Phosphorus saturation of Finnish soils : evaluating an easy oxalate extraction method

Selostus: Alumiini- ja rautaoksidien fosforikyllästysasteen arvioiminen suomalaisista peltomaista

Embedding, Extraction and Detection of Digital Watermark in Spectral Images

Tässä diplomityössä tutkitaan tekniikoita, joillavesileima lisätään spektrikuvaan, ja menetelmiä, joilla vesileimat tunnistetaanja havaitaan spektrikuvista. PCA (Principal Component Analysis) -algoritmia käyttäen alkuperäisten kuvien spektriulottuvuutta vähennettiin. Vesileiman lisääminen spektrikuvaan suoritettiin muunnosavaruudessa. Ehdotetun mallin mukaisesti muunnosavaruuden komponentti korvattiin vesileiman ja toisen muunnosavaruuden komponentin lineaarikombinaatiolla. Lisäyksessä käytettävää parametrijoukkoa tutkittiin. Vesileimattujen kuvien laatu mitattiin ja analysoitiin. Suositukset vesileiman lisäykseen esitettiin. Useita menetelmiä käytettiin vesileimojen tunnistamiseen ja tunnistamisen tulokset analysoitiin. Vesileimojen kyky sietää erilaisia hyökkäyksiä tarkistettiin. Diplomityössä suoritettiin joukko havaitsemis-kokeita ottamalla huomioon vesileiman lisäyksessä käytetyt parametrit. ICA (Independent Component Analysis) -menetelmää pidetään yhtenä mahdollisena vaihtoehtona vesileiman havaitsemisessa.

Local and Global Feature Extraction for Invariant Object Recognition

Perceiving the world visually is a basic act for humans, but for computers it is still an unsolved problem. The variability present innatural environments is an obstacle for effective computer vision. The goal of invariant object recognition is to recognise objects in a digital image despite variations in, for example, pose, lighting or occlusion. In this study, invariant object recognition is considered from the viewpoint of feature extraction. Thedifferences between local and global features are studied with emphasis on Hough transform and Gabor filtering based feature extraction. The methods are examined with respect to four capabilities: generality, invariance, stability, and efficiency. Invariant features are presented using both Hough transform and Gabor filtering. A modified Hough transform technique is also presented where the distortion tolerance is increased by incorporating local information. In addition, methods for decreasing the computational costs of the Hough transform employing parallel processing and local information are introduced.

On Option Price Information Content and Extraction of Implied Probability Distributions

In this study we used market settlement prices of European call options on stock index futures to extract implied probability distribution function (PDF). The method used produces a PDF of returns of an underlying asset at expiration date from implied volatility smile. With this method, the assumption of lognormal distribution (Black-Scholes model) is tested. The market view of the asset price dynamics can then be used for various purposes (hedging, speculation). We used the so called smoothing approach for implied PDF extraction presented by Shimko (1993). In our analysis we obtained implied volatility smiles from index futures markets (S&P 500 and DAX indices) and standardized them. The method introduced by Breeden and Litzenberger (1978) was then used on PDF extraction. The results show significant deviations from the assumption of lognormal returns for S&P500 options while DAX options mostly fit the lognormal distribution. A deviant subjective view of PDF can be used to form a strategy as discussed in the last section.

The Role of Surfactant Properties of Extractants in Hydrometallurgical LiquidLiquid Extraction Processes

The amphiphilic nature of metal extractants causes the formation of micelles and other microscopic aggregates when in contact with water and an organic diluent. These phenomena and their effects on metal extraction were studied using carboxylic acid (Versatic 10) and organophosphorus acid (Cyanex 272) based extractants. Special emphasis was laid on the study of phase behaviour in a pre neutralisation stage when the extractant is transformed to a sodium or ammonium salt form. The pre neutralised extractants were used to extract nickel and to separate cobalt and nickel. Phase diagrams corresponding to the pre neutralisation stage in a metal extraction process were determined. The maximal solubilisation of the components in the system water(NH3)/extractant/isooctane takes place when the molar ratio between the ammonia salt form and the free form of the extractant is 0.5 for the carboxylic acid and 1 for the organophosphorus acid extractant. These values correspond to the complex stoichiometry of NH4A•HA and NIi4A, respectively. When such a solution is contacted with water a microemulsion is formed. If the aqueous phase contains also metal ions (e.g. Ni²+), complexation will take place on the microscopic interface of the micellar aggregates. Experimental evidence showing that the initial stage of nickel extraction with pre neutralised Versatic 10 is a fast pseudohomogeneous reaction was obtained. About 90% of the metal were extracted in the first 15 s after the initial contact. For nickel extraction with pre neutralised Versatic 10 it was found that the highest metal loading and the lowest residual ammonia and water contents in the organic phase are achieved when the feeds are balanced so that the stoichiometry is 2NH4+(org) = Nit2+(aq). In the case of Co/Ni separation using pre neutralised Cyanex 272 the highest separation is achieved when the Co/extractant molar ratio in the feeds is 1 : 4 and at the same time the optimal degree of neutralisation of the Cyanex 272 is about 50%. The adsorption of the extractants on solid surfaces may cause accumulation of solid fine particles at the interface between the aqueous and organic phases in metal extraction processes. Copper extraction processes are known to suffer of this problem. Experiments were carried out using model silica and mica particles. It was found that high copper loading, aromacity of the diluent, modification agents and the presence of aqueous phase decrease the adsorption of the hydroxyoxime on silica surfaces.

Recovery of organic acids with liquid-liquid extraction contactors

Liquid-liquid extraction is a mass transfer process for recovering the desired components from the liquid streams by contacting it to non-soluble liquid solvent. Literature part of this thesis deals with theory of the liquid-liquid extraction and the main steps of the extraction process design. The experimental part of this thesis investigates the extraction of organic acids from aqueous solution. The aim was to find the optimal solvent for recovering the organic acids from aqueous solutions. The other objective was to test the selected solvent in pilot scale with packed column and compare the effectiveness of the structured and the random packing, the effect of dispersed phase selection and the effect of packing material wettability properties. Experiments showed that selected solvent works well with dilute organic acid solutions. The random packing proved to be more efficient than the structured packing due to higher hold-up of the dispersed phase. Dispersing the phase that is present in larger volume proved to more efficient. With the random packing the material that was wetted by the dispersed phase was more efficient due to higher hold-up of the dispersed phase. According the literature, the behavior is usually opposite.

Dental Health in Primary Teeth after Prevention of Mother-Child Transmission of Mutans Streptococci. A Historical Cohort Study on Restorative Visits and Maternal Prevention Costs

Mutansstreptokokkitartunnan ehkäisemisen pitkäaikaisvaikutukset maitohampaiden terveyteen. Kohorttitutkimus korjaavan hoidon määrästä ja kariesehkäisyn kustannuksista. Tutkimuksen tarkoituksena oli selvittää varhaisen mutansstreptokokki (MS)-kolonisaation ehkäisyn pitkäaikaisvaikutuksia korkean kariesriskin omaavien lasten maitohampaistossa sekä tarkastella MS-tartunnan estämisen kustannuksia. Tiedot lasten hampaiden terveydestä ja hammashoitotoimenpiteistä syntymästä 10-vuotiaaksi sekä äiteihin kohdistuneen kariesehkäisyn kustannuksista kerättiin Ylivieskan terveyskeskuksen asiakirjoista. Tutkimuksessa oli mukana yhteensä 507 lasta, heistä 148 oli osallistunut aikaisempaan Ylivieskan äiti-lapsitutkimukseen, jossa verrattiin äitien käyttämän ksylitolipurukumin ja äidille tehtyjen fluori- tai klooriheksidiinilakkausten vaikutusta pikkulasten hampaiden terveyteen. Maitohammaskariesta esiintyi 10-vuotiaaksi asti merkitsevästi vähemmän lapsilla, jotka eivät olleet saaneet MS-tartuntaa alle 2-vuotiaana, heidän maitohampaansa säilyivät 3,4 vuotta kauemmin täysin ehjinä (p<0.001) ja he tarvitsivat vähemmän maitohampaiden korjaavaa hoitoa (p=0.005) kuin lapset, joiden hampaisto oli kolonisoitunut MS-bakteerilla jo 2-vuotiaana. Koska ksylitoliryhmän lasten MS-kolonisaatio oli vähäisintä, heidän maitohampaissaan oli vähemmän kariesta ja korjaavan hoidon tarvetta kuin kahden muun korkeariskisen ryhmän lapsilla. Äitien käyttämän ksylitolipurukumin kustannukset olivat yhteensä 116 euroa ja lapsen maitohampaiden säilyminen täysin ehjinä vuoden pidempään maksoi 37 euroa. Kun MS-tartunta oli saatu estettyä, korkean kariesriskin omaavien lasten hampaiden terveys oli samalla tasolla kuin keskimäärin koko ikäkohortilla. Lapsen maitohampaat säilyvät terveinä pidempään ja korjaavan hoidon tarve vähenee, kun MS-kolonisaatio alle 2-vuotiaana saadaan estettyä. Lapsen MS-kolonisaatio vähenee merkitsevästi, kun äiti käyttää ksylitolipurukumia lapsen ollessa 0-2 vuoden ikäinen, siten pikkulapsen äidin säännöllinen ksylitolipurukumin käyttö saattaa olla julkisen tereydenhuollon kannalta tarkoituksenmukainenterveyttä edistävä menetelmä.

Rigid Rod Polymer Fillers in Acrylic Denture and Dental Adhesive Resin Systems

Polymeric materials have been used in dental applications for decades. Adhesion of polymeric materials to each other and to the tooth substrate is essential to their successful use. The aim of this series of studies was two-folded. First, to improve adhesion of poly(paraphenylene) based rigid rod polymer (RRP) to other dental polymers, and secondly, to evaluate the usability of a new dentin primer system based on RRP fillers. Poly(paraphenylene) based RRP would be a tempting material for dental applications because of its good mechanical properties. To be used in dental applications, reliable adhesion between RRP and other dental polymers is required. In this series of studies, the adhesion of RRP to denture base polymer and the mechanical properties of RRP-denture base polymer-material combination were evaluated. Also adhesion of BisGMA-TEGDMA-resin to RRP was determined. Different surface treatments were tested to improve the adhesion of BisGMA-TEGDMA-resin to RRP. Results were based on three-point bending testing, Vickers surface hardness test and scanning electron microscope analysis (SEM), which showed that no reliable adhesion between RRP and denture base polymer was formed. Addition of RRP filler to denture base polymer increased surface hardness and flexural modulus but flexural strength decreased. Results from the shear bond strength test and SEM revealed that adhesion between resin and RRP was possible to improve by surface treatment with dichloromethane (DCM) based primer and a new kind of adhesive surface can be designed. The current dentin bonding agents have good immediate bond strength, but in long term the bond strength may decrease due to the detrimental effect of water and perhaps by matrix metalloproteinases. This leads to problems in longevity of restorations. Current bonding agents use organic monomers. In this series of studies, RRP filled dentin primer was tested in order to decrease the water sorption of the monomer system of the primers. The properties of new dentin primer system were evaluated in vitro by comparing it to commercial etch and rinse adhesive system. The results from the contact angle measurements and SEM showed that experimental primer with RRP reinforcement provided similar resin infiltration to dentin collagen and formed the resin-dentin interface as the control primer. Microtensile bond strength test and SEM revealed that in short term water storing, RRP increased bond strength and primer with BMEP-monomer (bis[2-(methacryloyloxy)-ethyl]phosphate) and high solvent concentration provided comparable bonding properties to the commercial control primers. In long term water storing, the high solvent-monomer concentration of the experimental primers decreased bond strength. However, in low solvent-monomer concentration groups, the long-term water storing did not decrease the bond strength despite the existence of hydrophilic monomers which were used in the system. These studies demonstrated that new dentin primer system reached the mechanical properties of current traditional etch and rinse adhesive system in short time water storing. Improved properties can be achieved by further modifications of the monomer system. Studies of the adhesion of RRP to other polymers suggest that adhesion between RRP and other dental polymers is possible to obtain by certain surface treatments.

The Influence of Certain Processing Factors on the Durability of Yttrium Stabilized Zirconia Used As Dental Biomaterial

In dentistry, yttrium partially stabilized zirconia (ZrO2) has become one of the most attractive ceramic materials for prosthetic applications. The aim of this series of studies was to evaluate whether certain treatments used in the manufacturing process, such as sintering time, color shading or heat treatment of zirconia affect the material properties. Another aim was to evaluate the load-bearing capacity and marginal fit of manually copy-milled custom-made versus prefabricated commercially available zirconia implant abutments. Mechanical properties such as flexural strength and surface microhardness were determined for green-stage milled and sintered yttrium partially stabilized zirconia after different sintering time, coloring process and heat treatments. Scanning electron microscope (SEM) was used for analyzing the possible changes in surface structure of zirconia material after reduced sintering time, coloring and heat treatments. Possible phase change from the tetragonal to the monoclinic phase was evaluated by X-ray diffraction analysis (XRD). The load-bearing capacity of different implant abutments was measured and the fit between abutment and implant replica was examined with SEM. The results of these studies showed that the shorter sintering time or the thermocycling did not affect the strength or surface microhardness of zirconia. Coloring of zirconia decreased strength compared to un-colored control zirconia, and some of the colored zirconia specimens also showed a decrease in surface microhardness. Coloring also affected the dimensions of zirconia. Significantly decreased shrinkage was found for colored zirconia specimens during sintering. Heat treatment of zirconia did not seem to affect materials’ mechanical properties but when a thin coating of wash and glaze porcelain was fired on the tensile side of the disc the flexural strength decreased significantly. Furthermore, it was found that thermocycling increased the monoclinic phase on the surface of the zirconia. Color shading or heat treatment did not seem to affect phase transformation but small monoclinic peaks were detected on the surface of the heat treated specimens with a thin coating of wash and glaze porcelain on the opposite side. Custom-made zirconia abutments showed comparable load-bearing capacity to the prefabricated commercially available zirconia abutments. However, the fit of the custom-made abutments was less satisfactory than that of the commercially available abutments. These studies suggest that zirconia is a durable material and other treatments than color shading used in the manufacturing process of zirconia bulk material does not affect the material’s strength. The decrease in strength and dimensional changes after color shading needs to be taken into account when fabricating zirconia substructures for fixed dental prostheses. Manually copy-milled custom-made abutments have acceptable load-bearing capacity but the marginal accuracy has to be evaluated carefully.

Virtual Professional Network as a Value Creator in the Dental Business

The research of virtual professional networks has been enormous but the lack of research in the dental field was obvious. This study focuses on those uses and gratifications, and motives of participants that a virtual pro-fessional network should fulfil. The aim of this study is to understand the factors behind the successful virtual professional network, and motives of participants that support a particular business network’s building up for contributing its further success. In this study the focus is on particular mo-tives, needs and benefits of participants that are significant for the net-work’s further development. The study will explore relevant scientific research and theory that is char-acteristic in networking, and theories of user’s needs and motives. Empiri-cal data was collected from dental professionals by net based question-naire that was sent by e-mail. Data analysis was done by quantitative fac-tor analysis. The findings of this study were obvious that virtual knowledge of implantology is inadequate and knowledge is rather difficult to find in the Internet. Sharing of virtual knowledge, net-learning and communication were seen to improve the quality of impolantological professionalism and also the development of these areas was experienced essential. On the grounds of this study a host of a virtual professional network can focus on those aspects that serve the users at best, can develop professionalism in implantology and can profit in its own business operations.

Carbohydrate intake in children - associations with dietary intakes, growth, serum lipids,and dental health. The STRIP Project

This study is part of the STRIP study, which is a long-term, randomized controlled trial, designed to decrease the exposure of children in the intervention group (n=540) to known risk factors of atherosclerosis. The main focus of the intervention was the quality of dietary fat. The control group (n=522) did not receive any individualized counselling. Food consumption was evaluated with food records, and blood samples were drawn and growth was measured regularly for all participating children from 13 months to 9 years. A subsample of 66 children participated in a dental health survey. The number of studies on children’s carbohydrate intake, especially fibre intake, is insufficient. The current international recommendations for fibre intake in children are based on average assumptions and data extrapolated from intakes in adults and intake recommendations for adults. Finnish nutrition recommendations lack strict recommendations for dietary fibre in children. Due to fibre’s high bulk volume, excessive dietary fibre is considered to decrease energy density and hence it may have an adverse effect on growth. If fats are reduced from the diet, the low-fat diet may become high in sucrose. Therefore, especially in the STRIP study, it is important to determine the use of fibre and sucrose in children and possible associations with growth and nutrition as well as dental health. The results of the present study indicate that a high fibre intake does not displace energy or disturb growth in children and that children with high fibre intake have better quality of diet than those with low fibre intake. Additionally, dietary fibre intake associated inversely with serum cholesterol concentration. Other carbohydrates also affected serum lipid levels as well, since total carbohydrates, sucrose, and fructose increased serum triglyceride concentration. Total carbohydrate intake reduced HDL cholesterol concentration only in children with apoE3 or apoE4 phenotype. Over the period from the 1970s to the 1990s the dental health of children in Finland has substantially improved despite an increase in sucrose intake. The improvement was thought to be due to improved dental hygiene and the use of fluorine. However, during the past twenty years improvement in dental health has stopped. The present study showed that high long-term sugar intake increases risk of caries in children. High intake of sugar had also negative effects on the diet of children, because it worsens dietary quality by displacing essential nutrients. Furthermore, the quality of dietary fat was worse in children with high sucrose intake. In this study the children’s high sucrose intake was not associated with overweight, but interestingly, it associated inversely with growth.

Recovery of carboxylic acids from aqueous streams by extraction and back extraction

Separation of carboxylic acids from aqueous streams is an important part of their manufacturing process. The aqueous solutions are usually dilute containing less than 10 % acids. Separation by distillation is difficult as the boiling points of acids are only marginally higher than that of water. Because of this distillation is not only difficult but also expensive due to the evaporation of large amounts of water. Carboxylic acids have traditionally been precipitated as calcium salts. The yields of these processes are usually relatively low and the chemical costs high. Especially the decomposition of calcium salts with sulfuric acid produces large amounts of calcium sulfate sludge. Solvent extraction has been studied as an alternative method for recovery of carboxylic acids. Solvent extraction is based on mixing of two immiscible liquids and the transfer of the wanted components form one liquid to another due to equilibrium difference. In the case of carboxylic acids, the acids are transferred from aqueous phase to organic solvent due to physical and chemical interactions. The acids and the extractant form complexes which are soluble in the organic phase. The extraction efficiency is affected by many factors, for instance initial acid concentration, type and concentration of the extractant, pH, temperature and extraction time. In this paper, the effects of initial acid concentration, type of extractant and temperature on extraction efficiency were studied. As carboxylic acids are usually the products of the processes, they are wanted to be recovered. Hence the acids have to be removed from the organic phase after the extraction. The removal of acids from the organic phase also regenerates the extractant which can be then recycled in the process. The regeneration of the extractant was studied by back-extracting i.e. stripping the acids form the organic solution into diluent sodium hydroxide solution. In the solvent regeneration, the regenerability of different extractants and the effect of initial acid concentration and temperature were studied.

Extraction of polymeric galactoglucomannans from spruce wood by pressurized hot water

The major type of non-cellulosic polysaccharides (hemicelluloses) in softwoods, the partly acetylated galactoglucomannans (GGMs), which comprise about 15% of spruce wood, have attracted growing interest because of their potential to become high-value products with applications in many areas. The main objective of this work was to explore the possibilities to extract galactoglucomannans in native, polymeric form in high yield from spruce wood with pressurised hot-water, and to obtain a deeper understanding of the process chemistry involved. Spruce (Picea abies) chips and ground wood particles were extracted using an accelerated solvent extractor (ASE) in the temperature range 160 – 180°C. Detailed chemical analyses were done on both the water extracts and the wood residues. As much as 80 – 90% of the GGMs in spruce wood, i.e. about 13% based on the original wood, could be extracted from ground spruce wood with pure water at 170 – 180°C with an extraction time of 60 min. GGMs comprised about 75% of the extracted carbohydrates and about 60% of the total dissolved solids. Other substances in the water extracts were xylans, arabinogalactans, pectins, lignin and acetic acid. The yields from chips were only about 60% of that from ground wood. Both the GGMs and other non-cellulosic polysaccharides were extensively hydrolysed at severe extraction conditions when pH dropped to the level of 3.5. Addition of sodium bicarbonate increased the yields of polymeric GGMs at low additions, 2.5 – 5 mM, where the end pH remained around 3.9. However, at higher addition levels the yields decreased, mainly because the acetyl groups in GGMs were split off, leading to a low solubility of GGMs. Extraction with buffered water in the pH range 3.8 – 4.4 gave similar yields as with plain water, but gave a higher yield of polymeric GGMs. Moreover, at these pH levels the hydrolysis of acetyl groups in GGMs was significantly inhibited. It was concluded that hot-water extraction of polymeric GGMs in good yields (up to 8% of wood) demands appropriate control of pH, in a narrow range about 4. These results were supported by a study of hydrolysis of GGM at constant pH in the range of 3.8 – 4.2 where a kinetic model for degradation of GGM was developed. The influence of wood particle size on hot-water extraction was studied with particles in the range of 0.1 – 2 mm. The smallest particles (< 0.1 mm) gave 20 – 40% higher total yield than the coarsest particles (1.25 – 2 mm). The difference was greatest at short extraction times. The results indicated that extraction of GGMs and other polysaccharides is limited mainly by the mass transfer in the fibre wall, and for coarse wood particles also in the wood matrix. Spruce sapwood, heartwood and thermomechnical pulp were also compared, but only small differences in yields and composition of extracts were found. Two methods for isolation and purification of polymeric GGMs, i.e. membrane filtration and precipitation in ethanol-water, were compared. Filtration through a series of membranes with different pore sizes separated GGMs of different molar masses, from polymers to oligomers. Polysaccharides with molar mass higher than 4 kDa were precipitated in ethanol-water. GGMs comprised about 80% of the precipitated polysaccharides. Other polysaccharides were mainly arabinoglucuronoxylans and pectins. The ethanol-precipitated GGMs were by 13C NMR spectroscopy verified to be very similar to GGMs extracted from spruce wood in low yield at a much lower temperature, 90°C. The obtained large body of experimental data could be utilised for further kinetic and economic calculations to optimise technical hot-water extractionof softwoods.

Dental Health in Preschool and Schoolchildren in Relation to Dental Fear and Some Fear-Related Factors, and the Outcome of a Caries Prevention Program in Offspring of Fearful Mothers

Dental caries and dental fear and anxiety (DFA) are common interrelated problems but so far little is known about these problems in Estonia. The aim was to study dental health in relation to DFA, some fear-related factors, and to study the effect of a caries prevention program in children of fearful mothers. Dental health and DFA were assessed in two Estonian [2-4-year-olds (n=472) and 8-10-year-olds (n=344)], and the effect of some medical conditions on DFA in one Finnish child group [3-year-olds (n=148)]. 120 mother-child-pairs participated in the xylitol-based prevention program. Dental health was examined using the WHO or the ICDAS criteria and expressed as dmft/DMFT-indices. The modified children’s fear survey schedule dental subscale (MCFSS-DS) was used to assess DFA of schoolchildren, one single question to assess parental DFA, and the Corah’s dental anxiety scale (DAS) to assess DFA of mothers in the prevention study. Dentine caries was diagnosed in 42% of the 2-4-year-old and in 93% of the 8-10-year-old Estonian children. DFA of 8-10-year-olds (17%) was associated with experience of dental treatment, and maternal and paternal DFA. Dental apprehension at 9 years of age was associated with frequent exposure to invasive medical care. The xylitol-based prevention was successful irrespective of poor dental hygiene habits and maternal severe DFA. In conclusion, experience of operative dental treatment and DFA of Estonian children were closely associated. Invasive medical care and parental DFA were also linked to children’s DFA. Habitual use of xylitol by mothers was effective in preventing caries even in children of severely fearful mothers.