty still exists regarding the agents controlling the formation of aerosol nanoparticles. We have performed experiments in the Julich plant-atmosphere simulation chamber with instrumentation for the detection of sulfuric acid and nanoparticles, and present the first simultaneous chamber observations of nanoparticles, sulfuric acid, and realistic levels and mixtures of biogenic volatile compounds (BVOCs). We present direct laboratory observations of nanoparticle formation from sulfuric acid and realistic BVOC precursor vapour mixtures performed at atmospherically relevant concentration levels. We directly measured particle formation rates separately from particle growth rates. From this, we established that in our experiments, the formation rate was proportional to the product of sulfuric acid and biogenic VOC emission strength. The formation rates were consistent with a mechanism in which nucleating BVOC oxidation products are rapidly formed and activate with sulfuric acid. The growth rate of nanoparticles immediately after birth was best correlated with estimated products resulting from BVOC ozonolysis.
  • Kupiainen-Määttä, Oona (2016)
    Evaporation rates of small negatively charged sulfuric acid-ammonia clusters are determined by combining detailed cluster formation simulations with cluster distributions measured in the CLOUD experiment at CERN. The analysis is performed by varying the evaporation rates with Markov chain Monte Carlo (MCMC), running cluster formation simulations with each new set of evaporation rates and comparing the obtained cluster distributions to the measurements. In a second set of simulations, the fragmentation of clusters in the mass spectrometer due to energetic collisions is studied by treating also the fragmentation probabilities as unknown parameters and varying them with MCMC. This second set of simulations results in a better fit to the experimental data, suggesting that a large fraction of the observed HSO4- and HSO4-center dot H2SO4 signals may result from fragmentation of larger clusters, most importantly the HSO4-center dot(H2SO4)(2) trimer.
  • Kirkevag, Alf; Grini, Alf; Olivie, Dirk; Seland, Oyvind; Alterskjaer, Kari; Hummel, Matthias; Karset, Inger H. H.; Lewinschal, Anna; Liu, Xiaohong; Makkonen, Risto; Bethke, Ingo; Griesfeller, Jan; Schulz, Michael; Iversen, Trond (2018)
    We document model updates and present and discuss modeling and validation results from a further developed production-tagged aerosol module, OsloAero5.3, for use in Earth system models. The aerosol module has in this study been implemented and applied in CAM5.3-Oslo. This model is based on CAM5.3-CESM1.2 and its own predecessor model version CAM4-Oslo. OsloAero5.3 has improved treatment of emissions, aerosol chemistry, particle life cycle, and aerosol-cloud interactions compared to its predecessor OsloAero4.0 in CAM4-Oslo. The main new features consist of improved aerosol sources; the module now explicitly accounts for aerosol particle nucleation and secondary organic aerosol production, with new emissions schemes also for sea salt, dimethyl sulfide (DMS), and marine primary organics. Mineral dust emissions are updated as well, adopting the formulation of CESM1.2. The improved model representation of aerosol-cloud interactions now resolves heterogeneous ice nucleation based on black carbon (BC) and mineral dust calculated by the model and treats the activation of cloud condensation nuclei (CCN) as in CAM5.3. Compared to OsloAero4.0 in CAM4-Oslo, the black carbon (BC) mass concentrations are less excessive aloft, with a better fit to observations. Near-surface mass concentrations of BC and sea salt aerosols are also less biased, while sulfate and mineral dust are slightly more biased. Although appearing quite similar for CAM5.3-Oslo and CAM4-Oslo, the validation results for organic matter (OM) are inconclusive, since both of the respective versions of OsloAero are equipped with a limited number of OM tracers for the sake of computational efficiency. Any information about the assumed mass ratios of OM to organic carbon (OC) for different types of OM sources is lost in the transport module. Assuming that observed OC concentrations scaled by 1.4 are representative for the modeled OM concentrations, CAM5.3-Oslo with OsloAero5.3 is slightly inferior for the very sparsely available observation data. Comparing clear-sky column-integrated optical properties with data from ground-based remote sensing, we find a negative bias in optical depth globally; however, it is not as strong as in CAM4-Oslo, but has positive biases in some areas typically dominated by mineral dust emissions. Aerosol absorption has a larger negative bias than the optical depth globally. This is reflected in a lower positive bias in areas where mineral dust is the main contributor to absorption. Globally, the low bias in absorption is smaller than in CAM4-Oslo. The Angstrom parameter exhibits small biases both globally and regionally, suggesting that the aerosol particle sizes are reasonably well represented. Cloud-top droplet number concentrations over oceans are generally underestimated compared to satellite retrievals, but seem to be overestimated downwind of major emissions of dust and biomass burning sources. Finally, we find small changes in direct radiative forcing at the top of the atmosphere, while the cloud radiative forcing due to anthropogenic aerosols is now more negative than in CAM4-Oslo, being on the strong side compared to the multi-model estimate in IPCC AR5. Although not all validation results in this study show improvement for the present CAM5.3-Oslo version, the extended and updated aerosol module OsloAero5.3 is more advanced and applicable than its predecessor OsloAero4.0, as it includes new parameterizations that more readily facilitate sensitivity and process studies and use in climate and Earth system model studies in general.
  • Lu, Yiqun; Yan, Chao; Fu, Yueyun; Chen, Yan; Liu, Yiliang; Yang, Gan; Wang, Yuwei; Bianchi, Federico; Chu, Biwu; Zhou, Ying; Yin, Rujing; Baalbaki, Rima; Garmash, Olga; Deng, Chenjuan; Wang, Weigang; Liu, Yongchun; Petäjä, Tuukka; Kerminen, Veli-Matti; Jiang, Jingkun; Kulmala, Markku; Wang, Lin (2019)
    Gaseous sulfuric acid (H2SO4) is known as one of the key precursors for atmospheric new particle formation (NPF) processes, but its measurement remains challenging. Therefore, a proxy method that is able to derive gaseous sulfuric acid concentrations from parameters that can be measured relatively easily and accurately is highly desirable for the atmospheric chemistry community. Although such methods are available for clean atmospheric environments, a proxy that works well in a polluted atmosphere, such as that found in Chinese megacities, is yet to be developed. In this study, the gaseous sulfuric acid concentration was measured in February-March 2018, in urban Beijing using a nitrate based -long time-of-flight chemical ionization mass spectrometer (LToF-CIMS). A number of atmospheric parameters were recorded concurrently including the ultraviolet radiation B (UVB) intensity, the concentrations of O-3, NOx (sum of NO and NO2), SO2, and HONO, and aerosol particle number size distributions. A proxy for atmospheric daytime gaseous sulfuric acid concentration was derived via a statistical analysis method using the UVB intensity, [SO2], the condensation sink (CS), [O-3], and [HONO] (or [NOx]) as the predictor variables, where square brackets denote the concentrations of the corresponding species. In this proxy method, we considered the formation of gaseous sulfuric acid from reactions of SO2 and OH radicals during the daytime, and the loss of gaseous sulfuric acid due to its condensation onto the preexisting particles. In addition, we explored the formation of OH radicals from the conventional gas-phase photochemistry using O-3 as a proxy and from the photolysis of HONO using HONO (and subsequently NOx) as a proxy. Our results showed that the UVB intensity and [SO2] are dominant factors in the production of gaseous sulfuric acid, and that the simplest proxy could be constructed with the UVB intensity and [SO2] alone. When the OH radical production from both homogenously and heterogeneously formed precursors were considered, the relative errors were reduced by up to 20 %.
  • Berndt, Torsten; Mender, Bernhard; Scholz, Wiebke; Fischer, Lukas; Herrmann, Hartmut; Kulmala, Markku; Hansel, Armin (2018)
    alpha-Pinene (C10H16) represents one of the most important biogenic emissions in the atmosphere. Its oxidation products can significantly contribute to the secondary organic aerosol (SOA) formation. Here, we report on the formation mechanism of C-19 and C-20 accretion products from alpha-pinene oxidation, which are believed to be efficient SOA precursors. Measurements have been performed in a free-jet flow system. Detection of RO2 radicals and accretion products was carried out by recent mass spectrometric techniques using different ionization schemes. Observed C-10-RO2 radicals from alpha-pinene ozonolysis were O,O-C10H15(O-2)(x)O-2 with x = 0, 1, 2, 3 and from the OH radical reaction HO-C10H16(O-2)(alpha)O-2 with alpha = 0, 1, 2. All detected C 20 accretion products can be explained via the accretion reaction RO2 + R'O-2 -> ROOR' + O-2 starting from the measured C-10-RO2 radicals. We speculate that C-19 accretion products are formed in an analogous way assuming CH2O elimination. Addition of isoprene (C5H8), producing C-5-RO2 radicals, leads to C-15 accretion products formed via cross-reactions with C-10-RO2 radicals. This process is competing with the formation of C-19/C-20 products from the pure alpha-pinene oxidation. A similar behavior has been observed for ethylene additives that form C-12 accretion products. In the atmosphere, a complex accretion product spectrum from self- and cross-reactions of available RO2 radicals can be expected. Modeling atmospheric conditions revealed that C-19/C-20 product formation is only reduced by a factor of 1.2 or 3.6 in isoprene-dominated environments assuming a 2- or 15-fold isoprene concentration over alpha-pinene, respectively, as present in different forested areas.
  • Xavier, Carlton; Rusanen, Anton; Zhou, Putian; Chen, Dean; Pichelstorfer, Lukas; Pontus, Roldin; Boy, Michael (2019)
    In this study we modeled secondary organic aerosol (SOA) mass loadings from the oxidation (by O-3, OH and NO3) of five representative biogenic volatile organic compounds (BVOCs): isoprene, endocyclic bond-containing monoterpenes (alpha-pinene and limonene), exocyclic double-bond compound (beta-pinene) and a sesquiterpene (beta-caryophyllene). The simulations were designed to replicate an idealized smog chamber and oxidative flow reactors (OFRs). The Master Chemical Mechanism (MCM) together with the peroxy radical autoxidation mechanism (PRAM) were used to simulate the gas-phase chemistry. The aim of this study was to compare the potency of MCM and MCM + PRAM in predicting SOA formation. SOA yields were in good agreement with experimental values for chamber simulations when MCM + PRAM was applied, while a stand-alone MCM underpredicted the SOA yields. Compared to experimental yields, the OFR simulations using MCM + PRAM yields were in good agreement for BVOCs oxidized by both O-3 and OH. On the other hand, a stand-alone MCM underpredicted the SOA mass yields. SOA yields increased with decreasing temperatures and NO concentrations and vice versa. This highlights the limitations posed when using fixed SOA yields in a majority of global and regional models. Few compounds that play a crucial role (> 95% of mass load) in contributing to SOA mass increase (using MCM + PRAM) are identified. The results further emphasized that incorporating PRAM in conjunction with MCM does improve SOA mass yield estimation.
  • Shen, Yicheng; Virkkula, Aki; Ding, Aijun; Wang, Jiaping; Chi, Xuguang; Nie, Wei; Qi, Ximeng; Huang, Xin; Liu, Qiang; Zheng, Longfei; Xu, Zheng; Petäjä, Tuukka; Aalto, Pasi P.; Fu, Congbin; Kulmala, Markku (2018)
    Aerosol optical properties (AOPs) and supporting parameters-particle number size distributions, PM2 : 5 mass concentrations, and the concentrations of trace gases (NOx and NOy) - were measured at SORPES, a regional background station in Nanjing, China from June 2013 to May 2015. The aerosol was highly scattering: the average scattering coefficient was sigma(sp) =403 +/- 314Mm 1, the absorption coefficient sigma(ap) =26 +/- 19Mm 1, and the single-scattering albedo SS Lambda =0.93 +/- 0.03 for green light. The SSA in Nanjing appears to be slightly higher than published values from several other sites in China and elsewhere. The average Angstrom exponent of absorption (AAE) for the wavelength range 370-950 nm was 1.04 and the AAE range was 0.7-1.4. These AAE values can be explained with different amounts of non-absorbing coating on pure black carbon (BC) cores and different core sizes rather than contribution by brown carbon. The AOPs had typical seasonal cycles with high sigma(sp) and sigma(ap) in winter and low ones in summer: the averages were sigma(sp) =544 +/- 422 and sigma(ap) =36 +/- 24Mm 1 in winter and sigma(sp) =342 +/- 281 and sigma(ap) =20 +/- 13Mm 1 in summer. The intensive AOPs had no clear seasonal cycles, the variations in them were rather related to the evolution of pollution episodes. The diurnal cycles of the intensive AOPs were clear and in agreement with the cycle of the particle number size distribution. The diurnal cycle of SSA was similar to that of the air photochemical age, suggesting that the darkest aerosol originated from fresh traffic emissions. A Lagrangian retroplume analysis showed that the potential source areas of high sigma(sp) and sigma(ap) are mainly in eastern China. Synoptic weather phenomena dominated the cycle of AOPs on a temporal scale of 3-7 days. During pollution episodes, modeled boundary layer height decreased, whereas PM2.5 concentrations and sigma(sp) and sigma(ap) typically increased gradually and remained high during several days but decreased faster, sometimes by even more than an order of magnitude within some hours. During the growth phase of the pollution episodes the intensive AOPs evolved clearly. The mass scattering efficiency MSE of PM2.5 grew during the extended pollution episodes from similar to 4 to similar to 6m(2) g(-1) and the mass fraction of BCe decreased from similar to 10 to similar to 3% during the growth phase of the episodes. Particle growth resulted in the backscatter fraction decreasing from more than 0.16 to less than 0.10, SSA growing from less than 0.9 to more than 0.95, and radiative forcing efficiency (RFE) changing from less than -26Wm(-2) to more than 24Wm(-2), which means that the magnitude of RFE decreased. The RFE probability distribution at SORPES was clearly narrower than at a clean background site which is in agreement with a published RFE climatology.
  • 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.
  • Lu, Yiqun; Liu, Ling; Ning, An; Yang, Gan; Liu, Yiliang; Kurten, Theo; Vehkamäki, Hanna; Zhang, Xiuhui; Wang, Lin (2020)
    Sulfuric acid (SA)-dimethylamine (DMA)-H2O cluster formation has been proven to be responsible for a significant part of new particle formation (NPF) in a Chinese megacity. However, the possible involvement of common atmospheric acids in the subsequent growth of SA-DMA clusters remains elusive. We simulated formation and growth of clusters using atmospheric relevant concentrations of SA, DMA, and trifluoroacetic acid (TFA), a commonly observed atmospheric perfluorocarboxylic acid, using Density Functional Theory combined with Atmospheric Cluster Dynamics Code. The presence of TFA leads to complex cluster formation routes and an enhancement of NPF rates by up to 2.3 ([TFA] = 5.0 x 10(6) molecules cm(-3), [SA] = 1.0 x 10(6) molecules cm(-3), and [DMA] = 1.5 x 10(9) molecules cm(-3)). The agreement of (SA)(1)center dot(DMA)(1-2)center dot(TFA)(1) concentrations between simulations and ambient measurements during NPF events validates model predictions and implies that perfluorocarboxylic acids could potentially boost atmospheric SA-DMA NPF rates.
  • Joutsensaari, Jorma; Yli-Pirilä, Pasi; Korhonen, Hannele; Arola, Antti; Blande, James D.; Heijari, Juha; Kivimäenpää, Minna; Mikkonen, S.; Hao, Liging; Miettinen, Pasi; Lyytikainen-Saarenmaa, Päivi; Faiola, C. L.; Laaksonen, Ari; Holopainen, Jarmo K. (2015)
    Boreal forests are a major source of climate-relevant biogenic secondary organic aerosols (SOAs) and will be greatly influenced by increasing temperature. Global warming is predicted to not only increase emissions of reactive biogenic volatile organic compounds (BVOCs) from vegetation directly but also induce large-scale insect outbreaks, which significantly increase emissions of reactive BVOCs. Thus, climate change factors could substantially accelerate the formation of biogenic SOAs in the troposphere. In this study, we have combined results from field and laboratory experiments, satellite observations and global-scale modelling in order to evaluate the effects of insect herbivory and large-scale outbreaks on SOA formation and the Earth's climate. Field measurements demonstrated 11-fold and 20-fold increases in monoterpene and sesquiterpene emissions respectively from damaged trees during a pine sawfly (Neodiprion sertifer) outbreak in eastern Finland. Laboratory chamber experiments showed that feeding by pine weevils (Hylobius abietis) increased VOC emissions from Scots pine and Norway spruce seedlings by 10-50 fold, resulting in 200-1000-fold increases in SOA masses formed via ozonolysis. The influence of insect damage on aerosol concentrations in boreal forests was studied with a global chemical transport model GLOMAP and MODIS satellite observations. Global-scale modelling was performed using a 10-fold increase in monoterpene emission rates and assuming 10% of the boreal forest area was experiencing outbreak. Results showed a clear increase in total particulate mass (local max. 480 %) and cloud condensation nuclei concentrations (45 %). Satellite observations indicated a 2-fold increase in aerosol optical depth over western Canada's pine forests in August during a bark beetle outbreak. These results suggest that more frequent insect outbreaks in a warming climate could result in substantial increase in biogenic SOA formation in the boreal zone and, thus, affect both aerosol direct and indirect forcing of climate at regional scales. The effect of insect outbreaks on VOC emissions and SOA formation should be considered in future climate predictions.
  • 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.
  • Frege, Carla; Bianchi, Federico; Molteni, Ugo; Trostl, Jasmin; Junninen, Heikki; Henne, Stephan; Sipilä, Mikko; Herrmann, Erik; Rossi, Michel J.; Kulmala, Markku; Hoyle, Christopher R.; Baltensperger, Urs; Dommen, Josef (2017)
    The ion composition at high altitude (3454 m a.s.l.) was measured with an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF) during a period of 9 months, from August 2013 to April 2014. The negative mass spectra were dominated by the ions of sulfuric, nitric, malonic, and methanesulfonic acid (MSA) as well as SO5. The most prominent positive ion peaks were from amines. The other cations were mainly organic compounds clustered with a nitrogen-containing ion, which could be either NH4+ or an aminium. Occasionally the positive spectra were characterized by groups of compounds each differing by a methylene group. In the negative spectrum, sulfuric acid was always observed during clear sky conditions following the diurnal cycle of solar irradiation. On many occasions we also saw a high signal of sulfuric acid during nighttime when clusters up to the tetramer were observed. A plausible reason for these events could be evaporation from particles at low relative humidity. A remarkably strong correlation between the signals of SO5 and CH3SO3- was observed for the full measurement period. The presence of these two ions during both the day and the night suggests a non-photochemical channel of formation which is possibly linked to halogen chemistry. Halogenated species, especially Br- and IO3-, were frequently observed in air masses that originated mainly from the Atlantic Ocean and occasionally from continental areas based on back trajectory analyses. We found I2O5 clustered with an ion, a species that was proposed from laboratory and modeling studies. All halogenated ions exhibited an unexpected diurnal behavior with low values during daytime. New particle formation (NPF) events were observed and characterized by (1) highly oxygenated molecules (HOMs) and low sulfuric acid or (2) ammonia-sulfuric acid clusters. We present characteristic spectra for each of these two event types based on 26 nucleation episodes. The mass spectrum of the ammonia-sulfuric acid nucleation event compares very well with laboratory measurements reported from the CLOUD chamber. A source receptor analysis indicates that NPF events at the Jungfraujoch take place within a restricted period of time of 24-48 h after air masses have had contact with the boundary layer. This time frame appears to be crucial to reach an optimal oxidation state and concentration of organic molecules necessary to facilitate nucleation.
  • Fang, Jiaxi; Wang, Yang; Kangasluoma, Juha; Attoui, Michel; Junninen, Heikki; Kulmala, Markku; Petäjä, Tuukka; Biswas, Pratim (2017)
    Few studies reported the formation of Ti-containing clusters in the initial stages of TiO2 flame synthesis. The conversion from synthesis precursor to TiO2 monomers was commonly assumed to take place through global reaction such as thermal decomposition and/or hydrolysis at high temperatures. More recent studies have been able to identify stable intermediates of Ti-containing monomers, most commonly Ti(OH)(4), as the final step before the formation of TiO2. However, no larger Ti-containing cluster formation mechanisms or interactions between these monomers have been tracked. To investigate cluster formation pathways of TiO2 during flame synthesis, Charged clusters were measured in an atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer. TiO2 nanoparticles were synthesized by adding titanium tetraisopropoxide (TTIP) precursor to a premixed CH4/O-2/N-2 flat flame aerosol reactor. Pure TiO2 clusters were not detected by the APi-TOF. Results from measured mass spectra and mass defect plots show that for positively charged clusters, the abstraction of CH2 groups occurs simultaneously with the clustering of larger intermediate organometallic species. For negatively charged clusters, NOx formation pathways in the flame may play a role during the initial stages of TiO2 formation, since a lot of Ti-containing clusters were attached with nitrate-related species. These research findings provide insights on quantum dot synthesis and molecular doping where rapid dilution of the flame synthesized nanoparticles is needed to better control the particle size and chemical composition. The possible influences of and potential artifacts brought by the dilution system on observing the incipient particle formation in flames were also discussed.
  • 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)
  • Iyer, Siddharth; He, Xucheng; Hyttinen, Noora; Kurten, Theo; Rissanen, Matti P. (2017)
    The HO2 radical is an important atmospheric molecule that can potentially influence the termination of autoxidation processes of volatile organic compounds (VOCs) that lead to the formation of highly oxygenated multifunctional compounds (HOMs). In this work, we demonstrate the direct detection of the HO2 radical using an iodide-based chemical ionization mass spectrometer (iodide-CIMS). Expanding on the previously established correlation between molecule-iodide binding enthalpy and iodide-CIMS instrument sensitivity, the experimental detection of the HO2 radical was preceded by the quantum chemical calculation of the HO2*I- cluster (PBE/aug-cc-pVTZ-PP level), which showed a reasonably strong binding enthalpy of 21.60 kcal/mol. Cyclohexene ozonolysis intermediates and closed-shell products were next detected by the iodide-CIMS. The ozone-initiated cyclohexene oxidation mechanism was perturbed by the introduction of the HO2 radical, leading to the formation of closed-shell hydroperoxides. The experimental investigation once again followed the initial computational molecule-iodide binding enthalpy calculations. The quantum chemical calculations were performed at the PBE/aug-cc-pVTZ-PP level for radicals and DLPNO-CCSD(T)/def2-QZVPP//PBE/aug-cc-pVTZ-PP level for the closed-shell products. A comparison between the iodide-CIMS and nitrate-CIMS spectra with identical measurement steps revealed that the iodide-CIMS was able to detect the low-oxidized (O/C ratio 0.5 and 0.66) cyclohexene ozonolysis monomer products more efficiently than nitrate-CIMS. Higher-oxidized monomers (O/C ratio 1 to 1.5) were detected equally well by both methods. An investigation of dimers showed that both iodide- and nitrate-CIMS were able to detect the dimer compositions possibly formed from reactions between the peroxy radical monomers considered in this study. Additionally, iodide-CIMS detected organic ions that were formed by a previously suggested mechanism of dehydroxylation of peroxy acids (and deoxygenation of acyl peroxy radicals) by H2O*I- clusters. These mechanisms were computationally verified.
  • Rondo, L.; Ehrhart, S.; Kuerten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tome, A.; Trostl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J. (2016)
    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (
  • Praplan, A. P.; Schobesberger, S.; Bianchi, F.; Rissanen, M. P.; Ehn, M.; Jokinen, Tuija; Junninen, H.; Adamov, A.; Amorim, A.; Dommen, J.; Duplissy, J.; Hakala, J.; Hansel, A.; Heinritzi, M.; Kangasluoma, J.; Kirkby, J.; Krapf, M.; Kürten, A.; Lehtipalo, K.; Riccobono, F.; Rondo, L.; Sarnela, N.; Simon, M.; Tome, A.; Tröstl, J.; Winkler, P. M.; Williamson, C.; Ye, P.; Curtius, J.; Baltensperger, U.; Donahue, N. M.; Kulmala, Markku; Worsnop, D. R. (2015)
    This study presents the difference between oxidised organic compounds formed by alpha-pinene oxidation under various conditions in the CLOUD environmental chamber: (1) pure ozonolysis (in the presence of hydrogen as hydroxyl radical (OH) scavenger) and (2) OH oxidation (initiated by nitrous acid (HONO) photolysis by ultraviolet light) in the absence of ozone. We discuss results from three Atmospheric Pressure interface Time-of-Flight (APi-TOF) mass spectrometers measuring simultaneously the composition of naturally charged as well as neutral species (via chemical ionisation with nitrate). Natural chemical ionisation takes place in the CLOUD chamber and organic oxidised compounds form clusters with nitrate, bisulfate, bisulfate/sulfuric acid clusters, ammonium, and dimethylaminium, or get protonated. The results from this study show that this process is selective for various oxidised organic compounds with low molar mass and ions, so that in order to obtain a comprehensive picture of the elemental composition of oxidation products and their clustering behaviour, several instruments must be used. We compare oxidation products containing 10 and 20 carbon atoms and show that highly oxidised organic compounds are formed in the early stages of the oxidation.
  • Riva, Matthieu; Rantala, Pekka; Krechmer, Jordan E.; Peräkylä, Otso; Zhang, Yanjun; Heikkinen, Liine; Garmash, Olga; Yan, Chao; Kulmala, Markku; Worsnop, Douglas; Ehn, Mikael (2019)
    The impact of aerosols on climate and air quality remains poorly understood due to multiple factors. One of the current limitations is the incomplete understanding of the contribution of oxygenated products, generated from the gas-phase oxidation of volatile organic compounds (VOCs), to aerosol formation. Indeed, atmospheric gaseous chemical processes yield thousands of (highly) oxygenated species, spanning a wide range of chemical formulas, functional groups and, consequently, volatilities. While recent mass spectrometric developments have allowed extensive on-line detection of a myriad of oxygenated organic species, playing a central role in atmospheric chemistry, the detailed quantification and characterization of this diverse group of compounds remains extremely challenging. To address this challenge, we evaluated the capability of current state-of-the-art mass spectrometers equipped with different chemical ionization sources to detect the oxidation products formed from alpha-Pinene ozonolysis under various conditions. Five different mass spectrometers were deployed simultaneously for a chamber study. Two chemical ionization atmospheric pressure interface time-of-flight mass spectrometers (CI-APi-TOF) with nitrate and amine reagent ion chemistries and an iodide chemical ionization time-of-flight mass spectrometer (TOF-CIMS) were used. Additionally, a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF 8000) and a new "vocus" PTR-TOF were also deployed. In the current study, we compared around 1000 different compounds between each of the five instruments, with the aim of determining which oxygenated VOCs (OVOCs) the different methods were sensitive to and identifying regions where two or more instruments were able to detect species with similar molecular formulae. We utilized a large variability in conditions (including different VOCs, ozone, NOx and OH scavenger concentrations) in our newly constructed atmospheric simulation chamber for a comprehensive correlation analysis between all instruments. This analysis, combined with estimated concentrations for identified molecules in each instrument, yielded both expected and surprising results. As anticipated based on earlier studies, the PTR instruments were the only ones able to measure the precursor VOC, the iodide TOF-CIMS efficiently detected many semi-volatile organic compounds (SVOCs) with three to five oxygen atoms, and the nitrate CI-APi-TOF was mainly sensitive to highly oxygenated organic (O > 5) molecules (HOMs). In addition, the vocus showed good agreement with the iodide TOF-CIMS for the SVOC, including a range of organonitrates. The amine CI-APi-TOF agreed well with the nitrate CI-APi-TOF for HOM dimers. However, the loadings in our experiments caused the amine reagent ion to be considerably depleted, causing nonlinear responses for monomers. This study explores and highlights both benefits and limitations of currently available chemical ionization mass spectrometry instrumentation for characterizing the wide variety of OVOCs in the atmosphere. While specifically shown for the case of alpha-Pinene ozonolysis, we expect our general findings to also be valid for a wide range of other VOC-oxidant systems. As discussed in this study, no single instrument configuration can be deemed better or worse than the others, as the optimal instrument for a particular study ultimately depends on the specific target of the study.