Production of Mg(OH)2 from Mg-silicate rock for CO2 mineral sequestration

Sequestration of carbon dioxide in mineral rocks, also known as CO2 Capture and Mineralization (CCM), is considered to have a huge potential in stabilizing anthropogenic CO2 emissions. One of the CCM routes is the ex situ indirect gas/sold carbonation of reactive materials, such as Mg(OH)2, produced from abundantly available Mg-silicate rocks. The gas/solid carbonation method is intensively researched at Åbo Akademi University (ÅAU ), Finland because it is energetically attractive and utilizes the exothermic chemistry of Mg(OH)2 carbonation. In this thesis, a method for producing Mg(OH)2 from Mg-silicate rocks for CCM was investigated, and the process efficiency, energy and environmental impact assessed. The Mg(OH)2 process studied here was first proposed in 2008 in a Master’s Thesis by the author. At that time the process was applied to only one Mg-silicate rock (Finnish serpentinite from the Hitura nickel mine site of Finn Nickel) and the optimum process conversions, energy and environmental performance were not known. Producing Mg(OH)2 from Mg-silicate rocks involves a two-staged process of Mg extraction and Mg(OH)2 precipitation. The first stage extracts Mg and other cations by reacting pulverized serpentinite or olivine rocks with ammonium sulfate (AS) salt at 400 - 550 oC (preferably < 450 oC). In the second stage, ammonia solution reacts with the cations (extracted from the first stage after they are leached in water) to form mainly FeOOH, high purity Mg(OH)2 and aqueous (dissolved) AS. The Mg(OH)2 process described here is closed loop in nature; gaseous ammonia and water vapour are produced from the extraction stage, recovered and used as reagent for the precipitation stage. The AS reagent is thereafter recovered after the precipitation stage. The Mg extraction stage, being the conversion-determining and the most energy-intensive step of the entire CCM process chain, received a prominent attention in this study. The extraction behavior and reactivity of different rocks types (serpentinite and olivine rocks) from different locations worldwide (Australia, Finland, Lithuania, Norway and Portugal) was tested. Also, parametric evaluation was carried out to determine the optimal reaction temperature, time and chemical reagent (AS). Effects of reactor types and configuration, mixing and scale-up possibilities were also studied. The Mg(OH)2 produced can be used to convert CO2 to thermodynamically stable and environmentally benign magnesium carbonate. Therefore, the process energy and life cycle environmental performance of the ÅAU CCM technique that first produces Mg(OH)2 and the carbonates in a pressurized fluidized bed (FB) were assessed. The life cycle energy and environmental assessment approach applied in this thesis is motivated by the fact that the CCM technology should in itself offer a solution to what is both an energy and environmental problem. Results obtained in this study show that different Mg-silicate rocks react differently; olivine rocks being far less reactive than serpentinite rocks. In summary, the reactivity of Mg-silicate rocks is a function of both the chemical and physical properties of rocks. Reaction temperature and time remain important parameters to consider in process design and operation. Heat transfer properties of the reactor determine the temperature at which maximum Mg extraction is obtained. Also, an increase in reaction temperature leads to an increase in the extent of extraction, reaching a maximum yield at different temperatures depending on the reaction time. Process energy requirement for producing Mg(OH)2 from a hypothetical case of an iron-free serpentine rock is 3.62 GJ/t-CO2. This value can increase by 16 - 68% depending on the type of iron compound (FeO, Fe2O3 or Fe3O4) in the mineral. This suggests that the benefit from the potential use of FeOOH as an iron ore feedstock in iron and steelmaking should be determined by considering the energy, cost and emissions associated with the FeOOH by-product. AS recovery through crystallization is the second most energy intensive unit operation after the extraction reaction. However, the choice of mechanical vapor recompression (MVR) over the “simple evaporation” crystallization method has a potential energy savings of 15.2 GJ/t-CO2 (84 % savings). Integrating the Mg(OH)2 production method and the gas/solid carbonation process could provide up to an 25% energy offset to the CCM process energy requirements. Life cycle inventory assessment (LCIA) results show that for every ton of CO2 mineralized, the ÅAU CCM process avoids 430 - 480 kg CO2. The Mg(OH)2 process studied in this thesis has many promising features. Even at the current high energy and environmental burden, producing Mg(OH)2 from Mg-silicates can play a significant role in advancing CCM processes. However, dedicated future research and development (R&D) have potential to significantly improve the Mg(OH)2 process performance.

Electroactive ion exchange membranes based on conducting polymers

Ion exchange membranes are indispensable for the separation of ionic species. They can discriminate between anions and cations depending on the type of fixed ionic group present in the membrane. These conventional ion exchange membranes (CIX) have exceptional ionic conductivity, which is advantageous in various electromembrane separation processes such as electrodialysis, electrodeionisation and electrochemical ion exchange. The main disadvantage of CIX membranes is their high electrical resistance owing to the fact that the membranes are electronically non conductive. An alternative can be electroactive ion exchange membranes, which are ionically and electronically conducting. Polypyrrole (PPy) is a type of electroactive ion exchange material as well as a commonly known conducting polymer. When PPy membranes are repeatedly reduced and oxidised, ions are pumped through the membrane. The main aim of this thesis was to develop electroactive cation transport membranes based on PPy for the selective transport of divalent cations. Membranes developed composed of PPy films deposited on commercially available support materials. To carry out this study, cation exchange membranes based on PPy doped with immobile anions were prepared. Two types of dopant anions known to interact with divalent metal ions were considered, namely 4-sulphonic calix[6]arene (C6S) and carboxylated multiwalled carbon nanotubes (CNT). The transport of ions across membranes containing PPy doped with polystyrene sulphonate (PSS) and PPy doped with para-toluene sulphonate (pTS) was also studied in order to understand the nature of ion transport and permeability across PPy(CNT) and PPy(C6S) membranes. In the course of these studies, membrane characterisation was performed using electrochemical quartz crystal microbalance (EQCM) and scanning electron microscopy (SEM). Permeability of the membranes towards divalent cations was explored using a two compartment transport cell. EQCM results demonstrated that the ion exchange behaviour of polypyrrole is dependent on a number of factors including the type of dopant anion present, the type of ions present in the surrounding medium, the scan rate used during the experiment and the previous history of the polymer film. The morphology of PPy films was found to change when the dopant anion was varied and even when the thickness of the film was altered in some cases. In nearly all cases the permeability of the membranes towards metal ions followed the order K+ > Ca2+ > Mn2+. The one exception was PPy(C6S), for which the permeability followed the order Ca2+ ≥ K+ > Mn2+ > Co2+ > Cr3+. The above permeability sequences show a strong dependence on the size of the metal ions with metal ions having the smallest hydrated radii exhibiting the highest flux. Another factor that affected the permeability towards metal ions was the thickness of the PPy films. Films with the least thickness showed higher metal ion fluxes. Electrochemical control over ion transport across PPy(CNT) membrane was obtained when films composed of the latter were deposited on track-etched Nucleopore® membranes as support material. In contrast, the flux of ions across the same film was concentration gradient dependent when the polymer was deposited on polyvinylidene difluoride membranes as support material. However, electrochemical control over metal ion transport was achieved with a bilayer type of PPy film consisting of PPy(pTS)/PPy(CNT), irrespective of the type of support material. In the course of studying macroscopic charge balance during transport experiments performed using a two compartment transport cell, it was observed that PPy films were non-permselective. A clear correlation between the change in pH in the receiving solution and the ions transported across the membrane was observed. A decrease in solution pH was detected when the polymer membrane acted primarily as an anion exchanger, while an increase in pH occurred when it functioned as a cation exchanger. When there was an approximately equal flux of anions and cations across the polymer membrane, the pH in the receiving solution was in the range 6 - 8. These observations suggest that macroscopic charge balance during the transport of cations and anions across polypyrrole membranes was maintained by introduction of anions (OH-) and cations (H+) produced via electrolysis of water.

Dispersal and metacommunity dynamics in a soft-sediment benthic system : how well is the seafloor connected?

Connectivity depends on rates of dispersal between communities. For marine soft-sediment communities continued small-scale dispersal as post-larvae and as adults can be equally important in maintaining community composition, as initial recruitment of substrate by pelagic larvae. In this thesis post-larval dispersal strategies of benthic invertebrates, as well as mechanisms by which communities are connected were investigated. Such knowledge on dispersal is scarce, due to the difficulties in actually measuring dispersal directly in nature, and dispersal has not previously been quantified in the Baltic Sea. Different trap-types were used underwater to capture dispersing invertebrates at different sites, while in parallel measuring waves and currents. Local community composition was found to change predictably under varying rates of dispersal and physical connectivity (waves and currents). This response was, however, dependent on dispersal-related traits of taxa. Actively dispersing taxa will be relatively better at maintaining their position, as they are not as dependent on hydrodynamic conditions for dispersal and will be less prone to be passively transported by currents. Taxa also dispersed in relative proportions that were distinctly different from resident community composition and a significant proportion (40 %) of taxa were found to lack a planktonic larval life-stage. Community assembly was re-started in a large-scale manipulative field experiment over one year across several sites, which revealed how patterns of community composition (α-, β- and λ-diversity) change depending on rates of dispersal. Results also demonstrated that in response to small-scale disturbance, initial recruitment was by nearby-dominant species after which other species arrived from successively further away. At later assembly time, the number of coexisting species increased beyond what was expected purely by local niche requirements (species sorting), transferring regional differences in community composition (β-diversity) to the local scale (α-diversity, mass effect). Findings of this thesis complement more theoretical studies in metacommunity ecology by demonstrating that understanding how and when individuals disperse relative to underlying environmental heterogeneity is key to interpreting how patterns of diversity change across different spatial scales. Such information from nature is critical when predicting responses to, for example, different types of disturbances or management actions in conservation.

Structural and operational optimisation : applications in energy systems

In this work mathematical programming models for structural and operational optimisation of energy systems are developed and applied to a selection of energy technology problems. The studied cases are taken from industrial processes and from large regional energy distribution systems. The models are based on Mixed Integer Linear Programming (MILP), Mixed Integer Non-Linear Programming (MINLP) and on a hybrid approach of a combination of Non-Linear Programming (NLP) and Genetic Algorithms (GA). The optimisation of the structure and operation of energy systems in urban regions is treated in the work. Firstly, distributed energy systems (DES) with different energy conversion units and annual variations of consumer heating and electricity demands are considered. Secondly, district cooling systems (DCS) with cooling demands for a large number of consumers are studied, with respect to a long term planning perspective regarding to given predictions of the consumer cooling demand development in a region. The work comprises also the development of applications for heat recovery systems (HRS), where paper machine dryer section HRS is taken as an illustrative example. The heat sources in these systems are moist air streams. Models are developed for different types of equipment price functions. The approach is based on partitioning of the overall temperature range of the system into a number of temperature intervals in order to take into account the strong nonlinearities due to condensation in the heat recovery exchangers. The influence of parameter variations on the solutions of heat recovery systems is analysed firstly by varying cost factors and secondly by varying process parameters. Point-optimal solutions by a fixed parameter approach are compared to robust solutions with given parameter variation ranges. In the work enhanced utilisation of excess heat in heat recovery systems with impingement drying, electricity generation with low grade excess heat and the use of absorption heat transformers to elevate a stream temperature above the excess heat temperature are also studied.

Kaakkois-Suomen ekotehokkuusindikaattorit 2009

ECOREG-hankkeessa luodun alueellisen ekotehokkuuden seuranta- ja arviointijärjestelmän indikaattoreille tehtiin vuoden 2010 aikana viides vuosipäivitys vuosina 2005-2007 kehitetyn toimintamallin mukaisesti. Projektin yhteistyökumppaneina ovat toimineet Kaakkois-Suomen ELY-keskus, Kymenlaakson Liitto ja Etelä-Karjalan liitto. Tässä raportissa esitetään Kaakkois-Suomen ympäristö-, talous- ja sosiaalis-kulttuuristen indikaattorien kehittyminen indikaattorikohtaisesti valittuina aikasarjoina. Indikaattorien lisäksi raportissa käydään läpi vuosiraportoinnin käytännöt ja aikataulut sekä päivitysprosessin aikana esiin tulleet kehitystavoitteet. Lisäksi raportissa esitetään myös indikaattoriryhmäkohtaiset yhteenvedot sekä arviot alueellisen ekotehokkuuden kehittymisestä ja tilasta Kaakkois-Suomessa. Asiantuntija-arvioiden yhteenvedot indikaattorien kehityssuunnista ja tasoista kansalliseen tasoon verrattuna on esitetty sekä mallissa kehitettyjen tilaosoittimien, että sanallisten kuvausten avulla. Kaakkois-Suomen yleistä kehitystä ovat leimanneet vuoden 2008 lopussa alkanut ja seuraavana vuonna jatkunut taloudellinen taantuma. Metsäsektorin rakennemuutos jatkui voimakkaana ja se näkyi arvonlisäyksen osuuden pienenemisenä sekä Etelä-Karjalassa että Kymenlaaksossa. Lama ja metsäteollisuuden tuotantoa koskevat ratkaisut heijastuivat jonkin verran kummankin maakunnan talouteen ja työllisyys heikkeni vuonna 2009. Koko alueelle tyypillinen raskaan liikenteen suuri volyymi valtateillä kääntyi laskuun vuoden 2008 syksyllä ja pysyi edellisvuotta pienempänä tarkasteluvuoden aikana. Kehitys on ekotehokkuus-mielessä jatkunut sekä Etelä-Karjalassa että Kymenlaaksossa edellisvuosien tapaan myönteisesti, mutta talouden ja osittain sosiaalis-kulttuuristen indikaattoreiden osalta muuta maata hitaampana. Sosiaalisen hyvinvoinnin ja kulttuuri-indikaattorien kehitys etenkin ihmisten terveyttä ja hyvinvointia kuvaavalta osalta on Kymenlaaksossa heikentynyt entisestään sekä valtakunnalliseen tasoon että kehitykseen nähden. Etelä-Karjalassa pääosa sosiaalis-kulttuurista kehitystä kuvaavista indikaattoreista kehittyi myönteisesti, mutta tasossa jäätiin valtakunnan keskiarvosta. Talouden kehitys on indikaattorien mukaan ollut maakunnissa melko positiivista lamasta huolimatta; taso oli kuitenkin yleensä kansallisen tason alapuolella. Ympäristön osalta tilanne kehittyi edelleen yleensä positiivisesti. Teollisuuden päästövähennykset tosin johtuivat suurelta osin vähentyneestä tuotannosta. Otetun soran ja kallioiden määrä lisääntyivät kuitenkin kummassakin maakunnassa. Vuotta 2009 koskevassa raportissa on tuttuun tapaan esitetty päivitetyt viimeisimmät saatavilla olevat tilastotiedot. Raportin yhteenveto-osioissa on tuotu esille keskeisiä maakuntien kehitykseen vaikuttaneita tekijöitä. Kummatkin maakunnat ovat edelleen nettomaksajan roolissa. Muutokset edellyttävät sekä valtakunnallisilta että alueellisilta päätöksentekijöiltä panostusta alueen hyvinvointiin ja ihmisten terveyteen, työllisyyteen sekä ilmastomuutokseen maakuntien kehityksen turvaamiseksi ja ekotehokkuuden parantamiseksi.

Pirkanmaan pintavesien toimenpideohjelma vuoteen 2015

Vesienhoidon tavoitteena on vesien hyvän tilan turvaaminen. Vesienhoito on koko Euroopan laajuista, vesipolitiikan puitedirektiiviin pohjautuvaa työtä. Vesipolitiikan puitedirektiivi on Suomessa pantu toimeen lailla vesienhoidon järjestämisestä (2004) ja siihen liittyvillä asetuksilla vesienhoitoalueista (2004), vesienhoidon järjestämisestä (2006) ja ympäristölle vaarallisista ja haitallisista aineista (2006). Lisäksi on soveltuvin osin muutettu ympäristönsuojelulakia ja vesilakia. Näillä säädöksillä vesipuitedirektiivin mukainen toiminta on liitetty osaksi suomalaista vesien käyttöön, hoitoon ja suojeluun liittyvää toimintaa, jonka olennaisena perustana on edelleen ympäristönsuojelulain ja vesilain mukainen lupajärjestelmä. Vesienhoitotyöhön kuuluva biologista näkökulmaa painottava vesien tilan arviointi, tilan seuranta, tilatavoitteiden asettaminen ja tavoitteiden saavuttamiseksi tarpeelliset toimenpiteet kootaan vesienhoitosuunnitelmaksi, joka tehdään jokaiselle ns. vesienhoitoalueelle. Toimenpiteistä laaditaan erillinen toimenpideohjelma, jonka yhteenveto on osa vesienhoitosuunnitelmaa. Vesienhoidossa ja toimenpideohjelmien laadinnassa pyritään seuraaviin tavoitteisiin: • Pinta- ja pohjavesien tila ei heikkene • Pintavesien ekologinen ja kemiallinen tila on vuoteen 2015 mennessä vähintään hyvä • Pohjavesien kemiallinen ja määrällinen tila on vuoteen 2015 mennessä vähintään hyvä • Keinotekoisten ja voimakkaasti muutettujen vesien ekologinen tila on vuoteen 2015 mennessä vähintään niin hyvä kuin näiden vesien muuttunut tila mahdollistaa (ns. ”hyvä saavutettavissa oleva tila”) • Pilaavien sekä muiden haitallisten ja vaarallisten aineiden pääsyä vesiin rajoitetaan • Tulvien ja kuivuuden haitallisia vaikutuksia vähennetään

Role of the canonical transient receptor potential channel 2 (TRPC2) in thyroid cell function

Kalciumjonen reglerar flera processer i celler såsom transkribering av gener, celldelning, cellernas rörlighet och celldöd. Därför har cellerna utvecklat många mekanismer för att reglera den intracellulära kalciumkoncentrationen. Kalciumkanaler spelar en viktig roll i denna regleringsprocess. TRPC-kanalerna (eng. canonical transient receptor potential) är en familj av jonkanaler med sju medlemmar (TRPC1-7) vars regleringsmekanismer och fysiologiska roller är varierande. TRPC2-kanalens fysiologiska signifikans, samt hur kanalen regleras, är dåligt karakteriserad. För första gången, rapporterar vi närvaron av TRPC2 kanalen i råttans sköldkörtelceller samt primära sköldkörtelceller från råtta. Hos gnagare har TRPC2 antagits vara exklusivt uttryckt i det vomeronasala organet. För att undersöka den fysiologiska betydelsen av kanalen, har vi utvecklat stabila celler med nedreglerat TRPC2 (shTRPC2) m.h.a. shRNA-teknik. Nedreglering av TRPC2 resulterade i stora skillnader i flera viktiga cellulära funktioner och i regleringen av sköldkörtelcellernas cellsignalering. Nedreglering av TRPC2 orsakade minskad agonist-beroende frigivning av kalcium från det endoplasmatiska nätverket, samt minskat agonist-beroende inflöde av extracellulärt kalcium, men ökade det basala kalciuminflödet. Uttrycket av PKCβ1 och PKCδ, SERCA-aktiviteten och kalciumhalten i det endoplasmatiska nätverket minskade i shTRPC2 celler. Kommunikation mellan kalcium- och cAMP-signalering påvisades vara TRPC2-beroende, vilket visades reglera uttrycket av TSH-receptorn. Vi undersökte också betydelsen av TRPC2 kanalen i reglering av sköldkörtelcellers proliferation, migration, vidhäftning och invasion; processer som alla var dämpade i shTRPC2 celler. Samamnfattningsvis påvisade dessa resultat en ny och viktig fysiologisk betydelse för TRPC2 kanalerna.

Interdependence of Emerging Eastern European stock markets

One of the main developments in the global economy during the past decades has been the growth of emerging economies. Projections for their long-term growth, changes in the investment climate, corporate transparency and demography point to an increasing role for these emerging economies in the global economy. Today, emerging economies are usually considered as financial markets offering opportunities for high returns, good risk diversification and improved return-to-risk ratios. However, researchers have noted that these advantages may be in decline because of the increasing market integration. Nevertheless, it is likely that certain financial markets and specific sectors will remain partially segmented and somewhat insulated from the global economy for the year to come. This doctoral dissertation investigates several stock markets in Emerging Eastern Europe (EEE), including the ones in Russia, Poland, Hungary, the Czech Republic, Bulgaria and Slovenia. The objective is to analyze the returns and financial risks in these emerging markets from international investor’s point of view. This study also examines the segmentation/integration of these financial markets and the possibilities to diversify and hedge financial risk. The dissertation is divided into two parts. The first includes a review of the theoretical background for the articles and a review of the literature on EEE stock markets. It includes an overview of the methodology and research design applied in the analysis and a summary of articles from the second part of this dissertation and their main findings. The second part consists of four research publications. This work contributes to studies on emerging stock markets in four ways. First, it adds to the body of research on the pricing of risk, providing new empirical evidence about partial stock market segmentation in EEE. The results suggest that the aggregate emerging market risk is a relevant driver for stock market returns and that this market risk can be used to price financial instruments and forecast their performance. Second, it contributes to the empirical research on the integration of stock markets, asset prices and exchange rates by identifying the relationships between these markets through volatility and asset pricing. The results show that certain sectors of stock markets in EEE are not as integrated as others. For example, the Polish consumer goods sector, the Hungarian telecommunications sector, and the Czech financial sector are somewhat isolated from their counterparts elsewhere in Europe. Nevertheless, an analysis of the impact of EU accession in 2004 on stock markets suggests that most of the EEE markets are becoming increasingly integrated with the global markets. Third, this thesis complements the scientific literature in the field of shock and volatility spillovers by examining the mechanism of spillover distribution among the EU and EEE countries. The results illustrate that spillovers in emerging markets are mostly from a foreign exchange to the stock markets. Moreover, the results show that the effects of external shocks on stock markets have increased after the enlargement of the EU in 2004. Finally, this study is unique because it analyzes the effects of foreign macroeconomic news on geographically closely related countries. The results suggest that the effects of macroeconomic announcements on volatility are significant and have effect that varies across markets and their sectors. Moreover, the results show that the foreign macroeconomic news releases, somewhat surprisingly, have a greater effect on the EEE markets than the local macroeconomic news. This dissertation has a number of implications for the industry and for practitioners. It analyses financial risk associated with investing in Emerging Eastern Europe. Investors may use this information to construct and optimize investment portfolios. Moreover, this dissertation provides insights for investors and portfolio managers considering asset allocation to protect value or obtain higher returns. The results have also implications for asset pricing and portfolio selection in light of macroeconomic news releases.

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.

Occurrence and photochemical fate of selected pharmaceutical active ingredients in the aquatic environment

Läkemedel konsumeras årligen i enorma mängder världen över. Efter intag kommer en del av läkemedlets aktiva förening(ar) att utsöndras från kroppen med urin och fekalier för att sedan transporteras till avloppsreningsverk. Till följd av att reningsverken inte fullständigt förmår rena avloppsvattnet från dessa föreningar kommer de att kontinuerligt tillföras vattenmiljön. Således är det viktigt att utveckla analytiska metoder för att kunna studera halterna av de aktiva föreningarna i reningsverkens utloppsvatten och den närliggande vattenmiljön. Ute i naturen kommer föreningarna att utsättas för olika fysikaliska, kemiska och biologiska processer, vilka kan orsaka förändringar i deras kemiska struktur och därigenom deras identitet och biologiska aktivitet. En stor del av de befintliga aktiva föreningarna genomgår kemisk förändring då de i vattenmiljön utsätts för solljus (fototransformation). Genom fototransformation kan nya föreningar (transformationsprodukter) med andra kemiska och biologiska egenskaper bildas. Denna avhandling inriktar sig på de aktiva föreningarnas förekomst och fotokemiska öde i miljön. I avhandlingen presenteras framtagna analytiska metoder för kvantifiering av läkemedelsföreningar i avloppsvatten och ytvatten samt för studier av vissa utvalda föreningars fotokemiska transformationsvägar. Därtill beskrivs några syntetiska metoder för att få tillgång till transformationsprodukter av det antiinflammatoriska ämnet diklofenak.

Uudenmaan vesienhoidon toimenpideohjelma

Vesienhoidon toimenpideohjelmalla pyritään EU:n asettamaan tavoitteeseen pinta- ja pohjavesien hyvästä tilasta vuoteen 2015 mennessä. Toimenpideohjelmassa on esitetty tavoitetilan saavuttamiseksi tarvittavat toimenpiteet, niiden kustannukset sekä ohjauskeinojen kehittämistarve. Toimenpideohjelmassa esitetyistä toimenpiteistä ja niiden kustannuksista on esitetty yhteenveto valtioneuvoston 10.12.2009 hyväksymässä Kymijoen-Suomenlahden vesienhoitoalueen vesienhoitosuunnitelmassa. Toimenpideohjelma on laadittu yhteistyössäalueen toimijoiden kanssa ja sen laatimisen yhteydessä on järjestetty useita yleisötilaisuuksia ja seminaareja. Toimenpideohjelmassa on otettu huomioon vuosina 2006–2009 järjestettyjen kolmen kuulemiskierroksen palaute. Vesiensuojelun tehostaminen on erityisen tärkeää Uudellamaalla, koska alueen järvet, joet ja rannikkovedet ovat huonommassa tilassa kuin Suomessa keskimäärin. Vesiin kohdistuva ravinnekuormitus on suurta ja vesiä on muutettu suuresti rakentamalla, perkaamalla ja patoamalla. Alueen pinta- ja pohjavesien käyttötarpeet ovat tiheästä asutuksesta johtuen suuria. Ihmistoiminnot aiheuttavat pilaantumisriskin viidesosalle Uudenmaan pohjavesistä. Toimenpideohjelmassa Uudellemaalle esitettävien nykykäytännön mukaisten toimenpiteiden rahoitustarve on vuosina 2010–2015 noin 290 miljoonaa euroa vuodessa. Valtaosa nykykäytännön mukaisten toimenpiteiden kustannuksista koostuu yhdyskuntien ja haja-asutuksen jätevedenpuhdistuksesta sekä maatalouden vesiensuojelua koskevista ympäristötuista. Esitettävien lisätoimenpiteiden rahoitustarve on noin 31 miljoonaa euroa vuodessa. Lisätoimenpiteiden kustannuksista suurimman osan muodostavat maatalouden kuormituksen vähentämistoimenpiteet. Lisätoimenpiteitä on esitetty myös mm. vesistöjen kunnostukseen, uusien siirtoviemäreiden rakentamiseen sekä metsätalouden vesiensuojelun tehostamiseen. Pohjavesiä koskevilla lisätoimenpiteillä pyritään pohjavesien pilaantumisriskin vähentämisen mm. liikenteen, yhdyskuntien ja teollisuuden osalta. Keskeisenä pohjavesiä koskevana toimenpiteenä on esitetty myös pilaantuneiden maa-alueiden ja maa-ainesottoalueiden kunnostamista. Pohjavesialueiden suojelusuunnitelmien ja pohjavesiselvitysten laatimista tulee lisätä merkittävästi nykyisestä. Uudenmaan vesistöjen tila paranee selvästi voimakkaasti kuormitetuilla alueilla, jos esitetyt toimenpiteet toteutetaan. Monien vesistöjen ja koko Suomenlahden osalta hyvän tilan saavuttamiseksi tarvitaan kuitenkin yli vuoden 2015 ulottuvia toimia, koska vesien liiallinen kuormitus ja vesiä muuttavat toiminnot ovat jatkuneet hyvin pitkään. Suurella osalla huonossa tilassa olevista pohjavesialueista on arvioitu, että hyvä tila saavutetaan esitetyillä toimenpiteillä vuoteen 2015 mennessä. Viidellä pohjavesialueella tavoiteaikataulua on siirretty vuoteen 2027.

Experimental and discrete element simulation studies of bell-less charging of blast furnace

This thesis presents an experimental study and numerical study, based on the discrete element method (DEM), of bell-less charging in the blast furnace. The numerical models are based on the microscopic interaction between the particles in the blast furnace charging process. The emphasis is put on model validation, investigating several phenomena in the charging process, and on finding factors that influence the results. The study considers and simulates size segregation in the hopper discharging process, particle flow and behavior on the chute, which is the key equipment in the charging system, using mono-size spherical particles, multi-size spheres and nonspherical particles. The behavior of the particles at the burden surface and pellet percolation into a coke layer is also studied. Small-scale experiments are used to validate the DEM models.

Towards novel biogas upgrading processes

Biogas production has considerable development possibilities not only in Finland but all over the world since it is the easiest way of creating value out of various waste fractions and represents an alternative source of renewable energy. Development of efficient biogas upgrading technology has become an important issue since it improves the quality of biogas and for example facilitating its injection into the natural gas pipelines. Moreover, such upgrading contributes to resolving the issue of increasing CO2 emissions and addresses the increasing climate change concerns. Together with traditional CO2 capturing technologies a new class of recently emerged sorbents such as ionic liquids is claimed as promising media for gas separations. In this thesis, an extensive comparison of the performance of different solvents in terms of CO2 capture has been performed. The focus of the present study was on aqueous amine solutions and their mixtures, traditional ionic liquids, ‘switchable’ ionic liquids and poly(ionic liquid)s in order to reveal the best option for biogas upgrading. The CO2 capturing efficiency for the most promising solvents achieved values around 50 - 60 L CO2 / L absorbent. These values are superior to currently widely applied water wash biogas upgrading system. Regeneration of the solvent mixtures appeared to be challenging since the loss of initial efficiency upon CO2 release was in excess of 20 - 40 vol %, especially in the case of aqueous amine solutions. In contrast, some of the ionic liquids displayed reversible behavior. Thus, for selected “switchable” ionic and poly(ionic liquid)s the CO2 absorption/regeneration cycles were performed 3 - 4 times without any notable efficiency decrease. The viscosity issue, typical for ionic liquids upon CO2 saturation, was addressed and the information obtained was evaluated and related to the ionic interactions. The occurrence of volatile organic compounds (VOCs) before and after biogas upgrading was studied for biogas produced through anaerobic digestion of waste waters sludge. The ionic liquid [C4mim][OAc] demonstrated its feasibility as a promising scrubbing media and exhibited high efficiency in terms of the removal of VOCs. Upon application of this ionic liquid, the amount of identified VOCs was diminished by around 65 wt %, while the samples treated with the aqueous mixture of 15 wt % N-methyldiethanolamine with addition of 5 wt % piperazine resulted in 32 wt % reduction in the amounts of volatile organic compounds only.

Nivala - Haapajärven seudun liikenneturvallisuussuunnitelma

Pohjois-Pohjanmaan ELY-keskus sekä Nivalan, Haapajärven, Pyhäjärven, Kärsämäen sekä Reisjärven kunnat ovat laatineet yhdessä Nivala-Haapajärven seudun liikenneturvallisuussuunnitelman. Työn tuloksena laaditut kuntakohtaiset suunnitelmaraportit sisältävät sekä liikenneympäristön parantamissuunnitelmat että liikennekasvatustyön kehittämissuunnitelmat. Tähän raporttiin on koottu seudullinen yhteenveto laadituista kuntakohtaisista suunnitelmista. Liikenneympäristön parantamistoimenpiteiden suunnittelua ohjasivat työn aikana määritellyt kunnille yhteiset liikenneturvallisuuden parantamista koskevat periaatteet sekä tarkemmin kuntakohtaiset erityispiirteet. Myös liikennekasvatustyön kehittämissuunnitelmat laadittiin kunnille yhteisten periaatteiden ohjaamina. Suunnitelman laatimisen taustana on toiminut ELY:n laatima Pohjois-Pohjanmaan ja Kainuun liikenneturvallisuussuunnitelma. Haapajärven kaupunkiin on esitetty liikenneympäristön parantamistoimenpiteitä yhteensä 58 kohteeseen, Kärsämäen kuntaan 34 kohteeseen, Nivalan kaupunkiin 54 kohteeseen, Pyhäjärven kaupunkiin 58 kohteeseen sekä Reisjärven kuntaan 46 kohteeseen. Toimenpiteet painottuvat kaikissa suunnitelmissa keskustaalueille ja niiden läheisyyteen sekä yksittäisiin ongelmakohteisiin. Toimenpiteiden suunnittelussa on otettu huomioon edellä mainitut yleiset periaatteet sekä tiedossa olevien kaava-/ maankäyttöhankkeiden lähivuosina edellyttämät toimenpiteet. Toimenpiteiden toteuttaminen on vaiheistettu suunnitelmissa kolmeen ohjeelliseen kiireellisyysluokkaan; vuosina 2013-2016 ja 2017-2020 sekä vuoden 2021 jälkeen toteutettaviin toimenpiteisiin. Lisäksi erikseen on esitetty myös pienemmät ns. pikatoimenpiteet. Parantamistoimenpiteiden kustannuksiksi on arvioitu koko seudulla yhteensä 20,9 milj. €. Yksittäisiin kohteisiin ehdotettujen parantamistoimenpiteiden ohella on esitetty myös yleisperiaatteita koskien mm. asuinalueiden 30 km/h-rajoitusten käyttöönottoa ja väistämisvelvollisuuskäytäntöjä, hidasteiden käyttöperiaatteita, nopeusrajoitusten ajoratamaalauksia, suojateiden havaittavuuden parantamista, mopoilun kieltämistä kevyen liikenteen väylillä, tienvarsiraivauksia sekä mm. hajarakentamisen hallintaa. Lisäksi on esitetty esteettömyyden parantamisperiaatteita ja -toimenpiteitä. Liikennekasvatustyön kehittämissuunnitelmissa on määritelty kuntien liikenneturvallisuustyön nykytila, kuntakohtaisten liikenneturvallisuustyöryhmien toimintamallit ja tehtävät, hallintokuntakohtaiset liikennekasvatustyön tavoitteet sekä liikennekasvatustyön kehittämissuunnitelmien ensimmäiset askeleet. Lisäksi on esitetty keskeisten yhteistyökumppaneiden osallistuminen liikennekasvatustyöhön sekä esitetty seudulla tehtävän jatkuvan liikenneturvallisuustyön varmistamiseksi ns. seudullisen liikenneturvallisuustoimijamallin käyttöönottoa. Raportissa on esitetty myös liikenneturvallisuustyön seurannan toimintatavat.

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.