Numerical approaches to new particle formation and growth in the atmosphere

Aerosols impact the planet and our daily lives through various effects, perhaps most notably those related to their climatic and health-related consequences. While there are several primary particle sources, secondary new particle formation from precursor vapors is also known to be a frequent, global phenomenon. Nevertheless, the formation mechanism of new particles, as well as the vapors participating in the process, remain a mystery. This thesis consists of studies on new particle formation specifically from the point of view of numerical modeling. A dependence of formation rate of 3 nm particles on the sulphuric acid concentration to the power of 1-2 has been observed. This suggests nucleation mechanism to be of first or second order with respect to the sulphuric acid concentration, in other words the mechanisms based on activation or kinetic collision of clusters. However, model studies have had difficulties in replicating the small exponents observed in nature. The work done in this thesis indicates that the exponents may be lowered by the participation of a co-condensing (and potentially nucleating) low-volatility organic vapor, or by increasing the assumed size of the critical clusters. On the other hand, the presented new and more accurate method for determining the exponent indicates high diurnal variability. Additionally, these studies included several semi-empirical nucleation rate parameterizations as well as a detailed investigation of the analysis used to determine the apparent particle formation rate. Due to their high proportion of the earth's surface area, oceans could potentially prove to be climatically significant sources of secondary particles. In the lack of marine observation data, new particle formation events in a coastal region were parameterized and studied. Since the formation mechanism is believed to be similar, the new parameterization was applied in a marine scenario. The work showed that marine CCN production is feasible in the presence of additional vapors contributing to particle growth. Finally, a new method to estimate concentrations of condensing organics was developed. The algorithm utilizes a Markov chain Monte Carlo method to determine the required combination of vapor concentrations by comparing a measured particle size distribution with one from an aerosol dynamics process model. The evaluation indicated excellent agreement against model data, and initial results with field data appear sound as well.

Proton magnetic resonance spectroscopy of a boron neutron capture therapy 10B-carrier, L-p-boronophenylalanine-fructose complex

Boron neutron capture therapy (BNCT) is a radiotherapy that has mainly been used to treat malignant brain tumours, melanomas, and head and neck cancer. In BNCT, the patient receives an intravenous infusion of a 10B-carrier, which accumulates in the tumour area. The tumour is irradiated with epithermal or thermal neutrons, which result in a boron neutron capture reaction that generates heavy particles to damage tumour cells. In Finland, boronophenylalanine fructose (BPA-F) is used as the 10B-carrier. Currently, the drifting of boron from blood to tumour as well as the spatial and temporal accumulation of boron in the brain, are not precisely known. Proton magnetic resonance spectroscopy (1H MRS) could be used for selective BPA-F detection and quantification as aromatic protons of BPA resonate in the spectrum region, which is clear of brain metabolite signals. This study, which included both phantom and in vivo studies, examined the validity of 1H MRS as a tool for BPA detection. In the phantom study, BPA quantification was studied at 1.5 and 3.0 T with single voxel 1H MRS, and at 1.5 T with magnetic resonance imaging (MRSI). The detection limit of BPA was determined in phantom conditions at 1.5 T and 3.0 T using single voxel 1H MRS, and at 1.5 T using MRSI. In phantom conditions, BPA quantification accuracy of ± 5% and ± 15% were achieved with single voxel MRS using external or internal (internal water signal) concentration references, respectively. For MRSI, a quantification accuracy of <5% was obtained using an internal concentration reference (creatine). The detection limits of BPA in phantom conditions for the PRESS sequence were 0.7 (3.0 T) and 1.4 mM (1.5 T) mM with 20 × 20 × 20 mm3 single voxel MRS, and 1.0 mM with acquisition-weighted MRSI (nominal voxel volume 10(RL) × 10(AP) × 7.5(SI) mm3), respectively. In the in vivo study, an MRSI or single voxel MRS or both was performed for ten patients (patients 1-10) on the day of BNCT. Three patients had glioblastoma multiforme (GBM), and five patients had a recurrent or progressing GBM or anaplastic astrocytoma gradus III, and two patients had head and neck cancer. For nine patients (patients 1-9), MRS/MRSI was performed 70-140 min after the second irradiation field, and for one patient (patient 10), the MRSI study began 11 min before the end of the BPA-F infusion and ended 6 min after the end of the infusion. In comparison, single voxel MRS was performed before BNCT, for two patients (patients 3 and 9), and for one patient (patient 9), MRSI was performed one month after treatment. For one patient (patient 10), MRSI was performed four days before infusion. Signals from the tumour spectrum aromatic region were detected on the day of BNCT in three patients, indicating that in favourable cases, it is possible to detect BPA in vivo in the patient’s brain after BNCT treatment or at the end of BPA-F infusion. However, because the shape and position of the detected signals did not exactly match the BPA spectrum detected in the in vitro conditions, assignment of BPA is difficult. The opportunity to perform MRS immediately after the end of BPA-F infusion for more patients is necessary to evaluate the suitability of 1H MRS for BPA detection or quantification for treatment planning purposes. However, it could be possible to use MRSI as criteria in selecting patients for BNCT.

Experimental studies on new particle formation and ions

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.

Investigations of planetary boundary layer processes and particle formation in the atmosphere of planet Mars

The planet Mars is the Earth's neighbour in the Solar System. Planetary research stems from a fundamental need to explore our surroundings, typical for mankind. Manned missions to Mars are already being planned, and understanding the environment to which the astronauts would be exposed is of utmost importance for a successful mission. Information of the Martian environment given by models is already now used in designing the landers and orbiters sent to the red planet. In particular, studies of the Martian atmosphere are crucial for instrument design, entry, descent and landing system design, landing site selection, and aerobraking calculations. Research of planetary atmospheres can also contribute to atmospheric studies of the Earth via model testing and development of parameterizations: even after decades of modeling the Earth's atmosphere, we are still far from perfect weather predictions. On a global level, Mars has also been experiencing climate change. The aerosol effect is one of the largest unknowns in the present terrestrial climate change studies, and the role of aerosol particles in any climate is fundamental: studies of climate variations on another planet can help us better understand our own global change. In this thesis I have used an atmospheric column model for Mars to study the behaviour of the lowest layer of the atmosphere, the planetary boundary layer (PBL), and I have developed nucleation (particle formation) models for Martian conditions. The models were also coupled to study, for example, fog formation in the PBL. The PBL is perhaps the most significant part of the atmosphere for landers and humans, since we live in it and experience its state, for example, as gusty winds, nightfrost, and fogs. However, PBL modelling in weather prediction models is still a difficult task. Mars hosts a variety of cloud types, mainly composed of water ice particles, but also CO2 ice clouds form in the very cold polar night and at high altitudes elsewhere. Nucleation is the first step in particle formation, and always includes a phase transition. Cloud crystals on Mars form from vapour to ice on ubiquitous, suspended dust particles. Clouds on Mars have a small radiative effect in the present climate, but it may have been more important in the past. This thesis represents an attempt to model the Martian atmosphere at the smallest scales with high resolution. The models used and developed during the course of the research are useful tools for developing and testing parameterizations for larger-scale models all the way up to global climate models, since the small-scale models can describe processes that in the large-scale models are reduced to subgrid (not explicitly resolved) scale.

Adaptive tree multigrids and simplified spherical harmonics approximation in deterministic neutral and charged particle transport

A new deterministic three-dimensional neutral and charged particle transport code, MultiTrans, has been developed. In the novel approach, the adaptive tree multigrid technique is used in conjunction with simplified spherical harmonics approximation of the Boltzmann transport equation. The development of the new radiation transport code started in the framework of the Finnish boron neutron capture therapy (BNCT) project. Since the application of the MultiTrans code to BNCT dose planning problems, the testing and development of the MultiTrans code has continued in conventional radiotherapy and reactor physics applications. In this thesis, an overview of different numerical radiation transport methods is first given. Special features of the simplified spherical harmonics method and the adaptive tree multigrid technique are then reviewed. The usefulness of the new MultiTrans code has been indicated by verifying and validating the code performance for different types of neutral and charged particle transport problems, reported in separate publications.

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.

Irradiation of silicon particle detectors with MeV-protons

Silicon particle detectors are used in several applications and will clearly require better hardness against particle radiation in the future large scale experiments than can be provided today. To achieve this goal, more irradiation studies with defect generating bombarding particles are needed. Protons can be considered as important bombarding species, although neutrons and electrons are perhaps the most widely used particles in such irradiation studies. Protons provide unique possibilities, as their defect production rates are clearly higher than those of neutrons and electrons, and, their damage creation in silicon is most similar to the that of pions. This thesis explores the development and testing of an irradiation facility that provides the cooling of the detector and on-line electrical characterisation, such as current-voltage (IV) and capacitance-voltage (CV) measurements. This irradiation facility, which employs a 5-MV tandem accelerator, appears to function well, but some disadvantageous limitations are related to MeV-proton irradiation of silicon particle detectors. Typically, detectors are in non-operational mode during irradiation (i.e., without the applied bias voltage). However, in real experiments the detectors are biased; the ionising proton generates electron-hole pairs, and a rise in rate of proton flux may cause the detector to breakdown. This limits the proton flux for the irradiation of biased detectors. In this work, it is shown that, if detectors are irradiated and kept operational, the electric field decreases the introduction rate of negative space-charges and current-related damage. The effects of various particles with different energies are scaled to each others by the non-ionising energy loss (NIEL) hypothesis. The type of defects induced by irradiation depends on the energy used, and this thesis also discusses the minimum proton energy required at which the NIEL-scaling is valid.

Analysis of Atmospheric Particle Formation Events

Atmospheric aerosol particle formation events can be a significant source for tropospheric aerosols and thus influence the radiative properties and cloud cover of the atmosphere. This thesis investigates the analysis of aerosol size distribution data containing particle formation events, describes the methodology of the analysis and presents time series data measured inside the Boreal forest. This thesis presents a methodology to identify regional-scale particle formation, and to derive the basic characteristics such as growth and formation rates. The methodology can also be used to estimate concentration and source rates of the vapour causing particle growth. Particle formation was found to occur frequently in the boreal forest area over areas covering up to hundreds of kilometers. Particle formation rates of boreal events were found to be of the order of 0.01-5 cm^-3 s^-1, while the nucleation rates of 1 nm particles can be a few orders of magnitude higher. The growth rates of over 3 nm sized particles were of the order of a few nanometers per hour. The vapor concentration needed to sustain such growth is of the order of 10^7--10^8 cm^-3, approximately one order of magnitude higher than sulphuric acid concentrations found in the atmosphere. Therefore, one has to assume that other vapours, such as organics, have a key role in growing newborn particles to sizes where they can become climatically active. Formation event occurrence shows a clear annual variation with peaks in summer and autumns. This variation is similar to the variation exhibited the obtained formation rates of particles. The growth rate, on the other hand, reaches its highest values during summer. This difference in the annual behavior, and the fact that no coupling between the growth and formation process could be identified, suggest that these processes might be different ones, and that both are needed for a particle formation burst to be observed.

Non-Gaussianities and Preheating from N-flation and Magnetogenesis via rotating cosmic string loops

In this thesis we examine multi-field inflationary models of the early Universe. Since non-Gaussianities may allow for the possibility to discriminate between models of inflation, we compute deviations from a Gaussian spectrum of primordial perturbations by extending the delta-N formalism. We use N-flation as a concrete model; our findings show that these models are generically indistinguishable as long as the slow roll approximation is still valid. Besides computing non-Guassinities, we also investigate Preheating after multi-field inflation. Within the framework of N-flation, we find that preheating via parametric resonance is suppressed, an indication that it is the old theory of preheating that is applicable. In addition to studying non-Gaussianities and preheatng in multi-field inflationary models, we study magnetogenesis in the early universe. To this aim, we propose a mechanism to generate primordial magnetic fields via rotating cosmic string loops. Magnetic fields in the micro-Gauss range have been observed in galaxies and clusters, but their origin has remained elusive. We consider a network of strings and find that rotating cosmic string loops, which are continuously produced in such networks, are viable candidates for magnetogenesis with relevant strength and length scales, provided we use a high string tension and an efficient dynamo.

Shock acceleration in the solar corona

In this thesis acceleration of energetic particles at collisionless shock waves in space plasmas is studied using numerical simulations, with an emphasis on physical conditions applicable to the solar corona. The thesis consists of four research articles and an introductory part that summarises the main findings reached in the articles and discusses them with respect to theory of diffusive shock acceleration and observations. This thesis gives a brief review of observational properties of solar energetic particles and discusses a few open questions that are currently under active research. For example, in a few large gradual solar energetic particle events the heavy ion abundance ratios and average charge states show characteristics at high energies that are typically associated with flare-accelerated particles, i.e. impulsive events. The role of flare-accelerated particles in these and other gradual events has been discussed a lot in the scientific community, and it has been questioned if and how the observed features can be explained in terms of diffusive shock acceleration at shock waves driven by coronal mass ejections. The most extreme solar energetic particle events are the so-called ground level enhancements where particle receive so high energies that they can penetrate all the way through Earth's atmosphere and increase radiation levels at the surface. It is not known what conditions are required for acceleration into GeV/nuc energies, and the presence of both very fast coronal mass ejections and X-class solar flares makes it difficult to determine what is the role of these two accelerators in ground level enhancements. The theory of diffusive shock acceleration is reviewed and its predictions discussed with respect to the observed particle characteristics. We discuss how shock waves can be modeled and describe in detail the numerical model developed by the author. The main part of this thesis consists of the four scientific articles that are based on results of the numerical shock acceleration model developed by the author. The novel feature of this model is that it can handle complex magnetic geometries which are found, for example, near active regions in the solar corona. We show that, according to our simulations, diffusive shock acceleration can explain the observed variations in abundance ratios and average charge states, provided that suitable seed particles and magnetic geometry are available for the acceleration process in the solar corona. We also derive an injection threshold for diffusive shock acceleration that agrees with our simulation results very well, and which is valid under weakly turbulent conditions. Finally, we show that diffusive shock acceleration can produce GeV/nuc energies under suitable coronal conditions, which include the presence of energetic seed particles, a favourable magnetic geometry, and an enhanced level of ambient turbulence.