Element speciation and behaviour in metal-rich Boreal river and estuarine systems using ultrafiltration and chemical modelling

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations, but is to a great extent determined by their chemical form. Consequently, knowledge of aqueous metal species is essential in investigating potential metal toxicity and mobility. The overall aim of this thesis is, thus, to determine the species of major and trace elements and the size distribution among the different forms (e.g. ions, molecules and mineral particles) in selected metal-enriched Boreal river and estuarine systems by utilising filtration techniques and geochemical modelling. On the basis of the spatial physicochemical patterns found, the fractionation and complexation processes of elements (mainly related to input of humic matter and pH-change) were examined. Dissolved (<1 kDa), colloidal (1 kDa-0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic carbon (OC) and 44 metals/metalloids were investigated in the extremely acidic Vörå River system and its estuary in W Finland, and in four river systems in SW Finland (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), largely affected by soil erosion and acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these investigated waters. One of the most important findings of this study is that the very large amounts of metals known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si, U and the lanthanoids) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and especially dissolved Al is expected to have acute effects on fish and other organisms, but also other potentially toxic dissolved elements (e.g. Cd, Cu, Mn and Ni) can have fatal effects on the biota in these environments. In upstream areas that are generally relatively forested (higher pH and contents of OC) fewer bioavailable elements (including Al, Cu, Ni and U) may be found due to complexation with the more abundantly occurring colloidal OC. In the rivers in SW Finland total metal concentrations were relatively high, but most of the elements occurred largely in a colloidal or particulate form and even elements expected to be very soluble (Ca, K, Mg, Na and Sr) occurred to a large extent in colloidal form. According to geochemical modelling, these patterns may only to a limited extent be explained by in-stream metal complexation/adsorption. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of AS soils, known to exist in the catchment, could be clearly distinguished in the Sirppujoki River as it had very high concentrations of a metal sequence typical of AS soils in a dissolved form (Ba, Br, Ca, Cd, Co, K, Mg, Mn, Na, Ni, Rb and Sr). In the Paimionjoki River, metal concentrations (including Ba, Cs, Fe, Hf, Pb, Rb, Si, Th, Ti, Tl and V; not typical of AS soils in the area) were high, but it was found that the main cause of this was erosion of metal bearing phyllosilicates and thus these metals occurred dominantly in less toxic colloidal and particulate fractions. In the two nearby rivers (Laajoki and Mynäjoki) there was influence of AS soils, but it was largely masked by eroded phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high background metal concentrations due to erosion. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring, or geochemical modelling based on such data, can lead to a great overestimation of the water toxicity in this environment. The potentially toxic elements that are of concern in AS soil areas will ultimately be precipitated in the recipient estuary or sea, where the acidic metalrich river water will gradually be diluted/neutralised with brackish seawater. Along such a rising pH gradient Al, Cu and U will precipitate first together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides together with elements such as Ba, Cd, Co, Cu and Ni. Iron oxides, on the contrary, are not important scavengers of metals in the estuary, they are predicted to be associated only with As and PO4.

Índice de líquido amniótico: variabilidade inter e intra-observador

Objetivo: demonstrar a variação interobservador da medida ultra-sonográfica do índice de líquido amniótico (ILA) e da medida da área dos bolsões, bem como realizar uma comparação entre estes dois parâmetros. Além disto, procurou-se estabelecer a variação intra-observador existente na medição deste índice. Métodos: foram estudados os valores do ILA, como descrito por Phelan et al.18 , de um grupo de oitenta gestantes, consideradas clinicamente normais, atendidas na Escola de Ultra-sonografia e Reciclagem Médica Ribeirão Preto e no Departamento de Ginecologia e Obstetrícia da Faculdade de Medicina de Ribeirão Preto da Universidade de São Paulo (FMRP - USP). Todas as gestantes apresentavam idade gestacional acima de 24 semanas. Deste grupo, cinqüenta pacientes submeteram-se à avaliação do ILA por cinco ultra-sonografistas diferentes, com o uso do mesmo equipamento e no mesmo período de tempo, procurando-se estabelecer a variação interobservador deste índice. Além disto, foi realizada a medida planimétrica da área por parte de dois destes cinco ultra-sonografistas escolhidos aleatoriamente, na tentativa de verificar a variação interobservador na medida da área. Outro grupo composto por trinta gestantes foi avaliado por um mesmo observador ultra-sonografista na tentativa de se realizar a avaliação da variação intra-observador na medição do ILA. Resultados: observamos uma variação interobservador significante na medição do ILA e significante na medição da área. Não obstante, a variação intra-observador na medida do ILA foi considerada não-significante. Houve uma correlação entre as medidas do ILA e da área. Conclusões: o ILA apresenta maior aplicabilidade em relação à medida da área, além da maior facilidade de obtenção.

Acantose nigricante: inter-relações metabólicas inerentes à síndrome dos ovários policísticos

OBJETIVO: Estabelecer a prevalência da acantose nigricante (AN) no contexto da síndrome dos ovários policísticos (SOP) e as respectivas associações com a obesidade, a resistência insulínica (RI), a insulinemia e a síndrome metabólica (SM).MÉTODOS: Em um estudo transversal e prospectivo, foram selecionadas cem pacientes acometidas pela SOP, diagnosticadas segundo o Consenso de Rotterdam (2003). O exame cutâneo incluiu, além da verificação da presença da AN, a presença do hirsutismo (escore ≥8) e da acne. Foram investigados os dados clínicos e bioquímicos, os fatores de risco cardiovascular que se fazem presentes na SM, como circunferência abdominal (CA), obesidade, hipertensão e os índices de HDL e triglicérides. O modelo de aferição da resistência insulínica foi realizado por meio do teste homeostatic model assessment of insulin resistance(HOMA-IR).RESULTADOS: A prevalência da AN (53%) mostrou correspondência significativa com o hirsutismo (p=0,02), o índice de massa corpórea (IMC) (p<0,01), a insulinemia basal (p<0,01), o HOMA-IR (p<0,01) e a SM (p<0,05). A SM alcançou a prevalência de 36% e associou-se significativamente apenas com a AN (p<0,01). Conquanto ausente o diabetes mellitus, sobressaem as conotações do HOMA-IR alterado (p=0,01) com a SM (p<5%) e a AN (p<0,01).CONCLUSÕES: A AN integra o quadro fenotípico grave da SOP como mais um signo previsível dos riscos da doença cardiovascular.

Pipework data in design system integration

This thesis work describes the creation of a pipework data structure for design system integration. Work is completed in pulp and paper plant delivery company with global engineering network operations in mind. User case of process design to 3D pipework design is introduced with influence of subcontracting engineering offices. Company data element list is gathered by using key person interviews and results are processed into a pipework data element list. Inter-company co-operation is completed in standardization association and common standard for pipework data elements is found. As result inter-company created pipework data element list is introduced. Further list usage, development and relations to design software vendors are evaluated.

Experimental and discrete element simulation studies of bell-less charging of blast furnace

This thesis presents an experimental study and numerical study, based on the discrete element method (DEM), of bell-less charging in the blast furnace. The numerical models are based on the microscopic interaction between the particles in the blast furnace charging process. The emphasis is put on model validation, investigating several phenomena in the charging process, and on finding factors that influence the results. The study considers and simulates size segregation in the hopper discharging process, particle flow and behavior on the chute, which is the key equipment in the charging system, using mono-size spherical particles, multi-size spheres and nonspherical particles. The behavior of the particles at the burden surface and pellet percolation into a coke layer is also studied. Small-scale experiments are used to validate the DEM models.

Trust in inter-organisational dyadic relationships

Understanding the trust in organisations and the business relationships have been an emerging trend in past years. Researchers and executives and subject matter experts in companies have recognised the importance of managing the trust in inter-organisational relationships. Further, the interest both in academia and in business has raised an interest to under-stand dyadic relationships. The objective of this thesis was to examine trust in inter-organisational and inter-personal dyadic relationships. Trust and the dyadic relationships were analysed in information technolo-gy services and outsourcing industry. Dyads were established between the supplier company operating in the industry and its customers. The empiric part of the study was carried out by an email survey that was sent to 331 respondents resulting with effective response rate of 48.7 per cent. Statistical analyses were applied to analyse the data sample. In general, results indicated reputation, trustworthiness, capability and collaboration in dyadic trust relationships. Experience grown in duration of the relationship affected the trust positively. No drastic differences in trust were recognised when comparing supplier and customer responses.

Technology park as an element of innovative infrastructure- its role in internationalization support.

The Thesis concentrates on two central terms – Technology park and the resource-based view of the organization. General attention is devoted to competencies and capabilities of organizations that operate in foreign environment. It is difficult to go abroad without any experience and support from local government, especially for small or medium company. Technology and Science parks are the main sources of competitive advantage for this kind of organizations. They provide a huge range of services as well as business consultations and financial support on different stages of companies’ development. The Thesis was made with the assistance of Technopolis Oy in Lappeenranta. During the research companies in Finland and Russia were interviewed. Based on empirical findings important capabilities for entering foreign market were identified and some recommendations for the Technology park were given.

Towards Inter-organizational Working Capital Management

Working capital is an investment which is tied up into the inventories and accounts receivable and which is released with accounts payable. Due to the current business landscape with tightened financial conditions and finance markets, organizations emphasize efficient working capital management. With efficient working capital management, a company can reduce the need of finance, free up cash, increase profitability, improve liquidity, increase the efficiency of operations, and decrease (financing) costs. From the perspective of an individual company, efficient working capital management means decreasing inventory levels by shortening the cycle time of inventories, decreasing accounts receivable by shortening the trade credit terms and effective collection procedures, and increasing the level of accounts payable by paying the suppliers later. From an inter-organizational perspective, however, working capital should not be sub-optimized by a single company but holistic view to working capital management through the supply chain should be adopted to create value and improve performance together. The purpose of this research is to take academic research as well as practical management towards inter-organizational working capital management. The thesis discusses the benefits as well as mechanisms of working capital management in the inter-organizational context and has two main objectives: (1) to examine the effect of inter-organizational working capital management on performance in the value chain context and (2) to develop models of working capital management for internal as well as inter-organizational value chains. The results of the archival research conducted in the value chain of the pulp and paper industry and the value chain of the automotive industry indicate that companies can increase relative profitability by managing working capital comprehensively by taking into account all three components, and holistically though the value chain. Companies in the value chain benefit from different strategies in working capital management depending on the position of the company in the value chain. This can be taken into account in inter-organizational working capital management. The effects of inter-organizational working capital management actions on the financing costs of working capital were studied via simulations. Simulations also show that the value chain and individual companies benefit from an inter-organizational view to working capital management. Inter-organizational working capital management actions include for example: shortening the cycle time of inventories, reducing product costs, shifting inventories, shortening payment terms, and considering the cost of capital. The thesis also provides solutions for the practical requirements for tools to control working capital. The design science part of the research introduces the adjusted cash conversion cycle (ACCC) model for internal value chains, as well as models for working capital management in the inter-organizational value chain context: the working capital management model (WCMM) and the financial cycle time model (FCTM) designed in corporation and product levels respectively. This research contributes to literature on working capital management and interorganizational accounting. The research gives a holistic, inter-organizational view to the management of working capital. It advances the knowledge in working capital management on operational level, increases knowledge in the recently risen theme of supply chainoriented, collaborative working capital management, combines management accounting research with supply chain management research, and contributes to the demand of practical inter-organizational accounting methods. In addition, the research has strong practical focus as new managerial methods are introduced.

Tunable lumped-element bandpass filters for Cognitive Radio application

In this thesis the design of bandpass filters tunable at 400 MHz – 800 MHz was under research. Microwave filters are vital components which provide frequency selectivity in wide variety of electronic systems operating at high frequencies. Due to the occurrence of multi-frequency bands communication and diverse applications of wireless devices, requirement of tunable filters exists. The one of potential implementation of frequency-agile filters is frontends and spectrum sensors in Cognitive Radio (CR). The principle of CR is to detect and operate at a particular available spectrum without interfering with the primary user’s signals. This new method allows improving the efficiency of utilizing allocated spectrum such as TV band (400 MHz – 800 MHz). The focus of this work is development of sufficiently compact, low cost tunable filters with quite narrow bandwidth using currently available lumped-element components and PCB board technology. Filter design, different topologies and methods of tuning of bandpass filters are considered in this work. As a result, three types of topologies of bandpass filter were simulated and realised. They use digitally tunable capacitors (DTCs) for adjusting central frequency at TV "white space" spectrum. Measurements revealed that schematics presented in this work have proper output response and filters are successfully tuned by DTCs.

Application of the finite element method in cold forging processes

The demand for more efficient manufacturing processes has been increasing in the last few years. The cold forging process is presented as a possible solution, because it allows the production of parts with a good surface finish and with good mechanical properties. Nevertheless, the cold forming sequence design is very empirical and it is based on the designer experience. The computational modeling of each forming process stage by the finite element method can make the sequence design faster and more efficient, decreasing the use of conventional "trial and error" methods. In this study, the application of a commercial general finite element software - ANSYS - has been applied to model a forming operation. Models have been developed to simulate the ring compression test and to simulate a basic forming operation (upsetting) that is applied in most of the cold forging parts sequences. The simulated upsetting operation is one stage of the automotive starter parts manufacturing process. Experiments have been done to obtain the stress-strain material curve, the material flow during the simulated stage, and the required forming force. These experiments provided results used as numerical model input data and as validation of model results. The comparison between experiments and numerical results confirms the developed methodology potential on die filling prediction.

An alternative finite element formulation for determination of streamlines in two-dimensional problems

It is well known that the numerical solutions of incompressible viscous flows are of great importance in Fluid Dynamics. The graphics output capabilities of their computational codes have revolutionized the communication of ideas to the non-specialist public. In general those codes include, in their hydrodynamic features, the visualization of flow streamlines - essentially a form of contour plot showing the line patterns of the flow - and the magnitudes and orientations of their velocity vectors. However, the standard finite element formulation to compute streamlines suffers from the disadvantage of requiring the determination of boundary integrals, leading to cumbersome implementations at the construction of the finite element code. In this article, we introduce an efficient way - via an alternative variational formulation - to determine the streamlines for fluid flows, which does not need the computation of contour integrals. In order to illustrate the good performance of the alternative formulation proposed, we capture the streamlines of three viscous models: Stokes, Navier-Stokes and Viscoelastic flows.

Contact with friction using the augmented Lagrangian Method: a conditional constrained minimization problem

This work presents a formulation of the contact with friction between elastic bodies. This is a non linear problem due to unilateral constraints (inter-penetration of bodies) and friction. The solution of this problem can be found using optimization concepts, modelling the problem as a constrained minimization problem. The Finite Element Method is used to construct approximation spaces. The minimization problem has the total potential energy of the elastic bodies as the objective function, the non-inter-penetration conditions are represented by inequality constraints, and equality constraints are used to deal with the friction. Due to the presence of two friction conditions (stick and slip), specific equality constraints are present or not according to the current condition. Since the Coulomb friction condition depends on the normal and tangential contact stresses related to the constraints of the problem, it is devised a conditional dependent constrained minimization problem. An Augmented Lagrangian Method for constrained minimization is employed to solve this problem. This method, when applied to a contact problem, presents Lagrange Multipliers which have the physical meaning of contact forces. This fact allows to check the friction condition at each iteration. These concepts make possible to devise a computational scheme which lead to good numerical results.

An Hp-Adaptive Hierarchical Formulation for the Boundary Element Method Applied to Elasticity in Two Dimensions

This paper presents an HP-Adaptive Procedure with Hierarchical formulation for the Boundary Element Method in 2-D Elasticity problems. Firstly, H, P and HP formulations are defined. Then, the hierarchical concept, which allows a substantial reduction in the dimension of equation system, is introduced. The error estimator used is based on the residual computation over each node inside an element. Finally, the HP strategy is defined and applied to two examples.

Estudo de competição inter e intraespecífica envolvendo Glycine max (L. ) Merril e Cyperus rotundus (L.), em condições de casa de vegetação

O presente experimento teve por objetivo estudar os efeitos da competição inter e intraespecífica envolvendo Glycine max (L.) Merril e Cyperus rotundus L. sobre as características das plantas e acúmulos de N, P, K, Ca e Mg pelas espécies envolvidas. Para tanto, estipulou-se um tratamento em que se desenvolveram três plantas de Glycine max e outro em que se desenvolveram 3 tubérculos de Cyperus rotundus por vaso. Para estudar os efeitos da competição intraespecífica, em dois outros tratamentos dobraram-se as populações por vaso. No estudo da competição interespecífica permitiu-se o desenvolvimento de três plantas de Glycine max e de três tubérculos de Cyperus rotundus num mesmo vaso. De uma maneira geral, pôde-se observar que principalmente devido às diferenças no hábito de crescimento das duas espécies, a expressão da competição inter e intraespecífica, em cada uma delas, assume aspectos distintos. No caso de Cyperus rotundus, o efeito do dobro da densidade pôde ser compensado, em parte, pela maior produção de manifestações epígeas e de tubérculos, aliados ao maior desenvolvimento dos tubérculos na menor densidade de plantio. No caso da competição interespecífica, os resultados sugerem um efeito decisivo do sombreamento de Leguminosae sobre o comportamento da Cyperaceae. Os padrões de efeitos da competição pelos nutrientes foi determinado também pelas diferenças no recrutamento dos elementos do solo pelas espécies envolvidas.

Effect of plant row spacing and herbicide use on weed aboveground biomass and corn grain yield

The use of narrow plant spacing in corn (Zea mays) has been suggested as a technological alternative to obtain grain yield increases, due to a better use of resources. The regular pattern could diminish intraspecific competition while favoring interspecific competition with weeds. The objective of this study was to analyze the effect of corn row spacing on weed aboveground biomass and corn grain yield. Field experiments were conducted during 2002/2003 and 2003/2004 growing seasons. Three corn hybrids with two-row width (0.70 and 0.35 m) were tested. A greater photosynthetic photon flux density (PPFD) interception with a lower weed aboveground dry matter in narrow row arrangement was obtained. Corn grain yield was greater in the narrow row arrangement than in the wide row spacing. This increase in grain yield was related to a better resource use that allows for a reduced interspecific competition. The use of reduced spatial arrangement appeared to be an interesting alternative to increase both the grain yield potential and corn suppressive ability against weeds in corn dryland production systems.