Behavior of black liquor nitrogen in combustion : formation of cyanate

The Kraft pulping process is the dominant chemical pulping process in the world. Roughly 195 million metric tons of black liquor are produced annually as a by-product from the Kraft pulping process. Black liquor consists of spent cooking chemicals and dissolved organics from the wood and can contain up to 0.15 wt% nitrogen on dry solids basis. The cooking chemicals from black liquor are recovered in a chemical recovery cycle. Water is evaporated in the first stage of the chemical recovery cycle, so the black liquor has a dry solids content of 65-85% prior to combustion. During combustion of black liquor, a portion of the black liquor nitrogen is volatilized, finally forming N2 or NO. The rest of the nitrogen remains in the char as char nitrogen. During char conversion, fixed carbon is burned off leaving the pulping chemicals as smelt, and the char nitrogen forms mostly smelt nitrogen (cyanate, OCN-). Smelt exits the recovery boiler and is dissolved in water. The cyanate from smelt decomposes in the presence of water, forming NH3, which causes nitrogen emissions from the rest of the chemical recovery cycle. This thesis had two focuses: firstly, to determine how the nitrogen chemistry in the recovery boiler is affected by modification of black liquor; and secondly, to find out what causes cyanate formation during thermal conversion, and which parameters affect cyanate formation and decomposition during thermal conversion of black liquor. The fate of added biosludge nitrogen in chemical recovery was determined in Paper I. The added biosludge increased the nitrogen content of black liquor. At the pulp mill, the added biosludge did not increase the NO formation in the recovery boiler, but instead increased the amount of cyanate in green liquor. The increased cyanate caused more NH3 formation, which increased the NCG boiler’s NO emissions. Laboratory-scale experiments showed an increase in both NO and cyanate formation after biosludge addition. Black liquor can be modified, for example by addition of a solid biomass to increase the energy density of black liquor, or by separation of lignin from black liquor by precipitation. The precipitated lignin can be utilized in the production of green chemicals or as a fuel. In Papers II and III, laboratory-scale experiments were conducted to determine the impact of black liquor modification on NO and cyanate formation. Removal of lignin from black liquor reduced the nitrogen content of the black liquor. In most cases NO and cyanate formation decreased with increasing lignin removal; the exception was NO formation from lignin lean soda liquors. The addition of biomass to black liquor resulted in a higher nitrogen content fuel mixture, due to the higher nitrogen content of biomass compared to black liquor. More NO and cyanate were formed from the fuel mixtures than from pure black liquor. The increased amount of formed cyanate led to the hypothesis that black liquor is catalytically active and converts a portion of the nitrogen in the mixed fuel to cyanate. The mechanism behind cyanate formation during thermal conversion of black liquor was not clear before this thesis. Paper IV studies the cyanate formation of alkali metal loaded fuels during gasification in a CO2 atmosphere. The salts K2CO3, Na2CO3, and K2SO4 all promoted char nitrogen to cyanate conversion during gasification, while KCl and CaCO3 did not. It is now assumed that cyanate is formed when alkali metal carbonate or an active intermediate of alkali metal carbonate (e.g. -CO2K) reacts with the char nitrogen forming cyanate. By testing different fuels (bark, peat, and coal), each of which had a different form of organic nitrogen, it was concluded that the form of organic nitrogen in char also has an impact on cyanate formation. Cyanate can be formed during pyrolysis of black liquor, but at temperatures 900°C or above, the formed cyanate will decompose. Cyanate formation in gasifying conditions with different levels of CO2 in the atmosphere was also studied. Most of the char nitrogen was converted to cyanate during gasification at 800-900°C in 13-50% CO2 in N2, and only 5% of the initial fuel nitrogen was converted to NO during char conversion. The formed smelt cyanate was stable at 800°C 13% CO2, while it decomposed at 900°C 13% CO2. The cyanate decomposition was faster at higher temperatures and in oxygen-containing atmospheres than in an inert atmosphere. The presence of CO2 in oxygencontaining atmospheres slowed down the decomposition of cyanate. This work will provide new information on how modification of black liquor affects the nitrogen chemistry during thermal conversion of black liquor and what causes cyanate formation during thermal conversion of black liquor. The formation and decomposition of cyanate was studied in order to provide new data, which would be useful in modeling of nitrogen chemistry in the recovery boiler.

Comparing adult-youth and adult-adult online sexual solicitation: Manipulative behaviors, situational factors, and outcomes

Online sexual solicitation (solicitation) of youth has received widespread media and research attention during the last decade. The prevalence rates of youth who have experienced solicitation or solicitation attempts vary between studies depending on the methodology used (e.g., whether youth or adults are the target study group). In studies focusing on youth victims, the prevalence of solicitation attempts made by adults during the past year is typically reported to be between 5 and 9%. Adults who solicit youth online have been found to use deception and other manipulative behaviors to gain access to sexual activities with youth. However, previous studies have lacked a control group of adults who solicit other adults online. Without this comparison, one could argue that deceiving others online about one’s identity, and engaging in manipulative behaviors, is an inherent part of most online sexual interactions with strangers. Additionally, little is known about the associations between manipulative behaviors and the solicitation outcomes. In research concerning offline sexual behaviors, it has been noted that situational factors, such as sexual arousal, may alter both sexual interest and behavior. The effects of situational factors on online sexual behaviors have been less extensively studied (especially so with a quantitative approach); no studies have to date focused on adults’ solicitation of youth. Investigating the role of a lowered sexual age preference and the role of situational factors in the soliciting adults could be an important step in order to receive deeper knowledge of the role of traits and states in the context of solicitation. Additionally, there is a lack of knowledge of the effect of the age of the youth. Although previous studies on solicitation has found that older youth, compared with younger youth and children, are more often solicited, the possible reasons for this have not been investigated. Are adults who solicit youth affected by legal deterrence (through the legal age of consent), is it because older youth are more available online, or are the adults’ age preferences merely a product of a normally distributed age preference in the population? The purpose of the present thesis was fivefold: 1) to obtain an estimate of the frequency of adults’ solicitation of youth as self-reported and observed in actual behavior; 2) to explore whether the legal age of consent (LAC) affects solicitation frequency, or whether a normally distributed sexual age preference more accurately describe the proportion of solicited youth of different ages; 3) to investigate the associations of both traits (e.g., lower sexual age preference) and states (immediate situational factors, such as alcohol intoxication), and the solicitation target; 4) to explore whether adults who solicit youth and adults who solicit adults are equally deceitful and manipulative online, and whether the different solicitation outcomes are as common in both groups; and 5) to investigate whether the deceitful and manipulative behaviors engaged in had different associations with the solicitation outcomes depending on the age of the solicited. In the survey study, a convenience sample of 1393 adult participants (aged 18 years or older) self-reported any online communication with strangers during the past year. Of these, 56% (776 respondents) reported that they had solicited or attempted to solicit at least one stranger. Of the respondents, 453 (58.4%) were men, and 323 (41.6%) were women. Participants with only adult contacts (18 years or older) constituted the majority (640 respondents). In contrast, 136 individuals reported a youth contact (a 13 year old or younger, or a 14 to 17-year old). Approximately half of the participants were men in the adult contact group, while 75% of the participants were men in the youth contact group. Approximately 60% of the participants with youth contacts were recruited from two websites associated with a pedophilic sexual interest. In an online quasi-experimental study, with researchers impersonating youth of different ages (10–18 year olds) in chat rooms, 251 online conversations with chat room visitors made up the entire sample. All chat room visitors alleged to be men. The self-reported frequency of having solicited youth (0–17-year olds) during the past year was approximately 10% in our sample of adults who reported communicating with any strangers online. When we observed this behavior in chat rooms, we found that approximately 30% of the chat room visitors who believed they interacted with a 10 to 14 year old attempted to solicit the youth. We found that solicitation attempts increased equally much when increasing the age of the impersonated youth from 14 to 16, as from 16 to 18. Thus, we concluded that a normally distributed age preference in the population was a more plausible explanation to the effect of the age of the solicited, rather than the LAC (here; 15 and 16). If the chat room visitors would have been deterred only by the LAC, we would have expected that the change in amount of solicitation attempts from an illegal age group to a legal age group would have been significantly stronger than changes between age groups within illegal-illegal and legal-legal groups. Our subsample of survey participants from the pedophilia-related websites expectedly reported that they had solicited youth more often in comparison to the sample gathered through general (i.e., not associated with any particular sexual preference) websites. We also found that participants with a youth contact reported higher levels of sexual arousal and shame before the sexual interaction with their online contact, compared with participants with an adult contact. Additionally, the participants with youth contacts who reported consumption of child- and adolescent pornography also reported being more sexually aroused before the interaction, compared to the participants with youth contacts who did not report consumption of these kinds of pornography. We also found clear indications that the online sexual interaction had an alleviatory effect on reported levels of sadness, boredom and stress, independent of the age of the contact. Generally, the participants with youth and adult contacts reported deceiving their contacts as often and suggesting keeping the communication a secret from someone as often. Participants with a youth contact, however, reported using more persuasion techniques for online sexual purposes or for the purpose of an offline meeting, compared to those with an adult contact. In the chat rooms, we found that more indirect ways of future sexual communication (e.g., continuing chatting) was suggested by the chat room visitors that were under the assumption of interacting with youth aged 10 to 14, compared with more direct means (e.g., meeting offline). Survey participants with youth contacts who had used deception, suggested keeping the interactions a secret, and/or persuaded their contact by appealing to the contacts feelings of love and attachment for the participant had also more often engaged in cybersex with the contact. No other manipulative behaviors were associated with the other investigated solicitation outcomes (receiving a sexual picture, meeting offline, and engaging in sexual contact offline) within this group of participants. However, using deception, suggesting secrecy and using persuasion was also positively associated with certain solicitation outcomes within participants with an adult contact. In summary, adults’ solicitation of youth is much more frequent when observed in chat rooms than self-reported. Additionally, an underlying lowered sexual age preference seems to be a motivating factor on a group level in adults who solicit youth. We concluded that directed prevention efforts should be made on pedophiliarelated websites. Additionally, the role of situational factors, especially sexual arousal in persons with a pedo- or hebephilic sexual interest should be investigated further in the context of online sexual solicitation.

Designing sustainable industrial ecosystems : the case of a biogas-for-traffic solution

This thesis focuses on the development of sustainable industrial architectures for bioenergy based on the metaphors of industrial symbiosis and industrial ecosystems, which imply exchange of material and energy side-flows of various industries in order to improve sustainability of those industries on a system level. The studies on industrial symbiosis have been criticised for staying at the level of incremental changes by striving for cycling waste and by-flows of the industries ‘as is’ and leaving the underlying industry structures intact. Moreover, there has been articulated the need for interdisciplinary research on industrial ecosystems as well as the need to extend the management and business perspectives on industrial ecology. This thesis addresses this call by applying a business ecosystem and business model perspective on industrial symbiosis in order to produce knowledge on how industrial ecosystems can be developed that are sustainable environmentally and economically. A case of biogas business is explored and described in four research papers and an extended summary that form this thesis. Since the aim of the research was to produce a normative model for developing sustainable industrial ecosystems, the methodology applied in this research can be characterised as constructive and collaborative. A constructive research mode was required in order to expand the historical knowledge on industrial symbiosis development and business ecosystem development into the knowledge of what should be done, which is crucial for sustainability and the social change it requires. A collaborative research mode was employed through participating in a series of projects devoted to the development of a biogas-for-traffic industrial ecosystem. The results of the study showed that the development of material flow interconnections within industrial symbiosis is inseparable from larger business ecosystem restructuring. This included a shift in the logic of the biogas and traffic fuel industry and a subsequent development of a business ecosystem that would entail the principles of industrial symbiosis and localised energy production and consumption. Since a company perspective has been taken in this thesis, the role of an ecosystem integrator appeared as a crucial means to achieve the required industry restructuring. This, in turn, required the development of a modular and boundary-spanning business model that had a strong focus on establishing collaboration among ecosystem stakeholders and development of multiple local industrial ecosystems as part of business growth. As a result, the designed business model of the ecosystem integrator acquired the necessary flexibility in order to adjust to local conditions, which is crucial for establishing industrial symbiosis. This thesis presents a normative model for the development of a business model required for creating sustainable industrial ecosystems, which contributes to approaches at the policy-makers’ level, proposed earlier. Therefore, this study addresses the call for more research on the business level of industrial ecosystem formation and the implications for the business models of the involved actors. Moreover, the thesis increases the understanding of system innovation and innovation in business ecosystems by explicating how business model innovation can be the trigger for achieving more sustainable industry structures, such as those relying on industrial symbiosis.

Changing teachers´ practices in regular schools enrolling children with visual impairment

The number of persons with visual impairment in Tanzania is estimated to over 1.6 million. About half a million of these persons are children aged 7-13. Only about 1% of these children are enrolled in schools. The special schools and units are too few and in most cases they are far away from the children’s homes. More and more regular schools are enrolling children with visual impairment, but the schools lack financial resources, tactile teaching materials and trained special education teachers. Children with visual impairment enrolled in regular schools seldom get enough support and often fail in examinations. The general aim of this study was to contribute to increased knowledge and understanding about how teachers can change their teaching practices and thus facilitate the learning of children with visual impairment included in regular classrooms as they participate in an action research project. The project was conducted in a primary school in a poor rural region with a high frequency of blindness and visual impairment. The school was poorly resourced and the average number of pupils per class was 90. The teachers who participated in the collaborative action research project were the 14 teachers who taught blind or visually impaired pupils in grades 4 and 6, in total 6 pupils. The action research project was conducted during a period of 6 months and was carried out in five cycles. The teachers were actively involved in all the project activities; identifying challenges, planning solutions, producing teaching materials, reflecting on outcomes, collaborating and evaluating. Empirical data was collected with questionnaires, interviews, observations and focus group discussions. The findings of the study show that the teachers managed to change their teaching practices through systematic reflection, analysis and collaboration. The teachers produced a variety of tactile teaching materials, which facilitated the learning of the pupils with visual impairment. The pupils learned better and felt more included in the regular classes. The teachers gained new knowledge and skills. They grew professionally and started to collaborate with each other. The study contributes to new knowledge of how collaborative action research can be conducted in the area of special education in a Tanzanian school context. The study has also relevance to the planning of school-based professional development programs and teacher education programs in Tanzania and in other low-income countries. The results also point at strategies which can promote inclusion of children with disabilities in regular schools.

Thermal reactions of the major hydrocarbon components of biomass gasification gas

Gasification of biomass is an efficient method process to produce liquid fuels, heat and electricity. It is interesting especially for the Nordic countries, where raw material for the processes is readily available. The thermal reactions of light hydrocarbons are a major challenge for industrial applications. At elevated temperatures, light hydrocarbons react spontaneously to form higher molecular weight compounds. In this thesis, this phenomenon was studied by literature survey, experimental work and modeling effort. The literature survey revealed that the change in tar composition is likely caused by the kinetic entropy. The role of the surface material is deemed to be an important factor in the reactivity of the system. The experimental results were in accordance with previous publications on the subject. The novelty of the experimental work lies in the used time interval for measurements combined with an industrially relevant temperature interval. The aspects which are covered in the modeling include screening of possible numerical approaches, testing of optimization methods and kinetic modelling. No significant numerical issues were observed, so the used calculation routines are adequate for the task. Evolutionary algorithms gave a better performance combined with better fit than the conventional iterative methods such as Simplex and Levenberg-Marquardt methods. Three models were fitted on experimental data. The LLNL model was used as a reference model to which two other models were compared. A compact model which included all the observed species was developed. The parameter estimation performed on that model gave slightly impaired fit to experimental data than LLNL model, but the difference was barely significant. The third tested model concentrated on the decomposition of hydrocarbons and included a theoretical description of the formation of carbon layer on the reactor walls. The fit to experimental data was extremely good. Based on the simulation results and literature findings, it is likely that the surface coverage of carbonaceous deposits is a major factor in thermal reactions.

α-Pinene oxide and verbenol oxide isomerizations over heterogeneous catalysts

Terpenes are a valuable natural resource for the production of fine chemicals. Turpentine, obtained from biomass and also as a side product of softwood industry, is rich in monoterpenes such as α-pinene and β-pinene, which are widely used as raw materials in the synthesis of flavors, fragrances and pharmaceutical compounds. The rearrangement of their epoxides has been thoroughly studied in recent years, as a method to obtain compounds which are further used in the fine chemical industry. The industrially most desired products of α-pinene oxide isomerization are campholenic aldehyde and trans-carveol. Campholenic aldehyde is an intermediate for the manufacture of sandalwood-like fragrances such as santalol. Trans-carveol is an expensive constituent of the Valencia orange essence oil used in perfume bases and food flavor composition. Furthermore it has been found to exhibit chemoprevention of mammary carcinogenesis. A wide range of iron and ceria supported catalysts were prepared, characterized and tested for α-pinene oxide isomerization in order to selective synthesis of above mentioned products. The highest catalytic activity in the preparation of campholenic aldehyde over iron modified catalysts using toluene as a solvent at 70 °C (total conversion of α-pinene oxide with a selectivity of 66 % to the desired aldehyde) was achieved in the presence of Fe-MCM-41. Furthermore, Fe-MCM-41 catalyst was successfully regenerated without deterioration of catalytic activity and selectivity. The most active catalysts in the synthesis of trans-carveol from α-pinene oxide over iron and ceria modified catalysts in N,N-dimethylacetamide as a solvent at 140 °C (total conversion of α-pinene oxide with selectivity 43 % to trans-carveol) were Fe-Beta-300 and Ce-Si-MCM-41. These catalysts were further tested for an analogous reaction, namely verbenol oxide isomerization. Verbenone is another natural organic compound which can be found in a variety of plants or synthesized by allylic oxidation of α-pinene. An interesting product which is synthesized from verbenone is (1R,2R,6S)-3-methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol. It has been discovered that this diol possesses potent anti-Parkinson activity. The most effective way leading to desired diol starts from verbenone and includes three stages: epoxidation of verbenone to verbenone oxide, reduction of verbenone oxide and subsequent isomerization of obtained verbenol oxide, which is analogous to isomerization of α-pinene oxide. In the research focused on the last step of these synthesis, high selectivity (82 %) to desired diol was achieved in the isomerization of verbenol oxide at a conversion level of 96 % in N,N-dimethylacetamide at 140 °C using iron modified zeolite, Fe-Beta-300. This reaction displayed surprisingly high selectivity, which has not been achieved yet. The possibility of the reuse of heterogeneous catalysts without activity loss was demonstrated.

The multicultural moment : the history of the idea and politics of multiculturalism in Sweden in comparative, transnational and biographical context, 1964–1975

The emergence of the idea of multiculturalism in Swedish public discourse and social science in the latter half of the 1960s and introduction of official multiculturalism in 1975 constituted a major intellectual and political shift in the post-war history of Sweden. The ambition of the 1975 immigrant and minority policy to enable the preservation of ethno-cultural minorities and to create a positive attitude towards the new multicultural society among the majority population was also incorporated into Swedish cultural, educational and media policies. The rejection of assimilationism and the new commitment to ethno-cultural diversity, the multicultural moment, has earned Sweden a place on the list of the early adopters of official multiculturalism, together with Canada and Australia. This compilation thesis examines the origins and early post-war history of the idea of multiculturalism as well as the interplay between idea and politics in the shift from a public ideal of homogeneity to an ideal of multiculturalism in Sweden. It does so from a range of conceptual, comparative, transnational, and biographical perspectives. The thesis consists of an introduction (Part I) and four previously published studies (Part II). The primary research result of the thesis concerns the agency involved in the break-through and formal establishment of the idea of multiculturalism in Sweden. Actors such as ethnic activists, experts and officials were instrumental in the introduction and establishment of multiculturalism in Sweden, as they also had been in Canada and in Australia. These actors have, however, not previously been recognized and analysed as significant idea-makers and political agents in the case of Sweden. The intertwined connections between activists, social scientists, linguists, and officials facilitated the transfer of the idea of multiculturalism from a publically contested idea to public policy via the way of The Swedish Trade Union Confederation, academia and the Royal Commission of Immigration. The thesis furthermore shows that the political success of the idea of multiculturalism, such as it was within the limits of the universalist social democratic welfare state, was dependent on whom the claims-makers were, the status and positions they held, and the way the idea of multiculturalism was conceptualised and used. It was also dependent on the migratory context of labour immigration in the 1960s and 1970s and on whose behalf the advocates of multiculturalism made their claims. The majority of the labour immigrants were Finnish citizens from the former eastern half of the kingdom of Sweden who were net contributors to the Swedish welfare state. This facilitated the recognition of their ethno-cultural difference, and, following the logic of universalism, the ethno-cultural difference of other minority groups in Sweden. The historical significance of the multicultural moment is still evident in the contemporary immigration and integration policies of Sweden. The affirmation of diversity continues to set Sweden apart from the rest of Europe, now more so than in the 1970s, even though the migratory context has changed radically in the last 40 years.

JNK regulates dendrite and spine architecture in the central nervous system influencing spatial learning and motor tasks

JNK1 is a MAP-kinase that has proven a significant player in the central nervous system. It regulates brain development and the maintenance of dendrites and axons. Several novel phosphorylation targets of JNK1 were identified in a screen performed in the Coffey lab. These proteins were mainly involved in the regulation of neuronal cytoskeleton, influencing the dynamics and stability of microtubules and actin. These structural proteins form the dynamic backbone for the elaborate architecture of the dendritic tree of a neuron. The initiation and branching of the dendrites requires a dynamic interplay between the cytoskeletal building blocks. Both microtubules and actin are decorated by associated proteins which regulate their dynamics. The dendrite-specific, high molecular weight microtubule associated protein 2 (MAP2) is an abundant protein in the brain, the binding of which stabilizes microtubules and influences their bundling. Its expression in non-neuronal cells induces the formation of neurite-like processes from the cell body, and its function is highly regulated by phosphorylation. JNK1 was shown to phosphorylate the proline-rich domain of MAP2 in vivo in a previous study performed in the group. Here we verify three threonine residues (T1619, T1622 and T1625) as JNK1 targets, the phosphorylation of which increases the binding of MAP2 to microtubules. This binding stabilizes the microtubules and increases process formation in non-neuronal cells. Phosphorylation-site mutants were engineered in the lab. The non-phosphorylatable mutant of MAP2 (MAP2- T1619A, T1622A, T1625A) in these residues fails to bind microtubules, while the pseudo-phosphorylated form, MAP2- T1619D, T1622D, Thr1625D, efficiently binds and induces process formation even without the presence of active JNK1. Ectopic expression of the MAP2- T1619D, T1622D, Thr1625D in vivo in mouse brain led to a striking increase in the branching of cortical layer 2/3 (L2/3) pyramidal neurons, compared to MAP2-WT. The dendritic complexity defines the receptive field of a neuron and dictates the output to the postsynaptic cells. Previous studies in the group indicated altered dendrite architecture of the pyramidal neurons in the Jnk1-/- mouse motor cortex. Here, we used Lucifer Yellow loading and Sholl analysis of neurons in order to study the dendritic branching in more detail. We report a striking, opposing effect in the absence of Jnk1 in the cortical layers 2/3 and 5 of the primary motor cortex. The basal dendrites of pyramidal neurons close to the pial surface at L2/3 show a reduced complexity. In contrast, the L5 neurons, which receive massive input from the L2/3 neurons, show greatly increased branching. Another novel substrate identified for JNK1 was MARCKSL1, a protein that regulates actin dynamics. It is highly expressed in neurons, but also in various cancer tissues. Three phosphorylation target residues for JNK1 were identified, and it was demonstrated that their phosphorylation reduces actin turnover and retards migration of these cells. Actin is the main cytoskeletal component in dendritic spines, the site of most excitatory synapses in pyramidal neurons. The density and gross morphology of the Lucifer Yellow filled dendrites were characterized and we show reduced density and altered morphology of spines in the motor cortex and in the hippocampal area CA3. The dynamic dendritic spines are widely considered to function as the cellular correlate during learning. We used a Morris water maze to test spatial memory. Here, the wild-type mice outperformed the knock-out mice during the acquisition phase of the experiment indicating impaired special memory. The L5 pyramidal neurons of the motor cortex project to the spinal cord and regulate the movement of distinct muscle groups. Thus the altered dendrite morphology in the motor cortex was expected to have an effect on the input-output balance in the signaling from the cortex to the lower motor circuits. A battery of behavioral tests were conducted for the wild-type and Jnk1-/- mice, and the knock-outs performed poorly compared to wild-type mice in tests assessing balance and fine motor movements. This study expands our knowledge of JNK1 as an important regulator of the dendritic fields of neurons and their manifestations in behavior.

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

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

Functional cellulose microspheres for pharmaceutical applications

Dissolving cellulose is the first main step in preparing novel cellulosicmaterials. Since cellulosic fibres cannot be easily dissolved in water-based solvents, fibres were pretreated with ethanol-acid solution prior to the dissolution. Solubility and changes on the surface of the fibres were studied with microscopy and capillary viscometry. After the treatment, the cellulose fibres were soluble in alkaline urea-water solvent. The nature of this viscous solution was studied rheologically. Cellulose microspheres were prepared by extruding the alkaline cellulose solution through the needle into an acidic medium. By altering the temperature and acidity of the mediumit was possible to adjust the specific surface area and pore sizes of themicrospheres. A typical skin-core structure was found in all samples. Microspheres were oxidised in order to introduce anionic carboxylic acid groups (AGs). Anionic microspheres are more hydrophilic; their water-uptake increased 25 times after oxidation and they could swell almost to their original state (88%) after drying and shrinking. Swelling was studied in simulated physiological environments, corresponding to stomach acid and intestines (pH 1.2-7.4). Oxidised microspheres were used as a drug carriers. They demonstrated a highmass uniformity, which would enable their use for personalised dosing among different patients, including children. The drug was solidified in microspheres in amorphous form. This enhanced solubility and could be used for more challenging drugs with poor solubility. The pores of themicrospheres also remained open after the drug was loaded and they were dried. Regardless of the swelling, the drug was released at a constant rate in all environments.

Rigorous development of safety-critical systems

Nowadays, computer-based systems tend to become more complex and control increasingly critical functions affecting different areas of human activities. Failures of such systems might result in loss of human lives as well as significant damage to the environment. Therefore, their safety needs to be ensured. However, the development of safety-critical systems is not a trivial exercise. Hence, to preclude design faults and guarantee the desired behaviour, different industrial standards prescribe the use of rigorous techniques for development and verification of such systems. The more critical the system is, the more rigorous approach should be undertaken. To ensure safety of a critical computer-based system, satisfaction of the safety requirements imposed on this system should be demonstrated. This task involves a number of activities. In particular, a set of the safety requirements is usually derived by conducting various safety analysis techniques. Strong assurance that the system satisfies the safety requirements can be provided by formal methods, i.e., mathematically-based techniques. At the same time, the evidence that the system under consideration meets the imposed safety requirements might be demonstrated by constructing safety cases. However, the overall safety assurance process of critical computerbased systems remains insufficiently defined due to the following reasons. Firstly, there are semantic differences between safety requirements and formal models. Informally represented safety requirements should be translated into the underlying formal language to enable further veri cation. Secondly, the development of formal models of complex systems can be labour-intensive and time consuming. Thirdly, there are only a few well-defined methods for integration of formal verification results into safety cases. This thesis proposes an integrated approach to the rigorous development and verification of safety-critical systems that (1) facilitates elicitation of safety requirements and their incorporation into formal models, (2) simplifies formal modelling and verification by proposing specification and refinement patterns, and (3) assists in the construction of safety cases from the artefacts generated by formal reasoning. Our chosen formal framework is Event-B. It allows us to tackle the complexity of safety-critical systems as well as to structure safety requirements by applying abstraction and stepwise refinement. The Rodin platform, a tool supporting Event-B, assists in automatic model transformations and proof-based verification of the desired system properties. The proposed approach has been validated by several case studies from different application domains.

Pressurized hot water flow-through extraction of birch wood

Effective processes to fractionate the main compounds in biomass, such as wood, are a prerequisite for an effective biorefinery. Water is environmentally friendly and widely used in industry, which makes it a potential solvent also for forest biomass. At elevated temperatures over 100 °C, water can readily hydrolyse and dissolve hemicelluloses from biomass. In this work, birch sawdust was extracted using pressurized hot water (PHWE) flow-through systems. The hypothesis of the work was that it is possible to obtain polymeric, water-soluble hemicelluloses from birch sawdust using flow-through PHW extractions at both laboratory and large scale. Different extraction temperatures in the range 140–200 °C were evaluated to see the effect of temperature to the xylan yield. The yields and extracted hemicelluloses were analysed to obtain sugar ratios, the amount of acetyl groups, furfurals and the xylan yields. Higher extraction temperatures increased the xylan yield, but decreased the molar mass of the dissolved xylan. As the extraction temperature increased, more acetic acid was released from the hemicelluloses, thus further decreasing the pH of the extract. There were only trace amounts of furfurals present after the extractions, indicating that the treatment was mild enough not to degrade the sugars further. The sawdust extraction density was increased by packing more sawdust in the laboratory scale extraction vessel. The aim was to obtain extracts with higher concentration than in typical extraction densities. The extraction times and water flow rates were kept constant during these extractions. The higher sawdust packing degree decreased the water use in the extractions and the extracts had higher hemicellulose concentrations than extractions with lower sawdust degrees of packing. The molar masses of the hemicelluloses were similar in higher packing degrees and in the degrees of packing that were used in typical PHWE flow-through extractions. The structure of extracted sawdust was investigated using small angle-(SAXS) and wide angle (WAXS) x-ray scattering. The cell wall topography of birch sawdust and extracted sawdust was compared using x-ray tomography. The results showed that the structure of the cell walls of extracted birch sawdust was preserved but the cell walls were thinner after the extractions. Larger pores were opened inside the fibres and cellulose microfibrils were more tightly packed after the extraction. Acetate buffers were used to control the pH of the extracts during the extractions. The pH control prevented excessive xylan hydrolysis and increased the molar masses of the extracted xylans. The yields of buffered extractions were lower than for plain water extractions at 160–170 °C, but at 180 °C yields were similar to those from plain water and pH buffers. The pH can thus be controlled during extraction with acetate buffer to obtain xylan with higher molar mass than those obtainable using plain water. Birch sawdust was extracted both in the laboratory and pilot scale. The performance of the PHWE flow-through system was evaluated in the laboratory and the pilot scale using vessels with the same shape but different volumes, with the same relative water flow through the sawdust bed, and in the same extraction temperature. Pre-steaming improved the extraction efficiency and the water flow through the sawdust bed. The extracted birch sawdust and the extracted xylan were similar in both laboratory and pilot scale. The PHWE system was successfully scaled up by a factor of 6000 from the laboratory to pilot scale and extractions performed equally well in both scales. The results show that a flow-through system can be further scaled up and used to extract water-soluble xylans from birch sawdust. Extracted xylans can be concentrated, purified, and then used in e.g. films and barriers, or as building blocks for novel material applications.

Silicon-containing species in used lube oil re-refining

Nowadays, the re-refining of the used lube oils has gained worldwide a lot of attention due to the necessity for added environmental protection and increasingly stringent environmental legislation. One of the parameters determining the quality of the produced base oils is the composition of feedstock. Estimation of the chemical composition of the used oil collected from several European locations showed that the hydrocarbon structure of the motor oil is changed insignificantly during its operation and the major part of the changes is accounted for with depleted oil additives. In the lube oil re-refining industry silicon, coming mainly from antifoaming agents, is recognized to be a contaminant generating undesired solid deposits in various locations in the re-refining units. In this thesis, a particular attention was paid to the mechanism of solid product formation during the alkali treatment process of silicon-containing used lube oils. The transformations of a model siloxane, tetramethyldisiloxane (TMDS), were studied in a batch reactor at industrially relevant alkali treatment conditions (low temperature, short reaction time) using different alkali agents. The reaction mechanism involving solid alkali metal silanolates was proposed. The experimental data obtained demonstrated that the solids were dominant products at low temperature and short reaction time. The liquid products in the low temperature reactions were represented mainly by linear siloxanes. The prolongation of reaction time resulted in reduction of solids, whereas both temperature and time increase led to dominance of cyclic products in the reaction mixture. Experiments with the varied reaction time demonstrated that the concentration of cyclic trimer being the dominant in the beginning of the reaction diminished with time, whereas the cyclic tetramer tended to increase. Experiments with lower sodium hydroxide concentration showed the same effect. In addition, a decrease of alkali agent concentration in the initial reaction mixture accelerated TMDS transformation reactions resulting in solely liquid cyclic siloxanes yields. Comparison of sodium and potassium hydroxides applied as an alkali agent demonstrated that potassium hydroxide was more efficient, since the activation energy in KOH presence was almost 2-fold lower than that for sodium hydroxide containing reaction mixture. Application of potassium hydroxide for TMDS transformation at 100° C with 3 hours reaction time resulted in 20 % decrease of solid yields compared to NaOH-containing mixture. Moreover, TMDS transformations in the presence of sodium silanolate applied as an alkali agent led to formation of only liquid products without formation of the undesired solids. On the basis of experimental data and the proposed reaction mechanism, a kinetic model was developed, which provided a satisfactory description of the experimental results. Suitability of the selected siloxane as a relevant model of industrial silicon-containing compounds was verified by investigation of the commercially available antifoam agent in base-catalyzed conditions.

Spatial modeling techniques for mapping and characterization of acid sulfate soils

Acid sulfate (a.s.) soils constitute a major environmental issue. Severe ecological damage results from the considerable amounts of acidity and metals leached by these soils in the recipient watercourses. As even small hot spots may affect large areas of coastal waters, mapping represents a fundamental step in the management and mitigation of a.s. soil environmental risks (i.e. to target strategic areas). Traditional mapping in the field is time-consuming and therefore expensive. Additional more cost-effective techniques have, thus, to be developed in order to narrow down and define in detail the areas of interest. The primary aim of this thesis was to assess different spatial modeling techniques for a.s. soil mapping, and the characterization of soil properties relevant for a.s. soil environmental risk management, using all available data: soil and water samples, as well as datalayers (e.g. geological and geophysical). Different spatial modeling techniques were applied at catchment or regional scale. Two artificial neural networks were assessed on the Sirppujoki River catchment (c. 440 km2) located in southwestern Finland, while fuzzy logic was assessed on several areas along the Finnish coast. Quaternary geology, aerogeophysics and slope data (derived from a digital elevation model) were utilized as evidential datalayers. The methods also required the use of point datasets (i.e. soil profiles corresponding to known a.s. or non-a.s. soil occurrences) for training and/or validation within the modeling processes. Applying these methods, various maps were generated: probability maps for a.s. soil occurrence, as well as predictive maps for different soil properties (sulfur content, organic matter content and critical sulfide depth). The two assessed artificial neural networks (ANNs) demonstrated good classification abilities for a.s. soil probability mapping at catchment scale. Slightly better results were achieved using a Radial Basis Function (RBF) -based ANN than a Radial Basis Functional Link Net (RBFLN) method, narrowing down more accurately the most probable areas for a.s. soil occurrence and defining more properly the least probable areas. The RBF-based ANN also demonstrated promising results for the characterization of different soil properties in the most probable a.s. soil areas at catchment scale. Since a.s. soil areas constitute highly productive lands for agricultural purpose, the combination of a probability map with more specific soil property predictive maps offers a valuable toolset to more precisely target strategic areas for subsequent environmental risk management. Notably, the use of laser scanning (i.e. Light Detection And Ranging, LiDAR) data enabled a more precise definition of a.s. soil probability areas, as well as the soil property modeling classes for sulfur content and the critical sulfide depth. Given suitable training/validation points, ANNs can be trained to yield a more precise modeling of the occurrence of a.s. soils and their properties. By contrast, fuzzy logic represents a simple, fast and objective alternative to carry out preliminary surveys, at catchment or regional scale, in areas offering a limited amount of data. This method enables delimiting and prioritizing the most probable areas for a.s soil occurrence, which can be particularly useful in the field. Being easily transferable from area to area, fuzzy logic modeling can be carried out at regional scale. Mapping at this scale would be extremely time-consuming through manual assessment. The use of spatial modeling techniques enables the creation of valid and comparable maps, which represents an important development within the a.s. soil mapping process. The a.s. soil mapping was also assessed using water chemistry data for 24 different catchments along the Finnish coast (in all, covering c. 21,300 km2) which were mapped with different methods (i.e. conventional mapping, fuzzy logic and an artificial neural network). Two a.s. soil related indicators measured in the river water (sulfate content and sulfate/chloride ratio) were compared to the extent of the most probable areas for a.s. soils in the surveyed catchments. High sulfate contents and sulfate/chloride ratios measured in most of the rivers demonstrated the presence of a.s. soils in the corresponding catchments. The calculated extent of the most probable a.s. soil areas is supported by independent data on water chemistry, suggesting that the a.s. soil probability maps created with different methods are reliable and comparable.

Paul and death : a study in psychological coping

The present investigation looks into the attitudes toward death in Paul’s authentic letters, and puts them in relation to modern theories of psychological coping. Drawing on psychologically-oriented hermeneutic theory, and theories about psychological coping in particular, I argue that each case of psychological coping must be understood in its historical situation as strategies emanating from a specific person’s subjective appraisal (cf. Pargament, Lazarus and Folkman). Paul’s letters frequently refer to persecution and violent death. To aid in psychological coping is often integral to the purpose of the letters, which makes the perspective of psychological coping akin to their genre. In the course of a tentatively assumed chronological order of 1 Thessalonians, Galatians, 1 Corinthians, 2 Corinthians, Romans, Philippians, and Philemon, Paul moves from the perception of Jesus dying for the faithful to the understanding of dying with Jesus. His coping strategies concerning death are gradually transformed from conservative and deferring coping styles, to a more self-directing coping style, to collaborative and transformative coping styles, and finally to a new sense of deferring coping style in prison. The last case of deferring coping carries the traits of generosity and flexibility even in the face of death, which is in contrast to his previous letters. Through his correspondence, we see Paul’s attitude toward death transformed from denial to reaction, to processing, to acceptance (cf. Lindemann, Kübler-Ross, Bowlby, Parkes, among others). His strategies also shift in accordance with these understandings. Denial is accompanied by diversion, threat by aggression, processing by rumination, and acceptance by joy. The study shows the hermeneutic benefits of reading Paul’s letters as the rhetorically framed expressions of a person in a particular historical situation. The letters open small windows through which we can glimpse the coping process of a person of antiquity. In adopting the method of psychological exegesis, the study shows that the variety of attitudes toward death in Paul’s letters makes sense from the perspective of psychological coping. The psychological aspect of these letters is an underexamined richness that can extend into areas of contemporary individual and group identity, and from there to public policy and ethics.