Corrosion behaviour of boiler tube materials during combustion of fuels containing Zn and Pb

Många förbränningsanläggningar som bränner utmanande bränslen såsom restfraktioner och avfall råkar ut för problem med ökad korrosion på överhettare och/eller vattenväggar pga. komponenter i bränslena som är korrosiva. För att minimera problemen i avfallseldade pannor hålls ångparametrarna på en relativt låg nivå, vilket drastiskt minskar energiproduktionen. Beläggningarna i avfallseldade pannor består till största delen av element som är förknippade med högtemperaturkorrosion: Cl, S, alkalimetaller, främst K och Na, och tungmetaller som Pb och Zn, och det finns också indikationer av Br-förekomst. Det låga ångtrycket i avfallseldade pannor påverkar också stålrörens temperatur i pannväggarna i eldstaden. I dagens läge hålls temperaturen normalt vid 300-400 °C. Alkalikloridorsakad (KCl, NaCl) högtemperaturkorrosion har inte rapporterats vara relevant vid såpass låga temperaturer, men närvaro av Zn- och Pb-komponenter i beläggningarna har påvisats förorsaka ökad korrosion redan vid 300-400 °C. Vid förbränning kan Zn och Pb reagera med S och Cl och bilda klorider och sulfater i rökgaserna. Dessa tungmetallföreningar är speciellt problematiska pga. de bildar lågsmältande saltblandningar. Dessa lågsmältande gasformiga eller fasta föreningar följer rökgasen och kan sedan fastna eller kondensera på kallare ytor på pannväggar eller överhettare för att sedan bilda aggressiva beläggningar. Tungmetallrika (Pb, Zn) klorider och sulfater ökar risken för korrosion, och effekten förstärks ytterligare vid närvaro av smälta. Motivet med den här studien var att få en bättre insikt i högtemperaturkorrosion förorsakad av Zn och Pb, samt att undersöka och prediktera beteendet och motståndskraften hos några stålkvaliteter som används i överhettare och pannväggar i tungmetallrika förhållanden och höga materialtemperaturer. Omfattande laboratorie-, småskale- och fullskaletest utfördes. Resultaten kan direkt utnyttjas i praktiska applikationer, t.ex. vid materialval, eller vid utveckling av korrosionsmotverkande verktyg för att hitta initierande faktorer och förstå deras effekt på högtemperaturkorrosion.

Repair of segmental bone defects with fiber-reinforced composite: a study of material development and an animal model on rabbits

The Repair of segmental defects in load-bearing long bones is a challenging task because of the diversity of the load affecting the area; axial, bending, shearing and torsional forces all come together to test the stability/integrity of the bone. The natural biomechanical requirements for bone restorative materials include strength to withstand heavy loads, and adaptivity to conform into a biological environment without disturbing or damaging it. Fiber-reinforced composite (FRC) materials have shown promise, as metals and ceramics have been too rigid, and polymers alone are lacking in strength which is needed for restoration. The versatility of the fiber-reinforced composites also allows tailoring of the composite to meet the multitude of bone properties in the skeleton. The attachment and incorporation of a bone substitute to bone has been advanced by different surface modification methods. Most often this is achieved by the creation of surface texture, which allows bone growth, onto the substitute, creating a mechanical interlocking. Another method is to alter the chemical properties of the surface to create bonding with the bone – for example with a hydroxyapatite (HA) or a bioactive glass (BG) coating. A novel fiber-reinforced composite implant material with a porous surface was developed for bone substitution purposes in load-bearing applications. The material’s biomechanical properties were tailored with unidirectional fiber reinforcement to match the strength of cortical bone. To advance bone growth onto the material, an optimal surface porosity was created by a dissolution process, and an addition of bioactive glass to the material was explored. The effects of dissolution and orientation of the fiber reinforcement were also evaluated for bone-bonding purposes. The Biological response to the implant material was evaluated in a cell culture study to assure the safety of the materials combined. To test the material’s properties in a clinical setting, an animal model was used. A critical-size bone defect in a rabbit’s tibia was used to test the material in a load-bearing application, with short- and long-term follow-up, and a histological evaluation of the incorporation to the host bone. The biomechanical results of the study showed that the material is durable and the tailoring of the properties can be reproduced reliably. The Biological response - ex vivo - to the created surface structure favours the attachment and growth of bone cells, with the additional benefit of bioactive glass appearing on the surface. No toxic reactions to possible agents leaching from the material could be detected in the cell culture study when compared to a nontoxic control material. The mechanical interlocking was enhanced - as expected - with the porosity, whereas the reinforcing fibers protruding from the surface of the implant gave additional strength when tested in a bone-bonding model. Animal experiments verified that the material is capable of withstanding load-bearing conditions in prolonged use without breaking of the material or creating stress shielding effects to the host bone. A Histological examination verified the enhanced incorporation to host bone with an abundance of bone growth onto and over the material. This was achieved with minimal tissue reactions to a foreign body. An FRC implant with surface porosity displays potential in the field of reconstructive surgery, especially regarding large bone defects with high demands on strength and shape retention in load-bearing areas or flat bones such as facial / cranial bones. The benefits of modifying the strength of the material and adjusting the surface properties with fiber reinforcement and bone-bonding additives to meet the requirements of different bone qualities are still to be fully discovered.

Biodiversity and ecosystem functioning in angiosperm communities in the Baltic Sea

The biological variation in nature is called biodiversity. Anthropogenic pressures have led to a loss of biodiversity, alarming scientists as to what consequences declining diversity has for ecosystem functioning. The general consensus is that diversity (e.g. species richness or identity) affects functioning and provides services from which humans benefit. The aim of this thesis was to investigate how aquatic plant species richness and identity affect ecosystem functioning in terms of processes such as primary production, nutrient availability, epifaunal colonization and properties e.g. stability of Zostera marina subjected to shading. The main work was carried out in the field and ranged temporally from weeklong to 3.5 months-long experiments. The experimental plants used frequently co-occur in submerged meadows in the northern Baltic Sea and consist of eelgrass (Z. marina), perfoliate pondweed (Potamogeton perfoliatus), sago pondweed (P. pectinatus), slender-leaved pondweed (P. filiformis) and horned pondweed (Zannichellia palustris). The results showed that plant richness affected epifaunal community variables weakly, but had a strong positive effect on infaunal species number and functional diversity, while plant identity had strong effects on amphipods (Gammarus spp.), of which abundances were higher in plant assemblages consisting of P. perfoliatus. Depending on the starting standardizing unit, plant richness showed varying effects on primary production. In shoot density-standardized plots, plant richness increased the shoot densities of three out of four species and enhanced the plant biomass production. Both positive complementarity and selection effects were found to underpin the positive biodiversity effects. In shoot biomass-standardized plots, richness effects only affected biomass production of one species. Negative selection was prevalent, counteracting positive complementarity, which resulted in no significant biodiversity effect. The stability of Z. marina was affected by plant richness in such that Z. marina growing in polycultures lost proportionally less biomass than Z. marina in monocultures and thus had a higher resistance to shading. Monoculture plants in turn gained biomass faster, and thereby had a faster recovery than Z. marina growing in polycultures. These results indicate that positive interspecific interactions occurred during shading, while the faster recovery of monocultures suggests that the change from shading stress to recovery resulted in a shift from positive interactions to resource competition between species. The results derived from this thesis show that plant diversity affects ecosystem functioning and contribute to the growing knowledge of plant diversity being an important component of aquatic ecosystems. Diverse plant communities sustain higher primary productivity than comparable monocultures, affect faunal communities positively and enhance stability. Richness and identity effects vary, and identity has generally stronger effects on more variables than richness. However, species-rich communities are likely to contain several species with differing effects on functions, which renders species richness important for functioning. Mixed meadows add to coastal ecosystem functioning in the northern Baltic Sea and may provide with services essential for human well-being.

Identification and application of bile metabolites to assess the exposure of fish to pharmaceuticals in the environment

Thousands of tons of pharmaceuticals are consumed yearly worldwide. Due to the continuous and increasing consumption and their incomplete elimination in wastewater treatment plants (WWTP), pharmaceuticals and their metabolites can be detected in receiving waters, although at low concentrations (ng to low μg/L). As bioactive molecules the presence of pharmaceuticals in the aquatic environment must be considered potentially hazardous for the aquatic organisms. In this thesis, the biotransformation and excretion of pharmaceuticals in fish was studied. The main biotransformation pathways of three anti‐inflammatory drugs, diclofenac, naproxen and ibuprofen, in rainbow trout were glucuronidation and taurine conjugation of the parent compounds and their phase I metabolites. The same metabolites were present in fish bile in aquatic exposures as in fish dosed with intraperitoneal injection. Higher bioconcentration factor in bile (BCFbile) was found for ibuprofen when compared to diclofenac and naproxen. Laboratory exposure studies were followed by a study of uptake of pharmaceuticals in a wild fish population living in lake contaminated with WWTP effluents. Of the analyzed 17 pharmaceuticals and six phase I metabolites, only diclofenac, naproxen and ibuprofen was present in bream and roach bile. It was shown, that diclofenac, naproxen and ibuprofen excreted by the liver can be found in rainbow trout and in two native fish species living in the receiving waters. In the bream and roach bile, the concentrations of diclofenac, naproxen and ibuprofen were roughly 1000 times higher than those found in the lake water, while in the laboratory exposures, the bioconcentration of the compounds and their metabolites in rainbow trout bile were at the same level as in wild fish or an order of magnitude higher. Thus, the parent compounds and their metabolites in fish bile can be used as a reliable biomarker to monitor the exposure of fish to environmental pharmaceuticals present in water receiving discharges from WWTPs.

Prediction of 3D structure and ligand-binding properties : ABC transporters and flavodiiron proteins from Synechocystis sp. strain PCC 6803

Cyanobacteria are unicellular, non-nitrogen-fixing prokaryotes, which perform photosynthesis similarly as higher plants. The cyanobacterium Synechocystis sp. strain PCC 6803 is used as a model organism in photosynthesis research. My research described herein aims at understanding the function of the photosynthetic machinery and how it responds to changes in the environment. Detailed knowledge of the regulation of photosynthesis in cyanobacteria can be utilized for biotechnological purposes, for example in the harnessing of solar energy for biofuel production. In photosynthesis, iron participates in electron transfer. Here, we focused on iron transport in Synechocystis sp. strain PCC 6803 and particularly on the environmental regulation of the genes encoding the FutA2BC ferric iron transporter, which belongs to the ABC transporter family. A homology model built for the ATP-binding subunit FutC indicates that it has a functional ATPbinding site as well as conserved interactions with the channel-forming subunit FutB in the transporter complex. Polyamines are important for the cell proliferation, differentiation and apoptosis in prokaryotic and eukaryotic cells. In plants, polyamines have special roles in stress response and in plant survival. The polyamine metabolism in cyanobacteria in response to environmental stress is of interest in research on stress tolerance of higher plants. In this thesis, the potd gene encoding an polyamine transporter subunit from Synechocystis sp. strain PCC 6803 was characterized for the first time. A homology model built for PotD protein indicated that it has capability of binding polyamines, with the preference for spermidine. Furthermore, in order to investigate the structural features of the substrate specificity, polyamines were docked into the binding site. Spermidine was positioned very similarly in Synechocystis PotD as in the template structure and had most favorable interactions of the docked polyamines. Based on the homology model, experimental work was conducted, which confirmed the binding preference. Flavodiiron proteins (Flv) are enzymes, which protect the cell against toxicity of oxygen and/or nitric oxide by reduction. In this thesis, we present a novel type of photoprotection mechanism in cyanobacteria by the heterodimer of Flv2/Flv4. The constructed homology model of Flv2/Flv4 suggests a functional heterodimer capable of rapid electron transfer. The unknown protein sll0218, encoded by the flv2-flv4 operon, is assumed to facilitate the interaction of the Flv2/Flv4 heterodimer and energy transfer between the phycobilisome and PSII. Flv2/Flv4 provides an alternative electron transfer pathway and functions as an electron sink in PSII electron transfer.

Development of porous glass-fiber reinforced composite for bone implants. Evaluation of antimicrobial effect and implant fixation

Cranial bone reconstructions are necessary for correcting large skull bone defects due to trauma, tumors, infections and craniotomies. Traditional synthetic implant materials include solid or mesh titanium, various plastics and ceramics. Recently, biostable glass-fiber reinforced composites (FRC), which are based on bifunctional methacrylate resin, were introduced as novel implant solution. FRCs were originally developed and clinically used in dental applications. As a result of further in vitro and in vivo testing, these composites were also approved for clinical use in cranial surgery. To date, reconstructions of large bone defects were performed in 35 patients. This thesis is dedicated to the development of a novel FRC-based implant for cranial reconstructions. The proposed multi-component implant consists of three main parts: (i) porous FRC structure; (ii) bioactive glass granules embedded between FRC layers and (iii) a silver-polysaccharide nanocomposite coating. The porosity of the FRC structure should allow bone ingrowth. Bioactive glass as an osteopromotive material is expected to stimulate the formation of new bone. The polysaccharide coating is expected to prevent bacterial colonization of the implant. The FRC implants developed in this study are based on the porous network of randomly-oriented E-glass fibers bound together by non-resorbable photopolymerizable methacrylate resin. These structures had a total porosity of 10–70 volume %, of which > 70% were open pores. The pore sizes > 100 μm were in the biologically-relevant range (50-400 μm), which is essential for vascularization and bone ingrowth. Bone ingrowth into these structures was simulated by imbedding of porous FRC specimens in gypsum. Results of push-out tests indicated the increase in the shear strength and fracture toughness of the interface with the increase in the total porosity of FRC specimens. The osteopromotive effect of bioactive glass is based on its dissolution in the physiological environment. Here, calcium and phosphate ions, released from the glass, precipitated on the glass surface and its proximity (the FRC) and formed bone-like apatite. The biomineralization of the FRC structure, due to the bioactive glass reactions, was studied in Simulated Body Fluid (SBF) in static and dynamic conditions. An antimicrobial, non-cytotoxic polysaccharide coating, containing silver nanoparticles, was obtained through strong electrostatic interactions with the surface of FRC. In in vitro conditions the lactose-modified chitosan (chitlac) coating showed no signs of degradation within seven days of exposure to lysozyme or one day to hydrogen peroxide (H2O2). The antimicrobial efficacy of the coating was tested against Staphylococcus aureus and Pseudomonas aeruginosa. The contact-active coating had an excellent short time antimicrobial effect. The coating neither affected the initial adhesion of microorganisms to the implant surface nor the biofilm formation after 24 h and 72 h of incubation. Silver ions released to the aqueous environment led to a reduction of bacterial growth in the culture medium.

Composite artistry in the Book of Numbers : a study in biblical narrative conventions

The present thesis discusses the coherence or lack of coherence in the book of Numbers, with special regard to its narrative features. The fragmented nature of Numbers is a well-known problem in research on the book, affecting how we approach and interpret it, but to date there has not been any thorough investigation of the narrative features of the work and how they might contribute to the coherence or the lack of coherence in the book. The discussion is pursued in light of narrative theory, and especially in connection to three parameters that are typically understood to be invoked in the interpretation of narratives: 1) a narrative paradigm, or ‘story,’ meaning events related to each other temporally, causally, and thematically, in a plot with a beginning, middle, and end; 2) discourse, being the expression plane of a narrative, or the devices that an author has at hand in constructing a narrative; 3) the situation or languagegame of the narrative, prototypical examples being factual reports, which seeks to depict a state of affairs, and storytelling narratives, driven by a demand for tellability. In view of these parameters the present thesis argues that it is reasonable to form four groups to describe the narrative material of Numbers: genuine narratives (e.g. Num 12), independent narrative sequences (e.g. Num 5:1-4), instrumental scenes and situations (e.g. Num 27:1-5), and narrative fragments (e.g. Num 18:1). These groups are mixed throughout with non-narrative materials. Seen together, however, the narrative features of these groups can be understood to create an attenuated narrative sequence from beginning to end in Numbers, where one thing happens after another. This sequence, termed the ‘larger story’ of Numbers, concerns the wandering of Israel from Sinai to Moab. Furthermore, the larger story has a fragmented plot. The end-point is fixed on the promised land, Israel prepares for the wandering towards it (Num 1-10), rebels against wandering and the promise and is sent back into the wilderness (Num 13-14), returns again after forty years (Num 21ff.), and prepares for conquering the land (Num 22-36). Finally, themes of the promised land, generational succession, and obedience-disobedience, operate in this larger story. Purity is also a significant theme in the book, albeit not connected to plot in the larger story. All in all, sequence, plot, and theme in the larger story of Numbers can be understood to bring some coherence to the book. However, neither aspect entirely subsumes the whole book, and the four groups of narrative materials can also be understood to underscore the incoherence of the work in differentiating its variegated narrative contents. Numbers should therefore be described as an anthology of different materials that are loosely connected through its narrative features in the larger story, with the aim of informing Israelite identity by depicting a certain period in the early history of the people.

Comparison of Biomass Gasification Technologies for Natural Gas Substitution in Iron Ore Pelletizing Plants

The iron ore pelletizing process consumes high amounts of energy, including nonrenewable sources, such as natural gas. Due to fossil fuels scarcity and increasing concerns regarding sustainability and global warming, at least partial substitution by renewable energy seems inevitable. Gasification projects are being successfully developed in Northern Europe, and large-scale circulating fluidized bed biomass gasifiers have been commissioned in e.g. Finland. As Brazil has abundant biomass resources, biomass gasification is a promising technology in the near future. Biomasses can be converted into product gas through gasification. This work compares different technologies, e.g. air, oxygen and steam gasification, focusing on the use of the product gas in the indurating machine. The use of biosynthetic natural gas is also evaluated. Main parameters utilized to assess the suitability of product gas were adiabatic flame temperature and volumetric flow rate. It was found that low energy content product gas could be utilized in the traveling grate, but it would require burner’s to be changed. On the other hand, bio-SGN could be utilized without any adaptions. Economical assessment showed that all gasification plants are feasible for sizes greater than 60 MW. Bio-SNG production is still more expensive than natural gas in any case.

Unidirectional fiber-reinforced composite as an oral implant abutment material: Experimental studies of E-glass fiber/BisGMA-TEGDMA polymer in vitro

Fiber-reinforced composites (FRCs) are a new group of non-metallic biomaterials showing a growing popularity in many dental and medical applications. As an oral implant material, FRC is biocompatible in bone tissue environment. Soft tissue integration to FRC polymer material is unclear. This series of in vitro studies aimed at evaluating unidirectional E-glass FRC polymer in terms of mechanical, chemical, and biological properties in an attempt to develop a new non-metallic oral implant abutment alternative. Two different types of substrates were investigated: (a) Plain polymer (BisGMA 50%–TEGDMA 50%) and (b) Unidirectional FRC. The mechanical behavior of high fiber-density FRCs was assessed using a three-point bending test. Surface characterization was performed using scanning electron and spinning disk confocal microscopes. The surface wettability/energy was determined using sessile drop method. The blood response, including blood-clotting ability and platelet morphology was evaluated. Human gingival fibroblast cell responses - adhesion kinetics, adhesion strength, and proliferation activity - were studied in cell culture environment using routine test conditions. A novel tissue culture method was developed and used to evaluate porcine gingival tissue graft attachment and growth on the experimental composite implants. The analysis of the mechanical properties showed that there is a direct proportionality in the relationship between E-glass fiber volume fraction and toughness, modulus of elasticity, and load bearing capacity; however, flexural strength did not show significant improvement when high fiber-density FRC is used. FRCs showed moderate hydrophilic properties owing to the presence of exposed glass fibers on the polymer surface. Blood-clotting time was shorter on FRC substrates than on plain polymer. The FRC substrates also showed higher platelet activation state than plain polymer substrates. Fibroblast cell adhesion strength and proliferation rate were highly pronounced on FRCs. A tissue culture study revealed that gingival epithelium and connective tissue established an immediate close contact with both plain polymer and FRC implants. However, FRC seemed to guide epithelial migration outwards from the tissue/implant interface. Due to the anisotropic and hydrophilic nature of FRC, it can be concluded that this material enhances biological events related with soft tissue integration on oral implant surface.

Use of fiber-reinforced composite framework and thermochromic pigment in maxillofacial prostheses

The purpose of this investigation was to evaluate the possibility to enhance certain qualities of facial prostheses. Polymethyl methacrylate is still being used as base mate¬rial or clip carrier material, but it is hard and heavy, and debonding of the silicone from the acrylic base material is a frequent problem. This thesis aims to evaluate the use of fiber-reinforced composite (FRC) as framework material for maxillofacial silicone prostheses. FRC has been used as reinforcement in removable and fixed partial dentures since the 1990s. This material is lightweight and can be fabricated to compress the margins of the prosthesis slightly, to keep it tightly against the skin during jaw movements and facial expressions. Additionally, the use of a thermochromic pigment, colorless in room temperature and red in a cold environment, was studied in order to evaluate the possibility of using this color changing pigment in facial prostheses to mimic the color change of facial skin in cold weather. The tensile bond strength between pre-impregnated, unidirectional FRC and maxillofacial silicone elastomer was studied. Three different bonding agents or primers were compared. Bond strength was improved by one of the primers and by roughening the surface. The effect of a skin compressing glass fiber-reinforced composite framework on facial skin blood flow was studied by using a face mask, constructed with a compression pad corresponding to the outer margin of a glass fiber-reinforced framework beam of a facial prosthesis. The skin blood flow of ten healthy volunteers, aged 23-25 years, was measured during touch, light, and moderate compression of the skin, by using laser Doppler imaging technique. None of the compressions showed any marked effects on local skin blood flow. There were no significant differences between blood flow during compression and at baseline. Maxillofacial silicone elastomer was colored intrinsically with conventional color pigments: a control group containing only conventional pigments was compared to two test groups with 0.2 wt% and 0.6 wt% thermochromic pigment added. The color of the material was measured with a spectrophotometer in room temperature and after storage in a freezer. The color stability of the maxillofacial silicone elastomer colored with thermo¬chromic pigment was evaluated by artificial aging. The color dif¬ference of the L* (lightness) and a* values (redness), comparing color after the samples were stored at room temperature and in a freezer (-19°C), was statistically significant for both 0.2 wt% and 0.6 wt% thermo¬chromic pigment groups. The differences in the b* values (yellowness) were statistically significant for the 0.6 wt% group. Exposure to ultraviolet (UV) radiation led to visually noticeable and statistically signifi¬cant color changes (ΔE) in all color values in both test groups. The specimens containing thermochromic pigment were very sensitive to UV radiation. In conclusion, a framework of fiber-reinforced composite can successfully be bonded to maxillofacial silicone elastomer, and a framework beam, compressing the facial skin, did not remarkably alter the skin blood flow on healthy, young adults. The thermochromic pigment showed color change in maxillofacial silicone elastomer. However, artificial aging showed that it was too sensitive to UV radiation to be used, as such, in maxillofacial prostheses.

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.

Design and validation of stateful composite RESTful web services

A web service is a software system that provides a machine-processable interface to the other machines over the network using different Internet protocols. They are being increasingly used in the industry in order to automate different tasks and offer services to a wider audience. The REST architectural style aims at producing scalable and extensible web services using technologies that play well with the existing tools and infrastructure of the web. It provides a uniform set of operation that can be used to invoke a CRUD interface (create, retrieve, update and delete) of a web service. The stateless behavior of the service interface requires that every request to a resource is independent of the previous ones facilitating scalability. Automated systems, e.g., hotel reservation systems, provide advanced scenarios for stateful services that require a certain sequence of requests that must be followed in order to fulfill the service goals. Designing and developing such services for advanced scenarios with REST constraints require rigorous approaches that are capable of creating web services that can be trusted for their behavior. Systems that can be trusted for their behavior can be termed as dependable systems. This thesis presents an integrated design, analysis and validation approach that facilitates the service developer to create dependable and stateful REST web services. The main contribution of this thesis is that we provide a novel model-driven methodology to design behavioral REST web service interfaces and their compositions. The behavioral interfaces provide information on what methods can be invoked on a service and the pre- and post-conditions of these methods. The methodology uses Unified Modeling Language (UML), as the modeling language, which has a wide user base and has mature tools that are continuously evolving. We have used UML class diagram and UML state machine diagram with additional design constraints to provide resource and behavioral models, respectively, for designing REST web service interfaces. These service design models serve as a specification document and the information presented in them have manifold applications. The service design models also contain information about the time and domain requirements of the service that can help in requirement traceability which is an important part of our approach. Requirement traceability helps in capturing faults in the design models and other elements of software development environment by tracing back and forth the unfulfilled requirements of the service. The information about service actors is also included in the design models which is required for authenticating the service requests by authorized actors since not all types of users have access to all the resources. In addition, following our design approach, the service developer can ensure that the designed web service interfaces will be REST compliant. The second contribution of this thesis is consistency analysis of the behavioral REST interfaces. To overcome the inconsistency problem and design errors in our service models, we have used semantic technologies. The REST interfaces are represented in web ontology language, OWL2, that can be part of the semantic web. These interfaces are used with OWL 2 reasoners to check unsatisfiable concepts which result in implementations that fail. This work is fully automated thanks to the implemented translation tool and the existing OWL 2 reasoners. The third contribution of this thesis is the verification and validation of REST web services. We have used model checking techniques with UPPAAL model checker for this purpose. The timed automata of UML based service design models are generated with our transformation tool that are verified for their basic characteristics like deadlock freedom, liveness, reachability and safety. The implementation of a web service is tested using a black-box testing approach. Test cases are generated from the UPPAAL timed automata and using the online testing tool, UPPAAL TRON, the service implementation is validated at runtime against its specifications. Requirement traceability is also addressed in our validation approach with which we can see what service goals are met and trace back the unfulfilled service goals to detect the faults in the design models. A final contribution of the thesis is an implementation of behavioral REST interfaces and service monitors from the service design models. The partial code generation tool creates code skeletons of REST web services with method pre and post-conditions. The preconditions of methods constrain the user to invoke the stateful REST service under the right conditions and the post condition constraint the service developer to implement the right functionality. The details of the methods can be manually inserted by the developer as required. We do not target complete automation because we focus only on the interface aspects of the web service. The applicability of the approach is demonstrated with a pedagogical example of a hotel room booking service and a relatively complex worked example of holiday booking service taken from the industrial context. The former example presents a simple explanation of the approach and the later worked example shows how stateful and timed web services offering complex scenarios and involving other web services can be constructed using our approach.

International Advanced Water Technologies Centre, IAWTC/LADEC and LUT 2013 : Questionnaire Responses from Russian Drinking Water and Wastewater Treatment Plants

In this report, information is published concerning Russian water and wastewater treatment plants. The information is based on a questionnaire sent to 70 water and wastewater treatment plants in 2012-2013. The questionnaire was prepared by the International Advanced Water Technologies Centre (IAWTC) and Lahti Development Company (LADEC). The questions dealt with an assessment of the present state, the need for changes, renovation, investments, and how to improve the efficiency of the operation by training and investments. A significant need to renew the old pipelines, constructions, and processes was clearly evident. The aggregated answers can be utilized in Russia as internal benchmarking in order to arrange training and plant visits, which were requested in many of the answers. Sharing this open report with the respondents can aid networking and awareness of HELCOM requirements which relate to waste water treatment plants discharging their waste water directly or indirectly into the Baltic Sea. The aim of this report is to provide information for Finnish small and medium size companies (SMEs) as regards possible water related exportation to different parts of Russia.

Pp2a: At The Crossroads Between Growth and Defence In Plants

Living organisms manage their resources in well evolutionary-preserved manner to grow and reproduce. Plants are no exceptions, beginning from their seed stage they have to perceive environmental conditions to avoid germination at wrong time or rough soil. Under favourable conditions, plants invest photosynthetic end products in cell and organ growth to provide best possible conditions for generation of offspring. Under natural conditions, however, plants are exposed to a multitude of environmental stress factors, including high light and insufficient light, drought and flooding, various bacteria and viruses, herbivores, and other plants that compete for nutrients and light. To survive under environmental challenges, plants have evolved signaling mechanisms that recognise environmental changes and perform fine-tuned actions that maintain cellular homeostasis. Controlled phosphorylation and dephosphorylation of proteins plays an important role in maintaining balanced flow of information within cells. In this study, I examined the role of protein phosphatase 2A (PP2A) on plant growth and acclimation under optimal and stressful conditions. To this aim, I studied gene expression profiles, proteomes and protein interactions, and their impacts on plant health and survival, taking advantage of the model plant Arabidopsis thaliana and the mutant approach. Special emphasis was made on two highly similar PP2A-B regulatory subunits, B’γ and B’ζ. Promoters of B’γ and B’ζ were found to be similarly active in the developing tissues of the plant. In mature leaves, however, the promoter of B’γ was active in patches in leaf periphery, while the activity of B’ζ promoter was evident in leaf edges. The partially overlapping expression patterns, together with computational models of B’γ and B’ζ within trimeric PP2A holoenzymes suggested that B’γ and B’ζ may competitively bind into similar PP2A trimmers and thus influence each other’s actions. Arabidopsis thaliana pp2a-b’γ and pp2a-b’γζ double mutants showed dwarfish phenotypes, indicating that B’γ and B’ζ are needed for appropriate growth regulation under favorable conditions. However, while pp2a-b’γ displayed constitutive immune responses and appearance of premature yellowings on leaves, the pp2a-b’γζ double mutant supressed these yellowings. More detailed analysis of defense responses revealed that B’γ and B’ζ mediate counteracting effects on salicylic acid dependent defense signalling. Associated with this, B’γ and B’ζ were both found to interact in vivo with CALCIUM DEPENDENT PROTEIN KINASE 1 (CPK1), a crucial element of salicylic acid signalling pathway against pathogens in plants. In addition, B’γ was shown to modulate cellular reactive oxygen species (ROS) metabolism by controlling the abundance of ALTERNATIVE OXIDASE 1A and 1D in mitochondria. PP2A B’γ and B’ζ subunits turned out to play crucial roles in the optimization of plant choices during their development. Taken together, PP2A allows fluent responses to environmental changes, maintenance of plant homeostasis, and grant survivability with minimised cost of redirection of resources from growth to defence.

Portfolio Selection via Composite Measure Analysis: Evidence from the U.S. Stock Market

The aim of this research is to examine the pricing anomalies existing in the U.S. market during 1986 to 2011. The sample of stocks is divided into decile portfolios based on seven individual valuation ratios (E/P, B/P, S/P, EBIT/EV, EVITDA/EV, D/P, and CE/P) and price momentum to investigate the efficiency of individual valuation ratio and their combinations as portfolio formation criteria. This is the first time in financial literature when CE/P is employed as a constituent of composite value measure. The combinations are based on median scaled composite value measures and TOPSIS method. During the sample period value portfolios significantly outperform both the market portfolio and comparable glamour portfolios. The results show the highest return for the value portfolio that was based on the combination of S/P & CE/P ratios. The outcome of this research will increase the understanding on the suitability of different methodologies for portfolio selection. It will help managers to take advantage of the results of different methodologies in order to gain returns above the market.