Polymeeripinnoitteen aiheuttamat itseherätteiset värähtelyt nipillisessä telasysteemissä

Lukuisissa teollisuussovelluksissa materiaalien, kuten paperin ja teräslevyjen, muokkaamiseen käytettävät pyörivät nippitelat kärsivät aina erilaisten herätteiden synnyttämistä mekaanisista värähtelyistä, jotka voivat aiheuttaa virheitä valmistettaviin tuotteisiin. Tässä työssä tutkittiin viskoelastisia polymeerejä ja polymeeripinnoitteen nipilliseen telasysteemiin synnyttämiä haitallisia itseherätteisiä värähtelyjä. Työn polymeerejä käsittelevässä kirjallisuusosassa luotiin katsaus amorfisten polymeerien fysikaalisiin ominaisuuksiin. Kokeellisessa osuudessa tutkittiin tarkemmin kahden amorfisen telapinnoitepolymeerin termoreologisia ja mekaanisia ominaisuuksia suoritettujen DMTA-mittausten perusteella. Sovittamalla toisen polymeerin master-käyrään yleistetty lineaarisen standardiaineen malli saatiin selville polymeerin mekaaniset parametrit ja approksimaatio sen relaksaatiospektrille. Telapinnoitteen nipilliseen systeemiin synnyttämiä itseherätteisiä värähtelyjä ja niiden seurauksia tarkasteltiin kahdelle telalle ja polymeeripinnoitteelle kehitetyn analyyttisen mallin ja numeeristen laskujen avulla. Pinnoite mallinnettiin lineaarisen standardiaineen mukaisesti. Telasysteemin parametrit määritettiin DMTA-mittaustuloksista ja systeemiä vastaavasta koelaitteesta kokeellisella moodianalyysillä ja elementtimenetelmällä. Numeerisesta stabiilisuusanalyysistä ja liikeyhtälöiden integroinneista saadut tulokset kertovat telapinnoitteen aaltomaisista deformaatiomuodoista ja niiden synnyttämistä taajuusalueittain esiintyvistä epästabiileista värähtelyistä. Telasysteemi on epästabiili pinnoitedeformaatiokuvion systeemiin aiheuttaman herätevoiman taajuuden ollessa lähellä systeemin korkeampaa ominaistaajuutta. Numeerisista tuloksista voitiin ennustaa nopean ja hitaan barringin olemassaolo.

Lipase-catalyzed Approaches towards Secondary Alcohols: Intermediates for Enantiopure Drugs

The use of enantiopure intermediates for drug synthesis is a trend in pharmaceutical industry. Different physiological effects are associated with the enantiomers of chiral molecules. Thus, the safety profile of a drug based on an enantiopure active pharmaceutical ingredient is more reliable. Biocatalysis is an important tool to access enantiopure molecules. In biocatalysis, the advantage of selectivity (chemo-, regio- and stereoselectivity) is combined with the benefits of a green synthesis strategy. Chemoenzymatic syntheses of drug molecules, obtained by combining biocatalysis with modern chemical synthesis steps usually consists of fewer reaction steps, reduced waste production and improved overall synthetic efficiency both in yields and enantio- and/or diastereoselectivities compared with classical chemical synthesis. The experimental work together with the literature review clearly indicates that lipase catalysis is highly applicable in the synthesis of enantiopure intermediates of drug molecules as the basis to infer the correct stereochemistry. By lipase catalysis, enantiopure secondary alcohols used as intermediates in the synthesis of Dorzolamide, an antiglaucoma drug, were obtained. Enantiopure _-hydroxy nitriles as potential intermediates for the synthesis of antidepressant drugs with 1-aryl-3- methylaminopropan-1-ol structure were also obtained with lipases. Kinetic resolution of racemates was the main biocatalytic approach applied. Candida Antarctica lipase B, Burkholderia cepacia lipase and Thermomyces lanuginosus lipase were applied for the acylation of alcohols and the alcoholysis of their esters in organic solvents, such as in diisopropyl ether and tert-butyl methyl ether. Candida Antarctica lipase B was used under solvent free conditions for the acylation of ethyl 3-hydroxybutanoate.

Probiotic interventions in infancy: Benefit and Safety Assessment of Extended Applications

Immaturity of the gut barrier system in the newborn has been seen to underlie a number of chronic diseases originating in infancy and manifesting later in life. The gut microbiota and breast milk provide the most important maturing signals for the gut-related immune system and reinforcement of the gut mucosal barrier function. Recently, the composition of the gut microbiota has been proposed to be instrumental in control of host body weight and metabolism as well as the inflammatory state characterizing overweight and obesity. On this basis, inflammatory Western lifestyle diseases, including overweight development, may represent a potential target for probiotic interventions beyond the well documented clinical applications. The purpose of the present undertaking was to study the efficacy and safety of perinatal probiotic intervention. The material comprised two ongoing, prospective, double-blind NAMI (Nutrition, Allergy, Mucosal immunology and Intestinal microbiota) probiotic interventions. In the mother-infant nutrition and probiotic study altogether 256 women were randomized at their first trimester of pregnancy into a dietary intervention and a control group. The intervention group received intensive dietary counselling provided by a nutritionist, and were further randomized at baseline, double-blind, to receive probiotics (Lactobacillus rhamnosus GG and Bifidobacterium lactis) or placebo. The intervention period extended from the first trimester of pregnancy to the end of exclusive breastfeeding. In the allergy prevention study altogether 159 women were randomized, double-blind, to receive probiotics (Lactobacillus rhamnosus GG) or placebo 4 weeks before expected delivery, the intervention extending for 6 months postnatally. Additionally, patient data on all premature infants with very low birth weight (VLBW) treated in the Department of Paediatrics, Turku University Hospital, during the years 1997 - 2008 were utilized. The perinatal probiotic intervention reduced the risk of gestational diabetes mellitus (GDM) in the mothers and perinatal dietary counselling reduced that of fetal overgrowth in GDM-affected pregnancies. Early gut microbiota modulation with probiotics modified the growth pattern of the child by restraining excessive weight gain during the first years of life. The colostrum adiponectin concentration was demonstrated to be dependent on maternal diet and nutritional status during pregnancy. It was also higher in the colostrum received by normal-weight compared to overweight children at the age of 10 years. The early perinatal probiotic intervention and the postnatal probiotic intervention in VLBW infants were shown to be safe. To conclude, the findings in this study provided clinical evidence supporting the involvement of the initial microbial and nutritional environment in metabolic programming of the child. The manipulation of early gut microbial communities with probiotics might offer an applicable strategy to impact individual energy homeostasis and thus to prevent excessive body-weight gain. The results add weight to the hypothesis that interventions aiming to prevent obesity and its metabolic consequences later in life should be initiated as early as during the perinatal period.

The Structural Basis for inorganic Pyrophosphatase Catalysis and Regulation

Inorganic pyrophosphatases (PPases) are essential enzymes for every living cell. PPases provide the necessary thermodynamic pull for many biosynthetic reactions by hydrolyzing pyrophosphate. There are two types of PPases: integral membrane-bound and soluble enzymes. The latter type is divided into two non-homologous protein families, I and II. Family I PPases are present in all kingdoms of life, whereas family II PPases are only found in prokaryotes, including archae. Family I PPases, particularly that from Saccharomyces cerevisiae, are among the most extensively characterized phosphoryl transfer enzymes. In the present study, we have solved the structures of wild-type and seven active site variants of S. cerevisiae PPase bound to its natural metal cofactor, magnesium ion. These structures have facilitated derivation of the complete enzyme reaction scheme for PPase, fulfilling structures of all the reaction intermediates. The main focus in this study was on a novel subfamily of family II PPases (CBSPPase) containing a large insert formed by two CBS domains and a DRTGG domain within the catalytic domain. The CBS domain (named after cystathionine beta-synthase in which it was initially identified) usually occurs as tandem pairs with two or four copies in many proteins in all kingdoms of life. The structure formed by a pair of CBS domains is also known as a Bateman domain. CBS domains function as regulatory units, with adenylate ligands as the main effectors. The DRTGG domain (designated based on its most conserved residues) occurs less frequently and only in prokaryotes. Often, the domain co-exists with CBS domains, but its function remains unknown. The key objective of the current study was to explore the structural rearrangements in the CBS domains induced by regulatory adenylate ligands and their functional consequences. Two CBS-PPases were investigated, one from Clostridium perfringens (cpCBS-PPase) containing both CBS and DRTGG domains in its regulatory region and the other from Moorella thermoacetica (mt CBS-PPase) lacking the DRTGG domain. We additionally constructed a separate regulatory region of cpCBS-PPase (cpCBS). Both full-length enzymes and cpCBS formed homodimers. Two structures of the regulatory region of cpCBS-PPase complexed with the inhibitor, AMP, and activator, diadenosine tetraphosphate, were solved. The structures were significantly different, providing information on the structural pathway from bound adenylates to the interface between the regulatory and catalytic parts. To our knowledge, these are the first reported structures of a regulated CBS enzyme, which reveal large conformational changes upon regulator binding. The activator-bound structure was more open, consistent with the different thermostabilities of the activator- and inhibitor-bound forms of cpCBS-PPase. The results of the functional studies on wild-type and variant CBS-PPases provide support for inferences made on the basis of structural analyses. Moreover, these findings indicate that CBS-PPase activity is highly sensitive to adenine nucleotide distribution between AMP, ADP and ATP, and hence to the energy level of the cell. CBS-PPase activity is markedly inhibited at low energy levels, allowing PPi energy to be used for cell survival instead of being converted into heat.

PET and MR imaging in Parkinson’s disease patients with cognitive impairment. A study of dopaminergic dysfunction, amyloid deposition, cortical hypometabolism and brain atrophy

Parkinson’s disease (PD) is the second most common neurodegenerative disorder. It is characterized by a severe loss of substantia nigra dopaminergic neurons leading to dopamine depletion in the striatum. PD affects movement, producing motor symptoms such as rigidity, tremor and bradykinesia. Non-motor symptoms include autonomic dysfunction, neurobehavioral problems and cognitive impairment, which may lead to dementia. The pathophysiological basis of cognitive impairment and dementia in PD is unclear. The aim of this thesis was to study the pathophysiological basis of cognitive impairment and dementia in PD. We evaluated the relation between frontostriatal dopaminergic dysfunction and the cognitive symptoms in PD patients with [18F]Fdopa PET. We also combined [C]PIB and [¹⁸F]FDG PET and magnetic resonance imaging in PD patients with and without dementia. In addition, we analysed subregional striatal [¹⁸F]Fdopa PET data to find out whether a simple ratio approach would reliably separate PD patients from healthy controls. The impaired dopaminergic function of the frontostriatal regions was related to the impairment in cognitive functions, such as memory and cognitive processing in PD patients. PD patients with dementia showed an impaired glucose metabolism but not amyloid deposition in the cortical brain regions, and the hypometabolism was associated with the degree of cognitive impairment. PD patients had atrophy, both in the prefrontal cortex and in the hippocampus, and the hippocampal atrophy was related to impaired memory. A single 15-min scan 75 min after a tracer injection seemed to be sufficient for separating patients with PD from healthy controls in a clinical research environment. In conclusion, the occurrence of cognitive impairment and dementia in PD seems to be multifactorial and relates to changes, such as reduced dopaminergic activity, hypometabolism, brain atrophy and rarely to amyloid accumulation.

Kasvatus on kasvamaan saattamista. Kasvatusfilosofinen tutkimus J. A. Hollon sivistyskasvatusajattelusta

Tutkimukseni käsittelee J. A. Hollon (1885–1967) sivistyskasvatusajattelua. Hollo oli monitoiminen kulttuurivaikuttaja, joka toimi kriitikkona, kirjailijana, suomentajana ja kasvatustieteilijänä. Häntä voidaan pitää J. V. Snellmanin rinnalla yhtenä merkittävimpänä suomalaisena kasvatusajattelijana. Hänen kasvatusajattelustaan ei ole kuitenkaan aiemmin tehty väitöskirjatason tutkimusta. Tutkimuskysymykseni ovat seuraavat: 1. Millainen on Hollon näkemys kasvatuksesta, kasvatuksen maailmasta ja kasvatuksen teoriasta? 2. Mikä on Hollon käsitys kasvattajan ja kasvatettavan merkityksestä kasvatustapahtumassa? 3. Mitä asioita sisältyy sivistyskasvatuksen eli kasvamaan saattamisen elementteihin? Tutkimukseni on kasvatusfilosofinen. Tutkimusmenetelmäni on systemaattinen analyysi ja lähestymistapani on hermeneuttinen. Tutkimukseni pääaineistona ovat Hollon kasvatusta koskevat kirjoitukset, joista tärkeimmät ovat Mielikuvitus ja sen kasvattaminen I-II (1918, 1919), Kasvatuksen maailma (1927), Kasvatuksen teoria (1927) ja Itsekasvatus ja elämisen taito (1931). Hollon mukaan kasvatuksen maailma on suhteellisen itsenäinen elämänmuoto (Lebensform), jolla on oma ontologinen erityislaatunsa, so. sui generis. Kasvatusoppia ei pidä redusoida psykologiaan tai filosofiaan, koska sillä tavoin se menettää tieteellisen itsenäisyytensä. Hollon mielestä kasvatuksen teoria on teoria käytäntöä varten. Kasvatuksen teorian luomisessa tulee ottaa huomioon kasvatuksen maailman erityispiirteenä oleva kokonaisvaltainen näkökulma ja elämän palvelemisen päämäärä. Kasvattaminen on aina myös eettistä toimintaa. Kasvatuksen tavoitteena on hyvä elämä. Hollon mukaan kasvattajan tehtävä on luoda kasvatettavalleen eheä sivistyksellinen perusta. Tämä voi tapahtua vain laaja-alaisen sivistyskasvatuksen avulla, jonka runkona on antiikin humanistinen sivistysperinne. Sivistyskasvatukseen kuuluvat älyllinen, eettinen, uskonnollinen, esteettinen ja toiminnallinen kasvatus. Mielikuvituksen avulla kasvattaja voi yhdistää kasvatuksen osa-alueet eheäksi kokonaisuudeksi. Ilman mielikuvitusta erilaiset ilmiöt olisivat pirstaleisina, toisistaan erillisinä osina ihmisen mielessä. Opettajan persoona on merkittävä tekijä kasvatuksessa. Se tulee ottaa huomioon opettajankoulutuksen eli kasvattajan kasvattamisen valinnoissa. Opettaja-kasvattajan on tärkeää opiskella laajasti humanistisia opintoja, koska kasvatuksessa on kysymys ihmisestä. Ennen kaikkea kasvattajan eettistä ja esteettistä kykyä tulee harjoituttaa. Näin hän oppii käyttämään mielikuvitustaan kasvatustapahtumassa siten, että hän tulee kasvatuksellisesti näkeväksi kasvamaan saattajaksi, joka ymmärtää sen, mikä kussakin tilanteessa vaatii erityistä huomiota. Tutkimukseni osoittaa, että Hollon henkitieteellinen ja fenomenologis-hermeneuttinen kasvatusnäkemys ei ole vain vastaparadigma empiiriselle kasvatustieteelle, vaan myös nykyajan teknis-taloudelliselle eetokselle, joka yhtäältä uhkaa välineellistää kasvatuksen ja toisaalta väärällä tavoin tieteellistää kasvatuksen tutkimuksen. Tämän takia kasvatusoppi kysymyksineen uhkaa siirtyä kasvatuskeskustelussa syrjemmälle, jopa hävitä kokonaan. Kasvatuksen ja kasvatuksen tutkimuksen vaarana on niiden liiallinen sitouttaminen tuotantoelämän jatkeeksi, minkä seurauksena on ihmisyyden toteuttamisen vaikeutuminen. Tutkimuksen lopuksi esitän ideaalikoulunäkemykseni, joka perustuu osittain Hollon kasvatusnäkemykseen. Hollon näkemys on yhä ajankohtainen ja merkittävä kontribuutio kasvatusta, sen teoriaa ja käytäntöä koskevaan keskusteluun.

Pricing anomalies in the Finnish stock market

The aim of this thesis is to examine whether the pricing anomalies exists in the Finnish stock markets by comparing the performance of quantile portfolios that are formed on the basis of either individual valuation ratios, composite value measures or combined value and momentum indicators. All the research papers included in the thesis show evidence of value anomalies in the Finnish stock markets. In the first paper, the sample of stocks over the 1991-2006 period is divided into quintile portfolios based on four individual valuation ratios (i.e., E/P, EBITDA/EV, B/P, and S/P) and three hybrids of them (i.e. composite value measures). The results show the superiority of composite value measures as selection criterion for value stocks, particularly when EBITDA/EV is employed as earnings multiple. The main focus of the second paper is on the impact of the holding period length on performance of value strategies. As an extension to the first paper, two more individual ratios (i.e. CF/P and D/P) are included in the comparative analysis. The sample of stocks over 1993- 2008 period is divided into tercile portfolios based on six individual valuation ratios and three hybrids of them. The use of either dividend yield criterion or one of three composite value measures being examined results in best value portfolio performance according to all performance metrics used. Parallel to the findings of many international studies, our results from performance comparisons indicate that for the sample data employed, the yearly reformation of portfolios is not necessarily optimal in order to maximally gain from the value premium. Instead, the value investor may extend his holding period up to 5 years without any decrease in long-term portfolio performance. The same holds also for the results of the third paper that examines the applicability of data envelopment analysis (DEA) method in discriminating the undervalued stocks from overvalued ones. The fourth paper examines the added value of combining price momentum with various value strategies. Taking account of the price momentum improves the performance of value portfolios in most cases. The performance improvement is greatest for value portfolios that are formed on the basis of the 3-composite value measure which consists of D/P, B/P and EBITDA/EV ratios. The risk-adjusted performance can be enhanced further by following 130/30 long-short strategy in which the long position of value winner stocks is leveraged by 30 percentages while simultaneously selling short glamour loser stocks by the same amount. Average return of the long-short position proved to be more than double stock market average coupled with the volatility decrease. The fifth paper offers a new approach to combine value and momentum indicators into a single portfolio-formation criterion using different variants of DEA models. The results throughout the 1994-2010 sample period shows that the top-tercile portfolios outperform both the market portfolio and the corresponding bottom-tercile portfolios. In addition, the middle-tercile portfolios also outperform the comparable bottom-tercile portfolios when DEA models are used as a basis for stock classification criteria. To my knowledge, such strong performance differences have not been reported in earlier peer-reviewed studies that have employed the comparable quantile approach of dividing stocks into portfolios. Consistently with the previous literature, the division of the full sample period into bullish and bearish periods reveals that the top-quantile DEA portfolios lose far less of their value during the bearish conditions than do the corresponding bottom portfolios. The sixth paper extends the sample period employed in the fourth paper by one year (i.e. 1993- 2009) covering also the first years of the recent financial crisis. It contributes to the fourth paper by examining the impact of the stock market conditions on the main results. Consistently with the fifth paper, value portfolios lose much less of their value during bearish conditions than do stocks on average. The inclusion of a momentum criterion somewhat adds value to an investor during bullish conditions, but this added value turns to negative during bearish conditions. During bear market periods some of the value loser portfolios perform even better than their value winner counterparts. Furthermore, the results show that the recent financial crisis has reduced the added value of using combinations of momentum and value indicators as portfolio formation criteria. However, since the stock markets have historically been bullish more often than bearish, the combination of the value and momentum criteria has paid off to the investor despite the fact that its added value during bearish periods is negative, on an average.

Puomiankkurin uudelleensuunnittelu ja valmistus

Tämän diplomityön tavoitteena on ollut suunnitella uusi öljyntorjunnassa käytettävä puomiankkuri. Nykyisin käytössä olevat ankkurit ovat painavia, paljon tilaa vieviä, jäykkiä rakenteeltaan ja hankalia käyttää. Työn tavoitteena on ollut suunnitella rakenne, jossa muotoilun avulla pyritään korvaamaan ankkurin painoa ja saavuttaa hyvä tunkeutuminen eri pohjalaaduissa. Ankkurin suunnitteluun kuuluu merkittävänä osana materiaalinvalintaprosessi, jonka perusteella materiaaliksi valittiin kulutusteräs. Kulutusteräksen korkea lujuus ja hyvä kulumiskestävyys mahdollistavat ohuemman materiaalin käytön rakenteessa, jonka seurauksena rakenteen painoa saatiin vähennettyä merkittävästi. Ankkurin rakenteen suunnittelussa käytettiin hyväksi nykyisiä ankkurin rakenteita, joiden pohjalta hahmoteltiin eri variaatioita ankkureista. Suunnittelutyössä käytettiin hyväksi tyypillisiä ankkurirakenteita hyvien puolien kannalta, joita pyrittiin toteuttamaan uudessa ankkuri- rakenteessa. Ankkurin suunnittelu toteutettiin järjestelmällisen suunnittelun avulla, jossa ensin laadittiin ankkurille vaatimuslista. Tämän jälkeen laadittiin ankkurille toimintorakenne ja jakaminen osatoimintoihin. Ankkurin rakenteista toteutettiin kaksi eri versiota: sisävesillä ja merialueilla käytettävät ankkurit, joille laadittiin mitoitus. Työssä suunnitellun terävän tunkeutumisosan ja optimaalisen tunkeutumiskulman avulla ankkureiden painoa saatiin huomattavasti alhaisemmaksi, jonka seurauksena ankkurille saatiin kevyempi rakenne ja materiaalikustannukset pienenivät merkittävästi. Uusien ankkurien rakenne on pienemmän koon ja painon ansiosta käyttäjäystävällisempi.

Puomiankkurin uudelleensuunnittelu ja valmistus

Tämän diplomityön tavoitteena on ollut suunnitella uusi öljyntorjunnassa käytettävä puomiankkuri. Nykyisin käytössä olevat ankkurit ovat painavia, paljon tilaa vieviä, jäykkiä rakenteeltaan ja hankalia käyttää. Työn tavoitteena on ollut suunnitella rakenne, jossa muotoilun avulla pyritään korvaamaan ankkurin painoa ja saavuttaa hyvä tunkeutuminen eri pohjalaaduissa. Ankkurin suunnitteluun kuuluu merkittävänä osana materiaalinvalintaprosessi, jonka perusteella materiaaliksi valittiin kulutusteräs. Kulutusteräksen korkea lujuus ja hyvä kulumiskestävyys mahdollistavat ohuemman materiaalin käytön rakenteessa, jonka seurauksena rakenteen painoa saatiin vähennettyä merkittävästi. Ankkurin rakenteen suunnittelussa käytettiin hyväksi nykyisiä ankkurin rakenteita, joiden pohjalta hahmoteltiin eri variaatioita ankkureista. Suunnittelutyössä käytettiin hyväksi tyypillisiä ankkurirakenteita hyvien puolien kannalta, joita pyrittiin toteuttamaan uudessa ankkuri- rakenteessa. Ankkurin suunnittelu toteutettiin järjestelmällisen suunnittelun avulla, jossa ensin laadittiin ankkurille vaatimuslista. Tämän jälkeen laadittiin ankkurille toimintorakenne ja jakaminen osatoimintoihin. Ankkurin rakenteista toteutettiin kaksi eri versiota: sisävesillä ja merialueilla käytettävät ankkurit, joille laadittiin mitoitus. Työssä suunnitellun terävän tunkeutumisosan ja optimaalisen tunkeutumiskulman avulla ankkureiden painoa saatiin huomattavasti alhaisemmaksi, jonka seurauksena ankkurille saatiin kevyempi rakenne ja materiaalikustannukset pienenivät merkittävästi. Uusien ankkurien rakenne on pienemmän koon ja painon ansiosta käyttäjäystävällisempi.

Stochastic approximation methods in stochastic optimization

Stochastic approximation methods for stochastic optimization are considered. Reviewed the main methods of stochastic approximation: stochastic quasi-gradient algorithm, Kiefer-Wolfowitz algorithm and adaptive rules for them, simultaneous perturbation stochastic approximation (SPSA) algorithm. Suggested the model and the solution of the retailer's profit optimization problem and considered an application of the SQG-algorithm for the optimization problems with objective functions given in the form of ordinary differential equation.

Long-term nutrient load management and lake restoration: Case of Säkylän Pyhäjärvi (SW Finland)

Eutrophication caused by anthropogenic nutrient pollution has become one of the most severe threats to water bodies. Nutrients enter water bodies from atmospheric precipitation, industrial and domestic wastewaters and surface runoff from agricultural and forest areas. As point pollution has been significantly reduced in developed countries in recent decades, agricultural non-point sources have been increasingly identified as the largest source of nutrient loading in water bodies. In this study, Lake Säkylän Pyhäjärvi and its catchment are studied as an example of a long-term, voluntary-based, co-operative model of lake and catchment management. Lake Pyhäjärvi is located in the centre of an intensive agricultural area in southwestern Finland. More than 20 professional fishermen operate in the lake area, and the lake is used as a drinking water source and for various recreational activities. Lake Pyhäjärvi is a good example of a large and shallow lake that suffers from eutrophication and is subject to measures to improve this undesired state under changing conditions. Climate change is one of the most important challenges faced by Lake Pyhäjärvi and other water bodies. The results show that climatic variation affects the amounts of runoff and nutrient loading and their timing during the year. The findings from the study area concerning warm winters and their influences on nutrient loading are in accordance with the IPCC scenarios of future climate change. In addition to nutrient reduction measures, the restoration of food chains (biomanipulation) is a key method in water quality management. The food-web structure in Lake Pyhäjärvi has, however, become disturbed due to mild winters, short ice cover and low fish catch. Ice cover that enables winter seining is extremely important to the water quality and ecosystem of Lake Pyhäjärvi, as the vendace stock is one of the key factors affecting the food web and the state of the lake. New methods for the reduction of nutrient loading and the treatment of runoff waters from agriculture, such as sand filters, were tested in field conditions. The results confirm that the filter technique is an applicable method for nutrient reduction, but further development is needed. The ability of sand filters to absorb nutrients can be improved with nutrient binding compounds, such as lime. Long-term hydrological, chemical and biological research and monitoring data on Lake Pyhäjärvi and its catchment provide a basis for water protection measures and improve our understanding of the complicated physical, chemical and biological interactions between the terrestrial and aquatic realms. In addition to measurements carried out in field conditions, Lake Pyhäjärvi and its catchment were studied using various modelling methods. In the calibration and validation of models, long-term and wide-ranging time series data proved to be valuable. Collaboration between researchers, modellers and local water managers further improves the reliability and usefulness of models. Lake Pyhäjärvi and its catchment can also be regarded as a good research laboratory from the point of view of the Baltic Sea. The main problem in both of them is eutrophication caused by excess nutrients, and nutrient loading has to be reduced – especially from agriculture. Mitigation measures are also similar in both cases.

Improving the competitiveness of electrolytic Zinc process by chemical reaction engineering approach

This doctoral thesis describes the development work performed on the leachand purification sections in the electrolytic zinc plant in Kokkola to increase the efficiency in these two stages, and thus the competitiveness of the plant. Since metallic zinc is a typical bulk product, the improvement of the competitiveness of a plant was mostly an issue of decreasing unit costs. The problems in the leaching were low recovery of valuable metals from raw materials, and that the available technology offered complicated and expensive processes to overcome this problem. In the purification, the main problem was consumption of zinc powder - up to four to six times the stoichiometric demand. This reduced the capacity of the plant as this zinc is re-circulated through the electrolysis, which is the absolute bottleneck in a zinc plant. Low selectivity gave low-grade and low-value precipitates for further processing to metallic copper, cadmium, cobalt and nickel. Knowledge of the underlying chemistry was poor and process interruptions causing losses of zinc production were frequent. Studies on leaching comprised the kinetics of ferrite leaching and jarosite precipitation, as well as the stability of jarosite in acidic plant solutions. A breakthrough came with the finding that jarosite could precipitate under conditions where ferrite would leach satisfactorily. Based on this discovery, a one-step process for the treatment of ferrite was developed. In the plant, the new process almost doubled the recovery of zinc from ferrite in the same equipment as the two-step jarosite process was operated in at that time. In a later expansion of the plant, investment savings were substantial compared to other technologies available. In the solution purification, the key finding was that Co, Ni, and Cu formed specific arsenides in the “hot arsenic zinc dust” step. This was utilized for the development of a three-step purification stage based on fluidized bed technology in all three steps, i.e. removal of Cu, Co and Cd. Both precipitation rates and selectivity increased, which strongly decreased the zinc powder consumption through a substantially suppressed hydrogen gas evolution. Better selectivity improved the value of the precipitates: cadmium, which caused environmental problems in the copper smelter, was reduced from 1-3% reported normally down to 0.05 %, and a cobalt cake with 15 % Co was easily produced in laboratory experiments in the cobalt removal. The zinc powder consumption in the plant for a solution containing Cu, Co, Ni and Cd (1000, 25, 30 and 350 mg/l, respectively), was around 1.8 g/l; i.e. only 1.4 times the stoichiometric demand – or, about 60% saving in powder consumption. Two processes for direct leaching of the concentrate under atmospheric conditions were developed, one of which was implemented in the Kokkola zinc plant. Compared to the existing pressure leach technology, savings were obtained mostly in investment. The scientific basis for the most important processes and process improvements is given in the doctoral thesis. This includes mathematical modeling and thermodynamic evaluation of experimental results and hypotheses developed. Five of the processes developed in this research and development program were implemented in the plant and are still operated. Even though these processes were developed with the focus on the plant in Kokkola, they can also be implemented at low cost in most of the zinc plants globally, and have thus a great significance in the development of the electrolytic zinc process in general.