Nutrient enrichment and water depth modify consumer control in rocky shore macroalgal communities

The objective of my thesis is to assess mechanisms of ecological community control in macroalgal communities in the Baltic Sea. In the top-down model, predatory fish feed on invertebrate mesograzers, releasing algae partly from grazing pressure. Such a reciprocal relationship is called trophic cascade. In the bottom-up model, nutrients increase biomass in the food chain. The nutrients are first assimilated by algae and, via food chain, increase also abundance of grazers and predators. Previous studies on oceanic shores have described these two regulative mechanisms in the grazer - alga link, but how they interact in the trophic cascades from fish to algae is still inadequately known. Because the top-down and bottom-up mechanisms are predicted to depend on environmental disturbances, such as wave stress and light, I have studied these models at two distinct water depths. There are five factorial field experiments behind the thesis, which were all conducted in the Finnish Archipelago Sea. In all the experiments, I studied macroalgal colonization - either density, filament length or biomass - on submerged colonization substrates. By excluding predatory fish and mesograzers from the algal communities, the studies compared the strength of the top-down control to natural algal communities. A part of the experimental units were, in addition, exposed to enriched nitrogen and phosphorus concentrations, which enabled testing of bottom-up control. These two models of community control were further investigated in shallow (<1 m) and deep (ca. 3 m) water. Moreover, the control mechanisms were also expected to depend on grazer species. Therefore different grazer species were enclosed into experimental units and their impacts on macroalgal communities were followed specifically. The community control in the Baltic rocky shores was found to follow theoretical predictions, which have not been confirmed by field studies before. Predatory fish limited grazing impact, which was seen as denser algal communities and longer algal filaments. Nutrient enrichment increased density and filament length of annual algae and, thus, changed the species composition of the algal community. The perennial alga Fucus vesiculosusA and the red alga Ceramium tenuicorne suffered from the increased nutrient availabilities. The enriched nutrient conditions led to denser grazer fauna, thereby causing strong top-down control over both the annual and perennial macroalgae. The strength of the top-down control seemed to depend on the density and diversity of grazers and predators as well as on the species composition of macroalgal assemblages. The nutrient enrichment led to, however, weaker limiting impact of predatory fish on grazer fauna, because fish stocks did not respond as quickly to enhanced resources in the environment as the invertebrate fauna. According to environmental stress model, environmental disturbances weaken the top-down control. For example, on a wave-exposed shore, wave stress causes more stress to animals close to the surface than deeper on the shore. Mesograzers were efficient consumers at both the depths, while predation by fish was weaker in shallow water. Thus, the results supported the environmental stress model, which predicts that environmental disturbance affects stronger the higher a species is in the food chain. This thesis assessed the mechanisms of community control in three-level food chains and did not take into account higher predators. Such predators in the Baltic Sea are, for example, cormorant, seals, white-tailed sea eagle, cod and salmon. All these predatory species were recently or are currently under intensive fishing, hunting and persecution, and their stocks have only recently increased in the region. Therefore, it is possible that future densities of top predators may yet alter the strengths of the controlling mechanisms in the Baltic littoral zone.

Immunopathogenesis of Asthma and Atopic Diseases – The specific Role of a selected Panel of Genes in human T helper Cell Differentiation

T helper cell (Th) functions are crucial for proper immune defence against various intra- and extracellular pathogens. According to the specific immune responses, Th cells can be classified into subtypes, Th1 and Th2 cells being the most frequently characterized classes. Th1 and Th2 cells interact with other immune cells by regulating their functions with specific cytokine production. IFN, IL-2 and TNF- are the cytokines predominantly produced by Th1 cells whereas Th2 cells produce Th2-type cytokines, such as IL-4, IL-5 and IL-13. Upon TCR activation and in the presence of polarizing cytokines, Th cells differentiate into effector subtypes from a common precursor cell. IFN and IL-12 are the predominant Th1 polarizing cytokines whereas IL-4 directs Th2 polarization. The cytokines mediate their effects through specific receptor signalling. The differentiation process is complex, involving various signalling molecules and routes, as well as functions of the specific transcription factors. The functions of the Th1/Th2 cells are tightly regulated; however, knowledge on human Th cell differentiation is, as yet, fairly poor. The susceptibility for many immune-mediated disorders often originates from disturbed Th cell responses. Thus, research is needed for defining the molecular mechanisms involved in the differentiation and balanced functions of the Th cells. Importantly, the new information obtained will be crucial for a better understanding of the pathogenesis of immune-mediated disorders, such as asthma or autoimmune diseases. In the first subproject of this thesis, the role of genetic polymorphisms in the human STAT6, GATA3 and STAT4 genes were investigated for asthma or atopy susceptibility in Finnish asthma families by association analysis. These genes code for key transcription factors regulating Th cell differentiation. The study resulted in the identification of a GATA3 haplotype that associated with asthma and related traits (high serum IgE level). In the second subproject, an optimized method for human primary T cell transfection and enrichment was established. The method can be utilized for functional studies for the selected genes of interest. The method was also utilized in the third subproject, which aimed at the identification of novel genes involved in early human Th cell polarization (0-48h) using genome-wide oligonucleotide arrays. As a result, numerous genes and ESTs with known or unknown functions were identified in the study. Using an shRNA knockdown approach, a panel of novel IL-4/STAT6 regulated genes were identified in the functional studies of the genes. Moreover, one of the genes, NDFIP2, with a previously uncharacterized role in the human Th differentiation, was observed to promote IFN production of the differentiated Th1 cells. Taken together, the results obtained have revealed potential new relevant candidate genes serving as a basis for further studies characterizing the detailed networks involved in the human Th cell differentiation as well as in the genetic susceptibility of Th-mediated immune disorders.

Formation and Control of Trace Metal Emissions in Co-Firing of Biomass, Peat, and Wastes in Fluidised Bed Combustors

Environmentally harmful consequences of fossil fuel utilisation andthe landfilling of wastes have increased the interest among the energy producers to consider the use of alternative fuels like wood fuels and Refuse-Derived Fuels, RDFs. The fluidised bed technology that allows the flexible use of a variety of different fuels is commonly used at small- and medium-sized power plants ofmunicipalities and industry in Finland. Since there is only one mass-burn plantcurrently in operation in the country and no intention to build new ones, the co-firing of pre-processed wastes in fluidised bed boilers has become the most generally applied waste-to-energy concept in Finland. The recently validated EU Directive on Incineration of Wastes aims to mitigate environmentally harmful pollutants of waste incineration and co-incineration of wastes with conventional fuels. Apart from gaseous flue gas pollutants and dust, the emissions of toxic tracemetals are limited. The implementation of the Directive's restrictions in the Finnish legislation is assumed to limit the co-firing of waste fuels, due to the insufficient reduction of the regulated air pollutants in the existing flue gas cleaning devices. Trace metals emission formation and reduction in the ESP, the condensing wet scrubber, the fabric filter, and the humidification reactor were studied, experimentally, in full- and pilot-scale combustors utilising the bubbling fluidised bed technology, and, theoretically, by means of reactor model calculations. The core of the model is a thermodynamic equilibrium analysis. The experiments were carried out with wood chips, sawdust, and peat, and their refuse-derived fuel, RDF, blends. In all, ten different fuels or fuel blends were tested. Relatively high concentrations of trace metals in RDFs compared to the concentrations of these metals in wood fuels increased the trace metal concentrations in the flue gas after the boiler ten- to hundred-folds, when RDF was co-fired with sawdust in a full-scale BFB boiler. In the case of peat, lesser increase in trace metal concentrations was observed, due to the higher initial trace metal concentrations of peat compared to sawdust. Despite the high removal rate of most of the trace metals in the ESP, the Directive emission limits for trace metals were exceeded in each of the RDF co-firing tests. The dominat trace metals in fluegas after the ESP were Cu, Pb and Mn. In the condensing wet scrubber, the flue gas trace metal emissions were reduced below the Directive emission limits, whenRDF pellet was used as a co-firing fuel together with sawdust and peat. High chlorine content of the RDFs enhanced the mercuric chloride formation and hence the mercury removal in the ESP and scrubber. Mercury emissions were lower than theDirective emission limit for total Hg, 0.05 mg/Nm3, in all full-scale co-firingtests already in the flue gas after the ESP. The pilot-scale experiments with aBFB combustor equipped with a fabric filter revealed that the fabric filter alone is able to reduce the trace metal concentrations, including mercury, in the flue gas during the RDF co-firing approximately to the same level as they are during the wood chip firing. Lower trace metal emissions than the Directive limits were easily reached even with a 40% thermal share of RDF co-firing with sawdust.Enrichment of trace metals in the submicron fly ash particle fraction because of RDF co-firing was not observed in the test runs where sawdust was used as the main fuel. The combustion of RDF pellets with peat caused an enrichment of As, Cd, Co, Pb, Sb, and V in the submicron particle mode. Accumulation and release oftrace metals in the bed material was examined by means of a bed material analysis, mass balance calculations and a reactor model. Lead, zinc and copper were found to have a tendency to be accumulated in the bed material but also to have a tendency to be released from the bed material into the combustion gases, if the combustion conditions were changed. The concentration of the trace metal in the combustion gases of the bubbling fluidised bed boiler was found to be a summary of trace metal fluxes from three main sources. They were (1) the trace metal flux from the burning fuel particle (2) the trace metal flux from the ash in the bed, and (3) the trace metal flux from the active alkali metal layer on the sand (and ash) particles in the bed. The amount of chlorine in the system, the combustion temperature, the fuel ash composition and the saturation state of the bed material in regard to trace metals were discovered to be key factors affecting therelease process. During the co-firing of waste fuels with variable amounts of e.g. ash and chlorine, it is extremely important to consider the possible ongoingaccumulation and/or release of the trace metals in the bed, when determining the flue gas trace metal emissions. If the state of the combustion process in regard to trace metals accumulation and/or release in the bed material is not known,it may happen that emissions from the bed material rather than the combustion of the fuel in question are measured and reported.

Synteesikaasun liukoisuus ja aineensiirto fermentointiliuokseen

Työssä tutkittiin synteesikaasun komponenttien: hiilimonoksidin, vedyn ja hiilidioksidin liukoisuutta ja aineensiirtonopeutta fermentointiliuokseen. Kirjallisuusosassa käsitellään kaasujen liukoisuuksiin ja kaasu-nesteaineensiirtoon vaikuttavia tekijöitä ja esitellään korrelaatioita, jotka on kehitetty volumetrisen aineensiirtokertoimen ennustamiseen sekoitetussa fermentorissa. Kirjallisuus-osassa esitetään myös synteesikaasun komponenttien liukoisuudet veteen, etanoliin ja etikkahappoon 37 ºC lämpötilassa ja esitellään Flowbat-simulointiohjelman MHV2-mallin käyttöä kaasu-neste tasapainojen mallin-nuksessa. Työn kokeellisessa osassa tutkittiin synteesikaasun komponenttien liukoisuuksia veteen ja kasvatusalustaan sekä kehitettiin mittausmenetelmä kaasu-neste tasapainojen mittaukseen. Tasapainomittauksissa tutkittiin etanolin ja etikkahapon konsentraatioiden vaikutusta synteesikaasun liukoisuuteen. Lisäksi mallinnettiin kaasu-neste tasapainoja monikomponenttisysteemeissä MHV2-mallin avulla. Kokeellisen osan aineensiirtomittauksissa tutkittiin sekoitusnopeuden ja kaasun volumetrisen syöttönopeuden vaikutusta hiilimonoksidin ja vedyn volumetriseen aineensiirtokertoimeen kLa kahden litran tilavuuksisessa laboratoriofermentorissa. Mittaustulosten perusteella kasvatusalustan komponentit vaikuttavat merkittävästi hiilidioksidin liukoisuuteen. Lisäys etanolin ja etikkahapon konsentraatioissa parantaa hiilimonoksidin liukoisuutta kasvatusalustaan. Kaasun volumetrinen syöttönopeus ja sekoitusnopeus vaikuttavat voimakkaasti volumetrisen aineensiirtokertoimen arvoon. Tutkitussa systeemissä korkein teoreettinen solutiheys, joka voitiin saavuttaa suurimmalla hiilimonoksidin aineensiirto-nopeudella, oli 3 g/L. Tämä on kaksinkertainen verrattuna aiemmissa VTT:n kokeissa saavutettuihin solutiheyksiin.

Uuttoprosessin suunnittelu

Teknologian kehitys ja prosessien tiukempi valvonta ovat alentaneet selluteollisuuden häviöitä tehden prosesseista suljetumpia. Valitettavasti nämä edistysaskeleet teknologiassa ovat lisänneet prosessiin kuulumattomien yhdisteiden määrää kemikaalien talteenottokierrossa. Näistä kemikaaleista haitallisimpia ovat kloridi- ja kaliumyhdisteet, jotka tulevat prosessiin raaka-aineiden ja prosessikemikaalien mukana. Kloridi ja kalium muodostavat emäksisissä liuoksissa epäorgaanisia liukoisia yhdisteitä, jotka rikastuvat lipeäkiertoon. Soodakattilassa kloridien läsnäolo alentaa tuhkan sulamislämpötilaa sekä tarttumispistettä, lisää korroosiota ja saostumien muodostumista kattilan pinnalle. Nämä seuraukset voivat vähentää vuosituotantoa ja nostaa korjauskustannuksia. Kaliumin ja kloridin rikastumista talteenottokiertoon voidaan estää poistamalla ne prosessista. Prosessiin kuulumattomat yhdisteet tulisi poistaa talteenottoprosessista ja säilyttää samalla korkea kemikaalien talteenottoprosentti. Koska kaliumin ja kloridin rikastumiskertoimet soodakattilan tuhkassa ovat korkeita, on tuhkan käsittely tehokasta. Kloridin ja kaliumin poistoon on kehitetty menetelmiä, joilla voidaan vähentää hyödyllisten kemikaalien häviöitä. Näitä menetelmiä ovat uutto, ioninvaihto, elektrodialyysi, jäähdytyskiteytys ja haihdutuskiteytys. Menetelmissä tuhka jaetaan kloridi- ja kaliumpitoiseen osaan ja natriumsulfaattipitoiseen osaan. Kloridi ja kalium poistetaan prosessista ja loput palautetaan lipeäkiertoon. Kloridin ja kaliumin poistoa tuhkasta tutkittiin uuttamalla tuhkaa vedellä. Parhaissa käyttöolosuhteissa natriumsulfaatin liukoisuus veteen on huomattavasti alhaisempi kuin kaliumkloridin liukoisuus veteen. Optimaalinen uuttolämpötila ja tuhka-vesisuhde määritettiin siten, että kloridi- ja kaliumpitoisuudet suodoksessa olivat mahdollisimman korkeat sekä natriumin ja muiden anioneiden pitoisuudet suodoksessa mahdollisimman alhaiset. Saatuja tuloksia käytettiin jatkuvatoimisen uuttoprosessin suunnittelussa.

Food Safety Testing: Rapid Molecular Methods for Chemical and Biological Hazards

The central goal of food safety policy in the European Union (EU) is to protect consumer health by guaranteeing a high level of food safety throughout the food chain. This goal can in part be achieved by testing foodstuffs for the presence of various chemical and biological hazards. The aim of this study was to facilitate food safety testing by providing rapid and user-friendly methods for the detection of particular food-related hazards. Heterogeneous competitive time-resolved fluoroimmunoassays were developed for the detection of selected veterinary residues, that is coccidiostat residues, in eggs and chicken liver. After a simplified sample preparation procedure, the immunoassays were performed either in manual format with dissociation-enhanced measurement or in automated format with pre-dried assay reagents and surface measurement. Although the assays were primarily designed for screening purposes providing only qualitative results, they could also be used in a quantitative mode. All the developed assays had good performance characteristics enabling reliable screening of samples at concentration levels required by the authorities. A novel polymerase chain reaction (PCR)-based assay system was developed for the detection of Salmonella spp. in food. The sample preparation included a short non-selective pre-enrichment step, after which the target cells were collected with immunomagnetic beads and applied to PCR reaction vessels containing all the reagents required for the assay in dry form. The homogeneous PCR assay was performed with a novel instrument platform, GenomEra^™, and the qualitative assay results were automatically interpreted based on end-point time-resolved fluorescence measurements and cut-off values. The assay was validated using various food matrices spiked with sub-lethally injured Salmonella cells at levels of 1-10 colony forming units (CFU)/25 g of food. The main advantage of the system was the exceptionally short time to result; the entire process starting from the pre-enrichment and ending with the PCR result could be completed in eight hours. In conclusion, molecular methods using state-of-the-art assay techniques were developed for food safety testing. The combination of time-resolved fluorescence detection and ready-to-use reagents enabled sensitive assays easily amenable to automation. Consequently, together with the simplified sample preparation, these methods could prove to be applicable in routine testing.

New mechanisms regulating human Th1 and Th2 cell differentiation

Selective development of human T helper (Th) cells into functionally distinct Th1 and Th2 subtypes plays an essential role in the host immune response towards pathogens. However, abnormal function or differentiation of these cells can lead to development of various autoimmune diseases as well as asthma and allergy. Therefore, identification of key factors and the molecular mechanisms mediating Th1 and Th2 cell differentiation is important for understanding the molecular mechanisms of these diseases. The goal of this study was to identify novel factors involved in the regulation of Th1 and Th2 differentiation processes. A new method was optimized for enrichment of transiently transfected resting human primary T lymphocytes, that allowed the study of the influence of genes of interest in human Th1/Th2 cell differentiation and other primary Th cell functions. Functional characterization of PRELI, a novel activation-induced protein in human Th cells, identified it as a mitochondrial protein involved in the regulation of Th cell differentiation and apoptosis. By influencing the intracellular redox state, PRELI induces mitochondrial apoptosis pathway and downregulates STAT6 and Th2 differentiation. The data suggested that Calpain, an oxidative stress induced cysteine protease, is involved as a mediator in PRELI-induced downregulation of STAT6. PIM serine/threonine-specific kinases were identified as new regulators of human Th1 cell differentiation. PIM1 and PIM2 kinases were shown to be preferentially expressed in Th1 cells as compared to Th2 cells. RNA interference studies showed that PIM kinases enhance the production of IFN, the hallmark cytokine produced by Th1 cells. They also induce the expression of the key Th1-driving factor T-bet and the IL-12 signaling pathway during early phases of Th1 cell differentiation. Taken together, new regulators of human T helper cell differentiation were identified in this study, which provides new insights into the signaling mechanisms controlling the selective activation of human Th cell subsets.

Simplified sample handing in mass spectrometry based protein research - focus on protein phosphorylation

The human genome comprises roughly 20 000 protein coding genes. Proteins are the building material for cells and tissues, and proteins are functional compounds having an important role in many cellular responses, such as cell signalling. In multicellular organisms such as humans, cells need to communicate with each other in order to maintain a normal function of the tissues within the body. This complex signalling between and within cells is transferred by proteins and their post-translational modifications, one of the most important being phosphorylation. The work presented here concerns the development and use of tools for phosphorylation analysis. Mass spectrometers have become essential tools to study proteins and proteomes. In mass spectrometry oriented proteomics, proteins can be identified and their post-translational modifications can be studied. In this Ph.D. thesis the objectives were to improve the robustness of sample handling methods prior to mass spectrometry analysis for peptides and their phosphorylation status. The focus was to develop strategies that enable acquisition of more MS measurements per sample, higher quality MS spectra and simplified and rapid enrichment procedures for phosphopeptides. Furthermore, an objective was to apply these methods to characterize phosphorylation sites of phosphopeptides. In these studies a new MALDI matrix was developed which allowed more homogenous, intense and durable signals to be acquired when compared to traditional CHCA matrix. This new matrix along with other matrices was subsequently used to develop a new method that combines multiple spectra from different matrises from identical peptides. With this approach it was possible to identify more phosphopeptides than with conventional LC/ESI-MS/MS methods, and to use 5 times less sample. Also, phosphopeptide affinity MALDI target was prepared to capture and immobilise phosphopeptides from a standard peptide mixture while maintaining their spatial orientation. In addition a new protocol utilizing commercially available conductive glass slides was developed that enabled fast and sensitive phosphopeptide purification. This protocol was applied to characterize the in vivo phosphorylation of a signalling protein, NFATc1. Evidence for 12 phosphorylation sites were found, and many of those were found in multiply phosphorylated peptides

Adsorptive removal of harmful organic compound from aqueous solutions

Adsorption is one of the most commonly used methods in water treatment processes. It is attractive due to it easy operation and the availability of a wide variety of commercial adsorbents. This doctoral thesis focuses on investigating and explaining the influence of external phase conditions (temperature, pH, ionic strength, acidity, presence of cosolutes) on adsorption phenomena. In order to cover a wide range of factors and phenomena, case studies were chosen from various fields where adsorption is applied. These include the adsorptive removal of surface active agents (used in cleaning chemicals, for example) from aqueous effluents, the removal of hormones (estradiol) from drinking water, and the adsorption of antibiotics onto silica. The latter can beused to predict the diffusion of antibiotics in the aquatic system if they are released into the environment. Also the adsorption of living cells on functionalized polymers to purify infected water streams was studied. In addition to these examples, the adsorptive separation of harmful compounds from internal water streams within a chemical process was investigated. The model system was removal of fermentation inhibitors from lignocelluloses hydrolyzates. The detoxification of the fermentation broth is an important step in the manufacture of bioethanol from wood, but has not been studied previously in connection with concentrated acid hydrolyzates. New knowledge on adsorption phenomena was generated for all of the applications investigated. In most cases, the results could be explained by combining classical theories for individual phenomena. As an example, it was demonstrated how liquid phase aggregation could explain abnormal-looking adsorption equilibrium data. In addition to the fundamental phenomena, also process performance was of interest. This aspect is often neglected in adsorption studies. It was demonstrated that adsorbents should not be selected for a target application based on their adsorption properties only, but regeneration of the spent adsorbent must be considered. It was found that using a suitable amount of organic co-solvent in the regeneration can significantly improve the productivity of the process.

Distribution and role of macrophytes in coastal lagoons : implications of critical shifts

Crossroads, crucibles and refuges are three words that may describe natural coastal lagoon environments. The words refer to the complex mix of marine and terrestrial influences, prolonged dilution due to the semi-enclosed nature and the function of a habitat for highly diverse plant and animal communities, some of which are endangered. To attain a realistic picture of the present situation, high vulnerability to anthropogenic impact should be added to the description. As the sea floor in coastal lagoons is usually entirely photic, macrophyte primary production is accentuated compared with open sea environments. There is, however, a lack of proper knowledge on the importance of vegetation for the general functioning of coastal lagoon ecosystems. The aim of this thesis is to assess the role of macrophyte diversity, cover and species identity over temporal and spatial scales for lagoon functions, and to determine which steering factors primarily restrict the qualitative and quantitative composition of vegetation in coastal lagoons. The results are linked to patterns of related trophic levels and the indicative potential of vegetation for assessment of general conditions in coastal lagoons is evaluated. This thesis includes five field studies conducted in flads and glo-flads in the brackish water northern Baltic Sea. Flads and glo-flads are defined as a Baltic variety of coastal lagoons, which due to an inlet threshold and post-glacial landuplift slowly will be isolated from the open sea. This process shrinks inlet size, increases exposure and water retention, and is called habitat isolation. The studied coastal lagoons are situated in the archipelago areas of the eastern coast of Sweden, the Åland Islands and the south-west mainland of Finland, where land-uplift amounts to ca. 5 mm/ per year. Out of 400 evaluated sites, a total of 70 lagoons varying in inlet size, archipelago position and anthropogenic influence to cover for essential environmental variation were chosen for further inventory. Vegetation composition, cover and richness were measured together with several hydrographic and morphometric variables in the lagoons both seasonally and inter-annually to cover for general regional, local and temporal patterns influencing lagoon and vegetation development. On smaller species-level scale, the effects of macrophyte species identity and richness for the fish habitat function were studied by examining the influence of plant interaction on juvenile fish diversity. Thus, the active election of plant monoand polycultures by fish and the diversity of fish in the respective culture were examined and related to plant height and water depth. The lagoons and vegetation composition were found to experience a regime shift initiated by increased habitat isolation along with land-uplift. Vegetation composition altered, richness decreased and cover increased forming a less isolated and more isolated regime, named the vascular plant regime and charophyte regime, respectively according to the dominant vegetation. As total phosphorus in the water, turbidity and the impact of regional influences decreased in parallel, the dominance of charophytes and increasing cover seemed to buffer and stabilize conditions in the charophyte regime and indicated an increased functional role of vegetation for the lagoon ecosystem. The regime pattern was unaffected by geographical differences, while strong anthropogenic impact seemed to distort the pattern due to loss of especially Chara tomentosa L. in the charophyte regime. The regimes were further found unperturbed by short-time temporal fluctuations. In fact the seasonal and inter-annual dynamics reinforced the functional difference between the regimes by the increasing role of vegetation along habitat isolation and the resemblance to lake environments for the charophyte regime. For instance, greater total phosphorus and chlorophyll a concentrations in the water in the beginning of the season in the charophyte regime compared with the vascular plant regime presented a steeper reduction to even lower values than in the vascular plant regime along the season. Despite a regional importance and positive relationship of macrophyte diversity in relation to trophic diversity, species identity was underlined in the results of this thesis, especially with decreasing spatial scale. This result was supported partly by the increased role of charophytes in the functioning of the charophyte regime, but even more explicitly by the species-specific preference of juvenile fish for tall macrophyte monocultures. On a smaller species-level scale, tall plant species in monoculture seemed to be able to increase their length, indicating that negative selection forms preferred habitat structures, which increase fish diversity. This negative relationship between plant and fish diversity suggest a shift in diversity patterns among trohic levels on smaller scale. Thus, as diversity patterns seem complex and diverge among spatial scales, it might be ambiguous to extend the understanding of diversity relationships from one trophic level to the other. All together, the regime shift described here presents similarities to the regime development in marine lagoon environments and shallow lakes subjected to nutrient enrichment. However, due to nutrient buffering by vegetation with increased isolation and water retention as a consequence of the inlet threshold, the development seems opposite to the course along an eutrophication gradient described in marine lagoons lacking an inlet threshold, where the role of vegetation decreases. Thus, the results imply devastating consequences of inlet dredging (decreasing isolation) in terms of vegetation loss and nutrient release, and call for increased conservational supervision. Especially the red listed charophytes would suffer negatively from such interference and the consequences are likely to also deteriorate juvenile fish production. The fact that a new species to Finland, Chara connivens Salzm. Ex. Braun 1835 was discovered during this study further indicates a potential of the lagoons serving as refuges for rare species.

Elemental analysis of wood materials by external millibeam thick target PIXE

PIXE (Particle Induce X-ray Emission spectrometry) was used for analysing stem bark and stem wood of Scots pine, Norway spruce and Silver birch. Thick samples were irradiated, in laboratory atmosphere, with 3 MeV protons and the beam current was measured indirectly using a photo multiplicator (PM) tube. Both point scans and bulk analyses were performed with the 1 mm diameter proton beam. In bulk analyses, whole bark and sectors of discs of the stem wood were dry ashed at 550 ˚C. The ashes were homogenised by shaking and prepared to target pellets for PIXE analyses. This procedure generated representative samples to be analysed, but the enrichment also enabled quantification of some additional trace elements. The ash contents obtained as a product of the sample preparation procedure also showed to be of great importance in the evaluation of results in environmental studies. Spot scans from the pith of pine wood outwards, showed clearly highest concentrations of manganese, calcium and zinc in the first spot irradiated, or 2-3 times higher than in the surrounding wood. For stem wood from the crown part of a pine this higher concentration level was found in the first four spots/mms, including the pith and the two following growth rings. Zinc showed increasing concentrations outwards in sapwood of the pine stem, with the over-all lowest concentrations in the inner half of the sapwood. This could indicate emigration of this element from sapwood being under transformation to heartwood. Point scans across sapwood of pine and spruce showed more distinct variations in concentrations relative to hearth wood. Higher concentrations of e.g. zinc, calcium and manganese were found in earlywood than in denser latewood. Very high concentrations of iron and copper were also seen for some earlywood increments. The ash content of stem bark is up to and order higher than for the stem wood. However, when the elemental concentration in ashes of bark and wood of the same disc were compared, these are very similar – this when trees are growing at spots with no anthropogenic contamination from the atmosphere. The largest difference was obtained for calcium which appeared at two times high concentrations in ashes of bark than in ashes of the wood (ratio of 2). Pine bark is often used in monitoring of atmospheric pollution, where concentrations in bark samples are compared. Here an alternative approach is suggested: Bark and the underlying stem wood of a pine trees are dry ashed and analysed. The elemental concentration in the bark ash is then compared to the concentration of the same element in the wood ash. Comparing bark to wood includes a normalisation for the varying availability of an element from the soil at different sites. When this comparison is done for the ashes of the materials, a normalisation is also obtained for the general and locally different enrichment of inorganic elements from wood to bark. Already a ratio >2 between the concentration in the bark ash and the concentration in the wood ash could indicate atmospheric pollution. For monitoring where bark is used, this way of “inwards” comparison is suggested - instead of comparing to results from analyses of bark from other trees (read reference areas), growing at sites with different soil and, locally, different climate conditions. This approach also enables evaluation of atmospheric pollution from sampling of only relative few individual trees –preferable during forest felling.

Cultural Diversity, Social Cohesion, Religion: Core Values and Educational Policies in Four European Nations

In my doctoral thesis I evaluate strategies designed to cope with the multicultural nature of four European nations: Great Britain, The Netherlands, Sweden, and Denmark. I also analyse and clarify the question of the place of religion in present-day Europe. The empirical material analysed in the study consists of politicians’ statements and policy documents dealing with immigration policy and religious and values education in the four countries. In addition, I analyse statements issued by the Council of Europe regarding religious education, along with all cases relevant to religious education brought before the United Nations Human Rights Committee or the European Court of Human Rights. The theoretical framework is formed by the scholarly debate – among philosophers, sociologists and scholars of religion in education – concerning the question of a just society. Special emphasis is given to philosophical theories that are in favour of granting special group rights to religious minorities in the name of equal treatment. With regard to the question of the appropriate place of religion, I apply Kim Knott’s methodological model for locating religion in secular contexts, and Émile Durkheim’s theory as to the significance of religion and collective sentiments in uniting adherents or members of a group into a single moral community. The study shows that even when the positive side of immigration, as a potential force for the enrichment of the public culture, is acknowledged, there is anxiety as to the successful integration of immigrants. The premises and goals of immigration policies have also been questioned. One central problem is the incommensurability between the values upheld by Western liberal democracies and certain religious traditions, above all those of Islam. Great Britain, The Netherlands, Sweden, and Denmark have tightened control over their citizens’ ethical attitudes and want to regulate these as well. In coping with cultural diversity, the significance of education, especially religious education, plays a significant role; as future citizens, pupils are expected to internalise the society’s core values as well as gaining an understanding of different cultures and ways of life. It is also worth noting that both the Council of Europe and the European Court of Human Rights have recently expressed the view that one important goal of religious education is to enable pupils to be critical and autonomous with regard to different religions and moral positions. The study shows that religion is not seen as purely a personal matter. Religion is closely linked to individual and national identity, and religious traditions thus have a place in the public domain. It should be noted, however, that a religious tradition – more precisely, an interpretation of religious tradition – qualifies as a legitimate partner in the democratic decision-making process only if it shares similar values with Western European nations.

Application of capillary electrophoretic methods for determining carbohydrates and aliphatic carboxylic acids formed during wood processing

Knowledge of the behaviour of cellulose, hemicelluloses, and lignin during wood and pulp processing is essential for understanding and controlling the processes. Determination of monosaccharide composition gives information about the structural polysaccharide composition of wood material and helps when determining the quality of fibrous products. In addition, monitoring of the acidic degradation products gives information of the extent of degradation of lignin and polysaccharides. This work describes two capillary electrophoretic methods developed for the analysis of monosaccharides and for the determination of aliphatic carboxylic acids from alkaline oxidation solutions of lignin and wood. Capillary electrophoresis (CE), in its many variants is an alternative separation technique to chromatographic methods. In capillary zone electrophoresis (CZE) the fused silica capillary is filled with an electrolyte solution. An applied voltage generates a field across the capillary. The movement of the ions under electric field is based on the charge and hydrodynamic radius of ions. Carbohydrates contain hydroxyl groups that are ionised only in strongly alkaline conditions. After ionisation, the structures are suitable for electrophoretic analysis and identification through either indirect UV detection or electrochemical detection. The current work presents a new capillary zone electrophoretic method, relying on in-capillary reaction and direct UV detection at the wavelength of 270 nm. The method has been used for the simultaneous separation of neutral carbohydrates, including mono- and disaccharides and sugar alcohols. The in-capillary reaction produces negatively charged and UV-absorbing compounds. The optimised method was applied to real samples. The methodology is fast since no other sample preparation, except dilution, is required. A new method for aliphatic carboxylic acids in highly alkaline process liquids was developed. The goal was to develop a method for the simultaneous analysis of the dicarboxylic acids, hydroxy acids and volatile acids that are oxidation and degradation products of lignin and wood polysaccharides. The CZE method was applied to three process cases. First, the fate of lignin under alkaline oxidation conditions was monitored by determining the level of carboxylic acids from process solutions. In the second application, the degradation of spruce wood using alkaline and catalysed alkaline oxidation were compared by determining carboxylic acids from the process solutions. In addition, the effectiveness of membrane filtration and preparative liquid chromatography in the enrichment of hydroxy acids from black liquor was evaluated, by analysing the effluents with capillary electrophoresis.

Häiriöanalyysejä tehonkorotetun kiehutusvesivoimalaitoksen käytettävyyden varmistamiseksi

TVO suunnittelee reaktoritehon 10 %:n korotusta Olkiluoto 1 ja 2 -voimalaitoksille. Reaktoriteho nostetaan 2500 MW:sta 2750 MW:iin polttoaineen rikastusastetta nostamalla ja pääkiertovirtausta kasvattamalla. Samalla syöttövesivirtaus reaktoriin ja tuorehöyryvirtaus turpiineille kasvaa. Lauhteenpuhdistusjärjestelmän kapasiteettia ei voida kuitenkaan kasvattaa, joten massavirran lisäys toteutetaan ottamalla käyttöön korkeapainesivulauhteen eteenpäinpumppaus. Lauhteen esilämmityslinjojen, lauhteenpuhdistuksen ja syöttövesipumppujen massavirta säilyy siten nykyisellään. Muita merkittäviä tehonkorotukseen liittyviä laitosmuutoksia ovat pääkiertopumppujen uusinta ja korkeapaineturpiinin muutokset. Tehonkorotetun prosessin käytettävyyden varmistamiseksi tehdään häiriöanalyysejä Apros-prosessisimulointiohjelmistoa käyttäen. OL1 ja OL2 -laitoksista on olemassa validoitu 2500 MW:n laitosmalli, josta muokatulla 2750 MW:n laitosmallilla simuloinnit tehdään. Häiriöanalyysien avulla selvitetään säätöjärjestelmien kyky pitää prosessin tila hallinnassa ilman suojausautomaation laukeamista. Simuloituihin tapauksiin kuuluu pumppujen ja venttiilien vikaantumistapauksia sekä turpiini- ja reaktoripuolen pikasulku- ja osittaispikasulkutapauksia. Myös meriveden lämpötilan vaikutusta häiriötilanteisiin tarkastellaan. Analyysien perusteella voimalaitosten ohjaus- ja suojausautomaatio toimivat hyvin myös korotetulla teholla. Tehonkorotuksen jälkeiset suuremmat massavirrat aiheuttavat kuitenkin voimakkaampia reaktoripaineen ja -tehon vaihteluita varsinkin venttiilien sulkeutumistapauksissa. Simuloinnit osoittivat, että tehonkorotus 2500 MW:sta 2750 MW:iin on mahdollinen, mutta aiheuttaa pieniä muutoksia laitoksen suojausjärjestelmien laukaisurajoihin.