Surface studies of limestones and dolostones : characterisation using various techniques and batch dissolution experiments with hydrochloric acid solutions

In this thesis, stepwise titration with hydrochloric acid was used to obtain chemical reactivities and dissolution rates of ground limestones and dolostones of varying geological backgrounds (sedimentary, metamorphic or magmatic). Two different ways of conducting the calculations were used: 1) a first order mathematical model was used to calculate extrapolated initial reactivities (and dissolution rates) at pH 4, and 2) a second order mathematical model was used to acquire integrated mean specific chemical reaction constants (and dissolution rates) at pH 5. The calculations of the reactivities and dissolution rates were based on rate of change of pH and particle size distributions of the sample powders obtained by laser diffraction. The initial dissolution rates at pH 4 were repeatedly higher than previously reported literature values, whereas the dissolution rates at pH 5 were consistent with former observations. Reactivities and dissolution rates varied substantially for dolostones, whereas for limestones and calcareous rocks, the variation can be primarily explained by relatively large sample standard deviations. A list of the dolostone samples in a decreasing order of initial reactivity at pH 4 is: 1) metamorphic dolostones with calcite/dolomite ratio higher than about 6% 2) sedimentary dolostones without calcite 3) metamorphic dolostones with calcite/dolomite ratio lower than about 6% The reactivities and dissolution rates were accompanied by a wide range of experimental techniques to characterise the samples, to reveal how different rocks changed during the dissolution process, and to find out which factors had an influence on their chemical reactivities. An emphasis was put on chemical and morphological changes taking place at the surfaces of the particles via X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). Supporting chemical information was obtained with X-Ray Fluorescence (XRF) measurements of the samples, and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) measurements of the solutions used in the reactivity experiments. Information on mineral (modal) compositions and their occurrence was provided by X-Ray Diffraction (XRD), Energy Dispersive X-ray analysis (EDX) and studying thin sections with a petrographic microscope. BET (Brunauer, Emmet, Teller) surface areas were determined from nitrogen physisorption data. Factors increasing chemical reactivity of dolostones and calcareous rocks were found to be sedimentary origin, higher calcite concentration and smaller quartz concentration. Also, it is assumed that finer grain size and larger BET surface areas increase the reactivity although no certain correlation was found in this thesis. Atomic concentrations did not correlate with the reactivities. Sedimentary dolostones, unlike metamorphic ones, were found to have porous surface structures after dissolution. In addition, conventional (XPS) and synchrotron based (HRXPS) X-ray Photoelectron Spectroscopy were used to study bonding environments on calcite and dolomite surfaces. Both samples are insulators, which is why neutralisation measures such as electron flood gun and a conductive mask were used. Surface core level shifts of 0.7 ± 0.1 eV for Ca 2p spectrum of calcite and 0.75 ± 0.05 eV for Mg 2p and Ca 3s spectra of dolomite were obtained. Some satellite features of Ca 2p, C 1s and O 1s spectra have been suggested to be bulk plasmons. The origin of carbide bonds was suggested to be beam assisted interaction with hydrocarbons found on the surface. The results presented in this thesis are of particular importance for choosing raw materials for wet Flue Gas Desulphurisation (FGD) and construction industry. Wet FGD benefits from high reactivity, whereas construction industry can take advantage of slow reactivity of carbonate rocks often used in the facades of fine buildings. Information on chemical bonding environments may help to create more accurate models for water-rock interactions of carbonates.

Biomassan käsittely voimalaitoksissa

Tässä diplomityössä tutkitaan biomassan esikäsittelyä suurissa voimalaitoksissa. Työssä keskitytään puusta saataviin polttoaineisiin. Biomassan esikäsittely on tärkeä osa voimalaitoksen toimintaa. Sillä pyritään saamaan puulle halutut ominaisuudet loppukäyttöä, kuten polttoa tai kaasutusta varten. Puubiomassan tärkeimpiä ominaisuuksia ovat kosteus, palakoko ja tasalaatuisuus. Työ on jaettu neljään osaan. Ensimmäisessä osassa tutkitaan kiinteän biomassan ominaisuuksia ja ongelmia. Toisessa osassa esitellään erilaisia voimalaitoksissa käytettäviä puubiomassoja ja niiden erityisominaisuuksia ja -vaatimuksia. Kolmannessa osassa esitellään biomassan käsittelyä voimalaitoksella. Käsittely jaotellaan vastaanottoon, esikäsittelyyn, varastointiin ja käsittelylaitteistoihin. Kolmannessa osassa tutkitaan myös käsittelyn erityisvaatimuksia ja esitellään esimerkkejä biomassan kokonaiskäsittelystä laitoksella. Työn neljäs osa paneutuu biomassan käsittelyn turvallisuus- ja ympäristöasioihin. Puubiomassan esikäsittely on suunniteltava käytettävien puulaatujen ja -määrien mukaan. Biomassan kosteuden ollessa korkea, on tutkittava onko kuivurien käyttö kannattavaa ja perusteltua. Jos voimalaitokselle tuleva puu on epätasalaatuista tai sisältää epäpuhtauksia, on käytettävä erilaisia puhdistus- ja murskainlaitteistoja. Biomassan käsittelyssä syntyy melua ja päästöjä. Ympäristö- ja terveyshaittojen ehkäisemiseksi käsittelylaitteistoihin on suunniteltava tarpeelliset suojat ja varojärjestelmät.

De fine desiderii infiniti omnibus hominibus inditi

Invokaatio: D.D.

De oblectatione et appetitu mentis, de fine in media translato

Invokaatio: D.F.G.

Climatic changes: what if the global increase of CO2 emissions cannot be kept under control?

Climatic changes threaten the planet. Most articles related to the subject present estimates of the disasters expected to occur, but few have proposed ways to deal with the impending menaces. One such threat is the global warming caused by the continuous increase in CO2 emissions leading to rising ocean levels due to the increasing temperatures of the polar regions. This threat is assumed to eventually cause the death of hundreds of millions of people. We propose to desalinize ocean water as a means to reduce the rise of ocean levels and to use this water for populations that need good quality potable water, precisely in the poorest regions of the planet. Technology is available in many countries to provide desalinated water at a justifiable cost considering the lives threatened both in coastal and desertified areas.

Fine-tuning of defensive behaviors in the dorsal periaqueductal gray by atypical neurotransmitters

This paper presents an up-to-date review of the evidence indicating that atypical neurotransmitters such as nitric oxide (NO) and endocannabinoids (eCBs) play an important role in the regulation of aversive responses in the periaqueductal gray (PAG). Among the results supporting this role, several studies have shown that inhibitors of neuronal NO synthase or cannabinoid receptor type 1 (CB1) receptor agonists cause clear anxiolytic responses when injected into this region. The nitrergic and eCB systems can regulate the activity of classical neurotransmitters such as glutamate and γ-aminobutyric acid (GABA) that control PAG activity. We propose that they exert a ‘fine-tuning’ regulatory control of defensive responses in this area. This control, however, is probably complex, which may explain the usually bell-shaped dose-response curves observed with drugs that act on NO- or CB1-mediated neurotransmission. Even if the mechanisms responsible for this complex interaction are still poorly understood, they are beginning to be recognized. For example, activation of transient receptor potential vanilloid type-1 channel (TRPV1) receptors by anandamide seems to counteract the anxiolytic effects induced by CB1 receptor activation caused by this compound. Further studies, however, are needed to identify other mechanisms responsible for this fine-tuning effect.

Adenovirus-mediated siRNA targeting TNF-α and overexpression of bone morphogenetic protein-2 promotes early osteoblast differentiation on a cell model of Ti particle-induced inflammatory response in vitro

Wear particles are phagocytosed by macrophages and other inflammatory cells, resulting in cellular activation and release of proinflammatory factors, which cause periprosthetic osteolysis and subsequent aseptic loosening, the most common causes of total joint arthroplasty failure. During this pathological process, tumor necrosis factor-alpha (TNF-α) plays an important role in wear-particle-induced osteolysis. In this study, recombination adenovirus (Ad) vectors carrying both target genes [TNF-α small interfering RNA (TNF-α-siRNA) and bone morphogenetic protein 2 (BMP-2)] were synthesized and transfected into RAW264.7 macrophages and pro-osteoblastic MC3T3-E1 cells, respectively. The target gene BMP-2, expressed on pro-osteoblastic MC3T3-E1 cells and silenced by the TNF-α gene on cells, was treated with titanium (Ti) particles that were assessed by real-time PCR and Western blot. We showed that recombinant adenovirus (Ad-siTNFα-BMP-2) can induce osteoblast differentiation when treated with conditioned medium (CM) containing RAW264.7 macrophages challenged with a combination of Ti particles and Ad-siTNFα-BMP-2 (Ti-ad CM) assessed by alkaline phosphatase activity. The receptor activator of nuclear factor-κB ligand was downregulated in pro-osteoblastic MC3T3-E1 cells treated with Ti-ad CM in comparison with conditioned medium of RAW264.7 macrophages challenged with Ti particles (Ti CM). We suggest that Ad-siTNFα-BMP-2 induced osteoblast differentiation and inhibited osteoclastogenesis on a cell model of a Ti particle-induced inflammatory response, which may provide a novel approach for the treatment of periprosthetic osteolysis.

De praecipuo, hominibus in terra, a Deo proposito fine 1

Invokaatio: D.D.

Particle size and cholesterol content of a mayonnaise formulated by OSA-modified potato starch

Egg yolk was partially replaced (0, 25, 50, 75, and 100%) with octenyl succinic anhydride (OSA)-modified potato starch in a reduced-fat mayonnaise formulation to curtail the problems associated with high cholesterol and induced allergic reactions. The physicochemical properties included parameters such as: pH, fat content, and emulsion stability of the formulations analyzed. The samples with 75% and 100% egg yolk substitute showed the maximum emulsion stability (>95% after two of months storage), and they were selected according to cholesterol content, particle size distributions, dynamic rheological properties, microstructure, and sensory characteristic. A significant reduction (84-97%) in the cholesterol content was observed in the selected samples. Particle size analysis showed that by increasing the amount of OSA starch, the oil droplets with the peak size of 70 µm engulfed by this compound became larger. The rheological tests elucidated that in the absence of egg yolk, OSA starch may not result in a final product with consistent texture and that the best ratio of the two emulsifiers (OSA starch/egg yolk) to produce stable reduced-fat, low cholesterol mayonnaise is 75/25. The microscopic images confirmed the formation of a stable cohesive layer of starch surrounding the oil droplets emulsified in the samples selected.

Open publishing: lessons from particle physics

Syksy Räsänen's presentation at Kirjastoverkkopäivät, Helsinki 21.10.2015.

Climate change and global responsibility - the role of energy consumption, GDP and CO2 emissions

Climate change is one of the biggest challenges faced by this generation. Despite being the single most important environmental challenge facing the planet and despite over two decades of international climate negotiations, global greenhouse gas (GHG) emissions continue to rise. By the middle of this century, GHGs must be reduced by as much as 40-70% if dangerous climate change is to be avoided. In the Kyoto Protocol no quantitative emission limitation and reduction commitments were placed on the developing countries. For the planning of the future commitments period and possible participation of developing countries, information of the functioning of the energy systems, CO2 emissions development in different sectors, energy use and technological development in developing countries is essential. In addition to the per capita emissions, the efficiency of the energy system in relation to GHG emissions is crucial for the decision of future long-term burden sharing between countries. Country’s future development of CO2 emissions can be defined by the estimated CO2 intensity of the future and the estimated GDP growth. The changes in CO2 intensity depend on several factors, but generally developed countries’ intensity has been increasing in the industrialization phase and decreasing when their economy shifts more towards the system dominated by the service sector. The level of the CO2 intensity depends by a large extent on the production structure and the energy sources that are used. Currently one of the most urgent issues regarding global climate change is to decide the future of the Kyoto Protocol. Negotiations on this topic have already been initiated, with the aim of being finalised by the 2015. This thesis provides insights into the various approaches that can be used to characterise the concept of comparable efforts for developing countries in a future international climate agreement. The thesis examines the post-Kyoto burden sharing questions for developing countries using the contraction and convergence model, which is one approach that has been proposed to allocate commitments regarding future GHG emissions mitigation. This new approach is a practical tool for the evaluation of the Kyoto climate policy process and global climate change negotiations from the perspective of the developing countries.

Hodegus finnicus, omnibus hanc linguam discere cupientibus valdè utilis. Eller finsk wägwijsare, allom dem, som finska tunmåhlet ex fundamento declinera, conjugera, construera och elliest lära willia, ganska nyttig. Cum analysi grammaticâ, ut & tabellâ in fine appositâ, quae formationi genitivi singularis inservit. Nunc ad multorum finnicae linguae studiosorum desiderium in lucem productus, & necessariis observationibus, tam ad ipsam lecturam, quam scripturam finnicam spectantibus illustratus, â Matthia Martinio, Tavast-Finnone

Invokaatio: I.N.D.

Stochastic particle models: mean reversion and burgers dynamics. An application to commodity markets

The aim of this study is to propose a stochastic model for commodity markets linked with the Burgers equation from fluid dynamics. We construct a stochastic particles method for commodity markets, in which particles represent market participants. A discontinuity in the model is included through an interacting kernel equal to the Heaviside function and its link with the Burgers equation is given. The Burgers equation and the connection of this model with stochastic differential equations are also studied. Further, based on the law of large numbers, we prove the convergence, for large N, of a system of stochastic differential equations describing the evolution of the prices of N traders to a deterministic partial differential equation of Burgers type. Numerical experiments highlight the success of the new proposal in modeling some commodity markets, and this is confirmed by the ability of the model to reproduce price spikes when their effects occur in a sufficiently long period of time.