| 1. |
- Bengtsson, Åsa, 1974-
(författare)
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Solubility and Surface Complexation Studies of Apatites
- 2007
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Apatites are a diverse class of phosphate minerals that are important in a great variety of natural and industrial processes. They are, for example, used as raw material in fertiliser production and in the remediation of metal-contaminated soils. Hydroxyapatite Ca5(PO4)3OH, (HAP) and fluorapatite Ca5(PO4)3F, (FAP) are similar to the biological apatite that is the main constituent of mammalian bone and teeth, and they are therefore promising materials for artificial bone and tooth implants. This thesis is a summary of four papers with focus on dissolution and surface complexation reactions of HAP and FAP in the absence and presence of both organic ligands and the natural and commonly occurring iron oxide goethite (α-FeOOH). The dissolution and surface complexation of HAP and FAP was investigated with a combination of different techniques. Potentiometric acid/base titrations and batch experiments were combined with X-ray Photoelectron Spectroscopy (XPS) and Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) Spectroscopy to generate dissolution and surface complexation models for both apatites. The results from these studies showed that both apatites form surface layers that are different from their bulk compositions when equilibrated in aqueous solutions. The modeling efforts predicted speciation of these surfaces as well as the concentration of the dissolution products in the solution. The interaction between organic ligands and the apatite surfaces was also investigated and the results from this study show that the organic ligands form outer-sphere complexes on the apatite surfaces over a large pH interval, and that this adsorption enhances the dissolution of apatites. The presence of goethite also enhances the dissolution of FAP as it acts as a sink for the phosphate released from FAP. Phase transformation in this system was detected using ATR-FTIR as the phosphate adsorbed to the goethite surface precipitates as FePO4 (s) after approximately 15 days of reaction time. This changes the speciation, and possibly also the bioavailability of phosphate in this two-mineral system.
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| 2. |
- Lindegren, Malin, 1975-
(författare)
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Aqueous surface chemistry of Goethite : adsorption and desorption reactions involving phosphate and carboxylic acids
- 2009
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Phosphorus is an essential element for all known forms of life. In the form of phosphate, this nutrient is retained in soils and sediments by sorption on mineral particles, clays and other soil constituents. In addition, phosphate precipitates with metal ions to form a range of phosphate containing minerals, and only a minor part of phosphate is found dissolved in soil solution. One way of releasing sorbed phosphate is through ligand exchange reactions with for example carboxylic acids. This thesis summarizes five papers and focuses on the interactions of phosphate and carboxylates at the water-goethite interface. Quantitative adsorption data and spectroscopic evaluations of the surface complexation were used collectively to gain a better understanding of these processes. In agreement with previous studies, it was found that the number of carboxylic groups is important to the competitive ability of the organic acids towards phosphate. However, it was also shown that the positions of the functional groups are highly relevant to this ability. Furthermore, partially protonated species were – because of hydrogen bond interactions - shown to be more competitive than fully deprotonated equivalents. Another central finding in this work is that competitive interactions do not necessarily involve ligand-exchange reactions between inner sphere surface complexes. To study the lability of the complexes, desorption experiments were performed. Among the benzenecarboxylates, the order of increased lability matched that of the decreased ability to compete with phosphate for surface sites on the goethite. Also shown in this thesis is the ability of goethite to increase the dissolution of fluorapatite mainly through the high affinity of phosphate ions for the goethite surface.
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| 3. |
- Sundman, Ola, 1979-
(författare)
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Cation adsorption properties of substituted kraft fibres : an experimental and thermodynamic modelling study
- 2008
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Acid/base and metal ion adsorption properties have been investigated for a range of chemically modified bleached Kraft fibre materials (pulps). The studies were performed via potentiometric titrations, Flame Atomic Absorbtion (and Emission) Spectroscopy, Inductively Coupled Plasma Optical Emission Spectroscopy and Extended X-ray Absorbtion Fine Structure measurements. As a result of a chemical modification procedure, the total concentration of acidic carboxylate groups in the fibre materials ranged between 43 and 590 μmol/g. The preferable surface potential model for modelling the ionic strength dependent acid/base properties of fibre materials with low charge densities, i.e. unmodified fully bleached Kraft fibre materials, was found to be the Basic Stern Model. For fibre materials with high total charge, ≳100 μmol/g, this model resulted in poor fits to data, and for such materials a number of Constant Capacitance Models, one at each ionic strength, must be recommended. With respect to metal ion adsorption, the results have indicated that the unspecific Donnan theory could correctly model the simultaneous adsorption of several metal ions, i.e. K+, Na+, Mg2+, Ca2+ and Cu2+, provided that the salt concentration in the fibre suspension is low. In suspensions of high salt concentration it was, however, found that this very same model strongly underestimated the adsorption of Ca2+ and Cu2+. Here, the Donnan model had to be complemented by specific ion exchange equilibria. These results were corroborated by spectroscopic evidence of specific interactions between Cu2+-ions and fibres. The spectroscopic indication of a complex formed between two fibre surface carboxylate groups and one Cu2+-ion, agree with the specific ion exchange model. It was therefore concluded that specific metal ionfibre interactions cannot be neglected, especially at high salt concentrations. The interactions occurring between the polycation GaO4Al12(OH)24(H2O)127+ and fibre materials were studied by both adsorption and spectroscopic measurements. These indicate that GaO4Al12(OH)24(H2O)127+ is surprisingly stable in fibre suspensions and that intact GaO4Al12(OH)24(H2O)127+- ions are strongly adsorbed onto the fibres. Also for this ion, specific interactions has to be considered, since the strong adsorption registered was too strong to be explained by Donnan equilibria. In the thesis, the stochiometric composition and an equilibrium constant characterising these interactions is presented.
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| 4. |
- Norén, Katarina, 1978-
(författare)
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Coordination Chemistry of Monocarboxylate and Aminocarboxylate Complexes at the Water/Goethite Interface
- 2007
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis is a summary of five papers with focus on adsorption processes of various monocarboxylates and aminocarboxylates at the water/goethite interface. Interaction of organic acids at the water/mineral interfaces are of importance in biogeochemical processes, since such processes have potential to alter mobility and bioavailability of the acids and metal ions.In order to determine the coordination chemistry of acetate, benzoate, cyclohexanecarboxylate, sarcosine, MIDA (methyliminediacetic acid), EDDA (ethylenediamine-N,N’-diacetic acid) and EDTA (ethylenediamine-N,N’-tetraacetic acid) upon adsorption to the goethite (alpha-FeOOH) surface, a combination of quantitative measurements with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was utilized.Over the pH range studied here (pH 3- 9) all ligands, except for sarcosine, have been found to form surface complexes with goethite. In general, theses were characterized as outer sphere surface complexes i.e. with no direct interaction with surface Fe(III) metal ions. Furthermore, two types of different outer-sphere complexes were identified, the solvent-surface hydration-separated ion pair, and hydration-shared ion pair. For the monocarboxylate surface complexes distinction between these two could be made. At high pH values the solvent-surface hydration-separated ion pair was the predominating complex, while at low pH the surface complex is stabilized through the formation of strong hydrogen bonds with the goethite surface. However, it was not possible to clearly separate between the two outer-sphere complexes for coordination of the aminocarboxylates with the surface of goethite. Additionally, EDDA also formed an inner-sphere surface complex at high pH values. The EDDA molecule was suggested to coordinate to the surface by forming a five membered ring with an iron at the goethite surface, through the amine and carboxylate groups.Contrary to the other ligands studied, EDTA significantly induced dissolution of goethite. Some of the dissolved iron, in the form of the highly stable FeEDTA- solution complex, was indicated to re-adsorb to the mineral surface as a ternary complex. Similar ternary surface complexes were also found in the Ga(III)EDTA/goethite system, and quantitative and spectroscopic studies on adsorption of Ga(III) in presence and absence of EDTA showed that EDTA considerably effects speciation of gallium at goethite surface.The collective results in this thesis show that the affinity of these ligands for the surface of goethite is primarily governed by their chemical composition and structure, and especially important are the types, numbers and relative position of functional groups within the molecular structure.
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| 5. |
- Persson, Jonas, 1976-
(författare)
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Accurate Finite Difference Methods for Option Pricing
- 2006
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Stock options are priced numerically using space- and time-adaptive finite difference methods. European options on one and several underlying assets are considered. These are priced with adaptive numerical algorithms including a second order method and a more accurate method. For American options we use the adaptive technique to price options on one stock with and without stochastic volatility. In all these methods emphasis is put on the control of errors to fulfill predefined tolerance levels. The adaptive second order method is compared to an alternative discretization technique using radial basis functions. This method is not adaptive but shows potential in option pricing for one and several underlying assets. A finite difference method and a Monte Carlo method are applied to a new financial contract called Turbo warrant. A comparison of these two methods shows that for the case considered the finite difference method is superior.
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| 6. |
- Alenljung, Beatrice
(författare)
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Envisioning a Future Decision Support System for Requirements Engineering : A Holistic and Human-centred Perspective
- 2008
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Complex decision-making is a prominent aspect of requirements engineering (RE) and the need for improved decision support for RE decision-makers has been identified by a number of authors in the research literature. The fundamental viewpoint that permeates this thesis is that RE decision-making can be substantially improved by RE decision support systems (REDSS) based on the actual needs of RE decision-makers as well as the actual generic human decision-making activities that take place in the RE decision processes. Thus, a first step toward better decision support in requirements engineering is to understand complex decision situations of decision-makers. In order to gain a holistic view of the decision situation from a decision-maker’s perspective, a decision situation framework has been created. The framework evolved through an analysis of decision support systems literature and decision-making theories. The decision situation of RE decision-makers has been studied at a systems engineering company and is depicted in this thesis. These situations are described in terms of, for example, RE decision matters, RE decision-making activities, and RE decision processes. Factors that affect RE decision-makers are also identified. Each factor consists of problems and difficulties. Based on the empirical findings, a number of desirable characteristics of a visionary REDSS are suggested. Examples of characteristics are to reduce the cognitive load, to support creativity and idea generation, and to support decision communication. One or more guiding principles are proposed for each characteristic and available techniques are described. The purpose of the principles and techniques is to direct further efforts concerning how to find a solution that can fulfil the characteristic. Our contributions are intended to serve as a road map that can direct the efforts of researchers addressing RE decision-making and RE decision support problems. Our intention is to widen the scope and provide new lines of thought about how decision-making in RE can be supported and improved.
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| 7. |
- Doherty, Tanya, 1976-
(författare)
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HIV and Infant Feeding : Operational Challenges of Achieving Safe Infant Feeding Practices
- 2006
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis assesses the uptake of the national Prevention of Mother to Child Transmission of HIV (PMTCT) programme in South Africa, and the challenges of achieving safe infant feeding practices in the context of HIV. The research studies contained in this thesis utilised a variety of quantitative and qualitative research methods in order to provide a full understanding of the challenges of moving from efficacy to effectiveness in PMTCT programmes. The first paper utilised a cross-sectional approach to a programme evaluation, papers two and three utilised qualitative methodologies, and paper four was based on a longitudinal cohort study design. The findings highlight the low uptake of PMTCT interventions and inappropriate infant feeding choices. The experiences of women with HIV provide an important insight into the difficulties of operationalising the WHO/UNICEF HIV and infant feeding recommendations in real life settings, where rates of HIV disclosure are low and mixed feeding is the norm. Several personal and environmental characteristics were identified that contributed to success in maintaining exclusive infant feeding practices. The research provides some guidance on the definition of appropriateness in infant feeding choices, and highlights the poor outcomes associated with formula feeding under unsafe conditions. Modifying infant feeding practices is essential in order to reduce postnatal HIV transmission and improve child survival. Interventions to improve infant feeding need to include improving the quality of counselling and support provided by health workers, with more structured assessments used to guide infant feeding choices. Efforts are also needed at the community level to increase rates of disclosure and to promote exclusive infant feeding as a norm.
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| 8. |
- Henriksson, Per, 1975-
(författare)
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Sakrättsliga moment och deras ekonomiska konsekvenser
- 2009
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis is a study on the Swedish system concerning perfection of rights in rem, i.e. the requirements which must be fulfilled if a purchaser or pledgee is to become protected against third party’s rights on the seller’s or pledgor’s side. In the first part of the study the perfection requirements are analysed from a legal perspective. The study is based on eight case studies: assignment of goods; assignment of goods to consumers; assignment of real property; assignment of aircraft; security assignment of goods; security assignment of buildings; mortgage of real property; and pledge of patents. One finding is that the main purposes of the perfection requirements are to prevent fraudulent behaviour towards creditors, protect the interests of all creditors and thus promote a trustful business environment, and protect individual parties so that they engage in transactions. Another important conclusion in the first part of the study is that the economic consequences of the perfection requirements are considered when making new laws. The second part of the study is focused on analysing the economic efficiency of the Swedish perfection requirements. The general conclusion is that the current perfection requirements mostly are efficient. However, to achieve greater efficiency some main principles could be applied. To be protected against the creditors of a seller it would be more efficient with a general rule saying that a valid agreement as between the parties is sufficient. To be protected against the creditors of a pledgor it would on the other hand be more efficient with a general rule that the pledgor’s access to the property should be cut off or that the pledge is made known to the public. The conclusions is based on the assumption that protection against the rights of third party purchasers or pledgees only is achieved when the seller’s or pledgor’s access to sell or pledge the property again is cut off by a perfection requirement such as registration or delivery.
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| 9. |
- Persson, Alexander, 1978-
(författare)
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Apoptotic neutrophils enhance the immune response against Mycobacterium tuberculosis
- 2009
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Mycobacterium tuberculosis (Mtb) is the causative agent of tuberculosis, a disease that for years was considered to belong of the past, but tuberculosis is back causing over 2 million deaths per year. The infection can be dormant for decades and an active immune response can prevent the infection from progressing into active disease. However, the HIV/AIDS epidemic has caused an alarming rise in tuberculosis cases.The main infectious route for Mtb is through the airways into the lungs, where they encounter alveolar macrophages. Mtb are phagocytosed by these macrophages, but instead of being killing within the phagosome, Mtb modulates the cell to become a host in which the bacteria thrive. The lack of capacity to eradicate the infection stimulate cells of the immune system to gather around infected macrophages and form a granuloma that walls off the infection. Within this granuloma, Mtb can wait silently and later progress into active disease. However, only a fraction of exposed individuals develop disease, indicating that initial eradication of Mtb infections is possible. Such immediate response must be directed by the innate immunity comprised of phagocytes such as neutrophils (PMNs) and non-activated macrophages. Upon Mtb infection, macrophages become anergic and PMNs enter apoptosis. PMNs have a short lifespan and are cleared by neighbouring phagocytes, a mechanism described to resolve the inflammation and modulate tissue regeneration.We found that Mtb-induced apoptosis in PMNs was not dependent on phagocytosis of the bacteria, indicating that Mtb have the capacity to induce apoptosis in multiple PMNs. Complement-mediated phagocytosis induce survival signals such as Akt in PMNs, but despite this, complement-opsonized Mtb was able to override the anti-apoptotic activation in the cells. Since phagocytes clear apoptotic cells, we investigated how clearance of Mtb-induced apoptotic PMNs affected macrophages. We found that Mtb-induced apoptotic PMNs inflicted pro-inflammatory activation of the macrophages that cleared them. In addition, this activation was mediated by Hsp72 released from the Mtb-induced apoptotic PMNs. Furthermore, apoptotic PMNs can work in synergy with phagocytosed Mtb to activate macrophages and enhance intracellular killing of Mtb.Since dendritic cells are important for the regulation of immunity, we investigated whether Mtb-induced apoptotic PMNs affected the inflammatory response and maturation of dendritic cells. We found that Mtb-induced apoptotic PMNs trigger dendritic cells to enter a mature state able to activate naïve T-cell proliferation.We propose that infected apoptotic PMNs is a potent activator of the inflammatory response during infections. Taken together, PMNs not only kill their share of pathogens but also modulate other immune cells, thereby forming a link between the early innate and the adaptive immune response during microbial challenge with Mtb.
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| 10. |
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