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  • Rissanen, Antti (Edita prima Oy, 2011)
    This research is connected with an education development project for the four-year-long officer education program at the National Defence University. In this curriculum physics was studied in two alternative course plans namely scientific and general. Observations connected to the later one e.g. student feedback and learning outcome gave indications that action was needed to support the course. The reform work was focused on the production of aligned course related instructional material. The learning material project produced a customized textbook set for the students of the general basic physics course. The research adapts phases that are typical in Design Based Research (DBR). The research analyses the feature requirements for physics textbook aimed at a specific sector and frames supporting instructional material development, and summarizes the experiences gained in the learning material project when the selected frames have been applied. The quality of instructional material is an essential part of qualified teaching. The goal of instructional material customization is to increase the product's customer centric nature and to enhance its function as a support media for the learning process. Textbooks are still one of the core elements in physics teaching. The idea of a textbook will remain but the form and appearance may change according to the prevailing technology. The work deals with substance connected frames (demands of a physics textbook according to the PER-viewpoint, quality thinking in educational material development), frames of university pedagogy and instructional material production processes. A wide knowledge and understanding of different frames are useful in development work, if they are to be utilized to aid inspiration without limiting new reasoning and new kinds of models. Applying customization even in the frame utilization supports creative and situation aware design and diminishes the gap between theory and practice. Generally, physics teachers produce their own supplementary instructional material. Even though customization thinking is not unknown the threshold to produce an entire textbook might be high. Even though the observations here are from the general physics course at the NDU, the research gives tools also for development in other discipline related educational contexts. This research is an example of an instructional material development work together the questions it uncovers, and presents thoughts when textbook customization is rewarding. At the same time, the research aims to further creative customization thinking in instruction and development. Key words: Physics textbook, PER (Physics Education Research), Instructional quality, Customization, Creativity
  • Hirvonen, Sami-Pekka (Helsingin yliopisto, 2015)
    Poly(benzimidazobenzophenanthroline) (BBL), which may be doped into a p- and n-type semiconductor, has been chemically modified to enhance its processability. In its pristine form BBL is processable only in some concentrated acids and nitromethane/Lewis acid solutions. The corrosiveness of these solvents and moisture sensitivity of the solutions severely limits the possibilities for the use of BBL as an electroactive material in organoelectronic devices and limit the possibilities for its post synthetic chemical modification. In this work processable BBL derivatives have been prepared using two different approaches i) preparation of block-copolymers by attachment of water soluble polymers on BBL functional chain ends ii) attaching bulky side groups on one of the monomers and using that as a starting material in the polymerization reaction. Short BBLs of DP 10 or 20 were prepared with functional chain ends and monofunctional poly(ethylene oxide) (PEO) or poly(N-isopropylacrylamide) of several different molecular weights were attached at the chain ends. Elemental analysis showed that the extent of chain end substitution varied quite a lot when PEO was used. It was also shown that thermogravimetric analysis (TGA) was not suitable to determine the fraction of PEO in BBL-PEO block-copolymers. However, the extent of chain end substitution using PNIPAM was evaluated using TGA. BBL-PEOs could be processed into aqueous dispersions at concentrations ≥ 1.5 mg/ml by means of ultrasonication, and these dispersions were proven to be colloidally very stable. The dispersions could be used to spin- or drop cast films. At higher concentrations BBL-PEO dispersions were shown to form gels. The reason for the gelling is the packing of the polymer into nano-wire structures which then aggregate into 3D-network. SEM- and cryo-TEM imaging confirmed the existence of wire-type structures. Wire structures and gelation were also observed for aqueous dispersions of pristine BBL. BBL-PNIPAM block-copolymers were found to be indispersible in water with PNIPAM fractions lower than 35 mass %. However, they gelled upon ultrasonication. With higher PNIPAM fractions the polymers were dispersible and did not form gels in any of the studied concentrations. Dispersibility in water and the colloidal stability of BBL-PEOs and BBL-PNIPAMs was attributed to electrostatic stabilization as the particles showed negative zeta-potentials. Dispersible BBL-PNIPAMs were more stable due the high amount of dissociative groups originating from the partial degradation of the amide moieties during the coupling to BBL. One of the monomers used to prepare BBL, 1,4,5,8-naphthalenetetracarboxylic acid 1,8-monoanhydride, was successfully mono- and dibrominated. The bromine was then used as a functional group and replaced either directly with 2-ethyl-1-hexylamine or substituted with azide and reacted with 1-hexyne. The modified monomers were used in preparation of BBL. BBLs bearing either 2-ethyl-1-hexylamine or 4-butyl-1,2,3-triazole groups were found to be sparingly soluble in dimethylsulphoxide and N-methyl-2-pyrrolidone.
  • Alenius, Teija (Helsingin yliopisto, 2007)
    This thesis discusses the prehistoric human disturbance during the Holocene by means of case studies using detailed high-resolution pollen analysis from lake sediment. The four lakes studied are situated between 61o 40' and 61o 50' latitudes in the Finnish Karelian inland area and vary between 2.4 and 28.8 ha in size. The existence of Early Metal Age population was one important question. Another study question concerned the development of grazing, and the relationship between slash-and-burn cultivation and permanent field cultivation. The results were presented as pollen percentages and pollen concentrations (grains cm 3). Accumulation values (grains cm 2 yr 1) were calculated for Lake Nautajärvi and Lake Orijärvi sediment, where the sediment accumulation rate was precisely determined. Sediment properties were determined using loss-on-ignition (LOI) and magnetic susceptibility (k). Dating methods used include both conventional and AMS 14C determinations, paleomagnetic dating and varve choronology. The isolation of Lake Kirjavalampi on the northern shore of Lake Ladoga took place ca. 1460 1300 BC. The long sediment cores from Finland, Lake Kirkkolampi and Lake Orijärvi in southeastern Finland and Lake Nautajärvi in south central Finland all extended back to the Early Holocene and were isolated from the Baltic basin ca. 9600 BC, 8600 BC and 7675 BC, respectively. In the long sediment cores, the expansion of Alnus was visible between 7200 - 6840 BC. The spread of Tilia was dated in Lake Kirkkolampi to 6600 BC, in Lake Orijärvi to 5000 BC and at Lake Nautajärvi to 4600 BC. Picea is present locally in Lake Kirkkolampi from 4340 BC, in Lake Orijärvi from 6520 BC and in Lake Nautajärvi from 3500 BC onwards. The first modifications in the pollen data, apparently connected to anthropogenic impacts, were dated to the beginning of the Early Metal Period, 1880 1600 BC. Anthropogenic activity became clear in all the study sites by the end of the Early Metal Period, between 500 BC AD 300. According to Secale pollen, slash-and-burn cultivation was practised around the eastern study lakes from AD 300 600 onwards, and at the study site in central Finland from AD 880 onwards. The overall human impact, however, remained low in the studied sites until the Late Iron Age. Increasing human activity, including an increase in fire frequency was detected from AD 800 900 onwards in the study sites in eastern Finland. In Lake Kirkkolampi, this included cultivation on permanent fields, but in Lake Orijärvi, permanent field cultivation became visible as late as AD 1220, even when the macrofossil data demonstrated the onset of cultivation on permanent fields as early as the 7th century AD. On the northern shore of Lake Ladoga, local activity became visible from ca. AD 1260 onwards and at Lake Nautajärvi, sediment the local occupation was traceable from 1420 AD onwards. The highest values of Secale pollen were recorded both in Lake Orijärvi and Lake Kirjavalampi between ca. AD 1700 1900, and could be associated with the most intensive period of slash-and-burn from AD 1750 to 1850 in eastern Finland.
  • Hjort, Jan (Helsingin yliopisto, 2006)
    Determination of the environmental factors controlling earth surface processes and landform patterns is one of the central themes in physical geography. However, the identification of the main drivers of the geomorphological phenomena is often challenging. Novel spatial analysis and modelling methods could provide new insights into the process-environment relationships. The objective of this research was to map and quantitatively analyse the occurrence of cryogenic phenomena in subarctic Finland. More precisely, utilising a grid-based approach the distribution and abundance of periglacial landforms were modelled to identify important landscape scale environmental factors. The study was performed using a comprehensive empirical data set of periglacial landforms from an area of 600 km2 at a 25-ha resolution. The utilised statistical methods were generalized linear modelling (GLM) and hierarchical partitioning (HP). GLMs were used to produce distribution and abundance models and HP to reveal independently the most likely causal variables. The GLM models were assessed utilising statistical evaluation measures, prediction maps, field observations and the results of HP analyses. A total of 40 different landform types and subtypes were identified. Topographical, soil property and vegetation variables were the primary correlates for the occurrence and cover of active periglacial landforms on the landscape scale. In the model evaluation, most of the GLMs were shown to be robust although the explanation power, prediction ability as well as the selected explanatory variables varied between the models. The great potential of the combination of a spatial grid system, terrain data and novel statistical techniques to map the occurrence of periglacial landforms was demonstrated in this study. GLM proved to be a useful modelling framework for testing the shapes of the response functions and significances of the environmental variables and the HP method helped to make better deductions of the important factors of earth surface processes. Hence, the numerical approach presented in this study can be a useful addition to the current range of techniques available to researchers to map and monitor different geographical phenomena.
  • Oksanen, Esko (Helsingin yliopisto, 2009)
    Inorganic pyrophosphatases (PPases, EC hydrolyse pyrophosphate in a reaction that provides the thermodynamic 'push' for many reactions in the cell, including DNA and protein synthesis. Soluble PPases can be classified into two families that differ completely in both sequence and structure. While Family I PPases are found in all kingdoms, family II PPases occur only in certain prokaryotes. The enzyme from baker's yeast (Saccharomyces cerevisiae) is very well characterised both kinetically and structurally, but the exact mechanism has remained elusive. The enzyme uses divalent cations as cofactors; in vivo the metal is magnesium. Two metals are permanently bound to the enzyme, while two come with the substrate. The reaction cycle involves the activation of the nucleophilic oxygen and allows different pathways for product release. In this thesis I have solved the crystal structures of wild type yeast PPase and seven active site variants in the presence of the native cofactor magnesium. These structures explain the effects of the mutations and have allowed me to describe each intermediate along the catalytic pathway with a structure. Although establishing the ʻchoreographyʼ of the heavy atoms is an important step in understanding the mechanism, hydrogen atoms are crucial for the mechanism. The most unambiguous method to determine the positions of these hydrogen atoms is neutron crystallography. In order to determine the neutron structure of yeast PPase I perdeuterated the enzyme and grew large crystals of it. Since the crystals were not stable at ambient temperature, a cooling device was developed to allow neutron data collection. In order to investigate the structural changes during the reaction in real time by time-resolved crystallography a photolysable substrate precursor is needed. I synthesised a candidate molecule and characterised its photolysis kinetics, but unfortunately it is hydrolysed by both yeast and Thermotoga maritima PPases. The mechanism of Family II PPases is subtly different from Family I. The native metal cofactor is manganese instead of magnesium, but the metal activation is more complex because the metal ions that arrive with the substrate are magnesium different from those permanently bound to the enzyme. I determined the crystal structures of wild type Bacillus subtilis PPase with the inhibitor imidodiphosphate and an inactive H98Q variant with the substrate pyrophosphate. These structures revealed a new trimetal site that activates the nucleophile. I also determined that the metal ion sites were partially occupied by manganese and iron using anomalous X- ray scattering.
  • Henriksson, Krister (Helsingin yliopisto, 2005)
  • Mäkelä, Hanna (Helsingin yliopisto, 2015)
    Roughly three-quarters of Finland s area is covered by forests. Any climatological changes influencing the danger of forest fire are important to evaluate and consider. The objective of this thesis is to study the long-term past and future changes in climatically-driven forest fire danger in Finland based on the summertime mean temperature and precipitation sum. The work is composed of two parts. In the first part, long-term gridded datasets of observed monthly mean temperatures and precipitation sums for Finland are developed. In the second part, these gridded datasets are used together with calculated values of the Finnish Forest Fire Index and probabilistic climate model simulations (from the ENSEMBLES project) to estimate the number of forest fire danger days during the summer season (June-August). The long-term variation of Finland s climatological forest fire danger is studied roughly for 100 years backwards and into the future. One of the main achievements of this thesis is that it explores the possibility of quantifying past and future fire-weather using a relatively limited database with regard to both weather variables and their spatial coverage. This enables a wider exploitation of scattered data series from earlier times and can also provide opportunities for projections using data with a low resolution. The climatological forest fire danger in Finland varies considerably from year to year. There have not been any significant increasing or decreasing trends in the number of fire danger days during the 20th century (1908-2011). On average, the highest probability of forest fire danger occurs in June and July, when a fire hazard exists on roughly 35-40% of all days. The intra-seasonal variation of fire danger has been large enough to enable the occurrence of conflagrations even though the fire danger for the season as a whole has been at an average level. Despite the projected increase in average summertime precipitation, the Finnish climate will provide more favourable conditions for the occurrence of forest fires in the future than today. This is due to increases in the mean temperature. The probability of an increase in the number of fire danger days is 56-75% in the near future (2010-2029) and 71-91% by the end of the current century (2080-2099), depending on the region. This would indicate an increase of 1-2 and 7-10 days, respectively. It is thus clearly important to further develop existing tools for the forecasting of fire danger, and to maintain the capabilities of the fire prevention, surveillance and suppression services. Future projections of all relevant meteorological variables (temperature, precipitation, humidity, evaporation and wind speed) at higher temporal and spatial resolutions, in addition to information on the type of the summertime precipitation and the length of the dry periods, would notably improve the assessment of the future climatological forest fire danger.
  • Viskari, Toni (Helsingin yliopisto, 2012)
    Atmospheric aerosol particles have several important effects on the environment and human society. The exact impact of aerosol particles is largely determined by their particle size distributions. However, no single instrument is able to measure the whole range of the particle size distribution. Estimating a particle size distribution from multiple simultaneous measurements remains a challenge in aerosol physical research. Current methods to combine different measurements require assumptions concerning the overlapping measurement ranges and have difficulties in accounting for measurement uncertainties. In this thesis, Extended Kalman Filter (EKF) is presented as a promising method to estimate particle number size distributions from multiple simultaneous measurements. The particle number size distribution estimated by EKF includes information from prior particle number size distributions as propagated by a dynamical model and is based on the reliabilities of the applied information sources. Known physical processes and dynamically evolving error covariances constrain the estimate both over time and particle size. The method was tested with measurements from Differential Mobility Particle Sizer (DMPS), Aerodynamic Particle Sizer (APS) and nephelometer. The particle number concentration was chosen as the state of interest. The initial EKF implementation presented here includes simplifications, yet the results are positive and the estimate successfully incorporated information from the chosen instruments. For particle sizes smaller than 4 micrometers, the estimate fits the available measurements and smooths the particle number size distribution over both time and particle diameter. The estimate has difficulties with particles larger than 4 micrometers due to issues with both measurements and the dynamical model in that particle size range. The EKF implementation appears to reduce the impact of measurement noise on the estimate, but has a delayed reaction to sudden large changes in size distribution.
  • Pushkina, Diana (Helsingfors universitet, 2007)
    Short and long term environmental changes, variations in climate and vegetation during the late Neogene shaped the geographical ranges of large terrestrial mammals by allowing origination, distribution and dispersal of certain species that make up faunas. Climatic fluctuations were intensified during the latest Neogene, Pleistocene (1.8-0.01 Ma), at the end of which also human presence became more conspicuous. Both climate and humans have been linked to extensive alteration and extinctions in mammalian faunas across the world. This dissertation consists of a set of papers that examine different periods of the Neogene and associated faunas in northern Eurasia. Major trends in changing environments and climate were studied by means of the tooth crown height (hypsodonty) and dietary structure in herbivorous terrestrial mammals or/and species commonness (locality coverage, abundance proxy). This study was also intended to bring to light a great deal of information contained in Russian literature to fill in the gap between the European literature and not translated Russian records. Since the middle Miocene (~15-11 Ma), central Asia has been the focal point of the transformation in Eurasia towards more open and dry environment. The drying of the central part of Eurasia hampered the spread of temperate or mesophilic species between western and eastern sides of the continent, and created conditions for origination of the cold and arid adapted grazing fauna in north-eastern Eurasia. Throughout the climatically unstable late middle and late Pleistocene, Europe that was more maritime during interglacials than Siberia, experienced the most drastic faunal alternations between the interglacial Palaeoloxodon antiquus and glacial Mammuthus primigenius assemblages that permanently inhabited the Mediterranean and Siberia, respectively. During more climatically equable middle part of the middle Pleistocene (Holsteinian interglacial) that was climatically similar to the current Holocene, the interglacial species could have spread eastwards. The origins, dispersal and cohesiveness of the Palaeoloxodon antiquus assemblage in Eurasia are examined. During the latest Weichselian Glaciation (Late Glacial, 15 000-10 500 yr BP, latest late Paleolithic) and Holocene (last 10 000 yr) a rapid warming initiated fragmentation of dry and cold tundra-steppes when increased temperature and humidity produced boggy tundra in the north and forests in the south of the most part of northern Eurasia. The most significant change took place in central Asia influencing the glacial mammoth fauna decline as is seen in southern Siberia from decreased mean hypsodonty and the shift in dietary preferences from grazing towards browsing in herbivorous ungulates along with decreased mean body size in large mammals. It is difficult to disentangle the role of humans from climate effect in large mammal extinctions in Eurasia at the Weichselian-Holocene boundary because they pretty much coincided. The study is consistent with the idea that Eurasian late Pleistocene extinctions were first climatically driven, after which the impact of rapidly expanding humans must have become more manifest and crucial either by direct hunting or via indirect activities. Only the data for the extinct steppe bison may indicate a disproportionate selection by humans although more sufficient and recently updated data are needed. Key words: Pleistocene, Neogene, Paleolithic, interglacial, glacial, large mammals, distribution, hypsodonty, aridity, precipitation, body size, commonness, extinction, human influence.
  • Pohjola, Mia (Helsingin yliopisto, 2006)
    This thesis contains three subject areas concerning particulate matter in urban area air quality: 1) Analysis of the measured concentrations of particulate matter mass concentrations in the Helsinki Metropolitan Area (HMA) in different locations in relation to traffic sources, and at different times of year and day. 2) The evolution of traffic exhaust originated particulate matter number concentrations and sizes in local street scale are studied by a combination of a dispersion model and an aerosol process model. 3) Some situations of high particulate matter concentrations are analysed with regard to their meteorological origins, especially temperature inversion situations, in the HMA and three other European cities. The prediction of the occurrence of meteorological conditions conducive to elevated particulate matter concentrations in the studied cities is examined. The performance of current numerical weather forecasting models in the case of air pollution episode situations is considered. The study of the ambient measurements revealed clear diurnal variation of the PM10 concentrations in the HMA measurement sites, irrespective of the year and the season of the year. The diurnal variation of local vehicular traffic flows seemed to have no substantial correlation with the PM2.5 concentrations, indicating that the PM10 concentrations were originated mainly from local vehicular traffic (direct emissions and suspension), while the PM2.5 concentrations were mostly of regionally and long-range transported origin. The modelling study of traffic exhaust dispersion and transformation showed that the number concentrations of particles originating from street traffic exhaust undergo a substantial change during the first tens of seconds after being emitted from the vehicle tailpipe. The dilution process was shown to dominate total number concentrations. Minimal effect of both condensation and coagulation was seen in the Aitken mode number concentrations. The included air pollution episodes were chosen on the basis of occurrence in either winter or spring, and having at least partly local origin. In the HMA, air pollution episodes were shown to be linked to predominantly stable atmospheric conditions with high atmospheric pressure and low wind speeds in conjunction with relatively low ambient temperatures. For the other European cities studied, the best meteorological predictors for the elevated concentrations of PM10 were shown to be temporal (hourly) evolutions of temperature inversions, stable atmospheric stability and in some cases, wind speed. Concerning the weather prediction during particulate matter related air pollution episodes, the use of the studied models were found to overpredict pollutant dispersion, leading to underprediction of pollutant concentration levels.
  • Kohonen, Jukka (Helsingin yliopisto, 2015)
    Clustering is a central task in computational statistics. Its aim is to divide observed data into groups of items, based on the similarity of their features. Among various approaches to clustering, Bayesian model-based clustering has recently gained popularity. Many existing works are based on stochastic sampling methods. This work is concerned with exact, exponential-time algorithms for the Bayesian model-based clustering task. In particular, we consider the exact computation of two summary statistics: the number of clusters, and pairwise incidence of items in the same cluster. We present an implemented algorithm for computing these statistics substantially faster than would be achieved by direct enumeration of the possible partitions. The method is practically applicable to data sets of up to approximately 25 items. We apply a variant of the exact inference method into graphical models where a given variable may have up to four parent variables. The parent variables can then have up to 16 value combinations, and the task is to cluster them and find combinations that lead to similar conditional probability tables. Further contributions of this work are related to number theory. We show that a novel combination of addition chains and additive bases provides the optimal arrangement of multiplications, when the task is to use repeated multiplication starting from a given number or entity, but only a certain kind of function of the successive powers is required. This arrangement speeds up the computation of the posterior distribution for the number of clusters. The same arrangement method can be applied to other multiplicative tasks, for example, in matrix multiplication. We also present new algorithmic results related to finding extremal additive bases. Before this work, the extremal additive bases were known up to length 23. We have computed them up to length 24 in the unrestricted case, and up to length 41 in the restricted case.
  • Orponen, Tuomas (Helsingin yliopisto, 2012)
    The dissertation Exceptional sets in projection and slicing theorems contains a treatment of two classical topics in fractal geometry: projections and slicing. The thesis consists of an introductory chapter and two scientific articles; the new results extend a long line of research originated by J. M. Marstrand in 1954. The first paper deals with projecting a planar set K onto lines. The fractal geometer is interested in the following question: what is the relation between the dimensions of K and its projections? In 1954, Marstrand proved that if the dimension of K lies between zero and one, then the projections tend to preserve dimension; for almost every line the dimension of the projection equals dim K. During its nearly 60 years of existence, this theme has spawned countless variations. In the thesis, special attention is given to scrutinizing the words almost every line in Marstrand s theorem. The words cannot be entirely omitted (an illustrative example is given by projecting the y-axis onto the x-axis), but they can be sharpened in many cases. The definition used by Marstrand allows for a fairly large set of exceptional lines , the projection onto which fails to preserve the dimension of K. It turns out that better bounds for the size of this exceptional set can be obtained through a more intricate analysis. The second paper is thematically close akin to the first; it takes up another 1954 result by Marstrand, the slicing theorem , and examines the exceptional set estimates therein. To explain the slicing theorem, fix a planar set K with dimension greater than one. This time, the set K is intersected with various planar lines. What is the dimension of these slices of K? In general, one cannot expect to find a single constant answering the question: if K is bounded, many lines evade K altogether, and the corresponding slices have dimension zero. However, not all slices of K can be so small. Marstrand showed that in almost every direction many lines meet K in a set of dimension dim K 1. In Marstrand s original formulation, the same definition for the words almost every was used as in the projection theorem, and, again, bounds for the size of the exceptional set can be improved with new techniques. In the thesis, similar estimates are also derived in a variant of the theorem where planar lines are replaced by more complicated curves.
  • Paananen, Tomi (Helsingin yliopisto, 2009)
    This is a study of ultra-cold Fermi gases in different systems. This thesis is focused on exotic superfluid states, for an example on the three component Fermi gas and the FFLO phase in optical lattices. In the two-components case, superfluidity is studied mainly in the case of the spin population imbalanced Fermi gases and the phase diagrams are calculated from the mean-field theory. Different methods to detect different phases in optical lattices are suggested. In the three-component case, we studied also the uniform gas and harmonically trapped system. In this case, the BCS theory is generalized to three-component gases. It is also discussed how to achieve the conditions to get an SU(3)-symmetric Hamiltonian in optical lattices. The thesis is divided in chapters as follows: Chapter 1 is an introduction to the field of cold quantum gases. In chapter 2 optical lattices and their experimental characteristics are discussed. Chapter 3 deals with two-components Fermi gases in optical lattices and the paired states in lattices. In chapter 4 three-component Fermi gases with and without a harmonic trap are explored, and the pairing mechanisms are studied. In this chapter, we also discuss three-component Fermi gases in optical lattices. Chapter 5 devoted to the higher order correlations, and what they can tell about the paired states. Chapter 6 concludes the thesis.
  • Asmi, Eija (Helsingin yliopisto, 2010)
    Atmospheric aerosol particles have significant climatic effects. Secondary new particle formation is a globally important source of these particles. Currently, the mechanisms of particle formation and the vapours participating in this process are, however, not truly understood. The recently developed Neutral cluster and Air Ion Spectrometer (NAIS) was widely used in field studies of atmospheric particle formation. The NAIS was calibrated and found to be in adequate agreement with the reference instruments. It was concluded that NAIS can be reliably used to measure ions and particles near the sizes where the atmospheric particle formation begins. The main focus of this thesis was to study new particle formation and participation of ions in this process. To attain this objective, particle and ion formation and growth rates were studied in various environments - at several field sites in Europe, in previously rarely studied sites in Antarctica and Siberia and also in an indoor environment. New particle formation was observed at all sites were studied and the observations were used as indicatives of the particle formation mechanisms. Particle size-dependent growth rates and nucleation mode hygroscopic growth factors were examined to obtain information on the particle growth. It was found that the atmospheric ions participate in the initial steps of new particle formation, although their contribution was minor in the boundary layer. The highest atmospheric particle formation rates were observed at the most polluted sites where the role of ions was the least pronounced. Furthermore, the increase of particle growth rate with size suggested that enhancement of the growth by ions was negligible. Participation of organic vapours in the particle growth was supported by laboratory and field observations. It was addressed that secondary new particle formation can also be a significant source of indoor air particles. These results, extending over a wide variety of environments, give support to previous observations and increase understanding on new particle formation on a global scale.
  • Schobesberger, Siegfried (Helsingin yliopisto, 2014)
    Atmospheric aerosols have important effects on health and climate. An important source is the formation of aerosol particles from gas-phase precursors. In this thesis, the goal was to improve our understanding of how exactly this atmospheric particle formation proceeds. Attempts have been made to describe aerosol particle formation by classical nucleation theory. To test this theory, the heterogeneous nucleation of n-propanol vapor on 4 11 nm seed particles was investigated. The choice of seed particle material was found to determine if classical theories could be applied or not, probably because of material-specific inter-molecular interactions between the vapor and the seed particle. The classical theories fail to describe these interactions, which can be crucial in microscopic systems. The critical processes of atmospheric particle formation occur at sizes below 2 nm. In this thesis, novel techniques were employed to access this size range, primarily the atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer that can directly measure the composition of ions and ionic clusters up to a size of about 2 nm. APi-TOFs were employed at the CLOUD facility at CERN during experiments that focused on exploring particle formation from various systems of vapors. The results of the APi-TOF measurements were the key in revealing the detailed mechanisms of how clusters were initially formed by which vapors, and how these clusters grew to sizes > 2 nm. Clusters of sulfuric acid + ammonia and sulfuric acid + dimethylamine were shown to form and grow via strong hydrogen bonds. The APi-TOF measurements also showed that certain large monoterpene oxidation products, some of them very highly oxidized, can directly bind with bisulfate ions and with sulfuric acid molecules. The clusters then grow by the addition of more of these large oxidized organics and sulfuric acid molecules. Similarities with results from measurements in the boreal forest suggest that large oxidized organics indeed play a crucial role in ambient particle formation events. A light airplane was used to explore how the mechanisms of actual aerosol particle formation vary throughout the atmosphere above the boreal forest, from the canopy up into the free troposphere. They confirmed the extent of boundary layer new particle formation events, and showed indications of an important role of dynamical processes at the top of the boundary layer. Local enhancements of particle formation were observed in connection with clouds. This thesis goal was achieved chiefly by using state-of-the-art experimental techniques together with high-quality laboratory experiments as well as in the field, and by taking ambient measurements aloft. Hopes are that this work will prove to be an important contribution in advancing our knowledge of the detailed mechanisms of atmospheric aerosol particle formation.
  • Neitola, Kimmo (Helsingin yliopisto, 2015)
    Aerosols affect our everyday life in many ways. Changes in visibility, allergies to pollen, spray cans and dosing of some medication are just a few examples of common aerosols. Aerosols may have more profound way to affect every one of us; through climate. Possible changes in aerosol particle concentrations and compositions may alter large precipitation patterns and change cloud albedo, and lifetime. To be able to predict future changes in climate, profound understating of physical and chemical processes affecting the atmospheric aerosol population is crucial. Nucleation, i.e. gas-to-liquid phase transition, is the fundamental step in particle formation in the atmosphere. Sulphuric acid is established to be one of key components in atmospheric nucleation, but other stabilizing species are needed to participate in the process to ex-plain atmospheric nucleation. The identity of these species and the mechanisms of the process itself have been elusive. This thesis aims to gain insight on the species participating nucleation and the mechanism of the whole process. This thesis concentrates first to identify meteorological parameters controlling the atmos-pheric new particle formation. The information gathered from the field is used to design laboratory experiments more precise for the purpose of studying nucleation. The laboratory experiments were carried out using different flow tubes, first to test the limits of the Clas-sical Nucleation Theory and later on to investigate sulphuric acid-water binary and sul-phuric acid-water-base compound ternary nucleation. The precursor gas species were measured using mass spectrometers and ion chromatographs. The measured concentration of sulphuric acid from gas and particle phases were compared to theoretical prediction. The magnitude of the effect of base compounds on nucleation was estimated. The clustering of sulphuric acid molecules with other species was detected. Initial growth of clusters were studied in the point of view of sulphate containing species. The results from the laboratory experiments confirmed earlier results found in the literature that base compounds increase nucleation rates significantly. The measurements of the gas-phase concentrations of these compounds set an upper limit, where the increasing effect is saturated. Comparison of the sulphuric acid concentrations measured with different tech-niques and with the theoretical approach showed order-of-magnitude discrepancy. The discrepancy was found to be due to clustering of sulphuric acid molecules with various species. Sulphate-containing species was found to be responsible of the initial growth of clusters in the flow tube measurements. Even though the species participating nucleation are still an open question, the work done in this thesis has helped to identify few of these species and the magnitude of their effect on nucleation. This thesis also helps to under-stand the initial growth of clusters in flow tube experiments and to identify possible limitation on instruments used commonly in atmospheric measurements.
  • Hyvärinen, Antti-Pekka (Helsingin yliopisto, 2006)
    Aerosol particles play a role in the earth ecosystem and affect human health. A significant pathway of producing aerosol particles in the atmosphere is new particle formation, where condensable vapours nucleate and these newly formed clusters grow by condensation and coagulation. However, this phenomenon is still not fully understood. This thesis brings an insight to new particle formation from an experimental point of view. Laboratory experiments were conducted both on the nucleation process and physicochemical properties related to new particle formation. Nucleation rate measurements are used to test nucleation theories. These theories, in turn, are used to predict nucleation rates in atmospheric conditions. However, the nucleation rate measurements have proven quite difficult to conduct, as different devices can yield nucleation rates with differences of several orders of magnitude for the same substances. In this thesis, work has been done to have a greater understanding in nucleation measurements, especially those conducted in a laminar flow diffusion chamber. Systematic studies of nucleation were also made for future verification of nucleation theories. Surface tensions and densities of substances related to atmospheric new particle formation were measured. Ternary sulphuric acid + ammonia + water is a proposed candidate to participate in atmospheric nucleation. Surface tensions of an alternative candidate to nucleate in boreal forest areas, sulphuric acid + dimethylamine + water, were also measured. Binary compounds, consisting of organic acids + water are possible candidates to participate in the early growth of freshly nucleated particles. All the measured surface tensions and densities were fitted with equations, thermodynamically consistent if possible, to be easily applied to atmospheric model calculations of nucleation and subsequent evolution of particle size.
  • Eresmaa, Reima (Helsingin yliopisto, 2007)
    Data assimilation provides an initial atmospheric state, called the analysis, for Numerical Weather Prediction (NWP). This analysis consists of pressure, temperature, wind, and humidity on a three-dimensional NWP model grid. Data assimilation blends meteorological observations with the NWP model in a statistically optimal way. The objective of this thesis is to describe methodological development carried out in order to allow data assimilation of ground-based measurements of the Global Positioning System (GPS) into the High Resolution Limited Area Model (HIRLAM) NWP system. Geodetic processing produces observations of tropospheric delay. These observations can be processed either for vertical columns at each GPS receiver station, or for the individual propagation paths of the microwave signals. These alternative processing methods result in Zenith Total Delay (ZTD) and Slant Delay (SD) observations, respectively. ZTD and SD observations are of use in the analysis of atmospheric humidity. A method is introduced for estimation of the horizontal error covariance of ZTD observations. The method makes use of observation minus model background (OmB) sequences of ZTD and conventional observations. It is demonstrated that the ZTD observation error covariance is relatively large in station separations shorter than 200 km, but non-zero covariances also appear at considerably larger station separations. The relatively low density of radiosonde observing stations limits the ability of the proposed estimation method to resolve the shortest length-scales of error covariance. SD observations are shown to contain a statistically significant signal on the asymmetry of the atmospheric humidity field. However, the asymmetric component of SD is found to be nearly always smaller than the standard deviation of the SD observation error. SD observation modelling is described in detail, and other issues relating to SD data assimilation are also discussed. These include the determination of error statistics, the tuning of observation quality control and allowing the taking into account of local observation error correlation. The experiments made show that the data assimilation system is able to retrieve the asymmetric information content of hypothetical SD observations at a single receiver station. Moreover, the impact of real SD observations on humidity analysis is comparable to that of other observing systems.