Potential of kite aerial photography for peatland investigations with examples from Estonia

Tiivistelmä: Leijailmakuvausmenetelmän käyttömahdollisuudet soiden kartoituksessa - esimerkkejä Viron soilta

Applying geostatistics for investigations of forest ecosystems using remote sensing imagery

Abstract

Investigations of GaAs based heterostructures for spintronics

In the present work are reported investigations of structural, magnetic and electronic properties of GaAs/Ga1-xInxAs/GaAs quantum wells (QW) having a 0.5 - 1.8 monolayer thick Mn layer, separated from the quantum well by a 3 nm thick spacer. The structure of the samples is analyzed in details by photoluminescence and high-resolution X-ray difractometry and reflectometry, confirming that Mn atoms are practically absent from the QW. Transport properties and crystal structure are analyzed for the first time for this type of QW structures with so high mobility. Observedconductivity and the Hall effect in quantizing magnetic fields in wide temperature range, defined by transport of holes in the quantum well, demonstrate properties inherent to ferromagnetic systems with spin polarization of charge carriersin the QW. Investigation of the Shubnikov ¿ de Haas and the Hall effects gave the possibility to estimate the energy band parameters such as cyclotron mass andFermi level and calculate concentrations and mobilities of holes and show the high-quality of structures. Magnetic ordering is confirmed by the existence of the anomalous Hall effect.

Wet Oxidation of Concentrated Wastewaters: Process Combination and Reaction Kinetic Modeling

The accumulation of aqueous pollutants is becoming a global problem. The search for suitable methods and/or combinations of water treatment processes is a task that can slow down and stop the process of water pollution. In this work, the method of wet oxidation was considered as an appropriate technique for the elimination of the impurities present in paper mill process waters. It has been shown that, when combined with traditional wastewater treatment processes, wet oxidation offers many advantages. The combination of coagulation and wet oxidation offers a new opportunity for the improvement of the quality of wastewater designated for discharge or recycling. First of all, the utilization of coagulated sludge via wet oxidation provides a conditioning process for the sludge, i.e. dewatering, which is rather difficult to carry out with untreated waste. Secondly, Fe2(SO4)3, which is employed earlier as a coagulant, transforms the conventional wet oxidation process into a catalytic one. The use of coagulation as the post-treatment for wet oxidation can offer the possibility of the brown hue that usually accompanies the partial oxidation to be reduced. As a result, the supernatant is less colored and also contains a rather low amount of Fe ions to beconsidered for recycling inside mills. The thickened part that consists of metal ions is then recycled back to the wet oxidation system. It was also observed that wet oxidation is favorable for the degradation of pitch substances (LWEs) and lignin that are present in the process waters of paper mills. Rather low operating temperatures are needed for wet oxidation in order to destruct LWEs. The oxidation in the alkaline media provides not only the faster elimination of pitch and lignin but also significantly improves the biodegradable characteristics of wastewater that contains lignin and pitch substances. During the course of the kinetic studies, a model, which can predict the enhancements of the biodegradability of wastewater, was elaborated. The model includes lumped concentrations suchas the chemical oxygen demand and biochemical oxygen demand and reflects a generalized reaction network of oxidative transformations. Later developments incorporated a new lump, the immediately available biochemical oxygen demand, which increased the fidelity of the predictions made by the model. Since changes in biodegradability occur simultaneously with the destruction of LWEs, an attempt was made to combine these two facts for modeling purposes.

Experimental insights into deformation dynamics and intermittency in rapid granular shear flows

This work concerns the experimental study of rapid granular shear flows in annular Couette geometry. The flow is induced by continuous driving of the horizontal plate at the top of the granular bed in an annulus. The compressive pressure, driving torque, instantaneous bed height and rotational speed of the shearing plate are measured. Moreover, local stress fluctuations are measured in a medium made of steel spheres 2 and 3 mm in diameter. Both monodisperse packing and bidisperse packing are investigated to reveal the influence of size diversity in intermittent features of granular materials. Experiments are conducted in an annulus that can contain up to 15 kg of spherical steel balls. The shearing granular medium takes place via the rotation of the upper plate which compresses the material loaded inside the annulus. Fluctuations of compressive force are locally measured at the bottom of the annulus using a piezoelectric sensor. Rapid shear flow experiments are pursued at different compressive forces and shear rates and the sensitivity of fluctuations are then investigated by different means through monodisperse and bidisperse packings. Another important feature of rapid granular shear flows is the formation of ordered structures upon shearing. It requires a certain range for the amount of granular material (uniform size distribution) loaded in the system in order to obtain stable flows. This is studied more deeply in this thesis. The results of the current work bring some new insights into deformation dynamics and intermittency in rapid granular shear flows. The experimental apparatus is modified in comparison to earlier investigations. The measurements produce data for various quantities continuously sampled from the start of shearing to the end. Static failure and dynamic shearing ofa granular medium is investigated. The results of this work revealed some important features of failure dynamics and structure formation in the system. Furthermore, some computer simulations are performed in a 2D annulus to examine the nature of kinetic energy dissipation. It is found that turbulent flow models can statistically represent rapid granular flows with high accuracy. In addition to academic outcomes and scientific publications our results have a number of technological applications associated with grinding, mining and massive grain storages.

Mass transfer and particleinteractions in granular systems and suspension flows

The purpose of this study was to investigate some important features of granular flows and suspension flows by computational simulation methods. Granular materials have been considered as an independent state ofmatter because of their complex behaviors. They sometimes behave like a solid, sometimes like a fluid, and sometimes can contain both phases in equilibrium. The computer simulation of dense shear granular flows of monodisperse, spherical particles shows that the collisional model of contacts yields the coexistence of solid and fluid phases while the frictional model represents a uniform flow of fluid phase. However, a comparison between the stress signals from the simulations and experiments revealed that the collisional model would result a proper match with the experimental evidences. Although the effect of gravity is found to beimportant in sedimentation of solid part, the stick-slip behavior associated with the collisional model looks more similar to that of experiments. The mathematical formulations based on the kinetic theory have been derived for the moderatesolid volume fractions with the assumption of the homogeneity of flow. In orderto make some simulations which can provide such an ideal flow, the simulation of unbounded granular shear flows was performed. Therefore, the homogeneous flow properties could be achieved in the moderate solid volume fractions. A new algorithm, namely the nonequilibrium approach was introduced to show the features of self-diffusion in the granular flows. Using this algorithm a one way flow can beextracted from the entire flow, which not only provides a straightforward calculation of self-diffusion coefficient but also can qualitatively determine the deviation of self-diffusion from the linear law at some regions nearby the wall inbounded flows. Anyhow, the average lateral self-diffusion coefficient, which was calculated by the aforementioned method, showed a desirable agreement with thepredictions of kinetic theory formulation. In the continuation of computer simulation of shear granular flows, some numerical and theoretical investigations were carried out on mass transfer and particle interactions in particulate flows. In this context, the boundary element method and its combination with the spectral method using the special capabilities of wavelets have been introduced as theefficient numerical methods to solve the governing equations of mass transfer in particulate flows. A theoretical formulation of fluid dispersivity in suspension flows revealed that the fluid dispersivity depends upon the fluid properties and particle parameters as well as the fluid-particle and particle-particle interactions.

Expertise and decision making among clinicians in investigations of alleged child sexual abuse

The purpose of the present thesis was to explore different aspects of decision making and expertise in investigations of child sexual abuse (CSA) and subsequently shed some light on the reasons for shortcomings in the investigation processes. Clinicians’ subjective attitudes as well as scientifically based knowledge concerning CSA, CSA investigation and interviewing were explored. Furthermore the clinicians’ own view on their expertise and what enhances this expertise was investigated. Also, the effects of scientific knowledge, experience and attitudes on the decision making in a case of CSA were explored. Finally, the effects of different kinds of feedback as well as experience on the ability to evaluate CSA in the light of children’s behavior and base rates were investigated. Both explorative and experimental methods were used. The purpose of Study I was to investigate whether clinicians investigating child sexual abuse (CSA) rely more on scientific knowledge or on clinical experience when evaluating their own expertise. Another goal was to check what kind of beliefs the clinicians held. The connections between these different factors were investigated. A questionnaire covering items concerning demographic data, experience, knowledge about CSA, selfevaluated expertise and beliefs about CSA was given to social workers, child psychiatrists and psychologists working with children. The results showed that the clinicians relied more on their clinical experience than on scientific knowledge when evaluating their expertise as investigators of CSA. Furthermore, social workers possessed stronger attitudes in favor of children than the other groups, while child psychiatrists had more negative attitudes towards the criminal justice system. Male participants held less strong beliefs than female participants. The findings indicate that the education of CSA investigators should focus more on theoretical knowledge and decision making processes as well as the role of beliefs In Study II school and family counseling psychologists completed a Child Sexual Abuse Attitude and Belief Scale. Four CSA related attitude and belief subscales were identified: 1. The Disclosure subscale reflecting favoring a disclosure at any cost, 2. The Pro-Child subscale reflecting unconditional belief in children's reports, 3. The Intuition subscale reflecting favoring an intuitive approach to CSA investigations, and 4. The Anti Criminal Justice System subscale reflecting negative attitudes towards the legal system. Beliefs that were erroneous according to empirical research were analyzed separately. The results suggest that some psychologists hold extreme attitudes and many erroneous beliefs related to CSA. Some misconceptions are common. Female participants tended to hold stronger attitudes than male participants. The more training in interviewing children the participants have, the more erroneous beliefs and stronger attitudes they hold. Experience did not affect attitudes and beliefs. In Study III mental health professionals’ sensitivity to suggestive interviewing in CSA cases was explored. Furthermore, the effects of attitudes and beliefs related to CSA and experience with CSA investigations on the sensitivity to suggestive influences in the interview were investigated. Also, the effect of base rate estimates of CSA on decisions was examined. A questionnaire covering items concerning demographic data, different aspects of clinical experience, self-evaluated expertise, beliefs and knowledge about CSA and a set of ambiguous material based on real trial documents concerning an alleged CSA case was given to child mental health professionals. The experiment was based on a 2 x 2 x 2 x 2 (leading questions: yes vs no) x (stereotype induction: yes vs no) x (emotional tone: pressure to respond vs no pressure to respond) x (threats and rewards: yes vs no) between-subjects factorial design, in which the suggestiveness of the methods with which the responses of the child were obtained were varied. There was an additional condition in which the material did not contain any interview transcripts. The results showed that clinicians are sensitive only to the presence of leading questions but not to the presence of other suggestive techniques. Furthermore, the clinicians were not sensitive to the possibility that suggestive techniques could have been used when no interview transcripts had been included in the trial material. Experience had an effect on the sensitivity of the clinicians only regarding leading questions. Strong beliefs related to CSA lessened the sensitivity to leading questions. Those showing strong beliefs on the belief scales used in this study were even more prone to prosecute than other participants when other suggestive influences than leading questions were present. Controversy exists regarding effects of experience and feedback on clinical decision making. In Study IV the impact of the number of handled cases and of feedback on the decisions in cases of alleged CSA was investigated. One-hundred vignettes describing cases of suspected CSA were given to students with no experience with investigating CSA. The vignettes were based on statistical data about symptoms and prevalence of CSA. According to the theoretical likelihood of CSA the children described were categorized as abused or not abused. The participants were asked to decide whether abuse had occurred. They were divided into 4 groups: one received feedback on whether their decision was right or wrong, one received information about cognitive processes involved in decision making, one received both, and one did not receive feedback at all. The results showed that participants who received feedback on their performance made more correct positive decisions and participants who got information about decision making processes made more correct negative decisions. Feedback and information combined decreased the number of correct positive decisions but increased the number of correct negative decisions. The number of read cases had in itself a positive effect on correct positive decision.

Wet oxidation of recalcitrant lignin waters: Experimental and kinetic studies

The dissertation is based on four articles dealing with recalcitrant lignin water purification. Lignin, a complicated substance and recalcitrant to most treatment technologies, inhibits seriously pulp and paper industry waste management. Therefore, lignin is studied, using WO as a process method for its degradation. A special attention is paid to the improvement in biodegradability and the reduction of lignin content, since they have special importance for any following biological treatment. In most cases wet oxidation is not used as a complete ' mineralization method but as a pre treatment in order to eliminate toxic components and to reduce the high level of organics produced. The combination of wet oxidation with a biological treatment can be a good option due to its effectiveness and its relatively low technology cost. The literature part gives an overview of Advanced Oxidation Processes (AOPs). A hot oxidation process, wet oxidation (WO), is investigated in detail and is the AOP process used in the research. The background and main principles of wet oxidation, its industrial applications, the combination of wet oxidation with other water treatment technologies, principal reactions in WO, and key aspects of modelling and reaction kinetics are presented. There is also given a wood composition and lignin characterization (chemical composition, structure and origin), lignin containing waters, lignin degradation and reuse possibilities, and purification practices for lignin containing waters. The aim of the research was to investigate the effect of the operating conditions of WO, such as temperature, partial pressure of oxygen, pH and initial concentration of wastewater, on the efficiency, and to enhance the process and estimate optimal conditions for WO of recalcitrant lignin waters. Two different waters are studied (a lignin water model solution and debarking water from paper industry) to give as appropriate conditions as possible. Due to the great importance of re using and minimizing the residues of industries, further research is carried out using residual ash of an Estonian power plant as a catalyst in wet oxidation of lignin-containing water. Developing a kinetic model that includes in the prediction such parameters as TOC gives the opportunity to estimate the amount of emerging inorganic substances (degradation rate of waste) and not only the decrease of COD and BOD. The degradation target compound, lignin is included into the model through its COD value (CODligning). Such a kinetic model can be valuable in developing WO treatment processes for lignin containing waters, or other wastewaters containing one or more target compounds. In the first article, wet oxidation of "pure" lignin water was investigated as a model case with the aim of degrading lignin and enhancing water biodegradability. The experiments were performed at various temperatures (110 -190°C), partial oxygen pressures (0.5 -1.5 MPa) and pH (5, 9 and 12). The experiments showed that increasing the temperature notably improved the processes efficiency. 75% lignin reduction was detected at the lowest temperature tested and lignin removal improved to 100% at 190°C. The effect of temperature on the COD removal rate was lower, but clearly detectable. 53% of organics were oxidized at 190°C. The effect of pH occurred mostly on lignin removal. Increasing the pH enhanced the lignin removal efficiency from 60% to nearly 100%. A good biodegradability ratio (over 0.5) was generally achieved. The aim of the second article was to develop a mathematical model for "pure" lignin wet oxidation using lumped characteristics of water (COD, BOD, TOC) and lignin concentration. The model agreed well with the experimental data (R2 = 0.93 at pH 5 and 12) and concentration changes during wet oxidation followed adequately the experimental results. The model also showed correctly the trend of biodegradability (BOD/COD) changes. In the third article, the purpose of the research was to estimate optimal conditions for wet oxidation (WO) of debarking water from the paper industry. The WO experiments were' performed at various temperatures, partial oxygen pressures and pH. The experiments showed that lignin degradation and organics removal are affected remarkably by temperature and pH. 78-97% lignin reduction was detected at different WO conditions. Initial pH 12 caused faster removal of tannins/lignin content; but initial pH 5 was more effective for removal of total organics, represented by COD and TOC. Most of the decrease in organic substances concentrations occurred in the first 60 minutes. The aim of the fourth article was to compare the behaviour of two reaction kinetic models, based on experiments of wet oxidation of industrial debarking water under different conditions. The simpler model took into account only the changes in COD, BOD and TOC; the advanced model was similar to the model used in the second article. Comparing the results of the models, the second model was found to be more suitable for describing the kinetics of wet oxidation of debarking water. The significance of the reactions involved was compared on the basis of the model: for instance, lignin degraded first to other chemically oxidizable compounds rather than directly to biodegradable products. Catalytic wet oxidation of lignin containing waters is briefly presented at the end of the dissertation. Two completely different catalysts were used: a commercial Pt catalyst and waste power plant ash. CWO showed good performance using 1 g/L of residual ash gave lignin removal of 86% and COD removal of 39% at 150°C (a lower temperature and pressure than with WO). It was noted that the ash catalyst caused a remarkable removal rate for lignin degradation already during the pre heating for `zero' time, 58% of lignin was degraded. In general, wet oxidation is not recommended for use as a complete mineralization method, but as a pre treatment phase to eliminate toxic or difficultly biodegradable components and to reduce the high level of organics. Biological treatment is an appropriate post treatment method since easily biodegradable organic matter remains after the WO process. The combination of wet oxidation with subsequent biological treatment can be an effective option for the treatment of lignin containing waters.

Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis-trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair.

Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures

Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures Biocatalysis opens the door to green and sustainable processes in synthetic chemistry allowing the preparation of single enantiomers, since the enzymes are chiral and accordingly able to catalyze chemical reactions under mild conditions. Immobilization of enzymes enhances process robustness, often stabilizes and activates the enzyme, and enables reuse of the same enzyme preparation in multiple cycles. Although hundreds of variations of immobilization methods exist, there is no universal method to yield the highly active, selective and stable enzyme catalysts. Therefore, new methods need to be developed to obtain suitable catalysts for different substrates and reaction environments. Lipases are the most widely used enzymes in synthetic organic chemistry. The literature part together with the experimental part of this thesis discusses of the effects of immobilization methods mostly used to enhance lipase activity, stability and enantioselectivity. Moreover, the use of lipases in the kinetic resolution of secondary alcohols in organic solvents and in ionic liquids is discussed. The experimental work consists of the studies of immobilization of Burkholderia cepacia lipase (lipase PS) using three different methods: encapsulation in sol-gels, cross-linked enzyme aggregates (CLEAs) and supported ionic liquids enzyme catalysts (SILEs). In addition, adsorption of lipase PS on celite was studied to compare the results obtained with sol-gels, CLEAs and SILEs. The effects of immobilization on enzyme activity, enantioselectivity and hydrolysis side reactions were studied in kinetic resolution of three secondary alcohols in organic solvents, in ionic liquids (ILs), and in their mixtures. Lipase PS sol-gels were shown to be active and stable catalysts in organic solvents and solvent:IL mixtures. CLEAs and SILEs were highly active and enantioselective in organic solvents. Sol-gels and SILEs were reusable in several cycles. Hydrolysis side reaction was suppressed in the presence of sol-gels and CLEAs.

Development of racemization catalysts for dynamic kinetic resolution

Preparation of optically active compounds is of high importance in modern medicinal chemistry. Despite recent advances in the field of asymmetric synthesis, resolution of racemates still remains the most utilized way for preparation of single enantiomers in industrial scale due to its cost-efficiency and simplicity. Enzymatic kinetic resolution (KR) of racemates is a classical method for separation of enantiomers. One of its drawbacks is the limitation of target enantiomer yield to 50%. Dynamic Kinetic Resolution (DKR) allows to reach yields up to 100% by in situ racemization of the less reactive enantiomer. In the first part of this thesis, a number of half-sandwich ruthenium complexes were prepared and evaluated as catalysts for racemization of optically active secondary alcohols. A leading catalyst, Bn5CpRu(CO)2Cl, was identified. The catalyst discovered was extensively characterized by its application for DKR of a broad range of secondary alcohols in a wide range of reaction loadings (1 mmol – 1 mol). Cost-efficient chromatography-free procedure for preparation of this catalyst was developed. Further, detailed kinetic and mechanistic studies of the racemization reactions were performed. Comparison of racemization rates in the presence of Bn5CpRu(CO)2Cl and Ph5CpRu(CO)2Cl catalysts reveals that the performance of the catalytic system can be adjusted by matching of the electronic properties of the catalysts and the substrates. Moreover, dependence of the rate-limiting step from the electronic properties of the reagents was observed. Important conclusions about reaction mechanism were made. Finally, an alternative approach to DKR of amines based on space separated vessels was addressed. This procedure allows the combination of thermolabile enzyme with racemization catalysts active only at high temperatures.

How (not) to interview children : interviews with young children in sexual abuse investigations in Finland

The present thesis had two main objectives: The first was to assess how child sexual abuse (CSA) interviews in Finland are conducted through analysing the interviewing techniques applied and the language used by the interviewers, as well as to suggest ways to improve interviews if they were found to have deficiencies. The second main aim was to contribute to the growing research corpus concerning CSA interviews, in particular, by addressing how interviewers follow up information provided by the child, by analysing whether child health care professionals would use childadapted language, and by studying the kind of modifications in the verbal behaviour of interviewers and children that were associated with a) repeated interviews, b) a support person’s presence at the interview, and c) the use of anatomically detailed dolls. Two complementary samples of CSA interviews were analysed. The first one was composed of child interviews with 3-12-year-old children (N = 27) that had been considered problematic by lawyers or other involved professionals (Studies I and IV). The second sample consisted of unselected interviews (N = 43) with children aged 3 to 8 years conducted in a number of hospitals in different parts of the country (Studies II and III). Study I: The verbal interaction between interviewer and child was analysed in a sample of interviews that had been considered to be problematic by involved professionals. Results showed that interviewers used inappropriate questioning techniques, relying on option-posing, specific suggestive and unspecific suggestive questions to a significant extent, these comprising around 50% of all interviewer utterances. The proportion of invitations, which the research community recommends interviewers to rely on, was strikingly low. Invitations and directive utterances were associated with an increase in informative responses by the child in terms of response type, number of new details reported, as well as length of response. The opposite was true for option-posing and suggestive utterances. Longer questions by the interviewer (in number of words) often rendered no reply from the child, whereas shorter questions were followed by descriptive answers. Even after the child had provided an informative answer, interviewers failed to follow up the information in an adequate way and instead continued to rely on focused and leading questions. Study II: Due to the possible bias of the sample analysed in Study I, the most important analyses were rerun with the unselected sample and reported separately. Results were quite similar between the two studies, indicating that the problems observed in Study I, with interviewers relying on option-posing and suggestive questions to a significant extent, are likely to be general and not specific for those interviews. Even if suggestive questions were slightly less and invitations slightly more common in this sample than in the previous study, almost half of the interviewer questions were still optionposing or suggestive, and also in this sample, interviewers failed to follow up information by the child in a facilitating manner. Differentiating between judicial and contextual details showed that while facilitators, invitations, and directive utterances elicited more contextual than judicial details, the opposite was true for specific suggestive utterances. These results might be explained by the reluctance of children to describe sexual details related to the abuse events. Alternatively, they may also be due to children describing incorrect sexual details as a result of suggestive interviewing techniques. Study III: This study examined features of the language used by the interviewers. Interviewer utterances included multiple questions, long statements, complicated grammar and concepts, as well as unclear references to persons and situations. More than a fifth of the interviewer utterances were coded as belonging to at least one of these categories. The results suggest that even professionals who are experienced in interacting with children may have difficulties in using a child-sensitive language, adding to the pool of studies showing similar problems to occur in legal hearings with children conducted by lawyers. As children rarely comment on, or even recognise, their lack of comprehension, the use of a language that is too complex can have detrimental consequences for the outcomes of investigative interviews. Interviewers used different approaches to introduce the topic of abuse. While 15% of the children spontaneously addressed the topic of abuse, probably indicating that they felt confident with the interviewer and the situation, in almost 50% of the cases, the interviewer introduced the topic of abuse in a way that can be considered leading. Interviews were characterised by a lack of structure, apparent in frequent rapid switches of topic by the interviewer. This manner was associated with a decrease in the number of new details provided by the children. Study IV: This study analysed possible changes in the interview dynamics associated with repeated interviewing, the presence of a support person (related to the child), and the use of anatomically detailed (AD) dolls. Repeated interviewing, in combination with suggestive questions, has previously been found to seriously contaminate children’s accounts. In the present material, interviewers used significantly more suggestive utterances in the repeated condition, thus endangering the reliability of the children’s reports. Few studies have investigated the effects of a support person’s presence at the interview. The results of the present study showed that interviewers talked more and children provided less information when a support person was present. Supporting some earlier findings regarding the use of AD dolls, the present results showed that using AD dolls was associated with longer interviewer utterances and shorter, less responsive, and less detailed child responses. Interviewers used up to five times more unspecific suggestive utterances when dolls were used, for instance through repeatedly asking the child to show “what really happened” with the dolls. Conclusion: The results indicate that CSA interviews in Finland are not conducted in a manner that follows best practice as defined by the research community and as stated in a number of guidelines. When comparing these questioning strategies with the recommendations, which have been predominant in the field for more than ten years now, it can be concluded that the interviews analysed were conducted in a manner that undermines the possibility to elicit an uncontaminated and accurate narrative from the children. A particularly worrying finding was the fact that interviewers did not follow up relevant information by the children in an adequate way. A number of clinical implications can be drawn from the results, particularly concerning the need for improvement in the quality of CSA interviews. There is convincing research regarding how to improve CSA interviews, notably through training forensic child interviewers to use a structured interviewing protocol, and providing them with continuous supervision and feedback. Allocating appropriate resources to improve the quality of forensic child interviews is a matter of protecting the rights of all persons involved in CSA investigations, in particular those of the children.

On Bayesian predictive modeling : with applications on the analysis of chromatography data in forensic investigations

Med prediktion avses att man skattar det framtida värdet på en observerbar storhet. Kännetecknande för det bayesianska paradigmet är att osäkerhet gällande okända storheter uttrycks i form av sannolikheter. En bayesiansk prediktiv modell är således en sannolikhetsfördelning över de möjliga värden som en observerbar, men ännu inte observerad storhet kan anta. I de artiklar som ingår i avhandlingen utvecklas metoder, vilka bl.a. tillämpas i analys av kromatografiska data i brottsutredningar. Med undantag för den första artikeln, bygger samtliga metoder på bayesiansk prediktiv modellering. I artiklarna betraktas i huvudsak tre olika typer av problem relaterade till kromatografiska data: kvantifiering, parvis matchning och klustring. I den första artikeln utvecklas en icke-parametrisk modell för mätfel av kromatografiska analyser av alkoholhalt i blodet. I den andra artikeln utvecklas en prediktiv inferensmetod för jämförelse av två stickprov. Metoden tillämpas i den tredje artik eln för jämförelse av oljeprover i syfte att kunna identifiera den förorenande källan i samband med oljeutsläpp. I den fjärde artikeln härleds en prediktiv modell för klustring av data av blandad diskret och kontinuerlig typ, vilken bl.a. tillämpas i klassificering av amfetaminprover med avseende på produktionsomgångar.

The European Union and Assembling Biofuel Development – topological investigations concerning the associations between law, policy and space

Biofuels for transport are a renewable source of energy that were once heralded as a solution to multiple problems associated with poor urban air quality, the overproduction of agricultural commodities, the energy security of the European Union (EU) and climate change. It was only after the Union had implemented an incentivizing framework of legal and political instruments for the production, trade and consumption of biofuels that the problems of weakening food security, environmental degradation and increasing greenhouse gases through land-use changes began to unfold. In other words, the difference between political aims for why biofuels are promoted and their consequences has grown – which is also recognized by the EU policy-makers. Therefore, the global networks of producing, trading and consuming biofuels may face a complete restructure if the European Commission accomplishes its pursuit to sideline crop-based biofuels after 2020. My aim with this dissertation is not only to trace the manifold evolutions of the instruments used by the Union to govern biofuels but also to reveal how this evolution has influenced the dynamics of biofuel development. Therefore, I study the ways the EU’s legal and political instruments of steering biofuels are coconstitutive with the globalized spaces of biofuel development. My analytical strategy can be outlined through three concepts. I use the term ‘assemblage’ to approach the operations of the loose entity of actors and non-human elements that are the constituents of multi-scalar and -sectorial biofuel development. ‘Topology’ refers to the spatiality of this European biofuel assemblage and its parts whose evolving relations are treated as the active constituents of space, instead of simply being located in space. I apply the concept of ‘nomosphere’ to characterize the framework of policies, laws and other instruments that the EU applies and construes while attempting to govern biofuels. Even though both the materials and methods vary in the independent articles, these three concepts characterize my analytical strategy that allows me to study law, policy and space associated with each other. The results of my examinations underscore the importance of the instruments of governance of the EU constituting and stabilizing the spaces of producing and, on the other hand, how topological ruptures in biofuel development have enforced the need to reform policies. This analysis maps the vast scope of actors that are influenced by the mechanism of EU biofuel governance and, what is more, shows how they are actively engaging in the Union’s institutional policy formulation. By examining the consequences of fast biofuel development that are spatially dislocated from the established spaces of producing, trading and consuming biofuels such as indirect land use changes, I unfold the processes not tackled by the instruments of the EU. Indeed, it is these spatially dislocated processes that have pushed the Commission construing a new type of governing biofuels: transferring the instruments of climate change mitigation to land-use policies. Although efficient in mitigating these dislocated consequences, these instruments have also created peculiar ontological scaffolding for governing biofuels. According to this mode of governance, the spatiality of biofuel development appears to be already determined and the agency that could dampen the negative consequences originating from land-use practices is treated as irrelevant.

Emission, kinetic and magnetic phenomena in rare-earth and transition metal doped ZnSe single crystals

In this work emission, optical, electrical and magnetic properties of the d- and f- elements doped zinc selenide crystals were investigated within a wide temperature range. Doping was performed in various technological processes: during the growth by chemical vapor transport method; by thermal diffusion from the Bi or Zn melt. Concentration of the doping impurity in the crystals was controlled by amount of the dopant in the source material or by its concentration in the doping media. Special interest in the work was paid to the influence of the different concentrations of Cr and Yb impurities on ZnSe crystals’ properties, correlations between observed effects and similarities with the Ni, Mn and Gd dopants are analysed. Possibility of formation of the excitons bound to the doping d-ions was shown. In contrast to this, it was observed that f-elements do not bound excitons, but prevent formation of excitons bound to some uncontrolled impurities. A mechanism of Cr doping impurity interaction with background impurities and zinc selenide structural defects was proposed based on experimental data. An assumption about resonant energy transfer between double charged chromium ions and complexes based on crystals’ vacancy defects was made. A correlation between emission and magnetic properties of the d- ions doped samples was established. Based on this correlation a mechanism explaining the concentration quench of the emission was proposed. It was found that f-ions bind electrically active shallow and deep donor and acceptor states of background impurity to electrically neutral complexes. This may be observed as “purification” of ZnSe crystals by doping with the rare-earth elements, resulting i tendency of the properties of f-ion doped crystals to the properties of intrinsic crystals, but with smaller concentration of uncontrolled native and impurity defects. A possible interpretation of this effect was proposed. It was shown that selenium substituting impurities decrease efficiency of the Yb doping. Based on this experimental results an attempt to determine ytterbium ion surroundings in the crystal lattice was made. It was shown that co-doping of zinc selenide crystals with the d- and f- ions leads to the combination of the impurities influence on the material’s properties. On the basis of obtained data an interaction mechanism of the d- and f-elements co-dopants was proposed. Guided by the model of the ytterbium ion incorporation in the selenide sublattice of the ZnSe crystals, an assumption about stabilization of single charged chromium ions in the zinc sublattice crystal nodes, by means of formation of the local charge compensating clusters, was made.