USE OF A LOW-COST TEMPLATE-FREE ZSM-5 FOR ATMOSPHERIC PETROLEUM RESIDUE PYROLYSIS

To understand the physicochemical properties and catalytic activity during the pyrolysis of atmospheric petroleum residue, a template-free ZSM-5 zeolite was synthesized using a direct method without additional seeds or an organic structure director and compared with conventionally synthesized ZSM-5. The crystallinities of the two zeolites were evaluated by XRD and FTIR and were quite similar; however, structural analyses using SEM and argon physisorption revealed that the zeolites diverged in particle diameter and in the external surface area of the micropores. The synthesis procedure without a template incorporated additional aluminum into the crystalline network, according to ICP-AES and TPD NH3 experiments. The catalytic pyrolysis performed over the template-free ZSM-5 generated results comparable to those for pyrolysis performed over the conventional ZSM-5 according to its hydrocarbon distribution. The selectivity to aromatics compounds was exactly the same for both ZSM-5 zeolites, and these values stand out compared to thermal pyrolysis. The template-free ZSM-5 produced 20% of light hydrocarbons (C4-C6), where such compounds are olefins and paraffins of great interest to the petrochemical industry. Therefore, template-free ZSM-5 is promising for industrial use due to its lowered synthesis time, low-cost and significant distribution to light hydrocarbons.

Towards input/output-free modelling of linear infinite-dimensional systems in continuous time

This dissertation describes a networking approach to infinite-dimensional systems theory, where there is a minimal distinction between inputs and outputs. We introduce and study two closely related classes of systems, namely the state/signal systems and the port-Hamiltonian systems, and describe how they relate to each other. Some basic theory for these two classes of systems and the interconnections of such systems is provided. The main emphasis lies on passive and conservative systems, and the theoretical concepts are illustrated using the example of a lossless transfer line. Much remains to be done in this field and we point to some directions for future studies as well.

Solving Leontief Input-Output Model with Trapezoidal Fuzzy Numbers and Gauss-Seidel Algorithm

In this work a fuzzy linear system is used to solve Leontief input-output model with fuzzy entries. For solving this model, we assume that the consumption matrix from di erent sectors of the economy and demand are known. These assumptions heavily depend on the information obtained from the industries. Hence uncertainties are involved in this information. The aim of this work is to model these uncertainties and to address them by fuzzy entries such as fuzzy numbers and LR-type fuzzy numbers (triangular and trapezoidal). Fuzzy linear system has been developed using fuzzy data and it is solved using Gauss-Seidel algorithm. Numerical examples show the e ciency of this algorithm. The famous example from Prof. Leontief, where he solved the production levels for U.S. economy in 1958, is also further analyzed.

Carbon sequestration and nutrient reserves under differen t land use systems

This study evaluated the contribution of agroforestry (AFS) and traditional systems to carbon sequestration and nutrient reserves in plants, litter and soil. The study was carried out in the semiarid region of Brazil in a long-term experiment on an experimental farm of the goat and sheep section of the Brazilian Agricultural Research Corporation (Embrapa). Two agroforestry systems were investigated: agrosilvopastoral (ASP) and forest-pasture areas (SP) as well as traditional agriculture management (TM), two areas left fallow after TM (six fallow years - F6 and nine fallow years - F9) and one area of preserved Caatinga vegetation (CAT). Soil, litter and plants were sampled from all areas and the contents of C, N, P, K, Ca and Mg per compartment determined. The AFS (ASP and SP) had higher nutrient stocks than the traditional and intermediate stocks compared to the preserved Caatinga. In the ASP, a relevant part of the nutrients extracted by crops is returned to the system by constant inputs of litter, weeding of herbaceous vegetation and cutting of the legume crops. After fallow periods of six and nine years, carbon and nutrient stocks in the compartments soil, litter and herbaceous plants were similar to those of the preserved Caatinga (CAT), but still lower than under natural conditions in the woody vegetation.

Conservative nutrient use by big-leaf mahogany (Swietenia macrophylla king) planted under contrasting environmental conditions

We analyzed the nutritional composition and isotope ratios (C and N) of big-leaf mahogany (Swietenia macrophylla King) leaves in plantations established on contrasting soils and climates in Central America (State of Quintana Roo, Yucatán, México) and South America (State of Pará, Brazil). The objective was to determine the adaptability of this species to large differences in nutrient availability and rainfall regimes. Nutrient concentrations of leaves and soils were determined spectrophotometrically, and isotope ratios were measured using mass spectrometric techniques.In Pará soils were sandier, and acidic, receiving above 2000 mm of rain, whereas in Quintana Roo soils were predominantly clayey, with neutral to alkaline pH due to the underlying calcareous substrate, with about 1300 mm of rain. Leaf area/weight ratio was similar for both sites, but leaves from Quintana Roo were significantly smaller. Average N and K concentrations of adult leaves were similar, whereas Ca concentration was only slightly lower in Pará in spite of large differences in Ca availability. Leaves from this site had slightly higher P and lower Al concentrations. Differences in water use efficiency as measured by the natural abundance of 13C were negligible, the main effect of lower rainfall in Quintana Roo seemed to be a reduction in leaf area. The N isotope signature (δ15N) was more positive in Pará than in Quintana Roo, suggesting higher denitrification rates in the former. Results reveal a calciotrophic behavior and a remarkable capacity of mahogany to compensate for large differences in soil texture and nutrient availability.

Spatial variability of leaf nutrient contents in a drip irrigated citrus orchard

This study aimed to evaluate the spatial variability of leaf content of macro and micronutrients. The citrus plants orchard with 5 years of age, planted at regular intervals of 8 x 7 m, was managed under drip irrigation. Leaf samples were collected from each plant to be analyzed in the laboratory. Data were analyzed using the software R, version 2.5.1 Copyright (C) 2007, along with geostatistics package GeoR. All contents of macro and micronutrients studied were adjusted to normal distribution and showed spatial dependence.The best-fit models, based on the likelihood, for the macro and micronutrients were the spherical and matern. It is suggest for the macronutrients nitrogen, phosphorus, potassium, calcium, magnesium and sulfur the minimum distances between samples of 37; 58; 29; 63; 46 and 15 m respectively, while for the micronutrients boron, copper, iron, manganese and zinc, the distances suggests are 29; 9; 113; 35 and 14 m, respectively.

Nutrient loss in composting of agroindustrial residues

The management of composting may influence the characteristics of the produced compounds. The experiment used three frequencies of plowing, combined with the conditions: with and without coverage of the composting patio, with and without the use of commercial inoculant, resulting in 12 furrows, installed on the Experimental Center of Agricultural Engineering (NEEA), of the STATE UNIVERSITY OF WEST PARANÁ (UNIOESTE), Campus of Cascavel city - state of Paraná (PR), in Brazil. The waste and quantities used in kg were: corn cob (7.5); hatchery residue (5); floater sludge (31); ash (1); wheat cleaning residue (120); wheat pre-cleaning residue (120); corn peel (7.5); solid fraction of wash trucks used to transport chickens (2); solid fraction of pig manure (1) and coal (5), totaling 300kg of natural matter. The aim of this study was to evaluate the influence of plowings, patio coverage and inoculation in losses of N, P, K, Ca, Mg, Na, Cu, Zn, Mn, Fe. The furrows plowed three times a week in the first month showed significant higher losses of N (p<0.05). The coverage of the composting patio influenced significantly the losses of N, K, Mg and Na (p<0.05). The produced compounds had a high agronomic value in relation to macro and micronutrients. It is recommended the use of patio coverage and plowing twice a week in the first month and once a week in the subsequent months for a compound with higher concentrations of nutrients.

Sweet grape mini tomato grown in culture substrates and effluent with nutrient complementation

The objective of this study was to evaluate production of Sweet Grape mini tomato (Lycopersicum esculentum Mill.) using culture substrates and nutrient solution sewage effluent, applied by drip irrigation (fertigation). The experiment was conducted at the University of Goiás State (UEG-UnUCET), from June to November 2011 in Anápolis-GO, Brazil. The experimental design was a 2 x 3 factorial arrangement in a randomized complete block design with four repetitions. The plots were made by combining two nutrient solutions, effluent supplemented with mineral fertilizers (EcS); conventional nutrient solution (SnC); in addition three cultivation substrates: 60% of fine sand washed + 40% substrate composed by 20% coconut fiber plus 80% pine bark (S1); 20% coconut fiber and 80% pine bark (S2) and natural coconut fiber (S3). Sewage effluent were determined nitrate, calcium, potassium, manganese, total phosphate, total iron, magnesium, chloride, sulphate, boron, zinc and molybdenum. We evaluated average mass and average number of fruits per bunch, total fruit and total yield per plant. Statistical difference absence among tested solutions indicates sewage effluent can be used as an alternative source of nutrients in growing mini tomatoes in hydroponics.

Kirkkaasta sameaan : Meren kuormitus ja tila Saaristomerellä ja Ahvenanmaalla

Tässä raportissa tarkastellaan Saaristomeren ja Ahvenmaan merialueen kuormitusta ja tilaa ja niissä viime vuosikymmeninä tapahtuneita muutoksia vuosiin 2008 ja 2009 saakka. Pääpaino on ravinnekuormituksessa ja veden laadussa, mutta mukana on taustatietoa ja muun muassa katsaus kalakannoista. Saaristomeren ja Ahvenanmaan merialueen tila on heikentynyt huomattavasti viimeisten vuosikymmenten aikana. Erityisesti fosforin ja a-klorofyllin määrät ovat kasvaneet ja näkösyvyys pienenentynyt. Viimeisen kymmenen vuoden aikana pintaveden fosforipitoisuuden kasvu on laantunut suurimmassa osassa aluetta, mutta pohjanläheisessä vesikerroksessa ja talvella fosforipitoisuus on jatkanut kasvuaan monin paikoin viime vuosiin asti. Myös a-klorofyllin määrä on lisääntynyt ulko- ja välisaaristossa 2000-luvullakin. Viime vuosina klorofyllipitoisuuden kasvu on kuitenkin laantunut tai pitoisuus laskenut varsinkin rannikonläheisissä vesissä. Merialueen suurin paikallinen ravinnekuormittaja on maatalous, mutta varsinkin typpeä tulee runsaasti myös ilmalaskeumana. Sisäinen kuormitus ja virtausten mukana Suomenlahdelta ja muualta Itämereltä tulevat ravinteet heikentävät niin ikään merialueen tilaa. Muita ravinnelähteitä ovat mm. haja-asutus, jätevedenpuhdistamot ja kalankasvatus. Ahvenanmaan merialueelle ravinteita tulee enemmän muualta kuin Ahvenanmaalta. Hajakuormituksessa on tapahtunut viime vuosikymmeninä selviä vuodenaikaisia muutoksia. Vuosina 1990 – 2009 jokien mereen tuoma ravinne- ja kiintoainekuormitus on ollut talvisin ja syksyisin selvästi suurempaa kuin vuosina 1970 – 1989. Talviaikaisen kuormituksen lisääntyminen johtuu aiempaa lauhemmista talvista, ja antaa viitteitä ilmastonmuutoksen mukanaan tuomista muutoksista. Vaikka Saaristomeren ja Ahvenanmaan merialueen tilassa on ollut viime aikoina nähtävissä myönteisiäkin merkkejä, on niiden tila edelleen huolestuttava. Ainoa keino merialueen tilan parantamiseksi on kuormituksen huomattava vähentäminen. Vähentäminen koskee niin paikallisia ravinnelähteitä, erityisesti maataloutta, kuin muualta Itämereltä virtausten mukana tulevia ravinteita ja ilmalaskeumaa.

Testate amoebae (thecamoebians) as indicators of aquatic mine impact

The environmental impacts of a single mine often remain local, but acidic and metal-rich acid mine drainage (AMD) from the waste materials may pose a serious threat to adjacent surface waters and their ecosystems. Testate amoebae (thecamoebian) analysis was used together with lake sediment geochemistry to study and evaluate the ecological effects of sulphidic metal mines on aquatic environments. Three different mines were included in the study: Luikonlahti Cu-mine in Kaavi, eastern Finland, Haveri Cu-Au mine in Ylöjärvi, southern Finland and Pyhäsalmi Zn-Cu-S mine in Pyhäjärvi, central Finland. Luikonlahti and Haveri are closed mines, but Pyhäsalmi is still operating. The sampling strategy was case specific, and planned to provide a representative sediment sample series to define natural background conditions, to detect spatial and temporal variations in mine impacts, to evaluate the possible recovery after the peak contamination, and to distinguish the effects of other environmental factors from the mining impacts. In the Haveri case, diatom analyses were performed alongside thecamoebian analysis to evaluate the similarities and differences between the two proxies. The results of the analyses were investigated with multivariate methods (direct and indirect ordinations, diversity and distance measure indices). Finally, the results of each case study were harmonized, pooled, and jointly analyzed to summarize the results for this dissertation. Geochemical results showed broadly similar temporal patterns in each case. Concentrations of ions in the pre-disturbance samples defined the natural baseline against which other results were compared. The beginning of the mining activities had only minor impacts on sediment geochemistry, mainly appearing as an increased clastic input into the lakes at Haveri and Pyhäsalmi. The active mining phase was followed by the metallic contamination and, subsequently, by the most recent change towards decreased but still elevated metal concentrations in the sediments. Because of the delay in the oxidation of waste material and formation of AMD, the most intense, but transient metal contamination phase occurred in the post-mining period at Luikonlahti and Haveri. At Pyhäsalmi, the highest metal contamination preceded effluent mitigation actions. Spatial gradients were observed besides the temporal evolution in both the pre-disturbance and mine-impacted samples from Luikonlahti and Pyhäsalmi. The geochemical gradients varied with distance from the main source of contaminants (dispersion and dilution) and with water depth (redox and pH). The spatial extent of the highest metal contamination associated with these mines remained rather limited. At Haveri, the metallic impact was widespread, with the upstream site in another lake basin found to be contaminated. Changes in thecamoebian assemblages corresponded well with the geochemical results. Despite some differences, the general features and ecological responses of the faunal assemblages were rather similar in each lake. Constantly abundant strains of Difflugia oblonga, Difflugia protaeiformis and centropyxids formed the core of these assemblages. Increasing proportions of Cucurbitella tricuspis towards the surface samples were found in all of the cases. The results affirmed the indicator value of some already known indicator forms, but such as C. tricuspis and higher nutrient levels, but also elicited possible new ones such as D. oblonga ‘spinosa’ and clayey substrate, high conductivity and/or alkalinity, D. protaeiformis ‘multicornis’ and pH, water hardness and the amount of clastic material and Centropyxis constricta ‘aerophila’ and high metal and S concentrations. In each case, eutrophication appeared to be the most important environmental factor, masking the effects of other variables. Faunal responses to high metal inputs in sediments remained minor, but were nevertheless detectable. Besides the trophic state of the lake, numerical methods suggested overall geochemical conditions (pH, redox) to be the most important factor at Luikonlahti, whereas the Haveri results showed the clearest connection between metals and amoebae. At Pyhäsalmi, the strongest relationships were found between Ca- and S-rich present loading, redox conditions and substrate composition. Sediment geochemistry and testate amoeba analysis proved to be a suitable combination of methods to detect and describe the aquatic mine impacts in each specific case, to evaluate recovery and to differentiate between the effects of different anthropogenic and natural environmental factors. It was also suggested that aquatic mine impacts can be significantly mitigated by careful design and after-care of the waste facilities, especially by reducing and preventing AMD. The case-specific approach is nevertheless necessary because of the unique characteristics of each mine and variations in the environmental background conditions.

The effects of welding heat input on the usability of high strength steels in welded structures

High strength steel (HSS) has been in use in workshops since the 1980s. At that time, the significance of the term HSS differed from the modern conception as the maximum yield strength of HSSs has increased nearly every year. There are three different ways to make HSS. The first and oldest method is QT (quenched and tempered) followed by the TMCP (thermomechanical controlled process) and DQ (direct quenching) methods. This thesis consists of two parts, the first of which part introduces the research topic and discusses welded HSS structures by characterizing the most important variables. In the second part of the thesis, the usability of welded HSS structures is examined through a set of laboratory tests. The results of this study explain the differences in the usability of the welded HSSs made by the three different methods. The results additionally indicate that usage of different HSSs in the welded structures presumes that manufacturers know what kind of HSS they are welding. As manufacturers use greater strength HSSs in welded structures, the demands for welding rise as well. Therefore, during the manufacturing process, factors such as heat input, cooling time, weld quality, and more must be under careful observation.

Comparison of methods for determination of nutrient digestibility of a dry kibble diet for ocelots

In this experiment, methods of total fecal collection (TFC) and internal markers (acid-insoluble ash - AIA, crude fiber - CF, and acid-detergent fiber - ADF) were compared for determination of the coefficients of apparent digestibility (CAD) for dry matter (DM), crude protein (CP), ether extract (EE), nitrogen-free extracts (NFE), and gross energy (GE) of commercial feline dry kibble for ocelots (Leopardus pardalis). Six adult animals, weighing 12.45±1.37 kg, gradually received experimental kibble in their usual diet until the beginning of the experiment and were submitted to an adaptation period ten days prior to the collection period. CAD obtained by TFC, AIA, CF, and ADF were, respectively, 73.7, 76.83, 62.01, and 46.03% for dry matter; 81.9, 84.8, 75.8, and 63.8% for crude protein; 85, 86.7, 78.5, and 69.1% for ether extract; 78.52, 79.55, 69.11, and 53.04% for nitrogen-free extracts; and 80.5, 82.2, 71.4, and 58.4% for gross energy. The AIA method showed to be efficient in determining coefficients of apparent digestibility and may contribute to investigations on the digestibility of diets for wild felines. In comparison to the items of ocelot's usual diet, the kibble used in this paper provided an adequate nutritional supply with reduced daily costs per animal.

Application of a non isotropic turbulence model to stable atmospheric flows and dispersion over 3D topography

A non isotropic turbulence model is extended and applied to three dimensional stably stratified flows and dispersion calculations. The model is derived from the algebraic stress model (including wall proximity effects), but it retains the simplicity of the "eddy viscosity" concept of first order models. The "modified k-epsilon" is implemented in a three dimensional numerical code. Once the flow is resolved, the predicted velocity and turbulence fields are interpolated into a second grid and used to solve the concentration equation. To evaluate the model, various steady state numerical solutions are compared with small scale dispersion experiments which were conducted at the wind tunnel of Mitsubishi Heavy Industries, in Japan. Stably stratified flows and plume dispersion over three distinct idealized complex topographies (flat and hilly terrain) are studied. Vertical profiles of velocity and pollutant concentration are shown and discussed. Also, comparisons are made against the results obtained with the standard k-epsilon model.