Observations on the first steps of atmospheric particle formation and growth

Atmospheric aerosol particles have a significant impact on air quality, human health and global climate. The climatic effects of secondary aerosol are currently among the largest uncertainties limiting the scientific understanding of future and past climate changes. To better estimate the climatic importance of secondary aerosol particles, detailed information on atmospheric particle formation mechanisms and the vapours forming the aerosol is required. In this thesis we studied these issues by applying novel instrumentation in a boreal forest to obtain direct information on the very first steps of atmospheric nucleation and particle growth. Additionally, we used detailed laboratory experiments and process modelling to determine condensational growth properties, such as saturation vapour pressures, of dicarboxylic acids, which are organic acids often found in atmospheric samples. Based on our studies, we came to four main conclusions: 1) In the boreal forest region, both sulphurous compounds and organics are needed for secondary particle formation, the previous contributing mainly to particle formation and latter to growth; 2) A persistent pool of molecular clusters, both neutral and charged, is present and participates in atmospheric nucleation processes in boreal forests; 3) Neutral particle formation seems to dominate over ion-mediated mechanisms, at least in the boreal forest boundary layer; 4) The subcooled liquid phase saturation vapour pressures of C3-C9 dicarboxylic acids are of the order of 1e-5 1e-3 Pa at atmospheric temperatures, indicating that a mixed pre-existing particulate phase is required for their condensation in atmospheric conditions. The work presented in this thesis gives tools to better quantify the aerosol source provided by secondary aerosol formation. The results are particularly useful when estimating, for instance, anthropogenic versus biogenic influences and the fractions of secondary aerosol formation explained by neutral or ion-mediated nucleation mechanisms, at least in environments where the average particle formation rates are of the order of some tens of particles per cubic centimeter or lower. However, as the factors driving secondary particle formation are likely to vary depending on the environment, measurements on atmospheric nucleation and particle growth are needed from around the world to be able to better describe the secondary particle formation, and assess its climatic effects on a global scale.Hengittämämme ilma ei koostu pelkästään kaasumolekyyleistä: jokaisessa kuutiosenttimetrissä ilmaa on tyypillisesti tuhansia kiinteitä tai nestemäisiä pienhiukkasia. Nämä ilmakehän aerosolihiukkaset vaikuttavat merkittävästi ilmanlaatuun, ihmisten terveyteen ja maapallon ilmastoon. Hallitustenvälisen ilmastopaneelin (IPCC) viimeisimmän raportin mukaan epävarmuus pienhiukkasten globaaleista ilmastovaikutuksista on suurin ilmastonmuutoksen tieteellistä ymmärtämistä rajoittava yksittäinen tekijä. Jotta arvioita pienhiukkasten vaikutuksia ilmastoon voitaisiin tarkentaa, hiukkasten synty- ja kasvumekanismit sekä niihin ilmakehässä osallistuvat höyryt tulee selvittää. Tässä työssä tutkittiin pienhiukkasten muodostumista tiivistyvistä höyryistä pohjoisissa havumetsissä. Työssä yhtäältä havainnoitiin nanohiukkasten muodostumista ja kasvua vastikään kehitetyillä mittalaitteilla Hyytiälän metsäasemalla Juupajoella. Toisaalta selvitettiin eräiden ilmakehässä tavallisesti esiintyvien orgaanisten happojen, niin sanottujen dikarboksyylihappojen, tiivistymisominaisuuksia laboratoriokokeiden sekä massan- ja lämmönsiirron mallittamisen keinoin. Tutkimuksen neljä tärkeintä johtopäätöstä ovat 1) hiukkasten muodostumiseen pohjoisella havumetsävyöhykkeellä osallistuu sekä pääosin ihmisen toiminnasta peräisin olevia rikkiyhdisteitä että puiden emittoimia orgaanisia höyryjä; 2) ilmakehän hiukkasmuodostuksessa on merkittävä rooli 1-2 nanometrin molekyyliryppäillä, jotka toimivat tiivistymisytiminä höyryille, ja joita näyttäisi olevan ilmassa jatkuvasti; 3) hiukkasmuodostusprosessit ovat pääosin sähköisesti neutraaleja, toisin sanoen kosmisista säteistä ja maaperän radonista peräisin olevan ionisoivan säteilyn merkitys pohjoisten metsien hiukkasmuodostuksessa näyttäisi olevan pieni; 4) dikarboksyylihapot eivät ilmakehän olosuhteissa muodosta sellaisenaan hiukkasia, vaan voivat osallistua vain jo muodostuneiden hiukkasten kasvattamiseen. Tässä tutkimuksessa esitettyjä tuloksia voidaan käyttää arvioitaessa tiivistyvistä höyryistä muodostuneiden pienhiukkasten globaaleja ilmastovaikutuksia sekä esimerkiksi sitä, mikä on ollut ihmisen toiminnan vaikutus ilmakehän hiukkaspitoisuuksiin menneisyydessä ja miten se tulee tulevaisuudessa muuttumaan

Mass Accommodation of Water: Bridging the Gap Between Molecular Dynamics Simulations and Kinetic Condensation Models

The condensational growth of submicrometer aerosol particles to climate relevant sizes is sensitive to their ability to accommodate vapor molecules, which is described by the mass accommodation coefficient. However, the underlying processes are not yet fully understood. We have simulated the mass accommodation and evaporation processes of water using molecular dynamics, and the results are compared to the condensation equations derived from the kinetic gas theory to shed light on the compatibility of the two. Molecular dynamics simulations were performed for a planar TIP4P-Ew water surface at four temperatures in the range 268–300 K as well as two droplets, with radii of 1.92 and 4.14 nm at T = 273.15 K. The evaporation flux from molecular dynamics was found to be in good qualitative agreement with that predicted by the simple kinetic condensation equations. Water droplet growth was also modeled with the kinetic multilayer model KM-GAP of Shiraiwa et al. [ Atmos. Chem. Phys. 2012, 12, 2777]. It was found that, due to the fast transport across the interface, the growth of a pure water droplet is controlled by gas phase diffusion. These facts indicate that the simple kinetic treatment is sufficient in describing pure water condensation and evaporation. The droplet size was found to have minimal effect on the value of the mass accommodation coefficient. The mass accommodation coefficient was found to be unity (within 0.004) for all studied surfaces, which is in agreement with previous simulation work. Additionally, the simulated evaporation fluxes imply that the evaporation coefficient is also unity. Comparing the evaporation rates of the mass accommodation and evaporation simulations indicated that the high collision flux, corresponding to high supersaturation, present in typical molecular dynamics mass accommodation simulations can under certain conditions lead to an increase in the evaporation rate. Consequently, in such situations the mass accommodation coefficient can be overestimated, but in the present cases the corrected values were still close to unity with the lowest value at ≈0.99

What controls the observed size-dependency of the growth rates of sub-10 nm atmospheric particles?

The formation and growth of atmospheric particles involving sulfuric acid and organic vapors is estimated to have significant climate effects. To accurately represent this process in large-scale models, the correct interpretation of the observations on particle growth, especially below 10 nm, is essential. Here, we disentangle the factors governing the growth of sub-10 nm particles in the presence of sulfuric acid and organic vapors, using molecular-resolution cluster population simulations and chamber experiments. We find that observed particle growth rates are determined by the combined effects of (1) the concentrations and evaporation rates of the condensing vapors, (2) particle population dynamics, and (3) stochastic fluctuations, characteristic to initial nucleation. This leads to a different size-dependency of growth rate in the presence of sulfuric acid and/or organic vapors at different concentrations. Specifically, the activation type behavior, resulting in growth rate increasing with the particle size, is observed only at certain vapor concentrations. In our model simulations, cluster-cluster collisions enhance growth rate at high vapor concentrations and their importance is dictated by the cluster evaporation rates, which demonstrates the need for accurate evaporation rate data. Finally, we show that at sizes below similar to 2.5-3.5 nm, stochastic effects can importantly contribute to particle population growth. Overall, our results suggest that interpreting particle growth observations with approaches neglecting population dynamics and stochastics, such as with single particle growth models, can lead to the wrong conclusions on the properties of condensing vapors and particle growth mechanisms.Peer reviewe

Applicability of condensation particle counters to measure atmospheric clusters

This study presents an evaluation of a pulse height condensation particle counter (PH-CPC) and an expansion condensation particle counter (E-CPC) in terms of measuring ambient and laboratory-generated molecular and ion clusters. Ambient molecular cluster concentrations were measured with both instruments as they were deployed in conjunction with an ion spectrometer and other aerosol instruments in Hyytiälä, Finland at the SMEAR II station between 1 March and 30 June 2007. The observed cluster concentrations varied and ranged from some thousands to 100 000 cm -3. Both instruments showed similar (within a factor of ~5) concentrations. An average size of the detected clusters was approximately 1.8 nm. As the atmospheric measurement of sub 2-nm particles and molecular clusters is a challenging task, we conclude that most likely we were unable to detect the smallest clusters. Nevertheless, the reported concentrations are the best estimates to date for minimum cluster concentrations in a boreal forest environment

The roles of the atmosphere and ocean in driving Arctic warming due to European aerosol reductions

Clean air policies can have significant impacts on climate in remote regions. Previous modeling studies have shown that the temperature response to European sulfate aerosol reductions is largest in the Arctic. Here, we investigate the atmospheric and ocean roles in driving this enhanced Arctic warming using a set of fully‐coupled and slab‐ocean simulations (specified ocean heat convergence fluxes) with the Norwegian Earth system model (NorESM), under scenarios with high and low European aerosol emissions relative to year 2000. We show that atmospheric processes drive most of the Arctic response. The ocean pathway plays a secondary role inducing small temperature changes mostly in the opposite direction of the atmospheric response. Important modulators of the temperature response patterns are changes in sea‐ice extent and subsequent turbulent heat flux exchange, suggesting that a proper representation of Arctic sea‐ice and turbulent changes are key to predicting the Arctic response to mid‐latitude aerosol forcing

New particle formation from sulfuric acid and amines : Comparison of monomethylamine, dimethylamine, and trimethylamine

Amines are bases that originate from both anthropogenic and natural sources, and they are recognized as candidates to participate in atmospheric aerosol particle formation together with sulfuric acid. Monomethylamine, dimethylamine, and trimethylamine (MMA, DMA, and TMA, respectively) have been shown to enhance sulfuric acid-driven particle formation more efficiently than ammonia, but both theory and laboratory experiments suggest that there are differences in their enhancing potentials. However, as quantitative concentrations and thermochemical properties of different amines remain relatively uncertain, and also for computational reasons, the compounds have been treated as a single surrogate amine species in large-scale modeling studies. In this work, the differences and similarities of MMA, DMA, and TMA are studied by simulations of molecular cluster formation from sulfuric acid, water, and each of the three amines. Quantum chemistry-based cluster evaporation rate constants are applied in a cluster population dynamics model to yield cluster concentrations and formation rates at boundary layer conditions. While there are differences, for instance, in the clustering mechanisms and cluster hygroscopicity for the three amines, DMA and TMA can be approximated as a lumped species. Formation of nanometer-sized particles and its dependence on ambient conditions is roughly similar for these two: both efficiently form clusters with sulfuric acid, and cluster formation is rather insensitive to changes in temperature and relative humidity. Particle formation from sulfuric acid and MMA is weaker and significantly more sensitive to ambient conditions. Therefore, merging MMA together with DMA and TMA introduces inaccuracies in sulfuric acid-amine particle formation schemes.Peer reviewe

How Do Amines Affect the Growth of Recently Formed Aerosol Particles

Growth rates of recently born nanometer-scale particles were measured during the CLOUD experiments at CERN. Combining the data from several recently developed measurement techniques allowed us to follow the growth of the particles starting from molecules to molecular clusters and finally to climatically relevant particles. We studied the binary system with sulphuric acid and water, and the ternary systems with ammonia or dimethylamine added to the chamber, both in purely neutral situation, and with ionization from cosmic rays or the CERN particle beam